Topical compositions comprising terephthalylidene dicamphor sulfonic acid

Abstract

The present invention relates to a topical composition, comprising: (i) terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA); (ii) at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group; and (iii) at least one UV filter other than terephthalylidene dicamphor sulfonic acid selected from those disclosed herein; wherein the pH of the composition is within the range of 4.0 to 8.0. Additionally, the invention relates to the use of at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group, for improving the sensory properties of and / or reducing the generation of radicals upon UV exposure in a topical composition comprising TDSA.

Description

[0001] TOPICAL COMPOSITIONS COMPRISING TEREPHTHALYLIDENE DICAMPHOR SULFONIC ACID

[0002] Field of the invention

[0003] The present invention relates to a topical composition, comprising: (i) terephthalylidene-3,3'-dicamphor- 10, 10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA); (ii) at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group; and (iii) at least one UV filter other than terephthalylidene dicamphor sulfonic acid; wherein the pH of the composition is within the range of 4.0 to 8.0. Additionally, the invention relates to the use of at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group, for improving the sensory properties of and / or reducing the generation of radicals upon UV exposure in a topical composition comprising TDSA.

[0004] Background of the invention

[0005] To date sun care is positioned as an everyday product due to the rising education of the harmfulness of the sun as well as of indoor UV radiance. Therefore, there is generally a demand for sunscreen and daily care compositions with improved photoprotective properties.

[0006] One aspect to such an improved efficiency is a balanced protection by distributing UV filters in the oil and water phase, since without such a distribution and if only lipophilic UV filters are used, residual areas of the water phase leave the skin without UV protection after applying sunscreen compositions. Modern suncare formulations thus typically also include water-soluble UV filters.

[0007] Another aspect that plays an important role in consumer acceptance is the sensory profile of a topical compositions, such as a sunscreen or daily care composition. While the photoprotective properties are of high importance, a product can still fail at the consumer level if its sensory properties are unsatisfactory. It is thus important to provide for both, good photoprotection as well as a good sensory profile.

[0008] Accordingly, there is demand in this field for topical compositions that perform well on both accounts.

[0009] Terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA) is a known water-soluble UVA filter that has been widely used for some time. TDSA can be well combined with further water soluble and / or oil soluble and I or dispersible (particulate) UV filters in sunscreen and daily care compositions.

[0010] However, since TDSA is an acid, it is typically neutralized if formulated in a ready-to-use formulations, such as the topical compositions mentioned above. Summary of the invention

[0011] The present invention is based on the inventor’s surprising finding that the neutralizer used for neutralizing terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA) has an impact on sensory properties and photostability of topical compositions. In particular, compositions in which TDSA is neutralized with an organic pH neutralizer with at least one primary amino group, preferably tromethamine and L-arginine, have an improved sensory profile with reduced stickiness and / or squeakyness and less generation of free radicals upon UV exposure.

[0012] Additionally, compositions comprising TDSA and at least one organic pH neutralizer with at least one primary amino group can be more eco-friendly (e.g. there is no need of additional solubilizers and / or oil soluble UV filters which are under discussion can be replaced) and allow a balanced protection by using water soluble UV filters in combination with oil soluble UV filters. In the context of the present invention, a combination of the water soluble UVA filter TDSA and the oil soluble UVA-filter Uvinul A Plus (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate, DHHB) and / or BEMT is especially preferred. The use of water-soluble UV filters reduces the oil part in sun care products. Thus, the resulting products are easier to spread, show improved absorption, reduced stickiness and more silky feel.

[0013] Thus, in a first aspect, the present invention is directed to a topical composition, comprising:

[0014] (i) terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA);

[0015] (ii) at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group; and

[0016] (iii) at least one UV filter other than terephthalylidene dicamphor sulfonic acid selected from the group consisting of:

[0017] (a) at least one UVA filter, preferably selected from the group consisting of disodium phenyl dibenzimidazole tetrasulfonate (DPDT), hexyl 2-[4-(diethylamino)-2- hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate, DHHB), 1-(4-(1 ,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1 ,3-dione (INCI butyl methoxydibenzoylmethane, BMDBM), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), and combinations thereof; and / or

[0018] (b) at least one UVB filter, preferably selected from the group consisting of 4,4',4"-(1 ,3,5- triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone, EHT), 4,4'-[[6-[[4-[[(1 ,1-dimethylethyl)amino]carbonyl]phenyl]amino]-1 ,3,5- triazin-2,4-diyl]diimino]bis-benzoic acid-bis(2-ethylhexyl)ester (INCI diethylhexyl butamido triazone, DBT), phenylbenzimidazole sulfonic acid (PBSA), and combinations thereof; and / or

[0019] (c) at least one broadband UV filter, preferably selected from the group consisting of bis-ethylhexyloxyphenol methoxyphenyl triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine, BEMT), 2-(2H-benzotriazol-2-yl)-6-[(2- ethylhexyloxy)methyl]-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2- methyl-3-[1 ,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1-disiloxanyl]propyl]phenol (INCI drometrizole trisiloxane, DTS), 2,2'-methylenbis[6-(2H-benzotriazol-2-yl)-4- (1 ,1 ,3,3-tetramethylbutyl)phenol] (INCI methylene Bis-benzotriazolyl tetramethylbutylphenol, MBBT), phenylene bis-diphenyltriazine (PBDT), and combinations thereof; and / or

[0020] (d) at least one organic particulate UV filter, preferably selected from the group consisting of 2,2'-methylene bis[6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3- tetramethylbutyl)phenol] (INCI methylene bis-benzotriazolyl tetramethylbutylphenol), 2,4,6-tris(biphenyl-4-yl)-1 ,3,5-triazine (INCI trisbiphenyl triazine, TBPT), 1 ,1 ’-(1 ,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl]-methanone (INCI bis-(diethylaminohydroxybenzoyl benzoyl) piperazine), 5,6,5’,6’-tetraphenyl-3-3’-(1 ,4-phenylene)bis(1 ,2,4-triazine) (INCI phenylene bis-diphenyltriazine; PBDT), micronized 1 ,4-di(benzoxazole-2- yl)benzene and combinations thereof; and / or

[0021] (e) at least one inorganic UV filter, preferably selected from the group consisting of titanium dioxide, zinc oxide and mixtures thereof; wherein the pH of the composition is within the range of 4.0 to 8.0.

[0022] In various embodiments, the at least one organic pH neutralizer is selected from an amino acid, preferably a basic amino acid, more preferably L-lysine or L-arginine, most preferably L-arginine.

[0023] In another embodiment, the at least one organic pH neutralizer is selected from primary amino alcohols, preferably beta-amino alcohols, more preferably tris(hydroxymethyl)aminomethane (tromethamine).

[0024] In various embodiments, the amount of the at least one organic pH neutralizer is selected such that the pH of the composition is within the range of 4.0 to 8.0, preferably 5.0 to 7.5.

[0025] In various embodiments, the weight ratio of TDSA to the at least one organic pH neutralizer is in the range of 0.5:1 to 3:1 , preferably 1 :1 to 2.5:1.

[0026] In various embodiments, the TDSA is present in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1 .0 to 3.0 wt.-%, based on the total weight of the composition.

[0027] In various embodiments, the at least one organic pH neutralizer is present in an amount of about 0.2 to 10 wt.-% based on the total weight of the composition.

[0028] In various embodiments, the composition comprises the least one UV filter other than TDSA in an amount of 2 to 40 wt.-%, preferably of 5 to 35 wt.-%, more preferably of 5 to 30 wt.-%, still more preferably of 5 to 25 wt.-%, and, in particular, of 8 to 20 wt.-%, based on the total weight of the composition.

[0029] In various embodiments, the at least one UV filter other than TDSA comprises

[0030] (1) a UV filter that is solid at 25°C; and / or

[0031] (2) a UV filter that is soluble in or miscible with at least one cosmetic oil; and / or

[0032] (3) an organic UV filter; and / or

[0033] (4) a particulate UV filter.

[0034] In various embodiments, the topical composition comprising at least one UV filter selected from bisethylhexyloxyphenol methoxyphenyl triazine (BEMT), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), butyl methoxydibenzoylmethane (BMDBM), ethylhexyl triazone (EHT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), tris-biphenyl triazine (TBPT), and any combination of two or more thereof.

[0035] In various embodiments, the composition comprises DHHB, preferably in an amount of from 0.5 to 10 % by weight, more preferably 1 to 8 % by weight and more preferably 1 .5 to 5 % by weight, based on the total weight of the composition. In such embodiments, the weight ratio of TDSA to DHHB may be in the range of 5:1 to 0,5:5, preferably 3:1 to 1 :3.

[0036] In various embodiments, the composition comprises, in addition to TDSA and optionally DHHB,

[0037] (1) at least one broadband UV filter, preferably BEMT, preferably in an amount of from 0.5 to 10 % by weight, more preferably 1 to 5 % by weight and more preferably 2 to 4 % by weight, based on the total weight of the composition; and / or

[0038] (2) at least one UVB filter, preferably EHT, preferably in an amount of from 0.5 to 5 % by weight, more preferably 1 to 5 % by weight and more preferably 2 to 4 % by weight, based on the total weight of the composition; and / or

[0039] (3) at least one organic particulate UV filter, preferably MBBT or TBPT, preferably in an amount of from 0.5 to 10 % by weight, more preferably 1 to 5 % by weight and more preferably 2 to 4 % by weight, based on the total weight of the composition;

[0040] In various embodiments, the composition comprises TDSA, (1) and (2) and, optionally, also (3). In various embodiments, the composition comprises TDSA, DHHB, (1) and (2) and, optionally, also (3).

[0041] In various embodiments, the composition is free of at least one or more of parabens, triethanolamine (TEA) and organic UV filter compounds selected from the group of homomenthyl salicylate, ethylhexyl methoxycinnamate, octocrylene, and ethylhexyl salicylate. In various embodiments, it is free of at least TEA and octocrylene. In various embodiments, the composition further comprises at least one additive, preferably selected from the group consisting of cosmetic oils, emulsifiers, emollients, viscosity regulators (thickeners), buffering and pH adjustment agents (other than the organic pH neutralizer (ii)), stabilizers, sensory enhancers, humectants, film formers, UV scattering compounds, UV booster compounds, adjuvants, preservatives, perfumes, and combinations thereof.

[0042] In various embodiments, the composition

[0043] (i) comprises DHHB in a weight ratio of TDSA to DHHB in the range of 0.1 :1 to <1 :1 , preferably 0.1 :1 to <1 :1 , more preferably 0.1 :1 to 0.9:1 , even more preferably 0.2:1 to 0.8:1 or 0.3:1 to 0.8:1 ,

[0044] (ii) further comprises at least one further UV filter selected from EHMC, EHT, BMDBM and DBT,

[0045] (iii) is free of octocrylene, and

[0046] (iv) the composition is free of TEA

[0047] In still another aspect, the present invention is also directed to the use of at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group, for improving the stability of and / or the sensory properties of and / or reducing the generation of radicals upon UV exposure in a topical composition comprising TDSA, preferably a sunscreen or daily care composition comprising TDSA.

[0048] Brief description of the figures

[0049] Figure 1 shows a pairwise comparison of a composition according to invention (Inv. 4.1) and a reference formulation (Comp. 4.1) with respect to their sensory profiles.

[0050] Detailed description

[0051] Before describing preferred embodiments of the present invention in detail, definitions important for understanding the present invention are given.

[0052] 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.

[0053] 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%.

[0054] 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. Furthermore, the terms "first", "second", "third" or"(i)", "(ii)", "(iii)", "(iv)" 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.

[0055] As used herein the term “free of’ 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, means that the composition does not comprise said compound or group of compounds in an amount of more than 0.2 wt.-%, 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 0.1 wt.-%, preferably the composition does not comprise said compounds or group of compounds at all. Generally, it implies that the compound or group of compounds has not been purposively added and, if present, is for example only present as an impurity. The same definition is applied for the term “does not comprise”. 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.

[0056] 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% (± 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.

[0057] 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.

[0058] The term “topical composition” refers to any composition that can be applied to the human body, in particular on the skin. It can referto various formats and viscosities, e.g., to sprays, lotions, creams, oils, or gels, sticks, foams. Preferred embodiments are, for example sunscreen compositions or daily care compositions that provide UV protection. The topical composition may be a personal care composition, with said term generally referring to any product suitable to be applied to the human body, e.g. sunscreen compositions, bath and shower products, preparations containing fragrances and odoriferous substances, hair-care products, dentifrices, decorative preparations, and cosmetic formulations containing active ingredients.

[0059] The term “sunscreen composition” refers to any topical product, which absorbs and may further reflect and scatter 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 sunscreen composition comprises one or more active UV filtering agents, e.g., organic or inorganic UV filters, including those described herein, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, humectants, chelating agents, sensory enhancers, stabilizers, film formers, UV boosters, UV scattering compounds, pH adjusters, preservatives, moisturizers, anti-aging actives, vitamins, or fragrances / perfumes.

[0060] 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, bi-phasic formulation, lipophilic gel, hydrophilic gel, a vesicular dispersion of an ionic or nonionic amphiphilic lipid, a gel, a solid stick or an aerosol formulation.

[0061] The term “daily care composition” refers to any topical product which is intended to be used daily without or with a UV protection. In case UV protection is included, it absorbs and may further reflect and scatter certain parts of UV radiation and is used as an everyday care product for the human body, e.g., for face or body, and is, in the context of the present invention, referred to as a “daily care composition with photoprotection”. The daily care composition with photoprotection of the present invention typically comprises one or more active agents, e.g., organic and / or inorganic UV filters, including those described herein, 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, adjuvants, preservatives, or fragrances. Suitable daily care composition with photoprotection according to the present invention are, e.g., leave-on face and body care products. Suitable leave-on products for face and body are, e.g., decorative preparations (or make-up) and skin care preparations.

[0062] Suitable decorative preparations are, e.g., facial make-up in the form of day creams, day lotions or powder creams, face powder (loose or pressed), dry and moist make-up foundations, dry and moist make-up rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, rouge lip gloss, lip contour pencils, nail varnishes, and suntan lotions.

[0063] Suitable skin care preparations are, e.g., moisturizing, refining, and lifting preparations. The cited daily care compositions can be e.g. in the form of creams, ointments, pastes, foams, gels, lotions, powders, make-ups, sprays, sticks or aerosols.

[0064] Suitable bath and shower additives are, e.g., shower gels, bath-salts, bubble baths and soaps. Suitable preparations containing fragrances and odoriferous substances are in particular scents, perfumes, toilet waters and shaving lotions (aftershave preparations).

[0065] Suitable hair-care products are, e.g., shampoos for humans and animals, in particular dogs and sheep, hair conditioners, products for styling and treating hair, perming agents, hair sprays and lacquers, hair gels, hair fixatives and hair dyeing or bleaching agents.

[0066] Suitable dentifrices are, e.g., tooth creams, toothpastes, mouth-washes, mouth rinses, anti-plaque preparations and cleaning agents for dentures.

[0067] Suitable cosmetic formulations containing active ingredients are, e.g., vitamin containing preparations, vegetable extract containing preparations and antibacterial preparations.

[0068] The cited body-care products can be in the form of creams, ointments, pastes, foams, gels, lotions, powders, make-ups, sprays, sticks or aerosols.

[0069] The term “terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA) as used herein is a water-soluble UV(A) filter. It is commercially available from BASF SE under the trade name Uvinul® TS Hydro.

[0070] The term “UV-filter” as used herein refers to organic or inorganic compounds, which absorb and can additionally reflect UV radiation caused by sunlight. UV-filter can be classified based on their UV absorbance protection curve as UVA, UVB or broadband filters. Preferably, the term “UV filter” comprises or consists of any UV filter as defined in the Annex VI (version of 17 September 2024) of the Regulation (EC) No 1223 / 2009 of the European Parliament and of the Council.

[0071] The definition of “broadband” protection (also referred to as broad-spectrum or broad protection) is based, for example, on the “critical wavelength”. For broadband coverage, UVB and UVA protection must be provided. According to the US and European requirements, a critical wavelength of at least 370 nm is required for achieving broad spectrum protection. Furthermore, it is recommended in Europe by the European Commission that all sunscreens should have an UVA protection factor, which is at least one third of the 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.

[0072] The term “critical wavelength” is defined as the wavelength at which the area under the UV absorbance spectrum (% absorbance protection versus wavelength) represents 90 % of the total area under the absorbance spectrum 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 UVB, i.e. wavelengths from 290-320 nm, but extends to 370 nm in such a way that 90 % of the total area under the absorbance spectrum in the UV region are reached at 370 nm. The term “sun protection factor (SPF)” as used herein indicates how well the skin is protected by a sunscreen composition against erythema occurrence which is mainly caused by UVB 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 unprotected skin. For example, if a sunscreen composition with an SPF of 15 is evenly applied in an amount of 2mg / cm2to the skin of a person usually getting a sunburn after 10 minutes in the sun, the sunscreen allows the 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 dosage of 2 milligrams per square centimeter (mg / cm2).

[0073] The compositions further comprise at least one further UV filter different to TDSA as defined herein above.

[0074] This additional UV filter may be selected from organic and inorganic UV filters. In various embodiments, such additional UV filter is selected from inorganic UV filters. In various embodiments, it may be selected from organic UV filters. The additional UV filter may be a particulate or oil-soluble, oil miscible or water- soluble UV filter.

[0075] “Water soluble UV filters” have a solubility in water of at least 2.0 wt.-%, preferably at least 3.0 wt.-%, more preferably at least 5.0 wt.-%.

[0076] “Oil soluble” UV filters or “UV filters soluble in at least one cosmetic oil” have a solubility in common cosmetic oils, such as Ci2-Ci5-alkyl benzoate, dibutyl adipate, diisopropyl sebacate, phenethyl benzoate, coco-caprylate ( / caprate), propylheptyl caprylate, caprylic / capric triglyceride, cocoglycerides, propylene glycol dicaprylate / dicaprate, butylene glycol dicaprylate / dicaprate, triethyl citrate, isopropyl myristate, isopropyl palmitate, lauryl lactate, phenoxyethyl caprylate isopropyl lauroyl sarcosinate or dicaprylyl carbonate of at least 2 % by weight, preferably at least 5 % by weight, more preferably at least 7 % by weight.

[0077] If a UV filter is defined as being “oil-soluble” or “soluble in at least one cosmetic oil” herein, this means that it has a solubility of at least 2% by weight in any one or more of the afore-mentioned cosmetic oils, i.e. in one or more of Ci2-Ci5-alkyl benzoate, dibutyl adipate, diisopropyl sebacate, phenethyl benzoate, coco-caprylate ( / caprate), propylheptyl caprylate, caprylic / capric triglyceride, cocoglycerides, propylene glycol dicaprylate / dicaprate, butylene glycol dicaprylate / dicaprate, triethyl citrate, isopropyl myristate, isopropyl palmitate, lauryl lactate, phenoxyethyl caprylate isopropyl lauroyl sarcosinate, and dicaprylyl carbonate. In some embodiments, it may have the given solubility in all of the listed cosmetic oils.

[0078] The term insoluble, particulate organic UV filter refers to UV filters that are not soluble in water and not in cosmetic oils. This may mean that their solubility in water and the cosmetic oils mentioned above is below 2 % by weight, for example below 1 % by weight. The term “organic pH neutralizer” as used herein refers to organic alkaline compounds that are suitable to neutralize an aqueous solution of the acidic water-soluble UV(A) filter terephthalylidene-3,3'- dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA). Typically, the aqueous solution of terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA) in water has an acidic pH. Preferably, the pH neutralizer is used to increase the pH value of the aqueous solution, more prefably to a pH value of 4.0 to 8.0, in particular 5.0 to 7.5. In various embodiments, the organic pH neutralizer is specifically added with the object to neutralize the acidic TDSA to an extent that is compatible with the desired pH. Accordingly, the molar ratio of net basic groups in the organic pH neutralizer to the 2 carboxylic acid groups in the TDSA molecule can be selected accordingly. It may for example be in the range of 0.5:1 to 1 :1 . The term net basic groups relates to basic groups in the organic pH neutralizer that are available to neutralize the TDSA. For example, arginine contains two basic groups, the primary amino group and the guanidinium group, but also contains a carboxylic acid group. It thus has only one net basic group that is available to neutralize TDSA.

[0079] The inventors surprisingly found that specific pH neutralizers, in particular basic amino acids such as L- arginine or beta-amino alcohols such as tromethamine, provide improved sensory performance compared to other closely related neutralizing agents, such as triethanolamine (TEA). Further, it was surprisingly found that they reduce the generation of radicals upon UV exposure in topical compositions comprising TDSA.

[0080] The present invention provides for a topical composition, comprising:

[0081] (i) terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA);

[0082] (ii) at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group; and

[0083] (iii) at least one UV filter other than terephthalylidene dicamphor sulfonic acid selected from the group consisting of: organic UVA filters, organic UVB filters, organic broadband UV filters, organic particulate UV filters, and inorganic UV filters, preferably organic UV filters; wherein the pH of the composition is within the range of 4.0 to 8.0.

[0084] The composition preferably comprises the TDSA in an amount of about 0.2 to 10.0 wt.-%, relative to the total weight of the composition. The lower limit may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0 wt.-%, relative to the total weight of the composition. The upper limit may be 9.5%, 9.0, 8.5, 8.0, 7.5, 7.0, 6.5, 6.0, 5.5 or 5.0 wt.-%, relative to the total weight of the composition. Preferred ranges include about 0.5 to about 5.0 wt.-%, or about 0.7 to about 5.0 wt.-%, preferably about 1 .0 to about 3.0 wt.-%, relative on the total weight of the composition. Organic pH neutralizers comprised in the compositions of the invention comprise at least one primary amino group. Organic neutralizing agents that comprise secondary or tertiary amino groups, such as triethanolamine are thus not covered by this definition. In various embodiments, the organic pH neutralizer is selected from amino acids and primary amino alcohols. Preferred compounds are basic amino acids such as L-lysine or L-arginine, most preferably L-arginine, and beta-amino alcohols such as tris(hydroxymethyl)aminomethane.

[0085] In preferred embodiments, the at least one organic pH neutralizer is selected from an amino acid, preferably a basic amino acid, more preferably L-lysine or L-arginine, most preferably L-arginine.

[0086] In other preferred embodiments, the at least one organic pH neutralizer is selected from primary amino alcohols, preferably beta-aminoalcohols, more preferably tris(hydroxymethyl)aminomethane tromethamine.

[0087] In the most preferred embodiments, the organic pH neutralizing agent is L-arginine.

[0088] In various embodiments, the at least one organic pH neutralizer is present in an amount of about 0.2 to 10 wt.-%, preferably 0.3 to 5 wt.-%, more preferably 0.4 to 2.5 wt.-%, based on the total weight of the composition. In various embodiments, the amount of the neutralizer is selected such that the pH of the topical composition is within pH 4.0 to 8.0. In preferred embodiments, the pH is adjusted to pH 5.0 to 7.5. In various embodiments the organic pH neutralizer is used to at least partially neutralize the TDSA. This neutralization can be done before the neutralized TDSA is formulated into the remainder of the composition. In some embodiments, the TDSA and the neutralizer are thus combined and the combination is then subsequently added to the composition. The amount of TDSA and neutralizer may in such embodiment be selected such that the resulting pH of the combination of TDSA and neutralizer will adjust the pH of the composition to which the combination is added to the above given range.

[0089] In various embodiments, components (i) and (ii) are thus combined to form TDSA neutralized with the at least one organic pH neutralizer. Said “neutralized TDSA” (composed of (i) and (ii)) may then replace components (i) and (ii) (or, alternatively, (i) and part of (ii)) in all embodiments disclosed herein. This means that in all embodiments disclosed herein TDSA (i) and the neutralizer (ii) may be pre-combined and then mixed as neutralized TDSA with the remaining components.

[0090] In various embodiments, the weight ratio of TDSA to the at least one organic pH neutralizer is in the range of 0.5:1 to 4:1 . It is preferred that the weight ratio ofTDSA to the at least one organic pH neutralizer is in the range of 0.5:1 to 3:1 , preferably 1 :1 to 2.5:1. In various embodiments, the molar ratios of the available basic groups of the organic pH neutralizer to the acidic carboxylic acid groups of the TDSA is selected such that stoichiometrically the desired level of neutralization is achieved. This may mean a molar ratio of 0.5:1 to 1 .5:1 , typically 0.5:1 to 1 :1 or 0.6:1 to 0.9:1 . The compositions of the invention comprise at least one UV filter other than TDSA. This can be an organic or inorganic UV filter or both. The organic UV filters may be water-soluble or oil-soluble UV filters, oil miscible UV filters or may be particulate UV filters. The composition can of course comprise any combination of these types of UV filters.

[0091] In various embodiments, the at least one UV filter otherthan TDSA ofthe topical composition comprises

[0092] (1) a UV filter that is solid at 25°C; and / or

[0093] (2) a UV filter that is soluble in or miscible with at least one cosmetic oil; and / or

[0094] (3) an organic UV filter; and / or

[0095] (4) a particulate UV filter.

[0096] In various embodiments, the at least one UV filter other than TDSA is solid at 25°C and soluble in at least one cosmetic oil.

[0097] In various embodiments, the at least one UV filter other than TDSA comprises an organic UV filter.

[0098] Organic UV filters include triazine derivatives, triazole derivatives, benzotriazole derivatives, benzophenone derivatives, dibenzoylmethane derivatives, camphor derivatives, cinnamates, salicylates, benzimidazole sulfonic acid derivatives, silicone derivatives, para-amino benzoic acid (PABA) derivatives, and combinations thereof.

[0099] General examples of organic UV filters include, but are not limited to, ethylhexyl triazone (EHT), dimethyl para-aminobenzoate (ED PABA), PEG-25 PABA, ethylhexyl salicylate (EHS), iso-amyl methoxy cinnamate (IMC), phenyl benzimidazole sulfonic acid (PBSA), 4-methyl benzylidene camphor (4-MBC), butyl methoxy dibenzoylmethane (BMDBM), drometrizole trisiloxane (DTS), methylene bis- benzotriazolyl tetramethylbutylphenol (MBBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), menthyl anthranilate (MA), diethylhexyl butamido triazone (DBT), benzylidene malonate polysiloxane (BMP; polysilicone-15; PS-15), disodium phenyl dibenzimidazole tetrasulfonate (DPDT), homomethyl salicylate (HMS), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), tris biphenyl triazine (TBPT), 3,3’-(1 ,4-phenylene)bis(5,6-diphenyl-1 ,2,4-triazine) (PBDT), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), bis-(diethylaminohydroxybenzoyl benzoyl) piperazine (BDBP), and combinations thereof.

[0100] In various embodiments, the organic UV filter can be selected from the group consisting of disodium phenyl dibenzimidazole tetrasulfonate (DPDT), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), butyl methoxydibenzoylmethane (BMDBM), ethylhexyl triazone (EHT), diethylhexyl butamido triazone (DBT), phenylbenzimidazole sulfonic acid (PBSA), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), tris-biphenyl triazine (TBPT), drometrizole trisiloxane (DTS), phenylene bis-diphenyltriazine (PBDT), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), and combinations thereof. In various embodiments, the organic UV filter may comprise an UVA filter. Suitable UVA filters may be selected from the group consisting of disodium phenyl dibenzimidazole tetrasulfonate (DPDT), hexyl 2- [4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate, DHHB), 1-(4-(1 ,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1 ,3-dione (INCI butyl methoxydibenzoylmethane, BMDBM), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), and combinations thereof.

[0101] In various embodiments, the organic UV filter may comprise an UVB filter. Suitable UVB filters may be selected from the group consisting of 4,4',4"-(1 ,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2- ethylhexyl)ester (INCI ethylhexyl triazone, EHT), 4,4'-[[6-[[4-[[(1 ,1- dimethylethyl)amino]carbonyl]phenyl]amino]-1 ,3,5-triazin-2,4-diyl]diimino]bis-benzoic acid-bis(2- ethylhexyl)ester (INCI diethylhexyl butamido triazone, DBT), phenylbenzimidazole sulfonic acid (PBSA), and combinations thereof.

[0102] In various embodiments, the organic UV filter may comprise a broadband UV filter. Suitable broadband UV filters may be selected from the group consisting of bis-ethylhexyloxyphenol methoxyphenyl triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine, BEMT), 2-(2H-benzotriazol-2-yl)-6-[(2- ethylhexyloxy)methyl]-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3- tetramethyl-1-[(trimethylsilyl)oxy]-1-disiloxanyl]propyl]phenol (INCI drometrizole trisiloxane, DTS), 2,2'- methylenbis[6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol] (INCI methylene Bis- benzotriazolyl tetramethylbutylphenol, MBBT), phenylene bis-diphenyltriazine (PBDT), and combinations thereof.

[0103] In various embodiments, the organic UV filter may comprise an organic particulate UV filter, including the UVA, UVB and broadband UV filters described above in particulate form. Suitable organic particulate UV filters (i.e., insoluble, solid organic UV filters) may be selected from the group consisting of methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT; 2,2'-methylene bis[6-(2H-benzotriazol-2-yl)-4- (1 ,1 ,3,3-tetramethylbutyl)phenol]), tris-biphenyl triazine (TBPT; 2,4,6-tris(biphenyl-4-yl)-1 ,3,5-triazine), bis-(diethylaminohydroxybenzoyl benzoyl) piperazine (BDBP; 1 ,1 ’-(1 ,4-piperazinediyl)bis[1-[2-[4- (diethylamino)-2-hydroxybenzoyl]phenyl]-methanone), phenylene bis-diphenyltriazine (PBDT; 5, 6,5’, 6’- tetraphenyl-3-3’-(1 ,4-phenylene)bis(1 ,2,4-triazine)), 1 ,4-di(benzoxazole-2'-yl)benzene and combinations thereof.

[0104] Further examples of suitable organic particulate UV filters are described, e.g., in WO9703643, W02009077356, WO2015155158 and WO2019180042. Preferably, the particulate UV filters have a particle size Dn50 determined by light scattering of less than 2000 nm, preferably less than 1000 nm, more preferably less than 500 nm, wherein Dn50 refers to the particle size value, where half the number of the population lies below this value, and half the number of the population lies above this value, i.e., the median value of the particle size number distribution. The compositions of the invention may comprise at least one UV filter other than TDSA that is an inorganic UV filter. Suitable inorganic UV filters include, without limitation, titanium dioxide, zinc oxide, and mixtures thereof. In various embodiments, the inorganic UV filters may be applied as a nano material. In this connection it is to be understood that the term “nano material” follows the definition of the European Commission recommendation (2011 / 696 / EU, 2022 / C229 / 01). Accordingly, in a nano material 50 % of particles, based on a number-based size distribution, are smaller than 100 nm, including constituent particles present in aggregates or agglomerates. In another embodiment of the present invention, the inorganic UV filters may be applied as a non-nano material. Accordingly, in a non- nano material more than 50 % of the particles, based on a number-based size distribution, are larger than 100 nm. It is also possible to use mixtures of nano and non-nano inorganic UV filters. Furthermore, the inorganic UV filters may be coated or uncoated. If present, titanium dioxide is preferably coated, as uncoated titanium dioxide is photocatalytic and should be avoided in sunscreens. Coatings suitable in the context of inorganic UV filters may be organic and / or inorganic and are, for instance, disclosed in WO 2023 / 036749 A1 .

[0105] Generally, the composition comprises, in addition to terephthalylidene dicamphor sulfonic acid, at least one UVA filter, preferably selected from the group consisting of disodium phenyl dibenzimidazole tetrasulfonate (DPDT), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate, DHHB), 1-(4-(1 ,1-dimethylethyl)phenyl)-3-(4- methoxyphenyl)propane-1 ,3-dione (INCI butyl methoxydibenzoylmethane, BMDBM), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), and combinations thereof; and / or at least one UVB filter, preferably selected from the group consisting of 4,4',4"-(1 ,3,5- triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone, EHT), 4,4'-[[6-[[4-[[(1 ,1-dimethylethyl)amino]carbonyl]phenyl]amino]-1 ,3,5-triazin-2,4-diyl]diimino]bis- benzoic acid-bis(2-ethylhexyl)ester (INCI diethylhexyl butamido triazone, DBT), phenylbenzimidazole sulfonic acid (PBSA), and combinations thereof; and / or at least one broadband UV filter, preferably selected from the group consisting of bisethylhexyloxyphenol methoxyphenyl triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine, BEMT), 2-(2H-benzotriazol-2-yl)-6-[(2-ethylhexyloxy)methyl]-4-methylphenol, 2-(2H- benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1- disiloxanyl]propyl]phenol (INCI drometrizole trisiloxane, DTS), 2,2'-methylenbis[6-(2H- benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol] (INCI methylene Bis-benzotriazolyl tetramethylbutylphenol, MBBT), phenylene bis-diphenyltriazine (PBDT), and combinations thereof; and / or at least one organic particulate UV filter, preferably selected from the group consisting of 2,2'-methylene bis[6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol] (INCI methylene bis-benzotriazolyl tetramethylbutylphenol), 2,4,6-tris(biphenyl-4-yl)-1 ,3,5-triazine (INCI trisbiphenyl triazine, TBPT), 1 ,1 ’-(1 ,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl]-methanone (INCI bis-(diethylaminohydroxybenzoyl benzoyl) piperazine), 5,6,5’,6’-tetraphenyl-3-3’-(1 ,4-phenylene)bis(1 ,2,4-triazine) (INCI phenylene bis-diphenyltriazine; PBDT), micronized 1 ,4-di(benzoxazole-2'-yl)benzene and combinations thereof; and / or at least one inorganic UV filter, preferably selected from the group consisting of titanium dioxide, zinc oxide and mixtures thereof.

[0106] Preferably, the composition according to the invention comprises at least one UV filter selected from bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), butyl methoxydibenzoylmethane (BMDBM), ethylhexyl triazone (EHT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), tris-biphenyl triazine (TBPT), phenylene bis-diphenyl triazine (PBDT) and any combination of two or more thereof.

[0107] In various preferred embodiments, the at least one UV filter other than TDSA comprises at least one, preferably at least 2 or at least 3, of BEMT, EHT, BMDBM, DHHB, TBPT, MBBT, and PBSA. In various embodiments, the composition comprises at least DHHB. In various embodiments, the composition comprises at least BEMT. In various embodiments, the composition comprises at least EHT.

[0108] In various embodiments, the composition comprises at least one UVA filter, preferably selected from the group consisting of disodium phenyl dibenzimidazole tetrasulfonate (DPDT), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), butyl methoxydibenzoylmethane (BMDBM), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), and combinations thereof.

[0109] In various embodiments, the composition may comprise at least one UVB filter, preferably selected from the group consisting of ethylhexyl triazoneb (EHT), diethylhexyl butamido triazone (DBT), phenylbenzimidazole sulfonic acid (PBSA), polysilicone-15 (PS-15), and combinations thereof.

[0110] In various embodiments, the composition comprises at least one broadband UV filter, preferably selected from the group consisting of bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), drometrizole trisiloxane (DTS), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), phenylene bis-diphenyltriazine (PBDT), and combinations thereof.

[0111] In various embodiments, the composition comprises at least one organic particulate UV filter selected from the group consisting of methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), tris-biphenyl triazine (TBPT), bis-(diethylaminohydroxybenzoyl benzoyl) piperazine (BDBP), phenylene bis- diphenyltriazine (PBDT), micronized 1 ,4-di(benzoxazole-2'-yl)benzene and combinations thereof.

[0112] In some embodiments, the composition further comprises at least one inorganic UV filter, preferably selected from the group consisting of titanium dioxide, zinc oxide and mixtures thereof. In some embodiments, the composition comprises at least one UV filter other than TDSA selected from bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), ethylhexyl triazone (EHT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), trisbiphenyl triazine (TBPT), and any combination of two or more thereof.

[0113] In various embodiments, the composition comprises TDSA and DHHB. In such embodiments, the amount of DHHB in the composition may be at least equal to or higher than the amount of TDSA or neutralized TDSA in the composition.

[0114] In various embodiments, the composition comprises TDSA and ethylhexyl methoxycinnamate (EHMC), also referred to as octyl methoxycinnamate (OMC).

[0115] In various embodiments, the composition comprises at least one UVA filter, such as DHHB or BMDBM, and at least one UVB filter, such as EHT or PBSA.

[0116] In various embodiments, the composition comprises at least one broadband UV filter, such as BEMT or DTS, preferably BEMT, and at least one UVA filter, such as DHHB or BMDBM.

[0117] In various embodiments, the composition comprises at least one broadband UV filter, such as BEMT or PBDT, preferably BEMT, and at least one UVB filter, such as EHT or PBSA.

[0118] In various embodiments, the composition comprises at least one broadband UV filter, such as BEMT or PBDT, preferably BEMT, and at least one UVA filter, such as DHHB or BMDBM, and at least one UVB filter, such as EHT or PBSA.

[0119] In various embodiments, the composition comprises at least one particulate UV filter, such as MBBT or TBPT or PBDT, and at least one UVA filter, UVB filter and / or broadband UV filter, such as any one or more of DHHB, BMDBM, EHT, PBSA, and BEMT.

[0120] In various embodiments, the composition comprises at least one broadband UV filter, preferably BEMT. BEMT may, in all embodiments disclosed herein, be provided either as an oil soluble UV filter or encapsulated or dissolved in a polyacrylate matrix to be dispersible in water. In the latter case, it is for example available under the tradenames Tinosorb® S Aqua or Tinosorb® S Lite Aqua.

[0121] In some embodiments, the composition comprises (1) TDSA and (2) any one or more of diethylamino hydroxybenzoyl hexyl benzoate (DHHB), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), ethylhexyl triazone (EHT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), tris-biphenyl triazine (TBPT), phenylbenzimidazole sulfonic acid (PBSA), and phenylene bis-diphenyl triazine (PBDT). Specifically, the composition may comprise

[0122] (1) TDSA and DHHB;

[0123] (2) TDSA and EHT;

[0124] (3) TDSA and MBBT;

[0125] (4) TDSA and TBPT;

[0126] (5) TDSA and PBSA;

[0127] (6) TDSA and BEMT;

[0128] (7) TDSA and PBDT:

[0129] (8) TDSA, DHHB and EHT;

[0130] (9) TDSA, DHHB and MBBT,

[0131] (10)TDSA, DHHB and TBPT;

[0132] (11)TDSA, DHHB and PBSA;

[0133] (12)TDSA, DHHB and PBDT;

[0134] (13)TDSA, BEMT and DHHB;

[0135] (14)TDSA, EHT and MBBT;

[0136] (15)TDSA, EHT and TBPT;

[0137] (16)TDSA, EHT and PBSA;

[0138] (17)TDSA, EHT and BEMT;

[0139] (18)TDSA, EHT and PBDT;

[0140] (19)TDSA, MBBT and TBPT;

[0141] (20)TDSA, MBBT and PBSA;

[0142] (21)TDSA, MBBT and TDSA;

[0143] (22)TDSA; MBBT, and PBDT;

[0144] (23)TDSA, TBPT and PBSA;

[0145] (24)TDSA, TBPT and BEMT;

[0146] (25)TDSA; TBPT, and PBDT;

[0147] (26)TDSA, DHHB, EHT and MBBT;

[0148] (27)TDSA, DHHB, EHT and TBPT,

[0149] (28)TDSA, DHHB, EHT and PBSA;

[0150] (29)TDSA, DHHB, EHT and BEMT;

[0151] (30)TDSA, DHHB, EHT and PBDT;

[0152] (31)TDSA, EHT, MBBT and TBPT;

[0153] (32)TDSA, EHT, MBBT and PBSA;

[0154] (33)TDSA, EHT, MBBT and BEMT;

[0155] (34)TDSA, EHT, MBBT, and PBDT;

[0156] (35)TDSA, MBBT, TBPT and PBSA;

[0157] (36)TDSA, DHHB, EHT, MBBT, and TBPT;

[0158] (37)TDSA, DHHB, EHT, MBBT, and PBSA;

[0159] (38)TDSA, DHHB, EHT, MBBT and BEMT;

[0160] (39)TDSA, DHHB, EHT, MBBT and PBDT; (40)TDSA, DHHB, EHT, TBPT and PBSA;

[0161] (41)TDSA, DHHB, MBBT, PBSA and TBPT;

[0162] (42)TDSA, EHT, MBBT, TBPT and PBSA;

[0163] (43)TDSA, DHHB, BEMT, EHT, MBBT, and TBPT;

[0164] (44)TDSA, DHHB, BEMT, EHT, MBBT, and PBSA;

[0165] (45)TDSA, DHHB, BEMT, EHT, MBBT and PDBT;

[0166] (46)TDSA, DHHB, BEMT, EHT, TBPT and PBSA;

[0167] (47)TDSA, DHHB, BEMT, MBBT, PBSA and TBPT;

[0168] (48)TDSA, EHT, BEMT, MBBT, TBPT and PBSA;

[0169] (49)TDSA, DHHB, EHT, MBBT, TBPT and PBSA; or

[0170] (50)TDSA, DHHB, BEMT, EHT, MBBT, TBPT and PBSA.

[0171] In addition to those mentioned above, the composition may comprise one or more additional UV filter, such as BMDBM, for example BMDBM. In various embodiments, the composition may thus comprise:

[0172] (1) TDSA and BMDBM;

[0173] (2) TDSA, BMDBM and DHHB;

[0174] (3) TDSA, BMDBM and EHT;

[0175] (4) TDSA, BMDBM and MBBT;

[0176] (5) TDSA, BMDBM and TBPT;

[0177] (6) TDSA, BMDBM and PBSA;

[0178] (7) TDSA, BMDBM and BEMT;

[0179] (8) TDSA, BMDBM and PBDT;

[0180] (9) TDSA, DHHB, BMDBM and EHT;

[0181] (10)TDSA, DHHB, BMDBM and MBBT,

[0182] (11)TDSA, DHHB, BMDBM and TBPT;

[0183] (12)TDSA, DHHB, BMDBM and PBSA;

[0184] (13)TDSA, DHHB, BMDBM and BEMT;

[0185] (14)TDSA, EHT, BMDBM and MBBT;

[0186] (15)TDSA, EHT, BMDBM and TBPT;

[0187] (16)TDSA, EHT, BMDBM and PBSA;

[0188] (17)TDSA, EHT, BMDBM and BEMT;

[0189] (18)TDSA, MBBT, BMDBM and TBPT;

[0190] (19)TDSA, MBBT, BMDBM and PBSA;

[0191] (20)TDSA, TBPT, BMDBM and PBSA;

[0192] (21)TDSA, DHHB, EHT, BMDBM and MBBT;

[0193] (22)TDSA, DHHB, EHT, BMDBM and TBPT,

[0194] (23)TDSA, DHHB, EHT, BMDBM and PBSA;

[0195] (24)TDSA, DHHB, EHT, BMDBM and BEMT;

[0196] (25)TDSA, EHT, MBBT, BMDBM and TBPT; (26)TDSA, EHT, MBBT, BMDBM and PBSA;

[0197] (27)TDSA, EHT, MBBT, BMDBM and BEMT;

[0198] (28)TDSA, MBBT, TBPT, BMDBM and PBSA;

[0199] (29)TDSA, DHHB, EHT, MBBT, BMDBM and TBPT;

[0200] (30)TDSA, DHHB, EHT, MBBT, BMDBM and PBSA;

[0201] (31)TDSA, DHHB, EHT, TBPT, BMDBM and PBSA;

[0202] (32)TDSA, DHHB, MBBT, PBSA, BMDBM and TBPT;

[0203] (33)TDSA, EHT, MBBT, TBPT, BMDBM and PBSA;

[0204] (34)TDSA, DHHB, EHT, MBBT, TBPT, BMDBM and PBSA;

[0205] (35)TDSA, BEMT, DHHB, EHT, MBBT, BMDBM and TBPT;

[0206] (36)TDSA, BEMT, DHHB, EHT, MBBT, BMDBM and PBSA;

[0207] (37)TDSA, BEMT, DHHB, EHT, TBPT, BMDBM and PBSA;

[0208] (38)TDSA, BEMT, DHHB, MBBT, PBSA, BMDBM and TBPT;

[0209] (39)TDSA, BEMT, EHT, MBBT, TBPT, BMDBM and PBSA; or

[0210] (40)TDSA, BEMT, DHHB, EHT, MBBT, TBPT, BMDBM and PBSA.

[0211] In some embodiments, the composition comprises (1) TDSA, (2) diethylamino hydroxybenzoyl hexyl benzoate (DHHB) and (3) any one or more of bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), ethylhexyl triazone (EHT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), tris-biphenyl triazine (TBPT), phenylene bis-diphenyl triazine (PBDT), and phenylbenzimidazole sulfonic acid (PBSA).

[0212] Specifically, the composition may comprise

[0213] (1) TDSA, DHHB and BEMT;

[0214] (2) TDSA, DHHB and EHT;

[0215] (3) TDSA, DHHB and MBBT;

[0216] (4) TDSA, DHHB and TBPT;

[0217] (5) TDSA, DHHB and PBDT;

[0218] (6) TDSA, DHHB and PBSA;

[0219] (7) TDSA + DHHB + EHMC,

[0220] (8) TDSA + DHHB + DBT

[0221] (9) TDSA + PBSA + DBPT

[0222] (10)TDSA + PBSA + MBBT

[0223] (11)TDSA + PBSA + MBBT

[0224] (12)TDSA + PBSA + TBPT

[0225] (13)TDSA + PBSA + bis-(diethylaminohydroxybenzoyl benzoyl) piperazine

[0226] (14)TDSA + PBSA + phenylene bis-diphenyltriazine

[0227] (15)TDSA, DHHB, BEMT and EHT;

[0228] (16)TDSA, DHHB, BEMT and MBBT;

[0229] (17)TDSA, DHHB, BEMT and TBPT; (18)TDSA, DHHB, BEMT and PBSA;

[0230] (19)TDSA, DHHB, BEMT and PBDT;

[0231] (20)TDSA, DHHB, PBDT and EHT;

[0232] (21)TDSA, DHHB, PBDT and MBBT;

[0233] (22)TDSA, DHHB, PBDT and TBPT;

[0234] (23)TDSA, DHHB, PBDT and PBSA;

[0235] (24)TDSA, DHHB, EHT and MBBT;

[0236] (25)TDSA, DHHB, EHT and TBPT;

[0237] (26)TDSA, DHHB, EHT and PBSA;

[0238] (27)TDSA, DHHB, MBBT and TBPT;

[0239] (28)TDSA, DHHB, MBBT and PBSA;

[0240] (29)TDSA; DHHB, TBPT and PBSA;

[0241] (30)TDSA; DHHB, EHT, MBBT and TBPT;

[0242] (31)TDSA, DHHB, EHT, MBBT and PBSA;

[0243] (32)TDSA, DHHB, MBBT, TBPT and PBSA; or

[0244] (33)TDSA, DHHB, EHT, MBBT, TBPT and PBSA.

[0245] In some embodiments, the composition comprises TDSA, EHT, BEMT, and DHHB.

[0246] In some embodiments, the composition comprises TDSA, BEMT, EHT, DHHB, and TBPT.

[0247] In some embodiments, the composition comprises TDSA, BEMT, EHT, DHHB, PBSA and TBPT.

[0248] In some embodiments, the composition comprises TDSA, BEMT, DHHB, EHT and PBSA.

[0249] In some embodiments, the composition comprises TDSA, DHHB, and at least one of BMDBM, EHT, DBT and EHMC. In some embodiments, the composition comprises TDSA, DHHB, and BMDBM and, optionally, at least one of EHT, DBT and EHMC. In some embodiments, the composition comprises TDSA, DHHB, and EHT and, optionally, at least one of BMDBM, DBT and EHMC. In some embodiments, the composition comprises TDSA, DHHB, and DBT and, optionally, at least one of BMDBM, EHT and EHMC. In some embodiments, the composition comprises TDSA, DHHB, and EHMC and, optionally, at least one of BMDBM, DBT and EHT. In some embodiments, any of these compositions is free of octocrylene. In some embodiments, any such composition is free of TEA. In various embodiments, such a composition comprises TDSA, DHHB, and at least one of BMDBM, EHT, DBT and EHMC, is free of octocrylene and free of TEA and, optionally, the amount of DHHB is equal to or higher than that of TDSA I neutralized TDSA. In such embodiments, if said composition contains EHMC, it does not contain BMDBM. In various embodiments of said composition, the amount of TDSA, DHHB and optionally any other UV filter compound is >0.5 wt.-% relative to the total weight of the composition. In various embodiments, the composition comprises TDSA and one or more additional organic UV filters that are present in the water phase, for example organic UV filters that are water-soluble or water- dispersible. Such UV filters include, without limitation, PBSA and its salts. Such a composition may be a water-based sunscreen composition. In various embodiments, in such compositions, all UV filters are present in the water phase and not in the oil phase. In various embodiments, such compositions do not comprise TEA i.e. are free of TEA. In some embodiments, the composition comprises a water phase and all UV filters comprised in the composition are present in the water phase, said UV filters comprising TDSA and PBSA and optionally one or more further organic UV filters, and said composition is also free of TEA.

[0250] “Present in the water phase” or “present in the aqueous phase”, as interchangeably used in this context, refers to the property of being water-soluble or water-dispersible and being present predominantly, i.e. with more than 50 % by weight of its total weight, preferably at least 60, at least 70, at least 80% by weight or more, in the aqueous phase relative to the non-aqueous phase, i.e. typically the oil phase, for example in an emulsion. In other words, if such composition comprises at least two different phases, one being a water or aqueous phase, the UV filter compounds are predominantly present in the water phase and not in the other phases.

[0251] In all the above-listed embodiments of different UV filter combinations the compositions may comprise no other organic UV filter, or even no other UV filter substance besides those explicitly listed. This may mean that the at least one organic UV filter other than TDSA consists of the above-listed combinations.

[0252] In various embodiments in which the composition comprises BEMT, BEMT is comprised in an amount of from 0.5 to 10.0 wt.-%, for example 1 .0 to 9.0 wt.-% or 1 .5 to 8.5 wt.-% or 2.0 to 8.0 wt.-% or 2.0 to 7.0 wt.-% or 2.0 to 6.0 wt.-% or 2.0 to 5.5 wt.-%, or 2.0 to 5.0 wt.-%, or 3.0 to 7.0 wt.-% or 3.0 to 6.0 wt.- %, preferably 1.0 to 6.0 wt.-%, more preferably 2.0 to 5.0 wt.-%, based on the total weight of the composition.

[0253] In various embodiments in which the composition comprises EHT, EHT is comprised in an amount of from 0.5 to 5.0 wt.-%, for example 1 .0 to 5.0 wt.-% or 1 .5 to 4.5 wt.-% or 2.0 to 4.0 wt.-%, preferably 1 .0 to 4.0 wt.-%, more preferably 1 .5 to 3.0 wt.-%, based on the total weight of the composition.

[0254] In various embodiments in which the composition comprises PBSA, PBSA is comprised in an amount of from 0.5 to 5.0 wt.-%, for example 1 .0 to 5.0 wt.-% or 1 .5 to 4.5 wt.-% or 2.0 to 4.0 wt.-%, preferably 1.0 to 4.0 wt.-%, more preferably 1.5 to 3.0 wt.-%, based on the total weight of the composition. Such embodiments include those where the composition comprises an aqueous phase and, preferably, all UV filters comprised therein are present in said aqueous phase. In various embodiments, such compositions do not comprise TEA i.e. are free of TEA. In some embodiments, the composition comprises a water phase and the UV filters TDSA and PBSA and optionally one or more further organic UV filters are all present in the water phase. Such compositions are preferably free of TEA and, optionally, also octocrylene.

[0255] In various embodiments in which the composition comprises DHHB, DHHB is comprised in an amount of from 0.5 to 10.0 wt.-%, for example 1 .0 to 9.0 wt.-% or 1 .5 to 8.5 wt.-% or 2.0 to 8.0 wt.-% or 2.0 to 7.0 wt.-% or 2.0 to 6.0 wt.-% or 2.0 to 5.5 wt.-%, or 2.0 to 5.0 wt.-%, or 3.0 to 7.0 wt.-% or 3.0 to 6.0 wt.- %, based on the total weight of the composition.

[0256] In various embodiments in which the composition comprises TBPT, TBPT is comprised in an amount of from 0.5 to 10.0 wt.-%, for example 1 .0 to 9.0 wt.-% or 1 .5 to 8.5 wt.-% or 2.0 to 8.0 wt.-% or 2.0 to 7.0 wt.-% or 2.0 to 6.0 wt.-% or 2.0 to 5.5 wt.-%, or 2.0 to 5.0 wt.-%, or 3.0 to 7.0 wt.-% or 3.0 to 6.0 wt.-%, preferably 1.0 to 5.0 wt.-%, more preferably 2.0 to 4.0 wt.-%, based on the total weight of the composition.

[0257] In various embodiments in which the composition comprises BMDBM, BMDBM is comprised in an amount of from 0.5 to 5.0 wt.-%, for example 1.0 to 5.0 wt.-% or 1.5 to 4.5 wt.-% or 2.0 to 4.0 wt.-%, preferably 1.0 to 5.0 wt.-%, more preferably 2.0 to 5.0 wt.-%, based on the total weight of the composition.

[0258] In various embodiments in which the composition comprises MBBT, MBBT is comprised in an amount of from 0.5 to 10.0 wt.-%, for example 1 .0 to 9.0 wt.-% or 1 .5 to 8.5 wt.-% or 2.0 to 8.0 wt.-% or 2.0 to 7.0 wt.-% or 2.0 to 6.0 wt.-% or 2.0 to 5.5 wt.-%, or 2.0 to 5.0 wt.-%, or 3.0 to 7.0 wt.-% or 3.0 to 6.0 wt.- %, preferably 1.0 to 5.0 wt.-%, more preferably 1.5 to 4.0 wt.-%, based on the total weight of the composition.

[0259] In various embodiments in which the composition comprises PBDT, PBDT is comprised in an amount of from 0.5 to 10.0 wt.-%, for example 1 .0 to 9.0 wt.-% or 1 .5 to 8.5 wt.-% or 2.0 to 8.0 wt.-% or 2.0 to 7.0 wt.-% or 2.0 to 6.0 wt.-% or 2.0 to 5.5 wt.-%, or 2.0 to 5.0 wt.-%, or 3.0 to 7.0 wt.-% or 3.0 to 6.0 wt.- %, preferably 1.0 to 6.0 wt.-%, more preferably 2.0 to 5.0 wt.-%, based on the total weight of the composition.

[0260] In various embodiments, the composition comprises the at least one organic UV filter other than TDSA in an amount of 1 .5 to 40 wt.-%, 2.0 to 40 wt.-%, 2.5 to 40 wt.-%, 3.0 to 40 wt.-%, 3.5 to 40 wt.-% or 4.0 to 40.0 wt.-%, preferably of 5.0 to 35.0 wt.-%, more preferably of 6.0 to 35.0 wt.-% or of 7.0 to 30.0 wt.- %, still more preferably of 8.0 to 25.0 wt.-%, and in particular of 9.0 to 20.0 wt.-%, based on the total weight of the composition. Said amount may also apply to the total amount of all UV filters, including inorganic UV filters and TDSA. In various embodiments, the sunscreen or daily care composition comprises a total of 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, or 40 wt.-% of UV filters based on the total weight of the composition. The lower limit may be 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, or 6.0 wt.-%. The upper limit may be 40.0, 35.0, 30.0 29.0. 28.0. 27.0.26.0. or 25.0 wt.-% of UV filters based on the total weight of the composition.

[0261] In various embodiments, the weight ratio of the at least one broadband UV filter to at least one UVB filter, at least one UVA filter (including TDSA) or at least one particulate UV filter may be in the range of 1 :5 to 5:1 , for example 1 :3 to 3:1 .

[0262] In various embodiments, the weight ratio of the at least one UVA filter (including TDSA) to at least one UVB filter or at least one particulate UV filter may be in the range of 1 :5 to 5:1 , for example 1 :3 to 3:1 .

[0263] In various embodiments, the weight ratio of the at least one UVB filter to at least one particulate UV filter may be in the range of 1 :5 to 5:1 , for example 1 :3 to 3:1 .

[0264] In various embodiments, the weight ratio of the at least one particulate UV filter to at least one UVB filter or at least one UVA filter may be in the range of 1 :5 to 5:1 , for example 1 :3 to 3:1 .

[0265] In various embodiments, the composition comprises the at least one organic UV filter other than TDSA in an amount of 4.0 to 40.0 wt.-%, preferably of 5.0 to 35.0 wt.-%, more preferably of 6.0 to 35.0 wt.-% or of 7.0 to 30.0 wt.-%, still more preferably of 8.0 to 25.0 wt.-%, and in particular of 9.0 to 20.0 wt.-%, based on the total weight of the composition, and the TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1 .0 to 3.0 wt.-%, based on the total weight of the composition.

[0266] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1.0 to 3.0 wt.-%, based on the total weight of the composition, and BEMT in an amount of 0.5 to 10.0 wt.-%, preferably 1.0 to 6.0 wt.-%, more preferably 2.0 to 5.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to BEMT may, in various embodiments, be in the range of 0.1 :1 to 2:1 , 0.1 :1 to 1 .2:1 , preferably 0.2:1 to 1 :1 or 0.3:1 to 1 :1 .

[0267] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1.0 to 3.0 wt.-%, based on the total weight of the composition, and DHHB in an amount of from 0.5 to 10.0 wt.-%, preferably 2.0 to 8.0 wt.-%, more preferably 4.0 to 7.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to DHHB may, in various embodiments, be in the range of 0.05:1 to 5:1 , 0.1 :1 to 4:1 , 0.1 :1 to 3:1 , 0.1 :1 to 3:1 , 0.1 :1 to 2:1 , or 0.1 :1 to 1 :1 , preferably 0.2:1 to 0.8:1 or 0.3:1 to 0.8:1 . In various embodiments, the weight ratio of TDSA to DHHB is 0.1 :1 to 1 :1 , preferably 0.1 :1 to <1 :1 or 0.1 :1 to 0.9:1 , more preferably 0.2:1 to 0.8:1 or 0.3:1 to 0.8:1 . These ratios particularly apply to compositions that comprise TDSA, DHHB, and at least one of BMDBM, EHT, DBT and EHMC, in particular those free of octocrylene and free of TEA. In such compositions, the amount of DHHB may be >0.5 wt.-% relative to the total weight of the composition. In such compositions, the amount of TDSA may be >0.5 wt.-% relative to the total weight of the composition.

[0268] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1 .0 to 3.0 wt.-%, based on the total weight of the composition, and EHT in an amount of from 0.5 to 5.0 wt.-%, preferably 1.0 to 4.0 wt.-%, more preferably 1.5 to 3.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to EHT may, in various embodiments, be in the range of 0.1 :1 to 5:1 , 0.1 :1 to 4:1 , 0.1 :1 to 3:1 , 0.1 :1 to 3:1 , 0.1 :1 to 2:1 , or 0.2:1 to 2:1 , 0.3:1 to 2:1 , 0.4:1 to 2:1 , or 0.5:1 to 1 .5:1 , or 0.5:1 to 3.5:1 , or 1 :1 to 3:1 , or 1 :1 .5 to 1 :2.5, or 1 :1.8 to 1 :2.3.

[0269] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1.0 to 3.0 wt.-%, based on the total weight of the composition, and PBSA in an amount of from 0.5 to 5.0 wt.-%, preferably 1 .0 to 4.0 wt.-%, more preferably 1 .5 to 3.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to PBSA may, in various embodiments, be in the range of 0.1 :1 to 5:1 , 0.1 :1 to 4:1 , 0.1 :1 to 3:1 , 0.1 :1 to 3:1 , 0.1 :1 to 2:1 , or 0.2:1 to 2:1 , 0.3:1 to 2:1 , 0.4:1 to 2:1 , or 0.5:1 to 1.5:1 , preferably 0.5:1 to 1 :1. These ratios also apply to the above-described compositions where all UV filters are present in the aqueous phase.

[0270] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1.0 to 3.0 wt.-%, based on the total weight of the composition, and TBPT in an amount of from 0.5 to 10.0 wt.-%, preferably 1.0 to 5.0 wt.-%, more preferably 2.0 to 4.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to TBPT may, in various embodiments, be in the range of 0.1 :1 to 2:1 , 0.1 :1 to 1 .2:1 , preferably 0.2:1 to 1 :1 or 0.3:1 to 1 :1 , preferably 0.4:1 to 1 :1 .

[0271] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1 .0 to 3.0 wt.-%, based on the total weight of the composition, and BMDBM in an amount of from 0.5 to 5.0 wt.-%, preferably 1 .0 to 5.0 wt.-%, more preferably 2.0 to 5.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to BMDBM may, in various embodiments, be in the range of 0.1 :1 to 2:1 , 0.1 :1 to 1 .2:1 , preferably 0.2:1 to 1 :1 or 0.3:1 to 1 :1 , preferably 0.4:1 to 1 :1 .

[0272] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1 .0 to 3.0 wt.-%, based on the total weight of the composition, and EHMC in an amount of from 0.5 to 10.0 wt.-%, preferably 1.0 to 8.0 wt.-%, more preferably 2.0 to 5.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to EHMC may, in various embodiments, be in the range of 0.1 :1 to 2:1 , 0.1 :1 to 1 .2:1 , preferably 0.2:1 to 1 :1 or 0.3:1 to 1 :1 , preferably 0.4:1 to 1 :1 . In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1.0 to 3.0 wt.-%, based on the total weight of the composition, and MBBT in an amount of from 0.5 to 10.0 wt.-%, preferably 1 .0 to 5.0 wt.-%, more preferably 1 .5 to 4.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to MBBT may, in various embodiments, be in the range of 0.1 to 5:1 , 0.1 :1 to 4:1 , 0.1 :1 to 3:1 , 0.1 :1 to 3:1 , 0.1 :1 to 2:1 , or 0.2:1 to 2:1 , 0.3:1 to 2:1 , 0.4:1 to 2:1 , or 0.5:1 to 1 .5:1 , preferably 0.5:1 to 1 :1 .

[0273] In various embodiments, the composition comprises TDSA in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1 .0 to 3.0 wt.-%, based on the total weight of the composition, and DBT in an amount of from 0.5 to 10.0 wt.-%, preferably 1.0 to 5.0 wt.-%, more preferably 1.5 to 4.0 wt.-%, based on the total weight of the composition. The weight ratio of TDSA to DBT may, in various embodiments, be in the range of 0.1 to 5:1 , 0.1 :1 to 4:1 , 0.1 :1 to 3:1 , 0.1 :1 to 3:1 , 0.1 :1 to 2:1 , or 0.2:1 to 2:1 , 0.3:1 to 2:1 , 0.4:1 to 2:1 , or 0.5:1 to 1 .5:1 , preferably 0.5:1 to 1 :1 .

[0274] The above embodiments may further be combined such that the compositions contain TDSA in the given amounts and two or more of the above-listed UV filters in the given amounts for each of them.

[0275] In various embodiments, the composition is free of octocrylene.

[0276] In various embodiments, the composition is free of benzophenone-3.

[0277] In various embodiments, the composition is free of ethylhexyl methoxycinnamate (EHMC), also referred to as octyl methoxycinnamate. In various embodiments, the composition is free of EHMC and benzophenone-3 and optionally also free of octocrylene.

[0278] In some embodiments, the composition is free of at least one or more of fluorinated organic compounds, parabenes, and organic UV filter compounds selected from the group of homomethyl salicylate, ethylhexyl methoxycinnamate, benzophenone-3, and octocrylene. In particular embodiments, the composition is free of fluorinated organic compounds. In some embodiments, the composition is free of parabens. In various embodiments, the composition is free of homomethyl salicylate. In various embodiments, the composition is free of ethylhexyl methoxycinnamate. In various embodiments, the composition is free of octocrylene. In various embodiments, the composition is free of benzophenone- 3. In various embodiments, the composition is free of homomethyl salicylate, ethylhexyl methoxycinnamate, octocrylene, and benzophenone-3. In various embodiments, the composition is free of fluorinated organic compounds, parabenes, and organic UV filter compounds selected from the group of homomethyl salicylate, ethylhexyl methoxycinnamate, octocrylene, and benzophenone-3. In various embodiments, the composition does not comprise an inorganic UV filter. In various embodiments, the composition is free of TiC>2.

[0279] In various embodiments, the composition is free of triethanolamine (TEA). In preferred embodiments, all compositions disclosed herein are free of TEA. This particularly applies to those compositions that comprise TDSA in combination with DHHB and / or PBSA.

[0280] In various embodiments, the composition is a sunscreen or daily care composition that provides a SPF of more than 15, preferably of more than 30. In another preferred embodiment of the present invention, the sunscreen or daily care composition provides a SPF of more than 50, preferably of more than 60. In another preferred embodiment of the present invention, the sunscreen or daily care composition provides a SPF of more than 90, preferably of more than 100. The SPF may be determined according to any method known in the art.

[0281] Further, in connection with the above embodiments, it is to be understood that the composition may comprise at least one additive.

[0282] In various embodiment, the at least one additive is selected from the group consisting of emulsifiers, emollients, viscosity regulators (thickeners), stabilizers, humectants, chelating agents, film formers, UV scattering compounds, UV boosters, pH adjusters (other than the organic pH neutralizer), sensory enhancers, adjuvants, preservatives, moisturizers, anti-aging actives, vitamins, fragrances, and combinations thereof. All such additives commonly used in topical compositions such as sunscreen compositions or daily care compositions are well known and may be selected by those skilled in the art based on their routine knowledge.

[0283] In various embodiments, the composition contains only one pH neutralizer compound (ii). In various embodiments, the composition does not contain any other pH neutralizer besides (ii). In various embodiments, the composition contains pH neutralizer (ii) as the only pH adjusting agent to adjust or maintain the pH of the composition at the desired value. In this context, “other pH neutralizer” relates particularly to those compounds that are added with the intention to adjust the pH and which do not have any other (main) function in the composition, for example in that they are not predominantly used as a preservative, colorant, fragrance, emulsifier and the like. This term covers, for example, (alkali) metal hydroxides, oxides and carbonates, used to adjust an acidic pH to a more alkaline range.

[0284] In various embodiments, the compositions of the invention comprise at least one emulsifier. The at least one emulsifier may be selected from those disclosed herein below. In various embodiments, the amount of the at least one emulsifier is in the range of from 0.5 to 10 wt.-% relative to the total weight of the composition, for example 0.8 to 7 wt.-%. In various embodiments, the compositions of the invention comprise at least one emollient. The at least one emollient may be selected from those disclosed herein below. In various embodiments, the amount of the at least one emollient is in the range of from 0.5 to 40 wt.-% relative to the total weight of the composition, for example 3.0 to 30 wt.-%.

[0285] In various embodiments, the compositions of the invention comprise at least one emulsifier and at least one emollient, preferably in the amounts disclosed above.

[0286] Preferred O / 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, glyceryl oleate; glutamic 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 phosphate; fatty acid esters of polyglyceryl such as polyglyceryl-3-diisostearate, polyglyceryl-2- dipolyhydroxystearate; polyglyceryl-10 stearate, polyglyceryl-10 oleate, oxyalkenylated fatty alcohol such as ceteareth-20, steareth-21 , beneheth-25 oxyalkenylated fatty acid such as PEG-100 stearate oxyalkenylated organomodified silicone I polysiloxane I polyalkyl I polyether copolymers and derivatives.

[0287] - phospholipids based such as lecithin derivatives.

[0288] In various embodiments, the O / W emulsifier may be selected from any one or more of disodium cetearyl sulfosuccinate, sodium stearyl glutamate, potassium cetyl phosphate, polyglyceryl-10 stearate, polyglyceryl-10 oleate, cetearyl glucoside, lauryl glucoside, sucrose palmitate, glyceryl stearate SE, and glyceryl stearate citrate. The total amount of said at least one emulsifier in the composition may be in the range of from 0.2 to 10.0 wt.-% relative to the total weight of the composition, for example 0.5 to 8.0 wt.-%, or 1 .0 to 6.0 wt.-%.

[0289] In preferred embodiments, the topical composition comprises at least one emulsifier that is selected from polyglyceryl-10 stearate, polyglyceryl-10 oleate, sodium stearoyl glutamate and / or cetearyl glucoside.

[0290] Exemplary 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- dipolyhydroxystearate, polyglyceryl-4 isostearate Oxyakenylated fatty alcohol such steareth-2

[0291] Oxyakenylated fatty acid such as PEG-30 dipolyhydroxystearate organomodified silicone I polysiloxane I polyalkyl I polyether copolymers and derivatives such as cetyl dimethicone copolyol, cetyl PEG / PPG-10 / 1 Dimethicone, PEG-10 dimethicone

[0292] Suitable emollients include, without limitation, esters of linear or branched fatty acids with linear or branched fatty alcohols such as propylheptyl caprylate, coco caprylate, isopropyl myristate, ethylhexyl palmitate, lauryl lactate; 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-, triglycerides based on C6-C18 fatty acids such as caprylic I capric triglycerides, coco glycerides; guerbet alcohols such as octyldodecanol; hydrocarbons such as hydrogenated polyisobutene, mineral oil, squalene, isohexadecane; ethers such as dicaprylyl ether; silicone derivatives (organomodified polysiloxanes) such as dimethylpolysiloxane, cyclic silicones.

[0293] In various embodiments, the emollient may be selected of any one or more of propylheptyl caprylate, coco caprylate, isopropyl myristate, C12-15 alkyl benzoate, ethylhexyl palmitate, dibutyl adipate, dicaprylyl carbonate, lauryl lactate, propylene glycol dicaprylate I dicaprate, diisopropyl sebacate, dicaprylyl ether, and octyldodecanol. The total amount of the at least one emollient may be in the range of from 0.5 to 40 wt.-% relative to the total weight of the composition, for example 3.0 to 30 wt.-%.

[0294] In various embodiments, the emollient is selected of any one or more of

[0295] C12-15 alkyl benzoate; and / or dibutyl adipate; and / or dicaprylyl carbonate; and / or propylheptyl caprylate; and / or lauryl lactate; and / or octyldodecanol; preferably the total amount of emollient is 0.5 to 40 wt.-%, based on the total weight of the composition, for example 3.0 to 30 wt.-%.

[0296] Exemplary 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 dicocoyl pentaerythrityl distearyl citrate (Cutina® Shine) silica based derivatives such as silica, silica dimethyl silylate.

[0297] In various embodiments, the thickener may be selected from any one or more of cetyl alcohol, behenyl alcohol, cetyl palmitate, carnauba wax, dicocoyl pentaerythrityl distearyl citrate, and pentaerythrityl distearate.

[0298] Hydrophilic stabilizers / thickeners include, without limitation, natural gums such as xanthan gum, tara gum, carrageenan silicate derivatives such as magnesium aluminum silicates; cellulose derivatives such as hydroxypropyl cellulose, microcrystalline cellulose starch derivatives such as hydroxypropyl starch phosphate

[0299] - polyacrylates or homopolymers of reticulated acrylic acids or polyacrylamides such as carbomers, acrylate copolymers, acrylate I C10-C30-alkyl acrylate crosspolymer, acrylate I beheneth-25 methacrylate copolymer.

[0300] Also included may be UV protection scattering compounds. These include, without limitation: microcrystalline cellulose; calcium carbonate; hydroxyapatite; silica ; hollow spheres, such as styrene / acrylates copolymer.

[0301] 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,

[0302] Bis(Cyano Butylacetate) 10 Anthracenediylidene, polyester-25, butyloctyl salicylate.

[0303] Further components may belong to the class of film formers and film forming enhancers. Such compounds include, without limitation, hydrogenated dimer dilinoleyl / dimethylcarbonate copolymer; diisostearoyl polyglyceryl-3 dimer dilinoleate; polyglyceryl-3 stearate / sebacate crosspolymer; cellulose derivatives, such as methylcellulose and ethylcellulose; capryloyl glycerin / sebacic acid copolymer.

[0304] Suitable sensory enhancers include, without limitation, polyamide derivatives such as nylon-12, polymethyl methacrylates, silica, mica, polymethylsilsesquioxane, starch derivatives such as aluminum starch octenylsuccinate, dimethicone derivatives, boron nitride,

[0305] HDI / trimethylol hexyllactone crosspolymer, perlite.

[0306] Suitable humectants include, without limitation, glycerin; butylene glycol; propylene glycol; beta-glucan;

[0307] 1 ,2 pentadiol;

[0308] 1 ,2 hexandiol;

[0309] 1 ,2 octandiol;

[0310] 1 ,2 decandiol;

[0311] 2-Methyl-1 ,3-propandiol.

[0312] Suitable adjuvants include, without limitation, 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.

[0313] Preferred preservatives include the compounds listed in Annex V of the Regulation 1223 / 2009 / EC on cosmetic products, in particular, without limitation, benzyl alcohol; benzoic acid; zingerone; phenoxyethanol;

[0314] Suitable preservation enhancers (preservation boosters) of the composition include, without limitation, ethylhexylglycerin hydroxyacetophenone, phenylpropanol, hydroxyethoxyphenyl butanone, and glyceryl caprylate.

[0315] Suitable fragrances are selected from the group of fragrance compounds including, but not limited to, limonene, citral, linalool, alpha-isomethylionon, geraniol, citronellol, 2-isobutyl-4-hydroxy-4- methyltetrahydropyrane, 2-tert.-pentylcyclohexylacetate, 3-methyl-5-phenyl-1 -pentanol, 7-acetyl- 1 ,1 ,3,4,4, 6-hexamethyltetraline, adipine acid diester, alpha-amylcinnamaldehyde, alpha-methylionon, amyl C butylphenylmehtylpropionalcinnamal, amylsalicylate, amylcinnamylalcohol, anis alcohol, 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, hexylcalicylate, 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.

[0316] In connection with the above preferred embodiments, it is to be understood that if the topical composition, preferably the sunscreen or daily care composition comprises two or more additives, combinations of the additives as defined above are also part of the invention.

[0317] In various preferred embodiments, the topical composition, preferably the sunscreen or daily care composition, comprises

[0318] (i) terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA);

[0319] (ii) at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group, preferably, the organic pH neutralizer is L-arginine or tromethamine;

[0320] (iii) at least one UV filter other than terephthalylidene dicamphor sulfonic acid, preferably any one or more of DHHB, BEMT, and EHT;

[0321] (iv) at least one emulsifier; and

[0322] (v) at least one emollient; wherein the pH of the composition is within the range of 4.0 to 8.0.

[0323] Preferably,

[0324] (1) the composition is free of at least one or more of parabens, and organic UV filter compounds selected from the group of homomenthyl salicylate, ethylhexyl methoxycinnamate (EHMC), octocrylene, and ethylhexyl salicylate; and / or

[0325] (2) the composition further comprises at least one additive, preferably selected from the group consisting of emulsifiers, emollients, viscosity regulators (thickeners), buffering and pH adjustment agents, stabilizers, sensory enhancers, film formers, UV scattering compounds, UV protection booster compounds, adjuvants, preservatives, perfumes, and combinations thereof.

[0326] In various embodiments, the topical composition is free of at least one or more organic UV filters selected from octocrylene and ethylhexyl methoxycinnamate (EHMC).

[0327] The final formulations of the compositions may exist in a wide variety of presentation forms, for example: in the form of preparations as a W / O, O / W, oil-in-water-in-oil (O / W / O), water-in-oil-in water (W / O / W), a bi-phasic formulation, gel, clear hydrogel, transparent or non-transparent stick, or phase-inversion- technology (PIT) emulsion, a polymeric-based emulsion, and all kinds of microemulsions. The final formulations can be provided in different forms such as a gel, a cream, milk or lotion, in the form of a powder, in the form of a stick, in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste. Thus, in some embodiments, the topical composition, preferably the sunscreen or daily care composition, comprises water. In case water is present in the composition, it is preferably present in an amount of more than 5 wt.-%, based on the total weight of the composition. Typical amounts of water in the formulations range from 5.5 to 95 wt.-% or 10 to 85 wt.-% or 15 to 80 wt.-% of water relative to the total weight of the composition, such as 20 to 70 wt.-% or 30 to 60 wt.-% or 35 to 55 wt.-%.

[0328] For instance, when formulated as a W / O or an O / W dispersion, an optional cosmetically acceptable carrier preferably comprises 5.0 to 50.0 % of an oil phase, 1.0 to 10.0 % of an emulsifier and 30.0 to 90.0 % of water, each by weight based on the total weight of the carrier. The oil phase may comprise any lipophilic compounds conventionally used in cosmetic formulations, e.g., one or more of a ester oil, hydrocarbon oil, a wax, a natural oil, a silicone oil, fatty acid, a fatty acid ester or a fatty alcohol. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerin, and sorbitol. The emulsifier also may comprise any emulsifier conventionally used in cosmetic formulations, for example those described above.

[0329] In another aspect, the present invention is directed to the use of at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group, for improving the stability of and / or the sensory properties of and / or reducing the generation of radicals upon UV exposure in a topical composition comprising TDSA, preferably a sunscreen or daily care composition comprising TDSA. “Improving the stability” of a topical composition comprising TDSA refers to preventing sedimentation / precipitation of the TDSA, for example upon neutralization.

[0330] In various embodiments, the organic pH neutralizer is selected from an amino acid, preferably a basic amino acid, more preferably L-lysine or L-arginine, most preferably L-arginine, or from primary aminoalcohols, preferably beta-aminoalcohols, more preferably tris(hydroxymethyl)aminomethane tromethamine. In particularly preferred embodiments, the organic pH neutralizer is L-arginine.

[0331] It is to be understood that the above embodiments of the topical composition are also applicable for the uses of the present invention, and vice versa. This means that the compositions may, in various embodiments, comprise one of more UV filters other than TDSA and / or one or more additives, with preferred embodiments being disclosed above in connection with the compositions of the invention.

[0332] The present invention is further illustrated by the following non-limiting examples. Examples

[0333] Methods

[0334] SPF in vitro

[0335] SPF and UVA-PF in vitro determination was based on the assessment of UV-transmittance through a thin film of sunscreen sample spread on roughened PMMA plates (SB6 PMMA-plates from Helioscreen, Creil, France). The sunscreen formulation to be tested was applied on the PMMA plate with an amount of 1 .2mg / cm2. The formulation was distributed manually as equally as possible on the plate. The plates applied with formulation are then stored 30 minutes at 27° and in a dark place prior the measurement. 3 plates per formulation were evaluated and 5 measurements per plate performed.

[0336] In vitro transmission measurement was performed from 290-400 nm with 1 nm steps with the Labsphere UV Transmittance Analyzer UV 2000S. The plates were then irradiated with the UV dose according to the method ISO24443:2021 . The in vitro transmission measurement from 290-400 was performed again after UV irradiation.

[0337] The SPF in vitro was calculated using the in vitro transmission spectrum after UV irradiation according to equation 1

[0338] Equation 1 wherein, ser(A) is the erythema action spectrum and S(A) is the spectral irradiance received from the UV source and T(A) is the in vitro measured light transmittance.

[0339] The UVA-PF in vitro is calculated according to the method ISO24443:2021 using the in vitro after UV irradiation adjusted transmission spectrum according to equation 2

[0340] Equation 2 wherein, sPPD(h) is the Pigment persistence darkening (PPD) action spectrum and S(A) is the spectral irradiance received from the UVA source and T(A) is the in vitro measured adjusted (according to ISO24443) light transmittance.

[0341] SPF in vivo

[0342] The SPF in vivo was measured according to the norm ISO24444:2019 which uses the erythemal response of the skin to ultraviolet. The SPF in vivo is the ratio calculated from the energies required to induce a minimum erythemal response with and without tested sunscreen product applied to the skin of human test subjects.

[0343] SPF in silico Calculated with BASF’s digital sunscreen simulator tool (sunscreensimulator.basf.com)

[0344] Free radical generation measurement

[0345] We assessed the number of free radicals generated in the formulations after UV irradiation according to the approach described in Sohn M, et al. Impact of photostability and UVA / UVA-blue light protection on free radical generation. SOFW-Journal (2019). The free radicals were measured via electron spin resonance (ESR) spectroscopy using the photostable spin probe PCA, (2,2,5,5-tetramethyl pyrrolidine N-oxyl. The concentration of the spin marker added to the tested samples was followed by Electron Spin Resonance (ESR) spectroscopy before and after UV irradiation of the tested samples. The photostable spin marker will promtly react with free radicals eventually produced in the formulation under UV irradiation to be reduced to the ESR-silent hydroxylamine. The formulation was diluted in distillated water (1 :10 dilution factor) and a water solution of the spin marker PCA (2, 2, 5, 5, -tetramethyl pyrrolidine N-oxyl) was added to obtain a spin marker concentration of 0.01 mM. Knowing the concentration of the spin trap PCA within the formulation, the amount of reduced PCA was calculated. The sample was inserted in a capillary quartz tube to perform ESR measurement before and after 20 minutes of UV irradiation. The UV irradiation of the samples was performed with a xenon arc lamp Solar Simulatorfrom Newport-ORIEL Product Line 81260 equipped with a 300 W Xenon lamp. The irradiances as integrated values over the spectral ranges were 23.5 W / m2for the UVB range between 280 and 320 and 180 W / m2for the UVA range between 320 and 400 nm.

[0346] Pairwise Sensory test

[0347] At least 11 trained panellists for testing, all Chinese females. The volunteers are given 10 to 15 minutes to acclimatize to test environment: humidity 50 ± 10%, temperature on 21 ± 1 °C. Draw the test area (5cm x 8 cm) on both of the forearm. Apply 150pl of sample by the multi-pipette on to the test area.

[0348] Evaluate the sensory attributes on the Questionnaires.

[0349] Sensory attributes are defined as follows:

[0350] 1 . Distribution

[0351] 150 pL substance is applied on the inside of the forearms. With the tips of the index and middle finger the applied cream is distributed with 20 circling movements. During this action the resistance of the cream against the movement is evaluated. The less resistance means easier to distribute.

[0352] Score “-1” means significantly difficult distribution in comparison with the reference example;

[0353] Score “-0.5” means difficult distribution in comparison with the reference example;

[0354] Score “0” means identical distribution in comparison with the reference example; Score “0.5” means easier distribution in comparison with the reference example;

[0355] Score “1 ” means significantly easier distribution in comparison with the reference example.

[0356] 2. Watery feel (in use)

[0357] During the distribution, with the tips of the index and middle finger distributing the cream at 10 cirles, start evaluating which side of the forearms has more watery feel Score “-1” means significantly less watery in use in comparison with the reference example;

[0358] Score “-0.5” means less watery in use in comparison with the reference example;

[0359] Score “0” means identical watery in use in comparison with the reference example;

[0360] Score “0.5” means more watery in use in comparison with the reference example;

[0361] Score “1 ” means significantly more watery in use in comparison with the reference example.

[0362] 3. Oiliness (in use)

[0363] During the distribution, with the tips of the index and middle finger distributing the cream at 10 cirles, start evaluating which side of the forearms has more oily feel

[0364] Score “-1” means significantly more oiliness in use in comparison with the reference example;

[0365] Score “-0.5” means more oiliness in use in comparison with the reference example;

[0366] Score “0” means identical oiliness in use in comparison with the reference example;

[0367] Score “0.5” means less oiliness in use in comparison with the reference example;

[0368] Score “1 ” means significantly less oiliness in use in comparison with the reference example.

[0369] 4. Whitening

[0370] After distributing the cream with 20 circles, place the forearm under the light and observed which side of forearm remains whiter.

[0371] Score “-1” means significantly more whitening in comparison with the reference example;

[0372] Score “-0.5” means more whitening in comparison with the reference example;

[0373] Score “0” means identical whitening in comparison with the reference example;

[0374] Score “0.5” means less whitening in comparison with the reference example;

[0375] Score “1 ” means significantly less whitening in comparison with the reference example.

[0376] 5. Absorption I

[0377] 1 min after distribution, the volunteers have to recognize how the resistance of the cream is increasing which is an indication of the first absorption. The earlier this resistance is occurring the faster is the absorption.

[0378] Score “-1” means significantly slower Absorption I in comparison with the reference example;

[0379] Score “-0.5” means slower Absorption I in comparison with the reference example;

[0380] Score “0” means identical Absorption I in comparison with the reference example;

[0381] Score “0.5” means faster Absorption I in comparison with the reference example;

[0382] Score “1 ” means significantly faster Absorption I in comparison with the reference example.

[0383] 6. Absorption II

[0384] After 4 min reassess absorption.

[0385] Score “-1” means significantly slower Absorption II in comparison with the reference example;

[0386] Score “-0.5” means slower Absorption II in comparison with the reference example;

[0387] Score “0” means identical Absorption II in comparison with the reference example;

[0388] Score “0.5” means faster Absorption II in comparison with the reference example; Score “1 ” means significantly faster Absorption II in comparison with the reference example.

[0389] Before continuing, distribute samples on both forearms until all the samples have been fully absorbed.

[0390] 7. Shininess

[0391] After fully absorbed, observe the shininess under the light and access the which one has more relection Score “-1” means significantly more shininess in comparison with the reference example;

[0392] Score “-0.5” means more shininess in comparison with the reference example;

[0393] Score “0” means identical shininess in comparison with the reference example;

[0394] Score “0.5” means less shininess in comparison with the reference example;

[0395] Score “1 ” means significantly less shininess in comparison with the reference example.

[0396] 8. Stickiness

[0397] Pat the treated area with fingers lightly to assess the strength during raising up the forefinger. More strength means more sticky.

[0398] Score “-1” means significantly more stickiness in comparison with the reference example;

[0399] Score “-0.5” means more stickiness in comparison with the reference example;

[0400] Score “0” means identical stickiness in comparison with the reference example;

[0401] Score “0.5” means less stickiness in comparison with the reference example;

[0402] Score “1 ” means significantly less stickiness in comparison with the reference example.

[0403] 9. Oiliness

[0404] Slide the index and middle finger on the treated area to feel the oily feeling residue on the inner of forearm. It feels like kind of oil film covering the skin.

[0405] Score “-1” means significantly more oiliness in comparison with the reference example;

[0406] Score “-0.5” means more oiliness in comparison with the reference example;

[0407] Score “0” means identical oiliness in comparison with the reference example;

[0408] Score “0.5” means less oiliness in comparison with the reference example;

[0409] Score “1 ” means significantly less oiliness in comparison with the reference example.

[0410] 10. Waxy feel

[0411] Press the treated area with the index and middle finger strongly and move both fingers from upper side to down, in order to feel the waxy feeling residue on the forearm. More resistance means more waxy feel.

[0412] Score “-1” means significantly more waxy feel in comparison with the reference example;

[0413] Score “-0.5” means more waxy feel in comparison with the reference example;

[0414] Score “0” means identical waxy feel in comparison with the reference example;

[0415] Score “0.5” means less waxy feel in comparison with the reference example;

[0416] Score “1 ” means significantly less waxy feel in comparison with the reference example. 11. Residue / Filming

[0417] From overall view, feel the residue feeling on the inner of forearm. More product amount means more residue.

[0418] Score “-1” means significantly more residue / filming in comparison with the reference example;

[0419] Score “-0.5” means more residue / filming in comparison with the reference example;

[0420] Score “0” means identical residue / filming in comparison with the reference example;

[0421] Score “0.5” means less residue / filming in comparison with the reference example;

[0422] Score “1 ” means significantly less residue / filming in comparison with the reference example.

[0423] 12. Powdery feel

[0424] The powdery feel is a dry, smooth feeling that can be demonstrated with baby powder.

[0425] Score “-1” means significantly less powdery feel in comparison with the reference example;

[0426] Score “-0.5” means less powdery feel in comparison with the reference example;

[0427] Score “0” means identical powdery feel in comparison with the reference example;

[0428] Score “0.5” means more powdery feel in comparison with the reference example;

[0429] Score “1 ” means significantly more powdery feel in comparison with the reference example.

[0430] 13. Smoothness

[0431] After the complete absorption the treated area of the forearm is felt without any pressure

[0432] Score “-1” means significantly less smoothness in comparison with the reference example;

[0433] Score “-0.5” means less smoothness in comparison with the reference example;

[0434] Score “0” means identical smoothness in comparison with the reference example;

[0435] Score “0.5” means more smoothness in comparison with the reference example;

[0436] Score “1 ” means significantly more smoothness in comparison with the reference example.

[0437] 14. Light feel

[0438] After the complete absorption the treated area of the forearm is felt little residue, fresh, non-oily and absorbing fast.

[0439] Score “-1” means significantly less light feel in comparison with the reference example;

[0440] Score “-0.5” means less light feel in comparison with the reference example;

[0441] Score “0” means identical light feel in comparison with the reference example;

[0442] Score “0.5” means more light feel in comparison with the reference example;

[0443] Score “1 ” means significantly more light feel in comparison with the reference example.

[0444] 15. Soft feel

[0445] With a little pressure on the skin the softness is being felt. If there is no friction on the skin surface there is a soft skin feel, also in the third dimension, i.e. the elasticity of the skin is evaluated. This might be only noticeable after several applications.

[0446] Score “-1” means significantly less soft feel in comparison with the reference example;

[0447] Score “-0.5” means less soft feel in comparison with the reference example; Score “0” means identical soft feel in comparison with the reference example;

[0448] Score “0.5” means more soft feel in comparison with the reference example;

[0449] Score “1 ” means significantly more soft feel in comparison with the reference example. 16. Acceptance

[0450] The overall acceptance depends on the individual likes and dislikes. These are connected to age, skin type, gender etc. It is the most subjective parameter that is asked for in this sensory assessment.

[0451] Score “-1” means significantly less acceptance in comparison with the reference example;

[0452] Score “-0.5” means less acceptance in comparison with the reference example; Score “0” means identical acceptance in comparison with the reference example;

[0453] Score “0.5” means more acceptance in comparison with the reference example;

[0454] Score “1 ” means significantly more acceptance in comparison with the reference example.

[0455] Example 1

[0456] Table 1.1 : Test formulations

[0457] Inv. = Inventive example; Comp. = comparative example / reference

[0458] *Uvinul® TS Hydro is a 33% dispersion, 12% of Uvinul® TS Hydro corresponds therefore to about 4%

[0459] TDSA Manufacturing process:

[0460] 1 . Mix and heat phase B to 80 °C.

[0461] 2. Pre-mix phase A1 at room temperature, then add phase A1 into phase A, heat until 80 °C.

[0462] 3. Add phase B to the mixture of phase A+A1 under homogenization at 2000rpm at 80 °C. Then homogenize for 5 min at 2000 rpm. 4. Cool down to 50 °C, add phase C and D to the mixture and homogenize for 3min at 3000 rpm until uniform.

[0463] UV filter efficacy Both formulations (Inv. 1.1 comprises a combination of Uvinul® A Plus and Uvinul® TS Hydro as UVA filters and Ref. 1.1 comprises only Uvinul® A Plus) were tested for their UV-filter efficacy ((SPF + UVA- PF) / total amount of UV filter (in %)). The results obtained are shown in Table 1 .2 below.

[0464] Table 1.2

[0465] The results show that the inventive composition containing TDSA provided for a better UV filter efficacy, as calculated by adding the SPF in vitro and the UVA-PF in vitro and dividing the sum thereof by the total amount of UV filters in % in the composition (Inv: 12.8 wt.-%; Ref. 14.8 wt.-%).

[0466] Sensory test:

[0467] Further, both compositions were tested for their sensory profiles. Figure 1 (Pairwise comparison of Inv. 1.1 and Ref. 1.1) shows that using Uvinul® TS Hydro (TDSA) provides a sensory improvement. During application, the composition with Uvinul® TS Hydro showed less whitening and faster absorption after 1 min and 4 min in comparison to the reference formulation. After application, there are significant improvements for most attributes in skin finish stage.

[0468] Compositions Inv 1.1 and Ref .1.2 which differ by the used neutralizing agent were also evaluated with respect to their noodling effect (also termed pilling effect) as follows: 0.15 g of the sample composition were applied to the back of the hand and spread by drawing 20 circles with the index and middle fingers to distribute the product evenly. Any excess product was removed from the finger. After waiting for 1 min, 30 more circles were drawn on the area with the applied composition with the index and middle finger to observe the noodling (formation of white “noodles” of the composition). While in case of composition Ref. 1 .2 white residue noodles were observed, no such noodles were observed in case of composition Inv. 1.1.

[0469] Example 2

[0470] Free-radical generation was studied for 3 different formulations Table 2.1). The results are shown in

[0471] Table 2.2 below.

[0472] Table 2.1 : Test formulations

[0473] *Uvinul® TS Hydro is a 33% dispersion, 9% of Uvin TS Hydro corresponds therefore to about 3% TDSA

[0474] Table 2.2: Free radical generation

[0475] Table 2.2 shows that TDSA neutralized with L-arginine (Inv. 2.1) does generate significantly less or almost no free radicals upon UV exposure than the placebo formulation (without UV filters) or the formulation with TDSA neutralized with triethanolamine. Example 3

[0476] Table 3.1 : Performance in formulation with oil soluble UV filters

[0477] *Uvinul® TS Hydro is a 33% dispersion, 3% of Uvinul® TS Hydro corresponds therefore to about 1%

[0478] TDSA

[0479] Manufacturing instruction: Heat up part A and B to 75-85°C. Add part B into part A under stirring, homogenize shortly with an Ultra Turraxtype devide. Prepare part C and add to the emulsion (A+B) under stirring.

[0480] Add part D below 40°C. Check final pH and adjust if necessary.

[0481] As can be seen in Table 3.2, addition of Uvinul® TS Hydro to a sunscreen formulation comprising the oil soluble filters DHHB, BEMT and EHT significantly increases in vivo SPF and in vitro UVA-PF values when compared to what would have been expected based on in silico performance calculation with the addition of TDSA .

[0482] Table 3.2: Performance in formulation with oil soluble UV filters

[0483] Table 3.3: Performance in formulation with oil soluble and water soluble UV filters

[0484] *Uvinul® TS Hydro is a 33% dispersion, 3% of Uvinul® TS Hydro corresponds therefore to about 1 %

[0485] TDSA

[0486] Manufacturing instruction: Heat up part A and B to 75-85°C. Add part B into part A under stirring, homogenize shortly with an Ultra Turrax type device. Prepare part C and add to the emulsion (A+B) under stirring. Prepare part D and add to the emulsion (A+B+C) under stirring. Add part E below 40°C. Check final pH and adjust if necessary. As can be seen in Table 3.4, Uvinul® TS Hydro increases significantly SPF in vivo and UVA-PF in vitro in formulations containing oil soluble and water soluble UV filters when we compare to what would have been expected based on in silico performance calculation with the addition of TDSA .

[0487] Table 3.4: Performance in formulations with oil soluble and water soluble UV filters Example 4:

[0488] The solution of TDSA had a pH of about 1 (Uvinul TS Hydro) and was neutralized to achieve a a pH of

[0489] 6.5-7.0 with the different tested neutralizers

[0490] Table 4.1 : Stability tests of 10% TDSA with different Neutralization agents

[0491] KOH = potassium hydroxide, NaOH = sodium hydroxide, Tris = tromethamine, TEA = triethanolamine, THPED = tetrahydroxypropyl ethylenediamine

[0492] It can be seen from Table 4.1 that inorganic pH neutralizers engender a white precipitate of TDSA and are not suitable to be used with TDSA.

[0493] The stable mixtures of table 4.1 were also tested for sensory profile by trained human volunteers.

[0494] The trained panel was given 10 to 15 minutes to acclimatize to test environment: humidity 50 ± 10%, temperature on 21 ± 1 °C. Draw the test area (5cm x 8 cm) on both of the forearm. Apply 150ul of sample by the multi-pipette on to the test area. Evaluate the following sensory attributes after application.

[0495] Stickiness: Pat the treated area with fingers lightly to assess the strength during raising up the forefinger. More strength means more sticky.

[0496] Squeakiness: Press the treated area with the index and middle finger strongly and move both fingers from upper side to down, in order to feel the film residue on the forearm. Less continuous with more resistance means more squeakiness.

[0497] Table 4.2: Impact of neutralizer on sensory (stickiness during and after application)

[0498] *first sensory impression by trained panel of test subjects

[0499] According to Table 4.2, the best neutralizers for sensory are tromethamine and L-arginine since the skin feeling is less sticky and squeaky than with the other neutralizers.

Claims

Claims1. Topical composition, comprising:(i) terephthalylidene-3,3'-dicamphor-10,10'-disulfonic acid (INCI, terephthalylidene dicamphor sulfonic acid, TDSA);(ii) at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group; and(iii) at least one UV filter other than terephthalylidene dicamphor sulfonic acid, selected from the group consisting of:(a) at least one UVA filter, preferably selected from the group consisting of disodium phenyl dibenzimidazole tetrasulfonate (DPDT), hexyl 2-[4-(diethylamino)-2- hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate, DHHB), 1-(4-(1 ,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1 ,3-dione (INCI butyl methoxydibenzoylmethane, BMDBM), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), and combinations thereof; and / or(b) at least one UVB filter, preferably selected from the group consisting of 4,4',4"-(1 ,3,5- triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone, EHT), 4,4'-[[6-[[4-[[(1 ,1-dimethylethyl)amino]carbonyl]phenyl]amino]-1 ,3,5- triazin-2,4-diyl]diimino]bis-benzoic acid-bis(2-ethylhexyl)ester (INCI diethylhexyl butamido triazone, DBT), phenylbenzimidazole sulfonic acid (PBSA), and combinations thereof; and / or(c) at least one broadband UV filter, preferably selected from the group consisting of bisethylhexyloxyphenol methoxyphenyl triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine, BEMT), 2-(2H-benzotriazol-2-yl)-6-[(2-ethylhexyloxy)methyl]- 4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl- 1-[(trimethylsilyl)oxy]-1-disiloxanyl]propyl]phenol (INCI drometrizole trisiloxane, DTS), 2,2'-methylenbis[6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol] (INCI methylene Bis-benzotriazolyl tetramethylbutylphenol, MBBT), phenylene bisdiphenyltriazine (PBDT), and combinations thereof; and / or(d) at least one organic particulate UV filter, preferably selected from the group consisting of 2,2'-methylene bis[6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol] (INCI methylene bis-benzotriazolyl tetramethylbutylphenol), 2,4,6-tris(biphenyl-4-yl)-1 ,3,5- triazine (INCI trisbiphenyl triazine, TBPT), 1 ,1 ’-(1 ,4-piperazinediyl)bis[1-[2-[4- (diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (INCI bis-(diethylaminohydroxybenzoyl benzoyl) piperazine), 5,6,5’,6’-tetraphenyl-3-3’-(1 ,4- phenylene)bis(1 ,2,4-triazine) (INCI phenylene bis-diphenyltriazine; PBDT), micronized 1 ,4-di(benzoxazole-2-yl)benzene and combinations thereof; and / or(e) at least one inorganic UV filter, preferably selected from the group consisting of titanium dioxide, zinc oxide, and mixtures thereof; wherein the pH of the composition is within the range of 4.0 to 8.0.

2. The topical composition according to claim 1 , wherein the at least one organic pH neutralizer is selected from an amino acid, preferably a basic amino acid, more preferably L-lysine or L- arginine, most preferably L-arginine.

3. The topical composition according to claim 1 , wherein the at least one organic pH neutralizer is selected from primary amino alcohols, preferably beta-amino alcohols, more preferably tris(hydroxymethyl)aminomethane (tromethamine).

4. The topical composition according to any one of claims 1 to 3, wherein the amount of the at least one organic pH neutralizer is selected such that the pH of the composition is within the range of 4.0 to 8.0.

5. The topical composition according to any one of the preceding claims, wherein the weight ratio of TDSA to the at least one organic pH neutralizer is in the range of 0.5:1 to 3:1 , preferably 1 :1 to 2.5:1.

6. The topical composition according to any one of the preceding claims, wherein the TDSA is present in an amount of about 0.2 to 10.0 wt.-%, preferably about 0.5 to 5.0 wt.-%, more preferably about 0.7 to 5.0 wt.-%, even more preferably about 1 .0 to 3.0 wt.-%, based on the total weight of the composition.

7. The topical composition according to any one of the preceding claims, wherein the at least one organic pH neutralizer is present in an amount of about 0.2 to 10 wt.-% based on the total weight of the composition.

8. The topical composition according to any one of the preceding claims, wherein the composition comprises the least one UV filter other than TDSA in an amount of 2 to 40 wt.-%, preferably of 5 to 35 wt.-%, more preferably of 5 to 30 wt.-%, still more preferably of 5 to 25 wt.-%, and, in particular, of 8 to 20 wt.-%, based on the composition.

9. The topical composition according to any one of the preceding claims, wherein the at least one UV filter other than TDSA comprises(1) a UV filter that is solid at 25°C; and / or(2) a UV filter that is soluble in or miscible with at least one cosmetic oil; and / or(3) an organic UV filter; and / or(4) a particulate UV filter.

10. The topical composition according to any one of the preceding claims, wherein the at least one UV filter other than TDSA comprises at least one UV filter selected from bis-ethylhexyloxyphenolmethoxyphenyl triazine (BEMT), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate (MCE), butyl methoxydibenzoylmethane (BMDBM), ethylhexyl triazone (EHT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), tris-biphenyl triazine (TBPT), and any combination of two or more thereof.

11. The topical composition according to claim 10, wherein the composition comprises DHHB, preferably in an amount of from 0.5 to 10 % by weight, more preferably 1 to 8 % by weight and more preferably 1 .5 to 5 % by weight, based on the total weight of the composition.

12. The topical composition according to claim 10 or 1 1 , wherein the weight ratio of TDSA to DHHB is in the range of 5:1 to 0.5:5, preferably 3:1 to 1 :3.

13. The topical composition according to any one of the preceding claims, comprising(1) at least one broadband UV filter, preferably BEMT, preferably in an amount of from 0.5 to 10 % by weight, more preferably 1 to 5 % by weight and more preferably 2 to 4 % by weight, based on the total weight of the composition; and / or(2) at least one UVB filter, preferably EHT, preferably in an amount of from 0.5 to 10 % by weight, more preferably 1 to 5 % by weight and more preferably 2 to 4 % by weight, based on the total weight of the composition; and / or(3) at least one organic particulate UV filter, preferably MBBT or TBPT, preferably in an amount of from 0.5 to 10 % by weight, more preferably 1 to 5 % by weight and more preferably 2 to 4 % by weight, based on the total weight of the composition; wherein the composition preferably comprises (1) and (2) and, optionally, (3).

14. The topical composition according to any one of the preceding claims, wherein(1) the composition is free of at least one or more of parabens, triethanolamine (TEA), and organic UV filter compounds selected from the group of homomenthyl salicylate, ethylhexyl methoxycinnamate, octocrylene, and ethylhexyl salicylate;(2) the composition is free of triethanolamine (TEA) and octocrylene; and / or(3) the composition further comprises at least one additive, preferably selected from the group consisting of cosmetic oils, emulsifiers, emollients, viscosity regulators (thickeners), buffering and pH adjustment agents (other than the organic pH neutralizer (ii)), stabilizers, sensory enhancers, humectants, film formers, UV scattering compounds, UV booster compounds, adjuvants, preservatives, perfumes, and combinations thereof.

15. The composition of claim any one of the preceding claims, wherein(i) the composition comprises DHHB in a weight ratio of TDSA to DHHB in the range of 0.1 :1 to <1 :1 , preferably 0.1 :1 to <1 :1 ,(ii) the composition further comprises at least one further UV filter selected from EHMC, EHT, BMDBM and DBT,(iii) the composition is free of octocrylene, and(iv) the composition is free of TEA.

16. Use of at least one organic pH neutralizer, wherein the organic pH neutralizer comprises at least one primary amino group, for improving the sensory properties of and / or reducing the generation of radicals upon UV exposure in a topical composition comprising TDSA, preferably a sunscreen or daily care composition comprising TDSA.

Images