FR3055542A1 - PROCESS FOR TREATING KERATIN FIBERS USING ONE OR MORE DERIVATIVES OF ORTHO-DIHYDROXY-1,2-DIPHENYLETHYLENE, (HYDROGENO) CARBONATES AND ADDITIONAL POLYPHENOLS - Google Patents

Abstract

The present invention relates to a process for treating keratinous fibers, in particular human keratinous fibers such as the hair, comprising the application to said fibers of one or more ortho-dihydroxy-1,2-diphenylethylene derivatives, of one or more polyphenols other than ortho-dihydroxy-1,2-diphenylethylenes, one or more derivatives of manganese and / or zinc, and one or more (hydrogen carbonates). The present invention also relates to a multi-compartment device suitable for the implementation of the invention.

Description

® FRENCH REPUBLIC

NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number: 3,055,542 (to be used only for reproduction orders)

©) National registration number: 16 58270

COURBEVOIE

©) Int Cl ⁸ : A 61 K8 / 27 (2017.01), A 61 K8 / 30, A 61 Q 5/10

A1 PATENT APPLICATION

©) Date of filing: 06.09.16. ©) Applicant (s): L'OREAL Société anonyme— FR. (30) Priority: ©) Inventor (s): JEGOU GWENAELLE and PRUCHE FRANCIS. (43) Date of public availability of the request: 09.03.18 Bulletin 18/10. (56) List of documents cited in the report preliminary research: Refer to end of present booklet (© References to other national documents ©) Holder (s): L'OREAL Société anonyme. related: ©) Extension request (s): @) Agent (s): CASALONGA & ASSOCIES.

PROCESS FOR THE TREATMENT OF KERATINIC FIBERS USING ONE OR MORE DORTHO-DIHYDROXY-1,2-DIPHENYLETHYLENE DERIVATIVES, (HYDROGENO) CARBONATES AND ADDITIONAL POLYPHENOLS.

FR 3 055 542 - A1 (£ // The present invention relates to a process for treating keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said fibers of one or more ortho derivatives. dihydroxy-1,2-diphenylethylene, of one or more polyphenols other than ortho-dihydroxy-1,2diphenylethylenes, of one or more manganese and / or zinc derivatives, and of one or more (hydrogen) carbonates.

The present invention also relates to a device with several compartments suitable for implementing the invention.

i

Process for treating keratin fibers using one or more ortho-dihydroxy-1,2-diphenylethylene derivatives, (hydrogen) carbonates and additional polyphenols

The present invention relates to a process for the treatment of keratin fibers, in particular human keratin fibers such as the hair, comprising the application of one or more ortho-dihydroxy-1,2-diphenylethylene derivatives in combination with one or more manganese and / or zinc derivatives, one or more (hydrogen) carbonates and one or more polyphenols different from ortho-dihydroxy-1,2,2-diphenylethylene derivatives.

For a long time, many people have sought to modify the color of their hair and in particular to mask their gray hair. To do this, there are basically two types of coloring that have been developed.

The first type of coloring is the so-called permanent or oxidation coloring, which uses dye compositions containing oxidation dye precursors, generally called oxidation bases. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors.

Most of these permanent coloring procedures provide a good level of coverage for gray hair. However, they require the presence of an oxidizing agent in a strong alkaline medium (pH generally greater than 10) and these conditions are all the harder since the desired degree of coverage of the white hair of the hair is important.

The second type of coloring is the so-called semi-permanent coloring or direct coloring which consists in applying to the keratin fibers direct dyes which are colored and coloring molecules, having an affinity for the fibers, to be allowed to pause to allow the molecules to penetrate, by diffusion inside the fiber, then rinse them.

In order to achieve these colorations, the direct dyes generally used are chosen from benzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane direct dyes. Direct dyes can also be natural dyes.

However, the resulting colorings are particularly chromatic but temporary or semi-permanent colorations because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their poor resistance to washing.

In view of these drawbacks, consumers are increasingly looking for different coloring methods than the conventional oxidation coloring and direct coloring methods. Consumers are looking in particular for processes using natural type dyes, the implementation of which is not aggressive for keratin fibers and in particular which does not require the use of oxidizing agents, and which is more respectful of the environment. Consumers are in particular looking for well-tolerated coloring methods, which lead to the most natural appearance possible.

In traditional Chinese medicine, largely oral and based on the ancestral use of natural products, we know the use of plant extracts such as Black Shou Wu (hereinafter "B SW"), extracted from the roots Radix Poligoni Multiflori, which is used in particular as a hair loss and regrowth agent, conditioner and anti-dandruff agent.

Furthermore, the use of Poligonum Multiflorum extract has been mentioned for obtaining blonde colors, in particular in patent application DE 197 16 074.

There is a real need to develop new methods for coloring keratin fibers which make it possible to obtain hair coloring while overcoming the drawbacks mentioned above. These methods must in particular make it possible to cover gray hair.

There is also a need to achieve white hair coloring gradually to avoid a sudden change in the appearance of the user. Progressive coloring should have a natural effect. They must also make it possible to cover the hair in a uniform manner.

These methods must also be easy to apply.

The Applicant has surprisingly discovered that the use of one or more derivatives of ortho-dihydroxy-1,2-diphenylethylene, of one or more polyphenols different from orthodihydroxy-1,2-diphenylethylenes in a medium comprising salts or manganese and / or zinc oxides and (hydrogen) carbonates, made it possible to achieve the objectives set out above.

The present invention therefore relates to a process for treating keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said fibers of one or more derivatives of ortho-dihydroxy-1,2-diphenylethylene, d '' one or more additional polyphenols different from the ortho-dihydroxy-1,2,2-diphenylethylenes derivatives, from one or more manganese and / or zinc derivatives chosen from manganese salts or oxides and salts or oxides of zinc, and one or more (hydrogen) carbonates.

The process of the invention advantageously comprises:

a) the application to the fibers of a composition (A) comprising the ortho-dihydroxy-1,2-diphenylethylene derivative (s), the additional polyphenol (s) different from the ortho-dihydroxy-1,2-diphenylethylene derivatives, and the manganese and / or zinc derivative (s), and

b) the application to the fibers of a composition (B) comprising the (hydrogen) carbonate (s).

The method of the invention also relates to a device with several compartments comprising at least two compartments containing the respective compositions (A) and (B) above.

The treatment method according to the invention is a coloring method which makes it possible to obtain (re) pigmentation of the keratin fibers, which is both progressive and visible from the first application.

Unlike the conventional coloring methods, the method of the invention makes it possible to achieve true pigmentation or repigmentation of the keratin fibers, by returning to the original color or by providing it with nuances, or else by effecting a change in the color. In the case of white hair, the process allows the hair to be gradually re-pigmented according to the number of applications. It also helps prevent or delay the appearance of gray hair.

The process of the invention differs from oxidation coloring processes, since it does not use the condensation of coloring precursors in the presence of an oxidizing agent. It also does not correspond to a direct coloring process, since it does not use colored molecules. In particular, the ortho-dihydroxy-1,2-diphenylethylene derivatives used in the present invention are not colored molecules, on the contrary direct dyes.

The process according to the invention can be repeated, which makes it possible gradually to obtain a natural dark or even black coloring effect. In particular, the process of the invention makes it possible to obtain an excellent level of dark pigmentation and good coverage of gray hair from three applications. Repeated applications can take place one after the other or be separated by several hours or even days.

The process thus makes it possible to obtain a good intensity of coloring, in particular a good coverage of white hair over the whole of the hair, as well as a good homogeneity of the color along the keratin fibers.

Finally, the colors thus obtained are non-aggressive and well tolerated by keratin fibers. The process according to the invention does not damage the keratin fibers and provides them with a good level of conditioning, in particular in terms of flexibility, softness, smoothing and disentangling.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

In what follows, and unless otherwise indicated, the limits of a range of values are included in this range, in particular in the expressions "between" and "going from ... to ...".

Furthermore, the expressions “at least one” and “at least” used in the present description are respectively equivalent to the expressions “one or more” and “greater than or equal”.

By the term “substituted” or “optionally substituted”, is meant conventional substituents of the chemical radicals concerned such as alkyl, amino, aminoalkyl, hydroxy, hydroxyalkyl, halogenated, etc. substituents.

Ortho dihydroxy-L2-diphenylethylene derivatives

The present invention uses one or more ortho-dihydroxy-1,2-diphenylethylene derivatives, preferably present in composition (A).

By "ortho-dihydroxy-1,2-diphenylethylene derivatives" is meant compounds comprising in their chemical structure at least one ortho-dihydroxy-1,2-diphenylethylene group. Preferably, they comprise in their structure a 1,2-diphenylethylene orthodihydroxy group, or two ortho-dihydroxy1,2-diphenylethylene groups (in particular in the case of orthodihydroxy-1,2-diphenylethylene dimers). These compounds can be compounds whose hydroxy groups are protected, such as, for example, corresponding glycosylated derivatives.

The ortho-dihydroxy-1,2-diphenylethylene derivative (s) used according to the present invention can be of natural or synthetic origin.

These compounds are preferably chosen from: glycosylated derivatives such as 2,3,5,4'-tetrahydroxystilbene-2Ο-β-D-glucoside; trans-3 '^ - glucopyranosyl-4,5'-dihydroxy-3methoxystilbene; trans-3 '^ - glucopyranosyl-3,4,5'trihydroxystilbene; piceatannol 3-glucoside;

non-glycosylated derivatives such as trans-3-methoxy-3 ', 4,5'trihydroxystilbene; piceatannol (trans-3.3 ', 4.5 ¹ tetrahydroxystilbene); 5 - [(lE) -2-phenylethenyl] -1,2,3-benzenetriol; 4 - [(1Z) -2- (3,5-dihydroxyphenyl) ethenyl] -1,2-benzenediol; 5 [(1E) -2- (4-hydroxyphenyl) ethenyl] -1,2,3-benzenetriol; 5 - [(lE) -2 (3,4-dihydroxyphenyl) ethenyl] -1,2,3-benzenetriol; 4 - [(1E) -2- (2,4dihydroxyphenyl) ethenyl] -1,2-benzenediol; acid a - [[(2E) -3- [2 [(lE) -2- (3,4-dihydroxyphenyl) ethenyl] -3,4-dihydroxyphenyl] -l-oxo-2propen-l-yl] oxy ] -3,4-dihydroxy-benzenepropanoic; 2 - [(lE) -2- (3,4-dihydroxyphenyl) ethenyl] -6hydroxy-benzoic acid ethyl ester and 4 - [(lE) -2- (3,5-dimethoxyphenyl) ethenyl] 1.2- benzenediol; and optical and / or geometric isomers, salts and / or solvates and mixtures of such derivatives.

The ortho-dihydroxy-1,2-diphenylethylene derivative (s) which can be used according to the present invention can also be in the form of dimers, such as those described in Journal of Chemical Research (2004), (5), 339-340, as andalasin B extracted from the roots of Morus macroura.

Mention may also be made of condensed tannins of orthodihydroxy-1,2-diphenylethylene such as those described in Tetrahedron Letters (1983), 24 (38), 4147-50.

More preferably, the ortho-dihydroxy1,2- diphenylethylene derivative (s) are chosen from glycosylated derivatives, and better still, composition (A) comprises 2,3,5,4'tetrahydroxystilbene-2-O-P-D-glucoside.

According to a particularly preferred embodiment of the present invention, the ortho-dihydroxy-1,2-diphenylethylene derivative (s) are of natural origin. In this embodiment, the composition (A) comprises one or more plant extracts which can be chosen from, for example, Polygonum multiflorum, Radix Poligoni Multiflori, Fallopia multiflora, Smilax china, Morus australis Poir, Cistanche tubulosa, Millettia erythrocalyx, Artocarpus lakoocha, Cissus assamica, Veratrum maackii, Vitis vinifera, Vitis labrusca, Smilax stans, Picea abies, and Guibourtia coleosperma, said extracts containing the ortho-dihydroxy-1,2,2-diphenylethylene derivative (s).

The ortho-dihydroxy-1,2-diphenylethylene derivative (s) used in the present invention can be extracted from the plants mentioned above according, for example, to the protocol described in patent application CN 103405516.

The total amount of the ortho-dihydroxy-1,2-diphenylethylene derivative (s) present in composition (A) ranges preferably from 0.001 to 10% by weight, and more preferably from 0.01 to 5% by weight , relative to the total weight of the composition (A).

When these compounds are used in the form of plant extract, an extract content typically ranging from 0.1 to 50% by weight, and preferably from 0.5 to 30% by weight, is used relative to the total weight of the composition (A).

Manganese and / or zinc derivatives

The process of the invention also includes the application of one or more manganese (Mn) and / or zinc (Zn) derivatives chosen from salts or oxides.

This or these manganese and / or zinc derivatives are preferably contained in composition (A).

Within the meaning of the present invention, the term “salts” means the salts themselves in ionized form. These salts can be solvated, in particular hydrated.

The derivatives are preferably salts.

In particular, the derivatives of the invention are of oxidation state 2 such as Mn (II) and Zn (II).

The manganese and / or zinc salt or salts are advantageously chosen from chlorides, fluorides, iodides, bromides, sulfates, phosphates, nitrates, perchlorates, carbonates, carboxylates, and mixtures thereof.

The carboxylates which can be used in the invention also include salts of carboxylic acids comprising one or more hydroxy radicals, such as gluconates.

Examples of carboxylates that may be mentioned, for example: acetate, tartrate, lysinate, glutamate, lactate, glycinate, aspartate, stearate, acetylacetate.

The manganese and zinc derivatives can be introduced in solid form into the compositions or else be introduced in the form of an aqueous solution such as natural, mineral or thermal water, rich in these ions or even sea water (Dead Sea especially). They can also come from mineral compounds such as earths, ochres such as clays (green clay for example) or even plant extracts containing them (cf. for example the document FR 2 814 943).

Among the manganese salts, manganese chloride, manganese carbonate, manganese difluoride, manganese acetate tetrahydrate, manganese lactate trihydrate, manganese phosphate, manganese iodide, manganese iodide are preferred. manganese trihydrate, manganese bromide, manganese perchlorate tetrahydrate, manganese sulfate monohydrate, manganese gluconate and mixtures thereof.

Among the zinc salts, zinc sulfate, zinc gluconate, zinc chloride, zinc lactate, zinc acetate, zinc glycinate, zinc aspartate and mixtures thereof are preferred.

Preferably, the process 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 manganese carboxylates, in particular manganese gluconate and manganese halides, such as manganese chloride, and their mixtures.

More preferably, the manganese salt or salts are chosen from manganese chloride, manganese gluconate and their mixtures.

When the composition (A) comprises one or more manganese derivatives, the total concentration of the said derivative (s) in the composition (A) preferably ranges from 10 ' ³ to 10' ¹ mmol.l ' ¹ , and more preferably from 10 ' ² to 10' ¹ mmol.l ' ¹ .

When the composition (A) comprises one or more zinc derivatives, the total concentration of the said derivative (s) in the composition (A) ranges from 5.10 ' ² to 10 mmol.l' ¹ , and more preferably from 5.10 ' ¹ to 1 mmol .l ^-1.

Polyphenols different from ortho-dihydroxy-L2diphenylethylene derivatives

The process of the invention comprises the application to the keratin fibers of one or more additional polyphenol (s) different from the derivatives of ortho-dihydroxy-1,2-diphenylethylene.

These additional polyphenols are preferably chosen from orthodiphenols, that is to say the compounds comprising one or more aromatic rings, preferably benzene, comprising at least two hydroxy (OH) groups carried by two adjacent carbon atoms of the same ring aromatic. In particular, the orthodiphenol (s) useful in the invention are not self-oxidizing derivatives, in particular self-oxidizing derivatives with an indole motif. More particularly, they are not 5,6-dihydroxyindole.

The aromatic ring can more particularly be a condensed aryl or condensed heteroaromatic ring ie possibly containing one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, isoindole, indoline, isoindoline, ίο benzofuran, dihydrobenzofuran, chroman, isochroman, 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 cycle of the orthodiphenol derivatives according to the invention is a benzene cycle.

By condensed cycle, it is meant that at least two saturated or unsaturated cycles, heterocyclic or not, have a common bond, that is to say that at least one cycle is joined to another cycle.

Additional orthodiphenols can be salified or not. They can also be in the form of aglygone (without bound sugar) or in the form of glycosylated compounds.

According to a particularly preferred embodiment, the composition (A) comprises one or more orthodiphenol (s) of formula (I) below, or one of its oligomers, in salified form or not:

formula (I) in which the substituents Ri to R4, identical or different, represent:

- a hydrogen atom,

- a halogen atom,

- a hydroxy radical,

- a carboxyl radical,

- an alkyl or alkoxycarbonyl carboxylate radical,

- an optionally substituted amino radical,

- an optionally substituted linear or branched alkyl radical,

an optionally substituted linear or branched alkenyl radical,

- an optionally substituted cycloalkyl radical,

- an alkoxy radical,

- an alkoxyalkyl radical,

an alkoxyaryl radical, the aryl group possibly being substituted,

- an aryl radical,

- a substituted aryl radical,

a heterocyclic radical, saturated or not, carrying or not a cationic or anionic charge, optionally substituted and / or optionally condensed with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted particularly by one or more hydroxy or glycosyloxy groups ,

- a radical containing one or more silicon atoms, or two of the substituents carried by two adjacent carbon atoms (namely Ri and R2, R2 and R3 or R3 and R4) form jointly with the carbon atoms carrying them a saturated ring or unsaturated, 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.

Preferably, the additional orthodiphenol derivatives of formula (I) are chosen from those in which two adjacent substituents Ri - R2, R2 - R3 or R3 - R4 cannot form a cyclic radical with the carbon atoms which carry them. a pyrolytic radical. More particularly, R2 and R3 cannot form a pyrolytic radical condensed in the benzene ring carrying the two hydroxy.

Within the meaning of the present invention, and unless a different indication is given:

- Saturated or unsaturated cycles, possibly condensed, can also be optionally substituted.

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

- The alkenyl radicals are hydrocarbon radicals, linear or branched, C2-C20 unsaturated; 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 a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, and tetrahydronaphthyl.

- The alkoxy radicals are alkyl-oxy radicals with alkyl as defined above, preferably in C1-C10, such as methoxy, ethoxy, propoxy and butoxy.

- The alkyl alkoxy radicals are preferably alkoxy (C1-C20) alkyl (C1-C20) radicals, such as methoxymethyl, ethoxymethyl, methoxy ethyl, ethoxy ethyl, etc.

- The cycloalkyl radicals are generally the C4-C8 cycloalkyl radicals, preferably the cyclopentyl and cyclohexyl radicals. The cycloalkyl radicals can be cycloalkyl radicals substituted, in particular by alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups.

The additional orthodiphenols useful in the process of the invention can be natural or synthetic. Among the natural orthodiphenols, one includes the compounds which can be present in nature and which are reproduced by (hemi) chemical synthesis.

According to a particular embodiment of the invention, the method comprises the application of one or more additional synthetic orthodiphenol (s) which do not exist in nature.

According to another preferred embodiment of the invention, the additional orthodiphenols are natural orthodiphenols.

More particularly, the additional natural orthodiphenols which can be used in the process of the invention are chosen from:

flavanols like catechin and epichatechin gallate,

- flavonols such as quercetin,

- anthocyanidins such as cyanidine, delphinidine, petunidine, pelargonidine

- anthocyanins or anthocyanins such as delphinidin 3-O-glucoside also called myrtillin,

- orthohydroxybenzoates, for example gallic acid derivatives, and in particular gallates, for example propylgallate,

- flavones such as luteolin,

- 3,4-dihydroxyphenylalanine and its derivatives, such as L-3,4-dihydroxyphenylalanine methyl ester hydrochloride,

- 2,3-dihydroxyphenylalanine and its derivatives,

- 4,5-dihydroxyphenylalanine and its derivatives,

- dihydroxycinnamates such as caffeic acid and chlorogenic acid,

- orthopolyhydroxycoumarins,

- orthopolyhydroxyisocoumarins,

- orthopolyhydroxycoumarones,

- orthopolyhydroxyisocoumarones,

- orthopolyhydroxychalcones,

- orthopolyhydroxychromones,

- quinones,

- hydroxyxanthones,

- 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 and in particular proanthocyanidins Al, A2, Bl, B2, B3 and Cl,

- proanthocyanins,

- tannic acid,

- ellagic acid,

- and mixtures of the above compounds, and more particularly from catechin, quercetin, brazilin (CAS 474-07-7), hematein, hematoxylin, chlorogenic, caffeic, gallic acids, catechol, gallic acid, L DOPA, pelargonidine, cyanidine, T (-) - epicatechin, (-) epigallocatechin, T (-) - epigallocatechin 3-gallate (EGCG), (+) catechin, isoquercetin, pomiferin , esculetin, 6,7-dihydroxy3- (3-hydroxy-2,4-dimethoxyphenyl) coumarin, santalin AC, mangiferine, buteine, maritimetine, sulfuretine, robteine, betanidine, pericampylinone A ., theaflavin, proanthocyanidin A2, proanthocyanidin B2, proanthocyanidin Cl, procyanidins DP 4-8, tannic acid, purpurogallin, 5,6-dihydroxy-2-methyl-l, 4-naphthoquinone, l alizarin, wedelolactone, variegatic acid, gomphidic acid, xerocomic acid, carnosol, and the natural extracts containing them .

Preferably, the additional orthodiphenol (s) according to the invention are chosen from flavanols, flavonols, orthohydroxybenzoates, isoflavones and neoflavones.

According to one embodiment, the natural orthodiphenols are derived from extracts or are introduced in the form of extracts from animals, bacteria, fungi, algae, plants and fruits used in whole or in part. Particularly for plants, the extracts come from fruits including citrus fruits, vegetables, trees, shrubs and lychens. It is also possible to use mixtures of these extracts, rich in orthodiphenols as defined above.

Preferably, the additional orthodiphenol (s) are natural orthodiphenols, derived from plant extracts or parts of plants. These extracts of plants or parts of plants can be used directly in the process of the invention.

The extracts are obtained by extracting various parts of plants such as for example the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod, the peel.

Among the plant extracts, there may be mentioned extracts of tea leaves, of rose.

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

Among vegetable extracts, we can quote potato extracts, onion peels.

Among the extracts from tree wood, we can cite extracts of pine bark, extracts of logwood.

Mixtures of plant extracts can also be used.

According to a particular embodiment of the invention, the orthodiphenol (s) are natural extracts, rich in orthodiphenols. According to a preferred embodiment, the derivative (s) of additional orthodiphenols are only contained in natural extracts.

Preferably, the polyphenol (s) used in the process according to the invention are chosen from catechin, quercetin, haematin, hematoxylin, brazilin gallic acid, and the natural extracts containing them, chosen in particular from grape marc, pine bark, green tea, onion, cocoa bean, logwood, red wood and gall nut. Preferably, the extract used is logwood.

Even more preferably, the additional polyphenol or polyphenol (s) are chosen from catechin, quercetin, gallic acid and hematoxylin.

The natural extracts containing the additional polyphenols according to the invention can be in the form of powders or liquids. Preferably, the extracts containing the additional polyphenols according to the invention are in the form of powders.

According to the invention, the synthetic polyphenol (s), natural (s), and / or the natural extract (s) containing them preferably represent (s), from 0.001% to 20% weight of the total weight of the composition (A).

As regards the pure polyphenols or polyphenols, their content in the composition (A) is preferably between 0.001 and 5% by weight relative to the total weight of the composition (A).

With regard to the extracts, the extract content in the composition (A) is preferably between 0.5 and 20% by weight relative to the total weight of the composition (A).

According to a particularly preferred embodiment, the method according to the invention does not use oxidation dyes, nor direct dyes different from the derivatives of orthodihydroxy-1,2-diphenylethylene and the additional polyphenols described above.

The (hydrogen) carbonates

The (hydrogen) carbonate (s) used in the process of the invention are in particular chosen from the compounds 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 the groups R ”, identical or different, represent an atom of hydrogen, an optionally substituted (C 1 -C 6) alkyl group such as hydroxyethyl; when R ′ represents a hydrogen atom, the hydrogen carbonate is then called dihydrogen carbonate (CO2, H ₂ O); and

- Met ' ²⁺ (HCCL'h with Met' representing an alkaline earth metal.

More particularly, the (hydrogen) carbonate (s) are chosen from alkaline hydrogen carbonates, alkaline earth hydrogen carbonates, ammonium hydrogen carbonates and mixtures thereof; and more preferably from alkaline hydrogen carbonates, alkaline earth hydrogen carbonates and their mixtures.

Better still, the hydrogen carbonates are chosen from sodium, potassium, magnesium, calcium hydrogen carbonates and their mixtures, and in particular sodium hydrogen carbonate and potassium hydrogen carbonate. Even more preferably, the hydrogen carbonate used in the process of the invention is sodium hydrogen carbonate.

These (hydrogen) carbonates can come from natural water, for example spring water from the Vichy basin, from La Roche Posay, water from Badoit (cf. patent for example the document FR 2 814 943). Particularly, mention may be made of sodium carbonate Na ₂ C03, sodium hydrogencarbonate or sodium bicarbonate NaHCO3.

These hydrogen carbonates can also be generated in situ by any process making it possible to generate an HCO3 ’salt.

Composition (B) may contain a total amount of the (hydrogen) carbonates which preferably ranges from 0.1% to 15% by weight, and more preferably from 0.5% to 10% by weight, relative to the total weight of the composition (B).

According to a preferred embodiment, the total molar concentration of (hydrogen) carbonates is greater than the total molar concentration of manganese salts and zinc salts applied to the keratin fibers.

Metal salts different from manganese and zinc salts

The process according to the present invention can also comprise the application to the keratin fibers of one or more additional metal salt (s) divalent or trivalent different from the manganese salts and the zinc salts defined above.

By “metal salt” is meant, within the meaning of the present invention, the salts themselves, that is to say in ionized form, of the metals of columns 3 to 14 of the periodic table of the elements different from manganese and from zinc.

Among these additional metal salts, mention may in particular be made of hydroxides, halides, sulfates, phosphates, nitrates and carboxylates.

Preferably, the additional metal salt or salts are chosen from iron (II) salts and iron (III) salts.

More preferably, the additional metal salt or salts are chosen from iron sulphate, iron fumarate, iron gluconate, iron acetylacetonate, iron oxalate, mixed salts, such as the Mohr salt, and their mixtures; and better still iron sulfate.

According to a first preferred embodiment, the additional metal salt or salts are present in the composition (A).

According to a second preferred embodiment, the additional metal salt or salts are present in a composition (C) distinct from the compositions (A) and (B).

It is also possible to combine these two embodiments, and to use the additional metal salt or salts both in composition (A) and in a separate composition (C).

When they are used, the total amount of the additional metal salt (s) preferably ranges from 0.001 to 5% by weight, and more preferably from 0.01 to 4% by weight, relative to the total weight of the composition containing them.

Deglycosylation

In the case where one or more glycosylated derivatives of orthodihydroxy-1,2-diphenylethylene are used in the process of the invention, the process further comprises the use of an enzyme of the β-glucosidase type in order to promote deglycosylation and therefore to optimize the coloration obtained. One can also use any other means known for deglycosylating, such as those described for example in Kinetics and mechanism of 2,3,5,4'-tetrahydroxystilbene-2-O-f-dglycoside (THSG) degradation in aqueous solutions, .J. Pharm. Biomed. Anal. 2011 Apr 28; 55 (1): 211-5. Epub 2010 Dec 31.

The enzyme can be added extemporaneously in composition (A) comprising glycosylated 1,2-dihydroxy-diphenylethylene, immediately before the application of this composition to the fibers.

It is also possible to add the enzyme extemporaneously in composition (A) comprising dihydroxy-1,2-diphenylethylene glycosylated, add if necessary an aqueous solution at pH 5 to 9 if the initial composition did not contain water, maintain this new composition as it is from 10 min to 2 hours, preferably 15 to 1 hour before application to the fibers, said enzyme being able to be eliminated from this composition just before application to the fibers, by any means known to those skilled in the art .

Preferably, glucosidases of natural origin are used such as almond beta glucosidases, such as in particular sweet almond glucosidase EC 3.2.1.

One can use for example the β-Glucosidase of almonds marketed by the company Aldrich under the name 49290 SIGMA β-Glucosidase from almonds lyophilized, powder, ÎA6 U / mg. This composition can be applied in a 1 mg / ml solution for 30 min to 1 hour.

Preferably, the composition containing an enzyme of β-glucosidase type is applied at a temperature below 55 ° C and more preferably from 30 to 40 ° C. The pH of this composition can range from 5 to 9.

Surfactants

The compositions useful for the invention can optionally comprise one or more surfactants.

The surfactant (s) which can be used are preferably chosen from nonionic surfactants, anionic surfactants and amphoteric or zwitterionic surfactants.

The total amount of the surfactant (s) present in the compositions according to the invention can range from 0.1 to 30% by weight, and preferably from 0.5 to 20% by weight, relative to the total weight of each composition containing them.

Preferably, the surfactant (s) are present in the composition (B).

The essays

The compositions used in the present invention can be in any form compatible with an application to keratin fibers and in particular the hair.

In particular, the compositions (A), (B) and if appropriate (C) useful in the invention can be in the form of liquid compositions or powders. According to a preferred embodiment, the compositions (A), (B) and where appropriate (C) are in the form of liquid compositions, such as solutions.

It can be aqueous solutions, in particular hydroalcoholic. They generally comprise water or a mixture of water and one or more solvents, for example chosen from lower C1-C4 alcohols, such as ethanol, isopropanol, tert-butanol or n -butanol; polyols such as glycerol, propylene glycol and polyethylene glycols; and their mixtures.

When they are present, the total amount of the solvent (s) ranges preferably from 0.01% to 50% by weight, and more preferably from 0.05 to 30% by weight, relative to the weight of each composition. container.

When the composition which contains the metal salt (s) is in the form of a solution, the latter must not flocculate. Depending on the metal salt, those skilled in the art will choose the appropriate pH to avoid flocculation of the composition.

When it is aqueous, the composition (A) has an acidic pH, preferably ranging from 3 to 7. When it is aqueous, the composition (B) has a rather basic pH, preferably between 7.1 and 9.5. When it is aqueous, the composition (C) has a rather acidic pH, ranging from 2 to 7, preferably from 3 to 4.

Additives

The compositions useful in the invention can comprise one or more additives among which mention may be made of cationic, anionic, nonionic, amphoteric polymers or their mixtures, thickening agents, anti-dandruff agents, antiseborrhoeic agents, fall arrest agents and / or regrows hair, vitamins and pro-vitamins including panthenol, sun filters, sequestering agents, plasticizing agents, solubilizing agents, acidifying agents, opacifying or pearlescent agents, hydroxy acids, perfumes, preserving agents , fillers, preferably of natural origin. Mention may be made, as fillers, of pigments such as iron oxides originating from ochres, carbon black, chlorophyll, polymerized anthocyanins.

The above additives may be present in an amount for each of them between 0 and 20% by weight relative to the total weight of each composition containing them, in the case of a liquid composition.

The above additives may be present in an amount for each of them between 0 and 80% by weight relative to the total weight of each composition containing them, in the case of a solid composition.

The process

When the method according to the present invention is implemented from the compositions (A), (B) and if appropriate (C) described above, the compositions (A) and (B), as well as the composition (C ) when present, are applied to dry or wet keratin fibers, and preferably to wet keratin fibers.

According to a preferred embodiment, the composition (A) is then applied successively then the composition (B).

According to this embodiment, the method more preferably comprises:

- According to a first variant, the application to keratin fibers of the composition (A), then of the composition (B); preferably with a pause time between the application of the composition (A) and (B), which can vary from 30 seconds to 1 hour, preferably from 1 min to 30 min;

- According to a second variant, the application to the keratin fibers of the extemporaneous mixture of the composition (A) and of the composition (B), that is to say that the mixture of the compositions (A) and (B) is immediately applied to the fibers, without intermediate storage;

- According to a third variant, the application to the keratin fibers of a composition resulting from the mixture of the composition (A) with the composition (B), maintained before application to the fibers in a receptacle free of oxygen.

In the last two variants, the oxygen in the air acts directly on the hair at the time of application. This embodiment makes it possible to reduce the number of steps to be implemented.

According to the particular embodiment which implements one or more additional metal salts as defined above present in a composition (C) distinct from the compositions (A) and (B), the three compositions (A), (B) and ( C) are applied successively to the keratin fibers.

According to this embodiment, the composition (C) is applied after the composition (B) or before the composition (A), preferably with a pause time between the application of the composition (A) and (B) as defined above.

Each of the compositions (A), (B) and optionally (C), or the composition resulting from the mixing of these, is advantageously left in place on the keratin fibers for a period ranging from 30 seconds to 1 hour, and more preferably from 30 seconds to 30 minutes.

The process of the present invention can be repeated several times, in particular from 2 to 50 times, preferably from 3 to 30 times, depending on the degree of coloration desired. The higher the number of applications, the more intense and dark the coloring, thereby improving the repigmentation of gray hair.

Advantageously, the method of the invention is implemented by reapplying the compositions (A), (B) and optionally (C) several times to obtain, over time, a natural and visible coloration. For example, the application of the compositions according to the invention can be carried out after each shampoo, or for example 1 or 2 times a week.

The process of the invention can also comprise a rinsing step after the application of compositions (A) and (B) or after application of compositions (A), (B) and (C).

More preferably, the method comprises a single final rinsing step. In other words, the keratin fibers are rinsed only after the application of the last composition.

Device

Finally, the present invention relates to a device with several compartments comprising:

a first compartment containing the composition (A) as defined above;

a second compartment containing the composition (B) as defined above.

According to another embodiment of the device, it contains a compartment comprising a composition resulting from the mixture of the composition (A) with the composition (B), this compartment being free of oxygen.

The device according to the present invention can further comprise:

- an additional compartment containing the composition (C) as defined above, and / or

- an additional compartment containing a composition comprising a glucosidase.

The compositions of the compartments are intended to be applied successively to the keratin fibers according to the method as described above.

The following examples serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

In all of the examples below, the color of the locks was evaluated in the CIE L * a * b * system, using a Minolta Spectrophotometer CM2600D colorimeter.

In this L * a * b * system, the three parameters respectively designate the color intensity (L *), a * indicates the green / red color axis and b * the blue / yellow color axis. The higher the value of L *, the lighter the color. The higher the value of a *, the redder the color, the higher the value of b *, the more yellow the color.

In the examples which follow, all the amounts are indicated in percentage by weight relative to the total weight of each composition.

Example 1: according to the invention

at. Compositions tested

The following compositions A1 and B were prepared from the ingredients, the contents of which are indicated in the tables below.

Composition Al: __

Black shou wu 1% Manganese chloride 0.406% Hematoxylin (in the form of extract of logwood with 25% hematoxylin, ie a hematoxylin content of 0.075% of active material in the final composition) 0.3% Water Qsp 100

Black shou wu is a natural extract enriched in THSG, prepared according to the preparation process described in patent application CN103405516, and which contains 15 to 30% by weight of THSG. It contains a total amount of polyphenols including THSG from 25 to 50% by weight.

The term THSG designates 2,3,5,4'-tetrahydroxystilbene-2-O-3D-glucoside, which is a derivative of ortho-dihydroxy-1,2-diphenylethylene of formula:

HO

Composition B:

Sodium hydrogen carbonate 8 Cocoylbétaine 5 Water Qsp 100

at. Procedure

The compositions A1 and B thus obtained were then applied, according to the protocol below, to locks of Chinese hair (100% or 50% white) previously washed.

Protocol for an application:

The composition Al was firstly applied using a brush at the rate of 500 μl of composition Al to the locks of 0.5 g. The locks were then left to stand at 22 ° C for 5 minutes.

Then composition B was applied in identical quantity, namely 500 μl per wick of 0.5 g. The locks of hair were rubbed.

After 3 minutes of laying at 22 ° C, the locks of hair were rinsed with water, then left to dry.

The above protocol was repeated 1, 3 or 10 times on the locks.

The color of the locks obtained was evaluated in the system

CIE L * a * b * using a Minolta Spectrophotometer CM2600D colorimeter.

The tables below represent the values of the coloring intensities evaluated in the L * a * b * system (average value for 3 locks), obtained from 100% gray hair (Table 1) or 50% (Table 2 ).

Table 1

L * at* b * 100% hair white before treatment 67.2 1.15 20.33 After 1 application 51.51 -3.1 9.25 After 3 applications 45.83 -3.64 0.6 After 10 applications 29.75 1.32 -1.05

Table 2

L * at* b * Hair 50% white before treatment 35.11 0.95 7.19 After 3 applications 34.59 -1.44 2.01 After 10 applications 22.35 1.65 0.51

The above results show that the method according to the present invention makes it possible to darken 100% white hair (Table 1) and 50% white hair (Table 2) from the first applications.

In addition, the colors are much darker and more intense after 10 applications.

Example 2: according to the invention

a) Compositions tested

The following compositions A2, A2 ’, A3, A3’, A4, A4 ’, A5, A5’ and B were prepared from the ingredients, the contents of which are indicated in the tables below.

Composition A2 A2 ’ Black shou wu (identical extract to that of example 1) 5% 5% Manganese chloride 0.406% 0.406% Gallic acid 0.1% 1% Water Qsp 100 Qsp 100

Composition A3 A3 ’ Black shou wu (identical extract to that of example 1) 5% 5% Manganese chloride 0.406% 0.406% Catechine 0.1% 1% Water Qsp 100 Qsp 100

Composition A4 A4 ’ Black shou wu (identical extract to that of example 1) 5% 5% Manganese chloride 0.406% 0.406% Quercetine 0.1% 1% Water Qsp 100 Qsp 100

Composition AT 5 AT 5' Black shou wu (identical extract to that of example 1) 5% 5% Manganese chloride 0.406% 0.406% Tannic acid 0.1% 1% Water Qsp 100 Qsp 100

Composition B:

Sodium hydrogen carbonate 8 Cocoylbétaine 5 Water Qsp 100

b.) Procedure

The compositions A2, A2 ’, A3, A3’, A4, A4 ’, A5, A5’ and B thus obtained were then applied, according to the protocol below, to locks of Chinese hair (100% white) previously washed.

Protocol for an application:

Composition A was first applied using a brush at the rate of 500 μl to the locks each weighing 0.5 g. The locks were then left to stand at 22 ° C for 30 minutes.

Composition B was then applied in an identical amount, namely 500 μl per wick of 0.5 g. After 30 minutes of laying at 22 ° C, the locks of hair were rinsed with water, then left to dry.

The application was made once.

The color of the locks obtained was evaluated in the CIE L * a * b * system using a Minolta Spectrophotometer CM2600D colorimeter.

c) Results

The table below represents the values of the coloring intensities evaluated in the L * a * b * system (average value for 3 locks).

L * at* b * 100% hair white before treatment 67.2 1.15 20.33 A2 + B 50.26 5.25 16.84 A2 ’+ B 30.2 4.98 13.6 A3 + B 46.27 6.98 20.09 A3 ’+ B 41.94 5.64 21.05 A4 + B 49.65 6.49 16.5 A4 ’+ B 52.38 5.45 17.77 A5 + B 44.75 3.17 15.91 A5 ’+ B 45.79 4.17 18.67

The above results show that the method according to the present invention makes it possible to obtain various natural shades of the hair from the first application.

Example 3: according to the invention

a) Compositions tested

The following compositions A6, A6 ’, B, Cl and Cl’ were prepared from the ingredients, the contents of which are indicated in the tables below.

Compositions A:

Composition A6 A6 ’ Black shou wu (identical extract to that of example 1) 5% 5% Manganese chloride 0.406% 0.406% Hematoxylin (in the form log extract with 25% hematoxylin) 0.1% (0.025% ai) 1% (0.25% ai) Water Qsp 100 Qsp 100

ma = active ingredient

Composition B:

Sodium hydrogen carbonate 8 Cocoylbétaine 5 Water Qsp 100

Compositions C:

Composition Cl Cl ’ Sodium alginate 1% 1% FeSO4 0.1% 1%

b) Procedure

The compositions A, B and C thus obtained were then applied, according to the following protocol, to locks of Chinese hair (100% white) previously washed.

Protocol for an application:

Composition A was first applied with a brush at the rate of 500 μl of composition A to the locks each weighing 0.5 g. The locks were then left to stand at 22 ° C for 30 minutes.

Composition B was then applied in an identical amount, namely 500 μl per wick of 0.5 g.

After 30 minutes of laying at 22 ° C., 1 ml of composition C was applied to the locks, then each lock was rubbed and left to stand for one minute.

The locks were then rinsed with water and then allowed to dry.

The application was made once.

The color of the locks thus obtained was evaluated in the CIE L * a * b * system using a Minolta Spectrophotometer CM2600D colorimeter.

c) Results

The table below represents the values of the coloring intensities evaluated in the L * a * b * system (average value for 3 locks).

L * at* b * 100% hair white before treatment 67.2 1.15 20.33 A6 + B + Cl 29.61 5.68 7.42 A6 + B + Cl ’ 26.11 2.16 0.92 A6 ’+ B + Cl 16.49 1.2 0.05 A6 ’+ B + Cl’ 14.66 0.96 -0.46

The above results show that the process according to the present invention makes it possible to obtain, from the first application, significant pigmentation of the hair, with dark shades close to an HL2 level (two levels of pitch).

Example 4: comparative tests

at. Compositions tested

Compositions A:

Composition A7 AT 8 AT 8' A9 A9 ’ Black shou wu (identical extract to that of example 1) 5% - - 5% 5% Chloride manganese 0.406% 0.406% 0.406% 0.406% 0.406% Hematoxylin (extract of logwood with 25% hematoxylin) - 0.1% (0.025% my) 1% (0.25% ai) 0.1% (0.025% my) 1% (0.25% ai) Water Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100

ma = active ingredient

Composition B

Sodium hydrogenate 8 Cocoylbétaine 5 Water Qsp 100

b. Procedure

The compositions A and B thus obtained were then applied, according to the protocol below, to locks of Chinese hair (100% white) previously washed.

Protocol for an application:

Composition A was first applied with a brush at the rate of 500 μl of composition A to the locks each weighing 0.5 g. The locks were then left to stand at 22 ° C for 30 minutes.

Composition B was then applied in an identical amount, namely 500 μl per wick of 0.5 g.

The locks were then rinsed with water and then allowed to dry.

The color of the locks thus obtained was evaluated in the CIE L * a * b * system using a Minolta Spectrophotometer CM2600D colorimeter.

vs. Results

The table below represents the values of the coloring intensities evaluated in the L * a * b * system (average value for 3 locks), after one application.

Comparative example: A7 + B:

L * at* b * 100% hair white before treatment 67.2 1.15 20.33 After 1 application 51.45 5.74 16.95 After 3 applications 44.54 8.28 16.66 After 10 applications 45.4 9.53 17.9

Comparative example: A8 or A8 ’+ B:

L * at* b * 100% hair white before treatment 67.2 1.15 20.33 A8 + B, after 1 application 35.25 5.36 9.1 A8 ’+ B, after 1 application 27.45 7.25 10.22

Example according to the invention: A9 or A9 ’+ B:

L * at* b * 100% hair white before treatment 67.2 1.15 20.33 A9 + B, after 1 application 28.1 4.77 3.98 A9 ’+ B, after 1 application 22.35 3.86 -1.38

The above examples show that the process according to the invention, implementing the association of an orthodihydroxy-1,2-diphenylethylene derivative in combination with a polyphenol, makes it possible to obtain a higher coloring performance, with a black tone having a pitch comparable to that of natural black hair, which is more intense than the coloration obtained in the comparative processes using only one of these two compounds.

Claims (20)

1. A method for treating keratin fibers comprising the application to said fibers of one or more derivatives of orthodihydroxy-1,2-diphenylethylene, of one or more additional polyphenols different from derivatives of ortho-dihydroxy-1,2-diphenylethylenes , one or more manganese and / or zinc derivatives chosen from manganese salts or oxides and zinc salts or oxides, and one or more (hydrogen) carbonates. 2. Method according to claim 1, characterized in that it comprises: a) the application to the fibers of a composition (A) comprising the ortho-dihydroxy-1,2-diphenylethylene derivative (s), the additional polyphenol (s) different from the orthodihydroxy-1,2,2-diphenylethylene derivatives and the manganese and / or zinc derivative (s), and b) the application to the fibers of a composition (B) comprising the (hydrogen) carbonate (s). 3. Method according to any one of the preceding claims, characterized in that the ortho-dihydroxy1,2-diphenylethylene derivative (s) are chosen from: - glycosylated derivatives such as 2,3,5,4'tétrahydroxystilbène-2-O-3-D-glucoside; trans-3'-3glucopyranosyl-4,5'-dihydroxy-3-methoxystilbene; trans-3'-3glucopyranosyl-3,4,5'-trihydroxystilbene; piceatannol 3-glucoside; - non-glycosylated derivatives such as trans-3-methoxy3 ', 4,5'-trihydroxystilbene; piceatannol (trans-3.3 ', 4.5 ¹ tetrahydroxystilbene); 5 - [(lE) -2-phenylethenyl] -1,2,3-benzenetriol; 4 - [(1Z) -2- (3,5-dihydroxyphenyl) ethenyl] -1,2-benzenediol; 5 [(1E) -2- (4-hydroxyphenyl) ethenyl] -1,2,3-benzenetriol; 5 - [(lE) -2 (3,4-dihydroxyphenyl) ethenyl] -1,2,3-benzenetriol; 4 - [(1E) -2- (2,4dihydroxyphenyl) ethenyl] -1,2-benzenediol; acid a - [[(2E) -3- [2 [(lE) -2- (3,4-dihydroxyphenyl) ethenyl] -3,4-dihydroxyphenyl] -l-oxo-2propen-l-yl] oxy ] -3,4-dihydroxy-benzenepropanoic; 2 - [(lE) -2- (3,4-dihydroxyphenyl) ethenyl] -6hydroxy-benzoic acid ethyl ester and 4 - [(lE) -2- (3,5-dimethoxyphenyl) ethenyl] 1.2- benzenediol; and - optical and / or geometric isomers, salts and / or solvates and mixtures of such derivatives. 4. Method according to any one of the preceding claims, characterized in that the ortho-dihydroxy1.2- diphenylethylene derivative (s) are chosen from glycosylated derivatives, and preferably composition (A) comprises 2,3, 5,4'tetrahydroxystilbene-2-O-3-D-glucoside. 5. Method according to any one of the preceding claims, characterized in that the ortho-dihydroxy1,2-diphenylethylene derivative (s) are used in the form of plant extracts. 6. Method according to any one of claims 2 to 5, characterized in that the total amount of the ortho-hydroxy derivative (s) -l, 2-diphenylethylene present in the composition (A) ranges from 0.001 to 10% by weight, and preferably from 0.01 to 5% by weight, relative to the total weight of the composition (A). 7. Method according to any one of the preceding claims, characterized in that the manganese and / or zinc derivative or derivatives are chosen from manganese or zinc salts, preferably chlorides, fluorides, iodides, bromides, sulfates, phosphates, nitrates, perchlorates, carbonates, carboxylates, and mixtures thereof. 8. Method according to any one of the preceding claims, characterized in that it uses one or more Mn (II) salts, preferably chosen from manganese carboxylates, manganese halides and their mixtures, and more preferably from manganese chloride, manganese gluconate and mixtures thereof. 9. Method according to any one of claims 2 to 8, characterized in that the composition (A) comprises one or more manganese derivatives, in a total concentration ranging from 10 ' ³ to 10' ¹ mmol.l ' ¹ , and preferably from 10 ' ² to 10' ¹ mmol.l ' ¹ . 10. Method according to any one of claims 2 to 9, characterized in that the composition (A) comprises one or more zinc derivatives, in a total concentration ranging from 5.10 ' ² to 10 mmol.l' ¹ , and preferably 5.10 ' ¹ to 1 mmol.f ¹ . 11. Method according to any one of the preceding claims, characterized in that the additional polyphenols are chosen from orthodiphenols, that is to say the compounds comprising one or more aromatic rings, preferably benzene, comprising at least two groups hydroxy (OH) carried by two adjacent carbon atoms of the same aromatic ring. 12. Method according to any one of claims 2 to 9, characterized in that the composition (A) comprises one or more orthodiphenol (s) of formula (I) below, or one of its oligomers, in the form salified or not: in which the substituents Ri to R4, identical or different, represent: - a hydrogen atom, - a halogen atom, - a hydroxy radical, - a carboxyl radical, - an alkyl or alkoxycarbonyl carboxylate radical, - an optionally substituted amino radical, an optionally substituted linear or branched alkyl radical, an optionally substituted linear or branched alkenyl radical, - an optionally substituted cycloalkyl radical, - an alkoxy radical, - an alkoxyalkyl radical, an alkoxyaryl radical, the aryl group possibly being substituted, - an aryl radical, - a substituted aryl radical, a heterocyclic radical, saturated or not, carrying or not a cationic or anionic charge, optionally substituted and / or optionally condensed with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted particularly by one or more hydroxy or glycosyloxy groups , - a radical containing one or more silicon atoms, or two of the substituents carried by two adjacent carbon atoms (namely Ri and R ₂ , R ₂ and R3 or R3 and R ₄ ) form jointly with the carbon atoms carrying them 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. 13. Method according to any one of the preceding claims, characterized in that the additional polyphenol or polyphenol (s) are chosen from catechin, quercetin, hematinin, hematoxylin, brazilin, gallic acid , and the natural extracts containing them. 14. Method according to any one of claims 2 to 13, characterized in that the additional polyphenol (s) are present in the composition (A), with a content of pure polyphenol (s) of between 0.001 and 5% by weight relative to the total weight of the composition (A). 15. Method according to any one of the preceding claims, characterized in that the (hydrogen) carbonate (s) are chosen from the compounds 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 the groups R ”, identical or different, represent an atom d hydrogen, an optionally substituted (Ci-Ce) alkyl group such as hydroxyethyl; when R 'represents a hydrogen atom, the hydrogen carbonate is then called dihydrogen carbonate (CO2, H ₂ O); and - Met ' ²⁺ (HCO3O2 with Met' representing an alkaline earth metal; and preferably from alkaline hydrogen carbonates, alkaline earth hydrogen carbonates, ammonium hydrogen carbonates and mixtures thereof; and more preferably from alkaline hydrogen carbonates, alkaline earth hydrogen carbonates and their mixtures. 16. Method according to any one of claims 2 to 15, characterized in that the composition (B) contains the (hydrogen) carbonates a total amount ranging from 0.1% to 15% by weight, preferably from 0 , 5% to 10% by weight, relative to the total weight of the composition (B). 17. Method according to any one of the preceding claims, characterized in that it further comprises the application to the keratin fibers of one or more additional metal salt (s) divalent or trivalent different from manganese salts and zinc salts, preferably chosen from iron (II) salts and iron (III) salts. 18. Method according to any one of the preceding claims, characterized in that one or more glycosylated derivatives of tetrahydroxy-1,2-diphenylethylene are used and in that it further comprises the use of a β type enzyme -glucosidase. 19. Method according to any one of claims 2 to 18, characterized in that it comprises: - the application to keratin fibers of composition (A), then of composition (B); or the application to the keratin fibers of the extemporaneous mixture of the composition (A) and of the composition (B); or the application to the keratin fibers of a composition resulting from the mixture of the composition (A) with the composition (B), 5 maintained before application to the fibers in an oxygen-free receptacle. 20. Multi-compartment device comprising: - A first compartment containing the composition (A) as defined in any one of claims 2 to 14; and 10 - a second compartment containing the composition (B) as defined in any one of claims 2, 15 and 16.