EP0165115B1 - 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

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Publication number
EP0165115B1
EP0165115B1 EP85400885A EP85400885A EP0165115B1 EP 0165115 B1 EP0165115 B1 EP 0165115B1 EP 85400885 A EP85400885 A EP 85400885A EP 85400885 A EP85400885 A EP 85400885A EP 0165115 B1 EP0165115 B1 EP 0165115B1
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EP
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Prior art keywords
composition according
textile
additive
detergent
bleaching
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EP85400885A
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German (de)
French (fr)
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EP0165115A1 (en
Inventor
Frédéric Ricchiero
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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Priority claimed from FR8407469A external-priority patent/FR2564481B1/en
Priority claimed from FR8505126A external-priority patent/FR2579990A1/en
Priority claimed from FR8505124A external-priority patent/FR2579989A2/en
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Priority to AT85400885T priority Critical patent/ATE30243T1/en
Publication of EP0165115A1 publication Critical patent/EP0165115A1/en
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    • 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 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 in a cold washing.
  • such a product causes significant deterioration of the fibers.
  • the object of the invention is therefore a photoactivation bleaching system, which is simple to use, which is effective with respect to soiling while respecting the treated fiber as well as possible, and which involves a sensitizer, adsorption on the fiber is completely reversible on rinsing.
  • 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 (I):
  • the salts will generally be the sodium or potassium salts or disels.
  • the hydrogen atoms carried by the carbons located 1 to 8 can be substituted by atoms of CI, Br and I.
  • the products which are particularly suitable for the composition of the invention are those which, corresponding to formula I, 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 I, 3,4-dibromo fluorescein, ie phloxine tetrabromo-1,2,3,4 tetrachloro-5,6,7,8 fluorescein, diiodo-1,2 fluoresceine, diiodo-3,4 fluoresceine and tetraiode-1,2,3,4 tetrachloro-5 , 6,7,8 fluorescein or "Rose Bengal".
  • 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 ring carbon atom.
  • Another interesting additive is hexamethylenetetramine.
  • the bleaching systems comprising the 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 comprise 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.
  • composition may include any known additive of the anti-foam, anti-redepositing type, perfumes for example.
  • the proportions of the various constituents of the detergent composition will be selected such that once the composition dissolved in the washing bath, the sensitizer concentration and including eosin is between about 10 -6 M and 10 -5 M. Preferably this concentration should be located at about 2.5 to 10.10- 6 M. for higher values, the sensitizer in large quantities may have an internal filter effect affecting photoactivation upon irradiation of the washing bath.
  • the concentration of each sensitizer remains in the range fixed above.
  • the additive concentration must be between 10- 3 M and 10- 1 M. Below 10- 3 M there is no effect. Beyond 10-1M, there is no significant gain in money laundering. Preferably this concentration is located around 10-2M.
  • 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 comprising 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 contained therein are subjected to light irradiation in the visible range (400 - 800 nm), 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.
  • the dyed strips are finally dried with hot air, ironed between two sheets of filter paper and cut into test pieces.
  • the test pieces with a homogeneous dye are selected and stored in the dark. Reflectance measurements of the samples are carried out on a GARDNER XL-805 reflectometer (din standard 6033) in the trichromatic system La L b L.
  • 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 solution 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 deionized water protected from light and then dried between two 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.
  • Example 3 The procedure is the same as in Example 3 with a cotton fabric stained with wine (standard soiling EMPA 114).
  • the irradiation lasts 10 minutes.
  • 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 of 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 certain cases for the wine in particular, and in all case at a much lower temperature.

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  • 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)

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 détargents 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 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. It is also possible to use sodium hypochlorite in a cold washing. 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 FR-A-2.384.882 un système à base, à titre de sensibilisateur, de phtalocyanine 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. There is thus known from patent FR-A-2,384,882 a system based, as sensitizer, on sulfonated aluminum phthalocyanine. 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 photoactivation bleaching system, which is simple to use, which is effective with respect to soiling while respecting the treated fiber as well as possible, and which involves 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 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 photo-activation bleaching system, 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 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 (I):

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 (I):
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 par des atomes de CI, Br et I.The salts will generally be the sodium or potassium salts or disels. Furthermore, the hydrogen atoms carried by the carbons located 1 to 8 can be substituted by atoms of CI, 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 I, 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 I, 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 I, la dibromo-3,4 fluoresceine, la phloxine c'est-à-dire la tétrabromo-1,2,3,4 tétrachloro-5,6,7,8 fluoresceine, la diiodo-1,2 fluoresceine, la diiodo-3,4 fluoresceine et la tétraiode-1,2,3,4 tétrachloro-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 I, 3,4-dibromo fluorescein, ie phloxine tetrabromo-1,2,3,4 tetrachloro-5,6,7,8 fluorescein, diiodo-1,2 fluoresceine, diiodo-3,4 fluoresceine and tetraiode-1,2,3,4 tetrachloro-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 à 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 system with a single sensitizer.

On peut citer à titre de mélanges intéressants, la combinaison Eosine Yellow et Rose Bengale ainsi que la combinaison Eosine Yellow et le 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 atome 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 ring carbon atom.

Comme additif convenant particulièrement bien dans le cadre de l'invention on peut citer le 1,4 diaza bicyclo -(2,2,2) octane (DAECO) 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 (DAECO) 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 à une composition détergente solide ou liquide.The bleaching systems comprising the 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 comprise a base or "builder" of known type such as, for example, phosphates or polyphosphates of alkali metals soluble in water or else silicates.

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

Les proportions des différents constituants de la composition détergente seront choisies de telle manière qu'une fois la composition 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 élévées, 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 selected such that once the composition dissolved in the washing bath, the sensitizer concentration and including eosin is between about 10 -6 M and 10 -5 M. Preferably this concentration should be located at about 2.5 to 10.10- 6 M. for higher values, the sensitizer in large quantities may have an internal filter effect affecting photoactivation upon irradiation of the washing bath.

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 10-3M 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- 3 M and 10- 1 M. Below 10- 3 M there is no effect. Beyond 10-1M, there is no significant gain in money laundering. Preferably this concentration is located around 10-2M.

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 de textile en coton ou mixte.It should first of all be noted that they can be used for bleaching cotton or mixed textiles.

Le textile à traiter est d'abord plongé dans un bain lessiviel comprenant 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 comprising 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 soumis à une irradiation lumineuse dans le domaine du visible (400 - 800 nm) issue par exemple d'une lampe quartz halogène.Then the detergent bath and the textile contained therein are subjected to light irradiation in the visible range (400 - 800 nm), for example from a halogen quartz lamp.

Cette irradiation peut durer entre 10 et 60 minutes, généralement 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.

Il 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)
    Figure imgb0006
We start from the following products:
  • Eosine Y extra crystallized from the brand RAL
  • DABCO
  • Sodium dodecyl sulfate (SDS)
    Figure imgb0006

On forme un bain lessiviel comportant 3,1 g/I de builder, SDS : 0,1 M, éosine : 0,5.10-5M, DABCO : 10-2M, pH : 10,6.Forming a washing bath containing 3.1 g / l builder, SDS: 0.1M eosin: 0,5.10- 5M, 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/I dans l'eau distillée est chauffée à reflux (90°C) pendant 1 heure environ. Trois bandes de coton blanc sont introduites et maintenues 60 min 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 / l in distilled water is heated at reflux (90 ° C) for about 1 hour. Three strips of white cotton are introduced and kept for 60 min 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 éprouvettes présentant une teinture homogène sont sélectionnées et conservées à l'abri de la lumière. On effectue des mesures de réflectance des échantillons sur un réflectomètre GARDNER XL-805 (norme din 6033) dans le système trichromatique LaLbL.The dyed strips are finally dried with hot air, ironed between two sheets of filter paper and cut into test pieces. The test pieces with a homogeneous dye are selected and stored in the dark. Reflectance measurements of the samples are carried out on a GARDNER XL-805 reflectometer (din standard 6033) in the trichromatic system La 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 tain 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 solution 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 min.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 ertre deux feuilles de papier filtre.After irradiation, the samples are rinsed for 1 hour in 600 ml of deionized water protected from light and then dried between two sheets of filter paper.

Leur réflectance est comparée à celle de ces mêmes échantillons avant traitement (A ET) et d'échantillons équivalents traités dans les mêmes conditions et irradiés en absence d'éosine (ÂEdet) pour éliminer l'effet détergent et la photodecoloration de salissure.Their reflectance is compared with that of these same samples before treatment (A AND) and equivalent samples treated under the same conditions and irradiated in the absence of eosin (ÂE det ) to eliminate the effect. detergent and photodecoloration of soiling.

L'effet de blanchiment obtenu par photoactivation △Ebl est alors:

  • △Ebl = △ET - ΔEdet
The whitening effect obtained by photoactivation △ E bl is then:
  • △ E bl = △ E T - ΔEdet

Dans l'exemple présent on obtient △ET = 18 et △Ebl = 9In the present example we get △ E T = 18 and △ E bl = 9

Exemple 2Example 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 △Ebl = 14.We obtain an △ E T of 25, and △ E bl = 14.

Avec une irradiation de 15 minutes on obtient:

  • △ET = 21,
  • △Ebl = 11
With an irradiation of 15 minutes we obtain:
  • △ E T = 21,
  • Bl E bl = 11

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/I de builder, SDS : 0,1 M, éosine : 0,8 10-5M, HMTA : 10-2M, pH : 9,8.Forming a washing bath containing 3.1 g / l builder, SDS: 0.1M eosin 0.8 10 -5 M, HMTA: 10- 2 M, pH 9.8.

On procède de la même manière sur les mêmes échantillons et avec le même salissure que dans l'exemple 1. L'irradiation est cependant de 30 min.

  • On obtient les résultets suivants: .
  • △ET = 15 △Ebl = 11.
The procedure is the same on the same samples and with the same soiling as in Example 1. The irradiation is however 30 min.
  • The following results are obtained:.
  • △ E T = 15 △ E bl = 11.

Exemple 4Example 4

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

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

On obtient un △ET de 17 et △Ebl = 7We obtain an △ E T of 17 and △ E bl = 7

Exemple 5Example 5

On part des produits suivants:

  • - Tétrachloro-1,2,3,4 fluoresceine,
  • - Eosine Yellow extra cristallisée de la marque RAL,
  • - Phloxine,
  • - DABCO,
  • - Dodécylsulfate de sodium (SDS)
  • - Base "builder" de composition identique à celle de l'exemple 1.
We start from the following products:
  • - 1,2,3,4 Tetrachloro fluorescein,
  • - Eosine Yellow extra crystallized from the RAL brand,
  • - Phloxine,
  • - DABCO,
  • - Sodium dodecyl sulfate (SDS)
  • - "Builder" base of composition identical to that of Example 1.

On forme un bain lessiviel comportant 3,1 g/I de builder, SDS : 0,1 M, concentration respective pour chaque sensibilisateur: 10-5M, DABCO : 10-2M.Forming a washing bath containing 3.1 g / l builder, SDS 0.1 M concentration for each respective 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:

  • △ET = 13
  • △Edet = 3
  • △Ebl = 10
The following results are obtained:
  • △ E T = 13
  • △ E det = 3
  • △ E bl = 10

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 of 10- 5 M. The irradiation is 30 minutes.

Les résultats sont donnés ci-dessous:

Figure imgb0007
The results are given below:
Figure imgb0007

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 apparatus 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 minutes. Les résultats sont donnés ci-dessous;

Figure imgb0008
Washing is carried out at 60 ° C during a minute cycle. The results are given below;
Figure imgb0008

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 certain cases for the wine in particular, and in all case at a much lower temperature.

Claims (12)

1. Detergent composition characterized in that it contains, as system for bleaching by photoactivation, at least one sensitizing agent of the type of a soluble salt or disalt of an acid of general formula:
Figure imgb0013
in which the hydrogen atoms carried by the carbon atoms 1 to 8 may be substituted with halogen atoms or unsubstituted; and an additive of the cyclic tertiary mono-, di- or tetramine type.
2. Composition according to Claim 1, characterized in that the additive is a bridged cyclic tertiary mono-, di-or tetramine.
3. Composition according to Claim 2, characterized in that the additive is 1 A-diazabicyclo[2,2,2]octane.
4. Composition according to Claim 2, characterized in that the additive is 1-azabicyclo[2,2,2]octane.
5. Composition according to Claim 1, characterized in that the additive is hexamethylenetetramine.
6. Composition according to any one of the preceding claims, characterized in that the sensitizing agent is eosin of formula:
Figure imgb0014
it being possible for M to be an alkali metal or alkaline earth metal atom.
7. Composition according to any one of Claims 1 to 4, characterized in that it contains a mixture of eosin and Bengal rose as the sensitizing agents.
8. Composition according to any one of Claims 1 to 4, characterized in that it contains a mixture of eosin and 1,2-diiodofluorescein as the sensitizing agents.
9. Composition according to any one of Claims 1 to 4, characterized in that it contains a mixture of three sensitizing agents: 1) eosin or 1,2-diiodofluorescein, 2) phloxin or Bengal rose and 3) 1,2,3,4-tetrachloro- fluorescein.
10. Composition according to any one of the preceding claims, characterized in that it contains, in addition, an anionic surfactant.
11. Method for bleaching a textile, which employs a detergent composition according to any one of the preceding claims, characterized in that it comprises the following stages:
the textile is brought into contact with a detergent bath containing the said composition,
the detergent bath and the textile are subjected to a light radiation and
the textile and the detergent bath are separated and the textile is rinsed with water.
12. Method according to Claim 1, characterized in that at least a part of the rinsing is carried out under radiation.
EP85400885A 1984-05-15 1985-05-07 Detergent composition for bleaching by photoactivation and process for its use Expired EP0165115B1 (en)

Priority Applications (1)

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AT85400885T ATE30243T1 (en) 1984-05-15 1985-05-07 DETERGENT COMPOSITION FOR PHOTOACTIVATION BLEACHING AND ITS APPLICATION METHOD.

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FR8407469 1984-05-15
FR8407469A FR2564481B1 (en) 1984-05-15 1984-05-15 DETERGENT COMPOSITION FOR PHOTOACTIVATION BLEACHING AND METHOD OF USE
FR8505126 1985-04-04
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
FR8505124A FR2579989A2 (en) 1985-04-04 1985-04-04 Detergent composition for bleaching by photoactivation and its process of use
FR8505124 1985-04-04

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US5595572A (en) * 1993-02-16 1997-01-21 The Commonwealth Of Australia Commonwealth Scientific And Industrial Research Organization Wool and wool-blend fabric treatment
IL148139A0 (en) * 1999-08-13 2002-09-12 Photogen Inc Improved topical medicaments and methods for photodynamic treatment of disease
IN230386B (en) * 2003-06-18 2009-03-27 Unilever Nv
GB0325617D0 (en) * 2003-11-03 2003-12-10 Unilever Plc Red bleaching compositions
CA2635947A1 (en) * 2006-01-23 2007-08-02 The Procter & Gamble Company Enzyme and photobleach containing compositions
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
US20150211165A1 (en) * 2014-01-24 2015-07-30 The Procter & Gamble Company Method for Treating Laundry
US20150209808A1 (en) * 2014-01-24 2015-07-30 The Procter & Gamble Company Package for Light Activated Treatment Composition
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

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GB1372035A (en) * 1971-05-12 1974-10-30 Procter & Gamble Ltd Bleaching process
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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
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CH654424A5 (en) * 1983-03-25 1986-02-14 Ciba Geigy Ag METHOD FOR PREVENTING THE GELLING OF CONCENTRATED AQUEOUS PHOTOACTIVATOR SOLUTIONS.

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PT80464B (en) 1987-04-13
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NO165204C (en) 1991-01-09
DK212085A (en) 1985-11-16
PT80464A (en) 1985-06-01
NO851893L (en) 1985-11-18
DK158918B (en) 1990-07-30
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FI78502C (en) 1989-08-10
EP0165115A1 (en) 1985-12-18

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