Effective sunscreen composition with diethylamino hydroxybenzoyl hexyl benzoate and butyl methoxy dibenzoyl methane
阅读说明：本技术 具有二乙氨基羟基苯甲酰基苯甲酸己酯和丁基甲氧基二苯甲酰基甲烷的有效防晒组合物 (Effective sunscreen composition with diethylamino hydroxybenzoyl hexyl benzoate and butyl methoxy dibenzoyl methane ) 是由 M·索恩 S·克鲁斯 M·施尼德尔 S·阿克尔 于 2020-03-13 设计创作，主要内容包括：本发明涉及包含二乙氨基羟基苯甲酰基苯甲酸己酯、丁基甲氧基二苯甲酰基甲烷、二乙基己氧基苯酚甲氧基苯基三嗪、乙基己基三嗪酮和/或二乙基己基丁酰胺基三嗪酮的防晒或日用护理组合物,其中该组合物不含亚甲基二-苯并三唑基四甲基丁基苯酚、三-联苯基三嗪、二氧化钛和氧化锌并且其中该组合物以大于或等于0.8的比例包含二乙氨基羟基苯甲酰基苯甲酸己酯和丁基甲氧基二苯甲酰基甲烷。此外,本发明涉及所述组合物给药于敏感性皮肤的用途。此外,本发明涉及所述组合物在将该产品施用于皮肤上之后减少粘附砂量的用途。(The present invention relates to a sunscreen or household care composition comprising diethylaminohydroxybenzoyl hexyl benzoate, butyl methoxydibenzoyl methane, diethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone and/or diethylhexylbutamido triazone, wherein the composition is free of methylenebis-benzotriazolyl tetramethylbutyl phenol, tris-biphenyltriazine, titanium dioxide and zinc oxide and wherein the composition comprises diethylaminohydroxybenzoyl hexyl benzoate and butyl methoxydibenzoyl methane in a ratio of greater than or equal to 0.8. Furthermore, the invention relates to the use of said composition for administration to sensitive skin. Furthermore, the invention relates to the use of said composition for reducing the amount of adhering sand after application of the product on the skin.)
1. A sunscreen or household care composition comprising
(i)2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoic acid hexyl ester (INCI diethylaminohydroxybenzoyl benzoic acid hexyl ester); and
(ii)1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butyl methoxydibenzoylmethane); and
(iii)2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1,3, 5-triazine (INCI diethylhexyloxyphenol methoxyphenyl triazine); and
(iv)4, 4'- (1,3, 5-triazine-2, 4, 6-triyltrimethylamino) tribenzoic acid tris (2-ethylhexyl) ester (INCI ethylhexyl triazone) and/or 4,4' - [ [6- [ [4- [ [ (1, 1-dimethylethyl) amino ] carbonyl ] phenyl ] amino ] -1,3, 5-triazine-2, 4-diyl ] diimino ] dibenzoic acid bis (2-ethylhexyl) ester (INCI diethylhexyl butamidotriazone),
wherein the composition is free of 2,2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol ] (INCI methylenebis-benzotriazolyl tetramethylbutyl phenol), 2,4, 6-tris (biphenyl-4-yl) -1,3, 5-triazine (INCI tris-biphenyltriazine), titanium dioxide, zinc oxide, and benzylidene malonates according to the following preferred structure:
wherein
R1Is methyl, ethyl, propyl or n-butyl;
if R is1Is methyl, R is tert-butyl orA group of formula (II) or The group of (a) or (b),
wherein
R2And R3Independently of one another, hydrogen or methyl;
R4is methyl, ethyl or n-propyl;
R5and R6Independently of one another, hydrogen or C1-C3An alkyl group;
if R is1Is ethyl, propyl or n-butyl, then R is isopropyl; and
wherein the composition comprises (i) - (ii) in a ratio of greater than or equal to 0.8.
2. A sunscreen or household care composition according to claim 1, wherein said composition comprises (i) hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate) and (ii)1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butyl methoxydibenzoylmethane) in a ratio greater than or equal to 1.
3. A sunscreen or household care composition according to claim 1 or 2, wherein said composition comprises (i) hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoate (hexyl INCI diethylaminohydroxybenzoyl benzoate) and (ii)1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butylmethoxydibenzoylmethane) in a ratio of 1:1 to 10:1, preferably 1:1 to 5:1, more preferably 1:1 to 2:1, even more preferably 1:1 to 1.5: 1.
4. A sunscreen or daily care composition according to any of claims 1 to 3, wherein said composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone), ethylhexyl 2-cyano-3, 3-diphenylacrylate (INCI octocrylene), 2-ethylhexyl (2E) -3- (4-methoxyphenyl) acrylate (INCI ethylhexyl methoxycinnamate), and isoamyl 4-methoxycinnamate (INCI p-methoxycinnamate).
5. A sunscreen or household care composition according to any of claims 1 to 4, wherein said composition is free of parabens.
6. A sunscreen or household care composition according to any of claims 1 to 5, wherein said composition is provided in the form of a spray.
7. A sunscreen or household care composition according to any of claims 1 to 6, wherein said composition is free of emulsifiers.
8. A sunscreen or household care composition according to any of claims 1 to 7, wherein said composition is free of phenoxyethanol.
9. A sunscreen or daily care composition according to any of claims 1 to 8 wherein (iii) is an oil soluble UV filter or wherein (iii) is 2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1,3, 5-triazine (INCI diethylhexyloxyphenol methoxyphenyl triazine) dissolved in a polymer matrix that is dispersible in water.
10. A sunscreen or daily care composition according to any of claims 1 to 9 wherein said composition comprises hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate) in an amount of 1 to 10% by weight, based on the total weight of the composition.
11. A sunscreen or daily care composition according to any of claims 1 to 10 wherein said composition comprises 1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butyl methoxydibenzoylmethane) in an amount of 1 to 5% by weight, based on the total weight of the composition.
12. A sunscreen or daily care composition according to any of claims 1 to 11 wherein said composition comprises 2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1,3, 5-triazine (INCI diethylhexyloxyphenol methoxyphenyl triazine) in an amount of 0.5 to 5 wt. -%, preferably 0.8 to 3 wt. -%, based on the total weight of the composition.
13. A sunscreen or daily care composition according to any of claims 1 to 12 wherein the composition comprises tris (2-ethylhexyl) 4,4',4 "- (1,3, 5-triazine-2, 4, 6-triyltrimethylamino) tribenzoate (INCI ethylhexyltriazone) in an amount of from 0.5 to 5 wt%, preferably from 0.8 to 3 wt%, based on the total weight of the composition.
14. A sunscreen or household care composition according to any of claims 1 to 13, wherein said composition comprises di (2-ethylhexyl) 4,4' - [ [6- [ [4- [ [ (1, 1-dimethylethyl) amino ] carbonyl ] phenyl ] amino ] -1,3, 5-triazine-2, 4-diyl ] diimino ] dibenzoate (INCI diethylhexylbutamidotriazone) in an amount of 0.5 to 5% by weight, preferably 0.8 to 3% by weight, based on the total weight of the composition.
15. A sunscreen or household care composition according to any of claims 1 to 14, wherein said composition comprises at least one perfume.
16. A sunscreen or daily care composition according to any of claims 1 to 15 wherein said composition comprises at least one emollient with a polarity index <30 mN/m.
17. Use of a sunscreen or household care composition as defined in any of claims 1 to 16 to reduce the amount of adhering grits on the skin.
Examples
Method for producing sunscreen compositions
The ingredients of part a and the ingredients of part B provided below in tables 1.1, 1.2, 1.3 and 1.4 for each of the tested sunscreen compositions were combined and heated to 80 ℃ respectively, wherein part a was added to part B with stirring and further homogenized. The sunscreen composition is then cooled to room temperature with stirring. If present, part C was added and the pH of each composition was adjusted to 6.5-7.00 with NaOH (30%).
All amounts mentioned in the table below relate to the respective amounts in weight% based on the total weight of the composition.
Sunscreen composition
TABLE 1.1
TABLE 1.2
TABLE 1.3
TABLE 1.4
This amount relates to the active, 5% MBBT corresponds to 10% of the commercial product Tinosorb M.
Recovery measurements on photostability of BMDBM
The sunscreen and UV filter compositions as defined above were applied on a roughened quartz plate (2. mu.l/cm)2). Each plate was irradiated using Atlas CPS devices at different durations (MED ═ minimum erythema dose):
-0h (0MED, no irradiation)
-1h(5MED)，
-2h(10MED)，
-4h(20MED)。
A total of 4 plates were prepared for each irradiation condition. Plates were rinsed with tetrahydrofuran after irradiation. The rinse solution was further analyzed via HPLC to determine recovery of BMDBM.
TABLE 2.1
Comparative composition 1a
Comparative composition 1b
Comparative composition 1c
0MED
100％
100％
100％
5MED
98％
58％
62％
10MED
89％
31％
37％
20MED
83％
12％
14％
TABLE 2.2
Composition 2
Composition 3
0MED
100％
100％
5MED
79％
87％
10MED
62％
75％
20MED
33％
52％
TABLE 2.3
Composition 4
Composition 5
0MED
100％
100％
5MED
86％
97％
10MED
73％
77％
20MED
55％
61％
TABLE 2.4
Comparative composition 2a
Comparative composition 2b
Composition 6
0MED
100％
100％
100％
5MED
68％
55％
82％
10MED
43％
26％
63％
20MED
21％
11％
41％
Recovery measurement for photostability of BEMT
The sunscreen and UV filter compositions as defined above were applied on a roughened quartz plate (2. mu.l/cm)2). Each panel was irradiated using an Atlas CPS device at different durations:
-0h (0MED, no irradiation)
-1h(5MED)，
-2h(10MED)，
-4h(20MED)。
A total of 4 plates were prepared for each irradiation condition. Plates were rinsed with tetrahydrofuran after irradiation. The rinse solution was further analyzed via HPLC to determine recovery of BEMT.
TABLE 3.1
Comparative composition 1a
Comparative composition 1b
Comparative composition 1c
0MED
100％
100％
100％
5MED
103％
93％
92％
10MED
98％
86％
89％
20MED
100％
76％
76％
The person skilled in the art knows that more than 100% of the data after irradiation are due to common measurement fluctuations.
TABLE 3.2
Composition 2
Composition 3
0MED
100％
100％
5MED
99％
101％
10MED
102％
104％
20MED
95％
102％
The person skilled in the art knows that more than 100% of the data after irradiation are due to common measurement fluctuations.
TABLE 3.3
Composition 4
Composition 5
0MED
100％
100％
5MED
98％
106％
10MED
95％
98％
20MED
95％
97％
The person skilled in the art knows that more than 100% of the data after irradiation are due to common measurement fluctuations.
TABLE 3.4
Comparative composition 2a
Comparative composition 2b
Composition 6
0MED
100％
100％
100％
5MED
98％
93％
97％
10MED
92％
84％
92％
20MED
90％
78％
92％
Measurement of interfacial tension (polarity index)
Interfacial tension of the corresponding emollients listed below were measured using a Tensimat Densimat TD 2000.
TABLE 4.1
UV Filter Properties
The wavelength of the maximum absorption value (λ max) is an indicator describing the effect of the UV filter molecules. It gives the wavelength at which the absorption is maximum. For UVA filters, the wavelength of maximum absorption should be close to 359nm corresponding to the peak of the PPD (persistent tanning) effect spectrum. The PPD effect spectrum corresponds to the product of the PPD (permanent tanning) action spectrum and the light intensity (see ISO 24443).
The UV transmission spectrum of each UV filter-emollient mixture was measured from 290nm to 400nm using a UV/Vis Spectrophotometer Perkin Elmer Lambda 25. For each mixture 3 stock solutions were prepared with a concentration of 1mM UV filter. In addition, three dilutions of each stock solution were prepared so that there were a total of 9 measurements for each UV filter-emollient solution. All solutions were then packed in a UV transparent quartz cuvette with a 1cm path length to measure UV transmittance.
Lambda max value for BMDBM
TABLE 4.2
Lambda max value of DHHB
TABLE 4.3
Solubility measurement
0.02g of UV filter was added to 2ml of the corresponding emollient listed below, previously filled in 20ml vials with caps. The vial was placed in a constant temperature water bath (25 ℃) and the blend was stirred for 7 days. If the tested UV filters were completely soluble, additional filters were added until precipitation was observed. After 7 days the samples were centrifuged for 30 minutes at 13000 rpm. If the supernatant is cloudy, it is filtered through a 0.2 μm non-sterile Membrex 25 PET filter. Each sample was diluted with a suitable solvent prior to measurement or measured without further dilution in a 1cm path length quartz cuvette at lower concentrations. The concentration of the UV filter was then determined by UV/Vis spectroscopy using a Perkin Elmer Lambda 20 apparatus (method a according to Herzog b., Giesinger j., Schnyder m., SOFW Journal, 2013, 139(7), pages 7-14).
TABLE 4.4
TABLE 4.5
Measurement of amount of adhering sand
The ingredients of part a and the ingredients of part B provided below in table 5 for each test sunscreen composition were combined and heated to 80 ℃ respectively, wherein part a was added to part B with stirring and further homogenized. The sunscreen composition is then cooled to room temperature with stirring. Add part C and D and adjust the pH of each composition to 6.5-7.00 with NaOH.
TABLE 5
Comparative composition 3 and compositions 7, 8 and 9 were tested for their effect of preventing or at least minimizing sand adhesion on the skin after application of the sunscreen composition. The following methods were used:
50mg of the test formulation were applied as uniformly as possible by hand application onto PMMA plates (Helioscreen) of dimensions 5.0cm by 5.0 cm. The plates were left in the dark for 15 minutes to allow water evaporation and plate equilibration to achieve film formation prior to further processing. After the equilibration period each veneer was weighed with an analytical balance. The samples were covered with 10g of sand (No. 1.07711.1000, see sand, Merck KGaA). This amount allows an excessive coverage of the entire PMMA plate. The plate is then placed from the horizontal position to the vertical position, which is equivalent to a 90 ℃ turn, and held in the vertical position for 5 seconds. The synchronization steps are repeated for each side of the board. The panel with residual sand pick was weighed again and the amount of sand pick was calculated:
sand adhered to the panel (g) panel after sand contact (g) -sunscreen overlay (g)
The adhesion ratio of each composition is shown in table 6.
TABLE 6
95% confidence intervals
Comparative composition 3 exhibited greater sand adhesion than inventive compositions 7, 8 and 9.
In preferred embodiments, the present invention relates to the following other items.
1. A sunscreen or household care composition comprising:
(i)2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoic acid hexyl ester (INCI diethylaminohydroxybenzoyl benzoic acid hexyl ester); and
(ii)1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butyl methoxydibenzoylmethane); and
(iii)2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1,3, 5-triazine (INCI diethylhexyloxyphenol methoxyphenyl triazine); and
(iv)4, 4'- (1,3, 5-triazine-2, 4, 6-triyltrimethylamino) tribenzoic acid tris (2-ethylhexyl) ester (INCI ethylhexyl triazone) and/or 4,4' - [ [6- [ [4- [ [ (1, 1-dimethylethyl) amino ] carbonyl ] phenyl ] amino ] -1,3, 5-triazine-2, 4-diyl ] diimino ] dibenzoic acid bis (2-ethylhexyl) ester (INCI diethylhexyl butamidotriazone),
wherein the composition is free of 2,2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol ] (INCI methylenebis-benzotriazolyl tetramethylbutyl phenol), 2,4, 6-tris (biphenyl-4-yl) -1,3, 5-triazine (INCI tris-biphenyltriazine), titanium dioxide, and zinc oxide; and
wherein the composition comprises (i) - (ii) in a ratio of greater than or equal to 0.8.
2. A sunscreen or household care composition according to item 1, wherein the composition comprises (i) hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate) and (ii)1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butyl methoxydibenzoylmethane) in a ratio of greater than or equal to 1.
3. A sunscreen or household care composition according to item 1 or 2, wherein the composition comprises (i) hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoate (hexyl INCI diethylaminohydroxybenzoyl benzoate) and (ii)1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butylmethoxydibenzoylmethane) in a ratio of 1:1 to 10:1, preferably 1:1 to 5:1, more preferably 1:1 to 2:1, even more preferably 1:1 to 1.5: 1.
4. A sunscreen or daily care composition according to any of claims 1 to 3 wherein the composition is free of 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone), ethylhexyl 2-cyano-3, 3-diphenylacrylate (INCI octocrylene), 2-ethylhexyl (2E) -3- (4-methoxyphenyl) acrylate (INCI ethylhexyl methoxycinnamate), and isoamyl 4-methoxycinnamate (INCI p-methoxycinnamate).
5. A sunscreen or household care composition according to any of claims 1-4, wherein the composition is free of parabens.
6. A sunscreen or household care composition according to any of claims 1-5, wherein the composition is provided in the form of a spray.
7. A sunscreen or household care composition according to any of claims 1 to 6 wherein the composition is free of emulsifiers.
8. A sunscreen or household care composition according to any of claims 1-7, wherein the composition is free of phenoxyethanol.
9. A sunscreen or household care composition according to any of claims 1 to 8 wherein (iii) is an oil soluble UV filter or wherein (iii) is 2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1,3, 5-triazine (INCI diethylhexyloxyphenol methoxyphenyl triazine) dissolved in a water dispersible polymer matrix.
10. A sunscreen or household care composition according to any of claims 1-9, wherein the composition comprises hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate) in an amount of 1-10 wt. -%, based on the total weight of the composition.
11. A sunscreen or household care composition according to any of claims 1-10, wherein the composition comprises 1- (4- (1, 1-dimethylethyl) phenyl) -3- (4-methoxyphenyl) -1, 3-propanedione (INCI butyl methoxydibenzoylmethane) in an amount of 1 to 5% by weight, based on the total weight of the composition.
12. A sunscreen or daily care composition according to any of claims 1 to 11 wherein the composition comprises 2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1,3, 5-triazine (INCI diethylhexyloxyphenol methoxyphenyl triazine) in an amount of 0.5 to 5% by weight, preferably 0.8 to 3% by weight, based on the total weight of the composition.
13. A sunscreen or household care composition according to any of claims 1 to 12, wherein the composition comprises tris (2-ethylhexyl) 4,4',4 "- (1,3, 5-triazine-2, 4, 6-triyltrimethylamino) tribenzoate (INCI ethylhexyltriazone) in an amount of from 0.5 to 5 wt%, preferably from 0.8 to 3 wt%, based on the total weight of the composition.
14. A sunscreen or household care composition according to any of claims 1 to 13, wherein the composition comprises bis (2-ethylhexyl) 4,4' - [ [6- [ [4- [ [ (1, 1-dimethylethyl) amino ] carbonyl ] phenyl ] amino ] -1,3, 5-triazine-2, 4-diyl ] diimino ] dibenzoate (INCI diethylhexylbutamidotriazone) in an amount of 0.5 to 5% by weight, preferably 0.8 to 3% by weight, based on the total weight of the composition.
15. A sunscreen or household care composition according to any of claims 1 to 14, wherein the composition comprises a perfume.
16. Use of a sunscreen or household care composition as defined in any of claims 1 to 15 for administration to sensitive skin.
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