Photostabilizers, UV absorbers, and methods of photostabilizing compositions
View Patent ↗Polymers containing one or more novel photoactive moieties, sunscreen compositions including a mixture of a photoactive compound and a polymer containing one or more photoactive moieties are described herein. Also disclosed are methods for stabilizing a sunscreen composition, methods of filtering out ultra-violet light from a substrate by the addition of one or more of the foregoing polymers, methods accepting the triplet excited state energy with one or more of the foregoing polymer, and methods of increasing the UV-A Protective Value are described herein.
1. A compound of formula (I):
wherein R 2 is (a) phenyl substituted with 0, 1, 2, 3, or 4 R 6 substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R 6 substituents; R 1 is selected from the group consisting of aryl and substituted aryl; R 3 and R 4 are the same or different and are selected from the group consisting of C 1 -C 30 alkyl, C 3 -C 8 cycloalkyl, substituted alkyl, substituted cycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl, and substituted heterocycloalkyl; X is selected from the group consisting of O—C 1 -C 20 alkyl-O—, N(R 7 )-C 1 -C 20 alkyl-N(R 7 )—, and S—C 1 -C 20 alkyl-S—; R 7 is selected from the group consisting of hydrogen and C 1 -C 20 alkyl; R 5 is a structure of formula (II):
R 9 is (a) phenyl substituted with 0, 1, 2, 3, or 4 R 10 substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R 10 substituents; R 6 and R 10 are the same or different and are selected from the group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl, aryl, amino, substituted amino, amido, substituted amido, sulfate, carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether; R 8 is selected from the group consisting of aryl, and substituted aryl;
and n is an integer from 1 to 500.
2. The compound of claim 1 , wherein R 1 is selected from the group consisting of aryl and substituted aryl.
3. The compound of claim 1 , wherein R 1 is selected from the group consisting of naphthyl, phenyl, substituted naphthyl, and substituted phenyl.
4. The compound of claim 3 , wherein said substituted aryl and said substituted napthyl are substituted with an electron donating substituent selected from the group consisting of alkyl, alkenyl, aryl, alkoxy, amino, alkylamino, thioether, hydroxyl, oxycarbonyl, and amido.
5. The compound of claim 1 , wherein R 2 is 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R 6 substituents.
6. The compound of claim 1 , wherein R 2 is phenyl substituted with 0, 1, 2, 3, or 4 R 6 substituents.
7. The compound of claim 1 , wherein R 6 and R 10 are each electron donating substituents selected from the group consisting of alkyl, alkenyl, aryl, alkoxy, amino, thioether, hydroxyl, oxycarbonyl, and amido.
8. The compound of claim 1 , wherein X is O—C 1 -C 20 alkyl-O—.
9. The compound of claim 8 , wherein X is selected from the group consisting of
10. The compound of claim 1 , wherein said compound of formula (I) is:
11. A method of protecting human skin from ultra-violet radiation comprising applying a compound of claim 1 in a cosmetically acceptable carrier to said human skin.
12. A method of photostabilizing a dibenzoylmethane derivative in a composition, said method comprising the step of adding to said dibenzoylmethane derivative a photostabilizing amount of a compound of claim 1 .
13. The method of claim 12 , wherein said composition further comprises a photoactive compound selected from the group consisting of bis-ethylethoxyphenol-methoxyphenol triazine, methylene bis-benzotriazolyl tetramethylbutyl phenol, diethylamino-hydroxybenzoyl-hexyl benzoate, disodium phenyldibenzimidazoletetrasulfonate, octocrylene, di-octyl-naphthalate, and combinations thereof.
14. A method of quenching triplet excited state energy from a triplet-excited photoactive compound in a sunscreen composition comprising adding to said composition a compound of claim 1 .
15. A sunscreen composition, comprising a mixture of a photoactive compound and a compound of claim 1 .
16. The composition of claim 15 , wherein said photoactive compound is selected from the group consisting of bis-ethylethoxyphenol-methoxyphenol triazine, methylene bis-benzotriazolyl tetramethylbutyl phenol, diethylamino-hydroxybenzoyl-hexyl benzoate, disodium phenyldibenzimidazoletetrasulfonate, octocrylene, di-octyl-naphthalate, and combinations thereof.
17. The composition of claim 15 , wherein R 1 is selected from the group consisting of aryl and substituted aryl.
18. The composition of claim 15 , wherein R 1 is selected from the group consisting of naphthyl, phenyl, substituted naphthyl, and substituted phenyl.
19. The composition of claim 15 , wherein R 2 is 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R 6 substituents.
20. The composition of claim 15 , wherein R 2 is phenyl substituted with 0, 1, 2, 3, or 4 R 6 substituents.
21. The composition of claim 16 , wherein R 6 and R 10 are each electron donating substituents selected from the group consisting of alkyl, alkenyl, aryl, alkoxy, amino, alkylamino, thioether, hydroxyl, oxycarbonyl and amido.
22. The composition of claim 15 , wherein X is O—C 1 -C 20 alkyl-O—.
23. The composition of claim 22 , wherein X is selected from the group consisting of
24. The composition of claim 15 , wherein the photoactive compound is selected from the group consisting of p-aminobenzoic acid and salts and derivatives thereof; anthranilate and derivatives thereof; dibenzoylmethane and derivatives thereof; salicylate and derivatives thereof; cinnamic acid and derivatives thereof; dihydroxycinnamic acid and derivatives thereof; camphor and salts and derivatives thereof; trihydroxycinnamic acid and derivatives thereof; dibenzalacetone naphtholsulfonate and salts and derivatives thereof; benzalacetophenone naphtholsulfonate and salts and derivatives thereof; dihydroxy-naphthoic acid and salts thereof; o-hydroxydiphenyldisulfonate and salts and derivatives thereof; p-hydroxydiphenyldisulfonate and salts and derivatives thereof; coumarin and derivatives thereof; diazole derivatives; quinine derivatives and salts thereof; quinoline derivatives; hydroxy-substituted benzophenone derivatives; methoxy-substituted benzophenone derivatives; uric acid derivatives; vilouric acid derivatives; tannic acid and derivatives thereof; hydroquinone; benzophenone derivatives; 1,3,5-triazine derivatives; phenyldibenzimidazole tetrasulfonate and salts and derivatives thereof; terephthalylidene dicamphor sulfonic acid and salts and derivatives thereof; methylene bis-benzotriazolyl tetramethylbutylphenol and salts and derivatives thereof; bis-ethylhexyloxyphenol methoxyphenyl triazine and salts and derivatives thereof; diethylamino hydroxybenzoyl hexyl benzoate and salts and derivatives thereof; and combinations of the foregoing.
25. The composition of claim 15 , wherein the photoactive compound is a dibenzoylmethane derivative.
26. The composition of claim 25 , wherein said dibenzoylmethane derivative is selected from the group consisting of 2-methyldibenzoylmethane; 4 methyldibenzoylmethane; 4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane; 2,4-dimethyldibenzoylmethane; 2,5-dimethyldibenzoylmethane; 4,4′-diisopropyldibenzoylmethane; 4,4′-dimethoxydibenzoylmethane; 4-tert-butyl-4′-methoxydibenzoylmethane; 2-methyl-5-isopropyl-4′-methoxydibenzoylmethane; 2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane; 2,4-dimethyl-4′-methoxydibenzoylmethane; 2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane, and combinations thereof.
27. The composition of claim 15 , wherein said photoactive compound is selected from the group consisting of bis-ethylethoxyphenol-methoxyphenol triazine, methylene bis-benzotriazolyl tetramethylbutyl phenol, diethylamino-hydroxybenzoyl-hexyl benzoate, disodium phenyldibenzimidazoletetrasulfonate, octocrylene, di-octyl-naphthalate, and combinations thereof.
28. The composition of claim 27 , wherein said photoactive compound is bis-ethylethoxyphenol-methoxyphenol triazine.
29. The composition of claim 27 , wherein said photoactive compound is methylene bis-benzotriazolyl tetramethylbutyl phenol.
30. The composition of claim 27 , wherein said photoactive compound is diethylamino-hydroxybenzoyl-hexyl benzoate.
31. The composition of claim 27 , wherein said photoactive compound is disodium phenyldibenzimidazoletetrasulfonate.
32. The composition of claim 27 , wherein said photoactive compound is octocrylene.
33. The composition of claim 27 , wherein said photoactive compound is di-octyl-naphthalate.
34. The composition of claim 15 , wherein said composition has a UV-A Protection Value of at least about 8.0.
35. The composition of claim 34 , wherein said composition has a UV-A Protection Value in the range of about 10.0 to about 15.0.
36. A compound of formula (III):
wherein R l and R 8 are the same or different and are selected from the group consisting of aryl and substituted aryl; R 3 and R 4 are the same or different and are selected from the group consisting of C 1 -C 30 alkyl, C 3 -C 8 cycloalkyl, substituted alkyl, substituted cycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl, and substituted heterocycloalkyl; X is selected from the group consisting of O—C 1 -C 20 alkyl-O—, N(R 7 )-C 1 -C 20 alky-N(R 7 )—, and S—C 1 -C 20 alkyl-S—; R 7 is selected from the group consisting of hydrogen and C 1 -C 20 alkyl; R 9 and R 10 are the same or different and are each an electron donating group selected from the group consisting of alkyl, alkenyl, aryl, alkoxy, amino, alkylamino, thioether, hydroxyl, oxycarbonyl, and amido; and n is an integer from 1 to 500.
37. The compound of claim 36 , wherein R 1 and R 8 are the same or different and are selected from the group consisting of phenyl, and substituted phenyl.
38. The compound of claim 36 , wherein X is O—C 1 -C 20 alkyl-O—.
39. The compound of claim 38 , wherein X is selected from the group consisting of
40. The compound of claim 36 , wherein said compound of formula (III) is: