WO2018115354A1

WO2018115354A1 - Process for dyeing hair using (iso)verbascoside derivatives, (hydrogen) carbonates and/or hydroxides, and particular metal salts

Info

Publication number: WO2018115354A1
Application number: PCT/EP2017/084224
Authority: WO
Inventors: Francis Pruche; Gwenaëlle JEGOU
Original assignee: L'oreal
Priority date: 2016-12-23
Filing date: 2017-12-21
Publication date: 2018-06-28
Also published as: FR3060998A1

Abstract

The present invention relates to a process for dyeing hair, comprising the application to said hair of one or more compounds chosen from verbascoside, isoverbascoside and derivatives thereof; of one or more manganese and/or zinc derivatives chosen from manganese salts or oxides and zinc salts or oxides; and of one or more hydroxides and/or (hydrogen) carbonates. The present invention also relates to a multi-compartment device suitable for carrying out such a process.

Description

Process for dyeing hair using (iso)verbascoside derivatives, (hydrogen) carbonates and/or hydroxides, and particular metal salts

The present invention relates to a process for dyeing hair, comprising the application of one or more compounds chosen from verbascoside, isoverbascoside and derivatives thereof, in combination with one or more manganese and/or zinc derivatives, and one or more hydroxides and/or (hydrogen) carbonates.

Many people have sought for a long time to modify the colour of their hair and in particular to mask their grey hair. Essentially two types of dyeing have been developed for this purpose.

The first type of dyeing is "permanent" or oxidation dyeing, which uses dye compositions containing oxidation dye precursors, generally referred to as oxidation bases. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or colour modifiers. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

Most of these permanent dyeing processes provide a good level of coverage of grey hair. However, they require the presence of an oxidizing agent in a strongly alkaline medium (pH generally of greater than 10) and these conditions are all the harsher, the greater the desired degree of coverage of the grey hairs on the head.

The second type of dyeing is "semi-permanent" dyeing or direct dyeing, which consists in applying direct dyes to the keratin fibres, said dyes being coloured and colouring molecules that have an affinity for the fibres, and then leaving them to take, to allow the molecules to penetrate by diffusion to the interior of the fibre, and then rinsing the fibres. In order to perform these dyeing operations, the direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes. The direct dyes may also be natural dyes.

The colourings resulting therefrom are particularly chromatic colourings, but are, however, only temporary or semi-permanent since the nature of the interactions that bind the direct dyes to the keratin fibre and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power and their poor persistence with respect to washing.

Given these drawbacks, consumers are increasingly seeking dyeing processes other than the conventional oxidation dyeing and direct dyeing processes.

Consumers are especially seeking processes which use natural dyes, the use of which is not aggressive for the hair, and especially which do not require the use of oxidizing agents, and which are more environmentally friendly. Consumers are in particular seeking dyeing methods which are well tolerated and which lead to as natural an appearance as possible.

There is a real need to develop novel processes for dyeing hair, making it possible to obtain colouring of the hair while overcoming the abovementioned drawbacks. These processes must especially make it possible to cover grey hair.

There is also a need to obtain gradual colouring of grey hair, to avoid an abrupt change in the user's appearance. Gradual colourings must have a natural effect. They must also make it possible to uniformly cover the head of hair.

These processes must also be easy to apply.

The Applicant has discovered, surprisingly, that the use of one or more compounds chosen from verbascoside, isoverbascoside and derivatives thereof, in combination with one or more manganese and/or zinc derivatives, and one or more hydroxides and/or (hydrogen) carbonates, makes it possible to achieve the objectives set out above.

A subject of the present invention is therefore a process for dyeing hair, comprising the application to said hair of one or more compounds chosen from verbascoside, isoverbascoside and derivatives thereof; of one or more manganese and/or zinc derivatives chosen from manganese salts, manganese oxides, zinc salts and zinc oxides; and one or more hydroxides and/or (hydrogen) carbonates. According to one advantageous embodiment, the process according to the invention also comprises the application to the hair of one or more divalent or trivalent additional metal salts other than the manganese salts and the zinc salts.

The process of the invention advantageously comprises:

a) the application to the hair of a composition (A) comprising the compound(s) chosen from verbascoside, isoverbascoside and derivatives thereof, and the manganese and/or zinc derivative(s), and also

b) the application to the hair of a composition (B) comprising the hydroxide(s) and/or the (hydrogen) carbonate(s).

When the process according to the invention also comprises the application to the hair of one or more divalent or trivalent additional metal salts other than the manganese salts and the zinc salts, these additional metal salts can be present in the composition (A) and/or in the composition (B) and/or in a distinct additional composition (C).

Preferably, these additional metal salts are present in a distinct additional composition (C).

The present invention also relates to a multi-compartment device containing: in a first compartment, a composition (A) comprising one or more compounds chosen from verbascoside, isoverbascoside and derivatives thereof and one or more manganese and/or zinc derivatives; and in a second compartment, a composition (B) comprising one or more hydroxides and/or one or more (hydrogen) carbonates.

According to one advantageous embodiment, one or more divalent or trivalent additional metal salts other than the manganese salts and the zinc salts are present in the composition (A) and/or in the composition (B) of the kit, and/or in a distinct additional composition (C) present in a third compartment.

The process according to the invention is a dyeing process which makes it possible to obtain a (re-)pigmentation of the hair, which is both gradual and visible from the first application.

In the present application, the terms "fibre(s)" or "keratin fibre(s)" are equivalent to hair.

Unlike conventional dyeing processes, the process of the invention makes it possible to produce a real pigmentation or a re-pigmentation of the hair by returning to the original colour or by providing shades thereto, or else by changing the colour. In the case of grey hair, the process makes it possible to gradually re-pigment the hair, depending on the number of applications. It also makes it possible to prevent or delay the appearance of grey hair.

The process of the invention differs from oxidation dyeing processes because it does not employ the condensation of dye precursors in the presence of an oxidizing agent. It also does not correspond to a direct dyeing process because it does not employ coloured molecules. In particular, the (iso)verbascoside and derivatives thereof used in the present invention are not coloured molecules, unlike direct dyes.

The process according to the invention may be repeated, which makes it possible to gradually obtain a dark, ranging from brown to black, colouring effect with a very natural appearance. In particular, the process of the invention makes it possible to obtain an excellent level of dark pigmentation and good coverage of grey hair from a first application. The process can be repeated in order to increase the effect obtained. The repeated applications may take place one after the other or be separated by several hours or even several days.

The process thus makes it possible to obtain good colouring intensity, especially good coverage of grey hair over the whole head of hair, and also good colour homogeneity along the keratin fibres.

Finally, the colourings obtained in this way are not aggressive and are well tolerated by the hair. The process according to the invention does not damage the hair and provides it with a good level of conditioning, especially in terms of manageability, softness, smoothness and disentangling.

The process according to the invention also makes it possible to carry out a gradual re-pigmentation of the skin.

Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

In the text hereinbelow, and unless otherwise indicated, the limits of a range of values are included within that range, especially in the expressions "between" and "ranging from ... to

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

The term "substituted" or "optionally substituted" is intended to mean conventional substituents of the chemical radicals in question, such as alkyl, amino, aminoalkyl, hydroxyl, hydroxyalkyl, halogenated substituents, etc. The (iso)verbascoside derivatives

The present invention uses one or more compounds chosen from verbascoside, isoverbascoside and derivatives thereof.

These compounds are in particular present in the composition (A).

The terms "verbascoside derivatives" and "isoverbascoside derivatives" denote respectively compounds comprising in their chemical structure at least one verbascoside group and at least one isoverbascoside group, and which are substituted on one or more of the hydroxyl (-OH) groups.

Verbascoside is a glycoside that is known per se, the structure which is the following:

Isoverbascoside is also a known glycoside, the structure of which following:

in which:

- R is chosen from a hydrogen atom, an alkyl radical, an acetyl radical and benzene group, and

- Ri is chosen from hydrogen, an alkyl radical, and a benzene group. Mention may in particular be made of the following compounds:

2: R,-R₂-H

4: R, = acetyl, R₂=H

S; R_t = R₂= acetyl

The verbascoside and isoverbascoside derivatives are in particular described in Biotechnology Advances Volume 32, Issue 6, 1 November 2014, Pages 1065- Among these derivatives, use may in particular be made of the acetyl derivatives. The acetylation maybe partial, such as that for example described in Journal of Molecular Catalysis B: Enzymatic, Volume 104, June 2014, Pages 42-47.

These compounds may be of natural origin, or of synthetic origin (that is to say obtained by chemical synthesis, or by the biotechnological route).

They can be used in the form of extracts.

The extracts containing verbascoside, isoverbascoside or derivatives thereof may be natural, or obtained by the biotechnological route from cultures of cells of various species, for example: Syringa vulgaris, Buddleia davidii, Buddleja cordobensis grisebach.

The natural extracts are in particular plant extracts. Mention may for example be made of olive oil, or extracts of seaside twintip (Stemodia maritima Linn).

Verbascoside is particularly preferably used, and even more preferentially in natural extract form.

The total amount of the compounds chosen from verbascoside, isoverbascoside and derivatives thereof preferably ranges from 0.01% to 15% by weight, and more preferentially from 0.1% to 10% by weight, relative to the total weight of the composition (A).

When these compounds are used in the form of natural extract, a content of extract ranging from 0.1% to 50% by weight and preferably from 0.5% to 20% by weight relative to the total weight of the composition (A) is typically used.

According to a particularly preferred embodiment, the process according to the invention does not employ oxidation dyes or direct dyes, other than the compounds chosen from verbascoside, isoverbascoside and derivatives thereof, and also the optionally employed (poly)phenols described below.

The manganese and/or zinc derivatives

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

These manganese and/or zinc derivative(s) are preferably contained in the composition (A). For the purposes of the present invention, "salts" are intended to mean actual salts in the ionized form. These salts may be solvated, in particular hydrated.

The derivatives are preferably salts.

Particularly, the derivatives of the invention are in oxidation state II, such as Mn(II) and Zn(II).

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

The carboxylates of use in the invention also include carboxylic acid salts comprising one or more hydroxyl radicals such as gluconates.

By way of example of carboxylates, mention may be made, for example, of acetate, tartrate, lysinate, glutamate, lactate, glycinate, aspartate, stearate, acetylacetate.

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

Among the manganese salts, preference is given to manganese chloride, manganese carbonate, manganese difluoride, manganese acetate tetrahydrate, manganese lactate trihydrate, manganese phosphate, manganese iodide, manganese nitrate trihydrate, manganese bromide, manganese perchlorate tetrahydrate, manganese sulfate monohydrate, manganese gluconate and mixtures thereof.

Among the zinc salts, preference is given to zinc sulfate, zinc gluconate, zinc chloride, zinc lactate, zinc acetate, zinc glycinate, zinc aspartate and mixtures thereof.

Preferably, the process of the invention employs one or more manganese salts, in particular Mn(II) metal salts.

Even more preferentially, the manganese salt(s) are chosen from manganese carboxylates, especially manganese gluconate, and manganese halides, such as manganese chloride, and mixtures thereof.

Better still, the manganese salt(s) are chosen from manganese chloride, manganese gluconate and mixtures thereof. When the composition (A) comprises one or more manganese derivatives, the total concentration of said derivative(s) in the composition (A) preferably ranges from 10^"2 to 10 mmol.l^"1, and more preferentially from 10^"1 to 5 mmol.l^"1.

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

The amounts above are expressed relative to a composition (A) in liquid form. The (hydrogen) carbonates

The (hydrogen) carbonate(s) used in the process of the invention are especially chosen from the compounds of the following formulae:

R'⁺, HCO3^" with R' representing a hydrogen atom, an alkali metal, an ammonium R^M4N⁺- or phosphonium R^M4P⁺- group, in which the groups R", which may be identical or different, represent a hydrogen atom, an optionally substituted (Ci-

C₆)alkyl group such as hydroxyethyl; when R represents a hydrogen atom, the hydrogen carbonate is then referred to as dihydrogen carbonate (CO2, H₂0); and Met'²⁺ (HC0₃ ^")₂ with Met' representing an alkaline earth metal.

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

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

These (hydrogen) carbonates may originate from a natural water, for example spring water from the Vichy basin or from La-Roche-Posay or Badoit water (cf. for example, patent document FR 2 814 943). Mention may particularly be made of sodium carbonate Na₂C0₃, sodium hydrogen carbonate or sodium bicarbonate NaHC0₃. These hydrogen carbonates may also be generated in situ by any process making it possible to generate an HCO3^" salt.

The hydroxides

The hydroxides are in particular chosen from the hydroxides having the following formulae: sodium, potassium and calcium hydroxides. Calcium hydroxide is preferentially used.

The composition (B) may contain a total amount of the (hydrogen) carbonate(s) and/or of the hydroxide(s) which preferably ranges from 0.1% to 20% by weight and more preferentially from 0.5% to 15% by weight, and even better still from 1% 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 of zinc salts applied to the hair.

The metal salts other than the manganese and zinc salts

The process according to the present invention can also use one or more additional divalent or trivalent metal salt(s) other than the manganese salts and zinc salts defined above.

For the purposes of the present invention, "metal salt" is intended to mean actual salts, that is to say in ionized form, of the metals of columns 3 to 14 of the periodic table of the elements, other than manganese and zinc.

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

The additional metal salt(s) are preferably chosen from iron(II) salts and iron(III) salts.

More preferentially, the additional metal salt(s) are chosen from iron sulfate, iron fumarate, iron gluconate, iron acetylacetonate, iron oxalate, iron glycinate, mixed salts, such as Mohr's salt, and the mixtures thereof; and better still, iron sulfate.

These salts can be added as they are, or in the form of extracts (in particular of plant extracts such as, for example, lentil extracts, spinach extracts) or in the form of other natural mixtures containing them (for example, clays). According to a first preferred embodiment, the additional metal salt(s) are present in the composition (A).

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

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

The total amount of the additional metal salt(s) preferably ranges from 0.001% to 5% by weight and more preferentially from 0.01% to 4% by weight relative to the total weight of the composition containing same.

Surfactants

The compositions of use for the invention may optionally comprise one or more surfactants.

The surfactant(s) of use are preferably chosen from non- ionic surfactants, anionic surfactants and amphoteric or zwitterionic surfactants.

The total amount of surfactant(s) present in the compositions according to the invention may 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 same.

The surfactant(s) are preferably present in the composition (B).

The polyphenols other than the verbascoside and isoverbascoside derivatives

The process of the invention can also comprise the application to the hair of one or more additional phenol(s) different from the verbascoside derivatives and the isoverbascoside derivatives.

The additional phenol(s) are preferably contained in the composition (A).

These additional polyphenols are preferably chosen from ortho-diphenols, that is to say compounds comprising one or more aromatic rings, preferably benzene rings, comprising at least two hydroxyl groups (OH) borne by two adjacent carbon atoms of the same aromatic ring. The ortho-diphenol(s) of use in the invention are in particular not auto-oxidizable derivatives, especially auto-oxidizable derivatives with an indole unit. More particularly, they are not 5,6-dihydroxyindole.

The aromatic ring may more particularly be a fused aryl or fused heteroaromatic ring, i.e. optionally comprising one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chromane, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring comprising at least two hydroxyl groups borne by two adjacent carbon atoms of the aromatic ring. Preferentially, the aromatic ring of the ortho-diphenol derivatives according to the invention is a benzene ring.

"Fused ring" is intended to mean that at least two saturated or unsaturated and heterocyclic or non-heterocyclic rings have a common bond, that is to say that at least one ring is placed side-by-side with another ring.

The additional ortho-diphenols may or may not be salified. They may also be in the aglycone form (without bonded sugar) or in the form of glycosylated compounds.

According to a particularly preferred embodiment, the composition (A) comprises one or more ortho-diphenol(s) of formula (I) below, or an oligomer thereof, in salified or non-salified form:

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

a hydrogen atom,

a halogen atom,

a hydroxyl radical,

a carboxyl radical,

- an alkyl carboxylate or alkoxycarbonyl radical,

an optionally substituted amino radical,

an optionally substituted, linear or branched alkyl radical,

an optionally substituted, linear or branched alkenyl radical, an optionally substituted cycloalkyl radical,

an alkoxy radical,

an alkoxyalkyl radical,

an alkoxyaryl radical, the aryl group possibly being optionally substituted, - an aryl radical,

a substituted aryl radical,

a saturated or unsaturated heterocyclic radical optionally bearing a cationic or anionic charge, optionally substituted and/or optionally fused with an aromatic ring, preferably a benzene ring, said aromatic ring being optionally substituted, in particular with one or more hydroxyl or glycosyloxy groups, a radical containing one or more silicon atoms,

or two of the substituents borne by two adjacent carbon atoms (namely Ri and R₂, R₂ and R₃ or R₃ and R₄) form, together with the carbon atoms bearing them, a saturated or unsaturated, aromatic or non-aromatic ring, optionally containing one or more heteroatoms and optionally fused with one or more saturated or unsaturated rings optionally containing one or more heteroatoms.

Preferably, the additional ortho-diphenol derivatives of formula (I) are chosen from those in which two adjacent substituents Ri - R₂, R₂ - R₃ or R₃ - R₄ cannot form, with the carbon atoms which bear them, a cyclic radical, in particular a pyrrolyl radical. More particularly, R₂ and R₃ cannot form a pyrrolyl radical fused to the benzene ring bearing the two hydroxyls.

For the purposes of the present invention and unless otherwise indicated: The saturated or unsaturated, optionally fused rings may also be optionally substituted.

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

The alkenyl radicals are unsaturated, linear or branched, C2-C20 hydrocarbon- based radicals; preferably comprising at least one double bond, such as ethylene, propylene, butylene, pentylene, 2-methylpropylene and decylene.

The aryl radicals are monocyclic or fused or non- fused polycyclic carbon-based radicals, preferentially comprising from 6 to 30 carbon atoms, at least one ring of which is aromatic; the choice is preferentially made, from the aryl radical, of a phenyl, biphenyl, naphthyl, indenyl, anthracenyl and tetrahydronaphthyl. The alkoxy radicals are alkyl-oxy radicals with alkyl as defined previously, preferably Ci-Cio, such as methoxy, ethoxy, propoxy and butoxy.

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

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

The additional ortho-diphenols of use in the process of the invention may be natural or synthetic. The natural ortho-diphenols include the compounds which may be present in nature and which are reproduced by chemical (semi)synthesis.

According to a particular embodiment of the invention, the process comprises the application of one or more additional synthetic ortho-diphenol(s) that do not exist in nature.

According to another preferred embodiment of the invention, the additional ortho-diphenols are natural ortho-diphenols.

More particularly, the additional natural ortho-diphenols of use in the process of the invention are chosen from:

- flavanols, such as catechin and epicatechin gallate,

- flavonols, such as quercetin,

- anthocyanidins, such as cyanidin, delphinidin, petunidin or pelargonidin,

- anthocyanins or anthocyans such as delphinidin 3-O-glucoside, also referred to as myrtillin,

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

- flavones, such as luteolin,

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

- 2,3-dihydroxyphenylalanine and the derivatives thereof,

- 4,5-dihydroxyphenylalanine and the derivatives thereof,

- dihydroxycinnamates, such as caffeic acid and chlorogenic acid,

- ortho-polyhydroxycoumarins,

- ortho-polyhydroxyisocoumarins,

- ortho-polyhydroxycoumarones, - ortho-polyhydroxyisocoumarones,

- ortho-polyhydroxychalcones,

- ortho-polyhydroxychromones,

- quinones,

- hydroxyxanthones,

- 1 ,2-dihydroxybenzene and the derivatives thereof,

- 1,2,4-trihydroxybenzene and the derivatives thereof,

- 1,2,3-trihydroxybenzene and the derivatives thereof,

- 2,4,5-trihydroxytoluene and the derivatives thereof,

- proanthocyanidins and especially the proanthocyanidins Al, A2, Bl, B2,

B3 and CI,

- proanthocyanins,

- tannic acid,

- ellagic acid,

- and mixtures of the preceding compounds,

and more particularly from catechin, quercetin, brazilin (CAS 474-07-7), haematein, haematoxylin, chlorogenic, caffeic and gallic acids, catechol, L DOPA, pelargonidin, cyanidin, (-)-epicatechin, (-)-epigallocatechin, (-)-epigallocatechin 3- gallate (EGCG), (+)-catechin, isoquercetin, pomiferin, esculetin, 6,7-dihydroxy-3-(3- hydroxy-2,4-dimethoxyphenyl)coumarin, santalin AC, mangiferin, butein, maritimetin, sulfuretin, robtein, betanidin, pericampylinone A., theaflavin, proanthocyanidin A2, proanthocyanidin B2, proanthocyanidin CI, procyanidins DP 4-8, tannic acid, purpurogallin, 5,6-dihydroxy-2-methyl-l,4-naphthoquinone, alizarin, wedelo lactone, variegatic acid, gomphidic acid, xerocomic acid, carnosol, and the natural extracts containing same.

Preferentially, the additional ortho-diphenol(s) according to the invention are chosen from flavanols, flavonols, ortho-hydroxybenzoates, isoflavones and neoflavones.

According to one embodiment, the natural ortho-diphenols are derived from, or are introduced in the form of, extracts of animals, bacteria, fungi, algae, plants and fruits, used in their entirety or partially. In particular regarding plants, the extracts are derived from fruits, including citrus fruits, from vegetables, from trees, from shrubs and lichen. Use may also be made of mixtures of these extracts rich in ortho- diphenols as defined above. Preferably, the additional ortho-diphenol(s) are natural ortho-diphenols derived from extracts of plants or plant parts. These extracts of plants or plant parts may be used directly in the process of the invention.

The extracts are obtained by extraction of various plant parts, for instance the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod or the peel.

Mention may be made, among the extracts of plants, of extracts of rose or tea leaves.

Mention may be made, among the extracts of fruits, of extracts of apple, extracts of grape (in particular of grape seed) or extracts of cocoa beans and/or pods.

Mention may be made, among the extracts of vegetables, of extracts of potato or of onion peel.

Mention may be made, among the extracts of tree wood, of extracts of pine bark and extracts of logwood.

Use may also be made of mixtures of plant extracts.

According to a particular embodiment of the invention, the ortho- diphenol(s) are natural extracts rich in ortho-diphenols. According to a preferred embodiment, the additional ortho-diphenol derivative(s) are solely contained in natural extracts.

Preferentially, the polyphenol(s) used in the process according to the invention are chosen from catechin, quercetin, haematein, haematoxylin, brazilin, brazilein, gallic acid, and natural extracts containing same, chosen especially from grape marc, pine bark, green tea, onion, cocoa bean, logwood, redwood and gall nut. The extract used is preferably logwood.

Even more preferentially, the additional polyphenol(s) are chosen from catechin, quercetin, gallic acid and haematoxylin.

The natural extracts containing the additional polyphenols according to the invention may 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 or natural polyphenol(s) and/or the natural extract(s) containing same preferably represent(s) from 0.001% to 20% by weight of the total weight of the composition containing same, preferably the composition (A). As regards the pure ortho-diphenols, the content in the composition(s) containing same is preferably between 0.001% and 5% by weight of each of these compositions. The compositions

The compositions used in the present invention may be in any form which is compatible with an application to the hair.

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

They may be aqueous solutions, in particular aqueous-alcoholic solutions. They generally comprise water or a mixture of water and of one or more solvents, for example chosen from the lower Ci to C₄ alcohols, such as ethanol, isopropanol, tert- butanol or n-butanol; polyols such as glycerol, propylene glycol and polyethylene glycols; benzyl alcohol; and mixtures thereof, and ethyl carbonate.

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

When one or more compositions containing a metal salt is in the form of a solution, the latter must not flocculate. Those skilled in the art will choose the suitable pH to prevent flocculation of the composition, as a function of the metal salt.

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

The compositions (A), (B) and, where appropriate, (C) used in the present invention can also comprise one or more fatty substances, and in particular one or more oils.

The term "fatty substance" is intended to mean an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg; i.e. 1.013^χ 10⁵ Pa) (solubility of less than 5% and preferably of less than 1%, more preferably still of less than 0.1%). They bear in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.

The term "oil" is intended to mean a "fatty substance" that is liquid at ambient temperature (25°C) and at atmospheric pressure (760 mmHg or 1.013^χ 10⁵ Pa).

The term "non-silicone oil" is intended to mean an oil not containing any silicon (Si) atoms and the term "silicone oil" is intended to mean an oil containing at least one silicon atom.

More particularly, the fatty substance(s) are chosen from C6-C16 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, triglycerides of plant or synthetic origin, fluoro oils, fatty alcohols, esters of fatty acids and/or of fatty alcohols other than triglycerides and non-silicone waxes, in particular plant waxes, silicone or non-silicone waxes, silicone oils, and mixtures thereof.

It is recalled that the fatty alcohols, esters and acids more particularly contain at least one saturated or unsaturated, linear or branched hydrocarbon-based group, comprising 6 to 30 and better still from 8 to 30 carbon atoms, which is optionally substituted, in particular, with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

Among the fatty substances, preference is in particular given to those of plant origin, that is to say vegetable oils and plant waxes. By way of non-limiting example, mention is made of avocado oil, sweet almond oil, argan oil and shea butter.

The additives

The compositions of use in the invention may comprise one or more additives, among which mention may be made of cationic, anionic, non-ionic and amphoteric polymers or the mixtures thereof, thickeners, anti-dandruff agents, antiseborrheic agents, agents for preventing hair loss and/or promoting hair regrowth, vitamins and provitamins including panthenol, sunscreens, sequestrants, plasticizers, solubilizers, acidifying agents, opacifiers or nacreous agents, hydroxy acids, urea, fragrances, preservatives, or fillers, preferentially of natural origin. As fillers, mention may be made of pigments such as iron oxides derived from ochres, carbon black, chlorophyll or polymerized anthocyans.

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

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

The process

When the process according to the present invention is carried out starting with the compositions (A), (B) and where appropriate (C), the compositions (A) and (B), and also the composition (C) when it is present, are applied to dry or wet hair and preferably to wet hair.

According to one preferred embodiment, the process comprises the application of the composition (A), followed by the application of the composition (B).

The compositions (A) and (B) may also be mixed extemporaneously before their application to the hair. They may thus be kept, before application, in a compartment which does not contain oxygen. Oxygen from the air will then act directly on the hair. This embodiment makes it possible to reduce the number of steps to obtain pigmentation of the hair.

In this embodiment, the additional metal salt(s), when they are used, can also be present in the composition (A).

According to an also preferred embodiment, the additional metal salt(s) as defined above are present in a composition (C) separate from the compositions (A) and (B) and the three compositions (A), (B) and (C) are applied successively to the hair.

According to this particular embodiment, the process more preferentially comprises the application, to the hair:

- of the composition (A), then

- of the composition (B), then

- of the composition (C), or

- of the composition (C), then

- of the composition (A), then

- of the composition (B),

preferably with a time gap between the application of the composition (A) and of the composition (B).

Each of the compositions (A), (B) and optionally (C) is advantageously left in place on the hair for a duration ranging from 30 seconds to 1 hour, and more preferentially from 30 seconds to 30 minutes.

The process of the present invention may be repeated several times, especially from 2 to 50 times, preferably from 3 to 30 times, depending on the desired degree of colouring. The greater the number of applications, the more intense and the darker is the colouring, thereby improving the re-pigmentation of grey hair.

Advantageously, the process of the invention is carried out by re-applying the compositions (A), (B) and optionally (C) several times, to obtain, over time, a natural and visible colouring. For example, the compositions according to the invention may be applied after each shampooing operation, or for example once or twice per week.

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

More preferentially, the process comprises a single final rinsing step. In other words, the hair is only rinsed after the application of the final composition. Device

Finally, the present invention relates to a multi-compartment device comprising:

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

a second compartment containing the composition (B) as defined above; and - optionally, a third compartment containing the composition (C) as defined above.

According to another embodiment of the device, the latter contains a compartment comprising a composition resulting from the mixing of the composition (A) with the composition (B), this compartment not containing oxygen. The device according to the present invention can also comprise an additional compartment containing the composition (C) as defined previously.

The compositions of the compartments are intended to be applied successively to hair according to the process as described above.

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

EXAMPLES In all the examples below, the colour of the locks was evaluated in the CIE

L*a*b* system, using a Minolta Spectrophotometer CM2600D colorimeter.

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

In the examples that follow, all the amounts are indicated as weight percentages relative to the total weight of each composition.

Example 1 :

An aqueous solution containing 10 mg of verbascoside and manganese gluconate at a concentration of 1 mmol.l^"1 was applied to a lock of Caucasian hair comprising 90% natural grey hair. 1 ml of solution was applied to a lock of 0.5 g.

The lock was then left to stand at 22°C for 30 minutes.

1 ml of an aqueous solution of sodium hydrogen carbonate at 8% by weight of active material was then applied to the lock.

The lock was then left to stand at 22°C for 30 minutes.

1 ml of an aqueous solution of iron sulfate at 1% by weight of active material was then applied to the lock.

After a leave-on time of 3 minutes at 22°C, the lock of hair was rinsed with water and then left to dry.

This process resulted in the obtaining of a brown colouring of the lock, of natural appearance. The colour of the lock obtained was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM2600D colorimeter.

The table below represents the colouring intensity values, evaluated in the L*a*b* system.

Example 2:

An aqueous solution containing 50 mg of natural extract containing verbascoside (extract of Syringa Vulgaris cell culture with malodextrin, having a verbascoside content of 50% by weight) and manganese gluconate at a concentration of 1 mmol.l^"1 was applied to a lock of Caucasian hair comprising 90% natural grey hair. 1 ml of solution was applied to a lock of 0.5 g.

The lock was then left to stand at 22°C for 30 minutes.

1 ml of an aqueous solution of sodium hydrogen carbonate at 8%> by weight of active material was then applied to the lock.

The lock was then left to stand at 22°C for 30 minutes.

This process resulted in the obtaining of a brown colouring of the lock, of natural appearance.

The colour of the lock obtained was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM2600D colorimeter.

The table below represents the colouring intensity values, evaluated in the L*a*b* system. L* a* b*

Hair before

54.7 1.1 15.3 treatment

After treatment (1

22.4 4.7 1.3 application)

Examples 1 and 2 above show that the process according to the present invention makes it possible to darken the colour of the hair from the first application.

Claims

1. Process for dyeing hair, comprising the application to said hair of one or more compounds chosen from verbascoside, isoverbascoside and derivatives thereof; of one or more manganese and/or zinc derivatives chosen from manganese salts, manganese oxides, zinc salts and zinc oxides; and of one or more hydroxides and/or (hydrogen) carbonates.

2. Process according to Claim 1, characterized in that it comprises:

3. Process according to the preceding claim, characterized in that it also comprises the application to the hair of one or more divalent or trivalent additional metal salts other than the manganese salts and the zinc salts, these additional metal salts being present in the composition (A) and/or in the composition (B) and/or in a distinct additional composition (C).

4. Process according to any one of the preceding claims, characterized in that it uses verbascoside, preferably in the form of a natural extract.

5. Process according to any one of Claims 2 to 4, characterized in that the total amount of the compounds chosen from verbascoside, isoverbascoside and derivatives thereof ranges from 0.01% to 15% by weight, and more preferentially from 0.1% to 10% by weight, relative to the total weight of the composition (A).

6. Process according to any one of the preceding claims, characterized in that the manganese and/or zinc derivative(s) are chosen from manganese or zinc salts, and preferably from chlorides, fluorides, iodides, bromides, sulfates, phosphates, nitrates, perchlorates, carbonates, carboxylates, and mixtures thereof.

7. Process 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 mixtures thereof, and more preferentially from manganese chloride, manganese gluconate and mixtures thereof.

8. Process according to any one of Claims 2 to 7, characterized in that the composition (A) comprises one or more manganese derivatives in a total concentration ranging from 10^"2 to 10 mmol.l^"1, and more preferentially from 10^"1 to 5 mmol.l^"1, expressed relative to a composition (A) in liquid form.

9. Process according to any one of Claims 2 to 8, 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 from 5.10^"1 to 1 mmol.l^"1, expressed relative to a composition (A) in liquid form.

10. Process according to any one of the preceding claims, characterized in that the (hydrogen) carbonate(s) are chosen from the compounds of the following formulae:

- R'⁺, HCO3^" with R' representing a hydrogen atom, an alkali metal, an ammonium R^M4N⁺- or phosphonium R^M4P⁺- group wherein the R" groups, which may be identical or different, represent a hydrogen atom, or an optionally substituted (Ci-C₆)alkyl group such as hydroxyethyl; and

- Met'²⁺ (HCC"3^")2 with Met' representing an alkaline earth metal;

and preferably from alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, ammonium hydrogen carbonates and mixtures thereof; and more preferentially from alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates and mixtures thereof.

11. Process according to any one of the preceding claims, characterized in that the hydroxide(s) are chosen from sodium, potassium and calcium hydroxides, and preferably calcium hydroxide.

12. Process according to any one of Claims 2 to 11, characterized in that the composition (B) contains the (hydrogen) carbonate(s) and/or the hydroxide(s) in a total amount ranging from 0.1% to 15% by weight and preferably from 0.5% to 10% by weight relative to the total weight of the composition (B).

13. Process according to any one of Claims 3 to 12, characterized in that the additional metal salt(s) are chosen from iron(II) salts and iron(III) salts, preferably from iron sulfate, iron fumarate, iron gluconate, iron acetylacetonate, iron oxalate, iron glycinate, mixed salts, such as Mohr's salt, and mixtures thereof; and better still, iron sulfate.

14. Process according to any one of Claims 3 to 13, characterized in that the total amount of additional metal salt(s) ranges from 0.001% to 5% by weight and preferably from 0.01% to 4% by weight relative to the total weight of the composition containing same.

15. Process according to any one of Claims 3 to 14, characterized in that the additional metal salt(s) are present in a composition (C) distinct from the compositions (A) and (B), and the three compositions (A), (B) and (C) are applied successively to the hair.

16. Process according to Claim 15, characterized in that it comprises the application, to the hair:

- of the composition (A), then

- of the composition (B), then

- of the composition (C),

or

- of the composition (C), then

- of the composition (A), then

- of the composition (B).

17. Process according to any one of Claims 3 to 14, characterized in that the additional metal salt(s) are present in the composition (A), and the process comprises the application of the composition (A), followed by the application of the composition (B).

18. Multi-compartment device comprising:

- a first compartment containing the composition (A) as defined in any one of Claims 2 to 9;

a second compartment containing the composition (B) as defined in any one of Claims 10 to 12; and

- optionally, a third compartment containing the composition (C) in any one of Claims 3, 13 and 14.