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Title:
COSMETIC SUNSCREEN COMPOSITION AND USE OF A COSMETIC SUNSCREEN COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2023/235942
Kind Code:
A1
Abstract:
The present invention is directed to a new cosmetic sunscreen composition comprising (a) a UV filter system; and (b) an emollient system. The present invention is also directed to the use of a cosmetic sunscreen composition.

Inventors:
BORGES DE SÁ VITOR (BR)
Application Number:
PCT/BR2022/050213
Publication Date:
December 14, 2023
Filing Date:
June 10, 2022
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
OREAL (FR)
BORGES DE SA VITOR (BR)
International Classes:
A61K8/35; A61K8/37; A61K8/41; A61K8/46; A61K8/49; A61Q17/04
Domestic Patent References:
WO2020187771A12020-09-24
WO1993004665A11993-03-18
WO2004006878A12004-01-22
WO2005058269A12005-06-30
WO2006032741A12006-03-30
WO2004085412A22004-10-07
WO2006000035A12006-01-05
WO2006034982A12006-04-06
WO2006034991A12006-04-06
WO2006035007A12006-04-06
WO2006034992A12006-04-06
WO2006034985A12006-04-06
Foreign References:
US20100183531A12010-07-22
US20220168196A12022-06-02
US7470725B22008-12-30
US5624663A1997-04-29
EP0669323A11995-08-30
US2463264A1949-03-01
US5237071A1993-08-17
US5166355A1992-11-24
GB2303549A1997-02-26
DE19726184A11998-12-24
EP0893119A11999-01-27
EP0832642A21998-04-01
EP1027883A22000-08-16
EP1300137A22003-04-09
DE10162844A12003-07-03
DE19855649A12000-06-08
EP0967200A11999-12-29
DE19746654A11999-02-18
DE19755649A11999-06-17
EP1008586A12000-06-14
EP1133980A22001-09-19
EP1133981A22001-09-19
US6225467B12001-05-01
EP1990372A22008-11-12
US5601811A1997-02-11
Other References:
"Sunscreens based on the water dispersions of the UV particulate filters TBPT and MBBT stabilized with polyglyceryl-10 laurate ED - Darl Kuhn", IP.COM, IP.COM INC., WEST HENRIETTA, NY, US, 29 July 2016 (2016-07-29), XP013172320, ISSN: 1533-0001
BRINKER, C.J.SCHERER, G.W.: "Sol-Gel Science", 1990, ACADEMIC PRESS
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, February 1938 (1938-02-01), pages 309
VAN DE HULST, H.C.: "Light Scattering by Small Particles", 1957, WILEY
"IP.COM Journal", 20 September 2004, IP.COM INC., article "Symmetrical Triazine Derivatives"
Attorney, Agent or Firm:
NAKATA, Carolina et al. (BR)
Download PDF:
Claims:
SET OF CLAIMS

1 . A cosmetic sunscreen composition comprising:

(a) an UV filter system comprising phenylbenzimidazole sulfonic acid, ethylhexyl salicylate, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, methylene bis- benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate; and

(b) an emollient system comprising isopropyl myristate, isononyl isononanoate, and diisopropyl sebacate.

2. The composition, according to claim 1 , wherein the amount of the UV filter system ranges from 15.0 to 31.0 % 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 UV filter system comprises:

- from 1 .0 to 3.0 % by weight of phenylbenzimidazole sulfonic acid;

- from 3.0 to 5.5 % by weight of ethylhexyl salicylate;

- from 0.5 to 1 .5 % by weight of terephthalylidene dicamphor sulfonic acid;

- from 3.0 to 5.0 % by weight of butyl methoxydibenzoylmethane;

- from 3.0 to 4.5 % by weight of ethylhexyl triazone;

- from 3.0 to 6.0 % by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine;

- from 0.5 to 2.5 % by weight of diethylamino hydroxybenzoyl hexyl benzoate; and

- from 1.0 to 3.0 % by weight of methylene bis-benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate; including all ranges and sub-ranges there between, based on the total weight of the composition.

4. The composition, according to claim 1 , wherein the amount of the emollient system ranges from 5.0 to 15.0 % 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 emollient system comprises:

- from 0.5 to 3.0 % by weight of isopropyl myristate; - from 2.0 to 5.5 % by weight of isononyl isononanoate; and

- from 2.5 to 7.5 % by weight of diisopropyl sebacate; including all ranges and sub-ranges there between, based on the total weight of the composition.

6. The composition, according to claim 1 , wherein it further comprises silica silylate, in the range of from 0.1 to 2.5 % 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 it 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.

8. Use of a cosmetic sunscreen composition, comprising:

(a) an UV filter system comprising phenylbenzimidazole sulfonic acid, ethylhexyl salicylate, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, methylene bis- benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate; and

(b) an emollient system comprising isopropyl myristate, isononyl isononanoate, and diisopropyl sebacate; wherein said use if for manufacturing a daily product for the photoprotection of keratinous materials with high SPF, with dry touch and oil control.

Description:
COSMETIC SUNSCREEN COMPOSITION AND USE OF A COSMETIC SUNSCREEN COMPOSITION FIELD OF THE INVENTION

The present invention is directed to a new cosmetic sunscreen composition comprising (a) a UV filter system; and (b) an emollient system. The present invention is also directed to the use of 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.

Among the widely used UV filters, are octocrylene and homosalate. However, concern has been raised about the use of these UV filters in cosmetic sunscreen compositions since such raw materials are having their effects on the environment being studied more carefully, particularly regarding biodegrading difficulties. Furthermore, such UV filters are also being questioned in terms of human health and aquatic organisms.

Replacing octocrylene and homosalate in cosmetic sunscreen composition is not an easy task, since these UV filters also play a as emollients in the final composition, which affect the stability of the entire composition. Attempts to compensate the removal of such UV filters by increasing the amount of the remaining UV filters of the composition have proven to be insufficient. Additional modifications are necessary for a stable composition to be obtained.

Therefore, there is a need for new cosmetic sunscreen without the UV filters octocrylene and homosalate, that keep good cosmetically properties such as high SPF, and that do not feel heavy on the skin and that can control and reduce the oiliness of the skin after their application, leaving the skin with a matte finish, which is stable.

Furthermore, it is also desired to remove titanium dioxide from cosmetic sunscreen compositions, since this ingredient is associated with the formation of white film on the skin, after the application of the cosmetic composition.

That said, it is the objective of this invention to provide a stable cosmetic sunscreen composition without the UV filters octocrylene and homosalate, preferably without titanium dioxide, with high SPF.

The inventors of the present application have surprisingly managed to develop such new cosmetic sunscreen composition by combining a UV filter system with an emollient system.

SUMMARY OF THE INVENTION

The present invention is directed to new cosmetic sunscreen compositions comprising

(a) a UV filter system comprising phenylbenzimidazole sulfonic acid, ethylhexyl salicylate, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, methylene bis- benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate; and

(b) an emollient system comprising isopropyl myristate, isononyl isononanoate, and diisopropyl sebacate.

The present invention is also directed to the use of 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.

DETAILED DESCRIPTION OF THE INVENTION

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

(a) an UV filter system comprising phenylbenzimidazole sulfonic acid, ethylhexyl salicylate, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, methylene bis- benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate; and

(b) an emollient system comprising isopropyl myristate, isononyl isononanoate, and diisopropyl sebacate

In a preferred embodiment, the amount of the UV filter system of present invention ranges from about 15.0 to about 31.0 %, from about 17.5 to about

27.5 %, from about 20.0 to about 25.0 % by weight, including all ranges and subranges there between, based on the total weight of the composition.

In a further preferred embodiment, said UV filter system comprises from about 1 .0 to about 3.0 % by weight of phenylbenzimidazole sulfonic acid, from about 3.0 to about 5.5 % by weight of ethylhexyl salicylate, from about 0.5 to about 1 .5 % by weight of terephthalylidene dicamphor sulfonic acid, from about 3.0 to about 5.0 % by weight of butyl methoxydibenzoylmethane, from about 3.0 to about 4.5 % by weight of ethylhexyl triazone, from about 3.0 to about 6.0 % by weight of bisethylhexyloxyphenol methoxyphenyl triazine, from about 0.5 to about 2.5 % by weight of diethylamino hydroxybenzoyl hexyl benzoate, and from about 1.0 to about 3.0 % by weight of methylene bis-benzotriazolyl tetramethylbutylphenol (and) polyglyceryl- 10 laurate, including all ranges and sub-ranges there between, based on the total weight of the composition.

In a preferred embodiment, the amount of the emollient system of present invention ranges from about 5.0 to about 15.0 %, from about 7.5 to about

12.5 %, from about 9.0 to about 11.0 % by weight, including all ranges and subranges there between, based on the total weight of the composition.

In a further preferred embodiment, said emollient system comprises from about 0.5 to about 3.0 % by weight of isopropyl myristate, from about 2.0 to about 5.5 % by weight of isononyl isononanoate, and from about 2.5 to about 7.5 % by weight of diisopropyl sebacate, 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 silica silylate, in an amount that ranges from about 0.1 to about 2.5 %, from about 0.2 to about 2.3 %, from about 0.3 to about 1.5 %, from about 0.5 to about 1 .0 % 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 99, preferably from 40 to 80, more preferably about 80. 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, 90, 95 or 99.

In an embodiment, the cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 80.

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 reduction, and good stability.

Terms

As used herein, the expression “at least” is interchangeable with the expression “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 subrange, 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.

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%.

“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

When present in the cosmetic sunscreen composition of the present invention, the silica silylate, 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.

If present, the silica silylate (e.g., hydrophobic silica silylate particles) has 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 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, if present, 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 silica silylate particles 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.T 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 silylate particles 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 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 1100 and Enova Aerogel MT 1200.

Additional UV Filters

Apart from the UV filters present in the UV system of the present cosmetic sunscreen composition, said composition may comprise at least one additional UV filter selected from commonly used UV filters, excluding octocrylene and homosalate.

According to the present invention, the concentration of the at least one additional 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.

Salicylic derivatives:

Examples of suitable salicylic derivatives include, but are not limited to, 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 tetramethylbutylphenol, or in micronized form as an aqueous dispersion.

Triazine derivatives:

Examples of suitable triazine derivatives include, but are not limited to, diethylhexyl butamido 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.

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, benzophenone-4, aminobenzoic acid (PABA), 4-Bis(polyethoxy)-para-aminobenzoic acid polyethoxyethyl ester (PEG-25 PABA), camphor benzalkonium methosulfate, 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.

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.

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-30 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, triethanolamine, and mixtures thereof.

The composition may comprise at least one dye/pigment, preferably 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 about 17.0 to about 21 .0 %, such as from 18.0 to about 20.0 % or such as from about 18.5 to about 20.0 % by weight, based on 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 - hot oily phase comprising oil raw materials, preservatives, vitamins, and emulsifiers in a temperature ranging from about 75 S C to about 80 S C;

Step (B): Side Vessel - Room Temperature aqueous phase comprising aqueous raw materials;

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

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 s C.

Embodiments

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

- from about 22.0 to about 25.0 % by weight, based on the total weight of the composition, of phenylbenzimidazole sulfonic acid, ethylhexyl salicylate, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, and methylene bis-benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate;

- from about 8.5 to about 11 .0 % by weight, based on the total weight of the composition, of isopropyl myristate, isononyl isononanoate, and diisopropyl sebacate;

- from about 0.5 to about 1 .0 % by weight, based on the total weight of the composition, of silica silylate;

- from about 30.0 to about 40.0 % by weight, based on the total weight of the composition, of water; and

- from about 25.0 to about 30.0 % by weight, based on the total weight of the composition, of additional cosmetically acceptable ingredients selected from active compounds, fatty compounds, fillers, fragrances, polymers, solvents, vitamins, additional UV filters, preserving agents, surfactants and mixtures thereof.

A further example of a sunscreen cosmetic composition according to the present invention may comprise:

- from about 24.0 to about 31 .0 % by weight, based on the total weight of the composition, of phenylbenzimidazole sulfonic acid, ethylhexyl salicylate, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, and methylene bis-benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate;

- from about 7.0 to about 11 .0 % by weight, based on the total weight of the composition, of isopropyl myristate, isononyl isononanoate, and diisopropyl sebacate;

- from about 30.0 to about 45.0 % by weight, based on the total weight of the composition, of water; and

- from about 25.0 to about 30.0 % by weight, based on the total weight of the composition, of additional cosmetically acceptable ingredients selected from active compounds, fatty compounds, fillers, fragrances, polymers, solvents, vitamins, preserving agents, surfactants and mixtures thereof.

EXAMPLES

Examples 1 to 6

A suitable composition according to the state of the art is as Examples

1 to 3 and suitable cosmetic sunscreen compositions according to the present invention are as Examples 4 to 6, as follows: TESTS

Test 1 - Sun Protection Factor (SPF)

Inventive cosmetic sunscreen compositions according to Ex. 5 and Ex. 6 were tested to measure its SPF according to the ISO 24444-2019 method (SPF), in two phases.

In phase one (screening phase), the cosmetic compositions were applied on 5 subjects in order to access the approximate SPF factor. The cosmetic sunscreen composition according to Ex. 5 obtained an average static SPF of 88.2 (10.8) and an adjusted final SPF of 77.4, and the cosmetic sunscreen composition according to Ex. 6 obtained an average static SPF of 85.9 (12.7) and an adjusted final SPF of 73.2.

In phase two, only the composition of Ex. 5 was tested, with 10 subjects. The composition according to Ex. 5 obtained an average static SPF of 92.0 (6.2) and an adjusted final SPF of 85.8.

The results of the reference formula, tested in parallel, were integrated to the international data base and presented statistical results (Z-value) <1.6, showing that the results from the tested formulas are validated.

Test 2 - UVA Protection Factor (UVA-PF) in vivo

A Screening Evaluation of UVA Protection Factor was conducted with the sunscreen cosmetic compositions according to Ex. 5 and Ex. 6, in a study performed according to ISO 24442-201 1 method (UVA in vivo), with two phases - phase 1 (screening) and phase 2 (complement).

In phase 1 , the cosmetic sunscreen composition according to Ex. 5 demonstrated an average in vivo UVA-PF of 29.0 (± 0.0), and the cosmetic sunscreen composition according to Ex. 6 had an average in vivo UVA-PF of 26.7 (± 4.0).

For phase 2, only the composition according to Ex. 5 was tested with a broader group of subjects, and demonstrated an in vivo UVA-PF of 27.8 (± 1 .8).

Test 3 - Comparative Test

The cosmetic sunscreen composition of the present invention according to Ex. 4 was compared to a state-of-the-art cosmetic sunscreen composition according to Ex. 1 , which comprises octocrylene and homosalate, as well as titanium dioxide.

Both compositions were tested on a group of women, ages 18 to 55 years old, which were daily users of cosmetic sunscreen compositions for at least 1 year and 6 months, with oily or combination skin.

According to the tested women, the texture of the compositions according to Ex. 4 (inventive) and Ex. 1 (state-of-the-art) was very similar. However, the cosmetic sunscreen composition according to Ex. 4 (inventive) demonstrated a better resistance to water and to sweat, without ash effect, while maintaining a similar SPF profile.