阅读说明：本技术 具有改进效力的矿物防晒组合物 (Mineral sunscreen compositions having improved efficacy ) 是由 A·沙赫 B·S·博纳 于 2019-09-27 设计创作，主要内容包括：描述了具有改进效力的矿物防晒组合物。所述矿物防晒组合物包括：(a)一种或更多种矿物UV过滤剂；(b)一种或更多种茋类化合物；(c)乙基己基甲氧立林；(d)亚丁香基丙二酸二乙基己酯；和(e)化妆品可接受的载剂。所述矿物防晒组合物提供高防晒因子(SPF)而不需要大量的矿物UV过滤剂。此外,所述矿物防晒组合物比传统矿物防晒组合物更少不透明和白色,使它们对消费者有美学上的吸引力。(Mineral sunscreen compositions having improved efficacy are described. The mineral sunscreen composition comprises: (a) one or more mineral UV filters; (b) one or more stilbenes; (c) ethyl hexyl methoprim; (d) diethylhexyl syringylidenemalonate; and (e) a cosmetically acceptable carrier. The mineral sunscreen composition provides a high Sun Protection Factor (SPF) without the need for large amounts of mineral UV filters. Furthermore, the mineral sunscreen compositions are less opaque and white than traditional mineral sunscreen compositions, making them aesthetically appealing to consumers.)

1. A sunscreen composition comprising:

(a) one or more mineral UV filters;

(b) one or more stilbenes;

(c) ethyl hexyl methoprim;

(d) diethylhexyl syringylidenemalonate; and

(e) a cosmetically acceptable carrier.

2. The sunscreen composition of claim 1, wherein the one or more mineral UV filters are selected from the group consisting of titanium dioxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide, and mixtures thereof.

3. A sunscreen composition as claimed in claim 1 or 2 wherein the stilbene compound is selected from spruce neoside, resveratrol, piceatannol, pterostilbene and mixtures thereof.

4. A sunscreen composition as claimed in any one of the preceding claims wherein the total amount of stilbene compound, diethylhexyl syringylidenemalonate and ethylhexylmethoxylene in said sunscreen composition is from about 0.5% to about 6% by weight based on the total weight of said sunscreen composition.

5. The sunscreen composition of claim 4, wherein the weight ratio of piceid, ethylhexylmethoxylin, and diethylhexylidene malonate, relative to the total weight of the combination of piceid, ethylhexylmethoxylin, and diethylhexylidene malonate, is as follows:

-from about 0.1 to about 0.5 of said one or more stilbenes;

-ethylhexyl methoprene from about 0.3 to about 0.7; and

-diethylhexyl syringylidenemalonate from about 0.1 to 0.5.

6. A sunscreen composition as claimed in any one of the preceding claims wherein the amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is sufficient to increase the in vitro SPF of said sunscreen composition by at least 5% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is replaced by ethylhexylmethoxylene alone.

7. A sunscreen composition as claimed in any one of the preceding claims wherein the amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is sufficient to increase the in vitro SPF of said sunscreen composition by at least 5% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is replaced by diethylhexylidene malonate alone.

8. A sunscreen composition as in any of the preceding claims, wherein said sunscreen composition is free of butyl methoxydibenzoylmethane (avobenzone) and ethylhexyl methoxycinnamate (oxolanyl).

9. The sunscreen composition of any of the above claims, wherein the sunscreen composition is free of organic UV filters.

10. The sunscreen composition of any of the preceding claims, wherein the total amount of the one or more inorganic UV filters is from about 1 to about 25 wt%, based on the total weight of the sunscreen composition.

11. The sunscreen composition of claim 1, comprising:

(a) one or more mineral UV filters;

(b) at least 0.2% by weight of one or more stilbenes;

(c) at least 0.5% by weight of ethylhexyl methoprene; and

(d) at least 0.2% by weight of diethylhexyl syringylidenemalonate,

wherein weight percent is based on the total weight of the sunscreen composition; and wherein the total amount of stilbenes, ethylhexylmethoxylene and diethylhexylidene malonate does not exceed 6 wt. -%, based on the total weight of the sunscreen composition.

12. The sunscreen composition of claim 1, comprising:

(a) one or more mineral UV filters;

(b) from about 0.2 to about 3 weight percent of one or more stilbenes;

(c) about 0.5 to about 5 weight percent of ethylhexyl methoprene; and

(d) about 0.2 to about 2 weight percent diethylhexyl syringylidene malonate,

wherein weight percentages are based on the total weight of the sunscreen composition.

13. A sunscreen composition as claimed in claim 1 wherein the stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate are in amounts sufficient to:

-increasing the in vitro SPF of the sunscreen composition by at least 5% compared to an otherwise identical sunscreen composition in which the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is replaced by ethylhexylmethoxylene only; and is

-increasing the in vitro SPF of the sunscreen composition by at least 5% compared to an otherwise identical sunscreen composition in which the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexyl syringylidenemalonate is replaced by diethylhexyl syringylidenemalonate alone.

14. A sunscreen composition as claimed in claim 11 wherein the stilbene compound is selected from the group consisting of piceid, resveratrol and mixtures thereof.

15. The sunscreen composition of any of the above claims, further comprising:

(f) one or more silicone oils.

16. A sunscreen composition as claimed in any one of the preceding claims in the form of a lotion, cream, gel or spray.

17. The sunscreen composition of any of the above claims, wherein the cosmetically acceptable carrier comprises water.

18. A sunscreen composition as claimed in any one of the preceding claims in the form of an emulsion.

19. A sunscreen composition comprising:

(a) from about 1 to about 25 weight percent, based on the total weight of the sunscreen composition, of one or more mineral UV filters selected from titanium dioxide, iron oxide, and mixtures thereof;

(b) piceid;

(c) ethyl hexyl methoprim; and

(d) diethylhexyl syringylidenemalonate;

wherein the total amount of the combination of piceid, ethylhexylmethoxylene, and diethylhexylidene malonate is from about 1 weight percent to about 6 weight percent, based on the total weight of the sunscreen composition; and is

The weight ratio of piceid, ethylhexylmethoxylin and diethylhexylidene malonate, relative to the total weight of the combination of piceid, ethylhexylmethoxylin and diethylhexylidene malonate, is as follows:

-from about 0.1 to about 0.4 of said one or more stilbenes;

-ethylhexyl methoprene from about 0.3 to about 0.7; and

-diethylhexyl syringylidenemalonate from about 0.1 to 0.4.

20. A method of protecting skin from UV radiation, the method comprising applying to the skin an effective amount of a sunscreen composition according to any of the preceding claims.

FIELD OF THE DISCLOSURE

The present disclosure relates to mineral sunscreen compositions and to methods of using the mineral sunscreen compositions to protect keratinous substrates such as skin and hair from UV radiation.

Background

The negative effects of exposure to ultraviolet ("UV") light are well known. Prolonged exposure to sunlight causes damage to the skin such as sunburn and dries the hair causing it to become brittle. When skin is exposed to UV light having a wavelength of about 290 nm to about 400 nm, long-term damage may lead to serious conditions such as skin cancer.

UV light also contributes to aging by allowing free radicals to form in the skin. Free radicals include, for example, singlet oxygen, hydroxyl radicals, superoxide anions, nitric oxide and hydrogen radicals. Free radicals attack DNA, membrane lipids, and proteins, thereby generating carbon free radicals. These in turn react with oxygen to produce peroxyradicals, which can attack neighboring fatty acids to generate new carbon radicals. This cascade results in a chain reaction that produces lipid peroxidation products. Damage to the cell membrane results in a loss of cell permeability, increases the concentration of intercellular ions, and decreases the ability to excrete or detoxify waste products. The end result is a loss of skin elasticity and the appearance of wrinkles. This process is often referred to as photoaging.

Sunscreen preparations can be used to protect against UV damage and retard the signs of aging. The degree of UV protection provided by a sunscreen composition is directly related to the amount and type of UV filter contained therein. The greater the amount of UV filter, the greater the degree of UV protection. Nevertheless, it is desirable to achieve the best photoprotective efficacy with the least amount of UV filter. In particular, it is particularly desirable to achieve high photoprotection with a minimum amount of UV filter when formulated with mineral UV filters, since mineral UV filters also produce a white color when applied to the skin when used in large amounts in cosmetic formulations. The inventors of the present disclosure have discovered a way to obtain sunscreen values not previously attainable with such small amounts of total UV filter.

Disclosure of Invention

The present disclosure relates to sunscreen compositions that provide an unexpectedly high degree of efficacy and are aesthetically pleasing. The sunscreen composition includes mineral UV filters which are known to be non-irritating, natural and mild to the skin. One drawback of mineral-based sunscreen compositions is that they tend to appear white when applied to the skin. Consumers prefer sunscreen compositions to be natural (not noticeable). However, it is challenging to develop mineral-based sunscreen products with high Sun Protection Factors (SPF) that exhibit minimal or no whitening.

The present inventors have discovered a synergistic combination of ingredients that improves SPF without causing unacceptable whitening when applied to skin. This synergy allows high SPF to be achieved without the need for large amounts of mineral-based UV filters. Less mineral UV filters can be used to achieve the desired SPF, thus reducing the whiteness of the composition. The sunscreen composition generally comprises:

(a) one or more mineral UV filters;

(b) one or more stilbenes;

(c) ethylhexylmethoxylene (ethylhexylmethoxylene);

(d) diethylhexyl syringylidenemalonate; and

(e) a cosmetically acceptable carrier.

Ethylhexyl methoxylene and diethylhexyl syringylidenemalonate have been used to increase the SPF of organic UV filters. These compounds increase the SPF of organic UV filters by acting as highly efficient singlet quenchers. Organic UV filters absorb UV light and thus generate excited singlet or triplet states in the molecule, resulting in easy decomposition of the molecule and loss of photoprotective efficacy. Mineral UV filters do not need to be quenched by light stabilizing compounds because they remain light stable. Thus, there was no reason to include these compounds specifically in the case of mineral UV filters before the inventors' discovery. It is not known that ethylhexyl methoxylene, diethylhexyl syringylidenemalonate, or mixtures thereof can provide any particular benefit or enhancement to mineral UV filters.

The inventors have found that a combination comprising a stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate surprisingly increases (improves) the SPF of the mineral UV filter, which leads to a reduction of the amount of mineral UV filter in the sunscreen composition. Reducing the amount of mineral UV filter reduces whitening and improves the overall aesthetics of the sunscreen formulation compared to an equivalent composition at the same SPF without the combination.

In particular, the use of a particular combination of stilbenes, ethylhexylmethoxylene, and diethylhexylidene malonate results in an improved (enhanced) SPF over that achievable by using an equivalent amount of ethylhexylmethoxylene only or diethylhexylidene malonate only. While not wishing to be bound by any particular theory, it is believed that this combination increases the SPF of the mineral UV filters and reduces whiteness by allowing the use of less mineral UV filters that cause the sunscreen formulation to whiten after application to the skin.

In addition to the mineral sunscreen compositions described herein, the present disclosure relates to methods of protecting keratin substrates from Ultraviolet (UV) radiation, and methods of absorbing UV light using the mineral sunscreen compositions. Such methods include applying a sunscreen composition to a keratinous substrate, such as skin and/or hair, and subjecting the keratinous substrate to ultraviolet radiation. In addition, methods of increasing the SPF of a mineral UV filter, and methods of reducing the whiteness of a mineral sunscreen composition are described.

Brief Description of Drawings

An implementation of the present technique will now be described, by way of example only, with reference to the accompanying drawings, in which:

figure 1 is a contour plot of the predicted SPF values for a mineral sunscreen comprising a mixture of picroside (X2), ethylhexylmethoxylene (X1) and diethylhexyl syringylidenemalonate (X3); and is

Figure 2 is a graph showing the mixtures outlined in the examples, which were used to build a linear regression model to illustrate the effect of spruce neoside, ethylhexyl methoxylindane, and diethylhexyl syringylidenemalonate on mineral sunscreen compositions, emphasizing that particular mixtures exhibit the highest in vitro SPF and the highest predicted SPF compared to other mixtures prepared.

It should be understood that the various aspects are not limited to the arrangements and instrumentality shown in the attached drawings.

Detailed Description

Where the following terms are used in this specification, they are used as defined below.

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

The terms "a" and "an" and "the" are to be understood as encompassing the plural as well as the singular.

The term "mineral UV filter" is interchangeable with the terms "mineral UV screener", "inorganic UV filter", "inorganic UV screener", "mineral UV filter" and "inorganic UV filter". Mineral UV filters are compounds which do not comprise any carbon atoms in their chemical structure, which are capable of screening off or absorbing UV radiation between 280 and 400 nm.

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

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

All ranges and values disclosed herein are inclusive and combinable. For example, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value, resulting in a subrange, and the like. Moreover, all ranges provided are intended to include each and every specific range therein, as well as combinations of sub-ranges between given ranges. Thus, a range of 1-5 explicitly includes 1, 2, 3, 4, and 5, as well as sub-ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, and the like.

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" and are intended to be within +/-5% of the indicated number.

The phrase "at least one" as used herein is interchangeable with the phrase "one or more" and thus includes individual components as well as mixtures/compositions.

The term "treating" (and grammatical variations thereof) as used herein refers to applying a composition of the present disclosure to the surface of skin and/or hair. The term "treating" (and grammatical variations thereof) as used herein also refers to contacting skin or hair with a composition of the present disclosure.

The terms "substantially free of" or "substantially free of as used herein means the presence of less than about 2 weight percent of the particular material added to the composition based on the total weight of the composition. Nonetheless, the composition may include less than about 1 wt.%, less than about 0.5 wt.%, less than about 0.1 wt.%, less than about 0.01 wt.% of the specified material, or none of the specified material.

The term "active material" as used herein with respect to a percentage amount of an ingredient or material refers to an ingredient or material that is 100% active.

By "cosmetically acceptable" it is meant that the item is compatible with keratinous substrates such as skin and hair. For example, "cosmetically acceptable carrier" means a carrier that is compatible with keratin substrates such as skin and hair.

The term "mixtures thereof" does not require that the mixture include all of A, B, C, D, E and F (but may include all of A, B, C, D, E and F). Instead, it refers to a mixture that may include any two or more of A, B, C, D, E and F. 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".

Likewise, the term "their salts" also relates to "their various salts". Thus, where the disclosure refers to an element selected from the group consisting of A, B, C, D, E, F, their salts, and mixtures thereof, it refers to a compound that may include one or more of A, B, C, D and F, may include one or more of a salt, B salt, C salt, D salt, E salt, and F salt, or may include a mixture of any two of A, B, C, D, E, F, A salt, B salt, C salt, D salt, E salt, and F salt.

Reference throughout this disclosure to salts may include salts having counterions such as alkali metal, alkaline earth metal or ammonium counterions. This list of counterions is not limiting.

The term "stable emulsion" refers to a composition that does not undergo phase separation at temperatures up to 45 ℃ for at least two weeks.

The phrase "including endpoints" of concentration ranges means that the limits of the ranges are included in the defined interval.

As used herein, "volatile" means having a flash point of less than about 100 ℃.

As used herein, "non-volatile" means having a flash point above about 100 ℃.

The term "polymer" as defined herein includes homopolymers and copolymers formed from at least two different types of monomers.

The term "INCI" is an abbreviation for the International Nomenclature for cosmetic ingredients, which is a name system provided by the International Nomenclature Commission (International Nomenclature Committee) of the Personal Care Products Council (Personal Care Products), which describes Personal Care ingredients.

The term "weight ratio" or "mass ratio" as used herein relates to the amount of a substance in proportion to a mixture containing the substance and is calculated by dividing the amount by weight of the substance contained in the mixture by the weight of the mixture containing the substance. As an example, a weight ratio of 0.4 for substance a in a mixture of A, B and C indicates that the weight of substance a divided by the total weight of substances A, B and C is 0.4.

As used herein, all ranges provided are intended to include each specific range therein, and combinations of sub-ranges between given ranges. Thus, a range of 1-5 explicitly includes 1, 2, 3, 4, and 5, as well as sub-ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, and the like.

Some of the various categories of the determined components may overlap. In such cases where overlap may exist and the composition includes two components (or the composition includes more than two components that overlap), the compounds that overlap do not represent more than one component. For example, fatty acids can be characterized as both nonionic surfactants and fatty compounds. If a particular composition includes both a nonionic surfactant and a fatty compound, the single fatty acid will act as only a nonionic surfactant or only a fatty compound (the single fatty acid does not act as both a nonionic surfactant and a fatty compound).

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

The present disclosure relates to sunscreen compositions that provide an unexpectedly high degree of efficacy and are aesthetically pleasing. The sunscreen composition includes mineral UV filters which are known to be non-irritating, natural and mild to the skin. The inventors have found that a synergistic combination of stilbenes, ethylhexylmethoxylene and diethylhexylidene malonate unexpectedly increases the SPF of mineral based sunscreen compositions. This synergy allows high SPF to be achieved without the need for large amounts of mineral-based UV filters, thus reducing the whiteness associated with mineral-based sunscreen compositions. The sunscreen composition generally comprises:

(a) one or more mineral UV filters;

(b) one or more stilbenes;

(c) ethyl hexyl methoprim;

(d) diethylhexyl syringylidenemalonate; and

(e) a cosmetically acceptable carrier.

Non-limiting examples of useful mineral filters include titanium dioxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide, and mixtures thereof. Non-limiting examples of useful stilbenes include piceid, resveratrol, piceatannol, pterostilbene, and mixtures thereof. The sunscreen composition may optionally include organic UV filters, but organic UV filters are certainly not required and may optionally not be included. Thus, the sunscreen composition may be free or substantially free of organic UV filters. In some cases, the sunscreen composition may be free or substantially free of butyl methoxydibenzoylmethane (avobenzone) and ethylhexyl methoxycinnamate (oxcinonide).

The weight ratio of spruce neoside, ethylhexyl methoxylin and diethylhexyl syringylidenemalonate, relative to the total weight of the combination of spruce neoside, ethylhexyl methoxylin and diethylhexyl syringylidenemalonate, may be as follows:

-from about 0.1 to about 0.5 of one or more stilbenes;

-ethylhexyl methoprene from about 0.3 to about 0.7; and

-diethylhexyl syringylidenemalonate from about 0.1 to 0.5.

The amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is typically sufficient to increase the in vitro SPF of the sunscreen composition by at least 5% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is replaced by ethylhexylmethoxylene alone. Furthermore, the amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is typically sufficient to increase the in vitro SPF of the sunscreen composition by at least 5% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is replaced by diethylhexylidene malonate alone.

Mineral UV filtering agent

Non-limiting examples of mineral UV filters include treated or untreated metal oxides, such as pigments or nanopigments like titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide. Particularly preferred mineral UV filters include titanium dioxide and/or zinc oxide.

In some cases, the average particle size can be from about 5 nm to about 25 μm, from about 10 nm to about 10 μm, or from about 15 nm to about 5 μm. The mineral UV filter may be a nanopigment having an average particle size of about 5 nm to about 100 nm, about 5 nm to about 75 nm, or about 10 nm to 50 nm. Larger particle sizes, such as from about 1 μm to about 25 μm, from about 5 μm to about 20 μm, or from about 10 μm to about 15 μm, may also be used.

Treated pigments are pigments that have been surface treated with one or more compounds that have undergone chemical, electronic, mechanochemical, and/or mechanical properties, such as described, for example, in Cosmetics & Toiletries, 1990, 2 months, volume 105, pages 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithin, sodium, potassium, zinc, iron, or aluminum salts of fatty acids, metal (titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, silicon oxides, metal oxides, sodium hexametaphosphate, aluminum oxide, or glycerin.

The treated pigment may be titanium oxide treated with:

silica and alumina, such as the products "Microtitanium Dioxide MT 500 SA" and "Microtitanium Dioxide MT 100 SA" from Tayca, and the products "Tioveil Fin", "Tioveil OP", "Tioveil MOTG" and "Tioveil IPM" from Tioxide;

alumina and aluminium stearate, such as the product "micronized Dioxide MT 100T" from Tayca company;

alumina and aluminum laurate, such as the product "micronized Dioxide MT 100S" from Tayca corporation;

-iron oxide and iron stearate; such as the product "Microtitanium Dioxide MT 100F" from Tayca;

silica, alumina and silicones, such as the products "titanium Dioxide MT 100 SAS", "titanium Dioxide MT 600 SAS" and "titanium Dioxide MT 500 SAS" from the company Tayca;

sodium hexametaphosphate, such as the product "micronized Dioxide MT 150W" from Tayca corporation;

octyltrimethoxysilane, such as the product "T-805" from Degussa;

alumina and stearic acid, such as the product "UVT-M160" from Kemira corporation;

alumina and glycerol, such as the product "UVT-M212" from Kemira corporation;

alumina and silicones, such as the product "UVT-M262" from Kemira corporation.

Other titanium oxide pigments treated with silicone are: TiO treated with octyltrimethylsilane and having elementary particles with an average size between 25 and 40 nm₂Such as the product sold under the trade name "T805" by Degussa silicones corporation; TiO treated with polydimethylsiloxane and having primary particles with an average size of 21 nm₂Such as the one sold by the company Cardre under the trade name "70250 Cardre UF TiO2SI 3"; anatase/rutile TiO treated with Dimethylhydrogensiloxane and having an average base particle size of 25 nm₂Such as the product sold under the trade name "Microtitanium Dioxide USP Grade hydrophosphonic" by the company Color technologies.

Uncoated titanium oxide pigments are sold, for example, by the company Tayca under the name "titanium Dioxide MT 500B" or "titanium Dioxide MT 600B", by the company Degussa under the name "P25", by the company Wackher under the name "Oxyde titanium transfer PW", by the company Myoshi Kasei under the name "UFTR", by the company Tomen under the name "ITS" and by the company Tioxide under the name "Tioveil AQ".

Uncoated zinc oxide pigments are, for example:

those sold by the company Sunsmart under the name "Z-Cote";

-those sold under the name "Nanox" by Elementis; and

those sold under the name "Nanogard WCD 2025" by Nanophase Technologies.

Coated zinc oxide pigments are, for example:

those sold by the company Toshibi under the name "Zinc Oxide CS-5" (ZnO coated with polymethylhydrosiloxane);

those sold under the name "Nanogard Zinc Oxide FN" by the company Nanophase Technologies (in Finsolv TN, C)₁₂-C₁₅40% dispersion in alkyl benzoate);

those sold by the company Daito under the names "Daitosphere ZN-30" and "Daitosphere ZN-50" (dispersions in cyclomethicone/oxyethylenated polydimethylsiloxanes containing 30% or 50% of nano-zinc oxide coated with silica and polymethylhydrosiloxane);

those sold by the company Daikin under the name "NFD Ultrafine ZNO" (ZNO coated with perfluoroalkyl phosphate and perfluoroalkylethyl based copolymers, as a dispersion in cyclopentasiloxanes);

those sold under the name "SPD-Z1" by the company Shin-Etsu (ZnO coated with a silicone-grafted acrylic polymer, dispersed in cyclomethicone);

those sold under the name "Escalol Z100" by the ISP company (alumina-treated ZnO dispersed in ethylhexyl methoxycinnamate/PVP-hexadecene/polymethylsiloxane copolymer mixture);

those sold by the Fuji Pigment company under the name "Fuji ZNO-SMS-10" (ZnO coated with silica and polymethylsilsesquioxane); and

those sold by the company Elementis under the name "Nanox Gel TN" (dispersed at a concentration of 55% in C with a polycondensate of hydroxystearic acid)₁₂-C₁₅ZnO of alkyl benzoate).

Uncoated Cerium Oxide pigments are sold under the name "Colloidal Cerium Oxide" by Rhone-Poulenc. Uncoated Iron oxide nanopigments are sold, for example, by the company Arnaud under the names "Nanogard WCD 2002 (FE 45B)", "Nanogard Iron FE 45 BL AQ", "Nanogard FE 45R AQ" and "Nanogard WCD 2006 (FE 45R)", or by the company Mitsubishi under the name "TY-220". Coated Iron Oxide nanopigments are sold, for example, by the company Arnaud under the names "Nanogard WCD 2008 (FE 45B FN)", "Nanogard WCD 2009 (FE 45B 556)", "Nanogard FE 45 BL 345" and "Nanogard FE 45 BL", or by the company BASF under the name "Transparent Iron Oxide".

Mixtures of metal oxides, especially mixtures of titanium dioxide and cerium dioxide, may also be used, including: an equal weight mixture of silica coated titanium dioxide and cerium oxide sold under the name "Sunveil A" by Ikeda; and mixtures of alumina, silica and silicone coated titanium dioxide and zinc dioxide, such as the product "M261" sold by Kemira corporation; or a mixture of alumina, silica and glycerol coated titanium dioxide and zinc dioxide, such as the product "M211" sold by Kemira corporation.

The total amount of mineral UV filter in the mineral sunscreen composition may vary, but is typically from about 1 to about 30 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of mineral UV filter may be about 1 to about 25 wt%, about 1 to about 20 wt%, about 1 to about 15 wt%, about 1 to about 10 wt%, about 5 to about 30 wt%, about 5 to about 25 wt%, about 5 to about 20 wt%, about 5 to about 15 wt%, about 5 to about 10 wt%, based on the total weight of the sunscreen composition.

Stilbene compounds

Stilbene compounds are secondary substances of heartwood formation in trees and have phytoalexin properties. In chemical terms, they are derivatives of stilbene, often containing one or more phenolic functional groups. In biochemical terms, they belong to a family of phenylalanine derivatives known as phenylpropanoids. Many of their biosynthetic pathways are shared with those of aromatic chalcone-like compounds such as chalcones.

One well characterized botanical stilbene compound is resveratrol (3,5,4' -trihydroxy-trans-stilbene), a resorcinol derivative that was first isolated in 1939 from resveratrol (Veratrum album), found in red grape skins and other fruits and nuts including berries and peanuts. Non-limiting examples of stilbenes useful in the context of the present disclosure include piceid, resveratrol, piceatannol, pterostilbene, and mixtures thereof. In some cases, piceid and resveratrol are preferred stilbenes; spruce neo-glycoside is most preferred.

The total amount of stilbene compounds in the mineral sunscreen composition may vary, but is typically from about 0.1 to 8% by weight based on the total weight of the sunscreen composition. In some cases, the total amount of stilbene compounds in the sunscreen composition is from about 0.1 to about 7 wt%, from about 0.1 to about 6 wt%, from about 0.1 to about 5 wt%, from 0.1 to about 4 wt%, or from about 0.1 to about 3 wt%, preferably from about 0.1 to about 5 wt%, more preferably from about 0.1 to about 3 wt%, based on the total weight of the sunscreen composition.

Although the amount of stilbene compounds is described above, the weight ratio of the total amount of stilbene compounds in the sunscreen composition relative to the total amount of the combination of stilbene compounds, ethylhexylmethoxylene and diethylhexylidene malonate may be from about 0.1 to about 0.5. In some cases, the weight ratio may be about 0.1 to about 0.4, or about 0.2 to about 0.4.

Ethyl hexyl methogliline

The total amount of ethylhexyl methoprene in the mineral sunscreen composition can vary, but is typically from about 0.1 to about 8 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of ethylhexyl methoxycline in the sunscreen composition may be from about 0.1 to about 7 wt%, from about 0.1 to about 6 wt%, from about 0.1 to about 5 wt%, from 0.1 to about 4 wt%, or from about 0.1 to about 3 wt%, preferably from about 0.1 to about 5 wt%, more preferably from about 0.1 to about 3 wt%, based on the total weight of the sunscreen composition.

Although the amount of ethylhexyl methoxylindane is described above, the weight ratio of the total amount of ethylhexyl methoxylindane to the total amount of the combination of stilbene compound, ethylhexyl methoxylindane and diethylhexyl syringylidenemalonate in the sunscreen composition may be from about 0.25 to about 0.75. In some cases, the weight ratio can be about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.65, or about 0.3 to about 0.6.

Diethylhexylidene malonate

The total amount of diethylhexyl syringylidenemalonate in the mineral sunscreen composition may vary, but is typically from about 0.1 to about 8 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of diethylhexyl syringylidenemalonate in the sunscreen composition may be from about 0.1 to about 7 weight percent, from about 0.1 to about 6 weight percent, from about 0.1 to about 5 weight percent, from 0.1 to about 4 weight percent, or from about 0.1 to about 3 weight percent, preferably from about 0.1 to about 5 weight percent, more preferably from about 0.1 to about 3 weight percent, based on the total weight of the sunscreen composition.

Although the amount of diethylhexyl syringylidenemalonate is described above, the weight ratio of the total amount of diethylhexyl syringylidenemalonate to the combined total amount of stilbene compound, ethylhexylmethoxylene, and diethylhexyl syringylidenemalonate in the sunscreen composition may be from about 0.1 to about 0.5. In some cases, the weight ratio may be about 0.1 to about 0.45, or about 0.15 to about 0.4.

Combination of stilbene compounds, ethylhexylmethoxylene and diethylhexylmethylen syringylidene malonate

As already mentioned, the stilbene compounds, ethylhexylmethoxylene and diethylhexylidene malonate interact synergistically in combination, unexpectedly increasing the SPF of the mineral UV filter. Thus, the amount of stilbene compounds, ethylhexylmethoxylene and diethylhexylidene malonate and the weight ratio of these compounds to each other in the sunscreen composition are sufficient to improve the SPF of the sunscreen composition.

In one embodiment, the amount of stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate is sufficient to increase the in vitro SPF of the sunscreen composition by at least 5% as compared to an otherwise identical sunscreen composition in which the total amount of stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate is replaced by ethylhexylmethoxylene alone. In some cases, the in vitro SPF is increased by at least 6%, at least 7%, at least 8%, at least 9%, or at least 10%.

In another embodiment, the amount of stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate is sufficient to increase the in vitro SPF of the sunscreen composition by at least 5% as compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate is replaced by diethylhexylidene malonate alone. In some cases, the in vitro SPF is increased by at least 8%, or at least 10%, at least 12%, at least 15%, at least 18%, or at least 20%.

The weight ratio of stilbene compounds, ethylhexylmethoxylene, and diethylhexyl syringylidenemalonate to each other may be useful to achieve the desired SPF enhancement. Thus, in some embodiments, the weight ratio of stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate, relative to the total weight of the combination of stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate, is as follows:

-from about 0.1 to about 0.5, preferably from about 0.1 to about 0.4, more preferably from about 0.2 to about 0.4, of one or more stilbenes;

-ethylhexyl methoprene from about 0.25 to about 0.75, preferably from about 0.3 to about 0.7, more preferably from about 0.3 to about 0.6; and

-diethylhexyl syringylidenemalonate from about 0.1 to about 0.5, preferably from about 0.1 to about 0.45, more preferably from about 0.15 to about 0.4.

The total amount of the combination of stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate in the sunscreen composition can vary, but is typically from about 0.5 to about 10 weight percent, based on the total weight of the sunscreen composition. In some cases, the total amount of the combination of stilbene compound, ethylhexylmethoxylene, and diethylhexyl syringylidenemalonate in the sunscreen composition may be from about 0.5 to about 8 weight percent, from about 0.5 to about 5 weight percent, from about 0.5 to about 4 weight percent, from about 0.5 to about 3 weight percent, from about 1 to about 10 weight percent, from about 1 to about 8 weight percent, from about 1 to about 5 weight percent, from about 1 to about 4 weight percent, or from about 1 to about 3 weight percent, based on the total weight of the sunscreen composition. Irrespective of the total amount of stilbene, ethylhexylmethoxylene and diethylhexylidene malonate in the sunscreen composition, stilbene, ethylhexylmethoxylene and diethylhexylidene malonate may be present in the sunscreen composition according to the weight ratios set forth above.

Cosmetically acceptable carrier

The sunscreen composition includes a cosmetically acceptable carrier. The term "cosmetically acceptable" means that the material is compatible with the skin and hair. For example, a "cosmetically acceptable carrier" means a carrier that is compatible with the skin and hair and acceptable for application to the body.

The cosmetically acceptable carrier may include, for example, water and/or water-soluble solvents. Non-limiting examples of cosmetically acceptable carriers include glycerin, C1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, mineral oils, liposomes, lamellar lipid materials, water, or any combination thereof.

As examples of organic solvents, mention may be made, without limitation: monohydric and polyhydric alcohols such as ethanol, isopropanol, propanol, benzyl alcohol and phenethyl alcohol; or glycols or glycol ethers such as, for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof, such as, for example, the monomethyl ether of propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol, and alkyl ethers of diethylene glycol, for example, the monoethyl or monobutyl ether of diethylene glycol. Other suitable examples of organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propylene glycol, and glycerol. The organic solvent may be a volatile or non-volatile compound.

In some cases, the cosmetically acceptable carrier may comprise water, a mixture of water and at least one cosmetically acceptable organic solvent, or at least one cosmetically acceptable organic solvent. Additionally, the cosmetically acceptable carrier may be or include ethanol, glycol ethers, such as dipropylene glycol n-butyl ether, isododecane, mineral oil, propylene glycol, pentanediol, hexanediol, glycerin, and mixtures thereof.

The total amount of cosmetically acceptable carrier may vary, but in some cases may be from about 50 to about 95 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of cosmetically acceptable carrier is about 55 to about 95 weight percent, about 60 to about 95 weight percent, about 70 to about 95 weight percent, about 75 to about 95 weight percent, about 50 to about 90 weight percent, about 60 to about 90 weight percent, about 70 to about 90 weight percent, or about 75 to about 90 weight percent, based on the total weight of the sunscreen composition.

Oil/softening agent

Oils and/or emollients may optionally be included in the hair treatment composition. Examples of oils/emollients that may be included in the sunscreen composition include: hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for example heptanoic or octanoic triglycerides, or alternatively for example sunflower oil, corn oil, soybean oil, pumpkin oil, grape seed oil, sesame seed oil, hazelnut oil, almond oil, macadamia nut oil, arabian oil, coriander oil, castor oil, avocado oil, octanoic/decanoic triglycerides, such as those sold by the company Stearineries Dubois or sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea oil and octanediol; synthetic esters and ethers, especially esters and ethers of fatty acids, such as Purcellin oil, 2-octyldodecanol stearate, 2-octyldodecanol erucate, isostearyl isostearate; hydroxylated esters, for example isostearyl lactate, octyl hydroxystearate, octyldodecanol hydroxystearate, diisostearyl malate or triisocetyl citrate; fatty alcohol heptanoate, caprylate or caprate; polyol esters such as propylene glycol dicaprylate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, such as pentaerythritol tetraisostearate, or isopropyl lauroyl sarcosinate, especially sold under the trade name Eldew SL 205 by the company Ajinomoto; linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or non-volatile liquid paraffins and their derivatives, petroleum jelly, polydecenes,isohexadecane, isododecane, hydrogenated polyisobutenes, such as Parleam oil, or n-undecane (C)₁₁) And n-tridecane (C)₁₃) Sold by the Cognis company under the reference name Cetiol UT; fluoro oils partly based on hydrocarbons and/or silicones, such as those described in document JP- ｃA-2295912; silicone oils, for example volatile or non-volatile Polymethylsiloxanes (PDMS) having a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular volatile silicone oils, especially cyclomethicones (cyclic dimethicones), such as cyclohexadimethylsiloxane and cyclopentadimethylsiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups which are pendant or at the end of the silicone chain, these groups containing from 2 to 24 carbon atoms; phenylsilicones, for example phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes or 2-phenylethyl trimethylsiloxysilicates, and polymethylphenylsiloxanes; mixtures thereof.

Specific examples of additional oils/emollients include: cocoglycerides, cyclic polydimethylsiloxanes, dioctyl maleate, caprylic/capric triglycerides, isopropyl myristate, octyl stearate, isostearyl linoleate, lanolin oil, coconut oil, cocoa butter, olive oil, avocado oil, aloe vera extract, jojoba oil, castor oil, fatty acids, oleic acid, stearic acid, fatty alcohols, cetyl alcohol, diisopropyl adipate, hydroxybenzoates, C₉-C₁₅Benzoic acid esters of alcohols, isononyl isononanoate, alkanes, mineral oils, silicones, dimethylpolysiloxanes, ethers, polyoxypropylene butyl ether, polyoxypropylene cetyl ether, C₁₂-C₁₅Alkyl benzoates, aryl alkyl benzoates, isopropyl lauroyl sarcosinate, and any combination thereof.

The total amount of oil and/or emollient, if present, in the sunscreen composition may vary, but may be from about 1 to about 75 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of oil and/or softening agent may be about 1 to about 60 wt%, about 1 to about 50 wt%, about 1 to about 20 wt%, about 5 to about 70 wt%, about 5 to about 60 wt%, about 5 to about 50 wt%, about 10 to about 60 wt%, about 10 to about 50 wt%, about 25 to about 75 wt%, or about 30 to about 60 wt%, based on the total weight of the sunscreen composition.

Film forming agent

Film forming agents may be incorporated into the sunscreen composition to ensure uniform coverage of the UV filter and may be used to make the composition water resistant. Film formers are typically hydrophobic materials that impart film-forming and/or water-repellent properties. One such formulation is polyethylene, commercially available as Performalene 400 from New Phase Technologies, which is polyethylene having a molecular weight of 400. Another suitable film former is polyethylene 2000 (molecular weight 2000), commercially available as Performalene @fromNew Phase Technologies. In addition, another suitable film former is a synthetic wax, also available as Performa V-825 from New Phase Technologies. Other typical film formers include: acrylate/acrylamide copolymers, acrylate copolymers, acrylates/C₁₂-C₂₂Alkyl methacrylate copolymers, polyethylene, waxes, VP/dimethiconol acrylate/polycarboxypolyurethane, butylated PVP, PVP/hexadecene copolymers, octadecene/MA copolymers, PVP/eicosene copolymers, triacontyl PVP, rape/tung oil copolymers, decamethylcyclopentasiloxane (and) trimethylsiloxysilicate, and mixtures thereof. In some cases, the film former is Allianz OPT, tradename of ISP^®acrylate/C sold₁₂-C₂₂An alkyl methacrylate copolymer.

Many of the common film-forming polymers included in sunscreen compositions are insoluble in ethanol (such as PVP/eicosene copolymers). Common film formers employed in ethanol-based sunscreen products are Dermacryl LT or Dermacryl 79 (INCI name: acrylate/octylacrylamide copolymer) sold by Akzo Nobel. Dermacryl LT (CAS number: 80570-62-3) is a hydrophobic, high molecular weight carboxylated acrylic copolymer. It acts as a film former in a wide range of cosmetic formulations, imparting water repellency, improving occlusive properties and reducing active rub-off.

The total amount of film formers in the sunscreen composition, if present, may vary, but is typically from about 0.1 to about 40 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of film former may be about 0.1 to about 30 weight percent, about 0.1 to about 20 weight percent, about 0.1 to about 10 weight percent, about 1 to about 40 weight percent, about 1 to about 30 weight percent, about 1 to about 20 weight percent, or about 1 to about 10 weight percent, based on the total weight of the sunscreen composition.

Emulsifier

The sunscreen composition may optionally include at least one emulsifier, such as an amphoteric, anionic, cationic or nonionic emulsifier, alone or as a mixture, and optionally with a co-emulsifier. Emulsifiers are most commonly used when the sunscreen composition is in the form of an emulsion. The emulsifier is selected in a suitable manner according to the emulsion (W/O or O/W) to be obtained.

For W/O emulsions, examples of emulsifiers that may be mentioned include: dimethicone copolyols such as a mixture of cyclic dimethicone and dimethicone copolyol sold by Dow Corning under the trade name DC 5225C; and alkyl dimethicone copolyols such as lauryl dimethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning and the name Abil EM 90 by the company Goldschmidt^TMCetyl dimethicone copolyol is sold. Crosslinked elastomeric solid organopolysiloxanes containing at least one oxyalkylene group can also be used as surfactants for W/O emulsions, such as those obtained according to the procedures of examples 3, 4 and 8 of U.S. Pat. No. 5,412,004 and examples of U.S. Pat. No. 5,811,487, particularly the product of example 3 (synthetic example) of U.S. Pat. No. 5,412,004, such as the product sold by the company Shin-Etsu under the reference name KSG 21.

For O/W emulsions, examples of emulsifiers that may be mentioned include nonionic emulsifiers, such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; alkylene oxide fatty acid esters of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acid esters; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters such as sucrose stearate; and mixtures thereof.

The fatty acid esters of sugars useful as nonionic amphiphilic lipids may be chosen in particular from those comprising C₈-C₂₂Mixtures of fatty acids and esters or esters of sucrose, maltose, glucose or fructose and C₁₄-C₂₂Esters or mixtures of esters of fatty acids and methyl glucose.

C of fatty units forming esters usable in emulsions₈-C₂₂Or C₁₄-C₂₂The fatty acids comprise saturated or unsaturated linear alkyl chains having from 8 to 22 or from 14 to 22 carbon atoms, respectively. The fatty units of the ester may be chosen in particular from stearates, behenates, arachidonates, palmitates, myristates, laurates, capric esters and mixtures thereof.

By way of example of a mixture of fatty acids and esters or esters of sucrose, maltose, glucose or fructose, mention may be made of sucrose monostearate, sucrose distearate, sucrose tristearate and mixtures thereof, such as the products sold by Croda under the names Crodesta F50, F70, F110 and F160, having an HLB (hydrophilic lipophilic balance) of 5, 7, 11 and 16, respectively; and by way of example for esters or mixtures of esters of fatty acids and methylglucose, mention may be made of the distearate of methylglucose and of polyglycerol-3, sold under the name Tego-care 450 by the company Goldschmidt. Mention may also be made of glucose monoesters or maltose monoesters, such as methyl O-hexadecanoyl-6-D-glucoside and O-hexadecanoyl-6-D-maltoside.

The fatty alcohol ethers of the sugars useful as non-ionic amphiphilic lipids may be chosen in particular from those comprising C₈-C₂₂Fatty alcohol and ethers or mixtures of ethers of glucose, maltose, sucrose or fructose and C₁₄-C₂₂Ethers or mixtures of ethers of fatty alcohols and methyl glucose. They are in particular alkylpolyglycosides.

C of fatty units forming ethers usable in the disclosed emulsions₈-C₂₂Or C₁₄-C₂₂The fatty alcohol comprises a fatty alcohol havingSaturated or unsaturated linear alkyl chains of 8 to 22 or 14 to 22 carbon atoms. The fatty units of the ether may be chosen in particular from decyl, cetyl, behenyl, arachidyl, stearyl, palmityl, myristyl, lauryl, octyl and hexadecanoyl units, and mixtures thereof, such as cetearyl.

By way of example of fatty alcohol ethers for sugars, mention may be made of alkyl polyglycosides, such as decyl glucoside and lauryl glucoside, for example sold by the company Henkel under the names Plantaren 2000 and Plantaren 1200, respectively; cetearyl glucoside, optionally as a mixture with cetearyl alcohol, for example sold under the name Montanov 68 by the company Seppic, under the name Tego-care CG90 by the company Goldschmidt and under the name Emulgade KE3302 by the company Henkel; and arachidyl glucosides, for example in the form of a mixture of arachidyl alcohol and behenyl alcohol and arachidyl glucoside, sold under the name Montanov 202 by the Seppic company.

As non-ionic amphiphilic lipids of this type, more particularly sucrose monostearate, sucrose distearate, sucrose tristearate and mixtures thereof, distearate of methyl glucose and polyglycerol-3, and alkylpolyglycosides are used.

The glycerol fatty esters usable as the nonionic amphiphilic lipid may be chosen in particular from the group comprising esters formed from at least one acid comprising a saturated linear alkyl chain having from 16 to 22 carbon atoms and from 1 to 10 glycerol units. One or more of these glycerin fatty esters may be used in the emulsions of the present disclosure.

These esters may be chosen in particular from stearates, behenates, arachinates, palmitates and mixtures thereof. Stearates and palmitates are preferably used.

By way of example of surfactants which may be used in the emulsions of the present disclosure, mention may be made of decaglycerol monostearate, distearate, tristearate and pentastearate (10 glycerol units) (CTFA name: polyglyceryl-10 stearate, polyglyceryl-10 distearate, polyglyceryl-10 tristearate, polyglyceryl-10 pentastearate), such as the products sold by the Nikko company under the names Nikkol Decaglyn 1-S, 2-S, 3-S and 5-S, respectively; and diglycerol monostearate (CTFA name: polyglycerol-2 stearate), such as the product sold under the name Nikkol DGMS by the Nikko company.

The sorbitan fatty esters useful as the non-ionic amphiphilic lipids are in particular selected from the group comprising C₁₆-C₂₂Esters of fatty acids and sorbitan and C₁₆-C₂₂The group of oxyethylenated esters of fatty acids and of sorbitan. They are formed from at least one fatty acid comprising at least one saturated linear alkyl chain having from 16 to 22 carbon atoms each and sorbitol or ethoxylated sorbitol. The oxyethylenated esters generally comprise from 1 to 100 ethylene oxide units, and preferably from 2 to 40 Ethylene Oxide (EO) units.

These esters may be chosen in particular from stearates, behenates, arachinates, palmitates and mixtures thereof. Stearates and palmitates are preferably used.

By way of example for the sorbitan fatty esters and oxyethylenated sorbitan fatty esters, mention may be made of: sorbitan monostearate (CTFA name: sorbitan stearate), sold under the name Span 60 by ICI company; sorbitan monopalmitate (CTFA name: sorbitan palmitate) sold by ICI company under the name Span 40; or sorbitan 20 EO tristearate (CTFA name: polysorbate 65), sold under the name Tween 65 by ICI.

Ethoxylated fatty ethers are generally ethers consisting of 1 to 100 ethylene oxide units and at least one fatty alcohol chain having 16 to 22 carbon atoms. The fatty chain of the ether may be chosen in particular from behenyl, arachidyl, stearyl and cetyl units, and mixtures thereof, such as cetearyl. By way of example for ethoxylated fatty ethers, mention may be made of ethers of behenyl alcohol comprising 5, 10, 20 and 30 ethylene oxide units (CTFA name: behenyl polyether-5, behenyl polyether-10, behenyl polyether-20 and behenyl polyether-30), such as the products sold by the Nikko company under the names Nikkol BB5, BB10, BB20 and BB 30; and ethers of stearyl alcohol containing 2 ethylene oxide units (CTFA name: steareth-2), such as the product sold by the ICI company under the name Brij 72.

Ethoxylated fatty esters useful as nonionic amphiphilic lipids are esters comprised of 1 to 100 ethylene oxide units and at least one fatty acid chain containing 16 to 22 carbon atoms. The fatty chain of the ester may be chosen in particular from stearate, behenate, arachinate and palmitate units, and mixtures thereof. By way of example of ethoxylated fatty esters, mention may be made of esters of stearic acid comprising 40 ethylene oxide units, such as the product sold by the ICI company under the name Myrj 52 (CTFA name: PEG-40 stearate); and esters of behenic acid containing 8 ethylene oxide units (CTFA name: PEG-8 behenate), such as the product sold under the name Compritol HD5 ATO by the Gattefosse company.

The block copolymer of ethylene oxide and propylene oxide useful as the non-ionic amphiphilic lipid may be chosen in particular from poloxamers, and in particular poloxamer 231, such as the product sold under the name Pluronic L81 by ICI company, having formula (V) wherein x = z =6, y =39 (HLB 2); poloxamer 282, such as the product sold by ICI corporation under the name Pluronic L92, having the formula (V) where x = z =10, y =47 (HLB 6); and poloxamer 124, such as the product sold by ICI corporation under the name Pluronic L44, having the formula (V) where x = z =11, y =21 (HLB 16).

As nonionic amphiphilic lipids, mention may also be made of mixtures of nonionic surfactants described in document EP-A-705593, incorporated herein by reference.

Suitable hydrophobically modified emulsifiers include, for example, inulin lauryl carbamate, commercially available from Beneo Orafti under the trade name Inutec SP 1.

The total amount of emulsifier, if present, in the sunscreen composition may vary, but is typically from about 0.1 to about 30 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of emulsifier is from about 0.1 to about 20 weight percent, from about 0.1 to about 15 weight percent, from about 0.1 to about 10 weight percent, from about 0.5 to about 30 weight percent, from about 0.5 to about 20 weight percent, from about 0.5 to about 15 weight percent, from about 0.5 to about 10 weight percent, from about 1 to about 30 weight percent, from about 1 to about 20 weight percent, from about 1 to about 15 weight percent, from about 1 to about 10 weight percent, or from about 5 to about 5 weight percent, based on the total weight of the sunscreen composition.

Silicone oil

The sunscreen composition may optionally include one or more silicone oils. Non-limiting examples of silicone oils include polydimethylsiloxane, cyclic polydimethylsiloxane, silicone-11, phenyl trimethicone, trimethylsilylaminoisimethicone, and stearyloxytrimethylsilane. In some cases, the cosmetic composition includes a polydimethylsiloxane, and optionally an additional oil, including an additional silicone oil. Typically, the one or more silicone oils are non-volatile silicone oils. In some embodiments, the silicone oil is Polydimethylsiloxane (PDMS); polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendant and/or at the end of the silicone chain, each of said groups containing from 2 to 24 carbon atoms; or phenylsilicones such as phenyl trimethicone, phenyl dimethicone, phenyl (trimethylsiloxy) diphenylsiloxane, diphenyl polydimethylsiloxane, diphenyl (methyldiphenyl) trisiloxane or (2-phenylethyl) trimethylsiloxysilicate.

Further examples of silicone oils which may be mentioned include volatile linear or cyclic silicone oils, especially those having a centistokes of 8 (8X 10)⁶m²/s) viscosity and in particular those containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that can be used in the present disclosure, mention may be made, among others, of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

The total amount of silicone oil in the sunscreen composition, if present, may vary, but is typically from about 0.1 to about 40 weight percent based on the total weight of the sunscreen composition. In some cases, the total amount of silicone oil in the sunscreen composition may be from about 0.1 to about 30 wt%, from about 0.1 to about 20 wt%, from about 0.1 to about 10 wt%, from about 1 to about 40 wt%, from about 1 to about 30 wt%, from about 1 to about 20 wt%, from about 1 to about 10 wt%, from about 5 to about 40 wt%, from about 5 to about 30 wt%, from about 5 to about 20 wt%, or from about 5 to about 15 wt%, based on the total weight of the sunscreen composition.

Form(s) of

The form of the sunscreen composition is not limited. For example, the sunscreen composition may be in the form of a cream, gel, paste, lotion, rinse, foam, emulsion, spray, and the like. The sunscreen compositions may be prepared according to techniques well known to those skilled in the art, particularly those intended for use in the preparation of oil-in-water or water-in-oil emulsions. They may in particular be in the form of simple or complex emulsions (O/W, W/O, O/W/O or W/O/W emulsions), such as creams or emulsions, in the form of gels or cream-gels, or in the form of lotions.

Detailed description of the preferred embodiments

The mineral sunscreen composition does not require organic UV filters. Thus, in some embodiments, the mineral sunscreen composition may be free or substantially free of UV filters. In some embodiments, the mineral sunscreen composition may be free or substantially free of butyl methoxydibenzoylmethane (avobenzone) and/or free or substantially free of ethylhexyl methoxycinnamate (oxcinonide).

The combination of stilbene compounds, ethylhexylmethoxylene and diethylhexylidene malonate in the mineral sunscreen composition increases the SPF of the mineral sunscreen composition. In some embodiments, the mineral sunscreen composition comprising the stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate exhibits an in vitro SPF that is higher than the in vitro SPF of an otherwise identical mineral sunscreen composition without any (or all) of the stilbene compound, ethylhexylmethoxylene, and diethylhexylidene malonate.

In vitro SPF

SPF (sun protection factor) is a measure of how effectively a sunscreen composition will be able to provide protection against ultraviolet B (UV-B) radiation. UV-B rays tend to damage the epidermis, the outer layer of the skin, and are the main cause of reddening and sunburn. In vitro SPF can be determined using methods known in the art. Nevertheless, a preferred method for determining the SPF in vitro is Fageon, l, et al,Int. J. Cosmetic Sci.2009, 405-17, which is hereby incorporated by reference in its entirety.

Method

The present disclosure relates to methods of protecting keratin substrates, particularly the skin and/or hair, from ultraviolet radiation, methods of absorbing UV light, and methods of preventing sunburn. Such methods include applying a sunscreen composition to a keratinous substrate, such as skin and/or hair, and subjecting the keratinous substrate to ultraviolet radiation. Additionally, methods of increasing the SPF of a mineral UV filter and methods of decreasing the whiteness of a mineral sunscreen composition are contemplated. Such methods comprise combining effective amounts of stilbenes, ethylhexylmethoxylene, and diethylhexylidene malonate with one or more mineral UV filters and formulating the sunscreen compositions of the present disclosure.

Detailed description of the preferred embodiments

In some embodiments, a sunscreen composition of the present disclosure may comprise:

(a) from about 1 to about 25 wt%, preferably from about 1 to about 20 wt%, more preferably from about 5 to about 15 wt% of one or more mineral UV filters, for example one or more mineral UV filters selected from the group consisting of titanium dioxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide and mixtures thereof;

(b) from about 0.1 to about 8 wt%, preferably from about 0.1 to about 6 wt%, more preferably from about 0.1 to about 4 wt% of one or more stilbenes, such as picroside, resveratrol, piceatannol, pterostilbene, or mixtures thereof; preferably piceid;

(c) about 0.1 to about 8 weight percent, preferably about 0.1 to about 6 weight percent, more preferably about 0.1 to about 4 weight percent, of ethylhexyl methoxilin;

(d) about 0.1 to about 7 weight percent, preferably about 0.1 to about 6 weight percent, more preferably about 0.1 to about 4 weight percent diethylhexyl syringylidenemalonate; and

(e) from about 50 to about 95%, preferably from about 60 to about 90%, more preferably from about 70 to about 90%, by weight of a cosmetically acceptable carrier;

wherein all weight percents are based on the total weight of the sunscreen composition.

The total amount of stilbene compounds, ethylhexylmethoxylene, and diethylhexylidene malonate in the sunscreen composition may vary, but is typically from about 0.5 to about 10 weight percent, preferably from about 0.5 to about 8 weight percent, more preferably from about 1 to about 6 weight percent, based on the total weight of the sunscreen composition.

The weight ratio of spruce neoside, ethylhexyl methoxylin and diethylhexyl syringylidenemalonate, relative to the total weight of the combination of spruce neoside, ethylhexyl methoxylin and diethylhexyl syringylidenemalonate, may be as follows:

-from about 0.1 to about 0.5, preferably from about 0.1 to about 0.4, more preferably from about 0.2 to about 0.4, of one or more stilbenes;

-ethylhexyl methoprene from about 0.25 to about 0.75, preferably from about 0.3 to about 0.7, more preferably from about 0.3 to about 0.6; and

-diethylhexyl syringylidenemalonate from about 0.1 to 0.5, preferably from about 0.1 to about 0.45, more preferably from about 0.15 to about 0.4.

Furthermore, the amount of ethylhexyl methoxylindane and diethylhexyl syringylidenemalonate is typically sufficient to increase the in vitro SPF of the sunscreen composition by at least 5%, preferably at least 8%, more preferably at least 10% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compounds, ethylhexyl methoxylindane and diethylhexyl syringylidenemalonate is replaced by ethylhexyl methoxylindane alone.

The amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is typically sufficient to increase the in vitro SPF of the sunscreen composition by at least 5%, preferably at least 10%, more preferably at least 20% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is replaced by diethylhexylidene malonate alone.

The sunscreen composition may be free or substantially free of organic UV filters. In some cases, the sunscreen composition is free or substantially free of at least butyl methoxydibenzoylmethane (avobenzone) and ethylhexyl methoxycinnamate (oxcinonide).

In further embodiments, the sunscreen composition comprises:

(a) from about 1 to about 25 wt%, preferably from about 1 to about 20 wt%, more preferably from about 5 to about 15 wt% of one or more mineral UV filters, for example one or more mineral UV filters selected from the group consisting of titanium dioxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide and mixtures thereof;

(b) at least 0.2 wt%, preferably at least 0.2 wt% to about 6 wt%, more preferably at least 0.2 wt% to about 3 wt% of one or more stilbenes, such as piceid, resveratrol, piceatannol, pterostilbene, or mixtures thereof; preferably piceid;

(c) at least 0.5 wt.%, preferably at least 0.5 to about 8 wt.%, more preferably at least 0.5 to about 5 wt.% of ethylhexyl methoprene;

(d) at least 0.2 wt.%, preferably at least about 0.2 to about 6 wt.%, more preferably about 0.2 to about 2 wt.% diethylhexyl syringylidenemalonate;

wherein the total amount of stilbene compounds, ethylhexylmethoxylene and diethylhexylidene malonate does not exceed 10 wt.%, preferably 6 wt.%, more preferably 4 wt.%; and

(e) from about 50 to about 95%, preferably from about 60 to about 90%, more preferably from about 70 to about 90%, by weight of a cosmetically acceptable carrier; wherein the cosmetically acceptable carrier preferably comprises water;

wherein all weight percents are based on the total weight of the sunscreen composition.

The weight ratio of spruce neoside, ethylhexyl methoxylin and diethylhexyl syringylidenemalonate, relative to the total weight of the combination of spruce neoside, ethylhexyl methoxylin and diethylhexyl syringylidenemalonate, may be as follows:

-from about 0.1 to about 0.5, preferably from about 0.1 to about 0.4, more preferably from about 0.2 to about 0.4, of one or more stilbenes;

-ethylhexyl methoprene from about 0.25 to about 0.75, preferably from about 0.3 to about 0.7, more preferably from about 0.3 to about 0.6; and

-diethylhexyl syringylidenemalonate from about 0.1 to 0.5, preferably from about 0.1 to about 0.45, more preferably from about 0.15 to about 0.4.

Furthermore, the amount of ethylhexyl methoxylindane and diethylhexyl syringylidenemalonate is typically sufficient to increase the in vitro SPF of the sunscreen composition by at least 5%, preferably at least 8%, more preferably at least 10% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compounds, ethylhexyl methoxylindane and diethylhexyl syringylidenemalonate is replaced by ethylhexyl methoxylindane alone.

The amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is typically sufficient to increase the in vitro SPF of the sunscreen composition by at least 5%, preferably at least 10%, more preferably at least 20% compared to an otherwise identical sunscreen composition wherein the total amount of stilbene compound, ethylhexylmethoxylene and diethylhexylidene malonate is replaced by diethylhexylidene malonate alone.

The sunscreen composition may be free or substantially free of organic UV filters. In some cases, the sunscreen composition is free or substantially free of at least butyl methoxydibenzoylmethane (avobenzone) and ethylhexyl methoxycinnamate (oxcinonide).

The present disclosure will be better understood from the following examples, which are all intended for illustrative purposes only and are not intended to limit the scope of the present disclosure in any way.

Example 1

The effect of stilbenes (piceid), ethylhexylmethoxylene and diethylhexylidenemalonate on the in vitro SPF of mineral sunscreen compositions was investigated. The three components are used in various ratios to each other. The three components are added to the base sunscreen composition in a total amount of 3 wt%, based on the total weight of the final sunscreen composition, regardless of the ratio of the three components used. Details of the sunscreen compositions are provided in the table below.

The sunscreen composition may be prepared by adding the ingredients of phase B to a main beaker and heating to about 70 ℃ while mixing. Phase B1 was added to phase B and the mixture became more transparent. The mixture was homogenized for 20 minutes. In a separate beaker, combine and heat the ingredients of phase a to about 70 ℃ while mixing. Phase a was added to phase B and the combination was homogenized for 20 minutes while maintaining the temperature at about 70 ℃. The combination was then allowed to start cooling to room temperature. On cooling, when the mixture reaches about 60 ℃, phase C is added and the mixture is homogenized for about 2 minutes. When the mixture reached about 50 ℃, phase D was added and the mixture was homogenized for about 3 minutes. When the mixture reached about 45 ℃, phase E was added and the mixture was allowed to mix for about 5 minutes. When the mixture reaches about 40 ℃, phase F is added and the mixture is homogenized for about 5 minutes.

Using a solution adapted from Fageon, l.et al,Int. J. Cosmetic Sci.2009, 405-17, the in vitro SPF of the resulting sunscreen formulation is measured. A sample weighing 30 mg was transferred through an adjustable pipette and evenly applied to a grit-blasted PMMA (polymethylmethacrylate) plate (roughness 6 μm) measuring 5 cm by about 6 mm thick. The samples were applied evenly to the plates using a series of circular movements followed by left and right movements in a regular and controlled manner using the fingers in the finger sleeve, so that the amount of product left on the plates after said application in this way weighed about 15-20 mg. The plaques were dried at room temperature for 15 to 20 minutes and the in vitro SPF was measured using a Labsphere ultraviolet transmittance analyzer (model UV-2000, available from Solar Light, Pa., philiadelphia). The SPF of each panel was recorded as the average of 5 measurements across different areas of the panel. The SPF of each formulation was recorded as the average of at least two panels.

The results of various mixtures of piceid, ethylhexylmethoxylene and diethylhexylidene malonate were studied using an experimental design in which 16 sunscreen formulations containing mineral UV filters (prepared as described above) were prepared, each containing a total of 3% by weight of the mixture of piceid, ethylhexylmethoxylene and diethylhexylidene malonate. Details of the 3 wt% mixture are detailed in the table below. The amounts of piceid, ethylhexylmethoxylin and diethylhexylidene malonate are expressed in the following table as the weight ratio of the amount of each individual component to the total amount of the mixture of piceid, ethylhexylmethoxylin and diethylhexylidene malonate. For example, mixture #1 included 45 wt% spruce neo-glycoside, 10 wt% ethylhexyl methoxylene, and 45 wt% diethylhexyl syringylidenemalonate, based on the total weight of spruce neo-glycoside, ethylhexyl methoxylene, and diethylhexyl syringylidenemalonate. Mixture #1 was used in the base sunscreen composition described above in an amount of 3 wt%, based on the total weight of the sunscreen composition.

¹In vitro SPF measured on PMMA plates according to the procedure described above. The measured in vitro SPF was used to build a multiple linear regression model.

By fitting the data set to a multiple linear regression model (multiple R)²Value of>0.99), the measured SPF values of the 16 formulations in the above table were used to predict the SPF of all possible mixtures of spruce neoside, ethylhexyl methoxycline and diethylhexyl syringylidenemalonate. Multiple linear regression models were used to predict the in vitro SPF of approximately 24,000 simulated combinations of spruce neo-glycoside, ethylhexylmethoxylene, and diethylhexylidene malonate, used alone or as a mixture, when added at 3 wt% to a sunscreen. About 24,000 simulated combinations included mixtures containing one, two or all of spruce neo-glycoside, ethylhexyl methoxylindane and diethylhexyl syringylidenemalonate. Surprisingly, compositions 11, 12, 13 and 14 were predicted to have the highest in vitro SPF in all combinations. The in vitro SPF of the compositions 11, 12, 13 and 14 of the present invention was compared to compositions C-1 and C-2. For comparison, composition C-1 included ethylhexylmethoxylene, but not stilbenes (piceid) and diethylhexylidene malonate. Composition C-2 comprises diethylhexyl syringylidenemalonate, but does not comprise stilbenes (piceid) and ethylhexylmethoxylinde. The results of exemplary inventive compositions 11, 12, 13 and 14, together with comparative compositions C-1 and C-2, are shown in the following table and illustrate that the use of the inventive combination yields a higher thanThe measured in vitro SPF values achievable using ethylhexylmethoxyline or diethylhexyl syringylidenemalonate alone. In addition, figure 1 shows a contour plot of a linear regression model, demonstrating that the inventive combination yields predicted SPF values that are higher than can be achieved using ethylhexyl methoxycline alone, diethylhexyl syringylidenemalonate alone, or mixtures thereof.

¹In vitro SPF measured on PMMA plates.

²The total amount of (a), (b) and (c) in all sunscreen formulations is 3 wt. -%, based on the total weight of the sunscreen composition. The numerical values in the above tables indicating the amounts of (a), (b) and (c) reflect the weight ratio of each specified component based on the total amount of (a), (b) and (c).