WO2022221930A1

WO2022221930A1 - Cosmetic sunscreen composition, use of a cosmetic sunscreen composition, and process for manufacturing a cosmetic sunscreen composition

Info

Publication number: WO2022221930A1
Application number: PCT/BR2021/050169
Authority: WO
Inventors: Pedro Tupinamba Werneck BARROSO; Livia FERREIRA; Carlos GRANADOS CONTRERAS
Original assignee: L'oreal
Priority date: 2021-04-23
Filing date: 2021-04-23
Publication date: 2022-10-27
Also published as: BR112023014058A2; FR3122087A1

Abstract

The present invention is directed to new cosmetic sunscreen compositions comprising (a) silica silylate; (b) suspending agent selected from polyhydroxystearic acid, or a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate; and (c) at least one UV filter. The present invention is also directed to the use of a cosmetic sunscreen composition, and to a process for manufacturing a cosmetic sunscreen composition.

Description

COSMETIC SUNSCREEN COMPOSITION, USE OF A COSMETIC SUNSCREEN COMPOSITION, AND PROCESS FOR MANUFACTURING A COSMETIC

SUNSCREEN COMPOSITION FIELD OF THE INVENTION

The present invention is directed to a new cosmetic sunscreen composition comprising (a) silica silylate; (b) a suspending agent selected from polyhydroxystearic acid, or a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate, and (c) at least one UV filter. The present invention is also directed to the use of a cosmetic sunscreen composition, and to a process for manufacturing a cosmetic sunscreen 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 cosmetic sunscreen compositions used to accomplish photoprotection, namely, inorganic UV filters and organic UV filters.

The degree of UV protection afforded by a cosmetic sunscreen composition is directly related to the amount and type of UV filters contained therein. Particularly, cosmetic sunscreen compositions must provide good protection against the sun rays, a measure of which is the Sun Protection Factor (SPF) value, a desirable balance between UVA and UVB protection, particularly a minimum UVA protection factor, yet have satisfactory sensory perception, such as a smooth but not greasy feel upon application.

However, this combination of properties has been difficult to achieve, particularly because many sunscreen active compounds themselves have an oily or greasy feel, and increasing their content tends to cause the final product to suffer from that effect.

Also, most organic sunscreen filters are oil-like and/or oil-soluble materials. High levels of sunscreen filters in sunscreen products render the products less appealing for their greasy skin feel, stickiness, long drying time.

In this sense, a cosmetic ingredient used to help control the oiliness of the keratinous material after the application of the cosmetic sunscreen composition, and to provide a matte effect, is silica silylate. Nonetheless, an additional problem of cosmetic sunscreen compositions with this ingredient is that high concentrations of silica silylate tend to repel and agglomerate in emulsions, particularly in oil-in-water emulsions due to the presence of water on the external phase, resulting in an unstable cosmetic sunscreen composition.

Therefore, there is a need for new cosmetic sunscreen compositions with high SPF and a higher amount of silica silylate, that do not feel heavy on the skin and that are capable of controlling the oiliness of the skin after their application, leaving the skin with a matte finish, which is stable.

That said, it is the objective of this invention to provide a stable cosmetic sunscreen composition with higher amounts of silica silylate in an emulsion, particularly an oil-in-water emulsion.

The inventors of the present application have surprisingly managed to develop such new cosmetic sunscreen composition by using a suspending agent selected from polyhydroxystearic acid, or a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate.

SUMMARY OF THE INVENTION

The present invention is directed to new cosmetic sunscreen compositions comprising (a) silica silylate; (b) a suspending agent selected from polyhydroxystearic acid, or a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate; and (c) at least one UV filter. The present invention is also directed to the use of a cosmetic sunscreen composition, and to a process for manufacturing a cosmetic sunscreen composition.

Other features and advantages of the present invention will be apparent from the following more detailed description of the desirable embodiments which illustrates, by way of example, the principles of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 relates to microscopies using polarized light of a stable formula - test of Example 6.

Figure 2 relates to microscopies using polarized light of an unstable formula - test of Example 6.

Figure 3 relates to the double approach results of the Sun Protection Factor (SPF) - in vitro test of Example 8.

DETAILED DESCRIPTION OF THE INVENTION

In an embodiment, the cosmetic sunscreen composition of the present invention comprises:

(a) from about 0.1 to about 2.5 % by weight, based on the total weight of the composition, of silica silylate;

(b) from about 0.3 to about 5.0 % by weight, based on the total weight of the composition, of a suspending agent selected from polyhydroxystearic acid, or a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate;

(c) from about 15.0 to about 35.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition, of at least one UV filter.

In a preferred embodiment, the amount of the silica silylate ranges from about 0.1 to about 1 .0 %, from about 0.2 to about 2.3 %, from about 0.5 to about 1 .2 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

In a preferred embodiment, the suspending agent is polyhydroxystearic acid. In this case, the polyhydroxystearic acid is present at a range from about 0.4 to about 4.0%, from about 0.5 to about 3.0 %, from about 0.6 to about 2.0 %, from about 0.8 to about 1 .0 %, from about by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

In another preferred embodiment, the suspending agent is a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate, in a ratio of about 0.8:0.2. In this case, the mixture is present at a range from about 0.4 to about 4.0%, from about 0.5 to about 3.0 %, from about 0.6 to about 2.0 %, from about 0.8 to about 1 .2 %, from about by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

In a preferred embodiment, the cosmetic sunscreen composition further comprises cosmetically acceptable ingredients selected from active compounds, fatty compounds, fillers, fragrances, polymers, solvents, vitamins, additional UV filters, preserving agents, surfactants and mixtures thereof.

In a preferred embodiment, the cosmetic sunscreen composition of the present invention presents a Sun Protection Factor (SPF) ranging from 30 to 80, preferably from 40 to 70, more preferably about 70. In various embodiments, the cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or 90.

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

In a preferred embodiment, the cosmetic sunscreen composition of the present invention is in the form of an oil in water (O/W) emulsion.

The cosmetic sunscreen composition of the present invention can be used as a daily product for the photoprotection of keratinous materials with high SPF, with dry touch oil control and good stability.

Terms

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

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.

The terms “comprising,” “having,” and “including” are used in their open, non-limiting sense.

The compositions and methods of the present disclosure can comprise, consist of, or consist essentially of the essential elements and limitations of the disclosure described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful.

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

The terms “a,” “an,” and “the” are understood to encompass the plural as well as the singular. Thus, the term “a mixture thereof” also relates to “mixtures thereof.” Throughout the disclosure, the term “a mixture thereof” is used, following a list of elements as shown in the following example where letters A-F represent the elements: “one or more elements selected from the group consisting of A, B, C, D, E, F, and a mixture thereof.” The term, “a mixture thereof does not require that the mixture include all of A, B, C, D, E, and F (although all of A, B, C, D, E, and F may be included). Rather, it indicates that a mixture of any two or more of A, B, C, D, E, and F can be included. In other words, it is equivalent to the phrase “one or more elements selected from the group consisting of A, B, C, D, E, F, and a mixture of any two or more of A, B, C, D, E, and F.

All percentages, parts and ratios herein are based upon the total weight of the compositions of the present disclosure, unless otherwise indicated.

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” which can encompass +/- 10%, +/- 8%, +/- 6%, +/- 5%, +/- 4%, +/- 3%, +/- 2%, +/- 1%, or +/- 0.5%.

All numbers expressing pH values are to be understood as being modified in all instances by the term “about” which encompasses up to +/- 3%.

“Substituted," as used herein, means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen containing groups, ester groups, thiol groups, sulphonate groups, thiosulphate groups, siloxane groups, and polysiloxane groups. The substituent(s) may be further substituted.

Likewise, the term “a salt thereof” also relates to “salts thereof.” Thus, where the disclosure refers to “an element selected from the group consisting of A, B, C, D, E, F, a salt thereof, and a mixture thereof,” it indicates that that one or more of A,

B, C, D, and F may be included, one or more of a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included, or a mixture of any two of A, B,

C, D, E, F, a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included.

The salts referred to throughout the disclosure may include salts having a counter-ion such as an alkali metal, alkaline earth metal, or ammonium counter-ion. This list of counter-ions, however, is non-limiting.

All components and elements positively set forth in this disclosure can be negatively excluded from the claims. In other words, the compositions of the instant disclosure can be free or essentially free of all components and elements positively recited throughout the instant disclosure.

All publications and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. In the event of an inconsistency between the present disclosure and any publications or patent application incorporated herein by reference, the present disclosure controls.

Silica Silylate

The silica silylate of the present invention, which could also be mentioned as “silica aerogel”, 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 silica silylate (e.g., hydrophobic silica silylate particles) used in the present invention has a specific surface area per unit of mass (SM) ranging from about 500 to about 1500 m²/g, or alternatively from about 600 to about 1200 m²/g, or alternatively from about 600 to about 800 m²/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 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 particles used in the present invention may advantageously have a tamped (or tapped) density ranging from about 0.04 g/cm³ to about 0.10 g/cm³ _’ or alternatively from about 0.05 g/cm³ to about 0.08 g/cm³. 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 cm³ and m in g).

According to one embodiment, the silica silylate particles used in the present invention have a specific surface area per unit of volume Sv ranging from about 5 to about 60 m²/cm³, or alternatively from about 10 to about 50 m²/cm³, or alternatively from about 15 to about 40 m²/cm³. 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/cm³ and SM is the specific surface area per unit of mass expressed in m²/g, as defined above.

In some embodiments, the silica silylate 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 isonanoate) 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.

In the context of the present invention, the silica silylate is a "hydrophobic silica", meaning 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 silylate, 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 m²/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 m²/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 1100 and Enova Aerogel MT 1200.

UV Filters

The cosmetic sunscreen composition of the present invention comprises at least one UV filter.

According to the present invention, the concentration of the at least one UV filter ranges from about 15.0 to about 35.0 %, from about 16.0 to about 34.0 %, from about 17.0 to about 33.0 %, from about 18.0 to about 32.0 %, from about 19.0 to about 31 .0 %, from about 20.0 to about 21 .%, from about 20.0 to about 28.0 %, from about 21 .0 to about 27.0 %, from about 22.0 to about 26.0 %, from about 23.0 to about 25.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

Suitable UV filters 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 EP893119; 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, EP1133980 and EP1133981 , 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 herein below under their INCI name:

Cinnamic derivatives:

Examples of suitable cinnamic derivatives include, but are not limited to, ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, DEA methoxycinnamate, diisopropyl methylcinnamate, glyceryl ethylhexanoate dimethoxycinnamate.

Dibenzoylmethane derivatives:

Examples of suitable dibenzoylmethane derivatives include, but are not limited to, isopropyl dibenzoylmethane, butyl methoxydibenzoylmethane,

Salicylic derivatives:

Examples of suitable salicylic derivatives include, but are not limited to, homosalate, ethylhexyl salicylate, dipropylene glycol salicylate and TEA salicylate.

Beta, beta -Diphenylacrylate derivatives:

Examples of suitable beta, beta -diphenylacrylate derivatives include, but are not limited to, etocrylene.

Benzophenone derivatives:

Examples of suitable benzophenone derivatives include, but are not limited to, benzophenone-1 , benzophenone-2, benzophenone-3 or oxybenzone, benzophenone-4, benzophenone-5, benzophenone-6, benzophenone-8, benzophenone-9, benzophenone-12, n-hexyl 2-(4-diethylamino-2- hydroxybenzoyl)benzoate or as a mixture with octyl methoxycinnamate.

Benzylidenecamphor derivatives:

Examples of suitable benzylidenecamphor derivatives include, but are not limited to, 3-benzylidene camphor manufactured, 4-methylbenzylidene camphor, polyacrylamidomethyl benzylidene camphor manufactured.

Phenylbenzotriazole derivatives:

Examples of suitable phenylbenzotriazole derivatives include, but are not limited to, drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethylbutyl- phenol, or in micronized form as an aqueous dispersion.

Triazine derivatives:

Examples of suitable triazine derivatives include, but are not limited to, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, ethylhexyl triazone, 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 Henrietta, 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 06/035, 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, methyl anthranilate.

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.

4,4-Diarylbutadiene derivatives:

An example 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-ethylhexyl) imino-1 ,3,5-triazine, and mixtures thereof.

Preferably, the oil-soluble organic sunscreen ingredient will be chosen from ethylhexyl salicylate, 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 15.0 to about 25.0 %, from about 16.0 to about 24.0 %, from about 17.0 to about 23.0 %, from about 18.0 to about 22.0 %, from about 19.0 to about 21.0 %, from about 20.0 to about 20.5%, from about 20.0 to about 22.0 %, from about 20.0 to about 25.0 %,by weight, and most preferably about 18.0 to about 21.0 %,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, phenylbenzimidazole sulfonic acid, 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 ,811 , 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 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 10.0 % by weight, preferably in an amount of from about 0.5 to about 8.0 % by weight, and most preferably about by weight, based on the total weight of the composition.

In a preferred embodiment, the at least one UV filter is selected from bis- ethylhexyloxyphenol methoxyphenyl triazine, terephthalylidene dicamphor sulfonic acid, drometrizole trisiloxane, butyl methoxydibenzoylmethane, ethylhexyl salicylate, ethylhexyl triazone, phenylbenzimidazole sulfonic acid and mixtures thereof.

Additional Ingredients

In addition to the essential components described herein before, the cosmetic sunscreen composition of the present invention may further comprise any usual cosmetically acceptable ingredient, which may be chosen especially from such as active compounds, fatty compounds, fillers, fragrances, polymers, solvents, vitamins, preserving agents, surfactants and mixtures thereof

The cosmetic sunscreen composition of the present invention comprises water. The water used may be sterile demineralized water and/or deionized water and/or a floral water such as rose water, cornflower water, chamomile water or lime water, and/or a natural thermal or mineral water such as, for example: water from Vittel, water from the Vichy basin, water from Uriage, water from La Roche Posay, water from La Bourboule, water from Enghien-les-Bains, water from Saint Gervais-les-Bains, water from Neris-les-Bains, water from Allevar-les-Bains, water from Digne, water from Maizieres, water from Neyrac-les-Bains, water from Lons-le-Saunier, water from EauxBonnes, water from Rochefort, water from Saint Christau, water from Les Fumades, water from Tercis-les-Bains or water from Avene. Water may also comprise reconstituted thermal water, that is to say a water comprising trace elements such as zinc, copper, magnesium, etc., reconstituting the characteristics of a thermal water.

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, acrylates/Cio-3o alkyl acrylate crosspolymer, styrene/acrylates copolymer, hydroxyethylcellulose and mixtures thereof.

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

Additional suitable solvents include, but are not limited to, C12-15 alkyl benzoate, pentylene glycol, caprylyl glycol, propanediol, alcohol denaturated and mixtures thereof.

Adequate surfactants may be selected from potassium cetyl phosphate, sodium methyl stearoyl taurate and inulin lauryl carbamate, among others.

In various embodiments, the solvent is present in a concentration from about 15 to 100% by weight, or from about 25 to about 80% by weight, or from about 30 to about 70% by weight, or from about 35 to about 60% by weight, or preferably from about 40 to about 50% by weight, and more preferably from about 50 to about 55% 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.

The composition may comprise at least one dye/pigment, preferably titanium oxide or iron oxides.

Exemplary fat or oil materials include, but are not limited to, isopropyl lauroyl sarcosinate, stearyl alcohol, caprylic/capric triglyceride, diisopropyl sebacate, isopropyl myristate, neopentyl glycol diethylhexanoate and mixtures thereof. The composition may also comprise at least one filler, such as silica and/or cellulose.

The additional ingredients, without including solvents, may represent from 17% to 21 %, such as from 18% to 20% or such as from 18.5 to 20% 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.

PROCESS FOR MANUFACTURING A COSMETIC SUNSCREEN COMPOSITION

A non-limiting example regarding the preparation of the cosmetic sunscreen composition according to the present invention could be as follows:

Step (A): Main Vessel - Room Temperature Hot aqueous phase comprising aqueous raw materials in a temperature ranging from about 60-70 °C;

Step (B): Side Vessel - hot oily phase comprising oil raw materials, polymers, preservatives, vitamins, and emulsifier in a temperature ranging from about 75 ^QC to about 80 ^QC;

Step (C): the oily phase of step (B) is added to the aqueous phase of step (A), followed by mixing the mixture;

Step (D): the fillers are gradually added to the mixture obtained in step (C) and mixed until homogeneity, at a temperature of below about 30^QC;

Step (E): alcohol is added.

Embodiments

An example of a suitable cosmetic sunscreen composition according to the present invention comprises:

- from about 18.0 to about 22.0 % of bis-ethylhexyloxyphenol methoxyphenyl triazine, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, drometrizole trisiloxane, ethylhexyl salicylate and ethylhexyl triazone;

- from about 2.0 to about 6.0 % of polyhydroxystearic acid and/or neopentyl glycol, C12-22 alkyl acrylate/hydroxyethylacrylate copolymer, acrylates/Cio-30 alkyl acrylate crosspolymer, aluminum starch octenylsuccinate, hydroxyethylcellulose and polyhydroxystearic acid;

- from about 8.0 to about 11 .0 % of propanediol, caprylyl glycol and alcohol denatured ;

- from about 17.0 to about 21 .0 % of additional cosmetically acceptable ingredients, such as vitamins, fillers, fatty compounds and fragrances;

- from about 40.0 to about 50.0 % of water.

Another suitable cosmetic sunscreen composition according to the present invention comprises:

- from about 20.0 to about 21.0 % of bis-ethylhexyloxyphenol methoxyphenyl triazine, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, drometrizole trisiloxane, ethylhexyl salicylate and ethylhexyl triazone;

- from about 3.0 to about 5.0 % of polyhydroxystearic acid and/or neopentyl glycol, C12-22 alkyl acrylate/hydroxyethylacrylate copolymer, acrylates/Cio-30 alkyl acrylate crosspolymer, aluminum starch octenylsuccinate, hydroxyethylcellulose and polyhydroxystearic acid;

- from about 8.5 to about 10.0 % of propanediol, caprylyl glycol and alcohol denatured;

- from about 18.0 to about 20.5 % of additional cosmetically acceptable ingredients, such as vitamins, fillers, fatty compounds and fragrances;

- from about 43.0 to about 46.0 % of water.

An additional suitable cosmetic sunscreen composition according to the present invention comprises:

- from about 20.0 to about 20.5 % of bis-ethylhexyloxyphenol methoxyphenyl triazine, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, drometrizole trisiloxane, ethylhexyl salicylate and ethylhexyl triazone;

- from about 3.5 to about 4.7 % of polyhydroxystearic acid and/or neopentyl glycol, C12-22 alkyl acrylate/hydroxyethylacrylate copolymer, acrylates/C 10-30 alkyl acrylate crosspolymer, aluminum starch octenylsuccinate, hydroxyethylcellulose and polyhydroxystearic acid;

- from about 9.0 to about 10.0 % of propanediol, caprylyl glycol and alcohol denatured;

- from about 18.5 to about 20.0 % of additional cosmetically acceptable ingredients, such as vitamins, fillers, fatty compounds, fragrances, triethanolamine and disodium EDTA;

- from about 44.0 to about 45.0 % of water.

Wherein all percentages are based on the total weight of the cosmetic sunscreen composition.

EXAMPLES Examples 1 to 5

A suitable composition according to the state of the art is as Example 1 and a suitable cosmetic sunscreen composition according to the present invention is as Examples 2 to 5, as follows:

Example 6 Stability Test

The stability of the cosmetic sunscreen compositions of the present invention according to Examples 2 to 5 were evaluated. After their manufacturing, samples of the cosmetic sunscreen compositions according to Examples 1 to 5 were separated and placed in closed glass containers. The containers were filled from about 70% to about 80% in order to allow enough space for gas exchange.

After that, the samples were separated for a stability at three different temperatures, then following to a stability after 2 months. For each condition, a vial was prepared.

Condition I. Temperature of 4 °C (1 week, 1 month and 2 months) Condition II. Ambient Temperature of 25 °C (1 month and 2 months) Condition III. Temperature of 45 °C (1 month and 2 months) Condition IV. Temperature of 55 °C (1 week)

The stability control was made based on the following physical-chemical controls: color and odor, appearance, pH, viscosity, and microscopy (polarized and non-polarized light).

Results of Examples 2 to 5 The samples of the composition according to Examples 2 to 5 presented white color and fluid appearance. After the tests, all samples were stable and no formation of agglomerates or noodles was observed during application. No odor was observed, even at 45 ° C. The samples showed pH value and viscosity within the expected range. The pH was from about 5.8 ± 0.3 in all conditions evaluated and the viscosity range was from about 40M2 ± 10, wherein the measurement was carried out in a Reomat device.

The microscopies for the samples using 10x magnification and the presence or absence of polarized light revealed that the evaluated formulas were considered stable, with closed edges and good distribution of the micelles within each drop. For the samples and conditions evaluated, microscopies showed a slight spacing between the micelles and borders. However, macroscopically no phase separation was observed, and the formula were considered stable for use.

Microscopies using polarized light did not reveal crystals characteristic of crystallized sunscreens, only cellulose fiber was observed (as seen in Figure 1 , which is related to the composition of Example 5, but Examples 2 to 4 showed the same pattern of images).

Results of Example 1

The state-of-the-art composition according to Example 1 was tested with the same protocol.

The composition according to Example 1 showed white color and fluid appearance. Upon rest, the formula had a gelatinous surface, which after shaking returns to its fluid state. The formation of lumps and noodles was observed right after the formulation, which prevents the use of the product by the consumer, thus being considered unstable.

During stability, viscosity and pH were outside the acceptable range.

The microscopies results for the composition according to Example 1 are seen in Figure 2, using 10x magnification and the presence or absence of polarized light revealed that the formula is not stable, presenting regions with sparse micelles within the analyzed drop, which according to previous knowledge is related to the instability of emulsions. The image observed under microscopy may be related to macroscopic agglomeration seen in the formula in question. Microscopy under polarized light showed no crystals, only cellulose and silica fibers that can reflect in polarized light.

Example 7

Sun Protection Factor - in vivo

An inventive cosmetic sunscreen composition according to Example 5 was tested in vivo in order to evaluate the Sun Protection Factor of the formula. This test was conducted according to ISO 24444-2010 method (SPF).

The composition was applied on 5 subjects with wide circular movements without fingercot, with an application time between 22 and 25 seconds.

The cosmetic sunscreen composition according to Example 5 obtained an average static SPF of 71 .7 (16.5) and an adjusted final SPF of 55.2.

Example 8

Sun Protection Factor (SPF) - in vitro

An inventive cosmetic sunscreen composition according to Example 4 was tested in vitro to measure its SPF. For the composition, measurements were performed on 3 FID6 and 3 SB6 plates, for a total of 6 plates.

The Plates and the composition of Example 4 were put in a stove at 25°C for at least 12 hours before the test begins. A nitrile finger cot is placed on the application tool of the Flelioscreen FID-Spreadmaster.

The absorbance spectrum of the composition of Example 4 was measured between 290nm and 400nm on 9 spots distributed on the plate, for all 6 plates.

Before irradiation, the SPF vitro double approach was 113 ± 5, the SPF vitro FID6 was 98 ± 1 , and the SPF vitro SB6 was 104 ± 6. After irradiation, the SPF vitro double approach was 86 ± 2, the SPF vitro FID6 was 74 ± 1 , and the SPF vitro SB6 was 80 ± 3. The double approach results can be found in Figure 3.

As a result, the composition of Example 4 has SPF of 113 before exposition and a SPF of 86 after exposition.

Example 9

Matte effect - in vivo

An inventive cosmetic sunscreen composition according to Example 5 was tested in vivo to verify the matte effect against a market formula of the state-of- the-art, similar to the present invention but without silica silylate. Each composition was applied to half of the face of the volunteers.

Different parameters were evaluated right after the application, and others after 2 hour of application.

After that period, the formulas were evaluated again and a comparison between such formulas was made.

As a result, after the test, it was observed that the inventive cosmetic sunscreen composition according to Example 5 had a greater matte effect than the reference formula and without the presence of noodles.

Therefore, it was concluded that the inventive cosmetic sunscreen composition according to Example 5 indicated a success formulation with the addition of silica silylate in the presence of the suspending agent, while the market formula of the state-of-the-art presented noodle and did not show a matte effect.

Claims

1 . A cosmetic sunscreen composition comprising:

(a) from 0.1 to 2.5 % by weight, based on the total weight of the composition, of silica silylate;

(b) from 0.3 to 5.0 % by weight, based on the total weight of the composition, of a suspending agent selected from polyhydroxystearic acid, or a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate;

(c) from 15.0 to 25.0 % by weight, including all ranges and sub ranges there between, based on the total weight of the composition, of at least one UV filter; wherein the Sun Protection Factor (SPF) ranges from 30 to 90.

2. The composition, according to claim 1 , wherein the silica silylate ranges from 0.1 to 1 .0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

3. The composition, according to claim 1 , wherein the suspending agent is polyhydroxystearic acid.

4. The composition, according to claim 3, wherein the suspending agent ranges from 0.5 to 1 .0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

5. The composition, according to claim 1 , wherein the suspending agent is a mixture of polyhydroxystearic acid and neopentyl glycol diethylhexanoate, in a ratio of 0.8:0.2.

6. The composition, according to claim 4, wherein the suspending agent ranges from 0.5 to 1 .5 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

7. The composition, according to claim 1 , wherein the at least one UV filter selected from bis-ethylhexyloxyphenol methoxyphenyl triazine, terephthalylidene dicamphor sulfonic acid, drometrizole trisiloxane, butyl methoxydibenzoylmethane, ethylhexyl salicylate, ethylhexyl triazone, phenylbenzimidazole sulfonic acid and mixtures thereof.

8. The composition, according to claim 1 , wherein it further comprises cosmetically acceptable ingredients selected from active compounds, fatty compounds, fillers, fragrances, polymers, solvents, vitamins, preserving agents, surfactants and mixtures thereof.

9. Use of a cosmetic sunscreen composition, comprising:

(c) from 15.0 to 25.0 % by weight, including all ranges and sub ranges there between, based on the total weight of the composition, of at least one UV filter; wherein said use if for manufacturing a daily product for the photoprotection of keratinous materials with high SPF, with dry touch and oil control.

10. A process for manufacturing a cosmetic sunscreen composition, comprising:

(c) from 15.0 to 25.0 % by weight, including all ranges and sub ranges there between, based on the total weight of the composition, of at least one UV filter; wherein the process comprises the steps of:

Step (A): Main Vessel - Room Temperature Hot aqueous phase comprising aqueous raw materials in a temperature ranging from about 60-70°C;

Step (B): Side Vessel - hot oily phase comprising oil raw materials, polymers, preservatives, vitamins and emulsifier in a temperature ranging from 75 ^QC to 80 ^QC;

Step (D): the fillers are gradually added to the mixture obtained in step (C) and mixed until homogeneity, at a temperature of below 30^QC;

Step (E): alcohol is added.