SUNSCREEN SPRAY CONTAINING ETHYLCELLULOSE

DE502020011107D1Active Publication Date: 2025-06-12BEIERSDORF AG
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Patent Information

Application Number
DE502020011107
Authority / Receiving Office
DE · DE
Patent Type
Patents
Current Assignee / Owner
Priority Date
2019-08-28
Filing Date
2020-08-21
Publication Date
2025-06-12
Estimated Expiration
2040-08-21

AI Technical Summary

Technical Problem

Existing sunscreen sprays pose a health risk due to inhalable aerosol droplets that can penetrate the respiratory tract, with a significant portion depositing in the lungs, particularly those smaller than 10 micrometers in diameter.

Method used

Incorporating ethylcellulose into ethanolic sunscreen sprays, along with UV filters like Ethylhexyl Triazone and Diethylamino hydroxybenzoyl hexyl benzoate, ensures that droplets are at least 10 micrometers in size and less than 0.2% are smaller, preventing inhalation.

Benefits of technology

Prevents aerosol droplets from entering the lungs, reducing respiratory tract deposition and minimizing health risks associated with inhalation.

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Description

[0001] The present invention relates to the use of ethylcellulose in cosmetic, ethanolic sunscreen sprays for preventing the spray droplets from being respired, as well as to cosmetic preparations in the form of a sunscreen spray containing ethanol and ethylcellulose and ethylhexyl triazone and / or hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino hydroxybenzoyl hexyl benzoate).

[0002] The trend away from a refined pallor toward "healthy, athletically tanned skin" has been unbroken for years. To achieve this, people expose their skin to sunlight, as this triggers pigment formation in the form of melanin. However, the ultraviolet radiation from sunlight also has a damaging effect on the skin. In addition to acute damage (sunburn), long-term effects such as an increased risk of skin cancer occur with excessive exposure to light in the UVB range (wavelength: 280-320 nm). Excessive exposure to UVB and UVA radiation (wavelength: 320-400 nm) also leads to a weakening of the elastic and collagen fibers of the connective tissue. This leads to numerous phototoxic and photoallergic reactions and premature skin aging.

[0003] To protect the skin, a number of sunscreen filter substances have been developed that can be used in cosmetic preparations. These UVA and UVB filters are summarized in most industrialized countries in the form of positive lists, such as Annex 7 of the Cosmetics Regulation.

[0004] However, the large number of commercially available sunscreens should not obscure the fact that these state-of-the-art preparations have a number of disadvantages.

[0005] A popular application form for cosmetic sunscreens is sunscreen sprays. The product is pressed from the reservoir through a spray head under pressure, either by a piston pump or a propellant gas, and applied to the skin in the form of finely dispersed droplets. This application form usually eliminates the need for further rubbing and spreading of the product onto the skin. These finely dispersed droplets are commonly referred to as aerosols.

[0006] A disadvantage of the state of the art is the fact that these aerosols can be inhaled by the user when applying the sunscreen.

[0007] When aerosols are inhaled by humans, a portion of the inhaled aerosol particles are deposited in the respiratory tract. Approximately 10% of all inhaled aerosol particles remain in the respiratory tract. However, since the probability of a particle being deposited depends heavily on its size, this is only a rough guideline. Particles that can penetrate at least into the bronchial region are called respirable. This includes all aerosol particles with a diameter of less than approximately 10 micrometers (PM10). Larger particles are deposited in the nose or throat or cannot be inhaled at all. Particles with a diameter between 0.5 micrometers and 1 micrometer are deposited least. This also means that they penetrate particularly deeply into the lungs. Significantly larger and smaller particles are deposited more strongly in the upper regions, thus penetrating less deeply and placing less strain on the sensitive alveoli (Wikipedia).

[0008] The size of aerosol droplets in spray formulations usually depends on the spray head, the spray pressure and the composition of the sprayed preparation.

[0009] It was now the object of the present invention to develop a sun protection spray in which the formulation should be improved in such a way that the aerosol droplets (using standard spray heads and conventional spray pressures of 2.0 to 4.0 bar, preferably 2.7 bar) are no longer respirable, i.e. that the droplet size of the aerosol droplets should be at least 10 micrometers and at most 0.2% of the droplets could have a smaller droplet size.

[0010] Surprisingly, the problem is solved by the use of ethylcellulose in cosmetic, ethanolic sunscreen sprays to prevent the spray droplets from entering the lungs, characterized in that the cosmetic, ethanolic sunscreen spray contains 2,4,6-tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone) and / or hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino hydroxybenzoyl hexyl benzoate), whereby aerosols are no longer considered to be enter the lungs if their droplet size is at least 10 micrometers and at most 0.2% of the droplets have a smaller droplet size.

[0011] Therefore, the object of the present invention is further achieved by a cosmetic preparation in the form of a sun protection spray containing a) ethanol, b) ethylcellulose and c) 2,4,6-tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone) and / or hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino hydroxybenzoyl hexyl benzoate), characterized in that the sunscreen spray contains ethylcellulose in a concentration of 0.1 to 2% by weight, based on the total weight of the preparation.

[0012] According to the invention, the preparations with and without ethylcellulose were compared using a standard spray head (standard spray heads P72, Helios 5027 or 4061 from Aptar) and a spray pressure of 2.7 bar propellant gas 60% butane, 20% isobutane, 20% propane.

[0013] For the purposes of this disclosure, aerosols are considered to be no longer respirable if their droplet size is at least 10 micrometers under the measurement conditions specified above and if at most 0.2% of the droplets have a smaller droplet size.

[0014] In the context of the present disclosure, the phrases "according to the invention", "preparation according to the invention" etc. always refer to the preparations and uses according to the invention, ie also to preparations in which the uses according to the invention are realized.

[0015] In addition to the use in aerosol spray cans, it is also according to the invention to use the inventive use or preparation in so-called bag on valve systems. Here the pressure in the storage vessel is 7-10 bar.

[0016] Although the prior art includes WO 2016 / 008121 A1, JP 2019 108303A and EP 1 291 009 A2, these documents could not point the way to the present invention.

[0017] For use according to the invention, it is preferred if the sunscreen spray contains ethylcellulose in a concentration of 0.1 to 2.0% by weight, based on the total weight of the preparation. At higher concentrations, however, the spray pattern deteriorates. This may be due to the thickening properties of the ethylcellulose, which become apparent at higher concentrations.

[0018] It is advantageous according to the invention if the sun protection spray contains ethanol in a concentration of 20 to 80% by weight, preferably 30 to 70% by weight and particularly preferably 40 to 40% by weight, in each case based on the total weight of the preparation.

[0019] In connection with the UV filters Ethylhexyl Triazone and Diethylamino hydroxybenzoyl hexyl benzoate, three cases can be distinguished according to the invention: Preparations containing Ethylhexyl Triazone, preparations containing Diethylamino hydroxybenzoyl hexyl benzoate, and preparations containing Ethylhexyl Triazone and Diethylamino hydroxybenzoyl hexyl benzoate. For all of these embodiments, the following use concentrations are considered advantageous according to the invention: Advantageous embodiments of the present invention are characterized in that the preparation contains 2,4,6-tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone) in a concentration of 0.5 to 2.5% by weight, based on the total weight of the preparation.

[0020] Advantageous embodiments within the meaning of the present invention are characterized in that the preparation contains hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino hydroxybenzoyl hexyl benzoate) in a concentration of 0.5 to 2.5% by weight, based on the total weight of the preparation.

[0021] Advantageous embodiments of the present invention are characterized in that the ethylcellulose has a glass transition temperature of 129-133 °C. It is further characterized as advantageous according to the invention if it has a refractive index of 1.47.

[0022] Furthermore, it is advantageous in the context of the present invention if the ethylcellulose has an ethoxyl content of 48-49.5% by weight.

[0023] Advantageous embodiments of the present invention are characterized in that the ethylcellulose has an average molecular weight (weight average) M w of 215,000, measured by size exclusion chromatography.

[0024] Examples of ethylcelluloses which can be used which are advantageous according to the invention are the Ethocel Standard ®< products from the Dow Chemical Company or the ethylcellulose EC N200 PC ®< from the Aqualon company.

[0025] The preparation according to the invention usually contains additional UV filters.

[0026] According to the invention, it is advantageous if the preparation contains 4-(tert-butyl)-4'-methoxydibenzoylmethane.

[0027] The advantageous use concentration for 4-(tert-butyl)-4'-methoxydibenzoylmethane according to the invention is from 1 to 5% by weight, based on the total weight of the preparation.

[0028] Furthermore, it is advantageous according to the invention if the preparation contains one or more UV-B filters selected from the group of the compounds 2-ethylhexyl 2-hydroxybenzoate (INCI: Ethylhexyl Salicylate) and 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI: Homosalate).

[0029] The advantageous use concentration for 2-ethylhexyl 2-hydroxybenzoate (INCI: Ethylhexyl Salicylate) according to the invention is from 1 to 6% by weight, based on the total weight of the preparation.

[0030] The advantageous use concentration for 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI: Homosalate) according to the invention is from 1 to 10% by weight, based on the total weight of the preparation.

[0031] Furthermore, the advantageous embodiments of the present invention are characterized in that the preparation contains 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-Ethylhexyloxyphenol methoxyphenyl Triazine).

[0032] The advantageous use concentration according to the invention for 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-Ethylhexyloxyphenol methoxyphenyl Triazine) is from 0.5 to 5% by weight, based on the total weight of the preparation.

[0033] Furthermore, it may be advantageous according to the invention if the preparation contains ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: octocrylene).

[0034] In such a case, the advantageous use concentration for ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: octocrylene) according to the invention is from 2.5 to 10% by weight, based on the total weight of the preparation.

[0035] In any case, it is advantageous according to the invention if the preparation does not contain 3-(4-methylbenzylidene)-camphor, 2-hydroxy-4-methoxybenzophenone (INCI: oxybenzone), 2-ethylhexyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, parabens, methylisothiazolinone, chloromethylisothiazolinone and DMDM ​​hydantoin.

[0036] The advantageous embodiments according to the invention, on the other hand, are characterized in that the preparation contains one or more oils selected from the group of the compounds butylene glycol dicaprylate / dicaprate, phenethyl benzoate, C12-15 alkyl benzoate, dibutyl adipate; diisopropyl sebacate, dicaprylyl carbonate, di-C12-13 alkyl tartrate, butyloctyl salicylate, diethylhexyl syringylidene malonate, hydratenated castor oil dimerate, triheptanoin, C12-13 alkyl lactate, C16-17 alkyl benzoate, propylheptyl caprylate, caprylic / capric triglyceride, diethylhexyl 2,6-naphthalate, octyldodecanol, caprylic / capric triglyceride, ethylhexyl cocoate.

[0037] The use of dibutyl adipate, propylheptyl caprylate and C12-15 alkyl benzoate is preferred according to the invention.

[0038] A particularly advantageous embodiment of the present invention is characterized in that the preparation contains acrylate / octylacrylamide copolymer (INCI: Acrylates / Octylacrylamide Copolymer) and a maximum of 2.5% by weight, based on the total weight of the preparation, of glycerin. The use concentration for acrylate / octylacrylamide copolymer (INCI: Acrylates / Octylacrylamide Copolymer) is advantageously from 0.2 to 4% by weight, based on the total weight of the preparation.

[0039] However, if the concentration of glycerol used is more than 2.5% by weight, based on the total weight of the preparation, the use of acrylate / octylacrylamide copolymer (INCI: Acrylates / Octylacrylamide Copolymer) is preferably avoided according to the invention.

[0040] According to the invention, it is advantageous if the preparation is anhydrous. Preparations are considered anhydrous according to the invention if the water content of the preparation is less than 3% by weight, based on the total weight of the preparation.

[0041] Advantageous embodiments of the present invention are further characterized in that the preparation is free from titanium dioxide, zinc oxide and polysilicone-15.

[0042] According to the invention, it is advantageous if the preparation is stored in a compressed aerosol container and sprayed with the aid of a propellant gas. In such a case, it is preferred according to the invention if propane, n-butane, isobutane, or mixtures thereof are used as the propellant gas. Comparative test

[0043] The following formulations were prepared and the droplet size distribution was determined using the following method. Measurement method

[0044] Characterization of Sunscreen Sprays at the Fraunhofer Institute for Toxicology and Experimental Medicine ITEM

[0045] The release fraction is defined as the mass m of the aged spray / aerosol in the range of 0.6-10µm normalized to the total mass of the released spray product ( RF = m / M ).

[0046] The release fraction characterizes the application process by estimating the inhalation exposure for a defined application scenario. It is determined by spraying the product into a precisely defined control volume over a short period of time and performing time-resolved measurements of the droplet concentration. Examples

[0047] The following examples, except for examples 2, 3, 6, and 12, which lack the filters Ethylhexyl Triazone (INCI) and / or Diethylamino hydroxybenzoyl hexyl benzoate (INCI), are intended to illustrate the present invention without limiting it. Unless otherwise stated, all quantities, proportions, and percentages are based on the weight and the total amount or the total weight of the preparations.

Claims

1. Use of ethylcellulose in cosmetic, ethanolic sunscreen sprays to prevent the respirability of the spray droplets, characterized in that the cosmetic, ethanolic sunscreen spray comprises 2,4,6-tris[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone) and / or hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), where aerosols are no longer considered to be respirable when they have a droplet size of at least 10 micrometres and at most 0.2% of the droplets have a smaller droplet size.

2. Cosmetic preparation in the form of a sunscreen spray comprising a) ethanol, b) ethylcellulose, and c) 2,4,6-tris[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone) and / or hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), characterized in that the sunscreen spray comprises ethylcellulose in a concentration of 0.1% to 2% by weight, based on the total weight of the preparation.

3. Use according to Claim 1, characterized in that the sunscreen spray comprises ethylcellulose in a concentration of 0.1% to 2% by weight, based on the total weight of the preparation.

4. Use or preparation according to any of the preceding claims, characterized in that the sunscreen spray comprises ethanol in a concentration of 20% to 80% by weight, based on the total weight of the preparation.

5. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises 2,4,6-tris[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone) in a concentration of 0.5% to 2.5% by weight, based on the total weight of the preparation.

6. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate) in a concentration of 0.5% to 2.5% by weight, based on the total weight of the preparation.

7. Use or preparation according to any of the preceding claims, characterized in that the ethylcellulose has a glass transition temperature of 129-133°C.

8. Use or preparation according to any of the preceding claims, characterized in that the ethylcellulose has a refractive index of 1.47.

9. Use or preparation according to any of the preceding claims, characterized in that the ethylcellulose has an ethoxyl content of 48.0-49.5% by weight.

10. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises 4-(tert-butyl)-4'-methoxydibenzoylmethane.

11. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises one or more UV-B filters selected from the following group of compounds: 2-ethylhexyl 2-hydroxybenzoate (INCI: Ethylhexyl Salicylate) and 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI: Homosalate).

12. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine).

13. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: Octocrylene).

14. Use or preparation according to any of the preceding claims, characterized in that the preparation does not comprise any 3-(4-methylbenzylidene)camphor, 2-hydroxy-4-methoxybenzophenone (INCI: Oxybenzone), 2-ethylhexyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, any parabens, methylisothiazolinone, chloromethylisothiazolinone and DMDM hydantoin.

15. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises one or more oils selected from the following group of compounds: Butylene Glycol Dicaprylate / Dicaprate, Phenethyl Benzoate, C12-15 Alkyl Benzoate, dibutyl adipate; diisopropyl sebacate, dicaprylyl carbonate, Di-C12-13 Alkyl Tartrate, Butyloctyl Salicylate, Diethylhexyl Syringylidene Malonate, Hydrogenated Castor Oil Dimerate, Triheptanoin, C12-13 Alkyl Lactate, C16-17 Alkyl Benzoate, Propylheptyl Caprylate, Caprylic / Capric Triglyceride, Diethylhexyl 2,6-Naphthalate, Octyldodecanol, Caprylic / Capric Triglyceride, Ethylhexyl Cocoate.

16. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises acrylate / octylacrylamide copolymer (INCI: Acrylates / Octylacrylamide Copolymer) and at most 2.5% by weight, based on the total weight of the preparation, of glycerin.

17. Use or preparation according to any of the preceding claims, characterized in that the preparation is anhydrous.

18. Use or preparation according to any of the preceding claims, characterized in that the preparation is free of titanium dioxide, zinc oxide and Polysilicone-15.

19. Use or preparation according to any of the preceding claims, characterized in that the preparation is stored with an aerosol-pressurized gas container and sprayed using a propellant.

20. Use or preparation according to Claim 20, characterized in that the propellant used is propane, n-butane, isobutane or mixtures thereof.