UV filter composition comprising closed cell metal oxide particles

Abstract

The present invention relates to a method for increasing the Sun Protection Factor (SPF) of a UV filter composition, to the use of closed cell metal oxide particles for increasing the SPF of a UV filter composition and to a UV filter composition comprising closed cell metal oxide particles.

Description

[Technical field]

[0001] The present invention relates to a method for increasing the Sun Protection Factor (SPF) of a UV filter composition, to the use of closed cell metal oxide particles for increasing the SPF of a UV filter composition and to a UV filter composition comprising closed cell metal oxide particles. [Background technology]

[0002] UV filter compositions are used to prevent the harmful effects of solar radiation on human skin. A wide variety of UV absorbers are available, and UV filter compositions often contain one or more UV absorbers to achieve high UV protection, i.e. a high Sun Protection Factor (SPF).

[0003] However, there is still a problem to obtain UV filter compositions with high SPF.Some UV filters are characterized by low solubility in the formulation mediums usually used, and therefore it is difficult to incorporate such low-solubility UV filters in large amounts into UV filter compositions.In addition, the maximum amount of UV filters that can be incorporated into UV filter compositions is controlled by government regulations.Therefore, there is a need for a method to increase the SPF of UV filter compositions.

[0004] The agents used to increase the SPF of UV filter compositions may lead to undesirable effects such as scattering of solar radiation, which may result in unpleasant appearance such as whitening of the face.Therefore, it is desirable that the method for increasing the SPF of UV filter compositions maintains its transparency and does not lead to undesirable effects such as whitening effect. Summary of the Invention [Problem to be solved by the invention]

[0005] It is therefore an object of the present invention to provide a method for increasing the SPF of a UV filter composition.Furthermore, it is an object of the present invention to provide a UV filter composition that is free of undesirable appearance problems such as whitening effects. [Means for solving the problem]

[0006] Surprisingly, it has been found that by adding closed cell metal oxide particles to a UV filter composition, the Sun Protection Factor (SPF) of the UV filter composition can be increased.

[0007] Thus, an embodiment of the present invention relates to a method for increasing the sun protection factor of a UV filter composition, comprising adding closed cell metal oxide particles to the UV filter composition, the closed cell metal oxide particles comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume, the outer surface of the closed cell metal oxide particles being defined by the array of closed cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0008] Another aspect of the present invention relates to the use of closed cell metal oxide particles to increase the sun protection factor of UV filter compositions.The closed cell metal oxide particles comprise a metal oxide matrix that defines an array of closed cells, each closed cell enclosing a void volume, and the outer surface of the closed cell metal oxide particles is defined by the array of closed cells.The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.

[0009] Yet another aspect of the present invention relates to a UV filter composition comprising closed cell metal oxide particles in the range of 0.1-25.0 wt. %, based on the total weight of the UV filter composition. The closed cell metal oxide particles comprise a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume, and the outer surface of the closed cell metal oxide particles being defined by the array of closed cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof. [Brief description of the drawings]

[0010] [Figure 1] 1 is a graph showing the absorbance in the range of 290 to 450 nm of UV filter composition 1 (placebo), composition 2 (3 wt. % closed cell metal oxide particles according to Example 2) and composition 4 (comparative example). [Diagram 2] 1 is a graph of the absorbance in the range 290-450 nm of UV filter composition 1 (placebo), composition 2 (3 wt. % closed cell metal oxide particles according to Example 2) and composition 3 (commercial UV protection boost). [Diagram 3] 1 shows a chart for the lightness L* of UV filter composition 1 (placebo), composition 2 (3 wt. % closed cell metal oxide particles according to Example 2) and composition 3 (commercial UV protection boost). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Before describing the compositions and formulations of the present invention, it is to be understood that the invention is not limited to the particular compositions and formulations described, as such compositions and formulations may, of course, vary. It is also to be understood that the terms used herein are not intended to be limiting, since the scope of the invention claimed herein will be limited only by the appended claims.

[0012] Hereinafter, when a group is defined as including at least a certain number of embodiments, this is meant to include preferred groups consisting of only these embodiments. Furthermore, terms such as "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" in this specification and claims are used to distinguish similar components and are not necessarily intended to describe sequential or chronological order. Therefore, it should be understood that the terms used in this specification are interchangeable under appropriate circumstances and that the embodiments of the invention described herein can be implemented in other orders than those described or illustrated herein. Where the terms "first", "second", "third", or "(A)", "(B)" and "(C)", or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. refer to steps of a method or use or assay, unless otherwise specified in this application, as hereinbefore or hereinafter described, there is no time or consistency between the steps, i.e. the steps may be performed simultaneously or there may be a time interval of seconds, minutes, hours, days, weeks, months or even years between such steps.

[0013] Additionally, ranges defined throughout this specification are inclusive of the end values, i.e., a range of 1 to 10 is intended to include both 1 and 10. For the avoidance of doubt, the applicant reserves the right to any equivalents available under applicable law.

[0014] In the following text, various aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects, unless expressly indicated otherwise. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

[0015] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrase "one embodiment" or "an embodiment" in various places throughout this specification do not necessarily all refer to the same embodiment, although they may.

[0016] Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments. Additionally, as will be understood by one of ordinary skill in the art, some embodiments described herein may include some features included in other embodiments but not other features, meaning that combinations of features from different embodiments are within the scope of the invention and form different embodiments. For example, in the appended claims, any of the claimed embodiments may be used in any combination.

[0017] It has been found that it is possible to use closed cell metal oxide particles to increase the SPF of UV filter compositions.The present invention provides a method for increasing the SPF of UV filter compositions, and also provides UV filter compositions with high SPF.Furthermore, it is observed that the obtained UV filter compositions do not show the adverse effects on appearance, such as whitening effect, that are usually associated with the addition of agents that scatter radiation.

[0018] Closed cell metal oxide particles are structural colorants that interact with UV and visible radiation via light interference effects. Structural colorants are materials that contain nano-sized structured surfaces that are small enough to interfere with visible light and produce color. Bulk samples of closed cell metal oxide particles exhibit saturated colors with reduced undesirable light scattering when the porosity and / or microsphere diameter and / or pore size are within a certain range. As a result, the presence of closed cell metal oxide particles in the UV filter composition leads to a reduction in the amount of radiation that passes through the UV filter composition layer. Thus, an overall reduction in the transmittance of the dye or UV absorber is achieved without increasing its concentration.

[0019] Thus, one aspect of the present invention relates to a method for increasing the sun protection factor of a UV filter composition, comprising adding closed cell metal oxide particles to the UV filter composition, the closed cell metal oxide particles comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume, the outer surface of the closed cell metal oxide particles being defined by the array of closed cells, the metal oxide matrix comprising at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0020] Therefore, another aspect of the present invention relates to the use of closed cell metal oxide particles for increasing the sun protection factor of a UV filter composition, the closed cell metal oxide particles comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume, and the outer surface of the closed cell metal oxide particles being defined by the array of closed cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0021] In a preferred embodiment, the void volume is media impermeable.

[0022] In the context of the present invention, the SPF factor (Sun Protection Factor, SPF) is useful for evaluating photoprotective formulations (UV filter compositions) in humans (in vivo). SPF indicates how long a person using a UV filter agent can be exposed to the sun for longer than a particular individual's self-protection time without getting sunburn. SPF is determined in vitro by measuring the diffuse transmittance in the spectral range of 290-400 nm.

[0023] In the context of the present invention, the term "monodisperse" with respect to spheres, microspheres or nanospheres means particles having a generally uniform shape and a generally uniform diameter. This monodisperse population of spheres, microspheres or nanospheres may have 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the particles by number having a diameter within ±7%, ±6%, ±5%, ±4%, ±3%, ±2% or ±1% of the mean diameter of the population.

[0024] In the context of the present invention, the terms "particle", "microsphere", "microparticle", "nanosphere", "nanoparticle", "droplet" and the like also refer to, for example, a plurality thereof, a collection thereof, a population thereof, a sample thereof or a bulk sample thereof.

[0025] In the context of the present invention, the term "bulk sample" refers to a population of particles. For example, a bulk sample of particles is simply a bulk population of particles, e.g., ≧0.1 mg, ≧0.2 mg, ≧0.3 mg, ≧0.4 mg, ≧0.5 mg, ≧0.7 mg, ≧1.0 mg, ≧2.5 mg, ≧5.0 mg, ≧10.0 mg, or ≧25.0 mg. A bulk sample of particles may be substantially free of other components.

[0026] In the context of the present invention, the expression "exhibiting a color observable by the human eye" means that the color would be observed by an average person. This applies to a bulk sample distributed over any surface area, e.g. 1 cm 2 , 2cm 2, 3cm 2 , 4cm 2 , 5cm 2 Or 6 cm 2 7cm from either 2 , 8cm 2 , 9cm 2 , 10cm 2 , 11cm 2 , 12cm 2 , 13cm 2 , 14cm 2 Or 15cm 2 It can be for a bulk sample distributed over a surface area up to either the CIE 1931 2° standard observer and / or the CIE 1964 10° standard observer. The background for color observation can be any background, such as a white background, a black background, or a dark background between white and black.

[0027] In the context of the present invention, the term "micro" or "microscale", for example, when referring to a particle, means from 1 micrometer (μm) to less than 1000 μm. The term "nano" or "nanoscale", for example, when referring to a particle, means from 1 nanometer (nm) to less than 1000 nm.

[0028] In the context of the present invention, the term "medium impermeable" in relation to a volume means that the volume is shielded from infiltration by large molecules (e.g., molecules having a molecular weight greater than 5000 g / mol, such as polymers and oligomers). The volume may be permeable by solvents such as water, toluene, hexane and ethanol.

[0029] In the context of the present invention, the terms "microsphere", "nanosphere", "droplet" and the like referred to herein may refer to, for example, a plurality thereof, a collection thereof, a population thereof, a sample thereof or a bulk sample thereof.

[0030] In the context of the present invention, the term "micro" or "microscale" means from about 0.5 μm to 999 μm. The term "nano" or "nanoscale" means from about 1 nm to 999 nm.

[0031] In the context of the present invention, the terms "sphere" and "particle" are interchangeable.

[0032] Unless otherwise indicated, all parts and percentages referred to herein are by weight. Weight percent (wt%) is based on the total composition, i.e., dry solids content, without any volatiles, unless otherwise indicated.

[0033] In a preferred embodiment, the amount of closed cell metal oxide particles ranges from 0.1 to 25.0% by weight, based on the total weight of the UV filter composition.

[0034] In a preferred embodiment, the amount of closed cell metal oxide particles ranges from 0.5 to 10.0% by weight, based on the total weight of the UV filter composition.

[0035] In a preferred embodiment, the array of closed cells is an ordered array.

[0036] In a preferred embodiment, the array of closed cells is a random array.

[0037] The terms "ordered" and "disordered" closed cells refer to a structure of closed cells defined by a metal oxide matrix. In the case of an "ordered" array, the closed cells have a structure of a repeating pattern in the matrix. According to a preferred embodiment, the ordered array results in an angle-dependent color. In the case of a "disordered" array, the closed cells have a random structure with no particular pattern in the matrix. According to a preferred embodiment, the disordered array results in an angle-independent color.

[0038] The terms "ordered array of closed cells" and "ordered voids" are meant to be understood interchangeably. The terms "disordered array of closed cells" and "disordered voids" are meant to be understood interchangeably.

[0039] In a preferred embodiment, the closed cell metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm; more preferably 1.0 μm to 75.0 μm; even more preferably 2.0 μm to 50.0 μm; and most preferably 3.0 μm to 25.0 μm.

[0040] In a preferred embodiment, the closed cell metal oxide particles comprise primarily metal oxide, ie, they may consist essentially of or consist of metal oxide.

[0041] In a preferred embodiment, the amount of metal oxide in the closed cell metal oxide particles is in the range of 60.0 to 100.0 wt %, more preferably 65.0 to 99.9 wt %, even more preferably 70.0 to 99.9 wt %, and most preferably 75.0 to 99.0 wt %, based on the total weight of the closed cell metal oxide particles.

[0042] In a preferred embodiment, the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 500 nm.

[0043] In a preferred embodiment, the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 400 nm.

[0044] In a preferred embodiment, the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 300 nm; more preferably 10 nm to 300 nm; even more preferably 25 nm to 250 nm; and most preferably 50 nm to 200 nm.

[0045] In a preferred embodiment, the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.90.

[0046] In a preferred embodiment, the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.80; more preferably 0.20 to 0.75; even more preferably 0.30 to 0.70; and most preferably 0.40 to 0.70.

[0047] In a preferred embodiment, the metal oxide matrix comprises silica.

[0048] In a preferred embodiment, the metal oxide matrix comprises alumina.

[0049] In a preferred embodiment, the metal oxide matrix comprises titania.

[0050] In a preferred embodiment, the metal oxide matrix comprises silica and alumina.

[0051] In a preferred embodiment, the metal oxide matrix comprises silica and titania.

[0052] In a preferred embodiment, the metal oxide matrix comprises silica and zinc oxide.

[0053] The metal oxide particles are used in the preparation of a metal oxide matrix.

[0054] In a preferred embodiment, the metal oxide particles are fused together during preparation, resulting in a continuous metal oxide matrix.

[0055] In a preferred embodiment, a combination of two or more different types of metal oxide particles is used in the preparation of the closed cell metal oxide particles. The combination of metal oxide particles may include two or more populations having different compositions and / or morphologies.

[0056] In a preferred embodiment, the metal oxide particles comprise two or more populations having different particle sizes.

[0057] In a preferred embodiment, the metal oxide particles include particles where each particle is made from two or more different metal oxides.

[0058] In a more preferred embodiment, the metal oxide particles include particles where each particle is made from silica and titania.

[0059] In a preferred embodiment, the closed cells are monodisperse.

[0060] In a preferred embodiment, the closed cells have a bimodal distribution of monodisperse closed cells.

[0061] In a preferred embodiment, the closed cells are polydisperse.

[0062] In a preferred embodiment, the closed cell metal oxide particles are prepared using a polymeric sacrificial template.

[0063] According to one embodiment of the present invention, the closed cell metal oxide particle has an additional sealing layer. The sealing layer may be present on some or all of the closed cells of the closed cell metal oxide particle. In a particularly preferred embodiment, the sealing layer comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof. Most preferably, the sealing layer comprises silica.

[0064] According to another embodiment of the present invention, the closed cell metal oxide particles do not include a sealing layer.

[0065] In a preferred embodiment, the closed cell metal oxide particles are prepared by a method comprising the following steps. - generating droplets from a particle dispersion comprising first particles comprising a polymeric material and second particles comprising a metal oxide material; - drying the droplets to provide dried particles comprising an array of first particles, each of the first particles being coated with a layer of second particles; and - calcining or sintering the dried particles, which densifies the metal oxide material and removes the polymeric material to produce closed cell metal oxide particles each comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume, and an outer surface of the closed cell metal oxide particles being defined by the respective array of closed cells.

[0066] In a preferred embodiment, the first particle comprises a surface carrying a net positive charge and the second particle comprises a surface carrying a net negative charge.

[0067] In a preferred embodiment, the first particle comprises a surface that carries a net negative charge and the second particle comprises a surface that carries a net positive charge.

[0068] In a preferred embodiment, the surface charge promotes the formation of a layer of the second particle on the first particle.

[0069] In a preferred embodiment, the polymeric material comprises a polymer selected from poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, copolymers of methyl methacrylate and [2-(methacryloyloxy)ethyl]trimethylammonium chloride, derivatives thereof, salts thereof, copolymers thereof or mixtures thereof.

[0070] In a preferred embodiment, the first particles have an average diameter of from 50 nm to 500 nm.

[0071] In a preferred embodiment, the metal oxide material comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof.

[0072] In a preferred embodiment, the second particles have an average diameter of from 1 nm to 120 nm.

[0073] In a preferred embodiment, droplet generation is performed using microfluidic processes.

[0074] In a preferred embodiment, the generation and drying of the droplets is carried out using a spray drying process.

[0075] In a preferred embodiment, droplet generation is achieved using a vibrating nozzle.

[0076] In a preferred embodiment, drying of the droplets comprises evaporation, microwave irradiation, oven drying, drying under vacuum, drying in the presence of a desiccant, or a combination thereof.

[0077] In a preferred embodiment, the particle dispersion is an aqueous particle dispersion.

[0078] In a preferred embodiment, the weight ratio of the first particles to the second particles is selected from 1 / 10 to 10 / 1.

[0079] In preferred embodiments, the weight ratio of the first particles to the second particles is selected from 2 / 3, 1 / 1, 3 / 2 or 3 / 1.

[0080] In a preferred embodiment, the weight ratio of the first particles to the second particles is selected from 1 / 50 to 1 / 5.

[0081] In a preferred embodiment, the closed cell metal oxide particles are prepared by a method comprising: - generating droplets from a particle dispersion comprising polymer particles comprising a polymeric material in a sol-gel matrix of metal oxide particles; - drying the droplets to provide dried particles comprising an array of polymer particles each coated with a sol-gel matrix; and - calcining or sintering the dried particles to obtain closed cell metal oxide particles, which calcination or sintering removes the polymeric material and densifies the metal oxide material to produce closed cell metal oxide particles each comprising a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume inaccessible to a medium, and an outer surface of the closed cell metal oxide particles being defined by the respective array of closed cells.

[0082] In a preferred embodiment, the polymer particles comprise a surface that carries a net positive charge and the sol-gel matrix of the metal oxide material comprises a net negative charge.

[0083] In a preferred embodiment, the polymer particles comprise a surface that carries a net negative charge and the sol-gel matrix of the metal oxide material comprises a net positive charge.

[0084] Advantageously, depending on the composition of the metal oxide particles, their relative size and shape, bulk samples of the closed cell metal oxide particles may exhibit a color observable by the human eye, may appear white, or may exhibit characteristics in the UV range of the spectrum.

[0085] Bulk samples of the closed cell metal oxide particles described herein may exhibit angle-dependent or angle-independent color. "Angle-dependent" color means that the observed color has a dependence on the angle of incident light on the sample or the angle between the observer and the sample. "Angle-independent" color means that the observed color is substantially independent of the angle of incident light on the sample or the angle between the observer and the sample.

[0086] In a preferred embodiment, the angle-dependent color is achieved by an ordered arrangement of closed cells.

[0087] In a preferred embodiment, angle-independent color is achieved by a random array of closed cells.

[0088] In a preferred embodiment, angle-dependent color is achieved when the closed cells are monodisperse.

[0089] In a preferred embodiment, angle-independent color is achieved when the closed cells are polydisperse.

[0090] In a preferred embodiment, angle-independent color is achieved when the closed cells exhibit a bimodal distribution of monodisperse polymer particles.

[0091] In a preferred embodiment, angle-independent color is achieved independent of the polydispersity and shape of the matrix particles.

[0092] Any of the embodiments that exhibit angle-dependent or angle-independent color can be modified to exhibit effects in whiteness or the ultraviolet spectrum.

[0093] In a preferred embodiment, the closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. Contains monodisperse closed cells.

[0094] In a preferred embodiment, the closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. Monodisperse closed cell metal oxide particles comprising closed cells having a bimodal distribution.

[0095] In a preferred embodiment, the closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. Contains polydisperse closed cells.

[0096] In a preferred embodiment, the closed cell metal oxide particles further comprise a light absorber.

[0097] In a preferred embodiment, the light absorber is present in the range of 0.1 to about 40.0 weight percent, more preferably 0.5 to 25.0 weight percent, and most preferably 1.0 to 10.0 weight percent.

[0098] In a preferred embodiment, the light absorber comprises at least one ionic species.

[0099] In a preferred embodiment, the closed cell metal oxide particles exhibit color in the visible spectrum at wavelengths ranging from 380 nm to 800 nm.

[0100] In a preferred embodiment, the closed cell metal oxide particles are effective in a wavelength range in the ultraviolet spectrum selected from the group consisting of 100 nm to 400 nm.

[0101] In a preferred embodiment, the closed cell metal oxide particles exhibit efficacy in a wavelength range in the ultraviolet and visible spectrum selected from the group consisting of 200 nm to 500 nm.

[0102] In a preferred embodiment, the UV filter composition comprises a UV absorber selected from the group consisting of: (d1) p-aminobenzoic acid derivatives; (d2) Salicylic acid derivatives; (d3) benzophenone derivatives; (d4) dibenzoylmethane derivatives; (d5) diphenyl acrylate; (d6) 3-imidazol-4-yl-acrylic acid and its esters; (d7) benzofuran derivatives; (d8) polymeric UV absorbers; (d9) cinnamic acid derivative; (d 10 ) camphor derivatives; (d 11 ) hydroxyphenyltriazine derivatives; (d 12 ) benzotriazole derivatives; (d 13 ) trianilino-s-triazine derivatives; (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d 15 ) o-aminobenzoic acid methyl ester; (d 16 ) Homosalate; (d 17 ) tris-biphenyltriazine derivatives; (d 18 ) TiO2, ZnO and mica; (d 19 ) benzylidene malonate; (d 20 ) merocyanine derivatives; (d 21 ) phenylenebis-diphenyltriazine; (d 22 ) imidazoline derivatives; (d 23 ) diarylbutadiene derivatives; (d 24 ) aminohydroxybenzoyl hexyl benzoate derivatives; (d 25 ) bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives, and A mixture of them.

[0103] Examples of p-aminobenzoic acid derivatives (d1) that can be utilized according to the present invention are 4-aminobenzoic acid (PABA); [ka] of ethyl dihydroxypropyl-PABA; [ka] PEG-25PABA (wherein m, n and x have the same meaning and each represents an integer of 1 to 25); [ka] octyl dimethyl PABA of the formula: [ka] It is glycyl aminobenzoate.

[0104] Examples of salicylic acid derivatives (d2) that can be utilized according to the present invention are The following formula: [ka] of homomenthyl salicylate; The following formula: [ka] of triethanolamine salicylate; The following formula: [ka] amyl p-dimethylaminobenzoate; The following formula: [ka] of octyl salicylate; or The following formula: [ka] 4-Isopropylbenzyl salicylate It is.

[0105] Examples of benzophenone derivatives (d3) that can be utilized according to the present invention are benzophenone-3-(2-hydroxy-4-methoxybenzophenone); benzophenone-4-(2-hydroxy-4-methoxybenzophenone-5-sulfonic acid); benzophenone-8-(2,2'-dihydroxy-4-methoxybenzophenone); or [ka] (In the formula, R1 and R2 are hydrogen, C1-C 20 -Alkyl, C2-C 10 -Alkenyl, C3-C 10 -Cycloalkyl, C3-C 10 -cycloalkenyl, where the substituents R1 and R2, together with the nitrogen atom to which they are attached, can form a 5- or 6-membered ring; R3 and R4 are each independently selected from C1 to C 20 -Alkyl; C2-C 10 -Alkenyl; C3~C 10 -Cycloalkyl; C3-C 10 -Cycloalkenyl; C1-C 22 -Alkoxy; C1-C 20 -Alkoxycarbonyl; C1-C 12 -Alkylamino; C1-C 12 -dialkylamino; optionally substituted aryl; hetaryl; a substituent that confers solubility in water selected from the group consisting of a nitrile group and a carboxylate, sulfonate or ammonium group; X represents hydrogen; COOR5; or CONR6R7; R5, R6, and R7 are each independently hydrogen; 20 -Alkyl; C2-C 10 -Alkenyl; C3~C 10 -Cycloalkyl; C3-C 10 -cycloalkenyl; (YO) o -Z; or aryl; Z represents -CH2-CH3; -CH2-CH2-CH3; -CH2-CH2-CH2-CH3; or -CH(CH3)-CH3; m represents 0 to 3; n represents 0 to 4; and (o represents 1 to 20) is an amino-substituted hydroxybenzophenone.

[0106] In a more preferred embodiment, the UV absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

[0107] The benzophenone derivative (d3) has the following formula: [ka] (In the formula, R1 and R2 are each independently C1 to C 20 -Alkyl; C2-C 20 -Alkenyl; C3~C 10 -Cycloalkyl; C3-C 10 -cycloalkenyl, or R1 and R2 together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocycle; R3 is an alkylene, cycloalkylene, alkenylene or phenylene optionally substituted with a carbonyl or carboxyl group; * -CH2-C≡C-CH2- * or R3 together with A represents a divalent group of the formula (HBP-03b) [ka] forming a divalent group of n2 represents an integer of 1 to 3; A represents -O-; or -N(R5)-; and R5 represents hydrogen; C1-C5-alkyl; or hydroxy-C1-C5-alkyl. benzophenone derivatives according to the formula:

[0108] In a more preferred embodiment, [ka] The dimeric benzophenone derivative is used as a UV absorber (d3).

[0109] An example of a dibenzoylmethane derivative (d4) that can be utilized according to the present invention is butyl methoxydibenzoylmethane-[1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione].

[0110] Examples of diphenylacrylate derivatives (d5) that can be utilized according to the present invention are octocrylene (2-ethylhexyl 2-cyano-3,3'-diphenylacrylate) or etocrylene (ethyl 2-cyano-3,3'-diphenylacrylate).

[0111] Examples of benzofuran derivatives (d7) which can be used according to the invention are 3-(benzofuranyl) 2-cyanoacrylate, 2-(2-benzofuranyl)-5-tert-butylbenzoxazole or 2-(p-aminophenyl)benzofuran, in particular those of the formula [ka] It is a compound of the formula:

[0112] Examples of polymeric UV absorbers (d8) which can be used according to the invention and which contain one or more organosilicon groups are benzylidene malonate derivatives, in particular those of the formula [ka] (In the formula, R 24 represents hydrogen or methoxy, and r represents about 7. A compound of the formula: [ka] or a compound of the formula [ka] The corresponding polysilicone-15 is

[0113] Examples of cinnamic acid esters (d9) which can be utilized according to the present invention are octyl methoxycinnamate (4-methoxycinnamic acid 2-ethylhexyl ester), diethanolamine methoxycinnamate (diethanolamine salt of 4-methoxycinnamic acid), isoamyl p-methoxycinnamate (4-ethoxycinnamic acid 2-isoamyl ester), 2,5-diisopropyl methoxycinnamate or cinnamic acid amide derivatives.

[0114] Camphor derivatives (d 10 Examples of benzylidene camphor-[3-(4'-methyl)benzylidene bornan-2-one], 3-benzylidene camphor-(3-benzylidene bornan-2-one), polyacrylamidomethyl benzylidene camphor {N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer}, trimoniumbenzylidene camphor sulfate-[3-(4'-trimethylammonium)-benzylidene bornan-2-one methyl sulfate], terephthalenedicamphorsulfonic acid {3,3'-(1,4-phenylenedimethine)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]heptane-1-methanesulfonic acid} or a salt thereof, or benzylidene-camphorsulfonic acid [3-(4'-sulfo)benzylidene bornan-2-one] or a salt thereof.

[0115] Hydroxyphenyltriazine derivatives (d 11 Examples of ) are in particular those of the formula [ka] (In the formula, R1 and R2 are each independently hydrogen; 18 -Alkyl; C2-C 18-alkenyl; a radical of the formula -CH2-CH(-OH)-CH2-O-T1; [ka] A group of the formula: [ka] is the basis of; R3, R4 and R5 are each independently a hydroxyl; a C1-C5-alkoxy which is unsubstituted or substituted by one or more OH groups; an amino; a mono- or di-C1-C5-alkylamino; M; a group represented by the following formula (HPT-01b): [ka] is the basis of; R 10 , R 11 and R 12 are, independently of one another, C1-C which are unsubstituted or substituted with one or more OH groups; 14 - represents alkyl; R 13 is hydrogen; M; C1-C5-alkyl; or the following formula -(CH2) m3 represents the group -O-T1; R6 is a direct bond; a linear or branched C1-C4 alkylene group; or a group represented by the following formula -C m4 H 2m4 Or -C m4 H 2m4 represents the group -O-; R7, R8 and R9 are each independently selected from C1 to C 18 -Alkyl; C1-C 18 -alkoxy or the formula: [ka] represents a group; R 14 represents C1-C5-alkyl; M represents a metal cation; T1 represents hydrogen; or (C1-C8)-alkyl; m1, m2, and m3 each independently represent 1 to 3; m4 represents 2 to 14; and p1 represents 0 or a number from 1 to 5. It is a bis-resorcinyltriazine.

[0116] In a preferred embodiment, the compound class (d 11 )teeth, - 2-(4'-methoxyphenyl)-4,6-bis(2'-hydroxy-4'-n-octyloxyphenyl)-1,3,5-triazine; - 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; - 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethylcarboxyl)phenylamino]-1,3,5-triazine; - 2,4-bis{[4-(tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; - 2,4-bis{[4-(2''methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; - 2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethyltrisilyl-2''-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; - 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-[4-ethylcarboxyl)phenylamino]-1,3,5-triazine; 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)-1,3,5-triazine; or - 2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-[(2-ethylhexyl)oxy]-(bis-ethylhexyloxyphenol methoxyphenyl triazine) (the formula [ka] (corresponding to It is.

[0117] Benzotriazole derivatives (d 12 ) is the formula [ka] (In the formula, R1 is hydrogen; C1-C 12 -Alkyl; C1-C 12 -Alkoxy; C1-C 12 -Alkoxycarbonyl; C5~C 10 -cycloalkyl or -SO3M; R3 is hydrogen; C1-C 18 -Alkyl; C1-C 12 -alkoxy; or halogen; and n represents 1 or 2; For n=1, R2 is C1~C 20 -Alkyl; C5~C 10 -Cyclo-C1-C5-alkyl; C1-C 12 -Alkoxy-C1-C5-alkyl; C5-C 10 -Cycloalkoxy-C1-C5-alkyl;C6-C 10 -Aryl; C6~C 10 -aryl-C1-C5-alkyl; For n=2, R2 is a direct bond; or -(CH2) p - stands for; and p is an integer from 1 to 3. Corresponds to.

[0118] In a preferred embodiment, R1 is C1~C 12 -alkyl; or -SO3M; R3 represents hydrogen; halogen, preferably Cl; n represents 1; R2 is C1~C 12 -alkyl; and Compounds of formula (BT-01) where p represents 1-3 are possible.

[0119] In a more preferred embodiment, the benzotriazole derivative (d 12 ) is expressed as follows: [ka] It is a compound of the formula:

[0120] In a more preferred embodiment, the UV filter of formula BT-01 is R1 represents hydrogen; R3 is C1~C 18 - represents alkyl; n=2; and The compound is wherein R2 represents -CH2-.

[0121] In a more preferred embodiment, the benzotriazole derivative (d 12 ) is expressed as follows: [ka] It is a compound of the formula:

[0122] Trianilino-s-triazine derivatives (d 13 ) is the formula [ka] (In the formula, R1, R2 and R3 are each independently an optionally substituted C1-C 20 - represents alkyl, aryl or hetaryl; X represents O; or NR4; and R4 is hydrogen; or optionally substituted C1-C 20 -represents alkyl, aryl or hetaryl Corresponds to.

[0123] In a preferred embodiment, trianilino-s-triazine derivatives (d 13 ) The compound has the following formula: [ka] or ethylhexyl triazone corresponding to the formula: [ka] or diethylhexylbutamide triazone corresponding to the formula: [ka] is ethylhexyl bis-isopentyl benzoxazolyl phenyl melamine, which corresponds to

[0124] 2-Phenylbenzimidazole-5-sulfonic acid and its salts (d 14 An example of such a compound is disodium 2,2'-(1,4-phenylene)bis(6-sulfo-1H-1,3-benzimidazole-4-sulfonate (disodium bisdisulfuric acid).

[0125] Tris-biphenyl-triazine derivatives (d 17 ) is the formula [ka] (In the formula, A is the following formula: [ka] represents a group of R1 and R5 are each independently hydrogen; 18 -alkyl; or C6-C 12 - represents aryl; R2, R3 and R4 are each independently hydrogen; or [ka] wherein in formula (TBT-01a), at least one of the groups R2, R3 and R4 represents a group of formula (TBT-01c); R6, R7, R8, R9 and R 10 are each independently hydrogen; hydroxyl; halogen; C1-C 18 -Alkyl; C1-C 18 -Alkoxy; C6~C 12 -Aryl;Biphenylyl;C6~C 12 -Aryloxy; C1-C 18 -Alkylthio;Carboxyl;-COOM;C1~C 18 -Alkylcarboxyl; aminocarbonyl; or mono- or di-C1-C 18 -Alkylamino; C1-C 10 -Acylamino; -COOH; M represents an alkali metal ion; x represents 1 or 2; and y represents an integer from 2 to 10. Corresponds to.

[0126] In a preferred embodiment, the UV filters (d 17 ) is expressed as follows: [ka] Corresponds to.

[0127] Benzylidene malonates (d 19 ) is the formula [ka] (In the formula, R1 represents methyl; ethyl; propyl; or n-butyl; When R1 represents methyl, R is tert-butyl [ka] ;The following formula [ka] or a group of the formula [ka] represents a group of R2 and R3 are, independently of each other, hydrogen; or methyl; R4 is methyl; ethyl; or n-propyl; R5 and R6 are, independently of each other, hydrogen; or C1-C3-alkyl; When R1 represents ethyl; propyl; or n-butyl, R represents isopropyl. Corresponds to.

[0128] In a preferred embodiment, benzylidene malonates (d 19 ) are shown in the table below.

[0129] [Table 1]

[0130] [Table 2]

[0131] Phenylene-bis-diphenyltriazines (d 21 An example of a 5,6,5,6-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine is represented by the formula [Table 3] Corresponds to.

[0132] The imidazoline derivatives (d 22 An example of is ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

[0133] Diarylbutadiene derivatives (d 23 An example of is 1,1-dicarboxy-(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

[0134] Aminohydroxybenzoylhexylbenzoic acid derivatives (d 24 An example of a 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid hexyl ester is represented by the formula: [ka] Corresponds to.

[0135] Bis-(diethylaminohydroxybenzoyl)-piperazine derivatives (d 25 ) is the formula [ka] Corresponds to.

[0136] The above-mentioned UV filters (d1) to (d 25 Each of the filter groups (d1) to (d 25 Mixtures of two, three, four, five or six of the substance classes (d1) to (d 25 Mixtures of two, three, four, five or six UV filters from one or more representatives of the following classes can also be used according to the invention.

[0137] In a preferred embodiment, the UV filters (d) are representatives of the following compound classes: (d1) p-aminobenzoic acid derivatives; (d2) Salicylic acid derivatives; (d3) benzophenone derivatives; (d4) dibenzoylmethane derivatives; (d5) diphenyl acrylate; (d6) 3-imidazol-4-yl-acrylic acid and its esters; (d7) benzofuran derivatives; (d9) cinnamic acid derivative; (d 10 ) camphor derivatives; (d 11 ) hydroxyphenyltriazine derivatives; (d 12 ) benzotriazole derivatives; (d 13 ) trianilino-s-triazine derivatives; (d 15 ).o-aminobenzoic acid methyl ester; (d 16 ) Homosalate; (d 19 ) benzylidene malonate; and (d 20 ) Merocyanine derivatives.

[0138] In a more preferred embodiment, the following oil-soluble UV filters are used according to the invention: (d SOL-1 ) Benzophenone-3 (BP3); (d SOL-2 ) Benzophenone-4 (BP4); (d SOL-3 ) 3-benzylidenecamphor (3BC); (d SOL-4 ) Bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT); (d SOL-5 )Butyl methoxydibenzoylmethane (BMBM); (d SOL-6 )Diethylhexylbutamidotriazone (DBT); (d SOL-7 ) Drometrizole Trisiloxane (DTS); (d SOL-8) Ethylhexyl triazone (EHT); (d SOL-9 )Ethylhexyl methoxycinnamate; (d SOL-10 ) benzylidene malonate (BM); (d SOL-11 ) Diethylamino hydroxybenzoyl hexyl benzoate (DHHB); (d SOL-12 )Octocrylene; (d SOL-13 ) Polysilicone-15; (d SOL-14 ) Homosalate; (d SOL-15 ) Ethylhexyl salicylate; and (d SOL-16 ) Merocyanine.

[0139] In a more preferred embodiment, the following particulate UV filters are used according to the invention: Methylenebis-benzotriazolyltetramethylbutylphenol(nano)(MBBT); Tris-biphenyltriazine(nano)(TBPT); Bis-(diethylaminohydroxybenzoyl)piperazine (nano) (BDBP); and Phenylenebis-diphenyltriazine (PBDT).

[0140] In a most preferred embodiment, the UV filter is at least one selected from the group consisting of: (d 9a )Ethylhexyl methoxycinnamate; (d 11a ) Bis-ethylhexyloxyphenol methoxyphenyl triazine; (d 13a ) Ethylhexyl triazone; (d 3a )Diethylaminohydroxybenzoylhexyl benzoate; Merocyanine, Methylenebis-benzotriazolyltetramethylbutylphenol(nano)(MBBT); Tris-biphenyltriazine (nano) (TBPT); and Bis-(diethylaminohydroxybenzoyl)piperazine(nano)(BDBP).

[0141] In a particularly preferred embodiment, the UV filter is 9a ), (d 11a ), (d 13a ) and (d 3a ).

[0142] In a preferred embodiment, the method or use protects the skin from UV and high energy visible light.

[0143] In a preferred embodiment, the method or use protects the skin from ultraviolet light having a wavelength in the range of 280-400 nm and high-energy visible light having a wavelength in the range of 380-480 nm.

[0144] In a preferred embodiment, the method or use protects the skin from high energy visible light with a wavelength in the range 380-480 nm.

[0145] The increase in absorbance due to the presence of closed cell metal oxide particles was observed to be stronger in the ultraviolet range compared to the visible range.

[0146] In a preferred embodiment, the method further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.

[0147] In a preferred embodiment, the use further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.

[0148] UV filter composition comprising closed cell metal oxide particles Another aspect of the present invention relates to a UV filter composition comprising closed cell metal oxide particles in the range of 0.1-25.0 wt. %, based on the total weight of the UV filter composition. The closed cell metal oxide particles comprise a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume, and the outer surface of the closed cell metal oxide particles being defined by the array of closed cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.

[0149] In a preferred embodiment, the void volume is media impermeable.

[0150] In a preferred embodiment, the UV filter composition comprises (i) water; and (ii) closed cell metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition Includes.

[0151] In a preferred embodiment, the UV filter composition comprises (i) water; and (ii) closed cell metal oxide particles in the range of 0.5 to 10.0% by weight based on the total weight of the UV filter composition Includes.

[0152] In a preferred embodiment, the UV filter composition comprises Water b. oil; and c. Closed cell metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition Includes.

[0153] In a preferred embodiment, the oil is present in the form of a discontinuous phase in the range of 5.0 to 50.0% by weight, based on the total weight of the UV filter composition.

[0154] In a preferred embodiment, water is present in the form of a discontinuous phase in the range of 5.0 to 50.0% by weight, based on the total weight of the UV filter composition.

[0155] In a preferred embodiment, the UV filter composition comprises (i) oil; and (ii) closed cell metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition Includes.

[0156] In a preferred embodiment, the UV filter composition comprises (i) oil; and (ii) closed cell metal oxide particles in the range of 0.5 to 10.0% by weight based on the total weight of the UV filter composition Includes.

[0157] In a preferred embodiment, the amount of metal oxide in the closed cell metal oxide particles is in the range of 60.0 to 100.0 wt %, based on the total weight of the closed cell metal oxide particles.

[0158] In a preferred embodiment, the closed cell metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

[0159] In a preferred embodiment, the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.90.

[0160] In a preferred embodiment, the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.80.

[0161] In a preferred embodiment, the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 500 nm.

[0162] In a preferred embodiment, the closed cell metal oxide particles further comprise a light (UV-visible) absorber.

[0163] In a preferred embodiment, the light (UV-visible) absorber is present in the range of 0.1% to 40.0% by weight.

[0164] In a preferred embodiment, the UV filter composition further comprises a UV absorber selected from the group consisting of: (d1) p-aminobenzoic acid derivatives; (d2) Salicylic acid derivatives; (d3) benzophenone derivatives; (d4) dibenzoylmethane derivatives; (d5) diphenyl acrylate; (d6) 3-imidazol-4-yl-acrylic acid and its esters; (d7) benzofuran derivatives; (d8) polymeric UV absorbers; (d9) cinnamic acid derivative; (d 10 ) camphor derivatives; (d 11 ) hydroxyphenyltriazine derivatives; (d 12 ) benzotriazole derivatives; (d 13 ) trianilino-s-triazine derivatives; (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d 15 ) o-aminobenzoic acid methyl ester; (d 16 ) Homosalate; (d 17 ) tris-biphenyltriazine derivatives; (d 18 ) TiO2, ZnO and mica; (d 19 ) benzylidene malonate; (d 20 ) merocyanine derivatives; (d 21 ) phenylenebisdiphenyltriazine; (d 22 ) imidazoline derivatives; (d 23) diarylbutadiene derivatives; (d 24 ) aminohydroxybenzoyl hexyl benzoate derivatives; (d 25 ) bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives; and A mixture of them.

[0165] Representative examples of UV absorbers are described herein.

[0166] In a preferred embodiment, the UV filter composition is a sunscreen composition.

[0167] In a preferred embodiment, the UV filter composition is a day care composition.

[0168] In a preferred embodiment, the UV filter composition is at least one selected from the group consisting of a cream, a gel, a lotion, an alcoholic solution, an aqueous / alcoholic solution, an emulsion, a wax / fat composition, a stick formulation, a powder and an ointment.

[0169] Provided form The described final UV filter compositions can be present in various presentation forms, for example: - the form of liquid formulations as W / O, O / W, O / W / O, W / O / W or PIT emulsions and all kinds of microemulsions; - in the form of a gel, in the form of an oil, cream, milk or lotion, in the form of powders, lacquers, tablets or make-up, - Stick form, - in the form of a spray (propellant spray or pump spray) or aerosol, - foam morphology, - In paste form.

[0170] Of particular importance as UV filter compositions for the skin are sun protection preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pre-sun or post-sun preparations, but also skin tanning preparations, such as self-tanning creams. Of particular interest are sunscreen creams, sunscreen lotions, sunscreen milks and sunscreens in the form of sprays.

[0171] Furthermore, the UV filter composition may contain further adjuvants as described below.

[0172] 1) Oily phase In the context of the present invention, possible oily substances are, for example, gelbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms (e.g. Eutanol® G), linear C6-C 22 -Fatty acids, straight or branched, C6-C 22 -Esters with fatty alcohols or branched C6-C 13 -Carboxylic acid, linear or branched C6-C 22esters with fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, stearyl Isostearyl phosphate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate, and erucyl erucate. In addition, linear C6-C 22 - Esters of fatty acids with branched chain alcohols, in particular 2-ethylhexanol, C3-C 38 -Alkyl hydroxy carboxylic acid, linear or branched C6-C 22 - esters with fatty alcohols, in particular with diethylhexyl malate, esters of linear and / or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and / or gelbet alcohols, C6-C 10 -Triglycerides based on fatty acids, C6-C 18 -Liquid mono- / di- / triglyceride mixture based on fatty acids, C6-C 22 - esters of fatty alcohols and / or gelatin alcohols with aromatic carboxylic acids, in particular benzoic acid, C2-C 12- Esters of dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C 22 - fatty alcohol carbonates, such as dicaprylyl carbonate (Cetiol® OE), gelbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, C atoms, linear and / or branched C6-C of benzoic acid 22 Suitable for consideration are alcohols (for example Finsolv® TN), esters with linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, for example dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols (Hydagen® HSP, Sovermol® 750, Sovermol® 1102), silicone oils (cyclomethicone, silicone methicone type, etc.) and / or aliphatic or naphthenic hydrocarbons, for example mineral oil, petrolatum, squalane, squalene, isohexadecane or dialkylcyclohexanes.

[0173] In a particular embodiment, the oily substance is a medium polarity oil, particularly a C2-C 12 -Esters of dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms and / or linear and branched C6-C 22 fatty alcohol carbonates, whereby the adipic acid esters of linear or branched alcohols having 1 to 22 carbon atoms, in particular linear alcohols having 1 to 6 carbon atoms, are particularly suitable.

[0174] Linear and branched fatty alcohol carbonates, in particular dicaprylyl carbonate, are particularly preferably used as oily substances.

[0175] In a more preferred embodiment, dibutyl adipate is used as the oily substance.

[0176] In an even more preferred embodiment, the oil phase is selected from C12-15 alkyl benzoates, dibutyl adipate, dicaprylyl carbonate, propylheptyl caprylate, caprylic / capric triglyceride, dicaprylyl ether, butylene glycol dicaprylate / dicaprate, cococaprylate, octyldodecanol, dipropylheptyl carbonate, caprylyl-caprylate / caprate, cocoglycerides, ethylhexyl stearate, isohexadecane, isopropyl palmitate, and isopropyl myristate.

[0177] In another embodiment, the amount of oily phase ranges from 20 to 35% by weight, based on the total weight of the UV filter composition.

[0178] 2) Surfactants In a particular embodiment, the UV filter composition further comprises at least one surfactant in the range of 1.0 to 20.0 wt. %, based on the total weight of the UV filter composition.

[0179] In certain embodiments, the surfactant is selected from anionic surfactants, nonionic surfactants, and polymeric surfactants.

[0180] Anionic surfactants are characterized by one or more anionic groups that provide solubility in water and lipophilic groups, such as carboxylate, sulfate, sulfonate or phosphate groups.Furthermore, this molecule can contain polyglycol ether, ester, ether and hydroxyl groups.A large number of anionic surfactants that are acceptable to skin are known to those skilled in the art from related handbooks and are commercially available.

[0181] Representative examples of preferred anionic surfactants, in each case in the form of their salts, are ether-carboxylic acids, acyl sarcosides having 8 to 24 C atoms in the acyl group, acyltaurides having 8 to 24 C atoms in the acyl group, acyl isethionates having 8 to 24 C atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and monoalkyl polyoxyethyl sulfosuccinates having 8 to 24 C atoms and 1 to 6 oxyethyl groups in the alkyl group. Esters, linear alkane sulfonates with 8 to 24 C atoms, linear alpha-olefin sulfonates with 8 to 24 C atoms, alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 C atoms, alkyl sulfates, alkyl polyglycol ether sulfates, esters of tartaric and citric acid, alkyl and / or alkenyl ether phosphates, sulfated fatty acid alkylene glycol esters, monoglyceride sulfates and monoglyceride ether sulfates as well as C8 to C 30 - Condensation products of fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, the so-called protein fatty acid condensates, such as, for example, Lamepon®, Gluadin®, Hostapon® KCG or Amisoft®.

[0182] The salts of these surfactants are preferably chosen from sodium, potassium and ammonium and mono-, di- and trialkanalammonium salts having 2 to 4 C atoms in the alkanol group.

[0183] Particularly suitable anionic surfactants are liquid at room temperature, preferably at 18 to 25° C. A particularly desirable feature of these anionic surfactants is that they have a low water content of at most 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the anionic surfactant.

[0184] In a most preferred embodiment, the anionic surfactant is an alkyl(en)yl polyglycol ether citrate, in particular of formula (I): [ka] (In the formula, R1, R2 and R3 are each independently hydrogen or a group represented by formula (II) R4(OCH2CHR5) n represents a group of R4 represents a linear or branched alkyl and / or alkenyl group having 6 to 22 carbon atoms; R5 represents hydrogen or a methyl group, and n represents a number from 1 to 20, provided that at least one of the groups R1, R2 or R3 is other than hydrogen. It is a mixture of mono-, di- and triesters of citric acid and alkoxylated alcohols corresponding to the above.

[0185] Typical examples of the alcohol portion of the esters are addition products of an average of 1 to 20 moles, preferably 5 to 10 moles, of ethylene oxide and / or propylene oxide onto caproyl alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassydyl alcohol and mixtures of technical grades thereof.

[0186] Such alk(en)yl polyglycol ether citrates are advantageous in the agents according to the invention since they are liquid anionic surfactants having a low water content of up to 5% by weight, based on the anionic surfactant.

[0187] The anionic surfactant is preferably present in an amount ranging from 7 to 17% by weight, based on the total weight of the UV filter composition.

[0188] The agent according to the invention further comprises at least (c) 0.5 to 25% by weight of a further co-surfactant different from the anionic surfactant.

[0189] Suitable co-surfactants are, in principle, zwitterionic, amphoteric, cationic and / or non-ionic surfactants.

[0190] At least one quaternary ammonium group and at least one -COO (-) or -SO3 (-) These surface-active compounds having a group are zwitterionic surfactants. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates having 8 to 18 C atoms in the alkyl or acyl group, respectively, such as cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, such as cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivatives known under the INCI name cocamidopropyl betaine are preferred zwitterionic surfactants. Particularly preferred according to the invention are Tego® Betain 810 (INCI: capryl / capramidopropyl betaine) and surfactant mixtures of Rewopol® SBCS 50K (INCI: disodium PEG-5 lauryl citrate sulfosuccinate, sodium laureth sulfate) and Tego® Betain 810 (capryl / capramidopropyl betaine), especially in a weight ratio of 1:4 to 4:1, very particularly preferably 1:4 to 1:1.

[0191] Amphoteric surfactants are those that have C8 to C 18- is understood to mean a surface-active compound which, apart from the alkyl or acyl group, contains at least one free amino group and at least one -COOH or -SO3H group and is capable of forming inner salts. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with an alkyl group having 8 to 18 C atoms. Preferred amphoteric surfactants are N-coco-alkylaminopropionates, coco-acylaminoethylaminopropionates and C 12~18 -Acylsarcosine.

[0192] In particular, quaternary ammonium compounds can be used as cationic surfactants. Surfactants from this substance class have a particularly high affinity for the skin and can improve the degree of sensory smoothness. These include, among others, ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and trialkylmethylammonium chloride, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. In addition, extremely readily biodegradable quaternary ester compounds can be used as cationic surfactants, such as dialkylammonium methosulfate and methylhydroxyalkyldialkyloxyalkylammonium methosulfate sold under the trade name Stepantex® and the corresponding products of the Dehyquart® series. The term "ester quats" is generally understood to mean quaternized fatty acid triethanolamine ester salts. They impart a particularly soft feel to the composition. These are known substances which are prepared by the appropriate methods of organic chemistry.Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

[0193] Non-ionic surfactants are particularly preferably present as co-surfactants, for example: - addition products of 2 to 50 mol of ethylene oxide and / or 0 to 20 mol of propylene oxide onto linear fatty alcohols having 8 to 40 C atoms, onto fatty acids having 12 to 40 C atoms and onto alkylphenols having 8 to 15 C atoms in the alkyl group. - C of addition products of 1 to 50 moles of ethylene oxide on glycerol 12 / 18- fatty acid mono- and diesters; glycerol mono- and diesters, sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products, - alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogues; addition products of 7 to 60 moles of ethylene oxide on castor oil and / or hydrogenated castor oil; - polyol and / or polyglycerol esters, such as polyglycerol diisostearate or polyglycerol dimerate or polyglycerol 12-hydroxystearate; - addition products of 2 to 15 moles of ethylene oxide on castor oil and / or hydrogenated castor oil; - Straight chain, branched, unsaturated or saturated C6~C 22 partial or mixed esters based on fatty acids, ricinoleic acid and 12-hydroxystearic acid with pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose), such as glyceryl citrate stearate and glyceryl lactate stearate; - Wool wax alcohol; - polysiloxane / polyalkylpolyether copolymers and corresponding derivatives; mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglucose and a polyol, preferably glycerol or polyglycerol; - Polyalkylene glycol.

[0194] Addition products of ethylene oxide and / or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known and commercially available. These are homolog mixtures whose average degree of alkoxylation corresponds to the ratio of the amounts of substance of ethylene oxide and / or propylene oxide to the substrate with which the addition reaction is carried out. Depending on the degree of ethoxylation, they are W / O or O / W emulsifiers. For the preparations according to the invention, reaction products with 1 to 100 moles of ethylene oxide are particularly suitable.

[0195] Advantageous compounds from the group of nonionic surfactants are partial esters of polyols, in particular C3-C6-polyols, such as glyceryl monoesters, partial esters of pentaerythritol or sugar esters, such as sucrose distearate, sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate. , sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical grade mixtures thereof. Adducts of 1 to 30 moles, preferably 5 to 10 moles, of ethylene oxide onto sorbitan esters are also suitable nonionic surfactants.

[0196] Nonionic surfactants from the group of alkyl oligoglycosides may preferably be suitable in the context of the present invention, since they are particularly gentle on the skin. 22 -Alkyl mono- and oligoglycosides, their preparation and their use are known. Their preparation is carried out in particular by reaction of glucose or oligosaccharides with primary alcohols having 8 to 22 C atoms, preferably 12 to 22, particularly preferably 12 to 18 C atoms. As regards the glycosidic group, both monoglycosides in which a cyclic sugar residue is glycosidically linked to a fatty alcohol and oligomeric glycosides, preferably having a degree of oligomerization of up to 8, are suitable. In this specification, the degree of oligomerization is a statistical average value based on the historical distribution of the homologues of such technical grade products. Products sold under the name Plantacare® contain C8-C cyclic sugar residues glycosidically linked on oligoglucoside groups. 16 -alkyl groups, the average degree of oligomerization of which is from 1 to 2. Acylglucamides derived from glucamine are also suitable as nonionic surfactants.

[0197] Non-ionic surfactants, preferably polyols and / or polyglycerol esters, are very particularly preferably present as cosurfactants and / or alkyl oligoglycosides in the agents according to the invention as component (c).

[0198] The polyol component of these surfactants can be derived from materials having at least 2, preferably 3 to 12, especially 3 to 8 hydroxyl groups and 2 to 12 carbon atoms. Typical examples are as follows: - glycerol and polyglycerols; - alkylene glycols, such as ethylene glycol, diethylene glycol, propylene glycol; methylol compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; - alkyl oligoglucosides having 1 to 22, preferably 1 to 8 and in particular 1 to 4 carbons in the alkyl group, such as methyl and butyl glucoside; - sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol; - sugars having 5 to 12 carbon atoms, such as glucose or sucrose; - Amino sugars, for example glucamine.

[0199] Polyglycerol-based reaction products are of particular interest due to their excellent use properties.

[0200] The acid component of these surfactants can be derived from linear, branched, saturated and / or unsaturated carboxylic acids, optionally bearing functional groups such as hydroxyl groups. The acid component is particularly preferably a fatty acid having 12 to 22 carbon atoms, optionally bearing hydroxyl groups, in particular hydroxystearic acid.

[0201] In a preferred embodiment of the invention, diesters of polyhydroxystearic acid are used as glyceryl esters, for example polyglyceryl 2-dipolyhydroxystearate sold under the name Dehymuls® PGPH by BASF Personal Care and Nutrition GmbH.

[0202] In a preferred embodiment of the present invention, Eumulgin® SG, Eumulgin® Prisma, Emulgade® sucro and Emulgade® SucroPlus are used as surfactants.

[0203] In the agents according to the invention, the further cosurfactant is conventionally present in an amount ranging from 0.5 to 25% by weight, more preferably in an amount ranging from 3.0 to 18% by weight and particularly preferably in an amount ranging from 7 to 18% by weight.

[0204] 3) Additives In certain embodiments, the UV filter composition further comprises an additive selected from thickeners, active ingredients, preservatives and fragrances.

[0205] Thickener Suitable thickeners are anionic, zwitterionic, amphoteric and nonionic copolymers, such as vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate polymers, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymers and optionally polysaccharides, in particular xanthan gum, guar and guar derivatives, agar, alginates and tylose, cellulose and cellulose derivatives, such as carboxymethylcellulose, carboxymethylcellulose and hydroxycellulose, and also silicones.

[0206] Preferably, a thickener is added selected from the group of polyacrylates and crosslinked polyacrylates, such as Rheocare TTA®, Cosmedia® SP, Rheocare® C Plus, Tinovis® ADE, Tinovis® GTC.

[0207] Further preferred are thickeners from the group of polysaccharides such as Keltrol® T or Rheocare® XG and thickeners such as Hydagen® 558P, Hydagen® Clean, Rheocare® XGN, Tinovis® GTC, Cosmedia® ACE.

[0208] Preferably, the amount of thickener ranges from 0.5 to 5% by weight, in particular from 1 to 4% by weight, calculated as active substance, based on the total weight of the UV filter composition.

[0209] The thickening agent may be added to the concentrated drug before dilution with water is carried out, or may be contained in the water in which dilution of the concentrated drug is carried out.

[0210] According to a preferred process variant, the concentrated drug is mixed with a thickening agent, water for dilution is added to this mixture, and further formulation ingredients are optionally stirred in.

[0211] According to another preferred process variant, the water, the thickener and optionally other auxiliary substances are stirred together and the concentrated drug is added to this mixture.

[0212] The final UV filter formulations prepared by the process according to the invention are often particularly finely divided O / W emulsions with an average particle size of <10 μm, preferably <5 μm.

[0213] active compound Suitable biologically active compounds according to the invention are understood to mean, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and its fragmentation products, β-glucan, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts such as prune extract, bambara nut extract, etc., as well as vitamin complexes. Such active compounds are utilized in the final UV filter formulation as agents that scavenge free radicals and help in skin regeneration.

[0214] Preservatives Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and silver complexes known under the name Surfacine®.

[0215] perfume oil The perfume oils that can be mentioned are natural, vegetable and animal as well as synthetic odoriferous substances or their mixtures.Natural odoriferous substances are obtained by extracting in particular the flowers, stems, leaves, fruits, peels, roots and resins of plants.Animal raw materials are also possible, such as civet and castoreum.Typical synthetic odoriferous compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.Preferably, a mixture of various odoriferous substances is used that together produce a pleasant fragrance note.

[0216] In a preferred embodiment, the fragrance is selected from the group consisting of limonene, citral, linalool, alpha-isomethylione, 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, alpha-amylcinnamaldehyde, alpha-methylionone, amyl-C-butylphenylmethylpropional cinnamal, amyl salicylate, amyl cinnamyl alcohol, anise alcohol, benzoin, benzyl alcohol, benzyl benzoate, benzyl cinnamate, benzyl sarcosamine ... citronellol, citronellyl methyl crotonate, lemon oil, coumarin, diethylsuccinate, ethylinalol, eugenol, evernia furfurracea extract, evernia prunastri extract, farensole, guajac wood oil, hexyl cinnamal, hexyl salicylate, hydroxycitronellal, lavender oil, lemon oil, linalyl acetate, mandarin oil, menthyl PCA, methylheptenone, nutmeg oil, rosemary oil, sweet orange oil, terpineol, tonka bean oil, triethyl citrate, vanillin.

[0217] Auxiliary substances In certain embodiments, the final UV filter formulation further comprises auxiliary substances such as moisturizers / skin moisturizers, viscosity modifiers, oils, fats and waxes, surfactants, pearlescent waxes, super-oiling agents, stabilizers, cationic, zwitterionic or amphoteric polymers, further UV filters, biologically active compounds, film formers, swelling agents, hydrotropic substances, preservatives, solubilizers, fragrance oils, dyes, insect repellent active compounds, as listed by way of example below.

[0218] The humectant further optimizes the sensory properties of the composition and helps regulate skin moisture. The humectant may be present in an amount ranging from 0 to 5.0% by weight, based on the total weight of the UV filter composition.

[0219] Suitable substances are, in particular, amino acids, pyrrolidone carboxylic acid, lactic acid and its salts, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, collagen cleavage products, chitosan or chitosan salts / derivatives, in particular polyols and polyol derivatives (e.g. glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycols, e.g. PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-1 2, PEG-14, PEG-16, PEG-18, PEG-20), sugars and sugar derivatives (in particular fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sucrose, sorbitylsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and their salts), ethoxylated sorbitol (sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40), honey and hydrogenated honey, hydrogenated starch hydrolysates and mixtures of hydrogenated wheat protein with PEG-20 / acetate copolymer. Preferably, substances suitable according to the invention as humectants are glycerol, diglycerol, triglycerol and butylene glycol.

[0220] Possible insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or 3-(Nn-butyl-N-acetylamino)propionic acid ethyl ester) (which is sold under the name Insect Repellent 3535 by Merck KGaA) and butyl acetylaminopropionate, which are conventionally utilized in the compositions according to the invention in amounts ranging from 0 to 6% by weight, based on the total weight of the UV filter composition.

[0221] The viscosity of the agents according to the invention can be achieved by adding viscosity modifiers. Possible viscosity modifiers are in particular consistency-imparting agents, such as fatty alcohols or hydroxyfatty alcohols and partial glycerides having 12 to 22, preferably 16 to 18, carbon atoms, fatty acids or 12-hydroxy-fatty acids having 12 to 22 carbon atoms. Combinations of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length are also suitable, as they result in particularly stable and homogeneous emulsions. Viscosity modifiers also include thickeners such as Aerosil types (hydrophilic silicic acids), polysaccharides, especially xanthan gum, guar-guar, agar, alginates and tylose, carboxymethylcellulose and hydroxyethyl- and hydroxypropylcellulose, as well as high molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (e.g. Carbopols® and Pemulen types from Goodrich; Synthalens® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), non-crosslinked and polyol-crosslinked polyacrylic acids, polyacrylamides, polyvinyl alcohols and polyvinylpyrrolidones. Bentonites such as Bentone® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate, have also proven to be particularly effective. Surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, narrow homologue fatty alcohol ethoxylates, alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride may also be utilized to adjust the viscosity.

[0222] In the context of the present invention, fats and waxes are understood to mean all lipids with a fat or waxy consistency having a melting point above 20°C. These include, for example, classical triacylglycerols, i.e. triesters of fatty acids and glycerol, which can be of vegetable or animal origin. They can also be mixed esters, i.e. triesters of glycerol with various fatty acids or mixtures of various glycerides. Also included are mixtures of mono-, di- and triglycerides. Particularly suitable for the present invention are so-called hydrogenated fats and oils, which are obtained by partial hydrogenation. Preferred are hydrogenated vegetable fats and oils, such as hydrogenated castor oil, peanut oil, soybean oil, rapeseed oil, beet seed oil, cottonseed oil, soybean oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, corn oil, olive oil, sesame oil, cocoa butter and coconut oil. Particularly suitable are the oxidation-stable vegetable glycerides sold under the names Cegesoft® or Novata®.

[0223] Possible waxes are especially natural waxes, such as candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropidium fat, ceresin, ozocerite (earth wax), petrolatum, paraffin wax, microwaxes; chemically modified waxes (hard waxes), such as montan ester wax, sazol wax, hydrogenated jojoba wax, and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes.

[0224] In addition to fats, fat-like substances such as lecithin and phospholipids can also be used as additives. Lecithin is a glycerophospholipid formed by esterification of fatty acids, glycerol and choline phosphate, often called phosphatidylcholine (PC). As an example of a natural lecithin, mention may be made of cephalin, a derivative of 1,2-diacyl-sn-glycerol-3-phosphate, also called phosphatidic acid. In contrast, phospholipids are usually understood to mean mono-, preferably diesters of phosphoric acid and glycerol (glycerol phosphate). Sphingosine and sphingolipids are also possible fat-like substances.

[0225] Suitable pearlescent waxes are, for example, alkylene glycol esters, in particular ethylene glycol distearate; fatty acid alkanolamides, in particular coconut fatty acid diethanolamide; partial glycerides, in particular stearic acid monoglyceride; polybasic, optionally hydroxy-substituted carboxylic acids and C6-C 22 - esters with fatty alcohols, in particular long-chain esters of tartaric acid; fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, having a total of at least 24 carbon atoms, in particular Lauron®; distearyl ethers; fatty acids, such as stearic acid, C 12 ~C 22 -Hydroxy fatty acid, behenic acid, C 12 ~C 22 -Olefin epoxides and C 12 ~C 22 ring-opening products with fatty alcohols and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.

[0226] Usable super-oiling agents are, for example, substances such as lanolin and lecithin and polyethoxylated or acylated derivatives of lanolin and lecithin, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter of which also function as foam stabilizers.

[0227] So-called stabilizers which can be used are metal salts of fatty acids, such as magnesium stearate or ricinoleate, aluminium and / or zinc.

[0228] Suitable cationic polymers which further optimize the sensory properties of the compositions according to the invention and impart a sensation of softness to the skin are, for example, cationic cellulose derivatives, for example quaternized hydroxyethylcellulose available from Amerchol under the name Polymer JR 400®, cationic starch, copolymers of diallylammonium salts and acrylamide, quaternized vinylpyrrolidone / vinylimidazole polymers, for example Luviquat® (BASF), condensation products of polyglycols with amines, quaternized collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat® L / Grueau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid and dichloride. Copolymers with methyldiallylammonium (Merquat® 550 / Chemviron), polyaminopolyamides and crosslinked water-soluble polymers thereof, cationic chitin derivatives such as quaternized chitosan, condensation products of dihaloalkyls, such as dibromobutane, with bisdialkylamines, such as bis-dimethylamino-1,3-propane, optionally distributed in microcrystalline form, cationic guar gums, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

[0229] To improve skin feel, starch derivatives such as DryFlo® PC (INCI: Aluminum Starch Octenylsuccinate) can additionally be utilized.

[0230] Suitable silicone compounds have already been described under oily substances. In addition to dimethylpolysiloxanes, methylphenylpolysiloxanes and cyclic silicones, amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified silicone compounds are also suitable, which are liquid or resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200-300 dimethylsiloxane units and silicon dioxide or hydrogenated silicates, are also suitable.

[0231] So-called film-forming agents, which bring about a further improvement of the sensory properties of the preparations according to the invention, are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, collagen, hyaluronic acid and its salts and similar compounds, as well as polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series and quaternized cellulose derivatives, which have already been mentioned under the section on viscosity modifiers.

[0232] To improve the flow properties of the composition according to the invention, hydrotropic substances such as, for example, ethanol, isopropyl alcohol or polyols can be further utilized.Polyols possible according to the invention preferably have 2 to 15 carbon atoms and at least two hydroxyl groups.Polyols can also contain further functional groups, in particular amino groups, or can be modified with nitrogen.

[0233] The dyes which may be used are substances suitable and approved for cosmetic purposes.

[0234] The invention provides one or more of the following advantages.

[0235] 1. The present invention provides a method for increasing the sun protection factor of UV filter compositions using closed cell metal oxide particles.

[0236] 2. The method increases the SPF of a sunscreen formulation while minimizing or masking its whitening effect and maintaining its transparency.

[0237] 3. The closed cell metal oxide particles of the present invention can be used to increase the SPF of UV filter compositions.

[0238] 4. The closed cell metal oxide particles of the present invention are useful for increasing the SPF of a UV filter composition while minimizing or masking its whitening effect and maintaining its transparency.

[0239] Below, a list of embodiments is provided to further illustrate the present disclosure, but is not intended to limit the present disclosure to the specific embodiments listed below.

[0240] 1. A method for increasing the sun protection factor of a UV filter composition, comprising adding closed cell metal oxide particles to the UV filter composition, The closed cell metal oxide particles include a metal oxide matrix that defines an array of closed cells, each closed cell enclosing a void volume; the outer surface of the closed cell metal oxide particles is defined by an arrangement of closed cells; The method of claim 1, wherein the metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.

[0241] 2. The use of closed cell metal oxide particles to increase the sun protection factor of a UV filter composition, comprising: The closed cell metal oxide particles include a metal oxide matrix that defines an array of closed cells, each closed cell enclosing a void volume; the outer surface of the closed cell metal oxide particles is defined by an arrangement of closed cells; The metal oxide matrix used comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0242] 3. The method or use according to embodiment 1 or 2, wherein the void volume cannot accommodate the medium.

[0243] 4. The method or use according to any one of the preceding embodiments, wherein the amount of closed cell metal oxide particles is in the range of 0.1 to 25.0% by weight, based on the total weight of the UV filter composition.

[0244] 5. The method or use according to any one of the preceding embodiments, wherein the amount of closed cell metal oxide particles is in the range of 0.5 to 10.0% by weight, based on the total weight of the UV filter composition.

[0245] 6. The method or use according to any one of the preceding claims, wherein the array of closed cells is an ordered array.

[0246] 7. The method or use according to any one of the preceding claims, wherein the arrangement of closed cells is a disordered arrangement.

[0247] 8. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

[0248] 9. The method or use according to any one of the preceding embodiments, wherein the amount of metal oxide in the closed cell metal oxide particles is in the range of 60.0 to 100.0 wt. %, based on the total weight of the closed cell metal oxide particles.

[0249] 10. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 500 nm.

[0250] 11. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 400 nm.

[0251] 12. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 300 nm.

[0252] 13. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.90.

[0253] 14. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.80.

[0254] 15. The method or use according to any one of the preceding embodiments, wherein the metal oxide matrix comprises silica.

[0255] 16. The method or use according to any one of the preceding embodiments, wherein the metal oxide matrix comprises silica and alumina.

[0256] 17. The method or use according to any one of the preceding embodiments, wherein the metal oxide matrix comprises silica and titania.

[0257] 18. The method or use according to any one of the preceding embodiments, wherein the metal oxide matrix comprises silica and zinc oxide.

[0258] 19. The method or use according to any one of the preceding embodiments, wherein the closed cells are monodisperse.

[0259] 20. The method or use and cells according to any one of embodiments 1 to 18, wherein the closed cells have a bimodal distribution of monodisperse closed cells.

[0260] 21. The method or use according to any one of the preceding embodiments, wherein the closed cells are polydisperse.

[0261] 22. Closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and 20. The method or use according to any one of the preceding embodiments, wherein the closed cells are monodisperse.

[0262] 23. Closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. The method or use according to any one of embodiments 1 to 18 and embodiment 20, wherein the closed cells have a bimodal distribution of monodisperse closed cell metal oxide particles.

[0263] 24. Closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. The method or use according to any one of embodiments 1 to 18 and embodiment 21, wherein the closed cells are polydisperse.

[0264] 25. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles exhibit a color in the visible spectrum in the wavelength range of 380 nm to 800 nm.

[0265] 26. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles are effective in the wavelength range in the ultraviolet spectrum between 100 nm and 400 nm.

[0266] 27. The method or use according to any one of the preceding embodiments, wherein the closed cell metal oxide particles are effective in wavelength regions in the ultraviolet and visible spectrum ranging from 200 nm to 500 nm.

[0267] 28. The UV filter composition comprises (d1) p-aminobenzoic acid derivatives; (d2) Salicylic acid derivatives; (d3) benzophenone derivatives; (d4) dibenzoylmethane derivatives; (d5) diphenyl acrylate; (d6) 3-imidazol-4-yl-acrylic acid and its esters; (d7) benzofuran derivatives; (d8) polymeric UV absorbers; (d9) cinnamic acid derivative; (d 10 ) camphor derivatives; (d 11 ) hydroxyphenyltriazine derivatives; (d 12 ) benzotriazole derivatives; (d 13 ) trianilino-s-triazine derivatives; (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d 15 ) o-aminobenzoic acid methyl ester; (d 16 ) Homosalate; (d 17 ) tris-biphenyltriazine derivatives; (d 18 ) TiO2, ZnO and mica; (d 19 ) benzylidene malonate; (d 20 ) merocyanine derivatives; (d 21 ) phenylenebisdiphenyltriazine; (d 22 ) imidazoline derivatives; (d 23 ) diarylbutadiene derivatives; (d 24 ) aminohydroxybenzoyl hexyl benzoate derivatives; (d 25 ) bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives; and A mixture of them 28. The method or use according to any one of the preceding embodiments, comprising a UV absorber selected from the group consisting of:

[0268] 29. A method or use according to any one of embodiments 1 to 28 for protecting the skin from ultraviolet light and high-energy visible light.

[0269] 30. The method or use according to embodiment 29 for protecting the skin from ultraviolet light having a wavelength in the range of 280 to 400 nm and high-energy visible light having a wavelength in the range of 380 to 480 nm.

[0270] 31. The method or use according to embodiment 29 or 30, for protecting the skin from high-energy visible light with a wavelength in the range of 380 to 480 nm.

[0271] 32. The method according to any one of the preceding embodiments, further minimizing or masking the whitening effect of the UV filter composition and maintaining its transparency.

[0272] 33. Use according to any one of the preceding embodiments, which further minimizes or masks the whitening effect of a UV filter composition and maintains its transparency.

[0273] 34. A UV filter composition comprising 0.1 to 25.0 wt. % of closed cell metal oxide particles based on the total weight of the UV filter composition; The closed cell metal oxide particles include a metal oxide matrix that defines an array of closed cells, each closed cell enclosing a void volume; the outer surface of the closed cell metal oxide particles is defined by an arrangement of closed cells; The UV filter composition, wherein the metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0274] 35. A UV filter composition according to embodiment 34, wherein the void volume does not allow the medium to enter.

[0275] 36.a. Water; and b. Closed cell metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition 36. The UV filter composition according to embodiment 34 or 35, comprising

[0276] 37.a. Water; and b. Closed cell metal oxide particles in the range of 0.5 to 10.0% by weight based on the total weight of the UV filter composition 37. The UV filter composition according to embodiment 36, comprising:

[0277] 38.a. Water b. oil; and c. Closed cell metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition 38. The UV filter composition according to embodiment 36 or 37, comprising

[0278] 39. A UV filter composition according to embodiment 38, wherein the oil is present in the form of a discontinuous oil phase in the range of 5.0 to 50.0% by weight, based on the total weight of the UV filter composition.

[0279] 40. A UV filter composition according to embodiment 38, wherein water is present in the form of a discontinuous phase in the range of 5.0 to 50.0% by weight, based on the total weight of the UV filter composition.

[0280] 41.a. Oil; and b. Closed cell metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition 36. The UV filter composition according to embodiment 34 or 35, comprising

[0281] 42.a. Oil; and b. Closed cell metal oxide particles in the range of 0.5 to 10.0% by weight based on the total weight of the UV filter composition 42. The UV filter composition according to embodiment 41, comprising:

[0282] 43. The UV filter composition according to any one of embodiments 34 to 42, wherein the amount of metal oxide in the closed cell metal oxide particles is in the range of 60.0 to 100.0 wt.-%, based on the total weight of the closed cell metal oxide particles.

[0283] 44. A UV filter composition according to any one of embodiments 34 to 43, wherein the closed cell metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

[0284] 45. A UV filter composition according to any one of embodiments 34 to 44, wherein the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.90.

[0285] 46. ​​A UV filter composition according to any one of embodiments 34 to 45, wherein the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.80.

[0286] 47. A UV filter composition according to any one of embodiments 34 to 46, wherein the closed cell metal oxide particles have an average pore diameter in the range of 3 nm to 500 nm.

[0287] 48.(d1) p-Aminobenzoic acid derivatives; (d2) Salicylic acid derivatives; (d3) benzophenone derivatives; (d4) dibenzoylmethane derivatives; (d5) diphenyl acrylate; (d6) 3-imidazol-4-yl-acrylic acid and its esters; (d7) benzofuran derivatives; (d8) polymeric UV absorbers; (d9) cinnamic acid derivative; (d 10 ) camphor derivatives; (d 11 ) hydroxyphenyltriazine derivatives; (d 12 ) benzotriazole derivatives; (d 13 ) trianilino-s-triazine derivatives; (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d 15 ).o-aminobenzoic acid methyl ester; (d 16 ) Homosalate; (d 17 ) tris-biphenyltriazine derivatives; (d 18 ) TiO2, ZnO and mica; (d 19 ) benzylidene malonate; (d 20 ) merocyanine derivatives; (d 21 ) phenylenebisdiphenyltriazine; (d 22 ) imidazoline derivatives; (d 23 ) diarylbutadiene derivatives; (d 24 ) aminohydroxybenzoyl hexyl benzoate derivatives; (d 25 ) bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives; and A mixture of them 48. The UV filter composition according to any one of embodiments 34 to 47, further comprising a UV absorber selected from the group consisting of:

[0288] 49. A UV filter composition according to any one of embodiments 34 to 48, further comprising at least one surfactant in the range of 0.1 to 20.0 wt.-%, based on the total weight of the UV filter composition.

[0289] 50. A UV filter composition according to embodiment 49, wherein the surfactant is selected from anionic surfactants, nonionic surfactants and polymeric surfactants.

[0290] 51. The UV filter composition according to any one of embodiments 34 to 50, further comprising an additive selected from thickeners, active ingredients, preservatives and fragrances.

[0291] 52. A UV filter composition according to any one of embodiments 34 to 51, which is a sunscreen composition.

[0292] 53. A UV filter composition according to any one of embodiments 34 to 51, which is a day care composition.

[0293] 54. A UV filter composition according to any one of embodiments 34 to 51, which is at least one selected from a cream, a gel, a lotion, an alcoholic solution, an aqueous / alcoholic solution, an emulsion, a wax / fat composition, a stick formulation, a powder and an ointment.

[0294] While the invention has been described in terms of its specific embodiments, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the invention. EXAMPLES

[0295] The present invention is illustrated in detail by the following non-limiting examples. More specifically, the test methods specified below are part of the general disclosure of this application and are not limited to the specific examples.

[0296] material In the examples, the following materials were used: Eumulgin® Prisma is disodium cetearyl sulfosuccinate; Lanette® O is cetylstearyl alcohol; Cutina® PES is pentaerythrityl distearate; Cetiol® B is dibutyl adipate; Cetiol® Sensoft is propylheptyl caprylate; Uvinul® T150 is ethylhexyl triazone; Tinosorb® S is bis-ethylhexyloxyphenol methoxyphenyl triazine; Uvinul® A Plus is diethylamino hydroxybenzoyl hexyl benzoate; Rheocare® XGN is xanthan gum; and Cosmedia® SP is a sodium polyacrylate; Available from BASF. Euxyl® PE9010 is phenoxyethanol and ethylhexylglycerin and is available from Ashland. Neo Heliopan® OS is ethylhexyl salicylate and is available from Symrise.

[0297] method Average diameter or particle size: Particle size as used herein is synonymous with particle diameter and is determined, for example, by scanning electron microscopy (SEM) or transmission electron microscopy (TEM). Average particle size is D 50 "is synonymous with" and means that half of the population is above this point and the other half is below this point. Particle size refers to the primary particle. Particle size can be measured by laser light scattering techniques using dispersions or dry powders.

[0298] Average Porosity and Average Pore Size: Mercury porosimetry analysis can be used to characterize the porosity of particles. In mercury porosimetry, a controlled pressure is applied to a sample immersed in mercury. An external pressure is applied to cause the mercury to penetrate the voids / pores of the material. The amount of pressure required to invade the voids / pores is inversely proportional to the size of the voids / pores. Mercury porosimetry uses the Washburn equation to generate volume and pore size distributions from the pressure vs. intrusion data generated by the instrument. Porosity reported herein for closed cell metal oxide particles is calculated as the ratio of unoccupied space to the total particle volume. For example, the average porosity of a porous silica particle containing voids / pores with a mean diameter of 165 nm is 0.8.

[0299] In vitro SPF determination of example formulations In vitro SPF determination is carried out by measuring the diffuse transmittance in the UV region using a Labsphere Ultraviolet Transmittance Analyzer 2000S. To simulate the heterogeneous surface structure of human skin, substrates with rough or porous surfaces are used for such measurements. In this method, sandblasted 4-5 μm PMMA (polymethylmethacrylate) plates from Helioscience (France) were used as substrates.

[0300] The formula for Sunburn Protection Factor (SPF) was first introduced by Sayre in 1979 [1] and is expressed as the irradiance spectrum S of a UV source: s (λ) and the erythema action spectrum S erThe average reverse transmittance (1 / T) of each sunscreen in the spectral range of 290-400 nm, including the scale in (λ), is calculated.

number

[0301] References [1] RMSayre, PPAgin, GJLeVee, E. Marlowe. A comparison of in vivo and in vitro testing of sunscreening formulas, Photochem. Photobiol. 29 (1979) 559-566

[0302] Transparency / Whiteness Method: The prepared compositions were applied onto a PMMA plate, which was also used for the in vitro SPF measurement, and color measurements were performed. * a * b * From the parameters, L * means the brightness of the sample. * The difference is delta L * and can be used to compare the transparency or whiteness of samples.

[0303] experiment Preparation of closed-cell metal oxide particles Example 1: Preparation of closed cell silica particles An aqueous dispersion of positively charged poly(meth)acrylate nanoparticles was diluted to 1 wt% with deionized water and 3 wt% of negatively charged silica nanoparticles were added. The mixture was sonicated for 30 s to prevent aggregation. The aqueous nanoparticle dispersion and the oil phase (continuous oil phase containing 2 wt% polyethylene glycol-co-perfluoropolyester surfactant in fluorinated oil) were each injected by syringe pump into a microfluidic device with a 50 μm droplet junction. The system was allowed to equilibrate until monodisperse droplets were generated. The droplets were collected in a reservoir.

[0304] The collected droplets were dried in an oven at 50° C. for 4 hours. The dried powder was placed on a silicon wafer and calcined by heating from room temperature to 500° C. over 4 hours, holding at 500° C. for 2 hours, and then cooling to room temperature over 4 hours. This procedure yielded monodisperse closed cell silica particles with a diameter of 15 micrometers.

[0305] Example 2: Preparation of closed-cell silica particles with ordered porosity An aqueous suspension of positively charged spherical polymer nanoparticles (a copolymer of methyl methacrylate and 2-(methacryloyloxy)ethyl]trimethylammonium chloride with an average diameter of 436 nm) and negatively charged silica nanoparticles (with an average diameter of 7 nm) was prepared. Based on the weight of the aqueous suspension, the polymer nanoparticles were present at 1.8 wt % and the silica nanoparticles were present at 0.6 wt % (weight ratio of polymer nanoparticles to metal oxide nanoparticles is 3:1). The aqueous suspension was spray dried using a BUECHI lab-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100° C., atomizing gas pressure of 40 mm, aspirator rate of 100%, and flow rate of 30% (approximately 10 mL / min).

[0306] The spray dried powder was removed from the collection chamber of the spray dryer and spread on a silicon wafer for sintering. The spray dried powder was then calcined in a muffle furnace in a batch calcination process to densify and stabilize the silica nanoparticles, remove the polymer, and produce closed cell silica particles. The heating parameters were as follows: the particles were heated from room temperature to 550°C over 5 hours, held at 550°C for 2 hours, and then cooled to room temperature over 3 hours. The average closed cell silica particle size was 3.2±1.4 μm.

[0307] SEM images of the resulting closed-cell silica particles and cross-sections of the closed-cell silica particles each showed that the internal structure comprised an array of closed-cell silica shells enclosing relatively monodisperse, ordered voids.

[0308] Example 3: Preparation of closed cell titania particles An aqueous suspension of negatively charged spherical polystyrene nanoparticles (having an average diameter of 197 nm) and positively charged titania nanoparticles (having an average diameter of 15 nm) was prepared. Based on the weight of the aqueous suspension, the polymer nanoparticles were present at 1.8 wt % and the titania nanoparticles were present at 1.2 wt % (weight ratio of polymer nanoparticles to metal oxide nanoparticles is 3:2). The aqueous suspension was spray dried using a BUECHI lab-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100° C., atomizing gas pressure of 55 mm, aspirator rate of 100%, and flow rate of 30% (approximately 10 mL / min).

[0309] The spray dried powder was removed from the collection chamber of the spray dryer and spread on a silicon wafer for sintering. The spray dried powder was then calcined in a muffle furnace in a batch calcination process to densify and stabilize the titania nanoparticles, remove the polymer, and produce closed cell titania particles. The heating parameters were as follows: the particles were heated from room temperature to 300°C over 4 hours, held at 300°C for 6 hours, then heated to 550°C over 2 hours, held at 550°C for 2 hours, and cooled to room temperature over 4 hours. The average closed cell titania particle size was 2.8±1.5 μm.

[0310] SEM images of the resulting closed cell titania particles and cross-sections of the closed cell titania particles showed that the internal structure comprised an array of closed cell titania shells each containing relatively monodisperse voids.

[0311] Example 4: Preparation of closed cell silica particles by sol-gel Aqueous suspensions of positively charged spherical polymer nanoparticles (a copolymer of methyl methacrylate and 2-(methacryloyloxy)ethyl]trimethylammonium chloride with an average diameter of 254 nm) and the silica precursor tetramethyl orthosilicate (TMOS) were mixed at a pH range of 2-5. Based on the weight of the aqueous suspension, the polymer nanoparticles were present at 1.8 wt % and the TMOS was present at 3.6 wt % (weight ratio of polymer nanoparticles to metal oxide is 1:3). The aqueous suspension was spray dried using a BUECHI lab-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100 °C, atomizing gas pressure of 40 mm, aspirator rate of 100%, and flow rate of 30% (approximately 10 mL / min).

[0312] The spray-dried powder was removed from the collection chamber of the spray dryer and spread on a silicon wafer for sintering. The spray-dried powder was then calcined in a muffle furnace in a batch calcination process to convert the silica precursor to silica nanoparticles, densify the silica, remove the polymer, and produce closed cell silica particles. The heating parameters were as follows: the particles were heated from room temperature to 200°C over 3 hours, held at 200°C for 2 hours, then heated to 550°C over 2 hours, held at 550°C for 2 hours, and cooled to room temperature over 3 hours. The average closed cell silica particle size was 3.0±1.7 μm.

[0313] Example 5: Preparation of closed cell silica particles with disordered porosity An aqueous suspension of positively charged spherical polymer nanoparticles (copolymer of methyl methacrylate and 2-(methacryloyloxy)ethyltrimethylammonium chloride) of two different sizes (254 nm and 142 nm diameter, respectively) and negatively charged silica nanoparticles (with an average diameter of 7 nm) was prepared. Based on the weight of the aqueous suspension, the polymer nanoparticles were present at a total of 1.8 wt% (0.9 wt% respectively) and the silica nanoparticles were present at 0.6 wt%. The aqueous suspension was spray dried using a BUECHI lab-scale spray dryer under an inert atmosphere (nitrogen) at an inlet temperature of 100°C, atomizing gas pressure of 40 mm, aspirator rate of 100% and flow rate of 30% (approximately 10 mL / min).

[0314] The spray-dried powder was removed from the collection chamber of the spray dryer and spread on a silicon wafer for sintering. The spray-dried powder was then calcined in a muffle furnace in a batch calcination process to convert the silica precursor to silica nanoparticles, densify the silica, remove the polymer, and produce closed cell silica particles. The heating parameters were as follows: the particles were heated from room temperature to 550°C over 6 hours, held at 550°C for 2 hours, and then cooled to room temperature over 4 hours. The average closed cell silica particle size was 2.1±1.2 μm.

[0315] The closed cell silica particles (0.5 mg) were placed in a 6 cm 2 The samples were uniformly dispersed in a 20 mL clear glass vial with a 1.2 mm bottom. The samples exhibited an angle-independent blue color observable by the human eye.

[0316] Characterization Experiment 1: Sun Protection Factor (SPF) experiment To evaluate the SPF of the closed cell metal oxide particles, UV filter compositions were prepared according to Table 1.

[0317] Composition 1 was a base (placebo) composition containing the following UV filters: ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate and ethylhexyl salicylate. Appropriate additives were also present in the composition.

[0318] Composition 2 was a composition of the present invention having 3.00 wt. % of the closed cell metal oxide particles prepared according to Example 2.

[0319] Composition 3 is a comparative analysis composition having 3.00 wt. % of a commercially available SunSpheres™ polymer boost for UV protection in place of the closed cell metal oxide particles.

[0320] Composition 4 is a comparative analytical composition having 3.00 wt. % of commercially available porous silica microspheres in place of the closed cell metal oxide particles.

[0321] [Table 4]

[0322] [Table 5]

[0323] The SPF values ​​of these compositions were measured according to the in vitro SPF method ISO 24444 and the results are summarized in Table 2.

[0324] [Table 6]

[0325] FIG. 1 shows the absorbance of UV filter compositions 1, 2 and 4 in the range of 290 to 450 nm.

[0326] Composition 2, which contains 3% by weight of the closed cell metal oxide particles of Example 2, shows increased absorption over the entire UV range from 290 to 450 nm. The in vitro SPF of the composition could be increased by 27% by adding 3% by weight of the closed cell metal oxide particles according to Example 2, compared to the placebo composition 1. In contrast, the in vitro SPF of composition 4, which contains 3% of porous metal oxide particles (silica, Sunsil-130), remained almost the same as the placebo composition 1.

[0327] Figure 2 shows the absorbance in the range 290-450 nm of UV filter compositions 1, 2 and 3. Composition 2, containing 3 wt. % of the closed cell metal oxide particles of Example 2, was compared to reference composition 3, containing 3 wt. % of the commercial polymeric UV protection boost SunSpheres™ instead of the closed cell metal oxide particles. The results are shown in Figure 2.

[0328] As can be seen from FIG. 2, the closed cell metal oxide particles performed comparable to the commercial polymer boost.

[0329] Experiment 2: Transparency / whiteness experiment The whitening effect was determined by color measurements as described above for compositions 1, 2 and 3 prepared in experiment 2. The results for the formulations with UV filters are summarized in FIG.

[0330] From Figure 3, it is observed that Composition 3 (containing 3% Sunspheres®) significantly scatters visible light and therefore provides a strong whitening effect on the skin. * increased to 12 (4.5 units or 57 percentage points compared to placebo composition 1), whereas the delta L * increases only to 8.5 (1.0 unit or 11 percentage points compared to placebo composition 1). The closed cell metal oxide particles of the present invention do not produce a visible whitening effect. This is because the delta L greater than 4 * This is because only a difference between the two can be discerned by the untrained human eye.

Claims

1. A method for increasing the sun protection factor of a UV filter composition, comprising adding closed cell metal oxide particles to said UV filter composition, the closed cell metal oxide particles include a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume; an outer surface of the closed cell metal oxide particle is defined by an array of the closed cells; The method of claim 1, wherein the metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.

2. Use of closed cell metal oxide particles for increasing the sun protection factor of a UV filter composition, comprising: the closed cell metal oxide particles include a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume; an outer surface of the closed cell metal oxide particle is defined by an array of the closed cells; The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.

3. 3. The method or use of claim 1 or 2, wherein the void volume is impermeable to media.

4. The method or use according to any one of claims 1 to 3, wherein the amount of said closed cell metal oxide particles is in the range of 0.1 to 25.0 wt.-%, based on the total weight of the UV filter composition.

5. The method or use according to any one of claims 1 to 4, wherein the array of closed cells is an ordered array.

6. The method or use according to any one of claims 1 to 4, wherein the array of closed cells is a disordered array.

7. The method or use according to any one of claims 1 to 6, wherein the closed cell metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

8. 8. The method or use according to any one of claims 1 to 7, wherein the amount of metal oxide in the closed cell metal oxide particles is in the range of 60.0 to 100.0 wt%, based on the total weight of the closed cell metal oxide particles.

9. The method or use according to any one of claims 1 to 8, wherein the closed cell metal oxide particles have an average pore diameter in the range of from 3 nm to 500 nm.

10. The method or use according to any one of claims 1 to 9, wherein the closed cell metal oxide particles have an average porosity in the range of 0.10 to 0.

90.

11. The method or use according to any one of claims 1 to 10, wherein the metal oxide matrix comprises silica.

12. The closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. The method or use according to any one of claims 1 to 11, wherein the closed cells are monodisperse.

13. The closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. The method or use of any one of claims 1 to 11, wherein the closed cells have a bimodal distribution of monodisperse closed cell metal oxide particles.

14. The closed cell metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 3 nm to 500 nm; and d. The method or use according to any one of claims 1 to 11, wherein the closed cells are polydisperse.

15. 15. The method or use according to any one of the preceding claims, wherein the closed cell metal oxide particles exhibit a colour in the visible spectrum in the wavelength range of 380nm to 800nm.

16. The UV filter composition comprises (d １ ) p-aminobenzoic acid derivatives; (d ２ ) salicylic acid derivatives; (d ３ ) benzophenone derivatives; (d ４ ) dibenzoylmethane derivatives; (d ５ ) diphenyl acrylate; (d ６ ) 3-imidazol-4-yl-acrylic acid and its esters; (d ７ ) benzofuran derivatives; (d ８ ) polymeric UV absorbers; (d ９ ) Cinnamic acid derivatives; (d １０ ) camphor derivatives; (d １１ ) Hydroxyphenyltriazine derivatives; (d １２ ) benzotriazole derivatives; (d １３ ) trianilino-s-triazine derivatives; (d １４ ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d １５ ) methyl o-aminobenzoate; (d １６ ) Homosalate; (d １７ ) tris-biphenyltriazine derivatives; (d １８ ) TiO ２ , ZnO and mica; (d １９ ) benzylidene malonate; (d ２０ ) merocyanine derivatives; (d ２１ ) phenylene bisdiphenyl triazine; (d ２２ ) imidazoline derivatives; (d ２３ ) diarylbutadiene derivatives; (d ２４ ) aminohydroxybenzoyl hexyl benzoate derivatives; (d ２５ ) bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives; and A mixture of them The method or use according to any one of claims 1 to 15, comprising at least one UV absorber selected from the group consisting of:

17. 17. The method or use according to any one of claims 1 to 16 for protecting the skin from UV light and high energy visible light.

18. The method according to any one of claims 1 to 17, further minimizing or masking the whitening effect of the UV filter composition and maintaining its transparency.

19. Use according to any one of claims 1 to 17, which further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.

20. A UV filter composition comprising 0.1 to 25.0 wt.-% of closed cell metal oxide particles based on the total weight of the UV filter composition, the closed cell metal oxide particles include a metal oxide matrix defining an array of closed cells, each closed cell enclosing a void volume; an outer surface of the closed cell metal oxide particle is defined by an array of the closed cells; 1. A UV filter composition, wherein the metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

21. 21. The UV filter composition according to claim 20, wherein the void volume is impermeable to a medium.

22. (d １ ) p-aminobenzoic acid derivatives; (d ２ ) salicylic acid derivatives; (d ３ ) benzophenone derivatives; (d ４ ) dibenzoylmethane derivatives; (d ５ ) diphenyl acrylate; (d ６ ) 3-imidazol-4-yl-acrylic acid and its esters; (d ７ ) benzofuran derivatives; (d ８ ) polymeric UV absorbers; (d ９ ) Cinnamic acid derivatives; (d １０ ) camphor derivatives; (d １１ ) Hydroxyphenyltriazine derivatives; (d １２ ) benzotriazole derivatives; (d １３ ) trianilino-s-triazine derivatives; (d １４ ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d １５ ) Methyl o-aminobenzoate; (d １６ ) Homosalate; (d １７ ) tris-biphenyltriazine derivatives; (d １８ ) TiO ２ , ZnO and mica; (d １９ ) benzylidene malonate; (d ２０ ) merocyanine derivatives; (d ２１ ) phenylene bisdiphenyl triazine; (d ２２ ) imidazoline derivatives; (d ２３ ) diarylbutadiene derivatives; (d ２４ ) aminohydroxybenzoyl hexyl benzoate derivatives; (d ２５ ) bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives, and A mixture of them 22. The UV filter composition according to claim 20 or 21, further comprising at least one UV absorber selected from the group consisting of:

23. 23. A UV filter composition according to any one of claims 20 to 22, further comprising in the range of 0.1 to 20.0 wt.-%, based on the total weight of the UV filter composition, of at least one surfactant.

24. 24. The UV filter composition according to claim 23, wherein the surfactant is selected from anionic surfactants, nonionic surfactants and polymeric surfactants.

25. 25. The UV filter composition according to any one of claims 20 to 24, further comprising additives selected from thickeners, active ingredients, preservatives and fragrances.

26. The UV filter composition according to any one of claims 20 to 25, which is a sunscreen composition.

27. The UV filter composition according to any one of claims 20 to 25, which is a day care composition.

28. 28. The UV filter composition according to any one of claims 20 to 27, which is at least one selected from the group consisting of a cream, a gel, a lotion, an alcoholic solution, an aqueous / alcoholic solution, an emulsion, a wax / fat composition, a stick formulation, a powder and an ointment.

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