WO2021123329A1 - Hair dyeing composition comprising a direct dye, a scleroglucan gum and a non-ionic associative polymer - Google Patents

Hair dyeing composition comprising a direct dye, a scleroglucan gum and a non-ionic associative polymer Download PDF

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Publication number
WO2021123329A1
WO2021123329A1 PCT/EP2020/087251 EP2020087251W WO2021123329A1 WO 2021123329 A1 WO2021123329 A1 WO 2021123329A1 EP 2020087251 W EP2020087251 W EP 2020087251W WO 2021123329 A1 WO2021123329 A1 WO 2021123329A1
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alkyl
weight
chosen
groups
fatty
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PCT/EP2020/087251
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French (fr)
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Sabrina MULLER
Cindy YADEL
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L'oreal
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9728—Fungi, e.g. yeasts

Definitions

  • the present invention relates to the field of dyeing keratin fibres and more particularly to the field of hair dyeing.
  • the invention relates in particular to a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising one or more direct dye(s), in a total weight content ranging from 0.01% to 10% relative to the total weight of the composition, one or more scleroglucan gums and one or more non ionic associative polymers.
  • the invention also relates to a dyeing process comprising the application of said composition to keratin fibres, in particular human keratin fibres such as the hair.
  • colourings can be carried out by direct application to keratin fibres of the composition containing the direct dye(s) or by application of an extemporaneously prepared mixture of a composition containing the direct dye(s) with a composition containing an oxidizing bleaching agent which is preferably aqueous hydrogen peroxide solution.
  • an oxidizing bleaching agent which is preferably aqueous hydrogen peroxide solution.
  • compositions for direct dyeing of keratin fibres by combining surfactants and/or thickeners with the direct dyes in order to improve the physical properties and/or the colourings obtained.
  • compositions comprising a direct dye and a xanthan gum for obtaining better thickening of direct dyeing compositions are in particular known from document FR 2 548 893, it being possible for these compositions to optionally contain surfactants.
  • compositions do not give totally satisfactory cosmetic and/or dyeing properties, in particular with regard to the intensity of the colourings and their selectivities representative of colour differences between various parts of one or more strands of hair according to the degrees of sensitization.
  • compositions comprising a direct dye, a bioheteropolysaccharide, a cationic surfactant and an amphoteric surfactant, as described in document FR 2910282.
  • one of the objects of the present invention is to propose compositions for dyeing keratin fibres, preferably human keratin fibres such as the hair, which do not have the drawbacks mentioned above.
  • one of the objects of the present invention is to propose dyeing compositions which are capable of giving very good dyeing performance qualities, notably in terms of intensity and/or colour build up, and also in terms of selectivity, chromaticity and/or resistance to external agents, having good working qualities in particular when applied to keratin fibres, and giving the fibres good cosmetic properties (softness, smoothness) while at the same time being stable (notably not undergoing phase separation and having a viscosity and/or pH which change(s) little or not at all over time).
  • compositions for dyeing keratin fibres preferably human keratin fibres such as the hair, comprising: one or more direct dye(s); one or more scleroglucan gum(s); one or more non-ionic associative polymer(s), the direct dye(s) being present in a content ranging from 0.01% to 10% by weight relative to the total weight of the composition.
  • the invention also relates to a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, comprising the application to said fibres of a dye composition as defined previously.
  • compositions according to the invention can thus give very good dyeing performance on keratin fibres, notably in terms of build-up, intensity, chromaticity and/or selectivity. They also afford compositions which have good rheological properties so as not to run down onto the face, the scalp or beyond the areas that it is proposed to dye, when they are applied.
  • compositions according to the invention are stable.
  • the term “stable” in particular means that physical properties such as the appearance, the pH and/or the viscosity vary little or not at all over time, and in particular that the viscosity of the composition does not change or changes little during storage and/or that the composition does not undergo phase separation during storage.
  • compositions according to the invention have the advantage of being stable (not undergoing phase separation) independently of the pH.
  • compositions are preferably stable (do not undergo phase separation) even in the presence of a high content of certain compounds, for instance direct dyes.
  • compositions of the invention advantageously have good application qualities, such as ease of spreading and extending of the composition.
  • composition for dyeing or “dye composition” or “dyeing composition” means a composition intended to be applied to keratin fibres, preferably human keratin fibres and in particular the hair, in order to dye said fibres or said hair.
  • the dyeing composition according to the invention has a thickened texture, and is in cream or gel form, preferably in gel form.
  • the composition according to the invention generally has, at ambient temperature, a viscosity of greater than 50 cps, preferably between 200 and 100 000 cps, more preferentially between 300 and 50 000 cps, even more preferentially between 400 and 10 000 cps, and better still from 500 to 8000 cps, or even 600 to 2000, cps measured at 25°C at a spin speed of 200 rpm using a rheometer such as a Rheomat RM 180 equipped with a No. 3 or 4 spindle, the measurement being taken after 30 seconds of rotation of the spindle (after which time stabilization of the viscosity and of the spin speed of the spindle is observed).
  • a viscosity of greater than 50 cps, preferably between 200 and 100 000 cps, more preferentially between 300 and 50 000 cps, even more preferentially between 400 and 10 000 cps, and better still from 500 to 8000 cps, or even 600 to 2000,
  • the dyeing composition according to the present invention comprises at least one direct dye.
  • the direct dye(s) that may be used according to the invention are chosen from natural direct dyes, synthetic direct dyes, and mixtures thereof.
  • the direct dye(s) that may be used according to the invention are chosen from ionic direct dyes and non-ionic direct dyes, more particularly from cationic direct dyes, amphoteric direct dyes, anionic direct dyes, non-ionic direct dyes, and mixtures thereof.
  • the direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral (non-ionic), acidic (anionic) or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.
  • the cationic direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group.
  • the cationic direct dyes comprise at least one quaternized cationic chromophore.
  • cationic direct dyes As cationic direct dyes according to the invention, mention may be made of the following dyes: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bisisoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphen
  • cationic azo dyes mention may be made particularly of those resulting from the cationic dyes described in Kirk-Othmer’ s Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & Sons, updated on 19 April 2010.
  • the direct dye(s) are chosen from cationic dyes known as "basic dyes".
  • cationic quinone dyes those mentioned in the abovementioned Colour Index International are suitable for use and, among these, mention may be made, inter alia, of the following dyes:
  • azine dyes that are suitable for use, mention may be made of those listed in the Colour Index International, for example the following dyes:
  • the cationic direct dyes are chosen from those resulting from dyes of azo and hydrazono type.
  • the direct dyes are cationic azo dyes, described in EP 850 636, FR 2 788433, EP 920 856, WO 99/48465, FR 2 757385, EP 850637, EP 918 053, WO 97/44004, FR 2 570 946, FR 2285 851, DE 2 538 363, FR 2 189 006, FR 1 560664, FR 1 540423, FR 1 567219, FR 1 516943, FR 1 221 122, DE 4220388, DE 4 137005, WO 01/66646, US 5 708 151, WO 95/01772, WO
  • the cationic direct dye(s) comprise a quaternary ammonium group; more preferentially, the cationic charge is endocyclic.
  • cationic radicals are, for example, a cationic radical:
  • an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bistetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyry
  • Het + represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (Ci-Cx) alkyl group such as methyl;
  • Ar + represents an aryl radical, such as phenyl or naphthyl, having an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-C 8 )alkylammonium, such as trimethylammonium;
  • Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cx)alkyl, ii) optionally substituted (Ci-Cx)alkoxy, iii) (di)(Ci- C 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C 8 )alkylamino, v) optionally substituted N-(Ci-C 8 )alkyl-N-aryl(Ci- C 8 )alkylamino or alternatively Ar represents a jul
  • Ar represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (Ci- C 8 )alkyl, hydroxyl, (di)(Ci-C 8 )(alkyl)amino, (Ci-C 8 )alkoxy or phenyl groups;
  • R a and R b which may be identical or different, represent a hydrogen atom or a (Ci-C 8 )alkyl group, which is optionally substituted, preferentially with a hydroxyl group;
  • R a with a substituent of Het + and/or R b with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, R a and R b represent a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl group;
  • Q represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.
  • R 1 represents a (Ci-C4)alkyl group such as methyl
  • R 2 and R 3 which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, such as methyl;
  • R 4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cx)alkyl, optionally substituted (Ci-Cx)alkoxy, or (di)(Ci- C 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R 4 is a hydrogen atom,
  • - Z represents a CH group or a nitrogen atom, preferentially CH
  • - Q is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.
  • the dyes of formulae (C-II-1) and (C-IV-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
  • a halide such as chloride
  • an alkyl sulfate such as methyl sulfate or mesityl.
  • the direct dyes are fluorescent, that is to say that they contain at least one fluorescent chromophore as defined previously.
  • Fluorescent dyes that may be mentioned include the radicals resulting from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro ⁇ 2- [(2H-pyrrol-2-ylidene-kN)methyl] - 1 H-py rrolato-kN ⁇ borons (BODIPY ® ), diketopyrrolopyrroles, fluorindines, (poly)methines (notably cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyls), oxadiazoles,
  • the cationic dye(s) are fluorescent and comprise at least one quaternary ammonium radical such as those of formula (C- VI) below, and also the optical and geometric isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates:
  • W + represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (Ci-Cx)alkyl groups, optionally substituted notably with one or more hydroxyl groups;
  • Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (Ci-Cx)alkyl, preferably of C 1 -C 4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-Cx)alkoxy groups such as methoxy; v) one or more hydroxy(Ci-Cx)alkyl groups such as hydroxyethyl, vi) one or more amino groups or (di)(Ci-C 8 )alkylamino, preferably with the C 1 -C 4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or
  • * m' represents an integer between 1 and 4 inclusive, and in particular m is 1 or 2; more preferentially 1;
  • R c and R d which are identical or different, represent a hydrogen atom or an optionally substituted (Ci-Cx)alkyl group, preferentially of C1-C4, or alternatively R c contiguous with W + and/or R d contiguous with Ar form, with the atoms that carry them, a (hetero)cycloalkyl; particularly, R c is contiguous with W + and they form a (hetero)cycloalkyl such as cyclohexyl;
  • Q is an organic or mineral anionic counterion as defined above.
  • cationic direct dyes mention may also be made of triarylmethane cationic dyes.
  • the triarylmethane direct dye(s) according to the invention are chosen from the cationic dyes of formulae (C-VII) and (C-UIG) below:
  • Ri, R 2 , R 3 and R 4 which may be identical or different, represent a hydrogen atom or a group from among: (Ci-C 6 )alkyl which is optionally substituted, preferably with a hydroxyl group; aryl such as phenyl, aryl(Ci-C 4 )alkyl such as benzyl, heteroaryl, heteroaryl(Ci-C 4 )alkyl, or else two groups Ri and R 2 , and/or R 3 and R 4 , borne by the same nitrogen atom, form, together with the nitrogen atom which bears them, an optionally substituted heterocycloalkyl group such as morpholino, piperazino or piperidino; preferably, Ri, R 2 , R 3 and R 4 , which may be identical or different, represent a hydrogen atom or a (Ci-C 4 )alkyl group;
  • R 5 and 5 and/or R 7 and Rx and/or R 9 and Rio and/or Rn and R 12 and/or R 13 and R 14 and/or R 15 and R 16 form, together with the carbon atoms which bear them, an aryl or heteroaryl, preferably benzo, 6-membered fused ring, said ring possibly also being optionally substituted, preferably an unsubstituted benzo ring;
  • Q- represents an anionic counterion for achieving electrical neutrality, preferably chosen from halides such as chloride or bromide, and phosphate.
  • the cationic dye comprises one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, such that the overall resulting charge of the triarylmethane structure is cationic.
  • the triarylmethane dye(s) of the invention is/are chosen from those of formula (C-VII) or (C-VIF), in which, taken together or separately,
  • R 2 , R 3 and R 4 represent a hydrogen atom or a (Ci-C4)alkyl group such as methyl or ethyl;
  • R5, Rs, R7, R8, R9, Rio, R11, R12, Ri3, Ri4, Ri5 and Ri 6 represent a hydrogen atom, a halogen atom, such as chlorine, or a (Ci-C4)alkyl group such as methyl or ethyl, an amino group, a (di)(Ci-C4)(alkyl)amino group and, preferably, at least one of the groups R 9 , Rio, R 11 or R 12 represents a hydrogen atom, a halogen atom (Cl), or an amino group, or a (Ci-C4)(alkyl)amino or (di)(Ci-C4)(alkyl)amino group, preferably in the para position relative to the phenyl group.
  • a halogen atom such as chlorine
  • a (Ci-C4)alkyl group such as methyl or ethyl
  • an amino group a (di)(Ci-C4)(alkyl)a
  • the direct dye(s) of triarylmethane structure are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also known as HC Blue 15), and mixtures thereof.
  • the composition according to the invention may comprise one or more anionic direct dyes.
  • the anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances.
  • the term "anionic direct dye” means any direct dye including in its structure at least one CO 2 R or SO 3 R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion.
  • the anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.
  • the anionic direct dye(s) may be chosen, alone or as a mixture, from the anionic direct dyes of formulae (A-II), (A-IG), (A-III), (A- III'), (A-IV), (A-IV), (A-V), (A-V), (A- VI), (A- VII), (A- VIII) and (A-IX) below: a) the diaryl anionic azo dyes of formula (A-II) or (A-IG): (A-II)
  • RS, R9, Rio, RV, R'8, R' 9 and R'1 0 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • X, X' and X" which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
  • R" representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;
  • aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 ), M + and iv) alkoxy with M + as defined previously;
  • - cycloalkyl notably cyclohexyl
  • Ar-N N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (0) 2 S(0 )-, M + or phenylamino groups;
  • W represents a sigma bond s, an oxygen or sulfur atom, or a divalent radical i) - NR- with R as defined previously, or ii) methylene -C(R a )(R b )- with R a and R b , which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R a and R b form, together with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or R a and R b together form a cyclohexyl; it being understood that formulae (A-II) and (A-IG) comprise at least one sulfonate radical (0) 2 S(0 )-, M + or one carboxylate radical (O)CO -, M + on one of the rings A, A', B, B' or C; preferentially sodium sulfonate; As examples of dyes of formula (A-I
  • Acid Red 4 Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24,
  • dyes of formula (A-IG) mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38; b) the pyrazolone anionic azo dyes of formulae (A-III) and (A-IIG):
  • Rii, Ri2 and R13 which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0) 2 S(0 )-, M + with M + as defined previously;
  • Ri4 represents a hydrogen atom, an alkyl group or a group -C(0)0 , M + with M + as defined previously;
  • Ri5 represents a hydrogen atom
  • R16 represents an oxo group, in which case R'i 6 is absent, or alternatively R15 with R16 together form a double bond;
  • Ri7 and Rix which may be identical or different, represent a hydrogen atom, or a group chosen from:
  • Ar-0-S(0) 2 - with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups;
  • Ri9 and R20 together form either a double bond, or a benzo group D', which is optionally substituted;
  • R'i 6 , R'i9 and R'20 which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group; * R21 represents a hydrogen atom or an alkyl or alkoxy group;
  • R a and R b which may be identical or different, are as defined previously, preferentially R a represents a hydrogen atom and R b represents an aryl group;
  • Y represents either a hydroxyl group or an oxo group
  • formulae (A-III) and (A-IIG) comprise at least one sulfonate radical (0) 2 S(0 )-, M + or one carboxylate radical -C(0)0 , M + on one of the rings D or E; preferentially sodium sulfonate;
  • dyes of formula (A-III) mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and, as examples of dyes of formula (A-IIG), mention may be made of: Acid Yellow 17; c) the anthraquinone dyes of formulae (A-IV) and (A-IV):
  • R22, R-23, R-24, R-25, Hie and R27 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • Z' represents a hydrogen atom or a group NR 28 R 29 with R 28 and R 29 , which may be identical or different, representing a hydrogen atom or a group chosen from:
  • - aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, «-dodecyl, «-butyl; ii) (0) 2 S(0 ), M + with M + as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group;
  • Z represents a group chosen from hydroxyl and NR' IS R M with R' 28 and R' 29 , which may be identical or different, representing the same atoms or groups as R 28 and R 29 as defined previously; it being understood that formulae (A-IV) and (A-IV) comprise at least one sulfonate radical (0) 2 S(0 )-, M + or one carboxylate radical -C(0)0 , M + ; preferentially sodium sulfonate;
  • dyes of formula (A-IV) mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT violet No. 2; and, as examples of dyes of formula (A-IV), mention may be made of: Acid Black 48; d) the nitro dyes of formulae (A-V) and (A-V): in which formulae (A-V) and (A-V):
  • R30, R31 and R32 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;
  • R 30 , R 31 and R 32 represent a hydrogen atom
  • R c and R d which may be identical or different, represent a hydrogen atom or an alkyl group
  • W is as defined previously; W particularly represents an -NH- group;
  • ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group;
  • n 1 or 2;
  • * p represents an integer inclusively between 1 and 5;
  • * q represents an integer inclusively between 1 and 4;
  • J represents an oxygen or sulfur atom, or a divalent radical -S(0) m- with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;
  • M represents a hydrogen atom or a cationic counterion
  • formulae (A-V) and (A-V) comprise at least one sulfonate radical (0) 2 S(0 )-, M + or one carboxylate radical -C(0)0 , M + ; preferentially sodium sulfonate;
  • dyes of formula (A-V) mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (A-V), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-(2"-hydroxyethyl)amino-2'- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7; e) the triarylmethane dyes of formula (A- VI):
  • R37, R38, R39, R40, R41, R42, R43 and R44 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • X, X' and X which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
  • R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: ⁇ ; with G optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 )-, M + ; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X'-C(X)- and ix)
  • dyes of formula (A- VI) mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50; f) the xanthene-based dyes of formula (A- VII):
  • R49, R50, R51 and R52 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • R 53 , R 54 , R 55 and R 48 represent a hydrogen or halogen atom
  • G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly G represents an oxygen atom;
  • L represents an alkoxide O , M + ; a thioalkoxide S , M + or a group NR f , with R f representing a hydrogen atom or an alkyl group and M + as defined previously; M + is particularly sodium or potassium;
  • L' represents an oxygen or sulfur atom or an ammonium group: N + R f R g , with R f and R g , which may be identical or different, representing a hydrogen atom, an alkyl or optionally substituted aryl group; L' represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (0) m S(0 )-, M + groups with m and M + as defined previously;
  • Q and Q' which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q' represent an oxygen atom; * M + is as defined previously.
  • dyes of formula (A- VII) mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9; g) the indole-based dyes of formula (A- VIII):
  • R53, R54, R55, R56, R57, R58, R59 and R50 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly G represents an oxygen atom;
  • Ri and R h which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (A- VIII) comprises at least one sulfonate radical (0) 2 S(0 )-, M + or one carboxylate radical -C(0)0 , M + ; preferentially sodium sulfonate;
  • dyes of formula (A- VIII) mention may be made of: Acid Blue 74. h) the quinoline-based dyes of formula (A-IX):
  • R 6I represents a hydrogen or halogen atom or an alkyl group
  • R 62 , Res and R 54 which may be identical or different, represent a hydrogen atom or a group (0) 2 S(0 )-, M + with M + representing a hydrogen atom or a cationic counterion;
  • R51 with R52, or Rr > 1 with Rr > 4 together form a benzo group optionally substituted with one or more groups (0) 2 S(0 )-, M + with M + representing a hydrogen atom or a cationic counterion; it being understood that formula (A-IX) comprises at least one sulfonate radical (0) 2 S(0 )-, M + , preferentially sodium sulfonate.
  • dyes of formula (A-IX) mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
  • a dyeing composition comprises one or more anionic direct dyes chosen, alone or as a mixture, from the following anionic direct dyes:
  • the anionic dyes that are most particularly preferred are the dyes designated in the Colour Index under the code C.I. 58005 (monosodium salt of 1,2-dihydroxy- 9, 10-anthraquinone-3 -sulfonic acid), C.I. 60730 (monosodium salt of 2-[(9,10- dihydro-4-hydroxy-9,10-dioxo-l-anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-l-naphthalenyl)azo]benzenesulfonic acid), C.I.
  • the natural direct dyes that may be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts may also be used.
  • the dyeing composition comprises at least one direct dye chosen from cationic direct dyes, non-ionic direct dyes, such as neutral nitrobenzene direct dyes, neutral anthraquinone dyes, and mixtures thereof
  • the total content of direct dye(s) present in the dyeing composition according to the invention ranges from 0.01% to 10% by weight relative to the total weight of the dyeing composition.
  • the total content of direct dye(s) present in said dyeing composition ranges from 0.05% to 10% by weight, more preferentially ranges from 0.075% to 8% by weight, even more preferentially ranges from 0.1% to 6% relative to the total weight of the dyeing composition.
  • the composition comprises one or more scleroglucan gums.
  • Scleroglucan gums are polysaccharides of microbial origin produced by a fungus of Sclerotium type, in particular Sclerotium rolfsii. They are polysaccharides constituted solely of glucose units.
  • Scleroglucan gums may or may not be modified.
  • the scleroglucan gums used in the present invention are unmodified.
  • scleroglucan gums that may be used in the present invention are, in a nonlimiting manner, the products sold under the name Actigum CS, in particular Actigum CS 11 by the company Sanofi Bio Industries, and under the name Amigum or Amigel by the company Alban Muller International.
  • scleroglucan gums such as the gum treated with glyoxal described in French patent application No. 2633 940, may also be used.
  • the scleroglucan gum(s) are present in the composition preferably in a total content ranging from 0.1% to 10% by weight, preferentially from 0.2% to 5% by weight, more preferentially from 0.3% to 3% by weight and even more preferentially from 0.4% to 2% by weight, relative to the total weight of the composition.
  • composition according to the invention comprises one or more non-ionic associative polymers.
  • polymer is intended to mean any compound derived from the polymerization by polycondensation or from the radical polymerization of monomers, at least one of which is other than an alkylene oxide, and of a monofunctional compound of formula RX, R denoting an optionally hydroxylated C10-C30 alkyl or alkenyl group, and X denoting a carboxylic acid, amine, amide, hydroxyl or ester group. All the compounds resulting solely from the simple condensation of an alkylene oxide with a fatty alcohol, a fatty ester, a fatty acid, a fatty amide or a fatty amine are in particular excluded.
  • the associative polymers according to the invention are polymers comprising at least one fatty chain comprising from 8 to 30 carbon atoms and of which the molecules are capable, in the formulation medium, of associating with each other or with molecules of other compounds.
  • the fatty chain comprises from 10 to 30 carbon atoms.
  • amphiphilic polymers i.e. polymers comprising one or more hydrophilic parts or groups which make them water- soluble and one or more hydrophobic zones or groups (comprising at least one fatty chain) via which the polymers interact and assemble with each other or with other molecules.
  • hydrophobic group is intended to mean a group or a polymer bearing a saturated or unsaturated and linear or branched hydrocarbon-based chain.
  • the hydrophobic group comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and preferentially from 18 to 30 carbon atoms.
  • the hydrocarbon-based hydrophobic group originates from a monofunctional compound.
  • the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol, or else from a polyalkylenated fatty alcohol, such as steareth-100. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
  • fatty chain is understood to mean a linear or branched alkyl or alkenyl chain comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
  • fatty compound for instance a fatty alcohol, a fatty acid or a fatty amide
  • fatty compound is intended to mean a compound comprising, in its main chain, at least one saturated or unsaturated hydrocarbon-based chain, such as alkyl or alkenyl, comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
  • the non-ionic associative polymers are preferably chosen from: -(1) celluloses modified with groups comprising at least one fatty chain; preferably from:
  • hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably Cx to C22, preferably such as the cetylhydroxyethylcellulose sold notably under the reference Natrosol Plus Grade 330 CS (Ci 6 alkyls) sold by the company Ashland, or the product Polysurf 67CS sold by the company Ashland,
  • polyalkylene glycol ether alkyl phenol groups such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) ether of nonyl phenol) sold by the company Amerchol,
  • hydroxypropyl guars modified with groups comprising at least one fatty chain such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia;
  • copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer
  • polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;
  • polymers with an aminoplast ether backbone bearing at least one fatty chain such as the Pure Thix compounds sold by the company Sud-Chemie;
  • the non-ionic associative polymer(s) are chosen from celluloses modified with groups comprising at least one fatty chain.
  • the non-ionic associative polymer(s) are chosen from hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, and hydroxyethylcelluloses modified with polyalkylene glycol alkyl phenyl ether groups, and mixtures thereof.
  • the non-ionic associative polymer is cetylhydroxyethylcellulose.
  • the non-ionic associative polymer(s), which are preferably cellulose-based, are present in the composition in a total content ranging from 0.01% to 10% by weight, and more preferentially from 0.05% to 5% by weight, better still from 0.1% to 2% by weight, relative to the total weight of the composition.
  • composition according to the present invention may also comprise one or more surfactants.
  • the surfactant(s) may be chosen from anionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants and non-ionic surfactants, and mixtures thereof.
  • composition according to the invention may comprise at least one anionic surfactant.
  • anionic surfactant means a surfactant comprising, 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 , P0 3 2 , H2PO2, HP0 2 ⁇ , P0 2 2 P0H and PO .
  • the composition according to the invention may comprise one or more anionic surfactants.
  • the anionic surfactant(s) can be chosen from alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, a-olefm sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfo succinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkyl sulfo succinamates, acyl isethionates and N-(Ci-C 4 )alkyl N-acyl tau
  • These compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
  • the salts of C 6 -C 24 alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C 6 -C 24 alkyl polyglycoside-citrates, C 6 -C 24 alkyl polyglycoside- tartrates and C 6 -C 24 alkyl polyglycoside-sulfosuccinates.
  • anionic surfactant(s) 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.
  • 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.
  • amino alcohol salts examples include the salts of mono-, di- and triethanolamine, the salts of mono-, di- or triisopropanolamine, and the salts of 2-amino-2-methyl-l -propanol, of2-amino-2- m ethyl- 1,3 -propanediol and of tris(hydroxymethyl)aminomethane.
  • Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
  • the anionic surfactants optionally present may be mild anionic surfactants, i.e. anionic surfactants without a sulfate function.
  • 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 comprising from 2 to 50 ethylene oxide groups; alkyl-D-galactoside uronic acids; acyl sarcosinates, acyl glutamates; and alkyl polyglycoside carboxylic esters.
  • Use may be made most particularly of polyoxyalkylenated alkyl ether carboxylic acids, for instance lauryl ether carboxylic acid (4.5 EO), sold, for example, under the name Akypo RLM 45 CA from Kao.
  • lauryl ether carboxylic acid 4.5 EO
  • Akypo RLM 45 CA from Kao.
  • composition according to the invention may also optionally comprise one or more amphoteric or zwitterionic surfactants.
  • They may in particular be optionally quaternized secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.
  • Ra represents a C 10 -C 30 alkyl or alkenyl group derived from an acid Ra- COOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group,
  • R b represents a b-hydroxyethyl group
  • Rc represents a carboxymethyl group
  • B represents -CH2CH2OX'
  • X' represents the group -OB-COOH, OB-COOZ', -CH 2 CH 2 -COOH or - CH 2 CH 2 -C00Z', or a hydrogen atom
  • Y' represents -COOH, -COOZ', or the group CH 2 -CH0H-S03H or -CH 2 - CHOH-SO3Z',
  • Z' represents an ion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine,
  • R' a represents a C10-C30 alkyl or alkenyl group of an acid R' a -COOH preferably present in hydrolysed linseed oil or coconut oil, an alkyl group, in particular a C17 alkyl group and its iso form, or an unsaturated C17 group.
  • cocoamphodiacetate sold by Rhodia under the trade name Miranol® C2M Concentrate.
  • Y represents the group -COOH, -COOZ" or -CH 2 -CH(0H)S03H or the group -CH 2 CH(0H)S0 3 -Z";
  • R d and R e independently of each other, represent a C 1 -C 4 alkyl or hydroxyalkyl radical
  • Z" represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
  • R a " represents a C10-C30 alkyl or alkenyl group of an acid Rf'-COOH preferably present in hydrolysed linseed oil or coconut oil; n and ri denote, independently of each other, an integer ranging from 1 to 3.
  • amphoteric or zwitterionic surfactants it is preferred to use (C 8 -C 20 alkyl) betaines such as cocobetaine, (C 8 -C 20 alkyl) ami do(Ci- Ce alkyl) betaines such as cocamidopropyl betaine, and mixtures thereof. More preferentially, the amphoteric or zwitterionic surfactants(s) are chosen from cocamidopropyl betaine and cocobetaine.
  • composition according to the invention may also comprise at least one or more cationic surfactants.
  • the surfactant(s) are chosen from optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
  • quaternary ammonium salts examples include:
  • X in which the groups Rs to Rn, which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups Rs to Rn comprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms.
  • the aliphatic groups may include heteroatoms notably such as oxygen, nitrogen, sulfur and halogens.
  • the aliphatic groups are chosen, for example, from C 1 -C 30 alkyl, C 1 -C 30 alkoxy, polyoxy(C2-C 6 )alkylene, C1-C 30 alkylamide, (Ci2-C22)alkylamido(C2- C 6 )alkyl, (Ci 2 -C 22 )alkyl acetate, C 1 -C 30 hydroxyalkyl groups,
  • X is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C 4 )alkyl sulfates, and (Ci-C 4 )alkyl- or (Ci-C 4 )alkylarylsulfonates.
  • quaternary ammonium salts of formula (X) preference is given, firstly, to tetraalkyl ammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group includes from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride or benzyldimethylstearylammonium chloride, or, secondly, to distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or also, finally, to palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium
  • Ri2 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example derived from tallow fatty acids,
  • Ri 3 represents a hydrogen atom, a C1-C4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms
  • Ri 4 represents a C1-C4 alkyl group
  • Ri5 represents a hydrogen atom or a C1-C4 alkyl group
  • X is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C4)alkyl sulfates and (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonates.
  • R12 and R13 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, Ri4 denotes a methyl group and R15 denotes a hydrogen atom.
  • Ri4 denotes a methyl group
  • R15 denotes a hydrogen atom.
  • Ri 6 denotes an alkyl group including approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms,
  • Ri7 is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH 2 )3-N + (Ri6a)(Ri7a)(Ri8a),
  • Ri6a, Rna, Ri8a, Ri8, Ri9, R20 and R21 which may be identical or different, are chosen from hydrogen or an alkyl group comprising from 1 to 4 carbon atoms, and
  • X is an anion chosen from the group of halides, acetates, phosphates, nitrates, (Ci-C 4 )alkyl sulfates, (Ci-C 4 )alkylsulfonates or (Ci-C 4 )alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.
  • Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quatemium 89), and Finquat CT, sold by the company Finetex (Quaternium 75);
  • R 22 is chosen from C 1 -C 6 alkyl groups and C 1 -C 6 hydroxyalkyl or dihydroxyalkyl groups,
  • - R- 23 is chosen from:
  • - R 25 is chosen from:
  • R.24, R-26 and R28 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups,
  • - r, s and t which may be identical or different, are integers ranging from 2 to 6,
  • - y is an integer ranging from 1 to 10,
  • - x and z which may be identical or different, are integers ranging from 0 to
  • - X is a simple or complex organic or inorganic anion, with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R23 denotes R27, and that when z is 0 then R25 denotes R29.
  • the alkyl groups R22 may be linear or branched, and more particularly linear.
  • R 22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
  • the sum x + y + z is from 1 to 10.
  • R23 is a hydrocarbon-based group R27, it may be long and contain from 12 to 22 carbon atoms, or short and contain from 1 to 3 carbon atoms.
  • R25 is a hydrocarbon-based group R29, it preferably contains 1 to 3 carbon atoms.
  • R24, R26 and R28 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn- C21 alkyl and alkenyl groups.
  • x and z which may be identical or different, are equal to 0 or 1.
  • y is equal to 1.
  • r, s and t which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
  • the anion X is preferably a halide, preferably chloride, bromide or iodide, a (Ci-C4)alkyl sulfate or a (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonate.
  • a halide preferably chloride, bromide or iodide
  • a (Ci-C4)alkyl sulfate or a (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonate preferably a halide, preferably chloride, bromide or iodide, a (Ci-C4)alkyl sulfate or a (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonate.
  • methanesulfonate phosphate, nitrate, tosylate
  • an anion derived from an organic acid such as acetate or lactate
  • the anion X is even more particularly chloride, methyl sulfate or ethyl sulfate. Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (XIII) in which:
  • R22 denotes a methyl or ethyl group
  • - R-23 is chosen from:
  • - R 25 is chosen from:
  • R 24 , R 26 and R 28 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C 13 -C 17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C 13 -C 17 alkyl and alkenyl groups.
  • the hydrocarbon-based groups are linear.
  • acyl groups preferably contain 14 to 18 carbon atoms and are derived more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
  • alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
  • alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
  • Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company CECA or Rewoquat® WE 18 by the company Rewo-Witco.
  • composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
  • ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
  • Use may also be made of the behenoylhydroxypropyltrimethylammonium chloride sold, for example, by the company Kao under the name Quartamin BTC 131.
  • the ammonium salts containing at least one ester function contain two ester functions.
  • the cationic surfactant(s) are chosen from cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethyl methylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.
  • composition according to the invention may also optionally comprise one or more non-ionic surfactant(s).
  • non-ionic surfactants that may be used according to the invention may be chosen from:
  • - alcohols, a-diols and (Ci-C2o)alkylphenols these compounds being polyethoxylated and/or polypropoxylated and/or polyglycerolated, the number of ethylene oxide and/or propylene oxide groups possibly ranging from 1 to 100, and the number of glycerol groups possibly ranging from 2 to 30; or else these compounds comprising at least one fatty chain including from 8 to 40 carbon atoms and notably from 16 to 30 carbon atoms; in particular, oxyethylenated alcohols comprising at least one saturated or unsaturated, linear or branched Cx to C40 alkyl chain, comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and including one or two fatty chains; - condensates of ethylene oxide and propylene oxide with fatty alcohols;
  • polyethoxylated fatty amides preferably containing from 2 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;
  • polyoxyalkylenated preferably polyoxyethylenated, fatty acid esters containing from 2 to 150 mol of ethylene oxide, including oxyethylenated plant oils;
  • amine oxides such as (C10-C14 alkyl)amine oxides orN-(Cio-Ci4 acyl)aminopropylmorpholine oxides;
  • non-ionic surfactants of alkyl(poly)glycoside type represented notably by the following general formula:
  • - Ri represents a linear or branched alkyl or alkenyl radical including 6 to 24 carbon atoms and notably 8 to 18 carbon atoms, or an alkylphenyl radical of which the linear or branched alkyl radical includes 6 to 24 carbon atoms and notably 8 to 18 carbon atoms,
  • R2 represents an alkylene radical including 2 to 4 carbon atoms
  • - G represents a sugar unit including 5 to 6 carbon atoms
  • - 1 denotes a value ranging from 0 to 10 and preferably from 0 to 4,
  • - v denotes a value ranging from 1 to 15 and preferably from 1 to 4.
  • alkyl(poly)glycoside surfactants are compounds of the formula described above in which:
  • - Ri denotes a linear or branched, saturated or unsaturated alkyl radical including from 8 to 18 carbon atoms
  • R2 represents an alkylene radical including 2 to 4 carbon atoms
  • - 1 denotes a value ranging from 0 to 3 and preferably equal to 0,
  • - G denotes glucose, fructose or galactose, preferably glucose
  • the glucoside bonds between the sugar units are generally of 1-6 or 1-4 type and preferably of 1-4 type.
  • the alkyl(poly)gly coside surfactant is an alkyl(poly)glucoside surfactant.
  • C 8 /Ci 6 -Alkyl(poly)glucosides 1,4, and notably decyl glucosides and caprylyl/capryl glucosides, are most particularly preferred, preferably caprylyl/capryl glucosides.
  • (Cs/Cio) alkyl polyglucoside (2) in aqueous solution at 60%, such as those sold under the name Oramix CG 110 by the company SEPPIC.
  • non-ionic surfactants are chosen from:
  • - saturated or unsaturated, linear or branched, oxyethylenated fatty alcohols including at least one Cs to C40, notably C8-C20 and better still C10-C18 alkyl chain, and comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol, or even from 3 to 20 mol of ethylene oxide; and
  • the non-ionic surfactant(s) are chosen from alkyl(poly)glycosides.
  • the non-ionic surfactant(s) are chosen from (C6-C24 alkyl)(poly)glycosides, more preferentially from (Cs-Cis alkyl)(poly)glycosides, preferably from C 8 /Ci 6 -alkyl(poly)glucosides, preferably from decyl glucosides and/or caprylyl/capryl glucosides and/or cocoyl glucosides.
  • the non-ionic surfactant(s) are preferably chosen from (C6-C24 alkyl)polygly cosides.
  • the surfactant(s) are chosen from amphoteric or zwitterionic surfactants, cationic surfactants, non-ionic surfactants, and mixtures thereof.
  • the composition comprises at least one cationic surfactant and at least one non-ionic surfactant, preferably chosen from (C6-C24 alkyl)polygly cosides.
  • the composition comprises at least one cationic surfactant and at least one amphoteric or zwitterionic surfactant.
  • the composition comprises at least one amphoteric or zwitterionic surfactant and a non-ionic surfactant, preferably chosen from (C6-C24 alkyl)polygly cosides.
  • the composition preferably comprises one or more surfactants in a total content ranging from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight and better still from 0.1% to 5% by weight, or even from 0.5% to 5% by weight, relative to the total weight of the composition.
  • the composition comprises one or more cationic surfactants in a total content preferably ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight, better still from 0.1% to 3% by weight, relative to the total weight of the composition.
  • the composition comprises one or more amphoteric or zwitterionic surfactants in a total content preferably ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight, better still from 0.1% to 3% by weight, relative to the total weight of the composition.
  • the composition comprises one or more non-ionic surfactants in a total content ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight, better still from 0.1% to 3% by weight, relative to the total weight of the composition.
  • composition according to the present invention may also comprise one or more fatty substances.
  • fatty substance is intended to mean an organic compound that is insoluble in water at ordinary ambient temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1% and even more preferentially less than 0.1%). They bear in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups.
  • the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane.
  • fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids since salified fatty acids constitute soaps which are generally soluble in aqueous media.
  • the fatty substances are in particular chosen from C 6 -Ci 6 hydrocarbons or hydrocarbons comprising more than 16 carbon atoms and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, non-silicone waxes, and silicones.
  • the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 30 carbon atoms, which are optionally substituted, in particular with one or more (in particular 1 to 4) hydroxyl groups. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • C6-C16 alkanes they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
  • the linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam ⁇ .
  • the fatty substance(s) may be chosen from fatty alcohols and/or fatty esters.
  • the fatty alcohols that may be used in the compositions of the invention are saturated or unsaturated, and linear or branched, and comprise from 6 to 30 carbon atoms and more particularly from 8 to 30 carbon atoms. Examples that may be mentioned include cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol and linoleyl alcohol.
  • the wax(es) that may be used in the compositions of the invention are chosen especially from carnauba wax, candelilla wax, esparto grass wax, paraffin wax, ozokerite, plant waxes, for instance olive tree wax, rice wax, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant blossom sold by the company Bertin (France), animal waxes, for instance beeswaxes, or modified beeswaxes (cerabellina); other waxes or waxy starting materials that may be used according to the invention are especially marine waxes such as the product sold by the company Sophim under the reference M82, and polyethylene waxes or polyolefin waxes in general.
  • esters of fatty acids and/or of fatty alcohols advantageously different from the triglycerides mentioned above, mention may be made especially of esters of saturated or unsaturated, linear or branched C1-C26 aliphatic mono- or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic mono- or polyalcohols, the total carbon number of the esters more particularly being greater than or equal to 10.
  • dihydroabietyl behenate octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate;
  • 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.
  • esters mentioned above it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.
  • alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stea
  • composition may also comprise, as fatty ester, sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids.
  • sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids.
  • sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids.
  • sucrose glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance methylglucose.
  • the sugar esters of fatty acids may be notably chosen from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.
  • esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, notably, oleopalmitate, oleostearate and palmitostearate mixed esters.
  • monoesters and diesters and especially sucrose, glucose or methylglucose monooleate or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate or oleostearate.
  • esters or mixtures of esters of sugar and of fatty acid examples include:
  • Ryoto Sugar Esters for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% diester-triester-polyester;
  • sucrose mono-dipalmito-stearate sold by the company Goldschmidt under the name Tegosoft® PSE.
  • the fatty substance(s) are solid.
  • solid fatty substance is intended to mean a fatty substance that is solid at 25°C and at ambient temperature.
  • the fatty substance is chosen from C12-C20, preferably C16-C18, fatty alcohols, such as cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, oleyl alcohol or linoleyl alcohol, preferably cetyl alcohol, stearyl alcohol or cetylstearyl alcohol, preferably cetylstearyl alcohol.
  • fatty alcohols such as cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, oleyl alcohol or linoleyl alcohol, preferably cetyl alcohol, stearyl alcohol or cetylstearyl alcohol.
  • the composition according to the invention may comprise a total amount of fatty substances ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferentially from 1% to 8% by weight, relative to the total weight of the composition.
  • composition according to the invention may comprise a total amount of solid fatty substances ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferentially from 1% to 8% by weight, relative to the total weight of the composition.
  • the cosmetically acceptable medium that is suitable for dyeing keratin fibres also known as a dye support, generally comprises water or a mixture of water and of at least one organic solvent to dissolve the compounds that are not sufficiently water-soluble.
  • the organic solvents are chosen from linear or branched and preferably saturated monoalcohols or diols, comprising from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4- pentanediol), neopentyl glycol and 3-methyl-l,5-pentanediol; glycerol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycols or glycol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether, butylene glycol or dipropylene glycol; and also diethylene glycol alkyl ethers, notably of Ci- C4, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
  • the common solvents described above if they are present, usually represent from 1% to 40% by weight and more preferentially from 5% to 30% by weight relative to the total weight of the composition.
  • composition according to the invention generally comprises water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.
  • composition according to the invention preferably comprises water.
  • the water content ranges from 20% to 97% by weight, more preferentially from 40% to 95% by weight and better still from 60% to 90% by weight relative to the total weight of the composition. pH of the medium
  • the pH of the composition according to the invention generally ranges from
  • the pH of the composition according to the invention ranges from 3 to 11 and particularly ranges from 5 to 8, better still from 6 to 7.5.
  • pH adjuster
  • the cosmetically acceptable medium may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.
  • 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.
  • 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.
  • basifying agents examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (XIII) below: ⁇
  • W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; and 3 ⁇ 4, R7, Rx and R9, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxy alkyl radical.
  • composition according to the invention may also contain various additives conventionally used in hair dyeing compositions, such as mineral thickeners, and in particular fillers such as clays or talc; organic thickeners other than scleroglucan gums and non-ionic associative polymers; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents and/or opacifiers.
  • mineral thickeners such as clays or talc
  • organic thickeners other than scleroglucan gums and non-ionic associative polymers
  • antioxidants such as clays or talc
  • penetrants such as sodium metabisulfite
  • sequestrants such as sodium metabisulfite
  • fragrances such as sodium metabisulfite
  • dispersants such as sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisul
  • the above additives are generally present in an amount for each of them of between 0.01% and 40% by weight relative to the weight of the composition, and preferably between 0.1% and 20% by weight relative to the weight of the composition.
  • Another subject of the invention is a process for dyeing keratin fibres, comprising the application of a dyeing composition as described above to the keratin fibres.
  • the keratin fibres are human keratin fibres, preferably human hair.
  • composition is left in place for a time generally of about from 1 minute to 1 hour, preferably from 5 minutes to 30 minutes.
  • the temperature during the process is conventionally between ambient temperature (between 15 and 25°C) and 80°C and preferably between ambient temperature and 60°C.
  • the keratin fibres are optionally rinsed with water, optionally subjected to washing followed by rinsing with water, and are then dried or left to dry.
  • compositions according to the invention were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material:
  • compositions Al, A2 and A3 are homogeneous and in gel form. They have a viscosity of between 650 and 1550 cps (Al: 27 UD M3, A2: 24 UD M3, A3: 26 UD M3, measured on a Rheomat 25°C reading at 30s, rotational speed of 200 rpm).
  • compositions were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material:
  • compositions A and B were applied to locks of permanent-waved hair containing 90% grey hair.
  • the "mixture/lock" bath ratio is, respectively, 3/1 (g/g).
  • the leave-on time is 10 minutes, on a hotplate set at 27°C. On conclusion of the leave-on time, the locks are rinsed and then dried under a drying hood at 40°C.
  • the colour of the locks was evaluated in the CIE L* a* b* system, using a Datacolor Spectraflash SF600X spectrocolorimeter.
  • the three parameters respectively denote the intensity of the colour (L*), the green/red colour axis (a*) and the blue/yellow colour axis (b*).
  • L* the intensity of the colour
  • a* green/red colour axis
  • b* blue/yellow colour axis
  • compositions were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material: [TABLE 5]
  • compositions A, B and C were applied to locks of natural hair containing 90% grey hair at a rate of 3 g of composition per gram of lock.
  • the leave-on time is 30 minutes on a hotplate set at 27°C, then the locks are rinsed with water and dried under a drying hood at 40°C.
  • the colour of the locks was evaluated using a Konica Minolta CM-3600A colorimeter in the CIE L* a* b* system (illuminant D65, angle 10°, specular component included).
  • composition A according to the invention using both a non-ionic associative polymer and scleroglucan gum than with the comparative compositions B or C using only the non-ionic associative polymer or only the scleroglucan gum.
  • compositions were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material:
  • compositions D and E were applied to locks of natural hair containing 90% grey hair at a rate of 3g of composition per gram of lock.
  • the leave-on time is 30 minutes on a hotplate set at 27°C, then the locks are rinsed with water and dried under a drying hood at 40°C.
  • the colour of the locks was evaluated using a Konica Minolta CM-3600A colorimeter in the CIE L* a* b* system (illuminant D65, angle 10°, specular component included).
  • composition D A more intense colouring of the keratin fibres is obtained with the composition D according to the invention using both a non-ionic associative polymer and scleroglucan gum than with the comparative compositions E using only the scleroglucan gum.

Abstract

The present invention relates to a composition for direct dyeing of keratin fibres, in particular human keratin fibres such as the hair, comprising one or more direct dye(s) in a total weight content ranging from 0.01% to 10% relative to the total weight of the composition, one or more scleroglucan gums and one or more non-ionic associative polymers. The invention also relates to a process for dyeing keratin fibres, comprising the application of said composition to said fibres.

Description

HAIR DYEING COMPOSITION COMPRISING A DIRECT DYE, A SCLEROGLUCAN GUM AND A NON-IONIC ASSOCIATIVE POLYMER
The present invention relates to the field of dyeing keratin fibres and more particularly to the field of hair dyeing.
The invention relates in particular to a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising one or more direct dye(s), in a total weight content ranging from 0.01% to 10% relative to the total weight of the composition, one or more scleroglucan gums and one or more non ionic associative polymers.
The invention also relates to a dyeing process comprising the application of said composition to keratin fibres, in particular human keratin fibres such as the hair.
It is known practice to dye keratin fibres and in particular human hair with dye compositions containing direct dyes, in particular nitrobenzene dyes, acid azo dyes, cationic azo dyes, anthraquinone dyes, natural dyes.
These colourings can be carried out by direct application to keratin fibres of the composition containing the direct dye(s) or by application of an extemporaneously prepared mixture of a composition containing the direct dye(s) with a composition containing an oxidizing bleaching agent which is preferably aqueous hydrogen peroxide solution. In the latter case, the term lightening direct dyeing is then used.
It is already known practice to prepare compositions for direct dyeing of keratin fibres by combining surfactants and/or thickeners with the direct dyes in order to improve the physical properties and/or the colourings obtained.
Compositions comprising a direct dye and a xanthan gum for obtaining better thickening of direct dyeing compositions are in particular known from document FR 2 548 893, it being possible for these compositions to optionally contain surfactants.
However, these compositions do not give totally satisfactory cosmetic and/or dyeing properties, in particular with regard to the intensity of the colourings and their selectivities representative of colour differences between various parts of one or more strands of hair according to the degrees of sensitization.
In order to improve the dyeing and cosmetic properties of such compositions, it has already been proposed to use compositions comprising a direct dye, a bioheteropolysaccharide, a cationic surfactant and an amphoteric surfactant, as described in document FR 2910282.
There is a need to further improve dyeing compositions comprising direct dyes, in particular in terms of dyeing properties, cosmetic properties and use quality.
Thus, one of the objects of the present invention is to propose compositions for dyeing keratin fibres, preferably human keratin fibres such as the hair, which do not have the drawbacks mentioned above. In particular, one of the objects of the present invention is to propose dyeing compositions which are capable of giving very good dyeing performance qualities, notably in terms of intensity and/or colour build up, and also in terms of selectivity, chromaticity and/or resistance to external agents, having good working qualities in particular when applied to keratin fibres, and giving the fibres good cosmetic properties (softness, smoothness) while at the same time being stable (notably not undergoing phase separation and having a viscosity and/or pH which change(s) little or not at all over time).
These aims and others are achieved by the present invention, one subject of which is thus a composition for dyeing keratin fibres, preferably human keratin fibres such as the hair, comprising: one or more direct dye(s); one or more scleroglucan gum(s); one or more non-ionic associative polymer(s), the direct dye(s) being present in a content ranging from 0.01% to 10% by weight relative to the total weight of the composition.
The invention also relates to a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, comprising the application to said fibres of a dye composition as defined previously.
The compositions according to the invention can thus give very good dyeing performance on keratin fibres, notably in terms of build-up, intensity, chromaticity and/or selectivity. They also afford compositions which have good rheological properties so as not to run down onto the face, the scalp or beyond the areas that it is proposed to dye, when they are applied.
The compositions according to the invention are stable. For the purposes of the present invention, the term "stable" in particular means that physical properties such as the appearance, the pH and/or the viscosity vary little or not at all over time, and in particular that the viscosity of the composition does not change or changes little during storage and/or that the composition does not undergo phase separation during storage. In particular, it is desirable for the dyeing compositions to be stable over time, in particular stable after 1 month at 45°C, or even after 2 months at 45°C.
Furthermore, the compositions according to the invention have the advantage of being stable (not undergoing phase separation) independently of the pH. Finally, the compositions are preferably stable (do not undergo phase separation) even in the presence of a high content of certain compounds, for instance direct dyes.
Moreover, the compositions of the invention advantageously have good application qualities, such as ease of spreading and extending of the composition.
Other features and advantages of the invention will emerge 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 ...".
The expression "at least one " is equivalent to the expression " one or more" .
For the purposes of the present invention, the term "composition for dyeing" or "dye composition" or “dyeing composition” means a composition intended to be applied to keratin fibres, preferably human keratin fibres and in particular the hair, in order to dye said fibres or said hair.
Advantageously, the dyeing composition according to the invention has a thickened texture, and is in cream or gel form, preferably in gel form.
Thus, the composition according to the invention generally has, at ambient temperature, a viscosity of greater than 50 cps, preferably between 200 and 100 000 cps, more preferentially between 300 and 50 000 cps, even more preferentially between 400 and 10 000 cps, and better still from 500 to 8000 cps, or even 600 to 2000, cps measured at 25°C at a spin speed of 200 rpm using a rheometer such as a Rheomat RM 180 equipped with a No. 3 or 4 spindle, the measurement being taken after 30 seconds of rotation of the spindle (after which time stabilization of the viscosity and of the spin speed of the spindle is observed).
The direct dyes
The dyeing composition according to the present invention comprises at least one direct dye.
The direct dye(s) that may be used according to the invention are chosen from natural direct dyes, synthetic direct dyes, and mixtures thereof.
Preferably, the direct dye(s) that may be used according to the invention are chosen from ionic direct dyes and non-ionic direct dyes, more particularly from cationic direct dyes, amphoteric direct dyes, anionic direct dyes, non-ionic direct dyes, and mixtures thereof.
The direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral (non-ionic), acidic (anionic) or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.
The cationic direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group.
According to a particular embodiment of the invention, the cationic direct dyes comprise at least one quaternized cationic chromophore.
As cationic direct dyes according to the invention, mention may be made of the following dyes: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bisisoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines such as dimethines of stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.
For the cationic azo dyes, mention may be made particularly of those resulting from the cationic dyes described in Kirk-Othmer’ s Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & Sons, updated on 19 April 2010.
Among the azo dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954. According to a preferred embodiment of the invention, the direct dye(s) are chosen from cationic dyes known as "basic dyes".
Among the azo dyes described in the Colour Index International 3rd edition, mention may be made in particular of the following compounds:
-Basic Red 22 -Basic Red 76 -Basic Yellow 57 -Basic Brown 16 -Basic Brown 17
Among the cationic quinone dyes, those mentioned in the abovementioned Colour Index International are suitable for use and, among these, mention may be made, inter alia, of the following dyes:
-Basic Blue 22 -Basic Blue 99
Among the azine dyes that are suitable for use, mention may be made of those listed in the Colour Index International, for example the following dyes:
-Basic Blue 17 -Basic Red 2.
Among the cationic triarylmethane dyes that may be used according to the invention, mention may be made, in addition to those listed in the Colour Index, of the following dyes:
-Basic Green 1 -Basic Violet 3 -Basic Violet 14 -Basic Blue 7 -Basic Blue 26.
Mention may also be made of the cationic dyes described in US 5 888252, EP 1 133 975, WO 03/029359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954. Mention may also be made of those listed in the encyclopaedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the "Kirk-Othmer Encyclopedia of Chemical Technology", in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons.
Preferably, the cationic direct dyes are chosen from those resulting from dyes of azo and hydrazono type. According to a particular embodiment, the direct dyes are cationic azo dyes, described in EP 850 636, FR 2 788433, EP 920 856, WO 99/48465, FR 2 757385, EP 850637, EP 918 053, WO 97/44004, FR 2 570 946, FR 2285 851, DE 2 538 363, FR 2 189 006, FR 1 560664, FR 1 540423, FR 1 567219, FR 1 516943, FR 1 221 122, DE 4220388, DE 4 137005, WO 01/66646, US 5 708 151, WO 95/01772, WO
515 144, GB 1 195 386, US 3 524 842, US 5 879413, EP 1 062940, EP 1 133 976, GB 738 585, DE 2 527 638, FR 2275 462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chim. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211; Rev. Roum. Chim. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chim. Ind. (Milan) (1974), 56(9), 600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; MRL Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72. Preferably, the cationic direct dye(s) comprise a quaternary ammonium group; more preferentially, the cationic charge is endocyclic.
These cationic radicals are, for example, a cationic radical:
- bearing an exocyclic (di/tri)(Ci-C8)alkylammonium charge, or
- bearing an endocyclic charge, such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bistetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.
Mention may be made of the hydrazono cationic dyes of formulae (C-II) and (C-III), the azo dyes of formulae (C-IV) and (C-V) below, and also the optical and geometric isomers thereof and tautomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates:
Het+-C(Ra)=N-N(Rb)-Ar, Q
(C-II)
Het+-N(Ra)-N=C(Rb)-Ar, Q (C-III)
Het+-N=N-Ar, Q
(C-IV) Ar+-N=N-Ar", Q
(C-V) in which formulae (C-II) to (C-V):
* Het+ represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (Ci-Cx) alkyl group such as methyl;
* Ar+ represents an aryl radical, such as phenyl or naphthyl, having an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-C8)alkylammonium, such as trimethylammonium; * Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cx)alkyl, ii) optionally substituted (Ci-Cx)alkoxy, iii) (di)(Ci- C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted N-(Ci-C8)alkyl-N-aryl(Ci- C8)alkylamino or alternatively Ar represents a julolidine group;
* Ar" represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (Ci- C8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Ci-C8)alkoxy or phenyl groups;
* Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group, which is optionally substituted, preferentially with a hydroxyl group;
* or else the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl group;
* Q represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.
In particular, mention may be made of the azo and hydrazono direct dyes bearing endocyclic cationic charges, of formulae (C-II) to (C-V) as defined previously; more particularly the cationic direct dyes of formulae (C-II) to (C-V) bearing endocyclic cationic charges described in patent applications WO 95/15144, WO 95/01772 and EP-714954.
Preferentially, mention may be made of the following direct dyes:
Figure imgf000009_0001
(C-IV-1) in which formulae (C-II-1) and (C-IV-1):
- R1 represents a (Ci-C4)alkyl group such as methyl;
- R2 and R3, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, such as methyl; and
- R4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cx)alkyl, optionally substituted (Ci-Cx)alkoxy, or (di)(Ci- C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R4 is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferentially CH,
- Q is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.
In particular, the dyes of formulae (C-II-1) and (C-IV-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
Figure imgf000010_0001
Basic Yellow 87 with Q' being an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.
According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say that they contain at least one fluorescent chromophore as defined previously. Fluorescent dyes that may be mentioned include the radicals resulting from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro { 2- [(2H-pyrrol-2-ylidene-kN)methyl] - 1 H-py rrolato-kN}borons (BODIPY®), diketopyrrolopyrroles, fluorindines, (poly)methines (notably cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes and xanthenes.
Mention may also be made of the fluorescent dyes described in EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954 and those listed in the encyclopaedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the "Kirk-Othmer Encyclopedia of Chemical Technology", in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of "Ullmann’s Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons, and in the handbook — "A Guide to Fluorescent Probes and Labeling Technologies", 10th Ed., Molecular Probes/Invitrogen - Oregon 2005, circulated on the Internet or in the preceding printed editions.
According to one variant of the invention, the cationic dye(s) are fluorescent and comprise at least one quaternary ammonium radical such as those of formula (C- VI) below, and also the optical and geometric isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates:
W+-[C(Rc)=C(Rd)]m'-Ar, Q
(C-VI) in which formula (C-VI):
* W+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (Ci-Cx)alkyl groups, optionally substituted notably with one or more hydroxyl groups;
* Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (Ci-Cx)alkyl, preferably of C1-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-Cx)alkoxy groups such as methoxy; v) one or more hydroxy(Ci-Cx)alkyl groups such as hydroxyethyl, vi) one or more amino groups or (di)(Ci-C8)alkylamino, preferably with the C1-C4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;
* m' represents an integer between 1 and 4 inclusive, and in particular m is 1 or 2; more preferentially 1;
* Rc and Rd, which are identical or different, represent a hydrogen atom or an optionally substituted (Ci-Cx)alkyl group, preferentially of C1-C4, or alternatively Rc contiguous with W+ and/or Rd contiguous with Ar form, with the atoms that carry them, a (hetero)cycloalkyl; particularly, Rc is contiguous with W+ and they form a (hetero)cycloalkyl such as cyclohexyl;
* Q is an organic or mineral anionic counterion as defined above.
Among the cationic direct dyes, mention may also be made of triarylmethane cationic dyes.
Preferably, the triarylmethane direct dye(s) according to the invention are chosen from the cationic dyes of formulae (C-VII) and (C-UIG) below:
Figure imgf000012_0001
(C-UIG) and also the organic or mineral acid or base addition salts thereof, the geometrical isomers, optical isomers and tautomers thereof, and the mesomeric forms thereof, and the solvates thereof such as hydrates: in which preceding formulae (C-VII) and (C-VIf):
* Ri, R2, R3 and R4, which may be identical or different, represent a hydrogen atom or a group from among: (Ci-C6)alkyl which is optionally substituted, preferably with a hydroxyl group; aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, heteroaryl, heteroaryl(Ci-C4)alkyl, or else two groups Ri and R2, and/or R3 and R4, borne by the same nitrogen atom, form, together with the nitrogen atom which bears them, an optionally substituted heterocycloalkyl group such as morpholino, piperazino or piperidino; preferably, Ri, R2, R3 and R4, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group;
* R5, Rs, R7, R8, R9, Rio, R11, R12, Ri3, Ri4, Ri5 and Ri6, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) hydroxyl, ii) thiol, iii) amino, iv) (di)(Ci-C4)(alkyl)amino, v) (di)arylamino such as (di)phenylamino, vi) nitro, vii) acylamino (-NR-C(O)R') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R is a C1-C2 alkyl radical; viii) carbamoyl ((R)2N-C(0)-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-O-C(O)R') or (-C(O)OR'), in which the radical R is a hydrogen atom or a Ci- C4 alkyl optionally bearing at least one hydroxyl group and the radical R' is a C1-C2 alkyl radical; x) alkyl optionally substituted especially with a hydroxyl group; xi) alkylsulfonylamino (RSO2-NR-) in which the radical R represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R represents a C1-C4 alkyl radical or a phenyl radical; xii) aminosulfonyl ((R)2N- SO2-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, xiii) (Ci-C4)alkoxy, and xiv) (Ci-C4)alkylthio;
* or else two radicals borne by two contiguous carbon atoms R5 and 5 and/or R7 and Rx and/or R9 and Rio and/or Rn and R12 and/or R13 and R14 and/or R15 and R16 form, together with the carbon atoms which bear them, an aryl or heteroaryl, preferably benzo, 6-membered fused ring, said ring possibly also being optionally substituted, preferably an unsubstituted benzo ring;
* Q- represents an anionic counterion for achieving electrical neutrality, preferably chosen from halides such as chloride or bromide, and phosphate. When the cationic dye comprises one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, such that the overall resulting charge of the triarylmethane structure is cationic.
According to a preferred embodiment, the triarylmethane dye(s) of the invention is/are chosen from those of formula (C-VII) or (C-VIF), in which, taken together or separately,
- Ri, R2, R3 and R4 represent a hydrogen atom or a (Ci-C4)alkyl group such as methyl or ethyl;
- R5, Rs, R7, R8, R9, Rio, R11, R12, Ri3, Ri4, Ri5 and Ri6 represent a hydrogen atom, a halogen atom, such as chlorine, or a (Ci-C4)alkyl group such as methyl or ethyl, an amino group, a (di)(Ci-C4)(alkyl)amino group and, preferably, at least one of the groups R9, Rio, R11 or R12 represents a hydrogen atom, a halogen atom (Cl), or an amino group, or a (Ci-C4)(alkyl)amino or (di)(Ci-C4)(alkyl)amino group, preferably in the para position relative to the phenyl group.
Preferably, the direct dye(s) of triarylmethane structure are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also known as HC Blue 15), and mixtures thereof.
The composition according to the invention may comprise one or more anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as "acid" direct dyes owing to their affinity for alkaline substances. The term "anionic direct dye" means any direct dye including in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.
According to the invention, the anionic direct dye(s) may be chosen, alone or as a mixture, from the anionic direct dyes of formulae (A-II), (A-IG), (A-III), (A- III'), (A-IV), (A-IV), (A-V), (A-V), (A- VI), (A- VII), (A- VIII) and (A-IX) below: a) the diaryl anionic azo dyes of formula (A-II) or (A-IG):
Figure imgf000014_0001
(A-II)
Figure imgf000015_0001
(A-IG) in which formulae (A-II) and (A-II'):
* It?, RS, R9, Rio, RV, R'8, R'9 and R'10, which may be identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
- (0)2S(0 )-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO -, M+ with M+ as defined previously;
- R"-S(0)2-, with R" representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;
- R"'-S(0)2-X'- with R'" representing an alkyl or optionally substituted aryl group, X' as defined previously;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 ), M+ and iv) alkoxy with M+ as defined previously;
- optionally substituted heteroaryl; preferentially a benzothiazolyl group;
- cycloalkyl; notably cyclohexyl;
- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (0)2S(0 )-, M+ or phenylamino groups;
- or alternatively two contiguous groups R7 with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A'; and R'7 with R's or R's with R'9 or R'9 with R'io together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 )-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X"-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X" and Ar as defined previously;
* W represents a sigma bond s, an oxygen or sulfur atom, or a divalent radical i) - NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb form, together with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that formulae (A-II) and (A-IG) comprise at least one sulfonate radical (0)2S(0 )-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A', B, B' or C; preferentially sodium sulfonate; As examples of dyes of formula (A-II), mention may be made of: Acid Red
1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24,
Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food yellow 3 or sunset yellow; and, as examples of dyes of formula (A-IG), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38; b) the pyrazolone anionic azo dyes of formulae (A-III) and (A-IIG):
Figure imgf000016_0001
(A-III)
Figure imgf000017_0001
(A-IIG) in which formulae (A-III) and (A-IIG):
* Rii, Ri2 and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0)2S(0 )-, M+ with M+ as defined previously;
* Ri4 represents a hydrogen atom, an alkyl group or a group -C(0)0 , M+ with M+ as defined previously;
* Ri5 represents a hydrogen atom;
* R16 represents an oxo group, in which case R'i6 is absent, or alternatively R15 with R16 together form a double bond;
* Ri7 and Rix, which may be identical or different, represent a hydrogen atom, or a group chosen from:
- (0)2S(0 )-, M+ with M+ as defined previously;
- Ar-0-S(0)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups;
* Ri9 and R20 together form either a double bond, or a benzo group D', which is optionally substituted;
* R'i6, R'i9 and R'20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group; * R21 represents a hydrogen atom or an alkyl or alkoxy group;
* Ra and Rb, which may be identical or different, are as defined previously, preferentially Ra represents a hydrogen atom and Rb represents an aryl group;
* Y represents either a hydroxyl group or an oxo group;
* represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that formulae (A-III) and (A-IIG) comprise at least one sulfonate radical (0)2S(0 )-, M+ or one carboxylate radical -C(0)0 , M+ on one of the rings D or E; preferentially sodium sulfonate;
As examples of dyes of formula (A-III), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and, as examples of dyes of formula (A-IIG), mention may be made of: Acid Yellow 17; c) the anthraquinone dyes of formulae (A-IV) and (A-IV):
Figure imgf000018_0001
(A-IV)
Figure imgf000018_0002
(A-IV) in which formulae (A-IV) and (A-IV):
* R22, R-23, R-24, R-25, Hie and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- hydroxyl, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (0)2S(0 )-, M+ with M+ as defined previously;
- aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0 ), M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- (0)2S(0 )-, M+ with M+ as defined previously;
* Z' represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:
- alkyl; - polyhydroxy alkyl such as hydroxy ethyl;
- aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, «-dodecyl, «-butyl; ii) (0)2S(0 ), M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group;
- cycloalkyl; in particular cyclohexyl;
* Z represents a group chosen from hydroxyl and NR'ISRM with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (A-IV) and (A-IV) comprise at least one sulfonate radical (0)2S(0 )-, M+ or one carboxylate radical -C(0)0 , M+; preferentially sodium sulfonate;
As examples of dyes of formula (A-IV), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT violet No. 2; and, as examples of dyes of formula (A-IV), mention may be made of: Acid Black 48; d) the nitro dyes of formulae (A-V) and (A-V):
Figure imgf000019_0001
in which formulae (A-V) and (A-V):
* R30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;
- hydroxyl, mercapto; - nitro, nitroso;
- polyhaloalkyl;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°, X, X' and X" as defined previously; - (0)2S(0 )-, M+ with M+ as defined previously;
- (O)CO -, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R30, R31 and R32 represent a hydrogen atom;
* Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;
* W is as defined previously; W particularly represents an -NH- group;
* ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group;
* n is 1 or 2;
* p represents an integer inclusively between 1 and 5;
* q represents an integer inclusively between 1 and 4;
* u is 0 or 1 ; * when n is 1, J represents a nitro or nitroso group; particularly nitro;
* when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0)m- with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;
* M represents a hydrogen atom or a cationic counterion;
Figure imgf000020_0001
* which may be present or absent, represents a benzo group, optionally substituted with one or more groups R30 as defined previously; it being understood that formulae (A-V) and (A-V) comprise at least one sulfonate radical (0)2S(0 )-, M+ or one carboxylate radical -C(0)0 , M+; preferentially sodium sulfonate;
As examples of dyes of formula (A-V), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (A-V), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-(2"-hydroxyethyl)amino-2'- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7; e) the triarylmethane dyes of formula (A- VI):
Figure imgf000021_0001
(A- VI) in which formula (A- VI): * R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted with a group (0)mS(0 )-, M+ with M+ and m as defined previously;
* R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxyl, mercapto; - nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group; - (0)2S(0 )-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO -, M+ with M+ as defined previously;
- or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: Ί; with G optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 )-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X'-C(X)- and ix)
R°-X'-C(X)-X"-; with M+, R°, X, X' and X" as defined previously; particularly, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxyl group or (0)2S(0 )-, M+; and when R43 with R44 together form a benzo group, it is preferentially substituted with a group (0)2S(0>; it being understood that at least one of the rings G, H, I or G comprises at least one sulfonate radical (0)2S(0 )- or a carboxylate radical -C(0)0 ; preferentially sulfonate.
As examples of dyes of formula (A- VI), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50; f) the xanthene-based dyes of formula (A- VII):
Figure imgf000022_0001
(A- VII) in which formula (A- VII): * R45, R-46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;
* R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl; - alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- (0)2S(0 )-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO -, M+ with M+ as defined previously; particularly, R53, R54, R55 and R48 represent a hydrogen or halogen atom;
* G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly G represents an oxygen atom;
* L represents an alkoxide O , M+; a thioalkoxide S , M+ or a group NRf, with Rf representing a hydrogen atom or an alkyl group and M+ as defined previously; M+ is particularly sodium or potassium;
* L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom, an alkyl or optionally substituted aryl group; L' represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (0)mS(0 )-, M+ groups with m and M+ as defined previously;
* Q and Q', which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q' represent an oxygen atom; * M+ is as defined previously.
As examples of dyes of formula (A- VII), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9; g) the indole-based dyes of formula (A- VIII):
Figure imgf000023_0001
(A- VIII) in which formula (A- VIII):
* R53, R54, R55, R56, R57, R58, R59 and R50, which may be identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X' ’ - with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
- (0)2S(0 )-, M+ with M+ representing a hydrogen atom or a cationic counterion; - (O)CO -, M+ with M+ as defined previously;
* G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly G represents an oxygen atom;
* Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (A- VIII) comprises at least one sulfonate radical (0)2S(0 )-, M+ or one carboxylate radical -C(0)0 , M+; preferentially sodium sulfonate;
As an example of dyes of formula (A- VIII), mention may be made of: Acid Blue 74. h) the quinoline-based dyes of formula (A-IX):
Figure imgf000023_0002
(A-IX) in which formula (A-IX):
* R6I represents a hydrogen or halogen atom or an alkyl group;
* R62, Res and R54, which may be identical or different, represent a hydrogen atom or a group (0)2S(0 )-, M+ with M+ representing a hydrogen atom or a cationic counterion;
* or alternatively R51 with R52, or Rr> 1 with Rr>4, together form a benzo group optionally substituted with one or more groups (0)2S(0 )-, M+ with M+ representing a hydrogen atom or a cationic counterion; it being understood that formula (A-IX) comprises at least one sulfonate radical (0)2S(0 )-, M+, preferentially sodium sulfonate.
As examples of dyes of formula (A-IX), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
More particularly, a dyeing composition comprises one or more anionic direct dyes chosen, alone or as a mixture, from the following anionic direct dyes:
[TABLE 1]
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Most of these dyes are described in particular in the Colour Index published by The Society of Dyers and Colorists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.
The anionic dyes that are most particularly preferred are the dyes designated in the Colour Index under the code C.I. 58005 (monosodium salt of 1,2-dihydroxy- 9, 10-anthraquinone-3 -sulfonic acid), C.I. 60730 (monosodium salt of 2-[(9,10- dihydro-4-hydroxy-9,10-dioxo-l-anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-l-naphthalenyl)azo]benzenesulfonic acid), C.I. 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2- naphthalenesulfonic acid), C.I. 17200 (disodium salt of 5-amino-4-hydroxy-3- (phenylazo)-2,7-naphthalenedisulfonic acid), C.I. 20470 (disodium salt of 1-amino- 2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid), C.I. 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl(3- sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadien-l- ylidene]-3-sulfobenzenemethanaminium hydroxide, inner salt), C.I. 61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-l,4-anthracenediyl)diimino]bis[5-methyl]- benzenesulfonic acid.
Use may also be made of compounds corresponding to the mesomeric or tautomeric forms of structures (A-II) to (A-IX).
Among the natural direct dyes that may be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts may also be used. Preferably, the dyeing composition comprises at least one direct dye chosen from cationic direct dyes, non-ionic direct dyes, such as neutral nitrobenzene direct dyes, neutral anthraquinone dyes, and mixtures thereof
The total content of direct dye(s) present in the dyeing composition according to the invention ranges from 0.01% to 10% by weight relative to the total weight of the dyeing composition.
Preferably, the total content of direct dye(s) present in said dyeing composition ranges from 0.05% to 10% by weight, more preferentially ranges from 0.075% to 8% by weight, even more preferentially ranges from 0.1% to 6% relative to the total weight of the dyeing composition.
Scleroslucan sums
According to the invention, the composition comprises one or more scleroglucan gums.
Scleroglucan gums are polysaccharides of microbial origin produced by a fungus of Sclerotium type, in particular Sclerotium rolfsii. They are polysaccharides constituted solely of glucose units.
Scleroglucan gums may or may not be modified. Preferably, the scleroglucan gums used in the present invention are unmodified.
Examples of scleroglucan gums that may be used in the present invention are, in a nonlimiting manner, the products sold under the name Actigum CS, in particular Actigum CS 11 by the company Sanofi Bio Industries, and under the name Amigum or Amigel by the company Alban Muller International.
Other scleroglucan gums, such as the gum treated with glyoxal described in French patent application No. 2633 940, may also be used.
The scleroglucan gum(s) are present in the composition preferably in a total content ranging from 0.1% to 10% by weight, preferentially from 0.2% to 5% by weight, more preferentially from 0.3% to 3% by weight and even more preferentially from 0.4% to 2% by weight, relative to the total weight of the composition.
Non-ionic associative polymers
The composition according to the invention comprises one or more non-ionic associative polymers.
For the purposes of the present invention, the term "polymer" is intended to mean any compound derived from the polymerization by polycondensation or from the radical polymerization of monomers, at least one of which is other than an alkylene oxide, and of a monofunctional compound of formula RX, R denoting an optionally hydroxylated C10-C30 alkyl or alkenyl group, and X denoting a carboxylic acid, amine, amide, hydroxyl or ester group. All the compounds resulting solely from the simple condensation of an alkylene oxide with a fatty alcohol, a fatty ester, a fatty acid, a fatty amide or a fatty amine are in particular excluded.
The associative polymers according to the invention are polymers comprising at least one fatty chain comprising from 8 to 30 carbon atoms and of which the molecules are capable, in the formulation medium, of associating with each other or with molecules of other compounds.
Preferably, the fatty chain comprises from 10 to 30 carbon atoms.
A particular case of associative polymers is amphiphilic polymers, i.e. polymers comprising one or more hydrophilic parts or groups which make them water- soluble and one or more hydrophobic zones or groups (comprising at least one fatty chain) via which the polymers interact and assemble with each other or with other molecules.
The term “hydrophobic group” is intended to mean a group or a polymer bearing a saturated or unsaturated and linear or branched hydrocarbon-based chain. When it denotes a hydrocarbon-based group, the hydrophobic group comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and preferentially from 18 to 30 carbon atoms. Preferentially, the hydrocarbon-based hydrophobic group originates from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol, or else from a polyalkylenated fatty alcohol, such as steareth-100. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
For the purposes of the present invention, the term "fatty chain" is understood to mean a linear or branched alkyl or alkenyl chain comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
For the purposes of the present invention, the term "fatty compound", for instance a fatty alcohol, a fatty acid or a fatty amide, is intended to mean a compound comprising, in its main chain, at least one saturated or unsaturated hydrocarbon-based chain, such as alkyl or alkenyl, comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
The non-ionic associative polymers are preferably chosen from: -(1) celluloses modified with groups comprising at least one fatty chain; preferably from:
- hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably Cx to C22, preferably such as the cetylhydroxyethylcellulose sold notably under the reference Natrosol Plus Grade 330 CS (Ci6 alkyls) sold by the company Ashland, or the product Polysurf 67CS sold by the company Ashland,
- hydroxyethylcelluloses modified with polyalkylene glycol ether alkyl phenol groups, such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) ether of nonyl phenol) sold by the company Amerchol,
- and mixtures thereof;
-(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia;
-(3) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers, mention may be made, by way of example, of: the products Antaron V216 or Ganex V216 (vinylpyrrolidone/hexadecene copolymer) sold by the company ISP,
- the products Antaron V220 or Ganex V220 (vinylpyrrolidone/eicosene copolymer) sold by the company ISP;
-(4) copolymers of C1-C6 alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208;
-(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer; -(6) polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;
-(7) polymers with an aminoplast ether backbone bearing at least one fatty chain, such as the Pure Thix compounds sold by the company Sud-Chemie;
-(8) and mixtures thereof.
Particularly preferably, the non-ionic associative polymer(s) are chosen from celluloses modified with groups comprising at least one fatty chain.
Preferably, the non-ionic associative polymer(s) are chosen from hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, and hydroxyethylcelluloses modified with polyalkylene glycol alkyl phenyl ether groups, and mixtures thereof.
Preferably, the non-ionic associative polymer is cetylhydroxyethylcellulose.
The non-ionic associative polymer(s), which are preferably cellulose-based, are present in the composition in a total content ranging from 0.01% to 10% by weight, and more preferentially from 0.05% to 5% by weight, better still from 0.1% to 2% by weight, relative to the total weight of the composition.
Surfactants
Preferably, the composition according to the present invention may also comprise one or more surfactants.
The surfactant(s) may be chosen from anionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants and non-ionic surfactants, and mixtures thereof.
The composition according to the invention may comprise at least one anionic surfactant.
The term "anionic surfactant" means a surfactant comprising, 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 , P03 2 , H2PO2, HP02 ·, P02 2 P0H and PO .
The composition according to the invention may comprise one or more anionic surfactants. The anionic surfactant(s) can be chosen from alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, a-olefm sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfo succinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkyl sulfo succinamates, acyl isethionates and N-(Ci-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; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds (unless specified otherwise) generally comprising from 6 to 24 carbon atoms and the aryl group generally denoting a phenyl group.
These compounds may be oxyethylenated and then preferably comprise 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 especially be mentioned include the salts of mono-, di- and triethanolamine, the salts of mono-, di- or triisopropanolamine, and the salts of 2-amino-2-methyl-l -propanol, of2-amino-2- m ethyl- 1,3 -propanediol and of tris(hydroxymethyl)aminomethane.
Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
The anionic surfactants optionally 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 comprising from 2 to 50 ethylene oxide groups; alkyl-D-galactoside uronic acids; acyl sarcosinates, acyl glutamates; and alkyl polyglycoside carboxylic esters.
Use may be made most particularly of polyoxyalkylenated alkyl ether carboxylic acids, for instance lauryl ether carboxylic acid (4.5 EO), sold, for example, under the name Akypo RLM 45 CA from Kao.
The composition according to the invention may also optionally comprise one or more amphoteric or zwitterionic surfactants. They may in particular be optionally quaternized secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.
Mention may be made in particular of (Cx-Cio)alkyl betaines, sulfo betaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines or (C8-C2o)alkylamido(C6-C8)alkylsulfo betaines.
Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, as defined above, mention may also be made of the compounds of respective structures (Ai), (A2) and (A3) below:
Ra-CONHCH2CH2-N+(Rb)(Rc)(CH2COO-) (Ai) in which:
Ra represents a C10-C30 alkyl or alkenyl group derived from an acid Ra- COOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group,
Rb represents a b-hydroxyethyl group, and Rc represents a carboxymethyl group, and
R'a-CONHCH2CH2-N(B)(B') (A2) in which:
B represents -CH2CH2OX', B' represents -(CH2)Z-Y', with z = 1 or 2,
X' represents the group -OB-COOH, OB-COOZ', -CH2CH2-COOH or - CH2CH2-C00Z', or a hydrogen atom,
Y' represents -COOH, -COOZ', or the group CH2-CH0H-S03H or -CH2- CHOH-SO3Z',
Z' represents an ion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine,
R'a represents a C10-C30 alkyl or alkenyl group of an acid R'a-COOH preferably present in hydrolysed linseed oil or coconut oil, an alkyl group, in particular a C17 alkyl group and its iso form, or an unsaturated C17 group.
These compounds of formula (Ai) or (A2) are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodi acetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium caprylamphodipropionate, lauroamphodipropionic acid, cocoamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold by Rhodia under the trade name Miranol® C2M Concentrate.
Ra"-NHCH(Y")-(CH2)„CONH(CH2)„'-N(Rd)(Re) (A3) in which formula:
Y" represents the group -COOH, -COOZ" or -CH2-CH(0H)S03H or the group -CH2CH(0H)S03-Z";
Rd and Re, independently of each other, represent a C1-C4 alkyl or hydroxyalkyl radical;
Z" represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
Ra" represents a C10-C30 alkyl or alkenyl group of an acid Rf'-COOH preferably present in hydrolysed linseed oil or coconut oil; n and ri denote, independently of each other, an integer ranging from 1 to 3.
Among the compounds of formula (A3), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB. Among the abovementioned amphoteric or zwitterionic surfactants, it is preferred to use (C8-C20 alkyl) betaines such as cocobetaine, (C8-C20 alkyl) ami do(Ci- Ce alkyl) betaines such as cocamidopropyl betaine, and mixtures thereof. More preferentially, the amphoteric or zwitterionic surfactants(s) are chosen from cocamidopropyl betaine and cocobetaine.
The composition according to the invention may also comprise at least one or more cationic surfactants. Preferably, the surfactant(s) are chosen from optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
Examples of quaternary ammonium salts that may notably be mentioned include:
- those corresponding to the general formula (X) below:
X
Figure imgf000034_0001
(X) in which the groups Rs to Rn, which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups Rs to Rn comprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms. The aliphatic groups may include heteroatoms notably such as oxygen, nitrogen, sulfur and halogens.
The aliphatic groups are chosen, for example, from C1-C30 alkyl, C1-C30 alkoxy, polyoxy(C2-C6)alkylene, C1-C30 alkylamide, (Ci2-C22)alkylamido(C2- C6)alkyl, (Ci2-C22)alkyl acetate, C1-C30 hydroxyalkyl groups, X is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C4)alkyl sulfates, and (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonates.
Among the quaternary ammonium salts of formula (X), preference is given, firstly, to tetraalkyl ammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group includes from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride or benzyldimethylstearylammonium chloride, or, secondly, to distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or also, finally, to palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name Ceraphyl® 70 by the company Van Dyk;
- quaternary ammonium salts of imidazoline, for instance those of formula (XI) below:
Figure imgf000035_0001
(XI) in which
Ri2 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example derived from tallow fatty acids,
Ri3 represents a hydrogen atom, a C1-C4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, Ri4 represents a C1-C4 alkyl group,
Ri5 represents a hydrogen atom or a C1-C4 alkyl group, X is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C4)alkyl sulfates and (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonates.
Preferably, R12 and R13 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, Ri4 denotes a methyl group and R15 denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo,
- quaternary diammonium or triammonium salts, in particular of formula (XII) below:
Figure imgf000035_0002
(XII) in which Ri6 denotes an alkyl group including approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms,
Ri7 is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH2)3-N+(Ri6a)(Ri7a)(Ri8a),
Ri6a, Rna, Ri8a, Ri8, Ri9, R20 and R21, which may be identical or different, are chosen from hydrogen or an alkyl group comprising from 1 to 4 carbon atoms, and
X is an anion chosen from the group of halides, acetates, phosphates, nitrates, (Ci-C4)alkyl sulfates, (Ci-C4)alkylsulfonates or (Ci-C4)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.
Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quatemium 89), and Finquat CT, sold by the company Finetex (Quaternium 75);
- quaternary ammonium salts containing one or more ester functions, for instance those of formula (XIII) below:
Figure imgf000036_0001
(XIII) in which:
- R22 is chosen from C1-C6 alkyl groups and C1-C6 hydroxyalkyl or dihydroxyalkyl groups,
- R-23 is chosen from:
- the group
Figure imgf000036_0002
- linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups R27,
- a hydrogen atom,
- R25 is chosen from:
- the group
Figure imgf000036_0003
- linear or branched, saturated or unsaturated C1-C6 hydrocarbon-based groups R29,
- a hydrogen atom, - R.24, R-26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups,
- r, s and t, which may be identical or different, are integers ranging from 2 to 6,
- rl and tl, which may be identical or different, are equal to 0 or 1,
- r2 + rl = 2 r and tl + t2 = 2 t,
- y is an integer ranging from 1 to 10,
- x and z, which may be identical or different, are integers ranging from 0 to
10,
- X is a simple or complex organic or inorganic anion, with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R23 denotes R27, and that when z is 0 then R25 denotes R29.
The alkyl groups R22 may be linear or branched, and more particularly linear.
Preferably, R22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
Advantageously, the sum x + y + z is from 1 to 10.
When R23 is a hydrocarbon-based group R27, it may be long and contain from 12 to 22 carbon atoms, or short and contain from 1 to 3 carbon atoms.
When R25 is a hydrocarbon-based group R29, it preferably contains 1 to 3 carbon atoms.
Advantageously, R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn- C21 alkyl and alkenyl groups.
Preferably, x and z, which may be identical or different, are equal to 0 or 1. Advantageously, y is equal to 1.
Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
The anion X is preferably a halide, preferably chloride, bromide or iodide, a (Ci-C4)alkyl sulfate or a (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfonate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium bearing an ester functional group.
The anion X is even more particularly chloride, methyl sulfate or ethyl sulfate. Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (XIII) in which:
- R22 denotes a methyl or ethyl group,
- x and y are equal to 1,
- z is equal to 0 or 1,
- r, s and t are equal to 2,
- R-23 is chosen from:
- t ,1he group
Figure imgf000038_0001
- methyl, ethyl or C14-C22 hydrocarbon-based groups,
- a hydrogen atom,
- R25 is chosen from:
- the group
Figure imgf000038_0002
-
- a hydrogen atom,
- R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
Advantageously, the hydrocarbon-based groups are linear.
Among the compounds of formula (XIII), examples that may be mentioned include salts, notably the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are derived more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company CECA or Rewoquat® WE 18 by the company Rewo-Witco.
The composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
Use may also be made of the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
Use may also be made of the behenoylhydroxypropyltrimethylammonium chloride sold, for example, by the company Kao under the name Quartamin BTC 131.
Preferably, the ammonium salts containing at least one ester function contain two ester functions.
Preferably, the cationic surfactant(s) are chosen from cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethyl methylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.
The composition according to the invention may also optionally comprise one or more non-ionic surfactant(s).
The non-ionic surfactants that may be used according to the invention may be chosen from:
- alcohols, a-diols and (Ci-C2o)alkylphenols, these compounds being polyethoxylated and/or polypropoxylated and/or polyglycerolated, the number of ethylene oxide and/or propylene oxide groups possibly ranging from 1 to 100, and the number of glycerol groups possibly ranging from 2 to 30; or else these compounds comprising at least one fatty chain including from 8 to 40 carbon atoms and notably from 16 to 30 carbon atoms; in particular, oxyethylenated alcohols comprising at least one saturated or unsaturated, linear or branched Cx to C40 alkyl chain, comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and including one or two fatty chains; - condensates of ethylene oxide and propylene oxide with fatty alcohols;
- polyethoxylated fatty amides preferably containing from 2 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, preferably containing from 2 to 40 ethylene oxide units;
- fatty acid esters of sucrose;
- polyoxyalkylenated, preferably polyoxyethylenated, fatty acid esters containing from 2 to 150 mol of ethylene oxide, including oxyethylenated plant oils;
- N-(C6-C24 alkyl)glucamine derivatives;
- amine oxides such as (C10-C14 alkyl)amine oxides orN-(Cio-Ci4 acyl)aminopropylmorpholine oxides;
- and mixtures thereof.
Mention may also be made of non-ionic surfactants of alkyl(poly)glycoside type, represented notably by the following general formula:
RiO-(R20)t-(G)v in which:
- Ri represents a linear or branched alkyl or alkenyl radical including 6 to 24 carbon atoms and notably 8 to 18 carbon atoms, or an alkylphenyl radical of which the linear or branched alkyl radical includes 6 to 24 carbon atoms and notably 8 to 18 carbon atoms,
- R2 represents an alkylene radical including 2 to 4 carbon atoms,
- G represents a sugar unit including 5 to 6 carbon atoms,
- 1 denotes a value ranging from 0 to 10 and preferably from 0 to 4,
- v denotes a value ranging from 1 to 15 and preferably from 1 to 4.
Preferably, the alkyl(poly)glycoside surfactants are compounds of the formula described above in which:
- Ri denotes a linear or branched, saturated or unsaturated alkyl radical including from 8 to 18 carbon atoms,
- R2 represents an alkylene radical including 2 to 4 carbon atoms,
- 1 denotes a value ranging from 0 to 3 and preferably equal to 0,
- G denotes glucose, fructose or galactose, preferably glucose;
- the degree of polymerization, i.e. the value of v, possibly ranging from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization more particularly being between 1 and 2. The glucoside bonds between the sugar units are generally of 1-6 or 1-4 type and preferably of 1-4 type. Preferably, the alkyl(poly)gly coside surfactant is an alkyl(poly)glucoside surfactant. C8/Ci6-Alkyl(poly)glucosides 1,4, and notably decyl glucosides and caprylyl/capryl glucosides, are most particularly preferred, preferably caprylyl/capryl glucosides.
Among the commercial products, mention may be made of the products sold by the company Cognis under the names Plantaren® (600 CS/U, 1200 and 2000) or Plantacare® (818, 1200 and 2000); the products sold by the company SEPPIC under the names Oramix CG 110 and Oramix® NS 10; the products sold by the company BASF under the name Lutensol GD 70, or the products sold by the company Chem Y under the name AGIO LK.
Preferably, use is made of (Cs/Cio) alkyl polyglucoside (2) in aqueous solution at 60%, such as those sold under the name Oramix CG 110 by the company SEPPIC.
Preferentially, the non-ionic surfactants are chosen from:
- saturated or unsaturated, linear or branched, oxyethylenated fatty alcohols including at least one Cs to C40, notably C8-C20 and better still C10-C18 alkyl chain, and comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol, or even from 3 to 20 mol of ethylene oxide; and
- (C6-C24 alkyl)(poly)glycosides, and more particularly (Cs-Cis alkyl)(poly)glycosides;
- and mixtures thereof; and even more preferentially from (C6-C24 alkyl)(poly)glycosides, preferentially (Cs- Ci8 alkyl)(poly)glycosides.
Preferably, the non-ionic surfactant(s) are chosen from alkyl(poly)glycosides. Preferably, the non-ionic surfactant(s) are chosen from (C6-C24 alkyl)(poly)glycosides, more preferentially from (Cs-Cis alkyl)(poly)glycosides, preferably from C8/Ci6-alkyl(poly)glucosides, preferably from decyl glucosides and/or caprylyl/capryl glucosides and/or cocoyl glucosides. The non-ionic surfactant(s) are preferably chosen from (C6-C24 alkyl)polygly cosides.
Preferably, the surfactant(s) are chosen from amphoteric or zwitterionic surfactants, cationic surfactants, non-ionic surfactants, and mixtures thereof. According to one preferred embodiment, the composition comprises at least one cationic surfactant and at least one non-ionic surfactant, preferably chosen from (C6-C24 alkyl)polygly cosides.
According to another preferred embodiment, the composition comprises at least one cationic surfactant and at least one amphoteric or zwitterionic surfactant.
According to another preferred embodiment, the composition comprises at least one amphoteric or zwitterionic surfactant and a non-ionic surfactant, preferably chosen from (C6-C24 alkyl)polygly cosides.
When it comprises said surfactants, the composition preferably comprises one or more surfactants in a total content ranging from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight and better still from 0.1% to 5% by weight, or even from 0.5% to 5% by weight, relative to the total weight of the composition.
When it comprises said surfactants, the composition comprises one or more cationic surfactants in a total content preferably ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight, better still from 0.1% to 3% by weight, relative to the total weight of the composition.
When it comprises said surfactants, the composition comprises one or more amphoteric or zwitterionic surfactants in a total content preferably ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight, better still from 0.1% to 3% by weight, relative to the total weight of the composition.
When it comprises said surfactants, the composition comprises one or more non-ionic surfactants in a total content ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight, better still from 0.1% to 3% by weight, relative to the total weight of the composition.
Fatty substance
Preferably, the composition according to the present invention may also comprise one or more fatty substances.
The term "fatty substance" is intended to mean an organic compound that is insoluble in water at ordinary ambient temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1% and even more preferentially less than 0.1%). They bear in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane.
These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids since salified fatty acids constitute soaps which are generally soluble in aqueous media.
The fatty substances are in particular chosen from C6-Ci6 hydrocarbons or hydrocarbons comprising more than 16 carbon atoms and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, non-silicone waxes, and silicones.
It is recalled that, for the purposes of the invention, the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 30 carbon atoms, which are optionally substituted, in particular with one or more (in particular 1 to 4) hydroxyl groups. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
As regards the C6-C16 alkanes, they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane. The linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam©.
The fatty substance(s) may be chosen from fatty alcohols and/or fatty esters.
The fatty alcohols that may be used in the compositions of the invention are saturated or unsaturated, and linear or branched, and comprise from 6 to 30 carbon atoms and more particularly from 8 to 30 carbon atoms. Examples that may be mentioned include cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol and linoleyl alcohol.
The wax(es) that may be used in the compositions of the invention are chosen especially from carnauba wax, candelilla wax, esparto grass wax, paraffin wax, ozokerite, plant waxes, for instance olive tree wax, rice wax, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant blossom sold by the company Bertin (France), animal waxes, for instance beeswaxes, or modified beeswaxes (cerabellina); other waxes or waxy starting materials that may be used according to the invention are especially marine waxes such as the product sold by the company Sophim under the reference M82, and polyethylene waxes or polyolefin waxes in general.
As regards the esters of fatty acids and/or of fatty alcohols, advantageously different from the triglycerides mentioned above, mention may be made especially of esters of saturated or unsaturated, linear or branched C1-C26 aliphatic mono- or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic mono- or polyalcohols, the total carbon number of the esters more particularly being greater than or equal to 10.
Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2- ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.
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 in particular be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates.
Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.
The composition may also comprise, as fatty ester, sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term "sugar" is intended to mean oxygen-bearing hydrocarbon-based compounds which bear several alcohol functions, with or without aldehyde or ketone functions, and which include at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.
As suitable sugars, mention may be made for example of sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be notably chosen from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.
These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, notably, oleopalmitate, oleostearate and palmitostearate mixed esters.
More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleate or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate or oleostearate.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
Examples of esters or mixtures of esters of sugar and of fatty acid that may also be mentioned include:
- the products sold under the names F160, F140, FI 10, F90, F70 and SL40 by the company Crodesta, respectively denoting sucrose palmitate/stearates formed from 73% monoester and 27% diester and triester, from 61% monoester and 39% diester, triester and tetraester, from 52% monoester and 48% diester, triester and tetraester, from 45% monoester and 55% diester, triester and tetraester, from 39% monoester and 61% diester, triester and tetraester, and sucrose monolaurate;
- the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% diester-triester-polyester;
- the sucrose mono-dipalmito-stearate sold by the company Goldschmidt under the name Tegosoft® PSE.
Preferably, the fatty substance(s) are solid.
The term “solid fatty substance” is intended to mean a fatty substance that is solid at 25°C and at ambient temperature.
Preferably, the fatty substance is chosen from C12-C20, preferably C16-C18, fatty alcohols, such as cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, oleyl alcohol or linoleyl alcohol, preferably cetyl alcohol, stearyl alcohol or cetylstearyl alcohol, preferably cetylstearyl alcohol.
When it comprises said fatty substances, the composition according to the invention may comprise a total amount of fatty substances ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferentially from 1% to 8% by weight, relative to the total weight of the composition.
The composition according to the invention may comprise a total amount of solid fatty substances ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferentially from 1% to 8% by weight, relative to the total weight of the composition.
Medium
The cosmetically acceptable medium that is suitable for dyeing keratin fibres, also known as a dye support, generally comprises water or a mixture of water and of at least one organic solvent to dissolve the compounds that are not sufficiently water-soluble.
More particularly, the organic solvents are chosen from linear or branched and preferably saturated monoalcohols or diols, comprising from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4- pentanediol), neopentyl glycol and 3-methyl-l,5-pentanediol; glycerol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycols or glycol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether, butylene glycol or dipropylene glycol; and also diethylene glycol alkyl ethers, notably of Ci- C4, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
The common solvents described above, if they are present, usually represent from 1% to 40% by weight and more preferentially from 5% to 30% by weight relative to the total weight of the composition.
The composition according to the invention generally comprises water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.
The composition according to the invention preferably comprises water.
Preferably, the water content ranges from 20% to 97% by weight, more preferentially from 40% to 95% by weight and better still from 60% to 90% by weight relative to the total weight of the composition. pH of the medium
The pH of the composition according to the invention generally ranges from
1 to 12.
Preferably, the pH of the composition according to the invention ranges from 3 to 11 and particularly ranges from 5 to 8, better still from 6 to 7.5. pH adjuster
The cosmetically acceptable medium may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.
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.
Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (XIII) below:
Figure imgf000047_0001
\
R7 R9
(XIII) in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; and ¾, R7, Rx and R9, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxy alkyl radical.
Other additives
The composition according to the invention may also contain various additives conventionally used in hair dyeing compositions, such as mineral thickeners, and in particular fillers such as clays or talc; organic thickeners other than scleroglucan gums and non-ionic associative polymers; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents and/or opacifiers.
The above additives are generally present in an amount for each of them of between 0.01% and 40% by weight relative to the weight of the composition, and preferably between 0.1% and 20% by weight relative to the weight of the composition.
Needless to say, those skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the composition(s) that are useful in the dyeing process in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition(s).
Dyeing process
Another subject of the invention is a process for dyeing keratin fibres, comprising the application of a dyeing composition as described above to the keratin fibres.
Preferably, the keratin fibres are human keratin fibres, preferably human hair.
The composition is left in place for a time generally of about from 1 minute to 1 hour, preferably from 5 minutes to 30 minutes.
The temperature during the process is conventionally between ambient temperature (between 15 and 25°C) and 80°C and preferably between ambient temperature and 60°C.
After the treatment, the keratin fibres are optionally rinsed with water, optionally subjected to washing followed by rinsing with water, and are then dried or left to dry. EXAMPLES
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
Example 1:
The compositions according to the invention were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material:
[TABLE 2]
Figure imgf000049_0001
Figure imgf000050_0001
Compositions Al, A2 and A3 are homogeneous and in gel form. They have a viscosity of between 650 and 1550 cps (Al: 27 UD M3, A2: 24 UD M3, A3: 26 UD M3, measured on a Rheomat 25°C reading at 30s, rotational speed of 200 rpm).
Example 2:
The compositions were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material:
[TABLE 3]
Figure imgf000050_0002
Compositions A and B were applied to locks of permanent-waved hair containing 90% grey hair.
The "mixture/lock" bath ratio is, respectively, 3/1 (g/g). The leave-on time is 10 minutes, on a hotplate set at 27°C. On conclusion of the leave-on time, the locks are rinsed and then dried under a drying hood at 40°C.
The colour of the locks was evaluated in the CIE L* a* b* system, using a Datacolor Spectraflash SF600X spectrocolorimeter.
In this L* a* b* system, the three parameters respectively denote the intensity of the colour (L*), the green/red colour axis (a*) and the blue/yellow colour axis (b*). The higher the value of L*, the lighter the colour. The higher the value of a*, the redder the colour and the higher the value of b*, the yellower the colour.
The following results are obtained:
[TABLE 4]
Figure imgf000051_0001
A more intense colouring of the keratin fibres is obtained with the composition according to the invention using a non-ionic associative polymer, than with the comparative composition using polyquatemium-55. Example 3:
The compositions were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material: [TABLE 5]
Figure imgf000051_0002
Figure imgf000052_0001
Compositions A, B and C were applied to locks of natural hair containing 90% grey hair at a rate of 3 g of composition per gram of lock. The leave-on time is 30 minutes on a hotplate set at 27°C, then the locks are rinsed with water and dried under a drying hood at 40°C.
The colour of the locks was evaluated using a Konica Minolta CM-3600A colorimeter in the CIE L* a* b* system (illuminant D65, angle 10°, specular component included).
The following results are obtained:
[TABLE 6]
Figure imgf000052_0002
A more intense colouring of the keratin fibres is obtained with the composition A according to the invention using both a non-ionic associative polymer and scleroglucan gum than with the comparative compositions B or C using only the non-ionic associative polymer or only the scleroglucan gum.
Example 4:
The compositions were prepared from the ingredients in the following tables, in the proportions indicated in grams of active material:
[TABLE 7]
Figure imgf000053_0001
Compositions D and E were applied to locks of natural hair containing 90% grey hair at a rate of 3g of composition per gram of lock.
The leave-on time is 30 minutes on a hotplate set at 27°C, then the locks are rinsed with water and dried under a drying hood at 40°C. The colour of the locks was evaluated using a Konica Minolta CM-3600A colorimeter in the CIE L* a* b* system (illuminant D65, angle 10°, specular component included).
The following results are obtained:
[TABLE 8]
Figure imgf000054_0001
A more intense colouring of the keratin fibres is obtained with the composition D according to the invention using both a non-ionic associative polymer and scleroglucan gum than with the comparative compositions E using only the scleroglucan gum.

Claims

1. Composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising:
- one or more direct dye(s);
- one or more scleroglucan gum(s);
- one or more non-ionic associative polymer(s), the direct dye(s) being present in a total content ranging from 0.01% to 10% by weight relative to the total weight of the composition.
2. Composition according to Claim 1, in which the scleroglucan gum(s) are present in a total content ranging from 0.1% to 10% by weight, more preferentially from 0.2% to 5% by weight, and even more preferentially from 0.3% to 3% by weight, better still from 0.4% to 2% by weight, relative to the total weight of the composition.
3. Composition according to either one of the preceding claims, in which the direct dye(s) are chosen from cationic direct dyes, non-ionic direct dyes, anionic direct dyes, and mixtures thereof, preferably from non-ionic direct dyes, cationic direct dyes, and mixtures thereof.
4. Composition according to any one of the preceding claims, in which the direct dye(s) are present in a content ranging from 0.05% to 10% by weight, more preferentially ranging from 0.075% to 8% by weight, even more preferentially ranging from 0.1% to 6% by weight, relative to the total weight of the dyeing composition.
5. Composition according to any one of the preceding claims, in which said non-ionic associative polymer(s) are chosen from:
(1) celluloses modified with groups comprising at least one fatty chain;
(2) hydroxypropyl guars modified with groups comprising at least one fatty chain;
(3) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers;
(4) copolymers of C1-C6 alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer;
(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain;
(6) polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;
(7) polymers with an aminoplast ether backbone bearing at least one fatty chain;
(8) and mixtures thereof.
6. Composition according to any one of the preceding claims, in which said non-ionic associative polymer(s) are chosen from celluloses modified with groups comprising at least one fatty chain, preferably chosen from:
- hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, and mixtures thereof, preferably cetylhydroxyethylcellulose;
- hydroxyethylcelluloses modified with polyalkylene glycol alkyl phenol ether groups, such as polyethylene glycol (15) ether of nonyl phenol;
- and mixtures thereof.
7. Composition according to any one of the preceding claims, in which said non-ionic associative polymer(s) are chosen from celluloses modified with groups comprising at least one fatty chain, preferably chosen from hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, and mixtures thereof, preferably cetylhydroxyethylcellulose.
8. Composition according to any one of the preceding claims, in which said associative polymer(s) are present in a total content ranging from 0.01% to 10% by weight, preferentially from 0.05% to 5% by weight, better still from 0.1% to 2% by weight, relative to the total weight of the composition.
9. Composition according to any one of the preceding claims, which also comprises one or more surfactants, preferably chosen from cationic surfactants, amphoteric surfactants, non-ionic surfactants, and mixtures thereof.
10. Composition according to the preceding claim, in which said surfactant(s) is (are) cationic and are preferably chosen from optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof, preferably chosen from tetraalkylammonium chlorides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group comprises approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride or benzyldimethylstearylammonium chloride, or else, furthermore, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, finally, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride, and mixtures thereof.
11. Composition according to the preceding claim, in which the cationic surfactant(s) is (are) chosen from cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.
12. Composition according to Claim 9, in which said surfactant(s) is (are) amphoteric and are preferably chosen from (Cx-Cio)alkyl betaines, (C8-C2o)alkylamido(Ci-C6)alkyl betaines, and in particular from cocobetaine and cocoamidopropylbetaine.
13. Composition according to Claim 9, in which said surfactant(s) is (are) non-ionic and are preferably chosen from:
- saturated or unsaturated, linear or branched, oxyethylenated fatty alcohols comprising at least one Cs to C40, notably C8-C20, even better still C10-C18 alkyl chain, and comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol, or even from 3 to 20 mol of ethylene oxide; and
- alkyl polyglycosides, preferably (C6-C24 alkyl)(poly)glycosides, and more particularly (C8-C18 alkyl)(poly)glycosides;
- and mixtures thereof; and even more preferentially from alkyl polyglyco sides, preferably from (C6-C24 alkyl)(poly)glycosides such as (Cs-Cis alkyl)(poly)glycosides.
14. Composition according to any one of Claims 9 to 13, in which said surfactant(s) is (are) present in a total content ranging from 0.01% to 20% by weight, preferentially from 0.05% to 10% by weight, better still from 0.1% to 5% by weight, or even from 0.5% to 5% by weight, relative to the total weight of the composition.
15. Composition according to any one of the preceding claims, which also comprises one or more fatty substances, preferably chosen from fatty substances that are solid at 25°C and at atmospheric pressure.
16. Composition according to the preceding claim, in which the fatty substance(s) are chosen from C12-C20, preferably C16-C18, fatty alcohols, preferably from cetyl alcohol, stearyl alcohol, cetylstearyl alcohol, octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, oleyl alcohol or linoleyl alcohol, preferably from cetyl alcohol, stearyl alcohol and cetylstearyl alcohol.
17. Composition according to either one of Claims 15 and 16, in which the fatty substance(s) are present in a content ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, and more preferentially from 1% to 8% by weight, relative to the total weight of the composition.
18. Composition according to any one of the preceding claims, which has a viscosity greater than 50 cps, preferably of between 200 and 100000 cps, more preferentially between 300 and 50000 cps, and even more preferentially between 400 and 10 000 cps, better still from 500 to 8000 cps, or even 600 to 2000 cps, measured at 25°C.
19. Process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, which comprises the application to said fibres of a dye composition as defined according to any one of the preceding claims.
PCT/EP2020/087251 2019-12-20 2020-12-18 Hair dyeing composition comprising a direct dye, a scleroglucan gum and a non-ionic associative polymer WO2021123329A1 (en)

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