Coated powder having high light stability

Abstract

The coated powder comprises (a) particles and (b) a coating on the surface of the particles, the coating comprising (1) silica moieties, (2) organooxysilane moieties selected from the group consisting of mono-organooxysilane moieties, bi-organooxysilane moieties, and tri-organooxysilane moieties, and (3) poly(dialkyl)siloxane moieties. The amount by weight of the SiO2 equivalent of the organooxysilane moieties and silica moieties is determined based on the m of the specific surface area of ​​the particles to be coated. 2 / g is at least 0.0625% of the total weight of the coated powder.

Description

Technical Field

[0001] [Background Art] Particles are added to improve and modify the properties of many different types of compositions and products. Examples include ultraviolet (UV) light-absorbing particles, pigments, colorants, fillers, matting agents, light-scattering particles, abrasion-resistant particles, viscosity modifiers, magnetic particles, and reflective particles.

[0002] Particles containing oxides, particularly those containing zinc oxide, titanium oxide, silicon oxide, aluminum oxide, iron oxide, and / or rare earth metal oxides, are particularly suitable as additives. These oxides are thermodynamically stable, typically cannot react with environmentally widespread oxygen, and tend to have lower reactivity with water than many other oxide and non-oxide materials. These oxide materials have been used for centuries as pigments and abrasives.

[0003] Particles composed of titanium oxide, the most notable of the specific metal oxides, are usually colorless and transparent to visible light and are particularly interesting because they provide protection against exposure to UV light; however, due to the photocatalytic behavior of these oxides, they tend to have poor photo stability. Metal oxides exposed to UV radiation result in an increase in free radicals. These free radicals can cause destabilization of the formulation itself. Furthermore, free radicals can result in the formation of hydroperoxides and other peroxidic free radicals known to induce contact dermatitis and severe allergic reactions. These free radicals can also trigger a chain reaction that ultimately results in reactive oxygen species (ROS). These highly reactive derivatives react with cell components including lipid membranes and are thought to cause photoaging and skin cancer that appear in later life. ROS deplete and damage non-enzymatic and enzymatic antioxidant defense systems and cause persistent genetic damage. Other components in cosmetic compositions also have low photo stability and may generate additional free radicals on the skin surface.

[0004] It has been found that by coating particles, the photo-stability of the particles is improved. The coated powder is used to prepare cosmetic compositions for skin application, such as compositions for protecting the skin from UV radiation (e.g., sunscreens).

[0005] Coated powders can be produced by coating particles, which have chemical stability, photo-stability, and the ability to form dispersions with high weight loadings and low viscosities. For example, films that produce chemical and photo-stability have been found, and such coated particles can be used to form dispersions with high weight loadings and low viscosities. The film comprises (1) a silica moiety, (2) an organoxysilane moiety selected from the group consisting of mono-organoxysilane moieties, bi-organoxysilane moieties, and tri-organoxysilane moieties, and (3) a poly(dialkyl)siloxane moiety. See, for example, U.S. Patent No. 9,139,737.

[0006] Antioxidants are often used in cosmetic skin care products and lose their efficacy through an oxidation process under UV radiation. By adding coated powders that block and absorb UV radiation, the oxidation of antioxidants caused by UV radiation can be reduced. However, many UV-blocking particles, such as zinc oxide and titanium dioxide, exhibit photocatalytic activity and may cause the generation of free radicals in cosmetic compositions. This can potentially compromise the stability and effectiveness of antioxidants due to the immediate reaction between the antioxidant and the free radicals or the products generated by the free radicals.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0008] In a first aspect, the present invention is a coated powder comprising (a) particles and (b) a coating on the surface of the particles, the coating comprising (1) a silica moiety, (2) an organoxysilane moiety selected from the group consisting of mono-organoxysilane moieties, bi-organoxysilane moieties, and tri-organoxysilane moieties, and (3) a poly(dialkyl)siloxane moiety. The amount, by weight, of the organoxysilane moiety and the silica moiety is at least 0.0625% of the total weight of the coated powder per m 2 2 of the specific surface area of the particles being coated. 2 / g.

[0009] In a second aspect, the present invention is a dispersion comprising (1) a coated powder, (2) a fluid, and (3) an antioxidant.

[0010] In a third aspect, the present invention is a method for producing a coated powder, the method comprising coating the particles with a polymer by polymerizing a composition comprising (i) the particles, (ii) a first alkoxysilane selected from the group consisting of tetra-alkoxysilanes, poly(tetra-alkoxysilanes), and mixtures thereof, (iii) an organoalkoxysilane selected from the group consisting of mono-organoalkoxysilanes, bi-organoalkoxysilanes, tri-organoalkoxysilanes, and mixtures thereof, and (iv) a second alkoxysilane selected from the group consisting of poly(dialkyl)siloxanes and mixtures thereof. The amount, by weight, of the organoxysilane moiety and the silica moiety is at least 0.0625% of the total weight of the coated powder per m 2 2 of the specific surface area of the particles being coated. 2 / g.

[0011] In a fourth aspect, the present invention is a coated powder having super light stability.

[0012] In a fifth aspect, the present invention is a method of protecting skin from light, the method comprising coating the skin with a composition comprising the coated powder.

[0013] In a sixth aspect, the present invention is a method of protecting a keratinous material, comprising coating the keratinous material with a composition containing a coating powder.

[0014] In a seventh aspect, the present invention is a method of protecting the skin from light, comprising coating the skin with a dispersion.

[0015] In an eighth aspect, the present invention is a method of suppressing lipid peroxidation, comprising applying a composition containing a coating powder to the skin.

[0016] In a ninth aspect, the present invention is a method of preventing or reducing fine lines and wrinkles on the skin, comprising applying a composition containing a coating powder to the skin.

[0017] In a tenth aspect, the present invention is a method of preventing the loss of skin elasticity, comprising applying a composition containing a coating powder to the skin.

[0018] In an eleventh aspect, the present invention is a method of preventing the thinning of the skin, comprising applying a composition containing a coating powder to the skin.

[0019] Definitions The term "nanoparticle" means a particle having a particle size of up to 999 nm. Nanoparticles preferably have a particle size of 10 nm to 500 nm.

[0020] The term "micro particle" means a particle having a particle size of 1 μm to 100 μm.

[0021] The term "particle size" means the average diameter of the image of the particle when viewed with an electron microscope, unless otherwise specified. The term "average particle size" means the average of the particle sizes of a particle aggregate.

[0022] "High solids content" or "high weight loading" means that the composition mentioned has at least 50% by weight of solid particles.

[0023] "Alkyl" (or alkyl- or alk-) represents a substituted or unsubstituted, straight-chain, branched-chain or cyclic hydrocarbon chain, preferably containing 1 to 22 carbon atoms. More preferred alkyl groups are lower alkyl groups such as, for example, alkyl groups containing 1 to 10 carbon atoms. Preferred cycloalkyls have 3 to 10, preferably 3 to 6 carbon atoms in their ring structure. Suitable examples of unsubstituted alkyl groups include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, iso-butyl, tert-butyl, sec-butyl, cyclobutyl, pentyl, cyclopentyl, hexyl, and cyclohexyl.

[0024] "Alkenyl" represents a substituted or unsubstituted, straight-chain, branched-chain or cyclic, unsaturated hydrocarbon chain containing at least one double bond, preferably having 2 to 22, more preferably 2 to 6 carbon atoms. Exemplary unsubstituted alkenyl groups include ethenyl (or vinyl) (-CH=CH 2 ), 1-propenyl, 2-propenyl (or allyl) (-CH 2 -CH=CH 2 ), 1,3-butadienyl (-CH=CHCH=CH 2 ), 1-butenyl (-CH=CHCH 2 CH 3 ), hexenyl, pentenyl, and 1,3,5-hexatrienyl. Preferred cycloalkenyl groups contain 5 to 8 carbon atoms and at least one double bond. Examples of cycloalkenyl groups include cyclohexadienyl, cyclohexenyl, cyclopentenyl, cycloheptenyl, cyclooctenyl, cyclohexadienyl, cycloheptadienyl, and cyclooctatrieneyl.

[0025] "Alkynyl" represents a substituted or unsubstituted, straight-chain, branched-chain or cyclic, unsaturated hydrocarbon chain containing at least one triple bond, preferably having 2 to 22, more preferably 2 to 6 carbon atoms.

[0026] "Aryl" represents any aromatic carbocyclic or aromatic heterocyclic group, preferably having 3 to 10 carbon atoms. The aryl group can be cyclic (such as phenyl (or Ph), etc.) or polycyclic (such as naphthyl, etc.), and can be unsubstituted or substituted. Preferred aryl groups include phenyl, naphthyl, furyl, thienyl, pyridyl, indolyl, quinolinyl or isoquinolinyl.

[0027] "Heterocyclic radical" represents a stable, saturated, partially unsaturated, or aromatic ring, preferably containing 5 to 10 atoms, more preferably 5 or 6 atoms. The above ring can be substituted with substituents one or more times (preferably 1, 2, 3, 4 or 5 times). The above ring can be mono-, bi- or polycyclic. The heterocyclic group consists of 1 to 3 heteroatoms independently selected from the group consisting of carbon atoms and nitrogen, oxygen, and sulfur. The heteroatoms may or may not be protected. Examples of useful heterocyclic groups include substituted or unsubstituted acridine, benzothiazoline, benzimidazole, benzofuran, benzothiophene, benzthiazole, benzothiophenyl, carbazole, cinnoline, furan, imidazole, 1H-indazole, indole, isoindole, isoquinoline, isothiazole, morpholine, oxazole, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, pteridine, purine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, quinazoline, quinoline, quinoxaline, thiazole, 1, 3, 4-thiadiazole, thiophene, 1, 3, 5-triazine, and triazole.

[0028] "Substituted" means that the moiety contains at least 1, preferably 1 to 3 substituents. Suitable substituents include hydrogen (H) and hydroxyl (-OH), amino (-NH 2 )), oxy (-O-), carbonyl (-CO-), thiol, alkyl, alkenyl, alkynyl, alkoxy, halo, nitrile, nitro, aryl, and heterocyclic group.

[0029] Titanium dioxide (TiO 2) The light stability is measured using the test described below. This test is referred to as the "TiO 2 Light Stability Test". First, a stock solution of 25% resorcinol in ethanol is prepared. 8.9 g (±0.01 g) of Finsolv TN and 0.1 g (±0.005 g) of Hostaphat KW 340D are placed in a glass scintillation vial. Next, the capped vial is placed in an oven at 50 °C until the Hostaphat KW 340D is dissolved and the solution is homogeneous (approximately 15 minutes). After removing the vial from the oven, 1.0 g (±0.01 g) of the coated titanium dioxide powder is added to the solution. The solution is placed in an ultrasonic bath and sonicated for 15 minutes. 1.0 g (±0.01 g) of 25% resorcinol in ethanol from the first step is added to the scintillation vial and manually mixed well until homogeneous. A quartz cuvette is filled with this mixture and capped with a Teflon lid. Next, the mixture is tested using a Milton Roy Color Mate Colorimeter or a suitable equivalent colorimeter. Before testing the mixture, the colorimeter is calibrated using a white tile calibration standard. After recording the results of the "pre-irradiation sample", the cuvette containing the sample is placed in a QUV weatherometer. Next, the mixture is exposed to UV light for exactly 15 minutes at a constant temperature of 50 °C using a UVB bulb at 1.23 Wm -2 seconds -1 in a Q-Labs QUV weatherometer. Next, the test mixture is removed for immediate color measurement with a colorimeter. Light stability can be expressed as the total color change compared to a standard with respect to the described UV exposure time (ΔE in the L * a * b * color space). ΔE is calculated from the following equation according to the CIE76 definition:

[0030]

Equation

[0031] where

[0032]

Chem.

[0033] is the color coordinate of the test mixture after irradiation,

[0034]

Chem.

[0035] = 99.47,

[0036]

Chem.

[0037] = -0.16, and

[0038]

Chem.

[0039] = -0.17, corresponding to the color coordinates of the white control tile. Coated TiO 2 particles are "ultra-photostable" when ΔE is 15 or less in the above-mentioned photostability test.

[0040] TiO such as zinc oxide (ZnO) 2To test the photo-stability of other major compositions, the following test may be used. This test is referred to as the "DPPH photo-stability test". First, 0.025 g ± 0.001 g of coated ZnO powder is placed into four 50 mL disposable plastic beakers. 0.0125% DPPH (di(phenyl)-(2,4,6-trinitrophenyl)iminiazanium, also referred to as diphenylpicrylhydrazyl; CAS number 1898-66-4) is prepared in a BCS (ethylene glycol butyl ether) solution. 19.975 g ± 0.001 of 0.0125% DPPH in the BCS solution is added to each beaker containing the coated powder. This is thoroughly mixed with a glass stirring rod and each beaker is sonicated for 20 seconds to ensure good dispersion of the powder throughout the solution. After sonication, the sample is transferred to a labeled scintillation vial. The pre-irradiated sample is measured with a calibrated Milton Roy Color Mate Colorimeter or an appropriate equivalent colorimeter. After measurement, the sample is irradiated. Next, the test mixture is exposed to UV light for exactly 10 minutes at a constant temperature of 50 °C using a UVA or UVB bulb in a Q-Labs QUV weatherometer at 0.35 Wm -2 seconds -1 The UVA bulb is used to test particles that act as filters for UVA radiation and the UVB bulb is used to test particles that act as filters for UVB radiation. Finally, the post-irradiation sample is measured with a colorimeter. In this case, the photo-stability after UV exposure is indicated by the persistence of the purple color due to the absorption band of the dye at 520 nm. The photo-stability can be expressed as the total color change compared to a standard with respect to the described UV exposure time (L * a * b * color space ΔE). ΔE is calculated from the following equation according to the CIE76 definition:

[0041]

Equation

[0042] wherein,

[0043] [Chem.]

[0044] is the color coordinate of the test mixture after irradiation, and

[0045] [Chem.]

[0046] is the initial color coordinate of the test mixture before irradiation. The data is reported as the average ΔE value for four samples. The coated particles are "ultra-photostable" if the ΔE is 4.5 or less in the above-described photostability test.

[0047] The photostability of the coated effect pigment is measured using a modified version of the above-described test. This test is designated the "Effect Pigment Photostability Test". Modifications were necessary to remove noise in the colorimetric measurements induced by the reflectivity of the interference pigment itself in the sample. The test is described below. 0.0125% DPPH (di(phenyl)-(2,4,6-trinitrophenyl)iminonium azanium, also designated diphenylpicrylhydrazyl; CAS number 1898-66-4) is prepared in a BCS (ethylene glycol butyl ether) solution. A 20 ml aliquot of the DPPH solution is transferred to a labeled scintillation vial. This sample is measured with a calibrated Milton Roy Color Mate Colorimeter or a suitable equivalent colorimeter. Next, 0.025 g ± 0.001 g of the coated effect pigment powder is placed into four 50 mL disposable plastic beakers. 19.975 g ± 0.001 of 0.0125% DPPH in BCS solution is added to each beaker containing the coated powder. This is mixed thoroughly with a glass stirring rod and each beaker is sonicated for 20 seconds to ensure good dispersion of the powder throughout the solution. After sonication, each sample is transferred to a labeled scintillation vial. Next, the test mixture is placed in a Q-Labs QUV weatherometer with a UVB bulb at 0.35 Wm -2 seconds -1Use at a constant temperature of 50 °C and expose to UV light for exactly 10 minutes. Next, filter the irradiated sample through a suitable 1-μm filter to remove the effect pigments that can interfere with color measurement. Finally, measure the filtered post-irradiation sample with a colorimeter. As described above, the light stability after UV exposure is indicated by the persistence of the purple color due to the absorption band of the dye at 520 nm. The light stability can be expressed as the total color change compared to a standard with respect to the described UV exposure time (L * a * b * in the color space (ΔE). ΔE is calculated from the following equation according to the CIE76 definition:

[0048]

Number

[0049] wherein,

[0050]

Chemistry

[0051] are the color coordinates of the test mixture after irradiation, and

[0052]

Chemistry

[0053] are the initial color coordinates of the as-prepared DPPH solution. Report the data as the average ΔE value of four samples. The coated particles are considered "ultra-light stable" if the ΔE is 1.15 or less in the above light stability test, which represents half of the just noticeable difference value accepted based on CIE76.

[0054] The chemical reactivity is measured using the following chemical reactivity test. A 20 g glass vial is filled with a 4.5 g stock solution of 5% propyl gallate (propyl 3,4,5-trihydroxybenzoate, manufactured by Aldrich) in isopropyl alcohol. One-half of the number of grams of the powder to be evaluated is placed into the glass vial. Next, the glass vial is vigorously stirred for 30 seconds, such as by placing it in a bath-type ultrasonic processor. This mixture is left standing for 30 minutes. Next, the sample is gently mixed using a pipette and transferred to a cuvette (made of polycarbonate, polystyrene, or glass) having a path length of 1 cm. Next, the total color change (ΔE) is measured using a Data Color-International Spectraflash SF3000 colorimeter against a factory white color standard. The chemical reactivity is expressed as the total color change (ΔE). The powder is considered to be chemically reactive upon application if the chemical reactivity test results in a ΔE value greater than 20 and a sunburned brown appearance.

[0055] The hydrophobicity is measured using the following hydrophobicity test (this test is a visible water floatation test commonly used in the cosmetics industry and is described in U.S. Patent No. 4,454,288). Approximately 30 ml of deionized water is placed into a glass jar. Approximately 3.0 g ± 0.30 g of the powder to be tested is added to the glass jar. The glass jar is tightly sealed, and the sample is stirred 4 - 5 times and shaken vigorously 4 - 5 times to achieve intimate contact between the water and the powder. If the powder is floating (floating on the surface of the water) and the water is clear after 15 minutes, the powder is considered to be hydrophobic. If the powder is not floating and the water is clear after 15 minutes, or if the powder is floating but the water is not clear after 15 minutes, the sample is slightly hydrophobic.

[0056] The fluidity of the powder dispersion is measured using the following run-off distance test. The dispersion is produced at 50% solids in ethylhexyl benzoate (Finsolv® EB, manufactured by Innospec). Three drops (75 mg) of the dispersion are placed from a pipette onto a clean glass plate substrate while the surface is horizontal. Next, the glass plate substrate is held vertically at a 90° angle for 120 seconds to allow the dispersion to flow. The fluidity of the dispersion is represented by the distance the dispersion flows from the starting point. (This test was only used during the initial screening; a run-off distance of 164 ± 10 mm (reported as standard error) measured from the starting point corresponds to a viscosity of 145 ± 25 cP (reported as standard error) at a shear rate of 20 seconds -1 ). The coating powder is considered to produce an injectable dispersion if it exhibits a run-off distance greater than 100 mm in a 50% solids dispersion in ethylhexyl benzoate.)

[0057] The viscosity of the powder dispersion is measured using the following viscosity test. The powder dispersion is prepared at 50 wt% solids in capric / caprylic triglyceride (ALDO® MCT Special KFG, manufactured by Lonza, CAS number 73398-61-5), ethylhexyl benzoate (Finsolv® EB, manufactured by Innospec), and linear alkyl benzoate (Finsolv® TN C 12-15 Alkyl Benzoate CAS number: 68411-27-8), unless otherwise indicated. The viscosity is measured at 25 °C for each dispersion using a DVIII+ Ultra Rheometer manufactured by Brookfield with a CP52 spindle. The measurements are made at shear rates in the range of 0.1 second -1 ~100 seconds -1 .

[0058] The specific surface area of the particles is measured in m 2 / g and determined using the Brunauer-Emmett-Teller (BET) method.)

[0059] SiO2 The equivalent amount means the weight of SiO 2 present after converting all the silicon in the film into SiO 2 . For example, the "amount by weight of the SiO 2 equivalent amount" of that portion means that all the silicon forming the film is converted into SiO 2 and measured to determine the percentage of each portion in the coated powder.

[0060] The antioxidative power (AP) is measured using the AP method developed by Gematria Laboratories (Berlin, DE). This method determines the overall antioxidative power of the active ingredients, i.e., plant extracts, vitamins, etc., by observing the reduction activity against a stable test radical - DPPH using electron spin resonance (ESR) spectroscopy. The AP method utilizes the well - known DPPH method, and the main difference is that it uses both antioxidative ability and antioxidative activity to characterize the antioxidant being tested. For this purpose, different concentrations of the active ingredient are analyzed in real - time by ESR spectroscopy, and the decrease in the detected radical spin is tracked based on each setting. Using this innovative technology, important kinetic information that has been completely overlooked by most other test systems can be further obtained. Therefore, both the reaction time and the reduction potential of the antioxidant contribute to the calculation of AP. AP=(RA×N spin) / (w c ×t r )

[0061] AP can be expressed by the above - mentioned calculation formula, where RA is the constant reduction amplitude (1 / e 2 ), N spin is the amount of the reduced free radical characterized by the free electron (spin) of DPPH, w c is the characteristic weight of the antioxidant product, and t ris the reduction time (Jung K, Richter J, Kabrodt K, Lucke IM, Schellenberg I, Herrling T. The antioxidative power AP--A new quantitative time dependent (2D) parameter for the determination of the antioxidant capacity and reactivity of different plants. Spectrochim Acta A Mol Biomol Spectrosc. 63(2006):846-50). The obtained AP is expressed in antioxidative units (AU), and 1 AU corresponds to the activity of a 1 ppm solution of pure vitamin C (ascorbic acid) as a benchmark. This method enables a rapid and generally applicable technique for the measurement of AP over a very diverse range of classes of substances.

Brief Description of the Drawings

[0062]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0063] TiO 2Coatings of powders of this and other selected metal oxides are desirable for use in UV-protective topical skin compositions and other UV-protective coatings. However, for commercial desirability, such coating powders should be (a) photo-stable so that their color does not change significantly during exposure to UV light; (b) not chemically reactive so that they do not react with or discolor the composition during storage; and (c) able to be formed into high-weight loading dispersions with a minimal introduction of carrier fluid and having a viscosity low enough to enable easy handling and mixing when preparing consumer compositions, yet enabling a high SPF value for cost-effective transport and storage.

[0064] The multifunctional coating powders and high-dispersion solids described in U.S. Patent No. 9,139,737 are significantly improved over other existing coating powders, but can be further improved by increasing the photo-stability of the coating powders. Further, by adding antioxidants to the UV-protective composition, the amount of induced free radicals caused by UV radiation exposure is reduced.

[0065] This application utilizes coating powders that are chemically stable, have the ability to form high-weight loading dispersions, and in addition have excellent photo-stability. The coating powders are super photo-stable. The coating powders can be used to form compositions containing antioxidants and reduce the loss of antioxidants upon exposure to light.

[0066] The coating powders are particles coated with a polymer and are prepared by polymerizing a composition containing the particles and at least three components: (A) a first alkoxysilane selected from the group consisting of tetra-alkoxysilane, poly(tetra-alkoxysilane), and mixtures thereof; (B) an organoalkoxysilane selected from the group consisting of mono-organoalkoxysilane, bi-organoalkoxysilane, tri-organoalkoxysilane, and mixtures thereof; and (C) a second alkoxysilane selected from the group consisting of poly(dialkyl)siloxane and mixtures thereof.

[0067] The formed film contains portions corresponding to each of three constituent components: (A) a silica portion, (B) an organoxysilane portion selected from the group consisting of a mono-organoxysilane portion, a bi-organoxysilane portion, and a tri-organoxysilane portion, and (C) a poly(dialkyl)siloxane portion. The coated powder can be used to form a dispersion in a cosmetically acceptable fluid having a high solids content and a low viscosity.

[0068] When at least a specific amount of Si (measured as a weight equivalent) from all silanes is present in the film, excellent light stability has been found to occur. The composition ranges for each constituent component are based on the SiO 2 equivalent. All silane portions, i.e., SiO 2 derived from the silica portion and the organoxysilane portion, must be at least 0.0625% of the total weight of the coated powder per m 2 of the specific surface area of the particles to be coated. The silane portion can be mono-, di-, tri-, and tetra-functional. 2 / g.

[0069] The coated powder can be used to form a dispersion in a fluid having a high solids content and a low viscosity. The dispersion can be used to prepare a cosmetic composition for skin application, such as a composition (e.g., a sunscreen) for protecting the skin from UV radiation. Materials considered to be cosmetically acceptable are those listed in the International Nomenclature of Cosmetic Ingredients (INCI). Examples of cosmetically acceptable fluids are ethylhexyl benzoate (EB), linear alkyl benzoate (LAB), caprylic / capric triglyceride (CCT), squalane, natural oils, and various silicone fluids. Natural oils are oils derived from seeds, beans, fruits, flowers, skins, leaves, etc., and include their derivatives. Examples of natural oils are olive oil and soybean oil.

[0070] The coated powders, as well as the dispersions of the coated powders, can be used in various products. They are, in particular, in the case of TiO 2 - and ZnO-containing coated powders, added to dermatological compositions to provide UV protection for the skin; the coated powders can also be added as inorganic pigments to such compositions. The coated powders can also be added to shampoos, lotions, gels, hairsprays, aerosol foam creams or emulsions for washing, coloring and styling the hair, and, on the other hand, to provide UV protection for the hair. The coated powders can be added to paints, sealants and other coating agents for wood, plastics and other building materials; TiO 2 - and ZnO-containing coated powders also provide UV protection in such cases. The coated powders can also be added to resins, filled polymers and plastics, and inks. Magnetic fluids can be prepared when the metal oxide is magnetic, as in the case of certain iron oxides and rare earth oxides.

[0071] The particles preferably include metal oxides such as, for example, zinc oxide, titanium oxide, silicon oxide, aluminum oxide, iron oxide, bismuth oxide, cerium oxide, rare earth oxides, infrared-absorbing binary and ternary mixed metal oxides, and mixtures thereof. Examples include ZnO, TiO 2 , SiO 2 , Al 2 O 3 , Fe 2 O 3 , CeO 2 , SnO 2, zirconium-cerium oxide, mixed zirconium-rare earth oxides containing cerium, aluminosilicates (including amorphous aluminosilicates, crystalline aluminosilicates, and pumice), and other silicates, alumina, aluminosilicate, aluminum oxide containing magnesium aluminate (e.g., spinel), zinc oxide doped with trivalent metal cations (including aluminum-doped ZnO), antimony-tin oxide (ATO), indium-tin oxide (ITO), fluorine-doped tin oxide, and doped tungsten oxide are included. Oxidized minerals such as mica and natural mineral oxides can also be used. Other ceramic compositions including metals, carbides, and nitrides and mixtures thereof, as well as mixtures with oxides, can also be used.

[0072] The particles can be effect pigments. Effect pigments are typically flat or plate-like pigment particles coated with a thin layer of a secondary material having a higher refractive index. The composition of the underlying plate is typically mica, synthetic mica, silica, or alumina. The coating is typically titanium dioxide (typically in the anatase form), iron oxide, or bismuth oxychloride. The color of the pigment is controlled by the thickness of the coating layer. Effect pigments typically range in size from 1 to 100 μm. The pigments are also referred to as pearlescent pigments and interference pigments. These materials are commercially available (XIRALLIC®, PYRISMA®, COLORSTREAM®, and the IRIODIN® product line from EMD Performance Materials, MEARLIN® pearlescent pigments from BASF, and SYNCRYSTAL®, SYNAFIL®, MIRAGE®, and VISIONAIRE® effect pigments from Eckart).

[0073] Preferably, the particles have a particle size of up to 999 nm, including particle sizes of up to 100, 200, and 500 nm, more preferably a particle size of 10 nm to 500 nm, and most preferably a particle size of 15 nm to 250 nm such as 20, 30, 40, 50, 60, 70, 80, 90, and 100 nm. Preferably, the particles have an average particle size of up to 999 nm, including average particle sizes of up to 100, 200, and 500 nm, more preferably an average particle size of 10 nm to 500 nm, and most preferably an average particle size of 15 nm to 250 nm such as 20, 30, 40, 50, 60, 70, 80, 90, and 100 nm. Alternatively, the particles can have a particle size of 1 μm to 100 μm. The particles preferably have an average size of 1 to 10 μm.

[0074] The particles can preferably be coated by polymerizing the composition without using a solvent and using at least a part of the composition in the gas phase. The composition includes (A) a first alkoxysilane selected from the group consisting of tetra-alkoxysilane, poly(tetra-alkoxysilane), and mixtures thereof, (B) an organoalkoxysilane selected from the group consisting of mono-organoalkoxysilane, bi-organoalkoxysilane, tri-organoalkoxysilane, and mixtures thereof, and (C) a second alkoxysilane selected from the group consisting of poly(dialkyl)siloxane and mixtures thereof.

[0075] Preferably, the first alkoxysilane is present in an amount of 1.0 to 5% by weight, more preferably 0.5% to 7% by weight, and most preferably 1.5, 2, 2.5, 3, 3.5, 4, and 4.5% by weight of the coated powder. Preferably, the organoalkoxysilane is present in an amount of 0.1 to 1% by weight, more preferably 0.05 to 3% by weight, and most preferably 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9% by weight of the coated powder. Preferably, the second alkoxysilane is present in an amount of 0.75 to 2.5% by weight, more preferably 0.5% to 5% by weight, and most preferably 1.0, 1.25, 1.5, 1.75, 2.0, and 2.25% by weight of the coated powder.

[0076] The first alkoxysilane can be a tetra-alkoxysilane, poly(tetra-alkoxysilane), or a mixture thereof. The tetra-alkoxysilane is a compound of the formula (R a O) 4 Si, wherein each R a can be the same or different organic groups, and each R a is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 2, 3, 4, 5, 6, 7, 8, and 9 carbon atoms, including methyl, ethyl, and propyl. One example is tetraethoxysilane (TEOS). The poly(tetra-alkoxysilane) is an oligomer of one or more tetra-alkoxysilanes formed by partial hydrolysis. Preferably, the poly(tetra-alkoxysilane) contains 4 to 10 monomer units, more preferably 5, 6, 7, 8, and 9 monomer units.

[0077] The first alkoxysilane can contain a silica moiety. The silica moiety is a Si(O) 4 group bonded to 4 atoms, and [OSi(O 2 )] nIt can also exist in clusters such as O, where n is from 2 to 14, more preferably 4 to 10 including 5, 6, 7, 8 and 9.

[0078] The organoalkoxysilane is selected from the group consisting of mono-organoalkoxysilane, bi-organoalkoxysilane, tri-organoalkoxysilane, and mixtures thereof. The organoalkoxysilane has the formula R 1 n Si(OR b ) 4-n wherein n is 1, 2 or 3. R 1 is an organic group such as alkyl (e.g., linear alkyl, branched alkyl, cyclic alkyl, glycidoxyalkyl, methacryloxyalkyl and aminoalkyl), aryl, vinyl and heteroaryl. Examples of R 1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Preferably, R 1 contains 1 to 10 carbon atoms, more preferably 1 to 22 carbon atoms, more preferably 2, 3, 4, 5, 6, 7, 8 and 9 carbon atoms. Each R b can be the same or different organic groups, and each R b is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 2, 3, 4, 5, 6, 7, 8, and 9 carbon atoms, including methyl, ethyl, and propyl. An example of the organoalkoxysilane is triethoxyoctylsilane.

[0079] The organoalkoxysilane may contain an organoxysilane moiety. The organoxysilane moiety is 、R 1 n Si(O) (4-n) / 2 group, wherein n is an integer of 1, 2 or 3. R 1is an organic group such as alkyl (e.g., linear alkyl, branched alkyl, cyclic alkyl, glycidoxyalkyl, methacryloxyalkyl, and aminoalkyl), aryl, vinyl, and heteroaryl. R 1 Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Preferably, R1 contains 1 to 10 carbon atoms, more preferably 1 to 22 carbon atoms, and even more preferably 2, 3, 4, 5, 6, 7, 8, and 9 carbon atoms. An example of the organoxysilane moiety is octylsilane.

[0080] The second alkoxysilane is selected from the group consisting of poly(dialkyl)siloxane and mixtures thereof. The poly(dialkyl)siloxane is preferably an oligomer of the formula R c O ( R 2 2 (SiO) n (SiR 2 2 )OR c wherein n is an integer from 4 to 10, preferably including 5, 6, 7, 8, and 9. Each R 2 is an organic group such as methyl, ethyl, or phenyl, and each R c is a terminal blocking group such as alkyl including methyl, ethyl, and propyl that forms an alkyloxy group, or H that forms a hydroxyl group; both the hydroxyl and alkyloxy groups are reactive groups. It is also possible for 1 to 3 R 2 groups to be hydroxyl and / or alkyloxy groups. R 2 and R cEach independently contains 1 to 10 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 2, 3, 4, 5, 6, 7, 8 and 9 carbon atoms. Preferably, the poly(dialkyl)siloxane is polydimethylsiloxane or polydiethylsiloxane. Preferably, the poly(dialkyl)siloxane has a weight average molecular weight of 200 to 10,000, more preferably 500 to 5,000.

[0081] The second alkoxysilane may contain a poly(dialkyl)siloxane moiety. The poly(dialkyl)siloxane moiety is O bonded to other atoms ( R 2 2 SiO) n (SiR 2 2 )O or O ( R 2 2 SiO) n (SiR 2 2 )OR c group, where n is an integer from 2 to 14, preferably 4 to 10 including 5, 6, 7, 8, and 9. Each R 2 is independently an organic group such as methyl, ethyl, or phenyl, and each R c is a terminal blocking group such as alkyl including methyl, ethyl, and propyl that forms an alkyloxy group, or H that forms a hydroxyl group; both the hydroxyl and alkyloxy groups are reactive groups. It is also possible that 1 to 3 R 2 groups are hydroxyl and / or alkyloxy groups. R 2 and R c each independently contain 1 to 10 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 2, 3, 4, 5, 6, 7, 8 and 9 carbon atoms. Preferably, the poly(dialkyl)siloxane moiety is a polydimethylsiloxane moiety or a polydiethylsiloxane moiety.

[0082] Typically, the three components of the particles and the composition are thoroughly mixed together and then placed in a sealed container. The container is then evacuated and heated to a temperature at which at least two of the components become vapor. The temperature is maintained for a time sufficient to allow polymerization and the formation of a coating on the particles, preferably with continuous mixing during the polymerization process. By carrying out the polymerization reaction for a longer duration, a more complete coating of the particle surface is possible. Next, the container is filled with an inert gas stream that allows for the removal of volatile by-products such as alcohol, and then cooled to room temperature. The polymer coating formed contains three respective silane moieties: (1) a silica moiety, (2) an organoxysilane moiety selected from the group consisting of a mono-organoxysilane moiety, a bi-organoxysilane moiety, and a tri-organoxysilane moiety, and (3) a poly(dialkyl)siloxane moiety.

[0083] Preferably, the polymerization temperature is from 80 °C to 120 °C, more preferably from 90 °C to 110 °C including 92, 94, 96, 98, 100, 102, 104, 106, and 108 °C. Preferably, the amount of time for polymerization is from 0.5 to 10 hours, more preferably from 1 to 6 hours including 2, 3, 4, and 5 hours.

[0084] After the polymerization process, the coated powder is heated to 120 °C to evaporate any volatile compounds. This drying also removes a very small weight. The amount of silicon in the coating in terms of SiO 2 For the purpose of determining the amount in a substantial amount, the coated powder is heated to a temperature of 600 °C to 800 °C. This process can be carried out in a thermogravimetric device or other device. Due to the rapid oxidation to either 600 °C or 800 °C in air, all the silicon-containing portions in the coated powder are converted to SiO 2 The composition of the calcined powder can be confirmed by various assay methods.

[0085] A variety of techniques can be used to analyze the coated powder of the present invention. The inorganic oxide particles can be dissolved in various acids to determine the relative amounts of the polymer and the inorganic oxide. Next, the remaining polymer film can be examined using Fourier Transform Infrared Spectroscopy (FTIR) to determine the presence of different moieties and the relative amounts of each moiety. Other techniques such as mass spectrometry, thermogravimetric analysis (TGA), or inductively coupled plasma spectroscopy (ICP) can also be used to determine the relative monomer unit ratio. By using standards of known compositions, a reference can be established.

[0086] The coated powder may also be analyzed by solid state NMR, 13 C and 29 the NMR signals of Si can be examined to determine the presence of different moieties and the relative amounts of each moiety. Further, the inorganic oxide particles can be dissolved in various acids, and the remaining polymer film can be analyzed by NMR, 13 C and 29 the NMR signals of Si can be examined to determine the presence of different moieties and the relative amounts of each moiety. By using standards of known compositions, a reference can be established.

[0087] The coated powder can be examined for properties using light stability tests, chemical reactivity tests, and hydrophobicity tests. The coated powder is TiO 2In the light stability test, when the coated powder has a light stability of ΔE = 1 to 14 with ΔE being 15 or less, preferably ΔE = 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and 13, it is super light stable. In the DPPH light stability test, when the coated powder has a light stability of ΔE = 1 to 4 with ΔE being 4.5 or less, preferably ΔE = 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, and 1.0, the coated powder is super light stable. In the effect pigment light stability test, when the coated powder has a light stability of ΔE = 0.5 to 1.0 with ΔE being 1.15 or less, preferably 1.05, 0.95, 0.85, 0.75, 0.65, and 0.55, the coated powder is super light stable. Preferably, the coated powder has a chemical reactivity of ΔE = 0 to 20, more preferably ΔE = 0 to 17, and most preferably ΔE = 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16. Preferably, the coated powder is hydrophobic or slightly hydrophobic, and most preferably hydrophobic.

[0088] The coated powder can be used to form a dispersion using non-polar liquids, preferably cosmetic oils such as capric / caprylic triglyceride, linear alkyl benzoate, ethylhexyl benzoate, natural oils, and silicone oils. Preferably, the dispersion contains at least 50 wt% of the coated powder (solids), more preferably 50 - 65 wt% of the coated powder (solids), and at least 55 wt% of the coated powder (solids) such as at least 55 wt% of the coated powder (solids), at least 60 wt% of the coated powder (solids), and at least 65 wt% of the coated powder (solids). Such dispersions can be prepared by various conventional mixing processes including mixing using a rotor stator machine, planetary mixing, high-pressure homogenizer, ultrasonic mixing, and media milling. An additional emulsifier or dispersant can be included in the dispersion. Examples include tricereareth-4 phosphate (Hostaphat KW 340 D; manufactured by Clariant) at 5 - 15 wt% solids.

[0089] Surprisingly, the high solids dispersion of the coated powder has a relatively low viscosity. Preferably, the viscosity is at most 60,000 cP, more preferably at most 30,000 cP, and most preferably at most 6,000 cP. Examples include viscosities of 1,000 to 50,000 cP and 5,000 to 30,000 cP.

[0090] A preferred embodiment of the present invention includes the addition of an antioxidant to the dispersion containing the coated powder. The antioxidant is oxidized when exposed to UV radiation, resulting in a decrease in antioxidant power. In addition, zinc oxide and other metal oxides are photoreactive and generate free radicals upon UV radiation exposure. The metal oxides, in combination with the antioxidant, have a greater loss of AP than the antioxidant alone. However, by combining the coated powder with the antioxidant, the relative AP value of the dispersion remains higher than the relative AP value of the antioxidant alone. Since the coated powder is super light stable, the composition of the coated powder and the antioxidant exhibits a synergistic effect. The antioxidant can be effective because the UV radiation is blocked or absorbed by the particles and the AP value is retained.

[0091] The dispersion may contain one or more antioxidants. Antioxidants may include vitamins, antioxidant minerals, antioxidant proteins, antioxidant enzymes and coenzymes, phytonutrients, antioxidant hormones, mycosporine-like amino acids (MAA), antioxidants derived from seaweeds, and other types of antioxidants. The antioxidants can be water-soluble, fat-soluble, or both fat-soluble and water-soluble. Suitable vitamins include vitamin A (including retinoids and carotenoids), vitamin C (ascorbic acid), vitamin E (tocopherol), and vitamin K. Suitable retinoids include retinol, retinoic acid (tretinoin), retinal, and retinyl palmitate. Suitable minerals include copper, manganese, iodide, and zinc. Suitable enzymes and coenzymes include melatonin, superoxide dismutase, catalase, and glutathione peroxidase. Suitable phytonutrients include carotenoids, flavonoids, phenolic acids, and non-flavonoid phenolic acids. Suitable carotenoids include alpha-carotene, retinol, astaxanthin, beta-carotene, canthaxanthin, lutein, lycopene, and zeaxanthin. Suitable flavonoids include hindered phenols, apigenin, luteolin, tangeretin, isohamnetin, quercetin, myricetin, proanthocyanidins, quercetin, eriodictyol, hesperetin, naringenin, catechin, gallocatechin, epicatechin, epigallocatechin, thearubigin, daidzein, genistein, glycitein, resveratrol, pterostilbene, cyanidin, delphinidin, malvidin, pelargonidin, and petunidin. Suitable phenolic acids include phenol, polyphenol, alkylated phenol, and hindered phenol. Suitable phenols include butylated hydroxyanisole, butylated hydroxytoluene, cannabinoid, capsaicin, carvacrol, cresol, estradiol, eugenol, gallic acid, guaiacol, thymol, tyrosine, and sesamol. Gallic acid includes salts and esters of gallic acid also known as gallates.Suitable non-flavonoid phenolic acids include curcumin, flavonolignans, xanthones, and eugenol. Suitable mycosporine-like amino acids (MAAs) include mono-substituted MAAs such as mycosporine-glycine and mycosporine-taurine, di-substituted MAAs such as palitinic acid and shinorine, and derivatized MAAs such as palythine-threonine sulfate and palythine-threonine glycoside. Examples of suitable MAAs are found in (Wada et al., Mycosporine-Like Amino Acids and Their Derivatives as Natural Antioxidants. Antioxidants 2015, 4, 603-646). Antioxidants derived from seaweeds include ascorbate, glutathione, phlorotannin, echol, extronol, prenyltoluquinone, tetraprenyltoluquinol, sargothunbergol A, fucodifuroleol, terpenoids, phycocyanin, phycocyanobilin, fucoxanthin, phlorotannin, and lutein. Other possible organic antioxidants include bilirubin, citric acid, oxalic acid, phytic acid, n-acetylcysteine, uric acid, green tea, hydroxy-trolsols, dihydro-ketisetin, ubiquinone, glutathione, alpha-lipoic acid, folic acid, ellagic acid, caffeic acid, and phytoestrogens. The above antioxidants also include any salts, esters, or acid forms of the antioxidants.

[0092] The dispersion may contain one or more phytol extracts. A "phytol extract" is a substance obtained from plants. The phytol extract preferably imparts color. The phytol extract must be compatible with non-aqueous compositions, stable in air, non-staining to the skin, non-irritating to the skin at the usage amount, and non-toxic at the usage amount. The phytol extract has a purity level of at least 95%. Examples of suitable phytol extracts include curcumin, lycopene, beta-carotene, lutein, zeaxanthin, meso-zeaxanthin, and anthocyanin. Sources of curcumin include turmeric. Sources of lycopene include beet, cherry, guava, pink grapefruit, pomegranate, raspberry, red cabbage, red onion, strawberry, tomato, and watermelon. Sources of beta-carotene include apricot, cantaloupe, carrot, orange, papaya, peach, persimmon, pumpkin, butternut squash, sweet potato, winter squash, and yam. Sources of lutein, zeaxanthin, and meso-zeaxanthin include avocado, broccoli, Brussels sprouts, cabbage, green bean, leafy green, orange pepper, pea, spinach, yellow corn, and zucchini. Sources of anthocyanin include beet, blackcurrant, blueberry, cherry, eggplant, fig, grape, plum, prune, red cabbage, and red raspberry. The phytol extract may be chemically modified by hydrolysis, hydrogenation, esterification, or saponification. When a phytol extract that normally imparts color is chemically modified, it may no longer impart color. For example, curcumin imparts yellow, but hydrogenated tetra-hydrocurcumin is colorless.

[0093] The dispersion may contain one or more plant bioextracts. A "plant bioextract" is a natural extract of a plant that can provide fragrance and color. The plant bioextracts must be compatible with non-aqueous compositions, stable in air, non-staining to the skin, non-irritating to the skin in the amounts used, and non-toxic in the amounts used. Synthetic versions of plant bioextracts are outside the scope of the term "plant bioextract". Examples of suitable plant bioextracts include arnica extract (Arnica montana), basil extract (Ocimum basilicum), boswellia extract (Boswellia sacra), calendula extract (Calendula officinalis), chamomile extract (Anthemis nobilis), cinnamon oil (Cinnamomum verum), clove oil (Syzygium aromaticum), coptis extract (Coptis aspleniifolia), echinacea extract (Echinacea purpurea), eucalyptus oil (Eucalyptus occidentalis), ginger root extract (Zingiber officinale), grape seed extract (Vitis vinefera), green tea extract (Camilia sinensis), guggul resin extract (Commiphora wightii), horse chestnut seed extract (Aesculus hippocastanum), knotweed extract (Polygonum cuspidatum), licorice extract (Glycyrrhiza glabra), neem leaf extract (Azadirachta indica), olive fruit and olive leaf extract (Olea europaea), papaya extract (Caricapapaya), Peru balsam (Myroxylon balsamum), pineapple extract (Ananas comosus), pomegranate extract (Punica granatum L.), rosemary extract (Rosmarinus officinalis), sage extract (Salvia officinalis), sandalwood extract (Santalum album), turmeric extract (Curcuma longa), and witch hazel extract (Hamamelis japonica) are included. All of the above examples may include different species of the same genus of plants. For example, the witch hazel extract can be obtained from Hamamelis japonica, Hamamelis ovalis, Hamamelis mollis, or Hamamelis virginiana.

[0094] The composition may contain a phyt extract. The phyt extract may be selected to impart color. Phyt extracts that do not impart color may also be included in the composition. The phyt extract must be compatible with non-aqueous compositions, stable in air, non-staining to the skin, non-irritating to the skin at the usage amounts, and non-toxic at the usage amounts. The phyt extract has a purity level of at least 95%. Examples of suitable phyt extracts include curcumin, lycopene, beta-carotene, lutein, zeaxanthin, meso-zeaxanthin, and anthocyanin. Sources of curcumin include turmeric. Sources of lycopene include beet, cherry, persimmon, pink grapefruit, pomegranate, raspberry, red cabbage, red onion, strawberry, tomato, and watermelon. Sources of beta-carotene include apricot, cantaloupe, carrot, orange, papaya, peach, persimmon, pumpkin, winter squash, sweet potato, and yam. Sources of lutein, zeaxanthin, and meso-zeaxanthin include avocado, broccoli, Brussels sprouts, cabbage, green bean, leafy green vegetables, orange pepper, pea, spinach, yellow corn, and zucchini. Sources of anthocyanin include beet, blackcurrant, blueberry, cherry, eggplant, fig, grape, plum, prune, red cabbage, and red sorrel. The phyt extract may be chemically modified by hydrolysis, hydrogenation, esterification, or saponification. Phyt extracts that normally impart color, such as curcumin, may no longer impart color when chemically modified, such as to tetrahydrocurcumin. The composition may contain 0.01% to 5.0% of the phyt extract, preferably 0.01% to 1.0% of the phyt extract including 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, and 0.20% of the phyt extract.

[0095] The composition may contain a plant bio-extract. The plant bio-extract can provide fragrance and color. The plant bio-extract must be compatible with non-aqueous compositions such as being lipophilic or hydrophobic, stable in air, non-staining to the skin, non-irritating to the skin in the amount used, and non-toxic in the amount used. Examples of suitable plant bio-extracts include arnica extract (Arnica montana), basil extract (sweet basil), boswellia extract (Boswellia serrata), calendula extract (Calendula), chamomile extract (Roman chamomile), cinnamon oil (Cinnamomum zeylanicum), clove oil (Syzygium aromaticum), coptis extract (Coptis aspleniifolia), echinacea extract (Echinacea purpurea), eucalyptus oil (Eucalyptus occidentalis), ginger root extract (Zingiber officinale), grape seed extract (Vitis vinifera), green tea extract (Camellia sinensis), gum guggul extract (Commiphora wightii), horse chestnut extract (Aesculus hippocastanum), knotweed extract (Polygonum cuspidatum), licorice extract (Glycyrrhiza glabra), neem leaf extract (Azadirachta indica), olive fruit and olive leaf extract (Olea europaea), papaya extract (Carica papaya), peru balsam (Myroxylon balsamum), pineapple extract (Ananas comosus), pomegranate extract (Punica granatum L.), rosemary extract (Rosmarinus officinalis), sage extract (Salvia officinalis), sandalwood extract (Santalum album), turmeric extract (Curcuma longa), and witch hazel extract (Hamamelis japonica). The dispersion may contain an extract from an algal species.These species include Hijikia fusiformis, Spirulina platensis, Aphanizomenon, Spirulina maxima, Sargassum kjellamanianum, S. siliquastrum, Rhodomela confervoides, Symphjocladia latiuscula, Kappaphycus alvarezzi, Botryococcus braunii, Dunaliella salina, Cystoseira crinite, Ecklonia stolonifera, Sargassum thunbergii, S. sanbergii, and Ecklonia cava. The composition may contain 2.0% to 6.0% of a plant bioextract, preferably 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9% and 4.0% of the plant bioextract, ranging from 0.10% to 10.0%.

[0096] The composition may contain an oil-soluble antioxidant. When the antioxidant is present, the antioxidant is different from the phytogenic extract. Examples of suitable antioxidants include carotene, catechin, lycopene, resveratrol, vitamin E or vitamin A. "Vitamin E" can represent any tocopherol or tocotrienol compound that constitutes compounds of the vitamin E group such as alpha-tocopherol and gamma-tocotrienol. The composition may contain 0.01% to 5.0% of the antioxidant, preferably 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% and 2.0% of the antioxidant, and may contain 0.1% to 3.0% of the antioxidant.

[0097] The dispersion may contain one or more protist extracts. "Protist extract" is a substance obtained from protists. Protists include eukaryotes that are not animals, plants or fungi. The protist extract is preferably a substance rich in astaxanthin. Examples of suitable protist extracts include plankton extracts and algal extracts, specifically red algal extracts.

[0098] The dispersion may contain a protist extract. The protist extract is preferably a substance rich in astaxanthin. Examples of suitable protist extracts include plankton extracts and algal extracts, in particular red algal extracts. The dispersion may contain from 0.01% to 5.0% of the protist extract, preferably from 0.1% to 3.0% of the protist extract, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% and 2.0% of the protist extract. Cosmetic and dermatological preparations may contain cosmetic ingredients, adjuvants and / or additives, such as co-emulsifiers, fats and waxes, stabilizers, thickeners, biologically active ingredients, film formers, fragrances, pigments, pearlescent agents, preservatives, pigments, electrolytes, and pH regulators. Suitable co-emulsifiers are preferably emulsifiers which are also known W / O and O / W, such as, for example, polyglycerol esters, sorbitan esters or partially esterified glycerides. Typical examples of fats are glycerides; waxes such as beeswax, paraffin wax or microcrystalline wax, which may also be in combination with hydrophilic waxes. Stabilizers include, for example, metal salts of fatty acids such as magnesium stearate, aluminum stearate and / or zinc stearate. Examples of thickeners include crosslinked polyacrylic acid and its derivatives, xanthan gum, guar gum, agar, alginates and tyroses, polysaccharides such as carboxymethyl cellulose and hydroxyethyl cellulose, and fatty alcohols, monoglycerides and fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone. Biologically active ingredients include plant extracts, protein hydrolysates and vitamin complexes. Common film formers include, for example, hydrophilic colloids such as chitosan, microcrystalline chitosan or quaternized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, acrylic acid-based polymers, and quaternary cellulose derivatives. Examples of preservatives include parabens, diazolidinyl urea, iodopropynyl butylcarbamate, and sorbic acid.Examples of pearlescent agents include glycol distearates such as ethylene glycol distearate, fatty acids and fatty acid monoglycol esters. Dyes that can be used are substances suitable and approved for cosmetic purposes. Antioxidants such as amino acids, retinol, flavonoids, polyphenols, vitamin C and tocopherol may also be included.

[0099] Cosmetic and dermatological preparations can be in the form of solutions, dispersions or emulsions; for example, sun protection preparations can be in liquid, paste or solid form, such as oil-in-water creams, water-in-oil creams and lotions, aerosol foam creams, gels, fats, marking pencils, powders, sprays or alcohol-aqueous lotions. Solvents for these compositions include water; triglycerides of capric or caprylic acid, as well as fats and oils such as castor oil; fats, waxes and other natural and synthetic fatty substances, such as esters of fatty acids with lower carbon number alcohols such as isopropanol, propylene glycol or glycerin, or esters of lower carbon number alkanoic acids or fatty acids with fatty alcohols; lower carbon number alcohols, diols or polyols, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether. Other examples include isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, diisopropyl adipate, n-hexyl laurate, n-decyl oleate, glyceryl stearate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, elsyl oleate, and elsyl erucate.

[0100] Cosmetic and dermatological preparations can be in the form of a solid stick and can contain natural or synthetic waxes, fatty alcohols or fatty acid esters, such as liquid oils and fats like paraffin oil and castor oil, isopropyl myristate, semi-solid components such as yellow petrolatum and lanolin, beeswax, ceresin and microcrystalline wax, and solid components such as ozokerite, and high melting point waxes including carnauba wax and candelilla wax.

[0101] Cosmetic preparations can be in the form of a gel and preferably contain water, organic thickeners such as cellulose derivatives like gum arabic, xanthan gum, sodium alginate, and cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and inorganic thickeners such as aluminum silicate like bentonite, or a mixture of polyethylene glycol and polyethylene glycol stearate or polyethylene glycol distearate.

[0102] The coated powder and dispersion can also be included in paints, sealants and other coating agents, and may also contain binders such as polyacrylate, polyurethane, polyalkyd, polyepoxide, polysiloxane, polyacrylonitrile and / or polyester. Organic solvents can also be present and include ethanol, butyl acetate, ethyl acetate, acetone, butanol, alkanes, methanol, propanol, and pentanol; ethers / acetals such as tetrahydrofuran and 1,4-dioxane; ketones such as diacetone alcohol and methyl ethyl ketone; and polyhydric alcohol derivatives such as ethylene glycol, propylene glycol, and diethylene glycol or mixtures thereof. These compositions can be used to coat a variety of substrates, including wood, polyvinyl chloride (PVC), plastics, steel, aluminum, zinc, copper, medium density fiberboard (MDF), glass, and concrete. Depending on which coated powder is included, the composition can provide a transparent, UV-resistant, and / or more scratch-resistant film to the substrate.

[0103] A coated powder and a dispersion can be blended with a resin to provide an organic polymer composite. Examples of resins include polyethylene, polypropylene, polystyrene, polyethylene terephthalate, acrylonitrile styrene (AS) resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile ethylene styrene (AES) resin, polyvinylidene chloride, methacrylic acid resin, polyvinyl chloride, polyamide, polycarbonate, polyallyl ester, polyimide, polyacetal, polyether ketone, polyether sulfone, polyphenyl oxide and polyphenylene sulfide, as well as mixtures thereof. In these compositions, there may also be additives such as colorants, fluorescent agents, and antioxidants, anti-aging agents, UV absorbers, lubricants, antistatic agents, surfactants, fillers (the coated powder and dispersion can also act as fillers), plasticizers, stabilizers, foaming agents, expanding agents, electrically conductive powders, electrically conductive short fibers, deodorants, softeners, thickeners, viscosity depressants, diluents, water repellents, oil repellents, crosslinking agents and curing agents. These organic polymer compositions can be molded by various techniques including injection molding, blow molding, extrusion molding, calendering, flow molding, compression molding, melt blowing, and spunbonding, thereby producing shaped products such as fibers, threads, thin films, sheets, tapes, and injection molded products, as well as molded articles such as hollow fibers, pipes, and bottles. Alternatively, the composition can be subjected to a second molding method commonly applied to thermoplastic resins, such as vacuum forming, pneumatic forming, and lamination molding. [Examples]

[0104] TiO 2 , DPPH and the light stability tests of the effect pigments are customized tests. Different colorimeter light stability tests are designed to provide a high level of sensitivity to various materials. Each material has different absorption bands and reactivities, so different tests are required to accurately measure the resulting color changes upon UV radiation exposure. For example, TiO 2 is very reactive with DPPH, so typically, TiO2 It is not tested using DPPH. The three colorimetric tests can be carried out quickly and easily by comparing the color change in the sample with a standard. The test results can be verified by using other test methods such as electron spin resonance (ESR) spectroscopy.

Example

[0105] The improved light stability of the coated powder can be measured using the light stability test described above for TiO 2 In this test, the pass condition is that ΔE is 15 or less, based on experience with spectrophotometric tests including selected antioxidants and methods based on ESR. The data in Table 1 below is based on a constant 40 m 2 / g (35 nm) rutile phase TiO 2 particles. Since the coating degree on the coating surface is based on the surface area, the mass fraction of the coating components should be determined according to the specific surface area of the base particles. Modeling of the response suggests that the pass / fail condition is impaired when A + B exceeds 2.5% for the following cases. In this case, since the general base particles are 40 m 2 / g, the pass / fail boundary is represented by 0.0625% in terms of m 2 / g for all particle types. As shown in Table 1 below, all compositions meeting the criteria have a ΔE of 15 or less.

[0106]

Table 1

[0107] Since the coating is composed only of crosslinked polymer residues, the coating components are expressed as weight % of each part of the total powder (inorganic substrate plus coating), in contrast to the amount of reactants. Since not all constituent materials react with the particle surface, it is more accurate to measure the weight percentage of SiO 2 obtained from each part in the coating after calcination.

Example

[0108] A W / O formulation containing a physical UV filter (zinc oxide at 150 nm) was analyzed with respect to the amount of UV-induced free radicals using the following radical potential (RP) method.

[0109] The metastable spin probe PCA (2,2,5,5-tetramethylpyrrolidine N-oxyl) was added to the test product, the sample was inserted into a capillary quartz tube, and the concentration of the spin marker was monitored by ESR spectroscopy before and after exposure to defined UV radiation. The PCA spin probe is photostable and resistant to antioxidants but reacts immediately in the sample with UV-generated free radicals (mainly lipid peroxides and lipid radicals). The amount of UV-generated free radicals can be quantitatively detected from a calibration curve.

[0110] Materials and Methods A water / EtOH solution of the spin trap (PCA) was added to the W / O emulsion to obtain a final concentration of 0.01 mM PCA. The sample was inserted into an ESR capillary quartz tube (40 μL) before starting the ESR measurement and UV irradiation.

[0111] UV irradiation of the sample was carried out using a UV solar simulator 300 W Oriel (manufactured by Newport). The irradiation dose as the integrated value over the spectral range was E(UVB = 280 - 320) = 23.5 W / m 2 and E(UVA = 320 - 400 nm) = 180 W / m 2 The irradiation time was varied to test the effect of different UV doses. The radiation intensity was controlled before each measurement. Measurements were carried out using a commercially available high-sensitivity X-band benchtop Electron Spin Resonance Spectrometer MiniScope MS300 (manufactured by Magnettech GmbH, Berlin, Germany).

[0112] Results and Discussion The amount of UV-induced free radicals in the cosmetic complex was measured. By knowing the concentration of the spin trap PCA in the sample (0.01 mM), the reduced amount of PCA can be calculated. Since one electron is required to reduce one molecule of PCA, the radical concentration in the sample can be calculated using a calibration curve. The percentage of induced free radicals corresponding to each product is shown in Table 2.

[0113]

Table 2

[0114] Two different coating techniques regarding the coating of ZnO were tested. For the uncoated material, no protective effect was seen in the samples with a film formed from octyltriethoxysilane. In contrast, radical formation decreased to less than 3% in the samples containing ZnO with a multifunctional coating. The percentage change of induced free radicals regarding different products when the UV irradiation time changed is shown in Figure 1. The materials and monomers used to form the components of the multifunctional coating are shown in Table 3 below.

[0115]

Table 3

Examples

[0116] In the shown test design, antioxidants with different photolabilities were added to formulations containing ZnO using different coating techniques. The antioxidant activity of these formulations was determined using the AP method before and after UV irradiation of the formulations.

[0117] Antioxidants were selected according to the following criteria: (1) the antioxidants used are suitable for use in cosmetic formulations, and (2) five raw materials represent different classes of antioxidants with different molecular mechanisms, hydrophilic and lipophilic characteristics. The final concentration of each antioxidant was selected based on the antioxidant ability of the raw material. All concentrations were within the range of recommended use based on EU guidelines.

[0118] Antioxidants are oxidized when exposed to UV radiation, resulting in a decrease in antioxidant power (AP). Table 4 below shows that the AP decreases upon exposure to UV radiation. The information in the "After UV" column was collected 10 minutes after UV radiation exposure, which corresponds to 2.4 MED (minimal erythermal doses). While antioxidants reduce the number of free radicals, the AP of antioxidants decreases significantly upon exposure to UV radiation.

[0119]

Table 4

[0120] Materials and Methods The measurement of antioxidant capacity and reactivity was carried out by using ESR spectroscopy. This spectroscopic analysis technique is particularly suitable for the analysis of antioxidants in cosmetic products because it can quantify free radicals and is applicable to opaque, viscous, and colored samples. The measurements were carried out using an X-band ESR spectrometer Miniscope MS 300 (manufactured by Magnettech, Germany) and the following technical parameters: a sweep width of 60 G, a gain of 100, a modulation amplitude of 1 G, an attenuation of 7 mW, a central field of 3365 G, and a time constant of 0.14 s. Antioxidant power (AP) is a parameter that can quantify both the reactivity and rate of antioxidants. The test radical DPPH (2,2-diphenyl-1-picryl-hydrazyl, manufactured by Sigma-Aldrich, Munich, Germany) was used as the detection molecule. At least three concentrations of the test samples were prepared and added to DPPH to obtain an initial radical concentration of 0.1 mM. The signal intensity attenuation of each concentration of the test sample was recorded at different time intervals during the reaction until saturation was reached and all antioxidant active molecules reacted with the test radicals.

[0121] From these intensities, a first-order kinetics was obtained for each concentration set. Kinetic parameters were used to calculate the reaction time (t r ), and static parameters were used to calculate the characteristic weight (w c ).

[0122] For the direct comparison of different antioxidants, the AP method is standardized against the activity of vitamin C (ascorbic acid, obtained from Sigma-Aldrich, Munich, Germany, at the highest grade of purity). The antioxidant activity of a 1 ppm vitamin C solution is defined as antioxidant units (AU). For each formulation, the AP values before and after exposure to UV radiation were determined.

[0123] Results 300 mg of each formulation was applied onto a glass plate (microscope slide) and exposed to UV radiation for 10 minutes (22.7 J / cm 2 ) using a solar simulator (Honle SOL 2 solar simulator). The product was collected from the slide and the AP was determined. The sample weights before and after UV exposure were controlled for each sample. The weight loss due to water evaporation was less than 5% for all samples.

[0124] Formulations containing ZnO showed a relatively low protective effect during UV irradiation, independent of the coating. Therefore, the product containing 10% ZnO was diluted four-fold using a placebo. Therefore, the following experiments were carried out using formulations containing 2.5% ZnO. The formulations containing 2.5% ZnO showed a photoprotective effect against most of the antioxidants used due to the UV scattering effect.

[0125] Nevertheless, there was a significant difference between the two ZnO preparations: the antioxidants were less stable in formulations containing ZnO with a coating formed from octyltriethoxysilane compared to ZnO with a multifunctional coating.

[0126] The generation of UV-induced free radicals was evaluated for two ZnO-containing formulations (see Example 2 above). Particles with the multifunctional coating did not show radical generation, while high photocatalytic activity was observed in the formulation containing ZnO with a coating formed from octyltriethoxysilane. This photocatalytic activity mainly results in the generation of hydroperoxides, which are mainly hydroxyl radicals, and these react immediately with antioxidants, leading to oxidation and subsequent reduction of AP. Figure 2 shows that the relative AP value after UV irradiation is higher for the multifunctional coating than for the coating formed from octyltriethoxysilane. Data showing that the relative AP value after UV irradiation is higher for the multifunctional coating than for the coating formed from octyltriethoxysilane can be seen in Table 5.

[0127]

Table 5

Example

[0128] This example illustrates coated nanocrystalline TiO 2 powder. The coated powder is the coated powder (i) from Table 1. The coated powder contains, in terms of weight percent, 92.7% TiO 2 , 4.7% SiO 2 , 0.149% SiO 2 from the silicate moiety, and 2.5% SiO 2 from polydimethylsiloxane. The ΔE of this sample was 14.4 based on the photo-stability test. By using assays such as X-ray fluorescence (XRF) analysis and inductively coupled plasma spectroscopy (ICP), it is possible to determine the weight percent of each constituent of the calcined powder. The weight lost during calcination can be calculated using the ratio of the formula weights of the reactants and SiO 2 .

Example

[0129] (Virtual) This example illustrates coated nanocrystalline ZnO powder. Nanocrystalline ZnO (specific surface area = 17 m 2 / g, corresponding average particle size = 63 nm) is coated with a propylsilane moiety, a silicate moiety, and a polydimethylsiloxane moiety. The ZnO particles are coated with the moieties in the same relative ratio as in Example 4. The mixture is homogenized for 30 seconds and then transferred to a glass container, which is subsequently sealed. Next, the sealed container is transferred to an oven and heated to a temperature of 100 - 110 °C and held for 1.5 hours. Next, the obtained coated powder is dried by opening the container and returning the container to the same oven and holding it at a temperature of 100 - 110 °C for 1.5 hours. The obtained coated powder is highly hydrophobic and super photo-stable. The coated powder and the corresponding dispersion of this example are suitable for use in cosmetic sunscreen formulations.

Example

[0130] (Virtual) This example illustrates a high solids dispersion of a coated powder suitable for addition to cosmetic formulations. 460 g of ethylhexyl benzoate (Finsolv® EB; manufactured by Innospec) and 40 g of an emulsifier are placed in a jacketed steel container maintained at a constant temperature of 30 °C. The emulsifier tricereareth-4 phosphate (Hostaphat KW 340 D; manufactured by Clariant) is a waxy solid and an anionic O / W emulsifier, designed to be used in formulations requiring a certain level of viscosity such as cream preparations. The contents of the container are pre-mixed using a Coles type guillotine tooth high shear impeller under gentle mixing conditions for 5 minutes until the mixture is homogeneous. In the configuration used in this example, the impeller blade diameter is 1 / 3 of the container diameter and is placed 1 blade diameter from the bottom of the container. 500 g of the coated TiO 2 powder of Example 4 is added to the liquid contents under gentle mixing until all the powder is wet. Next, the mixer speed is increased to 2500 rpm for 15 minutes. The obtained dispersion is pourable.

Example

[0131] (Virtual) This example illustrates an oil-in-water type emulsified sunscreen preparation containing only an inorganic UV sunscreen agent. Put the following oil-phase components into a heated container and mix at a low intensity until it becomes transparent at 80°C.

[0132]

Table 6

[0133] Next, cool the oil-phase mixture to 60°C and mix with the coated TiO 2 powder (12.0 parts by weight) of Example 4, and then pass the mixture through a high-shear mixer until the mixture becomes homogeneous. Next, cool this mixture to 45°C.

[0134] Combine the following aqueous-phase components in a separate container.

[0135]

Table 7

[0136] Mix the homogenized oil-phase mixture and aqueous-phase mixture until a homogeneous emulsion is formed. Note that any fragrance (0.2 parts by weight) can be replaced with an equal amount of deionized water.

Example

[0137] (Virtual) This example illustrates a composition containing the coated powder of Example 5 and an antioxidant such as hydroxytyrosol. Combine 0.05% hydroxytyrosol with 2.5% ZnO. In this composition, the coated powder blocks the oxidation of the antioxidant by UV radiation, while the antioxidant increases the photo-stability of the composition, thus maintaining a higher level of AP.

Example

[0138] (Virtual) This example illustrates a composition containing the coating powder and tocopherol of Example 4. In this composition, the coating powder blocks the oxidation of the antioxidant by UV radiation, while the antioxidant increases the light stability of the composition, thus maintaining a higher level of AP.

Example

[0139] (Virtual) This example shows an example of the UV curable coating composition of the present invention. Mix the following components until homogeneous.

[0140]

Table 8

[0141] The composition of this example can be applied to a substrate as a wet film using a wire winding rod or a spray gun, and then cured using UV radiation to obtain a UV protection hard film.

Example

[0142] This example illustrates a composition containing an effect pigment. The effect pigment is typically a flat or flat-like pigment particle coated with a thin layer of a secondary material having a higher refractive index. The composition of the underlying flat plate is typically mica, synthetic mica, silica, or alumina. The coating is typically titanium dioxide (typically in the anatase form), iron oxide, and bismuth oxychloride.

[0143]

Table 9

[0144] The test was carried out at a concentration of 0.125 wt% of the effect pigment in a 0.125 wt% DPPH solution in butoxyethanol. The samples were irradiated with UVA radiation of 0.35 W / m 2 for 20 minutes. Four replicates of each sample were prepared. D-50 is measured in micrometers. In Table 9, ΔE is significant when the t-test is 1.53 or more.

[0145]

Table 10

[0146] (References) European Patent Specification No. 0761774 British Patent Specification No. 785,393 British Patent Specification No. 825,404 U.S. Patent Application Publication No. 20060167138 U.S. Patent Application Publication No. 20060210495 U.S. Patent No. 3,024,126 U.S. Patent No. 3,562,153 U.S. Patent No. 3,647,742 U.S. Patent No. 3,649,588 U.S. Patent No. 3,920,865 U.S. Patent No. 3,948,676 U.S. Patent No. 4,061,503 U.S. Patent No. 4,061,503 U.S. Patent No. 4,068,024 U.S. Patent No. 4,141,751 U.S. Patent No. 4,233,366 U.S. Patent No. 4,454,288 U.S. Patent No. 4,644,077 U.S. Patent No. 4,882,225 U.S. Patent No. 5,277,888 U.S. Patent No. 5,486,631 U.S. Patent No. 5,536,492 U.S. Patent No. 5,562,897 U.S. Patent No. 5,565,591 U.S. Patent No. 5,607,994 U.S. Patent No. 5,631,310 U.S. Patent No. 5,718,907 U.S. Patent No. 5,756,788 Specification U.S. Patent No. 5,843,525 Specification U.S. Patent No. 5,959,004 Specification U.S. Patent No. 5,993,967 Specification U.S. Patent No. 6,022,404 Specification U.S. Patent No. 6,045,650 Specification U.S. Patent No. 6,086,668 Specification U.S. Patent No. 6,214,106 Specification U.S. Patent No. 6,500,415 Specification U.S. Patent No. 7,182,938 Specification U.S. Patent No. 7,438,836 Specification International Publication No. 2009 / 131910 Pamphlet International Publication No. 95 / 23192 Pamphlet Jung K, Richter J, Kabrodt K, Lucke IM, Schellenberg I, Herrling T. The antioxidative power AP--A new quantitative time dependent (2D) parameter for the determination of the antioxidant capacity and reactivity of different plants. Spectrochim Acta A Mol Biomol Spectrosc. 63(2006):846-50 Jung K, Sacher M, Blume G, Jansen F, Herrling T. How Active are Biocosmetic Ingredients? SOFW-Journal 133 1 / 2 - 2007 Andersch Bjorkman Y(1), Hagvall L, Siwmark C, Niklasson B, Karlberg AT, Brared Christensson J. Air-oxidized linalool elicits eczema in allergic patients - a repeated open application test study. Contact Dermatitis. 2014 Mar;70(3):129-38 Jung K, Heinrich U, Tronnier H, Schnyder M, Herzog B, Herrling Th. High levels of free radicals in suncare products induce Acne Aestivalis in sensitive subjects. SOFW / 142 (2016): 2-8 Wlaschek M et al. Solar UV irradiation and dermal photoaging. J Photochem Photobiol B. 2001 Oct;63(1-3):41-51 Wada et al., Mycosporine-Like Amino Acids and Their Derivatives as Natural Antioxidants. Antioxidants 2015, 4, 603-646 Varahalaroa Vadlapudi, Antioxidant activities of marine algae: A review. Medicinal Plants as Antioxidant Agents: Understanding Their Mechanism of Action and Therapeutic Efficacy, 2012: 189-203 ISBN: 978-81-308-0509-2

Claims

1. (a) particles, and (b) (1) a silica portion, (2) an organoxysilane portion selected from the group consisting of a mono-organoxysilane portion, a bi-organoxysilane portion, and a tri-organoxysilane portion, and (3) a poly(dialkyl)siloxane portion a coating on the surface of the particles, and A coated powder containing, wherein the amount of the organoxysilane moiety and the silica moiety by equivalent weight is m of the specific surface area of the particles to be coated ２ per g, and is at least 0.0625% of the total weight of the coated powder ２ ​ the particles contain at least one oxide selected from the group consisting of ZnO, TiO₂, and mixtures thereof, the coated powder.

2. The coated powder according to Claim 1, wherein the particles have an average particle size of 15 to 150 nm.

3. The organoxysilane moieties each have the formula R １ ｎ SiO （４－ｎ）／２ (wherein n = 1, 2 or 3, and each R １ group is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl and heterocyclic radicals, and / or each R １ group has 1 to 18 carbon atoms and is independently selected from the group consisting of alkyl, alkenyl and aryl, and / or each R １ group is independently selected from the group consisting of alkyl, aryl, vinyl, glycidoxyalkyl, methacryloxyalkyl, aminoalkyl, and mercaptoalkyl); The poly(dialkyl)siloxane moieties each have the formula O(R ２ ２ SiO) ｎ (SiR ２ ２ )O or O(R ２ ２ SiO) ｎ (SiR ２ ２ )OR ｃ (wherein n is an integer from 2 to 14, each R ２ group is alkyl, and R ｃ is selected from the group consisting of H, methyl, ethyl, and propyl), and / or the organoxysilane contains a propylsilane moiety, and the poly(dialkyl)siloxane includes polydimethylsiloxane; and / or A poly(dialkyl)siloxane has the formula R ｃ O(R ２ ２ SiO) ｎ (SiR ２ ２ )OR ｃ (wherein n is an integer from 2 to 14, each R ２ group is an alkyl group, and each R ｃ group is an alkyl group or H), and / or the poly(dialkyl)siloxane is polydimethylsiloxane or polydiethylsiloxane, and / or the poly(dialkyl)siloxane is linear; The coated powder according to claim 1 or 2.

4. (1) The coated powder according to any one of Claims 1 to 3, (2) containing a fluid, and (3) optionally containing an antioxidant, a dispersion liquid, When the dispersion liquid is measured at a shear rate in the range of 0.1 second －１ to 100 seconds －１ at 25°C, it has a viscosity of up to 50,000 cP, or when the dispersion liquid is measured at a shear rate in the range of 0.1 second －１ to 100 seconds －１ at 25°C, it has a viscosity of up to 10,000 cP, the dispersion liquid.

5. The dispersion liquid according to Claim 4, further comprising a dispersion aid.

6. The dispersion liquid according to Claim 5, wherein the dispersion aid is selected from the group consisting of stearic acid, stearate, palmitic acid, palmitate, oleic acid, oleate, polyhydroxystearic acid, phosphate ester, linear alkyl-substituted amine, triglyceride ester, polyethylene glycerin ester, and mixtures thereof.

7. An oil-in-water or water-in-oil emulsion comprising the coated powder according to any one of Claims 1 to 3 and a liquid carrier, optionally, the liquid carrier is cosmetically acceptable, and / or the liquid carrier contains a member selected from the group consisting of alkyl benzoates, fatty acid esters, natural oils, silicone oils, and mixtures thereof, and / or the liquid carrier contains a member selected from the group consisting of ethyl benzoate, linear alkyl benzoates, caprylic / capric triglyceride, and mixtures thereof, the oil-in-water or water-in-oil emulsion.

8. A cosmetic composition comprising the coated powder according to any one of Claims 1 to 3.

9. A composition comprising the coated powder according to any one of Claims 1 to 3 and containing an antioxidant.

10. A dispersion liquid according to any one of Claims 4 to 6 and containing an antioxidant, wherein the antioxidant is: (i) vitamins, antioxidant minerals, antioxidant proteins, antioxidant enzymes and coenzymes, phytochemicals, and antioxidant hormones, and / or (ii) Ascorbic acid, tocopherol, green tea extract, hydroxytyrosol, retinol, retinal, retinoic acid (tretinoin), and quercetin anhydride The dispersion may be selected from the group consisting of. **Claim 11**: The dispersion according to claim 4, which is paint, stain, coating agent or ink. **Claim 12**: The dispersion according to any one of claims 4 to 6 and 10, comprising at least one extract from the group consisting of phyt extracts, plant bio extracts and protist extracts, or comprising an algal extract. **Claim 13**: The composition according to claim 8 or 9, which is an anhydrous preparation, aerosol foam cream, lotion, paste, gel, spray, stick or powder. **Claim 14**: The emulsion according to claim 7, comprising an antioxidant, wherein the antioxidant is: (i) vitamins, antioxidant minerals, antioxidant proteins, antioxidant enzymes and coenzymes, phytonutrients, and antioxidant hormones, and / or (ii) Ascorbic acid, tocopherol, green tea extract, hydroxytyrosol, retinol, retinal, retinoic acid (tretinoin), and quercetin anhydride The emulsion may be selected from the group consisting of. **Claim 15**: A paint, sealant or other coating agent for wood, plastic or other building materials, comprising the coated powder according to any one of claims 1 to 3. **Claim 16**: The emulsion according to claim 7 or 14, comprising at least one extract from the group consisting of phyt extracts, plant bio extracts and protist extracts, or comprising an algal extract. **Claim 17**: The emulsion according to any one of claims 7, 14 and 16, which is an aerosol foam cream, lotion, gel or spray. **Claim 18**: The composition according to claim 8 or 9, comprising an antioxidant, wherein the antioxidant is: (i) vitamins, antioxidant minerals, antioxidant proteins, antioxidant enzymes and coenzymes, phytonutrients, and antioxidant hormones, and / or (ii) Ascorbic acid, tocopherol, green tea extract, hydroxytyrosol, retinol, retinal, retinoic acid (tretinoin), and quercetin anhydride The composition may be selected from the group consisting of. **Claim 19**: The composition according to any one of claims 8, 9 and 18, which is paint, stain, coating agent or ink.

20. The composition according to any one of claims 8, 9, 18 and 19, comprising at least one extract from the group consisting of phytol extracts, plant bio-extracts and protist extracts, or comprising an algal extract.

21. The composition according to any one of claims 8, 9 and 18 to 20, which is an anhydrous preparation, an aerosol foam cream, a lotion, a paste, a gel, a spray, a stick or a powder.

22. The composition according to any one of claims 8, 9 and 18 to 21, for use in the following methods. A method of protecting the skin from light, comprising coating the skin with the composition; A method of protecting a keratinous material, comprising coating the keratinous material with the composition; A method of protecting human skin, comprising coating the skin with the composition; or A method of suppressing lipid peroxidation, comprising applying the composition to the skin;

23. The dispersion according to any one of claims 4 to 6 and 10 to 12, for use in the following methods. A method of protecting the skin from light, comprising coating the skin with the dispersion; A method of protecting a keratinous material, comprising coating the keratinous material with the dispersion; A method of protecting human skin, comprising coating the skin with the dispersion; or A method of suppressing lipid peroxidation, comprising applying the dispersion to the skin;

24. The emulsion according to any one of claims 7, 14, 16 and 17, for use in the following methods. A method of protecting the skin from light, comprising coating the skin with the emulsion; A method of protecting a keratinous material, comprising coating the keratinous material with the emulsion; A method of protecting human skin, comprising coating the skin with the emulsion; or A method of suppressing lipid peroxidation, comprising applying the emulsion to the skin;

25. The coated powder according to any one of claims 1 to 3, wherein the particles contain an effect pigment.

26. The coated powder according to any one of claims 1 to 3 and 25, further comprising a resin.

27. The dispersion according to any one of claims 4 to 6, 10 to 12 and 23, wherein the particles contain an effect pigment.

28. The dispersion according to any one of claims 4 to 6, 10 to 12, 23 and 27, further comprising a resin.

29. The emulsion according to any one of claims 7, 14, 16, 17 and 24, wherein the particles contain an effect pigment.

30. An emulsion according to any one of Claims 7, 14, 16, 17, 24, and 29, further comprising a resin.

31. A composition according to any one of Claims 8, 9, 13, and 18 to 22, wherein the particles contain an effect pigment.

32. A composition according to any one of Claims 8, 9, 13, 18 to 22, and 31, further comprising a resin.

33. A composition according to any one of Claims 8, 9, 13, 18 to 22, 31, and 32, for use in the following method. A method of preventing or reducing the formation of fine wrinkles and wrinkles on the skin, comprising coating the skin with the composition; A method of preventing the loss of skin elasticity, comprising coating the skin with the composition; or A method of preventing skin thinning, comprising applying the composition to the skin;

34. A dispersion according to any one of Claims 4 to 6, 10 to 12, 23, 27, and 28, for use in the following method. A method of preventing or reducing the formation of fine wrinkles and wrinkles on the skin, comprising coating the skin with the dispersion; A method of preventing the loss of skin elasticity, comprising coating the skin with the dispersion; or A method of preventing skin thinning, comprising applying the dispersion to the skin;

35. An emulsion according to any one of Claims 7, 14, 16, 17, 24, 29, and 30, for use in the following method. A method of preventing or reducing the formation of fine wrinkles and wrinkles on the skin, comprising coating the skin with the emulsion; A method of preventing the loss of skin elasticity, comprising coating the skin with the emulsion; or A method of preventing skin thinning, comprising applying the emulsion to the skin;

36. A method of protecting an antioxidant, comprising mixing the antioxidant with a coating powder according to any one of Claims 1 to 3, 25, and 26.

37. A method of protecting an antioxidant, comprising mixing the antioxidant with a dispersion according to any one of Claims 4 to 6, 10 to 12, 23, 27, 28, and 34.

38. A method of protecting an antioxidant, comprising mixing the antioxidant with an emulsion according to any one of Claims 7, 14, 16, 17, 24, 29, 30, and 35.

39. A method of protecting an antioxidant, comprising mixing the antioxidant with a composition according to any one of Claims 8, 9, 13, 18 to 22, and 31 to 33.

40. A method for producing a coating powder, comprising: (i) particles (ii)a first alkoxysilane that forms the silica moiety selected from the group consisting of tetra-alkoxysilane, poly(tetra-alkoxysilane), and mixtures thereof, (iii)an organoalkoxysilane selected from the group consisting of mono-organoalkoxysilane, bi-organoalkoxysilane, tri-organoalkoxysilane and mixtures thereof, and (iv)a second alkoxysilane selected from the group consisting of poly(dialkyl)siloxane and mixtures thereof coating the particles with a polymer by polymerizing a composition comprising The amount by weight of the organoxysilane moiety and the silica moiety, in terms of SiO ２ per gram of the specific surface area of the particles to be coated, is at least 0.0625% of the total weight of the coated powder, ２ ​ wherein the particles comprise at least one oxide selected from the group consisting of ZnO, TiO 2 and mixtures thereof, the manufacturing method.

41. The manufacturing method according to claim 40, wherein the particles have an average particle size of 15 to 150 nm.

42. The manufacturing method according to claim 40, wherein the particles contain an effect pigment.

43. The organoxysilane moieties each have the formula R １ ｎ SiO （４－ｎ）／２ wherein n = 1, 2 or 3, each R １ group is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl and heterocyclic radicals, and / or each R １ group has from 1 to 18 carbon atoms and is independently selected from the group consisting of alkyl, alkenyl and aryl, and / or each R １ group is independently selected from the group consisting of alkyl, aryl, vinyl, glycidoxyalkyl, methacryloxyalkyl, aminoalkyl, and mercaptoalkyl); The poly(dialkyl)siloxane moieties each have the formula O(R ２ ２ SiO) ｎ (SiR ２ ２ )O or O(R ２ ２ SiO) ｎ (SiR ２ ２ )OR ｃ (wherein n is an integer from 2 to 14, each R ２ group is alkyl, and R ｃ is selected from the group consisting of H, methyl, ethyl and propyl), and / or the organoxysilane contains a propylsilane moiety, and the poly(dialkyl)siloxane includes polydimethylsiloxane; and / or, A poly(dialkyl)siloxane has the formula R ｃ O(R ２ ２ SiO) ｎ (SiR ２ ２ )OR ｃ (wherein n is an integer from 2 to 14, each R ２ group is an alkyl group, and each R ｃ group is an alkyl group or H), and / or the poly(dialkyl)siloxane is polydimethylsiloxane or polydiethylsiloxane, and / or the poly(dialkyl)siloxane is linear; The manufacturing method according to any one of claims 40 to 42.

44. The polymerization is heating the composition in a sealed vacuum vessel; and / or maintaining the composition at a temperature sufficient to evaporate a portion of the composition, filling the vessel with an inert gas stream, and cooling the vessel; The manufacturing method according to any one of claims 40 to 43, comprising.

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