WO2013087634A2

WO2013087634A2 - Oxidative dyeing composition comprising a specific perimidine coupler in a medium with high fatty substance content, methods and suitable device

Info

Publication number: WO2013087634A2
Application number: PCT/EP2012/075098
Authority: WO
Inventors: Alain Lagrange; Marie MIGNON
Original assignee: L'oreal
Priority date: 2011-12-13
Filing date: 2012-12-11
Publication date: 2013-06-20
Also published as: FR2983713B1; WO2013087634A3; FR2983713A1

Abstract

Oxidative dyeing composition comprising a specific perimidine coupler in a medium with high fatty substance content, methods and suitable device The present invention relates to an oxidative dyeing composition for keratin fibres, in particular human keratin fibres such as the hair, comprising: - at least 25% by weight, relative to the total weight of the composition, of one or more fatty substances, - one or more surfactants, - one or more alkaline agents, - one or more oxidation bases, and - one or more perimidine couplers chosen from compounds having the following formula (I), their addition salts, their isomers, their tautomers, their solvates and their dimers: The invention also relates to methods using the composition according to the invention and to a multi-compartment device.

Description

Oxidative dyeing composition comprising a specific perimidine coupler in a medium with high fatty substance content, methods and suitable device

The present invention relates to an oxidative dyeing composition for keratin fibres, in particular human keratin fibres such as the hair, comprising at least 25% by weight, relative to the total weight of the composition, of one or more fatty substances, one or more surfactants, one or more alkaline agents, one or more oxidation bases and one or more specific perimidine couplers.

The invention also relates to dyeing methods using this composition in the presence of at least one chemical oxidizing agent, and to a multi-compartment device 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.

Many people have sought for a long time to modify the colour of their hair and in particular to mask their grey hairs. To do this, two main types of dyeing have been developed.

The first type of dyeing is "permanent" or oxidative dyeing, which uses dye compositions containing oxidative 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 via a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or 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 the molecules used as oxidation bases and couplers allows a rich palette of colours to be obtained.

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

The use of perimidine couplers is known in hair dyeing, in particular in document US 5,922,086. However, it has been observed that in classic formulations, the compositions using this type of coupler lead to weak and very selective colours.

Therefore there is a real need for proposing dyeing compositions and/or methods that lead to satisfactory levels of colour in terms of power and selectivity.

This aim is achieved by the present invention, which relates in particular to an oxidative dyeing composition for keratin fibres, in particular human keratin fibres such as the hair, comprising:

- at least 25% by weight, relative to the total weight of the composition, of one or more fatty substances,

- one or more surfactants,

- one or more alkaline agents,

- one or more oxidation bases, and

- one or more perimidine couplers chosen from compounds having the following formula (I), their addition salts, their isomers, their tautomers, their solvates and their dimers:

in which:

Ri, R₂, R₃, R4, R₅, 5 designate independently of each other, a hydrogen atom; an amino group; a halogen atom; a hydroxyl group; a Ci-Cs alkoxy group; a C2-C5-acylamino group; a CHO group;

a linear, branched or cyclic, saturated Ci-Cis alkyl or C2-C18 alkenyl group, where one or more carbon atoms can be replaced by one or more heteroatoms such as oxygen or sulfur or by an NH or N-alkyl group, where the alkyl groups can be substituted by one or more groups chosen from hydroxyl, nitro, nitrile, cyano, carboxylic acid, Ci-Cis alkyl ester, carbamate, carboxamide, amino, alkylamino, dialkylamino, carboxy, alkoxy, halogen atoms, C3-C6 cycloalkyl, a heterocycle containing 5 to 8 members and containing one or more heteroatoms such as nitrogen, sulfur or oxygen, where one or more carbon atoms in the cycloalkyl or heterocycle groups can be substituted by one or more groups chosen from hydroxyl, nitro, nitrile, cyano, carboxylic acid, C1-C18 alkyl ester, carbamate, carboxamide, amino, alkylamino, dialkylamino, carboxy, alkoxy, halogen atom;

Ri may also designate a radical from a perimidine group having formula (I), thereby leading to a dimer, where the two perimidine groups are then preferably connected by their carbon atom located at the 2-position,

or Ri designates a linear or branched C1-C10 alkylene chain that may contain one or more heteroatoms and be substituted by a perimidine radical from a group having formula (I), preferably via the carbon atom located at the 2-position,

groups Ri and R₂ may form a ring with the atoms bearing them, containing one or more heteroatoms, where this ring can be substituted by a Ci-C₆ alkyl group or a hydroxyl group.

Accordingly, the composition according to the invention, when used in the presence of at least one chemical oxidizing agent, leads to intense colours with low selectivity. Moreover, the colours obtained remain stable, in particular towards light.

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

In that which follows and unless otherwise indicated, the limits of a range of values are included within that 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 composition according to the invention comprises 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 chain containing 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 petrolatum or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated.

More particularly, the fatty substances are chosen from C₆-Ci6 hydrocarbons, hydrocarbons comprising more than 16 carbon atoms, non-silicone oils of animal origin, vegetable oils of triglyceride type, synthetic triglycerides, fluorinated oils, fatty alcohols, fatty acid and/or fatty alcohol esters other than the triglycerides and vegetable waxes, non-silicone waxes, 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 by 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 hydrocarbons, they are linear, branched or optionally cyclic, and are preferably alkanes. Mention may be made, by way of example, of hexane, dodecane or isoparaffins, such as isohexadecane or isodecane.

Mention may be made, as hydrocarbon oils of animal origin, of perhydrosqualene.

The triglyceride oils of vegetable or synthetic origin are preferably chosen from liquid triglycerides of fatty acids comprising from 6 to 30 carbon atoms, such as heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, maize oil, soybean oil, cucumber oil, grapeseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, such as those sold by Stearineries Dubois or those sold as Miglyol^® 810, 812 and 818 by Dynamit Nobel, jojoba oil or shea butter oil.

The linear or branched hydrocarbons of inorganic or synthetic origin having more than 16 carbon atoms are preferably chosen from liquid paraffins, petrolatum, liquid petrolatum, polydecenes or hydrogenated polyisobutene, such as Parleam®. The fluorinated oils can be chosen from perfluoromethylcyclopentane and perfluoro-l ,3-dimethylcyclohexane, sold as Flutec^® PCI and Flutec^® PC3 by BNFL Fluorochemicals; perfluoro-l ,2-dimethylcyclo butane; perfluoroalkanes, such as dodecafluoropentane and tetradecafluorohexane, sold as PF 5050^® and PF 5060^® by 3M, or bromoperfluorooctyl, sold as Foralkyl^® by Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; or perfluoromorpholine derivatives, such as 4-(trifluoromethyl)perfluoromorpholine, sold as PF 5052^® by 3M.

The fatty alcohols that may be used in the cosmetic composition 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. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and their mixture (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol.

The wax(es) that may be used in the cosmetic composition 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 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 Sophim as M82, and polyethylene waxes or polyolefin waxes in general.

The fatty acids that may be used in the cosmetic composition may be saturated or unsaturated and contain from 6 to 30 carbon atoms and in particular from 9 to 30 carbon atoms. They are more specifically chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid.

As regards the fatty acid and/or fatty alcohol esters, which are advantageously different than 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-Ci₅alkyl 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 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy

C2-C26 alcohols may also be used.

Mention may in particular be made 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 palmitates, 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" is understood to mean oxygen-bearing hydrocarbon-based compounds that contain several alcohol functions, with or without aldehyde or ketone functions, and that comprise at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Mention may be made, as suitable sugars, for example, of sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose and their derivatives, in particular alkyl derivatives, such as methyl derivatives, for example methylglucose.

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

The esters according to this alternative form can also be chosen from mono-, di-, tri- and tetraesters, polyesters and their mixtures.

These esters can, for example, be oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates or their mixtures, such as, in particular, oleate/palmitate, oleate/stearate or palmitate/stearate mixed esters.

More particularly, use is made of mono- and diesters and in particular mono- or di-oleate, -stearate, -behenate, -oleate/palmitate, -linoleate, -linolenate or - oleate/stearate of sucrose, glucose or methylglucose.

Mention may be made, by way of example, of the product sold as Glucate® DO by Amerchol, which is a methylglucose dioleate.

Mention may also be made, by way of examples of esters or mixtures of esters of sugar of fatty acid, of:

- the products sold as F160, F140, F110, F90, F70 and SL40 by Crodesta, respectively denoting sucrose palmitate/stearates formed of 73% monoester and 27% di- and triester, of 61% monoester and 39% di-, tri- and tetraester, of 52% monoester and 48%) di-, tri- and tetraester, of 45% monoester and 55% di-, tri- and tetraester, and of 39% monoester and 61% di-, tri- and tetraester, and sucrose monolaurate;

- the products sold as Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed of 20% monoester and 80% diester, triester and polyester; the sucrose monopalmitate/stearate-dipalmitate/stearate sold by Goldschmidt as Tegosoft^® PSE.

The silicones that can be used in the cosmetic composition according to the present invention are volatile or non-volatile, cyclic, linear or branched silicones, which are unmodified or modified by organic groups, having a viscosity from 5x 10^~6 to 2.5m²/s at 25°C, and preferably l lO^"5 to lm²/s.

The silicones which can be used in accordance with the invention can be provided 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 more detail in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academic Press. They can 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 comprising from 3 to 7 and preferably from 4 to 5 silicon atoms. They are, for example, octamethylcyclotetrasiloxane, sold in particular as Volatile Silicone^® 7207 by Union Carbide or Silbione^® 70045 V2 by

Rhodia, decamethylcyclopentasiloxane, sold as Volatile Silicone^® 7158 by Union

Carbide and Silbione^® 70045 V5 by Rhodia, and their mixtures.

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

D" D' D"— D'

CH₃ CH₃ with D" : — Si— O with D' : — Si— O

I I

CH₃ C₈H₁₇

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-l , l '-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 5x 10^"6 m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular as SH 200 by Toray Silicone. Silicones coming within this category are also described in the paper 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 by the organofunctional groups above, and their mixtures.

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 Standard ASTM 445 Appendix C.

Mention may be made, among these polydialkylsiloxanes, without implied limitation, of the following commercial products:

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

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

- the oils of the 200 series from Dow Corning, such as DC200 having 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 as dimethiconol (CTFA), such as the oils in the 48 series from Rhodia.

Mention may also be made, in this category of polydialkylsiloxanes, of the products sold as Abil Wax^® 9800 and 9801 by Goldschmidt, which are polydi(Ci- C2o)alkylsiloxanes.

The silicone gums which can be used in accordance with the invention are in particular polydialkylsiloxanes and preferably polydimethylsiloxanes having 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, isoparaffms, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures.

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

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

- the mixtures of a polydimethylsiloxane gum and of a cyclic silicone, such as the product SF 1214 Silicone Fluid from 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;

- the 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 General Electric. The product SF 1236 is the mixture of a gum SE 30 defined above having a viscosity of 20 m²/s and of an oil SF 96 with a viscosity of 5x 10^"6 m²/s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.

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

R₂Si0₂/2, R₃SiOi/₂, RSi0_3/2 and Si0_4/2

in which R denotes an alkyl having from 1 to 16 carbon atoms. Among these products, those which are particularly preferred are those in which R denotes a lower Ci-C₄ alkyl group, more particularly methyl.

Mention may be made, among these resins, of the product sold as Dow Corning 593 or those sold as Silicone Fluid SS 4230 and SS 4267 by General Electric, which are silicones having dimethyl/trimethylsiloxane structure.

Mention may also be made of the resins of the trimethylsiloxy silicate type, sold in particular as X22-4914, X21-5034 and X21-5037 by Shin-Etsu.

The organomodified silicones which can be used in accordance with the invention are silicones as defined above and comprising, in their structure, one or more organo functional groups attached via a hydrocarbon group. Besides the silicones described above, the organomodified silicones may be polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized by the organofunctional groups mentioned previously.

The polyalkylarylsiloxanes are chosen in particular from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with viscosity ranging from l x lO^"5 to 5x 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 in the 70 641 series from Rhodia;

- the oils in the Rhodorsil® 70 633 and 763 series from Rhodia;

- the oil Dow Coming 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 PN 1000 and PHI 000;

- some oils in the SF series from General Electric, such as SF 1023,

SF 1154, SF 1250 and SF 1265.

Mention may be made, among the organomodified silicones, of polyorganosiloxanes comprising:

polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C6-C24 alkyl groups, such as the products named dimethicone copolyol sold by Dow Coming as DC 1248 or the oils Silwet^® L 722, L 7500, L 77 and L 711 by Union Carbide, and the (Ci₂)alkyl methicone copolyol sold by Dow Coming as Q2 5200;

- substituted or unsubstituted amino groups, such as the products sold as GP 4 Silicone Fluid and GP 7100 by Genesee or the products sold as Q2 8220 and

Dow Corning 929 or 939 by Dow Corning. The substituted amino groups are in particular C₁-C4 aminoalkyl groups;

- alkoxylated groups, such as the product sold as Silicone Copolymer F- 755 by SWS Silicones, and Abil Wax^® 2428, 2434 and 2440 by Goldschmidt.

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

More particularly, the fatty substances are chosen from compounds that are liquid or pasty at room temperature and atmospheric pressure. Preferably, the fatty substance is a compound which is liquid at the temperature of 25°C and at atmospheric pressure.

The fatty substance(s) are advantageously chosen from C₆-Ci6 hydrocarbons, hydrocarbons comprising more than 16 carbon atoms, non-silicone oils of animal origin, vegetable oils of triglyceride type, synthetic triglycerides, fluorinated oils, fatty alcohols, fatty acid and/or fatty alcohol esters other than the triglycerides and vegetable waxes, non-silicone waxes, silicones and their mixtures.

Preferably, the fatty substance(s) are chosen from liquid petrolatum, polydecenes, fatty alcohols, liquid fatty acid and/or fatty alcohol esters and their mixtures.

Even more preferably, the fatty substances are chosen from liquid petrolatum and octyldodecanol.

The composition according to the invention has a fatty substance content of at least 25% by weight relative to the total weight of the composition. More specifically, 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.

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 or non-ionic surfactants, and preferentially non-ionic 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 counter-ion such as an alkali metal, an alkaline-earth metal or an ammonium.

Mention may be made, as examples of anionic surfactants which can be used in the composition according to the invention, of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, a-olefm 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 can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The salts of C₆-C24 alkyl monoesters and 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, it (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 aminoalcohol 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-l-propanol salts, 2-amino-2-methyl-l,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.

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

In particular, it is preferable to use (Ci2-C2o)alkyl sulfates, (Ci2-C2o)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal, ammonium, aminoalcohol and alkaline-earth metal salts, or a mixture of these compounds. Better still, it is preferable to use sodium lauryl ether sulfate comprising 2.2 mol of ethylene oxide.

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

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

Ra-C(0)-NH-CH₂-CH₂-N⁺(Rb)(Rc)-CH₂C(0)0^", M⁺ , X

(Al)

in which formula (Al):

Ra denotes a C₁₀-C₃₀ alkyl or alkenyl group derived from an acid RaCOOH preferably present in hydro lyzed coconut oil, a heptyl, nonyl or undecyl group;

Rb denotes a beta-hydroxyethyl group; and

Rc denotes a carboxymethyl group;

M+ denotes a cationic counter-ion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine, and

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

Ra'-C(0)-NH-CH₂-CH₂-N(B)(B') (A2)

in which formula (A2):

B denotes the group -CH₂-CH₂-0-X;

B' denotes the group -(CH₂)zY', where z = 1 or 2;

X denotes 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^* denotes the group -C(0)OH, -C(0)OZ', -CH₂-CH(OH)-S0₃H or the group -CH₂-CH(OH)-S0₃-Z';

Z' denotes a cationic counter-ion of an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine; Ra' denotes a C10-C₃₀ alkyl or alkenyl group of an acid Ra'-C(0)OH which is preferably present in coconut oil or in hydrolysed linseed oil, or an alkyl group, especially a C₁₇ group, and its iso form, or an unsaturated C₁₇ group.

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

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

Among the above-mentioned amphoteric or zwitterionic surfactants, use may be made preferably of (C₈-C2o)alkyl betaines, such as coco betaine, or (C₈- C2o)alkylamido(C₃-C₈)alkyl betaines such as cocamidopropyl betaine, and their mixtures. More preferably, the amphoteric or zwitterionic surfactant(s) are chosen from cocamidopropyl betaine and coco betaine.

The cationic surfactant(s) which 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 their mixtures.

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

those corresponding to the general formula (A3) below:

(A3)

in which formula (A3):

R8 to R11 , which may be identical or different, denote 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 Rs to Rn comprises from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms; and X- denotes an organic or inorganic anionic counter-ion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C4)alkyl sulfates, (Ci-C4)alkyl- or (Ci-C4)alkylaryl-sulfonates, particularly methyl sulfate and ethyl sulfate.

Aliphatic groups Rs to Ri i may also comprise heteroatoms such as oxygen, nitrogen, sulfur and halogens in particular.

Aliphatic groups Rs to Rn are chosen, for example, from C1-C30 alkyl, Ci- C30 alkoxy, polyoxy(C2-C6)alkylene, C1-C30 alkylamide, (Ci2-C22)alkylamido(C2- C₆)alkyl, (Ci2-C22)alkylacetate, and C1-C30 hydroxyalkyl groups, X^" is an anionic counter-ion chosen from halides, phosphates, acetates, lactates, (Ci-C4)alkyl sulfates, and (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonates.

Preference is given, among the quaternary ammonium salts having the formula (A3), firstly to tetraalkylammonium chlorides, such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group includes 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 as Ceraphyl® 70 by Van Dyk;

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

(A4)

in which formula (A4):

R12 denotes an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example tallow fatty acid derivatives;

Rn denotes a hydrogen atom, a C1-C4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms; Ri4 denotes a C₁-C4 alkyl group;

Ri5 denotes a hydrogen atom or a C₁-C₄ alkyl group;

X- denotes an organic or inorganic anionic counter-ion, such as that chosen from halides, phosphates, acetates, lactates, (Ci-C₄)alkyl sulfates, or (Ci-C₄)alkyl- or (Ci-C₄)alkylarylsulfo nates.

R12 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 R15 denotes a hydrogen atom. Such a product is sold, for example, as Rewoquat® W 75 by Rewo;

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

17 R ' ,

^R16— — (CH,)— N— R ^'21 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 by one or more oxygen atoms;

Ri7 is selected from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a -(CH₂)₃-N+(Ri6a)(Ri7a)(Ri8a) group, X-;

Ri6a, Ri7a, Ri8a, Ri8, Ri9, R₂o and R₂i, which may be 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, denote an organic or inorganic anionic counter-ion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci- C₄)alkyl sulfates, or (Ci-C₄)alkyl- or (Ci-C₄)alkylarylsulfo nates, in particular methyl sulfate and ethyl sulfate.

Such compounds are, for example, Finquat CT-P, provided by Finetex (Quaternium 89), or Finquat CT, provided by Finetex (Quaternium 75);

- quaternary ammonium salts comprising one or more ester functional groups, such as those of following formula (A6): O X (C HJ-R25

/

v24 0-C_rH_r2(OH)_r j N†C_tH₍₂(OH) O- X ^{, x}23

²² (A6) in which formula (A6):

R22 is chosen from Ci-C₆ alkyl groups and Ci-C₆ hydroxyalkyl or dihydroxyalkyl groups,

R23 is chosen from:

O

- the ²⁶ group,

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

- a hydrogen atom,

R25 is chosen from:

O

- the ^R2⁸ ^ group,

- 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 may be identical or different, are integers ranging from 2 to

6,

rl and tl, which may be identical or different, are equal to 0 or 1, with r2+rl=2r and tl+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- denotes an organic or inorganic anionic counter-ion,

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-C₂₁ hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn- C21 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 counter-ion X- is preferably a halide, such as chloride, bromide or iodide; a (Ci-C4)alkyl sulfate or a (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion compatible with the ammonium containing an ester function.

The anionic counter-ion 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 having 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

p

the group ²⁶

methyl, ethyl or C14-C22 hydrocarbon groups, a hydrogen atom,

- R25 is chosen from:

O the group ^R28 ^

a hydrogen atom,

- R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.

Advantageously, the hydrocarbon radicals are linear.

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

triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and their mixtures. 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 alkyldiisopropanolamme, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of plant or animal origin, or by transesterification of their methyl esters. 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, as Dehy quart® by Henkel, Stepanquat® by Stepan, Noxamium® by Ceca or Rewoquat® WE 18 by 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. Use may also be made of 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, provided by Kao as 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 their mixtures, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride and dipalmitoylethylhydroxyethylammonium methosulfate, and their mixtures.

Examples of non- ionic 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. 116-178. They are especially chosen from alcohols, a-diols and (Ci- C2o)alkylphenols, these compounds being polyethoxylated, polypropoxylated and/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-alkylglucamine and of N- acylmethylglucamine, aldobionamides and amine oxides.

The non-ionic surfactants are chosen more particularly from mono- or polyoxyalkylenated or mono- or polyglycerolated non-ionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or their combination, preferably oxyethylene units.

Mention may be made, as examples of oxyalkylenated non-ionic surfactants, of:

oxyalkylenated (Cs-C24)alkylphenols; saturated or unsaturated and linear or branched oxyalkylenated C8-C30 alcohols;

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

esters of saturated or unsaturated and linear or branched C8-C30 acids and of polyethylene glycols;

polyoxyethylenated esters of saturated or unsaturated and linear or branched C8-C30 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 non- ionic surfactants do not comprise oxypropylene units.

In accordance with a preferred embodiment of the invention, the oxyalkylenated non-ionic 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 non-ionic surfactants, monoglycerolated or polyglycerolated C8-C40 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 denotes a linear or branched C8-C40 and preferably C8-C30 alkyl or alkenyl radical; and

m denotes a number ranging from 1 to 30 and preferably from 1 to 10.

As examples of compounds having the formula (A7) that are suitable within the context of the invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol comprising 1.5 mol of glycerol, oleyl alcohol comprising 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol comprising 2 mol of glycerol (INCI 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 having the formula (A8) may denote a mixture of alcohols in the same way that the value of m denotes a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohols may coexist in the form of a mixture.

Use is more preferably made, among the mono- or polyglycerolated alcohols, of the Cs/Cio alcohol comprising 1 mol of glycerol, the C₁₀/C₁₂ alcohol comprising 1 mol of glycerol and the C₁₂ alcohol comprising 1.5 mol of glycerol.

Preferably, the surfactant used in the composition of the invention is a monooxyalkylenated or polyoxyalkylenated, particularly monooxyalkylenated or polyoxyalkylenated and monoglycerolated or polyglycerolated, non- ionic surfactant, more particularly monooxyethylenated or polyoxyethylenated, monooxypropylenated or polyoxypropylenated, or their combinations, more specifically monooxyethylenated or polyoxyethylenated.

Preferably, the surfactant(s) is (are) chosen from non-ionic surfactants or from anionic surfactants. More particularly, the surfactant(s) present in the composition is (are) chosen from non-ionic surfactants.

More preferably still, the non-ionic surfactants are chosen from polyoxyethylenated sorbitol esters and polyoxyethylenated fatty alcohols, and their mixtures.

In the composition of the invention, the amount of surfactant(s) in the composition preferably varies 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.

Alkaline agents

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

The alkaline agent(s) may be inorganic or organic or hybrid.

For the purposes of the present invention, the term "inorganic 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 a specific embodiment of the invention, the inorganic alkaline 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 inorganic alkaline agent has the following structure:

(Z₁ ^x-)_m(Z₂ ^y+)_n

In which:

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

Zi^x" designates an anion chosen from among C0₃ ^2", OH^",

HC0₃ ^2", Si0₃ ^2", HP0₄ ^2", P0₄ ^3", B₄O₇ ^2" ions, preferably from C0₃ ² , OH^", Si0₃ ^2" ions; 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 inorganic alkaline agent corresponds to the following formula (Z_! ^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^", 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 inorganic alkaline agent(s) are preferably chosen from ammonia, alkaline carbonates or bicarbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide (caustic soda), potassium hydroxide (potash), sodium metasilicate, potassium metasilicate and their mixtures, and more specifically, alkaline carbonates.

The organic alkaline agent(s) are preferably chosen from organic amines with a p¾ at 25°C below 12, preferably below 10 and even more advantageously below 6. It should be noted that it is the p¾ 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 alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds having formula (II) below: Rx Rz

^ N - W - N

Ry ^N Rt

Formula (II) in which W is a divalent Ci-C₆ alkylene radical optionally substituted with one or more hydroxyl groups or a Ci-C₆ alkyl radical, and/or optionally interrupted by one or more heteroatoms such as O, or nRu; Rx, Ry, Rz, Rt, Ru, which may be the same or different, denote a hydrogen atom or a Ci-C₆ alkyl radical or a Ci-C₆ hydroxyalkyl radical, or Ci-C₆ aminoalkyl.

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

"Alkanolamine" is understood to mean an organic amine comprising a primary, secondary or tertiary amine function and one or more linear or branched Ci- C8 alkyl groups carrying one or more hydroxyl radicals.

Organic amines chosen from alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines, comprising one to three identical or different C₁-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, Ν,Ν-dimethylethanolamine, 2-amino- 2-methyl-l-propanol, triisopropanolamine, 2-amino-2-methyl-l,3-propanediol, 3- amino- 1,2-propanediol, 3-dimethylamino-l,2-propanediol and tris(hydroxymethyl)aminomethane.

More particularly, the amino acids which can be used are of natural or synthetic origin, in their L, D or racemic form, and comprise at least one acid functional group chosen more particularly from carboxylic acid, sulfonic acid, phosphonic acid or phosphoric acid functional groups. The amino acids can be in the 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, iso leucine, 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 the formula (III) below:

NH,

/ ²

R CH₂— CH ^

^C¾^H (III)

Formula (III) in which, R denotes a group chosen from:

-(CH₂)₃NH₂

-(CH₂)₂NH₂; -(CH₂)₂NHCONH₂.

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

The organic amine can also be chosen from organic amines of heterocyclic type. Mention may in particular be made, in addition to histidine, already mentioned in the amino acids, of pyridine, piperidine, imidazole, triazole, tetrazole or benzimidazole.

The organic amine can 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 balenine.

The organic amine can also be chosen from compounds comprising a guanidine functional group. Mention may in particular be made, as amines of this type which can be used in the present invention, in addition to arginine, already mentioned as an amino acid, 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-l -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.

Use may in particular be made of guanidine carbonate or monoethanolamine hydrochloride. Preferably, the alkaline 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 having the formula (III), compounds including a guanidine function and their mixtures.

Even more preferentially, the alkaline agent(s) are chosen from alkanolamines such as monoethanolamine (MEA).

Advantageously, the composition according to the invention has a content of alkaline agents ranging from 0.01% to 30% by weight and preferably from 0.1% to 20% by weight relative to the weight of said composition.

According to a first specific embodiment, the composition according to the invention or else the method according to the invention does not employ aqueous ammonia or one of its salts as alkaline agent.

According to a second embodiment, if the composition or if the method according to the invention does use aqueous ammonia or one of its salts as alkaline 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 one of its salts, then the amount of alkaline 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 oxidation bases.

The oxidation bases may be chosen from heterocyclic bases, benzene bases, and their mixtures;

By way of example, the oxidation bases are chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols, heterocyclic bases, and their addition salts.

Mention may be made, by way of example, of para-phenylenediamines, of para-phenylenediamine, para-toluylenediamine, 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 -methyl aniline, N,N-bis-( -hydroxyethyl)- para-phenylenediamine, 4-N,N-bis-( -hydroxyethyl)amino 2-methyl aniline, 4-N,N- bis-( -hydroxyethyl)amino 2-chloro aniline, 2- -hydroxyethyl-para- phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para- phenylenediamine, N-( -hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl- para-phenylenediamine, Ν,Ν-dimethyl 3-methyl-para-phenylenediamine, N,N-(ethyl, -hydroxyethyl)-para-phenylenediamine, N-( ,y-dihydroxypropyl)-para- phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para- phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine, 2-β- acetylaminoethyloxy-para-phenylenediamine, N-( -methoxyethyl)-para- phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β hydroxy ethylamino 5 -amino toluene, 3-hydroxy-l-(4'-aminophenyl)pyrrolidine and their addition salts with an acid.

Among the para-phenylenediamines mentioned above, para- phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylenediamine, 2-β- 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 their addition salts with an acid, are particularly preferred.

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, Ν,Ν'- bis(4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'- amino-3'-methylphenyl)ethylenediamine, l,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[l,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[l,5-a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[l,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[l,5-a]pyrid-3-ylamine, (3- aminopyrazo lo [ 1 ,5 -a]pyrid-7-yl)methano 1, 2-(3 -aminopyrazo lo [ 1 ,5 -a]pyrid-5 - yl)ethano 1, 2-(3 -aminopyrazo lo [ 1 ,5 -a]pyrid-7-yl)ethano 1, (3 -aminopyrazo lo [ 1 ,5 - a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[l,5-a]pyridine, 3,4- diaminopyrazolo[l,5-a]pyridine, pyrazolo[l,5-a]pyridine-3,7-diamine, 7-(morpholin- 4-yl)pyrazolo[l,5-a]pyrid-3-ylamine, pyrazolo[l,5-a]pyridine-3,5-diamine, 5- (morpholin-4-yl)pyrazo lo [ 1 ,5-a]pyrid-3 -ylamine, 2- [(3 -aminopyrazo lo [ 1 ,5 -ajpyrid- 5 -yl)(2-hydroxyethyl)amino] ethanol, 2- [(3 -aminopyrazo lo [ 1 ,5-a]pyrid-7-yl)(2- hydroxyethyl)amino]ethanol, 3-aminopyrazolo[l ,5-a]pyridin-5-ol, 3- aminopyrazo lo [ 1 ,5 -a]pyridin-4-ol, 3 -aminopyrazo lo [ 1 ,5 -a]pyridin-6-ol, 3 - aminopyrazolo[l,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-triaminopyrimi dine 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- l-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 -tert-butyl-3- methylpyrazole, 4,5-diamino- 1 -( -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-l -isopropylpyrazole, 4,5-diamino-3- methyl- 1 -isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino- 1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-l-methyl-4- methylaminopyrazole, 3,5-diamino-4-( -hydroxyethyl)amino-l -methylpyrazole, and their addition salts. 4,5-Diamino-l-( -methoxyethyl)pyrazole may also be used.

Use will preferably be made of a 4,5-diaminopyrazole and more preferably still of 4,5-diamino- l-( -hydroxyethyl)pyrazole and/or one of its salts.

Mention may also be made, as pyrazole derivatives, of diamino-N,N- dihydropyrazolopyrazolones and in particular those described in Application FR-A-

2 886 136, such as the following compounds and their addition salts: 2,3-diamino- 6,7-dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2-amino-3-ethylamino-6,7- dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2-amino-3-isopropylamino-6,7- dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2-amino-3-(pyrrolidin- 1 -yl)-6,7- dihydro- lH,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- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2-amino-3- dimethylamino-6,7-dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2,3-diamino- 5,6,7,8-tetrahydro- lH,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- l-yl)-l,2-diethyl-l,2-dihydropyrazol-3-one or 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-lH,5H- pyrazolo[l,2-a]pyrazol-l-one and/or one of its salts. Use will preferably be made, as heterocyclic bases, of 4,5-diamino-l-( - hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-lH,5H-pyrazolo[l ,2- a]pyrazol-l-one and/or one of their salts.

Perimidine couplers having formula (I)

The composition according to the invention further comprises one or more perimidine couplers chosen from compounds having the following formula (I), their addition salts, their isomers, their tautomers, their solvates and their dimers:

in which:

Ri, R₂, R₃, R4, R5, 5 designate independently of each other, a hydrogen atom; an amino group; a halogen atom; a hydroxyl group; a Ci-Cs alkoxy group; a C₂-C₅ acylamino group; a CHO group;

a linear, branched or cyclic, saturated Ci-Cis alkyl or C₂-Cis alkenyl group, where one or more carbon atoms can be replaced by one or more heteroatoms such as oxygen or sulfur or by an NH or N-alkyl group, where the alkyl groups can be substituted by one or more groups chosen from hydroxyl, nitro, nitrile, cyano, carboxylic acid, Ci-Cis alkyl ester, carbamate, carboxamide, amino, alkylamino, dialkylamino, carboxy, alkoxy, halogen atoms, C₃-C₆ cycloalkyl, a heterocycle containing 5 to 8 members and containing one or more heteroatoms such as nitrogen, sulfur or oxygen, where one or more carbon atoms in the cycloalkyl or heterocycle groups can be substituted by one or more groups chosen from hydroxyl, nitro, nitrile, cyano, carboxylic acid, Ci-Cis alkyl ester, carbamate, carboxamide, amino, alkylamino, dialkylamino, carboxy, alkoxy, halogen atom; Ri may also designate a radical from a perimidine group having formula (I), thereby leading to a dimer, where the two perimidine groups are then preferably connected by their carbon atom located at the 2-position,

or Ri designates a linear or branched Ci-Cio alkylene chain that may contain one or more heteroatoms and substituted by a perimidine radical from a group having formula (I), preferably via the carbon atom located at the 2-position,

groups Ri and R₂ may form a ring with the atoms bearing them, containing one or more heteroatoms, where this ring can be substituted by a Ci-C₆ alkyl group or a hydroxy 1 group.

Preferably, the perimidine couplers according to the invention are chosen from:

,

CH2— (CH2) 4— CO2H

Compound 91 Compound 92

1 H-Perimidine-2-methanol lH-Perimidine-2-hexanoic acid

Compound 93 Compound 94

lH-Perimidine-2-pentanoic acid

lH-Perimidine-2-butanoic acid (CH₂)7-Me

Compound 95 Compound 96

lH-Perimidine-2-propanoic acid 1H-Perimidine, 2-nonyl-

2~ Bu-n

Compound 97 Compound 98

1H-Perimidine, 2-heptyl- 1H-Perimidine, 2-pentyl- (CH₂)i3-Me

Compound 99 Compound 100

1H-Perimidine, 2-heptadecyl- 1H-Perimidine, 2-pentadecyl- (CH₂)₉— Me

Compound 101

1H-Perimidine, 2-tridecyl- Compound 102

1H-Perimidine, 2-undecyl-

1H-Perimidine, 2-methyl-

1H-Perimidine, 1-nonyl-

1 A l i idi

Λ— N CH₂ CN fj i N (CH₂ ) 3 NMe ₂

Compound 237

1 H-Perimidine- 1 -acetonitrile

Compound 238

1 - 3 -(Dimethylamino)propyl]perimidine

Compound 239

1H-Perimidine, l-[2-(4- Compound 240

morpholinyl)ethyl] 1 H-Perimidine, 1 - [2-( 1 -piperidinyl)ethyl]

Compound 241

lH-Perimidine-l-ethanamine, N,N- Compound 242

diethyl 1 -(Methoxymethyl)perimidine

Compound 249

1 -Methylperimidine

perm n- -y epty -

9

2,2'-Bi-lH-perimidine

Compound 408

1H-Perimidine, 2,2'-(l,2- ethanediyl)bis-

NH

(CH₂) 3

(CH₂) 6 1

1 CH2

CH2

Me s

Compound 411

Compose 410 1 H-Perimidine, 1 -methyl-2- [ [4-( 1 H-

1 H-Perimidine, 1 -methyl-2- [ [7-( 1 H- perimidin-2-yl)butyl]thio]

perimidin-2-yl)heptyl]thio] -

and their addition salts, isomers, tautomers, and solvates.

Preferably, R₅ and P6 designate independently of each other a hydrogen atom; a C1-C4 alkoxy group; a linear or branched C1-C4 alkyl group; a hydroxyl group; a halogen atom.

More preferably still, R5 and P6 denote a hydrogen atom.

Preferably, R3 and R4 designate independently of each other a hydrogen atom; a C1-C4 alkoxy group; a linear or branched C1-C4 alkyl group; a hydroxyl group; an amino group; a C2-C4 acylamino group; a CHO group; a halogen atom.

More preferably still, R5 and R6 denote a hydrogen atom. Preferably, Ri or R₂ designate independently of each other a hydrogen atom, an amino group, C1-C4 aminoalkyl, C1-C4 dialkylamino, a C1-C10 thioalkyl group, a linear or branched Ci-Ci₂ alkyl or Ci-Ci₂ alkenyl group, where these groups can be substituted by one or more hydroxy, amino, dialkylamino, carboxy, C1-C4 alkoxy groups.

Additional couplers

The composition according to the invention may also comprise one or more additional couplers, different than the perimidine couplers having formula (I), usually used in oxidative dyeing.

Mention may in particular be made, among these couplers, of meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

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

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

The 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. The content of coupler(s) each advantageously represents 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 dyes

The composition according to the invention may optionally comprise one or more synthetic or natural direct dyes, chosen from ionic or non-ionic species, preferably cationic or non-ionic 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; 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, protocatechualdehyde, 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 cataplasms 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 may be an anhydrous or aqueous composition. It is preferably aqueous. 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 mo no methyl ether, diethylene glycol mo no methyl ether and monoethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxy ethanol, and their mixtures. The organic 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, non- ionic, amphoteric or zwitterionic polymers or their mixtures; inorganic thickeners, and in particular fillers such as clays or talc; organic thickeners with, in particular, anionic, cationic, non-ionic or amphoteric polymeric associative thickeners other than the polymers mentioned previously; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preservatives; 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 further comprise one or more inorganic or organic thickeners.

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

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

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

Organophilic clays that may be mentioned include quaternium-18 bentonites, such as those sold as 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 as 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 as Claytone HT and Claytone PS by Southern Clay; quaternium-18 hectorites, such as those sold as 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 inorganic thickeners are chosen from inorganic fillers, particularly kaolinite.

The organic thickeners may be chosen from associative or non-associative thickening polymers, particularly associative polymers.

According to the invention, "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 poly ethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be for example aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.

Such polyurethane polyethers are sold especially by Rohm & Haas as Aculyn 46® and Aculyn 44® [Aculyn 46® is a poly condensate 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 poly condensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexylisocyanate) (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

The composition according to the invention may comprise one or more chemical oxidizing agents.

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

One or more redox enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase), optionally in the presence of their respective donor or cofactor, may also be used as oxidizing agent.

This oxidizing agent advantageously consists of hydrogen peroxide, in particular in aqueous solution (aqueous hydrogen peroxide solution), whose concentration may vary, more particularly from 0.1% to 50% by weight, even more preferentially from 0.5% to 20% by weight and better still from 1% to 15% by weight relative to the composition.

Methods according to the invention

The composition used in the method 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 method 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 method is conventionally between room temperature (between 15°C and 25°C) and 80°C and preferably between room temperature and 60°C.

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

The composition applied in the method 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 method according to the invention (thus used with at least one chemical oxidizing agent) results from mixing two compositions.

Specifically, a composition (A) comprising at least one oxidation base, at least one perimidine coupler having formula (I) and at least one alkaline agent and a composition (B) comprising at least one chemical oxidizing agent are mixed, at least one of the compositions (A) and (B) comprising at least one fatty substance, at least one of the compositions (A) and (B) comprising at least one surfactant; the fatty substance content of the composition according to the invention resulting from mixing compositions (A) and (B) comprising at least 25% by weight of fatty substances.

At least one of compositions (A) and (B) is advantageously aqueous. Preferably, composition (A) is aqueous. Preferably, composition (B) is also aqueous.

In this alternative form, 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 alternative form, compositions (A) and (B) are preferably mixed in an (A)/(B) ratio by weight 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 method according to the invention (thus in the presence of at least one chemical oxidizing agent) results from mixing three compositions. In particular, the three compositions are aqueous or alternatively at least one of them is anhydrous.

More particularly, within the meaning of the invention, the term "anhydrous cosmetic composition" is understood to mean a cosmetic composition exhibiting a water content of less than 5% by weight, preferably of less than 2% by weight and more preferably still of 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 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.

Use is preferably made of two aqueous compositions (Β') and (C) and an anhydrous composition (Α').

The anhydrous composition (Α') then preferably comprises at least one fatty substance and more preferably at least one liquid fatty substance.

The composition (Β') then preferably comprises at least one oxidation base and at least one perimidine coupler having formula (I).

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

According to this preferred embodiment of the second alternative form, the alkaline agent(s) are included in the compositions (Α') and/or (Β') and preferably only in composition (Β'). As regards the surfactant(s), it is (they are) included in at least one of the compositions (Α'), (Β') and (C). According to this preferred embodiment, the composition according to the invention, that is to say resulting from mixing the three compositions (Α'), (Β') and (C), exhibits a fatty substance content of at least 25% by weight of fatty substances, relative to the weight of the composition resulting from mixing the three abovementioned compositions.

In this alternative form, compositions (Α'), (Β') and (C) are preferably mixed in an [(A')+(B')]/(C) ratio by weight ranging from 0.2 to 10 and more particularly from 0.5 to 2 and in an (Α')/(Β') ratio by weight 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 including composition (A) as described above and at least a second compartment including composition (B) as described above; compositions (A) and (B) of the compartments being intended to be mixed before application to give a composition according to the invention; whose amount of fatty substance represents at least 25% by weight, relative to the weight of the formulation resulting from mixing 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 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 mixing compositions (Α'), (Β') and (C).

The examples which follow serve to illustrate the invention without, however, exhibiting a limiting nature.

EXAMPLES

The following compositions are prepared in which the amounts are expressed in grams of as is materials. Composition (A)

Propylene glycol 6.2

Ethyl alcohol 8.25

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

Dipropylene glycol 3

Monoethano lamine 14.5

Sodium metabisulfite 0.7

Vitamin C: L-ascorbic acid 0.25

Diethylenetriaminepentaacetic acid,

pentasodium salt, as a 40% aqueous solution 1

Hydroxy ethylcellulose (Natrosol 250 HHR,

Aqualon) 3.5

Oxidation base 2x l0^"2 mol

Coupler having formula (I) 2x l0^"2 mol

Water qsp 100 g

Composition (C)

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

-10 parts of composition A,

-4 parts of composition B,

-16 parts of composition C.

The mixture obtained is then applied to a tress of natural hair containing 90%) white hairs (NW). The "mixture/tress" bath ratio is respectively 10/1 (g/g).

The leave-on time is 30 minutes at 27°C. After this time, the tresses are rinsed, then washed with Elseve multivitamin shampoo, and dried.

All the shades obtained are intense.

Claims

1. Oxidative dyeing composition for keratin fibres, in particular human keratin fibres such as the hair, comprising:

- one or more surfactants,

- one or more alkaline agents,

- one or more oxidation bases, and

in which:

Ri, R₂, R₃, R4, R5, 5 designate independently of each other, a hydrogen atom; an amino group; a halogen atom; a hydroxyl group; a Ci-Cs alkoxy group; a C₂-C₅acylamino group; a CHO group;

a linear, branched or cyclic, saturated Ci-Cis alkyl or C₂-Cis alkenyl group, where one or more carbon atoms can be replaced by one or more heteroatoms such as oxygen or sulfur or by an NH or N-alkyl group, where the alkyl groups can be substituted by one or more groups chosen from hydroxyl, nitro, nitrile, cyano, carboxylic acid, Ci-Cis alkyl ester, carbamate, carboxamide, amino, alkylamino, dialkylamino, carboxy, alkoxy, halogen atoms, C3-C6 cycloalkyl, a heterocycle containing 5 to 8 members and containing one or more heteroatoms such as nitrogen, sulfur or oxygen, where one or more carbon atoms in the cycloalkyl or heterocycle groups can be substituted by one or more groups chosen from hydroxyl, nitro, nitrile, cyano, carboxylic acid, Ci-Cis alkyl ester, carbamate, carboxamide, amino, alkylamino, dialkylamino, carboxy, alkoxy, halogen atom;

or Ri designates a linear or branched Ci-Cio alkylene chain that may contain one or more heteroatoms and be substituted by a perimidine radical from a group having formula (I), preferably via the carbon atom located at the 2-position,

2. Composition according to the preceding claim, characterized in that the fatty substance(s) are chosen from compounds that are liquid or pasty at room temperature and atmospheric pressure.

3. Composition according to Claim 1 or 2, characterized in that the fatty substance(s) are chosen from C₆-Ci6 hydrocarbons, hydrocarbons comprising more than 16 carbon atoms, non-silicone oils of animal origin, vegetable oils of triglyceride type, synthetic triglycerides, fluorinated oils, fatty alcohols, fatty acid and/or fatty alcohol esters other than the triglycerides and vegetable waxes, non- silicone waxes or silicones and their mixtures.

4. Composition according to any one of the preceding claims, characterized in that the fatty substance(s) are chosen from liquid petrolatum, polydecenes, fatty alcohols, liquid fatty acid and/or fatty alcohol esters and their mixtures.

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 non-ionic surfactants, particularly mono- or polyoxyalkylenated and mono- or polyglycerolated non-ionic surfactants.

7. Composition according to any one of the preceding claims, characterized in that the perimidine coupler(s) having formula (I) are chosen from: ,

car oxa e y e

CH2— (CH2 ) 4— CO2 H

Compound 91 Compound 92

1 H-Perimidine-2-methanol lH-Perimidine-2-hexanoic acid

CH2— CH2— CO2H

Compound 93 Compound 94

lH-Perimidine-2-pentanoic acid

lH-Perimidine-2-butanoic acid (CH 2 ) 7— Me

Compound 95 Compound 96

lH-Perimidine-2-propanoic acid 1H-Perimidine, 2-nonyl-

Br

Compound 213

lH-Perimidine-1 -propanoic acid Compound 214

1H-Perimidine, 7-bromo

Compound 216

lH-Perimidine-l-butanamine, N,N-

Compound 215

dimethyl-

1 H-Perimidin-7-ol

Compound 217

lH-Perimidine-l-ethanamine, N,N- Compound 218

dimethyl- 1 -Vinylperimidine

Compound 249

1 -Methylperimidine

Compound 307

Compound 308

N-(3 -methylbutyl)-2-( 1 H-perimidin

1H-Perimidine, 2

2-ylthio) acetamide

Compound 309

2-( 1 H-perimidin-2-ylthio)-ethyl Compound 310

acetate 1H-Perimidine, 2- (pentafluoroethoxy)-

Compound 312

1 -Hexyl-2-(nonylthio)- 1 H-perimidine

Compound 311

lH-Perimidin-2-amine, 5,8-bis(l,l

dimethylethyl)-N-methyl

9

2,2'-Bi-lH-perimidine

Compound 408

1H-Perimidine, 2,2'-(l,2- ethanediyl)bis-

NH

(CH₂) 3

(CH₂) 6 1

1 CH2

CH2

Me s

Compound 411

Compound 410 1 H-Perimidine, 1 -methyl-2- [ [4-( 1 H-

1 H-Perimidine, 1 -methyl-2- [ [7-( 1 H- perimidin-2-yl)butyl]thio]

perimidin-2-yl)heptyl]thio] -

and their addition salts, isomers, tautomers, and solvates.

8. Composition according to any one of the preceding claims, characterized in that the oxidation base(s) are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts.

9. Composition according to any one of the preceding claims, characterized in that the alkaline agent is an organic amine with a p¾, below 12, preferably below 10.

10. Composition according to any one of the preceding claims, characterized in that the alkaline agent is an organic amine chosen from alkanolamines, basic amino acids, compounds including a guanidine function and their mixtures.

11. Composition according to the preceding claim, characterized in that the alkaline agent is an alkanolamine, preferably monoethanolamine.

12. Composition according to any one of Claims 1 to 8, characterized in that the alkaline agent is an inorganic base chosen from ammonia, sodium carbonate, potassium carbonate, caustic soda, potash, sodium metasilicate, potassium metasilicate and their mixtures.

13. Composition according to the preceding claim, characterized in that the alkaline agent is an inorganic base chosen from alkaline carbonates.

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

15. Method 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 13, in the presence of at least one chemical oxidizing agent.

16. Method according to the preceding claim, characterized in that the composition results from mixing two compositions; preferably of a composition (A) comprising at least one oxidation base, at least one perimidine coupler having formula (I) and at least one alkaline 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 of the compositions (A) and (B) comprising at least one surfactant; the fatty substance content of the composition resulting from mixing compositions (A) and (B) comprising at least 25% by weight of fatty substances.

17. Method according to Claim 15, characterized in that the composition results from mixing three compositions, preferably two aqueous compositions (Β') and (C) and 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 perimidine coupler having formula (I), the composition (C) comprising at least one chemical oxidizing agent, one or more alkaline agents being included in the compositions (Α') and/or (Β') and preferably only in 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 mixing the three compositions (Α'), (Β') and (C) comprising at least 25% by weight of fatty substances.

18. Multi-compartment device comprising a first compartment including composition (A) as described in Claim 16 and at least a second compartment including composition (B) as described in Claim 16, the compositions of the compartments being intended to be mixed before application, provided that the amount of fatty substance represents at least 25% by weight, relative to the weight of the composition resulting from mixing (A) and (B).

19. Multi-compartment device comprising a first compartment including composition (Α') as described in Claim 17; and a second compartment including a cosmetic composition (Β') as described in Claim 17 and at least a third compartment comprising composition (C) as described in Claim 17; the compositions of the compartments being intended to be mixed before application, provided that the amount of fatty substance represents at least 25% by weight, relative to the weight of the composition resulting from mixing (Α'), (Β') and (C).