FR2863880A1 - Cosmetic composition especially useful as a shampoo or shower gel comprises water, anionic surfactant and ampholytic copolymer - Google Patents

Abstract

Cosmetic composition with a pH of at least 5.5 comprises water, 5-30 wt.% surfactant (anionic and optionally amphoteric) and 0.1-5 wt.% of an ampholytic copolymer comprising 0.1-50% dialkenyl quaternary ammonium salt units (I) and 50-99.9% hydrophilic acid-functional units. Cosmetic composition with a pH of at least 5.5 comprises water, 5-30 wt.% surfactant (anionic and optionally amphoteric) and 0.1-5 wt.% of an ampholytic copolymer comprising 0.1-50% dialkenyl quaternary ammonium salt units of formula (I) and 50-99.9% hydrophilic acid-functional units. H2C=CR1-(CH2)n-N+>R2R3-(CH2)m-CR4=CH2 X-> (I) R1, R4H or 1-6C alkyl; R2, R31-6C alkyl, hydroxyalkyl or aminoalkyl; m, n : 1-3; X : an anion.

Description

Cosmetic composition comprising an ampholytic copolymer

  The present invention relates to novel cosmetic compositions, more particularly for the treatment of skin or hair, comprising an artificial ampholytic copolymer. The invention also relates to the use of the polymer in cosmetic compositions.

  In cosmetic compositions intended for the treatment of skin or hair, intended to be applied and rinsed, such as shampoos or shower gels, it is sought to optimize certain properties such as viscosity, transparency and deposition of matter (effect conditioner), and / or, more generally, to optimize cosmetic effects such as softness, suppleness, detangling, shine, styling ability on dry or wet hair. Of course, besides the effects provided by the ingredients, one also seeks formulations that are easy to prepare, easy to implement, and sufficiently stable.

  It has thus been proposed to use, in formulations intended to be rinsed, derivatives of natural polymers, such as cationic derivatives of guar or cellulose.

  It has also been proposed to use synthetic copolymers comprising cationic (or potentially cationic) units, anionic units, and possibly neutral units. Thus, it has been proposed to use in certain formulations: copolymers derived from acrylic acid (AA, 2 to 40% by weight) and dimethyldiallylammonium chloride chloride (DADMAC, 60 to 90% by weight), for example in EP 269243 and EP 266111, EP 521748, a commercial polymer being Merquat 280 sold by Calgon - copolymers derived from acrylic acid (M, 35% by number), dimethyldiallylammonium chloride chloride (DADMAC, % by number), and acrylamide (AM, 35% by number), for example in the documents EP 522755, EP 522756 and EP 1115370, a commercial polymer being the Merquat plus 3330 marketed by Calgon, - copolymers derived from acrylic acid (M), methacrylamidopropyltrimethylammonium chloride (MAPTAC) and alkyl acrylate, for example described in EP 522756 and EP 1115370, a commercial polymer being the Merquat 2001 marketed by Calgon. (AA / MAPTAC / methyl acrylate).

  It is still sought to provide new cosmetic compositions intended to be rinsed having improved qualities in terms of stability and / or simplification of the formulations and / or transparency and / or cosmetic qualities (mentioned above) and / or deposition of material (depositing a polymer bearing cationic charges or depositing other materials such as mineral, vegetable or synthetic oils, for example silicone oils).

  For this purpose, the invention provides a cosmetic composition comprising water, a surfactant and an ampholytic copolymer comprising cationic units (c) and anionic or anionic units (a), characterized in that: the polymer comprises: - from 0.1 to 50% by number of units (c) deriving from the polymerization of at least one monomeric compound (c) of the following general formula I: R1 R2 R4 H2C = C + CH N + CH2 wherein: R 4 and R 4 represent, independently of one another, a hydrogen atom or a linear or branched C 1 -C 6 alkyl group; R2 and R3 represent, independently of one another, an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C1-C6 chain, preferably a methyl group; n and m are integers between 1 and 3; X, which are identical or different, represent counterions compatible with the water-soluble or water-dispersible nature of the polymer; from 50 to 99.9% by number of units (a) deriving from the polymerization of at least one monomeric (a) hydrophilic compound bearing a function with an acidic character copolymerizable with (c), anionic or capable of being anionic, the pH of the composition is greater than or equal to 5.5, preferably between 5.5 and 7.5, the proportion by weight of surfactant in the composition is between 5 and 30% by weight, the surfactant comprising an anionic surfactant and optionally an amphoteric surfactant, the proportion by weight of the copolymer in the composition is between 0.1 and 5%, preferably between 0.2 and 1.5%.

  Effects The use of the polymer in the composition according to the invention in particular provides an interesting transparency and / or an increase in viscosity. Both of these effects can make formulations simpler and / or less expensive. The compromise between transparency and high viscosity makes the compositions according to the invention particularly interesting. The compositions remain especially transparent even at relatively high levels of salts (for example up to 3%). The compositions also have satisfactory foaming properties, especially in hard water.

  Particularly advantageous compositions have a transmittance measured at 600 nanometers at least equal to 90%, preferably at least 95%.

  Polymer The copolymer comprises: from 0.1 to 50% by number of units (c) derived from the polymerization of at least one monomer compound (c) of the following general formula I: R1 R2 R4 H2C = C-CH -N [CH 2 C = CH 2 X -R 3 in which: - R 4 and R 4 represent, independently of one another, a hydrogen atom or a linear or branched C 1 -C 6 alkyl group; R2 and R3 represent, independently of one another, an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C1-C6 chain, preferably a methyl group; n and m are integers between 1 and 3; - X-, identical or different, represent counterions compatible with the water-soluble or water-dispersible nature of the polymer; from 50 to 99.9% by number of units (a) derived from the polymerization of at least one monomeric (a) hydrophilic compound bearing a function with an acidic character copolymerizable with (c), anionic or capable of being anionic.

  Preferably: R 1 represents a hydrogen atom, R 2 represents a methyl group, R 3 represents a methyl group, R 4 represents a hydrogen atom, and - m and n are equal to 1.

  The X- ion is advantageously chosen from halide, sulfate, methyl sulfate, hydrosulphate, phosphate, citrate, formate and acetate.

  The copolymer according to the invention advantageously has a molecular weight of at least 1,000, advantageously at least 10,000; it can be up to 20,000,000, advantageously up to 10,000,000. It is preferably between 100,000 and 400,000.

  Unless otherwise indicated, when reference is made to molecular weight, it will be the molecular weight in weight, expressed in g / mol. This can be determined by aqueous gel permeation chromatography (GPC) or measurement of the intrinsic viscosity in a 1 N solution of NaNO 3 at 30 C.

  The copolymer is preferably random.

  Preferably, the monomer (c) has the following structure: CH 3 H 2 CH 2 CH 2 N + CH 2 CH CH 2 XCH 3 X "being as defined above.

  A particularly preferred monomer is that of the above formula wherein X "represents Cl referred to as DADMAC (dimethyldiallylammonium chloride).

  The monomers (a) are advantageously water-soluble monoethylenically unsaturated C3-C8 carboxylic, sulphonic, sulfuric, phosphonic or phosphoric acids, their anhydrides and their water-soluble salts.

  Among the preferred monomers (a), there may be mentioned acrylic acid, methacrylic acid, α-ethacrylic acid, (3R-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacrylalanine, N-acryloyl-hydroxy-glycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfoethyl methacrylate, styrene sulfonic acid, vinyl sulfonic acid, vinylphosphonic acid, phosphonyl acrylate, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate, phophonopropyl methacrylate, and alkali metal salts and of these.

  DADMAC / acrylic acid (AA) copolymers are particularly preferred, with an AA / DADMAC ratio of between 4/4 and 8/4.

  It is specified that these copolymers have a negative or no average charge, at the pH of the composition or at the pH of use of the composition. This average load is defined by the following equation: [c] x, [a] 11a [c] c + [axx] a where: - [c] is the molar concentration in units (c), - [a] is the molar concentration in units (a), - Xc represents the possible degree of neutralization of the units (a) Ac (in the case where the units represent potentially cationic); Xc = [BH +] / ([B] + [BH +]), or - XA (a) are the possible neutralization rate of the units (c) (in the case of the units (c) Preferably terms, (a) and (b) In others are potentially anionic); XA = [A] / ([AH] + [Al.

  the copolymer does not comprise other units than the units, it is preferably not a terpolymer.

  The monomer preparation copolymers known to be free radical synthesis can be obtained according to the known techniques or copolymers, in particular by polymerization by ethylenically unsaturated starting processes which are compounds easily obtained by those skilled in the art. by implementing classical organic chemistry.

  oxygen-free, polymerization with or nitrogen. The radical polymerization is preferably carried out in an environment where ethanol, and reaction example in the presence of an inert gas (helium, argon, etc.) is carried out in an inert solvent, preferably methanol more preferred in the water.

  is initiated by addition of a polymerization initiator.

  Initiators used are the free radical initiators usually used in the art. Examples include organic peresters (t-butylperoxypivalate, t-amylperoxypivalate, t-butylperoxy-α-ethylhexanoate, etc.); organic compounds of the azo type, for example azobisamidinopropane hydrochloride, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile, etc.); inorganic and organic peroxides, for example hydrogen peroxide, benzyl peroxide and butyl peroxide, etc .; redox initiator systems, for example those comprising oxidizing agents, such as persulfates (especially ammonium or alkali metal persulfates, etc.); chlorates and bromates (including inorganic or organic chlorates and / or bromates); reducing agents such as sulphites and bisulphites (including inorganic and / or organic sulphites or bisulfites); oxalic acid and ascorbic acid as well as mixtures of two or more of these compounds.

  Preferred initiators are water soluble initiators. Especially preferred are sodium persulfate and azobisamidinopropane hydrochloride.

  Alternatively, the polymerization can be initiated by irradiation with ultraviolet light. The quantity of initiators used is in general, a sufficient quantity can carry out the initiation of the polymerization. Preferably, the initiators are present in an amount ranging from 0.001 to approximately 10% by weight relative to the total weight of the monomers, and preferably are included in an amount of less than 0.5 by weight relative to the total weight of the monomers, a preferred amount being in the range of 0.005 to 0.5% by weight based on the total weight of the monomers. The initiator is added to the polymerization mixture, either continuously or discontinuously.

  When it is desired to obtain high molecular weight copolymers, it is desirable to add fresh initiator during the polymerization reaction. Gradual or batch addition also allows for more efficient polymerization and shorter reaction time. The polymerization is carried out under effective reaction conditions to polymerize the monomers (c) and the monomers (a) in an oxygen-free atmosphere. Preferably, the reaction is conducted at a temperature of from about 30 to about 100 and preferably from 60 to 90 ° C. The oxygen-free atmosphere is maintained throughout the reaction, for example by maintaining the reaction time. a purge of nitrogen throughout the reaction.

  The composition advantageously comprises from 0.1% to 5% by weight of the polymer, preferably from 0.3 to 1.5% by weight. It is specified that the polymer can be introduced into the composition in the form of a more or less concentrated aqueous solution. The amounts mentioned above are quantities expressed as dry extract.

  Surfactant composition The composition is an aqueous composition comprising surfactants. It can be a mixture of different surfactants. The surfactants included in the composition comprise at least one anionic surfactant. The surfactants may also comprise amphoteric surfactants (true or zwitterionic amphoters), neutral surfactants and / or cationic surfactants. The compositions comprising at least one anionic surfactant and at least one amphoteric surfactant are particularly advantageous, in particular for reasons of softness. The total content of surfactants in the composition is between 5 and 30% by weight.

  For compositions for the treatment of hair, such as shampoos, the surfactant content is advantageously between 10 and 20% by weight. Such compositions may comprise salts, for example sodium or ammonium chloride, advantageously in a content of less than 3% by weight.

  For compositions intended for the treatment of the skin, such as gels, the content of surfactant is advantageously between 5 and 15% by weight. Such compositions also preferably comprise at least 2% by weight of salts, for example sodium or ammonium chloride.

  The proportion by weight of anionic surfactants relative to all the surfactants is preferably greater than 50%, preferably greater than 70%. Parameters (pH) The pH of the composition is greater than or equal to 5.5. It is for example between 5.5 and 7.5, preferably between 6 and 6.5. The pH obviously depends on the compounds present in the composition. Of course, it is possible to use in the composition pH-regulating agents, acids or bases, for example citric acid, or sodium, potassium or ammonium hydroxide.

  Natures of TA The anionic surfactants may be chosen from the following surfactants: alkyl ester sulfonates, for example of formula R-CH (SO 3 M) -CH 2 OOR ', or alkyl ester sulfates, for example of formula R-CH (OSO 3 M) -CH 2 O wherein R represents a C8-C20 alkyl radical, preferably a C10-C16 alkyl radical, R 'a C1-C6 alkyl radical, preferably a C1-C3 radical, and M an alkaline earth metal cation, for example sodium, or the ammonium cation. Mention may especially be made of methyl ester sulfonates whose radical R is C14-C16; alkylbenzenesulfonates, more particularly C9-C20, primary or secondary alkylsulfonates, especially C8-C22, alkylglycerol sulfonates; alkyl sulphates, for example of formula ROSO 3 M, where R represents a C 10 -C 24, preferably C 12 -C 20, alkyl or hydroxyalkyl radical; M a cation of the same definition as above; alkyl ether sulfates, for example of the formula RO (OA) n SO 3 M, where R represents a C 10 -C 24, preferably C 12 -C 20, alkyl or hydroxyalkyl radical; OA representing an ethoxylated and / or propoxylated group; M representing a cation of the same definition as above, n generally ranging from 1 to 4, such as, for example, lauryl ether sulfate with n = 2; alkylamidesulfates, for example of formula RCONHR'OSO3M where R represents a C2-C22 alkyl radical, preferably C6-C20, R 'a C2-C3 alkyl radical, M representing a cation of the same definition as above as well as their polyalkoxylated derivatives (ethoxylated and / or propoxylated) (alkylamidoether sulphates the salts of saturated or unsaturated fatty acids, for example those such as C8-C24, preferably C14-C20, and an alkaline earth cation, N-acyl N-alkyltaurates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates, mono and di phosphate esters, for example of the following formula: (RO) XP (= O) (OM) X or R represents an alkyl, alkylaryl, arylalkyl, aryl, optionally polyalkoxylated radical, x and x 'being equal to 1 or 2, with the proviso that the sum of x and x' is equal to 3 M represents an alkaline earth cation; Nonionic agents may be selected from the following surfactants: alkoxylated fatty alcohols; alkoxylated triglycerides alkoxylated fatty acids alkoxylated sorbitan esters alkoxylated fatty amines - alkoxylated di (1-phenylethyl) phenols - alkoxylated tri (1-phenylethyl) phenols - alkoxylated alkyl phenols - products resulting from the condensing the ethylene oxide with a hydrophobic compound resulting from the condensation of propylene oxide with propylene glycol, such as Pluronic marketed by BASF; the products resulting from the condensation of ethylene oxide with the compound resulting from the condensation of propylene oxide with ethylenediamine, such as Tetronic marketed by BASF; alkylpolyglycosides, such as those described in US Pat. No. 4,565,647; fatty acid amides, for example C 8 -C 20; The amphoteric surfactants (true amphoteric compounds comprising an ionic group and a potentially ionic group of opposite charge, or zwitterionic compounds comprising simultaneously two opposite charges) may be chosen from the following surfactants: betaines in general, in particular carboxybetaines from, for example, lauryl betaine (Mirataine BB from Rhodia) or octylbetaine; amidoalkyl betaines, such as cocamidopropyl betaine (CAPB) (Mirataine BDJ from Rhodia Chimie); sulfobetaines or sultaines, such as cocamidopropyl hydroxy sultaine (Mirataine CBS from Rhodia); alkylamphoacetates and alkylamphodiacetates, for example comprising a coco or lauryl chain (Miranol C2M, C32, L32 in particular, from Rhodia); alkylamphopropionates or alkylamphodipropionates (Miranol C2M SF); alkyl amphohydroxypropyl sultaines (Miranol CS).

  The cationic surfactants may be chosen from salts of primary, secondary or tertiary fatty amines, optionally polyethoxylated, quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium, or alkylpyridinium, imidazoline derivatives, cationic amine oxides.

  As examples of useful compositions, mention may be made of: Sodium compositions for shampoos typically comprising 12 to 16% by weight of sodium alkyl ether sulphate (for example sodium lauryl ether sulphate SLES) or of a mixture of sodium alkyl ether sulphate and sodium alkylsulfate (for example sodium lauryl sulphate SLS), 1 to 3% of an amphoteric surfactant (for example cocoamidopropylbetaine CAPB), 0.5 to 2% of a salt (for example sodium chloride).

  Ammonium compositions for shampoos typically comprising 12 to 16% by weight of ammonium alkyl ether sulphate (for example ammonium lauryl ether sulphate ALES) or of a mixture of ammonium alkyl ether sulphate and ammonium alkyl sulphate (for example ammonium lauryl sulphate ALS), 1 to 3% of an amphoteric surfactant (for example cocoamidopropylbetaine CAPB), 0 to 2% of a salt (for example ammonium chloride).

  - The sodium compositions for gel-shower typically comprising 6 to 10% by weight of sodium alkylethersulfate (for example sodium laurylethersulphate SLES) or of a mixture of sodium alkylethersulfate and sodium alkylsulfate (for example laurylsulphate). sodium SLS), 1 to 3% of an amphoteric surfactant (for example cocoamidopropylbetaine CAPB), 2 to 4% of a salt (for example sodium chloride).

  The sodium compositions for gel-shower typically comprising 6 to 10% by weight of ammonium alkyl ether sulphate (for example ALES ammonium lauryl ether sulphate) or of a mixture of ammonium alkyl ether sulphate and ammonium alkyl sulphate ( for example ammonium lauryl sulphate ALS), 1 to 3% of an amphoteric surfactant (for example cocoamidopropylbetaine CAPB), 0 to 4% of a salt (for example ammonium chloride).

  Other Compounds The composition may comprise any other compound used in cosmetic compositions intended to be rinsed (shampoo, shower gel ...).

  Examples include sequestering agents, foamers, foam modifiers, dyes, pearlizers, moisturizing agents, anti-dandruff or antiseborrhoeic agents, suspending agents, emulsifying agents, ceramides, pseudoceramides, electrolytes, fatty acids, fatty acid esters, hydroxy acids, thickeners, perfumes, preservatives, organic or inorganic sunscreens, proteins, vitamins, polymers, silicones. Some of these compounds are detailed below.

  Other Polymers The composition may comprise other polymers, synthetic or natural or from biological preparation processes, where appropriate functionalized, for example by cationic or neutral groups. These polymers may have an action of stabilization, structuring of the compositions, and / or a conditioning action (deposition on the surface of the skin or hair).

  By way of examples, mention may be made of cationic derivatives of polysaccharides, such as guar or cellulose derivatives. Cationic polymers functionalized with hydrophobic groups such as C 1 -C 14 and preferably C 2 -C 8 alkyl chains, optionally having a hydroxyl group, may be used. These hydrophobic groups are attached to the main polymer chain via ether bonds.

  Moreover, and in the case of cationic modified or non-hydrophobic cationic guars, the cationic group is a quaternary ammonium group bearing three radicals, identical or different, chosen from hydrogen, an alkyl radical comprising 1 to 22 carbon atoms, more particularly 1 to 14, advantageously 1 to 3 carbon atoms. Counterion is a halogen, preferably chlorine.

  In the case of hydrophobic or non-hydrophobic modified cationic celluloses, the cationic group is a quaternary ammonium group bearing three radicals, identical or different, chosen from hydrogen, an alkyl radical comprising 1 to 10 carbon atoms, more particularly 1 to 6, advantageously 1 to 3 carbon atoms. Counterion is a halogen, preferably chlorine.

  Among the cationic guar derivatives, mention may be made of hydroxypropyl trimonium chloride guar (Jaguar C13S, C14S, or C17 marketed by Rhodia Chimie) or hydroxypropyl guar hydroxypropyltrimonium chloride (Jaguar C162 marketed by Rhodia).

  Among the cationic cellulose derivatives, one may use the 1,2-poly (oxyethanediyl) hydroxy-2-trimethylammonium propyl cellulose or polyquaternium-10 ether, such as Polymer JR400 marketed by Union Carbide.

  Nonionic derivatives of polysaccharides, for example hydroxypropyl guar, may also be used.

  Synthetic polymers may also be suitable, and more particularly homopolymers such as polymethacrylamidopropyl trimonium chloride (Polycare 133 marketed by Rhodia Chimie).

  The cationic polymers more particularly have a molar mass by weight of at least 2000 g / mol and more preferably between 2.104 and 3.106 g / mol, depending on their degree of possible polymerization. The molar masses by weight of the polymers are usually measured by size exclusion. Optionally, they can be measured directly by light scattering or from intrinsic viscosity using a calibration according to G. Robinson's "Viscosity-Molecular weight relationship, intrinsic chain flexibility and dynamic solution properties of guar galactomannan", SB Ross Murphy, ER Morris, Carbohydrate Research 107, p.17-32, 1982.

  In the case of cationic derivatives of polysaccharides, the degree of hydroxyalkylation (molar substitution or MS) is preferably between 0 and 1.2. In the case of these polymers, the degree of cationicity (degree of substitution or DS) is more particularly between 0.01 and 0.6. This is for example the case of Jaguars C162 and C2000 marketed by Rhodia Chimie.

  - Other Conditioner (Silicone) The composition may comprise a silicone (silicone oil). Silicone is understood to mean any organosiloxane compound comprising alkyl groups (for example methyl) and / or functionalized with groups other than alkyl groups. The silicones are preferably present in the composition in the form of an emulsion (liquid droplets of silicone dispersed in the aqueous phase).

  Among the water-soluble silicone derivatives of the composition, mention may be made, inter alia, of dimethicone copolyols (Mirasil DMCO marketed by Rhodia Chimie).

  With regard to the silicones in the form of water-insoluble dispersions of the composition, non-water-soluble and non-volatile organopolysiloxanes (also hereafter referred to as "non-water-soluble and non-volatile silicones" may be conveniently used). ) among which may be mentioned oils, gums or resins polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, or their functionalized non-water-soluble derivatives, or their mixtures, non-volatile.

  Said organopolysiloxanes are considered as non-water-soluble and non-volatile, when their solubility in water is less than 50 g / liter and their intrinsic viscosity is at least 3000 mPa.s at 25 C.

  By way of examples of non-water-soluble and non-volatile organopolysiloxanes or silicones, mention may be made of silicone gums, for example the diphenyl dimethicone gum marketed by Rhodia Chimie, and preferably polydimethylsiloxanes having a viscosity of at least 6.105 mPa. at 25 ° C., and even more preferably, those having a viscosity greater than 2.sup.6 mPa.s at 25 ° C., such as Mirasil DM 500000 marketed by Rhodia Chimie. According to the invention, the organopolysiloxane or non-water-soluble silicone and

  nonvolatile is in a dispersed form within the cosmetic composition containing it.

  This is in the form of particles or droplets whose size can be chosen according to the nature of the cosmetic composition or the performance sought for said composition. In general, this size can vary from 0.01 to 70 microns.

  In a preferential manner, this size is of the order of 0.1 to 50 microns, especially of the order of 1 to 30 microns.

  To facilitate their implementation, these organopolysiloxanes may be previously dispersed or solubilized in silicone derivatives of low viscosity, volatile or not, and then emulsified in the cosmetic composition.

  Among these silicones of low viscosity, mention may be made of cyclic volatile silicones and polydimethyl siloxanes of low mass.

  It is also possible to use functionalized silicone derivatives such as amino derivatives directly in the form of emulsions or from a preformed microemulsion. These may be compounds known as amino silicones or hydroxylated silicones. Mirasil ADM-E (Amodimethicone) sold by the company Rhodia, and dimethiconol.

  - Other compounds It is also possible to use oils that can perform conditioning, protective or emollient functions. Such oils are generally chosen from alkylmonoglycerides, alkyldiglycerides and triglycerides, such as oils extracted from plants and plants (palm, coconut, cottonseed, soybean, sunflower, olive, coconut oil and palm oil). grapes, sesame, peanut, castor oil ...) or oils of animal origin (tallow, fish oils ...), derivatives of these oils such as hydrogenated oils, derivatives of lanolin, petrolatum, mineral oils or paraffinic oils, perhydrosqualane, squalene, diols such as 1-2-dodecanediol, cetyl alcohol, stearyl alcohol, oleic alcohol, fatty esters such as isopropyl palmitate , 2-ethylhexyl cocoate, myristyl myristate, lactic acid esters, stearic acid, behenic acid, isostearic acid.

  It is also possible to incorporate in the cosmetic composition, in the form of dispersions or solutions, bactericidal or fungicidal agents in order to improve the disinfection of the skin, such as, for example, triclosan; anti-dandruff agents, such as zinc pyrithione or octopyrox; insecticidal agents such as natural or synthetic pyrethroids.

  The cosmetic compositions may also contain agents for the protection of the skin and / or the hair against the aggressions of the sun and UV rays. Thus, the compositions may comprise sunscreens which are chemical compounds that strongly absorb UV radiation, such as the compounds authorized in the European Directive N 76/768 / EEC, its annexes and subsequent modifications of this directive.

  In the case where the various constituent elements of the cosmetic composition have too little solubility in the composition or when they are in solid form at ambient temperature, said constituent elements may advantageously be solubilized in an organic vehicle, such as mineral oils or natural, silicone derivatives, waxes, or else encapsulated in matrices such as polymers of latex type.

  The cosmetic compositions that are the subject of the invention may also contain fixing resins.

  These fixing resins, when they are present, are generally at concentrations of between 0.01 and 10%, preferably between 0.5 and 5%.

  The fixing resins used in the cosmetic compositions are more particularly chosen from the following resins: les methyl acrylate / acrylamide copolymers, polyvinyl methyl ether / maleic anhydride copolymers, vinyl acetate / crotonic acid copolymers, octyl acrylamide / methyl acrylate / butylaminoethyl methacrylate copolymers, polyvinyl pyrrolidone copolymers polyvinylpyrrolidone / methyl methacrylate copolymers, polyvinylpyrrolidone I vinyl acetate copolymers, polyvinyl alcohols, polyvinyl alcohol / crotonic acid copolymers, polyvinyl alcohol / maleic anhydride copolymers, hydroxypropyl celluloses, hydroxypropyl guars, sodium polystyrene sulfonates, polyvinylpyrrolidone / ethyl methacrylate / acid terpolymers methacrylic acid monomethyl ethers of poly (methyl vinyl ether / maleic acid), polyvinyl acetates grafted on polyoxyethylene trunks (EP-A-219 048), and the copolyesters derived therefrom. of a terephthalic and / or isophthalic and / or sulfoisophthalic acid and / or a diol, such as: - polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, (US Pat. A-3,959,230, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666); sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2-propylene diol (US-A-4,968,451); the polyester copolymers derived from dimethylterephthalate, isophthalic acid, dimethyl sulfoisophthalate and ethylene glycol (EP-A-540374); copolymers comprising polyester units derived from dimethylterephthalate, isophthalic acid, dimethyl sulphoisophthalate and ethylene glycol and polyorganosiloxane units (FR-A-2 728 915).

  sulphonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulphosuccinate and diethylene glycol (FRA-2,236,926); polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl, methyl units; (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or sulfopolyethoxy anionic groups (US-A-4,721,580), sulfoaroyles (US-A-4,877). 896); polyesters-polyurethanes obtained by reaction of a polyester obtained from adipic acid and / or terephthalic acid and / or sulfoisophthalic acid and a diol, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol and a diisocyanate (FR-A-2 334 698); Ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898, EP-A-11 984).

  Preferably, the fixing resins are chosen from polyvinylpyrrolidone (PVP), copolymers of polyvinylpyrrolidone and of methyl methacrylate, copolymer of polyvinylpyrrolidone and of vinyl acetate (VA), polyterephthalic copolymers of ethylene glycol, polyethylene glycol, copolymers of polyterephthalate sodium ethylene glycol I polyethylene glycol / polyisophthalate sulfonate, and mixtures thereof.

  These fixative resins are preferably dispersed or solubilized in the chosen vehicle.

  The cosmetic compositions which are the subject of the invention may also contain polymeric derivatives exerting a protective function.

  These polymeric derivatives may be present in amounts of about 0.01-10%, preferably about 0.1-5%, and most preferably about 0.2-3% by weight.

  These agents may especially be chosen from: nonionic cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose; polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted onto polyoxyethylene trunks (EP-A-219 048); polyvinyl alcohols.

  The cosmetic compositions which are the subject of the invention may also comprise plasticizing agents.

  Said agents, if they are present, can represent between 0.1 to 20% of the formulation, preferably from 1 to 15%.

  Particularly useful plasticizers include adipates, phthalates, isophthalates, azelates, stearates, silicone copolyols, glycols, castor oil, or mixtures thereof.

  It is also advantageous to add to these compositions metal sequestering agents, more particularly those sequestering calcium such as citrate ions.

  It is also possible to incorporate in the cosmetic compositions which are the subject of the invention humectants, among which are, inter alia, glycerol, sorbitol, urea, collagen, gelatin, aloe vera, acid hyaluronic or volatile water-soluble solvents such as ethanol or propylene glycol, the contents of which can reach up to 60% by weight of the composition.

  To further reduce the irritation or aggression of the scalp, it is also possible to add water-soluble or water-dispersible polymers such as collagen or certain non-allergenic derivatives of animal or vegetable proteins (hydrolysates of wheat proteins, for example), natural hydrocolloids ( guar gum, carob, tara, etc.) or from fermentation processes and the derivatives of these polycarbohydrates, such as modified nonionic celluloses such as, for example, hydroxyethylcellulose, or anionic such as carboxymethylcellulose; guar or carob derivatives such as their nonionic derivatives (for example hydroxypropylguar) or anionic derivatives (carboxymethylguar and carboxymethylhydroxypropylguar).

  To these compounds may be added in combination, powders or mineral particles such as calcium carbonate, sodium bicarbonate, calcium dihydrogenphosphate, inorganic oxides in powder form or in colloidal form (particles of smaller size or the order of a micrometer, sometimes a few tens of nanometers) such as titanium dioxide, silica, aluminum salts generally used as antiperspirants, kaolin, talc, clays and their derivatives, etc. .

  Preservatives such as methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid, sodium benzoate, GERMABEN or any chemical agent that prevents the proliferation of bacteria or mold and traditionally used cosmetic compositions, can also be used. be introduced into the cosmetic aqueous compositions according to the invention, generally at a level of 0.01 to 3% by weight.

  The amount of these products is usually adjusted to prevent any proliferation of bacteria, molds or yeasts in the cosmetic compositions.

  As an alternative to these chemical agents, water-activity-modifying agents can be used which can increase the osmotic pressure, such as carbohydrates or salts.

  To protect the skin and / or the hair from sun and UV rays, mineral particles such as zinc oxide, titanium dioxide or cerium oxides in the form of powder or particles can be added to these formulations. colloidal, alone or in combination. These powders may optionally be surface treated to increase the effectiveness of their anti-UV action or to facilitate their incorporation into cosmetic formulations or to inhibit surface photoreactivity.

  To these ingredients can be added, if necessary, and in order to increase the comfort during the use of the composition by the consumer, one or more perfumes, coloring agents among which may be mentioned the products described in the Annex IV ("List of colouring agents allowed for use in cosmetic products") of the European directive n 76/768 / EEC of 27 July 1976 known as the cosmetic directive, and / or opacifying agents such as pigments.

  Although this is not mandatory, the composition may also contain viscosifying or gelling polymers so as to adjust the texture of the composition, such as crosslinked polyacrylates (Carbopol marketed by Goodrich), non-cationic derivatives of cellulose such as hydroxypropylcellulose , carboxymethylcellulose, guars and their nonionic derivatives, xanthan gum and its derivatives, used alone or in combination, or the same compounds, generally in the form of water-soluble polymers modified with hydrophobic groups covalently bound to the polymer backbone as described in WO 92/16187 and / or water to bring the total of the constituents of the formulation to 100%.

  The cosmetic compositions which are the subject of the invention may also contain polymeric dispersing agents in an amount of about 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as: water-soluble salts of polycarboxylic acids with a weight-average molecular mass of the order of 2000 to 100000 g / mol, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and most particularly polyacrylates of molecular weight in the order of 2,000 to 10,000 g / mol (US-A-3,308,067), copolymers of acrylic acid and maleic anhydride with a weight-average molecular weight in the range of 5000 to 75,000 g / mol (EP-A-66 915); 5. polyethylene glycols with a weight-average molecular weight of the order of 1000 to 50000 g / mol.

  Other details or advantages of the invention will emerge more clearly from the following examples, without limitation.

Examples

  Compositions comprising ingredients selected from the following: Ingredient Type Compound SLES Surfactant sodium lauryl ether sulfate (2E0), EMPICOL anionic ESB / 3M marketed by Hunstman SLS Surfactant Anionic sodium lauryl sulphate ALES Surfactant lauryl ether ammonium sulfate (2E0), RHODAPEX - anionic EA-2 marketed by Rhodia ALS surfactant ammonium lauryl sulphate, RHODAPON L-22 anionic marketed by Rhodia CAPE surfactant Cocoamidopropyl betaine, MIRATAINE BET-C-30 amphoteric marketed by Rhodia Salt Sodium chloride or ammonium chloride Polymer A Copolymer comprising 40% by number of units derived from DADMAC and 60% by number of units derived from acrylic acid, molar mass of about 300,000.

  Polymer B Copolymer comprising 25% by number of units derived from DADMAC and 75% by number of units derived from acrylic acid, molar mass of about 300,000.

  Procedure 1. Mix the water and the polymer 2. Add the CAPB 3. Add the anionic surfactant 4. Adjust the pH to 6-6.5 by adding sodium hydroxide or citric acid 5. Add the The following compositions are produced, the amount by weight of each ingredient being given below: Example 1 2 3 4 5 6 7 8 9 10 11 SLES (%) 14 14 14 14 II ll 8 8 8 SLS (%) / II l / I / / I / / ALES (%) / II / 7 7 7 7 / l I ALS (%) / l II 7 7 7 7 / II CAPB (%) 2 2 2 2 2 2 2 2 2 2 2 NH4Cl (%) / I 1/25, 25 / I 0.25 III NaCl (%) 1.5 1.5 1.5 1.5 / III 3 3 3 Polymer 0.31 / I 0.31 II 0.5 0.5 IA (%) Polymer / I 1% II / 1% I / / / B (%) Water Up to 100% Examples 4, 8 and 11 are comparative examples.

  The transmittance (transparency) of the compositions is measured at 600 nm using a spectrophotometer (Jasco 7800 type).

  The Brookfield viscosity of the compositions is measured using a Brookfield DV-I viscometer at 22 ° C, 10 revolutions per minute, spindle 4 for viscosities less than 11000 mPa · s, spindle 5 for viscosities of 11000 to 30000 mPa.s, spindle 6 beyond.

Claims (12)

  1. Cosmetic composition comprising water, a surfactant and an ampholytic copolymer comprising cationic units (c) and anionic or anionic units (a), characterized in that: the polymer comprises: 0.1 to 50% by number of units (c) deriving from the polymerization of at least one monomer compound (c) of the following general formula I: R 1 R 2 R 4 H 2 C = C + CHN + L CHOC = CH 2 X-R 3 in which: R 4 and R 4 represent, independently of one another, a hydrogen atom or a linear or branched C 1 -C 6 alkyl group; R2 and R3 represent, independently of one another, an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C1-C6 chain, preferably a methyl group; n and m are integers between 1 and 3; X, which are identical or different, represent counterions compatible with the water-soluble or water-dispersible nature of the polymer; from 50 to 99.9% by number of units (a) deriving from the polymerization of at least one monomeric (a) hydrophilic compound bearing a function with an acidic character copolymerizable with (c), anionic or capable of being anionic, the pH of the composition is greater than or equal to 5.5, preferably between 5.5 and 7.5, the proportion by weight of surfactant in the composition is between 5 and 30% by weight, the surfactant comprising a anionic surfactant and optionally an amphoteric surfactant, the proportion by weight of the copolymer in the composition is between 0.1 and 5%, preferably between 0.2 and 1.5%.   2. Composition according to claim 1, characterized in that it is a shampoo comprising between 10 and 20% of surfactant, or a geldouche comprising between 5 and 15% of surfactant.   3. Composition according to one of the preceding claims, characterized in that: - units (c) are derived from dimethyldiallylammonium (DADMAC), the units (a) are derived from acrylic acid, - the ratio by number between the units (a ) and the units (c) is between 4/4 and 8/4. 5 4. Composition according to one of the preceding claims characterized in that the anionic surfactant is selected from aikylesters sulfonates, alkylbenzenesulfonates, alkylsulfates, alkylethersulfates, alkamides sulfates, alkylamidoethersulfates, fatty acids, N-acyl Nalkyltaurates alkylisethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates, mono and di ester phosphates, and salts thereof, alone or in mixtures.   5. Composition according to one of the preceding claims characterized in that it comprises an amphoteric surfactant selected from betaines, sulfobetaines, alkylamphoacetates, alkylamphopropionates, alkyl amphohydroxypropyl sultalnes.   6. Composition according to one of the preceding claims, characterized in that it comprises 12 to 16% by weight of sodium alkylethersulfate or a mixture of alkylethersulfate and sodium sodium alkylsulphate, 1 to 3% an amphoteric surfactant, and 0.5 to 2% of a salt.   7. Composition according to one of the preceding claims, characterized in that it comprises 12 to 16% by weight of ammonium alkyl ether sulphate or a mixture of ammonium alkyl ether sulphate and ammonium alkyl sulphate, 1 3% of an amphoteric surfactant, and 0 to 2% of a salt.   8. Composition according to one of the preceding claims, characterized in that it comprises 6 to 10% by weight of sodium alkylethersulfate or a mixture of sodium alkylethersulfate and sodium alkylsulfate, 1 to 3% an amphoteric surfactant, and 2 to 4% of a salt.   9. Composition according to one of the preceding claims, characterized in that it has a transmittance of at least 90%, preferably at least 95%.   10. Use of the copolymer in the composition according to one of the preceding claims as agent for increasing the viscosity.   11. Use of the copolymer in the composition according to one of the preceding claims as an agent for depositing on the hair or on the skin, or as a conditioner aid agent, on the hair or on the skin.   12. Use according to the preceding claim, characterized in that the composition has a transmittance measured at 600 nanometers at least equal to 90%, preferably at least 95%.