Composite material of bismuth oxycarbonate and organosilicon compounds for UV irradiation filtering

Abstract

This invention is based on the empirical formula (BiO) 2-x (CO3)(in the formula, -0.4

Description

[Technical Field]

[0001] The present invention relates to the field of sun protection, and more specifically to composite materials for the use of bismuth oxycarbonate and its solvates, such as its hydrate, and organosilicon compounds in ultraviolet irradiation filtering.

[0002] The present invention also relates to compositions, particularly cosmetic compositions, specifically compositions comprising composite materials of bismuth oxycarbonate and its solvates, such as its hydrate, with organosilicon compositions. [Background technology]

[0003] Keratin is exposed to sunlight on a daily basis.

[0004] Exposure to light with wavelengths between 280 nm and 400 nm is known to cause sunburn in the human epidermis. However, light with wavelengths between 280 and 320 nm, called UV-B rays, is harmful to the development of natural sunburn. This exposure also easily induces impairment of the biomechanical properties of the epidermis, which is reflected in the appearance of wrinkles and leads to premature skin aging.

[0005] UV-A rays, with wavelengths between 320 and 400 nm, are known to penetrate deeper into the skin than UV-B rays. UV-A rays promote rapid and persistent skin pigmentation. Under standard conditions, routine exposure to UV-A radiation, even for short periods, can also cause damage to collagen and elastin fibers, which is reflected in changes to skin microreliefs, the appearance of wrinkles, and uneven pigmentation (i.e., melasma, facial skin asymmetry, etc.).

[0006] Furthermore, prolonged exposure to the sun dries out hair and makes it more susceptible to damage. Therefore, protecting keratin, specifically human keratin found in skin and other tissues, is of paramount importance.

[0007] prior art To counteract these undesirable effects, it is customary to incorporate organic and / or inorganic anti-UV-A and / or anti-UV-B shielding agents into compositions intended to provide sun protection.

[0008] To date, numerous photoprotective cosmetic compositions for the skin have been proposed. These generally contain organic and / or inorganic UV shielding agents, which act by their own chemical properties and by their own physical properties through the absorption, reflection, or scattering of UV irradiation. They generally contain combinations of oil-soluble and / or water-soluble organic UV shielding agents with metal oxide pigments such as titanium dioxide (TiO2) or zinc oxide (ZnO).

[0009] Conventional organic shading agents must possess acceptable cosmetic properties, good solubility in conventional solvents, specifically oils, and good photostability, both individually and in combination. They must also be colorless or have a color acceptable to consumers as a cosmetic. These organic shading agents are generally used as mixtures, and such combinations of shading agents may limit the range of formulations.

[0010] In addition, because consumers perceive mineral sunscreens as safer, light protection using inorganic UV shields has garnered significant consumer interest in recent years. TiO2 and ZnO are the most commonly used mineral UV shields.

[0011] However, one of the major drawbacks of such mineral-based shading agents is that when applied to the skin, they cause a white cast that is undesirable for cosmetic use and generally not appreciated by users.

[0012] This effect is even more pronounced when the concentration of mineral shading agents in the composition is high, and therefore their concentrations in sunscreen formulations are limited.

[0013] To circumvent this problem, it is certainly possible to reduce the amount of inorganic shielding agent used, which would certainly result in a film with acceptable transparency on the skin. However, in that case, adequate protection in the UV range would no longer be obtained, and the advantages of such an option would be greatly limited.

[0014] Furthermore, in addition to noticeable white cast, using large quantities of these UV-blocking agents can lead to unpleasant irritation to the skin after application. Specifically, using a considerable amount of the product regularly can cause skin roughness and dryness.

[0015] Consumers are increasingly seeking products that are effective, very easy to apply, provide long-term comfort, and offer sufficient sensory characteristics. [Prior art documents] [Patent Documents]

[0016] [Patent Document 1] U.S. Patent No. 5,624,663 [Patent Document 2] European Patent No. 0669323 [Patent Document 3] U.S. Patent No. 2463264 [Patent Document 4] U.S. Patent No. 5,237,071 [Patent Document 5] U.S. Patent No. 5166355 [Patent Document 6] British Patent No. 2303549 [Patent Document 7] German patent no. 19726184 [Patent Document 8] European Patent No. 0893119 [Patent Document 9] European Patent No. 0832642 [Patent Document 10] European Patent No. 1027883 [Patent Document 11] European Patent No. 1300137 [Patent Document 12] Unique Country Permit No. 10162844

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Non-licensed literature

[0017] [Non-licensed document 1] CA Schneider, WS Rasband, KW Eliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat. Methods. 9 (2012) pp. 671~675 [Non-licensed document 2] Niら, Fabrication, modification and application of (BiO)2CO3-based photocatalysts:A review, Applied Surface Science, 365, 2016, pages 314~335 [Non-licensed document 3] Cheng, G., Shape-controlled solvothermal synthesis of bismuth subcarbonate nanomaterials, J. Solid State Chem. 183, pages 1878~1883 (2010)

Non-licensed Document 4

[0018] Therefore, there is still a demand for inorganic UV shielding agents that provide efficient light protection without the drawbacks mentioned above.

[0019] In particular, there is still a need for an inorganic UV screening agent that has the ability to efficiently block UV light, particularly in the UV-A and UV-B ranges, specifically UV-B light, has high transparency to visible light, does not cause whitening of the applied keratinous substances, and has good cosmetic properties.

[0020] Specifically, there is still a need for a mineral UV screening agent that is other than titanium dioxide or zinc oxide, specifically at high concentrations, is similarly effective, is transparent, does not cause roughness and dryness irritation to the skin, and is easy to formulate.

[0021] Specifically, the present invention aims to propose a novel mineral UV screening agent that makes it possible to meet these expectations.

Means for Solving the Problems

[0022] Thus, according to its first aspect, the present invention relates to a) particles of at least one of bismuth oxycarbonate of empirical formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm, and b) at least one organosilicon compound and relates to a composite material containing the same.

[0023] Preferably, the present invention relates to - a) a core containing at least particles of at least one of bismuth oxycarbonate of empirical formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm, - at least one layer that continuously or discontinuously surrounds said core and contains b) at least one organosilicon compound and relates to a composite material containing the same.

[0024] Preferably, the present invention relates to a) In the form of tubes, platelets and / or rods, preferably in the form of platelets and / or rods, the empirical formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), at least one kind of particles of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average size of said particles is less than 400 nm, particles, and b) at least one kind of organosilicon compound and relates to a composite material containing the same.

[0025] Preferably, the composite material according to the present invention has an average size of the maximum size of the composite material particles in the range of 0.005 μm to 10 μm.

[0026] Preferably, the average size of the maximum size of the composite material particles is in the range of 0.01 μm to 1 μm.

[0027] According to one embodiment, the composite material according to the present invention also includes, other than the bismuth oxycarbonate particles a) and its solvates, such as its hydrates, preferably selected from inorganic oxides or their hydrate forms, more preferably selected from Al(OH)3, Al2O3, SiO2, TiO2 and ZnO, even more preferably selected from Al(OH)3 or SiO2, one or more inorganic compounds c).

[0028] Surprisingly, as also shown from the examples below, the inventors have found that the composite material according to the present invention also has excellent effectiveness for ultraviolet irradiation, and particularly for UV-B light filtering, and high transparency in the visible range, and that the compositions containing them can give sufficient cosmetic properties for consumers.

[0029] For the purposes of the present invention, the term "composite material" means a particulate solid material of heterogeneous origin containing at least two immiscible components, the components of which are bonded through physical and / or chemical interactions.

[0030] For the purposes of this invention, the term "high transparency in the visible range" means particles having high transmittance of light rays between 400 and 780 nm.

[0031] For the purposes of this invention, the term "effectiveness of UV irradiation filtering" means particles in a dispersion medium containing the particles in a 0.005% mass fraction having an absorbance threshold in the UV range greater than 0.23, preferably 0.25 or higher, preferably 0.30 or higher, and more preferably 0.35 or higher. The higher the absorbance threshold, the greater the effectiveness of UV irradiation filtering.

[0032] UV-B irradiation refers to a wavelength range of 280-320 nm. UV-A irradiation refers to a wavelength range of 320-400 nm. Visible light refers to a wavelength range of 400-780 nm.

[0033] Therefore, for the purposes of the present invention, the term "UV shielding agent" is intended to refer to any compound that shields ultraviolet (UV) irradiation in the wavelength range of 280 nm to 400 nm. The term "UV-B shielding agent" is intended to refer to any compound that shields ultraviolet (UV) irradiation in the wavelength range of 280 nm to 320 nm. The term "UV-A shielding agent" is intended to refer to any compound that shields ultraviolet (UV) irradiation in the wavelength range of 320 nm to 400 nm.

[0034] This effectiveness of the composite material according to the present invention is, to the best of our knowledge, being characterized for the first time. The use of composite materials of bismuth oxycarbonate and its solvates, such as its hydrate, with organosilicon compounds in cosmetic compositions intended for efficient shielding from UV irradiation, particularly UV-B irradiation, has not been previously proposed.

[0035] The composite materials according to the present invention are specifically intended to protect keratinous substances, particularly skin and hair, from UV irradiation, especially in cosmetic compositions for sun protection, hair care, hair treatment, and makeup applications. Accordingly, according to another embodiment, the present invention also relates to non-therapeutic cosmetic uses of the composite materials according to the present invention, which include at least the application of compositions containing the composite materials according to the present invention to keratinous substances for filtering UV irradiation, preferably UV-B.

[0036] The present invention also relates to a non-therapeutic cosmetic method, which at least includes the application to a keratinous substance of a composition comprising a composite material of bismuth oxycarbonate and its solvates, such as its hydrate, as defined above, and an organosilicon compound, for filtering UV irradiation, preferably UV-B.

[0037] The present invention also relates to a method for preparing composite materials according to the present invention.

[0038] The term "keratinous substance" specifically refers to keratin fibers such as those found in the scalp, skin including the lips, and hair, eyelashes, and eyebrows, particularly skin and / or hair, preferably skin.

[0039] The term "at least one" is synonymous with "one or more."

[0040] Expressions such as "between... and...", "including...", "formed from...", and "within the range of..." should be understood to encompass both ends unless otherwise specified.

[0041] Other features, variations, and advantages of the compositions according to the present invention will become clearer by reading the following description and examples. [Brief explanation of the drawing]

[0042] [Figure 1] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a dispersion of composite material A at a concentration of 0.005 mass% in isododecane. [Figure 2] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material B dispersion containing 0.005 mass% in isododecane. [Figure 3] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a 0.005 mass% composite material C dispersion in a mixture of water / propylene glycol / polysorbate 20 in mass fractions of 49.85 / 49.85 / 0.30. [Figure 4] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a 0.005 mass% composite material D dispersion in a mixture of water / propylene glycol / polysorbate 20 in mass fractions of 49.85 / 49.85 / 0.30. [Figure 5] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a 0.005 mass% composite material E dispersion in a mixture of water / propylene glycol / polysorbate 20 in mass fractions of 49.85 / 49.85 / 0.30. [Figure 6] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a 0.005 mass% composite material F dispersion in a mixture of water / propylene glycol / polysorbate 20 in mass fractions of 49.85 / 49.85 / 0.30. [Figure 7] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material G dispersion containing 0.005 mass% in isododecane. [Figure 8] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material H dispersion containing 0.005 mass% in isododecane. [Figure 9] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material I dispersion containing 0.005 mass% in isododecane. [Figure 10] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material Z dispersion containing 0.005 mass% in isododecane. [Figure 11]Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of a 0.005 mass% composite material J dispersion in isododecane. [Figure 12] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of a 0.005 mass% composite material K dispersion in isododecane. [Figure 13] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of a 0.005 mass% composite material A dispersion A1 in caprylic / capric triglyceride. [Figure 14] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of a 0.005 mass% composite material A dispersion A2 in propylene carbonate. [Figure 15] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of composition A7 in which composite material A is 0.005 mass% in water. [Figure 16] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of composition A8 in which composite material A is 0.005 mass% in water.

Mode for Carrying Out the Invention

[0043] The present invention relates to a composite material comprising a) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, wherein the maximum average size of the particles is less than 400 nm, and b) at least one organosilicon compound.

[0044] Composite material As shown previously, the composite material comprises at least a) bismuth oxycarbonate particles and its solvates, such as its hydrates, and at least b) an organosilicon compound.

[0045] The composite material according to the present invention is of nanometer and / or micrometer size. In particular, the average size of the maximum size of the composite material particles is in the range of 0.005 μm to 10 μm.

[0046] Preferably, the average size of the maximum dimensions of the composite material particles is in the range of 0.01 μm to 1 μm.

[0047] The term "average dimension" is intended to indicate the numerical average of the dimensions of primary particles. Particle dimensions can be determined, for example, using a Hitachi HT7700 microscope, specifically by transmission electron microscopy at an accelerating voltage of 100 kV, by scanning electron microscopy, by measuring the specific surface area via the BET method, or by using a laser particle size analyzer. Preferably, particle dimensions are determined, for example, using a Hitachi HT7700 microscope, specifically by transmission electron microscopy at an accelerating voltage of 100 kV, or by scanning electron microscopy.

[0048] Prioritizing individualization, measurements are performed on the smallest individualizable or individualizable subjects. Numerical mean values ​​can be calculated by analyzing the obtained images using software, such as ImageJ software (CA Schneider, WS Rasband, KW Eliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat. Methods.9 (2012) pp. 671-675).

[0049] The average dimensions are selected from the average length L, average width l, average thickness e, or average diameter d.

[0050] The terms "average size of the maximum dimensions" or "maximum average dimensions" of a composite material or particles are intended to indicate the maximum average dimensions of a surface, for example, a face, and it is possible to measure two opposite points on an individual particle.

[0051] The "length" L of the composite material or particles is the maximum dimension of the composite material or particles that can be observed in an image taken perpendicular to the plane on which the composite material or particles are stationary.

[0052] The "width" l and "thickness" e of the composite material or particles are the lengths of the major axis and minor axis, respectively, of the smallest possible ellipse in which the median cross-sectional area of ​​the composite material or particles can be inscribed.

[0053] The "diameter" d of a composite material or particle is the maximum dimension that can be observed along a straight line passing through the center of a circle or sphere.

[0054] The composite material according to the present invention can have various shapes and structures. Specifically, the composite material according to the present invention can be spherical, cubic, plate-shaped, cylindrical, or tubular.

[0055] The shape of the composite materials specifically depends on the method of preparation and the conditions under which they are operated.

[0056] In particular, the composite material according to the present invention may be in the form of tubes, plates, fins, rods, spheres, flowers, tassels, threads, filaments, fibers, needles, cubes, or any mixture thereof.

[0057] The composite materials according to the present invention may also aggregate into the form of superstructures. For example, plates, tubes and / or rods may aggregate into the form of spheres, flowers or clusters of beads.

[0058] In one particular embodiment, the composite material according to the present invention is in the form of a sphere.

[0059] According to certain embodiments, the composite material according to the present invention is in the form of a tube, a plate and / or a rod. More preferably, the composite material according to the present invention is in the form of a plate and / or a rod.

[0060] Therefore, composite materials in the form of plates, rods, or tubes are specifically different from spherical or fibrous forms, or from flowers, tassels, threads, filaments, needles, or cubes.

[0061] It is understood that the composite materials according to the present invention may be used in mixed form. In particular, the composite materials according to the present invention may be used in a mixture of plates and / or rods and / or tubes in any proportion.

[0062] According to a preferred embodiment, the composite material according to the present invention is mainly, or without exception, in the form of a plate.

[0063] In the form of a "small plate," the composite material has a length greater than its width and a width greater than its thickness.

[0064] According to a preferred embodiment, the composite material is mainly, or without exception, in the form of a rod.

[0065] The "rod" form of the composite material has a solid cylindrical shape with a length L greater than its diameter d, or a prism shape with a solid polygonal base, preferably triangular or hexagonal, where the diameter d of the circle circumscribed within the polygonal base is less than the length L of the prism.

[0066] According to a preferred embodiment, the composite material is mainly, or without exception, in the form of a tube.

[0067] The "tube" type composite material has a hollow cylindrical shape, and its length L is greater than its diameter d.

[0068] For the purposes of this invention, the term “primarily in the form of plates / rods / tubes” is intended to indicate that at least 50%, particularly at least 70%, or even more specifically at least 90%, of the composite materials are in the form of plates / rods / tubes, respectively.

[0069] Bismuth oxycarbonate particles a) and their solvates, such as their hydrates, and organosilicon compounds b) can be arranged differently in a composite material.

[0070] According to one embodiment, the composite material may have at least one core and at least one coating or layer surrounding the core.

[0071] Therefore, the composite material may include at least one coating layer or a layer surrounding a core that is chemically different from the coating.

[0072] The coating can be formed from one or more layers.

[0073] The core of the composite material comprises at least a) bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and one or more particles of its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm.

[0074] According to a particular embodiment, the core of the composite material can consist of at least one inorganic compound c) different from said bismuth oxycarbonate particles a) and its solvates, such as its hydrates.

[0075] The composite material can contain the bismuth oxycarbonate particles a) and its solvates, such as its hydrates, as defined above, in the core and / or in the layer forming the coating.

[0076] According to a particular embodiment, the material contains at least one kind of bismuth oxycarbonate particles and its solvates, such as its hydrates, in the core as defined above.

[0077] According to another particular embodiment, the material contains bismuth oxycarbonate particles a) and its solvates, such as its hydrates, in the coating as defined above. According to one embodiment, the inorganic compound c), if present, can coat all or part of at least one kind of bismuth oxycarbonate particles a) and its solvates, such as its hydrates.

[0078] According to another embodiment, the inorganic compound c), if present, can be completely or partially coated by at least one kind of bismuth oxycarbonate particles a) and its solvates, such as its hydrates.

[0079] In particular, the molar ratio between the number of moles of the coating compound and the number of moles of the core compound ranges from 0.0001 to 20, preferably from 0.005 to 10, more preferably from 0.01 to 5, and even more preferentially from 0.05 to 3.

[0080] According to certain embodiments, the composite material according to the invention contains a layer surrounding at least one core.

[0081] Thus, according to certain embodiments, the composite material according to the invention contains a core containing at least: a) particles of bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm, said core being continuously or discontinuously surface-coated by a coating containing at least one organosilicon compound b).

[0082] According to a first variant of the invention, the composite material according to the invention is continuous, i.e. it contains a coating, also called a shell or envelope, surrounding the entire surface of the core.

[0083] According to a second variant of the invention, the composite material according to the invention is discontinuous, i.e. it contains a coating, also known as a shell or envelope, surrounding the core surface discontinuously. Preferably, 10% to 90%, more particularly 10% to 70%, even more particularly 30% to 50% of the core surface is coated with the coating.

[0084] According to one embodiment, the coating is a multilayer coating, i.e. it contains one or more inner layers and outer layers, in other words several completely or partially overlapping layers, each of which can be continuous or discontinuous.

[0085] In a multilayer coating, the term "inner layer" means any layer that is not an outer layer. This can be a layer directly applied to the core or any intermediate layer between the core and the outer layer.

[0086] In a multilayer coating, the term "outer layer" means the layer that forms the final layer of the coating not adjacent to the core. The outer layer is separated from the core by at least one inner layer. The outer layer has no coating.

[0087] In a multilayer coating consisting of two layers, the inner layer is the layer adjacent to the core, and the outer layer is the layer adjacent to the inner layer and not adjacent to the core.

[0088] In a multilayer coating consisting of more than two layers, the inner layer is the layer adjacent to the core and the intermediate layer between the core-adjacent layer and the outer layer.

[0089] The inner layer forming the multilayer coating of the composite material and the single outer layer of the composite material can be formed from the same or different compounds.

[0090] Each layer can consist of a single compound or a mixture of compounds.

[0091] In particular, the layer can extend concentrically with respect to the core.

[0092] In particular, the composite material according to the invention has a double layer surrounding the core, i.e., an inner layer and an outer layer.

[0093] According to a preferred embodiment, the composite material according to the invention preferably has at least one layer containing at least one organosilicon compound b).

[0094] According to a preferred embodiment, the composite material according to the invention - a) a core containing at least one kind of particles of bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6) and its solvates, such as its hydrates, and the maximum average dimension of the particles is less than 400 nm, and - at least one layer that continuously or discontinuously surrounds the core and contains b) at least one organosilicon compound comprises.

[0095] Preferably, the composite material according to the invention - a) a core comprising at least one particle of bismuth oxycarbonate of formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm, - a single layer adjacent to said core and comprising b) at least one organosilicon compound comprises.

[0096] According to another preferred embodiment, the composite material according to the invention - a) a core comprising at least one particle of bismuth oxycarbonate of formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm, and b) at least one organosilicon compound, - at least one layer surrounding said core and comprising b) at least one organosilicon compound comprises.

[0097] According to a preferred embodiment, the composite material according to the invention - a) a core comprising at least one particle of bismuth oxycarbonate of formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm, and b) at least one organosilicon compound, - a single layer adjacent to said core and comprising b) at least one organosilicon compound comprises.

[0098] According to a particular embodiment, the composite material according to the invention - a) a core comprising at least one particle of bismuth oxycarbonate of formula (I) (BiO) 2-xA core comprising at least one kind of particles of bismuth oxycarbonate (BiO) - An inner layer adjacent to the core and containing at least one kind of organosilicon compound - a) (BiO) 2-x A particle of bismuth oxycarbonate (BiO) (CO3) (where -0.4 < x < 0.6), and its solvate, such as its hydrate, and having a maximum average dimension of less than 400 nm, and at least one kind of organosilicon compound b), and an outer layer adjacent to the inner layer

[0099] According to another preferred embodiment, the composite material according to the present invention - a) (BiO) 2-x A particle of bismuth oxycarbonate (BiO) (CO3) (where -0.4 < x < 0.6), and its solvate, such as its hydrate, and having a maximum average dimension of less than 400 nm, and at least one kind of inorganic compound c) different from the bismuth oxycarbonate particles a), and at least one layer surrounding the core and containing at least one kind of organosilicon compound b Including

[0100] According to a preferred embodiment, the composite material according to the present invention - a) (BiO) 2-x A particle of bismuth oxycarbonate (BiO) (CO3) (where -0.4 < x < 0.6), and its solvate, such as its hydrate, and having a maximum average dimension of less than 400 nm, and at least one kind of inorganic compound c) different from the bismuth oxycarbonate particles a), and a single layer adjacent to the core and containing at least one kind of organosilicon compound b Including

[0101] According to certain embodiments, the composite material according to the invention comprises - a) at least one particle of bismuth oxycarbonate of formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, as a core, wherein the maximum average size of said particles is less than 400 nm, - an inner layer adjacent to said core and containing at least one inorganic compound c) different from said bismuth oxycarbonate particles a), - an outer layer adjacent to said inner layer and containing b) at least one organosilicon compound and comprising.

[0102] a) Bismuth oxycarbonate particles The bismuth oxycarbonate particles a) according to the invention are of formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, and the maximum average size of said particles is less than 400 nm. The value of x can be determined specifically by elemental analysis.

[0103] Preferably, x is equal to 0 and the empirical formula of the bismuth oxycarbonate particles is (BiO)2(CO3).

[0104] The bismuth oxycarbonate particles according to the invention, and their solvates, such as their hydrates, can be crystalline or amorphous.

[0105] According to one embodiment of the invention, the bismuth oxycarbonate particles are amorphous.

[0106] According to a preferred embodiment of the invention, the bismuth oxycarbonate particles are crystalline.

[0107] It is understood that the bismuth oxycarbonate particles can consist of a mixture of several bismuth oxycarbonate particles, and their solvates, such as their hydrates, having different empirical formulas and / or different shapes.

[0108] Therefore, bismuth oxycarbonate particles, and their solvates, such as their hydrates, can be a mixture of amorphous and crystalline particles.

[0109] For the purposes of the present invention, the term "crystalline" means that the atoms forming the bismuth oxycarbonate particles are arranged in an ordered manner. In other words, crystalline bismuth oxycarbonate particles are a structured material.

[0110] In contrast, "amorphous" particles are particles in which the atoms are disordered. The atoms of such particles exhibit no organization at the microscopic level.

[0111] Preferably, the crystalline particles required by the present invention are of the [Bi2O2] 2+ and [CO3] 2- and have the crystal phase of the natural mineral bismutite having alternating layers of.

[0112] Such particles crystallize in the orthorhombic system with the space group Imm2.

[0113] The bismutite crystal structure of bismuth oxycarbonate can have the following lattice parameters: a = 3.865 Å, b = 3.862 Å, c = 13.675 Å and V lattice = 0.204 nm 3 . This specific atomic arrangement specifically enables the growth of anisotropic objects.

[0114] Particles are considered "anisotropic" if the elongation coefficient R between their length L and their thickness e, i.e., R = L / e, is greater than 2.

[0115] According to the present invention, the maximum average dimension of bismuth oxycarbonate particles of formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and their solvates, such as their hydrates, is less than 400 nm.

[0116] Preferably, the maximum average dimension of said particles is 300 nm or less.

[0117] In particular, the maximum average dimension of the particles ranges from 10 nm to 300 nm, preferably from 25 nm to 250 nm, and more preferably from 25 nm to 200 nm.

[0118] According to the present invention, the bismuth oxycarbonate particles of the empirical formula (BiO) 2-x( CO3) (where -0.4 < x < 0.6) can be of any shape.

[0119] The shape of the particles specifically depends on the method of preparing them and the conditions of operation.

[0120] In particular, the particles according to the present invention can be in the form of tubes, small plates, thin plates, rods, spheres, flowers, clusters, threads, filaments, fibers, needles, cubes or any mixture thereof.

[0121] The particles according to the present invention may also aggregate in the form of superstructures. For example, small plates, tubes and / or rods can aggregate in the form of spheres, flowers or clusters.

[0122] According to a preferred embodiment, the particles according to the present invention are in the form of tubes, small plates and / or rods. Even more preferably, the particles according to the present invention are in the form of small plates and / or rods.

[0123] Therefore, particles in the form of small plates or rods or tubes are specifically different from spherical or fibrous forms or flowers, clusters, threads, filaments, needles or cubes.

[0124] It is understood that the particles according to the present invention can be used in the form of a mixture. In particular, the particles according to the present invention can be used as a mixture of small plates and / or rods and / or tubes in any proportion.

[0125] According to a preferred embodiment, the particles according to the present invention are mainly or exclusively in the form of small plates.

[0126] Particles in the form of "small plates" have a length greater than their width and a width greater than their thickness.

[0127] In particular, in the case of small plate forms, bismuth oxycarbonate particles and their solvates, such as their hydrates, - Average length L in the range of 15-300 nm, particularly in the range of 30-250 nm, preferably in the range of 50-200 nm, more preferably in the range of 70-150 nm. - An average width l in the range of 10 to 250 nm, particularly in the range of 20 to 200 nm, preferably in the range of 30 to 150 nm, and more preferably in the range of 50 to 120 nm. - Average thickness e in the range of 2 to 120 nm, particularly in the range of 5 to 100 nm, preferably in the range of 10 to 80 nm, more preferably in the range of 20 to 50 nm It has, - e <l<Lである。

[0128] According to a preferred embodiment, bismuth oxycarbonate particles and their solvates, such as their hydrates, are mainly or without exception in the form of rods.

[0129] The "rod" shaped particles are solid cylindrical in shape with a length L greater than their diameter d, or prism-shaped with a solid polygonal base, preferably triangular or hexagonal, where the diameter d of the circle circumscribed within the polygonal base is less than the length L of the prism.

[0130] In particular, when the particles are in the form of rods, whether cylindrical or polygonal, bismuth oxycarbonate particles and their solvates, such as their hydrates, - Average length L in the range of 30-300 nm, particularly in the range of 50-250 nm, preferably in the range of 70-230 nm, more preferably in the range of 70-140 nm. - Average diameter d in the range of 15-150 nm, particularly in the range of 20-130 nm, preferably in the range of 25-120 nm, more preferably in the range of 25-100 nm, and even more preferably in the range of 25-60 nm. It has, - L > d

[0131] According to a preferred embodiment, bismuth oxycarbonate particles and their solvates, such as their hydrates, are mainly or without exception in the form of tubes.

[0132] A "tubular" particle has a hollow cylindrical shape, and its length L is greater than its diameter d.

[0133] In particular, when in tubular form, bismuth oxycarbonate particles and their solvates, such as their hydrates, - Average length L in the range of 10-300 nm, particularly in the range of 20-250 nm, preferably in the range of 40-200 nm, more preferably in the range of 60-200 nm. - Average diameter d in the range of 2 to 30 nm, particularly in the range of 3 to 20 nm, and preferably in the range of 5 to 15 nm It has, - L > d

[0134] For the purposes of this invention, the term “primarily in the form of plates / rods / tubes” is intended to indicate that at least 50%, in particular at least 70%, or even more specifically at least 90%, of the particles are in the form of plates / rods / tubes, respectively.

[0135] Doping of particle a) According to certain embodiments, bismuth oxycarbonate particles and their solvates, such as their hydrates, can be doped.

[0136] In particular, bismuth oxycarbonate particles and their solvates, such as their hydrates, can be doped with one or more chemical elements that have the ability to be inserted into the structure or to partially replace already present elements.

[0137] Particles can be doped by substitution of all or some cations and / or all or some anions.

[0138] According to certain embodiments, the doping is limited to 20% of the composition with respect to the inserted cation or the cation as a substitution for bismuth.

[0139] According to this variation, the degree of doping is particularly in the range of 0.005% to 15%, preferably 0.05% to 12%, more preferably 0.1% to 10%, and even more preferably 0.5% to 6%.

[0140] In particular, bismuth oxycarbonate particles and their solvates, such as their hydrates, can be doped with cations derived from elements selected from aluminum (Al), silicon (Si), scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), silver (Ag), indium (In), lanthanum (La), cerium (Ce), tantalum (Ta), tungsten (W), and / or gold (Au).

[0141] Preferably, bismuth oxycarbonate particles can be doped with cations derived from elements selected from titanium, vanadium, manganese, iron, copper, zinc, lanthanum and / or cerium, more preferably manganese, iron and / or cerium, and even more preferably manganese or iron.

[0142] According to a variation of one embodiment, bismuth oxycarbonate particles are doped with manganese-derived cations, and the degree of doping is particularly in the range of 0.5% to 2%.

[0143] According to a variation of another embodiment, bismuth oxycarbonate particles are doped with iron-derived cations, and the degree of doping is particularly in the range of 0.5% to 2%.

[0144] According to another specific embodiment, the doping is limited to 20% of the composition with respect to the inserted anion or an anion as a substitution for a carbonate base, either in part or in whole.

[0145] According to this variation, the degree of doping is particularly in the range of 0.001% to 1%, preferably 0.002% to 0.5%, more preferably 0.003% to 0.2%, and even more preferably 0.005% to 0.1%.

[0146] In particular, bismuth oxycarbonate particles are produced using anions derived from elements selected from fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), and iodine (I), and / or, in particular, sulfate ions (SO4 2- ), sulfonate ion (S(=O)2-O - ), sulfite ions (SO3 2- ), phosphate ion (PO4 3- ) and / or iodate ion (IO3 - It can be doped using polyatomic anions selected from ). Preferably, the bismuth oxycarbonate particles are S 2- , SO3 2- SO4 2- Cl - and / or I - Using SO3, which is given higher priority. 2- SO4 2- and / or Cl - , with higher priority Cl - or SO4 2- It can be doped using this method.

[0147] According to a variation of one embodiment, bismuth oxycarbonate particles are doped with anions derived from chlorine, and the degree of doping is particularly in the range of 0.01% to 0.1%.

[0148] According to a variation of another embodiment, bismuth oxycarbonate particles are doped with anions derived from iodine, and the degree of doping is particularly in the range of 0.003% to 0.01%.

[0149] According to a variation of another embodiment, bismuth oxycarbonate particles are doped with sulfate ions, and the degree of doping is particularly in the range of 0.005% to 0.1%.

[0150] According to a variation of another embodiment, the bismuth oxycarbonate particles preferably use cations derived from elements selected from titanium, vanadium, manganese, iron, copper, zinc, lanthanum and / or cerium, more preferably manganese, iron and / or cerium, and even more preferably manganese or iron, and preferably use anions derived from elements selected from fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), iodine (I), and / or particularly sulfate ions (SO4 2- ), sulfonate ion (S(=O)2-O - ), sulfite ions (SO3 2- ), phosphate ion (PO4 3- ) and / or iodate ion (IO3 - Using polyatomic anions selected from ), S is preferred. 2- , SO3 2- SO4 2- Cl - and / or I - Using, and even more preferentially, SO3 2- SO4 2- and / or Cl - Using, and especially preferably Cl - , I - or SO4 2- It is doped using this method.

[0151] In a preferred embodiment, the bismuth oxycarbonate particles and their solvates, such as their hydrates, obtained by the present invention are undoped.

[0152] In another preferred embodiment, the bismuth oxycarbonate particles and their solvates, such as their hydrates, required by the present invention are doped. In another preferred embodiment, the bismuth oxycarbonate particles and their solvates, such as their hydrates, required by the present invention are a mixture of doped and undoped particles.

[0153] Protocol for preparing bismuth oxycarbonate particles a) Bismuth oxycarbonate particles a), and their solvates, such as their hydrates, can be obtained by any preparation method known to those skilled in the art.

[0154] For example, the synthesis of bismuth oxycarbonate particles is described in the paper by Ni et al. (Fabrication, modification and application of (BiO)2CO3-based photocatalysts: A review, Applied Surface Science, 365, 2016, pp. 314-335).

[0155] In particular, bismuth oxycarbonate particles and their solvates, such as their hydrates, can be prepared via a solvothermal pathway, an electrochemical pathway, coprecipitation, or reflux, and preferably via a solvothermal pathway or reflux.

[0156] According to a variation of the first embodiment, bismuth oxycarbonate particles and their solvates, such as their hydrates, are obtained via a solvothermal pathway, particularly from bismuth nitrate and various carbonating agents such as sodium carbonate, ammonium carbonate, or urea, in a protic polar solvent in the presence of a polyol. Such synthesis makes it possible to obtain bismuth oxycarbonate particles in the form of plates and / or rods, with a maximum dimension in the range of 50 to 300 nm.

[0157] Specifically, solvothermal synthesis of particles can be found in Cheng, G. et al. (Shape-controlled solvothermal synthesis of bismuth subcarbonate nanomaterials, J. Solid State Chem. 183, pp. 1878-1883 (2010)); Ruan, MM et al. (Facile Green Synthesis of Highly Monodisperse Bismuth Subcarbonate Micropompons Self-assembled by Nanosheets: Improved Photocatalytic Performance, Acta Physico-Chimica Sinica, 33, 2017, pp. 1033-1042); Quin et al. (Template-Free Fabrication of Bi2O3 and (BiO)2CO3 Nanotubes and Their Application in Water Treatment, Chem. Eur. J., 18, 2012, pp. 16491-16497); Cheng, G. et al. (Shape-controlled solvothermal synthesis of bismuth subcarbonate nanomaterials, J. Solid State Chem., 183, 2010, pp. 1878~1883); Liu, YY et al. (Preparation, electronic structure, and photocatalytic properties of Bi2O2CO3nanosheet, Appl. Surf. Sci., 257, 2010, pp. 172~175); Zheng et al. Journal of Molecular Catalysis A: Chemical, 2010, 317(1~2), pp. 34~40); Liu, SQThis is described in the papers by (The effects of citrate ion on morphology and photocatalytic activity of flower-like Bi2O2CO3, Ceram.Int., 40, 2014, pp. 2343-2348) or by Chen, R. et al. (Bismuth subcarbonate nanoparticles fabricated by water-in-oil microemulsion-assisted hydrothermal process exhibit anti-Helicobacter pylori properties, Mater.Res.Bull., 45, 2010, pp. 654-658).

[0158] The electron chemical synthesis of particles is specifically described in the paper by Hu, Y. et al. (Simple hydrolysis route to synthesize Bi2O2CO3 nanoplate from Bi nanopowder and its photocatalytic application, Materials Letters, 170, 2016, pp. 72-75).

[0159] The synthesis of particles by coprecipitation is specifically described in the paper by Chen, XY et al. (Controlled synthesis of bismuth oxo nanoscale crystals (BiOCl, BiOCl) 12 O 17 This method is described in "Cl2, α-Bi2O3, and (BiO)2CO3) by solution-phase methods" (J. Solid State Chem., 180, 2007, pp. 2510-2516).

[0160] The synthesis of particles by reflux is specifically described in the paper by Chen et al. (Fabrication of bismuth subcarbonate nanotube arrays from bismuth citrate, Chem.Commun., 2006, pp. 2265-2267).

[0161] According to a preferred embodiment, the bismuth oxycarbonate particles and solvates thereof, such as the hydrate, obtained by the present invention are obtained via a solvothermal pathway, for example, according to the method described by Chen et al., or by reflux, for example, according to the method described by Chen et al.

[0162] According to a preferred embodiment, the bismuth oxycarbonate particles and solvates thereof, such as the hydrate thereof, required by the present invention can be obtained by a preparation method using one or more bismuth(III) complexes, one or more carbonating agents, one or more polyols, and optionally one or more polar solvents other than polyols.

[0163] When particles used in accordance with the present invention are doped, one or more additional reagents containing doping elements may be added.

[0164] In particular, the bismuth(III) complex is selected from bismuth nitrate and its hydrate form, bismuth citrate and its hydrate form, bismuth sulfate and its hydrate form, and bismuth chloride and its hydrate form.

[0165] Bismuth(III) complexes can also be obtained from bismuth minerals, such as elemental bismuth and / or bismuth oxide and / or bismuth sulfide.

[0166] Preferably, the bismuth(III) complex is bismuth(III) nitrate of formula Bi(NO3)3·xH2O and its hydrate form, and more preferably, bismuth nitrate pentahydrate of formula Bi(NO3)3·5H2O.

[0167] In particular, the carbonating agent is selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, (NH4)2CO3, LiHCO3, NaHCO3, KHCO3, RbHCO3, CsHCO3, (NH4)HCO3, urea (NH2)2CO and urea derivatives, and CO2, preferably from Na2CO3, K2CO3, (NH2)2CO, and (NH4)2CO3, and more preferably from (NH2)2CO and / or (NH4)2CO3.

[0168] Polyols are compounds having multiple hydroxyl functional groups. Polyols can be selected from glycols, particularly ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol; short-chain or long-chain glycol polymers, such as polyethylene glycol, polypropylene glycol, polybutylene glycol; glycerol and its derivatives; or sugars, such as glucose, fructose, sucrose, xylitol, mannitol, such as D-mannitol, sorbitol, or maltitol.

[0169] According to one embodiment, the bismuth oxycarbonate particles and solvates thereof, such as the hydrate thereof, required by the present invention are obtained by a preparation method using a polyol or a mixture of polyols.

[0170] According to a variation of the first embodiment, the polyol can also be used as a solvent. Therefore, bismuth oxycarbonate particles and their solvates, such as their hydrates, can be obtained, for example, by the method described below.

[0171] Solution A is formed from a dissolved bismuth(III) complex, preferably at a concentration of 0.001 to 0.5 M, in a polyol or a mixture of polyols. Solution B is formed from a partially or completely dissolved carbonating agent, preferably at an amount of 1 to 100 equivalents relative to bismuth, in a polyol or a mixture of polyols, or a polyol or a mixture of polyols other than that used in Solution A.

[0172] In the case of cation-based doping, the dopant is preferably integrated into solution A. In the case of anion-based doping, the dopant is preferably integrated into solution B.

[0173] In the case of doping using one or more cations and / or one or more anions, the cationic dopant is preferably integrated into solution A, and the anionic dopant is preferably integrated into solution B. Solution A is then added to solution B at room temperature. If the polyol or mixture of polyols is not a liquid at room temperature, all solids are mixed together.

[0174] Next, the resulting mixture is heated at a temperature between 90 and 250°C for a reaction time between 10 minutes and 48 hours. If the desired reaction temperature is above the boiling point of the solvent, the solvothermal synthesis is carried out using an autoclave.

[0175] Preferably, the reaction temperature is between 95°C and 200°C, and the reaction time is between 1 and 24 hours, and more preferably, the reaction temperature is between 100°C and 180°C, and the reaction time is between 2 and 16 hours.

[0176] The resulting particles are isolated from the reaction medium by centrifugation and washed by a continuous cycle of dispersion and centrifugation.

[0177] After drying under vacuum at a temperature between 40°C and 60°C, a white powder is obtained.

[0178] When a polyol is used as the solvent, the resulting bismuth oxycarbonate particles and their solvates, such as the hydrate, are in the form of small plates, preferably having an average thickness e between 2 and 15 nm, and / or in the form of tubes.

[0179] According to a variation of another embodiment, the polyol is used only as an additive and not as a solvent. Thus, bismuth oxycarbonate particles and their solvates, such as their hydrates, can be obtained, for example, by the method described below.

[0180] Solution A is formed in a solvent, preferably a polar solvent, from a solution of a bismuth complex at a concentration of preferably 0.001 to 0.5 M, and its solvate, for example, its hydrate, and a polyol, preferably with a total polyol concentration of preferably 0.01 to 5 M. Solution B is formed in a polar solvent (miscible with the solvent from A) at an amount of 1 to 100 equivalents relative to the bismuth complex, which is the same as or different from that of Solution A, preferably the same.

[0181] In the case of cation-based doping, the dopant is preferably integrated into solution A. In the case of anion-based doping, the dopant is preferably integrated into solution B.

[0182] In the case of doping using one or more cations and / or one or more anions, the cationic dopant is preferably integrated into solution A, and the anionic dopant is preferably integrated into solution B.

[0183] Next, solution A is added to solution B at room temperature. The resulting mixture is then heated between 90°C and 250°C for 10 minutes to 48 hours. If the desired reaction temperature is above the boiling point of the solvent, the solvothermal synthesis is carried out using an autoclave.

[0184] Preferably, the reaction temperature is between 90°C and 150°C, and the reaction time is between 4 and 16 hours.

[0185] The resulting particles are isolated from the reaction medium by centrifugation and washed by a continuous cycle of dispersion and centrifugation.

[0186] After drying under vacuum at a temperature between 40°C and 60°C, a white powder is obtained.

[0187] When polyols are used solely as additives, they can be selected from ethylene glycol, propylene glycol, glycerol and / or sugars, preferably sugars, more preferably D-mannitol.

[0188] According to this variation, the synthesis method also uses solvents other than polyols, or mixtures of solvents other than polyols. In particular, the solvent or mixture of solvents is selected from polar solvents, preferably polar and protic solvents, such as water, C1-C6 alcohols such as ethanol or isopropanol, and mixtures thereof, with water being even more preferred as the solvent.

[0189] In particular, when a polyol is selected solely as an additive and water is selected as the solvent, bismuth oxycarbonate particles and their solvates, such as their hydrates, are preferably obtained in the form of plates and / or rods.

[0190] Organosilicon compounds (b) As previously mentioned, the composite material according to the present invention comprises b) at least one organosilicon compound.

[0191] The organosilicon compounds used in the composite material according to the present invention are selected from silanes and their polymerized forms, and siloxanes and their polymerized forms (silicones).

[0192] Preferably, the organosilicon compound is selected from silanes containing at least one hydrolyzable functional group.

[0193] In particular, organosilicon compounds are selected from alkoxysilanes, specifically monoalkoxysilanes, dialkoxysilanes, trialkoxysilanes, their oligomers, and their polymerized forms.

[0194] In the context of the present invention, the term "alkoxysilane" is used to mean a compound comprising at least one alkoxyl group, preferably two, three, or four alkoxyl groups, and more preferably at least one silicon atom having three alkoxyl groups.

[0195] The term "polymerized form of alkoxysilane" means a form of alkoxysilane partially or completely hydrolyzed by at least one compound having a hydroxyl group, including water. According to a preferred embodiment, the organosilicon compound is of the following formula (I): R 1 x Si(OR 2 ) (4-x) (I) (In the formula, - R 1 These are independently alkoxy groups containing 1 to 10 carbon atoms, NH2 amino groups, and C1-C 50 Specifically, C1~C 30 A hydrocarbon group (and / or the hydrocarbon group is optionally substituted with at least one group optionally selected from hydroxyl (OH) or thiol (SH)) containing 6 to 30 carbon atoms, an aryl group, or a (di)alkylamino group NR 3 R 4 (In the formula, R 3 and R 4 This independently represents a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms, an aminoalkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 12 carbon atoms, or a linear or branched (cyclo)alkyl group containing 1 to 20 carbon atoms, specifically 1 to 10 carbon atoms. - R 2 This represents an alkyl group containing a hydrogen atom or 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. - x represents an integer in the range of 1 to 3. All Rs 2 When all R groups represent hydrogen atoms, R 1 is understood to represent an alkoxy group containing 1 to 10 carbon atoms.) is selected from alkoxysilanes thereof, oligomers thereof, polymerized forms thereof, and / or mixtures thereof.

[0196] R 1 and R 2 may be the same or different.

[0197] The term "oligomer" means a compound obtained by oligomerization or polymerization of a compound of formula (I) containing at least two silicon atoms.

[0198] Preferably, R 1 is a C1 - C 50 , specifically C1 - C 30 hydrocarbon-based group, linear or branched, saturated or unsaturated, cyclic or acyclic, optionally interrupted by one or more atoms selected from O, NH, NR3, S, or a carbonyl diradical (CO) or combinations thereof, and / or said hydrocarbon-based group is optionally substituted by at least one group selected from a hydroxyl group (OH) or a thiol group (SH) or an aryl group containing 6 to 30 carbon atoms, such as phenyl.

[0199] Preferably, R 2 represents an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms, such as methyl or ethyl.

[0200] The alkoxysilane of formula (I), oligomers thereof, and / or mixtures thereof are - either alone or as a mixture, of the following formula (Ia) and / or (Ib) and / or (Ic):

[0201]

Chemical formula

[0202] or

[0203] [Chemical formula]

[0204] or R 1' y Si(OR 2' ) (4-y) (Ic) (wherein - Ra and Rb may be the same or different and represent a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and specifically 1 to 4 carbon atoms, a cycloalkyl group containing 3 to 20 carbon atoms, an aryl group containing 6 to 12 carbon atoms, or an aminoalkyl group containing 1 to 20 carbon atoms, - Rc is independently an alkyl group such as methyl containing 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly 1 to 4 carbon atoms (the alkyl group is optionally substituted with an aryl group), or an alkoxy group such as methoxy or ethoxy containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and particularly 1 to 2 carbon atoms, or an aryl group such as phenyl containing 6 to 12 carbon atoms, - Rd and Re may be the same or different and represent an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms, such as methyl or ethyl, - k represents an integer in the range of 0 to 5, preferably in the range of 0 to 3, - Rf is a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, and specifically 1 to 4 carbon atoms, or the following formula (II):

[0205] [Chemical formula]

[0206] (In the formula, Rn represents a hydroxide group (OH), an alkyl group containing 1 to 10 carbon atoms, preferably methyl, R' 1 C1~C 50 Specifically, C1~C 30 Represents a linear or branched, saturated or unsaturated, cyclic or acyclic hydrocarbon group, which is optionally occluded by one or more oxygen atoms, and / or the hydrocarbon group is substituted with at least one group selected from a hydroxyl group (OH) or an aryl group containing 6 to 12 carbon atoms, such as phenyl. R' 2 This represents an alkyl group containing 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, such as methyl or ethyl. (y represents an integer between 1 and 3, preferably y=1) (Represents the basis of) You can choose from these.

[0207] Specific examples of alkoxysilanes of formula (Ia), their oligomers and / or mixtures thereof include 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldiethoxysilane (APMDES), and N-cyclohexylaminomethyltriethoxysilane.

[0208] APTES can be purchased, for example, from Dow Corning under the name Xiameter OFS-6011 Silane, from Momentive Performance Materials under the name Silsoft A-1100, or from Shin-Etsu Chemical Co., Ltd. under the name KBE-903.

[0209] The compound of formula (Ia) may also be Dynasylan SIVO 210 or Dynasylan 1505, which are sold by Evonik.

[0210] N-cyclohexylaminomethyltriethoxysilane can be purchased, for example, from Wacker under the name Geniosil XL 926.

[0211] Among the alkoxysilanes of formula (Ib), their oligomers and / or their mixtures, specific examples include tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltriethoxysilane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane, and mixtures thereof.

[0212] According to a preferred embodiment, the organosilicon compound b) is selected from alkoxysilanes of formula (Ic), their oligomers, their polymerized forms, and / or their mixtures.

[0213] According to one embodiment, R' 1 represents a linear or branched, saturated, acyclic C1-C 30 , specifically C2-C 20 hydrocarbon-based group, such as an octyl, decyl, dodecyl, tetradecyl group, preferably an octyl or dodecyl group.

[0214] According to one embodiment, R' 1 represents a linear or branched, saturated or unsaturated, acyclic hydrocarbon-based group having one or more oxygen atoms interrupted, and the hydrocarbon-based group is optionally substituted with at least one hydroxyl (OH) group. In particular, R' 50 represents a 2-[methoxy(polyethyleneoxy)propyl (n = 1) group or a [hydroxy(polyethyleneoxy)propyl (n = 8-12) group. 30 1 1 1

[0215] According to one embodiment, R' 1 is a linear or branched, saturated, C1-C 20 , specifically C1-C 10 hydrocarbon-based group containing at least one hydroxyl group (OH) and / or at least one aryl group having 6 to 12 carbon atoms, such as phenyl, preferably at least one aryl group having 6 to 12 carbon atoms, such as phenyl substituted hydrocarbon-based group, and in particular, R' 1 represents a benzyl group.

[0216] According to a preferred embodiment, y = 3.

[0217] According to one embodiment, R' 2 represents a methyl or ethyl group.

[0218] According to one embodiment, the organosilicon compound b) is selected from octyltriethoxysilane, dodecyltriethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (n = 1) or [hydroxy(polyethyleneoxy)propyl]triethoxysilane (n = 8 to 12), benzyltriethoxysilane, triethoxy(2,4,4-trimethylpentyl)silane, their oligomers and / or polymerized forms and mixtures thereof.

[0219] According to one embodiment, the alkoxysilane selected from the compound of formula (I), its oligomer and / or mixture thereof is 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldiethoxysilane (APMDES), N-cyclohexylaminomethyltriethoxysilane, tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxy Silanes, propyltriethoxysilanes, isobutyltriethoxysilanes, phenyltriethoxysilanes, phenylmethyldiethoxysilanes, diphenyldiethoxysilanes, benzyltriethoxysilanes, benzylmethyldiethoxysilanes, dibenzyldiethoxysilanes, acetoxymethyltriethoxysilanes and mixtures thereof, more preferably selected from 3-aminopropyltriethoxysilane (APTES), tetraethoxysilanes (TEOS) and mixtures thereof.

[0220] According to one embodiment, the organosilicon compound is given by the following formula (III):

[0221] [ka]

[0222] (In the formula, - R1 independently represents a hydroxyl group or an alkoxy group containing 1-2 carbon atoms. - R2 independently represents a hydrogen atom, a hydroxyl group, an alkoxy group containing 1 to 10 carbon atoms, or an alkyl group containing 1 to 20 carbon atoms, and is optionally substituted with at least one group selected from a hydroxyl group (OH) or a thiol group (SH), wherein the alkyl group is preferably optionally substituted with at least one hydroxyl group (OH). - A independently represents an alkylene group containing 2-3 carbon atoms. - m represents an integer in the range of 1 to 3, n represents an integer in the range of 0 to 2, and m + n = 3. - Y independently represents an oxygen atom or a -NH-CO- group, or a -CO-NH- group or a -NH-CO-NH- group. - p is equal to 0 or 1, - q is equal to 0 or 1, - r is equal to 0 or 1, - x represents an integer in the range of 0 to 500, where, - If Y represents an -NH-CO- group or an -CO-NH- group, then p=1, q=0, and x>0. - If Y represents an -NH-CO-NH- group, then q=1, p=1, and x>0. - If r=0, then p=1 and q=0, - If x=0, then q=r=0 and p=1. It is selected from the following compounds.

[0223] According to one embodiment, the compound of formula (III) is: - R1 independently represents a hydroxyl group or an alkoxy group containing 1-2 carbon atoms. - R2 independently represents a hydrogen atom, a hydroxyl group, an alkyl group containing 1 to 10 carbon atoms, preferably a methyl group, or an alkoxy group containing 1 to 10 carbon atoms. - A represents an alkylene group containing 2-3 carbon atoms. - m represents an integer in the range of 1 to 3, n represents an integer in the range of 0 to 2, and m + n = 3. - Y represents an -NH-CO- group, an -CO-NH- group, or an -NH-CO-NH- group. - p is equal to 0 or 1, - q is equal to 0 or 1, - r is equal to 1, - x represents an integer in the range of 1 to 500. It is.

[0224] Compounds of formula (III) that may be used in the context of the present invention are: Compound of formula (IIIa) below:

[0225] [ka]

[0226] (In the formula, - R'2 and R''2 independently represent a hydrogen atom, a hydroxyl group, an alkyl group containing 1 to 10 carbon atoms, preferably a methyl group, or an alkoxy group containing 1 to 10 carbon atoms, preferably an alkoxy group. - A independently represents an alkylene group containing 2-3 carbon atoms. (x represents an integer in the range of 1 to 500) Compound of formula (IIIb) below:

[0227] [ka]

[0228] (In the formula, - R1 represents a hydroxyl group or an alkoxy group containing 1-2 carbon atoms, preferably an alkoxy group. - R'2 and R''2 independently represent alkyl groups containing one or two carbon atoms. - A independently represents an alkylene group containing 2-3 carbon atoms. (x represents an integer in the range of 1 to 500) Compounds of the following formula (IIIc):

[0229] [ka]

[0230] (In the formula, - R1 represents a hydrogen atom, a hydroxyl group, an alkyl group containing 1 to 10 carbon atoms, preferably a methyl group, or an alkoxy group containing 1 to 2 carbon atoms, preferably an alkoxy group containing 1 to 2 carbon atoms. - R'2 and R''2 independently represent an alkyl group containing a hydrogen atom, one or two carbon atoms, - A independently represents an alkylene group containing 2-3 carbon atoms. (x represents an integer in the range of 1 to 500) Compound of formula (IIId) below:

[0231] [ka]

[0232] (In the formula, - R1 represents a hydrogen atom, a hydroxyl group, an alkyl group containing 1 to 10 carbon atoms, preferably a methyl group, or an alkoxy group containing 1 to 2 carbon atoms, preferably an alkoxy group containing 1 to 2 carbon atoms. - R'2 and R''2 independently represent an alkyl group containing a hydrogen atom, one or two carbon atoms, - A independently represents an alkylene group containing 2-3 carbon atoms. (x represents an integer in the range of 1 to 500) You can choose from these. Among the polyoxyalkylenes of formula (IIIa), the following compounds can be listed.

[0233] [Table 1]

[0234] Among the compounds of formula (IIIb), PEO compounds: - Those having triethoxysilane terminal functional groups, for example, SP-1P-2-006 (CAS number: 666829-33-0) by Specific Polymers, SP-1P-2-007 (PEO18 bistriethoxysilane, CAS number: 623933-43-7), SP-1P-2-015 (PEO9 triethoxysilane, CAS number: 97969-60-3), SP-1P-2-016 (PEO21 triethoxysilane, CAS number: 97969-60-3), SP-1P-2-017 (PEO44 triethoxysilane, CAS number: 97969-60-3), SP-1P-2-018 (PEO11 bistriethoxysilane, CAS number: Compounds sold under the names 97969-60-3), SP-1P-2-019 (PEO25 bistriethoxysilane, CAS number: 666829-33-0), SP-1P-2-020 (PEO6 bistriethoxysilane, CAS number: 666829-33-0), SP-1P-2-035 (PEO5 bistriethoxysilane, CAS number: 328239-08-3), or those sold by Gelest, SIB1824.84 (bis(3-triethoxysilylpropyl) polyethylene oxide (25-30 EO), CAS number: 666829-33-0), - Those having a trimethoxysilane-terminated functional group, for example, those sold by Specific Polymers under the name SP-1P-2-013 (CAS number: 70776-52-2). One could list these:

[0235] Among the polyoxyalkylenes of formula (IIIb), PPO compounds: - Compounds having a triethoxysilane terminal functional group, for example, those sold by Specific Polymers under the names SP-1P-2-026 (PPO19 bistriethoxysilane, CAS number: 1017971-44-6) and SP-1P-2-036 (PEO bistriethoxysilane, CAS number: 1017971-44-6). One could list these:

[0236] Among the compounds of formula (IIIc), those having a triethoxysilane terminal functional group include the following compounds sold by Gelest: SIB1824.81 (bis[(3-triethoxysilylpropyl)aminocarbonyl]polyethylene oxide (7-10 EO), CAS number: 178884-91-8), SIB1824.82 (N,N'-bis-[(3-triethoxysilylpropyl)aminocarbonyl]polyethylene oxide (10-15 EO), CAS number: 178884-91-8).

[0237] Among the compounds of formula (IIId), examples include compounds having a triethoxysilane terminal functional group, such as those sold by Creative PEGWorks under the names PSB-3380, PSB-3381, PSB-3382, and PSB-3383.

[0238] According to a particular embodiment, the organosilicon compound of the composite material according to the present invention is selected from siloxanes.

[0239] Among siloxanes, examples include dimethylsiloxane, such as hexamethyldisiloxane, or decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethyltetrasiloxane, or polydimethylsiloxane.

[0240] Preferably, the organosilicon compound of the composite material according to the present invention is selected from alkoxysilanes, their oligomers, and / or polymerized forms.

[0241] Preferably, the organosilicon compound of the composite material according to the present invention is selected from octyltriethoxysilane, dodecyltriethoxysilane, triethoxy(2,4,4-trimethylpentyl)silane, benzyltriethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (n=1), and [hydroxy(polyethyleneoxy)propyl]triethoxysilane (n=8~12).

[0242] Preferably, the organosilicon compound of the composite material according to the present invention is selected from octyltriethoxysilane and dodecyltriethoxysilane.

[0243] According to a particular embodiment, the molar ratio between the organosilicon compound b) according to the present invention, bismuth oxycarbonate particles a), and its solvate, for example, its hydrate, is in the range of 0.0001 to 20, particularly 0.001 to 5, preferably 0.01 to 2, and more preferably 0.05 to 1.

[0244] Inorganic compounds c) According to certain embodiments, the composite material according to the present invention may also include at least one inorganic compound c) that is different from the bismuth oxycarbonate particles a) and its solvates, such as its hydrates.

[0245] Inorganic compound c) may be an amorphous or crystalline hydrate or ahydrate of an oxide, hydroxide or oxyhydroxide of an alkali metal or alkaline earth metal, specifically sodium, potassium, magnesium and calcium; or a transition metal, specifically titanium, aluminum, manganese, iron, copper, niobium and tantalum; or a lanthanide, specifically cerium; or a poor metal, specifically zinc, indium and bismuth.

[0246] Inorganic oxides may also exist as amorphous or crystalline hydrates or ahydrates of metalloid oxides, hydroxides, or oxyhydroxides.

[0247] In particular, inorganic compound c) may be in the form of amorphous or crystalline hydrates or ahydrates containing clay, of silicon oxides, hydroxides or oxyhydroxides, such as silica SiO2, lithium and / or sodium and / or potassium and / or ammonium and / or calcium and / or magnesium and / or aluminum and / or titanium and / or iron and / or zinc and / or bismuth silicates, or aluminum and / or calcium and / or magnesium and / or sodium and / or titanium and / or iron and / or zinc and / or bismuth borosilicates.

[0248] In particular, inorganic compound c) may be in amorphous or crystalline hydrate or nonhydrate form of inorganic carbides, sulfides, or nitrides, such as silicon carbide, iron sulfide, copper sulfide, and zinc sulfide, or, for example, boron nitride and silicon nitride.

[0249] Examples of metal oxides include Al2O3, Al(OH)3, SiO2, TiO2, MnO, MnO2, FeO(OH), Fe3O4, Fe2O3, Cu(OH)2, Cu2O, CuO, Zn(OH)2, ZnO, Nb2O5, In(OH)3, In2O3, Ce2O3, CeO2, Ta2O5, WO3, Bi2O3, and mixtures thereof, in hydrated or unhydrated forms.

[0250] Preferably, hydrated or unhydrated forms of Al2O3 such as Al(OH)3, SiO2, TiO2, ZnO, and mixtures thereof are used; more preferably, hydrated or unhydrated forms of Al2O3 such as Al(OH)3, or hydrated or unhydrated forms of SiO2, TiO2, ZnO, and mixtures thereof are used; and even more preferably, hydrated or unhydrated forms of Al2O3 such as Al(OH)3, or SiO2, and mixtures thereof are used.

[0251] According to a preferred embodiment, the composite material according to the present invention does not contain any inorganic compound c) other than the bismuth oxycarbonate particles a) and its solvates, such as its hydrate.

[0252] According to another preferred embodiment, the composite material according to the present invention comprises bismuth oxycarbonate particles a) and an inorganic compound c) different therefrom, such as its solvate, preferably an inorganic oxide, more preferably one selected from silica, alumina, titanium dioxide, and zinc oxide, and even better from silica.

[0253] According to another preferred embodiment, the composite material according to the present invention comprises only one inorganic compound c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic hydroxides or inorganic oxyhydroxides, more preferably from inorganic hydroxides, more preferably from Al(OH)3, Zn(OH)2, In(OH)3 or mixtures thereof, even more preferably from Al(OH)3, Zn(OH)2, and even better from Al(OH)3.

[0254] Preferably, the composite material according to the present invention contains one or more inorganic compounds c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic oxides, more preferably from zinc, titanium, silicon and / or aluminum oxides, and more preferably from silicon and / or aluminum oxides, which are optionally hydrated.

[0255] Preferably, the composite material according to the present invention comprises one or more inorganic compounds c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic oxides, more preferably selected from Al(OH)3, SiO2, TiO2, and ZnO, and even more preferably selected from Al(OH)3 or SiO2.

[0256] According to a particular embodiment, when one or more inorganic compounds c) are present, the average size of the maximum dimensions of the composite material particles is less than 10 μm, particularly less than 2.5 μm, preferably less than 1 μm, and more preferably less than 500 nm.

[0257] Method for preparing composite materials The composite material according to the present invention can be obtained specifically through the preparation method described below.

[0258] In particular, the composite material according to the invention can be obtained by chemically grafting or physically adsorbing an organosilicon compound b) directly onto the surface of the bismuth oxycarbonate particles a) defined above and its solvates, such as its hydrates, or onto the surface of particles comprising the bismuth oxycarbonate particles a) defined above and its solvates, such as its hydrates and an inorganic compound c).

[0259] In particular, the composite material according to the invention can be obtained by reaction with a functionalized alkoxysilane via a variation of the method specifically described by Zhang et al. (Preparation Method of Silicone Rubber Radiation Protection Nano Composite Material. CN109608890B, 2018) of one or more alkoxysilanes (preferably amphiphilic, more preferably octyltriethoxysilane or dodecyltriethoxysilane) in the inorganic part of the material under consideration.

[0260] Particles comprising at least one bismuth oxycarbonate particle defined above and its solvates, such as its hydrates, and one or more inorganic compounds c) can be prepared in one or more steps.

[0261] In particular, the composite material according to the invention can be obtained in one or more steps.

[0262] In particular, the method for preparing the composite material according to the invention is - At least one particle a) of bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6) and its solvates, such as its hydrates, the maximum average dimension of said particles being less than 400 nm, - Optionally, one or more precursors intended to form an inorganic compound c) different from the bismuth oxycarbonate particles and their solvates, such as their hydrates - One or more organosilicon compounds as defined above (b), particularly alkoxysilanes as defined above, - One or more additives of any choice, and - One or more solvents of your choice Use this.

[0263] According to certain embodiments, a method for preparing a composite material according to the present invention may include one or more separation steps, for example, by filtration and / or centrifugation.

[0264] According to certain embodiments, a method for preparing a composite material according to the present invention may include one or more heat treatment steps, in which case, one step is performed in an inert or non-inert atmosphere with or without a solvent, at a temperature in the range of 50°C to 1200°C, particularly to remove the solvent and / or other volatile residual molecules from the material, and / or to induce changes such as dehydration or crystallization.

[0265] In particular, the precursor intended to form an inorganic compound c) different from the bismuth oxycarbonate particles a) is selected from organic or inorganic compounds that bring the bismuth oxycarbonate particles a) and the inorganic compound c) particles together through chemical reaction or physical adsorption.

[0266] In particular, the precursor is - As previously defined inorganic compounds c), - Inorganic metal precursors of chemical elements and their hydrates, especially dissolved metal oxides, specifically sodium silicate or sodium aluminate, halides and their hydrates, nitrates and their hydrates, carbonates and their hydrates, sulfonates and their hydrates, sulfates and their hydrates, or phosphates and their hydrates. - Organometallic precursors and their hydrates, in particular alkoxides and their hydrates, carboxylates and their hydrates, lactates and their hydrates, or citrates and their hydrates, - those mixtures You can choose from these.

[0267] The precursor intended to form the auxiliary inorganic compound c) may also be selected from oxidation precursors, particularly air, hydrogen peroxide, peroxides and their hydrates, and / or sulfiding agents, particularly hydrogen sulfide, alkali metal sulfides and their hydrates, and / or nitriding agents.

[0268] According to a preferred embodiment, the method for preparing the composite material according to the present invention does not use a precursor to form an inorganic compound c) different from the bismuth oxycarbonate particles a).

[0269] According to a preferred embodiment, a method for preparing a composite material according to the present invention uses at least one precursor intended to form an inorganic compound c) different from the bismuth oxycarbonate particles a), the precursor being preferably selected from sodium silicate and sodium aluminate.

[0270] According to a particular embodiment, the method for preparing a composite material according to the present invention uses at least one solvent.

[0271] The choice of solvent may depend particularly on the precursors and additives used in the method.

[0272] In particular, the solvent can be selected from polar or nonpolar, protic or aprotic solvents. Preferably, the solvent used is a protic polar solvent, and is selected in particular from water, alcohols, polyols and mixtures thereof.

[0273] According to a particular embodiment, the method for preparing a composite material according to the present invention uses at least one additive.

[0274] In particular, additives can be selected from acids, especially mineral acids such as hydrochloric acid or sulfuric acid, and bases, preferably mineral bases such as sodium hydroxide or potassium hydroxide. Additives can also be selected from oxidizing agents, reducing agents, and / or any reagents required for the precipitation and / or adhesion of species.

[0275] The previously defined organosilicon compound b) can be used as a pure substance or a mixture. The previously defined organosilicon compound b) can be dissolved in a solvent or used without a solvent.

[0276] According to a specific embodiment, the present invention is directed to a method for preparing the previously defined composite material, (i) a) Dispersions of bismuth oxycarbonate of the empirical formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6) and its solvates, such as its hydrates, with a maximum average dimension of the particles less than 400 nm, are prepared in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L, (ii) preparing a solution of at least one organosilicon compound b), optionally as a mixture with at least one solvent, (iii) contacting the dispersion (i) and the solution (ii) to form a composite material, (iv) isolating the composite material is included.

[0277] In particular, the solvents in steps (i) and (ii) may be the same or different.

[0278] In particular, the solvent in step (i) is selected from protic polar solvents, more preferably from water, alcohols, polyols and mixtures thereof, and even more preferably the solvent is water.

[0279] In particular, the solvent in step (ii) is selected from protic polar solvents, more preferably from alcohols, and even more preferably the solvent is the alcohol corresponding to the alkoxide group of the organosilicon compound b).

[0280] According to a specific embodiment, the dispersion medium (i) can be heated to a temperature preferably below 80 °C for refluxing.

[0281] According to a particular embodiment, solution (ii) may be heated to a temperature of preferably 80°C before mixing in step (iii) in order to reflux.

[0282] According to a particular embodiment, the molar ratio of organosilicon compound b) / bismuth oxycarbonate a) in step (iii) is in the range of 0.0001 to 20, preferably in the range of 0.005 to 10, more preferably in the range of 0.01 to 5, and even more preferably in the range of 0.05 to 3. According to a particular embodiment, the pH in step (iii) is adjusted to be between 1.5 and 5, preferably between 2 and 4.

[0283] According to a particular embodiment, the pH in step (iii) is adjusted to be between 8 and 12, preferably between 9 and 11.

[0284] According to a particular embodiment, step (iii) is carried out with stirring.

[0285] According to a preferred embodiment, step (iii) is carried out while heating the reaction medium to a temperature preferably in the range of 70°C to 80°C.

[0286] According to a particular embodiment, step (iii) is carried out for a period of time ranging from 15 minutes to 48 hours, preferably 1 hour to 24 hours, and more preferably 2 hours to 8 hours.

[0287] According to certain embodiments, a cooling step can be performed between steps (iii) and (iv).

[0288] According to a particular embodiment, step (iv) can be carried out by centrifugal separation.

[0289] According to a particular embodiment, following step (iv), the washing step is performed, specifically in a continuous cycle, by an optional drying step such as oven drying, at a temperature in the range of 40°C to 100°C, and optionally under vacuum (pressure less than 100 mbar).

[0290] According to certain embodiments, the present invention is directed to a method for preparing the composite material defined above, (a) a dispersion of particles a) of bismuth oxycarbonate of empirical formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6) and its solvates, such as its hydrates, having a maximum average dimension of less than 400 nm, in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L, (b) preparing an aqueous sodium silicate solution; (c) contacting the dispersion (a) and the solution (b) to form particles of bismuth oxycarbonate and silica; (d) isolating the particles of bismuth oxycarbonate and silica; (e) dispersing the particles of bismuth oxycarbonate and silica (d) in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L; (f) preparing a solution of at least one organosilicon compound (b), optionally as a mixture with at least one solvent; (g) contacting the dispersion (e) and the solution (f) to form a composite material; (h) isolating the composite material comprising.

[0291] According to certain embodiments, the preparation method includes a calcination step (d') before step (e).

[0292] According to certain embodiments, the calcination step (d') is carried out at a temperature in the range of 200 °C to 400 °C, preferably 250 °C to 300 °C, particularly for a time in the range of 15 minutes to 2 hours.

[0293] In particular, the solvents in steps (a), (e) and (f) may be the same or different, preferably selected from protic polar solvents, more preferably water, alcohol, polyol and mixtures thereof.

[0294] According to a particular embodiment, the dispersion medium (a) may be heated to a temperature of preferably 100°C or lower in order to reflux.

[0295] According to a particular embodiment, the molar ratio of Si / Bi in step (c) is in the range of 0.001 to 10, preferably 0.01 to 2, and more preferably 0.1 to 1.

[0296] According to a particular embodiment, the pH in step (c) is adjusted to a pH in the range of 3 to 11, particularly 5 to 8, preferably 6 to 7.

[0297] According to a particular embodiment, step (c) is carried out with stirring.

[0298] According to a particular embodiment, step (c) is carried out for a period of time ranging from 15 minutes to 48 hours, preferably 1 hour to 24 hours, and more preferably 2 hours to 8 hours.

[0299] According to a preferred embodiment, step (c) is carried out at a temperature below 100°C.

[0300] According to a particular embodiment, step (d) can be carried out by centrifugal separation.

[0301] According to a particular embodiment, following step (d), the washing step is performed, specifically in a continuous cycle, optionally by a drying step such as oven drying, at a temperature in the range of 40°C to 100°C, optionally under vacuum (pressure less than 100 mbar).

[0302] According to certain embodiments, the dispersion medium (e) may be heated to a temperature of preferably 80°C or lower in order to reflux.

[0303] According to a particular embodiment, solution (f) may be heated to a temperature of preferably 80°C before mixing in step (g) in order to reflux.

[0304] According to a particular embodiment, in step (g), the molar ratio of organosilicon compound b) / bismuth oxycarbonate and silica particles is in the range of 0.0001 to 20, preferably 0.005 to 10, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

[0305] According to a particular embodiment, the pH in step (g) is adjusted to be between 1.5 and 5, preferably between 2 and 4.

[0306] According to a particular embodiment, the pH in step (g) is adjusted to be between 8 and 12, preferably between 9 and 11.

[0307] According to a particular embodiment, step (g) is carried out with stirring.

[0308] According to a preferred embodiment, step (g) is carried out at a temperature in the range of 70°C to 80°C.

[0309] According to a particular embodiment, step (g) is carried out for a period of time ranging from 15 minutes to 48 hours, preferably 1 hour to 24 hours, and more preferably 2 hours to 8 hours.

[0310] According to a particular embodiment, a cooling step can be performed between steps (g) and (h).

[0311] According to a particular embodiment, step (h) can be carried out by centrifugal separation.

[0312] According to a particular embodiment, following step (h), a cleaning step is performed, specifically in a continuous cycle, optionally by oven drying at a temperature in the range of 40°C to 100°C, optionally under vacuum (pressure less than 100 mbar).

[0313] According to certain embodiments, the present invention relates to a method for preparing a previously defined composite material, (1) Empirical formula (I)(BiO) 2-x(CO3) (where -0.4 < x < 0.6), bismuth oxycarbonate, and its solvates, such as its hydrates, particles a), wherein the maximum average dimension of the particles is less than 400 nm, preparing a dispersion of particles a) in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L, (2) preparing a solution of alumina in soluble and / or hydrated form, such as a solution of an aluminum salt, in at least one solvent, (3) contacting the dispersion (1) and the solution (2), (3') optionally, isolating the mixture obtained from step (3), (3'') optionally, subjecting the mixture isolated from step (3') to a firing step to obtain particles of bismuth oxycarbonate and alumina, (3''') optionally, dispersing the particles of bismuth oxycarbonate and alumina (3'') in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L, (4) preparing a solution of at least one organosilicon compound b), optionally as a mixture with at least one solvent, (5) contacting the mixture or dispersion (3''') obtained as a result of step (3) with the solution (4) to form a composite material, (6) isolating the composite material comprising.

[0314] According to a particular embodiment, the firing step is carried out at a temperature in the range of 200°C to 400°C, preferably 250°C to 300°C, particularly for a time in the range of 15 minutes to 12 hours.

[0315] Particularly, the solvents in steps (1), (2) and (4) may be the same or different, preferably selected from protic polar solvents, more preferably water, alcohol, polyol and mixtures thereof.

[0316] According to a particular embodiment, the bismuth oxycarbonate particles and their solvates, such as their hydrates, are present in the dispersion (1) at concentrations ranging from 0.05 g / L to 500 g / L, preferably 10 g / L to 250 g / L, and more preferably 50 g / L to 150 g / L.

[0317] According to a particular embodiment, the dispersion medium (1) may be heated to a temperature in the range of 40°C to 200°C, preferably 50°C to 100°C, for a time in particular in the range of 1 minute to 24 hours, preferably 20 minutes to 2 hours.

[0318] According to a particular embodiment, if the solvent or solvent mixture in step (1) contains water, the pH can be adjusted to between 5 and 10, preferably between 6 and 8, by adding, for example, at least one base, preferably a mineral base such as an alkali metal or alkaline earth metal hydroxide, and in particular, the pH can be adjusted using sodium hydroxide.

[0319] According to a preferred embodiment, the aluminum salt in step (2) is sodium aluminate. According to a particular embodiment, the molar ratio of Al / Bi in step (3) is in the range of 0.0001 to 20, preferably 0.005 to 10, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

[0320] According to a particular embodiment, the pH in step (3) is adjusted to pH 6.5 by adding, for example, at least one acid, preferably a mineral acid such as sulfuric acid.

[0321] According to a particular embodiment, step (3) is carried out while stirring.

[0322] According to a particular embodiment, step (3) is carried out for a period of time ranging from 1 minute to 24 hours, preferably from 20 minutes to 8 hours.

[0323] According to a preferred embodiment, step (3) is carried out at a temperature in the range of 60°C to 70°C.

[0324] According to a particular embodiment, the cleaning step is performed prior to step (4), specifically in a continuous cycle, optionally by oven drying at a temperature of, for example, 50°C, and optionally under vacuum (pressure less than 100 mbar).

[0325] According to certain embodiments, solution (4) may be heated to a temperature of preferably 80°C before mixing in step (5) in order to reflux.

[0326] According to certain embodiments, the dispersion medium (5) may be heated to a temperature of preferably 80°C or lower in order to reflux.

[0327] According to a particular embodiment, the molar ratio of organosilicon compound b) / bismuth oxycarbonate particles in step (5) is in the range of 0.0001 to 20, preferably 0.005 to 10, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

[0328] According to a particular embodiment, the pH in step (5) is adjusted to be between 1.5 and 5, preferably between 2 and 4.

[0329] According to a particular embodiment, the pH in step (5) is adjusted to be between 8 and 12, preferably between 9 and 11.

[0330] According to a particular embodiment, step (5) is carried out while stirring.

[0331] According to a preferred embodiment, step (5) is carried out at a temperature in the range of 70°C to 80°C.

[0332] According to a particular embodiment, step (5) is carried out for a period of time ranging from 15 minutes to 48 hours, preferably 1 hour to 24 hours, and more preferably 2 hours to 8 hours.

[0333] According to certain embodiments, a cooling step can be performed between steps (5) and (6).

[0334] According to a particular embodiment, step (6) can be carried out by centrifugal separation.

[0335] According to a particular embodiment, following step (6), the cleaning step is performed, specifically in a continuous cycle, optionally by oven drying at a temperature in the range of 40°C to 100°C, optionally under vacuum (pressure less than 100 mbar).

[0336] Cosmetic composition The composite material according to the present invention can be used in compositions, particularly in cosmetic compositions.

[0337] Therefore, the present invention also relates to compositions comprising at least one of the previously defined composite materials, specifically cosmetic compositions.

[0338] According to a preferred embodiment, the present invention also, i) At least one type of previously defined composite material, ii) at least one aqueous phase and / or at least one fatty phase, iii) At least one compound selected from 1) a UV shielding agent different from composite material i), 2) a coloring agent, 3) a cosmetic surfactant for caring for keratin substances, 4) a surfactant, 5) a thickener, and mixtures thereof. This also relates to compositions, including, and specifically to cosmetic compositions.

[0339] The composite material may be present in the composition, preferably a cosmetic composition, in an amount of 0.5% to 70% by mass, preferably 1% to 50% by mass, and more preferably 2% to 40% by mass, relative to the total mass of the composition.

[0340] aqueous phase The composition according to the present invention, specifically a cosmetic composition, may contain at least one aqueous phase.

[0341] The aqueous phase may include water and, optionally, a water-soluble solvent.

[0342] In the present invention, the term "water-soluble solvent" refers to a compound that is liquid at room temperature and is miscible with water (miscible with more than 50% by mass of water at 25°C and atmospheric pressure).

[0343] The water-soluble solvents that can be used in the compositions according to the present invention may also be volatile.

[0344] Among the water-soluble solvents that can be used in the composition according to the present invention, lower monoalcohols containing 1 to 5 carbon atoms, such as ethanol and isopropanol, C2-C 32 Polyols, C3 and C4 ketones, and C2-C4 aldehydes are specific examples.

[0345] Polyols are specifically mentioned as water-soluble solvents that can be used in the compositions according to the present invention. For the purposes of the present invention, the term "polyol" means any organic molecule containing at least two free hydroxyl groups.

[0346] Polyols suitable for use in the present invention may be linear, branched, or cyclic saturated or unsaturated alkyl compounds having at least two -OH functional groups, particularly at least three -OH functional groups, on the alkyl chain.

[0347] Polyols that are advantageously suitable for formulation in the composition according to the present invention are, specifically, those containing 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms.

[0348] Advantageously, the polyol can be selected from, for example, pentaerythritol, trimethylolpropane, caprylyl glycol, glycerol, polyglycerol, such as glycerol oligomers, such as diglycerol, polyethylene glycol, polypropylene glycol, and mixtures thereof.

[0349] fat phase The composition according to the present invention, specifically a cosmetic composition, may also include at least one fatty phase, particularly an oily phase.

[0350] For the purposes of the present invention, the term "fatty phase" means a phase comprising at least one fatty substance and all lipid-soluble and lipophilic raw materials used in the formulation of the composition of the present invention.

[0351] Preferably, the fatty phase includes at least one type of oil, specifically a cosmetic oil.

[0352] The term "oil" refers to a water-immiscible, non-aqueous compound that is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg).

[0353] The fatty phase may contain at least one volatile or non-volatile hydrocarbon oil and / or fatty substance.

[0354] Non-volatile hydrocarbon oils include plant-derived hydrocarbon oils, synthetic ethers containing 10 to 40 carbon atoms, linear or branched hydrocarbons of mineral or synthetic origin, synthetic esters, aliphatic alcohols that are liquid at room temperature and have branched and / or unsaturated carbon chains containing 12 to 26 carbon atoms, and C 12 ~C 22 Specific examples include higher fatty acids, carbonates, and mixtures thereof.

[0355] Examples of volatile hydrocarbon oils include hydrocarbon oils containing 8 to 16 carbon atoms.

[0356] Non-volatile silicone oils can be specifically selected from non-volatile polydimethylsiloxane (PDMS) and phenyl silicone. Examples of volatile silicone oils include volatile linear or cyclic silicone oils.

[0357] Volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof, can also be used.

[0358] The oily phase may also include other fatty substances mixed with or dissolved in oil. Other fatty substances that may be present in the oily phase may be, for example, fatty acids, waxes, gums, paste-like compounds, or mixtures thereof.

[0359] 1) Additional UV shielding agent According to a particular embodiment, the composition according to the present invention comprises a) at least one additional UV shielding agent other than the composite material required by the present invention and defined above.

[0360] For the purposes of this invention, the term "UV shielding agent other than composite materials" is intended to refer to any UV shielding agent that is determined by this invention and has different chemical properties from those of composite materials as defined above.

[0361] Therefore, the composite material according to the present invention can be used alone or in combination with other UV shielding agents, particularly selected from organic and / or inorganic UV shielding agents.

[0362] Therefore, the cosmetic composition may also contain one or more additional UV shielding agents selected from hydrophilic, lipophilic, or insoluble organic UV shielding agents and / or mineral UV shielding agents different from the composite materials according to the present invention.

[0363] The term "hydrophilic UV shielding agent" means any organic or inorganic compound for cosmetic or skin use, for filtering UV irradiation, that can be completely dissolved in molecular form in a liquid aqueous phase, or that can be a colloidal suspension (e.g., in micelle form) in a liquid aqueous phase.

[0364] The term "lipophilic UV shielding agent" means any organic or inorganic compound for cosmetic or skin use, for filtering UV irradiation, that can be completely dissolved in a liquid fatty phase in molecular form, or that can be a colloidal suspension (e.g., in micelle form) in a liquid fatty phase.

[0365] The term "insoluble UV shielding agent" refers to any organic or inorganic compound for cosmetic or skin use, used to filter UV irradiation, having a water solubility of less than 0.5% by mass, and having a solubility of less than 0.5% by mass in most organic solvents, such as liquid paraffin, aliphatic alcohol benzoate, and fatty acid triglycerides, e.g., Miglyol 812®. This solubility, determined at 70°C, is defined as the amount of product in solution in a solvent at equilibrium with an excess of solid in the suspension after being returned to room temperature. Solubility can be easily evaluated in the laboratory.

[0366] Additional organic UV shielding agents, specifically, - Cinnamon compounds, especially ethylhexyl methoxycinnamate, - Anthranilic acid compounds, especially menthyl anthranilate, - Salicylic acid compounds, especially homosalates and ethylhexyl salicylate, - Dibenzoylmethane compounds, especially butyl methoxydibenzoylmethane, - Benzylidene camphor compounds, particularly 3-benzylidene camphor, 4-methylbenzylidene camphor, benzylidene camphor sulfonic acid and terephthalylidene dicamphor sulfonic acid, - Benzophenone compounds, particularly oxybenzone and n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, - β,β-diphenylacrylic acid compounds, especially octocrylene, - Triazine compounds, particularly phenylenebis-diphenyltriazine, bis-ethylhexyloxyphenol methoxyphenyltriazine, ethylhexyltriazone and diethylhexylbutamidetriazone, - Benzotriazole compounds, especially drometrizole trisiloxane, - Benzalmalonate compounds, specifically those referred to in U.S. Patent No. 5,624,663, in particular polysilicone-15, - Benzimidazole derivatives, especially phenylbenzimidazole sulfonic acid, - Imidazolin compounds, especially ethylhexyl dimethoxybenzylidene dioxoimidazolin propionate, - Bis-benzazolyl compounds, for example those described in European Patent No. 0669323 and U.S. Patent No. 2463264, in particular disodium phenyldibenzimidazole tetrasulfonate, - Para-aminobenzoic acid compounds, especially PABA, ethylhexyldimethyl PABA and PEG-25 PABA, - Methylenebis(hydroxyphenylbenzotriazole) compounds, for example, those described in U.S. Patent No. 5,237,071, U.S. Patent No. 5,166,355, British Patent No. 2,303,549, German Patent No. 1,972,6184 and European Patent No. 0893,119, in particular methylenebisbenzotriazoltetramethylbutylphenyl - Benzoxazole compounds, for example, those described in the patent applications of European Patent No. 0832642, European Patent No. 1027883, European Patent No. 1300137 and German Patent No. 10162844, in particular 2,4-bis-[5-1(dimethylpropyl)benzoxazole-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine, - Polymeric shielding agents and silicone shielding agents, for example specifically those described in the patent application in International Publication No. 93 / 04665, - α-alkylstyrene dimers, for example, those described in the German patent application No. 19855649, - 4,4-diarylbutadiene compounds, for example those described in the patent applications of European Patent No. 0967200, German Patent No. 19746654, German Patent No. 19755649, European Patent No. 1008586, European Patent No. 1133980 and European Patent No. 0133981, in particular 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, and - those mixtures They are selected from among them.

[0367] Additional inorganic UV shielding agents are generally mineral UV shielding agents, and are particularly selected from metal oxides.

[0368] The metal oxides can be specifically selected from titanium oxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, and mixtures thereof.

[0369] The metal oxide particles may or may not be coated.

[0370] The coated particles are more specifically titanium dioxide coated with silica, titanium dioxide coated with silica and iron oxide, titanium dioxide coated with silica and alumina, titanium dioxide coated with alumina, titanium dioxide coated with alumina and aluminum stearate, titanium dioxide coated with silica, alumina and alginate, titanium dioxide coated with alumina and aluminum laurate, titanium dioxide coated with iron oxide and iron stearate, titanium dioxide coated with zinc oxide and zinc stearate, titanium dioxide coated with silica and alumina and treated with silicone, titanium dioxide coated with silica, alumina and aluminum stearate and treated with silicone, and silica Titanium dioxide coated with silicone, titanium dioxide coated with alumina and silicone, titanium dioxide coated with triethanolamine, titanium dioxide coated with stearic acid, titanium dioxide coated with sodium hexametaphosphate, or TiO2 treated with octyltrimethylsilane, TiO2 treated with polydimethylsiloxane, anatase / rutile TiO2 treated with polydimethylhydrogenosiloxane, TiO2 coated with triethylhexanoin, TiO2 coated with aluminum stearate and alumina, TiO2 coated with aluminum stearate, TiO2 coated with alumina and silicone, TiO2 coated with lauroyl lysine, or C 9~15 This is TiO2 coated with fluoroalcohol phosphoric acid and aluminum hydroxide.

[0371] Metal oxides can be optionally doped.

[0372] In this regard, examples include TiO2 particles doped with at least one transition metal, such as iron, zinc, or manganese, and more specifically, manganese.

[0373] The doped particles may be in the form of a dispersion, preferably an oily dispersion. The oil present in the oily dispersion is preferably selected from triglycerides, including capric acid / caprylic acid. The oily dispersion of titanium dioxide particles may additionally contain one or more dispersions, such as sorbitan esters or polyoxyalkylene-glycerol fatty acid esters. More specifically, an oily dispersion of manganese-doped TiO2 particles in capric acid / caprylic acid triglyceride, in the presence of tri-PPG-3 myristyl ether citrate, polyglyceryl-3 polyricinoleate, and sorbitan isostearate is an example. Other examples include mixtures of metal oxides, specifically mixtures of titanium dioxide and cerium dioxide, such as an equal mass mixture of silica-coated titanium dioxide and cerium dioxide, and mixtures of titanium dioxide and zinc dioxide coated with alumina, silica, and silicone, or alumina, silica, and glycerol.

[0374] 2) Coloring agents According to a particular embodiment, the composition according to the present invention comprises 2) at least one coloring agent.

[0375] Generally, the term "colorant" is understood to refer to any compound that has the ability to color a composition, that is, to absorb in the visible spectrum, and in particular to the human eye, to appear to have a color such as yellow, orange, red, purple, blue, or green.

[0376] Preferably, the composition according to the present invention comprises at least one pigment.

[0377] The term "pigment" should be understood to mean white or colored, mineral or organic particles that are insoluble in liquid lipophilic and hydrophilic phases, intended to color and / or opaque compositions containing them, and distinct from the composite materials according to the present invention. More specifically, pigments have little to no solubility in aqueous-alcoholic media.

[0378] The pigments that can be used are specifically organic and / or mineral pigments known in the art, specifically selected from Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry (Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a20 371 and the same book, "Pigments, Inorganic, 1. General", 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a20_243.pub3).

[0379] These pigments may be in the form of pigment powders or pastes. The pigments may or may not be coated. The pigments can be selected from, for example, mineral pigments, organic pigments, lakes, pigments with special effects such as pearlescent agents or glitter flakes, and mixtures thereof.

[0380] Pigments may also be mineral pigments. The term "mineral pigment" refers to any pigment that satisfies the definition in the chapter on inorganic pigments in Ullmann's Encyclopedia. Mineral pigments useful in this invention include iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, Prussian blue, and titanium dioxide.

[0381] The pigment can be an organic pigment.

[0382] The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's Encyclopedia.

[0383] Organic pigments can be specifically selected from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, or quinophthalone compounds.

[0384] Preferably, pigments suitable for use in the present invention are selected from carbon black, iron oxide, specifically red, brown, or black iron oxide, and iron oxide-coated mica, triarylmethane pigments, specifically blue and purple triarylmethane pigments, such as Blue 1 Lake, azo pigments, specifically red azo pigments, such as D&C Red 7, alkali metal salts of Risol Red, such as calcium salts of Risol Red B, and more preferably, the pigments used are selected from red iron oxide and azo pigments, specifically red azo pigments such as D&C Red 7.

[0385] The coloring agent may be present in the composition according to the present invention in an amount ranging from 0.001% to 10% by mass, and preferably from 0.005% to 5% by mass, relative to the total mass of the composition.

[0386] According to a particular embodiment of the present invention, the amount of pigment is in the range of 0.5% to 40%, and preferably 1% to 20%, relative to the mass of the composition of the present invention containing them.

[0387] 3) Cosmetic surfactants According to a particular embodiment, the composition according to the present invention comprises 3) at least one cosmetic surfactant for caring for keratinous substances, preferably for skin care. In particular, the cosmetic surfactant may be at least one hydrophilic surfactant and / or one lipophilic surfactant.

[0388] The term "hydrophilic surfactant" refers to a water-soluble or water-dispersible surfactant that has the ability to form hydrogen bonds.

[0389] Examples of cosmetic surfactants include humectants, depigmentation agents, desquamating agents, wetting agents, anti-aging agents, mattifying agents, scar-forming agents, antibacterial agents, vitamins and their derivatives or precursors, antioxidants, free radical scavengers, anti-fouling agents, self-tanning agents, anti-glycation agents, sedatives, deodorants, essential oils, NO synthase inhibitors, agents for promoting the synthesis and / or inhibiting the degradation of skin or epidermal polymers, agents for promoting fibroblast proliferation, agents for promoting keratinocyte proliferation, muscle relaxants, cooling agents, tension-imparting agents, depigmentation agents, pigment production promoters, keratolytic agents, slimming agents, agents acting on cellular energy metabolism, insect repellents, substance P antagonists or CRGP antagonists, agents for preventing hair loss, and mixtures thereof.

[0390] Specifically, activators are: - Vitamins and their derivatives, specifically their esters, such as niacinamide (3-pyridinecarboxamide), nicotinamide (vitamin B3), tocopherol (vitamin E) and its esters (e.g., tocopherol acetate), ascorbic acid and its derivatives (vitamin C), retinol (vitamin A), - Urea, hydroxyurea, glycerol, polyglycerol, glyceryl glucoside, diglyceryl glucoside, polyglyceryl glucoside, xylityl glucoside and plant extracts (specifically tea, mint, orchid, soybean, aloe vera, honey), and humectants or moisturizers, especially glycerol. - C-glycoside compounds, and preferably hydroxypropyltetrahydropyrantriol (INCI name) (or Proxylene), - Antioxidant compounds, - Anti-aging activators, such as hyaluronic acid compounds, and specifically sodium hyaluronate, salicylic acid compounds, and in particular 5-n-octanoylsalicylic acid (capryloylsalicylic acid), adenosine, and sodium salts of (3-hydroxy-2-pentylcyclopentyl)acetic acid. - Keratin-dissolving agents such as lactic acid or glycolic acid, - those mixtures You can choose from these.

[0391] Such activators may be present in the composition according to the present invention in a content ranging from 0.05% to 10% by mass, and preferably from 1.0% to 8.0% by mass, relative to the total mass of the composition.

[0392] 4) Surfactants According to a particular embodiment, the composition according to the present invention comprises 4) at least one surfactant.

[0393] Surfactants can be selected from nonionic, anionic, cationic, and amphoteric surfactants, as well as mixtures thereof. For definitions and functions of the emulsifying properties of surfactants, see Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 22, pp. 333-432, 3rd edition, 1979, Wiley, particularly pp. 347-377 of this reference for anionic, amphoteric, and nonionic surfactants.

[0394] Examples of amphoteric surfactants suitable for use in the present invention are specifically selected from betaines, preferably alkyl betaines, particularly lauryl betaine, N-alkylamide betaine and their derivatives, especially cocamidopropyl betaine, lauramidopropyl betaine, and N-disodium N-carboxyethoxyethyl N-cocoylamide ethylaminoacetic acid, sultaine, particularly cocoylamide propyl hydroxysultaine, and mixtures thereof.

[0395] Nonionic surfactants can be specifically selected from alkyl esters and polyalkyl esters of poly(ethylene oxide), oxyalkylene alcohols, alkyl ethers and polyalkyl ethers of poly(ethylene oxide), optionally alkyl esters and polyalkyl esters of polyoxyethylene-modified sorbitan, optionally alkyl ethers and polyalkyl ethers of polyoxyethylene-modified sorbitan, in particular alkyl esters and polyalkyl esters of sucrose, optionally alkyl esters and polyalkyl esters of polyoxyethylene-modified glycerol, optionally alkyl ethers and polyalkyl ethers of polyoxyethylene-modified glycerol, zwitter surfactants, cetyl alcohol, stearyl alcohol, and mixtures thereof.

[0396] Anionic surfactants include alkyl sulfates, carboxylates, amino acid derivatives, sulfonates, isethionates, taurates, sulfosuccinates, alkyl sulfoacetates, phosphates, and alkyl phosphates, polypeptides, and C 10 ~C 30 , and specifically C 16 ~C 25 The choice can be made from metal salts of fatty acids, particularly metal stearates and behenates, as well as mixtures thereof.

[0397] Cationic surfactants include alkylimidazolidinium, for example isostearylethylimonium ethosulfate, ammonium salts, for example (C 12~30 Alkyl)-tri(C 1~4 Alkyl)ammonium halides, such as N,N,N-trimethyl-1-docosaenaminium chloride (or behentrimonium chloride), can be selected. Silicone surfactants can be selected from dimethicone copolyols or silicone elastomers. The composition according to the present invention may contain a surfactant in an amount between 0.01% by mass and 2.0% by mass, preferably between 0.05% by mass and 1.5% by mass, and more preferably between 0.1% by mass and 1.0% by mass, based on the total mass of the composition.

[0398] 5) Thickening agents According to a particular embodiment, the composition according to the present invention comprises 5) at least one thickening agent, sometimes also called a gelling agent or viscosity modifier. The thickening agent may be synthetic, natural or of natural origin, preferably natural or of natural origin.

[0399] Such thickeners can be selected more specifically from natural polymers or polymers of natural origin, particularly those of plant origin.

[0400] These thickeners are preferably hydrophilic, i.e., soluble or dispersible in water. Advantageously, the thickeners are modified or natural polysaccharides, particularly modified or unmodified starches, fructans, guarans, glucans, amylose, amylopectin, glycogen, pullulan, dextran, cellulose and their derivatives, particularly methylcellulose, hydroxyalkylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, mannan, xylan, lignin, araban, galactan, galacturonan, alginate compounds, chitin, chitosan, glucuronoxylan, arabinoxylan, xyloglucan, glucomannan, pectic acid and pectin, arabinogalactan, carrageenan, agar, glycosaminoglycans Selected from ns), galactomannans and their nonionic derivatives, particularly hydroxypropyl guar and its ionic derivatives, such as gum arabic, sclerotium gum, tragacanth gum, ghati gum, karaya gum, locust bean gum, konjac gum, and guar gum, ns, microbial biopolysaccharide gums, particularly scleroglucan or xanthan gum, mucopolysaccharides, carboxyvinyl polymers, polyacrylamide, polymers and copolymers of 2-acrylamide 2-methylpropane sulfate, optionally crosslinked and / or neutralized, water-soluble or water-dispersible silicone derivatives, such as silicone acrylate, polyether silicone and cationic silicone, and mixtures thereof.

[0401] The thickening agent may be present in the composition according to the present invention in an amount ranging from 0.05% to 5.0% by mass, particularly 0.3% to 4.0% by mass, and more specifically 0.4% to 2.5% by mass, relative to the total mass of the composition.

[0402] Supplement The compositions according to the present invention may also contain at least one auxiliary agent that is common in the field of cosmetics, the auxiliary agent being selected from fragrances, film-forming polymers, pH adjusters (acids or bases), such as citric acid, tartaric acid or oxalic acid, chelating agents, preservatives, softeners, sweeteners, defoamers, fillers, trace elements, propellants, and mixtures thereof.

[0403] Those skilled in the art will understand that the selection of these, or any optional additional compounds, and / or their quantities, will be made with care such that the advantageous properties of the composition according to the present invention are not adversely affected, or substantially affected, by the intended addition.

[0404] Those skilled in the art will understand that the selection of these, or any optional additional compounds, and / or their quantities, will be made with care such that the advantageous properties of the particles according to the present invention are not adversely affected, or substantially affected, by the intended additions.

[0405] As mentioned above, the composition according to the present invention may be for cosmetic use, and is preferably for cosmetic use.

[0406] The compositions according to the present invention are generally suitable for topical application to the skin and therefore generally contain physiologically acceptable media, i.e., media compatible with the skin.

[0407] Preferably, it is a medium that is acceptable as a cosmetic, i.e., a medium that has a pleasant color, scent and feel and does not produce an unacceptable discomfort, i.e., a stinging pain or tightness, that would cause the user to want to avoid applying the composition.

[0408] Form of provision of the composition The composition, specifically the cosmetic composition containing the particles according to the present invention, can be prepared according to techniques well known to those skilled in the art.

[0409] The composition may be in any conventional form depending on the target application and is suitable for topical application, i.e., application to the surface of the keratin material under consideration.

[0410] The cosmetic composition may be in the form of an aqueous or water-alcohol gel. The cosmetic composition may also be in the form of a simple or complex (O / W, W / O, O / W / O, or W / O / W) emulsion, such as a cream, milk, or gel cream.

[0411] This composition can also be in an anhydrous form, for example, in the form of an oil.

[0412] The term "anhydrous composition" means a composition containing less than 5% by mass of water, or even less than 2% by mass of water, or more preferably less than 1% by mass of water, and specifically a composition that does not contain water, the water being water being added during the preparation of the composition and is instead residual water resulting from the mixing of raw materials.

[0413] The cosmetic composition can be used, for example, as a makeup product.

[0414] Cosmetic compositions, for example, can be used as facial and / or body care and / or UV protection products in liquid to semi-liquid consistency, and may have the appearance of creams, ointments, milks, cream gels, lotions, serums, pastes, or foams, to varying degrees being oily white or colored. Cosmetic compositions can optionally be applied to the skin in aerosol form. They may also be in solid form, such as stick form.

[0415] Cosmetic compositions may be in the form of products for caring for the skin or semi-mucous membranes, such as protective or cosmetic care compositions for the face, lips, hands, feet, folds of body structure, or body (e.g., day creams, night creams, day serums, night serums, makeup remover creams, makeup bases, protective or care body milks, after-sun milks, skincare or scalp care lotions, gels or foams, serums, masks, or aftershave compositions).

[0416] The composition can be applied by hand or using an applicator.

[0417] In particular, the cosmetic composition has an SPF of 5 or more, and preferably 10 or more.

[0418] For the purposes of this invention, the term "SPF" means an ultraviolet protection index that measures the level of protection from UV rays. The SPF value corresponds to the ratio between the minimum time required to obtain a tan (causing erythema) using an ultraviolet protective composition and the minimum time required to obtain the same tan without using an ultraviolet protective composition. More precisely, the term "SPF" is defined in the paper "A new substrate to measure sunscreen protection factors across the ultraviolet spectrum," J. Soc. Cosmet. Chem., 40, pp. 127-133 (May / June 1989).

[0419] The SPF (Sun Protection Factor) can be evaluated in vitro using a Labsphere® spectrophotometer. The material to which the UV-protective composition is applied is a sheet. Poly(methyl methacrylate) (PMMA) sheets have been found to be ideal for this protocol. The UV Protection Factor (SPF) of this composition can also be evaluated in vivo according to the ISO 24444 protocol "Cosmetics - Sun protection test methods - in vivo determination of the Sun Protection Factor (SPF) (2010)".

[0420] The term "UVAPF" refers to an index that characterizes protection from UV-A irradiation. In particular, this index could be measured in vivo using the PPD (Persistent Immediate Blackening) method. PPD measures the skin color observed 2–4 hours after exposure to UV-A light. This method has been adopted by the Japan Cosmetic Industry Association (JCIA) as the official test procedure for UV-A labeling of products since 1996 and is frequently used by testing laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin. Measurement standards for the efficacy of UVA protection issued on 21 November 1995 and in force since 1 January 1996). UV-A protection can also be evaluated in vitro using a Labsphere® spectrophotometer. The material to which the UV protective composition is applied is a sheet. Polymethyl methacrylate (PMMA) sheets have been found to be ideal for this protocol. The ISO 24443 protocol describes such an in vitro method.

[0421] Cosmetic use and makeup application methods The present invention also relates to non-therapeutic cosmetic uses of composite materials according to the present invention, which at least include the application of a composition comprising at least one of the previously defined composite materials to a keratinous substance for filtering UV irradiation, preferably UV-B.

[0422] The present invention also relates to a non-therapeutic cosmetic method, which at least includes the application to a keratinous substance of a composition comprising at least one of the previously defined composite materials for filtering UV irradiation, particularly UV-B.

[0423] In yet another aspect thereof, the present invention also relates to the non-therapeutic cosmetic use of a cosmetic composition comprising at least one of the previously defined composite materials for preventing the appearance of darker and / or more pigmented marks on the skin, particularly on the face, neck, arms, hands and / or shoulders, which give uneven color to the skin.

[0424] The present invention also covers non-therapeutic cosmetic methods, which include applying to a keratinous surface a cosmetic composition comprising at least one of the previously defined composite materials for limiting skin darkening and / or improving the tone and / or uniformity of facial skin.

[0425] The present invention also covers the non-therapeutic cosmetic use of cosmetic compositions comprising at least one of the previously defined composite materials for preventing premature aging of the skin, specifically the skin of the face, neck, arms, hands, and / or shoulders.

[0426] The present invention also relates to a non-therapeutic cosmetic method, which includes the application to a keratin surface of at least one cosmetic composition comprising at least one of the previously defined composite materials for preventing and / or treating signs of keratin aging.

[0427] In one embodiment, the present invention relates to a previously defined composite material for use as an agent for filtering UV irradiation, particularly UV-B irradiation.

[0428] For the purposes of the present invention, the terms “prevent” or “prevent” mean at least partially reducing the risk of certain phenomena occurring, such as signs of aging of keratinous material, or the appearance of darker and / or more intense colored marks on the skin, which give uneven color to the skin, and / or premature aging of the skin.

[0429] In the description and examples, percentages refer to percentages of mass or moles. The raw materials are mixed in an order and under conditions readily determined by those skilled in the art.

[0430] Next, the present invention will be described using the following embodiments as means, but these are, of course, given as non-limiting examples of the present invention. [Examples]

[0431] (Example 1) Preparation of bismuth oxycarbonate particles according to the present invention Bismuth oxycarbonate particles 1 are synthesized according to the preparation method described below.

[0432] A solution of bismuth nitrate pentahydrate Bi(NO3)3·5H2O (0.40 M) and D-mannitol (0.87 M) is prepared in 800 mL of water and stirred until the reagents are completely dissolved. Then, 160 mL of ammonium carbonate solution (2.1 equivalents relative to bismuth) is added. A white solid precipitate forms. This mixture is then transferred to a Teflon autoclave and heated at 125°C for 7.5 hours. Product 1 is isolated by centrifugation, washed three times with water, and then oven-dried at 60°C.

[0433] The morphology of bismuth oxycarbonate particles was determined by direct observation using a transmission electron microscope. 1–5 milligrams of dried particles were dispersed in 10 mL of anhydrous ethanol and treated in an ultrasonic bath for 2 minutes. Then, 5 μL of the dispersion was placed on an observation grid (copper with a carbon surface layer) and dried in ambient air.

[0434] Observations were performed using a Hitachi HT7700 transmission electron microscope with an acceleration voltage of 100kV. Average dimensions were obtained by measuring particle dimensions through image analysis using ImageJ software (CA Schneider, WS Rasband, KW Eliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat. Methods.9 (2012) pp. 671-675).

[0435] Bismuth oxycarbonate particles 1 are small plates having the following average dimensions: Average length L: 86nm Average width l: 53nm Average thickness e: 28nm

[0436] (Example 2) Synthesis of composite materials according to the present invention (Example 2.A) Synthesis of bismuth oxycarbonate-octyltriethoxysilane composite material A The bismuth oxycarbonate particles (253 mg) from Example 1 are stirred in 5 mL of distilled water at room temperature. Then, the temperature of the medium is raised to 50°C while stirring.

[0437] Add a solution of octyltriethoxysilane (99 mg) in ethanol (5 mL) dropwise.

[0438] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0439] Stir the mixture at 50°C for 3 hours.

[0440] After cooling to room temperature, composite material A is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0441] Composite material A is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0442] (Example 2.B) Synthesis of bismuth oxycarbonate-dodecyltriethoxysilane composite material B The bismuth oxycarbonate particles (253 mg) from Example 1 are stirred in 5 mL of distilled water at room temperature. Then, the temperature of the medium is raised to 50°C while stirring.

[0443] Add a solution of dodecyltriethoxysilane (119 mg) in ethanol (5 mL) dropwise.

[0444] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0445] Stir the mixture at 50°C for 3 hours.

[0446] After cooling to room temperature, composite material B is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0447] Composite material B is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0448] (Example 2.C) Synthesis of bismuth oxycarbonate-triethoxy(2,4,4-trimethylpentyl)silane composite material C The bismuth oxycarbonate particles (253 mg) from Example 1 are stirred in 5 mL of distilled water at room temperature. Then, the temperature of the medium is raised to 50°C while stirring.

[0449] Add a solution of triethoxy(2,4,4-trimethylpentyl)silane (99 mg) in ethanol (5 mL) dropwise.

[0450] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0451] Stir the mixture at 50°C for 3 hours.

[0452] After cooling to room temperature, composite material C is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0453] Composite material C is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0454] (Example 2.D) Synthesis of bismuth oxycarbonate-benzyltriethoxysilane composite material D The bismuth oxycarbonate particles (253 mg) from Example 1 are stirred in 5 mL of distilled water at room temperature. Then, the temperature of the medium is raised to 50°C while stirring.

[0455] Add a solution of benzyltriethoxysilane (91 mg) in ethanol (5 mL) dropwise.

[0456] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0457] Stir the mixture at 50°C for 3 hours.

[0458] After cooling to room temperature, composite material D is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0459] Composite material D is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0460] (Example 2.E) Synthesis of bismuth oxycarbonate-2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (n=1) composite material E The bismuth oxycarbonate particles (253 mg) from Example 1 are stirred in 5 mL of distilled water at room temperature. Then, the temperature of the medium is raised to 50°C while stirring.

[0461] Add a solution of 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (n=1) (85 mg) in ethanol (5 mL) dropwise.

[0462] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0463] Stir the mixture at 50°C for 3 hours.

[0464] After cooling to room temperature, composite material E is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0465] Composite material E was obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0466] (Example 2.F) Synthesis of bismuth oxycarbonate-[hydroxy(polyethyleneoxy)propyl]triethoxysilane (n=8~12) composite material F The bismuth oxycarbonate particles (253 mg) from Example 1 are stirred in 5 mL of distilled water at room temperature. Then, the temperature of the medium is raised to 50°C while stirring.

[0467] Add a 50% by mass solution of [hydroxy(polyethyleneoxy)propyl]triethoxysilane (n=8~12) (85 mg) in ethanol (4 mL) dropwise.

[0468] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0469] Stir the mixture at 50°C for 3 hours.

[0470] After cooling to room temperature, composite material F is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0471] Composite material F is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0472] (Example 2.G) Synthesis of bismuth oxycarbonate-silica-octyltriethoxysilane composite material G The bismuth oxycarbonate particles (2g) from Example 1 are stirred in 40mL of distilled water at room temperature. Then, the temperature of the medium is raised to 80°C while stirring.

[0473] At this temperature, 26.6 mL of an aqueous sodium silicate solution, prepared from a 26.9% by mass solution and diluted 10-fold, is added dropwise. During the addition, the pH is maintained at 6.5 using dilute sulfuric acid H2SO4 (0.2 M). Stirring and heating are maintained for 5 hours, after which the reaction medium is allowed to cool to room temperature. The intermediate materials, bismuth oxycarbonate and silica, are isolated by centrifugation, washed twice with water, and then oven-dried under vacuum (less than 100 mbar) at 60°C. The bismuth oxycarbonate-silica intermediate material (253 mg) is then stirred in 5 mL of distilled water at room temperature.

[0474] Next, raise the temperature of the medium to 50°C while stirring.

[0475] Add a solution of octyltriethoxysilane (99 mg) in ethanol (5 mL) dropwise.

[0476] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0477] Stir the mixture at 50°C for 3 hours.

[0478] After cooling to room temperature, composite material G is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0479] Composite material G is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0480] (Example 2.H) Synthesis of bismuth oxycarbonate-silica-dodecyltriethoxysilane composite material H The bismuth oxycarbonate particles (2g) from Example 1 are stirred in 40mL of distilled water at room temperature. Then, the temperature of the medium is raised to 80°C while stirring.

[0481] At this temperature, 26.6 mL of an aqueous sodium silicate solution, prepared from a 26.9% by mass solution and diluted 10-fold, is added dropwise. During the addition, the pH is maintained at 6.5 using dilute sulfuric acid H2SO4 (0.2 M). Stirring and heating are maintained for 5 hours, after which the reaction medium is allowed to cool to room temperature. The intermediate materials, bismuth oxycarbonate and silica, are isolated by centrifugation, washed twice with water, and then oven-dried under vacuum (less than 100 mbar) at 60°C. The bismuth oxycarbonate-silica intermediate material (253 mg) is then stirred in 5 mL of distilled water at room temperature.

[0482] Next, raise the temperature of the medium to 50°C while stirring.

[0483] Add a solution of dodecyltriethoxysilane (119 mg) in ethanol (5 mL) dropwise.

[0484] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0485] Stir the mixture at 50°C for 3 hours.

[0486] After cooling to room temperature, composite material H is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0487] Composite material H is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0488] (Example 2.I) Synthesis of Bismuth Oxycarbonate-Aluminum Hydroxide-Octyltriethoxysilane Composite Material I The bismuth oxycarbonate particles (2 g) from Example 1 were stirred in 40 mL of distilled water at a concentration of 100 g / L at room temperature. Then, the temperature of the medium was maintained at 70°C for 30 minutes. The pH was adjusted to 8 using sodium hydroxide.

[0489] Add a sodium aluminate aqueous solution at a concentration of 100 g / L, in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate is equal to 0.027.

[0490] Once the addition is complete, stir the reaction medium at 70°C for 1 hour. Adjust the pH to 6.5 by adding sulfuric acid.

[0491] The bismuth oxycarbonate-aluminum hydroxide intermediate material is isolated by centrifugation, washed with water, and then oven-dried under vacuum (pressure 10 mmHg) at 50°C.

[0492] Next, the bismuth oxycarbonate-aluminum hydroxide intermediate material (253 mg) is stirred in 5 mL of distilled water at room temperature.

[0493] Next, raise the temperature of the medium to 50°C while stirring.

[0494] Add a solution of octyltriethoxysilane (99 mg) in ethanol (5 mL) dropwise.

[0495] The pH is adjusted to 2 by adding dilute sulfuric acid H2SO4 (0.2M).

[0496] Stir the mixture at 50°C for 3 hours.

[0497] After cooling to room temperature, composite material I is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0498] Composite material I is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0499] (Example 2.J) Synthesis of bismuth oxycarbonate-titanium dioxide-octyltriethoxysilane composite material J Disperse bismuth oxycarbonate particles (2g) from Example 1 in 190mL of 2-propanol. Add 2.5mL of sodium hydroxide aqueous solution (5×10). -4 Add M) dropwise while stirring. Then, add a solution consisting of 116 μL of titanium isopropoxide in 10 mL of 2-propanol (0.05 equivalents relative to Bi) dropwise while stirring. Next, stir the resulting medium for 1 hour.

[0500] The intermediate material, bismuth oxycarbonate-titanium dioxide, is isolated by centrifugation, washed twice with ethanol, and dried under vacuum at 60°C (P < 100 mbar). Next, 500 mg of the intermediate material, bismuth oxycarbonate-titanium dioxide, is dispersed in 10 mL of water. The dispersion is heated at 50°C. Next, a solution of octyltriethoxysilane (180 mg) in 10 mL of ethanol is added dropwise while stirring. The pH is then adjusted to 2 using H2SO4 (0.25 M). The dispersion is then stirred and heated at 50°C for 3 hours.

[0501] Composite material J is isolated by centrifugation, washed twice with water and once with ethanol, and dried under vacuum at 60°C (P < 100 mbar).

[0502] Composite material J is obtained as a white powder and characterized by UV / Vis spectrophotometric analysis.

[0503] (Example 2.K) Synthesis of bismuth oxycarbonate-zinc oxide-octyltriethoxysilane composite material K 1 g of bismuth oxycarbonate particles according to Example 1 is dispersed in 90 mL of water. The pH of the dispersion is adjusted to 5 using H2SO4 (0.1 M). Next, a solution of zinc nitrate hexahydrate (58.3 mg, 0.05 equivalents relative to Bi) in 10 mL of water is added. The pH is then adjusted to 10 by adding NaOH (0.5 M) dropwise. The resulting medium is then heated at 70°C for 5 minutes with stirring, and then stirred for 1 hour. The white solid is isolated by centrifugation, washed twice with water and once with ethanol, and then dried at 50°C under vacuum for 1 hour. Next, 500 mg of the dried solid is placed in an alumina crucible and heated in a muffle furnace to a maximum of 200°C for 1 hour (heating rate 10°C / min). After cooling to room temperature, the intermediate material, bismuth oxycarbonate-zinc oxide, is obtained as a whitish powder.

[0504] Next, 300 mg of bismuth oxycarbonate-zinc oxide, an intermediate material, is dispersed in 10 mL of water. The dispersion is heated at 50°C. Then, a solution of octyltriethoxysilane (108 mg) in 10 mL of ethanol is added dropwise while stirring. The pH is then adjusted to 10 using NaOH (0.5 M). The dispersion is then stirred and heated at 50°C for 3 hours.

[0505] Composite material K is isolated by centrifugation, washed three times with ethanol, and dried under vacuum at 60°C (P < 100 mbar).

[0506] Composite material K is obtained as a whitish powder and characterized by UV / Vis spectrophotometric spectroscopy.

[0507] (Comparative example 2.L) Synthesis of bismuth oxycarbonate-octyltriethoxysilane composite material Z, not according to the present invention. Bismuth oxycarbonate particles (Alfa Aesar, approximately 500 nm in diameter, 50 nm thick, 253 mg in size), not according to the present invention, are stirred in 5 mL of distilled water at room temperature. Then, the temperature of the medium is raised to 50°C while stirring.

[0508] Add a solution of octyltriethoxysilane (99 mg) in ethanol (5 mL) dropwise. Adjust the pH to 2 by adding dilute sulfuric acid H2SO4 (0.2 M).

[0509] Stir the mixture at 50°C for 3 hours.

[0510] After cooling to room temperature, composite material Z is isolated by centrifugation, washed three times with water, then once with ethanol, and then oven-dried under vacuum (less than 100 mbar) at 80°C.

[0511] The composite material Z was obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0512] (Example 2.M) Summary of synthesis conditions for materials A-K and Z Table 2 below summarizes all the composite materials prepared in Examples 2.A to 2.L.

[0513] [Table 2]

[0514] (Example 3) Absorption spectrum of bismuth oxycarbonate composite material UV-visible spectral photometric and absorbance spectra were generated for the composite material prepared according to Example 2.

[0515] These were obtained by UV-Vis spectrophotometric analysis of dispersions in isododecane at a concentration of 0.005 mass% for composite materials A, B, G, H, I, J, K, and Z, and in water / propylene glycol / polysorbate 20 (Tween 20, sold by Acros Organics) at a mass fraction of 49.85 / 49.85 / 0.30, respectively.

[0516] The quartz cell used for absorbance measurements has a side length of 1 cm. The spectrophotometer used is a Thermo Fischer Scientific Genesys 10S.

[0517] Preparation of dispersions of products A, B, G, H, I, and Z A dispersion of a composite material of bismuth oxycarbonate and an organosilicon derivative is sonicated in isododecane at a concentration of 0.05% by mass for 1 minute, then stirred with a magnetic stirrer for 10 minutes. It is then sonicated again for 1 minute, diluted to 0.005% by mass of bismuth oxycarbonate, sonicated again for 1 minute, and stirred again with a magnetic stirrer for 5 hours. Immediately before absorption measurement, the sample is sonicated for 1 minute.

[0518] Preparation of dispersions of products C, D, E, and F Dispersions of composite materials of bismuth oxycarbonate and organosilicon derivatives are sonicated for 15 minutes at a concentration of 0.10% by mass in a mixture of water / propylene glycol / polysorbate 20 with mass fractions of 49.85 / 49.85 / 0.30, and then stirred with a magnetic stirrer for 2 hours. The dispersions are then diluted in the same solvent mixture to 0.005% by mass of bismuth oxycarbonate and stirred again for 10 minutes. Absorbance measurements are then performed.

[0519] The spectra of materials (A-I) according to the present invention are compared with those of bismuth oxycarbonate-octyltriethoxysilane particles (material Z) prepared from commercially available reference bismuth oxycarbonate (BiO)2CO3 (small plate particles with a diameter of approximately 500 nm and a thickness of 50 nm) obtained from Alfa Aesar, which are not according to the present invention.

[0520] If the UV absorbance exceeds a predetermined measurement threshold, the filtering of UV irradiation is considered effective. In particular, a composite material containing the composite material, in which a 0.005% mass fraction has a UV absorbance threshold of 0.25 or higher, is considered effective for filtering UV irradiation.

[0521] The absorption spectra are shown in Figures 1 to 12.

[0522] The results are listed in order in Table 3 below.

[0523] [Table 3]

[0524] The composite material according to the present invention exhibits good absorption of UV light and, as a result, efficient shielding of UV light, specifically in the UV-B range. In contrast, comparative composite material Z exhibits low absorbance and does not provide sufficient shielding across the entire UV range.

[0525] The absorption spectrum also shows that the composite material according to the present invention has high transparency in the visible range between 400 and 780 nm.

[0526] (Example 4) Absorption spectrum of composite material A according to Example 2.A The UV-visible absorbance spectrum of composite material A according to Example 2.A is measured in various solvents i). The measurement is performed using a dispersion of composite material A at a concentration of 0.005% by mass in solvent i).

[0527] Preparation of a dispersion of composite material A Composite material A, synthesized according to Example 2.A, is added to solvent i) at a concentration of 0.1% by mass.

[0528] The mixture is homogenized by magnetic stirring at 600 rpm for 5 minutes, then ultrasonically treated in an ultrasonic bath (Prolabo TP680 / DH) at 100% power in continuous mode for 15 minutes. Finally, the mixture is subjected to magnetic stirring at 600 rpm for 16 hours.

[0529] The resulting dispersion is referred to as An in Table 4 below.

[0530] [Table 4]

[0531] Dispersions A1 and A2, prepared according to the protocol described above, are each diluted by adding solvent i) to reach a final concentration of composite material A of 0.005% by mass, and then subjected to magnetic stirring at 600 rpm for 20 minutes before performing absorbance measurement.

[0532] The quartz cell used for absorbance measurement is 1 cm thick. The absorbance spectrum is acquired using a UV-2600 UV-Vis spectrophotometer (Shimadzu Corporation). The baseline is determined in advance in a quartz cell filled with solvent i).

[0533] If the measured UV absorbance exceeds a predetermined threshold, the filtering of UV light is considered efficient. In particular, when composite material A according to Example 2.A is dispersed in solvent i) at a concentration of 0.005 mass%, it is considered to efficiently filter UV light if the maximum absorbance measured in the UV range exceeds 0.25.

[0534] The absorption spectra of dispersions A1 and A2 according to Example 4 are shown in Figures 13 and 14.

[0535] The absorbance values ​​are reported in Table 5.

[0536] [Table 5]

[0537] (Example 5) Preparation of compositions A3, A4, A5, and A6 according to the present invention A solution of surfactant ii) is prepared by stirring in solvent i) at a concentration of 1% by mass until complete solubilization is achieved. Then, the solution is diluted in solvent i) to a concentration of 0.1% by mass.

[0538] During the preparation steps for the surfactant solutions for compositions A4, A5, and A6, the mixture of surfactant ii) and solvent i) was heated at 50°C until complete solubilization was achieved, and then cooled to room temperature before the addition step of composite material A as described below herein.

[0539] Composite material A, synthesized according to Example 2.A, is added to a diluted surfactant solution ii) in solvent i) at a concentration of 0.1% by mass.

[0540] The mixture is homogenized by magnetic stirring at 600 rpm for 5 minutes, then ultrasonically treated in an ultrasonic bath (Prolabo TP680 / DH) at 100% power in continuous mode for 15 minutes. Finally, the mixture is subjected to magnetic stirring at 600 rpm for 16 hours.

[0541] The composition obtained as a dispersion is referred to as An in Table 6 below.

[0542] [Table 6]

[0543] (Example 6) Absorbance spectra of compositions A3 to A6 according to the present invention Each of compositions A3 to A6 according to Example 5 was diluted by adding solvent i) to achieve a final concentration of 0.005% by mass in composite material A, and the mixture was then subjected to magnetic stirring at 600 rpm for 20 minutes before absorbance measurement. The quartz cell used for absorbance measurement was 1 cm thick. The absorbance spectrum was obtained using a UV-2600 UV-Vis spectrophotometer (Shimadzu Corporation). Baseline determination was performed in advance in a quartz cell filled with solvent i).

[0544] If the measured UV absorbance exceeds a predetermined threshold, the filtering of UV light is considered efficient. In particular, a composition containing 0.005% by mass of composite material A according to Example 2.A is considered to efficiently filter UV light if the maximum absorbance of these materials in the UV range exceeds 0.25.

[0545] The absorbance values ​​obtained for compositions A3, A4, A5, and A6 according to the present invention are reported in Table 7 below.

[0546] [Table 7]

[0547] Compositions A3, A4, A5, and A6 according to the present invention exhibit good absorption of UV light and, as a result, efficient filtering of UV light, particularly in the UV-B range.

[0548] The absorbance values ​​also indicate that compositions A3, A4, A5, and A6 according to the present invention have high transparency in the visible range between 400 and 780 nm.

[0549] (Example 7) Preparation of aqueous compositions A7 and A8 according to the present invention A solution of surfactant ii) is prepared by stirring it in water at a concentration of 1% by mass until it is completely solubilized. Then, the solution is diluted in water to a concentration of 0.1% by mass.

[0550] During the preparation of the surfactant solution for composition A7, lauryl glucoside (Plantacare 1200UP, an aqueous solution sold by BASF) was heated at 50°C until a homogeneous solution was obtained, and then introduced into water at a concentration of 1% by mass.

[0551] During the preparation step of the surfactant solution for composition A8, the mixture of PEG-150 distearate and water was heated at 50°C until completely solubilized, and then cooled to room temperature before the addition step of composite material A as described below herein.

[0552] Composite material A, synthesized according to Example 2.A, is added to a diluted aqueous solution of surfactant ii) at a concentration of 0.1% by mass.

[0553] The mixture is homogenized by magnetic stirring at 600 rpm for 5 minutes, then ultrasonically treated in an ultrasonic bath (Prolabo TP680 / DH) at 100% power in continuous mode for 15 minutes. Finally, the mixture is subjected to magnetic stirring at 600 rpm for 16 hours.

[0554] The composition obtained as a dispersion is referred to as An in Table 8 below.

[0555] [Table 8]

[0556] (Example 8) Absorbance spectra of aqueous compositions A7 and A8 according to the present invention Each of compositions A7 and A8 according to Example 7 was diluted by adding deionized water so that the final concentration of composite material A reached 0.005% by mass, and then subjected to magnetic stirring at 600 rpm for 20 minutes before absorption measurement.

[0557] The quartz cell used for absorbance measurement is 1 cm thick. The absorbance spectrum is acquired using a UV-2600 UV-Vis spectrophotometer (Shimadzu Corporation). The baseline is determined in advance in a quartz cell filled with water.

[0558] If the measured UV absorbance exceeds a predetermined threshold, the filtering of UV light is considered efficient. In particular, a composition containing 0.005% by mass of composite material A according to Example 2.A is considered to efficiently filter UV light if the maximum absorbance of these materials in the UV range exceeds 0.25.

[0559] The absorbance spectra of aqueous compositions A7 and A8 according to the present invention are shown in Figures 15 and 16.

[0560] The absorbance values ​​are reported in Table 9 below.

[0561] [Table 9]

[0562] The aqueous compositions A7 and A8 according to the present invention exhibit good absorption of UV light and, as a result, efficient filtering of UV light, particularly in the UV-B range.

[0563] The absorption spectra also show that compositions A7 and A8 according to the present invention have high transparency in the visible range between 400 and 780 nm.

Claims

1. a) Empirical formula (I) (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), at least one kind of particles of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average dimension of said particles is less than 400 nm, particles and b) At least one organosilicon compound and A composite material containing [the specified material].

2. The composite material according to claim 1, characterized in that it has an average size of the maximum particle dimensions in the range of 0.005 μm to 10 μm, preferably 0.01 μm to 1 μm.

3. The bismuth oxycarbonate particles a), and its solvates, for example other than its hydrate, preferably selected from inorganic oxides or their hydrate forms, more preferably Al(OH) 3 , Al 2 O 3 , SiO 2 , TiO 2 and ZnO, even more preferably Al(OH) 3 and SiO 2 selected from, the composite material according to claim 1 or 2, comprising one or more inorganic compounds c).

4. - a) Empirical formula (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), at least one core containing at least one kind of particles of bismuth oxycarbonate and its solvates, such as its hydrate, wherein the maximum average dimension of the particles is less than 400 nm, and - The core is surrounded by, b) at least one layer comprising at least one organosilicon compound and A composite material according to any one of claims 1 to 3, comprising:

5. - a) formula (I) (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), a core containing at least one kind of particles of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average dimension of the particles is less than 400 nm, and - An inner layer adjacent to the core, comprising at least one inorganic compound c) different from the bismuth oxycarbonate particles a), - Adjacent to the inner layer, b) an outer layer comprising at least one organosilicon compound A composite material according to any one of claims 1 to 4, comprising:

6. The composite material according to claim 4 or 5, wherein the molar ratio between the number of moles of the coating compound and the number of moles of the core compound is in the range of 0.0001 to 20, preferably 0.005 to 10, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

7. The composite material according to any one of claims 1 to 6, wherein the bismuth oxycarbonate particles are crystalline.

8. The bismuth oxycarbon particles are given by formula (BiO) 2 (CO 3 A composite material according to any one of claims 1 to 7, having )

9. The composite material according to any one of claims 1 to 8, wherein the maximum average size of the bismuth oxycarbonate particles is 300 nm or less.

10. The composite material according to any one of claims 1 to 9, wherein the bismuth oxycarbonate particles are in the form of tubes, plates and / or rods, preferably in the form of plates and / or rods.

11. The composite material according to any one of claims 1 to 10, wherein the organosilicon compound is selected from silane and its polymerized form, and siloxane and its polymerized form.

12. The composite material according to any one of claims 1 to 11, wherein the organosilicon compound is selected from alkoxysilanes, particularly from octyltriethoxysilane, dodecyltriethoxysilane, triethoxy(2,4,4-trimethylpentyl)silane, benzyltriethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (n=1) and [hydroxy(polyethyleneoxy)propyl]triethoxysilane (n=8 to 12), preferably from octyltriethoxysilane and dodecyltriethoxysilane.

13. The organosilicon compound b) has the empirical formula (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), and its solvates, such as its hydrates, as particles a), wherein the maximum average dimension of said particles is less than 400 nm, directly on the surface of particles a), or on the surface of particles comprising particles a) having the empirical formula (BiO) 2-x (CO 3 (where -0.4 < x < 0.6), and its solvates, such as its hydrates, as particles a), wherein the maximum average dimension of said particles is less than 400 nm, and an inorganic compound c) different from said bismuth oxycarbonate particles a), the method for preparing a composite material according to any one of claims 1 to 12, comprising the step of chemically grafting or physically adsorbing.

14. (i) Empirical formula (I) (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), bismuth oxycarbonate, and its solvates, for example, hydrates thereof, particles a), wherein the maximum average dimension of said particles is less than 400 nm, preparing a dispersion of particles a) in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L (ii) A step of preparing a solution of at least one organosilicon compound b) as a mixture with at least one solvent of any choice, (iii) A step of bringing the dispersion (i) and the solution (ii) into contact to form a composite material, (iv) Step of isolating the composite material The preparation method according to claim 13, including the method described in claim 13.

15. The preparation method according to claim 14, wherein the solvents in step (i) and (ii) are the same or different, preferably the solvent in step (i) is selected from protic polar solvents, more preferably from water, alcohol, polyol and mixtures thereof, and more preferably from water, and the solvent in step (ii) is selected from protic polar solvents, more preferably from alcohol, and more preferably from alcohol corresponding to the alkoxide group of organosilicon compound b).

16. A composition, specifically a cosmetic composition, comprising at least one composite material as described in any one of claims 1 to 12.

17. i) At least one composite material according to any one of claims 1 to 12, ii) at least one aqueous phase and / or at least one fatty phase, iii) At least one compound selected from 1) a UV shielding agent different from composite material i), 2) a coloring agent, 3) a cosmetic surfactant for caring for keratin substances, 4) a surfactant, 5) a thickener, and mixtures thereof. The composition according to claim 16, comprising:

18. The composition according to claim 16 or 17, wherein the composite material is present in a content of 0.5% to 70% by mass, preferably 1% to 50% by mass, and more preferably 2% to 40% by mass, based on the total mass of the composition.

19. Non-therapeutic cosmetic use of the composite material according to any one of claims 1 to 12 for filtering UV irradiation, preferably UV-B irradiation, comprising at least the application of a composition comprising the composite material according to any one of claims 1 to 12 to a keratinous substance.

20. A non-therapeutic cosmetic method for filtering UV irradiation, preferably UV-B irradiation, comprising at least the application of a composition comprising a composite material according to any one of claims 1 to 12 to a keratin substance.

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