COSMETIC SUNSCREEN COMPOSITION CONTAINING MYCOSPORIN ANALOGUE AMINO ACIDS

Abstract

The present invention relates to a composition and its use for protection against ultraviolet solar radiation. In particular, the invention relates to a composition comprising: - at least one mycosporin amino acid analogue, known as "MAA"; - at least one organic UVB filter or a broad-spectrum organic filter; - at least one organic UVA filter.

Description

Title of the invention: COSMETIC SUNSCREEN COMPOSITION CONTAINING AMINO ACIDS ANALOGUES OF MY-COSPORIN Scope of the invention

[0001] The present invention relates to a composition, in particular a cosmetic or dermatological composition, advantageously solar, comprising amino acids analogous to mycosporin and sun filters, as well as its use to protect the skin from ultraviolet radiation. Prior state of the art

[0002] Ultraviolet (UV) radiation consists of light with wavelengths between 100 nm and 400 nm, traditionally divided into three subgroups: UV-A (400-315 nm), UV-B (315-280 nm), and UV-C (280-100 nm). UV-C, with its shorter wavelength, is the most energetic and harmful form of UV radiation. It is filtered by the ozone layer in the atmosphere and does not reach the Earth's surface in significant quantities. Most skin damage is caused by UV-A and UV-B radiation.

[0003] UV-B rays induce the production of the skin's natural pigment called "melanin." This is the origin of the phenomenon commonly known as "tanning." UV-B rays also stimulate cells to produce a thicker epidermis. The reactions described above constitute a defense mechanism of the body against UV radiation.

[0004] The high energy of UV-B radiation generates molecular disorders (DNA alteration and protein damage) which, in the long term, saturate and disrupt the nuclear DNA repair system. This leads to permanent mutations in the genome of affected cells, which are the cause of skin cancers. This is a direct form of UV-B toxicity. As for UV-A radiation, it is known that it penetrates the deep layers of the skin, where it produces deleterious effects, particularly on connective tissue and blood vessels. It is notably responsible for the phenomenon known as "photoaging," that is, premature actinic aging of the skin.

[0005] Moreover, although UV-B rays are the primary cause of skin cancers, UV-A rays also make an indirect contribution to this type of damage. Indeed, both UV-A and UV-B rays are responsible for the production of free radicals, particularly ROS (Reactive Oxygen Species). These are highly unstable molecules with a very short half-life, on the order of from nanoseconds to milliseconds. ROS are capable of damaging intracellular structures (DNA, membranes, intracellular proteins, etc.) as well as extracellular structures (components of the extracellular matrix such as collagen fibers). ROS also exert an indirect harmful effect by causing the oxidation of membrane lipids, which induces the formation of reactive carbonyl species that contribute to amplifying tissue and cellular damage.

[0006] It is therefore necessary to combat the harmful effects of UV radiation, particularly UV-A and UV-B, taking into account inter-individual differences such as skin type (phototype) and sun exposure times. For this reason, sunscreen compositions have been developed to provide photoprotection for areas exposed to UV radiation. These compositions are available in the form of lotions, oils, oil-in-water or water-in-oil emulsions, foams, gels, sticks, or sprays. They contain a cosmetically acceptable base and one or more chemical filters or mineral sunscreens at various concentrations.

[0007] Mineral sunscreens, including zinc oxides and titanium dioxides, protect against UV radiation by reflecting sunlight. They therefore act like mirrors localized on the surface of the skin. Mineral sunscreens, at least in micrometric formulations, are safe for human use and pose no health risks.

[0008] However, they have other disadvantages: - Mineral sunscreens tend to dry out the skin and are difficult to spread, leaving white streaks on the skin which can be very unsightly; - The galenic assessment of compositions based on mineral screens is often poor, particularly in compositions free of silicones.

[0009] Chemical filters are organic compounds that absorb light, creating a filtering layer on the skin that neutralizes UV rays. Thus, when the sunscreen molecule receives UV radiation, it enters an excited state by absorbing the energy of the radiation and then returns to its stable state. Through this mechanism, the light radiation is converted into heat and dissipated. Chemical filters therefore act in the same way as melanin, the skin's natural photoprotective pigment. Most chemical or organic filters are lipophilic and are therefore suitable for use in highly water-resistant compositions. From a pharmaceutical standpoint, compositions based on organic filters are generally more popular than those based on mineral sunscreens, which improves user compliance.

[0010] In Europe, all organic filters or mineral screens authorized by regulations are listed (Annex VI of the European Directive on cosmetic products). This is a list currently comprising around thirty compounds, identified by their INCI designation, from which the cosmetics industry must choose ingredients to formulate sunscreens. However, this list is not fixed and is constantly evolving based on the results of scientific research. Indeed, several studies have shown that some of the organic filters on this list could pose risks to human health and the environment, particularly because they are suspected of acting as endocrine disruptors.

[0011] In particular, scientific results call into question the safety of benzophenone-4 or benzophenone-3 (Kinnberg et al. 2015; Zucchi et al. 2011), octyl methoxycinnamate (Szwarcfarb et al. 2008, Axelstad et al. 2011), 3-methylbenzylidene camphor and 4-methylbenzylidene camphor (Schlumpf et al. 2008; Petersen et al. 2007), octocrylene, isoamyl methoxycinnamate, or octyl dimethyl PABA (Schlumpf et al. 2001; Rehfeld et al. 2016; Ozäez et al. 2016).

[0012] In addition to the potential effects on humans, the impact of these molecules on natural environments cannot be ignored; indeed, the filters are continuously dispersed into bathing water or wastewater. This water pollution, combined with UV filters, inevitably affects the entire food chain, with unpredictable consequences for the balance of an ecosystem already compromised by human activities; among other examples of ecotoxic effects, sunscreens are believed to have a negative impact on marine reefs and are notably responsible for the phenomenon of coral bleaching (Danovaro et al. 2008).

[0013] The progressive reduction in the number of organic sunscreens, considered safe for human use and for the environment, is increasingly complicating the formulation of sun cosmetic products, in particular high protection factor sunscreens, i.e. with an SPF (Sun protection factor) greater than 20 or even 30. The formulation of high sun protection products is particularly difficult in the case of products intended for the Canadian and American markets, where only a portion of the latest generation filters used in Europe for the past two decades are authorized.

[0014] To compensate for the reduction in the number of usable sunscreens, sun protection agents are often formulated in cosmetic products. These sun protection agents are sometimes molecules similar to authorized sunscreens, or plastic derivatives, which can therefore suffer from the same drawbacks as organic sunscreens; in particular, their ecotoxicity could be significant.

[0015] An interesting family of protective agents is represented by mycosporine-like amino acids (MAAs). MAAs are small heterocyclic molecules (<400 Da) comprising cyclohexenone or cyclohexeminine chromophores.

[0016] MAAs are found naturally as secondary metabolites in marine organisms, such as corals, algae and cyanobacteria, so they are expected to be eco-compatible and respectful of aquatic ecosystems.

[0017] In particular, document EP2855441 discloses a family of MAA-type compounds having the following general IE formula:

[0018] [Chem.l]

[0019] This document specifies that these compounds, from the IE molecule family, absorb ultraviolet radiation and can be used as UV-blocking agents. As an example, compounds with formulas IAi and IE4 are given, having sun protection factors of 2.4 and 4.5 respectively.

[0020] Thus, although MAAs of the IE molecule family absorb UV radiation, the sun protection factor is insufficient for use in sun cosmetic compositions.

[0021] Although considered good candidates for the formulation of eco-friendly sun products, a solution must be found to improve the anti-UV potential of MAAs, in order to be able to use them in sun products.

[0022] Thus, the present invention aims to overcome the drawbacks of the prior art, by proposing a composition comprising MMAs and whose SPF is compatible with a topical solar application. Description of the invention

[0023] The Applicant found that, quite surprisingly, combining MMAs with organic filters resulted in an SPF for the combination that was higher than the sum of the respective SPFs of the MAAs and the organic filters.

[0024] This combination is therefore suitable for their implementation in high sun protection compositions with relatively low organic filter contents.

[0025] Thus, according to a first aspect, the invention relates to a composition, in particular a cosmetic or dermatological composition, comprising: -at least one mycosporine analogue amino acid called "MAA"; -at least one organic UVB filter and / or one broad-spectrum organic filter; -at least one organic UVA filter.

[0026] According to another aspect, the invention relates to a composition, in particular a com- cosmetic or dermatological position, including: -at least one MAA chosen from the group consisting of molecules A with formula IA or one of its acceptable salts, and / or the group consisting of molecules B with formula IB or one of its acceptable salts, said formula IA being:

[0027] Formula IA:

[0028] [Chem.2]

[0029] Formula IB:

[0030] [Chem.3]

[0031] In which: RI is hydrogen; alkyl; alkenyl; alkynyl; aryl; heterocycle; cycloalkyl; alkoxy; alcanoyl; hydroxyl; a sulfo group; a halogeno group; a phosphono group; an ester group; a carboxylic acid group; a phenyl group; an amino group; an alkylated fatty acid chain or a polyether; R2 is alkyl; alkenyl; alkynyl; aryl; heterocycle; cycloalkyl; alkoxy; alcanoyl; a sulfo group; a phosphono group; an ester group; a carboxylic acid group; hydroxyl; or a phenyl group; said composition further includes: -at least one UVB organic filter and one broad-spectrum organic filter or one of the two ; -at least one organic UVA filter.

[0032] The MAAs according to the invention are known to those skilled in the art and described for example in patent application WO2013 / 181741 which details their method of obtaining and purifying them.

[0033] According to a particular embodiment, RI is an alkoxy group of the type [CH3 ]-[CH2]nO-, where "n" is between 0 and 10. According to a preferred embodiment, "n" = 0 or "n" = 8.

[0034] According to a particular embodiment of the invention, R2 is a carboxylic acid group of the type [COOH]-[CH2]n-, where "n" is between 0 and 5, where preferably "n"=1 or "n"=0.

[0035] According to an alternative embodiment of the invention, R2 is an ester group of the type [CH3]-[CH2]n-[COOH]-, where "n" is between 0 and 5, where preferably "n"=1 or "n"=2.

[0036] According to another particular embodiment, RI is an alkoxy group of the type [CH3]-[CH2]nO-, where "n" = 0; and; R2 is an ester group of the type [CH3]-[CH2]n-[COOH]-, where "n" = 1 or "n" = 2 or R2 is a carboxylic acid group of the type [COOH]-[CH2]n-, where "n" is between 0 and 5, where preferably "n" = 1 or "n" = 0.

[0037] Thus, and according to a particular embodiment, MAA according to formula IA corresponds to the molecule of formula IIA below:

[0038] Formula IIA:

[0039] [Chem.4]

[0040] This molecule has the formula IIA: [N- [(3E)-3-[(4-methoxyphenyl)imino]-5,5-dimethyl-1 -cyclohexen-1 -yl]-Glycine, corresponding to CAS number 1509902-01-5] is marketed by ELKIMIA Inc. under the INCI name methoxyphenylimino dimethylcyclohexene glycine.

[0041] According to a preferred embodiment, MAA according to formula IB corresponds to the molecule of formula IIB1 below:

[0042]

[0043] Formula IIB1 [Chem. 5]

[0044]

[0045]

[0046]

[0047] This molecule has the formula IIB1 [3,5,6,7-tetrahydro-6,6-dimethyl-8-[[4-(octyloxy)phenyl]amino]-2H-l,4-Benzothiazine -3-carboxylic acid, corresponding to CAS number 1629023-01-3] is marketed by ELKIMIA Inc. under the INCI name caprylyloxyphenylamino dime-thyltetrahydro benzothiazine carboxylic acid. According to an alternative embodiment, MAA according to formula IB corresponds to the molecule of formula IIB2 below: Formula IIB2 [Chem. 6]

[0048] This molecule of formula IIB2 [3,5,6,7-tetrahydro-8-[(4-methoxyphenyl)amino]-6,6-dimethyl-2H-l,4-Benzothiazine-3-carboxylic acid corresponding to CAS number 1629023-04-6] is marketed by ELKIMIA Inc. under the INCI name methoxyphenylimino dimethyl-hexahydro benzothiazine carboxylic acid.

[0049] In a particular embodiment of the invention, the compositions according to the invention contain at least two MAAs as defined above, in particular chosen from the molecules corresponding to the INCI designations methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethyltetrahydro benzothiazine carboxylic acid, methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid.

[0050] According to a particular embodiment, the compositions according to the invention contain at least three MAAs.

[0051] By "acceptable salts", for the purposes of the invention, means any pharmacologically or cosmetically acceptable salt of MAA, such as, for example, salts of the type sulfate, citrate, acetate, oxalate, chloride, bromide, iodide, nitrate, bisulfate, phosphate, isonicotinate, lactate, salicylate, citrate, tartrate, oleate, tannate, pan-tothenate, bitartrate, ascorbate, succinate, maleate, gentisinate, fumarate, gluconate, glucuronate, saccharate, formate, benzoate, glutamate, methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate, pamoate and hydroxy-3-naphthoate.

[0052] According to a particular embodiment, the MAA(s) represent between 0.1% and 20% by mass relative to the total mass of the composition, preferably between 0.5% and 10%, even more advantageously between 1% and 2%.

[0053] For the purposes of this invention, "organic UVB filter" means any organic solar filter, whether hydrophilic or lipophilic, that absorbs mainly or exclusively in the UVB range.

[0054] According to a particular embodiment, the organic UVB filter is selected from salicylates. More specifically, the organic UVB filter is selected from compounds corresponding to the following INCI designations: ethylhexyl salicylate and homosalate, or phenylbenzimidazole sulfonic acid or ethylhexyl triazone.

[0055] One source of the latter is the raw material UVINUL™ T150 marketed by BASF.

[0056] The organic UVB filter corresponding to the INCI designation phenylbenzimidazole sulfonic acid is available from AAKO BV under the name AakoSun PBSA. The salicylates corresponding to the INCI designations octyl salicylate and homosalate are available from SYMRISE under the names Neo Heliopan™ OS and Neo Heliopan™ HMS, respectively.

[0057] According to a particular embodiment of the invention, said at least one filter Organic UVB represents between 1% and 20% by mass relative to the total mass of the composition, preferably between 2% and 15%.

[0058] For the purposes of this invention, "organic UVA filter" means any organic solar filter, whether hydrophilic or lipophilic, that absorbs mainly or exclusively in the UVA range.

[0059] According to a preferred embodiment, the composition according to the invention comprises at least one UVA sunscreen selected from the group comprising the compounds corresponding to the following INCI designations: butyl methoxydibenzoylmethane, di-thylamino hydroxybenzoyl hexyl benzoate, bis-(diethylaminohydroxybenzoyl benzoyl)piperazine, disodium phenyl dibenzimidazole tetrasulfonate, in particular butyl methoxydibenzoylmethane and diethylamino hydroxybenzoyl hexyl benzoate.

[0060] By way of example, the UVA filters according to the invention correspond to the raw material Parsol 1789® (INCI: butyl methoxydibenzoylmethane) marketed by the company DSM; the raw material UVINUL™ A+ (INCI: diethylamino hydroxybenzoyl hexyl benzoate) marketed by the company BASF; the raw material Cl332™ [INCI: bis-(diethylaminohydroxybenzoyl benzoyl)piperazine; CAS number 919803-06-8] marketed by the company BASF; or the material Neo Heliopan™ AP corresponding to the INCI designation disodium phenyl dibenzimidazole tetrasulfonate, and marketed by the company SYMRISE.

[0061] According to a particular embodiment, said at least one organic UVA filter represents between 1% and 10% by mass relative to the total mass of the composition, preferably between 2% and 7%.

[0062] For the purposes of this invention, "broad-spectrum organic filter" means any organic sunscreen, whether hydrophilic or lipophilic, that absorbs both UVB and UVA rays. In a preferred embodiment, the composition according to the invention comprises at least one broad-spectrum sunscreen selected from the group comprising compounds corresponding to the following INCI designations: bis ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, tris-biphenyl triazine, phenylene bis-diphenyltriazine, methylene bis-benzotriazolyl tetramethylbutylphenol and drometrizole trisiloxane, in particular bis ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, tris-biphenyl triazine, methylene bis-benzotriazolyl tetramethylbutylphenol.

[0063] These solar filters are available from the following suppliers: - PARSOL™ Shield marketed by the company SYMRISE and corresponding to the INCI designation: bis ethylhexyloxyphenol methoxyphenyl triazine; -1' UVASORB™ HEB marketed by the company SIGMA 3V and corresponding to the INCI designation: diethylhexyl butamido triazone; - TINOSORB™ A2B, marketed by BASF and corresponding to the de- INCI sign tris-biphenyl triazine; - TRIASORB™ marketed by the company PLANTES & INDUSTRIE and corresponding to the INCI designation: phenylene bis-diphenyltriazine (CAS number 55514-22-2); - MEXORYL™ XL, corresponding to the INCI designation: drometrizole trisiloxane; - TINOSORB™ M marketed by BASF and corresponding to the INCI designation: methylene bis-benzotriazolyl tetramethylbutylphenol.

[0064] According to a particular embodiment, said at least one broad-spectrum organic filter represents between 1% and 15% by mass relative to the total mass of the composition, preferably between 2% and 10%.

[0065] According to a preferred embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the INCI designations methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethyltetrahydro benzo-thiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least two organic UVB filters; -at least one organic UVA filter.

[0066] According to an alternative embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethyltetrahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least two broad-spectrum organic filters; -at least one organic UVA filter.

[0067] According to yet another embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethyltetrahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least one organic UVB filter; -at least one broad-spectrum organic filter; -at least one organic UVA filter.

[0068] According to yet another embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxy-phenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least one organic UVB filter; -at least two broad-spectrum organic filters; -at least one organic UVA filter.

[0069] According to yet another embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least two organic UVB filters; -at least one broad-spectrum organic filter; -at least one organic UVA filter.

[0070] According to another aspect, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least UVB filters corresponding to the following INCI designations: octyl sa-licylate and homosalate; - at least the organic UVA filter corresponding to the following INCI designation: butyl methoxydibenzoylmethane.

[0071] According to a particular embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least UVB filters corresponding to the following INCI designations: octyl sa-licylate and homosalate; - at least the organic UVA filter corresponding to the following INCI designation: diethylamino hydroxybenzoyl hexyl benzoate.

[0072] According to a different embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxy-phenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least broad-spectrum filters corresponding to the following INCI designations: diethylhexyl butamido triazone and bis-ethylhexyloxyphenol methoxyphenyl triazine; -at least one UVA sunscreen chosen from the group comprising the compounds corresponding to the following INCI designations: butyl methoxydibenzoylmethane, di-thylamino hydroxybenzoyl hexyl benzoate, bis-(diethylaminohydroxybenzoyl benzoyl)piperazine, disodium phenyl dibenzimidazole tetrasulfonate, in particular butyl methoxydibenzoylmethane and diethylamino hydroxybenzoyl hexyl benzoate, advantageously butyl methoxydibenzoylmethane and diethylamino hydroxybenzoyl hexyl benzoate.

[0073] According to a different embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least broad-spectrum filters corresponding to the following INCI designations: diethylhexyl butamido triazone and bis-ethylhexyloxyphenol methoxyphenyl triazine; -at least one UVA sunscreen corresponding to the following INCI designation: diethylamino hydroxybenzoyl hexyl benzoate.

[0074] According to an alternative embodiment, the composition according to the invention comprises: —at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least broad-spectrum filters corresponding to the following INCI designations: diethylhexyl butamido triazone and bis-ethylhexyloxyphenol methoxyphenyl triazine; -at least the organic UVB filter corresponding to the following INCI designation: ethylhyexl triazone; -at least the organic UVA filter corresponding to the following INCI designation: butyl methoxydibenzoylmethane.

[0075] According to a particular embodiment, the composition according to the invention comprises: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxy-phenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least the broad-spectrum organic filters corresponding to the following INCI designations: diethylhexyl butamido triazone and bis-ethylhexyloxyphenol methoxyphenyl triazine; -at least the organic UVB filter corresponding to the following INCI designation: ethylhexyl triazone; -at least the organic UVA filter corresponding to the following INCI designation: die-thylamino hydroxybenzoyl hexyl benzoate.

[0076] According to a particular embodiment, the composition according to the invention is free of the sunscreens corresponding to the following INCI designations: 4-methylbenzylidene camphor, 3-methylbenzylidene camphor, benzophenone-2, benzophenone-3, benzophenone-4, ethylhexyl methoxycinnamate, isoamyl methoxy-cinnamate, octocrylene, octyl dimethyl PABA.

[0077] Preferably, the composition also includes at least one sunscreen solubilizer. For the purposes of the invention, "solubilizer" means a compound that allows at least one triazine-derived sunscreen to be solubilized, dispersed and / or dissolved effectively and durably, i.e. by stabilizing it in its solubilized form and preventing or reducing its recrystallization or precipitation in the formulation throughout the product's use.

[0078] Thus, the compositions according to the invention further comprise at least one solubilizer selected from the group comprising the compounds corresponding to the following INCI designations: caprylyl caprylate / caprate, dibutyl adipate, dicaprylyl carbonate, diisopropyl sebacate, dicaprylyl ether, coco-caprylate, C12-15 alkyl benzoate, propylheptyl caprylate, butylene glycol dicaprylate / dicaprate, dipropylene glycol dibenzoate, neopentyl glycol diheptanoate, triheptanoin, Cl2-13 alkyl lactate, ethylhexyl benzoate, C12-C15 alkyl lactate, Cl2-13 alkyl tartrate, tridecyl salicylate, lauryl lactate, diethyl adipate, diisobutyl adipate, diisopropyl adipate, diethylhexyl adipate, diethylhexyl succinate, propanediol dicaprylate, propylene glycol dicaprylate / dicaprate, isopropyl lauroyl sarcosinate, propylene glycol dibenzoate, hydroxyl dime-thoxybenzyl malonate, phenoxyethyl caprylate, isodecyl salicylate, dimethyl capramide and phenethyl benzoate,in particular at least two solubilizers chosen from the following group: caprylyl caprylate / caprate, dibutyl adipate, dicaprylyl carbonate, diisopropyl sebacate, dicaprylyl ether, coco-caprylate, C12-15 alkyl benzoate, propylheptyl caprylate, butylene glycol dicaprylate / dicaprate.

[0079] Solubilizers suitable for use in a composition according to the invention are available on the market from several suppliers. By way of example, the following raw materials can be used in the composition according to the invention: - Several raw materials from the CETIOL™ range marketed by BASF, including CETIOL™ RLF, CETIOL™ B, CETIOL™ CC, CETIOL™ O, CETIOL™ C5, CETIOL™ AB, CETIOL™ SENSOFT corresponding respectively to the following INCI designations: caprylyl caprylate / caprate, dibutyl adipate, dicaprylyl carbonate, dicaprylyl ether, coco-caprylate, C12-15 alkyl benzoate, propylheptyl caprylate; - DUB™ DIS, DEA, DIBA, ZENOAT marketed by the company STEARINE DUBOIS corresponding respectively to the following INCI designations: diisopropyl sebacate, diethyl adipate, diisobutyl adipate and propanediol dicaprylate; - MIGLYOL™ 8810 and MIGLYOL™ T-C7 marketed by IOI Oleo GmbH correspond respectively to the following INCI designations: butylene glycol dicaprylate / dicaprate and triheptanoin; - Lexsolv™ A marketed by the company INOLEX corresponding to the following INCI designations: dipropylene glycol dibenzoate and neopentyl glycol di-heptanoate; - COSMACOL™ ELI, ETI, ESI and LL marketed by SASOL and corresponding respectively to the following INCI designations: C12-13 alkyl lactate, C12-13 alkyl tartrate, tridecyl salicylate and lauryl lactate; - Ceraphyl™ 41 ester marketed by the company ASHLAND and corresponding to the following INCI designation C12-C15 alkyl lactate; - Finsolv™ EB and PG 22 marketed by INNOSPEC and corresponding respectively to the following INCI designations: ethylhexyl benzoate and dipropylene glycol dibenzoate; - CRODAMOL™ DA, DOA, OSU and PC marketed by the company CRODA and corresponding respectively to the following INCI designations: diisopropyl adipate, diethylhexyl adipate, diethylhexyl succinate and propylene glycol dicaprylate / dicaprate; - The ELDEW™ SL-205 marketed by the company AJINOMOTO and corresponding to the following INCI designation: isopropyl lauroyl sarcosinate; - Lexfeel™ Shine marketed by the company INOLEX and corresponding to the INCI designation propylene glycol dibenzoate; - TEGOSOFT™ XC marketed by the company EVONIK and corresponding to the following INCI designation: phenoxyethyl caprylate; - RONACARE™ AP marketed by MERCK KGaA and corresponding to the following INCI designation: hydroxyl dimethoxybenzyl malonate; - DERMOL™ IDSA marketed by the company Alzo INTL and corresponding to the following INCI designation: isodecyl salicylate; - Spectrasolv™ DMDA marketed by the company Hallstar and corresponding to the following INCI designation: dimethyl capramide; - X-TEND™ 226 marketed by the company Ashland and corresponding to the following INCI designation: phenethyl benzoate.

[0080] According to a particular embodiment, the composition according to the invention comprises at least three solubilizers selected from the group comprising the compounds corresponding to the following INCI designations: caprylyl caprylate / caprate, dibutyl adipate, dicaprylyl carbonate, diisopropyl sebacate, dicaprylyl ether, coco-caprylate, C12-15 alkyl benzoate, propylheptyl caprylate, butylene glycol dicaprylate / dicaprate.

[0081] According to a particular embodiment, the composition according to the invention comprises at least the solubilizers corresponding to the following INCI designations: dibutyl adipate, dicaprylyl carbonate and diisopropyl sebacate.

[0082] According to another embodiment, the composition according to the invention comprises at least the solubilizers corresponding to the following INCI designations: dibutyl adipate, dicaprylyl carbonate, diisopropyl sebacate and propylheptyl caprylate.

[0083] According to a particular embodiment, the solubilizers represent between 5% and 80% by mass relative to the total mass of the composition, advantageously between 10% and 70%, preferably between 15% and 60%.

[0084] According to a particular embodiment, the composition according to the invention comprises mineral screens (or inorganic mineral filters), which correspond to metal oxides and / or other compounds that are difficult to dissolve or insoluble in water, in particular oxides of titanium (TiO2), zinc (ZnO), iron (Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (for example MnO), aluminum (Al2O3), or cerium (Ce2O3), or bismuth trioxide (Bi2O3).

[0085] Inorganic mineral filters can also be surface-treated or encapsulated to give them hydrophilic, amphiphilic, or hydrophobic properties. This surface treatment may consist of applying a thin hydrophilic and / or hydrophobic inorganic and / or organic film to the mineral filters.

[0086] According to a particular embodiment, the composition according to the invention comprises at least one mineral screen selected from the group comprising the compounds corresponding to the following INCI designations: zinc oxide, titanium dioxide and their mixtures.

[0087] By way of example, zinc oxide corresponds to the raw material Z-COTE® LSA and titanium dioxide to the raw material T-Lite®, marketed by BASF.

[0088] The lists of UV filters mentioned that can be implemented within the meaning of this inventions are of course given for illustrative purposes only and are not exhaustive.

[0089] According to a particular embodiment, the composition according to the invention has a sun protection factor called "SPF" equal to or greater than 20, advantageously equal to or greater than 30, preferably equal to or greater than 40, or even equal to or greater than 50.

[0090] According to a preferred embodiment, the composition according to the invention comprises a UV-A / UV-B protection ratio equal to or greater than 1 / 3.

[0091] In particular, the composition according to the invention has a critical wavelength (Xc) greater than 370 nm. This value, which is determined by in vitro methods known to those skilled in the art, corresponds to the wavelength for which the integral of the absorption spectrum curve starting at 290 nm reaches 90% of the integral between 290 and 400 nm.

[0092] The composition according to the invention may further comprise an SPF “booster,” i.e., an agent that enhances the sun protection factor, and / or a photo-stabilizer, i.e., an ingredient that increases the SPF or photo-stabilizes the filters, such an ingredient not itself being considered a sunscreen. Examples include: - Butyloctyl salicylate (INCI), a photostabilizer advantageously representing between 0.01% and 10% by weight relative to the total weight of the composition, even more advantageously between 0.1% and 2%. This raw material is, for example, marketed by the company HALLSTAR under the name Hallbrite® BHB; - benzotriazolyl dodecyl p-cresol (INCI), a photostabilizer advantageously representing between 0.01% and 10% by weight relative to the total weight of the composition, even more advantageously between 0.1% and 2%. This raw material is, for example, marketed by BASF under the name TINOGARD® TL; - Pongamol (INCI), a plant molecule that absorbs UV-A, advantageously representing between 0.5 and 2% by weight relative to the total weight of the composition, and even more advantageously around 1%. As an example, the raw material Pongamia Extract marketed by GIVAUDAN can be used in the context of the present invention; - Ethylhexyl methoxycrylene (INCI), a photostabilizer, solubilizer, and SPF booster, advantageously representing between 1% and 5% by weight relative to the total weight of the composition. The raw material SolaStay® SI, marketed by HALLSTAR, can be used within the scope of the present invention; - a styrene acrylate copolymer (INCI: styrene / acrylate copolymer), preferably representing between 1% and 10% by weight relative to the total weight of the composition according to the invention. The raw materials SunSpheres® H53 and SunSpheres® PGL Polymer, marketed by DOW CHEMICALS, may be used in the context of the present invention; - diethylhexyl syringylidene malonate (INCI), advantageously representing between 1% and 10% by weight relative to the total weight of the composition. The raw material OXYNET® ST, marketed by MERCK, can be used within the scope of the present invention; - a water-dispersible polyester, corresponding to the INCI designations polyester-5 (and) Sodium silicoaluminate, advantageously representing between 1% and 10% by weight relative to the total weight of the composition, in particular the EASTMANN AQTM38S Polymer marketed by the company SAFIC-ALCAN; - an acrylate copolymer having a glass transition temperature of -5°C to -15°C as measured by differential scanning calorimetry, said copolymer advantageously representing between 1% and 10% by weight relative to the total weight of the composition. For example, a polymer corresponding to the INCI designation Acrylate copolymer, such as the raw material EPITEX 66, marketed by DOW CHEMICALS, may be used in the context of the present invention.

[0093] In a preferred embodiment, the composition according to the invention further comprises other components which may contribute to internal protection by an action which may consist of DNA protection, a reduction of immunosuppression induced by UV radiation, an anti-radical action or a combined effect of these actions.

[0094] The protective action of a composition according to the invention against oxidative stress or against the effect of free radicals can be further improved if it also comprises one or more antioxidants, easily selected by those skilled in the art, for example from the following list: totarol, magnolol, honokiol, amino acids and their derivatives, peptides (D- and / or L-carnosine) and their derivatives (e.g., anserine, hypotaurine, taurine), carotenoids, carotenes (α-carotene, 3-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosylated esters, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, y-linolenic, cholesteryl and glyceryl) as well as salts thereof, dilauryl thiodipropionate,distearyl thiodipropionate, thiodipropionic acid and its derivatives, sulfoximine compounds (buthione sulfoximine, homocysteine ​​sulfoximine, buthione sulfones, penta-, hexa- and heptathione sulfoximine), chelating agents (such as α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (such as citric, lactic, or malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, ethylenediamine pentasodium tetramethylene phosphonate and its derivatives, unsaturated fatty acids and their derivatives, vitamin A and its derivatives, (vitamin A palmitate), coniferyl benzoate from benzoin resin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid and its derivatives, furfuryl-deneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nor-dihydroguaiaretic acid, trihydroxybutyrophenone, quercetin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (ZnO, ZnSO4), selenium and its derivatives (selenomethionine), stilbenes and their derivatives (stilbene oxide, trans-stilbene oxide).

[0095] In a particular embodiment, the composition according to the invention further comprises glycyrrhetinic acid, a derivative or a salt of this acid, used as a soothing (anti-inflammatory agent) and representing between 0.01% and 2% by weight relative to the total weight of the composition, preferably between 0.1% and 1%.

[0096] According to another preferred feature of the invention, the cosmetic and / or dermatological composition comprises at least one, or even all, of the following constituents exerting in vivo biological activity on skin, lip, hair and / or mucous membrane cells subjected to UV-A and / or UV-B radiation, respectively: - an anti-radical agent preserving cellular structures, such as for example vitamin E and / or its fat-soluble or water-soluble derivatives, in particular tocotrienol and / or tocopherol, advantageously representing between 0.001 and 10% by weight relative to the total weight of the composition, even more advantageously between 0.02 and 2%, preferably in the order of 0.04%; - an immunosuppression-limiting agent, such as vitamin PP, advantageously representing between 0.001 and 1% by weight relative to the total weight of the composition, even more advantageously from 0.01% to 0.3%; - a p53 protein protective agent, such as epigallocatechin gallate (EGCG), advantageously representing between 0.001 and 0.1% by weight relative to the total weight of the composition, even more advantageously from 0.005% to 0.05%.

[0097] The composition according to the invention may also include, in addition, peptide extracts of soy and / or wheat, such as those described in document EP 2 059 230.

[0098] In practice, the peptide extracts, which are derived from soybean and wheat seeds, are obtained by enzymatic hydrolysis of said seeds using peptidases, which allows the recovery of peptides with an average size of 700 Daltons. Preferably, the soybean peptide extract is the extract identified under CAS number 68607-88-5, and the wheat peptide extract is the extract identified under CAS number 70084-87-6. The wheat and soybean extracts may correspond to the following INCI designations, respectively: Hydrolyzed wheat protein and Hydrolyzed soy protein.

[0099] In a particular embodiment, the peptide extracts of soy and / or wheat are used together, for example in a weight ratio respectively between 80 / 20 and 20 / 80, advantageously between 70 / 30 and 30 / 70, preferably equal to 60 / 40.

[0100] In a particular embodiment, the soy and / or wheat peptide extracts are free from the synthetic tripeptide GHK (glycylhistidyllysine; INCI: Tripeptide-1). In practice, the soy and / or wheat peptide extracts represent from 0.01 to 20% by weight relative to the total weight of the composition, advantageously from 0.1% to 10%, and even more advantageously from 0.2% to 0.7%.

[0101] In an alternative embodiment, the composition according to the invention comprises, in accordance with the teachings of document FR 2 865 398, the combination of at least one amino acid chosen from the group consisting of ectoine, creatine, ergothioneine and / or carnosine, or their physiologically acceptable salts, and mannitol or a derivative of mannitol.

[0102] Preferably, the composition according to the invention comprises in a physiologically acceptable medium the amino acid or one of its salts, alone or in mixture in proportions of between 0.001% and 10% by weight relative to the total weight of the composition, and preferably between 0.01% and 5%.

[0103] The composition according to the present invention comprises, preferably, in a physiologically acceptable medium, mannitol or one of its derivatives, in proportions of between 0.01% and 30% by weight relative to the total weight of the composition, advantageously between 0.1% and 10%.

[0104] In a preferred embodiment, the composition according to the invention comprises ectoine and mannitol.

[0105] According to a particular embodiment, the composition according to the invention comprises one or more other tanning or self-tanning agents. These may be a self-tanner that reacts with the amino acids of the skin via a Maillard reaction or by way of a Michael addition, or a melanogenesis promoter or a pro-pigmenting compound that promotes the natural tanning of the skin.

[0106] Such a tanning or self-tanning agent is preferably present in the composition in an amount ranging from 0.01% to 20% by weight relative to the total weight of the composition, advantageously from 0.5% to 15%, even more advantageously from 1% to 8%.

[0107] Self-tanning substances may be 1,3-dihydroxyacetone (DHA), glycerolaldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone), 2-hydroxy-1,4-naphthoquinone (lawsone), or a combination thereof.

[0108] The progating substances may be the melanocyte-stimulating hormone (a-MSH), a-MSH peptide analogues, endothelin-1 receptor agonists, opiate p receptor agonists, cAMP-stimulating agents, tyrosinase-stimulating agents.

[0109] In a particular embodiment, the composition according to the invention further comprises, as a self-tanner, a combination of dihydroxy methylchromonyl palmitate and / or dimethylmethoxy chromanol, as well as a lipophilic form of tyrosine.

[0110] This combination of active ingredients effectively stimulates tanning. Dihydroxy methylchromonyl palmitate (CAS number: 1387636-35-2) corresponds, for example, to the cosmetic ingredient marketed by Merck under the name RonaCare® Bronzyl. Dimethylmethoxy chromanol (CAS number: 83923-51-7) corresponds, for example, to the cosmetic ingredient marketed by Lipotec SA under the name lipochromone-6.

[0111] According to a particular embodiment, dihydroxy methylchromonyl palmitate or dimethylmethoxy chromanol is included in the composition according to the invention at a level of 0.01% to 10% by weight relative to the total weight of the composition, advantageously from 0.05% to 10%, even more advantageously from 0.1% to 5%, more particularly from 0.1% to 0.5%.

[0112] The lipophilic form of tyrosine, in the sense of the invention, is a tyrosine-based ingredient and has a more pronounced lipophilic character than tyrosine. The lipophilic form of tyrosine can notably correspond to oleoyl tyrosine (CAS No. 147732-57-8), which is found, for example, in the liquid cosmetic ingredient TYR-OL, marketed by the company SEDERMA, and which comprises about 50% by weight of oleoyl tyrosine in butylene glycol (about 30% + about 20% oleic acid), or in the liquid cosmetic ingredient TYR-EXCEL, marketed by the company SEDERMA, which comprises about 50% by weight of oleoyl tyrosine, about 20% by weight of oleic acid (CAS No. 112-80-1) and about 30% by weight of Luffa cylindrica oil (sponge gourd seed oil; CAS No. 1242417-48-6).

[0113] According to another embodiment, the lipophilic form of tyrosine corresponds to a vegetable oil in which the tyrosine has been formulated.

[0114] According to a particular embodiment, the vegetable oil is high oleic sunflower oil, in particular deodorized. Thus, the raw material OLEOACTIF TYROSINE BASE HELIANTHUS ANNUS, marketed by the company OLEOS and corresponding to the INCI designations Helianthus annuus seed oil (and) tyrosine (and) glyceryl stearate, can be used in the context of the present invention.

[0115] In practice, the lipophilic form of tyrosine, such as in cosmetic ingredients based on oleoyl-tyrosine (advantageously at 50% by weight) or tyrosine formulated in vegetable oil, represents between 0.1% and 10% by weight relative to the total weight of the composition, advantageously between 1 and 3%, even more advantageously between 1% and 1.5%.

[0116] The composition according to the invention may also include active ingredients having depigmenting properties, such as: - lysine azeilate, or other derivatives or salts of azelaic acid; - of andrographolide, in particular the extract of Andrographis paniculata corresponding to the INCI designation Andrographis paniculata leaf extract; - native ascorbic acid (vitamin C) or its derivatives, in particular derivatives corresponding to the INCI Ascorbyl Glucoside, Ethyl ascorbic acid, Ascorbyl methylsilanol pectinate, Sodium ascorbyl phosphate and Ascorbyl tetraisopalmitate, advantageously ascorbyl glucoside; - arbutin or a plant extract containing it, in particular bearberry extract corresponding to the INCI designation Arctostaphylos uva-ursi leaf extract; - glabridin or a plant extract containing it, in particular licorice extracts corresponding to the INCI designation Glycyrrhiza glabra root extract, Gly-cyrrhiza inflata root extract, Glycyrrhiza uralensis root extract; - biomimetic peptides corresponding to the INCI designations hexapeptide 2 and / or nonapeptide-1; - an aqueous extract of an alga called Palmaria palmata, in particular the extract corresponding to the INCI designation Palmaria palmata extract; - 4-n-butylresorcinol; - vitamin PP, also called niacinamide or nicotinamide, and its derivatives; - or mixtures thereof.

[0117] The composition according to the invention may also include active ingredients having healing properties such as, for example, an antimicrobial agent selected from the active ingredients corresponding to the following INCI designations: copper sulfate, zinc sulfate, sodium hyaluronate, Vitis vinifera (grape) vine extract and mixtures thereof.

[0118] The composition according to the invention may also include active ingredients having sebocorrective, keratolytic, seboregulatory and / or anti-acne activity properties, in order to allow the formulation of sun products treating acne.

[0119] For example, the composition according to the invention may include an antimicrobial agent selected from the active ingredients corresponding to the following INCI designations: propyl gallate, dodecyl gallate, Ginkgo biloba leaf extract, bakuchiol, dihydromyricetin, zinc gluconate, salicylic acid and mixtures thereof.

[0120] The composition according to the invention may therefore further comprise at least one ingredient selected from the following list: - an agent capable of filtering visible light, in particular blue light; - an extract of the algae Laminaria ochroleuca, Blidingia minima or Laminaria saccharina; - an extract of the plant Zanthoxylum alatum; - panthenol; - an extract of juniper wood; - an excerpt from Boldo; - an excerpt from Meadowsweet; - an extract of karanja oil from Pongamia glabra; - linear paraffins; - ATP (adenosine-5 triphosphate), Gp4G (diguanosine tetraphosphate) or Ap4A (diadenosine tetraphosphate), - an amino acid chosen from the group consisting of decarboxycarnosine, glutamine and their salts.

[0121] The composition according to the invention may also include adjuvants such as those commonly used in the cosmetics industry, including preservatives, antioxidants, complexing agents, solvents, perfumes, fillers, bactericides, electrolytes, odor absorbers, colorants, or lipid vesicles. The choice of these adjuvants, as well as their concentrations, must be determined in such a way that they do not alter the properties and advantages sought for the composition of the present invention.

[0122] The composition of the invention is for topical application and more particularly for application on the skin, lips, hair and / or mucous membranes.

[0123] Thus and within the framework of the invention, such a composition is in particular intended for the protection of the skin and / or skin appendages, in particular mucous membranes, lips and hair, against UV radiation.

[0124] The composition of the invention can be presented in all the galenic forms normally used in the cosmetic and dermatological fields, such as, for example, but not limited to, an aqueous solution possibly gelled, a lotion-type dispersion, an O / W or W / O emulsion, more or less fluid, or a multiple emulsion such as a triple emulsion (W / O / W or W / O / O), or even in the form of a vesicular dispersion of ionic (liposomes) and / or non-ionic type, a biphasic composition without emulsifiers and gelling agents whose immiscible phases separate during storage, a foam, a stick, an anhydrous oil, a spray or a mist.

[0125] In a preferred embodiment, the composition according to the invention is a water-in-oil emulsion. In a particular embodiment, the water-in-oil emulsions according to the invention comprise PEG-30 dipolyhydroxystearate (INCI), or polyglyceryl-4 diisostearate / polyhydroxystearate / sebacate as emulsifiers. These materials The first two are available respectively from CRODA under the trade name Cithrol DPHS and from EVONIK under the name Isolan GPS.

[0126] In an alternative embodiment, the composition according to the invention is an oil-in-water emulsion. In a particular embodiment, the oil-in-water emulsions according to the invention comprise an emulsifier selected from the following group of compounds identified by their INCI name: sodium stearoyl glutamate, potassium cetyl phosphate, glyceryl stearate / PEG-100 stearate and C20-22 alkyl phosphate / C20-C22 alkyl alcohols, tribehenin PEG-20 esters, C14-C22 alcohols / C12-20 alkyl glucoside, cetearyl alcohol / coco-glucoside, polyglyceryl-6 stearate, polyglyceryl-6 behenate, and mixtures thereof. These raw materials are available from several suppliers.For example, the raw materials EMULGIN SG (INCI: sodium stearoyl glutamate; supplier: BASF); EMULIUM 22 (INCI: tribehenin PEG-20 esters; supplier: GATTEFOSSE); SENSANOV WR (INCI: C20-22 alkyl phosphate / C20-C22 alkyl alcohols; supplier: SEPPIC); MONTANOV L (INCI: C14-C22 alcohols / C12-20 alkyl glucoside), AMPHISOL K (INCI: potassium cetyl phosphate; supplier: DSM), MONTANOV 82 (INCI: cetearyl alcohol / coco-glucoside; supplier: SEPPIC) TEGO™ Care PBS 6 MB (INCI: poly-glyceryl-6 stearate & polyglyceryl-6 behenate; supplier: EVONIK) can be used in the compositions according to the invention.

[0127] According to another aspect, the invention relates to a composition as described above for its use for protection against ultraviolet solar radiation, in particular with a wavelength between 100 and 400 nm.

[0128] According to a particular embodiment, the invention relates to a composition comprising: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxy-phenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least one organic UVB filter or a broad-spectrum organic filter; -at least one organic UVA filter; for its use in protecting the skin, mucous membranes and / or hair against UV radiation.

[0129] According to a particular embodiment, the composition according to the invention is used to filter UV radiation between 280 and 400 nm, in particular between 300 and 380 nm.

[0130] According to a particular embodiment, the invention relates to a composition comprising: - at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the following INCI designations: methoxy-phenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid -at least one organic UVB filter or a broad-spectrum organic filter; -at least one organic UVA filter, for its use as a UV filtering agent, in particular for the wavelength spectrum between 280 and 400 nm, in particular between 300 and 380 nm.

[0131] According to a particular embodiment, the invention relates to the use of: -of at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the INCI designations methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethyltetrahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; with -at least one UVB organic filter or a broad-spectrum organic filter; with -at least one organic UVA filter; for its use in the preparation of a cosmetic composition.

[0132] The invention also relates to a cosmetic treatment method consisting of applying to the skin and its appendages a composition comprising: -at least one MAA as defined above, in particular chosen from the group consisting of molecules corresponding to the INCI designations methoxyphenylimino dimethylcyclohexene glycine, caprylyloxyphenylamino dimethyltetrahydro benzothiazine carboxylic acid and methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid; -at least one organic UVB filter or one broad-spectrum organic filter; -at least one organic UVA filter.

[0133] The manner in which the invention can be implemented and the resulting advantages will be more apparent from the following implementation examples, given by way of illustration and not limitation. Examples of implementation of the invention

[0134] The percentages indicated are given in mass of product relative to the total mass of the composition in the tables below.

[0135] [Tables 1] Ingrédients (dénomination INCI) Pourcentage (%) Aqua 52,70 Diethylamino hydroxybenzoyl hexyl benzoate (filtre UVA) 10,00 Bis-ethylhexyloxyphenol methoxyphenyl triazine (filtre à large spectre) 3,50 Diethylhexyl butamido triazone (filtre à large spectre) - methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid (MAA selon l’invention) 1,00 Hexyl laurate 10,00 Propanediol 5,00 Cl2-15 alkyl benzoate 4,00 Dicaprylyl carbonate 3,9988 Polyglyceryl-6 stéarate 2,2875 Glycerin 2,00 Microcrystalline cellulose 1,32 1,2-hexanediol 1,25 C20-22 alkyl phosphate 1,10 C20-22 alcohols 0,90 Caprylyl glycol 0,25 Polyglyceryl-6 behenate 0,2125 Sodium citrate 0,20 Cellulose gum 0,18 Sodium hydroxide 0,06 Xanthan gum 0,04 Tocopherol 0,0012

[0136] [Tableaux2] Ingrédients (dénomination INCI) Pourcentage (%) aqua 51,838 Homosalate (filtre UVB) 9,00 Ethylhexyl methoxycrylene 6,30 Glycerin 5,00 Ethylhexyl salicylate (filtre UVB) 4,50 Tribehenin PEG-20 esters 3,00 Silica 3,00 Butyl methoxydibenzoylmethane (filtre UVA) 2,70 Cl2-15 alkyl benzoate 2,50 Dimethicone 1,72 Butyloctyl salicylate 1,60 methoxyphenylimino dimethylcyclohexene glycine (MAA selon l’invention) 1,00 Benzotriazolyl dodecyl p-cresol 1.00 caprylyloxyphenylamino dimethyltetrahydro benzothiazine carboxylic acid (MAA selon l’invention) 1,00 Vp / eicosene copolymer 0,80 Cetearyl alcohol 0,80 C20-22 alkyl phosphate 0,55 PEG-100 stéarate 0,50 Pentylene glycol 0,50 Glyceryl stéarate 0,50 C20-22 alcohols 0,45 Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer 0,396 Poly silicone-11 0,28 1,2-hexanediol 0,25 Caprylyl glycol 0,25 Xanthan gum 0,20 Sodium citrate 0,20 Pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate 0,05 Sodium hydroxide 0,042 Sorbitan isostearate 0,027 Polysorbate 60 0,027 Aminoethanesulfinic acid 0,02 Exemple III - Emulsion solaire

[0137] [Tableaux3] Ingrédients (dénomination INCI) Pourcentage (%) Aqua 57,948 Homosalate (filtre solaire UVB) 9,00 Ethylhexyl methoxycrylene 6,30 Glycerin 5,00 Dibutyl adipate 5,00 Butyl methoxydibenzoylmethane (filtre solaire UVA) 4,50 Ethylhexyl salicylate (filtre soalire UVB) 4,50 Potassium cetyl phosphate 3,00 methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid (MAA selon l’invention) 1,00 Sodium stearoyl glutamate 1,00 Cetearyl alcohol 0,80 Pentylene glycol 0,50 Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer 0,396 Citric acid 0,302 Caprylyl glycol 0,25 1,2-hexanediol 0,25 Xanthan gum 0,20 Sorbitan isostearate 0,027 Polysorbate 60 0,027

[0138] Example IV - Measurement of the sun protection factor (SPF) obtained with compositions according to the invention IV-1 Purpose of the study

[0139] The objective of the study was the development of compositions with a high sun protection factor, i.e. with an SPF>20, incorporating organic UV filters and MAAs according to the invention. IV-2 Materials and methods

[0140] An in vitro method for measuring the solar protection factor was used. A first UV absorption measurement is carried out on a plate (PMMA molded plate or SB6 sandblasted plate, Helioscreen) coated with 15 lp of glycerin (white), thus eliminating the absorption of the substrate.

[0141] For formulas fiel and fie 2, the measurements were carried out using molded HD6 plates, according to the following protocol.

[0142] Next, the product under study is sampled and deposited in 16 spots onto the Helioscreen HD6 PMMA molded plate (5 x 5 cm). The weighed quantity is 32.5 mg, corresponding to a concentration of 1.3 mg / cm². The sample is spread uniformly using a robotic spreader (HD-SPREADMASTER - Helioscreen). The plate is then left in the dark at room temperature for at least 15 minutes. The plate is placed in the measurement chamber of the Labsphère UV 2000 S spectrophotometer to perform UV absorption measurements between 290 and 400 nm. Note that one measurement actually corresponds to the average of 9 measurements (9 points on the PMMA plate are measured).

[0143] In the cases of formulas Fig. 3 to Fig. 7, the protocol is identical but SB6 sandblasted plates were used. For these plates, the weighed quantity is 30 mg, which corresponds to a concentration of 1.2 mg / cm².

[0144] The theoretical SPF values ​​were calculated for individual filters, as in vitro SPF cannot be measured under these conditions. The BASF simulator was used for these measurements (Herzog et al. 2003).

[0145] The following formulas were developed and tested:

[0146] [Tables4] Ingrédients (dénomination INCI) Pourcentage (%) Fiel Fie 2 Water 52,70 48,70 Diethylamino hydroxybenzoyl hexyl benzoate (filtre UVA) 10,00 10,00 Bis-ethylhexyloxyphenol methoxyphenyl triazine (filtre à large spectre) 3,50 3,50 Diethylhexyl butamido triazone (filtre à large spectre) - 4,00 Methoxyphenylimino dimethylcy-clohexene glycine (MAA selon l’invention) 1,00 1,00 Hexyl laurate 10,00 10,00 Propanediol 5,00 5,00 Cl2-15 alkyl benzoate 4,00 4,00 Dicaprylyl carbonate 3,9988 3,9988 Polyglyceryl-6 stéarate 2,2875 2,2875 Glycerin 2,00 2,00 Microcrystalline cellulose 1,32 1,32 1,2-hexanediol 1,25 1,25 C20-22 alkyl phosphate 1,10 1,10 C20-22 alcohols 0,90 0,90 Caprylyl glycol 0,25 0,25 Polyglyceryl-6 behenate 0,2125 0,2125 Sodium citrate 0,20 0,20 Cellulose gum 0,18 0,18 Sodium hydroxide 0,06 0,06 Xanthan gum 0,04 0,04 Tocopherol 0,0012 0,0012

[0147] Tableau 4: Formules comparatives contenant des filtres à large spectre et UVA 30

[0148] [Tableaux5]Ingrédients (dénomination INCI) Pourcentage (%) Fie 3 Fie 4 Fie 5 Fie 6 Fie 7 Aqua 58,948 66,948 57,948 66,948 57,948 Homosalate (filtre solaire UVB) 9,00 - 9,00 - 9,00 Ethylhexyl salicylate (filtre solaire UVB) 4,50 4,50 4,50 4,50 4,50 Butyl methoxydiben-zoylmethane (filtre solaire UVA) 4,50 4,50 4,50 4,50 4,50 methoxyphenylimino di-methylhexahydro benzo-thiazine carboxylic acid (MAA selon l’invention) - - - 1,00 1,00 methoxyphenylimino di-methylcyclohexene glycine (MAA selon l’invention) - 1,00 1,00 1,00 1,00 Ethylhexyl me-thoxycrylene 6,30 6,30 6,30 6,30 6,30 Glycerin 5,00 5,00 5,00 5,00 5,00 Dibutyl adipate 5,00 5,00 5,00 5,00 5,00 Potassium cetyl phosphate 3,00 3,00 3,00 3,00 3,00 Sodium stearoyl glutamate 1,00 1,00 1,00 1,00 1,00 Cetearyl alcohol 0,80 0,80 0,80 0,80 0,80 Pentylene glycol 0,50 0,50 0,50 0,50 0,50 Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer 0,396 0,396 0,396 0,396 0,396 Citric acid 0,302 0,302 0,302 0,302 0,302 Caprylyl glycol 0,25 0,25 0,25 0,25 0.25 1,2-hexanediol 0.25 0.25 0.25 0.25 0.25, Xanthan gum 0.20 0.20 0.20 0.20 0.20 Sorbitan isostearate 0.027 0.027 0.027 0.027 0.027 Polysorbate 60 0.027 0.027 0.027 0.027 0.027

[0149] Table 5: Comparative formulas containing UVB and UVA filters IV-3 Results and discussion

[0150] The SPF (sun protection factor) conferred by the different filters was measured:

[0151] [Tableauxô] Formula Number of plates Average SPF Standard deviation Expected theoretical SPF for the 4.00% diethylhexyl butamido triazone broad-spectrum filter - 7.5 - Fie 1 3 5.3 0.17 Fie 2 3 21.01 1.01

[0152] Table 6: SPF measurements of figures 1 and 2

[0153] [Tables?] Formula Number of plates Average SPF Standard deviation Expected theoretical SPF for the 9% homosalate UVB filter - 4.6 - Fie 3 3 18.62 0.64 Fie 4 3 12.5 0.54 Fie 5 3 24.11 1.49 Fie 6 3 11.73 1.57 Fie 7 3 25.93 1.40

[0154] Table 7: SPF measurements from figures 3 to 7

[0155] In the case of tests relating to broad spectrum filters + UVA filter, a very low SPF was obtained for formula 1 (fig 1) containing an MAA according to the invention (INCI: Methoxyphenylimino dimethylcyclohexene glycine), a UVA filter and a broad spectrum filter.

[0156] The addition of a second broad spectrum filter made it possible to go from an SPF value of 5 to an SPF value of 21, whereas the theoretical expected contribution for the broad spectrum filter was 7.5.

[0157] For the tests relating to UVB +UVA filters, the addition of a UVB filter in formula 4, containing an MAA according to the invention (INCI: methoxyphenylimino dimethylcyclohexene glycine), makes it possible to increase the SPF value from 12.5 to an SPF value of 24.11. The addition of the same filter in the same concentration in formula 6, containing another MAA according to the invention (INCI: methoxyphenylimino dimethyl-hexahydro benzothiazine carboxylic acid) makes it possible to increase the SPF value from 11.73 to an SPF value of 25.93.

[0158] The expected theoretical contribution for the 9% homosalate UVB filter was 4.6.

[0159] The comparison between tests 3 and 5, which differ only in the presence of a MAA according to the invention, validates the solar protection amplifier function of MAA (SPF 18.62 ->24.11).

[0160] In conclusion, the combinations of filters and MAAs according to the invention make it possible to obtain products characterized by a good protection index (SPF > 20), while limiting the introduction of organic filters in the formulas thanks to the sun protection amplifier action of the MAAs.

[0161] Thus, the present invention makes it possible to reduce the quantity and concentration of organic filters required in a sunscreen product, while maintaining a high sun protection factor, i.e., greater than 20. The use of MAAs as a UV blocker, in combination with organic filters, is an eco-friendly, environmentally responsible, and safe solution for humans. References

[0162] Axelstad M., Boberg J., Hougaard K.S., Christiansen S., Jacobsen P.R., Mandrup K.R., Nellemann C., Lund S.P., Hass U. Effects of pre- and postnatal exposure to the UV-filter octyl methoxycinnamate (OMC) on the reproductive, auditory and neu-rological development of rat offspring. Toxicol. Appl. Pharmacol. 250 : 278-90 (2011).

[0163] Danovaro R., Bongiorni L., Corinaldesi C., Giovannelli D., Damiani E., Astolfi P., Greci L. Pusceddu A. (2008) Sunscreens cause coral bleaching by promoting viral infections. Environ Health Perspectll6(4):441-447.

[0164] Herzog, B., Mendrok, C. & Mongiat, S., Millier, S, Osterwalder, U. (2003). The Sunscreen Simulator: A Formulator’s Tool to Predict SPF and UVA Parameters. SOFW Journal. 129: 25.

[0165] Kinnberg K.L., Petersen G.I., Albrektsen M., Minghlani M., Awad S.M., Holbech B.F., Green J.W., Bjerregaard P., Holbech H.. Endocrine-disrupting effect of the ultraviolet filter benzophenone-3 in zebrafish, Danio rerio. Environ. Toxicol. Chem. 34 : 2833-40 (2015).

[0166] Ozâez, I., Morcillo, G., Martlnez-Guitarte, J.L. Ultraviolet filters differentially impact the expression of key endocrine and stress genes in embryos and larvae of Chironomus riparius. Sci. Total Environ. 557-558 : 240-247 (2016).

[0167] Petersen, G., Rasmussen, D., Gustavson, K. Study on enhancing the Endocrine Disrupter priority list with a focus on low production volume Chemicals Study on enhancing the Endocrine. Revised report to European Commission / DG Environment (2007).

[0168] Rehfeld A., et al. Organic Ultraviolet Filters Mimic the Action of Progestérone on Human Sperm and Interfère with Sperm Functions. FRI 105-133-Endocrine Disrupting Chemicals and Gene Régulation and Development (posters) (2016).

[0169] Schlumpf M., Cotton B., Conscience M., Haller V., Steinmann B., Lichtensteiger W. In vitro and in vivo estrogenicity of UV screens. Environ. Health Perspect. 109 : 239-44 (2001).

[0170] Schlumpf M., Durrer S., Faass O., Ehnes C., Fuetsch M., Gaille C., Henseler M., Hofkamp L., Maerkel K., Reolon S., Timms B., Tresguerres J.A., Lichtensteiger W. Developmental toxicity of UV filters and environmental exposure: a review. Int J Androl. 31 : 144-51 (2008).

[0171] Szwarcfarb B., Carbone S., Reynoso R., Bollero G., Ponzo O., Moguilevsky J., Scacchi P. Octyl-Methoxycinnamate (OMC), an Ultraviolet (UV) Filter, Alters LHRH and Amino Acid Neurotransmitters Release from Hypothalamus of Immature Rats. Exp. Clin. Endocrinol. DiahelesHb : 94-98 (2008).

[0172] Zucchi, S., Blüthgen, N., leronimo, A., Fent, K. The UV-absorber benzophenone-4 alters transcripts of genes involved in hormonal pathways in zebrafish (Danio rerio) eleuthero-embryos and adult males. Toxicol. Appl. Pharmacol. 250 : 137-46 (2011).

Claims

1. Claims Composition comprising: -at least one amino acid analogue of mycosporin called “MAA” chosen from the group consisting of molecules A of formula IA or one of its acceptable salts, and where appropriate, the group consisting of molecules B of formula IB or one of its acceptable salts, said formula IA being: Formula IA: [Chem. 2] said formula IB being: Formula IB: [Chem. 3] for each of the IA and IB formulas, - RI is hydrogen; alkyl; alkenyl; alkynyl; aryl; heterocycle; cycloalkyl; alkoxy; alkanoyl; hydroxyl; a sulfo group; a halogeno group; a phosphono group; an ester group; a carboxylic acid group; a phenyl group; an amino group; an alkylated fatty acid chain or a polyether; - R2 is alkyl; alkenyl; alkynyl; aryl; heterocycle; cycloalkyl; alkoxy; alkanoyl; a sulfo group; a phosphono group; an ester group; a carboxylic acid group; hydroxyl; or a phenyl group characterized in that it further comprises: - at least two organic filters chosen from organic UVB filters and / or broad spectrum organic filters; - at least one organic UVA filter.

2. Composition according to claim 1, characterized in that RI is an alkoxy group of the type [CH3]-[CH2]nO-, where “n” is between 0 and 10, preferably “n” 0 or “n” = 8.

3. Composition according to any one of the preceding claims, characterized in that R2 is a carboxylic acid group of the type [COOH]-[CH2]n-, where “n” is between 0 and 5, preferably “n”=1 or “n”=0.

4. Composition according to any one of the preceding claims, characterized in that said at least one MAA is chosen from the group comprising the following INCI designations: methoxyphenylimino di-methylcyclohexene glycine, caprylyloxyphenylamino dimethylte-trahydro benzothiazine carboxylic acid and methoxyphenylimino dime-thylhexahydro benzothiazine carboxylic acid.

5. Composition according to any one of the preceding claims, characterized in that said at least one organic UVA filter is chosen from the group comprising the compounds corresponding to the following INCI designations: butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, bis-(diethylaminohydroxybenzoyl benzoyl) piperazine, disodium phenyl dibenzimidazole tetrasulfonate, in particular butyl methoxydibenzoylmethane and diethylamino hydroxybenzoyl hexyl benzoate.

6. Composition according to any one of the preceding claims, characterized in that said at least one organic UVB filter is chosen from the group comprising the compounds corresponding to the following INCI designations: ethylhexyl salicylate, homosalate, phenylbenzimidazole sulfonic acid and ethylhexyl triazone.

7. Composition according to any one of the preceding claims, characterized in that said at least one broad-spectrum organic filter is chosen from the group comprising bis ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, tris-biphenyl triazine, phenylene bis-diphenyltriazine, methylene bis-benzotriazolyl tetramethylbutylphenol and drometrizole trisiloxane, in particular bis ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, tris-biphenyl triazine, methylene bis-benzotriazolyl tetramethylbutylphenol.

8. Composition according to any one of the preceding claims, characterized in that said at least one MAA represents between 0.1% and 20% by mass relative to the total mass of the composition, preferably between 0.5% and 10%, even more advantageously between 1 and 2%.

9. Composition according to any one of the preceding claims, characterized in that said at least one organic UVB filter represents between 1% and 20% by mass relative to the total mass of the composition, preferably between 2% and 15%.

10. Composition according to any one of the preceding claims, characterized in that said at least one organic UVA filter represents between 1% and 10% by mass relative to the total mass of the composition, preferably between 2% and 7%.

11. Composition according to any one of the preceding claims, characterized in that said at least one broad-spectrum organic filter represents between 1% and 15% by mass relative to the total mass of the composition, preferably between 2% and 10%.

12. Composition according to any one of the preceding claims, characterized in that it comprises - at least two organic UVB filters; - at least one organic UVA filter.

13. Composition according to any one of the preceding claims, characterized in that it comprises: - at least two broad-spectrum organic filters; - at least one organic UVA filter.

14. Composition according to any one of the preceding claims, characterized in that it comprises: - at least the UVB filters corresponding to the following INCI designations: octyl salicylate and homosalate; - at least the organic UVA filter corresponding to the following INCI designation: butyl methoxydibenzoylmethane.

15. Composition according to any one of the preceding claims, characterized in that it comprises: -at least the broad-spectrum filters corresponding to the following INCI designations: diethylhexyl butamido triazone and bis-ethylhexyloxyphenol methoxyphenyl triazine; -at least one UVA sun filter chosen from the group comprising the compounds corresponding to the following INCI designations: butyl me- thoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, bis-(diethylaminohydroxybenzoyl benzoyl) piperazine, disodium phenyl dibenzimidazole tetrasulfonate, in particular butyl methoxydiben-zoylmethane and diethylamino hydroxybenzoyl hexyl benzoate, advantageously butyl methoxydibenzoylmethane and diethylamino hydroxybenzoyl hexyl benzoate.

16. Composition according to any one of the preceding claims, characterized in that it is free from sunscreens corresponding to the following INCI designations: 4-methylbenzylidene camphor, 3-methylbenzylidene camphor, benzophenone-2, benzophenone-3, benzophenone-4, ethylhexyl methoxycinnamate, isoamyl methoxy-cinnamate, octocrylene, octyl dimethyl PABA.

17. Composition according to any one of the preceding claims, characterized in that it has a sun protection factor known as “SPF” equal to or greater than 20, advantageously equal to or greater than 30, preferably equal to or greater than 40, or even equal to or greater than 50.

18. Composition according to any one of the preceding claims, for its use for protection against solar radiation, in particular with a wavelength between 100 and 400 nm.