WO2012163898A1

WO2012163898A1 - Dye composition using a (hydroxy)indoline coupler in a medium rich in fatty substances, process and devices

Info

Publication number: WO2012163898A1
Application number: PCT/EP2012/060007
Authority: WO
Inventors: Alain Lagrange; Marie MIGNON
Original assignee: L'oreal
Priority date: 2011-05-31
Filing date: 2012-05-29
Publication date: 2012-12-06

Abstract

The present invention relates to a composition for dyeing keratin fibres, comprising: at least one fatty substance, at least one surfactant; at least one oxidation base, at least one indoline coupler of formula (B7) or of formula (B8), and also salts thereof, optical and geometrical isomers and tautomers thereof, and hydrates thereof, formulae (B7) and (B8) being the following: at least one basifying agent; the fatty substance content representing in total at least 25% by weight relative to the total weight of the composition; at least one oxidation base being chosen from heterocyclic oxidation bases when the coupler is of formula (B7). The present invention also relates to a process using this composition in the presence of at least one chemical oxidizing agent, and to multi-compartment devices suitable for the implementation of the invention.

Description

DYE COMPOSITION USING A (HYDROXY)INDOLINE COUPLER IN A MEDIUM RICH IN FATTY SUBSTANCES, PROCESS AND DEVICES

The present invention relates to a composition for dyeing keratin fibres, comprising one or more fatty substances and one or more surfactants, one or more oxidation bases and one or more couplers, of which at least one coupler is chosen from (hydroxy)indoline derivatives, one or more basifying agents, and the fatty substance content in the composition representing in total at least 25% by weight relative to the total weight of the composition.

The present invention also relates to a dyeing process using this composition in the presence of at least one chemical oxidizing agent, and to multi-compartment devices suitable for using this composition.

Many people have sought for a long time to modify the colour of their hair and in particular to mask their grey hair.

One of the dyeing methods is "permanent" or oxidation dyeing, which uses dye compositions containing oxidation dye precursors, generally known as oxidation bases.

These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or colouration modifiers, the latter being chosen especially from aromatic meia-diamines, meia-aminophenols, meia-diphenols and certain heterocyclic compounds such as indole compounds. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

It is also possible to use direct dyes in order especially to afford tints on the coloration obtained. These direct dyes are coloured and colouring molecules that have an affinity for the fibres. Examples that may be mentioned include nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes.

Permanent dyeing processes thus consist in using, with the dye composition, an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority of cases. The role of this oxidizing agent is to degrade the melanin of the hair, which, depending on the nature of the oxidizing agent present, leads to more or less pronounced lightening of the fibres. The oxidizing agent used is generally hydrogen peroxide.

One of the difficulties encountered during the implementation of the dyeing processes of the prior art arises from the fact that they are carried out under alkaline conditions and that the basifying agents most commonly used are aqueous ammonia and amines. Specifically, the basifying agent makes it possible to adjust the pH of the composition to an alkaline pH to enable activation of the oxidizing agent. In addition, this basifying agent causes swelling of the keratin fibre, with raising of the scales, which promotes the penetration of the oxidizing agent, and also of the dyes, essentially oxidation dyes, into the fibre, and thus increases the efficacy of the dyeing reaction.

However, these basifying agents, and especially aqueous ammonia, cause the user discomfort due to their strong characteristic odour.

Moreover, not only may the user be inconvenienced by the odour, but also may be confronted with greater risks of intolerance, for instance irritation of the scalp, which is especially reflected by stinging.

It is also important to obtain colorations that are light-fast, but the use of certain couplers, such as meia-phenylenediamines for example, induces degradation by solar radiation.

Moreover, it has been proposed in standard oxidation dyeing to use (hydroxy)indoline couplers in the presence of oxidation bases to obtain relatively photostable shades, but, firstly, with couplers of this type, the intensity of the coloration obtained over the whole head of hair (lengths, ends) is relatively poor, and, secondly, the coverage of the roots is not satisfactory.

One of the objects of the present invention is to propose compositions for dyeing human keratin fibres such as the hair that do not have the drawbacks of the existing compositions.

In particular, the composition according to the invention with chemical oxidizing agent makes it possible to obtain colours that are satisfactory, especially in terms of coverage or build-up of the colour at the root of the hair, which makes it possible to avoid a "root" effect of the coloration.

It is also possible to obtain colorations that are very stable towards light.

In addition, the invention makes it possible to to achieve substantial degrees of lightening while at the same time colouring, without using persalts or increasing the amount of chemical oxidizing agent or of basifying agent.

These aims and others are achieved by the present invention, one subject of which is thus a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising:

at least one fatty substance,

at least one surfactant,

at least one oxidation base,

- at least one basifying agent,

at least one coupler of formula (B7) or of formula (B8), and also salts thereof, optical and geometrical isomers and tautomers thereof, and hydrates thereof, the fatty substance content representing in total at least 25% by weight relative to the total weight of the composition; - formula (B7) being the following:

in which:

^* R¹ represents a hydrogen atom; a linear C1-C1₀ alkyl or C₂-Ci₀ alkenyl radical; a branched C3-C1₀ alkyl or alkenyl or a 3- to 8-membered cyclic radical optionally comprising one or more unsaturations; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being replaced with at least one oxygen, nitrogen or sulfur atom or with a group S0₂; the alkyl or alkenyl radical being optionally substituted;

^* R², independently of each other, represent:

a hydroxyl group;

· a halogen atom;

an optionally substituted, linear C1-C1₀ or branched C₃-C₈ alkyl radical;

an optionally substituted linear C₂-Ci₀ or branched C3-C1₀ alkenyl radical; the radical

R² being connected to the heterocycle via a carbon-carbon single bond;

a carboxyl or (d-C₈)alkoxycarbonyl group;

· two radicals R² borne by adjacent carbon atoms may form, together with the said carbon atoms, an optionally substituted 5- to 8-membered ring;

two radicals R² borne by the same carbon atom may form a group =CH-R' with R' representing a hydrogen atom or a linear C1-C9 or branched C₃-C₉ alkyl group; n is an integer ranging from 0 to 4; in the case where n is less than 4, the unsubstituted carbon atom(s) bear a hydrogen atom;

^* R³, independently of each other, represent:

a halogen atom;

an optionally substituted, linear C1-C1₀ or branched C₃-C₈ alkyl radical;

an optionally substituted linear C₂-Ci₀ or branched C3-C1₀ alkenyl radical;

· a hydroxyl radical, a Ci-C₈ alkoxy radical optionally bearing a hydroxyl group, a Ci-C₈ alkylthio radical;

an amino or mono- or dialkylamino group, the alkyl group(s), which may be identical or different, being Ci-C₈, optionally bearing a hydroxyl group;

-NH-CO-NHR" with R" representing a hydrogen atom or a C1-C4 alkyl group;

· a group -SR⁴ with R⁴ representing a hydrogen atom or a C1-C4 alkyl radical;

p is an integer ranging from 0 to 3; in the case where p is less than 3, the unsubstituted carbon atom(s) bear a hydrogen atom;

- formula (B8) being the following:

^* R¹ represents a hydrogen atom; a linear C1-C1₀ alkyl or C₂-Ci₀ alkenyl radical; a branched C3-C1₀ alkyl or alkenyl or a 3- to 8-membered cyclic radical optionally comprising one or more unsaturations; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being replaced with at least one oxygen, nitrogen or sulfur atom or with a group S0₂; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being substituted with one or more halogen atoms;

^* R², independently of each other, represent:

a halogen atom;

· a linear C1-C1₀ or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or C1-C4 alkoxy groups;

a linear C₂-Ci₀ or branched C3-C1₀ alkenyl radical; the said radical being optionally substituted with one or more hydroxyl or C1-C4 alkoxy groups, the radical being connected to the heterocycle via a carbon-carbon single bond;

a carboxyl or (CrC₈)alkylcarbonyl group;

two radicals R² borne by adjacent carbon atoms may form, together with the said carbon atoms, a 5- to 8-membered ring;

two radicals R² borne by the same carbon atom may form a group =CH-R' with R' representing a hydrogen atom or a linear C1-C9 or branched C₃-C₉ alkyl group; n is an integer ranging from 0 to 4; in the case where n is less than 4, the unsubstituted carbon atom(s) bear one or two hydrogen atoms;

^* R³ and R⁴, independently of each other, represent:

a hydrogen atom;

a halogen atom;

· a linear C1-C1₀ or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or CrC₈ alkoxy groups or halogen atoms;

a linear C₂-Ci₀ or branched C3-C1₀ alkenyl radical;

a Ci-C₈ alkoxy radical;

- at least one oxidation base being chosen from heterocyclic oxidation bases when the coupler is of formula (B7).

Another subject of the invention is a dyeing process using the composition of the invention in the presence of at least one chemical oxidizing agent, and multi-compartment devices that enable the use of the composition of the invention. Thus, the use of the dye composition of the invention in the presence of at least one chemical oxidizing agent leads to powerful, intense, chromatic and/or sparingly selective colorations, i.e. colorations that are uniform along the fibre.

The invention also makes it possible to cover keratin fibres particularly well at their root, especially down to three centimetres from the base of said fibres.

Moreover, the colours obtained after treating the fibres remain stable, in particular towards light.

The invention also makes it possible to reduce the amounts of active agents of the invention such as the dyes and/or basifying agents and/or oxidizing agents without loss of dyeing efficacy of the composition.

Furthermore, the processes according to the invention use formulations that are less malodorous during their application to the hair or during their preparation.

Other features and advantages of the invention will become more clearly apparent on reading the description and the examples that follow.

In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range.

The human keratin fibres treated via the process according to the invention are preferably the hair.

The expression "at least one" is equivalent to the expression "one or more".

Fatty substance:

As has already been mentioned, the composition of the invention comprises one or more fatty substances.

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

Preferably, the fatty substances of the invention do not contain any salified or unsalified carboxylic acid groups (COOH or COO^"). Particularly, the fatty substances of the invention are neither polyoxyalkylenated nor polyglycerolated.

The term "oil" means a "fatty substance" that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg).

The term "non-silicone o/V means an oil not containing any silicon atoms (Si) and the term "silicone o/V means an oil containing at least one silicon atom. More particularly, the fatty substances are chosen from C₆-Ci₆ alkanes, non-silicone oils of animal, plant, mineral or synthetic origin, fatty alcohols, esters of a fatty acid and/or of a fatty alcohol, non-silicone waxes and silicones.

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

As regards the C₆-Ci₆ alkanes, they are linear or branched, and possibly cyclic.

Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.

As oils of animal, plant, mineral or synthetic origin that may be used in the composition of the invention, examples that may be mentioned include:

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

- triglyceride oils of plant or synthetic origin, such as liquid fatty acid triglycerides containing from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol^® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil;

- linear or branched hydrocarbons of mineral or synthetic origin, containing more than 16 carbon atoms, such as liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam®;

fluoro oils, for instance perfluoromethylcyclopentane and perfluoro-1 ,3- dimethylcyclohexane, sold under the names Flutec^® PC1 and Flutec^® PC3 by the company BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050^® and PF 5060^® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl^® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052^® by the company 3M.

The fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated alcohols comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Examples that may be mentioned include cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol and linoleyl alcohol. As regards the esters of a fatty acid and/or of fatty alcohols, which are advantageously different from the triglycerides mentioned above, mention may be made especially of esters of saturated or unsaturated, linear or branched Ci-C₂6 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci-C₂6 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; Ci₂-Ci₅ 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; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2- ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Still within the context of this variant, esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C₂-C₂6 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.

Mention may be made especially of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates.

Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.

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

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

The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C₆-C₃o, and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

The esters according to this variant may also be chosen from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters.

More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates.

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

Examples of esters or mixtures of esters of sugar and of fatty acid that may also be mentioned include:

- the products sold under the names F160, F140, F1 10, F90, F70 and SL40 by the company Crodesta, respectively denoting sucrose palmitostearates formed from 73% monoester and 27% diester and triester, from 61 % monoester and 39% diester, triester and tetraester, from 52% monoester and 48% diester, triester and tetraester, from 45% monoester and 55% diester, triester and tetraester, from 39% monoester and 61 % diester, triester and tetraester, and sucrose monolaurate;

- the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% diester-tri ester-polyester;

- the sucrose monopalmitostearate-dipalmitostearate sold by the company

Goldschmidt under the name Tegosoft^® PSE.

The non-silicone wax(es) are chosen in particular from carnauba wax, candelilla wax, esparto wax, paraffin wax, ozokerite, plant waxes, such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute flower waxes, such as the blackcurrant blossom essential wax sold by Bertin (France), or animal waxes, such as beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy raw materials that can be used according to the invention are in particular marine waxes, such as that sold by Sophim under the reference M82, polyethylene waxes or polyolefin waxes in general.

The silicones that can be used in the cosmetic compositions of the present invention are volatile or non-volatile, cyclic, linear or branched silicones, which are unmodified or modified with organic groups, having a viscosity from 5x10^"6 to 2.5 m²/s at 25°C, and preferably 1 x10^"5 to 1 m²/s.

The silicones that can be used in accordance with the invention may be in the form of oils, waxes, resins or gums.

Preferably, the silicone is chosen from polydialkylsiloxanes, especially polydimethylsiloxanes (PDMSs), and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene) groups, amino groups and alkoxy groups.

Organopolysiloxanes are defined in greater detail in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academic Press. They may be volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and more particularly still from:

(i) cyclic polydialkylsiloxanes containing from 3 to 7 and preferably from 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone^® 7207 by Union Carbide or Silbione^® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone^® 7158 by Union Carbide, and Silbione^® 70045 V5 by Rhodia, and mixtures thereof.

Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone^® FZ 3109 sold by the company Union Carbide, of formula:

CH,

CH, with D" : - Si - O— with D' : - Si - O—

CH₃ ^C8 ^H 17

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1 ,1 '-bis(2,2,2',2',3,3'-hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x10^"6 m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics.

Use is preferably made of non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the organofunctional groups above, and mixtures thereof.

These silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes having trimethylsilyl end groups. The viscosity of the silicones is measured at 25°C according to ASTM standard 445 Appendix C.

Among these polydialkylsiloxanes, mention may be made, in a nonlimiting manner, of the following commercial products:

- the Silbione^® oils of the 47 and 70 047 series or the Mirasil^® oils sold by Rhodia, for instance the oil 70 047 V 500 000;

- the oils of the Mirasil^® series sold by the company Rhodia;

- the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm²/s;

- the Viscasil^® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes having dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax^® 9800 and 9801 by the company Goldschmidt, which are poly(CrC₂o)dialkylsiloxanes.

The silicone gums that can be used in accordance with the invention are especially polydialkylsiloxanes and preferably polydimethylsiloxanes with high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent. This solvent can be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecane, or mixtures thereof.

Products that can be used more particularly in accordance with the invention are mixtures such as:

- the mixtures formed from a hydroxy-terminated polydimethylsiloxane or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2 1401 sold by Dow Corning;

- mixtures of a polydimethylsiloxane gum and a cyclic silicone, such as the product SF 1214 Silicone Fluid from the company General Electric; this product is an SF 30 gum corresponding to a dimethicone, having a number-average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;

- mixtures of two PDMSs with different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is a mixture of a gum SE 30 defined above with a viscosity of 20 m²/s and of an oil SF 96 with a viscosity of 5x10^"6 m²/s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.

The organopolysiloxane resins that can be used in accordance with the invention are crosslinked siloxane systems containing the following units:

2Si02/2, R3S1O1/2, RS1O3/2 and Si0₄/₂

in which R represents an alkyl containing 1 to 16 carbon atoms. Among these products, the ones that are particularly preferred are those in which R denotes a C C₄ lower alkyl group, more particularly methyl.

Among these resins, mention may be made of the product sold under the name Dow Corning 593 or those sold under the names Silicone Fluid SS 4230 and SS 4267 by the company General Electric, which are silicones of dimethyl/trimethylsiloxane structure.

Mention may also be made of the trimethyl siloxysilicate type resins sold especially under the names X22-4914, X21 -5034 and X21 -5037 by the company Shin-Etsu.

The organomodified silicones that can be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

Besides the silicones described above, the organomodified silicones may be polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.

The polyalkylarylsiloxanes are chosen particularly from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity of from 1 *10^"5 to 5*10^"2 m²/s at 25°C.

Among these polyalkylarylsiloxanes, examples that may be mentioned include the products sold under the following names:

. the Silbione^® oils of the 70 641 series from Rhodia;

. the oils of the Rhodorsil^® 70 633 and 763 series from Rhodia;

. the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;

. the silicones of the PK series from Bayer, such as the product PK20;

. the silicones of the PN and PH series from Bayer, such as the products PN1000 and PH 1000;

. certain oils of the SF series from General Electric, such as SF 1023, SF 1 154, SF 1250 and SF 1265.

Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising: - polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C₆-C₂4 alkyl groups, such as the products known as dimethicone copolyol sold by the company Dow Corning under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 71 1 by the company Union Carbide, and the (Ci₂)alkylmethicone copolyol sold by the company Dow Corning under the name Q2 5200;

- substituted or unsubstituted amine groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee, or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amine groups are, in particular, Ci-C₄ aminoalkyl groups;

- alkoxy groups such as the product sold under the name Silicone Copolymer F-

755 by SWS Silicones, and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt.

Preferably, the fatty substances do not comprise any C₂-C₃ oxyalkylene units or any glycerolated units.

More particularly, the fatty substances are chosen from compounds that are liquid or pasty at room temperature (25°C) and at atmospheric pressure.

Preferably, the fatty substance is a compound that is liquid at a temperature of 25°C and at atmospheric pressure.

The fatty substances are advantageously chosen from C₆-Ci₆ alkanes, non-silicone oils of plant, mineral or synthetic origin, fatty alcohols, esters of a fatty acid and/or of a fatty alcohol, and silicones, or mixtures thereof.

Preferably, the fatty substance is chosen from liquid petroleum jelly, C₆-Ci₆ alkanes, polydecenes, liquid esters of a fatty acid and/or of a fatty alcohol, and liquid fatty alcohols, or mixtures thereof.

Better still, the fatty substance is chosen from liquid petroleum jelly, C₆-Ci₆ alkanes and polydecenes.

The composition according to the invention comprises at least 25% by weight of fatty substances.

The composition according to the invention more particularly has a fatty substance content ranging from 25% to 80% by weight, preferably from 30% to 70% by weight and more advantageously still from 30% to 60% by weight relative to the weight of the composition.

Surfactants:

The composition of the invention also comprises one or more surfactants.

In particular, the surfactant(s) are chosen from anionic, amphoteric, zwitterionic, cationic and nonionic surfactants, and preferentially nonionic surfactants.

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the groups -C(0)OH, -C(0)0^", -S0₃H, -S(0)₂0^", -OS(0)₂OH, -OS(0)₂0^", -P(0)OH₂, -P(0)₂0^",- P(0)0₂ ^", -P(OH)₂, =P(0)OH, -P(OH)0^", =P(0)0^", =POH, =PO^", the anionic parts comprising a cationic counterion such as an alkali metal, an alkaline-earth metal or an ammonium.

As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkyl sulfosuccinamates, acylisethionates and N-acyltaurates, polyglycoside polycarboxylic acid and alkyl monoester salts, acyl lactylates, salts of D-galactoside uronic acids, salts of alkyl ether carboxylic acids, salts of alkylaryl ether carboxylic acids, salts of alkylamido ether carboxylic acids; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.

These compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The salts of C₆-C₂₄ alkyl monoesters of polyglycoside-polycarboxylic acids can be selected from C₆-C₂₄ alkyl polyglycoside-citrates, C₆-C₂₄ alkyl polyglycoside-tartrates and C₆-C₂₄ alkyl polyglycoside-sulfosuccinates.

When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as the magnesium salts.

Examples of amino alcohol salts that may especially be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2- amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

Use is preferably made of alkali metal or alkaline-earth metal salts, and in particular sodium or magnesium salts.

Among the anionic surfactants mentioned, use is preferably made of (C₆-C₂₄)alkyl sulfates, (C₆-C₂₄)alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.

In particular, it is preferred to use (Ci₂-C₂₀)alkyl sulfates, (Ci₂-C₂₀)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds. Better still, it is preferred to use sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.

The amphoteric or zwitterionic surfactant(s), which are preferably non-silicone surfactant(s), which can be used in the present invention may especially be derivatives of optionally quaternized secondary or tertiary aliphatic amines, in which derivatives the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (C₈-C₂o)alkylbetaines, sulfobetaines, (C8-C2o)alkylamido(C₃-C₈)alkylbetaines and (C₈- C2o)alkylamido(C₆-C₈)alkylsulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that can be used, as defined above, mention may also be made of the compounds of respective structures (A1) and (A2) below:

R_a-C(0)-NH-CH2-CH2-N⁺(R_b)(R_c)-CH₂C(0)0-, M⁺, X^" (A1 )

in which formula (A1):

^■ R_a represents a Ci₀-C₃o alkyl or alkenyl group derived from an acid R_a-COOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;

^■ R_b represents a β-hydroxyethyl group; and

■ R_c represents a carboxymethyl group;

^■ M⁺ represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine, and

^■ X^" represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (CrC₄)alkyl sulfates, (Ci-C₄)alkyl or (Ci-C₄)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M⁺ and X^" are absent;

R_a-CiOJ-NH-CHz-CHz-NiBXB') (A2)

in which formula (A2):

■ B represents the group -CH₂-CH₂-0-X';

^■ B' represents the group -(CH₂)_zY\ with z = 1 or 2;

^■ X' represents the group -CH₂-C(0)OH, -CH₂-C(0)OZ', -CH₂-CH₂-C(0)OH, -CH₂-CH₂-C(0)OZ', or a hydrogen atom;

^■ Y' represents the group -C(0)OH, -C(0)OZ', -CH₂-CH(OH)-S0₃H or the group - CH₂-CH(OH)-S0₃-Z';

^■ Z' represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; ^■ R_a' represents a C10-C30 alkyl or alkenyl group of an acid R_a-C(0)OH preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially a Ci₇ alkyl group, and its iso form, or an unsaturated Ci₇ group.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol^® C2M Concentrate.

Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of (C₈-C₂o)alkylbetaines such as cocobetaine, and (C₈- C2o)alkylamido(C₃-C₈)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof. More preferentially, the amphoteric or zwitterionic surfactant(s) are chosen from cocamidopropylbetaine and cocobetaine.

The cationic surfactant(s) that can be used in the composition according to the present invention comprise, for example, salts of optionally polyoxyalkylenated primary, secondary or tertiary fatty amines, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may especially be mentioned include:

- those corresponding to the general formula (A3) below:

in which formula (A3):

^■ R₈ to Rii, which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups R₈ to Rn comprises from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms; and

^■ X^" represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (CrC₄)alkyl sulfates, (Ci-C₄)alkyl or

(CrC₄)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate.

The aliphatic groups of R₈ to Rn may also comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens.

The aliphatic groups of R₈ to Rn are chosen, for example, from C1-C30 alkyl, C1-C30 alkoxy, polyoxy(C₂-C₆)alkylene, Ci-C₃₀ alkylamide, (Ci₂-C22)alkylamido(C2-C₆)alkyl, (C12- C₂2)alkyl acetate, and Ci-C₃₀ hydroxyalkyl, X^" is an anionic counterion chosen from halides, phosphates, acetates, lactates, (CrC₄)alkyl sulfates, (CrC₄)alkyl or (d- C₄)alkylaryl sulfonates.

Among the quaternary ammonium salts of formula (A3), preference is given firstly to tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name Ceraphyl® 70 by the company Van Dyk;

- quaternary ammonium salts of imidazoline, for instance those of formula (A4) below:

in which formula (A4):

^■ Ri₂ represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example tallow fatty acid derivatives;

^■ Ri3 represents a hydrogen atom, a C₁-C4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms;

^■ Ri4 represents a C₁-C4 alkyl group;

^■ Ri5 represents a hydrogen atom or a C₁-C4 alkyl group;

^■ X^" represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (CrC₄)alkyl sulfates, (CrC₄)alkyl or (d-

C₄)alkylaryl sulfonates.

R-I2 and Ri₃ preferably denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example tallow fatty acid derivatives, Ri₄ denotes a methyl group, and Ri₅ denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;

- quaternary diammonium or triammonium salts, in particular of formula (A5) below:

R. R.

R N— (CH₂)₃— N— R, 2X^~

R. R,

(A5) in which formula (A5):

^■ Ri₆ denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;

^■ Ri7 is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH₂)₃-N⁺(R_16a)(R_17a)(R_18a), X-;

^■ R_16a, Rua, Riea, R18, Ri9, R20 and R21 , which may be identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms; and

^■ X^", which may be identical or different, represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (C

C₄)alkyl sulfates, (CrC₄)alkyl or (Ci-C₄)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate.

Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium 75);

- quaternary ammonium salts containing one or more ester functions, such as those of formula (A6) below:

in which formula (A6):

^■ R₂2 is chosen from CrC₆ alkyl and CrC₆ hydroxyalkyl or dihydroxyalkyl groups, ■ R23 is chosen from:

O

- the group ^{R¾5 C} ,

- linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups R₂₇,

- a hydrogen atom,

■ R25 is chosen from:

O

- the group ^R28 ^

- linear or branched, saturated or unsaturated Ci-C₆ hydrocarbon-based groups R₂₉,

- a hydrogen atom,

■ R₂4, R26 and R₂e, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups;

^■ r, s and t, which may be identical or different, are integers ranging from 2 to 6, ^■ l and t1 , which may be identical or different, are equal to 0 or 1 , with r2+r1 =2r and t1 +t2=2t,

^■ y is an integer ranging from 1 to 10,

^■ x and z, which may be identical or different, are integers ranging from 0 to 10, ■ X^" represents an organic or inorganic anionic counterion,

with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R₂3 denotes R₂7, and that when z is 0 then R₂₅ denotes R₂₉.

The alkyl groups R₂₂ may be linear or branched, and more particularly linear.

Preferably, R₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.

Advantageously, the sum x + y + z is from 1 to 10.

When R₂₃ is a hydrocarbon-based group R₂₇, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.

When R₂₅ is a hydrocarbon-based group R₂₉, it preferably contains 1 to 3 carbon atoms.

Advantageously, R₂₄, R₂₆ and R₂₈, which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn-C₂i hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn-C₂i alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0 or 1.

Advantageously, y is equal to 1 .

Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anionic counterion X^" is preferably a halide, such as chloride, bromide or iodide; a (CrC₄)alkyl sulfate or a (CrC₄)alkyl or (Ci-C₄)alkylaryl sulfonate. However, it is possible to use methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function.

The anionic counterion X^" is even more particularly chloride, methyl sulfate or ethyl sulfate.

Use is made more particularly in the composition according to the invention of the ammonium salts of formula (A6) in which:

- R₂₂ denotes a methyl or ethyl group,

- x and y are equal to 1 ,

- z is equal to 0 or 1 ,

- r, s and t are equal to 2,

- R₂₃ is chosen from: the group

methyl, ethyl or C14-C22 hydrocarbon-based groups,

a hydrogen atom,

- R25 is chosen from:

• the group

• a hydrogen atom,

- R24, R26 and R₂e, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.

Advantageously, the hydrocarbon-based radicals are linear.

Among the compounds of formula (A6), examples that may be mentioned include salts, especially the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,

monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyi sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco.

The composition according to the invention may contain, for example, a mixture of quaternary ammonium salts of monoesters, diesters and triesters with a weight majority of diester salts.

It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180. Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.

Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Among the cationic surfactants that may be present in the composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.

Examples of nonionic surfactants that can be used in the composition used according to the invention are described, for example, in the "Handbook of Surfactants" by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp. 1 16-178. They are especially chosen from alcohols, a-diols and (CrC₂o)alkylphenols, these compounds being polyethoxylated, polypropoxylated or polyglycerolated, and containing at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to especially range from 2 to 50, and for the number of glycerol groups to especially range from 2 to 30.

Mention may also be made of copolymers of ethylene oxide and propylene oxide, optionally oxyethylenated sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyalkylenated fatty acid esters, optionally oxyalkylenated alkyl polyglycosides, alkyl glucoside esters, derivatives of N-alkyl glucamine and of N-acyl methylglucamine, aldobionamides and amine oxides.

The nonionic surfactants are more particularly chosen from monooxyalkylenated or polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.

Examples of oxyalkylenated nonionic surfactants that may be mentioned include: · oxyalkylenated (C₈-C₂4)alkylphenols;

• saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃o alcohols;

• saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃o amides;

• esters of saturated or unsaturated, linear or branched C₈-C₃o acids and of polyethylene glycols;

· polyoxyethylenated esters of saturated or unsaturated, linear or branched C₈-C₃o acids and of sorbitol;

• saturated or unsaturated, oxyethylenated plant oils;

• condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures; • oxyethylenated and/or oxypropylenated silicones.

The surfactants contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100, preferably between 2 and 50 and preferably between 2 and 30. Advantageously, the nonionic surfactants do not comprise any oxypropylene units.

In accordance with one preferred embodiment of the invention, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C₈-C₃₀ alcohols comprising from 1 to 100 mol of ethylene oxide; polyoxyethylenated esters of linear or branched, saturated or unsaturated C₈-C₃₀ acids and of sorbitol comprising from 1 to 100 mol of ethylene oxide.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C₈-C₄o alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C₈-C₄₀ alcohols correspond to the formula (A7) below:

R2₉0-[CH2-CH(CH₂OH)-0]_m-H (A7)

in which formula (A8):

^■ R₂9 represents a linear or branched C₈-C₄₀ and preferably C₈-C₃o alkyl or alkenyl radical; and

^■ m represents a number ranging from 1 to 30 and preferably from 1 to 10.

As examples of compounds of formula (A7) that are suitable within the context of the invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (I NCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1 .5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (I NCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The glycerolated alcohol of formula (A7) may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohols may coexist in the form of a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is more particularly preferred to use the C₈/Ci₀ alcohol containing 1 mol of glycerol, the C1₀/C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1 .5 mol of glycerol.

Preferably, the surfactant used in the process of the invention in the composition is a monooxyalkylenated or polyoxyalkylenated, particularly monooxyethylenated or polyoxyethylenated, or monooxypropylenated or polyoxypropylenated, nonionic surfactant, or a combination thereof, more particularly monooxyethylenated or polyoxyethylenated. Preferably, the surfactant(s) are chosen from nonionic surfactants or from anionic surfactants. More particularly, the surfactant(s) present in the composition are chosen from nonionic surfactants.

More preferably still, the nonionic surfactants are chosen from polyoxyethylenated sorbitol esters and polyoxyethylenated fatty alcohols, and mixtures thereof.

In the composition of the invention, the amount of surfactant(s) in the composition preferably ranges from 0.1 % to 50% by weight and better still from 0.5% to 20% by weight relative to the total weight of the composition. Oxidation bases:

The composition of the invention comprises one or more oxidation bases chosen especially from heterocyclic bases, benzene bases, and salts thereof.

The benzene oxidation bases according to the invention are particularly chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols, and the addition salts thereof.

Among the para-phenylenediamines that may be mentioned, for example, are para- phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl- para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para- phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, Ν,Ν-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(P-hydroxyethyl)-para- phenylenediamine, 4-N,N-bis( -hydroxyethyl)amino-2-methylaniline, 4-N,N-bis( - hydroxyethyl)amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro- para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(P-hydroxypropyl)-para- phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl- para-phenylenediamine, N-ethyl-N-(P-hydroxyethyl)-para-phenylenediamine, Ν-(β,γ- dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N- phenyl-para-phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine, 2-β- acetylaminoethyloxy-para-phenylenediamine, N-(P-methoxyethyl)-para- phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β- hydroxyethylamino-5-aminotoluene, 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2- -hydroxyethyl-para- phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis( -hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine and 2- -acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred. Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N'-bis( -hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis( - hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis( -hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine and 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.

Among the para-aminophenols that may be mentioned, for example, are para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-( -hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols that may be mentioned, for example, are 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the addition salts thereof.

The heterocyclic bases are more particularly chosen from pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and the addition salts thereof.

In the case where the coupler is chosen from the compounds of formula (B7), the composition of the invention comprises one or more oxidation bases chosen from heterocyclic bases, and salts thereof.

In the case where the coupler is chosen from the compounds of formula (B8), and according to one particular embodiment of the invention, the composition comprises at least one heterocyclic oxidation base.

Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for instance 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.

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

Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in the patents DE 2359399; JP 88-169571 ; JP 05-63124; EP 0 770 375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4- hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives that may be mentioned are the compounds described in the 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 - methylpyrazole, 4,5-diamino-1-( -hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5- diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3-dimethylpyrazole, 4,5-diamino-3- methyl-1 -phenylpyrazole, 4,5-diamino-1 -methyl-3-phenylpyrazole, 4-amino-1 ,3-dimethyl- 5-hydrazinopyrazole, 1 -benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-ie f-butyl-1 - methylpyrazole, 4,5-diamino-1 -ie f-butyl-3-methylpyrazole, 4,5-diamino-1 -(β- hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1 -ethyl-3-methylpyrazole, 4,5-diamino-1 - ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1 -ethyl-3-hydroxymethylpyrazole, 4,5- diamino-3-hydroxymethyl-1 -methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - isopropylpyrazole, 4,5-diamino-3-methyl-1 -isopropylpyrazole, 4-amino-5-(2'- aminoethyl)amino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5- triaminopyrazole, 3,5-diamino-1 -methyl-4-methylaminopyrazole, 3,5-diamino-4-(P- hydroxyethyl)amino-1 -methylpyrazole, and the addition salts thereof. Use may also be made of 4,5-diamino-1-( -methoxyethyl)pyrazole.

Use will preferably be made of a 4,5-diaminopyrazole and more preferably still of 4,5-diamino-1-( -hydroxyethyl)pyrazole and/or a salt thereof.

Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and especially those described in patent application FR-A- 2 886 136, such as the following compounds and the addition salts thereof: 2,3-diamino- 6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one, 4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2- diethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-di(2-hydroxyethyl)-1 ,2-dihydropyrazol- 3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one, 2-amino-3-dimethylamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2,3- diamino-5,6,7,8-tetrahydro-1 H,6H-pyridazino[1 ,2-a]pyrazol-1 -one, 4-amino-1 ,2-diethyl-5- (pyrrolidin-1 -yl)-1 ,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1 -yl)-1 ,2- diethyl-1 ,2-dihydropyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one.

Use will preferably be made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one and/or a salt thereof.

As heterocyclic bases, use will preferably be made of 4,5-diamino-1-(P- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one and/or a salt thereof.

The heterocyclic oxidation base(s) each advantageously represent from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

Additional oxidation base:

In the case where the composition comprises at least one coupler of formula (B7), the composition of the invention may optionally comprise one or more additional oxidation bases, other than the abovementioned heterocyclic bases, chosen in particular from benzene-based oxidation bases, and the salts thereof as mentioned previously.

The additional oxidation base(s), if the composition comprises any, each advantageously represent from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

Hydroxyindoline couplers of formula (B7):

The composition according to the invention comprises one or more couplers of formula (B7) and also salts thereof, optical and geometrical isomers and tautomers thereof,

* R¹ represents a hydrogen atom; a linear C1-C1₀ alkyl or C₂-Ci₀ alkenyl radical; a branched C3-C1₀ alkyl or alkenyl or a 3- to 8-membered cyclic radical optionally comprising one or more unsaturations; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being replaced with at least one oxygen, nitrogen or sulfur atom or with a group S0₂; the alkyl or alkenyl radical being optionally substituted;

^* R², independently of each other, represent:

a hydroxyl group;

· a halogen atom;

an optionally substituted, linear C1-C1₀ or branched C₃-C₈ alkyl radical;

R² being connected to the heterocycle via a carbon-carbon single bond;

a carboxyl or (d-C₈)alkoxycarbonyl group;

^* R³, independently of each other, represent:

a halogen atom;

an optionally substituted, linear C1-C1₀ or branched C₃-C₈ alkyl radical;

-NH-CO-NHR" with R" representing a hydrogen atom or a C1-C4 alkyl group;

p is an integer ranging from 0 to 3; in the case where p is less than 3, the unsubstituted carbon atom(s) bear a hydrogen atom.

According to the invention, and unless otherwise specified, a linear or branched alkyl or alkenyl radical is said to be substituted when it bears one or more groups chosen from the following groups:

o halogen atoms, such as chlorine, bromine or fluorine,

o hydroxyl,

o Ci-C₆ alkoxy,

o amino,

o mono(Ci-C₆)alkylamino or di(Ci-C₆)alkylamino optionally substituted with one or more hydroxyl or amino groups,

o carboxyl or (Ci-C₈)alkoxycarbonyl. It should be noted that the term "carboxyl" means -COOM with M representing a hydrogen atom or a cation derived from an alkali metal or an alkaline-earth metal, or an organic cation such as ammonium.

When the group is cyclic or heterocyclic, it may be substituted on the carbon atom with one or more groups such as those mentioned for alkyl or alkenyl groups, and also with one or more CrC₄ alkyl radicals.

According to a particular variant of the invention, the coupler(s) of formula (B7) are chosen from those in which:

* R¹ represents a hydrogen atom; a linear C1-C10 alkyl or C₂-Ci₀ alkenyl radical; a branched C3-C10 alkyl or alkenyl or a 3- to 8-membered cyclic radical optionally comprising one or more unsaturations; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being replaced with at least one oxygen, nitrogen or sulfur atom or with a group S0₂; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being substituted with one or more hydroxyl, Ci-C₆ alkoxy, amino or Ci-C₆ mono- or dialkylamino groups, or halogen atoms;

* R², independently of each other, represent:

a hydroxyl group;

a halogen atom;

· a linear C1-C10 or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl, C C₄ alkoxy, carboxyl, (CrC₈)alkoxycarbonyl, amino or mono- or dialkylamino groups, the alkyl group being C C₄;

a linear C₂-Ci₀ or branched C3-C10 alkenyl radical; the said radical being optionally substituted with one or more hydroxyl, C C₄ alkoxy, carboxyl, amino or mono- or dialkylamino groups, the alkyl group(s), which may be identical or different, being

Ci-C₄, the radical R² being linked to the heterocycle via a carbon-carbon single bond;

carboxyl or (d-C₈)alkoxycarbonyl;

two radicals R² borne by adjacent carbon atoms may form, together with the said carbon atoms, an optionally substituted 5- to 8-membered ring;

* R³, independently of each other, represent:

a halogen atom;

a linear C1-C10 or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl, CrC₈ alkoxy, amino or mono- or dialkylamino groups, the alkyl group being Ci-C₄, or halogen atoms; an optionally substituted linear C₂-Ci₀ or branched C3-C10 alkenyl radical;

a hydroxyl radical, a Ci-C₈ alkoxy radical optionally bearing a hydroxyl group, a

Ci-C₈ alkylthio radical;

-NH-CO-NHR" with R" representing a hydrogen atom or a CrC₄ alkyl radical; a group -SR⁴ with R⁴ representing a hydrogen atom or a CrC₄ alkyl radical;

In accordance with one preferred embodiment of the invention, the coupler(s) of formula (B7) are chosen from those for which:

^* R¹ represents a hydrogen atom; a linear CrC₆ or branched C₃-C₆ alkyl radical, optionally substituted with one or more hydroxyl, Ci-C₄ alkoxy, amino or mono- or dialkylamino groups, or halogen atoms;

* R², independently of each other, represent:

a halogen atom;

a linear Ci-C₆ or branched C₃-C₆ alkyl radical, optionally substituted with one or more hydroxyl, CrC₄ alkoxy, carboxyl, (CrC₈)alkoxycarbonyl, amino or mono- or dialkylamino groups, the alkyl group being Ci-C₄;

· carboxyl or (Ci-C₈)alkoxycarbonyl;

a group =CH-R' with R' representing a hydrogen atom or a linear C1-C4 alkyl group; n is an integer ranging from 0 to 4; in the case where n is less than 4, the unsubstituted carbon atom(s) bear one or two hydrogen atoms;

^* R³, independently of each other, represent:

· a halogen atom such as chlorine, bromine or fluorine;

a linear Ci-C₆ or branched C₃-C₆ alkyl radical, optionally substituted with one or more hydroxyl, CrC₄ alkoxy, amino or mono- or dialkylamino groups, the alkyl group being Ci-C₄, or halogen atoms;

a hydroxyl radical, a Ci-C₄ alkoxy radical optionally bearing a hydroxyl group, a C1-C4 alkylthio radical;

-NH-CO-NHR" with R" representing a hydrogen atom or a C1-C4 alkyl radical; a group -SR⁴ with R⁴ representing a hydrogen atom or a C1-C4 alkyl radical;

Preferably, the coupler(s) of formula (B7) are chosen from the following compounds, and also the salts thereof, optical and geometrical isomers and tautomers thereof, and hydrates thereof:

In one variant of the invention, p denotes 0 or 1 and R³ denotes a hydroxyl group.

In one variant of the invention, R¹ denotes a hydrogen atom or a methyl group. The coupler(s) of formula (B7) each advantageously represent from 0.0001 % to 10% by weight relative to the total weight of the composition and preferably from 0.005% to 5% by weight relative to the total weight of the composition of the invention.

Indoline couplers of formula (B8):

The composition according to the invention comprises one or more indoline couplers.

As indicated previously, this or these coupler(s) are chosen from those of formula (B8), and also the salts thereof, optical and geometrical isomers or tautomers thereof, and hydrates thereof;

(B8) in which formula:

^* R¹ represents a hydrogen atom; a linear C1-C1₀ alkyl or C₂-Ci₀ alkenyl radical; a branched C₃-C₈ alkyl or alkenyl or a 3- to 8-membered cyclic radical optionally comprising one or more unsaturations; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being replaced with at least one oxygen, nitrogen or sulfur atom or with a group S0₂; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being substituted with one or more halogen atoms;

^* R², independently of each other, represent:

· a halogen atom;

a linear C1-C1₀ or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or C1-C4 alkoxy groups;

a carboxyl or (d-C₈)alkoxycarbonyl group;

two radicals R² borne by the same carbon atom may form a group =CH-R' with R' representing a hydrogen atom or a linear C1-C9 or branched C3-C9 alkyl group; n is an integer ranging from 0 to 4; in the case where n is less than 4, the unsubstituted carbon atom(s) bear one or two hydrogen atoms;

^* R³ and R⁴, independently of each other, represent:

a hydrogen atom;

· a halogen atom; a linear C₁-C₁₀ or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or CrC₈ alkoxy groups or halogen atoms;

a linear C₂-Ci₀ or branched C3-C₁₀ alkenyl radical;

a Ci-C₈ alkoxy radical;

It should be noted that the term "carboxyl" means -COOM with M representing a hydrogen atom or a cation derived from an alkali metal or an alkaline-earth metal, or an organic cation such as ammonium.

According to a preferred variant of the invention, the phenol-based coupler(s) of formula (B8) are chosen from those in which:

^* Ri denotes a hydrogen atom or a linear C₁-C₁₀ or branched C₃-C₈ alkyl radical;

^* R², independently of each other, represent:

a linear C₁-C₁₀ or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or C₁-C4 alkoxy groups;

a carboxyl or (Ci-C₈)alkoxycarbonyl group;

two radicals R² borne by the same carbon atom may form a group =CH₂;

n is an integer ranging from 0 to 4; in the case where n is less than 4, the unsubstituted carbon atom(s) bear a hydrogen atom;

^* R³ and R⁴, independently of each other, represent:

a hydrogen atom;

a bromine or chlorine atom;

a linear C₁-C₁₀ or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or CrC₈ alkoxy groups or fluorine atoms;

a Ci-C₈ alkoxy radical;

According to a first variant of the invention, R³ denotes a hydrogen atom.

In accordance with a second variant, n denotes 0 or 1 or 2. These two variants may also be combined.

Preferably, the indoline coupler(s) of formula (B8) are chosen from the following compounds, and also the salts thereof, optical and geometrical isomers and tautomers thereof, and hydrates thereof:

Preferably, R¹ denotes a hydrogen atom.

The indoline coupler(s) of formula (B8) each advantageously represent from 0.0001 % to 10% by weight relative to the total weight of the composition and preferably from 0.005% to 5% by weight relative to the total weight of the composition of the invention.

Additional couplers:

The composition of the invention may optionally comprise one or more additional couplers other than the couplers of formula (B7) or of formula (B8).

Among these additional couplers, mention may be made especially of meta- phenylenediamines, meia-aminophenols, meia-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.

Mention may be made, for example, of 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2,4-diamino-1-(3- hydroxyethyloxy)benzene, 2-amino-4-(3-hydroxyethylamino)-1 -methoxybenzene, 1 ,3- diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1 - dimethylaminobenzene, 1 -3-hydroxyethylamino-3,4-methylenedioxybenzene, a-naphthol, 2-methyl-1 -naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2- amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6- dimethoxypyridine, 1 -N-(3-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(3- hydroxyethylamino)toluene, 2,6-dihydroxy-4-methylpyridine, 1 -H-3-methylpyrazol-5-one, 1 -phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2,6- dimethyl[3,2-c]-1 ,2,4-triazole and 6-methylpyrazolo[1 ,5-a]benzimidazole, the addition salts thereof with an acid, and mixtures thereof.

The additional coupler(s), if it (they) are present, each advantageously represent from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

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

Additional dyes:

The composition of the invention may also comprise one or more direct dyes.

The latter dyes are more particularly chosen from ionic or nonionic species, preferably cationic or nonionic species. These direct dyes may be synthetic or of natural origin.

Examples of suitable direct dyes that may be mentioned include azo dyes; methine dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanin dyes, and natural direct dyes, alone or as mixtures.

More particularly, the azo dyes comprise an -N=N- function in which the two nitrogen atoms are not simultaneously engaged in a ring. However, it is not excluded for one of the two nitrogen atoms of the sequence -N=N- to be engaged in a ring.

The dyes of the methine family are more particularly compounds comprising at least one sequence chosen from >C=C< and -N=C< in which the two atoms are not simultaneously engaged in a ring. However, it is pointed out that one of the nitrogen or carbon atoms of the sequences may be engaged in a ring. More particularly, the dyes of this family are derived from compounds of the type such as methines, azomethines, monoarylmethanes and diarylmethanes, indoamines (or diphenylamines), indophenols, indoanilines, carbocyanins, azacarbocyanins and isomers thereof, diazacarbocyanins and isomers thereof, tetraazacarbocyanins and hemicyanins.

As regards the dyes of the carbonyl family, examples that may be mentioned include dyes chosen 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, diketopyrrolopyrrole and coumarin.

As regards the dyes of the cyclic azine family, mention may be made especially of azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine and pyronin.

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

As regards the dyes of porphyrin or phthalocyanin type, it is possible to use cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, for instance alkali metals, alkaline-earth metals, zinc and silicon.

Examples of particularly suitable direct dyes that may be mentioned include nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanin direct dyes, for instance tetraazacarbocyanins (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes; indigoid direct dyes; phthalocyanine direct dyes, porphyrin direct dyes and natural direct dyes, alone or as mixtures.

Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Extracts or decoctions containing these natural dyes and in particular henna- based poultices or extracts may also be used.

When they are present, the direct dye(s) more particularly represent from 0.0001 % to 10% by weight and preferably from 0.005% to 5% by weight of the total weight of the composition.

Basifying agents:

The composition according to the invention also comprises one or more basifying agents.

The basifying agent(s) may be mineral or organic or hybrid.

The mineral basifying agent(s) are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.

The organic basifying agent(s) are preferably chosen from organic amines with a pK_b at 25°C of less than 12, preferably less than 10 and even more advantageously less than 6. It should be noted that it is the pK_b corresponding to the function of highest basicity. In addition, the organic amines do not comprise any alkyl or alkenyl fatty chains comprising more than ten carbon atoms. The organic basifying agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (I) below:

N - W - N in which formula (I) W is a CrC₆ divalent alkylene radical optionally substituted with one or more hydroxyl groups or a CrC₆ alkyl radical, and/or optionally interrupted with one or more heteroatoms such as O, or NR_U; R_x, R_y, R_z, R_t and R_u, which may be identical or different, represent a hydrogen atom or a Ci-C₆ alkyl or CrC₆ hydroxyalkyl or CrC₆ aminoalkyl radical.

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

The term "alkanolamine" means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched CrC₈ alkyl groups bearing one or more hydroxyl radicals.

Organic amines chosen from alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising one to three identical or different Ci-C₄ hydroxyalkyl radicals are in particular suitable for performing the invention.

Among the compounds of this type, mention may be made of monoethanolamine

(MEA), 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(hydroxymethylamino)methane.

More particularly, the amino acids that can be used are of natural or synthetic origin, in their L, D or racemic form, and comprise at least one acid function chosen more particularly from carboxylic acid, sulfonic acid, phosphonic acid or phosphoric acid functions. The amino acids may be in neutral or ionic form.

As amino acids that can be used in the present invention, mention may be made especially of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.

Such basic amino acids are preferably chosen from those corresponding to formula (II) below, and also the salts thereof: in whi s a group chosen from:

; -(CH₂)₃NH₂ ;

-(CH₂)₂NH₂ ; -(CH₂)₂NHCONH₂ ; and

-(CH₂)₂NH C— NH₂

N^H

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

The organic amine may also be chosen from organic amines of heterocyclic type.

Besides histidine that has already been mentioned in the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may be made especially of carnosine, anserine and balenine.

The organic amine may also be chosen from compounds comprising a guanidine function. As amines of this type that can be used in the present invention, besides arginine, which has already been mentioned as an amino acid, mention may be made especially of 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 -sulfonic acid.

Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.

Guanidine carbonate or monoethanolamine hydrochloride may be used in particular.

Preferably, the basifying agent(s) present in the composition of the invention are chosen from alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, and preferably corresponding to those of formula (II). More preferably still, the basifying agent(s) are chosen from monoethanolamine (MEA) and basic amino acids in neutral or ionic form.

Advantageously, the composition according to the invention has a content of basifying agent(s) ranging from 0.01 % to 30% by weight and preferably from 0.1 % to 20% by weight relative to the weight of the composition. According to a first particular embodiment, the composition according to the invention or else the process according to the invention does not use aqueous ammonia, or a salt thereof, as basifying agent.

According to a second embodiment, if the composition or if the process according to the invention does use aqueous ammonia, or a salt thereof, as basifying agent, its content should advantageously not exceed 0.03% by weight (expressed as NH₃), preferably should not exceed 0.01 % by weight, relative to the weight of the composition of the invention.

Preferably, if the composition comprises aqueous ammonia, or a salt thereof, then the amount of basifying agent(s) other than the aqueous ammonia is greater than that of the aqueous ammonia (expressed as NH₃).

Chemical oxidizing agent

The composition of the invention may also comprise one or more chemical oxidizing agents.

The composition of the invention preferentially comprises one or more chemical oxidizing agents.

The term "chemical oxidizing agent" means an oxidizing agent other than atmospheric oxygen.

More particularly, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof and percarbonates of alkali metals or alkaline-earth metals.

This oxidizing agent is advantageously formed from hydrogen peroxide especially in aqueous solution (aqueous hydrogen peroxide solution), the concentration of which may range more particularly from 0.1 % to 50% by weight, more preferably still from 0.5% to 20% by weight and better still from 1 % to 15% by weight relative to the weight of the composition.

Preferably, the composition of the invention does not contain any peroxygenated salts. Solvent:

The composition according to the invention may also comprise one or more organic solvents.

Examples of organic solvents that may be mentioned include linear or branched C₂-

C₄ alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvent(s), if it is (they are) present, represent(s) a content usually ranging from 1 % to 40% by weight and preferably from 5% to 30% by weight relative to the weight of the composition.

Other additives:

The composition according to the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; mineral thickeners, and in particular fillers such as clays or talc; organic thickeners with, in particular, anionic, cationic, nonionic and amphoteric polymeric associative thickeners; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents; opacifiers.

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

The composition may especially comprise one or more mineral thickeners chosen from organophilic clays and fumed silicas, or mixtures thereof.

The organophilic clay may be chosen from montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof. The clay is preferably a bentonite or a hectorite.

These clays may be modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylaryl sulfonates and amine oxides, and mixtures thereof.

Organophilic clays that may be mentioned include quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by the company Rheox, Tixogel VP by the company United Catalyst, Claytone 34, Claytone 40 and Claytone XL by the company Southern Clay; stearalkonium bentonites such as those sold under the names Bentone 27 by the company Rheox, Tixogel LG by the company United Catalyst and Claytone AF and Claytone APA by the company Southern Clay; and quaternium-18/benzalkonium bentonites such as those sold under the names Claytone HT and Claytone PS by the company Southern Clay.

The fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible especially to obtain hydrophilic silicas having a large number of silanol groups at their surface. Such hydrophilic silicas are sold, for example, under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by the company Degussa, and Cab-O-Sil HS-5®, Cab-O-Sil EH-5®, Cab-O-Sil LM-130®, Cab- O-Sil MS-55® and Cab-O-Sil M-5® by the company Cabot. It is possible to chemically modify the surface of the silica via chemical reaction in order to reduce the number of silanol groups. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups may be:

- trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "silica silylate" according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R812® by the company Degussa and Cab-O-Sil TS-530® by the company Cabot.

- dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS- 720® by the company Cabot.

The fumed silica preferably has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.

Preferably, the composition comprises a hectorite, an organomodified bentonite or an optionally modified fumed silica.

When it is present, the mineral thickener represents from 1 % to 30% by weight relative to the weight of the composition.

The composition may also comprise one or more organic thickeners.

These thickeners may be chosen from fatty acid amides (coconut monoethanolamide or diethanolamide, oxyethylenated alkyl ether carboxylic acid monoethanolamide), polymeric thickeners such as cellulose-based thickeners (hydroxyethyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose), guar gum and derivatives thereof (hydroxypropyl guar), gums of microbial origin (xanthan gum, scleroglucan gum), crosslinked homopolymers of acrylic acid or of acrylamidopropanesulfonic acid and associative polymers (polymers comprising hydrophilic regions and hydrophobic regions having a fatty chain (alkyl or alkenyl chain comprising at least 10 carbon atoms) that are capable, in an aqueous medium, of reversibly associating with one another or with other molecules).

According to one particular embodiment, the organic thickener is chosen from cellulose-based thickeners (hydroxyethyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose), guar gum and derivatives thereof (hydroxypropyl guar), gums of microbial origin (xanthan gum, scleroglucan gum) and crosslinked homopolymers of acrylic acid or of acrylamidopropanesulfonic acid, and preferably from cellulose-based thickeners in particular with hydroxyethyl cellulose. The content of organic thickener(s), if it is (they are) present, usually ranges from 0.01 % to 20% by weight and preferably from 0.1 % to 5% by weight relative to the weight of the composition.

The composition of the invention may be in various forms, for instance a solution, an emulsion (milk or cream) or a gel.

Process of the invention:

The composition used in the process according to the invention corresponds to the composition as defined previously and that is free of chemical oxidizing agent; this composition also being used in the presence of at least one chemical oxidizing agent.

This composition used in the process according to the invention (i.e. used in the presence of at least one chemical oxidizing agent) is applied to dry or wet keratin fibres.

It is usually left in place on the fibres for a time generally of from 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.

The temperature during the dyeing process is conventionally between room temperature (between 15°C and 25°C) and 80°C and preferably between room temperature and 60°C.

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

The composition applied in the process according to the invention (i.e. used in the presence of at least one chemical oxidizing agent) is generally prepared by mixing at least two compositions, preferably two or three compositions.

In a first variant of the invention, the composition applied in the process according to the invention (thus used with at least one chemical oxidizing agent) results from the mixing of two compositions.

In particular, a composition (A) (that does not comprise any chemical oxidizing agent) comprising at least one oxidation base, at least one coupler of formula (B7) or of formula (B8) and at least one basifying agent is mixed with a composition (B) comprising at least one chemical oxidizing agent; at least one of the compositions (A) and (B) comprising at least one fatty substance, at least one surfactant, the fatty substance content of the composition applied in the process according to the invention, resulting from the mixing of compositions (A) and (B), comprising at least 25% by weight of fatty substance.

At least one of the compositions (A) and (B) is advantageously aqueous.

The expression "aqueous composition" means a composition comprising at least 5% by weight of water, relative to the weight of this composition. Preferably, an aqueous composition comprises more than 10% by weight of water and more advantageously still more than 20% by weight of water.

Preferably, composition (A) is aqueous. Preferably, composition (B) is also aqueous.

In this variant, composition (A) preferably comprises at least 50% by weight of fatty substances, and more preferably still at least 50% by weight of fatty substances that are liquid at room temperature (25°C), relative to the weight of this composition (A).

Preferably, composition (A) is a direct emulsion (oil-in-water: O/W) or an inverse emulsion (water-in-oil: W/O), and preferably a direct emulsion (O/W).

In this variant, compositions (A) and (B) are preferably mixed together in a weight ratio (A)/(B) ranging from 0.2 to 10 and better still from 0.5 to 2.

In a second variant of the invention, the composition used in the process according to the invention (thus in the presence of at least one chemical oxidizing agent) is derived from the mixing of three compositions. In particular, the three compositions are aqueous or alternatively at least one of them is anhydrous.

More particularly, for the purposes of the invention, the expression "anhydrous cosmetic composition" means a cosmetic composition with a water content of less than 5% by weight, preferably less than 2% by weight and more preferably still less than 1 % by weight relative to the weight of said composition. It should be noted that the water present in the composition is more particularly "bound water", such as water of crystallization in salts, or traces of water absorbed by the raw materials used in the preparation of the compositions according to the invention.

Preferably, use is made of two aqueous compositions (Β') and (C) and one anhydrous composition (Α').

The anhydrous composition (Α') (free of chemical oxidizing agent) then preferably comprises at least one fatty substance, and more preferably at least one liquid fatty substance.

Composition (Β') (free of chemical oxidizing agent) then preferably comprises at least one oxidation base and at least one coupler of formula (B7) or of formula (B8).

Composition (C) then preferably comprises at least one chemical oxidizing agent.

According to this preferred embodiment of the second variant, the basifying agent(s) may be included in compositions (Α') and/or (Β') and preferably only in composition (Β').

As regards the surfactant(s), it is (they are) preferably included in at least one of compositions (Α'), (Β') and (C).

According to this preferred embodiment, the composition used in the process according to the invention, i.e. the composition resulting from the mixing of the three formulations (Α'), (Β') and (C), has a fatty substance content of at least 25% by weight of fatty substance, relative to the weight of the composition resulting from the mixing of the three abovementioned compositions.

In this variant, compositions (Α'), (Β') and (C) are preferably mixed together in a weight ratio [(A')+(B')]/(C) ranging from 0.2 to 10 and more particularly from 0.5 to 2 and in a weight ratio (Α')/(Β') ranging from 0.5 to 10 and preferably from 1 to 5.

Devices:

Finally, the invention relates to a first multi-compartment device comprising a first compartment containing composition (A) as described above and at least a second compartment containing composition (B) as described above; the compositions (A) and (B) of the compartments being intended to be mixed together before application to give a composition according to the invention; the amount of fatty substance of which represents at least 25% by weight relative to the weight of the formulation resulting from the mixing of compositions (A) and (B).

The invention also relates to a second multi-compartment device comprising a first compartment containing composition (Α') as described above and a second compartment containing a cosmetic composition (Β') as described above and at least a third compartment comprising composition (C) as described above, the compositions of the compartments being intended to be mixed together before application to give the composition according to the invention; the amount of fatty substance in the composition representing at least 25% by weight relative to the weight of the composition of the invention, i.e. resulting from the mixing of compositions (Α'), (Β') and (C). The examples that follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES EXAMPLES A

The following compositions are prepared in which the amounts are expressed in grams of active materials.

Composition A

Liquid petroleum jelly 64.5

2-Octyldodecanol 1 1.5

Distearyldimethylammonium-modified hectorite 3

Propylene carbonate 1

Oxyethylenated sorbitan monolaurate (4 EO) 1 1 Glycol distearate 8

Oxyethylenated lauryl alcohol (2 EO) 1

Composition B

Propylene glycol 6.2

Ethyl alcohol 8.25

Hexylene glycol (2-methyl-2,4-pentanediol) 3

Dipropylene glycol 3

Monoethanolamine 14.5

Sodium metabisulfite 0.7

Vitamin C: L-ascorbic acid 0.25

Diethylenetriaminepentaacetic acid, pentasodium salt

as a 40% aqueous solution 1

Hydroxyethyl cellulose (Natrosol 250 HHR, Aqualon) 3.5

2,3-Diaminodihydropyrazolopyrazolone

dimethosulfonate (oxidation base) 2x10^"2 mol

1 -Methylindolin-4-ol (coupler) 2x10^"2 mol

Water qs 100 g

Composition C1 (oxidizing agent)

Cetylstearyl alcohol (Nafol 1618F) 8

Glycerol 0.5

Liquid petroleum jelly 20

Oxyethylenated cetylstearyl alcohol (33 EO) 3

Oxyethylenated rapeseed acid amide (4 EO) 1 .2

Tetrasodium pyrophosphate 0.03

Diethylenetriaminepentaacetic acid, pentasodium salt

0.15 as a 40% aqueous solution

Phosphoric acid 0.1

Tetramethylhexamethylenediamine/1 ,3- dichloropropylene polycondensate (40% aqueous 0.1 solution)

Polydimethyldiallylammonium chloride (40% aqueous

0.2 solution)

Hydrogen peroxide as a 50% aqueous solution 6

Sodium stannate 0.04

Vitamin E 0.1 Phosphoric acid qs pH 2.2

Water qs 100 g

At the time of use, the following are mixed together (by weight):

10 parts of composition A

4 parts of composition B

- 16 parts of composition C

The mixture obtained is then applied to locks of natural hair containing 90% grey hairs.

The "mixture/lock" bath ratio is respectively 10/1 (g/g).

The leave-on time is 30 minutes at 27°C.

After this time, the locks are rinsed, and then washed with shampoo and dried.

The results obtained with the composition of the invention were compared with those obtained with a composition of the prior art (Recital®) containing, in the mixture with the oxidizing agent, the same dyes at the same concentrations.

Calculation of the colour variation (AEg_h*)

The colour build-up (AE_ab*) was evaluated in the CIE L* a* b* system. In this L*, a*, b* system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis. The lower the value of L*, the darker or more intense the colour.

The value of AE_ab* was calculated from the values of L*a*b* according to equation (i) below:

Δ E_ab * = (L* - L₀ *)² + (a* - a₀ *)² + (b* - b₀ *)² _(i)

The colour build-up (AE_Lab*) was calculated on locks of untreated hair (L₀*, a₀* and bo*) and on locks of dyed hair (L*, a* and b*). The L*, a*, b* values for the untreated Natural Grey (NG) hair are as follows L*=57.93, a*=0.76, b*=14.32.

The greater the value of AE_ab*, the better the coverage of the treated fibres and thus of the roots.

Results

L* a* b* AE_ab*

Uncoloured hair - control 57.93 0.76 14.32 -

Coloured hair - invention 47.19 14.97 -0.19 22.97

Coloured hair - comparative 52.55 12.79 1 .58 18.33 It is seen, unexpectedly, that the composition according to the invention make it possible to obtain a much higher colour build-up AE_Lab* on 90% grey hair and thus much better colour coverage at the root than that obtained with a comparative composition. EXAMPLES B

Composition A

Liquid petroleum jelly 64.5

2-Octyldodecanol 1 1.5

Distearyldimethylammonium-modified hectorite 3

Propylene carbonate 1

Oxyethylenated sorbitan monolaurate (4 EO) 1 1

Glycol distearate 8

Oxyethylenated lauryl alcohol (2 EO) 1

Composition B

Propylene glycol 6.2

Ethyl alcohol 8.25

Hexylene glycol (2-methyl-2,4-pentanediol) 3

Dipropylene glycol 3

Monoethanolamine 14.5

Sodium metabisulfite 0.7

Vitamin C: L-ascorbic acid 0.25

Diethylenetriaminepentaacetic acid, pentasodium salt

as a 40% aqueous solution 1

Hydroxyethyl cellulose (Natrosol 250 HHR, Aqualon) 3.5

Oxidation base 2x10^"2 mol

Coupler 2*10^"2 mol

Water qs 100 g

Composition C1 (oxidizing agent)

Cetylstearyl alcohol (Nafol 1618F) 8

Glycerol 0.5

Liquid petroleum jelly 20

Oxyethylenated cetylstearyl alcohol (33 EO) 3 Oxyethylenated rapeseed acid amide (4 EO) 1 .2

Tetrasodium pyrophosphate 0.03

Diethylenetriaminepentaacetic acid, pentasodium salt

0.15

as a 40% aqueous solution

Phosphoric acid 0.1

Tetramethylhexamethylenediamine/1 ,3- dichloropropylene polycondensate (40% aqueous 0.1

solution)

Polydimethyldiallylammonium chloride (40% aqueous

0.2

solution)

Hydrogen peroxide as a 50% aqueous solution 6

Sodium stannate 0.04

Vitamin E 0.1

Phosphoric acid qs pH 2.2

Water qs 100 g

At the time of use, the following are mixed together (by weight):

10 parts of composition A

4 parts of composition B

- 16 parts of composition C

The "mixture/lock" bath ratio is respectively 10/1 (g/g).

The leave-on time is 30 minutes at 27°C.

After this time, the locks are rinsed, and then washed with shampoo and dried.

Calculation of the colour variation (AEg_h*)

The value of AE_ab* was calculated from the values of L*a*b* according to equation (i) below: Δ Ε_αέ * = (L* - L₀ *)² + (a* - a₀ *)² + (b* - b₀ *)² _(i)

Results

It is seen, unexpectedly, that the composition according to the invention makes it possible to obtain a much higher colour build-up AE_Lab* on 90% grey hair and thus much better colour coverage at the root than that obtained with a comparative composition.

Claims

1 . Composition for dyeing keratin fibres, in particular human keratin fibres, comprising:

- at least one fatty substance,

- at least one surfactant,

- at least one oxidation base,

- at least at least one basifying agent,

- at least one indoline coupler of formula (B7) or of formula (B8), and also salts thereof, optical and geometrical isomers and tautomers thereof, and hydrates thereof,

- the fatty substance content representing in total at least 25% by weight relative to the total weight of the composition;

- ng:

(B7) in which:

^• R¹ represents a hydrogen atom; a linear C1-C1₀ alkyl or C₂-Ci₀ alkenyl radical; a branched C₃-C1₀ alkyl or C₃-C1₀ alkenyl or a 3- to 8-membered cyclic alkyl or alkenyl radical optionally comprising one or more unsaturations; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being replaced with at least one oxygen, nitrogen or sulfur atom or with a group S0₂; the alkyl or alkenyl radical being optionally substituted;

^• R², independently of each other, represent:

• a hydroxyl group;

• a halogen atom;

• an optionally substituted, linear C1-C1₀ or branched C₃-C₈ alkyl radical;

• an optionally substituted linear C₂-Ci₀ or branched C3-C1₀ alkenyl radical; the radical R² being connected to the heterocycle via a carbon-carbon single bond;

• a carboxyl or (d-C₈)alkoxycarbonyl group;

• two radicals R² borne by adjacent carbon atoms may form, together with the said carbon atoms, an optionally substituted 5- to 8-membered ring;

• two radicals R² borne by the same carbon atom may form a group =CH-R' with R' representing a hydrogen atom or a linear C1-C9 or branched C₃-C₉ alkyl group;

• n is an integer ranging from 0 to 4; in the case where n is less than 4, the unsubstituted carbon atom(s) bear one or two hydrogen atoms;

^• R³, independently of each other, represent:

• a halogen atom; • an optionally substituted, linear C1-C1₀ or branched C₃-C₈ alkyl radical;

• an optionally substituted linear C₂-Ci₀ or branched C3-C1₀ alkenyl radical;

• a hydroxyl radical, a Ci-C₈ alkoxy radical optionally bearing a hydroxyl group, a d- C₈ alkylthio radical;

• an amino or mono- or dialkylamino group, the alkyl group(s), which may be identical or different, being Ci-C₈, optionally bearing a hydroxyl group;

• -NH-CO-NHR" with R" representing a hydrogen atom or a C1-C4 alkyl radical;

• a group -SR⁴ with R⁴ representing a hydrogen atom or a C1-C4 alkyl radical;

• p is an integer ranging from 0 to 3; in the case where p is less than 3, the unsubstituted carbon atom(s) bear a hydrogen atom;

- formula (B8) being the following:

(B8) in which formula:

^• R¹ represents a hydrogen atom; a linear C1-C1₀ alkyl or C₂-Ci₀ alkenyl radical; a branched C3-C1₀ alkyl or C3-C1₀ alkenyl or a 3- to 8-membered cyclic alkyl or alkenyl radical optionally comprising one or more unsaturations; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being replaced with at least one oxygen, nitrogen or sulfur atom or with a group S0₂; one or more of the carbon atoms of the alkyl or alkenyl radical possibly being substituted with one or more halogen atoms;

^• R², independently of each other, represent:

• a halogen atom;

• a linear C1-C1₀ or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or C1-C4 alkoxy groups;

• a linear C₂-Ci₀ or branched C3-C1₀ alkenyl radical; the said radical being optionally substituted with one or more hydroxyl or C1-C4 alkoxy groups, the radical being connected to the heterocycle via a carbon-carbon single bond;

• a carboxyl or (Ci-C₈)alkoxycarbonyl group;

• two radicals R² borne by adjacent carbon atoms may form, together with the said carbon atoms, a 5- to 8-membered ring;

• two radicals borne by the same carbon atom may form a group =CH-R' with R' representing a hydrogen atom or a linear C1-C9 or branched C₃-C₉ alkyl group;

^• R³ and R⁴, independently of each other, represent:

• a hydrogen atom;

• a halogen atom; • a linear C1-C10 or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or CrC₈ alkoxy groups or halogen atoms;

• a linear C₂-Ci₀ or branched C3-C10 alkenyl radical;

• a Ci-C₈ alkoxy radical;

- at least one oxidation base being chosen at least from heterocyclic oxidation bases when the coupler is of formula (B7).

2. Composition according to the preceding claim, characterized in that the fatty substance(s) are chosen from C₆-Ci₆ alkanes, non-silicone oils of mineral, plant, animal or synthetic origin, fatty alcohols, fatty acid esters, fatty alcohol esters, non-silicone waxes and silicones.

3. Composition according to either one of the preceding claims, characterized in that the fatty substance(s) are liquid at room temperature and at atmospheric pressure.

4. Composition according to any one of the preceding claims, characterized in that the fatty substance(s) are chosen from liquid petroleum jelly, C₆-Ci₆ alkanes, polydecenes, and esters of fatty acids or of fatty alcohols, which are liquid, or mixtures thereof.

5. Composition according to any one of the preceding claims, characterized in that the concentration of fatty substances ranges from 25% to 80% by weight, preferably from 30% to 70% by weight and more advantageously still from 30% to 60% by weight relative to the total weight of the composition.

6. Composition according to any one of the preceding claims, characterized in that the surfactant(s) are chosen from nonionic surfactants, preferably monooxyalkylenated or polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants.

7. Composition according to any one of the preceding claims, characterized in that the oxidation base(s) are chosen from pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and the addition salts thereof.

8. Composition according to the preceding claim, characterized in that the coupler(s) of formula (B7) are chosen from those in which:

^* R¹ represents a hydrogen atom; a linear CrC₆ or branched C₃-C₆ alkyl radical, optionally substituted with one or more hydroxyl, C1-C4 alkoxy, amino or C1-C4 mono- or dialkylamino groups, or halogen atoms;

^* R², independently of each other, represent: a halogen atom;

a linear Ci-C₆ or branched C₃-C₆ alkyl radical, optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, (CrC₈)alkoxycarbonyl, amino or mono- or dialkylamino groups, the alkyl group being Ci-C₄;

· carboxyl or (d-C₈)alkoxycarbonyl;

* R³, independently of each other, represent:

· a halogen atom;

a linear Ci-C₆ or branched C₃-C₆ alkyl radical, optionally substituted with one or more hydroxyl, C1-C4 alkoxy, amino or mono- or dialkylamino groups, the alkyl group being C1-C4, or halogen atoms;

a hydroxyl radical, a C1-C4 alkoxy radical optionally bearing a hydroxyl group, a C1-C4 alkylthio radical;

9. Composition according to any one of the preceding claims, characterized in that the coupler(s) of formula (B7) are chosen from the following compounds, and also the salts thereof, optical and geometrical isomers and tautomers thereof, and hydrates thereof:

C02H

10. Composition according to any one of Claims 1 to 9, p denoting 0 or 1 and R³ denoting a hydroxyl group.

1 1 . Composition according to any one of Claims 1 to 10, R¹ denoting a hydrogen atom or a methyl group.

12. Composition according to any one of Claims 1 to 7, characterized in that the indoline coupler(s) of formula (B8) are chosen from those in which:

* Ri denotes a hydrogen atom or a linear C₁-C₁₀ or branched C₃-C₈ alkyl radical;

* R², independently of each other, represent:

a linear C-I-C-IO or branched C₃-C₈ alkyl radical, optionally substituted with one or more hydroxyl or CrC₄ alkoxy groups;

carboxyl or (d-C₈)alkoxycarbonyl;

· two radicals R² borne by adjacent carbon atoms may form, together with the said carbon atoms, a 5- to 8-membered ring;

two radicals R² borne by the same carbon atom may form a group =CH₂;

n is an integer ranging from 0 to 4; in the case where n is less than 4, the unsubstituted carbon atom(s) bear one or two hydrogen atoms; ^* R³ and R⁴, independently of each other, represent:

a hydrogen atom;

a bromine or chlorine atom;

a Ci-C₈ alkoxy radical;

13. Composition according to any one of Claims 1 to 7 and 12, for which R³ denotes a hydrogen atom.

14. Composition according to any one of Claims 1 to 7 and 12 or 13, for which n denotes 0 or 1 or 2.

15. Composition according to any one of Claims 1 to 7 and 12 to 14, characterized in that the indoline coupler(s) of formula (B8) are chosen from the following compounds, and also the salts thereof, optical and geometrical isomers and tautomers thereof, and hyd

16. Composition according to any one of Claims 1 to 6 and 12 to 15, characterized in that the oxidation base(s) are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, o f/?o-aminophenols and heterocyclic bases, and the addition salts thereof.

17. Composition according to any one of the preceding claims, characterized in that the basifying agents are mineral, organic or hybrid and are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium carbonate or bicarbonate, potassium carbonate or bicarbonate, sodium hydroxide or potassium hydroxide, organic amines chosen from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (I) or mixtures thereof:

N - W - N in which formula (I) W is a CrC₆ divalent alkylene radical optionally substituted with one or more hydroxyl groups or a CrC₆ alkyl radical, and/or optionally interrupted with one or more heteroatoms such as O, or NR_U; R_x, R_y, R_z, R_t and R_u, which may be identical or different, represent a hydrogen atom or a Ci-C₆ alkyl or Ci-C₆ hydroxyalkyl or CrC₆ aminoalkyl radical.

18. Composition according to the preceding claim, characterized in that the basifying agent(s) are chosen from alkanolamines and amino acids in neutral or ionic form.

19. Composition according to any one of the preceding claims, characterized in that it comprises at least one chemical oxidizing agent, preferentially hydrogen peroxide.

20. Process for dyeing keratin fibres, in particular human keratin fibres, which consists in applying to said fibres a composition according to any one of Claims 1 to 19, in the presence of at least one chemical oxidizing agent.

21 . Process according to the preceding claim, characterized in that the composition results from the mixing of two compositions; preferably of a composition (A) comprising at least one oxidation base, at least one coupler of formula (B7) or of formula (B8) and at least one basifying agent and of a composition (B) comprising at least one chemical oxidizing agent, at least one of the compositions (A) and (B) comprising at least one fatty substance, at least one surfactant; the fatty substance content of the composition resulting from the mixing of compositions (A) and (B) comprising at least 25% by weight of fatty substances.

22. Process according to Claim 20, characterized in that the composition results from the mixing of two aqueous compositions (Β') and (C) and of an anhydrous composition (Α'), the anhydrous composition (Α') comprising at least one fatty substance, the composition (Β') comprising at least one oxidation base and at least one coupler of formula (B7), or of formula (B8), the composition (C) comprising at least one chemical oxidizing agent, one or more basifying agents being included in the compositions (Α') and/or (Β') and preferably only in the compositions (Β'), one or more surfactants being included in at least one of the compositions (Α'), (Β') and (C), the fatty substance content of the composition resulting from the mixing of the three compositions (Α'), (Β') and (C) comprising at least 25% by weight of fatty substances.

23. Multi-compartment device comprising a first compartment containing composition (A) as described in Claim 21 and at least a second compartment containing composition (B) as described in Claim 21 , the compositions of the compartments being intended to be mixed together before application, on condition that the amount of fatty substance represents at least 25% by weight relative to the weight of the composition resulting from the mixing of (A) and (B).

24. Multi-compartment device comprising a first compartment containing composition (Α') as described in Claim 22; and a second compartment containing a cosmetic composition (Β') as described in Claim 22 and at least a third compartment comprising composition (C) as described in Claim 22, the compositions of the compartments being intended to be mixed together before application, on condition that the amount of fatty substance represents at least 25% by weight relative to the weight of the composition resulting from the mixing of (Α'), (Β') and (C).