SUNSCREEN SPRAY CONTAINING HYDROXYPROPYLCELLULOSE

DE502020011062D1Active Publication Date: 2025-05-28BEIERSDORF AG
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Patent Information

Application Number
DE502020011062
Authority / Receiving Office
DE · DE
Patent Type
Patents
Current Assignee / Owner
Priority Date
2019-08-28
Filing Date
2020-08-21
Publication Date
2025-05-28
Estimated Expiration
2040-08-21

AI Technical Summary

Technical Problem

Existing sun protection sprays can result in aerosol droplets being inhaled, with a significant portion potentially reaching the lungs due to droplet sizes smaller than 10 micrometers, posing health risks.

Method used

Incorporating hydroxypropylcellulose in a concentration of 0.01 to 0.10 weight% in ethanolic sun protection sprays to prevent pulmonary deposition of aerosol droplets, ensuring that at least 99.8% of droplets are 10 micrometers or larger and no more than 0.2% are smaller.

Benefits of technology

The use of hydroxypropylcellulose effectively prevents the inhalation of small aerosol droplets into the lungs, significantly reducing the health risks associated with the use of sun protection sprays while maintaining effective sun protection.

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Description

[0001] The present disclosure relates to the use of hydroxypropylcellulose 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, hydroxypropylcellulose and ethylhexyl triazone.

[0002] The trend away from a refined pallor toward "healthy, athletic tan" 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 damage such as an increased risk of skin cancer occurs 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 current 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 the least deposited. 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 hydroxypropylcellulose in cosmetic, ethanolic sunscreen sprays to prevent the spray droplets from entering the lungs, characterized in that the sunscreen spray contains hydroxypropylcellulose in a concentration of 0.01 to 0.10% by weight, based on the total weight of the preparation, wherein aerosols are considered to be no longer entering 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] According to the invention, it is preferred for use if the cosmetic, ethanolic sunscreen spray contains 2,4,6-tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone).

[0012] 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) hydroxypropylcellulose and c) 2,4,6-tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone), characterized in that the sunscreen spray contains hydroxypropylcellulose in a concentration of 0.01 to 0.10% by weight, based on the total weight of the preparation.

[0013] Although the prior art includes WO 2017 / 046280 A1, this document could not point the way to the present invention.

[0014] According to the invention, the preparations with and without hydroxypropylcellulose 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 with the propellant gas 60% butane, 20% isobutane, 20% propane.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] According to the invention, it is particularly preferred if the sunscreen spray contains hydroxypropylcellulose in a concentration of 0.01 to 0.07% by weight, based on the total weight of the preparation. At higher concentrations, however, the spray pattern deteriorates.

[0019] This may be due to the thickening properties of hydroxypropyl cellulose, which come into effect at higher concentrations.

[0020] 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 60% by weight, in each case based on the total weight of the preparation.

[0021] 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.

[0022] Advantageous embodiments of the present invention are characterized in that the hydroxypropyl cellulose has an average molecular weight (weight average) M w of 1150000, measured by size exclusion chromatography.

[0023] Furthermore, it is advantageous in the sense of the present invention if the hydroxypropyl cellulose has a molar degree of substitution of 3.4 to 4.4.

[0024] The hydroxypropylcelluloses Klucel ®< H, H CS and HF Pharm from Aqualon can be used as hydroxypropylcelluloses advantageous according to the invention.

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

[0026] It is advantageous according to the invention if the preparation contains one or more UV-A filters selected from the group of the compounds 4-(tert-butyl)-4'-methoxydibenzoylmethane and / or hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino hydroxybenzoyl hexyl benzoate).

[0027] The advantageous use concentration for 4-(tert-butyl)-4'-methoxydibenzoylmethane according to the invention is from 1.0 to 5.0% by weight, based on the total weight of the preparation.

[0028] The advantageous use concentration for hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino hydroxybenzoyl hexyl benzoate) according to the invention is from 0.5 to 2.0% by weight, based on the total weight of the preparation.

[0029] 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).

[0030] The advantageous use concentration for 2-ethylhexyl 2-hydroxybenzoate (INCI: Ethylhexyl Salicylate) according to the invention is from 3 to 6% by weight, based on the total weight of the preparation.

[0031] The advantageous use concentration for 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI: Homosalate) according to the invention is from 3 to 10% by weight, based on the total weight of the preparation.

[0032] 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).

[0033] The advantageous use concentration according to the invention for 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-Ethylhexyloxyphenol methoxyphenyl Triazine) is from 1 to 5% by weight, based on the total weight of the preparation.

[0034] Furthermore, it may be advantageous according to the invention if the preparation contains ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: octocrylene).

[0035] 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.

[0036] 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), 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isoamyl ester, parabens, methylisothiazolinone, chloromethylisothiazolinone and DMDM ​​hydantoin.

[0037] 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.

[0038] The use of dibutyl adipate, propylheptyl caprylate and C12-15 alkyl benzoate is preferred according to the invention.

[0039] 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 4.0% by weight, based on the total weight of the preparation.

[0040] However, if the concentration of glycerin 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.

[0041] According to the invention, it is advantageous if the preparation is anhydrous. According to the invention, preparations are considered anhydrous if the water content of the preparation is less than 3% by weight, based on the total weight of the preparation.

[0042] Advantageous embodiments of the present invention are further characterized in that the preparation is free from titanium dioxide, zinc oxide and polysilicone-15.

[0043] According to the invention, it is advantageous if the preparation is stored in a compressed aerosol container and sprayed with 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. Comparison test

[0044] The following formulations were prepared and the droplet size distribution was determined using the following method. Measurement method

[0045] Characterization of Sunscreen Sprays at the Fraunhofer Institute for Toxicology and Experimental Medicine ITEM

[0046] 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 ).

[0047] 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

[0048] The following examples, except for Examples 14, 15, 16, 17, 21, and 22, which represent compositions not according to the invention, 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 hydroxypropylcellulose in cosmetic, ethanolic sunscreen sprays to prevent the respirability of the spray droplets, characterized in that the sunscreen spray comprises hydroxypropylcellulose in a concentration of 0.01% to 0.10% by weight, based on the total weight of the preparation, 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. Use according to Claim 1, 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).

3. Cosmetic preparation in the form of a sunscreen spray comprising a) ethanol, b) hydroxypropylcellulose and c) 2,4,6-tris[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: Ethylhexyl Triazone), characterized in that the sunscreen spray comprises hydroxypropylcellulose in a concentration of 0.01% to 0.10% 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 hydroxypropylcellulose has an average molecular weight (weight average) MW of 1 150 000, measured by size-exclusion chromatography.

7. Use or preparation according to any of the preceding claims, characterized in that the hydroxypropylcellulose has a molar degree of substitution of 3.4 to 4.4.

8. Use or preparation according to any of the preceding claims, characterized in that the preparation comprises one or more UV-A filters selected from the following group of compounds: 4-(tert-butyl)-4'-methoxydibenzoylmethane and / or hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate).

9. 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).

10. 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).

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

12. 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.

13. 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.

14. 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.

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

16. 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.

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

18. Use or preparation according to Claim 18, characterized in that the propellant used is propane, n-butane, isobutane or mixtures thereof.