Sunscreen composition comprising porous metal oxide spheres

Abstract

The present invention relates to a method of increasing the sun protection factor (SPF) of a sunscreen composition, the use of porous metal oxide spheres (e.g. microspheres) for increasing the SPF of a sunscreen composition and the preparation of a sunscreen composition comprising said porous spheres.

Description

[0001] The present invention relates to a method for increasing the sun protection factor (SPF) of a sunscreen composition, use of porous metal oxide spheres for increasing the SPF of a sunscreen composition, and preparation of a sunscreen composition comprising the porous spheres.

[0002] Sunscreen compositions are used to protect human skin from damaging solar radiation. Sunscreen compositions with high UV protection (high SPF) are needed to prevent the adverse effects of solar radiation, especially UV radiation. A wide range of UV absorbers can be used in sunscreen compositions.

[0003] However, providing sunscreen compositions with high SPF remains challenging due to various reasons, such as their low solubility or regulatory restrictions that limit the inclusion of large amounts of UV filters in cosmetic compositions. Furthermore, such compositions may be associated with issues such as a whitening effect. Therefore, there is a need for methods to increase the SPF of existing sunscreen compositions while maintaining their transparency.

[0004] Therefore, it is an object of the present invention to provide a method for increasing the SPF of a sunscreen composition. Furthermore, it is desirable that the sunscreen composition is not accompanied by adverse appearance problems, such as whitening effects.

[0005] Summary of the Invention

[0006] Surprisingly, it has been found that this object can be achieved by adding porous spheres (eg microspheres) containing metal oxides to sunscreen compositions, which increases the SPF of the sunscreen compositions.

[0007] Therefore, a primary aspect of the present invention is to provide a method for increasing the SPF of a sunscreen composition, comprising adding porous spheres (e.g., microspheres) comprising a metal oxide to the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0008] Another aspect of the present invention is the use of porous spheres (e.g., microspheres) comprising a metal oxide for increasing the sun protection factor of a sunscreen composition, wherein the metal oxide is at least one selected from silica, titanium dioxide, aluminum oxide, zirconium oxide, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0009] In another aspect, the present invention provides a sunscreen composition comprising water and porous spheres (e.g., microspheres), wherein the porous spheres comprise 0.1-10.0 wt. % of a metal oxide based on the total weight of the sunscreen composition, wherein the metal oxide is at least one selected from silica, titania, alumina, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide. Brief introduction of the attached figure

[0010] The disclosure described herein is illustrated by way of example and not limitation in the accompanying figures.

[0011] Figure 1 is a scanning electron microscope (SEM) photograph of porous silica spheres according to an embodiment of the present invention.

[0012] Figure 2 is a SEM photograph of porous silica spheres according to an embodiment of the present invention.

[0013] Figure 3 is a SEM photograph of porous titanium dioxide spheres according to an embodiment of the present invention.

[0014] Figure 4 is a SEM photograph of porous titanium dioxide spheres according to an embodiment of the present invention.

[0015] Figure 5 Depicted is a correlation graph of the absorbance of an aqueous dispersion containing Patent Blue V in the presence of porous silica spheres.

[0016] Figure 6 Depicted is a correlation graph of the UV absorbance of an aqueous dispersion containing benzophenone-4 in the presence of porous silica spheres.

[0017] Figure 7 Depicts the behavior of aqueous dispersions containing benzophenone-4 in the presence of different amounts of porous silica spheres at λ 最大 Correlation diagram of UV absorbance under .

[0018] Figure 8 Depicted in 130 commercial samples, containing benzophenone-4 aqueous dispersion at λ 最大 Correlation diagram of UV absorbance under .

[0019] Figure 9 Depicted is a correlation graph of the absorbance of an aqueous dispersion containing Patent Blue V in the presence of porous titanium dioxide spheres.

[0020] Figure 10 Depicted is a correlation graph of the UV absorbance of an aqueous dispersion containing porous titanium dioxide spheres.

[0021] Figure 11 Depicted is a correlation graph of the absorbance of a sunscreen composition comprising UV filters in the absence and presence of porous silica spheres.

[0022] Figure 12 Depicted is a correlation graph of the absorbance of a sunscreen composition without additional UV filters in the absence and presence of porous silica spheres.

[0023] Figure 13 Depicted is a graph showing the whitening effect of a sunscreen composition comprising UV filters in the absence and presence of porous silica spheres.

[0024] Figure 14 Depicted is a graph showing the whitening effect of a sunscreen composition without additional UV filters in the absence and presence of porous silica spheres.

[0025] Detailed description

[0026] Before describing the compositions and formulations of the present invention, it should be understood that the invention is not limited to the specific compositions and formulations described, as such compositions and formulations may, of course, vary. It should also be understood that the terminology used herein is not intended to be limiting, as the scope of the present invention as claimed is limited only by the appended claims.

[0027] If below group is defined as comprising at least a certain number of embodiments, then this means also comprising the group that is preferably only made up of these embodiments.In addition, the terms "first", "second", "third" or "a", "b", "c" etc. in the specification and claims are used to distinguish similar elements, and are not necessarily used to describe sequence or chronological order. Should be understood that the terms used in this way are interchangeable where appropriate, and the embodiments of the present invention described herein can be operated in a sequence different from that described or illustrated herein. In the case where the terms "first", "second", "third" or "(A)", "(B)" and "(C)" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to the step of method or purposes or measurement, there is no continuity of time or time interval between the steps, i.e., such steps can be carried out simultaneously or between these steps, there can be a time interval of seconds, minutes, hours, days, weeks, months or even years, unless otherwise stated in the application, as described above or below.

[0028] Furthermore, ranges defined throughout the specification are also inclusive, i.e., a range of 1-10 means that both 1 and 10 are included within the range. For the avoidance of doubt, applicants should be entitled to any equivalents under applicable law.

[0029] In the following paragraphs, different aspects of the present invention are defined in more detail. Each aspect so defined can be combined with any other aspect, unless explicitly stated otherwise. In particular, any feature indicated as preferred or advantageous can be combined with any other feature or features indicated as preferred or advantageous.

[0030] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may.

[0031] In addition, as those skilled in the art will appreciate from this disclosure, in one or more embodiments, specific features, structures, or characteristics may be combined in any suitable manner. Furthermore, although some embodiments described herein include some features without including other features included in other embodiments, the combination of features of different embodiments is intended to be within the scope of the present invention and to form different embodiments, as will be understood by those skilled in the art. For example, in the appended claims, any claimed embodiment may be used in any combination.

[0032] Surprisingly, it was discovered that the addition of porous spheres (e.g., microspheres) containing metal oxides to a sunscreen composition resulted in an increase in the SPF of the sunscreen composition. Furthermore, it was observed that the resulting sunscreen composition did not exhibit the whitening effect typically associated with the addition of scattering particles. Thus, the present invention provides a sunscreen composition with high SPF and low whitening.

[0033] The porous metal oxide spheres (e.g., microspheres) scatter light passing through the sunscreen composition. Thus, the presence of the porous metal oxide spheres (e.g., microspheres) in the sunscreen composition results in an overall increase in the path length of light passing through the sunscreen layer. Consequently, photon absorption by the UV filter or dye molecules present in the sunscreen composition is increased. Consequently, the absorbance of the dye or UV absorber is generally increased without increasing its concentration.

[0034] Therefore, a main aspect of the present invention is to provide a method for increasing the sun protection factor of a sunscreen composition. The method comprises adding porous spheres (e.g., microspheres) comprising a metal oxide to the sunscreen composition, wherein the metal oxide is preferably at least one selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0035] In certain embodiments, the metal oxide is at least one selected from silicon dioxide, zinc oxide, and titanium dioxide. In another embodiment, the metal oxide is silicon dioxide. In yet another embodiment, it is titanium dioxide.

[0036] Another aspect of the present invention is the use of porous spheres (e.g., microspheres) comprising a metal oxide for increasing the sun protection factor of a sunscreen composition, wherein the metal oxide is preferably at least one selected from silica, titanium dioxide, aluminum oxide, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0037] In certain embodiments, the metal oxide is at least one selected from silicon dioxide, zinc oxide, and titanium dioxide. In another embodiment, the metal oxide is silicon dioxide. In yet another embodiment, the metal oxide is titanium dioxide.

[0038] In certain embodiments, the porous spheres (e.g., microspheres) contain an additional light absorber. In a preferred embodiment, the additional light absorber is carbon black powder. In the context of the present invention, microspheres are spherical or quasi-spherical microparticles having an average diameter or particle size of typically 1-1000 μm (1 mm). Examples of microspheres include glass microspheres and polyethylene microspheres.

[0039] In the context of the present invention, the SPF factor ( Sun Protection Factor The SPF (Special Power Factor) is used to rate photoprotective preparations (sunscreen compositions) for humans (in vivo). It indicates how long a person wearing a sunscreen can be exposed to the sun without getting burned, compared to how long a particular individual could protect themselves.

[0040] SPF is determined in vitro by measuring diffuse transmittance in the spectral range of 290-400 nm.

[0041] In the context of the present invention, the term "monodisperse" in relation to spheres, microspheres or nanospheres means particles having a generally uniform shape and a generally uniform diameter. A monodisperse population of spheres, microspheres or nanospheres of the present invention may have 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the particles having a diameter, by number, within ±7%, ±6%, ±5%, ±4%, ±3%, ±2% or ±1% of the mean diameter of the population.

[0042] In the context of the present invention, the term "particle size" is synonymous with particle diameter and is determined, for example, using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Average particle size is synonymous with D50, meaning the point at which half of the population lies above and half below. Particle size refers to primary particles. Particle size can be measured using laser scattering techniques, either in dispersions or dry powders.

[0043] In certain embodiments, the porous spheres (eg, microspheres) are present in an amount of 0.1-10.0 weight percent, or 1.0-8.0 weight percent, or 2.0-7.0 weight percent, based on the total weight of the sunscreen composition.

[0044] In a particularly preferred embodiment, the porous spheres (eg, microspheres) are present in an amount of 5.5 weight percent, based on the total weight of the sunscreen composition.

[0045] In another particularly preferred embodiment, the porous spheres (eg, microspheres) are present in an amount of 2.0 weight percent, based on the total weight of the sunscreen composition.

[0046] In certain embodiments, the amount of metal oxide in the porous sphere is 60.0-99.9 wt%, or 65.0-99.0 wt%, or 75.0-98.0 wt%, or 80.0-95.0 wt%, based on the total weight of the porous sphere.

[0047] In certain embodiments, the porous spheres have an average diameter of 0.5-100.0 μm, or 1.0-90.0 μm, or 5.0-80.0 μm, or 10.0-70.0 μm, or 20.0-50.0 μm.

[0048] In certain embodiments, the porous spheres have an average porosity of 0.10-0.90.

[0049] In certain embodiments, the porous spheres have an average porosity of 0.10-0.80, or 0.30-0.80, or 0.15-0.75, or 0.25-0.60, or 0.30-0.50.

[0050] In certain embodiments, the porous spheres are monodisperse.

[0051] In certain embodiments, the average pore size of the porous sphere is 50-999 nm, or 100-900 nm, or 200-800 nm, or 300-700 nm, or 400-600 nm.

[0052] In certain embodiments, the porous sphere has more than one pore population each having an average pore size, wherein each population has a different average pore size. In another embodiment, the porous sphere has two pore populations, each having an average pore size.

[0053] In certain embodiments, the porous sphere:

[0054] a. having an average diameter of 0.5-100.0 μm;

[0055] b. having an average porosity of 0.10-0.90;

[0056] c. having an average pore size of 50-999 nm, and

[0057] d. is monodisperse.

[0058] In certain embodiments, the porous sphere:

[0059] a. having an average diameter of 0.5-100.0 μm;

[0060] b. having an average porosity of 0.10-0.80;

[0061] c. having an average pore size of 50-999 nm; and

[0062] d. is monodisperse.

[0063] In certain embodiments, the porous metal oxide spheres are prepared using a polymer sacrificial template.

[0064] For example, the porous sphere is prepared by a method comprising the following steps.

[0065] A liquid dispersion of polymer particles (e.g., nanoparticles) and a metal oxide is formed. Droplets of the dispersion are formed. The droplets are dried to provide polymer template spheres (e.g., microspheres) comprising polymer spheres and the metal oxide. The polymer spheres are removed from the template spheres to provide porous metal oxide spheres.

[0066] Another method for preparing porous spheres having at least two different average particle sizes comprises the following steps.

[0067] A liquid solution or dispersion is formed of monodisperse polymer particles (e.g., nanoparticles). At least one additional liquid solution or dispersion is formed of monodisperse polymer particles (e.g., nanoparticles). The average diameter of the monodisperse polymer particles of each solution or dispersion is different.

[0068] Each solution or dispersion is mixed together; wherein the metal oxide is added to one or more of the solutions or dispersions and / or wherein the metal oxide is added to the mixture, to obtain a final liquid dispersion of polymer particles and metal oxide.

[0069] Droplets of the final liquid dispersion are formed. The droplets are dried to provide polymer template spheres comprising monodisperse polymer spheres having a bimodal distribution and metal oxide. The polymer spheres are removed from the template spheres to provide porous metal oxide spheres, typically microspheres.

[0070] In certain embodiments, the method includes forming a liquid dispersion of polymer particles (eg, nanoparticles) and a metal oxide, spray drying the liquid dispersion to provide polymer template spheres, and removing the polymer spheres from the template spheres.

[0071] The droplets are aqueous droplets or oil droplets.In certain embodiments, a vibrating nozzle is used to form the droplets.

[0072] In certain embodiments, the method comprises providing a continuous phase, and mixing a liquid dispersion with the continuous phase to form an emulsion containing dispersed droplets of the liquid dispersion, and collecting the droplets.

[0073] In certain embodiments, drying comprises microwave irradiation, oven drying, vacuum drying, drying in the presence of a desiccant, or a combination thereof.

[0074] In certain embodiments, the weight ratio of polymer particles (eg, nanoparticles) to metal oxide is from 0.5:1 to 10.0:1.

[0075] In certain embodiments, the polymer is selected from the group consisting of poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, derivatives thereof, salts thereof, copolymers thereof, and combinations thereof.

[0076] In certain embodiments, the polymer spheres (eg, nanospheres) are removed from the template spheres (eg, microspheres) using techniques such as calcination, pyrolysis, or solvent removal.

[0077] In certain embodiments, the polymer spheres (eg, nanospheres) are removed from the template spheres (eg, microspheres) by calcining the template spheres at a temperature of 350-700°C for a period of 1-8 hours.

[0078] The porous spheres (eg, microspheres) comprising metal oxides are spherical or quasi-spherical and are micrometer-sized.

[0079] The polymer particles used as templates are spherical, nanoscale, and monodisperse. The metal oxide used can also be in particulate form and have nanoscale particles. Drying the polymer / metal oxide droplets and subsequently removing the polymer yields microspheres with uniform voids (pores). Thus, because the polymer particles are porous and monodisperse, the porous metal oxide spheres contain uniform pore sizes.

[0080] The pore size depends on the size of the polymer particles. Some shrinkage or compaction may occur during polymer removal, providing a pore size slightly smaller than the initial polymer particle size, for example 10-40% smaller than the polymer particle size. The pore size is uniform because the polymer particles are uniform in shape and size.

[0081] UV absorbers

[0082] In certain embodiments, the sunscreen composition further comprises a UV absorber selected from the group consisting of:

[0083] (d1) p-Aminobenzoic acid derivatives;

[0084] (d2) salicylic acid derivatives;

[0085] (d3) Benzophenone derivatives;

[0086] (d4) dibenzoylmethane derivatives;

[0087] (d5) diphenyl acrylate;

[0088] (d6) 3-Imidazol-4-yl-acrylic acid and its esters;

[0089] (d7) Benzofuran derivatives;

[0090] (d8) polymeric UV absorber;

[0091] (d9) Cinnamic acid derivatives;

[0092] (d 10 ) camphor derivatives;

[0093] (d 11 ) hydroxyphenyltriazine derivatives;

[0094] (d 12 )benzotriazole derivatives;

[0095] (d 13 ) triphenylamino-s-triazine derivatives;

[0096] (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts;

[0097] (d 15 ) anthranilic acid esters;

[0098] (d 16 ) High salicylic acid ester;

[0099] (d 17 ) tris-biphenyltriazine derivatives;

[0100] (d 18 ) TiO2 (partially encapsulated), ZnO and mica;

[0101] (d 19 )benzylidenemalonate;

[0102] (d 20 ) merocyanine derivatives;

[0103] (d 21 )phenylenebis-diphenyltriazine;

[0104] (d 22 ) imidazoline derivatives; and

[0105] (d 23)Diarylbutadiene derivatives.

[0106] Compounds that can be used as the p-aminobenzoic acid derivative (d1) are, for example:

[0107] 4-Aminobenzoic acid (PABA); formula (PABA 01) Ethyl dihydroxypropyl-PABA; formula (PABA 02) PEG-25-PABA;

[0108] wherein m, n and x have the same meaning and each represents up to 25; formula (PABA-03) Octyl dimethyl PABA; or formula (PABA-04) Glyceryl aminobenzoate.

[0109] Compounds that can be used as salicylic acid derivatives (d2) are, for example:

[0110] Formula (SAD-01) High in salicylic acid Ester; Formula (SAD-02) Triethanolamine salicylate; Formula (SAD-03) Amyl p-dimethylaminobenzoate; Formula (SAD-04) Octyl salicylate; or formula (SAD-05) 4-isopropylbenzyl salicylate.

[0111] Compounds that can be used as benzophenone derivatives (d3) are, for example:

[0112] Benzophenone-3 (2-hydroxy-4-methoxybenzophenone); Benzophenone-4 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid); Benzophenone-8 (2,2'-dihydroxy-4-methoxybenzophenone); or an amino-substituted hydroxybenzophenone of the formula:

[0113]

[0114] in:

[0115] R1 and R2 represent hydrogen, C1-C 20 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkenyl, in which the substituents R1 and R2 may form, together with the nitrogen atom to which they are bound, a 5- or 6-membered ring;

[0116] R3 and R4 independently represent C1-C 20 Alkyl; C2-C 10Alkenyl; 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; heteroaryl; a substituent imparting solubility in water selected from a nitrile group, a carboxylate group, a sulfonate group or an ammonium group;

[0117] X represents hydrogen; COOR5; or CONR6R7;

[0118] R5, R6, R7 are independently hydrogen; C1-C 20 Alkyl; C2-C 10 Alkenyl; C3-C 10 Cycloalkyl; C3-C 10 Cycloalkenyl; (YO) o -Z; or aryl;

[0119] Z represents -CH2-CH3; -CH2-CH2-CH3; -CH2-CH2-CH2-CH3; or -CH(CH3)-CH3;

[0120] m means 0-3;

[0121] n represents 0-4; and

[0122] o represents 1-20.

[0123] In a most preferred embodiment, the UV absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

[0124] According to the invention, it is also possible to use dimeric benzophenone derivatives corresponding to the following formula:

[0125]

[0126] in:

[0127] R1 and R2 independently represent C1-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 bound form a 5- or 6-membered heterocyclic ring;

[0128] R3 represents an alkylene group, a cycloalkylene group, an alkenylene group or a phenylene group which is optionally substituted by a carbonyl group or a carboxyl group; a diradical of the formula (HBP-03a)*-CH2-C≡C-CH2-*; or R3 together with A form the formula (HBP-03b) A divalent group, wherein:

[0129] n2 represents a number from 1 to 3;

[0130] A represents -O-; or -N(R5)-; and

[0131] R5 represents hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl.

[0132] In particular, a dimeric benzophenone derivative of the following formula can be preferably used as the UV absorber (d3):

[0133]

[0134] and

[0135]

[0136] An example of a dibenzoylmethane derivative (d4) which can be used according to the invention is butylmethoxydibenzoylmethane ([1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione]).

[0137] Examples of diphenylacrylate derivatives (d5) which can be used according to the invention are octocrylene (2-ethylhexyl-2-cyano-3,3′-diphenylacrylate) or etocorylene (ethyl 2-cyano-3,3′-diphenylacrylate).

[0138] 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 of the formula (BF-01): or (BF-02) of compounds.

[0139] Examples of polymeric UV absorbers (d8) containing one or more organosilicon groups which can be used according to the invention are benzalmalonate derivatives, in particular those of the formula (PUV-01) A compound wherein R 24 represents hydrogen or methoxy, and r represents about 7; Formula (PUV-02) Compound; Formula (PUV-03) or a compound corresponding to the following formula:

[0140]

[0141] Examples of cinnamic esters (d9) which can be used according to the invention are octyl methoxycinnamate (2-ethylhexyl 4-methoxycinnamate), diethanolamine methoxycinnamate (diethanolamine salt of 4-methoxycinnamic acid), isopentyl p-methoxycinnamate (2-isopentyl 4-ethoxycinnamate), 2,5-diisopropyl methylcinnamate or cinnamic acid amido derivatives.

[0142] The camphor derivatives (d 10 ) are 4-methylbenzylidenecamphor [3-(4'-methyl)benzylidenecamphor], 3-benzylidenecamphor (3-benzylidenecamphor), polyacrylamidomethylbenzylidenecamphor {N-[2(and 4)-2-oxybornyl-3-ylidenemethyl)benzyl]acrylamide polymer}, benzylidenecamphor trimethylammonium sulfate [3-(4'-trimethylammonium)-benzylidenecamphor methylsulfate], terephthalylidenecamphorsulfonic acid {3,3'-(1,4-phenylenedimethene)-bis-(7,7-dimethyl-2-oxybicyclo[2.2.1]heptane-1-methanesulfonic acid} or a salt thereof, or benzylidenecamphorsulfonic acid [3-(4'-sulfo)benzylidenecamphor] or a salt thereof.

[0143] The hydroxyphenyltriazine derivatives (d 11 ) are in particular bis-resorcinolyl triazines of the formula:

[0144]

[0145] in:

[0146] R1 and R2 independently represent hydrogen; C1-C 18 Alkyl; C2-C 18 Alkenyl; a group of the formula -CH2-CH(-OH)-CH2-O-T1; formula (HPT-01a) Group or (HPT-01h) Groups;

[0147] R3, R4 and R5 independently represent hydroxyl; C1-C5 alkoxy, which is unsubstituted or substituted by one or more OH groups; amino; mono- or di-C1-C5 alkylamino; M; formula (HPT-01b) Formula (HPT-01c) Formula (HPT-01d) Formula (HPT-01e) Formula (HPT-01f) or a group of formula (HPT-01g) Groups;

[0148] R 10 、R 11 and R 12 represents independently of one another a C1-C 14 alkyl;

[0149] R 13 represents hydrogen; M; C1-C5 alkyl; or -(CH2) m3 -O-T1 group;

[0150] R6 represents a direct bond; a straight chain or branched C1-C4 alkylene group; or a group of formula -C m4 H 2m4 or -C m4 H 2m4 -O- group;

[0151] R7, R8 and R9 are independently C1-C 18 Alkyl; C1-C 18 Alkoxy or formula (HPT-01m) Groups;

[0152] R 14 represents a C1-C5 alkyl group;

[0153] M represents a metal cation;

[0154] T1 represents hydrogen; or (C1-C8) alkyl;

[0155] m1, m2 and m3 independently represent 1-3;

[0156] m4 represents 2-14; and

[0157] p1 represents 0 or a number from 1 to 5.

[0158] Classes of compounds that may be mentioned (d 11 ) are:

[0159] -2-(4'-methoxyphenyl)-4,6-bis(2'-hydroxy-4'-n-octyloxyphenyl)-1,3,5-triazine;

[0160] -2,4-bis{[4-(3-(2-propoxy)-2-hydroxypropoxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;

[0161] -2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethylcarboxy)phenylamino]-1,3,5-triazine;

[0162] -2,4-bis{[4-(tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;

[0163] -2,4-bis{[4-(2"-methacryloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;

[0164] -2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethyltrimethylsilyl-2"-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;

[0165] -2,4-bis{[4-(3-(2-propoxy)-2-hydroxypropoxy)-2-hydroxy]phenyl}-6-[4-ethylcarboxyl)phenylamino]-1,3,5-triazine;

[0166] -2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)-1,3,5-triazine; or

[0167] - 2,2′-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-[(2-ethylhexyl)oxy]-(bis-ethylhexyloxyphenol methoxyphenyl triazine) corresponding to the following formula:

[0168]

[0169] The benzotriazole derivatives (d 12 ) corresponds to the following formula:

[0170]

[0171] in:

[0172] R1 represents hydrogen; C1-C 12 Alkyl; C1-C 12 Alkoxy; C1-C 12 Alkoxycarbonyl; C5-C 10 Cycloalkyl or -SO3M;

[0173] R3 represents hydrogen; C1-C 18 Alkyl; C1-C 12 alkoxy; or halogen; and

[0174] n represents 1 or 2;

[0175] If n=1, then

[0176] R2 represents C1-C20 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;

[0177] If n=2, then

[0178] R2 represents a direct bond; or -(CH2) p -;and

[0179] p is an integer from 1 to 3.

[0180] Preferably, compounds of formula (BT-01) are possible, wherein:

[0181] R1 represents C1-C 12 Alkyl; or -SO3M;

[0182] R3 represents hydrogen; halogen, preferably Cl;

[0183] n represents 1;

[0184] R2 is C1-C 12 alkyl; and

[0185] p means 1-3.

[0186] Very particularly preferred compounds are those of the formula:

[0187]

[0188] Furthermore, preferred UV filters of the formula BT-01 are those in which:

[0189] R1 represents hydrogen;

[0190] R3 represents C1-C 18 alkyl;

[0191] n = 2; and

[0192] R2 represents -CH2-.

[0193] Very particularly preferred compounds are those of the formula:

[0194]

[0195] The triphenylamino-s-triazine derivatives (d 13 ) corresponds to the following formula:

[0196]

[0197] in:

[0198] R1, R2 and R3 are each independently an optionally substituted C1-C 20 alkyl, aryl or heteroaryl;

[0199] X represents O; or NR4; and

[0200] R4 represents hydrogen; or optionally substituted C1-C 20 alkyl, aryl or heteroaryl.

[0201] A particularly preferred representative of this class of compounds is ethylhexyl triazone corresponding to the following formula:

[0202]

[0203] Or diethylhexylbutyramidotriazinone corresponding to the following formula:

[0204]

[0205] Or ethylhexyl bis-isoamylbenzoxazolylphenyl melamine corresponding to the following formula:

[0206]

[0207] Preferred tris-biphenyl-triazine derivatives (d 17 ) corresponds to formula (TBT-01) in:

[0208] A expression (TBT-01a) or a group of formula (TBT-01b) Groups;

[0209] R1 and R5 are independently hydrogen; C1-C 18 Alkyl; or C6-C 12 aryl;

[0210] R2, R3 and R4 independently represent hydrogen; or formula (TBT-01c) 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 independently of each other are hydrogen; hydroxyl; halogen; C1-C 18 Alkyl; C1-C 18 Alkoxy; C6-C 12 Aryl; biphenyl; C6-C 12 Aryloxy; C1-C18 Alkylthio; Carboxyl; COOM; C1-C 18 Alkylcarboxyl; aminocarbonyl; or mono- or di-C1-C 18 Alkylamino; C1-C 10 Amide group; COOH;

[0211] M represents an alkali metal ion;

[0212] x represents 1 or 2; and

[0213] y represents an integer from 2 to 10.

[0214] Preferably, the UV filters (d 17 ) corresponds to the compound of the formula:

[0215]

[0216] Preferred benzylidene malonates (d 19 ) corresponds to formula (MBM-01) in:

[0217] R1 represents methyl; ethyl; propyl; or n-butyl;

[0218] If R1 represents a methyl group, then

[0219] R represents tert-butyl; Formula (MBM-01a) or a group of formula (MBM-01b) a group; wherein:

[0220] R2 and R3 are independently hydrogen; or methyl;

[0221] R4 is methyl; ethyl; or n-propyl;

[0222] R5 and R6 are independently hydrogen; or C1-C3 alkyl;

[0223] If R1 represents ethyl; propyl; or n-butyl, then

[0224] R represents an isopropyl group.

[0225] Particularly preferred benzalmalonates (d 19 ) are listed in the following table:

[0226]

[0227]

[0228] Phenylene-bis-diphenyltriazine (d 21) is a representative example of 5,6,5,6-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine corresponding to the following formula:

[0229]

[0230] A representative example of the imidazoline derivative is ethylhexyldimethoxybenzylidenedioxyimidazoline propionate.

[0231] Diarylbutadiene derivatives (d 23 ) is a representative example of 1,1-dicarboxy-(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

[0232] According to the present invention, the above-mentioned UV filters (d1) to (d 23 ) can be used as a mixture. For example, according to the present invention, filter group (d1) to (d 23 ) of two, three, four, five or six. According to the present invention, it is also possible to use a mixture of substances selected from the substance classes (d1) to (d 23 ) are mixtures of two, three, four, five or six UV filters represented by one or more of ).

[0233] In a preferred embodiment, the UV filters (d) are representatives of the following compound classes:

[0234] (d1) p-Aminobenzoic acid derivatives;

[0235] (d2) salicylic acid derivatives;

[0236] (d3) Benzophenone derivatives;

[0237] (d4) dibenzoylmethane derivatives;

[0238] (d5) diphenyl acrylate;

[0239] (d6) 3-Imidazol-4-yl-acrylic acid and its esters;

[0240] (d7) Benzofuran derivatives;

[0241] (d9) Cinnamic acid derivatives;

[0242] (d 10 ) camphor derivatives;

[0243] (d 11 ) hydroxyphenyltriazine derivatives;

[0244] (d 12 )benzotriazole derivatives;

[0245] (d13 ) triphenylamino-s-triazine derivatives;

[0246] (d 15 ) anthranilic acid esters;

[0247] (d 16 ) High salicylic acid ester;

[0248] (d 19 )benzylidenemalonate; and

[0249] (d 20 ) merocyanine derivatives.

[0250] In a further preferred embodiment, the following oil-soluble UV filters are used according to the invention:

[0251] (d SOL-1 )benzophenone-3 (BP3);

[0252] (d SOL-2 )benzophenone-4 (BP4);

[0253] (d SOL-3 )3-benzylidenecamphor (3BC);

[0254] (d SOL-4 )Bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT);

[0255] (d SOL-5 )butyl methoxydibenzoylmethane (BMBM);

[0256] (d SOL-6 ) diethylhexyl butyramido triazone (DBT);

[0257] (d SOL-7 ) drometrizole trisiloxane (DTS);

[0258] (d SOL-8 ) ethylhexyl triazone (EHT);

[0259] (d SOL-9 ) ethylhexyl methoxycinnamate;

[0260] (d SOL-10 )benzylidenemalonate (BM);

[0261] (d SOL-11 ) diethylamino hydroxybenzoyl hexyl benzoate (DHHB);

[0262] (d SOL-12 )Octocrylene;

[0263] (d SOL-13 )polysilicone-15;

[0264] (d SOL-14 ) High salicylic acid esters; and

[0265] (d SOL-15 )Ethylhexyl salicylate.

[0266] In the most preferred embodiment, the UV filter is at least one selected from the following group:

[0267] (d 9a ) ethylhexyl methoxycinnamate,

[0268] (d 11a ) bis-ethylhexyloxyphenol methoxyphenyl triazine,

[0269] (d 13a ) ethylhexyl triazone, and

[0270] (d 3a )Diethylamino hydroxybenzoyl hexyl benzoate.

[0271] In a particularly preferred embodiment, the UV filter is selected from (d 9a )、(d 11a )、(d 13a ) and (d 3a ) of the UV filters.

[0272] It has been observed that the increase in absorbance due to the presence of porous metal oxide spheres (eg, microspheres) is stronger in the UV spectral range compared to the visible range.

[0273] In preferred embodiments, the method further minimizes or masks the whitening effect of the sunscreen composition while maintaining its clarity.

[0274] In a preferred embodiment, the use further minimizes or masks the whitening effect of the sunscreen composition and maintains its clarity.

[0275] The whitening effect of the sunscreen composition is determined by a test based on evaluating the light transmittance through a thin film of a sunscreen sample spread on a rough substrate.

[0276] Sunscreen composition

[0277] In another aspect, the present invention provides a sunscreen composition comprising water and 1.0-10.0 wt % of porous spheres (e.g., microspheres) comprising a metal oxide, based on the total weight of the sunscreen composition, wherein the metal oxide is at least one selected from silica, titania, alumina, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0278] In certain embodiments, the metal oxide is at least one selected from silicon dioxide, zinc oxide, and titanium dioxide. In another embodiment, the metal oxide is silicon dioxide. In yet another embodiment, the metal oxide is titanium dioxide.

[0279] In certain embodiments, the porous silica spheres have a refractive index of 1.4 to 1.5. When porous silica spheres having a refractive index within this range, for example, 1.3 to 1.6, are introduced into a sunscreen composition, the porous silica spheres do not affect the appearance of the sunscreen composition.

[0280] In certain embodiments, the amount of metal oxide in the porous sphere is 60.0-99.9 wt%, or 75.0-98.0 wt%, or 80.0-95.0 wt%, based on the total weight of the porous sphere.

[0281] In certain embodiments, the sunscreen composition comprises porous spheres having an average diameter of 0.5-100.0 μm; or 1.0-90.0 μm; or 5.0-80.0 μm; or 10.0-70.0 μm; or 20.0-50.0 μm.

[0282] In certain embodiments, the porous spheres have an average porosity of 0.10-0.90.

[0283] In certain embodiments, the sunscreen composition comprises porous spheres having an average porosity of 0.10-0.80; or 0.30-0.80; or 0.15-0.75; or 0.25-0.60; or 0.30-0.50.

[0284] In certain embodiments, the sunscreen composition comprises porous spheres having an average pore size of 50-999 nm; or 100-900 nm; or 200-800 nm; or 300-700 nm; or 400-600 nm.

[0285] In certain embodiments, the porous spheres are monodisperse.

[0286] In certain embodiments, the porous sphere:

[0287] a. having an average diameter of 0.5-100.0 μm;

[0288] b. having an average porosity of 0.10-0.90;

[0289] c. having an average pore size of 50-999 nm, and

[0290] d. is monodisperse.

[0291] In certain embodiments, the sunscreen composition comprises porous spheres as follows:

[0292] a. having an average diameter of 0.5-100.0 μm;

[0293] b. having an average porosity of 0.10-0.80;

[0294] c. having an average pore size of 50-999 nm; and

[0295] d. is monodisperse.

[0296] In certain embodiments, the sunscreen composition further comprises a UV absorber selected from the group consisting of:

[0297] (d1) p-Aminobenzoic acid derivatives;

[0298] (d2) salicylic acid derivatives;

[0299] (d3) Benzophenone derivatives;

[0300] (d4) dibenzoylmethane derivatives;

[0301] (d5) diphenyl acrylate;

[0302] (d6) 3-Imidazol-4-yl-acrylic acid and its esters;

[0303] (d7) Benzofuran derivatives;

[0304] (d8) polymeric UV absorber;

[0305] (d9) Cinnamic acid derivatives;

[0306] (d 10 ) camphor derivatives;

[0307] (d 11 ) hydroxyphenyltriazine derivatives;

[0308] (d 12 )benzotriazole derivatives;

[0309] (d 13 ) triphenylamino-s-triazine derivatives;

[0310] (d 14) 2-phenylbenzimidazole-5-sulfonic acid and its salts;

[0311] (d 15 ) anthranilic acid esters;

[0312] (d 16 ) High salicylic acid ester;

[0313] (d 17 ) tris-biphenyltriazine derivatives;

[0314] (d 18 ) TiO2 (partially encapsulated), ZnO and mica;

[0315] (d 19 )benzylidenemalonate;

[0316] (d 20 ) merocyanine derivatives;

[0317] (d 21 )phenylenebis-diphenyltriazine;

[0318] (d 22 ) imidazoline derivatives; and

[0319] (d 23 )Diarylbutadiene derivatives.

[0320] Representative examples of the UV absorber are as described above.

[0321] In certain embodiments, the sunscreen composition further comprises a dye selected from Acid Violet 43 and Acid Red 33.

[0322] 1) Oil phase

[0323] In certain embodiments, the sunscreen composition further comprises 5.0-50.0 wt. % of a discontinuous oil phase, based on the total weight of the sunscreen composition.

[0324] Possible oily substances in the context of the present invention are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms (e.g. G), straight chain C6-C 22 Fatty acids with straight or branched C6-C 22 Fatty alcohol esters, and branched C6-C 13 Carboxylic acid with straight chain or branched C6-C 22Esters of fatty alcohols, such as 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, palmitic acid Isostearyl ester, isostearyl stearate, 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, straight chain C6-C 22 Esters of fatty acids with branched alcohols, especially 2-ethylhexanol, C3-C 38 Alkyl hydroxycarboxylic acid with straight chain or branched C6-C 22 Esters of fatty alcohols, in particular diethylhexyl malate, esters of linear and / or branched fatty acids with polyols (for example propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, based on C6-C 10 Triglycerides of fatty acids, based on C6-C 18 Liquid mixture of mono-, di- and triglycerides of fatty acids, C6-C 22 Esters of fatty alcohols and / or Guerbet compounds 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 ( OE), Guerbet carbonates based on fatty alcohols having 6 to 18 carbon atoms, preferably 8 to 10 carbon atoms, benzoic acid and linear and / or branched C6-C 22 Esters of alcohols (e.g. TN), a linear or branched symmetrical or asymmetrical dialkyl ether in which each alkyl group has 6 to 22 carbon atoms, for example dioctyl ether ( OE), ring-opening products of epoxidized fatty acid esters and polyols ( HSP, 750, 1102), silicone oils (cyclodimethicone, polymethicone type, etc.) and / or aliphatic or cycloparaffinic hydrocarbons, such as mineral oil, Vaseline, petrolatum, squalane, squalene, isohexadecane or dialkylcyclohexanes.

[0325] In certain embodiments, 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, adipates of linear or branched alcohols having 1 to 22 carbon atoms, very particularly adipates of linear alcohols having 1 to 6 carbon atoms, are particularly suitable here.

[0326] Particular preference is given to using linear and branched fatty alcohol carbonates, in particular dicaprylyl carbonate, as the oily substance.

[0327] In a more preferred embodiment, dibutyl adipate is used as the oily substance.

[0328] In another embodiment, the amount of oil phase is 20-35 weight percent, based on the total weight of the sunscreen composition.

[0329] 2) Emulsifier

[0330] In certain embodiments, the sunscreen composition further comprises 1.0-20.0 weight percent of at least one emulsifier, based on the total weight of the sunscreen composition.

[0331] In certain embodiments, the emulsifier is selected from anionic emulsifiers, nonionic emulsifiers, and polymeric emulsifiers.

[0332] Anionic surfactants are characterized by one or more anionic groups that impart solubility in water, such as carboxylates, sulfates, sulfonates or phosphates, and a lipophilic group. In addition, the molecule may contain polyglycol ethers, esters, ethers and hydroxyl groups. Skin-tolerant anionic surfactants are known in large quantities to those skilled in the art from relevant manuals and are commercially available.

[0333] Representative examples of preferred anionic surfactants are, in each case in the form of their salts, ether carboxylic acids, acyl sarcosinates having 8 to 24 carbon atoms in the acyl group, acyl taurates having 8 to 24 carbon atoms in the acyl group, acyl isethionates having 8 to 24 carbon atoms in the acyl group, mono- and dialkyl sulfosuccinates having 8 to 24 carbon atoms in the alkyl group, monoalkylpolyoxyethyl sulfosuccinates having 8 to 24 carbon atoms and 1 to 6 oxyethyl groups in the alkyl group, linear alkanesulfonates having 8 to 24 carbon atoms, linear α-olefinsulfonates having 8 to 24 carbon atoms, α-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms, alkyl sulfates, alkyl polyglycol ether sulfates, esters of tartaric acid and citric acid, alkyl and / or alkenyl ether phosphates, sulfated fatty acid alkylene glycol esters, monoglyceride sulfates and monoglyceride ether sulfates and C8-C 30 Condensation products of fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, so-called protein fatty acid condensates, e.g. KCG or

[0334] The salts of these surfactants are preferably selected from the group consisting of sodium, potassium and ammonium and mono-, di- and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group.

[0335] Particularly suitable anionic surfactants are liquid at room temperature, preferably at 18-25° C. A particularly desirable feature of these anionic surfactants is that they have a low water content of up to 10% by weight, preferably 0.1-5% by weight, based on the total weight of the anionic surfactant.

[0336] In a most preferred embodiment, the anionic surfactant is an alk(en)yl polyglycol ether citrate, in particular a mixture of monoesters, diesters and triesters of citric acid with alkoxylated alcohols corresponding to formula (I):

[0337]

[0338] in:

[0339] R1, R2 and R3 independently represent hydrogen or a group of the formula

[0340] (II)R4(OCH2CHR5) n

[0341] in:

[0342] R4 represents a straight-chain or branched alkyl and / or alkenyl group having 6 to 22 carbon atoms,

[0343] R5 represents hydrogen or methyl, and

[0344] n represents a number from 1 to 20, with the proviso that at least one of the radicals R1, R2 or R3 is not hydrogen.

[0345] Typical examples of the alcohol part of the esters are addition products of an average of 1 to 20 mol, preferably 5 to 10 mol, of ethylene oxide and / or propylene oxide with hexanol, octanol, 2-ethylhexanol, decanol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, trans-octadecenol, petroselinol, arachidyl alcohol, eicosenyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical-grade mixtures thereof.

[0346] The alk(en)yl polyglycol ether citrates are advantageous for the agents according to the invention because they are liquid anionic surfactants having a low water content of up to 5% by weight, based on the anionic surfactant.

[0347] The anionic surfactant is preferably present in an amount of 7 to 17 wt. %, based on the total weight of the sunscreen composition.

[0348] Furthermore, the agent of the present invention comprises at least (c) 0.5 to 25% by weight of other co-surfactants other than anionic surfactants.

[0349] Suitable cosurfactants are in principle zwitterionic, amphoteric, cationic and / or nonionic surfactants.

[0350] The molecule contains at least one quaternary ammonium group and at least one -COO( - ) or -SO3( - ) group are known as zwitterionic surfactants. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinates, N-amidopropyl-N,N-dimethylammonium glycinates, for example cocoamidopropyldimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, each having 8 to 18 carbon atoms in the alkyl or acyl group, and cocoamidoethyl hydroxyethylcarboxymethylglycinate. Fatty acid amide derivatives known under the INCI name cocoamidopropyl betaine are preferred zwitterionic surfactants. According to the invention, particularly preferred are Betain 810 (INCI: Capryloyl / Capramidopropyl Betaine), and SBCS 50K (INCI: PEG-5 Lauryl Citrate Disodium Sulfosuccinate, Sodium Laureth Sulfate) Surfactant mixtures of Betain 810 (caprylyl / capramidopropyl betaine), in particular in a weight ratio of 1:4 to 4:1, very particularly preferably in a weight ratio of 1:4 to 1:1.

[0351] Amphoteric surfactants are understood to mean surfactants having in their molecules 18 Those surface-active compounds which, in addition to the alkyl or acyl groups, contain at least one free amino group and at least one -COOH or -SO3H group and are capable of forming internal 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, in each case having about 8 to 18 carbon atoms in the alkyl group. Preferred amphoteric surfactants are N-cocoalkylaminopropionates, cocoamidoethylaminopropionates and C 12-18 Acylsarcosine.

[0352] In particular, quaternary ammonium compounds can be used as cationic surfactants. Surfactants selected from this substance class have a particularly high affinity for the skin and can improve the perceived smoothness. These include, in particular, ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. In addition, very biodegradable esterquat compounds, such as those sold under the trade name Dialkylammonium methylsulfate and methylhydroxyalkyldialkanoyloxyalkylammonium methylsulfate sold The corresponding products of the esterquat series can be used as cationic surfactants. The term "esterquats" is generally understood to mean quaternized fatty acid triethanolamine ester salts. They impart a particularly soft feel to the composition. These are known substances prepared by relevant methods of organic chemistry. Other cationic surfactants that can be used according to the invention are quaternized protein hydrolysates.

[0353] Nonionic surfactants are particularly preferably present as cosurfactants, for example:

[0354] - 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 carbon atoms, fatty acids having 12 to 40 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group;

[0355] -1-50 mol of ethylene oxide addition product on glycerol C 12 / 18Fatty acid monoesters and diesters; glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and ethylene oxide addition products thereof,

[0356] - alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs; addition products of 7 to 60 mol of ethylene oxide on castor oil and / or hydrogenated castor oil;

[0357] - polyols and / or polyglycerol esters, for example polyglyceryl diisostearate or polyglyceryl dimer linoleate or polyglyceryl 12-hydroxystearate;

[0358] - addition products of 2 to 15 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0359] -Based on straight chain, branched, unsaturated or saturated C6-C 22 partial esters of fatty acids, ricinoleic acid and 12-hydroxystearic acid with pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose), or mixed esters, such as glyceryl stearate citrate and glyceryl stearate lactate;

[0360] - Wool wax alcohol;

[0361] - polysiloxane / polyalkyl polyether copolymers and corresponding derivatives;

[0362] - 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 polyols, preferably glycerol or polyglycerol; and

[0363] -polyalkylene glycol.

[0364] Addition products of ethylene oxide and / or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, mono- and diesters of glycerol and sorbitan mono- and diesters of fatty acids, or onto castor oil are known, commercially available products. These are homologous mixtures whose average degree of alkoxylation corresponds to the molar ratio of ethylene oxide and / or propylene oxide to substrate subjected to the addition reaction. Depending on the degree of ethoxylation, these are either W / O or O / W emulsifiers. Reaction products with 1 to 100 mol of ethylene oxide are particularly suitable for the preparations according to the invention.

[0365] Advantageous compounds from the group of nonionic surfactants are partial esters of polyols, in particular partial esters of C3-C6 polyols, for example monoglycerides, partial esters of pentaerythritol or sugar esters, for example sucrose distearate, sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucinate, 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. Suitable nonionic surfactants include addition products of 1 to 30 mol, preferably 5 to 10 mol, of ethylene oxide onto the aforementioned sorbitan esters.

[0366] The nonionic surfactants of the alkyl oligoglycoside group are particularly skin-friendly and can therefore be preferably used in the context of the present invention. 22 Alkyl mono- and oligoglycosides, their preparation and their use are known in the prior art. They are prepared, in particular, by reacting glucose or oligosaccharides with primary alcohols having 8 to 22 carbon atoms, preferably 12 to 22 carbon atoms, particularly preferably 12 to 18 carbon atoms. As regards the glycoside group, both monoglycosides in which the cyclic sugar residue is linked to the fatty alcohol by a glycosidic bond and oligoglycosides preferably having a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization here is a statistical mean value based on the conventional distribution of the homologs of the technical grade product, which is marketed under the trade name The oligoglycoside group contains C8-C 16 Alkyl groups whose average degree of oligomerization is 1 to 2. Acyl glucamides derived from glucosamine are also suitable as nonionic surfactants.

[0367] Nonionic surfactants, preferably polyols and / or polyglycerol esters, are very particularly preferably present as cosurfactants in the agents according to the invention as component (c), and / or alkyl oligoglycosides.

[0368] The polyol component of these surfactants can be derived from substances having at least 2, preferably 3 to 12, especially 3 to 8 hydroxyl groups and 2 to 12 carbon atoms. Typical examples are:

[0369] - glycerol and polyglycerol;

[0370] - alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol;

[0371] - methylol compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

[0372] - alkyl oligoglycosides having 1 to 22, preferably 1 to 8, in particular 1 to 4, carbon atoms in the alkyl group, for example methyl and butyl glucoside;

[0373] - sugar alcohols having 5 to 12 carbon atoms, for example sorbitol or mannitol;

[0374] - sugars with 5 to 12 carbon atoms, such as glucose or sucrose;

[0375] -Amino sugars, such as glucosamine.

[0376] Reaction products based on polyglycerol are particularly important due to their excellent performance properties.

[0377] The acid component of these surfactants can be derived from linear, branched, saturated and / or unsaturated carboxylic acids, optionally with functional groups such as hydroxyl groups. The acid component is particularly preferably a fatty acid having 12 to 22 carbon atoms, optionally with hydroxyl groups, and in particular hydroxystearic acid.

[0378] In a preferred embodiment of the present invention, the diester of polyhydroxystearic acid, polyglyceryl 2-dipolyhydroxystearate, is used, for example as available from BASF PerSonal Care and Nutrition GmbH under the trade name PGPH is sold as a glyceride.

[0379] In the agents according to the invention, further cosurfactants are generally present in an amount of 0.5 to 25% by weight, more preferably 3.0 to 18% by weight, particularly preferably 7 to 18% by weight.

[0380] 3) Additives

[0381] In certain embodiments, the sunscreen composition further comprises an additive selected from the group consisting of a thickener, an active ingredient, a preservative, and a fragrance.

[0382] thickener

[0383] Suitable thickeners are anionic, zwitterionic, amphoteric and nonionic copolymers, for example vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / 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, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and optionally polysaccharides, in particular xanthan gum, guar gum and guar gum derivatives, agar, alginates and tylose, cellulose and cellulose derivatives, for example carboxymethylcellulose, carboxymethylcellulose and hydroxycellulose, and furthermore silicones.

[0384] Preferably, a thickener is added, which is selected from polyacrylates and cross-linked polyacrylates, such as Rheocare SP, C Plus, ADE, GTC.

[0385] Furthermore, thickeners selected from polysaccharides, e.g. T or XG.

[0386] Preferably, the amount of thickener is 0.5 to 5% by weight, in particular 1 to 4% by weight, calculated as active substance and based on the total weight of the sunscreen composition.

[0387] The thickener may be added to the concentrate prior to dilution with water, or may be included in the water used to dilute the concentrate.

[0388] According to a preferred process variant, the concentrated reagent is mixed with the thickener, and water for dilution is added to this mixture, optionally stirring in the other formulation ingredients.

[0389] According to another preferred process variant, water, thickener and optionally further auxiliary substances are stirred with one another and the concentrating agent is added to this mixture.

[0390] The finished sunscreen formulations prepared by the process according to the invention are generally particularly finely divided O / W emulsions having an average particle size of <10 μm, preferably <5 μm.

[0391] Active compound

[0392] Suitable bioactive compounds according to the invention are understood to mean, for example, tocopherol, tocopheryl acetate, tocopheryl palmitate, ascorbic acid, (deoxy)ribonucleic acid and its fragmentation products, beta-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as Prunus extracts, Bambara nut extracts, and vitamin complexes. Such active compounds serve as agents for capturing free radicals and regenerating the skin in the finished sunscreen formulation.

[0393] preservative

[0394] Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentylene glycol or sorbic acid and those known under the names Known silver complexes.

[0395] spice oils

[0396] Fragrance oils that may be mentioned are natural, plant, animal, and synthetic aroma substances or mixtures thereof. Natural aroma substances are obtained, in particular, by extracting flowers, stems, leaves, fruits, peels, roots, and resins of plants. Animal sources are also possible, such as civet and castoreum. Typical synthetic aroma compounds are products of esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons. Preferably, mixtures of various aroma substances are used that together produce a pleasant fragrance note.

[0397] Auxiliary substances

[0398] In certain embodiments, the final sunscreen formulation further comprises auxiliary substances, such as moisturizers / skin wetting agents, viscosity regulators, oils, fats and waxes, surfactants, pearlescent waxes, fatliquors, stabilizers, cationic, zwitterionic or amphoteric polymers, other UV filters, bioactive compounds, film formers, swelling agents, hydrotropes, preservatives, solubilizers, fragrance oils, dyes, insect repellent active compounds, etc., which are listed below by way of example.

[0399] The role of the humectant is to further optimize the sensory properties of the composition and the moisture regulation of the skin.The humectant may be present in an amount of 0-5.0 wt %, based on the total weight of the sunscreen composition.

[0400] Suitable substances are, in particular, amino acids, pyrrolidonecarboxylic 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 (for example glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycols, for example PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG- PEG-18, PEG-20), sugars and sugar derivatives (especially fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sucrose, sorbitan silanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and its salts), ethoxylated sorbitol (sorbitan polyoxyethylene (6) ether, sorbitan polyoxyethylene (20) ether, sorbitan polyoxyethylene (30) ether, sorbitan polyoxyethylene (40) ether), honey and hardened honey, hardened starch hydrolysates, and mixtures of hardened wheat protein and PEG-20 / acetate copolymer. Substances preferably suitable as humectants according to the invention are glycerol, diglycerol, triglycerol and butylene glycol.

[0401] Possible insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or ethyl 3-(N-n-butyl-N-acetamido)propionate, which is sold by Merck KGaA under the name Insect Repellent 3535, and ethyl butylacetamidopropionate. These are generally used in the compositions according to the invention in an amount of 0 to 6% by weight, based on the total weight of the sunscreen composition.

[0402] The viscosity of the agent of the invention can be achieved by adding a viscosity modifier. Possible viscosity modifiers are in particular agents that impart consistency, for example fatty alcohols or hydroxy fatty alcohols and partial glycerides with 12 to 22, preferably 16 to 18, carbon atoms, fatty acids or 12-hydroxy fatty acids with 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, since this combination provides a particularly stable and uniform emulsion. Viscosity modifiers also include thickeners, for example Aerosil types (hydrophilic silicic acid), polysaccharides, in particular xanthan gum, guar gum, agar, alginates and tylose, carboxymethylcellulose and hydroxyethyl- and hydroxypropylcellulose, in addition polyethylene glycol monoesters and diesters of fatty acids of higher molecular weight, polyacrylates (for example available from Goodrich and Pemulen types; obtained 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 polyvinyl pyrrolidones. Bentonites, e.g. Gel VS-5PC (Rheox), a mixture of cyclopentasiloxane, disteardimonium hectorite, and propylene carbonate, has also proven to be particularly effective. Surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution, alkyl oligoglucosides, and electrolytes such as sodium chloride and ammonium chloride can also be used to adjust viscosity.

[0403] In the context of the present invention, fats and waxes are understood to mean all lipids which have a fatty or waxy consistency and a melting point above 20° C. These include, for example, the classic triacylglycerols, i.e. triesters of fatty acids with glycerol, which can be of vegetable or animal origin. These can also be mixed esters, i.e. triesters of glycerol with various fatty acids, or mixtures of various glycerides. These also include mixtures of mono-, di- and triglycerides. According to the invention, so-called hardened fats and oils obtained by partial hydrogenation are particularly suitable. Preference is given to hardened plant fats and oils, for example hydrogenated castor oil, peanut oil, soybean oil, rapeseed oil, beetseed 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 fat. Particularly suitable are oxidatively stable vegetable glycerides, which are known under the name or get.

[0404] Possible waxes are, in particular, natural waxes, such as candelilla wax, carnauba wax, Japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygium tallow, ceresin, ozokerite (mineral wax), petrolatum, paraffin, microcrystalline wax; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes.

[0405] In addition to fats, fatty 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, and is generally a so-called phosphatidylcholine (PC). Cephalin, also known as phosphatidic acid, is a derivative of 1,2-diacyl-sn-glycero-3-phosphate and can be mentioned as an example of natural lecithin. In contrast, phospholipids are generally understood to mean monoesters, preferably diesters (phosphoglycerides) of phosphoric acid and glycerol. Sphingosine and sphingolipids can also be used as fatty substances.

[0406] 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; optionally hydroxy-substituted polycarboxylic acids with C6-C 22 Esters of 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, which have a total of at least 24 carbon atoms, in particular Distearyl ether; fatty acids, such as stearic acid, C 12 -C 22 Hydroxy fatty acids, behenic acid, C 12 -C 22 Olefin epoxides and C 12 -C 22 Ring-opening products of fatty alcohols and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.

[0407] Fabricants which can be used are 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 simultaneously acting as foam stabilizers.

[0408] So-called stabilizers which can be used are metal salts of fatty acids, for example magnesium stearate, aluminum stearate and / or zinc stearate or magnesium ricinoleate.

[0409] Suitable cationic polymers which further optimize the sensory properties of the compositions according to the invention and impart a soft feel to the skin are, for example, cationic cellulose derivatives such as are available from Amerchol under the name Polymer JR The obtained quaternized hydroxyethyl cellulose, cationic starch, copolymers of diallyl ammonium salt and acrylamide, quaternized vinyl pyrrolidone / vinylimidazole polymers, e.g. (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as lauryldimonium hydroxypropyl hydrolyzed collagen Quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as amodimethicone, copolymer of adipic acid and dimethylaminohydroxypropyldiethylenetriamine Copolymer of acrylic acid and dimethyldiallylammonium chloride ( 550 / Chemviron), polyaminopolyamides and crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example quaternized chitosan, condensation products of dihaloalkyls, for example dibromobutane, with bisdialkylamines, for example bis-dimethylamino-1,3-propane, optionally distributed in microcrystalline form, cationic guar gum, for example from Celanese CBS, C-17, C-16, quaternized ammonium salt polymers such as those available from Miranol A-15, AD-1, AZ-1.

[0410] In addition, starch derivatives can be used to improve skin feel, such as Dry PC (INCI: Aluminum starch octenylsuccinate).

[0411] Suitable silicone compounds have already been mentioned in conjunction with the oily substances. In addition to dimethylpolysiloxane, methylphenylpolysiloxane, and cyclic siloxanes, amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside-, and / or alkyl-modified silicone compounds that are liquid or resinous at room temperature are also suitable. Furthermore, dimethicone, which is a mixture of polydimethylsiloxane with an average chain length of 200-300 dimethylsiloxane units and silicon dioxide or hydrogenated silicate, is suitable.

[0412] So-called film-forming agents which lead to a further improvement in the organoleptic 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, and also polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, acrylic polymers and quaternized cellulose derivatives, which have already been mentioned under viscosity regulators.

[0413] In addition, in order to improve the flow properties of the composition of the present invention, hydrophilic substances such as ethanol, isopropanol or polyols can be used. Possible polyols here preferably have 2 to 15 carbon atoms and at least 2 hydroxyl groups. The polyols may also contain other functional groups, in particular amino groups, or may be nitrogen-modified.

[0414] Dyes which can be used are substances which are suitable and approved for cosmetic purposes.

[0415] The present invention provides one or more of the following advantages:

[0416] 1. The present invention provides a method for increasing the sun protection factor of a sunscreen composition using porous spheres containing metal oxides.

[0417] 2. The method increases the SPF of a sunscreen formulation while minimizing or masking its whitening effect and maintaining its clarity.

[0418] 3. The porous metal oxide spheres of the present invention can be used to increase the SPF of sunscreen compositions.

[0419] 4. The porous metal oxide spheres of the present invention can be used to increase the SPF of a sunscreen composition while minimizing or masking its whitening effect and maintaining its transparency.

[0420] A list of embodiments is provided below to further illustrate the present disclosure and is not intended to limit the present disclosure to the specific embodiments listed below.

[0421] 1. A method for increasing the sun protection factor of a sunscreen composition, the method comprising adding porous spheres comprising a metal oxide to the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide and chromium oxide.

[0422] 2. Use of porous spheres comprising metal oxides for improving the sun protection factor of a sunscreen composition, wherein the metal oxide is at least one selected from silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide and chromium oxide.

[0423] 3. The method or use according to embodiment 1 or 2, wherein the porous spheres are present in an amount of 0.1-10.0 wt. %, based on the total weight of the sunscreen composition.

[0424] 4. The method or use according to any one of the preceding embodiments, wherein the amount of metal oxide in the porous sphere is 60.0-99.9 wt.%, based on the total weight of the porous sphere.

[0425] 5. The method or use according to any one of the preceding embodiments, wherein the porous spheres have an average diameter of 0.5-100.0 μm.

[0426] 6. A method or use according to any preceding claim, wherein the porous spheres have an average porosity of 0.10-0.90.

[0427] 7. The method or use according to any one of the preceding embodiments, wherein the porous spheres have an average porosity of 0.10-0.80.

[0428] 8. The method or use according to any one of the preceding embodiments, wherein the porous spheres are monodisperse.

[0429] 9. The method or use according to any one of the preceding embodiments, wherein the porous spheres have an average pore size of 50-999 nm.

[0430] 10. The method or use according to any one of the preceding embodiments, wherein the porous sphere has more than one population of pores, each population of pores having an average pore size, wherein each population has a different average pore size.

[0431] 11. The method or use according to any one of the preceding claims, wherein the porous sphere:

[0432] a. having an average diameter of 0.5-100.0 μm;

[0433] b. having an average porosity of 0.10-0.90;

[0434] c. having an average pore size of 50-999 nm, and

[0435] d. is monodisperse.

[0436] 12. The method or use according to any one of the preceding embodiments, wherein the porous sphere:

[0437] a. having an average diameter of 0.5-100.0 μm;

[0438] b. having an average porosity of 0.10-0.80;

[0439] c. having an average pore size of 50-999 nm; and

[0440] d. is monodisperse.

[0441] 13. The method or use according to any one of the preceding embodiments, wherein the sunscreen composition further comprises a UV absorber selected from the group consisting of:

[0442] (d1) p-Aminobenzoic acid derivatives;

[0443] (d2) salicylic acid derivatives;

[0444] (d3) Benzophenone derivatives;

[0445] (d4) dibenzoylmethane derivatives;

[0446] (d5) diphenyl acrylate;

[0447] (d6) 3-Imidazol-4-yl-acrylic acid and its esters;

[0448] (d7) Benzofuran derivatives;

[0449] (d8) polymeric UV absorber;

[0450] (d9) Cinnamic acid derivatives;

[0451] (d 10 ) camphor derivatives;

[0452] (d 11 ) hydroxyphenyltriazine derivatives;

[0453] (d 12 )benzotriazole derivatives;

[0454] (d 13 ) triphenylamino-s-triazine derivatives;

[0455] (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts;

[0456] (d 15 ) anthranilic acid esters;

[0457] (d 16 ) High salicylic acid ester;

[0458] (d 17 ) tris-biphenyltriazine derivatives;

[0459] (d 18 ) TiO2 (partially encapsulated), ZnO and mica;

[0460] (d 19 )benzylidenemalonate;

[0461] (d 20 ) merocyanine derivatives;

[0462] (d 21 )phenylenebis-diphenyltriazine;

[0463] (d 22 ) imidazoline derivatives; and

[0464] (d 23 )Diarylbutadiene derivatives.

[0465] 14. The method according to any one of the preceding embodiments, wherein the method further minimizes or masks the whitening effect of the sunscreen composition and maintains its clarity.

[0466] 15. The use according to any one of the preceding embodiments, wherein the use further minimizes or masks the whitening effect of the sunscreen composition and maintains its transparency.

[0467] 16. A sunscreen composition comprising water and 1.0-10.0 wt % of porous spheres comprising a metal oxide, based on the total weight of the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0468] 17. The sunscreen composition according to embodiment 16, further comprising 5.0-50.0 wt% of a discontinuous oil phase based on the total weight of the sunscreen composition.

[0469] 18. The sunscreen composition according to embodiment 16 or 17, further comprising 1.0-20.0 wt% of at least one emulsifier, based on the total weight of the sunscreen composition.

[0470] 19. The sunscreen composition according to embodiment 18, wherein the emulsifier is selected from anionic emulsifiers, nonionic emulsifiers and polymeric emulsifiers.

[0471] 20. The sunscreen composition according to any one of embodiments 16 to 19, further comprising an additive selected from the group consisting of a thickener, an active ingredient, a preservative, and a fragrance.

[0472] 21. The sunscreen composition according to any one of claims 16 to 20, wherein the amount of metal oxide in the porous sphere is 60.0 to 99.9 wt%, based on the total weight of the porous sphere.

[0473] 22. The sunscreen composition according to any one of embodiments 16 to 21, wherein the porous spheres have an average diameter of 0.5 to 100.0 μm.

[0474] 23. The sunscreen composition according to any one of claims 16 to 22, wherein the porous spheres have an average porosity of 0.10 to 0.90.

[0475] 24. The sunscreen composition according to any one of embodiments 16 to 23, wherein the porous spheres have an average porosity of 0.10 to 0.80.

[0476] 25. The sunscreen composition according to any one of embodiments 16 to 24, wherein the porous spheres have an average pore size of 50 to 999 nm.

[0477] 26. The sunscreen composition of any one of claims 16-25, wherein the porous spheres are monodisperse.

[0478] 27. The sunscreen composition according to any one of claims 16 to 26, wherein the porous spheres:

[0479] a. having an average diameter of 0.5-100.0 μm;

[0480] b. having an average porosity of 0.10-0.90;

[0481] c. having an average pore size of 50-999 nm, and

[0482] d. is monodisperse.

[0483] 28. The sunscreen composition according to any one of embodiments 16-27, wherein the porous sphere:

[0484] a. having an average diameter of 0.5-100.0 μm;

[0485] b. having an average porosity of 0.10-0.80;

[0486] c. having an average pore size of 50-999 nm; and

[0487] d. is monodisperse.

[0488] 29. The sunscreen composition according to any one of embodiments 16-28, wherein the sunscreen composition further comprises a UV absorber selected from the group consisting of:

[0489] (d1) p-Aminobenzoic acid derivatives;

[0490] (d2) salicylic acid derivatives;

[0491] (d3) Benzophenone derivatives;

[0492] (d4) dibenzoylmethane derivatives;

[0493] (d5) diphenyl acrylate;

[0494] (d6) 3-Imidazol-4-yl-acrylic acid and its esters;

[0495] (d7) Benzofuran derivatives;

[0496] (d8) polymeric UV absorber;

[0497] (d9) Cinnamic acid derivatives;

[0498] (d 10 ) camphor derivatives;

[0499] (d 11 ) hydroxyphenyltriazine derivatives;

[0500] (d 12 )benzotriazole derivatives;

[0501] (d 13 ) triphenylamino-s-triazine derivatives;

[0502] (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts;

[0503] (d 15 ) anthranilic acid esters;

[0504] (d 16 ) High salicylic acid ester;

[0505] (d 17 ) tris-biphenyltriazine derivatives;

[0506] (d 18 ) TiO2 (partially encapsulated), ZnO and mica;

[0507] (d 19 )benzylidenemalonate;

[0508] (d 20 ) merocyanine derivatives;

[0509] (d 21 )phenylenebis-diphenyltriazine;

[0510] (d 22 ) imidazoline derivatives; and

[0511] (d 23 )Diarylbutadiene derivatives.

[0512] 30. The sunscreen composition of any one of embodiments 16-29, wherein the sunscreen composition further comprises a dye selected from Acid Violet 43 and Acid Red 33.

[0513] Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are intended herein for purposes of illustration only and not limitation unless otherwise specified. Example

[0514] The present invention is further described with reference to the following examples. These examples are provided to illustrate the present invention, but are not intended to limit the scope of the present invention in any way.

[0515] Material

[0516] Acid Blue 3 (Proprietary Blue V) is 2-[(4-diethylaminophenyl)(4-diethylimino-2,5-cyclohexadien-1-ylidene)methyl]-4-hydroxy-1,5-benzenedisulfonate and was obtained from Sigma Aldrich.

[0517] Benzophenone-4 is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, available from BASF.

[0518] 130 was obtained from Sunjin Beauty Science (formerly Sunjin Chemical).

[0519] Obtained from Dow Chemicals.

[0520] method

[0521] Average diameter or particle size: Particle size is synonymous with particle diameter and is determined by scanning electron microscopy (SEM) or transmission electron microscopy (TEM).

[0522] Average Porosity and Average Pore Size: Mercury porosimetry was used to characterize the porosity of the spheres. Mercury porosimetry involves applying controlled pressure to a sample immersed in mercury. External pressure is applied to cause the mercury to penetrate the voids / pores of the material. The amount of pressure required to penetrate the voids / pores is inversely proportional to the size of the voids / pores. The mercury porosimeter uses the Washburn equation to generate volume and pore size distributions based on the pressure generated by the instrument relative to the intrusion data. For example, porous silica spheres containing voids / pores with an average size of 165 nm have an average porosity of 0.8.

[0523] Determination of in vitro SPF of formulation examples

[0524] In vitro SPF determination is performed by measuring diffuse transmission in the UV range using a Labsphere UV Transmittance Analyzer 2000S. To simulate the uneven surface structure of human skin, substrates with rough or porous surfaces are used for this measurement. For this method, sandblasted 4-5 μm PMMA (polymethyl methacrylate) plates obtained from Heliosince (France) are used as substrates.

[0525] The Sunburn Protection Factor (SPF) formalism was first introduced by Sayre in 1979 [1], whereby the average value of the inverse transmittance (1 / T) of each sunscreen in the spectral range 290–400 nm is calculated, including weighting by the radiation spectrum Ss(λ) and the erythema action spectrum Ser(λ) of the UV source:

[0526]

[0527] References

[0528] [1] RM Sayre, PPAgin, GJ LeVee, E. Marlowe, A comparison of in vivo and in vitro testing of sunscreening formulas, Photochem, Photobiol, 29 (1979), 559-566.

[0529] Clarity / Whitening Method: Color measurements were performed using the prepared compositions applied to PMMA plates, which were also used for in vitro SPF measurements. The L*a*b* parameters obtained are where L* refers to the lightness of the sample. The difference between L* and the blank sample is expressed as ΔL* and can be used to compare the clarity or whitening of the samples.

[0530] Preparation of porous metal oxide spheres

[0531] Example 1: Porous silica spheres

[0532] A styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a 3-necked reaction flask equipped with a thermometer, condenser, magnetic stirrer, and nitrogen atmosphere. The water was heated to 80°C, 10 g of styrene was added with stirring, and then 100 mg of acrylic acid dissolved in 10 mL of DI water was added via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture via syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was cooled to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0533] A polystyrene colloidal aqueous dispersion was diluted to 1% by weight with deionized water, 1% by weight of silica nanoparticles was added, and the mixture was sonicated to prevent particle agglomeration. The continuous oil phase used was a 0.1% by weight polyethylene glycol / perfluoropolyether surfactant in a fluorinated oil. The colloidal aqueous dispersion and the oil were each injected into a microfluidic device with a 50 μm droplet connection via a syringe associated with a pump. The system was allowed to equilibrate until monodisperse droplets were produced. The monodisperse droplets were collected in a reservoir.

[0534] The collected droplets were dried in an oven at 45°C for 4 hours to provide monodisperse polymer template spheres. The polymer template spheres were calcined by placing them on a silicon wafer, heating from room temperature to 500°C over 3 hours, holding at 500°C for 2 hours, and cooling back to room temperature over 3 hours to obtain monodisperse porous silica spheres with an average diameter of 15 microns. These porous silica spheres with an average diameter of 15 μm are porous silica microspheres. The average pore (void) diameter of the silica spheres is 170 nm, and the average porosity is 0.8.

[0535] The drying step can be performed using microwave irradiation, vacuum drying and / or drying in the presence of a desiccant.

[0536] Example 2: Porous silica spheres containing additional light absorbers

[0537] The product of Example 1 was physically mixed with an aqueous dispersion of carbon black or carbon black powder at different weight levels. Monodisperse silica spheres containing carbon black at levels of 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt% and 5 wt% based on the total weight of the spheres were obtained.

[0538] Example 3: Porous silica spheres by spray drying

[0539] A styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a 3-necked reaction flask equipped with a thermometer, condenser, magnetic stirrer, and nitrogen atmosphere. The water was heated to 80°C, and 10 g of styrene was added with stirring. Then, 100 mg of acrylic acid dissolved in 10 mL of DI water was added via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture via syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was cooled to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0540] A polystyrene colloidal aqueous dispersion was diluted to 1% by weight with deionized water, 1% by weight of silica nanoparticles was added, and the mixture was sonicated to prevent particle agglomeration. The aqueous dispersion was spray dried to provide polymer template spheres comprising polymer nanospheres and silica. These spheres were calcined by heating from room temperature to 500°C over 3 hours, holding at 500°C for 2 hours, and cooling back to room temperature over 3 hours to obtain porous silica spheres with an average diameter of 15 microns. The average pore (void) diameter of the silica spheres was 170 nm, and the average porosity was 0.8.

[0541] Example 4: Porous silica spheres

[0542] Porous silica sphere samples were prepared according to the procedure of Example 3. Polymer nanospheres with an average particle size of 421 nm were used, and the weight ratio of polymer to silica was 3:1.

[0543] Silica spheres having an average diameter of 3.63 μm and an average pore (void) diameter of 368 nm were obtained. Figure 1 Shown is an SEM photograph of porous silica spheres obtained according to Example 4. The average porosity of the silica spheres was 0.8.

[0544] Example 5: Porous silica spheres

[0545] Porous silica sphere samples were prepared according to the procedure of Example 3. Polymer nanospheres with an average particle size of 421 nm were used, and the weight ratio of polymer to silica was 3:1.

[0546] Silica spheres having an average diameter of 8.27 μm and a pore (void) size (average pore (void) diameter) of 365 nm were obtained. Figure 2 Shown is an SEM photograph of porous silica spheres obtained according to Example 5. The average porosity of the silica spheres was 0.8.

[0547] Example 6: Porous zinc oxide balls

[0548] Samples of porous zinc oxide spheres were prepared according to the procedure of Example 3, where zinc oxide was used instead of silicon dioxide. Polystyrene nanospheres with an average diameter of 230 nm were used, and the weight ratio of polymer to zinc oxide was 1:2.

[0549] Example 7: Porous Titanium Dioxide Spheres

[0550] Samples of porous titania spheres were prepared according to the procedure of Example 3, wherein titania was substituted for silica. Polymer nanospheres with an average particle size of 170 nm were used, and the weight ratio of polymer to titania was 3:1.

[0551] Titanium dioxide spheres having an average diameter of 2.85 μm and an average pore (void) diameter of 142 nm were obtained. Figure 3 Shown is an SEM photograph of porous titania spheres obtained according to Example 7. The average porosity of the titania spheres was 0.8.

[0552] Example 8: Porous Titanium Dioxide Spheres

[0553] Porous titania spheres were prepared by a procedure similar to Example 7. Polymer nanospheres with an average particle size of 285 nm were used, and the weight ratio of polymer to titania was 3:1.

[0554] Titanium dioxide spheres having an average diameter of 2.95 μm and an average pore (void) diameter of 243 nm were obtained. Figure 4 Shown is an SEM photograph of porous titania spheres obtained according to Example 8. The average porosity of the titania spheres was 0.8.

[0555] Example 9: Porous spheres comprising silicon dioxide and titanium dioxide

[0556] Porous spheres comprising silica and titania were prepared according to the method of Example 3, wherein the weight ratio of polymer to total metal oxides was 3:1 and the weight ratio of silica to titania was 9:1.

[0557] Example 10: Porous Spheres with Two Average Particle Sizes

[0558] Step 1) Polymer spheres having at least two different average particle sizes:

[0559] A styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a 3-necked reaction flask equipped with a thermometer, condenser, magnetic stirrer, and nitrogen atmosphere. The water was heated to 80°C, 10 g of styrene was added with stirring, and then 100 mg of acrylic acid dissolved in 10 mL of DI water was added via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture via syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was cooled to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0560] Similarly, a styrene / acrylic acid copolymer was prepared to produce polystyrene nanospheres with an average particle size of 350 nm.

[0561] The first polystyrene colloid aqueous dispersion (250nm) was mixed with the second polystyrene colloid aqueous dispersion (350nm) in a weight ratio of 7:3, and the mixture was diluted to 1% by weight with deionized water and subjected to ultrasonic treatment to prevent particle agglomeration. The continuous oil phase used was a 0.1% by weight polyethylene glycol / perfluoropolyether surfactant in a fluorinated oil. The colloid aqueous dispersion mixture and the oil were each injected into a microfluidic device with a 50 μm droplet connection through a syringe associated with a pump. The system was balanced until monodisperse droplets were produced. The monodisperse droplets were collected in a reservoir.

[0562] The collected droplets were dried in an oven at 45°C for 4 hours to provide monodisperse polymer spheres. The monodisperse polystyrene spheres comprised polystyrene nanospheres having a bimodal size distribution.

[0563] Step 2) Porous Metal Oxide Balls

[0564] Example 1 was repeated, adding 1 wt% silica nanoparticles to the aqueous mixture of the first and second colloidal dispersions before mixing with the oil phase to form a water-in-oil emulsion. Droplets collected from the microfluidic device were dried as in Example 1 to form polymer template spheres. The polymer template spheres were calcined by placing them on a silicon wafer, heating from room temperature to 500°C over 3 hours, holding at 500°C for 2 hours, and cooling back to room temperature over 3 hours. This provided monodisperse silica spheres with an average diameter of 15 microns, containing two different average pore sizes.

[0565] Example 11: Preparation of porous silica spheres with two average particle sizes by spray drying

[0566] A styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a 3-necked reaction flask equipped with a thermometer, condenser, magnetic stirrer, and nitrogen atmosphere. The water was heated to 80°C, 10 g of styrene was added with stirring, and then 100 mg of acrylic acid dissolved in 10 mL of DI water was added via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture via syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was cooled to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0567] Similarly, a styrene / acrylic acid copolymer was prepared to produce polystyrene nanospheres with an average particle size of 350 nm.

[0568] A first polystyrene colloidal aqueous dispersion (250 nm) was mixed with a second polystyrene colloidal aqueous dispersion (350 nm) in a weight ratio of 7:3, and the mixture was diluted to 1% by weight with deionized water, and 1% by weight of silica nanoparticles was added to the mixture, which was ultrasonically treated to prevent particle agglomeration. The aqueous dispersion was spray dried to provide polymer template spheres comprising monodisperse polymer nanospheres with a bimodal distribution and silica. The spheres were calcined by heating from room temperature to 500° C. over 3 hours, holding at 500° C. for 2 hours, and cooling back to room temperature over 3 hours to obtain porous silica spheres.

[0569] Example 12: Porous zinc oxide spheres with two average particle sizes

[0570] Samples of porous zinc oxide spheres were prepared according to the method of Example 11, wherein polystyrene nanospheres with average particle sizes of 250 nm and 320 nm were used at a weight ratio of 1:1, and wherein the weight ratio of polymer to zinc oxide was 1:2.

[0571] Example 13: Porous Spheres Comprising Silica and Titania with Two Average Particle Sizes

[0572] A sample of porous spheres comprising silica and titania was prepared according to the method of Example 11, wherein polystyrene nanospheres having average particle sizes of 350 nm and 460 nm were used in a weight ratio of 1:4, and wherein the weight ratio of polymer to total metal oxide was 3:1. The weight ratio of silica to titania was 9:1.

[0573] Performance measurement

[0574] Experiment 1: Improving the absorbance of dyes by porous silica spheres

[0575] The porous microspheres containing silica according to Example 3 were dispersed in an aqueous solution of a water-soluble dye. The water-soluble dye was Patent Blue V (also known as Acid Blue 3), whose chemical name is 2-[(4-diethylaminophenyl)(4-diethylimino-2,5-cyclohexadiene-1-ylidene)methyl]-4-hydroxy-1,5-benzenedisulfonate. 最大 =637nm has ε = 113900L mol -1 cm -1 The decimal molar extinction coefficient.

[0576] Another aqueous dispersion containing the porous silica microspheres of Example 3 but without the dye was used as a reference sample.

[0577] The dispersion was filled into a quartz cuvette (Hellma Analytics) with an optical thickness of 0.1 cm and the absorbance was measured using a Perkin Elmer Lambda 20 UV / vis spectrometer with an integrating sphere attachment (RSA-PE-20), which collected both directly transmitted and forward scattered light. Although the Perkin Elmer Lambda 20 is a dual-beam spectrometer, the integrating sphere attachment is a single-beam device.

[0578] The reference and sample dispersion cells are placed in the light beam at the transmission port of the integrating sphere, while the reflectance standard is mounted at the reflection port of the sphere. Measurements are performed with a spectral resolution of 2 nm. The absorbance of the reference dispersion is recorded first, followed by the corresponding sample.

[0579] Figure 5 The results show that the porous silica spheres of Example 3 contain a constant concentration (5.5·10 -6 mol / L) of patent blue V aqueous dispersion. Figure 5 In FIG. 1 , 1 represents the absorption spectrum of the reference sample; 2 represents the absorption spectrum of the aqueous dispersion containing porous silica spheres at a concentration of 2 wt %; and 3 represents the absorption spectrum of the aqueous dispersion containing porous silica spheres at a concentration of 5 wt %.

[0580] from Figure 5 It was observed that the presence of porous silica spheres increased the dye absorption efficiency, and the absorbance increased by about 1.5 times at a concentration of 5 wt% porous microspheres.

[0581] Experiment 2: Improving the absorbance of UV absorbers by porous silica spheres

[0582] The procedure of Experiment 2 was similar to that of Experiment 1, except that a water-soluble UV absorber, benzophenone-4, was used instead of Patent Blue V. The chemical name of this UV absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid. 最大 =The decimal extinction coefficient at 286nm is ε=13650L mol -1 cm -1 .

[0583] Figure 6 The results show that the presence of porous silica spheres in Example 3 contains 5.18·10 -5 The absorbance of a water dispersion of benzophenone-4 at a constant concentration of mol / L. Figure 6 In FIG. 1 , 1 represents the absorption spectrum of the reference sample; 2 represents the absorption spectrum of the aqueous dispersion containing porous silica spheres at a concentration of 2 wt %; and 3 represents the absorption spectrum of the aqueous dispersion containing porous silica spheres at a concentration of 5 wt %.

[0584] from Figure 6 It can be seen that the presence of porous silica spheres enhances the UV absorption efficiency of benzophenone-4. At a concentration of 5 wt % porous silica spheres, the absorbance of UV radiation increases by about 2.5 times.

[0585] Therefore, the increase in absorbance in the UV range (ie the increase in absorbance due to the presence of the porous spheres) is greater than in the visible range.

[0586] Experiment 3: Effect of concentration on UV absorption

[0587] A set of five aqueous dispersions containing benzophenone-4 and different concentrations of the porous silica particles of Example 3 were prepared by a procedure similar to that of Experiment 2. Similarly, a set of aqueous dispersions containing different concentrations of the porous silica particles of Examples 4 and 5 were prepared. A blank sample without any porous metal oxide particles was prepared for comparison. 最大 The UV absorbance of the aqueous dispersion was measured under 400 nm.

[0588] Figure 7The graph shows the absorbance curve of the aqueous dispersion containing benzophenone-4 at various concentrations of the porous silica spheres of Examples 3, 4 and 5 at an optical path length d of 0.1 cm. Figure 7 In the figure, 1 represents the absorption spectrum of the aqueous dispersion containing the porous silica spheres of Example 3; 2 represents the absorption spectrum of the aqueous dispersion containing the porous silica spheres of Example 4; 3 represents the absorption spectrum of the aqueous dispersion containing the porous silica spheres of Example 5; and blank represents the absorbance of the blank sample.

[0589] from Figure 7 It was observed that the UV absorption efficiency of benzophenone-4 increased with increasing concentration of porous silica spheres.

[0590] Experiment 4: Comparative Example

[0591] A set of commercial silica particles containing benzophenone-4 and different concentrations obtained from Sunjin were prepared by the procedure of Experiment 2. 130. Blank samples without porous metal oxide particles were prepared for comparison. 最大 The UV absorbance of the aqueous dispersion was measured under 400 nm.

[0592] Figure 8 The results show that the aqueous dispersion containing benzophenone-4 has an optical path length d of 0.1 cm and various concentrations of silica particles. 130 ℃. Figure 8 1 means included Absorption spectrum of an aqueous dispersion of 130 silica particles; blank represents the absorbance of a blank sample.

[0593] from Figure 8 It was observed that silica particles The presence of 130 had no effect on the UV absorption efficiency of benzophenone-4.

[0594] Experiment 5: Improving the absorbance of dyes by porous titanium dioxide spheres

[0595] The procedure of Experiment 5 was similar to that of Experiment 1, except that the porous titanium dioxide particles prepared according to Examples 7 and 8 were used instead of the porous silicon dioxide particles.

[0596] Figure 9 The visible range absorption spectra of the aqueous dispersions in the presence of porous titanium dioxide spheres of Examples 7 and 8 at concentrations of 0.2 wt% and 0.5 wt% at an optical path length d of 0.1 cm are shown. Figure 9In the figure, 1 represents the absorption spectrum of the aqueous dispersion containing the porous titanium dioxide spheres of Example 8 at a concentration of 0.5 wt%; 2 represents the absorption spectrum of the aqueous dispersion containing the porous titanium dioxide spheres of Example 7 at a concentration of 0.5 wt%; 3 represents the absorption spectrum of the aqueous dispersion containing the porous titanium dioxide spheres of Example 8 at a concentration of 0.2 wt%; 4 represents the absorption spectrum of the aqueous dispersion containing the porous titanium dioxide spheres of Example 7 at a concentration of 0.2 wt%; 5 represents the absorbance of the reference sample not containing any porous metal oxide spheres.

[0597] from Figure 9 It was observed that the presence of porous titania spheres increased the dye absorption efficiency and the absorbance increased by about 2.8 and 4 times at a porous microsphere concentration of 5 wt% of porous titania spheres from Examples 7 and 8, respectively.

[0598] Experiment 6: Absorption Spectra of Porous Titanium Dioxide Spheres

[0599] The porous titanium dioxide spheres prepared according to Examples 7 and 9 were dispersed in aqueous solutions without any dye or UV absorber. The UV absorption of these solutions was analyzed in a similar manner to Experiment 1.

[0600] Figure 10 The UV absorption spectra of aqueous dispersions containing porous titanium dioxide spheres of Examples 7 and 8 at concentrations of 0.2 wt % and 0.5 wt %, respectively, at an optical path length d of 0.1 cm are shown. Figure 10 In the figure, 1 represents the absorption spectrum of the aqueous dispersion of porous titanium dioxide spheres of Example 7 at a concentration of 0.4 wt%; 2 represents the absorption spectrum of the aqueous dispersion of porous titanium dioxide spheres of Example 8 at a concentration of 0.4 wt%; 3 represents the absorption spectrum of the aqueous dispersion of porous titanium dioxide spheres of Example 7 at a concentration of 0.2 wt%; and 4 represents the absorption spectrum of the aqueous dispersion of porous titanium dioxide spheres of Example 8 at a concentration of 0.2 wt%.

[0601] from Figure 10 It was observed that the aqueous dispersion containing porous titanium dioxide spheres exhibited broad UV absorption in the range of 250-390 nm, with maximum UV absorption in the range of 320-340 nm. Absorption was high in the UVB range of 290-320 nm, while absorption showed a sharp drop in the UVA range of 380-420 nm. Experiment 7: Sun Protection Factor (SPF) Experiment

[0602] To determine the SPF, two sets of compositions were prepared: a first set of compositions was prepared with UV filters in the oil phase and a second set of compositions was prepared without additional UV filters.

[0603] 3.1) Compositions with UV filters

[0604] The following composition was prepared:

[0605] Table 1: Formulations containing UV filters

[0606]

[0607] Procedure for preparing the base formulation: Heat phases A and B separately while stirring. Add phase A to phase B while stirring. Stir the mixture until a homogeneous mixture is obtained, then stir for 1 minute. Finally, cool the mixture to room temperature while stirring. Prepare the base formulation at 80°C.

[0608] Sample formulation:

[0609] Two formulations were prepared using 2% and 5.5% by weight of the porous spheres according to Example 3. The porous spheres were added to the base formulation with stirring and made up to 100% with water.

[0610] Reference formulation:

[0611] Commercially available products from Dow Chemicals were used. Preparation of a reference sample: 5.5% by weight of a commercial product was incorporated into the base formulation. It is a styrene-acrylate copolymer with hollow spherical morphology prepared by controlled emulsion polymerization.

[0612] Placebo formulation:

[0613] A placebo sample containing no particles was prepared by adding water to the base formulation to 100.

[0614] evaluate:

[0615] The SPF of these compositions were measured according to the in vitro SPF method (according to RM Sayre et al.) and the results are shown in Table 2.

[0616] Table 2: In vitro SPF evaluation of compositions comprising UV filters

[0617]

[0618] Figure 11 The absorbance of compositions 5, 6, 8 and 9 in the wavelength range of 290-450 nm is shown. Figure 11 , 1 represents the absorption spectrum of composition 9; 2 represents the absorption spectrum of composition 5; 3 represents the absorption spectrum of composition 6; and 4 represents the absorption spectrum of placebo composition 8.

[0619] The in vitro SPF increased by 20% with the addition of 2% porous silica spheres, and the in vitro SPF increased by 28% with the addition of 5.5% porous silica spheres. It can be concluded that at a particle concentration of 5.5%, the presence of the porous spheres increased the UV absorption efficiency at 312 nm (UVB peak maximum) by about 6.6 times and at 351 nm (UVA peak maximum) by about 5.3 times.

[0620] Including for comparative analysis An increase in SPF was also observed in the composition of Nanoparticles can be identified by the fraction of scattering at higher wavelengths above 400 nm, often referred to as “tailing.” This scattering results in an undesirable visible whitening effect on the skin.

[0621] 3.2) Formulations without additional UV filters

[0622] The following formulations were prepared using the procedure described in Experiment 3.1 above. The contents of the base composition and the reference composition are provided in Table 3.

[0623] Table 3: Base composition and reference composition without additional UV filters

[0624]

[0625] Placebo formulation:

[0626] A placebo sample containing no particles was prepared by adding water to the base formulation to 100.

[0627] Sample formulation:

[0628] Three formulations were prepared using 2%, 5.5% and 8% by weight of porous silica spheres from Example 3. The porous spheres were introduced into the base formulation with water.

[0629] Reference formulation:

[0630] The commercial product obtained from Dow Chemicals was used Preparation of a reference sample: 5.5% by weight of a commercial product was incorporated into the base formulation.

[0631] Table 4: Formulations without additional UV filters

[0632]

[0633] The SPF of these compositions were measured according to the in vitro SPF method (according to RM Sayre et al.) and the results are shown in Table 5.

[0634] Table 5: In vitro SPF evaluation of samples without additional UV absorbers

[0635]

[0636] Figure 12 The absorbance of the composition without additional UV filters in the range of 290-450 nm is shown. Figure 12 , 1 represents the absorption spectrum of composition 3; 2 represents the absorption spectrum of composition 2; 3 represents the absorption spectrum of composition 1; and 4 represents the absorption spectrum of the placebo composition.

[0637] The compositions with 5.5 wt% or 8 wt% of added particles showed increased absorption across the entire UV range of 290-450 nm. The in vitro SPF of the composition increased by 10% when 5.5 wt% of the porous spheres of Example 3 were added, and by 20% when 8 wt% of the porous spheres of Example 3 were added.

[0638] Experiment 4: Transparency / whitening experiment

[0639] The whitening data for the two series of formulations prepared in Example 3 were determined by color measurement as described above.

[0640] Figure 13 The results for formulations using UV filters are summarized in Figure 13 , 1 represents the absorption spectrum of composition 9; 2 represents the absorption spectrum of composition 5; 3 represents the absorption spectrum of composition 6; and 4 represents the absorption spectrum of placebo composition 8.

[0641] The results for formulations without UV filters are summarized in Figure 14 In. Figure 14 , 1 represents the absorption spectrum of the placebo composition; 2 represents the absorption spectrum of composition 1; 3 represents the absorption spectrum of composition 2; 4 represents the absorption spectrum of composition 3; and 5 represents the absorption spectrum of composition 4 containing the reference composition.

[0642] from Figure 13 and Figure 14 Observe that Significantly scatters visible light, thus producing a strong whitening effect on the skin. Figure 13 ΔL* increased by 8 (120%), Figure 14 The whitening effect was not observed with the porous spheres according to the invention. The brightness of the formulation containing the porous spheres according to the invention was the same as that of the reference. Only at the highest concentration of 8% by weight of porous spheres was a slight increase of 2.8 (29%) observed, which is not visible because only a difference of ΔL* greater than 4 can be detected by the untrained eye.

Claims

1. A method for increasing the sun protection factor of a sunscreen composition, the method comprising adding porous spheres comprising an oxide to the sunscreen composition, wherein the oxide is at least one selected from silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide, wherein the porous spheres have an average diameter of 0.5-100.0 μm, and the porous spheres contain uniform pore size, wherein the porous spheres have an average pore size of 50-999 nm.

2. Use of porous spheres comprising oxides for increasing the sun protection factor of a sunscreen composition, wherein the oxide is at least one selected from silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide and chromium oxide, wherein the porous spheres have an average diameter of 0.5-100.0 μm, and the porous spheres contain uniform pore size, wherein the porous spheres have an average pore size of 50-999 nm.

3. The method or use according to claim 1 or 2, wherein the porous spheres are present in an amount of 0.1 to 10.0 wt. %, based on the total weight of the sunscreen composition.

4. The method or use according to any one of the preceding claims, wherein the amount of oxide in the porous sphere is 60.0-99.9% by weight, based on the total weight of the porous sphere.

5. The method or use according to any one of the preceding claims, wherein the porous spheres have an average diameter of 1.0-90.0 μm.

6. A method or use according to any preceding claim, wherein the porous spheres have an average porosity of 0.10-0.

90.

7. A method or use according to any preceding claim, wherein the porous spheres have an average porosity of 0.10-0.

80.

8. A method or use according to any preceding claim, wherein the porous spheres are monodisperse.

9. The method or use according to any one of the preceding claims, wherein the porous sphere has more than one population of pores each having an average pore size, wherein each population has a different average pore size.

10. The method or use according to any one of the preceding claims, wherein the porous sphere: a. having an average diameter of 0.5-100.0 μm; b. having an average porosity of 0.10-0.90; c. having an average pore size of 50-999 nm, and d. is monodisperse.

11. The method or use according to any one of the preceding claims, wherein the porous sphere: a. having an average diameter of 0.5-100.0 μm; b. having an average porosity of 0.10-0.80; c. having an average pore size of 50-999 nm, and d. is monodisperse.

12. The method or use according to any one of the preceding claims, wherein the sunscreen composition further comprises a UV absorber selected from the group consisting of: (d1) p-Aminobenzoic acid derivatives; (d2) salicylic acid derivatives; (d3) Benzophenone derivatives; (d4) dibenzoylmethane derivatives; (d5) diphenyl acrylate; (d6) 3-Imidazol-4-yl-acrylic acid and its esters; (d7) Benzofuran derivatives; (d8) polymeric UV absorber; (d9) Cinnamic acid derivatives; (d 10 ) camphor derivatives; (d 11 ) hydroxyphenyltriazine derivatives; (d 12 )benzotriazole derivatives; (d 13 ) triphenylamino-s-triazine derivatives; (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d 15 ) anthranilic acid esters; (d 16 ) High salicylic acid ester; (d 17 ) tris-biphenyltriazine derivatives; (d 18 ) partially encapsulated TiO2, ZnO and mica; (d 19 )benzylidenemalonate; (d 20 ) merocyanine derivatives; (d 21 )phenylenebis-diphenyltriazine; (d 22 ) imidazoline derivatives; and (d 23 )Diarylbutadiene derivatives.

13. The method of any preceding claim, wherein the method further minimizes or masks the whitening effect of the sunscreen composition and maintains its clarity.

14. The use according to any one of the preceding claims, wherein the use further minimizes or masks the whitening effect of the sunscreen composition and maintains its transparency.

15. A sunscreen composition comprising water and 1.0-10.0 wt. % of porous spheres comprising an oxide, based on the total weight of the sunscreen composition, wherein the oxide is at least one selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, cerium dioxide, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide, wherein the porous spheres have an average diameter of 0.5-100.0 μm, and the porous spheres contain uniform pore size, wherein the porous spheres have an average pore size of 50-999 nm.

16. The sunscreen composition of claim 15, further comprising 5.0 to 50.0 weight percent of a discontinuous oil phase, based on the total weight of the sunscreen composition.

17. The sunscreen composition according to claim 15 or 16, further comprising 1.0 to 20.0 wt% of at least one emulsifier, based on the total weight of the sunscreen composition.

18. The sunscreen composition according to claim 17, wherein the emulsifier is selected from anionic emulsifiers, nonionic emulsifiers and polymeric emulsifiers.

19. The sunscreen composition according to any one of claims 15 to 18, further comprising an additive selected from the group consisting of a thickener, an active ingredient, a preservative and a fragrance.

20. The sunscreen composition according to any one of claims 15 to 19, wherein the amount of the oxide in the porous sphere is 60.0 to 99.9 wt%, based on the total weight of the porous sphere.

21. The sunscreen composition according to any one of claims 15 to 20, wherein the porous spheres have an average diameter of 1.0 to 90.0 μm.

22. The sunscreen composition according to any one of claims 15 to 21, wherein the porous spheres have an average porosity of 0.10 to 0.

90.

23. The sunscreen composition according to any one of claims 15 to 22, wherein the porous spheres have an average porosity of 0.10 to 0.

80.

24. The sunscreen composition according to any one of claims 15 to 23, wherein the porous spheres have an average pore size of 50 to 999 nm.

25. The sunscreen composition of any one of claims 15-24, wherein the porous spheres are monodisperse.

26. The sunscreen composition according to any one of claims 15 to 25, wherein the porous spheres: a. having an average diameter of 0.5-100.0 μm; b. having an average porosity of 0.10-0.90; c. having an average pore size of 50-999 nm, and d. is monodisperse.

27. The sunscreen composition according to any one of claims 15 to 26, wherein the porous spheres: a. having an average diameter of 0.5-100.0 μm; b. having an average porosity of 0.10-0.80; c. having an average pore size of 50-999 nm, and d. is monodisperse.

28. The sunscreen composition according to any one of claims 15 to 27, wherein the sunscreen composition further comprises a UV absorber selected from the group consisting of: (d1) p-Aminobenzoic acid derivatives; (d2) salicylic acid derivatives; (d3) Benzophenone derivatives; (d4) dibenzoylmethane derivatives; (d5) diphenyl acrylate; (d6) 3-Imidazol-4-yl-acrylic acid and its esters; (d7) Benzofuran derivatives; (d8) polymeric UV absorber; (d9) Cinnamic acid derivatives; (d 10 ) camphor derivatives; (d 11 ) hydroxyphenyltriazine derivatives; (d 12 )benzotriazole derivatives; (d 13 ) triphenylamino-s-triazine derivatives; (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts; (d 15 ) anthranilic acid esters; (d 16 ) High salicylic acid ester; (d 17 ) tris-biphenyltriazine derivatives; (d 18 ) partially encapsulated TiO2, ZnO and mica; (d 19 )benzylidenemalonate; (d 20 ) merocyanine derivatives; (d 21 )phenylenebis-diphenyltriazine; (d 22 ) imidazoline derivatives; and (d 23 )Diarylbutadiene derivatives.

29. The sunscreen composition of any one of claims 15 to 28, wherein the sunscreen composition further comprises a compound selected from the group consisting of Acid Violet 43 and Acid Red 33.

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