FR2791557A1 - Cosmetic make-up composition comprising an aqueous dispersion of film-forming polymer particles includes an associative polyurethane and a cation-containing silicate as thickeners - Google Patents

Abstract

Cosmetic make-up composition comprising an aqueous dispersion of film-forming polymer particles includes an associative polyurethane (I) and a cation-containing silicate (II) in amounts such that the composition has a viscosity of at least 1 Pa.s (measured at 25 deg C and 20 rpm). An Independent claim is also included for a make-up product comprising: a vessel that contains the make-up composition and has an opening for distributing the composition; and means for applying pressure to distribute the composition through the opening.

Description

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The subject of the present invention is a thickened composition for making up the skin or integuments, containing an aqueous polymer dispersion, the use of such a composition for making up the skin and integuments, as well as a process for makeup of these. The makeup composition and method according to the invention are more particularly intended for making up the skin of the face, including the lips and the eyelids, of the body, and of the integuments such as the eyelashes, the eyebrows, the hair and the nails. of human beings.

The invention also relates to a makeup product comprising this composition.

Make-up products are commonly used to add color, enhance certain parts of the skin or integuments, or even provide a shiny, matte, satin-like appearance to the skin or integuments. These products are usually applied as a uniform thin layer.

EP-A-143480, FR-A-2399238 and EP-A-648485 disclose fluid nail varnish compositions comprising an aqueous dispersion of film-forming polymer particles. These fluid compositions are generally packaged in a glass vial provided with an applicator member such as a brush. The application member makes it possible to apply the fluid composition in the form of a uniform thin layer. With these fluid compositions, it is often necessary to apply two layers of product in order to obtain a film which perfectly covers the nail, that is to say a film which does not allow the nail to be seen through the film. In addition, it is possible to remove too much product with the brush if the latter is not well drained and the excess product harms the proper application of the composition on the nail.

With the evolution of fashion, more demanding consumers are looking for new makeup products, such as products presented in a new type of packaging.

Thus, if one wishes to present a composition of nail varnish in a tube-shaped packaging, the fluid formulas known to date are not suitable. The composition must be thickened so that it can be distributed correctly with the tube. We therefore seek for this particular packaging a composition sufficiently thick and which has good spreading properties, in particular using a brush, to form a thin layer of makeup. In addition, the composition must have good storage stability.

The present invention therefore aims to provide a thickened makeup composition that can spread easily on the skin and on the integuments and providing a correct makeup film.

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The Applicant has found that such a makeup composition could be obtained using a combination of two thickening agents and having a particular high viscosity. A product of this viscosity can be easily removed and dosed, unlike a fluid product.

More specifically, the subject of the present invention is a cosmetic makeup composition comprising an aqueous dispersion of film-forming polymer particles, characterized in that the composition comprises at least one associative polyurethane and at least one silicate comprising at least one cation, the polyurethane and the silicate being present in an amount effective so that the composition has a viscosity of at least 1 Pa. s, measured at 25 ° C., at the speed of rotation of 20 revolutions / min.

Another object of the invention is a process for making up the skin and / or the integuments consisting in applying to the skin and / or the integuments a composition as defined above.

In practice, the composition according to the invention advantageously has a viscosity, measured at 25 ° C. and at a rotation speed of 20 revolutions / minute ranging from 1 Pa. S to 5 Pa. S (10 to 50 Poises), and better from 2 to 4 Pa. s (20 to 40 Poises).

The viscosity is measured with a BROOKFIELD VD2 + viscometer equipped with a mobile No. 3, the measurement being made after 10 minutes of rotation of the mobile (time after which the viscosity and the speed of rotation of the mobile are stabilized. ).

Associative polyurethanes are nonionic block copolymers comprising in the chain, both hydrophilic blocks of a nature most often polyoxyethylenated and hydrophobic blocks which can be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences.

In particular, these polymers comprise at least two lipophilic hydrocarbon chains, having from C6 to C30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains can be pendant chains or chains at the end of hydrophilic block. In particular, it is possible that one or more hanging chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

The polymers can be sequenced as a triblock or multiblock. The hydrophobic sequences can therefore be at each end of the chain (for example

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 example: triblock copolymer with a hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). The polymers can also be in grafts or in a star.

Preferably, the polymers are triblock copolymers in which the hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. In general, associative polyurethanes contain a urethane bond between the hydrophilic sequences, hence the origin of the name.

By way of example, associative polymers which can be used in the invention, mention may be made of the polymer C16-OE120-C16 sold by the company HULS (under the name Sérad FX1100, molecule with urethane function and average molecular weight by weight of 1300) , OE being an oxyethylenated unit. As associative polymer, it is also possible to use Rheolate 205 with urea function sold by the company RHEOX or even Rheolate 208 or 204. These associative polyurethanes are sold in pure form.

The product DW 1206B from RHOM & HAAS with a C20 alkyl chain and a urethane bond, sold at 20% as dry matter in water, can also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in an alcoholic medium. By way of example, such polymers that may be mentioned include Sérad FX1010, Sérad FX1035 and Serad 1070 sold by the company HULS, Rheolate 255, Rheolate 278 and Rheolate 244 sold by RHEOX. One can also use the product DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from the company RHOM & HAAS, or even Borchigel LW 44 from the company BORCHERS.

The polymers which can be used in the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271,380,389 (1993).

The composition according to the invention contains one or more associative polyurethanes in an amount sufficient to obtain a composition having the viscosity indicated above. Advantageously, the associative polyurethane can be present in an amount ranging from 0.1 to 5% by weight, relative to the total weight of the composition, and better still from 0.3% to 2% by weight.

The silicate present in the composition according to the invention may contain a cation chosen from the cations of calcium, magnesium, aluminum, sodium, potassium, lithium and their mixtures.

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As silicate which can be used in the invention, mention may be made of sodium and magnesium silicates and in particular sodium, lithium and magnesium silicate, such as the products sold by the company Laporte under the name Laponite XLG, Laponite RD, Laponite RDS , magnesium and aluminum silicates in particular hydrated as the product sold by the company Vanderbilt Company under the name Veegum ultra, which are synthetic smectite clays or calcium silicates and in particular that in synthetic form sold by # company under the name of Micro-cel C.

The silicate may be present in the composition according to the invention in an amount effective for stabilizing the composition and in particular in a content ranging from 0.3% to 9% by weight, relative to the total weight of the composition, and preferably from 0.8% to 3% by weight.

According to a particular embodiment according to the invention, the associative polyurethane and the silicate can be present in the composition according to an associative polyurethane / silicate weight ratio ranging from 0.1 to 2 and better still ranging from 0.5 to 1.2.

In the present application, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, an isolable film.

Among the film-forming polymers which can be used in the composition of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and mixtures thereof.

By radical film-forming polymer is meant a polymer obtained by polymerization of unsaturated monomers, in particular ethylenic, each monomer being capable of homopolymerizing (unlike polycondensates).

The film-forming polymers of free-radical type may in particular be vinyl polymers or copolymers, in particular acrylic polymers.

The vinyl film-forming polymers can result from the polymerization of ethylenically unsaturated monomers having at least one acid group and / or esters of these acid monomers and / or amides of these acid monomers.

Anionic radical film-forming polymers are preferably used, that is to say monomers having at least one monomer with an acid group.

As the monomer carrying an acid group, unsaturated carboxylic acids [alpha], ss-ethylenic acids such as acrylic acid, methacrylic acid can be used.

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 lique, crotonic acid, maleic acid, itaconic acid. Preferably (meth) acrylic acid and crotonic acid are used, and more preferably (meth) acrylic acid.

The esters of acidic monomers are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C1-C20 alkyl, of preferably in C1-C8, aryl (meth) acrylates, in particular C6-C10 aryl, hydroxyalkyl (meth) acrylates, in particular C2-C6 hydroxyalkyl.

Mention may be made, among alkyl (meth) acrylates, of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate.

Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

Among the aryl (meth) acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

Particularly preferred esters of (meth) acrylic acid are alkyl (meth) acrylates.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, that is to say that part or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

As amides of the acidic monomers, mention may, for example, be made of (meth) acrylamides, and in particular of N-alkyl (meth) acrylamides, in particular of C2-C12alkyl. cite N-ethyl acrylamide, Nt-butyl acrylamide and Nt-octyl acrylamide.

The film-forming vinyl polymers can also result from the homopolymerization or from the copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.

Examples of vinyl esters that may be mentioned include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.

As styrene monomers, mention may be made of styrene and alpha-methyl styrene.

The list of monomers given is not exhaustive and it is possible to use any monomer known to a person skilled in the art falling within the categories of acrylic and vinyl monomers (including the monomers modified by a silicone chain).

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As film-forming acrylic polymer which can be used according to the invention, mention may be made of those sold under the names NEOCRYL XK-90, NEOCRYL A-1070, NEOCRYL A-1090 #, NEOCRYL BT-62 #, NEOCRYL A-1079 #, NEOCRYL A- 523 # by the company ZENECA, DOW LATEX 432 # by the company DOW CHEMICAL.

Among the polycondensates which can be used as film-forming polymer, mention may be made of polyurethanes, polyesters, polyester amides, fatty chain polyesters, polyamides, and epoxy ester resins.

The polyesters can be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols.

The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2.2 acid -dimethylglutaric, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, acid 1,3- cyclohexanedicarboxylic, 1,4-cyclohexa-nedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norborane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5- acid naphthalenedicarboxylic, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers can be used alone or in combination of at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are preferably chosen.

The diol can be chosen from aliphatic, alicyclic, aromatic diols. Preferably, a diol chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol is used.

As other polyols, glycerol, pentaerythritol, sorbitol, trimethylol propane can be used.

The polyester amides can be obtained in a similar manner to the polyesters, by polycondensation of diacids with diamines or amino alcohols.

As diamine, ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine can be used. As amino alcohol, monoethanolamine can be used.

The polyester may also comprise at least one monomer carrying at least one group -SO3M, with M representing a hydrogen atom, an ammonium ion NH4 + or a metal ion, such as for example an ion Na +, Li +, K +, Mg2 +,

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 Ca2 +, Cu2 +, Fe2 +, Fe3 +. One can use in particular a bifunctional aromatic monomer comprising such a group -SO3M.

The aromatic nucleus of the bifunctional aromatic monomer further bearing a group -SO3M as described above can be chosen for example from benzene, naphthalene, anthracene, diphenyl, oxidiphenyl, sulfonyldiphenyl, methylenediphenyl nuclei. As an example of a bifunctional aromatic monomer further bearing a group -SO3M: sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, 4-sulfonaphthalene-2,7dicarboxylic acid.

It is preferred to use in the compositions which are the subject of the invention copolymers based on isophthalate / sulfoisophthalate, and more particularly copolymers obtained by condensation of di-ethylene glycol, cyclohexane di-methanol, isophthalic acid, sulfoisophthalic acid. Such polymers are sold, for example, under the brand name Eastman AQ by the company Eastman Chemical Products.

The polymers of natural origin, optionally modified, can be chosen from shellac resin, sandara gum, dammars, elemis, copals, water-insoluble cellulosic polymers, and mixtures thereof.

Mention may also be made of the polymers resulting from the radical polymerization of one or more radical monomers inside and / or partially at the surface, of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and / or alkyds. These polymers are generally called hybrid polymers.

The dispersion comprising one or more film-forming polymers can be prepared by a person skilled in the art on the basis of his general knowledge.

The size of the polymer particles in aqueous dispersion can range from 10 to 500 nm, and is preferably from 20 to 300 nm.

The polymer in aqueous dispersion can be present in the composition according to the invention in an amount effective for forming a film and in particular in a content ranging from 1% to 60% by weight, preferably from 5% to 45% by weight of material. dry film-forming polymers relative to the total weight of the composition.

To improve the film-forming properties of the composition according to the invention, the composition may contain plasticizing agents and / or coalescing agents which are well known to those skilled in the art.

The composition can comprise an aqueous medium which can consist essentially of water or alternatively of a hydroalcoholic mixture and in particular

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 containing lower C1-C5 monoalcohols. The water content in the composition can range from 30 to 99% by weight, relative to the total weight of the composition, and preferably from 60% to 80% by weight.

The composition can also comprise a coloring matter such as pulverulent compounds, for example in an amount of 0.1% to 25% of the total weight of the composition, preferably from 1% to 10% by weight. The pulverulent compounds can be chosen from pigments and / or nacres and / or fillers usually used in makeup compositions.

Advantageously, the composition according to the invention is well suited for the use of pulverulent compounds having a density greater than or equal to 2 kg / m3, and in particular ranging from 2 to 5 kg / m3 and better still from 2.5 to 4 kg. / m3. The association of thickeners makes it possible to prepare a stable composition with these pulverulent compounds, in particular at 45 ° C. for one month.

The pigments can be white or colored, mineral and / or organic, interference or not. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chrome and ferric blue. Among the organic pigments, there may be mentioned carbon black, pigments of the D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.

The pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica titanium with iron oxides, mica titanium with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type, guanine as well as pearlescent pigments based on bismuth oxychloride.

The pigments can comprise a coating well known to those skilled in the art. For example, the coating can be a silicone, a fluorinated compound or polyethylene.

Furthermore, the composition according to the invention may contain adjuvants commonly used in cosmetic compositions, in particular topical. By way of example of additives, mention may be made of dyes, lakes, anti-UV agents, preservatives, surfactants, spreading agents, perfumes, active agents and moisturizing agents. Of course, a person skilled in the art will take care to choose this or these optional adjuvants, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially,

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 not altered by the addition envisaged, and which therefore makes it possible to obtain a composition with the viscosity indicated above.

Due to its high viscosity, the composition according to the invention can be packaged in a particular packaging device.

Another object of the invention is a makeup product comprising on the one hand the makeup composition as described above, and on the other hand a particular conditioning device for said composition.

The packaging device for the composition according to the invention may comprise a reservoir, intended to contain the makeup composition, in communication with a dispensing orifice for the composition capable of being closed by a plug and comprising pressure means allowing the dispensing of composition through the hole. According to one embodiment of the packaging device, the reservoir may include a flexible wall constituting the pressure means allowing the composition to be distributed through the orifice of the reservoir. Such a reservoir may in particular be a flexible wall tube.

This dispensing device makes it possible to easily apply the composition to the skin and / or the integuments in the form of a hazelnut, the latter then being able to be spread over the skin and / or the integuments using an applicator such as a brush, a paint brush, a spatula, a foam tip applicator.

The composition can also be applied to the skin or the integuments using a stencil: the composition thus deposited in the hollowed out parts of the stencil retains its shape after removal of the stencil, thus giving a very decorative make-up on the skin.

The invention is illustrated in more detail in the following examples.

The description which follows refers to appended FIG. 1 which presents, in longitudinal section, a makeup product in accordance with the invention.

The packaging assembly represented in FIG. 1 is designated as a whole by the reference 1. It consists of a reservoir 2 in the form of a tube containing the composition P to be applied provided with a dispensing orifice 3 capable of being closed by a plug. The orifice 3 has a circular section S whose diameter d can for example range from 0.1 mm to 10 mm, and in particular from 0.8 mm to 2 mm.

The tube 2 is provided with a flexible wall 4. To apply the composition with the tube, pressure is exerted on the wall 4 using the fingers so that the composition

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 sition contained in the tube is expelled from the tank 2 through the dispensing orifice 3.

Thus, the flexible wall 4 of the tube 2 constitutes a pressure means allowing the distribution of the composition P through the orifice 3 of distribution.

With this conditioning device; composition P is distributed in the form of a hazelnut or pearl.

EXAMPLE 1 A varnish in the form of a cream for making up the nails having the following composition was prepared, by simple mixing at room temperature, with the following composition: aqueous dispersion of styrene / acrylate copolymer (JONCRYL SCX 82-11 from JOHNSON) at 42, 8% dry matter 28, g MA - Associative polyurethane (BORCHIGEL LW 44 from BORCHERS) at 50% in water 1 g MA - Magnesium and sodium silicate (Laponite XLG from LAPORTE) 1 g - Plasticizer 3 g - Coalescing agent 2 g - Silicone - Titanium mica-oxide - brown iron oxide (density 3 kg / m3) 3 g - Ethanol 4.8 g - Preservatives qs - Water qs 100 g The composition has a viscosity of 3, 5 Pa. S (35 poises) measured at 25 C, using the BROOKFIELD VD2 +, fitted with the No. 3 mobile, at a rotation speed of 20 revolutions / min (measurement made after 10 minutes of rotation).

The composition is perfectly stable for 1 month at 45 C.

The composition was packaged in a tube as described in Figure 1.

The composition was deposited on the nails and then spread over them using a brush. There was thus obtained a shiny nail polish with good hold.

 Furthermore, it has been found that a composition similar to that of Example 1 not containing laponite XLG is not stable for 1 month at 45 ° C.: the pigment settles.

Claims (26)

 CLAIMS 1. Cosmetic makeup composition comprising an aqueous dispersion of film-forming polymer particles, characterized in that the composition comprises at least one associative polyurethane and at least one silicate comprising at least one cation, the polyurethane and the silicate being present in one amount effective for the composition to have a viscosity of at least 1 Pa. s, measured at 25 ° C., at a speed of rotation of 20 revolutions / min. 2. Composition according to claim 1, characterized in that the viscosity is less than or equal to 5 Pa.s. 3. Composition according to any one of the preceding claims, characterized in that the composition has a viscosity ranging from 2 Pa. S to 4 Pa.s. 4. Composition according to any one of the preceding claims, characterized in that the associative polyurethane is a block or graft polymer comprising at least two alkyl chains having from C6 to C30 carbon atoms, separated by a hydrophilic block. 5. Composition according to one of the preceding claims, in which the associative polyurethane comprises a polyoxyethylenated hydrophilic block. 6. Composition according to one of the preceding claims, in which the associative polyurethane is a triblock polymer. 7. Composition according to any one of the preceding claims, characterized in that the associative polyurethane is present in a content ranging from 0.1% to 5% by weight relative to the total weight of the composition, and better still from 0, 3% to 2% by weight. 8. Composition according to any one of the preceding claims, characterized in that the cation of the silicate is chosen from the group formed by calcium, magnesium, aluminum, sodium, potassium, lithium and their mixtures. 9. Composition according to any one of the preceding claims, characterized in that the silicate is a clay of synthetic origin. 10. Composition according to any one of the preceding claims, characterized in that the silicate is a magnesium, lithium and sodium silicate. <Desc / Clms Page number 12> 11. Composition according to any one of the preceding claims, characterized in that the silicate is present in a content ranging from 0.3% to 9% by weight, relative to the total weight of the composition, and better still from 0, 8% to 3% by weight. 12. Composition according to any one of the preceding claims, characterized in that the associative polyurethane and the silicate are present in an associative polyurethane / silicate weight ratio ranging from 0.1 to 2, and better still from 0.5 to 1, 2. 13. Composition according to any one of the preceding claims, characterized in that the film-forming polymer is chosen from the group formed by radical polymers, polycondensates, polymers of natural origin and their mixtures. 14. Composition according to any one of the preceding claims, characterized in that the film-forming polymer is chosen from the group formed by vinyl polymers, polyurethanes, polyesters. 15. Composition according to any one of the preceding claims, characterized in that the film-forming polymer in aqueous dispersion is present in a content ranging from 1% to 60% by weight, relative to the total weight of the composition. 16. Composition according to any one of the preceding claims, characterized in that it also comprises at least one pulverulent coloring matter chosen from the group formed by pigments and nacres. 17. Composition according to claim 16, characterized in that the pulverulent coloring matter has a density greater than or equal to 2 kg / m3. 18. Composition according to any one of the preceding claims, characterized in that it also comprises at least one adjuvant chosen from the group formed by plasticizing agents, coalescing agents, dyes, lacquers, anti agents -UV, preservatives, surfactants, spreading agents, perfumes, active ingredients, moisturizers. 19. Composition according to any one of the preceding claims, characterized in that it is in the form of a nail polish, of a body makeup product. 20. Use of an associative polyurethane and of a silicate comprising at least one cation in a cosmetic makeup composition having a viscosity of at least <Desc / Clms Page number 13>  minus 1 Pa.s, measured at 25 ° C., at a rotation speed of 20 rpm, comprising an aqueous dispersion of film-forming polymer particles. 21. Use of an associative polyurethane and of a silicate comprising at least one cation in a makeup composition comprising an aqueous dispersion of particles of film-forming polymer, in an amount effective so that the composition has a viscosity of at least 1 Pa .s, measured at 25 C, at a rotation speed of 20 rpm. 22. Method for making up the skin and / or the integuments, characterized in that a composition according to any one of claims 1 to 19 is applied to the skin and / or the integuments. 23. A method of making up the skin according to claim 22, characterized in that the composition is applied to the skin using a stencil. 24. Make-up product (1) comprising a reservoir (2) containing a makeup composition (P) according to any one of claims 1 to 19, said reservoir being in communication with an orifice (3) for dispensing said composition and comprising pressure means (4) allowing the distribution of the composition through the orifice (3). 25. Product according to claim 24, characterized in that the reservoir comprises a flexible wall (4) constituting the pressure means allowing the distribution of the composition through the orifice. 26. Product according to one of claims 24 or 25, characterized in that the reservoir is a flexible wall tube.