Cosmetic composition comprising bis-ethylhexyloxyphenol methoxyphenyl triazine

Abstract

Disclosed is a cosmetic composition comprising (i) bemotrizinol (bis-ethylhexyloxyphenol methoxyphenyl triazine), (ii) a water-soluble organic UV filter or a salt thereof, (iii) at least one inorganic UV filter, wherein the cosmetic composition is free of UV filters from the group consisting of 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (anisotriazole), 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI homosalate), polysilicone-15, and 2-hydroxy-4-methoxybenzophenone (INCI benzophenone-3); and a method for increasing the water resistance of a cosmetic composition comprising bis-ethylhexyloxyphenol methoxyphenyl triazine (bemotrizinol), zinc oxide, and titanium dioxide, the method comprising the step of adding to the cosmetic composition a water-soluble organic UV filter or a salt thereof.

Description

Technical Field

[0001] This invention relates to a cosmetic composition comprising (i) bemotrizinol (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine), (ii) a water-soluble organic UV filter or a salt thereof, and (iii) at least one inorganic UV filter. Background Technology

[0002] UV radiation has harmful effects on human skin. In addition to the acute effects of sunburn, UV radiation is known to increase the risk of skin cancer. Furthermore, prolonged exposure to UV-A and UV-B light can cause phototoxicity and photosensitivity reactions on the skin and may accelerate skin aging.

[0003] To protect human skin from UV radiation, various sunscreen UV filters (also known as UV absorbers) exist, including UV-A filters, UV-B filters, and broadband filters. These filters are added to sunscreen or daily care compositions. UV filters are organic or inorganic, particulate or non-particulate compounds that have high absorption efficacy across the entire UV light spectrum. Generally, the UV radiation associated with sunscreen products can be divided into UV-A and UV-B radiation. Depending on the location of the maximum absorption, UV filters are classified as UV-A and UV-B filters. When a UV filter absorbs both UV-A and UV-B light, it is called a broadband absorber. Because broadband UV filters provide protection against both UV-A and UV-B radiation, it is preferable to add these types of UV filters to sunscreen or daily care compositions to ensure a broad and effective base of UV protection across the entire UV spectrum.

[0004] Typically, sunscreen compositions contain multiple UV filters and additional components to provide optimal protection across the entire UV-A and UV-B range. However, this approach can have several drawbacks. First, sourcing complex mixtures of different UV filters can be challenging and expensive, thus driving up the price of the final product. Additionally, specific combinations of UV filters can result in photoinstable formulations or components. For example, the combination of the UVA filter avobenzone and the UVB filter octinoxate has been found to cause photodegradation of avobenzone and further heterocyclic addition of both molecules, leading to a significant loss of UV protection. Finally, some of the most commonly used UV filters are under scrutiny due to their health and environmental risks. For instance, commonly used UV filters such as octocrylene, homosalate, octyl methoxycinnamate, and oxybenzone are suspected of exhibiting hormone-like behavior in humans.

[0005] Therefore, there is a desire to develop cosmetic compositions that provide excellent protection against UV radiation and have superior overall properties regarding skin feel, gloss, and stickiness, while requiring as few different UV filters as possible.

[0006] Therefore, the object of the present invention is to provide a composition that can be used in sun protection products having sun protection levels ranging from low to high SPF (6 to greater than 60), low gloss and low viscosity, while requiring small amounts of different UV filters.

[0007] Only a few UV filters can cover the entire range of harmful UV radiation without any known negative impacts on the environment or human health. Bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyltriazine; abbreviation: BEMT, compound (1)) stands out in this group of broadband UV filters because it exhibits a wide and high sun protection band in both the UV-A and UV-B ranges, with an E1,1 (the extinction coefficient of 1% of the filter at an optical thickness of 1 cm) > 730 in the UVB range and above 800 in the UVA range, while also possessing strong photostability and a good health and environmental profile.

[0008]

[0009] (1) Bemotriazine

[0010] The combination of bemotriazine with the inorganic UV filters zinc oxide and titanium dioxide provides a highly effective sunscreen composition that offers excellent UV protection across the entire relevant UV spectrum. Furthermore, all three UV filters are considered eco-friendly and environmentally friendly, and are particularly safe to use. In addition, zinc oxide and titanium dioxide are currently the only UV filters recognized by the FDA as Group 1 GRASE (Generally Recognized as Safe and Effective). Bemotriazine can be added to these two UV filters to become a third Group 1 GRASE UV filter.

[0011] Unfortunately, however, the combination of these three UV filters in cosmetic compositions has been found to have poor water resistance. Since sunscreen compositions are particularly relevant to use on the beach or near swimming pools during hot weather, poor water resistance is a major obstacle to their use.

[0012] Therefore, there is a need to develop cosmetic compositions containing bemotriazine alcohol and one or more inorganic UV filters with improved water resistance. Summary of the Invention

[0013] Surprisingly, it has now been found that the water resistance of such cosmetic compositions can be significantly increased by adding water-soluble organic UV filters or their salts.

[0014] In a first aspect, the present invention relates to a cosmetic composition comprising

[0015] (i) Bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine),

[0016] (ii) Water-soluble organic UV filter or its salt.

[0017] (iii) at least one inorganic UV filter,

[0018] The cosmetic composition does not contain UV filters from the group consisting of: hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate), 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (bisoctrizole), 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI homosalate), polysiloxane-15, and 2-hydroxy-4-methoxybenzophenone (INCI benzophenone-3). This cosmetic composition was found to provide excellent UV protection across the entire harmful UV spectrum, while also providing increased water resistance, compared to similar compositions that do not contain water-soluble organic UV filters or their salts. Particularly surprisingly, water-soluble UV filters can contribute to water resistance.

[0019] In a second aspect, the present invention relates to a method for increasing the water resistance of a cosmetic composition comprising bemotriazine, zinc oxide and titanium dioxide, the method comprising the step of adding a water-soluble organic UV filter or a salt thereof to the cosmetic composition.

[0020] The invention will be described with reference to specific embodiments and certain examples, but the invention is not limited thereto and is limited only by the appended claims.

[0021] definition

[0022] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular form “a / an” also includes the corresponding plural form.

[0023] In the context of this invention, the terms "about" and "approximately" indicate a range of precision that, as will be understood by those skilled in the art, still ensures the technical effect of the features discussed. These terms typically indicate a deviation from the indicated numerical value of ±15%, preferably ±10%, and more preferably ±5%.

[0024] It should be understood that the term "comprising" is not limiting. For the purposes of this invention, the term "consisting of" is considered a preferred embodiment of the term "made up of". If a group is defined below as including at least a certain number of embodiments, this means that a group preferably consisting only of those embodiments is also covered.

[0025] Furthermore, the terms “first,” “second,” “third,” or “(a),” “(b),” “(c),” “(d),” etc., used in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequential or chronological order. It should be understood that such terms are interchangeable where appropriate, and the embodiments of the invention described herein can be operated in orders other than those described or shown herein. Where the terms “first,” “second,” “third,” or “(a),” “(b),” “(c),” “(d),” “i,” “ii,” etc., relate to steps of a method, use, or experiment, unless otherwise indicated in this application set forth above or below, there is no temporal or time interval continuity between these steps; that is, these steps may be performed simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months, or even years between such steps.

[0026] As used herein, the terms "does not contain" or "does not contain" in the context of the composition of the invention not containing a specific compound or group of compounds (which may be grouped under a certain set of terms) means that the composition does not contain more than 0.1% of said compound or group of compounds by weight based on the total weight of the composition. Furthermore, it is preferred that the composition according to the invention does not contain more than 0.05% of said compound or group of compounds by weight, and preferably the composition does not contain any amount of said compound or group of compounds that can be measured using standard analytical equipment. Moreover, it should be understood that in the case where the composition does not contain compounds X and Y, the term "does not contain" or "does not contain" means that the composition must not contain either compound X or compound Y. In other words, the composition may not contain any compound selected from X and Y.

[0027] When referring to a composition and the weight percentage of its constituent ingredients, it should be understood that, according to the invention, the total amount of the ingredients does not exceed 100% (± 0.1%, due to rounding). If the given numerical value has no decimal places, the corresponding value includes the range resulting from normal rounding. For example, the value 10 thus includes the range of 9.5 to 10.4. This also applies if the number is given relative to the next decimal place. For example, the value 0.5 thus covers the range of 0.45 to 0.54.

[0028] It should be understood that the present invention is not limited to the specific methods, schemes, reagents, etc., described herein, as these can vary. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is to be limited only by the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

[0029] Cosmetic compositions herein refer to topical products. The term "topical product" means a product applied to the skin and can be a no-rinse or rinse-off product. Preferred topical products of the present invention are no-rinse products. Suitable no-rinse products of the present invention may be intended for use on the face and / or the body.

[0030] The cosmetic compositions of the present invention include sunscreens, daily skin care compositions, or color cosmetic preparations, and may refer to various forms, such as sprays, emulsions, creams, oils, gels, sticks, foams, powders, pastes, and aerosols.

[0031] The term "sunscreen composition" refers to any topical product that absorbs and can further reflect some portion of UV radiation. Therefore, the term "sunscreen composition" should be understood to include not only sunscreen compositions but also any cosmetic compositions that provide UV protection.

[0032] The term "daily skin care composition" refers to any topical product intended for daily use, with or without UV protection. In the case of UV protection, it absorbs and can further reflect and scatter UV radiation at certain points.

[0033] Suitable makeup formulations refer to cosmetic products, and include, for example, lipsticks, nail polishes, eyeshadows, mascaras, dry and wet cosmetics, blushes, powders, and sunscreens.

[0034] As used herein, the term "UV filter" or "ultraviolet filter" refers to an organic or inorganic compound that can absorb and further reflect and scatter UV radiation caused by sunlight. UV filters can be classified as UV-A filters, UV-B filters, or broadband filters based on their UV absorbance distribution. Preferably, the term "UV filter" includes any UV filter or a component thereof as defined in Annex VI of Regulation (EC) 1223 / 2009 of the European Parliament (version of November 11, 2022).

[0035] The water-soluble UV filter has a solubility in water of at least 2.0% by weight, preferably at least 3.0% by weight, and more preferably at least 5.0% by weight.

[0036] The oil-soluble filter has a solubility of at least 2.0%, preferably at least 3.0%, and more preferably at least 5.0% by weight in a particular emollient.

[0037] The term "emollient" refers to cosmetic oils used to protect, moisturize, and lubricate the skin. The word "emollient" is derived from the Latin word *mollire*, meaning to soften. Typically, emollients prevent moisture from evaporating from the skin by forming a occlusive coating. Alternatively or additionally, emollients improve the distribution of products on the skin. Emollients can be classified into different groups based on their polarity index.

[0038] As used herein, the term "Sun Protection Factor (SPF)" indicates the degree to which a sunscreen composition protects the skin from erythema (sunburn) primarily caused by UV-B radiation. Specifically, this factor indicates how long protected skin can be exposed to sunlight without getting sunburned, compared to untreated skin. For example, if a sunscreen composition with an SPF of 15 is applied evenly to the skin of someone who typically gets sunburned after 10 minutes in the sun, the sunscreen allows that person to stay in the sun 15 times longer. In other words, SPF 15 means that 1 / 15 of the intense UV radiation will reach the skin, assuming a thick, evenly applied dose of sunscreen at 2 mg / cm².

[0039] The definition of “broadband” protection (also known as broad-spectrum or wide-range protection) can be based on, for example, a “critical wavelength” or a UVA1 / UV ratio or UVA-PF. For broadband protection, both UV-B and UV-A protection must be provided. Under US requirements, a critical wavelength of at least 370 nm is needed to achieve broad-spectrum protection. In a proposed order (OTC000008) published on September 24, 2021, the FDA proposed adding an additional requirement for passing the broad-spectrum test: the product must have a UVA1 / UV ratio of at least 0.7. Furthermore, the European Commission recommends that all sunscreens or cosmetic compositions should have a UV-A protection factor that is at least one-third of the stated sun protection factor (SPF); for example, if a sunscreen composition has an SPF of 30, then the UVA protection factor must be at least 10.

[0040] The term "critical wavelength" is defined as a wavelength at which the area under the UV protection curve (protection percentage relative to wavelength) occupies 90% of the total area under the curve in the UV region (290-400 nm). For example, a critical wavelength of 370 nm indicates that the protection of a sunscreen composition is not limited to the wavelength of UV-B (i.e., the wavelength of 290-320 nm), but extends to 370 nm, such that at least 90% of the total area under the protection curve in the UV region is reached at 370 nm.

[0041] The term "application" refers to the act of applying a cosmetic composition to a person's skin. Detailed Implementation

[0042] The first aspect of the present invention relates to a cosmetic composition comprising

[0043] (i) Bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine),

[0044] (ii) Water-soluble organic UV filter or its salt.

[0045] (iii) at least one inorganic UV filter,

[0046] The cosmetic compositions of this invention do not contain UV filters from the group consisting of: 2-[4-(diethylamino)-2-hydroxybenzoyl]hexyl benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate), 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (benzotriazine), 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI homosalate), polysiloxane-15, and 2-hydroxy-4-methoxybenzophenone (INCI benzophenone-3). Compared to similar cosmetic compositions that do not contain water-soluble organic UV filters or their salts, the cosmetic compositions of this invention exhibit significantly improved water resistance as determined by contact angle measurement methods. Furthermore, the cosmetic compositions of this invention contain only environmentally and eco-friendly UV filters that are safe to use and do not pose a risk of hormonal imbalance.

[0047] According to one embodiment of the invention, the cosmetic composition is free of 2-ethylhexyl-2-cyano-3,3-diphenylprop-2-enoate (INCI octyl cyanobenzyl acrylate). Octyl cyanobenzyl acrylate is suspected of exhibiting hormone-like behavior in humans.

[0048] According to one embodiment of the invention, the cosmetic composition is free of 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (avobenzone). Under certain conditions, avobenzone can be unstable when combined with inorganic UV filters (such as zinc oxide or titanium dioxide). For this reason, it is preferred that the cosmetic composition does not contain avobenzone.

[0049] According to one embodiment of the invention, the cosmetic composition is free of (2E)-3-(4-methoxyphenyl)prop-2-enoic acid (RS)-2-ethylhexyl methoxycinnamate. Octyl methoxycinnamate is also suspected of exhibiting hormone-like behavior in humans.

[0050] According to one embodiment of the present invention, the cosmetic composition is free of 4,4',4''-(1,3,5-triazine-2,4,6-trimethyltriimino)tri-benzoic acid-tris(2-ethylhexyl) ester (octyltriazinone).

[0051] According to another embodiment of the invention, the cosmetic composition does not contain any additional organic UV filters. The UV filter combination of the sunscreen composition of the present invention provides excellent UV radiation protection without requiring any additional organic UV filters. By limiting the number of different UV filters to a combination of bemotriazine, one or more water-soluble organic UV filters or their salts, and at least one inorganic UV filter, the risk of allergic skin reactions is significantly reduced.

[0052] The cosmetic composition of the present invention comprises at least one inorganic UV filter (III). According to one embodiment of the present invention, the at least one inorganic UV filter (III) is selected from zinc oxide, titanium dioxide, and mixtures thereof. According to a particularly preferred embodiment of the present invention, the cosmetic composition comprises zinc oxide and titanium dioxide.

[0053] According to one embodiment of the invention, the water-soluble organic UV filter (ii) is selected from the group consisting of: phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole), [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1]heptyl]methyl]phenyl]methylene]-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptyl]methanesulfonic acid (Ekason), disodium phenyl dibenzimidazole tetrasulfonate (bisdisulizoledisodium), or salts thereof, and combinations thereof. These water-soluble organic UV filters are particularly suitable for increasing the water resistance of cosmetic compositions comprising bemotriazine and at least one inorganic UV filter.

[0054] According to a preferred embodiment of the invention, the water-soluble organic UV filter (ii) is phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole), or a salt thereof, or a mixture thereof. Ensolazole in acid or salt form is particularly suitable for increasing the water resistance of cosmetic compositions comprising bemotriazine and at least one inorganic UV filter.

[0055] According to one embodiment, the cosmetic composition further comprises an organic neutralizing agent. More preferably, ensolazole is used as a salt of an organic nitrogen compound. More preferably, the organic neutralizing agent is selected from tromethorphan, triethanolamine, tetrahydroxypropylethylenediamine, arginine, and aminomethylpropanol.

[0056] According to one embodiment of the invention, the molar ratio of the water-soluble organic UV filter (ii) to the organic neutralizer is 3:1 to 1:3, particularly 2:1 to 1:2 or 1.5:1 to 1:1.5. In one embodiment of the invention, the molar ratio of the water-soluble organic UV filter (ii) to the organic neutralizer is 1:1.

[0057] According to another preferred embodiment of the invention, the cosmetic composition comprises a hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer (a polymer of 2-hydroxyethyl acrylate and monosodium 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid (CAS111286-86-3). Such polymers are known in the art and are, for example, marketed by Seppic under the trade name SEPINOV. TM EMT 10 is available for sale. These polymers may be present in the described cosmetic composition in amounts of 0.3 to 3.0 wt.%, for example 0.5 to 2.0 wt.%, particularly 1.0 to 2.0 wt.%, based on the total weight of the cosmetic composition.

[0058] The cosmetic composition of the present invention comprises bemotriazine alcohol. According to one embodiment of the invention, the cosmetic composition comprises bemotriazine alcohol in an amount of 0.5 to 6.0 wt.% based on the total weight of the cosmetic composition. According to another embodiment of the invention, the cosmetic composition comprises bemotriazine alcohol in an amount of 0.5 to 5.5 wt.%, 1.0 to 5.0 wt.%, or 1.5 to 5.0 wt.%, or 2.0 to 5.0 wt.% based on the total weight of the cosmetic composition. According to yet another embodiment of the invention, the cosmetic composition comprises bemotriazine alcohol in an amount of 2.0 to 4.0 wt.%, or 2.0 to 3.0 wt.%, or 2.0 to 2.5 wt.% based on the total weight of the cosmetic composition. The cosmetic compositions described herein may, for example, contain amounts of bemotriazine based on the total weight of the cosmetic composition of 0.5 wt.%, or 1.0 wt.%, or 1.5 wt.%, or 2.0 wt.%, or 2.5 wt.%, or 3.0 wt.%, or 3.5 wt.%, or 4.0 wt.%, or 4.5 wt.%, or 5.0 wt.%, or 5.5 wt.%, or 6.0 wt.%.

[0059] The cosmetic compositions of the present invention comprise a water-soluble organic UV filter or a salt thereof. According to one embodiment of the invention, the cosmetic composition comprises a water-soluble organic UV filter or a salt thereof in an amount of 0.1 to 4.0 wt.%, particularly 0.2 to 3.5 wt.%, or 0.5 to 3.0 wt.%, or 1.0 to 2.5 wt.%, based on the total weight of the cosmetic composition. The cosmetic compositions described herein may, for example, comprise a water-soluble organic UV filter or a salt thereof in an amount of 0.5 wt.%, or 1.0 wt.%, or 1.5 wt.%, or 2.0 wt.%, or 2.5 wt.%, or 3.0 wt.%, or 3.5 wt.%, or 4.0 wt.%, based on the total weight of the cosmetic composition.

[0060] Particularly suitable water-soluble organic UV filters are ensolazole or its salts. According to one embodiment of the invention, the cosmetic composition comprises 0.1 to 4.0 wt.%, particularly 0.2 to 3.5 wt.%, or 0.5 to 3.0 wt.%, or 1.0 to 2.5 wt.%, based on the total weight of the cosmetic composition. The cosmetic compositions described herein may, for example, comprise 0.5 wt.%, or 1.0 wt.%, or 1.5 wt.%, or 2.0 wt.%, or 2.5 wt.%, or 3.0 wt.%, or 3.5 wt.%, or 4.0 wt.%, based on the total weight of the cosmetic composition.

[0061] According to one embodiment of the present invention, the cosmetic composition comprises zinc oxide.

[0062] If zinc oxide is present in the cosmetic composition, it is preferred that the zinc oxide is coated. Preferably, the zinc oxide is coated with an inorganic and / or organic surface coating.

[0063] In a preferred embodiment of the invention, zinc oxide is coated with an inorganic surface coating selected from the group consisting of sodium hexametaphosphate (NaPO3), sodium metaphosphate (NaPO3)n, silicon dioxide (SiO2) (also known as: silicon dioxide, e.g., CAS No.: 7631-86-9), iron oxide (Fe2O3), and mixtures thereof. It should be understood that these inorganic surface coatings may exist alone, in combination, and / or in combination with organic surface coatings.

[0064] In a preferred embodiment of the invention, the zinc oxide is coated with an organic surface coating selected from the group consisting of: fatty acids such as stearic acid or lauric acid, dimethyl polysiloxane (also known as dimethyl silicone oil), methyl polysiloxane (methyl silicone oil), simethicone (a mixture of dimethyl polysiloxane and silica gel having an average chain length of about 200 to about 350 dimethyl siloxane units), triethoxyoctylsilane, octyltrimethoxysilane, and mixtures thereof. It should be understood that these organic surface coatings may exist alone, in combination, and / or in combination with inorganic surface coatings. Preferably, the zinc oxide according to the invention is uncoated or coated with dimethyl silicone oil, methyl silicone oil, or triethoxyoctylsilane; most preferably, the zinc oxide according to the invention is coated with triethoxyoctylsilane.

[0065] According to one embodiment of the invention, the cosmetic composition comprises zinc oxide in an amount of 0.5 to 25.0 wt.%, or 0.5 to 20 wt.%, or 1.0 to 15.0 wt.%, or 1.5 to 10 wt.%, or 2.0 to 8.0 wt.%, or 2.5 to 6.0 wt.%, or 3.5 to 5.5 wt.% based on the total weight of the cosmetic composition. The cosmetic composition described herein may, for example, comprise 0.5 wt.%, or 1.0 wt.%, or 1.5 wt.%, or 2.0 wt.%, or 2.5 wt.%, or 3.0 wt.%, or 3.5 wt.%, or 4.0 wt.%, or 4.5 wt.%, or 5.0 wt.%, or 5.5 wt.%, or 6.0 wt.%, or 6.5 wt.%, or 7.0 wt.%, or 7.5 wt.%, or 8.0 wt.%, or 8.5 wt.%, or 9.0 wt.%, or 9.5 wt.%, or 10.0 wt.%, or 10.5 wt.%, or 11.0 wt.%, or 11.5 wt.%, or 12.0 wt.%, or 12.5 wt.%, or 13.0 wt.%, or 13.5 wt.%, or 14.0 wt.%, or 14.5 wt.% based on the total weight of the cosmetic composition. Zinc oxide in amounts of wt.%, or 15.0 wt.%, or 15.5 wt.%, or 16.0 wt.%, or 16.5 wt.%, or 17.0 wt.%, or 17.5 wt.%, or 18.0 wt.%, or 18.5 wt.%, or 19.0 wt.%, or 19.5 wt.%, or 20.0 wt.%, or 20.5 wt.%, or 21.0 wt.%, or 21.5 wt.%, or 22.0 wt.%, or 22.5 wt.%, or 23.0 wt.%, or 23.5 wt.%, or 24.0 wt.%, or 24.5 wt.%, or 25.0 wt.%.

[0066] According to one embodiment of the present invention, the cosmetic composition comprises titanium dioxide.

[0067] In a preferred embodiment of the invention, titanium dioxide (iii) is a nanomaterial. In this regard, it should be understood that the term "nanomaterial" follows European Commission Recommendation 2011 / 696 / EU. Thus, in nanomaterials, based on a quantity-based size distribution, 50% of the particles are less than 100 nm, including constituent particles in aggregates or clusters. In another preferred embodiment of the invention, titanium dioxide is a non-nanomaterial. Thus, in non-nanomaterials, based on a quantity-based size distribution, more than 50% of the particles are equal to or greater than 100 nm.

[0068] In a preferred embodiment of the invention, the titanium dioxide has a number-average fundamental particle size of less than 1000 nm, preferably less than 200 nm, more preferably less than 100 nm, and particularly less than 50 nm. More preferably, the titanium dioxide has a number-average fundamental particle size of 0.1 to less than 1000 nm, more preferably 1 to 100 nm, and particularly 2 to 50 nm. The number-average fundamental particle size of the titanium dioxide particles can be determined by any method known in the art, such as transmission electron microscopy (TEM).

[0069] According to a preferred embodiment of the invention, the titanium dioxide is coated. Uncoated titanium dioxide is photocatalytic and should be avoided in sunscreens. Preferably, the titanium dioxide is coated titanium dioxide, which is a pigment that has undergone one or more surface treatments to improve its chemical, electronic, mechanochemical and / or mechanical properties, preferably with compounds selected from the group consisting of: amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithin, sodium, potassium, zinc, and iron salts of fatty acids (stearic acid), (titanium) metal alkoxides, polyethylene, silicones (such as dimethyl silicone oil, cyclomethyl silicone oil, polysiloxane, simethicone, dimethyl silicone oil / methyl silicone oil copolymer and / or cyclopentasiloxane), proteins (collagen, elastin), alkanolamines, silicon dioxide, metal oxides, sodium hexametaphosphate, silicon dioxide and mixtures thereof, more preferably wherein the titanium dioxide is coated with stearic acid, silicon dioxide, dimethyl silicone oil and mixtures thereof.

[0070] Preferably, the coated titanium dioxide pigment is titanium oxide, and the coating contains:

[0071] -Silica, such as Sunveil from Ikeda, Eusolex TAVO from Merck, and Sunsil TIN 50 from Sunjin.

[0072] -Silica and iron oxide, such as Sunveil F from Ikeda Corporation; Microtitanium Dioxide MT 100 SA from Tayca Corporation; and Tioveil from Croda Corporation;

[0073] -Iron oxide and iron stearate, such as Microtitanium Dioxide MT100 F from Imperial Chemical Industries;

[0074] -Silica and silicones, such as UV-Titan X 195 from Sachtleben Pigments and ParsolTX from DSM Nutritional Products;

[0075] -Silica and cetyl phosphate, such as Eusolex T-easy from Merck;

[0076] - UV Titan M 262 (containing dimethyl silicone oil) from Sahaliben Pigment Company; Eusolex T-2000 (containing simethicone oil) from Merck.

[0077] - Triethanolamine, such as STT-65-S from Titan Kogyo Co., Ltd.;

[0078] - Stearic acid, such as Tipaque TTO-55 (C) from Ishihara Corporation;

[0079] - Sodium hexametaphosphate, such as Microtitanium Dioxide MT 150 W from Imperial Chemical Industries;

[0080] -Silicones, such as trimethoxyoctylsilane or simethicone;

[0081] -Octylated trimethylsilane, especially sold by Degussa Silices under the trade name T805;

[0082] - Polydimethylsiloxane, especially sold by Cardre under the trade name 70250 Cardre UFTiO2SI3;

[0083] - Anatase / rutile TiO2 treated with polydimethylsiloxane, especially that sold by ColorTechniques under the trade name Microtitanium Dioxide USP Grade Hydrophobie.

[0084] It may also be mentioned that titanium dioxide pigments are doped with at least one transition metal (such as iron, zinc, or manganese, and more particularly manganese). Preferably, the doped pigment is in the form of an oily dispersion. The oil present in the oily dispersion is preferably selected from triglycerides, including triglycerides of decanoic acid / caprylic acid.

[0085] According to one embodiment of the invention, the cosmetic composition comprises titanium dioxide in an amount of 0.5 to 25.0 wt.%, or 0.5 to 20 wt.%, or 1.0 to 15.0 wt.%, or 1.5 to 10 wt.%, or 2.0 to 8.0 wt.%, or 4.0 to 7.0 wt.%, or 4.5 to 5.5 wt.% based on the total weight of the cosmetic composition. The cosmetic composition described herein may, for example, comprise 0.5 wt.%, or 1.0 wt.%, or 1.5 wt.%, or 2.0 wt.%, or 2.5 wt.%, or 3.0 wt.%, or 3.5 wt.%, or 4.0 wt.%, or 4.5 wt.%, or 5.0 wt.%, or 5.5 wt.%, or 6.0 wt.%, or 6.5 wt.%, or 7.0 wt.%, or 7.5 wt.%, or 8.0 wt.%, or 8.5 wt.%, or 9.0 wt.%, or 9.5 wt.%, or 10.0 wt.%, or 10.5 wt.%, or 11.0 wt.%, or 11.5 wt.%, or 12.0 wt.%, or 12.5 wt.%, or 13.0 wt.%, or 13.5 wt.%, or 14.0 wt.%, or 14.5 wt.% based on the total weight of the cosmetic composition. wt.%, or 15.0 wt.%, or 15.5 wt.%, or 16.0 wt.%, or 16.5 wt.%, or 17.0 wt.%, or 17.5 wt.%, or 18.0 wt.%, or 18.5 wt.%, or 19.0 wt.%, or 19.5 wt.%, or 20.0 wt.%, or 20.5 wt.%, or 21.0 wt.%, or 21.5 wt.%, or 22.0 wt.%, or 22.5 wt.%, or 23.0 wt.%, or 23.5 wt.%, or 24.0 wt.%, or 24.5 wt.%, or 25.0 wt.% of titanium dioxide.

[0086] According to one embodiment of the present invention, the cosmetic composition comprises

[0087] (i) 0.5 to 6.0 wt.% of bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyltriazine);

[0088] (ii) 1.0 to 4.0 wt.% of phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole);

[0089] (iii) 0.5 to 25.0 wt.% of zinc oxide;

[0090] (iv) 0.5 to 25.0 wt.% titanium oxide;

[0091] Each is based on the total weight of the cosmetic composition.

[0092] According to one embodiment of the present invention, the cosmetic composition comprises

[0093] (i) 1.5 to 5.0 wt.% of bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine);

[0094] (ii) 1.5 to 3.0 wt.% of phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole);

[0095] (iii) 2.5 to 10.0 wt.% of zinc oxide;

[0096] (iv) 2.5 to 10.0 wt.% of titanium oxide;

[0097] (v) 0.5 to 4.0 wt.% of a neutralizing agent selected from tromethamine, triethanolamine, tetrahydroxypropylethylenediamine, arginine, and aminomethylpropanol.

[0098] Each is based on the total weight of the cosmetic composition.

[0099] According to one embodiment of the present invention, the cosmetic composition comprises

[0100] (i) 2.0 to 5.0 wt.% of bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyltriazine);

[0101] (ii) 2.0 to 2.5 wt.% of phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole);

[0102] (iii) 3.5 to 6.5 wt.% zinc oxide;

[0103] (iv) 3.5 to 6.5 wt.% titanium oxide;

[0104] (v) 0.7 to 2.5 wt.% of a neutralizing agent selected from tromethamine, triethanolamine, tetrahydroxypropylethylenediamine, arginine, and aminomethylpropanol.

[0105] Each is based on the total weight of the cosmetic composition.

[0106] According to a preferred embodiment of the invention, a cosmetic composition having a contact angle greater than 30° according to a contact angle measurement method is considered water-resistant. According to one embodiment of the invention, using a contact angle measurement method, the cosmetic composition exhibits a contact angle of at least 35°. According to another embodiment, using a contact angle measurement method, the cosmetic composition exhibits a contact angle of at least 40°.

[0107] The contact angle measurement method refers to a method for determining the water resistance of a composition containing a UV filter by measuring the wettability of a treated skin area. This method is described in detail in R. Hagens et al., “Contact angle measurement - a reliable supportive method for screening water-resistance of ultraviolet-protecting products in vivo”, International Journal of Cosmetic Science, 2007, 29, 283-291. It is based on the concept that the higher the wettability of the skin area treated with the sunscreen, the higher the wash-off rate of the locally applied UV filter compound. Further details of this method are disclosed in the experimental section.

[0108] The cosmetic compositions of the present invention preferably comprise additives, which are particularly selected from the group consisting of: emulsifiers, emollients, additional viscosity modifiers (thickeners), sensory enhancers, humectants, film-forming agents, UV scattering compounds, adjuvants (such as anti-aging active ingredients), vitamins, antioxidants, chelating agents, preservatives, fragrances, and combinations thereof.

[0109] Preferred O / W emulsifiers include, but are not limited to:

[0110] - Glucose derivatives, such as cetyl glucoside, arachidonic glucoside, lauryl glucoside, polyglyceryl-3-methyl gluconate distearate, and methyl sesquistearate glucose.

[0111] - Sucrose derivatives, such as sucrose polystearate and sucrose palmitate.

[0112] - Sorbitol derivatives, such as polysorbate derivatives,

[0113] Inulin derivatives, such as inulin lauryl carbamate,

[0114] - Glycerides of fatty acids, such as glyceryl stearate, glyceryl stearate SE, and glyceryl stearate citrate.

[0115] -Glutamic acid derivatives, such as sodium stearoyl glutamate,

[0116] - Sulfosuccinic acid derivatives, such as disodium cetearyl sulfosuccinate.

[0117] - Phosphoric acid derivatives, such as cetyl phosphate potassium, cetyl alcohol polyether-10 phosphate, and C20-22 alkyl phosphate.

[0118] - Polyglycerol-based fatty acid esters, such as polyglycerol-3-diisostearate, polyglycerol-2-dipolyhydroxystearate, and polyglycerol-10-stearate.

[0119] -Oxyolefinated fatty alcohols, such as cetearyl alcohol polyether-20, stearyl alcohol polyether-21, and behenyl alcohol polyether-25.

[0120] -O-olefinized fatty acids, such as PEG-100 stearate,

[0121] -Oxylenized organic modified silicone / polysiloxane / polyalkyl / polyether copolymers and derivatives

[0122] -Ethoxylated fatty acid soap

[0123] - Phospholipid-based, such as lecithin derivatives.

[0124] Preferred emulsifiers for forming W / O emulsions include, but are not limited to:

[0125] - Glycerides of fatty acids, such as glyceryl oleate and sorbitol laurate.

[0126] -Sorbitol esters, such as sorbitol oleate,

[0127] - Polyglycerol-based fatty acid esters, such as polyglycerol-3-diisostearate, polyglycerol-2-dipolyhydroxystearate, and polyglycerol-4-isostearate.

[0128] -Oxylenized fatty alcohols, such as stearyl alcohol polyether-2

[0129] -O-olefinically modified fatty acids, such as PEG-30 dimerized hydroxystearate.

[0130] - Organically modified silicone / polysiloxane / polyalkyl / polyether copolymers and derivatives, such as cetyl dimethyl silicone oil copolyol, cetyl PEG / PPG-10 / 1 dimethyl silicone oil, and PEG-10 dimethyl silicone oil.

[0131] Preferred emollients include, but are not limited to:

[0132] -Esters of straight-chain or branched fatty acids with straight-chain or branched fatty alcohols, such as propyl hepta-octanoate, cocoyl caprylate, isopropyl myristate, and ethylhexyl palmitate.

[0133] - Esters of aromatic carboxylic acids with straight-chain or branched fatty alcohols, such as benzoic acid C 12 -C 15 -alkyl esters, ethylhexyl benzoate, phenethyl benzoate

[0134] - Dicarboxylic acid esters containing straight-chain or branched alcohols, such as dibutyl adipate, dioctyl carbonate, and diisopropyl sebacate.

[0135] Esters of α-hydroxycarboxylic acids with straight-chain or branched fatty alcohols

[0136] - Esters of straight-chain or branched fatty acids with polyols, such as butylene glycol dioctanoate / didecanoate.

[0137] -Based on C6-C 18 Fatty acid monoglycerides, diglycerides, and triglycerides, such as caprylic / capric triglycerides and coconut oil glycerides.

[0138] -Gerbert alcohols, such as octyldodecynol.

[0139] - Hydrocarbons, such as hydrogenated polyisobutylene, mineral oil, squalene, and isohexadecane.

[0140] -Ethers, such as dioctyl ether,

[0141] - Silicone derivatives (organically modified polysiloxanes), such as dimethyl polysiloxane and cyclic silicones.

[0142] Preferred lipophilic thickeners include, but are not limited to:

[0143] - Fatty alcohols, such as cetyl alcohol, cetearyl alcohol, stearyl alcohol, betaine alcohol,

[0144] - Fatty acids, such as stearic acid and palmitic acid,

[0145] - Fatty acid esters, such as myristyl stearate, pentaerythritol distearate, cetyl palmitate, tribehenin, and dextrin palmitate.

[0146] - Waxes, such as beeswax, carnauba wax, microcrystalline wax, ceresin, ozocerite, rice bran wax, sunflower wax,

[0147] - Hydrogenated vegetable oil, hydrogenated castor oil, hydrogenated vegetable glycerides

[0148] - Hydrogenated castor oil / sebacic acid copolymer,

[0149] - Derivatives based on silica, such as silica and dimethylsilyl alkyl silica.

[0150] Hydrophilic stabilizers / thickeners include, but are not limited to:

[0151] -Natural gums, such as xanthan gum, tara gum, and carrageenan gum.

[0152] - Silicate derivatives, such as magnesium aluminum silicate,

[0153] - Cellulose derivatives, such as hydroxypropyl cellulose and microcrystalline cellulose,

[0154] - Starch derivatives, such as hydroxypropyl starch phosphate.

[0155] Hydrophilic stabilizers / thickeners include, but are not limited to:

[0156] -Natural gums, such as xanthan gum, tara gum, carrageenan gum, guar gum, agar gum, alginate, and gellan gum.

[0157] - Silicate derivatives, such as magnesium aluminum silicate,

[0158] - Cellulose derivatives, such as hydroxypropyl cellulose and microcrystalline cellulose,

[0159] - Starch derivatives, such as hydroxypropyl starch phosphate,

[0160] - Homopolymers of polyacrylates or network acrylics or polyacrylamides, such as carbomer, acrylate copolymers, acrylate / acrylic acid C10-C30-alkyl ester crosspolymers, acrylate / behenol polyether-25 methacrylate copolymers.

[0161] Preferred sensory enhancers include, but are not limited to:

[0162] - Polyamide derivatives, such as nylon-12,

[0163] - Polymethyl methacrylate,

[0164] -Silica,

[0165] -Mica,

[0166] - Polymethylsilsesquioxane,

[0167] - Starch derivatives, such as aluminum starch octenyl succinate.

[0168] -Dimethyl silicone oil derivatives

[0169] -boron nitride,

[0170] -HDI / trimethylolhexyl lactone crosslinking polymer

[0171] - Perlite.

[0172] It may also contain UV-protective scattering compounds. These include, but are not limited to:

[0173] - Microcrystalline cellulose,

[0174] -Calcium carbonate,

[0175] 2-hydroxyapatite,

[0176] -Silica,

[0177] - Hollow spheres, such as styrene / acrylate copolymer spheres.

[0178] Other components may fall into the categories of film-forming agents and film-forming enhancers. These compounds include, but are not limited to:

[0179] - Hydrogenated dimerized dilinoleyl / dimethyl carbonate copolymer

[0180] -Diisostearoyl polyglycerol-3-dimeric linoleate

[0181] - Polyglycerol-3-stearate / sebacate crosspolymer

[0182] - Cellulose derivatives, such as methylcellulose and ethylcellulose,

[0183] -Octaylglycerol / Sebacic acid copolymer.

[0184] It may also contain UV protection enhancer compounds. These include, but are not limited to:

[0185] -Benztriazolyldodecyl p-cresol

[0186] -Ethylhexylmethoxypolyacrylonitrile,

[0187] -Polyester-8,

[0188] - Diethylhexyl syringite

[0189] -Trimethoxybenzylpentanedione

[0190] Diethylhexyl 2,6-naphthalenedicarboxylate

[0191] -Bis(cyanoethyl butyl ester) 10-anthracene diene adipyl,

[0192] -Polyester-25,

[0193] - Butyl octyl salicylate.

[0194] Preferred wetting agents include, but are not limited to:

[0195] -glycerin,

[0196] -Butanediol,

[0197] -Propylene glycol,

[0198] -Sorbitol,

[0199] -β-glucan,

[0200] -1,2-pentanediol,

[0201] -1,2-hexanediol,

[0202] -1,2-octanediol,

[0203] -1,2-decanediol,

[0204] -2-Methyl-1,3-propanediol.

[0205] Preferred adjuvants include, but are not limited to:

[0206] -Tocopherol derivatives

[0207] -Retinol derivatives,

[0208] -Ascorbic acid derivatives

[0209] -Bisabolol,

[0210] -Allantoin,

[0211] -Panthenol,

[0212] - Chelating agents (EDTA, EDDS, EGTA, phytic acid, piroctone olamine).

[0213] -Ethylhexylglycerin,

[0214] -Hydroxyacetophenone,

[0215] -Octayloxyoxime acid,

[0216] - Propellants, such as propane, butane, isobutylene, and dimethyl ether.

[0217] - Insect repellents, such as butyl acetyl aminopropionate.

[0218] Preferred preservatives include, but are not limited to:

[0219] -Benzyl alcohol,

[0220] - Gingerone.

[0221] Preferred fragrances are selected from the group consisting of: limonene, citral, linalool, α-isomethylionone, geraniol, citronellol, 2-isobutyl-4-hydroxy-4-methyltetrahydropyran, 2-tert-butyl-pentylcyclohexyl acetate, 3-methyl-5-phenyl-1-pentanol, 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene, adipate, α-pentylcinnamaldehyde, α-methylionone Cinnamaldehyde, pentyl-C-butylphenylmethylpropionaldehyde, pentyl salicylate, pentylcinnamyl alcohol, anisole, benzoin, benzyl alcohol, benzyl benzoate, benzyl cinnamate, benzyl salicylate, bergamot oil, bitter orange oil, butylphenylmethylpropanol, cardamom oil, cedrol, cinnamaldehyde, cinnamyl alcohol, citronellol crotonate, lemon oil, coumarin, diethyl succinate, ethyl linalool, eugenol, evernia furfuracea extract, evernia prunastri extract, farnesol, guaiac oil, hexyl cinnamaldehyde, hexyl salicylate, hydroxycitronellol, lavender oil, lemon oil, linaylacetate, citrus oil, peppermint PCA, methyl heptenone, nutmeg oil, rosemary oil, sweet orange oil, terpineol, coumarin oil, triethyl citrate, vanillin, and combinations thereof.

[0222] Preferably, the cosmetic composition of the present invention comprises two or more of the above-described additives. In conjunction with the above preferred embodiments, it should be understood that if the cosmetic composition comprises two or more additives, then any combination of additives as defined above is also part of the present invention.

[0223] Based on the above preferred and particularly preferred embodiments, it should be understood that the cosmetic composition may further contain water.

[0224] In the presence of water in a cosmetic composition, it should be understood that it is preferably present in an amount greater than 5.0% by weight based on the total weight of the composition.

[0225] In one embodiment of the invention, the cosmetic composition may be provided in various forms, such as gels, creams, oils, emulsions, sticks, foams, pastes, or as a sprayable product. The cosmetic compositions of the invention can particularly be formulated as emulsions, such as water-in-oil (W / O), oil-in-water (O / W), water-in-oil-in-water (W / O / W), oil-in-water-in-oil (O / W / O), or single-phase oil, or oil-alcohol mixtures, or hydrophilic single-phase, or vesicular dispersions of ionic or nonionic amphiphilic lipids, or gels, or solid lipophilic sticks, solid hydrophilic sticks or powders, or aerosol formulations.

[0226] According to a preferred embodiment of the invention, the cosmetic composition has a UVA-PF of at least one-third of the SPF. Furthermore, it is preferred that the cosmetic composition exhibits a critical wavelength of at least 370 nm, thereby providing excellent protection across the entire harmful UV radiation range. More preferably, the cosmetic composition has a UVA1 / UV protection ratio equal to or better than 0.7 after 4 MED irradiation (according to the proposed FDA order (OTC000008) issued on September 24, 2021).

[0227] UVA-PF can be determined, either in vivo or in vitro, through simulation calculations using the BASF sunscreen simulator (https: / / sunscreensimulator.basf.com / ). The simulation calculations are based on B. Herzog et al., *Simulation of sunscreen performance*, *Pure Appl. Chem.* 2015;87(9-10):937-951, for determining protection against UVA radiation. The specific calculation method is described in detail in the section on pages 946-947 of the aforementioned reference. It simulates an in vivo UVA protection method based on persistent pigmentation (PPD). Preferably, UVA-PF is determined through simulation calculations.

[0228] More preferably, the cosmetic composition has an SPF (sun protection factor) value of at least 6 to 80.

[0229] According to one embodiment of the present invention, the cosmetic composition has an SPF greater than 15, greater than 30, or greater than 50.

[0230] SPF can be determined, either in vivo or in vitro, by means of simulation calculations using the BASF sunscreen simulator (https: / / sunscreensimulator.basf.com / ). Computer simulation of SPF calculations is based on the method described in B. Herzog et al., *Simulation of sunscreen performance*, Pure Appl. Chem. 2015; 87(9-10):937-951. Suitable in vitro methods can be performed as follows:

[0231] In vitro SPF determination was based on the assessment of the UV transmittance of a film of sunscreen sample spread on a rough substrate—SB6 PMMA plate (4-5 µm roughness, area 4.8 x 4.8 cm)—from Creil Helioscreen, France. The sunscreen formulation to be tested was prepared at 1.2 mg / cm². 2 Apply the appropriate amount to a PMMA plate. Perform three plates for each formulation and five measurements per plate. Manually distribute the formulation as evenly as possible on the plate. Before measurement, store the plates coated with the formulation at room temperature and in the dark for 30 minutes.

[0232] In vitro transmittance measurements were performed from 290–400 nm using a Labsphere UV Transmittance Analyzer UV 2000S in 1 nm increments. UV transmittance spectra were acquired, and in vitro SPF values ​​were calculated according to the following equation (average SPF of all 15 values ​​(from three plates, with 5 measurements per plate)).

[0233]

[0234] Where ser(λ) is the erythema spectrum, S(λ) is the spectral irradiance received from the UV source, and T(λ) is the transmittance measured in vitro.

[0235] In a preferred embodiment of the invention, the cosmetic composition provides photostability greater than 80%, preferably greater than 85%, and particularly greater than 90%. Preferably, the cosmetic composition provides photostability greater than 80%, preferably greater than 85%, and particularly greater than 90% after 10 MED, 20 MED, and / or 50 MED (for skin phototype II). The photostability of the composition is preferably determined by applying the respective composition to a rough quartz plate (2 µl / cm²). 2 The plate was then irradiated using an Atlas CPS device at a minimum erythema dose (MED), preferably 50 MED. The plate was then washed with tetrahydrofuran, and the wash solution was analyzed by HPLC to determine the recovery rate of the UV filter. An alternative preferred method for determining the photostability of the composition includes irradiating the PMMA plate covered with the sunscreen and evaluating the difference in absorbance spectra before and after irradiation.

[0236] A second aspect of the invention relates to a method for increasing the water resistance of a cosmetic composition comprising bis-ethylhexyloxyphenol methoxyphenyl triazine (bemotriazine), zinc oxide, and titanium dioxide, the method comprising the step of adding a water-soluble organic UV filter or a salt thereof to the cosmetic composition. Surprisingly, the addition of the water-soluble organic UV filter or a salt thereof increases the water resistance of the cosmetic composition comprising bemotriazine, zinc oxide, and titanium dioxide as a UV filter combination.

[0237] According to an embodiment of a second aspect of the invention, the cosmetic composition is free of UV filters derived from the group consisting of: 2-[4-(diethylamino)-2-hydroxybenzoyl]hexyl benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate), 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (benzotriazine), 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI homosalate), polysiloxane-15, and 2-hydroxy-4-methoxybenzophenone (INCI benzophenone-3).

[0238] The descriptions made regarding embodiments of the first aspect of the invention are also applicable to the second aspect of the invention in the same manner.

[0239] The invention is further illustrated by the following examples. Example

[0240] method

[0241] Water resistance contact angle method

[0242] Water resistance was determined using contact angle measurement and based on the method described in R. Hagens et al., “Contact angle measurement - a reliable supportive method for screening water-resistance of ultraviolet-protecting products in vivo”, International Journal of Cosmetic Science, 2007, 29, 283-291.

[0243] The method is carried out as follows: the sunscreen formulation is prepared at 1.2 mg / cm³. 2The appropriate dosage was applied to a rough substrate – SB6 PMMA plate, followed by a 30-minute drying time. To determine the contact angle between the water and the sunscreen-coated PMMA plate, an 8 µL drop of distilled water was placed on the sunscreen-coated PMMA plate using an automated application device (Easy Drop device from Krüss GmbH). During the first 5 seconds after droplet placement, the droplet profile was recorded at a rate of two images per second using an integrated charge-coupled device (CCD). Automated profile analysis was performed on the recorded images using analysis software (Software DAS), which calculated the contact angle between the virtual baseline (= PMMA surface) of all recorded images and the virtual tangent line passing through the contact point between the water surface and the plate (Tangent 1 process of the software used). For each formulation, five independent water droplets were measured on the same treated sunscreen-coated PMMA plate, and the resulting average contact angle for each plate was calculated. Three plates were measured for each formulation, and the average contact angle for the three plates was calculated.

[0244] If the contact angle is at least greater than 30°, the sunscreen composition is considered to be water-resistant.

[0245] Preparations

[0246] Prepare the following five formulations:

[0247]

[0248] Table 1: Formulations (IF.1, IF.2, IF.3) and comparative formulation CF.1 according to the present invention; BEMT = bis-ethylhexyloxyphenol methoxyphenyl triazine; PBSA = phenylbenzimidazole sulfonic acid; all values ​​are in wt.% and are based on the total weight of the formulation.

[0249] Z Cote HP1, from BASF SE.

[0250] Parsol TX, from DSM-Firmenich.

[0251] The formulation was prepared as follows: First, phase A was heated to 80°C with stirring in the absence of titanium dioxide (TiO2) and zinc oxide (ZnO). Then, TiO2 and ZnO were added to phase A at 80°C with stirring, and the mixture was homogenized using an Ultra Turrax apparatus. Phase B was heated to 80°C with stirring. Phase A was added to phase B with stirring, and then homogenized. Subsequently, component C was added, and the mixture was homogenized. Finally, the previously prepared and homogenized phase D was added to the mixture. The mixture was cooled to room temperature with stirring.

[0252] The water resistance of each of the four formulations was determined using the contact angle measurement method described above. The results are summarized in Table 2:

[0253]

[0254] As can be seen from Table 2, the contact angle of the comparative formulation CF.1 is below the water resistance threshold of greater than 30°, while the formulations IF.1, IF.2, and IF.3 of the present invention all have significantly larger contact angles greater than 40°. Therefore, the formulations IF.1-IF.3 of the present invention are all considered water-resistant, while the comparative formulations without PBSA do not meet the water resistance requirements.

[0255] Therefore, the addition of water-soluble organic UV filters such as phenylbenzimidazole sulfonic acid (ensolidazole) unexpectedly increases the water resistance of cosmetic compositions containing BEMT and at least one inorganic UV filter (particularly a mixture of zinc oxide and titanium dioxide).

Claims

1. A cosmetic composition comprising (i) Bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine), (ii) Water-soluble organic UV filter or its salt. (iii) at least one inorganic UV filter, The cosmetic composition does not contain UV filters from the group consisting of: 2-[4-(diethylamino)-2-hydroxybenzoyl]hexyl benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate), 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (octetrazol), 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI homosalate), polysiloxane-15, and 2-hydroxy-4-methoxybenzophenone (INCI benzophenone-3).

2. The cosmetic composition according to claim 1, wherein, This cosmetic composition does not contain 2-ethylhexyl-2-cyano-3,3-diphenylprop-2-enoate (INCI octyl cyanobenzyl acrylate).

3. The cosmetic composition according to any one of claims 1 or 2, wherein, The at least one inorganic UV filter (III) is selected from zinc oxide, titanium oxide and mixtures thereof.

4. The cosmetic composition according to any one of the preceding claims, wherein, This cosmetic composition does not contain (2E)-3-(4-methoxyphenyl)prop-2-enoic acid (RS)-2-ethylhexyl ester (octyl methoxycinnamate).

5. The cosmetic composition according to any one of the preceding claims, wherein, This cosmetic composition does not contain any additional organic UV filters.

6. The cosmetic composition according to any one of the preceding claims, wherein, The water-soluble organic UV filter (ii) is selected from the group consisting of: phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole), [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1]heptyl]methyl]phenyl]methylene]-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptyl]methanesulfonic acid (Ekason), disodium phenyl dibenzimidazole tetrasulfonate (bis(disulfonazole) disodium), or salts thereof, and mixtures thereof.

7. The cosmetic composition according to any one of the preceding claims, wherein, The water-soluble organic UV filter (ii) is phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole), or its salt, or mixtures thereof.

8. The cosmetic composition according to any one of the preceding claims, wherein, The cosmetic composition further contains an organic neutralizer.

9. The cosmetic composition according to any one of the preceding claims, wherein, The organic neutralizer is selected from tromethorphan, triethanolamine, tetrahydroxypropyl ethylenediamine, arginine, and aminomethylpropanol.

10. The cosmetic composition according to any one of the preceding claims, wherein, The cosmetic composition contains a copolymer of hydroxyethyl acrylate and sodium acryloyl dimethyl taurate.

11. The cosmetic composition according to any one of claims 1 to 10, wherein, The cosmetic composition contains (i) 0.5 to 6.0 wt.% of bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyltriazine); (ii) 1.0 to 4.0 wt.% of phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole); (iii) 0.5 to 25.0 wt.% of zinc oxide; (iv) 0.5 to 25.0 wt.% titanium oxide; Each is based on the total weight of the cosmetic composition.

12. The cosmetic composition according to any one of claims 1 to 10, wherein, The cosmetic composition contains (i) 1.5 to 5.0 wt.% of bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine); (ii) 1.5 to 3.0 wt.% of phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole); (iii) 2.5 to 10.0 wt.% of zinc oxide; (iv) 2.5 to 10.0 wt.% of titanium oxide; (v) 0.5 to 4.0 wt.% of a neutralizing agent selected from tromethamine, triethanolamine, tetrahydroxypropylethylenediamine, arginine, and aminomethylpropanol. Each is based on the total weight of the cosmetic composition.

13. The cosmetic composition according to any one of claims 1 to 10, wherein, The cosmetic composition contains (i) 2.0 to 5.0 wt.% of bemotriazine (INCI: bis-ethylhexyloxyphenol methoxyphenyltriazine); (ii) 2.0 to 2.5 wt.% of phenyl-3H-benzimidazole-5-sulfonic acid (ensolazole); (iii) 3.5 to 6.5 wt.% zinc oxide; (iv) 3.5 to 6.5 wt.% titanium oxide; (v) 0.7 to 2.5 wt.% of a neutralizing agent selected from tromethamine, triethanolamine, tetrahydroxypropylethylenediamine, arginine, and aminomethylpropanol. Each is based on the total weight of the cosmetic composition.

14. The cosmetic composition according to any one of the preceding claims, wherein, According to the contact angle measurement method, the cosmetic composition is considered to be water-resistant if it has a contact angle greater than 30°.

15. The cosmetic composition according to any one of the preceding claims, wherein, The cosmetic composition has an SPF greater than 15, 30, or 50, and / or has a contact angle greater than 30°, and / or has photostability greater than 80%.

16. A method for increasing the water resistance of a cosmetic composition comprising bis-ethylhexyloxyphenol methoxyphenyl triazine (bemotriazine), zinc oxide, and titanium dioxide, the method comprising the step of adding a water-soluble organic UV filter or a salt thereof to the cosmetic composition.

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