FR2873018A1 - SOLID WATER-IN-OIL COSMETIC EMULSION - Google Patents

Abstract

A solid water-in-oil emulsion comprises either an aqueous phase emulsified in a fatty phase, and at least one silicone surfactant having at least one polyhydroxylated chain; or an aqueous phase emulsified with at least one surfactant in the fatty phase, and at least one 8-22C alkyl dimethicone copolyol. The fatty phase comprises at least one ester oil and at least one wax.

Description

The present invention relates to a solid water-in-oil emulsion

  comprising a wax a particular oil and surfactant, usable in the cosmetic field. The invention also relates to a process for making up or caring for the skin of a human being comprising applying the composition to the skin.

  The makeup composition according to the invention is in particular a makeup composition for the skin, such as a foundation, an eyeshadow, a blusher, a concealer, a body makeup product, a red lips. More particularly, the invention relates to a foundation composition.

  The care composition may be a skin care product such as a skin care base, a care cream (day cream, night cream, anti-wrinkle cream), a makeup base; a care composition for the lips (lip balm); a sun protection or self-tanning composition; a deodorant.

  Skin makeup products such as foundations are known in the form of various galenics: loose powder, compact powder, cast solid product, stick, fluid cream.

  The cast solid products may be anhydrous or in the form of emulsions. The latter generally contain fatty substances such as oils and solid waxes, water and a particulate phase generally composed of fillers and pigments.

  The solid emulsion does not flow under its own weight at room temperature and is adapted to be packaged in a housing: to apply the product, the user can take the product directly by disintegrating it with the help of fingers or an applicator such as a sponge. For a good intake of the product by the user, it is necessary that the solid emulsion has a satisfactory hardness and in particular that this hardness varies little over time, especially after storage at temperatures higher than the ambient temperature (25 ° C.). VS). However, some solid emulsions may show a drop in their hardness over time: the product then has a tendency to soften it, making it more difficult or even unpleasant for the user who can hardly control the quantity of product taken. when taking. In addition, an initially strong and softening product is not attractive to the user.

  The object of the present invention is therefore to provide a solid makeup or skin care composition having a hardness that is stable over time, in particular after storage for at least one month at 37 ° C.

  Another object of the invention is to have a solid composition having good hardness while having a creamy and unctuous texture when applied to the skin.

  The inventors have discovered that by using a particular ester oil, a wax and a surfactant, it is possible to obtain a solid emulsion having a hardness that is stable over time, in particular after 1 month at 37 ° C., and also having a smooth texture. and creamy when applied to the skin.

  More specifically, the subject of the invention is a solid water-in-oil emulsion comprising an aqueous phase emulsified with an emulsifying surfactant in a fatty phase comprising an ester oil and a wax, a C8-C22 alkyl dimethicone copolyol, the emulsion having after at least one month at 37 ° C., a hardness such that the penetration force is greater than or equal to 45 g.

  The subject of the invention is also a cosmetic process for making up or non-therapeutic care of the skin, comprising applying to the skin a corn-position as defined above.

  By solid composition is meant a composition which does not flow under its own weight at ambient temperature (25 ° C.) after one hour.

  The solid emulsion according to the invention comprises at least one ester oil.

  By ester oil is meant a liquid oil at ambient temperature (25 C) comprising at least one ester function in its molecule. Advantageously, the ester oil is a monoester.

  The ester oil may be chosen preferably from the monoesters of formula RICOOR 2 in which R 1 represents a linear or branched hydrocarbon-based chain comprising from 4 to 40 carbon atoms, preferably from 4 to 30 carbon atoms, and preferably from 7 to to 20 carbon atoms, and R2 represents a branched hydrocarbon chain containing from 3 to 40 carbon atoms, preferably from 10 to 30 carbon atoms, and preferably from 16 to 26 carbon atoms.

  As an example of an ester oil, mention may be made of isodecyl neopentanoate; isocetyl octanoate; isononyl isononanoate, isodecyl isononanoate, tridecyl isononanoate; hexyl laurate, 2-hexyl decyl laurate; isopropyl myristate, isocetyl myristate, isotridecyl myristate and 2-octyldodecyl myristate; isopropyl palmitate, 2-ethyl hexyl palmitate, isooctyl palmitate, isoketyl palmitate, isodecyl palmitate, isostearyl palmitate, 2-octyl decyl palmitate; isopropyl isostearate, 2-octyl dodecyl stearate, isostearyl isostearate; 2-octyl dodecyl erucate; and their mixtures.

  The ester oil may be present in the emulsion according to the invention in a content ranging from 5% to 20% by weight, relative to the total weight of the composition, preferably ranging from 7% to 15% by weight, and preferably ranging from 8% to 12% by weight.

  The fatty phase may also comprise a volatile silicone oil.

  By "volatile oil" is meant an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 300 to 300 mmHg), and preferably ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01). at 10 mmHg).

  The volatile silicone oil may be chosen from linear or cyclic silicone oils having a viscosity at room temperature of less than 8 mm 2 / s and having in particular from 2 to 7 silicon atoms, these silicones possibly containing alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that may be used in the invention, there may be mentioned in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.

  The volatile silicone oil may be present in a content ranging from 5% to 40% by weight, relative to the total weight of the composition, preferably ranging from 10% to 30% by weight, and preferably ranging from 15% to 30% by weight.

  Advantageously, the total content of water and volatile silicone oil in the composition is less than or equal to 50% by weight, relative to the total weight of the composition, in particular ranges from 30% to 50% by weight, and preferably is from 40% to 50% by weight.

  The fatty phase of the emulsion may comprise an additional oil, different from the ester oils and volatile silicone oils described above.

  The additional oil may be chosen in particular from hydrocarbon-based oils or fluorinated oils, which are volatile or non-volatile.

  The term "hydrocarbon-based oil" means an oil formed essentially or even consisting of carbon and hydrogen atoms, and optionally of oxygen and nitrogen atoms, and not containing any silicon atom or fluorine. It may contain alcohol, ether, carboxylic acid, amine and / or amide groups.

  By fluorinated oil is meant an oil containing at least one fluorine atom. As volatile additional oil that can be used in the invention, mention may be made of: volatile hydrocarbon oils containing from 8 to 16 carbon atoms and mixtures thereof and in particular branched C 8 -C 16 alkanes such as isoalkanes (also known as isoparaffins) in C 8 -C16, isododecane, isodecane, isohexadecane and for example the oils sold under the trade names of Isopars 'or Permethyls', branched C8-C16 esters such as isohexyl neo-pentanoate and their mixtures; isododecane is preferably used; volatile fluorinated oils such as nonafluoroethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane and dodecafluoro-pentane, and mixtures thereof.

- and their mixtures.

  As nonvolatile additional oil that can be used in the invention, mention may be made of hydrocarbon-based oils of mineral or synthetic origin, such as linear or branched hydrocarbons, such as paraffin oil or its derivatives, liquid petroleum jelly, polydecenes or polyisobutene. hydrogenated such as Parléam marketed by the company Nippon Oil Fats, squalane of synthetic or vegetable origin; As non-volatile additional oil, mention may also be made of hydrocarbon-based vegetable oils with a high triglyceride content consisting of esters of fatty acids and glycerol, the fatty acids of which may have various chain lengths, the latter possibly being linear. or branched, saturated or unsaturated, especially fatty acid triglycerides including 4 to 22 carbon atoms, such as triglycerides of heptanoic, octanoic acids, and capric / caprylic acids or else hydroxylated triglycerides, such as sweet almond oil, calophyllum, palm, grape seed, sesame, arara, rapeseed, sunflower, cotton, apricot, castor oil, alfalfa, squash, blackcurrant, macadamia, muscat rose, hazelnut, avocado, jojoba, olive, sprouts of cereals (corn, wheat, barley, rye), shea butter; higher C8-C26 fatty acids such as oleic acid, linoleic acid, linolenic acid or isostearic acid; higher C8-C26 fatty alcohols such as oleic alcohol, linoleic or linolenic alcohol, isostearyl alcohol or octyl dodecanol; synthetic ethers containing at least 7 carbon atoms, silicone oils such as polydimethylsiloxanes (PDMS) which are liquid at room temperature, linear, optionally phenylated, such as phenyl trimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, liquid 2-phenylethyl trimethylsiloxysilicates, optionally substituted with aliphatic and / or aromatic groups such as alkyl, alkoxy or phenyl groups, during and / or at the end of the silicone chain, groups having from 2 to 24 carbon atoms and optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amine groups; and their mixtures.

  Advantageously, the additional oil may be present in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition, and preferably ranging from 0.1% to 5% by weight. In one embodiment of the emulsion according to the invention, the additional oil content may also be 0% by weight, relative to the total weight of the composition.

  According to a preferred embodiment of the invention, the emulsion contains as oil only an ester oil and optionally a volatile silicone oil, as described above.

  Advantageously, the wax present in the emulsion according to the invention may be chosen from waxes having a hardness ranging from 5 MPa to 9 MPa, and preferably from 6 MPa to 9 MPa, and preferably ranging from 7 MPa. at 9 MPa.

  For the purposes of the present invention, the term "wax" means a lipophilic fat compound, solid at room temperature (25 ° C.), with a reversible solid state change of state, having a melting point greater than 30 ° C. and up to 200 ° C. C, a hardness greater than 0.5 MPa, and having in the solid state an anisotropic crystalline organization. By bringing the wax to its melting temperature, it is possible to render it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, a recrystallization of the wax in the oils of the mixed.

  The hardness of the wax is determined by measuring the compressive strength measured at 20 C using the texturometer sold under the name TA-XT2i by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm moving at the measuring speed of 0.1 mmis, and penetrating into the wax at a penetration depth of 0.3 mm. To perform the hardness measurement, the wax is melted at a temperature equal to the melting point of the wax + 20 C. The melted wax is cast in a container 30 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C.) for 24 hours and then the wax is kept for at least 1 hour at 20 ° C. before carrying out the hardness measurement. The value of the hardness is the measured compressive force divided by the surface of the texturometer cylinder in contact with the wax.

  The waxes, in the sense of the application, may be hydrocarbon, silicone and / or fluorinated, optionally comprising ester or hydroxyl functions.

  The wax having the hardness as defined above may be chosen from carnauba wax, microcrystalline waxes, ozokerites, hydrogenated jojoba oil, and polyethylene waxes, such as that sold under the names "PERFORMALENE 400 POLYETHYLENE" by the New Phase Technologies, silicone waxes such as C24-C28 alkyl dimethyl siloxane alkyl such as that sold under the name "ABIL WAX 9810" by the company GOLDSCHMIDT, palm butter, C 20 alkyl stearate. -C40 sold under the name "Kester WAX K82H" by the company Kester Keunen, stearyl benzoate, Shellac wax, and mixtures thereof. A wax chosen from Carnauba wax, Candelilla wax, ozokerites, hydrogenated jojoba oil and polyethylene waxes is preferably used. Preferably, the wax is chosen from Candelilla wax, ozokerite, and mixtures thereof.

  The wax may be present in the composition according to the invention in a content ranging from 1% to 10% by weight, relative to the total weight of the composition, preferably ranging from 2% to 7% by weight, and preferably ranging from 2% to 5% by weight.

  The emulsion according to the invention comprises, as emulsifier, a C8-C22 alkyl dimethicone copolyol, that is to say an oxypropylenated and / or oxyethylenated poly (C 8 -C 22) alkyl dimethyl methyl siloxane.

  The C 8 -C 22 alkyl dimethicone copolyol is advantageously a compound of formula (I) below: embedded image in which: PE represents (-C 2 H 4 O) x (C 3 H 6 O) y R, R being chosen from a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms, x ranging from 0 to 100 and ranging from from 0 to 80, where x and y are not simultaneously 0 - m ranging from 1 to 40 -n ranging from 10 to 200 - o ranging from 1 to 100 - p ranging from 7 to 21 - q ranging from 0 to 4 and preferably: R = H m = 1 to 10 n = 10 to 100 o = 1 to 30 p = 15 q = 3 As alkyl C 8 -C 22 dimethicone copolyol, there may be mentioned cetyl dimethicone copolyol such as the product marketed under the name Abil EM-90 by the Goldschmidt company.

  The C8-C22 alkyl dimethicone copolyol may be present in the emulsion in a range of from 0.1% to 5% by weight, based on the total weight of the composition, and preferably ranging from 1% to 3% by weight.

  The emulsion may comprise an additional surfactant different from the C8-C22 alkyl dimethicone copolyol described above, in particular present in a content ranging from 0.05% to 3% by weight, relative to the total weight of the composition, and from preferably ranging from 0.1% to 2% by weight.

  The additional surfactant is a surfactant which makes it possible to obtain emulsion water-in-oil, in particular a surfactant having an HLB (hydrophilic / lipophilic balance) of less than 7; such an emulsifying surfactant may be chosen from polyol fatty acid esters such as mono-, di-, tri- or sesquiolates or sorbitol or glycerol stearates, glycerol or polyethylene glycol laurates; polymers of the polyoxyalkylenated glycol fatty acid ester type. It is also possible to use silicones with a polyhydroxy chain, in particular polyglycerolated chain, emulsifying silicone elastomers. By polyhydroxy chain is meant a hydrocarbon chain comprising at least two hydroxyl groups.

  As polyhydroxylated chain silicones, the silicone polymers represented by the following general formula (I ') can be used: ## STR1 ## wherein: a) a, b and c are such that a varies from 1 to 2.5; and b and c, independently of each other, vary from 0.001 to 1.5.

  b) RI, which may be identical or different, is chosen from: (C 1 -C 30) alkyl radicals, optionally substituted by one or more fluorine atoms, amino and / or carboxy groups, aryl and aralkyl radicals, and radicals of formula general (II): CdH2d-O- (C2H40) e (C3H6O) fR4 wherein: R4 is a C4 to C30 hydrocarbon radical, or a radical R5 (CO) - with R5 being a C1 to C30 hydrocarbon radical, and d, e and f being integers such that d varies from 0 to 15, e and f, independently of one another, range from 0 to 50, and combinations thereof.

  c) R2 is represented by the following general formula (III): -QOX (III) wherein: Q is a C2-C20 divalent hydrocarbon radical, which may include at least one ether link and / or at least one ester link, and X is a polyhydroxy hydrocarbon radical.

  d) R3 is an organosiloxane group of general formula (IV): R Cg H2 (SiO) h SiR3 (IV) g

R with:

  each of the radicals R representing, independently of one another, a radical chosen from C 1 to C 30 alkyl radicals, optionally substituted by one or more fluorine atoms, and aryl and aralkyl radicals, and h being integers such that g varies from 1 to 5 and h ranges from 0 to 500.

  When the radicals R represent a radical chosen from C1-C30 alkyl radicals, optionally substituted with one or more fluorine atoms, aryl radicals and aralkyl radicals, they have the same meaning as the radical R 'as defined previously. 10

  It should be noted that the radicals R ', R2 and R3 of the silicone polymers of general formula (I'), as defined above, are not distributed in a sequential manner, but randomly or statistically, this is that is, they appear in the polymer structure in no particular order.

  In a): - more particularly, a varies from 1.2 to 2.3. And, in particular, b and c, independently of each other, vary from 0.05 to 1.

  In b): when R 'is an alkyl radical, it may be a C 1 to C 30 alkyl radical, in particular a C 1 to C 25 alkyl radical, more particularly a C 1 to C 20 alkyl radical, in particular an alkyl radical, C.sub.1 -C.sub.10, in particular a C.sub.1 -C.sub.4 alkyl radical, and in particular a C.sub.1 -C.sub.4 alkyl radical. More particularly, it may be a methyl, ethyl, n- or iso-propyl, n- or iso- or tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or lauryl radical. It may also be a cycloalkyl radical such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. It can also be a monounsaturated or polyunsaturated alkyl radical, linear or branched. It may also be an alkyl radical substituted with one or more fluorine atoms, such as trifluoropropyl or heptadecafluorodecyl. It can also be an alkyl radical substituted with one or more amino groups, such as 2-aminoethyl, 3-aminopropyl or 2-aminylamino-3-aminopropyl. It may also be an alkyl group substituted by one or more carboxy groups, such as 3-carboxypropyl.

  R 'can also be an aryl or aralkyl radical such as the phenyl radical, the tolyl radical, the benzyl radical and the phenethyl radical.

  R 'can also be an organic group represented by the general formula (II): CdH2d-O- (C2H4O) e (C3H6O) fR4 (II) According to a particular embodiment, R' can be a hydroxylated radical or a radical resulting from the addition reaction of a saturated or unsaturated, branched or linear alkenyl ether, in which d = 0 and therefore of formula: -O- (C2H4O) e (C3H6O) fR4 In this case, when e and f are zero, then R 'is an alkoxy group having 4 to 30 carbon atoms, for example a lower alkoxy group of C4 to C10, such as butoxy or pentoxy or a higher alkoxy group, C11 to C30 such as oleoxy, stearoxy, eg, cetyl alcohol, oleic alcohol and stearyl alcohol, or a radical derived from an acid or a fatty acid, such as acetic acid, lactic acid, butyric acid, oleic acid, stearic acid and behenic acid.

  When e and f are greater than 1, then R 'is a hydroxyl radical from the addition reaction of an alkylene oxide.

  When e and f are zero, it is particularly advantageous if d is 3, 5 or 11. In this case, R ', depending on the nature of the substituent R 4, is an allyl ether, penthenyl ether or undecenyl ether radical, or an allylstearyl radical. ther, penthenylbehenyl ether, or undecenyloleyl ether.

  When e or f are different from zero, an alkoxy radical and an ester radical are present via a polyoxyalkylene group.

  Whatever e and f, it is particularly advantageous for d to be in the range of 3 to 5.

  According to one embodiment, the radical R 'can be any of the previously defined radicals, or a combination of two or more of these radicals.

  Advantageously, R 'is an alkyl radical chosen from the methyl radical, the lauryl radical, and combinations thereof.

  Moreover, when R 'corresponds to two or more radicals, for example a methyl radical and a lauryl radical, they appear in the structure randomly, and with a frequency that may be different for each of the radicals.

  In particular, at least 50% of the radicals R ', in particular at least 70% of the radicals R', and more particularly 100% of the radicals R 'are methyl radicals.

  In c): - Q can be in particular a divalent hydrocarbon radical chosen from: - (CH2) 2 -, - (CH2) 3-, CH2CH (CH3) CH2, (CH2) 4-, - (CH2) 5 -, - (CH2) 6-, - (CH2) 7- (CH2) 8-, - (CH2) 2-CH (CH2CH2CH3) -, -CH2-CH (CH2CH3) -, - (CH2) 3-0- (CH2) 2-, - (CH2) 3-O- (CH2) 2-O- (CH2) 2-, - (CH2) 3-O-CH2CH (CH3) - and CH2-CH (CH3) -COO ( CH2) 2-.

  Advantageously, Q is a divalent radical chosen from (CH2) 2 and (CH2) 3-.

  X may in particular be a polyhydroxylated hydrocarbon radical comprising at least two hydroxyl residues, and in particular a hydrocarbon graft chosen from glycerolated derivatives and osidic derivatives.

  The glycerol residues may be compounds having the following formulas, wherein Q has the same meaning as in general formula (III), and s and t are integers in the range of 1 to 20, in particular 1 at 15, in particular from 1 to 10, and more particularly from 1 to 5. CH2OH

H O 10 Q,

OH CH2OH

H

OH

OH

H

OH

  In the preceding formulas, one or more hydroxyl groups may be replaced by alkoxy groups or ester groups.

  The osidic radicals which can be used in the general formula (III) can be of the monosaccharide type, such as the glycosyl, mannosyl, galactosyl, ribosyl, arabinosyl, xylosyl or fructosyl groups, of the oligosaccharide type such as maltosyl, cellobiosyl or lactosyl. or maltotriosyl, or polysaccharide type such as cellulose or starch.

  In particular, the saccharide groups are of monosaccharide or oligosaccharide type.

  In d): each of the radicals R may in particular represent, independently of one another, a radical chosen from C 1 to C 20 alkyl radicals, more particularly C 1 to C 10, in particular C 1 to C alkyl radicals, optionally substituted with one or more fluorine atoms. When the radicals R represent a radical selected from alkyl radicals as defined above, optionally substituted with one or more fluorine atoms, they have the same meaning as the RI radical as defined above.

  - g, according to a particular embodiment, is 2 - h, according to a particular embodiment, is in the range of 1 to 50.

  According to a particular embodiment, the silicone polymer of general formula (I ') is such that: - a varies from 1 to 1.4, b and c, independently of one another, vary from 0.02 at 0.03, and - R 'is a C1 to C6 alkyl, in particular a C1 to C6, and more particularly a C1 to C4 alkyl radical.

  R2 is represented by the formula (IIIA): ## STR2 ## in which: n varies from 1 to 5, and - R3 is represented by the formula (IVA): -C2H4 (CH3) 2 SiO [(CH 3) 2 SiO] m Si (CH 3) 2 (IVA) in which: mvariates from 3 to 9.

  According to another particular embodiment, the silicone polymer of general formula (I), usable in the cosmetic compositions according to the present invention, is such that: a varies from 1 to 1.4, b and c, independently from one another, vary from 0.02 to 0.04, - RI is a methyl radical, R2 is represented by the formula (IIIA) in which n varies from 1 to 5, and - R3 is represented by the formula (IVA) wherein m varies from 3 to 9.

  For example, the silicone polymer of general formula (I ') used in the composition according to the invention is chosen from polyglyceryl-3-polymethylsiloxyethyl dimethicone, laurylpolyglyceryl-3-polymethylsiloxyethyl dimethicone and polyglyceryl-3 dimethicone. disiloxane, whose formulas are respectively: Pollyceryl-3-polymethylsiloxyethyl dimethicone (formula (V)): (CH) SiO 3

C 1 H 3 Si 0-1 CH Sx

  If O CH Gly i O CH Si (CH3) (V) a b

VS

  in which: SX: -C2H4 [(CH3) 2SiO1mSI (CH3) 3 Gly: -C3H60 [CH2-CH (OH) CH2O] nH with a = 1-1.4, b = 0.02-0.04, c = 0.02-0.04, m = 3-9, n = 1-5 Polyglyceryl-3-polymethylsiloxyethyl lauryl dimethicone (formula (VI)): ## STR1 ## wherein S 1, G 1, a, b, c, m and n have the same meaning as above and R 1 is either a methyl radical or a lauryl radical.

  3-polyglyceryl disiloxane dimethicone (formula (VII)): (CH 3) if () (CH) if () CH 3 SiO CH Sx SiO

CH

  ## STR2 ## wherein Gly, a, b, c, m and have the same meaning as above, and Sx: -O (CH 3) 2 SiO-Si (CH 3) 3 The silicone polymers of the formula (I ') are described in detail in the patent application EP 1,213,316, incorporated herein by reference.

  According to one particular embodiment, the silicone polymer of general formula (I ') is chosen from the polymers marketed by SHIN-ETSU under the references KF6100, KF6104 and KF6105.

  The polymer marketed under the reference KF6104 is particularly suitable for the preparation of the cosmetic compositions according to the invention.

  It is also possible as additional emulsifier an elastomeric crosslinking organopolysioloxane emulsifier, especially polyhydroxy chain.

  The elastomeric elastomeric crosslinked organopolysiloxane may be obtained by a crosslinking addition reaction of diorganopolysiloxane containing at least one silicon-bonded hydrogen and polyhydroxylated or polyoxyalkylenated compounds having ethylenically unsaturated groups, especially in the presence of platinum catalyst.

  Preferably, the crosslinked organopolysiloxane elastomer is obtained by crosslinking addition reaction (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) glycerolated or polyoxyalkylenated compounds having at least two ethylenically unsaturated groups, especially in the presence (C) of platinum catalyst.

  In particular, the organopolysiloxane may be obtained by reaction of dimethylvinylsiloxy-terminated polyglycerol compound and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst.

  The compound (A) is the basic reagent for the formation of organopolysiloxane elastomer and the crosslinking is carried out by addition reaction of the compound (A) with the compound (B) in the presence of the catalyst (C).

  The compound (A) is in particular an organopolysiloxane having at least 2 hydrogen atoms bonded to distinct silicon atoms in each molecule.

  The compound (A) may have any molecular structure, in particular a linear chain or branched chain structure or a cyclic structure.

  The compound (A) may have a viscosity at 25C ranging from 1 to 50,000 centistokes, in particular to be well miscible with the compound (B).

  The organic groups bonded to the silicon atoms of the compound (A) may be alkyl groups having from 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl (or lauryl), myristyl, cetyl stearyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group. Preferably, said organic group is chosen from methyl, phenyl and lauryl groups.

  The compound (A) can thus be chosen from trimethylsiloxy-terminated methylhydrogenpolysiloxanes, trimethylsiloxy-terminated dimethylsiloxane-methylhydrogenosiloxane copolymers, dimethylsiloxane-methylhydrogensiloxane cyclic copolymers, and trimethylsiloxy-terminated dimethylsiloxane-methylhydrogensiloxane-laurylmethylsiloxane copolymers.

  Compound (B) may be: - either a polyglycerolated compound corresponding to the following formula (B '): CmH2m-1 -O- [Gly] n-CmH2m-1 (B') in which m is an integer ranging from 2 at 6, n is an integer ranging from 2 to 200, preferably ranging from 2 to 100, preferably ranging from 2 to 50, preferably n ranging from 2 to 20, preferably ranging from 2 to 10, and preferably ranging from 2 to 5, and in particular 3; Gly denotes: -CH 2 -CH (OH) -CH 2 -O- or -CH 2 -CH (CH 2 OH) -O- - a polyoxyalkylene compound having two vinyl groups.

  Advantageously, the sum of the number of ethylenic groups per molecule of the compound (B) and the number of hydrogen atoms bonded to silicon atoms per molecule of the compound (A) is at least 4.

  It is advantageous that the compound (A) is added in an amount such that the molecular ratio between the total amount of hydrogen atoms bonded to silicon atoms in the compound (A) and the total amount of all the groups to Ethylenic unsaturation in the compound (B) is in the range of 1/1 to 20/1.

  The compound (C) is the catalyst for the crosslinking reaction, and is in particular chloroplatinic acid, chloroplatinicolefinic acid complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black, and platinum supported .

  The catalyst (C) is preferably added from 0.1 to 1000 parts by weight, more preferably from 1 to 100 parts by weight, as clean platinum metal per 1000 parts by weight of the total amount of the compounds (A) and ( B).

  The emulsifying silicone elastomer may be transported in gel form in at least one hydrocarbon oil and / or a silicone oil. In these gels, the emulsifying elastomer is often in the form of non-spherical particles.

  Polyoxyalkylenated elastomers are described in particular in patents US5236986, US5412004, US5837793 and US5811487, the contents of which are incorporated by reference.

  As the polyoxyalkylene silicone elastomer, those sold under the names "KSG-21", "KSG-20", "KSG-30", "KSG31", KSG-32 "," KSG-33 "," KSG- 210 "," KSG-310 "," KSG-320 "," KSG-330 "," KSG-340 "," X-226146 "by the company Shin Etsu," DC9010 "," DC9011 "by Dow Corning .

  Polyglycerolated elastomers are described in particular in the application WOA-25 2004/024798, the contents of which are incorporated herein by reference.

  As the polyglycerolated silicone elastomer, those sold under the names "KSG-710", "KSG-810", "KSG-820", "KSG-830", "KSG840" 30 by the company Shin Etsu can be used.

  As another additional surfactant that can be used in the invention for obtaining an W / O emulsion, mention may be made of polymers of the polyoxyalkylenated glycol fatty acid ester type having water-in-oil emulsifying properties.

  The fatty acid ester of said polymer is preferably polyhydroxylated. In particular, this polymer is a block polymer, preferably of ABA structure, comprising poly (hydroxylated ester) sequences and polyethylene glycol sequences.

  The fatty acid ester of said emulsifying polymer as defined above generally has a chain comprising from 12 to 20 carbon atoms, preferably from 14 to 18 carbon atoms. The esters may especially be chosen from oleates, palmitates or stearates.

  The polyethylene glycol sequences of said emulsifying polymer as defined above preferably comprise from 4 to 50 moles of ethylene oxide, and more preferably from 20 to 40 moles of ethylene oxide.

  A polymeric surfactant which is particularly suitable for producing the compositions of the invention is the polyethylene glycol dihydroxystearate 30 EO sold under the trade name Arlacel P 135 by the company ICI.

  The aqueous phase of the solid emulsion according to the invention comprises water. The water may be floral water such as cornflower water and / or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and / or thermal water. The water may be present in the emulsion according to the invention in a content ranging from 10% to 40% by weight, relative to the total weight of the composition, preferably ranging from 15% to 30% by weight, and preferably ranging from 15% to 25% by weight.

  The aqueous phase may also comprise water-miscible solvents (at room temperature - C), for example monoalcohols having from 2 to 6 carbon atoms, such as ethanol or isopropanol; the polyols having in particular 2 to 20 carbon atoms, preferably having 2 to 10 carbon atoms, and preferably having 2 to 6 carbon atoms, such as glycerine, propylene glycol, butylene glycol, pentylene glycol hexylene glycol, dipropylene glycol, diethylene glycol; glycol ethers (having in particular from 3 to 16 carbon atoms) such as the mono, di or tripropylene glycol (C1-C4) alkyl ethers, the mono, di or triethylene glycol (C1-C4) alkyl ethers; ; and their mixtures.

  The emulsion according to the invention may comprise a water-miscible organic solvent, in particular a polyol, in a content ranging from 1% to 20% by weight, relative to the total weight of the composition, and preferably ranging from 3% by weight. % to 15% by weight.

  The aqueous phase may further comprise stabilizing agents, for example sodium chloride, magnesium dichloride and magnesium sulfate.

  The aqueous phase may also comprise any water-soluble or water-dispersible compound compatible with an aqueous phase such as gelling agents, film-forming polymers, thickeners, surfactants and mixtures thereof.

  Preferably, the aqueous phase may be present in the emulsion according to the invention in a content ranging from 25% to 50%, by weight, preferably ranging from 25%. at 45% by weight, relative to the total weight of the emulsion, and preferably ranging from 25% to 35% by weight.

  The fatty phase of the emulsion may also comprise at least one pasty fatty substance.

  For the purposes of the present invention, the term "pasty" is intended to denote a lipophilic fatty compound having a reversible solid / liquid state change having, in the solid state, an anisotropic crystalline organization and having, at a temperature of 23 ° C., a liquid fraction. and a solid fraction ..

  For the purposes of the invention, the term "pasty compound" means a compound having a hardness at 20 ° C. ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 10 MPa.

  The hardness is measured according to a method of penetration of a probe into a sample of compound and in particular using a texture analyzer (for example TA-XT2i from Rhéo) equipped with a stainless steel cylinder. 2 mm in diameter. The hardness measurement is carried out at 20 C in the center of 5 samples.

  The cylinder is introduced into each sample at a pre-speed of 1 mm / sec and then at a measuring speed of 0.1 mm, the penetration depth being 0.3 mm. The measured value of the hardness is that of the maximum peak.

  This pasty compound is furthermore, at a temperature of 23 ° C., in the form of a liquid fraction and a solid fraction. In other words, the starting melting temperature of the pasty compound is less than 23 ° C. The liquid fraction of the pasty compound measured at 23 ° C. represents 9 to 97% by weight of the compound. This liquid fraction at 23 ° C is preferably between 15 and 85%, more preferably between 40 and 85% by weight.

  The liquid fraction by weight of the pasty compound at 23 ° C. is equal to the ratio of the enthalpy of fusion consumed at 23 ° C. on the heat of fusion of the pasty compound.

  The heat of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when the entirety of its mass is in crystalline solid form.

  The pasty compound is said to be in a liquid state when all of its mass is in liquid form.

  The enthalpy of melting of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the 2873018 19 company TA instrument, with a temperature rise of 5 or 10 C per minute, according to the standard ISO 11357-3: 1999. The enthalpy of fusion of the pasty compound is the amount of energy required to pass the compound from the solid state to the liquid state. It is expressed in J / g.

  The enthalpy of fusion consumed at 23 ° C. is the quantity of energy absorbed by the sample to change from the solid state to the state present at 23 ° C. consisting of a liquid fraction and a solid fraction. .

  The liquid fraction of the pasty compound measured at 32 ° C is preferably 30 to 100% by weight of the compound, preferably 80 to 100%, more preferably 90 to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32 C is 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32 C.

  The liquid fraction of the pasty compound measured at 32 ° C. is equal to the ratio of the enthalpy of fusion consumed at 32 ° C. on the heat of fusion of the pasty compound. The enthalpy of fusion consumed at 32 ° C. is calculated in the same way as the heat of fusion consumed at 23 ° C.

  The pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound can be obtained synthetically from starting materials of plant origin.

  The pasty compound is advantageously chosen from: - polymeric or non-polymeric silicone compounds, - fluorinated or non-polymeric compounds, - vinyl polymers, in particular: - homopolymers of olefins - copolymers of olefins - homopolymers and copolymers of dienes hydrogenated linear or branched oligomers, homo or copolymers of alkyl (meth) acrylates preferably having a C8-C30 alkyl group; homopolymers and copolymers of vinyl esters having C8-C30 alkyl groups; oligomers homo and copolymers of vinyl ethers having C 8 -C 30 alkyl groups; liposoluble polyethers resulting from the polyetherification between one or more C 2 -C 10 O diols, preferably C 2 -C 50 diols, and the esters thereof, and mixtures thereof.

  The pasty compound is preferably polymer, in particular hydrocarbon-rich.

  Silicone and / or fluorinated pasty compounds A preferred silicone and fluoro pasty compound is polymethyl trifluoropropyl methylalkyl dimethylsiloxane, manufactured under the name X22-1088 by Shin Etsu.

  Paste Polyether Compounds Among the liposoluble polyethers, copolymers of ethylene oxide and / or propylene oxide with C6-C30 long-chain alkylene oxides are particularly preferred, such as the weight ratio of the ethylene oxide and / or propylene oxide with alkylene oxide in the copolymer is from 5:95 to 70:30. In this family, mention will in particular be made of copolymers such as long-chain alkylene oxides are arranged in blocks having an average molecular weight of 1,000 to 10,000, for example a polyoxyethylenepolydodecyl glycol block copolymer such as dodecanediol ethers (22). mol) and polyethylene glycol (45 EO) marketed under the tradename ELFACOS ST9 by Akzo Nobel.

  Among the esters, the esters of an oligomeric glycerol, in particular the diglycerol esters, in particular the adipic acid and glycerol condensates, for which part of the hydroxyl groups of the glycerols have reacted with a mixture of acids, are particularly preferred. fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid and 12-hydroxystearic acid, such as those marketed under the trademark Softisan 649 by the company Sasol, the propionate arachidyl sold under the trademark Waxenol 801 by Alzo, phytosterol esters, non-crosslinked polyesters resulting from the polycondensation between a linear or branched C 4 -C 50 diacid or polycarboxylic acid and a C2-050 diol or polyol, aliphatic ester esters resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic carboxylic acid; and their mixtures.

  The aliphatic carboxylic acid comprises from 4 to 30 and preferably from 8 to 30 carbon atoms. It is preferably chosen from hexanoic acid, heptanoic acid, octanoic acid, 2-ethyl hexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, and acid. tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexydecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, acid isoarachidic acid, octyldodecanoic acid, henicosanoic acid, docosanoic acid, and mixtures thereof.

  The aliphatic carboxylic acid is preferably branched.

  The aliphatic hydroxy carboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid having from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to to 20 hydroxyl groups, preferably 1 to 10 hydroxyl groups and more preferably 1 to 6 hydroxyl groups. The aliphatic hydroxycarboxylic acid ester is chosen from: a) partial or total esters of linear, saturated monohydroxylated aliphatic monocarboxylic acids; b) partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids; c) partial or total esters of saturated monohydroxylated aliphatic polycarboxylic acids; d) partial or total esters of saturated polyhydroxylated aliphatic polycarboxylic acids; e) partial or total esters of C 2 to C 16 aliphatic polyols reacted with a mono- or polyhydroxylated aliphatic mono or poly carboxylic acid, and mixtures thereof.

  The aliphatic ester esters are advantageously chosen from: the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 1 (1: 1) or monoisostearate of hydrogenated castor, the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions 1 to 2 (1/2) or hydrogenated castor oil diisostearate, the resulting ester of the esterification reaction of hydrogenated castor oil with isostearic acid in the proportions 1 to 3 (1/3) or triisostea 15-spleen of hydrogenated castor oil, and mixtures thereof.

  Among the pasty compounds of plant origin, a mixture of soy sterols and oxyethylenated (5OE) oxypropylene pentaerythritol (5 PO), marketed under the reference Lanolide by the company VEVY, will preferably be chosen.

  As the pasty fatty substance, a block copolymer of ethylene oxide and / or of propylene oxide and of alkylene oxide having from 6 to 40 carbon atoms is preferably used, the copolymer having a mean molecular weight of weight ranging from 5000 to 8000.

  Advantageously, the alkylene oxide of the copolymer may comprise from 6 to 30 carbon atoms, preferably from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, and more preferably from 10 to 14 carbon atoms. carbon.

  The weight average molecular weight of the copolymer ranges from 5,000 to 8,000, preferably from 5,500 to 7,000, preferentially from 5,500 to 6,500, and more preferably from 5,800 to 6,200.

  The copolymer preferably comprises from 35 to 55 units of ethylene oxide and / or propylene oxide and from 15 to 30 alkylene oxide units having from 6 to 40 carbon atoms.

  In particular, the copolymer is such that the ratio between the number of units of ethylene oxide and / or propylene oxide and the number of alkylene oxide units having from 6 to 40 carbon atoms can from 1.5 to 2.5, preferably from 1.8 to 2.3 and preferably from 1.9 to 2.1.

  Such copolymers are described in particular in document FR-A-2425848 and sold under the name "ELFACOS ST 9" by the company Akzo Nobel.

  The pasty fatty substance may be present in the composition according to the invention in a content ranging from 1% to 25% by weight, relative to the total weight of the composition, preferably ranging from 1% to 18% by weight. and preferably ranging from 1% to 10% by weight.

  The solid emulsion according to the invention has a hardness after at least one month at 37 ° C., such that the penetration force is greater than 45 g, in particular from 45 g to 150 g.

  Hardness means after at least one month at 37 C the hardness measured after storage of the solid emulsion for at least one month at 37 C, and in particular one month from the end of the preparation of the solid emulsion.

  In particular, the solid emulsion has a hardness such that the penetration force after 24 hours at 20 ° C. (especially from the end of the preparation of the solid emulsion) and at least 1 month at 37 ° C. is greater than or equal to at 45 grams (g), especially ranges from 45 g to 150 g.

  Preferably, the hardness of the solid emulsion ranges from 50 g to 130 g, preferably from 60 g to 130 g, and more preferably from 70 g to 130 g.

  The hardness of the emulsion is measured according to the following protocol: At the end of preparation of the emulsion, the latter is hot cast in a cup and is kept 24 hours at 20 C. The strength of the solid emulsion is then measured penetration using a texturometer sold under the name TA-XT2i by the company RHEO, equipped with the measuring wheel TA24, 4 mm diameter, from the company STEVENS, using the following measurement conditions: Triggering force (trigger) = 1.0 g Pre-speed = 2.0 mm / s Penetration rate = 0.5 mm / s Depth of penetration = 2 mm The penetration force expressed in grams is read on the device.

  The solid emulsion is then stored for 1 month at 37 ° C. and the emulsion is then placed for 24 hours at 20 ° C. before carrying out the measurement of the hardness (called hardness after 1 month at 37 ° C.) according to the same conditions previously described. .

  The emulsion according to the invention may comprise at least one filler.

  By fillers, it is necessary to include particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured.

  The fillers can be mineral or organic of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (nylon), poly-R-alanine and polyethylene powders, tetrafluoroethylene (Teflon) polymer powders, lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel (Nobel Industry), acrylic acid copolymers, silicone resin microbeads (Toshiba Tospearls, for example) , elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocyanate, hydroxyapatite, hollow silica microspheres, glass or ceramic microcapsules, metal soaps derived from organic acids carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

  The fillers may be present in the composition in a content ranging from 0.1% to 25% by weight, relative to the total weight of the composition, preferably ranging from 1% to 20% by weight, and preferably ranging from 5% by weight. at 15% by weight.

  According to one embodiment of the invention, the emulsion may comprise particles of polymethyl methacrylate. In particular, these particles are not film-forming, that is to say that they do not form a continuous film when they are deposited on a support such as the skin.

  The polymethyl methacrylate powders are generally in the form of hollow or solid spherical particles of white color whose number average size is generally on a micrometer scale, in particular varies from 3 to 15 microns and generally varies from 3 to 10 microns. By average size in number, we denote the dimension given by the statistical size distribution to half of the population, called D50.

  It is also possible to characterize these particles of polymethylmethacrylate by their density, the latter being able to vary in particular according to the size of the spherical cavity of said particles.

  In the context of the present invention, this density is evaluated according to the following protocol, called the packed density: M = 40 g of powder is poured into a graduated cylinder; then the specimen is placed on the STAV 2003 device from STAMPF VOLUMETER; the test piece is then subjected to 1500 settlements; then the final volume Vf of compacted powder is measured directly on the test piece. The packed density is determined by the ratio mNf, in this case 40Nf (Vf being expressed in cm3 and m in g).

  In particular, the density of the polymethyl methacrylate particles that can be used according to the invention can vary from 0.3 to 1.5, especially from 0.5 to 1.5, and more particularly from 1 to 1.5.

  Representative and non-limiting examples of polymethyl methacrylate suitable for the invention include, in particular, polymethymethacrylate particles marketed by MATSUMOTO YUSHI CO under the name Micropearl M100, by LCW under the name Covabead LH 85 and those marketed by the company NIHON JUNYAKU under the name JURYMER MB1.

  The polymethyl methacrylate particles may be present in a content ranging from 0.5% to 10% by weight, relative to the total weight of the composition, preferably ranging from 0.5% to 7% by weight, preferably ranging from 1% to 20% by weight, and more preferably from 0.5% to 5% by weight.

  The emulsion according to the invention may comprise at least one dyestuff which may be chosen from water-soluble or fat-soluble dyes, pigments, pearlescent agents and mixtures thereof.

  By pigments, it is necessary to understand white or colored particles, mineral or organic, insoluble in the liquid organic phase, intended to color and / or opacify the composition.

  By nacres, it is necessary to include iridescent particles, in particular produced by certain shellfish in their shell or else synthesized, insoluble in the mid-40 place of the composition.

  By dyes, it is necessary to understand generally organic compounds soluble in fatty substances such as oils or in a hydroalcoholic phase.

  The pigments may be inorganic or organic pigments. As pigments, it is possible to use metal oxides such as iron oxides (in particular those of yellow, red, brown or black color), titanium dioxides, cerium oxide, zirconium oxide and chromium oxide. ; manganese violet, blue ultramarine, prussian blue, ultramarine blue, ferric blue, bismuth oxychloride, mother-of-pearl, mica coated with titanium or bismuth oxychloride, pearlescent pigments such as than titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride, and their mixtures.

  It is preferable to use pigments of iron oxides or of titanium dioxide. Advantageously, the pigments are treated with a hydrophobic agent to make them compatible with the organic phase of the composition. The hydrophobic treatment agent may be chosen from silicones such as meticones, dimethicones and perfluoroalkylsilanes; fatty acids such as stearic acid; metallic soaps such as aluminum dimyristate, hydrogenated tallow glutamate aluminum salt, perfluoroalkyl phosphates, perfluoroalkyl silanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups, amino acids; N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate, and mixtures thereof.

  The N-acyl amino acids may comprise an acyl group having from 8 to 22 carbon atoms, for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be aluminum, magnesium, calcium, zirconium, zin, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine. The alkyl term mentioned in the compounds mentioned above denotes in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 atoms. of carbon.

  Hydrophobic-treated pigments are described in particular in application EPA-1086683.

  The fat-soluble dyes are, for example, Sudan Red, D & C Red No. 17, D & C Green No. 6, β-Carotene, Soybean Oil, Sudan Brown, D & C Yellow No. 11, D & C Violet No. 2, D & C Orange No. 5, yellow quinoline, annatto, bromoacids.

  The water-soluble dyes are, for example, beet juice, methylene blue, caramel.

  The dyestuffs may be present in a content ranging from 0.5% to 30% by weight, relative to the total weight of the composition, preferably ranging from 3% to 20% by weight, and preferably ranging from 5% to 15% by weight. in weight.

  According to a particular embodiment of the invention, the emulsion may comprise at least one hydrophobic coated powdery material, especially at a content of less than or equal to 20% by weight (for example ranging from 0.1% to 20% by weight ), relative to the total weight of the composition. Said pulverulent material may be chosen from fillers, pulverulent dyestuffs, fillers and pigments as described above. Said pulverulent material is coated with a hydrophobic agent as described above.

  The composition may contain other usual cosmetic ingredients that can be chosen in particular from hydrophilic or lipophilic gelling agents and / or thickeners, antioxidants, perfumes, preservatives, neutralizers, sunscreens, vitamins, moisturizers, compounds and the like. self-tanning agents, anti-wrinkle active agents, emollients, hydrophilic or lipophilic active agents, free antiradical agents, sequestering agents, film-forming agents, and mixtures thereof.

  Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, impaired by the addition considered.

  The composition according to the invention can be prepared according to the following procedure: The mixture of the constituents of the oily phase is prepared on the one hand by mixing and heating the waxes, the block copolymer, at a temperature of between 70 ° C. and 120 ° C. ethylene oxide and / or propylene oxide and alkylene oxide having from 6 to 40 carbon atoms, the non-volatile oils and then adding with stirring, at a temperature between 60 C and 80 C, volatile oils, fillers and pigments.

  On the other hand, the mixture of constituents of the aqueous phase comprising water, surfactants, and water-miscible solvents is prepared by heating at a temperature of between 60 ° C. and 80 ° C.

  The aqueous phase is then added to the oily phase at a temperature of between 60 and 80 ° C., and the mixture is stirred with a turbine until the water-in-oil emulsion is obtained. The emulsion is then poured into a container, for example a cup, and then cooled to room temperature until the solid emulsion is obtained.

  The invention is further illustrated by the examples described below. EXAMPLE 1 A solid foundation was prepared having the following composition: Oily phase: Candelilla wax 1.8 g Ozokerite 1.2 g Isotridecyl isononanoate 9.0 g Cyclopentasiloxane 22.5 g 15 Iron oxides coated with disodium salt of stearoyl glutamate and aluminum hydroxyl 2.2 g titanium dioxide coated with disodium salt of stearoyl glutamate and aluminum hydroxyl 7.8 g hydrophobic fumed silica (Aerosil R972 from Degussa) 0 5 g Silica microspheres 9.0 g Polymethyl methacrylate 3 g Titanium dioxide nanopigments 3 g Copolymer of ethylene oxide (45%) and epoxydodecane (22 moles) sold under the name "ELFACOS ST 9" by the company AKZO NOBEL 4 g Polyglyceryl-4-isostearate 1.50 g Aqueous phase: 30 Water 20 g Butylene glycol 3 g Glycerine 5 g Magnesium sulfate 1 g Cetyl dimethicone copolyol (Abil EM 90 from GOLDSCHMIDT) 2 g Mixture of oxyethylenated oxypropylenated polydimethylsiloxane (18 EO / 18 OP), cyclopentasiloxane and water (10/88/2) (DC 2-5225 C from Dow Corning) 2 g Preservatives 1.50 g The composition was prepared according to the following procedure: C the mixture comprising the waxes, the copolymer ELFACOS ST 9 and the non-volatile oils until a homogeneous and clear mixture is obtained; then volatile oils, pigments and fillers are added with stirring at 70 ° C. The mixture of the ingredients of the aqueous phase is then prepared by heating at 70 ° C., and then the aqueous phase is introduced at 70 ° C. into the oily phase, with stirring, until the water-in-oil emulsion is obtained.

  The emulsion is cast at 70 ° C. in a previously heated cup and then allowed to cool to room temperature until the solid emulsion is obtained. A solid foundation was obtained having a hardness of 98 g measured at 24 hours at 20 ° C. and a hardness of 87 g measured after storage at 37 ° C. for 1 month, the hardness measurements being carried out according to the protocol previously described. This solid foundation therefore has a good stability of the hardness after a storage of one month.

  The foundation is unctuous and creamy when applied to the skin. Example 2: A solid foundation was prepared having the following composition: Oily phase: Candelilla wax 1.8 g Ozokerite 1.2 g Isodecyl neopentanoate 10.2 g Cyclopentasiloxane 22.5 g Iron oxides coated with disodium salt of stearoyl glutamate and aluminum hydroxyl 2.4 g titanium dioxide coated with disodium salt of stearoyl glutamate and aluminum hydroxyl 7.6 g hydrophobic fumed silica (Aerosil R972 from Degussa) 0 5 g Silica microspheres 9.0 g Polymethyl methacrylate 3 g Titanium dioxide nanopigments 3 g Copolymer of ethylene oxide (45%) and epoxydodecane (22 moles) sold under the name "ELFACOS ST 9" by the company AKZO NOBEL 4 g Polyglyceryl-3-diisostearate 0.3 g Aqueous phase: 20 g Water Butylene glycol 3 g Glycerine 5 g Magnesium sulphate 1 g Cetyl dimethicone copolyol 2 g (Abil EM 90 from GOLDSCHMIDT) Blend oxyethylenated oxyethylenated oxypropylenated polydimethylsiloxane 2 g (18 0E / 18 OP), cyclopentasiloxane and water (10/88/2) (DC 2-5225 C from Dow Corning) Preservatives 1.50 g The emulsion was prepared in the same manner as that of Example 1 .

  A solid foundation is obtained having a hardness of 87 g measured at 24 hours at 20 ° C. and a hardness of 78 g measured after storage at 37 ° C. for 1 month, the hardness measurements being carried out according to the protocol previously described. This solid foundation therefore has a good stability of the hardness after a storage of one month.

  When applied to the skin, the foundation is creamy and unctuous.

Claims (43)

  1. Water-in-oil solid emulsion comprising an aqueous phase emulsified with an emulsifying surfactant in a fatty phase comprising an ester oil and a wax, a C8-C22 alkyl dimethicone copolyol, the emulsion having, after at least one month at 37 C, a hardness such that the penetration force is greater than or equal to 45 g.   2. Emulsion according to claim 1, characterized in that the hardness is from 45 g to 150 g, preferably from 50 g to 130 g, preferably from 60 g to 130 g, and more preferably from 70 g. at 130 g.   3. Emulsion according to one of the preceding claims, characterized in that the ester oil is a monoester.   4. Emulsion according to any one of the preceding claims, characterized in that the ester oil is a monoester of formula R1000R2 in which RI represents a hydrocarbon chain, linear or branched, having from 4 to 40 carbon atoms, preferably from 4 to 30 carbon atoms, and preferably from 7 to 20 carbon atoms, and R2 represents a branched hydrocarbon chain containing from 3 to 40 carbon atoms, preferably from 10 to 30 carbon atoms, and preferably from 16 to 20 carbon atoms. at 26 carbon atoms.   5. Emulsion according to any one of the preceding claims, characterized in that the ester oil is chosen from isodecyl neopentanoate, isoketyl octanoate, isononyl isononanoate, isodecyl isononanoate. , tridecyl isononanoate, hexyl laurate, 2-hexyl-decyl laurate, isopropyl myristate, isocetyl myristate, isotridecyl myristate, 2octyldodecyl myristate, isopropyl palmitate, 2-ethyl hexyl palmitate, isooctyl palmitate, isoketyl palmitate, isodecyl palmitate, isostearyl palmitate, 2-octyl decyl palmitate, isopropyl isostearate, 2-octyl dodecyl stearate, isostearyl isostearate, 2-octyl dodecyl erucate, and mixtures thereof.   6. Emulsion according to any one of the preceding claims, characterized in that the ester oil is present in a content ranging from 5% to 20% by weight, relative to the total weight of the composition, preferably ranging from % to 15% by weight, and preferably ranging from 8% to 12% by weight.   7. Emulsion according to any one of the preceding claims, characterized in that the alkyl C8-C22 dimethicone copolyol is a compound of formula (I) below: CH3 Si 0 ICH2) q O I PE m   (CH 3) 3 SiOCH 3 SiOCH 2) p CH 3 CH 3 SiO CH 3 n Si (CH 3) 3 o (1) in which: - PE represents (-C 2 H 4 O) x- (C 3 H 6 O) r R, R being chosen from an atom hydrogen and an alkyl radical of 1 to 4 carbon atoms, x ranging from 0 to 100 and y ranging from 50 to 80, x and y not being simultaneously 0 - m ranging from 1 to 40 - n ranging from 10 to 200 - o ranging from 1 to 100 - p ranging from 7 and 21 - q ranging from 0 to 4.   8. Emulsion according to any one of the preceding claims, characterized in that the alkyl C8-C22 dimethicone copolyol is present in a content ranging from 0.1% to 5% by weight, relative to the total weight of the composition and preferably from 1% to 3% by weight.   9. Emulsion according to any one of the preceding claims, characterized in that it comprises an additional surfactant different from the alkyl C8-C22 dimethicone copolyol.   10. Emulsion according to the preceding claim, characterized in that the additional surfactant is selected from fatty acid esters of polyols such as mono-, di-, tri- or sesqui-oleates or stearates of sorbitol or glycerol, laurates of glycerol or polyethylene glycol; polymers of the polyoxyalkylene glycol fatty acid ester type, polyhydroxylated silicones, especially polyglycerolated silicones, and emulsifying silicone elastomers.   11. Emulsion according to claim 9 or 10, characterized in that the additional surfactant is present in a content ranging from 0.05% to 3% by weight, relative to the total weight of the composition, and preferably ranging from , 1% to 2% by weight.   12. Emulsion according to any one of the preceding claims, characterized in that the wax has a hardness ranging from 5 MPa to 9 MPa.   13. Emulsion according to any one of the preceding claims, characterized in that the wax has a hardness ranging from 6 MPa to 9 MPa, and preferably ranging from 7 MPa to 9 MPa.   14. Emulsion according to any one of the preceding claims, characterized in that the wax is chosen from carnauba wax, microcrystalline waxes, ozokerites, hydrogenated jojoba oil, polyethylene waxes, poly waxes. alkyl C24-C28 methyl dimethyl siloxane, palm butter, C20C40 alkyl stearate, stearyl benzoate, Shellac wax, and mixtures thereof.   15. Emulsion according to any one of the preceding claims, characterized in that the wax is chosen from carnauba wax, ozokerites, hydrogenated jojoba oil, polyethylene waxes.   16. Emulsion according to any one of the preceding claims, characterized in that the wax is chosen from Candelilla wax, ozokerite, and mixtures thereof.   17. Emulsion according to any one of the preceding claims, characterized in that the wax is present in a content ranging from 1% to 10% by weight, relative to the total weight of the composition, preferably ranging from 2% to 7% by weight, and preferably ranging from 2% to 5% by weight.   18. Emulsion according to any one of the preceding claims, characterized in that the fatty phase comprises a volatile silicone oil.   19. Emulsion according to the preceding claim, characterized in that the volatile siilcone oil is selected from octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.   20. Emulsion according to claim 18 or 19, characterized in that the volatile silicone oil is present in a content ranging from 5% to 40% by weight, relative to the total weight of the composition, preferably ranging from % to 30% by weight, and preferably ranging from 15% to 30% by weight.   21. Emulsion according to any one of the preceding claims, characterized in that it comprises an additional oil, different from ester oils and volatile silicone oils.   22. Emulsion according to the preceding claim, characterized in that the additional oil is selected from hydrocarbon oils, fluorinated oils, volatile or non-volatile.   23. Emulsion according to claim 21 or 22, characterized in that the additional oil is present in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition, and preferably ranging from 0.1% to 5% by weight.   24. Emulsion according to any one of the preceding claims, characterized in that it contains water in a content ranging from 10% to 40% by weight, relative to the total weight of the composition, preferably ranging from 15% to 30% by weight, and preferably ranging from 15% to 25% by weight.   25. Emulsion according to any one of the preceding claims, characterized in that it comprises a water-miscible solvent selected from monoalcohols having from 2 to 6 carbon atoms, the polyols having from 2 to 20 carbon atoms. glycol ethers having from 3 to 16 carbon atoms, and mixtures thereof.   26. Emulsion according to the preceding claim, characterized in that the water-miscible solvent is chosen from glycerine, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol. , mono-, di- or tripropylene glycol (C1-C4) alkyl ethers, mono-, di- or triethylene glycol (C1-C4) alkyl ethers, ethanol, isopropanol, and mixtures thereof.   27. Emulsion according to claim 25 or 26, characterized in that the organic solvent miscible with water is present in a content ranging from 1% to 20% by weight, relative to the total weight of the composition, and preferably ranging from 3% to 15% by weight.   28. Emulsion according to any one of the preceding claims, characterized in that it comprises a pasty fatty substance.   29. Emulsion according to the preceding claim, characterized in that the pasty fatty substance is a block copolymer of ethylene oxide and / or of propylene oxide and of alkylene oxide having from 6 to 40 carbon atoms, the copolymer having a weight average molecular weight of from 5,000 to 8,000.   30. Emulsion according to any one of the preceding claims, characterized in that it comprises at least one filler.   31. Emulsion according to the preceding claim, characterized in that the filler is selected from talc, mica, silica, kaolin, polyamide powders, poly-8-alanine powders, polyethylene powders, tetrafluoroethylene polymer powders, lauroyllysine, starch, boron nitride, hollow microspheres of polyvinylidene acrylonitrile chloride, hollow microspheres of acrylic acid copolymers, silicone resin microbeads, elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres, glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms carbon.   32. Emulsion according to claim 30 or 31, characterized in that the filler is present in a content ranging from 0.1% to 25% by weight, relative to the total weight of the composition, preferably from 1 % to 20% by weight, and preferably ranging from 5% to 15% by weight.   33. Emulsion according to any one of the preceding claims, characterized in that it comprises particles of polymethyl methacrylate.   34. Emulsion according to the preceding claim, characterized in that the polymethyl methacrylate particles are present in a content ranging from 0.5% to 10% by weight, relative to the total weight of the composition, preferably ranging from From 5% to 7% by weight, preferably from 1% to 20% by weight, and more preferably from 0.5% to 5% by weight.   35. Emulsion according to any one of the preceding claims, characterized in that it comprises at least one dyestuff.   36. Emulsion according to any one of the preceding claims, characterized in that it comprises at least one hydrophobic coated powdery material.   37. Emulsion according to the preceding claim, characterized in that the pulverulent material is chosen from fillers and pulverulent dyestuffs.   38. Emulsion according to claim 36 or 37, characterized in that the pulverulent material is coated with a hydrophobic agent chosen from silicones, fatty acids, metal soaps, perfluoroalkyl phosphates, perfluoroalkyl silanes and perfluoroalkyl silazanes. , hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups, amino acids, N-acyl amino acids or their salts, lecithin, isopropyl trisostearyl titanate, and mixtures thereof.   39. Emulsion according to any one of the preceding claims, characterized in that the hydrophobic coated powdery material and has a content less than or equal to 20% by weight, relative to the total weight of the composition.   40. Emulsion according to any one of the preceding claims, characterized in that it comprises a cosmetic ingredient selected from gelling agents and / or hydrophilic or lipophilic thickeners, antioxidants, perfumes, preservatives, neutralizers, sunscreens, vitamins, moisturizers, self-tanning compounds, anti-wrinkle active agents, emollients, hydrophilic or lipophilic active agents, anti-free radical agents, sequestering agents, film-forming agents, and mixtures thereof.   41. Composition according to any one of the preceding claims, characterized in that the composition is a foundation, an eyeshadow, a blusher, a concealer, a body makeup product, a lipstick. , a skincare base, a care cream; a care composition for the lips; a sun protection composition, a self-tanning composition; a deodorant.   42. A foundation composition comprising a composition according to any one of claims-1 to 41.   43. Cosmetic makeup or non-therapeutic skin care method comprising the application to the skin of a composition according to any one of the preceding claims.