Sunscreen composition with low stickiness

Abstract

To provide a sand-repellent sunscreen composition having a high ultraviolet protection factor in which organic UV filters such as triazine derivatives are stably dissolved.SOLUTION: Provided is a topical preparation comprising a UV filter combination of certain microfine zinc oxide, 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-Ethylhexyloxyphenol methoxyphenyl Triazine), 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof, and 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: Diethylhexyl butamido triazone).SELECTED DRAWING: None

Description

Detailed Description of the Invention

[0001] The present invention relates to a topical formulation comprising a combination of finely divided zinc oxide, the UV filters 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bisethylhexyloxyphenol methoxyphenyl triazine), 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof, and 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: Diethylhexylbutamidotriazon).

[0002] It is well known that ultraviolet (UV) rays from sunlight have a damaging effect on the skin. In addition to the well-known acute damage (sunburn), there is also long-term damage, such as an increased risk of developing skin cancer. Furthermore, exposure to UV rays is responsible for most of the wrinkles and age spots on people's faces. Therefore, various photoprotective UV filter substances have been developed that can be incorporated into topical sunscreen formulations to protect the skin from the harmful effects of UV rays.

[0003] Modern sunscreens are required to effectively and safely protect skin from the harmful effects of ultraviolet radiation. Therefore, sunscreens generally contain various UV-B (wavelength: 280-320 nm) and UV-A (wavelength: 320-400 nm) filters. However, these filters often make the sunscreen sticky, which means that sand will stick to the skin where the cream is applied, especially when used at the beach. The higher the UV filter content of the formulation, the greater this problem becomes. To address the stickiness issue, consumers tend to use less sunscreen, which leads to insufficient protection.

[0004] Even though many attempts have been made to develop sunscreen compositions with reduced stickiness, this problem has yet to be solved in the most satisfactory way, especially for formulations characterized by a high sun protection factor.

[0005] Therefore, there is a continuing need to develop new sunscreen formulations that have reduced stickiness.

[0006] It would therefore be advantageous to have available sunscreen compositions that have anti-sanding properties, and more particularly sunscreen compositions that have a high sun protection factor (SPF 20 or greater) and particularly low sand adhesion.

[0007] In addition to stickiness / grit, another problem with cosmetic sunscreen compositions is that UV filters do not exhibit particularly good solubility in the formulation when used in very high amounts. In particular, when developing formulations with high sun protection factors and high UV filter contents, developers face the problem of solubility of triazine derivatives. To solve this problem, octocrylene, a liquid UV-B filter, has been used as both a UV filter and a solvent.

[0008] The drawback of the prior art in this case is that, although octocrylene has been approved by regulatory authorities, its use is not entirely uncontroversial, and products have been given "bad marks" in evaluations by certain consumer magazines (e.g., Oko-test in Germany). The reason for this bad mark is that certain scientists have doubts that this UV filter may have hormone-like effects in some cases. Despite the fact that sunscreen compositions containing this UV filter have been used worldwide for decades and that no adverse effects on the human body have been found, some consumers still wish to avoid formulations containing this type of ingredient.

[0009] Therefore, it would be desirable to develop a sunscreen composition that overcomes the shortcomings of the prior art, has a high UV protection factor, and has sand-resistant properties, in which organic UV filters such as triazine derivatives are stably dissolved. Ideally, it would be possible to achieve this goal without using octocrylene as a solvent and stabilizer.

[0010] Accordingly, the present invention provides a topical sunscreen composition comprising: a.) finely divided zinc oxide, preferably having an average particle size Dn50 selected in the range of 50 to 200 nm, as determined by laser diffraction, and a surface coating selected from the group consisting of aluminum stearate, stearic acid, methicone, simethicone, triethoxycaprylylsilane, and octyltrimethoxysilane; b.) 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bisethylhexyloxyphenol methoxyphenyl triazine), c.) 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof; d.) 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: Diethylhexylbutamidotriazone) Contains a combination of UV filters.

[0011] The term finely divided zinc oxide refers to any zinc oxide particles suitable for use as a UV filter, i.e., zinc oxide having a particle size essentially useful for incorporation into sunscreen compositions. Advantageously, the finely divided zinc oxide consists of particles having a primary particle size of less than about 300 nm, e.g., less than about 200 nm or less than about 150 nm. Most preferably, in all embodiments of the present invention, the average particle size of the finely divided zinc oxide according to the present invention is selected in the range of 30 to 200 nm, preferably in the range of 50 to 200 nm, more preferably in the range of 75 to 150 nm, and most preferably in the range of 90 to 130 nm. Further preferred ranges include 30 to 150 nm and 30 to 130 nm.

[0012] As used herein, the term "average particle size" refers to the median diameter Dn50 (also known as Dn0.5) of the particle size distribution by number, as determined by laser diffraction using, for example, a Horiba particle size analyzer LA-960 or a Malvern Mastersizer 2000 (ISO 13320:2009).

[0013] The zinc oxide according to the invention more preferably has a Dn1 of >20 nm (1% below this diameter).

[0014] According to the present invention, it is also advantageous for the zinc oxide particles to be surface-coated. The surface coating may involve providing the metal oxide particles with a thin hydrophilic or hydrophobic inorganic or organic layer by methods known per se. According to the present invention, the various surface coatings may also contain water. The surface treatment may impart hydrophilic, amphiphilic or hydrophobic properties to the metal oxide.

[0015] Suitable inorganic surface coatings for the purposes of the present invention include, for example, aluminum oxide (Al2O3), aluminum hydroxide Al(OH)3, aluminum oxide hydrate (also known as alumina, CAS number: 1333-84-2), sodium hexametaphosphate (NaPO3)6, sodium metaphosphate (NaPO3) n, silicon dioxide (SiO2) (also known as silica, CAS number: 7631-86-9), and iron oxide (Fe2O3). These inorganic surface coatings may be present alone, in combination, and / or in combination with organic coating materials.

[0016] Examples of organic surface coatings suitable for use in the present invention include vegetable or animal-derived aluminum stearate, vegetable or animal-derived stearic acid, lauric acid, dimethylpolysiloxane (also known as dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of about 200 to about 350 dimethylsiloxane units and silica gel), triethoxycaprylylsilane, and octyltrimethoxysilane. These organic surface coatings can be present alone, in combination, and / or in combination with inorganic coating materials. Preferably, the zinc oxide of the present invention is uncoated or coated with dimethicone, methicone, or triethoxycaprylylsilane; most preferably, the zinc oxide of the present invention is surface-coated with triethoxycaprylylsilane.

[0017] Preferably, the amount of coating is selected in the range of 0.1 to 25 wt. %, preferably in the range of 0.25 to 10 wt. %, most preferably in the range of 0.5 to 7.5 wt. %, and even more preferably in the range of 1 to 5 wt. %, based on the weight of uncoated zinc oxide.

[0018] More preferably, the zinc oxide is a white powder consisting of zinc oxide present in a wurtzite crystalline structure.

[0019] Zinc oxide particles and pre-dispersions of zinc oxide particles for use according to the invention are available, for example, as MZ-505S (5% methicone coated) from Tayca, ZnO-C-DS4 (dimethicone coated) from Kobo or PARSOL® ZX (2-3.5% triethoxycaprylylsilane coated) from DSM Nutritional Products Ltd.

[0020] A particularly advantageous zinc oxide according to the invention is obtained by dissolving zinc oxide in water under strongly acidic conditions (e.g., HCl) and at high temperature, followed by recrystallization of zinc oxide particles by neutralization with NaOH, coating the particles thus obtained with triethoxycaprylylsilane, followed by dehydration, drying and grinding.

[0021] Most preferably, in all embodiments according to the present invention, the zinc oxide is a white powder consisting of zinc oxide present as a wurtzite crystalline structure coated with triethoxycaprylylsilane, the zinc oxide content of which is 96-98%, the triethoxycaprylylsilane content of which is 2-3.5%, and the average particle size of which is 90-130 nm, which is commercially available as PARSOL® ZX.

[0022] In all embodiments of the present invention, the amount of finely divided zinc oxide is preferably selected in the range of 0.1% to 20% by weight, more preferably in the range of 0.5% to 15% by weight, most preferably in the range of 1% to 10% by weight, for example in the range of 5% to 10% by weight, based on the total weight of the topical composition.

[0023] In all embodiments of the present invention, the amount of 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: bisethylhexyloxyphenol methoxyphenyl triazine) is preferably selected in the range of 0.1% to 10% by weight, more preferably in the range of 0.5% to 7.5% by weight, and most preferably in the range of 1% to 5% by weight, based on the total weight of the topical composition.

[0024] In all embodiments of the present invention, the amount of 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof is preferably selected in the range of 0.1% to 10% by weight, more preferably in the range of 0.5% to 7.5% by weight, and most preferably in the range of 1% to 5% by weight, based on the total weight of the topical composition.

[0025] In all embodiments of the present invention, the amount of 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: diethylhexylbutamidotriazone) is preferably selected in the range of 0.1% to 10% by weight, more preferably in the range of 0.5% to 7.5% by weight, and most preferably in the range of 1% to 5% by weight, based on the total weight of the topical composition.

[0026] The term "topical" as used herein is understood to mean external application to keratinous materials, in particular the skin, scalp, eyelashes, eyebrows, nails, mucous membranes and hair, preferably human skin.

[0027] Since the topical compositions according to the invention are intended to be applied topically, it is fully understood that the topical compositions according to the invention comprise a physiologically acceptable medium, i.e., a medium that is compatible with keratinous materials such as the skin, mucous membranes, and keratinous fibers. In particular, a physiologically acceptable medium is a cosmetically acceptable carrier.

[0028] As used herein, the term "cosmetically acceptable carrier" refers to any carrier, excipient, and / or diluent conventionally used in topical cosmetic compositions, particularly skin care formulations.

[0029] The exact amount of carrier will depend on the actual amount of UV filters and any other optional ingredients that one of ordinary skill in the art would classify as different from a carrier (eg, other active ingredients).

[0030] In an advantageous embodiment, the topical composition according to the invention comprises 50% to 99%, preferably 60% to 98%, more preferably 70% to 98%, in particular 80% to 95%, of a carrier based on the total weight of the topical composition.

[0031] In certain advantageous embodiments, the carrier further comprises at least 40% by weight, more preferably at least 50% by weight, most preferably at least 55% by weight of water, especially such as 55-90% by weight of water.

[0032] In particular, the topical composition according to the invention is a cosmetic or pharmaceutical composition, preferably a cosmetic (non-therapeutic) composition.

[0033] In one embodiment, the topical composition according to the invention is applied to mammalian keratinous tissue, in particular human skin or human scalp and hair.

[0034] The term "cosmetic composition" as used in this application refers to cosmetic compositions as defined under the heading "Kosmetika" in Römpp Lexikon Chemie, 10th edition 1997, Georg Thieme Verlag Stuttgart, New York, and cosmetic compositions disclosed in A. Domsch, "Cosmetic Compositions", Verlag für chemische Industrie (ed. H. Ziolkowsky), 4th edition, 1992.

[0035] Preferred topical compositions according to the present invention are skin care formulations, decorative formulations and functional formulations.

[0036] Examples of skin care preparations are, in particular, photoprotective preparations, anti-aging preparations, preparations for treating photoaging, body oils, body lotions, body gels, treatment creams, skin protective ointments, skin powders, moisturizing gels, moisturizing sprays, moisturizers for the face and / or body, tanning preparations (i.e. compositions for tanning and / or browning human skin artificially / without the use of sunlight), such as self-tanning creams, and skin whitening preparations.

[0037] Examples of decorative preparations are in particular lipsticks, eye shadows, mascaras, dry and wet make-up formulations, blushes and / or powders.

[0038] Examples of functional formulations are, but are not limited to, cosmetic or pharmaceutical compositions containing active ingredients such as hormone formulations, vitamin formulations, plant extract formulations, anti-aging formulations and / or antimicrobial (antibacterial or antifungal) formulations.

[0039] In certain embodiments, the topical compositions according to the invention are photoprotective preparations (sunscreens), such as sunscreen emulsions, sunscreen lotions, sunscreen creams, sunscreen oils, sunblocks or tropical's or daycare creams with SPF (sun protection factor). Of particular interest are sunscreen creams, sunscreen lotions, sunscreen emulsions and sunscreen preparations.

[0040] The compositions of the present invention (including the carrier) may contain conventional adjuvants and additives such as preservatives / antioxidants, fatty substances / oils, organic solvents, silicones, thickeners, emollients, emulsifiers, antifoaming agents, aesthetic ingredients such as fragrances, surfactants, fillers, anionic, cationic, nonionic or amphoteric polymers or mixtures thereof, propellants, acidifying or basifying agents, dyes, colorants / colorants, abrasives, absorbents, chelating and / or sequestrants, essential oils, skin fresheners, astringents, pigments or any other ingredient usually incorporated into compositions of this type.

[0041] According to the invention, the compositions according to the invention may comprise further ingredients such as skin lightening, sun protection, treatment of hyperpigmentation, ingredients for preventing or reducing acne, wrinkles, fine lines, atrophy and / or inflammation, chelating and / or sequestrants, anti-cellulite and slimming (e.g. phytanic acid), firming, moisturizing and revitalizing, self-tanning, soothing and agents for improving elasticity and skin barrier, and / or further UV filter substances, as well as carriers and / or excipients or diluents conventionally used in topical compositions.

[0042] Unless otherwise specified, the following excipients, additives, diluents, etc. are suitable for topical compositions according to the present invention. The required amounts of cosmetic and dermatological adjuvants and additives can be readily determined by one skilled in the art based on the desired product.

[0043] Additional ingredients can be added to the oily phase, to the aqueous phase or separately, as deemed appropriate, the mode of addition being easily adaptable by one skilled in the art.

[0044] Examples of cosmetic excipients, diluents, adjuvants, additives, and active ingredients commonly used in the skin care industry that are suitable for use in the cosmetic compositions of the present invention are, for example, but not limited to, those listed in the International Cosmetic Ingredient Dictionary & Handbook by the Personal Care Product Council (http: / / www.personalcarecouncil.org / ), available online at INFO BASE (http: / / online.personalcarecouncil.org / jsp / Home.jsp).

[0045] Cosmetically active ingredients useful herein can sometimes provide more than one benefit or operate via more than one mechanism of action.

[0046] Naturally, the skilled person will select the above-mentioned optional additional components, adjuvants, diluents and additives and / or their amounts, taking into account that the advantageous properties inherently associated with the combination according to the invention are not adversely affected or are not substantially adversely affected by the addition(s) envisaged.

[0047] The topical compositions according to the invention may be in the form of a suspension or dispersion in a solvent or fatty substance, or in the form of an emulsion or microemulsion (in particular of the oil-in-water (O / W) or water-in-oil (W / O) type, silicone-in-water (Si / W) or water-in-silicone (W / Si) type, PIT-emulsion, multiple emulsion (for example of the oil-in-water-in-oil (O / W / O) or water-in-oil-in-water (W / O / W) type), Pickering emulsion, hydrogel, alcoholic gel, lipogel, single- or multiphase solution or vesicle dispersion, or other conventional forms which can also be applied by pen, as a facial pack or as a spray.

[0048] The topical composition according to the invention is advantageously in the form of an oil-in-water (O / W) emulsion comprising an oily phase dispersed in an aqueous phase in the presence of an O / W emulsion. The preparation of such O / W emulsions is well known to those skilled in the art and is illustrated in the examples.

[0049] In one advantageous embodiment, the O / W emulsifier is a phosphate ester emulsifier. Among the preferred phosphate ester emulsifiers are C 8~10 Alkyl ethyl phosphate, C 9~15 Alkyl phosphate, ceteareth-2 phosphate, ceteareth-5 phosphate, ceteth-8 phosphate, ceteth-10 phosphate, cetyl phosphate, (C 6-10 ) Pareth-4 phosphate, (C 12-15 ) Pareth-2 phosphate, (C 12-15 ) oleth-3 phosphate, ceteareth-2 phosphate DEA, cetyl phosphate DEA, oleth-3 phosphate DEA, potassium cetyl phosphate, deceth-4 phosphate, deceth-6 phosphate and trilaureth-4 phosphate. A specific phosphate ester emulsifier according to the invention is potassium cetyl phosphate, available commercially, for example, as Amphisol® K from DSM Nutritional Products Ltd Kaiseraugst.

[0050] Further suitable O / W emulsifiers according to the invention are PEG-30 dipolyhydroxystearate, PEG-4 laurate, PEG-8 dioleate, PEG-40 sorbitol oleate, PEG-7 glyceryl cocoate, PEG-20 glyceryl almondate, PEG-25 hydrogenated castor oil, glyceryl stearate (and) PEG-100 stearate, PEG-7 olivoate, PEG-8 oleate, PEG-8 laurate, PEG-60 glyceryl almondate, PEG-20 methylglucose sesquistearate, PEG-40 stearate, PEG stearate Contains G-100, PEG-80 sorbitan laurate, steareth-2, steareth-12, oleth-2, ceteth-2, laureth-4, oleth-10, oleth-10 / polyoxyethylene(10) oleyl ether, ceteth-10, isosteareth-20, ceteareth-20, oleth-20, steareth-20, steareth-21, ceteth-20, isoceteth-20, laureth-23, steareth-100, glyceryl stearate citrate, glyceryl stearate (self-emulsifying), stearic acid, salt of stearic acid, polyglyceryl-3 methylglucose distearate. Further suitable emulsifiers include sorbitan oleate, sorbitan sesquioleate, sorbitan isostearate, sorbitan trioleate, lauryl glucoside, decyl glucoside, sodium stearoyl glutamate, sucrose polystearate, and hydrated polyisobutene. Furthermore, one or more synthetic polymers can be used as emulsifiers. For example, VP / eicosene copolymer, acrylates / C10-30 alkyl acrylate crosspolymer, acrylates / steareth-20 methacrylate copolymer, PEG-22 / dodecyl glycol copolymer, PEG-45 / dodecyl glycol copolymer, and mixtures thereof.

[0051] Another particularly suitable class of O / W emulsifiers are the nonionic self-emulsifying systems derived from olive oil, known for example as (INCI name) cetearyl olivate and sorbitan olivate (chemical composition: sorbitan and cetearyl esters of olive oil fatty acids) sold under the trade name OLIVEM 1000.

[0052] Further suitable are commercially available polymeric emulsifiers, for example hydrophobically modified polyacrylic acids such as (acrylates / C10-30 alkyl acrylate) crosspolymers available from Noveon under the tradenames Pemulen® TR-1 and TR-2.

[0053] Another type of particularly suitable emulsifier is polyglycerol esters or diesters of fatty acids, also called polyglyceryl esters / diesters (i.e. polymers in which fatty acids are linked by esterification with polyglycerol), such as Isolan GPS (INCI name (diisostearate / polyhydroxystearate / sebacic acid) polyglyceryl-4 (i.e. diester of polyglycerol-4 with a mixture of isostearic acid, polyhydroxystearic acid and sebacic acid)), available from Evonik, or Dehymuls PGPH (INCI Polyglyceryl-2 Dipolyhydroxystearate) available from Cognis.

[0054] Also suitable are polyethylene glycol ethers such as Brij 72 (polyoxyethylene (2) stearyl ether) or Brij 721 (polyoxyethylene (21) stearyl ether), available from Croda.

[0055] Particularly advantageous O / W emulsifiers according to the invention are polyglyceryl-3 methylglucose distearate, lauryl glucoside (and) polyglyceryl-2 dipolyhydroxystearate, glyceryl sterate citrate, sodium cetearyl sulfate, cetearyl glucoside; polyglyceryl-6 stearate (and) polyglyceryl-6 behenate, cetearyl olivate (and) sorbitan olivate, arachidyl alcohol (and) behenyl alcohol (and) arachidyl glucoside, cetearyl alcohol (and) coco glucoside, coco glucoside (and) coconut alcohol, PEG-100 stearate (and) glyceryl stearate, sodium stearoyl glutamate, steareth-20, steareth-21, steareth-25, steareth-2, ceteareth-25 and ceteareth-6 (all listed by their INCI names).

[0056] The most preferred O / W emulsifiers according to the present invention are one or more of ceteareth-6 (optionally in a mixture with stearyl alcohol) and ceteareth-25.

[0057] The at least one O / W or Si / W emulsifier is preferably used in an amount ranging from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight, most particularly from 0.5 to 4% by weight, based on the total weight of the composition.

[0058] Suitable W / O or W / Si emulsifiers according to the invention are polyglyceryl-2 dipolyhydroxystearate, PEG-30 dipolyhydroxystearate, cetyl dimethicone copolyol, polyglyceryl-3 diisostearate, polyglycerol esters of oleic acid / isostearic acid, polyglyceryl-6 hexalicinoleate, polyglyceryl-4 oleate, polyglyceryl-4 oleate / PEG-8-PG cocoate, magnesium stearate, sodium stearate, potassium laurate, potassium ricinoleate, sodium cocoate, sodium tallowate, sodium castorate, sodium oleate and mixtures thereof. Further suitable W / O emulsifiers are lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and / or PEG-9 polydimethylsiloxyethyl dimethicone, and / or cetyl PEG / PPG-10 / 1 dimethicone, and / or PEG-12 dimethicone crosspolymer, and / or PEG / PPG-18 / 18 dimethicone. The at least one W / O emulsifier is preferably used in an amount of about 0.001 to 10% by weight, more preferably 0.2 to 7% by weight, relative to the total weight of the composition.

[0059] The topical composition according to the invention further advantageously contains at least one co-surfactant, such as one selected from the group consisting of mono- and diglycerides and / or fatty alcohols. The co-surfactant is generally used in an amount selected from the range of 0.1 to 10% by weight, particularly from 0.5 to 7% by weight, and most particularly from 1 to 5% by weight, based on the total weight of the composition. Specific and preferred co-surfactants are selected from the list of alkyl alcohols, such as cetyl alcohol (Lorol C16, Lanette 16), cetearyl alcohol (Lanette O), stearyl alcohol (Lanette 18), behenyl alcohol (Lanette 22), glyceryl stearate, glyceryl myristate (Estol 3650), hydrogenated cocoglycerides (Lipocire Na10), and mixtures thereof.

[0060] In a particularly advantageous embodiment according to the invention, the emulsifier is selected from the group of ceteareth-6 and / or ceteareth-25 and the co-surfactant is selected from the group of behenyl alcohol, cetyl alcohol, cetearyl alcohol and / or stearyl alcohol.

[0061] The composition in the form of an O / W emulsion according to the invention can be provided, for example, in any formulation form of an O / W emulsion, such as a serum, a milk or a cream, which are prepared according to the usual methods. The composition that is the subject of the present invention is intended for topical application and can in particular constitute a dermatological or cosmetic composition, intended, for example, to protect human skin against the harmful effects of ultraviolet radiation (anti-wrinkle, anti-aging, moisturizing, sun protection, etc.).

[0062] According to an advantageous embodiment of the invention, the composition constitutes a cosmetic composition and is intended for topical application to the skin.

[0063] Finally, the subject of the present invention is a method for cosmetically treating keratinous materials, in particular skin, in which a composition as defined above is applied to said keratinous materials, in particular skin, said method being particularly suitable for protecting the skin from the harmful effects of ultraviolet radiation, in particular sunburn and / or photoaging.

[0064] In one advantageous embodiment of the invention, the topical composition according to the invention does not contain (i.e. does not comprise) 3-(4-methylbenzylidene)-camphor, 2-hydroxy-4-methoxybenzophenone (INCI: oxybenzone) and ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: octocrylene).

[0065] In another advantageous embodiment, the topical composition according to the invention does not contain (i.e. does not include) ethylhexyltriazone.

[0066] In another advantageous embodiment of the invention, the topical composition according to the invention further comprises one or more of dibutyl adipate, dicaprylyl carbonate, C12-15 alkyl benzoate, caprylyl carbonate, caprylic / capric triglyceride and mixtures thereof, preferably C12-15 alkyl benzoate and / or dicaprylyl carbonate.

[0067] In a further advantageous embodiment of the present invention, the topical composition of the present invention further comprises a preservative and / or co-preservative, preferably selected from the group consisting of phenoxyethanol, ethylhexylglycerin, hexylglycerin, glyceryl caprylate, caprylyl glycol, 1,2-hexanediol, propanediol, propylene glycol, p-hydroxyacetophenone, and mixtures thereof, most preferably selected from the group of p-hydroxyacetophenone, phenoxyethanol, and hexylglycerin, and mixtures thereof. When present, the preservative or co-preservative is preferably used in an amount of 0.01 to 2% by weight, more preferably 0.05 to 1.5% by weight, and most preferably 0.1 to 1.0% by weight, based on the total weight of the composition.

[0068] In another advantageous embodiment, the topical composition according to the invention is free of parabens, benzethonium chloride, piroctone olamine, lauroylarginate, methylisothiazolinone, chloromethylisothiazolinone, bronopol, benzalkonium chloride, formaldehyde-releasing compounds, salicylic acid, triclosan, DMDM ​​hydantoin, chlorphenesin, and IPBC (iodopropynyl butylcarbamate).

[0069] In a further advantageous embodiment, the topical composition of the present invention further comprises one or more of glycerin or polyhydroxystearic acid, and mixtures thereof.

[0070] In a further advantageous embodiment, the topical composition of the invention further comprises a thickening agent, preferably a gum such as xanthan gum or Caesalpina spinosa gum or a polyacrylate such as polyacrylate crosspolymer-6, and mixtures thereof.

[0071] Topical compositions according to the present invention generally have a pH in the range of 3 to 10, preferably in the range of 4 to 8, and most preferably in the range of 4 to 7. The pH can be readily adjusted, if necessary, using a suitable acid, such as citric acid, or base, such as NaOH, according to standard methods in the art.

[0072] Topical compositions according to the present invention may further contain one or more emollients that soothe and soften the skin. By way of example, the emollients may be dicaprylyl carbonate or alkyl benzoate (C 12-15 Further emollients are silicones (dimethicone, cyclomethicone), vegetable oils (grape seed, sesame seed, jojoba, etc.), butters (cocoa butter, shea butter), alcohols (stearyl alcohol, cetyl alcohol) and petrolatum derivatives (petrolatum, mineral oil).

[0073] In still other embodiments, the topical compositions of the present invention may include potassium cetyl phosphate and / or one or more of dibutyl adipate, dicaprylyl carbonate, and alkyl (C12-15) benzoate as emulsifiers.

[0074] In other embodiments, the topical compositions of the present invention may comprise any of the following compounds: limonene, citral, linalool, α-isomethyl ionone, geraniol, citronellol, 2-isobutyl-4-hydroxy-4-methyltetrahydropyran, 2-tert-pentylcyclohexyl acetate, 3-methyl-5-phenyl-1-pentanol, 7-acetyl-1,1,3,4,4,6-hexamethyltetralin, adipic acid diester, cinnamal, amyl salicylate, α-amyl cinnamaldehyde, α-methyl ionone, butylphenyl methylpropional, cinnamal, amyl cinnamyl alcohol, anise alcohol, benzoin, benzyl alcohol, benzyl benzoate, benzyl cinnamate, benzyl salicylate, benzyl benzoic acid, benzyl salicylate, benzyl cinnamate, benzyl salicylate, benzyl benzoate ... The fragrance may contain one or more aromatic substances selected from lugamot oil, bitter orange oil, butylphenyl methylpropional, cardamom seed oil, cedrol, cinnamal, cinnamyl alcohol, citronellyl methylcrotonate, citrus oil, coumarin, diethyl succinate, ethyl linalool, eugenol, evernia furfurracea extract, hornwort extract, farnesol, guaiawood oil, hexyl cinnamal, hexyl salicylate, hydroxycitronellal, lavender oil, lemon oil, linalyl acetate, mandarin oil, menthyl PCA, methylheptenone, nutmeg kernel oil, rosemary oil, sweet orange oil, terpineol, tonka bean oil, triethyl citrate, and vanillin.

[0075] In other embodiments, the topical compositions of the present invention may contain at least one salt of 2-phenylbenzimidazole-5-sulfonic acid.

[0076] In other embodiments, the composition may have an SPF of at least 20, preferably at least 30.

[0077] The topical compositions of the present invention allow for surprisingly low total amounts of UV filters.

[0078] The formulations of the present invention may contain, in addition to the claimed UV filter combination, one or more further UV filters. According to the invention, these are advantageously phenylene-1,4-bis(2-benzimidazyl)-3,3',5,5'-tetrasulfonate; 1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts; 4-(2-oxo-3-bornylidenemethyl)-benzenesulfonate; 2-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonate; 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol); 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol; 3-benzylidenecamphor; terephthalidenedicamphor sulfate di(2-ethylhexyl) 4-methoxybenzalmalonate; isoamyl 4-methoxycinnamate; hexyl 2-(4'-diethylamino-2'-hydroxybenzoyl)benzoate, ethylhexyl salicylate, homomenthyl salicylate, 2-ethylhexyl 2-hydroxybenzoate; dimethicodiethyl benzalmalonate; 3-(4-(2,2-bis-ethoxycarbonylvinyl)-phenoxy)propenyl)methoxysiloxane / dimethylsiloxane copolymer; 4-(tert-butyl)-4'-methoxydibenzoylmethane, 1,4-di(benzoxazol-2'-yl)benzene, and 2,4,6-tribiphenyl-4-yl-1,3,5-triazine.

[0079] In a preferred embodiment, the present invention does not include 1,4-di(benzoxazol-2'-yl)benzene, especially micronized 1,4-di(benzoxazol-2'-yl)benzene.

[0080] According to the invention, the topical composition is advantageously in the form of an emulsion or dispersion, preferably in the form of an emulsion, more preferably in the form of an O / W emulsion.

[0081] When the topical composition according to the invention is in the form of an O / W emulsion, the formulation advantageously comprises one or more O / W emulsifiers chosen from glyceryl stearate citrate, glyceryl stearate (self-emulsifying), stearic acid, stearates, polyglyceryl-3 methylglycose distearate, sodium cetearyl sulfate, potassium cetyl phosphate, polyglyceryl-10 stearate and sodium stearyl glutamate.

[0082] Advantageously, according to the invention, these O / W emulsifiers of the invention may be present in the formulation in a concentration of 0.001 to 10% by weight, preferably 0.1 to 7% by weight, based on the total weight of the formulation.

[0083] According to the invention, preferably the formulation comprises potassium cetyl phosphate as emulsifier.

[0084] According to the invention, the formulation also advantageously comprises cetyl alcohol, stearyl alcohol and / or glyceryl stearate.

[0085] According to the invention, advantageously, the formulations of the invention are free of polyethylene glycols, polyethylene glycol ethers and polyethylene glycol esters (so-called PEG derivatives).

[0086] The formulations of the present invention may advantageously comprise a moisturizer, which is a compound or mixture of compounds that endows the cosmetic formulation with the quality of reducing water loss from the stratum corneum (also called transepidermal water loss (TEWL)) and / or favorably influencing the hydration of the stratum corneum after the cosmetic formulation has been applied or spread on the skin surface.

[0087] Non-limiting examples of moisturizing agents useful in the present invention include glycerol, lactic acid and / or lactate salts, especially sodium lactate, butylene glycol, propylene glycol, biosaccharide gum-1, wild soybean, ethylhexyloxyglycerol, pyrrolidone carboxylic acid, and urea. It is particularly advantageous to use polymeric moisturizing agents, particularly those from the group of water-soluble and / or water-swellable and / or water-gellable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan, and / or fucose-rich polysaccharides, such as those registered in Chemical Abstracts under registration number 178463-23-5 and available, for example, from SOLABIAS.A. under the name Fucogel® 1000. Moisturizing agents can also be advantageously used as anti-wrinkle active ingredients, for example, to protect the skin from changes caused by skin aging.

[0088] Advantageously, but not necessarily, the cosmetic preparations of the present invention may further comprise fillers, which, for example, further improve the sensory and cosmetic properties of the formulation, evoking or emphasizing the feel of velvet or silk. Advantageous fillers within the meaning of the present invention are starch and starch derivatives (e.g., tapioca starch, cross-linked starch, aluminum and sodium octenyl succinate starch, etc.), pigments that essentially have no UV filtering or coloring effect (e.g., boron nitride, etc.), and / or Aerosils® (CAS No. 7631-86-9), and / or talc, and / or polyethylene, nylon, and dimethylsilylated silica.

[0089] Advantageous embodiments of the formulations of the invention also include those in which the formulation comprises one or more oils selected from butylene glycol dicaprylate / dicaprate, phenethyl benzoate, C12-15 alkyl benzoate, dibutyl adipate, diisopropyl sebacate, dicaprylyl carbonate, C12-13 dialkyl tartrate, butyloctyl salicylate, diethylhexyl syringylidene malonate, hydrogenated castor oil dimer acid esters, triheptanoin, C12-13 alkyl lactate, C16-17 alkyl benzoate, propylheptyl caprylate, caprylic / capric triglyceride, diethylhexyl naphthalene dicarboxylate, octyldodecanol, and ethylhexyl cocoate.

[0090] According to the invention, formulations comprising dibutyl adipate, dicaprylyl carbonate and / or alkyl benzoate (C12-15) are preferred.

[0091] The aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic adjuvants, such as, in each case individually or in combination, alcohols, in particular those with a small number of carbon atoms, preferably ethanol and / or isopropanol, or polyols with a small number of carbon atoms as well as their ethers, preferably propylene glycol, glycerol, electrolytes, self-tanning agents, and in addition to these, in particular one or more thickeners, which may advantageously be selected from the group of silicon dioxide, aluminum silicate, polysaccharides and / or derivatives thereof, such as hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously polyacrylates, preferably thickeners from the group of polyacrylates known as Carbopols (examples of which include Carbopols of type 980, 981, 1382, 2984 and 5984). Further advantageous thickeners according to the invention are those with the INCI name (Acrylates / C10-30 Alkyl Acrylate) Crosspolymer (e.g. Pemulen TR 1, Pemulen TR 2, Carbopol 1328 from NOVEON), as well as Aristoflex AVC (INCI: (Ammonium Acryloyldimethyltaurate / VP) Copolymer) and Simugel NS (INCI: (Hydroxyethyl Acrylate / Sodium Acryloyldimethyltaurate) Copolymer and Squalane and Polysorbate 60).

[0092] In this regard, it is preferred according to the invention that the formulation comprises xanthan gum, crosslinked acrylates / C10-30 alkyl acrylate polymer, (hydroxyethyl acrylate / sodium acryloyldimethyl taurate) copolymer and squalane and polysorbate 60, and / or vinylpyrrolidone / hexadecene copolymer.

[0093] According to the invention, it is particularly advantageous to include at least 2.5% by weight of glycerol, based on the total weight of the formulation.

[0094] Advantageously, according to the invention, the formulation comprises one or more alkanediols from the group 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 2-methyl-1,3-propanediol.

[0095] According to the invention, advantageously, the formulations according to the invention comprise ethanol, phenoxyethanol and / or ethylhexylglycerin.

[0096] Advantageously, according to the invention, the formulation of the invention comprises a film-forming agent. Film-forming agents within the meaning of the present invention are substances of various compositions characterized by the following property: when they are dissolved in water or another suitable solvent and this solution is applied to the skin, they form a film after the solvent has evaporated, which essentially serves to fix the light-screening substance on the skin and to increase the water resistance of the product.

[0097] It is particularly advantageous if the film-forming agent is selected from the group of polymers based on polyvinylpyrrolidone (PVP).

[0098] Particularly preferred are copolymers of vinylpyrrolidone, such as (VP / hexadecene) and (VP / eicosene) copolymers available from GAF Chemicals Corporation under the tradenames Antaron V216 and Antaron V220.

[0099] Similarly, other polymeric film-forming agents are advantageous, such as sodium polystyrene sulfonate, available from National Starch and Chemical Corp. under the trade name Flexan 130, and / or polyisobutene, available from Rewo under the trade name Rewopal PIB1000. Further examples of suitable polymers are polyacrylamide (Seppigel 305), polyvinyl alcohol, PVP, PVP / VA copolymer, polyglycol, acrylate / octylacrylamide copolymer (Dermacryl 79). It is also advantageous to use hydrogenated castor oil dimer dilinoleate (CAS 646054-62-8, INCI hydrogenated castor oil dimer dilinoleate), available from Kokyu Alcohol Kogyo under the trade name Risocast DA-H, or else benzyl ether myristate PPG-3 (CAS 403517-45-3), available from Croda Chemicals under the trade name Crodamol STS.

[0100] According to the invention, the preparations according to the invention are used not only to protect the skin against ageing, in particular against UV-induced skin ageing, but also as sun protection compositions.

[0101] According to the invention, the inventive UV filter combinations are also used to reduce the adhesion of sand to cosmetic formulations, in particular sunscreen compositions. In this particular case, according to the invention, a combination of finely divided zinc oxide, 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: bisethylhexyloxyphenol methoxyphenyl triazine), 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof, and 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: diethylhexylbutamidotriazon) is used to reduce the adhesion of sand to cosmetic formulations, in particular sunscreen compositions. In this context, it is particularly advantageous that the zinc oxide has an average particle size Dn50, determined by laser diffraction, chosen in the range of 50 to 200 nm, preferably in the range of 75 to 150 nm, most preferably in the range of 90 to 130 nm, and a surface coating chosen from the group consisting of triethoxycaprylylsilane, octyltrimethoxysilane and dimethicone, preferably triethoxycaprylylsilane and dimethicone, most preferably triethoxycaprylylsilane.

[0102] The following examples are provided to further illustrate the compositions and effects of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.

[0103] [Example 1] The formulations (O / W emulsions) outlined in Table 1 were prepared according to standard methods in the art and then tested for sand resistance according to the method outlined below. - 30mg of cream (2mg / cm) on PMMA plate 2 ) and spread evenly. - Air dry for 15 minutes - Weigh the PMMA board - Place 30g of sand (Spielsand (Hornbach) sand for sand play, particle size 0.06-1mm) on this PMMA plate so that the surface is completely covered. - Air dry for 15 minutes - Rotate the PMMA plate 180° without shaking it - Weigh the PMMA board - Calculate the amount of sand adhering to the board - Repeat the test using four plates for each sample

[0104] The results are shown in Table 1.

[0105] [Table 1]

[0106] As can be seen from Table 1, by using the combination according to the present invention, adhesion of sand to the plate is synergistically reduced, that is, the sand adhesion prevention property is synergistically improved.

[0107] [Example 2] The formulations (O / W emulsions) outlined in Table 2 were prepared according to standard methods in the art and then tested for sand resistance according to the method outlined below. - PMMA plate with cream 2mg / cm 2 Apply and spread evenly - Dry at 40°C for 15 minutes - Weigh the PMMA board - Place sand (5 kg of Kultpfoetchen terrarium sand, natural beige, particle size 0.4-0.8 mm) in a petri dish, place the board so that the side with the cream film faces the sand, place a weight (500 g) on ​​the board, and leave it for 5 minutes. - Remove the PMMA plate and rotate it 180° without shaking it. - Weigh the PMMA board - Calculate the amount of sand adhering to the board - Repeat the test using four plates for each sample

[0108] The results are shown in Table 2.

[0109] [Table 2]

[0110] As can be seen from Table 2, the use of the combination according to the invention reduces the adhesion of sand to the board. Furthermore, the use of zinc oxide coated with triethoxycaprylylsilane is advantageous over the use of zinc oxide coated with dimethicone.

Claims

1. 1. A topical composition comprising: a.) Finely divided zinc oxide having an average particle size D selected in the range of 30 to 200 nm, as determined by laser diffraction ｎ 50 and a surface coating selected from the group consisting of aluminum stearate, stearic acid, methicone, simethicone, triethoxycaprylylsilane, and octyltrimethoxysilane; b.) 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bisethylhexyloxyphenol methoxyphenyl triazine), c.) 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof; d.) 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: Diethylhexylbutamidotriazone) and A topical composition comprising a combination of UV filters of the formula:

2. The average particle diameter D ｎ 2. The topical composition of claim 1, wherein 50 is selected in the range of 50 to 200 nm, preferably in the range of 75 to 150 nm, most preferably in the range of 90 to 130 nm, as determined by laser diffraction.

3. 3. The topical composition of claim 1, wherein the finely divided zinc oxide is surface coated with triethoxycaprylylsilane.

4. 4. The topical composition according to any one of claims 1 to 3, wherein the amount of the finely divided zinc oxide is selected in the range of 0.1 wt. % to 20 wt. %, preferably in the range of 0.5 wt. % to 10 wt. %, most preferably in the range of 5 wt. % to 10 wt. %, based on the total weight of the composition.

5. 5. The topical composition of any one of claims 1 to 4, which does not contain 3-(4-methylbenzylidene) camphor, 2-hydroxy-4-methoxybenzophenone (INCI: Oxybenzone), and ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: Octocrylene).

6. The topical composition according to any one of claims 1 to 5, which is an O / W emulsion.

7. 7. The topical composition of any one of claims 1 to 6, comprising one or more of ceteareth-6 and ceteareth-25 as emulsifiers.

8. 8. The topical composition of any one of claims 1 to 7, comprising one or more of dibutyl adipate, dicaprylyl carbonate, and alkyl (C12-15) benzoate.

9. The topical composition of any one of claims 1 to 8, comprising one or more of ethanol, p-hydroxyacetophenone, phenoxyethanol, and ethylhexylglycerin.

10. 10. The topical composition of any one of claims 1 to 9, comprising one or more of xanthan gum, crosslinked acrylates / C10-30 alkyl acrylate polymer, (hydroxyethyl acrylate / sodium acryloyldimethyltaurate) copolymer and squalane and polysorbate 60, and vinylpyrrolidone / hexadecene copolymer.

11. The topical composition of any one of claims 1 to 10, comprising one or more of cetyl alcohol, cetearyl alcohol, stearyl alcohol and glyceryl stearate.

12. 12. The topical composition of any one of claims 1 to 11, having an SPF of at least 20.

13. 1. Use of finely divided zinc oxide to reduce the stickiness of a topical composition comprising 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-ethylhexyloxyphenol methoxyphenyl triazine), 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof, and 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: Diethylhexylbutamidotriazon).

14. 1. A method for reducing stickiness and / or sandiness of a topical composition comprising 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), 2-phenylbenzimidazole-5-sulfonic acid and / or one or more salts thereof, and 4,4'-((6((4(((1,1-dimethylethyl)amino)carbonyl)phenyl)-amino)-1,3,5-triazine-2,4-diyl)diimino)bis(2-ethylhexyl)benzoate (INCI: Diethylhexylbutamidotriazon), the method comprising incorporating finely divided zinc oxide into the topical composition prior to applying the composition to the skin.

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