EP4734950A1

EP4734950A1 - Composition comprising hyaluronic acid and/or a derivative thereof, an anionic surfactant, an alkaline agent, a dye, a solid fatty alcohol and a liquid fatty alcohol

Info

Publication number: EP4734950A1
Application number: EP24737754.2A
Authority: EP
Inventors: Julie BRUYERE; Maud Mario
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2023-06-30
Filing date: 2024-06-27
Publication date: 2026-05-06
Also published as: CN121368472A; WO2025003347A1; FR3150434A1

Abstract

The invention relates to a composition comprising at least one compound chosen from hyaluronic acid and/or a derivative thereof, at least one anionic surfactant, at least one alkaline agent, at least one dye, at least one solid fatty alcohol and at least one liquid fatty alcohol.

Description

Composition comprising hyaluronic acid and/or a derivative thereof, an anionic surfactant, an alkaline agent, a dye, a solid fatty alcohol and a liquid fatty alcohol.

The invention relates to a hair treatment composition comprising hyaluronic acid and/or a derivative thereof, at least one anionic surfactant, at least one alkaline agent, at least one dye, at least one liquid fatty alcohol and at least one solid fatty alcohol.
The invention also relates to a process for dyeing keratin fibres, notably the hair, using this composition.
Finally, the invention relates to the use of such a composition for dyeing keratin fibres, and notably the hair.
Many people have sought for a long time to modify the colour of their hair and in particular to mask their grey hair.
There are essentially three types of process for dyeing the hair:
a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural colour and which uses oxidation dyes which penetrate into the hair fibre and form the dye via an oxidative condensation process;
b) non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists in dyeing keratin fibres with dye compositions containing direct dyes;
c) temporary dyeing, which gives rise to a modification of the natural colour of the hair that remains from one shampoo wash to the next, and which serves to enhance or correct a shade that has already been obtained. It may also be likened to a “makeup” process.
It is thus known practice to dye keratin fibres, in particular human keratin fibres such as the hair, to obtain “permanent” dyeing with dye compositions containing oxidation dye precursors, notably oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols, or heterocyclic compounds such as pyrazoles, pyrazolinones or pyrazolopyridines. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give rise to coloured compounds via a process of oxidative condensation.
It is also possible to vary the shades obtained with these oxidation bases 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.
However, the use of these dye compositions may entail a certain number of drawbacks.
Specifically, after application to keratin fibres, the dyeing power obtained may not be entirely satisfactory, or may even be weak, and lead to a limited range of colours.
The colourings may also be insufficiently fast with respect to external agents such as light, shampoo washing or perspiration, and may also be too selective, i.e. the difference in colouring is too great along the same keratin fibre that is differently sensitized between its end and its root.
Consumers are moreover in search of dyeing products that are more environmentally friendly, notably based on ingredients of natural origin, and which have good application qualities, are easy to use and give good dyeing properties.
The formulation of environmentally-friendly cosmetic products, i.e. products whose design and development take account of environmental issues, is becoming a major preoccupation for contributing towards meeting the global challenges.
It thus proves essential to propose more sustainable compositions, thereby enabling these environmental challenges to be met.
Thus, there is a real need to provide a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, which is more environmentally friendly, without degrading the cosmetic properties, which is notably capable of producing good colour build-up, intensity and chromaticity, while at the same time having low selectivity and good fastness, notably good resistance to shampoo washing, and which is capable of delivering good dyeing performance, even after a period of storage, while at the same time having good application qualities and retaining good sensory performance notably in terms of sheen, suppleness, straightening, ease of combing such as disentangling, and smoothness of feel of keratin fibres such as the hair.
These aims and others are achieved by the present invention, one subject of which is thus a composition comprising:
- at least one compound chosen from hyaluronic acid and/or a derivative thereof, and mixtures thereof;
- at least one anionic surfactant;
- at least one alkaline agent;
- at least one dye;
- at least one liquid fatty alcohol and at least one solid fatty alcohol, the total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) ranges from 6% to 40% by weight relative to the total weight of the composition.
According to a preferred embodiment, the composition according to the invention is a composition for dyeing keratin fibres, notably the hair.
The composition according to the invention may notably lead to chromatic, powerful, intense and sparingly selective colourings, i.e. colourings that are uniform along the length of the fibre. It also allows various shades to be achieved in a very wide range of colours. It also enables good colour build-up.
This composition also gives particularly good coverage of depigmented keratin fibres such as grey hair.
Moreover, the composition according to the invention has good working qualities, notably a creamy texture allowing quick and easy mixing with an oxidizing composition, where appropriate, and easy and uniform spreading over the entire head of hair.
The composition according to the invention has improved resistance to shampoo washing and also good stability over time, notably little or no change in its viscosity during storage.
The composition according to the invention can also afford good cosmetic qualities, notably in terms of sheen, smoothness and suppleness, and a more natural and smoother feel and easier combing, while at the same time preserving the integrity of the fibre.
A subject of the invention is also a process for dyeing the hair using the composition of the invention.
A subject of the invention is also a kit comprising, in a first compartment, a composition as defined previously and, in a second compartment, an oxidizing composition comprising at least one chemical oxidizing agent.
According to the invention, the term “chemical oxidizing agent” means an oxidizing agent other than atmospheric oxygen.
Other subjects, features, 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, notably in the expressions “between” and “ranging from ... to ...”.
Moreover, the expression “at least one" used in the present description is equivalent to the expression “one or more".

Hyaluronic acid and/or a derivative thereof

The composition according to the invention comprises hyaluronic acid and/or a derivative thereof.
In the context of the present invention, the term “hyaluronic acid or a derivative thereof” notably covers the hyaluronic acid basic unit having the formula:
Hyaluronic acid belongs to the glycosaminoglycan (GAG) family.
GAGs are linear chains composed of a repetition of a basic diholoside always containing a hexosamine (glucosamine or galactosamine) and another saccharide (glucuronic acid, iduronic acid or galactose). Glucosamine is either N-sulfated or N-acetylated. On the other hand, galactosamine is always N-acetylated. In addition, there may be O-linked sulfates on hexosamine, uronic acid and galactose.
It is a polysaccharide made up of disaccharides which are themselves composed of D-glucuronic acid and N-acetylglucosamine linked together via alternating beta-1,4 and beta-1,3 glycoside bonds.
According to a particular embodiment, in the context of the present invention, the term “hyaluronic acid or a derivative thereof” comprises the linear polymer comprising the polymeric unit described above, having a molecular weight (MW) which may range between 380 and 13 000 000 daltons. This molecular weight mainly depends on the source from which the hyaluronic acid is obtained and/or on the preparation methods.
Thus, the term “hyaluronic acid or a derivative thereof” comprises all of the hyaluronic acid fractions or subunits having a molecular weight notably within the molecular weight range recalled above.
As hyaluronic acid derivatives, mention may be made in particular of hyaluronic acid salts, hyaluronic acid hydrolysates, quaternized hyaluronic acid derivatives and salts thereof and acetylated hyaluronic acid derivatives and mixtures thereof.
Hyaluronic acid salts that may notably be mentioned include potassium hyaluronate and sodium hyaluronate.
The term "quaternized hyaluronic acid derivatives" means cationic hyaluronic acid comprising at least one quaternary ammonium and/or a salt thereof.
As a quaternized hyaluronic acid derivative, the compound having the INCI name hydroxypropyltrimonium hyaluronate is preferably used.
As acetylated hyaluronic acid derivatives, mention may notably be made preferably of the compound having the INCI name Sodium Acetylated Hyaluronate.
The hyaluronic acid or a derivative thereof is preferably chosen from hyaluronic acid salts and mixtures thereof, and more preferentially sodium hyaluronate.
Hyaluronic acid or a derivative thereof may be present in the composition according to the present invention in a total content ranging from 0.001% to 10% by weight, preferentially from 0.003% to 5% by weight, more preferentially from 0.008% to 1% by weight, better still from 0.01% to 0.5% by weight, even better still from 0.02% to 0.1% relative to the total weight of the composition.
According to a particular embodiment, the total content of hyaluronic acid salts, preferably sodium hyaluronate, preferably ranges from 0.001% to 10% by weight, more preferentially from 0.003% to 5% by weight, better still from 0.008% to 1% by weight, even better still from 0.01% to 0.5% by weight, even better still from 0.02% to 0.1% relative to the total weight of the composition.

Anionic surfactant

The composition according to the present invention comprises one (or more) anionic surfactant(s).
The term “anionic surfactant” means a surfactant including, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the following groups: CO₂H, CO₂ ^-, SO₃H, SO₃ ^-, OSO₃H, OSO₃ ^-, H₂PO₃, HPO₃ ^-, PO₃ ^2-, H₂PO₂, HPO²-, PO₂ ^2-, POH and PO^-.
As examples of anionic surfactants that can be used in the composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, α-olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkyl sulfosuccinamates, acyl isethionates and N-(C1-C4)alkyl-N-acyl taurates, salts of alkyl monoesters of polyglycoside-polycarboxylic acids, 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, fatty acid salts, and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds (unless otherwise mentioned) generally including from 6 to 24 carbon atoms and the aryl group generally denoting a phenyl group.
These compounds may be oxyethylenated and then preferably include from 1 to 50 ethylene oxide units.
The salts of C₆-C₂₄ alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C₆-C₂₄ alkyl polyglycoside-citrates, C₆-C₂₄ alkyl polyglycoside-tartrates and C₆-C₂₄ alkyl polyglycoside-sulfosuccinates.
When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as the magnesium salt.
Examples of amino alcohol salts that may notably be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
The anionic surfactants that may be present may be mild anionic surfactants, i.e. anionic surfactants without a sulfate function.
As regards the mild anionic surfactants, mention may be made in particular of the following compounds and salts thereof, and also mixtures thereof: polyoxyalkylenated alkyl ether carboxylic acids, polyoxyalkylenated alkylaryl ether carboxylic acids, polyoxyalkylenated alkylamido ether carboxylic acids, in particular those including 2 to 50 ethylene oxide groups, alkyl D-galactoside uronic acids, acyl sarcosinates, acyl glutamates and alkylpolyglycoside carboxylic esters.
Use may be made most particularly of polyoxyalkylenated alkyl ether carboxylic acids, for instance lauryl ether carboxylic acid (4.5 OE) sold, for example, under the name Akypo RLM 45 CA from Kao.
The anionic surfactants present may be carboxylic acids comprising at least 8 carbon atoms, also known as fatty acids, optionally in salified form.
For the purposes of the present invention, the term “fatty acid” means an acid comprising at least one linear or branched, saturated or unsaturated hydrocarbon-based chain, such as an alkyl or alkenyl chain, including at least 6 carbon atoms, preferably from 8 to 24 carbon atoms, and better still from 10 to 22 carbon atoms.
The carboxylic acids comprising at least 6 carbon atoms (or fatty acids) according to the invention are neither (poly)oxyalkylenated, nor (poly)glycerolated; in particular, they are neither (poly)oxyethylenated, nor (poly)oxypropylenated.
They preferably have the structure R-COOH in which R denotes a linear or branched C₇-C₂₉, preferably C₉-C₂₃ and better still C₉-C₁₇ alkyl or alkenyl group.
Preferably, the fatty acid according to the invention is chosen from linear fatty acids, better still from unsaturated linear C₁₀-C₂₂ and notably C₁₀-C₁₈ fatty acids (R is a linear C₉-C₂₃ or even C₉-C₁₇ alkenyl).
According to a preferred embodiment, the anionic surfactants are chosen from fatty acids, alkyl sulfates, alkyl ether sulfates, and mixtures thereof, better still chosen from linear fatty acids, even better still from linear unsaturated C₁₀-C₂₂, notably C₁₀-C₁₈ fatty acids, and mixtures thereof such as oleic acid.
Among the anionic surfactants mentioned above, fatty acids are preferably used. Mention may notably be made of oleic, linoleic, linolenic and undecylenic acids, and mixtures thereof. More preferentially, oleyl alcohol will be used.
The total content of the anionic surfactant(s) in the composition preferably ranges from 0.01% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.5% to 8% by weight, and even better still from 0.8% to 6% by weight relative to the total weight of the composition.
According to a preferred embodiment, the total content of fatty acids, preferably of oleic acid, preferably ranges from 0.1% to 10% by weight, better still from 0.5% to 8% by weight and even better still from 0.8% to 6% by weight relative to the total weight of the composition.

Alkaline agent

The composition according to the present invention comprises at least one mineral, organic or hybrid alkaline agent and mixtures thereof.
For the purposes of the present invention, the terms “alkaline agent” and “basifying agent” are used interchangeably.
The mineral basifying agent(s) are preferably chosen from aqueous ammonia, alkali metal, alkaline-earth metal or ammonium (bi)carbonates, alkali metal or alkaline-earth metal phosphates such as sodium phosphates or potassium phosphates, sodium or potassium hydroxides, alkali metal or alkaline-earth metal silicates or metasilicates such as sodium metasilicate, and mixtures thereof, better still ammonium bicarbonate.
The organic basifying agent(s) are preferably chosen from alkanolamines, amino acids, organic amines other than alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, 1,3-diaminopropane, spermine, spermidine and mixtures thereof.
The term “alkanolamine” means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C₁-C₈ 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 C₁-C₄ hydroxyalkyl radicals are in particular suitable for performing the invention.
In particular, the alkanolamine(s) are chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethyl)aminomethane and mixtures thereof.
Advantageously, the amino acids are basic amino acids comprising an additional amine function. Such basic amino acids are preferably chosen from histidine, lysine, arginine, ornithine and citrulline.
The organic amine may also be chosen from organic amines of heterocyclic type.
Use may be made in particular of guanidine carbonate or monoethanolamine hydrochloride as hybrid compounds.
The alkaline agent(s) that are useful according to the invention are preferably chosen from alkanolamines such as monoethanolamine, diethanolamine or triethanolamine; aqueous ammonia, (bi)carbonates such as Na, K, Mg or Ca (bi)carbonates, ammonium (bi)carbonates, alkali metal or alkaline-earth metal silicates or metasilicates such as sodium metasilicate and mixtures thereof, more preferentially from alkanolamines and aqueous ammonia, better still from alkanolamines and even better still monoethanolamine.
In a particular embodiment, the composition according to the invention is free of aqueous ammonia.
The total content of the alkaline agent(s) preferably ranges from 0.01% to 30% by weight, more preferentially from 0.05% to 20% by weight, better still from 0.08% to 15% by weight, and even better still from 0.1% to 10% by weight, relative to the total weight of the composition.
According to a preferred embodiment, the total content of alkanolamine, preferably monoethanolamine, preferably ranges from 0.01% to 30% by weight, more preferentially from 0.05% to 20% by weight, better still from 0.08% to 15% by weight, even better still from 0.1% to 10% by weight, relative to the total weight of the composition.

Dye

The composition according to the invention comprises one (or more) dye(s) preferably chosen from oxidation dyes, direct dyes and mixtures thereof.
Preferably, the composition comprises one (or more) oxidation dye(s).
The oxidation dyes may be chosen from one or more oxidation bases, optionally in combination with one or more couplers.
Oxidation base
The oxidation bases may be present in the form of salts, solvates and/or solvates of salts.
The addition salts of the oxidation bases present in the composition according to the invention are notably chosen from the addition salts with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, methanesulfonates, phosphates and acetates, and the addition salts with a base such as sodium hydroxide, potassium hydroxide, aqueous ammonia, amines or alkanolamines.
Moreover, the solvates of the oxidation bases more particularly represent the hydrates of said oxidation bases and/or the combination of said oxidation bases with a linear or branched C₁ to C₄ alcohol such as methanol, ethanol, isopropanol or n-propanol. Preferably, the solvates are hydrates.
By way of example, the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and the corresponding addition salts, solvates, and solvates of the salts, and mixtures thereof.
Among the para-phenylenediamines that may be mentioned are, for example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-(γ-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4’-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4’-aminophenyl)pyrrolidine, and the addition salts, solvates and/or solvates of salts thereof.
Among the para-phenylenediamines mentioned above, particular preference is given to para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-(γ-hydroxypropyl)-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine, and the corresponding addition salts, solvates and/or solvates of salts thereof.
Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N’-bis(β-hydroxyethyl)-N,N’-bis(4’-aminophenyl)-1,3-diaminopropanol, N,N’-bis(β-hydroxyethyl)-N,N’-bis(4’-aminophenyl)ethylenediamine, N,N’-bis(4-aminophenyl)tetramethylenediamine, N,N’-bis(β-hydroxyethyl)-N,N’-bis(4-aminophenyl)tetramethylenediamine, N,N’-bis(4-methylaminophenyl)tetramethylenediamine, N,N’-bis(ethyl)-N,N’-bis(4’-amino-3’-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the corresponding addition salts, the solvates, solvates of the salts, and mixtures thereof.
Among the para-aminophenols that are mentioned are, for example, 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-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts, the solvates and solvates of the salts.
Among the ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the corresponding addition salts, the solvates and the solvates of the salts.
Among the heterocyclic bases that may be mentioned, for example, are pyridine, pyrimidine and pyrazole derivatives.
Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for example 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the corresponding addition salts, the solvates and the solvates of the salts.
Other pyridine oxidation bases that are useful in the present invention are the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol, 2-β-hydroxyethoxy-3-aminopyrazolo[1,5-a]pyridine and 2-(4-dimethylpiperazinium-1-yl)-3-aminopyrazolo[1,5-a]pyridine, and the corresponding addition salts, the solvates and the solvates of the salts.
More particularly, the oxidation bases that are useful in the present invention are chosen from 3-aminopyrazolo[1,5-a]pyridines and preferably substituted on carbon atom 2 with:
a) a (di)(C1-C6)(alkyl)amino group, said alkyl group possibly being substituted with at least one hydroxyl, amino or imidazolium group;
b) an optionally cationic 5- to 7-membered heterocycloalkyl group containing from 1 to 3 heteroatoms, optionally substituted with one or more (C1-C6)alkyl groups, such as a di(C1-C4)alkylpiperazinium group; or
c) a (C1-C6)alkoxy group optionally substituted with one or more hydroxyl groups, such as a β-hydroxyalkoxy group, and the corresponding addition salts, the solvates and the solvates of the salts.
Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; 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, the solvates and the solvates of the salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.
Among the pyrazole derivatives that may be mentioned are the compounds described in 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-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4’-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4’-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2’-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the corresponding addition salts, the solvates and the solvates of the salts. Use may also be made of 4,5-diamino-1-(β-methoxyethyl)pyrazole.
A 4,5-diaminopyrazole will preferably be used and even more preferentially 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a corresponding salt, a solvate and/or a solvate of a salt.
The pyrazole derivatives that may also be mentioned comprise diamino-N,N-dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and the corresponding addition salts: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,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-bis(2-hydroxyethyl)-1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,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 and 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, the salts thereof, the solvates thereof and the solvates of the salts thereof.
Use will preferably be made of 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a corresponding salt, solvate and/or solvate of a salt.
Use will preferably be made, as heterocyclic bases, of 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or 2-β-hydroxyethoxy-3-aminopyrazolo[1,5-a]pyridine and/or a corresponding salt, solvate and/or solvate of a salt.
Preferably, the oxidation base(s) are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and the corresponding addition salts, the solvates thereof and/or the solvates of the salts thereof, and mixtures thereof; more preferentially from 2-methoxymethyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-γ-hydroxypropyl-para-phenylenediamine, and the addition salts thereof, the solvates thereof and/or the solvates of the salts thereof, and mixtures thereof.
When the composition comprises at least one oxidation base, the oxidation base(s) are preferably present in a total content ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, more preferentially from 0.01% to 10% by weight, better still from 0.05% to 5%, even better still from 0.1% to 3% by weight, relative to the weight of the composition.
Oxidation coupler
The oxidation dye(s) may also be chosen from one or more couplers, which may be chosen from the couplers conventionally used for the dyeing of keratin fibres.
Preferably, the composition according to the invention comprises one or more couplers.
Among the couplers that are useful according to the invention, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents, and also the corresponding addition salts, the solvates and solvates of the salts thereof.
Mention may be made, for example, of 6-hydroxybenzomorpholine, hydroxyethyl-3,4-methylenedioxyaniline, 2-amino-5-ethylphenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol and 3-amino-2-chloro-6-methylphenol, the corresponding addition salts, the solvates and the solvates of the salts thereof, and the corresponding mixtures.
In general, the addition salts of the couplers that may be used in the context of the invention are chosen in particular from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts with a base such as sodium hydroxide, potassium hydroxide, aqueous ammonia, amines or alkanolamines.
Moreover, the solvates more particularly represent the hydrates of these couplers and/or the combination of these couplers with a linear or branched C1 to C4 alcohol such as methanol, ethanol, isopropanol or n-propanol. Preferably, the solvates are hydrates.
In a preferred embodiment, the composition according to the invention is free of oxidation couplers chosen from resorcinol and resorcinol derivatives such as 2-methylresorcinol or 4-chlororesorcinol, addition salts thereof, solvates thereof and the solvates of the salts thereof.
When the composition comprises one or more oxidation couplers, the total content of the coupler(s) present in the composition according to the invention ranges from 0.001% to 20% by weight, more preferentially from 0.005% to 15% by weight, better still from 0.01% to 10% by weight, even better still from 0.05% to 5% by weight, and even better still from 0.1% to 3% by weight, relative to the total weight of the composition.
When they are present, the total content of the oxidation dyes preferably ranges from 0.001% to 20% by weight, more preferentially from 0.005% to 15% by weight, better still from 0.01% to 10% by weight, even better still from 0.05% to 5% by weight, and even better still from 0.1% to 3% by weight, relative to the total weight of the composition.
The composition according to the invention may optionally comprise one or more synthetic or natural direct dyes, chosen from anionic and nonionic species, preferably cationic or nonionic species, either as sole dyes or in addition to the oxidation dye(s).
Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
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 relative to the total weight of the composition.
When they are present, the total content of the dye(s) ranges from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, more preferentially from 0.01% to 10% by weight, better still from 0.05% to 5% by weight and even better still from 0.1% to 3% by weight, relative to the total weight of the composition.
According to a preferred embodiment of the invention, the composition and similarly the ready-to-use composition contain at least one dye and preferably at least one oxidation dye as defined previously.

Fatty substance

The composition according to the invention comprises at least one liquid fatty alcohol and at least one solid fatty alcohol, the total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) ranges from 6% to 40% by weight relative to the total weight of the composition.
Preferably, the total content of solid fatty alcohol(s) is greater than or equal to 5% by weight relative to the total weight of the composition.
According to the invention, the term “fatty alcohols” means compounds containing at least one linear or branched, saturated or unsaturated hydrocarbon-based group comprising from 6 to 40 and better still from 8 to 30 carbon atoms, which are optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
The fatty alcohols that may be used in the present invention are neither (poly)oxyalkylenated nor (poly)glycerolated.
The term “liquid fatty alcohol” means a fatty alcohol with a melting point of less than or equal to 25°C at atmospheric pressure (1.013×10⁵ Pa) and the term “solid fatty alcohol” means a fatty alcohol with a melting point of greater than 25°C at atmospheric pressure (1.013×10⁵ Pa).
For the purposes of the present invention, the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (differential scanning calorimetry or DSC) as described in the standard ISO 11357-3; 1999. The melting point may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by the company TA Instruments. In the present patent application, all the melting points are determined at atmospheric pressure (1.013×10⁵ Pa).
The liquid fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated alcohols, preferably unsaturated or branched alcohols, including from 6 to 40 carbon atoms and preferably from 8 to 30 carbon atoms.
These fatty alcohols are neither oxyalkylenated nor glycerolated.
Examples that may be mentioned include octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol and linoleyl alcohol, and mixtures thereof; better still, the liquid fatty alcohol is oleyl alcohol.
According to a particular embodiment, the total content of liquid fatty alcohol(s) preferably ranges from 0.1% to 15% by weight, more preferentially from 0.5% to 10% by weight and better still from 1% to 5% by weight relative to the total weight of the composition.
The solid fatty alcohols may be saturated or unsaturated, and linear or branched, and include from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms. Preferably, the solid fatty alcohols have the structure R-OH with R denoting a linear alkyl group, optionally substituted with one or more hydroxyl groups, comprising from 8 to 40, preferentially from 10 to 30 carbon atoms, better still from 12 to 24 atoms and even better still from 14 to 22 carbon atoms.
The solid fatty alcohols that may be used are preferably chosen from saturated or unsaturated, linear or branched, preferably linear and saturated, (mono)alcohols including from 8 to 40 carbon atoms, preferentially from 10 to 30, better still from 12 to 24 and even better still from 14 to 22 carbon atoms.
The solid fatty alcohols that may be used may be chosen, alone or as a mixture, from: myristyl alcohol (or 1-tetradecanol); cetyl alcohol (or 1-hexadecanol); stearyl alcohol (or 1-octadecanol); arachidyl alcohol (or 1-eicosanol); behenyl alcohol (or 1-docosanol); lignoceryl alcohol (or 1-tetracosanol); ceryl alcohol (or 1-hexacosanol); montanyl alcohol (or 1-octacosanol); myricyl alcohol (or 1-triacontanol).
Preferentially, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, arachidyl alcohol, and mixtures thereof. Particularly preferably, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol and mixtures thereof such as cetylstearyl alcohol or cetearyl alcohol.
According to another particular embodiment, the total content of solid fatty alcohol(s) is greater than or equal to 5% by weight, preferably ranges from 6% to 40% by weight, more preferentially from 6.5% to 35% by weight, better still from 7% to 30% by weight, even better still from 7.5% to 25% by weight, or even from 10% to 20% by weight, relative to the total weight of the composition.
The total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) preferably ranges from 6.5% to 35% by weight, better still from 7% to 30% by weight, even better still from 7.5% to 25% by weight, or even from 8% to 20% by weight, relative to the total weight of the composition.
The composition according to the invention may also comprise one or more fatty substances other than the fatty acids and other than the liquid fatty alcohols and the solid fatty alcohols as defined previously.
The additional fatty substances that are useful according to the invention may be liquid fatty substances (or oils) and/or solid fatty substances. The term “liquid fatty substance” means a fatty substance with a melting point of less than or equal to 25°C at atmospheric pressure (1.013×10⁵ Pa) and the term “solid fatty substance” means a fatty substance with a melting point of greater than 25°C at atmospheric pressure (1.013×10⁵ Pa).
The term “fatty substance” means an organic compound that is insoluble in water at 25°C and at atmospheric pressure (1.013×10⁵ Pa) (solubility of less than 5% by weight, preferably less than 1% by weight, even more preferentially less than 0.1% by weight). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms and/or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
The additional fatty substances other than the fatty acids and other than the solid fatty alcohols and the liquid fatty alcohols, that may be used in the present invention, are neither (poly)oxyalkylenated nor (poly)glycerolated.
Preferably the additional fatty substances other than the fatty acids and other than the solid fatty alcohols and the liquid fatty alcohols, that are useful according to the invention, are non-silicone.
The term “non-silicone fatty substance” refers to a fatty substance not containing any Si-O bonds and the term “silicone fatty substance” refers to a fatty substance containing at least one Si-O bond.
More particularly, the additional liquid fatty substance(s) other than the liquid fatty acids and the liquid fatty alcohols may be chosen from liquid hydrocarbons comprising more than 6 carbon atoms, non-silicone oils of animal origin, oils of triglyceride type of plant or synthetic origin, fluoro oils, liquid esters of fatty acid and/or of fatty alcohol other than triglycerides, and mixtures thereof.
It is recalled that the fatty esters and acids more particularly contain at least one saturated or unsaturated, linear or branched hydrocarbon-based group comprising from 6 to 40 and better still from 8 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
By way of example, the liquid hydrocarbons comprising more than 6 carbon atoms may be linear, branched, optionally cyclic, and preferably saturated. Examples that may be mentioned include hexane, cyclohexane, undecane, dodecane, isododecane, tridecane or isoparaffins, such as isohexadecane or isodecane, and mixtures thereof.
The liquid hydrocarbons comprising more than 6 carbon atoms may also be chosen from linear or branched liquid hydrocarbons comprising more than 16 carbon atoms, which are of mineral or synthetic origin, and are preferably chosen from liquid paraffins or liquid petroleum jelly (or mineral oil), polydecenes, hydrogenated polyisobutene such as Parleam®, and mixtures thereof.
The liquid hydrocarbons comprising more than 6 carbon atoms may also be chosen from mixtures of alkanes containing from 8 to 28 carbon atoms, more particularly from 15 to 28 carbon atoms; mention may be made of mixtures having, for example, the following INCI names: C15-19 Alkane, C18-C21 Alkane, C21-C28 Alkane, for instance the products Gemseal 40, Gemseal 60 and Gemseal 120 sold by Total, Emogreen L19 sold by SEPPIC and Emogreen L15 sold by SEPPIC, more particularly Emogreen L19 sold by SEPPIC.
A hydrocarbon-based oil of animal origin that may be mentioned is perhydrosqualene.
The triglyceride oils of plant or synthetic origin are preferably chosen from liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stéarinerie Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil (shea olein), and mixtures thereof.
As regards the liquid fatty acid and/or fatty alcohol esters, other than the triglycerides mentioned previously, mention may be made notably of esters of saturated or unsaturated, linear C1 to C26 or branched C3 to C26 aliphatic mono- or polyacids and of saturated or unsaturated, linear C1 to C26 or branched C3 to C26 aliphatic mono- or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.
Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid is branched.
Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; isostearyl octanoate; isocetyl octanoate; octyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; octyl isononanoate; 2-ethylhexyl isononate; octyldodecyl erucate; oleyl erucate; ethyl palmitate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate; alkyl myristates such as isopropyl 2-octyldodecyl myristate, isobutyl stearate; 2-hexyldecyl laurate, and mixtures thereof.
Esters of C4 to C22 dicarboxylic or tricarboxylic acids and of C1 to C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C2 to C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
Mention may notably 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, and mixtures thereof.
The composition may also comprise, as fatty ester, sugar esters and diesters of C6 to C30 and preferably C12 to C22 fatty acids. It is recalled that the term “sugar” refers to oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which include at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides other than the anionic polysaccharides described hereinbelow.
Examples of suitable sugars that may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen notably from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched, saturated or unsaturated C6 to C30 and preferably C12 to C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
The esters may also be chosen from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.
These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates or mixtures thereof notably such as the mixed oleo-palmitate, oleo-stearate and palmito-stearate esters.
More particularly, use is made of monoesters and diesters and notably sucrose, glucose or methylglucose mono- or di-oleates, -stearates, -behenates, -oleopalmitates, -linoleates, -linolenates and -oleostearates, and mixtures thereof.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
Preferably, use will be made of a liquid ester of a monoacid and of a monoalcohol.
The additional solid fatty substances other than the solid fatty alcohols preferably have a viscosity of greater than 2 Pa.s, measured at 25°C and at a shear rate of 1 s^-1.
The additional solid fatty substance(s) other than solid fatty alcohols are preferably chosen from solid fatty acid and/or fatty alcohol esters, waxes, ceramides and mixtures thereof.
The solid esters of a fatty acid and/or of a fatty alcohol that may be used are preferably chosen from esters derived from a C9-C26 carboxylic fatty acid and/or from a C9-C26 fatty alcohol.
Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C2-C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
Mention may notably be made of octyldodecyl behenate, isocetyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate, cetyl octanoate, decyl oleate, hexyl stearate, octyl stearate, myristyl stearate, cetyl stearate, stearyl stearate, octyl pelargonate, cetyl myristate, myristyl myristate, stearyl myristate, diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, dioctyl maleate, octyl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, and mixtures thereof.
Preferably, the solid esters of a fatty acid and/or of a fatty alcohol are chosen from C9-C26 alkyl palmitates, notably myristyl, cetyl or stearyl palmitate; C9-C26 alkyl myristates, such as cetyl myristate, stearyl myristate and myristyl myristate; and C9-C26 alkyl stearates, notably myristyl, cetyl and stearyl stearate; and mixtures thereof.
Butters may also be used.
For the purposes of the present invention, the term “butter” (also referred to as a “pasty fatty substance”) means a lipophilic fatty compound with a reversible solid/liquid change of state, including at a temperature of 25°C and at atmospheric pressure (760 mmHg) a liquid fraction and a solid fraction. Preferably, the butter(s) according to the invention have a starting melting temperature above 25°C and an end melting temperature below 60°C.
Preferably, the particular butter(s) are of plant origin, such as those described in Ullmann’s Encyclopedia of Industrial Chemistry (“Fats and Fatty Oils”, A. Thomas, published online: JUN 15, 2000, DOI: 10.1002/14356007.a10_173, point 13.2.2.2. Shea Butter, Borneo Tallow, and Related Fats (Vegetable Butters)).
Mention may be made more particularly of shea butter, Karité Nilotica butter (Butyrospermum parkii), galam butter, (Butyrospermum parkii), Borneo butter or fat or tengkawang tallow (Shorea stenoptera), shorea butter, illipé butter, madhuca butter or Bassia madhuca longifolia butter, mowrah butter (Madhuca latifolia), katiau butter (Madhuca mottleyana), phulwara butter (M. butyracea), mango butter (Mangifera indica), murumuru butter (Astrocaryum murumuru), kokum butter (Garcinia indica), ucuuba butter (Virola sebifera), tucuma butter, painya butter (Kpangnan) (Pentadesma butyracea), coffee butter (Coffea arabica), apricot butter (Prunus armeniaca), macadamia butter (Macadamia ternifolia), grapeseed butter (Vitis vinifera), avocado butter (Persea gratissima), olive butter (Olea europaea), sweet almond butter (Prunus amygdalus dulcis), cocoa butter and sunflower butter.
An example of a preferred butter is shea butter.
In a known manner, shea butter is extracted from the fruit (also called “kernels” or “nuts”) of the Butyrospemum parkii tree. Each fruit contains between 45% and 55% fat, which is generally extracted and refined.
When they are present, the total content of the additional fatty substance(s) other than fatty acids and other than fatty alcohols described previously preferably ranges from 0.1% to 20% by weight, more preferentially from 0.5% to 15% by weight and better still from 1% to 10% by weight relative to the total weight of the composition.
Preferably, the composition according to the invention comprises at least one fatty substance derived from shea, preferably chosen from shea butter, shea butter oil and mixtures thereof.
In a preferred embodiment, the composition according to the invention comprises one or more fatty substances derived from shea, the total content of the fatty substance(s) derived from shea preferably ranging from 0.1% to 15% by weight, more preferentially from 0.5% to 10% by weight and better still from 1% to 8% by weight, relative to the total weight of the composition.

Surfactants other than anionic surfactants

The composition according to the invention may also comprise one or more surfactants other than anionic surfactants.
Preferably, the composition according to the present invention comprises one or more surfactants other than anionic surfactants.
These may be chosen from nonionic surfactants, cationic surfactants, amphoteric surfactants and/or mixtures thereof.
According to a preferred embodiment, the surfactants other than anionic surfactants are nonionic surfactants.
The nonionic surfactant(s) that may be used in the composition of the present invention are notably described, for example, in the “Handbook of Surfactants” by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pages 116-178.
Examples of nonionic surfactants that may be mentioned include the following compounds, alone or as a mixture:
- oxyalkylenated (C₈-C₂₄)alkylphenols;
- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated C₈-C₄₀ alcohols, preferably including one or two fatty chains;
- saturated or unsaturated, linear or branched, oxyalkylenated C₈ to C₃₀ fatty acid amides;
- esters of saturated or unsaturated, linear or branched, C₈ to C₃₀ acids and of polyethylene glycols;
- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, C₈ to C₃₀ acids and of sorbitol;
- fatty acid esters of sucrose;
- (C₈-C₃₀)alkyl(poly)glucosides, (C₈-C₃₀)alkenyl(poly)glucosides, which are optionally oxyalkylenated (0 to 10 oxyalkylene units) and comprising from 1 to 15 glucose units, (C₈-C₃₀)alkyl(poly)glucoside esters;
- saturated or unsaturated oxyethylenated plant oils;
- condensates of ethylene oxide and/or of propylene oxide;
- N-(C₈-C₃₀)alkylglucamine and N-(C₈-C₃₀)acylmethylglucamine derivatives;
- amine oxides.
They are notably chosen from alcohols, α-diols and (C₁-C₂₀)alkylphenols, these compounds being ethoxylated, propoxylated or glycerolated and containing at least one fatty chain including, for example, from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly ranging notably from 1 to 200, and the number of glycerol groups possibly ranging notably from 1 to 30.
Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols, ethoxylated fatty amides preferably containing from 1 to 30 ethylene oxide units, polyglycerolated fatty amides including on average from 1 to 5, and in particular from 1.5 to 4, glycerol groups, ethoxylated fatty acid esters of sorbitan containing from 1 to 30 ethylene oxide units, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, (C₆-C₂₄ alkyl)polyglycosides, oxyethylenated plant oils, N-(C₆-C₂₄ alkyl)glucamine derivatives, amine oxides such as (C₁₀-C₁₄ alkyl)amine oxides or N-(C₁₀-C₁₄ acyl)aminopropylmorpholine oxides.
The C₈-C₃₀ and preferably C₁₂-C₂₂ fatty acid esters (notably monoesters, diesters and triesters) of sorbitan may be chosen from:
sorbitan caprylate; sorbitan cocoate; sorbitan isostearate; sorbitan laurate; sorbitan oleate; sorbitan palmitate; sorbitan stearate; sorbitan diisostearate; sorbitan dioleate; sorbitan distearate; sorbitan sesquicaprylate; sorbitan sesquiisostearate; sorbitan sesquioleate; sorbitan sesquistearate; sorbitan triisostearate; sorbitan trioleate; and sorbitan tristearate.
The polyoxyethylenated C₈-C₃₀ (preferably C₁₂-C₁₈) fatty acid esters (notably monoesters, diesters and triesters) of sorbitan notably containing from 2 to 20 mol of ethylene oxide may be chosen from polyoxyethylenated esters of C₁₂-C₁₈ fatty acids, in particular lauric, myristic, cetylic or stearic acid, of sorbitan notably containing from 2 to 30 mol of ethylene oxide, such as:
polyoxyethylenated sorbitan monolaurate (4 OE) (Polysorbate-21),
polyoxyethylenated sorbitan monolaurate (20 OE) (Polysorbate-20),
polyoxyethylenated sorbitan monopalmitate (20 OE) (Polysorbate-40),
polyoxyethylenated sorbitan monostearate (20 OE) (Polysorbate-60),
polyoxyethylenated sorbitan monostearate (4 OE) (Polysorbate-61),
polyoxyethylenated sorbitan monooleate (20 OE) (Polysorbate-80),
polyoxyethylenated sorbitan monooleate (5 OE) (Polysorbate-81),
polyoxyethylenated sorbitan tristearate (20 OE) (Polysorbate-65),
polyoxyethylenated sorbitan trioleate (20 OE) (Polysorbate-85).
The polyoxyethylenated C₈-C₃₀ (preferably C₁₂-C₁₈) fatty acid esters (notably monoesters, diesters, triesters and tetraesters) of sorbitan, notably containing from 2 to 20 mol of ethylene oxide, may be chosen from polyoxyethylenated esters, notably containing from 2 to 20 mol of ethylene oxide, such as of C₁₂-C₁₈ fatty acids, in particular lauric, myristic, cetylic or stearic acid, and of sorbitan, such as:
- the ester polyoxyethylenated with 20 OE of sorbitan and of cocoic acid (PEG-20 sorbitan cocoate);
- the polyoxyethylenated esters (notably containing from 2 to 20 OE) of sorbitan and of isostearic acid (such as PEG-2 sorbitan isostearate; PEG-5 sorbitan isostearate; PEG-20 sorbitan isostearate such as the product sold under the name Nikkol TI 10 V by the company Nikkol),
- the polyoxyethylenated esters (notably containing from 2 to 20 OE) of sorbitan and of lauric acid (such as PEG-10 sorbitan laurate),
- the polyoxyethylenated esters (notably containing from 2 to 20 OE) of sorbitan and of oleic acid containing 10 oxyethylene groups (such as PEG-6 sorbitan oleate; PEG-20 sorbitan oleate),
- the polyoxyethylenated esters (notably containing from 3 to 20 OE) of sorbitan and of stearic acid (such as PEG-3 sorbitan stearate; PEG-4 sorbitan stearate; PEG-6 sorbitan stearate).
The surfactant(s) other than anionic surfactants are preferably chosen from nonionic surfactants, more preferentially chosen from saturated or unsaturated, C₈-C₂₄ fatty alcohols ethoxylated with from 1 to 200 ethylene oxide groups, C₈-C₃₀ fatty acid esters of sorbitan ethoxylated with from 1 to 30 ethylene oxide units, (C₆-C₂₄ alkyl)polyglycosides and mixtures thereof, better still from ethoxylated C₈-C₂₄ fatty alcohols, (C₆-C₂₄ alkyl)polyglycosides and mixtures thereof, even better still from alkylpolyglycosides such as cocoyl glucoside, caprylyl/capryl glucoside, lauryl glucoside, decyl glucoside, cetearyl glucoside and steareth-100.
Preferably, the surfactant(s) other than anionic surfactants and mixtures thereof represent from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight and better still from 0.5% to 6% by weight relative to the total weight of the composition.

Sequestrants

The composition according to the invention may comprise at least one sequestrant (or chelating agent).
The definition of a “sequestrant” (or “chelating agent”) is well known to those skilled in the art and refers to a compound or a mixture of compounds that are capable of forming a chelate with a metal ion. A chelate is an inorganic complex in which a compound (the sequestrant or chelating agent) is coordinated to a metal ion, i.e. it forms one or more bonds with the metal ion (formation of a ring including the metal ion).
A sequestrant (or chelating agent) generally comprises at least two electron-donating atoms which enable the formation of bonds with the metal ion.
In the context of the present invention, the sequestrant(s) may be chosen from carboxylic acids, preferably aminocarboxylic acids, phosphonic acids, preferably aminophosphonic acids, polyphosphoric acids, preferably linear polyphosphoric acids, salts thereof, and derivatives thereof.
The salts are notably alkali metal, alkaline-earth metal, ammonium and substituted ammonium salts.
According to the present invention, the sequestrants are preferably chosen from diethylenetriaminepentaacetic acid (DTPA) and salts thereof, diethylenediaminetetraacetic acid (EDTA) and salts thereof, ethylenediaminedisuccinic acid (EDDS) and salts thereof, etidronic acid and salts thereof, N,N-dicarboxymethylglutamic acid (GLDA) and salts thereof, and mixtures thereof.
More preferentially, the sequestrant(s) are chosen from N,N-dicarboxymethylglutamic acid (GLDA) and salts thereof, and mixtures thereof.
Among the salts of these compounds, the alkali metal salts and notably the sodium or potassium salts are preferred.
When the composition comprises one or more sequestrants, the total content of the sequestrant(s) preferably ranges from 0.001% to 15% by weight, more preferentially from 0.005% to 10% by weight, better still from 0.01% to 8% by weight, even better still from 0.05% to 5% by weight, relative to the total weight of the composition.

Thickening polymers

The composition according to the invention may also comprise at least one thickening polymer, preferably chosen from polysaccharides, more preferentially from anionic polysaccharides.
The term “polysaccharides” means polymers which contain at least 11 monosaccharide units. Preferentially, the polysaccharides of the invention include between 20 and 100 000 monosaccharide units.
The anionic polysaccharides according to the invention comprise one or more anionic or anionizable groups, and do not comprise any cationic or cationizable groups.
The anionic polysaccharides that are useful according to the invention may be chosen from those derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulfate; anhydrogalactose sulfate.
The anionic polysaccharides may be natural or synthetic.
According to a preferred embodiment, the anionic polysaccharides that are useful in the composition according to the invention are chosen from native gums such as:
• tree or shrub exudates, for instance: acacia gum (branched polymer of galactose, arabinose, rhamnose and glucuronic acid); ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid); karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid); gum tragacanth (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
• gums derived from algae, such as: alginates (polymers of mannuronic acid and glucuronic acid); carrageenans and furcellerans (polymers of galactose sulfate and anhydrogalactose sulfate);
• microbial gums such as: xanthan gums (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid); gellan gums (polymer of partially acylated glucose, rhamnose and glucuronic acid).
For the purposes of the present invention, the term “microbial gums” means substances synthesized by fermentation of sugars by microorganisms.
According to a preferred embodiment, the anionic polysaccharides that are useful in the composition according to the invention are chosen from anionic gums, better still from anionic microbial gums, more preferentially from xanthan gums.
When they are present, the total content of thickening polymers preferably ranges from 0.005% to 10% by weight relative to the total weight of the composition, preferably from 0.01% to 5% by weight, better still from 0.05% to 2% by weight relative to the total weight of the composition.
When they are present, the total content of anionic polysaccharides as defined previously preferably ranges from 0.005% to 10% by weight relative to the total weight of the composition, preferably from 0.01% to 5% by weight, better still from 0.05% to 2% by weight relative to the total weight of the composition.
When they are included in the composition, the total content of the anionic microbial gums as defined previously preferably ranges from 0.005% to 10% by weight relative to the total weight of the composition, preferably from 0.01% to 5% by weight, better still from 0.05% to 2% by weight relative to the total weight of the composition.

Glycoprotein

The composition according to the invention may also comprise at least one glycoprotein.
Preferably, the composition according to the invention comprises a glycoprotein.
The term "glycoprotein" means one or more oligosaccharides covalently bonded to a polypeptide chain via the -OH function of serine and threonine residues (O-linked) or via the amide function of an asparagine residue (N-linked).
The term "oligosaccharides" means short polymers consisting of several identical or different monosaccharide units linked together by glycosidic bonds.
Preferentially, the glycoproteins of the invention comprise from 1% to 70% by weight of oligosaccharides, more preferentially from 2% to 50% by weight, even more preferentially from 5% to 30% by weight relative to the total weight of the glycoprotein.
According to a preferred embodiment, the glycoprotein(s) according to the invention are produced from microorganisms, more preferentially extracted from bacteria, even more preferentially from gram-negative bacteria.
Preferably, the glycoprotein according to the invention is obtained by culturing the bacterial strain Pseudoalteromonas antarctica NF3.
Mention may be made, for example, of the compound known under the INCI name Pseudoalteromonas Ferment Extract, sold under the trade name Antarcticine® by the company Lipotec.
When the composition comprises one or more glycoproteins, the total content of the glycoprotein(s) preferably ranges from 0.001% to 1% by weight, more preferentially from 0.005% to 0.5% by weight, better still from 0.01% to 0.1% by weight, relative to the total weight of the composition.
According to one preferred embodiment, the composition according to the invention comprises:
- at least one compound chosen from hyaluronic acid and/or a derivative thereof, and mixtures thereof;
- at least one anionic surfactant, preferably chosen from fatty acids;
- at least one alkaline agent;
- at least one dye, preferably chosen from oxidation dyes;
- at least one liquid fatty alcohol and at least one solid fatty alcohol, the total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) ranges from 6% to 40% by weight relative to the total weight of the composition;
- at least one surfactant other than anionic surfactants, preferably chosen from saturated or unsaturated, C₈-C₂₄ fatty alcohols ethoxylated with from 1 to 200 ethylene oxide groups, C₈-C₃₀ fatty acid esters of sorbitan ethoxylated with from 1 to 30 ethylene oxide units, (C₆-C₂₄ alkyl)polyglycosides and mixtures thereof, better still from ethoxylated C₈-C₂₄ fatty alcohols, (C₆-C₂₄ alkyl)polyglycosides and mixtures thereof.

Solvents

The composition according to the invention may also comprise at least one organic solvent.
Examples of organic solvents that may be mentioned include linear or branched C₂-C₄ alkanols, such as ethanol, propanol and isopropanol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, glycerol, 1,3-propanediol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.
Preferably, the organic solvent(s) are chosen from polyols, more preferentially chosen from glycerol, propane-1,3-diol, and mixtures thereof.
The organic solvent(s) may be present in an amount ranging from 0.01% to 30% by weight, preferably from 1% to 25% by weight, better still from 2% to 20% by weight, even better still from 4% to 15% by weight relative to the total weight of the composition.
In addition, the composition according to the invention is preferably an aqueous composition. The composition preferably comprises water in an amount of greater than or equal to 5% by weight, preferably greater than or equal to 10% by weight, and better still greater than or equal to 15% by weight, relative to the total weight of the composition.

Additives

The composition according to the invention may optionally comprise one or more additives, other than the compounds described previously, and among which mention may be made of cationic, anionic, nonionic or amphoteric polymers or mixtures thereof other than the thickening polymers as described previously, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, plasticizers, solubilizers, opacifiers or nacreous agents, antioxidants, hydroxy acids, and fragrances.
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.
Preferably, the composition according to the invention does not comprise any chemical oxidizing agents. The composition may be intended to be mixed with an oxidizing composition.
Preferably, the composition according to the invention does not comprise any cationic polymers.
According to one embodiment, the composition according to the invention also comprises one or more chemical oxidizing agents as described below. According to this embodiment, the composition is a ready-to-use composition.
Preferably, the pH of the ready-to-use composition is between 8 and 11 and preferentially between 9 and 10.5.
According to another embodiment, the composition according to the invention does not comprise any chemical oxidizing agents. According to this embodiment, the composition is preferably intended for mixing with one or more chemical oxidizing agents.
Preferably, the pH of the composition not containing any chemical oxidizing agents is between 8 and 13, preferentially between 9 and 12.
According to another particular embodiment, the pH of the composition not containing any chemical oxidizing agents is between 7 and 10 and the pH of the ready-to-use composition is between 6 and 9.

Process

The present invention also relates to a process for dyeing keratin fibres, preferably the hair, which comprises the application to said keratin fibres of an effective amount of a composition as defined previously, in the presence of an oxidizing agent.
The composition may be applied to wet or dry keratin fibres. On conclusion of the treatment, the keratin fibres are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.
Preferably, the process according to the invention comprises a step of mixing the previously described composition, which does not comprise any chemical oxidizing agents, with an oxidizing composition comprising at least one chemical oxidizing agent. This mixing step is preferably performed at the time of use, just before applying to the hair the composition resulting from the mixing.
According to this preferred embodiment, at the time of use, the composition according to the invention results from the mixing of at least two compositions:
a composition comprising:
- at least one compound chosen from hyaluronic acid and/or a derivative thereof, and mixtures thereof;
- at least one anionic surfactant, preferably chosen from fatty acids;
- at least one alkaline agent;
- at least one dye, preferably chosen from oxidation dyes;
- at least one liquid fatty alcohol and at least one solid fatty alcohol, the total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) ranges from 6% to 40% by weight relative to the total weight of the composition; and
an oxidizing composition comprising one or more chemical oxidizing agents, preferably hydrogen peroxide.
Preferably, the process according to the invention comprises a step of mixing the composition according to the invention with an oxidizing composition comprising at least one chemical oxidizing agent. This mixing step is preferably performed at the time of use, just before applying to the hair the composition resulting from the mixing.
In a preferred embodiment, the process for dyeing keratin fibres, preferably the hair, according to the invention, comprises the step of applying to the keratin fibres a composition resulting from the mixing, at the time of use, of at least two compositions:
a) a dye composition comprising:
- at least one compound chosen from hyaluronic acid and/or a derivative thereof, and mixtures thereof;
- at least one anionic surfactant, preferably chosen from fatty acids;
- at least one alkaline agent;
- at least one dye, preferably at least one oxidation dye;
- at least one liquid fatty alcohol and at least one solid fatty alcohol, the total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) ranges from 6% to 40% by weight relative to the total weight of the composition;
- at least one surfactant other than anionic surfactants; and
b) an oxidizing composition comprising one or more chemical oxidizing agents.
More particularly, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof and percarbonates of alkali metals or alkaline-earth metals, and mixtures thereof. The oxidizing agent is preferably chosen from hydrogen peroxide.
The oxidizing composition is preferably an aqueous composition. In particular, it comprises more than 5% by weight of water, preferably more than 10% by weight of water and even more advantageously more than 20% by weight of water relative to the total weight of the oxidizing composition.
The oxidizing composition may also comprise one or more organic solvents chosen from those listed previously; these solvents more particularly representing, when they are present, from 0.01% to 40% by weight and preferably from 0.1% to 30% by weight relative to the weight of the oxidizing composition.
The oxidizing composition also preferably comprises one or more acidifying agents. Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
The oxidizing composition may also comprise fatty substances such as those described previously, preferably chosen from fatty alcohols, liquid hydrocarbons comprising more than 6 carbon atoms and mixtures thereof, surfactants and polymers.
Usually, the pH of the oxidizing composition, when it is aqueous, is less than 7.
Preferably, the oxidizing composition comprises hydrogen peroxide as oxidizing agent, in aqueous solution, the concentration of which ranges, more particularly, from 0.1% to 50%, more particularly between 0.5% and 20% and even more preferentially between 1% and 15% by weight, relative to the weight of the oxidizing composition.

Kit

Another subject of the invention is a multi-compartment device, preferably comprising two compartments, for dyeing keratin fibres, preferably the hair, comprising at least a first compartment containing the dye composition according to the invention and at least a second compartment containing an oxidizing composition as described above.
The compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means, which may be identical or different, such as fine brushes, coarse brushes or sponges.
The device mentioned above may also be equipped with a means for dispensing the desired mixture onto the hair, for instance the devices described in patent FR 2 586 913.
Finally, the present invention relates to the use of a composition as described above, for dyeing keratin fibres, and in particular the hair.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.

Examples

In the examples that follow, all the amounts are given as mass percentages of active material (AM) relative to the total weight of the composition (unless otherwise mentioned).

Compositions

The dye compositions A1, B1, A2, B2, A3, B3, A4 and B4 were prepared from the ingredients whose contents are indicated in the table below (% active material):
1. Dye compositions A1 and B1 (Example 1)

	A1 (invention)	B1 (comparative)
Oleic acid	2.70	2.70
Ammonium hydroxide	4.57	4.57
Ethanolamine	0.63	0.63
2-Amino-3-hydroxypyridine	0.04	0.04
Hydroxybenzomorpholine	0.30	0.30
Antioxidant	0.91	0.91
Hydroxyethyl-p-phenylenediamine sulfate	0.13	0.13
m-Aminophenol	0.05	0.05
EDTA	0.20	0.20
Cetearyl alcohol	16.20	16.20
Oleyl alcohol	2.70	2.70
Nonionic surfactant	3.60	3.60
Sodium hyaluronate	0.05	-
Hydroxyethyl-3,4-methylenedioxyaniline HCl	0.14	0.14
Toluene -2,5-diamine	0.33	0.33
Water	qs 100	Qs 100

At the time of use, each of the dye compositions A1 and B1 is mixed with 1.5 times its weight of oxidizing agent O. Each of the mixtures is then applied to locks of permanent-waved grey (PWG) hair, natural grey (NG) hair and and/or moderately sensitized hair (AS20), containing 90% white hairs, at a rate of 5 g of mixture/g of hair.
After a leave-on time of 35 minutes at 27°C, the hair is rinsed, washed with a standard shampoo and dried.

Results

The colorimetric measurements were performed using a Konica Minolta 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.

Selectivity

The dyeing selectivity is the variation of the colour between natural hair and permanent-waved hair. The natural hair is representative of the nature of the hair at the root, whereas the permanent-waved hair is representative of the nature of the hair at the end. The selectivity enables evaluation of the colour homogeneity along the entire length of the hair fibre.
The selectivity is measured by:
ΔE, which is the variation in colour between the natural hair and the permanent-waved hair, is obtained from the formula:
in which L* represents the intensity and a* and b* represent the chromaticity of the dyed natural hair, and L₀* represents the intensity and a₀* and b₀* represent the chromaticity of the dyed permanent-waved hair. The lower the value of ΔE, the lower the selectivity and the more uniform the colouring along the hair.

	Type of hair	L*	a*	b*	ΔE
A1 + O (invention)	NG	27.6	2.2	9.5	4.5
A1 + O (invention)	PWG	23.7	2.3	7.1	4.5
B1 + O (comparative)	NG	26.5	3.0	10.0	7.7
B1 + O (comparative)	PWG	20.5	2.7	5.1	7.7

The locks of hair treated with the mixture A1+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B1+O. In other words, the mixture A1+O according to the invention affords locks of hair with improved selectivity relative to those treated with the comparative mixture B1+O, and consequently improved colour homogeneity from the root to the tip of the hair.

Fastness

The persistence of the colouring is evaluated in the same manner. This is the colour difference ΔE (according to the above formula) between dyed locks (NG) before shampoo washing, and then after undergoing five shampoo washes. The lower the ΔE value, the more persistent the colour with respect to shampoo washing.

	Number of shampoo washes	L*	a*	b*	ΔE
A1 + O (invention)	0	27.6	2.2	9.5	0.9
A1 + O (invention)	5	28.3	2.5	9.1	0.9
B1 + O (comparative)	0	26.5	3.0	10.0	3.6
B1 + O (comparative)	5	30.0	2.3	9.9	3.6

The locks of hair treated with the mixture A1+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B1+O.
In other words, the mixture A1+O according to the invention affords a homogeneous coloured coating on hair which shows improved resistance to shampoo washing relative to hair treated with the comparative mixture B1+O.

Ease of combing

The performance in terms of ease of combing, i.e. ease of disentangling, was evaluated by five experts on moderately sensitized hair (AS20). Each of the five experts rated each lock, awarding "5 points" to very good combing properties, "2.5 points" to moderate combing properties and "0 points" to combing properties evaluated as poor.
To evaluate the ease of combing, the expert passes a comb through the lock, first with the large-toothed section and then with the small-toothed section, moving down from the top of the lock to the ends, so as to feel how easily the comb passes through the lock of hair.
The scores attributed by the experts are given below:

	Combing
	A1 + O (Invention)	B1 + O (comparative)
Expert 1	3.5	2
Expert 2	3.5	2.5
Expert 3	3.5	2.5
Expert 4	4	3
Expert 5	3	2.5
Mean	3.5	2.5

100% of the experts (5 out of 5) judged that the mixture A1+O according to the invention afforded better ease of combing performance than the comparative mixture B1+O not comprising sodium hyaluronate.
In addition, the mixture A1+O affords good sensory performance.
2. Dye compositions A2 and B2 (Example 2)

	A2 (invention)	B2 (comparative)
Oleic acid	2.70	2.70
Ammonium hydroxide	4.57	4.57
Ethanolamine	0.63	0.63
2-Amino-3-hydroxypyridine	0.04	0.04
Hydroxybenzomorpholine	0.30	0.30
Antioxidant	0.91	0.91
Hydroxyethyl-p-phenylenediamine sulfate	0.13	0.13
m-Aminophenol	0.05	0.05
EDTA	0.20	0.20
Cetearyl alcohol	5.00	3.00
Oleyl alcohol	1.00	1.00
Nonionic surfactant	3.60	3.60
Sodium hyaluronate	0.05	0.05
Hydroxyethyl-3,4-methylenedioxyaniline HCl	0.14	0.14
Toluene -2,5-diamine	0.33	0.33
Water	qs 100	Qs 100

At the time of use, each of the dye compositions A2 and B2 is mixed with 1.5 times its weight of oxidizing agent O. Each of the mixtures is then applied to locks of natural grey (NG) hair and moderately sensitized hair (AS20), at a rate of 5 g of mixture/g of hair.
After a leave-on time of 35 minutes at 27°C, the hair is rinsed, washed with a standard shampoo and dried.

Selectivity

The selectivity is then measured by means of ΔE, corresponding to the colour variation between natural grey (NG) hair and moderately sensitized (AS20) hair, the formula for which is described in Example 1.

	Type of hair	L*	a*	b*	ΔE
A2 + O (invention)	NG	25.2	2.8	7.8	5.3
A2 + O (invention)	AS20	20.9	2.7	4.8	5.3
B2 + O (comparative)	NG	29.6	2.0	9.8	9.7
B2 + O (comparative)	AS20	21.6	2.7	4.4	9.7

The locks of hair treated with the mixture A2+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B2+O. In other words, the mixture A2+O according to the invention affords locks of hair with improved selectivity relative to those treated with the mixture B2+O, and consequently improved colour homogeneity from the root to the tip of the hair.
In addition, the mixture A2+O affords good sensory performance.
Fastness
The persistence of the colouring is evaluated in the same manner. This is the colour difference ΔE (according to the above formula) between dyed locks before shampoo washing, and then after undergoing five shampoo washes. The lower the ΔE value, the more persistent the colour with respect to shampoo washing.

	Number of shampoo washes	L*	a*	b*	ΔE
A2 + O (invention)	0	21.4	2.3	5.1	0.7
A2 + O (invention)	5	21.7	2.4	5.7	0.7
B2 + O (comparative)	0	21.9	2.3	5.4	3.4
B2 + O (comparative)	5	24.7	2.8	7.2	3.4

The locks of hair treated with the mixture A2+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B2+O.
In other words, the mixture A2+O according to the invention affords a homogeneous coloured coating on hair which shows improved resistance to shampoo washing relative to hair treated with the comparative mixture B2+O.

3. Dye compositions A3 and B3 (Example 3)

	A3 (invention)	B3 (comparative)
Thickener	0.2	0.2
Oleic acid	2.70	2.70
Ethanolamine	6.25	6.25
Cocoyl glucoside	1.87	1.87
Shea olein	4.0	4.0
Hydroxybenzomorpholine	0.15	0.15
Solvent	10.0	10.0
Antioxidant	0.96	0.96
Tetrasodium glutamate diacetate	0.24	0.24
Hydroxyethyl-p-phenylenediamine sulfate	0.08	0.08
m-Aminophenol	0.15	0.15
Cetearyl alcohol	5	3
Oleyl alcohol	1	1
Sodium hyaluronate	0.05	0.05
Hydroxyethyl-3,4-methylenedioxyaniline HCl	0.08	0.08
Toluene -2,5-diamine	0.26	0.26
Water	qs 100	qs 100

At the time of use, each of the dye compositions A3 and B3 is mixed with 1.5 times its weight of oxidizing agent O. Each of the mixtures is then applied to locks of permanent-waved grey (PWG) hair and natural grey (NG) hair, containing 90% white hairs, at a rate of 5 g of mixture/g of hair.
After a leave-on time of 35 minutes at 27°C, the hair is rinsed, washed with a standard shampoo and dried.
Selectivity
The selectivity is then measured by means of ΔE, corresponding to the colour variation between natural grey (NG) hair and permanent-waved grey (PWG) hair, the formula for which is described in Example 1.

	Type of hair	L*	a*	b*	ΔE
A3 + O (invention)	NG	27.1	2.9	4.5	5.7
A3 + O (invention)	PWG	21.7	1.8	2.9	5.7
B3 + O (comparative)	NG	31.3	2.5	4.7	9.7
B3 + O (comparative)	PWG	21.6	2.0	4.2	9.7

The locks of hair treated with the mixture A3+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B3+O. In other words, the mixture A3+O according to the invention affords locks of hair with improved selectivity relative to those treated with the mixture B3+O, and consequently improved colour homogeneity from the root to the tip of the hair.
In addition, the mixture A3+O affords good sensory performance.
Fastness
The persistence of the colouring is evaluated in the same manner. This is the colour difference ΔE (according to the above formula) between dyed locks (AS20) before shampoo washing, and then after undergoing five shampoo washes. The lower the ΔE value, the more persistent the colour with respect to shampoo washing.

	Number of shampoo washes	L*	a*	b*	ΔE
A3 + O (invention)	0	22.0	2.3	3.5	1.9
A3 + O (invention)	5	23.2	2.7	4.9	1.9
B3 + O (comparative)	0	19.8	2.8	3.7	4.8
B3 + O (comparative)	5	24.4	2.8	5.1	4.8

The locks of hair treated with the mixture A3+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B3+O.
In other words, the mixture A3+O according to the invention affords a homogeneous coloured coating on hair which shows improved resistance to shampoo washing relative to hair treated with the comparative mixture B3+O.
4. Dye compositions A4 and B4

	A4 (invention)	B4 (comparative)
Thickener	0.2	0.2
Oleic acid	2.70	2.70
Ethanolamine	6.25	6.25
Cocoyl glucoside	1.87	1.87
Shea olein	4.0	4.0
Hydroxybenzomorpholine	0.15	0.15
Solvent	10.0	10.0
Antioxidant	0.96	0.96
Tetrasodium glutamate diacetate	0.24	0.24
Hydroxyethyl-p-phenylenediamine sulfate	0.08	0.08
m-Aminophenol	0.15	0.15
Cetearyl alcohol	16.30	16.30
Oleyl alcohol	2.70	2.70
Sodium hyaluronate	0.05	-
Hydroxyethyl-3,4-methylenedioxyaniline HCl	0.08	0.08
Toluene -2,5-diamine	0.26	0.26
Water	qs 100	qs 100

At the time of use, each of the dye compositions A4 and B4 is mixed with 1.5 times its weight of oxidizing agent O. Each of the mixtures is then applied to locks of NG and AS20 hair, at a rate of 5 g of mixture/g of hair.
After a leave-on time of 35 minutes on a plate thermostatically regulated at 27°C, the hair is rinsed, washed with a standard shampoo and dried.
Selectivity
The selectivity is then measured by means of ΔE, corresponding to the colour variation between natural grey (NG) hair and moderately sensitized (AS20) hair, the formula for which is described in Example 1.

	Type of hair	L*	a*	b*	ΔE
A4 + O (invention)	NG	36.7	1.2	9.1	9.4
A4 + O (invention)	AS20	27.8	3.7	10.8	9.4
B4 + O (comparative)	NG	37.5	1.2	9.4	11.7
B4 + O (comparative)	AS20	25.9	3.2	9.3	11.7

The locks of hair treated with the mixture A4+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B4+O. In other words, the mixture A4+O according to the invention affords locks of hair with improved selectivity relative to those treated with the mixture B4+O, and consequently improved colour homogeneity from the root to the tip of the hair.
In addition, the mixture A4+O affords good sensory performance.
Fastness
The persistence of the colouring is evaluated in the same manner. This is the colour difference ΔE (according to the above formula) between dyed locks before shampoo washing, and then after undergoing five shampoo washes. The lower the ΔE value, the more persistent the colour with respect to shampoo washing.

	Number of shampoo washes	L*	a*	b*	ΔE
A4 + O (invention)	0	27.8	3.7	10.8	1.3
A4 + O (invention)	5	29.0	4.0	10.9	1.3
B4 + O (comparative)	0	25.9	3.2	9.3	4.0
B4 + O (comparative)	5	29.8	3.4	10.6	4.0

The locks of hair treated with the mixture A4+O according to the invention have a much lower ΔE value than those treated with the comparative mixture B4+O.
In other words, the mixture A4+O according to the invention affords a homogeneous coloured coating on hair which shows improved resistance to shampoo washing relative to hair treated with the comparative mixture B4+O.
Combing and smooth feel
The ease of combing, i.e. ease of disentangling, and smooth feel performance were evaluated by five experts, on moderately sensitized hair (AS20). Each of the five experts rated each lock, awarding "5 points" to very good properties, "2.5 points" to moderate performance and "0 points" to poor performance.
The scores of each expert are then ranked so as to assign them a "rank". Rank 1 is assigned to the lock with the best performance in terms of ease of combing and smoothness of feel.
To evaluate the ease of combing, the expert passes a comb through the lock, first with the large-toothed section and then with the small-toothed section, moving down from the top of the lock to the ends, so as to feel how easily the comb passes through the lock of hair.
The scores attributed by the experts are given below:

	Combing
	A4+O (Invention)	B4 + O (comparative)		Rank A4+O (invention)	Rank B4+O (comparative)
Expert 1	4.5	4		1	2
Expert 2	3.5	3		1	2
Expert 3	3.5	3		1	2
Expert 4	4.5	3.5		1	2
Expert 5	4	3.5		1	2
Mean	4	3.4	∑Ranks	5	10

100% of the experts (5 out of 5) judged that the mixture A4+O according to the invention afforded better ease of combing performance than the comparative mixture B4+O not comprising sodium hyaluronate.
To evaluate the smooth feel, the expert takes the lock between thumb and forefinger and slides his or her fingers along the lock from the upper part to the ends. He or she evaluates whether the hair is smooth and if it has any bumps i.e. whether or not the fingers catch on the hair.

	Smooth feel
	A4+O (Invention)	B4 + O (comparative)		Rank A4+O (invention)	Rank B4+O (comparative)
Expert 1	4	3.5		1	2
Expert 2	4	3.5		1	2
Expert 3	3.5	3		1	2
Expert 4	5	4		1	2
Expert 5	4	3.5		1	2
Mean	4.1	3.5	∑Ranks	5	10

100% of the experts (5 out of 5) judged that the mixture A4+O according to the invention afforded better smoothness of feel performance than the comparative mixture B4+O not comprising sodium hyaluronate.

Claims

Composition comprising:
- at least one compound chosen from hyaluronic acid and/or a derivative thereof, and mixtures thereof;
- at least one anionic surfactant;
- at least one alkaline agent,
- at least one dye;
- at least one liquid fatty alcohol and at least one solid fatty alcohol, the total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) ranges from 6% to 40% by weight relative to the total weight of the composition.
Composition according to Claim 1, in which the compound(s) chosen from hyaluronic acid and/or a derivative thereof and mixtures thereof are chosen from hyaluronic acid salts, hyaluronic acid hydrolysates, quaternized hyaluronic acid derivatives and salts thereof and acetylated hyaluronic acid derivatives and mixtures thereof, preferably chosen from hyaluronic acid salts and mixtures thereof, more preferentially sodium hyaluronate.
Composition according to either of the preceding claims, in which the total content of the compound(s) chosen from hyaluronic acid and/or a derivative thereof and mixtures thereof ranges from 0.001% to 10% by weight, preferentially from 0.003% to 5% by weight, more preferentially from 0.008% to 1% by weight, better still from 0.01% to 0.5% by weight, even better still from 0.02% to 0.1% by weight relative to the total weight of the composition.
Composition according to any one of the preceding claims, in which the anionic surfactant(s) are chosen from fatty acids, alkyl sulfates, alkyl ether sulfates, and mixtures thereof, better still chosen from linear fatty acids, even better still chosen from linear unsaturated C₁₀-C₂₂ and notably C₁₀-C₁₈ fatty acids, and mixtures thereof, such as oleic acid.
Composition according to any one of the preceding claims, in which the total content of the anionic surfactant(s) ranges from 0.01% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.5% to 8% by weight, even better still from 0.8% to 6% by weight, relative to the total weight of the composition.
Composition according to any one of the preceding claims, in which the alkaline agent(s) are chosen from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; aqueous ammonia, (bi)carbonates such as Na, K, Mg or Ca (bi)carbonates, ammonium (bi)carbonates, alkali metal or alkaline-earth metal silicates or metasilicates such as sodium metasilicate and mixtures thereof, more preferentially from alkanolamines and aqueous ammonia, better still from alkanolamines and even better still monoethanolamine.
Composition according to any one of the preceding claims, in which the total content of alkaline agent ranges from 0.01% to 30% by weight, more preferentially from 0.05% to 20% by weight, better still from 0.08% to 15% by weight and even better still from 0.1% to 10% by weight relative to the total weight of the composition.
Composition according to any one of the preceding claims, in which the dye(s) are chosen from oxidation dyes, direct dyes and mixtures thereof, preferably chosen from oxidation dyes, preferentially chosen from oxidation bases optionally associated with one or more couplers.
Composition according to any one of the preceding claims, in which the liquid fatty alcohol(s) are chosen from saturated or unsaturated, linear or branched, preferably unsaturated or branched, alcohols including from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, preferentially chosen from octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol or linoleyl alcohol, and mixtures thereof; better still, the liquid fatty alcohol is oleyl alcohol.
Composition according to any one of the preceding claims, in which the solid fatty alcohol(s) are chosen from saturated or unsaturated, linear or branched, preferably linear and saturated, (mono)alcohols including from 8 to 40 carbon atoms, preferentially from 10 to 30, better still from 12 to 24, even better still from 14 to 22 carbon atoms, preferably chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol and arachidyl alcohol, and mixtures thereof, more preferentially chosen from cetyl alcohol, stearyl alcohol and mixtures thereof such as cetylstearyl or cetearyl alcohol.
Composition according to any one of the preceding claims, in which the total content of liquid fatty alcohol(s) and of solid fatty alcohol(s) ranges from 6.5% to 35% by weight, better still from 7% to 30% by weight, even better still from 7.5% to 25% by weight, or even from 8% to 20% by weight, relative to the total weight of the composition.
Composition according to any one of the preceding claims, in which the total content of solid fatty alcohol(s) is greater than or equal to 5% by weight, preferably ranges from 6% to 40% by weight, more preferentially from 6.5% to 35% by weight, better still from 7% to 30% by weight, even better still from 7.5% to 25% by weight, or even from 10% to 20% by weight, relative to the total weight of the composition.
Composition according to any one of the preceding claims, not comprising any chemical oxidizing agent.
Composition according to any one of Claims 1 to 12, comprising at least one chemical oxidizing agent, preferably hydrogen peroxide.
Process for dyeing keratin fibres, preferably the hair, comprising the application to the keratin fibres of the composition as defined according to Claim 14.
Process according to Claim 15, comprising the application to the fibres of a mixture of:
a) a composition according to any one of Claims 1 to 13,
b) an oxidizing composition comprising one or more chemical oxidizing agents, preferably hydrogen peroxide.
Multi-compartment device, preferably a two-compartment device, for dyeing keratin fibres, preferably the hair, comprising at least a first compartment containing a composition as defined according to any one of Claims 1 to 13 and at least a second compartment containing an oxidizing composition comprising one or more chemical oxidizing agents, preferably hydrogen peroxide.