WO2012175720A1

WO2012175720A1 - Hair dyeing process using a dihydroxyflavonoid, neoflavanol or neoflavanone derivative, manganese salts, hydrogen peroxide, (bi)carbonates, alkaline agents, and metal salts

Info

Publication number: WO2012175720A1
Application number: PCT/EP2012/062161
Authority: WO
Inventors: Christophe Rondot; Patrick Choisy
Original assignee: L'oreal
Priority date: 2011-06-23
Filing date: 2012-06-22
Publication date: 2012-12-27
Also published as: FR2976798B1; FR2976798A1

Abstract

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated with one or more cosmetic compositions containing, taken together or separately in said composition(s), the following ingredients: a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s); b) one or more manganese salt(s); c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s); d) one or more (bi)carbonate(s) or one or more bicarbonate-generating system(s); e) one or more alkalinizing agent(s) different from the bicarbonate(s); and f) one or more metal salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts; it being understood that: - the pH of at least one of the compositions comprising at least one of the ingredients a), b), d), e) and/or f) is alkaline, i.e. greater than 7, - the metal salt(s) f) is (are) applied in the final step of the dyeing process. The process according to the invention has the advantage of dyeing human keratin fibres with persistent and, surprisingly, chromatic coloration results, with a satisfactory coloration "uptake".

Description

^

HAIR DYEING PROCESS USING A DIHYDROXYFLAVONOID, NEOFLAVANOL OR NEOFLAVANONE DERIVATIVE, MANGANESE SALTS, HYDROGEN PEROXIDE, (BI)CARBONATES, ALKALINE AGENTS, AND

METAL SALTS

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated using one or more cosmetic compositions comprising a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s), b) one or more manganese salt(s), c) hydrogen peroxide or one or more hydrogen peroxide- generating system(s), d) one or more (bi)carbonate(s) or one or more (bi)carbonate-generating system(s), e) one or more alkalinizing agent(s) different from the (bi)carbonate(s) and f) one or more metal salt(s) chosen from molybdenum (Mo), aluminium (Al), zinc (Zn), calcium (Ca) and rhodium (Rh), it being understood that the ingredient(s) f) is (are) applied post-treatment.

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 colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured 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 in particular 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 fibres bases or a mixture of bases and couplers with hydrogen peroxide (H2O2 or aqueous hydrogen peroxide solution), as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres. The colorations resulting therefrom are permanent, strong and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing.

However, the commercial hair colourings which contain them generally have the drawback of staining clothing, of causing odour and comfort problems, and of damaging the keratin fibres. 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-diphenol compounds in the presence of a metal salt, in particular a manganese (Mn) and/or zinc (Zn) salt. 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 fibres, comprising a dye precursor that contains ortho-diphenols, Mn and/or Zn oxides and salts, alkalinizing 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 of keratin materials with atmospheric oxygen or any oxygen-generating system.

However, the colorations obtained are not strong enough, and are not very chromatic, in particular in the case of hair fibres.

Moreover, it is known practice to use metals at acid pH for dyeing keratin fibres in amounts similar to those employed for dyes using a mordanting process, making it possible to prepare the fibres, in order to obtain persistent dyeing.

However, this process generally has the drawback of not always respecting the cosmetic appearance of the keratin fibre. Furthermore, the metals used, such as iron, result in neutral shades that are not very chromatic. Generally, such metals do not make it possible to obtain chromatic shades.

There is therefore a real need to develop dyeing processes which make it possible to obtain strong, persistent and/or chromatic colorations using dihydroxyflavonoid derivatives, in particular using natural extracts rich in dihydroxyflavonoid(s), neoflavanol(s) or neoflavanone(s), and which are less aggressive on keratin fibres. In particular, there is a need to obtain colorations which satisfactorily withstand external agents (light, bad weather, shampooing) and which are persistent and homogeneous, i.e. which have a weak coloration selectivity between the root and the end, while at the same time remaining powerful and/or chromatic.

This objective is achieved by virtue of the present invention, the subject of which is a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated, in one or more steps, with one or more cosmetic compositions containing, taken together or separately in said composition(s), the following ingredients:

a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s);

b) one or more manganese salt(s);

c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s);

d) one or more (bi)carbonate(s) or one or more bicarbonate-generating system(s);

e) one or more alkalinizing agent(s) different from the bicarbonate(s); and f) one or more metal salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts;

it being understood that: - the pH of at least one of the compositions comprising at least one of the ingredients a), b), d), e) and/or f) is alkaline, i.e. greater than 7, and

- the metal salt(s) f) is (are) applied post-treatment, i.e. in the final step of the dyeing process.

Thus, the keratin fibres are treated at the end of the dyeing process with a composition comprising the metal salt(s).

In particular, the cosmetic composition comprising one or more metal salt(s) is applied to the keratin fibres post-treatment, especially zinc salts such as zinc acetate.

According to one particular embodiment of the dyeing process according to the invention, the compound(s) d) and e) are:

either in a mixture with the compounds a), b) and c);

or applied separately after application of a cosmetic composition comprising the compound(s) a), b) and c),

or applied together with the compound c) after application of a cosmetic composition comprising the ingredients a) and b).

According to one particular embodiment of the dyeing process of the invention, the metal salt(s) is (are) applied separately after application of the ingredients a) to e).

A subject of the present invention is also a cosmetic composition for dyeing keratin fibres, comprising:

a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s);

b) one or more manganese salt(s);

c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s);

it being understood that the pH of the composition is alkaline, i.e. greater than 7, preferably between 8 and 12 and more particularly between 8 and 10.5.

Another subject of the present invention relates to a multicompartment device comprising:

a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s);

b) one or more manganese salt(s); „

4

c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s);

d) one or more (bi)carbonate(s) or one or more (bi)carbonate-generating system(s);

it being understood that the pH of at least one of the compositions comprising at least one of the ingredients a), b), d), e) and/or f) is alkaline, i.e. greater than 7, and preferably between 8 and 12. It is particularly between 8 and 10.5.

The multicompartment device or "kit" is suitable for implementing the dyeing process according to the invention.

The process according to the invention has the advantage of dyeing human keratin fibres with persistent and, surprisingly, chromatic coloration results. In particular, the dyeing process according to the invention makes it possible to produce colorations that are resistant to washing, perspiration, sebum and light without modifying the fibres. Furthermore, the dyeing process implemented makes it possible to induce a satisfactory "uptake" of the coloration.

Another subject of the invention is the use of one or more salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts, for improving the chromaticity and/or the colour uptake of keratin fibres, in particular human keratin fibres such as the hair, dyed using one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s).

Other subjects, characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the description and the examples that follow. a) dihydroxyflavonoid, neoflavanol or neoflavanone derivatives

According to one particular embodiment of the invention, the process for dyeing keratin fibres or the composition uses or contains as ingredient a) one or more dihydroxyflavonoid derivatives or the dihydroxyflavonoid derivative mixture. The term "dihydroxyflavonoids" means a compound comprising at least two benzene rings A and B linked via a three-carbon chain closed in the form of a 6- membered heterocycle C comprising an oxygen atom, and at least one of the two benzene rings A or B of which comprises at least two hydroxyl groups (OH) borne by two adjacent carbon atoms (in the ortho position) of said benzene ring.

Mention may thus be made of flavone structures, flavonols, dihydroflavonols and flavanonols, flavanones, flavan-3-ols, flavan-3,4-diols and anthocyanidols, salified forms thereof, aglycone forms of thereof (without bonded sugars), and also heteroside forms thereof, methoxylated forms thereof, and the corresponding oligomers, as described in "Bruneton, J., Pharmacognosie - Phytochimie, plantes medicinales [Pharmacognosy phytochemistry medicinal plants], 4th ed., revised and extended, Paris, Tec & Doc - Editions medicales Internationales, 2009, p. 1288" and in "P. Sarni-Manchado, V. Cheynier, Les polyphenols en agroalimentaire [Polyphenols in food processing], Lavoisier, Editions Tec & Doc, 2006, p 398", in particular natural flavonoids, in particular flavonoids derived from animal extracts, from bacteria, from fungi, from algae, from plants and from fruits.

More particularly, the dihydroxyflavonoid derivatives a) represent compounds of formula (I) and also organic or inorganic acid salts thereof, optical, geometric and tautomeric isomers thereof, and solvates thereof such as the

• R\ R², R³, R⁴, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴, which may be identical or different, represent:

- a hydrogen atom,

- a halogen atom,

- a hydroxyl group,

- a (Ci-C6)alkyl group,

- a (Ci-C6)alkoxy group,

- a (Ci-C6>alkylthio group,

- a carboxyl group,

- an alkyl carboxylate or alkoxycarbonyl group,

- an optionally substituted amino group,

- an optionally substituted linear or branched alkenyl group,

- an optionally substituted cycloalkyl group, _r

6

- an aryl group,

- a substituted aryl group,

- a group containing one or more silicon atoms,

- a (di)((hydroxy)(Ci-C6)alkyl)amino group,

- an -O-sugar group such as -O-glucoside,

- an R-Z-C(X)-Y- group with R representing a hydrogen atom or a (Ci-C6)alkyl group, Y and Z, which may be identical different, represent a bond, or an oxygen or sulphur atom or an -N(R')- group with R' representing a hydrogen atom or a (Ci-C6)alkyl group, Y possibly also representing a (Ci-Ce)alkylene group; X representing an oxygen or sulphur atom, or N-R" with R" representing a hydrogen atom or a (Ci-Ce)alkyl group;

• R⁵, R⁶, R⁷, R⁸ and R⁹, which may be identical or different, represent a hydrogen atom, or a group chosen from hydroxyl or (Ci-Ce)alkyl;

· or else R⁵ with R⁶ and/or R⁷ with R⁸ form, together with the carbon atom which bears them, an oxo group;

• or else R⁸ and R⁹ together form a bond;

it being understood that:

- at least two contiguous radicals chosen from R¹, R², R³, R⁴, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ represent a hydroxyl group;

- when R⁵ with R⁶ and/or R⁷ with R⁸ together form an oxo group, or R⁸ with R⁹ together form a bond, then represents a single bond;

- when borne by the oxygen atom is a double bond, then the compound of formula (I) is cationic and an anionic counterion is associated therewith.

The dihydroxyflavonoid derivatives that are useful in the process of the invention may be natural or synthetic. Among the natural dihydroxyflavonoid derivatives are compounds that may be present in nature and that are reproduced by chemical (semi)synthesis. The dihydroxyflavonoid derivatives of the invention may be salts of acids or bases. The acids may be inorganic or organic. Preferably, the acid is hydrochloric acid, which results in chlorides. The bases may be inorganic or organic. In particular, the bases are alkali metal hydroxides such as sodium hydroxide, which leads to sodium salts.

More particularly, the dihydroxyflavonoids that may be used in the process of the invention according to a) are in particular:

- i) dihydroxyflavanols such as catechin and epichatechin gallate, their oligomers and polymers called proanthocyanidols or condensed tanins such as theaflavin, theaflavin 3'-O-gallate, theaflavin 3,3'-O-digallate, and proanthocyanidins A1 , A2, B1 , B2, B3 and C1 ;

- ii) dihydroxyflavonols such as quercetin, myricetol, fisetin, heterosides thereof,

- iii) dihydroxyflavones such as luteolin, heterosides thereof such as luteolol 7-O- glucoside, baicalin, or orientin;

- iv) dihydroxydihydroflavonols or dihydroxyflavanonols such as dihydroquercetol, heterosides thereof such as dihydroquercetol 3-O-rhamoside;

v) dihydroxyflavanones such as eriodictyol

vi) dihydroxyflavan-3,4-diols or dihydroxyleucoanthocyanidins such as

- vii) dihydroxyanthocyanidols (or dihydroxyanthocyanidins) constructed on the flavylium cation, such as cyanidol, delphinidine, aurantinidine, luteolinidine, heterosides thereof, such as dihydroxyanthocyans (or dihydroxyanthocyanosides, or anthocyanines on the English model), their oligomers and polymers such as proanthocyanines.

According to another particular embodiment of the invention, the process for dyeing keratin fibres or the composition uses or contains as ingredient a) one or more neoflavanol or neoflavanone derivatives or mixtures thereof; preferentially, neoflavonol derivatives.

More particularly, the neoflavanols and neoflavanones are of formula (II) and (III) and tautomeric forms thereof, stereoisomers thereof, addition salts thereof with a cosmetically acceptable acid or base, and also the hydrates;

in which formulae (II) and (III):

• represents a conjugated double or single carbon-carbon bond,

• X represents a group:

// /

HO— C or 0=C

\ \

• R¹, R², R³, R⁴, R⁵ and R⁶, which may be identical or different, represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted acyloxy group.

The compounds of formula(ll) as defined previously may be in two tautomeric forms denoted (Ma) and (Mb):

The alkyl radicals are linear or branched, saturated hydrocarbon-based radicals, generally of C1-C20, particularly of C1-C10, preferably C1-C6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl.

The alkoxy radicals are alkyloxy radicals with alkyl as defined previously, generally C1-C10 alkoxy radicals such as methoxy, ethoxy, propoxy and butoxy.

The alkoxyalkyl radicals are preferably (C1-C20) alkoxy(Ci-C2o)alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.

The alkyl or alkoxy 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 (Ci-C₄)alkyl radical, preferentially methyl;

- an amino radical substituted with one or two identical or different C1-C6 alkyl radicals, optionally bearing at least:

^* 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 Ci-C₄ alkyl group; and M^" represents the counterion of the organic or inorganic acid or of the corresponding halide,

^* or an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (Ci-C₄)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 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 Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'SO2-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 aminosulphonyl radical ((R)2N-SO2-) 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 (preferably with an alkali metal or a substituted or unsubstituted ammonium) form;

- 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 term "glycosyl radical" means a radical derived from a monosaccharide or polysaccharide.

According to one particular embodiment of the invention, the compounds of formula (II) or (III) comprise a radical R⁶ which represents a hydroxyl group.

Another particular embodiment of the invention relates to the compounds of formula (II) or (III) for which R¹ represents a hydrogen atom or a hydroxyl group. One particular embodiment of the invention relates to the compounds a) of formula (II).

More particularly, the process for dyeing keratin fibres uses as ingredient a) one or more compounds chosen from natural haematoxylin, haematein, brazilin and brazilein compounds.

Among the haematoxylin/haematein and brazilin/brazilein compounds, mention may be made, by way of example, of haematoxylin (Natural Black 1 ) and brazilin (Natural Red 24), compounds of the indochroman family, which are commercially available. Said compounds may exist in an oxidized form or be obtained by synthesis routes or routes of extraction from plants or vegetables known to be rich in these compounds.

The compounds of formulae (II) and (III) can be used in the form of extracts. Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis.

The extracts are obtained by extracting various plant parts, for instance the root, the wood, the bark or the leaves.

According to one embodiment, the natural haematoxylin/haematein and brazilin/brazilein compounds are derived from the wood of logwood or Brazilwood trees.

Preferably, the natural compound(s) of formula (II) or (III) of the invention are derived from plant extracts.

In particular, the ingredient a) represents at least 80% by weight relative to the total weight of the ingredients b), c), d), e) and f).

Mixtures of plant extracts may also be used.

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 synthetic or natural compound(s) of formulae (II) and (III), such as the haematoxylin/haematein and brazilin/brazilein compounds and/or the natural extract(s) used as ingredient a) in one or more composition(s) useful in the process according to the invention, preferably represent(s) from 0.001 % to 20% by weight of the total weight of the composition(s) containing the compound(s) of formulae (II) and (III) such as the haematoxylin/haematein and brazilin/brazilein compounds or the extract(s) .

As regards the pure compounds of formulae (II) and (III), such as the pure haematoxylin/haematein and brazilin/brazilein compounds, the content in the composition(s) containing them is preferably between 0.001 et 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. According to one particular embodiment of the invention, the composition comprises as ingredient a) one or more synthetic dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s) that do not exist in nature.

According to another preferred embodiment of the invention, the compound that is useful in the process for dyeing keratin fibres comprises as ingredient a) one or more natural dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s).

The compounds of formula (I), (II) or (III) that are useful in the process of the invention may be natural or synthetic. Among the natural compounds are compounds that are present in nature and that can be reproduced by chemical synthesis.

The salts of the compounds of formula (I), (II) or (III) of the invention may be salts of cosmetically acceptable acids or bases. The acids may be inorganic or organic. Preferably, the acid is hydrochloric acid, which results in chlorides.

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

Preferably, the compounds a) are chosen from catechin and haematoxylin.

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 dihydroxyflavonoid, neoflavanol or neoflavanone derivatives are derived from extracts of animals, of bacteria, of fungi, of algae, of plants and of fruits, used in their entirety or partially. In particular regarding the plants, the extracts are derived from fruits, including citrus fruits, from vegetables, from trees and from shrubs. Mixtures of these extracts that are rich in dihydroxyflavonoid derivative(s) as defined previously may also be used.

Preferably, the natural dihydroxyflavonoid, neoflavanol or neoflavanone derivatives of the invention are derived from extracts of plants or plant parts.

For the purposes of the invention, said extracts will be assimilated 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 and of rose. _{Λ Λ}

14

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

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

Among the extracts of tree wood, mention may be made of extracts of pine bark and extracts of logwood.

Mixtures of plant extracts may also be used.

According to one particular embodiment of the invention, the dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s) is (are) natural extract(s), rich in dihydroxyflavonoid(s), neoflavanol(s) or neoflavanone(s). According to one preferred mode, the dihydroxyflavonoid derivative(s) are solely natural extracts. More preferably ingredient(s) a) according to the invention are chosen from :

- dihydroxyflavanol such as catechin, especially associated with ingredient(s) f) chosen from zinc, calcium and rhodium ; and

- neoflavanol particularly of formula (lla)/(llb) such as haematoxylin, especially associated with ingredient(s) f) chosen from aluminium, zinc and molibdenium.

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

As regards the pure dihydroxyflavonoid, neoflavanol or neoflavanone derivatives, 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. AddjtjgnaJjjrthg-difDhen

According to one particular embodiment of the invention, the dyeing process may use one or more ortho-diphenol derivative(s) different from the dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s).

The ortho-diphenol derivative(s) may be present in one or more cosmetic compositions used during the dyeing process.

One particular embodiment of the invention relates to ortho-diphenol derivatives or mixtures of compounds comprising one or more aromatic rings, 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 is different from the dihydroxyflavonoid derivatives and is of formula (IV), or an oligomer thereof, in salified or non-salified form:

in which formula (IV) the substituents:

Ri to R₄, which may be identical or different, represent:

- a hydrogen atom;

- a halogen atom,

- a hydroxyl radical, _Λ

16

- 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, Ri to R₄ together form from one to four rings.

One particular embodiment of the invention concerns ortho-diphenol derivatives of formula (IV) in 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 hydroxyls.

The saturated or unsaturated, optionally fused rings may also be optionally substituted.

The alkenyl radicals are linear or branched, unsaturated C2-C20 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 non-fused, 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 alkyloxy radicals with alkyl as defined previously, preferably of C1-C10, such as methoxy, ethoxy, propoxy and butoxy.

The alkoxyalkyl radicals are preferably (Ci-C2o)alkoxy(CrC2o)alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.

The cycloalkyi radicals are generally C₄-Cs cycloalkyi radicals, preferably cyclopentyl and cyclohexyl radicals. The cycloalkyi radicals may be substituted cycloalkyi 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;

^■ one hydroxyl group,

^■ an 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 Ci-C₄ alkyl group; and M^" represents the counterion of the organic or inorganic acid or of the corresponding halide,

^■ or an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (Ci-C₄)alkyl radical, preferentially methyl; 1 o

- 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 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 Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'SO₂-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 aminosulphonyl radical ((R)₂N-SO₂-) 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 cyano group;

- a nitro group;

- a carboxyl or glycosylcarbonyl group;

- 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 C1-C10 and preferably Ci-Cs alkyl radical optionally substituted with one or more radicals chosen from the radicals hydroxyl, C₁-C₂ alkoxy, C₂-C₄ (poly)hydroxyalkoxy, acylamino, amino substituted with two Ci-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; an optionally cationic 5- or 6-nnennbered heteroaryl radical, preferentially imidazolium, optionally substituted with a (Ci-C₄)alkyl radical, preferentially methyl;

^■ one hydroxyl group,

^■ or an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (Ci-C₄)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 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 Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical

(R'SO2-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 aminosulphonyl radical ((R)2N-SO2-) 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 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 _2Q

a phenyl group optionally substituted with one or more hydroxyl groups. For the purposes of the present invention, 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 in particular 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 benzofuranyl, 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 inorganic or organic. Preferably, the acid is hydrochloric acid, which results in chlorides.

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

According to another preferred embodiment of the invention, the compound that is useful in the process for dyeing keratin fibres comprises 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 a) are in particular:

- anthocyanidins, for instance cyanidin, delphinidin and petunidin,

- anthocyanines or anthocyans, for instance myrtillin,

- ortho-hydroxybenzoates, for example gallic acid salts,

- hydroxystilbenes, for example 3,3',4,5'-tetrahydroxystilbene, 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,

- quinones,

- hydroxyxanthones,

- 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 in particular the proanthocyanidins A1 , A2, B1 , B2, B3 and C1 ,

- proathocyanines,

- tannic acid,

- ellagic acid,

- and mixtures of the preceding compounds.

According to one embodiment, the natural ortho-diphenols are derived from extracts of animals, of bacteria, of fungi, of algae, of plants and of fruits, used in their entirety or partially. In particular regarding the plants, the extracts are derived from fruits, including citrus fruits, from vegetables, from trees and from 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 as additional ortho-diphenols.

Among the plant extracts, mention may be made of extracts of tea leaves and of rose. ^

Among the extracts of tree wood, mention may be made of extracts of pine bark.

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 embodiment, the ortho-diphenol derivative(s) are solely natural extracts.

Preferentially, the ortho-diphenol(s) according to the invention is (are) chosen from gallic acid, and natural extracts containing them chosen from grape marc, pine bark, green tea, onion, cocoa bean, redwood and gall nut.

According to the invention, the natural and synthetic ortho-diphenol derivative(s), and/or the natural extract(s) used as ingredient a) in one or more cosmetic 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) manganese salt

The dyeing process according to the invention uses one or more manganese (Mn) salt(s). The manganese salt(s) may be used in one or more cosmetic compositions used during the dyeing process.

For the purposes of the present invention, the term "salts" means the oxides of these metals and salts per se derived in particular 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; sulphates; phosphates; nitrates; perchlorates and carboxylic acid salts and polymer salts, and also mixtures thereof.

More particularly, the manganese salt is different from manganese carbonate, manganese hydrogen carbonate or manganese dihydrogen carbonate.

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

As examples of polymer salts, mention may be made of manganese pyrrolidone carboxylate.

By way of example, mention may be made of manganese chloride, manganese fluoride, manganese acetate tetrahydrate, manganese lactate trihydrate, manganese phosphate, manganese iodide, manganese nitrate trihydrate, manganese bromide, manganese perchlorate tetrahydrate, manganese sulphate monohydrate and manganese gluconate. The salts advantageously used are manganese gluconate and manganese chloride.

The manganese 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 (in particular water from 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).

According to one preferred embodiment of the invention, the manganese salt(s) used represent(s) from 0.001 % to 0.1 % by weight, approximately, of the total weight of the composition(s) containing said metal salt(s), and even more preferentially from 0.05% to 10% by weight approximately.

Particularly, the metal salts b) of the invention are in oxidation state 2, such as Mn (II).

Even more preferentially, the manganese salt(s) is (are) chosen from carboxylic acid salts of manganese, in particular manganese gluconate, and manganese halides, such as manganese chloride. c) hydrogen peroxide or hydrogen peroxide-generating system In the context of the present invention, the third constituent is hydrogen peroxide or a hydrogen peroxide-generating system, such as:

a) urea peroxide;

b) polymeric complexes that can release hydrogen peroxide, such as polyvinylpyrrolidone/H₂O2 in particular in the form of powders, and the „„

24

other polymeric complexes described in US 5 008 093; US 3 376 1 10; US 5 183 901 ;

c) 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);

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

perborates; or

e) percarbonates.

According to one preferred embodiment of the invention, the composition contains one or more hydrogen peroxide-generating system(s), chosen from a) urea peroxide, b) polymeric complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H₂O2; c) oxidases; e) perborates and f) percarbonates.

Particularly, the third constituent is hydrogen peroxide.

Moreover, the composition(s) comprising the hydrogen peroxide or the hydrogen peroxide generator may also contain various adjuvants conventionally used in hair dye compositions and as defined hereinbelow.

According to one particular mode of the invention, the hydrogen peroxide used or the hydrogen peroxide-generating system(s) used preferably represent(s) from 0.001 % to 12% by weight of hydrogen peroxide relative to the total weight of the composition(s) containing it/them, and even more preferentially from 0.2% to 2.7% by weight. d) (bi)carbonate(s) or (bi)carbonate-generating system

In accordance with the present invention, the dyeing process uses one or more (bi)carbonates or one or more (bi)carbonate-generating systems. The term "(bi)carbonate-generating system" means a system which generates (bi)carbonate in situ, for instance carbon dioxide in water or by buffering carbonate with an inorganic or organic acid.

The (bi)carbonates or the (bi)carbonate-generating system(s) may be used in one or more cosmetic compositions during the dyeing process.

The (bi)carbonate(s) is (are) chosen from:

carbonates of alkali metals (Met²⁺, CO3^2"), of alkaline-earth metals (Met'²⁺, CO₃ ^2") of ammonium ((R"₄N⁺)₂,CO₃ ^2") or of phosphonium ((R" P⁺)₂,CO3^2" with Met' representing an alkaline-earth metal and Met representing an alkali metal, and R", which may be identical or different, ^

representing a hydrogen atom, or an optionally substituted group (Ci- C6>alkyl such as hydroxyethyl),

- bicarbonates, also known as hydrogen carbonates, of the following formulae: R'⁺, HCO3^" with R' representing a hydrogen atom, an alkali metal, an ammonium group R" N⁺- or a phosphonium group R" P⁺- in which R", which may be identical or different, represent a hydrogen atom, or an optionally substituted (Ci-Ce)alkyl group, such as hydroxyethyl, and, when R' represents a hydrogen atom, the hydrogen carbonate is then known as a dihydrogen carbonate (CO2, H₂O); and Met'²⁺ (HCO^3")2 with Met' representing an alkaline-earth metal.

More particularly, the (bi)carbonate(s) is (are) chosen from alkali metal, alkaline-earth metal or ammonium (bi)carbonates; preferentially, alkali metal or ammonium (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 spring water from the Vichy basin or from La Roche Posay or Badoit water (cf. for example, patent document FR 2 814 943). Particularly, mention may be made of sodium carbonate [497-19-8] = Na2CO3, sodium hydrogen carbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate =

Na(HCO₃)₂.

According to the invention, the (bi)carbonate agent(s) used preferably represent(s) from 0.001 % to 10% by weight of the total weight of the composition(s) containing the (bi)carbonate agent(s) and even more preferentially from 0.005% to 5% by weight.

Preferably, the (bi)carbonate used in the dyeing process and of the composition is ammonium bicarbonate or sodium bicarbonate (paragraph added according to the examples). e) alkalinizing agent(s) different from the bicarbonate(s)

The alklinizing agent used in the dyeing process according to the invention as fifth ingredient is different from the (bi)carbonate(s) e) as defined previously. It is an agent which makes it possible to increase the pH of the composition(s) in which it is present. The alkalinizing agent is a Br0nsted, Lowry or Lewis base. It may be inorganic or organic.

Particularly, said agent is chosen from i) aqueous ammonia, ii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, iii) oxyethylenated and/or oxypropylenated ^

26

ethylenediamines, iv) inorganic or organic hydroxides, v) alkali metal silicates such as sodium metasilicates, vi) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and vii) the compounds of formula (V) below:

N - W - N

/ \

R^{c Rd} (V)

in which formula (V):

- W is a (d-CsJalkylene divalent group, preferably propylene group, optionally substituted in particular with a hydroxyl group or a Ci-C₄ alkyl radical;

- R_a, R_b, Rc and R_d, which may be identical or different, represent a hydrogen atom or a Ci-C₄ alkyl or Ci-C₄ hydroxyalkyl radical.

The inorganic or organic hydroxides, particularly the inorganic or organic hydroxides, are preferably chosen from i) hydroxides of an alkali metal, ii) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, iii) hydroxides of a transition metal, such as hydroxides of metals from groups III, IV, V and VI, and iv) hydroxides of lanthanides or of actinides, quaternary ammonium hydroxides and guanidinium hydroxide.

Preferentially, whether for the composition according to the invention or the process implemented in the invention, the alkalinizing agent is not sodium hydroxide NaOH. More generally and preferentially, whether for the composition according to the invention or the process implemented in the invention, the alkalinizing agent is not an alkali metal hydroxide XOH, with X = alkali metal.

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

The alkalinizing agent(s) as defined previously preferably represent(s) from

0.001 % to 10% by weight of the weight of the composition(s) containing them. It (they) more particularly represent(s) from 0.005% to 8% by weight of the composition.

Preferably, the alkaline agent(s) is (are) chosen from alkanolamines, in particular monoethanolamine. f) molybdenum (Mo), aluminium (Al), zinc (Zn), calcium (Ca) and rhodium (Rh) salts The process of the invention comprises one or more Mo, Al, Zn, Ca or Rh salts. The term "metal salt" means the oxides of this metal and the salts per se derived in particular 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; sulphates; phosphates; nitrates and carboxylic acid salts and polymer salts, and also mixtures thereof.

According to one particular embodiment of the invention, the metal derivative(s) f) is (are) molybdenum (Mo), in particular the metal derivative(s) 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; http://www.wiley-vch.de/index.html, "Molybdenum and Molybdenum Compounds".

More particularly, the metal salts of the invention are chosen from:

i. Mo oxides such as:

- Mo (IV) oxides bearing /3-diketone ligands M0O2L2 with L ligand, which may be identical or different, preferentially identical, representing a /3-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 (Ci-Ce)alkyl group, and R' representing a hydrogen atom or a linear or branched (Ci-Ce)alkyl group, X representing an oxygen or sulphur atom or a group N(R) with R representing a hydrogen atom or a linear or branched (Ci-Ce)alkyl group, more particularly the Mo dioxide is of the formula MoO2[CH₃C(O)CHC(O)CH₃]2 [17524-05-9];

- molybdenum dioxide;

- dihalodioxomolybdenum (Hal)2MoO2 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], a 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 ); in particular Mo⁶⁺ ₃Mo⁵⁺ ₃Oi₈H, and the derivatives from condensation with phosphate ions;

ii. 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 [Mo6Hal₃]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;

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

iv. Mo sulphur derivatives chosen from:

Molybdenum disulphidess [1317-33-5], molybdenum(IV) sulphides, MoS₂;

- Mo sesquisulphides [12033-33-9]; dimolybdenum (III) trisulphides, Mo₂S_3;

v. 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 phthalocyanines as described in US 3 931 249;

vi. monomeric or polymeric molybdenum carboxylates; such as those of formula n[R-C(O)O^"].n[Mo] in which n represents an integer other than zero and preferentially equal to 2, and R represents an optionally substituted (Ci-Csjalkyl group; the monomeric or polymeric molybdenum carboxylates are particularly molybdenum acetate dimer [14221 -06-8].

Preferentially, the metal derivatives are chosen from Mo carboxylates and more particularly molybdenum acetate dimer.

In one preferred embodiment of the invention, the amount by weight of molybdenum is identical to that of the dyes.

According to one particular embodiment of the invention, the metal derivatives(s) f) is (are) chosen from aluminium salts and aluminium oxides and also the hydrates thereof and supported forms thereof. Examples that may be mentioned include aluminium oxides, hydroxides, sulphates, halides, carboxylates and phosphates such as those described in Ullmann's encyclopedia "Aluminium oxide", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002/14356007.a06 139, pp. 1 -40.

In particular, the aluminium hydroxide(s) and oxide(s) is (are) chosen from aluminium trihydroxide AI(OH)₃, aluminium oxide hydroxide AIO(OH), aluminium oxide AI2O3, hydrated or anhydrous, and alkali metal aluminates such as sodium aluminate NaAIO₂ [1302-42-7].

In particular, the aluminium sulphates are chosen from hydrated or anhydrous aluminium sulphate AI2O12S3 such as aluminium sulphate octahydrate.

In particular, the aluminium carboxylates are chosen from basic aluminium acetate C₄H₇O₅AI [142-03-0], aluminium oxalate, hydrated or anhydrous aluminium citrate, such as aluminium citrate hydrate [31 142-56-0], aluminium lactate and aluminium glycinate. In particular, the aluminium phosphates are chosen from aluminium phosphate AIPO₄ [7784-30-7].

Preferentially, the metal derivative is chosen from aluminium sulphate octahydrate, basic aluminium acetate C₄H₇O₅AI [142-03-0], aluminium oxalate, aluminium citrate hydrate [31 142-56-0], aluminium lactate, aluminium glycinate and aluminium phosphate AIPO₄ [7784-30-7].

In one preferred embodiment of the invention, the amount by weight of aluminium is likewise identical to that of the dyes. According to one particular embodiment of the invention, the metal derivative(s) f) is (are) chosen from zinc salts and also the hydrates thereof and the supported forms thereof that are different from the zinc salts according to b) as defined previously. Preferentially, the zinc is in oxidation state II, or Zn II.

Among the zinc salts, mention may be made of zinc sulphates; zinc halides such as zinc chloride; and zinc carboxylates such as zinc lactate, zinc acetate, zinc glycinate, zinc gluconate and zinc aspartate.

Preferentially, the zinc salt is zinc sulphate, zinc gluconate, zinc acetate or zinc glycinate.

In one preferred embodiment of the invention, the amount by weight of zinc is identical to that of the dyes.

According to one particular embodiment of the invention, the metal derivatives(s) f) is (are) chosen from calcium salts and also the hydrates thereof and supported forms thereof. By way of example, mention may be made of the hydroxides, sulphates, halides, carboxylates, phosphates, borates and carbonates.

In particular, the hydroxides are calcium hydroxide Ca(OH)₂.

According to one advantageous embodiment, the calcium salts are calcium sulphates, in particular those chosen from calcium sulphate CaSO₄ and gypsum.

According another variant, the calcium salts are calcium halides, in particular chosen from calcium chloride, calcium bromide and calcium iodide.

According to yet another variant of the invention, the calcium salts are calcium carboxylates, in particular chosen from calcium oxalate, calcium diacetate, calcium citrate, tricalcium 2-hydroxypropanoate-1 ,2,3-tricarboxylate [813-94-5], calcium lactate, calcium 2-hydroxypropanoate, hydrated or anhydrous calcium gluconate, calcium ascorbate, calcium 2-ethylbutanoate, calcium formate, calcium levulinate, calcium mesoxalate, calcium oleate, calcium palmitate, calcium propionate, calcium saccharate, calcium stearate, calcium steryl-2- lactylate, calcium succinate, calcium tartrate and calcium pyrrol idonecarboxylate. _3Q

According to another particular embodiment of the invention, the calcium salts are calcium phosphates, in particular chosen from calcium phosphate Ca3(PO₄)2, hydrated or anhydrous calcium hydrogen phosphate CaHPO₄, calcium hydroxyphosphate [Ca₅(OH)(PO₄)3] , hydrated or anhydrous calcium bis(dihydrogen phosphate) Ca(H₂PO₄)2, calcium pyrophosphate Ca2P2O₇, hydroxyapatite, calcium fluorophosphate and calcium glycerophosphate.

In particular, the calcium derivative is calcium borate.

More particularly, the calcium derivative is calcium carbonate or calcium dihydrogen carbonate.

Preferentially, the calcium derivative is chosen from calcium sulphate

CaSO₄, gypsum, calcium diacetate, hydrated or anhydrous calcium gluconate, calcium phosphate Ca3(PO₄)2, hydrated or anhydrous calcium hydrogen phosphate CaHPO₄, hydrated or anhydrous calcium bis(dihydrogen phosphate) Ca(H₂PO₄)2, calcium pyrrol idonecarboxylate and hydroxyapatite.

According to one preferred embodiment of the invention, the mole amount of calcium is identical to the mole amount of the dyes.

According to one particular embodiment of the invention, the metal derivatives(s) f) is (are) chosen from rhodium salts and also the hydrates thereof and supported forms thereof. The Rh salts may also be in the form of a complex.

By way of example, mention may be made of the rhodium salts described in Ullmann's encyclopedia « Platinum Group Metals and Compounds », 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002/14356007.a21 075, pp. 1 -78;

http://onlinelibrary.wiley.com/doi/10.1002/14356007.a21_075/pdf.

More specifically, mention may be made of Rh sulphates, halides and carboxylates.

In particular, the sulphate is rhodium +III sulphate (Rh₂(SO₄)₃) [10489-46-0].

According to one advantageous variant, the Rh salts are chosen from halides such as rhodium +III chlorides which are hydrated (RhCb 2.5H₂O) or anhydrous (RhCb), for instance rhodium chloride trihydrate.

In particular, the carboxylates are rhodium +III acetate [42204-14-8].

Preferentially, the rhodium derivative is chosen from rhodium sulphate and rhodium acetate.

In one preferred embodiment of the invention, the amount of rhodium is of the same order of magnitude as that of the dyes.

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

The metal salts f) 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 (in particular the Dead Sea). They may also originate from inorganic compounds, such as plant extracts containing them (cf. for patent example, document FR 2 814 943).

- 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 fibres and/or from the composition(s) comprising compounds a) to f) 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 f) as defined previously.

- cosmetic compositions:

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 another substance without chemically modifying it. - organic solvents:

Examples of organic solvents that may be mentioned include Ci-C₄ lower alkanols, 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 40% by weight approximately and more preferably still between 5 and 30% by weight approximately relative to the total weight of the dye composition.

- 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, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preservatives and opacifiers.

Said adjuvants are preferably chosen from surfactants such as anionic or nonionic surfactants or mixtures thereof and inorganic 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, those 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 dyeing process in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition(s).

- additional dyes:

The dyeing process using the ingredients a) to f) as previously defined and also optionally ortho-diphenol derivatives as previously defined, may also use 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 different from ortho-diphenols, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metal loporphyrin, phthalocyanine and methine cyanine direct dyes, and fluorescent dyes.

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.

According to the invention, the direct dye(s) used in the composition according to the invention which comprises the ingredients a) to f) as previously defined, or the composition(s) of the dyeing process according to the invention, preferably represent(s) from 0.001 % to 10% by weight approximately of the total weight of the composition(s) and even more preferentially from 0.05% to 5% by weight approximately. ^

The composition according to the invention or the composition(s) of the process using the ingredients a) to f) as previously defined may also comprise one or more oxidation bases and/or one or more couplers conventionally used for dyeing keratin fibres.

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 in particular of meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.

The oxidation base(s) present in said composition(s) that is (are) used in the process is (are) generally each present in an amount between 0.001 to 10% by weight of the total weight of the composition(s) containing it or them.

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 fibres. They may also be packaged in a propellant-free pump-dispenser bottle or under pressure in an aerosol container in the presence of a propellant and form a mousse.

- pH of the composition(s):

In accordance with the present invention, the pH of at least one of the cosmetic compositions comprising at least one of the ingredients a), b), d), e) and/or f) is alkaline, i.e. greater than 7, and preferably between 8 and 12, and more particularly between 8 and 10.

In other words, at least one of the cosmetic compositions used during the dyeing process of the invention has an alkaline pH, i.e. greater than 7.

According to one embodiment, the pH of the cosmetic composition(s) containing d) one or more (bi)carbonate(s) or one or more (bicarbonate- generating system(s) is (are) alkaline, i.e. greater than 7, preferably between 8 and 12, and more particularly between 8 and 10.

Preferably, the (bi)carbonate(s) or the bicarbonate-generating system(s) is (are) used in a single cosmetic composition and the pH of said composition is alkaline, i.e. greater than 7, preferably between 8 and 12, and more particularly between 8 and 10.

According to one particular embodiment of the invention, the pH of the cosmetic composition comprising d) one or more (bi)carbonates or one or more (bi)carbonate-generating system(s) and e) one or more alkalinizing agents(s) ^

different from the (bi)carbonate(s) is (are) alkaline, i.e. greater than 7, preferably between 8 and 12, and more particularly between 8 and 10.

In other words, preferably, the (bi)carbonate(s) or the (bicarbonate- generating system(s) and the alkalinizing agent(s) different from the (bi)carbonates e) is (are) used in a single composition and the pH of said composition is alkaline, i.e. greater than 7, preferably between 8 and 12, and more particularly between 8 and 10, in particular between 9 and 10.

Even more preferentially, the (bi)carbonate(s) chosen from ammonium bicarbonates and the alkalinizing agents chosen from alkanolamines is (are) used in a single cosmetic composition and the pH of said composition is alkaline, i.e. greater than 7, preferably between 8 and 12, and more particularly between 8 and 10, in particular between 9 and 10.

According to one embodiment, if one or more cosmetic compositions used during the dyeing process does not contain (bi)carbonates, the pH of the composition(s) containing hydrogen peroxide or a hydrogen peroxide-generating system is preferably less than 7, more particularly between 1 and 5.

Preferably, the composition(s) containing the ortho-diphenol(s) and not containing (bi)carbonates has (have) a pH of less than 7 and preferably between 3 and 6.5.

According to one particular embodiment of the invention, the cosmetic composition(s) containing the manganese or zinc salt(s) b) and not containing (bi)carbonates has (have) a pH of less than 7 and preferably between 3 and 6.5.

According to one particular embodiment of the invention, the cosmetic composition(s) containing the metal salt(s) f) and not containing (bi)carbonates has (have) a pH of less than 7 and preferably between 3 and 6.5.

The pH of these compositions may be adjusted to the desired value by means of alkalinizing agents as defined previously in d) or by means of acidifying agents usually used in the dyeing of keratin fibres, 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 inorganic or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulphuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.

Among the alkalinizing agents, they are agents as defined previously under the heading "c/J alkalinizing agent(s)".

-dyeing process in one or more steps

According to one embodiment, the process for dyeing keratin fibres is performed in a single step by applying to the keratin fibres an aqueous dye composition, comprising: ^

a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s);

b) one or more manganese salt(s);

c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s);

e) one or more alkalinizing agent(s) different from the (bi)carbonate(s); and f) one or more metal salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts.

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.

In this embodiment, the cosmetic dye composition comprising the ingredients a), b), c), d), e) and f) has an alkaline pH, i.e. therefore greater than 7, preferably between 8 and 12, and more particularly between 8 and 10.

According to another embodiment, the process for dyeing keratin fibres is performed in two or three steps.

According to one particular embodiment of the invention, the process for dyeing keratin fibres is carried out in two steps by applying to the keratin fibres a dye composition comprising the ingredients a), b), c), d) and e) as previously defined, and then, in a second step, a composition comprising the ingredient f) as previously defined is applied to said keratin fibres, it being understood that at least one of the two compositions is aqueous. Preferably, the composition comprising the dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s), is aqueous. Even more preferentially, the two compositions used in this embodiment are aqueous.

For this process, the leave-on time after application 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 application time of the composition comprising the ingredient f) during the second step is generally set at between 3 and 120 minutes, preferentially between 3 and 60 minutes and more preferentially between 5 and 30 minutes.

According to another embodiment, the process for dyeing keratin fibres is performed in three steps.

In a first variant of the process in three steps, the first step consists in applying to said fibres a composition comprising the ingredients a), b) and c) as previously defined, then, in a second step, a composition comprising the ingredients d) and e) as previously defined is applied to said fibres, and then, in a „

36

third step, a composition comprising the ingredient f) is applied to said fibres, it being understood that at least one of the three compositions is aqueous. Preferably, the composition comprising the dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s), is aqueous. Even more preferentially, the three compositions used in this embodiment are aqueous.

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

For the latter two processes, the leave-on time after application 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 application time of the composition used during the second step is generally set at between 3 and 120 minutes, preferentially between 3 and 60 minutes and more preferentially between 5 and 30 minutes. The application time of the composition used during the third step is generally set at between 3 and 120 minutes, preferentially between 3 and 60 minutes and more preferentially between 5 and 30 minutes.

According to one embodiment, the process for dyeing keratin fibres is carried out in one or more steps by applying to the keratin fibres one or more cosmetic compositions comprising:

a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s), in particular those chosen from catechin and quercetin;

b) one or more manganese salt(s) chosen from the carboxylic acid salts of manganese, in particular manganese gluconate:

c) hydrogen peroxide;

d) one or more (bi)carbonate(s), in particular ammonium bicarbonates;

e) one or more alkalinizing agents chosen from alkanolamines;

f) one or more salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts, in particular chosen from:

i) monomeric or polymeric molybdenum carboxylates; such as those of formula n[R-C(O)O^"].n[Mo] in which n represents an integer other than zero and preferentially equal to 2, and R represents an optionally substituted (Ci-Cs) alkyl group; the monomeric or polymeric molybdenum carboxylates are particularly molybdenum acetate dimer [14221 -06-8];

ii) aluminium sulphates such as aluminium sulphate octahydrate;

iii) zinc sulphates such as zinc sulphate heptahydrate;

iv) zinc carboxylates such as zinc acetate or glycinate; ^

v) calcium carboxylates such as calcium acetate or calcium pyrrol idonecarboxylate;

vi) rhodium III carboxylates;

it being understood that the composition comprising the ingredient d) has an alkaline pH, i.e. therefore greater than 7, in particular between 8 and 10, and that the composition comprising the ingredient(s) f) is applied to the keratin fibres in the final step of the dyeing process.

Preferably, the process for dyeing keratin fibres is carried out in three steps. In particular, the dyeing process is carried out in three steps by applying to the keratin fibres:

i) a cosmetic composition comprising a) one or more dihydroxyflavonoid derivative(s), b) one or more manganese salt(s) chosen from carboxylic acid salts of manganese, and c) hydrogen peroxide;

ii) a cosmetic composition comprising d) one or more (bi)carbonate(s) chosen from ammonium bicarbonates and e) one or more alkalinizing agents chosen from alkanolamines;

iii) a cosmetic composition comprising f) one or more salts chosen from:

- monomeric or polymeric molybdenum carboxylates; such as those of formula n[R-C(O)O^"].n[Mo] in which n represents an integer other than zero and preferentially equal to 2, and R represents an optionally substituted (Ci-Cs)alkyl group; the monomeric or polymeric molybdenum carboxylates are particularly molybdenum acetate dimer [14221 -06-8];

- aluminium sulphates such as aluminium sulphate octahydrate;

- zinc sulphates such as zinc sulphate heptahydrate;

- zinc carboxylates such as zinc acetate or glycinate;

- calcium carboxylates such as calcium acetate or calcium pyrrol idonecarboxylate;

- rhodium III carboxylates;

it being understood that the composition comprising the ingredients d) and e) has an alkaline pH, i.e. therefore greater than 7, in particular between 8 and 10, and that the composition comprising the metal salts is applied to the keratin fibres in the final step of the dyeing process.

More particularly, the dihydroxyflavonoid derivative(s), a) used in the composition may be chosen from catechin, quercetin, and natural extracts containing them. Even more particularly, the dihydroxyflavonoid(s) is (are) chosen from catechin and quercetin.

More particularly, the neoflavanol or neoflavanone derivative(s), a) used in the composition may be chosen from extracts of logwood and of redwood. When Jo

an additional ortho-diphenol is also present in the process, it is preferentially gallic acid and derivatives thereof, which are found in particular in extracts of gall nut.

Irrespective of the application method, the application temperature is generally between ambient temperature (15 to 25°C) and 80°C and more particularly between 15 and 45°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.

Use may be made, both as means for heating and for smoothing the hair, of a heating iron at a temperature of between 60 and 220°C and preferably between 120 and 200°C.

Irrespective of the application method, the keratin fibres may optionally be wiped and/or dried between each step; in particular, before carrying out the step comprising the application of a composition comprising the ingredient d), and in particular before carrying out the final step comprising the application of a composition containing the metal salt(s) f) as previously defined.

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

In all the particular embodiments and variants of the processes previously described, the compositions mentioned are ready-to-use compositions that may result from the extemporaneous mixing of two or more compositions and in particular of compositions present in dyeing kits.

- dyeing device or "kit"

Another subject of the invention is a multicompartment dyeing device or "kit". Advantageously, this kit comprises from 2 to 7 compartments containing from 2 to 7 compositions in which are distributed the ingredients a) one or more dihydroxyflavonoid derivative(s), b) one or more manganese salt(s), c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s), d) one or more (bi)carbonate(s) or one or more bicarbonate-generating system(s), e) one or more alkalinizing agent(s) different from the (bi)carbonate(s) and f) one or more salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts, it being possible for said compositions to be aqueous or pulverulent, with particularly at least said compositions being aqueous.

According to a first variant, the kit comprises seven compartments, the first six compartments comprising, respectively, the powdered ingredients a), b), c), d), e) and f) as defined previously and the sixth compartment containing an aqueous ^

composition such as water. In this case, the compound(s) c) is (are) hydrogen peroxide precursors.

Another variant concerns a six-compartment kit, at least one of which compartments contains an aqueous composition, the other compartments comprising an ingredient a) to f) as previously defined.

In another variant, the device comprises six compartments: a first compartment comprising a composition containing the ingredient a) as previously defined, a second compartment comprising the ingredient b) as previously defined, a third compartment comprising the ingredient c) as previously defined, a fourth compartment containing the ingredient d) as previously defined, a fifth compartment containing the ingredient e) as previously defined, and a sixth compartment containing the ingredient f) as previously defined, it being possible for said compositions to aqueous or pulverulent. Preferably, at least one of these compositions is aqueous.

Another preferred embodiment concerns a device comprising four compartments:

(i) a first compartment contains a composition containing:

a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s); and

(ii) a second compartment contains a composition containing:

b) one or more manganese salt(s),

c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s);

(iii) a third compartment contains a composition containing:

d) one or more (bi)carbonate(s) or one or more (bi)carbonate-generating system(s), and

e) one or more alkalinizing agent(s) different from the (bi)carbonate(s);

(iv) a fourth compartment contains a composition containing:

f) one or more salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts.

In this other embodiment, at least one of the four compositions is aqueous and the dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s) may be in powder form.

It is also possible to have a four-compartment kit, the first i) containing a composition comprising a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s) and b) one or more manganese salts, the second ii) containing a composition comprising c) hydrogen peroxide or a hydrogen peroxide-generating system, the third iii) containing a composition comprising d) the (bi)carbonate agent and e) the alkalinizing agent different from the (bi)carbonate, and the fourth iv) containing a composition comprising f) one or „_Λ

40

more salt(s) chosen from molybdenum, aluminium, zinc, calcium and rhodium salts.

In this other kit, at least one of the compositions is preferentially aqueous. In addition, more particularly, this composition contains hydrogen peroxide.

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

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

In these two variants of a three-compartment kit, the first composition contained in the first compartment comprising either the ingredients a), b) and c) as previously defined or the ingredients a), b), d) and e) as previously defined 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 comprising one or more treating agents.

The compositions of the device according to the invention are packaged 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 also be equipped with a means for dispensing the desired mixture on the hair, for instance the devices described in patent FR 2 586 913.

As previously indicated, a subject of the present invention is also a cosmetic composition for dyeing keratin fibres, comprising the ingredients a), b), c), d), e) and f), it being understood that the pH of the composition is alkaline, i.e. greater than 7 and preferably between 8 and 12. It is particularly between 8 and 10.5.

A subject of the invention is also the use of said cosmetic dye composition for dyeing keratin fibres.

The examples that follow serve to illustrate the invention without, however, being limiting in nature. EXAMPLES

Examples of dyeing

In the following example, the uptake of the coloration ΔΕ^* and the chromaticity C^* were compared between a dyeing process according to the invention and a dyeing process which is identical but which does not involve the use of a composition comprising salts.

1 . Compositions tested

(^*): present at 1 .5 x 10 mol. 2. Procedure:

Each composition A1 or A2 is applied to locks of hair comprising 90% white hairs that have been permanent-waved, in a proportion of 12 g of composition per gram 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 is wiped using an absorbent paper towel to remove the excess composition.

The composition B is then applied to each of the locks in a proportion of 4 g of composition per gram of locks. The pH of the composition B is 9.5. The leave- on time is 10 minutes at ambient temperature. The hair is then rinsed with water washed with a conventional shampoo and dried under a hood.

A composition C (C1 to C9) is then applied (post-treatment) to each of the locks in a proportion of 4 g of composition per gram of lock; the leave-on time is 10 minutes at ambient temperature. The hair is then rinsed with water washed with a conventional shampoo and dried under a hood.

3. Colorimetric results The uptake of the coloration ΔΕ^* and the chromaticity C^* is compared between a dyeing process according to the invention and a process that is identical but that uses water in place of the compositions C1 to C10 based on varied metal salts. The colour of the locks was evaluated in the CIE L^* a^* b^* system, using a

Minolta Spectrophotometer CM2600D colorimeter. In this L^* a^* b^* system, the three parameters denote, respectively, the colour intensity (L^*), the green/red colour axis (a^*) and the blue/yellow colour axis (b^*).

The variation in coloration between the locks of permanent-waved white hair comprising 90% white hairs (90 WP) that are untreated (control) and after treatment or dyeing are defined by (ΔΕ^*) according to the following equation:

ΔΕ* = y](L * -L₀ *)² + (a* -a₀ *)² + (b* -b₀ *)²

In this equation, L^*, a^* and b^* represent the values measured on locks of hair after dyeing and L₀ ^*, ao^* and bo^* represent the values measured on locks of undyed untreated hair. The higher the ΔΕ^* value, the better the colour uptake is.

The chromaticity was also measured by means of the values a^* and b^*, and is obtained from the following formula:

The higher the C^* value, the more chromatic is the colour obtained. ^

The values of the uptake of the coloration ΔΕ^* and the chromaticity C^* are given in the tables hereinafter :

Table 1:

Table 2:

According to tables 1 and 2, it appears visually that the process of the invention makes it possible to obtain a strong uptake and also better chromaticity of the coloration. This is confirmed by the colorimetric measurements which demonstrate that the dyeing process according to the invention makes it possible to produce colorations that are more chromatic, irrespective of the dihydroxyflavonoid derivative used, compared with a process which does not use a metal salt f).

The same tendency was observed for the colour uptake, which is very satisfactory.

Claims

C LAIMS

1. Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated with one or more cosmetic compositions containing, taken together or separately in said composition(s), the following ingredients:

a) one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s);

b) one or more manganese salt(s);

c) hydrogen peroxide or one or more hydrogen peroxide-generating system(s);

it being understood that:

- the pH of at least one of the compositions comprising at least one of the ingredients a), b), d), e) and/or f) is alkaline, i.e. greater than 7, and

- the metal salt(s) f) is (are) applied in the final step of the dyeing process.

2. Dyeing process according to Claim 1 , characterized in that the dihydroxyflavonoid derivative(s) is (are) chosen from natural dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s).

3. Dyeing process according to Claim 1 or 2, characterized in that a) the dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s) is (are) chosen from those of formula (I), (II) or (III) and also organic or inorganic acid salts thereof, optical, geometric and tautomeric isomers thereof, and solvates thereof such as the hydrates:

in which formula (I):

• ^{z z '} represents a single bond or a double bond;

• 10

R\ R², R³, R⁴, R¹ »11 »12

R^1j and R , which may be identical or different, represent:

- a hydrogen atom,

- a halogen atom,

- a hydroxyl group,

- a (Ci-C6)alkyl group,

- a (Ci-C6)alkoxy group,

- a (Ci-C6>alkylthio group,

- a carboxyl group,

- an alkyl carboxylate or alkoxycarbonyl group,

- an optionally substituted amino group,

- an optionally substituted linear or branched alkenyl group,

- an optionally substituted cycloalkyl group,

- an aryl group,

- a substituted aryl group,

- a group containing one or more silicon atoms,

- a (di)((hydroxy)(Ci-C6)alkyl)amino group,

- an -O-sugar group such as -O-glucoside,

- an R-Z-C(X)-Y- group with R representing a hydrogen atom or a (Ci-C6)alkyl group, Y and Z, which may be identical different, represent a bond, or an oxygen or sulphur atom or an -N(R')- group with R' representing a hydrogen atom or a (Ci-Ce)alkyl group, Y possibly also representing a (Ci-Ce)alkylene group; X representing an oxygen or sulphur atom, or N-R" with R" representing a hydrogen atom or a (Ci-Ce)alkyl group; • R⁵, R⁶, R⁷, R⁸ and R⁹, which may be identical or different, represent a hydrogen atom, or a group chosen from hydroxyl or (Ci-C6)alkyl;

• or else R⁵ with R⁶ and/or R⁷ with R⁸ form, together with the carbon atom which bears them, an oxo group;

· or else R⁸ and R⁹ together form a bond;

it being understood that:

- when borne by the oxygen atom is a double bond, then the compound of formula (I) is cationic and an anionic counterion is associated therewith;

in which formulae (II) and (III):

• represents a conjugated double or single carbon-carbon bond,

• X represents a group:

// /

HO— C or 0=C

\ \

4. Dyeing process according to any one of Claims 2 to 5, characterized in that the natural dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s) is (are) chosen from extracts of animals, of bacteria, of fungi, of algae, of plants and of fruits.

5. Dyeing process according to any one of the preceding claims, characterized in that the manganese salt(s) b) is (are) chosen from manganese oxides and the halides, sulphates, phosphates, nitrates and perchlorates, the carboxylic acid salts such as gluconates, and also mixtures thereof.

6. Dyeing process according to any one of the preceding claims, characterized in that the ingredient c) is hydrogen peroxide or urea peroxide.

7. Dyeing process according to any one of the preceding claims, characterized in that the (bi)carbonate(s) d) is (are) chosen from alkali metal, alkaline-earth metal or ammonium (bi)carbonates.

8. Dyeing process according to any one of the preceding claims, characterized in that the alkaline agent(s) e) different from the (bi)carbonate(s) is (are) chosen from:

- aqueous ammonia,

- alkanolamines,

- oxyethylenated ethylenediamines,

- oxypropylenated ethylenediamines,

- inorganic or organic hydroxides,

- alkali metal silicates,

- amino acids, and

- the compounds of formula (V) below:

N - W - N

/ \

^{Rc Rd} (V)

in which formula (V):

- W is an optionally substituted (Ci-Cs)alkylene divalent group;

9. Dyeing process according to any one of the preceding claims, characterized in that the metal derivative(s) f) is (are) chosen from:

• molybdenum oxides such as: - Mo (IV) oxides bearing /3-diketone ligands M0O2L2 with L ligand, which may be identical or different, preferentially identical, representing a /3-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 (Ci-Ce)alkyl group, and R' representing a hydrogen atom or a linear or branched (Ci-Ce)alkyl group, X representing an oxygen or sulphur atom or a group N(R) with R representing a hydrogen atom or a linear or branched (Ci-Ce)alkyl group, more particularly the Mo dioxide is of the formula MoO₂[CH₃C(O)CHC(O)CH₃]2;

- molybdenum dioxide;

- blue molybdenums [66771-43-5], a mixture of Mo oxide/Mo(VI) hydroxide and Mo(V) hydroxide; in particular Mo⁶⁺ ₃Mo⁵⁺ ₃OisH, and the derivatives from condensation with phosphate ions;

binary molybdenum 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 [Mo6Hals]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 a chlorine atom;

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

Mo sulphur derivatives chosen from:

- molybdenum disulphides, molybdenum(IV) sulphides, M0S2 and

- molybdenum sesquisulphides; dimolybdenum (III) trisulphides, M02S3; molybdenum porphyrins;

monomeric or polymeric molybdenum carboxylates; such as those of formula n[R-C(O)O^"].n[Mo] in which n represents an integer other than zero and preferentially equal to 2, and R represents an optionally substituted (CrCs) alkyl group; in particular molybdenum acetate dimer; aluminium trihydroxide AI(OH)₃, aluminium oxide hydroxide AIO(OH), aluminium oxide AI2O3, hydrated or anhydrous, alkali metal aluminates such as sodium aluminate NaAIO2_; • aluminium sulphates in particular chosen from hydrated or anhydrous aluminium sulphate AI2O12S3 such as aluminium sulphate octahydrate;

• aluminium carboxylates in particular chosen from basic aluminium acetate C₄H₇O₅AI, aluminium oxalate, hydrated or anhydrous aluminium citrate, such as aluminium citrate hydrate, aluminium lactate and aluminium glycinate;

• aluminium phosphates in particular chosen from aluminium phosphate AIPO₄;

• zinc sulphates;

· zinc halides such as zinc chloride;

• zinc carboxylates such as zinc lactate, zinc acetate, zinc glycinate, zinc gluconate and zinc aspartate;

• calcium hydroxides, calcium sulphates, calcium halides, calcium carboxylates, calcium phosphates, calcium borates, calcium carbonates; · rhodium sulphates such as rhodium +111 sulphate (Rh₂(SO₄)3), rhodium halides such as rhodium +111 chlorides which are hydrated (RhCl32.5H₂O) or anhydrous (RhCb), for instance rhodium chloride trihydrate, rhodium carboxylates such as rhodium +111 acetate.

10. Dyeing process according to any one of the preceding claims, characterized in that the metal derivative(s) f) is (are) chosen from: i) monomeric or polymeric molybdenum carboxylates; such as those of formula n[R-C(O)O^"].n[Mo] in which n represents an integer other than zero and preferentially equal to 2, and R represents an optionally substituted (Ci-Csjalkyl group; the monomeric or polymeric molybdenum carboxylates are particularly molybdenum acetate dimer;

ii) aluminium sulphates such as aluminium sulphate octahydrate;

iii) zinc sulphates such as zinc sulphate heptahydrate;

iv) zinc carboxylates such as zinc acetate or glycinate;

v) calcium carboxylates such as calcium acetate or calcium pyrrol idonecarboxylate; and

vi) rhodium III carboxylates.

1 1 . Process according to any one of the preceding claims, characterized in that the first step consists in applying to said fibres a composition comprising the ingredients a), b) and c) as defined according to any one of Clainns 1 to 6, then, in a second step, a composition comprising the ingredients d) and e) as defined according to any one of Claims 1 , 7 or 8, and then, in a third step, a composition comprising the ingredient f) as defined according to either one of Claims 9 and 10 is applied to said fibres, it being understood that at least one of the three compositions is aqueous.

12. Cosmetic composition for dyeing keratin fibres, containing the compounds a), b), c), d), e) and f) as defined according to any one of Claims 1 to 10.

13. Multicompartment device comprising from 2 to 6 compartments containing from 2 to 6 compositions, in which are distributed ingredients a), b), c), d), e) and f) as defined in any one of Claims 1 to 10, said compositions being aqueous or pulverulent, with at least one of these compositions being aqueous.

14. Use of one or more metal salt(s) as defined in any one of Claims 1 , 9 or 10, for improving the chromaticity and/or the colour uptake of keratin fibres, in particular human keratin fibres such as the hair, dyed using one or more dihydroxyflavonoid, neoflavanol or neoflavanone derivative(s) as defined in any one of Claims 1 to 4.