FR2954119A1 - Dyeing keratin fibers, comprises treating the fibers with one or more orthodiphenol derivatives, metal derivatives comprising e.g. metal salts, and alkalizing agents - Google Patents

Abstract

Method for dyeing keratin fibers, comprises treating the fibers with: (a) one or more orthodiphenol derivatives; (b) one or more metal derivatives comprising metal salts, metal complexes, metal oxides, metal oxanions, and/or their supported forms, where the metals are manganese (III) to manganese (VII) and (c) one or more alkalizing agents, provided that the pH at the end of the process is alkaline, greater than 7, preferably 8-10.5. An independent claim is included for a cosmetic composition for dyeing keratin fibers containing: (a)-(c); and optionally (d) one or more chemical oxidizing agents.

Description

The invention relates to a composition comprising a) at least one orthodiphenol derivative, b) at least one metal derivative of manganese (III) to (VII), c) at least one basifying agent; a process for dyeing keratinous fibers by treating said fibers employing ingredients a), b) and c) and their use for dyeing keratinous fibers from these ingredients.

It is known to obtain so-called "permanent" stains with dyeing compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and compounds. heterocyclic. 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 dyes are permanent, powerful, and resistant to external agents, including light, weather, washing, perspiration and friction,

However, commercial hair dyes that contain them may have disadvantages such as staining, odor problems, comfort and degradation of keratin fibers. This is particularly the case with oxidation stains.

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 including Mn and / or Zn. In particular patent applications FR 2 814 943, FR 2 814 945, FR 2 814 946, FR 2 814 947, provide compositions for dyeing the skin or keratin fibers, comprising a dye precursor which contains at least one orthodiphenol, salts and oxides of Mn and / or Zn, alkalines 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. However, the colorations obtained are insufficiently intense, especially in the case of hair fibers. It is also known to use metals to improve the hair coloring in amounts of metals of the same order of magnitude as that of the dyes using a mordenous method. However, this method generally has the disadvantage of not always respecting the cosmetics of the keratin fiber.

There is therefore a real need to develop staining methods that make it possible to obtain powerful colorations from orthodiphenols, in particular from natural extract rich in orthodiphenols, while limiting the discoloration of keratin fibers. In particular, there is a need to obtain less aggressive colorings for the hair and at the same time that resist external agents (light, bad weather, shampoo), which are stubborn and homogeneous, 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, wherein said fibers are treated by: a) one or more derivatives of orthodiphenol (s); b) one or more metal derivative (s) chosen from metal salts, metal complexes, metal oxides, metal oxanions, their supported forms and mixtures for which the metal (s) is (are) selected from manganese (III) to (VII); and (c) one or more basifying agent (s); it being understood that the pH at the end of the process is alkaline, ie greater than 7 and preferably between 8 and 12. Particularly between 8 and 10.5.

Another subject of the invention relates to a cosmetic composition for the dyeing of keratin fibers, comprising: one or more ingredient (s) a) as defined previously; one or more ingredient (s) as defined previously and one or more ingredient (s) as defined previously; it being understood that the pH of the composition is greater than 7 and preferably between 8 and 12. Particularly between 8 and 10.5.

Another object of the invention relates to a multi-compartment device comprising the ingredients a) to c) as defined above.

The method according to the invention has the advantage of coloring human keratinous fibers, with results of powerful coloring, chromatic, resistant to washes, perspiration, sebum and light and more durable without alteration of said fibers. In addition, the colorations obtained from the process give homogeneous colors from the root to the tip of a fiber (low color selectivity). a) orthodiphenol derivative:

A particular embodiment of the invention relates to derivatives of orthodiphenols or mixtures of compounds comprising at least one aromatic ring, preferably a benzene ring, comprising at least two hydroxy groups (OH) borne by two adjacent carbon atoms of the aromatic ring which are not autoxydisable indole derivatives. More particularly, they are different from 5,6-dihydroxyindole. 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 the orthodiphenol derivatives according to the invention is a benzene ring. By condensed ring is meant that at least two saturated or unsaturated rings, heterocyclic or not, have a common bond i.e. 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 a) represents a compound of formula (I), or one of these oligomers, in salified form or not: 4 OH (I) R 2 formula (I) in which the substituents: • R, at R4, which may be identical or different, represent: a hydrogen atom, a halogen atom, a hydroxyl radical, a carboxyl radical, an alkyl carboxylate or alkoxycarbonyl radical, an optionally substituted amino radical, a optionally substituted linear or branched alkyl radical, an optionally substituted linear or branched alkenyl radical, an optionally substituted cycloalkyl radical, an alkoxy radical, an alkoxyalkyl radical, an alkoxyaryl radical, the aryl group possibly being substituted, an aryl radical, - a substituted aryl radical, - a heterocyclic radical, saturated or unsaturated, bearing or not a cationic or anionic charge, optionally substituted and / or optionally condensed a with an aromatic ring preferably benzene, said aromatic ring being optionally substituted especially by one or more hydroxy or glycosyloxy groups, - a radical containing one or more silicon atoms, • 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 or unsaturated ring, aromatic or not, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. Particularly, R 1 to R 4 together form from one to four cycles. A particular embodiment of the invention relates to orthodiphenol derivatives of formula (I) including two adjacent substituents R 1 -R 2, R 2 -R 3 or R 3 -R 4 can not form with the carbon atoms that 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 C1-C2 alkoxy radical; a C1-C10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; 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 by 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 heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom which may or may not be different from nitrogen; quaternary ammonium -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 C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-alkyl radical; -C2; a carbamoyl radical ((R) 2 N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; an alkylsulphonylamino radical (R'SO2-NR-) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-alkyl radical; -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 ammonium, substituted or unsubstituted); 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, C1-C2alkoxy, (poly) -hydroxyalkoxy C2-C4, acylamino, amino substituted by two identical or different alkyl radicals, at C 1 -C 4, optionally carrying at least one hydroxyl group, or both radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, preferably from 5 to 6 members, optionally substituted saturated or unsaturated optionally comprising another heteroatom identical or different from the nitrogen; a halogen atom; a hydroxyl group; a C1-C2 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 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 bearing at least: a hydroxyl group; an amino group optionally substituted with one or two C 1 -C 3 alkyl radicals 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, 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 C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-alkyl radical; -C2; a carbamoyl radical ((R) 2 N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; an alkylsulphonylamino radical (R'SO2-NR-) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-alkyl radical; -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 carboxylic radical in acid or salified form (preferably with an alkali metal or ammonium, substituted or unsubstituted); 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 a radical derived from a mono or polysaccharide. The radicals containing one or more silicon atoms are preferably poly-dimethylsiloxane, poly-diphenylsiloxane, poly-dimethylphenylsiloxane, stearyloxy-ethylenic 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 groups, amine or ketone. These rings may contain one or more oxo groups on the carbon atoms of the heterocycle. Among the heterocyclic radicals which may be used, mention may be made of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl and thienyl groups. More preferably, the heterocyclic groups are fused groups such as benzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, 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 one particular embodiment of the invention, the composition comprises as ingredient i) one or more synthetic orthodiphenol derivative (s) which does not exist in nature.

According to another preferred embodiment of the invention, the method for dyeing keratin fibers uses 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 i) are in particular: flavanols such as catechin and epichatechin gallate, flavonols such as quercetin, anthocyanidins such as cyanidin, delphinidin, petunidine, anthocyanins or anthocyanins such as myrtilline, orthohydroxybenzoates, for example salts of gallic acid, flavones such as luteolin, hydroxystilbenes, for example 3,3'-tetrahydroxy, stilbene, optionally oxylated (for example glucosylated), 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, dihydroxycinnamates such as caffeic acid and chlorogenic acid, orthopolyhydroxycoumarines, orthopolyhydroxyisocoumarines, orthopolyhydroxycoumarones, orthopolyhydroxyisocoumarones, orthopolyhydroxychalcones, orthopolyhydroxychromones, orthopolyhydroxyquinones, orthopolyhydroxyxanthones, 1,2-dihydroxybenzene and its derivatives, 1,2,4-trihydroxybenzene and its derivatives, 1,2,3-trihydroxybenzene and its derivatives, 4,5 trihydroxytoluene and its derivatives, - proanthocyanidins and in particular proanthocyanidins Al, A2, B1, B2, B3 and Cl - proanthocyanins, - tannic acid, - ellagic acid, - and the mixtures of the preceding 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 used in whole or in part. Especially concerning the plants the extracts are from plant or part of plants such as fruits including citrus fruits, vegetables, trees, shrubs. It is also possible to use mixtures of these extracts, rich in othodiphenols 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 taken as a whole as compound 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 a particular embodiment of the invention, the orthodiphenol derivative (s) are natural extracts rich in orthodiphenols. According to a preferred mode, the orthodiphenol 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 synthetic orthodiphenol derivative (s), natural (s), and / or the natural extract (s) used as an ingredient (i) 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) containing the ortho-diphenol (s) or the the extracts. 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) metal derivative (s) of manqanes (III) to (VII) The process of the invention uses one or more metal derivative (s) b) which catalyze oxidation by oxygen of the 'air. These derivatives are chosen from metal salts, metal complexes, metal oxides, metal oxanions and their supported forms for which the metals are manganese (III) to (VII). By "metal salt" is meant a compound different from the alloys i.e. the salt consists of a metal combined with certain non-metallic elements. The formation of metal salts results from an oxidative attack. The metal is oxidized to a cationic species and then combines with an anionic species to give a salt. This formation takes place by applying the principles and oxidation-reduction reaction (chemical reaction during which an electrons transfer takes place in which the atom that captures the electrons is called "oxidant", the one that yields them, "reducer" ); or by chemical exchange reactions between a salt and another salt or an acid, in the presence or absence of oxygen in the air. These reactions are known to those skilled in the art.

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

The metal salts according to the invention can be introduced in solid form in the compositions or come from a natural, mineral or thermal water, rich in these ions or even seawater (dead sea in particular). They can also come from mineral compounds such as earth, ochres from which the plant extract containing them (see for example patent document FR 2 814 943).

By "metal complex" or "coordination compounds" are meant systems in which the metal ion, the central atom, is chemically bonded to one or more electron donors (ligands). A ligand comprising different coordinating groups (capable of coordination with a metal) gives metal compounds corresponding to coordination sphere principles with a number of specific electrons (internal complexes or chelates) - see Ullmann's Encyclopedia of Industrial Chemistry, "Metal complex dyes". 2005, p. More particularly, metal complex is understood to mean: i) metal dyes which are complexed dyes derived from azo, azomethine, hydrazone or formazan dyes (free, bidendates, tridendates, quadridendates) such as those described in Ullmann's Encyclopedia of Industrial Chemistry, "Metal Complex Dyes", 2005, p. 1-42; (ii) compounds of the type "aza [18] annulenes" or also known as "(metallo) porphyrins" and "phthalocyanines" which contain 4 and 8 nitrogen atoms respectively included in the perimeter of the macrocycle - see "Color Chemistry" , H. Zollinger, 3rd Ed., Wiley-VCH, 2003, chap.5. Aza [18] annulenes, p. 123-160. The metal ion is then at the center of said macrocycle linked by coordination with 2 hydrogen atoms to the nitrogen atoms of pyrroles, the metal may also be stabilized by one or more ligands bidendate or not; particularly the metal complex is: - a "metalloporphyrin" consisting of a skeleton with 4 pyrrole groups which are connected to their position a, a 'by 4 methine groups and contain 16 sp2 hybridized atoms, complexing the Mn - a "chlorine" ( corresponding to a porphyrin whose external C = C double bond of a pyrrole group was reduced) complexed with Mn.

By "form (s) supported (s)" means the forms where the metal derivative b) is impregnated on a material called "support". The optional supports of these metal derivatives may be chosen from carbon, silica, alumina, optionally charged polymers comprising counter-anions or counter-cations (counter-cation or counter-anion of the metal species). By way of example, the polymers may be polyethylene glycol (PEG) and polystyrene.

According to a preferred embodiment of the invention, the derivative (s) of manganese (III) to (VII) is (are) as defined for example in Ullmann's Encyclopedia, "Manganese Compounds", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a16 123 and Kirk-Othmer Encyclopedia of Chemical Technology, "Manganese Compounds", 2005 by John Wiley & Sons, Inc. DOI: 10.1002 / 0471238961.1301140716091901.a0l.pub2, Article Online Posting Date: April 15, 2005. According to a particular embodiment of the invention, the method uses derivatives of manganese (III) or Mn (III). Mention may especially be made of: i) alkali metal or alkaline earth metal manganates such as potassium manganate (III) [12142-17-5], KMnO2, ii) manganese (III) oxide, MnO (OH), iii) manganese sesquioxide [1317-34-6], iv) dimanganese trioxide [1317-34-6], Mn2O3, and these hydrates Mn2O3. nH2O [1332-63-4] or manganite, v) Mn3O4 trimanganese tetroxide, and the mixture of manganese oxide (II, III) [1317-35-7], vi) manganese (III) phosphate such as MnPO4 hydrate. H2O [14986-93-7], vii) manganese (III) sulphates such as Mn2 (SO4) 3 dimanganese trisulfate [13444-72-9], viii) manganese (III) trihalides and their hydrates such as than MnF3 [7783-53-1], and its hydrate, MnF3. 2H2O, ix) complexes of halogenides, halogenomanganates of type M2 (MnHaI5) or M (MnHaI4) with M a monovalent cationic counterion such as an alkaline metal, a proton or an ammonium, and Hal represents an atom halogen, particularly fluorine or chlorine, x) manganese (III) phosphate complexes of types, MH2 (Mn (PO4) 2), hydrates M3 [Mn (HPO4) (OH) 2]. H2O, with M as defined above, xi) pyrophosphates of type [Mn2 (H2P2O7) 3] 3 with M as defined above, xii) manganese cyanides (III) of type M3 [Mn (CN) 6] and M3 [Mn (CN) 5 (OH)] with M as defined above, and xiii) the permanganate acid anhydride Mn2O7 and xiii) the manganese (III) complexes with a gamma dithioketone / imino / ketone ligand 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 an atom of hydrogen or a linear or branched (C 1 -C 6) alkyl group, X represents an oxygen atom, a sulfur atom or an N (R) group with R representing a hydrogen atom or a group (C 1 -C 6) ) alkyl, linear or branched, more particularly the ligand is acetylacetone, the complex is then the manganese acetylacetonate (III) [14284-89-0] Mn (C5H702) 3., xiv) the manganese acetate III (Mn (Oac) 3) According to a particular embodiment of the invention uses the manganese (IV) or Mn (IV) derivatives. Mention may especially be made of i) manganese dioxide (IV) [1313-13-9], MnO2, or pyrolusite, manganites, their alkali metal salts such as K2O • 4MnO2, and its hydrates MnO2. 2H2O, ii) alkali metal permanganates such as KMnO4, ii) Mn (HaI) 4 type manganese (IV) tetrahalide, with Hal as defined previously, such as manganese tetrafluoride (IV) [15195- 58-1] MnF4, iii) the manganese (IV) salts of M2MnO3 type, with M as defined above, more particularly H2MnO3 or Li2MnO3, iv) the mannganese (IV) complexes of MMnX6 type, with X representing an atom of halogen, such as F, or Cl, a CN cyanide group, iodate, and M is as defined above, M particularly represents an alkali metal such as K, more particularly potassium hexafluoride manganese, K2MnF6, M2MnCI6 manganese hexachloride, with M as defined above, the alkali metal hexacyano such as K2Mn (CN) 6, v) the tricarbonylated manganese complexes such as the (C 1 -C 6) alkyl (C 5 -C 20) complex ) arylmanganese tricarbonyl especially methylcyclopentadienylmanganese tricarbonyl [1 2108-13-3], vi) triperoxymanganate (IV) type M2H2MnO (O2) 2 with M as defined above, such as K2H2MnO (O2) 2 and vii) Mn2O3 (1,4,7 trimethyl 1,4, 7 triazacyclononane) (PF6) 2 [116633-52-4].

According to a particular embodiment of the invention, the process uses derivatives of manganese (V) or Mn (V). Mention may especially be made of alkali metal Manganates (V) or also called hypomanganates such as potassium and sodium manganates [12142-41-5], K3MnO4, K2MnO4, KMnO4, NaMnO4, Na3MnO4 and Na2MnO4. According to a particular embodiment of the invention, the process uses derivatives of manganese (VI) or Mn (VI). Mention may especially be made of Manganates (VI) such as i) manganic acid [54065-28-0], H2MnO4, ii) manganate (VI) of rubidium [25583-21-5], and of cesium [25583- 22-6] and barium. According to a particular embodiment of the invention, the process uses derivatives of manganese (VII) or Mn (VII). It may be mentioned particularly i) hydrated permanganic acid HMnO4. 2H2O [24653-70-1], ii) permanganyl halides such as permanganyl fluoride [15586-97-7], MnO3F, iii) alkali metal, ammonium, phosphonium or arsenium permanganate, such as that [14333-13-2], MnO6 M, tetraphenylphosphonium permanganate [34209-26-2] (C6H5) 4P + MnO4, tetraphenylarsenium permanganate [4312-28-1] (C6H5) 4As + MnO4 and permanganate potassium KMnO4.

According to a preferred embodiment of the invention, the metal derivative (s) used represent from 0.0001% to 10% by weight approximately of the total weight of the composition (s) containing this or these metal salts and even more preferentially from 0.0001% to about 1% by weight. (c) basifying agent (s)

The basifying agent used in the dyeing process according to the invention as the third ingredient c) is an agent for increasing the pH of the composition (s) in which it is present. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. Particularly the said agent is chosen from i) (bi) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iv) oxyethylenated and / or oxypropylenated ethylenediamines, v ) inorganic or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) basic preference amino acids such as arginine, lysine, ornithine, citruline and histidine, and viii) the compounds of the following formula (II): ## STR2 ## wherein W is a propylene residue optionally substituted with a hydroxyl group or a C 1 -C 4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. The inorganic or organic hydroxides, particularly the inorganic or organic hydroxides, are preferably chosen from a) the hydroxides of an alkali metal, b) the hydroxides of an alkaline earth metal, such as sodium or potassium hydroxides, and ) transition metal hydroxides, such as group III, IV, V and VI metal hydroxides, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide. The hydroxide may be formed in situ such as, for example, guanidine hydroxide by reaction of calcium hydroxide and guanidine carbonate. By (bi) carbonates i) is understood to mean: a) 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", 5 which are identical or different, represent a hydrogen atom, a optionally substituted (C 1 -C 6) alkyl group such as hydroxyethyl), and b) bicarbonates, also known as hydrogenocarbonates, of the following formulas: - R '+, HCO3 with R' representing a hydrogen atom, an alkali metal, a 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; hydrogen hydrogen carbonate is then called dihydrogen carbonate (CO2, H2O); and - Met'2 + (HCO3) 2 with Met 'representing an alkaline earth metal.

More particularly, the basifying agent is chosen from alkali metal or alkaline earth metal (bi) carbonates; preferentially alkali metal (bi) carbonates. There may be mentioned carbonates or hydrogenocarbonates of Na, K, Mg, Ca and mixtures thereof, 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 (H003) 2.

According to a particularly advantageous embodiment, the alkalinizing agent (s) c) is (are) selected from alkanolamines and (bi) carbonates particularly alkaline or alkaline earth. In addition, they are preferably together during the coloring process.

The alkalinizing agent (s) as defined above preferably represent from 0.001% to 10% by weight relative to the weight of the composition (s) containing them. More particularly from 0.005% to 8% by weight of the composition.

Chemical Oxidizing Agents In the context of the present invention, the process of the invention can be carried out in the absence of a chemical oxidizing agent, that is to say by letting the oxygen of the air act. According to another dyeing process of the invention, said method uses a chemical oxidation agent.

By chemical oxidizing agent is meant: a) ozone; b) the persalts of alkali metal or quaternary ammonium are perborates, persulfates, percarbonates, peroxodiphosphates, Oxone® or potassium persulfate particularly the oxidant is selected from sodium perborate, sodium persulfate, potassium persulfate, ammonium persulfate, sodium percarbonate, potassium percarbonate; c) aliphatic organic C1-C6 and aromatic C6-C20 peracids and their percarboxylate forms: RC (O) O-OM 'with R representing a (C 1 -C 6) alkyl group, or (C 6 -C 20) aryl such that phenyl, M 'representing a hydrogen atom (peracid) an alkali metal or alkaline earth metal (percarboxylate) are selected from performic acid, peracetic acid, derivatives of perbenzoic acids, trifluoroacetic acid, acid peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid especially the oxidant is peracetic acid; d) organic peroxides chosen from dioxirane, C1-C6 alkyl peroxides, benzoyl peroxide, (C 1 -C 6) peroxo carboxylates, bis (tri) (C 1 -C 6) peroxides; alkylsilyl such as bis (trimethylsilyl) peroxide, C 1 -C 6 alkyl peroxydicarbonates, sodium nonanoyloxybenzene sulfonate as described in WO1995 / 000625 and US4,412,934. e) the oxidizing anions chosen from nitrites, nitrates, hypochlorites, hypobromites, hypoiodites, chlorites, bromites, iodites, chlorates, bromates, iodates, periodates, more particularly the oxidant is chosen from hypochlorite or alkali metal periodate such as sodium hypochlorite or sodium periodate; f) stable N-oxy radicals (NO.), chosen from i) heterocycles containing a sterically hindered N-oxide group such as the 2,2,6,6-tetra (C 1 -C 6) alkylpiperidinooxy radical; 2,2,6,6-tetra (C 1 -C 6) alkylmorpholinooxy; ii) the salts of Frémy nitrosodisulfonates, and iii) the morpholine N-oxide; the oxidant is particularly selected from the 2,2,6,6-tetramethylpiperidinyloxy radical; and (g) hypervalent iodine derivatives, chosen from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid derivatives, periodinanes, alkyls and benzoylhypoiodites, more preferably the oxidant is selected from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid, Dess-Martin periodinane; di (C 1 -C 6) dialkyl iodoaryl such as iodobenzene diacetate; h) the following organic compounds: N-halosuccinimides, trichloroisocyanuric acid, N-hydroxyphthalimide, linear or branched C1-C10 alkyl nitrites; The optional supports of these oxidants a) to h) can be selected from silica, alumina, coal, charged or neutral polymers i) hydrogen peroxide or system (s) generator (s) of peroxide d hydrogen such as: i-1) urea peroxide; i-2) polymeric complexes that can release hydrogen peroxide such as polyvinylpyrrolidone / H2O2 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; i-3) 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); i-4) metal peroxides generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; i-v) perborates; or i-vi) percarbonates.

Especially the fourth constituent is i).

According to a preferred embodiment of the invention, the method uses one or more hydrogen peroxide generator systems selected from among i) urea peroxide, i-2) complexes polymers capable of releasing hydrogen peroxide selected from polyvinylpyrrolidone / H 2 O 2; i-3) oxidases; i-v) perborates and i-vi) percarbonates. Moreover, the composition (s) comprising the chemical oxidizing agent (s) may also contain various adjuvants conventionally used in hair dyeing compositions and as defined hereinafter under the heading "cosmetic composition". Preferentially, the chemical oxidizing agents are chosen from alkali metal perborates such as sodium perborate, alkali metal persulfates such as sodium persulfate, potassium oxone or persulfate, and carboxylic acid peracids RC ( 0) O-OH with R representing a linear or branched C1-C6 alkyl group such as methyl, and alkaline earth metal hypochlorite such as calcium hypochlorite, alkali metal or alkaline earth metal periodate such as sodium periodate, di (C 1 -C 6) dialkyl iodoaryl such as iodobenzene diacetate.

According to a particular embodiment of the invention, the hydrogen peroxide or the chemical oxidizing agent or agents preferably represent from 0.001% to 12% by weight, expressed as hydrogen peroxide, relative to the total weight of the composition or compositions or containing them and even more preferably from 0.2% to 2.7% by weight.

photoirradiations by electromagnetic waves from the ultraviolet (UV) to infra red (IR) wave sender;

The method according to the invention may comprise a photoirradiation step with one or more electromagnetic waves. By "photoirradiation" is meant any exposure of the composition or part of the composition to a light wave during the hair dyeing process. The keratin fibers may also be irradiated once the fibers treated with ingredients a) to c) as defined above. The light spectrum may include wavelengths in the region of UV (10-400nm), visible (400-745nm), infrared (745nm to 100pm). According to one particular embodiment of the invention, the dyeing process takes place in the natural light of the sun or of the day. According to another method for dyeing keratinous fibers, the source of the photoirradiation is artificial. For the UV-emitting lamps, those described in Ullmann's Encyclopedia "Ultraviolet and Visible Spectroscopy" 2008 Wiley-VCH Verlag GmbH & Co KGaA, Weinheim, 10.1002 / 14356007.b05 383.pub2, point 3.2.

For lamps in general, mention may be made of those mentioned in Ullmann's Encyclopedia "Lamps" 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a15 115 and Ullmann's Encyclopedia "Photochemistry" 2005 Wiley-VCH Verlag GmbH & Co. KGaA , Weinheim 10.1002 / 14356007.a19 573, point 3.2 "light sources".

The lamps used in the process of the invention are in particular incandescent, halogen, fluorescent, mercury, low pressure lamps, low pressure lamps, for example sodium or neon lamps, high pressure lamps, for example mercury, halogen lamps, xenon flash lamps, fluorescent excimer lamps such as Xenon, Light Emitting Diodes or LEDs from 50 to 1000mW, lamps emitting black light or Wood's light, and lasers

Preferably, the artificial sources come from mercury, halogen and tungsten lamps, white neon tube, UV lamp emitting at 254 nm, or at 365 nm 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 keratinous fibers and / or of the composition or compositions comprising the compounds a) to c) as defined above or from one or more other compositions. Preferably the water comes from at least one composition comprising at least one compound selected from a) to c) as defined above.

cosmetic compositions:

The cosmetic compositions according to the invention are cosmetically acceptable i.e. 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: As an organic solvent, there may be mentioned, for example, C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol. The organic solvents are present in proportions preferably of between 1 and 60% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

Adjuvants: The composition (s) of the dyeing method according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants. or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, 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, agents clouding. 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, those 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 coloring process according to the invention are not not, or not substantially, impaired by the addition or additions envisaged. Additional dyes: The process using ingredients a) to c) as defined above and optionally one or more chemical oxidizing agent (s), water; or the cosmetic composition according to the invention comprising the ingredients a) to c) as defined above and optionally one or more chemical oxidizing agent (s), water; may further implement or include 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 different from orthodiphenols, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azine, triarylmethane, indoamine, methines, styrils, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and fluorescent dyes. All these additional dyes are different from orthodiphenol derivatives according to the invention and "metal-complex dyes" or porphyrins, metalloporphyrins, phthalocyanines, belonging to a) according to the invention.

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. The additional direct dye (s) used in the composition (s) preferably represent from 0.001% to 10% by weight approximately of the total weight of the composition (s) containing them and even more preferentially from 0.05% to 5% by weight approximately. The method using ingredients a) to c) as defined above and optionally the chemical oxidizing agent (s), and the water or the cosmetic composition according to the invention comprising the ingredients a) to c) as defined previously and optionally the chemical oxidizing agent (s) and water may also implement or comprise one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers. Among the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among these couplers, mention may notably be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The oxidation base (s) present in the composition (s) are in general present each in an amount of between 0.001% and 10% by weight relative to the total weight of the corresponding composition (s).

The cosmetic composition (s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream, 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) The process according to the invention uses ingredients a), b) and c), with the final pH which is basic or alkaline is greater than 7 and preferably between 8 and 12 Particularly between 8 and 10.5. It is the same for the compositions according to the invention which are basic or alkaline and which have a pH greater than 7, preferably between 8 and 12. Particularly between 8 and 10.5. The pH of these compositions can be adjusted to the desired value by means of alkalinizing agents as defined previously in c) or acidifying agents usually 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 alkalinizing agents that may be mentioned agents as defined above in "c) alkalinizing agent (s)".

Staining process in one or more steps According to a particular embodiment of the invention, the staining process is carried out, in one or more steps, by application to the keratinous fibers of one or more cosmetic compositions containing, taken together or separately in the said composition or compositions, the following ingredients: a) one or more derivatives of orthodiphenol (s) as defined above b) one or more metal derivative (s) chosen (s) from metal salts, metal complexes, metal oxides, metal oxanions, their supported forms and mixtures for which the metal (s) is (are) chosen from manganese (III) to (VII) as defined above and optionally one or more chemical oxidizing agents as defined above; c) one or more basifying agent (s) as defined above, it being understood that the pH at the end of the process is alkaline, greater than 7, preferably between 8 and 12. Particularly between 8 and 10.5 . The pause time between the stages of application of the compositions comprising ingredient (s) a), b) and / or c) is set between 3 and 120 minutes, preferably between 10 and 60 minutes and more particularly between 15 and 30 minutes. . The keratinous fibers may or may not be previously moistened. More particularly, in the process of the invention the compound (s) c) are either in admixture with a) and b) and optionally one or more chemical oxidizing agents as defined above; is applied separately after application of a cosmetic composition comprising ingredients a) and b) and optionally one or more chemical oxidizing agents as defined above; or else - is applied together with ingredient a) after application of a cosmetic composition comprising ingredient (s) b) and optionally one or more chemical oxidizing agents as defined above. A particular embodiment of the invention relates to staining methods in one or two steps.

According to a particular embodiment of the invention, the process for dyeing keratin fibers is in two steps. In a two-step process variant the first step consists in applying to said fibers a cosmetic composition comprising the ingredients a) and b) and optionally one or more chemical oxidizing agents as defined above, as defined above, then in a second step a cosmetic composition comprising ingredient c) as defined above is applied to said fibers, it being understood that at least one of the two cosmetic compositions is aqueous. According to a particularly advantageous process of the invention, the ingredient c) which is applied to the fibers comprises at least one (bi) carbonate as defined above. More particularly, the (bi) carbonate is in a composition in the presence of another alkaline agent, particularly an alkanolamine such as monoethanolamine. Preferably, the dyeing process according to the invention is carried out in two stages, the first step of which is to apply to the keratin fibers the ingredients a) and b) and optionally one or more chemical oxidizing agents as defined above; together then in a second step of applying together the ingredients c) and optionally followed by post-treatment steps such as rinsing for example with water, shampooing with a conventional shampoo and / or drying of keratinous fibers.

For these latter processes, the pause time after application of the cosmetic composition 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 pause time after application of the second cosmetic composition for 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.

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. 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.

Device or "kit" of dyeing:

Another object of the invention is a multi-compartment device or "kit" of dyeing. Advantageously, this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which the ingredients are distributed: a) one or more derivatives of orthodiphenol (s), b) one or more derivative (s) metal (s) chosen from metal salts, metal complexes, metal oxides, metal oxanions, their supported forms and mixtures for which the metal (s) is (are) chosen from manganese (III) ) to (VII) as defined above c) one or more basifying agent (s), d) and optionally a compartment contains one or more chemical oxidizing agents as defined above and / or water, and / or e) one or more photoirradition sources as defined above, said compositions comprising a), b) and / or c) being aqueous or powdery, with particularly at least one of these compositions being aqueous. 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 a means for delivering the desired mixture onto the hair, for example such as the devices described in the patent FR 2,586,913.

EXAMPLES OF COLORING

Colorimetric results: Hair coloring is visually assessed and read with the Minolta spectrocolorimeter (CM3600d, D65 illuminant, 10 ° angle, SCI values) for the L *, a *, b * colorimetric measurements. In this L * a * b * system, L * represents the intensity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The lower the value of L, the darker or more intense the color. The higher the value of a * the higher the shade is red and the higher the value of b * the hue is yellow. The color variation between the colored locks of untreated (control) and post-treatment untreated white hair is defined by (AE *) according to the following equation: DE * _J (L * ùLo *) 2 + (a * ùao * ) 2 + (b * ùbo *) 2 In this equation, L *, a * and b * represent the measured values after staining of the hair permed at 90% of whites and L * o, ao * and bo * represent the measured values hair permed at 90% untreated whites.

The higher the value of AE, the greater the difference in color between the control locks and the colored locks. 1. Treatment phase with orthodiphenols / extracts: Composition per 100 g: 32 g water 32 g ethanol 32 g propylene glycol 0.168 g of molecule or extract 1.37.10-4 mol of metal derivative

The treatment of the keratinous fibers is carried out by applying with a bath ratio 1 g of lock to 12 g of composition on 90% white permed hair. The pause time after application is 30 minutes in an oven 50 ° C under aluminum foil. 2. Color development phase: Alkaline composition (pH 9.5) per 100 g 2.6 g of ammonium bicarbonate 2 g of monoethanolamine Qsp 100 g water The treatment of the keratinous fibers is then carried out by hair application with a bath ratio of 1 g of hair for 2.5 g of revealing composition. The pause time after application is 10 minutes at room temperature. 3. Rinsing, shampooing and drying. The treatment is finished by rinsing with water, shampooing with a classic shampoo and drying in the hair dryer. Color / 4E results after treatment with locks: Examples Metal Catechin Quercetin Hematoxylin Hematoxylin 1 Mn2O3 (144.7 Orange 11.73 Beige 11.04 Brown 15.79 Violet 19.35 trimethyl 1,4,7-dime triazacyclonona ne) (PF6) 2 [116633-52-4 ].

2 Mn (OAc) 3 - Brown 8.04 beige 14.53 Brown 19.75 Gray- 19.84 2H20 clear -red violet Examples Metal Campeche extract 3 Mn2O3 (144,7 trimethyl 1,4,7 triazacyclononane) (PF6) 2 red brown 14.0 [116633- 52-4].

4 Mn (OAc) 3 - 2H20 brown red 14.3 From the results above in the tables, it is clear that the staining process and the composition according to the invention comprising a) an orthodiphenol and extract associated with b) a derivative of Mn according to the invention in c) alkaline medium can effectively stain that it is on the keratinous fibers characterized in particular by a significant difference in color between the pre-treatment locks (BN) and the colored locks (high AE).

Claims (18)

REVENDICATIONS1. A process for dyeing keratinous fibers, wherein said fibers are treated with: a) one or more orthodiphenol derivative (s), b) one or more metal derivative (s) selected from among metal salts, metal complexes, metal oxides, metal oxanions, their supported forms and mixtures for which the metal (s) is (are) selected from manganese (III) to (VII); and (c) one or more basifying agent (s); it being understood that the pH at the end of the process is alkaline, ie greater than 7 and preferably between 8 and 12. Particularly between 8 and 10.5. 2. The method of dyeing according to the preceding claim wherein the orthodiphenol (s) are chosen from derivatives (s) natural orthodiphenol (s). 3. A method of dyeing according to claim 1 or 2 wherein the ingredient i) is an aromatic ring orthodiphenol selected from benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chromane, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic rings having at least two groups hydroxy carried by two adjacent contiguous atoms of the aromatic ring. 4. The method of dyeing according to any one of the preceding claims wherein the ingredient i) has the following formula (I) or one of its oligomers, in salt form or not: OH (I) R2 formula (I) in which the substituents: R 1 to R 4, which may be identical or different, represent: a hydrogen atom, a halogen atom, a hydroxyl radical, a carboxyl radical, an alkyl carboxylate or alkoxycarbonyl radical, a radical. optionally substituted amino, an optionally substituted linear or branched alkyl radical, an optionally substituted linear or branched alkenyl radical, an optionally substituted cycloalkyl radical, an alkoxy radical, an alkoxyalkyl radical, an alkoxyaryl radical, the aryl group being to be optionally substituted, - an aryl radical, - a substituted aryl radical, - a heterocyclic radical, saturated or unsaturated, bearing or not a cationic or anionic charge, optionally subst ituated and / or optionally fused with an aromatic ring, said aromatic ring being optionally substituted, - a radical containing one or more silicon atoms, where two of the substituents carried by two adjacent carbon atoms R, - R2, R2-R3 or R3 - R4 together form a saturated or unsaturated ring, aromatic or not, substituted or unsubstituted, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings, optionally substituted, optionally containing one or more heteroatoms. 5. Staining process according to the preceding claim wherein the orthodiphenol (s) are chosen from: - flavonos, - anthocyanidins, - anthocyanins or anthocyanins, - orthohydroxybenzoates, - flavones, - hydroxystilbenes, - 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, dihydroxycinnamates, orthopolyhydroxycoumarines, orthopolyhydroxyisocoumarines, orthopolyhydroxycoumarones, orthopolyhydroxyisocoumarones, - orthopolyhydroxychalcones, - orthopolyhydroxychromones, - polyhydroxyquinones, - orthohydroxyxanthones, - 1,2 dihydroxybenzene and its derivatives, - 1,2,4 trihydroxybenzene and its derivatives, - 1,2,3 trihydroxybenzene and its derivatives, - 2,4,5 trihydroxytoluene and its derivatives, - proanthocyanidins, - proathocyanines, - tannic acid, - ellagic acid, - and mixtures of the above compounds. 6. The method of dyeing according to any one of claims 2 to 5 wherein the orthodiphenol (s) natural (s) i) are selected from the extracts of animals, bacteria, fungi, algae, plants. 7. The method of dyeing according to the preceding claim wherein the orthodiphenol (s) natural (s) i) are chosen from: - tea leaf extracts, extracts of rosemary leaves and extracts of mate leaves - fruit extracts, such as grape extracts, bean extracts and / or cocoa pods; - vegetable extracts, such as onion peel extracts; - wood extracts from trees, such as pine bark extracts, logwood extracts. 8. Staining process according to any one of the preceding claims wherein the metal derivative (s) b) are chosen from: A) the derivatives of manganese (III) or Mn (III) selected from i) to xiv ): i) alkali metal or alkaline earth metal manganates such as potassium manganate (III) [12142-17-5], KMnO2, ii) manganese (III) oxide, MnO (OH), iii) sesquioxide of manganese [1317-34-6], iv) dimanganese trioxide [1317-34-6], Mn2O3, and these hydrates Mn2O3. nH2O [1332-63-4] or manganite, v) Mn3O4 trimanganese tetroxide, and the mixture of manganese oxide (II, III) [1317-35-7], vi) manganese (III) phosphate such as MnPO4 hydrate. H2O [14986-93-7], vii) manganese (III) sulphates such as Mn2 (SO4) 3 dimanganese trisulfate [13444-72-9], viii) manganese (III) trihalides and their hydrates such as than MnF3 [7783-53-1], and its hydrate, MnF3. 2H2O, ix) complexes of halogenides, halogenomanganates of type M2 (MnHal5) or M (MnHaI4) with M a monovalent cationic counterion such as an alkali metal, a proton or an ammonium, and Hal represents an atom halogen, particularly fluorine or chlorine, x) manganese (III) phosphate complexes of types, MH2 (Mn (PO4) 2), hydrates M3 [Mn (HPO4) (OH) 2]. H2O, with M as defined above, xi) pyrophosphates of type [Mn2 (H2P2O7) 3] 3 with M as defined above, xii) manganese cyanides (III) of type M3 [Mn (CN) 6] and M3 [Mn (CN) 5 (OH)] with M as defined above, and xiii) the permanganate acid anhydride Mn2O7 and xiv) the manganese (III) complexes with gamma dithioketone ligand / imino / ketone ligand. 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 an atom of hydrogen or a linear or branched (C 1 -C 6) alkyl group, X represents an oxygen atom, a sulfur atom or an N (R) group with R representing a hydrogen atom or a group (C 1 -C 6) ) alkyl, linear or branched, more particularly the ligand is acetylacetone, the complex is then the acetylacetonate of Manganese (III) [14284-89-0] Mn (C5H702) 3; xv) manganese acetate III (Mn (Oac) 3); B) the manganese (IV) or Mn (IV) derivatives chosen from: i) Manganese dioxide (IV) [1313-13-9], MnO2, or pyrolusite, manganites, and their alkali metal salts such as K2O • 4MnO2, and its hydrates MnO2. 2H2O, ii) alkali metal permanganates such as KMnO4, iii) manganese (IV) tetrahalide Mn (HaI) 4, with Hal as defined above, such as manganese tetrafluoride (IV) [15195- 58-1] MnF4, iv) the manganese (IV) salts of M2MnO3 type, with M as defined above, more particularly H2MnO3 or Li2MnO3, v) the mannganese (IV) complexes of MMnX6 type, with X representing an atom of halogen, such as F, or Cl, a CN cyanide group, iodate, and M is as defined above, M particularly represents an alkali metal such as K, more particularly potassium hexafluoride manganese, K2MnF6, M2MnCI6 manganese hexachloride, with M as defined above, the alkali metal hexacyano such as K2Mn (CN) 6, vi) the tricarbonyl manganese complexes such as the (C 1 -C 6) alkyl (C 5 -C 20) complex ) arylmanganese tricarbonyl especially methyl-cyclopentadienylmanganese tricarbonyl [1 2108-13-3], and vii) triperoxymanganate (IV) type M2H2MnO (O2) 2 with M as defined above, such as K2H2MnO (02) 2; viii) Mn2O3 (1,4,7 trimethyl 1,4,7 triazacyclononane) (PF6) 2 [116633-52-4]; C) the manganese (V) or Mn (V) derivatives chosen from alkali metal Manganates (V) or also called hypomanganates such as potassium and sodium manganates [12142-41-5], K3MnO4, K2MnO4, KMnO4 NaMnO4, Na3MnO4 and Na2MnO4; D) the manganese (VI) or Mn (VI) derivatives chosen from Manganates (VI) such as i) manganic acid [54065-28-0], H2MnO4, ii) rubidium manganate (VI) [25583 -21-5], and cesium [25583-22-6] and barium; E) the manganese (VII) or Mn (VII) derivatives chosen from: i) hydrated permanganic acid HMnO4. 2H2O [24653-70-1], ii) permanganyl halides such as permanganyl fluoride [15586-97-7], MnO3F, and iii) alkali metal, ammonium, phosphonium or arsenium permanganates such as [14333-13-2], MnO6 M, tetraphenylphosphonium of permanganate [34209-26-2] (C6H5) 4P + MnO4, tetraphenylarsenium of permanganate [4312-28-1] (C6H5) 4As + MnO4 and the and KMnO4 potassium permanganate. 9. Coloring process according to any one of the preceding claims wherein the alkalinizing agent (s) c) is (are) chosen from: i) the (bi) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives; iv) oxyethylenated and / or oxypropylenated ethylenediamines; v) inorganic or organic hydroxides; vi) alkali metal silicates, such as sodium metasilicates, vii ) amino acids of basic preferences such as arginine, lysine, ornithine, citruline and histidine, and viii) compounds of the following formula (II): Ra \ R b NW-N i \ R ~ Rd (II) wherein W is a propylene residue optionally substituted by a hydroxy group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. 10. The method of dyeing according to any one of the preceding claims wherein the agent (s) alkalinizing (s) (c) is (are) selected from alkanolamines and (bi) carbonates particularly alkaline or alkaline earth. 15 11. The method of dyeing according to any one of the preceding claims which does not implement chemical oxidizing agent other than the oxygen of the air. 12. The method of dyeing according to any one of claims 1 to 10 which uses one or more chemical oxidizing (s) such that: a) ozone; b) the persalts of alkali metal or quaternary ammonium are perborates, persulfates, percarbonates, peroxodiphosphates, Oxone® or potassium persulfate particularly the oxidant is selected from sodium perborate, sodium persulfate, potassium persulfate, ammonium persulfate, sodium percarbonate, potassium percarbonate; c) aliphatic organic C1-C6 and aromatic C6-C20 peracids and their percarboxylate forms: RC (O) O-OM 'with R representing a (C 1 -C 6) alkyl group, or (C 6 -C 20) aryl such that phenyl, M 'representing a hydrogen atom (peracid) an alkali metal or alkaline earth metal (percarboxylate) are selected from performic acid, peracetic acid, perbenzoic acid derivatives, trifluoroacetic acid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid especially the oxidant is peracetic acid; d) organic peroxides chosen from dioxirane, C 1 -C 6 alkyl peroxides, benzoyl peroxide, (C 1 -C 6) alkyl peroxo carboxylates, and bis (C 1 -C 6) alkylsilyl peroxides such as bis (trimethylsilyl) peroxide, C 1 -C 6 alkyl peroxydicarbonates, sodium nonanoyloxybenzene sulfonate; e) the oxidizing anions chosen from nitrites, nitrates, hypochlorites, hypobromites, hypoiodites, chlorites, bromites, iodites, chlorates, bromates, iodates, periodates, more particularly the oxidant is chosen from hypochlorite or alkali metal periodate such as sodium hypochlorite or sodium periodate; f) stable N-oxy radicals (NO.), chosen from: i) heterocycles containing a sterically hindered N-oxide group, such as the 2,2,6,6-tetra (C 1 -C 6) alkylpiperidinooxy radical, 2,2,6,6-tetra (C1-C6) alkylmorpholinooxy; ii) the salts of Frémy nitrosodisulfonates, and iii) the morpholine N-oxide; the oxidant is especially selected from the 2,2,6,6-tetramethylpiperidinyloxy radical; g) hypervalent derivatives of iodine, chosen from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid derivatives, periodinans, alkyls and benzoylhypoiodites, more preferably the oxidant is chosen from iodotriacetate; iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid, Dess-Martin periodinane; diallkyl (C1-C6) carboxylate iodoaryl such as iodobenzene diacetate; h) the following organic compounds: N-halosuccinimides, trichloroisocyanuric acid, N-hydroxyphthalimide, linear or branched C1-C10 alkyl nitrites; the optional supports of these oxidants a) to h) being selectable from silica, alumina, charcoal, charged or neutral polymers; i) hydrogen peroxide or system (s) generator (s) of hydrogen peroxide such as: i-1) urea peroxide; i-2) polymeric complexes which can release hydrogen peroxide such as polyvinylpyrrolidone / H2O2 in particular being in the form of powders and other polymeric complexes; i-3) oxidases producing hydrogen peroxide in the presence of a suitable substrate; i-4) metal peroxides generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; i-v) perborates; or i-vi) percarbonates. 13. Method according to any one of the preceding claims in a step of applying to the keratinous fibers an aqueous composition comprising a), b), and c) as defined in any one of the preceding claims and optionally one or more oxidizing agent (s). (s) chemical (s) as defined in the preceding claim. 14. The method of dyeing according to any one of claims 1 to 12 in two steps consisting in the first step to be applied to the keratin fibers a composition comprising the ingredients a) and b) as defined in any one of claims 1 to 8 and optionally one or more chemical oxidizing agent (s) as defined in claim 12, then in a second step of applying a composition comprising c) as defined in claims 1, 9 or 10 particularly at a pH greater than 7 and preferably between 8 and 12. 15. The method of dyeing according to any one of claims 1 to 12 and 14 carried out in at least two stages ending in the treatment of keratin fibers with the ingredient c) as defined in claims 1, 9 or 10 and can be followed post-treatment steps such as shampooing with conventional shampoo, rinsing for example with water and / or drying keratin fibers by heat treatment. 16. A dyeing method according to any one of the preceding claims implementing one or more photoirradiation (s) by one or more electromagnetic wave (s) of wavelength between 10 nm in the UV field and 100 μm in the IR infrared domain, which comes especially from artificial photoirradiation, in particular UV-emitting lamps, incandescent, halogen, fluorescent, mercury, low-pressure lamps, low-pressure lamps, for example sodium or neon, high-pressure mercury lamps, halide lamps, xenon flash lamps, fluorescent excimer lamps such as xenon lamps, Light Emitting Diodes or LEDs from 50 to 1000mW , lamps emitting black light or Wood's light, and lasers 17. A cosmetic composition for dyeing keratin fibers containing: a) one or more ortho-diphenol derivatives, as defined in any one of claims 1 to 7; b) one or more metal derivative (s) chosen from metal salts, metal complexes, metal oxides, metal oxanions, their supported forms and mixtures for which the metal (s) is (are) chosen (s) from manganese (III) to (VII) as defined in any one of claims 1 or 8; c) one or more basifying agent (s) as defined in any one of claims 1, 9 or 10 and optionally d) one or more chemical oxidizing agent (s) (s) ) as defined in claim 12. 18. Use for dyeing keratinous fibers such as the hair of the following combination: a) one or more ortho-diphenol derivative (s), as defined in any one of claims 1 to at 7; b) one or more metal derivative (s) chosen from metal salts, metal complexes, metal oxides, metal oxanions, their supported forms and mixtures for which the metal (s) is (are) selected from manganese (III) to (VII) as defined in any one of claims 1 or 8; c) one or more basifying agent (s) as defined in any one of claims 1, 9 or 10 and optionally d) one or more chemical oxidizing agent (s) (s) ) as defined in claim 12.