Sunscreen composition containing non-nano organic UV screening agent

Abstract

The present invention relates to a sunscreen or daily care composition comprising: i) a particle size D N and ii) at least one particulate micronized organic UV filter having a particle size Dv90 of more than 100 nm and a particle size Dv90 of less than 20 μm; and ii) at least one further inorganic or organic UV filter.

Description

[Technical Field]

[0001] The present invention relates to a sunscreen or daily care composition comprising i) at least one micronized organic UV filter and ii) at least one further inorganic or organic UV filter. [Background technology]

[0002] The use of sunscreen compositions to protect skin from the harmful effects of sunlight is becoming more and more common. At the same time, consumer and regulatory expectations regarding the safety, performance, sustainability, and cost of sunscreen and daily care compositions are constantly increasing. Therefore, there is a need to develop high-performance sunscreen compositions that simultaneously meet other requirements from consumers and regulatory authorities.

[0003] Sunscreen compositions contain UV filters that absorb and effectively scatter UV radiation. One group of UV filters that has been found to be particularly effective at absorbing and scattering UV radiation is particulate nano-sized, insoluble organic crystalline UV filters. Particulate nano-sized, insoluble organic UV filters completely avoid the problem of low solubility and overcome the common solubility issue of organic UV filters by providing the UV filters as aqueous suspensions that can be used in various types of sunscreen products. Furthermore, particulate nano-sized UV filters have been found to be particularly effective UV absorbers. Due to the nano-sized scale of the UV filter particles, the number of molecules that UV light strikes is greater for nano-sized particulate materials than for materials with larger particles for the same mass of material. In addition, the surface coverage of the skin is increased for the same mass of material using nano-sized particles compared to larger particles. These effects are described in detail in the art, for example, in B. Herzog et al., "Physical properties of organic particulate UV absorbers used in sunscreens II. UV-attenuating efficiency as a function of particle size", Journal of Colloid and Interface Science 276 (2004), 354-363 and S. Mueller et al., "Micronization as a Tool in the Development of Innovative UV Filters", SOEFW-Journal, 131 (2005), 32-38.

[0004] Methods for preparing such particulate nano-sized insoluble organic UV filters are described, for example, in WO 97 / 03643 A1 and WO 2009 / 003934 A1. The particulate nano-sized insoluble organic UV filters are obtained by pulverizing in a ball mill using grinding beads.

[0005] Nano-sized UV screening agents disclosed in the art show excellent UV absorption properties.However, nano-sized materials have been under pressure in recent years due to consumer concerns about safety, especially about the possibility of nano-sized materials penetrating the skin.Although these concerns may be scientifically unfounded, consumers are increasingly demanding nano-free sunscreen and daily care products. Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the background outlined above, it was an object of the present invention to provide a sunscreen or daily care composition that has excellent UV absorption properties and does not rely on nano-sized UV screening agents. [Means for solving the problem]

[0007] Surprisingly, i) Particle size D N At least one particulate micronized organic UV filter having a particle size Dv90 of more than 100 nm and a particle size Dv90 of less than 20 μm; ii) at least one further inorganic or organic UV filter; A sunscreen or daily care composition comprising It was found that the film exhibits excellent UV absorption properties without relying on nano-sized organic UV screening agents. [Brief explanation of the drawings]

[0008] [Figure 1] 1 shows the particle size distribution of nano MBBT used in comparative composition CC1. [Figure 2] 1 shows the particle size distribution of non-nano MBBT used in composition IC1 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] definition As used in this specification and the appended claims, the singular forms "a" and "an" also include the respective plural forms unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" refer to a range of accuracy that a person skilled in the art would understand to still ensure the technical effect of the feature in question. This term typically denotes a deviation of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5% from the indicated numerical value. The term "comprising" should be understood to be open-ended. The term "consisting of" for the purposes of the present invention is considered to be a preferred embodiment of the term "comprising of". Hereinafter, when a group is defined as comprising at least a certain number of embodiments, this also means that preferred groups consisting only of these embodiments are also encompassed. Furthermore, the terms "first," "second," "third," or "(a)," "(b)," "(c)," "(d)," and similar terms in the specification and claims are used to distinguish between similar elements and do not necessarily describe sequential or chronological order. It is to be understood that terms so used are interchangeable under appropriate circumstances, and that the embodiments of the invention described herein can be performed in orders other than those described or illustrated herein. When terms such as "first," "second," "third," or "(a)," "(b)," "(c)," "(d)," "i," "ii," and the like refer to steps in a method, use, or assay, unless otherwise specified in this application, as described herein above or below, there is no time gap or inconsistency between the steps, i.e., the steps may be performed simultaneously, or there may be time gaps of seconds, minutes, hours, days, weeks, months, or even years between such steps. It is to be understood that the invention is not limited to the particular methods, procedures, reagents, etc. described herein, as these may vary.It should also be understood that the terms used herein are used only for the purpose of describing particular embodiments and are not intended to limit the scope of the present invention, which is limited only by the appended claims. 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.

[0010] As used herein, the term "does not comprise (free of)" in the context that the composition of the present invention does not comprise a particular compound or a particular group of compounds, which may be a group combined under a collective term, means that the composition does not comprise said compound or group of compounds in an amount greater than 0.8% by weight, based on the total weight of the composition. Furthermore, it is preferred that the composition according to the present invention does not comprise said compound or group of compounds in an amount greater than 0.5% by weight, and it is preferred that the composition is completely free of said compound or group of compounds.

[0011] When referring to weight percentages of compositions and the ingredients contained therein, it is to be understood that, according to the present invention, the total amount of ingredients does not exceed 100% (±1% rounded).

[0012] The term "sunscreen composition" or "sunscreen" refers to any topical agent that can absorb a specific portion of UV radiation and further reflect and scatter it. Therefore, it should be understood that the term "sunscreen composition" not only includes sunscreen compositions, but also any cosmetic composition that provides UV protection. The term "topical agent" refers to a product that is applied to the skin, and may refer to, for example, a spray, lotion, cream, oil, foam, powder, or gel. According to the present invention, the sunscreen composition may contain one or more active agents, such as organic and inorganic UV filters, and other ingredients or additives, such as emulsifiers, emollients, viscosity modifiers, stabilizers, preservatives, or fragrances.

[0013] The term "daily care composition" refers to any external preparation. Daily care compositions containing UV filters can absorb a certain portion of UV radiation, and can also reflect and scatter it, and are used as daily care products for the human body, for example, face or body. Daily care compositions can contain one or more active agents, such as organic and / or inorganic UV filters, and other ingredients or additives, such as emulsifiers, emollients, viscosity adjusters, stabilizers, preservatives, or fragrances. Suitable daily care compositions are those according to the present invention, such as leave-on face and body care products.

[0014] Suitable leave-on products for the face and body are, for example, daily care preparations, sun protection compositions, decorative preparations and skin care preparations.

[0015] Suitable decorative preparations are, for example, lipsticks, nail varnishes, eye shadows, mascaras, dry or wet make-up, blushers, powders, and depilatories.

[0016] Suitable skin care preparations are, for example, moisturizing, refining and lifting preparations.The daily care compositions mentioned can be in the form of cream, ointment, paste, foam, gel, lotion, powder, makeup, spray, stick or aerosol.The daily care composition with UV protection comprises UV filter i) and ii) and protects human skin from damage caused by UV light.

[0017] As used herein, the term "UV filter" or "ultraviolet filter" refers to an organic or inorganic compound that can absorb ultraviolet light from sunlight and also reflect and scatter it. UV filters can be classified into UV-A, UV-B, or broadband filters according to their UV protection curve. Preferably, the term "UV filter" includes or consists of any UV filter defined in Annex VI of Regulation (EC) No. 1223 / 2009 of the European Parliament and of the Council (December 3, 2020 edition).

[0018] The solubility of the water-soluble UV filter in water at 25°C is at least 2% by weight, preferably at least 3% by weight, more preferably at least 5% by weight.

[0019] The solubility of the oil-soluble UV filter in oil (emollient) at 25°C is at least 2% by weight, preferably at least 3% by weight, more preferably at least 5% by weight.

[0020] The prefixes Cn to Cm indicate in each case the possible number of carbon atoms in the group.

[0021] "C 12 ~C 15 The term "alkyl benzoate" refers to 12 ~C 15 It refers to the ester of alkyl chain-containing fatty alcohol and benzoic acid. 12 ~C 15 The alkyl chain is C 12 , C 13 , C 14 or C 15 is defined as an alkyl chain having a chain length of

[0022] As used herein, the term "Cn-Cm carboxylic acid" refers in each case to a straight-chain or branched carboxylic acid having n to m carbon atoms, for example 6 to 24 carbon atoms.

[0023] The term "Cn-Cm alcohol" as used herein refers in each case to a straight-chain or branched alcohol having n to m carbon atoms, for example, 3 to 24 carbon atoms or 6 to 24 carbon atoms or 1 to 22 carbon atoms.

[0024] The term "C2-C12 dicarboxylic acid" as used herein refers in each case to a dicarboxylic acid having 2 to 12 carbon atoms, such as butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid) or decanedioic acid (sebacic acid).

[0025] As used herein, the term "dialkyl ether" refers to a straight-chain or branched dialkyl ether, in each instance, having a total of 12 to 36 carbon atoms and containing at least one ether moiety.

[0026] As used herein, the term "C6-C22 alcohol carbonate" refers to a linear or branched alcohol carbonate, in each case having 6 to 22 carbon atoms and containing at least one functional group consisting of a carbonyl group flanked by two alkoxy groups.

[0027] The term "alkyl" as used herein refers, in each case by way of example, to 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, tert-butyl, 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.

[0028] The term "alkoxy" as used herein refers in each case to a straight-chain or branched alkyl group, usually having 1 to 20 carbon atoms, attached via an oxygen atom. Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butyloxy, 2-butyloxy, isobutyloxy, tert-butyloxy, etc.

[0029] The term "carboxyalkyl" as used herein includes carboxymethyl, carboxyethyl, carboxypropyl, carboxyisopropyl, carboxybutyl, carboxyisobutyl, carboxyamyl, carboxyhexyl, carboxyheptyl, carboxyoctyl, carboxyisooctyl, carboxynonyl, carboxydecyl, carboxyundecyl, carboxydodecyl, carboxytetradecyl, carboxyhexadecyl and carboxyoctadecyl, with carboxymethyl being preferred.

[0030] The term "cycloalkyl" as used herein refers, in each case, to a monocyclic alicyclic group typically 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.

[0031] As used herein, the term "substituted" means that a hydrogen atom bonded to the specified atom is replaced with a specifically stated substituent, provided that the substitution results in a stable or chemically feasible compound. Unless otherwise specified, a substituted atom can have one or more substituents, and each substituent is independently selected.

[0032] The term "emollient" relates to certain cosmetic oils used to protect, moisturize and lubricate the skin. The word emollient comes from the Latin "mollire" (to soften). Generally, emollients prevent the evaporation of water from the skin by forming an occlusive coating. Alternatively or additionally, emollients improve the distribution of the product on the skin. Emollients can be divided into different groups depending on their polarity index.

[0033] The term "sensitive skin" refers to skin whose natural barrier function is weakened and disrupted by triggers, which can be, for example, cold weather, extremely hot water, and potentially dangerous ingredients contained in sunscreen or daily care compositions.

[0034] As used herein, the term "Sun Protection Factor (SPF)" refers to how well a sunscreen composition protects skin, primarily from UV-B radiation. Specifically, this index 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 evenly applied to the skin of a person who normally burns after 10 minutes in the sun, the sunscreen will allow those skilled in the art to stay in the sun 15 times longer. In other words, SPF 15 refers to a sunscreen applied to a surface with a thickness of 2 milligrams per square centimeter (mg / cm). 2 This means that if a 15-fold reduction in UV radiation were to reach the skin, assuming it were applied evenly at a dose of 150 ...

[0035] The definition of "broad" protection (also called broad spectrum or broad-spectrum protection) can be based on the "critical wavelength" or UVA-PF. To cover a wide wavelength range, UV-B and UV-A must be protected. According to US requirements, to achieve broad-spectrum protection, the critical wavelength must be at least 370 nm. Furthermore, the European Commission recommends that all sunscreen 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, the UVA protection factor must be at least 10.

[0036] The term "critical wavelength" is defined as the wavelength at which the area under the UV protection curve (protection rate (%) for each wavelength) accounts for 90% of the total area under the curve in the UV range (290-400 nm). For example, a critical wavelength of 370 nm means that the protection provided by a sunscreen composition is not limited to UV-B wavelengths, i.e., wavelengths from 290 to 320 nm, but extends to at least 370 nm, with 90% of the total area under the protection curve in the UV range at 370 nm.

[0037] The term "administering" refers to applying a sunscreen or daily care composition to human skin.

[0038] The term "at least one particulate micronized organic UV filter i)" refers to particles of a UV filter. It is understood that at least one particulate micronized organic UV filter refers to one type of UV filter, not a single particle of a UV filter. Consequently, at least one particulate micronized organic UV filter i) refers to a plurality of particles of at least one UV filter having a specific particle size distribution of the particles.

[0039] The terms "nano" or "nanomaterial" used herein comply with European Commission Recommendation 2011 / 696 / EU. Accordingly, in nanomaterials, 50% or more of the particles, including aggregates or agglomerates, based on the particle size distribution by number are smaller than 100 nm. For the purposes of the present invention, the particulate non-nano UV screening agent i) preferably has a content of particles smaller than 100 nm, based on the particle size distribution by number, of less than 50%, more preferably less than 30%.

[0040] The size of the UV filter particles in the present invention is defined by the particle size distribution of the population of particles.

[0041] Particle size distribution can be characterized in terms of particle volume (mass) or in terms of particle number. For example, Dv90=1 μm means that 90% of the volume (or mass) of the dispersed material is made up of particles smaller than 1 μm, and 10% is larger. In contrast, D N 50 = 100 nm indicates that the particle size distribution is based on the number of particles, suggesting that 50% of the particles in the sample are smaller than 100 nm. Empirically, in polydisperse samples, small particles tend to be smaller than the number of particles in the distribution D N dominates Dv, while large particles dominate 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 can be obtained by electron microscopy. For laser diffraction, many commercially available instruments are available, for example, from Anton Paar (PSA series), Microtrac MRB (Sync), or Malvern Panalytical (Mastersizer series). Numerical results characterizing particle size distributions will vary within narrow ranges depending on the sensitivity and resolution of the selected instrument. Those skilled in the art know how to handle these discrepancies, and this type of instrument is routinely used in R&D and quality control laboratories. In contrast, electron microscopy is more expensive and less frequently used.

[0042] This D N The distinction between Dv and Dv is related to the classification of materials as "nano". According to the European Commission's Recommendation 2011 / 696 / EU, nanomaterials are those that N The resulting dispersion is a micronized dispersion with a .50 value of 100 nm or less. Methods found in the literature for the production of micronized organic UV absorbers ultimately result in nanodispersions (WO 2018069200). This seems desirable, since the effectiveness of UV absorber dispersions increases with decreasing particle size. Furthermore, depending on the material properties of the UV absorber crystals, the fracture mechanism in the milling equipment can also produce nanomaterials from crystals still in the micron range.

[0043] As used herein, the term "dispersion" refers to a system in which discrete particles of one material are dispersed in a continuous phase of another material. The two phases may be of the same or different states of matter. A particular subtype of dispersion is a "suspension," in which solid elements are dispersed (i.e., not dissolved) in a fluid.

[0044] Specific Embodiments of the Invention The present invention provides a sunscreen or daily care composition comprising: i) Particle size D N At least one particulate micronized organic UV filter having a particle size Dv90 of more than 100 nm and a particle size Dv90 of less than 20 μm; ii) at least one further inorganic or organic UV filter; The present invention relates to a sunscreen or daily care composition comprising:

[0045] It has been found that sunscreen or daily care compositions containing these ingredients provide surprisingly high UV protection without the need for nano-sized particulate UV filters. This finding is in contrast to the established belief that nano-sized particulate UV filters exhibit particularly high UV protection properties that cannot be achieved with the same type of non-nano-sized particulate UV filters. Previous studies have shown that the performance of nano-sized particulate UV filters, such as MBBT, far exceeds that of the same non-nano-sized UV filters. Surprisingly, in contrast to previous understanding of nano-sized UV filters, sunscreen products containing components i) and ii) according to the present invention exhibit similar UV protection compared to the same sunscreen product containing nano-sized component i). This was a completely unexpected finding in light of the previously established theoretical understanding of particulate UV filters. Without being bound to any particular scientific theory, it is believed that in sunscreen or daily care products, the complex interactions of different ingredients, in particular different UV filters i) and ii), result in a different UV attenuation behavior than suggested by the analysis of an aqueous suspension consisting solely of particulate micronized UV filters as UV absorbers.

[0046] The present invention makes it possible to provide consumers with sunscreen or daily care products that offer the same level of protection without the need for nano-sized UV particulate filters, which is a major breakthrough given the increasing consumer demand for cosmetics that do not contain nano-sized ingredients and the increasing regulatory demands on nanomaterials that make up cosmetics.

[0047] Particulate UV screening agent i) The at least one particulate micronized organic UV filter i) has a particle size D N The particle size range is found to be suitable for optimal UV attenuation. Larger particles are less suitable for sunscreen and daily care products because they do not provide the excellent UV attenuation desired in these applications. Furthermore, larger particles can have an unpleasant feel on the skin and appear white. Smaller particles are considered nanomaterials or close to being nanomaterials, which may lead to increased scrutiny by consumers and regulators.

[0048] As mentioned above, D N Value and D V The value makes it possible to describe the particle size distribution of the particles of the at least one particulate micronized organic UV filter. N The value describes the number of particles in the population that are below a certain threshold, e.g., particle diameter D N It should be understood that an organic UV filter having a particle size of more than 100 nm can also be expressed as an organic UV filter having a particle size of 100 nm or less for less than 50% of the particles (by number). N The particle size D is particularly useful for identifying and quantifying smaller particles within a population of particles of a particular material. N 50 can be determined, for example, by transmission electron microscopy (TEM) or scanning electron microscopy (SEM), preferably by transmission electron microscopy (TEM).

[0049] In the present invention, the particle diameter D of at least one particulate micronized organic UV screening agent N50 is greater than 100 nm. Consequently, less than 50% of the particles of the at least one particulate micronized organic UV filter i) have a particle size of less than 100 nm.

[0050] In a preferred embodiment of the present invention, the particle size D of the at least one particulate micronized organic UV filter i), preferably determined by transmission electron microscopy, N 10 is 30 nm or more, preferably 35 nm to 400 nm, more preferably 50 nm to 200 nm. In this way, the number of very small particles of the UV screening agent i) is particularly small.

[0051] In another preferred embodiment of the present invention, the particle size D of the at least one particulate micronized organic UV filter i), preferably determined by transmission electron microscopy, N 50 is 120 nm or more, preferably 0.12 to 0.5 μm, more preferably 0.12 to 0.3 μm. According to this preferred embodiment, the particle size of less than 50% of the particles of component i) is less than 120 nm.

[0052] In another preferred embodiment of the present invention, the particle size D of the at least one particulate micronized organic UV filter i), preferably determined by transmission electron microscopy, N 90 is 200 nm or more, preferably 0.2 to 1.0 μm, and more preferably 0.2 to 0.5 μm.

[0053] The particle size distribution of particles of particulate micronized organic UV filters i) can also be described by the Dv particle size distribution. The Dv value refers to the volume (or mass) distribution of particle sizes instead of the number of particle sizes. The Dv value is particularly useful for describing larger particles within a population of particles of a particular material.

[0054] The Dv90 value of the at least one particulate micronized organic UV filter i) is less than 20 μm. This means that 90% of the particles by volume (or mass) have a particle size of less than 20 μm. A Dv90 value greater than 20 μm may result in an unpleasant skin feel and a white appearance. Preferably, the particle size Dv90 of the at least one particulate micronized organic UV filter i) is less than 10 μm, more preferably less than 5 μm, even more preferably less than 3 μm, and most preferably less than 2.2 μm.

[0055] According to another preferred embodiment of the present invention, the particle size Dv50 of the at least one particulate micronized organic UV filter i) is less than 0.8 μm, preferably less than 0.6 μm, more preferably less than 0.5 μm, most preferably less than 0.4 μm.

[0056] According to another preferred embodiment of the present invention, the at least one particulate micronized organic UV filter i) has a Dv10 value of more than 0.1 μm, preferably between 0.1 and 0.4 μm.

[0057] The Dv90, Dv50 and Dv10 values ​​are preferably determined by laser diffraction using a "Mastersizer 2000" from Malvern Instruments, Ltd, UK.

[0058] Different D N It is immediately apparent that the Dv and Dv values ​​describe the particle size distribution of the at least one particulate micronized organic UV filter in different ways. N Various methods of describing particle size distribution in terms of values ​​can be variably combined to describe the particle size distribution of particles.

[0059] In a preferred embodiment of the present invention, at least one particulate micronized organic UV filter i) is an insoluble organic UV filter.In this context, the term insoluble UV filter is understood to refer to a UV filter that is not dissolved in water and cosmetic oil at 25°C.On the contrary, the solubility of a water-soluble UV filter in water is at least 2% by weight, preferably at least 3% by weight, more preferably at least 5% by weight at 25°C.The solubility of an oil-soluble UV filter in oil (emollient) is at least 2% by weight, preferably at least 3% by weight, more preferably at least 5% by weight at 25°C.The insoluble organic UV filter i) according to this preferred embodiment does not meet either of these two requirements, and is therefore considered to be "insoluble" in water and oil at 25°C.

[0060] The at least one finely divided organic UV filter i) is selected from the group consisting of tris-biphenyltriazine, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone, phenylenebis-diphenyltriazine, and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol]. These four UV filters are the most common particulate organic UV filters in the art and are particularly well suited as component i) of the sunscreen or daily care composition of the present invention.

[0061] Trisbiphenyltriazine has the following structure: [ka]

[0062] 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone has the following structure: [ka]

[0063] Phenylene bis-diphenyl triazine has the following structure: [ka]

[0064] 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] has the following structure: [ka]

[0065] More preferably, the at least one micronized organic UV filter i) is selected from the group consisting of tris-biphenyltriazine, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone, and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

[0066] According to one embodiment of the present invention, the at least one micronized organic UV filter i) is 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone.

[0067] According to another embodiment of the present invention, the at least one micronized organic UV filter i) is tris-biphenyltriazine. Tris-biphenyltriazine (also known as TBPT) is a broad-spectrum UV filter with high performance across the entire UV-A and UV-B spectrum.

[0068] According to another embodiment of the present invention, the at least one finely divided organic UV filter i) is 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol]. 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] is a highly effective broad-spectrum UV filter covering the entire UV-A and UV-B spectrum. This is the most preferred UV filter i) according to the present invention.

[0069] According to a preferred embodiment of the present invention, the sunscreen or daily care composition according to the invention comprises at least one particulate micronized organic UV filter i) in an amount of 0.1 to 20% by weight, in particular 0.5 to 15% by weight, preferably 1 to 10% by weight, more preferably 1.5 to 8% by weight and most preferably 2 to 5% by weight, each based on the total weight of the sunscreen or daily care composition.

[0070] Particle diameter D over 100 nm N At least one micronized organic UV filter i) having a particle size Dv90 of less than 50 and 20 μm can be prepared by the method disclosed in patent application PCT / EP2022 / 072536, which is incorporated herein by reference. The micronization process for preparing particulate micronized organic UV filter i) according to PCT / EP2022 / 072536 comprises milling a suspension of at least one organic UV filter in a mixture of water and a hydrophobic additive in a milling device at a temperature of 35-90°C.

[0071] Preferably, at least one particulate micronized organic UV filter i) is provided in the form of an aqueous suspension. The micronization process for preparing the non-nano organic particulate UV filter i) used in the sunscreen or daily care composition of the present invention provides an aqueous suspension of the particulate UV filter in an aqueous medium, as is clear from the disclosure of PCT / EP2022 / 072536. The aqueous suspension is then preferably used as such in the sunscreen or daily care composition.

[0072] The aqueous suspension preferably contains a dispersant, which is relevant to the micronization process. Generally, any type of dispersant commonly used in the micronization process for cosmetic applications can be used.

[0073] Suitable dispersants are in particular polyglycerol alkyl esters, preferably polyglycerol monoalkyl esters, and alkyl polyglucosides, preferably those having the formula CH0(CHO)H, where n is an integer ranging from 8 to 16 and x is the glucoside moiety (average degree of polymerization of CHO, ranging from 1.4 to 1.6), or esters thereof. Further suitable dispersants are disclosed in WO 2009068469.

[0074] According to the present invention, the average degree of polymerization of glycerol in the polyglycerol monoalkyl ester is preferably 5 or more.

[0075] In a preferred embodiment, the at least one polyglycerol monoalkyl ester is selected from the group consisting of decaglyceryl caprate, decaglyceryl monolaurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate, pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl stearate, pentaglyceryl isostearate, and combinations thereof. In a particularly preferred embodiment, the at least one polyglycerol monoalkyl ester is decaglyceryl monolaurate (INCI Polyglyceryl-10 Laurate).

[0076] A polyglycerol monoalkyl ester having an HLB (hydrophilic-lipophilic balance) of 14.5 or more is preferred, and an HLB of 15 or more is more preferred. The HLP value is calculated by the following formula: HLB=20·Mh / M (where Mh is the molecular weight of the hydrophilic portion of the molecule, and M is the molecular weight of the entire molecule).

[0077] If the HLB of the polyglycerol monoalkyl ester is less than 14.5, it may take longer to disperse the finely ground methylene bis-benzotriazolyl tetramethylbutylphenol in the aqueous phase component.Examples of polyglycerol monoalkyl esters with an average polymerization degree of 5 or more and an HLB of 14.5 or more include decaglyceryl caprate, decaglyceryl monolaurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl laurate, pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl stearate, and pentaglyceryl oleate.Examples of polyglycerol monoalkyl esters with an HLB of 15 or more include decaglyceryl caprate and decaglyceryl monolaurate.

[0078] Particularly preferred are polyglyceryl monolaurates, especially decaglyceryl monolaurate and decyl glucoside.

[0079] Preferably, the alkyl polyglucosides are composed of C1-C12 esters of compounds of formula CH2n+1O(C6H10O5)xH, i.e., esters formed by reacting a C1-C12 carboxylic acid with one or more free OH groups of the glucoside moiety (C6H10O). In this context, preferably, the esters are 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 of the glucoside moiety (C6H10O).

[0080] Preferably, the aqueous suspension comprises the dispersant in an amount of 1 to 20% by weight, more preferably 3 to 15% by weight, based on the total weight of the aqueous suspension.

[0081] According to another preferred embodiment of the invention, the aqueous suspension comprises at least one particulate micronized organic UV filter i) in an amount of 10 to 65% by weight, in particular 30 to 60% by weight, based on the total weight of the aqueous suspension.

[0082] The weight ratio of dispersant to at least one particulate micronized organic UV filter i) in the aqueous dispersion is preferably 0.01 to 0.5, more preferably 0.05 to 0.4, in particular 0.07 to 0.3.

[0083] Other excipients such as thickeners, antifoaming agents, pH adjusters, preservatives, etc. may be added to this preparation.

[0084] The aqueous suspension containing at least one particulate, micronized organic UV filter i) preferably also contains a hydrophobic additive. Preferably, the hydrophobic additive is selected from the group consisting of alcohols having 6 to 18 carbon atoms, C6 to C24 carboxylic acids, esters of C6 to C24 carboxylic acids with C3 to C24 alcohols, esters of hydroxycarboxylic acids with C6 to C24 alcohols, esters of carboxylic acids with polyhydric alcohols, liquid mono- / di- / triglyceride mixtures based on C6 to C18 carboxylic acids, esters of C6 to C24 alcohols with aromatic carboxylic acids or esters of oxocarboxylic acids, tricarboxylic acid esters, esters of C2 to C12 dicarboxylic acids with alcohols having 1 to 22 carbon atoms or esters of polyols having 2 to 10 carbon atoms and 2 to 6 hydroxy groups, substituted cyclohexanes, C6 to C22 alcohol carbonate esters, symmetrical or asymmetrical dialkyl ethers having a total of 12 to 36 carbon atoms, ring-opening products of epoxidized carboxylic acid esters with polyols, silicone oils, aliphatic or naphthenic hydrocarbons, diol esters, and mixtures thereof. Hydrophobic additives have been found to be useful in promoting Ostwald ripening of UV filter particles during the micronization process, leading to dissolution of nanoparticles formed during the milling process, and inducing crystal growth that counteracts the grinding action of the mill, thereby achieving an optimal non-nano size distribution during the milling process.

[0085] In a preferred embodiment of the present invention, the hydrophobic additive is contained in the aqueous suspension 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, based on the total weight of the aqueous suspension.

[0086] Additional UV filters ii) The sunscreen or daily care composition of the present invention further comprises at least one additional UV filter ii). The additional UV filter ii) can be an organic or inorganic UV filter.

[0087] According to a preferred embodiment, the sunscreen or daily care composition of the present invention further comprises at least one inorganic or organic UV filter ii) which is a UVA-absorbing filter, a broad-spectrum (UVA+UVB) filter or a UVB-absorbing filter. The combination of at least one UVA-absorbing filter, at least one broad-spectrum filter and at least one UVB-absorbing filter in the sunscreen or daily care composition of the present invention is a preferred embodiment.

[0088] According to a preferred embodiment, the sunscreen or daily care composition according to the invention comprises at least one further inorganic or organic UV screening agent ii) UVA absorbing filter: 4-(tert.-butyl)-4'-methoxydibenzoylmethane (INCI Butyl Methoxydibenzoylmethane), - 2-[4-(diethylamino)-2-hydroxybenzoyl]hexyl benzoate (INCI Diethylaminohydroxybenzoylhexylbenzoate), - [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1]heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphorsulfonic acid), - Phenyldibenzimidazole tetrasulfonate disodium; Broad spectrum (UVA+UVB) absorbing screener: - 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI Bis-ethylhexyloxyphenyl methoxyphenyl triazine), - 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1-disiloxanyl]propyl]phenol (INCI Drometrizole Trisiloxane), - Zinc oxide; UVB absorbing screeners: - 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI Phenylbenzimidazole Sulfonic Acid), - 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoic acid tris(2-ethylhexyl) ester (INCI Ethylhexyltriazone), - (RS)-2-Ethylhexyl-2-hydroxybenzoate (INCI Ethylhexyl Salicylate), - Dimethicone Diethyl Benzalmalonate, - diethylhexylbutamidotriazone, 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3-methoxypropylamino)cyclohex-2-en-1-ylidene]acetate, - titanium dioxide, - cerium oxide; and mixtures thereof.

[0089] The at least one further organic or inorganic UV filter ii) is preferably 4-(tert.-butyl)-4'-methoxydibenzoylmethane (INCI Butyl Methoxydibenzoylmethane), - hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI Diethylaminohydroxybenzoylhexylbenzoate), - 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI Bis-ethylhexyloxyphenyl methoxyphenyl triazine), - 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI Phenylbenzimidazole Sulfonic Acid), - (3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1]heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphorsulfonic acid), - phenyldibenzimidazole tetrasulfonate disodium, - (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI Ethylhexyl Methoxycinnamate), - 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoic acid tris(2-ethylhexyl) ester (INCI Ethylhexyltriazone), - Dimethicone Diethyl Benzalmalonate, - diethylhexylbutamidotriazone, 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3-methoxypropylamino)cyclohex-2-en-1-ylidene]acetate, - 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1-disiloxanyl]propyl]phenol (INCI Drometrizole Trisiloxane), - titanium dioxide, - zinc oxide, - cerium oxide, and mixtures thereof.

[0090] The combination of at least one particulate micronized organic UV filter i) with any one of these organic and inorganic UV filters provides a sunscreen composition with excellent UV protection properties.

[0091] at least one further organic or inorganic UV filter ii) 4-(tert.-butyl)-4'-methoxydibenzoylmethane (INCI Butyl Methoxydibenzoylmethane), - 2-[4-(diethylamino)-2-hydroxybenzoyl]hexyl benzoate (INCI Diethylaminohydroxybenzoylhexylbenzoate), - 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI Bis-ethylhexyloxyphenyl methoxyphenyl triazine), - 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoic acid tris(2-ethylhexyl) ester (INCI Ethylhexyltriazone), - 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI Phenylbenzimidazole Sulfonic Acid), - [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1]heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphorsulfonic acid), and mixtures thereof It is even more particularly preferred that the organic UV filter is selected from the group consisting of:

[0092] These are particularly useful UV screening agents that are environmentally friendly and safe, yet provide excellent UV protection.

[0093] Most preferably, the at least one further organic or inorganic UV filter ii) is - 2-[4-(diethylamino)-2-hydroxybenzoyl]hexyl benzoate (INCI Diethylaminohydroxybenzoylhexylbenzoate), - organic UV filters selected from the group consisting of 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid tris(2-ethylhexyl) ester (INCI Ethylhexyltriazine), and mixtures thereof.

[0094] The highly effective UV filters diethylaminohydroxybenzoylhexyl (DHHB) and 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid tris(2-ethylhexyl) ester (INCI ethylhexyltriazone) (EHT) combined with at least one particulate micronized organic UV filter provide particularly powerful sunscreen or daily care compositions across the entire relevant UV spectrum.

[0095] According to another preferred embodiment, the daily care or sunscreen composition does not contain any of the UV filters 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI octocrylene), (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate), and 3,3,5-trimethylcyclohexyl salicylate (INCI homosalate). There is growing concern that these UV filters may have adverse health effects, either directly or through decomposition products that may result from these UV filters. Therefore, it is preferred that the compositions of the present invention do not contain these filters.

[0096] According to a preferred embodiment, the amount of the at least one further inorganic or organic UV filter ii) is from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, most preferably from 1 to 10% by weight, respectively, based on the total weight of the sunscreen or daily care composition.

[0097] According to a preferred embodiment of the present invention, the at least one further organic or inorganic UV filter ii) is not a nano UV filter, i.e. the UV filter does not have a particle size distribution that can be considered as a nanomaterial.

[0098] Further ingredients of sunscreen or daily care compositions The sunscreen or daily care compositions of the present invention preferably comprise additives, in particular additives selected from the group consisting of emulsifiers, emollients, viscosity modifiers (thickeners), sensory enhancers, adjuvants, preservatives, fragrances and combinations thereof.

[0099] Preferred emulsifiers include: - glucose derivatives, such as cetearyl glucoside, arachidyl glucoside, lauryl glucoside, polyglyceryl-3 methylglucose distearate, methylglucose sesquistearate; - sucrose derivatives, for example sucrose polystearate, sucrose palmitate; - sorbitol derivatives; - glycerides of fatty acids, for example, glyceryl stearate, glyceryl oleate; glutamic acid derivatives, such as sodium stearoyl glutamate; sulfosuccinic acid derivatives, such as disodium cetearyl sulfosuccinate; - phosphoric acid derivatives, for example potassium cetyl phosphate; - fatty acid esters of polyglyceryl, for example, polyglyceryl-3 diisostearate, polyglyceryl-2 dipolyhydroxystearate; - Oxyalkenylated organically modified silicone / polysiloxane / polyalkyl / polyether copolymers and derivatives Examples include:

[0100] Preferred emollients include: esters of linear or branched fatty acids with linear or branched fatty alcohols, such as, for example, propylheptyl caprylate, coco-caprylate, isopropyl myristate, ethylhexyl palmitate; Esters of aromatic carboxylic acids with linear or branched fatty alcohols, e.g. C 12 ~C 15 -Alkyl benzoate, ethylhexyl benzoate, phenethyl benzoate; - dicarboxylic acid esters with linear or branched alcohols, such as dibutyl adipate, dicaprylyl carbonate, diisopropyl sebacate; - esters of hydroxycarboxylic acids with linear or branched fatty alcohols; - esters of linear or branched fatty acids with polyhydric alcohols, for example, butylene glycol di(caprylate / caprate); - C6~C 18 Mono-, di-, and triglycerides based on fatty acids, such as caprylic / capric triglyceride, cocoglyceride; Guerbet alcohols, for example octyldodecynol; - hydrocarbons, for example, hydrogenated polyisobutene, mineral oil, squalene, isohexadecane; - ethers, for example, dicaprylyl ether; Silicone derivatives (organo-modified polysiloxanes), such as dimethylpolysiloxane and cyclic silicones Examples include:

[0101] Preferred thickeners include: - fatty alcohols, such as cetyl alcohol, cetearyl alcohol, stearyl alcohol; - fatty acids, for example, stearic acid; - fatty acid esters, for example, myristyl stearate; waxes, such as beeswax, carnauba wax, microcrystalline wax, ceresin, ozocerite; polysaccharides or derivatives, such as xanthan gum, guar gum, agar gum, alginates, gellan gum, carraghenan; - polyacrylates or reticulated acrylic homopolymers or polyacrylamides, such as carbomers, acrylate copolymers, acrylates / alkyl acrylate C10-C30 crosspolymers, acrylates / beheneth-25 methacrylate copolymers; - silicate derivatives, for example magnesium silicate; cellulose derivatives, such as hydroxypropyl cellulose Examples include:

[0102] Preferred feel enhancers include: - polyamide derivatives, for example, nylon-12; - polymethyl methacrylate; - Silica; - Mica; - polymethylsilsesquioxane; - polyethylene; - starch derivatives, such as aluminum starch octenylsuccinate; - Dimethicone derivatives; - boron nitride; - (HDI / trimethylolhexyl lactone) crosspolymer Examples include:

[0103] Preferred humectants include: - 1,2 pentanediol; - 1,2 hexanediol; - 1,2 octanediol; - 1,2-decanediol; - 2-methyl-1,3-propanediol Examples include:

[0104] Preferred adjuvants include: - tocopherol derivatives; - Retinol derivatives; - ascorbic acid derivatives; - Bisabolol; - Allantoin; - Panthenol; - Chelating agents (EDTA, EDDS, EGTA, phytic acid, piroctone olamine); - Ethylhexylglycerin; - Hydroxyacetophenone; - caprylhydroxymic acid; - propellants, such as propane, butane, isobutene, dimethyl ether; - styrene / PVP or styrene / acrylamide copolymers; insect repellents, such as butylacetylaminopropionate Examples include:

[0105] Preferred preservatives include: - benzyl alcohol; - Zingerone Examples include:

[0106] Preferred fragrances are limonene, citral, linalool, alpha-isomethylione, geraniol, citronellol, 2-isobutyl-4-hydroxy-4-methyltetrahydropyran, 2-tert.-pentylcyclohexyl acetate, 3-methyl-5-phenyl-1-pentanol, 7-acetyl-1,1,3,4,4,6-hexamethyltetralin, adipic acid diester, alpha-amylcinnamaldehyde, alpha-methylionone, amyl-C-butylphenylmethylpropional cinnamal, amyl salicylate, amyl cinnamyl alcohol, anise alcohol, benzoin, benzyl alcohol, benzyl benzoate, benzyl cinnamate, benzyl salicylate, bergamot oil. , bitter orange oil, butylphenyl methylpropioli, cardamom oil, cedrol, cinnamal, cinnamyl alcohol, citronellyl methyl crotonate, lemon oil, coumarin, diethylsuccinate, ethyl linalool, eugenol, evernia furfracea extract, evernia prunastri extract, farensol, guajac wood oil, hexyl cinnamal, hexyl salicylate, hydroxycitronellal, lavender oil, lemon oil, linalyl acetate, mandarin oil, menthyl PCA, methylheptenone, nutmeg oil, rosemary oil, sweet orange oil, terpineol, tonka bean oil, triethyl citrate, vanillin, and combinations thereof.

[0107] In relation to the above-mentioned preferred embodiments, it should be understood that when the sunscreen or daily care composition comprises two or more additives, combinations of the additives defined above are also part of the present invention.

[0108] In connection with the above preferred and particularly preferred embodiments, it should be understood that the sunscreen or daily care composition may further comprise water.

[0109] It should be understood that when water is present in a sunscreen or daily care composition, it is preferably present in an amount greater than 5% by weight, based on the total weight of the composition. It should further be understood that when water is present in a sunscreen or daily care composition, the sunscreen or daily care composition can be an oil-in-water emulsion (O / W emulsion), a water-in-oil emulsion (W / O emulsion), a gel cream, or an oil-in-gel composition.

[0110] In one embodiment of the present invention, the sunscreen or daily care composition may be provided in various forms, for example, in the form of a gel, cream, oil, lotion, stick or sprayable product.

[0111] It is particularly preferred that the sunscreen or personal care compositions of the present invention are free of nano UV filters. As used herein, the term "free" means that the sunscreen or personal care composition contains less than 1 wt. %, preferably less than 0.5 wt. %, and most preferably less than 0.1 wt. %, respectively, of nano UV filters, based on the total weight of the sunscreen or personal care composition.

[0112] Even more preferably, the sunscreen or personal care compositions of the present invention are free of nanomaterials. As used herein, the term "free" means that the sunscreen or personal care composition contains less than 1% by weight, preferably less than 0.5% by weight, and most preferably less than 0.1% by weight, of nanomaterials, based on the total weight of the sunscreen or personal care composition.

[0113] The following examples further illustrate the present invention. [Example]

[0114] Two different sunscreen compositions were prepared. The first, designated Comparative Composition CC1 (CC1), contained nano-sized 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] (nano-MBBT). The second, designated Inventive Composition 1 (IC1), contained non-nano-MBBT.

[0115] Nano-MBBT for use in Composition CC1 was prepared on a laboratory scale according to Example A1, Dispersion 1, of WO 2017 / 198806. 0.51 kg of polyglyceryl-10 laurate (Dermofeel® G10L, Evonik Industries AG) was dissolved in 2.49 kg of deionized water. 3.00 kg of 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] (MBBT) was slowly added to the solution. The slurry was pre-milled for 40 minutes using a stainless steel rotor mill (MZ 80, Fryma Koruma, ProXES GmbH) operated in circulation mode at a flow rate of 2000 kg / h and a rotation speed of 2900 rpm. After pre-milling, the dispersion was stirred overnight at 70 rpm. 2 kg of the dispersion was milled in a stirred ball mill (Dyno®-Mill Multilab, Willy A. Bachofen AG) equipped with a 0.6 L milling vessel and 0.3-0.4 mm Y-ZrO2 milling beads (Silibeads®, Sigmund Lindner). The dispersion was circulated through the mill during the milling process. The particle size of the dispersion was controlled by laser diffraction using a Mastersizer 2000 from Malvern Pananalytical GmbH. The pressure in the mill was less than 0.5 bar, and the product temperature was below 40°C. Milling continued until the median particle size Dv50 was approximately 160 nm. The product was discharged and the active agent content was controlled.

[0116] The non-nano MBBT used in composition IC1 of the present invention was prepared using the method described in PCT / EP2022 / 072536. The slurry contained 50% UV-filtering agent MBBT, 6.5% polyglyceryl-10 laurate, and water to make up 100%. The slurry preparation and wet milling were performed in the same manner as for the nano MBBT dispersion described above. However, when the particle size Dv50 of the dispersion reached approximately 300 nm, milling in the stirred ball mill was stopped and the dispersion was discharged from the mill. 50 g of the dispersion was transferred to a beaker mill equipped with a stirrer, and 120 ml of Y-ZrO2 grinding beads (0.6-0.8 mm Y-ZrO2, Silibeads®, Sigmund Lindner) were added. The slurry / bead mixture was homogenized, and the stirrer speed was increased to 1200 rpm to initiate the milling process. The product temperature was set to 45°C by adjusting the cooling of the beaker mill. 0.3 g of C12-15 alkyl benzoate (Cetiol® AB, BASF Personal Care & Nutrition GmbH) was added to the suspension and milling continued. During milling, the product temperature was increased to 49-50°C. Particle size was monitored throughout the milling process, and an increase in Dv10 occurred in parallel with a decrease in Dv90, indicating a decrease in the nano fraction of particles during the micronization process. After 4 hours, the stirrer was stopped, the mixture was cooled, and the suspension was separated from the milling beads.

[0117] Dv and D of nano-MBBT and non-nano-MBBT N The particle size distribution for the values ​​is shown in Table 1.

[0118] Nano MBBT and non-nano MBBT D N Value(D N 10. D N 50, D NThe particle size (90) was determined using transmission electron microscopy (TEM). For TEM measurements, the dispersion was diluted 1:500 with distilled water. The dispersion was applied to a carbon-coated TEM carrier grid by dropping and drying at room temperature. Prior to use, the carbon-coated grid was treated in a plasma cleaner (Fischione Model 1020; supply gas: air; Fischione Instruments Inc., PA, USA) to ensure a hydrophilic surface. Samples were analyzed with a Thermo-Fisher (Waltham, MA, USA) Talos F200i transmission electron microscope in bright-field mode at 200 kV. Images were captured with a low-dose Thermo-Fisher Falcon 3 camera to avoid beam damage to the material. Automated particle size detection from micrographs was performed using the NanoDefine ParticleSizer plugin for ImageJ (FIJI).

[0119] The Dv values ​​(Dv10, Dv50, Dv90) of nano- and non-nano-MBBT were determined by laser diffraction analysis using a Malvern Mastersizer 2000 equipped with a HydroG dispersion unit. Data were analyzed in the Malvern standard mode, suitable for ground samples, using the optical properties of MBBT according to literature (B. Herzog et al., Journal Coll. Int. Sci. 271 (2004) 136-144).

[0120] [Table 1]

[0121] The particle size distribution of nano-MBBT used in comparative composition CC1 is also shown in Figure 1. The particle size distribution of non-nano-MBBT used in composition IC1 of the present invention is also shown in Figure 2.

[0122] Sunscreen compositions CC1 and IC1 were then prepared using the following ingredients (in weight percent based on the total weight of the respective composition):

[0123] [Table 2]

[0124] Compositions CC1 and IC1 were prepared by first preparing parts A and B separately and heating each to 80°C while stirring. With increasing stirring, part A was added to part B and homogenized with an Ultra Turrax at 10,000 rpm for 10 seconds. The mixture was then allowed to cool to room temperature (298K) while stirring. Next, part C was added to the mixture and the combined mixture was stirred. Finally, part D was added and the resulting final mixture was stirred at room temperature for an additional 30 minutes. The pH value of the mixture was adjusted to 6.0-6.5.

[0125] The absorption spectra of the two compositions were found to be very similar. The comparative composition CC1 had an in vitro sun protection factor (SPF) of 20.5, while the composition IC of the present invention had an SPF of 20.6. Thus, the two compositions provided comparable levels of UV protection. Surprisingly, composition IC1 containing non-nano MBBT was as effective as composition CC1 containing nano MBBT as a sunscreen composition.

Claims

1. 1. A sunscreen or daily care composition comprising: i) Particle size D Ｎ at least one particulate micronized organic UV filter having a Dv90 greater than 100 nm and a particle size Dv90 less than 20 μm; ii) at least one further inorganic or organic UV filter; and 1. A sunscreen or daily care composition comprising:

2. the particle size D of the at least one particulate micronized organic UV filter i) determined by transmission electron microscopy; Ｎ 10 is 30 nm or more, in particular 35 to 400 nm or 50 to 200 nm; and / or In particular, the particle diameter D determined by transmission electron microscopy Ｎ 50 is 120 nm or more, in particular 0.12 to 0.5 μm, or 0.12 to 0.3 μm; and / or In particular, the particle diameter D determined by transmission electron microscopy Ｎ 90 is greater than or equal to 200 nm, in particular between 0.2 and 1.0 μm, or between 0.2 and 0.5 μm.

3. the Dv10, determined by laser diffraction, of the at least one particulate micronized organic UV filter i) is greater than 0.1 μm, in particular between 0.1 and 0.4 μm; and / or the particle size Dv50 determined by laser diffraction is less than 0.8 μm, in particular less than 0.6 μm, or less than 0.5 μm, or less than 0.4 μm; 3. A sunscreen or daily care composition according to claim 1 or 2, characterized in that the particle size Dv90, determined by laser diffraction, is less than 10 μm, or less than 5 μm, or less than 3 μm, or less than 2.2 μm.

4. 4. Sunscreen or daily care composition according to claim 1, characterized in that the at least one particulate micronized organic UV filter i) is an insoluble organic UV filter.

5. 5. The sunscreen or daily care composition according to claim 4, characterized in that the at least one insoluble organic UV filter is selected from the group consisting of tris-biphenyltriazine, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone, phenylenebis-diphenyltriazine, and 2,2'-methylenebis[6-(2H-1,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol].

6. The at least one further inorganic or organic UV filter ii) is 4-(tert.-butyl)-4'-methoxydibenzoylmethane (INCI Butyl Methoxydibenzoylmethane), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI Diethylaminohydroxybenzoylhexylbenzoate), 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI Bis-ethylhexyloxyphenyl methoxyphenyl triazine), 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI Phenylbenzimidazole Sulfonic Acid), [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1]heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphorsulfonic acid), - disodium phenyldibenzimidazole tetrasulfonate, (RS)-2-ethylhexyl-(2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI Ethylhexyl Methoxycinnamate), 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoic acid tris(2-ethylhexyl) ester (INCI Ethylhexyltriazone), - Dimethicone diethylbenzalmalonate, - diethylhexylbutamidotriazone, 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3-methoxypropylamino)cyclohex-2-en-1-ylidene]acetate, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-disiloxanyl]propyl]phenol (INCI Drometrizole Trisiloxane), - titanium dioxide, - zinc oxide, - Cerium oxide and mixtures thereof 6. A sunscreen or daily care composition according to any one of claims 1 to 5, characterized in that it is selected from the group consisting of:

7. The at least one further inorganic or organic UV filter ii) is 4-(tert.-butyl)-4'-methoxydibenzoylmethane (INCI Butyl Methoxydibenzoylmethane), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI Diethylaminohydroxybenzoylhexylbenzoate), 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI Bis-ethylhexyloxyphenyl methoxyphenyl triazine), 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoic acid tris(2-ethylhexyl) ester (INCI Ethylhexyltriazone), 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI Phenylbenzimidazole Sulfonic Acid), 7. A sunscreen or daily care composition according to claim 6, characterized in that the organic UV filter is selected from the group consisting of [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1]heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphorsulfonic acid), and mixtures thereof.

8. The at least one further inorganic or organic UV filter ii) is hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI Diethylaminohydroxybenzoylhexylbenzoate), 8. A sunscreen or daily care composition according to claim 7, characterized in that the organic UV filter is selected from the group consisting of 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid tris(2-ethylhexyl)ester (INCI Ethylhexyltriazine), and mixtures thereof.

9. 9. The sunscreen or daily care composition according to any one of claims 1 to 8, characterized in that the sunscreen or daily care composition does not contain a particulate nano-UV filter.

10. A sunscreen or daily care composition according to any one of claims 1 to 9, characterized in that the sunscreen or daily care composition is free of nanomaterials.

11. 11. Sunscreen or daily care composition according to any one of claims 1 to 10, characterized in that the amount of the at least one particulate micronized organic UV filter i) is 0.1 to 20% by weight, in particular 0.5 to 15% by weight, or 1 to 10% by weight, or 1.5 to 8% by weight, or 2 to 5% by weight, each based on the total weight of the sunscreen or daily care composition.

12. 12. Sunscreen or daily care composition according to any one of claims 1 to 11, characterized in that the amount of the at least one further inorganic or organic UV filter ii) is 0.1 to 20 wt.-%, or 0.5 to 15 wt.-%, or 1 to 10 wt.-%, respectively, based on the total weight of the sunscreen or daily care composition.

13. 13. Sunscreen or daily care composition according to any one of claims 1 to 12, characterized in that the at least one particulate micronized organic UV filter i) is provided in the form of an aqueous suspension.

14. 14. Sunscreen or daily care composition according to claim 13, characterized in that the aqueous suspension comprises a dispersing agent, in particular the dispersing agent is selected from the group consisting of polyglycerol alkyl esters and alkyl polyglucosides.

15. 15. Sunscreen or daily care composition according to claim 13 or 14, characterized in that the aqueous suspension comprises a hydrophobic additive, in particular the hydrophobic additive is selected from the group consisting of alcohols having 6 to 18 carbon atoms; C6 to C24 carboxylic acids; esters of C6 to C24 carboxylic acids with C3 to C24 alcohols; esters of hydroxycarboxylic acids with C6 to C24 alcohols; esters of carboxylic acids with polyhydric alcohols; liquid mono- / di- / triglyceride mixtures based on C6 to C18 carboxylic acids; esters of C6 to C24 alcohols with aromatic carboxylic acids or with oxocarboxylic acids; tricarboxylic acid esters; esters of C2 to C12 dicarboxylic acids with alcohols having 1 to 22 carbon atoms or with polyols having 2 to 10 carbon atoms and 2 to 6 hydroxy groups; substituted cyclohexanes; C6 to C22 alcohol carbonate esters; symmetrical or asymmetrical dialkyl ethers having a total of 12 to 36 carbon atoms; ring-opening products of epoxidized carboxylic acid esters with polyols; silicone oils; aliphatic or naphthenic hydrocarbons; diol esters; and mixtures thereof.

Images