Composition comprising a novel UV filter combination

Abstract

The invention relates to a sunscreen composition comprising (i) at least 0.1 wt.% of a compound according to formula (Ia) or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, based on the total weight of the composition; and (ii) (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate), wherein the composition is free of 4-(tert.-butyl)-4'-methoxydibenzoylmethane (INCI butyl methoxydibenzoylmethane).

Description

[0001] Composition comprising a novel UV filter combination

[0002] Field of the invention

[0003] The present invention relates to a composition comprising a novel UV filter combination.

[0004] Background of the invention

[0005] UV radiation causes harmful effects on the human skin. Beside the acute effect of sunburn of the skin, UV radiation is also known to increase the risk of skin cancer. Furthermore, long time exposure to UV-A and UV-B light can cause phototoxic and photo allergenic reactions on the skin and can accelerate skin aging. In addition, UV radiation can impact the stability of active ingredients in different types of products.

[0006] To protect the human skin from UV radiation, various sun protecting UV filters (also referred to as UV absorbers) exist including UV-A filter, UV-B filter, and broadband filters. These filters are added to sunscreen or photoprotective daily care compositions. The UV filters are either organic or inorganic, particulate or non-particulate compounds, of which all have an absorption efficacy in the UV-light range. In general, the UV light relevant for suncare can be divided into UV-A radiation (320 to 400 nm) and UV-B radiation (290 to 320 nm). The UV-A range can be further divided into a UVA1 range (340 to 400 nm) and a UVA2 range (320 to 340 nm). Depending on the position of the absorption maxima, UV filters are divided into UV-A and UV-B filters. In case a UV filter absorbs both, UV-A and UV-B light, it is referred to as a broadband UV filter (broadband UV absorber). Some of these UV filters can also be used to protect active ingredients in different types of products.

[0007] Almost all of the UV filters currently on the market are synthetically derived from fossil resources and show low levels of biodegradability. However, increasing sustainability requirements regarding the biodegradability of components of cosmetic compositions including sunscreens as well as the need to move away from fossil resources for material sourcing have led to the development of some new, bio-based UV filters.

[0008] Among the most promising members of this new class of UV filters are mycosporine-like amino acids (MAAs) such as Shinorine (see Fig. 1). MAAs are biodegradable natural products that have been found to provide good protection against UV-induced skin damage (V. Geraldes et al. Mycosporine-Like Amino Acids (MAAs): Biology, Chemistry and Identification Features. Pharmaceuticals, 2021, 14(1), 63; A. Singh et al. Exploring Mycosporine-Like Amino Acids (MAAs) as Safe and Natural Protective Agents against UV-lnduced Skin Damage. Antioxidants, 2021, 10(5), 683).

[0009]

[0010] Fig. 1: Chemical structure of L-Serine, N-[3-[(carboxymethyl)amino]-5-hydroxy-5- (hydroxymethyl)-2-methoxy-2-cyclohexen-l-ylidene]; Shinorine (compound of formula (la))

[0011] Shinorine absorbs UV light effectively in the UVA2 range with a A (max) at 334 nm at pH 7 with a El,l (extinction 1% filter at an optical thickness of 1 cm) of more than 1200. To provide protection over the entire harmful UV irradiation spectrum, a composition must comprise further UV filters.

[0012] WO 02 / 39974 Al describes personal care compositions comprising (i) sunscreening compounds which are mycosporine-like amino acids (MAAs) of a certain structure and (ii) an additional inorganic or organic sunscreening agent.

[0013] WO 2024 / 027926 Al refers to sunscreen products, cosmetic or pharmaceutical preparations or homecare products comprising a photo-unstable UV-filter and as stabilizer therefore a certain mycosporine-like amino acid compound.

[0014] However, there remains a need to develop sunscreen compositions comprising biodegradable UV filters such as MAAs in combination with other UV filters to cover the entire harmful UV irradiation spectrum. Since Shinorine only absorbs in the UVA2 range, it must be combined with a UV-B filter to provide protection from UV irradiation over the entire relevant UV light spectrum. Unfortunately, however, it was discovered that Shinorine itself is unstable when combined with certain other UV filters.

[0015] Furthermore, there is a need to develop optimal UV protection systems for protecting active and / or photo-unstable ingredients from the impact of UV irradiation in different types of products, e.g. cosmetic compositions, cleaning compositions, and agrochemical compositions. Summary of the invention

[0016] It is therefore an object of the present invention to provide a composition that provides good UV coverage over the entire relevant UV radiation range.

[0017] It is another object of the present invention to provide such a coverage by using a biodegradable MAA as one of the UV filters.

[0018] It is a further object of the present invention to provide a composition with a UV filter combination with increased biodegradability.

[0019] Another object of the invention is to provide a composition with good photostability. It is also an object of the present invention to provide a photoprotective composition with good ecological properties.

[0020] According to a first aspect, the invention relates to a sunscreen composition comprising

[0021] (i) at least 0.1 wt.% of a compound according to formula (la)

[0022] U u' 'MU

[0023] .-I \ .1. \ J. or a salt, hydrate, stereoisomer, tautomer, or N-oxide thereof, based on the total weight of the composition, and

[0024] (ii) (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate), wherein the composition is free of 4-(tert.-butyl)-4’-methoxydibenzoylmethane (INCI butyl methoxydibenzoylmethane).

[0025] The combination of (i) a compound of formula (la) or a salt, hydrate, stereoisomer, tautomer, or N-oxide thereof and (ii) (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop- 2-enoate (INCI ethylhexyl methoxycinnamate) provides excellent UV protection.

[0026] Ethylhexyl methoxycinnamate is compatible with the compound of formula (la) or a salt, hydrate, stereoisomer, tautomer, or N-oxide thereof and does not negatively impact the photostability of the compound of formula (la). At the same time, the Shinorine compound of formula (la) is able to protect ethylhexyl methoxycinnamate at least partially from photodegradation. Therefore, the combination of a compound of formula (la), or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof with ethylhexyl methoxycinnamate provides a composition with excellent photostability and broad UV protection.

[0027] This was a surprising finding since the combination of the compound of formula (la) or a salt, hydrate, stereoisomer, tautomer, or N-oxide thereof with another common UV-B filter, 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI octocrylene), leads to the photodegradation of the compound of formula (la). Similarly, the combination of the compound of formula (la) with butyl methoxydibenzoylmethane (BMDBM) results in a photodegradation of the compound of formula (la). The mechanism of action is unclear. However, it was surprisingly found that the degradation of the MAA of formula (la) does not take place when ethylhexyl methoxycinnamate (abbreviation: EHMC) is used as UV-B filter.

[0028] An additional advantage of the composition of the present invention is the biodegradability of the UV filter combination. The two components (i) and (ii) in the composition of the present invention both exhibit a high biodegradability compared to other UV filters.

[0029] The present invention will be described with respect to particular embodiments and with reference to certain examples, but the invention is not limited thereto, and it is only defined by the appending claims.

[0030] Definitions

[0031] As used in this specification and in the appended claims, the singular forms of "a" and "an" also include the respective plurals unless the context clearly dictates otherwise.

[0032] In the context of the present invention, the terms "about" and "approximately" denote an interval of accuracy that a person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indicates a deviation from the indicated numerical value of ± 20 %, preferably ± 15 %, more preferably ± 10 %, and even more preferably ± 5 %.

[0033] It is to be understood that the term "comprising" is not limiting. For the purposes of the present invention the term "consisting of" is considered to be a preferred embodiment of the term "comprising of". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only.

[0034] Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.

[0035] As used herein the term “does not comprise” or “free of” means in the context that the composition of the present invention is free of a specific compound or group of compounds, which may be combined under a collective term, that the composition does not comprise said compound or group of compounds in an amount of more than 0.1 % by weight, based on the total weight of the composition. Furthermore, it is preferred that the composition according to the present invention does not comprise said compounds or group of compounds in an amount of more than 0.05 % by weight, preferably the composition does not comprise said compounds or group of compounds at all. Furthermore, it is to be understood that the term “free of” or “does not comprise”, in case the composition does not comprise a compound X and a compound Y means that the compositions must be free of both compounds X and Y. In other words, the composition may not contain any compound selected from X and Y.

[0036] When referring to compositions and the weight percent of the therein comprised ingredients it is to be understood that according to the present invention the overall amount of ingredients does not exceed 100% (± 0.1% due to rounding). If numerical values are given without any digits, the respective value comprises the range that arises from normal rounding. For example, a value of 10 thus comprises the range of from 9.5 to 10.4. The same applies if digits are given with respect to the next digit. For example, a value of 0.5 thus covers the range of from 0.45 to 0.54.

[0037] It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention that will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.

[0038] The term “sunscreen composition” refers to any topical product, which absorb and further may reflect certain parts of UV radiation. Thus, the term “sunscreen composition” is to be understood as not only including sunscreen compositions, but also any cosmetic compositions that provide UV protection. The term “topical product” refers to a product that is applied to the skin and can refer, e.g., to sprays, lotions, creams, oils, or gels, sticks, foams. The sunscreen composition may comprise one or more active agents, e.g., organic, or inorganic UV filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, sensory enhancers, humectants, film formers, UV scattering compounds, UV boosters, pH adjusters, preservatives, fragrances or adjuvants such as anti-aging actives, vitamins, antioxidants, moisturizers, chelating agents.

[0039] A sunscreen composition of the present invention may inter alia be formulated as a water-in oil (W / O) or an oil-in-water (O / W) dispersion, or an oil or oil-alcohol mixture, bi-phasic formulations, lipophilic gel, hydrophilic gel, or a vesicular dispersion of an ionic or nonionic amphiphilic lipid, or a gel, or a solid stick, or an aerosol formulation.

[0040] The term “UV filter” or “ultraviolet filter” (also referred to as UV absorbers) as used herein refers to organic or inorganic compounds, which can absorb and may further reflect and scatter UV radiation caused by sunlight. UV filter can be classified based on their UV absorbance profile as UV-A, UV-B, or broadband filters. Preferably, the term “UV filter” comprises or consists of any UV filter as defined in the Annex VI (version of 11.11.2022) of the Regulation (EC) No 1223 / 2009 of the European Parliament and of the Council.

[0041] The term “compound of formula (la)” comprises the compound(s) as defined herein as well as a salt, hydrate, stereoisomer, tautomer or N-oxide thereof.

[0042] Depending on the substitution pattern, the compounds according to the invention may have one or more centers of chirality. The invention provides both the single pure enantiomers or pure diastereomers of the compounds according to the invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds according to the invention or their mixtures. Suitable compounds according to the invention also include all possible geometrical stereoisomers (cis / trans isomers or E / Z isomers) and mixtures thereof. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis / trans isomers). The present invention relates to every possible stereoisomer of the compound of formula (la), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof. The compound of formula (la) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to amorphous and crystalline compound of formula (la), mixtures of different crystalline states of the respective compound of formula (la), as well as amorphous or crystalline salts thereof.

[0043] Salts of the compounds of the formula (la) may be pharmaceutically acceptable salts, such as those containing counterions present in drug products listed in the US FDA Orange Book database. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (la) has a basic functionality.

[0044] Suitable anionic counterions are in particular chloride, bromide, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4- alkanoic acids, preferably formate, acetate, trifluoroacetate, propionate and butyrate, furthermore lactate, gluconate, and the anions of poly acids such as succinate, oxalate, maleate, fumarate, malate, tartrate and citrate, furthermore sulfonate anions such as besylate (benzenesulfonate), tosylate (p-toluenesulfonate), napsylate (naphthalene-2- sulfonate), mesylate (methanesulfonate), esylate (ethanesulfonate), and ethanedisulfonate. They can be formed by reacting compounds according to the invention that have a basic functionality with an acid of the corresponding anion.

[0045] The term “hydrate” in connection with the compound of formula (la) refers to a compound of formula (la), which incorporates water molecules in the crystalline structure but does not alter the chemical structure of formula (la). Preferably, the compound of formula (la) (Shinorine) is used as hydrate.

[0046] Tautomers may be formed, if a substituent is present at the compound of formula (la), which allows for the formation of tautomers such as keto-enol tautomers or the like. The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.

[0047] The term "alkyl" as used herein denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2 methylbutyl, 3 methylbutyl, 2,2- dimethylpropyl, 1 ethylpropyl, 1, 1 -d imethy I propyl , and 1,2-dimethylpropyl. Methyl, ethyl, n-propyl, iso-propyl, and iso-butyl are particularly preferred.

[0048] The term “alkenyl” as used herein denotes in each case an unsaturated hydrocarbon group having usually 2 to 6, preferably 2 to 4 carbon atoms comprising at least one carbon-carbon double bond in any position, e.g. vinyl (ethenyl), allyl (2-propen-l-yl), 1- propen-l-yl, 2 propen-2-yl, methallyl (2-methylprop-2-en-l-yl), 2-buten-l-yl, 3-buten- 1-yl, 2-penten-l-yl, 3-penten-l-yl, 4-penten-l-yl, l-methylbut-2-en-l-yl, 2-ethylprop-2- en-l-yl and the like. If geometric isomers are possible with regard to the double bond, the present invention relates to both, the E- and Z-isomers. The bonding of vinyl is exemplified below:

[0049] The term “heterocyclyl” or “heterocyclic ring” as used herein includes, unless otherwise indicated, in general a 3- to 9-membered, preferably a 4- to 8-membered or 5- to 7- membered, more preferably 5- or 6-membered, in particular 5-membered monocyclic ring. The heterocycle is saturated, wherein saturated means that only single bonds are present. The heterocycle typically comprises one or more, e.g. 1, 2, 3, or 4, preferably 1, 2, or 3 heteroatoms selected from N, 0 and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. The remaining ring members are carbon atoms. The saturated heterocycle as used herein comprises at least one nitrogen atom, namely the nitrogen atom to which R2 and R3 are attached. Preferably, in addition to said nitrogen atom to which R2 and R3 are attached, the saturated heterocycle comprises 0, 1, or 2, preferably 0 or 1, more preferably 0 heteroatoms selected from N, 0 and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. The skilled person is aware that S, SO or SO2is to be understood as follows:

[0050] Further, a skilled person is aware that resonance structures of the oxidized forms may be possible. Examples of saturated heterocycles include pyrrolidine, pyrrolidinone, morpholine, thiomorpholine, piperidine or piperazine. The component (ii) of the composition of the present invention is (RS)-2-ethylhexyl- (2E)-3-(4-methoxyphenyl)prop-2-enoate. Alternative names for the same compound are ethylhexyl methoxycinnamate (INCI name) and the abbreviations EHMC or CMC. A product name of EHMC is Uvinul® MC80. All these names are used interchangeably in the present invention.

[0051] Water soluble UV filters have a solubility in water of at least 2 % by weight, preferably at least 3 % by weight, more preferably at least 5 % by weight.

[0052] Oil soluble filters have a solubility in specific emollients of at least 2 % by weight, preferably at least 3 % by weight, more preferably at least 5 % by weight.

[0053] The term “emollient” relates to cosmetic specific oils used for protecting, moisturizing and lubricating the skin. The word emollient is derived from the Latin word mol lire, to soften. In general, emollients prevent evaporation of water from the skin by forming an occlusive coating. Alternatively, or additionally, the emollients improve the distribution of the product on the skin. Emollients can be divided into different groups depending on their polarity index.

[0054] The term “sun protection factor (SPF)" as used herein indicates how well the skin is protected by a sunscreen composition from an erythema (sunburn) induced mainly from UV-B radiation. In particular, the factor indicates how much longer the protected skin may be exposed to the sun without getting a sunburn in comparison to untreated skin. For example, if a sunscreen composition with an SPF of 15 is evenly applied to the skin of a person usually getting a sunburn after 10 minutes in the sun, the sunscreen allows the skilled person to stay in the sun 15 times longer. In other words, SPF 15 means that 1 / 15 of the burning UV radiation will reach the skin, assuming sunscreen is applied evenly at a thick dosage of 2 milligrams per square centimeter (mg / cm2).

[0055] The definition of “broadband” protection (also referred to as broad-spectrum or broad protection) may be based for example on the “critical wavelength” or the UVA-PF. For broadband coverage, UV-B and UV-A protection must be provided. According to the US requirements, a critical wavelength of at least 370 nm is required for achieving broadspectrum protection. Furthermore, it is recommended by the European Commission that all sunscreens or cosmetic compositions should have an UV-A protection factor, which is at least one third of the labelled sun protection factor (SPF), e.g. if the sunscreen composition has an SPF of 30 the UVA protection factor has to be at least 10. The term “critical wavelength” is defined as the wavelength at which the area under the UV protection curve (% protection versus wavelength) represents 90 % of the total area under the curve in the UV region (290-400 nm). For example, a critical wavelength of 370 nm indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 290-320 nm, but extends to 370 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at minimum at 370 nm.

[0056] The term “administration” refers to the application of a composition to the skin of a person.

[0057] Particular embodiments of the invention

[0058] The first aspect of the invention relates to a sunscreen composition comprising

[0059] (i) at least 0.1 wt.% of a compound according to formula (la) or a salt, hydrate, stereoisomer, tautomer, or N-oxide thereof, based on the total weight of the composition, and

[0060] (ii) (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate), wherein the composition is free of 4-(tert.-butyl)-4’-methoxydibenzoylmethane (INCI butyl methoxydibenzoylmethane).

[0061] The sunscreen composition of the present invention exhibits good UV protection within the entire relevant UV range with a bio-based, biodegradable MAA according to the compound of formula (la) as the UVA filter. Additionally, ethylhexyl methoxycinnamate (EHMC) also exhibits a comparatively good biodegradation compared to other UV filters Therefore, the inventive composition shows an improved ecological footprint compared to alternative sunscreen compositions which are based purely on UV filters from fossil sources. Meanwhile, the inventive composition comprising the UV filter combination of the compound of formula (la) and ethylhexyl methoxycinnamate shows excellent photostability - in particular regarding EHMC which degrades under UV irradiation in the absence of the compound of formula (la).

[0062] The compound of formula (la) provides excellent UV protection in the UVA2 range. According to another preferred embodiment of the invention, the composition further comprises a UV-A filter and / or a broad-spectrum UV filter. In this manner, the composition can provide excellent UV protection across the entire harmful UV range. It is particularly preferred that the UV-A filter is selected from hexyl 2-[4- (diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-l-(sulfomethyl)-3- bicyc Io [2.2.1] hepta ny I ide ne] methyl] phenyl] methyl ide ne] -7,7 -di methyl -2 -oxo-1 - bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, l,l'-(l,4-piperazinediyl)bis[l-[2- [4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (INCI Bis- (diethylaminohydroxybenzoyl benzoyl) piperazine), 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3- methoxypropylamino)cyclohex-2-en-l-ylidene]acetate (I NCI methoxypropyl ami no cyclohexenylidene ethoxyethylcyanoacetate) and mixtures thereof.

[0063] It is particularly preferred that the composition of the invention comprises hexyl 2- [4- (diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and / or 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3-methoxypropylamino)cyclohex-2- en-l-ylidene]acetate (INCI methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate). It is more preferred that the composition of the invention comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3- methoxypropylamino)cyclohex-2-en-l-ylidene]acetate (I NCI methoxypropyl ami no cyclohexenylidene ethoxyethylcyanoacetate). The combination of these two UV filters with Shinorine allows for an optimized UV-A coverage since the three filters have distinct absorption spectra in the UV-A range which complement each other perfectly.

[0064] It is particularly preferred that the broad-spectrum UV filter is selected from 2,4-bis-{[4- (2-ethyl-hexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bisethylhexyloxyphenyl methoxyphenyl triazine), 2,2’-methylenebis[6-(27 / -l,2,3- benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] (INCI methylene bis- benzotriazolyl tetra methyl butyl phenol), 2 -(2 H- benzotriazo 1-2 -y I) -4- methyl -6- [2- methyls’ [1,3,3,3-tetramethy 1-1 -[(tri methylsilyl)oxy]-l-disiloxany I] propyl] phenol (INCI drometrizole trisiloxane), phenylene bis-diphenyltriazine, zinc oxide, and mixtures thereof. These broad-spectrum UV filters provide excellent broad-spectrum UV protection and are well suited for the combination with the UV-A filter components of the inventive composition. According to one embodiment of the invention, the composition further comprises one or more other UV-B filters. This is particularly useful for compositions that achieve high sun protection factors (SPF) of 30 or more. It is particularly preferred that the composition comprises a UV-B filter selected from 2-phenyl-lH-benzimidazole-5- sulfonic acid (INCI phenylbenzimidazole sulfonic acid), tris-biphenyl triazine, dimethicone diethyl benzalmalonate (INCI Po lysi I icon e- 15) , diethylhexyl butamido triazone, 4,4’,4”-(l,3,5-triazin-2,4,6-triyltrii mi no) tris- benzoic acid tris (2 -ethyl hexyl) ester (INCI ethylhexyl triazone), (RS)-2-ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, cerium oxide, and mixtures thereof.

[0065] Components (i) and (ii) of the inventive composition can be combined in broadly varying amounts. According to a preferred embodiment, the composition comprises the compound of formula (la) in an amount of from 0.2 to 20.0 wt.%, in particular from 0.5 to 15.0 wt.%, from 1.0 to 12.0 wt.%, from 1.5 to 10.0 wt.%, and from 3.0 to 8.0 wt.%, each based on the total weight of the composition. These amounts are particularly well- suited for applications in sunscreen compositions.

[0066] According to another preferred embodiment of the invention, the composition comprises (RS) -2 -ethy I hexy I - (2 E) -3 -(4- meth oxy phenyl) pro p-2 -enoate (INCI ethyl hexyl methoxycinnamate) in an amount of from 0.1 to 10.0 wt.%, in particular from 0.5 to 8.0 wt.% or from 1.0 to 7.0 wt.% or from 2.0 to 5.0 wt.%, each based on the total weight of the composition. These amounts are particularly well-suited for applications in sunscreen compositions.

[0067] In case the UV filters in the composition function as stabilizers to stabilize / protect active and / or photo-unstable ingredients in the composition, it is preferred that the composition comprises (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate) in an amount of from 0.001 to 1.0 wt.%, in particular from 0.01 to 0.5 wt.% or from 0.05 to 0.3 wt.%, based on the total weight of the composition.

[0068] It is particularly preferred that the weight ratio of the compound of formula (la) to (RS)- 2 -ethy I hexy I - (2 E) -3 -(4- meth oxy phenyl) pro p-2 -enoate (I NCI ethyl hexyl methoxycinnamate) is from 10:1 to 1:10, in particular from 5:1 to 1:5. The ratio is based on the amount of each component in wt.%. For example, a ratio of the compound of formula (la) to ethylhexyl methoxycinnamate (EHMC) of 5:1 would be met in a composition comprising 5.0 wt.% compound of formula (la) and 1.0 wt.% EHMC. It is further particularly preferred that the composition further comprises a compound according to formula (II) or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof. The compound of formula (II) is a side product when isolating the compound of formula (la) from natural origin - therefore its presence may be used to show that the compound of formula (la) is biobased and sourced from natural resources.

[0069] In case the compound of formula (II) is present in the inventive composition, it is preferred that the weight ratio of the compound of formula (la) to the compound of formula (II) in the composition is in the range from 100:1 to 2:1, in particular from 50:1 to 5:1 or from 25:1 to 10:1.

[0070] According to another preferred embodiment of the invention, the composition is free of all of the UV filters 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI octocrylene) and 3,3,5-trimethyl-cyclohexyl salicylate (INCI Homosalate). There is a growing concern that these UV filters may have negative health and / or environmental effects. In addition to this, at least 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI octocrylene) was discovered herein to negatively impact the stability of Shinorine. Consequently, it is preferable that the composition is free of these filters.

[0071] The inventive composition is free of 4-(tert.-butyl)-4’-methoxydibenzoylmethane (INCI butyl methoxydibenzoylmethane).

[0072] According to a preferred embodiment, the composition comprises an anhydrous solution. Anhydrous solution herein means that the anhydrous solution has a water content of less 2.0 wt.%, preferred less than 1.5 wt.%, more preferred less than 1.0 wt.%, even more preferred less than 0.5 wt.%, most preferred less than 0.1 wt.%, based on the total weight of the anhydrous solution. In a particularly preferred embodiment of the invention, the compound of formula (la) or a salt, hydrate, stereoisomer, tautomer, or N- oxide thereof is present in the anhydrous solution in the composition.

[0073] In a preferred embodiment of the present invention, the composition comprises a base, in particular selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline.

[0074] It is further preferred that the base is present in the composition in an amount of from 0.1 % to 3.0 % by weight, preferably in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the composition.

[0075] According to a particularly preferred embodiment of the invention, the composition comprises an anhydrous solution, wherein the anhydrous solution comprises (a) the compound of formula (la) or a salt, hydrate, stereoisomer, tautomer, or N-oxide thereof, and (b) a base, in particular selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline. It has been found that having the compound of formula (la) in combination with a base in an anhydrous solution within the inventive composition is particularly well suited to ensure a long shelf-life stability of the compound of formula (la).

[0076] According to one particularly preferred embodiment of the invention, the composition comprises the anhydrous solution comprising (a) the compound of formula (la) or a salt, hydrate, stereoisomer, tautomer, or N-oxide thereof, and (b) a base, and further the composition comprises a hydrous solution, wherein the anhydrous solution and the hydrous solution are not miscible. Not miscible herein means that the solubility of the anhydrous solution in the hydrous solution or vice versa of the hydrous solution in the anhydrous solution is less than 10.0 wt.%, based on the total weight of the composition, at 25 ° C.

[0077] The inventive composition preferably comprises additives, in particular selected from the group consisting of emulsifiers, emollients, viscosity regulators (thickeners), stabilizers, sensory enhancers, humectants, film formers, UV scattering compounds, UV boosters, pH adjusters, preservatives, fragrances, perfumes or adjuvants such as antiaging actives, vitamins, antioxidants, chelating agents and combinations thereof. Preferred 0 / W emulsifiers include, without limitation, glucose derivatives such as cetearyl glucoside, arachidyl glucoside, lauryl glucoside, polyglyceryl-3 methylglucose distearate, methyl glucose sesquistearate, sucrose derivative such as sucrose polystearate, sucrose palmitate, sorbitol derivatives such as polysorbate derivatives, inulin derivatives such as inulin lauryl carbamate, glycerides of fatty acids such as glyceryl stearate, glyceryl stearate SE, glyceryl stearate citrate, glumatic acid derivatives such as sodium stearoyl glutamate, sulfosuccinic acid derivatives such as disodium cetearyl sulfosuccinate, phosphoric acid derivatives such as potassium cetyl phosphate, ceteh-10 phosphate, C20-22 alkyl phopshate; fatty acid esters of polyglyceryl such as polyglyceryl-3-diisostearate, polyglyceryl-2-dipolyhydroxystearate; polyglyce ry I - 10 stearate, oxyalkenylated fatty alcohol such as ceteareth-20, steareth-21, beneheth-25, oxyalkenylated fatty acid such as PEG-100 stearate, oxyalkenylated organomodified silicone / polysiloxane / polyalkyl / polyether copolymers and derivatives, ethoxylated fatty acid soap, phospholipids based such as lecithin derivatives.

[0078] Preferred emulsifiers to form a W / O emulsion include, without limitation, glycerides of fatty acids such glyceryl oleate, sorbitan laurate, sorbitan esters such as sorbitan oleate, fatty acid esters of polyglyceryl such as polyglyceryl-3-diisostearate, polyglyceryl -2 -di poly hydroxystea rate, polyglyceryl -4 isostearate, Oxyakenylated fatty alcohol such steareth-2,

[0079] Oxyakenylated fatty acid such as PEG-30 dipolyhydroxystearate, organomodified silicone / polysiloxane / polyalkyl / polyether copolymers and derivatives such as cetyl dimethicone copolyol, cetyl PEG / PPG-10 / 1 Dimethicone, PEG-10 dimethicone.

[0080] Preferred emollients include esters of linear or branched fatty acids with linear or branched fatty alcohols such as propylheptyl caprylate, coco caprylate, isopropyl myristate, ethylhexyl palmitate, esters of aromatic carboxylic acids with linear or branched fatty alcohols such as C12-C15-alkyl benzoate, ethylhexyl benzoate, phenethyl benzoate, dicarboxylic acid esters with linear or branched alcohols such as dibutyl adipate, dicaprylyl carbonate, diisopropyl sebacate, esters of hydroxycarboxylic acids with linear or branched fatty alcohols, esters of linear or branched fatty acids with polyhydric alcohol such as butylene glycol dicaprylate / dicaprate, mono-, di-, tri-glycerides based on C6-C18fatty acids such as caprylic / capric triglycerides, coco glycerides, guerbet alcohols such as octyldodecynol, hydrocarbons such as hydrogenated polyisobutene, mineral oil, squalene, isohexadecane, ethers such as dicaprylyl ether, silicone derivatives (organomodified polysiloxanes) such as dimethylpolysiloxane, cyclic silicones.

[0081] Preferred lipophilic thickeners include, without limitation, fatty alcohols such as cetyl alcohol, cetearyl alcohol, stearyl alcohol; behenyl alcohol fatty acids such as stearic acid; palmitic acid, fatty acid esters such as myristyl stearate, pentaerythrityl distearate, cetyl palmitate; Tribehenin, dextrin palmitate, waxes such as beeswax, carnauba wax, microcrystalline wax, ceresin, ozocerite; Oryza Sativa bran Wax, sunflower wax, hydrogenated vegetable oil, hydrogenated castor oil, hydrogenated vegetable glycerides, hydrogenated castor oil / sebacic acid copolymer, silica based derivatives such as silica, silica dimethyl silylate, polyacrylates or homopolymers of reticulated acrylic acids or polyacrylamides such as carbomers, acrylate copolymers, acrylate / C10-C30-a I kyl acrylate crosspolymer, acrylate / beheneth-25 methacrylate copolymer.

[0082] Hydrophilic stabilizers / thickeners include, without limitation, natural gums such as xanthan gum, tara gum, carrageenan, guar gum, agar gum, alginates, gel Ian gum, silicate derivatives such as magnesium aluminium silicates, cellulose derivatives such as hydroxypropyl cellulose, microcrystalline cellulose, starch derivatives such as hydroxypropyl starch phosphate. polyacrylates or homopolymers of reticulated acrylic acids or polyacrylamides such as carbomers, acrylate copolymers, acrylate / C10-C30-a I kyl acrylate crosspolymer, acrylate / beheneth-25 methacrylate copolymer.

[0083] Also included may be UV protection scattering compounds. These include, without limitation: microcrystalline cellulose, calcium carbonate, hydroxyapatite, silica,

[0084] Hollow sphere such as Styrene / Acrylates Copolymer.

[0085] Also included may be UV protection booster compounds (UV boosters). These include, without limitation: benzotriazolyl dodecyl p cresol, ethylhexyl methoxycrylene, polyester-8, diethylhexyl syringylidenemalonate, trimethoxybenzylidene pentanedione, diethylhexyl 2,6-naphthalate,

[0086] Bis(Cyano Butylacetate) 10 Anthracenediylidene, polyester-25, butyloctyl salicylate.

[0087] Preferred sensory enhancers include polyamide derivatives such as nylon-12, polymethyl methacrylates, silica, mica, poly methyl si I sesquioxane, starch derivatives such as aluminum starch octenylsuccinate, dimethicone derivatives, boron nitride,

[0088] HDI / trimethylol hexyllactone crosspolymer, perlite. Preferred humectants include glycerin, butylene glycol, propylene glycol, sorbitol beta-glucan,

[0089] 1,2 pentadiol,

[0090] 1,2 hexandiol,

[0091] 1,2 octandiol,

[0092] 1,2 decandiol,

[0093] 2- Methyl- 1,3- propandiol.

[0094] Preferred adjuvants include ethanol, dyes, pigments such as iron oxides, tocopherol derivatives, retinol derivatives, ascorbic acid derivatives, bisabolol, allantoin, panthenol, chelating agents (EDTA, EDDS, EGTA, phytic acid, piroctone olamine); ethylhexyl glycerin, hydroxyacetophenone, caprylhydroxymic acid, propellants such as propane, butane, isobutene, dimethyl ether, insect repellants such as butylacetylaminopropionate.

[0095] Preferred preservatives include benzyl alcohol, zingerone.

[0096] Preferred perfumes are selected from the group consisting of limonene, citral, linalool, alpha-isomethylionon, geraniol, citronellol, 2-isobutyl-4-hydroxy-4- m ethyl tetra hydro pyrane, 2 -tert. -pentyl cyclohexyl acetate, 3-methy I -5- pheny 1-1- pentanol,

[0097] 7-acetyl-l,l,3,4,4,6-hexamethyltetraline, adipine acid diester, alpha- amylcinnamaldehyde, alpha-methylionon, amyl C butylphenylmehtylpropionalcinnamal, amylsalicylate, amylcinnamylalcohol, anisalcohol, benzoin, benzylalcohol, benzylbenzoate, benzylcinnamate, benzylsalicylate, bergamot oil, bitter orange oil, butylphenylmethylpropioal, cardamom oil, cedrol, cinnamal, cinnamylalcohol, citronnellylmethylcrotonate, lemon oil, coumarin, diethylsuccinate, ethyllinalool, eugenol, evernia furfuracea extracte, evernia prunastri extracte, farensol, guajak wood oil, hexylcinnamal, hexy leal icylate, hydroxycitronellal, lavender oil, lemon oil, linaylacetate, mandarine oil, menthyl PCA, methylheptenone, nutmeg oil, rosemary oil, sweet orange oil, terpineol, tonka bean oil, triethylcitrate, vanillin and combinations thereof.

[0098] It is preferably that the inventive composition comprises two or more of the additives described above. In connection with the above preferred embodiments, it is to be understood that if the composition comprises two or more additives, combinations of any of the additives as defined above are also part of the invention.

[0099] In connection with the above preferred and particularly preferred embodiments, it is to be understood that the composition may further comprise water.

[0100] In case water is present in the composition it is to be understood that it is preferably present in an amount of more than 5 % by weight, based on the total weight of the composition. Further, it is to be understood that in case water is present in the composition, the composition can be an oil in water emulsion (O / W emulsion), a water in oil emulsion (W / O emulsion), a bi-phasic formulation, a gel cream or an oil in gel.

[0101] In one embodiment of the present invention, the composition can be provided in different forms, e.g. gels, creams, oils, lotions, sticks, in the form of a sprayable product, or a two-phase systems in which the oil and aqueous phase are in separate compartments and mix during use of the product (e.g. application on skin).

[0102] The inventive composition is a sunscreen composition, wherein the UV filters act primarily as active agents protecting the skin and / or hair of a user from UV irradiation.

[0103] The inventive composition exhibits excellent protection in the UV-A range. According to a preferred embodiment of the invention, the composition has a UVA-PF that is at least one third of the SPF It is furthermore preferred that the composition shows a critical wavelength of at least 370 nm, thus providing excellent protection along the entire harmful UV radiation range. The UVA PF can exemplarily be determined by simulation calculation or in vivo or in vitro. Preferably, the UVA PF is determined by simulation calculation. Calculation methods to determine the UVA-PF are described, inter alia, by B. Herzog et a / , in Simulation of sunscreen performance, Pure Appi. Chem. 2015; 87(9- 10):937-951. To calculate the UVA-PF, the method based on persistent pigment darkening (PPD) action spectrum provided in the Herzog reference mentioned in this paragraph is particularly well-suited.

[0104] It is further preferred that the composition has a SPF (sun protection factor) value of minimum 6 up to 50+ (according to the EC recommendation). The SPF can exemplarily be determined by simulation calculation using BASF sunscreen simulator (https: / / sunscreensimulator.basf.com / ) or in vivo or in vitro. A suitable in vitro method may be performed as follows:

[0105] SPF in vitro determination is based on the assessment of UV-transmittance through a thin film of sunscreen sample spread on roughened substrate - SB6 PMMA-plates (4- 5pm roughness, area 4.8 x 4.8 cm) from Helioscreen, Creil, France. The sunscreen formulation to be tested was applied on the PMMA plate with an amount of 1.2mg / cm2. Three plates and 5 measurements per plate were done per formulation. The formulation was distributed manually as equal as possible on the plate. The plates applied with formulation were stored 30 minutes at room temperature and in a dark place prior the measurement.

[0106] In vitro transmission measurement were performed from 290-400 nm with 1 nm steps with the Labsphere UV Transmittance Analyzer UV 2000S. The UV transmission spectrum was acquired and the SPF in vitro values were calculated according to equation below (mean SPF of all 15 values (from the three plates and 5 measurements per plate)) where, E( A ) is the erythema action spectrum and S( ) is the spectral irradiance received from the UV source and T(A ) is the in vitro measured light transmittance.

[0107] The composition of the present invention has the advantage of having a low ecological impact, in particular due to the presence of the compound of formula (la). To further increase the biodegradability and sustainability of the inventive composition, it is preferred that the inventive composition is free of microplastic. According to a particularly preferred embodiment, the inventive composition is free of synthetic polymer. It is more preferred that the inventive composition is free of microplastic and free of synthetic polymer. The term “free of” herein means that the composition comprises less than 0.1 wt.%, preferably less than 0.001 wt.% and most preferred less than 0.0001 wt.% of microplastic or synthetic polymer, each based on the total weight of the composition.

[0108] According to one preferred embodiment, the inventive composition is free of synthetic polymer material. According to this embodiment, the composition does not contain any microplastics, synthetic thickener or any other synthetic polymer materials. The term “free of” herein means that the composition comprises less than 0.1 wt.%, preferably less than 0.001 wt.% and most preferred less than 0.0001 wt.% of synthetic polymer material, each based on the total weight of the composition.

[0109] The present invention is further illustrated by the following examples.

[0110] Examples

[0111] Methods

[0112] Photostability

[0113] The photostability of the UV filters in several formulations was tested.

[0114] To mimic a thin film of a composition on the skin, Quartz glass plates (106-QS from Hellma 0.3mm, sandblasted internal surface / polished external surface; the structure of the plates is further described in B. Herzog, L. Amorbs-Galicia, M. Sohn et a , Analysis of photokinetics of 2’-ethylhexyl-4-methoxycinnamate in sunscreens, Photochem.

[0115] Photobiol. Sci., 2019, 18(7), 1773-1781) were filled with the formulations IF.l, CF.l, CF.2, and CF.3. The plates were irradiated using Atlas CPS device. In total, four plates were prepared for each irradiation condition. Before and after different MED (minimal erythemal dose) (for skin phototype II) irradiation doses, each cuvette was rinsed off with an adequate solvent. The rinsing solution was further analyzed via HPLC to determine the recovery of the UV filters.

[0116] Determination of UVA-PF / PPD

[0117] The simulated UVA-PF in vivo values were calculated using the model published by B. Herzog et a / , in Simulation of sunscreen performance, Pure Appt. Chem. 2015; 87(9- 10):937-951 for determining the protection against UVA radiation. The specific calculation method is described in detail in said reference by B. Herzog et al. in the section on pages 946-947. It mimics the in vivo method for UVA protection based on the persistent pigment darkening (PPD). Formulations

[0118] The following sunscreen formulations were prepared in order to test the photostability of the UV filters and to determine the UVA-PF of the sunscreen formulations:

[0119] The formulations were prepared in the following way: Part A was prepared by mixing all ingredients at 80° C until complete dissolution, except for the compound of formula (la) and Na2CO3powder which were added after cooling when Part A had a temperature below 40° C. The compound of formula (la) and the Na2CO3powder remained undissolved. Part A was prepared in a bottle and stored for 3 weeks at 40 ° C.

[0120] The rest of the formulation was prepared on the day of the photostability measurement. Part B was prepared by heating water and glycerin at 70° C and dispersing xanthan gum under agitation. Part B was led to cool down to about 40-45 ° C before being introduced into the Part A bottle. The formulation was then homogenized with an Ultra turrax type device. Finally, part C was added, and the formulation was briefly homogenized again.

[0121] The photostability tests were performed on the five formulations as discussed above. The results for the recovery of the compound of formula (la) after UV light irradiation with a minimal erythema dose (MED) of 0 MED, 10 MED, and 30 MED are shown for compositions IF.l, CF.l, CF.2, and CF.4 in Table 1: Table 1: HPLC recovery of compound of formula (la) after UV light irradiation

[0122] As is apparent from the results in table 1, the amount of the compound of formula (la) (Shinorine) after irradiation with 10 MED is substantially the same for the composition IF.l comprising EHMC and Shinorine as it is for the composition CF.l comprising only Shinorine as UV filter. In contrast, the compositions CF.2 comprising Octocrylene and Shinorine and CF.4 comprising butyl methoxydibenzoylmethane (BMDBM) and Shinorine show a significant drop in the amount of Shinorine recovered already at an irradiation dose of 10 MED. At 30 MED, the inventive composition provides the same HPLC recovery of Shinorine as a composition comprising Shinorine as sole UV filter. In contrast, the composition comprising octocrylene as UV-B filter shows a significant drop in Shinorine recovered after 30 MED (72% in HPLC after 30 MED irradiation). Similarly, the composition comprising the UV-A filter butyl methooxydibenzoylmethane (BMDBM) shows a substantial drop in Shinorine after 30 MED (83% in HPLC after 30 MED irradiation).

[0123] It was further evaluated how the compound of formula (la) (Shinorine) impacts the photostability of (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate). Ethylhexyl methoxycinnamate by itself is not photostable. There is a substantial drop in the HPLC recovery for ethylhexyl methoxycinnamate (EHMC) at any irradiation rate. At 30 MED, only 31% of EHMC was recovered (see Table 3). Interestingly, in a composition in accordance with the present invention comprising Shinorine, the HPLC recovery of EHMC at 30 MED was substantially higher at 69%. Consequently, the use of Shinorine increases the photostability of EHMC in a composition. Table 3: HPLC recovery of ethylhexyl methoxycinnamate after UV light irradiation

Claims

Claims1. Sunscreen composition comprising(i) at least 0.1 wt.% of a compound according to formula (la)or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, based on the total weight of the composition, and(ii) (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate), wherein the composition is free of 4-(tert.-butyl)-4’-methoxydibenzoylmethane (INCI butyl methoxydibenzoylmethane).

2. Composition according to claim 1, wherein the composition further comprises a UV-B filter selected from 2-phenyl-lH-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), tris-biphenyl triazine, dimethicone diethyl benzalmalonate (INCI Po lysi I icon e- 15) , diethylhexyl butamido triazone, 4, 4’, 4”- (1,3,5- triazi n -2,4,6-triyltriim ino)tris-benzoic acid tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2-ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, cerium oxide, and mixtures thereof and / or wherein the composition further comprises a broad-spectrum UV filter selected from 2,4- bis-{[4- (2 -ethy I - h exy I oxy) -2 - hydroxy]-phenyl}-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bis-ethylhexyloxyphenyl meth oxy phenyl triazine), 2,2’ -methyl ene bis [6- (2 H- 1,2,3 -benzotriazo 1-2 -y I) -4- (2,4,4- trimethylpentan-2-yl)phenol] (INCI methylene bis-benzotriazolyl tetra methyl butyl phenol), 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[l,3,3,3- tetramethyl-l-[(t rim ethyl silyl) oxy] -1-disiloxanyl] propyl] phenol (I NCI drometrizole trisiloxane), phenylene bis-diphenyltriazine, zinc oxide, and mixtures thereof and / or wherein the composition further comprises a UV-A filter selected from hexyl 2- [4- (diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-l-(sulfomethyl)-3- bicyc Io [2.2.1] hepta ny I ide ne] methyl] phenyl] methyl ide ne] -7,7 -di methyl -2 -oxo-1 - bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, l,l'-(l,4-piperazinediyl)bis[l-[2- [4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (INCI Bis- (diethylaminohydroxybenzoyl benzoyl) piperazine), 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3-methoxy propy la mi no) eye Io hex-2 -en-l-y I idene] acetate (I NCI methoxypropyl ami no cyclohexenylidene ethoxyethylcyanoacetate), and mixtures thereof.

3. Composition according to one of claims 1 or 2, wherein the composition comprises the compound of formula (la) in an amount of from 0.2 to 20.0 wt.%, in particular from 0.5 to 15.0 wt.%, from 1.0 to 12.0 wt.%, from 1.5 to 10.0 wt.%, and from 3.0 to 8.0 wt.%, each based on the total weight of the composition.

4. Composition according to any one of the preceding claims, wherein the composition comprises (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate) in an amount of from 0.1 to 10.0 wt.%, in particular from 0.5 to 8.0 wt.% or from 1.0 to 7.0 wt.% or from 2.0 to 5.0 wt.%, each based on the total weight of the composition.

5. Composition according to any one of the preceding claims, wherein the weight ratio of the compound of formula (la) to (RS)-2-ethylhexyl-(2E)-3-(4- methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate) is from 10:1 to 1:10, in particular from 5:1 to 1:5.

6. Composition according to any one of the preceding claims, wherein the composition further comprises a compound according to formula (II)or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof.

7. Composition according to claim 6, wherein the weight ratio of the compound of formula (la) to the compound of formula (II) in the composition is in the range from 100:1 to 2:1, in particular from 50:1 to 5:1 or from 25:1 to 10:1.

8. Composition according to any one of the preceding claims, wherein the composition is free of all of the UV-filters 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI octocrylene) and 3,3,5-trimethyl-cyclohexyl salicylate (INCI Homosalate).

9. Composition according to any one of the preceding claims, wherein the composition comprises a base, in particular selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline.

10. Composition according to any one of the preceding claims, wherein the composition is in the form of an emulsion, in particular an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion.

11. Composition according to any one of the preceding claims, wherein the cosmetic composition has a SPF of at least 15, in particular at least 30.

12. Composition according to any one of the preceding claims, wherein the composition is free of microplastic and / or wherein the composition is free of synthetic polymer.

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