Cosmetic composition understanding a photoprotective system and use of a photoprotective system

Abstract

Photoprotective system consisting of 4 sunscreens. The present invention relates to a cosmetic or pharmaceutical composition containing at least one cosmetically or pharmaceutically acceptable excipient and a photoprotective system consisting of: (a) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine, (b) 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, (c) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate, and (d) a sunscreen selected from the group consisting of ethyl hexyl triazone, diethyl hexyl butamido triazone and 2-ethyl hexyl salicylate, wherein the photoprotective system represents between 4% and 20% by weight of the composition relative to the total weight of the composition.

Description

Cosmetic composition comprising a photoprotective system and use of a photoprotective system.

[0001] The present invention relates to a cosmetic or pharmaceutical composition containing at least one cosmetically or pharmaceutically acceptable excipient and a photoprotective system consisting of 4 lipophilic or dispersed filters, in particular hydrodispersed filters, wherein the photoprotective system represents between 4% and 20% by weight of the composition in relation to the total weight of the composition.

[0002] The potentially harmful effects of ultraviolet rays on the skin are well known, and a range of sun protection products, generally referred to as sunscreens, are marketed. However, many of the compositions offered on the market are unsatisfactory, either from the user's point of view, in terms of tolerance and toxicity, or due to their environmental impact. In reality, sunscreens are essentially composed of organic chemical filters, many of which are not exactly harmless, especially when several of them are combined, which creates a risk of harmful interactions between the different compounds. For this reason, it is advantageous to minimize, on the one hand, the number of ultraviolet filters that make up a photoprotective composition and, on the other hand, the concentration of said filters in the composition in order to improve the results in terms of tolerance and toxicity for the user.This is also beneficial for the environment, since the UV filters present in sunscreen are often released into the oceans.

[0003] It should be noted that most commercial sunscreens contain a substantial number of distinct UV filters, also present in high concentrations.

[0004] This is explained by the need for photoprotective products to have the broadest possible UV absorption spectrum in order to efficiently protect the user from the rays. Petition 870260060871, dated 06 / 22 / 2026, page 20 / 69 2 / 24 ultraviolet.

[0005] Furthermore, some sunscreens are not sufficiently photostable, meaning they tend to degrade after prolonged exposure to ultraviolet rays and, from then on, cease to adequately protect the user. In particular, it is known that the butyl methoxydibenzoylmethane (BMDBM) molecule, a UVA filter widely used in commercial sunscreens, is cleaved, forming different chemical components that lack absorption capacity when exposed to UV radiation, unless associated with other compounds that improve its photostability.

[0006] The intensive research conducted by the Applicant, which places the protection of the user and the environment at the center of its attention for the development of new solar products, has allowed it to establish a photoprotective system that, although composed of only 4 sunscreens present in controlled quantities, provides complete and effective protection against UV rays and is highly photostable.

[0007] Furthermore, unlike most sunscreens currently available on the market, the composition developed by the Applicant is distinguished by the excellent results obtained in in vitro eye tolerance tests. This is a considerable advantage, as sunscreens often come into contact with the user's eyes after sweating or after bathing.

[0008] The present invention relates, firstly, to a cosmetic or pharmaceutical composition containing at least one cosmetically or pharmaceutically acceptable excipient and to a photoprotective system consisting of:

[0009] (a) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine,

[0010] (b) 2,4-bis[4-(2-ethyl hexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)- 1,3,5-triazine, Petition 870260060871, dated 06 / 22 / 2026, page 21 / 69 3 / 24

[0011] (c) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate, and

[0012] (d) a sunscreen selected from the group consisting of ethyl hexyl triazone, diethyl hexyl butamido triazone and 2-ethyl hexyl salicylate,

[0013] wherein the photoprotective system represents between 4% and 20% by weight of the composition in relation to the total weight of the composition,

[0014] and said composition does not contain any other sunscreen besides those that make up said photoprotective system.

[0015] For the purposes of this invention, a “photoprotective system” means a combination of compounds that, after application to a given surface (skin, hair, etc.), prevents or at least limits contact of said radiation with said surface through mechanisms of absorption and / or reflection and / or diffusion of UVA and / or UVB radiation.

[0016] The term ultraviolet radiation or UV radiation, commonly abbreviated to UV, refers to both solar ultraviolet radiation and artificial ultraviolet radiation generated by tanning lamps, for example.

[0017] The term UVA radiation or simply UVA refers to ultraviolet rays with a wavelength λ between 320 and 400 nm.

[0018] The term UVB radiation or simply UVB refers to ultraviolet rays with a wavelength λ between 290 and 320 nm.

[0019] The term sunscreen or UV filter refers to a substance capable of filtering UV rays to protect a surface, usually the skin or hair, against the harmful effects of such radiation.

[0020] A sunscreen is classified as a UVA or UVB filter, depending on whether the type of ray to be filtered is primarily a UVA ray or a UVB ray.

[0021] A broad-spectrum or broad-range sunscreen filters Petition 870260060871, dated 06 / 22 / 2026, page 22 / 69 4 / 24 simultaneously blocks UVA and UVB rays.

[0022] Depending on the radiation filtration mechanism, that is, according to the radiation that is absorbed and / or reflected, or even diffused by the sunscreen, these are strictly classified as:

[0023] - filters stricto sensu, which mostly absorb radiation, and

[0024] - the protectors, which absorb and reflect radiation.

[0025] However, in the description that follows, the term sunscreen, sometimes abbreviated to sunscreen, will be used interchangeably, whether in the case of a sunscreen or a sunblock.

[0026] A sunscreen can be “liposoluble” or “water-soluble,” depending on whether it dissolves more easily in lipids or water, or it can be insoluble. However, an insoluble sunscreen can be incorporated into a sun protection composition, typically in dispersed form, especially water-dispersed form, when it is dispersed in an aqueous phase.

[0027] The photoprotective system comprising a composition according to the invention contains only 4 sunscreens of the fat-soluble or non-soluble type and is therefore free of water-soluble filters.

[0028] The absence of water-soluble filters in a composition according to the invention is particularly advantageous, since water-soluble filters are generally more easily assimilated by marine organisms than fat-soluble or non-soluble filters. As a result, the Applicant's choice to use only fat-soluble or dispersed filters, in particular water-dispersed filters, minimizes the impact of the composition according to the invention on the marine environment.

[0029] In one particular embodiment, the photoprotective system represents between 6% and 19%, mainly between 7% and 18%, in particular between 8% and 17% by weight of the composition in relation to the weight Petition 870260060871, dated 06 / 22 / 2026, page 23 / 69 5 / 24 of the total composition.

[0030] In another particular type, which provides especially high sun protection, the photoprotective system represents between 8% and 20%, especially between 10% and 20%, particularly between 12% and 17%, advantageously between 14% and 17%, for example between 15% and 16% by weight of the composition in relation to the total weight of the composition.

[0031] The photoprotective system comprising a composition according to the invention consists of the filters specified below.

[0032] (a) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine, (no. CAS: 55514-22-2), also known as phenylene bis-diphenyltriazine.

[0033] This is essentially a UVA filter, with a maximum absorption wavelength λmáχ equal to 355 nm of the non-soluble type. In particular, it is a water-dispersible filter.

[0034] Phenylene bis-diphenyltriazine is normally presented in the form of an aqueous dispersion containing between 20% and 50%, in particular between 40% and 50% by weight of active substance in relation to the total weight of the dispersion.

[0035] As an advantageous aspect, the method of preparing the aqueous dispersion consists of grinding the insoluble organic filter into particles using a grinding apparatus and in the presence of a grinding aid.

[0036] Classically, wet grinding methods (wet grinding, wet mixing) are used, and the grinding aid allows for a more adequate dispersion of the particles. These techniques are well known to the person skilled in the art.

[0037] The grinding apparatus may be, for example, a microbead mill, a vibratory mill or a ball mill.

[0038] Depending on the grinding method, the grinding aid is chosen from the group formed by anionic, non-ionic or amphoteric surfactants, emulsifiers and dispersants such as PPG-1 Petition 870260060871, dated 06 / 22 / 2026, page 24 / 69 6 / 24 PEG-9 Lauryl Glycol Ether (Eumulgin® L, marketed by BASF).

[0039] In a particular embodiment, phenylene bis-diphenyltriazine represents between 1% and 5%, especially between 2% and 5%, particularly between 2% and 4%, typically between 3% and 4% by weight of the composition relative to the total weight of the composition.

[0040] It should be noted that these mass percentages, as well as those indicated later in the description, are expressed as a mass percentage of the active substance relative to the total mass of the composition.

[0041] In a particular embodiment, the D50 size of the phenylene bis-diphenyltriazine particles is between 100 and 1000 nm, more particularly between 100 and 500 nm, even more particularly between 120 and 400 nm, especially between 120 and 250 nm, particularly between 120 and 200 nm, typically between 150 and 200 nm.

[0042] The term “size D50” or “median” designates the size for which the cumulative function F(D) corresponds to 50%, where F(D) is defined by the following relation: [Matt.1] Di F(Dd = I f(D)dD 0

[0043] where:

[0044] f(D) is the particle size distribution in number, and Di is a size class.

[0045] The value of D50 will be determined according to the method described in the examples in this description.

[0046] (b) 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)1,3,5-triazine (CAS No.: 187393-00-6), also known as bis-ethylhexyloxyphenol methoxyphenyl triazine or BEMT, marketed by BASF under the name Tinosorb S®.

[0047] This is a broad-spectrum, lipophilic filter that has two absorption peaks at 310 and 340 nm. Petition 870260060871, dated 06 / 22 / 2026, page 25 / 69 7 / 24

[0048] In a particular embodiment, BEMT represents between 1% and 4%, in particular between 2% and 3% by weight of the composition in relation to the total weight of the composition.

[0049] (c) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (no. CAS: 302776-68-7), also known as diethylaminohydroxybenzoyl hexyl benzoate or DHHB, marketed by BASF under the name Uvinul A Plus®.

[0050] This is a lipophilic UVA filter, which has a maximum absorption wavelength Àmax equal to 354 nm.

[0051] In a particular embodiment, DHHB represents between 1% and 10%, for example between 3% and 10%, in particular between 4% and 9%, typically between 5% and 8%, especially between 6% and 7% or advantageously between 5% and 6% by weight of the composition in relation to the total weight of the composition.

[0052] (d) a sunscreen selected from the group consisting of ethyl hexyl triazone, diethyl hexyl butamido triazone and 2-ethyl hexyl salicylate.

[0053] These three filters are lipophilic UVB filters.

[0054] Ethyl hexyl triazone or EHT (CAS No.: 88122-99-00), marketed by BASF under the name Uvinul T 150®, has a maximum absorption wavelength Àmax equal to 314 nm.

[0055] Diethylhexyl butamido triazone (CAS No.: 154702-15-5), marketed by 3V Sigma under the name Uvasorb HEB®, has a maximum absorption wavelength Àmax equal to 310 nm.

[0056] 2-Ethylhexyl salicylate (CAS No.: 118-60-5), also known as octyl salicylate or ethyl hexyl salicylate (EHS), is marketed by Aako BV under the name Aako Sun EHS®.

[0057] In a particular embodiment, the sunscreen (d) represents between 1% and 5%, especially between 2% and 4%, especially between 3% and 4% by weight of the composition in relation to the total weight of the composition. Petition 870260060871, dated 06 / 22 / 2026, page 26 / 69 8 / 24

[0058] Advantageously, the sunscreen (d) corresponds to ethyl hexyl triazone or diethyl hexyl butamido triazone, preferably ethyl hexyl triazone.

[0059] In a particular embodiment, the sunscreen (d) corresponds to ethyl hexyl triazone and represents between 1% and 5%, especially between 2% and 4%, especially between 3% and 4% by weight of the composition in relation to the total weight of the composition.

[0060] In an advantageous embodiment, the cosmetic or pharmaceutical composition according to the invention contains at least one cosmetically or pharmaceutically acceptable excipient and a photoprotective system consisting of:

[0061] (a) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine,

[0062] (b) 2,4-bis[4-(2-ethyl hexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)1,3,5-triazine,

[0063] (c) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate, and

[0064] (d) ethyl hexyl triazone,

[0065] wherein the photoprotective system represents between 4% and 20%, for example between 6% and 19%, especially between 7% and 18%, in particular between 8% and 17%, advantageously between 14% and 17%, typically between 15% and 16% by weight of the composition in relation to the total weight of the composition,

[0066] and contains no other sunscreen besides those that constitute the said photoprotective system.

[0067] In this advantageous embodiment, phenylene bis-diphenyltriazine advantageously represents between 1% and 5%, especially between 2% and 5%, particularly between 2% and 4%, typically between 3% and 4% by weight of the composition relative to the total weight of the composition, BEMT advantageously represents between 1% and 4%, particularly between 2% and 3% by weight of the composition relative to the total weight of the composition, DHHB advantageously represents between 1% and 10%, especially between Petition 870260060871, dated 06 / 22 / 2026, page 27 / 69 9 / 24 3% and 10%, in particular between 4% and 9%, typically between 5% and 8%, for example between 6% and 7% or more advantageously between 5% and 6% by weight of the composition relative to the total weight of the composition, and ethyl hexyl triazone advantageously represents between 1% and 5%, especially between 2% and 4%, in particular between 3% and 4% by weight of the composition relative to the total weight of the composition.

[0068] In particular, the photoprotective system comprising a composition according to the invention is photostable.

[0069] The term photostable in the context of the present invention means that, after an irradiation of 5 DEM and preferably 10 DEM, at least 80%, preferably at least 85% and advantageously at least 90% of the total FPS (290 to 400 nm) are preserved.

[0070] The term FPS designates the sun protection factor, commonly referred to by its English acronym SPF (sun protection factor).

[0071] The FPS value will be determined according to the method described in the examples in this description.

[0072] In a particular embodiment, the FPS of a composition according to the invention is greater than or equal to 50 and, advantageously, greater than or equal to 60.

[0073] In another particular modality, the SPF / UVA ratio is less than or equal to 3, according to the regulations in force. The denominator of said quotient represents the UVA part (320 to 400 nm) of the total SPF, and can be calculated according to the method recommended by COLIPA (Fédération Européenne des Industries de la Parfumerie - European Federation of Perfume Industries), in its standards published in March 2011.

[0074] The photoprotective system that ensures the characteristics specified above in relation to SPF and SPF / UVA ratio then typically represents between 8% and 20%, especially between 10% and 20%, particularly between 12% and 17%, advantageously between 14% and 17%, by Petition 870260060871, dated 06 / 22 / 2026, page 28 / 69 10 / 24 example between 15% and 16% by weight of the composition in relation to the total weight of the composition.

[0075] In addition to the photoprotective system, the composition according to the invention contains at least one cosmetically or pharmaceutically acceptable excipient.

[0076] In the present invention, the expression "cosmetically or pharmaceutically acceptable" means something that is useful for the preparation of a cosmetic or pharmaceutical composition, generally safe, non-toxic and not undesirable from a biological or other standpoint, and that is acceptable for human cosmetic or pharmaceutical use.

[0077] By “pharmaceutically or cosmetically acceptable excipient” is meant any cosmetically or pharmaceutically acceptable adjuvant that enables the manufacture, preservation or administration of the composition.

[0078] The compositions according to the invention may therefore contain classic pharmaceutical or cosmetic adjuvants, in particular chosen from among fatty substances, organic solvents, thickeners, opacifiers, stabilizers, emollients, antifoaming agents, perfumes, preservatives, polymers, fillers, sequestrants, bactericides, odor absorbers, alkalizing or acidifying agents, surfactants, free radical scavengers, vitamins E and C, alpha-hydroxy acids, emulsifiers, active agents (in particular softeners, moisturizing agents, antioxidants) or any other ingredient commonly used in the pharmaceutical or cosmetic field, in particular for the manufacture of sun protection compositions.

[0079] Fatty bodies can be composed of an oil or a wax or mixtures of these elements, in addition to containing fatty acids, fatty alcohols and fatty acid esters.

[0080] The composition may additionally contain a miscible polyol. Petition 870260060871, dated 06 / 22 / 2026, page 29 / 69 11 / 24 in water at room temperature (about 25°C), especially chosen from polyols having particularly 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and preferably 2 to 6 carbon atoms, such as glycerin; glycol derivatives such as propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol; glycol ethers such as C1-C4 alkyl ethers of mono, di or tripropylene glycol, C1-C4 alkyl ethers of mono, di or triethylene glycol and mixtures thereof.

[0081] The composition may also contain thickening agents or rheology-modifying agents such as, for example, hydrophobically modified ethoxylated non-ionic urethanes, polycarboxylic acids, thickeners such as acrylate / steareth-20 methacrylate copolymers, carbomers, cross-linked acrylate copolymers and mixtures of these substances.

[0082] The composition may also contain alkalizing or acidifying agents and, more particularly, acids and bases that allow adjusting the pH range of said composition. The bases may be mineral (sodium hydroxide, potassium carbonate, ammonium hydroxide, etc.) or organic such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine and mixtures thereof.

[0083] The composition may also contain emulsifiers. Examples of emulsifiers include, but are not limited to, anionic, cationic and non-ionic emulsifiers such as sodium lauryl sulfate, sodium dioctyl sulfosuccinate, sodium stearate, sorbitan ester; ethoxylated fatty acids; ethoxylated fatty alcohols such as trideceth-9 and PEG-5 ethylhexanoate; any other emulsifier known to those skilled in the art; and mixtures thereof.

[0084] The compositions according to the invention may also contain other active agents chosen particularly from among agents Petition 870260060871, dated 06 / 22 / 2026, p. 30 / 69 12 / 24 moisturizers, exfoliating agents, barrier function enhancers, depigmenting agents, antioxidant agents, dermocontraction agents, antiglycation agents, agents that stimulate the synthesis of dermal and / or epidermal macromolecules and / or inhibit their degradation, agents that stimulate the proliferation of fibroblasts or keratinocytes and / or the differentiation of keratinocytes, NO synthase inhibitors, agents that enhance sebaceous gland activity, firming agents, lipo-restructuring agents, slimming agents, agents that promote cutaneous microcirculation, calming and / or irritating agents, oil regulators or antiseborrheic agents, astringent agents, healing agents, anti-inflammatory agents, anti-acne agents, and mixtures thereof.

[0085] In a particular embodiment, the composition according to the invention contains dibutyl adipate.

[0086] In another particular embodiment, the composition according to the invention is free of ethanol and isopropanol.

[0087] In a particular embodiment, the composition according to the invention is silicone-free.

[0088] In an advantageous embodiment, the composition according to the invention contains the following three emollients: C12-C15 alkyl benzoate, dicaprylyl carbonate and caprylic / capric triglycerides.

[0089] In this advantageous embodiment, the composition according to the invention may also contain one or more components selected from the group consisting of stearyl alcohol, glyceryl monostearate, glyceryl behenate, PEG-100 stearate, VP / eicosene copolymer, a polyacrylate, potassium cetyl phosphate, glyceryl stearate, lauryl glucoside, polyglyceryl-2 dipolyhydroxystearate and isopropyl adipate.

[0090] The compositions according to the invention may be Petition 870260060871, dated 06 / 22 / 2026, page 31 / 69 13 / 24 presented in any form suitable for topical application, especially to the skin and / or hair.

[0091] In particular, they may be in the form of emulsions obtained by dispersing a fatty phase in an aqueous phase, for example, an oil-in-water or water-in-oil or multiple emulsion, or in the form of a gel or an anhydrous liquid, paste or solid product, or in the form of a dispersion in the presence of spherules. The compositions according to the invention may also be less fluid and be in the form of a white or colored cream, an ointment, a milk, a lotion, a serum, a paste, a mask, a powder, a solid stick, or optionally an aerosol, a foam or a spray. These compositions may also be water-resistant.

[0092] In a particular embodiment, the composition according to the invention is in the form of an emulsion, for example, an oil-in-water or water-in-oil emulsion, preferably an oil-in-water emulsion.

[0093] The composition according to the invention is, more specifically, a sun protection composition, often called a sun composition, intended for protecting the skin (face and / or body) and / or hair against ultraviolet rays.

[0094] The present invention also relates to a method of protecting the skin (face and / or body) and / or hair against ultraviolet rays, comprising applying to the skin (face and / or body) and / or hair a composition described above.

[0095] The present invention also relates to a composition as described above for use as protection for the skin (face and / or body) and / or hair against ultraviolet rays.

[0096] The present invention also relates to the use of a composition as described above for skin protection. Petition 870260060871, dated 06 / 22 / 2026, page 32 / 69 14 / 24 (face and / or body) and / or hair against ultraviolet rays. EXAMPLES

[0097] The following abbreviations have been adopted: Table 1 MED: Minimum erythema dose SPF: Sun protection factor MTT: 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide PEG: Polyethylene glycol PMMA: Polymethyl methacrylate UV: Ultraviolet radiation VP: N-vinylpyrrilidone I. Compositions

[0098] In the formulas below, 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)bis[1,2,4]triazine is in the form of an aqueous dispersion containing 45% (w / w) by weight of active substance and is characterized by a D50 between 150 and 250 nm. 1.1. Formula 1 Table 2 Ingredients % (w / w) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine 3-4 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2-3 Diethylaminohydroxybenzoyl hexyl benzoate 6-7 Ethyl hexyl Triazone 3-4 Glycerin 5.0 Demineralized water qs to 100 Xanthan gum 0.2 C12-C15 alkyl benzoate 12.0 Dicaprylyl carbonate 9.0 Caprylic / capric triglycerides 9.0 Petition 870260060871, dated 06 / 22 / 2026, page 33 / 69 15 / 24 Preservatives Qs Stearyl alcohol 1.0 Glyceryl monostearate 0.5 Glyceryl behenate 0.4 PEG-100 stearate 0.5 VP / eicosene copolymer 1.0 Polyacrylate 0.2 Potassium cetyl phosphate 2.0 I.2. Formula 2 Table 3 Ingredients % (w / w) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine 3-4 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2-3 Diethylaminohydroxybenzoyl hexyl benzoate 6-7 Ethyl hexyl Triazone 3-4 Glycerin 5.0 Demineralized water qs to 100 Xanthan gum 0.2 C12-C15 alkyl benzoate 12.0 Dibutyl adipate 9.0 Caprylic / capric triglycerides 9.0 Preservatives qs Stearyl alcohol 1.0 Glyceryl monostearate 0.5 Glyceryl behenate 0.4 PEG-100 stearate 0.5 VP / eicosene copolymer 1.0 Polyacrylate 0.2% Cetylphosphate potassium 2.0% 1.3. Formula 3 Petition 870260060871, dated 06 / 22 / 2026, page 34 / 69 16 / 24 Table 4 Ingredients % (w / w) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine 3-4 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2-3 Diethylaminohydroxybenzoyl hexyl benzoate 6-7 Diethylhexyl butamido triazone 3-4 Glycerin 5.0 Demineralized water qs to 100 Xanthan gum 0.2 C12-C15 alkyl benzoate 12.0 Dibutyl adipate 9.0 Caprylic / capric triglycerides 9.0 Preservatives qs Stearyl alcohol 1.0 Glyceryl monostearate 0.5 Glyceryl behenate 0.4 PEG-100 stearate 0.5 VP / eicosene copolymer 1.0 Polyacrylate 0.2 Cetyl phosphate potassium 2.0 1.4. Formula 4 Table 5 Ingredients % (w / w) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine 3-4 Bis-Ethyl hexyloxyphenol Methoxyphenyl Triazine 2-3 Diethylamino hydroxybenzoyl hexyl benzoate 6-7 Ethyl hexyl Triazone 3-4 Glycerin 6.0 Petition 870260060871, dated 06 / 22 / 2026, pp. 35 / 69 17 / 24 Demineralized water qs to 100 ml Xanthan gum 0.2g C12-C15 alkyl benzoate 12.0g Dicaprylyl carbonate 9.0g Caprylic / capric triglycerides 9.0g Preservatives qs Glyceryl stearate 0.5g Glyceryl behenate 0.4g Lauryl glucoside 1.5g Polyacrylate 0.2g Polyglyceryl-2 dipolyhydroxystearate 1.5g 1.4. Formula 5 Table 6 Ingredients % (w / w) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine 4-5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2-3 Diethylaminohydroxybenzoyl hexyl benzoate 6-7 Diethylhexyl butamido triazone 3-4 Glycerin 3.0 Demineralized water qs to 100 Xanthan gum 0.2 C12-C15 alkyl benzoate 18.0 Isopropyl adipate 6.0 Dicaprylyl carbonate 6.0 Preservatives qs Stearyl alcohol 1.0 Polyacrylate 0.2 Potassium cetyl phosphate 2.0 Petition 870260060871, dated 06 / 22 / 2026, pp. 36 / 69 18 / 24 1.5. Formula 6 Table 7 Ingredients % (w / w) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine 3-3,5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2,5-3 Diethylaminohydroxybenzoyl hexyl benzoate 5-6 Ethyl hexyl triazone 3,5-4 Glycerin 5.0 Demineralized water qs to 100 Xanthan gum 0.2 C12-C15 alkyl benzoate 12.0 Dicaprylyl carbonate 9.0 Caprylic / capric triglycerides 9.0 Preservatives qs Stearyl alcohol 1.0 Glyceryl monostearate 0.5 Glyceryl behenate 0.4 PEG-100 stearate 0.5 VP / eicosene copolymer 1.0 Polyacrylate 0.2 Cetyl phosphate potassium 2.0 II. Determination of the particle size of 5,6,5',6'-tetraphenyl-3,3'(1,4-phenylene)-bis[1,2,41-triazine]

[0099] The D50 of phenylene bis-diphenyltriazine particles is determined using a Mastersizer 3000 liquid-based laser diffraction granulometer.

[0100] A sample of aqueous dispersion of phenylene bisdiphenyltriazine is placed under magnetic stirring (2500 rpm) for 2 minutes. Petition 870260060871, dated 06 / 22 / 2026, pp. 37 / 69 19 / 24

[0101] One ml of the sample is collected and placed in a vial which is then filled to 100 ml with ultrapure water.

[0102] The solution thus obtained is subjected to magnetic stirring (2500 rpm) for 30 seconds. The solution for examination is collected and introduced into the measuring container until the 15% obscuration limit is reached.

[0103] Three independent trials are performed and 3 independent measurements (red laser: background noise measurement, 10 s, sample measurement, 10 s; blue laser: background noise measurement, 10 s, sample measurement, 10 s) are performed per trial.

[0104] The results are obtained in volume and then converted into numbers by a computer program. III. Evaluation of sun protection

[0105] The evaluation of the parameters that allow quantifying the photoprotection ensured by a composition according to the invention is carried out in accordance with the methods recommended by COLIPA (Fédération Européenne des Industries de la Parfumerie, European Federation of Perfume Industries), in its standards published in March 2011. III.1. Material The UV spectrometer

[0106] The spectrophotometer measures the spectral transmittance through a plate with and without a layer of the sunscreen composition on its surface.

[0107] The spectrophotometer must allow measurements between 290 nm and 400 nm. To reduce variability between measurement readings and compensate for the lack of uniformity in the product layer, it is recommended that the reading range of the areas be at least 0.5 cm2.

[0108] The spectrophotometer used for these measurements is the Petition 870260060871, dated 06 / 22 / 2026, pp. 38 / 69 20 / 24 Labsphere® UV-1000S or 2000S. The plate

[0109] The plate is the material onto which the sunscreen composition is applied. This material must be UV transparent, non-fluorescent, photostable, and inert to the compounds of the tested compositions. For this protocol, PMMA plates are ideal. UV Source

[0110] The UV source is a solar simulator with a xenon arc lamp that diffuses a Visible + UVA + UVB spectrum. The UV source used for this study is the Suntest CPS+ (Atlas). 111.2. Methods for determining SPF and photostability Measurements of transmission through an untreated plate.

[0111] First, it is necessary to determine the transmission of UV radiation is applied through the control plate. This plate is prepared by spreading a few microliters of glycerin over its surface to completely cover it. - Sample application

[0112] The test sample is applied to the PMMA plate at a dose of 1.3 mg / cm2 (effective amount remaining on the plate). To ensure dose accuracy and reproducibility of results, the application area is larger than 10 cm2.

[0113] The test sample is applied in the form of a large number of small drops of the same volume, distributed across the entire surface of the plate.

[0114] To ensure that the amount of product is correct, a method for validating the amount of product applied must be established (e.g., weighing the plate before and after product application).

[0115] After applying the defined amount of sample, the sample should be spread across the entire plate as quickly as possible. Petition 870260060871, dated 06 / 22 / 2026, pp. 39 / 69 21 / 24 possible (less than 30 seconds). The sample is then placed in the dark for 15 minutes at room temperature to encourage the formation of a homogeneous film. - Measurement of transmission through a sample-treated plate

[0116] The sample-treated plate is analyzed in the spectrophotometer, and the average value of UV ray transmission through the sample is determined for each wavelength from 290 nm to 400 nm (using the data from the monochromatic absorbances measured in the different regions of the plate). - Number of measurements

[0117] It is necessary to prepare at least three PMAAA plates for each sample. Each plate must be measured in at least nine different fields, unless almost the entire surface of the plate is measured by spectrophotometry. - Calculation of SPF in vitro (Sun Protection Factor, commonly referred to by its English acronym SPF)

[0118] The calculation is performed based on absorbance data A(λ) before and after radiation at doses of 5 and 10 DEM, according to the following formula: [Matt. 2] £λ_“4θο nmEÇAysÇX). dA FPS in vitro = , ---—---------------P!400 nm10-^)^J!=290 nmv'

[0119]

[0120]

[0121]

[0122]

[0123] where: E(λ) corresponds to the erythrocyte efficacy spectrum, S(λ) corresponds to the spectral solar irradiance, A(λ) corresponds to the absorbance of the sample, dλ is the wavelength variation (1 nm). - Photostability calculation [Matt. 3] Petition 870260060871, dated 06 / 22 / 2026, pp. 40 / 69 22 / 24 FPS after irradiation Total UV Photostability = -----------;------;-----x 100 FPS before irradiation

[0124] The compositions according to the invention can be classified according to the categories indicated below based on their photostability. Table 8 Category % of total FPS retained after radiation 5 MED A > 90% B 85% - < 90% C 80% - < 85% D < 80% 111.3. Results

[0125] The results below were obtained for formulas 1 and 2: Table 9 Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 SPF in vitro > 70 > 80 > 80 > 60 > 80 SPF / UVA ratio < 3 < 3 < 3 < 3 < 3 Total photostability after irradiation at 5 MED Category A Category A Category A Category A Category A IV. Assessment of ocular tolerance IV.1. In vitro model in reconstructed human corneal epithelium (CHR)

[0126] This test is an alternative method to experiments performed on animals for evaluating the ocular irritation potential of the reconstructed human corneal epithelium.

[0127] The principle is based on determining the mean cytotoxicity index in 24 hours by applying the products to reconstructed human corneal epithelia.

[0128] Cell viability is studied by MTT reduction Petition 870260060871, dated 06 / 22 / 2026, pp. 41 / 69 23 / 24 incorporated into living cells in tetrazolium salt, which forms violet crystals, measurable by colorimetry.

[0129] The calculated parameter is MCtah (“median 24-hour cytotoxicity index”), that is, the average mortality caused per hour. This parameter allows us to establish whether or not the product is irritating.

[0130] The method description is found in the article Doucet et al., Toxicology in vitro, 2006, 20, 499-512.

[0131] The compositions according to the invention can be classified according to the rating system indicated below, based on their MCI24h. Table 10 MCl24h Category 4: Non-irritating < 4 3: Slightly irritating 4 - < 7 2: Moderately irritating 7 - < 17 1: Very irritating > 17 IV.2. Method of “Neutral Red Incorporation” (IVN)

[0132] This test is an alternative method to experiments performed with animals for evaluating the potential for ocular irritation.

[0133] The principle is based on the evaluation of cytotoxicity through the determination of the concentration causing 50% mortality (LC50), using the technique of incorporating neutral red into rabbit corneal fibroblasts of the SIRC cell line after a contact time of 30 or 60 seconds.

[0134] The method is described in the decree of 27 December 1999 published in the Official Journal of France on 30 December 1999.

[0135] After incubation of the neutral red staining solution with the culture cells on a plate, each dilution of the product is contacted with the cells for 60 seconds or 30 seconds before being rinsed away. Cell viability is assessed by Petition 870260060871, dated 06 / 22 / 2026, pp. 42 / 69 24 / 24 spectrophotometry after addition of the developing solution.

[0136] The cytotoxicity of the product is provided by a scale specified in the Official Journal of France of December 30, 1999, which includes 4 categories: Table 11 Cytotoxicity Category 4 Negligible 3 Very mild 2 Moderate 1 Severe IV.3. Results

[0137] The results below were obtained for formulas 1 and 2: Table 12 Formula 1 Formula 2 HCE Model Note 3 Note 4 NRR Method Note 4 Note 4

[0138] The results are good for in vitro ocular tolerance tests for both formulas tested.

Claims

1. A cosmetic composition characterized in that it comprises at least one cosmetically acceptable excipient and a photoprotective system consisting of: (a) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine, (b) 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)1,3,5-triazine, (c) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate, and (d) a sunscreen selected from the group consisting of ethylhexyl triazone, diethylhexyl butamido triazone and 2-ethylhexyl salicylate, wherein the photoprotective system represents between 4% and 20%, in particular between 6% and 19%, especially between 7% and 18%, typically between 8% and 17% by weight of the composition in relation to the total weight of the composition, said composition not comprising any other sunscreen filter besides those that constitute said photoprotective system.

2. Composition according to claim 1, characterized in that 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)bis[1,2,4]triazine represents between 1% and 5%, especially between 2% and 5%, particularly between 2% and 4% by weight, typically between 3% and 4% of the composition relative to the total weight of the composition.

3. Composition, according to claim 1 or 2, characterized in that 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]6-(4-methoxyphenyl)-1,3,5-triazine represents between 1% and 4%, in particular between 2% and 3% by weight of the composition relative to the total weight of the composition.

4. Composition, according to any one of claims 1 to 3, characterized in that hexyl 2-[4(diethylamino)-2-hydroxybenzoyl]benzoate represents between 1% and 10%, especially between 3% and 10%, in particular between 4% and 9%, typically between 5% and 8%, for example between 5% and 6% by weight of the composition Petition 870260060871, dated 06 / 22 / 2026, page 12 / 69 2 / 3 in relation to the total weight of the composition.

5. Composition, according to any one of claims 1 to 4, characterized in that the sunscreen (d) represents between 1% and 5%, especially between 2% and 4%, in particular between 3% and 4% by weight of the composition relative to the total weight of the composition.

6. Composition, according to any one of claims 1 to 5, characterized in that the sunscreen (d) is ethyl hexyl triazone.

7. Composition according to any one of claims 1 to 6, characterized in that the D50 particle size of 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine is between 100 and 1000 nm.

8. Composition, according to any one of claims 1 to 7, characterized in that it comprises C12-C15 alkyl benzoate, dicaprylyl carbonate and caprylic / capric triglycerides.

9. Composition, according to any one of claims 1 to 8, characterized in that it is free of ethanol and isopropanol.

10. Composition, according to any one of claims 1 to 9, characterized in that it is in the form of an emulsion.

11. Use of a photoprotective system consisting of: (a) 5,6,5',6'-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine, (b) 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)1,3,5-triazine, (c) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate, and (d) a sunscreen selected from the group consisting of ethyl hexyl triazone, diethyl hexyl butamido triazone and 2-ethyl hexyl salicylate, Petition 870260060871, dated 06 / 22 / 2026, p. 13 / 69 3 / 3 characterized by being for the preparation of a cosmetic composition, as defined in any one of claims 1 to 10, for the protection of the skin (face and / or body) and / or hair against ultraviolet rays.