FR2745175A1 - Cosmetic hair styling compositions - Google Patents

Abstract

A capillary cosmetic composition for setting the hair comprising (a) 0.1-30 (2-10) wt. % of at least one amphoteric surfactant derived from an aminoacid and containing at most 1 wt. % inorganic salts on surfactant; (b) 0.01-10 % of a fixative resin of anionic, cationic, nonionic or amphoteric type or a mixture of these and (c) a cosmetically acceptable vehicle.

Description

The present invention relates to hair cosmetic compositions comprising surfactants derived from amino acids and fixing resins.

The cosmetic compositions are generally formulated by placing one or more active or treating ingredients, and optionally additives, in a cosmetically acceptable vehicle.

However, the nature of the vehicle does not always make it possible to solubilize all the ingredients and the use of surfactants is then necessary to compatibilize the ingredients in the vehicle in the form of a dispersion or an emulsion.

Regardless of the nature of the vehicle, even when the composition does not pose a problem of compatibility, it may be desirable to incorporate surfactants into the composition to obtain particular properties during use, for example to promote the formation of foam .

Unfortunately, the surfactants are themselves sometimes incompatible with other ingredients of the composition and may be at the origin of cloudiness or opacity, or of inhomogeneity or even demixing in the composition, adversely affecting, on the one hand, the aesthetics of the product and, secondly, the regularity of the deposit of the agents on the hair and more generally to the desired properties, for example to the formation of foam.

Thus, in the field of hair compositions intended to modify permanently or temporarily the external appearance of the hair, a major difficulty consists in compatibilizing the surfactants and the fixing resins. A number of solutions exist but often require the use of irritating surfactants for the skin and (or the eye.

However, in recent years, there is a very important need for surfactants which are both effective and which are not irritating to the skin or the eyes and which can be used without particular precautions with maximum safety.

Researches of non-irritating products have converged on amphoteric surfactants (that is to say having an overall electrical charge of zero) of the betaine or amphoacetate type, the synthetic processes of which are generally based on a carboxylation reaction of a fatty amine, for example an alkylamidoethylethanolamine or an alkylimidazoline, on monochloroacetic acid or its sodium salt. This synthesis thus leads to the release of Na + Cl-, the Cl- anion from monochloroacetic acid, as well as the release of sodium glycolate from the hydrolysis of the starting acid.

The major disadvantages encountered with the surfactants of the above type are as follows - significant increase in the viscosity of the surfactant solution which does not allow
to concentrate the solutions beyond a concentration by weight of about 30% because the
viscosity increases sharply, which prevents the marketing of solutions
concentrated; - deterioration of the cold behavior and emulsifying and stabilizing properties; - problem of compatibility with the other additives of the compositions (agents
thickeners, preservatives, silicone emulsions, fixative resins, agents
conditioners, etc.).

The present invention aims to solve the compatibility problems posed by these surfactants in the presence of fixative resins in hair cosmetic compositions.

 It has been unexpectedly found that the performance of the cosmetic compositions which are the subject of the invention can be achieved by careful control of the levels of inorganic salts (in particular NaCl) in these amphoteric surfactants: by limiting this content to a certain amount. less than or equal to 1% by weight, not necessarily zero, these surfactants are fully compatible with fixing resins and the ingredients of the composition can be applied homogeneously to the hair to effectively develop their properties.

The present invention relates to a cosmetic composition for the hair comprising: a) from 0.1 to 30% of an amphoteric surfactant derived from an amino acid having an inorganic salt content of at most 1% by weight; 0.01 to 10% of a fixing resin which may be of anionic, cationic, nonionic or amphoteric nature, or a mixture; (c) a cosmetically acceptable vehicle.

The compositions forming the subject of the invention can be formulated in a large number of types of products, such as foams, gels, conditioners, rinsing formulas, shampoos.

The products described as constituting compositions which are the subject of the invention can be used in this type of formulations for the hair and more particularly in formulations of mousse, styling gels or any formulation used for styling or to facilitate the combing of hair. hair.

In the present application, the term "amino acid", as well known to those skilled in the art, a compound carrying at least one amine function and an acid function such as those present in amino acids and natural acids, including carboxylic acid, sulfonic acid, phosphonic acid functions.

Surfactants derived from amino carboxylic acid or amino acid sulfonic used according to the invention are amphoteric surfactants comprising: at least one ammonium function or an amino function capable of being protonated, and at least one carboxylic acid function or sulfonic, respectively.

These surfactants may be in particular betaine or sulfobetaine surfactants, including amidoalkylbetaines and amidoalkyl sulfobetaines, or alternatively amphoacetate surfactants or amphodiacetates.

Among the surfactants of betaine type, mention will be made, for example
betaines of formula 1:
R1 R2 R3 NR4 C (O) O- (1)
sulfobetaines of formula 2:
R1R2R3NR4SO3- (2)
amidoalkyl betaines of formula 3:
R1C (O) -NH R4 N (R2 R3) R5 C (O) O- (3)
and the amidoalkylsulfobetaines of formula 4:
R1C (O) -NH R4 N (R2 R3) R5 SO3- (4) in which the radical R1 represents an alkyl or alkenyl radical having from 10 to 24 carbon atoms, the radicals R2, and R3, which are identical or different, represent an alkyl radical having 1 to 4 carbon atoms, and the radicals R4 and R5, which may be identical or different, represent an alkylene radical having from 1 to 4 carbon atoms.

The betaines of formula (1) can be obtained in particular by carboxylation of the amine of formula R1 R2R3N by the halocarboxylic acid of formula Hal-R4COOH or a salt thereof, whereas the sulphobetaines of formula (2) can be obtained in particular by sulfonation of the amine of formula R1 R2R3N with halosulfonic acid of formula
Hal-R4-SO3H or a salt thereof in the presence of an alkaline agent. These reactions are accompanied by the release of the corresponding alkaline halide salt.

The amidoalkyl betaines or sulfobetaines are obtained analogously from the corresponding amidoalkylamine.

dans laquelle R1 a la signification ci-dessus et représente le plus souvent des chaînes coco et lauryle, R6 et R7 identiques ou différents, représentent un radical alkylène ayant 2 à 6 atomes de carbone, et M représente un atome d'hydrogène ou de métal alcalin, ou un ion ammonium.Among the surfactants of the amphoacetate type, mention will be made more particularly of alkylamphoacetates corresponding to the general formula (5):

in which R 1 has the above meaning and most often represents coco and lauryl chains, R 6 and R 7, which are identical or different, represent an alkylene radical having 2 to 6 carbon atoms, and M represents a hydrogen or metal atom. alkali, or an ammonium ion.

et leurs homologues répondant plus généralement à la formule (5)

formules dans lesquelles R1, R6, R7 et M ont les significations ci-dessus.
Un procédé généralement utilisé pour préparer les alkylamphoacétates est la réaction d'une alkylimidazoline de formule (6).

The present invention more particularly relates to cosmetic compositions comprising amphoteric surfactants such as alkylamphoacetates, and more particularly the amidoamine derivatives listed in the RCosmetics dictionary.
Toiletries Fragrance Association Edition 1994 under the names alkylamphoacetate or alkylamphodiacetate and having the formula

and their counterparts more generally responding to formula (5)

formulas in which R1, R6, R7 and M have the meanings above.
A method generally used to prepare alkylamphoacetates is the reaction of an alkylimidazoline of formula (6).

in which R 1, R 6 and R 7 have the meanings given above, or of one of its open-ring derivatives with a monohaloacetic acid, preferably chloroacetic acid or one of its salts in the presence of an alkaline agent (see in particular US
A 2,528,378 and US-A-2,773,068).

Preferably the pH of the reaction mixture is set to not exceed 10 during the reaction (see European Patent Application EP-A-0 647 469).

The alkali is preferably sodium hydroxide and the pH is preferably maintained between 8.5 and 9.5, the temperature of the reaction being preferably between 75 and 85 ° C.

For the purposes of the present invention, the various surfactants derived from carboxylic or sulphonic amino acids described above must have a low content of inorganic salts, in particular alkali halides which may derive from their synthesis, namely at most 1% by weight. . Absolute purity with respect to the inorganic salts is not necessary and very good properties are observed for contents of 0.05 to 1% by weight.

The surfactants with a low content of inorganic salts constituting cosmetic hair compositions which are the subject of the invention may be obtained according to various purification methods well known to those skilled in the art, such as, for example, the purification by dialysis or electrodialysis of solutions. aqueous surfactants as described in the French patent application No. 95 04 014 filed by the Applicant on April 5, 1995, the precipitation of inorganic salts, in particular by a third solvent, or liquid liquid extraction, or according to methods of synthesis that does not lead to the formation of inorganic salts. For example, an alkylamphoacetate suitable for the invention can be obtained directly by reaction of an aminoalkylalkanolamine of formula (7):
In which R 1, R 6 and R 7 have the meaning indicated above with formaldehyde and a cyanide of formula (8): ## STR2 ##
XCN (8)
in which X represents a hydrogen atom or an alkali metal, in particular lithium,
sodium or potassium, provided that if X is a hydrogen atom, the
nitrile obtained with an alkaline agent.

Such a cyanide process is described in British Patent Application No. 94.23573
deposited on November 22, 1994. The alkaline agent is preferably sodium hydroxide.

Preferably, R6 and R7 are identical and represent an ethylene radical in the
formula (7).

The preferred methods of preparation of the surfactants suitable for the compositions
The cosmetics which are the subject of the invention are the electrodialysis of aqueous solutions of surfactants or the cyanide process.

In general, the amino acid-derived surfactants having an inorganic salt content of at most 1% by weight, used in the hair cosmetic compositions that are the subject of the invention, are present in an amount corresponding to about 0, 1-30%, advantageously 0.5-30% by weight relative to the total weight of the formulation, preferably from 2 to 10%. The quantities can be adjusted to obtain the best level of performance.

The fixative resins used as constituents of the hair cosmetic compositions that are the subject of the invention are generally present at concentrations of 0.01 to 10% by weight relative to the total weight of the formulation, preferably from 0.5 to 5%.

The fixing resins that may be used according to the invention are preferably chosen from the following resins: acrylate / acrylamide copolymers, polyvinylmethyl ether / maleic anhydride, vinyl acetate / crotonic acid, octylacrylamide / acrylate / butylaminoethyl methacrylate, polyvinylpyrrolidone ( PVP), polyvinylpyrrolidone copolymers, especially polyvinylpyrrolidone and methyl methacrylate copolymers, polyvinylpyrrolidone and vinyl acetate (VA) copolymers, polyvinyl alcohol, copolymers of polyvinyl alcohol and crotonic acid, copolymers of polyvinyl alcohol and maleic anhydride, sodium polystyrene sulfonate; a polyvinylpyrrolidone / ethyl methacrylate / methacrylic acid terpolymer, poly (methylvinyl ether / maleic acid) monomethyl ether; polycondensates of ethylene glycol terephthalate / ethylene glycol, polycondensates of diester, sulphoisophthalic / glycol terephthalic acid or anhydride, and mixtures thereof, polyvinyl acetate grafted onto polyoxyalkylene trunks such as polyvinyl acetate) grafted on polyoxyethylene trunks (EP-A-219 048), polyester copolymers based on ethylene terephthalate and / or propylene terephthalate units, and polyoxyethylene terephthalate, with a ratio of the number of ethylene terephthalate units and / or propylene terephalate at the number of polyoxyethylene terephthalate units of the order of 1/10 to 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of from 300 to 5000, preferably from 600 to 5000 (US-A-3,959,230, US-A-3,893,929, US-A-4,118,996, US-A-4,702,857, US-A-4,770,666); sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1,2-propylene diol having from 1 to 4 sulfonated groups (US-A-4,968,451); polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl or 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); polyesterpolyurethanes obtained by reacting a polyester with a number-average molecular mass of 300-4000 obtained from adipic acid and / or terephthalic acid and / or sulfoisophthalic acid and a diol having a mass of less than 300, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 600-4000 and a diisocyanate (FR-A-2 334 698); sulphonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulphosuccinate and diethylene glycol (FR-A-2,236,926); sulfonated polyesters obtained by condensation of dimethyl terephthalate / sodium dimethylsulfonate isophthalic acid / ethylene glycol (EP-A-540 374), or mixtures thereof.

In addition, cationic resins can also be used. These cationic resins consist entirely or partly of cationic monomers such as, for example, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, diallyldimethylammonium chloride, or mixtures thereof.

Preferably, the fixing resins which are the subject of the invention will be of the polyvinylpyrrolidone (PVP) type, copolymers of polyvinylpyrrolidone and methyl methacrylate, copolymer of polyvinylpyrrolidone and of vinyl acetate (VA), polycondensates of ethylene terephthalate glycol / ethylene glycol, diester polycondensates, terephthalic acid / anhydride / sulfoisophthalic acid / glycol, and mixtures thereof.

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

The cosmetic compositions forming the subject of the invention comprise a vehicle, or a mixture of several vehicles, which are compatible with a capillary application. These vehicles may be present in particular at concentrations of between 0.5% and 99.5%, preferably between 5 and 99.5%. The term "compatible with a hair application" means here that the vehicle does not damage or exert any negative effects on the appearance of the hair or does not cause irritation of the skin and / or the eye and / or the scalp.

Vehicles compatible with the applications described in this invention include, for example, those used in sprays, foams, tonics, gels, shampoos, or rinse lotions. The choice of the appropriate vehicle will depend on the nature of the constituents, in particular the resin, and whether the formulated product is intended to be left on the surface where it has been applied (eg sprays, foams, tonic lotion, or gels) or rinsed after use (eg shampoo, conditioner, rinse lotions).

The vehicles that may be used include a large number of products commonly used in hair cosmetic compositions. The vehicles may comprise a solvent for solubilizing or dispersing the ingredients used, such as water, C1-C6 alcohols, and mixtures thereof, in particular water and methanol, ethanol,
Isopropanol, and mixtures thereof.

The problem of compatibility is particularly crucial in the case where a vehicle comprising a phase of hydrophilic nature is brought into contact with lipophilic ingredients, since the homogeneity of the composition directly depends on the possible interactions between its constituents. This is the case, in particular, when the vehicle and hydrophilic base, including water or alcohols or is of water / oil emulsion type.

 The vehicles may also include a wide variety of other compounds such as ketones such as acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as freons), linalool, esters (such as ethyl acetate, dibutyl phthalate) and volatile silicones (in particular siloxanes such as phenyl pentamethyl siloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopenta siloxane, cyclodimethicone, and dimethicone), and mixtures thereof.

When these cosmetic hair compositions are in the form of sprays, tonic lotions, gels, or foams, the preferred solvents include water,
Ethanol, volatile silicone derivatives, and mixtures thereof. The solvents used in these mixtures may be miscible or immiscible with each other.

Foams and aerosol sprays can also use any propellant capable of generating the products in the form of foam (in the case of foams) or in the form of fine, uniform sprays. By way of examples, mention may be made of trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethyl ether, propane, n-butane, or isobutane.

These vehicles can take a lot of forms. For example, vehicles in the form of emulsions include water-in-oil, oil-in-water, and oil-in-silicone emulsions. These emulsions cover a wide range of viscosity, from 0.1 to 200 Pa.s. These emulsions can also be delivered in the form of sprays using either a device of mechanical pump type, or in the form of aerosol pressurized by the use of a propellant gas. These vehicles can also be delivered in the form of foam. Examples which may be mentioned are anhydrous liquid solvents, such as oils, alcohols and silicones, homogeneous aqueous mixtures such as hydroalcoholic mixtures, and rheologically modified versions of these two systems, for example when the viscosity of the system has been increased by the addition of gums, resins, polymers, or salts).

The cosmetic compositions which are the subject of the invention may contain conditioning agents. Among the conditioning agents that can be used in the context of this invention, there are the conditioning agents of animal origin, such as hydrolysates of animal proteins and their salts, such as the dimethyl or trimethyl ammonium stearate salts of collagen hydrolysates, silk, keratin; cationic copolymer conditioning agents of synthetic origin, better known under the name polyquaternium, such as the copolymer of N, N'-bis ((dimethylamino) -3 propyl) urea and of oxy-1,1 'bis (chloro-2) ethane or polyquaternium-2, the copolymer of diallyldimethylammonium chloride and acrylamide or polyquaternium-7; cationic derivatives of polysaccharides, such as cocodimonium hydroxyethylcellulose, guar hydroxypropyl trimonium chloride, hydroxypropyl guar hydroxypropyltrimonium chloride (Jaguar C13S, Jaguar C162 marketed by Rhone-Poulenc), poly (oxyethanediyl-1,2) ether; 2-hydroxy-trimethylammonium-3-propyl cellulose or polyquaternium-10, silicones and silicone derivatives such as amodimethicone, cyclomethicone, copolyol cetyl dimethicone, cyclomethicone, dimethicone copolyol, trimethylsilyl amodimethicone, polyquaternium Surfactants of the cationic type such as distearyl dimethyl ammonium chloride.

The conditioning agents used as constituents of the hair cosmetic compositions that are the subject of the invention are preferably chosen from conditioning agents of synthetic origin, in particular the polyquaterniums -2, -7, and -10, and the cationic derivatives of polysaccharides. such as cocodimonium hydroxyethylcellulose, hydroxypropyl trimonium guar chloride, hydroxypropyl guar hydroxypropyltrimonium chloride.

It will be preferred to use the cationic derivatives of polysaccharides, and in particular the guar derivatives such as hydroxypropyl trimonium guar chloride and hydroxypropyl guar hydroxypropyl trimonium chloride.

The performance of the cosmetic compositions which are the subject of the invention can also be improved by the use of plasticizing agents. The plasticizer may advantageously represent from 0.1 to 20% by weight of the formulation, preferably from 1 to 15% .Advantageous plasticizing agents that may be mentioned include adipates, phthalates, isophthalates and azelates. stearates, silicone copolyols, glycols, castor oil, or mixtures thereof.

These cosmetic hair compositions may also comprise surfactants which serve to disperse, emulsify, solubilize, stabilize various compounds used for their emollient or humectant properties. The surfactants can be used in these compositions at concentrations advantageously varying from 0.05 to 50% by weight of the preparation. Anionic, nonionic, cationic, zwitterionic or amphoteric surfactants or mixtures of these surfactants are thus found.

In particular, surfactants such as the alkyl ester sulfonates of formula R-CH (SO 3 M) -COOR ', where R represents a C 8 -C 20 alkyl radical, preferably C 10 -C 16 alkyl radical, R', an alkyl radical of C1 -C6, preferably C1-C3 and M an alkaline cation (especially sodium, potassium, lithium), a substituted or unsubstituted ammonium (especially methyl-, dimethyl-, trimethyl-, tetramethylammonium, or dimethylpiperidinium) or derivative of an alkanolamine (especially monoethanolamine, diethanolamine or triethanolamine). Mention may especially be made of methyl ester sulfonates whose radical R is C14-C16; alkyl sulphates of formula ROSO3M, where R represents a C10-C24, preferably C12-C20, and especially C12-C18, alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above; as well as their ethoxylated (EO) and / or propoxylated (PO) derivatives, having on average from 0.5 to 6 units, preferably from 0.5 to 3 EO and / or OP units; alkylamide sulphates of formula RCONHR'OSO3M where R represents an alkyl radical in
C2-C22, preferably C6-C20, R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, and their ethoxylated derivatives (EO) and / or propoxylated (PO), with an average of 0.5 to 60 EO and / or
OP; saturated or unsaturated C8-C24, preferably C14-C20 fatty acid salts, C8-C20 alkylbenzenesulfonates, primary or secondary alkylsulfonates,
C8-C22, alkylglycerol sulphonates, sulphonated polycarboxylic acids disclosed in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, alkylisethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters sulfosuccinates, N-acyl sarcosinates, sulphates of alkylg lycosides, polyethoxycarboxylates, the cation of which is an alkali metal (especially sodium, potassium, lithium), a substituted or unsubstituted ammonium (especially methyl-, dimethyl-, trimethyl) -, tetramethylammonium or dimethylpiperidinium) or derivative of an alkanolamine (in particular monoethanolamine, diethanolamine or triethanolamine)
In addition to these products may be present in said compositions, one or more other additives selected from those types described below - nonionic surfactants, such as for example. polyoxyalkylenated alkylphenols (especially polyoxyethylenated, polyoxypropylenated, polyoxybutylenated) whose alkyl substituent is C 6 -C 12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the TRITON X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy .; glucosamides, glucamides; glycerolamides derived from N-alkylamines (US-A-5,223,179 and FR-A-1,585,966) polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (especially oxyethylene, oxypropylene); for example, we can mention the
TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide Corp.,
NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by
Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy.

. the products resulting from the condensation of ethylene oxide with a hydrophobic compound resulting from the condensation of propylene oxide with propylene glycol, such as PLURONIC marketed by BASF; . amine oxides such as C10-C18 alkyl dimethylamine oxides, C8-C22 alkoxy ethyl dihydroxy ethylamine oxides; the alkylpolyglycosides described in US-A-4,556,547 and their polyoxyalkylenated derivatives; . C 8 -C 20 fatty acid amides ethoxylated fatty acids amides, amines, ethoxylated amidoamines - cationic surfactants, for example
alkyldimethylammonium halides - amphoteric and zwitterionic surfactants containing not more than 1% of inorganic salts, for example the condensation products of fatty acids and of protein hydrolysates, alkylamphopropionates or -dipropionates, which are used to decrease irritation caused by other surfactants, mainly anionic surfactants.

It is also advantageous to add to these hair compositions sequestering agents of metals, more particularly those sequestering calcium such as citrate ions or emollient agents such as silicones or oils or fats used in this respect in the cosmetics industry (especially oils minerals, fatty acid esters, triglycerides, ....).

It is also possible to advantageously incorporate the humectant agents with the hair cosmetic compositions which are the subject of the invention. There may be mentioned glycerol, sorbitol,
Urea, collagen, gelatin, aloe vera, hyaluronic acid. Emollients which are generally chosen from alkylmonoglycerides, alkyldiglycerides and triglycerides, such as oils extracted from plants and plants (especially palm, coconut, cottonseed, soybean, sunflower, olive, grapeseed, sesame, peanut, castor oil ...) or o

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 (hydrolisates of wheat proteins for example), natural hydrocolloids ( such as guar gum, carob, tara, etc.) or from fermentation processes such as xanthan gum and derivatives of these polycarbohydrates such as modified celluloses (for example hydroxyethylcellulose, carboxymethylcellulose), guar or carob derivatives as their nonionic derivatives (for example hydroxypropylguar), anionic derivatives (carboxymethylguar) or mixed nonionic / anionic derivatives such as carboxy-hydroxypropyl guars.

The basic constituents may optionally be added in combination with powders or mineral particles such as calcium carbonate, mineral oxides in the form of powder or in colloidal form (particles of smaller size or of the order of one micrometer, sometimes of some tens of nanometers) such as titanium dioxide, silica, aluminum salts, kaolin, talc, clays and their derivatives.

Preservatives such as the methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid, sodium benzoate, the product sold under the trademark GERMABEN or any chemical agent avoiding bacterial proliferation or molds and traditionally used in the compositions Cosmetics may advantageously be introduced into the compositions of the invention, especially up to 0.01 to 3% by weight. The amount of these products is generally adjusted to prevent any proliferation of bacteria, molds or yeasts in the cosmetic compositions.

As an alternative to these chemical agents, it is sometimes possible to use agents that modify the activity of water and strongly increase the osmotic pressure, such as carbohydrates or salts.

To protect the hair from sun and UV rays, we can add to these formulations sunscreens which are either chemical compounds strongly absorbing UV radiation such as the compounds authorized in the European directive N 76/768 / CEE, its annexes and subsequent amendments to this Directive, or titanium dioxide or cerium oxides in the form of powder or colloidal particles. These powders may optionally be surface treated to increase the effectiveness of their anti-UV action, to facilitate their incorporation into cosmetic formulations or to inhibit surface photoreactivity.

To these ingredients it is generally possible to add to increase the approval during the use of the composition by the consumer, one or more perfumes, coloring agents of the composition among which may be mentioned the products described in Annex IV ("list of the european directive n 76/768 / EEC of 27 July 1976, known as the "cosmetic directive". and / or opacifying agents such as pigments. It is also possible to incorporate in the composition bactericidal or fungicidal agents in order to improve the disinfection of the scalp, for example triclosan. Finally, the composition may also contain viscosifying or gelling polymers, such as crosslinked polyacrylates-particularly CARBOPOL brand products sold by GOODRICH-, cellulose derivatives such as hydroxypropylcellulose. carboxymethylcellulose, guars and their derivatives, carob, gum of tara or cassia, xanthan gum, alginates, carrageenans, derivatives of chitin such as chitosan .... used alone or in combination, or 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, especially in amounts of the order of 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as water-soluble salts of polycarboxylic acids with a molecular mass of about 2,000 to 100,000, 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 especially polyacrylates with a molecular weight of about 2,000 to 10,000 (US-A-3,308,067), copolymers of aryl and maleic anhydride with a molecular weight of about 5,000 to 75,000 (EP
A-66 915) polyethylene glycols of molecular weight of the order of 1000 to 50 000.

The invention also relates to a method for manufacturing a composition as described above, characterized in that it comprises the steps of:
a) purifying an amino acid derivative surfactant having an inorganic salt content of greater than 1% by weight, by a suitable separation technique to obtain a surfactant having a content of said salts of at most 1% by weight. and
b) mixing the surfactant thus obtained with the fixative resin and the vehicle, and optionally the other ingredients.

Another method which is the subject of the invention is characterized in that it comprises the steps of: a) preparing a surfactant of formula (5) by reacting an aminoalkylalkanolamine of formula (7)
Wherein R 1, R 6 and R 7 have the above meanings, with a cyanide of formula (8)
XCN (8)
in which X represents a hydrogen or alkali metal atom, followed by an alkaline hydrolysis of the nitrile formed in the case where X is a hydrogen atom, and b) mixing the surfactant having an inorganic salt content of from plus 1% by weight thus obtained, with the fixative resin and the vehicle, and optionally the other ingredients.

The following examples illustrate the invention.

REFERENCE EXAMPLE: Preparation of cocoamphomonoacetate with low inorganic salt content
A pilot electrodialyzer of the TS-2-10P type marketed by the Company is used.
Eurodia. This electrodialyzer has a total effective membrane surface of 2000 cm 2 and comprises 10 cells with 2 compartments of 200 cm 2 of useful unit area.

The anionic and cationic membranes used are membranes marketed by Eurodia or Tokoyama Soda whose references are respectively
Neosepta AM1 and Neosepta CMX.

2 liters of cocoamphomonoacetate solution at 26% by weight are electrodialized. This starting material was prepared by reaction of cocoimidazoline with chloroacetic acid according to Example 3 of European Patent Application EP-A-0 647 469, the pH being adjusted to 7 by the addition of HCl.

The reaction is carried out at ambient temperature with a current density of 18.4 mA / cm 2. The initial NaCl content is 8.5% based on the total weight of the solution. The viscosity of the initial solution is 44 mPa.s.

Electrodialysis is stopped after 8 hours.

The final content of sodium chloride is determined and a value of 0.6% is found, the sodium glycolate is also measured and it is found that it passes from a content of 1.2% to 0.6% . The final viscosity is 71 mPa.s. The concentration of cocoamphomonoacetate increases from 26% to 33%.

The irritant potential was evaluated by the Eytex method on the product itself and in formulation.

EXAMPLES OF HAIR COSMETIC COMPOSITIONS COMPRISING
FIXING RESINS
The different fixative resins used are the following: * Luviskol VA 37 - E (BASF)
polyvinylpyrrolidone / vinyl acetate copolymer in solution (at 50 Yo in ethanol) * Polycare PS 20 (Rhône-Poulenc)
Hydrodispersible sulfonated polyester polymer e * Polycare PS 30 (Rhône Poulenc)
Hydrodispersible sulfonated polyester polymer
For comparative purposes, relatively high sodium chloride cocoamphodiacetate containing 1% NaCl, sold under the tradename Miranol C2M, is used.

Examples 1-2
These examples illustrate the compatibility of the surfactant of the reference example with the Luviskol fixative resin. A water-based shampoo composition of pH 6 is formulated comprising the surfactant of the reference example, the fixing resin and optionally an anionic surfactant (sodium laureth-2 sulfate - Empicol ESB).

Examples I and 2
Analogous compositions are prepared in which the surfactant of the reference example is replaced or supplemented with Miranol C2M (cocoamphoacetate containing 11% by weight of sodium chloride).

The result of the evaluation of the compatibility of the constituents is recorded in Table I below.

Table i

<tb> Ingredients <SEP> Ex. <SEP> i <SEP> Ex. <SEP> comp. <SEP> i <SEP> Ex. <SEP> 2 <SEP> Ex. <SEP> comp <SEP> 2
<tb> product <SEP> of <SEP> example <SEP> 5% <SEP> 5% <SEP> 3%
<tb> of <SEP> reference
<tb> Miranol <SEP> C2M <SEP> conc <SEP> - <SEP> 5% <SEP> - <SEP> 3%
<tb> Location <SEP> ESB <SEP> - <SEP> - <SEP> 9% <SEP> 9%
<tb> Luviskol <SEP> VA <SEP> 37 <SEP> E <SEP> 5% <SEP> 5% <SEP> 5% <SEP> 5%
<tb> Water <SEP> qs <SEP> qs <SEP> qs
<tb> ASPECT <SEP> compatible <SEP> incompatible <SEP> sol. <SEP> soil. <SEP> opaque
<tb><SEP> (demixion) <SEP> translucent <SEP> white
<Tb>
The formulations of Examples 1 and 2 are interesting: the product of the reference example makes it possible to obtain a translucent solution, whereas the formulations with the
Miranol C2M give incompatible compositions (opaque or demixion).

Examples 3 and 4
These examples illustrate the compatibility of the product of the reference example with the Luviskol fixative resin, in the presence of the anionic surfactant and a hydroxypropylguar hydroxypropyltrimonium chloride (JAGUAR C162) or polyquaternium 7 (MIRAPOL 550) chloride-based conditioner.
Water-based compositions of pH 6, the formula of which is shown in Table 2 below, are prepared and the appearance of which is evaluated visually.

Comparative Examples 3 to 5
Analogous compositions are prepared in which the surfactant of the reference example is replaced by Miranol C2M (11% NaCl) or Tegobetaine
L7 (cocoamidopropylbetaine containing 8% inorganic salts).

The result of the evaluation of the compatibility of the constituents is recorded in Table 2.

Table 2

<tb><SEP> Ingredients
Ex. <SEP> Ex.
<tb><SEP> Product <SEP> of <SEP> Example <SEP> 5.6 <SEP>% <SEP> - <SEP> - <SEP> 5.6 <SEP>%
<tb><SEP> of <SEP> reference
<tb><SEP> Miranol <SEP> C2M <SEP> conc <SEP> - <SEP> 5.6% <SEP> - <SEP> - <SEP> 5.6%
<tb><SEP> Tegobetaine <SEP> L7 <SEP> - <SEP> - <SEP> 5.6% <SEP> - <SEP>
<tb><SEP> Luviskol <SEP> VA <SEP> 37 <SEP> E <SEP> 2.0 <SEP>% <SEP><SEP> 2.0 <SEP>% <SEP><SEP> 2, 0 <SEP>% <SEP><SEP> 3.0 <SEP>% <SEP><SEP> 3.0 <SEP>%
<tb><SEP> Empicol <SEP> BSE <SEP> 14.0% <SEP> 14.0% <SEP> 14.0% <SEP> 14.0% <SEP> 14.0%
<tb><SEP> Jaguar <SEP> C162 <SEP> 0.5% <SEP> 0.5% <SEP> 0.5% <SEP> - <SEP>
<tb><SEP> Mirapol <SEP> 550 <SEP> - <SEP> - <SEP> - <SEP> 0.7% <SEP> 0.7%
<tb> Water <SEP> qs <SEP> qs <SEP> qs <SEP> qs <SEP> qs
<tb><SEP> ASPECT <SEP> limpid <SEP> demixion <SEP> disorder <SEP> clear <SEP> opaque
<Tb>
The formulations of Examples 3 and 4 appear interesting: in combination with cationic polymers and a resin. the surfactant which is poor in inorganic salts makes it possible to obtain compatible and clear formulations, unlike Miranol C2M or the
Tegobetaine L7.

Example 5 and Comparative Example 6
Compositions analogous to those of the preceding examples are prepared using the surfactant of Reference Example and Polycare PS30 resin in a purely aqueous vehicle without other ingredients. The water and the Polycare are mixed and heated at a temperature of 65 ° C. and left stirring for 15 minutes.

The pH is then adjusted to 6.5.

The formulas of the compositions and the result of the visual evaluation are shown in Table 3
Table 3

<tb> Ingredients
<tb><SEP> Ex <SEP> 5 <SEP> Ex. <SEP> comp. <SEP> 6
<tb> Product <SEP> of <SEP> Example <SEP> 10.0 <SEP>%
<tb> of <SEP> reference <SEP> 1
<tb> Miranol <SEP> C2M <SEP> conc <SEP> - <SEP> 10.0% <SEP>
<tb> Polycare <SEP> PS <SEP> 30 <SEP> 5.0 <SEP>% <SEP> 5.0 <SEP>%
<tb> Water <SEP> qs <SEP> qs
<tb> ASPECT <SEP> limpid <SEP> demixion
<Tb>
The following test is intended to show that the resin retains its fixing power when using the composition of Example 5 as a shampoo to rinse. A loop remanence test was carried out with the shampoo of Example 5 containing the resin, and a control shampoo (T) containing 10% of the product of the reference example and 90% of water, the pH of the formulations. being adjusted to 6.5 (zero viscosity).

* Protocol
Two batches of 3 locks of hair of length = 18 cm and mass = 2 g are pretreated according to a protocol known to those skilled in the art, then subjected to 2 successive washes with 3 ml of the shampoo tested, respectively that of the Example 5 and the shampoo (T). The locks are wound on rolls of diameter 26 mm, and placed in an oven at 60 ° C. for 1 h 30 min under a relative humidity of 60%. After leaving the oven, the locks are unwound and periodically measures the length of the locks. Table 4 presents the results.

Table 4

<tb> Time <SEP> elapsed <SEP> | <SEP> Length <SEP> of <SEP> loop <SEP> | <SEP> RETENTION <SEP> FROM
<tb><SEP> (average <SEP> in <SEP> cm) <SEP> BUCKLES
<tb> (%)
<tb> Witness <SEP> Ex.5 <SEP> Witness <SEP> Ex.5
<tb><SEP> 0 <SEP> min <SEP> 3,4 <SEP> 3,4 <SEP> 100 <SEP> 100
<tb><SEP> 10 <SEP> min <SEP> 3.8 <SEP> 3.5 <SEP> 97 <SEP> 99
<tb><SEP> 30 <SEP> min <SEP> 3.8 <SEP> 3.5 <SEP> | <SEP> 97 <SEP> 99 <SEP>
<tb><SEP> 1h <SEP> 4.1 <SEP> 3.8 <SEP> 94 <SEP> 97
<tb><SEP> 2h <SEP> 4.5 <SEP> 3.8 <SEP> 91 <SEP> 97
<tb><SEP> 5h <SEP> 8.2 <SEP> 5.65 <SE> 62 <SEP> 82
<Tb>
These results show that the product of the reference example associated with the resin
Polycare PS 30 makes it possible to formulate a shampoo with interesting fixing properties with 82% loop retention after 5 hours.

The following two examples illustrate the preparation of hair products according to the invention
Example 6: Preparation of a structuring shampoo

<tb><SEP> component <SEP>% <SEP> weight
<tb><SEP> A) <SEP> agent <SEP> structuring
<tb> polyvinylpyrrolidone <SEP> 1
<tb> ocatmethyl <SEP> cyclotetra <SEP> siloxane <SEP> 3
<tb><SEP> B) <SEP> Premix
<tb><SEP> gum <SEP> sillcone <SEP> 0.5
<tb><SEP> dimethicone <SEP> 0.5
<tb><SEP> C) <SEP> main <SEP> mixture
<tb> product <SEP> of <SEP> the <SEP> example of <SEP> reference <SEP> 3
<tb><SEP> lauryl <SEP> ammonium sulfate <SEP><SEP> 8
<tb> cocoamide <SEP> of <SEP> monoethanolamine <SEP> 2
<tb><SEP> distearate <SEP> of ethylene <SEP> glycol <SEP> 1
<tb><SEP> gum <SEP> xanthan <SEP> 1
<tb><SEP> conservative <SEP> 1.2
<tb><SEP> acid <SEP> citric <SEP> qs <SEP> pH <SEP> 6.5 <SEQ> qs
<tb><SEP> water <SEP> distilled <SEP> qs <SEP> 100
<Tb>
The structuring agent and the premix are separately prepared in a conventional manner. The main mixture is prepared by first dissolving the xanthan gum in water. The other compounds are then added and the main mixture heated with stirring at 80 ° C. for 30 minutes. The structuring agent and the premix are then added sequentially, and the residual mixture is then allowed to return to ambient temperature with stirring.

EXAMPLE 7: Preparation of a styling mousse

<tb><SEP> ingredients <SEP> p / p
<tb><SEP> water <SEP> qs <SEP> 100
<tb><SEP> polyvinylpyrrolidone <SEP> 3
<tb> product <SEP> of <SEP> the <SEP> example of <SEP> reference <SEP> 0.5
<tb><SEP> sodium <SEP> methyl <SEP> oleyl <SEP> taurate <SEP> 2
<tb><SEP> DMDM <SEP> hydantoin <SEP> 0.8
<tb><SEP> alcohol <SEP> isostearic <SEP> ethoxylated <SEP> 0.1
<tb><SEP> perfume <SEP> 0.1
<tb><SEP> gas <SEP> propellant <SEP> 7
<tb><SEP> EDTA <SEP> disodium <SEP> 0.2
<Tb>

Claims (15)

 A hair cosmetic composition comprising a) from 0.1 to 30% of at least one amphoteric amino acid derivative surfactant having an inorganic salt content of at most 1% by weight relative to said surfactant; b) from 0.01 to 10% of an anionic, cationic, nonionic amphoteric fixing resin, or a mixture; and c) a cosmetically acceptable vehicle.  2. The composition of claim 1, wherein the surfactant is derived from amino carboxylic acid or sulfonic acid and is selected from surfactants betaine, sulfobetaine, amidoalkylbétaine, amidoalkylsulfobétaine and amphoacétate.  3. Composition according to claim 2, in which the surfactant derived from amino carboxylic or sulphonic acid is chosen from betaines of formula 1:  R1 R2 R3 NR4 C (O) O- (i) - sulfobetaines of formula 2:  R1 R2 R3NR4 SQ (2) - amidoalkyl betaines of formula 3:  R 1 C (O) -NHR 4 N (R 2 R 3) R 5 C (O) O- (3) - amidoalkylsulfobetaines of formula 4:  R1C (O) - NH R4 N (R2 R3) R5 SO3- (4) - alkylamphoacetates of formula 5,  R1C (O) - NH - R6 - N - R7 - OH (5)  Wherein R 1 represents an alkyl or alkenyl radical having from 10 to 24 carbon atoms, the radicals R 2 and R 3, which may be identical or different, represent an alkyl radical having from 1 to 4 carbon atoms, the radicals R4 and R5, which are identical or different, represent an alkylene radical having from 1 to 4 carbon atoms, the radicals R6 and R7, which may be identical or different, represent an alkylene group having 2 to 6 carbon atoms, and M represents a hydrogen or an alkali metal atom or an ammonium group.  4. A composition according to any one of the preceding claims wherein the surfactant has an inorganic salt content of 0.05 to 1% by weight.  5. Composition according to any one of the preceding claims wherein the surfactant having said content of inorganic salts is obtained by a dialysis process, in particular by electrodialysis, precipitation of inorganic salts or liquid-liquid extraction.  6. Composition according to claim 3, wherein the amino acid derivative surfactant is an alkylamphoacetate of formula (5) obtained by reaction of an aminoalkylalkanolamine of formula (7) Wherein R 1, R 6 and R 7 have the above meanings, with a cyanide of formula (8) XCN (8) wherein X represents a hydrogen or alkali metal atom, followed by an alkaline hydrolysis of the nitrile formed in the case where X is a hydrogen atom.  A composition according to any one of the preceding claims, comprising from 2 to 10% of an amino acid derivative surfactant having said content of inorganic salts.  8. Composition according to any one of the preceding claims; wherein the fixative resin is selected from polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, ethylene glycol terephthalate glycol polyethylene condensates, diester polycondensates, terephthalic acid / sulfoisophthalic anhydride / glycol, and mixtures thereof.  9. Composition according to any one of the preceding claims comprising from 0.5 to 5% of fixing resin.  10. Composition according to any one of the preceding claims comprising from 0.5 to 99.5% by weight of said vehicle.  11. Composition according to any one of the preceding claims, characterized in that the vehicle comprises water, alcohols, hydrocarbons, halogenated hydrocarbons, esters. ketones, volatile silicones and a mixture of these products.  12. Composition according to any one of the preceding claims further comprising at least one conditioning agent of anionic, cationic, nonionic or amphoteric nature.  13. Composition according to any one of the preceding claims further comprising at least one of anionic, cationic, nonionic or amphoteric surfactants; sequestering, humectant or emollient agents protective agents of the skin or scalp such as water-soluble or water-dispersible polymers, non-allergenic derivatives of animal or vegetable proteins, hydrocolloids and their derivatives.  14. A method of manufacturing a composition according to any one of claims 1 to 13, characterized in that it comprises the steps of: a) purifying an amino acid derivative surfactant having an inorganic salt content greater than 1 % by weight, by a suitable separation technique to obtain a surfactant having a content of said salts of at most 1% by weight, and b) mixing the surfactant thus obtained with the fixative resin and the vehicle, and optionally the others ingredients.  15. The method of manufacturing a composition according to any one of claims 1 to 13, characterized in that it comprises the steps of: a) preparing a surfactant of formula (5) by reaction of an aminoalkylalkanolamine of formula (7) Wherein R 1, R 6 and R 7 have the above meanings, with a cyanide of formula (8) XCN (8) wherein X represents a hydrogen or alkali metal atom, followed by an alkaline hydrolysis of the nitrile formed in the case where X is a hydrogen atom, and b) mixing the surfactant having a salt content inorganic of at most 1% by weight thus obtained, with the fixative resin and the vehicle, and optionally the other ingredients.