EFFICIENT SUNSCREEN COMPOSITIONS WITH DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE AND BUTYL METHOXYDIBENZOYLMETHANE FREE OF OCTOCRYLENE

Abstract

The present invention relates to sunscreen or daily care composition comprising (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane); and (iii) 2,4-bis-{[4-(2-ethy-hexyoxy)-2-hydroxy]-pheny}-6-(4-methoxypheny)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine); and (iv) 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone) and/or 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 diethyl-hexyl-butamidotriazone); and (v) at least one organic particulate UV filter, wherein the composition is free of ethylhexyl-2-cyano-3, 3-diphenyl-acrylate (INCI octocrylene), 2-ethylhexyl-(2E)-3-(4-methoxyphenyl) acrylate (INCI ethylhexyl methoxy cinnamate) and pp benzylidene malonates, and wherein the composition comprises diethylamino hydroxybenzoyl hexylbenzoate and butyl methoxydibenzoylmethane in a ratio of larger or equal to 0.8. Furthermore, the present invention relates to the use of said composition for the administration to sensitive skin. In addition, the present invention relates to the use of said composition to reduce sand adhesion after application of the composition on the skin.

Claims

1.-19. (canceled)

20. A sunscreen or daily care composition comprising (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane); and (iii) 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine); and (iv) 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone) and/or 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-butamidotriazone); and (v) at least one organic particulate UV filter, wherein the composition is free of ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene), 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate) and benzylidene malonates according to the following preferred structures: ##STR00013## wherein R.sup.1 is methyl, ethyl, propyl or n-butyl; if R.sup.1 is methyl, then R is tert. butyl or a radical of formula ##STR00014## or a radical of formula ##STR00015## wherein R.sup.2 and R.sup.3 are independently from each other hydrogen or methyl; R.sup.4 is methyl, ethyl or n-propyl; R.sup.5 and R.sup.6 are independently from each other hydrogen or C.sub.1-C.sub.3-alkyl; if R.sup.1 is ethyl, propyl or n-butyl, then R is isopropyl; and wherein the composition comprises (i) to (ii) in a ratio of larger or equal to 0.8.

21. The sunscreen or daily care composition according to claim 20, wherein the composition comprises (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in a ratio of larger or equal to 1.

22. The sunscreen or daily care composition according to claim 20, wherein the composition comprises (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in a ratio of from 1:1 to 10:1.

23. The sunscreen or daily care composition according to claim 20, wherein the composition is free of titanium dioxide and zinc oxide.

24. The sunscreen or daily care composition according to claim 20, wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and isoamyl-4-methoxycinnamate (INCI isoamyl-p-methoxy cinnamate).

25. The sunscreen or daily care composition according to claim 20, wherein the composition is free of parabens.

26. The sunscreen or daily care composition according to claim 20, wherein the composition is provided in the form of a sprayable product.

27. The sunscreen or daily care composition according to claim 20, wherein the composition is free of emulsifier.

28. The sunscreen or daily care composition according to claim 20, wherein the composition is free of phenoxyethanol.

29. The sunscreen or daily care composition according to claim 20, wherein (iii) is an oil soluble UV filter or wherein (iii) is 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine) dissolved in a polymer matrix to be dispersible in water.

30. The sunscreen or daily care composition according to claim 20, wherein the composition comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 1% to 10% by weight, based on the total weight of the composition.

31. The sunscreen or daily care composition according to claim 20, wherein the composition comprises 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in an amount of from 1% to 5% by weight, based on the total weight of the composition.

32. The sunscreen or daily care composition according to claim 20, wherein the composition comprises 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine) in an amount of from 0.5% to 5% by weight, based on the total weight of the composition.

33. The sunscreen or daily care composition according to claim 20, wherein the composition comprises 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone) in an amount of from 0.5% to 5% by weight based on the total weight of the composition.

34. The sunscreen or daily care composition according to claim 20, wherein the composition comprises 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-butamidotriazone) in an amount of from 0.5% to 5% by weight, based on the total weight of the composition.

35. The sunscreen or daily care composition according to claim 20, wherein the at least one organic particulate UV filter is 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), 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), micronized 1,4-di(benzoxazole-2′-yl)benzene and combinations thereof.

36. The sunscreen or daily care composition according to claim 20, wherein the composition has a sun protection factor (SPF) of at least 20.

37. The sunscreen or daily care composition according to claim 20, wherein the composition has a b* value of <25.

38. Use of a sunscreen or daily care composition as defined in claim 20 to reduce sand adhesion on the skin.

39. The sunscreen or daily care composition according to claim 20, wherein the composition comprises (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in a ratio of from 1:1 to 5:1.

Description

EXAMPLES

[0330] Process of Manufacture of Sunscreen Compositions

[0331] The ingredients of part A, as well as the ingredients of part B as provided below in Tables 1.1, 1.2, 1.3 and 1.4 for each tested sunscreen composition were combined and heated to 80° C. respectively, wherein part A was added to part B under stirring and was further homogenized. Subsequently, the sunscreen composition was cooled down to room temperature under stirring. If present, part C was added and the pH of each composition was adjusted to 6.5-7.00 with NaOH.

[0332] All amounts referred to in the following tables refer to the respective amounts in % by weight, based on the total weight of the composition.

[0333] Sunscreen Compositions

TABLE-US-00001 TABLE 1.1 Ingredient Comparative Comparative Comparative (Trade Name) composition 1a composition 1b composition 1c Part A Dibutyl adipate 15.00 15.00 10.00 (Cetiol B) C.sub.12-C.sub.15 alkyl benzoate 10.00 10.00 10.00 (Cetiol AB) Stearyl alcohol 2.50 2.50 2.50 (Lanette 18) Preservative 1.00 1.00 1.00 BMDBM 4.00 4.00 4.00 DHHB (Uvinul A Plus) — — 2.00 BEMT (Tinosorb S) 1.00 1.00 1.00 OCR (Uvinul N539T) 10.00 — — Part B Water qsp 100% qsp 100% qsp 100% Glycerin 2.00 2.00 2.00 Disodium EDTA 0.20 0.20 0.20 Acrylates/Beheneth-25 2.00 2.00 2.00 methacrylate copolymer (Tinovis GTC) Xanthan Gum 0.50 0.50 0.50 (Rheocare XGN)

TABLE-US-00002 TABLE 1.2 Ingredient (Trade Name) Composition 2 Composition 3 Composition 4 Part A Dibutyl adipate (Cetiol B) 15.00 15.00 15.00 C.sub.12-C.sub.15 alkyl benzoate 10.00 10.00 10.00 (Cetiol AB) Stearyl alcohol 2.50 2.50 2.50 (Lanette 18) Preservative 1.00 1.00 1.00 BMDBM 4.00 4.00 4.00 DHHB (Uvinul A Plus) 4.00 6.00 8.00 BEMT (Tinosorb S) 1.00 1.00 1.00 OCR (Uvinul N539T) — — — Part B Water qsp 100% qsp 100% qsp 100% Glycerin 2.00 2.00 2.00 Disodium EDTA 0.20 0.20 0.20 Acrylates/Beheneth-25 2.00 2.00 2.00 methacrylate copolymer (Tinovis GTC) Xanthan Gum 0.50 0.50 0.50 (Rheocare XGN)

TABLE-US-00003 TABLE 1.3 Ingredient (Trade Name) Composition 5 Part A Dibutyl adipate (Cetiol B) 15.00 C.sub.12-C.sub.15 alkyl benzoate (Cetiol AB) 10.00 Stearyl alcohol (Lanette 18) 2.50 Preservative 1.00 BMDBM 4.00 DHHB (Uvinul A Plus) 10.00 BEMT (Tinosorb S) 1.00 OCR (Uvinul N539T) — Part B Water qsp 100% Glycerin 2.00 Disodium EDTA 0.20 Acrylates/Beheneth-25 2.00 methacrylate copolymer (Tinovis GTC) Xanthan Gum (Rheocare XGN) 0.50

TABLE-US-00004 TABLE 1.4 Comparative Comparative Ingredient (Trade Name) composition 2a composition 2b Composition 6 Part A Dibutyl adipate (Cetiol B) 10.00 10.00 10.00 C.sub.12-C.sub.15 alkyl benzoate 10.00 10.00 10.00 (Cetiol AB) Stearyl alcohol 2.50 2.50 2.50 (Lanette 18) BMDBM 3.00 3.00 3.00 DHHB (Uvinul A Plus) — — 5.00 BEMT (Tinosorb S) 1.00 1.00 1.00 Part B Water qsp 100% qsp 100% qsp 100% Glycerin 2.00 2.00 2.00 Disodium EDTA 0.20 0.20 0.20 (EDTA BD) Acrylates/Beheneth-25 2.00 2.00 2.00 methacrylate copolymer (Tinovis GTC UP) Xanthan Gum 0.50 0.50 0.50 (Rheocare XGN) Part C MBBT* (Tinosorb M) 5.00 — — *The amount refers to active matter, 5% of MBBT corresponds to 10% of the commercial product Tinosorb M.

[0334] Recovery measurements on photo stability of BMDBM

[0335] The sunscreen or UV filter compositions as defined above are applied on roughened quartz plates (2 μl/cm.sup.2). Plates are irradiated using Atlas CPS device at different duration times (MED=Minimal Erythema Dose): [0336] 0 h (0 MED, no irradiation) [0337] 1 h (5 MED), [0338] 2 h (10 MED), [0339] 4 h (28 MED).
In total, four plates are prepared for each irradiation condition. After irradiation, each plate is rinsed off with tetrahydrofuran. The rinsing solution is further analyzed via HPLC to determine the recovery of BMDBM.

TABLE-US-00005 TABLE 2.1 Comparative Comparative Comparative composition 1a composition 1b composition 1c  0 MED 100%  100%  100%   5 MED 98% 58% 62% 10 MED 89% 31% 37% 20 MED 83% 12% 14%

TABLE-US-00006 TABLE 2.2 Composition 2 Composition 3  0 MED 100%  100%   5 MED 79% 87% 10 MED 62% 75% 20 MED 33% 52%

TABLE-US-00007 TABLE 2.3 Composition 4 Composition 5  0 MED 100% 100%  5 MED  86%  97% 10 MED  73%  77% 20 MED  55%  61%

TABLE-US-00008 TABLE 2.4 Comparative Comparative composition 2a composition 2b Composition 6  0 MED 100% 100% 100%  5 MED  68%  55%  82% 10 MED  43%  26%  63% 20 MED  21%  11%  41%

[0340] Recovery Measurements on Photo Stability of BEMT

[0341] The sunscreen or UV filter compositions as defined above are applied on roughened quartz plates (2 μl/cm.sup.2). Plates are irradiated using Atlas CPS device at different duration times (MED=Minimal Erythema Dose): [0342] 0 h (0 MED, no irradiation) [0343] 1 h (5 MED), [0344] 2 h (10 MED), [0345] 4 h (20 MED).
In total, four plates are prepared for each irradiation condition. After irradiation, each plate is rinsed off with tetrahydrofuran. The rinsing solution is further analyzed via HPLC to determine the recovery of BEMT.

TABLE-US-00009 TABLE 3.1 Comparative Comparative Comparative composition 1a composition 1b composition 1c  0 MED 100% 100% 100%  5 MED 103%  93%  92% 10 MED  98%  86%  89% 20 MED 100%  76%  76%

[0346] A Person Skilled in the Art is Aware that Data Above 100% after Irradiation are Due to Common Measurement Fluctuations.

TABLE-US-00010 TABLE 3.2 Composition 2 Composition 3  0 MED 100% 100%  5 MED  99% 101% 10 MED 102% 104% 20 MED  95% 102%

[0347] A Person Skilled in the Art is Aware that Data Above 100% after Irradiation are Due to Common Measurement Fluctuations.

TABLE-US-00011 TABLE 3.3 Composition 4 Composition 5  0 MED 100% 100%  5 MED  98% 106% 10 MED  95%  98% 20 MED  95%  97%

[0348] A Person Skilled in the Art is Aware that Data Above 100% after Irradiation are Due to Common Measurement Fluctuations.

TABLE-US-00012 TABLE 3.4 Comparative Comparative composition 2a composition 2b Composition 6  0 MED 100% 100% 100%  5 MED  98%  93%  97% 10 MED  92%  84%  92% 20 MED  90%  78%  92%

[0349] Measurement of Interfacial Tension (Polarity Index)

[0350] Interfacial tension of the respective emollients as listed below was measured using a Tensimat Densimat TD2000.

TABLE-US-00013 TABLE 4.1 polarity index [mN/m] polarity index >30 hydrogenated polyisobutene 45 mN/m (reference mineral oil 43 emollients) cyclopentasiloxane 32 polarity index <30 octyldodecanol 25 mN/m butylene glycol 22 dicaprylate/dicaprate C12-15 alkyl benzoate 22 caprylic capric triglyceride 21 propylene glycol 20 dicaprylate/dicaprate diisopropyl sebacate 19 phenethyl benzoate 19 dibutyl adipate 14 diisopropyl adipate 12 triethyl citrate 7 tributyl citrate 10

[0351] UV Filter Performance

[0352] The wavelength of maximum absorbance (λmax) is an indicator to describe the performance of a UV filter molecule. It gives the wavelength at which the absorbance is at maximum. For a UVA filter, the wavelength of maximum absorbance should be close to 359 nm that corresponds to the apex of the PPD (persistent pigment darkening) effectiveness spectrum. The PPD effectiveness spectrum corresponds to the multiplication of the PPD (persistent pigment darkening) action spectrum with the light intensity (see ISO 24443).

The UV transmission spectrum of each UV filter-emollient mixture was measured from 290 to 400 nm using a UV/Vis spectrophotometer Perkin Elmer Lambda 25. Three stock solutions with a concentration of 1 mM of UV filter were prepared for each mixture. Further, three dilutions of each stock solution were prepared resulting in nine measurements in total per UV filter-emollient solution. Then, all solutions were filled in UV transparent quartz cuvette of 1 cm optical path-length for UV Transmission measurements.

[0353] λMax Values of BMDBM

TABLE-US-00014 TABLE 4.2 λmax values [nm] (BMDBM) polarity index >30 mN/m mineral oil 355 (reference emollients) hydrogenated 354 polyisobutene cyclomethicone 350 polarity index <30 mN/m diisopropyl adipate 357 isopropyl myristate 357 dicaprylyl carbonate 357 dibutyl adipate 358 caprylic capric 358 triglyceride C12-15 alkyl 359 benzoate phenethyl benzoate 362 diisopropyl sebacate 357 octyldodecanol 357 triethyl citrate 359 tributyl citrate 359

[0354] λMax Values of DHHB

TABLE-US-00015 TABLE 4.3 λmax values [nm] (DHHB) polarity index >30 mN/m hydrogenated 345 (reference emollients) polyisobutene cyclomethicone 345 mineral oil 346 polarity index <30 mN/m phenethyl benzoate 355 dibutyl adipate 351 C12-15 alkyl 351 benzoate diisopropyl adipate 351 butylene glycol 350 dicaprylate/dicaprate caprylic capric 350 triglyceride diisopropyl sebacate 350 octyldodecanol 349 triethyl citrate 353 tributyl citrate 352

[0355] Solubility Measurements

[0356] 0.02 g of UV Filter are added to 2 ml of the respective emollient as displayed below, previously filled into a 20 ml vial with cap. The vial is placed in a thermostated water bath (25° C.) and the blend is stirred for seven days. If the tested UV-filter is fully soluble, additional filter is added until precipitation is observed. After seven days, the sample is centrifuged for 30 minutes at 13000 rpm. If the supernatant is turbid, it is filtered through a 0.2 μm non steril Membrex 25 PET filter. Prior to the measurement, the samples were either diluted with a suitable solvent, or, in case of lower concentrations measured without further dilution in quartz cuvettes of 1 cm optical path-length. The concentration of UV-filter is then determined with UV/Vis-spectroscopy using a Perkin Elmer Lambda 20 device (according to Method A in Herzog B., Giesinger J., Schnyder M., SOFW Journal, 2013, 139 (7), pages 7-14).

TABLE-US-00016 TABLE 4.4 solubility [%] (BMDBM) polarity index >30 mN/m mineral oil <1 (reference emollients) hydrogenated <1 polyisobutene cyclomethicone <1 diisopropyl adipate 10 polarity index <30 mN/m dibutyl adipate 18 caprylic capric 12 triglyceride C12-15 alkyl 14 benzoate phenethyl benzoate 25 diisopropyl sebacate 16 octyldodecanol 2 triethyl citrate 15 tributyl citrate 18

TABLE-US-00017 TABLE 4.5 solubility [%] (DHHB) polarity index >30 mN/m mineral oil <1 (reference emollients) hydrogenated <1 polyisobutene cyclomethicone <1 polarity index <30 mN/m phenethyl benzoate 57 dibutyl adipate 31 C12-15 alkyl 22 benzoate diisopropyl adipate 21 butylene glycol 23 dicaprylate/dicaprate propylene glycol 22 dicaprylate/dicaprate caprylic capric 14 triglyceride diisopropyl sebacate 41 octyldodecanol 2.5 triethyl citrate 29 tributyl citrate 29.4

[0357] Sand Adhesion Test

[0358] The ingredients of part A, as well as the ingredients of part B as provided below in Table 5 for each tested sunscreen composition were combined and heated to 80° C. respectively, wherein part A was added to part B under stirring and was further homogenized. Subsequently, the sunscreen composition was cooled down to room temperature under stirring. Parts C and 0 were added and the pH of each composition was adjusted to 6.5-7.00 with NaOH.

TABLE-US-00018 TABLE 5 Comparative Ingredient Composition Composition Composition Composition (Trade Name) 3 7 8 9 Part A Stearyl phosphate 5.00 5.00 5.00 5.00 Phenethyl benzoate 3.00 3.00 3.00 3.00 Triisodecyl trimellitate 3.00 3.00 3.00 3.00 Dimethyl capramide 1.00 1.00 1.00 1.00 Tricontanyl PVP 1.00 1.00 1.00 1.00 Ethoxydiglycol oleate 1.50 1.50 1.50 1.50 Squalane 3.00 3.00 3.00 3.00 C12-15 alkyl 2.00 2.00 2.00 2.00 benzoate (Cetiol AB) Glyceryl stearate 2.00 2.00 2.00 2.00 Cetyl alcohol 2.00 2.00 2.00 2.00 (Lanette 16) Bis-ethylhexyloxyphenol 2.00 2.00 2.00 5.00 Methoxyphenyl Triazine (Tinosorb S) Propanedioic acid, 10.00 2-[(4-methoxyphenyl) methylene]-, 1,3-bis((2- methylbutyl) ester Diethylhexyl Butamino 8.00 4.00 Triazone Diethylamino 4.00 4.00 4.00 4.00 Hydroxy-benzoyl Hexyl Benzoate (Uvinul A Plus) Ethylhexyl Triazone 2.00 4.00 5.00 (Uvinul T150) Butyl 3.00 3.00 3.00 3.00 Methoxydibenzoyl- methane Part B Aqua qsp 100% qsp 100% qsp 100% qsp 100% Steareth-10 allyl 0.50 0.50 0.50 0.50 ether/acrylates Glycerine 2.50 2.50 2.50 2.50 Diazolidinyl urea (and) 0.15 0.15 0.15 0.15 iodopropynyl butylcarbamate Sodium Stearoyl 0.70 0.70 0.70 0.70 Gluta Sclerotium Gum 0.10 0.10 0.10 0.10 Part C Cyclopentasiloxane 1.50 1.50 1.50 1.50 (and) dimethiconol Triethanolamine 1.85 1.85 1.85 1.85 Citric acid (and) silver 0.10 0.10 0.10 0.10 citrate Part D Methylene Bis- 3.00 3.00 3.00 3.00 Benzotria-zoly1 Tetramethylbutyl- phenol* SPF cal. 52 52 53 53 *The amount refers to active matter, 3% MBBT corresponds to 6% of the commercial product Tinosorb M
Comparative Composition 3 and Compositions 7, 8 and 9 have been tested for their performance to prevent or at least minimize sand adhesion on the skin after application of the sunscreen composition. The following method has been used:
50 mg of the test formulation was applied on PMMA plates (Helioscreen) with a dimension of 5.0 cm×5.0 cm by manual application as homogeneous as possible. The plates were placed for 15 minutes in the dark to allow water evaporation and equilibration of the plate to achieve the film formation before further processing. After equilibration period, each single plate was weighted with an analytical balance. The sample was covered with 10 g of sand (ref. 1.07711.1000 seesand, Merck KGaA). This amount allows a coverage in excess of the entire PMMA plate. Afterwards, the plate was put from the horizontal position in the vertical position equaling a 90° C. turn and kept for 5 seconds in the vertical position. The same step was repeated for each side of the plate. The plate with the remaining stuck sand was weighed again and the amount of stuck sand calculated according to the following formula:

Sand adhered on the plate (mg)=plate after sand contact (mg)−sunscreen-covered plate (mg)

The sand adhesion rates for each composition are as shown in Table 6.

TABLE-US-00019 TABLE 6 Cornparative Composition Composition Composition Composition 3 7 8 9 Sand 0.527 0.5239 0.4978 0.5194 adhesion 0.5437 0.5388 0.5122 0.5232 tests 0.5581 0.5428 0.5063 0.5399 0.5599 0.5138 0.5142 0.4891 0.5493 0.5155 0.4947 0.5012 Average 0.548 0.527 0.505 0.515 sand adhesion
Comparative Composition 3 shows a stronger stickiness to sand than the inventive Compositions 7, 8 and 9.

Color Test

[0359] The ingredients of part A, as well as the ingredients of part B as provided below in Table 7 for each tested sunscreen composition were combined and heated to 80° C. respectively, wherein part A was added to part B under stirring and was further homogenized. Subsequently, the sunscreen composition was cooled down to room temperature under stirring. Parts C and 0 were added and the pH of each composition was adjusted to 6.5-7.00 with NaOH.

TABLE-US-00020 TABLE 7 Comparative Ingredient (Trade Name) Composition 4 Composition 10 Composition 11 Part A Octyldodecanol (Eutanol G) 4.00 4.00 4.00 caprylic/capric triglycerides 1.00 1.00 1.00 glyceryl stearate 1.00 1.00 1.00 hydrogenated coco-glycerides 1.00 1.00 1.00 ethylhexyl cocoate 4.00 4.00 4.00 sodium stearoyl glutamate 0.30 0.30 0.30 (Emulgin SG) silica dimethyl silylate 2.00 2.00 2.00 Bis-ethylhexyloxyphenol 1.00 1.00 1.00 Methoxyphenyl Triazine (Tinosorb S) Diethylhexyl Butamino 1.00 1.00 5.00 Triazone Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A 5.00 5.00 5.00 Plus) Ethylhexyl Triazone 4.00 4.00 (Uvinul T150) Butyl 3.50 3.50 3.50 Methoxydibenzoylmethane Titanium dioxide (and) 1.50 Triethoxycaprylylsilane Homosalate 7.00 7.00 7.00 Ethylhexyl Salicylate 3.50 3.50 3.50 Part B Aqua qsp 100% qsp 100% qsp 100% Sodium hydroxyde 0.025 0.025 0.025 Xanthan gum 0.50 0.50 0.50 Acrylates/C10-30 alkyl acrylate 0.10 0.10 0.10 crosspolymer Part C Methylene Bis-Benzotriazolyl 1.50 1.50 Tetramethylbutyl phenol * Part D Phenoxyethanol 0.60 0.60 0.60 Alcohol denat 6.00 6.00 6.00 SPF cal. 40 42 42 * The amount refers to active matter, 1,5% MBBT corresponds to 3% of the commercial product Tinosorb M

[0360] Comparative Composition 4 and Compositions 10 and 11 have been tested for their color. The principle is that the brighter the color of the product is, the more the product is accepted by the consumer. The following method has been used:

[0361] The color of a cosmetic sunscreen formulation is assessed based on the determination of the L*a*b* color space parameters. With this method, the color difference between several samples can be identified based on numerical values. In the L*a*b* system, L corresponds to the lightness, a to the red/green coordinate and b to the yellow/blue coordinate. The advantage of this method is that it is not dependent on the device used for the measurements. The formulation to be measured is filled into transparent petri dish (58×15 mm). The lid is placed on the petri dish carefully to avoid any air bubbles underneath the lid. L*a*b* parameters are measured of the sunscreen containing petri dish with a Remission Spectrometer Datacolor SF400 (light D65, observer 10°). Sunscreens very often show a yellow color, which is not desired by the end consumer. To increase the consumer compliance, a sunscreen should be less yellow as possible. Therefore, the parameter b* is taken for the evaluation of the yellow color of the formulation, the higher the b* value, the higher the measured yellow tone.

[0362] The evaluation of the color of Comparative Composition 4 and Compositions 9 and 10 is shown in Table 8 below.

TABLE-US-00021 TABLE 8 Comparative Composition 4 Composition 10 Composition 11 b* value 28.43 18.98 20.47 As can been seen from the b*value, the color of Comparative Composition 4 is much more yellow than the color of the inventive Compositions 10 and 11.

[0363] In a preferred embodiment, the present invention relates to the following further items.

1. A sunscreen or daily care composition comprising [0364] (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and [0365] (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane); and [0366] (iii) 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine); and [0367] (iv) 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone) and/or 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-butamidotriazone),
wherein the composition is free of ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene) and 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate); and wherein the composition comprises (i) to (ii) in a ratio of larger or equal to 0.8.
2. The sunscreen or daily care composition according to item 1, wherein the composition comprises (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in a ratio of larger or equal to 1.
3. The sunscreen or daily care composition according to item 1 or 2, wherein the composition comprises (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in a ratio of from 1:1 to 10:1, preferably in a ratio of from 1:1 to 5:1, more preferably in a ratio of from 1:1 to 2:1 and even more preferably in a ratio of from 1:1 to 1.5:1.
4. The sunscreen or daily care composition according to any one of items 1 to 3, wherein the composition is free of titanium dioxide, and zinc oxide.
5. The sunscreen or daily care composition according to any one of items 1 to 4, wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and isoamyl-4-methoxycinnamate (INCI isoamyl-p-methoxy cinnamate).
6. The sunscreen or daily care composition according to any one of items 1 to 5, wherein the composition is free of parabens.
7. The sunscreen or daily care composition according to any one of items 1 to 6, wherein the composition is provided in the form of a sprayable product.
8. The sunscreen or daily care composition according to any one of items 1 to 7, wherein the composition is free of emulsifier.
9. The sunscreen or daily care composition according to any one of items 1 to 8, wherein the composition is free of phenoxyethanol.
10. The sunscreen or daily care composition according to any one of items 1 to 9, wherein (iii) is an oil soluble UV filter or wherein (iii) is 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine) dissolved in a polymer matrix to be dispersible in water.
11. The sunscreen or daily care composition according to any one of items 1 to 10, wherein the composition comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 1% to 10% by weight, based on the total weight of the composition.
12. The sunscreen or daily care composition according to any one of items 1 to 11, wherein the composition comprises 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in an amount of from 1% to 5% by weight, based on the total weight of the composition.
13. The sunscreen or daily care composition according to any one of items 1 to 12, wherein the composition comprises 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine) in an amount of from 0.5% to 5% by weight, preferably in an amount of from 0.8% to 3% by weight, based on the total weight of the composition.
14. The sunscreen or daily care composition according to any one of items 1 to 13, wherein the composition comprises 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone) in an amount of from 0.5% to 5% by weight, preferably in an amount of from 0.8% to 3% by weight, based on the total weight of the composition.
15. The sunscreen or daily care composition according to any one of items 1 to 14, wherein the composition comprises 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-butamidotriazone) in an amount of from 0.5% to 5% by weight, preferably in an amount of from 0.8% to 3% by weight, based on the total weight of the composition.
16. The sunscreen or daily care composition according to any one of items 1 to 15, wherein the composition has a sun protection factor (SPF) of at least 20.
17. Use of a sunscreen or daily care composition as defined in any one of items 1 to 15 for the administration to sensitive skin.