Sunscreen Compositions Comprising Colour Pigments

Abstract

Disclosed are cosmetic formulation comprising (a) particulates having an absorption in the range of 400 to 800 nm; and (b) UV filters selected from (b.sub.1) particulate organic UV-filters; and (b.sub.2) soluble organic UV filters.

Claims

1. Cosmetic formulation comprising (a) particulates having an absorption in the range of 400 to 800 nm; and (b) UV filters selected from (b.sub.1) particulate organic UV-filters; and (b.sub.2) soluble organic UV filters.

2. Cosmetic formulation according to claim 1, wherein (a) is selected from (a.sub.1) inorganic colour pigments; and (a.sub.2) organic colour pigments.

3. Cosmetic formulation according to claim 1 or 2, wherein the inorganic pigments (a.sub.1) are selected from iron (III) oxide, magnetite and mixtures of these pigments; manganese doped TiO.sub.2 or ZnO; ultramarine pigments; chromium oxide green; chromium hydrate green; metal-particles; mica, bismuth oxychloride; glass flakes (borosilicates); interference-pigments based on mica (synthetic or of natural origin); or borosilicates (glass flakes), typically coated with thin layers of titanium dioxide (rutile or anastas), iron oxides or mixtures thereof and talcum.

4. Cosmetic formulation according to any of claims 1 to 3, wherein the organic pigments (a.sub.2) are selected from D&C Red 30 (Vat Red 1); D&C Red 36 (Pigment Red 4); Carmine; D&C Red 6 Ba Lake; D&C Red 7 Ca Lake; D&C Red 30 Al Lake; D&C Red 30 Talc Lake; D&C Red 27 Al Lake; D&C Red 28 Al Lake; D&C Red 33 Al Lake; and D&C Red 21 Al Lake.

5. Cosmetic formulation according to any of claims 1 to 4, wherein the particulate organic UV-filter (b.sub.1) is selected from benztriazoles of formula ##STR00027## wherein R.sub.1 and R.sub.2 independently from each other are C.sub.1-C.sub.18alkyl which may be substituted by one or more radicals selected from C.sub.1-C.sub.4alkyl, C.sub.5-C.sub.12cycloalkyl and C.sub.6-C.sub.10aryl.

6. Cosmetic formulation according to claim 5, wherein the particulate organic UV-filters (b.sub.1) corresponds to formula ##STR00028##

7. Cosmetic formulation according to any of claims 1 to 4, wherein the particulate organic UV-filter (b.sub.1) is selected from the triazine derivatives of formula ##STR00029## wherein R.sub.3 and R.sub.4 independently from each other are hydrogen; C.sub.1-C.sub.18alkyl; or C.sub.6-C.sub.12aryl; R.sub.5, R.sub.6 and R.sub.7 independently from each other are hydrogen; hydroxy; halogen; C.sub.1-C.sub.18alkyl; C.sub.1-C.sub.18alkoxy; C.sub.6-C.sub.12aryl; biphenylyl; C.sub.6-C.sub.12aryloxy; C.sub.1-C.sub.18alkylthio; carboxy; —COOM; C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; mono- or di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or —COOH; and M is an alkali metal ion.

8. Cosmetic formulation according to claim 7, wherein R.sub.3 and R.sub.4 are hydrogen.

9. Cosmetic formulation according to claim 7 or 8, wherein R.sub.5 and R.sub.6 are hydrogen; and R.sub.7 is hydrogen; phenyl; or biphenylyl.

10. Cosmetic formulation according to any of claims 7 to 9, wherein the particulate organic UV-filter (b.sub.1) corresponds to the formula ##STR00030##

11. Cosmetic formulation according to any of claims 1 to 10, wherein (b.sub.1) represents a mixture of the compounds of formula (2) and (4).

12. Cosmetic formulation according to any of claims 1 to 4, wherein the particulate organic UV-filter (b.sub.1) is selected from the compounds of formula ##STR00031## wherein R.sub.8 and R.sub.9 independently from each other are C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.20alkenyl; C.sub.3-C.sub.10cycloalkyl; C.sub.3-C.sub.10cycloalkenyl; or R.sub.8 and R.sub.9 together with the linking nitrogen atom form a 5- or 6-membered heterocyclic ring; R.sub.10 is an alkylene-, cycloalkylene, alkenylene or phenylene radical which is optionally substituted by a carbonyl- or carboxy group; a radical of formula *—CH.sub.2—C≡C—CH.sub.2—* ; or R.sub.10 together with A forms a bivalent radical of the formula (1a) ##STR00032## wherein n.sub.2 is a number from 1 to 3.

13. Cosmetic formulation according to claim 12, wherein the particulate organic UV-filter (b.sub.1) corresponds to formula ##STR00033##

14. Cosmetic formulation according to any of claims 1 to 13, wherein the soluble organic UV-filter (b.sub.2) is selected from the triazine derivative of formula ##STR00034## wherein R.sub.12 and R.sub.13, independently of one another, are C.sub.1-C.sub.18alkyl; or C.sub.2-C.sub.18alkenyl; A.sub.l is a radical of the formula (7a) ##STR00035## R.sub.14 is hydrogen; C.sub.1-C.sub.10alkyl, —(CH.sub.2CHR.sub.5—O).sub.n.sub.1—R.sub.15; or a radical of the formula —CH.sub.2—CH(—OH)—CH.sub.2—O-T.sub.1; R.sub.15 is hydrogen; M; C.sub.1-C.sub.5alkyl; or a radical of the formula —(CH.sub.2).sub.m.sub.2—O-T.sub.1; T.sub.1 is hydrogen; or C.sub.1-C.sub.18alkyl; Q.sub.1 C.sub.1-C.sub.18alkyl; M is a metal cation; m.sub.2 is 1 to 4; and n.sub.1 is 1-16.

15. Cosmetic formulation according to claim 14, wherein the soluble organic UV-filter (b.sub.2) corresponds to formula ##STR00036##

16. Cosmetic formulation according to any of claims 1 to 13, wherein the soluble organic UV-filter (b.sub.2) is a dibenzoylmethane derivative.

17. Cosmetic formulation according to any of claims 1 to 13, wherein the soluble organic UV-filter (b.sub.2) is a 2-hydroxy benzophenone derivative of formula ##STR00037## wherein R.sub.16 and R.sub.17 independently from each other are hydrogen, C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.10alkenyl; C.sub.3-C.sub.10cyclalkyl; or C.sub.3-C.sub.10cycloalkenyl; R.sub.18 and R.sub.19 independently from each other are C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.10alkenyl; C.sub.3-C.sub.10cycloalkenyl; C.sub.1-C.sub.12alkoky; C.sub.1-C.sub.20alkoxycarbonyl; C.sub.1-C.sub.12alkylamino; di(C.sub.1-C.sub.12)alkylamino; aryl or heteroaryl radical which is optionally substituted; or a water-solubilizing substitutent selected from a carboxylate group, a sulphonate group or an ammonium residue; X is hydrogen; COR.sub.19; COOR.sub.19; or CONR.sub.19R.sub.20; R.sub.19 and R.sub.20 independently from each other are hydrogen; C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.10alkenyl; C.sub.3-C.sub.10cycloalkenyl; a —(Y—O)—Z— group; or aryl; Y is *—(CH.sub.2).sub.2—*; *—(CH.sub.2).sub.3—*; *—(CH.sub.2).sub.4—*; or *—(CH)—(CH.sub.3)—CH.sub.2—*; Z is *—CH.sub.2—CH.sub.3; *—CH.sub.2—CH.sub.2—CH.sub.3; *—CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.3; or *—CH(CH.sub.3)—CH.sub.3; m is a number from 0 to 3; n is a number from 0 to 3; o is 1; or 2.

18. Cosmetic formulation according to claim 17, wherein the soluble organic UV-filter (b.sub.2) is Diethylamino Hydroxybenzoyl Hexyl Benzoate [CAS Regno. 302776-68-7].

19. Cosmetic formulation according to any of claims 1 to 4, wherein the soluble organic UV-filter (b.sub.2) is a merocyanine derivative of formula ##STR00038## wherein R.sub.21 and R.sub.22 are each independently of the other hydrogen; C.sub.1-C.sub.22alkyl; cyclo-C.sub.3-C.sub.8alkyl; or unsubstituted or C.sub.1-C.sub.6alkyl- or C.sub.1-C.sub.6alkoxy-substituted C.sub.6-C.sub.20aryl; or R.sub.21 and R.sub.22 together with the nitrogen atom linking them form a —(CH.sub.2).sub.m— ring which is uninterrupted or interrupted by —O— or by —NH—; R.sub.23 is a cyano group; —COOR.sub.25; —CONHR.sub.25; —COR.sub.25; or —SO.sub.2R.sub.25; —CONR.sub.25R.sub.26; R.sub.24 is a cyano group; —COOR.sub.27; —CONHR.sub.27; —COR.sub.27; or —SO.sub.2R.sub.27; —CONR.sub.26R.sub.28; R.sub.25, R.sub.26, R.sub.27 and R.sub.28 are each independently of the other C.sub.1-C.sub.22alkyl; cyclo-C.sub.3-C.sub.8alkyl; or unsubstituted or C.sub.1-C.sub.6alkyl-substituted C.sub.6-C.sub.20aryl; or R.sub.21 and R.sub.22, R.sub.23 and R.sub.24, R.sub.25 and R.sub.26 or R.sub.27 and R.sub.28 together form a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; Z.sub.1 and Z.sub.2 are each independently of the other a *—(CH.sub.2).sub.l—* group which is uninterrupted or interrupted by —O—, —S—, or by —NR.sub.29—, and/or is unsubstituted or substituted by C.sub.1-C6alkyl; R.sub.29 is C.sub.1-C.sub.5alkyl; l is a number from 1 to 4; m is a number from 1 to 7; n is from 1 to 4; when n=2, R.sub.21, R.sub.23 or R.sub.24 is a bivalent alkyl group; or R.sub.23 and R.sub.24 together with the 2 nitrogen atoms linking them form a —(CH.sub.2).sub.m— ring; when n=3, R.sub.21, R.sub.23 or R.sub.24 is a trivalent alkyl group; when n=4, R.sub.21, R.sub.23 or R.sub.24 is a tetravalent alkyl group.

20. Cosmetic formulation according to claim 19, wherein the soluble organic UV-filter (b.sub.2) is a merocyanine derivative of formula ##STR00039##

21. Cosmetic formulation according to cany of claims 1 to 20, wherein (b) represents a mixture of at least one particulate organic UV filter (b.sub.1) and at least one soluble organic UV filter (b.sub.2).

22. Cosmetic formulation according to claims 1 to 15, wherein (b) represents a mixture selected from (mix.sub.1) the compounds of formulae (2), (4) (8) and butyl methoxydibenzoylmethane; (mix.sub.2) the compounds of formulae (2), (4), (6) and butyl methoxydibenzoylmethane; (mix.sub.3) the compounds of formulae (8), (12) and butyl methoxydibenzoylmethane; (mix.sub.4) the compounds of formulae (2), (4), (6), (8), (11), (12) and butyl methoxydibenzoyl-methane; (mix.sub.4) the compounds of formulae (2), (4) and (6); (mix.sub.5) the compounds of formulae (2), (4), (6) and (8).

23. Cosmetic formulation according to claim 1, comprising (a) particulates selected from interference-pigments based on mica and coated with iron oxide; and (b) mixture of particulate organic UV filters selected from triazine and benzotriazole derivatives.

24. Cosmetic formulation according to claim 23, wherein the particulate UV filters (b.sub.1) is a mixture of the compound of formulas (2) and (4).

25. Cosmetic formulation according to claim 1, comprising 01 to 10% b.w of particulates (a); and 0.1 to 40% b.w of UV filters (b).

26. Cosmetic formulation according to claim 25, wherein the formulation is free of soluble organic UV filters (b.sub.2) and other soluble UV filters.

27. Use of the composition according to any of claims 1 to 26 for minimizing and/or masking the whitening effect and/or the particular color of a sunscreen composition.

28. Use of the composition according to any of claims 1 to 26 for the visualization of a consistent application of a sunscreen formulation.

29. Use of the composition according to any of claims 1 to 26 for the protection against electromagnetic radiation in the range >380 nm.

30. Use of the composition according to any of claims 1 to 26 for adjusting a natural skin-like color tone of the sunscreen formulation.

31. Use of the composition according to any of claims 1 to 26 for promoting an even skin tone.

32. Use of the composition according to any of claims 1 to 26 for minimising fine lines and wrinkles.

Description

EXAMPLES

[0198] Preparation of Sunscreen Formulation

[0199] Examples 1, 2 and 4 show advantage over Examples 3 and 5 which do not contain color pigments.

TABLE-US-00005 INCI Ex. 1 Ex. 2 Ex. 3 Part A Glyceryl Stearate (and) PEG 100 Stearate 2.00 2.00 2.00 Butylene Glycol Cocoate 5.00 5.00 5.00 Isopropyl Palmitate 4.00 4.00 4.00 Trioctanion 4.00 4.00 4.00 TiO.sub.2 (and) Stearic Acid (and) Aluminium Hydroxide 3.20 3.20 3.20 Part B Water Tinoderm SGP (Ciba) 3.00 3.00 3.00 Disodium EDTA 0.20 0.20 0.20 Xanthan Gum 0.20 0.20 0.20 Potassium cetyl Phosphate 1.50 1.50 1.50 Part B2 Calisha Contemporary jet black (Iron oxide) 0.01 0.005 — Calisha Contemporary medium red (iron oxide) 0.1 0.025 — Calisha Contemporary yellow (iron oxide) 0.55 0.27 — Part C Phenyl Trimethicone 2.00 2.00 2.00 Cyclomethicone 4.00 4.00 4.00 Dimethicone (and) Dimethicone/Vinyl Dimethicone 3.00 3.00 3.00 Crosspolymer Part D Mica (and) Titanium Dioxide (and) Red iron oxide (and) Cetyl 0.30 Dimethicone Micronized Methylene Bis-Benzotriazolyl Tetra- 4.00 5.00 3.00 methylbutylphenol Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-4-yl)-(CAS 5.00 5.00 5.00 Regn. 31274-51-8) Phenoxyethanol (and) Methylparaben (and) Ethylparaben (and) 1.00 Butylparaben (and) Propylparaben Isobutylparaben Tinoderm E 0.50 Water ad 100 ad 100 ad 100 INCI Ex. 4 Ex. 5 Phase A Glyceryl Stearate (and) PEG 100 Stearate 5.00 5.00 Phenethyl Benzoate 6.00 6.00 Isopropyl Palmitate 5.00 5.00 Triheptanoin 3.00 3.00 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.00 2.00 Ethylhexyl Triazone 1.50 1.50 Phase B Water Butylene Glycol 2.00 2.00 Sodium EDTA 0.20 0.20 Phase B2 Calisha Contemporary jet black (Iron oxide) 0.01 Calisha Contemporary medium red (iron oxide) 0.08 Calisha Contemporary yellow (iron oxide) 0.55 Phase C Sodium Acrylates Copolymer (and) Mineral Oil (and) PPG-1 1.20 1.20 Trideceth-6 Phase D Cyclomethicone 3.00 3.00 Cyclomethicone 4.00 4.00 Phase E Methylene Bis-Benzotriazolyl Tetramethylbutylphenol 14.00 14.00 Methylparaben (and) Ethylparaben (and) Butylparaben 1.00 1.00 (and) Propylparaben Water ad 100 ad 100

[0200] Manufacturing Process:

[0201] Heat up part A and B to 75° C.

[0202] Add Amphisol K into B and stirr for 5 more minutes, then Add part B2.

[0203] Add part A into part B, then homogenize with an Ultra Turrax for 1 min pos 21200 g

[0204] Add part C by 60° C., and turrax again

[0205] Add part D below 50° C.

[0206] B. Application Examples

TABLE-US-00006 Example B1: O/W Emulsion (1) Part INCI A B C A Glyceryl Stearate (and) PEG 100 Stearate 2.00 2.00 2.00 Butylene Glycol Cocoate 5.00 5.00 5.00 Isopropyl Palmitate 4.00 4.00 4.00 Triethylhexanoin 4.00 4.00 4.00 TIO2 (and) Stearic Acid (and) Aluminum Hydroxide 3.20 3.20 3.20 B Pentylene Glycol (and) Sclerotium Gum 3.00 3.00 3.00 Disodium EDTA 0.20 0.20 0.20 Xanthan Gum 0.20 0.24 0.24 Potassium cetyl Phosphate 1.50 1.50 1.50 B 2 Iron Oxides (CALISHA Contemprorary Jet Black Oxide) 0.01 0.005 0.005 Iron Oxides (CALISHA Contemporary Medium Red 0.10 0.025 0.025 Oxide) Iron Oxides (CALISHA Contemporary Yellow Oxide) 0.55 0.27 0.27 C Phenyl Trimethicone 2.00 2.00 2.00 Cyclomethicone 4.00 4.00 4.00 Dimethicone (and) Dimethicone/Vinyl Dimethicone 3.00 3.00 3.00 Crosspolymer D Micronized Methylene Bis-Benzotriazolyl Tetramethyl- 4.00 4.00 4.00 butylphenol Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]-4-yl)- 5.00 5.00 5.00 (CAS Regn. 31274-51-8) Micronized Methanone, 1,1′-(1,4-piperazinediyl)bis[1-[2-[4- 1.00 2.00 4.00 (diethylamino)-2-hydroxybenzoyl]phenyl]- (CAS Regn. 919803-06-8) Mica (and) Titanium Dioxide (and)Tin oxide 0.30 0.30 Phenoxyethanol (and) Methylparaben (and) Ethylparaben 1.00 1.00 1.00 (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Aqua (and) Tocopheryl Acetate (and) Caprylic/Capric 0.50 Triglyceride (and) Polysorbate 80 (and) Lecithin Water ad ad ad 100 100 100

TABLE-US-00007 Example B2: O/W Emulsion (2) INCI A B C D E F Glyceryl Stearate (and) PEG 100 Stearate 5.00 5.00 5.00 5.00 5.00 5.00 Phenethyl Benzoate 6.00 6.00 6.00 6.00 6.00 6.00 Isopropyl Palmitate 5.00 5.00 5.00 5.00 5.00 5.00 Triethylhexanoin 3.00 3.00 3.00 3.00 3.00 3.00 Bis-Ethylhexyloxyphenol Methoxyphenyl 2.00 2.00 2.00 2.00 2.00 2.00 Triazine Ethylhexyl Triazone 1.50 1.50 1.50 1.50 1.50 1.50 Butylene Glycol 2.00 2.00 2.00 2.00 2.00 2.00 Disodium EDTA 0.20 0.20 0.20 0.20 0.20 0.20 Iron Oxides (CALISHA Contemprorary Jet 0.01 0.02 0.01 0.01 0.01 0.01 Black Oxide) Iron Oxides (CALISHA Contemporary 0.08 0.5 0.08 0.08 0.08 0.08 Medium Red Oxide) Iron Oxides (CALISHA Contemporary Yellow 0.55 0.5 0.55 0.55 0.55 0.55 Oxide Sodium Acrylates Copolymer (and) Mineral 1.20 1.20 1.20 1.20 1.20 1.20 Oil (and) PPG-1 Trideceth-6 Cyclomethicone 4.00 4.00 4.00 4.00 4.00 4.00 Micronized Methylene Bis-Benzotriazolyl 4.00 4.00 4.00 1.00 2.00 2.00 Tetramethylbutylphenol Butyl Methoxydibenzoymethane 0.5 4.00 4.00 0.5 Ethylhexyl Methoxycinnamate 0.5 3.00 3.00 0.5 Octocrylene 0.5 4.00 4.00 0.5 Propanedinitrile, 2-[3-[bis(2-ethylhexyl)- 2.00 0.5 amino]-2-cyclohexen-1-ylidene]-(CAS Regn. 923271-36-7) or merocyanine derivative of formula (14) or 1,3,5-Triazine-2,4,6-triamine, N2,N4-bis[4-[5-(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]- N6-(2-ethylhexyl)-(Uvasorb K2A) (CAS Regn 288254-16-0) Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1- 2.00 1.00 0.5 methylpropyl)amino]-2-cyclohexen-1-ylidene]-, 2-ethylhexyl ester (CAS Regn. 923271-35-6) Uvinul A plus (CAS Regn. 302776-68-7) 0.5 0.5 2.00 2.00 Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′- 2.00 2.00 2.00 2.00 2.00 2.00 biphenyl]-4-yl)-(CAS Regn. 31274-51-8) 2,4-Pentadienoic acid, 5-(diethylamino)-2- 2.00 0.5 0.5 0.5 0.5 (phenylsulfonyl)-, octyl ester (CAS Regn. 98835-90-6) Micronized Methanone, 1,1′-(1,4-piperazine- 2.00 2.00 2.00 2.00 2.00 diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]- (CAS Regn. 919803-06-8) Mica (and) Titanium Dioxide (and)Tin oxide 1.00 1.00 1.00 1.00 1.00 1.00 Phenoxyethanol (and) Methylparaben (and) 1.00 1.00 1.00 1.00 1.00 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Water ad ad ad ad ad ad 100 100 100 100 100 100

TABLE-US-00008 Example B3: O/W Emulsion (3) INCI A B C D E F Tribehenin PEG-20 esters 5.00 5.00 5.00 5.00 5.00 5.00 Stearyl Alcohol 0.50 0.50 0.50 0.50 0.50 0.50 Dibutyl Adipate 5.00 5.00 5.00 5.00 5.00 5.00 PPG-2 Myristyl Ether Propionate 5.00 5.00 5.00 5.00 5.00 5.00 Triheptanoin 3.00 3.00 3.00 3.00 3.00 3.00 Ethylhexyl Salicylate 5.00 5.00 5.00 5.00 5.00 5.00 Butyl Methoxydibenzoymethane 3.00 3.00 3.00 3.00 3.00 3.00 Bis-Ethylhexyloxyphenol Methoxyphenyl 3.00 3.00 3.00 3.00 3.00 3.00 Triazine Ethylhexyl Triazone 3.00 3.00 3.00 3.00 3.00 3.00 Micronized Methylene Bis-Benzotriazolyl 2.00 2.00 2.00 2.00 2.00 2.00 Tetramethylbutylphenol Butyl Methoxydibenzoymethane 4.00 0.5 0.5 0.5 Bis-Ethylhexyloxyphenol Methoxyphenyl 1.00 1.00 1.00 1.00 1.00 1.00 Triazine Ethylhexyl Triazone 0.5 0.5 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate 4.00 Octocrylene 4.00 0.5 0.5 0.5 Propanedinitrile, 2-[3-[bis(2-ethylhe- 2.00 0.5 1.0 xyl)amino]-2-cyclohexen-1-ylidene]- (CAS Regn. 923271-36-7) or merocya- nine derivative of formula (14) or 1,3,5- Triazine-2,4,6-triamine, N2,N4-bis[4-[5- (1,1-dimethylpropyl)-2-benzoxazolyl]- phenyl]-N6-(2-ethylhexyl)- (Uvasorb K2A) (CAS Regn 288254-16-0) Acetic acid, 2-cyano-2-[5,5-dimethyl-3- 2.00 [(1-methylpropyl)amino]-2-cyclohexen-1- ylidene]-, 2-ethylhexyl ester (CAS Regn. 923271-35-6) Uvinul A plus (CAS Regn. 302776-68-7) 2.00 Micronized 1,3,5-Triazine, 2,4,6-tris- 2.00 5.00 2.00 2.00 2.00 4.00 ([1,1′-biphenyl]-4-yl)- (CAS Regn. 31274-51-8) 2,4-Pentadienoic acid, 5-(diethylamino)- 2.00 2-(phenylsulfonyl)-, octyl ester (CAS Regn. 98835-90-6) Micronized Methanone, 1,1′-(1,4-pipe- 2.00 2.00 5.00 4.00 2.00 2.00 razinediyl)bis[1-[2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl]- (CAS Regn. 919803-06-8) Sodium Polyacrylate 0.60 0.60 0.60 0.60 0.60 Disodium EDTA 0.20 0.20 0.20 0.20 0.20 0.20 Xanthan Gum 0.50 0.50 0.50 0.50 0.50 Iron Oxides (CALISHA Contemprorary 0.020 0.020 0.020 0.020 0.020 0.020 Black Oxide) Iron Oxides (CALISHA Contemporary 0.08 0.08 0.08 0.08 0.08 Salmon Red) Iron Oxides (CALISHA Contemporary 0.55 0.55 0.55 0.55 0.55 Sun Yellow) Cyclomethicone 5.00 5.00 5.00 5.00 5.00 5.00 Mica (and) Titanium Dioxide (and) Iron 0.50 0.50 0.50 0.50 0.50 0.50 Oxides (and) Cetyl Dimethicone Mica (and) Titanium Dioxide (and) Cetyl 0.50 0.50 0.50 0.50 0.50 0.50 Dimethicone (and) Iron Oxides (and) Carmine Phenoxyethanol (and) Methylparaben 1.00 1.00 1.00 1.00 1.00 1.00 (and) Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutyl- paraben Water ad ad ad ad ad ad 100 100 100 100 100 100

TABLE-US-00009 Example B4: W/O Emulsion (1) INCI A B C D E Polyglyceryl-4 Isostearate (and) Cetyl PEG/PPG- 4.50 4.50 4.50 4.50 4.50 10/1 Dimethicone (and) Hexyl Laurate Cetyl PEG/PPG-10/1 Dimethicone 2.20 2.20 2.20 2.20 2.20 Sorbitan Sesquioleate 1.00 1.00 1.00 1.00 1.00 Cera Alba 1.80 1.80 1.80 1.80 1.80 Hydrogenated Vegetable Oil 2.00 2.00 2.00 2.00 2.00 Phenethyl Benzoate 2.00 2.00 2.00 2.00 2.00 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.00 1.00 3.00 1.00 1.00 Ethylhexyl Methoxycinnamate 5.00 5.00 5.00 10.00 5.00 Titanium Dioxide (and) Silica (and) Dimethicone 5.00 5.00 5.00 5.00 5.00 Iron Oxides (and) Cetyl Dimethicone 0.13 0.13 0.13 0.13 0.13 Iron Oxides (and) Cetyl Dimethicone 0.60 0.60 0.60 0.60 0.60 Iron Oxides (and) Cetyl Dimethicone 0.20 0.20 0.20 0.20 0.20 Cyclomethicone (and) Disteardimonium Hectorite 5.00 5.00 5.00 5.00 5.00 (and) Propylene Carbonate Cyclopentasiloxane 6.00 6.00 6.00 6.00 6.00 Ethyl Trisiloxane 8.00 8.00 8.00 8.00 8.00 Dimethicone 6.00 6.00 6.00 6.00 6.00 Cyclopentasiloxane (and) C30-45 Alkyl Cetearyl 1.00 1.00 1.00 1.00 1.00 Dimethicone Crosspolymer (and) PEG/PPG-20/23 Dimethicone Water ad ad ad ad ad 100 100 100 100 100 Sodium Chloride 1.00 1.00 1.00 1.00 1.00 Pentylene Glycol (and) Scerotium Gum 3.00 3.00 3.00 3.00 3.00 Aqua (and) Retinyl Palmitate (and) Capryic/Capric 3.00 3.00 3.00 3.00 3.00 Triglyceride (and) Polysorbate 80 (and) Lecithin (and) Benzalkonium Chloride Butylen Glycol 3.00 3.00 3.00 3.00 3.00 Phenoxyethanol (and) Methylparaben (and) 1.00 1.00 1.00 1.00 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Aluminum Starch Octenylsuccinate 2.00 2.00 2.00 2.00 2.00 Talc 2.00 2.00 2.00 2.00 2.00 Silica 5.00 5.00 5.00 5.00 5.00 Mica (and) Iron Oxides (and) Cetyl Dimethicone 2.00 2.00 2.00 2.00 2.00 Mica (and) Titanium Dioxide (and) Iron Oxides (and) 1 0.5 Cetyl Dimethicone Micronized Methylene Bis-Benzotriazolyl Tetra- 0.5 6.00 4.00 2.00 1.00 methylbutylphenol Butyl Methoxydibenzoymethane 5.00 5.00 5.00 5.00 5.00 Ethylhexyl Triazone 0.60 0.60 0.60 0.60 0.60 Octocrylene 4.00 0.5 0.5 0.5 0.5 Propanedinitrile, 2-[3-[bis(2-ethylhexyl)amino]-2- 2.00 1.00 5.00 2.00 1.00 cyclohexen-1-ylidene]-(CAS Regn. 923271-36-7) or merocyanine derivative of formula (14) or 1,3,5- Triazine-2,4,6-triamine, N2,N4-bis[4-[5-(1,1-di- methylpropyl)-2-benzoxazolyl]phenyl]-N6-(2-ethylhexyl)- (Uvasorb K2A) (CAS Regn 288254-16-0) Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1-methyl- 6.00 6.00 6.00 6.00 6.00 propyl)amino]-2-cyclohexen-1-ylidene]-, 2-ethyl- hexyl ester (CAS Regn. 923271-35-6) Uvinul A plus (CAS Regn. 302776-68-7) 8.00 8.00 8.00 8.00 8.00 Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′-biphenyl]- 6.00 6.00 6.00 6.00 6.00 4-yl)-(CAS Regn. 31274-51-8) 2,4-Pentadienoic acid, 5-(diethylamino)-2-(phenylsulfonyl)-, 1.00 1.00 1.00 1.00 1.00 octyl ester (CAS Regn. 98835-90-6) Micronized Methanone, 1,1′-(1,4-piperazine- 1.00 3.00 2.00 4.00 0.5 diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]- phenyl]-(CAS Regn. 919803-06-8)

TABLE-US-00010 Example B5: W/O Emulsion (2) INCI A B C D E PEG-30 Dipolyhydroxystearate 3.00 3.00 3.00 3.00 3.00 Butylen Glycol Cocoate 2.00 2.00 2.00 2.00 2.00 Isodecyl neopentanoate 4.00 4.00 4.00 4.00 4.00 Isopropyl Isosterate 3.00 3.00 3.00 3.00 3.00 Beeswax 1.00 1.00 1.00 1.00 1.00 Hydrogenated Castor Oil 0.80 0.80 0.80 0.80 0.80 Ethylhexyl Methoxycinnamate 5.00 5.00 5.00 5.00 5.00 Iron Oxides (and) Cetyl Dimethicone (Calisha 0.10 0.10 0.10 0.10 0.10 Contemporary Black Oxide OD) Iron Oxides (and) Cetyl Dimethicone (Calisha 0.57 0.57 0.57 0.57 0.57 Contemporary Yellow Oxide OD) Iron Oxides (and) Cetyl Dimethicone (Calisha 0.13 0.13 0.13 0.13 0.13 Contemporary Medium Red Oxide OD) Caprylyl Methicone 2.50 2.50 2.50 2.50 2.50 Water ad ad ad ad ad 100 100 100 100 100 Sodium Chloride 1.00 1.00 1.00 1.00 1.00 Pentylene Glycol (and) Scerotium Gum 3.00 3.00 3.00 3.00 3.00 Aqua (and) Retinyl Palmitate (and) 3.00 3.00 3.00 3.00 3.00 Caprylic/Capric Triglyceride (and) Polysorbate 80 (and) Lecithin (and) Benzalkonium Chloride Butylen Glycol 5.00 5.00 5.00 5.00 5.00 Polysorbate 80 0.25 0.25 0.25 0.25 0.25 Caprylyl Methicone 5.50 5.50 5.50 5.50 5.50 Dimethicone 7.00 7.00 7.00 7.00 7.00 Micronized Methylene Bis-Benzotriazolyl Tetra- 3.00 6.00 3.00 6.00 2.00 methylbutylphenol Phenoxyethanol (and) Methylparaben (and) 1.00 1.00 1.00 1.00 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Silica 3.00 3.00 3.00 3.00 3.00 Nylon-12 6.00 6.00 6.00 6.00 6.00 Bis-Ethylhexyloxyphenol Methoxyphenyl 1.00 1.00 1.00 1.00 1.00 Triazine Butyl Methoxydibenzoymethane 5.00 5.00 5.00 5.00 5.00 Bis-Ethylhexyloxyphenol Methoxyphenyl 0.13 0.13 0.13 0.13 0.13 Triazine Ethylhexyl Triazone 0.60 0.60 0.60 0.60 0.60 Octocrylene 4.00 0.5 0.5 0.5 0.5 Propanedinitrile, 2-[3-[bis(2-ethylhexyl)amino]-2- 2.00 1.00 5.00 2.00 1.00 cyclohexen-1-ylidene]-(CAS Regn. 923271-36- 7) or merocyanine derivative of formula (14) or 1,3,5-Triazine-2,4,6-triamine, N2,N4-bis[4-[5- (1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]-N6- (2-ethylhexyl)-(Uvasorb K2A) (CAS Regn 288254-16-0 Acetic acid, 2-cyano-2-[5,5-dimethyl-3-[(1- 6.00 6.00 6.00 6.00 6.00 methylpropyl)amino]-2-cyclohexen-1-ylidene]-, 2-ethylhexyl ester (CAS Regn. 923271-35-6) Uvinul A plus (CAS Regn. 302776-68-7) 8.00 8.00 8.00 8.00 8.00 Micronized 1,3,5-Triazine, 2,4,6-tris([1,1′- 6.00 6.00 6.00 6.00 6.00 biphenyl]-4-yl)-(CAS Regn. 31274-51-8) 2,4-Pentadienoic acid, 5-(diethylamino)-2- 1.00 1.00 1.00 1.00 1.00 (phenylsulfonyl)-, octyl ester (CAS Regn. 98835- 90-6) Micronized Methanone, 1,1′-(1,4-piperazine- 1.00 3.00 2.00 4.00 0.5 diyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]- (CAS Regn. 919803-06-8) (Manganese modified) Titanium Dioxide 4.00 1.00 Diethylhexyl Syringylidene Malonate 2.00 1.00 3.00 4.00 0.5 Propanedioic acid, 2-[(4-hydroxy-3,5-dimethoxy- 1.00 1.00 5.00 phenyl)methyl]-, 1,3-bis(2-ethylhexyl) ester; (CAS Regn. 872182-46-2)