WO2013092482A2

WO2013092482A2 - Oxidation dye composition rich in fatty substances, processes and suitable device for same

Info

Publication number: WO2013092482A2
Application number: PCT/EP2012/075780
Authority: WO
Inventors: Marie MIGNON; Alain Lagrange
Original assignee: L'oreal
Priority date: 2011-12-20
Filing date: 2012-12-17
Publication date: 2013-06-27
Also published as: WO2013092482A3; FR2984146B1; FR2984146A1

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 basifying agent, at least one chemical oxidizing agent and at least one sparingly reactive oxidation base chosen from ionic or nonionic, benzenic or heterocyclic compounds, bearing at least one amine function; the benzenic compounds also comprise an additional amine or hydroxyl function para or ortho to the first amine function; the said compounds having an HOMO energy value of less than or equal to (-180-a) expressed in kcal/mol with: - for the nonionic benzenic compounds bearing an additional amine function: a = 0 - for the ionic benzenic compounds bearing an additional amine function: a = -4 - for the ionic or nonionic benzenic compounds bearing an additional hydroxyl function: a = 7 - for the ionic or nonionic heterocyclic compounds: a = 8; the fatty substance content representing in total at least 25% by weight relative to the total weight of the composition. The invention also relates to processes using the composition according to the invention and multi-compartment devices.

Description

OXIDATION DYE COMPOSITION RICH IN FATTY SUBSTANCES, PROCESSES AND

SUITABLE DEVICE FOR SAME

The present invention relates to a composition for the oxidation dyeing of keratin fibres, in particular human keratin fibres such as the hair, comprising at least one fatty substance, at least one surfactant, at least one basifying agent, at least one benzenic or heterocyclic oxidation base of low reactivity and at least one chemical oxidizing agent, the fatty substance content representing at least 25% by weight relative to the total weight of the composition.

The invention also relates to dyeing processes using this composition, and to two- compartment or three-compartment devices that are suitable for using this composition. The present invention relates to the field of dyeing keratin fibres and more particularly to the field of hair dyeing using oxidation dyes.

These compounds, also known as oxidation bases, are small, colourless or weakly coloured compounds, which, when combined with oxidizing agents, produce coloured species within the keratin fibre by means of an oxidative condensation reaction. In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds.

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 meta-diamines, meta-aminophenols, meta-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.

There is, however, an ongoing search for novel tints and shades. Not all the compounds that can potentially be used as oxidation bases for cosmetic applications are used, since the dyeing performance qualities obtained are unsatisfactory. In particular, the colourations obtained are not strong enough, or give heterogeneous colourations, which is obviously prohibitive. It has been observed that certain sparingly reactive amino benzenic or heterocyclic oxidation bases fall within this case.

One of the objects of the present invention is to significantly improve the dyeing performance qualities that are obtained with sparingly reactive oxidation bases relative to the qualities that would be obtained if they were present in standard dye compositions.

This aim is achieved by the present invention, one subject of which is especially 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 basifying agent,

^* at least one chemical oxidizing agent,

^* at least one oxidation base chosen from ionic or nonionic, benzenic or heterocyclic compounds containing at least one amine function; the benzenic compounds also comprise an additional amine or hydroxyl function para or ortho to the first amine function; the said compounds having an HOMO energy value of less than or equal to (- 180-a) expressed in kcal/mol with:

- for the nonionic benzenic compounds bearing an additional amine function: a = 0

- for the ionic benzenic compounds bearing an additional amine function: a = -4

- for the ionic or nonionic benzenic compounds bearing an additional hydroxyl function: a = 7

- for the ionic or nonionic heterocyclic compounds: a = 8;

^* the fatty substance content representing in total at least 25% by weight relative to the total weight of the composition.

The present invention also relates to dyeing processes using this composition, and to two-compartment or three-compartment devices that are suitable for using this composition.

Thus, the use of the composition according to the invention leads to strong colourations, or alternatively to better uptake of dye into the fibre, and sparingly selective colourations.

Furthermore, the colourations remain stable, in particular with respect to light and shampooing.

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

In that which follows and unless otherwise indicated, the limits of a range of values are included in this range.

The human keratin fibres treated by the method according to the invention are preferably the hair.

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

The compositions according to the invention comprise one or more fatty substances.

The term "fatty substance" means an organic compound that is insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably 1 % and even more preferentially 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, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids, since salified fatty acids constitute soaps that are generally soluble in aqueous media.

More particularly, the fatty substances are chosen from C₆-Ci₆ hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, plant oils of triglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols, esters of fatty acids and/or of fatty alcohols other than triglycerides and plant waxes, non-silicone waxes and silicones.

It is recalled that, for the purposes of the invention, the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 30 carbon atoms, which are optionally substituted, in particular with one or more (in particular 1 to 4) hydroxyl groups.

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

A hydrocarbon-based oil of animal origin that may be mentioned is perhydrosqualene.

The triglyceride oils of plant or synthetic origin are preferably chosen from 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.

The linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms are preferably chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam®.

The fluoro oils may be chosen from 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 may be used in the composition according to the invention are saturated or unsaturated, and linear or branched, and comprise from 6 to 30 carbon atoms and more particularly 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.

The wax(es) that may be used in the cosmetic composition according to the invention are chosen especially from carnauba wax, candelilla wax, esparto grass wax, paraffin wax, ozokerite, plant waxes, for instance olive wax, rice wax, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant blossom sold by the company Bertin (France), animal waxes, for instance beeswaxes, or modified beeswaxes (cerabellina); other waxes or waxy starting materials that may be used according to the invention are especially marine waxes such as the product sold by the company Sophim under the reference M82, and polyethylene waxes or polyolefin waxes in general.

As regards the esters of a fatty acid and/or of a fatty alcohol, 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 mono- or polyacids and of saturated or unsaturated, linear or branched Ci-C₂6 aliphatic mono- or polyalcohols, the total carbon number of the esters more particularly being 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 isononanoate; 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-

C₃o, and preferably C12-C22 fatty acids. It is recalled that the term "sugar" means oxygen- bearing hydrocarbon-based compounds bearing 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 in particular mono- or dioleate, -stearate, -behenate, -oleate/palmitate, -linoleate, -linolenate or -oleate/stearate of sucrose, glucose or methylglucose.

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 palmitate/stearates 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 monopalmitate/stearate-dipalmitate/stearate sold by the company Goldschmidt under the name Tegosoft^® PSE.

The silicones that can be used in the anhydrous cosmetic compositions (B) 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 x 10^"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, in particular 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:

with D": . — Si - O— with D': - Si - O—

I I

CH₃ C₈H₁₇

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 polydi(CrC₂o)alkylsiloxanes.

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 or 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 the company Dow Corning;

- mixtures of a polydimethylsiloxane gum and of 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:

R₂Si0₂/₂, 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 group.

Besides the silicones described above, the organomodified silicones may be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized by 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:

- Silbione® oils of the 70 641 series from Rhodia;

- 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 ambient 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 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, triglycerides, fatty alcohols, esters of a fatty acid and/or of a fatty alcohol other than triglycerides, and silicones, or mixtures thereof.

Preferably, the fatty substance(s) are chosen from liquid petroleum jelly, polydecenes, fatty alcohols and liquid esters of a fatty acid and/or of a fatty alcohol, or mixtures thereof.

Even more preferentially, the fatty substance(s) are chosen from liquid petroleum jelly and octyldodecanol, alone or as a mixture. The composition according to the invention has a fatty substance content of at least 25% by weight. More particularly, 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 total weight of the composition.

Surfactants

The composition according to 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^", -SO₃H, -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, alkylarylpolyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkylether sulfosuccinates, alkylamide sulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamat.es, acylisethionates and N-acyltaurates, salts of alkyl monoesters of polyglycoside- polycarboxylic acids, acyllactylates, D-galactoside uronic acid salts, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts; 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 can 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 chosen 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 aminoalcohol 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.

Alkali metal or alkaline-earth metal salts, and in particular sodium or magnesium salts, are preferably used.

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-C₂o)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, the 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-C₂₀)alkyl betaines, sulfobetaines, (C8-C₂o)alkylamido(C₃-C₈)alkyl betaines and (C₈- C₂o)alkylamido(C₆-C₈)alkyl sulfobetaines.

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, (CrC₄)alkyl- or (d-

C₄)alkylarylsulfonates, 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 or -CH₂-CH₂-C(0)OZ\ or a hydrogen atom;

■ Y' represents the group -C(0)OH, -C(0)OZ' or -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 Ci₀-C₃o alkyl or alkenyl group of an acid R_a-C(0)OH preferably present in hydrolysed linseed oil or coconut 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-C₂₀)alkyl betaines such as coco betaine, and (C₈- C₂o)alkylamido(C₃-C₈)alkyl betaines such as cocamidopropyl betaine, and mixtures thereof. More preferentially, the amphoteric or zwitterionic surfactant(s) are chosen from cocamidopropyl betaine and coco betaine.

The cationic surfactant(s) that can be used in the composition according to the 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 ge below:

(A3)

in which formula (A3):

^■ R₈ to Rii, which are 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 (d- C₄)alkylarylsulfonates, 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, C₁-C30 alkylamide, (Ci₂-C₂₂)alkylamido(C₂-C₆)alkyl, (C₁₂- C₂₂)alkyl acetate and hydroxy(CrC₃o)alkyl groups, and X^" is an anionic counterion chosen from halides, phosphates, acetates, lactates, (Ci-C₄)alkyl sulfates, or (Ci-C₄)alkyl- or (d- C₄)alkylarylsulfonates.

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 d-d alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms;

^■ Ri4 represents a d-d alkyl group;

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

^■ X^" represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (Ci-C₄)alkyl sulfates, or (Ci-C₄)alkyl- or (d- C₄)alkylarylsulfonates. R-12 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;

- di- or triquaternary ammonium salts, in particular of formula (A5) below:

in which formula (A5):

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

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

^■R_16a, Ri7a, Riea, Ri8, Ris>, R20 and R21 , which are identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms; and

^■X^", which are identical or different, represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (CrC₄)alkyl sulfates, or (CrC₄)alkyl- or (Ci-C₄)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.

Such compounds are, for example, Finquat CT-P, provided by the company Finetex (Quaternium 89), and Finquat CT, provided 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 ^{R26 C} ,

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

- a hydrogen atom,

■ R25 is chosen from: - the group ²⁸

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

- a hydrogen atom,

^■ R24, R26 and R₂₈, 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 are identical or different, are integers having values from 2 to 6,

^■ l and t1 , which are identical or different, have the value 0 or 1 , with r2+r1 =2r and t1 +t2=2t,

^■ y is an integer having a value from 1 to 10,

" x and z, which are identical or different, are integers having values from 0 to 10,

^■ X^" represents an organic or inorganic anionic counterion,

with the proviso that the sum x + y + z has a value from 1 to 15, that, when x has the value 0, then R23 denotes R27 and that, when z has the value 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 are identical or different, are chosen from saturated or unsaturated and linear or branched Cn-C₂i hydrocarbon groups, and more particularly from saturated or unsaturated and linear or branched Cn-C₂i alkyl and alkenyl groups.

Preferably, x and z, which are identical or different, have the value 0 or 1 .

Advantageously, y is equal to 1 .

Preferably, r, s and t, which are identical or different, have the value 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)alkylarylsulfonate. 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 functional group.

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:

O

• the group ^R2S ^

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

· a hydrogen atom,

- R25 is chosen from:

O

• the group ^R28 ^

• a hydrogen atom,

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

Advantageously, the hydrocarbon 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 vegetable 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 dialkyl 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 monoester, diester and triester salts 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 and/or polyglycerolated, and containing at least one fatty chain comprising, for example, from 8 to 40 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to especially range from 2 to 200, 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, oxyethylenated and/or oxypropylenated silicones and amine oxides.

The nonionic surfactants are more particularly chosen from mono-oxyalkylenated or polyoxyalkylenated and monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or their combination, preferably oxyethylene units.

Examples of oxyalkylenated nonionic surfactants that may be mentioned include:

• oxyalkylenated (C₈-C₂4)alkylphenols;

· saturated or unsaturated and linear or branched oxyalkylenated C₈-C₃o alcohols;

• saturated or unsaturated and linear or branched oxyalkylenated C₈-C₃₀ amides;

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

• saturated or unsaturated oxyethylenated vegetable 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 oxypropylene units.

In accordance with a 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; and polyoxyethylenated esters of saturated or unsaturated and linear or branched 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 (A7):

^■ 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 comprising 1 .5 mol of glycerol, oleyl alcohol comprising 4 mol of glycerol (I NCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol comprising 2 mol of glycerol (I NCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol comprising 2 mol of glycerol, cetearyl alcohol comprising 6 mol of glycerol, oleocetyl alcohol comprising 6 mol of glycerol, and octadecanol comprising 6 mol of glycerol.

The 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(s) used in the composition of the invention are chosen from nonionic monooxyalkylenated or polyoxyalkylenated surfactants, more particularly monooxyethylenated or polyoxyethylenated, or monooxypropylenated or polyoxypropylenated, nonionic surfactants, 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.

Basifying agents:

As indicated previously, the composition according to the invention comprises one or more basifying agents.

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

For the purposes of the present invention, the term "mineral compound" means any compound bearing in its structure one or more elements from columns 1 to 13 of the Periodic Table of the Elements other than hydrogen.

According to one particular embodiment of the invention, the mineral basifying agent contains one or more elements from columns 1 and 2 of the Periodic Table of the Elements other than hydrogen.

In one preferred variant, the mineral basifying agents has the following structure:

in which:

Z₂ denotes a metal from columns 1 to 13 and preferably 1 or 2 of the Periodic Table of the Elements, such as sodium or potassium;

Zi^x" denotes an anion chosen from the ions C0₃ ^2", OH^", HC0₃ ^2", Si0₃ ^2", HP0₄ ^2", P0₄ ^3" and B₄0₇ ^2", and preferably from the ions C0₃ ^2", OH^" and Si0₃ ^2";

x denotes 1 , 2 or 3;

y denotes 1 , 2, 3 or 4;

m and n denote, independently of each other, 1 , 2, 3 or 4;

with n.y = m.x.

Preferably, the mineral basifying agent corresponds to the following formula (Zi^x" )m(Z2^y+)n, in which Z₂ denotes a metal from columns 1 and 2 of the Periodic Table of the Elements; Zi^x" denotes an anion chosen from the ions C0₃ ^2", OH^" and Si0₃ ^2", x is 1 , y denotes 1 or 2, and m and n denote, independently of each other, 1 or 2 with n.y = m.x.

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, sodium metasilicate or potassium metasilicate, or mixtures thereof, preferably 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,

Advantageously, the basifying agent is chosen from aqueous ammonia, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate and potassium metasilicate, and a mixture thereof, and preferably from alkali metal carbonates.

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 functional group 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:

^Rx\ / ^Rz

^ N W - N

Ry Rt _(l)

in which formula (I) W is a divalent CrC₆ alkylene residue optionally substituted with a hydroxyl group or a Ci-C₆ alkyl radical; and/or optionally interrupted with one or more heteroatoms such as O, or NRu; Rx, Ry, Rz, Rt and Ru, which may be identical or different, represent a hydrogen atom or a Ci-C₆ alkyl, Ci-C₆ 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 implementing the invention.

Among the compounds of this type, mention may be made of monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 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(hydroxymethyl)aminomethane. 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:

_ / ²

R CH₂— CH ^

^C<¾H (ID

i mula (II) R represents a group chosen from:

-(CH₂)₂NH₂ ; -(CH₂)₂NHCONH₂

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 can be used in the present invention, mention may be made especially of carnosine, anserine and baleine.

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 aqueous ammonia, alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, and preferably corresponding to those of formula (II).

Even more preferentially, the basifying agent(s) are chosen from alkanolamines such as monoethanolamine (MEA) and better still from alkanolamines such as monoethanolamine (MEA).

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 said 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).

Oxidation bases:

The composition according to the invention comprises one or more "sparingly reactive" oxidation bases.

As indicated previously, the oxidation base(s) are chosen from ionic or nonionic, benzenic or heterocyclic compounds containing at least one amine function; the benzenic compounds also comprise an additional amine or hydroxyl function para or ortho to the first amine function; the said compounds having an HOMO energy value of less than or equal to (-180-a) expressed in kcal/mol with:

- for the ionic benzenic compounds bearing an additional amine function: a = -4

- for the ionic (cationic or anionic) or nonionic benzenic compounds bearing an additional hydroxyl function: a = 7

- for the ionic (cationic or anionic) or nonionic heterocyclic compounds: a = 8; ^• the fatty substance content representing in total at least 25% by weight relative to the total weight of the composition.

The HOMO energy value calculations are performed using the GEOMOS software (Geometry Optimisation of Molecular Orbitals-Solid/Solvent) (QCPE 584a software; 1989).

It is recalled that HOMO corresponds to the highest occupied molecular orbital. According to one particular embodiment of the invention, the sparingly reactive oxidation base(s) are chosen from:

• benzenic compounds comprising an amine function non substituted or substituted with a C1-C4 alkyl group optionally bearing a hydroxyl group and also comprising an additional amine function non substituted or substituted with a C1-C4 alkyl group optionally bearing a hydroxyl group, or an additional hydroxyl function;

• aromatic or non-aromatic 5- to 6-membered heterocyclic compounds, containing 1 to 3 heteroatoms, preferably nitrogen, optionally substituted with a hydrogen or C1-C4 alkyl group, the said heterocycle being optionally fused to a heterocyclic or non- heterocyclic 5- or 6-membered nucleus comprising 1 or 2 heteroatoms, advantageously nitrogen, optionally substituted with a hydrogen or C1-C4 alkyl group;

• the compounds may optionally be substituted with a C1-C2 alkyl group; trifluoromethyl; a halogen such as chlorine or fluorine; nitro; carboxylic in acid form or in the form of an alkali metal, alkaline-earth metal or ammonium salt; sulfonic in acid form or in the form of an alkali metal, alkaline-earth metal or ammonium salt; sulfonamido optionally substituted preferably with one or two identical or different groups, representing a Ci-C₆ alkyl group optionally bearing a hydroxyl group; amido optionally substituted preferably with one or two identical or different groups, representing a Ci-C₆ alkyl group optionally bearing a hydroxyl group; preferably, a Ci-C₂ alkyl group; trifluoromethyl; a halogen such as chlorine or fluorine; carboxylic in acid form or in the form of an alkali metal, alkaline-earth metal or ammonium salt; sulfonic in acid form or in the form of an alkali metal, alkaline-earth metal or ammonium salt; sulfonamido optionally substituted preferably with one or two identical or different groups, representing a Ci-C₆ alkyl group optionally bearing a hydroxyl group; amido optionally substituted preferably with one or two identical or different groups representing a Ci-C₆ alkyl group optionally bearing a hydroxyl group;

• and the addition salts thereof with an acid. Preferably, the sparingly reactive oxidation base(s) comprise at least one primary amine function.

Examples of such bases that may be mentioned include 2-trifluoromethyl-p- phenylenediamine, 2-amino-5-hydroxybenzoic acid, 2,5-diaminobenzenesulfonic acid, 5- aminosalicylic acid and 3,5-diamino-1 ,2,4-triazole, and the addition salts thereof with acids.

The content of oxidation base(s) of this type usually ranges from 0.001 % to 20% by weight relative to the weight of the composition, and more preferentially from 0.1 % to 10% by weight relative to the weight of the composition.

Couplers:

The composition according to the invention may also comprise one or more additional couplers, usually used in oxidation dyeing.

Among these couplers, mention may be made especially of meta- phenylenediamines, meta-aminophenols, meta-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, sesamol, 1 -3-hydroxyethylamino-3,4-methylenedioxybenzene, oc- 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, 6-hydroxyindoline, 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 they are present in the composition, 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 bases:

The composition according to the invention may optionally comprise at least one additional oxidation base, other than the sparingly reactive oxidation base(s) defined previously.

Additional oxidation bases that may be mentioned include benzenic or heterocyclic oxidation bases and mixtures thereof, such as para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, 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, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis( -hydroxyethyl)-para- phenylenediamine, 4-N,N-bis( -hydroxyethyl)amino-2-methylaniline, 4-N,N-bis( - hydroxyethyl)amino-2-chloroaniline, 2- -hydroxyethyl-para-phenylenediamine, 2-fluoro- para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-( -hydroxypropyl)-para- phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl- para-phenylenediamine, N-ethyl-N-( -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 and 3-hydroxy-1 -(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Preference is particularly given, among the abovementioned para- phenylenediamines, to 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, 2-( -acetylaminoethyloxy)-para- phenylenediamine and their addition salts with an acid.

Mention may be made, among bis(phenyl)alkylenediamines, by way of example, of

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, 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and their addition salts.

Mention may be made, among para-aminophenols, by way of example, of para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2-

(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino-2-

(aminomethyl)phenol, 4-amino-2-[( -hydroxyethyl)aminomethyl]phenol, 4-amino-2- fluorophenol and their addition salts with an acid. Mention may be made, among ortho-aminophenols, by way of example, of 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2- aminophenol and their addition salts.

Mention may be made, among heterocyclic bases, by way of example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Mention may be made, among pyridine derivatives, of the compounds described, for example, in Patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl)amino-3-aminopyridine, 3,4-diaminopyridine and their addition salts.

Other pyridine oxidation bases of use in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or their addition salts described, for example, in Patent Application FR 2 801 308. Mention may be made, by way of example, of pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[1 ,5-a]pyrid-3-ylamine, 2- (morpholin-4-yl)pyrazolo[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-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, pyrazolo[1 ,5- a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[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, 3- aminopyrazolo[1 ,5-a]pyridin-7-ol and their addition salts.

Mention may be made, among pyrimidine derivatives, of the compounds described, for example, in Patents DE 2359399, JP 88-169571 , JP 05-63124 and 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 their addition salts and their tautomeric forms, 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-tert-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-( - hydroxyethyl)amino-1 -methylpyrazole, and the addition salts thereof. 4,5-Diamino-1-(P- methoxyethyl)pyrazole may also be used.

Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially 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 one of its salts.

Use will preferably be made, as heterocyclic bases, 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 one of their salts.

The additional 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.

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

Other additional dyes: The composition according to the invention may optionally comprise one or more synthetic or natural direct dyes, chosen from ionic or nonionic species, preferably cationic or nonionic species.

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

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

When they are present, the direct dye(s) more particularly represent from 0.001 % to 10% by weight and preferably from 0.005% to 5% by weight of the total weight of the composition.

The composition according to the invention is preferably an aqueous composition. The term "aqueous composition" is understood to mean a composition comprising more than 5% by weight of water, preferably more than 10% by weight of water and more advantageously still more than 20% by weight of water.

Solvents:

The composition according to the invention may optionally 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, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvent(s), if they are present, represent 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 other than the polymers mentioned previously; 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 the composition.

According to one embodiment of the invention, the composition may also comprise one or more mineral or organic thickeners.

The mineral thickeners may be chosen from organophilic clays and mineral fillers.

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 can be modified with a chemical compound chosen from quaternary ammoniums, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and their mixtures.

Mention may be made, as organophilic clays, of quaternium-18 bentonites, such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites, such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone APA by Southern Clay; quaternium-18/benzalkonium bentonites, such as those sold under the names Claytone HT and Claytone PS by Southern Clay; quaternium-18 hectorites, such as those sold under the names Bentone Gel DOA, Bentone Gel EC05, Bentone Gel EUG, Bentone Gel IPP, Bentone Gel ISD, Bentone Gel SS71 , Bentone Gel VS8 and Bentone Gel VS38 by Rheox, and Simagel M and Simagel SI 345 by Biophil.

Preferably, the mineral thickeners are chosen from inorganic fillers, in particular kaolinite.

The organic thickener(s) may be chosen from associative or non-associative thickening polymers, in particular associative thickening polymers.

According to the invention, the term "associative thickening polymer" means a thickening polymer comprising at least one C₈-C₃₀ fatty chain and at least one hydrophilic unit.

Preferably, the associative thickening polymers are chosen from polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.

Such polyurethane polyethers are sold especially by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].

When they are present, the thickeners represent from 1 % to 30% by weight relative to the weight of the composition.

Chemical oxidizing agents:

As indicated previously, the composition according to the invention comprises one or more chemical oxidizing agents (in other words, an oxidizing agent which is not only atmospheric oxygen).

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

This chemical 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 composition.

Processes according to the invention:

The process according to the invention thus consists in using the composition as defined previously.

This composition used in the process according to the invention is applied to wet or dry 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 ambient temperature (between 15°C and 25°C) and 80°C and preferably between ambient 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 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 is derived from the mixing of two compositions.

In particular, a composition (A) comprising at least one sparingly reactive oxidation base, optionally at least one coupler, optionally at least one additional oxidation base, 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 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.

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

In this variant, composition (A) preferably comprises at least 10% by weight, more particularly at least 20%, preferably at least 30% and even more preferentially at least 50% by weight of fatty substances, and even more preferentially 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 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 the said composition. It should be noted that the water present in the composition is more particularly "bound water", such as the water of crystallization of the salts or traces of water absorbed by the starting 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') then preferably comprises at least one fatty substance, and more preferentially at least one liquid fatty substance.

Composition (Β') then preferably comprises at least one sparingly reactive oxidation base, optionally at least one coupler, and optionally at least one additional oxidation base. 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 according to the invention, i.e. the composition derived from the mixing of the three compositions (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 derived 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 according to the invention, i.e. the composition derived 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

Preparation of the dye compositions The compositions that follow are prepared; the amounts are expressed in gram unless otherwise indicated.

Oxidizing composition C

Dyeing process

The three compositions detailed above are mixed together at the time of use in the following proportions:

10 g of composition A

4 g of composition B

15 g of composition C

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

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

The leave-on time is 35 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 as the composition of the invention. Results

The colourations obtained are measured using a Minolta CM2600D spectrocolorimeter.

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^* indicates the blue/yellow colour axis. The lower the value of L^*, the darker or more intense the colour.

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

ΔΕ * = (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 greater the value of ΔΕ^*, the better the coverage of the treated fibres and thus of the roots.

As seen in the table above, improved uptake of the weak bases in the oil-rich support of the invention is obtained, when compared with a standard support.

Claims

1 . 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 basifying agent,

* at least one chemical oxidizing agent,

* at least one sparingly reactive oxidation base chosen from ionic or nonionic, benzenic or heterocyclic compounds containing at least one amine function; the benzenic compounds also comprise an additional amine or hydroxyl function para or ortho to the first amine function; the said compounds having an HOMO energy value of less than or equal to (-180-a) expressed in kcal/mol with:

- for the ionic benzenic compounds bearing an additional amine function: a = -4

- for the ionic or nonionic heterocyclic compounds: a = 8;

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

2. Composition according to either of the preceding claims, characterized in that the fatty substance(s) are chosen from C₆-Ci₆ hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, plant oils of triglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols, esters of fatty acids and/or of fatty alcohols other than triglycerides, and plant waxes non-silicone waxes and silicones and more particularly from liquid petroleum jelly, polydecenes, fatty alcohols, and liquid esters of fatty acids and/or of fatty alcohols or mixtures thereof, and preferably from liquid petroleum jelly and octyldodecanol, alone or as a mixture.

3. 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 even more advantageously from 30% to 60% by weight relative to the total weight of the composition.

4. 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.

5. Composition according to any one of the preceding claims, characterized in that the sparingly reactive oxidation base(s) are chosen from:

• and the addition salts thereof with an acid.

6. Composition according to any one of the preceding claims, characterized in that the sparingly reactive oxidation base(s) comprise at least one primary amine function.

7. Composition according to any one of the preceding claims, characterized in that the sparingly reactive oxidation base(s) are chosen from 2-trifluoromethyl-p- phenylenediamine, 2-amino-5-hydroxybenzoic acid, 2,5-diaminobenzenesulfonic acid, 5- aminosalicylic acid and 3,5-diamino-1 ,2,4-triazole, and the addition salts thereof with acids.

8. Composition according to any one of the preceding claims, characterized in that the sparingly reactive oxidation base(s) represent from 0.001 % to 20% by weight relative to the weight of the composition and more preferentially from 0.1 % to 10% by weight relative to the weight of the composition.

9. Composition according to any one of the preceding claims, characterized in that the basifying agent is an organic amine with a pK_b of less than 12, more particularly chosen from alkanolamines, basic amino acids, compounds comprising a guanidine function, and mixtures thereof, and preferably an alkanolamine, in particular monoethanolamine.

10. Composition according to any one of Claims 1 to 8, characterized in that the basifying agent is a mineral base chosen from aqueous ammonia, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate and potassium metasilicate, and a mixture thereof, and preferably from alkali metal carbonates.

1 1 . Process for dyeing keratin fibres, in particular human keratin fibres, which consists in applying to the said fibres a composition according to any one of Claims 1 to 10.

12. Process according to the preceding claim, characterized in that the composition is derived from the mixing of two compositions; preferably of a composition (A) comprising at least one sparingly reactive oxidation base 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 and 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.

13. Process according to Claim 1 1 , characterized in that the composition is derived from the mixing of three compositions, preferably of two aqueous compositions (Β') and (C) and of an anhydrous composition (Α'), the anhydrous composition (Α') comprising at least one fatty substance, composition (Β') comprising at least one sparingly reactive oxidation base, 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 composition (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.

14. Multi-compartment device comprising a first compartment containing composition (A) as described in Claim 12 and at least a second compartment containing composition (B) as described in Claim 12, 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 derived from the mixing of (A) and (B).

15. Multi-compartment device comprising a first compartment containing composition (Α') as described in Claim 13; and a second compartment containing a cosmetic composition (Β') as described in Claim 13 and at least a third compartment comprising composition (C) as described in Claim 13, 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 derived from the mixing of (Α'), (Β') and (C).