DYE COMPOSITION FOR DYEING KERATINOUS FIBERS AND KIT COMPRISING SAME

Abstract

DYE COMPOSITION FOR DYEING KERATINOUS FIBERS AND KIT COMPRISING SAME The present invention relates to a dye composition for dyeing keratinous fibers and a kit comprising it. The dye composition comprises i) at least one oxidative base selected from aminopyrazoles, their addition salts and mixtures thereof; ii) at least one λ-carrageenan type polysaccharide; and iii) at least one hydrophilic gelling polymer selected from anionic acrylic copolymers. The present invention also relates to a process for dyeing keratinous fibers. Figure for abstract: none

Description

Title of the invention: DYE COMPOSITION FOR DYEING KERATINOUS FIBERS AND KIT INCLUDING THIS ONE Technical field

[0001] The present invention relates to a cosmetic composition. In particular, the present invention relates to a dye composition for dyeing keratinous fibers and a kit comprising the same. The present invention also relates to a process for dyeing keratinous fibers. STATE OF THE ART

[0002] Many people have long sought to change the color of their hair, and in particular to dye it, for example, to hide their gray hair.

[0003] The dye product may comprise both at least one oxidative dye and at least one oxidant. For better use, the oxidative dye and the oxidant may be placed respectively in a multi-compartment package and mixed immediately before use.

[0004] 4,5-Diamino-l-([3-hydroxyethyl)pyrazole or the like are often used in dye compositions to provide a bright red hair color. However, 4,5-diamino-l-([3-hydroxyethyl]pyrazole or similar may present a stability problem in hair coloring products.

[0005] It is desirable that hair coloring products be stable.

[0006] Additionally, consumers often expect hair dye products to be easily applied, which can be achieved when the products are in cream form.

[0007] There is therefore a need to develop a hair dye composition comprising 4,5-diamino-l-([3-hydroxyethyl)pyrazole or the like, which is stable and preferably in the form of a liquid cream so as to be easily applied. Summary of the invention

[0008] An objective of the present application is to provide a hair dye composition comprising 4,5-diamino-l-([3-hydroxyethyl)pyrazole or the like, which is stable and preferably in the form of a liquid cream so as to be easily applied.

[0009] Another objective of the present application is to provide a process for dyeing hair.

[0010] Thus, in a first aspect, the present invention provides a composition of dye for dyeing keratinous fibers, comprising:

[0011] i) at least one oxidative base chosen from aminopyrazoles, their addition salts and their mixtures;

[0012] ii) at least one X-carrageenan type polysaccharide; and

[0013] iii) at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers.

[0014] The dye composition for dyeing keratinous fibers according to the present invention is stable and, in certain embodiments, is in the form of a liquid cream and can be easily applied.

[0015] The dye composition according to the present invention can be used for dyeing keratinous fibers in combination with a developer composition.

[0016] In a second aspect, the present invention provides a kit for dyeing keratinous fibers, comprising:

[0017] A) the colorant composition according to the first aspect of the present invention; and

[0018] B) a developer composition for dyeing keratinous fibers.

[0019] In a third aspect, the present invention provides a process for dyeing keratinous fibers, comprising:

[0020] mixing the dye composition according to the present invention and a developer composition for dyeing keratinous fibers immediately before use;

[0021] applying the resulting mixture to the keratinous fibers; and

[0022] rinsing the mixture on the keratinous fibers with water, optionally washing the keratinous fibers with a shampoo before rinsing the keratinous fibers with water.

[0023] In a third aspect, the present invention provides a use of an X-carrageenan type polysaccharide for improving the stability of a dye composition comprising at least one oxidative base chosen from aminopyrazoles, their addition salts and their mixtures.

[0024] Other subjects and characteristics, aspects and advantages of the present invention will become even more apparent from the detailed description and examples which follow. DETAILED DESCRIPTION OF THE INVENTION

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as that commonly recognized by those skilled in the art in the field to which the present invention pertains. Where the definition of a term in the present invention conflicts with the meaning commonly recognized by those skilled in the art in the field to which the present invention pertains, the definition described herein invention will apply.

[0026] As used herein, unless otherwise indicated, the limits of a range of values ​​are included within that range, particularly in the expressions "between...and..." and "from...to...".

[0027] Furthermore, the expression “at least one” used in the present description is equivalent to the expression “one or more”.

[0028] Throughout the present application, the term "comprising" should be interpreted to encompass all specifically mentioned features as well as optional, additional, and unspecified features. As used herein, the use of the term "comprising" also discloses the embodiment in which no features other than the specifically mentioned features are present (i.e., "consisting of").

[0029] Unless otherwise specified, all numerical values ​​expressing an amount of ingredients and the like that are used in the description and claims are to be understood as being modified by the term "about". Accordingly, unless otherwise specified, the numerical values ​​and parameters described herein are approximate values ​​that may be changed depending on the desired objective, if necessary.

[0030] For the purposes of the present invention, the expression “keratinous fibers” includes animal keratinous fibers and human keratinous fibers such as hair.

[0031] In the present invention, all percentages refer, unless otherwise specified, to a percentage by weight.

[0032] The colorant composition according to the present invention comprises:

[0033] i) at least one oxidative base chosen from aminopyrazoles, their addition salts and their mixtures;

[0034] ii) at least one X-carrageenan type polysaccharide; and

[0035] iii) at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers. Oxidative bases

[0036] According to the first aspect, the dye composition of the present invention comprises at least one oxidative base selected from aminopyrazoles and its addition salts.

[0037] Examples of aminopyrazoles include 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-([3-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-l-tert-butyl-3-methylpyrazole, 4,5-diamino-l-(2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4, 5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-l,3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(2-hydroxyethyl)amino-1-methylpyrazole.

[0038] Examples of addition salts of aminopyrazoles include their sulfates, chlorides and dimethosulfonates.

[0039] Preferably, the oxidative base is chosen from diaminopyrazoles, their addition salts and their mixtures.

[0040] More preferably, the oxidative base is chosen from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-([3-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-l-(4'-chlorobenzyl)pyrazole, 4,5-diamino-l, 3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3-phenylpyrazole, l-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole, 4,5-diamino-l-tert-butyl-3-methylpyrazole, 4,5-diamino-l-(2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- (4'-methoxyphenyl)pyrazole, 4,5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, their sulfates, chlorides and dimethosulfonates, and mixtures thereof.

[0041] In some embodiments, the oxidative base is selected from 4,5-diamino-l-([3-hydroxyethyl)pyrazole (also referred to as l-hydroxyethyl-4,5-diamino pyrazole), its sulfates, chlorides, dimethosulfonates and mixtures thereof.

[0042] Advantageously, the oxidative base is present in the dye composition of the present invention in an amount ranging from 0.5% by weight to 8% by weight, or from 0.6% by weight to 6% by weight, or from 0.7% by weight to 7% by weight, preferably from 0.8% by weight to 6% by weight, or from 1% by weight to 5% by weight, or from 1.1% by weight to 4% by weight, and more preferably from 1.2% by weight to 3% by weight or from 1.2% to 2.5% by weight, relative to the total weight of the dye composition. Polysaccharide of the A-carrageenan type

[0043] According to the first aspect, the colorant composition of the present invention comprises at least one X-carrageenan type polysaccharide.

[0044] In some embodiments, the X-carrageenan polysaccharide is not chemically modified.

[0045] Preferably, the molecular weight (Mw) of the X-carrageenan polysaccharide ranges from 100,000 to 1,000,000. More preferably, the molecular weight (Mw) of the X-carrageenan ranges from 250,000 to 800,000.

[0046] Non-limiting examples of X-carrageenan that may be used in accordance with the present disclosure include Satiagum UTC 10 from Degussa, Welgeenan ED 1039 from Eurogum and Satiagum VPC 430 from CARGILL. Advantageously, the X-carrageenan type polysaccharide is present in the colorant composition of the present invention in an amount ranging from 0.01% to 2% or from 0.05% by weight to 1.8% by weight, or from 0.08% by weight to 1.6% by weight, preferably from 0.1% by weight to 1.5% by weight, or from 0.12% by weight to 1.4% by weight, and more preferably from 0.15% by weight to 1.2% by weight, or from 0.2% by weight to 1% by weight, relative to the total weight of the colorant composition. Hydrophilic gelling polymers

[0047] According to the first aspect, the colorant composition of the present invention comprises at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers.

[0048] According to the present invention, the expression "hydrophilic gelling polymer" designates a polymer capable of thickening an aqueous medium. Preferably, the thickening polymer has, at 1% in water or in a 50 / 50 water / alcohol mixture by weight at 25°C, a viscosity greater than 100 centipoises at a shear rate of 1 s A. These viscosities can be measured using in particular viscometers or rheometers having a cone-plate geometry.

[0049] For the purposes of the present invention, the expression “acrylic copolymer” designates a polymer resulting from the copolymerization of at least two chemically different monomers, at least one of which is chosen from unsaturated carboxylic acids, preferably acrylic acid or methacrylic acid.

[0050] According to a particular embodiment of the invention, the anionic acrylic copolymer(s) are chosen from:

[0051] - anionic copolymers derived from at least one unsaturated carboxylic acid and of at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms;

[0052] - anionic associative acrylic copolymers, and

[0053] - their mixtures.

[0054] As used herein, the term "acrylic associative polymer" means an amphiphilic homopolymer which is capable, in an aqueous medium, of combining in a reactive manner. reversible with itself or with other molecules. It generally includes, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group.

[0055] The expression "hydrophobic group" designates a group or a polymer carrying a saturated or unsaturated and linear or branched hydrocarbon-based chain. When it designates a hydrocarbon-based group, the hydrophobic group comprises at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms, from 12 to 24 carbon atoms and preferably from 16 to 22 carbon atoms. Preferably, the hydrocarbon-based hydrophobic group comes from a monofunctional compound. For example, the hydrophobic group can be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol, or from a polyalkylenated fatty alcohol, such as steareth-50.

[0056] In the context of the invention, the anionic copolymer(s) derived from at least one unsaturated carboxylic acid and at least one ester of an unsaturated carboxylic acid and a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms are different from the anionic associative acrylic copolymer(s).

[0057] The anionic copolymer(s) derived from at least one unsaturated carboxylic acid and at least one ester of an unsaturated carboxylic acid and a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms are copolymers comprising, among their monomers, one or more unsaturated carboxylic acids, which are more particularly α,[3-monoethylenically unsaturated, and one or more esters of an unsaturated carboxylic acid, which are more particularly α,[3-monoethylenically unsaturated, and a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms.

[0058] More particularly, the unsaturated carboxylic acid, which is in particular α,[3-monoethylenically unsaturated, is a monomer corresponding to the formula (I) below: H2C--C.........C —OH R' 6 w

[0059] in which R1 denotes H or CH3 or C2H5, which corresponds to acrylic acid, methacrylic acid or ethacrylic acid units.

[0060] Preferably, the other monomeric ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms is a monomer of formula (II) below: H2C^C-----------Ç.......OR2 O (he)

[0061] in which R1 denotes H or CH3 or C2H5 (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), and R2 denotes an alkyl group comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms.

[0062] As esters of an unsaturated carboxylic acid and of a fatty monoalcohol comprising from 1 to 6 carbon atoms according to formula (II), mention may be made more particularly of methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate, and the corresponding methacrylates, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.

[0063] According to one embodiment, these anionic copolymers can be crosslinked, for example, with a crosslinking agent, which is a well-known copolymerizable unsaturated polyethylene monomer, for example diallyl phthalate, allyl (meth)acrylate, divinylbenzene, ethylene glycol (poly)dimethacrylate or methylenebisacrylamide.

[0064] Among the anionic copolymers of this type, polymers consisting of the following monomers will be used more particularly:

[0065] (i) an unsaturated carboxylic acid, in particular a,[3-monoethylenically unsaturated, corresponding to formula (I) below: ........C—OH Ô (j)

[0066] in which R1 denotes H or CH3 or C2H5, which corresponds to acrylic acid, methacrylic acid or ethacrylic acid units;

[0067] (ii) of an ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, of formula (II) below: HSC=C..........Ç.....OR2 R' O w

[0068] in which R1 denotes H or CH3 or C2H5 (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), and R2 denotes an alkyl group comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms,

[0069] (iii) and optionally a crosslinking agent, which is a poly-unsaturated monomer

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] well-known copolymerizable ethylene oxide, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide. Examples of anionic copolymers as defined above are the crosslinked copolymer of acrylic acid and ethyl acrylate sold under the trade name Aculyn 33 by the company Rohm & Haas, which is in aqueous dispersion containing 28% by weight of active material, the crosslinked copolymer of methacrylic acid / ethyl acrylate in the form of an aqueous dispersion at 30% by weight (INCI name: Acrylates Copolymer) sold under the name Carbopol Aqua SF-1 Polymer by the company Lubrizol, and the copolymer of (meth)acrylic acid and a C1-C4 alkyl (meth)acrylate sold under the name Synthalen W400 by the company 3V Sigma, at 30% by weight of active material in water. Preferably, these anionic copolymers are chosen from crosslinked copolymers of (meth)acrylic acid and a Cr-C4 alkyl (meth)acrylate, and better still from crosslinked copolymers of (meth)acrylic acid and ethyl (meth)acrylate. Among the anionic associative acrylic copolymers which can be used in the context of the invention, we can cite: (1) copolymers derived from the polymerization of: (i) (meth)acrylic acid and / or its C1-C4 alkyl ester> (ii) a monomer of formula (III) below: CHg - CR* GH2 OR (H!) in which R' denotes H or CH3, B denotes the ethyleneoxy group (-CH2-CH2-O-), n is zero or denotes an integer ranging from 1 to 100 (in particular from 5 to 15) and R denotes a hydrocarbon-based group chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl groups comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms and even more particularly from 16 to 20 carbon atoms. A monomer of formula (III) which is more particularly preferred is a monomer in which R' denotes H, n is equal to 10 and R denotes a stearyl group (Cl8). Among these anionic associative acrylic copolymers, those which are particularly preferred are polymers formed from 20% to 60% by weight of (meth)acrylic acid, from 5% to 60% by weight of C1-C4 alkyl (meth)acrylate, from 2% to 50% by weight of monomer of formula (III), and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylene monomer, for example, diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

[0079] Among these latter polymers, preference is given most particularly to terpolymers of methacrylic acid, ethyl acrylate and polyoxyethylenated stearyl alcohol allyl ether containing 10 mol of ethylene oxide (INCI name: Steareth-10 allyl ether / acrylates copolymer), in particular in respective weight proportions of 40 / 50 / 10, such as the product sold under the name Salcare SC 80 by the company Ciba;

[0080] (2) associative polymers comprising at least one hydrophilic unit of type unsaturated ethylenic carboxylic acid and at least one hydrophobic unit of (C10-C30) alkyl ester of unsaturated carboxylic acid type.

[0081] Preferably, these polymers are chosen from the copolymers of one (i) monomer of formula (IV) below: H^C———-C--C—OH r1 $ (IV)

[0082] in which R1 denotes H or CH3 or C2H5, and (ii) a monomer of the following formula (V) (monomer of (Ci0-C30)alkyl ester of unsaturated carboxylic acid type): H2C=CR1-COOR3 (V)

[0083] in which R1 denotes H or CH3 or C2H5 and preferably H or CH3, R3 denotes a C10-C30 and preferably C[2-C22] alkyl group.

[0084] In this polymer, monomer (IV) constitutes the hydrophilic unit and monomer (V) constitutes the hydrophobic unit.

[0085] The (Ci0-C30) alkyl esters of unsaturated carboxylic acids include, for example, lauryl (meth)acrylate, stearyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate and dodecyl (meth)acrylate.

[0086] Anionic polymers of this type are described and prepared, for example, according to US Patents 3,915,921 and US Patents 4,509,949.

[0087] Among the anionic associative polymers of this type which will be used more particularly, there are polymers formed from a mixture of monomers comprising:

[0088] (i) acrylic acid,

[0089] (ii) an ester of formula (V) described above in which R1 denotes H or CH3 and R 3 denotes an alkyl group containing from 12 to 22 carbon atoms,

[0090] (iii) and optionally a crosslinking agent, which is a well-known copolymerizable poly-ethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

[0091] Among the anionic associative polymers of this type, we will use more particu- lately:

[0092] those consisting of 95% to 60% by weight of acrylic acid, 4% to 40% by weight of Cio-C3o alkyl acrylate, and 0 to 6% by weight of a polymerizable crosslinking monomer, or alternatively those consisting of 98% to 96% by weight of acrylic acid, 1% to 4% by weight of a Cio-C3o alkyl acrylate and 0.1% to 0.6% by weight of a polymerizable crosslinking monomer, such as those described above.

[0093] Among the aforementioned polymers, those which are most particularly preferred are the products sold by the company Lubrizol under the trade names Pemulen TRI, Pemulen TR2, Carbopol 1382, Carbopol ETD 2020, Carbopol Ultrez 20 and Carbopol Ultrez 21 (INCI name: Acrylates / CiO_3o alkyl acrylate crosspolymer), and even more preferably Pemulen TRI and Carbopol 1382;

[0094] (3) acrylic terpolymers comprising:

[0095] (a) from 19.5% to 70% by weight of an a,[3-monoethylenically unsaturated containing 3 to 5 carbon atoms,

[0096] (b) from 20% to 80% by weight of C1-C4 alkyl (meth)acrylates,

[0097] (c) from 0.5% to 60% by weight of a non-ionic urethane macromonomer of formula (VI) below: CHÿ CH^-CH..........C.....NH-CU-O-(QH2CH / ))p.....R2 IL. CHj

[0098] in which p ranges from 6 to 150 and R2 is chosen from linear alkyl radicals comprising from 18 to 26 and preferably from 20 to 24 carbon atoms. Preferably, the radical R2 is a behenyl radical.

[0099] These terpolymers are described in particular in patent application EP-A-0 173 109.

[0100] The α,[3-monoethylenically unsaturated carboxylic acid (a) may be chosen from acrylic acid, methacrylic acid and crotonic acid. It is preferably (meth)acrylic acid. Preferably, the monomer (a) is methacrylic acid.

[0101] The terpolymer contains a monomer (b) chosen from C1-C4 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate. The monomer (b) is preferably chosen from methyl acrylate and ethyl acrylate.

[0102] These terpolymers are generally in the form of an aqueous dispersion.

[0103] A terpolymer of methacrylic acid / methyl acrylate / condensate of dimethyl m-isopropenyl benzyl isocyanate and be-alcohol is preferably used. polyoxyethylenated henyl ester (40 EO) (INCI name: Polyacrylate-3), such as the product sold in the form of an aqueous dispersion at 25% by weight, under the name Viscophobe DB 1000 by The Dow Chemical Company;

[0104] (4) copolymers of an α,[3-monoethylenically unsaturated carboxylic acid and of an ester of an α,[3-monoethylenically unsaturated carboxylic acid and of a polyoxyethylenated C12-C30 fatty alcohol, in particular with 10 to 50 ethylene oxide units, and of an ester of an α,[3-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.

[0105] Examples of such copolymers that may be cited include:

[0106] - polymers of acrylic acid, methyl acrylate and methacrylate of polyoxyethylene stearyl 20 EO crosslinked with pentaerythrityl allyl ether or trimethylolpropane allyl ether (INCI name: Acrylates / steareth-20 methacrylate crosspolymer) sold under the name Aculyn 88 Polymer by The Dow Chemical Company,

[0107] - crosslinked polymers of acrylic acid, methyl acrylate and me polyoxyethylene behenyl acrylate 25 EO (INCI name: Acrylates / beheneth-25 methacrylate copolymer), such as the product sold under the name Novethix L-10 Polymer by Lubrizol Advanced Materials, Inc.,

[0108] - polymers of acrylic acid, methyl acrylate and methacrylate of polyoxyethylenated C12-C24 alkyl 25 EO (INCI name: Acrylates / palmeth-25 acrylate copolymer), such as the product sold under the name Synthalen W2000 L by the company 3V Group,

[0109] - polymers of methacrylic acid, ethyl methacrylate, methacrylate of C16-C22 alkyl ether of polyethylene glycol containing 25 ethylene glycol units, of 2-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)ethyl methacrylate ether and of polypropylene glycol containing 5 propylene glycol units and of polyethylene glycol containing 25 ethylene glycol units (INCI name: Polyacrylate-33), such as the product sold under the name Rheomer® 33 by the company Rhodia Novecare.

[0110] - polyoxyethylenated (20 EO) acrylic acid / acrylate terpolymer ethyl / stearyl methacrylate (INCI name: Acrylates / steareth-20 methacrylate copolymer) sold in particular under the name Aculyn 22 by The Dow Chemical Company,

[0111] - polyoxyethylenated (25 EO) acrylic acid / acrylate terpolymer ethyl / behenyl methacrylate (INCI name: Acrylates / beheneth-25 methacrylate copolymer) sold in particular under the name Aculyn 28 Polymer by The Dow Chemical Company;

[0112] (5) copolymers of (meth)acrylic acid, of crosslinked alkyl (meth)acrylate in C1-C4, C10-C30 alkyl ether polyethylene glycol methacrylate containing 25 mol of ethylene oxide and polyethylene glycol allyl ether containing 20 ethylene oxide / polypropylene glycol units containing 5 propylene oxide units, such as the product sold under the name Fixate® PlusPolymer by the company Lubrizol (INCI name: Polyacrylate-14).

[0113] According to a particular embodiment, the associative polymers as described above have a weight-average molecular weight of less than 500,000 and even more preferably less than 100,000, preferably ranging from 5000 to 80,000, which can be measured by methods known to those skilled in the art.

[0114] Preferably, the anionic acrylic copolymers are chosen from:

[0115] - anionic copolymers derived from at least one carboxylic acid a,[3-monoethylenically unsaturated and at least one ester of an a,[3-monoethylenically unsaturated carboxylic acid and a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, and in particular an acrylate copolymer;

[0116] - anionic associative acrylic copolymers, which are preferentially chosen from copolymers of an α,[3-monoethylenically unsaturated carboxylic acid, of an ester of an α,[3-monoethylenically unsaturated carboxylic acid and of a polyoxyethylenated C12-C30 fatty alcohol, in particular with 10 to 50 ethylene oxide units, and of an ester of an α,[3-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol; and in particular the copolymer of acrylates / steareth-20 methacrylate and the copolymer of acrylates / beheneth-25 methacrylate; and

[0117] - their mixtures.

[0118] More preferably, the anionic acrylic copolymer(s) are chosen from anionic copolymers derived from at least one unsaturated carboxylic acid and from at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, and in particular an acrylate copolymer.

[0119] Advantageously, the hydrophilic gelling polymer is present in the dye composition of the present invention in an amount ranging from 0.4% by weight to 4.8% by weight, or from 0.5% by weight to 4.5% by weight, preferably from 0.6% by weight to 4.2% by weight, or from 0.7% by weight to 3.9% by weight, and more preferably from 0.8% by weight to 3.6% by weight, from 0.9% by weight to 3.3% by weight, or from 1.0% by weight to 3.0%, relative to the total weight of the dye composition. Polar oils

[0120] Preferably, the colorant composition according to the present invention further comprises one or more polar oils.

[0121] The term "oil" means a fatty substance which is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg).

[0122] The term "fatty substance" means an organic compound insoluble in water at normal temperature (25°C) and atmospheric pressure (750 mmHg). Insoluble means that the solubility is less than 5% and such that it is less than 1%, and further such that it is less than 0.1%.

[0123] The oils have in their structure a chain of at least two siloxane groups or at least one hydrocarbon chain having at least 6 carbon atoms.

[0124] Preferably, the polar oil has a polarity index value of less than 26 mN / m. The term "polarity index" refers to the polarity or surface tension (in 103 Newton / meter), as measured by the ring method using a ring tensiometer at 20°C relative to air.

[0125] The polar oil is, for example, selected from fatty alcohols, esters of fatty acids and fatty alcohols, silicones; and mixtures thereof.

[0126] Examples of the polar oil that may be cited include, but are not limited to, isopropyl palmitate (25.2 mN / m), octyldodecanol (24.8 mN / m), isopropyl myristate (24.2 mN / m), ethylhexyl palmitate (23.1 mN / m), disiloxane (22.7 mN / m), isopropyl stearate (21.9 mN / m), caprylic / capric triglyceride (21.3 mN / m), isopropyl isostearate (21.2 mN / m), jojoba seed oil (20.8 mN / m), peanut oil (20.5 mN / m), sweet almond oil (20.3 mN / m), sunflower seed oil (19.3 mN / m), decyl oleate (18.7 mN / m), avocado oil (18.3 mN / m), olive oil (16.9 mN / m), castor oil (13.7 mN / m), Calendula Officinalis flower oil (11.1 mN / m), wheat germ oil (8.3 mN / m) and mixtures thereof.

[0127] Preferably, the polar oil is chosen from fatty acid esters containing 7 to 19 carbon atoms and fatty alcohols containing 3 to 20 carbon atoms, in which the total number of carbon atoms is between 10 and 30.

[0128] More preferably, the polar oil is chosen from isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate and mixtures thereof.

[0129] Advantageously, the polar oil is present in the dye composition of the present invention in an amount ranging from 10% by weight to 65% by weight, preferably from 15% by weight to 55% by weight, more preferably from 20% by weight to 45% by weight, relative to the total weight of the dye composition. Surfactants

[0130] Preferably, the dye composition according to the present invention further comprises one or more surfactants.

[0131] Preferably, the surfactant is chosen from non-ionic surfactants, amphoteric surfactants, anionic surfactants and combinations thereof.

[0132] Preferably, the surfactant system comprises at least one non-ionic surfactant, at least one amphoteric surfactant and at least one anionic surfactant. Amphoteric Surfactants

[0133] Useful amphoteric surfactants include betaines, alkyl sultaines, alkyl amphoacetates and alkyl amphodiacetates, alkyl amphoproprionates and mixtures thereof. Non-limiting examples of useful amphoteric surfactants are provided below.

[0134] (a) Betaines

[0135] Useful betaines include those of the following formulas (VlIa-VIId): (¾ (Vlla) Ch (Vllb) r ô a È VII (VI|C) R:;::'"""' W ■ CH?L S' V : VH g (Vlld)

[0136] in which Rio is an alkyl group having 8 to 18 carbon atoms; and n is an integer from 1 to 3.

[0137] Particularly useful betaines include, for example, cocobetaine, cocamidopropyl betaine, lauryl betaine, laurylhydroxy sulfobetaine, lauryldimethyl betaine, cocamidopropyl hydroxysultaine, behenyl betaine, capryl / capramidopropyl betaine, lauryl hydroxysultaine, stearyl betaine, and mixtures thereof. Typically, at least one betaine compound is selected from coco betaine, cocamidopropyl betaine, behenyl betaine, capryl / capramidopropyl betaine and lauryl betaine, and mixtures thereof. Particularly preferred betaines include coco betaine and cocamidopropyl betaine.

[0138] (b) Alkyl sultaines

[0139] Non-limiting examples of alkyl sultaines include hydroxyl sultaines of formula (VIII) | cb oh uh (VIII)

[0140] wherein R is an alkyl group having 8 to 18 carbon atoms. More specific examples include, but are not limited to, cocamidopropyl hydroxysultaine, lauryl hydroxysultaine, and mixtures thereof.

[0141] (c) Alkyl amphoacetates and alkyl amphodiacetates

[0142] Useful alkyl amphoacetates and alkyl amphodiacetates include those of formulas (IX) and (X): OH

[0143] wherein R is an alkyl group having 8 to 18 carbon atoms. Sodium is shown as a cation in the above formulas but the cation may be an alkali metal ion such as sodium or potassium, ammonium ions, or alkano-lammonium ions such as monoethanolammonium or triethanolammonium ions. A more specific, but not limiting, example is sodium lauroamphoacetate.

[0144] (d) Alkyl amphopropionates

[0145] Non-limiting examples of amphopropionates include cocoamphopropionate, ca-prylamphopropionate, cornamphopropionate, caproamphopropionate, oleoampho-propionate, isostearoamphopropionate, stearoamphopropionate, lauroampho-propionate, their salts and mixtures thereof.

[0146] Advantageously, the amphoteric surfactant, where appropriate, is present in an amount ranging from 1% by weight to 9% by weight, preferably from 2% by weight to 7% by weight, or from 3% by weight to 5% by weight, relative to the total weight of the dye composition. Anionic surfactants

[0147] The anionic surfactants may be sulfate, sulfonate and / or carboxylic (or carboxylate) surfactants, or mixtures thereof. The sulfate, sulfonate or carboxylic (or carboxylate) surfactants may, in various embodiments, comprise saturated or unsaturated hydrocarbon chains. The anionic surfactants may optionally be in salt form, or in the form of alkali or alkaline earth metal, ammonium or amino alcohol salts.

[0148] The anionic sulfate surfactants comprise at least one sulfate function. The anionic sulfate surfactants that can be used comprise at least one sulfate function (-OSO3H or -OSO3). They can be chosen, by way of non-limiting example, from alkyl or alkenyl sulfates, alkyl or alkenyl ether sulfates, al-kylamido or alkenylamido ether sulfates, alkylaryl or alkenylaryl polyether sulfates, monoglyceride sulfates and the salts of these compounds. In various embodiments, the alkyl or alkenyl groups of these compounds comprise up to 30 carbon atoms, such as, for example, from 6 to 30 carbon atoms, such as from 8 to 28, from 8 to 22 or from 8 to 18 carbon atoms, and the aryl group may optionally denote a phenyl or benzyl group.In at least some embodiments, these compounds may optionally be polyoxyalkylenated, especially polyoxyethylene, comprising for example from 1 to 50 ethylene oxide units, such as from 2 to 10 ethylene oxide units.

[0149] In certain embodiments, the sulfate anionic surfactants are selected from alkyl or alkenyl sulfates, such as C6-C24 alkyl or alkenyl sulfates or C12-C20 alkyl or alkenyl sulfates, or from alkyl or alkenyl ether sulfates, optionally having from 2 to 20 ethylene oxide units, such as C6-C24 alkyl or alkenyl ether sulfates, or C12-C20 alkyl or alkenyl ether sulfates.

[0150] The anionic sulfonate surfactants comprise at least one sulfonate function (-SO3H or -SO3) and may optionally also comprise one or more sulfate functions.

[0151] The anionic sulfonate surfactants which can be used comprise at least one sulfonate function (-SO3H or -SO3). They can be chosen from the following compounds: alkylsulfonates, alkenylsulfonates, alkylamidesulfonates, alkenylamide-sulfonates, alkylarylsulfonates, alkenylarylsulfonates, α-olefinsulfonates, paraffin sulfonates, alkylsulfosuccinates, alkenylsulfosuccinates, alkyl or alkenyl ether sulfo-succinates, alkylamidesulfosuccinates, alkenylamidesulfosuccinates, alkylsul-foacetates, alkenylsulfoacetates, β-acyltaurates, acylisethionates, alkylsulfolaurates, al-kenylsulfolaurates, and the salts of these compounds; the alkyl or alkenyl groups of these compounds comprising up to 30 carbon atoms, such as, for example, from 6 to 30 carbon atoms, such as from 8 to 28, from 8 to 22 or from 8 to 18 carbon atoms; the aryl group preferably designating a phenyl or benzyl group; these compounds being optionally polyoxyalkylenated, in particular polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.

[0152] In some embodiments, the anionic sulfonate surfactants are selected from those having up to 30 carbon atoms, such as 6 to 30, 8 to 28, 8 to 22 or 8 to 18 carbon atoms, for example alkyl or alkenyl sulfosuccinates, such as C6-C24 alkyl or alkenyl sulfosuccinates or C8-C[8 alkyl or alkenyl sulfosuccinates, alkyl or alkenyl ether sulfosuccinates, such as C6-C24 alkyl or alkenyl ether sulfosuccinates or C8-C[8 alkyl or alkenyl ether sulfosuccinates, or acyl isethionates, such as C6-C24 acyl isethionates or C8-C18 acyl isethionates. In some embodiments, the anionic surfactant is selected from lauryl sulfosuccinates.

[0153] The carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-OOH or -COO) and may optionally also comprise one or more sulfate and / or sulfonate functions. The carboxylic anionic surfactants which may be used thus comprise at least one carboxylic or carboxylate function (-OOH or -COO).They may be chosen from the following compounds: acylglycinates, acyllactylates, acylsarcosinates, acyl-glutamates, alkyl-D-galactosideuronic acids, alkyl or alkenyl ether carboxylic acids, alkyl(C6-30) or alkenyl aryl ether carboxylic acids, alkylamido or alkenylamido ether carboxylic acids; and also the salts of these compounds; alkyl, alkenyl and / or acyl groups of these compounds comprising up to 30 carbon atoms, such as from 6 to 30 carbon atoms, in particular from 8 to 28, better still from 8 to 22 or even from 8 to 18 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds being optionally polyoxyalkylenated, in particular polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.

[0154] In some embodiments, C6-C24 or C8-C[8] alkyl or alkenyl monoesters of polyglycosidepolycarboxylic acids, such as C6-C24 or C8-Ci8 alkyl or alkenyl polyglycoside citrates, C6-C24 or C8-Ci8 alkyl polyglycoside tartrates, C6-C24 or C8-Ci8 alkyl or alkenyl polyglycoside sulfosuccinates, and salts thereof, may be selected.

[0155] In other embodiments, polyoxyalkylenated alkyl(amido) or alkenyl(amido) ether carboxylic acids and their salts, in particular those comprising from 2 to 50 alkylene oxide groups and in particular ethylene oxide, such as the compounds sold by the company Kao under the name Akypo, may be chosen. For example, polyoxyalkylenated alkyl(amido) or alkenyl(amido) ether carboxylic acids of formula (XI) may be chosen: R WOCJUK < >< ' H ( X OA (XI)

[0156] in which:

[0157] - Ri represents a linear, branched or cyclic C5-C24 alkyl or alkenyl radical, optionally substituted, an alkyl(C8-C9)phenyl radical, a radical R2CONH-CH2 -CH2- with R2 denoting a linear or branched C9-C2i alkyl or alkenyl radical, preferably, Ri is a C8-C20 and preferably C8-C18 alkyl radical, and aryl preferably denotes phenyl;

[0158] - n is an integer or decimal number (average value) ranging from 2 to 24 and preferably entially from 2 to 10; and

[0159] A denotes H, ammonium, Na, K, Li, Mg or a residue of monoethanolamine or triethanolamine.

[0160] In some embodiments, the polyoxyalkylenated alkyl(amido) or alkenyl(amido) ether carboxylic acids of formula (XI) may be those where R 1 is selected from a C 12 -C 14 alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical; A is selected from hydrogen or a sodium atom, and n ranges from 2 to 20, preferably from 2 to 10. In other embodiments, the polyoxyalkylenated alkyl(amido) or alkenyl(amido) ether carboxylic acids of formula (XI) may be those where R 1 is selected from a C 12 alkyl radical; A is selected from hydrogen or a sodium atom, and n ranges from 2 to 10.

[0161] In certain embodiments, the carboxylic anionic surfactant may be chosen from acylglutamates, in particular C6-C24 or even C12-C20, such as stearoylglutamates, and in particular disodium stearoylglutamate, acylsarcosinates, in particular C6-C24 or even C12-C20, such as palmitoylsarcosinates, and in particular sodium palmitoylsarcosinate, acyllactylates, in particular C12-C28 or even C14-C24, such as behenoyllactylates, and in particular sodium behenoyllactylate, C6-C24 and in particular C12-C20 acylglycinates, C6-C24 alkyl ether carboxylates and in particular (C12-C20) alkyl ether carboxylates, and C6-C24 polyoxyalkylenated alkyl(amido) ether carboxylic acids, in particular those comprising from 2 to 50 ethylene oxide groups.

[0162] As noted herein, the anionic surfactant may optionally be in salt form. In this case, the salt may, for example, be selected from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline earth metal salts, such as the magnesium salt. In preferred embodiments, alkali metal or alkaline earth metal salts may be selected.

[0163] Advantageously, the anionic surfactant, where appropriate, is present in an amount ranging from 0.05% by weight to 7% by weight, preferably from 0.25% by weight to 4%. by weight, or from 0.5% by weight to 1% by weight, relative to the total weight of the dye composition. Nonionic surfactants

[0164] Nonionic surfactants selected from the group consisting of polyoxyalkylenated and polyglycerolated nonionic surfactants are particularly useful.For example, useful nonionic surfactants include hydrogenated castor oil (e.g., PEG-25 hydrogenated castor oil, PEG-30 hydrogenated castor oil, PEG-35 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-45 hydrogenated castor oil, PEG-50 hydrogenated castor oil, PEG-54 hydrogenated castor oil, PEG-55 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-65 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG-100 hydrogenated castor oil, and PEG-200 hydrogenated castor oil), polyol esters with fatty acids or their alkoxylated derivatives (e.g., glyceryl distearate, glyceryl hydroxystearate, glyceryl laurate, glyceryl linoleate, glyceryl myristate, glyceryl oleate, glyceryl stearate, one of their ethoxylated derivatives, or one of their mixtures), and ethoxylated fatty alcohols (or C8-C30 alcohols).

[0165] In some cases, the one or more nonionic surfactants may include PEG-40 hydrogenated castor oil, oleth-5, polysorbate 80, or a mixture thereof.

[0166] The non-ionic surfactant may be, for example, chosen from alcohols, alpha-diols, alkylphenols and fatty acid esters, these compounds being ethoxylated, propoxylated or glycerolated and comprising at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, knowing that the number of ethylene oxide or propylene oxide groups may range from 2 to 50, and that the number of glycerol groups may range from 1 to 30. Maltose derivatives may also be mentioned.Mention may also be made, in a non-limiting manner, of copolymers of ethylene oxide and / or propylene oxide; condensates of ethylene oxide and / or propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 moles of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1.5 to 5 glycerol groups, such as from 1.5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 moles of ethylene oxide; ethoxylated oils of vegetable origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; mono or diesters of polyethoxylated fatty acids of alkylpolyglycosides (C6-C24) of glycerol; ÎV-alkylglucamine (C6-C24) derivatives, amine oxides such as alkylamine (C10-C14) oxides or / V-acylaminopropylmorpholine (C10-C14) oxides; and mixtures thereof.

[0167] Examples of oxyalkylenated nonionic surfactants that may be mentioned include: oxyalkylenated (C8-C24) alkylphenols, oxyalkylenated C8-C30 alcohols, saturated or unsaturated, linear or branched, oxyalkylenated C8-C30 amides alkylenated, saturated or unsaturated, linear or branched, esters of saturated or unsaturated, linear or branched C8-C30 acids and polyethylene glycols, polyoxyalkylenated esters of saturated or unsaturated, linear or branched C8-C30 acids and sorbitol, saturated or unsaturated, oxyalkylenated vegetable oils, condensates of ethylene oxide and / or propylene oxide, among others, alone or in mixtures.

[0168] As examples of polyglycerolated nonionic surfactants, C8-C40 polyglycerolated alcohols may be used. In particular, C8-C40 polyglycerolated alcohols correspond to the following formula XII: RO.......[CHZ......CH(CH2OH).......O]..^......H or RO.......[CH (XII) (CH3ÔH)—CH2bV-H

[0169] in which R represents a linear or branched alkyl or alkenyl radical, C8-C40 and preferably C8-C30, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

[0170] Examples of compounds suitable in the context of the invention include lauryl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 moles of glycerol, oleyl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 moles of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 moles of glycerol, cetearyl alcohol containing 6 moles of glycerol, oleocetyl alcohol containing 6 moles of glycerol, and octadecanol containing 6 mol of glycerol.

[0171] Alcohol can represent a mixture of alcohols in the same way that the value of m represents a statistical value, meaning that in a commercial product several species of polyglycerolated fatty alcohol can coexist as a mixture.

[0172] The non-ionic surfactants may be chosen from polyol esters with saturated or unsaturated chain fatty acids containing, for example, from 8 to 24 carbon atoms, preferably from 12 to 22 carbon atoms, and their alkoxylated derivatives, preferably with an alkylene oxide number of 10 to 200, and more preferably from 10 to 100, such as glyceryl esters of a C8-C24 fatty acid or acids, preferably C12-C22, and their alkoxylated derivatives, preferably with an alkylene oxide number of 10 to 200, and more preferably from 10 to 100; polyethylene glycol esters of a C8-C24 fatty acid or acids, preferably C[2-C22, and their alkoxylated derivatives, preferably with an alkylene oxide number of 10 to 200, and more preferably of 10 to 100;sorbitol esters of a C8-C24 fatty acid or acids, preferably C[2-C22, and their alkoxylated derivatives, preferably with an alkylene oxide number of 10 to 200, and more preferably of 10 to 100; sugar esters (sucrose, glucose, ; alkylglycose) of a C8-C24 fatty acid or acids, preferably C12-C22, and their alkoxylated derivatives, preferably with an alkylene oxide number of 10 to 200, and more preferably 10 to 100; fatty alcohol ethers; sugar ethers of a C8-C24 fatty alcohol or alcohols, preferably C12-C22, and mixtures thereof.

[0173] Examples of ethoxylated fatty esters that may be cited include adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene groups, such as compounds with the INCI names: PEG-9 to PEG-50 laurate; PEG-9 to PEG-50 palmitate; PEG-9 to PEG-50 stearate; PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate; and the compound polyethylene glycol 100 EO monostearate (INCI name: PEG-100 stearate) and mixtures thereof.

[0174] As glyceryl esters of fatty acids, mention may be made in particular of glyceryl stearate (glyceryl mono-, di- and / or tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate and mixtures thereof.

[0175] As glyceryl esters of C8-C24 alkoxylated fatty acids, mention may be made, for example, of polyethoxylated glyceryl stearate (glyceryl mono-, di- and / or tristearate) such as PEG-20 glyceryl stearate.

[0176] The sorbitol esters of C8-C24 fatty acids and their alkoxylated derivatives may be chosen from sorbitan palmitate, sorbitan trioleate and alkoxylated sorbitan fatty acid esters containing, for example, from 20 to 100 EO, such as, for example, polyethylene sorbitan trioleate (polysorbate 85) or the compounds marketed under the trade names Tween 20 or Tween 60 by Ubiqema.

[0177] As esters of fatty acids and glucose or alkylglucose, mention may be made of glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, fatty esters of methylglucoside, and more specifically the diester of methylglucoside and oleic acid (INCI name: Methyl glucose dioleate), the mixed ester of methylglucoside and the mixture of oleic acid / hydroxystearic acid (INCI name: Methyl glucose dioleate / hydroxystearate), the ester of methylglucoside and isostearic acid (INCI name: Methyl glucose isostearate), the ester of methylglucoside and lauric acid (INCI name: Methyl glucose laurate), the mixture of monoester and of methylglucoside diester and isostearic acid (INCI name: Methyl glucose sesquiisostearate), the mixture of monoester and diester of methylglucoside and stearic acid (INCI name: Methyl glucose sesquistearate) and, in particular,the product marketed under the name Glucate SS by AMERCHOL and their mixtures.,

[0178] As ethoxylated ethers of fatty acids and glucose or alkylglucose, mention may be made, for example, of ethoxylated ethers of fatty acids and methylglucose and, in par In particular, polyethylene glycol ether of the diester of methylglucose and stearic acid with approximately 20 moles of ethylene oxide (INCI name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, polyethylene glycol ether of the mixture of monoester and diester of methylglucose and stearic acid with approximately 20 moles of ethylene oxide (INCI name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof.

[0179] Examples of sucrose esters that may be mentioned are sucrose palmitostearate, sucrose stearate and sucrose monolaurate.

[0180] As sugar ethers, alkylpolyglucosides may be used, and for example, decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl / capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818 / UP by Henkel, cetostearyl glucoside optionally mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside,for example in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example in the form of the mixture (35 / 65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and their mixtures may in particular be cited.

[0181] Advantageously, the non-ionic surfactant, where appropriate, is present in an amount ranging from 0.05% by weight to 3.5% by weight, preferably from 0.25% by weight to 2.5% by weight, more preferably from 0.5% by weight to 1.5% by weight, relative to the total weight of the dye composition.

[0182] Advantageously, the surfactant is present in the dye composition of the present invention in an amount ranging from 0.1% to 30% by weight, or 0.3% by weight to 25% by weight, preferably from 0.5% by weight to 20% by weight, or 0.8% by weight to 18% by weight, or from 1% by weight to 15% by weight, more preferably 1.5% by weight to 12%, or from 2% by weight to 10% by weight, relative to the total weight of the dye composition.

[0183] In the presence of polar oils and surfactants, the composition according to the present invention will have a cream texture and can be easily applied. Adjuvants

[0184] The colorant composition according to the present invention may also comprise one or more cosmetic adjuvants.

[0185] For example, the colorant composition may comprise one or more additives well known in the art, such as anionic, nonionic or amphoteric polymers or mixtures thereof, hair loss prevention agents, sequestrants, surfactants, plasticizers, solubilizers, acidifying agents, alkaline agents, antioxidants, opacifiers, reducing agents and preservatives.

[0186] It goes without saying that the person skilled in the art will take care to select these optional additional compounds in such a way that the advantageous properties intrinsically associated with the invention are not, or not substantially, negatively affected by the envisaged addition(s). Aqueous phase

[0187] The colorant composition of the present invention may comprise an aqueous phase.

[0188] Preferably, the aqueous phase comprises water.

[0189] The aqueous phase may also comprise one or more water-miscible or partially water-miscible compounds (at room temperature of 20 to 25°C), for example C2-C8 lower polyols, monoalcohols or polyol ethers (containing in particular from 3 to 16 carbon atoms). The solvent for the dye composition of the present invention may include water, or even consist essentially of water.

[0190] Advantageously, the aqueous phase is present in an amount ranging from approximately 15% by weight to approximately 80% by weight, preferably from approximately 20% by weight to approximately 70% by weight, or from approximately 25% by weight to approximately 60% by weight, relative to the total weight of the dye composition.

[0191] Advantageously, the water is present in an amount ranging from 15% by weight to 80% by weight, preferably from 20% by weight to 70% by weight, more preferably from 25% by weight to 60% by weight, relative to the total weight of the dye composition.

[0192] Preferably, the dye composition according to the present invention is free of ammonia.

[0193] According to a particular embodiment, the dye composition according to the present invention comprises, relative to the total weight of the dye composition:

[0194] (i) from 1.2% by weight to 2.5% by weight of at least one oxidative base chosen from 4,5-diamino-l-([3-hydroxyethyl]pyrazole, its sulfate, chloride, dimethosulfonate and mixtures thereof;

[0195] (ii) from 0.2% by weight to 1% by weight of at least one X-carrageenan type polysaccharide;

[0196] (iii) from 1.0% by weight to 3.0% by weight of at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers;

[0197] (iv) from 20% by weight to 45% by weight of at least one polar oil chosen from isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate and mixtures thereof; and

[0198] (v) from 2% to 10% by weight of at least one surfactant chosen from coco-betaine, cocamidopropyl betaine, sodium laureth sulfate, sodium lauryl sulfate, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, caprylyl / capryl glucoside and mixtures thereof. Necessary

[0199] According to the second aspect, the kit of the present invention comprises:

[0200] A) the colorant composition according to the first aspect of the present invention; and

[0201] B) a developer composition for dyeing keratinous fibers.

[0202] The developer composition is not particularly limited, it may be any developer composition used for dyeing keratinous fibers, especially hair, commonly known in the art.

[0203] Preferably, the developer composition is preferably placed separately from the colorant composition. Use

[0204] According to the third aspect, the present invention provides a process for dyeing keratinous fibers, comprising:

[0205] mixing the dye composition according to the present invention and a developer composition for dyeing keratinous fibers immediately before use;

[0206] applying the resulting mixture to the keratinous fibers; and

[0207] rinsing the mixture on the keratinous fibers with water, optionally washing the keratinous fibers with a shampoo before rinsing the keratinous fibers with water.

[0208] In particular, keratinous fibers are hair.

[0209] The mixed compositions, including the dye composition and the developer composition, are usually left in place on the fibers for a period of time generally ranging from 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.

[0210] The temperature during the process is conventionally between 20°C and 80°C and preferably between 20 and 60°C. After the treatment, the human keratinous fibers are advantageously rinsed with water. They may optionally be further washed with shampoo, then rinsed with water, before being dried or allowed to dry.

[0211] The process can be repeated several times to obtain the desired coloring.

[0212] The aforementioned kit can also be equipped with means allowing the desired mixture to be supplied to the hair, for example the device described in patent FR 2 586 913.

[0213] In the third aspect, the present invention provides a use of an X-carrageenan type polysaccharide for improving the stability of a colorant composition comprising at least one oxidative base selected from aminopyrazoles, their addition salts and their mixtures.

[0214] The inventors have discovered that with the presence of an X-carrageenan type polysaccharide, a dye composition comprising at least one oxidative base selected from aminopyrazoles, their addition salts and their mixtures, will be stable, for example, there will be no phase separation after storage for a period of time. EXAMPLES

[0215] The following examples are given for the purpose of illustration of the present invention and should not be construed as limiting the scope.

[0216] The main raw materials used, trade names and their supplier are listed in Table 1.

[0217] [Table 1] Table 1 INCI name Trade name Supplier PEG-40 hydrogenated castor oil EUMULGIN CO 40-SC BASF Cocamidopropyl betaine DEHYTON PK 45 BASF Sodium lauryl sulfate TEXAPON LS 30 BASF Acrylates copolymer CARBOPOL AQUA SF-1 POLYMER LUBRIZOL Ethylhexyl palmitate CEGESOFT C 24 BASF Ascorbic acid ASCORBIC ACID 100 MESH CSPC WEISHENG PHARMACEUTI CAL Sodium metabisulfite SODIUM METABISULPHITE HP ESSECO Ethanolamine MONOETHANOLAMINE CARE BASF Tetrasodium glutamate diacetate DISSOLVINE GL-47-S AKZO NOBEL (NOURYON) 5-Amino-6-chloro-o-cresol 5-AMINO-6-CHLORO-O-CRE SOL DRAGON CHEMICAL m-Aminophenol RODOL EG LOWENSTEIN 1-Hydroxyethyl 4,5-diamino pyrazole sulfate JAROCOL AHP VIVIMED Hydroxypropyl guar JAGUAR HP 105 SGI RHODIA CG-131 CP KELCO Hydroxypropyl methyl-cellulose and cellulose gum and xanthan gum Texturpure TM sa-1 Ashland Inventive Example 1 and Comparative Examples 1 to 4

[0218] The dye compositions according to inventive example (EI) 1 and comparative examples (CE) 1 to 4 were prepared with the ingredients listed in Table 2 (the contents were expressed as percentages by weight of ingredients relative to the total weight of each composition, unless otherwise indicated):

[0219] [Table 2] Table 2 Ingredients El. 1 EC. 1 EC. 2 EC.3 EC.4 Acrylates copolymer 2,4 2,4 2,4 2,4 2,4 Hydroxypropyl guar / / 0,5 / / X-carrageenan 0,5 / / / / K-carrageenan / / / 0,5 / i-carrageenan / / / / 0,5 Hydroxypropyl methylcellulose and cellulose gum and xanthan gum / / 0.5 / / Ethanolamine 9.3 9.3 9.3 9.3 9.3 Ethylhexyl palmitate 30.0 30.0 30.0 30.0 30.0 Ascorbic acid 0.25 0.25 0.25 0.25 0.25 Tetrasodium glutamate diacetate 0.2 0.2 0.2 0.2 0.2 Sodium metabisulfite 0.7 0.7 0.7 0.7 0.7 Sodium lauryl sulfate 0.7 0.7 0.7 0.7 0.7 Cocamidopropyl betaine 3.8 3.8 3.8 3.8 3.8 PEG-40 hydrogenated castor oil 1.0 1.0 1.0 1.0 1.0 m-Aminophenol 0.3 0.3 0.3 0.3 0.3 5-amino-6-chloro-o-cresol 0.7 0.7 0.7 0.7 0.7 1-Hydroxyethyl 4,5-diamino pyrazole sulfate 1.6 1.6 1.6 1.6 1.6 Water QS100 QS100 QS100 QS100 QS100

[0220] The composition of inventive example 1 is a composition according to the present invention.

[0221] The composition of Comparative Example 1 does not comprise at least one X-carrageenan type polysaccharide.

[0222] The composition of Comparative Example 2 comprises hydroxypropyl methylcellulose and cellulose gum and xanthan gum instead of an X-carrageenan type polysaccharide.

[0223] The composition of Comparative Example 3 comprises a k-Carrageenan type polysaccharide instead of an X-Carrageenan type polysaccharide.

[0224] The composition of Comparative Example 4 comprises an i-carrageenan type polysaccharide instead of an X-carrageenan type polysaccharide.

[0225] Preparation procedure:

[0226] The compositions listed above were prepared as follows, taking as an example the composition of Invention Example 1:

[0227] 1) adding acrylate copolymer to water and mixing for 5 minutes;

[0228] 2) addition of PEG-40 hydrogenated castor oil, sodium lauryl sulfate and coca- midopropyl betaine into the resulting system and mix for 15 minutes;

[0229] 3) adding ethanolamine to the obtained system and mixing for 5 to 10 minutes ;

[0230] 4) addition of ethylhexyl palmitate premixed with X-carrageenan in the obtained system and mixing it for 15 minutes; and

[0231] 5) addition of tetrasodium glutamate diacetate, ascorbic acid, metabisulfite sodium, m-aminophenol, 5-amino-6-chloro-o-cresol and 1-hydroxyethyl 4,5-diamino pyrazole sulfate, and mixing for 15 minutes to obtain a dye composition. Assessment Viscosity

[0232] The viscosity of each colorant composition was measured to verify whether the composition is acceptable for pumping and application.

[0233] Viscosity was measured by a Mettler RM 180 Rheomat with spindle #3 at 25°C to verify whether the viscosity of each colorant composition is within a range of 600 to 1500 mPa.s. Stability

[0234] The stability of a test composition was evaluated as follows:

[0235] Each composition was prepared and aged for 24 hours at room temperature, then contained in a cosmetic bottle, then placed in an oven or refrigerator to be stored for a period of time:

[0236] 50°C: 2 weeks;

[0237] 45°C: 1 month or 2 months;

[0238] Room temperature (20C to 25°C): 1 month or 2 months;

[0239] 4°C: 1 month or 2 months.

[0240] It was then checked whether the appearance of the test composition was visibly modified.

[0241] If there is no phase separation after storage, then the test composition is considered stable.

[0242] If there is phase separation after storage, the test composition is considered unstable. Application Properties

[0243] Each of the dye compositions of Inventive Example 1 and Comparative Examples 1 to 4 was applied to a half mannequin head by hand. The time T required to uniformly apply the compositions was recorded and compared, wherein each composition was applied twice by different in-house hair experts, then the average time was calculated and the scores were given according to the following standard.

[0244] 10: T < 100 seconds;

[0245] 9:100 <T<110 secondes ;

[0246] 8:110 <T<120 secondes ;

[0247] 7:120 <T<130 secondes ;

[0248] 6:130 <T<120 secondes ;

[0249] 5:140 <T<150 secondes ;

[0250] 4:150 <T<160 secondes ;

[0251] 3:160 <T<170 secondes ;

[0252] 2:170 <T<180 secondes ;

[0253] 1 : > 180 seconds.

[0254] The results are summarized in Table 3.

[0255] [Table 3] Table 3 Properties El. 1 EC.l EC. 2 EC. 3 EC. 4 Viscosity (mPa.s) 1150.05 1304.85 1099.84 2354.95 2116.55 Stability 2W, 50°C Stable Unstable Unstable Unstable Unstable IM, RT Stable Stable Stable Stable Stable IM, 4°C Stable Stable Stable Stable Stable IM, 45°C Stable Unstable Stable Unstable Stable 2M, RT Stable Stable Stable Stable Stable 2M, 4°C Stable Stable Stable Stable Stable 2M, 45°C Stable Unstable Unstable Unstable Unstable Application score 9 9 4 7 8

[0256] It can be seen from Table 3 that the compositions according to the present invention are stable and can be applied easily.

Claims

Claims

1. Dye composition for dyeing keratinous fibers, comprising: i) at least one oxidative base chosen from aminopyrazoles, their addition salts and their mixtures; ii) at least one polysaccharide of X-carrageenan type; and iii) at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers.

2. Dye composition according to claim 1, wherein the oxidative base is selected from diaminopyrazoles, their addition salts, and mixtures thereof, preferably the oxidative base is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-([3-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, l-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-l-tert-butyl-3-methylpyrazole, 4,5-diamino-l-(2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl- 1-isopropylpyrazole, 4,5-diamino-3-methyl- 1-isopropylpyrazole, their sulfates, chlorides and dimethosulfonates, and mixtures thereof,more preferably the oxidative base is 4,5-diamino-l-([3-hydroxyethyl)pyrazole, its sulfate, its chloride, its dimethosulfonate and their mixtures.,

3. A dye composition according to any one of claims 1 to 2, wherein the anionic acrylic copolymers are chosen from - anionic copolymers derived from at least one unsaturated carboxylic acid and at least one ester of an unsaturated carboxylic acid and a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms; - anionic associative acrylic copolymers; and - their mixtures; preferentially, the anionic acrylic copolymers are chosen from - anionic copolymers derived from at least one α,[3-monoethylenically unsaturated carboxylic acid and at least one ester of an α,[3-monoethylenically unsaturated carboxylic acid and a monoalcohol comprising from 1 to 6 carbon atoms and preferentially from 1 to 4 carbon atoms; - copolymers of an α,[3-monoethylenically unsaturated carboxylic acid, of an ester of an α,[3-monoethylenically unsaturated carboxylic acid and of a polyoxyethylenated C12-C30 fatty alcohol, in particular with 10 to 50 ethylene oxide units, and of an ester of an α,[3-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol; and - mixtures thereof.

4. A dye composition according to any one of claims 1 to 3, further comprising one or more polar oils, preferably the polar oil has a polarity index value of less than 26 mN / m, more preferably the polar oil is selected from fatty alcohols, fatty acid esters of fatty alcohols, silicones and mixtures thereof; even more preferably is selected from fatty acid esters containing 7 to 19 carbon atoms and fatty alcohols containing 3 to 20 carbon atoms, wherein the total number of carbon atoms is between 10 and 30; most preferably selected from isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate and mixtures thereof.

5. A dye composition according to any one of claims 1 to 4, further comprising one or more surfactants, preferably the surfactant is selected from nonionic surfactants, amphoteric surfactants, anionic surfactants and combinations thereof, more preferably the amphoteric surfactants are selected from betaines, alkyl sultaines, alkyl amphoacetates, alkyl amphoproprionates and mixtures thereof, and preferably from coco-betaine, cocami-dopropyl betaine and mixtures thereof; the anionic surfactants are chosen from sulfate surfactants, sulfonate, carboxylic (or carboxylate) and mixtures thereof, and preferably chosen from sodium laureth sulfate, sodium lauryl sulfate and mixtures thereof; and / or the non-ionic surfactants are chosen from polyoxyalkylenated and polyglycerolated hydrogenated castor oils, glyceryl esters of fatty acids, glyceryl esters of C8-C24 alkoxylated fatty acids, esters of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and glucose or alkylglucose, alkylpolyglucosides and mixtures thereof, and preferably from PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, caprylyl / capryl glucoside and mixtures thereof.

6. A dye composition according to any one of claims 1 to 5, further comprising water, preferably in an amount ranging from 15% by weight to 80% by weight, more preferably from 20% by weight to 70% by weight, even more preferably from 25% by weight to 60% by weight, relative to the total weight of the dye composition.

7. A dye composition according to any one of claims 1 to 6, comprising, relative to the total weight of the dye composition: i) from 1.2% by weight to 2.5% by weight of at least one oxidative base chosen from 4,5-diamino-1-([3-hydroxyethyl)pyrazole, its sulfate, chloride, dimethosulfonate and mixtures thereof; ii) from 0.2% by weight to 1% by weight of at least one X-carrageenan type polysaccharide; iii) from 1.0% by weight to 3.0% by weight of at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers; iv) from 20% by weight to 45% by weight of at least one liquid polar fatty substance chosen from isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate and mixtures thereof;and v) from 2% by weight to 10% by weight of at least one surfactant selected from coco-betaine, cocamidopropyl betaine, sodium laureth sulfate, sodium lauryl sulfate, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, caprylyl / capryl glucoside, and combinations thereof.;

8. A kit for dyeing keratinous fibers, comprising: A) the dye composition according to any one of claims 1 to 7; and B) a developer composition for dyeing keratinous fibers. tineuses.

9. A process for dyeing keratinous fibers, comprising mixing the dye composition as defined in any one of claims 1 to 7 and a developer composition for dyeing keratinous fibers immediately before use; applying the resulting mixture to the keratinous fibers; and rinsing the mixture from the keratinous fibers with water, optionally washing the keratinous fibers with a shampoo before rinsing the keratinous fibers with water.