UV filter composition comprising hybrid 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 hybrid metal oxide particles for increasing the SPF of a UV filter composition and to a UV filter composition comprising hybrid 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 hybrid metal oxide particles for increasing the SPF of a UV filter composition and to a UV filter composition comprising hybrid 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 hybrid metal oxide particles to a UV filter composition, the Sun Protection Factor (SPF) of the UV filter composition can be increased.

[0007] Thus, one aspect of the invention relates to a method for increasing the sun protection factor of a UV filter composition, comprising adding hybrid metal oxide particles to the UV filter composition, the hybrid metal oxide particles comprising a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles, the metal oxide particles comprising at least one second metal oxide; the first metal oxide and the second metal oxide are independently 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 hybrid metal oxide particles for increasing the sun protection factor of a UV filter composition, the hybrid metal oxide particles comprising a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles, the metal oxide particles comprising at least one second metal oxide; the first metal oxide and the second metal oxide are independently at least one 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] The hybrid metal oxide particles are non-porous.

[0010] Yet another aspect of the invention relates to a UV filter composition comprising hybrid metal oxide particles in the range of 0.1 to 25.0 wt. %, based on the total weight of the UV filter composition, wherein the hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having an array of metal oxide particles embedded therein, and the metal oxide particles comprise at least one second metal oxide; and the metal oxide is independently at least one 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]

[0011] [Figure 1] 1 shows the relative absorbance values ​​(RAV) of UV filter composition 1 (placebo), composition 2 (3 wt. % hybrid metal oxide particles according to example 1) and composition 3 (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. % hybrid metal oxide particles according to Example 1) and composition 3 (comparative example). [Diagram 3] FIG. 1 shows a chart for the lightness L* of UV filter composition 1 (placebo), composition 2 (3 wt. % hybrid metal oxide particles according to example 1) and composition 3 (commercial UV protection boost). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] 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.

[0013] 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.

[0014] Furthermore, 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.

[0015] 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.

[0016] 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.

[0017] Furthermore, particular features, structures or characteristics may be combined in any suitable manner in one or more embodiments, as would be apparent to one of ordinary skill in the art from this disclosure. 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 others, 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.

[0018] It has been found that it is possible to use hybrid 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 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.

[0019] Hybrid metal oxide particles are structural colorants that interact with UV and visible radiation via light interference effects. Structural colorants are materials that contain nanoscale structured surfaces that are small enough to interfere with visible light and produce color. Bulk samples of hybrid 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 hybrid 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.

[0020] Thus, one aspect of the invention relates to a method for increasing the sun protection factor of a UV filter composition, comprising adding hybrid metal oxide particles to the UV filter composition, the hybrid metal oxide particles comprising a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles, the metal oxide particles comprising at least one second metal oxide; the first metal oxide and the second metal oxide are independently 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] The hybrid metal oxide particles are non-porous.

[0022] Another aspect of the present invention relates to the use of hybrid metal oxide particles for increasing the sun protection factor of a UV filter composition, the hybrid metal oxide particles comprising a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles, the metal oxide particles comprising at least one second metal oxide; the first metal oxide and the second metal oxide are independently at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0023] The hybrid metal oxide particles are non-porous.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] In the context of the present invention, the term "micro" or "microscale" means 0.5 μm to 999 μm. The term "nano" or "nanoscale" means 1 nm to 999 nm.

[0032] In the context of the present invention, the terms "sphere" and "particle" are interchangeable.

[0033] In the context of the present invention, the term "continuous matrix" means that at least one first metal oxide forms a continuous subpopulation as a homogeneous phase. This homogeneous oxide phase can be crystalline or amorphous. The oxide phase of the particles of the first metal oxide is essentially free of the second metal oxide. The second metal oxide particles are embedded within the continuous population of particles of the at least one first metal oxide and form separate sections within the continuous matrix that exhibit a different refractive index than the continuous matrix itself. This differs from doped metal oxide materials, in which the doped metal is included within the (crystalline) structure of the doped metal oxide, and both metals are homogeneously distributed within the doped metal oxide.

[0034] 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.

[0035] In a preferred embodiment, the amount of hybrid metal oxide particles ranges from 0.1 to 25.0% by weight, based on the total weight of the UV filter composition.

[0036] In a more preferred embodiment, the amount of hybrid metal oxide particles is in the range of 0.5 to 10.0 wt.%, based on the total weight of the UV filter composition, in an even more preferred embodiment, the amount of hybrid metal oxide particles is in the range of 1.0 to 8.0 wt.%, most preferably 1.0 to 5.0 wt.%, based on the total weight of the UV filter composition.

[0037] In a preferred embodiment, the hybrid 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.

[0038] In a preferred embodiment, the amount of metal oxide in the hybrid metal oxide particles is in the range of 60.0 to 100.0 wt %, based on the total weight of the hybrid metal oxide particles.

[0039] In a more preferred embodiment, the amount of metal oxide in the hybrid metal oxide particles is in the range of 75.0 to 99.9 wt %, even more preferably 90.0 to 99.9 wt %, and most preferably 95.0 to 99.9 wt %, based on the total weight of the hybrid metal oxide particles.

[0040] In a preferred embodiment, the amount of the first metal oxide is in the range of 2 to 90 wt %, based on the total weight of the hybrid metal oxide particles. In a more preferred embodiment, the amount of the first metal oxide is in the range of 5 to 80 wt %, even more preferably 7 to 70 wt %, and most preferably 10 to 50 wt %, based on the total weight of the hybrid metal oxide particles.

[0041] In a preferred embodiment, the first metal oxide is selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0042] In a preferred embodiment, the first metal oxide is titania.

[0043] In a preferred embodiment, the amount of the second metal oxide is in the range of 10 to 98 wt.%, based on the total weight of the hybrid metal oxide particles. In a more preferred embodiment, the amount of the second metal oxide is in the range of 5 to 80 wt.%, even more preferably 7 to 70 wt.%, and most preferably 10 to 50 wt.%, based on the total weight of the hybrid metal oxide particles.

[0044] In a preferred embodiment, the first metal oxide particles are fused together during preparation resulting in a continuous first metal oxide matrix.

[0045] In a preferred embodiment, the second metal oxide is selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0046] In a preferred embodiment, the second metal oxide is silica.

[0047] In a preferred embodiment, the metal oxide particles comprising at least one second metal oxide have an average diameter in the range of 50 nm to 999 nm. In a preferred embodiment, the metal oxide particles comprising at least one second metal oxide have an average diameter in the range of 75 nm to 600 nm; most preferably 100 to 500 nm.

[0048] In a particularly preferred embodiment of the present invention, the second metal oxide particles have an average diameter at least 3 times larger than that of the first metal oxide, preferably the second metal oxide has an average diameter at least 5 times, more preferably at least 8 times, even more preferably at least 10 times, particularly preferably at least 12 times, most preferably at least 15 times larger than that of the first metal oxide. The smaller first metal oxide forms a continuous matrix in which the larger particles of the second metal oxide are embedded. The formation of a continuous matrix of the first metal oxide and the embedding of the second metal oxide in the matrix works particularly well due to the favorable difference in average diameter between the first metal oxide and the second metal oxide.

[0049] In a preferred embodiment, the weight ratio of the first metal oxide to the second metal oxide is in the range of 1:50 to 10: 1. In a more preferred embodiment, the weight ratio of the first metal oxide to the second metal oxide is in the range of 1:20 to 10: 1, even more preferably 1:10 to 10: 1, and most preferably 1:4 to 4:1.

[0050] In a preferred embodiment, the weight ratio of the first metal oxide to the second metal oxide is 2:3.

[0051] In a preferred embodiment, the first metal oxide particles and / or the second metal oxide particles comprise a combination of different types of particles. For example, the first metal oxide particles can be a mixture of two different metal oxides (i.e., a discrete distribution of metal oxide particles), such as a mixture of alumina and silica particles, each of which is characterized by the same or similar size distribution.

[0052] In some embodiments, the first metal oxide particles and / or the second metal oxide particles comprise more complex compositions and / or morphologies. For example, the first metal oxide particles may comprise particles in which each particle comprises two or more metal oxides (e.g., silica-titania particles). Such particles may comprise, for example, an amorphous mixture of two or more metal oxides or may have a core-shell configuration (e.g., titania-coated silica particles, polymer-coated silica, carbon black-coated silica, etc.).

[0053] In a preferred embodiment, the continuous matrix further comprises at least one binder.

[0054] In a preferred embodiment, the binder is selected from silica, sodium silicate, magnesium silicate, calcium silicate, aluminum silicate, aluminum oxide hydroxide, sodium oxide, calcium carbonate, calcium aluminate, bentonite, kaolinite, montmorillonite, and combinations thereof.

[0055] In a preferred embodiment, the second metal oxide particles have a core-shell structure.

[0056] In a preferred embodiment, the second metal oxide particles are spherical metal oxide particles.

[0057] In a preferred embodiment, the arrangement of the second metal oxide particles is an ordered arrangement.

[0058] In a preferred embodiment, the arrangement of the second metal oxide particles is a disordered arrangement.

[0059] The terms "ordered array" and "disordered array" of second metal oxide particles refer to a structural arrangement of the second metal oxide particles defined by a continuous matrix of at least the first metal oxide. In the case of an "ordered array", the second metal oxide particles are arranged in a repeating pattern in the continuous matrix. According to preferred embodiments, such an ordered array results in an angle-dependent color. In the case of a "disordered array", the second metal oxide particles are randomly distributed within the continuous matrix. According to preferred embodiments, such a disordered array results in an angle-independent color.

[0060] The term "surface functionalization" in the present invention refers to the alteration of a material surface by imparting physical or chemical properties different from those originally found on the material surface. In the present invention, the surface modification is preferably the formation of covalent bonds by a surface functionalizing agent (e.g., a silane coupling agent as a surface functionalizing agent).

[0061] In a preferred embodiment, the second metal oxide particles have a surface functionalization. Examples of surface functionalization include silane coupling agents (e.g., silane-functionalized silica).

[0062] In a preferred embodiment, surface functionalization is performed on the first metal oxide particles and / or the second metal oxide particles prior to self-assembly and densification.

[0063] In some embodiments, surface functionalization is performed on the hybrid metal oxide particles after densification.

[0064] In a preferred embodiment, the hybrid metal oxide particles include surface functionalization.

[0065] In a preferred embodiment, the surface functionalization is carried out using a silane compound.

[0066] In a preferred embodiment, the hybrid metal oxide particles are - generating droplets from a particle dispersion comprising first metal oxide particles and second metal oxide particles; - drying the droplets to provide dried particles comprising a discrete matrix of first metal oxide particles having embedded therein second metal oxide particles; and - heating the dried particles to obtain hybrid metal oxide particles comprising a continuous matrix formed from the first metal oxide particles having an array of second metal oxide particles embedded therein. It is prepared by a method comprising:

[0067] In a preferred embodiment, the step of heating the particles includes sintering or calcining the dried particles to densify the first metal oxide particles to form a continuous matrix.

[0068] In a preferred embodiment, the droplets further comprise a binder, and the step of heating the dried particles facilitates forming a continuous matrix from the binder and the first metal oxide particles.

[0069] In a preferred embodiment, the first metal oxide particles have an average diameter of 1 nm to 120 nm. According to a more preferred embodiment of the present invention, the first metal oxide particles have an average diameter of 2 nm to 60 nm, even more preferably 3 nm to 20 nm.

[0070] In a preferred embodiment, the second metal oxide particles have an average diameter of from 50 nm to 999 nm.

[0071] In a preferred embodiment, one or more of the first metal oxide particles or the second metal oxide particles comprises a core-shell structure.

[0072] In a preferred embodiment, the step of generating the droplets is carried out using a microfluidic process.

[0073] In a preferred embodiment, the steps of generating and drying the droplets are carried out using a spray drying process.

[0074] In a preferred embodiment, the step of generating the droplets is carried out using a vibrating nozzle.

[0075] In a preferred embodiment, the step of drying the droplets comprises evaporation, microwave irradiation, oven drying, drying under vacuum, drying in the presence of a desiccant, or a combination thereof.

[0076] In a preferred embodiment, the liquid dispersion is an aqueous dispersion, an oil-based dispersion, an organic solvent dispersion, or a combination thereof.

[0077] In a preferred embodiment, the particle size ratio of the first metal oxide particles to the second metal oxide particles is 1:20 to 1:5.

[0078] In a preferred embodiment, the hybrid metal oxide particles are - generating droplets from a particle dispersion comprising a sol-gel matrix of particles comprising a precursor of a first metal oxide and a second metal oxide; and - Drying the droplets and densifying the sol-gel matrix into a continuous matrix to produce hybrid metal oxide particles. It is prepared by a method comprising:

[0079] In a preferred embodiment, the precursor is at least one selected from a metal alkoxide or a metal chloride.

[0080] In a preferred embodiment, the second metal oxide particles are spherical metal oxide particles.

[0081] In a preferred embodiment, the hybrid metal oxide particles are having an average diameter in the range of 0.5 μm to 100.0 μm; comprising at least one first metal oxide as a continuous matrix; second metal oxide particles having an average diameter in the range of 50 nm to 999 nm; and The second metal oxide particles are monodisperse.

[0082] In a preferred embodiment, the hybrid metal oxide particles are having an average diameter in the range of 0.5 μm to 100.0 μm; comprising at least one first metal oxide as a continuous matrix; second metal oxide particles having an average diameter in the range of 50 nm to 999 nm; and It has a bimodal distribution of monodisperse second metal oxide particles.

[0083] In a preferred embodiment, the hybrid metal oxide particles are having an average diameter in the range of 0.5 μm to 100.0 μm; comprising at least one first metal oxide as a continuous matrix; second metal oxide particles having an average diameter in the range of 50 nm to 999 nm; and The second metal oxide particles are polydisperse.

[0084] In a preferred embodiment, the hybrid metal oxide particles exhibit color in the visible spectrum in the wavelength range of 380 nm to 800 nm.

[0085] In a preferred embodiment, the hybrid metal oxide particles are effective in wavelength regions in the ultraviolet spectrum ranging from 100 nm to 400 nm.

[0086] In a preferred embodiment, the hybrid metal oxide particles are effective in wavelength regions in the ultraviolet and visible spectrum ranging from 200 nm to 500 nm.

[0087] In a preferred embodiment, the hybrid metal oxide particles exhibit angle-dependent color. By "angle-dependent" color, we mean 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.

[0088] In a preferred embodiment, the hybrid metal oxide particles exhibit angle-independent color. By "angle-independent" color we mean 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.

[0089] Angle-dependent color can be achieved, for example, by using monodisperse metal oxide particles (e.g., the second metal oxide particles in this embodiment). Angle-dependent color can also be achieved if the step of drying the droplets is performed slowly to allow the particles to order.

[0090] Angle-independent color can be achieved if the step of drying the droplets is performed rapidly and does not allow the particles to order.

[0091] The following embodiments may be utilized to achieve angle-dependent color resulting from ordered template particles, where the template particles and matrix particles comprise different metal oxides (e.g., titania matrix particles and silica template particles). As a first exemplary embodiment of angle-dependent color, monodisperse, spherical template particles are embedded in a matrix particle, which is then densified. As a second exemplary embodiment of angle-dependent color, two or more types of template particles that are collectively monodisperse, spherical are embedded in a matrix particle, which is then densified. The angle-dependent color is achieved regardless of the polydispersity and shape of the matrix particle.

[0092] The following embodiment may be utilized to achieve angle-independent color arising from disordered template particles, where the template particles and matrix particles comprise different metal oxides (e.g., titania matrix particles and silica template particles): As a first exemplary embodiment of angle-independent color, polydisperse template particles are embedded in matrix (e.g., metal oxide) particles, and the matrix particles are then densified.

[0093] As a second exemplary embodiment of angle-independent color, two different sizes of spherical template particles (i.e., a bimodal distribution of monodisperse template particles) are embedded in a matrix particle, which is then densified. The matrix particle can be spherical or non-spherical.

[0094] As a third exemplary embodiment of angle-independent color, two different sized polydisperse spherical template particles are embedded in a matrix particle, which is then densified.

[0095] Angle-independent color is achieved independent of the polydispersity and shape of the matrix particles.

[0096] Any of the embodiments that exhibit angle-dependent or angle-independent color can be modified to exhibit whiteness or effects in the ultraviolet spectrum (eg, reflectance, absorbance).

[0097] In a preferred embodiment, the hybrid metal oxide particles further comprise a light absorber.

[0098] In a preferred embodiment, the light absorber is present in the range of 0.1 to 40.0% by weight, more preferably 0.5 to 25.0% by weight, and most preferably 1.0 to 10.0% by weight.

[0099] In a preferred embodiment, the light absorber comprises at least one ionic species.

[0100] 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 ) phenylenebisdiphenyltriazine; (d 22 ) imidazoline derivatives; (d 23 ) diarylbutadiene derivatives; (d 24 ) aminohydroxybenzoyl hexyl benzoate derivatives; and (d25 ) Bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivative.

[0101] Examples of p-aminobenzoic acid derivatives (d1) that can be utilized according to the present invention include 4-aminobenzoic acid (PABA); [ka] Ethyl dihydroxypropyl-PABA; of the following formula (PABA-02): [ka] PEG-25PABA (wherein m, n and x have the same meaning and each represents an integer of 1 to 25); [ka] or the following formula (PABA-04): [ka] It is glycyl aminobenzoate.

[0102] An example of a salicylic acid derivative (d2) that can be utilized according to the present invention is represented by the following formula (SAD-01): [ka] Homomenthyl salicylate of the following formula (SAD-02): [ka] Triethanolamine salicylate of the formula (SAD-03) [ka] p-Dimethylaminobenzoic acid amyl; the following formula (SAD-04): [ka] or the following formula (SAD-05): [ka] The compound is 4-isopropylbenzyl salicylate.

[0103] 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-C10 -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.

[0104] In a more preferred embodiment, the UV absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

[0105] 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; [ka] 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 invention; which may also be utilized in accordance with the present invention.

[0106] In a more preferred embodiment, [ka] The dimeric benzophenone derivative is used as a UV absorber (d3).

[0107] 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].

[0108] 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).

[0109] 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 following formula (BF01): [ka] It is a compound of the formula:

[0110] 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 (PUV-01) [ka] (In the formula, R 24 represents hydrogen or methoxy, and r is about 7; The following formula: [ka] or The following formula: [ka] The corresponding polysilicone-15 is

[0111] 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.

[0112] 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.

[0113] Hydroxyphenyltriazine derivatives (d 11 Examples of ) are in particular those of the formula (HPT-01) [ka] (In the formula, R1 and R2 are each independently hydrogen; 18 -Alkyl; C2-C 18 -alkenyl; a radical 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; amino; mono- or di-C1-C5-alkylamino; M; [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 following formula (HPT-01m) [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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] In a more preferred embodiment, the benzotriazole derivative (d 12 ) is expressed as follows: [ka] It is a compound of the formula:

[0118] 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-.

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

[0120] 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.

[0121] 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

[0122] 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).

[0123] Tris-biphenyl-triazine derivatives (d 17 ) is the formula [ka] (In the formula, A is the following formula (TBT-01a) [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 a group represented by the following formula (TBT-01c): [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.

[0124] In a preferred embodiment, the UV filters (d 17 ) is expressed as follows: [ka] Corresponds to.

[0125] 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.

[0126] In a preferred embodiment, benzylidene malonates (d 19 ) are shown in the table below.

[0127] [Table 1]

[0128] 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 [ka] Corresponds to.

[0129] The imidazoline derivatives (d 22 An example of is ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

[0130] Diarylbutadiene derivatives (d 23 An example of is 1,1-dicarboxy-(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

[0131] 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.

[0132] Bis-(diethylaminohydroxybenzoyl)-piperazine derivatives (d 25 ) is the formula [ka] (BDBP).

[0133] 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.

[0134] 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.

[0135] 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); (dSOL-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.

[0136] In a more preferred embodiment, the following particulate UV filters are used according to the invention: Methylenebisbenzotriazolyltetramethylbutylphenol(nano)(MBBT); (TBT-02) Tris-biphenyltriazine (nano) (TBPT); Bis-(diethylaminohydroxybenzoyl)piperazine (nano) (BDBP); and Phenylenebis-diphenyltriazine (PBDT).

[0137] 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; (d3a )Diethylaminohydroxybenzoylhexyl benzoate; Merocyanine; Methylenebisbenzotriazolyltetramethylbutylphenol(nano)(MBBT); (TBT-02) Tris-biphenyltriazine (nano) (TBPT); and Bis-(diethylaminohydroxybenzoyl)piperazine(nano)(BDBP).

[0138] In a particularly preferred embodiment, the UV filter is 9a ), (d 11a ), (d 13a ) and (d 3a ).

[0139] In a preferred embodiment, the method or use is applied to protect the skin from UV radiation and high energy visible light.

[0140] In a preferred embodiment, the method or use is utilized to protect 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.

[0141] The method or use is utilized to protect the skin from high energy visible light with wavelengths in the range 380-480 nm.

[0142] In a preferred embodiment, the method further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.

[0143] In a preferred embodiment, the use further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.

[0144] UV filter composition comprising hybrid metal oxide particles Another aspect of the present invention relates to a UV filter composition comprising hybrid metal oxide particles in the range of 0.1-25.0 wt. %, based on the total weight of the UV filter composition. The hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles comprising at least one second metal oxide. The first and second metal oxides are at least one independently selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0145] In a preferred embodiment, the hybrid metal oxide particles are non-porous.

[0146] In a more preferred embodiment, the amount of hybrid metal oxide particles is in the range of 0.5 to 10.0 wt.%, based on the total weight of the UV filter composition, in an even more preferred embodiment, the amount of hybrid metal oxide particles is in the range of 1.0 to 8.0 wt.%, most preferably 1.0 to 5.0 wt.%, based on the total weight of the UV filter composition.

[0147] In a preferred embodiment, the UV filter composition comprises a) water; and b) Hybrid metal oxide particles in the range of 0.1 to 25.0 wt. % based on the total weight of the UV filter composition Includes.

[0148] In a preferred embodiment, the UV filter composition comprises a) water; and b) Hybrid metal oxide particles in the range of 0.5 to 10.0 wt. % based on the total weight of the UV filter composition Includes.

[0149] In a preferred embodiment, the UV filter composition comprises a) water; b) oil; and c) Hybrid 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.

[0150] 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.

[0151] 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.

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

[0153] In a preferred embodiment, the UV filter composition comprises a) oil; and b) Hybrid metal oxide particles in the range of 0.5 to 10.0 wt. % based on the total weight of the UV filter composition Includes.

[0154] In a preferred embodiment, the hybrid metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

[0155] In a preferred embodiment, the amount of metal oxide in the hybrid metal oxide particles is in the range of 60.0 to 100.0 wt %, based on the total weight of the hybrid metal oxide particles.

[0156] In a preferred embodiment, the hybrid metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

[0157] In a preferred embodiment, the hybrid metal oxide particles further comprise a light (UV-visible) absorber.

[0158] In a preferred embodiment, the light (UV-visible) absorber is present in the range of 0.1% to 40.0% by weight.

[0159] 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 ) phenylenebisdiphenyltriazine; (d 22 ) imidazoline derivatives; (d 23) diarylbutadiene derivatives; (d 24 ) aminohydroxybenzoyl hexyl benzoate derivatives; and (d 25 ) Bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivative.

[0160] Representative examples of UV absorbers are described herein.

[0161] In a preferred embodiment, the UV filter composition is a sunscreen composition.

[0162] In a preferred embodiment, the UV filter composition is a day care composition.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] Furthermore, the UV filter composition may contain further adjuvants as described below.

[0167] 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.

[0168] 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.

[0169] Linear and branched fatty alcohol carbonates, in particular dicaprylyl carbonate, are particularly preferably used as oily substances.

[0170] In a more preferred embodiment, dibutyl adipate is used as the oily substance.

[0171] 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.

[0172] 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.

[0173] 2) Surfactants In a preferred embodiment, the UV filter composition further comprises at least one emulsifier in the range of 1.0 to 20.0% by weight, based on the total weight of the UV filter composition.

[0174] In a preferred embodiment, the emulsifier is selected from the group consisting of anionic emulsifiers, cationic emulsifiers, non-ionic emulsifiers and polymeric emulsifiers.

[0175] Anionic surfactants are characterized by one or more anionic groups and lipophilic groups that provide solubility in water, such as carboxylate, sulfate, sulfonate or phosphate groups.Furthermore, this molecule can contain polyglycol ether, ester, ether and hydroxyl groups.Many anionic surfactants that are acceptable to skin are known to those skilled in the art from related handbooks and are commercially available.

[0176] 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®.

[0177] 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.

[0178] 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.

[0179] 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 of 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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] Suitable co-surfactants are, in principle, zwitterionic, amphoteric, cationic and / or non-ionic surfactants.

[0185] 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.

[0186] Amphoteric surfactants are those that have C8 to C 18It 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.

[0187] 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.

[0188] 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-polyalkyl-polyether 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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).

[0193] 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, such as glucamine.

[0194] Polyglycerol-based reaction products are of particular interest due to their excellent use properties.

[0195] 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.

[0196] 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.

[0197] In a preferred embodiment of the present invention, Eumulgin® SG, Eumulgin® Prisma, Emulgade® sucro and Emulgade® SucroPlus are used as surfactants.

[0198] 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.

[0199] 3) Additives In a preferred embodiment, the UV filter composition further comprises an additive selected from the group consisting of thickeners, active ingredients, preservatives and fragrances.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] Preservatives Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and silver complexes known under the name Surfacine®.

[0210] 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.

[0211] 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, benzyl salicylate ... 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.

[0212] 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.

[0213] 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.

[0214] 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.

[0215] 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.

[0216] 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-hydroxyfatty 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.

[0217] 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®.

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] So-called stabilizers which can be used are metal salts of fatty acids, such as magnesium stearate or ricinoleate, aluminium and / or zinc.

[0223] 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.

[0224] To improve skin feel, starch derivatives such as DryFlo® PC (INCI: Aluminum Starch Octenylsuccinate) can additionally be utilized.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] The dyes which may be used are substances suitable and approved for cosmetic purposes.

[0229] The invention provides one or more of the following advantages.

[0230] 1. The present invention provides a method for increasing the sun protection factor of UV filter compositions using hybrid metal oxide particles.

[0231] 2. The method of the present invention increases the SPF of a sunscreen formulation while minimizing or masking its whitening effect and maintaining its transparency.

[0232] 3. The hybrid metal oxide particles of the present invention can be used to increase the SPF of UV filter compositions.

[0233] 4. The hybrid 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.

[0234] 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.

[0235] 1. A method for increasing the sun protection factor of a UV filter composition, comprising adding hybrid metal oxide particles to the UV filter composition, The hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having an array of metal oxide particles embedded therein, the metal oxide particles comprising at least one second metal oxide; The method wherein the first metal oxide and the second metal oxide are independently selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0236] 2. The use of hybrid metal oxide particles to increase the sun protection factor of a UV filter composition, comprising: The hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having an array of metal oxide particles embedded therein, the metal oxide particles comprising at least one second metal oxide; The first metal oxide and the second metal oxide are independently at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0237] 3. The method or use according to embodiment 1 or 2, wherein the hybrid metal oxide particles are non-porous.

[0238] 4. The method or use according to any one of the preceding embodiments, wherein the amount of hybrid 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.

[0239] 5. The method or use according to any one of the preceding embodiments, wherein the amount of hybrid 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.

[0240] 6. The method or use according to any one of the preceding embodiments, wherein the hybrid metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

[0241] 7. The method or use according to any one of the preceding embodiments, wherein the amount of metal oxide in the hybrid metal oxide particles is in the range of 60.0 to 100.0 wt.%, based on the total weight of the hybrid metal oxide particles.

[0242] 8. The method or use according to any one of the preceding embodiments, wherein the amount of the first metal oxide is in the range of 2 to 90% by weight, based on the total weight of the hybrid metal oxide particles.

[0243] 9. The method or use according to any one of the preceding embodiments, wherein the first metal oxide is selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0244] 10. The method or use according to any one of the preceding embodiments, wherein the first metal oxide is titania.

[0245] 11. The method or use according to any of the preceding embodiments, wherein the amount of the second metal oxide is in the range of 10 to 98% by weight, based on the total weight of the hybrid metal oxide particles.

[0246] 12. The method or use according to any one of the preceding embodiments, wherein the second metal oxide is selected from silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide and mixtures thereof.

[0247] 13. The method or use according to any one of the preceding embodiments, wherein the second metal oxide is silica.

[0248] 14. The method or use according to any of the preceding embodiments, wherein the metal oxide particles comprising at least one second metal oxide have an average diameter in the range of 50 nm to 999 nm.

[0249] 15. The method or use according to any one of the preceding embodiments, wherein the weight ratio of the first metal oxide to the second metal oxide is in the range of 1:50 to 10:1.

[0250] 16. The method or use according to any one of the preceding embodiments, wherein the weight ratio of the first metal oxide to the second metal oxide is 2:3.

[0251] 17. The method or use according to any one of the preceding embodiments, wherein the continuous matrix further comprises at least one binder.

[0252] 18. The method or use according to embodiment 17, wherein the binder is selected from silica, sodium silicate, magnesium silicate, calcium silicate, aluminum silicate, aluminum oxide hydroxide, sodium oxide, calcium carbonate, calcium aluminate, bentonite, kaolinite, montmorillonite, and combinations thereof.

[0253] 19. The method or use according to any one of the preceding embodiments, wherein the second metal oxide particles have a core-shell structure.

[0254] 20. The method or use according to any one of the preceding embodiments, wherein the second metal oxide particles are spherical metal oxide particles.

[0255] 21. The method or use according to any one of the preceding embodiments, wherein the arrangement of the second metal oxide particles is an ordered arrangement.

[0256] 22. The method or use according to any one of the preceding embodiments, wherein the arrangement of the second metal oxide particles is a disordered arrangement.

[0257] 23. The method or use according to any one of the preceding embodiments, wherein the second metal oxide particles have a surface functionalization.

[0258] 24. The method or use according to any one of the preceding embodiments, wherein the hybrid metal oxide particles comprise a surface functionalization.

[0259] 25. The method or use according to embodiment 23 or 24, wherein the surface functionalization is carried out using a silane compound.

[0260] 26. Hybrid metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. comprising at least one first metal oxide as a continuous matrix; c. a second metal oxide particle having an average diameter in the range of 50 nm to 999 nm; and d. The method or use according to any of embodiments 1 to 25, wherein the second metal oxide particles are monodisperse.

[0261] 27. Hybrid metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. comprising at least one first metal oxide as a continuous matrix; c. a second metal oxide particle having an average diameter in the range of 50 nm to 999 nm; and d. The method or use of any one of the preceding embodiments, having a bimodal distribution of monodisperse second metal oxide particles.

[0262] 28. Hybrid metal oxide particles are a. having an average diameter in the range of 0.5 μm to 100.0 μm; b. comprising at least one first metal oxide as a continuous matrix; c. a second metal oxide particle having an average diameter in the range of 50 nm to 999 nm; and d. The method or use of any one of the preceding embodiments, wherein the second metal oxide particles are polydisperse.

[0263] 29. The method or use according to any one of the preceding embodiments, wherein the hybrid metal oxide particles exhibit a color in the visible spectrum in the wavelength range of 380 nm to 800 nm.

[0264] 30. The method or use according to any one of the preceding embodiments, wherein the hybrid metal oxide particles are effective in the wavelength range in the ultraviolet spectrum ranging from 100 nm to 400 nm.

[0265] 31. The method or use according to any one of the preceding embodiments, wherein the hybrid metal oxide particles are effective in wavelength regions in the ultraviolet and visible spectrum ranging from 200 nm to 500 nm.

[0266] 32. 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; and (d 25 ) Bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives 32. The method or use according to any one of the preceding embodiments, further comprising a UV absorber selected from the group consisting of:

[0267] 33. A method or use according to any one of embodiments 1 to 32 for protecting the skin from ultraviolet light and high-energy visible light.

[0268] 34. The method or use according to embodiment 33 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.

[0269] 35. The method or use according to embodiment 33 or 34, for protecting the skin from high-energy visible light with a wavelength in the range of 380 to 480 nm.

[0270] 36. 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.

[0271] 37. 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.

[0272] 38. A UV filter composition comprising hybrid metal oxide particles in the range of 0.1 to 25.0 wt. % based on the total weight of the UV filter composition; The hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having an array of metal oxide particles embedded therein, the metal oxide particles comprising at least one second metal oxide; The UV filter composition, wherein the first metal oxide and the second metal oxide are at least one independently selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.

[0273] 39. A UV filter composition according to embodiment 38, wherein the hybrid metal oxide particles are non-porous.

[0274] 40.a. Water; and b. Hybrid metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition 40. The UV filter composition according to embodiment 38 or 39, comprising

[0275] 41.a. Water; and b. Hybrid metal oxide particles in the range of 0.5 to 10.0% by weight based on the total weight of the UV filter composition 41. The UV filter composition according to embodiment 40, comprising:

[0276] 42.a.Water; b. oil; and c. Hybrid metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition 40. The UV filter composition according to embodiment 38 or 39, comprising

[0277] 43. A UV filter composition according to embodiment 42, wherein 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.

[0278] 44. A UV filter composition according to embodiment 42, 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.

[0279] 45.a. Oil; and b. Hybrid metal oxide particles in the range of 0.1 to 25.0% by weight based on the total weight of the UV filter composition 40. The UV filter composition according to embodiment 38 or 39, comprising

[0280] 46.a. Oil; and b. Hybrid metal oxide particles in the range of 0.5 to 10.0% by weight based on the total weight of the UV filter composition 46. ​​The UV filter composition according to embodiment 45, comprising:

[0281] 47. A UV filter composition according to any one of embodiments 38 to 46, wherein the hybrid metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

[0282] 48. The UV filter composition according to any one of embodiments 38 to 47, wherein the amount of metal oxide in the hybrid metal oxide particles is in the range of 60.0 to 100.0 wt.-%, based on the total weight of the hybrid metal oxide particles.

[0283] 49.(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; and (d 25 ) Bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivatives 49. The UV filter composition according to any one of embodiments 38 to 48, further comprising a UV absorber selected from the group consisting of:

[0284] 50. The UV filter composition according to any one of embodiments 38 to 49, further comprising at least one emulsifier in the range of 1.0 to 20.0 wt.-%, based on the total weight of the UV filter composition.

[0285] 51. A UV filter composition according to embodiment 50, wherein the emulsifier is selected from the group consisting of anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers and polymeric emulsifiers.

[0286] 52. The UV filter composition according to any one of embodiments 38 to 51, further comprising an additive selected from the group consisting of thickeners, active ingredients, preservatives and fragrances.

[0287] 53. A UV filter composition according to any one of embodiments 38 to 52, which is a sunscreen composition.

[0288] 54. A UV filter composition according to any one of embodiments 38 to 52, which is a day care composition.

[0289] 55. A UV filter composition according to any one of embodiments 38 to 54, 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.

[0290] 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

[0291] 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.

[0292] 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.

[0293] 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.

[0294] 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 hybrid metal oxide particles is calculated as the ratio of unoccupied space to the total particle volume. For example, porous silica particles containing voids / pores with an average diameter of 165 nm have an average porosity of 0.8.

[0295] 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.

[0296] 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 er The average reverse transmittance (1 / T) of each sunscreen in the spectral range of 290-400 nm, including the scale in (λ), is calculated.

number

[0297] 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

[0298] 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.

[0299] experiment Example 1: Preparation of hybrid silica / zinc oxide particles An aqueous suspension of 100 nm spherical silica nanoparticles and zinc oxide nanoparticles was prepared. The aqueous suspension contained 1.8 wt. % 100 nm silica nanoparticles and 1.2 wt. % zinc oxide nanoparticles based on the total weight of the aqueous suspension. 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).

[0300] 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 fired in a muffle furnace in a batch firing process to densify and stabilize the particles. The heating parameters were as follows: the particles were heated from room temperature to 500°C over 4 hours, held at 500°C for 2 hours, and then cooled to room temperature over 4 hours.

[0301] Example 2: Hybrid titania / silica particles with angle-dependent / ordered structure An aqueous suspension of 180 nm spherical silica nanoparticles and 5 nm titania nanoparticles was prepared. The aqueous suspension contained 1.8 wt% silica nanoparticles and 1.2 wt% titania nanoparticles based on the total weight of the aqueous suspension. 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).

[0302] 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 fired in a muffle furnace in a batch firing process to densify and stabilize the particles. The heating parameters were as follows: the particles were heated from room temperature to 550°C over 12 hours, held at 550°C for 2 hours, and then cooled to room temperature over 3 hours.

[0303] Example 3: Disordered hybrid silica / titania particles An aqueous suspension of 180 nm spherical silica nanoparticles, 160 nm spherical silica nanoparticles, and 5 nm titania nanoparticles was prepared. The aqueous suspension contained 1.2 wt% 180 nm silica nanoparticles, 0.6 wt% 160 nm silica nanoparticles, and 1.2 wt% titania nanoparticles based on the total weight of the aqueous suspension. 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).

[0304] 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 fired in a muffle furnace in a batch firing process to densify and stabilize the particles. The heating parameters were as follows: the particles were heated from room temperature to 550°C over 7 hours, held at 550°C for 2 hours, and then cooled to room temperature over 4 hours.

[0305] SEM images of the hybrid metal oxide particles confirmed the presence of disordered template (silica) nanoparticles, which exhibited angle-independent blue coloration when dispersed in mineral oil containing 1 wt% carbon black per mass of colorant.

[0306] Example 4: Hybrid zinc oxide / silica particles produced by sol-gel process An aqueous suspension of 135 nm zinc oxide nanoparticles was prepared. The aqueous suspension contained 1.8 wt% of 135 nm zinc oxide nanoparticles based on the total weight of the aqueous suspension. TEOS was then dissolved in the suspension at a concentration of 17.4 mg / mL. 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).

[0307] 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 fired in a muffle furnace in a batch firing process to densify and stabilize the particles. The heating parameters were as follows: the particles were heated from room temperature to 500°C over 4 hours, held at 500°C for 2 hours, and then cooled to room temperature over 4 hours.

[0308] Example 5: Hybrid Alumina / Silica Particles An aqueous suspension of 300 nm spherical alumina nanoparticles and 5 nm silica nanoparticles was prepared. The aqueous suspension contained 1.8 wt% 300 nm alumina nanoparticles and 1.2 wt% 5 nm silica nanoparticles based on the total weight of the aqueous suspension. 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).

[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 fired in a muffle furnace in a batch firing process to densify and stabilize the particles. The heating parameters were as follows: the particles were heated from room temperature to 500°C over 4 hours, held at 500°C for 2 hours, and then cooled to room temperature over 4 hours.

[0310] Characterization Experiment 1: Light attenuation by hybrid metal oxide particles To determine the light attenuation properties, a dispersion (Dispersion 1) of the hybrid metal oxide particles obtained in Example 1 was prepared at a concentration of 1.67 mg / mL in an oil (such as mineral oil) with a refractive index of about 1.5. For comparison, two dispersions (Dispersions 2 and 3) were prepared in the same manner as Dispersion 1, but using silica nanoparticles and zinc oxide nanoparticles, respectively, instead of the hybrid metal oxide particles.

[0311] Dispersions 1, 2 and 3 were placed into separate wells, 300 μL per well, of a UV-clear 96-well microtiter plate, and the UV-visible light transmittance through the wells was measured using a plate reader spectrophotometer. The output is expressed in relative absorbance values ​​(RAV) minus the UV-visible light attenuation of the blank, oil only as background.

[0312] The RAV values ​​of the hybrid metal oxide particles, silica and zinc oxide particles are shown in Figure 1. A higher RAV value indicates a greater attenuation of UV light.

[0313] As is apparent from Figure 1, the hybrid metal oxide particles have significantly higher RAV values ​​compared to the single metal oxide particles (silica and zinc oxide). Furthermore, the RAV value of the hybrid metal oxide particles is higher than the sum of the individual RAV values ​​of the single metal oxide particles.

[0314] Experiment 2: Sun Protection Factor (SPF) experiment using hybrid SiO2 / ZnO particles To evaluate the SPF of the hybrid metal oxide particles, UV filter compositions were prepared according to Table 1.

[0315] 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.

[0316] Composition 2 was a composition of the present invention having 3.00 wt. % of the hybrid metal oxide particles prepared according to Example 1.

[0317] Composition 3 is a comparative analysis composition having 1.20 wt. % of commercial zinc oxide particles instead of the hybrid metal oxide particles, which corresponds to 3.0 wt. % of the hybrid metal oxide particles in Experiment 1.

[0318] [Table 2]

[0319] [Table 3]

[0320] 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.

[0321] [Table 4]

[0322] FIG. 2 shows the absorbance of UV filter compositions 1, 2 and 3 in the range of 290 to 450 nm.

[0323] Composition 2, which contains 3% by weight of hybrid metal oxide particles, shows increased absorption over the entire UV range from 290 to 450 nm. The in vitro SPF value of composition 2 shows an increase of 22% compared to the placebo composition by adding 3% by weight of hybrid metal oxide particles according to Example 1. On the other hand, the in vitro SPF value of composition 3, which contains 1.2% metal oxide particles (ZnO), is only increased by 14% compared to the placebo composition.

[0324] Experiment 3: Transparency / whiteness experiment The whitening effect was determined by the color measurements described above for compositions 1, 2 and 3 prepared in experiment 2. The results for these compositions are summarized in FIG.

[0325] FIG. 3 shows the lightness values ​​L * Shows the difference.

[0326] From FIG. 3, it is observed that composition 2 (containing 3.0 wt. % hybrid metal oxide particles) exhibits lower scattering of visible light and therefore produces a lower whitening effect on the skin.

[0327] In contrast, Composition 3 (containing 1.2% ZnO) was shown to exhibit higher scattering of visible light and therefore produce a higher whitening effect on the skin. * increases to 8.3, whereas the delta L of composition 2 (3% hybrid metal oxide particles) * It is shown that only increases to 8.1.

[0328] Thus, compositions containing the hybrid metal oxide particles of the present invention exhibit lower Delta L values ​​compared to compositions containing the same amount of single metal oxide particles. * The values ​​showed an increase.

Claims

1. A method for increasing the sun protection factor of a UV filter composition, comprising adding hybrid metal oxide particles to said UV filter composition, The hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles, the metal oxide particles comprising at least one second metal oxide; The method of claim 1, wherein the first metal oxide and the second metal oxide are independently 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 hybrid metal oxide particles for increasing the sun protection factor of a UV filter composition, comprising: The hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles, the metal oxide particles comprising at least one second metal oxide; The first metal oxide and the second metal oxide are independently at least one 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 hybrid metal oxide particles are non-porous.

4. 3. The method or use according to claim 1 or 2, wherein the amount of the hybrid metal oxide particles ranges from 0.1 to 25.0 wt. %, based on the total weight of the UV filter composition.

5. The method or use according to claim 1 or 2, wherein the hybrid metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

6. 3. The method or use according to claim 1 or 2, wherein the amount of said metal oxide in said hybrid metal oxide particles is in the range of 60.0 to 100.0 wt %, based on the total weight of said hybrid metal oxide particles.

7. 3. The method or use according to claim 1 or 2, wherein the amount of the first metal oxide is in the range of 2 to 90 wt %, based on the total weight of the hybrid metal oxide particles.

8. 3. The method or use of claim 1 or 2, wherein the first metal oxide is titania.

9. 3. The method or use according to claim 1 or 2, wherein the amount of the second metal oxide is in the range of 10 to 98 wt % based on the total weight of the hybrid metal oxide particles.

10. 3. The method or use according to claim 1 or 2, wherein the second metal oxide is silica.

11. 3. The method or use of claim 1 or 2, wherein the metal oxide particles comprising at least one second metal oxide have an average diameter in the range of 50 nm to 999 nm.

12. 3. The method or use according to claim 1 or 2, wherein the weight ratio of the first metal oxide to the second metal oxide is in the range of 1:50 to 10:

1.

13. 3. The method or use according to claim 1 or 2, wherein the weight ratio of the first metal oxide to the second metal oxide is 2:

3.

14. 3. The method or use of claim 1 or 2, wherein the continuous matrix further comprises at least one binder.

15. 15. The method or use of claim 14, wherein the binder is selected from silica, sodium silicate, magnesium silicate, calcium silicate, aluminum silicate, aluminum oxide hydroxide, sodium oxide, calcium carbonate, calcium aluminate, bentonite, kaolinite, montmorillonite, and combinations thereof.

16. The method or use according to claim 1 or 2, wherein the second metal oxide particles have a core-shell structure.

17. 3. The method or use of claim 1 or 2, wherein the arrangement of the second metal oxide particles is an ordered arrangement.

18. 3. The method or use of claim 1 or 2, wherein the arrangement of the second metal oxide particles is a disordered arrangement.

19. 3. The method or use of claim 1 or 2, wherein the second metal oxide particles have a surface functionalization.

20. 3. The method or use of claim 1 or 2, wherein the hybrid metal oxide particles comprise a surface functionalization.

21. 3. The method or use of claim 1 or 2, wherein the hybrid metal oxide particles exhibit a color in the visible spectrum in the wavelength range of 380 nm to 800 nm.

22. 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 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 ) 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 ) phenylenebisdiphenyltriazine; (d ２２ ) imidazoline derivatives; (d ２３ ) diarylbutadiene derivatives; (d ２４ ) aminohydroxybenzoyl hexyl benzoate derivatives; and (d ２５ ) Bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivative 3. The method or use of claim 1 or 2, further comprising a UV absorber selected from the group consisting of:

23. 3. The method or use according to claim 1 or 2 for protecting the skin from ultraviolet light and high-energy visible light.

24. 10. The method according to claim 1, further minimizing or masking the whitening effect of the UV filter composition and maintaining its transparency.

25. 3. The use according to claim 2, which further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.

26. A UV filter composition comprising hybrid metal oxide particles in the range of 0.1 to 25.0 wt. %, based on the total weight of the UV filter composition; The hybrid metal oxide particles comprise a continuous matrix of at least one first metal oxide having embedded therein an array of metal oxide particles, the metal oxide particles comprising at least one second metal oxide; the first metal oxide and the second metal oxide are at least one independently selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.

27. 27. The UV filter composition according to claim 26, wherein the hybrid metal oxide particles are non-porous.

28. a. Water; and b. 0.1 to 25.0 wt. % of the hybrid metal oxide particles based on the total weight of the UV filter composition 27. The UV filter composition according to claim 26, comprising:

29. a. water; b. oil; and c. 0.1 to 25.0 wt. % of the hybrid metal oxide particles based on the total weight of the UV filter composition 27. The UV filter composition according to claim 26, comprising:

30. a. oil; and b. 0.1 to 25.0 wt. % of the hybrid metal oxide particles based on the total weight of the UV filter composition 27. The UV filter composition according to claim 26, comprising:

31. 27. The UV filter composition according to claim 26, wherein the hybrid metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.

32. (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 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 ) 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 ) phenylenebisdiphenyltriazine; (d ２２ ) imidazoline derivatives; (d ２３ ) diarylbutadiene derivatives; (d ２４ ) aminohydroxybenzoyl hexyl benzoate derivatives; and (d ２５ ) Bis-(diethylaminohydroxybenzoylbenzoyl)-piperazine derivative 27. The UV filter composition according to claim 26, further comprising a UV absorber selected from the group consisting of:

33. 27. The UV filter composition according to claim 26, further comprising at least one emulsifier in the range of 1.0 to 20.0 wt.-%, based on the total weight of the UV filter composition.

34. 34. The UV filter composition according to claim 33, wherein the emulsifier is selected from the group consisting of anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers and polymeric emulsifiers.

35. 27. The UV filter composition according to claim 26, further comprising an additive selected from the group consisting of thickeners, active ingredients, preservatives and fragrances.

36. 27. The UV filter composition according to claim 26, which is a sunscreen composition.

37. 27. The UV filter composition according to claim 26, which is a day care composition.

38. 27. The UV filter composition according to claim 26, which is at least one selected from the group consisting of a cream, emulsion, milk, lotion, ointment, oil, gel, spray, aerosol, daily care lotion, water-resistant emulsion, oil-in-water emulsion, and oil-in-water lotion.

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