Dyeing method employing an expanded oxidizing composition

The present invention relates to a method for dyeing keratin fibres, and more particularly keratin fibres such as the hair, that employs a dyeing composition and an expanded oxidizing composition.

The present invention also relates to an expanded oxidizing composition (B) and a ready-to-use composition for the oxidation dyeing o f keratin fibres, and more particularly o f human keratin fibres such as the hair, o f the type comprising the mixing o f a dyeing composition (A) with an expanded oxidizing composition (B) .

Lastly, the present invention relates to a kit for the oxidation dyeing o f keratin fibres, comprising the compositions according to the invention.

Many people have for a long time sought to modify the co lour of their hair, and especially to dye it in order, for example, to mask their grey hair.

In order to dye human keratin fibres durably, dyeing methods have been developed which are referred to as permanent, and are also called oxidation dyeing. These methods employ dyeing compositions containing oxidation dye precursors, also known generally as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para- aminopheno ls and heterocyclic compounds. These oxidation bases are co lourless or weakly co loured compounds which, in combination with oxidizing products, are able to give rise to coloured compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or co loration modifiers, the latter being chosen especially from aromatic meta- diaminobenzenes, from meta-aminophenols, from meta-dipheno ls and from certain heterocyclic compounds such as indole compounds .

The second type o f dyeing is so-called semi-permanent or direct dyeing, which invo lves app lying direct dyes to the keratin fibres, these dyes being co loured and colouring mo lecules having an affinity for said fibres, and then leaving them to act, and subsequently rinsing them.

In order to perform these dyeings, the direct dyes generally employed are chosen from direct nitrobenzene, anthraquinone, nitropyridine, azo, xanthenes, acridine, azine or triarylmethane dyes, and from natural dyes .

The compositions containing one or more direct dyes are applied to the keratin fibres for a time required in order for the desired co loration to be obtained, and are then rinsed. The resulting co lorations are generally chromatic co lorations which are, however, temporary or semi-permanent, since the nature of the interactions which bond the direct dyes to the keratin fibre, and their desorption from the surface and/or from the core of the fibre, are responsible for their low tinctorial power and their low resistance to washing or perspiration.

In order to improve this direct dyeing, proposals have been made to use it as the oxidation dyeing in the presence of oxidizing agents . In that case, it is referred to as direct lightening dyeing.

The oxidizing compositions generally take the form o f so lutions, gels or more or less fluid creams . Users o f cosmetic products are now increasingly looking for products that are pleasant to use and that have a novel texture.

The Applicant has now discovered that the use o f an expanded oxidizing composition, in the course of a dyeing method, allows a new texture to be obtained, with good use qualities, particularly in terms o f ease o f application, whether used alone, sequentially or as a mixture with an optionally expanded dyeing composition.

More particularly, oxidizing compositions, and possibly the dyeing compositions, used in the method according to the invention take the form o f compositions which have been expanded or are intended to be so .

An expanded composition in the sense of the present patent application refers to a composition into which a gas is introduced in order to give the composition the appearance o f a foam and to reduce its density, more particularly for the purpose of forming gaseous cells within the composition that are separated by thin sheets o f base composition and hence to endow the composition with a foam texture .

The present invention therefore has as a subj ect a method for dyeing keratin fibres, employing a dyeing composition (A) and an expanded oxidizing composition (B),

- said dyeing composition (A) comprising one or more dyes, and

- said expanded oxidizing composition (B) comprising one or more oxidizing agents and from 30 to 70 % by weight relative to the total weight of the expanded oxidizing composition, o f one or more gases.

The expanded composition (B), and also the mixture o f the dyeing composition (A) with the expanded oxidizing composition (B) in the method according to the invention, exhibit very good service qualities, and in particular an especially pleasant and lightened texture.

In particular, the mixing o f the compositions (A) and (B) is very easy to accomplish and very easy to apply and to spread over lo cks o f hair, and more particularly to the roots .

In addition, it does not run and remains well located at the points of application and spreads easily from the roots to the ends .

Lastly, the use of the method according to the invention results in a co loration having very good qualities, especially in terms o f establishment, intensity, uniformity and selectivity o f the co loration obtained.

The invention also relates to an expanded oxidizing composition comprising one or more oxidizing agents and from 30 to 70 % by weight relative to the total weight o f the expanded oxidizing composition, of one or more gases, and to a ready-to-use composition for the oxidation dyeing o f keratin fibres and more particularly o f human keratin fibres such as the hair, comprising the extemporaneous mixing o f an optionally expanded dyeing composition (A) with an expanded oxidizing composition (B), which compositions may be present in dyeing kits.

Another subj ect of the invention is a co louring kit comprising first an optionally expanded dyeing composition (A), and secondly an expanded oxidizing composition (B) .

Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples that fo llow.

In that which fo llows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "of between" and "ranging from ... to

Moreover, the expression " at least one" used in the present description is equivalent to the expression "one or more" .

According to the invention, the method for dyeing keratin fibres emp loys a dyeing composition (A) and an expanded oxidizing composition (B),

- said dyeing composition (A) comprising one or more dyes, and

- said expanded oxidizing composition (B) comprising one or more oxidizing agents and from 30 to 70 % by weight relative to the total weight of the expanded oxidizing composition, o f one or more gases.

The dyeing composition (A) may also be expanded and may further comprise one or more gases .

The gas content by weight varies preferably from 1 % to 70%, more preferably from 20% to 60% and more preferably still from 30% to 50%) of the expanded dyeing composition (A) .

More particularly, the gas content in the expanded dyeing composition (A) varies from 30%> to 70%> by weight, and even more preferably from 30% to 60% by weight relative to the total weight o f the expanded dyeing composition (A) .

The gas or gases used in the expanded compositions o f the invention is or are preferably air, an inert gas or a mixture thereof. An inert gas in the sense o f the present invention is a gas lacking chemical reactivity in the environment in which it is located. More particularly, the gas according to the invention is inert towards the oxidation of dyes.

Examples o f inert gas are nitrogen, carbon dioxide, nitrogen oxides or a noble gas, or a mixture thereof. The inert gas or gases is or are, better still, chosen from nitrogen, argon, helium, carbon dioxide and mixtures thereof, and better still from nitrogen, argon and mixtures thereof.

The expanded compositions used in the method of the invention are formed stably in the form o f a fo am with the aid o f a base composition and one or more gases .

The gas or gases may represent in particular from 1 0% to 500% of the vo lume o f the unexpanded composition, preferably from 30% to 200%, more preferably from 35 % to 150% and better still from 40% to

140% .

This vo lume may be calculated by comparing the density o f the base composition and that of the expanded composition.

This vo lume corresponds to the degree of expansion o f the composition (or level of gas introduced into the composition), and may in particular be calculated by the following formula:

Degree of expansion = ^{d before e " d foam} x lOO

Without limitation, this degree o f expansion may in particular be measured on a composition which has already been expanded, using the fo llowing protocol:

the expanded composition is introduced into a 100 ml beaker so as to occupy the total beaker vo lume, while avoiding formation o f air bubbles during the filling of the j ar;

it is left to stand for 10 minutes and then the vo lume V I , corresponding to the vo lume o f the expanded composition, is recorded; a turbine is introduced, and the beaker and the turbine are placed under a vacuum bell j ar;

the vacuum is actuated and the blade of the turbine is rotated at a slow speed (500 rpm) for 10 minutes;

- the vacuum is disconnected and the vo lume V2, corresponding to the vo lume o f the unexpanded base composition, is recorded.

The degree o f expansion is then calculated by the fo llowing formula:

V - V

Degree of expansion =— ^— - x 100

Besides air, the gases able to produce the expanded composition are, in particular, inert gases, for example nitrogen, carbon dioxide, nitrogen oxides, noble gases, or a mixture o f said gases. When the composition comprises a compound which is sensitive to oxidation, it is preferable to use an oxygen-free gas such as nitrogen, argon or carbon dioxide .

The quantity o f gas introduced into the base composition contributes to the adjustment in density of the expanded composition to the desired value.

The expanded composition o f the invention may have a density of less than 0.95 g/cm ³ . The expanded composition o f the invention advantageously possesses a density ranging from 0.2 to 0.9 g/cm ³ and preferably from 0.3 to 0.8 g/cm ³ , this density being measured at a temperature o f approximately 20°C and at atmospheric pressure in the fo llowing protocol.

The test is carried out on a composition vo lume o f 25 ml, introduced into a 25 ml (Vi ) smooth plexiglas® j ar which defines a cylindrical filling space with a height of 15 mm and a base with a diameter of 46 mm. The j ar has a bottom wall 10 mm thick and a side wall 12 mm thick.

Prior to measurement, the composition to be characterized and the j ar are maintained at a temperature of the order of 20°C . The j ar is tared and the weight value is noted (Mi ) . The expanded composition is subsequently introduced into the jar so as to occupy its total vo lume, while avoiding the formation o f air bubbles during the filling o f the j ar. The combination is left to stand at ambient temperature for 24 hours. The top of the j ar is subsequently levelled before it is weighed (M ₂ ) . The density is evaluated according to the convention p = (M ₂ -Mi )/25.

The expanded composition according to the invention preferably exhibits a satisfactory stability, which may be evaluated by measuring a vo lume o f foam (V ₂ ) remaining in the j ar after one month at 45 °C , according to the protocol described above for the measurement of density.

The ratio V ₂ /Vi corresponds to the ratio between the vo lume o f the expanded composition after one month at 45 °C and the vo lume o f the expanded composition after 24 hours.

The expression "satisfactory stability" is applied in particular to expanded compositions having a ratio V ₂ /Vi of more than 0.85 , in particular more than 0.90, for example more than 0.95.

The gas content by weight varies from 30% to 70%, preferably from 30% to 60% and more preferably from 30% to 50% of the expanded oxidizing composition.

As indicated previously, the oxidizing composition (B) according to the invention comprises one or more oxidizing agents.

The oxidizing agent used in the context of the invention is a chemical oxidizing agent other than atmospheric oxygen.

The said oxidizing agent or agents is or are chosen preferably from the group consisting o f hydrogen peroxide, urea peroxide, alkali metal bromides or ferricyanides, peroxygenated salts, as for examp le persulfates, perborates, peracids and precursors thereo f, and alkali metal or alkaline-earth metal percarbonates .

Very particularly, the oxidizing agent is hydrogen peroxide .

The oxidizing agent or agents may represent from 0. 1 % to 20% by weight, preferably from 0. 1 %> to 15 %> by weight and better still from 2% to 12% by weight, relative to the total weight of the oxidizing composition (B).

As indicated above, the dyeing composition (A) according to the invention comprises one or more dyes .

The dyes are chosen from oxidation dyes and direct dyes .

The oxidation dyes that may be used in the present invention are generally chosen from oxidation bases, optionally combined with one or more couplers .

The oxidation bases may be chosen especially from para- phenylene diamines, bis (phenyl) alky lene diamines, para-aminophenols, ortho-aminopheno ls and heterocyclic bases, and the addition salts thereo f.

Among the para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2- chloro-para-phenylenediamine, 2,3 -dimethyl-para-phenylenediamine, 2, 6 -dimethyl-para-pheny lene diamine, 2,6-diethyl-para-phenylene- diamine, 2,5 -dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, Ν,Ν-diethyl-para-phenylenediamine, N,N-dipropyl- para-phenylenediamine, 4 - amino -N,N- diethyl- 3 -methylaniline, N,N- bis( -hydro xyethyl)-para-phenylenediamine, 4-N,N-bis( - hydroxy ethyl) amino -2 -methylaniline, 4 -N,N-bis( - hydroxy ethyl) - amino -2 -chloro aniline, 2- β -hydroxy ethyl-para-phenylenediamine, 2- fluoro -para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β -hydroxy propyl) -para-phenylenediamine, 2-hydroxymethyl-para- phenylenediamine, N, N- dimethyl- 3 -methyl-para-phenylenediamine, N,N-(ethyl- -hydroxy ethyl)-para-phenylenediamine, Ν-(β ,γ- dihydroxypropyl) -para-phenylenediamine, N- (4 '-aminophenyl) -para- phenylenediamine, N-phenyl-para-phenylenediamine, 2-β- hydroxyethyloxy-para-phenylenediamine, 2- -acetylaminoethyloxy- para-phenylenediamine, N-( -methoxy ethyl) -para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β- hydroxyethylamino-5 -aminotoluene and 3 -hydroxy- 1 -(4'- aminophenyl)pyrrolidine, and the addition salts thereof with an acid. Among the para-phenylenediamines mentioned above, para- phenylenediamine, para-tolylenediamine, 2-isopropyl-para- phenylenediamine, 2-P-hydroxyethyl-para-phenylenediamine, 2-β- hydroxyethyloxy-para-phenylenediamine, 2, 6 -dimethyl-par a- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3 -dimethyl- para-phenylenediamine, N, N-bis( - hydroxy ethyl) -par a-phenylene- diamine, 2-chloro-para-phenylenediamine and 2-β- acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereo f with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines, examples that may be mentioned include N,N'-bis( -hydroxyethyl)-N,N'-bis(4'- aminophenyl)- l ,3 -diaminopropanol, N, N'-bis( -hydroxy ethyl)-N, N'- bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)- tetramethylenediamine, N,N'-bis( -hydroxy ethyl)-N, N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)- tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3 '- methylphenyl)ethylenediamine, 1 , 8-bis(2,5 -diaminophenoxy)-3 ,6- dioxaoctane and the addition salts thereof.

Among the para-aminophenols, examples that may be mentioned include para-aminophenol, 4-amino-3 -methylpheno l, 4- amino-3 -fluoropheno l, 4-amino-3 -chlorophenol, 4-amino-3 - hydroxymethylpheno l, 4-amino-2-methylpheno l, 4-amino-2- hydroxymethylpheno l, 4-amino-2-methoxymethylpheno l, 4-amino-2- aminomethylpheno l, 4-amino-2-( -hydroxyethyl-aminomethyl)pheno l and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminopheno ls, examples that may be mentioned include 2-aminophenol, 2-amino-5 -methylpheno l, 2-amino- 6-methylpheno l and 5 -acetamido-2-aminopheno l, and the addition salts thereo f.

Among the heterocyclic bases, examples that may be mentioned include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described, for example, in patents GB 1 026978 and GB 1 153 196, for instance 2,5-diaminopyridine, 2-(4- methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.

Other pyridine oxidation bases that are useful in the present invention are the 3-aminopyrazolo[ 1 ,5-a]pyridine oxidation bases or the addition salts thereof described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[ 1 ,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[ 1 ,5-a]pyrid-3- ylamine, 2-(morpholin-4-yl)pyrazolo[ 1 ,5-a]pyrid-3-ylamine, 3-amino- pyrazolo[ 1 ,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[ 1 ,5- a]pyrid-3-ylamine, (3-aminopyrazolo[ 1 ,5-a]pyrid-7-yl)methanol, 2-(3- aminopyrazolo[ 1 ,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[ 1 ,5- a]pyrid-7-yl)ethanol, (3-aminopyrazolo[ 1 ,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[ 1 ,5-a]pyridine, 3,4-diaminopyrazolo[ 1 ,5- ajpyridine, pyrazolo[l ,5-a]pyridine-3,7-diamine, 7-(morpholin-4- yl)pyrazolo[ 1 ,5-a]pyrid-3-ylamine, pyrazolo[l ,5-a]pyridine-3,5- diamine, 5-(morpholin-4-yl)pyrazolo[l ,5-a]pyrid-3-ylamine, 2-[(3- aminopyrazolo[ 1 ,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3- aminopyrazolo[ 1 ,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3- aminopyrazolo[ 1 ,5-a]pyridin-5-ol, 3-aminopyrazolo[ 1 ,5-a]pyridin-4- ol, 3-aminopyrazolo[ 1 ,5-a]pyridin-6-ol, 3-aminopyrazolo[ 1 ,5- a]pyridin-7-ol, 2-(2-hydroxyethoxy)-3-aminopyrazolo[l ,5-a]pyridine, and 2-(4-methylpiperazinium- 1 -yl)-3-aminopyrazolo[ 1 ,5-a]pyridine chloride, and the addition salts thereof.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in the patents DE 2359399; JP 88- 169571; JP 05-63124; EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6- triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists. Among the heterocyclic bases, mention may be made of the compounds of the formula (PI), their addition salts and their solvates:

in which formula (PI):

X denotes a group -CO- or -CR3-,

Y denotes a nitrogen atom or a group -NR1,

Y' denotes a nitrogen atom or a group -NR2,

where R3 represents a hydrogen atom or a C1-C4, alkyl group which is optionally substituted by one or more hydroxyl or amino groups,

Rl represents a C1-C4 alkyl group which is substituted by one or more hydroxyl or amino groups,

R2 represents a C1-C4 alkyl group which is optionally substituted by one or more hydroxyl or amino groups,

it being possible for Rl and R2 and for R2 and R3 respectively to form, with the atoms which carry them, a saturated or unsaturated, 5- to 7-membered heterocycle which is optionally substituted by one or more halogen atoms, or one or more hydroxyl, amino and/or C1-C4 alkyl groups,

R4 represents an amino group, a C1-C4 alkyl group which is optionally substituted by one or more hydroxyl or amino groups, or a C1-C4 alkoxy group which is optionally substituted by one or more hydroxyl or amino groups,

and the ring system containing X, Y and Y' comprises at least one double bond.

The heterocyclic bases of formula (PI) or their addition salts according to the invention may be present in the form of solvates, for example hydrates or solvates of a linear or branched alcohol such as ethanol or isopropanol.

In one preferred variant of the invention, this or these heterocyclic bases is or are chosen from the compounds of formula (Pl') _? their addition salts and their solvates:

where Rl and R4 have the same definitions as before.

Preferably, Rl represents a C1-C4 alkyl group which is substituted by at least one hydroxyl group, more particularly a hydroxyethyl group, and R4 represents an amino group.

In this variant, preference will be given to using 2-(4,5- diamino-lH-pyrazol-l-yl)ethanol or an addition salt thereof.

In a second variant, Rl and R2, or R2 and R3, respectively, form, with the atoms which carry them, a saturated or unsaturated, 5- to 7-membered heterocycle which is optionally substituted by one or more halogen atoms, or one or more hydroxyl, amino and/or C1-C4 alkyl groups.

In this second variant, the heterocyclic base or bases is or are chosen preferably from:

a) the compounds of formula (PI"), their addition salts, and their solvates

where R4 has the same meaning as before, and preferably R4 represents an amino group;

b) the compounds of formula (Ρ1"'), their addition salts and their solvates:

where R4 has the same meaning as above, R4 preferably representing a C1-C4 alkoxy group which is optionally substituted by one or more hydroxyl groups, more particularly a hydroxyethoxy group; and c) mixtures thereof.

Among these compounds of formula (PI"), preference will be given to using 2,3-diamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol- 1-one or an addition salt thereof.

Among these compounds of formula (Ρ1"'), preference will be given to using 2-{[3-aminopyrazolo[l,5-a]pyrid-2-yl]oxy}ethanol or an addition salt thereof.

In one preferred embodiment of the invention, the heterocyclic base or bases is or are chosen from the compounds of formula (PI"), their addition salts and their solvates.

In another preferred embodiment of the invention, the heterocyclic base or bases is or are chosen from the compounds of formula (Ρ1"'), their addition salts and their solvates.

Heterocyclic bases which will be used with preference are 2- (4,5-diamino-lH-pyrazol-l-yl)ethanol, and/or 2-{[3- aminopyrazolo[l,5-a]pyrid-2-yl]oxy}ethanol, and/or 2,3-diamino-6,7- dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one, and/or 2-(2- hydroxyethoxy)-3-amino-pyrazolo[ 1 ,5-a]pyridine and/or one of their salts.

In one particular embodiment of the invention, the oxidation base or bases is or are chosen from the compounds of formula (PI), their addition salts and their solvates, optionally in combination with one or more para-phenylenediamines and/or one or more para- aminophenols.

The couplers that may be used in the present invention may be chosen from those conventionally used for the dyeing of keratin fibres. Among these couplers, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers, and also the addition salts thereof.

Examples that may be mentioned include 1,3- dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 4-chloro- 1 ,3- dihydroxybenzene, 1 - hydroxy- 3 -amino benzene, 1 -met hy 1-2 -hydroxy- 4 - β-hydroxyethylamino benzene, 4-amino-2-hydroxytoluene, 5 -amino -6- chloro-2 methylphenol, 2,4-diamino- 1 -(P-hydroxyethyloxy)benzene, 2- amino-4-(P-hydroxyethylamino)- 1 -methoxybenzene, 1,3- diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3- ureidoaniline, 3-ureido- 1 -dimethylaminobenzene, sesamol, 1-β- hydroxyethylamino-3,4-methylenedioxybenzene, a-naphthol, 2- methyl- 1 -naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N- methylindole, 2-amino-3-hydroxypyridine, 6- hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (P-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(P- hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4- methylpyridine, 1 -H-3-methylpyrazol-5-one, l-phenyl-3- methylpyrazol-5-one, 2,6-dimethylpyrazolo[ 1 ,5-b]- 1 ,2,4-triazole, 2,6- dimethyl[3,2-c]-l,2,4-triazole and 6-methylpyrazolo[ 1 ,5- ajbenzimidazole, the addition salts thereof with an acid, and mixtures thereof.

In general, the addition salts of the oxidation bases and of the couplers that may be used in the context of the invention are especially chosen from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The direct dye(s) may be chosen from synthetic direct dyes and natural direct dyes.

A direct dye is any dye which does not require the presence of a chemical oxidizing agent other than air for colouring.

A synthetic direct dye is any direct dye that does not exist in the natural state, including dyes obtained semi-synthetically. Examples o f suitable synthetic direct dyes that may be mentioned include azo , methine, carbonyl, azine, xanthene, (hetero)aryl nitro , tri(hetero)arylmethane, (metallo)porphyrin and phthalocyanine direct dyes, alone or as mixtures.

More particularly, the synthetic azo direct dyes include a -N=N- function in which the two nitrogen atoms are not simultaneously part of a ring system. However, it is not excluded for one o f the two nitrogen atoms o f the sequence -N=N- to be part of a ring system.

Examples o f azo direct dyes that may be mentioned include the fo llowing dyes, described in Colour Index International, 3rd edition:

- Disperse Red 17

- Basic Red 22

- Basic Red 76

- Basic Yellow 57

- Basic Brown 16

- Basic Brown 17

- Disperse Black 9.

The direct dyes o f the methine family are more particularly compounds comprising at least one sequence chosen from >C=C< and -N=C< in which the two atoms are not simultaneously part of a ring system. However, it is pointed out that one o f the nitrogen or carbon atoms of the sequences may be part of a ring system.

More particularly, the methine dyes are derived from methine, azomethine, hydrazono, mono- and diarylmethane, indoamine (or diphenylamine), indopheno l, indoaniline and (hemi)cyanine compounds, such as styryl, streptocyanine, carbocyanine, azacarbocyanine, diazacarbocyanine and tetraazacarbocyanine, such as tetraazapentamethine, dyes, and optical and geometric isomers thereo f.

Among the azo, azomethine, methine or tetraazapentamethine direct dyes that may be used according to the invention, mention may be made o f the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2189006, FR 2285851, FR 2140205, EP 1378544, EP 1674073.

Among the indoamine dyes that can be used according to the invention, mention may be made of the following compounds:

- 2- β -hydroxy ethylamino -5- [bis( -4 '-hydroxy et hyl) amino ]- anilino- 1 ,4-benzoquinone,

- 2- β -hydroxy ethylamino -5 -(2 ' -methoxy-4 '-amino) anilino - 1 ,4- benzoquinone,

- 3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-6-methoxy- 1 ,4-benzoquinone imine,

- 3-N-(3 '-chloro-4'-methylamino)phenylureido-6-methyl- 1 ,4- benzoquinone imine,

- 3-[4'-N-(ethyl,carbamylmethyl)amino]phenylureido-6-methyl- 1 ,4-benzoquinone imine.

Among the tetraazapentamethine dyes that may be used according to the invention, mention may be made of the following compounds appearing in the table below:

X ^" representing an anion preferably chosen from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate .

As regards the synthetic direct dyes of the carbonyl family, examples that may be mentioned include dyes chosen from quinone, acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazo lanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone,

(iso)vio lanthrone, isoindo linone, benzimidazolone, isoquino linone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole and coumarin dyes .

Among the quinone direct dyes, mention may be made o f the fo llowing dyes :

- Disperse Red 15

- Solvent Vio let 13

- Disperse Vio let 1

- Disperse Vio let 4

- Disperse Blue 1

- Disperse Vio let 8

- Disperse Blue 3

- Disperse Red 1 1

- Disperse Blue 7

- Basic Blue 22

- Disperse Vio let 15

- Basic Blue 99 and also the following compounds :

1 -N-methylmorpho liniumpropylamino-4-hydroxyanthra- quinone;

- 1 -aminopropylamino-4-methylaminoanthraquinone;

- 1 -aminopropylaminoanthraquinone;

- 5 " -hydroxyethyl- 1 ,4-diaminoanthraquinone;

- 2-amino ethylaminoanthraquinone; and

- 1 ,4-bis( ,y-dihydroxypropylamino)anthraquinone.

As regards the synthetic direct dyes of the azine family, mention may be made especially o f azine, fluorindine, acridine, (di)oxazine and (di)thiazine dyes .

Examples o f azine dyes that may be mentioned include the fo llowing compounds :

- Basic Blue 17

- Basic Red 2.

As regards the synthetic direct dyes o f the xanthene family, mention may be made especially o f xanthene, thioxanthene and pyronine dyes .

The nitro(hetero)aryl synthetic direct dyes are more particularly nitrobenzene or nitropyridine direct dyes .

Among the nitrobenzene direct dyes that may be used according to the invention, mention may be made in a nonlimiting manner of the following compounds :

- 1 ,4-diamino-2-nitrobenzene

- 1 -amino-2-nitro-4-B-hydroxyethylaminobenzene

- 1 - amino -2 -nitro -4 -bis( - hydroxy ethyl) aminobenzene

- 1 ,4-bis(P-hydroxyethylamino)-2-nitrobenzene

- 1 - β- hydroxy ethylamino -2 -nitro -4 -bis( - hydro xyethylamino)benzene

- 1 -P-hydroxyethylamino-2-nitro-4-aminobenzene

- 1 - β -hydroxy ethylamino -2 -nitro -4 -(ethyl) ( β- hydroxyethyl)aminobenzene

- 1 - amino -3 -methy 1-4- β -hydroxy ethylamino -6 -nitrobenzene

- 1 - amino -2 -nitro -4- β -hydro xy ethylamino -5 -chlorobenzene - 1 ,2-diamino-4-nitrobenzene

- 1 - amino -2- β -hydro xyethylamino- 5 -nitrobenzene

- 1 ,2-bis-( -hydroxyethylamino)-4-nitrobenzene

- 1 -amino-2-tris(hydroxymethyl)methylamino-5 -nitrobenzene - 1 -hydroxy-2-amino-5 -nitrobenzene

- 1 -hydroxy-2-amino-4-nitrobenzene

- 1 -hydroxy- 3 -nitro -4 -amino benzene

- 1 -hydroxy-2-amino-4,6-dinitrobenzene

- 1 - -hydroxyethyloxy-2- -hydroxyethylamino- 5 -nitrobenzene - 1 -methoxy-2- -hydroxyethylamino-5 -nitrobenzene

- 1 - -hydroxyethyloxy-3 -methylamino-4-nitrobenzene

- 1 -β ,γ-dihy droxypropyloxy- 3 -methylamino -4 -nitrobenzene

- 1 - β -hydroxy ethylamino -4- β ,γ-dihy droxypropyloxy-2 - nitrobenzene

- 1 - ,y-dihydroxypropylamino-4-trifluoromethyl-2- nitrobenzene

- 1 - -hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene

- 1 - β-hydroxyet hylamino- 3 -methyl-2 -nitrobenzene

- 1 -β -amino ethylamino -5 -methoxy-2-nitrobenzene

- 1 -hydroxy-2-chloro-6-ethylamino-4-nitrobenzene

- 1 -hydro xy-2-chloro-6-amino-4-nitrobenzene

- 1 -hy dro xy- 6 -bis( -hydroxyethyl)amino- 3 -nitrobenzene

- 1 -P-hydroxyethylamino-2-nitrobenzene

- 1 -hydro xy-4-β -hydro xyethylamino -3 -nitrobenzene.

Among the triarylmethane dyes that may be used according to the invention, mention may be made of the following compounds :

- Basic Green 1

- Basic Vio let 3

- Basic Vio let 14

- Basic Blue 7

- Basic Blue 26.

As regards the (metallo)porphyrin or phthalocyanine synthetic direct dyes, use may be made o f cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, such as, for example, alkali metals and alkaline-earth metals, zinc and silicon.

Examples o f particularly suitable synthetic direct dyes that may be mentioned include nitrobenzene dyes; azo, methine, azomethine, hydrazono or styryl direct dyes; azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes, and in particular anthraquinone, naphthoquinone or benzoquinone dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes, indigoid direct dyes, phthalocyanine direct dyes and porphyrin direct dyes, alone or as mixtures.

These dyes may be monochromophoric dyes (meaning that they comprise only one dye) or polychromophoric dyes, preferably di- or trichromophoric dyes; the chromophores may be identical or different, from the same chemical family or a different family. It should be noted that a polychromophoric dye comprises a plurality o f groups each derived from a mo lecule that absorbs in the visible region between 400 and 800 nm. Furthermore, this absorbance o f the dye does not require any prior oxidation thereof, or combination with any other chemical species .

In the case o f po lychromophoric dyes, the chromophores are connected together by means o f at least one linker L, which may be cationic or non-cationic.

The linker L is preferably a linear, branched or cyclic C 1 - C20 alkyl chain which is optionally interrupted and/or terminated by at least i) a heteroatom (such as nitrogen N(R), N ⁺ R, R' , Q ^" , oxygen or sulfur), ii) a group C(O), C(S), S(O), or S(0) ₂ or iii) a combination thereo f, optionally interrupted by at least one heterocycle which is or is not fused with a phenyl nucleus, and which comprises at least one quaternized nitrogen atom forming part of said ring system, and optionally at least one other heteroatom (such as oxygen, nitrogen or sulfur), optionally interrupted by at least one substituted or unsubstituted phenyl or naphthyl, optionally at least one quaternary ammonium group substituted by two C 1 - C 1 5 alkyl groups which are optionally substituted; the linker does not contain a nitro , nitroso or peroxo group, and R and R', which are identical or different, represent a hydrogen atom or a Ci-C ₆ alkyl group which is optionally substituted, preferably by at least one hydroxyl group, and Q ^" represents an organic or inorganic anionic counterion such as a halide or an alkylsulfate.

If the heterocycles or aromatic nuclei are substituted, they are substituted, for example, with one or more Ci-Cs alkyl groups optionally substituted with a hydroxyl, C1-C2 alkoxy, C2-C4 hydroxyalkoxy, acetylamino or amino group substituted with one or two C1-C4 alkyl groups, optionally bearing at least one hydroxyl group, or the two groups possibly forming, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; a halogen atom; a hydroxyl group; a C1-C2 alkoxy group; a C2-C4 hydroxyalkoxy group; an amino group; an amino group substituted with one or two identical or different C1-C4 alkyl groups, optionally bearing at least one hydroxyl group.

According to one particularly advantageous embodiment of the invention, the dye or dyes is or are chosen from (poly)azo dyes such as (di)azo dyes; hydrazono dyes; (poly)methine dyes such as styryl dyes; anthraquinone dyes or naphthalimide dyes. Preferably, these dyes are (poly)cationic.

According to an even more preferred embodiment of the invention, the dyes are chosen from cationic dyes known as "basic dyes".

Mention may be made of the cationic hydrazono dyes of formulae (I) and (Γ), the azo dyes (II) and (ΙΓ) and the diazo dyes (III) below: Het ⁺ -C(R ^a )=N-N(R ^b )-Ar, Het ⁺ -N(R ^a )-N=C(R ^b )-Ar, -N=N

Q- Q- Q-

(I) (Γ) (Π)

Ar ⁺ -N=N-Ar", Q- and Het ⁺ -N=N-Ar' (Ι ) N-Ar, Q

(HI) in which formulae (I), (Γ), (II), (H')and (III):

-Het ⁺ represents a cationic heteroaryl group, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially by one or more Ci-Cs alkyl groups such as methyl;

- Ar+ represents an aryl group, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-Cs alkyl)ammonium such as trimethylammonium;

- Ar represents an aryl group, especially phenyl, which is optionally substituted, preferentially with one or more electron- donating groups such as i) optionally substituted (Ci-Cs)alkyl, ii) optionally substituted (Ci-Cs)alkoxy, iii) (di)(Ci-Cs alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8 alkyl)amino, v) optionally substituted N-(d-Cs alkyl)-N- aryl(Ci-C8 alkyl)amino or alternatively Ar represents a julolidine group;

- Ar' is an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferentially with one or more Ci- C8 alkyl, hydroxyl or Ci-Cs alkoxy groups;

- Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more Ci-Cs alkyl, hydroxyl, (di)(Ci-Cs alkyl)amino, Ci-Cs alkoxy or phenyl groups; - R ^a and R ^b , which are identical or different, represent a hydrogen atom or a Ci-Cs alkyl group, which is optionally substituted, preferentially with a hydroxyl group;

or alternatively the substituent R ^a with a substituent of Het ⁺ and/or R ^b with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl;

particularly, R ^a and R ^b represent a hydrogen atom or a C1-C4 alkyl group, which is optionally substituted with a hydroxyl group;

- Q ^" represents an organic or inorganic anionic counterion, such as a halide or an alkylsulfate.

In particular, the dyes of the invention are cationically charged, endocyclic, azo and hydrazono dyes of formulae (I), (Γ) and (II) as defined above. The dyes of formulae (I), (Γ) and (II) described in patent applications WO 95/15144, WO 95/01772 and EP 714954 are more particularly preferred.

Dyes of the invention are preferably chosen from the following compounds:

in which formulae (1-1) and (II-l):

- R ¹ represents a C1-C4 alkyl group such as methyl;

- R ² and R ³ which are identical or different, represent a hydrogen atom or a C1-C4 alkyl group such as methyl; and

- R ⁴ represents a hydrogen atom or an electron-donating group such as optionally substituted Ci-Cs alkyl, optionally substituted Ci- Cs alkoxy, or (di)(Ci-Cs alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R ⁴ is a hydrogen atom; - Z represents a CH group or a nitrogen atom, preferentially

CH;

- Q- is as defined previously.

In particular, the dyes o f formulae (1- 1 ) and (H- l ) are chosen from Basic Red 5 1 , Basic Yellow 87 and Basic Orange 3 1 or their derivatives :

where Q ^" is as defined previously, and represents in particular a halide such as a chloride, or an alkyl sulfate such as methyl sulfate or mesityl.

Mention may also be made o f l -(4 ' -aminodiphenylazo)-2- methy 1-4 -bis(P-hydroxyethyl)amino benzene.

Among the polychromophoric dyes, mention may be made more particularly o f the symmetrical or non-symmetrical di- or trichromophoric azo and/or azomethine (hydrazone) dyes, comprising on the one hand at least one 5 - or 6-membered aromatic heterocycle, optionally fused, which comprises at least one quaternized nitrogen atom forming part of the said heterocycle, and optionally at least one other heteroatom (such as nitrogen, sulfur or oxygen), and, on the other hand, at least one optionally substituted phenyl or naphthyl group optionally bearing at least one group OR in which R represents a hydrogen atom, an optionally substituted C i -C ₆ alkyl group, an optionally substituted phenyl nucleus, or at least one group N(R' ) ₂ with R' , which may be identical or different, representing a hydrogen atom, an optionally substituted C i - C ₆ alkyl group or an optionally substituted phenyl nucleus; the groups R' possibly forming, with the nitrogen atom to which they are attached, a saturated, 5 - or 6- membered heterocycle, or else one and/or both of the groups R' may each form a saturated, 5 - or 6-membered heterocycle with the carbon atom of the aromatic ring that is ortho to the nitrogen atom.

Aromatic cationic heterocycles that may preferably be mentioned include 5 - or 6-membered rings containing 1 to 3 nitrogen atoms and preferably 1 or 2 nitrogen atoms, one being quaternized; said heterocycle moreover being optionally fused to a benzene nucleus. It should similarly be noted that the heterocycle may optionally comprise another heteroatom other than nitrogen, for instance sulfur or oxygen.

If the heterocycles or phenyl or naphthyl groups are substituted, they are substituted, for example, with one or more C i - C s alkyl groups optionally substituted with a hydroxyl, C 1 - C2 alkoxy, C2 - C ₄ hydroxyalkoxy, acetylamino or amino group substituted with one or two C 1 - C4 alkyl groups, optionally bearing at least one hydroxyl group, or the two groups possibly forming, with the nitrogen atom to which they are attached, a 5 - or 6-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; a halogen atom; a hydroxyl group; a C 1 - C2 alkoxy group; a C2 - C4 hydroxyalkoxy group; an amino group; an amino group substituted with one or two identical or different C 1 - C4 alkyl groups, optionally bearing at least one hydroxyl group .

These polychromophores are connected together via at least one linker L as defined previously.

The bonding between the linker and each chromophore generally takes place via a heteroatom substituent on the phenyl or naphthyl nucleus or via the quaternized nitrogen atom o f the cationic heterocycle.

The dye may comprise identical or different chromophores . As examples of such dyes, reference may be made especially to patent applications EP 1 637 566, EP 1 619 221 , EP 1 634 926, EP 1 619 220, EP 1 672 033 , EP 1 671 954, EP 1 671 955 , EP 1 679 3 12, EP 1 671 95 1 , EP 167 952, EP 167 971 , WO 06/063 866 , WO 06/063 867, WO 06/063 868 , WO 06/063 869, EP 1 408 91 9, EP 1 377 264, EP 1 377 262, EP 1 377 261 , EP 1 377 263 , EP 1 399 425 , EP 1 399 1 17, EP 1 416 909, EP 1 399 1 16 and EP 1 671 560.

It is equally also possible to use cationic synthetic direct dyes which are mentioned in the fo llowing patent applications : EP 1 006 153 , which describes dyes comprising two chromophores o f anthraquinone type connected via a cationic linker; EP 1 433 472, EP 1 433 474, EP 1 433 47 1 and EP 1 433 473 , which describe identical or different dichromophoric dyes, connected via a cationic or non- cationic linker, and also EP 6 29 1 333 , which especially describes dyes comprising three chromophores, one of them being an anthraquinone chromophore, to which are attached two chromophores of azo or diazacarbocyanine type or an isomer thereof.

The term "natural dyes" means any dye or dye precursor that is naturally occurring and that is produced either by extraction (and possible purification) from a plant or animal matrix, optionally in the presence o f natural compounds such as ash or ammonia, or via chemical synthesis.

Natural dyes that may be mentioned include lawsone, henna, curcumin, chlorophyllin, alizarin, kermesic acid, purpurin, purpurogallin, indigo, Tyrian purple, sorghum, carminic acid, catechin, epicatechin, juglone, bixin, betanin, quercetin, chromene dyes and chroman dyes, including haematein and brazilein and laccaic acids .

Preferably, the natural dyes used in the invention are chosen from curcumin, chlorophyllin, chromene dyes, chroman dyes and laccaic acids. According to the invention, the terms "chromene dye" and "chroman dye" mean dyes which comprise in their structure at least one bicycle of formula (IV) below:

IV the endocyclic bond representing a carbon-carbon single bond or a carbon-carbon double bond, as illustrated by formula IV- 1 denoting the chromene family and formula IV-2 denoting the chroman family below :

IV- 1 IV-2

More particularly, the dyes having in their structure a bicycle of formula (IV) are chosen from the dyes having the fo llowing formulae :

- formula (V), comprising in its structure the bicycle o f formula IV-2,

in which:

i) represents a carbon-carbon single bond or a carbon- carbon double bond, the sequence o f these bonds denotes two carbon-carbon single bonds and two carbon-carbon double bonds, the said bonds being conjugated,

ii) X represents a group :

// /

HO-C or 0=C

\ \

iii) R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , which may be identical or different, represent, independently o f each other, a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted acyloxy group, and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereo f with a cosmetically acceptable acid or base, and the hydrates thereof, and

- formula (VI), comprising in its structure the bicycle o f formula IV- 1 ,

in which:

- Rii, Ri2, Ri3, Ri6, Ri9 and R20, which may be identical or different, represent, independently of each other, a hydrogen atom or a C1-C4 alkyl group,

- Ri4, Ri5, Ri7 and Ris, which may be identical or different, represent, independently of each other, a hydrogen atom, a hydroxyl group or a C1-C4 alkoxy group,

and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the hydrates thereof.

As regards the dyes of formula (V) as defined previously, they may be in two tautomeric forms noted (Va) and (Vb):

The alkyl groups mentioned in the preceding definitions of th substituents are linear or branched, saturated hydrocarbon groups generally C1-C20, particularly C1-C10 and preferably Ci-C ₆ , such a methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkoxy groups are alkyl-oxy groups with alkyl groups as defined previously and preferably the alkoxy groups are CI -CIO, such as methoxy, ethoxy, propoxy and butoxy.

The alkyl or alkoxy groups, when they are substituted, may be substituted with at least one substituent borne by at least one carbon atom, chosen from:

- a halogen atom;

- a hydroxyl group;

- a C1-C2 alkoxy group;

- a C1-C10 alkoxycarbonyl group;

- a C2-C4 (poly)hydroxyalkoxy group;

- an amino group;

- a 5- or 6-membered heterocycloalkyl group;

- an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium, optionally substituted with a (Ci-C4)alkyl group, preferentially methyl;

- an amino group substituted with one or two identical or different Ci-C ₆ alkyl groups, optionally bearing at least:

* one hydroxyl group,

* an amino group optionally substituted with one or two optionally substituted C1-C3 alkyl groups, it being possible for the said alkyl groups to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7- membered heterocycle, optionally comprising at least one other nitrogen or non-nitrogen heteroatom,

* one quaternary ammonium group -N ⁺ R'R"R"', M ^" for which R', R" and R'", which are identical or different, represent a hydrogen atom or a C1-C4 alkyl group; and M ^" represents the counterion of the corresponding organic acid, inorganic acid or halide,

* or an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium, optionally substituted with a (C1-C4) alkyl group, preferentially methyl; - an acylamino group (-NR-COR') in which the group R is a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group and the group R' is a C1-C2 alkyl group;

- a carbamoyl group ((R) ₂ N-CO-) in which the groups R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group;

- an alkylsulfonylamino group (R'S0 ₂ -NR-) in which the group R represents a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group and the group R' represents a Ci- C ₄ alkyl group, or a phenyl group;

- an aminosulfonyl group ((R) ₂ N-S0 ₂ -) in which the groups R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group;

- a carboxylic group in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);

- a cyano group;

- a nitro group;

- a carboxyl or glycosylcarbonyl group;

- a phenylcarbonyloxy group optionally substituted by one or more hydroxyl groups;

- a glycosyloxy group; and

- a phenyl group optionally substituted by one or more hydroxyl groups.

The term "glycosyl group" means a group originating from a mono- or polysaccharide.

Preferably, the alkyl or alkoxy groups of formula (V) are unsubstituted.

According to one particular embodiment of the invention, the dyes of formula (V) comprise a group R ⁶ which represents a hydroxyl group.

In one preferred variant, X represents a group 0=C.

Another particular embodiment of the invention relates to the dyes of formula (V), for which the group R ¹ represents a hydrogen atom or a hydroxyl group. More particularly, the dyes of formula (V) are chosen from haematein and brazilein.

Brazilein is a conjugated form of a chroman compound of formula IV-2. The tautomeric structures (Va) and (Vb) illustrated above are found in the scheme below.

Brazilein and haematein or the haematoxylin/haematein and brazilin/brazilein pairings may be obtained synthetically or by extraction of plants known to be rich in these dyes.

The dyes of formula (V) may be used in the form of extracts. Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpinia brasiliensis.

The extracts are obtained by extracting the various plant parts, for instance the root, the wood, the bark or the leaves.

According to one particular embodiment of the invention, the natural dyes of formula (V) are obtained from logwood, pernambuco wood, sappan wood and Brazil wood. The salts o f the dyes o f formulae (V) and (VI) of the invention may be salts of cosmetically acceptable acids or bases.

The acids can be inorganic or organic. Preferably, the acid is hydrochloric acid, which results in chlorides .

The bases can be inorganic or organic. In particular, the bases are alkali metal hydroxides such as sodium hydroxide, which leads to sodium salts.

Preferably, the dye(s) of formulae (V) and (VI) included in the composition according to the invention are derived from plant extracts . Use may also be made of mixtures of plant extracts .

The natural extracts of the dyes according to the invention may be in the form o f powders or liquids. Preferably, the extracts are in powder form.

In another variant of the invention, the natural dyes are chosen from laccaic acids.

For the purposes o f the present invention, the term " laccaic acid" means a compound having in its structure a unit of the type :

Preferably, the laccaic acids o f the invention are of formula (VII) below :

(VII) with Ri denoting a phenyl group substituted with at least one hydroxyl group, and preferably with a hydroxyl group that is advantageously in the ortho position relative to the bond attaching it to the fused nuclei.

In particular, the phenyl group Ri comprises, besides a hydroxyl group, at least one group -CH2R2 , R2 denoting an acetamidomethyl (CH3 CONHCH2-) , hydroxymethyl (HOCH2-) or 2- aminoacetic acid group (HC"2C(NH2)CH-) .

Preferentially, the laccaic acids o f the invention are chosen from laccaic acids A, B, C and D, or mixtures thereo f, and more particularly chosen from A, B and C , or mixtures thereof.

Laccaic acid A G : -CH ₂ CH ₂ NHC(0)CH ₃

Laccaic acid B G : -CH2 CH2OH

Laccaic acid C G : -CH ₂ CH(NH ₂ )C(0)OH

Laccaic acid D G : -CH2CH2NH2

Laccaic acid A, B, C and D

A laccaic acid according to the invention that may especially be used is the dye CI Natural Red 25 , CI 75450, CAS - 60687-93 -6 , which is o ften referred to as laccaic acid. This is a dye o f natural origin originating from the secretions of an insect, Coccus laccae (Lacifer Lacca Kerr), which is generally found on the twigs o f certain trees native to South-East Asia.

CI Natural Red 25 generally contains two major constituents in its composition: laccaic acid A and laccaic acid B . It may also contain a small amount of laccaic acid C . It is obviously also possible to use the purified forms o f the laccaic acids of formula (VII) .

Even more preferentially, the natural direct dyes are chosen from haematein and brazilein.

The dyeing composition (A) preferably comprises at least one oxidation dye, optionally in combination with at least one direct dye.

The dye or dyes may represent from 0.0001 % to 20% by weight, preferably from 0.01 % to 15 % by weight, better still from 0. 1 %) to 10%) by weight, relative to the total weight of the dyeing composition (A).

The dyeing composition (A) and the oxidizing composition (B) generally comprise water or a mixture of water and at least one organic so lvent to solubilize the compounds which would not be sufficiently so luble in water. Examples of organic solvents that may be mentioned include C 1 - C 4 alcoho ls, such as ethano l and isopropano l, polyo ls and polyo l ethers, for instance 2-butoxyethanol, propylene glyco l, propylene glyco l monomethyl ether, diethylene glyco l monoethyl ether and monomethyl ether, and also aromatic alcoho ls, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

If present, the organic solvents represent preferably from 1 % to

40%) by weight and more preferably still from 5 % to 30%> by weight, relative to the total weight of the dyeing composition (A) or of the expanded oxidizing composition (B) .

According to one embodiment, the dyeing composition (A) according to the invention comprises one or more alkaline agents.

They may be any agent allowing an increase in the pH o f the composition in which it is present.

The alkaline agent may be a Bronsted-Lowry or Lewis base. It may be inorganic or organic.

In particular, the alkaline agent(s) may be chosen from:

a) aqueous ammonia,

b) alkanolamines such as mono-, di- and triethanolamines, isopropanolamine and 2-amino-2-methyl- 1 -propanol, and also derivatives thereof, c) oxyethylenated and/or oxypropylenated ethylenediamines, d) inorganic or organic hydroxides,

e) alkali metal silicates such as sodium metasilicates,

f) amino acids, preferably basic amino acids, such as arginine, lysine, ornithine, citrulline and histidine,

g) carbonates and bicarbonates, particularly of a primary amine, secondary amine or tertiary amine, or of an alkali metal or alkaline-earth metal, or of ammonium, and

h) the compounds of formula (VIII) below:

^RX \ / ^RZ

^N W-N

^{Ry XRt} (viii) in which W is a Ci-C ₆ alkylene residue optionally substituted with a hydroxyl group or a Ci-C ₆ alkyl group; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a Ci-C ₆ alkyl, Ci-C ₆ hydroxyalkyl or Ci-C ₆ aminoalkyl group.

Examples of such compounds of formula (VIII) that may be mentioned include 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.

The inorganic or organic hydroxides are preferably chosen from hydroxides of an alkali metal, hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, hydroxides of a transition metal, such as hydroxides of metals from groups III, IV, V and VI of the Periodic Table of the Elements, hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.

The hydroxide may be formed in situ, for instance guanidine hydroxide, formed by reacting calcium hydroxide and guanidine carbonate.

The alkaline agents which are preferred are chosen in particular from aqueous ammonia, sodium or ammonium carbonate, sodium or ammonium bicarbonate, arginine, an alkanolamine o f class b), better still an alkano lamine of class b) such as monoethanolamine.

When the alkaline agent or agents is or are present, the amount thereo f may vary from 0. 1 % to 30% by weight, preferably from 0.5 % to 20%) by weight and better still from 1 % to 10%> by weight, relative to the total weight of the expanded dyeing composition (A) .

The dyeing composition (A) and/or the expanded oxidizing composition (B) according to the invention may further comprise one or more cationic polymers, preferably with a cationic charge density o f greater than or equal to 4 meq/g.

More preferably still, the cationic charge density is greater than or equal to 5 milliequivalents per gram, and more preferably may vary from 5 to 20 meq/g.

The cationic charge density o f a polymer corresponds to the number of mo les o f cationic charges per unit mass o f po lymer under conditions in which it is totally ionized. It may be determined by calculation if the structure of the polymer is known, i. e. the structure of the monomers constituting the polymer and their mo lar proportion or weight proportion. It may also be determined experimentally by the Kjeldahl method.

The cationic polymers having a cationic charge density o f greater than or equal to 4 meq/g that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of hair treated with detergent compositions, i. e. especially those described in patent application EP- A-0 337 354 and in French patent applications FR-A-2 270 846, 2 383 660 , 2 598 61 1 , 2 470 596 and 2 5 19 863.

In general, for the purposes o f the present invention, the term "cationic polymer" denotes any polymer comprising cationic groups and/or groups that may be ionized into cationic groups .

The cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and/or quaternary amine groups that may either form part of the main polymer chain or may be carried by a side substituent directly connected thereto . The cationic polymers used generally have a number-average mo lecular mass o f between 500 and 5 x 10 ⁶ approximately and preferably between 10 ³ and 3 x 10 ⁶ approximately.

Among the cationic polymers, mention may be made more particularly o f polymers o f the polyamine, polyaminoamide and polyquaternary ammonium type . These are known products .

The polymers o f po lyamine, polyamidoamide and polyquaternary ammonium type that can be used in accordance with the present invention, and that can in particular be mentioned, are those described in French patents No . 2 505 348 or 2 542 997. Among these polymers, mention may be made of:

( 1 ) Quaternized or non-quaternized vinylpyrro lidone/dialkylaminoalkyl (meth)acrylate copolymers.

(2) Polymers composed of piperazinyl units and of divalent alkylene or hydroxyalkylene groups containing straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quaternization products o f these polymers. Such polymers are described, in particular, in French patents 2 162 025 and 2 280 36 1 .

(3) Water-so luble polyaminoamides prepared in particular by polycondensation o f an acidic compound with a polyamine; these polyamino amides can be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bisunsaturated derivative, a bishalohydrin, a bisazetidinium, a bishaloacyldiamine or an alkyl bishalide or alternatively by an oligomer resulting from the reaction o f a difunctional compound reactive with respect to a bishalohydrin, a bisazetidinium, a bishalo acyldiamine, an alkyl bishalide, an epihalohydrin, a diepoxide or a bisunsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mo l per amine group of the polyaminoamide; these polyamino amides can be alkylated or, if they comprise one or more tertiary amine functions, quaternized. Such polymers are especially described in French patents 2 252 840 and 2 368 508. (4) Polyaminoamide derivatives resulting from the condensation o f polyalkylene-polyamines with polycarboxylic acids, fo llowed by alkylation with difunctional agents. Mention may be made, for example, o f adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are especially described in French patent 1 583 363.

(5) Polymers obtained by reacting a polyalkylene-polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms . The mo lar ratio between the polyalkylene-polyamine and the dicarboxylic acid is between 0.8 : 1 and 1 .4 : 1 ; the polyaminoamide resulting therefrom is reacted with epichlorohydrin in a mo lar ratio o f epichlorohydrin relative to the secondary amine group of the polyamino amide o f between 0.5 : 1 and 1 .8 : 1 . Such polymers are described in particular in US patents 3 227 61 5 and 2 961 347.

(6) Alkyldiallylamine or dialkyldiallylammonium cyclopolymers, such as homopolymers or copolymers comprising units corresponding to the formulae (IX) or (IX' ) :

in which formulae k and t are equal to 0 or 1 , the sum k + t being equal to 1 ; R _{1 2} denotes a hydrogen atom or a methyl group; Ri o and Ri i , independently o f each other, denote an alkyl group containing from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably contains 1 to 5 carbon atoms, or a lower amidoalkyl group, or Ri o and Rn can denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl; Y ^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are especially described in French patent 2 080 759 and in its Certificate of Addition 2 190 406.

Mention may be made, for example, o f the diallyldimethylammonium chloride homopolymer so ld under the name "MERQUAT ^® 100" by the company NALCO (LUBRIZOL), and the diallyldimethylammonium chloride-acrylamide copolymers .

(7) The diquaternary ammonium polycondensates containing repeating units corresponding to the formula:

in which formula (X) :

Ri 3 , Ri 4 , Ri 5 and Ri ₆ , which may be identical or different, represent aliphatic, alicyclic or arylaliphatic groups containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic groups, or alternatively R13 , R14 , R1 5 and Ri 6 , together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively R13 , R14 , R1 5 and Ri 6 represent a linear or branched C i -C ₆ alkyl group substituted with a nitrile, ester, acyl or amide group or a group -CO-O-R17-D or -CO-NH-R17-D where R17 is an alkylene group and D is a quaternary ammonium group ,

Ai and B i represent polymethylene groups containing from 2 to 20 carbon atoms, which may be linear or branched, and saturated or unsaturated, and which may contain, linked to or inserted in the main chain, one or more aromatic rings, or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X ^" denotes an anion derived from an inorganic or organic acid, Ai , Ri 3 and R1 5 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene group, B i can also denote a group -(CH2) _n -CO-D-OC-(CH2) _n - , in which D denotes :

a) a glyco l residue o f formula: -O-Z-O-, where Z denotes a linear or branched hydrocarbon-based group or a group corresponding to one of the following formulae :

-(CH2-CH ₂ -0)x-CH2-CH ₂ - - [CH2-CH(CH ₃ )-0] _y -CH2-CH(CH ₃ )-,

in which x and y denote an integer from 1 to 4 , representing a defined and unique degree o f polymerization or any number from 1 to 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue, such as a piperazine derivative;

c) a bis-primary diamine residue of formula : -NH-Y-NH- , where Y denotes a linear or branched hydrocarbon group, or alternatively the divalent group

-CH2-CH2-S-S-CH2-CH2- ;

d) a ureylene group of formula: -NH-CO-NH- .

Preferably, X ^" is an anion such as chloride or bromide.

These polymers generally have a number-average mo lecular mass of between 1 000 and 100 000.

Polymers o f this type are described in particular in French patents 2 320 330, 2 270 846, 2 3 16 271 , 2 336 434 and 2 4 13 907 and US patents 2 273 780, 2 375 853 , 2 388 614, 2 454 547, 3 206 462, 2 261 002, 2 271 378 , 3 874 870, 4 001 432, 3 929 990, 3 966 904, 4 005 193 , 4 025 617 , 4 025 627 , 4 025 653 , 4 026 945 and 4 027 020.

Use may be made more particularly o f polymers that are composed o f repeating units corresponding to the formula: in which Ri, R ₂ , R3 and R ₄ , which may be identical or different, denote an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X ^" is an anion derived from an inorganic or organic acid.

A compound of formula (a) that is particularly preferred is the one for which Ri, R ₂ , R3 and R ₄ represent a methyl group and n = 3, p = 6 and X = CI, which is known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

(8) Polyquaternary ammonium polycondensates composed of units of formula (XI): is R 20

I

N +— (CH _? )r NH— CO (CH _? )q— CO NH — (CH ₂ )s ^■ N +- I X-

^R 19 ( _XI ) 21

in which formula:

Ri8, Ri9, R20 et R21, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or -CH ₂ CH2(OCH ₂ CH2)pOH group,

where p is equal to 0 or to an integer between 1 and 6, with the proviso that Ris, R19, R20 and R21 do not simultaneously represent a hydrogen atom,

r and s, which may be identical or different, are integers between 1 and 6,

q is equal to 0 or to an integer between 1 and 34,

X denotes a halogen atom, A denotes a dihalide group or preferably represents - CH2 - CH2 -

Such compounds are described especially in patent application EP-A- 122 324.

Mention may be made among these, for examp le, of the Mirapol ^® A 15 , Mirapo l ^® AD 1 , Mirapol ^® AZ 1 and Mirapol ^® 1 75 products sold by the company Mirano l.

(9) Homopolymers or copolymers derived from acrylic or methacrylic acids and comprising units :

C

in which the groups R22 independently denote H or CH3 ,

the groups A2 independently denote a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms,

the groups R23 , R24 and R25 , which may be identical or different, independently denote an alkyl group of 1 to 1 8 carbon atoms or a benzyl group,

the groups R26 and R27 represent a hydrogen atom or an alkyl group of 1 to 6 carbon atoms,

X2 ^" denotes an anion, for examp le methosulfate or halide, such as chloride or bromide.

The comonomer or comonomers that can be used in preparing corresponding copolymers belong to the family o f acrylamides, methacrylamides, diacetoneacrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls, or alkyl esters, acrylic or methacrylic acids, vinylpyrrolidone or vinyl esters.

(10) Quaternary polymers of vinylpyrrolidone and of vinylimidazole.

(11) Crosslinked polymers of methacryloyloxy(Ci-C4)alkyltri(Ci- C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide.

Other cationic polymers that may be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, polyquaternary ureylenes and chitin derivatives.

Among all of the cationic polymers which can be used in the context of the present invention, preference is given to employing dialkyldiallylammonium halide homopolymers and copolymers such as Polyquaternium-6, sold for example under the name "MERQUAT® 100" by the company NALCO (LUBRIZOL), polycondensates having repeating diquaternary or polyquaternary ammonium units, more particularly polycondensates composed of repeating units conforming to the formula (a), such as the compound known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

As other cationic polymers suitable in the present invention, mention may be made, in particular, of cellulosic polymers, as for example the cellulose ether derivatives that contain quaternary ammonium groups and are described in French patent No. 1 492597.

It is also possible to mention cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, described especially in patent US 4 131 576, such as hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted especially with a meth- acryloylethyltrimethylammonium, methacrylamidopropyltrimethyl- ammonium or dimethyldiallylammonium salt.

It is also possible to mention cationic guar gum derivatives.

In one particular embodiment, the expanded dyeing composition (A) further comprises one or more cationic polymers having a charge density o f greater than or equal to 4 meq/g, as described above.

When the cationic polymer or polymers having a charge density preferably greater than or equal to 4 meq/g is or are present, their amount varies, for example, from 0. 1 % to 10% by weight and preferably from 0.2% to 5 % by weight, relative to the total weight o f the dyeing composition (A) or the expanded oxidizing composition (B) .

The dyeing composition (A) and/or the expanded oxidizing composition (B) according to the invention may further contain one or more liquid fatty substances, in particular in an amount greater than or equal to 10%> by weight, relative to the total weight of the dyeing composition (A) or the expanded oxidizing composition (B) .

The term "fatty substance" means an organic compound that is inso luble in water at standard temperature (25 °C) and at atmospheric pressure (760 mmHg, i. e . 1 .013 x 10 ⁵ Pa), i. e . with a solubility o f less than 5 %, preferably o f less than 1 % and even more preferably o f less than 0. 1 % .

The fatty substances are preferably non-siliceous, meaning that their structure does not contain a silicon atom. They generally have in their structure a hydrocarbon chain comprising at least 6 carbon atoms and not comprising any siloxane group .

In addition, the fatty substances are generally so luble in organic so lvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamet hy Icy clop entasiloxane .

The liquid fatty substances that may be used in the invention are liquid at ambient temperature (25 °C) and under atmospheric pressure (760 mmHg, i. e. 1 .013 x 10 ⁵ Pa) . They preferably have a viscosity o f less than or equal to 2 Pa. s, better still less than or equal to 1 Pa. s, and even better still less than or equal to 0. 1 Pa. s at a temperature of 25 °C and at a shear rate of 1 s ^{" 1} .

The liquid fatty substances that may be used in the composition according to the invention are generally not oxyalkylenated and preferably do not contain any carboxylic acid COOH functions.

The liquid fatty substances are preferably chosen from hydrocarbons, fatty alcoho ls, fatty esters, fatty ethers, and mixtures thereo f.

Even more preferentially, they are chosen from hydrocarbons, fatty alcoho ls and fatty esters, and mixtures thereof.

The term "liquid hydrocarbon" means a hydrocarbon composed so lely o f carbon and hydrogen atoms, which is liquid at standard temperature (25 ° C) and at atmospheric pressure (760 mmHg, i. e . 1 .01 3 x 10 ⁵ Pa), which is of mineral or plant or synthetic origin.

More particularly, the liquid hydrocarbons are chosen from:

- linear or branched, optionally cyclic, C ₆ - C i 6 alkanes . Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane,

- linear or branched hydrocarbons o f synthetic, animal or mineral origin, with more than 1 6 carbon atoms, such as liquid paraffins or liquid petrolatum, polydecenes, hydrogenated polyisobutene such as that sold under the brand name Parleam® by the company NOF Corporation, and squalane.

In one preferred variant, the liquid hydrocarbon(s) is (are) chosen from liquid paraffins and liquid petrolatum.

The term "liquid fatty alcoho l" is understood to mean a nonglycerolated and nonoxyalkylenated fatty alcohol which is liquid at standard temperature (25 °C) and at atmospheric pressure (760 mmHg, i. e. 1 .013 10 ⁵ Pa) .

Preferably, the liquid fatty alcoho ls o f the invention comprise from 8 to 30 carbon atoms . The liquid fatty alcohols of the invention may be saturated or unsaturated.

The saturated liquid fatty alcohols are preferably branched. They may optionally comprise in their structure at least one aromatic or non-aromatic ring. They are preferably acyclic.

More particularly, the liquid saturated fatty alcohols of the invention are chosen from octyldodecanol, isostearyl alcohol and 2- hexyldecanol.

Octyldodecanol is most particularly preferred.

The unsaturated liquid fatty alcohols contain in their structure at least one double or triple bond, and preferably one or more double bonds. When several double bonds are present, there are preferably 2 or 3 of them, and they may be conjugated or unconjugated.

These unsaturated fatty alcohols may be linear or branched. They may optionally comprise in their structure at least one aromatic or non-aromatic ring. They are preferably acyclic.

More particularly, the unsaturated liquid fatty alcohols of the invention are chosen from oleyl alcohol, linoleyl alcohol, linolenyl alcohol and undecylenyl alcohol.

Oleyl alcohol is most particularly preferred.

The term "liquid fatty ester" means an ester derived from a fatty acid and/or from a fatty alcohol that is liquid at standard temperature (25°C) and at atmospheric pressure (760 mmHg, i.e. 1.013 x 10 ⁵ Pa).

The esters are preferably liquid esters of saturated or unsaturated and linear or branched C1-C26 aliphatic mono- or polyacids and of saturated or unsaturated and linear or branched C1-C26 aliphatic mono- or polyalcohols, the total number of carbon atoms in the esters being greater than or equal to 10.

Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the invention are derived is branched.

Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, isopropyl palmitate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C4-C22 dicarboxylic or tricarboxylic acids and of Ci- C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C4-C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy non-sugar alcohols may also be used.

Mention may be made especially of diethyl sebacate, diisopropyl sebacate, bis(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl glycol diheptanoate, and diethylene glycol diisononanoate.

The composition may also comprise, as liquid fatty ester, sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon- based compounds which contain a plurality of alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar and fatty acid esters may be chosen in particular from the group comprising the esters or mixtures of sugar esters described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, and polyesters, and mixtures thereof. These esters may be, for example, o leates, laurates, palmitates, myristates, behenates, cocoates, stearates, lino leates, lino lenates, caprates or arachidonates, or mixtures thereof, such as, especially, oleopalmitate, oleostearate or palmitostearate mixed esters .

More particularly, use is made o f monoesters and diesters and especially o f sucrose, glucose or methylglucose mono- or dio leates, stearates, behenates, o leopalmitates, lino leates, lino lenates or oleostearates .

An example that may be mentioned is the product sold under the name Glucate® DO by the company AMERCHOL, which is a methylglucose dio leate .

Finally, use may also be made o f natural or synthetic glycero l esters of mono-, di- or triacids .

Among these, mention may be made of plant oils .

As oils o f plant origin or synthetic triglycerides that may be used in the composition o f the invention as liquid fatty esters, examples that may be mentioned include :

- triglyceride oils o f plant or synthetic origin, such as liquid fatty acid triglycerides containing from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, o live oil, rapeseed oil, coconut oil, wheatgerm oil, sweet almond oil, safflower oil, candlenut oil, camelina oil, tamanu oil, babassu oil and pracaxi oil, caprylic/capric acid triglycerides, for instance those so ld by the company STEARINERIES DUBOIS or those so ld under the names Miglyo l® 8 10, 8 12 and 8 1 8 by the company DYNAMIT NOBEL, jojoba oil and shea butter oil.

Liquid fatty esters derived from monoalcohols will preferably be used as esters according to the invention.

Isopropyl myristate and isopropyl palmitate are particularly preferred.

The liquid fatty ethers are chosen from liquid dialkyl ethers such as dicaprylyl ether. The liquid fatty substances are preferably chosen from liquid paraffins or liquid petrolatum, octyldodecanol, isostearyl alcoho l, 2- hexyldecanol, o leyl alcoho l, lino leyl alcohol, lino lenyl alcoho l and undecylenic alcoho l, ethyl and isopropyl palmitates, alkyl myristates such as isopropyl or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate, and vegetable oils.

More preferably still, the liquid fatty substances are chosen from liquid paraffins or liquid petrolatum.

When the liquid fatty substance or substances is or are present, the amount thereof varies preferably, for examp le, from 10% to 90% by weight, better still from 20%> to 80%> by weight, even better still from 30%) to 80%>, more preferably still from 50%> to 80%> by weight, relative to the total weight of the dyeing composition (A) or the expanded oxidizing composition (B) .

In one particularly advantageous variant of the invention, the composition (A) comprises one or more liquid fatty substances, particularly in an amount greater than or equal to 10% by weight, relative to the total weight o f the dyeing composition (A), preferably chosen from linear or branched hydrocarbons, o f mineral, animal or synthetic origin, with more than 16 carbon atoms, more particularly liquid petrolatum.

The dyeing composition (A) and/or the expanded oxidizing composition (B) according to the invention may further comprise one or more anionic, nonionic, cationic or amphoteric surfactants, preferably nonionic surfactants, and even better still nonionic surfactants which are oxyalkylenated.

Examples o f oxyalkylenated nonionic surfactants that may be used in the composition used according to the invention are described in, for example, "Handbook of Surfactants" by M.R. PORTER, published by Blackie & Son (Glasgow and London), 1991 , pp . 1 16- 178. They are chosen in particular from alcohols, a-dio ls and alkyl(C i - C ₂ o)phenols, these compounds being polyethoxylated and/or polypropoxylated and having at least one fatty chain containing, for example, from 8 to 22 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to range in particular from 1 to 1 00.

Mention may also be made of copolymers of ethylene oxide and propylene oxide, oxyethylenated esters of fatty acids and sorbitan, polyoxyalkylenated fatty acid esters and oxyalkylenated alky lpoly glycosides.

Unless otherwise mentioned, a "fatty" compound, as for example a fatty acid, denotes a compound which comprises, in its main chain, at least one saturated or unsaturated hydrocarbon chain, such as alkyl or alkenyl, containing at least 8 carbon atoms, preferably from 8 to 30 carbon atoms, and better still from 10 to 22 carbon atoms.

The oxyalkylenated nonionic surfactant or surfactants particularly preferred in the invention is or are chosen from polyoxyalkylenated, better still polyethoxylated, fatty alcoho ls, having at least one fatty chain comprising preferably from 8 to 22 carbon atoms, it being possible for the number of ethylene oxide groups to range in particular from 1 to 100, better still from 1 to 50. Mention may be made, for example, o f the compounds with INCI name o leth- 30, oleth-20, oleth- 10, steareth-2, deceth-3 , deceth-5 or laureth- 12.

When the preferably nonionic surfactant or surfactants is or are present, the amount thereo f varies for example from 0. 1 % to 30% by weight, and preferably from 1 % to 20% by weight, relative to the total weight of the dyeing composition (A) or the expanded oxidizing composition (B).

According to one embodiment, the dyeing composition (A) and/or the expanded oxidizing composition (B) may also comprise a nonionic ether of polyoxyalkylenated fatty alcohols .

The term "nonionic ether o f po lyoxyalkylenated fatty alcoho ls" is understood to mean an ether derived or resulting from fatty alcoho ls, i. e. long-chain alcoho ls, preferably C 8 - C 40 alcoho ls, which comprises one or more divalent C i -C ₆ alkoxyl groups : - [0-Alk] _p - , where p is an integer ranging from 1 to 200 and Alk represents a C i -C ₆ alkylene group such as ethylene or propylene, preferably ethylene; and in which one o f the fatty chains may be substituted, preferably substituted by one or more hydroxyl groups, including at least one hydroxyl group located in beta position to an ether function.

According to one particular embodiment of the invention, the nonionic ether or ethers o f po lyalkylenated fatty alcoho ls are chosen from the compounds of formula (XII) below:

R-(0-Alk) _n -0-R' (XII),

and also the optical isomers and geometrical isomers thereof;

in which formula (XII) :

- R denotes a saturated or unsaturated, linear or branched C 10- C30 hydrocarbon group,

R' denotes a saturated or unsaturated, linear or branched C 10- C30 hydrocarbon group which may be substituted by a hydroxyl group, preferably substituted by the hydroxyl group which is located in β to the ether function,

n is an integer ranging from 1 to approximately 1 00, and

Alk represents a (C i - C ₆ ) alkylene group which is linear or branched, preferably linear, such as ethylene or propylene, preferably ethylene.

According to one particularly advantageous embodiment o f the invention, the group Alk in the formula (XII) represents a group

More particularly, the nonionic ether o f formula (XII) is such that R and R' , independently o f one another, denote a hydrocarbon group which is linear or branched, preferably linear, and is saturated or unsaturated, preferably saturated, this group being C 12-C20 , preferably C _{1 4} -C _{1 8} ; R' may be substituted by at least one hydroxyl group, and n denotes an integer greater than or equal to 20, ranging for example from 20 to 100, preferably from 40 to 80.

R and R' preferably denote an alkyl group .

According to a more preferred embodiment, the nonionic ether of formula (XII) is such that : R denotes a preferably linear C _{1 6} -C _{1 8} alkyl group, and R' denotes a preferably linear C _{1 4} alkyl group which is substituted by an OH group, and n is 60.

The ether of formula (XII) is preferably of the formula below:

where R is a cetyl or stearyl group where n = 60.

Such a compound is denoted, for example, in the CTFA dictionary under the name Ceteareth-60 myristyl glyco l or alternatively hydrogenated talloweth-60 myristyl glyco l. A Ceteareth- 60 myristyl glyco l is so ld, for examp le, by the company AKZO under the trade name ELFACOS GT 282 S .

In the composition (A) or (B) according to the invention, the nonionic ether or ethers o f po lyoxyalkylenated fatty alcoho ls is or are present in a concentration ranging preferably from 0.001 % to 10%, more preferably from 0.001 % to 5 %, by weight, relative to the total weight of the composition of the invention.

The pH of the dyeing composition (A) may vary generally from 3 to 12 approximately, and preferably from 5 to 1 1 approximately. It may be adjusted to the desired value by means o f acidifying or basifying agents customarily used in the dyeing of keratin fibres, or alternatively using standard buffer systems .

Among the acidifying agents, mention made be made, by way of example, o f inorganic or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids .

As far as the basifying agents are concerned, those referred to above may be used.

The pH o f the expanded oxidizing composition varies preferably from 1 .5 to 8.5 , more preferably from 2 to 7 and better still from 2 to 4.

The dyeing composition (A) and/or the expanded oxidizing composition (B) may also comprise various adjuvants which are conventionally used in compositions for the co louring or lightening o f hair, such as anionic, nonionic or amphoteric polymers or mixtures thereo f; associative polymers; antioxidants; penetrants; sequestrants such as etidronic acid or pentasodium pentetate; fragrances; dispersants; film-formers; ceramides; preservatives; opacifiers, and polyo ls, more particularly polyols with molecular weights of less than 500.

Amphoteric polymers include, in particular, the polymers comprising as monomers at least one monomer derived from a vinyl compound carrying a carboxyl group, such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and at least one basic monomer derived from a substituted vinyl compound containing at least one basic atom, chosen in particular from the following :

a) dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylates, dialkylaminoalkylmethacrylamides and dialkylaminoalkylacrylamides. Such compounds are described in patent US 3 836 537.

b) trialkylaminoalkyl methacrylate salts and trialkylaminoalkyl acrylate salts, and salts o f trialkylaminoalkylmethacrylamide and o f trialkylaminoalkylacrylamide. Mention may in particular be made o f the acrylic acid/acrylamidopropyltrimethylammonium chloride copolymer available from the company Stockhausen under the name Polymere W3794. Mention may also be made o f the acrylic acid/ acrylamidopropyltrimethyl ammonium/ chloride/acrylamide copolymers available from the company Nalco under the names Merquat 200 1 and Merquat 2003.

The associative polymers may be anionic, cationic, amphoteric or nonionic, preferably nonionic and cationic . For the purposes o f the present invention, the term "associative polymers" means water- so luble polymers that are capable, in an aqueous medium, of reversibly combining with each other or with other mo lecules. Their chemical structure comprises at least one hydrophilic region and at least one hydrophobic region characterized by at least one C 8 - C 30 fatty chain.

Mention may be made more particularly o f the nonionic associative polymers chosen from polyether polyurethanes having hydrophilic and hydrophobic sequences, nonionic cellulo se derivatives comprising at least one fatty chain, and cationic associative polymers, chosen from quaternized cellulose derivatives comprising at least one fatty chain.

Polyo ls with a mo lecular mass o f less than 500 include sorbito l, glucose, fructose, xylo se, trehalo se, sucrose, maltose, lactose, polyethylene glycols and C 3 - C 8 dio ls or trio ls, particularly butanedio l.

Preference is given to non-etherified polyols and non-esterified polyo ls.

Particularly preferred polyo ls are glycerol and 1 ,2-propylene glyco l, and preferably glycerol.

The above adjuvants are generally present in an amount, for each o f them, o f between 0.01 % and 20% by weight, relative to the weight of the composition.

Preferably, the expanded compositions o f the invention are not conditioned in a pressurized container.

The method of oxidation-co louring keratin fibres invo lves applying the optionally expanded dyeing composition (A) and the expanded oxidizing composition (B), as described above, to the keratin fibres, sequentially or simultaneously.

In a first variant o f the method according to the invention, the dyeing composition (A) is mixed at the time o f use with the expanded oxidizing composition (B), and the resulting mixture is then applied to the keratin fibres.

In a second variant of the method according to the invention, the dyeing composition (A) is applied to the keratin fibres before or after the expanded oxidizing composition (B) .

The method may be repeated several times in order to obtain the desired coloration.

The compositions described previously are applied to wet or dry keratin fibres.

The composition(s) are usually left in place on the fibres for a time generally ranging from 1 minute to 1 hour and preferably from 5 minutes to 30 minutes . The temperature during the method is conventionally between 20 and 80°C , preferably between 20 and 60°C .

After the treatment, the human keratin fibres are advantageously rinsed with water. They may optionally be washed with a shampoo, fo llowed by rinsing with water, before being dried or left to dry.

The invention relates also to the expanded oxidizing composition as described above.

The invention further relates to a ready-to-use composition which results from the extemporaneous mixing o f the optionally expanded dyeing composition (A) and of the expanded oxidizing composition (B) as described above.

The compositions (A) and (B) are preferably mixed in a (A)/(B) weight ratio of from 0. 1 to 5 , better still from 0.2 to 2.

Another subj ect of the invention concerns a multi-compartment device, or a kit for dyeing keratin fibres, comprising at least two compartments :

- a first compartment containing a dyeing composition (A) as described above; and

- a second compartment containing an expanded oxidizing composition (B) as described above.

In a first variant o f the invention, only the oxidizing composition (B) is expanded.

In a second variant of the invention, the two compositions (A) and (B) are expanded.

According to one variant o f the invention, the kit also comprises an additional compartment containing an additional composition comprising one or more treating agents.

The compositions of the kit are packaged in separate compartments, which may be optionally accompanied by suitable identical or different application means, such as fine brushes, coarse brushes or sponges . The abovementioned kit may also be equipped with means allowing the delivery to the hair o f the desired mixture, such as, for example, the device described in patent FR 2 586 913.

The examples that fo llow are given purely as illustrations o f the present invention.

EXAMPLES

Example 1

A base oxidizing composition, referred to hereinafter as oxidizing composition 1 , is prepared from the ingredients indicated in the table below. The amounts indicated are expressed in % by weight of active substance relative to the total weight of the oxidizing composition 1 .

Oxidizing composition 1 :

Oxidizing composition 1 is expanded using a Minimondomix expander from the company HAAS , with introduction o f nitrogen. Oxidizing composition 1 is metered using a diaphragm pump to the aerating head; at the same time, the gas is metered by means o f a vo lumetric flowmeter. Both arrive perpendicularly in the part of the aerator upstream o f the rotor. By combining the flow o f oxidizing composition 1 and gas with the actuation o f the rotor, mixing takes place continuously and regularly, to give, at the outlet o f the device, the oxidizing composition 2.

At a constant flow rate of oxidizing composition 1 , the degree of expansion may easily be adapted depending on the vo lume o f gas introduced in the Minimondomix.

Oxidizing composition 2 is composed of 60 g o f oxidizing composition 1 and 40 g of nitrogen.

Oxidizing composition 2 has the appearance o f an oily, aerated cream (of chocolate mousse type) .

At the time o f use, 1 0 g o f oxidizing composition 2 are mixed with 10 g o f dyeing composition (INOA® Nuance 5) . Mixing is performed very easily. The mixture is subsequently applied to the lo cks at 10 g o f mixture per gram o f hair. App lication is easy. The mixture is left to act for 30 minutes.

The original appearance o f the oxidizing composition is retained on mixing with the dyeing cream.

The hair is then rinsed, washed with a standard shampoo and dried.

The hair co loration is evaluated visually. A light brown co lour is obtained.

Similar results are obtained when the nitrogen is replaced by carbon dioxide or argon. Example 2

An expanded dyeing composition is prepared in the manner set out below, and the expanded oxidizing composition (oxidizing composition 2) prepared in Example 1 is used.

First, a base dyeing composition, referred to hereinafter as dyeing composition 1 , is prepared from the ingredients indicated in the table below. The amounts indicated are expressed in % by weight o f active substance relative to the total weight of the dyeing composition 1 .

Dyeing composition 1 :

% by weight

Resorcino l 0.67

Ethano lamine 4.28

Hydroxybenzomorpholine 0.033

Ascorbic acid 0. 12

Glycerol 5

m-Aminopheno l 0. 12

2,4-Diaminophenoxyethano l HC1 0.02

Deceth-5 1 .08

Sodium metabisulfite 0.22

Mineral oil paraffinum liquidum 60

Carbomer 0.098

Oleth- 10 1

Oleth-20 4

C 20 -22 alcoho ls 4.6

2,5 -Diaminotoluene 0.7623

Cetyl palmitate 2

Ceteareth-60 myristyl glyco l 0.01

Water qs 100 Dyeing composition 1 is expanded by means o f a Minimondomix expander from the company HAAS, with introduction of nitrogen. Dyeing composition 1 is metered by means of a diaphragm pump to the aeration head; at the same time, the gas is metered by means of a vo lumetric flowmeter. The two arrive perpendicularly in the part of the aerator upstream o f the rotor. By combining the flow o f dyeing composition 1 and gas with the actuation of the rotor, mixing is carried out continuously and regularly, to give the dyeing composition 2 at the outlet of the device.

At a constant rate of dyeing composition 1 , the degree o f expansion can be easily adapted depending on the vo lume o f gas introduced into the Minimondomix.

Dyeing composition 2 is composed of 60 g o f dyeing composition 1 and 40 g o f nitrogen. Dyeing composition 2 and oxidizing composition 2 have the appearance o f oily, aerated creams (of chocolate mousse type) .

At the time o f use, 10 g o f dyeing composition 2 are mixed with 10 g of oxidizing composition 2. Mixing is performed very easily. The mixture is subsequently applied to the locks at 1 0 g of mixture per gram o f hair. Application is easy. The mixture is left to act for 30 minutes.

The original appearance o f the dyeing composition and the oxidizing composition is retained on mixing.

The hair is then rinsed, washed with a standard shampoo and dried.

The hair co loration is evaluated visually. A light brown co lour is obtained.

Similar results are obtained when the nitrogen is replaced by carbon dioxide or argon.