Sunscreen containing terephthalylidene dicamphor sulfonic acid and glycols
Patent Information
- Application Number
- EP2024709339
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-03-30
- Filing Date
- 2024-03-01
- Publication Date
- 2026-02-11
AI Technical Summary
Terephthalylidene dicamphor sulfonic acid, a water-soluble UV-A filter, has limited stability in the aqueous phase of sunscreens, prone to crystallization at cooler temperatures, restricting its use to concentrations below 0.4% by weight, which is insufficient for effective UV protection.
A cosmetic preparation combining terephthalylidene dicamphor sulfonic acid with one or more glycols and water, specifically using triethanolamine salt, propane-1,2-diol, propane-1,3-diol, and 1,2-hexanediol, along with other UV filters like disodium phenyldibenzimidazole tetrasulfonate and 2-phenylbenzimidazole-5-sulfonic acid, to enhance solubility and stability, maintaining effective UV protection.
The formulation prevents crystallization of terephthalylidene dicamphor sulfonic acid at higher concentrations, ensuring stable and effective UV protection even at lower temperatures, achieving a sun protection factor of greater than or equal to 15 without a lipophilic phase.
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Abstract
Description
[0001] Description
[0002] Sunscreen with terephthalylidene dicamphorsulfonic acid and glycols The present invention relates to a cosmetic preparation containing a salt of terephthalylidene dicamphorsulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), one or more glycols and water.
[0003] 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 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 causes numerous phototoxic and photoallergic reactions and results in premature skin aging.
[0004] 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.
[0005] However, the multitude of commercially available sunscreens should not obscure the fact that these state-of-the-art preparations have a number of disadvantages. For many years, there has been a steadily growing demand for UV-A filter substances. This is due not least to numerous government regulations that require sunscreens to provide a balanced ratio of UV-A and UV-B protection. However, the number of UV-A filters available in cosmetics is very limited. Oil-soluble compounds such as butyl methoxydibenzoylmethane or diethylamino hydroxybenzoyl hexyl benzoate are primarily used.
[0006] To achieve particularly high UV protection, however, it is necessary to incorporate UV-A filters into the aqueous phase as well. Terephthalylidene dicamphorsulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) was developed for this purpose about 30 years ago as a water-soluble UV-A filter substance. However, this substance has the disadvantage that it can only be incorporated into the aqueous phase of a sunscreen in limited quantities, as it tends to recrystallize from the aqueous phase during prolonged storage at cool temperatures (e.g., in winter at temperatures below 10°C).
[0007] It was therefore the object of the present invention to develop an aqueous phase for a cosmetic preparation or an aqueous cosmetic preparation with terephthalylidene dicamphorsulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), in which the risk of crystallization is effectively suppressed even at higher concentrations (ie greater than 0.4% by weight), in particular in cold conditions (ie below 10 °C) of this UV filter substance.
[0008] The problem is solved by a cosmetic preparation containing a) a salt of terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), b) one or more glycols c) water.
[0009] The object is further achieved by the use of one or more glycols to increase the solubility of salts of terephthalylidene dicamphorsulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) in the aqueous phase of cosmetic preparations. For the purposes of the present invention, glycols are defined exclusively as compounds that have two hydroxyl groups (OH groups). Glycerin, by definition, is not a glycol for the purposes of the present invention.
[0010] Furthermore, within the scope of the present disclosure, designations 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, the concentration stated as “total weight of the aqueous phase” applies to the entire preparation.
[0012] According to the invention, it is advantageous if the triethanolamine salt is used as the salt of terephthalylidenedicamphersulfonic acid. Furthermore, it is advantageous within the meaning of the present invention if the aqueous phase contains from 0.5 to 3% by weight of terephthalylidenedicamphersulfonic acid, based on the total weight of the aqueous phase. According to the invention, the concentration range of 2 to 3% by weight of terephthalylidenedicamphersulfonic acid, based on the total weight of the aqueous phase, is preferred.
[0013] Advantageous embodiments of the present invention are characterized in that one or more compounds are selected from the group consisting of propane-1,2-diol, propane-1,3-diol, and butane-1,3-diol as glycols. Preferred according to the invention are propane-1,2-diol and propane-1,3-diol, with propane-1,3-diol being particularly preferred.
[0014] According to the invention, it is also particularly preferred if the glycols advantageous according to the invention are additionally combined with 1,2-hexanediol.
[0015] According to the invention, it is advantageous if the preparation contains the glycols in a total concentration of 1 to 10% by weight, based on the total weight of the aqueous phase. According to the invention, the concentration range of 4 to 8% by weight of glycols, based on the total weight of the aqueous phase, is preferred.
[0016] If the preparation according to the invention contains a combination of glycols advantageous according to the invention with 1,2-hexanediol, the preferred use concentration according to the invention is from 1,2, hexanediol 0.2 to 0.5% by weight, based on the total weight of the aqueous phase.
[0017] Particularly advantageous embodiments according to the invention are obtained when the preparation additionally contains glycerol.
[0018] In such a case, the advantageous embodiments of the present invention are characterized in that the preparation contains glycerol in a concentration of 1 to 10% by weight, based on the total weight of the aqueous phase.
[0019] Furthermore, it is preferred according to the invention if the weight ratio of the total amount of glycols to glycerol is from 1:1 to 2:1.
[0020] With regard to the weight ratio of terephthalylidene dicamphorsulfonic acid to the total amount of glycols, it is advantageous according to the invention if the weight ratio of terephthalylidene dicamphorsulfonic acid to the total amount of glycols is from 1:1 to 1:4.
[0021] To ensure complete protection against UV rays from sunlight, the preparation must contain additional UV filter substances. According to the invention, it has proven particularly advantageous if the preparation contains a salt of disodium phenyldibenzimidazoletetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) and / or 2-phenylbenzimidazole-5-sulfonic acid salts.
[0022] If the preparation according to the invention contains disodium phenyldibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate), the advantageous embodiments according to the invention are characterized in that the preparation contains disodium phenyldibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) in a concentration of 0.5 to 3% by weight, based on the total weight of the aqueous phase.
[0023] Furthermore, in such a case it is advantageous according to the invention if the triethanolamine salt is used as the salt of disodium phenyldibenzimidazoletetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate).
[0024] If the preparation according to the invention contains 2-phenylbenzimidazole-5-sulfonic acid salts, it is advantageous according to the invention if the preparation contains 2-phenylbenzimidazole-5-sulfonic acid in a concentration 1 of 5 to 10% by weight, based on the total weight of the aqueous phase.
[0025] Furthermore, 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.
[0026] Further advantageous embodiments of the present invention are characterized in that the preparation contains ethanol.
[0027] If the aqueous phase of the preparation contains ethanol, this is preferably used according to the invention in a concentration 2 of 15 to 25% by weight, based on the total weight of the aqueous phase.
[0028] Furthermore, it is advantageous in the sense of the present invention if the preparation contains ethylhexylglycerin.
[0029] The advantageous use concentration for ethylhexylglycerol according to the invention is from 0.1 to 0.3% by weight, based on the total weight of the aqueous phase.
[0030] It is further advantageous within the meaning of the present invention if the preparation contains one or more compounds selected from the group consisting of xanthan gum (INCI: Xanthan Gum), welan gum (INCI: Welan Gum), gelan gum (INCI: Gelan Gum), sclerotium gum (INCI: Scerotium Gum), cellulose, and / or cellulose derivatives. A particularly advantageous embodiment of the present invention is when the preparation does not contain a lipophilic phase, but is an aqueous preparation. According to the invention, this preferably has a sun protection factor of greater than or equal to 15. In such a case, perfume substances are not counted as part of the lipophilic phase.
[0031] According to the invention, the preparation according to the invention advantageously contains film formers. Film formers within the meaning of the present invention are substances of various compositions that are 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, it forms a film after the solvent evaporates, which essentially serves to fix the light filters to the skin and thus increase the water resistance of the product.
[0032] According to the invention, it is advantageous if the preparation according to the invention contains corn starch, malodextrin, and / or pullulan. These compounds can act as film formers according to the invention.
[0033] Last but not least, the invention relates to a process for producing a preparation which is characterized in that first terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) and optionally disodium phenyldibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) are added to water with stirring and dissolved with the aid of triethanolamine, then optionally 2-phenylbenzimidazole-5-sulfonic acid is added with stirring and dissolved with the aid of NaOH, then a pH of at least 6.4 is adjusted with the aid of NaOH, and in a further step the glycol is added with stirring and, after the addition of glycol, further components are added if necessary.
[0034] Comparison experiment
[0035] An aqueous solution of
[0036] 3 wt% terephthalylidenedicamphersulfonic acid, (9 wt% of a 33% aqueous solution) 3 wt% 2-phenylbenzimidazole-5-sulfonic acid and
[0037] 2 wt.% disodium phenyldibenzimidazoletetrasulfonic acid was prepared, which was adjusted to pH 7.5 with 2.5 wt.% triethanolamine solution.
[0038] Four variants of this clear solution were produced:
[0039] 1 without further additives, with 10% by weight glycerol, with 10% by weight propane-1,3-diol and with a mixture of 5% by weight glycerol and 5% by weight propane-1,3-diol.
[0040] Samples of all variants were tested at different temperatures (-10 °C, -6 °C, 20 °C) for
[0041] The samples were stored for 5 days, after which the amount of precipitate formed was visually determined and the precipitate itself was analyzed microscopically. The following results were obtained at all storage temperatures:
[0042] Without further additives: very high precipitation. With 10% by weight glycerol: high precipitation. With 10% by weight propane-1,3-diol: little precipitation. With a mixture of 5% by weight glycerol and 5% by weight propane-1,3-diol: no precipitation.
[0043] The precipitates were always terephthalylidenedicamphersulfonic acid.
[0044] Examples
[0045] The following examples 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
Patent claims 1 . Cosmetic preparation containing 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 to increase the solubility of salts of terephthalylidene dicamphorsulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) 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 dicamphorsulfonic acid.
4. Preparation or use according to one of the preceding claims, characterized in that the aqueous phase contains from 0.5 to 3% by weight of terephthalylidenedicamphorsulfonic acid, based on the total weight of the aqueous phase.
5. Preparation or use according to one of the preceding claims, characterized in that the glycols used are one or more compounds selected from the group consisting of propane-1,2-diol, propane-1,3-diol and butane-1,3-diol.
6. Preparation or use according to one of the preceding claims, characterized in that the preparation additionally contains glycerin.
7. Preparation or use according to one of the preceding claims, characterized in that the preparation contains the 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 one of the preceding claims, characterized in that the preparation contains glycerol in a concentration of 1 to 10 % by weight, based on the total weight of the aqueous phase.
9. Preparation or use according to one of the preceding claims, characterized in that the weight ratio of the total amount of glycols to glycerol is from 1:1 to 2:
1.
10. Preparation or use according to one of the preceding claims, characterized in that the weight ratio of terephthalylidenedicamphersulfonic acid to the total amount of glycols is from 1:1 to 1:
4. 11 . Preparation or use according to one of the preceding claims, characterized in that the preparation contains a salt of disodium phenyldibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonates) and / or 2-phenylbenzimidazole-5-sulfonic acid salts.
12. Preparation or use according to one of the preceding claims, characterized in that the preparation contains disodium phenyldibenzimidazoletetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) in a concentration of 0.5 to 3% by weight, based on the total weight of the aqueous phase.
13. Preparation or use according to one of the preceding claims, characterized in that the preparation uses the triethanolamine salt as the salt of disodium phenyldibenzimidazoletetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate).
14. Preparation or use according to one of the preceding claims, characterized in that the preparation contains 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 one of the preceding claims, characterized in that the preparation uses the sodium salt as the salt of 2-phenylbenzimidazole-5-sulfonic acid.
16. Preparation or use according to one of the preceding claims, characterized in that the preparation contains ethanol.
17. Cosmetic preparation or use according to one of the preceding claims, characterized in that the preparation contains ethylhexylglycerin.
18. Preparation or use according to one of the preceding claims, characterized in that the preparation does not contain a lipophilic phase, but is an aqueous preparation.
19. Cosmetic preparation or use according to one of the preceding claims, characterized in that the preparation contains one or more compounds selected from the group xanthan gum (INCI: Xanthan Gum), welan gum (INCI: Welan Gum), gelan gum (INCI: Gelan Gum), sclerotium gum (INCI: Scerotium Gum), cellulose and / or cellulose derivatives.
20. Cosmetic preparation or use according to one of the preceding claims, characterized in that the preparation contains corn starch, malodextrin and / or pullulan. 21 . A process for the preparation of a preparation according to one of the preceding claims, characterized in that first terephthalylidene dicamphor sulfonic acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid) and optionally disodium phenyldibenzimidazole tetrasulfonate (INCI: Disodium Phenyl Dibenzimidazole Tetrasulfonate) are added to water with stirring and dissolved with the aid of triethanolamine, then optionally 2-phenylbenzimidazole-5-sulfonic acid is added with stirring and dissolved with the aid of NaOH, then a pH of at least 6.4 is adjusted with the aid of NaOH, and in a In a further step, the glycol is added while stirring and, after the addition of glycol, other ingredients are added if necessary.