FR2976798A1 - METHOD FOR HAIR COLORING FROM DIHYDROXYFLAVONOIDES, NEOFLAVANOLS OR NEOFLAVANONES DERIVATIVES, MANGANESE SALTS, HYDROGEN PEROXIDE, (BI) CARBONATES, ALKALI AGENTS, AND METAL SALTS - Google Patents

Abstract

The present invention relates to a method for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, wherein said fibers are treated with one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the following ingredients: a) one or more derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s); (b) one or more manganese salt (s); (c) hydrogen peroxide or one or more hydrogen peroxide generator systems; d) one or more (bi) carbonate (s) or one or more system (s) generating (s) of (bi) carbonate (s); e) one or more basifying agent (s) different from (s) bicarbonate (s); and f) one or more metal salt (s) selected from molybdenum, aluminum, 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, ie greater than 7, metal salt (s) f) is (are) applied in the last step of the coloring process. The process according to the invention has the advantage of coloring human keratin fibers, with stubborn and surprisingly chromatic coloring results with a satisfactory "rise" in the coloration.

Description

PROCESS FOR HAIR COLORING FROM DIHYDROXYFLAVONOIDES, NEOFLAVANOLS OR NEOFLAVANONES DERIVATIVES, MANGANESE SALTS, HYDROGEN PEROXIDE, (BI) CARBONATES, ALKALI AGENTS, AND METALLIC SALTS The present invention relates to a method for coloring keratinous fibers, in particular human keratinous fibers such as the hair, wherein said fibers are treated from one or more cosmetic compositions comprising a) one or more derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s), (b) one or more manganese salt (s), (c) hydrogen peroxide or one or more hydrogen peroxide generator systems, (d) one or more (bi) carbonate (s) or one or more system (s) generating (s) of (bi) carbonate (s), e) one or more agent (s) alkalinizing (s) different (s) carbonate (s) and f) one or more metal salt (s) selected from molybdenum (Mo), aluminum (Al) , zinc (Zn) calcium (Ca) and rhodium (Rh) being understood that the ingredient (s) f) is (are) applied (s) in post-treatment. It is known to obtain so-called "permanent" dyes with dyeing compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained can be varied by combining these oxidation bases with couplers or color 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 bases or a mixture of bases and couplers to the keratinous fibers with hydrogen peroxide (H2O2 or hydrogen peroxide) as an oxidizing agent, to be allowed to diffuse, then to rinse the fibers. The resulting colorations are permanent, powerful, and resistant to external agents, including light, weather, washing, perspiration and friction, However, the commercial hair colorations that contain them generally have the disadvantage of staining clothing, lead to problems of smell and comfort, and degrade keratin fibers. This is particularly the case with oxidation dyes. In the field of coloring, it is also known to color keratin materials such as hair or skin from orthodiphenol compounds in the presence of a metal salt, especially manganese (Mn) and / or zinc (Zn) . In particular, the patent applications FR 2814943, FR 2814945, FR 2814946 and FR 2814947 provide compositions for dyeing the skin or keratinous fibers, comprising a dye precursor which contains orthodiphenols, salts and oxides of Mn and / or or Zn, alkalizing agents of the hydrogencarbonate type in a particular ratio Mn, Zn / hydrogen carbonate and optionally an enzyme. According to these documents, it is possible to obtain dyes of keratin materials with oxygen from the air or any system generating oxygen. However, the colorations obtained are insufficiently intense and are not very chromatic, especially in the case of hair fibers.

Furthermore, it is known to use acid-level metals for dyeing keratinous fibers in amounts similar to those used for dyes by using an etching process, which makes it possible to prepare the fibers in order to obtain stubborn dyes. . However, this process generally has the disadvantage of not always respecting the cosmetics of the keratin fiber. In addition, the metals used, such as iron, lead to neutral and non-chromatic shades. In general, such metals do not make it possible to obtain chromatic nuances. There is therefore a real need to develop staining processes which make it possible to obtain intense, stubborn and / or chromatic colorings from dihydroxyflavonoid derivatives, in particular from natural extracts rich in dihydroxyflavonoid (s), neoflavanol (s). ) or neoflavanone (s), and less aggressive for keratinous fibers. In particular, there is a need to obtain stains which are satisfactorily resistant to external agents (light, bad weather, shampoos) which are stubborn and homogeneous, ie having a low selectivity of the coloring between the root and the tip, while remaining powerful and / or chromatic. This object is achieved by the present invention which relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated, in one or more steps, with one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the following ingredients: a) one or more derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s); (b) one or more manganese salt (s); (c) hydrogen peroxide or one or more hydrogen peroxide generator systems; d) one or more (bi) carbonate (s) or one or more system (s) generating (s) of (bi) carbonate (s); e) one or more basifying agent (s) different from (s) bicarbonate (s); and f) one or more metal salt (s) selected from molybdenum, aluminum, 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, ie greater than 7, and the metal salt (s) f) is (are) applied in post-treatment, ie in the last step of the dyeing process.

Thus, the keratinous fibers are treated at the end of the dyeing process with a composition comprising the salt (s) and the metal salt (s). In particular, the cosmetic composition comprising one or more titanium salt (s) is applied to the keratin fibers in post-treatment. According to a particular embodiment of the dyeing process according to the invention, the compound (s) d) and e) are: - either in mixture with the compounds a), b) and c), - is applied separately after application of a cosmetic composition comprising the compound (s) a), b) and c) - is applied together with the compound c) after application of a cosmetic composition comprising the ingredients a) and b).

According to a particular embodiment of the dyeing process of the invention, the titanium salt or salts are found to be applied separately after the application of ingredients a) to e). The present invention also relates to a cosmetic composition for dyeing keratinous fibers comprising: a) one or more derivative (s) of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s); (b) one or more manganese salt (s); (c) hydrogen peroxide or one or more hydrogen peroxide generator systems; d) one or more (bi) carbonate (s) or one or more system (s) generating (s) of (bi) carbonate (s); e) one or more basifying agent (s) different from (s) bicarbonate (s); and f) one or more metal salt (s) selected from molybdenum, aluminum, zinc, calcium and rhodium salts; it being understood that the pH of the composition is alkaline is greater than 7, and preferably between 8 and 12; especially between 8 and 10.5.

Another object of the present invention is a multi-compartment device comprising: a) one or more derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s); (b) one or more manganese salt (s); (c) hydrogen peroxide or one or more hydrogen peroxide generator systems; d) one or more (bi) carbonate (s) or one or more system (s) generating (s) of (bi) carbonate (s); e) one or more basifying agent (s) different from (s) bicarbonate (s); and f) one or more metal salt (s) selected from molybdenum, aluminum, zinc, calcium and rhodium salts; it being understood that the pH of at least one of the compositions comprising at least one of ingredients a), b), d), e) and / or f) is alkaline, ie greater than 7, and preferably between 8 and 12. Particularly between 8 and 10.5.

The multi-compartment device or "kit" is suitable for carrying out the coloring process according to the invention.

The method according to the invention has the advantage of coloring human keratin fibers, with results of stubborn and surprisingly chromatic colorations. In particular, the dyeing method according to the invention makes it possible to lead to colorings resistant to washing, transpiration, sebum and light without altering the fibers. In addition, the dyeing process used makes it possible to induce a "rise" in the satisfactory coloration.

Another object of the invention is the use of one or more salt (s) chosen from molybdenum, aluminum, zinc, calcium and rhodium salts to improve the chromaticity and / or the increasing the color of the keratinous fibers, in particular human keratinous fibers such as the hair, stained with one or more derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s).

Other objects, features, aspects and advantages of the present invention will become more apparent upon reading the description and examples which follow. a) derivatives of dihydroxyflavonoids, neoflavanols or neoflavanones

According to a particular embodiment of the invention, the method for dyeing keratin fibers or the composition uses or contains as ingredient a) one or more dihydroxyflavonoid derivatives or the mixture derived from dihydroxyflavonoids. By dihydroxyflvonoids is meant a compound comprising at least two benzene rings A and B connected by a closed three-carbon chain to a 6-membered C-heterocycle comprising an oxygen atom, and of which at least one of the two benzene rings A or B comprises at least two hydroxy groups (OH) carried by two adjacent carbon atoms (in ortho) of said benzene ring.

The flavone structures, flavonols, dihydroflavonols and flavanonols, flavanones, flavan-3-ols, flavan-3,4-diols and anthocyanidols, their salified forms, their aglycone forms (without bound sugars) may be cited as such. as well as their heteroside forms, their methoxylated derivatives, and the corresponding oligomers, as described in "Bruneton, J., Pharmacognosie - Phytochimie, medicinal plants, 4th ed., revised and expanded, Paris, Tec & Doc - International Medical Editions , 2009, 1288 p. And in "P. Sarni-Manchado, V. Cheynier, polyphenols in food, Lavoisier, Editions Tec & Doc, 2006, 398 p", including natural flavonoids, including flavonoids derived from animal extracts, bacteria , mushrooms, seaweed, plants and fruits.

More particularly the dihydroxyflavonoid derivatives a) represent compounds of formula (1) as well as their salts of organic or mineral acid, its optical isomers, geometric, tautomers and their solvates such as hydrates: R13 R14 R12 formula (1) in which : - - represents a single bond or a double bond; - R1 R2, R3, R4, R1 °, R11 R12R13 and R14, identical or different, represent: - a hydrogen atom, - a halogen atom, - a hydroxy group, - a (C1-C6) alkyl group a (C1-C6) alkoxy group, a (C1-C6) alkylthio group, a carboxyl group, an alkyl or alkoxycarbonyl carboxylate group, an optionally substituted amino group, a linear or branched alkenyl group; optionally substituted, - an optionally substituted cycloalkyl group, R11 (I) 6 - an aryl group, - a substituted aryl group, - a group containing one or more silicon atoms - a (di) ((hydroxy) (C1-C6) ) alkyl) amino, -O-sugar group such as -O-glucoside, -RZC (X) -Y- group with R representing a hydrogen atom, or a group (C1-COalkyl, Y and Z, identical or different, represent a bond, or an oxygen atom, sulfur or a group -N (R ') - with R' representing a hydrogen atom or a group (C1-COalkyl, Y may also represent Senter a (C1-COalkylène; X representing an oxygen atom, sulfur, or NR "with R" representing a hydrogen atom or a group (C1-COalkyl) - R5, R6, R ', R5 and R9, identical or different, represent an atom hydrogen, or a group selected from hydroxy or (C1-COalkyl); or alternatively R5 with R6 and / or R 'together with R5 together with the carbon atom which carry them an oxo group; - or else R5 and R9 together form a bond, it being understood that: - at least two radicals chosen from R1, R2, R3, R4, R10, R11, R12R13 and R13, which are contiguous, represent a hydroxyl group: - when R5 with R6 and / or R 'with R5 form together an oxo group, or R5 with R9 together form a bond, then - represent a single bond - when - carried by the oxygen atom is a double bond, then the compound of formula (1) is cationic and it is associated anionic counterion.

The dihydroxyflavonoid derivatives useful in the process of the invention may be natural or synthetic. Among the natural dihydroxyflavonoid derivatives are compounds which may be present in nature and which are reproduced by chemical (hemi) synthesis. The salts of the dihydroxyflavonoid derivatives of the invention may be salts of acids or bases. The acids can be mineral or organic. Preferably the acid is hydrochloric acid which leads to chlorides. The bases can be mineral or organic. Especially the bases are alkali hydroxides such as sodium hydroxide which leads to sodium salts. More particularly, the dihydroxyflavonoids which can 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 tannins, such as theaflavin, theaflavin 3'-O-gallate, 3,3'-O-digallate theaflavin, A1, A2, B1, B2, B3 and Cl proanthocyanidins.

Flavan-3-ol 10 - ii) dihydroxyflavonols such as quercetin, myricetol, fisetine, their glycosides, their methoxylated derivatives such as rhamnetine. iii) dihydroxyflavones such as luteolin, their glycosides, such as luteolol 7-O-glucoside, baicalin and orientine. - iv) dihydroxydihydroflavonols or dihydroxyflavanonols such as dihydroquercetol, their glycosides such as dihydroquercetol 3-O-rhamoside - v) dihydroxyflavanones such as eriodictyol. O 3-hydroxy-2-phenylchromen-4-one Flavonol O 2 -phenylchromen-4-one Flavone O 3-hydroxy-2,3-dihydro-2-phenylchromen-4-one Dihydroflavonol or Flavanonol - vi) Dihydroxyflavan-3 , 4-diols or dihydroxyleucoanthocyanidines such as leucocyanidol (= procyanidol). O-2,3-dihydro-2-phenylchromen-4-one Flavanone Flavan-3,4-diol (vii) dihydroxyanthocyanidols (or dihydroxyanthocyanidines) constructed on the flavylium cation such as cyanidol, delphinidine, aurantinidine, luteolinidine, their glycosides such as dihydroxyanthocyananes (or dihydroxyanthocyanosides, or anthocyanins on the English model), their oligomers and polymers such as proanthocyanins. According to another particular embodiment of the invention, the method for dyeing keratinous fibers or the composition uses or contains as ingredient a) one or more derivatives of neoflavanols or neoflavanones or their mixtures; preferentially derived from neoflavanols.

More particularly neoflavanols and neoflavanones are of formula (II) and (III) and their tautomeric forms, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, as well as hydrates; Cation flavylium Anthocyanidol or Anthocyanidine formulas (II) and (III) in which: - represents a conjugated single or double carbon - carbon bond, - X represents a group: // / HO-C or O = C \ \ - R ', R2, R3, R4, R5 and R6, identical or different, represent an atom

hydrogen, a hydroxy group, an optionally substituted alkyl group, optionally substituted alkoxy, or an optionally substituted acyloxy group.

The compounds of formula (II) as defined above can be in two tautomeric forms noted (Ila) and (Ilb): The alkyl radicals are hydrocarbon radicals, saturated, linear or branched, generally C1- C 20, especially C 1 -C 10, preferably C 1 -C 6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkoxy radicals are alkyl-oxy radicals with alkyl as defined above, in general the C1-C10 alkoxy radicals, such as methoxy, ethoxy, propoxy and butoxy. The alkoxyalkyl radicals are preferably (C1-C20) alkoxy (C1-C20) alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, and the like. The alkyl or alkoxy radicals, when they are optionally substituted, may be substituted by at least one substituent carried by at least one carbon atom, chosen from: a halogen atom; a hydroxyl group; a C 1 -C 2 alkoxy radical; a C1-C10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted by a (C1-C4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a hydroxyl group, an amino group optionally substituted with one or two C 1 -C 3 alkyl radicals optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom which may or may not be different from nitrogen, a quaternary ammonium group -N + R'R "R" ', M- for which R', R ", R" ', which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group; and M- represents the counter-ion of the organic acid, mineral or of the corresponding halide, or a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical; preferentially methyl; an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is an alkyl radical; C, -C2; a carbamoyl radical ((R) 2NCO-) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'SO 2 -NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R 'radical represents an alkyl radical in C1-C4, a phenyl radical; an aminosulphonyl radical ((R) 2 N -SO 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group, - a radical carboxylic acid in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); a cyano group; a nitro group; a carboxy or glycosylcarbonyl group; a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; a glycosyloxy group; and a phenyl group optionally substituted by one or more hydroxyl groups. By glycosyl radical is meant a radical derived from a mono or polysaccharide.

According to a particular embodiment of the invention, the compounds of formula (II) or (III) comprise an R 6 radical which represents a hydroxyl group.

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

More particularly, the process for dyeing keratin fibers uses as ingredient a) one or more compounds chosen from the natural compounds of hematoxylin, haematein, brazilin and braziléine.

Among the hematoxylin / haematein and brazilin / braziline compounds, mention may be made, by way of example, of hematoxylin (Natural Black 1) and braziline (Natural Red 24), compounds of the family of indochromanes, which are accessible in the trade. These last 25 can exist in an oxidized form and can be obtained by synthesis routes or extraction routes of plants or plants known to be rich in these compounds. ## STR1 ## Hematéine (oxidized form) belonging to Braziléine (oxidized form) belonging to formula (II) (family: neoflavone) formula (II) (family: neoflavanol) HO HO HO HO OH HO OO HO HO Hematoxylin (Natural Black 1 - Braziline (Natural Red 24 - CAS 517-28-2) belonging to the formula (III) CAS 474-07-7) belonging to the formula (III) (family: neoflavanol) (family: neoflavanol) The compounds of formula (II) and (III) can be used in the form of extracts. The following plant extracts (genus and species) may be used: Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis. The extracts are obtained by extraction of various parts of plants such as, for example, the root, the wood, the bark, the leaf. According to one embodiment, the hematoxylin / hamein and natural brazilin / braziléine compounds are derived from the woods. Preferably, the compound (s) of formula (II) or (III) of the invention are derived from plant extracts. Particularly ingredient a) is at least 80% by weight based on the total weight of ingredients b), c), d), e) and f). It is also possible to use mixtures of plant extracts.

The natural extracts according to the invention can be in the form of powders or liquids. The extracts of the invention are preferably in the form of powders. According to the invention, the compound (s) of formula (II) and (III), synthetic (s), natural (s), such as the compounds of hematoxylin / hamein and brazilin / braziléine and / or the or the natural extract (s) used as ingredient (a) in one or more compositions (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 formula (II) and (III), such as the haematoxylin / haematin and brazilin / braziléine compounds or the extract (s).

With regard to pure compounds of formula (II) and (III) such as the compounds of hematoxylin / hamein and braziline / braziléine, the content in the composition or compositions containing them is preferably between 0.001 and 5%. by weight of each of these compositions. With regard to the extracts, the content in the composition or compositions containing the extracts as such 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 dihydroxyflavonoid derivative (s), neoflavanol (s) or neoflavanone (s), synthetic (s) which do not exist in nature. According to another preferred embodiment of the invention, the composition that is useful in the process for dyeing keratinous fibers comprises as ingredient a) one or more dihydroxyflavonoid derivative (s), neoflavanol (s) or neoflavanone (s), natural (s). The compounds of formula (1), (II) or (III) useful in the process of the invention may be natural or synthetic. Among the natural compounds are included compounds that are present in nature and that can be reproduced by chemical synthesis. The salts of the compounds of formula (1), (II) or (III) of the invention may be cosmetically acceptable salts of acids or bases. The acids can be mineral or organic. Preferably the acid is hydrochloric acid which leads to chlorides.

The bases can be mineral or organic. Especially the bases are alkali hydroxides such as sodium hydroxide which leads to sodium salts. The compounds a) are preferably chosen from catechin and hematoxylin.

When the dye precursors have D and L forms, both forms can be used in the compositions according to the invention, as well as the racemates. According to one embodiment, the derivatives of dihydroxyflavonoids, neoflavanols or natural neoflavanones are derived from extracts of animals, bacteria, fungi, algae, plants and fruits used in their entirety or partially.

In particular concerning the plants the extracts are from fruits including citrus fruits, vegetables, trees, shrubs. It is also possible to use mixtures of these extracts, rich in dihydroxyflavonoid derivatives as defined above. Preferably the dihydroxyflavonoid derivative (s), neoflavanols or natural neoflavanones of the invention are derived from plant extracts or parts of plants. Within the meaning of the invention, these extracts will be assimilated as compounds a). The extracts are obtained by extraction of various parts of plants such as for example root, wood, bark, leaf, flower, fruit, seed, pod, peel.

Among the plant extracts, there may be mentioned the extracts of tea leaves, rose. Among the fruit extracts, mention may be made of extracts of apple, grapes (in particular grape seeds), or extracts of beans and / or pods of cocoa. Among the vegetable extracts, there may be mentioned potato extracts, onion peels.

Among the extracts of wood of trees, one can quote the extracts of bark of pine, extracts of logwood. It is also possible to use mixtures of plant extracts.

According to one particular embodiment of the invention, the dihydroxyflavonoids derivative (s), neoflavanols or neoflavanones are natural extracts rich in dihydroxyflavonoids, neoflavanols or neoflavanones. According to a preferred mode, the dihydroxyflavonoid derivative (s) are only natural extracts. The natural extracts according to the invention can be in the form of powders or liquids. The extracts of the invention are preferably in the form of powders. According to the invention, the derivative (s) dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s), synthetic (s), natural (s), and / or the natural extract (s) (s) ) used as ingredient a) in one or more composition (s) useful in the process according to the invention preferably represents from 0.001% to 20% by weight of the total weight of the composition (s). compositions containing the dihydroxyflavonoid (s) or extract (s). As regards the derivatives of dihydroxyflavonoids, neoflavanols or pure neoflavanones, the content in the composition or compositions containing them is preferably between 0.001 and 5% by weight of each of these compositions.

With regard to the extracts, the content in the composition or compositions containing the extracts as such is preferably between 0.5 and 20% by weight of each of these compositions.

Additional orthodip derivative According to a particular embodiment of the invention, the dyeing process may use one or more ortho-diphenol derivative (s) different from the dihydroxyflavonoid derivative (s). (s), neoflavanol (s) or neoflavanone (s). The derivative (s) of orthodiphenol (s) may be present in one or more cosmetic compositions used during the dyeing process. A particular embodiment of the invention relates to derivatives of orthodiphenols or mixtures of compounds comprising one or more aromatic rings, preferably a benzene ring, comprising at least two hydroxy groups (OH) borne by two adjacent carbon atoms of the aromatic ring.

The aromatic ring may be more particularly a fused aryl or fused heteroaromatic ring, optionally containing one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, and the like. isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring having at least two hydroxy groups carried by two adjacent carbon atoms of the aromatic ring. Preferably, the aromatic ring of orthodiphenol derivatives according to the invention is a benzene ring. By condensed ring is meant that at least two saturated or unsaturated cycles, heterocyclic or not, have a common bond, that is to say that at least one cycle is attached to another cycle. Orthodiphenols according to the invention may be salified or not. They can also be in the form of aglygone (without bound sugar) or in the form of glycosylated compounds.

More particularly, the orthodiphenol derivative is different from the dihydroxyflavonoid derivatives and is of formula (IV), or one of these oligomers, in salified form or not: formula (IV) in which the substituents: carboxyl, carboxylate and alkyl or alkoxycarbonyl, optionally substituted amino, optionally substituted linear or branched alkyl, optionally substituted linear or branched alkenyl, optionally substituted cycloalkyl, alkoxy, alkoxyalkyl, alkoxyaryl, the optionally substituted aryl group, aryl, substituted aryl, a heterocyclic radical. saturated or unsaturated, with or without a cationic or anionic charge, optionally substituted and / or optionally fused with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted especially by one or more hydroxyl or glycosyloxy groups, radical containing one or more silicas R 1, R, R 4, which may be identical or different, represent: a hydrogen atom, a halogen atom, a a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-an-a hydroxy radical, radical radical radical radical radical radical radical radical radical Radical radical - where two of the substituents carried by two adjacent carbon atoms R, - R2, R2 - R3 or R3 - R4 together with the carbon atoms carrying them a saturated ring or unsaturated, aromatic or otherwise, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. Especially, R, R4 together form one to four cycles. A particular embodiment of the invention relates to orthodiphenol derivatives of formula (IV) in which two adjacent substituents R 1 -R 2, R 2 -R 3 or R 3 -R 4 can not form, with the carbon atoms which carry them, a pyrrolyl radical. . More particularly, R2 and R3 can not form a pyrrolyl radical fused to the benzene ring carrying the two hydroxy. The saturated or unsaturated cycles, optionally condensed, may also be optionally substituted.

The alkyl radicals are hydrocarbon radicals, saturated, linear or branched, generally C 1 -C 20, particularly C 1 -C 10, preferably C 1 -C 6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkenyl radicals are hydrocarbon radicals, linear or branched, unsaturated C2-C20; preferably comprising at least one double bond such as ethylene, propylene, butylene, pentylene, methyl-2-propylene and decylene. The aryl radicals are mono or polycyclic carbon radicals, condensed or not, preferably comprising from 6 to 30 carbon atoms and of which at least one ring is aromatic; preferably chosen from the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, and tetrahydronaphthyl. The alkoxy radicals are alkyl-oxy radicals with alkyl as defined above, preferably C1-C10, such as methoxy, ethoxy, propoxy and butoxy. The alkoxyalkyl radicals are preferably the (C1-C20) alkoxy (C1-C20) alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, and the like.

The cycloalkyl radicals are in general the C 4 -C 8 cycloalkyl radicals, preferably the cyclopentyl and cyclohexyl radicals. The cycloalkyl radicals may be substituted cycloalkyl radicals, in particular with alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups. The alkyl or alkenyl radicals, when they are optionally substituted, may be substituted with at least one substituent carried by at least one carbon atom, chosen from: a halogen atom; a hydroxyl group; a C 1 -C 2 alkoxy radical; a C1-C10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least one hydroxyl group, an amino group optionally substituted with one or two optionally substituted C 1 -C 3 alkyl radicals; , said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered saturated or unsaturated heterocycle optionally comprising at least one other non-nitrogen heteroatom or another, an ammonium group; quaternary group -N + R'R "R" ', M- for which R', R ", R" ', which may be identical or different, represent a hydrogen atom, or a C 1 -C 4 alkyl group; and M- represents the counterion of the corresponding organic acid, mineral acid or halide, or a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferentially methyl; an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is an alkyl radical; C, -C2; a carbamoyl radical ((R) 2 N-CO-) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'SO 2 -NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R 'radical represents an alkyl radical in C1-C4, a phenyl radical; an aminosulphonyl radical ((R) 2 N -SO 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); a cyano group; a nitro group; a carboxy or glycosylcarbonyl group; a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; a glycosyloxy group; and a phenyl group optionally substituted by 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 carried by at least one carbon atom, chosen from: a C 1 -C 6 alkyl radical; preferably C1-C8, optionally substituted by one or more radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) poly (C 2 -C 4) -alkyl-hydroxyalkyl, amino substituted by two identical or different alkyl radicals, , C1-C4, optionally carrying at least one hydroxyl group or, the two radicals may form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 members, preferably 5 or 6 members optionally substituted, saturated or unsaturated optionally comprising another heteroatom identical to or different from nitrogen; a halogen atom; a hydroxyl group; a C 1 -C 2 alkoxy radical; a C 1 -C 10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least one hydroxyl group, an amino group optionally substituted with one or two C 1 -C 3 alkyl radicals; optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocycle comprising saturated or unsaturated optionally comprising at least one other heteroatom different or different from nitrogen, a quaternary ammonium group -N + R'R "R" ', M- for which R', R ", R" ', which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group; and M- represents the counter-ion of the organic acid, mineral or of the corresponding halide, or a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical; preferentially methyl; an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a C 1 -C alkyl radical; , -C2; a carbamoyl radical ((R) 2 N-CO-) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'SO 2 -NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R 'radical represents an alkyl radical in C1-C4, a phenyl radical; an aminosulphonyl radical ((R) 2 N -SO 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group, - a radical carboxylic acid in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); a cyano group; a nitro group; a polyhaloalkyl group, preferentially trifluoromethyl; a carboxy or glycosylcarbonyl group; a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; a glycosyloxy group; and a phenyl group optionally substituted by one or more hydroxyl groups. By glycosyl radical is meant in the sense of the present invention a radical derived from a mono or polysaccharide.

The radicals containing one or more silicon atoms are preferably poly-dimethylsiloxane, poly-diphenylsiloxane, poly-dimethylphenylsiloxane, stearoxydimethicone radicals. The heterocyclic radicals are, in general, radicals comprising in at least one ring one or more heteroatoms chosen from O, N and S, preferably O or N, optionally substituted with in particular one or more alkyl, alkoxy, carboxylic acid, hydroxyl or amine groups. or ketone. These rings may contain one or more oxo groups on the carbon atoms of the heterocycle. Among the heterocyclic radicals that can 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, chromannyl, isochromannyl, indolinyl, isoindolinyl, coumarinyl, isocoumarinyl, these groups may be substituted, in particular by one or more OH groups. Orthodiphenols useful in the process of the invention may be natural or synthetic. Natural orthodiphenols include compounds that may be present in nature and are reproduced by (hemi) chemical synthesis. The salts of the orthodiphenols of the invention may be salts of acids or bases. The acids can be mineral or organic. Preferably, the acid is hydrochloric acid which leads to chlorides. The bases can be mineral or organic. Especially the bases are alkali hydroxides such as sodium hydroxide which leads to sodium salts. According to a particular embodiment of the invention, the composition comprises as ingredient a) one or more synthetic orthodiphenol derivative (s) which do not exist in nature. According to another preferred embodiment of the invention, the composition that is useful in the keratinous fiber coloring process comprises as ingredient a) one or more natural orthodiphenol derivative (s).

More particularly, the orthodiphenols that can be used in the process of the invention according to a) are in particular: anthocyanidins such as cyanidine, delphinidin, petunidine, anthocyanins or anthocyanins such as myrtillin, orthohydroxybenzoates, for example the salts of gallic acid, hydroxystilbenes, for example tetrahydroxy-3,3 ', 4,5'-stilbene, optionally oxylated (for example glucosylated), 3,4-dihydroxyphenylalanine and its derivatives, 3-dihydroxyphenylalanine and its derivatives, - 4,5-dihydroxyphenylalanine and its derivatives, - dihydroxycinnamates such as caffeic acid and chlorogenic acid, - orthopolyhydroxycoumarines, - orthopolyhydroxyisocoumarines, - orthopolyhydroxycoumarones, - orthopolyhydroxyisocoumarones, - orthopolyhydroxychalcones, - orthopolyhydroxychromones, - quinones, - hydroxyxanthones, - 1,2 dihydroxybenzene and its derivatives, - 1,2,4 trihydroxybenz ene and its derivatives, 1,2,3-trihydroxybenzene and its derivatives, 2,4,5-trihydroxytoluene and its derivatives, proanthocyanidines and especially proanthocyanidines A1, A2, B1, B2, B3 and C1, proathocyanines, - tannic acid, - ellagic acid, - and mixtures of the above compounds.

When the dye precursors have D and L forms, both forms can be used in the compositions according to the invention, as well as the racemates. According to one embodiment, natural orthodiphenols are derived from extracts of animals, bacteria, fungi, algae, plants and fruits used in whole or in part. In particular concerning the plants the extracts are from fruits including citrus fruits, vegetables, trees, shrubs. It is also possible to use mixtures of these extracts, rich in ortho-diphenols as defined above. Preferably, the natural orthodiphenol (s) of the invention are derived from extracts of plants or parts of plants. Within the meaning of the invention, these extracts will be assimilated as additional orthodiphenols. The extracts are obtained by extraction of various parts of plants such as for example root, wood, bark, leaf, flower, fruit, seed, pod, peel. Among the plant extracts, there may be mentioned the extracts of tea leaves, rose. Among the fruit extracts, mention may be made of extracts of apple, grapes (in particular grape seeds), or extracts of beans and / or pods of cocoa. Among the vegetable extracts, there may be mentioned potato extracts, onion peels. Among the extracts of wood of trees, mention may be made of pine bark extracts. It is also possible to use mixtures of plant extracts. According to a particular embodiment of the invention, the orthodiphenol derivative (s) are natural extracts rich in orthodiphenols. According to a preferred embodiment, the orthodiphenol derivative (s) are only natural extracts. Preferably, the ortho-diphenol (s) according to the invention are chosen from gallic acid, and the natural extracts the containers chosen from grape pomace, pine bark, green tea, onion, cocoa bean, red wood and walnut.

The natural extracts according to the invention can 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 orthodiphenol derivative (s), natural (s), and / or the natural extract (s) used as an ingredient (a) in one or more cosmetic 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 orthodiphenols or the extract (s). As regards pure orthodiphenols, the content in the composition or compositions containing them is preferably between 0.001 and 5% by weight of each of these compositions. With regard to the extracts, the content in the composition or compositions containing the extracts as such 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 salts (Mn). 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 the salts themselves, 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 salts of carboxylic acids and polymeric salts and mixtures thereof. More particularly, the manganese salt is different from manganese carbonate, manganese hydrogencarbonate or manganese dihydrogen carbonate.

The carboxylic acid salts useful in the invention also include hydroxylated carboxylic acid salts such as gluconate. By way of example of polymeric 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 sulfate monohydrate and manganese gluconate. The salts used advantageously are manganese gluconate and manganese chloride.

The manganese salts may be introduced in solid form in the compositions or may come from natural water, mineral or thermal, rich in these ions or seawater (dead sea in particular). They can also come from mineral compounds such as earths, ochres such as clays (green clay for example) or even plant extract containing them (see for example patent document FR 2,814,943). According to a preferred embodiment of the invention, the manganese salt or salts used represent from 0.001% to approximately 1% by weight of the total weight of the composition (s) containing the metal salt (s) and even more preferably from From about 0.05% to about 10% by weight. In particular, the metal salts b) of the invention are of oxidation levels 2 such as Mn (II). Even more preferably, the manganese salt or salts are chosen from carboxylic acid salts of manganese, in particular manganese gluconate, and manganese halides, such as manganese chloride.

(c) Hydrogen peroxide or hydrogenator peroxide generator system

In the context of the present invention, the third constituent is hydrogen peroxide or a system for generating hydrogen peroxide such as: a) urea peroxide; b) polymeric complexes which can release hydrogen peroxide such as polyvinylpyrrolidone / 1-12O2 in particular being in the form of powders and other polymer complexes described in US 5,008,093; US 3,376,110; US 5,183,901; c) oxidases producing 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 generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; perborates; or e) percarborates.

According to a preferred embodiment of the invention, the composition contains one or more hydrogen peroxide generator system (s) chosen from a) urea peroxide, b) polymeric complexes which can release hydrogen peroxide selected from polyvinylpyrrolidone / 1-12O2; c) oxidases; e) perborates and f) percarborates. In particular, the third component is hydrogen peroxide.

Furthermore, the composition or compositions comprising hydrogen peroxide or the hydrogen peroxide generator may or may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined below.

According to one particular embodiment of the invention, the hydrogen peroxide or hydrogen peroxide generator system (s) used is preferably from 0.001% to 12% by weight of hydrogen peroxide per relative to the total weight of the composition or compositions containing them or, more preferably, from 0.2% to 2.7% by weight. (d) (bi) carbonate (s) or system that binds (bi) carbonate (s)

According to the present invention, the dyeing process uses one or more (bi) carbonates or one or more systems generating (bi) carbonates. By "Ocarbonate generating system" is meant a system that generates in situ the (bi) carbonate such as for example carbon dioxide in water or by dabbing carbonate with a mineral or organic acid. ) carbonates or the (bi) carbonate-generating system (s) may be used in one or more cosmetic compositions during the coloring process The one or more (bi) carbonates is or are selected from: - the alkali metal carbonates (Met2 +, CO32-), alkaline earth metal (Met2 +, CO32-), ammonium ((R "4N +) 2, CO32-) or phosphonium (R" 4P +) 2, CO32-with Met representing an alkaline earth metal and Met representing an alkali metal, and R ", which may be identical or different, represent a hydrogen atom, an optionally substituted (C 1 -C 4 alkyl) group, such as hydroxyethyl, or bicarbonates, also known as hydrogenocarbonates. , of the following formulas: R '+, HCO3 with R' representing an atom hydrogen, an alkali metal, an ammonium group R "4N + - or phosphonium R" 4P + - where R ", which may be identical or different, represent a hydrogen atom, an optionally substituted (C 1 -C 6 -alkyl) group such as hydroxyethyl and when R 'represents a hydrogen atom, the hydrogencarbonate is then called dihydrogen carbonate (CO2, H2O); and Met'2 + (HCO3-) 2 with Met 'representing an alkaline earth metal.

More particularly, the (bi) carbonate is (are) chosen from alkali metal, alkaline earth metal or ammonium (bi) carbonates; preferentially the (bi) carbonates of alkali metals or of ammonium. There may be mentioned carbonates or hydrogenocarbonates of Na, K, Mg, Ca and their mixtures, and in particular Na hydrogen carbonate. These hydrogencarbonates can come from natural water, for example spring water from the Vichy basin, from La Roche Posay, Badoit water (see patent, for example FR 2 814 943). Particularly mention may be made of sodium carbonate [497-19-8] = Na2CO3, sodium hydrogencarbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2. According to the invention, the (bi) carbonate agent (s) used represent, preferably, 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 by 0.005%. at 5% by weight.

Preferably, the (bi) carbonate used in the coloring process of the composition is ammonium (bi) carbonate or sodium bicarbonate (paragraph added according to the examples).

e) alkaliizing agent (s) different from the bicarbonate (s) The alkalinizing agent used in the dyeing process according to the invention as the fifth ingredient is different from the one or more ) carbonates e) as defined above. It is an agent for increasing the pH of the composition or compositions in which it is found. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. In particular, said agent is chosen from: i) ammonia, ii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iii) oxyethylenated and / or oxypropylenated ethylenediamines, iv) mineral or organic hydroxides, v ) alkali metal silicates such as sodium metasilicates, vi) basic amino acids such as arginine, lysine, ornithine, citroline and hystidine, and vii) compounds of formula (V) following: RR a \, b NWN i \ R ~ Rd (V) Formula (V) in which: - W is a divalent group (C, -C $) alkylene, preferably propylene, optionally substituted in particular with a hydroxyl group or a C 1 -C 4 alkyl radical; - Ra, Rb, Rc and Rd, identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl radical. The inorganic or organic hydroxides, particularly the inorganic or organic hydroxides, are preferably chosen from i) the hydroxides of an alkali metal, ii) the hydroxides of an alkaline earth metal, such as hydroxides of sodium or potassium, iii) hydroxides of a transition metal, such as hydroxides of metals of groups III, IV, V and VI, iv) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide. Preferably, for the composition according to the invention or the process used in the invention, the basifying agent is not sodium hydroxide NaOH. More generally, and preferably for the composition according to the invention or the method used in the invention, the basifying agent is not an alkali metal hydroxide XOH with X = alkali metal. The hydroxide may be formed in situ such as, for example, guanidine hydroxide by reaction of calcium hydroxide and guanidine carbonate. The alkalinizing agent (s) e) as defined above preferably represent from 0.001% to 10% by weight of the weight of the composition or compositions containing them. More particularly from 0.005% to 8% by weight of the composition. Preferably, the alkaline agent (s) are chosen from alkanolamines, in particular monoethanolamine.

f) salts of molybdenum (Mo), aluminum (Al), zinc (Zn), calcium (Ca) and rhodium (Rh) The process of the invention comprises one or more salts of Mo, Al, Zn , Ce or Rh. "Metal salt" is understood to mean the oxides of this metal and the salts themselves, especially those resulting from the action of an acid on a metal. The salts are preferably not oxides. Among the salts, mention may be made of halides such as chlorides, fluorides and iodides; sulphates, phosphates; nitrates and salts of carboxylic acids and polymeric salts and mixtures thereof. The carboxylic acid salts useful in the invention also include hydroxylated carboxylic acid salts such as gluconate.

According to a particular embodiment of the invention, the metal derivative (s) f) is (are) molybdenum (Mo). Especially metal derivatives of oxidation number (II) to (VI) and are as described in Kirk-Othmer Encyclopedia of Chemical Technology Copyright © 2001 John Wiley & Sons, Inc. Last updated: 17 Sep 2009, "Molybdenium 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. oxides of Mo such that: the oxides of Mo (IV) to ligand / i-diketones M002L2 with L ligand, identical or different, preferably identical represent a / i-diketone of type RC (X) -C (R ') -C (X) R "with R and R", which may be identical or different, represent a linear or branched (C 1 -C 6) alkyl group and R 'represents a hydrogen atom or a group (C 1 -C 6) alkyl, linear or branched, X represents an oxygen atom, sulfur or a group N (R) with R representing a hydrogen atom or a group (C, -C 6) alkyl, linear or branched, more particularly the dioxide Mo is MoO2 [CH3C (O) CHC (O) CH3] 2 [17524-05-9]; - molybdenum dioxide; - dihalo-dioxomolybdenum (Hal) 2MoO2 with identical or different Hal is as defined above, especially Hal are identical and represent a chlorine atom; blue molybdenum or "molybdenum blues" [66771-43-5], a mixture of Mo oxide / hydroxides of Mo (VI) and Mo (V) as described in Article V. K. Rudenko, Koord. Khim. (1979) 307; (Sov, J. Coord Chem (Engl Transi) 5 (1979) 231, especially Mo6 + 3 Mo5 + 3 O1 $ H, and the condensation derivatives with phosphate ions, ii the halides of Mo binary oxidation states (II) to (VI), hexacoordinated by 6 halogens of Mo (V), (IV) and (III), the Mo atoms being linked by halogen bonds such as the halogenide of Mo (II) containing clusters [Mo6Hal $] 4+ linked to halogen atoms to give Mo61-1al12 with Hal, identical or different, as defined above and more particularly Hal represents Cl, 4Mo molybdenum tetrahalides (Hal) with Hal ', identical or different, as defined previously, such as MoCl4; iv sulfur-containing derivatives of Mo selected from: - Molybdenum disulfides [1317-33-5], molybdenum sulphides (IV), MoS2 - the sesquisulphide of Mo [12033-33-9], trisulphides of dimolybdenum (III), Mo2S3, v. porphyrins of Mo 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. mono or polymeric molybdenum carboxylates; as those of formula n [R-C (O) O -] n [Mo] in which n represents an integer different from zero and preferably equal to 2, and R represents an optionally substituted (C 1 -C 6) alkyl group; the mono or polymeric molybdenum carboxylates are particularly dimeric molybdenum acetate [14221-06-8]. Preferably, the metal derivatives are chosen from Mo carboxylates and more particularly dimeric molybdenum acetate.

In a preferred embodiment of the invention, the mass quantity of molybdenum is the same as the mass of dyes.

According to a particular embodiment of the invention, the metal derivative (s) f) is (are) chosen from aluminum salts and aluminum oxides and their hydrates and their forms. supported. By way of example, mention may be made of oxides, hydroxides, sulphates, halides, carboxylates and aluminum phosphates, such as those described in Ullmann's encyclopedia "Aluminum oxide", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002 / 14356007.a06 139, pp. 1-40. In particular, the aluminum hydroxide (s) and oxide (s) are (are) chosen from aluminum trihydroxide (Al) (OH) 3, aluminum oxide hydroxide A10 (OH), and Al2O3 aluminum oxide hydrated or unhydrated, the alkali metal aluminates such as sodium aluminate NaAlO 2 [1302-42-7].

In particular, the aluminum sulphates are chosen from hydrated or unhydrated aluminum sulphate Al 2 O 12 S 3, such as aluminum sulphate octahydrate. Particularly the aluminum carboxylates are selected from basic aluminum acetate C41-17O5AI [142-03-0], aluminum oxalate, hydrated or unhydrated aluminum citrate such as aluminum citrate hydrated [31142-56-0], aluminum lactate, aluminum glycinate. Especially the aluminum phosphates are chosen from aluminum phosphate AIPO4 [7784-30-7]. Preferably, the metal derivative is chosen from aluminum sulfate octahydrate, basic aluminum acetate C41-17O5AI [142-03-0], aluminum oxalate, hydrated aluminum citrate [31142-56 -0], aluminum lactate, aluminum glycinate, aluminum phosphate AIPO4 [7784-30-7]. In a preferred embodiment of the invention, the quantity by weight of aluminum is the same is the same as the mass of dyes According to a particular embodiment of the invention, the metal derivative (s) f) is (are) chosen from zinc salts and their hydrates and their supported forms different from the zinc salts according to b) as defined above. Preferably Zinc is in the oxidation state of II or Zn II. Among the zinc salts, mention may be made of zinc sulphates; zinc halides such as zinc chloride; zinc carboxylates such as zinc lactate, zinc acetate, zinc glycinate, zinc gluconate, and zinc aspartate. Preferentially zinc sulphate, zinc gluconate, zinc acetate, zinc glycinate. In a preferred embodiment of the invention, the mass quantity of zinc is identical to that of the dyes.

According to a particular embodiment of the invention, the metal derivative (s) f) is (are) chosen from calcium salts and their hydrates and their supported forms. By way of example, mention may be made of hydroxides, sulphates, halides, carboxylates, phosphates, borates and carbonates. Especially the hydroxides are calcium hydroxide Ca (OH) 2. According to one advantageous variant, the calcium salts are calcium sulphates, in particular those chosen from calcium sulphate CaSO.sub.4 and gypsum. According to another variant, the calcium salts are calcium halides, chosen in particular from calcium chloride, calcium bromide and calcium iodide. According to yet another variant of the invention, the calcium salts are calcium carboxylates chosen in particular from calcium oxalate, calcium diacetate, calcium citrate, 2-hydroxypropanoate-1,2,3-tricarboxylate and tricalcium [813-94-5], calcium lactate, calcium 2-hydroxypropanoate, hydrated or unhydrated calcium gluconate, calcium ascorbate, calcium 2-ethylbutanolate, calcium formate, levulinate of calcium, calcium mesoxalate, calcium oleate, calcium palmitate, calcium propionate, calcium saccharate, calcium stearate, calcium stearyl-2-lactylate, calcium succinate, tartrate of calcium, and calcium pyrrolidonecarboxylate. According to another particular embodiment of the invention, the calcium salts are calcium phosphates chosen in particular from calcium phosphate Ca3 (PO4) 2, calcium hydrogen phosphate CaHPO4 hydrated or not hydrated, calcium hydroxyphosphate [Ca5 ( OH) (PO4) 3], calcium bis (dihydrogenophosphate) Ca (H2PO4) 2 hydrated or unhydrated, calcium pyrophosphate Ca2P2O7, hydroxyapatite, calcium fluorophosphate, calcium glycerophosphate. In particular, the calcium derivative is calcium borate. More particularly, the calcium derivative is calcium carbonate, calcium dihydrogen carbonate.

Preferably, the calcium derivative is chosen from calcium sulphate CaSO4, gypsum, calcium diacetate, hydrated or non-hydrated calcium gluconate, calcium phosphate Ca3 (PO4) 2, calcium hydrogen phosphate CaHPO4 hydrated or unhydrated, calcium bis (dihydrogen phosphate) Ca (H2PO4) 2 hydrated or unhydrated, calcium pyrrolidonecarboxylate, hydroxyapatite.

According to a preferred embodiment of the invention, the molar amount of calcium is identical to the molar amount of the dyes.

According to a particular embodiment of the invention, the metal derivative (s) f) is (are) chosen from among the rhodium salts and their hydrates and their supported forms. The salts of Rh can also be in the form of 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, there may be mentioned sulphates, halides, carboxylates of Rh. Especially the sulphates is rhodium sulphate + III (Rh2 (SO4) 3) [10489-46-0]. According to an advantageous variant, the Rh salts are chosen from halides such as hydrated (RhC132.5H2O) or non-hydrated (RhCl3) rhodium + III chlorides, such as rhodium chloride trihydrate. Especially the carboxylates are rhodium acetate + III [42204-14-8].

Preferably, the rhodium derivative is chosen from rhodium sulfate and rhodium acetate. In a preferred embodiment of the invention, the amount of rhodium is of the same order of magnitude as that of the dyes.

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

The metal salts f) according to the invention can be introduced in solid form in the compositions or come from natural water, mineral or thermal, rich in these ions or seawater (dead sea in particular). They can also come from mineral compounds such as plant extracts containing them (see for example patent 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 come from the wetting of the keratin fibers and / or the composition or compositions comprising the compounds a) to f) as defined above 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 above.

The cosmetic compositions according to the invention are cosmetically acceptable, that is to say that they comprise a coloring support which generally contains water or a mixture of water and one or more organic solvents or a mixture of organic solvents. By "organic solvent" is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it. - organic solvents:

Examples of organic solvents that may be mentioned are lower C 1 -C 4 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, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol. The organic solvents are present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. - the additives:

The composition (s) of the dyeing method according to the invention may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidant agents, penetration, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents .

Said adjuvants are preferably chosen from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the dyeing process according to the invention do not not, or not substantially, impaired by the addition or additions envisaged.

- the additional dyes:

The dyeing process employing the ingredients a) to f) as defined above as well as possibly derivatives of orthodiphenols as defined above, can further implement one or more additional direct dyes. These direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and / or nonaromatic dyes of current use such as neutral, benzene neutral, acidic or cationic direct dyes, direct dyes neutral azo, acidic or cationic, natural direct dyes other than orthodiphenols, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine, triarylmethane, indoamine, methines, styryl, porphyrin, metalloporphyrin, direct dyes, phthalocyanines, methine cyanines, and fluorescent dyes. Among the natural direct dyes that may be mentioned are lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

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

The composition according to the invention or the composition (s) of the process implementing the ingredients a) to f) as defined above may also comprise one or more oxidation bases and / or one or more couplers conventionally used to the dyeing of keratinous fibers. Among the oxidation bases, mention may be made of para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among these couplers, it is possible to mention in particular, meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The oxidation base (s) present in said composition (s) used in the process are generally present in an amount ranging from 0.001 to 10% by weight of the weight. total of the composition (s) containing them.

The cosmetic composition (s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream, a gel or in any other form suitable for carrying out a dyeing keratinous fibers. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam.

- pH of the composition (s):

According to 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, ie greater than 7, 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, that is, that is to say greater than 7. According to one embodiment, the pH of the cosmetic composition or compositions containing d) one or more (bi) carbonate (s) or one or more system (s) generator (s) of (bi) carbonate (s) is alkaline, ie greater than 7, preferably between 8 and 12 and more particularly between 8 and 10.

Preferably, the (bi) carbonates or the (bi) carbonate (s) generator system (s) are used in a single cosmetic composition and the pH of said composition is alkaline, ie greater than 7, preferably between 8 and 12 and, more particularly, between 8 and 10. According to a particular embodiment of the invention, the pH of the cosmetic composition comprising d) one or more (bi) carbonates or one or more systems generator (s) of (bi) carbonate (s) and e) one or more basifying agent (s) different from (bi) carbonate (s) is alkaline, greater than 7, preferably between 8 and 12 and, more particularly, between 8 and 10. In other words, preferably, the (bi) carbonate (s) or (b) carbonate (s) generator system (s) and the alkalinizing agent (s) ( s) different (s) carbonates (e) are implemented in a single composition and the pH of said composition is alkali n, being greater than 7, preferably between 8 and 12 and, more particularly, between 8 and 10, in particular between 9 and 10. Even more preferably, the (bi) carbonate (s) chosen from ammonium bicarbonates and the alkalinizing agents chosen from alkanolamines are used in a single cosmetic composition and the pH of said composition is alkaline, ie greater than 7, preferably between 8 and 12 and, more particularly, between 8 and 10, especially between 9 and 10. According to one embodiment, if one or more cosmetic compositions used during the dyeing process do not contain (bi) carbonates, the pH of the composition (s) containing hydrogen peroxide or a system hydrogen peroxide generator is preferably less than 7, more preferably between 1 and 5. Preferably, the one or more compositions containing the ortho-diphenol (s) and not containing any (Bi) carbonates have a pH below 7, and preferably between 3 and 6.5. According to a particular embodiment of the invention, the cosmetic composition (s) containing the manganese or zinc salt (s) b) and not containing (bi) carbonates have a pH of less than 7, and preferably of between 3 and 6.5.

According to one particular embodiment of the invention, the cosmetic composition (s) containing the titanium salt (s) f) and not containing (bi) carbonates have a pH of less than 7, and preferably of between 3 and 6, 5. The pH of these compositions can be adjusted to the desired value by means of alkalinizing agents as defined previously in d) or from acidifying agents normally used for dyeing keratin fibers or else using conventional buffer systems. . Among the acidifying agents of the compositions used in the invention, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the basifying agents, these are the agents as defined previously in "d) alkalinizing agent (s)".

staining process in one or more steps According to one embodiment, the method for staining the keratinous fibers is carried out in a single step by applying to the keratinous fibers an aqueous dye composition comprising: a) one or more derivatives (s); ) dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s); (b) one or more manganese salt (s); (c) hydrogen peroxide or one or more hydrogen peroxide generator systems; d) one or more (bi) carbonate (s) or one or more system (s) generating (s) of (bi) carbonate (s); E) one or more basifying agent (s) different from (s) bicarbonate (s); and f) one or more metal salt (s) selected from molybdenum, aluminum, calcium zinc and rhodium salts.

The pause time after application is generally set between 3 and 120 minutes and preferably between 10 and 60 minutes and more preferably between 15 and 45 minutes. In this embodiment, the dye cosmetic composition comprising the ingredients a), b), c), d), e) and f) has an alkaline pH, thus greater than 7, preferably between 8 and 12 and, more particularly, between 8 and 10. According to another embodiment, the method for dyeing keratin fibers is in two or three steps. According to one particular embodiment of the invention, the method for dyeing keratinous fibers is carried out in two stages by the application to the keratinous fibers of a dye composition comprising ingredients a), b), c), d) and e) as defined above, then, in a second step, a composition comprising the ingredient f) as defined above is applied to said keratin fibers, it being understood that at least one of the two compositions is aqueous. Preferably, the composition comprising the dihydroxyflavonoid derivative (s), neoflavanol (s) or neoflavanone (s), is aqueous. Even more preferentially, the two compositions used in this embodiment are aqueous. For this process, the pause time after application for the first step is generally set between 3 and 120 minutes and preferably between 10 and 60 minutes and more preferably between 15 and 45 minutes. The application time of the composition comprising the ingredient f) during the second step is generally set between 3 and 120 minutes and preferably between 3 and 60 minutes and more preferably between 5 and 30 minutes. According to another embodiment, the method for dyeing keratin fibers is in three steps. In a first variant of the three-step process, the first step consists in applying to said fibers a composition comprising ingredients a), b) and c) as defined above, then, in a second step, a composition comprising the ingredients of and e) as defined above is applied to said fibers, and then, in a third step, a composition comprising the ingredient f) is applied to said fibers, it being understood that at least one of the three compositions is aqueous. Preferably, the composition comprising the dihydroxyflavonoid derivative (s), neoflavanol (s) or neoflavanone (s), is aqueous. Even more preferentially, the three compositions used in this embodiment are aqueous. In a second variant of the three-step process, the first step consists in applying to said fibers a composition comprising the ingredients a) and b) as defined above, then, in a second step, a composition c), d) and e) as defined above is applied to said fibers, then, in a third step, a composition comprising the ingredient f) is applied to said fibers, it being understood that at least one of the three compositions is aqueous. For these last two processes, the pause time after application for the first step is generally set between 3 and 120 minutes and preferably between 10 and 60 minutes and more preferably between 15 and 45 minutes. The application time of the composition used during the second step is generally set between 3 and 120 minutes and preferably between 3 and 60 minutes and more preferably between 5 and 30 minutes. The application time of the composition used in the third step is generally set between 3 and 120 minutes and preferably between 3 and 60 minutes and more preferably between 5 and 30 minutes.

According to one embodiment, the process for dyeing keratinous fibers is carried out in one or more steps by applying to the keratinous fibers of one or more cosmetic compositions comprising: a) one or more derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (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 salts. , aluminum, zinc, calcium and rhodium, in particular chosen from: i) mono or polymeric molybdenum carboxylates; as those of formula n [R-C (O) O -] n [Mo] in which n represents an integer different from zero preferably equal to 2 and R represents an optionally substituted (C 1 -C 6) alkyl group; the mono or polymeric molybdenum carboxylates are particularly dimeric molybdenum acetate [14221-06-8], ii) aluminum sulphates such as aluminum 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 pyrrolidone carboxylate; vi) rhodium III carboxylates; it being understood that the composition comprising ingredient d) has an alkaline pH, ie greater than 7, in particular between 8 and 10, and that the composition comprising 37 or the ingredients f) is applied to the keratinous fibers at the last step of the coloring process.

Preferably, the process for dyeing keratinous fibers is carried out in three steps. In particular, the dyeing process is carried out in three stages by application to the keratin fibers: i) of a cosmetic composition comprising a) one or more derivatives of dihydroxyflavonoide (s), b) one or more salt (s) ) of manganese selected from the 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 selected from: - mono or polymeric molybdenum carboxylates; as those of formula n [R-C (O) O -] n [Mo] in which n represents an integer different from zero preferably equal to 2 and R represents an optionally substituted (C 1 -C 6) alkyl group; the mono or polymeric molybdenum carboxylates are particularly dimeric molybdenum acetate [14221-06-8]; aluminum sulphates such as aluminum sulphate octahydrate; zinc sulphates such as zinc sulphate heptahydrate; zinc carboxylates such as zinc acetate or glycinate; calcium carboxylates such as calcium acetate or pyrrolidone carboxylate; rhodium III carboxylates; it being understood that the composition comprising the ingredients d) and e) has an alkaline pH, that is to say greater than 7, in particular between 8 and 10, and that the composition comprising the titanium salts is applied to the keratin fibers at the last stage of the coloring process. More particularly, the derivative (s) of dihydroxyflavonoid (s), a) used in the composition may be selected from catechin, quercetin, and natural extracts containing them. Even more particularly, the dihydroxyflavonoide (s) are chosen from catechin and quercetin.

More particularly, the derivative (s) of neoflavanol (s) or neoflavanone (s), a) used in the composition may be selected from extracts of logwood and red wood. When an additional orthodiphenol is furthermore in the process, it is preferentially gallic acid and its derivatives which are found in particular in gall nut extracts. 38 Whatever the mode of application , the application temperature is generally between room temperature (15 to 25 ° C) and 80 ° C and more particularly between 15 and 45 ° C. Thus, it is advantageous, after application of the composition according to the invention, to subject the hair to a heat treatment by heating at a temperature of between 30 and 60 ° C. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices. Both heating and smoothing of the hair can be used as a heating iron at a temperature of between 60 and 220 ° C and preferably between 120 and 200 ° C. Whatever the mode of application, a wiping and / or drying of the keratinous fibers may optionally be carried out between each step, in particular before carrying out the step comprising the application of a composition comprising ingredient d), and in particular before carrying out the last step comprising the application of a composition containing the metal salt (s) f) as defined above. A particular embodiment of the invention relates to a dyeing process which is carried out at room temperature (25 ° C). In all the particular modes and variants of the processes described above, the compositions mentioned are ready-to-use compositions which 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 object of the invention is a multi-compartment device or "kit" of dyeing. Advantageously, this kit comprises from 2 to 7 compartments containing from 2 to 7 compositions in which the ingredients are distributed a) one or more derivative (s) of dihydroxyflavonoide (s), b) one or more salt (s) of manganese (c) hydrogen peroxide or one or more hydrogen peroxide generator systems, (d) one or more (bi) carbonate (s) or one or more generator system (s) of bicarbonate (s), e) one or more agent (s) alkalinizing (s) different from the (bi) carbonate (s) and f) one or more salt (s) selected (s) among the molybdenum salts, aluminum, zinc, calcium and rhodium, said compositions being aqueous or powdery, with particularly at least said compositions being aqueous.

According to a first variant, the kit comprises seven compartments, the first six compartments respectively comprising the powder ingredients a), b), c), d), e) and f) as defined above and in the sixth compartment containing a composition. aqueous such as water. In this case, the compound (s) c) are precursors of hydrogen peroxide. Another variant relates to a kit with six compartments, one of which contains an aqueous composition, and whose other compartments comprise an ingredient a) to f) as defined above. In another variant, the device comprises six compartments: a first compartment comprising a composition containing ingredient a) as defined above, a second compartment comprising ingredient b) as defined above, a third compartment comprising ingredient c ) as defined above, a fourth compartment containing ingredient d) as defined above, a fifth compartment containing ingredient e) as defined above, and a sixth compartment containing ingredient f) as defined above, said compositions that can be aqueous or powdery. Preferably, at least one of these compositions is aqueous. Another preferred embodiment relates to a device comprising four compartments: (i) a first compartment contains a composition containing: a) one or more derivative (s) of dihydroxyflavonoide (s), neoflavanol (s) or neoflavanone (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 generator systems; (iii) a third compartment contains a composition containing: (d) one or more (bi) carbonate (s) or a plurality of (bi) carbonate (s) generator systems; and e) one or more basifying agent (s) different from the (b) carbonate (s), (iv) a fourth compartment contains a composition containing: f) one or more salt (s) chosen (s) among the salts of molybdenum, aluminum, zinc, calcium and rhodium. In this other embodiment, at least one of the four compositions is aqueous and the derivative (s) dihydroxyflavonoide (s), neoflavanol (s) or neoflavanone (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 derivatives dihydroxyflavonoide (s), neoflavanol (s) or neoflavanone (s) and b) one or more salts of manganese, the second ii) containing a composition comprising c) hydrogen peroxide or a hydrogen peroxide generating system and the third iii) containing a composition comprising d) the agent (bi) carbonate and e) the agent alkalinizing agent different from the (bi) carbonate, and the fourth (iv) containing a composition comprising f) one or more salt (s) chosen from molybdenum, aluminum, zinc, calcium and rhodium salts.

In this other kit at least one of the compositions is preferably aqueous. And more particularly this composition contains hydrogen peroxide. According to a particular embodiment of the invention, the kit comprises three compartments: a first compartment comprising a composition containing ingredients a), b), c) as defined above, a second compartment containing ingredients d) and e) such that defined above, and a third compartment containing the ingredient f) as defined above. Among the kits with three compartments are also possible the kits which contain in a first compartment a composition comprising the ingredients a), b), d), and e) as defined above, in a second compartment a composition comprising the ingredient c ) as defined above, and in a third compartment a composition comprising the ingredient f) as defined above. In these two variants of three-compartment kit, the first composition contained in the first compartment comprising either ingredients a), b) and c) as defined above or ingredients a), b), d) and e) such that defined above is in powder form and preferably the second composition is aqueous. According to one variant, the device according to the invention further comprises an additional composition comprising one or more treatment agents.

The compositions of the device according to the invention are packaged in separate compartments, possibly accompanied by appropriate, identical or different application means, such as brushes, brushes or sponges. The device mentioned above can also be equipped with means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2586913. As indicated above, the present invention also relates to a composition cosmetic composition for dyeing keratinous fibers comprising ingredients a), b), c), d), e) and f) it being understood that the pH of the composition is alkaline is greater than 7, and preferably between 8 and 12 Particularly between 8 and 10.5. The subject of the invention is also the use of said dye cosmetic composition for dyeing keratinous fibers. The following examples serve to illustrate the invention without however being limiting in nature. EXAMPLES Examples of coloring

In the following example, the rise in the 4E * coloration and the chromaticity C * were compared between a dyeing method according to the invention and an identical dyeing process, but which does not imply the use of a composition. comprising titanium salts.

1. Compositions tested Compositions Al A2 Catechin 0.420 g - Hematoxylin - 0.420 g Manganese gluconate 0.003 g 0.003 g Hydrogen peroxide 1.2 g 1.2 g Ethanol 13.2 g 13.2 g Propylene glycol 13.2 g 13 , 2 g Water Qs 100g Qs 100g Composition B (developer) Amount Sodium bicarbonate 2.6 g Monoethanolamine 2 Demineralized water qs 100 g Compositions Cl C2 C3 C4 C5 C6 C7 C8 C9 Aluminum sulphate octahydrate Zinc sulphate heptahydrate Zinc acetate dihydrate Basic aluminum acetate Calcium acetate Calcium pyrrolidone carboxylate Rhodium acetate III Zinc glycinate Molybdenum acetate dimer Water Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp Demineralized q 100 100 100 100 100 100 100 100 100 (*): present at 1.5. 10-3 mol. . Operating mode

Each composition A1 or A2 is applied to strands of hair 90% white permed, at a rate of 12 grams of composition per 1 gram of hair. It is then left for 30 minutes at a temperature of 50 ° C. At the end, the impregnated hair is wiped with an absorbent paper towel to remove the excess composition. Composition B is then applied to each of the locks at a rate of 4 grams of composition for one gram of locks. The pH of composition B is 9.5. The exposure time is 10 minutes at room temperature. The hair is then rinsed with water, washed with a classic shampoo and dried in the helmet. A composition C (Cl to C9) is then applied (post-treatment) on each of the locks at a rate of 4 grams of composition per gram of lock; the exposure time is 10 minutes at room temperature. The hair is then rinsed with water, washed with a classic shampoo and dried in the helmet.

3. Colorimetric results The rise in the 4E * coloration and the chromaticity C * are compared between a dyeing process according to the invention and an identical method, but which uses water instead of the compositions C1 to C10 based on various metal salts.

The color of the locks was evaluated in the CIE L * a * b * system using a Minolta Spectrophotometer CM2600D colorimeter. In this system L * a * b *, the three parameters denote respectively the intensity of the color (L *), a * indicates the green / red color axis and b * the blue / yellow color axis. The color variation between the locks of white hair with 90% untreated (90 BP) untreated white (control) and after treatment or staining are defined by (AE *) according to the following equation: DE * = .J (L) * -Lo *) 2 + (a * -ao *) 2 + (b * -bo *) 2 In this equation, L *, a * and b * represent the values measured on locks of hair after staining and Lo * , ao * and bo * represent the values measured on locks of unstained virgin hair. The higher the value of 4E *, the better the color rise. The chromaticity has also been measured by the values a * and b * and is obtained from the following formula: C * _ Va * 2 + b * 2 The greater the value of C *, the more chromatic the color obtained.

The values of the rise in 4E * staining and chromaticity C * are given in the following tables: Ingredients a) Catechin Quercetin 4E * C * 4E * C * Without metal salts 22 19.8 11.9 18, (Comparative) With Cl (Invention) 15.2 24.3 With C2 (Invention) 26.0 21.6 With C3 (Invention) 26.0 22.1 15.7 20.6 With C4 (Invention) 18, 1 25.4 With C5 (invention) 25.7 22.5 With C6 (invention) 24.8 21.5 With C7 (invention) 22.3 20.8 With C8 (invention) 15.0 22.1 With C9 (Invention) 14.1 21.9 It appears visually that the method of the invention makes it possible to obtain a stronger rise as well as a better color chromaticity. This is confirmed by the colorimetric measurements which demonstrate that the dyeing process according to the invention makes it possible to lead to more chromatic colorings whatever the dihydroxyflavonide derivative used with respect to a process which does not use metal salt f). The same trend has been observed for the rise of the color which is very satisfactory.

Claims (14)

REVENDICATIONS1. A process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, wherein said fibers are treated with one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the following ingredients: a) one or several derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s); (b) one or more manganese salt (s); (c) hydrogen peroxide or one or more hydrogen peroxide generator systems; d) one or more (bi) carbonate (s) or one or more system (s) generating (s) of (bi) carbonate (s); e) one or more basifying agent (s) different from (s) bicarbonate (s); and f) one or more metal salt (s) selected from molybdenum, aluminum, 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, ie greater than 7, and the metal salt (s) f) is (are) applied in the last step of the dyeing process. 2. Staining process according to claim 1, characterized in that the derivative (s) of dihydroxyflavonoid (s) are chosen from the derivative (s) of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s), natural (s). 3. Staining process according to claim 1 or 2, characterized in that a) the derivative (s) dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s), is (are) chosen (s) among those of formula (1), (II) or (III) as well as their salts of organic or mineral acid, their optical isomers, geometric, tautomers and their solvates such as hydrates: R13 R14 R12 formula (1) in which: represents a single bond or a double bond; - R1 R2, R3, R4, R1 °, R11 R12R13 and R14, identical or different, represent: - a hydrogen atom, - a halogen atom, - a hydroxy group, - a (C1-C6) alkyl group a (C1-C6) alkoxy group, a (C1-C6) alkylthio group, a carboxyl group, an alkyl or alkoxycarbonyl carboxylate group, an optionally substituted amino group, a linear or branched alkenyl group; optionally substituted, - an optionally substituted cycloalkyl group, - an aryl group, - a substituted aryl group, - a group containing one or more silicon atoms, - a (di) ((hydroxy) (C1-C6) alkyl) amino group a -O-sugar group such as -O-glucoside, -RZC (X) -Y- group with R representing a hydrogen atom, or a (C1-C6) alkyl group, Y and Z, which are identical or different, represent a bond, or an oxygen atom, sulfur or a group -N (R ') - with R' representing a hydrogen atom or a group (C1-C6) alkyl, Y may also represent a (C1-C6) alkylene group; X represents an oxygen, sulfur, or N-R "atom with R" representing a hydrogen atom or a (C1-C6) alkyl group; - R6, R6, R ', R $ and R9, identical or different, represent a hydrogen atom, or a group selected from hydroxy or (C1-C6) alkyl; R11 (1) - or then R5 with R6 and / or R 'with R5 together with the carbon atom carrying them an oxo group; or else R5 and R9 together form a bond; it being understood that: at least two radicals chosen from R1, R2, R3, R4, R10, R11, R12R13 and R13, which are contiguous, represent a hydroxyl group; - when R5 with R6 and / or R 'with R5 together form an oxo group, or R5 with R9 together form a bond, then - represent a single bond; when - carried by the oxygen atom is a double bond, then the compound of formula (1) is cationic and it is associated with it an anionic counterion; formulas (II) and (III) in which: - represents a single or double conjugated carbon - carbon bond, 15 - X represents a group: // / HO-C or O = C \ \ - R1, R2, R3, R4 , R5 and R6, which may be identical or different, represent a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, optionally substituted alkoxy, or an optionally substituted acyloxy group. 20 4. The method of dyeing according to any one of claims 2 to 5, characterized in that the derivative (s) of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s), natural (s) is (are ) selected from animal extracts, bacteria, fungi, algae, plants and fruits. 5. Staining process according to any one of the preceding claims, characterized in that the salt (s) of manganese (b) is (are) OH selected from among the oxides of manganese and the halides, the sulphates phosphates, nitrates and perchlorates, salts of carboxylic acids such as gluconates and mixtures thereof. 6. Coloring method according to any one of the preceding claims, characterized in that ingredient c) is hydrogen peroxide or urea peroxide. 7. Coloring process according to any one of the preceding claims, characterized in that the (bi) carbonate (s) d) is (are) chosen from alkali, alkaline earth or alkali (bi) carbonates or ammonium. 8. dyeing process according to any one of the preceding claims, characterized in that the agent (s) alkali (s) e) different (s) or (s) bicarbonate (s) is (are) chosen (s) among: - ammonia, - alkanolamines, - ethylenediamines oxyethylenated - ethylenediamines oxypropylenes, - the mineral or organic hydroxides, - silicates of alkali metals, - amino acids, and - compounds of formula (V ) following: RR a \, b NWN i \ R ~ Rd (V) formula (V) in which: - W is a divalent group (C, -C) optionally substituted alkylene; - Ra, Rb, R, and Rd, identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl radical. 9. The method of dyeing according to any one of the preceding claims, characterized in that the derivative (s) metal (s) f) is (are) chosen from: - molybdenum oxides such as: - the oxides of Mo (IV) with ligand / i-diketones M0O2L2 with L ligand, identical or different, preferably identical represent a / i-diketone of type RC (X) -C (R ') - C (X) R "with R and R ", which may be identical or different, represent a linear or branched (C1-C6) alkyl group, and R 'represents a hydrogen atom or a linear or branched (C1-C6) alkyl group, X represents an atom of oxygen, sulfur or a group N (R) with R representing a hydrogen atom or a linear or branched (C1-C6) alkyl group, more particularly the Mo dioxide is of formula MoO2 [CH3C (O) CH C (O) CH3] 2; - molybdenum dioxide; dihalogenodioxomolybdenum (HaI) 2MoO2 with identical or different Hal is as defined above, particularly Hal are identical and represent a chlorine atom; blue molybdenum or "molybdenum blues" [66771-43-5], a mixture of Mo oxide / hydroxides of Mo (VI) and Mo (V); especially Mo6 + 3 Mo5 + 3 O18H, and the condensation derivatives of with the phosphate ions; the binary molybdenum halides of oxidation state (II) to (VI), hexacoordinated by 6 halogens of Mo (V), (IV) and (III), the Mo atoms being linked by halogen bonding such that the Mo (II) halide containing [Mo6Hal8] 4+ clusters bound to halogen atoms to give Mo6Hal12 with Hal, which are identical or different, as defined previously and more particularly Hal represents a chlorine atom; - Molybdenum tetrahalides (HaI) 4Mo with Hal ', identical or different, as defined above, such as MoCl4; sulfur-containing Mo derivatives chosen from: molybdenum disulphides, molybdenum (IV) sulphides, MoS2 and molybdenum sesquisulphide; trisulfides of dimolybdenum (III), Mo2S3; porphyrins of molybdenum; mono or polymeric molybdenum carboxylates; as those of formula n [R-C (O) O -] n [Mo] in which n represents an integer different from zero and preferably equal to 2, and R represents an optionally substituted (C1-C $) alkyl group; especially dimeric molybdenum acetate; aluminum trihydroxide Al (OH) 3, aluminum oxide hydroxide A10 (OH), hydrated or unhydrated aluminum oxide Al 2 O 3, alkali metal aluminates such as sodium aluminate NaAlO 2; aluminum sulphates chosen in particular from hydrated or unhydrated aluminum sulphate Al 2 O 12 S 3, such as aluminum sulphate octahydrate; aluminum carboxylates, especially chosen from basic aluminum acetate C41-17O5AI, aluminum oxalate, hydrated or non-hydrated aluminum citrate such as hydrated aluminum citrate, aluminum lactate , and aluminum glycinate; aluminum phosphates, chosen especially from aluminum 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 sulfate + III (Rh2 (SO4) 3), rhodium halides such as hydrated (RhCl3 2.5H2O) or non-hydrated (RhCl3) rhodium + III chlorides, such as rhodium trihydrate., rhodium carboxylates such as rhodium acetate + III. 10. Staining process according to any one of the preceding claims, characterized in that the metal derivative (s) f) is (are) chosen from: i) the molybdenum carboxylates mono or polymeric ; as those of formula n [R-C (O) O -] n [Mo] in which n represents an integer different from zero preferably equal to 2 and R represents an optionally substituted (C 1 -C 3) alkyl group; the mono or polymeric molybdenum carboxylates are particularly dimeric molybdenum acetate; ii) aluminum sulphates such as aluminum 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 pyrrolidone carboxylate; and vi) rhodium carboxylates III.35 11. Method according to any one of the preceding claims, characterized in that the first step consists in applying to said fibers a composition comprising the ingredients a), b) and c) as defined according to any one of claims 1 to 6, then, in a second step, a composition comprising the ingredients d) and e) as defined in any one of claims 1, 7 or 8, then, in a third step, a composition comprising the ingredient f) such as defined in any one of claims 9 or 10 is applied to said fibers, it being understood that at least one of the three compositions is aqueous. 12. Cosmetic composition for dyeing keratinous fibers containing compounds a), b), c), d), e) and f) as defined according to any one of claims 1 to 10. 13. Multi-compartment device comprising 2 to 6 compartments containing from 2 to 6 compositions in which are distributed ingredients a), b), c), d), e) and f) as defined according to any of Claims 1 to 10, said compositions being aqueous or powdery, 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, to improve the chromaticity and / or the rise of the color of the fibers. keratinous agents, in particular human keratinous fibers such as the hair, stained from one or more derivatives of dihydroxyflavonoid (s), neoflavanol (s) or neoflavanone (s), as defined in any of claims 1 to 4.