WATER-RESISTANT COSMETIC COMPOSITION COMPRISING LIGHT GREEN CLAY AND A PROBIOTIC-DERIVED ACTIVE INGREDIENT

FIELD OF THE INVENTION

The present invention relates to a new cosmetic composition comprising light green clay and a probiotic-derived active ingredient and having high SPF values. The cosmetic formulation has enhanced water-resistance and anti-oiliness effect when compared to cosmetic compositions of the prior art. The cosmetic composition of the present invention also presents a soft sensorial to the skin and dry touch after application. The present invention is also related to the use of said cosmetic composition.

BACKGROUND OF THE INVENTION

The photoprotection of keratinous materials, including both skin and hair, is considered of great importance in order to protect from sun-damage, sunburn, photo aging, as well as to decrease the chances of skin cancer development caused by exposure to ultraviolet (“UV”) radiation. There are typically two types of UVA/UVB sunscreen compositions used to accomplish photoprotection, namely, inorganic UV filters and organic UV filters.

The degree of UV protection afforded by a sunscreen composition is directly related to the amount and type of UV filters contained therein. The higher the amount of UV filters, the greater the degree of UV protection (UVA/UVB).

Particularly, sunscreen compositions must provide good protection against the sun, a measure of which is the Sun Protection Factor (SPF) value, yet have satisfactory sensory perception, such as a good spreadability and dry touch after application, thereby being smooth but not greasy feel upon application.

Moreover, conventional sunscreen compositions are expected to possess water-resistance properties in order to inhibit the protective composition from being easily removed from a keratinous substrate surface by sweat and exposure to water.

Water-resistant sunscreen compositions do not easily“run off” or wash off when the skin and hair are exposed to water, rain, and tears or upon sweating nor easily transfer from the skin or hair because of normal every day activity. These products also tend to have long wearing and transfer-resistant properties, that is, they adhere longer to surfaces and to keratinous substrates. Commercial products which have these properties may require high amounts of paraffin, fatty alcohols, petrolatum, vaseline, waxes or oils, e.g., mineral oil. Other customary barrier agents are silicones and conventional film forming agents or polymers. However, such ingredients still present many disadvantages; for example, high levels of oils and hydrocarbon -based ingredients make the skin or hair greasy, waxes can give an unpleasant aesthetic look and feel, and silicones can leave residues and may give an uncomfortable feel and wear.

Thus, there still exists a need to find other materials or sunscreen compositions that can provide a water-resistant and protective barrier to the skin and which do not require the customary barrier agents, simultaneously providing a soft sensorial to the skin, dry touch after application and anti-oiliness effect.

Considering the current needs of the state of the art and the difficulties to overcome them, the inventors developed a water-resistant cosmetic composition by combining a lysate of at least one microorganism of the genus Bifidobacterium, light green clay, a surfactant system comprising at least one anionic surfactant and at least one nonionic surfactant and a high SPF UV filter system.

The cosmetic composition according to the present invention surprisingly showed enhanced water-resistance property, anti-oiliness effect, achieved high SPF values and presented satisfactory sensory perception, such as clean skin sensation, shine control, matte effect, pleasant and easy application, fresh feel, hydration, good texture, comfort sensation and dry touch to the skin after application.

Thus, the inventors succeeded to overcome the problems of the state of the art and surprisingly revealed a cosmetic composition having the aforementioned technical advantages.

SUMMARY OF THE INVENTION

The present invention is directed to a new cosmetic composition comprising: (a) a lysate of at least one microorganism of the genus Bifidobacterium, (b) light green clay, (c) a surfactant system comprising at least one anionic surfactant and at least one nonionic surfactant, and (d) UV filter system.

The present invention also relates to the use of the cosmetic composition for the manufacture of a product to be used as sunscreen daily product.

DETAILED DESCRIPTION OF THE INVENTION

In an embodiment, the cosmetic composition of the present invention comprises: (a) at least about 0.5% by weight, based on the total weight of the composition, of a lysate of at least one microorganism of the genus Bifidobacterium.

(b) at least about 0.1 % by weight, based on the total weight of the composition, of light green clay;

(c) at least about 3% by weight, based on the total weight of the composition, of a surfactant system comprising at least one anionic surfactant and at least one nonionic surfactant; and

(d) UV filter system.

The cosmetic composition according to the present invention surprisingly showed enhanced water-resistance property, anti-oiliness effect, achieved high SPF values and presented good sensorial properties, such as clean skin sensation, shine control, matte effect, pleasant and easy application, fresh feel, hydration, good texture, comfort sensation and dry touch to the skin after application.

In a preferred embodiment, the amount of the lysate of at least one microorganism of the genus Bifidobacterium in the cosmetic composition of the present invention ranges from about 0.5% to about 15% by weight and preferably from about 1 % to about 10% by weight, more preferably from about 1 % to about 8% by weight, based on the total weight of the composition.

In a preferred embodiment, the at least one microorganism of the genus Bifidobacterium species is selected from the group consisting of Bifidobacterium longum, Bifidobacterium bifidum, Bifidobacterium breve, Bifidobacterium animalis, Bifidobacterium lactis, Bifidobacterium infantis, Bifidobacterium adolescentis or Bifidobacterium pseudocatenulatum.

The amount of light green clay in the cosmetic composition of the invention preferably ranges from about 0.1 % to about 10% by weight, preferably in an amount of from about 0.5% to about 8% by weight, more preferably from about 0.5% to about 5% by weight, based on the total weight of the composition.

In a preferred embodiment, the amount of surfactant system in the cosmetic composition of the present invention ranges from about 3% to about 20% by weight and preferably from about 3% to about 15% by weight, more preferably from about 3% to about 10% by weight, based on the total weight of the composition.

The surfactant system of the present invention comprises at least one anionic surfactant, preferably in an amount ranging from about 0.1 % to about 10% by weight and preferably from about 0.1 % to about 8% by weight, more preferably from about 0.1 % to about 5% by weight, based on the total weight of the composition.

In a preferred embodiment, the at least one anionic surfactant of the present invention is selected from the group consisting of potassium cetyl phosphate, sodium methyl stearoyl taurate, and mixtures thereof.

Additionally, the surfactant system of the present invention comprises at least one nonionic surfactant, preferably in an amount ranging from about 0.5% to about 15% by weight, preferably from 0.5% to about 10% by weight, more preferably from about 1 % to about 8% by weight, based on the total weight of the composition.

In a preferred embodiment, the at least one nonionic surfactant of the present invention is select from the group consisting of stearyl alcohol, stearic acid, glyceryl stearate, PEG-100 stearate, poloxamer 338 and polyglyceryl-10 laurate.

In a preferred embodiment, the cosmetic composition of the present invention has an amount of UV filter system ranging from about 0.1 % to about 50% by weight, preferably in an amount from about 5% to about 40% by weight, more preferably from about 5% to about 30% by weight, most preferably about 10% to about 30% by weight, based on the total weight of the composition.

The UV filter system of the present invention may comprise at least one UV filter selected from the group of inorganic UV filters and organic UV filters, and mixtures thereof. In a preferred embodiment, the UV filter system comprise at least one UV filter selected from the group consisting of phenylbenzimidazole sulfonic acid, butyl methoxydibenzoylmethane, titanium dioxide, ethylhexyl triazone, terephthalylidene dicamphor sulfonic acid, octocrylene, homosalate, bis- ethylhexyloxyphenol methoxyphenyl triazine, methylene bis-benzotriazolyl tetramethylbutylphenol and mixtures thereof.

In a preferred embodiment, the cosmetic composition according to the present invention further comprises at least one filler selected from the group consisting of silica, octenylsuccinic anhydride-esterified starch salts, and mixtures thereof. Preferably, the silica is hydrophobic silica, more preferably silica silylate. In a preferred embodiment, the amount of the at least one filler ranges from about 5% to about 20% by weight, more preferably from about 5% to about 15% by weight, and most preferably from about 5% to about 10% by weight, based on the total weight of the composition. The cosmetic composition of the present invention can further comprise at least one fatty compound selected from the group of oils, waxes, fatty acids, fatty alcohols, and mixtures thereof. Preferably, the at least one fatty compound is selected from the group consisting of oils, more preferably from synthetic esters. Said at least one fatty compound is preferably in an amount ranging from 5% by weight to 20% by weight, based on the total weight of composition, preferably from about 5% by weight to about 15% by weight, based on the total weight of the composition

The cosmetic composition of the present invention is in the form of an oil in water (O/W) emulsion and can be used as a daily product for the skin.

In another preferred embodiment, the composition of the present invention presents a SPF of 30, 50, 60, 70, 90 or 100.

In another preferred embodiment, the present invention is related to the use of a composition for manufacturing a product for preventing sunburn, which can be used as sunscreen daily product.

The cosmetic composition according to the present invention can be prepared according to the following steps:

(a) preparing an oily phase by mixing the organic UV filters, the surfactant system and all the oily ingredients, for example, fatty compounds, wherein the oily phase is heated until complete homogenization; and

(b) adding an aqueous phase to the oily phase of step (a) under mixing until complete formation of the emulsion.

(c) adding shear sensitive and/or heat sensitive ingredients.

In a particular embodiment, the aqueous phase of step (b) is prepared by mixing water, green clay, lysate and all the aqueous ingredients.

TERMS

As used herein, the expression“at least” means one or more and thus includes individual components as well as mixtures/combinations.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or process conditions are to be understood as being modified in all instances by the term“about,” meaning within +/- 5% of the indicated number.

As used herein, all ranges provided are meant to include every specific range within, and combination of sub ranges between, the given ranges. Thus, a range from 1 -5, includes specifically 1 , 2, 3, 4 and 5, as well as sub ranges such as 2-5, 3-5, 2-3, 2-4, 1 -4, etc. All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc.

LYSATE

The microorganisms of the genus Bifidobacterium species used as actives according to the invention are employed in the form of a lysate. A lysate commonly denotes a material obtained after destruction or dissolution of biological cells by a phenomenon called cell lysis, thus causing the release of the intracellular biological constituents naturally contained in the cells of the microorganism in question.

In the sense of the present invention, the term“lysate” is used without distinction to denote all of the lysate obtained by lysis of the microorganism in question or only a fraction thereof.

Thus, the invention relates to the application of a lysate of Bifidobacterium species and/or a fraction thereof.

The lysate used is therefore formed wholly or partly from the intracellular biological constituents and from the constituents of the cell walls and membranes.

More precisely, it contains the cellular cytoplasmic fraction containing the enzymes such as lactic acid dehydrogenase, phosphatases, phosphoketolases, and transaldolases and the metabolites. For purposes of illustration, the constituents of the cell walls are notably peptidoglycan, murein or mucopeptide and teichoic acid and the constituents of the cell membranes are glycerophospholipid compounds.

This cell lysis can be performed by various technologies, for example osmotic shock, thermal shock, with ultrasound, or under mechanical stress such as centrifugation. According to a preferred embodiment, the lysate is obtained by disintegration by ultrasound.

More particularly, said lysate can be obtained according to the technology described in U.S. Pat. No. 4,464, 362, and notably according to the following protocol.

A microorganism of the Bifidobacterium species type considered is cultivated anaerobically in a Suitable culture medium, for example according to the conditions described in documents U.S. Pat. No. 4,464,362 and EP 0043 128. When the stationary phase of development is reached, the culture medium can be inactivated by pasteurization, for example at a temperature of 60 to 65° C for 30 min. The microorganisms are then collected by a conventional separation technique, for example membrane filtration, centrifuged and resuspended in a sterile NaCI solution at a physiological concentration. The lysate can be obtained by ultrasonic disintegration of said medium in order to release its cytoplasmic fractions, the fragments of cell wall and the products resulting from metabolism. Then all the components in their natural distribution are stabilized in a weakly acid aqueous solution.

In this way a lysate is generally obtained that has a concentration of the order of 0.1 % to 50%, in particular from 1 % to 20%, and notably about 5% by weight of active substance(s) relative to its total weight.

The lysate can be used in various forms, in the form of a solution or in a pulverulent form.

A microorganism belonging to the genus Bifidobacterium species is more particularly selected from the species: Bifidobacterium longum, Bifidobacterium bifidum, Bifidobacterium breve, Bifidobacterium animalis, Bifidobacterium lactis, Bifidobacterium inf antis, Bifidobacterium adolescentis or Bifidobacterium pseudocatenulatum, and mixtures thereof. The species Bifidobacterium longum is quite particularly suitable for the invention.

Preferably, the amount of the lysate of at least one microorganism of the genus Bifidobacterium in the cosmetic composition of the present invention ranges from about 0.5% to 15% by weight and preferably from about 1 % to about 10% by weight, more preferably from about 1 % to about 8% by weight, based on the total weight of the composition.

LIGHT GREEN CLAY

For the purposes of the present invention, the term“clay” is directed to a natural mineral derived from sedimentary rocks composed of extremely fine particles of silicates and several trace elements, exhibiting different types and concentrations of metals, for example, titanium, magnesium, copper, zinc, aluminum, calcium, potassium, nickel, lithium and iron.

The light green clay of the present invention is a kaolin having a natural light green color, which may be in the form of a powder with a preferable maximum medium diameter of up to 50 pm, more preferably up to 30 pm.

In a preferred embodiment, the light green clay of the present invention comprises at least one of silicon dioxide (S1O2), ferric oxide (Fe203), aluminum oxide (AI2O3) and titanium dioxide (T1O2), whose amounts may vary depending on the soil, water and climate processes to which the natural mineral was subjected. The amount of light green clay in the cosmetic composition of the present invention is at least 0.1 % by weight, preferably from about 0.5% to about 10% by weight, more preferably in an amount of from about 0.5% to about 8% by weight, even more preferably from about 0.5% to about 5% by weight, based on the total weight of the composition.

SURFACTANT SYSTEM

The cosmetic composition according to the present invention comprises a surfactant system comprising at least one anionic surfactant and at least one nonionic surfactant. Preferably, the amount of surfactant system in the cosmetic composition of the present invention ranges from about 3% to about 20% by weight and preferably from about 3% to about 15% by weight, more preferably from about 3% to about 10% by weight, based on the total weight of the composition.

Nonionic surfactants

The surfactant system according to the present invention comprises at least one nonionic surfactant.

Non-limiting examples of nonionic surfactants useful in the present invention include, for example, alkyl- and polyalkyl- esters of glycerol, polyglycerol ester of fatty acids, mixtures of alkyl- and polyalkyl- esters of glycerol with polyglyceryl, such as polyglyceryl-3 methylglucose distearate, fatty acids, oxyalkylenated (more particularly polyoxyethylenated), fatty acid esters of glycerol; oxyalkylenated fatty acid esters of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acid esters; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters, for instance sucrose stearate; fatty alcohols, fatty alcohol ethers of sugars, especially alkyl polyglucosides (APGs) such as decyl glucoside, lauryl glucoside, cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol, and also arachidyl glucoside, for example in the form of a mixture of arachidyl alcohol, behenyl alcohol and arachidyl glucoside. According to one particular embodiment of the invention, the mixture of the alkyl polyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition. Mention may also be made of lecithins and derivatives (e.g. Biophilic), sugar esters and sodium stearoyl lactylate.

Alkyl- esters of glycerol includes glyceryl esters of fatty acids, such as glyceryl stearate (glyceryl mono-, di-, and/or tristearate), glyceryl laurate or glyceryl ricinoleate, and mixtures thereof. As polyoxyalkylenated derivatives thereof, mono-, di-, or triester of fatty acids with a polyoxyalkylenated glycerol (mono, di-, or triester of fatty acids with a polyalkylene glycol ether of glycerol) can be cited, preferably polyoxyethylenated glyceryl stearate (mono-, di-, and/or tristearate), such as PEG-20 glyceryl stearate (mono-, di-, and/or tristearate).

Polyglycerol esters of fatty acids may be selected from esters derived from the reaction of polyglycerol having from 2 to 12 glycerol units, preferably from 3 to 10 glycerol units and of at least one fatty acid comprising from 8 to 24 carbon atoms, preferably from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms and more preferably 10 to 14 carbon atoms. Fatty acids containing from 8 to 24 carbon atoms may be linear or branched, saturated or unsaturated. The fatty acids may be selected from oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid, myristic acid, linoleic acid, capric acid, caprylic acid, or mixtures thereof.

According to a preferred embodiment, polyglycerol esters of fatty acid are selected from esters derived from the reaction of polyglycerol comprising 2 to 12 glycerol units, preferably from 4 to 10 glycerol units, and of at least a fatty acid having less than 16 carbon atoms, preferably less than 15 carbon atoms, for example from 8 to 16 carbon atoms and better still from 8 to 14 carbon atoms.

According to one embodiment, the polyglycerol ester of fatty acid is selected from polyglycerol esters derived from the reaction comprising 4 to 10 glycerol units and of at least one fatty acid comprising from 8 to 12 carbon atoms preferably 10 to 12 carbon atoms such as lauric acid and / or capric acid. There may be mentioned for example the ester from polyglyceryl-10 reaction (glycerol homopolymer comprising 10 glycerol units) and lauric acid (INCI name: polyglyceryl-10 laurate) such as that marketed by the company Dr Straetmans under the DERMOFEEL reference G 10 L, the ester from the reaction polyglycerol-4 (glycerol homopolymer comprising 4 glycerol units) and capric acid (INCI name: polyglyceryl-4 caprate) such as that marketed by Evonik under the reference Tegosoft PC 41 .

Examples of oxyalkylenated fatty acid esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (PEG-100 stearate); and mixtures thereof.

Possible fatty alcohols to be used in the present invention includes alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.

The fatty alcohols may have the structure R-OH wherein R is chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be chosen from C12-C20 alkyl and C12-C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group.

As examples of the fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

The fatty acids used in the context of the invention are more particularly chosen from carboxylic acids, saturated or unsaturated, having from 6 to 30 carbon atoms, preferably from 9 to 30 carbon atoms. They are advantageously chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid.

Other examples of nonionic surfactants to be used in the surfactant system of the present invention include polycondensates of ethylene oxide and of propylene oxide of the structure below:

H-(0-CH2-CH2)a-(0-CH(CH ₃ )-CH2)b-(0-CH2-CH2)a -0H, in which a, a’ range from 2 to 150, and b ranges from 1 to 100.

In the chemical structure described above, preferably, a and a’ range from 10 to 130 and b ranges from 20 to 80, better still a and a’ range from 50 to 130 and b ranges from 30 to 80, and even better still a and a’ range from 80 to 130 and b ranges from 40 to 80. According to one particular embodiment, a and a’ are identical.

The polycondensate of ethylene oxide and propylene oxide that is useful in the composition of the invention preferably has a weight-average molecular weight ranging from 250 to 19 000, better still ranging from 1200 to 15 000, in particular ranging from 1500 to 10 000 and even better still ranging from 1500 to 5000. Advantageously, the polycondensate of ethylene oxide and propylene oxide has a cloud point, at 10 g/l in distilled water, greater than or equal to 20°C and preferably greater than or equal to 60°C. The cloud point is measured according to standard ISO 1065.

As polycondensate products of ethylene oxide and propylene oxide that may be used according to the invention, mention may be made of the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensate products sold under the name Synperonic, for instance Synperonic® PE/F32 (INCI name: Poloxamer 108), Synperonic® PE/F108 (INCI name: Poloxamer 338), Synperonic® PE/L44 (INCI name: Poloxamer 124), Synperonic® PE/L42 (INCI name: Poloxamer 122), Synperonic® PE/F127 (INCI name: Poloxamer 407), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/L64 (INCI name: Poloxamer 184), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/F87 (INCI name: Poloxamer 237) by the company Croda, or Lutrol® F68 (INCI name: Poloxamer 188) by the company BASF.

In a preferred embodiment, the at least one nonionic surfactant of the present invention is select from the group consisting of stearyl alcohol, stearic acid, glyceryl stearate, PEG-100 stearate, poloxamer 338 and polyglyceryl-10 laurate.

Preferably, the amount of the at least one nonionic surfactant in the surfactant system of the cosmetic composition of the present invention ranges from about 0.5% to about 15% by weight and preferably from about 0.5% to about 10% by weight, more preferably from about 1 % to about 8% by weight, based on the total weight of the composition.

Anionic surfactants

The surfactant system according to the present invention comprises at least one anionic surfactant.

Non-limiting anionic surfactant(s) that may be used in the present invention are also selected from the group comprising , alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, sulfonates, such as alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, alpha-olefin sulfonates, paraffin sulfonates, sulfosuccinates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, N-acyl N-methyltaurates, N-acylisethionates, N-acyltaurates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, mixed esters of organic acids with glycerol, such as glyceryl stearate citrate and as glyceryl stearate lactate, salts of D-galactoside uronic acids, salts of alkyl ether carboxylic acids, salts of alkyl aryl ether carboxylic acids, and salts of alkylamido ether carboxylic acids; or the non-salified forms of all of these compounds, the alkyl and acyl groups of all of these compounds containing from 6 to 24 carbon atoms and the aryl group denoting a phenyl group. Some of these compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The anionic surfactant may also be chosen in particular from anionic derivatives of proteins of vegetable origin or of silk proteins, phosphates and alkyl phosphates, carboxylates, sulphosuccinates, amino acid derivatives, alkyl sulphates, alkyl ether sulphates, sulphonates, isethionates, taurates, alkyl sulphoacetates, polypeptides, anionic derivatives of alkyl poly glucosides, and their mixtures.

1 ) Anionic derivatives of proteins of vegetable origin are protein hydrolysates comprising a hydrophobic group, it being possible for the said hydrophobic group to be naturally present in the protein or to be added by reaction of the protein and/or of the protein hydrolysate with a hydrophobic compound. The proteins are of vegetable origin or derived from silk, and the hydrophobic group can in particular be a fatty chain, for example an alkyl chain comprising from 10 to 22 carbon atoms. Mention may more particularly be made, as anionic derivatives of proteins of vegetable origin, of apple, wheat, soybean or oat protein hydrolysates comprising an alkyl chain having from 10 to 22 carbon atoms, and their salts. The alkyl chain can in particular be a lauryl chain and the salt can be a sodium, potassium and/or ammonium salt.

2) Mention may be made, as phosphates and alkyl phosphates, for example, of monoalkyl phosphates and dialkyl phosphates, such as lauryl monophosphate, such as the product sold under the name MAP20® by Kao Chemicals, the potassium salt of dodecyl phosphate, the mixture of mono- and diesters (predominantly diester), for example sold under the name Crafol AP-31® by Cognis, the mixture of octyl phosphate monoester and diester, such as the product sold under the name Crafol AP-20® by Cognis, the mixture of ethoxylated (7 mol of EO) 2- butyloctyl phosphate monoester and diester, such as the product sold under the name Isofol 12 7 EO-Phosphate Ester® by Condea, the potassium or triethanolamine salt of mono(C12-C13)alkyl phosphate, such as the products sold under the references Arlatone MAP230K-40® and Arlatone MAP 230T-60® by Uniqema, potassium lauryl phosphate, such as the product sold under the name Dermalcare MAP XC-99/09R) by Rhodia Chimie, and potassium cetyl phosphate, for example, sold under the name Arlatone MAP 160K by Uniqema.

3) Mention may be made, as carboxylates, of:

amido ether carboxylates (AEC), such as sodium lauryl amido ether carboxylate (3 EO), for example, sold under the name Akypo Foam 30® by Kao Chemicals;

polyoxyethylenated carboxylic acid salts, such as oxyethylenated (6 EO) sodium lauryl ether carboxylate (65/25/10 C12-C14-C16), for example, sold under the name Akypo Soft 45 NV® by Kao Chemicals, polyoxyethylenated and carboxymethylated fatty acids originating from olive oil, such as the one sold under the name Olivem 400® by Biologia E Tecnologia, or oxyethylenated (6 EO) sodium tridecyl ether carboxylate, for example, sold under the name Nikkol ECTD-6NEX® by Nikkol; and

salts of fatty acids (soaps) having a C6 to C22 alkyl chain which are neutralized with an organic or inorganic base, such as potassium hydroxide, sodium hydroxide, triethanolamine, N-methylglucamine, lysine and arginine.

4) Mention may in particular be made, as amino acid derivatives, of alkali salts of amino acids, such as:

sarcosinates, such as sodium lauroyl sarcosinate, for example, sold under the name Sarkosyl NL 97® by Ciba or sold under the name Oramix L 30® by Seppic, sodium myristoyl sarcosinate, such as the product sold under the name Nikkol Sarcosinate MN® by Nikkol, or sodium palmitoyl sarcosinate, sold under the name Nikkol Sarcosinate PN® by Nikkol;

alaninates, such as sodium N-lauroyl-N-methyl amidopropionate, for example, sold under the name Sodium Nikkol Alaninate LN 30® by Nikkol or sold under the name Alanone ALE® by Kawaken, or triethanolamine N-lauroyl-N-methylalanine, for example, sold under the name Alanone ALTA® by Kawaken;

glutamates, such as triethanolamine monococoyl glutamate, such as the product sold under the name Acylglutamate CT-12® by Ajinomoto, triethanolamine lauroyl glutamate, for example, such as the product sold under the name Acylglutamate LT-12® by Ajinomoto, and sodium stearoyl glutamate; aspartates, such as the mixture of triethanolamine N-lauroyl aspartate and triethanolamine N-myristoyl aspartate, for example, sold under the name Asparack® by Mitsubishi;

glycine derivatives (glycinates), such as sodium N-cocoyl glycinate, for example, sold under the names Amilite GCS-12® and Amilite GCK 12 by Ajinomoto;

citrates, such as the citric monoester of oxyethylenated (9 mol) coco alcohols, sold under the name Witconol EC 1 129 by Goldschmidt; and

galacturonates, such as sodium dodecyl D-galactoside uronate, sold by

Soliance.

5) Mention may be made, as sulphosuccinates, for example, of oxyethylenated (3 EO) lauryl (70/30 C12/C14) alcohol monosulphosuccinate, such as the product sold under the names Setacin 103 Special® and Rewopol SB-FA 30 K 4® by Witco, the disodium salt of a hemisulphosuccinate of C12-C14 alcohols, for example, sold under the name Setacin F Special Paste® by Zschimmer Schwarz, oxyethylenated (2 EO) disodium oleamidosulphosuccinate, such as the product sold under the name Standapol SH 135® by Cognis, oxyethylenated (5 EO) lauramide monosulphosuccinate, for example, sold under the name Lebon A-5000® by Sanyo, the disodium salt of oxyethylenated (10 EO) lauryl citrate monosulphosuccinate, for example, sold under the name Rewopol SBCS 50® by Witco, or ricinoleic monoethanolamide monosulphosuccinate, for example, sold under the name Rewoderm S 1333® by Witco. Use may also be made of polydimethylsiloxane sulphosuccinates, such as disodium PEG-12 dimethicone sulphosuccinate, for example, sold under the name Mackanate-DC 30 by MacIntyre.

6) Mention may be made, as alkyl sulphates, for example, of triethanolamine lauryl sulphate (CTFA name: TEA lauryl sulphate), such as the product sold by Fluntsman under the name Empicol TL40 FL or the product sold by Cognis under the name Texapon T42, which products are at 40% in aqueous solution. Mention may also be made of ammonium lauryl sulphate (CTFA name: ammonium lauryl Sulphate), such as the product sold by Huntsman under the name Empicol AL 30FL, which is at 30% in aqueous Solution.

7) Mention may be made, as alkyl ether sulphates, for example, of sodium lauryl ether sulphate (CTFA name: sodium laureth sulphate), such as that sold under the names Texapon N40 and Texapon AOS 225 UP by Cognis, or ammonium lauryl ether sulphate (CTFA name: ammonium laureth sulphate), such as that sold under the name Standapol EA-2 by Cognis.

8) Mention may be made, as sulphonates, for example, of a- olefinsulphonates, such as sodium a -olefin sulphonate (C14-C16), such as the product sold under the name Bio-Terge AS-40® by Stepan, sold under the names Witconate AOS Protege® and Sulframine AOS PH 12® by Witco or sold under the name Bio- Terge AS-40 CG® by Stepan, secondary sodium olefinsulphonate, for example, sold under the name Hostapur SAS 30® by Clariant; or linear alkylarylsulphonates, such as sodium xylenesulphonate, for example, sold under the names Manrosol SXS30®, Manrosol SXS40® and Manrosol SXS93® by Manro.

9) Mention may be made, as isethionates, of acylisethionates, such as Sodium cocoylisethionate, such as the product sold under the name Jordapon Cl P® by Jordan.

10) Mention may be made, as taurates, of the sodium salt of palm kernel oil methyltaurate, for example, sold under the name Hostapon CT Pate ® by Clariant; N-acyl-N-methyl taurates, such as Sodium N-cocoyl-N-methyltaurate, for example, sold under the name Hostapon LT-SF® by Clariant or sold under the name Nikkol CMT-30-T® by Nikkol, or sodium palmi toyl methyltaurate, such as the one sold under the name Nikkol PMT® by Nikkol. The preferred is sodium methyl stearoyl taurate (for example, Nikkol SMT Nikkol).

1 1 ) The anionic derivatives of alkyl polyglucosides can in particular be citrates, tartrates, sulphosuccinates, carbonates and glycerol ethers obtained from alkyl polyglucosides. Mention may be made, for example, of the sodium salt of cocoylpolyglucoside (1 ,4) tartaric ester, for example, sold under the name Eucarol AGE-ET® by Cesalpinia, the disodium salt of cocoylpolyglucoside (1 ,4) sulphosuccinic ester, such as the product sold under the name Essai 512 MP® by Seppic, or the sodium salt of cocoylpolyglucoside (1 ,4) citric ester, for example, sold under the name Eucarol AGE-EC® by Cesalpinia.

In a preferred embodiment, the at least one anionic surfactant of the present invention is select from the group consisting of potassium cetyl phosphate, sodium methyl stearoyl taurate, and mixtures thereof.

Preferably, the amount of the at least one anionic surfactant in the surfactant system of the cosmetic composition of the present invention ranges from about 0.1 % to about 10% by weight and preferably from about 0.1 % to about 8% by weight, more preferably from about 0.1 % to about 5% by weight, based on the total weight of the composition.

FILLERS

The water-resistant cosmetic composition according to the present invention can further comprise at least one filler selected from the group consisting of silica, octenylsuccinic anhydride-esterified starch salts, and mixtures thereof. Preferably, the silica comprises silica aerogel.

The amount of the at least one filler in the cosmetic composition of the invention is at least about 5% by weight, based on the total weight of the composition, preferably ranging from about 5% to about 20% by weight, more preferably from about 5% to about 15% by weight, and most preferably from about 5% to about 10% by weight, based on the total weight of the composition.

Silica

In a preferred embodiment, the silica of the present invention comprises silica aerogel. The“silica aerogel” according to the present invention is a porous material obtained by replacing (by drying) the liquid component of a silica gel with air. Silica aerogels are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, such as, but not limited to, supercritical carbon dioxide (CO2). This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying processes are described in detail in Brinker, C.J., and Scherer, G.W., Sol-Gel Science: New York: Academic Press, 1990.

The hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from about 500 to about 1500 m ² /g, or alternatively from about 600 to about 1200 m ² /g, or alternatively from about 600 to about 800 m ² /g, and a size expressed as the mean volume diameter (D[0.5]), ranging from about 1 to about 30 pm, or alternatively from about 5 to about 25 pm, or alternatively from about 5 to about 20 pm, or alternatively from about 5 to about 15 pm. The specific surface area per unit of mass may be determined via the BET (Brunauer-Emmett-Teller) nitrogen absorption method described in the Journal of the American Chemical Society, vol. 60, page 309, February 1938, corresponding to the international standard ISO 5794/1 . The BET specific surface area corresponds to the total specific surface area of the particles under consideration. The size of the silica aerogel particles may be measured by static light scattering using a commercial granulometer such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is especially described in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

The silica aerogel particles used in the present invention may advantageously have a tamped (or tapped) density ranging from about 0.04 g/cm ³ to about 0.10 g/cm ³ _’ or alternatively from about 0.05 g/cm ³ to about 0.08 g/cm ³ . In the context of the present invention, this density, known as the tamped density, may be assessed according to the following protocol: 40 g of powder are poured into a measuring cylinder; the measuring cylinder is then placed on a Stav 2003 machine from Stampf Volumeter; the measuring cylinder is then subjected to a series of 2500 packing motions (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); the final volume Vf of packed powder is then measured directly on the measuring cylinder. The tamped density is determined by the ratio m/Vf, in this instance 40/Vf (Vf being expressed in cm ³ and m in g).

According to one embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of volume Sv ranging from about 5 to about 60 m ² /cm ³ , or alternatively from about 10 to about 50 m ² /cm ³ , or alternatively from about 15 to about 40 m ² /cm ³ . The specific surface area per unit of volume is given by the relationship: Sv = SM.r where r is the tamped density expressed in g/cm ³ and SM is the specific surface area per unit of mass expressed in m ² /g, as defined above.

In some embodiments, the silica aerogel particles, according to the invention, have an oil-absorbing capacity, measured at the wet point, ranging from about 5 to about 18 ml/g, or alternatively from about 6 to about 15 ml/g, or alternatively from about 8 to about 12 ml/g. The oil-absorbing capacity measured at the wet point, noted Wp, corresponds to the amount of water that needs to be added to 100 g of particle in order to obtain a homogeneous paste. Wp is measured according to the wet point method or the method for determining the oil uptake of a powder described in standard NF T 30-022. Wp corresponds to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measuring the wet point, described below: An amount = 2 g of powder is placed on a glass plate, and the oil (isononyl isononanoate) is then added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is performed using a spatula, and addition of oil is continued until a conglomerate of oil and powder has formed. At this point, the oil is added one drop at a time and the mixture is then triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste must be able to be spread on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil uptake corresponds to the ratio Vs/m.

The aerogels used, according to the present invention, are hydrophobic silica aerogels, preferably of silylated silica (INCI name: silica silylate). The term "hydrophobic silica" means any silica whose surface is treated with silylating agents, for example, halogenated silanes, such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes, such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example, trimethylsilyl groups. Preparation of hydrophobic silica aerogel particles that have been surface-modified by silylation, is found in U.S. Patent No. 7,470,725, incorporated herein by reference. In one embodiment, hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups are desirable.

Suitable examples of hydrophobic silica aerogels, may include, but are not limited to, the aerogels sold under the tradenames of VM-2260 (INCI name: Silica silylate) and VM-2270 (INCI name: Silica silylate), both available from Dow Corning Corporation (Midland, Michigan). The particles of VM-2260 have a mean size of about 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m ² /g. The particles of VM-2270 have a mean size ranging from 5 to 15 microns and a specific surface area per unit of mass ranging from 600 to 800 m ² /g. Another suitable example of a hydrophobic silica aerogel may include, but is not limited to, the aerogels commercially available from Cabot Corporation (Billerica, Massachusetts) under the tradename of Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova Aerogel MT 1 100 and Enova Aerogel MT 1200.

The silica aerogel is preferably hydrophobic silica aerogel, more preferably silica silylate.

Octenylsuccinic Anhvdride-Esterified Starch Salts

Among the octenylsuccinic anhydride-esterified starch salts that may be formulated according to the invention, mention may be made of the calcium, sodium or aluminum salts obtained by reacting octenylsuccinic anhydride with a maize starch, and in particular the following esterified maize starch salts designated below under their INCI name: aluminum starch octenylsuccinate, sodium starch octenylsuccinate, calcium starch octenylsuccinate. Aluminum starch octenylsuccinate will more particularly be used.

UV FILTER SYSTEM

The composition, according to the present invention, comprises a UV filter system. The UV filter system may comprise at least one UV filter selected from the group of inorganic UV filters and organic UV filters, and mixtures thereof.

The composition according to the present invention, may comprise the UV filter system in an amount of from about 0.1 % by weight to about 50% by weight, and in some embodiments from about 5% by weight to about 40% by weight, and in some embodiments from about 5% by weight to about 30% by weight in relation to the total weight of the composition.

Inorganic UV Filters

The composition, according to the present invention, comprise a UV filter system comprising at least one inorganic UV filter. If two or more inorganic UV filters are used, they may be the same or different.

The inorganic UV filter used for the present invention may be active in the UV-A and/or UV-B region. The inorganic UV filter may be hydrophilic and/or lipophilic. The inorganic UV filter is in some embodiments insoluble in solvents, such as water, and ethanol commonly used in cosmetics.

It is in some embodiments desirable that the inorganic UV filter be in the form of a fine particle such that the mean (primary) particle diameter thereof ranges from about 1 nm to about 50 nm, and in some embodiments from about 5 nm to about 40 nm, and in some embodiments from about 10 nm to about 30 nm. The mean (primary) particle size or mean (primary) particle diameter here is an arithmetic mean diameter.

The inorganic UV filter can be selected from the group consisting of silicon carbide, metal oxides which may or may not be coated, and mixtures thereof. And in some embodiments, the inorganic UV filters are selected from pigments (mean size of the primary particles: generally from about 5 nm to about 50 nm, and in some embodiments from about 10 nm to about 50 nm) formed of metal oxides, such as, for example, pigments formed of titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide, or cerium oxide, which are all UV photoprotective agents that are well known per se. And in some embodiments, the inorganic UV filters are selected from titanium dioxide, zinc oxide, and, in some embodiments, titanium oxide.

The inorganic UV filter may or may not be coated. The inorganic UV filter may have at least one coating. The coating may comprise at least one compound selected from the group consisting of alumina, silica, aluminum hydroxide, silicones, silanes, fatty acids or salts thereof (such as sodium, potassium, zinc, iron, or aluminum salts), fatty alcohols, lecithin, amino acids, polysaccharides, proteins, alkanolamines, waxes, such as beeswax, (meth)acrylic polymers, organic UV filters, and (per)fluoro compounds. It is in some embodiments desirable for the coating to include at least one organic UV filter. As the organic UV filter in the coating, a dibenzoylmethane derivative, such as butyl methoxydibenzoylmethane (Avobenzone) and 2,2'-Methylenebis[6-(2H- Benzotriazol-2-yl)-4-(l,l,3,3-Tetramethyl-Butyl) Phenol] (Methylene Bis-Benzotriazolyl Tetramethylbutylphenol), such as marketed as "TINOSORB M" by BASF, may be desirable.

In a known manner, the silicones in the coating(s) may be organosilicon polymers or oligomers comprising a linear or cyclic and branched or cross-linked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitable functional silanes and essentially composed of repeated main units in which the silicon atoms are connected to one another via oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being connected directly to said silicon atoms via a carbon atom.

The term "silicones" also encompasses silanes necessary for their preparation, in particular alkylsilanes.

The silicones used for the coating(s) can be and in some embodiments are selected from the group consisting of alkylsilanes, polydialkylsiloxanes, and polyalkylhydrosiloxanes. And in some embodiments still, the silicones are selected from the group consisting of octyltrimethylsilane, polydimethylsiloxanes, and polymethylhydrosiloxanes.

Of course, the inorganic UV filters made of metal oxides may, before their treatment with silicones, have been treated with other surfacing agents, in particular with cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or their mixtures. The coated inorganic UV filter may have been prepared by subjecting the inorganic UV filter to one or more surface treatments of a chemical, electronic, mechano-chemical, and/or mechanical nature with any of the compounds as described above, as well as polyethylenes waxes, metal alkoxides (titanium or aluminum alkoxides), metal oxides, sodium hexametaphosphate, and those shown, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64.

The coated inorganic UV filters may be titanium oxides coated: with silica, such as the product "Sun veil" from Ikeda, and "Sunsil TIN 50" from Sunjin Chemical; with silica and with iron oxide, such as the product "Sunveil F" from Ikeda; with silica and with alumina, such as the products "Microtitanium Dioxide MT 500 SA" from Tayca, "Tioveil" from Tioxide, and "Mirasun TiW 60" from Rhodia; with alumina, such as the products "Tipaque TTO-55 (B)" and "Tipaque TTO-55 (A)" from Ishihara, and "UVT 14/4" from Kemira; with alumina and with aluminum stearate, such as the product "Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z or MT-01 " from Tayca, the products "Solaveil CT-10 W" and "Solaveil CT 100" from Uniqema, and the product "Eusolex T-AVO" from Merck; with alumina and with aluminum laurate, such as the product "Microtitanium Dioxide MT 100 S" from Tayca; with iron oxide and with iron stearate, such as the product "Microtitanium Dioxide MT 100 F" from Tayca; with zinc oxide and with zinc stearate, such as the product "BR351 " from Tayca; with silica and with alumina and treated with a silicone, such as the products "Microtitanium Dioxide MT 600 SAS", "Microtitanium Dioxide MT 500 SAS", and "Microtitanium Dioxide MT 100 SAS" from Tayca; with silica, with alumina and with aluminum stearate and treated with a silicone, such as the product "STT-30-DS" from Titan Kogyo; with silica and treated with a silicone, such as the product "UV- Titan X 195" from Kemira; with alumina and treated with a silicone, such as the products "Tipaque TTO-55 (S)" from Ishihara or "UV Titan M 262" from Kemira; with triethanolamine, such as the product "STT-65-S" from Titan Kogyo; with stearic acid, such as the product "Tipaque TTO-55 (C)" from Ishihara; or with sodium hexametaphosphate, such as the product "Microtitanium Dioxide MT 150 W" from Tayca. Other titanium oxide pigments treated with a silicone are, and in some embodiments T1O2 treated with octyltrimethylsilane and for which the mean size of the individual particles is from 25 and 40 nm, such as that marketed under the trademark "T 805" by Degussa Silices, T1O2 treated with a polydimethylsiloxane and for which the mean size of the individual particles is 21 nm, such as that marketed under the trademark "70250 Cardre UF Ti02Sb" by Cardre, and anatase/rutile T1O2 treated with a polydimethylhydrosiloxane and for which the mean size of the individual particles is 25 nm, such as that marketed under the trademark "Microtitanium Dioxide USP Grade Hydrophobic" by Color Techniques.

And in some embodiments, the following coated TiC>2 can be used as the coated inorganic UV filter: Stearic acid (and) Aluminum Hydroxide (and) TiC>2, such as the product "MT-100 TV" from Tayca, with a mean primary particle diameter of 15 nm; Dimethicone (and) Stearic Acid (and) Aluminum Hydroxide (and) T1O2, such as the product "S A-TTO-S4" from Miyoshi Kasei, with a mean primary particle diameter of 15 nm; Silica (and) T1O2, such as the product "MT-100 WP" from Tayca, with a mean primary particle diameter of 15 nm; Dimethicone (and) Silica (and) Aluminum Hydroxide (and) T1O2, such as the product "MT -Y02" and "MT -Y-1 10 M3S" from T ayca, with a mean primary particle diameter of 10 nm; Dimethicone (and) Aluminum Hydroxide (and) T1O2, such as the product "SA-TTO-S3" from Miyoshi Kasei, with a mean primary particle diameter of 15 nm; Dimethicone (and) Alumina (and) T1O2, such as the product "UV TITAN Ml 70" from Sachtleben, with a mean primary particle diameter of 15 nm;. and Silica (and) Aluminum Hydroxide (and) Alginic Acid (and) T1O2, such as the product "MT- 100 AQ" from Tayca, with a mean primary particle diameter of 15 nm. In terms of UV filtering ability, T1O2 coated with at least one organic UV filter is more desirable. For example, Avobenzone (and) Stearic Acid (and) Aluminum Hydroxide (and) T1O2, such as the product "HXMT-100ZA" from Tayca, with a mean primary particle diameter of 15 nm, can be used.

The uncoated titanium oxide pigments are, for example, marketed by Tayca under the trademarks "Microtitanium Dioxide MT500B" or "Microtitanium Dioxide MT600B", by Degussa under the trademark "P 25", by Wacker under the trademark "Oxyde de titane transparent PW", by Miyoshi Kasei under the trademark "UFTR", by Tomen under the trademark "ITS" and by Tioxide under the trademark "Tioveil AQ". The uncoated zinc oxide pigments are, for example, those marketed under the trademark "Z-cote" by Sunsmart; those marketed under the trademark "Nanox" by Elementis; and those marketed under the trademark "Nanogard WCD 2025" by Nanophase Technologies. The coated zinc oxide pigments are, for example, those marketed under the trademark "Oxide Zinc CS-5" by Toshiba (ZnO coated with polymethylhydrosiloxane); those marketed under the trademark "Nanogard Zinc Oxide FN" by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alkyl benzoate); those marketed under the trademark "Daitopersion Zn-30" and "Daitopersion Zn-50" by Daito (dispersions in oxyethylenated polydimethylsiloxane/cyclopolymethylsiloxane comprising 30% or 50% of zinc nano oxides coated with silica and polymethylhydrosiloxane); those marketed under the trademark "NFD Ultrafine ZnO" by Daikin (ZnO coated with phosphate of perfiuoroalkyl and a copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane) ; those marketed under the trademark "SPD-Z1 " by Shin-Etsu (ZnO coated with a silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxane); those marketed under the trademark "Escalol Z100" by ISP (alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone mixture); those marketed under the trademark "Fuji ZnO-SMS-10" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); and those marketed under the trademark "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate). The uncoated cerium oxide pigments are marketed, for example, under the trademark "Colloidal Cerium Oxide" by Rhone- Poulenc.

The uncoated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD 2002 (FE 45B)", "Nanogard Iron FE 45 BL AQ", "Nanogard FE 45R AQ", and "Nanogard WCD 2006 (FE 45R)", or by Mitsubishi under the trademark "TY-220".

The coated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD 2008 (FE 45B FN)", "Nanogard WCD 2009 (FE 45B 556)", "Nanogard FE 45 BL 345", and "Nanogard FE 45 BL", or by BASF under the trademark "Oxyde de fer transparent".

Mention may also be made of mixtures of metal oxides, in particular, of titanium dioxide and of cerium dioxide, including a mixture of equal weights of titanium dioxide coated with silica and of cerium dioxide coated with silica, such as marketed by Ikeda under the trademark "Sunveil A", and also a mixture of titanium dioxide and of zinc dioxide coated with alumina, with silica and with silicone, such as the product "M 261 " marketed by Kemira, or coated with alumina, with silica and with glycerol, such as the product "M 21 1 " marketed by Kemira.

Coated inorganic UV filters are desirable, because the UV filtering effects of the inorganic UV filters can be enhanced. In addition, the coating(s) may help uniformly or homogeneously disperse the UV filters in the composition, according to the present invention.

Organic UV Filters The composition, according to the present invention, comprises a UV filter system comprising at least one organic UV filter. If two or more organic UV filters are used, they may be the same or different.

The organic UV filter used for the present invention may be active in the UV- A and/or UV-B region. The organic UV filter may be hydrophilic and/or lipophilic.

The organic UV filter may be solid or liquid. The terms "solid" and "liquid" mean solid and liquid, respectively, at 25°C under 1 atm.

The organic UV filter can be selected from the group consisting of anthranilic compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic compounds; camphor compounds; benzophenone compounds; b,b-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole compounds; imidazoline compounds; bis-benzoazolyl compounds; p-aminobenzoic acid (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; screening polymers and screening silicones; dimers derived from a-alkylstyrene; 4,4- diarylbutadienes compounds; guaiazulene and derivatives thereof; rutin and derivatives thereof; flavonoids; bioflavonoids; oryzanol and derivatives thereof; quinic acid and derivatives thereof; phenols; retinol; cysteine; aromatic amino acids; peptides having an aromatic amino acid residue; and mixtures thereof.

Mention may be made, as examples of the organic UV filter(s), of those denoted below under their INCI names, and mixtures thereof. Anthranilic compounds: menthyl anthranilates, such as marketed under the trademark "Neo Heliopan MA" by Haarmann and Reimer. The dibenzoylmethane compounds: Butyl methoxydibenzoylmethane, such as marketed in particular under the trademark "Parsol 1789" by Hoffmann-La Roche; and isopropyl dibenzoylmethane. Cinnamic compounds: Ethylhexyl methoxycinnamate, such as marketed in particular under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, such as marketed under the trademark "Neo Heliopan E 1000" by Haarmann and Reimer; cinoxate (2- ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethylhexanoate dimethoxycinnamate. Salicylic compounds: Homosalate (homomentyl salicylate), such as marketed under the trademark "Eusolex HMS" by Rona/EM Industries; ethylhexyl salicylate, such as marketed under the trademark "Neo Heliopan OS" by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, such as marketed under the trademark "Dipsal" by Scher; and TEA salicylate, such as marketed under the trademark "Neo Heliopan TS" by Haarmann and Reimer. Camphor compounds, in particular, benzylidenecamphor derivatives: 3-benzylidene camphor, such as manufactured under the trademark "Mexoryl SD" by Chimex; 4- methylbenzylidene camphor, such as marketed under the trademark "Eusolex 6300" by Merck; benzylidene camphor sulfonic acid, such as manufactured under the trademark "Mexoryl SL" by Chimex; camphor benzalkonium methosulfate, such as manufactured under the trademark "Mexoryl SO" by Chimex; terephthalylidene dicamphor sulfonic acid, such as manufactured under the trademark "Mexoryl SX" by Chimex; and polyacrylamidomethyl benzylidene camphor, such as manufactured under the trademark "Mexoryl SW" by Chimex. Benzophenone compounds: Benzophenone-1 (2,4-dihydroxybenzophenone), such as marketed under the trademark "Uvinul 400" by BASF; benzophenone-2 (Tetrahydroxybenzophenone), such as marketed under the trademark "Uvinul D50" by BASF; Benzophenone-3 (2- hydroxy-4-methoxybenzophenone) or oxybenzone, such as marketed under the trademark "Uvinul M40" by BASF; benzophenone-4 (hydroxymethoxy benzophonene sulfonic acid), such as marketed under the trademark "Uvinul MS40" by BASF; benzophenone-5 (Sodium hydroxymethoxy benzophenone Sulfonate); benzophenone-6 (dihydroxy dimethoxy benzophenone); such as marketed under the trademark "Helisorb 1 1 " by Norquay; benzophenone-8, such as marketed under the trademark "Spectra-Sorb UV-24" by American Cyanamid; benzophenone-9 (Disodium dihydroxy dimethoxy benzophenonedisulfonate), such as marketed under the trademark "Uvinul DS-49" by BASF; and benzophenone-12, and n-hexyl 2-(4- diethylamino-2-hydroxybenzoyl)benzoate (such as UVINUL A+ by BASF) b,b- Diphenylacrylate compounds: Octocrylene, such as marketed in particular under the trademark "Uvinul N539" by BASF; and Etocrylene, such as marketed in particular under the trademark "Uvinul N35" by BASF. Triazine compounds: Diethylhexyl butamido triazone, such as marketed under the trademark "Uvasorb HEB" by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, bis- ethylhexyloxyphenol methoxyphenyl triazine, such as marketed under the trademark «TINOSORB S » by CIBA GEIGY, and ethylhexyl triazone, such as marketed under the trademark «UVTNUL T150 » by BASF. Benzotriazole compounds, in particular, phenylbenzotriazole derivatives: 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylpheno, branched and linear; and those described in USP 5240975. Benzalmalonate compounds: Dineopentyl 4'-methoxybenzalmalonate, and polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, such as marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche. Benzimidazole compounds, in particular, phenylbenzimidazole derivatives: Phenylbenzimidazole sulfonic acid, such as marketed in particular under the trademark "Eusolex 232" by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, such as marketed under the trademark "Neo Heliopan AP" by Haarmann and Reimer. Imidazoline compounds: Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate. Bis-benzoazolyl compounds: The derivatives as described in EP-669,323 and U.S. Pat. No. 2,463,264. Para-aminobenzoic acid compounds: PABA (p-aminobenzoic acid), ethyl PABA, Ethyl dihydroxypropyl PABA, pentyl dimethyl PABA, ethylhexyl dimethyl PABA, such as marketed in particular under the trademark "Escalol 507" by ISP, glyceryl PABA, and PEG-25 PABA, such as marketed under the trademark "Uvinul P25" by BASF. Methylene bis-(hydroxyphenylbenzotriazol) compounds, such as 2,2'-methylenebis[6- (2H-benzotriazol-2-yl)-4-methyl-phenol], such as marketed in the solid form under the trademark "Mixxim BB/200" by Fairmount Chemical, 2,2'-methylenebis[6-(2H- benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)phenol], such as marketed in the micronized form in aqueous dispersion under the trademark "Tinosorb M" by BASF, or under the trademark "Mixxim BB/100" by Fairmount Chemical, and the derivatives as described in U.S. Pat. Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE-197,26, 184, and EP-893,1 19, and Drometrizole trisiloxane, such as marketed under the trademark "Silatrizole" by Rhodia Chimie or- "Mexoryl XL" by L’Oreal. Benzoxazole compounds: 2,4-bis[5-l(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]- 6-(2-ethylhexyl)imino- 1,3,5-triazine, such as marketed under the trademark of Uvasorb K2A by Sigma 3V. Screening polymers and screening silicones: The silicones described in WO 93/04665. Dimers derived from a-alkylstyrene: The dimers described in DE-19855649. 4,4- Diarylbutadiene compounds: l,l-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

It is in some embodiments desirable that the organic UV filter(s) be selected from the group consisting of: butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, l,r-(l,4- piperazinediyl)bis[l-[2-[4-(diethylamino)-2-hydroxybenzoyl]p henyl]-methanone 4- methylbenzylidene camphor, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, 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' -aminobenzalmalonate)-6- [(3 - { 1 ,3 ,3 ,3 -tetramethyl- 1 - [(trimethylsilyloxy] - disiloxanyl}propyl)amino]-s-triazine, 2,4,6-tris-(di-phenyl)-triazine, 2,4,6-tris-(ter-phenyl)-triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane, polysilicone-15, dineopentyl 4'-methoxybenzalmalonate, l,l- dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-bis[5-l

(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-eth ylhexyl)imino-l,3,5-triazine, camphor benzylkonium methosulfate, and mixtures thereof.

FATTY COMPOUNDS

In addition to the constituents of the water-resistant cosmetic composition described above, the composition of the present invention can also comprise at least one fatty compound selected from the group consisting of oils, waxes, fatty acids, fatty alcohols, and mixtures thereof.

The proportion of additional fatty compounds in the cosmetic composition according to the invention is generally from about 5% by weight to about 20% by weight, based on the total weight of composition, preferably from about 5% by weight to about 15% by weight, based on the total weight of the composition.

The waxes useful for the present invention may be of mineral, fossil, animal, or vegetable origin, hydrogenated oils, or mixtures thereof. Non-limiting examples of waxes include hydrocarbon-based waxes such as beeswax, candelilla wax, carnauba wax, couricury wax, Japan wax, cork fiber waxes or sugar cane waxes, paraffin waxes, lignite waxes, microcrystalline waxes, lanolin wax, montan wax, ozokerites, synthetic wax, polyethylene waxes, the waxes obtained by Fischer-Tropsch synthesis, hydrogenated oils and glycerides that are solid at 25° C. It is also possible to use silicone waxes, among which mention may be made of alkyl, alkoxy and/or esters of polymethylsiloxane.

Oils which can be used in the invention, mention may be made to polar or slightly polar oils, i.e. oils including an alkyl chain, preferably a C3-C40 alkyl chain. Non-limiting examples of oils to be used in the present invention include:

linear or branched hydrocarbons such as liquid paraffin, isohexadecane, liquid petroleum jelly and light naphthalene oils, and lanolin, hydrocarbon-based oils of plant origin, such as glyceride triesters, which are generally triesters of fatty acids and of glycerol, the fatty acids of which can have varied chain lengths from C to C24, it being possible for these chains to be saturated or unsaturated and linear or branched; these oils are in particular wheat germ oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin seed oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil and musk rose oil; or also caprylic/capric acid triglycerides,

synthetic esters, for instance oils of formula RCOOR' in which R represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R' represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms, on condition that R + R’ is >10, for instance, cetearyl octanoate, isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, 2- ethylphenyl benzoate, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters; citrates or tartrates, such as di(linear C12-C13 alkyl) tartrates, and also di(linear C14-C15 alkyl) tartrates, or acetates.

silicone oils such as polydimethylsiloxanes (PDMS's), optionally including a C3-C40 alkyl or alkoxy chain or a phenyl chain, such as phenyltrimethicones, optionally fluorinated polyalkylmethylsiloxanes, such as polymethyltrifluoropropyldimethylsiloxanes, or with functional groups such as hydroxyl, thiol and/or amine groups; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorosilicones and perfluoro oils;

mixtures thereof.

Non-liming examples of fatty alcohols useful for the present invention are those liquid at room temperature, containing a branched and/or unsaturated carbon- based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or 2- undecylpentadecanol. Non-limiting examples of fatty acids useful for the present invention are higher fatty C12-C22 acids, such as oleic acid and linoleic acid

Preferably, the at least one fatty compound is selected from oils, more preferably from synthetic esters, even more preferably synthetic oils selected from the group consisting of isononyl isononanoate, diisopropyl sebacate and mixtures thereof.

ADDITIONAL INGREDIENTS

In addition to the essential components described hereinbefore, the composition of the invention may further comprise any usual cosmetically acceptable ingredient, which may be chosen especially from perfume/fragrance, preserving agents, solvents, actives, vitamins, additional fillers, silicones, polymers, and mixtures thereof.

A person skilled in the art will take care to select the optional additional ingredients and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

Suitable polymers include, but are not limited to polylactic acid (PLA), xanthan gum, poly C10-30 alkyl acrylate, acrylates/Cio-C3o alkyl acrylate crosspolymer, styrene/acrylates copolymer, lauryl methacrylate/glycol dimethacrylate crosspolymer, ammonium acryloyldimethyltaurate/vp copolymer, dimethicone/vinyl dimethicone crosspolymer and mixtures thereof.

In a preferred embodiment, the cosmetic composition according to the present invention comprises a polymer system comprising at least one polymer selected from the group consisting of polylactic acid (PLA), xanthan gum, poly C10-C30 alkyl acrylate, acrylates/Cio-C3o alkyl acrylate crosspolymer, styrene/acrylates copolymer, lauryl methacrylate/glycol di methacrylate crosspolymer, ammonium acryloyldimethyltaurate/vp copolymer and dimethicone/vinyl dimethicone crosspolymer. In a preferred embodiment, the amount of the polymer system in the composition of the present invention ranges from about 0.5% to 10% by weight, preferably from about 0.5% to about 8% by weight, more preferably from about 0.5% to about 5% by weight, based on the total weight of the composition.

Non-limiting example of preserving agent which can be used in accordance with the invention include phenoxyethanol.

Suitable additional fillers of the invention could be as examples of oil absorbing fillers: mica, magnesium oxide, nylon-12, nylon-66, cellulose, talc, talc (and) methicone, talc (and) dimethicone, perlite, sodium silicate, pumice, PTFE, polymethyl methacrylate, alumina, calcium sodium borosilicate, magnesium carbonate.

Suitable solvents include, but are not limited to water, alcohols, glycols and polyols such as glycerin, caprylyl glycol, pentylene glycol, propylene glycol, butylene glycol, and mixtures thereof.

In various embodiments, the solvent is present in a concentration from about 15 to 90% by weight, or from about 20 to about 85% by weight, or from about 30 to about 75% by weight, or from about 35 to about 75% by weight, or preferably from about 40 to about 75% by weight, based on the total weight of the combinations and/or compositions of the present disclosure.

Suitable additional actives include, but are not limited to, disodium EDTA, triethanolamine, and mixtures thereof.

Examples of silicones used in the composition of the present invention but not limited to are dimethicone and caprylyl methicone.

Non-limiting example of vitamins suitable for the composition of the present invention includes tocopherol.

The additional ingredients, including the solvents and the polymer system, may represent from 20% to 90%, such as from 25% to 85% or such as from 30 to 80% by weight, based on the total weight of the composition of the invention.

By way of non-limiting illustration, the invention will now be described with reference to the following examples.

EXAMPLES

EXAMPLES 1 TO 3 - COSMETIC COMPOSITIONS

A composition according to the prior art is as Example 1 below, and compositions according to the present invention are as Examples 2 and 3, as follows:

EXAMPLE 4 - CUTANEOUS ACCEPTABILITY

The cosmetic composition according to Example 3 was tested in regard to its cutaneous acceptability. The study was performed with 40 female adults and 15 male adults subjects aged between 21 and 68 years old, which were submitted to dermatologic control after 28 days of use of the composition in normal or reasonable conditions.

During the study, there was no adverse event in the subjects with certain/likely/possible imputability with the product or with the study procedure.

Under the study conditions, considering the local intolerance events reported by the subjects or observed by the dermatologist, the product according to the present invention presented a good tolerance on the cutaneous level.

EXAMPLE 5 - ACCEPTANCE ASSESSMENT

The cosmetic composition according to Example 3 was assessed as to check the cosmetic acceptance through a self-assessment questionnaire. The study was performed with 60 female subjects aged from 18 to 61 years old. The assessment was performed after the product application (Ti), nine hours after the product application (Tgh) and twelve hours after the product application (Ti2h). The results are summarized in the table below.

The results demonstrate that the composition according to the present invention has pleasant sensorial properties on the skin, having a positive assessment by the studied subjects.

EXAMPLE 6 - SPF AND WATER RESISTANCE EVALUATION

The compositions according to the present invention were submitted to a SPF and a Water Resistance evaluation. The tests were performed following the ISO/EN 24444 Cosmetics Sun protection test-in vivo determination of the Sun Protection Factor (SPF) (2010). The Water resistance evaluation was performed according to the Colipa Guidelines (December 2005). The results are summarized in the table below.

It can be seen from the tests performed that examples 2 and 3 according to the present invention showed enhanced water-resistance when compared to a composition according to the prior art (example 1 ).