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

Abstract

The present invention relates to sunscreen or daily care compositions comprising diethylamino hydroxybenzoyl hexyl benzoate, at least one organic particulate UV filter and at least one UV filter selected from triazine derivatives, wherein the composition does not comprise octocrylene. Furthermore, the present invention relates to the use of said composition to reduce fabric staining and to facilitate the washability of a sunscreen or daily care composition.

Claims

1.-15. (canceled)

16. A sunscreen or daily care composition, in the form of an emulsion, comprising (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 2.5% to 9% by weight based on the total weight of the composition; and (ii) at least one organic particulate UV filter; and (iii) at least one UV filter selected from triazine derivatives 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), 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 combinations thereof; wherein the composition does not comprise ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene).

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).

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 16, wherein the composition further comprises at least one emollient with a polarity index of <30 mN/m.

21. The sunscreen or daily care composition according to claim 20, wherein the at least one emollient is selected from the group consisting of C.sub.12-C.sub.15 alkyl benzoate, caprylic/capric triglyceride, butylene glycol dicaprylate/dicaprate, propylene glycol dicaprylate/dicaprate, diisopropyl sebacate, octyldodecanol, isopropyl palmitate, isopropyl myristate, dicaprylyl carbonate, phenethyl benzoate, dibutyl adipate, diisopropyl adipate, triethyl citrate and tributyl citrate.

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 3% 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 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.

24. The sunscreen or daily care composition according to claim 16, wherein the composition comprises the at least one UV filter selected from triazine derivatives in an amount of from 0.5% to 5% by weight, based on the total weight of the composition.

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

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

27. The sunscreen or daily care composition according to claim 16, wherein the composition has an UV-A protection, which is at least one third of the sun protection factor of the sunscreen composition.

28. A sunscreen or daily care composition, in the form of an emulsion, comprising (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and (ii) at least one organic particulate UV filter; and (iii) at least one UV filter selected from triazine derivatives; wherein the composition does not comprise ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene) to reduce fabric staining of a sunscreen or daily care composition.

29. A sunscreen or daily care composition, in the form of an emulsion, comprising (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and (ii) at least one organic particulate UV filter; and (iii) at least one UV filter selected from triazine derivatives; wherein the composition does not comprise ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene) to facilitate the washability of a sunscreen or daily care composition.

30. A sunscreen composition comprising (i) diethylamino hydroxybenzoyl hexyl benzoate; and (ii) bis-ethylhexyloxyphenol methoxyphenyl triazine; and (iii) ethylhexyl triazone; and (iv) methylene bis-benzotriazolyl tetramethylbutylphenol or trisbiphenyl triazine, wherein the sunscreen composition has an in vitro Boots rating UVA:UVB ratio of at least 0.9 before and 0.86 after an UV irradiation of 17.5 J/cm.sup.2.

Description

EXAMPLES

[0315] Process of Manufacture of Sunscreen Compositions

[0316] The ingredients of part A, as well as the ingredients of part B as provided below in Tables 1.1 and 1.2 for each tested sunscreen composition were combined and heated under stirring to 75-80° 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 part C was added if present.

[0317] All amounts referred to in the following tables refer to the respective amounts in % by weight, based on the total weight of the composition.

TABLE-US-00001 TABLE 1.1 Base Comparative Comparative Ingredient (Trade Name) composition composition 1a composition 1b Part A C.sub.12-C.sub.15 alkyl benzoate (Cetiol AB)  3.00  3.00  3.00 Dibutyl adipate (Cetiol B) 17.00 17.00 17.00 Cetearyl alcohol (Lanette O)  2.50  2.50  2.50 EHT (Uvinul T 150)  3.00  3.00  3.00 DHHB (Uvinul A Plus)  4.00  4.00  4.00 BEMT (Tinosorb S)  1.00  1.00  1.00 Titanium Dioxide —  3.00 — PBSA — —  3.00 EHMC (Uvinul MC 80) — — — DBT (Uvasorb HEB) — — — Part B Water qsp 100% qsp 100% qsp 100% Glycerin  3.00  3.00  3.00 Disodium EDTA (EDTA BD)  0.20  0.20  0.20 Xanthan Gum (Rheocare XG)  0.15  0.15  0.15 Potassium cetyl phosphate  2.50  2.50  2.50 (Amphisol K) Part C TBPT (Tinosorb A2B) — — —

TABLE-US-00002 TABLE 1.2 Comparative Comparative Ingredient (Trade Name) composition 1c composition 1d Composition 1 Part A C.sub.12-C.sub.15 alkyl benzoate  3.00  3.00  3.00 (Cetiol AB) Dibutyl adipate (Cetiol B) 17.00 17.00 17.00 Cetearyl alcohol (Lanette O)  2.50  2.50  2.50 EHT (Uvinul T 150)  3.00  3.00  3.00 DHHB (Uvinul A Plus)  4.00  4.00  4.00 BEMT (Tinosorb S)  1.00  1.00  1.00 Titanium Dioxide — — — PBSA EHMC (Uvinul MC 80)  3.00 — — DBT (Uvasorb HEB) —  3.00 — Part B Water qsp 100% qsp 100% qsp 100% Glycerin  3.00  3.00  3.00 Disodium EDTA (EDTA BD)  0.20  0.20  0.20 Xanthan Gum (Rheocare XG)  0.15  0.15  0.15 Potassium cetyl phosphate  2.50  2.50  2.50 (Amphisol K) Part C TBPT (Tinosorb A2B) — —  3.00* *Active amount

[0318] SPF and UV-A Measurements:

[0319] The SPF and UVA protection of the base composition, comparative compositions and composition 1 were determined according to standard procedures (ISO 24444, ISO 24443).

TABLE-US-00003 TABLE 2 SPF in vivo UVA-PF/SPF Base composition 17.2 >1/3 Comparative composition 1a 25.1 <1/3 Comparative composition 1b 28.8 <1/3 Comparative composition 1c 28.2 <1/3 Comparative composition 1d 37.2 <1/3 Composition 1 43.0 >1/3

[0320] Measurement of UVA Protection According to Boots Star Rating System

[0321] Process of Manufacture of Sunscreen Composition

[0322] The ingredients of part A, as well as the ingredients of part B as provided below in Table 3 were combined and heated under stirring to 75-80° 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 and part C was added.

TABLE-US-00004 TABLE 3 Ingredient (Trade Name) Composition 2 Part A Succrose polystearate  3.00 (Emulgade Sucro) Disodium cetearyl sulfosuccinate  1.00 (Emulgin Prisma) Dibutyl adipate (Cetiol B)  8.00 C.sub.12-15 alkyl benzoate (Cetiol AB)  6.00 Diisopropyl sebacate (Dib Dis)  5.00 Isopropyl myristate (IPM)  3.00 Cetearyl alcohol (Lanette O)  2.00 Ethylhexylglycerin (Sensiva SC 50)  0.50 DHHB (Uvinul A Plus) 10.00 BEMT (Tinosorb S)  2.00 EHT (Uvinul T150)  2.50 Part B Water qsp 100% Glycerin  6.20 Xanthan Gum (Rheocare XGN)  0.30 Part C MBBT (Tinosorb M)*  3.00 TBPT (Tinosorb A2B)*  2.00 *The amount refers to active matter, 3% MBBT correspond to 6% of the commercial product Tinosorb M; 2% TBPT correspond to 4% of the commercial product Tinosorb A26.

[0323] For each sunscreen composition, the UVA:UVB ratio is measured before and after irradiation with a fixed dose of 17.5 J/cm.sup.2 of UV radiation. The measurement of the initial UVA:UVB absorbance ratio, requires a transmission measurement through the sunscreen sample at least fifteen minutes and no more than 30 minutes after application of the sunscreen sample to the substrate. The second UVA:UVB absorbance ratio measurement is the post absorbance measurement, which takes into account any photo-degradation of the UV filter of the sunscreen sample. Therefore, the sunscreen sample of the initial UVA:UVB ratio is exposed to a fixed dose of 17.5 J/cm.sup.2 of UV radiation. The UVA:UVB ratio before and after irradiation is displayed below and in FIG. 1.

[0324] UVA: UVB ratio of composition 2 before irradiation: 0.90

[0325] UVA: UVB ratio of composition 2 after irradiation: 0.91

[0326] Fabric Staining Measurements

[0327] Process of Manufacture of Sunscreen Compositions

[0328] The ingredients of part A as well as the ingredients of part B as provided below in Table 4 for each tested sunscreen composition were combined and heated under stirring at 80° C. respectively wherein part A was added to part B under stirring and further homogenized. Part C was added and stirred and the sunscreen composition was cooled down to room temperature. Then, part D was added and stirred in.

TABLE-US-00005 TABLE 4 Comparative Ingredient (Trade Name) Composition 1e Composition 3 Part A Glyceryl stearate  1.00  1.00 Sodium Stearyl Glutamate  0.30  0.30 Stearyl Alcohol  1.00  1.00 Butylene Glycol Dicaprylate/Dicaprate  4.00  4.00 Dibutyl adipate (Cetiol B)  3.00  3.00 C12-15 Alkyl Benzoate (Cetiol AB)  5.00  5.00 Phenoxyethanol  1.00  1.00 VP/Hexadecene Copolymer  0.50  0.50 Silica Dimethyl Silylate  1.00  1.00 Butyl Methoxydibenzoylmethane  4.75  1.00 Ethylhexyl Salicylate  4.75  4.75 Ethylhexyl Triazone (Uvinul T 150)  3.00  3.00 Bis-Ethylhexyloxyphenol  4.00 — Methoxyphenyl Triazine (Tinosorb S) Diethylamino Hydroxybenzoyl Hexyl  1.00  3.00 Benzoate (Uvinul A Plus) Part B Aqua qsp 100% qsp 100% Glycerin  7.50  7.50 Acrylates/C10-30 Alkyl Acrylate  0.10  0.10 Crosspolymer Xanthan gum  0.40  0.40 Dissodium EDTA  0.20  0.20 Part C Phenylbenzimidazole Sulfonic Acid  1.00  1.00 Water  5.00  5.00 Sodium Hydroxyde qs qs Part D Methylene Bis-Benzotriazolyl —  4.00 Tetramethylbutyl-phenol (nano)* Ethanol  3.00  3.00 SPF kal. 36   36   UVA-PF kal. 13.2  14.9  *50% water dispersion: 4% Methylene Bis-Benzotriazolyl Tetramethylbutylphenol corresponds to 8% of supplied product (Tinosorb M)

[0329] Fabric staining of Composition 3 as well as Comparative Composition 1e has been measured as described above. The results are shown in Table 5.

TABLE-US-00006 TABLE 5 Comparative Composition 1e Composition 3 Δb* (before washing) 10.9  10.3  SD (before washing)  0.04  0.17 Δb* (after 1 cycle)  7.30  6.00 SD (after 1 cycle)  0.04  0.04 Δb* (after 3 cycles)  3.90  2.80 SD (after 3 cycles)  0.09  0.12

[0330] As can be seen from the results above, comparative Composition 1e exhibits a stronger fabric staining than Composition 3. Inventive Composition 3, however, containing Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (nano) instead of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine shows a significant fabric staining reduction.

[0331] Measurement of Interfacial Tension (Polarity Index)

[0332] Interfacial tension of the respective emollients as listed below was measured using a Tensimat Densimat TD2000.

TABLE-US-00007 TABLE 6.1 polarity index [mN/m] polarity index hydrogenated 45 >30 mN/m polyisobutene (reference mineral oil 43 emollients) cyclopentasiloxane 32 polarity index octyldodecanol 25 <30 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

[0333] UV Filter Performance

[0334] 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).

[0335] The UV transmission spectrum of each DHHB—emollient mixture was measured from 290 to 400 nm using a UVNis spectrophotometer Perkin Elmer Lambda 25. Three stock solutions with a concentration of 1 mM of DHHB were prepared for each mixture. Further, three dilutions of each stock solution were prepared resulting in nine measurements in total per DHHB—emollient solution. Then, all solutions were filled in UV transparent quartz cuvette of 1 cm optical path-length for UV Transmission measurements. λmax values of DHHB

TABLE-US-00008 TABLE 6.2 λmax values [nm] (DHHB) polarity index hydrogenated 345 >30 mN/m polyisobutene (reference cyclomethicone 345 emollients) mineral oil 346 polarity index phenethyl benzoate 355 <30 mN/m 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

[0336] Solubility Measurements

[0337] 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-00009 TABLE 6.3 solubility [%] (DHHB) polarity index mineral oil <1   >30 mN/m hydrogenated <1   (reference polyisobutene emollients) cyclomethicone <1   polarity index phenethyl benzoate 57   <30 mN/m 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 

[0338] In a particularly preferred embodiment, the present invention refers to the following further items: [0339] 1. A sunscreen or daily care composition comprising [0340] (i) hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate); and [0341] (ii) at least one organic particulate UV filter; and [0342] (iii) at least one UV filter selected from triazine derivatives;
wherein the composition does not comprise ethylhexyl-2-cyano-3,3-diphenyl-acrylate (INCI octocrylene). [0343] 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). [0344] 3. The sunscreen or daily care composition according to item 1 or 2, wherein the composition is free of parabens. [0345] 4. The sunscreen or daily care composition according to any one of items 1 to 3, wherein the at least one UV filter selected from triazine derivatives is 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), 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. [0346] 5. The sunscreen or daily care composition according to any one of items 1 to 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), 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) and combinations thereof. [0347] 6. The sunscreen or daily care composition according to any one of items 1 to 5, wherein the composition further comprises at least one emollient with a polarity index of <30 mN/m. [0348] 7. The sunscreen or daily care composition according to item 6, wherein the at least one emollient is selected from the group consisting of C.sub.12-C.sub.15 alkyl benzoate, caprylic/capric triglyceride, butylene glycol dicaprylate/dicaprate, propylene glycol dicaprylate/dicaprate, diisopropyl sebacate, octyldodecanol, isopropyl palmitate, isopropyl myristate, dicaprylyl carbonate, phenethyl benzoate, dibutyl adipate and diisopropyl adipate. [0349] 8. The sunscreen or daily care composition according to any one of items 1 to 7, wherein the composition comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) in an amount of from 0.5% to 10% by weight, based on the total weight of the composition. [0350] 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, preferably in an amount of from 1% to 5% by weight, based on the total weight of the composition. [0351] 10. The sunscreen or daily care composition according to any one of items 1 to 9, wherein the composition comprises the at least one UV filter selected from triazine derivatives 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. [0352] 11. The sunscreen or daily care composition according to any one of items 1 to 10, wherein the composition comprises perfume. [0353] 12. The sunscreen or daily care composition according to any one of items 1 to 11, wherein the composition is free of phenoxyethanol. [0354] 13. The sunscreen or daily care composition according to any one of items 1 to 12, wherein the composition has an UV-A protection, which is at least one third of the sun protection factor of the sunscreen composition. [0355] 14. Use of a composition as defined in any one of items 1 to 13 to reduce fabric staining of a sunscreen or daily care composition. [0356] 15. Use of a composition as defined in any one of items 1 to 13 to facilitate the washability of a sunscreen or daily care composition.