Sunscreen containing terephthalylidene dicaphor sulfonic acid and glycols.

Description

Sunscreen containing terephthalylidene dicaphor sulfonic acid and glycols. DESCRIPTION

[0001] The present invention relates to a cosmetic preparation comprising a salt of terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), one or more glycols and water.

[0002] For many years, there has been an uninterrupted trend from aristocratic pallor to a healthy, athletic brown complexion. To achieve this, people expose their skin to solar radiation, as this causes the formation of pigments in the direction of melanin formation. However, ultraviolet radiation from sunlight also has a detrimental effect on the skin. In addition to acute damage (sunburns), long-term damage, such as an increased risk of developing skin cancer, occurs in the case of excessive irradiation with UVB light (wavelength: 280-320 nm). Excessive exposure to UVB and UVA radiation (wavelength: 320-400 nm) further leads to the weakening of elastic and collagen fibers in connective tissue. This leads to various phototoxic and photoallergic reactions, resulting in premature skin aging.

[0003] Therefore, to protect the skin, a range of photoprotective filter substances has been developed that can be used in cosmetic preparations. In most industrialized countries, these UVA and UVB filters are grouped together in the form of positive lists, such as Annex 7 of the Kosmetikverordnung [German Cosmetics Ordinance].

[0004] The multiplicity of commercially available sunscreens should not, however, distract from the fact that these prior art preparations have a range of disadvantages.

[0005] For many years, there has been a steadily increasing demand for UV-A filtering substances. This can be attributed, among other things, to the numerous government regulations requiring that sunscreens Petition 870250088610, dated 09 / 30 / 2025, page 9 / 63 2 / 9 sunscreens have a balanced ratio of UV-A and UV-B protection. However, the number of UV-A filters that can be used in cosmetics is very limited. Essentially, oil-soluble compounds are used, such as butyl methoxydibenzoylmethane or diethylaminohydroxybenzoyl hexyl benzoate.

[0006] To obtain particularly high UV protection, however, it is necessary to incorporate UV-A filters into the aqueous phase. For this purpose, terephthalylidene Dicamphor Sulfonic Acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) was developed about 30 years ago as a water-soluble UV-A filter substance. However, this substance has the disadvantage of only being able to be incorporated into the aqueous phase of a sunscreen in a limited quantity, since it tends to crystallize back from the aqueous phase in the case of prolonged storage at cold temperatures (e.g., in winter at temperatures below 10 °C).

[0007] Therefore, the objective of the present invention was to develop an aqueous phase for a cosmetic preparation or an aqueous cosmetic preparation with terephthalylidene Dicamphor Sulfonic Acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) in which the risk of crystallization of this UV filter substance, even at relatively high concentrations (i.e., above 0.4% by weight), particularly under cold conditions (i.e., below 10 °C), is effectively suppressed. The objective is achieved through a cosmetic preparation that includes a) a salt of terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), b) one or more glycols, c) water.

[0008] The objective is also achieved by using one or more glycols to increase the solubility of terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) salts in the aqueous phase of cosmetic preparations.

[0009] Within the scope of the present invention, glycols are defined Petition 870250088610, dated 09 / 30 / 2025, p. 10 / 63 3 / 9 exclusively as compounds having 2 hydroxyl groups (OH groups). By definition, glycerin is not considered a glycol within the scope of the present invention.

[0010] Furthermore, within the scope of the present disclosure, designations such as "according to the invention," "advantageous according to the invention," etc., always refer to the preparation according to the invention, the use according to the invention, and the process according to the invention (see below).

[0011] If the preparation according to the invention is an aqueous preparation, then the specification of total weight concentration of the aqueous phase applies to the entire preparation.

[0012] It is advantageous according to the invention if the triethanolamine salt is used as the salt of terephthalylidene dicamphor sulfonic acid.

[0013] In the context of the present invention, it is also advantageous if the aqueous phase comprises from 0.5% to 3% by weight of terephthalylidene dicamphor sulfonic acid, based on the total weight of the aqueous phase. The concentration range of 2% to 3% by weight of terephthalylidene dicamphor sulfonic acid, based on the total weight of the aqueous phase, is preferred herein according to the invention.

[0014] The embodiments of the present invention that are advantageous according to the invention are characterized by the fact that, as glycols, one or more compounds are selected from the group of 1,2-propanediol, 1,3-propanediol and 1,3-butanediol. Propane-1,2-diol and propane-1,3-diol are preferred according to the invention, with propane-1,3-diol being particularly preferred according to the invention.

[0015] Additionally, it is very particularly preferred, according to the invention, that the glycols that are advantageous according to the invention are further combined with hexane-1,2-diol.

[0016] It is advantageous according to the invention that the preparation comprises glycols in a total concentration of 1% to 10% by weight, based on the total weight of the aqueous phase. The concentration range of 4% to 8% by weight of glycols, based on the total weight of the aqueous phase, is preferred according to the invention. Petition 870250088610, dated 09 / 30 / 2025, page 11 / 63 4 / 9

[0017] If the preparation according to the invention comprises a combination of glycols that are advantageous according to the invention with hexane-1,2-diol, then the preferred concentration used according to the invention for hexane-1,2-diol is 0.2% to 0.5% by weight, based on the total weight of the aqueous phase.

[0018] The embodiments that are particularly advantageous according to the invention are obtained when the preparation additionally comprises glycerin.

[0019] In such a case, the embodiments of the present invention that are advantageous according to the invention are characterized by the fact that the preparation comprises glycerin in a concentration of 1% to 10% by weight, based on the total weight of the aqueous phase.

[0020] It is also preferred according to the invention if the weight ratio between the total amount of glycols and glycerin is from 1:1 to 2:1.

[0021] With regard to the weight ratio between terephthalylidene dicamphor sulfonic acid and the total amount of glycols, it is advantageous according to the invention if the weight ratio between terephthalylidene dicamphor sulfonic acid and the total amount of glycols is from 1:1 to 1:4.

[0022] To ensure complete protection against UV rays from sunlight, it is necessary that the preparation additionally includes UV filter substances.

[0023] According to the invention, it has proven particularly advantageous that the preparation comprises a salt of disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) and / or salts of 2-phenylbenzimidazole-5-sulfonic acid.

[0024] If the preparation according to the invention comprises disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate), then the embodiments that are advantageous according to the invention are characterized by the fact that the preparation comprises disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Petition 870250088610, dated 09 / 30 / 2025, page 12 / 63 5 / 9 Phenyl Dibenzimidazole Tetrasulfonate) at a concentration of 0.5% to 3% by weight, based on the total weight of the aqueous phase.

[0025] Moreover, in such a case, it is advantageous according to the invention if the triethanolamine salt is used as the disodium phenyl dibenzimidazole tetrasulfonate salt (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate).

[0026] If the preparation according to the invention comprises salts of 2-phenylbenzimidazole-5-sulfonic acid, then it is advantageous according to the invention if the preparation comprises 2-phenylbenzimidazole-5-sulfonic acid at a concentration of 1% to 5% by weight, based on the total weight of the aqueous phase.

[0027] Moreover, in such a case, it is advantageous according to the invention if the sodium salt is used as the salt of 2-phenylbenzimidazole-5-sulfonic acid.

[0028] Other embodiments of the present invention that are advantageous according to the invention are characterized by the fact that the preparation comprises ethanol.

[0029] If the aqueous phase of the preparation comprises ethanol, then it is preferably used according to the invention at a concentration of 2% to 15% by weight, based on the total weight of the aqueous phase.

[0030] Furthermore, it is advantageous, in the context of the present invention, that the preparation comprises ethylhexylglycerin.

[0031] The advantageous concentration of use according to the invention for ethylhexylglycerin herein is 0.1% to 0.3% by weight, based on the total weight of the aqueous phase.

[0032] In the context of the present invention, it is also advantageous that the preparation comprises one or more compounds selected from the group of xanthan gum (INCI: Xanthan Gum), welan gum (INCI: Welan Gum), gellan gum (INCI: Gellan Gum), sclerotium gum (INCI: Scerotium Gum), cellulose and / or cellulose derivatives.

[0033] It is an embodiment of the present invention that is particularly advantageous according to the invention if the preparation does not comprise a lipophilic phase, but is an aqueous preparation. According to the invention, this Petition 870250088610, dated 09 / 30 / 2025, page 13 / 63 6 / 9 preparations preferably have a sun protection factor greater than or equal to 15. In such a case, perfumes are not counted as part of the lipophilic phase.

[0034] According to the invention, the preparation according to the invention advantageously comprises film formers. In the context of the present invention, film formers are substances of varying composition characterized by the following property: if a film former is dissolved in water or other suitable solvents and the solution is then applied to the skin, after evaporation of the solvent, it forms a film that essentially serves to fix the light filters to the skin and thus increase the water resistance of the product.

[0035] According to the invention, it is advantageous that the preparation according to the invention comprises corn starch, maltodextrin and / or pullulan. According to the invention, these compounds can act as film formers.

[0036] Lastly, but not least, the invention provides a process for producing a preparation, which is characterized in that terephthalylidene Dicamphor Sulfonic Acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) and, optionally, disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) are first added to water while stirring and dissolved with the aid of triethanolamine, then optionally 2-phenylbenzimidazole-5-sulfonic acid is added while stirring and dissolved with the aid of NaOH, then NaOH is used to establish a pH of at least 6.4, and in a further step glycol is added while stirring and, after the addition of glycol, additionally other constituents are added. Comparative experiment

[0037] An aqueous solution of 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 Petition 870250088610, dated 09 / 30 / 2025, page 14 / 63 7 / 9 2% by weight of disodium phenyl dibenzimidazole tetrasulfonate that was adjusted to a pH of 7.5 using a 2.5% by weight triethanolamine solution.

[0038] Four variants were produced from this transparent solution: without additional additives, with 10% by weight glycerin, with 10% by weight propane-1,3-diol and with a mixture of 5% by weight glycerin and 5% by weight propane-1,3-diol.

[0039] Samples of all variants were stored at different temperatures (-10 °C, -6 °C, 20 °C) for 5 days, then the amount of precipitate formed was determined optically and the precipitate itself was analyzed microscopically. The following result was obtained at all storage temperatures: Without additional additives: very large amount of precipitate. With 10% by weight of glycerin: a large amount of precipitate. With 10% by weight of propane-1,3-diol: little precipitate. With a mixture of 5% by weight glycerin and 5% by weight propane-1,3-diol: no precipitate.

[0040] The precipitates were always terephthalylidene dicamphor sulfonic acid. Examples The following examples are intended to illustrate the present invention without limiting it. Unless otherwise indicated, all quantities, proportions and percentages are based on weight and total quantity or total weight of the preparations. Petition 870250088610, dated 09 / 30 / 2025, page 15 / 63 8 / 9 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9 Ex 10 Disodium phenyl dibenzimidazole tetrasulfonate 2 1 2 1 2 2 2 0 2 2 Phenylbenzimidazole Sulfonic Acid 4 3 3 2 4 3 3 2 3 3 Dicamphor Sulfonic Acid 3 3 3 3 2.5 2.5 2 3 3 2.5 Glycerin 10 0 5 0 2 0 2 2 5 5 Propylene glycol 0 10 5 0 7 0 3.5 8 0 5 Butylene Glycol 0 0 0 10 0 10 5 0 0 0 Triethanolamine 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Sodium Hydroxide 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Xanthan Gum 1 2 1 1 2 1 1 0.5 1 2 Ethylhexylglycerin 0.2 0.2 0.2 0 0.1 0.2 0.2 0.2 0.2 0.2 Petition 870250088610, dated 09 / 30 / 2025, page 16 / 63 9 / 9 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9 Ex 10 EDTA Trissodium 0.5 0.5 0.5 0.2 0.5 1 0.5 0.7 0.5 0.5 Phenoxetol 0.3 0.5 0.8 0.2 0.5 0.05 0.5 Hexano-1.2- 0.3 0.2 0.3 0 0.1 0.2 0.3 0.2 0.2 0.2 diol 5 5 5 5 5 5 5 5 Ethanol 0 0 0 15 5 5 0 0 0 0 0 0 0 000 0.5 0 Cornstarch 0 0 0 0 0 0 0 0 0 0 0.1 Water Adi Adi Adi Adi Adi Adi Adi Adi Adi Addition icing icing 100 100

Claims

1. Cosmetic preparation characterized by comprising a) a salt of terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), b) one or more glycols, c) water.

2. Use of one or more glycols characterized by being able to increase the solubility of terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) salts in the aqueous phase of cosmetic preparations.

3. Preparation according to claim 1, or use according to claim 2, characterized in that the triethanolamine salt is used as the salt of terephthalylidene dicamphor sulfonic acid.

4. Preparation or use, according to any of the preceding claims, characterized in that the aqueous phase comprises from 0.5% to 3% by weight of terephthalylidene dicamphor sulfonic acid, based on the total weight of the aqueous phase.

5. Preparation or use, according to any of the preceding claims, characterized in that, as glycols, one or more compounds selected from the group of propane-1,2-diol, propane-1,3-diol and butane-1,3-diol.

6. Preparation or use, according to any of the preceding claims, characterized in that the preparation additionally comprises glycerin.

7. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises glycols in a total concentration of 1% to 10% by weight, based on the total weight of the aqueous phase.

8. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises glycerin in a concentration of 1% to 10% by weight, based on the total weight of the aqueous phase.

9. Preparation or use, according to any of the preceding claims, characterized in that the weight ratio between the total amount of glycols and glycerin is from 1:1 to 2:

1.

10. Preparation or use, according to any of the preceding claims, characterized in that the weight ratio of terephthalylidene dicamphor sulfonic acid to the total amount of glycols is from 1:1 to 1:

4.

11. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises a salt of disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) and / or salts of 2-phenylbenzimidazole-5-sulfonic acid.

12. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises 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.

13. Preparation or use, according to any of the preceding claims, characterized in that the preparation of the triethanolamine salt is used as the disodium phenyl dibenzimidazole tetrasulfonate salt (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate).

14. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises 2-phenylbenzimidazole-5-sulfonic acid in a concentration of 1% to 5% by weight, based on the total weight of the aqueous phase.

15. Preparation or use, according to any of the preceding claims, characterized in that the sodium salt preparation is used as the salt of 2-phenylbenzimidazole-5-sulfonic acid. Petition 870250088610, dated 09 / 30 / 2025, page 19 / 63 3 / 3 16. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises ethanol.

17. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises ethylhexylglycerin.

18. Preparation or use, according to any of the preceding claims, characterized in that the preparation does not comprise a lipophilic phase, but is an aqueous preparation.

19. Preparation or use, according to any of the preceding claims, characterized in that the preparation comprises one or more compounds selected from the group of xanthan gum (INCI: Xanthan Gum), welan gum (INCI: Welan Gum), gellan gum (INCI: Gellan Gum), sclerotium gum (INCI: Scerotium Gum), cellulose and / or cellulose derivatives.

20. Cosmetic preparation or use, according to any of the preceding claims, characterized in that the preparation comprises corn starch, maltodextrin and / or pullulan.

21. Process for producing a preparation as defined in any of the preceding claims, characterized in that terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) and, optionally, disodium phenyl dibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) are first added to water while stirring and dissolved with the aid of triethanolamine, then optionally 2-phenylbenzimidazole-5-sulfonic acid is added while stirring and dissolved with the aid of NaOH, then NaOH is used to establish a pH of at least 6.4, and in a further step glycol is added while stirring and, after the addition of glycol, additionally other constituents are added.