WO2010100231A1

WO2010100231A1 - Device for dispensing a colouring composition for keratin fibres and associated process

Info

Publication number: WO2010100231A1
Application number: PCT/EP2010/052761
Authority: WO
Inventors: Jean-Baptiste Saunier
Original assignee: L'oreal
Priority date: 2009-03-04
Filing date: 2010-03-04
Publication date: 2010-09-10
Also published as: FR2942704A1; FR2942704B1

Abstract

Device for dispensing a colouring composition for keratin fibres and associated process This device (10) comprises a first reservoir (16A to 16D) containing a dye composition, a second reservoir (18A to 18B) containing a second composition, and a third reservoir (20A to 20B) containing a third composition. It comprises a dispenser (22) capable of removing some dye composition, some second composition, and some third cosmetic composition and dispensing them into a packaging (26). The third composition is an anhydrous composition free from dyeing and oxidising agents, containing an oil. The control unit (24) comprises means (82) for controlling the dispenser (22) in such a way that the total mass of anhydrous composition dispensed to form each dose of colouring composition is more than 20 % of the total mass of the dose of colouring composition.

Description

Device for dispensing a colouring composition for keratin fibres and associated process

The present invention relates to a device for dispensing a colouring composition for keratin fibres, the device being of the type comprising: - a first reservoir containing a first composition, this composition having a dyeing effect;

- a second reservoir containing a second composition which is different from the first dye composition, this composition having an oxidising effect;

- a third reservoir containing a third composition which is different from the first composition and different from the second composition;

- a dispenser which is capable of removing a first mass of first composition from the first reservoir, a second mass of second composition from the second reservoir and a third mass of third composition from the third reservoir, and for dispensing them into a packaging to form, after mixing, a dose of colouring composition in the packaging. Colouring compositions of this type are intended to dye or highlight human keratin fibres such as hair.

Methods of dyeing human keratin fibres include oxidation or permanent dyeing. This mode of dyeing makes use of one or more precursors of oxidation dyes, conventionally one or more oxidation bases, optionally associated with one or more couplers.

In general, the oxidation bases are colourless or faintly coloured compounds which when combined with oxidising products make it possible to obtain dyed substances by a process of oxidative condensation.

It is known to alter the shades obtained with these oxidation bases by combining them with one or more couplers. The variety of molecules involved in the oxidation bases and the couplers allows a wide range of colours to be obtained.

Direct or semi-permanent dyeing is also known. In a conventionally used process, direct dyes are applied to the keratin fibres. These direct dyes are dyed and dyeing molecules which have an affinity for the fibres. After the application of the dye, there is a pause to allow the molecules of the dye to penetrate into the fibres by diffusion within the fibre, before rinsing.

This type of process does not generally require the use of an oxidising agent to develop the dyeing. However, the use thereof is not excluded for obtaining a highlighted effect along with the dyeing. Dyeing of this type is therefore known as direct or semi- permanent dyeing in conditions involving highlighting. Permanent or even semi-permanent dyeing processes in conditions involving highlighting make use, together with the dye composition, of an aqueous composition comprising at least one oxidising agent at an alkaline pH in the vast majority of cases.

The purpose of this oxidising agent is to decompose the melanin in the hair, leading to more or less pronounced highlighting of the fibres, and in the case of oxidation dye, to allow the condensation of the molecules of dyes.

In a conventional manner, it is known to mix a dye composition which has already been formulated and received in a first packaging, with an oxidising composition received in a second packaging to prepare the colouring composition immediately before the use thereof, owing to the high reactivity of the oxidising agent.

In this case, it is easy to adjust the proportions of dye composition and oxidation composition to form a dose of colouring composition of a suitable mass for carrying out the dyeing.

However, in some cases, the colouring composition is formed from at least three different compositions, in highly variable proportions, in particular to obtain shades or oxidation strengths which are not commercially available. It is awkward to adjust the individual proportions of each composition as a function of the total mass of colouring composition desired using conventional packagings, in particular in a commercial environment such as a hairdressing salon or at the home of an individual. To alleviate this problem, a dispensing device of the aforementioned type is known for example from US 2005/0165705 and allows the user to select a recipe for the colouring composition to be prepared as a function of the desired colour, then to prepare and to dispense a dose of a selected mass of the colouring composition based on the recipe selected by the user. For this purpose, the device comprises a plurality of reservoirs each containing various dye compositions, at least one reservoir containing an oxidising agent and at least one reservoir containing an alkaline agent.

A device of this type is not completely satisfactory. In fact, to allow a wide variety of shades to be achieved while keeping the volume of the dispensing device low, it is necessary to provide low-volume dyeing containers, generally formed by plastics material pouches.

These reservoirs therefore have to be changed frequently, and this can pose problems in relation to cleanliness, in particular when drops of dye lost during the disconnection of the containers contaminate the inside of the dispensing device. One object of the invention is to provide a dispensing device which allows complex doses of colouring compositions of a mass selected by the user to be provided in a simple manner while reducing the risk of contamination of the device by dyeing substances.

For this purpose, the invention relates to a device of the above-mentioned type, characterised in that the third composition is anhydrous, free from dyeing and oxidising agent, and comprises one or more fats, the control unit comprising means for controlling the dispenser in such a way that the total mass of anhydrous composition dispensed from the, or from each third reservoir to form each dose of colouring composition is more than 20 % of the total mass of the dose of colouring composition. The device according to the invention may comprise one or more of the following features, taken individually or in any technically possible combination:

- the fat or fats contain one or more oils;

- the oil is selected from mineral oils, vegetable oils, animal oils, synthetic oils, or mixtures thereof, and is advantageously vaseline oil; - the fat content of the anhydrous composition is between 10 % and 99 % by weight based on the weight of the anhydrous composition;

- the control unit comprises means for controlling the dispenser in such a way that the total mass of dye composition dispensed from the, or from each first reservoir to form each dose of colouring composition is less than 25 % of the total mass of the dose; - the volume of the third reservoir is greater, advantageously at least two times greater, than the volume of the first reservoir;

- the control unit comprises a man-machine interface which can be controlled by a user to select at least one of the total mass of the dose and at least one parameter representing the colour produced by the colouring composition applied to the keratin fibres, advantageously the shade or the strength; and

- it comprises a plurality of third reservoirs each containing different anhydrous cosmetic compositions free from dyeing and oxidising agent, the control comprising a man-machine interface can be controlled by a user to select the or each anhydrous cosmetic composition which is to be put in the dose. More generally, the invention relates to a device for dispensing a colouring composition for keratin fibres, the device being of the type comprising:

- a first reservoir containing a first composition, this first composition having a dyeing effect,

- a second reservoir containing a second composition which is different from the first composition, this second composition having an oxidising effect, - a third reservoir containing a third composition which is different from the first composition and different from the second composition,

- a dispenser which is capable of removing a first mass of first composition from the first container, a second mass of second composition from the second container, and a third mass of third composition from the third container, and for dispensing them into a packaging to form, after mixing, a dose of colouring composition in the packaging; characterised in that the third composition is anhydrous, contains neither oxidising agent nor dye, and comprises one or more fats.

Advantageously, the or each fat is selected from alkanes, fatty alcohols, fatty acids, fatty acid esters, fatty alcohol esters, mineral oils, vegetable oils, animal oils, synthetic oils, silicones, waxes, or mixtures thereof.

In a variant, the control unit comprises means for controlling the dispenser in such a way that the total mass of anhydrous composition is more than 20 % of the total mass of the dose of colouring composition. The device according to the invention may further comprise one or more of the features defined above, taken individually or in any technically possible combination. The invention further relates to a process for dispensing a colouring composition for keratin fibres, characterised in that it comprises the following steps:

- providing a device of the type defined above, - controlling the dispenser using the control unit to remove the first mass of dye composition, the second mass of second composition, and the third mass of anhydrous composition and to dispense them into a packaging to form a dose, the total mass of anhydrous cosmetic composition dispensed from the or from each third reservoir to form each dose of colouring composition being more than 20 % of the total mass of the dose of colouring composition.

The process according to the invention may comprise the following feature:

- the total mass of dye composition dispensed the or from each first reservoir to form each dose of colouring composition is less than 25 % of the total mass of the dose.

Within the context of the present invention, the term 'a' should be taken to mean 'at least one' unless indicated otherwise.

A better understanding of the invention will be gained upon reading the following description, given merely by way of example and with reference to the appended drawings, in which:

- Fig. 1 is a schematic plan view of a first dispensing device according to the invention; - Fig. 2 is a schematic cross-sectional view along a vertical plane of a dispensing device assembly according to Fig. 1 ;

- Fig. 3 shows a man-machine interface in the control unit of the device of Fig. 1 ; and - Fig. 4 is a view analogous to Fig. 1 of a second device according to the invention.

Figs. 1 to 3 show a first device 10 for dispensing a colouring composition 12 according to the invention.

This device 10 is intended for the preparation and dispensing of individual doses 14 of the colouring composition 12 of a mass selected by a user, and having keratin fibre dyeing properties selected by the user, such as the shade or the oxidising strength.

As will be seen in detail below, the colouring composition is of the type disclosed in the Applicant's French Applications Nos. 0760273, 0760274 and n°0760277.

In the present example, the colouring composition comprises at least one first dye composition comprising one or more oxidation dyes and/or direct dyes, a second oxidising composition comprising one or more oxidising agents, and according to the invention, a third cosmetic composition formed by a anhydrous cosmetic composition comprising one or more preferably oily fats and advantageously one or more surfactants.

Referring to Fig. 1 , the first device 10 comprises a plurality of first removable reservoirs 16A to 16D containing different first dye compositions, a plurality of second removable reservoirs 18A to 18B containing different second oxidising compositions, and a plurality of third reservoirs 2OA to 2OB containing, according to the invention, different anhydrous cosmetic compositions, free from dyeing and oxidising agents and comprising one or more preferably oily fats.

The first device 10 further comprises a dispenser 22 for selectively removing a selected first mass of dye composition from one or more first reservoirs 16A to 16D, a second selected mass of oxidising composition from one or more second reservoirs 18A to 18B, and a third selected mass of anhydrous composition from one or more third reservoirs 2OA to 2OB.

The device 10 further comprises a control unit 24 for the dispenser 22, which can be controlled by a user.

The device 10 further comprises a removable packaging 26 for receiving the dose 14 of colouring composition 12 and a measurement assembly 28 for measuring the mass of the dose 14 contained in the packaging 26.

In the example shown in Fig. 1 , the first reservoirs 16A to 16D, the second reservoirs 18A to 18B, and the third reservoirs 2OA to 2OB are mounted on a turntable 30 which is driven in rotation relative to a fixed frame of the device 10 about a vertical central axis A-A', under the control of the unit 24.

The reservoirs 16A to 16D, 18A to 18B and 2OA to 2OB are in an angular distribution around the periphery of the table in such a way as to be brought selectively opposite the packaging 26 arranged on the measurement assembly 28 by displacing the table 30.

In the example shown in Fig. 1 , each first reservoir 16A to 16D is formed by a flexible pouch 32 which is held in a removable position, on the table 30, by a support.

The flexible pouch 32 substantially exclusively contains dye composition in a liquid form, and does not contain a significant amount of air.

A 'significant amount of air' is understood to be an amount greater than 5 % of the volume of the pouch 32.

Each dye composition comprises one or more oxidation dyes, or one or more direct dyes, or mixtures thereof. The oxidation dyes are generally selected from oxidation bases optionally combined with one or more couplers.

Examples of oxidation bases are defined, for example in French patent application No. 0760273. The oxidation bases are selected from paraphenylenediamines, bis- phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and the addition salts thereof.

Exa m p l e s of paraphenylenediamines, include paraphenylenediamine, paratoluylenedi a m i n e , 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylened i a m i n e , 2 , 6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylened i a m i n e , 2 , 5-dimethyl paraphenylened i a m i n e , N , N-dimethyl paraphenylenediamine, N,N-diethyl paraphenylenediamine, N,N-dipropyl paraphenylenediamine, 4-amino N,N-diethyl 3-methyl aniline, N ,N-bis-(β-hydroxyethyl) paraphenylenediamine, 4-N,N-bis-(β-hydroxyethyl)amino 2-methyl aniline,

4-N,N-bis-(β-hydroxye t h y I ) a m i n o 2-chloro aniline, 2-β-hydroxyethyl paraphenylened i a m i n e , 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N-(β-hydroxypropyl) p a raphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N,N-(ethyl, β- hydroxyethyl) paraphenylenediamine, N-(β,γ-dihydroxypropyl) paraphenylenediamine,

N-(4'-aminophen y I ) p a r aphenylenediamine, N-phenyl paraphenylenediamine,

2-β-hydroxyet h y l o x y p a r aphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, N-(β-methoxyethyl) paraphenylene-diamine, 4- aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2-β hydroxyethylamino 5-amino toluene, 3-hydroxy 1-(4'-aminophenyl)pyrrolidine and the acid addition salts thereof.

Of th e a bove m e nti o n ed pa raphenylenediamines, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy pa raphenylene-diamine, 2,6-dimethyl paraphenylened i a m i n e , 2 , 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N,N-bis-(β-hydroxyeth y l ) pa raphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and the acid addition salts thereof are particularly preferred. Examples of bis-phenylalkylenediamines include N,N'-bis-(β-hydroxyethyl) N, N'- bis-(4'-aminophen y l ) 1 ,3-diamino propanol, N,N'-bis-(β-hydroxyethyl ) N , N '-bis-(4'- aminophenyl) ethylenediamine, N,N'-bis-(4-aminophenyl) tetramethylenediamine, N,N'-bis-(β-hydroxyethyl) N ,N'-bis-(4-aminophenyl) tetramethylenediamine, N,N'-bis-(4- methyl-aminophen y I ) tetramethylenediamine, N,N'-bis-(et h y l ) N , N '-bis-(4'-amino, 3'-methylphenyl) ethylenediamine, 1 ,8-bis-(2,5-diamino phenoxy)-3,6-dioxaoctane, and the addition salts thereof.

Examples of para-aminophenols include para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro p henol, 4-amino-3-chlorophenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2- methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2-(β-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and the acid addition salts thereof.

Examples of ortho-aminophenols include 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and the addition salts thereof. Examples of heterocyclic bases include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Examples of pyridine derivatives include the compounds disclosed in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2-(4-methoxyphenyl)amino 3-amino pyridine, 3,4-diamino pyridine, and the addition salts thereof. Other pyridine oxidation bases which can be used in the present invention are 3- amino pyrazolo-[1 ,5-a]-pyridine oxidation bases or addition salts thereof disclosed for example in patent application FR 2801308. Examples include pyrazolo[1 ,5-a]pyridin-3- ylamine; 2-acetylamino pyrazolo-[1 ,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo[1 ,5- a]pyridin-3-y l a m i n e ; 3-amino-pyrazolo[1 ,5-a]pyridin-2-carboxylic acid; 2-methoxy- pyrazolo[1 ,5-a]pyridin-3-ylamino; (3-amino-pyrazolo[1 ,5-a]pyridin-7-yl)-methanol; 2-(3- amino-pyrazolo[1 ,5-a]pyridin-5-yl)-ethanol; 2-(3-amino-pyrazolo[1 ,5-a]pyridin-7-yl)- ethanol; (3-amino-pyrazolo[1 ,5-a]pyridin-2-yl)-methanol; 3,6-diamino-pyrazolo[1 ,5- a]pyridine; 3,4-diamino-pyrazolo[1 ,5-a]pyridine; pyrazolo[1 ,5-a]pyridin-3,7-diamine; 7- morpholin-4-yl-pyrazolo[1 ,5-a]pyridin-3-ylamine; pyrazolo[1 ,5-a]pyridin-3,5-diamine; 5- morpholin-4-yl-pyrazolo[1 ,5-a]pyridin-3-ylamine; 2-[(3-amino-pyrazolo[1 ,5-a]pyridin-5-yl)- (2-hydroxyethyl)-amino]-ethanol; 2-[(3-amino-pyrazolo[1 ,5-a]pyridin-7-yl)-(2-hydroxyethyl)- amino]-ethanol; 3-amino-pyrazolo[1 ,5-a]pyridin-5-o I ; 3-amino-pyrazolo[1 ,5-a]pyridin-4-ol; 3-amino-pyrazolo[1 ,5-a]pyridin-6-ol; 3-amino-pyrazolo[1 ,5-a]pyridin-7-ol; and also the addition salts thereof. Examples of pyrimidine derivatives include the compounds disclosed in patents

DE 2359399; JP 88-169571 ; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-h y d r o x y 4 , 5 , 6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine,

2,5,6-triaminopyrimidine and the addition salts thereof and the tautomeric forms thereof if a tautomeric equilibrium exists.

Pyrazole derivatives include the compounds disclosed in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino 1 -methyl pyrazole, 4,5-diamino i-(β-hydroxyethyl) pyrazole, 3,4-diamino pyrazole,4,5-diamino 1-(4'-chlorobenzyl) pyrazole, 4,5-diamino 1 ,3- dimethyl pyrazole, 4,5-diamino 3-methyl 1 -phenyl pyrazole, 4,5-diamino 1 -methyl 3-phenyl pyrazole, 4-amino 1 ,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1 -methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino i-(β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1 -ethyl 3-methyl pyrazole, 4,5-d iami no 1 -ethyl 3-(4'-methoxyphenyl) pyrazole, 4,5-d iam ino 1 -ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1 -methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5-(2'-aminoethyl)amino 1 ,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5- triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4-(β-hydroxyethyl)amino 1-methyl pyrazole, and the addition salts thereof. 4-5-diamino 1- (β-methoxyethyl)pyrazole may also be used.

Another suitable heterocyclic base is 2,3 diamino 6,7 dihydro 1 H5H [pyrazolol ,2, a] pyrazol-1-one or a salt thereof.

Examples of couplers are defined for example in French patent application No. 0760273. The couplers are generally selected from meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers, and the addition salts thereof. Examples include 1 , 3-d i hydroxy benzene, 1 ,3-dihydroxy 2-methyl benzene, 4- chloro 1 ,3-dihydroxy benzene, 2,4-diamino i-(β-hydroxyethyloxy) benzene, 2-amino 4-(β- hydroxyet h y l a m i n o ) 1-methoxybenzene, 1 ,3-d i a m i n o be n zene, 1 ,3-bis-(2,4- diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2 methyl-1-naphthol, 6- hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6- hyd roxy benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β- hydroxyethyl)amino-3,4-methylene dioxybenzene, 2,6-bis-(β-hydroxyethylamino)toluene, 6-hydroxy indoline, 2, 6-dihydroxy 4-methyl pyridine, 1-H 3-methyl pyrazole 5-one, 1- phenyl 3-methyl pyrazole 5-one, 2,6-dimethyl pyrazolo [1 ,5-b]-1 ,2,4-triazole, 2,6-dimethyl [3,2-c]-1 ,2,4-triazole, 6-methyl pyrazolo [1 ,5-a]-benzimidazole, the acid addition salts thereof, and mixtures thereof.

The addition salts of the oxidation bases and couplers are in particular selected from the acid addition salts such as the hydrochlorides, hydrobromides, su lphates, citrates, succinates, tartrates, lactates, tosylates, benzene sulphonates, phosphates and acetates.

The dye compositions provided in each first reservoir 16A to 16D are relatively highly concentrated. Thus, the oxidation base or bases are each advantageously from 0.001 % by mass to 30 % by mass based on the total mass of the dye composition, and preferably from 0.005 % by mass to 20 % by mass based on the total mass of the dye composition. The coupler or couplers each advantageously represent from 0.001 % by mass to 20 % by mass based on the total mass of the dye composition, and preferably from 0.001 % by mass to 20 % by mass based on the total mass of the dye composition.

The direct dyes are advantageously selected from the ionic or non-ionic type, preferably the cationic or non-ionic types.

Examples of direct dyes include azo, methine, carbonyl, azine, nitrated, (hetero)aryl, tri-(hetero)aryl methane, porphyrine, phthalocyanine direct dyes and natural direct dyes, individually or in a mixture.

Examples of dyes of this type are disclosed in the Applicant's French application No. 0760273.

More particularly, azo dyes comprise a -N=N- functional group in which the two nitrogen atoms are not simultaneously engaged in a ring. However, this does not exclude the possibility of one of the two nitrogen atoms in the -N=N- bond being engaged in a ring. Dyes in the methine family are more particularly compounds comprising at least one bond selected from >C=C< and -N=C< in which the two atoms are not simultaneously engaged in a ring. It should however be noted that one of the nitrogen or carbon atoms of the bonds may be engaged in a ring. More particularly, dyes in this family are based on compounds of the following type: methine, azomethine, mono- and di-arylmethane, i n d oa m i n es (or diphenylamines), indophenols, indoanilines, carbocyanines, azacarbocyanines and the isomers thereof, diazacarbocyanines and the isomers thereof, tetraazacarbocyanines and hemicyanines.

Examples of dyes from the carbonyl family include dyes selected from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine, dicetopyrrolopyrrole, coumarin. Dyes from the cyclic azine family include in particular azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine, pyronine.

The (hetero)aromatic nitrated dyes are more particularly benzene nitrated or pyridine nitrated direct dyes.

For dyes of the porphyrine or phthalocyanine type, it is possible to use compounds which are optionally cationic, optionally comprising one or more metals or metal ions, such as alkali and alkaline earth metals, zinc and silicon.

Examples of particularly suitable direct dyes include nitrated dyes from the benzene range; azo; azomethine; methine direct dyes; azacarbocyanines such as tetraazacarbocyanine (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine; xanthene; triarylmethane; indoamine; indigoid direct dyes; phthalocyanines, porphyrines and natural direct dyes, individually or in mixtures.

These dyes may be monochromophore (i.e. containing only one dye) or polychromophore dyes, preferably di- or tri-chromophore; the chromophores may be identical or non-identical, from the same or different chemical families. It should be noted that a polychromophore dye comprises a plurality of radicals each based on a molecule which absorbs in the visible range between 400 and 800 nm. Moreover, this absorbency of the dye does not necessitate oxidation thereof beforehand, nor combination with one or more other chemical substances. In polychromophore dyes, the chromophores are interconnected by at least one linker which may be cationic.

The linker is preferably a linear, branched or cyclic C₁-C₂0 alkyl chain optionally containing at least one heteroatom (such as nitrogen, oxygen) and/or at least one group comprising said heteroatom (CO, SO₂), optionally containing at least one heterocycle, optionally condensed, having a phenyl ring and comprising at least one quaternised nitrogen atom engaged in said cycle and optionally at least one other heteroatom (such as oxygen, nitrogen or sulphur), optionally containing at least one phenyl or naphthyl group, optionally substituted, optionally at least one quaternary ammonium group substituted by two C-ι-C-₁5 alkyl groups, optionally substituted; the linker not comprising any nitro, nitroso or peroxo groups.

If the heterocycles or aromatic rings are substituted, then they are substituted for example by one or more CrC₈ alkyl radicals, optionally substituted by a hydroxyl group,

C₁-C2 alkoxy group, C2-C4 hydroxyalkoxy group, acetylamino group, amino group substituted by one or two CrC₄ alkyl radicals, optionally carrying at least one hydroxyl group or it being possible for the two radicals to form, together with the nitrogen atom to which they are attached, a heterocycle having 5 or 6 bonds, optionally comprising another heteroatom identical to or different from nitrogen; a halogen atom; a hydroxyl group; a Cr

C₂ alkoxy radical; a C₂-C₄ hydroxyalkoxy radical; an amino radical; an amino radical substituted by one or two identical or different d-C₄ alkyl radicals optionally carrying at least one hydroxyl group.

The following is a non-limiting list of benzene direct dyes which may be used according to the invention:

1 ,4-diamino-2-nitrobenzene, - 1-amino-2 nitro-4-β- hydroxyethylaminobenzene

1-amino-2 nitro-4-bis(β-hydroxyethyl)-aminobenzene 1 ,4-bis(β -hydroxyethylamino)-2-nitrobenzene

1- β -hydroxyethylamino-2-nitro-4-bis-(β-hydroxyethylamino)-benzene 1- β -hydroxyethylamino-2-nitro-4-aminobenzene - 1 -β-hydroxyethylamino-2-nitro-4-(ethyl)(β-hydroxyethyl)-aminobenzene

1 -amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene 1 -amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene 1 ,2-diamino-4-nitrobenzene 1 -amino-2-β-hydroxyethylamino-5-nitrobenzene - 1 ,2-bis-(β-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-aminobenzene 1 -Hydroxy-2-amino-4,6-dinitrobenzene - 1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene

1 -Methoxy-2-β-hydroxyethylamino-5-nitrobenzene 1 -β-hydroxyethyloxy-3-methylamino-4-nitrobenzene 1- β,γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene 1-β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-2-nitrobenzene - 1-β,γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene

1 -β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene 1 -β-hydroxyethylamino-3-methyl-2-nitrobenzene 1 -β-aminoethylamino-5-methoxy-2 -nitrobenzene 1 -Hydroxy^-chloro-δ-ethylamino^-nitrobenzene - 1-Hydroxy-2-chloro-6-amino-4-nitrobenzene

1 -Hydroxy-6-bis-(β-hydroxyethyl)-amino-3-nitrobenzene 1 -β-hydroxyethylamino-2-nitrobenzene 1-Hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

The azo, azomethine, methine or tetraazapentamethine direct dyes which can be used according to the invention include the cationic dyes disclosed in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2189006, FR 2285851 , FR-2140205, EP 1378544, EP 1674073.

Therefore, in particular, this includes the following dyes of formulae (I) to (IV), and preferably the compounds of formulae (I) and (III):

in which:

D represents a nitrogen atom or the group -CH,

Ri and R₂, are the same or different and represent a hydrogen atom; a C₁-C₄ alkyl radical which may be substituted by a -CN, -OH or -NH₂ radical or forms, together with a carbon atom of the benzene ring, an optionally oxygenated or nitrogenated heterocycle which may be substituted by one or more CrC₄ alkyl radicals; a 4'-aminophenyl radical, R₃ and R'₃, are the same or different and represent a hydrogen or halogen atom selected from chlorine, bromine, iodine and fluorine, a cyano, CrC₄ alkyl, d-C₄ alkoxy or acetyloxy radical,

X ^" represents an anion preferably selected from chloride, methyl sulphate and acetate,

A represents a group selected from the following structures A1 to A18:

MO ^A12

^Λ13 A

in which R₄ represents a d-C₄ alkyl radical which may be substituted by a hydroxyl radical and R₅ represents a d-C₄ alkoxy radical;

in which:

R₆ represents a hydrogen atom or a CrC₄ alkyl radical,

R₇ represents a hydrogen atom, an alkyl radical which may be substituted by a - CN radical or by an amino group, a 4'-aminophenyl radical, or forms together with R₆ an optionally oxygenated and/or nitrogenated heterocycle which may be substituted by a d- C₄ alkyl radical,

R₈ and R₉ are the same or different and represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a d-C₄ alkyl or d-C₄ alkoxy radical, or a -CN radical,

B represents a group selected from the following structures B1 to B6:

B4 B5 B6 in which R₁₀ represents a Ci-C₄ alkyl radical, Rn and Ri₂, are the same or different and represent a hydrogen atom or a CrC₄ alkyl radical;

(ill) (in¹) in which:

Ri₃ represents a hydrogen atom, a Ci-C₄ alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine, Ri₄ represents a hydrogen atom, a CrC₄ alkyl radical or forms together with a carbon atom of the benzene ring, a heterocycle which is optionally oxygenated and/or substituted by one or more d-C₄ alkyl groups,

Ri₅ represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine,

Ri6 and Ri₇, are the same or different and represent a hydrogen atom or a d-C₄ alkyl radical,

D₁ and D₂ are the same or different and represent a nitrogen atom or the group - CH, m = 0 or 1 , it being understood that when R₁₃ represents a non-substituted amino group, D₁ and D₂ simultaneously represent a -CH group and m = 0,

X ^" represents an anion preferably selected from chloride, methyl sulphate and acetate, E represents a group selected from the following structures E1 to E8:

in which R' represents a C₁-C₄ alkyl radical; when m = 0 and D₁ represents a nitrogen atom, E may also represent a group of the following structure E9: R'

N

E9

N+ I R' in which R' represents a CrC₄ alkyl radical.

G H = H J (IV) in which: the symbol G represents a group selected from the following structures Gi to G3:

G₁ G₂ G₃ in which structures G-| to G3,

R₁8 represents a d-C₄ alkyl radical, a phenyl radical which may be substituted by a CrC₄ alkyl radical or a halogen atom selected from chlorine, bromine, iodine and fluorine; Rig represents a d-C₄ alkyl radical or a phenyl radical;

R₂0 and R₂₁ are the same or different and represent a CrC₄ alkyl radical, a phenyl radical, or form together in Gi a benzene ring substituted by one or more CrC₄ alkyl, Cr C₄ alkoxy or NO₂ radicals, or form together in G₂ a benzene ring optionally substituted by one or more CrC₄ alkyl, CrC₄ alkoxy or NO₂ radicals; R₂₀ may also represent a hydrogen atom;

Z represents an oxygen or sulphur atom or a -NR₁₉;

M represents a -CH, or -CR group (R representing CrC₄ alkyl), or -NR₂₂(X^')_r;

K represents a -CH, or -CR group (R representing CrC₄ alkyl), or -NR₂₂(X^')_r group;

P represents a -CH, or -CR group (R representing CrC₄ alkyl), or -NR₂₂(X^')_r; r represents zero or 1 ;

R₂₂ represents an O^~ atom, a CrC₄ alkoxy radical or a CrC₄ alkyl radical;

R₂₃ and R₂₄ are the same or different and represent a hydrogen atom or a halogen atom selected from chlorine, bromine, iodine and fluorine, a CrC₄ alkyl or CrC₄ alkoxy radical, or a -NO₂ radical; X represents an anion preferably selected from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate; subject to the condition that, if R₂₂ represents O^~, then r represents zero; if K or P or M represents -N-alkyl d-C₄ X^~, then R₂3 or R₂₄ may or may not differ from a hydrogen atom; if K represents -NR₂₂(X^"),- , then M= P= -CH, -CR; if M represents -NR₂₂(X^"),- , then K= P= -CH, -CR; if P represents -NR₂₂(X^')_r , then K= M and they represent -CH or -CR; if Z represents a sulphur atom with R₂₁ representing CrC₄ alkyl, then R₂₀ is different from a hydrogen atom; if Z represents -NR₂₂ with R₁₉ representing C₁-C₄ alkyl, then at least one of the radicals R₁₈, R₂o or R₂₁ of the group of structure G₂ is different from a C₁-C₄ alkyl radical; the symbol J represents:

-(a) a group of the following structure J₁:

in which structure J₁,

R₂₅ represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a C₁-C₄ alkyl, or C₁-C₄ alkoxy radical, or an -OH, -NO₂, -NHR₂₈, -

NR₂gR3o, -NHCO C₁-C₄ alkyl radical, or forms together with R₂6 a ring of 5 or 6 bonds containing or not containing one or more heteroatoms selected from nitrogen, oxygen or sulphur;

R₂₆ represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a C₁-C₄ alkyl or C₁-C₄ alkoxy radical, or forms together with R₂₇ or R₂₈ a ring of 5 or 6 bonds optionally containing one or more heteroatoms selected from nitrogen, oxygen or sulphur;

R₂₇ represents a hydrogen atom, a -OH radical, a -NHR₂₈ radical, a -NR₂₉R3o radical; R₂₈ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkyl or C₂-C₄ polyhydroxyalkyl radical, or a phenyl radical;

R₂₉ and R₃o, are the same or different and represent a C₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkyl or C₂-C₄ polyhydroxyalkyl radical;

-(b) a nitrogenated heterocyclic group with 5 or 6 bonds possibly containing other heteroatoms and/or carbonyl groups and possibly being substituted by one or more C₁-C₄ alkyl, amino or phenyl radicals, and in particular a group of the following structure J₂:

in which structure J₂,

R₃₁ and R₃₂ are the same or different and represent a hydrogen atom, a C₁-C4 alkyl radical, a phenyl radical;

CH,

Y represents the radical -CO- or the radical — ^c — ; n = 0 or 1 , and when n represents 1 , U represents the radical -CO-.

In the structures (I) to (IV) defined above, the d-C₄ alkyl or alkoxy group preferably represents methyl, ethyl, butyl, methoxy, ethoxy.

Of the compounds of formulae (I) and (III), the following compounds are preferred:

Examples of azo direct dyes also include the following dyes disclosed in the

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.

They also include 1-(4'-aminodiphenylazo)-2-methyl-4bis-(β-hydroxyethyl) aminobenzene.

The quinone direct dyes include the following dyes: - Disperse Red 15

- Solvent Violet 13

- Disperse Violet 1

- Disperse Violet 4

- Disperse Blue 1 - Disperse Violet 8

- Disperse Blue 3

- Disperse Red 11

- Disperse Blue 7

- Basic Blue 22 - Disperse Violet 15

- Basic Blue 99 as well as the following compounds:

- 1 -N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone - 1 -aminopropylamino-4-methylaminoanthraquinone - 1-aminopropylaminoanthraquinone

- 5-β-hydroxyethyl-1 ,4-diaminoanthraquinone

- 2-aminoethylaminoanthraquinone

- 1 ,4-bis-(β,γ-dihydroxypropylamino)-anthraquinone. The azine dyes include the followings compounds: - Basic Blue 17

- Basic Red 2.

The triarylmethane dyes which can be used according to the invention include the following compounds:

- Basic Green 1 - Basic Violet 3

- Basic Violet 14

- Basic Blue 7

- Basic Blue 26

The indoamine dyes which can be used according to the invention include the following compounds:

- 2-β-hydroxyethlyamino-5-[bis-(β-4'-hydroxyethyl)amino]anilino-1 ,4-benzoquinone - 2-β-hydroxyethylamino-5-(2'-methoxy-4'-amino)anilino-1 ,4-benzoquinone

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

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

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

The dyes of the tetraazapentamethine type which can be used according to the invention include the following compounds shown in the table below:

X represents an anion preferably selected from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate.

The polychromophore dyes more particularly include di- or tri- chromophore azo and/or azomethine (hydrazone) dyes, optionally symmetric, comprising on the one hand at least one aromatic heterocycle comprising 5 or 6 bonds, optionally condensed, comprising at least one quaternised hydrogen atom engaged in said heterocycle and optionally at least one other heteroatom (such as nitrogen, sulphur, oxygen), and on the other hand, at least one phenyl or naphthyl group, optionally substituted, optionally carrying at least one OR group with R representing a hydrogen atom, an optionally substituted d-C₆ alkyl radical, an optionally substituted phenyl ring, or carrying at least one N(R')₂ group with the two R' optionally being identical, representing a hydrogen atom, an optionally substituted CrC₆ alkyl radical, an optionally substituted phenyl ring; it being possible for the R' radicals to form together with the nitrogen atom to which they are bound a saturated heterocycle of 5 or 6 bonds, or else for one and/or both R' radicals each to form with the carbon atom of the aromatic ring placed in the ortho position of the nitrogen atom a saturated heterocycle of 5 or 6 bonds.

Aromatic cationic heterocycles are preferably cycles with 5 or 6 bonds comprising 1 to 3 nitrogen atoms, preferably 1 or 2 nitrogen atoms, one being quaternised; said heterocycle further optionally being condensed to a benzene ring. It should also be noted that the heterocycle may optionally comprise another heteroatom different from nitrogen, such as sulphur or oxygen.

If the heterocycles or phenyl or naphthyl groups are substituted, they are substituted by one or more CrC₈ alkyl radicals optionally substituted by a hydroxyl group, C₁-C2 alkoxy group, C₂-C4 hydroxyalkoxy group, acetylamino group or amino substituted by one or two d-C₄ alkyl radicals, optionally carrying at least one hydroxyl group or it being possible for the two radicals to form together with the nitrogen atom to which they are attached a heterocycle with 5 or 6 bonds, optionally comprising another heteroatom the same as or different from nitrogen; a halogen atom; a hydroxyl group; a d-C₂ alkoxy radical; a C₂-C₄ hydroxyalkoxy radical; an amino radical; an amino radical substituted by one or two identical or different d-C₄ alkyl radicals optionally carrying at least one hydroxyl group.

These polychromophores are interconnected by at least one linker optionally comprising at least one quaternised nitrogen atom which is optionally engaged in a saturated or unsaturated, optionally aromatic heterocycle.

Preferably, the linker is a linear, branched or cyclic, C₁-C20 alkyl chain, optionally containing at least one heteroatom (such as nitrogen, oxygen) and/or at least one group comprising said heteroatom (CO, SO₂), optionally containing at least one heterocycle which is optionally condensed to a phenyl ring and comprising at least one quaternised nitrogen atom engaged in said cycle and optionally at least one other heteroatom (such as oxygen, nitrogen or sulphur), optionally containing at least one phenyl or naphthyl group which is optionally substituted, optionally at least one quaternary ammonium group substituted by two optionally substituted C₁-C₁5 alkyl groups; the linker not comprising any nitro, nitroso or peroxo groups.

The bond between the linker and each chromophore is generally provided by a heteroatom substituting the phenyl or naphthyl ring or by the quaternised nitrogen atom of the cationic heterocycle.

The dye may or may not comprise identical chromophores.

For examples of dyes of this type, reference may in particular be made to patent applications EP 1637566, EP 1619221 , EP 1634926, EP 1619220, EP 1672033, EP 1671954, EP 1671955, EP 1679312, EP 1671951 , EP167952, EP167971 , WO 06/063866, WO 06/063867, WO 06/063868, WO 06/063869, EP 1408919, EP 1377264, EP 1377262, EP 1377261 , EP 1377263, EP 1399425, EP 13991 17, EP 1416909, EP 1399116, EP 1671560.

It is also equally possible to use the cationic direct dyes mentioned in applications

EP 1006153, which discloses dyes comprising two chromophores of the anthraquinone type bound by a cationic linker; EP 1433472, EP 1433474, EP 1433471 and EP 1433473, which disclose identical or non-identical dichromophore dyes bound by a cationic or non- cationic linker, and also EP 6291333 which in particular discloses dyes comprising three chromophores, one of wh ich is an anthraquinone chromophore to which two chromophores of the azo or diazacarbocyanine type or one of the isomers thereof are bound.

The natural direct dyes which can be used according to the invention include lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin and the orceins. It is also possible to use extracts or decoctions containing these natural dyes and in particular henna-based cataplasms or extracts.

If present, the direct dyes are more particularly from 0.01 % by mass to 20 % by mass based on the total mass of the dye composition and preferably from 0.05 % by mass to 10 % by mass of the total mass of the composition.

In a variant, the dye composition comprises one or more organic amines of which the pKb is less than 12, preferably and advantageously less than 6, at 25°C.

It should be noted that this is the pKb corresponding to the functional group with the highest basicity.

Examples of organic amines are given in French application No. 0760273. According to a first variant of the invention, the organic amine comprises one or two primary, secondary or tertiary amine functions, and one or more linear or branched CrC₈ alkyl groups carrying one or more hydroxyl radicals. Organic amines selected from alkanolamines such as mono-, di- or tri- alkanolamines, comprising one to three identical or non-identical C₁-C₄ hydroxyalkyl radicals, are particularly suitable for carrying out the invention.

C o m po u n d s of t h i s ty pe i n c l u d e monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N- dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-

2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3-dimethylamino-1 ,2-propanediol and tris-hydroxymethylaminomethane.

Organic amines of the following formula are also suitable:

Rx_{x y} Rz

_/ N W - N R^y " ^Rt in which W is a C-i-Cβ alkylene radical optionally substituted by a hydroxyl group or a CrCβ alkyl radical; Rx, Ry, Rz and Rt are the same or different and represent a hydrogen atom, or a CrC₆ alkyl, CrC₆ hydroxyalkyl or CrC₆ aminoalkyl radical.

Examples of amines of this type include 1 ,3 diaminopropane, 1 ,3 diamino 2 propanol, spermine and spermidine.

In a further variant of the invention, the organic amine is selected from amino acids.

More particularly, the amino acids which can be used are of natural or synthetic origin and in the L, D, or racemic form thereof, and comprise at least one acid function selected more particularly from carboxylic, su lphonic, phosphonic or phosphoric acid functions. The amino acids may be in a neutral or ionic form.

Advantageously, the am i no acids are basic amino acids comprising a supplementary amine function optionally included in a ring or in a ureido function.

Basic amino acids of this type are preferably selected from those of the following formula (I): χNH₂

R-CH₂ —CH_χ (I)

CO₂H where R represents a group selected from:

-(CH₂)₂NH₂ ; -(CH₂)₂NHCONH₂ -(CH₂)₂NH C -NH₂

NH

The compounds corresponding to formula (I) are histidine, lysine, arginine, ornithine and citrulline.

Amino acids which can be used in the present invention include in particular aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N- phenylalanine, proline, serine, taurine, threonine, tryptophane, tyrosine and valine.

The amino acid or amino acids may be used in a mixture with one or more additives in a solid or paste form, and preferably in a powdered form. The additives may be selected from clays, salts, anionic, non-ionic, cationic or zwitterionic surfactants, natural or synthetic thickening agents, optionally modified starch, glass beads, silica, nylon, alumina, titanium dioxide, zeolites, poly(methyl methacrylate) (PMMA), chitosan, maltodextrin, cyclodextrin, the mono- or disaccharides such as glucose, sucrose, sorbitol or fructose, zinc or zirconium oxide, silicabades, talc, borosilicates, in particular calcium borosilicate, polyethylene, polytetrafluoroethylene (PTFE), cellulose and its derivatives, super- absorbent compounds, magnesium or calcium carbonates, polyacrylamide, porous hydroxyapatite, sawdust, rockweed powder, crosslinked polyvinylpyrrolidone, calcium alginate, activated carbon, particles of poly(vinylidene/acrylonitrile chloride), in particular those marketed as 'Expancel^®' by AKZO NOBEL under the specific names 'Expancel^® WE' or 'DE' Expancels, and mixtures thereof.

In a preferred variant of the invention, the organic amine is selected from basic amino acids. The particularly preferred amino acids are arginine, lysine, histidine, or mixtures thereof.

In a further variant of the invention, the organic amine is selected from the organic amines of the heterocyclic type. In addition to the histidine mentioned in the amino acids above, these include pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

In a further variant of the invention, the organic amine is selected from the amino acid dipeptides. Amino acid dipeptides which can be used in the present invention include in particular carnosine, anserine and baleine. In a further variant of the invention, the organic amine is selected from the compounds comprising a guanidine function. Amines of this type which can be used in the present invention include in particular, in addition to arginine which was mentioned a b ove a s a n a m i n o a c i d, creatine, creatinine, 1 ,1-dimethylguanidine, 1 , 1- diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3- guanidinopropionic acid, 4-guanidinobutyric acid and 2-

([amino(imino)methyl]amino)ethane-1-sulphonic acid.

The organic amine contained in the anhydrous composition is preferably an alkanolamine. More preferably, the organic amine is selected from 2-amino 2-methyl 1- propanol, monoethanolamine or mixtures thereof. Even more preferably, the organic amine is monoethanolamine.

Advantageously, each dye composition has an organic amine content of from 0.1 % by mass to 50 % by mass, preferably from 0.5 % by mass to 20 % by mass based on the total mass of the dye composition. The or each dye composition may be an anhydrous or aqueous composition. An aqueous composition is understood to mean a composition comprising more than 5 % by mass of water, preferably more than 10 % by mass of water and advantageously more than 20 % by mass of water.

This composition may equally comprise one or more solvents of the type disclosed in French application No. 0760273.

In the example shown in Fig. 1 , at least two first reservoirs 16A to 16D comprise two different dye compositions producing different shades. It is possible to obtain an extremely high number of different shades by mixing different proportions of each different dye composition contained in the reservoirs 16A to 16D respectively. In a variant disclosed in French application No. 0760273, one reservoir may contain a dye composition which is free from dye for dilution.

In the example shown in Fig. 1 , the number of first reservoirs 16A to 16D containing different dye compositions is equal to 4. More generally, this number may be between 1 and 50. Each second reservoir 18A to 18B is formed by a flexible pouch 34 containing substantially exclusively an oxidising composition in a liquid or paste form, without containing a significant amount of air.

A 'significant amount of air' is understood to mean an amount greater than 5 % by volume of the volume of the pouch 34. The oxidising composition comprises at least one oxidising agent.

In particular, the or each oxidising agent is selected from hydrogen peroxide, urea peroxide, bromites or ferrocyanides of alkali metals, peroxygenated salts such as persulphates, perborates and percarbonates of alkali or alkaline earth metals, peracids and the precursors thereof. The oxidising agent advantageously consists of hydrogen peroxide, in particular in aqueous solution, the titre of which may vary, more particularly from 1 to 40 volumes and even more preferably from 5 to 40 volumes.

Depending on the degree of highlighting desired, the oxidising agent may also comprise an oxidising agent which is preferably selected from peroxygenated salts.

Preferably, the oxidising composition is an aqueous composition, comprising more than 5 % by mass of water, preferably more than 10 % by mass of water, and advantageously more than 20 % by mass of water. It may also comprise one or more organic solvents of the type defined in application No. 0760273. Preferably, the oxidising composition is an aqueous composition.

It may also comprise one or more organic solvents.

Examples of organic solvents include linear or branched C₂-C₄ alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propyleneglycol, dipropyleneglycol, propyleneglycol monomethylether, diethyleneglycol monoethylether and monomethylether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The or each solvent represents, when used, a content conventionally of from 1 % to 40 % by mass based on the total mass of the oxidising composition, and preferably from 5 % to 30 % by mass. In some variants, the oxidising composition comprises one or more acidifying agents such as the inorganic or organic acids disclosed in French application No. 0760273.

In the example shown in Fig. 1 , each second reservoir 18A, 18B contains an oxidising composition having a different concentration of oxidising agent and therefore a different oxidising strength. In this way, it is possible to obtain a plurality of different oxidising strengths in the dose 14 by varying the relative ratios by mass of each oxidising composition coming from the reservoirs 18A to 18B respectively in the dose 14.

In the example shown in Fig. 1 , the number of second reservoirs 18A to 18B containing different oxidising compositions is equal to 2. More generally, this number may be between 1 and 5.

Each third reservoir 2OA, 2OB is formed, in the example shown in Fig. 1 , by a high- volume container containing the oil-based anhydrous cosmetic composition.

The volume of each container 2OA, 2OB is greater than the volume of each pouch 32 forming a first reservoir 16A to 16D respectively and is preferably greater than the volume of each pouch 34 forming a second reservoir 18A, 18B. Advantageously, the volume of each container 36 forming a third reservoir is greater than the volume of each pouch 32, 34, and advantageously between one and four times the volume of each pouch 32, 34.

Each container 2OA, 2OB comprises a different anhydrous composition. According to the invention, the anhydrous composition is free from direct dye or from oxidation dye of the type defined above, for example comprising less than 0.005 % by mass of these dyes based on the mass of the anhydrous composition. This composition is further free from oxidising agents.

In the context of the invention, an 'anhydrous composition' is understood to mean a composition having a water content of less than 5 % by mass, preferably less than 2 % by mass, and advantageously less than 1 % by mass based on the total mass of the composition.

The water may be free or may be in the form of bound water, like the water of crystallisation of salts or the traces of water absorbed by the raw materials used when producing the compositions according to the invention.

The anhydrous cosmetic composition comprises at least one fat. A 'fat' is understood in the context of the present invention to mean an organic compound which is insoluble in water at room temperature (25 ⁰C) and atmospheric pressure (1 bar), this solubility being at least less than 5 % and preferably less than 1 % or even less than 0.1 %.

It has a structure exhibiting at least one hydrocarbon chain containing at least six carbon atoms or a linkage of at least two siloxane groups.

The fats are soluble in the organic solvents under the same temperature and pressure conditions as chloroform, ethanol or benzene for example. The fats are advantageously selected from compounds which are in liquid or paste form at room temperature and atmospheric pressure. They are preferably selected from alkanes, fatty alcohols, fatty acids, fatty acid esters, fatty alcohol esters, mineral oils, vegetable oils, animal oils, synthetic oils, silicones, waxes, or mixtures thereof.

These compounds are defined in detail in French application No. 0760273. It is noted that in the context of the invention, the alcohols, esters and fatty acids more particularly have at least one linear or branched, saturated or unsaturated hydrocarbon group containing 6 to 30 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may contain one to three carbon-carbon double bonds, optionally conjugated. The alkanes comprise 6 to 30 carbon atoms and are linear or branched and optionally cyclic. Examples include hexane and dodecane. Examples of oils which can be used in the composition according to the invention include:

- hydrocarbon oils of animal origin, such as a perhydrosqualene;

- hydrocarbon oils of vegetable origin, such as the liquid triglycerides of fatty acids comprising from 6 to 30 atoms of carbon, such as the triglycerides of heptanoic or octanoic acid, or even for example sunflower, maize, soya, squash, grapeseed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor and avocado oils, the triglycerides of the caprylic/capric acids, such as those sold by Stearineries Dubois or those sold as Miglyol^® 810, 812 and 818 by Dynamit Nobel, jojoba oil, and shea butter oil; - linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils, optionally volatile, and the derivatives thereof, vaseline, vaseline oil, polydecenes, hydrogenated polyisobutene such as Parleam^®; isoparaffins such as isohexadecane and isodecane.

- the fatty alcohols are saturated or unsaturated, linear or branched, and comprise 8 to 30 carbon atoms, and include cetyl alcohol, stearyl alcohol and the mixture thereof

(cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, oleic alcohol or linoleic alcohol;

- partially hydrocarbon and/or silicon fluorinated oils, such as those disclosed in document JP-A-2-295912; fluorinated oils also include perfluoromethylcyclopentane and perfluoro-1 ,3 dimethylcyclohexane, sold as "FLUTEC^® PC1 " and "FLUTEC^® PC3" by BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold as "PF 5050^®" and "PF 5060^®" by 3M, or else bromoperfluorooctyl sold as "FORALKYL^®" by Atochem; nonafluoro- methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine, sold as "PF 5052^®" by 3M.

The wax or waxes are selected in particular from Carnauba wax, Candelilla wax, and esparto wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant flower sold by BERTIN (France), animal waxes such as beeswax, or modified beeswaxes (cerabellina); other waxes or waxy raw materials which can be used according to the invention are in particular marine waxes such as those sold by SOPHIM under reference M82, and polyethylene or in general polyolefin waxes.

The fatty acids may be saturated or unsaturated and comprise from 6 to 30 carbon atoms, in particular from 9 to 30 carbon atoms. They are more particularly selected from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid. The esters are esters of aliphatic, saturated or unsaturated, linear or branched C₁-

C₂₆ mono or polyacids and of aliphatic, saturated or unsaturated, linear or branched C₁- C₂₆ mono or polyalcohols, the total carbon number of the esters being greater than or equal to 10. The monoesters include, dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; Ci₂-C₁₅ alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, mirystyl, stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate. Even in this variant, it is also possible to use esters of C4-C2₂ di or tricarboxylic acids and C₁-C₂₂ alcohols and esters of mono, di or tricarboxylic acids and C₂-C₂₆ di, tri, tetra or pentahydroxy alcohols.

These include in particular: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylnate; octyldodec y I s tearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; and polyethylene glycol distearates.

Of the above-mentioned esters, it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecylpalmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, hexyl stearate, butyl stearate, isobutyl stearatemyristate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate.

As a fatty ester, the composition may also include esters and di-esters of C6-C30, preferably C₁₂-C₂₂ fatty acid sugars. It should be noted that 'sugar' is understood to mean oxygenated hydrocarbon compounds which have a plurality of alcohol functions, with or without aldehyde or ketone functions, and comprising at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides. Examples of suitable sugars include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and in particular the alkyl derivatives thereof, such as the methyl derivatives such as methylglucose.

The esters of sugars and fatty acids may be selected in particular from the group containing esters or mixtures of esters of sugars described above and C₆-C₃O, preferably

C₁₂-C₂₂, linear or branched, saturated or unsaturated fatty acids. If they are unsaturated, these compounds may contain one to three carbon-carbon double bonds, optionally conjugated.

The esters in this variant may also be selected from the mono-, di-, tri- and tetra- esters, the polyesters and mixtures thereof.

These esters may be for example oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates, or mixtures thereof such as in particular oleo-palmitate, oleo-stearate or palmito-stearate mixed esters. More particularly, the mono- and di- esters and in particular the mono- or di- oleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose are used.

These include for example the product sold as Glucate® DO by Amerchol, which is a methylglucose dioleate. Other examples of esters or of mixtures of esters of fatty acid sugar include:

- the products sold as F160, F140, F110, F90, F70, SL40 by Crodesta, respectively representing sucrose palmito-stearates formed from 73 % monoester and 27 % di- and tri-ester, 61 % monoester and 39 % di-, tri-, and tetra-ester, 52 % monoester and 48 % di-, tri-, and tetra-ester, 45 % monoester and 55 % di-, tri-, and tetra-ester, 39 % monoester and 61 % di-, tri-, and tetra-ester and sucrose mono-laurate;

- the products sold as Ryoto Sugar Esters for example under the reference B370 and corresponding to saccherose behenate formed from 20 % monoester and 80 % di- tri ester-polyester;

- the sucrose mono-di-palmito-stearate sold by Goldschmidt as Tegosoft® PSE. The silicones which can be used in the cosmetic compositions of the present invention are volatile or non-volatile, cyclic, linear or branched silicones, optionally modified by organic groups, having a viscosity of 5x10^"6 at 2.5m²/s at 25 ⁰C and preferably of 1x10^"5 at 1 m²/s.

The silicones which can be used according to the invention may be in the form of oils, waxes, resins or rubbers. Preferably, the silicone is selected from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organo-modified polysiloxanes comprising at least one functional group selected from poly(oxyalkylene) groups, amino groups and alkoxy groups. Organopolysiloxanes are defined in greater detail in "Chemistry and Technology of

Silicones" (1968), Academie Press, by Walter NOLL. They may be volatile or non-volatile. If they are volatile, the silicones are more particularly selected from those having a boiling point of between 60 ⁰C and 260 ⁰C, and even more particularly from:

(i) cyclic polydialkylsiloxanes comprising 3 to 7, preferably 4 to 5 silicone atoms. This may be for example octamethylcyclotetrasiloxane sold in particular as

VOLATILE SILICONE^® 7207 by UNION CARBIDE or as SILBIONE^® 70045 V2 by

RHODIA, decamethylcyclopentasiloxane sold as VOLATILE SILICONE^® 7158 by UNION

CARBIDE and as SILBIONE® 70045 V5 by RHODIA, and mixtures thereof.

They also include cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as SILICONE VOLATILE^® FZ 3109 sold by UNION CARBIDE, of formula:

with D"- - Ξι - 0 — with D¹ - Si - O -

C H₃ C₈H ₁₇

They also include mixtures of cyclic polydialkylsiloxanes with organic compounds derived from silicon, such as the mixture octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1 ,1 '-(hexa-2,2,2',2',3,3'-trimethylsilyloxy) bis-neopentane;

(ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity less than or equal to 5x10^"6m²/s at 25 ⁰C. This may for example be decamethyltetrasiloxane sold in particular as "SH 200" by TORAY SILICONE. Silicones included in this class are also described in the article "Volatile Silicone fluids for cosmetics" published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, P. 27-32 - TODD & BYERS.

It is preferable to use non-volatile polydialkylsiloxanes, polydialkylsiloxane rubbers and resins, polyorganosiloxanes modified by the organic functional groups above, and mixtures thereof. These silicones may more particularly be selected from polydialkylsiloxanes, which include primarily polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ⁰C in accordance with the standard ASTM 445 Appendix C.

These polydialkylsiloxanes include, but are not limited to, the following commercial products:

- the SILBIONE® oils of the 47 and 70 047 ranges or the MIRASIL® oils sold by RHODIA such as, for example, the oil 70 047 V 500 000;

- the oils in the MIRASIL® range sold by RHODIA;

- the oils in the 200 range from DOW CORNING such as DC200 having a viscosity of 60 000 mm²/s;

- the VISCASIL® oils from GENERAL ELECTRIC and some oils in the SF (SF 96, SF 18) range from GENERAL ELECTRIC.

These also include polydimethylsiloxanes with dimethylsilanol end groups, known as dimethiconol (CTFA), such as the oils in the 48 range from RHODIA. This class of polydialkylsiloxanes also include the products sold as "ABIL WAX®

9800 and 9801 " by GOLDSCHMIDT, which are polydialkyl (CrC₂₀) siloxanes.

The silicone rubbers which can be used according to the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes having high average number molecular masses of between 200,000 and 1 ,000,000, used individually or in a mixture in a solvent. This solvent may be selected from the volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or mixtures thereof.

Products which may more particularly be used according to the invention are mixtures such as: - mixtures formed from a hydroxylated polydimethylsiloxane at a chain end, or dimethiconol (CTFA), and from a cyclic polyd imethylsiloxane also known as cyclomethicone (CTFA) such as the product Q2 1401 sold by DOW CORNING;

- mixtures of a polydimethylsiloxane rubber and a cyclic silicone such as the product SF 1214 Silicone Fluid sold by GENERAL ELECTRIC, this product being an SF 30 rubber corresponding to a dimethicone, having an average number molecular weight of 500,000, solubilised in the SF 1202 Silicone Fluid oil corresponding to decamethylcyclopentasiloxane;

- mixtures of two PDMS of different vicosities, and more particularly of a PDMS rubber and a PDMS oil, such as the product SF 1236 sold by GENERAL ELECTRIC. The product SF 1236 is a mixture of an SE 30 rubber as defined above having a viscosity of 20 m²/s and of an SF 96 oil having a viscosity of 5x10^"6m²/s. This product preferably comprises 15 % of SE 30 rubber and 85 % of an SF 96 oil.

The organopolysiloxane resins which can be used according to the invention are cross-linked siloxane systems comprising the units: R₂SiO₂₇₂, RsSiOv₂, RSiO₃/₂ and SiO₄/2 in which R represents an alkyl having 1 to 16 carbon atoms. Of these products, those which are particularly preferred are those in which R represents a lower, CrC₄ alkyl group, more particularly methyl.

These resins include the product sold as "DOW CORNING 593" or those sold as "SILICONE FLUID SS 4230 and SS 4267" by GENERAL ELECTRIC which are silicones having a dimethyl/trimethyl siloxane structure.

They also include resins of the trimethylsiloxysilicate type sold in particular as X22-4914, X21-5034 and X21-5037 by SHIN-ETSU.

The organo-modified silicones which can be used according to the invention are silicones as defined above and comprise in the structure thereof one or more organic functional groups fixed by a hydrocarbon group.

Furthermore, in the silicones described above, the organo-modified silicones may be polydiaryl siloxanes, in particular polydiphenylsiloxanes, and polyalkyl-arylsiloxanes functionalised by the aforementioned organic functional groups. The polyalkylarylsiloxanes are in particular selected from the polydimethyl/methylphenylsiloxanes, the linear and/or branched polydimethyl/diphenylsiloxanes of a viscosity of from 1x10^"5 to 5x10^"2m²/s at 25 ⁰C.

Examples of these polyalkylarylsiloxanes include the products sold under the following tradenames: . the SILBIONE® oils as in the 70 641 range from RHODIA;

. the oils in the RHODORSIL® 70 633 and 763 ranges from RHODIA; . the oil DOW CORNING 556 COSMETIC GRAD FLUID sold by DOW CORNING; . the silicones in the PK range from BAYER, such as the product PK20; . the silicones in the PN, PH range from BAYER such as the products PN1000 and PH1000;

. some oils in the SF range from GENERAL ELECTRIC such as SF 1023, SF 1 154, SF 1250 and SF 1265.

The organo-modified silicones include the polyorganosyloxanes comprising: - polyethyleneoxy and/or polypropyleneoxy groups, optionally comprising C₆-C₂₄ alkyl groups, such as the products named dimethicone copolyol, sold by DOW CORNING as DC 1248, or the oils SILWET® L 722, L 7500, L 77, L 71 1 sold by UNION CARBIDE and the alkyl (Ci₂)-methicone copolyol sold by DOW CORNING as Q2 5200;

- substituted or non-substituted amino groups, such as the products sold as GP 4 Silicone Fluid and GP 7100 by GENESEE or the products sold as Q2 8220 and DOW CORNING 929 or 939 by DOW CORNING. The substituted amino groups are in particular CrC₄ alkyl groups;

- alkoxy groups, such as the products sold as "SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX® 2428, 2434 and 2440 by GOLDSCHMIDT.

Preferably, the fat is a compound which is liquid at a temperature of 25 ⁰C and at atmospheric pressure.

Preferably, the fat is selected from vaseline oil, polydecenes, liquid esters or mixtures thereof.

In the example shown in Fig. 1 , the fats contained in each anhydrous composition are oils as defined above, in particular vaseline oil. This fat is liquid at a temperature of 25 ⁰C and at atmospheric pressure.

Even more preferably, the anhydrous composition contains one or more fats which are liquid at 25 ⁰C and at atmospheric pressure (1 bar).

The anhydrous cosmetic composition has a fat content advantageously of between 10 % and 99 % by mass, preferably between 20 % by mass and 90 % by mass, and even more preferably between 25 % and 80 % by mass based on the total mass of the anhydrous composition.

Advantageously, the anhydrous cosmetic composition comprises at least one surfactant selected from non-ionic or anionic surfactants.

These surfactants used are disclosed for example in French application No. 0760273.

The anionic surfactants are more specifically selected from the salts (in particular alkaline metal salts, in particular of sodium, ammonium salts, amine salts, amino alcohol salts or salts of alkaline earth metals such as magnesium) of the following compounds: alkylsulphates, alkylethersulphates, alkylamidoethersulphat.es, alkylaryl- polyethersulphates, monoglyceride sulphates; alkylsulphonates, alkylamidesulphonates, alkylarylsulphonates, α-olefin- sulphonates, paraffin-sulphonates;

- alkylphosphates, alkyletherphosphates;

- alkylsulphosuccinat.es, alkylethersulphosuccinat.es, alkylamide-sulphosuccinates; alkylsulphosuccinamat.es;

- alkylsulphoacetates; - acylsarcosinates; acylisethionates and N-acyltaurates;

- salts of fatty acids such as oleic, ricinoleic, palmitic and stearic acids, acids of coprah oil or hydrogenated coprah oil;

- salts of acids of uronic alkyl D galactoside; - the acyl-lactylates;

- salts of polyoxyalkylene carboxylic alkylether acids, polyoxyalkylene carboxylic alkylarylether acids, polyoxyalkylene carboxylic alkylamidoether acids, in particular those comprising from 2 to 50 ethylene oxide groups;

- and mixtures thereof. It should be noted that the alkyl or acyl radical of these different compounds advantageously comprises from 6 to 24 carbon atoms, and preferably from 8 to 24 carbon atoms, and the aryl radical preferably represents a phenyl or benzyl group.

The non-ionic surfactants are more particularly selected from the mono- or polyoxyalkylene and mono- or poly-glycerol non-ionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.

Examples of oxyalkylene non-ionic surfactants include:

• oxyalkylene alkyl(C₈-C₂₄)phenols,

• oxyalkylene, saturated or unsaturated, linear or branched C₈-C₃O alcohols, • oxyalkylene, saturated or unsaturated, linear or branched C₈-C₃₀, amides ,

• oxyalkylene, saturated or unsaturated, linear or branched C₈-C₃₀ amines,

• esters of saturated or unsaturated, linear or branched C₈-C₃₀ acids and of polyethyleneglycols,

• esters of saturated or unsaturated, linear or branched C₈-C₃₀ acids and of polyoxyethylene sorbitol,

• saturated or unsaturated oxyethylene vegetable oils,

• condensates of ethylene oxide and/or of propylene oxide, inter alia, individually or in mixtures.

The surfactants have a number of moles of ethylene and/or propylene oxide of between 1 and 50, preferably between 2 and 30. Advantageously, the non-ionic surfactants do not contain any oxypropylene units.

In a preferred embodiment of the invention, the oxyalkylene non-ionic surfactants are selected from oxyethylene C₈-C₃₀ alcohols and oxyethylene C₈-C₃₀ amines. Mono- or poly-glycerol C₈-C₄₀ alcohols are a preferred example of mono- or poly- glycerol non-ionic surfactants. In particular, the mono- or poly-glycerol Cs-C₄₀ alcohols correspond to the following formula:

RO-[CH₂-CH(CH₂OH)-O]_m-H in which R represents a linear or branched C₈-C₄₀, preferably C₈-C₃₀ alkyl or alkenyl radical, and m represents a number of from 1 to 30 and preferably from 1 to 10.

Examples of compounds which are suitable within the scope of the invention include lauric alcohol with 4 moles of glycerol (INCI name: POLYGLYCERYL-4 LAURYL ETHER), lauric alcohol with 1.5 moles of glycerol, oleic alcohol with 4 moles of glycerol (INCI name: POLYGLYCERYL-4 OLEYL ETHER), oleic alcohol with 2 moles of glycerol (INCI name: POLYGLYCERYL-2 OLEYL ETHER), cetearylic alcohol with 2 moles of glycerol, cetearylic alcohol with 6 moles of glycerol, oleocetylic alcohol with 6 moles of glycerol, and octadecanol with 6 moles of glycerol.

The alcohol may represent a mixture of alcohols and the value of m represents a statistical value, which means that in a commercial product, a plurality of species of polyglycerol fatty alcohols may exist in the form of a mixture.

With regard to the mono- or poly-glycerol alcohols, it is particularly preferred to use C₈/Cio alcohol with one mole of glycerol, Ci_θ/Ci₂ alcohol with 1 mole glycerol and Ci₂ alcohol with 1.5 moles of glycerol.

The surfactant content of the anhydrous composition is more particularly from 0.1 % by mass to 50 % by mass, advantageously from 0.5 % by mass to 30 % by mass based on the total mass of the anhydrous composition.

Each anhydrous composition may also contain various additives as defined in the Applicant's French application No. 0760273.

These additives are conventionally used in compositions for dyeing hair, such as anionic, cationic, non-ionic, amphoteric, zwitterionic polymers or mixtures thereof; mineral thickeners, and in particular ingredients such as clays and talc, organic thickeners, including in particular associative anionic, cationic, non-ionic and amphoteric polymer thickeners; antioxidants; penetration agents, sequestering agents; aromas, dispersants; film-forming agents; ceramides; preservatives; opacifying agents. The additives are generally contained in an amount in each case of between 0.01

% by mass and 20 % by mass based on the total mass of the anhydrous composition. This anhydrous composition is advantageously in the form of a gel or a cream.

In one variant, the anhydrous composition comprises one or more organic amines with a pKb at 25 ⁰C of less than 12, preferably and advantageously less than 6. It should be noted that this is the pKb corresponding to the function of the highest basicity. Examples of organic amines are provided in French application No. 0760273.

The organic amine content of the anhydrous composition is therefore from 0.1 % by mass to 40 % by mass, preferably from 0.5 % by mass to 20 % by mass based on the total mass of the composition. In the example shown in Fig. 1 , the third reservoirs 2OA, 2OB respectively each contain different anhydrous compositions. Thus, in one example, the anhydrous composition contained in the first of these is a basic anhydrous composition whilst the composition contained in a second such reservoir is formed of the basic anhydrous composition contained in the first such reservoir, to which an additive such as an aroma has been added.

The dispenser 22 is capable of removing selectively, under the control of the unit 24, a first selected mass of each dye composition contained in each first reservoir 16A to 16D, a second selected mass of each oxidising composition contained in each second reservoir 18A to 18B, and a third selected mass of each anhydrous composition contained in each third reservoir 2OA, 2OB and for transferring them to the packaging 26 to form the dose 14.

Thus, the dose 14 contains a total mass of dye composition formed by the sum of the first masses of each dye composition introduced into the dose, a total mass of oxidising composition formed by the sum of the second masses of each oxidising composition introduced into the dose and a total mass of anhydrous composition formed by the sum of the third masses of each anhydrous composition introduced into the dose.

The percentage by mass of dye composition in the dose is thus between 5 % by mass and 25 % by mass, preferably between 10 % by mass and 20 % by mass. The percentage by mass of oxidising composition in the dose is between 35 % by mass and 80 % by mass, preferably between 45 % by mass and 60 % by mass, and the percentage by mass of anhydrous composition in the dose is between 20 % by mass and 50 % by mass, preferably between 30 % by mass and 40 % by mass.

In the example shown in Fig. 1 , the dispenser 22 comprises, associated with each reservoir 16A to 16D, 18A to 18B, 2OA to 2OB, a pumping assembly 48 arranged along the peripheral edge of the turntable 30. Only one pumping assembly 48 associated with any one reservoir will be disclosed below, the other pumping assemblies being of an analogous construction.

Referring to Fig. 2, each pumping assembly 48 comprises a removal duct 50, a pump 52 connected to the removal duct 50 and a dispensing duct 54 tapped onto the removal duct 50, opposite the pump 52. The removal duct 50 connects a lower outlet 56 provided in the reservoir 16A to

16D, 18A, 18B, 2OA, 2OB to a lower end of the piston pump 52.

It is provided with a removal valve 60 capable of selectively closing the duct 50 under the control of the unit 24. The dispensing duct 54 is tapped onto the removal duct 50 between the removal valve 60 and the lower end of the pump 52. It opens at a free end located above and opposite the packaging 26. It is provided, upstream from the free end 62 thereof, with a dispensing valve 64 capable of selectively closing the duct 54 under the control of the unit

24, when the removal valve 60 is closed. The pump 52 comprises a cylinder 66 opening into the removal duct 50 at the lower end 58, a piston 68 mounted movably in the cylinder 66, and a device 70 for actuating the piston 68.

The piston 68 and cylinder 66 define an internal fluid removal volume connected to the removal duct 50 via the lower end 58. The piston 68 is movable in the cylinder 66 between a lower idle position located in the vicinity of the end 58, in which the internal fluid removal volume is at a minimum, and an upper pumping position in which the internal fluid removal volume is at a maximum.

In this example, the measurement assembly 28 comprises a balance which supports the packaging 26. The balance is connected to the control unit 24 to transmit to said unit 24 the measured weight of the container 26 and of the compositions successively added into the packaging to form the dose 14.

The control unit 24 comprises a man-machine interface 80, shown for example in

Fig. 3, and control means 82 for each pumping assembly 48 of the dispenser 22, said means being connected to the interface 80. The interface 80 comprises means for inputting a total mass of the desired dose

14 and means for inputting parameters of the desired colouring composition.

A parameter of the desired colouring composition is understood to mean for example the shade thereof, the strength thereof, and the type of anhydrous composition selected to form it. The input means are for example a keyboard and/or a mouse connected to a computer, a touch screen, or a magnetic card or smartcard containing the various parameters.

A user can therefore, using the input means, define the total mass of the dose 14 which he desires, the shade selected for the dose 14, the strength for the dose 14 and the type of anhydrous composition used in the dose 14. The control means 82 are connected to the interface 80. They comprise a calculator and a memory capable of converting the data input by the user into control commands for each pumping assembly 48.

In this way, based on the shade input by the user and the total mass of the dose 14 input by the user, the calculator can determine, for each dye composition contained in each reservoir 16A to 16D, whether this dye composition is to be introduced into the packaging 26 to form the dose and, so, calculate the first mass of this dye composition which is to be introduced into the dose 14 by the dispenser 22 in order to produce the desired shade, based on a recipe optionally contained in the memory. Based on the oxidising strength input by the user via the interface 80, and the total mass of the dose 14 input by the user, the calculator can determine, for each oxidising composition contained in each reservoir 18A to 18B, whether this dye composition is to be introduced into the packaging 26 to form the dose 14 and, if so, calculate the second mass of this oxidising composition which is to be introduced into the dose 14 by the dispenser 22 in order to obtain the desired oxidising strength.

Based on the type of anhydrous composition input by the user via the interface 80, and the total mass of the dose 14 input by the user, the calculator can determine, for each anhydrous composition contained in each reservoir 2OA to 2OB, whether this anhydrous composition is to be introduced into the packaging 26 to form the dose 14 and, so, calculate the third mass of this anhydrous composition which is to be introduced into the dose 14 by the dispenser 22.

According to the invention and thanks to the presence of anhydrous composition in the third reservoirs 2OA, 2OB, the control unit 24 is programmed to control the dispenser 22 in such a way that the total mass of anhydrous cosmetic composition coming from the third reservoirs 2OA, 2OB into the dose 14 represents more than 20 % of the total mass of the dose 14, advantageously more than 25 % and even more advantageously more than 30 %.

The control unit 24 is also programmed in such a way that the total mass of dye composition coming from the first reservoirs 16A to 16D is less than 25 % of the total mass of the dose 24.

Owing to the device 10 according to the invention, the reservoirs 16A to 16D containing each concentrated dye composition can therefore be selected to have a relatively low volume. This makes it possible to increase the number of reservoirs carried by a single device 10, and therefore to increase the shade selection options for the dyeing. Furthermore, the low mass of dye composition required to prepare each dose 14 reduces the number of replacements of the pouches 32 which form the first reservoirs 16A to 16D. This reduces the problems caused by contamination of the dispensing device 10 by the dye compositions. On the other hand, the third reservoirs 2OA, 2OB containing anhydrous composition are refilled more frequently or are formed by higher-volume containers.

A first process for dispensing a colouring composition according to the invention will now be described.

Initially, the user activates the interface 80 and selects the total mass of the dose 14 which he wishes to obtain, the shade which he is selecting, the oxidising strength selected and the type of anhydrous composition which he wishes to use.

Based on the information input by the user via the interface 80, the calculator of the control means 82 determines which of the compositions contained in the reservoirs

16A to 16D, 18A to 18B and 2OA to 2OB are to be removed, and what mass of each composition removed is to be introduced into the packaging to form the dose 14, as explained above.

During this calculation, as shown above, the total mass of anhydrous composition coming from the third reservoirs 2OA, 2OB is calculated by the control unit 24 so as to represent more than 20 % of the total mass of the dose 14, and the total mass of dye composition coming from the various first reservoirs 16A to 16D is calculated by the control unit 24 to represent less than 25 % of the total mass of the dose 14. Subsequently, based on the compositions selected by the calculator, the control means 82 activate the turntable 30 to successively bring each pump assembly 48 of a reservoir containing a composition to be removed opposite the packaging 26. For each composition to be removed, the control means 82 open the removal valve 60 of the corresponding removal duct 50 and close the dispensing valve 64 on the corresponding dispensing duct 54.

The control means 82 then activate the actuation device 70 of the piston 68 to displace the piston 68 from the lower position thereof to the upper position thereof and to pump into the cylinder 66 the mass of composition to be dispensed into the packaging 26, directing it from the reservoir through the removal duct 50.

When this determined mass is located in the cylinder 66, the control means 82 close the removal valve 60 and open the dispensing valve 64 to hydraulically connect the lower end 58 of the cylinder 66 to the free end 62 of the dispensing duct 54. Subsequently, the piston 68 is displaced into the lower position thereof to transfer the mass of composition selected into the packaging 26 from the cylinder 66 via the dispensing duct 54.

The mass of the composition added to the packaging 26 is measured on the measurement assembly 28 and is transmitted to the control means 82 for verification.

Subsequently, the table 30 is rotated in such a way as to place a different dispensing assembly 48 opposite the packaging 26.

Once all the compositions selected by the calculator have been transferred into the container 26, the dose 14 can be formed by mixing these different compositions to obtain the colouring composition 12. This mixing may be performed manually by the user or by mixing means provided on the device 10.

The packaging 26 is then extracted from the machine by the user and the dose 14 of colouring composition 12 prepared in this manner is applied after a short interval, for example less than one hour, to the keratin fibres of a human being or animal. In the second device 110 according to the invention and shown in Fig. 4, the third reservoirs 2OA, 2OB are formed by flexible pouches 1 12 similar to the pouches 32 forming the first reservoirs 16A to 16D.

The pouches 1 12 are changed more frequently than the pouches 32 containing the dye compositions. In a variant (not shown), the reservoirs 16A to 16D, 18A to 18B, and 2OA to 2OB are arranged so as to be fixed relative to a frame of the machine, without a turntable. The packaging 26 can then be mounted so as to be movable relative to each reservoir 16A to 16D, 18A to 18B, and 2OA to 2OB during the formation of the dose 14.

In a further variant, the reservoirs 16A to 16D, 18A to 18B, and 2OA to 2OB and the packaging 26 are arranged so as to be fixed relative to a frame of the machine during the formation of the dose 14.

In another variant, the interface 80 comprises means for inputting the tone and colour of the keratin fibres which are to receive the colouring composition before receiving this composition, and means for entering a proposed shade and oxidising strength depending on the tone and colour input by the user.

Examples of doses 14 of colouring compositions prepared using a device 10 according to the invention are disclosed below: Composition

A TMHC machine made by Fast & Fluid Management was configured with the following preparations: Preparations 1 and 2:

Preparation 3:

Preparation 4:

On demand, the following compositions were dispensed:

They were applied to strands for thirty minutes at 10 grammes per gramme of hair, which was 90 % white. After rinsing, final treatment and drying, the following results were obtained:

As mentioned above, when a series of successive doses 14 of colouring composition are dispensed by the devices 10, 1 10 according to the invention, the total mass of anhydrous composition dispensed from the, of from each third reservoir 2OA, 20B is always more than 20% of the total mass of each dose 14, due to the control unit 24 having means 82 for controlling the dispenser 22.

Claims

1.- Device (10; 1 10) for dispensing a colouring composition for keratin fibres, the device (10; 1 10) being of the type comprising:

- a first reservoir (16A to 16D) containing a first composition, this composition having a dyeing effect;

- a second reservoir (18A to 18B) containing a second composition which is different from the first dye composition, this composition having an oxidising effect;

- a third reservoir (2OA to 20B) containing a third composition which is different from the first composition and different from the second composition; - a dispenser (22) which is capable of removing a first mass of first composition from the first reservoir (16A to 16D), a second mass of second composition from the second reservoir (18A to 18B) and a third mass of third composition from the third reservoir (2OA to 20B), and for dispensing them into a packaging (26) to form, after mixing, a dose (14) of colouring composition (12) in the packaging (26), characterised in that the third composition is anhydrous and free from dyeing and oxidising agents, and comprises one or more fats, the control unit (24) comprising means (82) for controlling the dispenser (22) in such a way that the total mass of anhydrous composition dispensed from the, or from each third reservoir (2OA to 20B) to form each dose (14) of colouring composition is more than 20 % of the total mass of the dose (14) of colouring composition.

2.- Device (10; 1 10) according to claim 1 , characterised in that the fat or fats contain one or more oils.

3.- Device (10; 1 10) according to claim 2, characterised in that the oil is selected from mineral oils, vegetable oils, animal oils, synthetic oils, or mixtures thereof, and is advantageously vaseline oil.

4.- Device (10; 1 10) according to any one of the preceding claims, characterised in that the fat content of the anhydrous composition is between 10 % and 99 % by mass based on the weight of the anhydrous composition.

5.- Device (10; 1 10) according to any one of the preceding claims, characterised in that the control unit (24) comprises means (82) for controlling the dispenser (22) in such a way that the total mass of dye composition dispensed from the, of from each first reservoir (16A to 16D) to form each dose (14) of colouring composition is less than 25 % of the total mass of the dose (14).

6.- Device (10) according to any one of the preceding claims, characterised in that the volume of the third reservoir (2OA to 20B) is greater, advantageously at least two times greater, than the volume of the first reservoir (16A to 16D).

7.- Device (10; 1 10) according to any one of the preceding claims, characterised in that the control unit (24) comprises a man-machine interface (80) which can be controlled by a user in such a way as to select at least one of the total mass of the dose (14) and at least one parameter representative of the colour produced by the colouring composition when applied to keratin fibres, advantageously the shade or the strength.

8.- Device (10; 1 10) according to any one of the preceding claims, characterised in that it comprises a plurality of third reservoirs (2OA to 20B) each containing different anhydrous cosmetic compositions free from dyeing and oxidising agents, the control unit (24) comprising a man-machine interface (80) which can be controlled by a user in such a way as to select the or each anhydrous cosmetic composition which is to be placed in the dose.

9.- Process for dispensing a colouring composition for keratin fibres, characterised in that it comprises the following steps:

- providing a device (10; 110) according to any one of the preceding claims,

- controlling the dispenser (22) via the control unit (24) to remove the first mass of dye composition, the second mass of second composition , and the third mass of anhydrous composition and to dispense them into a packaging (26) to form a dose (14), the total mass of anhydrous cosmetic composition dispensed from the, or from each third reservoir (2OA to 20B) to form each dose (14) of colouring composition being at least 20 % of the total mass of the dose (14) of colouring composition.

10.- Process according to claim 9, characterised in that the total mass of dye composition dispensed from the, or from each first reservoir (16A to 16D) to form each dose (14) of colouring composition is less than 25 % of the total mass of the dose (14).