FR2996122A1 - Coloring keratinous fibers, preferably hair, comprises treating fibers with composition including naphthoquinone derivative, magnesium/zinc salt, hydrogen peroxide, bicarbonates and optionally alkalizing agent different from bicarbonate - Google Patents

Abstract

Coloring keratinous fibers, preferably human keratinous fibers such as hair, comprises treating keratinous fibers with cosmetic composition including (a) naphthoquinone derivative, (b) manganese salt or zinc salt, (c) hydrogen peroxide, (d) (bi)carbonates and (e) optionally alkalizing agent different from bicarbonate. An independent claim is included for a device comprising compartments in which the ingredients of composition are distributed.

Description

The present invention relates to a method for dyeing keratinous fibers, in particular human keratin fibers such as the hair, wherein said fibers are processed from one or more cosmetic compositions comprising a) one or more derivative (s) (naphthos) quinone, b) one or more manganese salt (s) or zinc, (c) hydrogen peroxide or one or more hydrogen peroxide generator systems, (d) one or more (bi) carbonate (s) or one or more generator systems (s) ( s) (bi) carbonate (s), and optionally e) one or more basifying agent (s) different (s) of (bi) carbonate (s).

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 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 to the keratinous fibers, bases or a mixture of bases and couplers with hydrogen peroxide (H 2 O 2 or hydrogen peroxide) as an oxidizing agent, to be allowed to diffuse, then to rinse the fibers. The resulting colorations are permanent, strong, and resistant to external agents, including light, weather, washing, perspiration and friction. However, commercial hair colourants that contain them generally have the disadvantage of staining clothing, lead to odor and comfort problems, 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 including manganese and / or zinc. In particular, the documents FR 2814943, FR 2814946, FR2814947, FR 2817469, FR 2838053, FR 2847810, WO2009 / 010684, FR2939654, FR2939645, FR2939648, FR2939644 and FR2939646 provide compositions for coloring the skin or keratinous fibers, comprising a dye precursor which contains at least one orthodiphenol, salts and oxides of manganese and / or zinc, alkalis of the hydrogencarbonate type in a particular ratio: salts and oxides of manganese and zinc / hydrogencarbonate, 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, especially in the case of hair fibers.

There is therefore a need to develop staining processes which make it possible to obtain intense coloring from particular dye precursors, in particular from natural extracts rich in particular dye precursors, while limiting the discoloration of the keratinous fibers. . In particular, there is a need to obtain less aggressive colorings for the hair and at the same time that are resistant to external agents (light, bad weather, shampoo), which are stubborn and homogeneous while remaining intense and 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 said composition or compositions, the following ingredients: a) one or more derivatives (naphthos) quinone, b) one or more manganese salt (s) or one or more zinc salts, ) hydrogen peroxide or one or more hydrogen peroxide generator systems, d) one or more (bi) carbonate (s) or one or more generator systems (s) of bi) carbonate (s), and optionally e) one or more basifying agent (s) different (s) of (s) or (s) bicarbonate (s). According to a particular embodiment of the dyeing process according to the invention, the compound (s) d) and optionally e) are: - either applied in admixture with the compounds a), b) and c), - is applied separately after applying a cosmetic composition comprising the compound (s) a), b) and c), or is applied together with the compound c) after application of a cosmetic composition comprising the ingredients a) and b), or applied together with compounds a) and c) after application of a cosmetic composition comprising ingredient b). The present invention also relates to a cosmetic composition for dyeing keratinous fibers comprising: a) one or more derivative (s) (naphthos) quinone, b) one or more salt (s) of manganese or one or more salt (s) ) zinc, (c) hydrogen peroxide or one or more hydrogen peroxide generator systems, (d) one or more (bi) carbonate (s) or generator system (s) (s) (bi) carbonate (s), and optionally e) one or more basifying agent (s) different (s) of (s) or (s) bicarbonate (s). Preferably, the dye composition is aqueous. Another subject of the present invention relates to a multi-compartment device comprising: a) one or more derivative (s) (naphthos) quinone, b) one or more salt (s) of manganese or one or more salt (s) of zinc (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) (bi) carbonate (s), and optionally e) one or more basifying agent (s) different (s) of (s) or (s) bicarbonate (s).

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 keratinous fibers, with results of intense 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 according to the present invention give homogeneous colors from the root to the tip of the fibers (low color selectivity). Other objects, features, aspects and advantages of the present invention will become more apparent upon reading the description and examples which follow. a) derivative (naphtho) quinone According to the present invention, the dyeing process uses one or more derivative (s) (naphthos) quinone. One particular embodiment relates to aromatic (naphtho) quinone derivatives or mixtures of the (naphtho) quinone derivatives, comprising at least one aromatic carbon cycle comprising at least two oxy (= O) groups borne by the two carbons situated in position 1 and 4. (in the para position) of said ring, it being understood that two adjacent carbon atoms of the aromatic ring can not carry two hydroxyl (OH) groups.

The aromatic ring may be more particularly a condensed ring, that is to say that at least one saturated or non-saturated, non-aromatic ring, optionally containing one or more heteroatoms, is attached to said aromatic ring. The (naphtho) quinones according to the invention can be salified or not. They can also be in the form of aglycone (without bound sugar) or in the form of glycosylated compounds. More particularly, the derivative (naphtho) quinone a) represents a compound of formula (I) or one of its oligomers, enantiomers, diastereoisomers, in salified or non-salified form, in the form of an aglycone or not: (I) I) in which the substituents: R1 to R6, which may be identical or different, represent: a hydrogen atom, a halogen atom, a hydroxyl radical, a carboxyl radical, an alkyl carboxylate radical or an alkoxycarbonyl radical, an alkylcarbonyloxy group, an HC (O) -O- group, an optionally substituted amino group, an optionally substituted linear or branched alkyl group, an optionally substituted linear or branched alkenyl radical, an optionally substituted cycloalkyl radical, an optionally substituted alkylcarbonyl radical, a carboxyaldehyde 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 fused with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted especially by one or more hydroxyl or glyco syloxy groups; - a radical containing one or more silicon atoms, - or two of the substituents carried by two adjacent carbon atoms R1-R2, R3-R4, R4-R5 or R5-R6 together with the carbon atoms carrying them a ring saturated or unsaturated, nonaromatic, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms.

In particular, R1 to R6 together form two to four rings. It being understood that two hydroxy radicals can not be carried by adjacent carbons of the aromatic ring. 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 C 1 -C 10, such as methoxy, ethoxy, propoxy and butoxy. The alkoxyalkyl radicals are preferably the (C 1 -C 20) alkoxy (C 1 -C 20) 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 halogenated radicals are fluorine, chlorine, bromine and iodine atoms. The alkylcarbonyl radicals are alkylcarbonyl radicals with alkyl as defined above, preferably C1-C10, such as acetyl, propionyl. The alkoxycarbonyl radicals are -OC (O) alkyl radicals as defined above, such as acetate, propionate , citrate, tartrate, gluconate, lactate. 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 quaternary ammonium radical -N-PR'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 1 represents the counterion of the corresponding organic, inorganic or halide acid; 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: 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, different from or different from nitrogen, o a group quaternary ammonium -N-PR'R "R" ', 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 counter-ion of the corresponding organic or inorganic acid, or a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted by a (C 1 -C 4) alkyl radical; preferentially methyl; an acylamino radical (-N (R) -C (O) R ') 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 a C1-C2 alkyl radical; a carbamoyl radical ((R) 2 N-C (O) -) 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'S (O) 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 radical R 'represents a radical; C1-C4 alkyl, a phenyl radical; an aminosulfonyl radical ((R) 2 N -S (O) 2 -) in which the R radicals, 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; a carboxylic radical in acid or salified form (preferably with an alkali metal or an 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 with one or more non-adjacent 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 Ci-Cio alkyl radical, preferably C 1 -C 8, optionally substituted by one or more radicals selected from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (PolY) -hydroxyalkoxy, acylamino, amino substituted by two identical or different alkyl radicals, C 1 -C 8 C4, optionally carrying at least one hydroxyl group or both radicals may form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 members, preferably 5 or 6 members, saturated or unsaturated optionally substituted optionally comprising another heteroatom identical to or different from the nitrogen; a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C1-C10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; 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: 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, different from or different from nitrogen, o a group quaternary ammonium -N + R'R "R" ', 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 counter-ion of the corresponding organic or inorganic acid, or a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted by a (C 1 -C 4) alkyl radical; preferentially methyl; an acylamino radical (-N (R) -C (O) R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group and the radical R is a C1-C2 alkyl radical; a carbamoyl radical ((R) 2 N-C (O) -) 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'S (O) 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 radical R 'represents a radical; C1-C4 alkyl, a phenyl radical; an aminosulfonyl radical ((R) 2 N -S (O) 2 -) in which the R radicals, 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; a carboxylic radical in acid or salified form (preferably with an alkali metal or an 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 "optionally substituted amino" radical is meant an amino radical in which one or two of the hydrogen atoms may be replaced by one or two identical or different C1-C6 alkyl radicals optionally carrying at least: o a grouping hydroxy, an amino group optionally substituted by one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, saturated or unsaturated; optionally substituted optionally comprising at least one other heteroatom different or different from nitrogen, 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, 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 non-adjacent OH groups.

More particularly, the (naphtho) quinones that can be used in the process of the invention according to a) are of formula (I) in which the substituents R1 to R6, which are identical or different, represent: a hydrogen atom; a hydroxyl radical; - an alkyl radical, - an alkenyl radical, - an alkoxy radical, - an alkylcarbonyl radical, - an alkoxycarbonyl radical, - a halogen radical. Even more preferentially, the (naphtho) quinones that can be used in the process of the invention according to i) are of formula (I) in which the substituents: R 1 and R 2, which are identical or different, represent: a hydrogen atom; a hydroxyl radical, an alkyl radical, an alkenyl radical, an alkoxy radical, an alkylcarbonyl radical, an alkoxycarbonyl radical, a halogen radical. R3 and R6, which may be identical or different, represent: a hydrogen atom, a hydroxyl radical, an alkyl radical, an alkoxy radical, an alkoxycarbonyl radical, an alkenyl radical. R4 and R5, which may be identical or different, represent: a hydrogen atom, a hydroxyl radical, an alkyl radical, an alkoxy radical, an alkoxycarbonyl radical, an alkenyl radical or an alkylcarbonyl radical. Preferably, the (naphtho) quinones according to the invention do not comprise two hydroxy groups carried by two adjacent carbons. According to a particular embodiment of the invention the (naphtho) quinones a) are quinones of formula (Ia) as follows: O (la) Compound (Ta) with R1, R2, R3 and R4 as defined above. Preferably, the substituents R1 and R3, which are identical or different, preferably identical, represent a hydroxyl or alkoxy group which is particularly hydroxy, and / or R2 and R4, which are identical or different, represent a hydrogen atom or an alkyl or alkoxy group, particularly R2 is alkoxy and R4 is alkyl. According to another particular embodiment of the invention, the (naphtho) quinones a) are naphthoquinones of the following formula (Ib): O (Ib) Compound (Ib) with R1, R2, R3, R4, R5 and R6 such as than previously defined. Preferably, taken together or separately, R 1 represents a hydrogen atom, a hydroxyl or alkoxy group; R2 represents a hydrogen atom or alkoxy; R3 represents a hydrogen atom or a hydroxy group; R4 represents a hydrogen atom, a hydroxy group or alkyl; R5 represents a hydrogen atom or a hydroxy group; and / or R6 represents a hydrogen atom. According to a particular embodiment of the invention, the (naphthos) quinones a) are chosen from the following compounds: ## STR1 ## dihydroxy-3-methoxy-6-methylcyclohexa-2,5-diene-1,4-dione in which the formula is 1-methyl-4-hydroxy-2-methoxy-1,4-naphthoquinone; lawsone 6 0 1 0 el 0 0 2,5-dimethoxycyclohexa-2,5-diene-1,4-dione 0 7 ,, OH OH O 2-hydroxy juglone 8 0 ,, OH 0 0 2-hydroxy-5-methoxy -1,4-naphthoquinone 9 0 OH-7-methyl-juglone More preferentially the (naphtho) quinones a) are chosen from compounds 1, 2, 3, 5, 7, 8 and 9. The (naphtho) quinones useful in the process of the invention may be natural or synthetic. Natural (naphtho) quinones include compounds that may be present in nature and that are reproduced by (hemi) chemical synthesis. The (naphtho) quinone salts 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 (naphthio) quinone derivative (s) which do not exist in nature. According to another preferred embodiment of the invention, the composition that is useful in the process for staining keratinous fibers comprises as ingredient a) one or more natural (naphthoquinone) derivative (s).

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 natural (naphtho) quinones are derived from extracts of animals, bacteria, fungi, algae, plants and fruits used in whole or in part. Especially 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 (naphtho) quinones as defined above. Preferably, the natural or (naphtho) quinones 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 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. It is also possible to use mixtures of plant extracts. Preferably these extracts do not contain orthodiphenols. According to a particular embodiment of the invention, the (naphtho) quinone derivative (s) are natural extracts rich in (naphtho) quinones. According to a preferred mode, the derivative (s) of (naphtho) quinones 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) of synthetic (naphtho) quinone (s), natural (s), and / or the natural extract (s) used (s) as an ingredient a) in one or more composition (s) useful in the process according to the invention preferably represent (s) from 0.001% to 20% by weight of the total weight of the composition (s) containing the naphthol (s) ) quinones or the extract (s). As regards the pure (naphtho) quinones, 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 or Zinc Salt The dyeing process according to the invention uses one or more manganese salts (Mn) or one or more zinc salts (Zn). The manganese or zinc 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, such as manganese oxides, 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; carboxylic acid salts 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. As an example of polymeric salts, mention may be made of polyvinylpyrrolidone carboxylate of manganese. 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 sulfate monohydrate and manganese gluconate. The salts used advantageously are manganese gluconate and manganese chloride.

Among the zinc salts, mention may be made of zinc sulfate, zinc gluconate, zinc chloride, zinc lactate, zinc acetate, zinc glycinate and zinc aspartate. Preferably, the manganese salts are chosen from i) oxides of manganese and ii) halides, sulphates, phosphates, nitrates and perchlorates, salts of carboxylic acids such as gluconates and mixtures thereof, and salts of zinc are selected from zinc sulfate, zinc gluconate, zinc chloride, zinc lactate, zinc acetate, zinc glycinate and zinc aspartate; and more particularly, salts b) are carboxylic acid salts of manganese. The manganese and zinc salts 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 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 or zinc salts or salts used represent from 0.001% to 0.1% by weight approximately of the total weight of the composition (s) containing the metal salt (s) and still more preferably from 0.05% to 10% by weight approximately. In particular, the metal salts of the invention are of oxidation states 2 such as Mn (II) and Zn (II). Preferably, the dyeing method of the invention uses one or more manganese salts, in particular the metal salts of Mn (II). Even more preferably, the manganese salt or salts are chosen from carboxylic acid salts of manganese, especially manganese gluconate and manganese halides, such as manganese chloride; and more particularly manganese gluconate. c) hydrogen peroxide and hydrogen peroxide In the context of the present invention, the third component is hydrogen peroxide or a hydrogen peroxide generating system such as: a) urea peroxide; b) polymer complexes which can release hydrogen peroxide, such as polyvinylpyrrolidone / H 2 O 2, in particular being in the form of powders and the 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; e) perborates; or f) 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 releasing hydrogen peroxide selected from polyvinylpyrrolidone / H2O2; c) oxidases; e) perborates and f) percarborates. In particular, the third component is hydrogen peroxide or urea 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 (generator) of (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.

The (bi) carbonates or the (bi) carbonate generating system (s) may be used in one or more cosmetic compositions during the coloring process. By "(bi) carbonate carbonate generator 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. The (bi) carbonate is or is selected from: a) alkali metal (Met2 +, CO32-), alkaline earth metal (Met2 +, CO32-), ammonium carbonates ((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 are identical or different, represent a hydrogen atom, a optionally substituted (C1-C6) alkyl group such as hydroxyethyl, b) bicarbonates, also known as hydrogenocarbonates, of the following formulas: R '+, HCO3- with R' representing a hydrogen atom, an alkali metal, an ammonium group R "4N + - or phosphonium R" 4P + - where R ", identical or different, represent a hydrogen atom, an optionally substituted (CiC6) alkyl group such as hydroxyethyl and when R 'represents a hydrogen atom the hydrogen carbonate 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 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 (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. e) basifying agent (s) different from or of bicarbonate (s) The basifying agent, which can be used in the dyeing process according to the invention as the fifth ingredient, is different from or (bi) carbonates d) 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) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citruline and hystidine, and vii) compounds of formula (II) ) wherein: - W is a divalent group (Ci-C8) alkylene, preferably propylene, optionally substituted in particular with a hydroxyl group or an alkyl radical - Ra, Rb, R 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 are preferably selected from i) the hydroxides of an alkali metal, ii) the hydroxides of an alkaline earth metal, such as hydroxides of sodium or potassium, iii) the hydroxides of a metal of such as the hydroxides of Group III, IV, V and VI metals, iv) the 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 agent (s) alkalinizing (s) d) as defined above may represent preferably from 0.001% to 10% by weight of the weight 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. 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 d) and optionally e) 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 d) and optionally e) as defined above. cosmetic compositions: 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 solvents. organic 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, mention may be made, for example, of 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 adjuvants: The composition or compositions that are useful for carrying out the dyeing method according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic surfactants, 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 , antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides preservatives, 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, 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. the additional dyes: The dyeing process using the ingredients a) to d) and optionally e) as defined previously may furthermore use 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, acid or cationic, natural direct dyes such as 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, satin, curcumin, spinulosine, 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 ingredients a) to d) and optionally e) as defined above, or the composition (s) of the dyeing process according to the invention. The invention preferably represents from 0.001% to 10% by weight of the total weight of the composition or the composition (s) and even more preferably from 0.05% to 5% by weight approximately. The composition according to the invention or the composition (s) of the process implementing the ingredients a) to e) 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, bis-phenylalkylenediamines, 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 said composition (s) are used in the process are generally present each in an amount of between 0.001 to 10% by weight of the total weight. 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 one embodiment, the pH of the cosmetic composition (s) containing d) one or more (bi) carbonate (s) or one or more system (s) generator (s) (bi) carbonate (s) is alkaline, is 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 composition cosmetic composition comprising d) one or more (bi) carbonates or one or more generator systems of (bi) carbonate (s) and optionally e) one or more agent (s) alkalinizing (s) different from (bi) carbonate ( s) is alkaline, ie greater than 7, preferably between 8 and 12.

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 for generating peroxide of hydrogen is preferably less than 7, more particularly between 1 and 5. In particular, the cosmetic composition consisting solely of hydrogen peroxide has a pH of less than 7. Preferably, the composition or compositions containing the derivative (s) ( naphtho) quinone and not containing (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.

The pH of these compositions can be adjusted to the desired value by means of alkalinizing or acidifying agents usually used in 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, there may be mentioned alkalinizing agents d) defined above. 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); ) (naphthos) quinone, (b) one or more manganese salt (s) or one or more zinc salts, (c) hydrogen peroxide or one or more hydrogen peroxide generator (s) systems hydrogen, d) one or more (bi) carbonate (s) or a plurality of (s) carbonate generator (s), and optionally e) one or more basifying agent (s) different from (bi) carbonate (s).

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. According to another particular embodiment of the invention, the method for dyeing keratin fibers is carried out in two stages.

In a first two-step process variant, the first step consists in applying to said fibers a composition comprising the ingredients a), b), c) as defined above, then in a second step a composition comprising the ingredients d) and optionally e) as defined above is applied to said fibers, preferably being understood that at least one of the two compositions is aqueous. According to a preferred embodiment, the composition comprising ingredients a), b) and c) is aqueous. According to another embodiment of the invention the composition comprising the ingredients d) and optionally e) is an aqueous composition. Preferably, the two compositions are aqueous. In addition, these compositions may contain one or more fatty substances such as liquid petrolatum. In a second variant of two-step keratinous fiber staining 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 second composition comprising the ingredients c), d) and optionally e) as defined above is applied to said fibers. In a third variant of the two-step keratinous fiber staining process, the first step comprises applying to said fibers a composition comprising ingredient b), as defined above, then in a second step a composition comprising the ingredients a) , c), d) and optionally e) as defined above is applied to said fibers. According to a particular dyeing process of the invention, said method is carried out in at least two stages ending in the treatment of keratinous fibers with ingredient d), and optionally e), and may be followed by post-treatment stages. treatment such as washing with a conventional shampoo, rinsing for example with water and / or drying the keratinous fibers by heat treatment as defined below; it being understood that said process does not involve intermediate rinsing just before the step which uses ingredient d). Preferably, the process according to the invention is carried out in at least two stages does not involve intermediate rinsing between the first and the second stage ie between the application of the mixture of ingredients a), b), c) and d) or between the application of mixture a), b) and mixture c), d). According to a particularly advantageous method, the keratinous fibers are just before the step which uses ingredient d): a) either wiped mechanically as described below, b) be dried by heat with a heat treatment as described below, c) either not rinsed, that is to say that the steps are done successively.

Preferably, between the first and second stages of the dyeing process of the invention, the fibers are: a) mechanically wiped as described below, b) heat-dried with a heat treatment as described herein after, c) either not rinsed, that is to say that steps 1 and 2 are successively. More preferably, between the first and second stages, the fibers are preferably wiped with a towel or absorbent paper, or are heat-dried with a heat treatment at a temperature particularly between 60 and 220 °. C and preferably between 120 and 200 ° C. According to another particular embodiment of the invention, between the application of the mixture of ingredients a), b), c) and d) or between the application of mixture a), b) and mixture c), d), the locks are rinsed very rapidly, between 1 second and 1 minute, more particularly between 1 second and 30 seconds, and preferably between 2 and 5 seconds, such as 2 seconds, under the water of a faucet or spray jet. This rapid rinsing step is followed by mechanical wiping as described below.

For these last three 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 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 45 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.

Whatever the mode of application, 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 containing ingredient d). 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 may be 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 4 or even 5 compartments containing from 2 to 4, or even 5 compositions in which the ingredients are distributed: a) one or more derivative (s) (naphthos) quinone, b) one or more manganese salt (s) or one or more zinc salts, (c) hydrogen peroxide or one or more hydrogen peroxide generator systems, (d) one or more (bi) carbonate (s) or one or more system (s) generator (s) of bicarbonate (s), and optionally e) one or more agent (s) alkalinizing (s) different from (bi) carbonate (s), said compositions being aqueous or powdery, 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 patent FR 2586913. The following examples serve to illustrate the invention without however presenting a Limiting Characteristics. Staining Examples In the following example, the rise in AE * staining was evaluated from the color of the colored hair and the initial color of the uncolored hair. 1. Compositions tested Composition Derivative (naphthos) quinone a) 0.420g Manganese Gluconate b) 0.003g Hydrogen Peroxide * c) 1.2g Ethanol 13.2g Propylene Glycol 13.2g Water Qsp 100g (*) 0.144 g 167-volume hydrogen peroxide The (naphtho) quinone derivatives used in composition A have the following structure: No. Ingredient a) 1 OH OH Lele OH 0 Flaviolin 2 OH OH O O I 2,5-dihydroxy-3- methoxy-6-methylcyclohexa-2,5-diene-1,4-dioneyl ether OH 0 Juglone 0 o leiel4, OH 0 5-hydroxy-2-methoxy-1,4-naphthoquinone 0 o leiel5, 0 Methyl lawsone 6 2,5-dimethoxycyclohexa-2,5-diene-1,4-dione 7 0 -OH-hydroxy-2-hydroxy-hydroxy-8-hydroxy-5-methoxy 1,4-naphthoquinone 0 9 OH 0 7-methyl juglone Composition B developer Amount Sodium bicarbonate d) 2,6g Monoethanolamine e) 2g Demineralized water qs 100g 2. Procedure Composition A is applied to strands of natural hair at 90 ° C. % permanent whites, at a rate of 12 grams of composition for 1 gram of hair. It is then left to stand for 30 minutes at a temperature of 50 ° C. under aluminum foil. 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 per 1 gram of lock. Composition B has a pH = 9.5. The pause 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 4E * staining is measured. 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. Variation in staining between white locks of hair with 90% of untreated white (90 BP) (Lo * = 47.7, ao * = 0.4, bo * = 9.2) and after staining (L * a * b *) are defined by (AE *) according to the following equation: 4E * =. \ / (L * -L0 *) 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 AE *, the better the rise of the color.

The value of the increase of the coloring AE * is given in the table below: No. AE * AL * Aa * Ab * 1 32 28 15 1 2 17 16 1 6 3 27 27 6 1 5 10 9 3 0 7 18 12 11 8 8 19 12 10 11 9 19 14 6 12 It can be seen that the dyeing process according to the invention makes it possible to lead to a very satisfactory increase in color.

Claims (21)

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 derivative (s) (naphthos) quinone, b) one or more manganese salt (s) or one or more zinc salt (s), c) hydrogen peroxide or one or more generator systems (s) ) hydrogen peroxide, d) one or more (bi) carbonate (s) or one or more bi-carbonate (s) generator system (s), and optionally e) one or more agent (s) ) different alkalinizing agent (s) from the bicarbonate (s). 2. Staining process according to claim 1, characterized in that the derivative (naphtho) quinone a) represents a compound of formula (I) or one of its oligomers, enantiomers, diastereoisomers, in salified form or not, in the form of aglycone or not: (I) formula (I) in which the substituents: R1 to R6, which may be identical or different, represent: a hydrogen atom, a halogen atom, a hydroxyl radical, a carboxyl radical; an alkylcarbonyloxy group; an HC (O) -O- group; an alkyl or alkoxycarbonyl carboxylate group; an optionally substituted amino group; an optionally substituted linear or branched alkyl group; a linear or branched alkenyl group; optionally substituted, - an optionally substituted cycloalkyl radical, - an alkylcarbonyl radical, - a carboxyaldehyde 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 with an aromatic ring, preferably benzene, said ring aromatic being optionally substituted especially by one or more hydroxy or glycosyloxy groups, - a radical containing one or more silicon atoms, - or two of the substituents borne by two adjacent carbon atoms R1-R2, R3-R4, R4-R5 or R5 -R6 together with the carbon atoms carrying them a saturated or unsaturated, non-aromatic ring, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms, it being understood that two hydroxyl radicals can not be carried by adjacent carbons of the aromatic ring. 3. A method of dyeing according to claim 1 or 2, characterized in that the derivatives (naphtho) quinone are selected parmiceux of formula (I) wherein the substituents R1 to R6, identical or different, represent: - a hydrogen atom - a radical - a radical - a radical - a radical - a radical - a radical a radical 4. Process hydroxy, alkyl, alkenyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, halogen. staining composition according to any one of claims 1 to 3, characterized in that the (naphtho) quinone derivatives are chosen from those of formula (I) in which the substituents: R 1 and R 2, which are identical or different, represent: hydrogen atom, - a hydroxy radical, - an alkyl radical, - an alkenyl radical, - an alkoxy radical, - an alkylcarbonyl radical, - an alkoxycarbonyl radical, - a halogen radical. R3 and R6, which may be identical or different, represent: a hydrogen atom, a hydroxyl radical, an alkyl radical, an alkoxy radical, an alkoxycarbonyl radical, an alkenyl radical. R4 and R5, which may be identical or different, represent: a hydrogen atom, a hydroxyl radical, an alkyl radical, an alkoxy radical, an alkoxycarbonyl radical, an alkenyl radical or an alkylcarbonyl radical. 5. Staining process according to any one of claims 1 to 4, characterized in that the derivatives (naphtho) quinone a) are quinones of formula (la): 0 0 (la) compound (Ta) with R1, R2, R3 and R4 as defined in any one of claims 2 to 4, especially the substituents R1 and R3, identical or different, preferably identical, represent a hydroxyl or alkoxy group, more particularly hydroxy, and / or R2 and R4, identical or different, represent a hydrogen atom or an alkyl or alkoxy group, particularly R2 is alkoxy and R4 is alkyl. 6. A method of dyeing according to any one of claims 1 to 4, characterized in that the derivatives (naphtho) quinone a) are naphthoquinones of formula (Ib): (Ib) compound (Ib) with R1, R2, R3, R4, R5 and R6 as defined in any one of claims 2 to 4, especially, taken together or separately, R1 represents a hydrogen atom, a hydroxy group or an alkoxy group; R2 represents a hydrogen atom or alkoxy; R3 represents a hydrogen atom or a hydroxy group; R4 represents a hydrogen atom, a hydroxy group or alkyl; R5represents a hydrogen atom, or a hydroxy group; and / or R6 represents a hydrogen atom. 7. The method of dyeing according to any one of the preceding claims, characterized in that the derivatives (naphthos) quinone a) are chosen from the following compounds: No. Ingredient a) 1 0 HO OH lele OH 0 Flavioline 2 0 si OH HO 0 0 1 2,5-Dihydroxy-3-methoxy-6-methylcyclohexa-2,5-diene-1,4-dione 0 leiel OH 0 Juglone 0 o leiel4, OH 0 5-hydroxy-2-methoxy-1 , 4-naphthoquinone o, leiel5, 0 Methyl lawsone 5-dimethoxycyclohexa-2,5-diene-1,4-dione 7 0 ,, OH OH O 2-hydroxy juglone 8 0, Preferably, the (naphtho) quinones a) are chosen from compounds 1, 2, 3, 5, 7, 8, 8-hydroxy-5-methoxy-1, 4-naphthoquinone and the like. and 9. 8. Staining process according to any one of the preceding claims, characterized in that the derivatives (naphthos) quinone are natural, more particularly chosen from animal extracts, bacteria, fungi, algae, plants and of fruits. 9. Staining process according to any one of the preceding claims, characterized in that: - the manganese salts, ingredient b), are chosen from: i) oxides of manganese and ii) halides, sulphates, phosphates, nitrates and perchlorates, the salts of carboxylic acids such as gluconates and mixtures thereof, and the zinc salts, ingredient b), are chosen from zinc sulphate, zinc gluconate, zinc chloride and lactate. zinc, zinc acetate, zinc glycinate and zinc aspartate; and more particularly, salts b) are carboxylic acid salts of manganese. 10. The method of dyeing according to any one of the preceding claims, characterized in that the ingredient c) is hydrogen peroxide or urea peroxide. 11. The method of dyeing according to any one of claims 1 to 10, wherein the composition comprises as ingredient c): - polymeric complexes which can release hydrogen peroxide selected from polyvinylpyrrolidone / H2O2; oxidases producing hydrogen peroxide in the presence of a suitable substrate; - perborates; or - percarborates. 12. Coloring method according to any one of the preceding claims, characterized in that the or (bi) carbonates, ingredient d), are alkali, alkaline-earth or ammonium (bi) carbonates. 13. The method of dyeing according to any one of the preceding claims, characterized in that the alkali or different alkali or (s) bicarbonate (s), ingredient e), are selected from: - ammonia, - the alkanolamines, oxyethylenated ethylenediamines, oxypropylenated ethylenediamines, mineral or organic hydroxides, alkali metal silicates, amino acids, and compounds of the following formula (II): Ra Rb N-W-N Rc Rd (II) formula (II) wherein: - W is a divalent group (C 1 -C 8) alkylene, preferably propylene, optionally substituted in particular with a hydroxyl group or a C 1 -C 4 alkyl radical; - Ra, Rb, R, and Rd, identical or different, represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroxyalkyl radical; preferably, the alkaline agent (s) e) are chosen from alkanolamines, in particular monoethanolamine. 14. The method of dyeing according to any one of the preceding claims, characterized in that it is carried out in one step and that it consists in applying to the keratinous fibers an aqueous composition comprising the ingredients a), b), c) , d) and optionally e) as defined in any one of the preceding claims. 15. Coloring process according to any one of claims 1 to 13, characterized in that it is carried out in two stages and consists in applying to said fibers a composition comprising the ingredients a), b) and c) as defined in any one of claims 1 to 11, then in a second step to apply to said fibers a composition comprising the ingredients d) and optionally e) as defined in any one of claims 1, 12 and 13 . 16. The method of dyeing according to any one of claims 1 to 13, characterized in that it is carried out in two steps and that it consists in applying to said fibers a composition comprising the ingredients a) and b) as defined according to any one of claims 1 to 9, then in a second step to be applied to said fibers a composition comprising the ingredients c), d) and optionally e) as defined in any one of claims 1 and 11 to 13 . 17. The method of dyeing according to any one of claims 1 to 13, characterized in that it is carried out in two steps and that it consists in applying to said fibers a composition comprising ingredient b), as defined according to claim 1 or 9, then in a second step a composition comprising the ingredients a), c), d) and optionally e) as defined in any one of claims 1 to 8 and 10 to 12. 18. The method of dyeing according to any one of claims 1 to 13 and 15 to 17, carried out in at least two stages ending in the treatment of keratin fibers with the ingredient d) as defined in claims 1 or 8 and which can be followed by post-treatment steps such as washing with a conventional shampoo, rinsing for example with water and / or drying the keratinous fibers by heat treatment; it being understood that said process does not involve intermediate rinsing just before the step which uses ingredient d). 19. The method of dyeing according to any one of claims 1 to 13 and 15 to 17, wherein the keratinous fibers are just before the step that uses the ingredient d): a) is wiped mechanically, b) either dried by heat with a heat treatment, c) not rinsed that is to say that the steps are done successively. 20. Cosmetic composition for dyeing keratinous fibers containing compounds a), b), c), d) and optionally e) as defined according to any one of claims 1 to 13. 21. Multi-compartment device, characterized in that it comprises 2 to 5 compartments containing 2 to 5 compositions, in which are distributed ingredients a), b), c), d), and optionally e) such that defined according to any one of claims 1 to 13, said compositions being aqueous or powdery, at least one of these compositions being aqueous.