WO2021121859A1 - Hair treatment process - Google Patents

Hair treatment process Download PDF

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Publication number
WO2021121859A1
WO2021121859A1 PCT/EP2020/082846 EP2020082846W WO2021121859A1 WO 2021121859 A1 WO2021121859 A1 WO 2021121859A1 EP 2020082846 W EP2020082846 W EP 2020082846W WO 2021121859 A1 WO2021121859 A1 WO 2021121859A1
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WIPO (PCT)
Prior art keywords
alkyl
linear
branched
group
better still
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PCT/EP2020/082846
Other languages
French (fr)
Inventor
Andreia TEIXEIRA
Christelle MORVAN
Estelle Mathonneau
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L'oreal
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Publication of WO2021121859A1 publication Critical patent/WO2021121859A1/en

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    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • 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
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits

Definitions

  • the present invention relates to a process for the cosmetic treatment of the hair, consisting in sequentially applying a cosmetic care composition, in particular hair- care composition, comprising one or more particular anionic surfactants, one or more preferably associative cationic polymers and one or more organosilanes, and a cosmetic washing composition comprising one or more anionic surfactants.
  • Hair may be damaged or embrittled by the action of external atmospheric agents such as light and bad weather, or by mechanical or chemical treatments, such as brushing, combing, dyeing, bleaching, permanent-waving and/or relaxing.
  • mechanical or chemical treatments such as brushing, combing, dyeing, bleaching, permanent-waving and/or relaxing.
  • haircare compositions may be conditioning shampoos or hair conditioners, which may be in the form of gels, hair lotions or more or less thick creams.
  • conditioning agents which are intended mainly to repair or limit the harmful or undesirable effects brought about by the various treatments or at tacking factors to which hair fibers are more or less repeatedly subjected.
  • organosilanes in cos metic care compositions, to give hair satisfactory conditioning properties.
  • Such com- positions are described, for example, in patent applications FR 2910276, EP 2343042 and EP 2111848.
  • care compositions described in these documents afford conditioning and disentangling properties that are not sufficiently long-lasting. Specifically, these properties generally do not sufficiently resist washing and tend to diminish from the first shampoo wash. In other words, even though these haircare compositions make it possible to obtain suitable results during and just after their use (at TO), it was found that these effects had a tendency to disappear gradually with hair washes; it was thus necessary to regularly renew the application of hair treatments to maintain adequate conditioning effects.
  • WO 2016/083578 has therefore proposed a hair composition for caring for the hair, capable of affording conditioning properties which are not only satisfac tory, but also persistent with respect to washing, for example persistent at least after three shampoo washes.
  • This care composition comprises the combination of orga- nosilanes, cationic polymers of high charge density and cationic surfactants; it can confer on the hair a cosmetic care that is persistent with respect to shampoo washes, in particular softness, suppleness, smoothness, lightness, volume, and a non-greasy and non-laden natural feel.
  • This composition also provides hair with im proved disentangling ability. These properties show good resistance to the various attacking factors to which hair may be subjected, such as light, bad weather, wash ing and perspiration. They are particularly persistent with respect to shampoo wash- ing, especially after at least three shampoo washes.
  • a hair treatment process comprising the sequential application of a composition comprising organosilanes and of a composition for caring for or washing the hair has also been proposed, for example by EP 2111849.
  • This document describes in particular the use of a composition comprising an organosilane as a pre-shampoo, that is to say applied to the hair before washing with a shampoo comprising at least one anionic surfactant and an amphoteric surfactant.
  • This process makes it possible in particular to obtain supple, smooth hair which disentangles well.
  • FR 3060369 describes a hair treatment process wherein, firstly, a care composition containing 3-aminopropyltri- ethoxysilane and polyquaterniun-6 is applied to the hair, then the hair is washed with a shampoo containing laureth-5 carboxylic acid.
  • the care composition does not contain a surfactant of alkyl(amido) ether carboxylic type.
  • the care composition according to the invention has improved use qualities, in par ticular facilitated distribution on the hair, and improved rinsing.
  • the individual strands of the hair are more separated, and the hair is smooth to the touch and disentangles easily; it is easier to style.
  • a subject of the present invention is thus a hair treatment process comprising:
  • step (ii) a step of washing said hair, comprising the application of a cosmetic washing composition comprising one or more anionic surfactants, said steps (i) and (ii) being carried out successively, the time separating said steps (i) and (ii) being at most 60 minutes.
  • step (i) may be before or after step (ii).
  • the care step (i) can precede the washing step (ii), it being understood that the step (ii) of washing the hair is carried out at most 60 minutes after the care step (i); in this embodiment, the care composition of step (i) can be considered to be a pre-shampoo.
  • the care step (i) can also follow the washing step (ii), it being understood that the care step (i) is carried out at most 60 minutes after the washing step (ii); in this embodiment, the care composition of step (i) can be considered to be a conditioner.
  • the hair treatment process according to the invention comprises:
  • step (ii) of washing said hair comprising the application of a cosmetic washing composition comprising one or more anionic surfactants, said step (ii) of washing the hair being carried out at most 60 minutes after said step
  • the care composition used in step (i) is a pre-sham- poo composition.
  • the hair treatment process according to the invention comprises:
  • a cosmetic care composition comprising:
  • step (i) being carried out at most 60 minutes after said step (ii) of washing the hair.
  • the care composition used in step (i) is a conditioner composition.
  • the hair treatment process according to the invention thus comprises a step (i) that consists in applying to the hair a cosmetic care composition as defined below.
  • This step may or may not be followed by a leave-on step, for example a leave-on time of from 1 to 15 minutes, in particular 2 to 5 minutes.
  • This step may also be optionally followed by a rinsing step, for example rinsing with water.
  • said step (i) is followed by a rinsing step.
  • the process according to the invention com prises an intermediate rinsing step between steps (i) and (ii), in particular when the care step (i) precedes the washing step (ii).
  • the process according to the invention can also comprise an intermediate rinsing step between steps (i) and (ii), when the care step (i) follows the washing step (ii).
  • the hair treatment process according to the invention also comprises a washing step (ii) that consists in applying to the hair a cosmetic washing composition as de- fined below.
  • This step may or may not be followed by a leave-on step, for example a leave-on time of from 1 to 15 minutes, in particular 2 to 5 minutes. It can also be optionally followed by a rinsing step, for example rinsing with water; and/or by a drying step, in particular in the case where step (i) precedes the washing step (ii). Preferably, said washing step (ii) is followed by a rinsing step and optionally by a drying step.
  • step of applying (i) the care composition and the washing step (ii) are carried out successively, or sequentially, which means that one of the application steps is prior to the other application step; it being possible for intermediate steps, for exam- pie leave-on and/or rinsing and/or drying steps, to be present between these two steps.
  • the application step (i) is carried out before the washing step (ii).
  • the time separating said step (i) of applying the care composition and the step (ii) of washing the hair is at most 60 minutes; it may for example be between 30 seconds and 60 minutes, in particular between 1 and 30 minutes, or even between 2 and 20 minutes, even better still between 3 and 15 minutes, and most particularly between 4 and 10 minutes.
  • care composition denotes a composition which provides haircare, in particular conditioning; it is a cosmetic composition and is in no way a pharmaceutical composition. This composition can also be called a pre shampoo or conditioner, depending on whether it is applied before or after the wash ing step (the shampoo washing).
  • the expression “at least one” is equivalent to the expres sion “one or more” and can be substituted for said expression; the expression “be tween ... and” is equivalent to the expression “ranging from ... to” and can be sub stituted for said expression, and implies that the limits are included.
  • the hair treatment process according to the invention thus comprises a step (i) con sisting in applying to the hair a cosmetic care composition comprising one or more particular anionic surfactants, one or more cationic polymers and one or more orga- nosilanes. a) Alkyl(amido) ether carboxylic acid anionic surfactants
  • the cosmetic care composition according to the present invention comprises one or more alkyl(amido) ether carboxylic anionic surfactants.
  • anionic surfactant is intended to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups.
  • a species is termed as being “anionic” when it bears at least one permanent negative charge or when it can be ionized as a negatively charged species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.
  • the anionic surfactants are chosen from alkyl(amido) ether carboxylic acids (or car- boxylates) and/or salts thereof. They can be chosen from the following compounds, alone or as a mixture: alkyl ether carboxylic acids, alkyl(C6-C3o aryl) ether carboxylic acids, alkylamido ether carboxylic acids, and also the salts of these compounds; the alkyl and/or acyl groups of these compounds comprising from 6 to 30 carbon atoms, especially from 12 to 28, even better still from 14 to 24, or even from 16 to 22, carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these com pounds possibly being polyoxyalkylenated, especially polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units, better still from 2 to 10 ethylene oxide units.
  • polyoxyalkylenated alkyl(amido) ether carboxylic acids that may be used are preferably chosen from those of formula (I) below:
  • Ri represents a linear or branched C6-C24 alkyl or alkenyl radical, a (C8-C9)al- kylphenyl radical, a radical R 2 CONH-CH 2 -CH 2 - with R 2 denoting a linear or branched C9-C21 alkyl or alkenyl radical; preferably, Ri is a C8-C20, preferably Cs- C18, alkyl radical,
  • - n is an integer or decimal number (mean value) ranging from 2 to 24, preferably from 2 to 10,
  • - A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue.
  • Use may also be made of mixtures of compounds of formula (I), in particular mix tures of compounds bearing different groups Ri.
  • polyoxyalkylenated alkyl(amido) ether carboxylic acids that are particularly pre ferred are those of formula (I) wherein:
  • - Ri denotes a C8-C22, in particular C10-C16, or even C12-C14, alkyl radical, or alternatively a (C8-C9)alkylphenyl radical;
  • - A denotes a hydrogen or sodium atom
  • - n ranges from 2 to 20, preferably from 2 to 10.
  • Ri denotes a C12-C14 alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical
  • A denotes a hydrogen or sodium atom and n ranges from 2 to 10.
  • said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magne sium salt.
  • alkali metal salts such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts
  • alkaline-earth metal salts such as the magne sium salt.
  • amino alcohol salts that may be mentioned include monoeth- anolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2-amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)amino- methane salts.
  • Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are
  • Akypo® RLM 45 (INCI: Laureth-5 carboxylic acid), Akypo® RLM 100, and Akypo® RLM 38.
  • the anionic surfactants are chosen, alone or as a mixture, from: - (C6-C24)alkyl ether carboxylic acids and in particular (C12-C20)alkyl ether carbox ylic acids, and salts thereof;
  • C6-C24 polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids, in particular those comprising from 1 to 50, in particular from 2 to 10, ethylene oxide groups; and salts thereof; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.
  • the composition comprises said alkyl(amido) ether carboxylic anionic surfactant(s) in a total content ranging from 0.5% to 12% by weight, better still from 1 % to 10% by weight, preferentially from 1.5% to 8% by weight, even better still from 2% to 7% by weight, relative to the total weight of the composition.
  • composition according to the invention can optionally comprise one or more additional anionic surfactants, different than the anionic surfactants described above. Preferably, it does not comprise any additional anionic surfactants.
  • additional anionic surfactants different than the anionic surfactants described above. Preferably, it does not comprise any additional anionic surfactants.
  • the cosmetic care composition comprises one or more cationic, preferably associ- ative, polymers.
  • cationic polymer is intended to mean any nonsilicone polymer (polymer not comprising any silicon atoms) containing cationic groups and/or groups that can be ionized into cationic groups and not containing any anionic groups and/or groups that can be ionized into anionic groups.
  • the cationic polymers that can be used preferably have a cationic charge density greater than or equal to 4 milliequivalents/gram (meq/g), better still greater than or equal to 5 meq/g, or even ranging from 5 to 20 meq/g.
  • the cationic charge density of a polymer corresponds to the number of moles of cationic charges per unit mass of polymer under conditions in which it is totally ion ized. It may be determined by calculation if the structure of the polymer is known, i.e. the structure of the monomers constituting the polymer and their molar propor tion or weight proportion. It may also be determined experimentally by the Kjeldahl method.
  • the cationic polymers that may be used preferably have a weight-average molar mass (Mw) of between 500 and 5*10 6 approximately, preferably between 10 3 and 3x10 6 approximately.
  • the cationic polymers that can be used may be associative or nonassociative.
  • association polymer is intended to mean an amphiphilic polymer that is capable, in an aqueous medium, of reversibly combining with itself or with other molecules. It generally includes, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group.
  • the hy drophobic group may be a fatty hydrocarbon-based chain such as a linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl group comprising at least 8 carbon atoms, preferably 8 to 30 carbon atoms, better still from 12 to 24 carbon atoms.
  • cationic polymers mention may be made of:
  • - A which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;
  • R4, R5 and R6, which may be identical or different, represent an alkyl group con- taining from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group con taining from 1 to 6 carbon atoms;
  • R1 and R2 which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
  • - X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
  • the copolymers of family (1) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitro- gen with lower (C1-C4) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
  • - vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers such as those sold under the name Styleze CC 10 by ISP
  • - quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP
  • - preferably crosslinked polymers of methacryloyloxy(C1-C4)alkyltri(C1-C4)al- kylammonium salts such as the polymers obtained by homopolymerization of dime thylaminoethyl methacrylate quaternized with methyl chloride, or by copolymeriza- tion of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide.
  • Use may be made more particularly of a crosslinked acrylamide/methacryloyloxy- ethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dis- persion comprising 50% by weight of said copolymer in mineral oil.
  • This dispersion is sold under the name Salcare® SC 92 by the company Ciba.
  • Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopoly mer comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba;
  • cationic polysaccharides in particular cationic galactomannan gums and cellu loses.
  • cationic polysaccharides mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cel- lulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
  • the cellulose ether derivatives comprising quaternary ammonium groups are in par ticular described in FR 1492597, and mention may be made of the polymers sold under the name Ucare Polymer JR (JR 400 LT, JR 125 and JR 30M) or LR (LR 400 and LR 30M) by the company Amerchol. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have re acted with an epoxide substituted with a trimethylammonium group.
  • cationic cellulose copolymers or cellulose derivatives grafted with a water-sol uble quaternary ammonium monomer are described in particular in patent US 4131576, and mention may be made of hydroxyalkyl celluloses, for instance hy droxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
  • the commercial products corresponding to this defi nition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.
  • guar gums comprising cationic trialkylammonium groups.
  • Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrirnethylammonium salt (for example, a chloride).
  • a 2,3-epoxypropyltrirnethylammonium salt for example, a chloride.
  • prod ucts are in particular sold under the names Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 by the company Rhodia;
  • polymers constituted of piperazinyl units and of divalent alkylene or hydroxy- alkylene radicals bearing linear or branched chains, optionally interrupted with oxy gen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers;
  • water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldia- mine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a bifunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-un- saturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyamino
  • polyaminoamide derivatives resulting from the condensation of polyalkylene pol yamines with polycarboxyl ic acids followed by alkylation with bifunctional agents Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldial- kylenetriamine polymers wherein the alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl.
  • alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl.
  • these derivatives mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/di- ethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the com- pany Sandoz;
  • Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or else under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer;
  • cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium such as the ho mopolymers or copolymers comprising, as main constituent of the chain, units cor responding to formula (I) or (II): wherein
  • - R12 denotes a hydrogen atom or a methyl radical
  • - R10 and R11 independently of one another, denote a C1 -C6 alkyl group, a C1 -C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively R10 and R11 may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R10 and R11 , independently of one an other, preferably denote a C1-C4 alkyl group; - Y is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
  • R13, R14, R15 and R16 which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals, or else R13, R14, R15 and R16, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non nitrogen heteroatom; or else R13, R14, R15 and R16 represent a linear or branched C1 -C6 alkyl radical substituted with a nitrile, ester, acyl, amide or -C0-0-R17-D or -CO-NH-R17-D group, where R17 is an alkylene and D is a quaternary ammonium group;
  • A1 and B1 represent linear or branched, saturated or unsaturated, divalent polymethylene groups comprising from 2 to 20 carbon atoms, which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hy droxyl, quaternary ammonium, ureido, amide or ester groups, and
  • - X denotes an anion derived from a mineral or organic acid; it being understood that A1 , R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH2)n-CO-D-OC-(CH2)p- with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting: a) a glycol residue of formula -0-Z-0-, wherein Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the follow ing formulae: -(CH2CH20)x-CH2CH2- and -[CH2CH(CH3)0]y-CH2CH(CH3)-, wherein x and y denote an integer from 1 to 4, representing a defined and unique degree
  • R1 , R2, R3 and R4 which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers rang ing from 2 to 20, and X- is an anion derived from a mineral or organic acid.
  • R18, R19, R20 and R21 which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, b-hydroxyethyl, b-hydroxypropyl or - CH2CH2(OCH2CH2)pOH radical, wherein p is equal to 0 or to an integer between 1 and 6, with the proviso that R18, R19, R20 and R21 do not simultaneously repre sent a hydrogen atom,
  • - r and s which may be identical or different, are integers between 1 and 6,
  • - X- denotes an anion such as a halide
  • - A denotes a divalent dihalide radical or preferably represents -CH2-CH2-0-CH2-
  • Examples that may be mentioned include the products Mirapol® A 15, Mirapol® AD1 , Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol; (10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the com pany BASF;
  • polyamines such as Polyquart® FI sold by Cognis, referred to under the name Polyethylene glycol (15) tallow polyamine in the CTFA dictionary;
  • these polymers may be in particular chosen from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
  • these cationic polymers are chosen from polymers comprising, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to
  • polymers may be obtained, for example, by partial hydrolysis of polyvinylfor- mamide. This hydrolysis may take place in acidic or basic medium.
  • the weight-average molecular weight of said polymer, measured by light scattering, may range from 1000 to 3000000 g/mol, preferably from 10000 to 1 000000 and more particularly from 100000 to 500000 g/mol.
  • the polymers comprising units of formula (A) and optionally units of formula (B) are in particular sold under the name Lupamin by the company BASF, for instance, in a non-limiting manner, the products provided under the names Lupamin 9095, Lu pamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
  • Cationic polymers chosen from those of families (1), (2), (7) and (10) mentioned above are most particularly preferred, better still those of families (1), (7) and (10).
  • associative cationic polymers that may be used, mention may be made, alone or as a mixture, of:
  • R and R’ which may be identical or different, represent a hydrophobic group or a hydrogen atom
  • X and X’ which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively the group L”; L, L’ and L”, which may be identical or different, represent a group derived from a diisocyanate;
  • P and P’ which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group;
  • Y represents a hydrophilic group;
  • r is an integer between 1 and 100 inclusive, preferably between 1 and 50 inclusive and in particular between 1 and 25 inclusive;
  • n, m and p are each, independently of one another, between 0 and 1000 inclusive; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
  • the only hydrophobic groups are the groups R and R’ at the chain ends.
  • One preferred family of cationic associative polyurethanes is the one corresponding to formula (la) described above, wherein:
  • R and R’ both independently represent a hydrophobic group
  • X and X’ each represent a group L”, n and p are integers that are between 1 and 1000 inclusive, and L, L', L", P, P', Y and m have the meaning indicated above.
  • Another preferred family of cationic associative polyurethanes is the one corre sponding to formula (la) above wherein:
  • the polymers do not include any units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation),
  • the protonated amine functions result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R’Q, wherein R and R’ are as defined above and Q denotes a leaving group such as a halide or a sulfate.
  • R and R’ both independently represent a hydrophobic group
  • L, L’, Y and m have the meaning given above.
  • the number-average molecular weight (Mn) of the cationic associative polyure thanes is preferably between 400 and 500000 inclusive, in particular between 1000 and 400000 inclusive and ideally between 1000 and 300000 inclusive.
  • hydrophobic group is intended to mean a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain.
  • the hy- drophobic group includes at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
  • the hydrocarbon-based group is derived from a monofunctional com pound.
  • the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocar- bon-based polymer, for instance polybutadiene.
  • X and/or X’ denote(s) a group comprising a tertiary or quaternary amine
  • X and/or X’ may represent one of the following formulae: wherein:
  • R2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
  • A- is a physiologically acceptable anionic counterion such as a halide, for instance a chloride or bromide, or a mesylate.
  • the groups L, U and L represent a group of formula: wherein: Z represents -0-, -S- or -NH-;
  • R4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P.
  • the groups P and P’ comprising an amine function may represent at least one of the following formulae: wherein:
  • R5 and R7 have the same meanings as R2 defined above;
  • R6, R8 and R9 have the same meanings as R1 and R3 defined above;
  • R10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, 0, S and P; and
  • A- is a physiologically acceptable anionic counterion such as a halide, for in stance chloride or bromide, or mesylate.
  • hydrophilic group is intended to mean a polymeric or non-polymeric water-soluble group.
  • ethylene glycol diethylene glycol and propylene glycol.
  • hydrophilic polymer in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers.
  • the hydrophilic compound is preferen tially a polyether and in particular a poly(ethylene oxide) or polypropylene oxide).
  • the cationic associative polyurethanes of formula (la) according to the invention are formed from diisocyanates and from various compounds bearing functions contain ing labile hydrogen.
  • the functions containing labile hydrogen may be alcohol, pri mary or secondary amine or thiol functions, giving, after reaction with the diisocya nate functions, polyurethanes, polyureas and polythioureas, respectively.
  • polyurethanes encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
  • a first type of compound involved in the preparation of the polyurethane of formula (la) is a compound comprising at least one unit bearing an amine function.
  • This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to a preferential embodiment, this compound includes two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, sec ondary amine or thiol function.
  • a mixture of multifunctional and difunctional com pounds wherein the percentage of multifunctional compounds is low may also be used.
  • this compound may include more than one unit containing an amine function.
  • it is a polymer bearing a repetition of the unit containing an amine function.
  • HZ-(P)n-ZH or HZ-(P')p-ZH, wherein Z, P, P’, n and p are as defined above.
  • Z, P, P’, n and p are as defined above. Examples that may be mentioned include N-methyldiethanolamine, N-tert-butyldi- ethanolamine and N-sulfoethyldiethanolamine.
  • the second compound included in the preparation of the polyurethane of formula (la) is a diisocyanate corresponding to the formula:
  • methylenediphenyl diisocyanate By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, tolulene diisocya nate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
  • a third compound involved in the preparation of the polyurethane of formula (la) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (la).
  • This compound is formed form a hydrophobic group and a function containing labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
  • this compound may be a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol.
  • this compound may be, for example, a-hydroxylated hydrogenated polybutadiene.
  • the hydrophobic group of the polyurethane of formula (la) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit.
  • the hydrophobic group is introduced via the quater- nizing agent.
  • This quaternizing agent is a compound of the type RQ or R’Q, wherein R and R’ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
  • the cationic associative polyurethane may also comprise a hydrophilic block.
  • This block is provided by a fourth type of compound involved in the preparation of the polymer.
  • This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture wherein the percentage of multifunctional compound is low.
  • the functions containing labile hydrogen are alcohol, primary or secondary amine or thiol functions.
  • This compound may be a polymer terminated at the chain ends with one of these functions containing labile hydrogen.
  • ethylene glycol, diethylene glycol and propylene glycol mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
  • hydrophilic polymer When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers.
  • the hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or polypropylene oxide).
  • the hydrophilic group termed Y in formula (la) is optional. Specifically, the units containing a quaternary or protonated amine function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solu- tion.
  • hydrophilic group Y is optional, cationic associative pol yurethanes comprising such a group are, however, preferred.
  • quaternized cellulose derivatives and in particular quaternized celluloses mod- ified with groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyl groups, or linear or branched alkylaryl groups, preferably linear or branched alkyl groups, these groups comprising at least 8 car bon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof.
  • groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyl groups, or linear or branched alkylaryl groups, preferably linear or branched alkyl groups, these groups comprising at least 8 car bon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof.
  • quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyl groups, or linear or branched alkylaryl groups, preferably linear or branched alkyl groups, these groups comprising at least 8 car bon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof.
  • hydroxyethylcelluloses of formula (lb) wherein: - R represents an ammonium group RaRbRcN+-, Q- wherein Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched C1- C30 alkyl, and Q- represents an anionic counterion such as a halide, for instance a chloride or bromide; preferably an alkyl;
  • R’ represents an ammonium group R’aR’bR’cN+-, Q’- wherein R’a, R’b and R’c, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C30 alkyl, and Q’- represents an anionic counterion such as a halide, for instance a chloride or bromide; preferably an alkyl; it being understood that at least one of the radicals Ra, Rb, Rc, R'a, R'b and R'c represents a linear or branched C8-C30 alkyl;
  • x and y which may be identical or different, represent an integer between 1 and 10 000.
  • At least one of the radicals Ra, Rb, Rc, R'a, R'b and R'c represents a linear or branched C8-C30, better still C10-C24, or even C10-C14, alkyl; mention may be made in particular of the dodecyl radical (C12).
  • the other radical(s) represent a linear or branched C1-C4 alkyl, in particular methyl.
  • R may be a group chosen from -N + (CH3)3, Q 1 and - N + (Ci2H25)(CH3)2, Q 1 , preferably an -N + (CH3)3, Q 1 group.
  • R' may be a group -N + (Ci2H25)(CH3)2, Q 1 .
  • aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
  • C18 alkyl such as the prod uct Crodacel QS®, sold by the company Croda.
  • R represents a trimethylammonium halide and R' represents a dimethyldodecylammo- nium halide; preferentially, R represents trimethylammonium chloride (CH3)3N+-, Cl- and R’ represents dimethyldodecylammonium chloride (CH3)2(C12H25)N+-, Cl- .
  • This type of polymer is known under the INCI name Polyquaternium-67; as com conciseal products, mention may be made of the Softcat Polymer SL® polymers, such as SL-100, SL-60, SL-30 and SL-5, from the company Amerchol/Dow Chemical.
  • the polymers of formula (lb) are those of which the viscosity is between 2000 and 3000 cPs inclusive, preferentially between 2700 and 2800 cPs.
  • Softcat Polymer SL-5 has a viscosity of 2500 cPs
  • Softcat Polymer SL-30 has a viscosity of 2700 cPs
  • Softcat Polymer SL-60 has a viscosity of 2700 cPs
  • Softcat Polymer SL-100 has a viscosity of 2800 cPs.
  • cationic polyvinyllactams in particular those comprising:
  • - X denotes an oxygen atom or an NR6 radical
  • R1 and R6 denote, independently of one another, a hydrogen atom or a linear or branched C1-C5 alkyl radical
  • R2 denotes a linear or branched C1-C4 alkyl radical
  • - R3, R4 and R5 denote, independently of one another, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (lllc):
  • - Y, Y1 and Y2 denote, independently of one another, a linear or branched C2-C16 alkylene radical, - R7 denotes a hydrogen atom, or a linear or branched C1 -C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical,
  • R8 denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical
  • n denote, independently of one another, an integer ranging from 0 to 100 inclusive
  • - x denotes an integer ranging from 1 to 100 inclusive
  • - Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate; with the proviso that: - at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9-
  • the cationic poly(vinyllactam) polymers according to the invention may be cross- linked or non-crosslinked and may also be block polymers.
  • the counterion Z- of the monomers of formula (lc) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.
  • R3, R4 and R5 denote, independently of one another, a hydrogen atom or a linear or branched C1-C30 alkyl radical.
  • the monomer b) is a monomer of formula (lc) for which, prefer entially, m and n are equal to zero.
  • the vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc): wherein:
  • - s denotes an integer ranging from 3 to 6
  • R9 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical
  • R10 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical, with the proviso that at least one of the radicals R9 and R10 denotes a hydrogen atom.
  • the monomer (IVc) is vinylpyrrolidone.
  • the cationic poly(vinyllactam) polymers according to the invention may also contain one or more additional monomers, preferably cationic or nonionic monomers.
  • terpolymers comprising, by weight, 40% to 95% of mono mer (a), 0.1 % to 55% of monomer (c) and 0.25% to 50% of monomer (b) will be used.
  • Such polymers are in particular described in patent application WO-OO/68282.
  • cationic polymer(vinyllactam) polymers As cationic polymer(vinyllactam) polymers according to the invention, the following are in particular used: vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethac- rylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethac- rylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethac- rylamidopropylammonium tosylate or chloride terpolymers.
  • the vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethac- rylamidopropylammonium chloride terpolymer is in particular sold by the company ISP under the names Styleze W10® and Styleze W20L® (INCI name: Polyquater- nium-55).
  • the weight-average molecular weight (Mw) of the cationic poly(vinyllactam) poly mers is preferably between 500 and 20000000, more particularly between 200000 and 2000000 and preferentially between 400000 and 800000.
  • Mw weight-average molecular weight
  • D the cationic polymers obtained by polymerization of a monomer mixture com prising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers, and one or more associative vinyl monomers, as described in patent application WO 2004/024779.
  • Such a polymer is, for example, the compound sold by the company Lubrizol under the name Carbopol Aqua CC® and which corresponds to the INCI name Polyacry- late-1 crosspolymer.
  • the associative or nonassociative cationic polymers that can be used in the context of the invention are chosen, alone or as a mixture, from:
  • alkyldiallylamine or dialkyldiallylammonium cyclopolymers and in particular homo polymers or copolymers of dimethyldiallylammonium salts (for example chloride); - optionally crosslinked homopolymers or copolymers of methacryloyloxy(C1 -C4)al- kyltri(C1 -C4)alkylammonium salts;
  • the cationic polymers are chosen from associative cationic polymers, preferentially from the cationic polymers (B) derived from quaternized cellulose, and the hydroxyethylcelluloses of formula (lb) above.
  • the cationic polymers are chosen from the hydroxyethylcelluloses of formula (lb) above, in particular those for which R represents a trimethylammonium halide and R' represents a dimethyldodecylammonium halide, preferentially R rep- resents a trimethylammonium chloride (CH ) N + -, Cl and R’ represents a dimethyl- dodecylammonium chloride (CH ) (Ci H )N + -, Cl , which corresponds to Polyqua- ternium-67.
  • the care composition according to the invention may comprise the cationic poly mers) in a total amount of between 0.1% and 8% by weight, in particular from 0.2% to 5% by weight, preferentially from 0.3% to 2% by weight and even better still from 0.4% to 1.4% by weight, relative to the total weight of the composition.
  • the care composition according to the invention may comprise the associative cat ionic polymer(s) in a total amount of between 0.1% and 8% by weight, in particular from 0.2% to 5% by weight, preferentially from 0.3% to 2% by weight and even better still from 0.4% to 1.4% by weight, relative to the total weight of the composition.
  • the weight ratio between the total amount of anionic surfactants and the total amount of cationic polymers present in the care composition is less than or equal to 6, better still less than or equal to 5.5, even better still less than or equal to 5, or even less than or equal to 4.5.
  • the weight ratio between the total amount of alkyl(amido) ether carbox- ylic anionic surfactants and the total amount of associative cationic polymers pre sent in the care composition is less than or equal to 6, better still less than or equal to 5.5, even better still less than or equal to 5, or even less than or equal to 4.5.
  • the care composition according to the invention comprises one or more orga- nosilanes, preferably chosen from the compounds of formula (II) and/or oligomers thereof and/or hydrolysis products thereof:
  • R1Si(OR2)z(R3)x(OH)y (II) wherein: - R1 is a cyclic or acyclic, linear or branched, saturated or unsaturated C1-C22, in particular C2-C20, hydrocarbon-based chain, which may be substituted with a group chosen from amine groups NH2 or NHR (R being a linear or branched C1-C20, in particular C1-C6, alkyl, or a C3-C40 cycloalkyl or a C6-C30 aromatic radical); the hydroxyl group (OH), a thiol group, an aryl group (more particularly benzyl), which is possibly substituted with an NH2 or NHR group; it being possible for R1 to be interrupted with a heteroatom (O, S or NH) or a carbonyl group (CO),
  • R2 and R3 which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms,
  • - y denotes an integer ranging from 0 to 3
  • - z denotes an integer ranging from 0 to 3
  • oligomer is intended to mean the polymerization products of the com pounds of formula (II) comprising from 2 to 10 silicon atoms.
  • R2 represents an alkyl group comprising from 1 to 4 carbon atoms, bet ter still a linear alkyl group comprising from 1 to 4 carbon atoms, and preferably the ethyl group.
  • z ranges from 1 to 3.
  • y 0.
  • R1 represents a linear alkyl group comprising from 7 to 18 carbon atoms and more particularly from 7 to 12 carbon atoms, or a C1-C6, preferably C2-C4, aminoalkyl group. More particularly, R1 represents an oc tyl group.
  • R1 is a linear or branched, saturated or unsaturated C1-C6 hydrocarbon-based chain.
  • R1 preferably repre sents a saturated linear C1-C3 alkyl group, preferably a methyl group.
  • R1 preferably represents a C1-C6, preferably C2-C4, ami noalkyl group.
  • the composition according to the invention comprises one or more orga- nosilanes chosen from methyltriethoxysilane (MTES), octyltriethoxysilane (OTES), dodecyltriethoxysilane, octadecyltriethoxysilane, hexadecyltriethoxysilane, 3-ami- nopropyltriethoxysilane (APTES), 2-aminoethyltriethoxysilane (AETES), 3-ami- nopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3- (m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-(2- aminoethylaminomethyl)phenethyltrimethoxysilane, and oligomers thereof, and/or mixture
  • the organosilane(s) are present in the care composition according to the invention in a total content ranging from 0.1 % to 10% by weight, preferentially from 0.5% to 7% by weight and better still from 1 % to 4% by weight, relative to the total weight of the care composition.
  • d/ Organic acids ranging from 0.1 % to 10% by weight, preferentially from 0.5% to 7% by weight and better still from 1 % to 4% by weight, relative to the total weight of the care composition.
  • the care composition may optionally comprise one or more organic acids, in partic ular as neutralizing agent for the organosilane(s).
  • organic acid is intended to mean an organic acid and/or the associated bases thereof with a pKa of less than or equal to 7, preferably less than or equal to 6, especially ranging from 1 to 6, preferably from 2 to 5.
  • the organic acid(s) are chosen from carbox- ylic acids, sulfonic acids and mixtures thereof.
  • the organic acid(s) are chosen from saturated or unsaturated carboxylic acids.
  • the organic acid(s) are chosen from lactic acid, propanoic acid, butanoic acid, acetic acid, citric acid, maleic acid, glycolic acid, salicylic acid, malic acid, tartaric acid and mixtures thereof, and more preferably lactic acid.
  • the care composition may comprise the organic acid(s), when they are present, in a content ranging from 0.1 % to 10% by weight, preferably from 1 % to 8% by weight and even better still from 3% to 6% by weight, relative to the total weight of the composition.
  • Amphoteric surfactants e) Amphoteric surfactants
  • the care composition according to the invention may optionally comprise one or more amphoteric surfactants.
  • amphoteric or zwitterionic surfactant(s) are nonsilicone surfactants. They may in particular be optionally quaternized secondary or tertiary aliphatic amine derivatives, wherein the aliphatic group is a linear or branched chain com prising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phospho- nate group.
  • - R a represents a Cio to C30 alkyl or alkenyl group derived from an acid R a COOH preferably present in hydrolyzed coconut kernel oil, or a heptyl, nonyl or undecyl group;
  • - R b represents a b-hydroxyethyl group;
  • - M + represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
  • - X represents an organic or mineral anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C4)alkyl sulfates, (Ci-C4)alkyl- or (C-i- C4)alkylaryl-sulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M + and X- are absent;
  • - B represents the group -CH 2 CH 2 OX’
  • - X represents the group -CH 2 COOH, -CH 2 -COOZ’, -CH 2 CH 2 COOH or CH 2 CH 2 - COOZ’, or a hydrogen atom;
  • - Y' represents the group -COOH, -COOZ' or -CH 2 CH(0H)S0 3 H or the group CH 2 CH(0H)S0 3 -Z';
  • - 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 Cio to C30 alkyl or alkenyl group of an acid R a -COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil, or an alkyl group, in particular a C17 group, and its iso form, or an unsaturated C17 group.
  • cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate.
  • - Y represents the group -COOH, -COOZ" or -CH 2 -CH(0H)S0 3 H or the group CH 2 CH(0H)S0 3 -Z";
  • R d and R e independently of one another, represent a Ci to 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 to C30 alkyl or alkenyl group of an acid R a" -COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil;
  • n denote, independently of one another, an integer ranging from 1 to 3.
  • Mention may be made, among the compounds of formula (II), of the compound clas sified in the CTFA dictionary under the name sodium diethylaminopropyl cocoas- partamide and sold by the company Chimex under the name Chimexane HB. These compounds may be used alone or as mixtures.
  • amphoteric or zwitterionic surfactants use is preferably made of (Cs- C2o)alkylbetaines such as cocoylbetaine, (C8-C2o)alkylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof, and the compounds of for mula (IV) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide).
  • amphoteric or zwitterionic surfactants are chosen from (Cs-C2o)al- kylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine.
  • the care composition according to the invention comprises one or more amphoteric surfactants.
  • am- photeric surfactant(s) are preferably present in a total content ranging from 0.1 % to 10% by weight, preferentially in a content ranging from 0.5% to 5% by weight and even better still from 1% to 3% by weight, relative to the total weight of the care composition.
  • the cosmetic care composition according to the invention may optionally comprise one or more nonionic surfactants, in particular such as those described in the Hand book of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and Lon don), 1991, pp 116-178.
  • nonionic surfactants in particular such as those described in the Hand book of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and Lon don), 1991, pp 116-178.
  • nonionic surfactants examples include the following com pounds, alone or as a mixture:
  • esters of fatty acids and of sucrose - (C8-C3o)alkyl(poly)glucosides, (C8-C3o)alkenyl(poly)glucosides, which are option ally oxyalkylenated and which comprise from 1 to 15 glucose units, (Cs-C3o)al- kyl(poly)glucoside esters;
  • the oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
  • the number of moles of ethylene oxide and/or of propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol in particular ranges from 1 to 50 and better still from 1 to 10.
  • the nonionic surfactants according to the invention do not comprise any oxypropylene units.
  • they comprise a number of moles of ethylene oxide ranging from 1 to 250, in particular from 2 to 100 and better still from 2 to 50.
  • nonionic surfactant(s) that may be used in the care composition according to the invention are preferentially chosen, alone or as a mixture, from:
  • nonionic surfactant(s) are chosen, alone or as a mixture, from:
  • - saturated or unsaturated, preferably saturated (hydrogenated), oxyethylenated plant oils comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50; mention may particularly be made of PEG-40 hydrogenated castor oil;
  • the care composition according to the invention comprises one or more nonionic surfactants.
  • the care composition according to the invention comprises the nonionic surfactant(s) in a total content ranging from 0.1 % to 10% by weight, preferably from 0.5% to 8% by weight and preferentially from 1 % to 5% by weight, relative to the total weight of the care composition. q / Other ingredients
  • the care composition may comprise a cosmetically acceptable medium, that is to say a medium compatible with topical application to keratin fibers, in particular the hair.
  • the care composition according to the invention may comprise water or a mixture of water and one or more cosmetically acceptable solvents chosen from C1-C4 al cohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glyc erol, propylene glycol, hexylene glycol, and polyethylene glycols; and mixtures thereof.
  • C1-C4 al cohols such as ethanol, isopropanol, tert-butanol or n-butanol
  • polyols such as glyc erol, propylene glycol, hexylene glycol, and polyethylene glycols
  • the care composition according to the invention comprises a total water content of between 40% and 98% by weight, preferably between 50% and 95%, preferentially between 60% and 92% by weight, even better still between 65% and 95% by weight, or even between 70% and 90% by weight, relative to the total weight of the composition.
  • the pH of the care composition according to the invention generally ranges from 3 to 9, preferably from 3 to 8, preferentially from 3.5 to 7 and better still from 4 to 6, or even from 4.5 to 5.5.
  • the cosmetic care composition according to the invention may further comprise at least one standard cosmetic ingredient, in particular chosen from plant, mineral, an imal or synthetic oils; liquid fatty alcohols; liquid fatty esters; solid fatty substances and in particular waxes, solid fatty esters, solid alcohols; sunscreens; moisturizers; antidandruff agents; antioxidants; pearlescent agents and opacifiers; plasticizers or coalescence agents; preservatives; sequestrants (EDTA and salts thereof); color ants.
  • the composition may of course comprise several cosmetic ingredients fea tured in the above list.
  • the hair treatment process according to the invention also comprises a step, termed washing step, (ii) that consists in applying to the hair a cosmetic washing composi tion, comprising one or more anionic surfactants.
  • said washing composition, or shampoo can also comprise one or more amphoteric surfactants and/or one or more nonionic surfactants. a / Anionic surfactants
  • the cosmetic washing composition comprises one or more anionic surfactants.
  • anionic surfactant is intended to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups.
  • a species is termed as being “anionic” when it bears at least one permanent negative charge or when it can be ionized as a negatively charged species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.
  • the anionic surfactants may be sulfate, sulfonate and/or carboxylic (or carboxylate) surfactants. Needless to say, a mixture of these surfactants may be used.
  • the carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-COOH or -COO ) and may optionally also comprise one or more sulfate and/or sulfonate functions;
  • the sulfonate anionic surfactants comprise at least one sulfonate function (-SO 3 H or -SO3-) and may optionally also comprise one or more sulfate functions, but do not comprise any carboxylate functions; and
  • the sulfate anionic surfactants comprise at least one sulfate function but do not comprise any carboxylate or sulfonate functions.
  • the carboxylic anionic surfactants that may be used thus include at least one car- boxylic or carboxylate function (-COOH or -COO ).
  • acylglycinates may be chosen from the following compounds: acylglycinates, acyllactylates, acylsarcosinates, acylglutamates; alkyl ether carboxylic acids, alkyl(C6-30 aryl)ether carboxylic acids, alkyl-D-galactosideuronic acids, alkylamido ether car boxylic acids; and also the salts of these compounds; the alkyl and/or acyl groups of these compounds comprising from 6 to 30 carbon atoms, in particular from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being pol- yoxyalkylenated, in particular polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units, better still from 2 to 10 ethylene oxide units.
  • C6-C24 alkyl monoesters of polyglycoside-polycar- boxylic acids such as C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl polyglyco- side-tartrates and C6-C24 alkyl polyglycoside-sulfosuccinates, and salts thereof.
  • carboxylic surfactants mention may be made most particularly of polyoxyalkylenated alkyl(amido) ether carboxylic acids and salts thereof, in particu lar those comprising from 2 to 50 alkylene oxide, in particular ethylene oxide, groups, such as the compounds sold by the company Kao under the Akypo names.
  • the polyoxyalkylenated alkyl(amido) ether carboxylic acids that may be used are preferably chosen from those of formula (1):
  • Rr represents a linear or branched C6-C24 alkyl or alkenyl radical, a (C8-C9)al- kylphenyl radical, a radical R 2 CONH-CH2-CH2- with R ? denoting a linear or branched C9-C21 alkyl or alkenyl radical; preferably, Rr is a C8-C20, preferably C8- C18, alkyl radical;
  • - n’ is an integer or decimal number (mean value) ranging from 2 to 24 and preferably from 2 to 10, - A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue.
  • Use may also be made of mixtures of compounds of formula (1), in particular mix tures of compounds bearing different groups Rr.
  • polyoxyalkylenated alkyl(amido) ether carboxylic acids that are particularly pre ferred are those of formula (1 ) wherein:
  • Rr denotes a linear or branched C8-C22, in particular C10-C16 or even C12-C14 alkyl radical, or alternatively a (C8-C9)alkylphenyl radical;
  • - A denotes a hydrogen or sodium atom, and
  • - n’ ranges from 2 to 20, preferably from 2 to 10.
  • Rr denotes a C12-C14 alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical
  • A de notes a hydrogen or sodium atom and n’ ranges from 2 to 10.
  • Akypo® RLM 45 (INCI: Laureth-5 carboxylic acid), Akypo® RLM 100, and Akypo® RLM 38.
  • carboxylic anionic surfactants are chosen, alone or as a mixture, from:
  • acylglutamates in particular of C6-C24 or even C12-C20, such as stearoylgluta- mates, and in particular disodium stearoylglutamate;
  • acylsarcosinates in particular of C6-C24 or even C12-C20, such as palmitoylsar- cosinates, and in particular sodium palmitoylsarcosinate;
  • acyllactylates in particular of C12-C28 or even C14-C24, such as behenoyllac- tylates, and in particular sodium behenoyllactylate; - C6-C24 and in particular C12-C20 acylglycinates;
  • C6-C24 polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids, in particular those comprising from 2 to 50 ethylene oxide groups; in particular in acid form or in the form of alkali metal or alkaline-earth metal, ammo nium or amino alcohol salts.
  • Polyoxyalkylenated (C6-C24)alkyl ether carboxylic acids and salts thereof are prefer ably used.
  • the sulfonate anionic surfactants that may be used include at least one sulfonate function (-SO 3 H or -SOz ⁇ ). They may be chosen from the following compounds: al- kylsulfonates, alkyl ether sulfonates, alkylamidesulfonates, alkylarylsulfonates, a- olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccin- ates, alkylamidesulfosuccinates, alkylsulfoacetates, N-acyltaurates, acylisethio- nates; alkylsulfolaurates; and also the salts of these compounds; the alkyl groups of these compounds comprising from 6 to 30 carbon atoms, in par ticular from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon
  • the sulfate anionic surfactants that may be used include at least one sulfate function (-OSOsH or -OSO3-).
  • alkyl sulfates alkyl sulfates, alkyl ether sul fates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; and the salts of these compounds; the alkyl groups of these compounds comprising from 6 to 30 carbon atoms, in par ticular from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, in particular polyoxyethyle- nated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.
  • the sulfate anionic surfactants are chosen, alone or as a mixture, from:
  • alkyl ether sulfates in particular of C6-C24 or even C12-C20, preferably comprising from 2 to 20 ethylene oxide units; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.
  • said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magne sium salt.
  • amino alcohol salts examples include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanola- mine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2-amino-2- methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
  • Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
  • the anionic surfactants are chosen, alone or as a mixture, from:
  • C6-C24 polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids and salts thereof, in particular those comprising from 2 to 50 alkylene oxide, in particular ethylene oxide, groups; - C6-C24 and in particular C12-C20 acylglutamates;
  • the composition comprises one or more sulfate anionic surfactants, preferably one or more C6-C24 and in particular C12-C20 alkyl sulfates, and/or one or more C6-C24 and in particular C12-C20 alkyl ether sulfates; preferably comprising from 2 to 20 ethylene oxide units; particularly in the form of alkali metal or alka line-earth metal, ammonium or amino alcohol salts.
  • the anionic surfactant(s) are preferably present in the washing composition in a total content ranging from 2% to 30% by weight, in particular from 4% to 25% by weight, better still from 5% to 20% by weight and even better still from 6% to 15% by weight, relative to the total weight of the composition.
  • b / Amphoteric surfactants are preferably present in the washing composition in a total content ranging from 2% to 30% by weight, in particular from 4% to 25% by weight, better still from 5% to 20% by weight and even better still from 6% to 15% by weight, relative to the total weight of the composition.
  • the washing composition according to the invention may also comprise one or more amphoteric surfactants.
  • amphoteric or zwitterionic surfactant(s) are nonsilicone surfactants. They may in particular be optionally quaternized secondary or tertiary aliphatic amine derivatives, wherein the aliphatic group is a linear or branched chain com prising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phospho- nate group.
  • R a represents a C 10 to C30 alkyl or alkenyl group derived from an acid R a COOH preferably present in hydrolyzed coconut kernel oil, or a heptyl, nonyl or undecyl group;
  • R b represents a b-hydroxyethyl group
  • R c represents a carboxymethyl group
  • - M + represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
  • - X represents an organic or mineral anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C 4 )alkyl sulfates, (Ci-C 4 )alkyl- or (Ci- C 4 )alkylaryl-sulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M + and X- are absent;
  • - B represents the group -CH 2 CH 2 OX’
  • - X represents the group -CH 2 COOH, -CH 2 -COOZ’, -CH 2 CH 2 COOH or CH 2 CH 2 -
  • - Y' represents the group -COOH, -COOZ' or -CH 2 CH(0H)S0 3 H or the group CH 2 CH(0H)S0 3 -Z';
  • - 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 C 10 to C30 alkyl or alkenyl group of an acid R a -COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil, or an alkyl group, in particular a C 17 group, and its iso form, or an unsaturated C 17 group.
  • - Y represents the group -COOH, -COOZ" or -CH 2 -CH(0H)S0 3 H or the group CH 2 CH(0H)S0 3 -Z";
  • R d and R e independently of one another, represent a Ci to 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 C 10 to C30 alkyl or alkenyl group of an acid R a" -COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil;
  • n denote, independently of one another, an integer ranging from 1 to 3.
  • Mention may be made, among the compounds of formula (II), of the compound clas sified in the CTFA dictionary under the name sodium diethylaminopropyl cocoas- partamide and sold by the company Chimex under the name Chimexane HB. These compounds may be used alone or as mixtures.
  • amphoteric or zwitterionic surfactants use is preferably made of (Cs- C2o)alkylbetaines such as cocoylbetaine, (C8-C2o)alkylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof, and the compounds of for mula (IV) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide).
  • amphoteric or zwitterionic surfactants are chosen from (C 8 -C 2 o)al- kylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine.
  • the amphoteric surfactant(s) are present in the washing composition in a total content ranging from 3% to 20% by weight, preferentially in a content ranging from 3.5% to 15% by weight and even better still from 4% to 10% by weight, relative to the total weight of the composition.
  • the cosmetic washing composition may also comprise one or more nonionic sur factants, in particular such as those described in the Handbook of Surfactants by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp 116-178.
  • nonionic surfactants examples include the following com pounds, alone or as a mixture:
  • the oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
  • the number of moles of ethylene oxide and/or of propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol in particular ranges from 1 to 50 and better still from 1 to 10.
  • the nonionic surfactants according to the invention do not comprise any oxypropylene units.
  • they comprise a number of moles of ethylene oxide ranging from 1 to 250, in particular from 2 to 100 and better still from 2 to 50.
  • nonionic surfactant(s) that may be used in the washing composition according to the invention are preferentially chosen, alone or as a mixture, from:
  • - saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide; they preferably include one or two fatty chains;
  • - monoglycerolated or polyglycerolated Cs to C40 alcohols comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol;
  • the nonionic surfactant(s) are chosen, alone or as a mixture, from: - saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and comprising one or two fatty chains, in particular at least one C8-C20 and in particular C10-C18 alkyl chain;
  • the washing composition may comprise one or more nonionic surfac tants of alkyl(poly)glycoside type of general formula:
  • R1 represents a linear or branched alkyl or alkenyl radical comprising 6 to 24 car bon atoms and in particular 8 to 18 carbon atoms, or an alkylphenyl radical of which the linear or branched alkyl radical includes 6 to 24 carbon atoms and in particular 8 to 18 carbon atoms; preferably a saturated or unsaturated, linear or branched alkyl radical comprising from 8 to 18 carbon atoms;
  • R2 represents an alkylene radical comprising 2 to 4 carbon atoms
  • - G represents a sugar unit comprising 5 to 6 carbon atoms; preferably glucose, fructose or galactose; even better still glucose;
  • - 1 denotes a value ranging from 0 to 10, preferably from 0 to 4, better still from 0 to 3 and even better still 0;
  • - v denotes a value ranging from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization (v) 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.
  • the alkyl (poly)glycoside surfactant is an alkyl (poly)glucoside surfactant.
  • the washing composition according to the invention comprises the nonionic surfactant(s), when they are present, in a total content ranging from 0.05% to 15% by weight, preferably from 0.1 % to 10% by weight and preferentially from 0.2% to 5% by weight, relative to the total weight of the washing composition.
  • d Other ingredients
  • the washing composition according to the invention may comprise water or a mix ture of water and one or more cosmetically acceptable solvents chosen from C1-C4 alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glycerol, propylene glycol and polyethylene glycols; and mixtures thereof.
  • the washing composition according to the invention has a total water content of between 20% and 95% by weight, preferably between 30% and 90%, preferentially between 40% and 85% by weight and even better still between 50% and 80% by weight relative to the total weight of the composition.
  • the pH of the washing composition according to the invention generally ranges from 3 to 9, preferably from 3 to 7, preferentially from 3.5 to 6 and better still from 4 to 5.5.
  • the cosmetic washing composition according to the invention may further comprise at least one standard cosmetic ingredient, in particular chosen from polymeric or nonpolymeric conditioning agents; mention may in particular be made of cationic polymers, amphoteric polymers, silicones, organomodified silicones such as amino silicones; plant, mineral, animal or synthetic oils; liquid fatty alcohols; liquid fatty esters; solid fatty substances and in particular waxes, solid fatty esters, solid alco hols; ceram ides; sunscreens; moisturizers; antidandruff agents; antioxidants; pearlescent agents and opacifiers; plasticizers or coalescence agents; preserva- tives; sequestrants (EDTA and salts thereof); colorants.
  • the composition may of course comprise several cosmetic ingredients featured in the above list. Those skilled in the art will take care to select the ingredients making up the composition, and also the amounts thereof, such that the advantageous properties of the compo sition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.
  • composition according to the invention is prepared (% by weight of active material):
  • This composition can be used as a conditioner or as a pre-shampoo.
  • the composition When it is used as a pre-shampoo, the composition is applied to half a head, on medium-long to long wet hair, in a proportion of 10 g per half head. It is left on for 5 minutes and then rinsed off with water.
  • a commercial shampoo (comprising in particular NaLES + cocamidopropylbetaine + cocobetaine + cationic guar + PDMS + amodimethicone) is then applied, to the whole of the head, in a proportion of 16 g per head, and is then rinsed off with water.
  • a commercial conditioner (comprising in particular BETAC and CETAC cationic sur factants + cetearyl alcohol + cetyl esters + amodimethicone) is applied, in a propor tion of 10 g per half head, to the half head that did not receive the pre-shampoo according to the invention, it is left on for 5 minutes and is then rinsed off with water. The hair is then dried with a hairdryer.
  • the hair treated according to the invention is smoother to the touch.
  • the expert evaluates blind, in the following way:
  • the expert evaluates whether (or not) the hair exhibits rough patches, and whether (or not) it catches the fingers, and gives a score, ranging from 0 (very poor) to 5
  • the hair is smooth to the touch and visually more coated, it has a uniform feel, the hair is supple, the strands are more individual, it is easy to disentangle.
  • the hair treated with the invention is significantly smoother to the touch than the hair treated with the comparative composition.
  • Example 2 The following composition B according to the invention and comparative composi tion C were prepared (% by weight of active material AM):
  • a commercial shampoo (comprising in particular NaLES + cocamidopropylbetaine + cocobetaine + cationic guar + PDMS + amodimethicone) is then applied, to the locks, in a proportion of 0.4 g per gram of hair, and is then rinsed off with water and dried in an oven at 60°C.
  • the suppleness evaluation is tactile. The hair is taken in both hands and it is sought to fold it. An evaluation is made of the capacity of the hair to easily curve, its malle ability.
  • the expert takes the lock between the thumb and index finger and slides the fingers along the lock from the upper part to the ends.
  • the expert evaluates whether the hair is soft and supple, whether it exhibits rough patches, whether it catches the figures, and whether it feels uniform.
  • a fine comb is run through the lock from top to bottom. As the comb passes through the lock, the earlier it blocks, the more diffi cult it will be to disentangle the lock.

Abstract

The present invention relates to a hair treatment process comprising: (i) a step of applying, to the hair, a cosmetic care composition comprising: - one or more alkyl(amido) ether carboxylic anionic surfactants, - one or more cationic, preferably associative, polymers, and - one or more organosilanes, and (ii) a step of washing said hair, comprising the application of a cosmetic washing composition comprising one or more anionic surfactants, said steps (i) and (ii) being carried out successively, the time separating said steps (i) and (ii) being at most 60 minutes.

Description

DESCRIPTION
Title of the invention: Hair treatment process
The present invention relates to a process for the cosmetic treatment of the hair, consisting in sequentially applying a cosmetic care composition, in particular hair- care composition, comprising one or more particular anionic surfactants, one or more preferably associative cationic polymers and one or more organosilanes, and a cosmetic washing composition comprising one or more anionic surfactants.
Hair may be damaged or embrittled by the action of external atmospheric agents such as light and bad weather, or by mechanical or chemical treatments, such as brushing, combing, dyeing, bleaching, permanent-waving and/or relaxing. To over- come these drawbacks, it is common practice to make use of hair treatments which can condition the hair. These haircare compositions may be conditioning shampoos or hair conditioners, which may be in the form of gels, hair lotions or more or less thick creams.
To improve the cosmetic properties of these compositions, it is known practice to introduce therein conditioning agents, which are intended mainly to repair or limit the harmful or undesirable effects brought about by the various treatments or at tacking factors to which hair fibers are more or less repeatedly subjected.
With this aim, it has already been proposed to use, inter alia, organosilanes in cos metic care compositions, to give hair satisfactory conditioning properties. Such com- positions are described, for example, in patent applications FR 2910276, EP 2343042 and EP 2111848.
However, the care compositions described in these documents afford conditioning and disentangling properties that are not sufficiently long-lasting. Specifically, these properties generally do not sufficiently resist washing and tend to diminish from the first shampoo wash. In other words, even though these haircare compositions make it possible to obtain suitable results during and just after their use (at TO), it was found that these effects had a tendency to disappear gradually with hair washes; it was thus necessary to regularly renew the application of hair treatments to maintain adequate conditioning effects.
Application WO 2016/083578 has therefore proposed a hair composition for caring for the hair, capable of affording conditioning properties which are not only satisfac tory, but also persistent with respect to washing, for example persistent at least after three shampoo washes. This care composition comprises the combination of orga- nosilanes, cationic polymers of high charge density and cationic surfactants; it can confer on the hair a cosmetic care that is persistent with respect to shampoo washes, in particular softness, suppleness, smoothness, lightness, volume, and a non-greasy and non-laden natural feel. This composition also provides hair with im proved disentangling ability. These properties show good resistance to the various attacking factors to which hair may be subjected, such as light, bad weather, wash ing and perspiration. They are particularly persistent with respect to shampoo wash- ing, especially after at least three shampoo washes.
A hair treatment process comprising the sequential application of a composition comprising organosilanes and of a composition for caring for or washing the hair has also been proposed, for example by EP 2111849. This document describes in particular the use of a composition comprising an organosilane as a pre-shampoo, that is to say applied to the hair before washing with a shampoo comprising at least one anionic surfactant and an amphoteric surfactant. This process makes it possible in particular to obtain supple, smooth hair which disentangles well.
Mention may also be made, in the prior art, of FR 3060369 which describes a hair treatment process wherein, firstly, a care composition containing 3-aminopropyltri- ethoxysilane and polyquaterniun-6 is applied to the hair, then the hair is washed with a shampoo containing laureth-5 carboxylic acid. The care composition does not contain a surfactant of alkyl(amido) ether carboxylic type. However, it is still possible to improve the performance results provided by care or shampoo compositions, in particular the cosmetic properties, such as disentangling and smoothness to the touch, and also individual strand separation; this being im mediately, at the time of application of the composition to the hair (at TO), but also persistently, that is to say after several shampoo washes, for example persistence after 2 to 4 shampoo washes.
The care composition according to the invention has improved use qualities, in par ticular facilitated distribution on the hair, and improved rinsing.
At the end of the process according to the invention, the individual strands of the hair are more separated, and the hair is smooth to the touch and disentangles easily; it is easier to style.
These cosmetic properties are persistent with respect to subsequent shampoo washing, this being up to 3 shampoo washes, without having to reapply the pre shampoo.
A subject of the present invention is thus a hair treatment process comprising:
(i) a step of applying, to the hair, a cosmetic care composition comprising:
- one or more alkyl(amido) ether carboxylic anionic surfactants,
- one or more cationic, preferably associative, polymers, and - one or more organosilanes, and
(ii) a step of washing said hair, comprising the application of a cosmetic washing composition comprising one or more anionic surfactants, said steps (i) and (ii) being carried out successively, the time separating said steps (i) and (ii) being at most 60 minutes.
The term “successively” or “sequentially” is intended to mean that the two steps are not carried out at the same time, but that one precedes the other; step (i) may be before or after step (ii).
Thus, the care step (i) can precede the washing step (ii), it being understood that the step (ii) of washing the hair is carried out at most 60 minutes after the care step (i); in this embodiment, the care composition of step (i) can be considered to be a pre-shampoo. The care step (i) can also follow the washing step (ii), it being understood that the care step (i) is carried out at most 60 minutes after the washing step (ii); in this embodiment, the care composition of step (i) can be considered to be a conditioner.
Thus, according to a first embodiment, the hair treatment process according to the invention comprises:
(i) a step of applying, to the hair, a cosmetic care composition comprising:
- one or more alkyl(amido) ether carboxylic anionic surfactants,
- one or more cationic, preferably associative, polymers, and
- one or more organosilanes, followed (ii) by a step of washing said hair, comprising the application of a cosmetic washing composition comprising one or more anionic surfactants, said step (ii) of washing the hair being carried out at most 60 minutes after said step
(i).
According to this embodiment, the care composition used in step (i) is a pre-sham- poo composition.
According to a second embodiment, the hair treatment process according to the invention comprises:
(ii) a step of washing said hair, comprising the application of a cosmetic washing composition comprising one or more anionic surfactants, followed
(i) by a step of applying, to the hair, a cosmetic care composition comprising:
- one or more alkyl(amido) ether carboxylic anionic surfactants,
- one or more cationic, preferably associative, polymers, and
- one or more organosilanes, said step (i) being carried out at most 60 minutes after said step (ii) of washing the hair.
According to this embodiment, the care composition used in step (i) is a conditioner composition. The hair treatment process according to the invention thus comprises a step (i) that consists in applying to the hair a cosmetic care composition as defined below. This step may or may not be followed by a leave-on step, for example a leave-on time of from 1 to 15 minutes, in particular 2 to 5 minutes. This step may also be optionally followed by a rinsing step, for example rinsing with water. Preferably, said step (i) is followed by a rinsing step. Preferably, the process according to the invention com prises an intermediate rinsing step between steps (i) and (ii), in particular when the care step (i) precedes the washing step (ii). The process according to the invention can also comprise an intermediate rinsing step between steps (i) and (ii), when the care step (i) follows the washing step (ii).
The hair treatment process according to the invention also comprises a washing step (ii) that consists in applying to the hair a cosmetic washing composition as de- fined below.
This step may or may not be followed by a leave-on step, for example a leave-on time of from 1 to 15 minutes, in particular 2 to 5 minutes. It can also be optionally followed by a rinsing step, for example rinsing with water; and/or by a drying step, in particular in the case where step (i) precedes the washing step (ii). Preferably, said washing step (ii) is followed by a rinsing step and optionally by a drying step.
The step of applying (i) the care composition and the washing step (ii) are carried out successively, or sequentially, which means that one of the application steps is prior to the other application step; it being possible for intermediate steps, for exam- pie leave-on and/or rinsing and/or drying steps, to be present between these two steps.
Preferably, the application step (i) is carried out before the washing step (ii).
The time separating said step (i) of applying the care composition and the step (ii) of washing the hair is at most 60 minutes; it may for example be between 30 seconds and 60 minutes, in particular between 1 and 30 minutes, or even between 2 and 20 minutes, even better still between 3 and 15 minutes, and most particularly between 4 and 10 minutes. In the present description, the term “care composition” denotes a composition which provides haircare, in particular conditioning; it is a cosmetic composition and is in no way a pharmaceutical composition. This composition can also be called a pre shampoo or conditioner, depending on whether it is applied before or after the wash ing step (the shampoo washing).
In the present description, the expression “at least one” is equivalent to the expres sion “one or more” and can be substituted for said expression; the expression “be tween ... and” is equivalent to the expression “ranging from ... to” and can be sub stituted for said expression, and implies that the limits are included.
A / Care composition
The hair treatment process according to the invention thus comprises a step (i) con sisting in applying to the hair a cosmetic care composition comprising one or more particular anionic surfactants, one or more cationic polymers and one or more orga- nosilanes. a) Alkyl(amido) ether carboxylic acid anionic surfactants
The cosmetic care composition according to the present invention comprises one or more alkyl(amido) ether carboxylic anionic surfactants.
The term “anionic surfactant” is intended to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups.
In the present description, a species is termed as being “anionic” when it bears at least one permanent negative charge or when it can be ionized as a negatively charged species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.
The anionic surfactants are chosen from alkyl(amido) ether carboxylic acids (or car- boxylates) and/or salts thereof. They can be chosen from the following compounds, alone or as a mixture: alkyl ether carboxylic acids, alkyl(C6-C3o aryl) ether carboxylic acids, alkylamido ether carboxylic acids, and also the salts of these compounds; the alkyl and/or acyl groups of these compounds comprising from 6 to 30 carbon atoms, especially from 12 to 28, even better still from 14 to 24, or even from 16 to 22, carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these com pounds possibly being polyoxyalkylenated, especially polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units, better still from 2 to 10 ethylene oxide units.
The polyoxyalkylenated alkyl(amido) ether carboxylic acids that may be used are preferably chosen from those of formula (I) below:
Ri-(OC2H4)n-OCH2COOA wherein:
- Ri represents a linear or branched C6-C24 alkyl or alkenyl radical, a (C8-C9)al- kylphenyl radical, a radical R2CONH-CH2-CH2- with R2 denoting a linear or branched C9-C21 alkyl or alkenyl radical; preferably, Ri is a C8-C20, preferably Cs- C18, alkyl radical,
- n is an integer or decimal number (mean value) ranging from 2 to 24, preferably from 2 to 10,
- A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue.
Use may also be made of mixtures of compounds of formula (I), in particular mix tures of compounds bearing different groups Ri.
The polyoxyalkylenated alkyl(amido) ether carboxylic acids that are particularly pre ferred are those of formula (I) wherein:
- Ri denotes a C8-C22, in particular C10-C16, or even C12-C14, alkyl radical, or alternatively a (C8-C9)alkylphenyl radical;
- A denotes a hydrogen or sodium atom, and
- n ranges from 2 to 20, preferably from 2 to 10.
Even more preferentially, use is made of the compounds of formula (I) wherein Ri denotes a C12-C14 alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical; A denotes a hydrogen or sodium atom and n ranges from 2 to 10.
When the anionic surfactant is in salt form, said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magne sium salt. Examples of amino alcohol salts that may be mentioned include monoeth- anolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2-amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)amino- methane salts. Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
Among the commercial products, use may preferably be made of the products sold by the company KAO under the names: Akypo® NP 70 (Ri = nonylphenyl, n = 7, A = H),
Akypo® NP 40 (Ri = nonylphenyl, n = 4, A = H),
Akypo® OP 40 (Ri = octylphenyl, n = 4, A = H),
Akypo® OP 80 (Ri = octylphenyl, n = 8, A = H),
Akypo® OP 190 (Ri = octylphenyl, n = 19, A = H), Akypo® RLM 38 (Ri = (Ci2-Cu)alkyl, n = 4, A = H),
Akypo® RLM 38 NV (Ri = (Ci2-Cu)alkyl, n = 4, A = Na),
Akypo® RLM 45 CA (Ri = (Ci2-Cu)alkyl, n = 4.5, A = H),
Akypo® RLM 45 NV (Ri = (Ci2-Cu)alkyl, n = 4.5, A = Na),
Akypo® RLM 100 (Ri = (Ci2-Cu)alkyl, n = 10, A = H), Akypo® RLM 100 NV (Ri = (Ci2-Cu)alkyl, n = 10, A = Na),
Akypo® RLM 130 (Ri = (Ci2-Cu)alkyl, n = 13, A = H),
Akypo® RLM 160 NV (Ri = (Ci2-Cu)alkyl, n = 16, A = Na), or by the company Sandoz under the names:
Sandopan DTC-Acid (Ri = (Ci3)alkyl, n = 6, A = H), Sandopan DTC (Ri = (Ci3)alkyl, n = 6, A = Na),
Sandopan LS 24 (Ri = (Ci2-Cu)alkyl, n = 12, A = Na),
Sandopan JA 36 (Ri = (Ci3)alkyl, n = 18, A = H), and more particularly the products sold under the following names:
Akypo® RLM 45 (INCI: Laureth-5 carboxylic acid), Akypo® RLM 100, and Akypo® RLM 38.
Preferentially, the anionic surfactants are chosen, alone or as a mixture, from: - (C6-C24)alkyl ether carboxylic acids and in particular (C12-C20)alkyl ether carbox ylic acids, and salts thereof;
- polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids, in particular those comprising from 1 to 50, in particular from 2 to 10, ethylene oxide groups; and salts thereof; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.
Preferably, the composition comprises said alkyl(amido) ether carboxylic anionic surfactant(s) in a total content ranging from 0.5% to 12% by weight, better still from 1 % to 10% by weight, preferentially from 1.5% to 8% by weight, even better still from 2% to 7% by weight, relative to the total weight of the composition.
The composition according to the invention can optionally comprise one or more additional anionic surfactants, different than the anionic surfactants described above. Preferably, it does not comprise any additional anionic surfactants. b / Cationic polymers
The cosmetic care composition comprises one or more cationic, preferably associ- ative, polymers.
The term “cationic polymer” is intended to mean any nonsilicone polymer (polymer not comprising any silicon atoms) containing cationic groups and/or groups that can be ionized into cationic groups and not containing any anionic groups and/or groups that can be ionized into anionic groups.
The cationic polymers that can be used preferably have a cationic charge density greater than or equal to 4 milliequivalents/gram (meq/g), better still greater than or equal to 5 meq/g, or even ranging from 5 to 20 meq/g. The cationic charge density of a polymer corresponds to the number of moles of cationic charges per unit mass of polymer under conditions in which it is totally ion ized. It may be determined by calculation if the structure of the polymer is known, i.e. the structure of the monomers constituting the polymer and their molar propor tion or weight proportion. It may also be determined experimentally by the Kjeldahl method.
The cationic polymers that may be used preferably have a weight-average molar mass (Mw) of between 500 and 5*106 approximately, preferably between 103 and 3x106 approximately.
The cationic polymers that can be used may be associative or nonassociative.
The term “associative polymer” is intended to mean an amphiphilic polymer that is capable, in an aqueous medium, of reversibly combining with itself or with other molecules. It generally includes, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group. In particular, the hy drophobic group may be a fatty hydrocarbon-based chain such as a linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl group comprising at least 8 carbon atoms, preferably 8 to 30 carbon atoms, better still from 12 to 24 carbon atoms.
Among the cationic polymers, mention may be made of:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or am- ides and comprising at least one of the units having the following formula:
Figure imgf000009_0001
wherein: - R3, which may be identical or different, denote a hydrogen atom or a CH3 radical;
- A, which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;
- R4, R5 and R6, which may be identical or different, represent an alkyl group con- taining from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group con taining from 1 to 6 carbon atoms;
- R1 and R2, which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
- X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
The copolymers of family (1) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitro- gen with lower (C1-C4) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Among these copolymers of family (1), mention may be made of:
- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as that sold under the name Hercofloc by the company Hercules,
- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chlo ride, such as those sold under the name Bina Quat P 100 by the company Ciba Geigy, - the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, such as that sold under the name Reten by the company Hercules,
- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the products known as Copolymer 845, 958 and 937,
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP,
- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as those sold under the name Styleze CC 10 by ISP, - quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, such as the product sold under the name Gafquat HS 100 by the company ISP, - preferably crosslinked polymers of methacryloyloxy(C1-C4)alkyltri(C1-C4)al- kylammonium salts, such as the polymers obtained by homopolymerization of dime thylaminoethyl methacrylate quaternized with methyl chloride, or by copolymeriza- tion of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. Use may be made more particularly of a crosslinked acrylamide/methacryloyloxy- ethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dis- persion comprising 50% by weight of said copolymer in mineral oil. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopoly mer comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba;
(2) cationic polysaccharides, in particular cationic galactomannan gums and cellu loses. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cel- lulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
The cellulose ether derivatives comprising quaternary ammonium groups are in par ticular described in FR 1492597, and mention may be made of the polymers sold under the name Ucare Polymer JR (JR 400 LT, JR 125 and JR 30M) or LR (LR 400 and LR 30M) by the company Amerchol. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have re acted with an epoxide substituted with a trimethylammonium group. The cationic cellulose copolymers or cellulose derivatives grafted with a water-sol uble quaternary ammonium monomer are described in particular in patent US 4131576, and mention may be made of hydroxyalkyl celluloses, for instance hy droxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this defi nition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.
The cationic galactomannan gums are described more particularly in patents US 3589578 and US 4031307, and mention may be made of guar gums comprising cationic trialkylammonium groups. Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrirnethylammonium salt (for example, a chloride). Such prod ucts are in particular sold under the names Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 by the company Rhodia;
(3) polymers constituted of piperazinyl units and of divalent alkylene or hydroxy- alkylene radicals bearing linear or branched chains, optionally interrupted with oxy gen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers;
(4) water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldia- mine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a bifunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-un- saturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides can be alkylated or, if they include one or more tertiary amine functions, they can be quaternized;
(5) polyaminoamide derivatives resulting from the condensation of polyalkylene pol yamines with polycarboxyl ic acids followed by alkylation with bifunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldial- kylenetriamine polymers wherein the alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/di- ethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the com- pany Sandoz;
(6) polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid cho sen from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms; the mole ratio between the polyalkylene polyamine and the di carboxylic acid preferably being between 0.8:1 and 1.4:1 ; the resulting polyamino- amide being reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide preferably of between 0.5:1 and 1.8:1. Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or else under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer;
(7) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the ho mopolymers or copolymers comprising, as main constituent of the chain, units cor responding to formula (I) or (II):
Figure imgf000012_0001
wherein
- k and t are equal to 0 or 1 , the sum k + t being equal to 1 ;
- R12 denotes a hydrogen atom or a methyl radical; - R10 and R11 , independently of one another, denote a C1 -C6 alkyl group, a C1 -C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively R10 and R11 may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R10 and R11 , independently of one an other, preferably denote a C1-C4 alkyl group; - Y is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
Mention may be made more particularly of the homopolymer of dimethyldial- lylammonium salts (for example chloride) for example sold under the name Mer- quat 100 by the company Nalco and the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide, in particular sold under the name Merquat 550 or Merquat 7SPR;
(8) quaternary diammonium polymers comprising repeating units of formula:
Figure imgf000013_0001
wherein:
- R13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals, or else R13, R14, R15 and R16, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non nitrogen heteroatom; or else R13, R14, R15 and R16 represent a linear or branched C1 -C6 alkyl radical substituted with a nitrile, ester, acyl, amide or -C0-0-R17-D or -CO-NH-R17-D group, where R17 is an alkylene and D is a quaternary ammonium group;
- A1 and B1 represent linear or branched, saturated or unsaturated, divalent polymethylene groups comprising from 2 to 20 carbon atoms, which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hy droxyl, quaternary ammonium, ureido, amide or ester groups, and
- X denotes an anion derived from a mineral or organic acid; it being understood that A1 , R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH2)n-CO-D-OC-(CH2)p- with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting: a) a glycol residue of formula -0-Z-0-, wherein Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the follow ing formulae: -(CH2CH20)x-CH2CH2- and -[CH2CH(CH3)0]y-CH2CH(CH3)-, wherein x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue, such as a piperazine derivative; c) a bis-primary diamine residue of formula -NH-Y-NH-, wherein Y denotes a linear or branched hydrocarbon-based radical, or else the divalent radical -CH2- CH2-S-S-CH2-CH2-; d) a ureylene group of formula -NH-CO-NH-. Preferably, X- is an anion, such as chloride or bromide. These polymers have a number-average molar mass (Mn) generally of between 1000 and 100 000.
Mention may be made more particularly of polymers that are constituted of repeating units corresponding to the formula: wherein R1 , R2, R3 and R4, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers rang ing from 2 to 20, and X- is an anion derived from a mineral or organic acid. A particularly preferred compound of formula (IV) is the one for which R1, R2, R3 and R4 represent a methyl radical, n = 3, p = 6 and X = Cl, known as Flexadime- thrine chloride according to the INCI (CTFA) nomenclature;
(9) polyquaternary ammonium polymers comprising units of formula (V):
Figure imgf000014_0001
wherein:
- R18, R19, R20 and R21, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, b-hydroxyethyl, b-hydroxypropyl or - CH2CH2(OCH2CH2)pOH radical, wherein p is equal to 0 or to an integer between 1 and 6, with the proviso that R18, R19, R20 and R21 do not simultaneously repre sent a hydrogen atom,
- r and s, which may be identical or different, are integers between 1 and 6,
- q is equal to 0 or to an integer between 1 and 34,
- X- denotes an anion such as a halide, - A denotes a divalent dihalide radical or preferably represents -CH2-CH2-0-CH2-
CH2-;
Examples that may be mentioned include the products Mirapol® A 15, Mirapol® AD1 , Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol; (10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the com pany BASF;
(11) polyamines such as Polyquart® FI sold by Cognis, referred to under the name Polyethylene glycol (15) tallow polyamine in the CTFA dictionary;
(12) polymers comprising in their structure:
(a) one or more units corresponding to formula (A) below: (b) optionally one or more units corresponding to formula (B) below:
Figure imgf000015_0001
In other words, these polymers may be in particular chosen from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
Preferably, these cationic polymers are chosen from polymers comprising, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to
100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).
These polymers may be obtained, for example, by partial hydrolysis of polyvinylfor- mamide. This hydrolysis may take place in acidic or basic medium. The weight-average molecular weight of said polymer, measured by light scattering, may range from 1000 to 3000000 g/mol, preferably from 10000 to 1 000000 and more particularly from 100000 to 500000 g/mol.
The polymers comprising units of formula (A) and optionally units of formula (B) are in particular sold under the name Lupamin by the company BASF, for instance, in a non-limiting manner, the products provided under the names Lupamin 9095, Lu pamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
Cationic polymers chosen from those of families (1), (2), (7) and (10) mentioned above are most particularly preferred, better still those of families (1), (7) and (10).
Among the associative cationic polymers that may be used, mention may be made, alone or as a mixture, of:
- (A) cationic associative polyurethanes, which can be represented by general for mula (la) below: R-X-(P)n-[L-(Y)m]r-L'-(P')p-X'-R' wherein:
R and R’, which may be identical or different, represent a hydrophobic group or a hydrogen atom;
X and X’, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively the group L”; L, L’ and L”, which may be identical or different, represent a group derived from a diisocyanate;
P and P’, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group; Y represents a hydrophilic group; r is an integer between 1 and 100 inclusive, preferably between 1 and 50 inclusive and in particular between 1 and 25 inclusive; n, m and p are each, independently of one another, between 0 and 1000 inclusive; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
Preferably, the only hydrophobic groups are the groups R and R’ at the chain ends. One preferred family of cationic associative polyurethanes is the one corresponding to formula (la) described above, wherein:
R and R’ both independently represent a hydrophobic group,
X and X’ each represent a group L”, n and p are integers that are between 1 and 1000 inclusive, and L, L', L", P, P', Y and m have the meaning indicated above.
Another preferred family of cationic associative polyurethanes is the one corre sponding to formula (la) above wherein:
- n = p = 0 (the polymers do not include any units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation),
- the protonated amine functions result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R’Q, wherein R and R’ are as defined above and Q denotes a leaving group such as a halide or a sulfate.
Yet another preferred family of cationic associative polyurethanes is the one corre sponding to formula (la) above wherein:
R and R’ both independently represent a hydrophobic group, X and X’ both independently represent a group comprising a quaternary amine, n = p = 0, and
L, L’, Y and m have the meaning given above.
The number-average molecular weight (Mn) of the cationic associative polyure thanes is preferably between 400 and 500000 inclusive, in particular between 1000 and 400000 inclusive and ideally between 1000 and 300000 inclusive.
The term “hydrophobic group” is intended to mean a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain. When it denotes a hydrocarbon-based radical, the hy- drophobic group includes at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms. Preferentially, the hydrocarbon-based group is derived from a monofunctional com pound.
By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocar- bon-based polymer, for instance polybutadiene.
When X and/or X’ denote(s) a group comprising a tertiary or quaternary amine, X and/or X’ may represent one of the following formulae:
Figure imgf000017_0001
wherein:
R2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P; R1 and R3, which may be identical or different, denote a linear or branched C1-C30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
A- is a physiologically acceptable anionic counterion such as a halide, for instance a chloride or bromide, or a mesylate.
The groups L, U and L” represent a group of formula:
Figure imgf000017_0002
wherein: Z represents -0-, -S- or -NH-; and
R4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P.
The groups P and P’ comprising an amine function may represent at least one of the following formulae: wherein:
R5 and R7 have the same meanings as R2 defined above; R6, R8 and R9 have the same meanings as R1 and R3 defined above;
R10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, 0, S and P; and A- is a physiologically acceptable anionic counterion such as a halide, for in stance chloride or bromide, or mesylate.
As regards the meaning of Y, the term “hydrophilic group” is intended to mean a polymeric or non-polymeric water-soluble group.
By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol. When it is a hydrophilic polymer, in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers. The hydrophilic compound is preferen tially a polyether and in particular a poly(ethylene oxide) or polypropylene oxide). The cationic associative polyurethanes of formula (la) according to the invention are formed from diisocyanates and from various compounds bearing functions contain ing labile hydrogen. The functions containing labile hydrogen may be alcohol, pri mary or secondary amine or thiol functions, giving, after reaction with the diisocya nate functions, polyurethanes, polyureas and polythioureas, respectively. In the pre- sent invention, the term “polyurethanes” encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
A first type of compound involved in the preparation of the polyurethane of formula (la) is a compound comprising at least one unit bearing an amine function. This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to a preferential embodiment, this compound includes two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, sec ondary amine or thiol function. A mixture of multifunctional and difunctional com pounds wherein the percentage of multifunctional compounds is low may also be used.
As mentioned above, this compound may include more than one unit containing an amine function. In this case, it is a polymer bearing a repetition of the unit containing an amine function.
Compounds of this type may be represented by one of the following formulae: HZ-(P)n-ZH, or HZ-(P')p-ZH, wherein Z, P, P’, n and p are as defined above. Examples that may be mentioned include N-methyldiethanolamine, N-tert-butyldi- ethanolamine and N-sulfoethyldiethanolamine.
The second compound included in the preparation of the polyurethane of formula (la) is a diisocyanate corresponding to the formula:
0=C=N-R4-N=C=0 wherein R4 is defined above.
By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, tolulene diisocya nate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
A third compound involved in the preparation of the polyurethane of formula (la) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (la).
This compound is formed form a hydrophobic group and a function containing labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
By way of example, this compound may be a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound includes a polymeric chain, it may be, for example, a-hydroxylated hydrogenated polybutadiene.
The hydrophobic group of the polyurethane of formula (la) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quater- nizing agent. This quaternizing agent is a compound of the type RQ or R’Q, wherein R and R’ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture wherein the percentage of multifunctional compound is low.
The functions containing labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing labile hydrogen. By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or polypropylene oxide).
The hydrophilic group termed Y in formula (la) is optional. Specifically, the units containing a quaternary or protonated amine function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solu- tion.
Although the presence of a hydrophilic group Y is optional, cationic associative pol yurethanes comprising such a group are, however, preferred.
- (B) quaternized cellulose derivatives, and in particular quaternized celluloses mod- ified with groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyl groups, or linear or branched alkylaryl groups, preferably linear or branched alkyl groups, these groups comprising at least 8 car bon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof. Preferably, mention may be made of quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyl groups, or linear or branched alkylaryl groups, preferably linear or branched alkyl groups, these groups comprising at least 8 car bon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof.
Preferentially, mention may be made of the hydroxyethylcelluloses of formula (lb):
Figure imgf000020_0001
wherein: - R represents an ammonium group RaRbRcN+-, Q- wherein Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched C1- C30 alkyl, and Q- represents an anionic counterion such as a halide, for instance a chloride or bromide; preferably an alkyl;
- R’ represents an ammonium group R’aR’bR’cN+-, Q’- wherein R’a, R’b and R’c, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C30 alkyl, and Q’- represents an anionic counterion such as a halide, for instance a chloride or bromide; preferably an alkyl; it being understood that at least one of the radicals Ra, Rb, Rc, R'a, R'b and R'c represents a linear or branched C8-C30 alkyl;
- n, x and y, which may be identical or different, represent an integer between 1 and 10 000.
Preferably, in formula (lb), at least one of the radicals Ra, Rb, Rc, R'a, R'b and R'c represents a linear or branched C8-C30, better still C10-C24, or even C10-C14, alkyl; mention may be made in particular of the dodecyl radical (C12). Preferably, the other radical(s) represent a linear or branched C1-C4 alkyl, in particular methyl. Preferably, in formula (lb), only one of the radicals Ra, Rb, Rc, R'a, R'b and R'c represents a linear or branched C8-C30, better still C10-C24, or even C10-C14, alkyl; mention may be made in particular of the dodecyl radical (C12). Preferably, the other radicals represent a linear or branched C1-C4 alkyl, in particular methyl. Even better still, R may be a group chosen from -N+(CH3)3, Q1 and - N+(Ci2H25)(CH3)2, Q1 , preferably an -N+(CH3)3, Q1 group.
Even better still, R' may be a group -N+(Ci2H25)(CH3)2, Q1 .
The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
Mention may notably be made of the polymers having the following INCI names:
- Polyquaternium-24, such as the product Quatrisoft LM 200®, sold by the company Amerchol/Dow Chemical;
- PG-Hydroxyethylcellulose Cocodimonium Chloride, such as the product Crodacel QM®;
- PG-Hydroxyethylcellulose Lauryldimonium Chloride (C12 alkyl), such as the prod uct Crodacel QL®; and
- PG-Hydroxyethylcellulose Stearyldimonium Chloride (C18 alkyl), such as the prod uct Crodacel QS®, sold by the company Croda.
Mention may also be made of the hydroxyethylcelluloses of formula (lb) wherein R represents a trimethylammonium halide and R' represents a dimethyldodecylammo- nium halide; preferentially, R represents trimethylammonium chloride (CH3)3N+-, Cl- and R’ represents dimethyldodecylammonium chloride (CH3)2(C12H25)N+-, Cl- . This type of polymer is known under the INCI name Polyquaternium-67; as com mercial products, mention may be made of the Softcat Polymer SL® polymers, such as SL-100, SL-60, SL-30 and SL-5, from the company Amerchol/Dow Chemical.
More particularly, the polymers of formula (lb) are those of which the viscosity is between 2000 and 3000 cPs inclusive, preferentially between 2700 and 2800 cPs. Typically, Softcat Polymer SL-5 has a viscosity of 2500 cPs, Softcat Polymer SL-30 has a viscosity of 2700 cPs, Softcat Polymer SL-60 has a viscosity of 2700 cPs and Softcat Polymer SL-100 has a viscosity of 2800 cPs. - (C) cationic polyvinyllactams, in particular those comprising:
-a) at least one monomer of vinyllactam or alkylvinyllactam type; -b) at least one monomer of structure (lc) or (lie) below:
Figure imgf000022_0001
(lie) R4 wherein:
- X denotes an oxygen atom or an NR6 radical,
- R1 and R6 denote, independently of one another, a hydrogen atom or a linear or branched C1-C5 alkyl radical,
- R2 denotes a linear or branched C1-C4 alkyl radical, - R3, R4 and R5 denote, independently of one another, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (lllc):
- (Y2)— (CH2-CH{R7)-0)— R8 (lllc)
- Y, Y1 and Y2 denote, independently of one another, a linear or branched C2-C16 alkylene radical, - R7 denotes a hydrogen atom, or a linear or branched C1 -C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical,
- R8 denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical,
- p, q and r denote, independently of one another, 0 or 1 ,
- m and n denote, independently of one another, an integer ranging from 0 to 100 inclusive,
- x denotes an integer ranging from 1 to 100 inclusive,
- Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate; with the proviso that: - at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9-
C30 alkyl radical,
- if m and/or n is other than zero, then q is equal to 1 ,
- if m = n = 0, then p or q is equal to 0. The cationic poly(vinyllactam) polymers according to the invention may be cross- linked or non-crosslinked and may also be block polymers.
Preferably, the counterion Z- of the monomers of formula (lc) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion. Preferably, R3, R4 and R5 denote, independently of one another, a hydrogen atom or a linear or branched C1-C30 alkyl radical.
More preferentially, the monomer b) is a monomer of formula (lc) for which, prefer entially, m and n are equal to zero.
The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc):
Figure imgf000023_0001
wherein:
- s denotes an integer ranging from 3 to 6,
- R9 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical,
- R10 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical, with the proviso that at least one of the radicals R9 and R10 denotes a hydrogen atom.
Even more preferentially, the monomer (IVc) is vinylpyrrolidone.
The cationic poly(vinyllactam) polymers according to the invention may also contain one or more additional monomers, preferably cationic or nonionic monomers.
As compounds that are particularly preferred, mention may be made of the following terpolymers comprising at least: a) one monomer of formula (IVc), b) a monomer of formula (lc) wherein p = 1 , m = n = q = 0, R3 and R4 denote, independently of one another, a hydrogen atom or a C1-C5 alkyl radical and R5 denotes a linear or branched C9-C24 alkyl radical, and c) a monomer of formula (lie) wherein p = 1 , m = n = q = 0, and R3 and R4 denote, independently of one another, a hydrogen atom or a linear or branched C1-C5 alkyl radical.
Even more preferentially, terpolymers comprising, by weight, 40% to 95% of mono mer (a), 0.1 % to 55% of monomer (c) and 0.25% to 50% of monomer (b) will be used. Such polymers are in particular described in patent application WO-OO/68282.
As cationic polymer(vinyllactam) polymers according to the invention, the following are in particular used: vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethac- rylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethac- rylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethac- rylamidopropylammonium tosylate or chloride terpolymers. The vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethac- rylamidopropylammonium chloride terpolymer is in particular sold by the company ISP under the names Styleze W10® and Styleze W20L® (INCI name: Polyquater- nium-55).
The weight-average molecular weight (Mw) of the cationic poly(vinyllactam) poly mers is preferably between 500 and 20000000, more particularly between 200000 and 2000000 and preferentially between 400000 and 800000. - (D) the cationic polymers obtained by polymerization of a monomer mixture com prising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers, and one or more associative vinyl monomers, as described in patent application WO 2004/024779.
Among these copolymers, mention may be made more particularly of the products of the polymerization of a monomer mixture comprising:
- a di(C1-C4 alkyl)amino(C1-C6 alkyl) methacrylate,
- one or more C1-C30 alkyl esters of (meth)acrylic acid,
- a polyethoxylated C10-C30 alkyl methacrylate (20-25 mol of ethylene oxide unit),
- a 30/5 polyethylene glycol/polypropylene glycol allyl ether, - a hydroxy(C2-C6 alkyl) methacrylate, and
- an ethylene glycol dimethacrylate.
Such a polymer is, for example, the compound sold by the company Lubrizol under the name Carbopol Aqua CC® and which corresponds to the INCI name Polyacry- late-1 crosspolymer.
Preferably, the associative or nonassociative cationic polymers that can be used in the context of the invention are chosen, alone or as a mixture, from:
- alkyldiallylamine or dialkyldiallylammonium cyclopolymers, and in particular homo polymers or copolymers of dimethyldiallylammonium salts (for example chloride); - optionally crosslinked homopolymers or copolymers of methacryloyloxy(C1 -C4)al- kyltri(C1 -C4)alkylammonium salts;
- quaternary polymers of vinylpyrrolidone and of vinylimidazole;
- the cationic polymers (B) derived from quaternized cellulose, and the hydroxyeth- ylcelluloses of formula (lb) above.
Better still, the cationic polymers are chosen from associative cationic polymers, preferentially from the cationic polymers (B) derived from quaternized cellulose, and the hydroxyethylcelluloses of formula (lb) above. Preferentially, the cationic polymers are chosen from the hydroxyethylcelluloses of formula (lb) above, in particular those for which R represents a trimethylammonium halide and R' represents a dimethyldodecylammonium halide, preferentially R rep- resents a trimethylammonium chloride (CH ) N+-, Cl and R’ represents a dimethyl- dodecylammonium chloride (CH ) (Ci H )N+-, Cl , which corresponds to Polyqua- ternium-67. The care composition according to the invention may comprise the cationic poly mers) in a total amount of between 0.1% and 8% by weight, in particular from 0.2% to 5% by weight, preferentially from 0.3% to 2% by weight and even better still from 0.4% to 1.4% by weight, relative to the total weight of the composition. The care composition according to the invention may comprise the associative cat ionic polymer(s) in a total amount of between 0.1% and 8% by weight, in particular from 0.2% to 5% by weight, preferentially from 0.3% to 2% by weight and even better still from 0.4% to 1.4% by weight, relative to the total weight of the composition. Preferably, the weight ratio between the total amount of anionic surfactants and the total amount of cationic polymers present in the care composition is less than or equal to 6, better still less than or equal to 5.5, even better still less than or equal to 5, or even less than or equal to 4.5.
Preferably, the weight ratio between the total amount of alkyl(amido) ether carbox- ylic anionic surfactants and the total amount of associative cationic polymers pre sent in the care composition is less than or equal to 6, better still less than or equal to 5.5, even better still less than or equal to 5, or even less than or equal to 4.5. cl Orqanosilanes The care composition according to the invention comprises one or more orga- nosilanes, preferably chosen from the compounds of formula (II) and/or oligomers thereof and/or hydrolysis products thereof:
R1Si(OR2)z(R3)x(OH)y (II) wherein: - R1 is a cyclic or acyclic, linear or branched, saturated or unsaturated C1-C22, in particular C2-C20, hydrocarbon-based chain, which may be substituted with a group chosen from amine groups NH2 or NHR (R being a linear or branched C1-C20, in particular C1-C6, alkyl, or a C3-C40 cycloalkyl or a C6-C30 aromatic radical); the hydroxyl group (OH), a thiol group, an aryl group (more particularly benzyl), which is possibly substituted with an NH2 or NHR group; it being possible for R1 to be interrupted with a heteroatom (O, S or NH) or a carbonyl group (CO),
- R2 and R3, which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms,
- y denotes an integer ranging from 0 to 3, - z denotes an integer ranging from 0 to 3, and
- x denotes an integer ranging from 0 to 2, with z + x + y = 3, The term “oligomer” is intended to mean the polymerization products of the com pounds of formula (II) comprising from 2 to 10 silicon atoms.
Preferably, R1 is a linear or branched, preferably linear, saturated C1 -C22, in par ticular C1-C12, hydrocarbon-based chain, which may be substituted with an amine group NH2 or NHR (R = C1-C20, in particular C1-C6, alkyl).
Preferably, R2 represents an alkyl group comprising from 1 to 4 carbon atoms, bet ter still a linear alkyl group comprising from 1 to 4 carbon atoms, and preferably the ethyl group.
Preferably, z ranges from 1 to 3.
Preferably, y = 0.
Preferentially, z = 3, and therefore x = y = 0.
In one embodiment of the invention, R1 represents a linear alkyl group comprising from 7 to 18 carbon atoms and more particularly from 7 to 12 carbon atoms, or a C1-C6, preferably C2-C4, aminoalkyl group. More particularly, R1 represents an oc tyl group.
In another embodiment of the invention, R1 is a linear or branched, saturated or unsaturated C1-C6 hydrocarbon-based chain. In this variant, R1 preferably repre sents a saturated linear C1-C3 alkyl group, preferably a methyl group.
In another embodiment of the invention, R1 is a linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based chain, substituted with an amine group NH2 or NHR (R = C1-C20, in particular C1-C6, alkyl, C3-C40 cycloalkyl or C6-C30 aromatic). In this variant, R1 preferably represents a C1-C6, preferably C2-C4, ami noalkyl group.
Preferably, the composition according to the invention comprises one or more orga- nosilanes chosen from methyltriethoxysilane (MTES), octyltriethoxysilane (OTES), dodecyltriethoxysilane, octadecyltriethoxysilane, hexadecyltriethoxysilane, 3-ami- nopropyltriethoxysilane (APTES), 2-aminoethyltriethoxysilane (AETES), 3-ami- nopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3- (m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-(2- aminoethylaminomethyl)phenethyltrimethoxysilane, and oligomers thereof, and/or mixtures thereof; and more particularly chosen from methyltriethoxysilane (MTES) and 3-aminopropyltriethoxysilane (APTES) and oligomers thereof, hydrolysis prod ucts thereof and/or mixtures thereof; and even better still chosen from 3-ami- nopropyltriethoxysilane (APTES), oligomers thereof and/or hydrolysis products thereof.
Preferably, the organosilane(s) are present in the care composition according to the invention in a total content ranging from 0.1 % to 10% by weight, preferentially from 0.5% to 7% by weight and better still from 1 % to 4% by weight, relative to the total weight of the care composition. d/ Organic acids
The care composition may optionally comprise one or more organic acids, in partic ular as neutralizing agent for the organosilane(s). For the purposes of the present invention, the term “organic acid” is intended to mean an organic acid and/or the associated bases thereof with a pKa of less than or equal to 7, preferably less than or equal to 6, especially ranging from 1 to 6, preferably from 2 to 5.
According to a preferred embodiment, the organic acid(s) are chosen from carbox- ylic acids, sulfonic acids and mixtures thereof. In particular, the organic acid(s) are chosen from saturated or unsaturated carboxylic acids. Preferably, the organic acid(s) are chosen from lactic acid, propanoic acid, butanoic acid, acetic acid, citric acid, maleic acid, glycolic acid, salicylic acid, malic acid, tartaric acid and mixtures thereof, and more preferably lactic acid.
The care composition may comprise the organic acid(s), when they are present, in a content ranging from 0.1 % to 10% by weight, preferably from 1 % to 8% by weight and even better still from 3% to 6% by weight, relative to the total weight of the composition. e) Amphoteric surfactants
The care composition according to the invention may optionally comprise one or more amphoteric surfactants.
In particular, the amphoteric or zwitterionic surfactant(s) are nonsilicone surfactants. They may in particular be optionally quaternized secondary or tertiary aliphatic amine derivatives, wherein the aliphatic group is a linear or branched chain com prising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phospho- nate group.
Mention may in particular be made of (C8-C2o)alkylbetaines, (C8-C2o)alkylsulfobeta- ines, (C8-C2o)alkylamido(C3-C8)alkylbetaines and (C8-C2o)alkylamido(C6-C8)alkyl- sulfobetaines. Among the optionally quaternized derivatives of secondary or tertiary aliphatic amines that may be used, as defined above, mention may also be made of the com pounds having the respective structures (II) and (III) below:
Ra-CONHCH2CH2-N+(Rb)(Rc)-CH2COO-, M+, X (II) wherein:
- Ra represents a Cio to C30 alkyl or alkenyl group derived from an acid RaCOOH preferably present in hydrolyzed coconut kernel oil, or a heptyl, nonyl or undecyl group; - Rb represents a b-hydroxyethyl group; and
- Rc represents a carboxymethyl group;
- M+ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; and
- X represents an organic or mineral anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C4)alkyl sulfates, (Ci-C4)alkyl- or (C-i- C4)alkylaryl-sulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M+ and X- are absent;
Ra'-CONHCH2CH2-N(B)(B') (III) wherein:
- B represents the group -CH2CH2OX’;
- B' represents the group -(CH2)ZY\ with z = 1 or 2;
- X represents the group -CH2COOH, -CH2-COOZ’, -CH2CH2COOH or CH2CH2- COOZ’, or a hydrogen atom;
- Y' represents the group -COOH, -COOZ' or -CH2CH(0H)S03H or the group CH2CH(0H)S03-Z';
- 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 Cio to C30 alkyl or alkenyl group of an acid Ra-COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil, or an alkyl group, in particular a C17 group, and its iso form, or an unsaturated C17 group.
These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, diso dium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoam- phodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropi- onate, disodium capryloamphodipropionate, lauroamphodipropionic acid and co- coamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate.
Use may also be made of compounds of formula (IV): Ra'-NHCH(Y")-(CH2)nCONH(CH2)n'-N(Rd)(Re) (IV) wherein:
- Y" represents the group -COOH, -COOZ" or -CH2-CH(0H)S03H or the group CH2CH(0H)S03-Z";
- Rd and Re, independently of one another, represent a Ci to 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 to C30 alkyl or alkenyl group of an acid Ra"-COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil;
- n and n' denote, independently of one another, an integer ranging from 1 to 3. Mention may be made, among the compounds of formula (II), of the compound clas sified in the CTFA dictionary under the name sodium diethylaminopropyl cocoas- partamide and sold by the company Chimex under the name Chimexane HB. These compounds may be used alone or as mixtures.
Among the amphoteric or zwitterionic surfactants, use is preferably made of (Cs- C2o)alkylbetaines such as cocoylbetaine, (C8-C2o)alkylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof, and the compounds of for mula (IV) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide).
Preferentially, the amphoteric or zwitterionic surfactants are chosen from (Cs-C2o)al- kylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine.
Preferably, the care composition according to the invention comprises one or more amphoteric surfactants.
When they are present in the care composition according to the invention, the am- photeric surfactant(s) are preferably present in a total content ranging from 0.1 % to 10% by weight, preferentially in a content ranging from 0.5% to 5% by weight and even better still from 1% to 3% by weight, relative to the total weight of the care composition. f/ Nonionic surfactants
The cosmetic care composition according to the invention may optionally comprise one or more nonionic surfactants, in particular such as those described in the Hand book of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and Lon don), 1991, pp 116-178.
Examples of nonionic surfactants that may be mentioned include the following com pounds, alone or as a mixture:
- oxyalkylenated (C8-C24)alkylphenols;
- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated Cs to C40 alcohols, preferably comprising one or two fatty chains;
- saturated or unsaturated, linear or branched, oxyalkylenated Cs to C30 fatty acid amides;
- esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of pol yethylene glycols; - preferably oxyethylenated esters of saturated or unsaturated, linear or branched,
Cs to C30 acids and of sorbitol;
- esters of fatty acids and of sucrose; - (C8-C3o)alkyl(poly)glucosides, (C8-C3o)alkenyl(poly)glucosides, which are option ally oxyalkylenated and which comprise from 1 to 15 glucose units, (Cs-C3o)al- kyl(poly)glucoside esters;
- saturated or unsaturated oxyethylenated plant oils;
- condensates of ethylene oxide and/or of propylene oxide;
- N-(C8-C3o)alkylglucamine and N-(C8-C3o)acylmethylglucamine derivatives;
- amine oxides.
The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
The number of moles of ethylene oxide and/or of propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol in particular ranges from 1 to 50 and better still from 1 to 10. Advantageously, the nonionic surfactants according to the invention do not comprise any oxypropylene units.
Preferably, they comprise a number of moles of ethylene oxide ranging from 1 to 250, in particular from 2 to 100 and better still from 2 to 50.
The nonionic surfactant(s) that may be used in the care composition according to the invention are preferentially chosen, alone or as a mixture, from:
- saturated or unsaturated, linear or branched, oxyethylenated Cs to C40, better still C10-C32 and even better still C10-C24 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol of eth ylene oxide and better still from 2 to 20 mol of ethylene oxide; they preferably com prise one or two fatty chains; preferably a single fatty chain;
- saturated or unsaturated oxyethylenated plant oils comprising from 1 to 100, pref erably from 2 to 50, mol of ethylene oxide;
- esters of saturated or unsaturated, linear or branched Cs to C30, better still C10- C32 and even better still C12-C24 acids and of polyethylene glycol, in particular comprising from 2 to 250 mol of ethylene oxide, better still from 10 to 200 or even from 50 to 200 mol of ethylene oxide.
More preferentially, the nonionic surfactant(s) are chosen, alone or as a mixture, from:
- saturated, linear, oxyethylenated C8 to C40, better still C10-C32 and even better still C10-C24 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol of ethylene oxide and better still from 2 to 20 mol of ethylene oxide, comprising a single fatty chain; mention may particularly be made of laureth-4;
- saturated or unsaturated, preferably saturated (hydrogenated), oxyethylenated plant oils, comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50; mention may particularly be made of PEG-40 hydrogenated castor oil;
- mono- or diesters of saturated, linear C8 to C30, better still C10-C32 and even better still C12-C24 acids and of polyethylene glycol, in particular comprising from 2 to 250 mol of ethylene oxide, better still from 10 to 200 or even from 50 to 200 mol of ethylene oxide; mention may particularly be made of PEG-150 distearate.
Preferably, the care composition according to the invention comprises one or more nonionic surfactants.
Preferably, when they are present, the care composition according to the invention comprises the nonionic surfactant(s) in a total content ranging from 0.1 % to 10% by weight, preferably from 0.5% to 8% by weight and preferentially from 1 % to 5% by weight, relative to the total weight of the care composition. q / Other ingredients
The care composition may comprise a cosmetically acceptable medium, that is to say a medium compatible with topical application to keratin fibers, in particular the hair.
The care composition according to the invention may comprise water or a mixture of water and one or more cosmetically acceptable solvents chosen from C1-C4 al cohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glyc erol, propylene glycol, hexylene glycol, and polyethylene glycols; and mixtures thereof.
Preferably, the care composition according to the invention comprises a total water content of between 40% and 98% by weight, preferably between 50% and 95%, preferentially between 60% and 92% by weight, even better still between 65% and 95% by weight, or even between 70% and 90% by weight, relative to the total weight of the composition.
The pH of the care composition according to the invention generally ranges from 3 to 9, preferably from 3 to 8, preferentially from 3.5 to 7 and better still from 4 to 6, or even from 4.5 to 5.5.
The cosmetic care composition according to the invention may further comprise at least one standard cosmetic ingredient, in particular chosen from plant, mineral, an imal or synthetic oils; liquid fatty alcohols; liquid fatty esters; solid fatty substances and in particular waxes, solid fatty esters, solid alcohols; sunscreens; moisturizers; antidandruff agents; antioxidants; pearlescent agents and opacifiers; plasticizers or coalescence agents; preservatives; sequestrants (EDTA and salts thereof); color ants. The composition may of course comprise several cosmetic ingredients fea tured in the above list. Those skilled in the art will take care to select the ingredients making up the composition, and also the amounts thereof, such that the advanta geous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition. B / Washing composition
The hair treatment process according to the invention also comprises a step, termed washing step, (ii) that consists in applying to the hair a cosmetic washing composi tion, comprising one or more anionic surfactants. In a known manner, said washing composition, or shampoo, can also comprise one or more amphoteric surfactants and/or one or more nonionic surfactants. a / Anionic surfactants
The cosmetic washing composition comprises one or more anionic surfactants. The term “anionic surfactant” is intended to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups.
In the present description, a species is termed as being “anionic” when it bears at least one permanent negative charge or when it can be ionized as a negatively charged species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.
The anionic surfactants may be sulfate, sulfonate and/or carboxylic (or carboxylate) surfactants. Needless to say, a mixture of these surfactants may be used.
It is understood in the present description that: - the carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-COOH or -COO ) and may optionally also comprise one or more sulfate and/or sulfonate functions;
- the sulfonate anionic surfactants comprise at least one sulfonate function (-SO3H or -SO3-) and may optionally also comprise one or more sulfate functions, but do not comprise any carboxylate functions; and
- the sulfate anionic surfactants comprise at least one sulfate function but do not comprise any carboxylate or sulfonate functions.
The carboxylic anionic surfactants that may be used thus include at least one car- boxylic or carboxylate function (-COOH or -COO ).
They may be chosen from the following compounds: acylglycinates, acyllactylates, acylsarcosinates, acylglutamates; alkyl ether carboxylic acids, alkyl(C6-30 aryl)ether carboxylic acids, alkyl-D-galactosideuronic acids, alkylamido ether car boxylic acids; and also the salts of these compounds; the alkyl and/or acyl groups of these compounds comprising from 6 to 30 carbon atoms, in particular from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being pol- yoxyalkylenated, in particular polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units, better still from 2 to 10 ethylene oxide units. Use may also be made of the C6-C24 alkyl monoesters of polyglycoside-polycar- boxylic acids, such as C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl polyglyco- side-tartrates and C6-C24 alkyl polyglycoside-sulfosuccinates, and salts thereof. Among the above carboxylic surfactants, mention may be made most particularly of polyoxyalkylenated alkyl(amido) ether carboxylic acids and salts thereof, in particu lar those comprising from 2 to 50 alkylene oxide, in particular ethylene oxide, groups, such as the compounds sold by the company Kao under the Akypo names. The polyoxyalkylenated alkyl(amido) ether carboxylic acids that may be used are preferably chosen from those of formula (1):
Rr-(OC2H4)n'-OCH2COOA (1) wherein:
- Rr represents a linear or branched C6-C24 alkyl or alkenyl radical, a (C8-C9)al- kylphenyl radical, a radical R2CONH-CH2-CH2- with R? denoting a linear or branched C9-C21 alkyl or alkenyl radical; preferably, Rr is a C8-C20, preferably C8- C18, alkyl radical;
- n’ is an integer or decimal number (mean value) ranging from 2 to 24 and preferably from 2 to 10, - A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue.
Use may also be made of mixtures of compounds of formula (1), in particular mix tures of compounds bearing different groups Rr.
The polyoxyalkylenated alkyl(amido) ether carboxylic acids that are particularly pre ferred are those of formula (1 ) wherein:
- Rr denotes a linear or branched C8-C22, in particular C10-C16 or even C12-C14 alkyl radical, or alternatively a (C8-C9)alkylphenyl radical; - A denotes a hydrogen or sodium atom, and
- n’ ranges from 2 to 20, preferably from 2 to 10.
Even more preferentially, use is made of the compounds of formula (1) wherein Rr denotes a C12-C14 alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical, A de notes a hydrogen or sodium atom and n’ ranges from 2 to 10.
Among the commercial products, use may preferably be made of the products sold by the company KAO under the names:
Akypo® NP 70 (Ri = nonylphenyl, n = 7, A = H)
Akypo® NP 40 (Ri = nonylphenyl, n = 4, A = H) Akypo® OP 40 (Ri = octylphenyl, n = 4, A = H)
Akypo® OP 80 (Ri = octylphenyl, n = 8, A = H)
Akypo® OP 190 (Ri = octylphenyl, n = 19, A = H)
Akypo® RLM 38 (Ri = (Ci2-Cu)alkyl, n = 4, A = H)
Akypo® RLM 38 NV (Ri = (Ci2-Cu)alkyl, n = 4, A = Na) Akypo® RLM 45 CA (Ri = (Ci2-Cu)alkyl, n = 4.5, A = H)
Akypo® RLM 45 NV (Ri = (Ci2-Cu)alkyl, n = 4.5, A = Na)
Akypo® RLM 100 (Ri = (Ci2-Cu)alkyl, n = 10, A = H)
Akypo® RLM 100 NV (Ri = (Ci2-Cu)alkyl, n = 10, A = Na) Akypo® RLM 130 (Ri = (Ci2-Cu)alkyl, n = 13, A = H)
Akypo® RLM 160 NV (Ri = (Ci2-Cu)alkyl, n = 16, A = Na), or by the company Sandoz under the names:
Sandopan DTC-Acid (Ri = (Ci3)alkyl, n = 6, A = H) Sandopan DTC (Ri = (Ci3)alkyl, n = 6, A = Na)
Sandopan LS 24 (Ri = (C-i2-Cu)alkyl, n = 12, A = Na)
Sandopan JA 36 (Ri = (Ci3)alkyl, n = 18, A = H), and more particularly the products sold under the following names:
Akypo® RLM 45 (INCI: Laureth-5 carboxylic acid), Akypo® RLM 100, and Akypo® RLM 38.
Preferentially, the carboxylic anionic surfactants are chosen, alone or as a mixture, from:
- acylglutamates, in particular of C6-C24 or even C12-C20, such as stearoylgluta- mates, and in particular disodium stearoylglutamate;
- acylsarcosinates, in particular of C6-C24 or even C12-C20, such as palmitoylsar- cosinates, and in particular sodium palmitoylsarcosinate;
- acyllactylates, in particular of C12-C28 or even C14-C24, such as behenoyllac- tylates, and in particular sodium behenoyllactylate; - C6-C24 and in particular C12-C20 acylglycinates;
- (C6-C24)alkyl ether carboxylates, and in particular (C12-C20)alkyl ether carbox- ylates; in particular those comprising from 2 to 50 ethylene oxide groups;
- polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids, in particular those comprising from 2 to 50 ethylene oxide groups; in particular in acid form or in the form of alkali metal or alkaline-earth metal, ammo nium or amino alcohol salts.
Polyoxyalkylenated (C6-C24)alkyl ether carboxylic acids and salts thereof are prefer ably used.
The sulfonate anionic surfactants that may be used include at least one sulfonate function (-SO3H or -SOz~). They may be chosen from the following compounds: al- kylsulfonates, alkyl ether sulfonates, alkylamidesulfonates, alkylarylsulfonates, a- olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccin- ates, alkylamidesulfosuccinates, alkylsulfoacetates, N-acyltaurates, acylisethio- nates; alkylsulfolaurates; and also the salts of these compounds; the alkyl groups of these compounds comprising from 6 to 30 carbon atoms, in par ticular from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, in particular polyoxyethyle- nated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units. Preferentially, the sulfonate anionic surfactants are chosen, alone or as a mixture, from:
- C6-C24 and in particular C12-C20 olefin sulfonates;
- C6-C24 and in particular C12-C20 alkylsulfosuccinates, in particular lau- rylsulfosuccinates;
- C6-C24 and in particular C12-C20 alkyl ether sulfosuccinates;
- (C6-C24)acylisethionates and preferably (C12-C18)acylisethionates; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.
The sulfate anionic surfactants that may be used include at least one sulfate function (-OSOsH or -OSO3-).
They may be chosen from the following compounds: alkyl sulfates, alkyl ether sul fates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; and the salts of these compounds; the alkyl groups of these compounds comprising from 6 to 30 carbon atoms, in par ticular from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, in particular polyoxyethyle- nated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.
Preferentially, the sulfate anionic surfactants are chosen, alone or as a mixture, from:
- alkyl sulfates, in particular of C6-C24 or even C12-C20, and
- alkyl ether sulfates, in particular of C6-C24 or even C12-C20, preferably compris ing from 2 to 20 ethylene oxide units; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.
When the anionic surfactant is in salt form, said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magne sium salt.
Examples of amino alcohol salts that may be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanola- mine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2-amino-2- methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
Preferentially, the anionic surfactants are chosen, alone or as a mixture, from:
- C6-C24 and in particular C12-C20 alkyl sulfates; - C6-C24 and in particular C12-C20 alkyl ether sulfates; preferably comprising from 2 to 20 ethylene oxide units;
- C6-C24 and in particular C12-C20 alkylsulfosuccinates, in particular lau- rylsulfosuccinates; - C6-C24 and in particular C12-C20 olefin sulfonates;
- C6-C24 and in particular C12-C20 alkyl ether sulfosuccinates;
- (C6-C24)acylisethionates and preferably (C12-C18)acylisethionates;
- C6-C24 and in particular C12-C20 acylsarcosinates; in particular palmitoylsar- cosinates; - (C6-C24)alkyl ether carboxylates, preferably (C12-C20)alkyl ether carboxylates; in particular those comprising from 2 to 50 ethylene oxide groups;
- polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids and salts thereof, in particular those comprising from 2 to 50 alkylene oxide, in particular ethylene oxide, groups; - C6-C24 and in particular C12-C20 acylglutamates;
- C6-C24 and in particular C12-C20 acylglycinates; in particular in acid form or in the form of alkali metal or alkaline-earth metal, ammo nium or amino alcohol salts. Preferentially, the composition comprises one or more sulfate anionic surfactants, preferably one or more C6-C24 and in particular C12-C20 alkyl sulfates, and/or one or more C6-C24 and in particular C12-C20 alkyl ether sulfates; preferably compris ing from 2 to 20 ethylene oxide units; particularly in the form of alkali metal or alka line-earth metal, ammonium or amino alcohol salts.
The anionic surfactant(s) are preferably present in the washing composition in a total content ranging from 2% to 30% by weight, in particular from 4% to 25% by weight, better still from 5% to 20% by weight and even better still from 6% to 15% by weight, relative to the total weight of the composition. b / Amphoteric surfactants
The washing composition according to the invention may also comprise one or more amphoteric surfactants.
In particular, the amphoteric or zwitterionic surfactant(s) are nonsilicone surfactants. They may in particular be optionally quaternized secondary or tertiary aliphatic amine derivatives, wherein the aliphatic group is a linear or branched chain com prising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phospho- nate group.
Mention may in particular be made of (C8-C2o)alkylbetaines, (C8-C2o)alkylsulfobeta- ines, (C8-C2o)alkylamido(C3-C8)alkylbetaines and (C8-C2o)alkylamido(C6-C8)alkyl- sulfobetaines. Among the optionally quaternized derivatives of secondary or tertiary aliphatic amines that may be used, as defined above, mention may also be made of the com pounds having the respective structures (II) and (III) below:
Ra-CONHCH2CH2-N+(Rb)(Rc)-CH2COO-, M+, X (II) wherein:
- Ra represents a C10 to C30 alkyl or alkenyl group derived from an acid RaCOOH preferably present in hydrolyzed coconut kernel oil, or a heptyl, nonyl or undecyl group;
- Rb represents a b-hydroxyethyl group; and
- Rc represents a carboxymethyl group;
- M+ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; and
- X represents an organic or mineral anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C4)alkyl sulfates, (Ci-C4)alkyl- or (Ci- C4)alkylaryl-sulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M+ and X- are absent;
Ra'-CONHCH2CH2-N(B)(B') (III) wherein:
- B represents the group -CH2CH2OX’;
- B' represents the group -(CH2)ZY\ with z = 1 or 2; - X represents the group -CH2COOH, -CH2-COOZ’, -CH2CH2COOH or CH2CH2-
COOZ’, or a hydrogen atom;
- Y' represents the group -COOH, -COOZ' or -CH2CH(0H)S03H or the group CH2CH(0H)S03-Z';
- 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 to C30 alkyl or alkenyl group of an acid Ra-COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil, or an alkyl group, in particular a C17 group, and its iso form, or an unsaturated C17 group. These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, diso dium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoam- phodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropi- onate, disodium capryloamphodipropionate, lauroamphodipropionic acid and co- coamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate. Use may also be made of compounds of formula (IV):
Ra"-NHCH(Y")-(CH2)nCONH(CH2)n'-N(Rd)(Re) (IV) wherein:
- Y" represents the group -COOH, -COOZ" or -CH2-CH(0H)S03H or the group CH2CH(0H)S03-Z";
- Rd and Re, independently of one another, represent a Ci to 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 to C30 alkyl or alkenyl group of an acid Ra"-COOH which is preferably present in coconut kernel oil or in hydrolyzed linseed oil;
- n and n' denote, independently of one another, an integer ranging from 1 to 3. Mention may be made, among the compounds of formula (II), of the compound clas sified in the CTFA dictionary under the name sodium diethylaminopropyl cocoas- partamide and sold by the company Chimex under the name Chimexane HB. These compounds may be used alone or as mixtures.
Among the amphoteric or zwitterionic surfactants, use is preferably made of (Cs- C2o)alkylbetaines such as cocoylbetaine, (C8-C2o)alkylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof, and the compounds of for mula (IV) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide).
Preferentially, the amphoteric or zwitterionic surfactants are chosen from (C8-C2o)al- kylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine.
Preferably, the amphoteric surfactant(s) are present in the washing composition in a total content ranging from 3% to 20% by weight, preferentially in a content ranging from 3.5% to 15% by weight and even better still from 4% to 10% by weight, relative to the total weight of the composition.
3/ Nonionic surfactants
The cosmetic washing composition may also comprise one or more nonionic sur factants, in particular such as those described in the Handbook of Surfactants by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp 116-178.
Examples of nonionic surfactants that may be mentioned include the following com pounds, alone or as a mixture:
- oxyalkylenated (C8-C24)alkylphenols;
- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated Cs to C40 alcohols, preferably comprising one or two fatty chains;
- saturated or unsaturated, linear or branched, oxyalkylenated Cs to C30 fatty acid amides; - esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of pol yethylene glycols;
- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of sorbitol;
- esters of fatty acids and of sucrose;
- (C8-C3o)alkyl(poly)glucosides, (C8-C3o)alkenyl(poly)glucosides, which are option ally oxyalkylenated and which comprise from 1 to 15 glucose units, (C8-C3o)al- kyl(poly)glucoside esters;
- saturated or unsaturated oxyethylenated plant oils;
- condensates of ethylene oxide and/or of propylene oxide;
- N-(C8-C3o)alkylglucamine and N-(C8-C3o)acylmethylglucamine derivatives;
- amine oxides.
The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
The number of moles of ethylene oxide and/or of propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol in particular ranges from 1 to 50 and better still from 1 to 10. Advantageously, the nonionic surfactants according to the invention do not comprise any oxypropylene units.
Preferably, they comprise a number of moles of ethylene oxide ranging from 1 to 250, in particular from 2 to 100 and better still from 2 to 50.
The nonionic surfactant(s) that may be used in the washing composition according to the invention are preferentially chosen, alone or as a mixture, from:
- saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide; they preferably include one or two fatty chains;
- saturated or unsaturated oxyethylenated plant oils comprising from 1 to 100 and preferably from 2 to 50 mol of ethylene oxide;
- (C8-C3o)alkyl(poly)glucosides, which are optionally oxyalkylenated, preferably with 0 to 10 mol of ethylene oxide and comprising 1 to 15 glucose units;
- monoglycerolated or polyglycerolated Cs to C40 alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol;
- saturated or unsaturated, linear or branched, oxyalkylenated Cs to C30 fatty acid amides;
- esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of pol yethylene glycols;
- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of sorbitol.
More preferentially, the nonionic surfactant(s) are chosen, alone or as a mixture, from: - saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and comprising one or two fatty chains, in particular at least one C8-C20 and in particular C10-C18 alkyl chain;
- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Ce to C30 acids and of sorbitol; and
- (C8-C3o)alkyl(poly)glucosides, which are optionally oxyalkylenated, preferably comprising from 1 to 10 mol of ethylene oxide and comprising 1 to 15 glucose units.
In particular, the washing composition may comprise one or more nonionic surfac tants of alkyl(poly)glycoside type of general formula:
R10-(R20)t-(G)v wherein:
- R1 represents a linear or branched alkyl or alkenyl radical comprising 6 to 24 car bon atoms and in particular 8 to 18 carbon atoms, or an alkylphenyl radical of which the linear or branched alkyl radical includes 6 to 24 carbon atoms and in particular 8 to 18 carbon atoms; preferably a saturated or unsaturated, linear or branched alkyl radical comprising from 8 to 18 carbon atoms;
- R2 represents an alkylene radical comprising 2 to 4 carbon atoms;
- G represents a sugar unit comprising 5 to 6 carbon atoms; preferably glucose, fructose or galactose; even better still glucose;
- 1 denotes a value ranging from 0 to 10, preferably from 0 to 4, better still from 0 to 3 and even better still 0;
- v denotes a value ranging from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization (v) 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)glycoside surfactant is an alkyl (poly)glucoside surfactant.
Preferably, the washing composition according to the invention comprises the nonionic surfactant(s), when they are present, in a total content ranging from 0.05% to 15% by weight, preferably from 0.1 % to 10% by weight and preferentially from 0.2% to 5% by weight, relative to the total weight of the washing composition. d / Other ingredients
The washing composition according to the invention may comprise water or a mix ture of water and one or more cosmetically acceptable solvents chosen from C1-C4 alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glycerol, propylene glycol and polyethylene glycols; and mixtures thereof. Preferably, the washing composition according to the invention has a total water content of between 20% and 95% by weight, preferably between 30% and 90%, preferentially between 40% and 85% by weight and even better still between 50% and 80% by weight relative to the total weight of the composition.
The pH of the washing composition according to the invention generally ranges from 3 to 9, preferably from 3 to 7, preferentially from 3.5 to 6 and better still from 4 to 5.5.
The cosmetic washing composition according to the invention may further comprise at least one standard cosmetic ingredient, in particular chosen from polymeric or nonpolymeric conditioning agents; mention may in particular be made of cationic polymers, amphoteric polymers, silicones, organomodified silicones such as amino silicones; plant, mineral, animal or synthetic oils; liquid fatty alcohols; liquid fatty esters; solid fatty substances and in particular waxes, solid fatty esters, solid alco hols; ceram ides; sunscreens; moisturizers; antidandruff agents; antioxidants; pearlescent agents and opacifiers; plasticizers or coalescence agents; preserva- tives; sequestrants (EDTA and salts thereof); colorants. The composition may of course comprise several cosmetic ingredients featured in the above list. Those skilled in the art will take care to select the ingredients making up the composition, and also the amounts thereof, such that the advantageous properties of the compo sition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.
The present invention is illustrated in greater detail in the examples that follow (AM = active material). Example 1
The following care composition according to the invention is prepared (% by weight of active material):
[Table 1]
Figure imgf000041_0001
Figure imgf000042_0001
This composition can be used as a conditioner or as a pre-shampoo.
When it is used as a pre-shampoo, the composition is applied to half a head, on medium-long to long wet hair, in a proportion of 10 g per half head. It is left on for 5 minutes and then rinsed off with water.
A commercial shampoo (comprising in particular NaLES + cocamidopropylbetaine + cocobetaine + cationic guar + PDMS + amodimethicone) is then applied, to the whole of the head, in a proportion of 16 g per head, and is then rinsed off with water. A commercial conditioner (comprising in particular BETAC and CETAC cationic sur factants + cetearyl alcohol + cetyl esters + amodimethicone) is applied, in a propor tion of 10 g per half head, to the half head that did not receive the pre-shampoo according to the invention, it is left on for 5 minutes and is then rinsed off with water. The hair is then dried with a hairdryer.
An expert then evaluates, blind, each of the sides of the head; the evaluation is performed on 6 volunteers.
Observations at TO: - on damp hair (before drying): the hair treated according to the invention is smoother to the touch and more supple; it is less tangled;
- on dried hair: the hair treated according to the invention is smoother to the touch.
Regarding more particularly the criterion of smoothness to the touch, the expert evaluates blind, in the following way:
- the smoothness evaluation is tactile: on each half head, a lock of hair is taken at the root and it is made to slide between the fingers over the entire length of the lock all the way to the ends (to be repeated at several places on the half head);
- the expert evaluates whether (or not) the hair exhibits rough patches, and whether (or not) it catches the fingers, and gives a score, ranging from 0 (very poor) to 5
(very good), in increments of 0.5.
The following results are obtained (mean over 6 models): [Table 2]
Figure imgf000042_0002
At TO, the hair treated with the invention is significantly smoother to the touch than the hair treated with the comparative composition. Observations after 3 shampoo washes (persistence):
After 3 shampoo washes, it is observed that the hair treated according to the inven tion remains easier to disentangle and still appears to be more coated.
The provision of a strong cosmetic effect is observed on the side tested according to the invention, whether on damp hair or on dry hair: the hair is smooth to the touch and visually more coated, it has a uniform feel, the hair is supple, the strands are more individual, it is easy to disentangle.
The following results are obtained (mean over 6 models): [Table 3]
Figure imgf000043_0001
After 3 shampoo washes, the hair treated with the invention is significantly smoother to the touch than the hair treated with the comparative composition.
Example 2 The following composition B according to the invention and comparative composi tion C were prepared (% by weight of active material AM):
[Table 4]
Figure imgf000043_0002
Figure imgf000044_0002
Protocol i) Pre-shampoo
Compositions B and C were applied to locks of moderately sensitized hair (alkaline solubility = 20%, AS20) in a proportion of 0.4 g of composition per g of hair. They are left on for 5 minutes and then rinsed off with water. ii) Shampoo
A commercial shampoo (comprising in particular NaLES + cocamidopropylbetaine + cocobetaine + cationic guar + PDMS + amodimethicone) is then applied, to the locks, in a proportion of 0.4 g per gram of hair, and is then rinsed off with water and dried in an oven at 60°C.
This shampoo-washing protocol was repeated twice in order to evaluate the persis tence of the cosmetic properties with respect to 3 shampoo washes. Results (persistence, with respect to 3 shampoo washes, of the cosmetic proper ties: disentangling, smoothness and suppleness)
The performance results in terms of cosmetic properties (disentangling, smoothness and suppleness) were evaluated on dry hair, during a blind test.
An expert graded each of the locks on a scale ranging from 0 (very poor) to 5 (very good).
- The suppleness evaluation is tactile. The hair is taken in both hands and it is sought to fold it. An evaluation is made of the capacity of the hair to easily curve, its malle ability.
- In order to evaluate the smooth feel, the expert takes the lock between the thumb and index finger and slides the fingers along the lock from the upper part to the ends.
The expert evaluates whether the hair is soft and supple, whether it exhibits rough patches, whether it catches the figures, and whether it feels uniform.
- In order to evaluate the disentangling, a fine comb is run through the lock from top to bottom. As the comb passes through the lock, the earlier it blocks, the more diffi cult it will be to disentangle the lock.
The following results are obtained: [Table 5]
Figure imgf000044_0001

Claims

1. A hair treatment process comprising: (i) a step of applying, to the hair, a cosmetic care composition comprising:
- one or more alkyl(amido) ether carboxylic anionic surfactants,
- one or more cationic, preferably associative, polymers, and
- one or more organosilanes, and
(ii) a step of washing said hair, comprising the application of a cosmetic washing composition comprising one or more anionic surfactants, said steps (i) and (ii) being carried out successively, the time separating said steps (i) and (ii) being at most 60 minutes, in particular between 30 seconds and 60 minutes, especially between 1 and 30 minutes, or even between 2 and 20 minutes, even better still between 3 and 15 minutes, and most particularly between 4 and 10 minutes.
2. The process as claimed in claim 1, wherein:
- step (i) is followed by a leave-on step, for example a leave-on time of from 1 to 15 minutes, in particular 2 to 5 minutes; and/or a rinsing step, for example with water; and/or
- the washing step (ii) is followed by a leave-on step, for example a leave-on time of from 1 to 15 minutes, in particular 2 to 5 minutes; and/or a rinsing step, for example with water; and/or a drying step.
3. The process as claimed in either of the preceding claims, wherein the care com position comprises one or more polyoxyalkylenated alkyl(amido) ether carboxylic anionic surfactants of formula (I):
Ri-(OC2H4)n-OCH2COOA wherein: - Ri represents a linear or branched C6-C24 alkyl or alkenyl radical, a (C8-C9)al- kylphenyl radical, a radical R2CONH-CH2-CH2- with R2 denoting a linear or branched C9-C21 alkyl or alkenyl radical; preferably, Ri is a C8-C20, preferably Cs- C18, alkyl radical,
- n is an integer or decimal number (mean value) ranging from 2 to 24 and preferably from 2 to 10,
- A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue.
4. The process as claimed in claim 3, wherein the care composition comprises one or more polyoxyalkylenated alkyl(amido) ether carboxylic anionic surfactants of for mula (I) wherein:
- Ri denotes a C8-C22, in particular C10-C16 or even C12-C14 alkyl radical, or alternatively a (C8-C9)alkylphenyl radical; - A denotes a hydrogen or sodium atom, and
- n ranges from 2 to 20, preferably from 2 to 10; preferentially wherein Ri denotes a C12-C14 alkyl, cocoyl, oleyl, nonylphenyl or oc- tylphenyl radical; A denotes a hydrogen or sodium atom and n ranges from 2 to 10.
5. The process as claimed in one of the preceding claims, wherein the care compo sition comprises one or more alkyl(amido) ether carboxylic anionic surfactants cho sen, alone or as a mixture, from:
- (C6-C24)alkyl ether carboxylic acids and in particular (C12-C20)alkyl ether carbox ylic acids, and salts thereof;
- polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids, in particular those comprising from 1 to 50, in particular from 2 to 10, ethylene oxide groups; and salts thereof; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.
6. The process as claimed in one of the preceding claims, wherein the care compo sition comprises said alkyl(amido) ether carboxylic anionic surfactant(s) in a total content ranging from 0.5% to 12% by weight, better still from 1 % to 10% by weight, preferentially from 1 .5% to 8% by weight, even better still from 2% to 7% by weight, relative to the total weight of the composition.
7. The process as claimed in one of the preceding claims, wherein the care compo sition comprises one or more associative cationic polymers, in particular chosen, alone or as a mixture, from:
- (A) cationic associative polyurethanes, which can be represented by general for mula (la) below: R-X-(P)n-[L-(Y)m]r-L'-(P')p-X'-R' wherein:
R and R’, which may be identical or different, represent a hydrophobic group or a hydrogen atom;
X and X’, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively the group L”;
L, L’ and L”, which may be identical or different, represent a group derived from a diisocyanate;
P and P’, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group;
Y represents a hydrophilic group; r is an integer between 1 and 100 inclusive, preferably between 1 and 50 inclusive and in particular between 1 and 25 inclusive; n, m and p are each, independently of one another, between 0 and 1000 inclusive; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group. - (B) quaternized cellulose derivatives, and in particular quaternized celluloses mod ified with groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyl groups, or linear or branched alkylaryl groups, preferably linear or branched alkyl groups, these groups comprising at least 8 car- bon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof.
- (C) cationic polyvinyllactams, in particular those comprising:
-a) at least one monomer of vinyllactam or alkylvinyllactam type; -b) at least one monomer of structure (lc) or (lie) below:
Figure imgf000047_0001
FL
_ / 3
GHj C(R1}-CO_ X (Y)-(CH2-CH2-0)- (CH2-CH (R2)-0 )- (Y, )— N ^
(lie) R4 wherein:
- X denotes an oxygen atom or an NR6 radical,
- R1 and R6 denote, independently of one another, a hydrogen atom or a linear or branched C1-C5 alkyl radical,
- R2 denotes a linear or branched C1-C4 alkyl radical,
- R3, R4 and R5 denote, independently of one another, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (lllc):
— (Y2)r— (CH2-CH(R7)-0)— R8 (lllc) - Y, Y1 and Y2 denote, independently of one another, a linear or branched C2-C16 alkylene radical,
- R7 denotes a hydrogen atom, or a linear or branched C1 -C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical,
- R8 denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical, - p, q and r denote, independently of one another, 0 or 1 ,
- m and n denote, independently of one another, an integer ranging from 0 to 100 inclusive,
- x denotes an integer ranging from 1 to 100 inclusive,
- Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate; with the proviso that:
- at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9- C30 alkyl radical,
- if m and/or n is other than zero, then q is equal to 1 , - if m = n = 0, then p or q is equal to 0. - (D) the cationic polymers obtained by polymerization of a monomer mixture com prising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers, and one or more associative vinyl monomers, such as the products of the polymerization of a mixture of monomers comprising:
- a di(C1-C4 alkyl)amino(C1-C6 alkyl) methacrylate,
- one or more C1-C30 alkyl esters of (meth)acrylic acid,
- a polyethoxylated C10-C30 alkyl methacrylate (20-25 mol of ethylene oxide unit), - a 30/5 polyethylene glycol/polypropylene glycol allyl ether,
- a hydroxy(C2-C6 alkyl) methacrylate, and
- an ethylene glycol dimethacrylate.
8. The process as claimed in one of the preceding claims, wherein the care compo- sition comprises one or more cationic polymers chosen from quaternized hydroxy- ethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyl groups, or linear or branched alkylaryl groups, preferably linear or branched alkyl groups, these groups comprising at least 8 carbon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof; preferentially chosen from the hydroxyethylcelluloses of formula (lb):
Figure imgf000048_0001
wherein: - R represents an ammonium group RaRbRcN+-, Q- wherein Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched C1- C30 alkyl, and Q- represents an anionic counterion such as a halide, for instance a chloride or bromide; preferably an alkyl;
- R’ represents an ammonium group R’aR’bR’cN+-, Q’- wherein R’a, R’b and R’c, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C30 alkyl, and Q’- represents an anionic counterion such as a halide, for instance a chloride or bromide; preferably an alkyl; it being understood that at least one of the radicals Ra, Rb, Rc, R'a, R'b and R'c represents a linear or branched C8-C30 alkyl; - n, x and y, which may be identical or different, represent an integer between 1 and
10 000.
9. The process as claimed in one of claims 1 to 6, wherein the care composition comprises one or more associative or nonassociative cationic polymers, in particular chosen, alone or as a mixture, from: - alkyldiallylamine or dialkyldiallylammonium cyclopolymers, and in particular homo polymers or copolymers of dimethyldiallylammonium salts (for example chloride);
- optionally crosslinked homopolymers or copolymers of methacryloyloxy(C1-C4)al- kyltri(C1 -C4)alkylammonium salts;
- quaternary polymers of vinylpyrrolidone and of vinylimidazole; - the cationic polymers (B) derived from quaternized cellulose, and hydroxyethyl- celluloses of formula (lb) as defined in claim 8; in particular those for which R rep resents a trimethylammonium halide and R' represents a dimethyldodecylammo- nium halide, preferentially R represents a trimethylammonium chloride (CH3)3N+-, Cl and R’ represents a dimethyldodecylammonium chloride (CH3)2(Ci2H25)N+-, Cl .
10. The process as claimed in one of the preceding claims, wherein the care com position comprises the cationic polymer(s) in a total amount of between 0.1% and 8% by weight, in particular from 0.2% to 5% by weight, preferentially from 0.3% to 2% by weight, even better still from 0.4% to 1.4% by weight, relative to the total weight of the composition; and/or the care composition comprises the associative cationic polymer(s) in a total amount of between 0.1% and 8% by weight, in partic ular from 0.2% to 5% by weight, preferentially from 0.3% to 2% by weight, even better still from 0.4% to 1.4% by weight, relative to the total weight of the composi tion.
11. The process as claimed in one of the preceding claims, wherein the weight ratio between the total amount of anionic surfactants and the total amount of cationic polymers present in the care composition is less than or equal to 6, better still less than or equal to 5.5, even better still less than or equal to 5, or even less than or equal to 4.5, and/or the weight ratio between the total amount of alkyl(amido) ether carboxylic anionic surfactants and the total amount of associative cationic polymers present in the care composition is less than or equal to 6, better still less than or equal to 5.5, even better still less than or equal to 5, or even less than or equal to 4.5.
12. The process as claimed in one of the preceding claims, wherein the care com position comprises one or more organosilanes chosen from the compounds of for mula (II) and/or oligomers thereof and/or hydrolysis products thereof:
R1Si(OR2)z(R3)x(OH)y wherein:
- R1 is a cyclic or acyclic, linear or branched, saturated or unsaturated C1-C22, in particular C2-C20, hydrocarbon-based chain, which may be substituted with a group chosen from the amine groups NH2 or NHR (R being a linear or branched C1-C20, in particular C1-C6, alkyl, or a C3-C40 cycloalkyl or a C6-C30 aromatic radical); the hydroxyl group (OH), a thiol group, an aryl group (more particularly benzyl), which is possibly substituted with an NH2 or NHR group; it being possible for R1 to be interrupted with a heteroatom (O, S or NH) or a carbonyl group (CO),
- R2 and R3, which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms,
- y denotes an integer ranging from 0 to 3,
- z denotes an integer ranging from 0 to 3, and
- x denotes an integer ranging from 0 to 2, with z + x + y = 3; preferably, R1 being a linear or branched, preferably linear, saturated C1-C22, in particular C1-C12, hydrocarbon-based chain, which may be substituted with an amine group NH2 or NHR (R = C1-C20, in particular C1-C6, alkyl); preferably, R2 representing an alkyl group comprising from 1 to 4 carbon atoms, better still a linear alkyl group comprising from 1 to 4 carbon atoms, and even better still an ethyl group; preferably, z ranging from 1 to 3, better still z = 3 and x = y = 0.
13. The process as claimed in one of the preceding claims, wherein the orga- nosilane(s) are present in the care composition in a total content ranging from 0.1 % to 10% by weight, preferentially from 0.5% to 7% by weight and better still from 1 % to 4% by weight, relative to the total weight of the care composition.
14. The process as claimed in one of the preceding claims, wherein the care com position comprises one or more amphoteric surfactants, preferably chosen from (Cs- C2o)alkylbetaines such as cocoylbetaine, (C8-C2o)alkylamido(C3-C8)alkylbetaines such as cocam idopropylbetaine, and mixtures thereof.
15. The process as claimed in one of the preceding claims, wherein the care com position comprises one or more nonionic surfactants, preferentially chosen, alone or as a mixture, from:
- saturated or unsaturated, linear or branched, oxyethylenated Cs to C40, better still C10-C32 and even better still C10-C24 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol of eth ylene oxide and better still from 2 to 20 mol of ethylene oxide; they preferably com prise one or two fatty chains; preferably a single fatty chain;
- saturated or unsaturated oxyethylenated plant oils comprising from 1 to 100 and preferably from 2 to 50 mol of ethylene oxide;
- esters of saturated or unsaturated, linear or branched Cs to C30, better still C10- C32 and even better still C12-C24 acids and of polyethylene glycol, in particular comprising from 2 to 250 mol of ethylene oxide, better still from 10 to 200 or even from 50 to 200 mol of ethylene oxide.
16. The process as claimed in one of the preceding claims, wherein the cosmetic washing composition comprises one or more anionic surfactants chosen, alone or as a mixture, from:
- C6-C24 and in particular C12-C20 alkyl sulfates; - C6-C24 and in particular C12-C20 alkyl ether sulfates; preferably comprising from 2 to 20 ethylene oxide units;
- C6-C24 and in particular C12-C20 alkylsulfosuccinates, in particular laurylsulfosuc- cinates;
- C6-C24 and in particular C12-C20 olefin sulfonates; - C6-C24 and in particular C12-C20 alkyl ether sulfosuccinates;
- (C6-C24)acylisethionates and preferably (C12-C18)acylisethionates;
- C6-C24 and in particular C12-C20 acylsarcosinates; in particular palmitoylsar- cosinates;
- (C6-C24)alkyl ether carboxylates, preferably (C12-C20)alkyl ether carboxylates; in particular those comprising from 2 to 50 ethylene oxide groups;
- polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids and salts thereof, in particular those comprising from 2 to 50 alkylene oxide, in particular ethylene oxide, groups;
- C6-C24 and in particular C12-C20 acylglutamates; - C6-C24 and in particular C12-C20 acylglycinates; in particular in acid form or in the form of alkali metal or alkaline-earth metal, ammo nium or amino alcohol salts; preferentially, the composition comprises one or more sulfate anionic surfactants, preferably one or more C6-C24 and in particular C12-C20 alkyl sulfates, and/or one or more C6-C24 and in particular C12-C20 alkyl ether sulfates; preferably compris ing from 2 to 20 ethylene oxide units; particularly in the form of alkali metal or alka line-earth metal, ammonium or amino alcohol salts.
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