SUNSCREEN COMPOSITIONS

FIELD OF THE INVENTION

The present invention is directed to sunscreen compositions with high SPF, which comprise an association of a blend of at least two polymers and a polylactic acid-based resin (PLA), the process of manufacturing the compositions and their uses.

BACKGROUND OF THE INVENTION

The photoprotection of keratinous substrates, 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 UVB radiation causes skin reddening and sunburn, tends to damage the skin more superficial epidermal layers. It plays a key role in the development of skin cancer and a contributory role in tanning and photoaging.

The UVA radiation is the dominant tanning ray, and we now know that tanning, whether outdoors or in a salon, causes cumulative damage over time. A tan result from injury to the skin's DNA; the skin darkens in an imperfect attempt to prevent further DNA damage. These imperfections, or mutations, can lead to skin cancer.

The long UVA radiations are the less energetic UVA radiation and therefore, they were considered as“less dangerous”. But they are numerous in our environment, as they represent more than 75% of UV rays reaching earth. So it is worth studying their skin impact as they will be repeated every day for a long period of time.

Thus, the UV filters may either protect against UVA radiation (long-wave), UVB radiation (shortwave), or both. In the past, it was commonly held that protection against UVB radiation was the primary or even sole consideration in sun-protection. However, more recent research has revealed that exposure to UVA radiation may also be dangerous and lead to undesirable effects. As such, the current trend in sun-protection endeavors is typically to protect against both UVA and UVB in a single composition, and to increase both the Sun Protection Factor (“SPF”) and the UVA ratings of the composition.

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. Thus, due to the damages caused by sun exposures, many sunscreen compositions have been proposed to overcome the effects induced by UVA and/or UVB radiation. They generally contain organic or mineral UV-screening agents, which function according to their own chemical nature and according to their own properties by absorption, reflection or scattering of the UV radiation. Also, they generally contain mixtures of liposoluble organic screening agents and/or of water-soluble UV-screening agents combined with metal oxide pigments such as titanium dioxide or zinc oxide. The sunscreen compositions having UVA or UVB or UVA/UVB filter systems commonly used in the sunscreen cosmetic market are generally in the form of oil, an oil-in-water emulsion (stabilized dispersion of an oily phase in an aqueous phase) or a water-in-oil emulsion (stabilized dispersion of an aqueous phase in an oily phase) comprising at least one oily phase comprising solvents and oils.

However, most of the available sunscreens on the market when applied to the skin presents heavy, oily and sticky sensation.

Thus, considering the consumer’s needs, it is desired a sunscreen composition with high SPF associated with a clear and light sensation on the skin, non- greasy sensory effect, good oil absorption, long lasting, auto-adaption to hot climate and season and pleasure upon application with easy spreadability.

The challenge of formulating a sunscreen composition having high FPS associated with the unique sensorial described above is that usual ingredients of the state of the art do not achieve a stable and effective sunscreen composition.

The proposed sunscreen composition comprising the combination of a blend of at least two polymers and a polylactic acid-based resin (PLA), providing the benefits described above is not disclosed in the state of the art.

US 8,636,992 relates to chemical compositions comprising thickening components but is silent regarding a polylactic acid-based resin (PLA).

US 2006/005131 1 is related to a hair treatment composition contains a combination of an anionic polysaccharide, a second homopolymer or copolymer, which is built up from acrylamidoalkylsulfonic acids, methacrylamidoalkylsulfonic acids, but is also silent regarding a polylactic acid-based resin (PLA).

WO 2012/030750 describes an acrylic copolymer suitable both as a hair fixative/film former and a thickening agent in hair styling and personal care compositions, but does not disclose a polylactic acid-based resin (PLA). Thus, the inventors succeeded to overcome the problems of the state of the art and surprisingly revealed stable sunscreen compositions with high SPF, by the combination of a blend of at least two polymers and a polylactic acid-based resin (PLA).

SUMMARY OF THE INVENTION

The present invention is directed to provide stable sunscreen compositions with high SPF which comprise an association of a blend of at least two polymers and a polylactic acid-based resin (PLA), the process of manufacturing the composition and their uses.

The composition of the present invention presents a high level of UV- protection in order to protect the keratin fibers from the damages of the sun, a clear and light sensation on the skin, non-greasy sensory effect, good oil absorption, long lasting, auto-adaption to hot climate and season and pleasure upon application with easy spreadability.

DETAILED DESCRIPTION OF THE INVENTION

The sunscreen composition of the present invention comprises:

(a) a blend of at least two polymers comprising:

(i) a first polymer selected from rheology modifier polymer, preferably taurate modifier polymer and most preferably ammonium acryloyldimethyltaurate/VP copolymer;

(ii) a second polymer selected from anionic polymers, preferably acrylates/C-io-30 alkyl acrylate crosspolymer;

(b) a polylactic acid-based resin (PLA); and

(c) a UV filter system.

The composition according to the invention provides excellent sensorial performance as well as surprisingly high SPF values associated to a strong stability of the composition over time.

The pH of the sunscreen composition of the invention is preferably within the range of about 6.2 to about 7.5, more preferably, of about 6.5.

The density of the sunscreen composition of the invention is preferably within the range of about 0.9 g/cm ³ to about 1 .1 g/cm ³ , more preferably, of about 1 .0 g/cm ³ .

Preferably, the polymers of the invention are a mixture of anionic and rheology modifier polymers. In an embodiment, the amount of the blend of at least two polymers in the sunscreen composition of the invention ranges from about 0.2 to about 3.5% by weight, or from about 0.3 to about 2% by weight, from about 0.5 to about 1 % by weight or from about 0.6 to about 0.8% by weight, including all ranges and sub-ranges therebetween, relative to the total weight of the composition.

In a preferred embodiment, the blend of at least two polymers in the sunscreen composition of the invention employs a first polymer in an amount preferably ranging from about 0.05 to about 1 % by weight and preferably from about 0.1 to about 0.5% by weight, or more preferably from about 0.1 to about 0.5% by weight, including all ranges and sub-ranges therebetween, relative to the total weight of the composition.

In a preferred embodiment, the blend of at least two polymers in the sunscreen composition of the invention employs a second polymer in an amount preferably ranging from about 0.05 to about 1 % by weight and preferably from about 0.1 to about 0.5% by weight, or more preferably from about 0.1 to about 0.5% by weight, including all ranges and sub-ranges therebetween, relative to the total weight of the composition.

The amount of the polylactic acid-based resin (PLA) in the sunscreen composition of the invention ranges from about 0.1 to about 3% by weight, or from about 0.2 to about 2% by weight, or from about 0.1 to about 1 % by weight, including all ranges and sub-ranges therebetween, relative to the total weight of the composition.

In a preferred embodiment, the sunscreen composition of the present invention may present a Sun Protection Factor ranging from 30 to 90.

In various embodiments, the sunscreen composition of the present invention may present a Sun Protection Factor of 30, 35, 40, 45, 50, 55, 60, 65, 70, 80 and 90.

In an embodiment, the sunscreen composition of the present invention may present a Sun Protection Factor of 50.

In an embodiment, the sunscreen composition of the present invention may present a Sun Protection Factor of 70.

In an embodiment, the sunscreen composition of the present invention may present a Sun Protection Factor of 90.

The Sun Protection Factors 50, 70 and 90 means that if one burns in the sun after 10 minutes with no sunscreen, it will take fifty, seventy or ninety times longer to burn equivalently when the product is applied as directed. The sunscreen composition of the invention is in the form of an oil in water (O/W) emulsion.

The sunscreen composition of the invention can be used as a daily product for the skin.

The sunscreen composition of the present invention presents a clear and light sensation on the skin, non-greasy sensory effect, good oil absorption, long lasting, auto-adaption to hot climate and season and pleasure upon application with easy spreadability.

The present invention is related to a process of manufacturing a composition for preventing sunburns that provides for the consumer feeling of comfort in extreme conditions of heat and sweat.

In another preferred embodiment, the present invention is related to the use of a composition for manufacturing a sunscreen for preventing sunburn.

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 reaction 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.

POLYMERS

The suitable polymers of the present invention are selected from rheology modifier polymers and anionic polymers which may be water-soluble or water-dispersible at a pH of 7 and at room temperature (25 °C). According to the present invention, the suitable polymers of the present invention could be as follows.

The rheology modifier polymers are pre-neutralized and preferably selected from taurate polymers. Such polymers comprise an ionic monomer portion, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), as well as a further, less polar monomer portion (vinylpyrrolidone or beheneth-25 methacrylate). These polymers are used as thickener and as stabilizer for oil-in-water emulsions and form extremely stable emulsions already at low concentrations. In particular, these polymers can be used in conjunction with almost any oil phase, comprising silicone oils, hydrocarbons/waxes and ester oils.

Examples of taurate polymers are Acrylates/Vinyl Isodecanoate Crosspolymer (Stabylen 30 from 3V), Acrylates/C10-30 Alkyl Acrylate Crosspolymer (Pemulen TR1 and TR2), Carbomers (Aqua SF-1 ), Ammonium Acryloyldimethyltaurate/VP Copolymer (Aristoflex AVC from Clariant), Ammonium Acryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer (Aristoflex HMB from Clariant), Acrylates/Ceteth-20 Itaconate Copolymer (Structure 3001 from National Starch), Polyacrylamide (Sepigel 305 from SEPPIC), Non-ionic thickener, (Aculyn 46 from Rohm and Haas), or mixtures thereof.

Anionic polymers may be polymers with anionic groups distributed along the polymer backbone. Anionic groups, which may include carboxylate, sulfonate, sulphate, phosphate, nitrate, or other negatively charged or ionizable groupings, may be disposed upon groups pendant from the backbone or may be incorporated in the backbone itself.

The anionic polymers may comprise at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of (Cio-C3o)alkyl ester of unsaturated carboxylic acid type.

In certain exemplary and non-limiting embodiments, the copolymers are chosen from the copolymers resulting from the polymerization of:

(1 ) at least one monomer of formula (I):

CH ₂ =CH(R- _! )COOH )

wherein Ri is chosen from H or CH3 or C2H5, providing acrylic acid, methacrylic acid, or ethacrylic acid monomers, and

(2) at least one monomer of (Cio-C3o)alkyl ester of unsaturated carboxylic acid type corresponding to the monomer of formula (II):

CH ₂ =CH(R )COOR »)

Non-limiting examples of (Cio-C3o)alkyl esters of unsaturated carboxylic acids are for example chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate and the corresponding methacrylates, such as lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate, and mixtures thereof.

Additionally, crosslinked polymers may be chosen according to further exemplary embodiments. For example, such polymers may be chosen from polymers resulting from the polymerization of a mixture of monomers comprising:

(1 ) acrylic acid,

(2) an ester of formula (II) described above, in which R2 is chosen from H or CH3, R3 denoting an alkyl radical having from 12 to 22 carbon atoms, and

(3) a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

For example, acrylate/Cio-C3o alkyl acrylate copolymers (INCI name: Acrylates/Cio-3o Alkyl Acrylate Crosspolymer), such as the products sold by Lubrizol under the trade names PEMULEN TR1 , PEMULEN TR2, CARBOPOL 1382 and CARBOPOL EDT 2020 may be chosen.

Anionic polymers useful herein include, for example: Polyacrylic acid; Polymethacrylic acid; Carboxyvinylpolymer; acrylate copolymers such as Acrylate/C 10-30 alkyl acrylate crosspolymer, Acrylic acid/vinyl ester copolymer/AcrylatesNinyl Isodecanoate crosspolymer, Acrylates/Palmeth-25 Acrylate copolymer, Acrylate/Steareth-20 Itaconate copolymer, and Acrylate/Celeth-20 Itaconate copolymer; sulfonate polymers such as Polysulfonic acid, Sodium Polystyrene Sulfonate supplied from Akzo Nobel under the tradename FLEXAN II, copolymers of methacrylic acid and acrylamidomethylpropane sulfonic acid, and copolymers of acrylic acid and acrylamidomethylpropane sulfonic acid; carboxymethycellulose; carboxy guar gum; copolymers of ethylene and maleic acid; and acrylate silicone polymer. In some instances, the anionic polymers include, for example, Carbomer supplied from Noveon under the tradename CARBOPOL 981 and CARBOPOL 980; Acrylates/C10-30 Alkyl Acrylate Crosspolymer having tradenames Pemulen TR-1 , PEMULEN TR-2, CARBOPOL 1342, CARBOPOL 1382, and CARBOPOL ETD 2020, all available from Noveon; sodium carboxymethylcellulose supplied from Hercules as CMC series; and Acrylate copolymer having a tradename Capigel supplied from Seppic; acrylates copolymer having the tradename CARBOPOL Aqua SF-1 and available from Lubrizol as an aqueous dispersion, and acrylates crosspolymer-4 having the tradename CARBOPOL Aqua SF-2 and available from Lubrizol as an aqueous dispersion.

In an embodiment, the anionic polymer of the invention is carbomer which may be commercially available from the supplier Lubrizol under the tradename of CARBOPOL 980. Exemplary of non-ionic polymers could be as follows:

(i) hydroxyethylcellulose, for instance the product NATROSOL 250 HHR PC or NATROSOL 250 HHR CS sold by the company Ashland;

(ii) celluloses modified with groups comprising at least one fatty chain; examples that may be mentioned include:

- hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the product NATROSOL Plus Grade 330 CS (C16 alkyls) sold by the company Ashland, or the product BERMOCOLL EHM 100 sold by the company AkzoNobel; methyl hydroxyethylcellulose; methyl ethyl hydroxyethylcellulose, known as the product STRUCTURE CEL 8000 M sold by the company AkzoNobel; or hydroxypropyl cellulose, known as the product KLUCEL MF PHARM HYDROXYPROPYLCELLULOSE sold by the company Ashland;

- hydroxyethylcelluloses modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500 (nonylphenyl polyethylene glycol (15) ether) sold by the company Amerchol; or

(iii) hydroxypropyl guars such as hydroxypropyl guar sold by as the product JAGUAR HP 105 by the company Rhodia and hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18 (Cu alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia.

Polylactic acid (PLA)

The compositions of the invention comprise porous microparticles of a polylactic acid-based resin, sometimes referred to herein as “polylactic acid microparticles” or“PLA.”

The PLA microparticles may have an enthalpy of fusion of 5 J/g or more, preferably 10 J/g or more, more preferably 20 J/g or more, and most preferably 30 J/g or more. Further, the upper limit is preferably 100 J/g or less, although it is not limited in particular. Enthalpy of fusion refers to a value calculated from a peak area, which shows heat capacity of fusion at approximately 160 °C, in a differential scanning calorimetry (DSC) where a temperature is raised to 200 °C with the temperature rise of 20 °C per minute.

Enthalpy of fusion can be adjusted by controlling the co-polymerization ratio (L/D) between L-lactic acid and D-lactic acid which constitute the polylactic acid-based resin. When the L/D ratio is 95/5 or more, enthalpy of fusion becomes 5 J/g or more and the polylactic acid-based resin becomes crystalline. It is preferred that the co polymerization ratio of L-lactic acid is high because higher ratios facilitate crystallization. L/D is more preferably 97/3 or more, and most preferably 98/2 or more. L/D is 100/0 or less. Because optical isomers such as L and D have molecular structures that are mirror images of each other and physical properties are not different, enthalpy of fusion remains unchanged when the above-described L/D is substituted with D/L and consequently suitable resins include ones in which L/D is substituted with D/L.

Further, the polylactic acid-based resin may contain copolymerization ingredients other than lactic acid. The other copolymerization ingredient units can be, for example, a multivalent carboxylic acid, a polyhydric alcohol, a hydroxycarboxylic acid or a lactone. Exemplary multivalent carboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5- sodium sulfoisophthalic acid and 5-tetrabutyl phosphonium sulfoisophthalic acid. Exemplary polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1 ,4- cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, an aromatic polyhydric alcohol produced by an addition reaction of ethylene oxide to a bisphenol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Exemplary hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6- hydroxycaproic acid and hydroxybenzoic acid. Exemplary lactones include glycolide, e-caprolactone glycolide, e-caprolactone, b-propiolactone, d-butyrolactone, b- butyrolactone, g-butyrolactone, pivalolactone and d-valerolactone. The volume content of the other copolymerization units is preferably 30 mol % or less, more preferably 20 mol % or less, further more preferably 10 mol % or less, most preferably 5 mol % or less, relative to the total monomer units of the polylactic acid-based resin as 100 mol%. Although molecular mass and molecular mass distribution of the polylactic acid-based resin are not limited in particular, the lower limit of weight average molecular mass of the polylactic acid-based resin is preferably 10,000 or more, more preferably 50,000 or more, further more preferably 100,000 or more, most preferably 200,000 or more. Further, although not limited in particular, the upper limit of weight average molecular mass is preferably 1 ,000,000 or less. The weight average molecular mass referred to herein is weight average molecular mass in terms of polymethyl methacrylate (PMMA), measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

The PLA microparticles may have a number average particle diameter of 90 pm or less, preferably 50 pm or less, more preferably 30 pm or less. This improves smoothness. Further, in uses such as cosmetics, because coagulation of particles tends to occur when the number average particle diameter is too small, the lower limit of the number average particle diameter is generally 1 pm or more, preferably more than 1 pm, more preferably 2 pm or more, most preferably 3 pm or more.

The particle diameter distribution index is preferably 2 or less in order to improve flow of the particles and impart a smoother touch. The upper limit of the particle diameter distribution index is preferably 1 .5 or less, more preferably 1 .3 or less, most preferably 1 .2 or less. Further, the lower limit is 1 in theory.

The above-described number average particle diameter of polylactic acid-based resin microparticles having porous shapes can be calculated by measuring diameters of 100 random particles in a scanning electron microscope image and computing the arithmetic average thereof. If a shape of a particle in the SEM image is not a perfect circle, for example, an ellipse, the maximum diameter of the particle is used as its diameter. To measure the particle diameter precisely, the measurement is carried out with a magnification of at least 1000 times or more, preferably with a magnification of 5000 times or more.

The particle diameter distribution index is calculated on the basis of the conversion equations described below, using measurements of the particle diameters obtained by measurement described above:

mi wherein Ri: particle diameter of single particle, n: the number of measurements (=100), Dn: number average particle diameter, Dv: volume average particle diameter, PDI: particle diameter distribution index.

Although the actual amount of pores in a porous microparticle of polylactic acid-based resin is difficult to measure directly, it is possible to use linseed oil absorption capacity as an indirect index, which is defined in pigment test methods such as Japan Industrial Standards (Refined Linseed Oil Method, JIS K 5101 ).

In particular, in the uses such as cosmetics and paints, higher linseed oil capability is preferable, and the lower limit of linseed oil capability is preferably 90 mL/100 g or more, more preferably 100 mL/100 g or more, further more preferably 120 mL/100 g or more, particularly preferably 150 mL/100 g or more, remarkably preferably 200 mL/100 g or more, most preferably 300 mL/100 g or more. The upper limit of linseed oil absorption capability is preferably 1000 mL/100 g or less.

Further, it is preferred that the above-described porous microparticles of polylactic acid-based resin have enthalpy of fusion of 5 J/g or more. Higher enthalpy of fusion brings higher crystallization tendency and, as a result, heat resistance and durability tend to become high. The lower limit of enthalpy of fusion is preferably 10 J/g or more, more preferably 20 J/g or more, further more preferably 30 J/g or more. Further, the upper limit is preferably 100 J/g or less. Enthalpy of fusion can be calculated from an area of peak showing thermal capacity of fusion at approximately 160 °C in Differential Scanning calorimetry (DSC) in which a temperature is raised to 200 °C with a temperature rise of 20 °C per minute.

Sphericity of the above-described porous microparticles of polylactic acid-based resin is preferably 80 or more, more preferably 85 or more, further more preferably 90 or more, particularly preferably 92 or more, most preferably 95 or more. Further, in theory, the upper limit is 100. When sphericity is within the above-described range, it becomes possible to achieve an improvement in quality such as slidability. The sphericity is calculated by observing particles by a scanning electron microscope, measuring both the longest diameters and the shortest diameters of 30 random particles and subsequently substituting the measurements into the equation described below: wherein S: Sphericity, n: the number of measurements (=30), Ds: the shortest diameter of single particle, DL: the longest diameter of single particle.

UV Filter System

Non-limiting suitable UV filter system of the present invention could be as follows:

OIL-SOLUBLE ORGANIC SUNSCREEN INGREDIENT

The “oil-soluble organic sunscreen ingredient” means any organic compound for screening out UV radiation, which can be fully dissolved in molecular form or miscible in an oil phase or which can be dissolved in colloidal form (for example in micellar form) in an oil fatty phase.

Non-limiting examples of oil-soluble organic sunscreen ingredients useful in the invention include, for example, cinnamic derivatives; anthranilates; salicylic derivatives; dibenzoylmethane derivatives; camphor derivatives; benzophenone derivatives; diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives, especially those cited in patent US5624663; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP669323 and US2463264; p-aminobenzoic acid (PABA) derivatives; methylene bis(hydroxyphenylbenzotriazole) derivatives as described in applications US5237071 , US5166355, GB2303549, DE19726184 and EP8931 19; benzoxazole derivatives as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; screening polymers and screening silicones such as those described especially in patent application WO 93/04665; dimers derived from alkyl- styrene such as those described in patent application DE 19855649; 4,4- diarylbutadienes such as those described in patent applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1 133980 and EP1 133981 , merocyanine derivatives such as those described in patent applications WO 04/006878, WO 05/058269 and WO 06/032741 ; and mixtures thereof, the entire contents of the patents and patent applications being incorporated by reference in their entirety.

As examples of other suitable oil-soluble organic sunscreen ingredients, mention may be made of those denoted hereinbelow under their INCI name:

Cinnamic derivatives:

Examples of suitable cinnamic derviatives include, but are not limited to, ethylhexyl methoxycinnamate sold in particular under the trade name“Parsol ^® MCX” by DSM Nutritional Products, isopropyl methoxycinnamate, isoamyl methoxycinnamate sold under the trade name“Neo Heliopan ^® E 1000” by Symrise, DEA methoxycinnamate, diisopropyl methylcinnamate, glyceryl ethylhexanoate dimethoxycinnamate.

Dibenzoylmethane derivatives:

Examples of suitable dibenzoylmethane derivatives include, but are not limited to, butyl methoxydibenzoylmethane sold especially under the trade name “Parsol ^® 1789” by DSM, isopropyl dibenzoylmethane.

Salicylic derivatives:

Examples of suitable salicylic derivatives include, but are not limited to, 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“DipsalTM” by Scher, TEA salicylate sold under the name“Neo Heliopan ^® TS” by Symrise.

beta, beta -Diphenylacrylate derivatives:

Examples of suitable beta, beta -Diphenylacrylate derivatives include, but are not limited to, octocrylene sold in particular under the trade name“Uvinul ^® N539” by BASF, etocrylene sold in particular under the trade name“Uvinul ^® N35” by BASF.

Benzophenone derivatives:

Examples of suitable benzophenone derivatives include, but are not limited to, benzophenone-1 sold under the trade name “Uvinul ^® 400” by BASF, benzophenone-2 sold under the trade name“Uvinul ^® D50” by BASF, benzophenone-

3 or oxybenzone sold under the trade name“Uvinul ^® M40” by BASF, benzophenone-

4 sold under the trade name “Uvinul ^® MS40” by BASF, benzophenone-5, benzophenone-6 sold under the trade name “Helisorb ^® 1 1” 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+” or as a mixture with octyl methoxycinnamate under the trade name“Uvinul ^® A+B” by BASF.

Benzylidenecamphor derivatives:

Examples of suitable benzylidenecamphor derivatives include, but are not limited to, 3-Benzylidene camphor manufactured under the name“Mexoryl™ SD” by Chimex, 4-methylbenzylidene camphor sold under the name“Eusolex ^® 6300” by Merck, polyacrylamidomethyl benzylidene camphor manufactured under the name “Mexoryl™ SW” by Chimex.

Phenylbenzotriazole derivatives:

Examples of suitable phenylbenzotriazole derivatives include, but are not limited to, drometrizole trisiloxane sold under the name“silatrizole” by Rhodia Chimie, methylene bis-benzotriazolyl tetramethylbutyl-phenol sold in solid form under the trade name“MIXXIM BB/100” by Fairmount Chemical, or in micronized form as an aqueous dispersion under the trade name“Tinosorb ^® M” by Ciba Specialty Chemicals.

Triazine derivatives:

Examples of suitable triazine derivatives include, but are not limited to, bis-Ethylhexyloxyphenol methoxyphenyl triazine sold under the trade name“Tinosorb ^® S” by BASF, ethylhexyl triazone sold in particular under the trade name“Uvinul ^® T 150” by BASF, diethylhexyl butamido triazone sold under the trade name“Uvasorb ^® FIEB” by Sigma 3V, 2,4,6-tris(dineopentyl 4’-aminobenzalmalonate)-s-triazine, 2,4,6- tris(diisobutyl 4’-aminobenzalmalonate)-S triazine, 2,4-bis(dineopentyl 4'- aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s-triazine, symmetrical triazine screening agents described in patent US 6,225,467, patent application WO 2004/085412 (see compounds 6 and 9) or the document "Symmetrical Triazine Derivatives" IP.COM Journal, IP.COM Inc., West Flenrietta, NY, US (20 September 2004), especially 2,4, 6-tris(biphenyl)-1 ,3, 5-triazines (in particular 2,4, 6-tris(biphenyl-4- yl)-1 ,3,5-triazine and 2,4,6-tris(terphenyl)-1 ,3,5-triazine, which is included in patent applications WO 06/035000, WO 06/034982, WO 06/034991 , WO 06/035007, WO 2006/034992 and WO 2006/034985).

Anthranilic derivatives:

An example of a suitable anthranilic derivative includes, but is not limited to, menthyl anthranilate sold under the trade name“Neo Fleliopan ^® MA” by Symrise.

Imidazoline derivatives:

An example of a suitable imidazoline derivative includes, but is not limited to, ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

Benzalmalonate derivatives:

An example of a suitable Benzalmalonate derivative includes, but is not limited to, polyorganosiloxane containing benzalmalonate functions, for instance polysilicone-15, sold under the trade name“Parsol ^® SLX” by DSM Nutritional Products.

4,4-Diarylbutadiene derivatives: An examples of a suitable 4,4-diarylbutadiene derivative includes, but is not limited to, 1 -Dicarboxy(2,2’-dimethylpropyl)-4, 4-diphenyl-butadiene.

Benzoxazole derivatives:

An example of suitable benzoxazole derivative includes, but is not limited to, 2,4-bis[5-(1 -dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylh exyl) imino-1 ,3,5-triazine sold under the name Uvasorb ^® K2A by Sigma 3V, and mixtures thereof.

Preferably, the oil-soluble organic sunscreen ingredient will be chosen from butyl methoxydibenzoylmethane, ethylhexyl salicylate, ethylhexyl triazone, octocrylene, drometrizole trisiloxane, bis-ethylhexyloxyphenol methoxyphenyl triazine, and mixtures thereof.

The oil-soluble organic sunscreen ingredient is preferably present in the composition according to the invention in an amount of from about 3% to about 25% by weight, preferably in an amount of from about 5% to about 20% by weight, and most preferably about 7% to about 18% by weight, based on the total weight of the composition.

WATER-SOLUBLE ORGANIC SUNSCREEN INGREDIENT

The “water-soluble organic sunscreen ingredient” means any organic compound for screening out UV radiation, which can be fully dissolved in molecular form or miscible in a liquid aqueous phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

Non-limiting examples of water-soluble organic sunscreen ingredients useful in the invention include, for example, terephthalylidene dicamphor sulfonic acid (Ecamsule), phenylbenzimidazole sulfonic acid (Ensulizole), benzophenone-4, aminobenzoic acid (PABA), 4-Bis(polyethoxy)-para-aminobenzoic acid polyethoxyethyl ester (PEG-25 PABA), camphor benzalkonium methosulfate, methylene bis-benzotriazolyl tetramethylbutylphenol (Bisoctrizole), disodium phenyl dibenzimidazole tetrasulfonate (Bisdisulizole disodium), and tris-biphenyl triazine; their derivatives and corresponding salts; naphthalene bisimide derivatives such as those described in European patent application EP1990372 A2, the entire contents of which is hereby incorporated by reference; and cinnamido amine cationic quaternary salts and derivatives such as those described in United States Patent 5,601 ,81 1 , the entire contents of which is hereby incorporated by reference, and mixtures thereof.

The salts of the compounds that may be used according to the invention are chosen in particular from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminum, manganese or copper; salts of ammonium of formula NH4+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2- hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts. Salts chosen from sodium, potassium, magnesium, strontium, copper, manganese or zinc salts are preferably used. The sodium salt is preferably used.

Preferably, the water-soluble organic sunscreen ingredient will be chosen from terephthalylidene dicamphor sulfonic acid, methylene bis-benzotriazolyl tetramethylbutylphenol, and mixtures thereof.

The water-soluble organic sunscreen ingredient is preferably present in the composition according to the invention in an amount of from about 0.1 % to about 10% by weight, preferably in an amount of from about 0.5% to about 8% by weight, and most preferably about 1 % to about 7% by weight, based on the total weight of the composition.

SILICA-COATED TITANIUM DIOXIDE SUNSCREEN INGREDIENT

The “silica-coated titanium dioxide sunscreen ingredient” means spherical beads which are formed by encapsulating titanium dioxide particles in silica.

Non-limiting examples of silica coated titanium dioxide sunscreen ingredients useful in the invention include, for example, titanium dioxide coated with silica, such as the product“Sunsil Tin50” from Sunjin Chemical known under the INCI name silica (and) titanium dioxide having a composition of silica:titanium dioxide of about 55:45 and having a particle size from about 2 microns to about 7 microns.

The silica-coated titanium dioxide sunscreen ingredient is preferably present in the composition according to the invention in an amount of from about 1 % to about 10% by weight, preferably in an amount of from about 2% to about 10% by weight, and most preferably about 5% to about 10% by weight, based on the total weight of the composition.

The suitable UV filter system of the present invention comprises terephthalylidene dicamphor sulfonic acid, octocrylene and butyl methoxydibenzoylmethane sulfonic acid, which are preferably known as Mexoryl™ SX and UV System, respectively. According to the invention, the concentration of the mixture of sunscreen/UV filters in the system may be between about 5% to about 35%, preferably between about 7% to about 30% and even more preferably between about 10 to about 29% by weight of the total weight of the composition.

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 such as additional sunscreens, perfume/fragrance, preserving agents, solvents, actives, surfactants, fat materials, vitamins, fillers, silicones 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.

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

Suitable fillers of the invention could be as examples of oil-absorbing fillers: mica, silica, zea may (corn) starch, magnesium oxide, nylon-12, nylon-66, cellulose, polyethylene, talc, talc (and) methicone, talc (and) dimethicone, perlite, sodium silicate, pumice, ptfe, polymethyl methacrylate, oryza sativa (rice) starch, aluminum starch octenylsuccinate, potato starch modified, alumina, silica silylate, calcium sodium borosilicate, magnesium carbonate, hydrated silica, dimethicone/vinyl dimethicone crosspolymer, sodium carboxylmethyl starch.

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 00% by weight, or from about 20 to about 80% by weight, or from about 30 to about 70% by weight, or from about 35 to about 75% by weight, or preferably from about 40 to about 70% by weight, and more preferably from about 45 to about 65% by weight, including ranges and sub-ranges there between, 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. In addition to the emulsifying agents of the present disclosure, surfactants may also be used in the compositions of the present invention non-limiting examples of surfactants suitable for use are fatty acids, glyceryl esters in addition to glyceryl stearate, alkoxylated fatty alcohols, such as stearic acid, laureth-12, glyceryl isostearate, disodium stearoyl glutamate, potassium cetyl phosphate, poloxamer 338, sodium methyl stearoyl taurate and mixtures thereof.

Exemplary fat or oil materials include, but are not limited to, esters, fatty acids, synthetic oils, and hydrocarbons/paraffins, such as stearyl alcohol, myristic acid, palmitic acid silicones mineral oil, plant/vegetable oils, and mixtures thereof.

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

The additional ingredients may represent from 60% to 85%, such as from 60% to 82% or such as from 65 to 80% by weight of the total weight of the composition.

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

EXAMPLES

Examples 1 to 6

A suitable composition of the invention is as Examples 1 and Example 2 is considered the closest prior art, as follows:

Example 3

A non-limiting example regarding the preparation of the composition of Example 1 , could be as follows:

Step (A): The aqueous phase comprising water, preservatives and surfactants is mixed at a room temperature;

Step (B): The thickening polymers are added to the aqueous phase by mixing well;

Step (C): Subsequently, the polymer is neutralized; Step (D): The oily phase comprising the PLA, UV filter system and fatty compound is heated up to 70 °C;

Step (E): The emulsion is achieved by the addition of oily phase on the neutralized aqueous phase with a cold bath, and

Step (F): Adding the fillers and fragrance to the emulsion of Step (E) by mixing well.

Example 4

An in vitro study was conducted in order to evaluate the UVA Protection (SPF) and wave-length of the composition of Example 1 , which was applied in a standardized quantity on PMMA Sunplates, according to COLIPA methodology“In vitro method for the determination of the UVA protection factor and critical wave-length values of sunscreen products” (201 1 ).

^* Confidence Interval.

The composition of Example 1 has an average UVA SPF of 28.2.

Example 5

An in vivo study was conducted in order to evaluate the Sun Protection Factor (SPF) of the composition of Example 1 , applied in standardized and defined zones, on 10 healthy adult subject’s back, followed by exposure to UV radiation according to the ISO/EN24444 Cosmetics Sun Protection test methods - In vivo determination of the Sun Protection Factor (SPF) (2010).

^* Confidence Interval.

The composition of Example 1 has an average SPF of 91 .8.

Example 6

A qualitative in vivo test (Quali-Flome Flash-Sequential monadic) was conducted with 12 volunteers, women, between 18 and 55 years old, having oily skin, during 7 days, in order to compare the performance of the compositions of Examples 1 and 2.

As a result, the volunteers considered the composition of Example 1 superior than the composition of Example 2 regarding the evaluated attributes: