Non-nano UV filter dispersions

Abstract

The present invention relates to a method for manufacturing an aqueous suspension (1) of at least one micronized organic UV filter and to an aqueous suspension (1) comprising at least one micronized organic UV filter. The present invention relates to a process of manufacturing an aqueous suspension (1) of at least one micronized organic UV filter as well as to an aqueous suspension (1) comprising at least one micronized organic UV filter.

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing an aqueous suspension (1) of at least one micronized organic UV filter and to the aqueous suspension (1) containing at least one micronized organic UV filter and its use. [Previous Technology]

[0002] Micronization of organic UV filter (also known as UV absorber) dispersions is known in the literature.

[0003] Suitable organic microparticle UV absorbers for use in cosmetic sunscreens are described, for example, in WO9703643, WO2009077356 and WO2015155158.

[0004] WO9703643 provides a method for producing a composition of a micronized organic UV absorber, the method comprising milling the UV absorber in the presence of an alkyl polyglucoside. The average particle size of the micronized organic UV filter is 0.01 to 2 µm, particularly 0.05 to 1 µm.

[0005] WO2009003934 describes other methods for producing novel nanoscale formulations of micronized insoluble UV absorbers. These dispersions are prepared by grinding the UV absorber in the presence of an antifoaming agent used as a dispersant aid in an apparatus comprising yttrium-stabilized zirconia grinding beads.

[0006] Regarding the use of defoamers in the grinding process, WO2018069200 states that defoaming is significantly reduced if a specific particle size of the coarse UV absorber is selected. Specifically, in order to achieve a particle size Dv50 < 200 nm (measured by light scattering) of the dispersion of the UV absorber in a mixture of water and alkyl polyglucoside, the particle size distribution Dv90 of the UV absorber solid, as measured by laser diffraction, needs to be within 1 to 150 µm.

[0007] A grinding aid for producing micronized organic UV absorbers is exemplarily described in WO2009068469.

[0008] None of these disclosures teach how to prepare a non-nano UV absorber suspension that still provides effective UV protection. In view of the ongoing public discussions regarding the use of nanomaterials in products such as cosmetics, there is a continued need to develop a method for generating a UV absorber suspension that does not contain nanomaterials.

[0009] The particle size distribution of a suspension can be characterized relative to particle volume (mass) or particle number. For example, Dv90 = 1 µm means that 90% of the volume (or mass) of the dispersed material consists of particles smaller than 1 µm, and 10% is larger. Conversely, DN30 = 100 nm refers to a number-based size distribution and indicates that 30% of all particles in the sample are smaller than 100 nm. As a rule of thumb, in polydisperse samples, small particles predominate in the number-based distribution DN, while large particles predominate in Dv. Measurement techniques differ in their sensitivity to particle number or particle mass. Volume-based distributions can be obtained by laser diffraction, and number-based distributions by electron microscopy. As for laser diffraction, it is available in many commercially available instruments, such as those from Anton Paar (PSA series), Microtrac MRB (Sync), or Malvern Panalytical (Mastersizer series). Depending on the sensitivity and resolution of the instrument chosen, the numerical results characterizing the particle size distribution vary within a small range. Skilled experts know how to handle such deviations and routinely use such instruments in R&D and quality control laboratories. In contrast, electron microscopes are more expensive and used less frequently.

[0010] This distinction between DN and Dv is related to the "nano" classification of materials. According to the European Commission's recommendation 2011 / 696 / EU, micronized dispersions with a DN50 value of 100 nm or less are considered nanomaterials. Methods for producing micronized organic UV absorbers, as seen in the literature, typically stop at nano-dispersions, i.e., UV absorber particles Dv50 of insoluble organic UV absorbers with a size in the range of 50 to 150 nm (WO2018069200). This appears ideal because the efficiency of UV absorber dispersions increases with decreasing particle size. Furthermore, depending on the mechanical properties of the UV absorber crystals, a breakage mechanism in a grinding apparatus can produce nanomaterials still in the µm range from the crystals.

[0011] Against the above background, one object of the present invention is to provide a formulation comprising a micron-sized non-nano-sized organic UV filter, preferably wherein the micron-sized non-nano-sized organic UV filter is an insoluble organic UV filter. Furthermore, one object of the present invention is that the non-nano-sized organic UV filter still provides effective UV protection efficiency. Another object of the present invention is to provide a method for manufacturing a formulation comprising a micron-sized non-nano-sized organic UV filter, preferably wherein the micron-sized non-nano-sized organic UV filter is an insoluble organic UV filter. Another object of the present invention is to provide a formulation that does not contain nanomaterials. [Summary of the Invention]

[0012] Surprisingly, it has been found that if a hydrophobic additive is added to the milling machine at an adjusted temperature during the milling process, nanomaterials are avoided during the micronization process, thereby maintaining the sufficient efficiency of the UV filter.

[0013] Therefore, according to the first sample A, the present invention relates to a method for preparing an aqueous suspension (1) of at least one organic UV filter having a particle size DN30 of 100 nm or larger, the method comprising the step of grinding (2) a suspension (2) containing at least one organic UV filter in a mixture of water and hydrophobic additives at a temperature of 35 to 90°C in a grinding apparatus.

[0014] In view of the EC Nano recommendation, it can be noted that, in principle, the present invention can also be used to achieve an aqueous suspension (1) of at least one organic UV filter having a particle size within DN30 and DN50 of 100 nm. In view of the fluctuations in particle size distribution, it is preferable to aim for fewer particles approaching the nanomaterial boundary and to avoid analyzing every single batch in actual production.

[0015] In the following, preferred embodiments of the above manufacturing method are described in more detail. Furthermore, preferred embodiments of the aqueous suspension (1) and its uses are described in more detail. It should be understood that each preferred embodiment is relevant on its own and in combination with other preferred embodiments.

[0016] In a preferred embodiment A1 of the first state sample, the at least one organic UV filter in the aqueous suspension (1) preferably has a particle size DN10 of 100 nm or larger, preferably 0.1 to 0.4 µm, more preferably 0.1 to 0.2 µm, as measured by transmission electron microscopy; and / or preferably a particle size DN50 of 120 nm or larger, preferably 0.12 to 0.5 µm, more preferably 0.12 to 0.3 µm, as measured by transmission electron microscopy; and / or preferably a particle size DN90 of 200 nm or larger, preferably 0.2 to 1.0 µm, more preferably 0.2 to 0.5 µm, as measured by transmission electron microscopy; and / or a particle size Dv10 of greater than 0.1 µm, preferably 0.1 to 0.4 µm, as measured by laser diffraction; and / or a particle size of less than 2.2 µm, preferably less than 2.0 µm, as measured by laser diffraction. μm, preferably less than 1.5 µm, with Dv90, where Dv10 and Dv90 were measured using a Mastersizer 2000 from Malvern Panalytical.

[0017] In a preferred embodiment A2 of the first state sample, during the grinding step, the particle population of less than 100 nm in the aqueous suspension (1) is reduced, preferably, wherein the particle population of less than 100 nm in the aqueous suspension (1) is reduced by increasing the temperature of the suspension (2) in the grinding apparatus. The terms "reduced" and "increased temperature" are both in comparison to a grinding step that produces an aqueous suspension (1) having DN30 of 99 nm or smaller.

[0018] In a preferred embodiment A3 of the first state sample, the temperature of the suspension (2) in the grinding step is in the range of 40 to 80°C, preferably 40 to 70°C, and particularly 45 to 65°C.

[0019] In a preferred embodiment A4 of the first state sample, the hydrophobic additive is a cosmetic oil, preferably selected from the group consisting of: alcohols having 6 to 18 carbon atoms; C6-C24 carboxylic acids; esters of C6-C24 carboxylic acids and C3-C24 alcohols; esters of hydroxycarboxylic acids and C6-C24 alcohols; esters of carboxylic acids and polyols; liquid mono- / di- / tri-glycerol ester mixtures based on C6-C18 carboxylic acids; esters of C6-C24 alcohols and aromatic carboxylic acids or oxycarboxylic acids; tricarboxylic acid esters; C2-C12 dicarboxylic acids and alcohols having 1 to 22 carbon atoms or having 2 to 10 carbon atoms and 2 to 6 carbon atoms. Esters of hydroxyl polyols; substituted cyclohexanes; C6-C22 alcohol carbonates; symmetrical or asymmetric dialkyl ethers having a total of 12 to 36 carbon atoms; ring-opening products of epoxidized carboxylic acid esters and polyols; polysiloxanes; aliphatic or cycloalkanes; diol esters; and mixtures thereof, particularly selected from the group consisting of: esters of C6-C24 alcohols (preferably C10 to C17 alcohols) with aromatic carboxylic acids (preferably benzoic acid) or with hydroxycarboxylic acids (preferably lactic acid esters) or with oxycarboxylic acids (preferably acetopropionates); dicarboxylic acid esters, preferably di-n-butyl adipate; tricarboxylic acid esters, preferably tributyl citrate; and mixtures thereof.

[0020] In a preferred embodiment A5 of the first state sample, the at least one organic UV filter is an insoluble organic UV filter, preferably selected from the group consisting of: oxadiphenylamine UV filter, triazine UV filter, piperazine UV filter, triazole UV filter, vinyl-containing oxadiamine UV filter, cinnamic acid oxadiamine UV filter, sulfonated benzimidazole and mixtures thereof, more preferably selected from the group consisting of: oxadiphenylamine UV filter (1) having formula (1) wherein R1 and R2 are independently C1-C18 alkyl or C1-C18 alkoxy; triazine UV filter (2) having formula (2) wherein R3, R4 and R 5 is independently H; OH; C1-C18 alkoxy; NH2; NH-R6 or N(R6)2, wherein R6 is a C1-C18 alkyl; OR6, wherein R6 has the foregoing meaning; phenyl; phenoxy; aniline; pyrrole, wherein the corresponding phenyl, phenoxy, aniline or pyrrole moiety is substituted as needed by one, two or three of the following substituents: OH, carboxyl, CO-NH2, C1-C18 alkyl or -alkoxy, C1-C18 carboxyalkyl, C5-C8 cycloalkyl, phenyl, methylene camphoryl, group -(CH=CH)mC(=O)-OR6 (where m is 0 or 1 and R6 has the aforementioned meaning), or a group or corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4 alkylammonium, mono-, di- or tri-C2-C4 alkylammonium salt or its C1-C18 alkyl ester; phenyl bis-diphenyltriazine; piperazine UV filter; triazole UV filter having formula (31), (32) or (33) (31)(32)(33) where T1 is C1-C18 alkyl or hydrogen and T2 is C1-C18-alkyl, which is substituted with phenyl as needed; vinyl-containing amide UV filter having formula (4) (4) where R9 is C1-C18 alkyl or phenyl substituted with one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the aforementioned meaning); R10, R11, R12 and R 13 is the same or different and each is independently C1-C18 alkyl or hydrogen; Y is N or O; and m has the meaning of the foregoing; a cinnamic acid amide UV filter (5) having formula (5) wherein R 14 is hydroxyl or C1-C4 alkoxy; R 15 is hydrogen or C1-C4 alkyl; and R 16 is -(CONH)m-phenyl, wherein m has the meaning of the foregoing and the phenyl is substituted as needed by one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the meaning of the foregoing); a sulfonated benzimidazole UV filter (6) having formula (6) wherein M is hydrogen or alkali metal, alkaline earth metal or zinc;And mixtures thereof, or even more preferably, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine, 1,1'-(1,4-piperazinidyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methyl ketone, phenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol], and particularly, wherein the at least one organic UV filter is selected from the group consisting of phenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

[0021] In a preferred embodiment A6 of the first state sample, the hydrophobic additive is included in the aqueous suspension (1) in an amount of 0.01 to 10.0% by weight, preferably 0.01 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, and particularly 0.05 to 1.0% by weight.

[0022] In a preferred embodiment A7 of the first state sample, the grinding step is carried out in a ball mill, vibratory mill, wet rotor mill, stirred media mill or colloid mill, preferably a wet rotor mill or stirred media mill, and particularly in a stirred media mill with grinding beads, preferably glass beads, zirconia or mixed ceramic grinding beads, having a diameter of 0.1 to 10 mm, preferably 0.15 to 5 mm, and particularly 0.2 to 3 mm.

[0023] In a preferred embodiment A8 of the first state sample, the at least one organic UV filter of the suspension (2) has a particle size Dv90 in the range of 0.01 to 300 µm, preferably 0.1 to 250 µm, as determined by laser diffraction.

[0024] In the second state sample B, the present invention relates to an aqueous suspension (1) comprising a) 10 to 65% by weight of at least one organic UV filter having a particle size of DN30 of 100 nm or larger, b) 0.01 to 10.0% by weight of a hydrophobic additive selected from the group consisting of: alcohols having 6 to 18 carbon atoms; C6-C24 carboxylic acids; esters of C6-C24 carboxylic acids and C3-C24 alcohols; esters of hydroxycarboxylic acids and C6-C24 alcohols; esters of carboxylic acids and polyols; liquid mono- / di- / tri-glycerol mixtures based on C6-C18 carboxylic acids; esters of C6-C24 alcohols and aromatic carboxylic acids or oxycarboxylic acids; tricarboxylic acid esters; esters of C2-C12 dicarboxylic acids and alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups; substituted cyclohexane; C6-C22 alcohol carbonates; symmetrical or asymmetrical dialkyl ethers having a total of 12 to 36 carbon atoms; ring-opening products of epoxidized carboxylic acid esters and polyols; polysiloxane oils; aliphatic or cycloalkanes; diol esters; and mixtures thereof, and c) All water amounts are based on the total amount of aqueous suspension (1).

[0025] In a preferred embodiment B1 of the second state sample, the hydrophobic additive is selected from the group consisting of: esters of C6-C24 alcohols (preferably C10 to C17 alcohols) with aromatic carboxylic acids (preferably benzoic acid) or with hydroxycarboxylic acids (preferably lactate) or with oxycarboxylic acids (preferably acetopropionate); dicarboxylic acid esters, preferably di-n-butyl adipate; tricarboxylic acid esters, preferably tributyl citrate; and mixtures thereof.

[0026] In a preferred embodiment B2 of the second state sample, the at least one organic UV filter is an insoluble organic UV filter, preferably selected from the group consisting of: oxadiphenylamine UV filter, triazine UV filter, piperazine UV filter, triazole UV filter, vinyl-containing oxadiamine UV filter, cinnamic acid oxadiamine UV filter, sulfonated benzimidazole and mixtures thereof, more preferably selected from the group consisting of: oxadiphenylamine UV filter (1) having formula (1) wherein R1 and R2 are independently C1-C18 alkyl or C1-C18 alkoxy; triazine UV filter (2) having formula (2) wherein R3, R4 and R 5 is independently H; OH; C1-C18 alkoxy; NH2; NH-R6 or N(R6)2, wherein R6 is a C1-C18 alkyl; OR6, wherein R6 has the foregoing meaning; phenyl; phenoxy; aniline; pyrrole, wherein the corresponding phenyl, phenoxy, aniline or pyrrole moiety is substituted as needed by one, two or three of the following substituents: OH, carboxyl, CO-NH2, C1-C18 alkyl or -alkoxy, C1-C18 carboxyalkyl, C5-C8 cycloalkyl, phenyl, methylene camphoryl, group -(CH=CH)mC(=O)-OR6 (where m is 0 or 1 and R6 has the aforementioned meaning), or a group or corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4 alkylammonium, mono-, di- or tri-C2-C4 alkylammonium salt or its C1-C18 alkyl ester; phenyl bis-diphenyltriazine; piperazine UV filter; triazole UV filter having formula (31), (32) or (33) (31)(32)(33) where T1 is C1-C18 alkyl or hydrogen and T2 is C1-C18-alkyl, which is substituted with phenyl as needed; vinyl-containing amide UV filter having formula (4) (4) where R9 is C1-C18 alkyl or phenyl substituted with one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the aforementioned meaning); R10, R11, R12 and R 13 is the same or different and each is independently C1-C18 alkyl or hydrogen; Y is N or O; and m has the meaning of the foregoing; a cinnamic acid amide UV filter (5) having formula (5) wherein R 14 is hydroxyl or C1-C4 alkoxy; R 15 is hydrogen or C1-C4 alkyl; and R 16 is -(CONH)m-phenyl, wherein m has the meaning of the foregoing and the phenyl is substituted as needed by one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the meaning of the foregoing); a sulfonated benzimidazole UV filter (6) having formula (6) wherein M is hydrogen or alkali metal, alkaline earth metal or zinc;And mixtures thereof, or even more preferably, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine, 1,1'-(1,4-piperazinidyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methyl ketone, phenyl bis-diphenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol], and particularly, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

[0027] In a preferred embodiment B3 of the second state sample, the aqueous suspension (1) contains 0.01 to 8.0% by weight, more preferably 0.01 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, and particularly 0.05 to 1.0% by weight of hydrophobic additives.

[0028] In a preferred embodiment B4 of the second state sample, the at least one organic UV filter has a particle size DN10 of 100 nm or larger, preferably 0.1 to 0.4 µm, more preferably 0.1 to 0.2 µm, as measured by transmission electron microscopy; and / or a particle size DN50 of 120 nm or larger, preferably 0.12 to 0.5 µm, more preferably 0.12 to 0.3 µm, as measured by transmission electron microscopy; and / or a particle size DN90 of 200 nm or larger, preferably 0.2 to 1.0 µm, more preferably 0.2 to 0.5 µm, as measured by transmission electron microscopy; and / or a particle size Dv10 of greater than 0.1 µm, preferably 0.1 to 0.4 µm, as measured by laser diffraction; and / or a particle size of less than 2.2 µm, preferably less than 2.0 µm, more preferably less than 1.5 µm, as measured by laser diffraction. The particle size Dv90 is µm, where Dv10 and Dv90 were measured using a Mastersizer 2000 from Malvern Panalytical.

[0029] In the third state sample C, the present invention relates to the aqueous suspension (1) according to the second state sample B and all embodiments thereof, which is used in sunscreens or daily care compositions.

Implementation Method

[0030] Before describing in detail the exemplary embodiments of the present invention, definitions that are important for understanding the present invention are given.

[0031] As used in this specification and the accompanying claims, unless the context clearly indicates otherwise, the singular forms of "a" and "an" also include the corresponding plurals. In the context of this invention, the terms "about" and "approximately" represent intervals that those skilled in the art will understand to still ensure the accuracy of the technical effect of the stated features. The terms generally indicate a deviation from the specified value of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5%. It should be understood that the term "comprising" is not limiting. For the purposes of this invention, the term "consisting of" is considered a preferred embodiment of the term "comprising of". If a group is defined below as including at least a certain number of embodiments, this is also intended to cover a group preferably consisting only of such embodiments. Furthermore, the terms "first," "second," "third," or "(a)," "(b)," "(c)," "(d)," etc., and similar terms are used in this description and the claims to distinguish between similar elements and are not necessarily used for the order of description or chronological order. It should be understood that such terms may be interchanged where appropriate and that embodiments of the invention described herein may be operated in a different order than that described or illustrated herein. If the terms "first," "second," "third," or "(a)," "(b)," "(c)," "(d)," "i," "ii," etc., relate to steps of a method or use or testing, there is no temporal or time interval consistency between the steps; that is, such steps may be performed simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months, or even years between such steps, unless otherwise indicated in this application as stated above or below. It should be understood that the invention is not limited to the specific methods, schemes, reagents, etc., described herein, as these are subject to change. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention to the extent that it is limited only to the claims appended. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

[0032] As used herein, the terms "does not contain" or "does not contain" mean, in the context that the composition of the present invention does not contain a specific compound or group of compounds (which may be combined under the general term), that the composition does not contain more than 0.8% by weight of that compound or group of compounds based on the total weight of the composition. Furthermore, preferably, the composition of the present invention does not contain more than 0.5% by weight of such compounds or group of compounds, and more preferably, the composition does not contain such compounds or group of compounds at all.

[0033] When referring to the composition and the weight percentage of the components contained therein, it should be understood that, according to the present invention, the total amount of the components does not exceed 100% (±1% due to rounding).

[0034] The terms "sunscreen composition" or "sunscreen" refer to any topical product that absorbs and can further reflect and scatter a specific portion of UV radiation. Therefore, the term "sunscreen composition" should be understood to include not only sunscreen compositions but also any cosmetic composition that provides UV protection. The term "topical product" refers to a product applied to the skin and may refer to, for example, a spray, lotion, cream, oil, foam, powder, or gel. According to the invention, a sunscreen composition may contain one or more active agents (e.g., organic and inorganic UV filters) and other ingredients or additives (e.g., emulsifiers, emollients, viscosity modifiers, stabilizers, preservatives, or fragrances).

[0035] Regarding suitable inorganic UV filters, titanium dioxide, zinc oxide and cerium oxide may be nominated.

[0036] The term "daily care composition" refers to any topical product that absorbs and can further reflect and scatter UV radiation in a specific portion and is used as a daily care product for the human body (e.g., for the face or body). A daily care composition may contain one or more active agents (e.g., organic and / or inorganic UV filters) and other ingredients or additives (e.g., emulsifiers, softeners, viscosity modifiers, stabilizers, preservatives, or fragrances). Suitable daily care compositions are those according to the present invention, such as leave-on facial or body care products.

[0037] Suitable leave-on products for face and body include, for example, sunscreen compositions, decorative preparations and skin care preparations.

[0038] Suitable decorative preparations include, for example, lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions.

[0039] Suitable skin care formulations include, for example, moisturizing, conditioning, and lifting formulations. The daily care compositions cited may be in the form of creams, ointments, balms, foams, gels, lotions, powders, foundations, sprays, sticks, or aerosols. The daily care compositions are therapeutic daily care compositions because they contain a UV filter contained in the aqueous suspension (1) prepared in this invention.

[0040] The term "UV filter" or "ultraviolet filter" as used herein refers to an organic or inorganic compound that absorbs and further reflects and scatters UV radiation caused by sunlight. UV filters can be classified as UV-A, UV-B, or broadband filters based on their UV protection profile.

[0041] The water-soluble UV filter has a solubility in water of at least 2% by weight, preferably at least 3% by weight, and more preferably at least 5% by weight.

[0042] The prefix Cn-Cm indicates the possible number of carbon atoms in the group in each case.

[0043] The term "benzoic acid C12-C15 alkyl ester" refers to an ester of benzoic acid and a fatty alcohol containing a C12-C15 alkyl chain. A C12-C15 alkyl chain is defined as an alkyl chain having a C12, C13, C14 or C15 chain length.

[0044] The term "Cn-Cm carboxylic acid" as used herein refers in each case to a straight-chain or branched carboxylic acid having n to m carbon atoms (such as 6 to 24 carbon atoms).

[0045] The term "Cn-Cm alcohol" as used herein in each case means a straight-chain or branched-chain alcohol having n to m carbon atoms, such as having 3 to 24 carbon atoms, or 6 to 24 carbon atoms, or 1 to 22 carbon atoms.

[0046] The term "C2-C12 dicarboxylic acid" as used herein refers to a dicarboxylic acid having 2 to 12 carbon atoms in each case, such as succinic acid, pentanedioic acid, adipic acid, or decanedioic acid.

[0047] The term "dialkyl ether" as used herein in each case means a straight-chain or branched dialkyl ether having a total of 12 to 36 carbon atoms and comprising at least one ether moiety.

[0048] The term "C6-C22 alcohol carbonate" as used herein in each case refers to a straight-chain or branched-chain alcohol carbonate having 6 to 22 carbon atoms and containing at least one functional group consisting of a carbonyl group with two alkoxy groups attached to it.

[0049] The term "alkyl" as used herein in each case means, by way of example, a straight-chain or branched alkyl group having 1 to 18 carbon atoms. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tributyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl.

[0050] The term "alkoxy" as used herein in each case means a straight-chain or branched alkyl group bonded by an oxygen atom and generally having 1 to 20 carbon atoms. Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butyloxy, 2-butyloxy, isobutyloxy, tributyloxy, and the like.

[0051] The term "carboxyalkyl" as used herein includes carboxymethyl, carboxyethyl, carboxypropyl, carboxyisopropyl, carboxybutyl, carboxyisobutyl, carboxypentyl, carboxyhexyl, carboxyheptyl, carboxyoctyl, carboxyisooctyl, carboxynonyl, carboxydecyl, carboxyundecyl, carboxydodecyl, carboxytetradecyl, carboxyhexadecyl and carboxyoctadecyl, with carboxymethyl being preferred.

[0052] The term "cycloalkyl" as used herein in each case means a monocyclic cycloaliphatic group generally having 3 to 10 or 5 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl, or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0053] The term "substituted" as used herein means that the hydrogen atom bonded to the specified atom is replaced by a specified substituent, provided that the substitution results in a stable or chemically feasible compound. Unless otherwise indicated, the substituted atom may have one or more substituents, each of which is independently selected.

[0054] The term "emollient" refers to cosmetic-specific oils used to protect, moisturize, and lubricate the skin. The word emollient comes from the Latin word mollire (to soften). Generally, emollients prevent water from evaporating from the skin by forming a sealing coating. They can be classified into different groups depending on their polarity index.

[0055] The term "sensitive skin" refers to skin whose natural barrier function is weakened and has been broken by triggering factors. Triggering factors may be, for example, cold weather, extreme hot water, and key ingredients that may be contained in sunscreens or daily care compositions.

[0056] The term "Sun Protection Factor (SPF)" as used herein indicates the degree to which skin is protected primarily from UV-B radiation by a sunscreen composition. Specifically, the factor indicates how long protected skin can be exposed to sunlight without sunburn compared to untreated skin. For example, if a sunscreen composition with an SPF of 15 is applied evenly to the skin of a person who typically gets sunburned after 10 minutes in the sun, the sunscreen allows a skilled person to remain in the sun for 15 times longer. In other words, SPF 15 means that assuming the sunscreen is applied evenly in a thick dose of 2 mg / cm², 1 / 15 of the burning UV radiation will reach the skin.

[0057] The definition of "broadband" protection (also known as wide-area or broad-spectrum protection) is based on the "critical wavelength." For broadband coverage, both UV-B and UV-A protection must be provided. According to US requirements, a critical wavelength of at least 370 nm is required to achieve wide-area protection. In addition, the European Commission recommends that all sunscreens or cosmetic compositions should have a UV-A protection factor of at least one-third of the labeled sun protection factor (SPF). For example, if a sunscreen composition has an SPF of 30, then the UVA protection factor must be at least 10.

[0058] The term "critical wavelength" is defined as the wavelength at which the area under the UV protection curve (protection % per wavelength) accounts for 90% of the total area under the curve in the UV region (290 to 400 nm). For example, a critical wavelength of 370 nm indicates that the protection of the sunscreen composition is not limited to the wavelength of UV-B, i.e., the wavelength of 290 to 320 nm, but is extended to 370 nm in this way, achieving 90% of the total area under the protection curve in the UV region.

[0059] The term "application" refers to the application of sunscreen or daily care composition to human skin.

[0060] As used herein, the term "nanomaterials" follows the recommendation of European Commission 2011 / 696 / EU. Therefore, in nanomaterials, 50% or more of the particles, based on a size distribution based on quantity, are smaller than 100 nm, including constituent particles in aggregates or agglomerates. Since this 50% threshold is difficult to implement in conventional production, according to the spirit of the invention, non-nano UV absorber dispersions containing preferably less than 30% and more preferably less than 10% of particles smaller than 100 nm refer to a particle size distribution based on quantity.

[0061] The term "dispersion" as used herein refers to a system in which distributed particles of one material are dispersed in a continuous phase of another material. The two phases may be in the same or different material states. A particular subtype of dispersion is a "suspension," in which the solid portion is dispersed (i.e., insoluble) in a fluid.

[0062] The following describes a preferred embodiment of the method for manufacturing the aqueous suspension (1) and the aqueous suspension (1) and its uses. It should be understood that the preferred embodiments of the present invention are preferably alone or in combination with each other.

[0063] As indicated above, in one embodiment of the present invention, there is a method (1) for preparing an aqueous suspension of at least one organic UV filter having a particle size of DN30 of 100 nm or larger, the method comprising the step of grinding (2) a suspension (2) containing at least one organic UV filter in a mixture of water and hydrophobic additives at a temperature of 35 to 90°C in a grinding apparatus.

[0064] The particle size DN30 can be determined, for example, by transmission electron microscopy (TEM) or scanning electron microscopy (SEM), preferably by transmission electron microscopy (TEM). It should be understood that an organic UV filter having a particle size DN30 of 100 nm or larger can also be referred to as an organic UV filter, wherein less than 30% (quantity assessment) of the particles are less than 100 nm.

[0065] In a preferred embodiment A1 of the first state sample, the at least one organic UV filter in the aqueous suspension (1) preferably has a particle size DN10 of 100 nm or larger, preferably 0.1 to 0.4 µm, more preferably 0.1 to 0.2 µm, as measured by transmission electron microscopy; and / or preferably a particle size DN50 of 120 nm or larger, preferably 0.12 to 0.5 µm, more preferably 0.12 to 0.3 µm, as measured by transmission electron microscopy; and / or preferably a particle size DN90 of 200 nm or larger, preferably 0.2 to 1.0 µm, more preferably 0.2 to 0.5 µm, as measured by transmission electron microscopy; and / or a particle size Dv10 of greater than 0.1 µm, preferably 0.1 to 0.4 µm, as measured by laser diffraction; and / or a particle size of less than 2.2 µm, preferably less than 2.0 µm, as measured by laser diffraction. μm, preferably less than 1.5 µm, with Dv90, where Dv10 and Dv90 were measured using a Mastersizer 2000 from Malvern Panalytical.

[0066] In a preferred embodiment of the present invention, the at least one organic UV filter in the aqueous suspension (1) has a particle size Dv10 of greater than 0.1 µm to 0.4 µm, preferably 0.15 to 0.3 µm, as determined by laser diffraction using a Mastersizer 2000 from Malvern Panalytical; and / or a particle size Dv50 of 0.2 µm to 0.8 µm, preferably 0.4 to 0.6 µm, as determined by laser diffraction; and / or a particle size Dv90 of 0.5 µm to 3 µm, preferably 0.5 to 2.2 µm, as determined by laser diffraction.

[0067] In a preferred embodiment of the present invention, less than 10% (quantity assessment) of the particles are less than 100 nm. Preferably, the quantity assessment is determined by transmission electron microscopy.

[0068] In a preferred embodiment of the present invention, the particle population smaller than 100 nm in the aqueous suspension (1) is reduced during the grinding step. Preferably, the particle population smaller than 100 nm in the aqueous suspension (1) is reduced by increasing the temperature of the suspension (2) in the grinding apparatus. The terms "reduced" and "increased temperature" are used in comparison with a grinding step that produces an aqueous suspension (1) having DN30 of 99 nm or smaller.

[0069] In a preferred embodiment of the present invention, the temperature of the suspension (2) in the grinding step is in the range of 40 to 80°C, preferably 40 to 70°C, and particularly 45 to 65°C.

[0070] In a preferred embodiment of the present invention, the grinding step is performed for 1 to 40 hours, more preferably 2 to 17 hours, or 5 to 15 hours, or 6 to 12 hours.

[0071] In a preferred embodiment of the present invention, the hydrophobic additive is a cosmetic oil, preferably selected from the group consisting of: alcohols having 6 to 18 carbon atoms; C6-C24 carboxylic acids; esters of C6-C24 carboxylic acids and C3-C24 alcohols; esters of hydroxycarboxylic acids and C6-C24 alcohols; esters of carboxylic acids and polyols; liquid mono- / di- / tri-glycerol mixtures based on C6-C18 carboxylic acids; esters of C6-C24 alcohols and aromatic carboxylic acids or oxycarboxylic acids; tricarboxylic acid esters; C2-C12 dicarboxylic acids and alcohols having 1 to 22 carbon atoms or having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups. Esters of polyols containing alkyl groups; substituted cyclohexane; C6-C22 alcohol carbonates; symmetrical or asymmetric dialkyl ethers having a total of 12 to 36 carbon atoms; ring-opening products of epoxidized carboxylic acid esters and polyols; polysiloxanes; aliphatic or cycloalkanes; diol esters; and mixtures thereof, particularly selected from the group consisting of: esters of C6-C24 alcohols (preferably C10 to C17 alcohols) with aromatic carboxylic acids (preferably benzoic acid) or with hydroxycarboxylic acids (preferably lactic acid esters) or with oxycarboxylic acids (preferably acetopropionate esters); dicarboxylic acid esters, preferably di-n-butyl adipate; tricarboxylic acid esters, preferably tributyl citrate; and mixtures thereof.

[0072] Preferred C3-C24 alcohols include, for example, isopropanol, n-butanol, isobutanol, tripentanol, n-hexanol, 3-methyl-3-pentanol, n-heptanol, n-octanol, n-nonanol, 2-ethylhexanol, decyl alcohol / capric alcohol, n-undecyl alcohol, lauryl alcohol, myristol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0073] Preferred C6-C24 alcohols are, for example, n-hexanol, 3-methyl-3-pentanol, n-heptanol, n-octanol, n-nonanol, 2-ethylhexanol, decyl alcohol / capric alcohol, n-undecyl alcohol, lauryl alcohol, myristol, cetyl alcohol, stearyl alcohol, oleyl alcohol and betaine alcohol.

[0074] Preferably, it is an ester of a C6-C24 alcohol (preferably a C10-C20 alcohol, or even more preferably a C12 to C15 alcohol) and an aromatic carboxylic acid (especially benzoic acid). Finsolv® TN is recommended as a suitable ester of benzoic acid with a straight-chain and / or branched-chain C6-C22 alcohol.

[0075] Preferably, the substances are monoesters of carboxylic acids and alcohols having 3 to 24 carbon atoms. This group includes carboxylic acids having 6 to 24 carbon atoms (e.g., hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, isotride-canoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linolenic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, benzyl acid, and erucic acid) and their technical-grade mixtures (e.g., in the pressure removal of natural fats and oils, in the synthesis by Roelen's carbonylation). The esterification products of aldehydes obtained in the reduction of oxosynthesis or in the dimerization of unsaturated fatty acids and alcohols (e.g., isopropanol, hexanol, octanol, 2-ethylhexanol, decanol, lauryl alcohol, isotearyl alcohol, myristol, cetyl alcohol, palm oil alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, transoleyl alcohol, petroselinyl alcohol, linolenic acid alcohol, elaeostearyl alcohol, arachidonic acid alcohol, gadoleyl alcohol, betaine alcohol, erucyl alcohol, and brassidyl alcohol) and their technical-grade mixtures (e.g., obtained by high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes as monomers in the dimerization of unsaturated fatty alcohols via Roche carbonylation synthesis). Of particular importance are isopropyl myristate, C16-C18 alkyl isononanoate, 2-ethylhexyl stearate, cetyl oleate, tricaprylate, caprinate / caprylate, and n-butyl stearate.

[0076] Regarding suitable esters of hydroxycarboxylic acids and C6-C24 alcohols, dioctyl malate may be nominated.

[0077] Regarding suitable polyols, propylene glycol, dimer glycol or trimer glycol may be nominated.

[0078] Preferably, the triglyceride is based on a C6-C10 carboxylic acid.

[0079] Preferably, it is an ester of a C2-C10 dicarboxylic acid (more preferably C4-C8 dicarboxylic acid) and a dicarboxylic acid, and a straight-chain or branched-chain alcohol having 1 to 16 carbon atoms (more preferably 2 to 8 carbon atoms). Preferred dicarboxylic acid esters are di-n-butyl adipate, di-(2-ethylhexyl adipate), di-(2-ethylhexyl succinate), and diisotridecyl acetate.

[0080] Preferably, it is a straight or branched, symmetrical or asymmetric dialkyl ether having a total of 12 to 24 carbon atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether, n-hexyl-n-undecyl ether, di-tert-butyl ether, diisopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methylpentyl-n-octyl ether.

[0081] The preferred ester of C6-C24 alcohol and hydroxycarboxylic acid is lauryl lactate, and the preferred ester of C6-C24 alcohol and side-oxycarboxylic acid is lauryl acetate.

[0082] Preferred glycol esters are ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butylene glycol diisostearate and neopentyl glycol dioctanoate.

[0083] Preferred polyols are propylene glycol, hexanediol, glycerol and sorbitol.

[0084] In a preferred embodiment of the present invention, the hydrophobic additive is selected from alkyl benzoates, such as C12 to C15 alkyl benzoates (e.g., available from Cetiol AB), dibutyl adipate (e.g., Cetiol B), and mixtures thereof.

[0085] In a preferred embodiment of the present invention, the at least one organic UV filter is an insoluble organic UV filter. In this regard, it should be understood that the term insoluble UV filter refers to a UV filter that is insoluble in water and cosmetic oils at 25°C. Conversely, a water-soluble UV filter has a solubility of at least 2% by weight, preferably at least 3% by weight, and more preferably at least 5% by weight in water, and an oil-soluble UV filter has a solubility of at least 2% by weight, preferably at least 5% by weight, and more preferably at least 7% by weight in common cosmetic oils (such as C12-C15-alkyl benzoate, dibutyl adipate, diisopropyl sebacate, phenethyl benzoate, or dioctyl carbonate).

[0086] In a preferred embodiment of the present invention, the at least one organic UV filter is selected from the group consisting of oxadiphenylamine UV filter, triazine UV filter, piperazine UV filter, triazole UV filter, vinyl-containing oxadiamine UV filter, cinnamic acid oxadiamine UV filter, sulfonated benzimidazole and mixtures thereof.

[0087] In a preferred embodiment of the present invention, the at least one organic UV filter is selected from the group (1) of oxadiphenylamine UV filters having formula (1), wherein R1 and R2 are independently C1-C18 alkyl or C1-C18 alkoxy; and the triazine UV filter (2) having formula (2), wherein R3, R4 and R 5 is independently H; OH; C1-C18 alkoxy; NH2; NH-R6 or N(R6)2, wherein R6 is a C1-C18 alkyl; OR6, wherein R6 has the foregoing meaning; phenyl; phenoxy; aniline; pyrrole, wherein the corresponding phenyl, phenoxy, aniline or pyrrole moiety is substituted as needed by one, two or three of the following substituents: OH, carboxyl, CO-NH2, C1-C18 alkyl or -alkoxy, C1-C18 carboxyalkyl, C5-C8 cycloalkyl, phenyl, methylene camphoryl, group -(CH=CH)mC(=O)-OR6 (where m is 0 or 1 and R6 has the aforementioned meaning), or a group or corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4 alkylammonium, mono-, di- or tri-C2-C4 alkylammonium salt or its C1-C18 alkyl ester; phenyl bis-diphenyltriazine; piperazine UV filter; triazole UV filter having formula (31), (32) or (33) (31)(32)(33) where T1 is C1-C18 alkyl or hydrogen and T2 is C1-C18-alkyl, which is substituted with phenyl as needed; vinyl-containing amide UV filter having formula (4) (4) where R9 is C1-C18 alkyl or phenyl substituted with one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the aforementioned meaning); R10, R11, R12 and R 13 is the same or different and each is independently C1-C18 alkyl or hydrogen; Y is N or O; and m has the meaning of the foregoing; a cinnamic acid amide UV filter (5) having formula (5) wherein R 14 is hydroxyl or C1-C4 alkoxy; R 15 is hydrogen or C1-C4 alkyl; and R 16 is -(CONH)m-phenyl, wherein m has the meaning of the foregoing and the phenyl is substituted as needed by one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the meaning of the foregoing); a sulfonated benzimidazole UV filter (6) having formula (6) wherein M is hydrogen or alkali metal, alkaline earth metal or zinc; and mixtures thereof.

[0088] In a preferred embodiment of the present invention, the at least one organic UV filter is selected from the group (1) of oxadiphenylamine UV filters having formula (1), wherein R1 and R2 are independently C1-C18 alkyl or C1-C18 alkoxy; and the triazine UV filter (2) having formula (2), wherein R3, R4 and R 5 is independently H; OH; C1-C18 alkoxy; NH2; NH-R6 or N(R6)2, wherein R6 is a C1-C18 alkyl; OR6, wherein R6 has the foregoing meaning; phenyl; phenoxy; aniline; pyrrole, wherein the corresponding phenyl, phenoxy, aniline or pyrrole moiety is substituted as needed by one, two or three of the following substituents: OH, carboxyl, CO-NH2, C1-C18 alkyl or -alkoxy, C1-C18 carboxyalkyl, C5-C8 cycloalkyl, phenyl, methylene camphoryl, group -(CH=CH)mC(=O)-OR6 (where m is 0 or 1 and R6 has the foregoing meaning), or group or its C1-C18 alkyl ester; phenyl bis-diphenyltriazine; piperazine UV filter; triazole UV filter having formula (31), (32) or (33) (31)(32)(33) wherein T 1 is a C1-C18 alkyl or hydrogen and T2 is a C1-C18 alkyl, which is substituted with a phenyl group as needed; a vinyl-containing acetamide UV filter (4) having formula (4) wherein R9 is a C1-C18 alkyl or phenyl group substituted with one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (wherein R6 has the foregoing meaning); R10, R11, R12 and R13 are the same or different and each is independently a C1-C18 alkyl or hydrogen; Y is N or O; and m has the foregoing meaning; a cinnamic acid acetamide UV filter (5) having formula (5) wherein R14 is hydroxyl or C1-C4 alkoxy; R15 is hydrogen or C1-C4 alkyl; and R 16 is -(CONH)m-phenyl, wherein m has the foregoing meaning and the phenyl group is substituted as required by one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the foregoing meaning); a sulfonated benzimidazole UV filter of formula (6) wherein M is hydrogen; and mixtures thereof.

[0089] In a preferred embodiment of the present invention, the at least one organic UV filter is selected from the group consisting of: triphenyltriazine, 1,1'-(1,4-piperazinidyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methyl ketone, phenyl bis-diphenyltriazine, 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] and mixtures thereof, and in particular, wherein the at least one organic UV filter is selected from the group consisting of: triphenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

[0090] In a preferred embodiment of the present invention, the at least one organic UV filter is 2,2′-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

[0091] In a preferred embodiment of the present invention, the at least one organic UV filter is a broadband filter.

[0092] In a preferred embodiment of the present invention, the hydrophobic additive is included in the aqueous suspension (1) in an amount of 0.01 to 10.0% by weight, more preferably 0.01 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, and particularly 0.05 to 1.0% by weight.

[0093] In another preferred embodiment of the invention, the hydrophobic additive is included in the aqueous suspension (1) in an amount of 0.001 to 10.0% by weight, preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3.0% by weight, and particularly 0.2 to 1.0% by weight.

[0094] In a preferred embodiment of the present invention, the aqueous suspension (1) does not contain alkyl polyglucosides.

[0095] In a preferred embodiment of the present invention, the aqueous suspension (1) further comprises a dispersant.

[0096] Suitable dispersants are polyglycerol alkyl esters, preferably polyglycerol monoalkyl esters and alkyl polyglucosides, which preferably have the formula CnH2n+1O(C6H10O5)xH, where n is an integer in the range of 8 to 16 and x is the average degree of polymerization of the glucoside moiety (C6H10O) in the range of 1.4 to 1.6, or esters thereof. Other suitable dispersants are disclosed in WO2009068469.

[0097] According to the present invention, the polyglycerol monoalkyl ester preferably has an average degree of polymerization of 5 or greater.

[0098] In a preferred embodiment, the at least one polyglycerol monoalkyl ester is selected from the group consisting of decaglycerol decanoate, decaglycerol monolaurate, decaglycerol myristate, decaglycerol oleate, decaglycerol stearate, decaglycerol isostearate, hexaglycerol decanoate, hexaglycerol laurate, hexaglycerol myristate, hexaglycerol oleate, hexaglycerol stearate, hexaglycerol isostearate, pentaglycerol decanoate, pentaglycerol laurate, pentaglycerol myristate, pentaglycerol oleate, pentaglycerol stearate, pentaglycerol isostearate, and combinations thereof. In a particularly preferred embodiment, the at least one polyglycerol monoalkyl ester is decaglycerol monolaurate (INCI polyglycerol-10 laurate).

[0099] Polyglycerol monoalkyl esters with an HLB (hydrophilic-lipophilic balance) of 14.5 or greater are preferred, and those with an HLB of 15 or greater are even more preferred. The HLB value is determined by the following formula: HLB = 20 • M h / M, where M h is the molecular weight of the hydrophilic portion of the molecule and M is the molecular weight of the entire molecule.

[0100] Polyglycerol monoalkyl esters having an HLB of less than 14.5 may require a longer time to allow micronized methylenebis-benzotriazolyltetramethylbutylphenol to disperse in the aqueous phase. Examples of polyglycerol monoalkyl esters having an average degree of polymerization of 5 or greater or having an HLB of 14.5 or greater may include decaglycerol decanoate, decaglycerol monolaurate, decaglycerol myristate, decaglycerol oleate, decaglycerol stearate, decaglycerol isostearate, hexaglycerol laurate, pentaglycerol laurate, pentaglycerol myristate, pentaglycerol stearate and pentaglycerol oleate, and those having an HLB of 15 or greater may include decaglycerol decanoate and decaglycerol monolaurate.

[0101] The preferred form is polyglycerol monolaurate, especially decapolyglycerol monolaurate and decyl glucoside.

[0102] Preferably, the alkyl polyglucoside is a C1-C12 ester of a compound of the formula CnH2n+1O(C6H10O5)xH (i.e., an ester formed by reacting a C1-C12 carboxylic acid with one or more free OH groups on the glucosinolate moiety (C6H10O). More preferably, the ester is formed by reacting formic acid, acetic acid, propionic acid, butyric acid, sulfosuccinic acid, citric acid, or tartaric acid with one or more free OH groups on the glucosinolate moiety (C6H10O).

[0103] Preferably, the aqueous suspension (1) contains a dispersant in an amount of 1 to 15% by weight, more preferably 5 to 40% by weight, and particularly 6 to 20% by weight, based on the total weight of the aqueous suspension (1).

[0104] The weight ratio of the dispersant to at least one organic UV filter is preferably 0.05 to 0.5, more preferably 0.08 to 0.4, and particularly 0.1 to 0.3.

[0105] Other excipients may be added to the formulation, such as thickeners, defoamers, pH adjusters, and preservatives.

[0106] Examples of other excipients that can be used to prepare at least one micronized organic UV filter include rheology modifiers, solvents, pH adjusters or buffers, defoamers and preservatives.

[0107] Rheology modifiers can be added to the UV-protective composition as needed, which helps to stabilize the composition over time. Examples of water-based thickeners include natural ingredients and their derivatives (such as gums and alginates) or synthetic / semi-synthetic ingredients (such as modified starch, modified cellulose, and polyacrylates). A preferred rheology modifier is xanthan gum.

[0108] Suitable solvents for the grinding process are water, brine, (poly)ethylene glycol, glycerin, or cosmetically acceptable oils. Other suitable solvents are disclosed in the sections "Esters of Fatty Acids," "Natural and Synthetic Triglycerides, Including Glyceryl Esters and Derivatives," "Perlescent Waxes," "Hydrocarbon Oils," and "Polysiloxanes or Silicon Oxides" of IPCOM Nº000031257D. Preferred solvents are water, butanediol, and octanediol.

[0109] Suitable pH adjusters include NaOH, TEA and citric acid.

[0110] The suitable defoamer is simethicone.

[0111] The suitable preservative is COSING Annex V.

[0112] In a preferred embodiment of the present invention, the grinding step is carried out in a ball mill, a vibratory mill, a wet rotor mill, a stirred media mill, or a colloid mill, preferably a wet rotor mill or a stirred media mill, and particularly in a stirred media mill having grinding beads (preferably glass beads, zirconia beads, or mixed ceramic grinding beads) having a diameter of 0.1 to 10 mm, preferably 0.15 to 5 mm, and particularly 0.2 to 3 mm.

[0113] Preferably, the grinding beads are yttrium-stabilized zirconium oxide with high density and high sphericity.

[0114] The typical yttrium-stabilized zirconia grinding beads according to the present invention have the following properties: Chemical composition: 95% ZrO2, 5% Y2O3 Specific density: 6.1 g / cm3 Flexural strength: 1200 MPa Hardness (Hv10): 1250 Elastic modulus: 210 GPa Fracture toughness: 6.0 Mpamº Such grinding beads are available, for example, from Tosho Ceramics, Japan.

[0115] The method according to the present invention may also be called the micronization method.

[0116] Typically, the micronization method begins with the synthesis of a solid UV filter initial material, which is then processed as needed. Typical process steps involve, for example, crystallization or recrystallization steps to remove impurities or achieve a specific crystal structure, solid / liquid separation steps (such as filtration), purification steps (such as washing UV filter particles), and drying steps to remove residual solvents. Processing steps such as coalescence or re-coalescence may also be considered to improve flow behavior, increase the shelf life of the material, or reduce dust formation during processing. UV filter materials may be pre-milled to break up crystalline blocks or agglomerates or even break down crystals to smaller sizes. Preferably, UV filter materials can be used for micronization as powder or particles, but other solid forms (such as polycrystalline materials) may also be processed.

[0117] The UV filter material is then formulated into a liquid slurry suitable for wet milling. The slurry contains a solvent (preferably water) and a compound capable of wetting at least one organic UV filter solid in the solvent. The slurry is prepared in an apparatus that allows for the preparation of the liquid formulation, the incorporation of at least one organic UV filter, and the formation of a homogeneous dispersion for further processing. For wet milling, the slurry contains dispersants, such as surfactants, emulsifiers, and / or polymers capable of stabilizing crystal surfaces. These dispersants can be formulated into a slurry in a single step or metered into the slurry during the process. The slurry may contain other excipients, such as organic solvents, preservatives, pH adjusters or buffers, defoamers, etc.

[0118] In order to carry out the present invention, it is necessary to have a hydrophobic additive in the dispersion as it passes through the grinding device.

[0119] Micronization of at least one organic UV filter dispersion can be performed in more than one processing step. Depending on the properties of the at least one organic UV filter and the target particle size of the dispersion, the selected equipment may require specific properties of the slurry. For example, to operate a stirred ball mill, the maximum particle size in the dispersion must not be exceeded to prevent mill clogging. For this reason, pre-grinding devices, such as colloid mills, can be used, or more than one stirred ball mill can be used along the processing line. Experts familiar with this technology will be able to design equipment and processes in a way that achieves economical and efficient production.

[0120] In a preferred embodiment of the present invention, at least one organic UV filter in the suspension (2) has a particle size Dv90, as determined by laser diffraction, in the range of 0.01 to 300 µm, preferably 0.1 to 250 µm.

[0121] In principle, all apparatuses used for wet milling can be used to perform the present invention. Preferably, the particle size of the aqueous suspension (1) of the present invention, which includes at least one organic UV filter, is adjusted so that the product has high performance while safely satisfying non-nano properties during production. The shear / stress generated in a stirred ball mill can break the particles into nanoscale. However, the present invention can also be used to suppress the accumulation of nanoparticles that can be generated when at least one organic UV filter particle is subjected to impact forces, for example, in a wet rotor mill.

[0122] Preferably, the present invention is carried out in an apparatus for holding grinding beads (such as a stirred ball mill).

[0123] In a preferred embodiment of the present invention, a triggering mechanism is required to activate the effect of the hydrophobic additive. Specifically, the effect of the present invention occurs only at elevated product temperatures, which are provided by adjusting the product temperature in the grinding equipment to provide an effective on / off mechanism.

[0124] Without being constrained by theory, it is hypothesized that the combined effect of hydrophobic additives and temperature enhances the osmotic-ripening of UV absorber particles. This leads to the dissolution of nanoparticles and induces crystal growth, which counteracts the grinding action in the mill. Osmotic-ripening can then be effectively suppressed by cooling the dispersion after it leaves the mill. Experts familiar with this technology have found that combinations of process parameters can achieve non-nano particle size distributions within the target range.

[0125] As described above, the present invention further relates to an aqueous suspension (1) in the second state, comprising a) 10 to 65% by weight of at least one organic UV filter having a particle size of DN30 of 100 nm or larger, b) 0.01 to 10.0% by weight of a hydrophobic additive selected from the group consisting of: alcohols having 6 to 18 carbon atoms; C6-C24 carboxylic acids; esters of C6-C24 carboxylic acids and C3-C24 alcohols; esters of hydroxycarboxylic acids and C6-C24 alcohols; esters of carboxylic acids and polyols; liquid mono- / di- / tri-glycerol mixtures based on C6-C18 carboxylic acids; esters of C6-C24 alcohols and aromatic carboxylic acids or oxycarboxylic acids; tricarboxylic acid esters; esters of C2-C12 dicarboxylic acids and alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups; substituted cyclohexane; C6-C22 alcohol carbonates; symmetrical or asymmetrical dialkyl ethers having a total of 12 to 36 carbon atoms; ring-opening products of epoxidized carboxylic acid esters and polyols; polysiloxane oils; aliphatic or cycloalkanes; diol esters; and mixtures thereof, and c) All water amounts are based on the total amount of aqueous suspension (1).

[0126] In a preferred embodiment of the present invention, the hydrophobic additive is selected from the group consisting of: esters of C6-C24 alcohols (preferably C10 to C17 alcohols) with aromatic carboxylic acids (preferably benzoic acid) or with hydroxycarboxylic acids (preferably lactate) or with oxycarboxylic acids (preferably acetylpropionate); dicarboxylic acid esters, preferably di-n-butyl adipate; tricarboxylic acid esters, preferably tributyl citrate; and mixtures thereof.

[0127] In a preferred embodiment of the present invention, the at least one organic UV filter is an insoluble organic UV filter, preferably selected from the group consisting of: oxadiphenylamine UV filter, triazine UV filter, piperazine UV filter, triazole UV filter, vinyl-containing oxadiamine UV filter, cinnamic acid oxadiamine UV filter, sulfonated benzimidazole and mixtures thereof, more preferably selected from the group consisting of: oxadiphenylamine UV filter (1) having formula (1) wherein R1 and R2 are independently C1-C18 alkyl or C1-C18 alkoxy; triazine UV filter (2) having formula (2) wherein R3, R4 and R 5 is independently H; OH; C1-C18 alkoxy; NH2; NH-R6 or N(R6)2, wherein R6 is a C1-C18 alkyl; OR6, wherein R6 has the foregoing meaning; phenyl; phenoxy; aniline; pyrrole, wherein the corresponding phenyl, phenoxy, aniline or pyrrole moiety is substituted as needed by one, two or three of the following substituents: OH, carboxyl, CO-NH2, C1-C18 alkyl or -alkoxy, C1-C18 carboxyalkyl, C5-C8 cycloalkyl, phenyl, methylene camphoryl, group -(CH=CH)mC(=O)-OR6 (where m is 0 or 1 and R6 has the aforementioned meaning), or a group or corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4 alkylammonium, mono-, di- or tri-C2-C4 alkylammonium salt or its C1-C18 alkyl ester; phenyl bis-diphenyltriazine; piperazine UV filter; triazole UV filter having formula (31), (32) or (33) (31)(32)(33) where T1 is C1-C18 alkyl or hydrogen and T2 is C1-C18-alkyl, which is substituted with phenyl as needed; vinyl-containing amide UV filter having formula (4) (4) where R9 is C1-C18 alkyl or phenyl substituted with one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the aforementioned meaning); R10, R11, R12 and R 13 is the same or different and each is independently C1-C18 alkyl or hydrogen; Y is N or O; and m has the meaning of the foregoing; a cinnamic acid amide UV filter (5) having formula (5) wherein R 14 is hydroxyl or C1-C4 alkoxy; R 15 is hydrogen or C1-C4 alkyl; and R 16 is -(CONH)m-phenyl, wherein m has the meaning of the foregoing and the phenyl is substituted as needed by one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the meaning of the foregoing); a sulfonated benzimidazole UV filter (6) having formula (6) wherein M is hydrogen or alkali metal, alkaline earth metal or zinc;And mixtures thereof, or even more preferably, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine, 1,1'-(1,4-piperazinidyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methyl ketone, phenyl bis-diphenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol], and particularly, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

[0128] In a preferred embodiment of the present invention, the aqueous suspension (1) contains 0.01 to 8.0% by weight, more preferably 0.01 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, and particularly 0.05 to 1.0% by weight of hydrophobic additives.

[0129] In another preferred embodiment of the invention, the hydrophobic additive is included in the aqueous suspension (1) in an amount of 0.05 to 5.0% by weight, preferably 0.1 to 3.0% by weight, and particularly 0.2 to 1.0% by weight, based on the total amount of the aqueous suspension (1).

[0130] In a preferred embodiment of the present invention, at least one organic UV filter in the aqueous suspension preferably has a particle size DN10 of 100 nm or larger, preferably 0.1 to 0.4 µm, more preferably 0.1 to 0.2 µm, as measured by transmission electron microscopy; and / or preferably a particle size DN50 of 120 nm or larger, preferably 0.12 to 0.5 µm, more preferably 0.12 to 0.3 µm, as measured by transmission electron microscopy; and / or preferably a particle size DN90 of 200 nm or larger, preferably 0.2 to 1.0 µm, more preferably 0.2 to 0.5 µm, as measured by transmission electron microscopy; and / or a particle size Dv10 of greater than 0.1 µm, preferably 0.1 to 0.4 µm, as measured by laser diffraction; and / or a particle size of less than 2.2 µm, preferably less than 2.0 µm, more preferably less than 1.5 µm, as measured by laser diffraction. The particle size Dv90 is µm, where Dv10 and Dv90 were measured using a Mastersizer 2000 from Malvern Panalytical.

[0131] In a preferred embodiment of the present invention, the at least one organic UV filter has a particle size DN10 of 100 nm or larger, preferably 0.1 to 0.4 µm, more preferably 0.1 to 0.2 µm as measured by transmission electron microscopy; and / or a particle size DN50 of 150 nm or larger, preferably 0.15 to 0.5 µm, more preferably 0.15 to 0.3 µm as measured by transmission electron microscopy; and / or a particle size DN90 of 200 nm or larger, preferably 0.2 to 1.0 µm, more preferably 0.2 to 0.5 µm as measured by transmission electron microscopy; and / or a particle size Dv10 of greater than 0.1 µm as measured by laser diffraction; and / or a particle size Dv90 of less than 2.2 µm as measured by laser diffraction.

[0132] In a preferred embodiment of the present invention, the at least one organic UV filter has a specific surface area of ​​8 to 32 m² / g, preferably 10 to 30 m² / g, and particularly 13 to 28 m² / g, as determined by laser diffraction.

[0133] Other preferred embodiments of hydrophobic additives, at least one organic UV filter, dispersant, other excipients and the like, and the amounts of the remaining components have been described above and are also applied to aqueous suspensions (1).

[0134] As described above, the present invention further relates to the aqueous suspension (1) described herein in the third state sample, which is used in sunscreens or daily care compositions.

[0135] It should be understood that preferred embodiments and amounts of components of the aqueous suspension (1) (such as hydrophobic additives, at least one organic UV filter, dispersant, other excipients and the like) have already been described above and are also used in this application.

[0136] The sunscreens or daily care compositions described herein are suitable for application to any skin type, and are particularly suitable for application to sensitive skin. Example Comparative Example A Micronization of a 2,2′-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] (also known as methylenebis-benzotriazolyltetramethylbutylphenol and MBBT) dispersion

[0137] 600 g of Plantacare® 2000 UP (an alkyl polyglucan solution, wherein the alkyl polyglucan is decyl glucan, 50% of the active material, from BASF) was dissolved in 1400 g of deionized water. 2000 g of Tinosorb MBBT (MBBT, from BASF) was added to this solution and homogenized. The dispersion was then milled at 26°C in a stirred ball mill (Dyno Mill Multilab, from Bachofen) equipped with a 1.4 L milling vessel and ceramic disc. 2 mm glass beads were used as milling beads, and the dispersion was circulated through the mill during the milling process. The process was stopped after 90 minutes, with a total milling energy of 0.93 kWh. The product was separated from the milling beads.

[0138] Volume-based particle size distribution was determined by laser diffraction (Mastersizer 2000, Malvern Panalytical). Specific absorbance E(1,1) was measured using a Lambda 25 spectrometer equipped with an Ulbricht Kugel. E(1,1) is related to the UV filter performance of the dispersion. Specific surface area (SSA) was determined by laser diffraction (Mastersizer 2000, Malvern Panalytical). Results: Particle size (volume-based): Dv10 - Dv50 - Dv90 (nm) = 85 - 205 - 1583; SSA = 33.9 m² / g; E(1,1) = 329

[0139] In the following examples, UV absorber 1 represents MBBT as in Example 1, UV absorber 2 represents 2,4,6-triazine [1,1'-diphenyl]-4-yl-1,3,5-triazine, UV absorber 3 represents bis-(diethylaminohydroxybenzoylbenzoyl)piperazine, and UV absorber 4 represents 3,3'-(1,4-epenylphenyl)bis(5,6-diphenyl-1,2,4-triazine). Wet milling of UV absorber dispersions in Comparative Examples B1 to B10

[0140] UV absorbers were micronized using different formulations and grinding equipment. The micronization process was monitored during the grinding process by collecting two samples (a) and (b). Volume-based particle size distribution was obtained by laser diffraction. The results are summarized in Table 1. Table 1: Different grinding conditions and their results; PSD results are volume-based. serial number Composition (weight %) Grinding equipment Laser diffraction D V10-D V 50-D V 90 (nm); SSA (m² / g) UV absorber 1 B1 50% UV absorber, 1.8% alkyl polyglucoside, water to 100 Dyno Multilab; Y-ZrO2 beads, 1.4 to 1.6 mm a) 98 – 848 – 3210; 23.1 b) 83 – 211 – 2129; 32.9 B2 50% UV absorber 1, 7.5% alkyl polyglucoside, water to 100 Dyno Multilab; Y-ZrO2 beads, 0.6 to 0.8 mm a) 78 – 205 – 1943 b) 70 – 150 – 1100 B3 50% UV absorber, 1.5% sodium cocoyl glutamate, 0.5% octane glycol, 0.01% defoamer, water to 100% beaker mill; Glass beads, 1 mm a) 83 – 205 – 724; 36.8 b) 77 – 159 – 349; 43.5 B4 50% UV absorber, 1.8% decaglycerol monolaurate, 7% butylene glycol, water to 100% Dyno Multilab; Y-ZrO2 beads, 1.0 to 1.2 mm a) 91 – 972 – 4571; 24.6 b) 86 – 268 – 2975; 30.2 UV absorber 2 B5 50% UV absorber 2, 7.5% alkyl polyglucoside, water to 100 Dyno Multilab; Y-ZrO2 beads, 0.3 to 0.4 mm a) 97 – 523 – 1978; 24.3 b) 81 – 195 – 1142; 37.8 B6 50% UV absorber 2, 10% lauryl alkoxylate, water to 100 beaker mill; Glass beads, 0.5 to 0.8 mm a) 112 – 615 – 1584; 20.5 b) 111 – 249 – 541; 29.2 UV absorber 3 B7 50% UV absorber, 3.6% alkyl polyglucoside, 1% sodium lauryl myristyl ether sulfate, 0.2% defoamer, water to 100% LMZ 10; Y-ZrO2 beads, 0.3 to 0.4 mm a) 62 – 140 – 724 b) 58 – 91 – 168 B8 50% UV absorber, 3.5% disodium C12-18 alkyl sulfosuccinate, 1% sodium cocoyl hydrolysate, and water to 100%. Dyno Multilab; Y-ZrO2 beads, 1.0 to 1.2 mm a) 83 – 273 – 1834; 23.9 b) 71 – 138 – 905; 35.6 B9 50% UV absorber, 3.5% sodium cocoyl glutamate, 1% sodium cocoyl glutamate hydrolyzed wheat protein, water to 100 beaker mill; Y-ZrO2 beads, 1.0 to 1.2 mm a) 80 – 169 – 1241; 28.6 b) 70 – 131 – 574; 37.8 UV absorber 4 B10 50% UV absorber 4, 10% lauryl alkoxylate, water to 100 beaker mill; Y-ZrO2 beads, 1.0 to 1.2 mm a) 69 – 126 – 757; 38.7 b) 63 – 109 – 194; 46.7

[0141] The micronization of the UV absorber dispersion was carried out using different equipment and formulations. The micronization process was observed in a decrease in PSD results (especially Dv50 and Dv90) and an increase in SSA. Due to the limited sensitivity of laser diffraction to nanoparticles, the Dv10 value decreased only slightly. Comparative Example C1

[0142] The micronized dispersion containing 50% UV absorber 1 and 7.5% alkyl polyglucoside was analyzed by laser diffraction and TEM. The results are summarized in Table 2. The grinding process was carried out using Y-ZrO2 beads in a stirred media mill (LMZ). Table 2: Comparison of PSD (laser diffraction) and PSD (TEM) values ​​of sample C1. Example PSD (Laser Diffraction) D V 10-D V 50-D V 90 (nm); SSA (m² / g) PSD (TEM) Quantity distribution Material C1 99-326-2400; 26 D N 50: 115.5 nm Particles < 100 nm: 37%

[0143] TEM analysis yields quantity distributions suitable for application to nanomaterials according to standard 2011 / 696 / EU.

[0144] The results confirm that even with a Dv10 of approximately 100 nm and a Dv90 much higher than 2 µm from laser light diffraction, material C1 represents a boundary / near-nanometer scheme. A comparison with Table 1 shows that most or all of the materials in Examples B1 to B10 are nanomaterials. Comparative Examples C2 to C4: Addition of Oil

[0145] Material C1 is used as a starting material.

[0146] Oil was added to Examples C2 through C4, and the grinding process continued. All experiments were conducted using a beaker mill with 2 mm glass beads. The temperature of the product was controlled during the grinding process. Samples were collected and PSD was measured at specified grinding durations (e.g., 4 hours). Table 3: Addition of sunflower oil; PSD results are based on volume. serial number Added oil relative to C1 weight % T(°C) Laser diffraction D V 10-D V 50-D V 90 (nm); SSA (m² / g) C2 No additives 49 2 hours 20 minutes: 93 -257- 1584; 29.9 5 hours 20 minutes: 94 -240-1120; 31.4 8 hours: 90 -225- 863; 33.5 C3 0.1% sunflower oil 49 10 to 12 hours: 22℃ 4 hours: 94 -241-1136; 31.4 8 hours: 86 -210- 681; 35.9 10 hours: 82 -197- 513; 38.1 12 hours: 80 -188- 455; 39.7 C4 0.5% sunflower oil 52 10 to 12 hours: 22℃ 4 hours: 93 -236- 1075; 32.0 8 hours: 85 -207- 582; 36.4 10 hours: 80 -190- 462; 39.4 12 hours: 79 -183- 422; 40.7

[0147] Adding a small amount of sunflower oil has no significant effect on the micronization process. PSD decreases with milling duration, regardless of the product temperature in the mill. Examples C5 to C10 of the present invention.

[0148] Material C1 is used as a starting material.

[0149] Oil was added to Examples C5 through C10 and the grinding process continued. All experiments were conducted using a beaker mill with 2 mm glass beads. The temperature of the product was controlled during the grinding process. Samples were collected and PSD was measured at specified grinding durations (e.g., 2 hours). Table 4: Addition of Cetiol AB (C12-15 alkyl benzoate); PSD results are based on volume. serial number Added oil relative to C1 weight % T(°C) Laser diffraction D V 10-D V 50-D V 90 (nm); SSA (m² / g) C5 0.1% Cetiol AB 54 2 hours: 102-280-1710; 27.4 5 hours 30 hours: 96-245-1170; 30.8 7 hours: 95-241-1000; 31.5 9 hours and 30 minutes: 134-298-1070; 23.8 C6 0.25% Cetiol AB 52 2 hours: 105-293-1850; 26.3 5 hours 30 minutes: 103-266-1460; 28.3 7 hours: 102-259-1240; 29.0 9 hours and 30 minutes: 141-308-1130; 22.6 C7 0.5% Cetiol AB 60 2 hours: 107-311-2110; 25.3 5 hours 30 minutes: 204-492-2100; 14.3

[0150] In contrast to Examples C2 to C4, D V50 and D V90 decrease less during the short grinding duration. As the process continues, D V10 and D V50 begin to increase, which is attributed to particle growth during the micronization process.

[0151] Further analysis of the final material obtained in instance C7.

[0152] E(1,1) was determined using a Lambda 25 spectrometer equipped with an Ulbricht Kugel.

[0153] TEM analysis was performed to obtain quantity-based particle size distribution and particle morphology. The results are summarized in Table 5. Table 5: Comparison of PSD (laser diffraction) and PSD (TEM) values ​​of sample C7. PSD (Laser Diffraction) D V 10-D V 50-D V 90 (nm); SSA (m² / g) PSD (TEM) Quantity distribution E(1,1) Material C7 204-492-2100; 14.3 D N 10: 152.2 nm D N 50: 277.4 nm Particles < 100 nm: 2.8% 211

[0154] TEM revealed that the particles in sample C7 were crystalline, and no aggregates were detected. Nanoparticles were almost non-existent, which corresponds to the strong increase in the Dv10 value obtained by laser diffraction.

[0155] This confirms that the fraction of nanoparticles < 100 nm can be reduced by using the process according to the present invention. A non-nano UV filter dispersion with good performance is achievable. Table 6: Addition of Cetiol B (dibutyl adipate); PSD results are based on volume. serial number Added oil relative to C1 weight % T(°C) Laser diffraction D V 10-D V 50-D V 90 (nm); SSA (m² / g) C8 0.5% Cetiol B 54 3 hours: 102-280-1620; 27.3 5 hours 30 minutes: 148-339-1330; 20.5 6 hours 30 minutes: 159-349-1280; 19.5 C9 0.5% Cetiol B Temperature rises after 8 hours 31 49 to 50 4 hours: 96-250-1217; 30.3 8 hours: 88-219-770; 34.6 11 hours 30 minutes: 83-201-541; 37.5 C10 0.5% Cetiol B The temperature dropped after 8 hours 52 35 4 hours: 152-345-1338; 20 8 hours: 184-368-1196; 17.7 11 hours 30 minutes: 150-304-912; 22

[0156] At elevated temperatures of 52 to 54°C, Cetiol B exhibits effects similar to Cetiol AB. Examples D1 to D4 according to the invention...

[0157] Oil was added to an MBBT suspension containing 50% MBBT, water, and polyglycerol laurate. The suspension was micronized using 2 mm glass beads (in Examples D1 and D2) and 0.6 to 0.8 mm Y-stabilized ZrO2 beads (in Examples D3 and D4). Particle size was measured before oil addition and after the times shown in the table. In Example D1, the temperature of the suspension was increased after the first sample was collected. Table 7: Milling of UV absorber 1 at different temperatures and oil concentrations; PSD results are based on volume. serial number Added oil relative to CO weight % T(°C) Laser diffraction D V 10-D V 50-D V 90 (nm); SSA (m² / g) D1 10% Polyglycerol Laurate and 0.3% Cetiol B 30 61 Start: 76-178-834; 41.2 2 hours 30 minutes: 161-324-1030; 20.4 D2 10% Polyglycerol Laurate and 0.4% Cetiol AB 56 56 Start: 78-191-1414; 38.5 3 hours 15 minutes: 134-286-1037; 24.2 D3 8.5% Polyglycerol Laurate and 0.6% Cetiol AB 46 48 Start: 85-210-697; 36.0 3 hours and 50 minutes: 111-249-625; 29.1 D4 8.5% Polyglycerol Laurate and 0.6% Cetiol AB 48 49 Start: 97-252-1200 30.1 1 hour 10 minutes: 145-318-1200; 21.5

[0158] Milling MBBT on a PSD in a polyglycerol laurate solution containing oil at elevated temperatures exhibits a similar effect to that in Example C7. According to Examples D5 to D6 of the present invention, dispersions containing 50% UV absorber 2, deca-polyglycerol monolaurate, and oil were micronized under different conditions using 0.6 to 0.8 mm Y-ZrO2 beads. Table 8: Milling of UV absorber 2 in a polyglycerol laurate solution containing added oil at different temperatures and oil concentrations; PSD results are based on volume. serial number UV absorber 2 suspension T(°C) Laser diffraction D V 10-D V 50-D V90 (nm); SSA (m² / g) D5 11% Polyglycerol Laurate and 0.6% Cetiol AB 49 53 52 Start: 126-1600-4000; 14.3 1 hour 00 minutes: 96-807-2010; 22.8 2 hours 00 minutes: 240-657-1900; 20.4 D6 11% Polyglycerol Laurate and 0.3% Cetiol AB 46 47 47 47 Start: 97-888-2200; 21.8 1 hour 00 minutes: 202-450-1800; 15.1 1 hour 55 minutes: 143-297-1300; 22.5 2 hours 20 minutes: 126-267-787; 26.1

[0159] Milling TBPT onto PSD in a polyglycerol laurate solution containing added oil at elevated temperatures exhibits a similar effect to that in Example C7. Shelf life stability

[0160] The product obtained in Example C7 was stored at 40°C for 5 weeks, and the particle size was measured using laser diffraction. PSD, initial: D V10- D V50- D V90 (nm): 159-349-1280; SSA (m² / g): 19.5 PSD, 5wks@40°C: D V10- D V50- D V90 (nm): 169-366-1250; SSA (m² / g): 18.4

Claims

1. A method for manufacturing an aqueous suspension (1) of at least one organic UV filter having a particle size DN30 of 100 nm or larger, the method comprising the step of grinding (2) a suspension (2) containing the at least one organic UV filter in a mixture of water and a hydrophobic additive in a grinding apparatus at a temperature of 35 to 90°C.

2. The method of claim 1, wherein the at least one organic UV filter in the aqueous suspension (1) preferably has a particle size DN10 of 100 nm or larger, preferably 0.1 to 0.4 µm, more preferably 0.1 to 0.2 µm, as determined by transmission electron microscopy; and / or preferably a particle size DN50 of 120 nm or larger, preferably 0.12 to 0.5 µm, more preferably 0.12 to 0.3 µm, as determined by transmission electron microscopy; and / or preferably a particle size DN90 of 200 nm or larger, preferably 0.2 to 1.0 µm, more preferably 0.2 to 0.5 µm, as determined by transmission electron microscopy; and / or a particle size Dv10 of greater than 0.1 µm, preferably 0.1 to 0.4 µm, as determined by laser diffraction; and / or a particle size of less than 2.2 µm, preferably less than 2.0 µm, as determined by laser diffraction. μm, preferably less than 1.5 µm, with Dv90, where Dv10 and Dv90 were measured using a Mastersizer 2000 from Malvern Panalytical.

3. As in request item 1 or 2, wherein, During the grinding step, the population of particles smaller than 100 nm in the aqueous suspension (1) is reduced. Preferably, the population of particles smaller than 100 nm in the aqueous suspension (1) is reduced by increasing the temperature of the suspension (2) in the grinding apparatus.

4. The method of any one of claims 1 to 3, wherein the temperature in the grinding step is in the range of 40 to 80°C, preferably 40 to 70°C, and particularly in the range of 45 to 65°C.

5. The method of any one of claims 1 to 4, wherein the hydrophobic additive is a cosmetic oil, preferably selected from the group consisting of: alcohols having 6 to 18 carbon atoms; C6-C24 carboxylic acids; esters of C6-C24 carboxylic acids and C3-C24 alcohols; esters of hydroxycarboxylic acids and C6-C24 alcohols; esters of carboxylic acids and polyols; liquid mono- / di- / tri-glycerol mixtures based on C6-C18 carboxylic acids; esters of C6-C24 alcohols and aromatic carboxylic acids or oxycarboxylic acids; tricarboxylic acid esters; C2-C12 dicarboxylic acids and alcohols having 1 to 22 carbon atoms or having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups. Esters of polyols containing alkyl groups; substituted cyclohexane; C6-C22 alcohol carbonates; symmetrical or asymmetric dialkyl ethers having a total of 12 to 36 carbon atoms; ring-opening products of epoxidized carboxylic acid esters and polyols; polysiloxanes; aliphatic or cycloalkanes; diol esters; and mixtures thereof, particularly selected from the group consisting of: esters of C6-C24 alcohols (preferably C10 to C17 alcohols) with aromatic carboxylic acids (preferably benzoic acid) or with hydroxycarboxylic acids (preferably lactic acid esters) or with oxycarboxylic acids (preferably acetopropionate esters); dicarboxylic acid esters, preferably di-n-butyl adipate; tricarboxylic acid esters, preferably tributyl citrate; and mixtures thereof.

6. The method of any one of claims 1 to 5, wherein the at least one organic UV filter is an insoluble organic UV filter, preferably selected from the group consisting of: oxadiphenylamine UV filter, triazine UV filter, piperazine UV filter, triazole UV filter, vinyl-containing oxadiamine UV filter, cinnamic acid oxadiamine UV filter, sulfonated benzimidazole and mixtures thereof, more preferably selected from the group consisting of: oxadiphenylamine UV filter (1) having formula (1) wherein R1 and R2 are independently C1-C18 alkyl or C1-C18 alkoxy; triazine UV filter (2) having formula (2) wherein R3, R4 and R 5 is independently H; OH; C1-C18 alkoxy; NH2; NH-R6 or N(R6)2, wherein R6 is a C1-C18 alkyl; OR6, wherein R6 has the foregoing meaning; phenyl; phenoxy; aniline; pyrrole, wherein the corresponding phenyl, phenoxy, aniline or pyrrole moiety is substituted as needed by one, two or three of the following substituents: OH, carboxyl, CO-NH2, C1-C18 alkyl or -alkoxy, C1-C18 carboxyalkyl, C5-C8 cycloalkyl, phenyl, methylene camphoryl, group -(CH=CH)mC(=O)-OR6 (where m is 0 or 1 and R6 has the aforementioned meaning), or a group or corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4 alkylammonium, mono-, di- or tri-C2-C4 alkylammonium salt or its C1-C18 alkyl ester; phenyl bis-diphenyltriazine; piperazine UV filter; triazole UV filter having formula (31), (32) or (33) (31)(32)(33) where T1 is C1-C18 alkyl or hydrogen and T2 is C1-C18-alkyl, which is substituted with phenyl as needed; vinyl-containing amide UV filter having formula (4) (4) where R9 is C1-C18 alkyl or phenyl substituted with one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the aforementioned meaning); R10, R11, R12 and R 13 is the same or different and each is independently C1-C18 alkyl or hydrogen; Y is N or O; and m has the meaning of the foregoing; a cinnamic acid amide UV filter (5) having formula (5) wherein R 14 is hydroxyl or C1-C4 alkoxy; R 15 is hydrogen or C1-C4 alkyl; and R 16 is -(CONH)m-phenyl, wherein m has the meaning of the foregoing and the phenyl is substituted as needed by one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the meaning of the foregoing); a sulfonated benzimidazole UV filter (6) having formula (6) wherein M is hydrogen or alkali metal, alkaline earth metal or zinc;And mixtures thereof, or even more preferably, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine, 1,1'-(1,4-piperazinidyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methyl ketone, phenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol], and particularly, wherein the at least one organic UV filter is selected from the group consisting of phenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

7. The method of any one of claims 1 to 6, wherein the hydrophobic additive is included in the aqueous suspension (1) in an amount of 0.01 to 10.0% by weight, preferably 0.01 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, and particularly 0.05 to 1.0% by weight.

8. The method of any one of claims 1 to 7, wherein the grinding step is carried out in a ball mill, a vibratory mill, a wet rotor mill, a stirred media mill, or a colloid mill, preferably a wet rotor mill or a stirred media mill, and particularly in a stirred media mill having grinding beads, preferably glass beads, zirconia beads, or mixed ceramic grinding beads, the beads having a diameter of 0.1 to 10 mm, preferably 0.15 to 5 mm, and particularly 0.2 to 3 mm.

9. The method of any one of claims 1 to 8, wherein at least one organic UV filter in the suspension (2) has a particle size Dv90, as determined by laser diffraction, in the range of 0.01 to 300 µm, preferably 0.1 to 250 µm.

10. An aqueous suspension (1) comprising a) 10 to 65% by weight of at least one organic UV filter having a particle size of DN30 of 100 nm or larger; b) 0.01 to 10.0% by weight of a hydrophobic additive selected from the group consisting of: alcohols having 6 to 18 carbon atoms; C6-C24 carboxylic acids; esters of C6-C24 carboxylic acids and C3-C24 alcohols; esters of hydroxycarboxylic acids and C6-C24 alcohols; esters of carboxylic acids and polyols; liquid mono- / di- / tri-glycerol ester mixtures based on C6-C18 carboxylic acids; esters of C6-C24 alcohols and aromatic carboxylic acids or oxycarboxylic acids; tricarboxylic acid esters; esters of C2-C12 dicarboxylic acids and alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups; substituted cyclohexane; C6-C22 alcohol carbonates; symmetrical or asymmetric dialkyl ethers having a total of 12 to 36 carbon atoms; ring-opening products of epoxidized carboxylic acid esters and polyols; polysiloxane oils; aliphatic or cycloalkanes; diol esters; and mixtures thereof, and c) All water amounts are based on the total amount of the aqueous suspension (1).

11. The aqueous suspension of claim 10, wherein the hydrophobic additive is selected from the group consisting of: esters of C6-C24 alcohols (preferably C10 to C17 alcohols) with aromatic carboxylic acids (preferably benzoic acid) or with hydroxycarboxylic acids (preferably lactate) or with oxycarboxylic acids (preferably acetopropionate); dicarboxylic acid esters, preferably di-n-butyl adipate; tricarboxylic acid esters, preferably tributyl citrate; and mixtures thereof.

12. The aqueous suspension (1) of claim 10 or 11, wherein the at least one organic UV filter is an insoluble organic UV filter, preferably selected from the group consisting of: oxadiphenylamine UV filter, triazine UV filter, piperazine UV filter, triazole UV filter, vinyl-containing oxadiamine UV filter, cinnamic acid oxadiamine UV filter, sulfonated benzimidazole and mixtures thereof, more preferably selected from the group consisting of: oxadiphenylamine UV filter (1) having formula (1) wherein R1 and R2 are independently C1-C18 alkyl or C1-C18 alkoxy; triazine UV filter (2) having formula (2) wherein R3, R4 and R 5 is independently H; OH; C1-C18 alkoxy; NH2; NH-R6 or N(R6)2, wherein R6 is a C1-C18 alkyl; OR6, wherein R6 has the foregoing meaning; phenyl; phenoxy; aniline; pyrrole, wherein the corresponding phenyl, phenoxy, aniline or pyrrole moiety is substituted as needed by one, two or three of the following substituents: OH, carboxyl, CO-NH2, C1-C18 alkyl or -alkoxy, C1-C18 carboxyalkyl, C5-C8 cycloalkyl, phenyl, methylene camphoryl, group -(CH=CH)mC(=O)-OR6 (where m is 0 or 1 and R6 has the aforementioned meaning), or a group or corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4 alkylammonium, mono-, di- or tri-C2-C4 alkylammonium salt or its C1-C18 alkyl ester; phenyl bis-diphenyltriazine; piperazine UV filter; triazole UV filter having formula (31), (32) or (33) (31)(32)(33) where T1 is C1-C18 alkyl or hydrogen and T2 is C1-C18-alkyl, which is substituted with phenyl as needed; vinyl-containing amide UV filter having formula (4) (4) where R9 is C1-C18 alkyl or phenyl substituted with one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the aforementioned meaning); R10, R11, R12 and R 13 is the same or different and each is independently C1-C18 alkyl or hydrogen; Y is N or O; and m has the meaning of the foregoing; a cinnamic acid amide UV filter (5) having formula (5) wherein R 14 is hydroxyl or C1-C4 alkoxy; R 15 is hydrogen or C1-C4 alkyl; and R 16 is -(CONH)m-phenyl, wherein m has the meaning of the foregoing and the phenyl is substituted as needed by one, two or three substituents selected from OH, C1-C18 alkyl, C1-C18 alkoxy or CO-OR6 (where R6 has the meaning of the foregoing); a sulfonated benzimidazole UV filter (6) having formula (6) wherein M is hydrogen or alkali metal, alkaline earth metal or zinc;And mixtures thereof, or even more preferably, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine, 1,1'-(1,4-piperazinidyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methyl ketone, phenyl bis-diphenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol], and particularly, wherein the at least one organic UV filter is selected from the group consisting of: phenyltriazine and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

13. The aqueous suspension (1) of any one of claims 10 to 12, wherein the aqueous suspension (1) contains the hydrophobic additive in an amount of 0.01 to 8.0% by weight, more preferably 0.01 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, and particularly in an amount of 0.05 to 1.0% by weight, based on the total amount of the aqueous suspension (1).

14. The aqueous suspension (1) of any one of claims 10 to 13, wherein the at least one organic UV filter has a particle size DN10 of 100 nm or larger, preferably 0.1 to 0.4 µm, more preferably 0.1 to 0.2 µm, as determined by transmission electron microscopy; and / or a particle size DN50 of 120 nm or larger, preferably 0.12 to 0.5 µm, more preferably 0.12 to 0.3 µm, as determined by transmission electron microscopy; and / or a particle size DN90 of 200 nm or larger, preferably 0.2 to 1.0 µm, more preferably 0.2 to 0.5 µm, as determined by transmission electron microscopy; and / or a particle size Dv10 of greater than 0.1 µm, preferably 0.1 to 0.4 µm, as determined by laser diffraction; and / or a particle size of less than 2.2 µm, preferably less than 2.0 µm, as determined by laser diffraction. μm, preferably less than 1.5 µm, with Dv90, where Dv10 and Dv90 were measured using a Mastersizer 2000 from Malvern Panalytical.

15. An aqueous suspension (1) of any one of claims 10 to 14, used in a sunscreen or daily care composition.