Effective sunscreen composition with diethylamino hydroxybenzoyl hexyl benzoate and butyl methoxy dibenzoyl methane and without octocrylene
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且不含奥克立林的有效防晒组合物 (Effective sunscreen composition with diethylamino hydroxybenzoyl hexyl benzoate and butyl methoxy dibenzoyl methane and without octocrylene ) 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,其中该组合物不含奥克立林和甲氧基肉桂酸乙基己基酯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组合物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 diethylamino hydroxybenzoyl hexyl benzoate, butyl methoxydibenzoyl methane, diethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone and/or diethylhexyl butamido triazone, wherein the composition is free of octocrylene and ethylhexyl methoxycinnamate and wherein the composition comprises diethylamino hydroxybenzoyl 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 applying the composition to 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',4 "- (1,3, 5-triazine-2, 4, 6-triyltrimethylamino) tris (2-ethylhexyl) tribenzoate (INCI ethylhexyl triazone) and/or bis (2-ethylhexyl) 4,4' - [ [6- [ [4- [ [ (1, 1-dimethylethyl) amino ] carbonyl ] phenyl ] amino ] -1,3, 5-triazine-2, 4-diyl ] diimino ] dibenzoate (INCI diethylhexyl butamidotriazone); and
(v) at least one organic particulate UV filter,
wherein the composition is free of ethylhexyl 2-cyano-3, 3-diphenylacrylate (INCI octocrylene), 2-ethylhexyl 3- (4-methoxyphenyl) acrylate (INCI ethylhexyl methoxycinnamate), 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 or formulaA group of formula (II) orOrThe 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 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 household care composition according to any of claims 1 to 3 wherein said composition is free of titanium dioxide and zinc oxide.
5. A sunscreen or daily care composition according to any of claims 1 to 4 wherein said composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and isoamyl 4-methoxycinnamate (INCI p-methoxycinnamate isoamyl).
6. A sunscreen or household care composition according to any of claims 1 to 5, wherein said composition is free of parabens.
7. A sunscreen or household care composition according to any of claims 1 to 6 wherein said composition is provided in the form of a sprayable product.
8. A sunscreen or household care composition according to any of claims 1 to 7 wherein said composition is free of emulsifiers.
9. A sunscreen or household care composition according to any of claims 1 to 8, wherein said composition is free of phenoxyethanol.
10. A sunscreen or daily care composition according to any of claims 1 to 9 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.
11. A sunscreen or daily care composition according to any of claims 1 to 10 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.
12. A sunscreen or daily care composition according to any of claims 1 to 11 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.
13. A sunscreen or daily care composition according to any of claims 1 to 12 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.
14. A sunscreen or household care composition according to any of claims 1 to 13, wherein said 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.
15. A sunscreen or household care composition according to any of claims 1 to 14, 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.
16. A sunscreen or household care composition according to any of claims 1 to 15 wherein said at least one organic particulate UV filter is selected from 2,2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol](INCI methylenebis-benzotriazolyl tetramethylbutylphenol), 2,4, 6-tris (biphenyl-4-yl) -1,3, 5-triazine (INCI terphenyl triazine), 1' - (1, 4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl ] -benzene]Phenyl radical]Methanone (INCI bis (diethylaminohydroxybenzoyl benzoyl) piperazine), 5,6,5',6' -tetraphenyl-3-3 ' - (1, 4-phenylene) bis (1,2, 4-triazine) (INCI phenylenedi-diphenyltriazine), micronized 1, 4-bis (benzo-c-hydroxybenzoyl) piperazine), and a process for their preparationOxazol-2' -yl) benzene and combinations thereof.
17. A sunscreen or household care composition according to any of claims 1-16, wherein said composition has a Sun Protection Factor (SPF) of at least 20.
18. A sunscreen or household care composition according to any of claims 1-17, wherein said composition has a b value < 25.
19. Use of a sunscreen or household care composition as defined in any of claims 1 to 18 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.
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
Will be as defined aboveThe sunscreen or UV filter composition of (2. mu.l/cm) is applied to a roughened quartz plate2). 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 or UV filter composition as defined above was 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 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 indicated 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 25PET 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
This amount relates to the active, 3% MBBT corresponds to 6% of the commercial product Tinosorb M.
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 according to the formula:
sand adhered to the plate (mg) plate after sand contact (mg) -sunscreen overlay plate (mg)
The sand sticking rate of each composition is shown in table 6.
TABLE 6
Comparative composition 3 exhibited greater sand adhesion than inventive compositions 7, 8 and 9.
Color testing
The ingredients of part a and the ingredients of part B provided below in table 7 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 7
This amount relates to the active, 1.5% MBBT corresponds to 3% of the commercial product Tinosorb M.
Comparative composition 4 and compositions 10 and 11 were tested for color. The principle is that the brighter the color of a product, the more acceptable the product is to the consumer. The following methods were used:
the color of the cosmetic sunscreen formulations was evaluated based on the determination of L a b color space parameters. Using this method it is possible to determine the color difference between several samples on the basis of numerical values. In the system L a b L corresponds to the luminance, a to the red/green coordinates and b to the yellow/blue coordinates. The advantage of this method is that it is not dependent on the device used for the measurement. The formulations to be measured are filled into transparent petri dishes (58 × 15 mm). The lid was carefully placed on the petri dish to avoid any air bubbles under the lid. Parameters la a b of the petri dish containing the sunscreen (light D65, observer 10 °) were measured with a mission Spectrometer Datacolor SF 400. Sunscreens are generally yellow in color, which is undesirable to the end consumer. To improve consumer compliance, sunscreens are therefore as less yellow as possible. Thus, the parameter b is taken to evaluate the yellow color of the formulation, the higher the value b, the higher the measured yellow hue.
The color evaluations of comparative composition 4 and compositions 9 and 10 are shown in table 8 below.
TABLE 8
Comparative composition 4
Composition 10
Composition 11
b value
28.43
18.98
20.47
As can be seen from the b values, the hue of comparative composition 4 is much more yellow than the hues of inventive compositions 10 and 11.
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 ethylhexyl 2-cyano-3, 3-diphenylacrylate (INCI octocrylene) and 2-ethylhexyl (2E) -3- (4-methoxyphenyl) acrylate (INCI ethylhexyl methoxycinnamate); and wherein the composition comprises (i) - (ii) in a ratio 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 household care composition according to any of claims 1-3, wherein the composition is free of titanium dioxide and zinc oxide.
5. A sunscreen or daily care composition according to any of claims 1 to 4, wherein the composition does not comprise 2-hydroxy-4-methoxybenzophenone (INCI oxybenzone) and isoamyl 4-methoxycinnamate (INCI p-methoxycinnamate).
6. A sunscreen or household care composition according to any of claims 1 to 5, wherein the composition is free of parabens.
7. A sunscreen or household care composition according to any of claims 1-6, wherein the composition is provided in the form of a sprayable product.
8. A sunscreen or household care composition according to any of claims 1 to 7 wherein the composition is free of emulsifiers.
9. A sunscreen or household care composition according to any of claims 1-8, wherein the composition is free of phenoxyethanol.
10. A sunscreen or household care composition according to any of claims 1-9 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.
11. A sunscreen or household care composition according to any of claims 1-10, wherein the composition comprises hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl ] benzoate (INCI diethylaminohydroxybenzoyl hexyl benzoate) in an amount of 1-10% by weight, based on the total weight of the composition.
12. A sunscreen or household care composition according to any of claims 1-11, 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 weight%, 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 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.
14. A sunscreen or household care composition according to any of claims 1 to 13, 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.
15. A sunscreen or household care composition according to any of claims 1 to 14, 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.
16. A sunscreen or household care composition according to any of claims 1-15, wherein the composition has a Sun Protection Factor (SPF) of at least 20.
17. Use of a sunscreen or household care composition as defined in any of claims 1 to 15 for administration to sensitive skin.