[go: up one dir, main page]

EP0165115A1 - Detergent composition for bleaching by photoactivation and process for its use - Google Patents

Detergent composition for bleaching by photoactivation and process for its use Download PDF

Info

Publication number
EP0165115A1
EP0165115A1 EP85400885A EP85400885A EP0165115A1 EP 0165115 A1 EP0165115 A1 EP 0165115A1 EP 85400885 A EP85400885 A EP 85400885A EP 85400885 A EP85400885 A EP 85400885A EP 0165115 A1 EP0165115 A1 EP 0165115A1
Authority
EP
European Patent Office
Prior art keywords
composition according
textile
additive
detergent
bleaching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85400885A
Other languages
German (de)
French (fr)
Other versions
EP0165115B1 (en
Inventor
Frédéric Ricchiero
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Rhone Poulenc Chimie de Base SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR8407469A external-priority patent/FR2564481B1/en
Priority claimed from FR8505124A external-priority patent/FR2579989A2/en
Priority claimed from FR8505126A external-priority patent/FR2579990A1/en
Application filed by Rhone Poulenc Chimie SA, Rhone Poulenc Chimie de Base SA filed Critical Rhone Poulenc Chimie SA
Priority to AT85400885T priority Critical patent/ATE30243T1/en
Publication of EP0165115A1 publication Critical patent/EP0165115A1/en
Application granted granted Critical
Publication of EP0165115B1 publication Critical patent/EP0165115B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds

Definitions

  • the present invention relates to a detergent composition for photoactivation bleaching and its method of use.
  • bleaching is understood to mean the elimination of colored stains or stains resistant to the action of the alkaline aqueous medium and of the detergents present in the usual detergents. In addition to this bleaching action, bleaching also includes a disinfectant or antiseptic action in the detergent bath.
  • bleaching is obtained in particular by the addition of perborate to the washing medium.
  • the washing must be carried out at a temperature of 80 to 90 ° C.
  • Sodium hypochlorite can also be used in a cold wash.
  • such a product causes significant deterioration of the fibers.
  • the object of the invention is therefore a bleaching system by photoactivation, which is simple to use, which is effective with respect to soiling while respecting the treated fiber as well as possible, and involving a sensitizer, adsorption on the fiber is completely reversible on rinsing.
  • the detergent composition according to the invention is characterized in that it contains, as a bleaching system by photoactivation, at least one sensitizing agent consisting of a soluble salt or disel of an acid of general formula: in which the hydrogen atoms carried by carbons 1 to 8 may or may not be substituted, in particular by halogens; and an additive of the cyclic tertiary mono, di- or tetramine type.
  • a product belonging to the family of xanthene dyes and more specifically of the fluorescein type is used. As indicated above, these products correspond to the water-soluble salts or disels of the acid of formula (1):
  • the salts will generally be the sodium or potassium salts or disels.
  • the hydrogen atoms carried by the carbons identified 1 to 8 can be substituted in particular by atoms of Cl, Br and I.
  • the products which are particularly suitable for the composition of the invention are those which, corresponding to formula 1, have the property of being adsorbed on the fiber in a reversible manner.
  • they have an absorption spectrum located substantially in the visible light range, that is to say between 400 and 800 nm, more precisely between 400 and 600 nm.
  • M can be an alkali or alkaline earth metal.
  • 1,2-dibromo fluorescein that is to say the dibromo salt or disel of formula 1, 3,4-dibromo fluorescein, ie phloxine tetrabromo-1,2,3,4 tetrachloro-5,6,7,8 fluorescein, diodo-1,2 fluoresceine, diodo-3,4 fluoresceine and tetraiodo-1,2,3,4 têtrachloro-5 , 6,7,8 fluorescein or "Rose Bengal”.
  • 1,2-dibromo fluorescein that is to say the dibromo salt or disel of formula 1, 3,4-dibromo fluorescein, ie phloxine tetrabromo-1,2,3,4 tetrachloro-5,6,7,8 fluorescein, diodo-1,2 fluoresceine, diodo-3,4 fluoresceine and tetraiodo
  • compositions comprising a combination of several sensitizing agents of the type described above.
  • the bleaching system of the invention comprises an additive which, as indicated above, is chosen from the group of cyclic tertiary mono-, di- or tetramines.
  • an additive which, as indicated above, is chosen from the group of cyclic tertiary mono-, di- or tetramines.
  • amines of the above type are used but which are also bridged; by this is meant the amines in which a nitrogen atom is linked transversely to another nitrogen atom or to a carbon atom of the ring.
  • DABCO 1,4 diaza bicyclo - (2,2,2) octane
  • ABCO quinuclidine
  • Another interesting additive is hexamethylenetetramine.
  • Bleaching systems comprising products of the type defined above can be incorporated into a solid or liquid detergent composition.
  • this detergent composition may include a surfactant. It is preferable that this surfactant is anionic or, if a mixture of surfactants is used that there is in this mixture at least one anionic surfactant. Mention may be made, for example, as anionic surfactants which can be used in the context of the invention, of the water-soluble salts of alkyl sulphate.
  • composition may also include a base or "builder" of known type such as, for example, phosphates or polyphosphates of alkali metals soluble in water or else silicates.
  • a base or "builder” of known type such as, for example, phosphates or polyphosphates of alkali metals soluble in water or else silicates.
  • the composition may include any known additive of the arti-nousse type, anti-redepositing, perfumes for example.
  • the proportions of the various constituents of the detergent composition will be chosen such that once the composition has dissolved in the detergent bath, the concentration of sensitizer and in particular of eosin is between approximately 10 -6 M and 10 -5 M. Preferably, this concentration should be located around 2.5 and 10.10 -6 M. For higher values, the sensitizer in too large a quantity can have an internal filtering effect which is detrimental to photoactivation during irradiation of the bath. detergent.
  • the concentration of each sensitizer remains in the range fixed above.
  • the additive concentration must be between 10 M and 10 -1 M. Below 10 -3 M there is no effect. Beyond 10 -1 M, there is no significant gain in money laundering. Preferably, this concentration is located around 10 -2 M.
  • the constituents of the detergent composition will preferably be chosen so that the pH of the detergent bath is between 9 and 11.
  • compositions of the invention can be used in an extremely simple manner.
  • the textile to be treated is first immersed in a detergent bath containing the composition according to the invention.
  • the textile is kept there with stirring at room temperature and in the dark or in ambient light to allow the deposition of the sensitizer.
  • the detergent bath and the textile which is contained there are asleep to a light irradiation in the visible range (400 - 800nm) resulting for example from a halogen quartz lamp.
  • This irradiation can last between 10 and 60 minutes, generally between 10 and 30 minutes. Generally during this irradiation, the temperature of the detergent bath is kept close to ambient.
  • the bath is separated from the textile and the latter is then rinsed with water for a few minutes to remove the sensitizer.
  • a washing bath comprising 3.1 g / l of builder, SDS: 0.1 M, eosin: 0.5.10 -5 M, DABCO: 10 -2 M, pH: 10.6.
  • the dyed strips are finally dried with hot air, ironed between two sheets of filter paper and cut into test pieces.
  • the specimens having a homogeneous dye are selected and stored in the dark.
  • a sample of stained cotton fabric prepared in the above manner and of known reflectance is then introduced into the washing bath and kept under stirring, at room temperature and in the dark, to allow the deposition of eosin.
  • the detergent bath containing the fabric is then irradiated.
  • the light irradiation is ensured by a HEDLER projector type "DE LUXE 2000" equipped with a quartz - halogen lamp 1000 w (CSRAM - HALOGEN SUPERPHOT).
  • the distance between the surface of the detergent bath and the lamp is approximately 30 cm.
  • the irradiation lasts 60 min.
  • the temperature of the detergent bath is maintained at around 25 ° C.
  • the samples are rinsed for 1 hour in 600 ml of permuted water protected from light and then dried between those sheets of filter paper.
  • Example 2 The procedure is the same as in Example 1 with a cotton fabric stained with wine (standard soiling EMPA 114).
  • the irradiation lasts 30 minutes.
  • a washing bath comprising 3.1 g / l of builder, SDS: 0, M, eosin: 0.8 10 -5 M, HMTA: 10 -2 M, p H: 9.8.
  • the irradiation lasts 10 minutes.
  • a washing bath comprising 3.1 g / l of builder, SDS: 0.1 M, respective concentration for each sensitizer: 10 -5 M, DABCO: 10 -2 M.
  • the samples are prepared, washed and analyzed as described in Example 1. However, the irradiation is 20 minutes.
  • a whitening effect greater or close to that obtained with a system with a single sensitizer (as in the case of Examples 2 or 3) is obtained for the same soiling with a shorter irradiation time.
  • Example 2 The procedure is the same as in Example 1 on the same soiling (NESTEA).
  • the sensitizer concentration is 10 -5 M.
  • the irradiation is 30 minutes.
  • the system of the invention provides a bleaching of the same order of magnitude, or even greater than that obtained with a perborate system, with a washing time less in some cases for the wine in particular, and in all cases at a much lower temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une composition détergente contenant un système de blanchiment par photoactivation. Ce système est caractérisé par ce qu'il est constitué d'un agent sensibilisateur appartenent à la famille des colorant xanthéniques du type de la fluoroesceine et d'une mono-, di- ou tétramine tertiaire cyclique.The invention relates to a detergent composition containing a photoactivation bleaching system. This system is characterized by the fact that it consists of a sensitizing agent belonging to the family of xanthene dyes of the fluoroescein type and of a cyclic tertiary mono-, di- or tetramine.

Description

La présente invention concerne une composition détergente pour le blanchiment par photoactivation et son procédé d'utilisation.The present invention relates to a detergent composition for photoactivation bleaching and its method of use.

Au cours d'un cycle de lavage, on entend par blanchiment l'élimination des taches ou salissures colorées résistant à l'action du milieu aqueux alcalin et des détergents présents dans les lessives habituelles. Outre cette action décolorante, le blanchiment inclut aussi une action désinfectante ou antiseptique du bain lessiviel.During a washing cycle, the term “bleaching” is understood to mean the elimination of colored stains or stains resistant to the action of the alkaline aqueous medium and of the detergents present in the usual detergents. In addition to this bleaching action, bleaching also includes a disinfectant or antiseptic action in the detergent bath.

A l'heure actuelle, le blanchiment est obtenu notamment par l'addition de perborate au milieu lessiviel. Cependant dans un tel cas le lavage doit être effectué à une température de 80 à 90°C. On peut aussi utiliser l'hypochlorite de sodium dans un lavage à froid. Toutefois, un tel produit entraîne une détérioration non négligeable des fibres.At present, bleaching is obtained in particular by the addition of perborate to the washing medium. However in such a case the washing must be carried out at a temperature of 80 to 90 ° C. Sodium hypochlorite can also be used in a cold wash. However, such a product causes significant deterioration of the fibers.

Le besoin s'est donc fait sentir d'un système de blanchiment pouvant être employé à une température basse, proche de l'ambiante et sans dommage pour la fibre lavée.There has therefore been a need for a bleaching system which can be used at a low temperature, close to ambient and without damage to the washed fiber.

On a proposé de tels systèmes mettant en oeuvre des sensibilisateurs, en fait un composé organométallique coloré, agissant par photoactivation. On connaît ainsi d'après le brevet français N° 2.384.882 un système à base, à titre de sensibilisateur, de phtalo- cyanine d'aluminium sulfonée. Le problème est que ce type de produit reste fixé sur la fibre et colore ainsi le tissu lavé. Pour cette raison un tel système est inapplicable en pratique.Such systems have been proposed using sensitizers, in fact a colored organometallic compound, acting by photoactivation. A system based on sulphonated aluminum phthalocyanine is thus known from French Patent No. 2,384,882. The problem is that this type of product remains attached to the fiber and thus colors the washed fabric. For this reason such a system is inapplicable in practice.

L'objet de l'invention est donc un système de blanchiment par photoactivation, qui soit d'une utilisation simple, qui soit efficace vis-à-vis des salissures tout en respectant au mieux la fibre traitée, et mettant en jeu un sensibilisateur dont l'adsorption sur la fibre soit totalement réversible au rinçage.The object of the invention is therefore a bleaching system by photoactivation, which is simple to use, which is effective with respect to soiling while respecting the treated fiber as well as possible, and involving a sensitizer, adsorption on the fiber is completely reversible on rinsing.

Dans ce but la composition détergente selon l'invention est caractérisée en ce qu'elle contient à titre de système de blanchiment par photoactivation au moins un agent sensibilisateur constitué par un sel ou disel soluble d'un acide de formule générale :

Figure imgb0001
dans laquelle les atomes d'hydrogènes portés par les carbones 1 à 8 peuvent être substitués ou non, notamment par des halogènes ; et un additif du type mono, di- ou tétramine tertiaire cyclique.For this purpose, the detergent composition according to the invention is characterized in that it contains, as a bleaching system by photoactivation, at least one sensitizing agent consisting of a soluble salt or disel of an acid of general formula:
Figure imgb0001
 in which the hydrogen atoms carried by carbons 1 to 8 may or may not be substituted, in particular by halogens; and an additive of the cyclic tertiary mono, di- or tetramine type.

Par ailleurs, les compositions détergentes de l'invention peuvent être mises en oeuvre pour le blanchiment d'un textile selon un procédé qui comporte les étapes suivantes :

  • - on met en contact le textile avec un bain lessiviel comprenant ladite composition,
  • - on soumet le bain lessiviel et le textile à une irradiation lumineuse,
  • - on sépare le textile et le bain lessiviel et on rince à l'eau le textile.
Furthermore, the detergent compositions of the invention can be used for bleaching a textile according to a process which comprises the following stages:
  • the textile is brought into contact with a detergent bath comprising said composition,
  • - the detergent bath and the textile are subjected to light irradiation,
  • - the textile and the detergent bath are separated and the textile is rinsed with water.

D'autres caractéristiques et avantages de l'invention seront mieux compris à la lecture de la description qui va suivre.Other characteristics and advantages of the invention will be better understood on reading the description which follows.

En ce qui concerne le sensibilisateur, on emploie un produit appartenant à la famille des colorants xanthéniques et plus précisément du type de la fluorescéine. Comme indiqué plus haut ces produits correspondent aux sels ou disels solubles dans l'eau de l'acide de formule (1) :

Figure imgb0002
As regards the sensitizer, a product belonging to the family of xanthene dyes and more specifically of the fluorescein type is used. As indicated above, these products correspond to the water-soluble salts or disels of the acid of formula (1):
Figure imgb0002

Les sels seront généralement les sels ou disels de sodium ou de potassium. Par ailleurs, les atomes d'hydrogène portés par les carbones reperés 1 à 8 peuvent être substitués notamment par des atomes de Cl, Br et I.The salts will generally be the sodium or potassium salts or disels. Furthermore, the hydrogen atoms carried by the carbons identified 1 to 8 can be substituted in particular by atoms of Cl, Br and I.

D'une manière générale, les produits qui conviennent particulièrement pour la composition de l'invention sont ceux qui, répondant à la formule 1, ont la propriété de s'adsorber sur la fibre d'une manière réversible. En outre, ils sont dotés d'un spectre d'absorption situé sensiblement dans le domaine de la lumière visible c'est-à-dire entre 400 et 800 nm, plus précisément entre 400 et 600 nm.In general, the products which are particularly suitable for the composition of the invention are those which, corresponding to formula 1, have the property of being adsorbed on the fiber in a reversible manner. In addition, they have an absorption spectrum located substantially in the visible light range, that is to say between 400 and 800 nm, more precisely between 400 and 600 nm.

Parmi les produits particulièrement efficaces de ce type, on peut citer l'éosine "Yellow" c'est-à-dire le produit de formule :

Figure imgb0003
Among the particularly effective products of this type, there may be mentioned "Yellow" eosin, that is to say the product of formula:
Figure imgb0003

M pouvant être un métal alcalin ou alcalino-terreux.M can be an alkali or alkaline earth metal.

Comme autres composés intéressants, on peut citer la dibromo-1,2 fluoresceine, c'est-à-dire le sel ou le disel dibromé de formule 1, la dibromo-3,4 fluoresceine, la phloxine c'est-à-dire la tétrabromo-1,2,3,4 tétrachloro-5,6,7,8 fluoresceine, la diodo-1,2 fluoresceine, la diodo-3,4 fluoresceine et la tétraiodo-1,2,3,4 têtrachloro-5,6,7,8 fluoresceine ou "Rose Bengale".As other compounds of interest, mention may be made of 1,2-dibromo fluorescein, that is to say the dibromo salt or disel of formula 1, 3,4-dibromo fluorescein, ie phloxine tetrabromo-1,2,3,4 tetrachloro-5,6,7,8 fluorescein, diodo-1,2 fluoresceine, diodo-3,4 fluoresceine and tetraiodo-1,2,3,4 têtrachloro-5 , 6,7,8 fluorescein or "Rose Bengal".

Par ailleurs, il est intéressant de préparer des compositions comprenant une combinaison de plusieurs agents sensibilisateurs du type décrit ci-dessus.Furthermore, it is advantageous to prepare compositions comprising a combination of several sensitizing agents of the type described above.

Grâce a un tel mélange de sensibilisateurs, on peut augmenter la quantité d'énergie lumineuse absorbée lors de l'irradiation du bain lessiviel et améliorer ainsi le rendement du système de blanchiment. On peut aussi avec un tel système réduire le temps d'irradiation pour obtenir un résultat identique à celui obtenu . avec un système à un seul sensibilisateur.Thanks to such a mixture of sensitizers, it is possible to increase the quantity of light energy absorbed during the irradiation of the detergent bath and thus improve the efficiency of the bleaching system. It is also possible with such a system to reduce the irradiation time to obtain a result identical to that obtained. with a single sensitizer system.

On peut citer à titre de mélanges intéressants, la combinaison Eosine Yellow et Rose Bengale ainsi que la combinaison Eosine Yellow et la diodo-1,2 fluoresceine.As interesting mixtures, mention may be made of the combination Eosine Yellow and Rose Bengal as well as the combination Eosine Yellow and 1,2-diodo fluorescein.

On peut aussi citer les combinaisons ternaires suivantes : 1) tétrachloro-1,2,3,4 fluoresceine, 2) Eosine Yellow ou diodo-1,2 fluoresceine, 3) phloxine ou Rose Bengale.Mention may also be made of the following ternary combinations: 1) tetrachloro-1,2,3,4 fluorescein, 2) Eosine Yellow or diodo-1,2 fluoresceine, 3) phloxine or Rose Bengal.

Par ailleurs, le système de blanchiment de l'invention comporte un additif qui comme indiqué plus haut est choisi dans le groupe des mono-, di- ou tétramines tertiaires cycliques. Avantageusement, on utilise des amines du type précédent mais qui sont en outre pontées ; on entend par là les amines dans lesquelles un atone d'azote est lié transversalement à un autre atome d'azote ou à un atome de carbone du cycle.Furthermore, the bleaching system of the invention comprises an additive which, as indicated above, is chosen from the group of cyclic tertiary mono-, di- or tetramines. Advantageously, amines of the above type are used but which are also bridged; by this is meant the amines in which a nitrogen atom is linked transversely to another nitrogen atom or to a carbon atom of the ring.

Comme additif convenant particulièrement bien dans le cadre de l'invention on peut citer le 1,4 diaza bicyclo -(2,2,2) octane (DABCO) de formule ci-dessous :

Figure imgb0004
ou encore le 1 aza bicyclo-(2,2,2)octane ou quinuclidine (ABCO) de formule :
Figure imgb0005
 As an additive which is particularly suitable in the context of the invention, mention may be made of 1,4 diaza bicyclo - (2,2,2) octane (DABCO) of formula below:
Figure imgb0004
 or also 1 aza bicyclo- (2,2,2) octane or quinuclidine (ABCO) of formula:
Figure imgb0005

Un autre additif intéressant est l'hexaméthylènetétramine.Another interesting additive is hexamethylenetetramine.

Les systèmes de blanchiment comprenant les produits du type définis ci-dessus -peuvent être incorporés a une composition détergente solide ou liquide.Bleaching systems comprising products of the type defined above can be incorporated into a solid or liquid detergent composition.

Ainsi outre le système de blanchiment, cette composition détergente pourra comprendre un agent tensio-actif. Il est préférable que ce tensio-actif soit anionique ou, si l'on utilise un mélange de tensio-actifs qu'il y ait dans ce mélange au moins un tensio-actif anionique. On peut citer par exemple comme tensio-actifs anionique utilisable dans le cadre de l'invention les sels solubles dans l'eau d'alkyl sulfate.Thus, in addition to the bleaching system, this detergent composition may include a surfactant. It is preferable that this surfactant is anionic or, if a mixture of surfactants is used that there is in this mixture at least one anionic surfactant. Mention may be made, for example, as anionic surfactants which can be used in the context of the invention, of the water-soluble salts of alkyl sulphate.

La composition pourra aussi comprendre une base ou "builder" de type connu tel que par exemple des phosphates ou polyphosphates de métaux alcalins solubles dans l'eau ou encore des silicates.The composition may also include a base or "builder" of known type such as, for example, phosphates or polyphosphates of alkali metals soluble in water or else silicates.

Erfin, la composition pourra comprendre tout additif connu du type arti-nousse, anti-redéposant, parfums par exemple.Erfin, the composition may include any known additive of the arti-nousse type, anti-redepositing, perfumes for example.

Les proportions des différents constituants de la composition détergente seront choisies de telle manière qu'une fois la compo- siticn dissoute dans le bain lessiviel, la concentration en sensibilisateur et notamment en éosine soit comprise entre environ 10-6M et 10-5M. De préférence, cette concentration devra être située aux environs de 2,5 et 10.10-6M. Pour des valeurs plus élevées, le sensibilisateur en trop grande quantité peut avoir un effet de filtre interne nuisant à la photoactivation lors de l'irradiation du bain lessiviel.The proportions of the various constituents of the detergent composition will be chosen such that once the composition has dissolved in the detergent bath, the concentration of sensitizer and in particular of eosin is between approximately 10 -6 M and 10 -5 M. Preferably, this concentration should be located around 2.5 and 10.10 -6 M. For higher values, the sensitizer in too large a quantity can have an internal filtering effect which is detrimental to photoactivation during irradiation of the bath. detergent.

On notera que dans le cas de l'emploi d'un mélange de sensibilisateurs, de préférence, la concentration en chaque sensibilisateur reste dans le domaine fixé ci-dessus.It will be noted that in the case of the use of a mixture of sensitizers, preferably, the concentration of each sensitizer remains in the range fixed above.

La concentration en additif doit être comprise entre 10 M et 10-1M. En-deçà de 10-3M on ne note pas d'effet. Au-delà de 10-1M, on ne note pas de gain notable en blanchiment. De préférence cette concentration est située aux environs de 10-2M.The additive concentration must be between 10 M and 10 -1 M. Below 10 -3 M there is no effect. Beyond 10 -1 M, there is no significant gain in money laundering. Preferably, this concentration is located around 10 -2 M.

Enfin les constituants de la composition détergente seront choisis de préférence de manière à ce que le pH du bain lessiviel soit compris entre 9 et 11.Finally, the constituents of the detergent composition will preferably be chosen so that the pH of the detergent bath is between 9 and 11.

Les compositions de l'invention peuvent être mises en oeuvre d'une manière extrêmement simple.The compositions of the invention can be used in an extremely simple manner.

On notera tout d'abord qu'elles peuvent être utilisées pour le blanchiment ce textile en coton ou mixte.It should first of all be noted that they can be used for bleaching this cotton or mixed textile.

Le textile à traiter est d'abord plongé dans un bain lessiviel conprenant la composition selon l'invention. Le textile y est maintenu sous agitation à température ambiante et dans le noir ou à la lumière ambiante pour permettre la déposition du sensibilisateur.The textile to be treated is first immersed in a detergent bath containing the composition according to the invention. The textile is kept there with stirring at room temperature and in the dark or in ambient light to allow the deposition of the sensitizer.

Ensuite le bain lessiviel et le textile qui y est contenu sont sormis à une irradiation lumineuse dans le domaine du visible (400 - 800nm) issue par exemple d'une lampe quartz halogène.Then the detergent bath and the textile which is contained there are asleep to a light irradiation in the visible range (400 - 800nm) resulting for example from a halogen quartz lamp.

Cette irradiation peut durer entre 10 et 60 minutes, généra- lement entre 10 et 30 minutes. D'une manière générale pendant cette irradiation, la température du bain lessiviel est maintenue voisine de l'ambiante.This irradiation can last between 10 and 60 minutes, generally between 10 and 30 minutes. Generally during this irradiation, the temperature of the detergent bath is kept close to ambient.

Après irradiation, on sépare le bain du textile et celui-ci est ensuite rincé à l'eau pendant quelques minutes pour éliminer le sensibilisateur.After irradiation, the bath is separated from the textile and the latter is then rinsed with water for a few minutes to remove the sensitizer.

I1 est à noter qu'il peut être avantageux d'effectuer au moins une partie du rinçage sous irradiation. On permet ainsi notamment d'accélérer l'élimination du sensibilisateur.It should be noted that it may be advantageous to carry out at least part of the rinsing under irradiation. This makes it possible in particular to accelerate the elimination of the sensitizer.

Des exemples concrets mais non limitatifs de l'invention vont maintenant être donnés.Concrete but nonlimiting examples of the invention will now be given.

EXEMPLE 1EXAMPLE 1

On part des produits suivants :

  • Eosine Y extra cristallisée de la marque R.A.L. DABCO
  • Dodécylsulfate de sodium (SDS)
  • Base "builder" de composition (% en poids) Tripolyphosphate de Na : 71 Pyrophosphate de Na : 5 Phosphate trisodique anhydre : 1 Silicate en poudre : 23
We start from the following products:
  • Eosine Y extra crystallized from the brand RAL DABCO
  • Sodium dodecyl sulfate (SDS)
  • Composition "builder" base (% by weight) Na tripolyphosphate: 71 Na pyrophosphate: 5 Anhydrous trisodium phosphate: 1 Silicate powder: 23

On forme un bain lessiviel comportant 3,1 g/1 de builder, SDS : 0,1 M, éosine : 0,5.10-5 M, DABCO : 10-2M, pH : 10,6.A washing bath is formed comprising 3.1 g / l of builder, SDS: 0.1 M, eosin: 0.5.10 -5 M, DABCO: 10 -2 M, pH: 10.6.

Par ailleurs, on utilise des échantillons de coton préparés de la manière suivante :

  • Une solution de thé soluble commercial (NESTEA) à 12 g/1 dans l'eau distillée est chauffée à reflux (90°C) pendant 1 heure environ. Trois bandes de coton blanc sont introduites et maintenues 60 mn dans la solution à une température de 80° à 90°C. Les bandes sont alors essorées, aplanies et séchées à l'air ambiant. Elles sont ensuite lavées en machine, en eau douce, à 30°C, sans prélavage puis abondamment rincées.
In addition, cotton samples prepared in the following manner are used:
  • A solution of commercial soluble tea (NESTEA) at 12 g / 1 in distilled water is heated at reflux (90 ° C) for about 1 hour. Three strips of white cotton are introduced and kept for 60 minutes in the solution at a temperature of 80 ° to 90 ° C. The strips are then wrung, leveled and dried in the ambient air. They are then machine washed, in fresh water, at 30 ° C, without prewash and then thoroughly rinsed.

Les bandes teintes sont enfin séchées à l'air chaud, repassées entre deux feuilles de papier filtre et découpées en éprouvettes. Les éprcuvettes présentant une teinture homogène sont sélectionnées et conservées à l'abri de la lumière. 0n effectue des mesures de réflectance des échantillons sur un réflectomètre GARDNER XL-805 (norme din 6033) dans le système trichromatique haLbL.The dyed strips are finally dried with hot air, ironed between two sheets of filter paper and cut into test pieces. The specimens having a homogeneous dye are selected and stored in the dark. We perform reflectance measurements of the samples on a GARDNER XL-805 reflectometer (din standard 6033) in the trichromatic system ha L b L.

Un échantillon de tissu de coton taché préparé de la manière ci-dessus et de réflectance connue, est alors introduit dans le bain lessiviel et maintenu sous agitation, à température ambiante et dans le noir, pour permettre la déposition d'éosine. Le bain lessiviel contenant le tissu est ensuite irradié.A sample of stained cotton fabric prepared in the above manner and of known reflectance is then introduced into the washing bath and kept under stirring, at room temperature and in the dark, to allow the deposition of eosin. The detergent bath containing the fabric is then irradiated.

L'irradiation lumineuse est assurée par un projecteur HEDLER type "DE LUXE 2000" muni d'une lampe quartz - halogène 1000 w (CSRAM - HALOGEN SUPERPHOT). La distance entre la surface du bain lessiviel et la lampe est de 30 cm environ.The light irradiation is ensured by a HEDLER projector type "DE LUXE 2000" equipped with a quartz - halogen lamp 1000 w (CSRAM - HALOGEN SUPERPHOT). The distance between the surface of the detergent bath and the lamp is approximately 30 cm.

L'irradiation dure 60 mn.The irradiation lasts 60 min.

Durant l'irradiation la température du bain lessiviel est maintenue aux alentours de 25°C.During irradiation the temperature of the detergent bath is maintained at around 25 ° C.

Après irradiation, les échantillons sont rincés 1 heure dans 600 ml d'eau permutée à l'abri de la lumière puis séchés entre ceux feuilles de papier filtre.After irradiation, the samples are rinsed for 1 hour in 600 ml of permuted water protected from light and then dried between those sheets of filter paper.

Leur réflectance est comparée à celle de ces mêmes échantillons avant traitement (△ET) et d'échantillons équivalents traités dans les mêmes conditions et irradiés en absence d'éosine (_Edet) pour éliminer l'effet détergent et la photodécoloration de la salissure.Their reflectance is compared with that of these same samples before treatment (△ E T ) and equivalent samples treated under the same conditions and irradiated in the absence of eosin (_E det ) to eliminate the detergent effect and the photodecoloration of the dirt .

L'effet de blanchiment obtenu par photoactivation - Eb1 est alors :

Figure imgb0006
The whitening effect obtained by photoactivation - E b1 is then:
Figure imgb0006

Dans l'exemple présent on obtient ∠ET = 18 et ∠Eb1 = 9 EXEMPLE 2In the present example we obtain ∠E T = 18 and ∠E b1 = 9 EXAMPLE 2

On procède de la même manière que dans l'exemple 1 avec un tissu de coton taché de vin (salissure standard EMPA 114).The procedure is the same as in Example 1 with a cotton fabric stained with wine (standard soiling EMPA 114).

L'irradiation dure 30 minutes.The irradiation lasts 30 minutes.

On obtient un ∠ET de 25, et ∠Eb1 = 14.We obtain a ∠E T of 25, and ∠E b1 = 14.

Avec une irradiation de 15 minutes on obtient :

Figure imgb0007
With an irradiation of 15 minutes we obtain:
Figure imgb0007

EXEMPLE 3EXAMPLE 3

On part des mêmes produits que dans l'exemple 1 sauf que le DABCO est remplacé par l'hexaméthylène tétramine (HMTA).We start from the same products as in Example 1 except that DABCO is replaced by hexamethylene tetramine (HMTA).

On forme un bain lessiviel comportant 3,1 g/1 de builder, SDS : 0, M, éosine : 0,8 10-5M, HMTA : 10-2M, pH : 9,8.A washing bath is formed comprising 3.1 g / l of builder, SDS: 0, M, eosin: 0.8 10 -5 M, HMTA: 10 -2 M, p H: 9.8.

On procède de la même manière sur les mêmes échantillons et avec la même salissure que dans l'exemple 1. L'irradiation est cependant de 30 mn.The procedure is the same on the same samples and with the same soiling as in Example 1. The irradiation is, however, 30 min.

On obtient les résultats suivants :

Figure imgb0008
The following results are obtained:
Figure imgb0008

EXEMPLE 4EXAMPLE 4

On procède de la même manière que dans l'exesple 3 avec un tissu de coton taché de vin (salissure standard EKPA 114).The procedure is the same as in example 3 with a cotton fabric stained with wine (standard soiling EKPA 114).

L'irradiation dure 10 minutes.The irradiation lasts 10 minutes.

On obtient unWe get a

Figure imgb0009
Figure imgb0009

EXEMPLE 5EXAMPLE 5

On part des produits suivants :

  • - Tétrachloro-1,2,3,4 fluoresceine,
  • - Eosine Yellow extra cristallisée de la marque RAL,
  • - Phloxine,
We start from the following products:
  • - 1,2,3,4 Tetrachloro fluorescein,
  • - Eosine Yellow extra crystallized from the RAL brand,
  • - Phloxine,

- DABCO,- DABCO,

  • - Dodécylsulfate de sodium (SDS)- Sodium dodecyl sulfate (SDS)
  • - Base "builder" de composition identique à celle de l'exemple 1.- "Builder" base of composition identical to that of Example 1.

On forme un bain lessiviel comportant 3,1 g/1 de builder, SDS : 0,1 M, concentration respective pour chaque sensibilisateur : 10-5 M, DABCO : 10-2M.A washing bath is formed comprising 3.1 g / l of builder, SDS: 0.1 M, respective concentration for each sensitizer: 10 -5 M, DABCO: 10 -2 M.

Les échantillons sont préparés, lavés et analysés comme décrit dans l'exemple 1. Toutefois l'irradiation est de 20 minutes.The samples are prepared, washed and analyzed as described in Example 1. However, the irradiation is 20 minutes.

On utilise la même salissure (NESTEA).We use the same soiling (NESTEA).

On obtient les résultats suivants :

Figure imgb0010
The following results are obtained:
Figure imgb0010

On obtient pour une même salissure un effet de blanchiment supérieur ou voisin de celui obtenu avec un système à un seul sensibilisateur (comme dans le cas des exemples 2 ou 3) avec un temps d'irradiation inférieur.A whitening effect greater or close to that obtained with a system with a single sensitizer (as in the case of Examples 2 or 3) is obtained for the same soiling with a shorter irradiation time.

EXEMPLE 6EXAMPLE 6

Dans cet exemple, on essaie plusieurs systèmes comprenant tous le même additif le DABCO mais des sensibilisateurs différents.In this example, we are testing several systems, all comprising the same additive DABCO but different sensitizers.

On procède de la même manière que dans l'exemple 1 sur la même salissure (NESTEA). La concentration en sensibilisateur est de 10-5M. L'irradiation est de 30 minutes.The procedure is the same as in Example 1 on the same soiling (NESTEA). The sensitizer concentration is 10 -5 M. The irradiation is 30 minutes.

Les résultats sont donnés ci-dessous :

Figure imgb0011
The results are given below:
Figure imgb0011

EXEMPLE 7 COMPARATIFCOMPARATIVE EXAMPLE 7

On traite les mêmes tissus que dans les exemples précédents avec les mêmes salissures dans un appareil Linitest avec la même formulation de base et le même détergent en remplaçant le système sensibilisateur-additif par du perborate (15 % en poids) et de la TAED (3 %).The same fabrics are treated as in the previous examples with the same soiling in a Linitest device with the same basic formulation and the same detergent by replacing the sensitizer-additive system with perborate (15% by weight) and TAED (3 %).

Le lavage est effectué à 60°C au cours d'un cycle de 40 minutes. Les résultats sont donnés ci-dessous :

Figure imgb0012
Washing is carried out at 60 ° C during a 40 minute cycle. The results are given below:
Figure imgb0012

On peut voir que le système de l'invention procure un blanchiment- du même ordre de grandeur, voire même supérieur à celui obtenu avec un système au perborate, avec un temps de lavage inférieur dans certains cas pour le vin en particulier, et dans tous les cas à une température très inférieure.It can be seen that the system of the invention provides a bleaching of the same order of magnitude, or even greater than that obtained with a perborate system, with a washing time less in some cases for the wine in particular, and in all cases at a much lower temperature.

Bien entendu, l'invention n'est nullement limitée aux modes de réalisation décrits qui n'ont été donnés qu'à titres d'exemples. En particulier, elle comprend tous les moyens constituant des équivalents techniques des moyens décrits ainsi que leur combinaison si celles-ci sont mises en oeuvre dans le cadre de la protection comme revendiquée.Of course, the invention is in no way limited to the embodiments described which have been given only by way of examples. In particular, it includes all the means constituting technical equivalents of the means described as well as their combination if these are used in the context of protection as claimed.

Claims (12)

1. Composition détergente caractérisée en ce qu'elle contient à titre de système de blanchiment par photoactivation au moins un agent sensibilisateur du type sel ou disel soluble d'un acide de formule générale :
Figure imgb0013
dans laquelle les atomes d'hydrogène portés par les carbones 1 à 8 peuvent être substitués ou non, notamment par des halogènes ; et un additif du type mono- di- ou tétramine tertiaire cyclique.1. A detergent composition characterized in that it contains as bleaching system photoactiv at io n at least one sensitizing agent of the type or disalt salt soluble of a acid of general formula:
Figure imgb0013
 in which the hydrogen atoms carried by carbons 1 to 8 may or may not be substituted, in particular by halogens; and an additive of the cyclic tertiary monodi or tetramine type. 2. Composition selon la revendication 1 caractérisée en ce que l'additif est une mono-, di- ou tétramine tertiaire cyclique pontée.2. Composition according to claim 1 characterized in that the additive is a bridged cyclic tertiary mono-, di- or tetramine. 3. Composition selon la revendication 2 caractérisée en ce que l'additif est le 1,4 diaza bicyclo-(2,2,2) octane.3. Composition according to claim 2 characterized in that the additive is 1,4 diaza bicyclo- (2,2,2) octane. 4. Composition selon la revendication 2 caractérisée en ce que l'additif est le 1 aza bicyclo-(2,2,2)octane.4. Composition according to claim 2 characterized in that the additive is 1 aza bicyclo- (2,2,2) octane. 5. Composition selon la revendication 1, caractérisé en ce que l'additif est l'hexaméthylène têtramine.5. Composition according to claim 1, characterized in that the additive is hexamethylene tetamine. - 6. Composition selon l'une quelconque des revendications précédentes caractérisée en ce que l'agent sensibilisateur est l'éosine de formule :
Figure imgb0014
M pouvant être un métal alcalin ou alcalino-terreux.- 6. Composition according to any one of the preceding claims, characterized in that the sensitizing agent is eosin of formula:
Figure imgb0014
 M can be an alkali or alkaline earth metal. 7. Composition selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'elle comporte comme agents sensibilisateurs un mélange d'éosine et de rose bengale.7. Composition according to any one of claims 1 to 4, characterized in that it comprises, as sensitizing agents, a mixture of eosin and bengal rose. 8. Composition selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'elle comporte comme agents sensibilisateurs un mélange d'éosine et de diodo-1,2 fluoresceine.8. Composition according to any one of claims 1 to 4, characterized in that it comprises, as sensitizing agents, a mixture of eosin and 1,2-diodo fluorescein. 9. Composition selon l'une quelconque des revendications 1 à 4 caractérisé en ce qu'elle comporte un mélange de trois agents sensibilisateurs : 1) l'éosine ou la diodo-1,2 fluoresceine, 2) la phloxine ou Rose Bengale, 3) la tétrachloro-1,2,3,L- fluoresceine.9. Composition according to any one of claims 1 to 4 characterized in that it comprises a mixture of three sensitizing agents: 1) eosine or 1,2-diodo fluorescein, 2) phloxine or Rose Bengal, 3 ) tetrachloro-1,2,3, L- fluorescein. 10. Composition selon l'une quelconque des revendications précédentes caractérisée en ce qu'elle contient en outre un agent tensio-actif anionique.10. Composition according to any one of the preceding claims, characterized in that it also contains an anionic surfactant. 11. Procédé de blanchiment d'un textile mettant en oeuvre une composition détergente selon l'une quelconque des revendications précédentes caractérisé en ce qu'il comporte les étapes suivantes : - on met en contact le textile avec un bain lessiviel comprenant ladite composition, - on soumet le bain lessiviel et le textile à une irradiation lumineuse, - on sépare le textile et le bain lessiviel et on rince à l'eau le textile. 11. Process for bleaching a textile using a detergent composition according to any one of the preceding claims, characterized in that it comprises the following steps: the textile is brought into contact with a detergent bath comprising said composition, - the detergent bath and the textile are subjected to light irradiation, - the textile and the detergent bath are separated and the textile is rinsed with water. 12. Procédé selon la revendication 11 caractérisé en ce qu'on effectue au moins une partie du-rinçage sous irradiation.12. Method according to claim 11 characterized in that at least part of the rinsing is carried out under irradiation.
EP85400885A 1984-05-15 1985-05-07 Detergent composition for bleaching by photoactivation and process for its use Expired EP0165115B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85400885T ATE30243T1 (en) 1984-05-15 1985-05-07 DETERGENT COMPOSITION FOR PHOTOACTIVATION BLEACHING AND ITS APPLICATION METHOD.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
FR8407469A FR2564481B1 (en) 1984-05-15 1984-05-15 DETERGENT COMPOSITION FOR PHOTOACTIVATION BLEACHING AND METHOD OF USE
FR8407469 1984-05-15
FR8505126 1985-04-04
FR8505124 1985-04-04
FR8505124A FR2579989A2 (en) 1985-04-04 1985-04-04 Detergent composition for bleaching by photoactivation and its process of use
FR8505126A FR2579990A1 (en) 1985-04-04 1985-04-04 Detergent composition for bleaching by photoactivation based on xanthene dyes and on a tertiary tetramine and its process of use

Publications (2)

Publication Number Publication Date
EP0165115A1 true EP0165115A1 (en) 1985-12-18
EP0165115B1 EP0165115B1 (en) 1987-10-14

Family

ID=27251215

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85400885A Expired EP0165115B1 (en) 1984-05-15 1985-05-07 Detergent composition for bleaching by photoactivation and process for its use

Country Status (10)

Country Link
US (1) US4668418A (en)
EP (1) EP0165115B1 (en)
JP (1) JPS6116999A (en)
DE (1) DE3560774D1 (en)
DK (1) DK158918C (en)
ES (1) ES8608035A1 (en)
FI (1) FI78502C (en)
GR (1) GR851172B (en)
NO (1) NO165204C (en)
PT (1) PT80464B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595572A (en) * 1993-02-16 1997-01-21 The Commonwealth Of Australia Commonwealth Scientific And Industrial Research Organization Wool and wool-blend fabric treatment
ATE406157T1 (en) * 1999-08-13 2008-09-15 Provectus Pharmatech Inc IMPROVED TOPICAL MEDICATIONS AND METHODS FOR THE PHOTODYNAMIC TREATMENT OF DISEASES
DE602004012854T2 (en) * 2003-06-18 2009-05-14 Unilever N.V. BLUE AND RED BALANCING
GB0325617D0 (en) * 2003-11-03 2003-12-10 Unilever Plc Red bleaching compositions
JP5117403B2 (en) * 2006-01-23 2013-01-16 ザ プロクター アンド ギャンブル カンパニー Composition comprising an enzyme and a photobleaching agent
KR101452947B1 (en) 2008-03-21 2014-10-21 제이더블유중외제약 주식회사 Composition for Cleaning Contact Lenses and Method for Preparing thereof
US9642687B2 (en) 2010-06-15 2017-05-09 The Procter & Gamble Company Methods for whitening teeth
US20150209808A1 (en) * 2014-01-24 2015-07-30 The Procter & Gamble Company Package for Light Activated Treatment Composition
US20150211165A1 (en) * 2014-01-24 2015-07-30 The Procter & Gamble Company Method for Treating Laundry
ES2941364T3 (en) 2018-06-11 2023-05-22 Procter & Gamble Photoactivator device for washing machine
EP3805346B1 (en) 2019-10-08 2024-08-14 The Procter & Gamble Company A method of laundering fabric
DE102021213793A1 (en) * 2021-12-03 2023-06-07 Henkel Ag & Co. Kgaa N-substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl)benzamides as photoactivators in detergents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372035A (en) * 1971-05-12 1974-10-30 Procter & Gamble Ltd Bleaching process
US3927967A (en) * 1972-06-02 1975-12-23 Procter & Gamble Photoactivated bleaching process and composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE37879B1 (en) * 1972-07-10 1977-11-09 Procter & Gamble Bleaching process
US4256598A (en) * 1978-01-11 1981-03-17 The Procter & Gamble Company Composition for combined washing and bleaching of fabrics
IN153407B (en) * 1979-09-28 1984-07-14 Ciba Geigy Ag
JPS5792095A (en) * 1980-12-01 1982-06-08 Kao Corp Bleaching agent composition
ATE12254T1 (en) * 1980-12-22 1985-04-15 Unilever Nv COMPOSITION CONTAINING A PHOTOACTIVATOR WITH IMPROVED BLEACHING EFFECT.
US4417994A (en) * 1981-01-24 1983-11-29 The Procter & Gamble Company Particulate detergent additive compositions
CH654424A5 (en) * 1983-03-25 1986-02-14 Ciba Geigy Ag METHOD FOR PREVENTING THE GELLING OF CONCENTRATED AQUEOUS PHOTOACTIVATOR SOLUTIONS.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372035A (en) * 1971-05-12 1974-10-30 Procter & Gamble Ltd Bleaching process
US3927967A (en) * 1972-06-02 1975-12-23 Procter & Gamble Photoactivated bleaching process and composition

Also Published As

Publication number Publication date
EP0165115B1 (en) 1987-10-14
FI78502C (en) 1989-08-10
NO165204B (en) 1990-10-01
JPS6116999A (en) 1986-01-24
ES543156A0 (en) 1986-06-01
NO165204C (en) 1991-01-09
DK212085D0 (en) 1985-05-14
NO851893L (en) 1985-11-18
PT80464A (en) 1985-06-01
US4668418A (en) 1987-05-26
FI851920A0 (en) 1985-05-14
DK158918C (en) 1991-01-21
DK212085A (en) 1985-11-16
GR851172B (en) 1985-11-25
FI851920A7 (en) 1985-11-16
DK158918B (en) 1990-07-30
FI78502B (en) 1989-04-28
DE3560774D1 (en) 1987-11-19
PT80464B (en) 1987-04-13
ES8608035A1 (en) 1986-06-01

Similar Documents

Publication Publication Date Title
EP0165115B1 (en) Detergent composition for bleaching by photoactivation and process for its use
US4166718A (en) Process for bleaching textiles
KR100262995B1 (en) Low hue photobleaches
DE2222829C2 (en) Procedure for removing stains from textiles
US4077768A (en) Inhibiting dye transfer in washing or bleaching
US4311605A (en) Compositions for treating textiles
FR2564837A1 (en) WATER-SOLUBLE AZAPHTALOCYANINES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS PHOTOACTIVATORS
EP0279134A1 (en) Antiredeposition latex for washing textiles
JPS58150000A (en) Detergent bleaching method for clothes
CN1250473A (en) Low hue photobleaches
KR100505528B1 (en) Fabric Flexible Composition
EP0960185B1 (en) Photobleaching compositions effective on dingy fabric
CA2000967A1 (en) High efficiency, low temperature bleaching compositions for textile and cellulose matters and bleaching process
FR2924445A1 (en) PHOTOACTIVE TEXTILE FIBERS DEPOLLUENTS AND DISINFECTANTS.
US2624710A (en) Composition for laundering textiles and for imparting a whitening effect thereon
FR2579990A1 (en) Detergent composition for bleaching by photoactivation based on xanthene dyes and on a tertiary tetramine and its process of use
FR2502170A1 (en) DEINFECTANT CLEANING REINFORCING DEVICE FOR CHEMICAL CLEANING
FR2515683A1 (en) COMPOSITION FOR BLEACHING AND WASHING CONTAINING A PERACID
FR2564481A1 (en) Detergent composition for bleaching by photoactivation and process for its use
EP0437988B1 (en) Detergent additive based on polyphosphate and an active optical agent, method of its production and its use in detergent composition
CN1205378C (en) Method for the use of hydrophobic bleadching systems in textile preparation
US5152921A (en) Liquid detergents compositions containing 2-2-dichloro-5,5-disulfodistyrylbiphenyl as the fluorescent whitener
BE787276A (en) Peroxide bleaching agent - contg peroxy bleach aldehyde or ketone activator and buffer
BE897905A (en) Whitening and washing composition based on a peroxyacid
JPH11217557A (en) Dye remover and method for removing dye from dye-containing water

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19851123

17Q First examination report despatched

Effective date: 19861126

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHONE-POULENC CHIMIE

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 30243

Country of ref document: AT

Date of ref document: 19871015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3560774

Country of ref document: DE

Date of ref document: 19871119

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19880531

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19900425

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19900427

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19900504

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19900529

Year of fee payment: 6

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19900531

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19900607

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19900611

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19900629

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19900712

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19910507

Ref country code: AT

Effective date: 19910507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19910508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19910531

Ref country code: CH

Effective date: 19910531

Ref country code: BE

Effective date: 19910531

BERE Be: lapsed

Owner name: RHONE-POULENC CHIMIE

Effective date: 19910531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19911201

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19920131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920303

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 85400885.1

Effective date: 19911209