Solid composition in powder form comprising a film-forming polymer in the solid state.

Abstract

A solid composition in powder form comprising a film-forming polymer in the solid state. The present invention therefore relates to a solid composition in powder form, particularly for coating keratinous materials, more specifically for makeup and / or skincare of keratinous materials, such as skin, notably comprising a physiologically acceptable medium and containing at least: a) a powdered phase, and b) at least one film-forming polymer in the solid state. Another object of the invention relates to a method for manufacturing a solid composition as defined above, consisting of grinding said film-forming polymer in the solid state with at least a portion of the powdered phase, in particular the particulate coloring matter present in the composition.The invention also relates to a method of coating keratinous materials, more particularly of caring for and / or making up keratinous materials, such as skin, characterized in that it comprises the application on keratinous materials of a solid composition as defined above.

Description

Title of the invention: Solid composition in powder form comprising a film-forming polymer in the solid state.

[0001] The present invention relates to the field of solid cosmetic care and / or makeup compositions.

[0002] The dosage forms conventionally used for solid compositions are generally loose, pressed or compact powders. By way of illustration and not limitation of the solid dosage forms more particularly considered in the field of makeup, mention may in particular be made of loose, pressed or compact powders of the foundation and blush or eyeshadow type.

[0003] The above-mentioned powders mainly have the function of providing color, mattness and even, for those more particularly intended for facial skin, of improving the hold of the foundation or, if used alone, of providing coverage (powder foundation).

[0004] These galenic forms are particularly appreciated by users due to their lightness, softness and non-sticky or greasy feel.

[0005] Generally speaking, these compositions combine a generally predominant pulverulent phase with a binder phase most often represented by a liquid fatty phase. The pulverulent phase is formed essentially of fillers combined with pigments, the quantity of the latter being modulated to provide the desired makeup effect, generally colored. As regards fillers, preference is generally given to choosing materials capable of exhibiting an absorbent and / or adsorbent capacity with respect to the associated binder phase.

[0006] Makeup compositions in powder form generally have poor staying power. This is explained in particular by the fact that these compositions generally do not contain a film-forming polymer to improve the resistance of the deposit. It nevertheless remains possible to produce makeup compositions comprising a film-forming polymer solubilized in a volatile solvent in order to convey said film-forming polymer. Such state-of-the-art compositions comprising a solubilized film-forming polymer are described in particular in patent application EP2408419A1 and patents EP2616043B1 and FR 1057468B1. However, these compositions in powder form require the use of sealed packaging to prevent evaporation of the volatile solvent. This is restrictive and represents a cost.In addition, these compositions tend to degrade over time gradually with use, due to the evaporation of the solvent.

[0007] There therefore remains a need to produce new cosmetic powders for the care and / or makeup of keratin materials such as skin having a strong hold based on film-forming polymer without the drawbacks mentioned above, in particular having good stability over time as they are used without the need to use sealed packaging.

[0008] The applicant has surprisingly discovered that this objective is achieved with a solid composition in powder form, in particular for coating keratin materials, more particularly for making up and / or caring for keratin materials, such as the skin, in particular comprising a physiologically acceptable medium and containing at least: a) a powdery phase, and b) at least one film-forming polymer in the solid state.

[0009] This discovery is the basis of the invention.

[0010] The present invention therefore relates to a solid composition in powder form, in particular for coating keratin materials, more particularly for making up and / or caring for keratin materials, such as the skin, in particular comprising a physiologically acceptable medium and containing at least: a) a powdery phase, and b) at least one film-forming polymer in the solid state.

[0011] Another subject of the invention relates to a process for manufacturing a solid composition in powder form as defined above, consisting of grinding in the solid state said film-forming polymer with at least part of the pulverulent phase, in particular the particulate coloring materials present in the composition.

[0012] Another subject of the invention also relates to a solid composition in powder form capable of being obtained by said preparation process.

[0013] The invention also relates to a process for coating keratin materials, more particularly for caring for and / or making up keratin materials, such as the skin, characterized in that it comprises the application to the keratin materials of a composition as defined above.

[0014] Another subject of the invention relates to a process for coating keratin materials, more particularly for caring for and / or making up keratin materials, such as the skin, characterized in that it comprises a) the application to the keratin materials of a first layer with a care composition (A) (Base Coat) comprising, in particular in a physiologically acceptable medium, at least one oily phase; and b) on the first layer formed by said composition (A), the application of a second layer with a composition (B) (Top Coat) consisting of a composition as defined previously. Definitions

[0015] In the context of the present invention, the term “keratin material” is understood to mean in particular the skin (body, face, eye contour, eyelids).

[0016] By "physiologically acceptable" is meant compatible with the skin and / or its appendages, which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness), likely to deter the consumer from using this composition.

[0017] For the purposes of the present invention, the term "solid composition" is understood to mean the state of the composition at room temperature (25°C) and atmospheric pressure (760 mm Hg or 105 Pa), that is to say a composition of high consistency, which retains its shape during storage. In contrast to so-called fluid compositions, it does not flow under its own weight. It is advantageously characterized by a hardness, in particular by carrying out a Zwick measurement, the measurement of this hardness being carried out by means of a truncated measuring tip and a measuring force is applied to the sample to be tested. The tip penetrates the sample, and the durometer measures the distance of its displacement in the powder. This displacement is translated into Shore A hardness units.

[0018] The composition according to the invention preferably comprises less than 3.0% by weight of water relative to the total weight of the composition, preferably less than 2.0% by weight, or is even free of water.

[0019] By “loose powder” is meant a product consisting of particles which are not subject to cohesion.

[0020] By “compact powder” is meant a mass of product whose cohesion is ensured at least in part by compacting or preferably pressing during manufacturing.

[0021] The composition according to the invention advantageously comprises a dry extract content greater than or equal to 85%, better still 90%, or even 95%.

[0022] For the purposes of the present invention, “dry extract content” means the content of non-volatile matter.

[0023] The quantity of dry extract (abbreviated ES) of a composition according to the invention is measured using a commercial halogen desiccator “HALOGEN MOISTURE ANALYZER HR 73®” from METTLER TOLEDO. The measurement is based on the weight loss of a sample dried by halogen heating and therefore represents the percentage of residual matter once the water and volatile matter have evaporated.

[0024] This technique is perfectly described in the documentation of the device provided by METTLER TOLEDO. The measurement protocol is as follows: Approximately 2 g of the composition, hereinafter the sample, is spread on a metal dish which is introduced in the halogen desiccator mentioned above. The sample is then subjected to a temperature of 105 °C until a constant weight is obtained. The Wet Mass of the sample, corresponding to its initial mass, and the Dry Mass of the sample, corresponding to its mass after halogen heating, are measured using a precision balance. The experimental error related to the measurement is of the order of plus or minus 2%. The Dry Extract content is calculated as follows:

[0025] [Math 1) Dry Extract Content (expressed in % by weight) = 100 x (Dry Mass / Total Mass)

[0026] Preferably, the composition comprises a proportion of volatile oil of less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight relative to the total weight of the composition, preferably the composition is free of volatile oil.

[0027] By “oil” is meant a fatty substance which is liquid at room temperature (25°C) and atmospheric pressure (760mm Hg or 101,325 Pa).

[0028] For the purposes of the invention, the term "volatile oil" means any oil capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 to 40,000 Pa, in particular ranging from 2.66 Pa to 13,000 Pa, and more particularly ranging from 2.66 Pa to 1,300 Pa.

[0029] The volatile oil or oils may be chosen from hydrocarbon oils, silicone oils, and mixtures thereof.

[0030] The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

[0031] For the purposes of the present invention, the term “silicone oil” means an oil comprising at least one Si-O group, and more particularly an organopolysiloxane.

[0032] Preferably, the solid composition according to the invention is in the form of loose powder or compact powder.

[0033] Preferably, the solid composition according to the invention is an eyeshadow, an eyebrow composition, an eyeliner, a blush, or a powder applicable to the face. Even more preferably, the composition is an eyeshadow or a blush. Powder phase

[0034] A solid composition according to the invention preferably has a powder phase content greater than or equal to 50.0% by weight, in particular greater than or equal to 60.0% by weight, and more particularly ranging from 60 to 80% by weight, relative to the total weight of the composition.

[0035] The powdery phase comprises at least one filler and / or at least one particulate coloring matter. Charges

[0036] By "fillers" is meant colorless or white, solid particles of all shapes, which are in an insoluble form and dispersed in the medium of the composition. Of mineral or organic nature, they make it possible to give the composition softness, mattness and uniformity to the makeup.

[0037] The filler or fillers used in the composition of the invention is (are) chosen from mineral fillers, organic fillers and their mixtures.

[0038] The filler or fillers used in the composition of the invention is (are) present in the composition of the invention, preferably, at a content ranging from 0 to 90% by weight, more preferably from 50 to 80% by weight relative to the total weight of the composition.

[0039] The filler or fillers used in the composition of the invention is (are) present, preferably, at a content ranging from 0 to 95% by weight, more preferably from 25 to 90% by weight relative to the total weight of the pulverulent phase.

[0040] Among the mineral fillers that can be used in the compositions according to the invention, mention may be made of talcs, natural micas, synthetic micas such as fluorphlogopite, silica, magnesium and aluminum silicates, kaolin, bentone, calcium carbonate and magnesium hydrogen carbonate, hydroxyapatite, boron nitride, hollow silica microspheres (Silica Beads from Maprecos), silica-based fillers such as Aerosil 200®, Aerosil 300®; Sunsphere H-33®, Sunsphere H-51® marketed by Asahi Glass; Chemicelen® marketed by Asahi Chemical; silica and titanium dioxide composites, such as the TSG® series marketed by Nippon Sheet Glass, perlite powders, and mixtures thereof.

[0041] Among the organic fillers that can be used in the compositions according to the invention, mention may be made of polyamide powders (Nylon® Orgasol from Atochem), poly-[3-alanine and polyethylene, polytetrafluoroethylene powders (Teflon®), lauroyl-lysine, starches such as native corn starches with the INCI name: ZEA MAYS (CORN) STARCH, modified starches such as aluminum starch octenyl-succinate (DRY FLO), tetrafluoroethylene polymer powders, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example, zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate, Polypore® L 200 (Chemdal Corporation), silicone resin microbeads (Tospearl® of Toshiba, for example), spherical organopolysiloxane elastomer powders with INCI name: DIMETHICONE / VINYL DIMETHICONE CROSSPOLYMER (DOWSIL TREFIL E-506 S SILICONE POWDER®, DOWSIL 9506 POWDER® from DOW CORNING CHEMICAL), polyurethane powders, in particular, crosslinked polyurethane powders comprising a copolymer, said copolymer comprising trimethylol hexyllactone, such as the hexamethylene diisocyanate / trimethylol hexyllactone polymer, marketed under the name PLASTIC POWDER D-400® or PLASTIC POWDER D-800® by the company TOSHIKI, Carnauba microwaxes, such as that marketed under the name MicroCare 350® by the company MICRO POWDERS, synthetic wax microwaxes, such as that marketed under the name MicroEase 114S® by the company MICRO POWDERS, microwaxes consisting of a mixture of Carnauba wax and polyethylene wax, such as those marketed under the names Micro Care 300® and 310® by the company MICRO POWDERS, microwaxes made from a mixture of Carnauba wax and synthetic wax,such as that marketed under the name Micro Care 325® by the company MICRO POWDERS, polyethylene microwaxes, such as those marketed under the names Micropoly 200®, 220®, 220L® and 250S® by the company MICRO POWDERS; fibers of synthetic or natural, mineral or organic origin. They can be short or long, single or organized, for example braided, hollow or solid. Their shape can be of any shape and in particular of circular or polygonal section (square, hexagonal or octagonal) depending on the specific application envisaged. In particular, their ends are blunt and / or polished to avoid injury, the fibers have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm. Their section can be included in a circle with a diameter ranging from 2 nm to 500 pm, preferably ranging from 100 nm to 100 pm and better still from 1 pm to 50 pm; and their mixtures. Particulate coloring matter

[0042] The particulate coloring matter(s) according to the invention is (are) preferably chosen from pigments, nacres, reflective particles and mixtures thereof.

[0043] A composition according to the invention may comprise a content of particulate coloring matter(s) preferably ranging from 5 to 90% by weight, and preferentially ranging from 10 to 70% by weight relative to the total weight of the composition.

[0044] The pulverulent phase of the composition according to the invention may comprise a content of particulate coloring matter(s) preferably ranging from 5 to 100% by weight, and preferentially ranging from 10 to 75% by weight relative to the total weight of the powder phase. Pigments

[0045] By "pigments" we mean particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium,

[0046] The pigments can be white or colored, mineral and / or organic.

[0047] Among the mineral pigments, mention may be made of titanium dioxides, oxides zirconium or cerium, as well as zinc oxides, iron oxides (black, yellow or red), chromium oxides, manganese violet, blue, pink or ultramarine violet, chromium hydrate and ferric blue, bismuth oxychloride, metal powders such as aluminum powder, copper powder.

[0048] According to a particular form of the invention, the mineral pigment comprises at least one lipophilic or hydrophobic coating.

[0049] According to a particular embodiment of the invention, the pigments may be coated according to the invention with at least one compound chosen from metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; silicone surface agents such as organopolysiloxanes, alkylalkoxysilanes such as triethoxycaprylylsilane; fluorinated surfactants such as perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups;fluorosilicone surfactants such as perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trial-koxysilanes; and mixtures thereof.

[0050] According to a particular embodiment, the pigments may be coated according to the invention with an N-acylated amino acid or one of its salts which may comprise an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.

[0051] The amino acid may be, for example, lysine, glutamic acid or alanine. The salts of these compounds may be aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts. Thus, according to a particularly preferred embodiment, the pigments may be coated with an N-acylated amino acid derivative which may in particular be a glutamic acid derivative and / or one of its salts, and more particularly a stearoyl glutamate, such as, for example, aluminum stearoyl glutamate. Examples of pigments treated with aluminum stearoyl glutamate include titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the commercial reference NAI® by the company by MIYOSHI KASEI.

[0052] According to a particular embodiment, the pigments may be coated according to the invention with isopropyl triisostearyl titanate. Examples of pigments treated with isopropyl titanium triisostearate (ITT) include those sold under the commercial reference BWB0-I2® (Iron Oxide CI77499 and Isopropyl Titanium triisostearate), BWY0-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate) and BWRO-12® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by the company KOBO.

[0053] The organic pigments can be chosen from the materials below and their mixtures: - cochineal carmine - organic pigments of azo, anthraquinone, indigoid, xanthenic, pyrenic, quinolinic, triphenylmethane, fluorane dyes.

[0054] Among the organic pigments, mention may in particular be made of the D&C certified pigments known under the following names: D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6.

[0055] The chemical materials corresponding to each of the organic coloring materials cited above are mentioned in the work “International Cosmetic Ingredient Dictionary and Handbook”, 1997 Edition, pages 371 to 386 and 524 to 528, published by “The Cosmetic, Toiletry, and Fragrance Association”.

[0056] More particularly, the pigments will be chosen from titanium dioxides, iron oxides (black, yellow or red), and their mixtures; said pigments optionally comprising at least one lipophilic or hydrophobic coating. Mother-of-pearl

[0057] By "mother-of-pearl" is meant colored particles of any shape, iridescent or not, in particular produced by certain molluscs in their shell or synthesized and which present a color effect by optical interference.

[0058] Examples of nacres include nacreous pigments such as titanium mica coated with iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, and nacreous pigments based on bismuth oxychloride. They may also be mica particles on the surface of which at least two successive layers of metal oxides and / or organic coloring materials are superimposed.

[0059] The mother-of-pearls can more particularly have a yellow color or reflection, pink, red, bronze, orange, brown, green, blue, purple and / or copper.

[0060] As an illustration of the mother-of-pearls that can be introduced into the composition, mention may be made of gold-colored mother-of-pearls marketed in particular by the company ENGELHARD under the name Brillant Gold 212G® (Timica), Gold 222C® (Cloisonne), Sparkle Gold® (Timica), Gold 4504® (Chromalite) and Monarch Gold 233X® (Cloisonne); bronze mother-of-pearls marketed in particular by the company MERCK under the name Bronze Fine® (17384) (Colorona) and Bronze® (17353) (Colorona) and by the company ENGELHARD under the name Super Bronze® (Cloisonne); orange mother-of-pearls marketed in particular by the company ENGELHARD under the name Orange 363C® (Cloisonne) and Orange MCR 101® (Cosmica) and by the company MERCK under the name Passion Orange® (Colorona) and Matte Orange® (17449) (Microna); brown mother-of-pearls marketed in particular by the company ENGELHARD under the name Nu-antique Copper 340XB® (Cloisonne) and Brown CL4509® (Chromalite);copper-reflecting mother-of-pearl, notably marketed by ENGELHARD under the name Copper 340A® (Timica); red-reflecting mother-of-pearl, notably marketed by MERCK under the name Sienna Fine® (17386) (Colorona); yellow-reflecting mother-of-pearl, notably marketed by ENGELHARD under the name Yellow® (4502) (Chromalite); red-tinted mother-of-pearl with a gold reflection, notably marketed by ENGELHARD under the name Sunstone G012® (Gemtone); pink mother-of-pearl, notably marketed by ENGELHARD under the name Tan opale G005® (Gemtone);black mother-of-pearl with a gold sheen, notably marketed by the company ENGELHARD under the name Nu Antique Bronze 240 AB® (Timica), blue mother-of-pearl notably marketed by the company MERCK under the name Matte Blue® (17433) (Microna), white mother-of-pearl with a silver sheen, notably marketed by the company MERCK under the name Xirona Silver® and pinkish-orange, golden-green mother-of-pearl notably marketed by the company MERCK under the name Indian Summer® (Xirona) and their mixtures.;

[0061] Still as an example of nacres, we can also cite particles comprising a borosilicate substrate coated with titanium oxide.

[0062] Particles with a glass substrate coated with titanium oxide are sold in particular under the name METASHINE MC1080RY by the company TOYAL.

[0063] Finally, as examples of mother-of-pearl, we can also cite polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004® (silver flakes).

[0064] A composition according to the invention may comprise a nacre content preferably ranging from 1 to 50% by weight, more preferably ranging from 1 to 30% by weight. weight relative to the total weight of the composition. Reflective particles

[0065] The term “reflective particles” means particles whose size, structure, in particular the thickness of the layer(s) constituting it and their physical and chemical nature, and surface condition, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when the latter is applied to the support to be made up, highlights visible to the naked eye, that is to say brighter points which contrast with their environment by appearing to shine.

[0066] The reflective particles may be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them and more particularly so as to optimize this effect in terms of color rendering. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or reflection.

[0067] These particles can have various shapes, in particular being platelet-shaped or globular, in particular spherical.

[0068] The reflective particles, whatever their shape, may have a multi-layer structure or not and, in the case of a multi-layer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

[0069] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, in particular titanium or iron oxides obtained by synthesis.

[0070] When the reflective particles have a multi-layer structure, they may for example comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate may be single-material, multi-material, organic and / or inorganic.

[0071] More particularly, it can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and their mixtures, this list not being limiting.

[0072] The reflective material may comprise a layer of metal or a metallic material.

[0073] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0074] Still as an example of reflective particles comprising a mineral substrate coated with a layer of metal, mention may also be made of particles comprising a borosilicate substrate coated with silver.

[0075] Platelet-shaped particles with a silver-coated glass substrate are sold under the name MICROGLASS METASHINE REFSX 2025 PS® by the company TOYAL. Particles with a nickel / chromium / molybdenum alloy-coated glass substrate are sold under the name CRYSTAL STAR GF 550®, GF 2525® by the same company.

[0076] It is also possible to use particles comprising a metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium, said substrate being coated with at least one layer of at least one metallic oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

[0077] Examples include aluminum, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE® by the company ECKART.

[0078] According to a particular form of the invention, the particulate coloring matter(s) is (are) chosen from - titanium dioxides (CI: 77891) such as the commercial product HOMBITAN FF PHARMA® sold by the company VENATOR; - yellow iron oxides (CI: 77492), red iron oxides (CI: 77491), black iron oxides (CI: 77499), and their mixtures such as commercial products sold under the name SUNPURO® from the company SUN; - pearlescent agents such as those based on mica coated with titanium dioxide and / or iron oxide, such as the product sold under the trade name TIMIRON PEARL SHEEN MP 30® by the company MERCK; those based on mica, barium sulfate and titanium dioxide, such as the product sold under the trade name RONAFLAIR LOW LUSTER PIGMENT® by the company MERCK; - bismuth oxychloride such as the product sold under the trade name RONAFLAIR LF 2000® by the company MERCK; - their mixtures.

[0079] More particularly, the particulate coloring matter(s) will be chosen from pigments, and more particularly from titanium dioxides, iron oxides (black, yellow or red), and mixtures thereof; said pigments optionally comprising at least one lipophilic or hydrophobic coating agent. Film-forming polymer

[0080] The solid composition in the form of a loose or compact powder of the invention comprises at least one film-forming polymer in the solid state.

[0081] For the purposes of the invention, the term “polymer” means a compound corresponding to the re petition of one or more motifs (these motifs being derived from compounds called monomers). This or these motifs are repeated at least twice and preferably at least 3 times.

[0082] By "film-forming polymer" is meant a polymer capable of forming, on its own or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on keratin materials, and preferably a cohesive film, and better still a film whose cohesion and mechanical properties are such that said film can be isolated and handled in isolation, for example when said film is produced by casting onto a non-stick surface such as a Teflon-coated or silicone-coated surface.

[0083] By "polymer in the solid state" is meant the state of the polymer at room temperature (25°C) and at atmospheric pressure (760 mm Hg or 105 Pa); the latter not being present in the composition of the invention in a fluid form in the solubilized state in an organic solvent, in particular a volatile organic solvent.

[0084] Preferably, a composition according to the invention comprises from 5% to 60% by weight, more preferably from 10 to 50% by weight, more particularly from 20% to 40% by weight of active material of film-forming polymer(s) relative to the total weight of the composition.

[0085] The film-forming polymers in accordance with the invention are preferably chosen from hydrophobic film-forming polymers.

[0086] For the purposes of the present invention, the term "hydrophobic film-forming polymer" is intended to denote a film-forming polymer lacking an affinity for water and as such not suitable for formulation in the solute state in an aqueous medium. In particular, the term "hydrophobic polymer" is intended to mean a polymer having a solubility in water at 25°C of less than 1% by weight.

[0087] In particular, the hydrophobic film-forming polymer is a polymer chosen from the group comprising film-forming polymers soluble in an organic solvent medium, in particular liposoluble polymers; this means that the polymer is soluble or miscible in the organic medium and will form a single homogeneous phase when it is incorporated into the medium.

[0088] According to a particular form of the invention, the hydrophobic film-forming polymer(s) is (are) chosen from - a silicone resin; - a copolymer comprising carboxylate groups and poly-dimethylsiloxane groups; - a vinyl polymer comprising at least one unit derived from carbo-siloxane dendrimer; - an ethylenic block copolymer; - a polysaccharide grafted with organosiloxane groups; - a polysaccharide ether; - a norbornene polymer grafted with organosiloxane groups; - their mixtures. Silicone resins

[0089] More generally, the term "resin" means a compound whose structure is three-dimensional. "Silicone resins" are also called "silicone resins" or "siloxane resins".

[0090] The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known as "MDTQ", the resin being described according to the different siloxane monomeric units that it comprises, each of the letters "MDTQ" characterizing a type of unit.

[0091] The letter “M” represents the Monofunctional unit of formula RlR2R3SiOi / 2, the silicon atom being linked to a single oxygen atom in the polymer comprising this unit.

[0092] The letter "D" means a Difunctional unit RlR2SiO2 / 2 in which the silicon atom is linked to two oxygen atoms.

[0093] The letter “T” represents a Trifunctional unit RlSi3 / 2.

[0094] Such resins are described for example in "Encyclopedia of Polymer Science and Engineering, vol. 15, John and Wiley and Sons, New York, (1989), pp. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or US 5,082,706, US 5,319,040, US 5,302,685 and US 4,935,484.

[0095] In the M, D, T units defined above, R, namely RI, R2 and R3, represents a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

[0096] Finally, the letter “Q” signifies a Tetrafunctional SiO4 / 2 unit in which the silicon atom is linked to four oxygen atoms themselves linked to the rest of the polymer.

[0097] Various silicone resins with different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the radical R, the length of the polymer chain, the degree of branching and the size of the pendant chains.

[0098] As silicone resins which can be used in the compositions according to the invention, it is possible to use, for example, silicone resins of the MQ type, of the T type or of the MQT type. MQ Resins:

[0099] As an example of MQ type silicone resins, mention may be made of alkylsiloxy- silicates of formula [(Ri)3SiOi / 2]x(SiO4 / 2)y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the RI group represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

[0100] As an example of MQ silicone resins, we will cite those with the INCI name Trimethyl-siloxysilicate such as those marketed under the reference SR1000® by the company General Electric and under the reference BELSIL TMS 803® by the company Wacker. T resins:

[0101] As an example of T-type silicone resins, mention may be made of polysilsesquioxanes of formula (RSiO3 / 2)x (T units) in which x is greater than 100 and such that the R group is an alkyl group having from 1 to 10 carbon atoms, said polysilsesquioxanes being able to further comprise Si-OH terminal groups.

[0102] Preferably, polymethylsilsesquioxane resins may be used in which R represents a methyl group, such as, for example, those marketed by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: polymer comprising repeating units CH3SiO3 / 2 (T units), which may also comprise up to 1% by weight of (CH3)2SiO2 / 2 units (D units) and having an average molecular weight of approximately 10,000 g / mol. MQT Resins:

[0103] As a resin comprising MQT units, those cited in document US 5,110,890 are known in particular.

[0104] A preferred form of MQT type resins are MQT-propyl resins (also called MQTPr). Such resins which can be used in the compositions according to the invention are in particular those described and prepared in application WO 2005 / 075542.

[0105] The MQ-T-propyl resin preferably comprises the units: (i) (Rl3SiO1 / 2)a (ii) (R22SiO2 / 2)b (iii) (R3SiO3 / 2)cet (iv) (SiO4 / 2)d with RI, R2 and R3 independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group, a, b, c and d being molar fractions, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6 a + b + c + d=l, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

[0106] Preferably, the siloxane resin comprises the units: (i) (Rl3SiO1 / 2)a (ii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with RI and R3 independently representing an alkyl group having from 1 to 8 carbon atoms, RI preferably being a methyl group and R3 preferably being a propyl group, a being between 0.05 and 0.5, preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or between 0.2 and 0.55, a + b + c + d= 1, and a, b, c and d being molar fractions, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

[0107] The siloxane resins which can be used according to the invention can be obtained by a process comprising the reaction of A) an MQ resin comprising at least 80 mol% of (Rl3SiOi / 2)a and (SiO 4 / 2)d units RI representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than zero, the ratio a / d being between 0.5 and 1.5; and B) a propyl resin T comprising at least 80 mol% of (R3SiO3 / 2)c units, R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than zero, provided that at least 40 mol% of the R3 groups are propyl groups, where the mass ratio A / B is between 95:5 and 15:85, preferably the mass ratio A / B is 30:70.

[0108] Advantageously, the mass ratio A / B is between 95:5 and 15:85. Preferably, the ratio A / B is less than or equal to 70:30. These preferred ratios have proven to allow comfortable deposits.

[0109] Preferably, the composition according to the invention comprises, as silicone resin, at least one MQ type resin, more particularly of the Trimethylsiloxysilicate type, such as those marketed under the reference SR 1000® by the company Momentive Performance Materials and under the reference TMS 803® by the company Wacker.

[0110] Copolymers comprising carboxylate groups and polydimethylsiloxane groups

[0111] By “copolymer comprising carboxylate groups and polydimethylsiloxane groups” is meant in the present application, a copolymer obtained from (a) one or more carboxylic monomers (acid or ester), and (b) one or more polydimethylsiloxane (PDMS) chains.

[0112] In the present application, the term “carboxylic monomer” means both carboxylic acid monomers and carboxylic acid ester monomers.

[0113] Thus, the monomer (a) may be chosen for example from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, their esters and mixtures of these monomers.

[0114] As esters, the following monomers may be mentioned: acrylate, methacrylate, maleate, fumarate, itaconoate and / or crotonoate.

[0115] According to a preferred embodiment of the invention, the monomers in the form of esters are more particularly chosen from linear or branched alkyl acrylates and methacrylates, preferably C1-C24 and better still C1-C22, the alkyl radical being preferentially chosen from methyl, ethyl, stearyl, butyl, ethyl-2-hexyl radicals, and mixtures thereof.

[0116] Thus, according to a particular embodiment of the invention, the copolymer comprises as carboxylate groups, at least one group chosen from acrylic acid, methacrylic acid, methyl, ethyl, stearyl, butyl, ethyl-2-hexyl acrylates or methacrylates, and mixtures thereof.

[0117] In the present application, the term "polydimethylsiloxanes" (also called organopolysiloxanes or, in abbreviation, PDMS), in accordance with general acceptance, is intended to mean any organosilicon polymer or oligomer with a linear structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of main units in which the silicon atoms are linked together by oxygen atoms (siloxane bond °Si-O-Si°), comprising trimethyl radicals directly linked via a carbon atom to said silicon atoms.The PDMS chains which can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, that is to say that the PDMS can have for example a polymerizable radical group on both ends of the chain or have a polymerizable radical group on one end of the chain and a group. terminal trimethylsilyl on the other end of the chain. The polymerizable radical group can be in particular an acrylic or methacrylic group, in particular a CH2=CR1-COO-R2 group where RI represents a hydrogen or a methyl group and R2 represents -CH2-, -(CH2)n- with n = 3, 5, 8 or 10, -CH2-CH(CH3)-CH2-, -CH2-CH2-CH2-CH2-, -CH2-CH2-O-CH2-CH2-CH(CH3)-CH2-, -CH2-CH2-O-CH2-CH2-O-CH2-CH2-CH2-,

[0118] The copolymers used in the composition of the invention are generally obtained according to the usual polymerization and grafting methods, for example by radical polymerization (A) of a PDMS comprising at least one polymerizable radical group (for example on one of the ends of the chain or on both) and (B) of at least one carboxylic monomer, as described for example in documents US-A-5,061,481 and US-A-5,219,560.

[0119] The copolymers obtained generally have a molecular weight ranging from 3000 to 200000, and preferably from 5000 to 100000.

[0120] As copolymers which can be used in the composition of the invention, mention may be made, for example, of copolymers of acrylic acid and stearyl acrylate with polydimethylsiloxane grafts, copolymers of stearyl methacrylate with polydimethylsiloxane grafts, copolymers of acrylic acid and stearyl methacrylate with polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts.

[0121] Mention may in particular be made, as a copolymer which can be used in the composition of the invention, of the copolymer with the INCI name ACRYLATES / ETHYLHEXYL ACRYLATE / DIMETHICONE METHACRYLATE such as the commercial product KP-561® sold by the company SHIN ETSU.

[0122] Vinyl polymers grafted with a carbosiloxane dendrimer

[0123] The vinyl polymer has a backbone and at least one side chain, which comprises a carbosiloxane dendrimer-derived unit having a carbosiloxane dendrimer structure.

[0124] The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure having branched groups having high molecular weights, said structure having high regularity in the radial direction starting from the bond to the backbone. Such carbosiloxane dendrimer structures are described as a highly branched siloxane-silylalkylene copolymer in Japanese Patent Application Laid-Open Kokai 9-171154.

[0125] A vinyl polymer according to the invention may contain units derived from carbosiloxane den-drimers which may be represented by the following general formula (I): [Chem 1] (I) in which: - R1 represents an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms; - X' represents a silylalkyl group which, when i = 1, is represented by the formula (II): [Chem 2]

[0126] (II) in which: R1 is as defined above in formula (I), R2 represents an alkylene radical of 2 to 10 carbon atoms, R3 represents an alkyl group of 1 to 10 carbon atoms, Xi+1 is chosen from: a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 5 to 10 carbon atoms and a silylalkyl group defined above of formula (II), i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a' is an integer from 0 to 3; Y represents a radically polymerizable organic group chosen from: organic groups containing a methacrylic group or an acrylic group, said organic groups being represented by the formulas: [Chem. 3] R- O OR [Chem 4] R; O I II H,C=C—C — N RH in which: R4 represents a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and R5 represents an alkylene group of 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, with methylene and propylene groups being preferred; and organic groups containing a styryl group of formula: [Chem 5] in which: R6 represents a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, the methyl group being preferred; R7 represents an alkyl group of 1 to 10 carbon atoms; R8 represents an alkylene group of 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, the ethylene group being preferred; b is an integer from 0 to 4; and c is 0 or 1, so if c is 0, -(R8)c- represents a bond.

[0127] According to one embodiment, R1 may represent an aryl group having from 5 to 10 carbon atoms or an alkyl group having from 1 to 10 carbon atoms. The alkyl group may preferably be represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group. The aryl group may preferably be represented by a phenyl group and a naphthyl group. Methyl and phenyl groups are more particularly preferred, and the methyl group is most preferred.

[0128] According to one embodiment, R2 represents an alkylene group having from 2 to 10 carbon atoms, in particular a linear alkylene group, such as an ethylene, propylene, butylene or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1-methylpentylene or 1,4-dimethylbutylene group. ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene groups are most preferred.

[0129] According to one embodiment, R3 is chosen from methyl, ethyl, propyl, butyl and isopropyl groups.

[0130] In formula (II), i indicates the number of generations and thus corresponds to the number of repetitions of the silylalkyl group.

[0131] For example, when the number of generations is equal to one, the carbo-siloxane dendrimer can be represented by the following general formula: [Chem 6] R1 IK O—Si—R I. wherein Y, R1, R2 and R3 are as defined above, R12 represents a hydrogen atom or is the same as R1; a1 is the same as a'. Preferably, the total average number of 0R3 groups in a molecule is in the range of 0 to 7. When the number of generations is equal to 2, the carbosiloxane dendrimer can be represented by the following general formula: [Chem 7] HAS' wherein Y, R1, R2, R3 and R12 are the same as defined above; a1 and a2 represent the a' of the indicated generation. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 25.

[0132] In the case where the number of generations is equal to 3, the carbosiloxane dendrimer is represented by the following general formula: [Chem 8] wherein Y, R1, R2, R3 and R12 are the same as defined above; a1, a2 and a3 represent the a' of the indicated generation. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 79.

[0133] A vinyl polymer having at least one carbosiloxane dendrimer-derived unit has a side molecular chain containing a carbosiloxane dendrimer structure, and may be derived from the polymerization: (A) from 0 to 99.9 parts by weight of a vinyl monomer; and (B) from 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing a radically polymerizable organic group, represented by the general formula (I) as defined above.

[0134] The vinyl-type monomer which is component (A) in the vinyl polymer having at least one carbosiloxane dendrimer-derived unit is a vinyl-type monomer which contains a radical-polymerizable vinyl group. There is no particular limitation with respect to such a monomer.

[0135] The following are examples of this vinyl-type monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower alkyl methacrylate analog; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, or a higher methacrylate analog; vinyl acetate, vinyl propionate, or a lower fatty acid ester thereof; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate, or a higher fatty acid ester thereof;styrene, vinyl toluene, benzyl methacrylate, phenoxyethyl methacrylate, vinyl pyrrolidone, or analogous aromatic vinyl monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylmethacrylamide, or analogous vinyl monomers that contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or; vinyl-like monomers that contain hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or vinyl-like monomers that contain a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, or a vinyl-like monomer with ether linkages; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or a silicone analogous compound having unsaturated groups; butadiene; vinyl chloride;vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid; a radically polymerizable unsaturated monomer having a sulfonic acid group such as a styrene sulfonic acid group; a quaternary ammonium salt derived from methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and a methacrylic acid ester of an alcohol having a tertiary amine group such as a methacrylic acid ester of diethylamine. ;

[0136] Multifunctional vinyl-type monomers can also be used.

[0137] The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris-(2-hydroxyethyl)isocyanurate dimethacrylate, tris-(2-hydroxyethyl)isocyanurate trimethacrylate, styryl-capped polydimethylsiloxane having divinylbenzene groups on both ends, or analogous silicone compounds having unsaturated groups.

[0138] A carbosiloxane dendrimer, which is component (B), may be represented by formula (I) as defined above.

[0139] The following represent preferred examples of group Y of formula (I): an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group, and a 5-hexenyl group.

[0140] A carbosiloxane dendrimer according to the present invention can be represented by the following average structural formulas:

[0141] Thus, according to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula: R1 I 2 If—R-

[0142] in which: Y, R1, R2 and R3 are as defined in formulas (I) and (II) above; a1, a2 and a3 meet the definition of a' according to formula (II); and R12 is H, an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms.

[0143] According to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by one of the following formulas: H,C=C—C—O —CH —S; HJ -—CH —K-—O —Si ■ Pi o

[0144] The vinyl polymer comprising the carbosiloxane dendrimer according to the invention can be manufactured according to the method for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154.

[0145] For example, it can be produced by subjecting to a hydrosilylation reaction an organosilicon compound which contains a hydrogen atom bonded to a silicon atom, represented by the following general formula (IV): [Chem 9] R1 / —Si—O—Si—H (IV) where RI being as defined above in formula (I), and an organosilicon compound which contains an alkenyl group.

[0146] In the above formula, the organosilicon compound can be represented by 3-methacryloxypropyltris-(dimethylsiloxy)silane, 3-acryloxypropyltris-(dimethylsiloxy)silane, and 4-vinylphenyltris-(dimethylsiloxy)silane. The organosilicon compound which contains an alkenyl group can be represented by vinyl tris-(trimethylsiloxy)silane, vinyl tris-(dimethylphenylsiloxy)silane, and 5-hexenyltris-(trimethylsiloxy)silane.

[0147] The hydrosilylation reaction is carried out in the presence of a chloroplatinic acid, of a vinylsiloxane and platinum complex, or of an analogous transition metal catalyst.

[0148] A vinyl polymer having at least one carbosiloxane dendrimer-derived unit may be chosen from polymers such that the unit of a carbosiloxane dendrimer derivative is a carbosiloxane dendritic structure represented by the following formula (III): [Chem 10] (III) wherein Z is a divalent organic group, "p" is 0 or 1, R1 is as defined above in formula (IV) and X' is a silylalkyl group represented by formula (II) as defined above.

[0149] In a vinyl polymer having at least one carbosiloxane dendrimer-derived unit, the polymerization ratio between components (A) and (B), in terms of the weight ratio between (A) and (B), is in a range of 0 / 100 to 99.9 / 0.1, or even 0.1 / 99.9 to 99.9 / 0.1, and preferably in a range of 1 / 99 to 99 / 1. A ratio between components (A) and (B) of 0 / 100 means that the compound becomes a homopolymer of component (B).

[0150] A vinyl polymer having at least one carbosiloxane dendrimer-derived unit can be obtained by the copolymerization of components (A) and (B), or by the polymerization of only component (B).

[0151] The polymerization may be a radical polymerization or an ionic polymerization, however radical polymerization is preferred.

[0152] The polymerization can be carried out by causing a reaction between components (A) and (B) in a solution for a period of 3 to 20 hours in the presence of a radical initiator at a temperature of 50°C to 150°C.

[0153] A suitable solvent for this purpose is hexane, octane, decane, cyclohexane, or a similar aliphatic hydrocarbon; benzene, toluene, xylene, or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, or ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, or similar esters; methanol, ethanol, isopropanol, butanol, or similar alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, or a similar organosiloxane oligomer.

[0154] A radical initiator may be any compound known in the art for conventional radical polymerization reactions. Specific examples of such radical initiators are 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) or analogous azobis-type compounds; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, or a similar organic peroxide. These radical initiators may be used alone or in a combination of two or more. The radical initiators may be used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of components (A) and (B). A chain transfer agent may be added.The chain transfer agent may be 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane having a mercaptopropyl group or a similar mercapto-type compound; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane, or a similar halogenated compound.

[0155] In the manufacture of the vinyl-type polymer, after polymerization, the residual unreacted vinyl monomer can be removed under vacuum heating conditions.

[0156] To facilitate the preparation of raw material for cosmetic products, the number average molecular weight of the vinyl polymer which contains a carbosiloxane dendrimer may be chosen in the range between 3,000 and 2,000,000, preferably between 5,000 and 800,000. It may be a liquid, a gum, a paste, a solid, a powder, or any other form. Preferred forms are solutions formed by dilution in solvents, a dispersion, or a powder.

[0157] A vinyl polymer suitable for the invention may also be one of the polymers described in the examples of application EP 0 963 751.

[0158] According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer can be obtained from the polymerization: - from 0 to 99.9 parts by weight of one or more acrylate or methacrylate monomer(s); and - from 100 to 0.1 parts by weight of an acrylate or methacrylate monomer of a tri[tri(trimethylsiloxy)silylethyl dimethylsiloxy]silylpropyl carbosiloxane dendrimer.

[0159] The monomers (Al) and (B 1) correspond respectively to particular monomers (A) and (B).

[0160] According to one embodiment, a vinyl polymer having at least one carbosiloxane dendrimer-derived unit may comprise a tri[tri(trimethylsiloxy)silylethyl dimethylsiloxy]silylpropyl carbosiloxane dendrimer-derived unit corresponding to one of the formulas: Or Hc=CH-C—O— G,H — Ss II O

[0161] According to a preferred embodiment, a vinyl polymer having at least one carbosiloxane dendrimer-derived unit used in the invention comprises at least one butyl acrylate monomer.

[0162] According to one embodiment, a vinyl polymer may further comprise at least one fluorinated organic group. A fluorinated vinyl polymer may be one of the polymers described in the examples of application WO 03 / 045337.

[0163] The vinyl polymers grafted with at least one carbosiloxane dendrimer-derived unit which may be particularly suitable for the present invention are those with the INCI name: ACRYLATES / POLYTRIMETHYLSILOXYMETHACRYLATE and corresponding to the polymer in the solid state of the commercial products DOWSIL FA 4002 ID SILICONE ACRYLATE® and DOWSIL FA 4004 ID SILICONE ACRYLATE® sold by the company Dow Corning. Ethylene block copolymers

[0164] According to a preferred form, the ethylenic block copolymer (also called ethylenic block polymer) in accordance with the invention contains at least one first block having a glass transition temperature (Tg) greater than or equal to 40°C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40°C, and at least one second block having a glass transition temperature less than or equal to 20°C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20°C, said first block and said second block being linked together by a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second monomers constituting the second block, and said block copolymer having a polydispersity index I greater than 2.

[0165] The block polymer used according to the invention thus comprises at least one first block and at least one second block.

[0166] By "at least" one sequence, we mean one or more sequences.

[0167] By "blocked" polymer is meant a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences.

[0168] By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.

[0169] The block ethylenic polymer used according to the invention is prepared exclusively from monofunctional monomers.

[0170] This means that the block ethylenic polymer used according to the present invention does not contain multifunctional monomers, which make it possible to break the linearity of a polymer in order to obtain a branched or even crosslinked polymer, depending on the level of multifunctional monomer. The polymer used according to the invention also does not contain macromonomers (by "macromonomer" is meant a monofunctional monomer having a pendant group of polymeric nature, and preferably having a molecular mass greater than 500 g / mol, or a polymer comprising on only one of its ends a polymerizable terminal group (or with ethylenic unsaturation)), which are used in the preparation of a grafted polymer.

[0171] It is specified that in the above and below the terms "first" and "second" sequences in no way condition the order of said sequences (or blocks) in the structure of the polymer.

[0172] The first block and the second block of the polymer used in the invention may advantageously be incompatible with each other.

[0173] By "blocks incompatible with each other", it is meant that the mixture formed by a polymer corresponding to the first block and by a polymer corresponding to the second block, is not miscible in the polymerization solvent, predominant by weight, of the block polymer, at room temperature (25°C) and atmospheric pressure (105 Pa), for a content of the mixture of said polymers greater than or equal to 5% by weight, relative to the total weight of the mixture of said polymers and said polymerization solvent, it being understood that: (i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10 / 90 to 90 / 10, and that ii) each of the polymers corresponding to the first and second sequences has an average molecular mass (by weight or by number) equal to that of the polymer sequenced + / - 15%.

[0174] In the case of a mixture of polymerization solvents, assuming two or more solvents are present in identical mass proportions, said mixture of polymers is immiscible in at least one of them.

[0175] Of course, in the case of a polymerization carried out in a single solvent, the latter is the majority solvent.

[0176] The block polymer according to the invention comprises at least one first block and at least one second block linked together by an intermediate segment comprising at least one monomer constituting the first block and at least one monomer constituting the second block. The intermediate segment (also called intermediate block) has a glass transition temperature Tg between the glass transition temperatures of the first and second blocks.

[0177] The intermediate segment is a sequence comprising at least one monomer constituting the first sequence and at least one monomer constituting the second sequence of the polymer allowing these sequences to be "compatibilized".

[0178] Advantageously, the intermediate segment comprising at least one monomer constituting the first sequence and at least one monomer constituting the second sequence of the polymer is a random polymer.

[0179] Preferably, the intermediate sequence is derived essentially from monomers constituting the first sequence and the second sequence.

[0180] By "essentially" is meant at least 85%, preferably at least 90%, better still 95% and even better still 100%.

[0181] By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.

[0182] Preferably, the polymer according to the invention does not comprise silicon atoms in its skeleton.

[0183] By "backbone" is meant the main chain of the polymer, as opposed to the pendant side chains.

[0184] Preferably, the polymer according to the invention is not water-soluble, that is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without modification of pH, at an active material content of at least 1% by weight, at room temperature (25°C).

[0185] Preferably, the polymer according to the invention is not an elastomer.

[0186] By "non-elastomeric polymer" is meant a polymer which, when subjected to a stress intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its initial length when the stress ceases.

[0187] The polydispersity index of the polymer of the invention is greater than 2.

[0188] Advantageously, the block polymer used in the compositions according to the invention has a polydispersity index I greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better still greater than or equal to 2.8 and in particular, ranging from 2.8 to 6.

[0189] The polydispersity index I of the polymer is equal to the ratio of the weight-average mass Mw to the number-average mass Mn.

[0190] The weight-average (Mw) and number-average (Mn) molar masses are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

[0191] The weight-average mass (Mw) of the polymer according to the invention is preferably less than or equal to 300,000 g / mol, it ranges for example from 35,000 to 200,000 g / mol, and better still from 45,000 to 150,000 g / mol.

[0192] The number-average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70,000 g / mol, it ranges for example from 10,000 to 60,000 g / mol, and better still from 12,000 to 50,000 g / mol.

[0193] Preferably, the polydispersity index of the polymer according to the invention is greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better still greater than or equal to 2.8 and in particular, ranging from 2.8 to 6.

[0194] First sequence having a Tg greater than or equal to 40°C

[0195] The sequence having a Tg greater than or equal to 40°C has for example a Tg ranging from 40 to 150°C, preferably greater than or equal to 50°C, ranging for example from 50°C to 120°C, and better still greater than or equal to 60°C, ranging for example from 60°C to 120°C.

[0196] The indicated glass transition temperatures of the first and second sequences may be theoretical Tgs determined from the theoretical Tgs of the constituent monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 3rd ed, 1989, John Wiley, according to the following relationship, called Fox's Law: [Math 2] 1 / Tg= S (œi / Tgi), i being the mass fraction of monomer i in the sequence considered and Tgi being the glass transition temperature of the homopolymer of monomer i.

[0197] Unless otherwise indicated, the Tgs indicated for the first and second sequences in the present application are theoretical Tgs.

[0198] The difference between the glass transition temperatures of the first and second sequences is generally greater than 10°C, preferably greater than 20°C, and better still greater than 30°C.

[0199] The sequence having a Tg greater than or equal to 40°C may be a homopolymer or a copolymer.

[0200] The block having a Tg greater than or equal to 40°C may be derived in whole or in part from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40°C. This block may also be called a “rigid block”.

[0201] In the case where this sequence is a homopolymer, it is derived from monomers, which are such that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40°C. This first sequence can be a homopolymer, consisting of a single type of monomer (the Tg of the corresponding homopolymer of which is greater than or equal to 40°C).

[0202] In the case where the first sequence is a copolymer, it may be derived in whole or in part from one or more monomers, the nature and concentration of which are chosen so that the Tg of the resulting copolymer is greater than or equal to 40°C. The copolymer may for example comprise: - monomers which are such that the homopolymers prepared from these monomers have Tgs greater than or equal to 40°C, for example a Tg ranging from 40°C to 150°C, preferably greater than or equal to 50°C, ranging for example from 50°C to 120 - monomers which are such that the homopolymers prepared from these monomers have Tgs of less than 40°C, chosen from monomers having a Tg of between 20°C and 40°C and / or monomers having a Tg of less than or equal to 20°C, for example a Tg ranging from -100°C to 20°C, preferably less than 15°C, in particular ranging from -80°C to 15°C and better still less than 10°C, for example ranging from -50°C to 0°C, as described below.

[0203] The first monomers whose homopolymers have a glass transition temperature greater than or equal to 40°C are preferably chosen from the following monomers, also called main monomers: - methacrylates of formula CH2=C(CH3)-COORi in which R 1 represents an unsubstituted, linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R 1 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl, such as isobornyl methacrylate, - acrylates of formula CH2=CH-COOR2 in which R2 represents a C4 to C12 cycloalkyl group such as an isocarboxyl group or a tert-butyl group, - (meth)acrylamides of formula: [Chem 11] Or R7 and R8, identical or different, each represent a hydrogen atom or a linear or branched C1 to C12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl group; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group, R' denotes H or methyl.

[0204] Examples of monomers include N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide, and mixtures thereof.

[0205] The first block is advantageously obtained from at least one acrylate monomer of formula CH2=CH-COOR2 and at least one methacrylate monomer of formula CH2=C(CH3)-COOR2 in which R2 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl, such as isobornyl. The monomers and their proportions are preferably chosen such that the glass transition temperature of the first block is greater than or equal to 40°C.

[0206] According to one embodiment, the first sequence is obtained from: i) at least one acrylate monomer of formula CH2=CH-COOR2 in which R2 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl group, such as isobornyl, ii) and at least one methacrylate monomer of formula CH2=C(CH3)-COOR'2 in which R'2 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl group, such as isobornyl.

[0207] According to one embodiment, the first sequence is obtained from at least one acrylate monomer of formula CH2=CH-COOR2 in which R2 represents a C8 to C12 cycloalkyl group, such as isobornyl, and at least one methacrylate monomer of formula CH2=C(CH3)-COOR'2 in which R'2 represents a C8 to C12 cycloalkyl group, such as isobornyl.

[0208] Preferably, R2 and R'2 independently or simultaneously represent an isobornyl group.

[0209] Preferably, the block copolymer comprises from 50 to 80% by weight of methacrylate / isobutyl acrylate, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acrylic acid.

[0210] The first sequence can be obtained exclusively from said monomer acrylate and said methacrylate monomer.

[0211] The acrylate monomer and the methacrylate monomer are preferably in mass ratios of between 30:70 and 70:30, preferably between 40:60 and 60:40, in particular of the order of 50:50.

[0212] The proportion of the first sequence advantageously ranges from 20 to 90% by weight of the polymer, better still from 30 to 80% and even better still from 60 to 80%.

[0213] According to one embodiment, the first sequence is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.

[0214] Second sequence of glass transition temperature lower than 20°C.

[0215] The second sequence advantageously has a glass transition temperature Tg of less than or equal to 20°C, for example a Tg ranging from -100°C to 20°C, preferably less than or equal to 15°C, in particular ranging from -80°C to 15°C and better still less than or equal to 10°C, for example ranging from -100°C to 10°C, in particular ranging from -30°C to 10°C.

[0216] The second block is derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20°C.

[0217] This sequence may also be referred to as a “soft sequence.”

[0218] The monomer having a Tg less than or equal to 20°C (called second monomer) is preferably chosen from the following monomers: - acrylates of formula CH2=CHCOOR3, with R3 representing an unsubstituted C1 to C12 alkyl group, linear or branched, with the exception of the tert-butyl group, in which one or more heteroatoms chosen from O, N, S are optionally intercalated, - methacrylates of formula CH2=C(CH3)-COOR4, with R4 representing an unsubstituted linear or branched C6 to C12 alkyl group, in which one or more heteroatoms chosen from O, N and S are optionally intercalated; - vinyl esters of formula R5-CO-O-CH =CH2 where R5 represents a linear or branched C4 to C12 alkyl group; - vinyl alcohol and C4 to C12 alcohol ethers, - C4 to C12 N-alkyl acrylamides, such as N-octylacrylamide,

[0219] - and mixtures thereof.

[0220] Preferred monomers having a Tg of less than or equal to 20°C are isobutyl acrylate, 2-ethylhexyl acrylate or mixtures thereof in all proportions.

[0221] Each of the first and second sequences may contain, in a minority proportion, at least one monomer constituting the other sequence.

[0222] Thus the first sequence can contain at least one monomer constituting the second sequence and vice versa.

[0223] Each of the first and / or second sequences may comprise, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers cited previously.

[0224] The nature and quantity of this or these additional monomers are chosen so that the sequence in which they are found has the desired glass transition temperature.

[0225] This additional monomer is for example chosen from: - ethylenically unsaturated monomers comprising at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and salts thereof, - methacrylates of formula CH2=C(CH3)-COOR6in which R6 represents a linear or branched alkyl group, containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate, - methacrylates of formula CH2=C(CH3)-COOR9, R9 representing a linear or branched C6 to C12 alkyl group, in which there are optionally intercalated one or more heteroatoms chosen from O, N and S, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I, F); - acrylates of formula CH2=CHCOORi0, R10 representing a linear or branched C1 to C12 alkyl group substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R10 represents a C1 to C12 alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene unit 5 to 10 times, for example methoxy-POE, or R8 represents a polyoxyethylene group comprising 5 to 10 ethylene oxide units.

[0226] In particular, the first sequence may comprise as additional monomer: - (meth)acrylic acid, preferably acrylic acid, - tert-butyl acrylate - methacrylates of formula CH2=C(CH3)-COORi in which Ri represents an unsubstituted, linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, - (meth)acrylamides of formula:

[0227] where R7 and RJ, identical or different, each represent a hydrogen atom or a linear or branched C1 to C12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl group; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group, R' denotes H or methyl.

[0228] Examples of (meth)acrylamides monomers include N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide and mixtures thereof.

[0229] The additional monomer may represent 0.5 to 30% by weight of the weight of the polymer. According to one embodiment, the polymer of the invention does not contain any additional monomer.

[0230] Preferably, the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first block and isobutyl acrylate and acrylic acid monomers in the second block.

[0231] Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent proportion by weight in the first block and isobutyl acrylate and acrylic acid monomers in the second block.

[0232] Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block, the first block representing 70% by weight of the polymer.

[0233] Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the block with a Tg greater than 40°C represents 70% by weight of the polymer, and the acrylic acid represents 5% by weight of the polymer.

[0234] According to one embodiment, the first sequence does not comprise any additional monomer.

[0235] According to a preferred embodiment, the second block comprises acrylic acid as an additional monomer. In particular, the second block is advantageously obtained from an acrylic acid monomer and at least one other monomer having a Tg less than or equal to 20°C.

[0236] According to a preferred embodiment, the composition according to the invention comprises at least one copolymer comprising at least one acrylate monomer of formula CH2 = CH-COOR2 in which R2 represents a C8 to C12 cycloalkyl group and / or at least one methacrylate monomer of formula CH2=C(CH3)-COOR'2 in which R'2 represents a C8 to C12 cycloalkyl group, at least one second acrylate monomer of formula CH2=CHCOOR3, in which R3 represents an unsubstituted C1 to C12 alkyl group, linear or branched, with the exception of the tert-butyl group, and at least one acrylic acid monomer.

[0237] Preferably, the copolymer used in the compositions according to the invention is obtained from at least one isobutyl methacrylate monomer, at least one isobutyl acrylate monomer, at least one isobutyl acrylate monomer and at least one acrylic acid monomer, in particular is chosen from the polymers with the INCI name ACRYLIC ACID / ISOBUTYL ACRYLATE / ISOBORNYL ACRYLATE COPOLYMER in their solid form such as those of the commercial products MEXOMER PAS® and MEXOMER PAZ® manufactured and sold by the company NOVEAL.

[0238] Advantageously, the copolymer used in the invention comprises from 50 to 80% by weight of methacrylate / isobutyl acrylate mixture, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acrylic acid.

[0239] The block copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, and in particular from 2 to 15% by weight, for example from 3 to 15% by weight, in particular from 4 to 15% by weight, or even from 4 to 10% by weight of acrylic acid monomers, relative to the total weight of said copolymer.

[0240] The monomers constituting the second sequence and their proportions are chosen such that the glass transition temperature of the second sequence is less than or equal to 20°C. Intermediate segment

[0241] The intermediate segment (also called intermediate block) links the first block and the second block of the polymer used according to the present invention. The intermediate segment results from the polymerization:+ (i) the first monomer(s), and optionally the additional monomer(s), remaining available after their polymerization at a conversion rate of at most 90% to form the first block, ii) and the second monomer(s), and optionally the additional monomer(s), added to the reaction mixture.

[0242] The formation of the second sequence is initiated when the first monomers no longer react or no longer incorporate into the polymer chain either because they are all consumed either because their reactivity no longer allows them to be.

[0243] Thus the intermediate segment comprises the first available monomers, resulting from a conversion rate of these first monomers less than or equal to 90%, during the introduction of the second monomer(s) during the synthesis of the polymer.

[0244] The intermediate segment of the block polymer is a random polymer (may also be referred to as a random sequence). That is, it comprises a random distribution of the first monomer(s) and the second monomer(s) as well as any additional monomer(s) that may be present.

[0245] Thus, the intermediate segment is a random sequence, as are the first sequence and the second sequence if they are not homopolymers (i.e., if they are both formed from at least two different monomers). Process for preparing the copolymer:

[0246] The ethylenic block copolymer according to the invention is prepared by free radical polymerization, according to the well-known techniques of this type of polymerization.

[0247] The free radical polymerization is carried out in the presence of an initiator whose nature is adapted, in a known manner, according to the desired polymerization temperature and the polymerization solvent. In particular, the initiator may be chosen from peroxide-functional initiators, redox couples, or other radical polymerization initiators known to those skilled in the art.

[0248] In particular, as peroxide-functional initiator, mention may be made, for example, of: a) peroxyesters, such as tert-butyl-peroxyacetate, tert-butyl perbenzoate, tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S® from Akzo Nobel), 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141® from Akzo Nobel); (b) peroxydicarbonates, such as di-isopropylperoxydicarbonate; (c) peroxyketones, such as methyl ethyl ketone peroxide; d) hydroperoxides, such as hydrogen peroxide (H2O2), tert-butylhydroperoxide; e) diacyl peroxides, such as acetyl peroxide, benzoyl peroxide; (f) dialkyl peroxides, such as di-tert-butyl peroxide; (g) inorganic peroxides, such as potassium peroxodisulfate (K2S2O8);

[0249] As an initiator in the form of an oxidation-reduction couple, mention may be made of the potassium thiosulfate + potassium peroxodisulfate couple for example.

[0250] According to a preferred embodiment, the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms. Preferably, the initiator used is 2.5-Bis(2-ethylhexanoylperoxy)-2.5-dimethylhexane marketed under the reference Trigonox® 141 by the company Akzo Nobel.

[0251] The block copolymer used according to the invention is prepared by ra- polymerization free dical and not by controlled or living polymerization. In particular, the polymerization of the ethylenic block copolymer is carried out in the absence of control agents, and in particular in the absence of control agents conventionally used in living or controlled polymerization processes such as nitroxides, alkoxyamines, dithioesters, dithiocarbamates, dithiocarbonates or xanthates, trithiocarbonates, copper-based catalysts, for example.

[0252] Block copolymers such as those described above are described in particular in patent applications EP-A-1411069 and EP-A-1882709.

[0253] The synthetic solvent used for the polymerization of the film-forming copolymer is generally chosen from volatile oils whose flash point is less than 80°C, such as isododecane for example.

[0254] Polysaccharides grafted with organosiloxane groups

[0255] Among the polysaccharides grafted with organosiloxane groups, mention may be made of polysaccharides obtained by reaction a) of a polysaccharide with b) an organopolysiloxane comprising an isocyanate group of the following formula (1): [Chem 12] R1a / R2 \ O=C=N-(-CH2|-Si—+O-SÎ-R3) (1) V R4 Aa wherein R1, R2, R3 and R4 independently represent a radical selected from an alkyl group having from 1 to 8 carbon atoms, a fluoroalkyl group having from 1 to 8 carbon atoms and an aryl group having from 6 to 12 carbon atoms; n is an integer from 1 to 10 and a is an integer from 0 to 3; and (c) an organic compound comprising an isocyanate group of the following formula (2): [Chem 13] OON-R5 (2) in which R5 represents an alkyl group having from 3 to 30 carbon atoms, an aryl group having from 6 to 12 carbon atoms or an aralkyl group having from 6 to 30 carbon atoms or a group of the following formula (3): [Chem 14] -R^X-R7 (3) in which R6 represents a divalent hydrocarbon group having 2 to 8 carbon atoms; R7 is an alkyl group having 1 to 30 carbon atoms; X denotes a group -NHCONH or NHCOO-. O=C=N-(-CH2j”Si

[0256] The polysaccharide is preferably chosen from pullulans, celluloses, chitins, chitosans, starches, mannans, hyaluronic acid and their forms modified by alkylation, acylation, cationization or addition of a polyoxyalkylenated chain. More particularly, it is chosen from a pullulan or a cellulose, in particular a hydroxypropylcellulose.

[0257] The organopolysiloxane comprising an isocyanate group of formula (1) is preferably chosen from the compound of the following formula: [Chem 15] / PO-Si-CH \ ch3

[0258] The organic compound comprising an isocyanate group of formula (2) is preferably chosen from stearyl isocyanate or a compound of structure 2NHCOOC12 H2S

[0259] These polysaccharides grafted with organosiloxane groups as well as their synthesis are described in patents EP2647366B1, KR10-1666267B1 and application WO2023 / 068123.

[0260] Among the polysaccharides grafted with organosiloxane groups, the polymer with the INCI name TRIMETHYLSILOXYSILYLCARBAMOYL PULLULANE will be used in the solid state such as that in the product sold under the trade name TSPL-30-ID® or the product TSPL-30-D5® by the company Shin Etsu. Polysaccharide ethers

[0261] By "polysaccharide ether" is meant an alkyl polysaccharide whose alkyl group comprises from 1 to 30, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms.

[0262] Preferably, the alkyl polysaccharides according to the invention are derivatives of cellulose, pullulan or guar or their mixtures.

[0263] According to a particular embodiment, the alkyl polysaccharide(s) are chosen from alkylcelluloses whose linear or branched alkyl group comprises from 1 to 20 carbon atoms, in particular from 2 to 15 carbon atoms.

[0264] Alkylcellulose is an alkyl ether of cellulose comprising a chain consisting of [3-anhydroglucose] units linked together by acetal bonds. Each anhydroglucose unit has three replaceable hydroxyl groups, all or part of these hydroxyl groups being able to react according to the following reaction: Cell-OM + R-Hal Cell-OR + MHal with Hal representing a halogen such as Cl, M representing a counter ion ca- tionic such as alkali metal Na+ or K+, or alkaline earth metal, preferably an alkali metal such as Na, Cell representing a polysaccharide radical such as cellulose, R representing a linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably from 2 to 3 carbon atoms such as methyl or ethyl, and MHal the salt generated such as sodium chloride.

[0265]

[0067] Advantageously, the compound(s) E are chosen from ethylcellulose, propylcellulose and mixtures thereof, preferably ethylcellulose.

[0266] The ethylcellulose polymers used in a cosmetic composition according to the invention are preferably polymers having a degree of substitution in ethoxy groups ranging from 2.5 to 2.6 per anhydroglucose unit, in other words comprising a content of ethoxy groups ranging from 44% to 50%.

[0267] The average molar mass of ethylcellulose is preferably chosen so that the viscosity of a 5% by weight solution in an 80 / 20 mixture (toluene / ethanol) at 25°C ranges from 4 to 300 mPa.s, preferably from 5 to 200 mPa.s, for example from 5 to 150 mPa.s. (ASTM D 914 standard).

[0268] The ethylcellulose used in the composition according to the invention is more particularly in powder form.

[0269] It is for example marketed under the trade names ETHOCEL Standard® from Dow Chemicals, including ETHOCEL Standard 7 FP Premium® and ETHOCEL standard 100 FP Premium®. Other commercially available products, such as those marketed by Ashland, Inc., under the names Aqualon Ethylcellulose® type-K, type-N and type-T, preferably type-N, such as N7, N100, are particularly suitable for carrying out the invention.

[0270] According to another particular embodiment, the polysaccharide ether(s) are chosen from alkylguars, i.e. guar gums modified by substitution of hydroxy hydrogen with a linear or branched alkyl group, comprising from 1 to 20 carbon atoms, in particular from 2 to 10 carbon atoms, preferably from 2 to 3 carbon atoms such as 2 carbon atoms. Advantageously, the alkyl polysaccharide is ethylguar. Ethylguar is known in particular under the INCI name: Cl-5 ALKYL GALACTOMANNAN such as the commercial products ASI D-5783 MODIFIED POLYSACCHARIDE ETHYL GUAR® and N HANCE AG 200 sold by the company ASHLAND, the commercial product LANCO-GEL CP 5® sold by the company LANGER.

[0271] According to another particular embodiment, the polysaccharide ether(s) are chosen from alkylpullulans such as myristoyl pullulan such as the commercial product MYRISTOYL PULLULAN® sold by the company KATAKURA CHIKKARIN.

[0272] Norbornene polymers grafted with organosiloxane groups

[0273] Among the norbornene polymers grafted with organosiloxane groups, mention may be made of norbornene resins modified by a linear, branched or monocyclic organosiloxane as described in patent JP4475413B2.

[0274] They respond to the following formula: [Chem 16] where R1 to R16, which may be identical or different, represent a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, an organooxycarbonyl group having 2 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a cyanose group, an amide group, an imide group or a group (SiR19)3 where R19 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an organooxy group having 1 to 10 carbon atoms, an amide group, an imide group or a group O(SiR202O)pSiR203 where R20 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and p is an integer from 0 to 20; the acid anhydride groups may be the same as or different from each other, and any two of the groups R1 to R16 may form an acid anhydride group; R17 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms; R18 is a single bond; X is the formula: -(SiR212O)qSiR213-Si(OSiR223)rR203 r where R20 is a substituted or unsubstituted monovalent hydrocarbon group having from 1 to 10 carbons, and R21 are substituted or unsubstituted monovalent hydrocarbon groups having from 1 to 20 carbons, which may be the same as or different from each other and R22 is R21 or a group (OSiR212)sR21 where s is an integer from 0 to 20, q is an integer from 1 to 100, r is 2 or 3, and t is an integer from 0 to 10 m is 0, 1 or 2; n is an integer from 10 to 1,000,000.

[0275] Among these polymers, we can cite in particular that of INCI name: NORBORNENE / TRIS(TRIMETHYLSILOXY) SILYLNORBORNENE in solid state such as that in the commercial product NBN-30-ID® sold by SHIN ETSU. Manufacturing process

[0276] Another subject of the invention relates to a process for manufacturing a solid composition as defined above, consisting of grinding in the solid state said film-forming polymer with at least part of the pulverulent phase, in particular the particulate coloring materials present in the composition.

[0277] Another subject of the invention also relates to a solid composition in the form of a loose or compact powder capable of being obtained by said preparation process.

[0278] The powder phase, the film-forming polymer, and any additional ingredients are mixed dry, in proportions in accordance with the invention, then part or all of the powder phase and the film-forming polymer are subjected to a dry grinding step. Among the different dry grinding processes, micronizing powder mills by friction, collision, or a combination thereof can be used, making it possible to obtain very fine grinding qualities (D50 < 100m), such as air jet mills (or neutral gas), pin mills, or knife mills.

[0279] By grinder-micronizer according to the invention, is meant a grinder making it possible to refine particles to sizes of the order of a few microns, or even of the order of a micron, or even smaller. As commercial references of grinders for dry grinding, mention may be made in particular of the CHRISPRO Jet Mill® air jet mill, manufactured by MICRO-45 MACINAZIONE SA (Italy), the HOSOKAWA® pin mill supplied by ALPINE AG (Germany), and the IKA® type M20 knife mill, marketed by the company IKA Werke GmbH & Co. KG (Germany).

[0280] In particular, air jet, pin or knife mills can be used, more preferably a pin or knife mill will be used, preferably a pin mill.

[0281] According to a particular embodiment of the invention, the solid composition in powder form capable of being obtained according to this process, has a particle size profile with a D50 ranging from 1 to 15 pm, and preferably from 1 to 10 pm.

[0282] The granulometric analysis of the solid composition in powder form is generally carried out by simple dispersion of said particles in a liquid dispersant and is measured at 25°C, for example using a laser granulometer, according to the supplier's recommendations. Adjuvants

[0283] The composition may comprise other ingredients (adjuvants) usually used in cosmetics such as preservatives, cosmetic active ingredients, moisturizing agents, UV filters, perfumes, preservatives.

[0284] Of course, those skilled in the art will take care to choose the possible adjuvant(s) added to the composition according to the invention in such a way that the advantageous properties intrinsically attached to the composition in accordance with the invention are not, or not substantially, altered by the envisaged addition. Cosmetic applications

[0285] The composition of the invention in the form of compact powder can be a skin care product.

[0286] The composition of the invention in the form of compact powder may be a skin makeup product, in particular for the face such as a foundation, for the cheeks such as a blush, for the eyelids such as an eyeshadow.

[0287] According to a particular embodiment, the composition of the invention can be used as a second layer (Top Coat) applied to a first layer (Base Coat) formed by a first care composition comprising at least one oily phase in order to reinforce the composition of the invention, in particular more resistant to sebum.

[0288] Another subject of the invention relates to a process for coating keratin materials, more particularly for caring for and / or making up keratin materials, such as the skin, characterized in that it comprises a) the application to the keratin materials of a first layer with a care composition (A) (Base Coat) comprising, in particular in a physiologically acceptable medium, at least one oily phase; and b) on the first layer formed by said composition (A), the application of a second layer with a composition (B) (Top Coat) consisting of a composition as defined previously.

[0289] The term “oily phase” means a liquid phase at room temperature (25°C) and atmospheric pressure comprising oils, waxes, pasty bodies and possibly all organic solvents and ingredients which are soluble or miscible in said phase.

[0290] The volatile oil or oils may be chosen from mineral oils, oils of vegetable origin, synthetic oils, in particular chosen from hydrocarbon and / or silicone oils, and mixtures thereof. They may be volatile or non-volatile.

[0291] By "non-volatile oil" is meant an oil remaining on the skin or keratin fiber at room temperature and atmospheric pressure for at least several hours. and having in particular a vapor pressure of less than 2.66 Pa, preferably less than 0.13 Pa. For example, the vapor pressure can be measured using the static method or by the isothermal thermogravimetry effusion method, according to the vapor pressure (OECD standard 104).

[0292] Another subject of the invention relates to a kit for coating keratin materials such as skin, in particular a kit for caring for and / or making up materials comprising at least two compartments, namely a) a first compartment comprising a composition (A) as defined previously; and b) a second compartment comprising a composition (B) as defined previously Together

[0293] According to another aspect, the invention also relates to a cosmetic assembly comprising: (i) a container delimiting one or more compartments (d), said container being closed by a closing element; and ii) a makeup and / or care composition in accordance with the invention placed inside said compartment(s).

[0294] The container may for example be in the form of a pot or a box.

[0295] The closure element may be in the form of a lid or a tear-off seal. In particular, this closure element may comprise a cap mounted to be movable by translation or by pivoting relative to the container housing said makeup and / or care composition(s).

[0296] It is understood that in the context of the present invention the weight percentages given for a compound or a family of compounds are always expressed by weight relative to the total weight of the composition.

[0297] Throughout the application, the expression "has a" or "includes a" must be understood as meaning "having at least one" or "comprising at least one", unless otherwise specified.

[0298] It is understood that the following examples are provided for illustrative purposes and are in no way limiting of the scope of the protection conferred by the present application. Examples

[0299] The following compositions were prepared according to the following procedures.

[0300] [Tables 1] Ingredients Example of composition according to the invention (1) Comparative example outside the invention (2) Comparative example outside the invention (3) Pigments Titanium dioxide (68.5%) Yellow iron oxide (25%) Red iron oxide (5%) Black iron oxide (1.5%) qsp 100 qsp 100 qsp 100 Resin Trimethyl Siloxysilicate 30 20 - Isododecane 20 - Protocol for preparing the example composition according to the invention (1):

[0301] The Trimethylsiloxy silicate resin and the pigments were pre-mixed with a spatula, then 50 grams of the mixture were ground for 15 seconds using an IKA type M20® knife mill, marketed by IKA Werke GmbH & Co. KG (Germany). The lid was then opened, the edges and the lid as well as the grinding chamber were scraped with a brush to check that there was no agglomeration (powder stuck to the walls). Then grinding was carried out again for 15 seconds.

[0302] Protocol for preparing the comparative example outside the invention (2):

[0303] The Trimethylsiloxysilicate resin and the isododecane were mixed with stirring in a Moritz mixer or with vigorous stirring in a Rayneri mixer until the resin was completely dissolved. Then the pigments were added, and the mixture was placed in an extruder. Any equipment or combination of equipment that can control a mechanical action that will knead the product as it is prepared, such as continuously operating processes of the scraped surface exchanger type, or even, preferably, of the twin-screw mixer / extruder type (called "extruder" for simplification in the remainder of this document) are suitable for implementation. Mention may be made, in particular, of the BC-21® and BC-45® models from Clextral, or the Prism Eurolab® model from ThermoRhéo.

[0304] Protocol for preparing the comparative example outside the invention (3)

[0305] The comparative example outside the invention (3) is obtained by simply mixing the ingredients with a spatula. Non-transfer tests

[0306] The compositions of examples (1), (2) and (3) were each applied by spreading with the finger on a synthetic skin of the "Bioskin Plate®" type marketed by the company MAPRECOS. The quantity deposited is 10 mg on a surface equivalent to a disc 5 cm in diameter. When the composition contains a volatile solvent (case of comparative example outside the invention 2), the deposit was left to dry until the volatile solvent had completely evaporated. The surface was then rubbed with a tissue to remove the excess. A drop of water was then placed on the surface for 1 minute. Then a cotton pad of the DemakUp ® brand was applied to the surface to absorb the drop of water. The color of the product transferred to the cotton pad was then visually evaluated.

[0307] Time stability test in a permeable container

[0308] The compositions of examples (1), (2) and (3) were each introduced into a metal cup measuring 59mm x 43mm x 5mm, then placed in the case of the product Vichy Dermablend Compact Foundation Correcting Cream 12h Shade 15 Opal. This case has openings underneath and is not airtight. The case with the product is then weighed, and the loss of mass is measured over time, ensuring that the openings of the case are in contact with the ambient air.

[0309] The results are shown in the following table.

[0310] [Tables2] Performances Example of composition according to the invention (1) Comparative example outside the invention (2) Comparative example outside the invention (3) Transfer on cotton No trace on the cotton No trace on the cotton Colored trace on the cotton Stability over time in a permeable container Constant performance Drying over time Constant performance

[0311] The composition according to the invention (1) was the only powder to exhibit both good transfer resistance and constant performance over time.

[0312] The example of composition according to the invention (1), obtained according to the grinding process according to the invention, was then compared to an identical composition obtained by simple mixing of the ingredients with a spatula (4).

[0313] It was observed that the composition obtained according to the grinding process according to the invention (1) presented, when applied to the skin, a more homogeneous deployment of the color and a better fidelity of the shade, compared to the composition obtained by simple mixing of the ingredients with a spatula (4).

Claims

Claims

1. Solid composition in powder form, in particular for coating keratin materials, more particularly for making up and / or caring for keratin materials, such as the skin, in particular comprising a physiologically acceptable medium and containing at least: a) a powdery phase, and b) at least one film-forming polymer in the solid state.

2. Composition according to claim 1, preferably comprising less than 3.0% by weight of water relative to the total weight of the composition, preferably less than 2.0% by weight, or even is free of water.

3. Composition according to claim 1 or 2, comprising a dry extract content greater than or equal to 85%, better still 90%, or even 95%.

4. Composition according to any one of the preceding claims, comprising a proportion of volatile oil of less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight relative to the total weight of the composition, preferably the composition is free of volatile oil.

5. Composition according to any one of the preceding claims, in the form of loose powder or compact powder.

6. Composition according to any one of the preceding claims, having a powder phase content greater than or equal to 50.0% by weight, in particular greater than or equal to 60.0% by weight, and more particularly ranging from 60 to 80% by weight, relative to the total weight of the composition.

7. A composition according to any preceding claim, wherein the powder phase comprises at least one filler and / or at least one particulate coloring matter.

8. Composition according to claim 7, where the filler or fillers is (are) present at a content ranging from 0 to 90% by weight, more preferably from 50 to 80% by weight relative to the total weight of the composition.

9. Composition according to claim 7 or 8, where the filler or fillers is (are) present at a content ranging from 0 to 95% by weight, more preferably from 25 to 90% by weight relative to the total weight of the powder phase.

10. A composition according to claim 7, wherein the content of material(s) particulate colorant(s) varies from 5 to 90% by weight, and preferably ranging from 10 to 70% by weight relative to the total weight of the composition.

11. Composition according to claim 7, wherein the powder phase comprises a content of particulate coloring matter(s) preferably ranging from 5 to 100% by weight, and preferably ranging from 10 to 75% by weight relative to the total weight of the powder phase.

12. Composition according to any one of claims 7, 10 and 11, where the particulate coloring material(s) is (are) chosen from pigments, nacres, reflective particles and mixtures thereof, and more particularly chosen from titanium dioxides, iron oxides and mixtures thereof; said pigments optionally comprising at least one lipophilic or hydrophobic coating.

13. Composition according to the invention according to any one of the preceding claims, comprising from 5% to 60% by weight, more preferably from 10 to 50% by weight, more particularly from 20% to 40% by weight of active material of film-forming polymer(s) relative to the total weight of the composition.

14. Composition according to any one of the preceding claims, wherein the film-forming polymer(s) is (are) hydrophobic, in particular liposoluble.

15. Composition according to any one of the preceding claims, where the hydrophobic film-forming polymer(s) in the solid state is (are) chosen from - a silicone resin; - a copolymer comprising carboxylate groups and polydimethylsiloxane groups; - a vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer; - a block ethylenic copolymer; - a polysaccharide grafted with organosiloxane groups; - a polysaccharide ether; - a norbornene polymer grafted with organosiloxane groups; - mixtures thereof.

16. Composition according to claim 15, wherein the silicone resin is Tri-methylsiloxysilicate.

17. A composition according to claim 15, wherein the copolymer comprising carboxylate groups and polydimethylsiloxane groups is chosen from those with the INCI name ACRYLATES / ETHYLHEXYL ACRYLATE / DIMETHICONE METHACRYLATE.

18. Composition according to claim 15, wherein the vinyl polymer comprising at least one carbosiloxane dendrimer-derived unit is chosen from that of the INCI name ACRYLATES / POLYTRIMETHYLSILOXYMETHACRYLATE in the solid state.

19. Composition according to claim 15, wherein the ethylenic block copolymer is obtained from at least one isobornyl methacrylate monomer, at least one isobornyl acrylate monomer, at least one isobutyl acrylate monomer and at least one acrylic acid monomer, in particular is chosen from the polymers with the INCI name ACRYLIC ACID / ISOBUTYL ACRYLATE / ISOBORNYL ACRYLATE COPOLYMER.

20. Composition according to claim 15, where the polysaccharide grafted with organosiloxane groups is that of INCI name: TRIME-THYLSILOXYSILYLCARBAMOYL PULLULANE in the solid state.

21. A composition according to claim 15, wherein the polysaccharide ether is selected from Ethyl Cellulose, Ethyl Guar and Myristoyl Pullulan.

22. Composition according to claim 15, where the norbornene polymer grafted with organosiloxane groups is that of INCI name: NORBORNENE / TRIS(TRIMETHYLSILOXY) SILYL-NORBORNENE in the solid state

23. A method of manufacturing a solid composition as defined in any one of the preceding claims, consisting of grinding in the solid state said film-forming polymer with at least part of the powder phase, in particular the particulate coloring materials present in the composition.

24. Solid composition in powder form obtainable by the process according to claim 23.

25. Cosmetic assembly comprising: i) a container delimiting one or more compartments (d), said container being closed by a closing element; and ii) a solid composition in powder form as defined in any one of claims 1 to 22 and 24 arranged inside said compartment(s).

26. Process for coating keratin materials, more particularly for making up and / or caring for keratin materials, such as skin, characterized in that it comprises the application to keratin materials of a composition in powder form according to any one of claims 1 to 22 and 24.

27. ​​Process for coating keratin materials, more particularly for caring for and / or making up keratin materials, such as the skin, characterized in that it comprises a) the application to the keratin materials of a first layer with a care composition (A) (Base Coat) comprising, in particular in a physiologically acceptable medium, at least one oily phase; and b) on the first layer formed by said composition (A), the application of a second layer with a composition (B) (Top Coat) consisting of a composition as defined in any one of claims 1 to 22 and 24.

28. Kit for coating keratin materials such as skin, in particular for care and / or makeup, comprising at least two compartments, namely a) a first compartment comprising a composition (A) according to claim 27; and b) a second compartment comprising a composition (B) consisting of a composition as defined in any one of claims 1 to 22 and 24.

Images