EP0182693B1 - Oxidant bleaching processes performed in an acid environment - Google Patents

Oxidant bleaching processes performed in an acid environment Download PDF

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Publication number
EP0182693B1
EP0182693B1 EP85402091A EP85402091A EP0182693B1 EP 0182693 B1 EP0182693 B1 EP 0182693B1 EP 85402091 A EP85402091 A EP 85402091A EP 85402091 A EP85402091 A EP 85402091A EP 0182693 B1 EP0182693 B1 EP 0182693B1
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EP
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Prior art keywords
bleaching
bath
vanadate
chlorite
hydrogen peroxide
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EP85402091A
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German (de)
French (fr)
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EP0182693A1 (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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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/0024Dyeing and bleaching in one process
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3932Inorganic compounds or complexes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

  • the present invention relates to an improvement made to the oxidative bleaching processes carried out in an acid medium, by the action of hydrogen peroxide.
  • bleaching in an alkaline medium is not suitable for certain fibers, such as synthetic fibers.
  • other desiderata can rule out the use of an alkaline medium even with fibers, such as cellulosic fibers, which are not altered in such a medium. For example, we may want to keep the natural fats of fibers of vegetable or animal origin, fats which would be saponified in an alkaline medium.
  • the Applicant has therefore looked into the problem of industrial improvement of bleaching in an acid medium, by the action of hydrogen peroxide.
  • FR-A-2 471 437 describes a process for bleaching fibrous materials using hydrogen peroxide or alkaline peroxides in the presence of a stabilizing agent chosen from chlorites of alkali and alkaline earth metals.
  • the pH of the bleaching bath can be between 4 and 13.
  • the Applicant has experimentally found that the introduction of a chlorite and a small amount of a vanadate into an aqueous and acid dilution of hydrogen peroxide makes it possible to greatly increase the whitening activity of the acid oxidizing solution and of industrially perform bleaching under good pH and temperature conditions.
  • the present invention therefore relates to a process for bleaching fibers using an acid solution of hydrogen peroxide, characterized in that the acid solution is activated using a chlorite and a vanadate chosen from vanadates of alkali metals and ammonium, present simultaneously in the acid solution, the chlorite being present in an amount of 0.1 to 10 g per liter of bath and the vanadate being present in the amount of 0.01 to 1 g per liter of bath .
  • the acid pH range of the bath can be between 3 and 6 and the temperatures between 30 and 130 ° C, preferably between 60 and 90 ° C.
  • the necessary amounts of sodium chlorite will preferably be between 1 and 4 g per liter of the bath.
  • the necessary quantities of hydrogen peroxide will depend on the peculiarities of the bleaching process; these quantities could therefore be very variable and be, for example, between 1 and 100 g / l of a 35% hydrogen peroxide solution.
  • the amounts of vanadate will preferably be between 0.1 and 0.4 g per liter of bleaching bath.
  • An unbleached cotton fabric is treated by operating comparatively in baths respectively having the following composition:
  • a fabric made up of cellulosic fibers, part of which has been dyed beforehand with reactive dyes in order to constitute a dyed fabric article, is treated in the respective bleaching baths having the following composition:
  • a fabric consisting of unbleached cotton fibers and triacetate fibers is treated in the bleaching baths below, containing dispersed dyes, in order to dye the triacetate fiber at the same time as the bleaching of the cellulosic fiber.
  • the following operating conditions are adopted: Bath ratio 1 to 10.
  • the temperature of the baths is brought to 80 ° C., this temperature is maintained for 20 minutes, then the temperature is brought to 110 ° C.
  • the sample from bath b has a weaker and duller coloration, the cellulosic fiber is not bleached and is heavily soiled by the dispersed dye.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Paper (AREA)
  • Coloring (AREA)
  • Treatment Of Fiber Materials (AREA)

Description

La présente invention concerne une amélioration apportée aux procédés de blanchiment oxydant réalisés en milieu acide, par l'action de peroxyde d'hydrogène.The present invention relates to an improvement made to the oxidative bleaching processes carried out in an acid medium, by the action of hydrogen peroxide.

On sait que l'efficacité blanchissante des dilutions de peroxyde d'hydrogène n'est pas très élevée en milieu acide et ne permet généralement pas de réaliser le blanchiment d'une fibre. C'est pour cette raison que le peroxyde d'hydrogène ou les peroxydes alcalins sont généralement utilisés en milieu alcalin.It is known that the bleaching efficiency of dilutions of hydrogen peroxide is not very high in an acid medium and generally does not allow the bleaching of a fiber. It is for this reason that hydrogen peroxide or alkaline peroxides are generally used in an alkaline medium.

Différents composés ont été préconisés pour accroître la stabilité et l'efficacité des peroxydes en milieu alcalin. L'emploi de silicates, de différents complexes de magnésium ou de divers autres sels est par exemple recommandé.Different compounds have been recommended to increase the stability and efficiency of peroxides in an alkaline medium. The use of silicates, different magnesium complexes or various other salts is for example recommended.

Cependant, le blanchiment en milieu alcalin ne convient pas à certaines fibres, telles que les fibres synthéthiques. Par ailleurs, d'autres désiderata peuvent faire écarter l'emploi d'un milieu alcalin même avec des fibres, comme les fibres cellulosiques, qui ne sont pas altérées dans un tel milieu. Par exemple, on peut vouloir conserver les graisses naturelles de fibres d'origine végétale ou animale, graisses qui seraient saponifiées en milieu alcalin.However, bleaching in an alkaline medium is not suitable for certain fibers, such as synthetic fibers. In addition, other desiderata can rule out the use of an alkaline medium even with fibers, such as cellulosic fibers, which are not altered in such a medium. For example, we may want to keep the natural fats of fibers of vegetable or animal origin, fats which would be saponified in an alkaline medium.

La demanderesse s'est donc penchée sur le problème de l'amélioration industrielle du blanchiment en milieu acide, par action de peroxyde d'hydrogène.The Applicant has therefore looked into the problem of industrial improvement of bleaching in an acid medium, by the action of hydrogen peroxide.

Des composés divers, tels que des sels métalliques dérivant par exemple du fer ou du cuivre, sont susceptibles d'accroître la vitesse de décomposition de bains de peroxyde d'hydrogène en milieu acide. Il apparaît toutefois que ce type d'activation se traduit par la libération de molécules d'oxygène, ce qui est un processus pratiquement sans effet sur le blanchiment d'une fibre et ne peut donc être retenu.Various compounds, such as metal salts deriving for example from iron or copper, are capable of increasing the rate of decomposition of hydrogen peroxide baths in acid medium. However, it appears that this type of activation results in the release of oxygen molecules, which is a process which has practically no effect on the bleaching of a fiber and therefore cannot be retained.

L'emploi de divers autres composés a également été préconisé sans cependant jamais conduire à une efficacité blanchissante suffisante pour permettre véritablement de réaliser le blanchiment en milieu acide à l'aide de peroxyde d'hydrogène.The use of various other compounds has also been recommended without, however, ever leading to sufficient bleaching efficiency to truly allow bleaching in an acid medium using hydrogen peroxide.

FR-A-2 471 437 décrit un procédé de blanchiment de matériaux fibreux à l'aide d'eau oxygénée ou de peroxydes alcalins en présence d'un agent de stabilisation choisi parmi les chlorites de métaux alcalins et alcalino-terreux. Le pH du bain de blanchiment peut se situer entre 4 et 13.FR-A-2 471 437 describes a process for bleaching fibrous materials using hydrogen peroxide or alkaline peroxides in the presence of a stabilizing agent chosen from chlorites of alkali and alkaline earth metals. The pH of the bleaching bath can be between 4 and 13.

La demanderesse a trouvé expérimentalement que l'introduction d'un chlorite et d'une faible quantité d'un vanadate dans une dilution aqueuse et acide de peroxyde d'hydrogène permet d'accroître fortement l'activité blanchissante de la solution oxydante acide et de réaliser industriellement le blanchiment dans de bonnes conditions de pH et de temperature.The Applicant has experimentally found that the introduction of a chlorite and a small amount of a vanadate into an aqueous and acid dilution of hydrogen peroxide makes it possible to greatly increase the whitening activity of the acid oxidizing solution and of industrially perform bleaching under good pH and temperature conditions.

L'emploi de chlorite de sodium seul, sans vanadate, dans la solution acide de peroxyde d'hydrogène, ne permet pas d'accroître suffisamment l'activité blanchissante du milieu oxydant. Si l'on peut dans ce cas observer une amélioration de l'effet blanchissant, cette amélioration ne se manifeste cependant que d'une façon modérée et à la condition de réaliser le blanchiment à des températures relativement élevées de l'ordre de 120 à 130°C. Comparativement, la présence de vanadate permet d'enregistrer une efficacité nettement plus importante du pouvoir blanchissant, et ce, dans un domaine de température nettement plus acceptable, l'efficacité se manifestant déjà à partir de 40° C.The use of sodium chlorite alone, without vanadate, in the acid solution of hydrogen peroxide, does not make it possible to sufficiently increase the whitening activity of the oxidizing medium. If an improvement in the whitening effect can be observed in this case, this improvement only manifests itself in a moderate manner and on condition that the bleaching is carried out at relatively high temperatures of the order of 120 to 130 ° C. Comparatively, the presence of vanadate makes it possible to record a significantly greater efficiency of the whitening power, and this, in a clearly more acceptable temperature range, the effectiveness already manifesting from 40 ° C.

De plus, il devient possible, comme l'a observé la demanderesse, de réaliser au cours d'une même opération, à la fois, le blanchiment et la teinture des fibres, en particulier des fibres de synthèse, dont la teinture s'effectue généralement dans un domaine de pH acide.In addition, it becomes possible, as observed by the applicant, to carry out, during the same operation, both bleaching and dyeing of fibers, in particular synthetic fibers, the dyeing of which takes place. generally in an acid pH range.

Divers autres avantages sont également offerts, tels que la possibilité de blanchir en milieu acide des articles tissés teints, en évitant le risque d'altération des divers coloris, ou la possibilité de réaliser le désencollage enzymatique au cours du processus de blanchiment, en éliminant, de façon économique, les produits d'encollage.Various other advantages are also offered, such as the possibility of bleaching dyed woven articles in an acid medium, avoiding the risk of alteration of the various colors, or the possibility of carrying out enzymatic desizing during the bleaching process, by eliminating, economically, sizing products.

La présente invention a donc pour objet un procédé de blanchiment de fibres au moyen d'une solution acide de peroxyde d'hydrogène, caractérisé en ce que la solution acide est activée au moyen d'un chlorite et d'un vanadate choisi parmi les vanadates de métaux alcalins et d'ammonium, présents simultanément dans la solution acide, le chlorite étant présent à raison de 0,1 à 10 g par litre de bain et le vanadate étant présent à raison de 0,01 à 1 g par litre de bain.The present invention therefore relates to a process for bleaching fibers using an acid solution of hydrogen peroxide, characterized in that the acid solution is activated using a chlorite and a vanadate chosen from vanadates of alkali metals and ammonium, present simultaneously in the acid solution, the chlorite being present in an amount of 0.1 to 10 g per liter of bath and the vanadate being present in the amount of 0.01 to 1 g per liter of bath .

Le domaine de pH acide du bain peut être compris entre 3 et 6 et les températures entre 30 et 130° C, de préférence entre 60 et 90° C.The acid pH range of the bath can be between 3 and 6 and the temperatures between 30 and 130 ° C, preferably between 60 and 90 ° C.

La préférence sera donnée parmi les chlorites, à l'emploi du chlorite de sodium. Les quantités nécessaires de chlorite de sodium seront comprises de préférence entre 1 et 4 g par litre du bain.Preference will be given among chlorites, to the use of sodium chlorite. The necessary amounts of sodium chlorite will preferably be between 1 and 4 g per liter of the bath.

Les quantités nécessaires de peroxyde d'hydrogène seront fonction des particularités du procédé de blanchiment; ces quantités pourront donc être très variables et se situer, par exemple, entre 1 et 100 g/I d'une solution de peroxyde d'hydrogène à 35 %.The necessary quantities of hydrogen peroxide will depend on the peculiarities of the bleaching process; these quantities could therefore be very variable and be, for example, between 1 and 100 g / l of a 35% hydrogen peroxide solution.

Les quantités de vanadate seront comprises, de préférence, entre 0,1 et 0,4 g par litre de bain de blanchiment.The amounts of vanadate will preferably be between 0.1 and 0.4 g per liter of bleaching bath.

Le procédé de l'invention permet de bénéficier d'avantages importants dans la préparation et la teinture des différentes fibres. Parmi ces avantages, on peut notamment retenir:

  • - La possibilité de blanchir à l'aide de peroxyde d'hydrogène l'ensemble des différentes fibres qui sont particulièrement sensibles au milieu alcalin, comme par exemple les fibres synthétiques.
  • - La possibilité de blanchir des articles tissés teints sans risque de dégradation des divers coloris.
  • - La réalisation simultanée du blanchiment et de la teinture.
  • - La réalisation d'un désencollage enzymatique au cours du procédé de blanchiment.
The process of the invention makes it possible to benefit from significant advantages in the preparation and dyeing of the different fibers. Among these advantages, we can notably note:
  • - The possibility of bleaching using hydrogen peroxide all the different fibers which are particularly sensitive to the alkaline medium, such as for example synthetic fibers.
  • - The possibility of bleaching dyed woven articles without risk of degradation of the various colors.
  • - Simultaneous bleaching and dyeing.
  • - Carrying out an enzymatic desizing during the bleaching process.

Les exemples suivants donnés à titre indicatif et non limitatifs permettront d'illustrer de façon plus concrète les possibilités offertes par la présente invention.The following examples, given by way of indication and without limitation, will illustrate the possibilities offered by the present invention in a more concrete manner.

EXEMPLE 1:EXAMPLE 1:

On traite un tissu de coton écru en opérant comparativement dans des bains ayant respectivement la composition suivante:

Figure imgb0001
An unbleached cotton fabric is treated by operating comparatively in baths respectively having the following composition:
Figure imgb0001

On adopte dans tous les cas les conditions suivantes:

  • Rapport de bain 1 à 10 - (entre le poids de fibre et le volume de bain)
  • Température 90° C
  • Durée 60 minutes.
Après traitement, on rince puis sèche les différents échantillons.The following conditions are adopted in all cases:
  • Bath ratio 1 to 10 - (between fiber weight and bath volume)
  • Temperature 90 ° C
  • Duration 60 minutes.
After treatment, the various samples are rinsed and then dried.

On observe que l'échantillon blanchi dans le bain c présente un niveau de blancheur nettement plus élevé que celui des échantillons issus des autres bains avec en outre une bonne élimination des coques de la fibre. La détermination du degré de blancheur permet d'enregistrer les résultats suivants:

  • Bain = degré de blanc de l'échantillon = 71 %
  • Bain b = degré de blanc de l'échantillon = 74 %
  • Bain c = degré de blanc de l'échantillon = 81 %
  • Bain d = degré de blanc de l'échantillon = 72 %.
It is observed that the sample bleached in bath c has a significantly higher whiteness level than that of samples from other baths with, in addition, good elimination of the shells of the fiber. The determination of the degree of whiteness makes it possible to record the following results:
  • Bath = degree of white of the sample = 71%
  • Bath b = degree of white in the sample = 74%
  • Bath c = degree of white in the sample = 81%
  • Bath d = degree of white of the sample = 72%.

Exemple 2:Example 2:

Un tissu constitué de fibres cellulosiques dont une partie a été préalablement teinte à l'aide de colorants réactifs afin de constituer un article tissu teint, est traité dans les bains de blanchiment respectifs ayant la composition suivante:

Figure imgb0002
A fabric made up of cellulosic fibers, part of which has been dyed beforehand with reactive dyes in order to constitute a dyed fabric article, is treated in the respective bleaching baths having the following composition:
Figure imgb0002

On adopte les conditions opératoires suivantes:

  • Rapport de bain 1 à 10
  • Durée 1 heure
  • Température 80° C.
The following operating conditions are adopted:
  • Bath ratio 1 to 10
  • Duration 1 hour
  • Temperature 80 ° C.

On rince après traitement puis on sèche. On observe les résultats suivants pour les échantillons issus des divers bains:

Figure imgb0003
Rinse after treatment and then dry. The following results are observed for the samples from the various baths:
Figure imgb0003

Exemple 3:Example 3:

On traite un tissu constitué de fibres de coton écru et de fibres de triacétate dans les bains de blanchiment ci-dessous, additionnés de colorants dispersés, afin de réaliser la teinture de la fibre de triacétate en même temps que le blanchiment de la fibre cellulosique.

Figure imgb0004
On adopte les conditions opératoires suivantes: Rapport de bain 1 à 10.A fabric consisting of unbleached cotton fibers and triacetate fibers is treated in the bleaching baths below, containing dispersed dyes, in order to dye the triacetate fiber at the same time as the bleaching of the cellulosic fiber.
Figure imgb0004
The following operating conditions are adopted: Bath ratio 1 to 10.

On porte la température des bains à 80° C, maintient cette température pendant 20 minutes, puis porte la température à 110°C.The temperature of the baths is brought to 80 ° C., this temperature is maintained for 20 minutes, then the temperature is brought to 110 ° C.

On maintient une température de 110°C pendant 30 minutes, refroidit puis rince la matière teinte.Maintaining a temperature of 110 ° C for 30 minutes, cooling and then rinsing the dyed material.

Après teinture, on observe sur l'échantillon issu du bain a un excellent coloris sur la partie triacétate avec une fibre de coton blanchie et très peu salie par le colorant disperse.After dyeing, we observe on the sample from the bath an excellent color on the triacetate part with a cotton fiber bleached and very little soiled by the disperse dye.

Comparativement, l'échantillon issu du bain b possède une coloration plus faible et plus terne, la fibre cellulosique n'est pas blanchie et se trouve fortement salie par le colorant dispersé.Comparatively, the sample from bath b has a weaker and duller coloration, the cellulosic fiber is not bleached and is heavily soiled by the dispersed dye.

Exemple 4:Example 4:

On traite un tissu de coton écru et encollé de la façon suivante:

  • On imprègne ce tissu par foulardage dans un bain ayant la composition suivante:
    Figure imgb0005
  • On exprime après imprégnation de façon à maintenir 90 % du bain d'imprégnation, met en rouleau puis porte ce rouleau dans une chambre de vaporisage pendant 90 minutes à la température de 80° C.
  • On rince après traitement puis sèche le tissu obtenu..
  • On observe après traitement un degré de blanc moyen avec une bonne élimination des coques de la fibre. On constate également un excellent désencollage de l'article blanchi qui correspond ainsi à un tissu parfaitement préparé pour subir toute autre opération de teinture ou finissage.
We treat an unbleached and glued cotton fabric as follows:
  • This fabric is impregnated by padding in a bath having the following composition:
    Figure imgb0005
  • It is expressed after impregnation so as to maintain 90% of the impregnation bath, rolls up and then carries this roll in a vaporization chamber for 90 minutes at a temperature of 80 ° C.
  • Rinse after treatment and then dry the fabric obtained.
  • After treatment, an average degree of white is observed, with good elimination of the fiber shells. There is also an excellent desizing of the bleached article which thus corresponds to a fabric perfectly prepared for undergoing any other dyeing or finishing operation.

Claims (7)

1. A process for bleaching fibers by means of an acid hydrogen peroxide solution, characterized in that the acid solution is activated with a chlorite and a vanadate selected among alkaline metal vanadates and ammonium vanadate, which are simultaneously present in the acid solution, the amount of chlorite being between 0.1 and 10 g/I of bath and the amount of vanadate being between 0.01 and 1 g of vanadate per liter of bath.
2. A process as claimed in claim 1, characterized in that the acid solution has a pH of between 3 and 6.
3. A process as claimed in claims 1 or 2, characterized in that the chlorite is sodium chlorite.
4. A process as claimed in claim 1, characterized in that the amount of vanadate is between 0.1 and 0.4 g/I.
5. A process as claimed in claim 1, characterized in that the amount of chlorite is between 1 and 4 g/I.
6. A process as claimed in any of claims 1 to 5, characterized in that the bleaching is carried out at a temperature of between 30 and 1300 C.
7. A process as claimed in claim 6, characterized in that the temperature is between 60 and 90° C
EP85402091A 1984-10-31 1985-10-30 Oxidant bleaching processes performed in an acid environment Expired EP0182693B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8416682A FR2572430B1 (en) 1984-10-31 1984-10-31 IMPROVEMENT IN OXIDIZING BLEACHING PROCESSES CARRIED OUT IN AN ACID MEDIUM.
FR8416682 1984-10-31

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EP0182693A1 EP0182693A1 (en) 1986-05-28
EP0182693B1 true EP0182693B1 (en) 1988-08-31

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EP (1) EP0182693B1 (en)
JP (1) JPS61502265A (en)
DE (1) DE3564713D1 (en)
FR (1) FR2572430B1 (en)
WO (1) WO1986002674A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19530786A1 (en) * 1995-08-22 1997-02-27 Hoechst Ag A bleaching composition containing polyoxometalates as a bleach catalyst
DE19942224A1 (en) * 1999-09-03 2001-03-08 Henkel Kgaa Use of transition metal complex compounds to enhance the bleaching effect of peroxygen compounds in acidic systems

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2471437A1 (en) * 1979-12-14 1981-06-19 Protex Manuf Prod Chimiq Bleaching of fibrous material by oxidn. - using hydrogen peroxide or alkali metal peroxide stabilised with an alkali(ne earth) chlorite

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FR2572430A1 (en) 1986-05-02
JPS61502265A (en) 1986-10-09
WO1986002674A1 (en) 1986-05-09
JPS6339704B2 (en) 1988-08-08
DE3564713D1 (en) 1988-10-06
EP0182693A1 (en) 1986-05-28
FR2572430B1 (en) 1987-01-23

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