The invention relates to compositions comprising disubstituted terephthalates and also light protection filter substances, deodorant and/or antiperspirant active ingredients.
In the case of frequent or large area applications of sunscreen preparations, it cannot be excluded that high dose UV light protection filter substances are applied to the skin in gram amounts. These amounts of UV light protection filter substances have to be incorporated, dissolved homogeneously and stably, into the formulation.
To dissolve these UV light protection filter substances, use is often made of oily components which have a good dissolution capacity for UV light protection filter substances. One compound class used with good dissolution capacity are aliphatic benzoic esters. A typical representative of this compound class is C12-C15 alkyl benzoate, which has been established worldwide as an ingredient for sunscreen formulations.
EP2165696 discloses the use of phenoxyalkyl esters of C6-C12 alkyl- and cycloalkylcarboxylic acids for preparing a cosmetic, dermatological or pharmaceutical formulation and use as solubilizer or solvent for at least one UV light protection filter substance.
EP2062566 discloses the use of isononyl benzoate for preparing a cosmetic, dermatological or pharmaceutical formulation and use as solubilizer or solvent for at least one UV light protection filter substance.
The need for highly concentrated sunscreen formulations with respect to the UV light protection filter substances is due to increased health awareness and still growing recreational behaviour of consumers.
The object of the invention was to provide substances having good dissolution capacity for UV light protection filter substances but also for deodorant and antiperspirant active ingredients.
Surprisingly, it has been found that disubstituted terephthalates have excellent dissolution properties for UV light protection filter substances but also for deodorant and antiperspirant active ingredients.
The present invention therefore relates to compositions comprising disubstituted terephthalates and also light protection filter substances, deodorant and/or antiperspirant active ingredients as described in claim 1.
The invention further relates to the use of disubstituted terephthalates as solubilizers or solvents in a cosmetic or pharmaceutical composition.
One advantage of the present invention is that the disubstituted terephthalates readily dissolve light protection filters for different UV ranges over a broad temperature range.
A further advantage of the present invention is that sunscreen formulations comprising disubstituted terephthalates, when applied to the skin, are characterized by a relatively low oily and well-absorbed skin feel compared to sunscreen formulations comprising C12-15 alkyl benzoates.
A further advantage of the present invention is that sunscreen formulations comprising disubstituted terephthalates have higher storage stabilities, and thereby have a longer shelf life, compared to sunscreen formulations comprising C12-15 alkyl benzoates.
Another advantage of the present invention is that the disubstituted terephthalates stably disperse inorganic pigments and are therefore also suitable for preparing compositions comprising deodorant and/or antiperspirant active ingredients.
A further advantage of the present invention is that the disubstituted terephthalates have good spreadability and thus achieve homogeneous distribution of the light protection factors on the skin.
Unless stated otherwise, all percentages (%) given are percentages by mass.
The present invention therefore relates to a composition comprising
A) at least one substance of the general formula (I)
where R1 and R2 are each independently, the same or different, selected from the group of organic radicals comprising 2 to 18 carbon atoms, preferably aliphatic, especially alkyl radicals, particularly preferably alkyl radicals comprising 4 to 8 carbon atoms; and
B) at least one substance selected from the group of UV light protection filter substances, deodorant and antiperspirant active ingredients, especially UV light protection filter substances.
Substances of the general formula (I) are synthetically accessible, as described, for example, in EP3351526.
In accordance with the invention, R1 and R2 are each independently, the same or different, selected from the group of branched alkyl radicals, particularly preferably comprising 4 to 8 carbon atoms, especially isopentyl.
The UV light protection filter substances present can be, for example, organic substances which are capable of absorbing ultraviolet radiation and emitting again the absorbed energy in the form of longer-wave radiation, for example heat.
UVB filters can be oil-soluble or water-soluble. Oil-soluble UVB light protection filters include, for example:
3-benzylidenecamphor derivatives, e.g. 3-(4-methylbenzylidene)camphor (INCI: 4-Methylbenzylidene Camphor), 4-aminobenzoic acid derivatives such as e.g. 2-ethylhexyl 4-(dimethylamino)benzoate (INCI: Ethylhexyl Dimethyl PABA), 2-hydroxyethyl 4-{bis[2-(2-hydroxyethoxy)ethyl]amino}benzoate (INCI: PEG-25 PABA), esters of cinnamic acid such as e.g. 2-ethylhexyl 4-methoxycinnamate (INCI; Ethylhexyl Methoxycinnamate), isopentyl 4-methoxycinnamate (INCI: Isoamyl p-Methoxycinnamate), 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: Octocrylene), esters of salicylic acid such as e.g. 2-ethylhexyl salicylate (INCI: Ethylhexyl Salicylate), homomenthyl salicylate (INCI: Menthyl Salicylate), 3,3,5-trimethylcyclohexyl salicylate (INCI: Homosalate), 2-hydroxybenzoic acid 2,2′,2″-nitrilotriethanol (1:1) (INCI: TEA-Salicylate), derivatives of benzophenone such as e.g. 2-hydroxy-4-methoxybenzophenone (INCI: Benzophenone-3), 2,2′-dihydroxy-4-methoxybenzophenone (INCI: Benzophenone-8), 2-hydroxy-4-methoxy-4′-methylbenzophenone (INCI: Benzophenone-10), triazine derivatives such as e.g. tris(2-ethylhexyl) 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tribenzoate (INCI: Ethylhexyl Triazone, obtainable for example under the trade name Uvinul T 150 from BASF), iscotrizinole (INCI: Diethylhexyl Butamido Triazone) and 2,4,6-tri(4-biphenylyl)-1,3,5-triazine (INCI: Tris-Biphenyl Triazine). Another UVB filter is 3-(4-(2,2-bisethoxycarbonylvinyl)phenoxy)propenyl)methoxysiloxane/dimethylsiloxane copolymer (INCI: Polysilicone-15), which can be obtained for example under the trade name Parsol SLX. Possible water-soluble UVB light protection filters are, for example: salts of 2-phenylbenzimidazole-5-sulfonic acid such as the alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof and also the sulfonic acid itself with the INCI name Phenylbenzimidazole Sulfonic Acid, sulfonic acid derivatives of benzophenone such as e.g. 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid (NCI: Benzophenone-4) and salts thereof, benzensulfonic acid derivatives of 3-benzylidenecamphor such as e.g. 4-[(E)-(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2-ylidene)methyl]benzenesulfonic acid (INCI: Benzylidene Camphor Sulfonic Acid) and salts thereof.
Typical suitable oil-soluble broadband UVA light protection filters are, for example, derivatives of benzoylmethane such as for example 1-(4-methoxyphenyl)-3-[4-(2-methyl-2-propanyl)phenyl]-1,3-propanedione (INCI: Butyl Methoxydibenzoylmethane), 1-(4-isopropylphenyl)-3-phenyl-1,3-propanedione (INCI: Isopropyl Dibenzoylmethane), triazine derivatives such as e.g. 2,2′-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis{5-[(2-ethylhexyl)oxy]phenol} (INCI: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, obtainable for example under the trade name Tinosorb S from BASF), N,N′-bis[4-[5-(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]-N″-(2-ethylhexyl)-1,3,5-triazine-2,4,6-triamine (INCI: Ethylhexyl Bis-Isopentylbenzoxazolylphenyl Melamine, obtainable under the trade name Uvasorb K2A from 3V Sigma) and derivatives of benzophenone such as e.g. hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate).
Possible water-soluble broadband UVA light protection filters are, for example: 3,3′-(1,4-phenylenedimethylene)bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]hept-1-ylmethanesulfonic acid) and salts thereof, especially the corresponding sodium, potassium or triethanolammonium salt, which is also referred to as benzene-1,4-di(2-oxo-3-bornylidenemethyl-10-sulfonic acid) and has the INCI name Terephthalylidene Dicamphor Sulfonic Acid (obtainable under the trade name Mexoryl SX), 2,2′-(1,4-phenylene)bis(6-sulfa-1H-benzimidazole-4-sulfonic acid) and salts thereof, the corresponding sodium, potassium or triethanolammonium salts, e.g. disodium 2,2′-(1,4-phenylene)bis(6-sulfo-1H-benzimidazol-4-sulfonate) with the INCI name Disodium Phenyl Dibenzimidazole Tetrasulfonate, trade name e.g. Neo Heliopan AP.
Further broadband UVA filters are, e.g. 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethyl-2-pentanyl)phenol] (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, obtainable for example under the trade name Tinosorb M from BASF), 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol (INCI: Drometrizole Trisiloxane, trade name: Mexoryl XL), (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 2-aminobenzoate (INCI: Menthyl Anthranilate) and 2-ethoxyethyl (2E)-3-(4-methoxyphenyl)acrylate (INCI: Cinoxate).
The UV filters can also obviously be present in mixtures in the compositions according to the invention.
Besides the soluble substances specified, insoluble pigments are also suitable for this purpose, namely finely dispersed metal oxides or salts, such as for example titanium dioxide, zinc oxide, iron oxide, aluminium oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate. The particles here should have an average diameter of less than 100 nm, e.g. between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, although it is also possible to use those particles which have an ellipsoidal shape or a shape which deviates in some other way from the spherical form. Also possible, however, are micronized organic pigments such as for example 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethyl-2-pentanyl)phenol] (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutyiphenol, obtainable for example under the trade name Tinosorb M from BASF) having a particle size of <200 nm, which can be obtained, for example, as a 50% aqueous dispersion.
In addition, further suitable UV light protection filters can be found in the overview by P. Finkel in SÖFW-Journal 122, 543 (1996) or the chapter The Chemistry of Ultraviolet Filters by N. A. Shaath in Principles and Practice of Photoprotection, S. Q. Wang, H. W. Lim (eds.), Springer International Publishing Switzerland 2016.
It is preferred in accordance with the invention that component B) of the composition according to the invention is selected from at least two, preferably at least three, particularly preferably at least four, selected from the group of UV light protection filter substances.
It is preferred in accordance with the invention that component B) of the composition according to the invention is selected from the group of organic UV light protection filter substances, especially from the group of triazine derivatives.
It is particularly preferred in accordance with the invention that component B) of the composition according to the invention is selected from the group of UV light protection filter substances comprising, preferably consisting of,
butyl methoxydibenzoylmethane,
ethylhexyl triazone,
bis-ethylhexyloxyphenol methoxyphenyl triazine,
diethylhexyl butamido triazone,
diethylamino hydroxybenzoyl hexyl benzoate,
benzophenone-3,
4-methylbenzylidene camphor.
It is furthermore preferred in accordance with the invention that component B) of the composition according to the invention is selected from the group of deodorant and antiperspirant active ingredients comprising, preferably consisting of, astringents, preferably aluminium salts, zinc salts and aluminium-zirconium complexes. From this group, particular preference is given to the presence of basic aluminium chlorides such as aluminium chlorohydrate (“ACH”) or aluminium-zirconium-glycine salts (“ZAG”),
A preferred composition according to the invention is characterized in that component A) is present in an amount of 0.1% by weight to 60% by weight, preferably 0.5% by weight to 30% by weight, particularly preferably 1% by weight to 20% by weight, and component B) is present in an amount of 0.1% by weight to 50% by weight, preferably 1% by weight to 40% by weight, particularly preferably 3% by weight to 30% by weight.
The compositions according to the invention can comprise e.g. at least one further, additional component selected from the group of
Substances which can be used as exemplary representatives of the individual groups are known to those skilled in the art and can be found for example in German application DE 102008001788.4. This patent application is hereby incorporated as reference and thus forms part of the disclosure. As regards further optional components and the amounts used of these components, reference is made expressly to the relevant handbooks known to the person skilled in the art, e.g. K. Schrader, “Grundlagen and Rezepturen der Kosmetika [Fundamentals and formulations of cosmetics]”, 2nd edition, pages 329 to 341, Hüthig Buch Verlag Heidelberg.
The amounts of the particular additives are determined by the intended use.
Typical boundary formulations for the respective applications are known prior art and are contained for example in the brochures of the manufacturers of the particular base and active ingredients. These existing formulations can generally be adopted unchanged. However, if required, for adjustment and optimization, the desired modifications can be undertaken by simple tests without complication.
Compositions according to the invention can be used, for example, as skin care, facial care, head care, body care, intimate care, foot care, hair care, nail care, dental care or oral care products.
Compositions according to the invention can be used, for example, in the form of an emulsion, a suspension, a solution, a cream, a salve, a paste, a gel, an oil, a powder, an aerosol, a stick, a spray, a cleansing product, a make-up or sunscreen preparation or a facial toner.
The present invention further relates to the use of at least one substance of the general formula (I)
where R1 and R2 are each independently, the same or different, selected from the group of organic radicals comprising 2 to 18 carbon atoms, preferably aliphatic, especially alkyl radicals, particularly preferably alkyl radicals comprising 4 to 8 carbon atoms;
as solubilizer or solvent in a cosmetic or pharmaceutical composition, particularly as solubilizer or solvent for at least one substance selected from the group of UV light protection filter substances, deodorant and antiperspirant active ingredients, especially UV light protection filter substances.
In the use according to the invention, preference is given to using the components specified above as components preferably present in the context of the compositions according to the invention.
The examples which follow describe the present invention by way of example, without any intention of restricting the invention, the scope of which is apparent from the entirety of the description and the claims, to the embodiments cited in the examples.
The following figures are part of the examples:
To test the dissolution capacity of UV light protection filters, three representative UVA or UVB light protection filters were selected representatively. These are:
To determine the dissolution capacity for these three UV light protection filters, a certain amount (50 g) of one of the compounds according to the invention was initially charged in each case and temperature-controlled at 22° C. A percentage by weight of a UV light protection filter was added and stirred until this amount had fully and homogeneously dissolved. This procedure was repeated until the maximal soluble amount of the UV light protection filter had been exceeded. For complete dissolution at higher concentrations, a longer stirring time of several hours is often required. If the maximum concentration had been roughly determined in this manner, a fine determination of the concentration range was repeated around this maximum concentration using smaller weighed amounts of the UV light protection filter.
The dialkyl terephthalates used dissolve the UV light protection filters investigated better than C12-15 alkyl benzoate and 2-phenoxyethyl octanoate.
In particular, the dialkyl terephthalates used are characterized by excellent properties in the dissolution capacity for EHT.
The formulations shown in Table 1 were prepared. The influence on skin feel of the formulations was investigated by a test panel. Thirteen people each applied a defined amount of approx. 25 μl of both formulations to a defined test field on the inside of the forearm without knowing the composition of the formulations. The formulations were spread with a finger by circular movements in the test field. The parameters oiliness and absorption were assessed during spreading of the sample. After absorption was complete, there was a pause and, after 5 minutes, the skin feel on the test field was re-assessed.
The formulations shown in Table 2 were prepared. The influence on skin feel of the formulations was investigated by a test panel. Fourteen people each applied a defined amount of approx. 25 μl of both formulations to a defined test field on the inside of the forearm without knowing the composition of the formulations. The formulations were spread with a finger by circular movements in the test field. The parameters oiliness and absorption were assessed during spreading of the sample. After absorption was complete, there was a pause and, after 5 minutes, the skin feel on the test field was re-assessed.
The oil-in-water sunscreen emulsions shown in Table 1 were prepared. The viscosities of the formulations are comparable (7-8, or 9 Pa·s; Brookfield viscosity, measured with spindle 4, 5 rpm).
All the formulations are low-viscosity lotions. The formulations were stored at 40° C. and 45° C. for three months. After three months, both samples stored at 40° C. and at 45° C. showed significant oil separation of the formulation comprising C12-15 alkyl benzoate, but not in the formulations according to the invention comprising dialkyl terephthalates.
The formulation examples listed below are listed using di(iso)pentyl terephthalate.
All the following listed formulation examples are in each case additionally formulated, instead of di(iso)pentyl terephthalate, with di(neo)pentyl terephthalate, di(n-)pentyl terephthalate, (iso/neo)pentyl terephthalate, (iso/n-)pentyl terephthalate, (neo/n-)pentyl terephthalate, di(iso)hexyl terephthalate, di(2-ethylhexyl) terephthalate, di(n-)butane terephthalate, di(2-methylpropane) terephthalate and n-butane/2-methylpropane terephthalate.
Number | Date | Country | Kind |
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19195485.8 | Sep 2019 | EP | regional |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2020/073921 | 8/27/2020 | WO |