WO2011157666A1

WO2011157666A1 - Cosmetic use of a natural extract derived from beetroot peel for dyeing hair composition comprising the extract, an oxidizing agent, a basifying agent an optional metallic derivative

Info

Publication number: WO2011157666A1
Application number: PCT/EP2011/059756
Authority: WO
Inventors: Frédéric Guerin; Patrick Choisy
Original assignee: L'oreal
Priority date: 2010-06-16
Filing date: 2011-06-13
Publication date: 2011-12-22
Also published as: FR2961398A1; FR2961398B1

Abstract

The invention relates to a composition comprising a) at least one natural extract derived from beetroot, rich in indoles and indolines, especially beetroot peel, b) at least one chemical oxidizing agent, d) at least one basifying agent to a process for dying keratin materials that uses ingredients a), b) and d) and to the use of the extract of beetroot peel in combination with a) and b) for keratin materials. This hair dyeing process and the composition make it possible to obtain better colorations, which are more uniform, chromatic and fast, and which do not impair the cosmetic properties of keratin fibers, using an extract of ortho-diphenols, which are especially natural.

Description

COSMETIC USE OF A NATURAL EXTRACT DERIVED FROM BEETROOT PEEL FOR DYEING HAIR COMPOSITION COMPRISING THE EXTRACT, AN OXIDIZING AGENT, A BASIFYING AGENT AN OPTIONAL METALLIC DERIVATIVE.

The invention relates to a composition comprising a) at least one natural extract derived from beetroot, rich in indoles and indolines, especially beetroot peel, b) at least one chemical oxidizing agent; to a process for treating keratin materials that uses ingredients a), and b) at least one oxidizing agent, and to the use of the extract of beetroot peel as an agent for treating keratin materials.

It is known practice to obtain "permanent" colorations with dye compositions containing oxidation dye precursors, which are generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds, which, when combined with oxidizing products, may give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers, the latter being chosen especially from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds. This oxidation dyeing process consists in applying to the keratin fibers bases or a mixture of bases and couplers with hydrogen peroxide H₂0₂ or aqueous hydrogen peroxide solution, as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibers. The colorations resulting therefrom are permanent, strong and resistant to external agents, especially to light, bad weather, washing, perspiration and rubbing.

However, commercial hair dyes that contain them may have drawbacks such as staining, and problems of odour, discomfort and degradation of the keratin fibers. This is particularly the case with oxidation dyeing. In the field of dyeing, it is also known practice to dye keratin materials such as the hair or the skin using ortho-diphenols in the presence of a metal salt especially of Mn and/or Zn. In particular, patent applications FR 2 814 943, FR 2 814 945, FR 2 814 946 and FR 2 814 947 propose compositions for dyeing the skin or keratin fibers, comprising a dye precursor that contains at least one ortho-diphenol, Mn and/or Zn oxides and salts, alkaline agents of hydrogen carbonate type in a particular Mn, Zn/hydrogen carbonate ratio and optionally an enzyme. According to said documents, it is possible to obtain colorations on keratin materials with atmospheric oxygen. However, the colorations obtained are not strong enough, especially in the case of hair fibers.

Beetroot (Beta vulgaris convar. Vulgaris var. esculenta, egypta, little ball, Forono, rubia L.) is a root vegetable.

Beetroot is a plant grown for its fleshy root, which is used as a legume in human nutrition, as a forage plant and for the production of sugar. Beetroot, or garden beet or Beta vulgaris convar vulgaris, is from the family of Chenopodiaceae, of the tribe of cyclolobae, according to the standard classification, or from the family of Amaranthaceae, according to the phylogenetic classification. Beetroot pigments are known as betalains, consisting of two sub-classes, betacyanins or red pigments and betaxanthins or yellow pigments, these pigments being highly water-soluble.

When beetroot powder is used as a food colorant, it is used for its red-pink-violet color. However, the use of beetroot peel extract has not been used hitherto for treating keratin materials. For example, it is not known practice to use beetroot extract for dyeing the hair. There is a real need to develop processes for treating keratin materials from natural extract, especially keratin fibers, in particular human keratin fibers such as the hair, which can produce powerful colorations while at the same time limiting the bleaching of the keratin fibers.

In particular, there is a need to obtain colorations that are less aggressive on keratin fibers, especially the hair, and that are simultaneously resistant to external agents such as light, bad weather and shampooing, that are fast and uniform, with little selectivity of coloration between the root and the end of the hairs, while at the same time remaining powerful and/or chromatic. This aim is achieved by the present invention, the subject of which is the use of beetroot extract, more specifically of extract of beetroot peel, as an agent for coloring keratin materials, in particular the hair. This extract can produce a dark color, in particular black, in an oxidizing medium. Another subject of the invention is a process for treating keratin materials, in which said materials are treated with:

a) one or more extract(s) of beetroot peel, and

b) one or more oxidizing agent(s). Another subject of the invention relates to a cosmetic composition for dyeing keratin fibers, comprising:

a) one or more extract(s) of beetroot peel; b) one or more oxidizing agent(s);

and optionally:

c) one or more metallic derivatives and/or one or more pro-oxidizing clay(s); and/or d) one or more basifying agent(s);

it being understood that when the composition does not contain c) or d), then the oxidizing agent(s) are chemical oxidizing agents other than atmospheric oxygen.

Another subject of the invention concerns a multi-compartment device comprising the ingredients a), b) and optionally c) and d) as defined previously.

The use of beetroot extract according to the invention has the advantage of enabling the treatment of keratin materials without impairing said materials. This use in particular makes it possible to color human keratin fibers, with powerful, chromatic dyeing results that are resistant to washing, perspiration, sebum and light, and which are moreover long-lasting without impairing said fibers. It is in particular possible to obtain black from beetroot peel extract in an oxidizing medium. Furthermore, the colorations obtained using the process give uniform colors from the root to the end of a fiber, and little coloration selectivity. a) beetroot extract:

The extract of beetroot or Beta vulgaris is preferentially an extract obtained from beetroot, especially from the periphery or outer part of beetroot, more particularly from beetroot skin or peel {Eur. Food. Res. Technol., Tytti S. Kujala et al., 214, 505-510 (2002)).

The term "beetroot skin" more particularly denotes the peripheral part of the tuber situated between the epidermis and the pericarp (cf. Hermann et al., Journal of Experimental Botany, Vol. 58, No. 1 1 , pp. 3047-3060, 2007).

The extracts are obtained by extracting the various plant parts, for instance the root, the leaves or the peel. Preferentially, the extract is obtained from extraction of beetroot peel.

The extraction is performed via standard methods known to those skilled in the art. Mention may be made, for example, of the method described in Eur. Food. Res. Technol., Tytti S. Kujala et al., 214, 505-510 (2002).

The natural beetroot extracts according to the invention may be in the form of powders or liquids. Preferentially, the extracts of the invention are in the form of powders, such as beetroot peel extract powder.

According to one preferred embodiment of the invention, the beetroot peel extract is rich in indoline and/or indolidine. It is understood by the term "rich in indole or indoline" that the proportion of indoline and/or indolidine is preferentially between 10% and 15%. According to one particular embodiment of the invention, the beetroot peel extract contains at least 0.5 mg of isobetanin per gram of peel extract (the amount may be determined, for example, by means of the technique used by T.S. Kujal et al. Eur. Food Res. Technol. 214, 505-510 (2002)).

Isobetalaine or (2S)-4-[2-[[(2R)-2-carboxy-5-( -D-glucopyranosyloxy)-2,3-dihydro-6-hydroxy- 1 /-/-indol]-1 -yl]ethenyl]-2,3-dihydro-2,6-pyridinedicarboxylic acid - Cas No.: 15121 -53-6. According to the invention, the beetroot extract(s) used as ingredient a) in one or more composition(s) that are useful in the process according to the invention preferably represent from 0.001 % to 20% by weight relative to the total weight of the composition(s) containing said extract(s). According to one particular embodiment, the process of the invention is performed using a composition also comprising one or more ortho-diphenols.

The additional ortho-diphenol(s): The term "ortho-diphenols" means organic compounds comprising at least one aromatic ring, preferably a benzene ring, comprising at least two hydroxyl groups (OH) borne by two adjacent carbon atoms of the aromatic ring.

The aromatic ring may more particularly be a fused aryl or fused heteroaromatic ring, i.e. optionally containing one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring comprising at least two hydroxyl groups borne by two adjacent carbon atoms of the aromatic ring. Preferentially, the aromatic ring of the ortho-diphenol derivatives according to the invention is a benzene ring.

The term "fused ring" means that at least two saturated or unsaturated, heterocyclic or non-heterocyclic rings have a common bond, i.e. at least one ring is fused to another ring.

The ortho-diphenols according to the invention may or may not be salified. They may also be in aglycone form (without attached sugar) or in the form of glycosylated compounds.

More particularly, the ortho-diphenol derivative a) represents a compound of formula (I), or an oligomer thereof, in salified or non-salified form:

in which formula (I) the substituents:

• R-i to R₄, which may be identical or different, represent:

a hydrogen atom,

a halogen atom,

a hydroxyl radical,

- a carboxyl radical,

an alkyl carboxylate or alkoxycarbonyl radical,

an optionally substituted amino radical,

an optionally substituted linear or branched alkyl radical,

an optionally substituted linear or branched alkenyl radical,

- an optionally substituted cycloalkyl radical,

an alkoxy radical,

an alkoxyalkyl radical,

an alkoxyaryl radical, the aryl group possibly being optionally substituted, an aryl radical,

- a substituted aryl radical,

a saturated or unsaturated heterocyclic radical, optionally bearing a cationic or anionic charge, optionally substituted and/or optionally fused with an aromatic ring, preferably a benzene ring, said aromatic ring being optionally substituted particularly with one or more hydroxyl or glycosyloxy groups,

- a radical containing one or more silicon atoms, • in which two of the substituents borne by two adjacent carbon atoms Ri - R₂, R2 - R₃ or R₃ - R₄ form, together with the carbon atoms that bear them, a saturated or unsaturated, aromatic or non-aromatic ring, optionally containing one or more heteroatoms and optionally fused with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. Particularly, R-i to R₄ together form from one to four rings.

One particular embodiment of the invention concerns ortho-diphenol derivatives of formula (I), of which two adjacent substituents Ri - R₂, R2 - R₃ or R₃- R₄ cannot form with the carbon atoms that bear them a pyrrolyl radical. More particularly, R₂ and R₃ cannot form a pyrrolyl radical fused to the benzene ring bearing the two hydroxyl groups.

The saturated or unsaturated, optionally fused rings may also be optionally substituted. The alkyl radicals are linear or branched, saturated hydrocarbon-based radicals, generally of C1-C2₀, particularly of C1-C1₀, preferably Ci-C₆ alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl.

The alkenyl radicals are linear or branched, unsaturated C₂-C₂o hydrocarbon-based radicals; preferably comprising at least one double bond, such as ethylene, propylene, butylene, pentylene, 2-methylpropylene and decylene.

The aryl radicals are fused or nonfused monocyclic or polycyclic carbon-based radicals, preferentially comprising from 6 to 30 carbon atoms, and of which at least one ring is aromatic; the aryl radical is preferentially chosen from phenyl, biphenyl, naphthyl, indenyl, anthracenyl and tetrahydronaphthyl.

The alkoxy radicals are alkyl-oxy radicals with alkyl as defined previously, preferably of Ci-Cio Such as methoxy, ethoxy, propoxy and butoxy.

The alkoxyalkyl radicals are preferably (Ci-C2o)alkoxy(Ci-C₂o)alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.

The cycloalkyl radicals are generally C₄-C₈ cycloalkyl radicals, preferably cyclopentyl and cyclohexyl radicals. The cycloalkyl radicals may be substituted cycloalkyl radicals, in particular substituted with alkyl, alkoxy, carboxylic acid, hydroxyl, amine and ketone groups.

The alkyl or alkenyl radicals, when they are optionally substituted, may be substituted with at least one substituent borne by at least one carbon atom, chosen from:

- a halogen atom;

- a hydroxyl group;

- a C1-C2 alkoxy radical;

- a C1-C1₀ alkoxycarbonyl radical;

- a C₂-C₄ (poly)hydroxyalkoxy radical; - an amino radical;

- a 5- or 6-membered heterocycloalkyl radical;

- an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (CrC₄)alkyl radical, preferentially methyl;

- a quaternary ammonium group -N⁺R'R"R"', M^" for which R', R" and R"\ which may be identical or different, represent a hydrogen atom or a Ci-C₄ alkyl group; and M^" represents the counterion of the organic or mineral acid or of the corresponding halide;

- an amino radical substituted with one or two identical or different Ci-C₆ alkyl radicals, optionally bearing at least:

* one hydroxyl group,

^* one amino group optionally substituted with one or two optionally substituted Ci-C₃ alkyl radicals, said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen,

^* a quaternary ammonium group -N⁺R'R"R"', M^" as defined previously,

^* or an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (CrC₄)alkyl radical, preferentially methyl;

- an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom, a Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a Ci-C₂ alkyl radical; a carbamoyl radical ((R)₂N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom, a Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group; an alkylsulfonylamino radical (R'S0₂-NR-) in which the radical R represents a hydrogen atom, a Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a Ci-C₄ alkyl radical or a phenyl radical; an aminosulfonyl radical ((R)₂N-S0₂-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group,

- a carboxylic radical in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);

- a cyano group;

- a nitro group;

- a carboxyl or glycosylcarbonyl group;

- a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; - a glycosyloxy group; and

- a phenyl group optionally substituted with one or more hydroxyl groups. The aryl or heterocyclic radicals or the aryl or heterocyclic part of the radicals, when they are optionally substituted, may be substituted with at least one substituent borne by at least one carbon atom, chosen from:

- a C-I-C-IO and preferably Ci-C₈ alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, CrC₂ alkoxy, C₂-C₄ (poly)hydroxyalkoxy, acylamino, amino substituted with two C C₄ alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6-membered heterocycle optionally comprising another heteroatom identical to or different from nitrogen;

- a halogen atom;

- a hydroxyl group;

- a C1-C2 alkoxy radical;

- a C1-C1₀ alkoxycarbonyl radical;

- a C₂-C₄ (poly)hydroxyalkoxy radical;

- an amino radical;

- a 5- or 6-membered heterocycloalkyl radical;

* one hydroxyl group,

* one amino group optionally substituted with one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen,

* a quaternary ammonium group -N⁺R'R"R"', M^" for which R', R" and R"\ which may be identical or different, represent a hydrogen atom or a C C₄ alkyl group; and M^" represents the counterion of the organic or mineral acid or of the corresponding halide;

* or an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (CrC₄)alkyl radical, preferentially methyl;

- an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom, a C C₄ alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-C2 alkyl radical; a carbamoyl radical ((R)₂N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C C₄ alkyl radical optionally bearing at least one hydroxyl group; an alkylsulfonylamino radical (R'S0₂-NR-) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a C1-C4 alkyl radical or a phenyl radical; an aminosulfonyl radical ((R)₂N-S0₂-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group;

- a cyano group;

- a nitro group;

- a polyhaloalkyl group, preferentially trifluoromethyl;

- a carboxyl or glycosylcarbonyl group;

- a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups;

- a glycosyloxy group; and

- a phenyl group optionally substituted with one or more hydroxyl groups.

The term "glycosyl radical" means a radical derived from a monosaccharide or polysaccharide. The radicals containing one or more silicon atoms are preferably polydimethylsiloxane, polydiphenylsiloxane, polydimethylphenylsiloxane or stearoxydimethicone radicals.

The heterocyclic radicals are generally radicals comprising in at least one ring one or more heteroatoms chosen from O, N and S, preferably O or N, optionally substituted especially with one or more alkyl, alkoxy, carboxylic acid, hydroxyl, amine or ketone groups. These rings may contain one or more oxo groups on the carbon atoms of the heterocycle.

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

More preferably, the heterocyclic groups are fused groups such as benzofuryl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromanyl, isochromanyl, indolinyl, isoindolinyl, coumarinyl or isocoumarinyl groups, these groups possibly being substituted, in particular with one or more OH groups.

The ortho-diphenols that are useful in the process of the invention may be natural or synthetic. Among the natural ortho-diphenols are compounds that may be present in nature and that are reproduced by chemical (semi)synthesis.

The ortho-diphenol salts of the invention may be salts of acids or bases. The acids may be mineral or organic. Preferably, the acid is hydrochloric acid, which leads to chlorides.

The bases may be mineral or organic. In particular, the bases are alkali metal hydroxides such as sodium hydroxide, which leads to sodium salts.

According to one particular embodiment of the invention, the composition comprises as ingredient i) one or more synthetic ortho-diphenol derivative(s) that do not exist in nature.

According to another preferred embodiment of the invention, the process for dyeing keratin fibers uses as ingredient a) one or more natural ortho-diphenol derivative(s).

More particularly, the ortho-diphenols that may be used in the process of the invention according to i) are in particular:

- flavanols, for instance catechin and epicatechin gallate,

- flavonols, such as quercetin,

- anthocyanidins, for instance cyanidin, delphinidin and petunidin,

- anthocyanins or anthocyans, for instance myrtillin,

- ortho-hydroxybenzoates, for example gallic acid salts,

- flavones, such as luteolin,

- hydroxystilbenes, for example tetrahydroxy-3,3',4,5'-stilbene, optionally oxylated (for example glucosylated),

- 3,4-dihydroxyphenylalanine and derivatives thereof,

- 2,3-dihydroxyphenylalanine and derivatives thereof,

- 4,5-dihydroxyphenylalanine and derivatives thereof,

- dihydroxycinnamates such as caffeic acid and chlorogenic acid,

- ortho-polyhydroxycoumarins,

- ortho-polyhydroxyisocoumarins,

- ortho-polyhydroxycoumarones,

- ortho-polyhydroxyisocoumarones,

- ortho-polyhydroxychalcones,

- ortho-polyhydroxychromones,

- ortho-polyhydroxyquinones,

- ortho-polyhydroxyxanthones,

- 1 ,2-dihydroxybenzene and derivatives thereof,

- 1 ,2,4-trihydroxybenzene and derivatives thereof,

- 1 ,2,3-trihydroxybenzene and derivatives thereof,

- 2,4,5-trihydroxytoluene and derivatives thereof,

- proanthocyanidins and especially the proanthocyanidins A1 , A2, B1 , B2, B3 and C1 ,

- proanthocyanins, - ortho-hydroxycoumestanes,

- ortho-hydroxypterocarpanes,

- ortho-hydroxyneoflavans

- tannic acid,

- ellagic acid,

- and mixtures of the preceding compounds, particularly catechin, quercetin, braziline, hematin, hematoxylin, chlorogenic acid, caffeic acid, gallic acid, catechol, gallic acid, L-DOPA, pelargonidin, cyanidin, (-)-epicatechin, (-)-epigallocatechin, (-)-epigallocatechin 3-gallate (EGCG), (+)-catechin, isoquercetin, pomiferin, esculetin, 6,7-dihydroxy-3-(3-hydroxy-2,4-dimethoxyphenyl)coumarin, santalin AC, mangiferin, butein, maritimetin, sulfuretin, robtein, betanidin, pericampylinone A, theaflavin, proanthocyanidin A2, proanthocyanidin B2, proanthocyanidin C1 , procyanidins DP 4-8, tannic acid, purpurogallin, 5,6-dihydroxy-2-methyl-1 ,4-naphthoquinone, alizarin, wedelolactone, variegatic acid, gomphidic acid, xerocomic acid, carnosol, and natural extracts containing them.

When the dye precursors have D and L forms, the two forms may be used in the compositions according to the invention, as may the racemic mixtures.

According to one embodiment, the natural ortho-diphenols are derived from extracts of animals, bacteria, fungi, algae or plants, used in their entirety or partially. In particular as regards plants, the extracts are derived from plant or plant parts such as fruit, including citrus fruit, legumes, trees and shrubs. Mixtures of these extracts that are rich in ortho-diphenols as defined previously may also be used.

Preferably, the natural ortho-diphenol(s) of the invention are derived from extracts of plants or plant parts.

For the purposes of the invention, said extracts will be assimilated in their entirety as compound a).

The extracts are obtained by extraction of various plant parts, for instance the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the clove or the peel.

Among the plant extracts, mention may be made of extracts of tea leaves, of reseda, of cosmos, of coreopsis or of broom.

Among the fruit extracts, mention may be made of extracts of apple, of grape (in particular of grape seed), of pomegranate, or extracts of cocoa beans and/or pods.

Among the legume extracts, mention may be made of extracts of potato or of onion peel.

Among the tree wood extracts, mention may be made of extracts of pine bark and extracts of logwood, braziletto, oak, chestnut, sumach, tara, valonia, catechu, divi-divi, mimosa, pernambuco, dyer's mulberry, quebracho, gambier or myrobalan wood.

Among the gall extracts, mention may be made of extracts of maple, ash, beech, American mountain ash and above all oak gall nut.

Mixtures of plant extracts may also be used.

According to one particular embodiment of the invention, the ortho-diphenol derivative(s) are natural extracts, rich in ortho-diphenols. According to one preferred mode, the ortho-diphenol derivative(s) are solely natural extracts.

Preferentially, the ortho-diphenol(s) according to the invention are chosen from catechins, quercetin, haematin, haematoxylin, brasilin, gallic acid, and natural extracts containing them chosen from grape marc, pine bark, green tea, onion, cocoa bean, logwood, redwood and gall nut, extracts of quebracho wood and extracts of braziletto wood.

The natural extracts according to the invention may be in the form of powders or liquids. Preferably, the extracts of the invention are in the form of powders.

According to the invention, the natural, synthetic ortho-diphenol derivative(s), and/or the natural extract(s) used as ingredient i) in one or more composition(s) that are useful in the process according to the invention preferably represent from 0.001 % to 20% by weight relative to the total weight of the composition(s) containing the ortho-diphenol(s) or the extract(s).

As regards the pure ortho-diphenols, the content in the composition(s) containing them is preferably between 0.001 % and 5% by weight of each of these compositions.

As regards the extracts, the content in the composition(s) containing the extracts per se is preferably between 0.5% and 20% by weight of each of these compositions. b) The oxidizing agent (s);

The oxidizing agent that is useful in the present invention may be derived from atmospheric oxygen and/or from one or more supported or unsupported chemical oxidizing agent(s). More precisely, the oxidizing agent that is useful according to the invention is other than c) metallic derivatives and pro-oxidizing clays as defined below.

Particularly:

a) ozone;

b) alkali metal or quaternary ammonium persalts such as perborates, persulfates, percarbonates or peroxodiphosphates, Oxone® or potassium persulfate; the oxidizing agent is particularly chosen from sodium perborate, sodium persulfate, potassium persulfate, ammonium persulfate, sodium carbonate and potassium carbonate; c) aliphatic Ci-C₆ and aromatic C₈-C₂o organic peracids, and the percarboxylate forms thereof: R-C(0)0-OM' with R representing a group (CrC₆)alkyl or (C₆-C₂o)aryl such as phenyl, M' representing a hydrogen atom (peracid) or an alkali metal or alkaline- earth metal (percarboxylate), are chosen from performic acid, peracetic acid, perbenzoic acid derivatives, trifluoroacetic acid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid; the oxidizing agent is particularly peracetic acid;

d) organic peroxides chosen from dioxirane, Ci-C₆ alkyl peroxides, benzoyl peroxide, peroxo(CrC₆)alkyl carboxylates, bis(tri)(C₁-C₆)alkylsilyl peroxides such as bis(trimethylsilyl) peroxide, Ci-C₆ alkyl peroxydicarbonates, and sodium nonanoyloxybenzene sulfonate as described in patents WO 1995/000 625 and US 4

412 934;

e) oxidizing anions chosen from nitrites, nitrates, hypochlorites, hypobromites, hypoiodites, chlorites, bromites, iodites, chlorates, bromates, iodates and periodates; the oxidizing agent is more particularly chosen from an alkali metal hypochlorite or periodate such as sodium hypochlorite or sodium periodate;

f) stable radicals containing an N-oxy (NO) group, chosen from i) heterocycles containing a sterically hindered N-oxide group such as the radical 2,2,6,6-tetra(Cr C6)alkylpiperidinooxy-2,2,6,6-tetra(Ci-C₆)alkylmorpholinooxy; ii) Fremy salts, nitrosodisulfonates, and iii) morpholine N-oxide; the oxidizing agent is particularly chosen from the 2,2,6,6-tetramethylpiperidyloxy radical;

g) multivalent iodine derivatives, chosen from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid derivatives, periodinanes, alkyl and benzoyl hypoiodites; more preferentially, the oxidizing agent is chosen from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid, Dess- Martin's periodinane; iodoaryl di(CrC₆)alkylcarboxylate such as iodobenzene diacetate;

h) the following organic compounds: N-halosuccinimides, trichloroisocyanuric acid, N- hydroxyphthalimide, linear or branched C-I-C-IO alkyl nitrites;

i) hydrogen peroxide or system(s) that generate hydrogen peroxide

such as:

i-1 ) urea peroxide;

i-2) polymeric complexes that can release hydrogen peroxide, such as polyvinylpyrrolidone/H₂02 in particular in the form of powders, and the other polymeric complexes described in US 5 008 093; US 3 376 1 10; US 5 183 901 ; i-3) oxidases that produce hydrogen peroxide in the presence of a suitable substrate

(for example glucose in the case of glucose oxidase or uric acid with uricase);

i-4) metal peroxides that generate hydrogen peroxide in water, for instance calcium peroxide or magnesium peroxide;

i-v) perborates; or

i-vi) percarbonates.

The optional supports for these oxidizing agents a) to h) may be chosen from clays, montmorillonites, silica, alumina, charcoal and charged or neutral polymers.

According to one preferred embodiment of the invention, the process uses one or more system(s) that generate hydrogen peroxide, chosen from i) urea peroxide, i-2) polymeric complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H₂0₂; i-3) oxidases; i-v) perborates and i-vi) percarbonates.

Moreover, the composition(s) comprising the chemical oxidizing agent(s) may also contain various adjuvants conventionally used in hair dye compositions and as defined hereinbelow under the heading "cosmetic composition".

Preferentially, the chemical oxidizing agents are chosen from alkali metal perborates such as sodium perborate, persulfates of an alkaline agent such as sodium persulfate, Oxone or potassium persulfate, carboxylic acid peracids R-C(0)0-OH with R representing a linear or branched CrC₆ alkyl group such as methyl, and alkaline-earth metal hypochlorite such as calcium hypochlorite, alkali metal or alkaline-earth metal periodate such as sodium periodate, and iodoaryl di(CrC₆)alkylcarboxylates such as iodobenzene diacetate.

Particularly, the second constituent is atmospheric oxygen; preferentially, the process according to the invention and the composition are free of chemical oxidizing agent.

According to a second preferred embodiment, the oxidizing agent(s) are i) hydrogen peroxide or system(s) that generate hydrogen peroxide, preferentially H₂0₂.

According to one particular mode of the invention, the hydrogen peroxide or the chemical oxidizing agent(s) preferably represent from 0.001 % to 12% by weight expressed as hydrogen peroxide relative to the total weight of the composition(s) containing them, and even more preferentially from 0.2% to 2.7% by weight. c) additional metallic derivative(s) and/or pro-oxidizing clay(s)

Metallic derivatives and/or pro-oxidizing clays c) may be added to the process for treating keratin materials or to the composition according to the invention.

The metallic derivatives are in particular derivatives whose metal is in the Periodic table of the Elements in columns NIB, IVB, VB, VIB, VIIB, VII I B, IB and MB, or is aluminum Al. The metallic derivative(s) are chosen in particular from metal salts, metal complexes, metal oxides, metal oxoanions and supported forms thereof for which the metals are 1 ) Cu; 2) Au; 3) Mo; 4) Ag; 5) W; 6) V; 7) Ru; 8) Mg; 9) Ce; 10) Re; 1 1 ) Ti; 12) Si; 13) Sn; 14) Zr; 15) Nb; 16) In; 17) Se; 18) Al as defined previously, these derivatives particularly not being able to represent i) Mg, Sn, Al or Cu halide, ii) Cu and Ag nitrate, and iii) Cu sulfate; 19) Mn and 20) Zn.

More particularly, the metal(s) are chosen from:

1 ) the following copper derivative(s):

i) copper (Cu) oxide(s) of oxidation state I or II (Cu I or II);

ii) metallic copper complexes such as Cu I and II metalloporphyrin(s), and copper phthalocyanins and chlorophyllins;

iii) Cu I and II salts chosen from:

a) Cu II halides of formula CuHal(R²) with Hal representing a halogen atom, and R² representing a hydroxyl group, (CrC₆)alkoxy, or R¹-C(0)0- with R¹ representing a group (CrC₆)alkyl,

b) Cu II (CrCi₆)alkylcarboxylates such as Cu acetate,

c) Cu ((CrCi₆)alkyl)sulfates such as Cu ammoniacal lauryl sulfate, d) Cu (bi)carbonates such as Cu carbonate,

e) Cu II (CrCi₆)alkylpolycarboxylates such as Cu citrate Cu3(C6H₅0₇)2, or Cu succinate,

f) Cu II (Ci-Ci₆)alkyl polycarboxylates with the alkyl group optionally interrupted with one or more heteroatoms such as a nitrogen atom, for instance Cu edetate,

g) Cu II (poly)hydroxy(CrCi₆)alkyl carboxylates such as Cu gluconate, Cu glycocholate or Cu lactate,

h) heterocycloalkyl carboxylates such as Cu pidolate,

i) Cu deoxyribonucleate,

j) Cu oxalate,

k) Cu [(poly)(CrCi₆)alkyl](poly)phosphates such as Cu diphosphate;

iv) metallic Cu(l) or (II) complexes comprising ligands, particularly those bearing mono-, di-, tri- or tetra-functionalized ligands such as:

a) Cu(ll) complexes bearing a bisazomethine ligand of formula (a) below:

(a)

and also the hydrates thereof, in which formula (a):

o E represents a linear or branched divalent (CrC₆)alkylene chain optionally substituted with oxo or linear or branched (C₂-C₆)alkylene groups,

o either J is present and represents a group as defined for E and, in this case, X represents a heteroatom chosen from N and P;

o or J is absent and X represents a heteroatom such as O, S, N(R'), or P(R') with R' representing a hydrogen atom or a linear or branched (C C₆)alkyl group,

o A and B, which may be identical or different, are optionally substituted aryl groups, or optionally substituted heteroaryl groups; and

o R' is as defined for N(R') and P(R');

b) Cu(ll) complexes bearing an azomethine ligand such as those of formula (β) below:

and also the hydrates thereof, in which formula (β): X, J, A, B, R' and J are as defined previously in formula (a);

c) azo direct dye derivatives bearing a copper complex, such as those of formula (γ) below:

with X, J, A and B as defined previously in formula (a);

d) the Cu(ll) complexes derived from dyes are particularly Cu complexes of: 2,2'- dihydroxyazo; 2,2'-hydroxyaminoazo; 2,2'-dihydroxyazomethine, 2,2'- dihydroxycarboxyazo; 2,2'-dihydroxycarboxyazomethine; tridentate ligands derived from formazans,

2) gold (Au),

3) molybdenum (Mo),

4) silver (Ag) I and II oxides, Ag I and II salts chosen from silver halides, Ag sulfate, [R¹- C(0)0]_nAg with n= 1 or 2, R¹ representing a group (CrC₆)alkyl such as Ag acetate, Ag lactate, silver complexes such as Ag I metalloporphyrins, Ag I phthalocyanins or Ag I chlorophyllins,

5) tungsten (W),

6) vanadium (V),

7) ruthenium (Ru),

8) magnesium (Mg) II oxide, Mg II salts chosen from Mg sulfate, Mg II metalloporphyrins, Mg II phthalocyanins, Mg II chlorophyllins, Mg II chlorophylls,

9) cerium (Ce),

10) rhenium (Re),

11 ) titanium (Ti),

12) silicon (Si),

13) tin (Sn) oxides,

14) zirconium (Zr),

15) niobium (Nb),

16) indium (In),

17) selenium (Se),

18) aluminum (Al) oxides, and

19) manganese (Mn), particularly manganese salts, more particularly manganese (II) salts such as manganese halides, for example MnCI₂,

20) zinc (Zn).

The term "metal salt" means a compound other than alloys, i.e. the salt is formed from a metal combined with certain nonmetallic elements.

The formation of metal salts derives from oxidative attack. The metal is oxidized to a cationic species and then combines with an anionic species to give a salt. This formation takes place by applying redox principles and the redox reaction (chemical reaction during which an electron transfer takes place in which the atom that captures the electrons is known as the "oxidizing agent"; the atom that yields the electrons is the "reducing agent"); or via chemical exchange reactions between one salt and another salt or an acid, in the presence or absence of atmospheric oxygen. These reactions are known to those skilled in the art.

Preferentially, the salts according to the invention are soluble in water to a proportion of at least 0.0001 g/L.

The metal salts according to the invention may be introduced in solid form into the compositions or may originate from a natural, mineral or spring water that is rich in these ions, or alternatively from seawater (especially the Dead Sea). They may also originate from mineral compounds, for instance earths, ochres such as clays (for example green clay) or even from a plant extract containing them (cf. for example patent FR 2 814 943).

The terms "metal complex" and "coordination compounds" mean systems in which the metal ion, the central atom, is chemically bonded to one or more electron donors (ligands). A ligand comprising various coordinating groups (capable of coordinating with a methyl) gives methyl compounds corresponding to coordination sphere principles with a given number of electrons (internal complexes or chelates) - see Ullmann's Encyclopedia of Industrial Chemistry, "Metal complex dyes", 2005, p. 1 -42 - More particularly, the term "metal complex" means:

i) metallic dyes or "metal-complex dyes", which are complex dyes derived from azo, azomethine, hydrazono, formazans (free, bidentate, tridentate, tetradentate) such as those described in Ullmann's Encyclopedia of Industrial Chemistry, "Metal complex dyes", 2005, p. 1 -42, which preferentially comprise Cu and Mg; ii) compounds of the "aza[18]annulene" type, also known as "(metallo)porphyrins" and "phthalocyanins" which contain 4 and 8 nitrogen atoms, respectively, included in the parameter of the macrocycle - see the book "Color Chemistry", H. Zollinger, 3rd Ed., Wiley-VCH, 2003, chap.5. Aza[18]annulenes, p. 123-160. The metal ion is then at the center of said macrocycle bonded by coordination with two hydrogen atoms to the nitrogen atoms of pyrroles, the metal also possibly being stabilized with one or more bidentate or non-bidentate ligands; the metal ion preferentially being Mg²⁺ or Cu²⁺;

the metal complex is particularly:

a "metalloporphyrin" formed from a backbone bearing 4 pyrrole groups that are connected at their α,α' position via 4 methine groups and contain 16 sp² hybridized atoms, complexing a metal such as Cu or Mg, or

a "chlorine" (corresponding to a porphyrin in which an external C=C double bond of a pyrrole group has been reduced) complexed to a metal, preferentially Mg²⁺ such as the chlorophyll chromophore: chlorophyllin;

iii) "phthalocyanins", which are tetraaza analogs of tetrabenzoporphyrins, such as Monastral Fast Blue B (C.I. Pigment Blue 15); Monastral Fast Blue G (C.I. Pigment Blue 16) (see "Color Chemistry" H. Zollinger, 3rd Ed., Wiley-VCH, 2003, chap. 5. Aza[18]annulenes, p. 140); the sulfonyl derivatives Sirius light Turquoise Blue G (C.I. Direct Blue 86, copper phthalocyanin tetrasulfonic acid) and "phthalocyanins" as described in Ullmann's Encyclopedia of Industrial Chemistry,

"Phthalocyanins", 2005, p. 1 -34, which comprise Cu and Si.

The term "metal oxide(s)" means the compounds of general formula A_xO_y with A representing a metal element and 1 < x < 4 and 1 < y < 12.

The term "metal oxoanion(s)" means the compounds of general formula Z_zA_xO_ywith A representing a metal element, Z representing an alkali metal such as Li, Na, K or a hydrogen atom or an ammonium ion, and 1 < z < 6, 1 < x < 4 and 1 < y < 12. The term "supported form(s)" means the forms in which the metal derivative b) is impregnated onto a material known as a "support". The optional supports for these metal derivatives may be chosen from charcoal, silica, alumina, optionally charged polymers comprising counter-anions or counter-cations (counter-cation or counter-anion of the metallic species). By way of example, the polymers may be polyethylene glycol (PEG) and polystyrene.

1 ) According to one preferred embodiment of the invention, the metal derivative(s) are chosen from:

i) copper (Cu) oxide(s) of oxidation state I or II (Cu I or II),

ii) metallic copper complexes such as Cu I and II metalloporphyrins, copper phthalocyanins as described in US 3 931 249, and copper chlorophyllins,

iii) Cu I and II salts chosen from:

a) Cu II halides of formula CuHal(R²) with Hal representing a halogen atom, and R² representing a hydroxyl group, (CrC₆)alkoxy, or R¹-C(0)0- with R¹ as defined previously,

b) Cu II (CrCi₆)alkylcarboxylates such as Cu acetate,

c) Cu ((CrCi₆)alkyl)sulfates such as Cu ammoniacal lauryl sulfate,

d) Cu (bi)carbonates such as Cu carbonate,

e) Cu II (CrCi₆)alkylpolycarboxylates such as Cu citrate Cu₃(C6H₅07)2, or Cu succinate,

f) Cu II (Ci-Ci₆)alkyl polycarboxylates with the alkyl group optionally interrupted with one or more heteroatoms such as a nitrogen atom, for instance Cu edetate, g) Cu II (poly)hydroxy(CrCi₆)alkyl carboxylates such as Cu gluconate, Cu glycocholate or Cu lactate,

h) heterocycloalkyl carboxylates such as Cu pidolate,

i) Cu deoxyribonucleate,

j) Cu oxalate,

k) Cu [(poly)(CrCi₆)alkyl](poly)phosphates such as Cu diphosphate,

iv) metallic Cu (I) or (II) complexes comprising ligands such as the metal complex dyes described in Ullmann's Encyclopedia, 2005 Wiley-VCH Verlag GmbH & Co, KgA, Weinheim, 10.1002/14356007. a16_299, pp. 1 -42, particularly those bearing mono-, di-, tri- or tetra- functionalized ligands such as:

a) Cu(ll) complexes bearing a bisazomethine ligand such as those of formula (a) below:

(^a) and also the hydrates thereof,

in which formula (a):

o E represents a linear or branched divalent (CrC₆)alkylene chain optionally substituted with oxo groups, or a linear or branched (C₂-

C₆)alkylene chain such as ethylene -CH₂-CH₂-, or arylene such as ortho- phenylene or heteroarylene,

o either J is present and represents a group as defined for E and, in this case, X represents a heteroatom chosen from N and P,

o or J is absent and X represents a heteroatom such as O, S, N(R'), or

P(R') with R' representing a hydrogen atom or a linear or branched (C

C₆)alkyl group, preferentially X = O,

o A and B, which may be identical or different, particularly identical, are optionally substituted aryl groups, or optionally substituted heteroaryl groups; preferentially, A and B are aryls such as phenyl, and

o R' is as defined for N(R') and P(R'), preferentially R' is a hydrogen atom; more particularly, the Cu complex is such that X = O, E = ethylene, J is absent, R' = H, A and B = phenyl substituted para to the oxygen atom with a sulfate group of an alkali metal such as sodium, or such as Brilliant Red [76683-16-4];

and also the hydrates thereof,

in which formula (β): X, J, A, B, R' and J are as defined previously in formula (a), particularly R' represents a hydrogen atom, B represents a phenyl, X represents an oxygen atom, A represents a phenyl optionally substituted para to the oxygen with a phenyl or a naphthyl, such as Pigment Yellow 1 17 [21405-81 - 2] and Pigment Yellow 129 [68859-61 -0];

azo direct dye derivatives bearing a copper complex, such as those of formula (γ) below:

(Ύ) with X, J, A and B as defined previously in formula (a), in particular, the compounds of formula (γ) are chosen from Acid Dyes such as Sirius Light Blue 3 RL [13217-74-8], C.I. Direct Blue 93, Benzo Fast Red CGL, C.I. Direct Red 180, and [92341 -30-5], [1 19103-25-2], [1 16932-38-8], [1 13989- 79-0];

bisazo direct dye copper complex and derivatives such as Direct Blue 80 [12222-003];

formazan dyne derivatives or formazan dyes as described in Ullmann's Encyclopedia, 2005 Wiley-VCH Verlag GmbH & Co, KgA, Weinheim, 10.1002/14356007.a16_299, p. 27, point 6 and 6.1.2: Bidentates such as [53708-91 -1], Tridentates or Tetradentates such as [36090-18-3] and [109973- 79];

d) the Cu(ll) complexes derived from dyes are particularly Cu complexes of: 2,2'- dihydroxyazo; 2,2'-hydroxyaminoazo; 2,2'-dihydroxyazomethine, 2,2'- dihydroxycarboxyazo; 2,2'-dihydroxycarboxyazomethine; tridentate ligands derived from formazans.

More particularly, the metallic copper derivative is chosen from copper gluconate, cupric chlorophyllin a or b, and CuHal(OH) with Hal a representing a halogen atom, such as CuCI(OH).

2) According to one preferred embodiment of the invention, the metal derivative(s) are gold (Au). More particularly:

i) gold I and III oxides such as Au₂0₃,

ii) Au I and III hydroxides such as Au(OH)₃, AuOH, Au(0)OH,

iii) gold I salts particularly of formula AuHal with Hal representing a halogen atom (F, CI, Br, I) such as AuCI or Aul,

iv) gold III salts chosen particularly from the following formulae:

• Au(Hal)₃ with Hal, which may be identical or different, as defined previously, for instance AuCI₃, and AuBr₃,

• hydrated or non-hydrated ZAu(Hal)₄, with Z representing a hydrogen atom, an alkali metal such as Li, Na, K or an ammonium NH₄ ⁺, and Hal, which may be identical or different, as defined previously, for instance KAuCI₄ or HAuCI₄,

• Au(R)₃ with R, which may be identical or different, representing:

- a (CrC₆)alkylcarbonyloxo group, in which the alkyl group is linear or branched, such as methyl or tert-butyl, such as Au(OAc)₃,

- or alternatively one or two of the groups R representing a ligand L bearing at least one electron-donating group such as amino, phosphino, hydroxyl or thiol, or the ligand is a "persistent" carbene particularly of "Arduengo" type (Imidazol- 2-ylidenes); preferentially, the ligand is a phosphino such as triphenylphosphine, for example (Ph₃P)AuOC(0)'Bu,

v) metallic Au complexes such as Au I and III metalloporphyrins, Au I and III phthalocyanins or Au I and III chlorophyllins a or b.

Preferentially, the metallic derivative(s) are chosen from Au I and III oxides such as Au₂0₃, gold hydroxides and Au III salts such as ZAu(Hal)₄ and Au(R)₃. More preferentially, the metallic derivative is chosen from oxides and hydroxides such as Au₂0₃, Au(OH)₃, AuOH.

3) According to one particular embodiment of the invention, the metal derivative(s) are silver (Ag). More particularly: i) silver I and II oxides such as Ag₂0 and AgO;

ii) silver I salts chosen particularly from the following formulae:

• AgHal with Hal representing a halogen atom (F, CI, Br, I) such as AgCI, AgBr, Agl;

· Ag_xR³ _z, with R³, which may be identical or different, representing:

^■ a sulfate group such as Ag₂S0₄

^■ a group (CrC₆)alkylcarbonyloxo in which the alkyl group is linear or branched and may be optionally substituted with a hydroxyl group, such as Ag acetate, Ag propionate or Ag lactate

■ x and z as defined previously

^■ with the exception of silver nitrate Ag(N0₃);

iii) Ag I metalloporphyrins;

iv) Ag I phthalocyanins as described in US 3 931 249; and

v) Ag I chlorophyllins a or b.

4) According to one particular embodiment of the invention, the metallic derivative(s) is molybdenum (Mo);

in particular the metallic derivatives of oxidation state (II) to (VI) and are as described in Kirk-Othmer's Encyclopedia of Chemical Technology Copyright © 2001 by John Wiley & Sons, Inc. Last updated: 17 Sep 2009, "Molybdenum compounds", Edward I. Stieffel, pp. 871 -895 or Ullmann's Encyclopedia; WILEY-VCH Verlag GmbH & Co. KGaA © 2000-2005, "Molybdenum and Molybdenum Compounds".

More particularly:

a) particularly VI Mo oxides such as:

- molybdenum(VI) oxide, of formula Mo0₃;

Mo (IV) oxides bearing ^-diketone ligands Mo0₂L₂ with L ligand, which may be identical or different, preferentially identical, representing a ^-diketone of the type R-C(X)-C(R')-C(X)R" with R and R", which may be identical or different, representing a linear or branched group (CrC₆)alkyl, and R' represents a hydrogen atom or a linear or branched group (CrC₆)alkyl, X represents an oxygen or sulfur atom or a group N(R) with R representing a hydrogen atom or a linear or branched group (CrC₆)alkyl, more particularly, the Mo dioxide is of the formula Mo02[CH₃C(0)CHC(0)CH₃]2 [17524-05-9];

Mo (VI) oxide complexes derived from Mo0₃ and from a C₂-Ci₀ hydroxycarboxylic acid ligand, especially citric acid or maleic acid, as described in the article C. B. Knobler et al., J. Chem. Soc. Dalton Trans. 1983, 1299, or C₂-C₁0 polyols comprising from 2 to 5 hydroxyl groups, especially ethylene glycol and glycerol, as described in the article F. A. Schroder, J. Scherle, Z. Naturforsch. B: Anorg. Chem. Org. Chem. 28B (1973) 46; see also C. B. Knobler, B.R. Penfold, G. T. Wilkins, J. Chem. Soc. Dalton Trans. 1980, 248,

- the monohydrate, Mo0₃ ^■ H₂0 [39082-25-2], the dihydrate, Mo0₃ ^■ 2H₂0 [25942- 34-1], molybdic acid (H₂Mo0₄ H₂0);

molybdenum dioxide;

dihalodioxomolybdenum (Hal)₂Mo0₂ with Hal, which may be identical or different, as defined previously, particularly Hal are identical and represent a chlorine atom;

blue molybdenums [66771-43-5], mixture of Mo oxide/Mo(VI) hydroxide and Mo(V) hydroxide as described in the article V. K. Rudenko, Koord. Khim. 5 (1979) 307; (Sov. J. Coord. Chem. (Engl. Transl.) 5 (1979) 231 ); particularly Mo⁶⁺3 Mo⁵⁺3 Oi₈H, and condensation derivatives with phosphate ions;

mixtures of Mo oxides of different valences Mo(VI)-Mo(V) (Mo oxide bronzes) as described in the article M. Greenblat, Chem. Rev. 88 (1988) 31 ; more particularly the binary bronzes and the tertiary bronzes A0.₃₃M0O₃ (A = Li, K, Rb, Cs, Tl); A0.₃M0O₃ (A = K, Rb, Tl); Ao.₉Mo₈Oi7 (A = Li, Na, K, Tl), and the rare- earth metal bronzes La₂Mo₂0₇;

b) Mo oxoanions chosen from the molybdates Z₂Mo0₄ with Z, which may be identical or different, as defined previously, such as sodium molybdate Na₂Mo0₄, ammonium molybdate (NH₄)₂Mo0₄;

) polyoxometallates such as: [XY_uMoi_2-u0₄o]^(3+u)" (Z)(3_+u) with X and Y chosen from P, Si, V; 0 < u < 6, and Z is as defined previously in which Z represents a hydrogen atom; particularly the polyoxometallate is of formula H₅PV₂Moio0₄₀,

) binary Mo halides of oxidation states (II) to (VI), hexacoordinated with 6 halogens of Mo(V), (IV) and (III), the Mo atoms being bonded via halogen bonds such as Mo(ll) halide containing [Mo₆Hal₈]⁴⁺ clusters bonded to halogen atoms to give Mo₆Hali₂ with Hal, which may be identical or different, as defined previously and more particularly Hal represents CI;

) molybdenum tetrahalides (Hal)₄Mo with Hal', which may be identical or different, as defined previously, such as MoCI₄;

Mo sulfur derivatives chosen from:

molybdenum disulfides [1317-33-5], molybdenum(IV) sulfides, MoS₂, the molybdates of formula (Z)₂MoS₄, with Z, which may be identical or different, as defined previously, particularly Z representing an ammonium such as tetrathiomolybdate (NH₄)₂[MoS₄] [15060-55-6];

- Mo sesquisulfide [12033-33-9]; dimolybdenum (III) trisulfides, Mo₂S_3; tetrasulfide salts Z M0S24^" with Z as defined previously, preferentially representing ammonium;

g) oxomolybdenum (VI) derivatives chosen from:

Mo(0)Hal₄ with Hal, which may be identical or different, being as defined previously, particularly Hal represents an F or CI atom;

Mo(0)₂Hal₂ with Hal, which may be identical or different, being as defined previously, particularly Hal represents an F, CI or Br atom;

h) trihalooxomolybdenum (V) derivatives and adducts thereof with organic ligands L as defined previously, L preferentially representing:

- a bidentate group R-C(X)-CR'R"-C(X)-R"' with R and R"", which may be identical or different, representing a linear or branched group (CrC₆)alkyl, and R' and R", which may be identical or different, representing a hydrogen atom or a linear or branched group (CrC₆)alkyl, preferentially R' and R" represent a hydrogen atom, X represents an oxygen or sulfur atom or a group N(R) with R representing a hydrogen atom or a linear or branched group (CrC₆)alkyl, such as acetylacetone;

a bidentate group of the 2,2-bipyridyl type;

i) the oxomolybdenum derivative of formula Mo(0)Hal₃ ^'2 L with L and Hal as defined previously, preferentially L represents an R"-0-R' with R and R' as defined previously, such as diethyl ether and a heteroaryl group such as pyridine;

j) molybdates, isopolymolybdates, and heteropolymolybdates containing a tetrahedral anion [Mo0₄]^2~ such as ammonium heptamolybdate (isopolymolybdate), (NR'₄)₆Mo₇0₂₄ hydrate, with R', which may be identical or different, being as defined previously, particularly R' is a hydrogen atom;

k) molybdates of divalent cations, especially those that are water-soluble, such as the molybdates of Mg²⁺ and the molybdates of trivalent cations, especially of formula A₂(Mo0₄)₃ or A₂Mo₃Oi₂, with A representing an atom chosen from Al, Cr, Bi and Lanthanide;

I) heteropolymolybdates bearing [Mo0₆] octahedra incorporating heteroatoms other than oxygen, chosen especially from S, N and P; more specifically, the heteromolybdates are of formula [X⁺ _nMoi₂0₄o]^(8"n)", containing tetracoordinated heteroatoms (X) such as [12026-57-2], Η₃[ΡΜθι₂0₄ο] ^■ 28H₂0,

m) Mo complexes with organosulfur ligands such as phosphorodithioates or dithiophosphates and dithiocarbamates, [Mo₂0₃L₄] and [Mo₂0₂S₂L₂] with L as defined previously, particularly L represents (RO)₂PS^~ ₂, R₂NCS^~ with R, which may be identical or different, being as defined previously; n) molybdenum hexacarbonyl [13939-06-5], Mo(CO)_6;

o) organic pigments derived from alkali metal and alkaline-earth metal molybdates, such as sodium molybdate derivatives such as derivatives of i) Diarylmethane (Auramine C.I. 655), ii) Triarylmethane (Malachite Green C.I. 657, Brilliant

Green C.I. 662; Rhoduline Blue 6G C.I. 658, Acronol Brilliant Blue C.I. 664,

Methyl Violet B C.I. 680; Victoria Pure Blue BO C.I. Pr198); iii) Xanthene (Rhodamine B C.I. 749, Rhodamine 6G); and

P) Ca and Sr molybdates and

q) Mo porphyrins as described in the article by T. Ma, K. Inoue, E. Abe, J. Yu, X.

Wang, B. Zhang, J Electroanal. Chem. 537 (2002) 31 , and Mo phthalocyanins as described in US 3 931 249.

Preferentially, the metallic derivative is chosen from the compounds of formula Z₂Mo0₄ such as Na₂Mo0₄.

5) According to one particular variant of the invention, the metallic derivative(s) are tungsten (W). More particularly i) tungsten VI oxides, ii) tungsten oxoanions, preferentially the hydrated or non-hydrated alkali metal tungstates Z₂W0₄, with Z, which may be identical or different, as defined previously, iii) polyoxometallates such as [XY_uW₁₂-_u0₄o]^(4+u)";(Z)_(4+U) with X and Y chosen from P, Si, V; 0 < u < 6, particularly the polyoxometallate is of formula H₄SiW₁₂O₄₀.

Preferentially, the metallic derivative is chosen from alkali metal tungstates such as sodium tungstate Na₂W0₄. 6) According to one particular variant of the invention, the metallic derivative(s) are vanadium (V). More particularly i) vanadium oxides such as V₂0₅, ii) vanadium oxoanions chosen from vanadates and metavanadates such as vanadium oxide acetylacetonate VO(acac)₂, VOS0₄, ammonium vanadate and iii) polyoxometallates such as [XV_uM₁₂-_u0₄o]^q" ;(Z)_q with M = W, Mo; X = P, Si; 0 < u < 6 and q=3+x if M=Mo or q=4+x if M=W and Z is as defined previously, particularly the polyoxometallate is of formula H₅PV₂Moio0₄₀ and iv) vanadium complexes such as those described in US 3 931 249.

Preferentially, the metallic derivative is chosen from those of formula [XV_uMoi2-_u0₄o]^(3+u);(Z)_(3+u) as defined previously and particularly H₅PV₂Moi₀O₄₀. 7) According to one particular embodiment of the invention, the metallic derivative(s) are ruthenium (Ru). More particularly i) ruthenium oxides, ii) ruthenium oxoanions such as alkali metal perruthenates, and iii) ruthenium complexes such as (Hal)₂RuL₄ with Hal, which may be identical or different, as defined previously and L, which may be identical or different, being ligands as defined previously.

Preferentially, the metallic derivative is chosen from RuCI₂(PPh₃)4, potassium perruthenate.

8) According to one particular embodiment of the invention, the metallic derivative(s) are magnesium (Mg), particularly i) magnesium II oxide, ii) magnesium II salts such as magnesium II sulfate, iii) magnesium II metalloporphyrins, iv) magnesium II phthalocyanins, v) magnesium II chlorophyllins, vi) magnesium II chlorophylls, metal complex dyes as described in Ullmann's Encyclopedia, 2005 Wiley-VCH Verlag GmbH & Co, KgA, Weinheim, 10.1002/14356007. a16_299, pp. 1 -42), in particular those derived from formazans as described in Ullmann's Encyclopedia, 2005 Wiley-VCH Verlag GmbH & Co, KgA, Weinheim, 10.1002/14356007.a16_299, p. 27, point 6.1 .2.

Preferentially, the metallic derivative is chosen from magnesium chlorophyllin a or b and magnesium chlorophyll a or b:

9) According to one particular embodiment of the invention, the metallic derivative(s) are cerium (Ce). More particularly cerium IV oxides, and cerium III and IV salts.

Preferentially, the metallic derivative is chosen from cerium ammonium nitrate, cerium ammonium sulfate and cerium nitrate and cerium oxides, and also salts thereof, hydrates thereof and supported forms thereof. Examples of cerium oxides that may be mentioned include cerium oxides and hydroxides such as those described in point 4.2 of Ullmann's encyclopedia "Cerium Mischmetal, Cerium Alloys, and Cerium Compounds", 2005 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002/14356007.a06 139, pp. 12. More particularly, the cerium oxide(s) are chosen from cerium (IV) oxide hydrate [63394-44-5], [67285-52-3], cerium (III) rare-earth metal oxide hydrates, cerium (IV) oxide [1306-38-3], Ce0₂. Preferentially, the metal oxide(s) are cerium (IV) oxide Ce0₂.

10) According to one particular embodiment of the invention, the metallic derivative(s) are rhenium (Re). More particularly R'Re0₃ with R' representing a hydrogen atom or a linear or branched group (CrC₆)alkyl, such as CH₃Re0₃ or rhenium complexes such as the phthalocyanins described, for example, in US 3 931 249.

11 ) According to one particular embodiment of the invention, the metallic derivative(s) are titanium (Ti). More particularly titanium IV salts such as Ti(S0₄)₂, titanium complexes such as the phthalocyanins described, for example, in US 3 931 249 or titanium oxides and hydroxides such as those described in Ullmann's encyclopedia "Titanium, Titanium Alloys, and Titanium Compounds", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002/14356007.a27 095, pp. 1 -33.

Particularly, the titanium oxide(s) are chosen from titanium (III) hydroxide and oxide

Ti(OH)₃ and Ti0₃, dititanium trioxide Ti₂0₃, alkaline-earth metal titanium trioxides, alkaline- earth metal titanium pentoxides, the titanates of general formula M"Ti0₄ in which M" represents a metal Mg, Zn, Mn or Co, peroxytitanic acid and the peroxytitanates H₄Ti0₅, titanium (II) dioxide Ti0₂, titanium disulfide TiS₂.

The oxides may originate from minerals such as anatase and rutile that contain Ti0₂; perovskite containing calcium trioxide CaTi0₃, a sphene or titanite containing CaTi(Si0₄)0.

Preferentially, the metallic derivative(s) are Ti0₂.

12) According to one particular variant of the invention, the metallic derivative(s) are silicon oxides, and also salts thereof, hydrates thereof and supported forms thereof.

Preferentially the metal oxide(s) are silicon (IV) oxide Si0₂.

13) According to one particular variant of the invention, the metallic derivative(s) are tin oxides, and also salts thereof, hydrates thereof and supported forms thereof. By way of example, mention may be made of tin oxides such as those described in points 10 and 1 1 of Ullmann's encyclopedia "Tin, Tin Alloys, and Tin Compounds", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a27 049, pp. 27-29,

particularly tin (II) oxide hydrated such as 5 SnO -2H₂0 and tin (II) oxide, tin (IV) oxide hydrate Sn0₂ - nH₂0 and tin (IV) oxide Sn0₂, alkali metal salts such as tin sodium potassium hydroxide of formula M₂ [Sn(OH)₆] with M representing an alkali metal, the tin hydroxides of formula R₃SnOH, R₂SnOH₂, or RSnOH₃, with R which represents a hydrocarbon-based group such as linear or branched (CrC₆)alkyl, or linear or branched (d- C₆)alkoxy or (di) (Ci-C₆)alkylamino.

Preferentially, the metallic derivative(s) are tin (IV) oxide Sn0₂. 14) According to one particular embodiment of the invention, the metallic derivative(s) are zirconium (Zr), particularly zirconium complexes such as the phthalocyanins described, for example, in US 3 931 249 and titanium oxides, and also salts thereof, hydrates thereof and supported forms thereof. Examples of Zr oxides that may be mentioned include Zr oxides and hydroxides such as those described in points 2.2, 2.3 and 2.5 of Ullmann's encyclopedia "Zirconium and Zirconium Compounds", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002/14356007. a28 543, pp. 15-18, more particularly zirconium oxide [1314-23-4], Zr0₂, zirconium oxide hydrate [Zr₄(OH)₈ - 16H₂0]₈, zirconium hydroxide dihalide such as zirconium hydroxide dichloride [22196-48-1], and also the compounds of formula Zr(OH)₂Hal2 ^■ 7H₂0, with Hal representing a halogen atom such as chlorine, zirconium oxyhalides such as zirconium oxychloride, zirconium halide oxides such as zirconium oxide dichloride, ZrOCI₂ -8H₂0, [Zr₄(OH)₈ ^■ 16H₂0]CI₈ ^■ 12H₂0 and zirconium monohalide such as zirconium hydroxide monochloride [Zr₄(OH)₁₂ ^■ 16H₂0]CI₄.

Preferentially, the metallic derivatives are zirconium (II) oxide Zr0₂. 15) According to one particular embodiment of the invention, the metallic derivative(s) are niobium oxides, and also salts thereof, hydrates thereof and supported forms thereof. Examples that may be mentioned include niobium oxide and hydroxides such as those described in points 5.1 and 5.2 of Ullmann's encyclopedia "Niobium and Niobium Compounds", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002/14356007.a17 251 , pp. 5-6.

In particular, the niobium oxide(s) are chosen from niobium pentoxide Nb₂0₅ [1313- 96-8], alkali metal niobium trioxide such as lithium niobium trioxide LiNb0₃ [12031 -63-9] or KNb0₃ [12030-85-2] and niobium oxyhalides such as the chlorine oxychloride [13597-20-1], NbOCI₃.

Preferentially, the metal oxide(s) are niobium pentoxide Nb₂0₅.

16) According to one particular variant of the invention, the metallic derivative is chosen from indium oxides and salts thereof, hydrates thereof and supported forms thereof. Examples that may be mentioned include indium oxides such as those described in point 7 of Ullmann's encyclopedia "Indium and Indium Compounds", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a14 157, pp. 7,

particularly the indium (III) oxide of formula ln₂0₃, indium (II) oxide [12136-26-4] of formula InO, and indium (I) oxide [12030-22-7] of formula ln₂0, indium hydroxide [56108-30- 6], of formula ln(OH)₃, preferentially indium (III) oxide ln₂0₃.

17) According to one particular embodiment of the invention, the metallic derivative(s) are selenium (Se), more particularly Se0₂.

18) According to one particular embodiment of the invention, the metallic derivative(s) are chosen from aluminum oxides and also the salts thereof, hydrates thereof and supported forms thereof. Examples that may be mentioned include aluminum oxides and hydroxides such as those described in Ullmann's encyclopedia "Aluminum oxide", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002/14356007.a06 139, pp. 1 -40.

In particular, the aluminum hydroxide(s) and oxide(s) are chosen from aluminum trihydroxide AI(OH)₃, aluminum oxide hydroxide AIO(OH), dialuminum trioxide Al₂0₃ hydrated or anhydrous, and alkali metal aluminates such as sodium aluminate NaAI0₂ [1302-42-7].

19) According to one particular embodiment of the invention, the metallic derivative(s) are chosen from manganese salts and oxides, and the salts per se derived especially from the action of an acid on a metal. Preferably, the salts are not oxides. Among the salts, mention may be made of halides such as chlorides, fluorides and iodides; sulfates, phosphates; nitrates; perchlorates and carboxylic acid salts and polymer complexes that can support said salts, and also mixtures thereof.

More particularly, manganese salt is other than manganese carbonate, manganese hydrogen carbonate or manganese dihydrogen carbonate.

As examples of polymer complexes that can support said salts, mention may be made of manganese pyrrolidone carboxylate.

The carboxylic acid salts that may be used in the invention also include salts of hydroxylated carboxylic acids such as gluconate.

By way of example, mention may be made of manganese fluoride, manganese chloride, manganese acetate tetrahydrate, manganese lactate trihydrate, manganese phosphate, manganese iodide, manganese nitrate trihydrate, manganese bromide, manganese perchlorate tetrahydrate, manganese sulfate monohydrate and manganese gluconate. The salts advantageously used are manganese gluconate and manganese chloride. 20) According to one particular embodiment of the invention, the metallic derivative(s) are chosen from zinc salts and oxides, and the salts per se derived especially from the action of an acid on a metal. Among the zinc salts, mention may be made of zinc sulfate, zinc gluconate, zinc chloride, zinc lactate, zinc acetate, zinc glycinate and zinc aspartate.

The manganese and zinc salts may be introduced in solid form into the compositions or may be derived from a natural, mineral or spring water that is rich in these ions or alternatively from seawater (especially the Dead Sea). They may also originate from mineral compounds, for instance earths, ochres such as clays (for example green clay) or even from a plant extract containing them (cf. for example patent FR 2 814 943).

Preferentially, the metal oxide(s) are dialuminum trioxide oxide Al₂0_3.

One preferred embodiment of the invention concerns metal derivatives that are in only one metallic species chosen from 1 ) and 20) as defined previously.

More particularly, the metallic derivative(s) are chosen from compounds of formula ZAu(Hal)₄; Au(R)₃ Au₂0₃; Z₂Mo0₄; Z₂W0₄; [XY_xMoi_2-x0₄o]^(3+x)"(Z)₍3_+x); Ti0_2; Si0₂; Sn0₂; Zr0₂ or ln₂0₃.

According to one preferred embodiment of the invention, the metallic derivative(s) b) are gold (Au). More particularly, the metallic derivative(s) b) are gold (Au), with the exception of gold salts.

Particularly, the metallic derivatives of the invention are in oxidation state II, such as Mn (II) and Zn (II). Preferentially, the metal salt of the invention is a manganese salt and more particularly Mn (II), more preferentially an Mn (II) halide such as MnCI₂.

According to one preferred embodiment of the invention, the metallic derivative(s) used represent from 0.0001 % to 10% by weight approximately relative to the total weight of the composition(s) containing this or these metal salts, and even more preferentially from 0.0001 % to 0.1 % by weight approximately.

Pro-oxidizing clays:

The third constituent of the process of the invention, and of the composition, may be one or more pro-oxidizing clays, i.e. clays that catalyze the oxidation via atmospheric oxygen.

Mention may be made of the clays described in Ullman's Encyclopedia, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim "Clays": http://www.mrw.interscience.wiley.com/ emrw/9783527306732/ueic/article/a07_109/current/pdf

Among the clays that may be mentioned are:

- Amorphous clays I) of the allophane group [12172-71 -3] constituted especially by silica and alumina, and are generally associated with halloysite (see below).

- 2-layer crystalline clays II) A) composed of a layer of tetrahedral silica and a layer of octahedral alumina:

1 ) of the same dimension as the group of [1332-58-7] kaolin, mineral group comprising:

o kaolinite [1318-74-7], of formula Si₂0₅Al2(OH)₄,

o dickite [1318-45-2],

o nacrite [12279-65-1 ], and

o halloysite [12244-16-5] and minerals thereof, dehydrated, of identical chemical formula to kaolinite;

the mineral kaolin is derived from hydrated aluminum silicates constituted especially of aluminum and of silicon such as 2H₂0 ^■ Al₂0₃ ^■ 2 Si0₂; kaolinite is formed from a single layer of tetrahedral silica associated with a single layer of octahedral alumina. It is generally of formula AI₂Si₂0₅(OH)₄.

2) elongates such as halloysite [12244-16-5] of identical formula to kaolinite.

- 3-layer clays III) composed of two layers of tetrahedral silica and one central octahedral or trioctahedral layer:

1 ) with an expanded network which comprises smectites [12199-37-0] derived especially from bentonite:

a) of the same dimension: i) montmorillonite [1318-93-0] including alkali metals or alkaline-earth metals such as sodium and/or calcium, particularly those of formula

known under the name Sommieres earth; ii) sauconite

[12424-32-7] which corresponds to smectite in which the zinc has replaced a few aluminum atoms, and iii) vermiculite [1318-00-9];

b) Elongate such as nontronite [12174-06-0], saponite [1319-41 -1] or hectorite

[12173-47-6];

2) of unexpanded network such as the group of illites [12173-60-3] which especially comprise water and potassium aluminum silicates of formula (OH)₄K₂(Si₆AI₂)AI₄O₂₀ or KAI₂(AISi₃Oio)(OH)₂.

- clays IV) as a regular mixture of layers belonging to the group of chlorites.

- clays of type V) with a structural sequence of silica in tetrahedral form connected to octahedral groups of oxygen atoms and hydroxyl groups also containing an aluminum and magnesium, such as palygorskite [12174-11-7] or attapulgite [1337-76-4] which generally have a structure of the type (OH₂)₄(OH)₂Mg₅Si₈0₂o -4H₂0. Mention may also be made of sepiolite [15501 -74-3], which forms part of the clays of type V).

- Clays of type VI obtained synthetically from laponite of formula:

Na⁺o,7[(Si8Mg5,₅Lio.3)0₂o(OH)₄]^"o,7 which is a family of synthetic smectite, or synthetic or nonsynthetic hydrotalcite of the type Mg₆AI₂(C0₃)(OH)₁₆ ^«4(H₂0). Particularly, the clays that are advantageous for the invention are clays chosen from montmorillonites, attapulgites, bentonites, vermiculites, goethites, hydroxyapatites, laponites and hydrotalcite.

According to the invention, the term "clay" also means:

o mixtures of clays, especially natural clays, also known as layer-to-layer mixtures, such as the mixtures illite— smectite, illite— chlorite, smectite-chlorite, vermiculite— illite, and smectite-kaolinite,

o modified clays are clays that have undergone chemical modifications and that are not found in nature in this form. These modifications may be obtained via physical processes (temperature), or chemical processes (the addition of a neutralizing counterion such as mineral or organic acids or bases, by ion exchange, by addition of a polymerizable or non-polymerizable anionic or cationic surfactant or alternatively a natural or synthetic polymer). Mention may be made particularly as modified clays of bentones such as stearalkonium hectorite or stearalkonium bentonite.

The pH of untreated kaolin is between 4.5 and 6.5, but may be increased with soluble salts. Preferentially, the pH is between 7.4 and 9.

Preferentially, the pro-oxidizing clays are chosen from i) commercial montmorillonites such as MK10, MKSF, ii) basified montmorillonites such as K10 or KSF noted OH^", iii) acidified montmorillonites such as K10 or KSF noted H⁺, iv) hydrotalcite, v) goethite, vi) basified goethites, noted OH^", vii) acid-treated goethites, noted H+, viii) bentonite, ix) bentonites treated with an alkaline agent, noted OH^", x) bentonite treated with an acidic agent, noted H⁺.

Acidified clays (noted H⁺) may become acidified by being pretreated in acidic medium: The process for performing the acidification of the clay (noted H⁺) is typically that of mixing one weight of clay per 10 volumes of an acidic aqueous solution (for example 1 N hydrochloric acid). Said mixing is generally performed with stirring at room temperature at 25°C for several hours (2 hours). The clay is then left to settle, and then washed. The washing is stopped when the pH is >3.

Basified clays (noted OH^") may become basified by being pretreated in alkaline medium:

The process for performing the basification of the clay is typically that of mixing one weight of clay per 10 volumes of basic aqueous solution (for example sodium hydroxide). Said mixing is generally performed with stirring at room temperature at 25°C for several hours (2 hours). The clay is then left to settle, and then washed. The washing is stopped when the pH is < 8.

The clays preferentially have a particle size < 10 μηη and more particularly < 2 μηη. d) Additional basifying agent(s)

One or more basifying agents may be used in the dyeing process according to the invention as fourth ingredient d), which is an agent for increasing the pH of the composition(s) in which it is present. The basifying agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic.

Particularly, said agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicate, vii), amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and viii) the compounds of formula (II) below:

N W N

/ \

^Rc %!)

in which W is a propylene residue optionally substituted with a hydroxyl group or a Ci-C₄ alkyl radical; R_a, R_b, R_c and R_d, which may be identical or different, represent a hydrogen atom or a C C₄ alkyl or d-C₄ hydroxyalkyl radical.

The mineral or organic hydroxides are preferably chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metal, such as hydroxides of metals from groups III, IV, V and VI, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.

The hydroxide may be formed in situ, for instance guanidine hydroxide, by reacting calcium hydroxide and guanidine carbonate.

The term "(bi)carbonates i)" means:

a) carbonates of alkali metals (Met₂ ⁺, C0₃ ^2"), of alkaline-earth metals (Met'²⁺, C0₃ ^2"), of ammonium ((R"₄N⁺)₂,C0₃ ^2") or of phosphonium ((R"₄P⁺)₂,C0₃ ^2"), with Met' representing an alkaline-earth metal and Met representing an alkali metal, and R", which may be identical or different, represent a hydrogen atom, an optionally substituted group (CrC₆)alkyl such as hydroxyethyl,

and

b) bicarbonates, also known as hydrogen carbonates, of the following formulae:

> R'⁺, HC0₃ ^" with R' representing a hydrogen atom, an alkali metal, an ammonium group R"₄N⁺- or a phosphonium group R"₄P⁺- in which R", which may be identical or different, represent a hydrogen atom, an optionally substituted group (CrC₆)alkyl such as hydroxyethyl and, when R' represents a hydrogen atom, the hydrogen carbonate is then known as a dihydrogen carbonate (C0₂, H₂0); and

> Met'²⁺ (HC0₃ ^")₂ with Met' representing an alkaline-earth metal.

More particularly, the alkaline agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates; preferentially alkali metal (bi)carbonates.

Mention may be made of Na, K, Mg and Ca carbonates or hydrogen carbonates and mixtures thereof, and in particular sodium hydrogen carbonate. These hydrogen carbonates may originate from a natural water, for example source water of the Vichy basin, La Roche Posay water, or Badoit water (cf. for example patent FR 2 814 943). Particularly, mention may be made of sodium carbonate [497-19-8] = Na₂C0₃, sodium hydrogen carbonate or sodium bicarbonate [144-55-8] = NaHC0₃, and sodium dihydrogen carbonate = Na(HC0₃)₂.

According to one particularly advantageous embodiment, the basifying agent(s) c) are chosen from alkanolamines and (bi)carbonates, particularly of alkali metals or alkaline-earth metals. Furthermore, they are preferentially together during the dyeing process. The basifying agent(s) as defined previously preferably represent from 0.001 % to

10% by weight relative to the weight of the composition(s) containing them, and more particularly from 0.005% to 8% by weight of the composition. water:

According to one embodiment of the invention, water is preferably included in the process of the invention. It may originate from the moistening of the keratin fibers and/or from the composition(s) comprising compounds a) to d) as defined previously or from one or more other compositions. Preferably, the water comes from at least one composition comprising at least one compound chosen from a) to d) as defined previously.

The compositions:

Another subject of the invention concerns a composition comprising:

a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously;

and optionally: c) one or more metallic derivatives and/or one or more pro-oxidizing clay(s) as defined previously, preferably chosen from Mn and Zn salts; and/or

d) one or more basifying agent(s) as defined previously;

According to one particular embodiment of the invention, the composition comprises:

a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously; and

c) one or more metallic derivatives as defined previously, preferably chosen from Mn and Zn salts.

According to one variant of the invention, the composition comprises:

a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously; and

c) one or more pro-oxidizing clay(s).

In another advantageous variant of the invention, the composition comprises:

a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously;

c) one or more metallic derivatives preferably chosen from Mn and Zn salts, as defined previously, and

one or more pro-oxidizing clay(s). A particularly advantageous composition comprises:

a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously; and

d) one or more basifying agent(s) as defined previously. According to one advantageous variant of the invention, the composition comprises: a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously;

c) one or more metallic derivatives, preferably chosen from Mn and Zn salts, and/or one or more pro-oxidizing clay(s) as defined previously; and

d) one or more basifying agent(s) as defined previously.

When the composition contains one or more basifying agents, the pH of said composition is preferably alkaline, i.e. greater than 7, and in particular between 8 and 12 and more particularly between 8 and 10.5.

According to one particularly advantageous mode of the invention, the composition according to the invention is aqueous.

The compositions used in the invention are cosmetic. The cosmetic compositions according to the invention are cosmetically acceptable, i.e. they comprise a dye support that generally contains water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.

The term "organic solvent" means an organic substance that is capable of dissolving or dispersing in another substance without chemically modifying it.

The organic solvents:

Examples of organic solvents that may be mentioned include Ci-C₄ lower alcohols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.

The organic solvents are present in proportions preferably of between 1 % and 60% by weight approximately and even more preferentially between 5% and 30% by weight approximately relative to the total weight of the dye composition.

The adjuvants:

The composition(s) of the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or nonvolatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.

Said adjuvants are preferably chosen from surfactants such as anionic or nonionic surfactants or mixtures thereof and mineral or organic thickeners.

The above adjuvants are generally present in an amount for each of them of between

0.01 % and 40% by weight relative to the weight of the composition, and preferably between 0.1 % and 20% by weight relative to the weight of the composition. Needless to say, a person skilled in the art will take care to select this or these additional compound(s) such that the advantageous properties intrinsically associated with the composition(s) that is (are) useful in the reshaping process in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition(s).

The additional dyes:

The process using ingredients a) to c) as defined previously, the water; or the cosmetic composition according to the invention comprising ingredients a) to c) as defined previously, the water; may also use or comprise one or more additional direct dyes.

These direct dyes are chosen, for example, from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes other than ortho-diphenols, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine, cyanine and methine direct dyes, and fluorescent dyes. All these additional dyes are other than the ortho- diphenol derivatives according to the invention and the "metal-complex dyes" or the porphyrins, metalloporphyrins and phthalocyanins belonging to a) according to the invention.

Among the natural direct dyes, mention may be made of lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts, may also be used.

The additional direct dye(s) used in the composition(s) preferably represent from 0.001 % to 10% by weight approximately relative to the total weight of the composition(s) containing them, and even more preferentially from 0.05% to 5% by weight approximately.

The process using ingredients a) to c) as defined previously and water or the cosmetic composition according to the invention comprising ingredients a) to c) as defined previously and water may also use or comprise one or more oxidation bases and/or one or more couplers conventionally used for the dyeing of keratin fibers.

Among the oxidation bases, mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.

Among these couplers, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.

The oxidation base(s) present in the composition(s) are each generally present in an amount of between 0.001 % and 10% by weight relative to the total weight of the corresponding composition(s). The cosmetic composition(s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream or a gel, or in any other form that is suitable for dyeing keratin fibers. They may also be conditioned in a pump-dispenser bottle without a propellant or under pressure in an aerosol can in the presence of a propellant and form a mousse. pH of the composition (s)

The process according to the invention uses the ingredients a), b) and c), with a final pH that is basic or alkaline, i.e. above 7, preferably between 8 and 12 and particularly between 8 and 1 1 . This is likewise the case for the compositions according to the invention, which are basic or alkaline and which have a pH above 7, preferably between 8 and 12 and particularly between 8 and 1 1 .

The pH of these compositions may be adjusted to the desired value by means of basifying agents as defined previously in c) or of acidifying agents usually used in the dyeing of keratin fibers, or alternatively by means of standard buffer systems.

Among the acidifying agents for the compositions used in the invention, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

Among the basifying agents, they are agents as defined previously under the heading "el) basifying agent(s)" . e) Process for dyeing in one or more steps

One subject of the invention is a process for dyeing, in one or more steps, by applying to keratin materials one or more cosmetic compositions containing, taken together or separately in said composition(s), the following ingredients:

a) one or more beetroot peel extract(s) as defined previously, and

b) one or more oxidizing agent(s) as defined previously.

According to one particular embodiment of the invention, the dyeing process is performed, in one or more steps, by applying to keratin fibers one or more cosmetic compositions containing, taken together or separately in said composition(s), the following ingredients:

a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously; and c) one or more metallic derivatives, preferably chosen from Mn and Zn salts, and/or one or more pro-oxidizing clay(s) as defined previously.

According to another particular embodiment of the invention, the dyeing process is performed, in one or more steps, by applying to keratin fibers one or more cosmetic compositions containing, taken together or separately in said composition(s), the following ingredients:

a) one or more beetroot peel extract(s) as defined previously;

b) one or more oxidizing agent(s) as defined previously; and

d) one or more basifying agent(s),

it being understood that the pH of said composition is greater than 7, preferably between 8 and 12 and more particularly between 8 and 10.5, with at least one of said compositions being aqueous. According to another particular embodiment of the invention, the dyeing process is performed, in one or more steps, by applying to keratin fibers one or more cosmetic compositions containing, taken together or separately in said composition(s), the following ingredients:

a) one or more extract(s) of beetroot peel;

b) one or more oxidizing agent(s);

c) one or more metallic derivatives, preferably chosen from Mn and Zn salts, and/or one or more pro-oxidizing clay(s); and

d) one or more basifying agent(s),

it being understood that the pH of said composition is greater than 7, preferably between 8 and 12 and more particularly between 8 and 10.5, with at least one of said compositions being aqueous.

Preferentially, a) the extract(s) with b) the oxidizing agent as defined previously and optionally with a metallic derivative as defined previously, particularly an Mn (II) halide such as MnCI₂.

According to one preferred mode of the invention, in the dyeing process and the composition of the invention, ingredient b) comprises only metallic derivatives. According to another advantageous mode of the invention, ingredient b) contains only pro-oxidizing clays.

According to a third variant, ingredient b) contains a mixture of pro-oxidizing clays and of metallic derivatives.

The leave-on time between the steps of applying the compositions comprising ingredients a), b), c) and/or d) is set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more particularly between 15 and 45 minutes.

The keratin fibers may or may not be moistened beforehand.

More particularly, in the process of the invention, the compound(s) d) are:

- either in a mixture with ingredients a), b) and c);

- or applied separately after application of a cosmetic composition comprising ingredients a), b) and c); or alternatively

- applied together with ingredient c) after application of a cosmetic composition comprising ingredients a) and b).

One particular embodiment of the invention concerns processes for dyeing in one or two steps.

According to one particular mode of the invention, the process for dyeing keratin fibers is performed in a single step by applying to the keratin fibers an aqueous cosmetic dye composition comprising a), b), c) and d) as defined previously.

The leave-on time after application is generally set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more preferentially between 15 and 45 minutes.

According to another particular embodiment of the invention, the process for dyeing keratin fibers is performed in two steps.

In a first two-step process variant, the first step consists in applying to said fibers a cosmetic composition comprising ingredients a), b) and c) as defined previously, and then, in a second step, a cosmetic composition comprising ingredient d) as defined previously is applied to said fibers, it being understood that at least one of the two cosmetic compositions is aqueous.

In a second variant of the process for dyeing keratin fibers in two steps, the first step consists in applying to said fibers a cosmetic composition comprising ingredients a) and b) as defined previously, and then, in a second step, a second cosmetic composition comprising ingredients c) and d) as defined previously is applied to said fibers, it being understood that at least one of the two compositions is aqueous. According to a particular dyeing process of the invention, said process is performed in at least two steps ending with the treatment of the keratin fibers with ingredient d) and may be followed by post-treatment steps such as shampooing with a standard shampoo, rinsing, for example with water, and/or drying the keratin fibers by heat treatment as defined below; it being understood that said process does not involve intermediate rinsing just before the step that uses ingredient d).

Preferentially, the dyeing process according to the invention is performed in two steps, of which the first step is that of applying to the keratin fibers ingredients a) and b) together, and then, in a second step, applying together ingredients c) and d), or, in a first step, applying together ingredients a), b) and c) and then, in a second step, applying d). These processes may be followed by post-treatment steps such as rinsing, for example with water, shampooing with a standard shampoo and/or drying of the keratin fibers. Preferentially, the process according to the invention in at least two steps does not involve intermediate rinsing between the first and the second step, i.e. between the application of the mixture of ingredients a), b), c) and d) or between the application of mixture a), b) and of mixture c), d).

According to a particularly advantageous process, the keratin fibers are, just before the step uses ingredient d):

1 ) either wiped mechanically as described below,

2) or dried by heat with a heat treatment as described below,

3) or not rinsed, i.e. the steps are performed successively. Preferably, between the first and the second step of the dyeing process of the invention, the fibers are:

1 ) either wiped mechanically as described below,

2) or dried by heat with a heat treatment as described below,

3) or not rinsed, i.e. steps 1 and 2 are performed successively.

According to a particularly preferred process of the invention, just before the step that uses ingredient d), the fibers are 1 ) mechanically wiped.

More preferentially, between the first and second step, the fibers are wiped, preferentially using a towel or absorbent paper, or are dried by heat with a heat treatment at a temperature particularly between 60 and 220°C and preferably between 120 and 200°C. According to another particular mode of the invention, between the application of the mixture of ingredients a), b), c) and d) or between the application of mixture a), b) and mixture c), d), the locks are rinsed very rapidly, between 1 second and 1 minute, more particularly between 1 second and 30 seconds and preferentially between 2 and 5 seconds, such as 2 seconds, under tap water or with an intense-jet showerhead. This rapid rinsing step is followed by mechanical wiping as described below.

For these processes, the leave-on time after application of the cosmetic composition for the first step is generally set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more preferentially between 15 and 45 minutes. The leave-on time after application of the second cosmetic composition for the second step is generally set at between 3 and 120 minutes, preferentially between 3 and 60 minutes and more preferentially between 5 and 60 minutes, such as 30 minutes. Irrespective of the application method, the application temperature is generally between room temperature (15 to 25°C) and 80°C and more particularly between 25 and 55°C. Thus, after application of the composition according to the invention, the head of hair may advantageously be subjected to a heat treatment by heating to a temperature of between 30 and 60°C. In practice, this operation may be performed using a styling hood, a hairdryer, an infrared ray dispenser or other standard heating appliances.

It is possible to use, both as heating means and as hair straightening means, a heating iron at a temperature of between 60 and 220°C and preferably between 120 and 200°C.

One particular mode of the invention concerns a dyeing process that is performed at room temperature (25°C).

In all the particular modes and variants of the processes described previously, the compositions mentioned are ready-to-use compositions that may result from the extemporaneous mixing of two or more compositions and especially of compositions present in dyeing kits. f) step(s) of mechanical wiping and/or drying:

According to one particular mode of the invention, the process for dyeing keratin fibers comprises at least one intermediate step of mechanical wiping of the fibers and/or of drying and/or non-rinsing. The steps of intermediate mechanical wiping and drying are also known as "controlled non-rinsing" to distinguish from "standard abundant rinsing with water" and "non-rinsing".

The term "mechanical wiping of the fibers" means rubbing an absorbent article on the fibers and physical removal, by means of the absorbent article, of the excess ingredient(s) that have not penetrated the fibers. The absorbent article may be a piece of fabric such as a towel, particularly a terry towel, a cloth or absorbent paper such as household roll towel.

According to one particularly advantageous process of the invention, the mechanical wiping is performed without total drying of the fiber, leaving the fiber moist. The term "drying" means the action of evaporating the organic solvents and/or water that are in one or more compositions used in the process of the invention, comprising or not comprising one or more ingredients a) to d) as defined previously. The drying may be performed with a source of heat (convection, conduction or radiation) by sending, for example, a stream of hot gas such as air necessary to evaporate the solvent(s). Sources of heat that may be mentioned include a hairdryer, a hairstyling hood, a hair-straightening iron, an infrared ray dispenser or other standard heating appliances.

Q) Dyeing device or "kit":

Another subject of the invention is a multi-compartment dyeing device or "kit". Advantageously, this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which are distributed the ingredients a) one or more beetroot extract(s), b) one or more chemical oxidizing agent(s), and optionally c) one or more metallic derivative(s) and/or pro-oxidizing clay(s), and optionally d) one or more oxidizing agent(s), and d) one or more basifying agent(s), said compositions being aqueous or pulverulent, particularly with at least one of these compositions being aqueous.

According to a first variant, the kit comprises five compartments, the first four compartments comprising, respectively, the powdered ingredients a), b), c) and d) as defined previously and the fifth compartment containing an aqueous composition such as water. In this case, the compound(s) c) are hydrogen peroxide precursors.

Another variant concerns a four-compartment kit, at least one of which contains an aqueous composition, and comprising ingredients a) to d) as defined previously.

In another variant of the four-compartment device: the first compartment comprises a cosmetic composition containing ingredient a), the second compartment comprises a composition containing ingredient b), the third compartment comprises a composition containing ingredient c) and the fourth compartment contains a composition containing ingredient d); at least one of these compositions preferably being aqueous.

Another preferred embodiment concerns a device comprising three compartments: (1 ) a first compartment contains a composition containing:

a) one or more beetroot extract(s); and

(2) a second compartment contains a composition containing:

b) one or more metallic derivative(s) and/or pro-oxidizing clay(s),

c) one or more oxidizing agent(s);

(3) a third compartment contains d) one or more basifying agent(s).

In this other embodiment, at least one of the three compositions is preferably aqueous and the beetroot extract(s) may be in powder form.

Use may also be made of a three-compartment kit, the first 1 ) containing a composition comprising ingredients a) and b) as defined previously, the second 2) containing a composition comprising ingredient c) as defined previously, and the third 3) containing a composition comprising ingredient d) as defined previously. In this other kit, at least one of the compositions is preferably aqueous. This composition preferably contains hydrogen peroxide.

According to one particular mode of the invention, the kit comprises two compartments: a first compartment comprising a composition containing ingredients a), b) and c) as defined previously, and a second compartment containing ingredient d) as defined previously.

Among the two-compartment kits, it is also possible to have kits that contain, in a first compartment, a composition comprising ingredients a), b) and d) as defined previously and, in a second compartment, a composition comprising compound c) as defined previously.

In these two variants of two-compartment kits, the first composition contained in the first compartment comprising either a), b) and c) or a), b) and d) is in powder form and, preferably, the second composition is aqueous.

According to one variant, the device according to the invention also comprises an additional composition (d') comprising one or more treating agents.

The compositions of the device according to the invention are conditioned in separate compartments, optionally accompanied by suitable application means, which may be identical or different, such as fine brushes, coarse brushes or sponges.

The device mentioned above may advantageously be equipped with a means for dispensing the desired mixture on the hair, such as the devices described in patent FR 2 586 913.

EXAMPLES OF DYEING

Compositions A1 to A7 were prepared as follows:

Next, compositions B2 !, B4, B6 and B7 were prepared as fo Hows: oomposiuon (g R9

Sodium bicarbonate 8.4

Demineralized water qs 100g

For tests 1 to 7 :

Composition Ai is applied to locks of dry natural hair containing 90% white hairs, with a bath ratio of 5 g of formula per 1 g of hair. The composition is then left to stand on the locks for 30 minutes at a temperature of 50°C. After this, the hair impregnated with the first composition is wiped using an absorbent paper towel to remove the excess formula.

Composition Bi is then applied to the hair with a bath ratio of 4 g per 1 g of lock; the leave-on time is 10 minutes at room temperature. After a few minutes, a very intense coloration appears.

Colorimetric results: The coloration of the hair is evaluated visually and read on a Minolta spectrocolorimeter (CM3600d, illuminant D65, angle 10°, SCI values) for the L^*, a^*, b^* colorimetric measurements.

In this L^*, a^*, b^* system, L^* represents the intensity of the color, a^* indicates the green/red color axis and b^* the blue/yellow color axis. The lower the value of L, the darker or more intense the color. The higher the value of a^*, the redder the shade, and the higher the value of b^*, the yellower the shade.

The variation in coloration between the dyed locks of permanent-waved gray hair that are untreated (control) and after treatment are defined by (ΔΕ^*) according to the following equation:

In this equation, L^*, a^* and b^* represent the values measured after dyeing permanent-waved hair containing 90% white hairs, and L₀ ^*, a₀ ^* et b₀ ^* represent the values measured for untreated permanent-waved hair containing 90% white hairs.

The higher the value of ΔΕ, the greater the difference in color between the control locks and the dyed locks.

After rinsing, shampooing and drying the locks under a hood, the coloration of the hair is evaluated visually and read on a Minolta spectrocolorimeter (CM3600d, illuminant D65, angle 10°, SCI values) for the L^*, a^*, b^* colorimetric measurements.

It appears from the results of the above table that the process according to the invention can produce a very dark coloration when compared with the untreated lock (significantly lower L and AL). In addition, the process according to the invention has very strong dyeing power (very high ΔΕ).

Claims

1. A process for dyeing keratin materials, which comprises the application of: a) one or more extract(s) of beetroot peel;

b) one or more oxidizing agent(s); and

d) one or more basifying agent(s).

2. The dyeing process as claimed in claim 1 , which comprises the application of:

a) one or more extract(s) of beetroot peel;

b) one or more oxidizing agent(s);

c) one or more metallic derivatives and/or one or more pro-oxidizing clay(s); and

d) one or more basifying agent(s).

3. The dyeing process as claimed in either of the preceding claims, in which the oxidizing agent is solely atmospheric oxygen.

4. The dyeing process as claimed in either of claims 1 and 2, in which the oxidizing agent(s) are chosen from:

a) ozone;

b) alkali metal or quaternary ammonium persalts such as perborates, persulfates, percarbonates or peroxodiphosphates, Oxone® or potassium persulfate; the oxidizing agent is particularly chosen from sodium perborate, sodium persulfate, potassium persulfate, ammonium persulfate, sodium percarbonate and potassium percarbonate; c) aliphatic Ci-C₆ and aromatic C₈-C₂o organic peracids, and the percarboxylate forms thereof: R-C(0)0-OM' with R representing a group (CrC₆)alkyl or (C₆-C₂o)aryl such as phenyl, M' representing a hydrogen atom (peracid) or an alkali metal or alkaline- earth metal (percarboxylate), are chosen from performic acid, peracetic acid, perbenzoic acid derivatives, trifluoroacetic acid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid; the oxidizing agent is particularly peracetic acid;

d) organic peroxides chosen from dioxirane, Ci-C₆ alkyl peroxides, benzoyl peroxide, peroxo(CrC₆)alkyl carboxylates, bis(tri)(CrC₆)alkylsilyl peroxides such as bis(trimethylsilyl) peroxide, Ci-C₆ alkyl peroxydicarbonates, and sodium nonanoyloxybenzene sulfonate;

f) stable radicals containing an N-oxy (NO) group, chosen from i) heterocycles containing a sterically hindered N-oxide group such as the radical 2,2,6,6-tetra(Ci- C6)alkylpiperidinooxy-2,2,6,6-tetra(Ci-C₆)alkylmorpholinooxy; ii) Fremy salts, nitrosodisulfonates, and iii) morpholine N-oxide; the oxidizing agent is particularly chosen from the 2,2,6,6-tetramethylpiperidyloxy radical;

i) hydrogen peroxide or system(s) that generate hydrogen peroxide,

the optional supports for these oxidizing agents a) to h) possibly being chosen from clays, montmorillonites, silica, alumina, charcoal and charged or neutral polymers; particularly, the oxidizing agent(s) are chosen from hydrogen peroxide and system(s) that generate hydrogen peroxide.

5. The dyeing process as claimed in claim 2, in which the pro-oxidizing clay(s) are chosen from allophanes, of the kaolin group; smectites, elongates, illites; chlorites, palygorskite or attapulgite, sepiolite, hydroxyapatites, laponites and hydrotalcite; particularly, the clays are chosen from montmorillonites, attapulgites, bentonites, vermiculites, goethites, laponites and hydrotalcite; particularly, the clay(s) have particle sizes < 10 μηη.

6. The dyeing process as claimed in claim 2, in which the metallic derivative(s) are chosen from metal salts, metal complexes, metal oxides, metal oxoanions and supported forms thereof for which the metals are 1 ) Cu; 2) Au; 3) Mo; 4) Ag; 5) W; 6) V; 7) Ru; 8) Mg; 9) Ce; 1 0) Re; 1 1 ) Ti; 12) Si; 13) Sn; 14) Zr; 15) Nb; 16) In; 1 7) Se; 18) Al; 19) Mn and 20) Zn.

7. The dyeing process as claimed in claim 2 or 6, in which the metallic derivative(s) are chosen from manganese salts, more particularly salts of manganese of oxidation state (II).

8. The dyeing process as claimed in any one of claims 1 to 7, in which the basifying agent(s) are chosen from:

i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates, vii) amino acids, and viii) the compounds of formula (II) below:

N W N

/ \

^Rc %!)

in which W is a propylene residue optionally substituted with a hydroxyl group or a Ci-C₄ alkyl radical; R_a, Rb, R_c and R_d, which may be identical or different, represent a hydrogen atom or a C C₄ alkyl or d-C₄ hydroxyalkyl radical.

9. The dyeing process as claimed in any one of claims 1 to 8, in which the basifying agent(s) d) are chosen from alkanolamines and alkali metal or alkaline-earth metal (bi)carbonates.

10. The process as claimed in any one of the preceding claims, in one step, which consists in applying to keratin fibers an aqueous composition comprising a), b), d) and optionally c) as defined in any one of the preceding claims.

11. The dyeing process as claimed in any one of claims 2 to 10, in two steps, which consists, in the first step, in applying to keratin materials, especially keratin fibers, a composition comprising ingredients a), b) and c) as defined in any one of claims 1 and 4 to 10, and then, in a second step, in applying a composition comprising d) as defined in claim 1 , 8 or 9, particularly at a pH above 7 and preferably between 8 and 12.

12. The dyeing process as claimed in any one of claims 2 to 10, in two steps, which consists, in the first step, in applying to keratin materials, especially keratin fibers, a composition comprising ingredients a) and b) as defined in either of claims 1 and 4, and then, in a second step, in applying a composition comprising c) and d) as defined in any one of claims 1 and 5 to 9, particularly at a pH above 7 and preferably between 8 and 12.

13. A composition containing:

a) one or more extract(s) of beetroot peel;

b) one or more oxidizing agent(s); d) one or more basifying agent(s) as defined in claim 1 , 2, 8 or 9;

and optionally:

c) one or more metallic derivatives as defined in claim 1 , 2, 6 or 7 and/or one or more pro-oxidizing clay(s) as defined in claim 1 , 2 or 5; and/or

it being understood that when the composition does not contain c), the oxidizing agent(s) are chosen from those of claim 4.

14. Use of the composition as defined in claim 13, for dyeing keratin materials.

15. The use as claimed in the preceding claim, in which the keratin materials are the hair.