Screen composition containing porous metal oxide spheres

Abstract

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

Description

[Technical Field]

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

[0002] Sunscreen compositions are used to shield human skin from sun damage. Sunscreen compositions with high UV protection (high SPF) are necessary to counteract the harmful effects of sun radiation, particularly ultraviolet radiation. A wide variety of UV absorbers are available for use in sunscreen compositions.

[0003] However, challenges remain in providing sunscreen compositions with high SPF due to various reasons, such as limitations on incorporating high amounts of UV filters into cosmetic compositions due to their low solubility or regulatory restrictions. Furthermore, such compositions may be associated with problems, such as a whitening effect. Therefore, there is a need for a method to increase SPF while maintaining the transparency of existing sunscreen compositions. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In view of the above, the object of the present invention is to provide a method for increasing the SPF of a sunscreen composition. Furthermore, the sunscreen composition is required to be free from undesirable appearance issues, such as a whitening effect. [Means for solving the problem]

[0005] Surprisingly, it was found that the objective could be achieved by adding porous spheres containing metal oxides (e.g., microspheres) to the sunscreen composition, thereby increasing the SPF of the sunscreen composition.

[0006] In view of the above, the main aspect of the present invention is to provide a method for increasing the SPF of a sunscreen composition. The method comprises the step of adding porous spheres (e.g., microspheres) containing a metal oxide to a sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0007] Another aspect of the present invention is the use of porous spheres (e.g., microspheres) containing a metal oxide to enhance the ultraviolet protection index of a sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0008] In yet another embodiment, the present invention provides a sunscreen composition comprising water and porous spheres (e.g., microspheres), wherein the porous spheres contain a metal oxide in an amount ranging from 0.1 to 10.0% by weight relative to the total weight of the sunscreen composition, and the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0009] The disclosures described herein are illustrated by the accompanying figures and are not limited to them. [Brief explanation of the drawing]

[0010] [Figure 1] This figure shows a scanning electron microscope (SEM) image of a porous silica sphere according to an embodiment of the present invention. [Figure 2] This figure shows an SEM image of a porous silica sphere according to an embodiment of the present invention. [Figure 3] This figure shows an SEM image of a porous titania sphere according to an embodiment of the present invention. [Figure 4]This figure shows an SEM image of a porous titania sphere according to an embodiment of the present invention. [Figure 5] This figure shows a graph relating to the absorbance of an aqueous dispersion containing Patent Blue V in the presence of porous silica spheres. [Figure 6] This figure shows a graph of the UV absorbance of an aqueous dispersion containing benzophenone-4 in the presence of porous silica spheres. [Figure 7] This figure shows a graph of UV absorbance at λmax of aqueous dispersions containing benzophenone-4 in the presence of varying amounts of porous silica spheres. [Figure 8] This figure shows a graph of the UV absorbance at λmax of an aqueous dispersion containing benzophenone-4 in the presence of the commercially available sample Sunsil® 130. [Figure 9] This figure shows a graph relating the absorbance of an aqueous dispersion containing Patent Blue V in the presence of porous titania spheres. [Figure 10] This figure shows a graph relating to the UV absorbance of an aqueous dispersion containing porous titania spheres. [Figure 11] This figure shows graphs relating to the absorbance of sunscreen compositions containing a UV filter in the absence and presence of porous silica spheres. [Figure 12] This figure shows graphs relating to the absorbance of sunscreen compositions without additional UV filters, both in the absence and in the presence of porous silica spheres. [Figure 13] This figure shows a chart illustrating the whitening effect of sunscreen compositions containing a UV filter in the absence and presence of porous silica spheres. [Figure 14] This figure shows a chart relating to the whitening effect of sunscreen compositions without additional UV filters, both in the absence and in the presence of porous silica spheres. [Modes for carrying out the invention]

[0011] Before describing the compositions and formulations of the present invention, it should be understood that the present invention is not limited to the specific compositions and formulations described herein, for such compositions and formulations can naturally vary. It should also be understood that the scope of the present invention is limited only by the appended claims, and therefore the terms used herein are not intended to be limiting.

[0012] Where a group is defined below to include at least a certain number of embodiments, this is preferably intended to also include groups consisting only of these embodiments. Furthermore, terms such as “first,” “second,” “third,” or “a,” “b,” “c,” etc., in the text and claims are not necessarily used to describe the order in which they occurred or in chronological order, but are used to identify similar elements. It should be understood that terms used in this way are interchangeable under appropriate circumstances, and that embodiments of the invention described herein can be operated in an order other than that described or illustrated herein. Where terms such as “first,” “second,” “third,” or “(A),” “(B),” and “(C),” or “(a),” “(b),” “(c),” “(d),” “i,” “ii,” etc., relate to a method, use, or steps of an assay, there is no time or time interval coherence between steps. That is, unless otherwise indicated in the applications described above or below herein, steps may be performed simultaneously, or there may be time intervals of seconds, minutes, hours, days, weeks, months, or years between such steps.

[0013] Furthermore, the ranges defined throughout this specification include both end values; that is, the range 1 to 10 means that both 1 and 10 are included within that range. To avoid misunderstanding, the applicant shall be granted rights to either equivalent in accordance with applicable law.

[0014] Different embodiments of the present invention are defined in more detail in the following sections. Each of these embodiments may be combined with any or more other embodiments unless otherwise explicitly stated. In particular, any feature indicated as preferred or advantageous may be combined with any or more other features indicated as preferred or advantageous.

[0015] Throughout this specification, any reference to “one embodiment” or “embodiment” means that certain features, structures, or characteristics described in relation to the embodiment are included in at least one embodiment of the present invention. Therefore, while the phrases “in one embodiment” or “in an embodiment” appearing in various places throughout this specification do not necessarily all refer to the same embodiment, they may sometimes.

[0016] Furthermore, specific features, structures, or properties can be combined in one or more embodiments in any preferred manner that will be apparent to those skilled in the art from this disclosure. Moreover, some embodiments described herein may or may not include features included in other embodiments, but combinations of features from different embodiments are within the scope of the present invention and constitute different embodiments as understood by those skilled in the art. For example, any of the claimed embodiments in the appended claims can be used in any combination.

[0017] Surprisingly, it was found that adding porous spheres containing metal oxides (e.g., microspheres) to a sunscreen composition increased the SPF of the sunscreen composition. Furthermore, it was observed that the resulting sunscreen composition did not exhibit the whitening effect usually associated with the addition of scattering particles. As a result, the present invention provides a sunscreen composition having high SPF and low whitening.

[0018] Porous metal oxide spheres (e.g., microspheres) scatter light passing through the sunscreen composition. As a result, the presence of porous metal oxide spheres (e.g., microspheres) in the sunscreen composition increases the overall path length of light traveling through the sunscreen layer. Consequently, photon absorption by UV filter or dye molecules present in the sunscreen composition increases. Therefore, an overall increase in the absorbance of the dye or UV absorber is achieved without increasing its concentration.

[0019] In view of the above, the main aspect of the present invention is to provide a method for increasing the ultraviolet protection index of a sunscreen composition. The method comprises the step of adding porous spheres (e.g., microspheres) containing a metal oxide to a sunscreen composition, wherein the metal oxide is preferably at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0020] In some embodiments, the metal oxide is at least one selected from the group consisting of silica, zinc oxide, and titania. In another embodiment, the metal oxide is silica. In yet another embodiment, the metal oxide is titania.

[0021] Another aspect of the present invention is the use of porous spheres (e.g., microspheres) containing a metal oxide to enhance the ultraviolet protection index of a sunscreen composition, wherein the metal oxide is preferably at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0022] In some embodiments, the metal oxide is at least one selected from the group consisting of silica, zinc oxide, and titania. In another embodiment, the metal oxide is silica. In yet another embodiment, the metal oxide is titania.

[0023] In some embodiments, the porous spheres (e.g., microspheres) contain an additional light absorber. In preferred embodiments, the additional light absorber is carbon black powder. In the context of the present invention, microspheres are spherical or spherical-like fine particles typically having an average diameter or particle size ranging from 1 μm to 1000 μm (1 mm). Examples of microspheres include glass microspheres and polyethylene microspheres.

[0024] In the context of this invention, the SPF factor (ultraviolet protection index, SPF) serves to evaluate a photoprotective preparation (sunscreen composition) in humans (in vivo). It indicates how long a person wearing the sunscreen can be exposed to the sun without suffering sunburn, which can occur within that particular individual's self-protection time.

[0025] SPF is determined in vitro by measuring diffuse transmission in the spectral range of 290–400 nm.

[0026] In the context of the present invention, the term “monodisperse” with respect to spheres, microspheres, or nanospheres means particles having a generally uniform shape and a generally uniform diameter. The monodisperse population of spheres, microspheres, or nanospheres may, based on number, consist of 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% particles having a diameter within ±7%, ±6%, ±5%, ±4%, ±3%, ±2%, or ±1% of the mean diameter of the population.

[0027] In the context of this invention, the term "particle size" is synonymous with particle diameter and is determined, for example, by scanning electron microscopy (SEM) or transmission electron microscopy (TEM). Average particle size is synonymous with D50, meaning that half of the population is above this point and half is below it. Particle size refers to primary particles. Particle size can be measured using a dispersion or dry powder by laser light scattering techniques.

[0028] In some embodiments, porous spheres (e.g., microspheres) are present in amounts ranging from 0.1 to 10.0% by weight, or from 1.0 to 8.0% by weight, or from 2.0 to 7.0% by weight, relative to the total weight of the sunscreen composition.

[0029] In a particularly preferred embodiment, porous spheres (e.g., microspheres) are present in an amount of 5.5% by weight relative to the total weight of the sunscreen composition.

[0030] In another particularly preferred embodiment, porous spheres (e.g., microspheres) are present in an amount of 2.0% by weight relative to the total weight of the sunscreen composition.

[0031] In some embodiments, the amount of metal oxide in the porous sphere is in the range of 60.0 to 99.9% by weight, or 65.0 to 99.0% by weight, or 75.0 to 98.0% by weight, or 80.0 to 95.0% by weight, relative to the total weight of the porous sphere.

[0032] In some embodiments, the porous spheres have an average diameter in the range of 0.5 μm to 100.0 μm, or 1.0 μm to 90.0 μm, or 5.0 μm to 80.0 μm, or 10.0 μm to 70.0 μm, or 20.0 μm to 50.0 μm.

[0033] In some embodiments, the porous sphere has an average porosity in the range of 0.10 to 0.90.

[0034] In some embodiments, the porous sphere has an average porosity in the range of 0.10 to 0.80, or 0.30 to 0.80, or 0.15 to 0.75, or 0.25 to 0.60, or 0.30 to 0.50.

[0035] In some embodiments, the porous spheres are monodisperse.

[0036] In some embodiments, the porous sphere has an average pore diameter in the range of 50 nm to 999 nm, or 100 nm to 900 nm, or 200 nm to 800 nm, or 300 nm to 700 nm, or 400 nm to 600 nm.

[0037] In some embodiments, the porous sphere has one or more pore clusters, each having an average pore diameter, and each cluster has a different average pore diameter. In another embodiment, the porous sphere has two pore clusters, each having an average pore diameter.

[0038] In some embodiments, the porous sphere is a. Having an average diameter in the range of 0.5 μm to 100.0 μm, b. Having an average porosity in the range of 0.10 to 0.90, c. Having an average pore diameter in the range of 50 nm to 999 nm, d. It is a simple variance.

[0039] In some embodiments, the porous sphere is a. Having an average diameter in the range of 0.5 μm to 100.0 μm, b. Having an average porosity in the range of 0.10 to 0.80, c. Having an average pore diameter in the range of 50 nm to 999 nm, d. It is a simple variance.

[0040] In some embodiments, porous metal oxide spheres are prepared using a polymer sacrificial template.

[0041] Porous spheres are prepared by a method including, for example, the following steps:

[0042] 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 obtain polymer template spheres (e.g., microspheres) containing polymer spheres and metal oxides. The polymer spheres are removed from the template spheres to obtain porous metal oxide spheres.

[0043] An alternative method for preparing porous spheres having at least two different average particle sizes includes the following steps:

[0044] A liquid solution or dispersion of monodisperse polymer particles (e.g., nanoparticles) is formed. Another at least one more liquid solution or dispersion of monodisperse polymer particles (e.g., nanoparticles) is formed. The average diameter of the monodisperse polymer particles in each solution or dispersion is different.

[0045] Each of the solutions or dispersions is mixed together. A metal oxide is added to one or more of the solutions or dispersions, and / or to the mixture, to obtain a final liquid dispersion of polymer particles and metal oxides.

[0046] Droplets of the final liquid dispersion are formed. The droplets are dried to obtain monodisperse polymer spheres with a bimodal distribution and polymer template spheres containing metal oxides. The polymer spheres are removed from the template spheres to obtain porous metal oxide spheres, which are typically microspheres.

[0047] In some embodiments, the method includes the steps of forming a liquid dispersion of polymer particles (e.g., nanoparticles) and a metal oxide, spray-drying the liquid dispersion to obtain polymer template spheres, and removing the polymer spheres from the template spheres.

[0048] The droplets are either aqueous or oily. In some embodiments, a vibrating nozzle is used to form the droplets.

[0049] In some embodiments, the method includes the steps of preparing a continuous phase, mixing a liquid dispersion with the continuous phase to form an emulsion containing dispersed liquid dispersion droplets, and collecting the droplets.

[0050] In some embodiments, drying requires microwave irradiation, oven drying, drying under vacuum, drying in the presence of a desiccant, or a combination thereof.

[0051] In some embodiments, the weight ratio of polymer particles (e.g., nanoparticles) to metal oxides is in the range of 0.5:1 to 10.0:1.

[0052] In some embodiments, the polymer is selected from the group consisting of poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, their derivatives, their salts, their copolymers, and combinations thereof.

[0053] In some embodiments, polymer spheres (e.g., nanospheres) are removed from template spheres (e.g., microspheres) using techniques such as calcination, thermal decomposition, or solvent removal.

[0054] In some embodiments, polymer spheres (e.g., nanospheres) are removed from a template sphere (e.g., microspheres) by baking the template sphere at a temperature in the range of 350-700°C for 1-8 hours.

[0055] Porous spheres containing metal oxides (e.g., microspheres) are spherical or spherical-like and on a micron scale.

[0056] The polymer particles used as templates are spherical, nanoscale polymer particles that are monodisperse. The metal oxides used are in the form of particles, and may also be nanoscale particles. By drying the polymer / metal oxide droplets and then removing the polymer, microspheres with uniform voids (pores) are obtained. Therefore, the porous metal oxide spheres have uniform pore diameters as a result of the polymer particles being porous and monodisperse.

[0057] Pore ​​diameter depends on the size of the polymer particles. Some shrinkage or compression may occur during polymer removal, resulting in pore diameters somewhat smaller than the original polymer particle size, for example, 10% to 40% smaller. The pore diameter is uniform, ensuring that the shape and size of the polymer particles are uniform.

[0058] UV absorber In some embodiments, the sunscreen composition is (d1) p-aminobenzoic acid derivative, (d2) Salicylic acid derivatives, (d3) Benzophenone derivatives, (d4) Dibenzoylmethane derivatives, (d5) Diphenyl acrylate, (d6) 3-Imidazole-4-yl acrylic acid and its esters, (d7) Benzofuran derivatives, (d8) High molecular weight UV absorber, (d9) Cinnamic acid derivatives, (d 10 ) Camphor derivatives, (d 11 ) Hydroxyphenyltriazine derivatives, (d 12 ) Benzotriazole derivatives, (d 13 ) Trianilino-s-triazine derivatives, (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts, (d 15) Menthylo - aminobenzoate, (d 16 ) Homosalate, (d 17 ) Tris - biphenyltriazine derivative, (d 18 ) TiO2 (partially encapsulated), ZnO and mica, (d 19 ) Benzylidene malonate, (d 20 ) Merocyanine derivative, (d 21 ) Phenylenebis diphenyltriazine, (d 22 ) Imidazoline derivative, and (d 23 ) Diarylbutadiene derivative further comprises a UV absorber selected from the group consisting of.

[0059] Compounds that can be used as examples for p - aminobenzoic acid derivatives (d1) are 4 - aminobenzoic acid (PABA); formula (PABA - 01)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0060] Compounds that can be used as examples for salicylic acid derivatives (d2) are formula (SAD - 01) [ka] Homomenthyl salicylate; formula (SAD-02) [ka] Triethanolamine salicylate; formula (SAD-03) [ka] amyl p-dimethylaminobenzoate; formula (SAD-04) [ka] Octyl salicylate; or formula (SAD-05) [ka] It is 4-isopropylbenzyl salicylate.

[0061] Compounds that can be used as examples for benzophenone derivatives (d3) include benzophenone-3 (2-hydroxy-4-methoxybenzophenone); benzophenone-4 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid); benzophenone-8 (2,2'-dihydroxy-4-methoxybenzophenone); or formula (HBP-01) [ka] It is an amino-substituted hydroxybenzophenone. [In the formula, R1 and R2 are hydrogen, C1~C 20 -Alkyl, C2~C 10 -Alkenil, C3~C 10 -Cycloalkyl, C3~C 10 - Represents a cycloalkenyl, where substituents R1 and R2, together with the nitrogen atom to which they are bonded, can form a 5-membered or 6-membered ring. R3 and R4 operate independently of each other, C1~C 20 -alkyl;C2~C1O -Alkenil; C3~C 10 -Cycloalkyl; C3~C 10 -Cycloalkenyl; C1~C 22 -alkoxy;C1~C 20 -Alkoxycarbonyl;C1~C 12 -Alkylamino;C1~C 12 - Represents a substituent selected from the group consisting of dialkylamino; optionally substituted aryl; hetalil; nitrile group, and carboxylate, sulfonate, or ammonium group, which imparts solubility in water. X represents hydrogen; COOR5; or CONR6R7. R5, R6, and R7 are hydrogen; C1~C 20 -alkyl;C2~C 1O -Alkenil; C3~C 10 -Cycloalkyl; C3~C 10 -Cycloalkenyl; (YO) o -Z; or represents the aryl group. Z represents -CH2-CH3;-CH2-CH2-CH3;-CH2-CH2-CH2-CH3; or -CH(CH3)-CH3. m represents a value between 0 and 3. n represents a value from 0 to 4. [o represents numbers from 1 to 20].

[0062] In the most preferred embodiment, the UV absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

[0063] Formula (HBP-03) [ka] [In the formula, R1 and R2 are independent of each other, C1~C 20 -alkyl;C2~C 20 -Alkenil; C3~C 10 -Cycloalkyl; C3~C 10- Represents a cycloalkenyl, or R1 and R2, together with the nitrogen atom to which they are bonded, form a 5-membered or 6-membered heterocyclic ring. R3 represents an alkylene, cycloalkylene, alkenylene, or phenylene which may be substituted with a carbonyl or carboxyl group; formula (HBP-03a) *-CH2-C≡C-CH2-* represents a divalent free radical, or R3 together with A represents formula (HBP-03b) [ka] [In the formula, n2 represents a numerical value between 1 and 3. A represents -O-; or -N(R5)-, R5 represents a divalent group of hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl. [to form] Dimeric benzophenone derivatives corresponding to these can also be used in accordance with the present invention.

[0064] In particular, formula (HBP-04) is preferred. [ka] and formula (HBP-05) [ka] The dimeric benzophenone derivative can be used as a UV absorber (d3).

[0065] An example of a dibenzoylmethane derivative (d4) that can be used according to the present invention is butylmethoxydibenzoylmethane-[1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione].

[0066] Examples of diphenyl acrylate derivatives (d5) that can be used according to the present invention are octocrylene (2-ethylhexyl 2-cyano-3,3'-diphenylacrylate) or etocrylene (ethyl 2-cyano-3,3'-diphenylacrylate).

[0067] Examples of benzofuran derivatives (d7) that can be used in accordance with the present invention include 3-(benzofuranyl)2-cyanoacrylate, 2-(2-benzofuranyl)-5-tert-butylbenzoxazole, or 2-(p-aminophenyl)benzofuran, particularly formula (BF-01). [ka] Or formula (BF-02) [ka] It is a compound of [the compound].

[0068] Examples of polymeric UV absorbers (d8) used in accordance with the present invention and containing one or more organosilicon groups include benzylidene malonate derivatives, particularly formula (PUV-01). [ka] [In the formula, R 24 The compound, formula (PUV-02), where represents hydrogen or methoxy, and r represents approximately 7. [ka] Compound, formula (PUV-03) [ka] Compounds of the formula (PUV-04) [ka] This is polysilicone-15, which corresponds to this product.

[0069] Examples of cinnamic acid esters (d9) that can be used according to the present invention include octyl methoxycinnamate (2-ethylhexyl 4-methoxycinnamate), diethanolamine methoxycinnamate (diethanolamine salt of 4-methoxycinnamic acid), isoamyl p-methoxycinnamate (2-isoamyl 4-ethoxycinnamate), 2,5-diisopropyl methoxycinnamate, or cinnamic acid amide derivatives.

[0070] Camphor derivatives (d) that can be used according to the present invention 10 Examples of these include 4-methylbenzylidene camphor [3-(4'-methyl)benzylidenebornan-2-one], 3-benzylidene camphor (3-benzylidenebornan-2-one), polyacrylamide methylbenzylidene camphor {N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer}, trimonium benzylidene camphor sulfate [3-(4'-trimethylammonium)-benzylidenebornan-2-one methyl sulfate], terephthalylidene dicamhor sulfonic acid {3,3'-(1,4-phenylenedimethine)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]heptane-1-methanesulfonic acid} or its salts, or benzylidene camphor sulfonic acid [3-(4'-sulfo)benzylidenebornan-2-one] or its salts.

[0071] Hydroxyphenyltriazine derivatives (d) that can be used in accordance with the present invention 11 An example of this is equation (HPT-01) [ka] [In the formula, R1 and R2 are hydrogen atoms, independently of each other; C1~C 18 -alkyl;C2~C 18 -Alkenil; formula [ka] The basis; formula (HPT-01a) [ka] The basis of; or formula (HPT-01h) [ka] It represents the basis of, R3, R4, and R5 are independently hydroxyl; unsubstituted or substituted with one or more OH groups; C1-C5 alkoxy; amino; mono- or di-C1-C5 alkylamino; M; formula (HPT-01b) [ka] ;Formula (HPT-01c) [ka] Formula (HPT-01d) [ka] ;Formula (HPT-01e) [ka] ;Formula (HPT-01f) [ka] ; or formula (HPT-01g) [ka] It represents the basis of, R 10 , R 11 and R 12 These C1-C atoms are either unsubstituted or substituted by one or more OH groups, independently of each other. 14 - Represents alkyl, R 13 is hydrogen; M; C1~C5-alkyl; or formula-(CH2) m3 - Represents the base of O-T1, R6 is a direct bond; a linear or branched C1-C4 alkylene group; or a C1-C4 alkylene group. m4 H 2m4 Or -Cm4 H 2m4 It represents the -O- group, R7, R8, and R9 operate independently of each other, C1~C 18 -Alkyl;C1~C 18 -Alkoxy or formula (HPT-01m) [ka] It represents the basis of, R 14 represents C1-C5 alkyl, M represents a metal cation. T1 represents hydrogen; or (C1~C8)-alkyl, m1, m2, and m3 represent 1 to 3 independently of each other. m4 represents 2 to 14. p1 is a bis-resorcinyl triazine representing a number between 0 and 5.

[0072] The list of possible compound classes (d 11 A typical example of this is: - 2-(4'-methoxyphenyl)-4,6-bis(2'-hydroxy-4'-n-octyloxyphenyl)-1,3,5-triazine, - 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, - 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethylcarboxyl)phenylamino]-1,3,5-triazine, - 2,4-bis{[4-(tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, - 2,4-bis{[4-(2"methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, - 2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethyltrisilyl-2"-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, - 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-[4-ethylcarboxyl)phenylamino]-1,3,5-triazine, - 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrole-2-yl)-1,3,5-triazine, or - Formula (BRT-02) [ka] The corresponding compound is 2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-[(2-ethylhexyl)oxy]-(bis-ethylhexyloxyphenol methoxyphenyl triazine)].

[0073] Benzotriazole derivatives (d) that can be used in accordance with the present invention 12 An example of this is equation (BT-01) [ka] [In the formula, R1 is hydrogen; C1~C 12 -Alkyl;C1~C 12 -alkoxy;C1~C 12 -Alkoxycarbonyl;C5~C 10 - Represents cycloalkyl or -SO3M, R3 is hydrogen; C1~C 18 -Alkyl;C1~C 12 - Represents alkoxy; or halogen, n represents either 1 or 2. If n=1, R2 is C1~C 20 -alkyl;C5~C 10 -Cyclo-C1~C5-alkyl;C1~C 12-alkoxy-C1~C5-alkyl;C5~C 10 -Cycloalkoxy-C1~C5-alkyl;C6~C 10 -Aryl;C6~C 10 - Represents aryl-C1~C5-alkyl, If n=2, R2 is directly bonded; or -(CH2) p - represents, [where p is an integer between 1 and 3].

[0074] Preferably, a compound of formula (BT-01) [In the formula, R1 is C1~C 12 -Alkyl; or -SO3M represents, R3 represents hydrogen; halogen, preferably Cl. n represents 1, R2 is C1~C 12 - Represents alkyl, [p represents 1-3] It is available.

[0075] A particularly preferred compound is formula BT-02 [ka] It belongs to them.

[0076] Furthermore, the preferred UV filter of formula BT-01 is, in formula, R1 represents hydrogen, R3 is C1~C 18 - Represents alkyl, n=2, R2 represents -CH2-.

[0077] A particularly preferred compound is formula (BT-03) [ka] It belongs to them.

[0078] Trianilino-s-triazine derivatives (d) that can be used in accordance with the present invention 13 An example of this is equation (TAT-01) [ka] [In the formula, R1, R2, and R3 may be substituted independently of each other in C1-C 20 - Represents alkyl, aryl, or hetalil, X represents O; or NR4, R4 is hydrogen; or C1-C which may be substituted. 20 - Corresponds to [representing alkyl, aryl, or hetalil].

[0079] A particularly preferred representative of this class of compounds is formula (TAT-02) [ka] Ethylhexyl triazone, which corresponds to Or formula (TAT-03) [ka] Diethylhexylbutamide triazone, which corresponds to diethylhexylbutamide triazone Or formula (TAT-04) [ka] The corresponding ethylhexylbis-isopentylbenzoxazolylphenylmelamine is the one that corresponds to it.

[0080] Preferred tris-biphenyl-triazine derivatives that can be used in accordance with the present invention (d 17 ) is formula (TBT-01) [ka] [In the formula, A is given by equation (TBT-01a) [ka] ; or formula (TBT-01b) [ka] It represents the basis of, R1 and R5 are hydrogen, independently of each other; C1~C 18 -alkyl; or C6~C 12 - Represents aryl, R2, R3, and R4 are hydrogen, independently of each other; or formula (TBT-01c) [ka] In formula (TBT-01a), at least one of the R2, R3, and R4 groups represents the group of formula (TBT-01c), R6, R7, R8, R9 and R 10 These are independent of each other: hydrogen; hydroxyl; halogen; C1~C 18 -Alkyl;C1~C 18 -alkoxy;C6~C 12 -aryl; biphenylyl; C6~C 12 -Aryloxy;C1~C 18 -alkylthio;carboxyl;-COOM;C1~C 18 -alkylcarboxyl; aminocarbonyl; or mono- or di-C1~C 18 -Alkylamino;C1~C 10 -Acylamino; represents -COOH, M represents alkali metal ions, x represents either 1 or 2. [where y represents an integer between 2 and 10].

[0081] Preferably, a UV filter (d) that can be used in accordance with the present invention. 17 ) is formula (TBT-02) [ka] and formula (TBT-03) [ka] It corresponds to the compound.

[0082] A preferred benzylidene malonate (d) that can be used according to the present invention 19 is of formula (MBM-01) [Chemical formula] [wherein R1 represents methyl; ethyl; propyl; or n-butyl, when R1 represents methyl, R is tert-butyl, [Chemical formula] a group of formula (MBM-01a) [Chemical formula] or a group of formula (MBM-01b) [Chemical formula] represents, R2 and R3 each independently represent hydrogen; or methyl, R4 represents methyl; ethyl; or n-propyl, R5 and R6 each independently represent hydrogen; or C1-C3-alkyl, when R1 represents ethyl; propyl; or n-butyl, R represents isopropyl].

[0083] Particularly preferred benzylidene malonates (d) that can be used according to the present invention 19 are listed in the following table.

[0084] [Table 1]

[0085] Phenylene-bis-diphenyltriazine (d 21A typical example of this is 5,6,5,6-tetraphenyl-3,3'-(1,4-phenylene)-bis[1,2,4]triazine, which corresponds to the following formula.

[0086] [Table 2]

[0087] A typical example of an imidazoline derivative is ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

[0088] Diarylbutadiene derivatives (d 23 A typical example of this is 1,1-dicarboxy-(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

[0089] The above UV filters (d1)~(d 23 Each of the above can be used as a mixture according to the present invention. For example, filter group (d1) to (d 23 A mixture of 2, 3, 4, 5, or 6 of the following substances can be used in accordance with the present invention. Substance class (d1) to (d 23 A mixture of two, three, four, five, or six UV filters from one or more representatives of the ) can also be used in accordance with the present invention.

[0090] In a preferred embodiment, UV filter (d) is representative of the following compound class. (d1) p-aminobenzoic acid derivative, (d2) Salicylic acid derivatives, (d3) Benzophenone derivatives, (d4) Dibenzoylmethane derivatives, (d5) Diphenyl acrylate, (d6) 3-Imidazole-4-yl acrylic acid and its esters, (d7) Benzofuran derivatives, (d9) Cinnamic acid derivatives, (d 10 ) Camphor derivatives, (d 11 ) Hydroxyphenyltriazine derivatives, (d 12 ) Benzotriazole derivatives, (d 13 ) Trianilinino-s-triazine derivatives, (d 15 ) Menthylo-aminobenzoate, (d 16 ) Homosalate, (d 19 ) Benzylidenemalonate, and (d 20 ) Merocyanine derivatives.

[0091] In a more preferred embodiment, the following oil-soluble UV filters are used according to the present invention. (d SOL-1 ) Benzophenone-3 (BP3), (d SOL-2 ) Benzophenone-4 (BP4), (d SOL-3 ) 3-Benzylidenecamphor (3BC), (d SOL-4 ) Bis-ethylhexyl oxy-phenol methoxyphenyltriazine (BEMT), (d<7-digit tag preserved as is>) Butyl methoxydibenzoylmethane (BMBM), (d SOL-6 ) Diethylhexyl butamidotriazone (DBT), (d SOL-7 ) Drometrizole trisiloxane (DTS), (d SOL-8 ) Ethylhexyl triazone (EHT), (d SOL-9 ) Ethylhexyl methoxycinnamate, (d SOL-10 ) Benzylidenemalonate (BM), (d SOL-11 ) Diethylamino hydroxybenzoyl hexyl benzoate (DHHB), (d SOL-12 ) Octocrylene, (dSOL-13 ) Polysilicone-15, (d SOL-14 ) Homosalate, and (d SOL-15 Ethylhexyl salicylate.

[0092] In the most preferred embodiment, the UV filter is (d 9a ) Ethylhexyl methoxycinnamate, (d 11a ) Bis-ethylhexyloxyphenol methoxyphenyl triazine, (d 13a ) Ethylhexyltriazone, and (d 3a ) Diethylaminohydroxybenzoyl hexyl benzoate It is at least one selected from the group consisting of the following:

[0093] In a particularly preferred embodiment, the UV filter is (d 9a ), (d 11a ), (d 13a ) and (d 3a A mixture of UV filters selected from the group consisting of ).

[0094] The increase in absorbance due to the presence of porous metal oxide spheres (e.g., microspheres) was observed to be stronger in the UV spectral region compared to the visible region.

[0095] In a preferred embodiment, the method further minimizes or masks the whitening effect of the sunscreen composition and maintains its transparency.

[0096] In a preferred embodiment, the use further minimizes or masks the whitening effect of the sunscreen composition and maintains its transparency.

[0097] The whitening effect of the sunscreen composition is determined by testing based on the evaluation of the light transmittance through a thin film of the sunscreen sample spread on a roughened substrate.

[0098] Sunscreen composition In yet another embodiment, the present invention provides a sunscreen composition comprising water and porous spheres (e.g., microspheres), wherein the porous spheres contain a metal oxide in an amount ranging from 1.0 to 10.0% by weight relative to the total weight of the sunscreen composition, and the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

[0099] In some embodiments, the metal oxide is at least one selected from the group consisting of silica, zinc oxide, and titania. In another embodiment, the metal oxide is silica. In yet another embodiment, the metal oxide is titania.

[0100] In some embodiments, the porous silica spheres have a refractive index in the range of 1.4 to 1.5. When porous silica spheres having a refractive index in the same range, for example, 1.3 to 1.6, are incorporated into a sunscreen composition, the porous silica spheres do not affect the appearance of the sunscreen composition.

[0101] In some embodiments, the amount of metal oxide in the porous sphere is in the range of 60.0 to 99.9% by weight, or 75.0 to 98.0% by weight, or 80.0 to 95.0% by weight, relative to the total weight of the porous sphere.

[0102] In some embodiments, the sunscreen composition includes porous spheres having an average diameter in the range of 0.5 μm to 100.0 μm, or 1.0 μm to 90.0 μm, or 5.0 μm to 80.0 μm, or 10.0 μm to 70.0 μm, or 20.0 μm to 50.0 μm.

[0103] In some embodiments, the porous sphere has an average porosity in the range of 0.10 to 0.90.

[0104] In some embodiments, the sunscreen composition comprises porous spheres having an average porosity in the range of 0.10 to 0.80, or in the range of 0.30 to 0.80, or in the range of 0.15 to 0.75, or in the range of 0.25 to 0.60, or in the range of 0.30 to 0.50.

[0105] In some embodiments, the sunscreen composition comprises porous spheres having an average pore diameter in the range of 50 nm to 999 nm, or in the range of 100 nm to 900 nm, or in the range of 200 nm to 800 nm, or in the range of 300 nm to 700 nm, or in the range of 400 nm to 600 nm.

[0106] In some embodiments, the porous spheres are monodisperse.

[0107] In some embodiments, the porous spheres a. have an average diameter in the range of 0.5 μm to 100.0 μm, b. have an average porosity in the range of 0.10 to 0.90, c. have an average pore diameter in the range of 50 nm to 999 nm, d. are monodisperse.

[0108] In some embodiments, the sunscreen composition a. has an average diameter in the range of 0.5 μm to 100.0 μm, b. has an average porosity in the range of 0.10 to 0.80, c. has an average pore diameter in the range of 50 nm to 999 nm, d. is monodisperse and comprises porous spheres.

[0109] In some embodiments, the sunscreen composition (d1) a p-aminobenzoic acid derivative, (d2) a salicylic acid derivative, (d3) a benzophenone derivative, (d4) a dibenzoylmethane derivative, (d5) a diphenyl acrylate, (d6) 3-Imidazole-4-yl acrylic acid and its esters, (d7) Benzofuran derivatives, (d8) High molecular weight UV absorber, (d9) Cinnamic acid derivatives, (d 10 ) Camphor derivatives, (d 11 ) Hydroxyphenyltriazine derivatives, (d 12 ) Benzotriazole derivatives, (d 13 ) Trianilino-s-triazine derivatives, (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts, (d 15 ) o-Menthyl aminobenzoate, (d 16 ) Homosalate, (d 17 ) Tris-biphenyltriazine derivatives, (d 18 ) TiO2 (partially encapsulated), ZnO and mica, (d 19 ) Benzylidene malonate, (d 20 ) Merocyanine derivatives, (d 21 ) Phenylenebis-diphenyltriazine, (d 22 ) Imidazolin derivatives, and (d 23 ) Diarylbutadiene derivatives The further comprises a UV absorber selected from the group consisting of the following.

[0110] Representative examples of UV absorbers are listed above.

[0111] In some embodiments, the sunscreen composition further comprises a dye selected from the group consisting of acid violet 43 and acid red 33.

[0112] 1) Oil phase In some embodiments, the sunscreen composition further comprises a discontinuous oil phase in the range of 5.0 to 50.0% by weight relative to the total weight of the sunscreen composition.

[0113] In the context of the present invention, usable oily substances include, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms (e.g., Eutanol® G), linear C6-C6 22 - Fatty acids and linear or branched C6-C 22 - Fatty alcohol esters and branched C6-C 13 -Carboxylic acid and linear or branched C6-C 22 - Esters 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, isostearyl palmitate, stearyl These include isostearyl phosphate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate, and erucate. Furthermore, linear C6~C 22 - Fatty acids and branched alcohols, especially esters of 2-ethylhexanol, C3~C 38-alkylhydroxycarboxylic acid and linear or branched C6-C6 22 - Esters of fatty alcohols, especially diethylhexyl malate, linear and / or branched fatty acids and polyhydric alcohols (e.g., propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, C6-C 10 - Fatty acid-based triglycerides, C6~C 18 - Fatty acid-based liquid mono / di / triglyceride mixture, C6~C 22 - Fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially esters of benzoic acid, C2-C 12 - Esters of dicarboxylic acids and linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C 22 - Fatty alcohol carbonates, such as dicaprylyl carbonate (Cetiol® OE), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10 C atoms, benzoic acid and linear and / or branched C6-C 22 - Suitable candidates for consideration include alcohol esters (e.g., Finsolv® TN), linear or branched symmetric or asymmetric dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters and polyols (Hydagen® HSP, Sovermol® 750, Sovermol® 1102), silicone oils (cyclomethicone, silicone methicone type, etc.), and / or aliphatic or naphthenic hydrocarbons, such as mineral oil, petrolatum, petrolatum, squalane, squalene, isohexadecane, or dialkylcyclohexane.

[0114] In some embodiments, the oily substance is a moderately polar oil, particularly C2-C 12-Esters of dicarboxylic acids and linear or branched alcohols having 1 to 22 carbon atoms, and / or linear and branched C6-C6 alcohols. 22 - These are fatty alcohol carbonates. Linear or branched alcohols having 1 to 22 carbon atoms, and especially linear alcohols having 1 to 6 carbon atoms, are particularly suitable in this case as adipic acid esters.

[0115] Linear and branched fatty alcohol carbonates, particularly dicaprylyl carbonate, are especially preferred as oily substances.

[0116] In a more preferred embodiment, dibutyl adipate is used as the oily substance.

[0117] In another embodiment, the amount of the oil phase is in the range of 20 to 35% by weight relative to the total weight of the sunscreen composition.

[0118] 2) Emulsifier In some embodiments, the sunscreen composition further comprises at least one emulsifier in an amount ranging from 1.0 to 20.0% by weight relative to the total weight of the sunscreen composition.

[0119] In some embodiments, the emulsifier is selected from the group consisting of anionic emulsifiers, nonionic emulsifiers, and polymer emulsifiers.

[0120] Anionic surfactants are characterized by one or more anionic groups that impart solubility in water, such as carboxylate, sulfate, sulfonate, or phosphate groups, and lipophilic groups. Furthermore, molecules may contain polyglycol ethers, esters, ethers, and hydroxyl groups. Many anionic surfactants that are well-tolerated by the skin are known to those skilled in the art from relevant handbooks and are commercially available.

[0121] Typical examples of preferred anionic surfactants are, in all cases, in the form of their salts, ether-carboxylic acids, acyl sarcosides having 8 to 24 carbon atoms in the acyl group, acyl taurides 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, and monoalkyl polysulfosuccinates having 8 to 24 carbon atoms and 1 to 6 oxyethyl groups in the alkyl group. Oxyethyl esters, linear alkanesulfonates having 8 to 24 carbon atoms, linear α-olefin sulfonates having 8 to 24 carbon atoms, α-sulfo-fatty 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 and protein hydrolysates and / or amino acids and their derivatives, so-called protein fatty acid condensates, such as Lamepon®, Gluadin®, Hostapon®, KCG or Amisoft®.

[0122] The salts of these surfactants are preferably selected from sodium, potassium, and ammonium, as well as mono, di, and trial canal ammonium salts having 2 to 4 carbon atoms in the alkanol group.

[0123] Particularly suitable anionic surfactants are liquid at room temperature, preferably 18-25°C. A particularly desirable characteristic of these anionic surfactants is that they have a low water content of at most 10% by weight, preferably 0.1-5% by weight, relative to the total weight of the anionic surfactant.

[0124] In the most preferred embodiment, the anionic surfactant is an alkyl or alkenyl polyglycol ether citrate, and in particular formula (I) [ka] [In the formula, R1, R2, and R3 are independent of each other and are hydrogen or formula (II) R4(OCH2CHR5) n It represents the basis of, R4 represents a linear or branched alkyl and / or alkenyl group having 6 to 22 carbon atoms. R5 represents a hydrogen or methyl group. n represents a number from 1 to 20, provided that at least one of the R1, R2, or R3 groups is not hydrogen, and the mixture is a mixture of citric acid and mono, di, and triesters of alkoxylated alcohols.

[0125] Typical examples of the alcohol portion of the esters are the addition products of ethylene oxide and / or propylene oxide in an average of 1 to 20 mol, preferably 5 to 10 mol, to caproyl alcohol, caprylic alcohol, 2-ethylhexyl alcohol, caprin alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitrail alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadleyl alcohol, behenyl alcohol, erucyl alcohol, and brassidyl alcohol, as well as mixtures thereof in their technical grades.

[0126] Such alkyl or alkenyl polyglycol ether citrates are advantageous for the agents according to the present invention because they are liquid anionic surfactants having a low water content of up to 5% by weight relative to the anionic surfactant.

[0127] Preferably, the anionic surfactant is present in an amount ranging from 7% to 17% by weight of the total weight of the sunscreen composition.

[0128] The agent according to the present invention further comprises at least (c) 0.5 to 25% by weight of another co-surfactant different from the anionic surfactant.

[0129] Suitable co-surfactants are, in principle, zwitterionic, amphoteric, cationic, and / or nonionic surfactants.

[0130] Surface-active compounds having at least one quaternary ammonium group and at least one -COO(-) or -SO3(-) group in the molecule are called zwitterionic surfactants. Particularly preferred zwitterionic surfactants are so-called betaines, for example, N-alkyl-N,N-dimethylammonium glycinates, e.g., coco-alkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinate, e.g., coco-acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline, as well as coco-acylaminoethylhydroxyethylcarboxymethyl glycinate, all of which have 8 to 18 carbon atoms in the alkyl or acyl group in each case. Fatty acid amide derivatives known by the INCI name cocamidopropyl betaine are preferred zwitterionic surfactants. According to the present invention, surfactant mixtures of Tego® Betain 810 (INCI: capryl / capramidopropyl betaine), and Rewopol® SBCS 50K (INCI: PEG-5 lauryl citrate sulfosuccinate disodium, sodium laureth sulfate) and Tego® Betain 810 (capryl / capramidopropyl betaine) in a weight ratio of particularly 1:4 to 4:1, and most preferably 1:4 to 1:1, are particularly preferred.

[0131] Amphoteric surfactants have C8-C in their molecule. 18-It is understood to mean a surface-active compound that contains at least one free amino group and at least one -COOH or -SO3H group in addition to an alkyl or acyl group, and that can form an intramolecular salt. Examples of preferred amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid, and alkylaminoacetic acid, all of which have about 8 to 18 carbon atoms in the alkyl group. Preferred amphoteric surfactants are N-coco-alkylaminopropionate, coco-acylaminoethylaminopropionate, and C 12~18 - It is acylsarcosine.

[0132] Quaternary ammonium compounds can be used particularly as cationic surfactants. Surfactants from this class of substances have particularly high affinity for the skin and can improve the degree of smoothness. These include, in particular, ammonium chlorides and bromides, such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and trialkylmethylammonium chloride, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Furthermore, highly biodegradable quaternary ester compounds, such as dialkylammonium methosulfate and methylhydroxyalkyldialcoyloxyalkylammonium methosulfate sold under the trade name Stepantex® and corresponding products in the Dehyquart® series, can be used as cationic surfactants. The term "esterquart" is generally understood to mean quaternized fatty acid triethanolamine ester salts. These impart a particularly soft feel to compositions. These are known substances that can be prepared by appropriate organic chemistry methods. Another cationic surfactant that can be used according to the present invention is a quaternized protein hydrolysate.

[0133] Nonionic surfactants, for example - Addition products of 2 to 50 mol of ethylene oxide and / or 0 to 20 mol of propylene oxide to 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 an alkyl group. - Addition product of 1-50 mol of ethylene oxide to glycerol 12 / 18 - Fatty acid mono and diesters; glycerol mono and diesters and sorbitan mono and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms, and their ethylene oxide addition products. - Alkyl mono and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs; addition products of 7 to 60 mol of ethylene oxide to castor oil and / or hydrogenated castor oil. - Polyols and / or polyglycerol esters, for example, polyglycerol diisostearate or polyglycerol dimarate or polyglycerol 12-hydroxystearate, - Addition product of 2 to 15 mol of ethylene oxide to castor oil and / or hydrogenated castor oil, - Linear, branched, unsaturated, or saturated C6-C 22 - Partial esters or mixed esters based on fatty acids, ricinoleic acid and 12-hydroxystearic acid, and pentaerythritol, dipentaerythritol, sugar alcohols (e.g., sorbitol), alkyl glucosides (e.g., methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g., cellulose), such as glyceryl stearate citrate and glyceryl stearate lactate. - Wool wax alcohol, - Polysiloxane / polyalkyl polyether copolymers and corresponding derivatives, - Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol, and - Polyalkylene glycol It is particularly preferable that it exists as a co-surfactant.

[0134] Addition products of ethylene oxide and / or propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono and diesters of fatty acids, and sorbitan mono and diesters, or castor oil are known and commercially available products. These are mixtures of homologs whose average degree of alkoxylation corresponds to the molar ratio of ethylene oxide and / or propylene oxide to the substrate on which the addition reaction is carried out. These are W / O or O / W type emulsifiers depending on the degree of ethoxylation. Reaction products with 1 to 100 mol of ethylene oxide are particularly suitable for the preparations according to the present invention.

[0135] Favorable compounds from the nonionic surfactant group include polyols, particularly partial esters of C3-C6 polyols, such as glyceryl monoesters, pentaerythritol, or partial esters of sugar esters, such as sucrose distearate, sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, These include 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 mixtures thereof in their technical grades. Addition products of 1 to 30 mol, preferably 5 to 10 mol, of ethylene oxide relative to the sorbitan esters described are also suitable nonionic surfactants.

[0136] Nonionic surfactants from the alkyl oligoglycoside group are particularly gentle on the skin and therefore may be preferred in the context of the present invention. C8~C 22 - Alkyl mono and oligoglycosides, their preparation and use are known from the prior art. Their preparation is carried out by the reaction of glucose or oligosaccharide with a primary alcohol having 8 to 22 carbon atoms, preferably 12 to 22, and especially preferably 12 to 18 carbon atoms. With respect to the glycosidic group, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to a fatty alcohol and oligomeric glycosides having a maximum of preferably about 8 degrees of oligomerization are preferred. Here, the degree of oligomerization is a statistical mean based on the usual distribution of homologs of such technical grade products. Products available under the name Plantacare® have C8-C glycosidic groups with an average degree of oligomerization of 1-2. 16 -Contains alkyl groups. Acylglucamide derived from glucamine is also suitable as a nonionic surfactant.

[0137] A nonionic surfactant, preferably a polyol and / or polyglycerol ester, is most preferably present as a co-surfactant and / or alkyl oligoglycoside in the agent according to the present invention as component (c).

[0138] The polyol components of these surfactants can be derived from substances having at least two, preferably three to twelve, and especially three to eight hydroxyl groups and two to twelve carbon atoms. Typical examples are: - Glycerol and polyglycerol, - Alkylene glycols, e.g., ethylene glycol, diethylene glycol, propylene glycol, - Methylol compounds, for example, particularly trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol, - Alkyl oligoglucosides having 1 to 22, preferably 1 to 8, and particularly 1 to 4 carbon atoms in the alkyl group, such as methyl and butyl glucosides. - Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol. - Sugars having 5 to 12 carbon atoms, such as glucose or sucrose. - Amino sugars, such as glucamine That is the case.

[0139] Reaction products based on polyglycerols are particularly important due to their excellent usability.

[0140] The acidic component of these surfactants can be derived from linear, branched, saturated, and / or unsaturated carboxylic acids optionally having a functional group, such as a hydroxyl group. Particularly preferred are fatty acids having 12 to 22 carbon atoms optionally having a hydroxyl group, especially hydroxystearic acid.

[0141] In a preferred embodiment of the present invention, polyglyceryl 2-dipolyhydroxystearate, a diester of polyhydroxystearate, is used as a glyceryl ester, for example, sold by BASF Personal Care and Nutrition GmbH under the name Dehymuls® PGPH.

[0142] In the agent according to the present invention, another co-surfactant is usually present in an amount in the range of 0.5 to 25% by weight, more preferably in the range of 3.0 to 18% by weight, and particularly preferably in the range of 7 to 18% by weight.

[0143] 3) Additives In some embodiments, the sunscreen composition further comprises additives selected from the group consisting of thickeners, active ingredients, preservatives, and fragrances.

[0144] Thickening agent Suitable thickeners include anionic, zwitterionic, amphoteric, and nonionic copolymers, such as vinyl acetate / crotonic acid copolymer, vinylpyrrolidone / vinyl acrylate copolymer, vinyl acetate / butyl maleate / isobornyl acrylate copolymer, methyl vinyl ether / maleic anhydride copolymer and its esters, acrylamidopropyltrimethylammonium chloride / acrylate copolymer, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate polymer, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymer, and optionally polysaccharides, particularly xanthan gum, guar and guar derivatives, agar, alginate and tyrose, cellulose and cellulose derivatives, such as carboxymethylcellulose, carboxymethylcellulose and hydroxycellulose, and also silicones.

[0145] Preferably, a thickener selected from the group consisting of polyacrylates and crosslinked polyacrylates, such as Rheocare TTA®, Cosmedia® SP, Rheocare® C Plus, Tinovis® ADE, and Tinovis® GTC, is added.

[0146] A thickener derived from polysaccharides, such as Keltrol® T or Rheocare® XG, is even more preferred.

[0147] Preferably, the amount of the thickener, calculated as an active substance, is in the range of 0.5 to 5% by weight, particularly 1 to 4% by weight, relative to the total weight of the sunscreen composition.

[0148] A thickening agent can be added to the concentrated agent before diluting it with water, or it can be included in the water used to dilute the concentrated agent.

[0149] According to a variation of the preferred method, a concentrated agent is mixed with a thickener, water for dilution is added to this mixture, and other formulation components are optionally stirred.

[0150] According to a variation of another preferred method, water, a thickener, and optionally other auxiliary substances are stirred together, and a concentrated agent is added to this mixture.

[0151] The final sunscreen formulation prepared by the method according to the present invention is often a particularly finely milled O / W type emulsion having an average particle size of <10 μm, preferably <5 μm.

[0152] active compound Suitable bioactive compounds according to the present invention should be understood to mean, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and its fragmentation products, β-glucan, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as Prunus extract, Bambara nut extract, and vitamin complexes. Such active compounds are used as agents in the final sunscreen formulation to scavenge free radicals and regenerate the skin.

[0153] Preservatives Suitable preservatives include, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol, or sorbic acid, and a silver complex known by the name Surfacine®.

[0154] perfume oil The aromatic oils that can be enumerated are natural, plant, animal, and synthetic aromatic substances or mixtures thereof. Natural aromatic substances are obtained, in particular, by extraction of the flowers, stems, leaves, fruits, fruit peels, roots, and resins of plants. Animal raw materials, such as civet and castoreum, are also available. Typical synthetic aromatic compounds are ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type products. Preferably, mixtures of various aromatic substances that together produce a pleasant aromatic note are used.

[0155] Auxiliary substances In some embodiments, the final sunscreen formulation further includes, for example, auxiliary substances listed below, such as water-retaining agents / skin moisturizers, viscosity modifiers, oils, fats and waxes, surfactants, pearlescent waxes, super-oiling agents, stabilizers, cationic, zwitterionic or amphoteric polymers, other UV filters, bioactive compounds, coating agents, swelling agents, hydrotropic substances, preservatives, solubilizers, fragrance oils, dyes, insect repellent compounds, and the like.

[0156] Moisture-retaining agents further contribute to optimizing the sensory properties of the composition and regulating skin moisture. Moisture-retaining agents can be present in an amount ranging from 0 to 5.0% by weight relative to the total weight of the sunscreen composition.

[0157] Suitable substances include, in particular, amino acids, pyrrolidone carboxylic acid, lactic acid and its salts, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, collagen cleavage products, chitosan or chitosan salts / derivatives, especially polyols and polyol derivatives (e.g., glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycol, e.g., PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10 These include PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), sugars and sugar derivatives (particularly fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sucrose, sorbitylsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and its salts), ethoxylated sorbitol (Sorbeth-6, Sorbeth-20, Sorbeth-30, Sorbeth-40), honey and hydrogenated honey, hydrogenated starch hydrolysates, and mixtures of hydrogenated wheat protein and PEG-20 / acetate copolymer. Preferably, substances suitable as moisture-retaining agents according to the present invention are glycerol, diglycerol, triglycerol, and butylene glycol.

[0158] Available insect repellents include, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol, or ethyl 3-(Nn-butyl-N-acetylamino)propionate, sold by Merck KGaA under the name Insect Repellent 3535, and butylacetylaminopropionate. These are typically used in the compositions according to the present invention in amounts ranging from 0 to 6% by weight relative to the total weight of the sunscreen composition.

[0159] The viscosity of the active agent according to the present invention can be achieved by adding a viscosity modifier. Available viscosity modifiers include, in particular, viscosity-imparting agents such as fatty alcohols or hydroxy fatty alcohols and partial glycerides having 12 to 22 carbon atoms, preferably 16 to 18 carbon atoms, fatty acids having 12 to 22 carbon atoms, or 12-hydroxy fatty acids. Combinations of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length are also suitable, because such combinations yield particularly stable and homogeneous emulsions. Viscosity modifiers also include thickeners such as Aerosil-type (hydrophilic silicic acid), polysaccharides, especially xanthan gum, guar-guar, agar, alginates and tyrose, carboxymethylcellulose and hydroxyethyl and hydroxypropylcellulose, as well as high molecular weight polyethylene glycol mono and diesters of fatty acids, polyacrylates (e.g., Pemulen type from Carbopols® and Goodrich; Synthalens® from Sigma; Keltrol type from Kelco; Sepigel type from Seppic; Salcare type from Allied Colloids), non-crosslinked and polyol-crosslinked polyacrylic acids, polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone. Bentonite, such as Bentone® Gel VS-5PC (Rheox), a mixture of cyclopentasiloxane, disteardimonium hectorite, and propylene carbonate, has also been found 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 narrowed homologous distribution, alkyl oligoglucosides, and electrolytes, such as sodium chloride or ammonium chloride, can also be used to adjust viscosity.

[0160] In the context of the present invention, fats and waxes are understood to mean all lipids having a fat- or wax-like consistency and a melting point above 20°C. These include, for example, classic triacylglycerols, i.e., triesters of fatty acids and glycerol, which may be of plant or animal origin. These may also be mixed esters, i.e., triesters of glycerol and various fatty acids, or mixtures of various glycerides. These also include mixtures of mono, di, and triglycerides. So-called hydrogenated fats and oils obtained by partial hydrogenation are particularly preferred according to the present invention. Hydrogenated fats and oils of plants, such as hydrogenated castor oil, peanut oil, soybean oil, rapeseed oil, beet seed oil, cottonseed oil, soybean oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, corn oil, olive oil, sesame oil, cocoa butter, and coconut fat are preferred. Oxidation-stable plant glycerides, available under the names Cegesoft® or Novata®, are particularly preferred.

[0161] Available waxes include, in particular, natural waxes such as candelilla wax, carnauba wax, wood wax, esparto grass wax, cork crow, guarma wax, rice germ oil wax, sugarcane wax, aurichale wax, montan wax, beeswax, shellac wax, whale wax, lanolin (wool wax), tail ridge fat, ceresin, ozocerite (ground wax), petrolatum, paraffin wax, and microwax; chemically modified waxes (hard waxes) such as montan ester wax, Sasol wax, hydrogenated jojoba wax, and synthetic waxes such as polyalkylene wax and polyethylene glycol wax.

[0162] 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 often called phosphatidylcholine (PC). Cephalin, also known as phosphatidic acid, is a derivative of 1,2-diacyl-sn-glycerol-3-phosphate and can be cited as an example of natural lecithin. In contrast, phospholipids are generally understood to mean monoesters, preferably diesters (glycerol phosphate), of phosphate and glycerol. Sphingosine and sphingolipids can also be used as fatty substances.

[0163] Suitable pearlescent waxes include, for example, alkylene glycol esters, specifically ethylene glycol distearate; fatty acid alkanolamides, specifically coconut fatty acid diethanolamide; partial glycerides, specifically stearic acid monoglyceride; and polybasic, optionally with hydroxysubstituted carboxylic acids and C6-C6. 22 - Esters of fatty alcohols, specifically long-chain esters of tartaric acid; fatty substances having a total of at least 24 carbon atoms, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, specifically Lauron®; distearyl ethers; fatty acids, such as stearic acid, C 12 ~C 22 -Hydroxy fatty acids, behenic acid, C 12 ~C 22 -Olefin epoxide 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.

[0164] The super-oiling agents that can be used are substances such as lanolin and lecithin, as well as polyethoxylated or acylated derivatives of lanolin and lecithin, polyol fatty acid esters, monoglycerides, and fatty acid alkanolamides, the latter of which also function as foam stabilizers.

[0165] The so-called stabilizers that can be used are metal salts of fatty acids, such as magnesium stearate, aluminum and / or zinc, or magnesium ricinoleate, aluminum and / or zinc.

[0166] Furthermore, suitable cationic polymers for optimizing the sensory properties of the composition according to the present invention and imparting a soft feeling to the skin include, for example, cationic cellulose derivatives, such as quaternized hydroxyethylcellulose available from Amerchol under the name Polymer JR 400 (registered trademark), a copolymer of cationic starch, diallylammonium salt and acrylamide, quaternized vinylpyrrolidone / vinylimidazole polymers, such as Luviquat (registered trademark) (BASF), condensation products of polyglycol and amine, quaternized collagen polypeptides, such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat (registered trademark) L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as amodimethicone, a copolymer of adipic acid and dimethylaminohydroxypropyl diethylenetriamine (Cartaretine (registered trademark) / Sandoz), and a copolymer of acrylic acid and dimethyldiallylammonium chloride (Merquat (registered trademark)). 550 / Chemviron), polyaminopolyamides and their crosslinked water-soluble polymers, cationic chitin derivatives, e.g., quaternary chitosan, condensation products distributed in the form of microcrystalline dihaloalkyls at any option, e.g., dibromobutan and bis-dialkylamines, e.g., condensation products of bis-dimethylamino-1,3-propane, cationic guar gum, e.g., Jaguar® CBS from Celanese, Jaguar® C-17, Jaguar (registered trademark) C-16, Quaternary ammonium salt polymer, e.g., Mirapol (registered trademark) from Miranol A-15, Mirapol (registered trademark) AD-1, Mirapol (registered trademark) AZ-1.

[0167] Furthermore, starch derivatives, such as Dry Flo® PC (INCI: aluminum starch octenylsuccinate), can be used to improve skin sensation.

[0168] Suitable silicone compounds have already been listed along with oily substances. In addition to dimethylpolysiloxane, methylphenylpolysiloxane and cyclic silicones, amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside-, and / or alkyl-modified silicone compounds are also suitable, which may be liquid or resinous at room temperature. Simethicone, which is a mixture of dimethicone having dimethylsiloxane units with an average chain length of 200-300 and silicon dioxide or hydrogenated silicate, is even more suitable.

[0169] The so-called coating agents that lead to further improvements in the sensory properties of the preparations according to the present invention are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, collagen, hyaluronic acid and its salts and similar compounds, as well as polymers of polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, acrylic acid series and quaternized cellulose derivatives already listed as viscosity modifiers.

[0170] To improve the flow properties of the composition according to the present invention, hydrotropic substances, such as ethanol, isopropyl alcohol, or polyols, can be further utilized. The polyols available here preferably have 2 to 15 carbon atoms and at least 2 hydroxyl groups. The polyol may also contain other functional groups, particularly amino groups, or the polyol may be modified with nitrogen.

[0171] The dyes that can be used are substances that are suitable for cosmetic purposes and are approved.

[0172] The present invention offers one or more of the following advantages: 1. The present invention provides a method for increasing the ultraviolet protection index of a sunscreen composition using porous spheres containing a metal oxide. 2. The method involves minimizing or masking the whitening effect of the sunscreen formulation, while maintaining its transparency and increasing its SPF. 3. The porous metal oxide spheres of the present invention can be used to increase the SPF of a sunscreen composition. 4. The porous metal oxide spheres of the present invention are useful for minimizing or masking the whitening effect of a sunscreen composition, thereby increasing its SPF while maintaining its transparency.

[0173] The following is a list of embodiments that further illustrate this disclosure, without the intention of limiting this disclosure to the specific embodiments listed below. 1. A method for increasing the ultraviolet protection index of a sunscreen composition, comprising the step of adding porous spheres containing a metal oxide to the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide. 2. Use of porous spheres containing a metal oxide to enhance the ultraviolet protection index of a sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide. 3. The method or use according to Embodiment 1 or 2, wherein the porous spheres are present in an amount ranging from 0.1 to 10.0% by weight relative to the total weight of the sunscreen composition. 4. The method or use according to any one embodiment of the prior embodiments, wherein the amount of metal oxide in the porous sphere is in the range of 60.0 to 99.9% by weight relative to the total weight of the porous sphere. 5. The method or use of any one embodiment of the preceding embodiments, wherein the porous sphere has an average diameter in the range of 0.5 μm to 100.0 μm. 6. The method or use of any one embodiment of the preceding embodiments, wherein the porous sphere has an average porosity in the range of 0.10 to 0.90. 7. The method or use of any one embodiment of the preceding embodiments, wherein the porous sphere has an average porosity in the range of 0.10 to 0.80. 8. A method or use of any one embodiment of the prior embodiments, wherein the porous spheres are monodisperse. 9. The method or use of any one embodiment of the preceding embodiments, wherein the porous sphere has an average pore diameter in the range of 50 nm to 999 nm. 10. The method or use of any one embodiment of the preceding embodiments, wherein the porous sphere has more than one pore group, each having an average pore diameter, and each group has a different average pore diameter. 11. A porous sphere, a. Having an average diameter in the range of 0.5 μm to 100.0 μm, b. Having an average porosity in the range of 0.10 to 0.90, c. Having an average pore diameter in the range of 50 nm to 999 nm, d. It is a simple variance. A method or use of any one embodiment of a prior embodiment. 12. A porous sphere, a. Having an average diameter in the range of 0.5 μm to 100.0 μm, b. Having an average porosity in the range of 0.10 to 0.80, c. Having an average pore diameter in the range of 50 nm to 999 nm, d. It is a simple variance. A method or use of any one embodiment of a prior embodiment. 13. Sunscreen composition, (d1) p-aminobenzoic acid derivative, (d2) Salicylic acid derivatives, (d3) Benzophenone derivatives, (d4) Dibenzoylmethane derivatives, (d5) Diphenyl acrylate, (d6) 3-Imidazole-4-yl acrylic acid and its esters, (d7) Benzofuran derivatives, (d8) High molecular weight UV absorber, (d9) Cinnamic acid derivatives, (d 10 ) Camphor derivatives, (d 11 ) Hydroxyphenyltriazine derivatives, (d 12 ) Benzotriazole derivatives, (d 13 ) Trianilino-s-triazine derivatives, (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts, (d 15 ) o-Menthyl aminobenzoate, (d 16 ) Homosalate, (d 17 ) Tris-biphenyltriazine derivatives, (d 18 ) TiO2 (partially encapsulated), ZnO and mica, (d 19 ) Benzylidene malonate, (d 20 ) Merocyanine derivatives, (d 21 ) Phenylenebis-diphenyltriazine, (d 22 ) Imidazolin derivatives, and (d 23 ) Diarylbutadiene derivatives A method or use according to any one embodiment of the prior embodiments, further comprising a UV absorber selected from the group consisting of the following. 14. A method according to any one embodiment of the prior embodiments, further comprising minimizing or masking the whitening effect of a sunscreen composition and maintaining its transparency. 15. Furthermore, use according to any one of the prior embodiments, which minimizes or masks the whitening effect of the sunscreen composition and maintains its transparency. 16. A sunscreen composition comprising water and porous spheres, wherein the porous spheres contain a metal oxide in an amount of 1.0 to 10.0% by weight relative to the total weight of the sunscreen composition, and the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide. 17. The sunscreen composition according to Embodiment 16, further comprising a discontinuous oil phase in the range of 5.0 to 50.0% by weight relative to the total weight of the sunscreen composition. 18. The sunscreen composition according to Embodiment 16 or 17, further comprising at least one emulsifier in an amount ranging from 1.0 to 20.0% by weight relative to the total weight of the sunscreen composition. 19. The sunscreen composition according to Embodiment 18, wherein the emulsifier is selected from the group consisting of anionic emulsifiers, nonionic emulsifiers, and polymer emulsifiers. 20. A sunscreen composition according to any one embodiment of Embodiments 16 to 19, further comprising an additive selected from the group consisting of thickeners, active ingredients, preservatives, and fragrances. 21. A sunscreen composition according to any one embodiment of Embodiments 16 to 20, wherein the amount of metal oxide in the porous spheres is in the range of 60.0 to 99.9% by weight relative to the total weight of the porous spheres. 22. A sunscreen composition according to any one embodiment of Embodiments 16 to 21, wherein the porous spheres have an average diameter in the range of 0.5 μm to 100.0 μm. 23. A sunscreen composition according to any one embodiment of Embodiments 16 to 22, wherein the porous spheres have an average porosity in the range of 0.10 to 0.90. 24. A sunscreen composition according to any one embodiment of Embodiments 16 to 23, wherein the porous spheres have an average porosity in the range of 0.10 to 0.80. 25. A sunscreen composition according to any one embodiment of Embodiments 16 to 24, wherein the porous spheres have an average pore diameter in the range of 50 nm to 999 nm. 26. A sunscreen composition according to any one embodiment of Embodiments 16 to 25, wherein the porous spheres are monodisperse. 27. A porous sphere, a. Having an average diameter in the range of 0.5 μm to 100.0 μm, b. Having an average porosity in the range of 0.10 to 0.90, c. Having an average pore diameter in the range of 50 nm to 999 nm, d. It is a simple variance. A sunscreen composition according to any one embodiment of Embodiments 16 to 26. 28. A porous sphere, a. Having an average diameter in the range of 0.5 μm to 100.0 μm, b. Having an average porosity in the range of 0.10 to 0.80, c. Having an average pore diameter in the range of 50 nm to 999 nm, d. It is a simple variance. A sunscreen composition according to any one embodiment of Embodiments 16 to 27. 29. (d1) p-aminobenzoic acid derivative, (d2) Salicylic acid derivatives, (d3) Benzophenone derivatives, (d4) Dibenzoylmethane derivatives, (d5) Diphenyl acrylate, (d6) 3-Imidazole-4-yl acrylic acid and its esters, (d7) Benzofuran derivatives, (d8) High molecular weight UV absorber, (d9) Cinnamic acid derivatives, (d 10 ) Camphor derivatives, (d 11 ) Hydroxyphenyltriazine derivatives, (d 12 ) Benzotriazole derivatives, (d 13 ) Trianilino-s-triazine derivatives, (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts, (d 15 ) o-Menthyl aminobenzoate, (d 16 ) Homosalate, (d 17 ) Tris-biphenyltriazine derivatives, (d 18 ) TiO2 (partially encapsulated), ZnO and mica, (d 19 ) Benzylidene malonate, (d 20 ) Merocyanine derivatives, (d 21 ) Phenylenebis-diphenyltriazine, (d 22 ) Imidazolin derivatives, and (d 23 ) Diarylbutadiene derivatives A sunscreen composition according to any one embodiment of Embodiments 16 to 28, further comprising a UV absorber selected from the group consisting of the following. 30. A sunscreen composition according to any one embodiment of Embodiments 16 to 29, further comprising a dye selected from the group consisting of acid violet 43 and acid red 33.

[0174] While the present invention has been described in general terms, further understanding can be gained by referring to several specific examples described herein, which are merely illustrative and not intended to limit the invention unless otherwise specified. [Examples]

[0175] The present invention will be further described in combination with the following examples. These examples are provided to illustrate the present invention and are not intended to limit the scope of the invention in any way.

[0176] material Acid Blue 3 (Patent Blue V) is 2-[(4-diethylaminophenyl)(4-diethylimino-2,5-cyclohexadiene-1-ylidene)methyl]-4-hydroxy-1,5-benzene-disulfonate and is available from Sigma Aldrich.

[0177] Benzophenone-4 is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, available from BASF.

[0178] Sunsil® 130 is available from Sunjin Beauty Science (formerly Sunjin Chemical).

[0179] Sunsphere® is available from Dow Chemicals.

[0180] method Average diameter or particle size: Particle size is synonymous with particle diameter and was determined by scanning electron microscopy (SEM) or transmission electron microscopy (TEM).

[0181] Average Porosity and Average Pore Diameter: The porosity of the spheres was characterized using mercury porosimetry analysis. In mercury porosimetry, a controlled pressure is applied to a sample immersed in mercury. The external pressure causes 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. A mercury porosimeter generates volume and pore diameter distributions from pressure-vs-penetration data generated by the instrument using the Washburn equation. For example, a porous silica sphere containing voids / pores with an average size of 165 nm has an average porosity of 0.8.

[0182] Determination of in vitro SPF for formulation examples In vitro SPF determination is performed by measuring diffuse transmission in the UV range using a Labsphere Ultraviolet Transmittance Analyzer 2000S. To simulate the heterogeneous surface structure of human skin, substrates with rough or porous surfaces are employed for such measurements. In this method, sandblasted 4-5 μm PMMA (polymethyl methacrylate) plates from Helioscience (France) are used as the substrate.

[0183] The sun protection factor (SPF) format was first introduced by Sayre[1] in 1979, and it calculates the average of the reciprocals (1 / T) of the transmission of each sunscreen in the spectral range of 290–400 nm, including weighting by the irradiance spectrum Ss(λ) and erythematizing spectrum Ser(λ) of the UV source.

[0184]

number

[0185] References [1] RM Sayre, PP Agin, GJ LeVee, E. Marlowe. A comparison of in vivo and in vitro testing of sunscreening formulas, Photochem. Photobiol. 29 (1979) 559 - 566

[0186] Transparency / Whitening Method: Color measurements were performed using a prepared composition coated on a PMMA plate, the same plate used for in vitro SPF measurements. From the obtained L*a*b* parameters, L* represents the lightness of the sample. The difference in L* compared to a blank sample is expressed as ΔL* and can be used to compare the transparency or whitening of the samples.

[0187] Preparation of porous metal oxide spheres [Example 1] Porous silica spheres Styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a three-neck reaction flask equipped with a thermometer and condenser under a nitrogen atmosphere while magnetically stirring. The water was heated to 80°C, and 10 g of styrene was added while stirring. Then, 100 mg of acrylic acid dissolved in 10 mL of DI water was added by syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture by syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was allowed to cool to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0188] An aqueous polystyrene colloidal dispersion was diluted to 1% by weight with deionized water, and 1% by weight silica nanoparticles were added. The mixture was then subjected to ultrasonic treatment to prevent particle aggregation. The continuous oil phase used was 0.1% by weight polyethylene glycol / perfluoropolyether surfactant in fluorinated oil. The aqueous colloidal dispersion and the oil were injected into a microfluidic device with a 50 μm droplet junction using syringes connected to a pump. The system was equilibrated until monodisperse droplets were formed. The monodisperse droplets were collected in a reservoir.

[0189] The collected droplets were dried in an oven at 45°C for 4 hours to obtain monodisperse polymer template spheres. The polymer template spheres were placed on a silicon wafer and sintered by heating from room temperature to 500°C for 3 hours, holding at 500°C for 2 hours, and then cooling back to room temperature for 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 were porous silica microspheres. The average pore (void) diameter of the silica spheres was 170 nm, and the average porosity was 0.8.

[0190] The drying step can be carried out by using microwave irradiation, drying under vacuum, and / or drying in the presence of a desiccant.

[0191] [Example 2] Porous silica spheres containing additional light absorbers The product of Example 1 was physically mixed with an aqueous dispersion of carbon black or carbon black powder at various weight levels. Monodisperse porous silica spheres were obtained containing carbon black at levels of 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, and 5% by weight relative to the total weight of the spheres.

[0192] [Example 3] Porous silica spheres dried by spray drying Styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a three-neck reaction flask equipped with a thermometer and condenser under a nitrogen atmosphere while magnetically stirring. The water was heated to 80°C, and 10 g of styrene was added while stirring. Then, 100 mg of acrylic acid dissolved in 10 mL of DI water was added by syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture by syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was allowed to cool to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0193] An aqueous polystyrene colloidal dispersion was diluted to 1% by weight with deionized water, and 1% by weight silica nanoparticles were added. The mixture was subjected to ultrasonic treatment to prevent particle aggregation. The aqueous dispersion was spray-dried to obtain polymer template spheres containing polymer nanospheres and silica. The spheres were calcined by heating them from room temperature to 500°C for 3 hours, holding them at 500°C for 2 hours, and then cooling them back to room temperature for 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.

[0194] [Example 4] Porous silica spheres Samples of porous silica spheres 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.

[0195] Silica spheres with an average diameter of 3.63 μm and an average pore (void) diameter of 368 nm were obtained. Figure 1 shows an SEM image of the porous silica spheres obtained according to Example 4. The average porosity of the silica spheres was 0.8.

[0196] [Example 5] Porous silica spheres Samples of porous silica spheres 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.

[0197] Silica spheres with an average diameter of 8.27 μm and an average pore (void) diameter of 365 nm were obtained. Figure 2 shows an SEM image of the porous silica spheres obtained according to Example 5. The average porosity of the silica spheres was 0.8.

[0198] [Example 6] Porous zinc oxide spheres Samples of porous zinc oxide spheres were prepared by replacing silica with zinc oxide and following the procedure of Example 3. Polystyrene nanospheres with an average diameter of 230 nm were used, and the weight ratio of polymer to zinc oxide was 1:2.

[0199] [Example 7] Porous titania sphere Silica was replaced with titania, and porous titania sphere samples were prepared according to the procedure of Example 3. Polymer nanospheres with an average particle size of 170 nm were used, and the weight ratio of polymer to titania was 3:1.

[0200] Titania spheres with an average diameter of 2.85 μm and an average pore (void) diameter of 142 nm were obtained. Figure 3 shows an SEM image of the porous titania spheres obtained according to Example 7. The average porosity of the titania spheres was 0.8.

[0201] [Example 8] Porous titania sphere Porous titania spheres were prepared using the same procedure as in 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.

[0202] Titania spheres with an average diameter of 2.95 μm and an average pore (void) diameter of 243 nm were obtained. Figure 4 shows an SEM image of the porous titania spheres obtained according to Example 8. The average porosity of the titania spheres was 0.8.

[0203] [Example 9] Porous spheres containing silica and titania Porous spheres containing silica and titania were prepared according to the method of Example 3, with a weight ratio of 3:1 between the polymer and the total metal oxide. The weight ratio of silica to titania was 9:1.

[0204] [Example 10] Porous sphere with two average particle sizes Step 1) Polymer spheres having at least two different average particle sizes Styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a three-neck reaction flask equipped with a thermometer and condenser under a nitrogen atmosphere while magnetically stirring. The water was heated to 80°C, and 10 g of styrene was added while stirring. Then, 100 mg of acrylic acid dissolved in 10 mL of DI water was added by syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture by syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was allowed to cool to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0205] Similarly, styrene / acrylic acid copolymers were prepared to produce polystyrene nanospheres with an average particle size of 350 nm.

[0206] A first aqueous polystyrene colloidal dispersion (250 nm) was mixed with a second aqueous polystyrene colloidal dispersion (350 nm) in a weight ratio of 7:3. The mixture was diluted to 1% by weight with deionized water and subjected to ultrasonic treatment to prevent particle aggregation. The continuous oil phase used was 0.1% by weight of polyethylene glycol / perfluoropolyether surfactant in fluorinated oil. The aqueous colloidal dispersion mixture and the oil were injected into a microfluidic device having a 50 μm droplet junction, respectively, using syringes connected to a pump. The system was equilibrated until monodisperse droplets were formed. The monodisperse droplets were collected in a reservoir.

[0207] The collected droplets were dried in an oven at 45°C for 4 hours to obtain monodisperse polymer spheres. The monodisperse polystyrene spheres contain polystyrene nanospheres having a bimodal particle size distribution.

[0208] Step 2) Porous metal oxide spheres After adding 1% by weight of silica nanoparticles to an aqueous mixture of the first and second colloidal dispersions, the mixture was combined with the oil phase to form a water-in-oil emulsion, and Example 1 was repeated. Similar to Example 1, droplets recovered from the microfluidic device were dried to form polymer template spheres. The polymer template spheres were placed on a silicon wafer and calcined by heating from room temperature to 500°C for 3 hours, holding at 500°C for 2 hours, and then cooling back to room temperature for 3 hours. Monodisperse silica spheres with an average diameter of 15 microns and containing two different average pore sizes were obtained.

[0209] [Example 11] Preparation of porous silica spheres with two average particle sizes via spray drying. Styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water was added to a three-neck reaction flask equipped with a thermometer and condenser under a nitrogen atmosphere while magnetically stirring. The water was heated to 80°C, and 10 g of styrene was added while stirring. Then, 100 mg of acrylic acid dissolved in 10 mL of DI water was added by syringe. 100 mg of ammonium persulfate was dissolved in 10 mL of DI water and added to the stirred mixture by syringe. The reaction mixture was stirred at 80°C for 24 hours. The polymer colloidal dispersion was allowed to cool to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0210] Similarly, styrene / acrylic acid copolymers were prepared to produce polystyrene nanospheres with an average particle size of 350 nm.

[0211] A first aqueous polystyrene colloidal dispersion (250 nm) was mixed with a second aqueous polystyrene colloidal dispersion (350 nm) in a weight ratio of 7:3. The mixture was diluted to 1% by weight with deionized water, and 1% by weight of silica nanoparticles were added to the mixture. The mixture was then subjected to ultrasonic treatment to prevent particle aggregation. The aqueous dispersions were spray-dried to obtain monodisperse polymer nanospheres and polymer template spheres containing silica with a bimodal distribution. The spheres were calcined by heating them from room temperature to 500°C for 3 hours, holding them at 500°C for 2 hours, and then cooling them back to room temperature for 3 hours to obtain porous silica spheres.

[0212] [Example 12] Porous zinc oxide spheres with two average particle sizes Using polystyrene nanospheres with average particle sizes of 250 nm and 320 nm in a 1:1 weight ratio, and with a polymer-to-zinc oxide weight ratio of 1:2, samples of porous zinc oxide spheres were prepared according to the method of Example 11.

[0213] [Example 13] Porous spheres containing silica and titania, having two average particle sizes. Using polystyrene nanospheres with average particle sizes of 350 nm and 460 nm in a weight ratio of 1:4, and with a weight ratio of polymer to total metal oxides of 3:1, porous sphere samples containing silica and titania were prepared according to the method of Example 11. The weight ratio of silica to titania was 9:1.

[0214] Determination of characteristics Experiment 1: Increase in dye absorbance using porous silica spheres 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 (alternative name Acid Blue 3), whose chemical name is 2-[(4-diethylaminophenyl)(4-diethylimino-2,5-cyclohexadiene-1-ylidene)methyl]-4-hydroxy-1,5-benzene-disulfonate. It is λ max At 637 nm, ε = 113900 Lmol -1 cm -1 It has a molar extinction coefficient of .

[0215] Another aqueous dispersion containing porous silica microspheres, but without dyes, as described in Example 3, served as a reference sample.

[0216] The dispersion was packed into a quartz cuvette with an optical thickness of 0.1 cm (Hellma Analytics), and the absorbance was measured by collecting both directly transmitted and forward scattered light using a Perkin Elmer Lambda 20 UV / vis spectrometer equipped with an integrating sphere accessory (RSA-PE-20). The Perkin Elmer Lambda 20 is a double-beam spectrometer, but the integrating sphere accessory is a single-beam device.

[0217] The reference and sample dispersion cells were placed in the light beam at the transmittance port of the integrating sphere, and a reflectance standard was mounted at the reflectance port of the integrating sphere. Measurements were performed with 2 nm spectral resolution. First, the absorbance of the reference dispersion was recorded, followed by the absorbance of the corresponding sample.

[0218] Figure 5 shows the results of adding Patent Blue V to a constant concentration (5.5-10) in the presence of porous silica spheres according to Example 3. -6 The absorbance of an aqueous dispersion containing (mol / L) at a path length d of 0.1 cm is shown. In Figure 5, 1 refers to the absorption spectrum of the reference sample. 2 refers to the absorption spectrum of an aqueous dispersion containing porous silica spheres at a concentration of 2 wt%. 3 refers to the absorption spectrum of an aqueous dispersion containing porous silica spheres at a concentration of 5 wt%.

[0219] Figure 5 shows that the presence of porous silica spheres increases the effectiveness of the dye absorbance, with the absorbance increasing by approximately 1.5 times at a porous microsphere concentration of 5% by weight.

[0220] Experiment 2: Increase in absorbance of UV absorber using porous silica spheres The procedure for Experiment 2 was the same as that for Experiment 1, except that the 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. The molar extinction coefficient of benzophenone-4 is λ max At 286 nm, ε = 13650 Lmol -1 cm -1 That is the case.

[0221] Figure 6 shows the case where benzophenone-4 is added to a constant concentration of 5.18·10 in the presence of porous silica spheres according to Example 3. -5 The absorbance of an aqueous dispersion containing mol / L at a path length d of 0.1 cm is shown. In Figure 6, 1 refers to the absorption spectrum of the reference sample. 2 refers to the absorption spectrum of an aqueous dispersion containing porous silica spheres at a concentration of 2 wt%. 3 refers to the absorption spectrum of an aqueous dispersion containing porous silica spheres at a concentration of 5 wt%.

[0222] Figure 6 shows that the presence of porous silica spheres increases the effectiveness of benzophenone-4's UV absorbance, with the ultraviolet absorbance increasing by approximately 2.5 times at a porous silica sphere concentration of 5% by weight.

[0223] Therefore, the boosting of absorbance, i.e., the increase in absorbance due to the presence of porous spheres, is greater in the UV range compared to the visible range.

[0224] Experiment 3: Effect of concentration on UV absorption Sets of five aqueous dispersions containing benzophenone-4 and porous silica particles of Example 3 at different concentrations were prepared using the same procedure as in Experiment 2. Similarly, one set each of aqueous dispersions containing porous silica particles at different concentrations for Examples 4 and 5 was prepared. Blank samples containing no porous metal oxide particles were prepared for comparison. λ of UV absorber max The UV absorbance of the aqueous dispersion was measured.

[0225] Figure 7 shows a graph plotting the absorbance of aqueous dispersions containing benzophenone-4 at a path length d of 0.1 cm for various concentrations of porous silica spheres from Examples 3, 4, and 5. In Figure 7, 1 refers to the absorption spectrum of the aqueous dispersion containing porous silica spheres from Example 3. 2 refers to the absorption spectrum of the aqueous dispersion containing porous silica spheres from Example 4. 3 refers to the absorption spectrum of the aqueous dispersion containing porous silica spheres from Example 5. Blank refers to the absorbance of the blank sample.

[0226] Figure 7 shows that the effectiveness of benzophenone-4 in terms of UV absorbance increases as the concentration of porous silica spheres increases.

[0227] Experiment 4: Comparative Example A set of five aqueous dispersions containing benzophenone-4 and Sunsil® 130, a commercially available silica particle from Sunjin, at different concentrations was prepared using the same procedure as in Experiment 2. A blank sample without porous metal oxide particles was prepared for comparison. The λ of the UV absorber max The UV absorbance of the aqueous dispersion was measured.

[0228] Figure 8 shows a graph plotting the absorbance of aqueous dispersions containing benzophenone-4 at various concentrations at a path length d of 0.1 cm, along with various concentrations of Sunsil® 130 silica particles. In Figure 8, 1 refers to the absorption spectrum of the aqueous dispersion containing Sunsil® 130 silica particles. Blank refers to the absorbance of the blank sample.

[0229] Figure 8 shows that the presence of silica particles Sunsil® 130 does not affect the effectiveness of the UV absorbance of benzophenone-4.

[0230] Experiment 5: Increase in dye absorbance using porous titania spheres The procedure for Experiment 5 was the same as that for Experiment 1, except that the porous silica particles were replaced with porous titania particles prepared according to Examples 7 and 8.

[0231] Figure 9 shows the visible region absorption spectra at a path length d of 0.1 cm for aqueous dispersions of porous titania spheres according to Examples 7 and 8, at concentrations of 0.2 wt% and 0.5 wt%. In Figure 9, 1 refers to the absorption spectrum of the aqueous dispersion containing 0.5 wt% of the porous titania spheres of Example 8. 2 refers to the absorption spectrum of the aqueous dispersion containing 0.5 wt% of the porous titania spheres of Example 7. 3 refers to the absorption spectrum of the aqueous dispersion containing 0.2 wt% of the porous titania spheres of Example 8. 4 refers to the absorption spectrum of the aqueous dispersion containing 0.2 wt% of the porous titania spheres of Example 7. 5 refers to the absorbance of a reference sample that does not contain any of the porous metal oxide spheres.

[0232] From Figure 9, it was observed that the presence of porous titania spheres increased the effectiveness of the dye absorbance, with absorbance increasing by approximately 2.8 times and 4 times at porous microsphere concentrations of 5% by weight of porous titania spheres from Examples 7 and 8, respectively.

[0233] Experiment 6: Absorption spectrum of a porous titania sphere Porous titania spheres prepared according to Examples 7 and 9 were dispersed in aqueous solutions containing neither dyes nor UV absorbers. The UV absorption of these solutions was analyzed in the same manner as in Experiment 1.

[0234] Figure 10 shows the UV absorption spectra at a path length d of 0.1 cm for aqueous dispersions containing porous titania spheres according to Examples 7 and 8 at concentrations of 0.2 wt% and 0.5 wt%, respectively. In Figure 10, 1 refers to the absorption spectrum of the aqueous dispersion containing porous titania spheres at a concentration of 0.4 wt% of Example 7. 2 refers to the absorption spectrum of the aqueous dispersion containing porous titania spheres at a concentration of 0.4 wt% of Example 8. 3 refers to the absorption spectrum of the aqueous dispersion containing porous titania spheres at a concentration of 0.2 wt% of Example 7. 4 refers to the absorption spectrum of the aqueous dispersion containing porous titania spheres at a concentration of 0.2 wt% of Example 8.

[0235] Figure 10 shows that the aqueous dispersion containing porous titania spheres exhibits broad UV absorbance in the range of 250–390 nm, with maximum UV absorbance in the range of 320–340 nm. Absorption is high in the UVB range of 290–320 nm, while it drops sharply in the UVA range of 380–420 nm.

[0236] Experiment 7: UV Protection Factor (SPF) Experiment Two sets of compositions were prepared to determine the SPF. A first set of compositions was prepared containing a UV filter in the oil phase, and a second set of compositions was prepared without the additional UV filter.

[0237] 3.1) Composition containing a UV filter The following compositions were prepared.

[0238] [Table 3] TIFF2022524538000055.tif234137

[0239] Preparation procedure for the basic formulation: Phase A and Phase B were heated separately with stirring. Phase A was incorporated into Phase B under stirring. The mixture was stirred until a homogeneous mixture was obtained, and then stirred for 1 minute. Finally, the mixture was cooled to room temperature under stirring. The basic formulation was prepared at 80°C.

[0240] Sample preparation: Two formulations were prepared using 2% by weight and 5.5% by weight of the porous spheres according to Example 3, respectively. The porous spheres were incorporated into the base formulation under stirring, and water was added to make a total volume of 100.

[0241] Reference formulation: The reference sample was prepared using the marketed product "SunSpheres®" from Dow Chemicals. 5.5% by weight of the marketed product was incorporated into the base formulation. SunSpheres® is a styrene-acrylate copolymer in the form of hollow spheres, prepared by controlled emulsion polymerization.

[0242] Placebo formulation: A placebo sample free of particles was prepared by adding water to the base formulation to make a total volume of 100.

[0243] evaluation: The SPF of these compositions was measured according to the in vitro SPF method (by RM Sayre et al.), and the results are shown in Table 2.

[0244] [Table 4]

[0245] Figure 11 shows the absorbance of compositions 5, 6, 8, and 9 in the wavelength range of 290–450 nm. In Figure 11, 1 refers to the absorption spectrum of composition 9. 2 refers to the absorption spectrum of composition 5. 3 refers to the absorption spectrum of composition 6. 4 refers to the absorption spectrum of placebo composition 8.

[0246] In vitro SPF increased by 20% with the addition of 2% porous silica spheres, and even by 28% with the addition of 5.5% porous silica spheres. It can be concluded that the presence of porous spheres increases the effectiveness of UV absorbance by approximately 6.6 times at 312 nm (maximum UVB peak) and by approximately 5.3 times at 351 nm (maximum UVA peak) at a particle concentration of 5.5%.

[0247] An increase in SPF was also observed in compositions containing Sunspheres® for comparative analysis. However, the nanoparticle properties of Sunspheres® can be recognized by scattering at wavelengths above 400 nm, commonly referred to as "tailing." This scattering leads to a visible and undesirable whitening effect on the skin.

[0248] 3.2) Formulations that do not contain additional UV filters The following formulations were prepared using the procedure described above in Experiment 3.1 of this specification. The contents of the basic and reference compositions are shown in Table 3.

[0249] [Table 5]

[0250] Placebo formulation: A placebo sample free of particles was prepared by adding water to the base formulation to make a total volume of 100.

[0251] Sample preparation: Three formulations were prepared using porous silica spheres from Example 3 in concentrations of 2% by weight, 5.5% by weight, and 8% by weight, respectively. The porous spheres were incorporated into the basic formulations together with water.

[0252] Reference formulation: The reference sample was prepared using the marketed product "SunSpheres®" from Dow Chemicals. 5.5% by weight of the marketed product was incorporated into the base formulation.

[0253] [Table 6]

[0254] The SPF of these compositions was measured according to the in vitro SPF method (by RMSayre et al.), and the results are shown in Table 5.

[0255] [Table 7]

[0256] Figure 12 shows the absorbance of compositions without additional UV filters in the range of 290–450 nm. In Figure 12, 1 refers to the absorption spectrum of composition 3. 2 refers to the absorption spectrum of composition 2. 3 refers to the absorption spectrum of composition 1. 4 refers to the absorption spectrum of the placebo composition.

[0257] Compositions containing 5.5% by weight or 8% by weight of added particles show increased absorption across the entire UV range of 290 to 450 nm. The in vitro SPF of the composition can be increased by 10% with the addition of 5.5% by weight of the porous spheres according to Example 3, and by 20% with the addition of 8% by weight of the porous spheres according to Example 3.

[0258] Experiment 4: Transparency / Whitening Experiment The whitening data for both formulation series prepared in Experiment 3 was determined by the color measurement described above.

[0259] The results for formulations containing a UV filter are summarized in Figure 13. In Figure 13, 1 refers to the absorption spectrum of composition 9. 2 refers to the absorption spectrum of composition 5. 3 refers to the absorption spectrum of composition 6. 4 refers to the absorption spectrum of placebo composition 8.

[0260] The results for formulations without a UV filter are summarized in Figure 14. In Figure 14, 1 refers to the absorption spectrum of the placebo composition. 2 refers to the absorption spectrum of composition 1. 3 refers to the absorption spectrum of composition 2. 4 refers to the absorption spectrum of composition 3. 5 refers to the absorption spectrum of composition 4, which contains the reference composition.

[0261] From Figures 13 and 14, it is observed that "Sunspheres®" significantly scatter visible light, and therefore produce a strong whitening effect on the skin. ΔL* increases by 8 (120%) in Figure 13 and by 7.5 (77%) in Figure 14. Conversely, the porous spheres of the present invention do not produce this whitening effect. The brightness of formulations containing the porous spheres of the present invention is the same as the brightness of the reference. Only in the case of the highest concentration of 8% by weight porous spheres is a slight increase of 2.8 (29%) observed, but this is invisible to the untrained human eye, as only a ΔL* difference greater than 4 can be perceived.

Claims

1. 1. A method for increasing the sun protection factor of a sunscreen composition, comprising the step of 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 silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

2. Use of porous spheres containing a metal oxide for increasing the UV protection factor of a sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

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

4. 4. The method or use according to any one of claims 1 to 3, wherein the amount of metal oxide in the porous spheres is in the range of 60.0 to 99.9 wt. % relative to the total weight of the porous spheres.

5. 5. The method or use according to any one of claims 1 to 4, wherein the porous spheres have an average diameter in the range of 0.5 μm to 100.0 μm.

6. 6. The method or use according to any one of claims 1 to 5, wherein the porous spheres have an average porosity in the range of 0.10 to 0.

90.

7. 7. The method or use according to any one of claims 1 to 6, wherein the porous spheres have an average porosity in the range of 0.10 to 0.

80.

8. 8. The method or use according to any one of claims 1 to 7, wherein the porous spheres are monodisperse.

9. 9. The method or use according to any one of claims 1 to 8, wherein the porous spheres have an average pore diameter in the range of 50 nm to 999 nm.

10. 10. The method or use according to any one of claims 1 to 9, wherein the porous spheres have more than one population of pores, each with an average pore diameter, and each population has a different average pore diameter.

11. The porous spheres are a. have an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 50 nm to 999 nm; d. monodisperse; 11. The method or use according to any one of claims 1 to 10.

12. The porous spheres are a. have an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.80; c. having an average pore diameter in the range of 50 nm to 999 nm; d. monodisperse; 12. The method or use according to any one of claims 1 to 11.

13. The sunscreen composition comprises: (d 1 ) p-aminobenzoic acid derivatives, (d 2 ) salicylic acid derivatives, (d 3 ) benzophenone derivatives, (d 4 ) dibenzoylmethane derivatives, (d 5 ) diphenyl acrylate, (d 6 ) 3-imidazol-4-yl-acrylic acid and its esters, (d 7 ) benzofuran derivatives, (d 8 ) Polymeric UV absorbers, (d 9 ) cinnamic acid derivatives, (d 10 ) camphor derivatives, (d 11 ) hydroxyphenyltriazine derivatives, (d 12 ) benzotriazole derivatives, (d 13 ) trianilino-s-triazine derivatives, (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts, (d 15 ) Menthyl o-aminobenzoate, (d 16 ) Homosalate, (d 17 ) tris-biphenyltriazine derivatives, (d 18 ) TiO 2 (partially encapsulated), ZnO and mica, (d 19 ) benzylidene malonate, (d 20 ) merocyanine derivatives, (d 21 ) phenylenebisdiphenyltriazine, (d 22 ) imidazoline derivatives, and (d 23 ) Diarylbutadiene derivatives 13. The method or use according to any one of claims 1 to 12, further comprising a UV absorber selected from the group consisting of:

14. 14. The method of any one of claims 1 to 13, further comprising minimizing or masking the whitening effect of the sunscreen composition and maintaining its transparency.

15. 15. The use according to any one of claims 1 to 14, which further minimizes or masks the whitening effect of a sunscreen composition and maintains its transparency.

16. A sunscreen composition comprising water and porous spheres, wherein the porous spheres contain a metal oxide in the range of 1.0 to 10.0 wt % based on the total weight of the sunscreen composition, and the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, and chromium oxide.

17. 17. The sunscreen composition of claim 16, further comprising in the range of 5.0 to 50.0 wt. % of a discontinuous oil phase, based on the total weight of the sunscreen composition.

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

19. 19. The sunscreen composition of claim 18, wherein the emulsifier is selected from the group consisting of anionic emulsifiers, nonionic emulsifiers, and polymeric emulsifiers.

20. 20. The sunscreen composition of claim 16, further comprising an additive selected from the group consisting of a thickener, an active ingredient, a preservative, and a fragrance.

21. 21. The sunscreen composition according to any one of claims 16 to 20, wherein the amount of metal oxide in the porous spheres ranges from 60.0 to 99.9% by weight, based on the total weight of the porous spheres.

22. 22. The sunscreen composition according to any one of claims 16 to 21, wherein the porous spheres have an average diameter in the range of 0.5 μm to 100.0 μm.

23. 23. The sunscreen composition according to any one of claims 16 to 22, wherein the porous spheres have an average porosity in the range of 0.10 to 0.

90.

24. 24. The sunscreen composition according to any one of claims 16 to 23, wherein the porous spheres have an average porosity in the range of 0.10 to 0.

80.

25. 25. The sunscreen composition according to any one of claims 16 to 24, wherein the porous spheres have an average pore diameter in the range of from 50 nm to 999 nm.

26. 26. The sunscreen composition of any one of claims 16 to 25, wherein the porous spheres are monodisperse.

27. The porous spheres are a. have an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.90; c. having an average pore diameter in the range of 50 nm to 999 nm; d. monodisperse; 27. A sunscreen composition according to any one of claims 16 to 26.

28. The porous spheres are a. have an average diameter in the range of 0.5 μm to 100.0 μm; b. having an average porosity in the range of 0.10 to 0.80; c. having an average pore diameter in the range of 50 nm to 999 nm; d. monodisperse; 28. A sunscreen composition according to any one of claims 16 to 27.

29. (d 1 ) p-aminobenzoic acid derivatives, (d 2 ) salicylic acid derivatives, (d 3 ) benzophenone derivatives, (d 4 ) dibenzoylmethane derivatives, (d 5 ) diphenyl acrylate, (d 6 ) 3-imidazol-4-yl-acrylic acid and its esters, (d 7 ) benzofuran derivatives, (d 8 ) Polymeric UV absorbers, (d 9 ) cinnamic acid derivatives, (d 10 ) camphor derivatives, (d 11 ) hydroxyphenyltriazine derivatives, (d 12 ) benzotriazole derivatives, (d 13 ) trianilino-s-triazine derivatives, (d 14 ) 2-phenylbenzimidazole-5-sulfonic acid and its salts, (d 15 ) Menthyl o-aminobenzoate, (d 16 ) Homosalate, (d 17 ) tris-biphenyltriazine derivatives, (d 18 ) TiO 2 (partially encapsulated), ZnO and mica, (d 19 ) benzylidene malonate, (d 20 ) merocyanine derivatives, (d 21 ) phenylenebisdiphenyltriazine, (d 22 ) imidazoline derivatives, and (d 23 ) Diarylbutadiene derivatives 29. The sunscreen composition of any one of claims 16 to 28, further comprising a UV absorber selected from the group consisting of:

30. 30. The sunscreen composition of any one of claims 16 to 29, further comprising a dye selected from the group consisting of Acid Violet 43 and Acid Red 33.

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