FR2814943A1 - Coloring composition for skin and keratin fibers, comprises color precursor and catalytic system containing salts or oxides of manganese and-or zinc and alkaline hydrocarbonates - Google Patents

Abstract

Coloring composition for skin and/or keratin fibers contains at least one color precursor and a catalytic system whose first component is selected from salts and oxides of bivalent manganese and/or zinc, and second component is chosen from alkaline and alkaline earth hydrocarbonates and their mixtures. Coloring composition for skin and/or keratin fibers contains: (1) at least one color precursor selected from compounds having at least one aromatic ring of which at least two consecutive C atoms carry hydroxyl groups; and (2) a catalytic system whose first component is selected from salts and oxides of bivalent manganese and/or zinc, and second component is chosen from alkaline and alkaline earth hydrocarbonates and their mixtures. First and second component of catalytic system are taken in such proportions that (Mn(II))/(HCO3) is up to 1, when (Mn(II)) is not 0; (Zn(II))/(HCO3) is up to 1 when (Zn(II)) is not 0; and (Mn(II) + (Zn(II))/(HCO3) is up to 1 when neither of (Mn(II)) and (Zn(II)) is 0, with (Mn(II)), (Zn(II)) and (HCO3) representing respectively molar concentrations of Mn(II), Zn(II) and (HCO3) in the composition. Independent claims are also included for (1) the process of revealing coloration of weakly colored or colorless base composition comprising, in physiologically acceptable medium, at least one color precursor selected from compounds having at least one aromatic ring of which at least two consecutive C atoms carry hydroxyl groups, by adding to this composition, in presence of oxygen, a sufficient amount of catalytic system as described above, and placing the mixture in oxygen containing medium; (2) process of production of colorant composition, comprising adding to water a tablet comprising, in physiologically acceptable excipient, at least one color precursor as defined above, alkaline or alkaline earth hydrocarbonate, and optionally at least one Mn(II) and/or Zn(II) in appropriate quantities if water does not contain Mn(II) and/or Zn(II) in required proportion; (3) process of production of colorant composition comprising adding to water a tablet containing at least one color precursor as defined, and a tablet containing catalytic system as described above, both in physiologically acceptable excipients; and (4) process of coloration of skin and/or keratin fibers by application of layer of composition as claimed.

Description

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The present invention relates generally to a coloring composition, in particular for dyeing the skin and / or keratin fibers, a process for obtaining such a coloring composition and its use for coloring the skin. and / or keratinous fibers.

 In the field of dyeing of the skin and / or keratinous fibers such as the hair, the eyelashes, the eyebrows and the hairs, enzymatic catalysts are currently used to activate the coloration of color precursors. Thus, the coloration of polyphenols by oxidation is activated in the presence of natural polyphenoloxidase. By way of example, catechin, in the presence of natural polyphenoloxidase, gives an orange-yellow coloring and dihydroxyphenylanaline (L. DOPA) gives melanin. The main advantage of these enzymatic catalysts consists of obtaining pigments of colors and original shades, without the use of oxidizing compounds. However, the major disadvantage of this staining process is the use of enzymes, for which the toxicological risks, the stability in the compositions, the reproducibility, the price and the immobilization often necessary are factors which greatly limit their applications. .

 On the other hand, these catalysts are of a protein nature and the use of proteins is not without risk for use in cosmetology or dermatology, in particular because of sensitization reactions.

 The use of enzymatic catalysts in cosmetic preparations of the self-tanning type does not always allow a uniform coloration of the skin. The application throughout the body of compositions containing dihydroxyacetone (or DHA), typically used in this type of application, is long and tedious, and obtaining a uniform coloration is difficult.

 In the field of bronzing and self-tanning creams, an improvement has been obtained by using instead of enzymatic catalysts, chemical catalysts. Thus, the application WO 92/20321 A describes a cream promoting the browning of fair skin during exposure to the sun or UVB rays, the composition of which comprises a sunscreen, a physiologically acceptable medium and a pseudocatalase. The pseudocatalase is a coordination complex of a transition metal whose metal is Cu (I), Fe (tri) or Mn (II) and the ligand of bicarbonate. By pseudocatalase is meant a

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composé physiologiquement acceptable qui catalyse la dismutation de H202 in vivo de manière analogue à une catalase.

physiologically acceptable compound which catalyzes the disproportionation of H 2 O 2 in vivo in a catalase-like manner.

 For the treatment of skin depigmentation linked to blockages of the transformation of tyrosine into melanine, such as for example vitiligo, the application WO 92/20354 describes a composition containing, in a physiologically acceptable medium, a pseudocatalase.

 This pseudocatalase is a coordination complex of Fe (tri), Cu (I) or Mn (tri), the ligand being bicarbonate.

 The article by K. Schallreuter (Pseudocatalase is a bis-manganese III-EDTA- (HC03) 2 complex activated by UVB or natural sun; J Investing Dermator Symp Proc 1999 Sep; 451; 91-6) mentions the use of a mixture of sodium hyrogenocarbonate and manganese having a pseudocatalase activity for the treatment of vitiligo. However, there is no indication in all these documents concerning the coloring.

 In the field of hair dyeing, the European patent EP 621.029 A describes a composition comprising sodium chlorite, a water-soluble salt of Fe, Mn or Cu, or a chelate of this salt and an oxidation dye precursor.

.. ammonium ou aminé. Hair coloring requires the use of H202-

.. ammonium or amine.

 There is therefore a need for staining compositions, in particular for dyeing the skin and / or keratinous fibers, not requiring the use of enzymatic systems.

 The Applicant has found, quite surprisingly, that it is possible to obtain coloring compositions comprising at least one dye precursor capable of staining, in the presence of oxygen, by oxidation by means of a system. enzymatic (oxidase), replacing the enzymatic system with a purely chemical system.

 Thus, the chemical catalytic system of the invention behaves as a pseudo-oxidase capable of mimicking the oxidase activity without the disadvantages associated with the use of an enzymatic system.

 The subject of the present invention is therefore a dyeing composition, in particular for dyeing the skin and / or keratin fibers, which does not require the presence of enzymes.

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La présente invention concerne également un procédé pour révéler la coloration d'une composition de base peu ou pas colorée comprenant au moins un précurseur de colorant par oxydation qui consiste à ajouter à la composition de base un système catalytique purement chimique et à mettre la composition de base additionnée du système catalytique en présence d'un milieu oxydant tel qu'un milieu contenant de l'oxygène.

The present invention also relates to a method for revealing the coloration of a base composition with little or no color comprising at least one oxidation dye precursor which consists of adding to the base composition a purely chemical catalytic system and to put the composition of base addition of the catalyst system in the presence of an oxidizing medium such as an oxygen-containing medium.

 The present invention also relates to a process for obtaining a coloring composition as defined above.

 The present invention further relates to a method of dyeing the skin and / or keratin fibers using a composition as defined above.

proportions du premier constituant et du second constituant étant telles que :

[Mn (7 (II)] IHCO31 < lavec [Zn (II)] 0 [COJ M7/) +Z. (//)] [HCO3]

où [Mn (II)], [Zn (II)] et [HCO3] représentent respectivement les concentrations molaires en Mn (II), Zn (II) et HCO3 dans la composition. Finally, the present invention relates to packaging and dosage forms of the coloring composition or constituents of the coloring composition according to the invention.
The composition for coloring the skin and / or keratin fibers according to the invention comprises, in a physiologically acceptable medium, an effective amount of at least one dye precursor chosen from compounds comprising at least one aromatic ring having at least one two hydroxyl (OH) groups carried by two consecutive carbon atoms of the aromatic ring and an effective amount of a catalytic system comprising a first component selected from the salts and oxides of Mn (II), and / or Zn (II) and their mixtures and a second component selected from alkaline hydrogen carbonates, alkaline earth hydrogencarbonates and mixtures thereof,

proportions of the first constituent and the second constituent being such that:

[Mn (7 (II)] 1HCO3 2 <lavec [Zn (II)] O [COJ M7 /) + Z. (//)] [HCO3]

where [Mn (II)], [Zn (II)] and [HCO3] represent the molar concentrations of Mn (II), Zn (II) and HCO3 respectively in the composition.

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[mn (II)] Generally, the ratio [Mn ranges from 10-5 to 10-1, preferably from [HCO] 10-3 to 10-2 and is typically of the order of 5. 10-3.

à 100 fois supérieur au rapport dans le cas de Mn (tri). In the case of Zn (II), the ratio '-' is generally of the order of 10 IHCO31

100 times higher than the ratio in the case of Mn (sorting).

Typically, this ratio is 10-4 or more, preferably 10-3 or higher, and preferably of the order of 5-10.

In the case of a mixture of Mn (II) and Zn (II), the ratio generally varies from 10-5 to 10-1, preferably 10-3 to 10-2, this ratio being chosen higher when the proportion Zn (II) in the mixture increases.

 Generally, the molar concentration of Mn (II), Zn (II), or Mn (II) + Zn (II) in the final composition varies from 10-3 to 10 mM / l, preferably from 10-2 to 1 mM / 1.

10-3 à 10''mM/1, de préférence 10-2 à 10-1 mM/1. When only one or more salts or oxides of Mn (II) are used, the molar concentration of Mn (II) in the final composition is typically

10-3 at 10 "mM / l, preferably 10-2 at 10-1 mM / l.

 Preferably, when only one or more Zn (II) salts or oxides are used, the concentration of Zn (II) in the final composition is 5. 10-2 to 10 mM / l, more preferably 5. 10- 1 to 1 mM / l.

 Among the salts of Mn (II) and Zn (II) suitable for the present invention, mention may be made of chloride, fluoride, iodide, sulfate, phosphate, nitrate and perchlorate, the carboxylic acid salts and their mixtures.

 By way of example, mention may be made of manganese chloride, manganese carbonate (for example rhodochrosite), Mn (II) difluoride, Mn (II) acetate tetrahydrate, Mn (II) lactate trihydrate , Mn (II) phosphate, Mn (II) iodide, Mn (II) nitrate trihydrate, Mn (II) bromide and Mn (II) perchlorate tetrahydrate, and Mn sulphate ( II) monohydrate.

 Particularly preferred salts are MnCl and ZnCl2.

 The carboxylic acid salts also include hydroxyl carboxylic acid salts such as gluconate.

 Among the alkaline and alkaline-earth hydrogenocarbonates, mention may be made of the hydrogenocarbonates of Na, K, Mg, Ca and mixtures thereof, preferentially Na hydrogen carbonate.

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As indicated above, the chemical catalytic system according to the invention constitutes a pseudo-oxidase in that it oxidizes the polyphenols, in the presence of oxygen, as would a natural enzymatic catalyst having a polyphenoloxidase activity.

 On the other hand, the catalytic system according to the invention has no pseudocatalase activity in that it does not cause the disproportionation of hydrogen peroxide at 0.3% by weight (ie 1 volume of oxygen).

 In addition, the pseudo-oxidase activity is related to the use of the catalytic system according to the invention. Thus, each of the components of the catalytic system taken separately has no pseudo-oxidase activity. Just as replacing the salt of Mn (II) or Zn (II) with another salt, Fe, Cu or even Mn (III) does not lead to a catalytic system having a pseudooxidase activity.

 The dye precursors of the compositions of the invention are compounds or mixtures of compounds comprising at least one aromatic ring, preferably a benzene ring, comprising at least two hydroxyl groups (OH) borne by two consecutive carbon atoms of the aromatic ring.

 The aromatic ring may be a fused aromatic ring optionally containing one or more heteroatoms, such as naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, indole, isoindole, indoline , isoindoline, benzofuran, dihydrobenzofuran, chroman, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline.

The dye precursors according to the invention may be represented by the formula:

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dans laquelle les substituts R1 à R4, identiques ou différents, représentent un atome d'hydrogène, un radical halogène, hydroxyle, carboxyle, carboxylate d'alkyle, amino éventuellement substitué, alkyle linéaire ou ramifié éventuellement substitué, alcényle linéaire ou ramifié éventuellement substitué, cycloalkyle éventuellement substitué, alcoxy, alcoxyalkyle, alcoxyaryle, le groupe aryle pouvant être éventuellement substitué, aryle, aryle substitué, un radical hétérocyclique éventuellement substitué, un radical contenant un ou plusieurs atomes de silicium, où deux des substituants R1 à R4 forment conjointement un cycle saturé ou insaturé contenant éventuellement un ou plusieurs hétéroatomes et éventuellement condensé avec un ou plusieurs cycles saturés ou insaturés contenant éventuellement un ou plusieurs hétéroatomes.

in which the substituents R1 to R4, which may be identical or different, represent a hydrogen atom, a halogen, hydroxyl, carboxyl, alkyl carboxylate, optionally substituted amino, optionally substituted linear or branched alkyl radical, optionally substituted linear or branched alkenyl, optionally substituted cycloalkyl, alkoxy, alkoxyalkyl, alkoxyaryl, the optionally substituted aryl group, aryl, substituted aryl, an optionally substituted heterocyclic radical, a radical containing one or more silicon atoms, wherein two of the substituents R1 to R4 together form a ring saturated or unsaturated optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms.

 The saturated or unsaturated cycles, optionally condensed, may also be optionally substituted.

 The alkyl radicals are generally C 1 -C 10 alkyl radicals, preferably C 1 -C 6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl.

 The alkoxy radicals are in general C 1 -C 20 alkoxy radicals, such as methoxy, ethoxy, propoxy and butoxy.

 Alkoxyalkyl radicals are preferably (C1-C20) alkoxy (C1-C20) alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, and the like.

 The cycloalkyl radicals are in general the C 4 -C 8 cycloalkyl radicals, preferably the cyclopentyl and cyclohexyl radicals. The cycloalkyl radicals may be substituted cycloalkyl radicals, in particular with alkyl, alkoxy, carboxylic acid, hydroxyl, amine and ketone groups.

 The alkenyl radicals are preferably C1-C20 radicals, such as ethylene, propylene, butylene, pentylene, methyl-2-propylene and decylene.

 The radicals containing one or more silicon atoms are preferably polydimethylsiloxane, polydiphenylsiloxane, polydimethylphenylsiloxane and steroxydimethicone radicals.

 The heterocyclic radicals are generally radicals comprising one or more heteroatoms chosen from O, N and S, preferably O or N, optionally substituted by one or more alkyl, alkoxy, carboxylic acid, hydroxyl, amine or ketone groups.

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Among the preferred heterocyclic radicals, mention may be made of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl and thienyl groups.

 More preferably, the heterocyclic groups are fused groups such as benzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromannyl, isochromannyl, indolinyl, isoindolinyl, coumarinyl, isocoumarinyl, these groups may be substituted, in particular by one or more OH groups.

éventuellement osylés (par exemple glucosylés) ; - la 3, 4-dihydroxyphénylalanine et ses dérivés ; - la 2, 3-dihydroxyphenylalanine et ses dérivés ; - la 4, 5-dihydroxyphenylalanine et ses dérivés ; - le 4, 5-dihydroxyindole et ses dérivés ; - le 5, 6-dihydroxyindole et ses dérivés ; - le 6, 7-dihydroxyindole et ses dérivés ; - le 2, 3-dihydroxyindole et ses dérivés ; - les dihydroxycinnnamates tels que l'acide caféique et l'acide chlorogénique ; - les hydroxycoumarines ; - les hydroxyisocoumarines ; - les hydroxycoumarones ; - les hydroxyisocoumarones ; - les hydroxychalcones ; - les hydroxychromones ; - les anthocyanes ; The preferred dye precursors are: flavanols such as catechin and epichatechin gallate, flavonols such as quercetin, anthocyanidins such as peonidine, anthocyanins, for example oenine, hydroxybenzoates, for example gallic acid, flavones such as luteolin, iridoids such as oleuropein, these products may be osylated (for example glucosylated) and / or in the form of oligomers (procyanidines); hydroxystilbenes, for example tetrahydroxy-3,3 ', 4,5'-stilbene,

optionally osylated (for example glucosylated); 3,4-dihydroxyphenylalanine and its derivatives; 2,3-dihydroxyphenylalanine and its derivatives; 4,5-dihydroxyphenylalanine and its derivatives; 4,5-dihydroxyindole and its derivatives; - 5,6-dihydroxyindole and its derivatives; 6,7-dihydroxyindole and its derivatives; 2,3-dihydroxyindole and its derivatives; - Dihydroxycinnnamates such as caffeic acid and chlorogenic acid; hydroxycoumarines; hydroxyisocoumarines; - hydroxycoumarones; hydroxyisocoumarones; hydroxychalcones; - hydroxychromones; anthocyanins;

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- les quinones ; - les hydroxyxanthones ; et - les mélanges de ceux-ci.

quinones; hydroxyxanthones; and - mixtures thereof.

 When the dye precursors have D and L forms, both forms can be used in the compositions according to the invention.

 By varying the nature of the different dye precursors and their proportions in the composition, the color of the final coloring composition can be varied. This gives a palette of colors.

 For example, with a 1/10 ratio of chlorogenic acid and catechin, a light brown color is obtained and with a 1/1 ratio a mahogany coloring.

 The polymers formed in particular with catechin, gallic acid and their derivatives (tannins) have antimicrobial properties by imprisoning the microorganisms during the polymerization. These tannins also have interesting astringent properties for the skin.

 The precursors of dyes may be extracts of plants, fruits, citrus fruits, vegetables and mixtures of these extracts, which contain many polyphenols as defined above.

 Herbal extracts include rose and tea extracts.

 Among the fruit extracts, mention may be made of apple, grape (in particular grape seed) and banana extracts.

 Among the vegetable extracts, mention may be made of potato extract.

 Mixtures of plant and / or fruit extracts such as mixtures of apple and tea extracts and mixtures of grape and apple extracts can also be used.

 Depending on the fruit parts used, for example pulp or grape seeds, the coloring obtained is different.

 The amount of dye precursor in the final composition should be sufficient to obtain visible color. This amount can vary widely depending upon the nature of the precursor and the intensity desired for the coloring.

 In general, a suitable coloration will be obtained when the amount of dye precursor is such that the dye precursor content in the final dye composition is at least 10 micromoles per milliliter of final composition.

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Le milieu physiologiquement acceptable est un milieu solide ou liquide ne nuisant pas à la propriété de coloration des précurseurs ni à l'effet catalytique du système catalytique.

The physiologically acceptable medium is a solid or liquid medium that does not adversely affect the precursor staining property or the catalytic effect of the catalytic system.

 The physiologically acceptable medium is preferably a solubilizing medium of the dye precursor and bacteriostatic property.

Among the precursor solvents suitable for the formulation of the compositions according to the invention, mention may be made of water, alcohols, polar solvents and mixtures thereof.

The alcohols are preferably lower (C 1 -C 6) alkanols such as ethanol and isopropanol and alkanediols such as ethylene glycol, propylene glycol and pentane diol.

 Among the polar solvents, mention may be made of ethers, esters (in particular acetates), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), ketones (in particular acetone) and their mixtures.

 The physiologically acceptable medium preferably comprises water (in particular distilled or permuted) or a water / alcohol mixture, in particular water / ethanol.

 The amount of alcohol in the water / alcohol mixture may be up to 80% by weight of the water / alcohol mixture, preferably 1 to 50% by weight and more preferably 5 to 20% by weight.

 The physiologically acceptable medium may be a solid medium such as an excipient for the formulation of pebbles and tablets, in particular effervescent.

 The compositions according to the invention may also comprise any conventional adjuvant, in usual proportion, which does not adversely affect the desired properties, in particular the coloring effect of the compositions.

 The compositions of the invention may for example comprise sunscreens and UV protection, such as organic filters such as benzophenone, benzylidene, triazine derivatives, hydroxyphenyl benzotriazole derivatives, derivatives of the cinnamic acid, oxybenzone derivatives, octoclylene, benzilidenecamphor derivatives and mineral filters such as ZnO, shots.

 When the compositions according to the invention comprise pigments and conventional dyes, they can be used to obtain products such as foundations whose coloring action provided to the skin by the skin.

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pigments et/ou colorants est prolongée dans le temps. En effet, par suite du frottement notamment des joues et du cou, un fond de teint classique et par suite son effet colorant tend à disparaître. L'utilisation d'une composition selon l'invention dans une formulation de fond de teint permettrait donc de pallier cet effet.

pigments and / or dyes is extended in time. Indeed, as a result of friction including cheeks and neck, a classic foundation and therefore its coloring effect tends to disappear. The use of a composition according to the invention in a foundation formulation would thus make it possible to overcome this effect.

 Preferably, the compositions according to the invention are free of chelating agents of the Mn (II) and / or Zn (II) salts used, since these agents tend to inhibit the oxidation of the dye precursors.

 To reveal the coloration of the compositions according to the invention, it is sufficient to put the composition containing at least one dye precursor and an effective amount of the catalyst system according to the invention, in the presence of an oxidizing medium such as a medium containing oxygen (for example oxygen from the air).

 The compositions according to the invention are useful for coloring the skin and / or keratin fibers such as the hair, the eyelashes, the eyebrows and the hairs. They can also be used for coloring foods.

 For the coloration of the skin and keratinous fibers, various methods of applying the compositions according to the invention may be used.

 According to a first method, the skin or the keratinous fibers, in the presence of oxygen, for example oxygen of the air, is applied to a composition comprising all the ingredients of the composition, that is to say at the same time the dye precursor (s) and the catalyst system.

 According to a second method, it is first possible to apply a film of a base composition of one or more dye precursors in a physiologically acceptable medium to the skin or to the keratinous fibers, and then to the base composition film, a film of the catalytic system in a physiologically acceptable medium, which in the presence of oxygen, will reveal the coloring of the base composition.

 We can of course reverse the order of application of the films.

 The application of the films can be done by any known means, in particular by spraying.

 The compositions of the invention may, depending on the choice of dye precursors, constitute artificial tanning compositions which, when sunscreens have been incorporated, give the skin an appearance

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artificiellement bronzé, tout en permettant une exposition sans risque au soleil ou aux UV po ur un bronzage naturel.

artificially tanned, while allowing safe exposure to the sun or UV for a natural tan.

 The compositions of the invention may also make it possible to mask pigmentation defects such as vitiligo, the pregnancy mask, as well as skin imperfections such as age spots and rosacea.

 The coloration of the composition may be determined by the choice of dye precursors as a function of the defect to be masked.

 The compositions of the invention have the advantage of not requiring the use of hydrogen peroxide.

 The compositions according to the invention can be presented and be packaged in different forms.

 According to a first embodiment, the compositions according to the invention may be packaged in the form of a single-compartment aerosol in which there is the composition containing the dye precursor (s) and the catalytic system, and a conventional inert propellant gas such as nitrogen, a saturated hydrocarbon such as isopropane or a fluorinated hydrocarbon, for example a Freon®.

 In a second embodiment, the composition according to the invention may be packaged in the form of a kit comprising two distinct containers, one for the base composition containing the dye precursor (s), the other for the catalytic system, the base composition and the catalyst system being mixed or applied successively at the time of use.

 In a third embodiment, the composition may be contained in a single compartment pump system, without air intake, or in a two compartment pump system, the base composition being in a compartment and the catalytic system in the compartment. 'other.

 In a fourth embodiment, the composition according to the invention may be in the form of rollers, in particular for the bath. Each roller may comprise, mixed with an excipient, the dye precursor (s) and the catalytic system, the excipient preventing the reaction in the presence of oxygen or the dye precursor (s) and the catalytic system are contained in separate rollers.

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By disintegrating either the single roller or a roller of each of the constituents in water, for example the water of a bath, the coloring composition according to the invention is produced.

 The rollers, as is conventional, may be effervescent pebbles.

 The excipient used may be any conventional excipient such as a mixture of talc, stearate (especially magnesium), citric acid and / or tartaric, and alkali and / or alkaline earth hydrogen carbonate.

 The amount of citric and / or tartaric acid present should be such that there is no neutralization of the hydrogencarbonate resulting in a lack of free hydrogen carbonate relative to Mn (II) and / or Zn (II) .

 On the other hand, since water, especially tap water and certain spring or mineral waters, generally contain manganese (II), it is sometimes sufficient to put in the water the only roller containing water. hydrogen carbonate and the precursor (s) of staining, the Mn (II) content of the catalytic system then being provided by the Mn (II) present in the water.

 Similarly, some plant extracts (eg tea leaf extracts) may contain significant amounts of manganese (II). Depending on these contents, an adjustment of the concentrations of the catalytic system is carried out so as to have a satisfactory result.

 Of course, the intensity of the color can be varied by disintegrating several pebbles in the water.

 On the other hand, the coloring rate can be accelerated by adding to the composition a compound or a formulation of oxygen generating compounds, for example by contact with water. Thus, such a compound or formulation, for example sodium peroxide, can be incorporated in a roller.

 The following examples illustrate the present invention. In the examples, unless otherwise indicated, all percentages and parts are by weight.

EXAMPLE 1
Several dye composition formulations were prepared by varying the [MnCl 2] / [NaHCO 3] molar ratio of the catalyst system.

The formulations are given in Table 1 below:

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TABLEAU

BOARD

<Tb>
<tb> Formulation <SEP> Precursor <SEP> of <SEP> Staining <SEP> Medium <SEP> Catalyst System <SEP>
<tb> NO <SEP> physiologically
<tb> acceptable
<tb> Nature <SEP> Concentration <SEP> Ratio <SEP> Concentration <SEP> Concentration
<tb> (mM / l) <SEP> MnCl 2 <SEP> MnCl 2 <SEP> NaHCO 3
<tb> NaHCO3 <SEP> (mM / l) <SEP> (mM / l)
<tb> 1 <SEP> Catechin <SEP> 1 <SEP> Solution <SEP> saline <SEP> with <SEP> 10-3 <SEP> 10-2 <SEP> 10
<tb> 2 <SEP> Catechin <SEP> 1 <SEP> Buffer <SEP> phosphate <SEP> 2.5 <SEP> 10-3 <SEP> 2.5. <SEP> 10-2 <SEP> 10
<tb> 3 <SEP> Catechin <SEP> 1 <SEP> From <SEP> Dulbecco <SEP> (PBS) <SEP> 5. <SEP> 10-3 <SEP> 5. <SEP> 10-2 <SEP > 10
<tb> 4 <SEP> Catechin <SEP> 1 <SEP> or <SEP> into <SEP> g / l <SEP>: <SEP> 10 '<SEP> 10-1 <SEP> 10
<tb> 5 <SEP> L-DOPA <SEP> 1 <SEP> KH2PO4 <SEP>: <SEP> 0.2 <SEP> 10-3 <SEP> 10-2 <SEP> 10
<tb> 6 <SEP> L-DOPA <SEP> 1 <SEP> MnCl 2 <SEP>: <SEP> 0.2 <SEP> 2.5. <SEP> 10-3 <SEP> 2.5. <SEP> 10-2 <SEP> 10
<tb> 7 <SEP> L-DOPA <SEP> 1 <SEP> NaCl <SEP>: <SEP> 8, <SEP> 0 <SEP> and <SEP> 5. <SEP> 10-3 <SEP> 5 <SEP> 10-2 <SEP> 10
<tb> Na2HPO4 <SEP>#<SEP> 1.15
<tb> 8 <SEP> L-DOPA <SEP> 1 <SEP> and <SEP> 10 <SEP>% <SEP> in <SEP> weight <SEP> 10-2 <SEP> 10-1 <SEP> 10
<tb> ethanol
<Tb>

détermination de Vmax s'effectue sur 8 points pendant les 40 premières minutes. Les lectures en densité optique ont été effectuées à 475 nm avec un lecteur de densité optique Labsystem iEMS. Maximum air velocity (Vmax) values of the above formulations were measured. The maximum speed is the increase of the optical millidensity (mDo) per minute over the kinetic zone in which this speed is maximum. A measurement is made every minute and the

Vmax is determined on 8 points during the first 40 minutes. The optical density readings were taken at 475 nm with an Labsystem iEMS optical density meter.

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Les résultats sont donnés dans le Tableau II ci-dessous : TABLEAU fi

The results are given in Table II below:

<Tb>
<tb> Formulation <SEP>? <SEP> Vmax
<tb> 1 <SEP> 135
<tb> 2 <SEP> 155, <SEP> 8
<tb> 3 <SEP> 177, <SEP> 8
<tb> 4 <SEP> 158
<tb> 5 <SEP> 38, <SEP> 3
<tb> 6 <SEP> 48, <SEP> 8
<tb> 7 <SEP> 61
<tb> 8 <SEP> 55, <SEP> 8
<Tb>

The coloring compositions according to the invention have numerous advantages in the field of the coloration of the skin and the hair. For example, the resistance on the skin is enhanced by performing the reaction in situ. The coloration can be carried out with natural extracts containing polyphenols and have a henna-like coloring without the disadvantage of the presence of naphthoquinones in these colors. Another advantage is to have reactions like certain enzymes without the problems related to their uses in the cosmetic and dermatological field.

 For the more biological field the vectorization of such assets is easier because of the size and the toxicological risk significantly less than the use of proteins. The half-life of such a mixture is probably greater than a protein which would undergo without rapid immobilization a rapid degradation by the proteases of the tissues.

 The use of a bronzing composition for the bath has the advantage of avoiding the consumer exposure to UV for a long time to have a result (the association with a high filtering formulation is possible and provides a more effective safety screws to UV).

 The use of sodium hydrogencarbonate does not appear to present toxicological risks (authorized use in cosmetics) and the amount of manganese is extremely low. For example, for a bath with a green tea extract (long), 20 g of sodium hydrogencarbonate and 100 mg of

<Desc / Clms Page number 15>

 manganese, a ratio [Mn (II)] / [HC03] of the order of 1/500, are sufficient to have a color development in a bath of 100 liters. Some natural extracts (for example of tea) contain Mn (II) and, in this case, it will suffice to adapt the dosage of the formulation according to the Mn (II) content of the natural extract.

Claims (57)

 where [Mn (II)], [Zn (II)] and [HC031 represent respectively molar concentrations of Mn (II), Zn (II) and HC03 in the composition.

 [Mn (II)] 0 [c <9] with [Zn (II) O] [CO] [M] + Z (7 /)] [770 (9)]

 l. Composition for coloring the skin and / or keratinous fibers, characterized in that it comprises, in a physiologically acceptable medium, an effective amount of at least one dye precursor chosen from compounds comprising at least one aromatic ring having at least two hydroxyl groups carried by two consecutive carbon atoms of the aromatic ring and an effective amount of a catalytic system comprising a first component selected from the salts and oxides of Mn (II) and / or Zn (tri) and their mixtures and a second constituent selected from alkaline hydrogen carbonates, alkaline earth hydrogencarbonates and mixtures thereof, the proportions of the first and second constituent being such that:

2. Composition according to claim 1, characterized in that the ratio [Mn (II) varies varies from 10-5 to preferably from 10-3 to 10-2 and better is of the order [HCO3] of 5. 10 -3. 3. Composition according to claim 1 or 2, characterized in that the ratio [Zn ranges from 10-4 to <1, preferably from 10-3 to <1, and better is [HCO3] in the order of 5. 10-1. 4. Composition according to any one of the preceding claims, characterized in that the ratio varies from 10 to 10, preferably from 10 to 10 -2. <Desc / Clms Page number 17>

 5. Composition according to any one of the preceding claims, characterized in that the salts of Mn (II) and Zn (tri) are chosen from chloride, fluoride, iodide, sulfate, phosphate, nitrate, perchlorate, sodium salts and carboxylic acids and mixtures thereof.  6. Composition according to claim 5, characterized in that the salt of Mn (II) and / or Zn (II) is chloride.  7. Composition according to Claim 5, characterized in that the carboxylic acid salts are hydroxylated carboxylic acid salts.  8. Composition according to Claim 7, characterized in that the hydroxylated carboxylic acid salt is gluconate.  9. Composition according to any one of the preceding claims, characterized in that the hydrogencarbonate is selected from sodium hydrogen carbonate, potassium hydrogencarbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate and mixtures thereof.  10. Composition according to any one of the preceding claims, characterized in that the aromatic ring comprising at least two hydroxyl groups on two consecutive carbon atoms of the dye precursor is a benzene ring or a condensed aromatic ring.  11. Composition according to claim 10, characterized in that the dye precursor is a compound of formula:

 in which the substituents R1 to R4, which may be identical or different, represent a hydrogen atom, a halogen, a hydroxyl, carboxyl, alkyl carboxylate, optionally substituted amino, optionally substituted linear or branched alkyl radical, optionally substituted linear or branched alkenyl , optionally substituted cycloalkyl, alkoxy, alkoxyalkyl, alkoxyalkyl, <Desc / Clms Page number 18>  aryl group may be optionally substituted, aryl, substituted aryl, an optionally substituted heterocyclic radical, a radical optionally containing one or more silicon atoms, wherein two of the substituents R 1 to R 4 may together form a saturated or unsaturated ring optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms.

 12. The composition according to claim 1, wherein the dye precursor is chosen from flavanols, optionally osylated and / or in the form of oligomers, the optionally osylated hydroxystilbenes, 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, 4,5 Dihydroxyindole and its derivatives, 5,6-dihydroxyindole and its derivatives, 6,7-dihydroxyindole and its derivatives, 2,3-dihydroxyindole and its derivatives, dihydroxycinnamates, hydroxycoumarines, hydroxyisocoumarines, hydroxycoumarones, hydroxyisocoumarones hydroxychalcones, hydroxychromones, anthocyanins, quinones, hydroxyxantones, and mixtures of two or more of the foregoing compounds.  13. Composition according to any one of claims 1 to 10, characterized in that the dye precursor is selected from extracts of plants, fruits, citrus fruits, vegetables and mixtures thereof.  14. Composition according to Claim 13, characterized in that the dye precursor is chosen from tea, grape, apple, banana and potato extracts and their mixtures.  15. Composition according to any one of the preceding claims, characterized in that the dye precursor is present in an amount of at least 10 micromoles per milliliter of composition.  16. Composition according to any one of the preceding claims, characterized in that the physiologically acceptable medium is a solubilizing medium of the dye precursor, preferably bacteriostatic property. <Desc / Clms Page number 19>

17. Composition according to any one of the preceding claims, characterized in that the physiologically acceptable medium comprises a solvent or a solvent mixture of the dye precursor.  18. A composition according to claim 17, characterized in that the solvent is selected from water, alcohols, ethers, dimethylsulfoxide, N-methylpryrrolidone, acetones and mixtures thereof.  19. Composition according to claim 18, characterized in that the alcohol is an alkanol or an alkanediol.  20. Composition according to claim 18, characterized in that the solvent is a water / alcohol mixture.  21. Composition according to claim 20, characterized in that alcohol represents up to 80% by weight of the mixture, preferably 1 to 50% by weight and better still 5 to 20% by weight.  22. Composition according to any one of the preceding claims, characterized in that it is free from any chelating agent of the salt of Mn (II) and / or Zn (sil).  23. Composition according to any one of the preceding claims, characterized in that it is in the form of two separate components, a first component comprising the catalytic system dissolved in a physiologically acceptable medium and a second component comprising the dye precursor dissolved in a physiologically acceptable medium.  24. Composition according to any one of claims 1 to 22, characterized in that it is packaged in the form of an aerosol or a pump system without air intake.  25. Composition according to claim 23, characterized in that it is packaged in a pump system with two separate compartments, each of the components being contained separately in one of the two compartments.  26. Composition according to any one of claims 1 to 14, characterized in that it is packaged in the form of a roller.  27. Composition according to claim 26, characterized in that the tablet comprises an excipient containing citric acid and / or tartaric in stoichiometric amount relative to the alkali and / or alkaline earth hydrogencarbonate.  28. Composition according to any one of claims 1 to 14, characterized in that it is packaged in the form of two rollers, a <Desc / Clms Page number 20>  first roller comprising the catalyst system and an excipient and a second roller comprising the dye precursor and an excipient.  29. Composition according to any one of claims 26 to 28, characterized in that the roller or rollers are effervescent rollers.  30. A method for revealing the coloration of a base composition with little or no color comprising in a physiologically acceptable medium, at least one dye precursor chosen from compounds comprising at least one aromatic ring having at least two hydroxyl groups carried by two atoms. consecutive carbon of the aromatic ring, characterized in that it consists in adding to the base composition, in the presence of oxygen, an effective amount of a catalytic system comprising a first component selected from the salts and oxides of Mn (II and / or Zn (II) and mixtures thereof and a second component selected from alkaline hydrogen carbonates,

 alkaline earth hydrogenocarbonates and mixtures thereof, the proportions of the first and second constituent being such that:

 <[Mn (II) O [Oe]) [Zn (II))] [CH 2 Cl 2 (MnO) + Z)] [fCO]

 where [Mn (II)], [Zn (II)] and [HCO3] respectively represent the molar concentrations of Mn (II), Zn (II) and HCO3 in the composition and to add the base composition plus the catalytic system to presence of a medium containing oxygen.

31. Process according to claim 30, characterized in that the ratio [Mn (II) 1 varies from 10-5 to 10 ', preferably from 10-3 to 10-2 and better is of the order IHCO31

 of 5. 10- '. <Desc / Clms Page number 21>

32. The method of claim 30 or 31, characterized in that the ratio [Zn (II varies from 10-4 to <1, preferably from 10-3 to <1, and better is [77C (9: j] the order of 5, 10-1, 33. Process according to any one of claims 30 to 32, characterized in that the ratio [Mn] varies from 10-5 to 10, preferably from 10-3 to 10-2.

34. Process according to any one of claims 30 to 33, characterized in that the salt of Mn (II) and the salt of Zn (II) are chosen from chloride, fluoride, iodide, sulfate, acetate, phosphate, carboxylic acid salts and mixtures thereof.  35. Process according to any one of Claims 30 to 34, characterized in that the salt of Mn (II) and / or salt of Zn (II) is chloride.  36. Process according to any one of claims 30 to 35, characterized in that the carboxylic acid salts are hydroxylated carboxylic acid salts.  37. Process according to any one of claims 30 to 36, characterized in that the hydroxylated carboxylic acid salt is gluconate.  38. Process according to any one of claims 30 to 37, characterized in that the hydrogencarbonate is chosen from sodium hydrogen carbonate, potassium hydrogencarbonate, magnesium hydrogen carbonate, calcium hydrogencarbonate and mixtures thereof. .  39. Process according to any one of claims 30 to 38, characterized in that the aromatic ring comprising at least two hydroxyl groups on two consecutive carbon atoms of the dye precursor is a benzene ring or a condensed aromatic ring. <Desc / Clms Page number 22>  optionally one or more silicon atoms, or two of the substituents R 1 to R 4 may together form a saturated or unsaturated ring optionally containing one or more heteroatoms and optionally fused with one or more saturated or unsaturated rings optionally containing one or more heteroatoms.

 in which the substituents R to R, identical or different, represent a hydrogen atom, a halogen, a hydroxyl, carboxyl, alkyl carboxylate, optionally substituted amino, optionally substituted linear or branched alkyl group, optionally substituted linear or branched alkenyl , optionally substituted cycloalkyl, alkoxy, alkoxyalkyl, alkoxyaryl, the aryl group may be optionally substituted, aryl, substituted aryl, an optionally substituted heterocyclic radical, a radical containing

 40. Process according to any one of claims 30 to 39, characterized in that the dye precursor is a compound of formula:

 41. Method according to any one of claims 30 to 39, characterized in that the dye precursor is chosen from flavanols, flavonols, anthocyaninidines, anthocyanins, hydroxybenzoates, flavones, iridoids, these compounds may be optionally osylated and / or in the form of oligomers, the optionally osylated hydroxystilbenes, 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyindole and its derivatives, 5,6-dihydroxyindole and its derivatives, 6,7-dihydroxyindole and its derivatives, 2,3-dihydroxyindole and its derivatives, dihydroxycinnamates, hydroxycoumarines, hydroxyisocoumarines, hydroxycoumarones, hydroxyisocoumarones, hydroxychalcones, hydroxychromones, <Desc / Clms Page number 23>  anthocyanins, quinones, hydroxyxantones, and mixtures of two or more of the foregoing compounds.

 42. Process according to any one of claims 30 to 39, characterized in that the dye precursor is chosen from extracts of plants, fruits, citrus fruits, vegetables and their mixtures.  43. The method of claim 42, characterized in that the dye precursor is selected from tea extracts, grape, apple, banana, potato and mixtures thereof.  44. Process according to any one of claims 30 to 43, characterized in that the dye precursor is present in an amount of at least 10 micromoles per milliliter of composition.  45. Process according to any one of claims 30 to 44, characterized in that the physiologically acceptable medium is a solubilizing medium of the dye precursor, preferably having a bacteriostatic property.  46. Process according to any one of claims 30 to 45, characterized in that the physiologically acceptable medium comprises a solvent or a solvent mixture of the dye precursor.  47. The method of claim 46, characterized in that the solvent is selected from water, alcohols, ethers, dimethylsulfoxide, Nvinylpyrrolidone, acetone and mixtures thereof.  48. Process according to claim 47, characterized in that the alcohol is an alkanol or an alkanediol.  49. Process according to claim 48, characterized in that the solvent is a water / alcohol mixture.  50. Process according to claim 49, characterized in that the alcohol mixture represents up to 80% by weight of the mixture, preferably 1 to 50% by weight and better still 5 to 20% by weight.  51. Process according to any one of claims 30 to 50, characterized in that it is free from any chelating agent of the salt of Mn (II) and / or Zn (II).  52. A process for obtaining a coloring composition, characterized in that it consists in adding to water a roller comprising in a physiologically acceptable excipient at least one dye precursor, as defined in claim 1, of alkaline or alkaline earth hydrogencarbonate <Desc / Clms Page number 24>  53. A process for obtaining a coloring composition, characterized in that it consists in adding to water a roller containing in a physiologically acceptable excipient at least one dye precursor and a roller containing in a physiologically acceptable excipient, a catalytic system, the precursor and the catalytic system being as defined in claim 1.

 [Mn /)] and / or [Zn (II)] j [C <9J ''

 and optionally at least one salt or oxide of Mn (II) and / or Zn (II) in appropriate amounts if the water does not contain Mn (II) and / or Zn (tri) in the required proportions, so than

 54. The method of claim 52 or 53, characterized in that the roller or rollers are effervescent rollers.  55. A method of dyeing the skin and / or keratin fibers, characterized in that it consists in applying to the skin and / or the keratinous fibers a layer of a composition according to any one of claims 1 to 22.  56. Process according to claim 55, characterized in that the layer is obtained by applying to the skin and / or the keratin fibers a first film of a base composition containing the dye precursor (s) in a physiologically acceptable medium and by applying to the first film a second film of a catalytic composition comprising the catalytic system in a physiologically acceptable medium and vice versa.  57. Process according to claim 55 or 56, characterized in that the films are applied by spraying.