WO2017109132A1 - Process using a composition comprising a neutralized fatty acid, and a particular clay - Google Patents

Abstract

The present invention relates to a process for treating keratin fibres, in particular human keratin fibres such as the hair, using a cosmetic composition comprising one or more neutralized fatty acids and one or more particular clays, and also to the use of said composition. A subject of the present invention is also a cosmetic composition comprising at least two different neutralized fatty acids, one or more particular clays, and one or more amphoteric or zwitterionic surfactants.

Description

Process using a composition comprising a neutralized fatty acid, and a

particular clay

The present invention relates to a process for treating keratin fibres, in particular human keratin fibres such as the hair, using a cosmetic composition comprising one or more neutralized fatty acids and one or more particular clays, and also to the use of said composition.

A subject of the present invention is also a cosmetic composition comprising at least two different neutralized fatty acids, one or more particular clays, and one or more amphoteric or zwitterionic surfactants.

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

A first 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 affinity for the fibres, and then leaving them on for a time, to allow the molecules to penetrate by diffusion to the interior of the fibre, and then rinsing the fibres. This process is generally performed in an alkaline medium.

However, although being particularly chromatic, the resulting colourings are temporary or semi-permanent. Specifically, the nature of the interactions that bind the direct dyes to the keratin fibre and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power and their poor persistence with respect to washing.

A second type of dyeing also exists, which makes it possible to obtain

"permanent" colourings. These permanent colourings are obtained via a process of oxidation dyeing using dye compositions containing oxidation dye precursors, generally known as oxidation bases. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.

The shades obtained with these oxidation bases may be varied by combining them with couplers or colour modifiers. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained. Most of these permanent dyeing processes provide a good level of coverage of grey hair. However, they require the presence of an oxidizing agent in an alkaline medium. Furthermore, these conditions are all the more harsh the greater the desired degree of coverage of the grey hairs in a head of hair.

Now, one of the difficulties of these direct dyeing and oxidation dyeing processes arises especially from this alkaline medium, and more particularly from aqueous ammonia, which is the alkaline agent most commonly used. The use of aqueous ammonia is particularly advantageous in processes of this type. The reason for this is that it makes it possible to adjust the pH of the composition to an alkaline pH to enable activation of the oxidizing agent. It especially causes swelling of the keratin fibre, with opening of the scales, which promotes the penetration of the direct dyes and oxidation dyes into the fibre, and thus increases the efficacy of the dyeing reaction.

However, this alkaline agent is highly volatile, and this causes unpleasantness to the user on account of the strong and fairly unpleasant characteristic odour of ammonia that is given off during the process.

Moreover, the amount of ammonia given off requires the use of levels which are greater than those necessary, in order to compensate for this loss. This is not without consequences for the user, who not only remains inconvenienced by the odour, but may also be confronted with greater risks of intolerance, for instance irritation of the scalp, which is reflected especially by stinging.

It was thus proposed to replace all or some of the aqueous ammonia with one or more other alkaline agents, such as alkanolamines, and especially with monoethanolamine. The reason for this is that, unlike aqueous ammonia, this alkaline agent has the advantage of being sparingly odorous and sparingly volatile. However, after application of a dye product containing monoethanolamine followed by shampooing, the monoethanolamine is not entirely removed from the fibre, given its low volatility. The presence of residual monoethanolamine molecules inside the fibre may lead to embrittlement of the fibre and damage its integrity, which may be reflected by unfavourable cosmetic properties.

Thus, there is a real need to provide a composition that can reinforce and/or improve the integrity of fibres that have undergone dyeing (direct or oxidation dyeing) in the presence of alkanolamines, and especially of monoethanolamine. The Applicant has discovered, surprisingly, that a process for treating keratin fibres using a composition comprising one or more neutralized fatty acids and one or more particular clays makes it possible to achieve the objectives outlined above; especially to improve the integrity of fibres that have undergone direct and/or oxidation dyeing.

One subject of the present invention is especially a process for treating keratin fibres and in particular human keratin fibres such as the hair, comprising the following steps:

- a first step of direct and/or oxidation dyeing of keratin fibres, and then

- a second step of applying to said keratin fibres a composition comprising one or more fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases or in the form of fatty acid salts, and one or more clays chosen from the smectite family.

The process according to the present invention makes it possible especially to reinforce and improve the integrity of keratin fibres, and in particular of keratin fibres that have undergone direct and/or oxidation dyeing.

The process according to the invention also gives the hair good cosmetic properties, while at the same time preserving the dyeing qualities.

A subject of the present invention is also a cosmetic composition comprising:

- at least two different fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases,

- one or more clays chosen from the smectite family, and

- one or more amphoteric or zwitterionic surfactants;

the total amount of fatty acids, expressed relative to the fatty acids in free form, ranges from 1% to 15% by weight, relative to the total weight of the composition.

Finally, the present invention relates to the use of a composition as defined previously for treating keratin fibres, in particular human keratin fibres such as the hair, which have undergone direct and/or oxidation dyeing.

Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range, especially in the expressions "between" and "ranging from ... to Moreover, the expressions "at least one", "at least two" and "at least" used in the present description are equivalent to the expressions "one or more", "two or more" and "greater than or equal to", respectively. Neutralized fatty acids

The composition applied to the keratin fibres during the second step of the process according to the present invention comprises one or more fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases or in the form of fatty acid salts.

The fatty acids are advantageously chosen from carboxylic acids comprising a linear or branched, saturated or unsaturated alkyl chain containing from 6 to 30 carbon atoms and more preferentially from 10 to 18 carbon atoms.

Preferably, the fatty acids are chosen from lauric acid, palmitic acid and myristic acid, and mixtures thereof, and, more preferentially, the fatty acids are lauric acid and myristic acid.

The fatty acids are generally introduced into the composition in free form, i.e. in acid form (-COOH). The addition of one or more mineral bases then allows them to be neutralized within the composition itself.

The total amount of fatty acids, expressed relative to the fatty acids in free form, preferably ranges from 1% to 30% by weight, more preferentially from 1% to 20% by weight and better still from 3% to 15% by weight relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

The mineral base(s) used for neutralizing the fatty acids are advantageously chosen from alkali metal hydroxides, alkaline-earth metal hydroxides and aqueous ammonia, and mixtures thereof.

More preferentially, the mineral base(s) are chosen from alkali metal hydroxides, and better still the mineral base is potassium hydroxide.

The total amount of mineral base(s), present in the composition according to the invention, preferably ranges from 0.5% to 10% by weight and more preferentially from 1% to 5% by weight relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

The fatty acid salts are preferably chosen from the sodium salts and the potassium salts of said fatty acids. More preferentially, the fatty acid salts are chosen from potassium laurate, sodium laurate, potassium myristate and sodium myristate, and mixtures thereof.

Clays

The composition applied to the keratin fibres during the second step of the process according to the present invention also comprises one or more clays chosen from the smectite family.

Smectites belong to the general family of silicates, and more particularly of phyllosilicates.

Silicates correspond to optionally hydrated silica in which some of the silicon atoms are replaced with metal cations such as Al³⁺, B³⁺, Fe³⁺, Ga³⁺, Be²⁺, Zn²⁺, Mg²⁺, Co³⁺, Ni³⁺, Na⁺, Li⁺, Ca²⁺, Cu²⁺.

The structure of phyllosilicates usually corresponds to a stack of tetrahedral sheets (Si0₄) and octahedral Al(OH)₆ sheets with the possibility of replacement of the Al ions with other metal ions (Mg, Fe, etc.) in the octahedral sheets. This consequently results in a complex classification of these minerals into various groups depending on their chemical structure, i.e. as a function of the combination of these sheets in the "interfoliar" spaces. The most commonly known phyllosilicates are the kaolinite, talc, mica, smectite or sepiolite groups. Besides the chemical composition/structure of phyllosilicates, one of the parameters for distinguishing them is their cationic exchange capacity (CEC) in relation with the presence of cations in the interfoliar spaces.

These clays may be of natural or synthetic origin. Clays that are cosmetically compatible and acceptable with keratin materials are preferably used.

The clay(s) of the smectite type, present in the composition according to the invention, are preferably chosen from montmorillonite, hectorite, bentonite, beidellite and saponite, and mixtures thereof, and, more preferentially, the clay is montmorillonite.

Preferably, the clay(s) that may be used in the present invention have a cationic exchange capacity (CEC) of greater than 45 meq./100 g (or 45 cmol/kg, i.e. 45 centimol of positive charge per kg). The CEC value may be determined according to various techniques, and especially those described in the Handbook of Clay Science 2nd Edition Part B: Techniques and Applications (Chapter 2.11.4) edited by F. Bergaya and G. Lagaly. The total amount of clay(s) of the smectite type, present in the composition according to the invention, preferably ranges from 0.5% to 20% by weight and more preferentially from 1% to 10% by weight relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

The composition applied to the keratin fibres during the second step of the process according to the present invention may also optionally comprise one or more additional clays, other than clays chosen from the smectite family, as described previously.

These additional clays preferably have a CEC value lower than the CEC value of the clays chosen from the smectite family, and especially a CEC value of less than 45 meq./100 g.

The additional clay(s) are preferably chosen from sepiolite, talc, kaolin and mica, and mixtures thereof.

Surfactants

The composition applied to the keratin fibres during the second step of the process according to the present invention may also optionally comprise one or more surfactants.

The surfactant(s) that may be used in the composition according to the invention may be chosen from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric or zwitterionic surfactants.

The composition applied to the keratin fibres during the second step of the process according to the present invention may comprise one or more nonionic surfactants.

The nonionic surfactants that may be used are described, for example, in the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178.

Examples of nonionic surfactants that may be mentioned include the following nonionic surfactants:

- oxyalkylenated (Cs-C24)alkylphenols;

- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated Cs to C₄o alcohols, comprising one or two fatty chains;

- saturated or unsaturated, linear or branched, oxyalkylenated C8-C30 fatty acid amides; - esters of saturated or unsaturated, linear or branched, C₈-C30 acids and of polyethylene glycols;

- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, C₈- C30 acids and of sorbitol;

- esters of fatty acids and of sucrose;

(C₈-C3o)alkyl(poly)glucosides, (C₈-C3o)alkenyl(poly)glucosides, which are optionally oxyalkylenated (0 to 10 oxyalkylene units) and comprising from 1 to 15 glucose units, (Cs-C3o)alkyl (poly)glucoside esters;

- saturated or unsaturated oxyethylenated plant oils;

- condensates of ethylene oxide and/or of propylene oxide;

- N-(C₈-C3o)alkylglucamine and N-(C₈-C3o)acylmethylglucamine derivatives;

- aldobionamides;

- amine oxides;

- oxyethylenated and/or oxypropylenated silicones;

- and mixtures thereof.

The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or their combination, preferably oxyethylene units.

The number of moles of ethylene oxide and/or of propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol ranges in particular from 1 to 50 and better still from 1 to 10.

Advantageously, the nonionic surfactants according to the invention do not comprise any oxypropylene units.

As examples of glycerolated nonionic surfactants, use is preferably made of monoglycerolated or polyglycerolated C₈-C40 alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol.

Mention may be made, as examples of compounds of this type, of lauryl alcohol comprising 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 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. Preference is more particularly given, among the glycerolated alcohols, to the use 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.

The nonionic surfactant(s) that may be used in the dye composition according to the invention are preferentially chosen from:

- oxyethylenated Cs to C₄o alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and comprising one or two fatty chains;

- saturated or unsaturated oxyethylenated vegetable oils comprising from 1 to 100 and preferably from 2 to 50 mol of ethylene oxide;

- (C8-C3o)alkyl(poly)glucosides, which are optionally oxyalkylenated (0 to 10 OE) and comprising 1 to 15 glucose units;

- monoglycerolated or polyglycerolated Cs to C₄o alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol;

- saturated or unsaturated, linear or branched, oxyalkylenated C8-C30 fatty acid amides;

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

- and mixtures thereof.

The composition applied to the keratin fibres during the second step of the process according to the present invention may comprise one or more cationic surfactants.

The term "cationic surfactant" means a surfactant that is positively charged when it is contained in the composition applied to the keratin fibres during the second step of the process according to the invention. This surfactant may bear one or more permanent positive charges or may contain one or more cationizable functions in the compositions according to the invention.

The cationic surfactant(s) are preferably chosen from primary, secondary or tertiary fatty amines, which are optionally polyoxyalkylenated, or salts thereof, and quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one Cs to C30 hydrocarbon- based chain.

Examples of quaternary ammonium salts that may especially be mentioned include: (i) those corresponding to the general formula (I) below:

(I)

in which the groups R₂8 to R31 , which may be identical or different, represent a linear or branched aliphatic group containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R₂8 to R31 denoting a group containing from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms. The aliphatic groups may comprise heteroatoms such as, in particular, oxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen, for example, from C₁-C30 alkyl, C1-C30 alkoxy, polyoxy(C₂-C6)alkylene, C1-C30 alkylamide, (Ci2-C₂2)alkylamido(C₂- C₆)alkyl, (Ci₂-C₂₂)alkyl acetate, and C₁-C30 hydroxyalkyl groups, X^" is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C₄)alkyl sulfates, and (Ci-C₄)alkyl- or (Ci-C₄)alkylarylsulfo nates.

Preference is given, among the quaternary ammonium salts of formula (I), on the one hand, to tetraalkylammonium salts, such as, for example, dialkyldimethylammonium or alkyltrimethylammonium salts, in which the alkyl group comprises approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, or also, on the other hand, to palmitylamidopropyltrimethylammonium salts, stearamidopropyltrimethylammonium salts, stearamidopropyldimethylcetearylammonium salts or stearamidopropyldimethyl(myristyl acetate)ammonium salts sold under the name Ceraphyl^® 70 by Van Dyk. It is preferred in particular to use the chloride salts of these compounds;

(ii) quaternary ammonium salts of imidazoline, for instance those of formula (II) below:

(II) in which:

R32 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example derived from tallow fatty acids,

R33 represents a hydrogen atom, a Ci to C₄ alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms,

R₃₄ represents a Ci to C₄ alkyl group,

R35 represents a hydrogen atom or a Ci to C₄ alkyl group,

X^" is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl- or alkylaryl-sulfonates in which the alkyl and aryl groups preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms.

Preferably, R₃₂ and R₃₃ denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R₃₄ denotes a methyl group and R₃₅ denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat^® W 75 by Rewo;

(iii) di- or triquaternary ammonium salts, in particular of formula (III):

in which:

R₃6 denotes an alkyl radical including approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms, R37 is chosen from hydrogen, an alkyl radical comprising from 1 to 4 carbon atoms and a group (R₃6a)(R37a)(R38a)N-(CH₂)3,

R₃6a, R₃7a, R₃8a, R₃8, R₃9, R40 and R41 , which may be identical or different, are chosen from hydrogen and an alkyl radical comprising from 1 to 4 carbon atoms, and X^" is an anion chosen from the group of halides, acetates, phosphates, nitrates and methyl sulfates.

Such compounds are, for example, Finquat CT-P, available from Finetex (Quatemium 89), and Finquat CT, available from Finetex (Quatemium 75);

(iv) quaternary ammonium salts comprising at least one ester function, such as those of formula (IV) below:

(C_sH_2sO)_z— R '45

X

(OC_rH_2r) -N (C_tH_2tO)_x-

^R42 (IV) in which:

P4₂ is chosen from Ci to C₆ alkyl groups and Ci to C₆ hydroxyalkyl dihydroxyalkyl groups;

R43 is chosen from:

O

- the group ⁴⁶

- groups R47, which are saturated or unsaturated and linear or branched Ci to C₂₂ hydrocarbon-based groups,

- a hydrogen atom,

R45 is chosen from:

O

R,

- the group ⁴⁸

- groups R49, which are saturated or unsaturated and linear or branched Ci to C₆ hydrocarbon-based groups,

- a hydrogen atom,

R44, R46 and R48, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C₇ to C₂₁ hydrocarbon-based groups, r, s and t, which may be identical or different, are integers having values from 2 to 6; y is an integer having a value from 1 to 10;

x and z, which may be identical or different, are integers having a value from 0 to 10; X^" is a simple or complex and organic or mineral anion;

with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R43 denotes R47, and that when z is 0 then R45 denotes R49.

The alkyl groups R42 may be linear or branched, and more particularly linear.

Preferably, R42 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 R43 is a hydrocarbon-based group R47, 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 R45 is a hydrocarbon-based group R49, it preferably contains 1 to 3 carbon atoms.

Advantageously, R44, P ₆ and R48, which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn to C₂₁ hydrocarbon- based groups, and more particularly from linear or branched, saturated or unsaturated Cn to C21 alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, have the value 0 or

1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, have the value 2 or

3 and more particularly still are equal to 2.

The anion X^" is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate. 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 which is compatible with the ammonium having an ester function.

The anion X^" is more particularly still chloride or methyl sulfate.

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

R42 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;

R43 is chosen from:

- the group

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

- a hydrogen atom;

R45 is chosen from:

O

- the group ^⁴⁸ ^

- a hydrogen atom;

R44, R46 and R48, which may be identical or different, are chosen from saturated or unsaturated and linear or branched C₁₃ to C₁₇ hydrocarbon-based groups and preferably from saturated or unsaturated and linear or branched C₁₃ to C₁₇ alkyl and alkenyl groups.

Advantageously, the hydrocarbon-based groups are linear.

Examples that may be mentioned include the compounds having formula

(IV) such as the diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,

monoacyloxyethyldihydroxyethylmethylammonium,

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

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine, which are optionally oxyalkylenated, with C₁₀ to C₃o fatty acids or with mixtures of C₁₀ to C₃o fatty acids of vegetable or animal origin, or by transesterification of their methyl esters. This esterification is followed by a quaternization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably a methyl or ethyl sulfate), methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

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

The composition applied to the keratin fibres during the second step of the process according to the present invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.

It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.

Preferably, the ammonium salts comprising at least one ester function comprise two ester functions.

Among the quaternary ammonium salts containing at least one ester function, which may be used, it is preferred to use dipalmitoylethylhydroxyethyl- methylammonium salts.

The cationic surfactants are preferably chosen from those of formula (I) and those of formula (IV) and more preferably still from those of formula (I).

The composition applied to the keratin fibres during the second step of the process according to the present invention may comprise one or more anionic 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 -COOH, -COO^", -S0₃H, -S0₃ ^", -OS0₃H, -OS0₃ ^", -P0₂H₂, -P0₂H^", -P0₂ ^2", -P(OH)₂, =P(0)OH, -P(OH)0^", =P(0)0^", =POH and =PO , the anionic parts comprising a cationic counterion such as an alkali metal, an alkaline-earth metal or an ammonium.

As examples of anionic surfactants that may be used in the dye composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, a-olefm sulfonates, paraffin sulfonates, alkyl sulfo succinates, alkyl ether sulfo succinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkyl sulfosuccinamates, acylisethionates and N-acyltaurates, polyglucoside- 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 40 carbon atoms and the aryl group denoting a phenyl group.

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

The salts of C₆ to C₂₄ alkyl monoesters of polyglucoside-polycarboxylic acids may be chosen from C₆ to C₂₄ alkyl polyglucoside-citrates, C₆ to C₂₄ alkyl polyglucoside-tartrates and C₆ to C₂₄ alkyl polyglucoside-sulfosuccinates.

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

Mention may in particular be made, as examples of amino alcohol salts, of mono-, di- and triethanolamine salts, mono-, di- or triisopropanolamine salts, 2- amino-2-methyl-l-propanol salts, 2-amino-2-methyl-l,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

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

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

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

The composition applied to the keratin fibres during the second step of the process according to the present invention may comprise one or more amphoteric or zwitterionic surfactants. In particular, the amphoteric or zwitterionic surfactant(s), which are preferably non-silicone, which may be used in the composition according to the present invention may in particular be derivatives of optionally quaternized, secondary or tertiary aliphatic amines, in which derivatives the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.

Mention may in particular be made of (C₈-C₂o)alkyl betaines, (C₈-C₂o)alkyl sulfobetaines, (C₈-C₂o)alkylamido(C₃-C₈)alkyl betaines and (C₈-C₂o)alkylamido(C6- C₈)alkyl sulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, as defined above, mention may also be made of the compounds having the respective structures (V) and (VI) below: R_a-CONHCH₂CH₂-N⁺(R_b)(R_c)-CH₂COO^", M⁺ , X^" (V) in which:

Ra represents a C₁₀ to C₃₀ alkyl or alkenyl group derived from an acid RaCOOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group; - Rb represents a beta-hydroxyethyl group; and

Rc represents a carboxymethyl group;

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

- X^" represents an organic or mineral anionic counterion, 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;

R_a.-CONHCH₂CH₂-N(B)(B') (VI) in which:

B represents the group -CH₂CH₂OX';

B' represents the group -(CH₂)_ZY', with z = 1 or 2; - X^* represents the group -CH₂COOH, -CH₂-COOZ', -CH₂CH₂COOH, CH₂CH₂-COOZ', or a hydrogen atom;

Y' represents the group -COOH, -COOZ' or

-CH₂CH(OH)S0₃H or the group CH₂CH(OH)S0₃-Z';

- Z' represents a cationic counterion resulting from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine;

- Ra' represents a C₁₀ to C₃o alkyl or alkenyl group of an acid Rv-COOH which is preferably present in hydrolysed linseed oil or coconut oil, or an alkyl group, in particular a C₁₇ alkyl group, and its iso form, or an unsaturated C₁₇ group.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium caprylamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium caprylamphodipropionate, 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.

Use may also be made of compounds of formula (VII): Ra_"-NHCH(Y")-(CH₂)_nCONH(CH₂)_n.-N(R_d)(R_e) (VII) in which:

- Y" represents the -COOH, -COOZ" or -CH₂-CH(OH)S0₃H group or the CH₂CH(OH)S0₃-Z" group;

- Ra and R_e, independently of each other, represent a Ci to C₄ alkyl or hydroxyalkyl radical;

- Z" represents a cationic counterion resulting from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine;

- Ra" represents a C₁₀ to C₃o alkyl or alkenyl group of an acid R^-COOH preferably present in hydrolysed linseed oil or coconut oil;

- n and n' denote, independently of each other, an integer ranging from 1 to 3.

Mention may be made, among the compounds of formula (VII), of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by Chimex under the name Chimexane HB.

These compounds may be used alone or as mixtures.

Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of (C8-C2o)alkylbetaines such as cocoyl betaine, (C₈- C2o)alkylamido(C₃-C8)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof, and the compounds of formula (VII) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide).

The surfactant(s) present in the composition applied to the keratin fibres during the second step of the process according to the invention are preferably chosen from amphoteric and zwitterionic surfactants, and more preferentially (C₈- C2o)alkylbetaines such as cocoyl betaine, (C₈-C2o)alkylamido(C₃-C₈)alkylbetaines such as cocamidopropyl betaine, and mixtures thereof.

Preferably, the total amount of the surfactant(s), present in the composition according to the invention, may range from 0.5% to 20% by weight, and preferably from 1% to 15% by weight, relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

Silicones

The composition applied to the keratin fibres during the second step of the process according to the present invention may optionally also comprise one or more silicones.

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

Preferably, the silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organomodified polysiloxanes containing at least one functional group chosen from amino groups, aryl groups, hydroxyl groups and alkoxy groups. Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academie Press. They may be volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point 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. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone^® 7207 by Union Carbide or Silbione^® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone^® 7158 by Union Carbide, and Silbione^® 70045 V5 by Rhodia, and mixtures thereof.

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

D" - D' - D" - D'

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

C 8_DH" 7

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-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 5x10^"6 m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company

Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers,

"Volatile Silicone Fluids for Cosmetics".

Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organofunctional groups, and mixtures thereof, are preferably used.

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

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

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

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

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

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

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

In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax^® 9800 and 9801 by the company Goldschmidt, which are poly(Ci-C2o)dialkylsiloxanes.

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

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

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

- mixtures of a polydimethylsiloxane gum and 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; - mixtures of two PDMSs with different viscosities, and more particularly of a PDMS gum and of 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, with a viscosity of 20 mVs 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 that may be used in accordance with the invention are crosslinked siloxane systems containing the following units:

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

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

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

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

The organomodified silicones that may 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-based group.

The organomodified silicones may be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.

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

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

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

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

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

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

- the silicones of the PN and PH series from Bayer, such as the products PN1000 and PH1000; - certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

Among the organomodified silicones, mention may also be made of polyorganosiloxanes comprising:

- substituted or unsubstituted amine groups, such as the products sold under the names GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C1 -C4 aminoalkyl groups;

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

Goldschmidt.

- hydroxyl groups, such as the product sold under the name Belsil DM 3560 VP by the company Wacker.

Organic solvents

The composition applied to the keratin fibres during the second step of the process according to the present invention may also optionally comprise one or more organic solvents.

Examples of organic solvents that may be mentioned include linear or branched C₂ to C₄ alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol mo no methyl ether and monoethyl ether, and also aromatic alcohols or ethers, for instance benzyl alcohol or phenoxy ethanol, and mixtures thereof.

The total amount of organic solvent(s), when they are present in the composition, preferably ranges from 0.01% to 20% by weight and more preferentially from 0.1% to 10% by weight, relative to the total weight of the composition.

Additives

The composition applied to the keratin fibres during the second step of the process according to the present invention may also optionally comprise one or more additives, different from the compounds of the invention and among which mention may be made of fatty substances, cationic, anionic, nonionic or amphoteric polymers or mixtures thereof, antidandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or for promoting hair regrowth, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, sequestrants, plasticizers, solubilizers, acidifying agents, mineral or organic thickeners, especially polymeric thickeners, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances, preserving agents, pigments and ceramides.

Needless to say, those skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the ready-to-use composition.

Treatment process

Preferably, the step of direct and/or oxidation dyeing of the keratin fibres uses one or more alkaline agents.

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

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

The organic alkaline agent(s) are preferably chosen from organic amines with a pKt at 25°C of less than 12, preferably of less than 10 and more advantageously still of less than 6. It should be noted that it concerns the pKb corresponding to the function having the highest basicity. In addition, the organic amines do not comprise any alkyl or alkenyl fatty chain 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 of formula (VIII) below:

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

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

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

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

Among the compounds of this type, mention may be made of monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Ν,Ν-dimethylethanolamine, 2-amino-2- methyl-l-propanol, triisopropanolamine, 2-amino-2-methyl-l ,3-propanediol, 3- amino-l ,2-propanediol, 3-dimethylamino-l ,2-propanediol and tris(hydroxymethyl)aminomethane.

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

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

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

Such basic amino acids are preferably chosen from those corresponding to formula (IX) below, and also the salts thereof

R-CH₂-CH(NH₂)-C(0)-OH (IX) in which R represents a group chosen from imidazolyl, preferably imidazolyl-4-yl; aminopropyl; aminoethyl;

-(CH₂)₂N(H)-C(0)-NH₂; and -(CH₂)₂-N(H)-C(NH)-NH₂.

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

The organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

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

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

Guanidine carbonate or monoethanolamine hydrochloride may be used in particular.

Preferably, the alkaline agent(s) used in the first step of the treatment process according to the present invention are chosen from aqueous ammonia and alkanolamines, and mixtures thereof, and more preferentially from alkanolamines. Better still, the alkaline agent is monoethanolamine.

The direct and/or oxidation dyeing step also uses a dye composition comprising one or more oxidation dyes and/or one or more direct dyes.

The oxidation dyes that may be used in the dyeing step are oxidation dye precursors.

As oxidation dye precursors, use may be made of oxidation bases and couplers. By way of example, the oxidation bases are chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, the addition salts thereof and mixtures thereof.

Among the para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para- phenylenediamine, Ν,Ν-dimethyl-para-phenylenediamine, N,N-diethyl-para- phenylenediamine, Ν,Ν-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3- methylaniline, N,N-bis( -hydroxyethyl)-para-phenylenediamine, 4-N,N-bis( - hydroxyethyl)amino-2-methylaniline, 4-N,N-bis( -hydroxyethyl)amino-2- chloroaniline, 2- -hydroxyethyl-para-phenylenediamine, 2-Y-hydroxypropyl-para- phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para- phenylenediamine, N-( -hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl- para-phenylenediamine, N,N-dimethyl-3 -methyl-para-phenylenediamine, N-ethyl-N- ( -hydroxyethyl)-para-phenylenediamine, 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- -hydroxyethylamino-5-aminotoluene and 3-hydroxy-l-(4'-aminophenyl)pyrrolidine, and addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para- phenylenediamine, para-tolylenediamine, 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 addition salts thereof with an acid, are particularly preferred.

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

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

Among the ortho-aminophenols, examples that may be mentioned include 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido2- aminophenol, and addition salts thereof.

Among the heterocyclic bases, examples that may be mentioned include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

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

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

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

Among the pyrazole derivatives mention may be made of the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5- diamino- 1 -methylpyrazole, 4,5-diamino- 1 -( -hydroxyethyl)pyrazole, 3,4- diaminopyrazole, 4,5-diamino- 1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino- 1,3- dimethylpyrazole, 4,5-diamino-3-methyl- 1 -phenylpyrazole, 4,5-diamino- 1 -methyl-3- phenylpyrazole, 4-amino- l,3-dimethyl-5-hydrazinopyrazole, l-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- 1 - isopropylpyrazole, 4,5-diamino-3-methyl- 1 -isopropylpyrazole, 4-amino-5-(2'- aminoethyl)amino-l,3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5- triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino-4- ( -hydroxyethyl)amino-l -methylpyrazole, and addition salts thereof. Use may also be made of 4,5-diamino- l-( -methoxyethyl)pyrazole.

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

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

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

Heterocyclic bases that will preferentially be used include 4,5-diamino- 1-(β- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-lH,5H-pyrazolo[l,2- a]pyrazol-l-one and/or 2-[(3-aminopyrazolo[l,5-a]pyridin-2-yl)oxy]ethanol and/or a salt or solvate thereof.

Among the couplers that may be used in the composition according to the invention, mention may be made especially of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3-benzodioxoles, quino lines, and the addition salts of these compounds with an acid.

These couplers are more particularly chosen from 2,4-diamino-l-( - hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-( -hydroxyethyl)amino-2- methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, l,3-dihydroxy-2- methylbenzene, 4-chloro- 1 ,3-dihydroxybenzene, 2-amino-4-( -hydroxyethylamino)- 1-methoxybenzene, 5-amino-6-chloro-2-methylphenol, 1,3-diaminobenzene, 1,3- bis(2,4-diaminophenoxy)propane, sesamol, l-amino-2-methoxy-4,5- methylenedioxybenzene, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy- N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, l-H-3- methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-l,2,4-triazole and 2,6-dimethylpyrazolo[l,5-b]-l,2,4- triazole, 6-hydroxybenzomorpholine, addition salts thereof with an acid, and mixtures thereof. The addition salts of the oxidation bases and of the couplers are in particular chosen 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) are each generally present in an amount ranging from

0.0001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of the composition comprising them.

The coupler(s) are each generally present in an amount ranging from 0.0001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of the composition comprising them.

The direct dyes that may be used in the dyeing step may be synthetic or natural direct dyes. The direct dyes may in particular be cationic or nonionic. Examples of particularly suitable direct dyes that may be mentioned include nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanines, for instance tetraazacarbocyanines (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes; indigoid direct dyes; phthalocyanine direct dyes, porphyrin direct dyes and natural direct dyes, alone or as mixtures. In particular, mention may be made of direct dyes from among: azo; methine; carbonyl; azine; nitro (hetero)aryl; tri(hetero)arylmethane; porphyrin; phthalocyanine and natural direct dyes, alone or as mixtures.

The composition applied to the keratin fibres during the second step of the process of the invention preferably comprises at least two different fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases or in the form of fatty acid salts, and one or more clays chosen from the smectite family.

In particular, the process according to the invention is performed on wet or dry keratin fibres.

According to a preferred embodiment, the process of the invention may optionally comprise a step of rinsing of the keratin fibres with water between the first and the second step.

The process according to the invention preferably comprises a step of rinsing of the fibres with water on conclusion of the second step of the process of the invention. On conclusion of the process of the invention, the keratin fibres may preferably be dried or left to dry.

Cosmetic composition

A subject of the present invention is also a cosmetic composition comprising:

- at least two different fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases, as defined previously,

- one or more clays chosen from the smectite family, as defined previously, and

- one or more amphoteric or zwitterionic surfactants, as defined previously;

the total amount of fatty acids, expressed relative to the fatty acids in free form, ranges from 1% to 15% by weight, relative to the total weight of the composition.

For the purposes of the present invention, the term "different" refers to two fatty acids whose chemical structures are different.

The cosmetic composition according to the present invention may optionally also comprise one or more silicones, as defined previously.

The cosmetic composition according to the present invention may also optionally comprise one or more organic solvents, as defined previously.

Use

Finally, the present invention relates to the use of a composition comprising one or more fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases or in the form of fatty acid salts, as defined previously, and one or more clays chosen from the smectite family, as defined previously, for treating keratin fibres, in particular human keratin fibres such as the hair, which have undergone direct and/or oxidation dyeing.

Preferably, the composition is that described previously, i.e. it comprises at least two different fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases or in the form of fatty acid salts, and one or more clays chosen from the smectite family.

According to the present application, "keratin fibres" means human keratin fibres and more specifically hair.

The examples that follow serve to illustrate the invention without, however, being limiting in nature. EXAMPLES a. Compositions

Composition (Al) according to the present invention and comparative compositions (Bl), (B2) and (B3) were prepared from the ingredients whose contents are indicated, as mass percentage of active material relative to the total weight of the composition, in the table below.

b. Procedure

Locks of hair, weighing 1 g each, were first washed with a DOP^® shampoo, before being dyed using the oxidation dye product sold under the name ΪΝΟΑ2^®. The dyeing process uses monoethanolamine.

The locks thus dyed were then rinsed, and then washed with compositions (Al), (Bl), (B2) and (B3). Each composition was applied at a rate of 0.4 g of composition per gram of lock.

The denaturing temperature was then determined for each of the locks, by means of DSC (differential scanning calorimetry) analytical measurements according to the following protocol.

Fibres of about 1 mm were cut with scissors. Next, 2.5 mg of hair and 12.5 mg of ultrapure water were weighed out in a closed stainless-steel crucible placed under high pressure. The following thermal programme was then applied: heating from 10°C to 180°C at a temperature increase rate of 10°C/min.

Two tests per treatment were performed.

The higher the denaturing temperature, the better the integrity of the fibre. c. Results

The averages of the results obtained are given in the table below (n

The results show that the fibres onto which composition (Al) of the invention was applied have a higher denaturing temperature than the fibres treated with the comparative compositions (Bl), (B2) and (B3).

The process according to the present invention improves the integrity of fibres that have undergone beforehand an oxidation dyeing process.

Claims

1 . Process for treating keratin fibres and in particular human keratin fibres such as the hair, comprising the following steps:

- a first step of direct and/or oxidation dyeing of keratin fibres, and then

- a second step of applying to said keratin fibres a composition comprising one or more fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases or in the form of fatty acid salts, and one or more clays chosen from the smectite family.

2. Process according to the preceding claim, characterized in that the fatty acids are chosen from carboxylic acids comprising a linear or branched, saturated or unsaturated alkyl chain containing from 6 to 30 carbon atoms and preferably from 10 to 18 carbon atoms.

3. Process according to either of the preceding claims, characterized in that the fatty acids are chosen from lauric acid, palmitic acid and myristic acid, and mixtures thereof, and, preferably, the fatty acids are lauric acid and myristic acid.

4. Process according to any one of the preceding claims, characterized in that the total amount of fatty acids, expressed relative to the fatty acids in free form, ranges from 1% to 30% by weight, preferably from 1% to 20% by weight and more preferentially from 3% to 15% by weight, relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

5. Process according to any one of the preceding claims, characterized in that the mineral base(s) are chosen from alkali metal hydroxides, alkaline-earth metal hydroxides and aqueous ammonia, and mixtures thereof; preferably from alkali metal hydroxides; and, more preferentially, the mineral base is potassium hydroxide.

6. Process according to any one of the preceding claims, characterized in that the total amount of mineral base(s) ranges from 0.5% to 10% by weight and preferably from 1% to 5% by weight relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

7. Process according to any one of Claims 1 to 4, characterized in that the fatty acid salts are chosen from the sodium salts and the potassium salts of said fatty acids, and preferably from potassium laurate, sodium laurate, potassium myristate and sodium myristate, and mixtures thereof.

8. Process according to any one of the preceding claims, characterized in that the clay(s) are chosen from montmorillonite, hectorite, bentonite, beidellite and saponite, and mixtures thereof, and, preferably, the clay is montmorillonite.

9. Process according to any one of the preceding claims, characterized in that the total amount of clay(s) ranges from 0.5% to 20% by weight and preferably from 1% to 10% by weight relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

10. Process according to any one of the preceding claims, characterized in that the composition applied to the keratin fibres during the second step of the process also comprises one or more surfactants chosen from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric and zwitterionic surfactants, and preferably chosen from amphoteric or zwitterionic surfactants.

1 1 . Process according to Claim 10, characterized in that the total amount of surfactant(s) ranges from 0.5% to 20% by weight and preferably from 1% to 15% by weight relative to the total weight of the composition applied to the keratin fibres during the second step of the process.

12. Process according to any one of the preceding claims, characterized in that the step of direct and/or oxidation dyeing of the keratin fibres uses one or more alkaline agents, preferably chosen from alkanolamines, and, more preferentially, the alkaline agent is monoethanolamine.

13. Cosmetic composition comprising:

- at least two different fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases,

- one or more clays chosen from the smectite family, and - one or more amphoteric or zwitterionic surfactants;

the total amount of fatty acids, expressed relative to the fatty acids in free form, ranges from 1% to 15% by weight, relative to the total weight of the composition.

14. Use of a composition comprising one or more fatty acids, chosen from fatty acids in a form neutralized with one or more mineral bases or in the form of fatty acid salts, and one or more clays chosen from the smectite family, for treating keratin fibres, and in particular human keratin fibres such as the hair, which have undergone direct and/or oxidation dyeing.