EFFICIENT SUNSCREEN COMPOSITIONS WITH DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE, BUTYL METHOXYDIBENZOYLMETHANE AND ORGANIC PARTICULATE UV FILTER

Abstract

The present invention relates to sunscreen or daily care compositions comprising hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) and at least one organic particulate UV filter, wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene).

Claims

1.-15. (canceled)

16. A sunscreen or daily care composition comprising (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 1% to 9% by weight based on the total weight of the composition; and (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane); and (iii) at least one organic particulate UV filter; and (iv) at least one emollient with a polarity index of <30 mN/m, wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone), ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene) 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.

17. The sunscreen or daily care composition according to claim 16, wherein the composition does not comprise 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate) and isoamyl-4-methoxycinnamate (INCI isoamyl-p-methoxy cinnamate).

18. The sunscreen or daily care composition according to claim 16, wherein the composition is free of parabens.

19. The sunscreen or daily care composition according to claim 16, 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.

20. The sunscreen or daily care composition according to claim 19, 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), 5,6,5′,6′-tetraphenyl-3-3′-(1,4-phenylene)bis(1,2,4-triazine) (INCI phenylene bis-diphenyltriazine), and combinations thereof.

21. The sunscreen or daily care composition according to claim 16, wherein the composition is free of phenoxyethanol.

22. The sunscreen or daily care composition according to claim 16, wherein the composition comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 2% to 8% by weight based on the total weight of the composition.

23. The sunscreen or daily care composition according to claim 16, 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.

24. The sunscreen or daily care composition according to claim 16, wherein the composition comprises the at least one organic particulate UV filter in an amount of from 0.5% to 10% by weight, based on the total weight of the composition.

25. The sunscreen or daily care composition according to claim 16, wherein the composition further comprises at least one UV filter selected from 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), 4,4′-[[6-[]4-[[(1,1,dimenthylethyl)amino]carbonyl]phenyl]amino]-1,3,5-triazin-2,4-diyl]diimino]bis-benzoic acid-bis(2-ethylhexyl)ester (INCI diethylhexyl-butamidotriazone), 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine) and combinations thereof.

26. The sunscreen or daily care composition according to claim 16, wherein the composition comprises at least one perfume.

27. The sunscreen or daily care composition according to claim 16, wherein the at least one particulate UV filter (iii) is 2,2′-methylene bis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (INCI methylene bis-benzotriazolyl tetramethylbutylphenol).

28. The sunscreen or daily care composition according to claim 16, wherein the composition comprises (iii) to (ii) in a ratio of 1:1.

29. The sunscreen or daily care composition according to claim 16, wherein the at least one emollient with a polarity index of <30 mN/m is selected from esters of linear or branched fatty acids with linear or branched fatty alcohols, di- and tricarboxylic acid esters with linear or branched alcohols, esters of hydroxycarboxylic acids with linear or branched fatty alcohols, esters of linear or branched fatty acids with polyhydric alcohol and mono-, di-, and tri-glycerides based on D.sub.6-D.sub.18 fatty acids.

30. Use of hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and at least one organic particulate UV filter for photostabilizing 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane) in a sunscreen or daily care composition, wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene).

31. The sunscreen or daily care composition according to claim 16, wherein the composition comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 4% to 6% by weight based on the total weight of the composition.

Description

EXAMPLES

[0273] Process of Manufacture of Sunscreen Compositions

[0274] The ingredients of part A, as well as the ingredients of part B as provided below in Table 1 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 and the pH of each composition was adjusted to 6.5-7.00 with NaOH.

[0275] All amounts referred to in the following tables refer to the respective amounts in % by weight, based on the total weight of the composition.

[0276] Sunscreen Compositions

TABLE-US-00001 TABLE 1 Comparative Comparative composition composition Composition Ingredient (Trade Name) 1a 1b 1 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 5.00 5.00 5.00 DHHB (Uvinul A Plus) 3.00 3.00 3.00 OCR (Uvinul N539T) 5.00 — — 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 methacrylate copolymer 2.00 2.00 2.00 (Tinovis GTC) Xanthan Gum (Rheocare 0.50 0.50 0.50 XGN) Part C MBBT (Tinosorb M)* — — 5.00 *The amount refers to active matter, 5% MBBT corresponds to 10% of the commercial product Tinosorb M.

[0277] Recovery Measurements on Photo Stability of BMDBM

[0278] The comparative compositions 1a and 1b, and composition 1 are applied on roughened quartz plates (2 μl/cm.sup.2). Plates are irradiated using Atlas CPS device at different duration times: [0279] 0 h (0 MED, no irradiation) [0280] 1 h (5 MED), [0281] 2 h (10 MED), [0282] 4 h (24 MED).

[0283] 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-00002 TABLE 2 Comparative Comparative Composition composition 1a composition 1b 1  0 MED 100% 100% 100%  5 MED  92%  63%  65% 10 MED  83%  28%  44% 20 MED  64%  5%  18% MED (Minimal Erythema Dose)

[0284] Measurement of Interfacial Tension (Polarity Index)

[0285] Interfacial tension of the respective emollients as listed below was measured using a Tensimat Densimat TD2000.

TABLE-US-00003 TABLE 3.1 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

[0286] UV Filter Performance

[0287] 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.

[0288] λMax Values of BMDBM

TABLE-US-00004 TABLE 3.2 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

[0289] λMax Values of DHHB

TABLE-US-00005 TABLE 3.3 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

[0290] Solubility Measurements

[0291] 0.02 g of UV Filter are added to 2 ml of the respective emollient as listed 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-00006 TABLE 3.4 solubility [%] (BMDBM) polarity index > 30 mN/m mineral oil <1 (reference emollients) hydrogenated <1 polyisobutene cyclomethicone <1 polarity index < 30 mN/m diisopropyl adipate 10 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-00007 TABLE 3.5 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 29.0 tributyl citrate 29.4

[0292] In a particularly preferred embodiment, the present invention refers to the following further items.

1. A sunscreen or daily care composition comprising [0293] (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and [0294] (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane); and [0295] (iii) at least one organic particulate UV filter;
wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene).
2. The sunscreen or daily care composition according to item 1, wherein the composition does not comprise 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate) and isoamyl-4-methoxycinnamate (INCI isoamyl-p-methoxy cinnamate).
3. The sunscreen or daily care composition according to item 1 or 2, wherein the composition is free of parabens.
4. The sunscreen or daily care composition according to any one of items 1 to 3, 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.
5. The sunscreen or daily care composition according to item 4, 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), 5,6,5′,6′-tetraphenyl-3-3′-(1,4-phenylene)bis(1,2,4-triazine) (INCI phenylene bis-diphenyltriazine), and combinations thereof.
6. The sunscreen or daily care composition according to any one of items 1 to 5, wherein the composition is free of phenoxyethanol.
7. The sunscreen or daily care composition according to any one of items 1 to 6, 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.
8. The sunscreen or daily care composition according to any one of items 1 to 7, 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.
9. The sunscreen or daily care composition according to any one of items 1 to 8, wherein the composition comprises the at least one organic particulate UV filter in an amount of from 0.5% to 10% by weight, based on the total weight of the composition.
10. The sunscreen or daily care composition according to any one of items 1 to 9, wherein the composition further comprises at least one UV filter selected from 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), 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), 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine) and combinations thereof.
11. The sunscreen or daily care composition according to any one of items 1 to 10, wherein the composition comprises perfume.
12. The sunscreen or daily care composition according to any one of items 1 to 11 comprising [0296] (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and [0297] (ii) 1-(4-(1,1-dimethylethyl)phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (INCI butyl methoxydibenzoylmethane); and [0298] (iii) 2,2′-methylene bis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (INCI methylene bis-benzotriazolyl tetramethylbutylphenol);
wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene).
13. The sunscreen or daily care composition according to item 12, wherein the composition comprises (iii) to (ii) in a ratio of 1:1.
14. The sunscreen or daily care composition according to item 12 or 13, wherein the composition comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 1% to 8% by weight, based on the total weight of the composition.
15. The sunscreen or daily care composition according to any one of items 12 to 14, 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.
16. The sunscreen or daily care composition according to any one of items 12 to 15, wherein the composition comprises 2,2′-methylene bis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (INCI methylene bis-benzotriazolyl tetramethylbutylphenol) in an amount of from 1% to 10% by weight, based on the total weight of the composition.