Anhydrous fluorinated composition and care or cosmetical products containing it

The present invention relates to an anhydrous and homogeneous composition comprising in combination at least one fluorinated oil and at least one fluorinated wax with carbon skeleton.

The present invention also relates to make-up or care products containing such an anhydrous composition.

The use of fluorinated oils in the formulation of cosmetic compositions is particularly sought-after insofar as fluorinated oils confer good film-forming properties and resistance to water and sebum.

However, such compositions are difficult to produce because of the inherent incompatibility of fluorinated oils with many polar and nonpolar hydrocarbon compounds.

Homogeneous combinations of fluorinated oils and waxes have already been made using surfactants, but until now it has not been possible to obtain compositions, in particular anhydrous, based on fluorinated oils in the absence surfactants.

After numerous studies on various types of compounds, it has been found, surprisingly and unexpectedly, that by combining certain fluorinated oils with at least one fluorinated wax with carbon skeleton, anhydrous mixtures of perfect homogeneity could be produced.

It has also been found that this particular combination could advantageously constitute the fatty phase of various makeup and care compositions having in particular an excellent texture and conferring on the skin, after application, a great softness and a pleasant touch.

The present invention therefore relates to an anhydrous and homogeneous composition or phase comprising in combination at least one fluorinated oil and at least one fluorinated wax with carbon skeleton, optionally interrupted by an oxygen atom.

The expression “fluorinated wax with carbon skeleton” is understood to mean a compound solid at room temperature having a melting point greater than or equal to approximately 30 ° C. and comprising a number of fluorine atoms preferably greater than that of the atoms of hydrogen, the carbon skeleton being able to be interrupted by at least one oxygen atom. This wax contains only fluorine, hydrogen and carbon atoms and possibly oxygen.

By oil is meant a non-aqueous liquid compound, at room temperature (25 ° C).

Among the fluorinated oils compatible with fluorinated waxes with a carbon skeleton, mention may in particular be made of perfluorinated compounds, fluorinated silicones, fluoroalkyl and heterofluoroalkyl compounds.

By perfluorinated compounds is meant according to the invention, compounds in which all the hydrogen atoms have been substituted by fluorine atoms.<ul id="ul0001" list-style="none"><li><b>AT</b> - Among the perfluorinated compounds corresponding to this definition, there may be mentioned in particular:<ul id="ul0002" list-style="none"><li>1) the perfluoropolyethers corresponding to the following formulas (l) and (ll);<chemistry id="chem0001" num="0001"><img file="EP0953331A2_D0001.tif" /></chemistry> in which :<ul id="ul0003" list-style="none" compact="compact"><li>n is 7 to 30; and<chemistry id="chem0002" num="0002"><img file="EP0953331A2_D0002.tif" /></chemistry></li><li>the m / m 'ratio being from 20 to 40, and</li><li>the molecular weight being from 500 to 20,000.</li></ul> Among these perfluoropolyethers of formulas (l) and (ll), mention may be made, respectively, of that sold under the name of "FLUORTRESS LM36^®"by the company DUPONT, and those sold under the general name of" FOMBLIN "by the company MONTEFLUOS for example FOMBLIN HC R^® of vapor pressure 10^-7 mm Hg.</li><li>2) the perfluorocycloalkyl compounds of formula (III) below:         (CF₂)_e (CF-CCF₂)_p-F)_g     (III) in which :<ul id="ul0004" list-style="none" compact="compact"><li>e is equal to 4 or 5,</li><li>g is 1 or 2, and</li><li>p is 1, 2 or 3;</li></ul> provided that when g = 2, the groupings are not necessarily in alpha with respect to each other. Among the compounds of formula (III), mention may in particular be made of perfluoromethylcyclopentane and perfluorodimethylcyclohexane, sold respectively under the names of "FLUTEC PC1^®"vapor pressure 368 mbar and" FLUTEC PC3^®"by the company BNFL FLUOROCHEMICALS Ltd.; and</li><li>3) perfluorophenanthrene sold under the name of "FLUTEC PC11^®"by the company BNFL FLUOROCHEMICALS Ltd.</li></ul></li></ul><ul id="ul0005" list-style="none"><li><b>B</b> - Among the fluorinated silicones, mention may in particular be made of the fluoro-silicone compounds corresponding to the following formula (IV):<chemistry id="chem0003" num="0003"><img file="EP0953331A2_D0003.tif" /></chemistry> in which :<ul id="ul0006" list-style="none" compact="compact"><li>k is 1 to 17,</li><li>l is 1 to 18,</li><li>p is 1 to 6, and</li><li>R₁ represents a hydrogen atom or a C 1 alkyl radical₁-VS₆,</li><li>R₂ represents a C 1 alkyl radical₁-VS₆ or the radical -OSi (R₃)₃, and</li><li>R₃ represents a C 1 alkyl radical₁-VS₄.</li></ul> Among the compounds corresponding to formula (IV), there may be mentioned in particular:<ul id="ul0007" list-style="dash" compact="compact"><li>N - (- 2-F-octyl-ethyloxycarbonyl) -3-aminopropyl bis (trimethylsiloxy) methylsilane,</li><li>N - (- 2-F-hexyl-ethyloxycarbonyl) -3-aminopropyl bis (trimethylsiloxy) methylsilane,</li><li>N - (- 2-F-butyl-ethyloxycarbonyl) -3-aminopropyl bis (trimethylsiloxy) methylsilane,</li><li>N - (- 2-F-octyl-ethyloxycarbonyl) -3-aminopropyl tris (trimethylsiloxy) silane,</li><li>N - (- 2-F-hexyl-ethyloxycarbonyl) -3-aminopropyl tris (trimethylsiloxy) silane, and</li><li>N - (- 2-F-butyl-ethyloxycarbonyl) -3-aminopropyl tris (trimethylsiloxy) silane.</li></ul></li><li><b>VS</b> - Among the fluoroalkyl or heterofluoroalkyl compounds, mention may be made of those corresponding to the following formula (V):         CH₃- (CH₂)_h- [Z]_t- (CF₂)_j-CF₃     (V)    in which :<ul id="ul0008" list-style="none" compact="compact"><li>t is 0 or 1,</li><li>h is 0, 1, 2 or 3,</li><li>i is 2, 3, 4 or 5, and</li><li>Z represents O, S or NR₄</li><li>R₄ representing hydrogen, a radical - (CH₂)_h-CH₃ or - (CF₂)_i-CF₃.</li></ul> Among the compounds of formula (V), mention may in particular be made of methoxynonafluorobutane sold under the name "MSX 4518^®"by the company 3M (t = 1, Z = O, n = 0 and m = 3) or ethoxynonafluorobutane sold under the name" HFE 7200 "by the company Archimex (t = 1, Z = O, n = 1 and m = 3). The oils of the invention have a boiling temperature &lt;220 ° C, preferably less than 120 ° C. Among the fluorinated waxes with a carbon skeleton, as defined above, capable of forming an anhydrous composition homogeneous with the fluorinated oils, mention may in particular be made of fluorinated esters corresponding to the following formula (VI):<chemistry id="chem0004" num="0004"><img file="EP0953331A2_D0004.tif" /></chemistry> in which :<ul id="ul0009" list-style="none" compact="compact"><li>R₄ represents a hydrogen atom or the radical<chemistry id="chem0005" num="0005"><img file="EP0953331A2_D0005.tif" /></chemistry></li><li>A represents an alkylene or alkenylene chain, linear or branched, optionally hydroxylated, at C₁-VS₁₈,</li><li>it's 1 to 17, and</li><li>d is 1 to 18.</li></ul>Among the compounds of formula (VI), mention may especially be made of dodecane 1,12, 2F-octyl-ethyl dioate of the following formula:<chemistry id="chem0006" num="0006"><img file="EP0953331A2_D0006.tif" /></chemistry>    and C-perfluoroalkyl tri-citrates₁-VS₆, more particularly perfluorobutyl tri-citrate sold under the name "ZONYL TBC^®"by the DUPONT Company. As other fluorinated waxes which can be used in the invention, mention may be made of polytetrafluoroethylene (PTFE) waxes. Preferably, waxes having a melting point ranging from 45 ° C. to 150 ° C. are used, in particular such as the fluorinated esters of formula (VI). In the anhydrous composition according to the invention, the fluorinated oils are generally present in a proportion of between 20 and 95% by weight, but preferably between 60 and 80% by weight relative to the total weight of the composition. The fluorinated waxes with a carbon skeleton are generally present in a proportion of between 5 and 80% by weight, but preferably between 20 and 40% by weight relative to the total weight of the composition. According to a particular embodiment, the anhydrous composition as defined above, can also contain one or more other fatty substances which can be chosen from oils, waxes, gums and / or so-called pasty fatty substances.<ul id="ul0010" list-style="none"><li><b>at</b> - The oils of the anhydrous composition can be of mineral, animal, vegetable or synthetic origin, these can be volatile or not at room temperature. As mineral oil, mention may in particular be made of paraffin oil. As oil of animal origin, there may be mentioned in particular squalene or perhydrosqualene. As vegetable oil, there may be mentioned in particular sweet almond oil, calophyllum oil, palm oil, avocado oil, jojoba oil, sesame oil, olive oil, castor oil and cereal germ oils such as for example wheat germ oil. As synthetic oil, there may be mentioned in particular:<ul id="ul0011" list-style="none"><li>(1) the esters of formula:         R₅-COOR₆in which :<ul id="ul0012" list-style="none" compact="compact"><li>R₅ represents the remainder of a higher C fatty acid₇-VS₂₀, and</li><li>R₆ represents a C hydrocarbon radical₃-VS₃₀.</li></ul></li><li>Among these esters, mention may especially be made of: Purcellin oil, butyl myristate, isopropyl myristate, cetyl myristate, isopropyl palmitate, butyl stearate, hexadecyl stearate, stearate isopropyl, octyl stearate, isoketyl stearate, decyl oleate, hexyl laurate, isononyl isononanoate, lanolic acid esters such as isopropyl lanolate and isocetyl lanolate. As other synthetic oils, mention may also be made of isododecane, isohexadecane, polyisobutenes and hydrogenated polyisobutene as well as acetylglycerides, octanoates and decanoates of polyalcohols such as those of glycol and glycerol, ricinoleates of alcohols or polyalcohols such as cetyl ricinoleate, propylene glycol dicaprylate and diisopropyl adipate;</li><li>(2) fatty alcohols such as oleic alcohol, linoleic alcohol, linolenic alcohol, isostearyl alcohol and octyldodecanol;</li><li>(3) silicone oils such as optionally functionalized linear polydiorganosiloxanes, cyclic polydiorganosiloxanes and in particular cyclotetra- and penta-dimethicones and organopolysiloxanes such as alkyl, alkoxy or phenyl dimethicones and in particular phenyltrimethi-cone;</li></ul></li></ul>The oils can represent from 0 to 50% and better still from 0 to 20% of the total weight of the composition.</li><li><b>b</b>- The waxes of the anhydrous composition, other than fluorinated waxes, can be of mineral, fossil, animal, vegetable, synthetic origin or even be hydrogenated oils or fatty fatty esters at 25 ° C. Among the mineral waxes, mention may in particular be made of microcrystalline waxes, paraffin, petrolatum and ceresin. Among the fossil waxes, there may be mentioned ozokerite and montan wax. Among the waxes of animal origin, mention may be made of beeswax, spermaceti, lanolin wax and also derivatives derived from lanolin such as lanolin alcohols, hydrogenated lanolin, hydroxylated lanolin, acetylated lanolin , lanolin fatty acids and acetylated lanolin alcohol. Among the waxes of vegetable origin, mention may in particular be made of candellila wax, carnauba wax, Japanese wax and cocoa butter. Among the synthetic waxes, mention may in particular be made of homopolymers of ethylene and copolymers of ethylene and of a monomer corresponding to the following formula:         CH₂= CH-R₇in which : R₇ represents a radical in C₁-VS₃₀, an aryl or aralkyl radical; R₇ preferably being a methyl, ethyl, propyl, isopropyl, butyl, decyl, dodecyl or octadecyl radical. It is also possible to use waxes obtained by Fis-her-Tropsch synthesis as well as silicone waxes. Among the hydrogenated oils which are concrete at 25 ° C., there may be mentioned in particular hydrogenated castor oil, hydrogenated palm oil, hydrogenated tallow and hydrogenated coconut oil. Among the concrete fatty esters at 25 ° C., there may be mentioned in particular propylene glycol mono-myristate and myristyl myristate. As waxes which can be used in the compositions according to the invention, mention may also be made of cetyl alcohol, stearyl alcohol, mono-, di- and triglycerides concrete at 25 ° C., stearic monoethanolamide, rosin and its derivatives such than the abietates of glycol and glycerol, the sugar glycerides and the oleates, myristates, lanolates, stearates and dihydroxystearates of calcium, magnesium, zinc and aluminum. Preferably, waxes having a melting point ranging from 45 ° C. to 150 ° C. are used. They represent in particular from 0 to 20% of the total weight of the composition.</li><li><b>vs</b>- The fatty substances of the pasty type can be of mineral, animal, vegetable or synthetic origin. Among the pasty fatty substances, there may be mentioned in particular synthetic esters such as arachidyl propionate, vinyl polylaurate, polyethylene waxes and organopolysiloxanes such as alkyldimethicones, alkoxydimethicones or esters of dimethicones. The present invention also relates to a makeup or care composition or product containing an anhydrous and homogeneous composition or phase as defined above. According to a first particular embodiment, the makeup or care product is anhydrous and contains the anhydrous and homogeneous composition in a proportion of between approximately 0.5 and 100% by weight relative to the total weight of the product. This anhydrous product can be in the form of a stick such as for example a lipstick or a concealer, or in the form of an anhydrous compact such as for example a foundation , an eyeshadow, a blush or a mascara. When the anhydrous product is in the form of a stick or a compact, it may contain pigments as well as fillers in the form of fine particles having an average size of between 0.02 and 50 μm. The pigments can be mineral or organic or in the form of metallic lacquers. Among these pigments, mention may be made of titanium dioxide, zinc oxide, D&amp;C Red No, 36 and D&amp;C orange No. 17, calcium lakes of D&amp;C Red No. 7, 11, 31 and 34, lacquer barium by D&amp;C Red No. 12, strontium lacquer D&amp;C Red No. 13, aluminum lacquers by FD&amp;C Yellow No. 5, FD&amp;C Yellow No. 6, D&amp;C Red No. 27, D&amp;C Red No. 21, from FD&amp;C Blue No. l, iron oxides, manganese violet, chromium oxide and overseas blue.</li></ul>

The fillers can be of natural or synthetic origin. Among these, we can notably cite:<ul id="ul0013" list-style="none" compact="compact"><li>i) mineral powders such as talc, kaolin, mica, silica, silicates, alumina, zeolites, hydroxyapatite, sericite, micatitanes, barium sulphate, bismuth oxychloride, boron nitride and metal powders such as aluminum powder;</li><li>ii) vegetable powders such as starch, corn, wheat or rice powders;</li><li>iii) organic powders such as nylon, polyamide, polyester, polytetrafluoroethylene or polyethylene powders.</li></ul>

These different powders can also be coated, for example, with metal salts of fatty acids, amino acids, lecithin, collagen, silicone compounds, fluorinated compounds or by any other usual coating.

In addition to the pigments as defined above, at least one dye may also be present and, among these, mention may be made of eosin derivatives such as D&amp;C Red No. 21 and halogenated fluoroscein derivatives such than D&amp;C Red No. 27, D&amp;C orange No. 5 in combination with D&amp;C Red No. 21 and D&amp;C orange No. 10.

In make-up or care products, the proportion of pigments and / or dyes is generally between approximately 0.1 and 25% and better still between 0.1 and 15% by weight relative to the total weight of these products.

The fillers can generally be present in make-up or care products in a maximum proportion of approximately 98% by weight relative to the total weight of these products.

Anhydrous products as defined above, can of course also contain one or more conventional cosmetic or dermatological additives or adjuvants.

According to a second embodiment, the makeup or care product is a dispersion, in the form of a stable water-in-oil (W / O) or oil-in-water (O / W) emulsion , which essentially consists of (i) an anhydrous and homogeneous composition or phase as defined above in a proportion of between approximately 0.1 and 50% by weight relative to the total weight of the composition, (ii) an aqueous phase in a proportion of between approximately 4 and 97% by weight relative to the total weight of the composition, and (iii) of at least one emulsifying agent in a proportion of between approximately 0.5 and 10% by weight relative to the total weight of the dispersion.

As emulsifier or surfactant which can be used in the compositions in the form of a W / O or O / W emulsion, mention may in particular be made of silicone surfactants, and in particular those belonging to the family of dimethicone copolyols and alkyl- or alkoxydimethicones copolyols. Among the latter, there may be mentioned in particular the compounds corresponding to the following general formula:<chemistry id="chem0007" num="0007"><img file="EP0953331A2_D0007.tif" /></chemistry> in which :<ul id="ul0014" list-style="none" compact="compact"><li>R₈ is a hydrogen atom, a C alkyl₁-VS₁₆, an alkoxy or acyl,</li><li>R₉ is a C alkyl or alkoxy radical₈-VS₄₅,</li><li>u = 0 to 200,</li><li>v = 1 to 40,</li><li>w = 0 to 100,</li></ul> the molecular weight of the radical -O- (C₂H₄O)_x-(VS₃H₆O)_y-R₈ being from 250 to 2000, x and y being chosen such that the weight ratio of the oxyethylen / oxypropylene groups is between 100: 0 and 20:80.

Among the commercial products which may contain all or part of the al-kyldimethicones copolyols, mention may in particular be made of those sold under the names of "ABIL WE09^®"," ABIL EM90^®"or" ABIL WS08^®"by the company GOLDSCHMIDT, of" Q2 5200^®"or" Q2 3225C^®"by the company DOW CORNING and" 218 | 138® "by the company GENERAL ELECTRIC.

The surfactants can also be chosen from anionic or nonionic surfactants. On this subject, see the document "Encyclopedia of Chemical Technology, KlRK-OTHMER", volume 22, pages 333-432, 3^th edition, 1979 WILEY, for the definition of the properties and functions (emulsifier) ​​of surfactants, in particular pages 347-377 of this reference, for anionic and nonionic surfactants.

The surfactants of these two groups preferably used in the compositions according to the invention are:<ul id="ul0015" list-style="none" compact="compact"><li>- among the nonionic surfactants: fatty acids, fatty alcohols, polyethoxylated or polyglycerolated fatty alcohols, such as polyethoxylated stearyl or cetylstearyl alcohols, fatty acid and sucrose esters, alkyl glucose esters, in particular esters of alkyl glucose alkyl fatty (C₁ -VS₆) polyoxyethylenated glucose, and</li><li>- among anionic surfactants: amine stearates.</li></ul>

These dispersions are preferably in the form of creams and can be used as make-up or care products.

The products or compositions as described above, whether they are of the anhydrous type or in the form of a dispersion, have excellent cosmetic properties such as in particular an excellent texture, as well as very good resistance on the skin vis -to friction, water or sebum.

These products or compositions as just described above, may also contain one or more conventional cosmetic adjuvants such as vitamins, hormones, antioxidants, preservatives, perfumes, thickeners, agents moisturizers, humectants, anionic, nonionic or amphoteric polymers, cosmetic or dermatological active ingredients.

The invention is illustrated by the following examples, the amounts of which are expressed by weight.

EXAMPLES OF COSMETIC COMPOSITION

<ul id="ul0016" list-style="none"><li><u><i>Example 1</i></u>: <b>Lipstick</b> A lipstick is prepared according to the invention by mixing the following ingredients:<ul id="ul0017" list-style="dash" compact="compact"><li>Polyperfluoroisopropylether sold under the name of "FLUORTRESS LM 36^®" by the Society</li><li>DUPONT 5 g</li><li>Dodecane 1.12 2F-octyl-ethyl dioate 40 g</li><li>Perfluorodecaline 35 g</li><li>Methoxynonafluorobutane sold under the name of "MS X 4518^®"by the company 3M 10 g</li><li>Pigments 10</li></ul></li><li><i><u>Example 2</u></i>: <b>Stick foundation</b> A foundation is prepared according to the invention, by mixing the following ingredients:<ul id="ul0018" list-style="dash" compact="compact"><li>Dodecane 1.12 2F-octyl-ethyl dioate 30 g</li><li>N - (- 2-F-octyl-ethyloxycarbonyl) -3-amino-propyl bis (trimethylsiloxy) methylsilane 60 g</li><li>Pigments 10 g</li></ul></li><li><u><i>Example 3</i></u>: Care cream A water-in-oil emulsion is prepared with the following ingredients according to the conventional methods of manufacturing emulsions:<ul id="ul0019" list-style="dash" compact="compact"><li>FLUORTRESS LM 36 (1) g</li><li>Zonyl TBC (2) 8 g</li><li>Tri-fluoromethyl C_1-4 alkyl dimethicone (Shin</li><li>Etsu) 12 g</li><li>Abil WE 09 (3) 5 g</li><li>Salt 0.7 g</li><li>Water qps100 g<ul id="ul0020" list-style="none" compact="compact"><li>(1) polyperfluoroisopropyl ether (Dupont de Nemours)</li><li>(2) tri-perfluoroalkyl ethyl citrate (Dupont de Nemours)</li><li>(3) 4-polyglyceryl isostearate / cetyl dimethicone copolyol / hexyl laurate</li><li>(Goldschmidt).</li></ul></li></ul></li></ul>