Sunscreen containing terephthalylidene dicamphor sulfonic acid and glycols
The use of glycols in sunscreen formulations stabilizes terephthalylidene dicamphor sulfonic acid, addressing crystallization issues at low temperatures, ensuring effective UV protection by maintaining solubility and stability.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- BEIERSDORF AG
- Filing Date
- 2024-03-01
- Publication Date
- 2026-04-14
AI Technical Summary
Conventional sunscreen formulations with terephthalylidene dicamphor sulfonic acid as a UV-A filter face issues with crystallization at low temperatures, limiting its use in the aqueous phase due to solubility constraints, especially at higher concentrations.
A cosmetic formulation incorporating specific glycols, such as propane-1,2-diol and propane-1,3-diol, along with terephthalylidene dicamphor sulfonic acid, enhances its solubility and stability, preventing crystallization even at low temperatures.
The formulation effectively maintains the solubility and stability of terephthalylidene dicamphor sulfonic acid, ensuring high UV protection without crystallization, even at low temperatures, by using glycols and other additives like 1,2-hexanediol and glycerin, achieving a UV protection index of 15 or more.
Smart Images

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Abstract
Description
Technical Field
[0001] The present invention relates to a cosmetic formulation containing a salt of terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), one or more glycols, and water.
[0002] Over the years, the aspiration has continuously continued from refined whiteness to "healthy and sporty person-like brown skin". To achieve this, people expose their skin to sunlight. This is because it causes pigment production in the sense of melanin production. However, the ultraviolet rays of sunlight also have an adverse effect on the skin. In addition to acute damage (sunburn), excessive exposure to light in the UVB region (wavelength: 280 - 320 nm) also causes long-term damage such as an increased risk of skin cancer. Moreover, the effects of excessive irradiation of UVB and UVA irradiation (wavelength: 320 - 400 nm) lead to the weakening of elastic fibers and collagen fibers in connective tissue. This results in numerous phototoxic and photoallergy reactions, ultimately leading to premature skin aging.
[0003] Therefore, in order to protect the skin, a series of sunscreen filter substances that can be used in cosmetic formulations have been developed. These UVA and UVB filters are summarized in the form of a positive list such as Annex 7 of cosmetic regulations in most developed countries.
[0004] However, although there are many commercially available sunscreens, it must not be overlooked that the conventional formulations have various drawbacks.
[0005] Over the years, the demand for UV-A filtering substances has steadily increased. This is particularly due to numerous government regulations that mandate a balanced ratio of UV-A and UV-B protection in sunscreens. However, the number of UV-A filters available for use in cosmetics is very limited. In practice, those used are oil-soluble compounds such as butyl methoxydibenzoylmethane or diethylamino hydroxybenzoylhexyl benzoate.
[0006] However, to obtain particularly high UV protection, it is necessary to incorporate a UV-A filter into the aqueous phase as well. For this purpose, terephthalylidene dicamphor sulfonic acid (INCI) was developed about 30 years ago as a water-soluble UV-A filter material. However, this material has the drawback that the amount that can be incorporated into the aqueous phase of sunscreen is limited. This is because the material tends to recrystallize from the aqueous phase when stored for long periods at low temperatures (for example, below 10°C in winter).
[0007] Therefore, the object of the present invention was to develop a cosmetic formulation or aqueous phase for an aqueous cosmetic formulation containing terephthalylidene dicamphor sulfonic acid (INCI) that effectively suppresses the risk of crystallization of the UV filter material, even at higher concentrations (i.e., above 0.4% by weight) and especially at low temperatures (i.e., below 10°C).
[0008] This challenge is, a) Salt of terephthalylidene dicamphor sulfonic acid (INCI), b) One or more glycols, c) water This is resolved by cosmetic formulations containing [the specified ingredient].
[0009] Furthermore, this problem can be solved by using one or more glycols to enhance the solubility of terephthalylidene dicamphor sulfonic acid (INCI) salts in the aqueous phase of cosmetic formulations.
[0010] Within the scope of this invention, glycols refer only to compounds having two hydroxyl groups (OH groups). Glycerin, within the scope of this invention, does not belong to the category of glycols by definition.
[0011] Furthermore, within the scope of this disclosure, expressions such as "by the present invention" and "advantageous by the present invention" always refer to the formulations, uses, and methods of the present invention according to the present invention (see below).
[0012] When the formulation according to the present invention is an aqueous formulation, the concentration specification "total weight of the aqueous phase" applies to the entire formulation.
[0013] According to the present invention, it is advantageous to use triethanolamine salt as the salt of terephthalylidene dicamphor sulfonic acid.
[0014] Furthermore, in the sense of the present invention, it is advantageous that the aqueous phase contains 0.5 to 3% by weight of terephthalylidene dicamphor sulfonic acid based on the total weight of the aqueous phase. According to the present invention, it is advantageous that the concentration of terephthalylidene dicamphor sulfonic acid is in the range of 2 to 3% by weight based on the total weight of the aqueous phase.
[0015] An embodiment of the present invention that is more advantageous is characterized in that one or more compounds are selected as glycols from the group consisting of propane-1,2-diol, propane-1,3-diol, and butane-1,3-diol. According to the present invention, propane-1,2-diol and propane-1,3-diol are preferred, and according to the present invention, propane-1,3-diol is particularly preferred.
[0016] Furthermore, according to the present invention, it is highly preferable to additionally combine glycols that are more advantageous in the present invention with 1,2-hexanediol.
[0017] According to the present invention, it is advantageous for the formulation to contain glycols in a total concentration of 1 to 10% by weight based on the total weight of the aqueous phase. According to the present invention, a glycol concentration range of 4 to 8% by weight based on the total weight of the aqueous phase is preferred.
[0018] When the formulation according to the present invention contains a combination of glycols and 1,2-hexanediol that are advantageous according to the present invention, the preferred concentration of 1,2-hexanediol used according to the present invention is 0.2 to 0.5% by weight based on the total weight of the aqueous phase.
[0019] A particularly advantageous embodiment of the present invention is obtained when the formulation additionally contains glycerin.
[0020] In such cases, an embodiment of the present invention that is more advantageous is characterized in that the formulation contains glycerin at a concentration of 1 to 10% by weight based on the total weight of the aqueous phase.
[0021] Furthermore, according to the present invention, it is preferable that the weight ratio of the total amount of glycols to glycerin is 1:1 to 2:1.
[0022] Regarding the weight ratio of terephthalylidene dicamphor sulfonic acid to the total amount of glycols, according to the present invention, it is advantageous for the weight ratio of terephthalylidene dicamphor sulfonic acid to the total amount of glycols to be 1:1 to 1:4.
[0023] To ensure complete protection from sunlight's UV rays, the formulation needs to include another UV filtering substance.
[0024] According to the present invention, it has been found to be particularly advantageous when the formulation contains salts of disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) and / or 2-phenylbenzimidazole-5-sulfonate.
[0025] When the formulation according to the present invention contains disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate), an advantageous embodiment according to the present invention is that the formulation contains disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) at a concentration of 0.5 to 3% by weight based on the total weight of the aqueous phase.
[0026] Moreover, in such a case, according to the present invention, it is advantageous to use the triethanolamine salt as the salt of disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate).
[0027] When the formulation according to the present invention contains 2-phenylbenzimidazole-5-sulfonate, according to the present invention, it is advantageous when the formulation contains 2-phenylbenzimidazole-5-sulfonic acid at a concentration of 1 to 5% by weight based on the total weight of the aqueous phase.
[0028] Moreover, in such a case, according to the present invention, it is advantageous to use the sodium salt as the salt of 2-phenylbenzimidazole-5-sulfonic acid.
[0029] A further advantageous embodiment of the present invention according to the present invention is that the formulation contains ethanol.
[0030] When the aqueous phase of the complex contains ethanol, according to the present invention, it is preferable to use ethanol at a concentration of 2 to 15% by weight based on the total weight of the aqueous phase.
[0031] Moreover, in the context of the present invention, it is advantageous for the formulation to contain ethylhexyl glycerin.
[0032] The advantageous concentration of ethylhexyl glycerin used according to the present invention is 0.1 to 0.3% by weight based on the total weight of the aqueous phase.
[0033] Furthermore, in the context of the present invention, it is advantageous when the formulation contains one or more compounds selected from the group consisting of xanthan gum (INCI: Xanthan Gum), welan gum (INCI: Welan Gum), gellan gum (INCI: Gelan Gum), sclerotium gum (INCI: Scerotium Gum), cellulose and / or cellulose derivatives.
[0034] A particularly advantageous embodiment of the present invention is presented when the formulation does not contain a lipophilic phase and is an aqueous formulation. According to the present invention, this preferably has an ultraviolet protection index of 15 or more. In such a case, fragrance substances are not counted as part of the lipophilic phase.
[0035] Advantageously according to the present invention, the formulation according to the present invention contains a film-forming agent. A film-forming agent in the context of the present invention is a substance of various compositions characterized by the following properties. By dissolving the film-forming agent in water or other suitable solvents and then applying the solution to the skin, a film is formed after the solvent has evaporated, and this film substantially serves to fix the light filters on the skin and thus enhance the water resistance of the product.
[0036] According to the present invention, it is advantageous when the formulation according to the present invention contains corn starch, maltodextrin, and / or pullulan. According to the present invention, these compounds can act as film-forming agents.
[0037] The present invention provides a method for producing a compound, characterized in that, first, terephthalylidene dicamphor sulfonic acid (INCI) and optionally disodium phenyl dibenzimidazole tetrasulfonate (INCI) are added to water while stirring and dissolved with triethanolamine, then optionally 2-phenylbenzimidazole-5-sulfonic acid is added while stirring and dissolved with NaOH, then the pH is adjusted to at least 6.4 with NaOH, and in a further step, glycol is added while stirring, and after the addition of glycol, further components are optionally added.
[0038] Official Exam 3% by weight of terephthalylidene dicamphor sulfonic acid (9% by weight of a 33% aqueous solution) 3% by weight of 2-phenylbenzimidazole-5-sulfonic acid, and Phenyldibenzimidazole tetrasulfonate disodium 2% by weight An aqueous solution was prepared from the mixture and its pH was adjusted to 7.5 with a 2.5% by weight triethanolamine solution.
[0039] From this clear solution, four variations: One is without further additives, One is the addition of 10% by weight of glycerin. One is the addition of 10% by weight of propane-1,3-diol. One is the addition of a mixture of 5% by weight glycerin and 5% by weight propane-1,3-diol. We prepared it.
[0040] For all variations, samples were stored at different temperatures (-10°C, -6°C, 20°C) for 5 days, after which the amount of precipitate formed was measured optically, and the precipitate itself was analyzed under a microscope. The following results were obtained at all storage temperatures: No further additives: a very large amount of precipitate Addition of 10% by weight of glycerin: large amount of precipitate Addition of 10% by weight of propane-1,3-diol: small amount of precipitate Addition of a mixture of 5% by weight glycerin and 5% by weight propane-1,3-diol: No precipitate formed. This was obtained.
[0041] The precipitate was always terephthalylidene dicamphor sulfonic acid.
[0042] Examples The following examples are for illustrative purposes only and do not limit the present invention. Unless otherwise specified, all quantities, proportions, and percentages are based on weight and total amount or the total weight of the mixture.
[0043] [Table 1]
Claims
1. a) Salt of terephthalylidene dicamphor sulfonic acid (INCI), b) One or more glycols, c) water A cosmetic formulation containing the following ingredients.
2. Use of one or more glycols to enhance the solubility of terephthalylidene dicamphor sulfonic acid (INCI) salts in the aqueous phase of cosmetic formulations.
3. The cosmetic formulation according to claim 1 or the use according to claim 2, characterized in that triethanolamine salt is used as the salt of terephthalylidene dicamphor sulfonic acid.
4. The cosmetic formulation or use according to any one of claims 1 to 3, characterized in that the aqueous phase contains 0.5 to 3% by weight of terephthalylidene dicamphor sulfonic acid based on the total weight of the aqueous phase.
5. A cosmetic formulation or use according to any one of claims 1 to 4, characterized in that one or more compounds are selected as glycols from the group consisting of propane-1,2-diol, propane-1,3-diol, and butane-1,3-diol.
6. The cosmetic formulation or use according to any one of claims 1 to 5, characterized in that the formulation additionally contains glycerin.
7. The cosmetic formulation or use according to any one of claims 1 to 6, characterized in that the formulation contains the glycols at a total concentration of 1 to 10% by weight based on the total weight of the aqueous phase.
8. The cosmetic formulation or use according to any one of claims 1 to 7, characterized in that the formulation contains glycerin at a concentration of 1 to 10% by weight based on the total weight of the aqueous phase.
9. A cosmetic formulation or use according to any one of claims 1 to 8, characterized in that the weight ratio of the total amount of glycols to glycerin is 1:1 to 2:
1.
10. A cosmetic formulation or use according to any one of claims 1 to 9, characterized in that the weight ratio of terephthalylidene dicamphor sulfonic acid to the total amount of glycols is 1:1 to 1:
4.
11. The cosmetic formulation or use according to any one of claims 1 to 10, characterized in that the formulation contains a salt of disodium phenyl dibenzimidazole tetrasulfonate (INCI) and / or 2-phenylbenzimidazole-5-sulfonate.
12. The cosmetic formulation or use according to any one of claims 1 to 11, characterized in that the formulation contains disodium phenyl dibenzimidazole tetrasulfonate (INCI) at a concentration of 0.5 to 3% by weight based on the total weight of the aqueous phase.
13. A cosmetic formulation or use according to any one of claims 1 to 12, characterized in that triethanolamine salt is used as the salt of disodium phenyl dibenzimidazole tetrasulfonate (INCI).
14. The cosmetic formulation or use according to any one of claims 1 to 13, characterized in that the formulation contains 2-phenylbenzimidazole-5-sulfonic acid at a concentration of 1 to 5% by weight based on the total weight of the aqueous phase.
15. A cosmetic formulation or use according to any one of claims 1 to 14, characterized in that a sodium salt is used as the salt of 2-phenylbenzimidazole-5-sulfonic acid.
16. The cosmetic formulation or use according to any one of claims 1 to 15, characterized in that the formulation contains ethanol.
17. The cosmetic formulation or use according to any one of claims 1 to 16, characterized in that the formulation contains ethylhexylglycerin.
18. The cosmetic formulation or use according to any one of claims 1 to 17, characterized in that the formulation does not contain a lipophilic phase and is an aqueous formulation.
19. The cosmetic formulation or use according to any one of claims 1 to 18, characterized in that the formulation contains one or more compounds selected from the group consisting of xanthan gum (INCI), welan gum (INCI), gelan gum (INCI), scerotium gum (INCI), cellulose, and / or cellulose derivatives.
20. The cosmetic formulation or use according to any one of claims 1 to 19, characterized in that the formulation contains corn starch, maltodextrin and / or pullulan.
21. A method for producing a cosmetic formulation according to any one of claims 1 to 20, characterized in that first, terephthalylidene dicamphor sulfonic acid (INCI) and optionally disodium phenyl dibenzimidazole tetrasulfonate (INCI) are added to water while stirring and dissolved with triethanolamine, then optionally 2-phenylbenzimidazole-5-sulfonic acid is added while stirring and dissolved with NaOH, then the pH is adjusted to at least 6.4 with NaOH, and in a further step, glycol is added while stirring, and optionally further components are added after the addition of glycol.