FR2739022A1 - Aq. cosmetic compsn. causing less environmental pollution - Google Patents

Abstract

Cosmetic or dermatological compsn. contains, in a cosmetically acceptable aq. medium, at least (A) a film-forming oligomer which is soluble or dispersible in the medium, having a mol. wt. determined by steric exclusion chromatography of <= 50000 (500-45000); and (B) a rigid, non film-forming particles having a average particle size of <= 1 mu m dispersed in the medium.

Description

AQUEOUS COSMETIC OR DERMATOLOGICAL COMPOSITION
COMPRISING A FILM-FORMING OLIGOMER AND PARTICLES
RIGID AND NON-FILMABLE POLYMER NANOMETRICS;
USES.

The subject of the present invention is cosmetic or dermatological compositions comprising, in a cosmetically acceptable aqueous medium, at least one film-forming oligomer, soluble or dispersible in said medium, and at least nanometric particles of polymer, rigid and non-film-forming, as well as their uses in the field of cosmetics or dermopharmacy, in particular in products for maintaining the hairstyle, products for coating the eyelashes and eyebrows, products for make-up and / or nail care.

Film-forming polymers soluble in aqueous and hydroalcoholic media such as polyvinylpyrrolidone, vinylpyrrolidonelvinyl acetate copolymers, copolymers of vinylelotrotonic acid, anionic or amphoteric acrylic resins are commonly used in products for fixing the hair, mascaras or products for the care and / or makeup of the nails.

The most widespread hair products for fixing hair on the cosmetics market are spray compositions essentially consisting of a solution, most often hydroalcoholic, and a film-forming polymer soluble in water and in alcohol, such as those mentioned above, mixed with various cosmetic adjuvants. This solution is generally packaged either in a suitable aerosol container pressurized with a propellant, or in a pump bottle.

For a certain number of years, a very particular interest has manifested itself for aerosol lacquers or pump bottles with high concentrations of water "with a high dry extract" of film-forming polymer.

Throughout the description, the term “aerosol or pump bottle with a high dry extract in lacquering product” will be understood to mean any aqueous formulation packaged in one of these forms containing more than 5% by weight in dry matter of lacquering product relative to the total weight of said formulation.

On the one hand, it is sought to reduce the concentrations of volatile compounds at atmospheric pressure called VOCs (Volatile Organic Compound) present in the compositions to be sprayed in the form of an aerosol or of a pump bottle. Indeed,
The use of alcohol, alone or mixed with a small amount of water, as well as the use of propellants, may present certain drawbacks such as an increase in flammability or a nuisance towards the environment.

VOCs are mainly propellants such as hydrocarbons or dimethyl ether (DME) and solvents such as ethanol.

On the other hand, it is sought to reduce the drying times of the sprayed product and to increase its lacquering power after spraying on the hair. The use of water-soluble film-forming polymers in aerosols or pump bottles with high concentrations of water, in particular in water / ethanol / dimethyl ether spraying systems having a maximum VOC level of 55%, requires higher concentrations of dry extract of polymer compared to those used in organic spraying systems (100% VOC) to obtain fixing properties and satisfactory drying times. Indeed,
The increase in the water concentration in the aerosol packaging or pump bottles leads to a strong decrease in the lacquering power as well as to much longer drying times.

The film-forming polymers usually used in this type of composition have molecular weights measured in steric exclusion chromatography generally greater than 50,000 and preferably greater than 100,000.

The increase in their concentration in aerosol lacquers or pump bottles with high water contents, leads to too high viscosities so that it is no longer possible to obtain a satisfactory spraying of the product at the outlet of the aerosol or of the pump bottle. .

To remedy these problems of viscosity of the juice in the spraying device, one solution would consist in using film-forming oligomers which are soluble or dispersible in the medium of the composition to be sprayed, providing a low viscosity. However, most of the oligomers, of molecular weight less than 50,000, used in products for maintaining the hair have insufficient mechanical properties to obtain satisfactory lacquering power, even at high concentrations.

The Applicant has surprisingly discovered that by combining film-forming oligomers, of molecular weight less than 50,000, soluble or dispersible in aqueous media, nanometric particles of polymer, rigid and non-film-forming, it was possible to produce aerosol lacquers or pump bottles with high dry extract in lacquering agent, having good diffusion during application, good lacquering power and good drying speed. This combination is particularly suitable for aerosol hair compositions with a high dry extract of the eaulethanollDME type having a maximum VOC level of 55%.

The Applicant has discovered that this particular combination of polymers constitutes a coating agent for keratin materials, having both good - cosmetic properties, in particular in terms of touch and disentangling, good film-forming properties, mechanical properties satisfactory for fixing the hair, good adhesion properties on the eyelashes and eyebrows as well as satisfactory mechanical properties for coating the nails.

After application to the keratinous support and drying, the deposition of a composite material is obtained, the structure of which consists of a hydrophilic continuous material formed by the film-coated oligomer, said matrix containing a multitude of rigid nodules consisting of nanometric particles of non-film-forming polymer.

According to the respective proportions of the film-forming oligomer and of the non-film-forming and rigid polymer particles, it is possible to produce cosmetic hair compositions having good lacquering power, good resistance to humidity by reducing the sticking effect by hydroscopicity that could provide the hydrophilic oligomer and good elimination in washing due to the hydrophilic nature of the continuous matrix of the composite deposit.

The combination in accordance with the present invention also allows the production of products for coating the eyelashes and the eyebrows, in particular cream mascaras and water-resistant (waterproof) mascaras, having good adhesion power on the eyelashes and eyebrows, no sticky effect on the surface of the film and easily removable in the wash with a makeup remover with low surfactant content.

The combination according to the invention also allows the production of products for makeup and / or nail care having good adhesion to the nail, good hardness and good rigidity. They are also completely removable with water or in the presence of a makeup remover with a low surfactant content.

The cosmetic or dermatological compositions in accordance with the invention are characterized in that they contain in a cosmetically acceptable aqueous medium at least: (A) a film-forming oligomer soluble or dispersible in said medium, having a molecular weight measured by chromatography d steric exclusion, less than or equal to 50,000 (B) an aqueous dispersion of rigid and non-film-forming polymer particles whose average size is less than or equal to 500 nm and with a glass transition temperature Tg greater than 50 C.

The oligomers soluble or dispersible in the aqueous medium of the compositions of the invention preferably have a molecular weight measured in steric exclusion chromatography ranging from 500 to 45,000.

Their glass transition temperature T′g preferably ranges from −50 ° C. to + 50 ° C. and more particularly from −30 to + 40 ° C. They are preferably soluble in aqueous or hydroalcoholic media.

The oligomers used in the compositions according to the invention can be nonionic such as the copolymers of vinylpyrrolidonelvinyl acetate. They can be amphoteric such as N-octylacrylamide / methyl methacrylate / hydroxypropyl methacrylate / acrylic acid / t-butylaminoethyl methacrylate copolymers such as the product sold under the name
AMPHOMER by the National Starch Society. They can also be an ionic.

Particularly preferred oligomers are anionic oligomers containing monomers carrying ionized or ionizable anionic groups, in particular carboxylic acid groups and / or sulfonic acid groups. These groups are preferably partially or completely neutralized in order to obtain better solubility of the oligomer in the aqueous medium of the composition and better elimination on washing.

Among the anionic oligomers used according to the invention, mention may be made of copolymers of vinyl esters such as vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl benzoates substituted or not, with a monomer of the type maleic acid or crotonic acid. Mention may in particular be made of the vinyl acetate crotonic acid copolymer of composition identical to that of the product LUVISET CA66 sold by the company BASF, but of molecular weight less than or equal to 50,000.

Mention may also be made of copolymers of C1 C8 (meth) acrylic acid esters such as, for example, tert-butyl acrylate, ethyl acrylate, methyl methacrylate, isobutyl acrylate with acrylic acid monomer and / or methacrylic acid monomer. It is possible, for example, to use an ethyl acrylate / tert-butyl acrylate / methacrylic acid copolymer with a composition identical to that of the product sold under the name LUVIMER 100 P by
BASF, but of molecular weight less than or equal to 50,000.

The film-forming oligomers according to the invention can be prepared in conventional manner by radical polymerization or copolymerization in solution, suspension or in emulsion.

They are preferably prepared in solution in an organic solvent from the monomer (s) mixed in the solvent in the presence of a free radical initiator. They can then be purified by precipitation in a solvent such as petroleum ether.

It is also possible to operate semi-continuously using a base stock containing only the solvent part, a small part of the monomer mixture and a part of the initiator. It is then heated to the reaction temperature and a simultaneous double casting is carried out of the remainder of the mixture of monomers and of the remainder of initiator dissolved in an amount of solvent.

In the case of anionic oligomers, the oligomers thus obtained can then be partially or completely neutralized by a non-volatile monobasic compound such as a mineral base such as sodium hydroxide or potassium hydroxide, or an amino alcohol for example taken from the group consisting of 2-amino-2-methyl-propanol-1 (AMP), triethanolamine, triisopropanolamine (TIPA), monoethanolamine, tri [(hydroxy-2) propyl-1 amine, 2-amino-methyl2-propanediol-1,3 (AMPD), 2-amino-2-hydroxymethyl-1,3-propanediol.

The rigid and non-film-forming polymer particles used according to the present invention have a glass transition temperature greater than 50 ° C. and more particularly greater than 70 ° C.

Their average particle size is less than 500 nm, preferably less than 300 nm and more particularly less than 100 nm.

The polydispersity in size of the polymer particles, measured in quasi-elastic light scattering, is preferably less than 0.35.

The rigid and non-film-forming polymer particles of the invention are more preferably made of crosslinked polymer.

The crosslinking agents are preferably chosen from those commonly used in radical polymerization. Mention may be made, for example, of diacrylates or dimethacrylates of ethylene glycol, of polyethylene glycol, of propylene glycol, of divinylbenzene, of pentaerythritol di- or tri-methacrylate; the diacrylates or dimethylacrylates of alkylenediols such as hexanediol dimethacrylate. They are used in amounts preferably ranging from 0.1 to 50% by weight relative to the weight of the monomers constituting the polymer of the latex.

In aqueous media containing volatile organic compounds, in particular those present in aerosol lacquers or pump bottles of the invention, a dispersion of polymer particles preferably comprising ionized or ionizable anionic groups, in particular acid groups, is used. carboxylic or sulfonic acid to provide good stabilization of the latex (in particular in a hydroalcoholic medium).

These acid groups are preferably present in amounts less than or equal to 10% by weight, more particularly less than or equal to 8% by weight and even more particularly ranging from 3 to 8% by weight relative to the weight of the polymer.

These acid groups are preferably partially or totally neutralized by a volatile mineral base or an amino alcohol as defined above.

Among the polymers constituting the rigid and non-film-forming particles of the invention, there may be mentioned for example the polymers or copolymers, preferably crosslinked, obtained by polymerization or copolymerization of a monomer or of a mixture of monomers chosen from the group consisting of acrylates or methacrylates of linear, cyclic or branched C1-C10 alkyl such as methyl methyl methacrylate, tert-butyl methacrylate, cyclohexymethacrylate, acrylate or isobornyl methacrylate; styrene; vinyltoluene vinyl chloride, vinyl benzoate or vinyl tert-butylbenzoate, acrylic acid, methacrylic acid.

Particularly preferred polymers are crosslinked copolymers of at least one linear, cyclic or branched C 1 -C 8 alkyl methacrylate and acrylic acid and / or methacrylic acid.

The dispersions of polymer particles or "latex" according to the invention can be obtained by emulsion polymerization in batch, according to a process comprising:
a) producing a base stock in the reactor containing water,
optionally a tampon and an emulsifying agent;
b) the addition to the base stock, at room temperature, of the monomers;
c) the emulsification of the monomers,
d) heating to the polymerization temperature of the reaction medium in
presence of a radical initiator.

One can also operate semi-continuously using a base stock containing only the aqueous part, a small part of the monomer mixture and a part of the initiator. It is then heated to the reaction temperature and a simultaneous double casting is carried out of the remainder of the mixture of monomers and of the remainder of initiator dissolved in an amount of water.

The cosmetically acceptable aqueous medium of the invention preferably consists of water or a mixture of water and at least one cosmetically acceptable solvent compatible with the rigid, non-film-forming latex and the film-forming oligomer such as than a monoalcohol, a polyalcohol, a glycol ether,
Acetone or an ester, alone or as a mixture. It more particularly consists of water or water and a lower C1-C4 alcohol such as ethanol or isopropanol.

The concentration of organic solvent in the composition of the invention is preferably between 15 and 35% by weight and more particularly between 20 and 30% by weight relative to the total weight of the composition.

When the composition according to the invention is packaged under pressure in an aerosol device in order to obtain a lacquer, it comprises at least one propellant which can be chosen from volatile hydrocarbons such as nbutane, propane, isobutane, pentane, chlorinated and / or fluorinated hydrocarbons and their mixtures; carbon dioxide, nitrous oxide, dimethyl ether, nitrogen or compressed air. The concentration of the propellant in the aerosol device depends on the nature of the propellant chosen.

Dimethyl ether is particularly preferred. It is used in the aerosol lacquers of the invention as propellant in concentrations preferably ranging from 30 to 45% by weight relative to the total weight of the composition.

The concentration of volatile organic compound (VOC) in a composition according to the invention packaged in the form of an aerosol or pump bottle is preferably less than or equal to 55% by weight and more particularly between 30 and 55% by weight relative the total weight of the formulation packaged in an aerosol or pump bottle.

The pH of the compositions according to the invention is generally between 2 and 9 and in particular between 3 and 8. It can be adjusted to the value chosen by means of alkanizing or acidifying agents usually used in cosmetics.

In the mixture constituted by the rigid and non-film-forming polymer particles and by the film-forming oligomer, the proportions in particles preferably vary, from 5 to 95% by weight in dry matter relative to the weight of the mixture. These proportions vary depending on the intended application of the composition.

When the compositions of the invention are in the form of an aerosol lacquer or pump bottle, the dry matter proportions of the rigid and non-film-forming particles preferably vary from 5 to 60% by weight and those of oligomer vary from 40 95% by weight relative to the weight of the particle-oligomer mixture. The composite material obtained after deposition and drying on a keratinous support consists of a continuous matrix of film-coated oligomer containing a multitude of rigid nanometric particles which serve to increase the rigidity of the matrix.

When the compositions of the invention are in the form of an aerosol lacquer or a pump bottle with a high dry extract, it is also possible to use a mixture consisting of a high concentration of dry matter of rigid and non-film-forming particles, ranging preferably from 70 to 95% by weight relative to the weight of the non-film-forming particles / oligomer mixture. This particular embodiment of the invention makes it possible to obtain on deposition a composite material mainly consisting of a matrix of rigid particles bonded together by the film-forming oligomer, having good lacquering power on the hair. This embodiment makes it possible to optimize the viscosity of the juice in the spraying device by using lower concentrations of oligomer while obtaining good lacquering power.

The compositions according to the invention may optionally additionally contain a plasticizing agent to improve the mechanical properties, the cosmetic properties and the adhesion to keratin materials of the composite material deposited after application and drying. The presence of a plasticizing agent is not compulsory for adjusting the lacquering power in the lacquer formulations of the invention, unlike conventional lacquer formulations.

Among the plasticizing agents which can be used according to the invention, there may be mentioned:
- CARBITOLS from the UNION CARBIDE Company, namely CARBITOL or
diethylene glycol ethyl ether, methyl CARBITOL or diethylene glycol
methyl ether, butyl CARBITOL or diethylene glycol butyl ether or
hexyl CARBITOL or diethylene glycol hexyl ether,
- CELLOSOLVES from the UNION CARBIDE Company, namely CELLOSOLVE
or ethylene glycol ethyl ether, butyl CELLOSOLVE or ethylene glycol
butyl ether, hexyl CELLOSOLVE or ethylene glycol hexyl ether,
- propylene glycol derivatives and in particular propylene glycol
phenyl ether, propylene glycol diacetate, dipropylene glycol butyl ether,
tripropylene glycol butyl ether, as well as DOWANOLS from the company DOW
CHEMICAL namely DOWANOL PM or propylene glycol methyl ether,
DOWANOL DPM or dipropylene glycol methyl ether and DOWANOL TPM or
tripropylene glycol methyl ether.

We can also cite:
- diethylene glycol methyl ether or DOWANOL DM from the company DOW
CHEMICAL,
- castor oil oxyethylenated to 40 moles of ethylene oxide such as that
sold by RHÔNE POULENC under the name of
"MULGOFEN LE-719",
- benzyl alcohol,
- triethyl citrate sold by the company PFIZER under the name of "CITROFLEX-2",
- 1,3-butylene glycol,
- diethyl, dibutyl and diisopropyl phthalates and adipates,
- diethyl and dibutyl tartrates,
- diethyl, dibutyl and 2-diethylhexyl phosphates, and
- glycerol esters such as glycerol acetate (diacetin) and
glycerol triacetate (triacetin).

The plasticizing agent is present in a proportion preferably ranging from 0 to 20% by weight relative to the weight of the mixture constituted by the film-forming oligomer and the non-film-forming particles. This proportion varies depending on the application envisaged.

An object of the invention relates to the use of the combination consisting of the aqueous dispersion of rigid and non-film-forming particles and of the film-forming oligomer as defined above as a coating agent for keratin materials in and for the preparation. of a cosmetic or dermatological composition.

The compositions according to the invention as defined above can be used as a base of hair product for shaping and / or maintaining the hairstyle, in particular aerosol sprays or pump-dispensers for fixing the hair, lotions for styling or brushing, styling mousse.

The hair compositions for maintaining the hairstyle in accordance with the present invention preferably contain the mixture consisting of rigid, non-film-forming polymer particles and the film-forming oligomer in proportions ranging from 3 to 20% by weight. dry matter relative to the total weight of the composition.

The hair compositions in accordance with the invention may contain, in addition to conventional cosmetic additives such as preservatives, softeners, sequestrants, perfumes, dyes, viscosity modifiers, pearlescent agents, hydrating agents, anti-dandruff agents, anti-seborrheic agents, sunscreens, hair conditioning agents, antioxidants, proteins, vitamins.

The compositions according to the present invention can be used as a base for an aqueous product for coating the eyelashes and the eyebrows, such as a mascara, in particular a cream mascara or a water-resistant (waterproof) mascara.

The compositions for coating the eyelashes and the eyebrows in accordance with the invention contain the combination of polymers as defined above in proportions ranging, preferably from 2 to 15% by weight in dry matter relative to the total weight of the composition. The cosmetically acceptable aqueous medium is generally water or an aqueous-alcoholic medium.

The compositions for coating the eyelashes and the eyebrows in accordance with the invention generally comprise at least one wax.

The waxes used in the mascara compositions according to the invention are chosen from waxes, solid and rigid, of animal, vegetable, mineral or synthetic origin and their mixtures.

Among the animal waxes, mention may be made of beeswax, lanolin wax, and Chinese insect waxes.

Among the vegetable waxes, mention may in particular be made of rice wax, carnauba wax, candellila wax, ouricurry wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax.

Among the mineral waxes, mention may in particular be made of montan wax, microcrystalline waxes, paraffins and ozokerite.

Among the synthetic waxes, mention may in particular be made of polyethylene waxes, the waxes obtained by the synthesis of FISHER and TROPSCH and the waxy copolymers as well as their esters.

It is also possible to use in the compositions according to the invention, the waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains, linear or branched, of C8-C32.

Among these, mention may in particular be made of hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil.

The mascara compositions according to the invention can also contain pigments.

These pigments can be organic or mineral or can also be pearlescent pigments. Such pigments are well known and are described in particular in FR 83-09997 (2,528,699).

The mascara compositions according to the invention can be in different forms. They can in particular be in the form of oil-in-water or water-in-oil emulsions or in the form of dispersions.

The mascaras compositions can also contain anionic surfactants and / or nonionic surfactants.

Among the anionic surfactants which can be used alone or as a mixture, there may be mentioned in particular the alkaline salts, the ammonium salts, the amine salts or the amino alcohol salts of the following compounds:
- alkyl sulfates, alkyl ether sulfates, alkyllamide sulfates, ether sulfates,
alkylaryl polyether sulfates, monoglyceride sulfates,
- alkyl sulfonates, alkyllamide sulfonates, alkylarylsulfonates, α-olefins
sulfonates, sulfonate paraffins,
- acoylsulfosuccinates, alkyl ether sulfosuccinates, alkylamides sulfo
succinates,
- alkylsulfosuccinamates,
- alkyl sulfoacetates, alkyl polyglycerol carboxylates,
- alkyl phosphates / alkyl phosphate phosphates,
- alkylsarcosinates, alkylpolypeptidates, alkyllamidopolypeptidates,
alkyliso-thionates, and alkylltaurates.

The term alkyl used means above a hydrocarbon chain generally having from 12 to 18 carbon atoms.

Mention may also be made, as anionic surfactants which can be used in the compositions according to the invention, of fatty acid salts, such as those of oleic, ricinoleic, palmitic, stearic acid, coconut oil acids or hydrogenated coconut oil, and in particular the amine salts such as amine stearates.

Mention may also be made, as anionic surfactants, of acyl lactylates whose acyl radical comprises from 8 to 20 carbon atoms, and the carboxylic acids of polyglycolic ethers corresponding to the formula: R4- (OCH2-CH2) n-OCH2- COOH in which: R4 represents a linear alkyl radical having from 12 to 18 carbon atoms and n is an integer between 5 and 15, and the salts of said acids. Amine stearates are preferably used as an ionic surfactant.

Among the nonionic surfactants which can be used alone or as a mixture in the mascara compositions according to the invention, there may be mentioned in particular alcohols, alkylphenols and polyethoxylated, polypropoxylated or polyglycerolated fatty acids with a fatty chain having from 8 to 18 carbon atoms.

Mention may also be made of copolymers of ethylene and propylene oxides, condensates of ethylene and propylene oxides on fatty alcohols, polyethoxylated fatty amides, polyethoxylated fatty amines, ethanolamides, acid esters glycol fatty acids, fatty acid esters of sorbitan oxyethylenated or not, fatty acid esters of sucrose, fatty acid esters of polyethylene glycols, phosphoric triesters and fatty acid esters of glucose derivatives.

Mention may also be made of the condensation products of a monoalcohol, an alpha-diol, an alkylphenol, an amide or a diglycolamide with glycidol or a glycidol precursor as described in patent FR 71 -17206 (2.091.516), of formula: R5-CHOH-CH2-O- (CH2-CHOH-CH2-O) pH in which:
R5 represents an aliphatic, cycloaliphatic, cycloal iphatic or arylaliphatic radical preferably having between 7 and 21 carbon atoms, the aliphatic chains possibly comprising ether, thioether or hydroxymethylene groups and p is an integer between 1 and 10.

Mention may also be made of the compounds described in patent FR 1,477,048 of formula: R6O- [C2H3O- (CH2OH)] qH in which:
R5 represents an alkyl, alkenyl or alkylaryl radical, and q is a statistical value between 1 and 10.

Mention may also be made of the compounds described in French patent FR 76-31975 (2,328,763) of formula:
R7CON H-CH2-CH20-C H2-C H20- (C H2-CHOH-CH2-O) rH in .which:
R7 represents a linear or branched, saturated or unsaturated aliphatic radical, which may optionally contain one or more hydroxyl group (s), having between 8 and 30 carbon atoms, of natural or synthetic origin, and r is an integer or decimal between 1 and 5 and denotes the average degree of condensation.

The mascara compositions according to the invention can also comprise at least one conventional additive chosen from a softener, a preservative, a sequestering agent, a perfume, a thickening agent, an oil, a silicone, a cohesion agent, an alkalizing agent. or acidifier and a filler.

The thickening agents which can be used in the mascara compositions according to the invention can be of natural or synthetic origin.

Among the thickening agents of synthetic origin, mention may in particular be made of water-soluble cellulose derivatives, cellulose ethers derivatives having quaternary ammonium groups, starch derivatives, cationic polysaccharides, salts of acrylic or methacrylic polymers, polyenes and polysiloxanes. A thickening of the mascara compositions according to the invention can also be obtained by adding a mixture of polyethylene glycol and polyethylene glycol stearate and / or distearate or a mixture of phosphoric esters and fatty amides.

Among the fillers that can be used in the mascara compositions according to the invention, there may be mentioned in particular those described in FR 91-10791 (2,680,681).

The compositions for coating the eyelashes in accordance with the invention have good adhesion to the eyelash, without sticky effect on the surface of the film and are very easily removed using an aqueous make-up remover containing a small amount of surfactants. .

The compositions according to the invention can also be used as bases for aqueous products for coating the nails which are easily and completely removable by simple washing of the hands with water, without having to use make-up remover with a high concentration of surfactant or even hot water and / or heavily soapy water.

They can be used as an undercoat of a conventional solvent-based nail varnish, as an easy-to-remove aqueous varnish or else as a nail care base containing in solution or in dispersion in the aqueous medium the composition of active ingredients such as protective agents, hardeners and / or for nail care.

When said composition is used as an undercoat of solvent varnish, it is noted that the nail does not tend to tint during the subsequent application of the solvent varnish, as is the case in the prior art ; this being due to the fact that the nail is not in direct contact with said varnish.

When pigments are introduced into said compositions, they can be used as a varnish.

In the particular mode of use as nail care, one can imagine depositing the base containing the active agents on the nail in the evening, which allows the treatment of the nail overnight, then an elimination of this base. morning by simple hand washing.

Among the active agents which can be used, mention may be made of vitamins and their derivatives; raw materials of biological origin and their derivatives such as keratin, proteins, hydrolysates, chitosan, melanin, trace elements, collagen; glycerin; phospholipids; urea; formal.

The compositions for coating the nail according to the invention contain the combination of rigid and non-film-forming polymer particles and of the film-forming oligomer in proportions ranging, preferably, from 15 to 30% by weight in dry matter per relative to the total weight of the composition.

Another subject of the invention consists in a process for the non-therapeutic treatment of keratin materials such as the hair, the eyelashes or the nails, characterized in that it consists in applying directly to the keratin materials a cosmetic composition as defined above.

The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES
EXAMPLE 1 Preparation of a compatible non-film-forming acrylic latex
in a water / ethanol / DME aerosol lacquer medium at a rate of
55% maximum VOC
Composition of the latex polymer: - methyl methacrylate 91% by weight - methacrylic acid 5% by weight - ethylene glycol dimethacrylate (crosslinking) 4% by weight
Procedure:
The following mixture is introduced into a cylindrical reactor with mechanical central agitation, thermometer, refrigerant and nitrogen sparging: - permuted water 28 g - NaHCO3 0.7 g - nonylphenolpolyoxyethylene (with 25 oxyethylene units) and
sulfated at the end of the chain sold under the name AD 33 6.56 g
by the company SEPPIC
The mixture is dissolved with stirring and bubbling with nitrogen. Then, with stirring and at room temperature, the mixture of monomers consisting of: - methyl methacrylate 91 g - methacrylic acid 5g - ethylene glycol dimethylacrylate (crosslinker) 4 g is added
The monomer emulsion is produced at 250 revolutions / minute with nitrogen bubbling. We bring this emulsion to 72 "C and add, at this temperature,
The initiator, that is to say: 0.5 g of potassium persulfate dissolved in 20 g of deionized water.

It is left to react under these conditions at 72 "C for 3 hours, then the temperature is raised to 85" C and it is left to react again for 5 hours.

It then returns to ambient temperature with stirring. The latex is collected and filtered.

A stable latex is obtained with a dry matter concentration of polymer equal to 25% by weight.

The temperature Tg measured by DSC (Differential Calorimetry) is 115 "C.

The particle sizes are determined by quasi-elastic light scattering on a COULTER N4 SD device from the company COULTRONIX: - average particle size 65 nm - polydispersity in size <0.1
EXAMPLE 2 Preparation of a compatible film-forming acrylic oligomer
in a water / ethanollDME aerosol lacquer medium at
55% maximum VOC
Composition of the oligomer: - isobutyl acrylate 50% by weight - tert-butyl acrylate 40% by weight - acrylic acid 10% by weight
Procedure:
The following mixture is introduced into a cylindrical reactor with mechanical central agitation, thermometer, refrigerant and nitrogen sparging: - isobutyl acrylate 50 g - tert-butyl acrylate 40 g - methacrylic acid 10 g - azobisisobutylacrylonitrile (initiator) 29 - ethanol 200 g
The mixture is stirred and bubbled with nitrogen at reflux of the methanol (78 ° C.). It is left to react for 12 hours under these conditions. It returns to ambient temperature.

The polymer is then purified by precipitation of the alcoholic solution in 5 l of petroleum ether. The precipitate is then dried until a constant weight is obtained.

The yield obtained after drying is 90%. The acid number obtained is 81.5. The molecular weight at the top of the peak measured by steric exclusion chromatography is 36,800 (elution in tetrahydrofuran relative to polystyrene standards). The temperature T'g measured by DSC is 27 "C.

A concentrated alcoholic oligomer solution 100% neutralized with 2-amino-2-methyl-propanol-1 (AMP) is produced from the following mixture: - Oligomer of Example 2 100 g - AMP 12.44 g - Ethanol 112.44 g
The mixture is stirred for 24 hours at room temperature. A 50% by weight solution of dry matter of oligomer is thus obtained.

EXAMPLE 3 Preparation of a compatible film-forming acrylic oligomer
in a water / ethanol / DME aerosol lacquer medium at a rate of
55% maximum VOC
Composition of the oligomer: - isobutyl acrylate 90% by weight - acrylic acid 10% by weight
Procedure:
The following mixture is introduced into a cylindrical reactor with mechanical central agitation, thermometer, refrigerant and nitrogen sparging: - isobutyl acrylate 90 g - acrylic acid 10 g - azobisisobutylacrylonitrile 29 - ethanol 200 g
The operation is carried out under the same conditions as those of Example 2.

The yield obtained after drying is 95%. The acid number obtained is 81.

The molecular weight at the top of the peak measured by steric exclusion chromatography is 33400 (elution in tetrahydrofuran relative to polystyrene standards). The temperature T'g measured by DSC is 0 "C.

A concentrated alcoholic oligomer solution 100% neutralized with 2-amino-2-methylpropanol (AMP) is produced from the following mixture: - Oligomer of Example 3 100 g - AMP 12.44 g - Ethanol 112 , 44g
The mixture is stirred for 24 hours at room temperature. An oligomer solution containing 50% dry matter is thus obtained.

EXAMPLE 4 Preparation of a compatible film-forming oligomer
in a medium aerosol aerosol eauléthanollDME at rate of
55% maximum VOC
Composition of the oligomer: - crotonic acid 10% by weight - vinyl acetate 90% by weight
Procedure:
In a cylindrical reactor with mechanical central stirring, thermometer, refrigerant and nitrogen bubbling, the following mixture is successively introduced to form the base stock: - crotonic acid 1 g - vinyl acetate 9g - ethyl acetate 80 g - tertio- butyl peroxy2-ethylhexanoate 0.7 g
sold under the name TRIGONOX 21 S
by AKZO
The mixture is stirred and bubbled at 78 "C (reflux) and allowed to react for 15 minutes. Double casting is then started simultaneously with the remainder of the monomer mixture on the one hand and the initiator dissolved in the remainder of solvent d On the other hand, the mixture of monomers consisting of: - crotonic acid 9g - vinyl acetate 81 g was introduced into a first introduction ampoule.
This mixture is poured into the reaction medium with stirring and at reflux for 4 hours. Simultaneously, the mixture consisting of - ethyl acetate 80 g - tert-butyl peroxy2-ethylhexanoate 29 was introduced into a second introduction ampoule.
sold under the name TRIGONOX 21 S
by AKZO
This second mixture is poured simultaneously with the first into the reaction medium for 4 h 30.

At the end of the two additions, the mixture is left to react again for 2 hours at reflux. The final initiator is then poured into the solvent. For this, the mixture consisting of: - ethyl acetate 30 g - tert-butyl peroxy2-ethylhexanoate 19 was again introduced into an introduction funnel
sold under the name TRIGONOX 21 S by AKZO
This mixture is added over 1 hour to the medium with stirring and at reflux.

Leave to react again 4 hours at the end of the introduction. It is then brought back to room temperature and the polymer is purified by precipitating the solution in 10 l of petroleum ether. The precipitate is dried until a constant weight is obtained.

Yield: 76.2%
Acid number: 75.9%
(i.e. 11.7% crotonic acid)
Temperature T'g measured by DSC: 40 "C
Molecular weight measured in chroma-: 23,000 steric exclusion tography
EXAMPLE 5: Water / ethanol / DME aerosol lacquer with 55% VOC for the
hair fixing containing a mixture consisting of
30% by weight in dry matter of rigid latex and not
film-forming and 70% by weight in dry matter of oligomer
COMPOSITION BEFORE PACKAGING: - Alcoholic solution at 50% by weight of oligomer of Example 2 166.709 - Deionized water 854.87 g - Ethanol 395.72 g - Dispersion at 25% by weight of non-film-forming particles 100.009
from example 1
AEROSOL LACQUER 55% VOC :: - Composition above 35 g - Dimethylether 15 9
This lacquer contains 5% by weight of dry matter
After application to the hair, excellent lacquering power, good cosmetic properties and good removal of the deposit with shampoo are obtained.

EXAMPLE 6 Water / ethanollDME aerosol lacquer with 55% VOC for the
hair fixing containing a mixture consisting of
50% by weight in dry matter of rigid latex and not
film-forming and 50% by weight in dry matter of oligomer
COMPOSITION BEFORE PACKAGING: - Alcoholic solution at 50% by weight of oligomer of Example 2 50.00 g - Deionized water 354.18 g - Ethanol 196.10 9 - Dispersion at 25% by weight of non-film-forming particles 100, 00 g
from example 1
AEROSOL LACQUER 55% VOC: - Composition above 35 g - Dimethylether 15 g
This lacquer contains 5% by weight of dry matter
After application to the hair, excellent lacquering power, good cosmetic properties and total elimination of the deposit with shampoo are obtained.

EXAMPLE 7 Aerosol lacquer eauléthanollDME with 55% VOC for the
hair fixing containing a mixture consisting of
50% by weight in dry matter of rigid latex and not
film-forming and 50% by weight in dry matter of oligomer
COMPOSITION BEFORE PACKAGING: - Alcoholic solution at 50% by weight of oligomer of Example 3 50.00 g - Deionized water 354.18 g - Ethanol 196.10 g - Dispersion at 25% by weight of non-film-forming particles 100, 00 g
from example 1
AEROSOL LACQUER 55% VOC: - Composition above 35 g - Dimethylether 15 9
This lacquer contains 5% by weight of dry matter
After application to the hair, excellent lacquering power, good cosmetic properties and total elimination of the deposit with shampoo are obtained.

EXAMPLE 8 Water / ethanol / DME aerosol lacquer with 55% VOC for the
hair fixing containing a mixture consisting of
50% by weight in dry matter of rigid latex and not
film-forming and 50% by weight in dry matter of oligomer
COMPOSITION BEFORE PACKAGING: - Oligomer of Example 4 3.20 g - AMP to neutralize the oligomer at 100% 0.38 g - Permuted water 50.58 g - Ethanol 31.57 g - Dispersion at 25% by weight of non-film-forming particles 14.28 g
from example 1
AEROSOL LACQUER 55% VOC: - Composition above 35 g - Dimethylether 15 9
This lacquer contains 5% by weight of dry matter
After application to the hair, excellent lacquering power, good cosmetic properties and total elimination of the deposit with shampoo are obtained.

EXAMPLE 9 Water / ethanol / DME aerosol lacquer for fixing the hair
45% VOC containing a mixture of 50%
weight of rigid non-film-forming latex dry matter and
50% by weight in dry matter of film-forming oligomer
COMPOSITION BEFORE PACKAGING: - Alcoholic solution at 50% by weight of oligomer of Example 2 11.54 g - Deionized water 55.06 g - Ethanol 10.32 g - Dispersion at 25% by weight of non-film-forming particles 23, 08 g
from example 1
AEROSOL LACQUER AT 45% VOC: - Composition above 65 g - Dimethylether 35 g
This lacquer contains 7.5% by weight of dry matter
After application to the hair, excellent lacquering power, good cosmetic properties and total elimination of the deposit with shampoo are obtained.

EXAMPLE 10 Water / ethanol / DME aerosol lacquer for fixing the hair
33.5% VOC containing a mixture of 43%
weight of rigid non-film-forming latex dry matter and
57% by weight in dry matter of film-forming oligomer
COMPOSITION BEFORE PACKAGING: - Alcoholic solution at 50% by weight of oligomer of Example 2 10 g - Permuted water 75 g - Dispersion at 25% by weight of non-film-forming particles 5 g
from example 1
AEROSOL LACQUER AT 45% VOC: - Composition above 70 g - Dimethylether 30 g
This lacquer contains 6.125% by weight of dry matter
After application to the hair, very little rewetting of the hair is obtained, despite the large amount of water contained in the spray, rapid fixing of the hairstyle and good lacquering power, a pleasant touch and easy disentangling by brushing. There is also a total elimination of the deposit with shampoo.

Claims (47)

1. Cosmetic or dermatological composition, characterized in that it contains in a cosmetically acceptable aqueous medium at least: (A) a film-forming oligomer soluble or dispersible in said medium, having a molecular weight measured by steric exclusion chromatography, lower or equal to 50,000; (B) an aqueous dispersion of rigid and non-film-forming polymer particles whose average size is less than or equal to 500 nm and with a glass transition temperature Tg greater than 50 C. 2. Composition according to claim 1, characterized in that the film-forming oligomer has a molecular weight measured in steric exclusion chromatography ranging from 500 to 45,000. 3. Composition according to claim 1 or 2, characterized in that the film-forming oligomer has a glass transition temperature T'g ranging from - 50 "C to + 50" C. 4. Composition according to any one of claims 1 to 3, according to which the film-forming oligomer is soluble in aqueous or hydroalcoholic medium. 5. Composition according to any one of claims 1 to 4, according to which the film-forming oligomer is a nonionic, anionic or amphoteric polymer. 6. Composition according to any one of claims 1 to 5, according to which the film-forming oligomer is an anionic polymer carrying ionized or ionizable anionic groups which can be partially or completely neutralized. 7. Composition according to claim 6, according to which the anionic groups are carboxylic acid and / or sulfonic acid groups. 8. Composition according to claim 7, according to which the carboxylic acid and / or sulfonic acid groups are present in proportions less than or equal to 10% by weight relative to the weight of the oligomer. 9. Composition according to any one of claims 1 to 8, according to which the film-forming oligomer is chosen from the group consisting of copolymers of vinyl esters and crotonic acid and / or maleic acid; copolymers of esters of (meth) acrylic acid in C1-Cs and of acrylic acid eVou of methacrylic acid. 10. Composition according to any one of claims 1 to 9, according to which the rigid and non-film-forming polymer particles have a glass transition temperature Tg greater than 70 "C. 11. Composition according to any one of claims 1 to 10, according to which the rigid and non-film-forming polymer particles have an average size less than or equal to 300 nm and preferably less than or equal to 100 nm. 12. Composition according to any one of claims 1 to 11, according to which the polydispersity in size of the rigid and non-film-forming polymer particles, measured in quasi-elastic light scattering, is less than 0.35. 13. Composition according to any one of claims 1 to 12, according to which the polymer constituting the rigid and non-film-forming particles is crosslinked. 14. Composition according to claim 13, characterized in that the crosslinking agent is present in proportions ranging from 0.1 to 50% by weight relative to the weight of said polymer. 15. Composition according to any one of claims 1 to 14, according to which the polymer constituting the rigid and non-film-forming particles is an anionic polymer comprising ionized or ionizable anionic groups which can be partially or completely neutralized. 16. Composition according to claim 15, according to which the anionic groups are carboxylic acid and / or sulfonic acid groups. 17. Composition according to claim 16, according to which the carboxylic acid and / or sulfonic acid groups are present in proportions less than or equal to 10% by weight relative to the weight of the polymer. 18. Composition according to any one of claims 1 to 17, characterized in that the polymer constituting the rigid and non-film-forming particles is a polymer or copolymer obtained by polymerization or copolymerization of a monomer or a mixture of monomers chosen from the group consisting of C1-C10 linear, cyclic or branched alkyl acrylates or methacrylates, styrene, vinyltoluene, vinyl chloride, vinyl benzoate, vinyl tert-butylbenzoate, Acrylic acid, Acid methacrylic. 19. Composition according to any one of claims 1 to 18, characterized in that the polymer constituting the rigid and non-film-forming particles is a crosslinked copolymer of at least one linear, cyclic or branched C alkyl methacrylate , -C8 and acrylic acid and / or methacrylic acid. 20. Composition according to any one of claims 1 to 19, characterized in that the cosmetically acceptable aqueous medium consists of water or a mixture of water and at least one cosmetically acceptable solvent 21. Composition according to claim 20, characterized in that the solvent is chosen from the group consisting of monoalcohols, polyalcohols, glycol ethers, acetone or esters, alone or as a mixture. 22. Composition according to any one of claims 1 to 21, characterized in that the cosmetically acceptable aqueous medium consists of water or water and a lower C1-C4 alcohol. 23. Composition according to any one of claims 1 to 22, characterized in that the concentration of organic solvent is between 15 and 35% by weight relative to the total weight of the composition. 24. Composition according to any one of claims 1 to 23, characterized in that it is packaged in a pressurized aerosol device or a pump bottle. 25. Composition according to claim 24, characterized in that it is packaged in a pressurized aerosol device in the presence of a propellant. 26. Composition according to claim 25, according to which the propellant is chosen from the group consisting of volatile hydrocarbons, chlorinated and / or fluorinated hydrocarbons and their mixtures; carbon dioxide, nitrous oxide, dimethyl ether, nitrogen or compressed air. 27. Composition according to claim 25, according to which the propellant is dimethyl ether. 28. Composition according to claim 27, according to which the dimethyl ether concentration is between 30 and 45% by weight relative to the total weight of the composition. 29. Composition according to any one of claims 24 to 28, according to which the concentration of volatile organic compound (VOC) is less than or equal to 55% by weight relative to the total weight of the composition packaged in aerosol or in pump bottle. 30. Composition according to any one of claims 24 to 29, characterized in that in the mixture constituted by rigid and non-film-forming particles and by the film-forming oligomer, the proportions in particles vary from 5 to 95% by weight in material dry relative to the weight of the mixture. 31. Composition according to claims 30, characterized in that in the mixture constituted by the rigid and non-film-forming particles and by the film-forming isomer, the proportions in particles vary from 40 to 95% by weight in dry matter relative to the weight of the mixture. 32. Composition according to claims 30, characterized in that in the mixture constituted by the rigid and non-film-forming particles and by the film-forming oligomer, the proportions in particles vary from 70 to 95% by weight in dry matter relative to the weight of the mixture. 33. Composition according to any one of claims 1 to 32, characterized in that it additionally contains a plasticizing agent. 34. Use of the combination consisting of rigid and non-film-forming particles and of the film-forming oligomer as defined in any one of claims 1 to 33 as a coating agent for keratin materials in and for the preparation of a cosmetic composition or dermatological. 35. Use as a base of hair product for shaping and maintaining the hairstyle of the composition as defined according to any one of claims 1 to 33. 36. Hair product for shaping and / or maintaining the hairstyle, characterized in that it consists of a composition as defined according to any one of claims 1 to 33. 37. Hair product according to claim 36, characterized in that it contains the mixture consisting of rigid and non-film-forming particles and by the film-forming oligomer in proportions ranging from 3 to 20% by weight in dry matter relative to the total weight of the composition. 38. Hair product for shaping and / or maintaining the hairstyle according to claim 36 or 37, characterized in that it is a product chosen from the group consisting of aerosol lacquers or bottles. pumps for fixing the hair, lotions for styling and lotions for brushing, styling mousse. 39. Use as a product base for coating the eyelashes and the eyebrows with the composition as defined according to any one of claims 1 to 23, 30 and 33. 40. Product for coating the eyelashes and the eyebrows, characterized in that it consists of a composition as defined according to any one of claims 1 to 23, 30 and 33. 41. Product for coating the eyelashes and the eyebrows according to claim 40, characterized in that it contains the mixture constituted by rigid and non-film-forming particles and by the film-forming oligomer in proportions ranging from 2 to 15%. by weight in dry matter relative to the total weight of the composition. 42. Product for coating the eyelashes and eyebrows according to claim 40 or 41, characterized in that it is a mascara. 43. Use as a product base for coating the nails of the composition as defined according to any one of claims 1 to 23, 30 and 33. 44. Product for coating the nails, characterized in that it consists of a composition as defined according to any one of claims 1 to 23, 30 and 33. 45. Product for coating the nails according to claim 44, characterized in that it contains the mixture constituted by rigid and non-film-forming particles and by the film-forming oligomer in proportions ranging from 15 to 30% by weight in dry matter. relative to the total weight of the composition. 46. Product for coating the nails according to claim 44 or 45, characterized in that it is chosen from the group consisting of a nail varnish with easy removal in the wash, an undercoat of a nail varnish, a nail care base containing protective agents, hardeners and / or for nail care. 47. A method of non-therapeutic treatment of keratin materials such as the hair, the eyelashes, the eyebrows or the nails, characterized in that it consists in applying directly to the keratin materials a cosmetic composition as defined according to any one from claims 1 to 33.