SUNSCREEN FORMULATIONS OPTIMIZED FOR THE FORMATION OF VITAMIN D

Abstract

The present invention relates to a sunscreen formulation comprising at least one of the UV filters (A) selected from (a) triazine derivatives; (b) cinnamic acid derivatives; (c) bis-resorcinyl triazines; (f) benzimidazole derivatives; (is) 4-Methylbenzylidene Camphor; (h) benzoyl piperazine derivatives; (j) benzoxazole derivatives; (k) diarylbutadiene derivatives; (I) phenyl benzotriazole derivatives; (n) benzylidene malonates; (o.sub.3) TEA-Salicylate; (r) imidazoline derivatives; (u) inorganic UV filters selected from metal oxides; (v) naphthalates; and (w) merocyanine derivatives; and optionally comprising at least one of the UV filters (B) selected from (d) aminobenzophenone derivatives; (e) dibenzoylmethane derivatives; (g) ,-Diphenylacrylate derivatives; (i.sub.5) camphor derivatives different from; (o.sub.3) salicylate derivatives different from; (p) anthranilate derivatives; and (s) benzalmalonate derivatives; wherein the ratio R of the effective irradiance for previtamin D.sub.3 formation E.sub.pvd to the effective irradiance for erythema formation E.sub.er on the skin is at least 1.8, for increasing the transmittance of UV radiation on human skin for the production of cholecalciferol (previtamin D.sub.3) and simultaneously for the use in a method for protecting the human skin against UV radiation when exposed to the sun, which method comprises applying said sunscreen formulation to the skin.

Claims

1-18. (canceled)

19. A sunscreen formulation comprising at least one UV filter (A) selected from the group consisting of: (a) triazine derivatives; (b) cinnamic acid derivatives; (c) bis-resorcinyl triazines; (f) benzimidazole derivatives; (i.sub.5) 4-Methylbenzylidene Camphor; (h) benzoyl piperazine derivatives; (j) benzoxazole derivatives; (k) diarylbutadiene derivatives; (l) phenyl benzotriazole derivatives; (n) benzylidene malonates; (o.sub.3) TEA-Salicylate; (r) imidazoline derivatives; (u) inorganic UV filters selected from metal oxides; (v) naphthalates; and (w) merocyanine derivatives; and optionally comprising at least one UV filter (B) selected from the group consisting of: (d) aminobenzophenone derivatives; (e) dibenzoylmethane derivatives; (g) ,-Diphenylacrylate derivatives; (i.sub.5) camphor derivatives different from; (o.sub.3) salicylate derivatives different from; (p) anthranilate derivatives; and (s) benzalmalonate derivatives; wherein the ratio R of the effective irradiance for previtamin D.sub.3 formation E.sub.pvd to the effective irradiance for erythema formation E.sub.er on the skin is at least 1.8, for increasing the transmittance of UV radiation on human skin for the production of cholecalciferol (previtamin D.sub.3) and simultaneously for the use in a method for protecting the human skin against UV radiation when exposed to the sun, which method comprises applying said sunscreen formulation to the skin.

20. The sunscreen formulation of claim 19, wherein the sunscreen formulation has an SPF of at least 2.

21. The sunscreen formulation of claim 19, wherein the sunscreen formulation has an SPF of at least 6.

22. The sunscreen formulation of claim 19, wherein the UV filters are selected from the group consisting of: (a.sub.1) ethylhexyl triazone; (a.sub.2) tris-bephenyl triazine; (a.sub.3) diethylhexyl butamido triazone; (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (c.sub.2) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine/polymethyl methacrylate; (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (e.sub.1) butyl methoxy dibenzoyl methane; (f.sub.1) phenyl benzimidazole sulfonic acid; (f.sub.2) disodium phenyl dibenzimidazole tetrasulfonate; (g.sub.1) octocrylene; (h.sub.1) 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; (l.sub.2) drometrizole trisiloxane; (l.sub.6) 2-(2h-benzotriazol-2-yl)-6-(2-ethylhexyloxymethyl)-4-methyl-phenol; (i.sub.1) terephthalylidene dicamphor sulfonic acid; (n.sub.1) compound of formula (BM9); (o.sub.1) ethylhexyl salicylate; (o.sub.4) homosalate; (p.sub.1) menthyl anthranilate; (s.sub.1) polysilicone-15; (u.sub.1) zinc oxide; and (u.sub.3) titanium dioxide.

23. The sunscreen formulation of claim 19, wherein the UV filters are selected from the group consisting of: (a.sub.1) ethylhexyl triazone; (b.sub.1) ethylhexyl methoxy cinnamate; (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; (e.sub.1) butyl methoxy dibenzoyl methane; (f.sub.1) phenyl benzimidazole sulfonic acid; (g.sub.1) octocrylene; and (u.sub.3) titanium dioxide.

24. The sunscreen formulation of claim 19, wherein the UV filters are selected from the group consisting of: (b.sub.1) ethylhexyl methoxy cinnamate; (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; (e.sub.1) butyl methoxy dibenzoyl methane; (f.sub.1) phenyl benzimidazole sulfonic acid; and (g.sub.1) octocrylene.

25. The sunscreen formulation of claim 19, wherein the UV filters are selected from the group consisting of: (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; and (e.sub.1) butyl methoxy dibenzoyl methane.

26. The sunscreen formulation of claim 23, wherein the sunscreen formulation has an SPF of at least 6.

27. The sunscreen formulation of claim 19, wherein the UV filters are selected from the group consisting of: (a) 0.1-40% by weight of triazine derivatives; (b) 0.1-30% by weight of cinnamic acid derivatives; (c) 0.1-10% by weight of bis-resorcinyl triazines; (f) 0.1-10% by weight of benzimidazole derivatives; (i.sub.5) 0.1-10% by weight of 4-Methylbenzylidene Camphor; (h) 0.1-10% by weight of benzoyl piperazine derivatives; (j) 0.1-10% by weight of benzoxazole derivatives; (k) 0.1-20% by weight of diarylbutadiene derivatives; (l) 0.1-30% by weight of phenyl benzotriazole derivatives; (n) 0.1-20% by weight of benzylidene malonates; (o.sub.3) 0.1-15% by weight of TEA-Salicylate; (r) 0.1-10% by weight of imidazoline derivatives; (u) 0.1-50% by weight of inorganic UV filters selected from metal oxides; (v) 0.1-20% by weight of naphthalates; and (w) 0.1-20% by weight of merocyanine derivatives; and optionally comprising at least one UV filters (B) selected from the group consisting of: (d) 0.1-20% by weight of aminobenzophenone derivatives; (e) 0.1-5% by weight of dibenzoylmethane derivatives; (g) 0.1-1% by weight of ,-Diphenylacrylate derivatives; (i) 0.1-10% by weight of camphor derivatives different from (i.sub.5); (o) 0.1-35% by weight of salicylate derivatives different from (o.sub.3); (p) 0.1-10% by weight of anthranilate derivatives; and (s) 0.1-10% by weight of benzalmalonate derivatives.

28. The sunscreen formulation of claim 19, wherein the sunscreen comprises the UV filters selected from the group consisting of: (a.sub.1) 1-3% by weight of ethylhexyl triazone; (b.sub.1) 1-3.5% by weight of ethylhexyl methoxycinnamate; (c.sub.1) 0.6-10% by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine; (d.sub.1) 0.8-10% by weight of diethylamino hydroxybenzoyl hexyl benzoate; (e.sub.1) 2-3% by weight of butyl methoxydibenzoylmethane; (f.sub.1) 2-3% by weight of phenyl benzimidazole sulfonic acid; (g.sub.1) 2.0-2.5% by weight of octocrylene; (l.sub.1) 2-7.5% by weight of methylene bis-benzotriazolyl tetramethylbutylphenol; and (u.sub.3) 3.0-3.5% by weight of titanium dioxide.

29. The sunscreen formulation of claim 19, wherein the sunscreen comprises the UV filter combination of: (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; and (e.sub.1) butyl methoxy dibenzoyl methane; wherein the sunscreen has a SPF of >15.

30. The sunscreen formulation of claim 19, wherein the sunscreen comprises the UV filter combination of: (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; and (e.sub.1) butyl methoxy dibenzoyl methane; wherein the sunscreen has a SPF>30.

31. The sunscreen formulation of claim 19, wherein the UV filters are broadband (spectrum of 340 to 400 nm) UV filters selected from the group consisting of: (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (c.sub.2) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine/polymethyl methacrylate; (f.sub.2) disodium phenyl dibenzimidazole tetrasulfonate; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; (l.sub.2) drometrizole trisiloxane; (u.sub.1) zinc oxide; (e.sub.1) butyl methoxy dibenzoyl methane; (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (i.sub.1) terephthalylidene dicamphor sulfonic acid; and (p.sub.1) menthyl anthranilate.

32. The sunscreen formulation of claim 19, comprising a UV filter selected from the group consisting of: (a) triazine derivatives; (b) cinnamic acid derivatives; (c) bis-resorcinyl triazines; (f) benzimidazole derivatives; (h) benzoyl-piperazine derivatives; (i.sub.5) 4-Methylbenzylidene Camphor; (l) phenyl benzotriazole derivatives; (n) benzylidene malonates; (o.sub.3) TEA-Salicylate; (r) imidazoline derivatives; (u) inorganic UV filters selected from metal oxides; (v) naphthalates; and (w) merocyanine derivatives; wherein the sunscreen formulation contains only one of the selected UV filters.

33. The sunscreen formulation of claim 32, wherein the UV filters are broadband (spectrum of 340 to 400 nm) UV filters selected from the group consisting of: (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (c.sub.2) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine/polymethyl methacrylate; (f.sub.2) disodium phenyl dibenzimidazole tetrasulfonate; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; (i.sub.1) terephthalylidene dicamphor sulfonic acid; and (u.sub.1) zinc oxide; wherein the sunscreen formulation contains only one of the selected UV filters.

34. The sunscreen formulation of claim 19, wherein the UV filters are particulate UV filters selected from the group consisting of: (a.sub.2) tris-biphenyl triazine; (c.sub.2) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine/polymethyl methacrylate; (h.sub.1) 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; (u.sub.1) zinc oxide; and (u.sub.3) titanium dioxide.

35. The sunscreen formulation of claim 19, wherein the UV filters are non-particulate UV filters selected from the group consisting of: (a.sub.1) ethylhexyl triazone. (a.sub.3) diethylhexyl butamido triazone; (c.sub.1) bis-ethylhexyloxyphenol methoxyphenyl triazine; (d.sub.1) diethylamino hydroxybenzoyl hexyl benzoate; (e.sub.1) butyl methoxy dibenzoyl methane; (f.sub.1) phenyl benzimidazole sulfonic acid; (f.sub.2) disodium phenyl dibenzimidazole tetrasulfonate; (g.sub.1) octocrylene; (h.sub.1) 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine; (l.sub.1) methylene bis-benzotriazolyl tetramethyl butylphenol; (l.sub.2) drometrizole trisiloxane; (l.sub.6) 2-(2h-benzotriazol-2-yl)-6-(2-ethylhexyloxymethyl)-4-methyl-phenol; (i.sub.1) terephthalylidene dicamphor sulfonic acid; (n.sub.1) compound of formula (BM9); (o.sub.1) ethylhexyl salicylate; (o.sub.4) homosalate; (p.sub.1) menthyl anthranilate; and (s.sub.1) polysilicone-15.

36. The sunscreen formulation of claim 19, wherein the ratio of the effective irradiance for vitamin D formation E.sub.pvd and the effective irradiance for erythema formation E.sub.er on the skin is >2.0.

Description

EXAMPLE A1: SPF 6 SUNSCREENS

[0392] Table 1 shows the compositions as well as the calculated values of SPF, E.sub.pvd/E.sub.er ratio, UVA-PF, UVA-PF/SPF-ratio and critical wavelength CW for four SPF 6 sunscreens as explained above.

TABLE-US-00003 TABLE 1 UV filter compositions for SPF 6 with different levels of E.sub.pvd/E.sub.er ratio and UVA protection filter UVA- CW Type composition SPF E.sub.pvd/E.sub.er UVA-PF PF/SPF [nm] F3 A1.3 0.6% EHMC 7.2 1.94 7.1 0.99 377 1% MBBT 1% BEMT 1% DHHB F4 A1.4 7.5% DHHB, 7.1 2.17 16.4 2.32 379 3% BMDBM

[0393] FIG. 3 shows the spectral transmittances of sunscreen films referring to the four different types of UV filter compositions leading to SPF 6.

EXAMPLE A2: SPF 15 SUNSCREENS

[0394] Table 2 shows the compositions as well as the calculated values of SPF, E.sub.Pvd/E.sub.er ratio, UVA-PF, UVA-PF/SPF-ratio and critical wavelength CW for four SPF 15 sunscreens.

TABLE-US-00004 TABLE 2 UV filter compositions for SPF 15 with different levels of E.sub.pvd/E.sub.er ratio and UVA protection UVA- CW Type filter composition SPF E.sub.pvd/E.sub.er UVA-PF PF/SPF [nm] A2.3 2% MBBT, 15.7 1.91 15.6 0.99 378 2% BEMT, 2% BMDBM, 2.5% OCR A2.4 3% BMDBM, 15.5 2.11 30.2 1.95 380 3.1% MBBT, 10% DHHB

[0395] In FIG. 4 the simulated spectral transmittances of sunscreen films referring to the four different types of UV filter compositions leading to SPF 15 are depicted.

EXAMPLE A3: SPF 30 SUNSCREENS

[0396] Table 3 shows the compositions and the calculated values of SPF, E.sub.pvd/E.sub.er ratio, UVA-PF, UVA-PF/SPF-ratio and critical wavelength CW for four SPF 30 sunscreens

TABLE-US-00005 TABLE 3 UV filter compositions for SPF 30 with different levels of E.sub.pvd/E.sub.er ratio and UVA protection UVA- CW Type filter composition SPF E.sub.pvd/E.sub.er UVA-PF PF/SPF [nm] A3.3 2.2% PBSA, 33.2 1.84 33.5 1.01 378 3% BEMT, 4.5% MBBT, 4.5% DHHB A3.4 1.9% BEMT, 33.1 2.00 49.5 1.50 380 3% BMDBM, 7.4% MBBT, 10% DHHB

[0397] FIG. 5 shows the simulated spectral transmittances of sunscreen films referring to the four different types of UV filter compositions leading to SPF 30.

[0398] The examples A3.3 and A3.4 demonstrate that the transmittance of sunscreens for vitamin D.sub.3-effective radiation can be optimized even if the SPF is the same.

EXAMPLE A4: DETERMINATION OF RECOMMENDED AMOUNT OF VITAMIN D/DAY

[0399] The exposure time t.sub.PVD for getting the recommended Vitamin D intake of 2000 IU/day is t.sub.PVD=4AF.sub.PVD minutes when the protected skin is exposed to the above mentioned maximum solar input. The attenuation factors AV.sub.PVD and the exposure times t.sub.PVD for the 4 examples of sunscreens are given in table 4.

TABLE-US-00006 TABLE 4 Attenuation factors AF.sub.PVD for vitamin D.sub.3-effective radiation and exposure times t.sub.PVD needed per day for getting the recommended amount of 2000 IU vitamin D.sub.3/day regarding 4 variations of sunscreens with SPF 6, 15 and 30 respectively Sunscreen type SPF 6 15 30 1 (state of the art) AF.sub.PVD 10.7 40.2 67.0 t.sub.PVD [min] 42.8 160.8 268 2 (state of the art) AF.sub.PVD 7.8 16.2 34.0 t.sub.PVD [min] 31.2 64.8 136 3 AF.sub.PVD 7.2 15.4 33.1 t.sub.PVD[min] 28.8 61.6 132.4 4 AF.sub.PVD 6.1 13.7 30.6 t.sub.PVD[min] 23.1 52.2 116.6

[0400] The exposure times t.sub.PVD for sun exposure with sunscreens e.g. with SPF=30 are with about 2 hours within the usual time frame of sun bathers. Thus it makes really sense to optimize sunscreens in terms of low attenuation factors AV.sub.PVD.

TABLE-US-00007 Weight Type [%] UV Filter Composition SPF E.sub.vitD/E.sub.er A2.4 4 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 15.7 2.00 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 8 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine 5 Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine/Polymethyl Methacrylate A3.3 20 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- 32.9 1.96 piperazine 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 3 Diethylamino Hydroxybenzoyl Hexyl Benzoate 2 Ethylhexyl Triazone 7.5 Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine/Polymethyl Methacrylate A5.3 1 Phenyl Benzimidazole Sulfonic Acid 61.2 1.94 3 Ethylhexyl Triazone 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 6 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 8 Diethylamino Hydroxybenzoyl Hexyl Benzoate 20 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi- perazine 10 Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine/Polymethyl Methacrylate A3.3 12 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 30.1 1.82 12 Tris-Biphenyl Triazine A2.4 14 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 15.0 2.04 20 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi- perazine A3.3 12 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 30.0 1.83 5 Titanium Dioxide A3.4 16 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 30.7 2.03 3 Titanium Dioxide 4 Diethylamino Hydroxybenzoyl Hexyl Benzoate 20 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi- perazine A3.3 14 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 30.9 1.84 5 Drometrizole trisiloxane A2.3 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 15.6 1.86 5 Compound of formula (PBT2) 2 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A2.4 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 16.3 2.02 3 Compound of formula (PBT2) 16 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A4.3 16 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 50.5 1.81 3.5 Titanium Dioxide 6% Compound of formula (PBT2) 6 Drometrizole trisiloxane A2.4 14 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 30.7 1.85 3 Titanium Dioxide 4 Compound of formula (PBT2) A5.3 16 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 60.2 1.89 3.5 Titanium Dioxide 6 BTEM 6 Drometrizole trisiloxane 10 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi- perazine A1.4 9 Diethylamino Hydroxybenzoyl Hexyl Benzoate 6.3 2.18 A1.3 3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 7.3 1.87 A2.4 3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 15.6 2.05 20 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A3.3 2 Octocrylene 30.6 1.94 2 Butyl Methoxy Dibenzoyl Methane 2.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 8 Terephthalylidene Dicamphor Sulfonic Acid 12 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A2.3 3 Polisilicone-15 16.3 1.87 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 4 Disodium Phenyl Dibenzimidazole Tetrasulfonate A2.3 1 Diethylhexyl Butamido Triazone 15.5 1.81 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 3 Disodium Phenyl Dibenzimidazole Tetrasulfonate A2.3 25 Zinc Oxide 15.7 1.92 1.2 Titanium Dioxide A3.4 9 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 31.2 2.01 1.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 25 Zinc Oxide 20 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A1.3 15 Zinc Oxide 6.6 1.97 A3.3 4 Ethylhexyl Salicylate 30.9 1.89 2 Butyl Methoxy Dibenzoyl Methane 1.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.5 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 3 Benzophenone-3 3 Titanium Dioxide 16 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A3.3 4 Ethylhexyl Salicyate 31.4 1.89 2 Butyl Methoxy Dibenzoyl Methane 1.5 TinosorbS 1.5 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 3 Benzophenone-4 3 Titanium Dioxide 16 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A3.3 4 Homomenthyl Salicyate 30.8 1.90 2 Butyl Methoxy Dibenzoyl Methane 1.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.5 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol 3 Benzophenone-4 3 Titanium Dioxide 16 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- piperazine A1.4 5 Terephthalylidene Dicamphor Sulfonic Acid 6.06 2.03 A2.3 2 Octocrylene 15.2 1.91 1 Butyl Methoxy Dibenzoyl Methane 4 Terephthalylidene Dicamphor Sulfonic Acid 1 Benzophenone-3 5 Menthyl Anthranilate A3.3 3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 30.0 1.96 5 Diethylamino Hydroxybenzoyl Hexyl Benzoate 5 Compound of formula (BM9) 12 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi- perazine A3.4 3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 30.1 2.01 6 Diethylamino Hydroxybenzoyl Hexyl Benzoate 4 Compound of formula (BM9) 16 1,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi- perazine A3.3 3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 30.1 1.87 10 Diethylamino Hydroxybenzoyl Hexyl Benzoate 3 Ethylhexyl Triazone A0.3 0.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.1 1.95

B. Examples for Cosmetic Formulations

[0401]

TABLE-US-00008 Example B1: Type 1.3, SPF = 6 % w/w, as Trade Name INCI Name supplied Part A Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate 1.00 (DHHB) Uvinul MC 80 Ethylhexyl Methoxycinnamate 0.60 Tinosorb S Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.00 Cetiol AB C12-15 Alkyl Benzoate 8.00 Part B Water Aqua Qs to 100 Butylene glycol Butylene glycol 2.50 Mais PO4 PH B Distarch phosphate 2.00 Tinovis GTC Acrylates/beheneth-25 methylacrylate copolymer 1.50 Part C Sodium hydroxide Water (and) sodium hydroxide Qs to pH 7 (30% solution) Part D Tinosorb M Methylene Bis-Benzotriazolyl Tetramethyl- 1.00 butylphenol Ethanol 96% Alcohol 5.00

[0402] The formulation is prepared as follows: Parts A and B are prepared and separately heated to 80 C. Then part A is added to part B under stirring. After short homogenization part C is added under stirring. After cooling down to room temperature the ingredients of part D are added in the listed order.

TABLE-US-00009 Example B2: Type 1.4, SPF = 6 % w/w as Trade Name INCI Name supplied Part A Cetiol CC Dicaprylyl carbonate 5.00 Cetiol B Dibutyl adipate 4.00 Cetiol C5 Coco-caprylate 3.00 Cetiol AB C12-15 Alkyl Benzoate 5.00 Sensiva SC 50 Ethylhexyl glycerol 0.50 Parsol 1789 Butyl Methoxydibenzoyl- 3.00 methane Uvinul A Plus Diethylamino 7.5 Hydroxybenzoyl Hexyl Benzoate Part B Water Aqua Qs to 100 Glycerin 85% Glycerol 3.00 Protectol PE Phenoxyethanol 1.00 Eumulgin SG Sodium Stearoyl Glutamate 0.80 Edeta BD Disodium EDTA 0.20 Keltrol CG RD Xanthan Gum 0.20 Part C Tinovis ADE sodium acrylates copolymer 1.00 (and) hydrogenated poly- decene (and) PPG-1 tri- deceth-6 Part D Orgasol Caresse Polyamide-5 3.00 Sodium Hydroxide Water (and) Sodium 0.20 (30% solution) Hydroxide

[0403] The formulation is prepared as follows: Part A is heated to 80 C., cooled down to room temperature and incorporated into part B under stirring. After homogenization (with an ultra-turrax type device) part C is added, again followed by homogenization. Finally the ingredients of part D are added and the formulation is homogenized again.

TABLE-US-00010 Example B3: Type 2.3, SPF = 15 % w/w, as Trade Name INCI Name supplied Part A Parsoll 1789 Butyl Methoxy Dibenzoyl 3.00 Methane Uvinul A plus Diethylamino 10.00 Hydroxybenzoyl Hexyl Benzoate Cetiol AB C12-15 Alkyl Benzoate 8.00 Part B Water Aqua Qs to 100 Butylene glycol Butylene glycol 2.50 Mais PO4 PH B Distarch phosphate 2.00 Tinovis GTC Acrylates/beheneth-25 1.50 methylacrylate copolymer Part C Sodium hydroxide Water (and) sodium Qs to (30% solution) hydroxide pH 7 Part D Tinosorb M Methylene Bis-Benzotriazolyl 3.10 Tetramethyl-butylphenol Ethanol 96% Alcohol 5.00

[0404] The formulation is prepared as follows: Parts A and B are prepared and separately heated to 80 C. Then part A is added to part B under stirring. After short homogenization part C is added under stirring. After cooling down to room temperature the ingredients of part D are added in the listed order.

TABLE-US-00011 Example B4: Type 2.4, SPF = 15 % w/w, as Trade Name INCI Name supplied Part A Parsol 1789 Butyl Methoxydibenzoyl- 3.00 methane Uvinul N 539 Octocrylene 2.50 Tinosorb S Bis-Ethylhexyloxyphenol 2.00 Methoxyphenyl Triazine (BEMT) Cetiol AB C12-15 Alkyl Benzoate 15.0 Part B Water Aqua Qs to 100 Butylene glycol Butylene glycol 2.50 Mais PO4 PH B Distarch phosphate 2.00 Tinovis GTC Acrylates/beheneth-25 1.50 methylacrylate copolymer Part C Sodium hydroxide Water (and) sodium Qs to (30% solution) hydroxide pH 7 Part D Tinosorb M Methylene Bis-Benzotriazolyl 2.00 Tetramethyl-butylphenol Ethanol 96% Alcohol 3.00

[0405] The formulation is prepared as follows: Parts A and B are prepared and separately heated to 80 C. Then part A is added to part B under stirring. After short homogenization part C is added under stirring. After cooling down to room temperature the ingredients of part D are added in the listed order.

TABLE-US-00012 Example B5: Type 3.3, SPF = 30 % w/w, as Trade Name INCI Name supplied Part A Uvinul A plus Diethylamino 4.50 Hydroxybenzoyl Hexyl Benzoate Tinosorb S Bis-Ethylhexyloxyphenol 3.00 Methoxyphenyl Triazine Cetiol AB C12-15 Alkyl Benzoate 12.0 Cetiol B Dibutyl adipate 5.00 Part B Water Aqua Qs to 100 Butylene glycol Butylene glycol 2.50 Mais PO4 PH B Distarch phosphate 2.00 Tinovis GTC Acrylates/beheneth-25 1.50 methylacrylate copolymer Part C Water Aqua 9.00 Eusolex 232 Phenyl Benzimidazole 3.00 Sulfonic Acid Tris Amino Ultra Tromethamine Qs to Pur pH 7 Part D Tinosorb M Methylene Bis-Benzotriazolyl 4.50 Tetramethyl-butylphenol Ethanol 96% Alcohol 3.00

[0406] The formulation is prepared as follows: Parts A and B are prepared and separately heated to 80 C. Then part A is added to part B under stirring. After short homogenization part C is added under stirring. After cooling down to room temperature the ingredients of part D are added in the listed order.

TABLE-US-00013 Example B6: Type 3.4, SPF = 30 % w/w, as Trade Name INCI Name supplied Part A Parsol 1789 Butyl Methoxydibenzoyl- 3.00 methane Uvinul A plus Diethylamino 10.0 Hydroxybenzoyl Hexyl Benzoate Tinosorb S Bis-Ethylhexyloxyphenol 1.90 Methoxyphenyl Triazine Cetiol AB C12-15 Alkyl Benzoate 14.0 Cetiol B Dibutyl adipate 8.00 Part B Water Aqua Qs to 100 Butylene glycol Butylene glycol 2.50 Mais PO4 PH B Distarch phosphate 2.00 Tinovis GTC Acrylates/beheneth-25 1.50 methylacrylate copolymer Part C Sodium hydroxide Water (and) sodium Qs to (30% solution) hydroxide pH 7

TABLE-US-00014 Example B7: Type 3.4, SPF = 30 Part D Tinosorb M Methylene Bis-Benzotriazolyl 7.40 Tetramethylbutylphenol Ethanol 96% Alcohol 3.00

[0407] The formulation is prepared as follows: Parts A and B are prepared and separately heated to 80 C. Then part A is added to part B under stirring. After short homogenization part C is added under stirring. After cooling down to room temperature the ingredients of part D are added in the listed order.