Patent Application
20170181939
The present invention relates to a composition in the form of an oil-in-water emulsion comprising a) at least one continuous aqueous phase, b) at least one oily phase dispersed in said aqueous phase, c) at least one mixture of surfactants comprising i) one or more fatty acid esters of a polyalkylene glycol, ii) one or more fatty acid esters of glycerol, iii) one or more fatty acids in free form and iv) one or more alkali metal salts of an ester of phosphoric acid and of a fatty alcohol, and d) one or more UV-screening agents.
It is known that light radiation with wavelengths of between 280 nm and 400 nm permits tanning of the human epidermis and that rays with wavelengths more particularly between 280 and 320 nm, known as UVB rays, cause skin redness which can harm the development of a natural tan.
For these reasons, and also for aesthetic reasons, there is constant demand for means for controlling this natural tanning in order thus to control the colour of the skin; this UVB radiation should thus be screened out.
It is also known that UVA rays, with wavelengths between 320 and 400 nm, which cause tanning of the skin, are liable to induce adverse changes therein, in particular in the case of sensitive skin or skin that is continually exposed to solar radiation. UVA rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature ageing of the skin.
Thus, for aesthetic and cosmetic reasons, for instance conservation of the skin's natural elasticity, more and more people wish to control the effect of UVA rays on their skin. It is thus desirable also to screen out UVA radiation.
For the purpose of protecting the skin and keratin materials against UV radiation, cosmetic anti-sun compositions comprising UV-screening agents that are active with respect to the screening out of UVA and UVB radiation are generally used.
Among the various textures which currently exist, anti-sun compositions which are in the form of a fluid are generally highly liked by consumers since their fluidity allows them to be applied rapidly and easily over the whole of the body. In particular, these compositions in fluid form may be oil-in-water emulsions and may be sprayed onto the skin in the form of droplets of milk in order to obtain very safe tanning By way of example, milk sprays are among the most fluid anti-sun compositions used, which can be deposited on the skin using an aerosol device or a spray pump device.
However, such compositions are generally difficult to spray, making their distribution on the skin usually not very uniform. Furthermore, these compositions need to be spread once again by the user in order to be sure to benefit from good protection against ultraviolet radiation.
The quality of spraying of a composition onto a surface is generally related to its viscosity, which should be as low as possible, which goes against its stability and its screening efficiency. Indeed, if the photoprotective composition is very fluid, then, on the one hand, it will be difficult to stabilize it and, on the other hand, it will result in an uneven deposit on the skin, which is not favourable to obtaining efficient protection against ultraviolet radiation.
Moreover, once sprayed, the compositions generally produce a relatively film-forming and tacky feel which is unliked by users.
There is therefore a real need to provide compositions in the form of oil-in-water emulsions which do not have the abovementioned drawbacks, in particular which are stable and fluid while at the same time being capable of efficiently screening out ultraviolet radiation.
The applicant has discovered, surprisingly, that, by combining one or more fatty acid esters of a polyalkylene glycol, one or more fatty acid esters of glycerol, one or more fatty acids in free form and one or more alkali metal salts of an ester of phosphoric acid and of a fatty alcohol in a composition in the form of an oil-in-water emulsion comprising one or more UV-screening agents, it is possible to obtain an anti-sun composition having a very high sun protection factor (SPF), which is stable and extremely fluid.
A sun protection factor (SPF) which can reach a value of 50 is intended. The level of sun protection is defined by the sun protection factor (SPF) which is determined according to the “in vitro” method described by B. L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133 (1989). The measurements were made using a UV-1000S spectrophotometer from the company Labsphere. Each composition is applied to a rough plate of PMMA, in the form of a homogeneous and even deposit in a proportion of 1 mg/cm2.
The term “extremely fluid” is intended to mean that the viscosity of the compositions of the invention is less than or equal to 0.10 Pa·s at a temperature of 25° C., the viscosity being measured using a Rheomat 180 (from the company Lamy), equipped with an MS-R1, MS-R2, MS-R3, MS-R4 or MS-R5 spindle chosen according to the consistency of the composition, rotating at a rotation speed of 200 rpm.
The term “stable emulsions” is intended to mean emulsions which, after 2 months of storage at from 25° C. to 45° C., do not exhibit any macroscopic change in colour, in odour or in viscosity, nor any variation in pH, and also no variation in microscopic appearance.
In other words, it is noted that the combination of surfactants used to stabilize the compositions in the form of an oil-in-water emulsion in accordance with the invention makes it possible to obtain photoprotective compositions which efficiently protect against UVA and UVB rays, and which are extremely fluid and stable.
Thus, the spraying qualities of the compositions according to the invention are improved by virtue of their considerable fluidity.
In particular, it is noted that the compositions according to the invention comprising such a combination of surfactants are more stable and more fluid and produce better performance levels in terms of sun protection factor than identical compositions not comprising the set of abovementioned surfactants.
In addition, the compositions according to the invention have good cosmetic properties and also exhibit good persistence with respect to water.
A subject of the present invention is in particular a composition in the form of an oil-in-water emulsion comprising:
a) a continuous aqueous phase,
b) an oily phase dispersed in said aqueous phase,
c) at least one mixture of surfactants comprising:
d) one or more UV-screening agents;
said composition having a viscosity of less than or equal to 0.10 Pa·s at a temperature of 25° C., according to the measurement method described hereinafter.
The invention also relates to the use of the mixture of surfactants as described previously, for stabilizing a composition in the form of an oil-in-water emulsion containing one or more UV-screening agents.
The invention also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the skin, of at least one composition as defined previously.
The invention also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material of at least one composition as defined previously.
Other subjects and characteristics, aspects and advantages of the invention will become even more clearly apparent on reading the description and the examples which follow.
Preferably, the composition comprises a physiologically acceptable medium and more preferentially a cosmetically acceptable medium.
For the purposes of the present invention, the term “physiologically acceptable medium” is intended to mean a medium that is suitable for the topical administration of a composition. A physiologically acceptable medium is preferentially a cosmetically or dermatologically acceptable medium, i.e. a medium that has no unpleasant odour or appearance, and that is entirely compatible with the topical administration route.
The viscosity of the compositions of the invention is measured using a Rheomat 180 (from the company Lamy), equipped with an MS-R1, MS-R2, MS-R3, MS-R4 or MS-R5 spindle chosen according to the consistency of the composition, rotating at a rotation speed of 200 rpm.
The term “fatty acid ester of a polyalkylene glycol” is intended to mean the esters of polyethylene glycol and of fatty acids, in particular of saturated or unsaturated fatty acids comprising from 12 to 30 carbon atoms, preferably from 14 to 26 carbon atoms, such as oleic alcohol or stearic acid, and comprising from 1 to 200 oxyethylene (OE) groups, preferably from 1 to 100 oxyethylene groups, such as polyethylene glycol 2 OE monostearate (INCI name: PEG-2 stearate) or polyethylene glycol 100 OE monostearate (INCI name: PEG-100 stearate). These polyethylene glycol esters may consists of 1 to 10 fatty chains.
Preferably, the fatty acid ester of a polyalkylene glycol of the compositions of the invention is PEG-100 stearate.
The fatty acid ester of a polyalkylene glycol may be present in a content ranging from 0.1% to 15% by weight relative to the total weight of the composition and preferably ranging from 0.5% to 5% by weight.
The term “fatty acid ester of glycerol” is intended to mean the esters of glycerol and of fatty acids, in particular of saturated or unsaturated fatty acids comprising from 12 to 30 carbon atoms, preferably from 14 to 26 carbon atoms, such as oleic alcohol or stearic acid, and comprising from 1 to 20 glyceryl groups, preferably from 1 to 10 glycerl units, such as glyceryl monostearate, glyceryl isostearate, diglyceryl distearate, tetraglyceryl tristearate, decaglyceryl decastearate, diglyceryl monostearate, hexaglyceryl tristearate, decaglyceryl pentastearate, the ester of glycerol and of palmitic and stearic acids, or glyceryl mono- and dibehenate.
Preferably, the fatty acid ester of glycerol of the compositions of the invention is chosen from glyceryl monostearate, glyceryl isostearate, and mixtures thereof.
Even more preferentially, the fatty acid ester of glycerol is a mixture of glyceryl monostearate and glyceryl isostearate.
The fatty acid ester of glycerol may be present in a content ranging from 0.1% to 15% by weight relative to the total weight of the composition and preferably from 0.5% to 5% by weight.
The term “fatty acid in free form” is intended to mean fatty acids, in particular saturated or unsaturated fatty acids comprising from 12 to 30 carbon atoms, preferably from 14 to 26 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, cetylic acid, cetearylic acid and behenic acid.
Preferably, the fatty acid in free form of the compositions of the invention is stearic acid.
The fatty acid in free form of the compositions of the invention may be present in a content ranging from 0.1% to 15% by weight relative to the total weight of the composition and preferably from 0.5% to 5% by weight.
The term “alkali metal salt of an ester of phosphoric acid and of a fatty alcohol” is intended to mean the alkali metal salts of esters of phosphoric acid and of a fatty alcohol comprising from 14 to 36 carbon atoms, preferably from 14 to 36 carbon atoms, such as cetyl alcohol or myristyl alcohol, and in particular:
Preferably, the alkali metal salt of an ester of phosphoric acid and of a fatty alcohol of the compositions of the invention is the potassium salt of monocetyl phosphate.
The alkali metal salt of an ester of phosphoric acid and of a fatty alcohol of the compositions of the invention may be present in a content ranging from 0.1% to 15% by weight relative to the total weight of the composition and preferably from 0.5% to 5% by weight.
The term “high sun protection factor (SPF)” is intended to mean a sun protection factor (SPF) which can reach a value greater than or equal to 50. This range of high SPFs (greater than or equal to 50) is not, however, limiting for the compositions of the invention.
The level of sun protection is defined by the sun protection factor (SPF) which is determined according to the “in vitro” method described by B. L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133 (1989). The measurements were made using a UV-1000S spectrophotometer from the company Labsphere. Each composition is applied to a rough plate of PMMA, in the form of a homogeneous and even deposit in a proportion of 1 mg/cm2.
Preferably, the composition according to the invention has a sun protection factor value of between 6 and 70, preferably between 10 and 65 and even more preferably between 15 and 60.
Preferably, the composition according to the invention has a viscosity of less than 0.08 Pa·s and even more preferably less than 0.06 Pa·s at a temperature of 25° C., the viscosity being measured using a Rheomat 180 (from the company Lamy), equipped with an MS-R1, MS-R2, MS-R3, MS-R4 or MS-R5 spindle chosen according to the consistency of the composition, rotating at a rotation speed of 200 rpm.
The compositions according to the present invention also comprise one or more UV-screening agents in free form, chosen from water-soluble, liposoluble or insoluble organic UV-screening agents, and/or one or more inorganic pigments. It will preferentially consist of at least one hydrophilic, lipophilic or insoluble organic UV-screening agent.
The term “water-soluble UV-screening agent” is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid aqueous phase or else can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.
The term “liposoluble UV-screening agent” is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid fatty phase or else can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.
The term “insoluble UV-screening agent” is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation which has a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in the majority of organic solvents such as liquid paraffin, fatty alcohol benzoates and fatty acid triglycerides, for example Miglyol 812® sold by the company Dynamit Nobel. This solubility, determined at 70° C., is defined as the amount of product in solution in the solvent at equilibrium with an excess of solid in suspension after returning to ambient temperature. It may be readily evaluated in the laboratory.
The organic UV-screening agents in free form are chosen in particular from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, in particular those cited in patent U.S. Pat. No. 5,624,663; benzimidazole compounds; imidazoline compounds; bis-benzazolyl compounds, as described in patents EP 669 323 and U.S. Pat. No. 2,463,264; p-aminobenzoic (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds, as described in applications U.S. Pat. No. 5,237,071, U.S. Pat. No. 5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119; benzoxazole compounds, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 101 62 844; screening polymers and screening silicones, such as those described in particular in application WO 93/04665; α-alkylstyrene-based dimers, such as those described in patent application DE 198 55 649; 4,4-diarylbutadiene compounds, as described in applications EP 0 967 200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133 980 and EP 133 981; merocyanines as described in patent U.S. Pat. No. 4,195,999, application WO 2004/006878, applications WO 2008/090066, WO 2011/113718 and WO 2009/027258, and the documents IP COM Journal No. 000179675D published on 23 Feb. 2009, IP COM Journal No. 000182396D published on 29 Apr. 2009, IP COM Journal No. 000189542D published on 12 Nov. 2009 and IP COM Journal No. IPCOM000011179D published on 4 Mar. 2004, and mixtures thereof.
As examples of organic photoprotective agents, mention may be made of those denoted hereinbelow under their INCI name:
Cinnamic Compounds:
Ethylhexyl methoxycinnamate sold in particular under the trade name Parsol MCX® by DSM Nutritional Products,
Isopropyl methoxycinnamate,
Isoamyl p-methoxycinnamate sold under the trade name Neo Heliopan E 1000® by Symrise,
DEA methoxycinnamate,
Diisopropyl methylcinnamate,
Glyceryl ethylhexanoate dimethoxycinnamate.
Dibenzoylmethane Compounds:
Butylmethoxydibenzoylmethane, sold in particular under the trade name Parsol 1789® by DSM Nutritional Products,
Isopropyldibenzoylmethane.
para-Aminobenzoic Compounds:
PABA,
Ethyl PABA,
Ethyl dihydroxypropyl PABA,
Ethylhexyl dimethyl PABA, sold in particular under the name Escalol 507® by ISP,
Glyceryl PABA,
PEG-25 PABA, sold under the name Uvinul P 25® by BASF.
Salicylic Compounds:
Homosalate, sold under the name Eusolex HMS® by Rona/EM Industries,
Ethylhexyl salicylate, sold under the name Neo Heliopan OS® by Symrise,
Dipropylene glycol salicylate, sold under the name Dipsal® by Scher,
TEA salicylate, sold under the name Neo Heliopan TS® by Symrise.
β,β-Diphenylacrylate Compounds:
Octocrylene, sold in particular under the trade name Uvinul N 539® by BASF,
Etocrylene, sold in particular under the trade name Uvinul N 35® by BASF.
Benzophenone Compounds:
Benzophenone-1, sold under the trade name Uvinul 400® by BASF,
Benzophenone-2, sold under the trade name Uvinul D 50® by BASF,
Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul M 40® by BASF,
Benzophenone-4, sold under the trade name Uvinul MS 40® by BASF,
Benzophenone-5,
Benzophenone-6, sold under the trade name Helisorb 11® by Norquay,
Benzophenone-8, sold under the trade name Spectra-Sorb UV-24® by American Cyanamid,
Benzophenone-9, sold under the trade name Uvinul DS 49® by BASF,
Benzophenone-12,
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, sold under the trade name Uvinul A Plus® or, as a mixture with octyl methoxycinnamate, under the trade name Uvinul A Plus B® by BASF,
1,1′-(1,4-Piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]methanone] (CAS 919803-06-8), such as described in patent application WO 2007/071 584; this compound advantageously being used in micronized form (mean size of 0.02 to 2 μm), which may be obtained, for example, according to the micronization process described in patent applications GB-A-2 303 549 and EP-A-893 119, and especially in the form of an aqueous dispersion.
Benzylidenecamphor Compounds:
3-Benzylidenecamphor, manufactured under the name Mexoryl SD® by Chimex,
4-Methylbenzylidenecamphor, sold under the name Eusolex 6300® by Merck,
Benzylidenecamphorsulfonic acid, manufactured under the name Mexoryl SL® by Chimex,
Camphor benzalkonium methosulfate, manufactured under the name Mexoryl SO® by Chimex,
Terephthalylidenedicamphorsulfonic acid, manufactured under the name Mexoryl SX® by Chimex,
Polyacrylamidomethylbenzylidenecamphor, manufactured under the name Mexoryl SW® by Chimex.
Phenylbenzimidazole Compounds:
Phenylbenzimidazolesulfonic acid, sold in particular under the trade name Eusolex 232® by Merck.
Bis-benzazolyl Compounds:
Disodium phenyl dibenzimidazole tetrasulfonate, sold under the trade name Neo Heliopan AP® by Symrise.
Phenylbenzotriazole Compounds:
Drometrizole trisiloxane, manufactured under the name Mexoryl XL® by Chimex.
Methylenebis(hydroxyphenylbenzotriazole) Compounds:
Methylenebis(benzotriazolyl)tetramethylbutylphenol, in particular in solid form, such as the product sold under the trade name Mixxim BB/100® by Fairmount Chemical, or in the form of an aqueous dispersion of micronized particles with a mean particle size ranging from 0.01 to 5 μm, more preferentially from 0.01 to 2 μm and more particularly from 0.020 to 2 μm, with at least one alkylpolyglycoside surfactant having the structure CnH2n+1O(C6H10O5)xH, in which n is an integer from 8 to 16 and x is the mean degree of polymerization of the (C6H10O5) unit and ranges from 1.4 to 1.6, as described in patent GB-A-2 303 549, sold in particular under the trade name Tinosorb M® by the company BASF, or in the form of an aqueous dispersion of micronized particles with a mean particle size ranging from 0.02 to 2 μm, more preferentially from 0.01 to 1.5 μm and more particularly from 0.02 to 1 μm, in the presence of at least one polyglyceryl mono(C8-C20)alkyl ester with a degree of glycerol polymerization of at least 5, such as the aqueous dispersions described in patent application WO 2009/063 392.
Triazine Compounds:
Anthranilic Compounds:
Menthyl anthranilate, sold under the trade name Neo Heliopan MA® by Symrise.
Imidazoline Compounds:
Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
Benzalmalonate Compounds:
Polyorganosiloxane comprising benzalmalonate functional groups, such as Polysilicone-15, sold under the trade name Parsol SLX® by Hoffmann LaRoche.
4,4-Diarylbutadiene Compounds:
Benzoxazole Compounds:
2,4-bis[5-(1,1-dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine, sold under the name Uvasorb K2A® by Sigma 3V.
The preferential organic screening agents in free form are chosen from:
Ethylhexyl methoxycinnamate,
Ethylhexyl salicylate,
Homosalate,
Butylmethoxydibenzoylmethane,
Octocrylene,
Phenylbenzimidazolesulfonic acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
4-Methylbenzylidenecamphor,
Terephthalylidenedicamphorsulfonic acid,
Disodium phenyl dibenzimidazole tetrasulfonate,
Methylenebis(benzotriazolyl)tetramethylbutylphenol,
Bis(ethylhexyloxyphenol)methoxyphenyltriazine
Ethylhexyl triazone,
Diethylhexyl butamido triazone,
2,4,6-tris(dineopentyl 4′-aminobenzalmalonate)-s-triazine,
2,4,6-tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine,
2,4-bis(n-butyl 4′-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine,
2,4-bis(dineopentyl 4′-aminobenzalmalonate)-6-(n-butyl 4′-aminobenzoate)-s-triazine,
Drometrizole trisiloxane,
Polysilicone-15,
1,1-dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene,
2,4-bis[5-(1,1-dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,
and mixtures thereof.
The particularly preferred organic screening agents in free form are chosen from:
Ethylhexyl methoxycinnamate,
Ethylhexyl salicylate,
Homosalate,
Butylmethoxydibenzoylmethane,
Octocrylene,
Phenylbenzimidazolesulfonic acid,
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
Terephthalylidenedicamphorsulfonic acid,
Methylenebis(benzotriazolyl)tetramethylbutylphenol,
2,4,6-tris(diphenyl)triazine,
Bis(ethylhexyloxyphenol)methoxyphenyltriazine,
Ethylhexyl triazone,
Diethylhexyl butamido triazone,
Drometrizole trisiloxane,
and mixtures thereof.
The inorganic UV-screening agents used in accordance with the present invention are metal oxide pigments. More preferentially, the inorganic UV-screening agents of the invention are metal oxide particles with a mean elementary particle size of less than or equal to 0.5 μm, more preferentially between 0.005 and 0.5 μm, even more preferentially between 0.01 and 0.2 μm, better still between 0.01 and 0.1 μm and more particularly between 0.015 and 0.05 μm.
They may be chosen in particular from titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, or mixtures thereof
Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0 518 773. Commercial pigments that may be mentioned include the products sold by the companies Sachtleben Pigments, Tayca, Merck and Degussa.
The metal oxide pigments may be coated or uncoated.
The coated pigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
The coated pigments are more particularly titanium oxides that have been coated:
Mention may also be made of TiO2 pigments doped with at least one transition metal such as iron, zinc or manganese and more particularly manganese. Preferably, said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric/caprylic acids. The oily dispersion of titanium oxide particles may also comprise one or more dispersants, for instance a sorbitan ester, for instance sorbitan isostearate, or a polyoxyalkylenated fatty acid ester of glycerol, for instance TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium oxide particles comprises at least one dispersant chosen from polyoxyalkylenated fatty acid esters of glycerol. Mention may be made more particularly of the oily dispersion of TiO2 particles doped with manganese in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate and sorbitan isostearate having the INCI name: titanium dioxide (and) TRI-PPG-3 myristyl ether citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate, for instance the product sold under the trade name Optisol TD50® by the company Croda.
The uncoated titanium oxide pigments are sold, for example, by the company Tayca under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 B®, by the company Degussa under the name P 25, by the company Wackherr under the name Transparent titanium oxide PW®, by the company Miyoshi Kasei under the name UFTR®, by the company Tomen under the name ITS® and by the company Tioxide under the name Tioveil AQ®.
The uncoated zinc oxide pigments are for example:
The coated zinc oxide pigments are for example:
The uncoated cerium oxide pigments may be, for example, those sold under the name Colloidal Cerium Oxide® by the company Rhone-Poulenc.
The uncoated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2002® (FE 45B®), Nanogard Iron FE 45 BL AQ®, Nanogard FE 45R AQ® and Nanogard WCD 2006® (FE 45R®) or by the company Mitsubishi under the name TY-220®.
The coated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2008 (FE 45B FN)®, Nanogard WCD 2009® (FE 45B 556®), Nanogard FE 45 BL 345® and Nanogard FE 45 BL® or by the company BASF under the name Transparent Iron Oxide®.
Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and of cerium dioxide, including the equal-weight mixture of titanium dioxide and cerium dioxide coated with silica, sold by the company Ikeda under the name Sunveil A®, and also the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, such as the product M 261® sold by the company Sachtleben Pigments, or coated with alumina, silica and glycerol, such as the product M 211® sold by the company Sachtleben Pigments.
According to the invention, coated or uncoated titanium oxide pigments are particularly preferred.
The UV-screening agents according to the invention are preferably present in the compositions according to the invention in a content ranging from 0.1% to 45% by weight and in particular from 5% to 30% by weight relative to the total weight of the composition.
The compositions according to the invention are oil-in-water emulsions. The emulsification processes that may be used are of the paddle or propeller and rotor-stator type.
As indicated previously, the compositions according to the invention comprise at least one continuous aqueous phase.
The aqueous phase contains water and optionally other water-soluble or water-miscible organic solvents.
An aqueous phase that is suitable for use in the invention may comprise, for example, a water chosen from a natural spring water, such as water from La Roche-Posay, water from Vittel or waters from Vichy, or a floral water.
The water-soluble or water-miscible solvents that are suitable for use in the invention comprise short-chain monoalcohols, for example C1-C4 monoalcohols, such as ethanol or isopropanol; diols or polyols, such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol and sorbitol, and mixtures thereof.
According to a preferred embodiment, use may more particularly be made of ethanol, propylene glycol, glycerol, and mixtures thereof.
According to one particular form of the invention, the overall aqueous phase, including all the hydrophilic substances of the composition capable of being dissolved in this same phase, may represent from 5% to 95% by weight and preferentially from 10% to 80% by weight, relative to the total weight of the composition.
According to one preferred embodiment of the invention, the compositions of the invention do not comprise any aqueous-phase-thickening or -gelling polymer.
As indicated above, the composition according to the invention comprises at least one oily phase dispersed in the aqueous phase.
For the purposes of the invention, the term “oily phase” is intended to mean a phase comprising at least one oil and all of the liposoluble and lipophilic ingredients and the fatty substances used for the formulation of the compositions of the invention.
The term “oil” is intended to mean any fatty substance that is in liquid form at ambient temperature (20-25° C.) and at atmospheric pressure (760 mmHg).
An oil that is suitable for use in the invention may be volatile or non-volatile.
An oil that is suitable for use in the invention may be chosen from hydrocarbon-based oils, silicone oils and fluoro oils, and mixtures thereof.
A hydrocarbon-based oil that is suitable for use in the invention may be an animal hydrocarbon-based oil, a plant hydrocarbon-based oil, a mineral hydrocarbon-based oil or a synthetic hydrocarbon-based oil.
An oil that is suitable for use in the invention may be advantageously chosen from mineral hydrocarbon-based oils, plant hydrocarbon-based oils, synthetic hydrocarbon-based oils and silicone oils, and mixtures thereof.
For the purposes of the present invention, the term “silicone oil” is intended to mean an oil comprising at least one silicon atom, and in particular at least one Si—O group.
The term “hydrocarbon-based oil” is intended to mean an oil containing mainly hydrogen and carbon atoms.
The term “fluoro oil” is intended to mean an oil comprising at least one fluorine atom.
A hydrocarbon-based oil that is suitable for use in the invention may also optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl, amine, amide, ester, ether or acid groups, and in particular in the form of hydroxyl, ester, ether or acid groups.
The oily phase may comprise one or more volatile or non-volatile hydrocarbon-based oils and/or one or more volatile and/or non-volatile silicone oils.
For the purposes of the invention, the term “volatile oil” is intended to mean an oil that is capable of evaporating on contact with the skin or the keratin fibre in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil(s) of the invention are volatile cosmetic oils which are liquid at ambient temperature and which have a non-zero vapour pressure, at ambient temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10−3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
The term “non-volatile oil” is intended to mean an oil that remains on the skin or the keratin fibre at ambient temperature and atmospheric pressure for at least several hours, and that especially has a vapour pressure of less than 10−3 mmHg (0.13 Pa).
Among the non-volatile hydrocarbon-based oils that can be used according to the invention, mention may be made of glyceride triesters and in particular caprylic/capric acid triglycerides such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, fatty amides such as isopropyl N-lauroyl sarcosinate, such as the product sold under the trade name Eldew SL 205® from Ajinomoto, synthetic esters, and in particular isononyl isononanoate, diisopropyl sebacate, C12-C15 alkyl benzoate, such as the product sold under the trade name Finsolv TN® or Witconol TN® by the company Witco or Tegosoft TN® by the company Evonik Goldschmidt, 2-ethylphenylbenzoate, such as the commercial product sold under the name X-Tend 226® by the company ISP, and fatty alcohols, in particular octyldodecanol.
As volatile hydrocarbon-based oils that may be used according to the invention, mention may be made in particular of hydrocarbon-based oils having from 8 to 16 carbon atoms and in particular of branched C8-C16 alkanes, such as C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, the oils sold under the Isopar or Permethyl trade names, branched C8-C16 esters, isohexyl neopentanoate, and mixtures thereof.
Among the non-volatile silicone oils, mention may be made of non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendent and/or at the end of the silicone chain, which groups each contain from 2 to 24 carbon atoms, or phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyl(trimethylsiloxy)diphenylsiloxanes, diphenyl dimethicones, diphenyl(methyldiphenyl)trisiloxanes or (2-phenylethyl)trimethylsiloxysilicates.
Among the volatile silicone oils, mention may for example be made of volatile linear or cyclic silicone oils, especially those with a viscosity ≦8 centistokes (8×10−6 m2/s) and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oil that may be used in the invention, mention may be made in particular of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
Among the volatile fluoro oils, mention may be made of nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane and dodecafluoropentane, and mixtures thereof.
An oily phase according to the invention may also comprise other fatty substances, mixed with or dissolved in the oil.
Another fatty substance that may be present in the oily phase may be, for example:
The compositions of the invention preferably comprise raw materials which do not themselves filter out UV radiation, but make it possible to amplify the screening performance of the compositions of the invention: these are efficiency boosters. Mention is for example made of the particles of styrene/alkyl acrylate copolymer sold under the name Sunspheres Powder by Dow Chemical; mention is also made of waxes such as polymethylene wax (Cirebelle 303 sold by the company Cirebelle). Mention is also made of gelling lipophilic polymers such as the semi-crystalline polyacrylates sold under the names Intelimer IPA 13-1, Intelimer IPA 13-6 or Uniclear 100 VG by the company Air Products and Chemicals, or else Uniclear 100 VG-PA.
The compositions of the invention may contain any of the additives normally used in cosmetics and will find uses in the field of anti-sun, care and makeup products.
The aqueous phase may contain glycols, such as dipropylene glycol, glycerol and butylene glycol, active agents, salts, fillers, organic particles, hydrophilic polymers such as carboxyvinyl polymers (carbomers), polymers derived from 2-acrylamido-2-methylpropanesulfonic acid, synthetic neutral polymers such as N-vinylpyrrolidone, polysaccharides such as guar gums, xanthan gums and cellulose-based derivatives, synthetic clays, water-soluble or water-dispersible silicone derivatives, such as acrylic silicones, silicone polyethers and cationic silicones.
As active agents, use may in particular be made of vitamins (A, C, E, K, PP, etc), alone or as a mixture, and also derivatives thereof, keratolytic and/or desquamating agents (salicylic acid and derivatives thereof, alpha-hydroxy acids, ascorbic acid and derivatives thereof), anti-inflammatories, calmatives, depigmenting agents, tensioning agents such as synthetic polymers, plant proteins, polysaccharides of plant origin optionally in the form of microgels, starches, wax dispersions, mixed silicates and colloidal particles of inorganic fillers; matting agents, agents for preventing hair loss and/or hair restorers, or else anti-wrinkle agents, and mixtures thereof.
The oily phase may contain lipophilic gelling agents, surfactants, waxes, organic or inorganic particles and, in addition to the polar oil(s) of the invention, oils of alkane, silicone or fluoro type.
The present invention also relates to the use of the mixture of surfactants as described previously, for stabilizing a composition in the form of an oil-in-water emulsion containing one or more UV-screening agents.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
I. Compositions Tested
The compositions (A) to (A5) are prepared, the amounts of which are expressed as percentage by weight unless otherwise indicated.
The following compositions (B) and (C) according to the invention are also prepared, the amounts of which are expressed as percentage by weight unless otherwise indicated.
II. Procedure for the Compositions
The aqueous phase (I) and the oily phase (II) are prepared by mixing the ingredients with mechanical stirring at a temperature of 80° C.; the solutions obtained are macroscopically homogeneous.
The emulsion is prepared by slowly introducing the oily phase (II) into the aqueous phase (I) with stirring using a homogenizer of COS 1000 type at a speed of 4000 rpm for 15 minutes. The emulsion obtained is cooled, with stirring, to 40° C. and then the phase (III) is added with gentle stirring, followed by the phase (IV).
The emulsion obtained is cooled to ambient temperature with slow stirring. The emulsion is characterized by drops having a size of between 500 nanometres and 10 μm and has a viscosity of less than 100 mPa·s.
III. Protocol for Evaluating In Vitro the Screening Efficiency
The sun protection factor (SPF) is determined according to the “in vitro” method described by B. L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133 (1989). The measurements were made using a UV-1000S spectrophotometer from the company Labsphere. Each composition is applied to a rough plate of PMMA, in the form of a homogeneous and even deposit in a proportion of 1 mg/cm2.
III. Protocol for Evaluating the Stability of the Compositions
The stability of the compositions of the invention is evaluated by macroscopic and microscopic observations of their appearance and by measuring their viscosity.
A composition is judged to be stable when its macroscopic appearance and microscopic appearance, its pH and its viscosity do not vary for 2 months at from 25° C. to 45° C.
IV. Protocol for Evaluating the Viscosity of the Emulsions
The viscosity of the compositions is measured using a Rheomat 180 (from the company Lamy), equipped with an MS-R1, MS-R2, MS-R3, MS-R4 or MS-R5 spindle chosen according to the consistency of the composition, rotating at a rotation speed of 200 rpm.
VI. Results
No change in terms of the macroscopic and microscopic appearances and in terms of viscosity is noted after two months of storage at from 25° C. to 45° C. for compositions A, B and C.
These results show that only the combination of at least one fatty acid ester of a polyalkylene glycol (PEG-100 stearate), at least one fatty acid ester of glycerol (i.e.: mixture of glyceryl monostearate and glyceryl isostearate), at least one fatty acid in free form (i.e. stearic acid) and at least one alkali metal salt of an ester of phosphoric acid and of a fatty alcohol makes it possible to obtain an oil-in-water emulsion which is stable and extremely fluid and has a high SPF protection level.
For the combinations of surfactants not comprising the collection of surfactants of the invention, the performance levels in terms of screening efficiency, stability and viscosity are inferior to those of the combination of the composition according to the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1454854 | May 2014 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2015/061805 | 5/28/2015 | WO | 00 |
