Composite material of bismuth oxycarbonate and organic compound containing carboxyl groups for UV irradiation filtering

Abstract

Composite material of bismuth oxycarbonate and organic compound containing carboxyl groups for UV irradiation filtering 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 particularly to the use of bismuth oxycarbonate and its solvates, such as its hydrates, and organic compounds containing carboxyl groups, in the filtering of ultraviolet radiation, for composite materials for such use.

[0002] The present invention also relates to compositions, particularly cosmetic compositions, specifically compositions containing a composite material of bismuth oxycarbonate and its solvates, such as its hydrates, and an organic compound containing a carboxyl group and / or its salt.

Background Art

[0003] Keratinous substances are exposed to sunlight daily.

[0004] Irradiation with light having a wavelength between 280 nm and 400 nm is known to cause sunburn of human epidermis. However, light rays having a wavelength between 280 and 320 nm are called UV-B rays and are harmful to the occurrence of natural sunburn. This exposure is also likely to induce disorders in the biomechanical properties of the epidermis, which is reflected in the appearance of wrinkles and leads to premature aging of the skin.

[0005] UV-A rays having a wavelength between 320 and 400 nm are also known to penetrate deeper into the skin than UV-B rays. UV-A rays promote rapid and persistent pigmentation of the skin. Under standard conditions, exposure to daily UV-A irradiation can also cause damage to collagen and elastin fibers even in a short period, which is reflected in changes in the microrelief of the skin, the appearance of wrinkles, and uneven pigmentation (i.e., liver spots, unevenness of facial muscles, etc.).

[0006] Furthermore, prolonged exposure to the sun also dries out the hair and makes it more vulnerable to damage. Therefore, it is of utmost importance to protect keratinous substances, specifically human keratinous substances such as the skin.

[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, acting according to their own chemical properties and their own physical properties in terms of 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 major drawback 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 will certainly result in a film with acceptable transparency on the skin. However, in that case, adequate protection in the UV range is no longer obtained, and the advantages of such an option are 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. 5624663 [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 literature 1

Non-licensed Document 2

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 blocker that has the ability to efficiently block UV light, particularly in the UV-B and UV-A ranges, specifically UV-B light, has high transparency to visible light, does not cause whitening of the applied keratinous substance, and has good cosmetic properties.

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

[0021] Specifically, the present invention aims to provide a novel mineral UV blocker 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) at least one particle of bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6) and its solvates, such as its hydrates, wherein the maximum average size of said particles is less than 400 nm, and b) at least one organic compound containing a carboxyl group and / or one of its salts and relates to a composite material containing the same.

[0023] 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.

[0024] Preferably, the average size of the maximum size of the composite material particles is in the range of 0.01 μm to 1 μm.

[0025] Preferably, the composite material according to the present invention comprises the bismuth oxycarbonate particles a) and one or more inorganic compounds c) other than its solvates, for example its hydrates, preferably inorganic oxides, more preferably selected from zinc oxide, titanium oxide, silicon oxide and / or aluminum oxide, preferably silicon oxide and / or aluminum oxide, and optionally hydrated.

[0026] Surprisingly, and as illustrated by the following examples, the inventors have discovered that the composite materials according to the present invention also possess excellent effectiveness against ultraviolet irradiation, and in particular UV-B light filtering, as well as high transparency in the visible range, making it possible for compositions containing them to provide consumers with sufficient cosmetic properties.

[0027] For the purposes of this invention, the term "composite material" means a particulate solid material of heterogeneous origin comprising at least two immiscible components, wherein the components are bonded together via physical and / or chemical interactions.

[0028] For the purposes of this invention, the term "high transparency in the visible range" means particles having high transmittance of light between 400 and 780 nm.

[0029] 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 0.25, 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.

[0030] 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.

[0031] 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.

[0032] 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, and organic compounds containing carboxyl groups in cosmetic compositions intended for efficient shielding from UV irradiation, particularly UV-B irradiation, has not been previously proposed.

[0033] 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 the fields of sun protection, hair care, hair treatment, and makeup. Accordingly, according to another embodiment, the present invention also relates to non-therapeutic cosmetic uses of the composite materials according to the present invention, including the application of compositions containing at least the composite materials according to the present invention to keratinous substances for filtering UV irradiation, preferably UV-B irradiation.

[0034] 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 organic compound containing a carboxyl group, for filtering UV irradiation, preferably UV-B irradiation.

[0035] The present invention also relates to a method for preparing composite materials according to the present invention.

[0036] 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.

[0037] The term "at least one" is synonymous with "one or more."

[0038] Expressions such as "between... and...", "including...", "formed from...", and "within the range of..." should be understood to encompass both ends unless otherwise specified.

[0039] 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]

[0040] [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 composite material C dispersion containing 0.005 mass% in isododecane. [Figure 4] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material D dispersion containing 0.005 mass% in isododecane. [Figure 5] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material E dispersion containing 0.005 mass% in isododecane. [Figure 6] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material F dispersion containing 0.005 mass% in isododecane. [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 J dispersion containing 0.005 mass% in isododecane. [Figure 11] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material K dispersion containing 0.005 mass% in isododecane. [Figure 12] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material L dispersion containing 0.005 mass% in isododecane. [Figure 13] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material M dispersion containing 0.005 mass% in isododecane. [Figure 14] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material N dispersion containing 0.005 mass% in isododecane. [Figure 15] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material O dispersion containing 0.005 mass% in isododecane. [Figure 16] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material P dispersion containing 0.005 mass% in isododecane. [Figure 17] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material Q dispersion containing 0.005 mass% in isododecane. [Figure 18] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material R dispersion containing 0.005 mass% in isododecane. [Figure 19] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material S dispersion containing 0.005 mass% in isododecane. [Figure 20] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material T dispersion containing 0.005 mass% in isododecane. [Figure 21] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material U dispersion containing 0.005 mass% in isododecane. [Figure 22] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material V dispersion containing 0.005 mass% in isododecane. [Figure 23] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material Y dispersion containing 0.005 mass% in isododecane. [Figure 24] 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 25] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material AA dispersion containing 0.005 mass% in isododecane. [Figure 26] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material AB dispersion containing 0.005 mass% in isododecane. [Figure 27] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material AD dispersion containing 0.005 mass% in isododecane. [Figure 28] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of a composite material AF dispersion containing 0.005 mass% in isododecane. [Figure 29] This figure shows the absorption spectrum obtained by UV-Vis spectrophotometric spectroscopy of composite material D dispersion D1, which contains 0.005% by mass in caprylic acid / capric triglyceride. [Figure 30]Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of a 0.005 mass% composite material O dispersion O1 in capric / caprylic triglyceride. [Figure 31] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of a 0.005 mass% composite material O dispersion O2 in isopropyl myristate. [Figure 32] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of composition D8 diluted with deionized water and containing 0.005 mass% of composite material D. [Figure 33] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of composition O10 diluted with deionized water and containing 0.005 mass% of composite material O. [Figure 34] Figure showing the absorption spectrum obtained by UV-visible spectrophotometry of composition O11 diluted with deionized water and containing 0.005 mass% of composite material O.

DETAILED DESCRIPTION OF THE INVENTION

[0041] The present invention relates to bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, particles a), wherein the maximum average dimension of said particles is less than 400 nm, and a composite material comprising at least one organic compound b) containing a carboxyl group and / or one of its salts.

[0042] 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) one organic compound containing a carboxyl group and / or one of its salts.

[0043] The composite material according to the present invention is of nanometer and / or micrometer size. In particular, the average size of the maximum dimension of the composite material particles is in the range of 0.005 μm to 10 μm.

[0044] Preferably, the average size of the maximum dimensions of the composite material particles is in the range of 0.01 μm to 1 μm.

[0045] 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.

[0046] Preferably, particle dimensions are determined using, for example, a Hitachi HT7700 microscope, specifically by transmission electron microscopy at an accelerating voltage of 100 kV, or by scanning electron microscopy. Preferably, measurements are performed on the smallest individualized or individualizable object. 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).

[0047] The average dimensions are selected from the average length L, average width l, average thickness e, or average diameter d.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] The shape of the composite materials specifically depends on the method of preparation and the conditions under which they are operated.

[0054] 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.

[0055] 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.

[0056] In certain embodiments, the composite material according to the present invention is in the form of a sphere.

[0057] 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.

[0058] 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.

[0059] It is understood that the composite material according to the present invention may be used in the form of a mixture. In particular, the composite material according to the present invention may be used in a mixture of plates and / or rods and / or tubes in any proportion.

[0060] According to a preferred embodiment, the composite material according to the present invention is mainly, or without exception, in the form of a plate.

[0061] In the form of a "small plate," the composite material has a length greater than its width and a width greater than its thickness.

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

[0063] The "rod" shaped composite material has a solid cylindrical form with a length L greater than its diameter d, or it has a prism shape with a solid polygonal base, preferably triangular or hexagonal, where the diameter d of the internal circle circumscribing the polygonal base is less than the length L of the prism.

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

[0065] The "tube" type composite material has a hollow cylindrical shape, and its length L is greater than its diameter d.

[0066] 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 constituent materials are in the form of plates / rods / tubes.

[0067] Bismuth oxycarbonate particles a), and their solvates, such as their hydrates, and one of the organic compounds b) and / or salts thereof containing a carboxyl group may be arranged differently in the composite material.

[0068] According to one embodiment, the composite material may have at least one core and at least one coating as one or more layers surrounding the core.

[0069] Thus, the composite material may include at least one coating as one or more layers surrounding the core, which is chemically different from the coating.

[0070] The coating may be formed from one or more layers.

[0071] 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, and the maximum average dimension of the particles is less than 400 nm.

[0072] According to a particular embodiment, the core of the composite material may consist of at least a) the bismuth oxycarbonate particles and at least one inorganic compound c) different from its solvates, such as its hydrates.

[0073] The composite material may contain the bismuth oxycarbonate particles a) as defined above, and its solvates, such as its hydrates, in the core and / or in the layer forming the coating.

[0074] According to a particular embodiment, the material contains at least one of the bismuth oxycarbonate particles a) as defined above, and its solvates, such as its hydrates, in the core.

[0075] According to another particular embodiment, the material contains the bismuth oxycarbonate particles a) as defined above, and its solvates, such as its hydrates, in the coating. According to one embodiment, when present, the inorganic compound c) may coat all or part of at least one of the bismuth oxycarbonate particles a) and its solvates, such as its hydrates.

[0076] According to another embodiment, when present, the inorganic compound c) may be completely or partially coated by at least one of the bismuth oxycarbonate particles a) and its solvates, such as its hydrates.

[0077] In particular, 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.

[0078] According to a particular embodiment, the composite material according to the invention contains a layer surrounding at least one core.

[0079] Thus, according to a particular embodiment, the composite material according to the invention comprises at least a) bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, in the form of particles, the maximum average dimension of said particles being less than 400 nm, and the surface of said core being coated by a coating comprising at least one organic compound and / or one salt thereof containing carboxyl groups either continuously or discontinuously, said composite material comprising particles.

[0080] According to a first variant of the invention, the composite material according to the invention comprises a coating, also called a shell or an envelope, which is continuous, i.e. surrounds the entire surface of the core.

[0081] According to a second variant of the invention, the composite material according to the invention comprises a coating, also known as a shell or an envelope, which is discontinuous, i.e. surrounds the core surface discontinuously. Preferably, 10% to 90%, more particularly 10% to 70%, and even more particularly 30% to 50% of the core surface is coated with the coating.

[0082] According to one embodiment, the coating is a multilayer coating, i.e. it comprises one or more inner layers and outer layers, in other words several whole or partially overlapping layers which can each be continuous or discontinuous.

[0083] In multilayer coatings, the term "inner layer" refers to any layer other than the outer layer. This could be a layer directly superimposed on the core, or any intermediate layer between the core and the outer layers.

[0084] In multilayer coatings, the term "outer layer" refers to the final layer of coating that is not adjacent to the core. The outer layer is separated from the core by at least one inner layer. The outer layer does not have a coating.

[0085] In a multilayer coating consisting of two layers, the inner layer is adjacent to the core, while the outer layer is adjacent to the inner layer but not to the core.

[0086] In multilayer coatings consisting of more than two layers, the inner layers are the layers adjacent to the core and the intermediate layers between the core-adjacent layers and the outer layers.

[0087] The inner layers forming the multilayer coating of the composite material and the single outer layer of the composite material may be formed from the same or different compounds.

[0088] Each layer may consist of a single compound or a mixture of compounds. In particular, the layers may extend concentrically with respect to the core.

[0089] In particular, the composite material according to the present invention has a double layer surrounding the core, in other words, an inner layer and an outer layer.

[0090] According to a preferred embodiment, the composite material according to the present invention preferably has at least one layer comprising b) at least one organic compound and / or a salt thereof containing a carboxyl group.

[0091] According to a preferred embodiment, the composite material according to the present invention is - At least a) empirical formula (BiO) 2-x(CO3) (where -0.4 < x < 0.6), and a core containing particles of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average dimension of said particles is less than 400 nm, and - at least one layer that continuously or discontinuously surrounds said core and contains at least one kind of a) at least one organic compound containing a carboxyl group and / or one of its salts is included. Preferably, the composite material according to the present invention - at least a) an empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and a core containing particles of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average dimension of said particles is less than 400 nm, - a single layer adjacent to said core and containing at least one kind of a) at least one organic compound containing a carboxyl group and / or one of its salts is included.

[0092] According to another preferred embodiment, the composite material according to the present invention - at least a) an empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and particles of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average dimension of said particles is less than 400 nm, and a core containing at least one kind of a) at least one organic compound containing a carboxyl group and / or one of its salts - at least one layer that surrounds said core and contains at least one kind of a) at least one organic compound containing a carboxyl group and / or one of its salts is included.

[0093] According to a preferred embodiment, the composite material according to the present invention - a) at least particles of an empirical formula (BiO) 2-x [[ID=3 =2]](CO3) (where -0.4 < x < 0.6), and particles of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average dimension of said particles is less than 400 nm, and a core containing at least one kind of a) at least one organic compound containing a carboxyl group and / or one of its salts - A single layer adjacent to the core and containing one kind of at least one organic compound containing a carboxyl group or a salt thereof is included.

[0094] According to a specific embodiment, the composite material according to the present invention - At least a) an oxycarbonate bismuth of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and a core containing particles of its solvate, such as its hydrate, wherein the maximum average dimension of the particles is less than 400 nm - An inner layer adjacent to the core and containing one kind of at least one organic compound containing a carboxyl group and / or a salt thereof - Adjacent to the inner layer, at least a) an oxycarbonate bismuth of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and particles of its solvate, such as its hydrate, wherein the maximum average dimension of the particles is less than 400 nm, and b) an outer layer containing one kind of at least one organic compound containing a carboxyl group and / or a salt thereof is included.

[0095] According to another preferred embodiment, the composite material according to the present invention - At least a) an oxycarbonate bismuth of the empirical formula (BiO) 2-x (CO3), and particles of its solvate, such as its hydrate, wherein the maximum average dimension of the particles is less than 400 nm, and a core containing at least one inorganic compound c) different from the oxycarbonate bismuth particles a) and its solvate, such as its hydrate - At least one layer surrounding the core and containing one kind of at least one organic compound containing a carboxyl group and / or a salt thereof is included.

[0096] According to a preferred embodiment, the composite material according to the present invention - At least a) an oxycarbonate bismuth of the empirical formula (BiO) 2-x(CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, particles wherein the maximum average dimension of said particles is less than 400 nm, particles, and the bismuth oxycarbonate particles a), and its solvates, such as its hydrates, and at least one inorganic compound c) different from the same, a core - adjacent to said core, a single layer containing one kind of at least one organic compound containing a carboxyl group or a salt thereof comprising.

[0097] According to a particular embodiment, the composite material according to the invention is - at least a) empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, a core containing particles, wherein the maximum average dimension of said particles is less than 400 nm, a core, - adjacent to said core, an inner layer containing at least one inorganic compound c) different from the bismuth oxycarbonate particles a) and its solvates, such as its hydrates, - adjacent to said inner layer, an outer layer containing one kind of at least one organic compound containing a carboxyl group and / or a salt thereof comprising.

[0098] a) Bismuth oxycarbonate particles The bismuth oxycarbonate particles a) according to the invention have the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates. The value of x can specifically be determined by elemental analysis.

[0099] Preferably, x is equal to 0, and the empirical formula of the bismuth oxycarbonate particles is (BiO)2(CO3). [[ID=3,2]]

[0100] The bismuth oxycarbonate particles according to the invention can be crystalline or amorphous.

[0101] According to one embodiment of the invention, the bismuth oxycarbonate particles are amorphous.

[0102] According to a preferred embodiment of the present invention, the bismuth oxycarbonate particles are crystalline.

[0103] It is understood that bismuth oxycarbonate particles may consist of a mixture of several types of bismuth oxycarbonate particles having different empirical formulas and / or different shapes.

[0104] Therefore, bismuth oxycarbonate particles can be a mixture of amorphous and crystalline particles.

[0105] For the purposes of this invention, "crystalline" means that the atoms forming the bismuth oxycarbonate particles are arranged in an ordered manner. In other words, crystalline bismuth oxycarbonate particles are an organized substance.

[0106] In contrast, "amorphous" particles are particles in which atoms are disordered. The atoms of such particles exhibit no structure whatsoever at the microscopic level.

[0107] Preferably, the crystalline particles obtained by the present invention are lamellae, which are [Bi2O2] 2+ and [CO3] 2- It has a crystalline phase of the natural mineral bismutite, which has alternating layers.

[0108] Such particles crystallize together with the space group Imm2 in an orthorhombic system.

[0109] The bismutite crystal structure of bismuth oxycarbonate may have the following lattice parameters: a=3.865Å, b=3.862Å, c=13.675Å and V lattice = 0.204nm 3 This specific atomic arrangement enables the growth of anisotropic materials.

[0110] A particle is considered "anisotropic" if its extension coefficient R, i.e., R = L / e, between its length L and thickness e, is greater than 2.

[0111] According to the present invention, the bismuth oxycarbonate particles of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, have a maximum average dimension of less than 400 nm. Preferably, the maximum average dimension of said particles is 300 nm or less. According to the present invention, the bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, can be of any shape.

[0112] The shape of said particles specifically depends on the method of preparing them and the conditions of operation.

[0113] In particular, the particles according to the present invention can be in the form of tubes, small plates, thin plates, rods, spheres, flowers, rosettes, threads, filaments, fibers, needles, cubes or any mixture thereof.

[0114] 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 rosettes.

[0115] 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 preferentially, the particles according to the present invention are in the form of small plates and / or rods.

[0116] Thus, particles in the form of small plates or rods or tubes are specifically different from spherical or fibrous forms or flowers, rosettes, threads, filaments, needles or cubes.

[0117] 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.

[0118] According to a preferred embodiment, the particles used according to the present invention are mainly or exclusively in the form of small plates.

[0119] "Plate-like" particles have a length greater than their width and a width greater than their thickness.

[0120] In particular, when in plate form, 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。

[0121] 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. The "rod" shaped particles have a solid cylindrical shape with a length L greater than its diameter d, or a prismatic shape with a solid polygonal base, preferably triangular or hexagonal, where the diameter d of the circle circumscribing the base of the polygon is less than the length L of the polygon.

[0122] 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

[0123] 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. The "tubular" particles have a hollow cylindrical shape, with a length L greater than its diameter d.

[0124] 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

[0125] 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.

[0126] Particle doping According to certain embodiments, bismuth oxycarbonate particles a) and their solvates, such as their hydrates, can be doped.

[0127] In particular, bismuth oxycarbonate particles can be doped with one or more chemical elements that have the ability to be inserted into the structure or to partially replace elements that are already present.

[0128] Particles can be doped by substitution of all or some cations and / or all or some anions.

[0129] According to certain embodiments, doping is in part with respect to the inserted cation or the cation as a substitution for bismuth, with respect to bismuth limited to 20% of the composition. According to this variation, the degree of doping is 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%.

[0130] In particular, bismuth oxycarbonate particles 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).

[0131] Preferably, bismuth oxycarbonate particles can be doped with cations derived 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.

[0132] 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%.

[0133] According to a variation of another embodiment, bismuth oxycarbonate particles are doped with cations derived from iron, with the degree of doping being particularly in the range of 0.5% to 2%.

[0134] 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 partially or entirely.

[0135] 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%.

[0136] In particular, bismuth oxycarbonate particles are subjected to 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 - They can be doped with polyatomic anions selected from ). Preferably, the bismuth oxycarbonate particles are S 2- , SO3 2- SO4 2- Cl - and / or I - Therefore, SO3 is given higher priority. 2- SO4 2- and / or Cl - , with higher priority Cl - or SO4 2- It can be doped by.

[0137] 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%.

[0138] 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%.

[0139] 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%.

[0140] According to a variation of another embodiment, the bismuth oxycarbonate particles are preferably composed of 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 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 - ) is selected from polyatomic anions, with S being preferred. 2- , SO3 2- SO4 2- Cl - and / or I - Therefore, SO3 is given even higher priority. 2- SO4 2- and / or Cl - by, and especially preferably with Cl - , I - Or SO4 2- It is doped by.

[0141] In a preferred embodiment, the bismuth oxycarbonate particles and their solvates, such as their hydrates, obtained by the present invention are undoped.

[0142] 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.

[0143] 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.

[0144] 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).

[0145] 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.

[0146] 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, and their solvates, such as their hydrates.

[0147] Specifically, solvothermal synthesis of particles is described in the following works: 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 Nnosheets: 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. exposed, Journal of Molecular Catalysis A: Chemical, 2010, 317(1~2), pp. 34~40); Liu, SQThe effects of citrate ion on morphology and photocatalytic activity of flower-like Bi2O2CO3 are described in the paper by Chen, R. et al. (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). The electrochemical synthesis of the 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).

[0148] 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).

[0149] 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).

[0150] According to a preferred embodiment, the bismuth oxycarbonate particles a) and their solvates, such as their hydrates, obtained by 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. According to a preferred embodiment, the bismuth oxycarbonate particles and their solvates, such as their hydrates, 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.

[0151] When particles used in accordance with the present invention are doped, one or more additional reagents containing doping elements may be added.

[0152] 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.

[0153] Bismuth(III) complexes can also be obtained from bismuth minerals, such as elemental bismuth and / or bismuth oxide and / or bismuth sulfide.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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. 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.

[0163] The resulting particles are isolated from the reaction medium by centrifugation and washed by a continuous cycle of dispersion and centrifugation.

[0164] After drying under vacuum at a temperature between 40°C and 60°C, a white powder is obtained.

[0165] When a polyol is used as a solvent, the resulting bismuth oxycarbonate particles and their solvates, such as their hydrates, are in the form of small plates, preferably having an average thickness e between 2 and 15 nm, and / or tubes. 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.

[0166] 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 a solution of polyols at 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) that is the same as or different from the one in Solution A, preferably the same, from a partially or completely dissolved carbonate agent, preferably in an amount of 1 to 100 equivalents relative to the bismuth complex.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] Preferably, the reaction temperature is between 90°C and 150°C, and the reaction time is between 4 and 16 hours.

[0171] The resulting particles are isolated from the reaction medium by centrifugation and washed by a continuous cycle of dispersion and centrifugation.

[0172] After drying under vacuum at a temperature between 40°C and 60°C, a white powder is obtained.

[0173] When polyols are used solely as additives, they may be selected from ethylene glycol, propylene glycol, glycerol and / or sugars, preferably sugars, more preferably D-mannitol.

[0174] 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.

[0175] 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.

[0176] Organic compounds containing a carboxyl group (b) The one or more organic compounds b) containing carboxyl groups in the composite material according to the present invention are organic compounds, i.e., compounds containing carbon, hydrogen and oxygen atoms, and may further contain one or more heteroatoms selected from nitrogen and sulfur, and the organic compounds may be cyclic or acyclic, aromatic or non-aromatic, linear or branched, saturated or unsaturated, polymeric or non-polymeric, lipophilic and / or hydrophilic, and contain one or more carboxyl groups, i.e., one or more carboxylic acid functional groups -C(O)-OH, and carboxylate salts -C(O)-O having (non)organic, i.e., organic or inorganic bases. - M + It also contains the salt known as M + represents a cationic counterion, more specifically an alkali metal or alkaline earth metal, such as sodium or potassium, preferably an alkali metal, such as sodium.

[0177] The one or more organic compounds b) containing a carboxyl group in the present invention are preferably nonpolymeric.

[0178] Here, compounds containing a carboxyl group are intended to refer to and include, in particular, monoacids (containing a single carboxyl group -C(O)OH and / or one of its salts having a (non)organic base) and polyacids (containing two or more carboxyl groups and / or its salts having a (non)organic base), i.e., simple carboxylic acids and polycarboxylic acids, either alone or in mixtures.

[0179] Each organic compound b) containing a carboxyl group according to the present invention preferably contains only one or two carboxyl groups, or only one or two carboxylate groups.

[0180] According to certain embodiments, one or more compounds b) containing a carboxyl group exist partially or completely in the form of a carboxylate salt associated therewith.

[0181] In general, any organic compound having at least one carboxyl functional group -C(O)OH (also called a carboxyl group) is suitable in the context of the present invention. The acid used is preferably compatible with keratinous substances for cosmetic purposes and is acceptable. The organic compounds containing carboxyl groups according to the present invention preferably do not have therapeutic effects.

[0182] One or more organic compounds containing a carboxyl group are preferably selected from hydrophilic, lipophilic, or amphiphilic molecules.

[0183] More specifically, one or more organic compounds containing a carboxyl group contain 2 to 40 carbon atoms, preferably 2 to 30 carbon atoms, more specifically 3 to 26 carbon atoms, better 4 to 24 carbon atoms, and even better 6 to 20 carbon atoms.

[0184] According to one embodiment, one or more organic compounds b) containing a carboxyl group contain 2 to 8 carbon atoms. Such acid b) is preferably saturated and optionally contains one or more hydroxyl groups.

[0185] According to another embodiment, one or more organic compounds b) containing a carboxyl group are selected from amino acids, preferably amino acids with "acid" in their name such as aspartic acid and glutamic acid, or N-acyl derivatives of amino acids. More specifically, the N-acyl derivatives of amino acids have a (hydroxy)(C7~C) such as a lauroyl group as the N-terminal amine functional group. 29 These are amino acids that are acylated by an alkylcarbonyl group. Possible examples include N-lauroylglycine, N-lauroyl glutamate, or salts thereof.

[0186] More preferably, one or more organic compounds b) containing a carboxyl group are selected from lipophilic or amphiphilic organic molecules.

[0187] According to a particular embodiment of the present invention, one or more organic compounds b) containing a carboxyl group are saturated, linear or branched fatty acids which are optionally substituted with one or more hydroxyl groups, preferably unsubstituted, and / or optionally shielded with one or more heteroatoms, such as O, N and S, preferably O, and the fatty acid is more specifically C8-C 24 , and especially C8~C 20 The fatty acids are selected from caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, palmitic acid, 3-[2-(2-methoxyethoxy)ethoxy]propanoic acid, salts thereof having a (non)organic base, especially alkali metal salts, such as sodium salts, and mixtures thereof.

[0188] More specifically, they are C8~C 20 They are selected from sodium salts of fatty acids. More specifically, they are selected from salts of (non)organic bases containing stearic acid, particularly alkali metal or alkaline earth metal salts of stearic acid, and more precisely, alkali metal salts such as sodium stearic acid (INCI name: sodium stearate).

[0189] According to another specific embodiment of the present invention, one or more organic compounds b) containing a carboxyl group are selected from unsaturated fatty acids or salts thereof that are optionally substituted with one or more hydroxyl groups, more specifically C8-C8 24 , and especially C8~C 20 A selection of fatty acids, preferably myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, ricinoleic acid, linoleic acid, linolenic acid, arachidonic acid, and / or salts thereof, more specifically selected from their sodium salts.

[0190] According to a preferred embodiment, one or more organic compounds b) containing a carboxyl group are selected from fatty acids, more specifically linear or branched, saturated or unsaturated fatty acids which are optionally substituted with one or more hydroxyl groups and / or optionally shielded by one or more heteroatoms selected from O, N and S, preferably O, and the fatty acid contains 8 to 20 carbon atoms.

[0191] According to a particular embodiment, one or more organic compounds b) containing a carboxyl group include one or more cyclic groups, preferably C6 cyclic groups, more preferably aromatic groups such as phenyl, which are optionally substituted, preferably with one or more hydroxyl groups. Possible examples include capryloyl salicylic acid or a salt thereof.

[0192] The acid in question is preferably a linear fatty acid containing 8 to 20 carbon atoms.

[0193] The fatty acids of the present invention may be saturated or unsaturated.

[0194] For example, fatty acids can be selected from stearic acid, oleic acid, palmitic acid, palmitoleic acid, sapienic acid, lauric acid, myristic acid, myristoleic acid, capric acid, caprylic acid, sebacic acid, triisostearic acid, isostearic acid, linoleic acid, linolenic acid, heptanoic acid, stearidonic acid, hexanoic acid, arachidic acid, and / or one of their salts, as well as mixtures thereof.

[0195] Fatty acids can be in mixtures; that is, in commercially available products, especially when their chain lengths differ, two or more types may be adjacent to each other in a mixture form.

[0196] The one or more organic compounds b) containing a carboxyl group can preferably be selected from stearic acid, oleic acid, lauroyl glutamic acid, capryloyl salicylic acid, 3-[2-(2-methoxyethoxy)ethoxy]propanoic acid, or one of their salts, and mixtures thereof. According to a particular embodiment, the molar ratio between b) one of the organic compounds containing a carboxyl group and / or a salt thereof and a) bismuth oxycarbonate particles and its solvate, for example, its hydrate, is, according to the present invention, between 0.0001 and 20, more preferably between 0.01 and 5, and even more preferably between 0.05 and 3.

[0197] 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.

[0198] The inorganic compound c) may be amorphous or crystalline, alkali metal or alkaline earth metal, specifically sodium, potassium, magnesium and calcium, or transition metal, specifically titanium, aluminum, manganese, iron, copper, niobium and tantalum, or lanthanide, specifically cerium, or poor metal, specifically zinc, indium and bismuth, in hydrated or unhydrated form of oxide, hydroxide or oxyhydroxide.

[0199] The inorganic oxide can also be in an amorphous or crystalline, hydrated or non-hydrated form of a metalloid oxide or hydroxide or oxyhydroxide.

[0200] In particular, the inorganic compound c) can be in an amorphous or crystalline, hydrated or non-hydrated form of an oxide or hydroxide or oxyhydroxide of silicon, such as silicates of silicon with 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, borosilicates of aluminum and / or calcium and / or magnesium and / or sodium and / or titanium and / or iron and / or zinc and / or bismuth, etc., including clay.

[0201] In particular, the inorganic compound c) can be in an amorphous or crystalline, hydrated or non-hydrated form of an inorganic carbide or sulfide or nitride, such as silicon carbide, sulfides of iron, copper and zinc, or nitrides of boron and silicon, for example.

[0202] Examples of metal oxides include hydrated or non-hydrated forms of 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 also mixtures thereof.

[0203] Preferably, hydrated or non-hydrated forms of Al2O3, Al(OH)3, SiO2, TiO2, ZnO and mixtures thereof are used, more preferably, hydrated or non-hydrated forms of Al2O3, Al(OH)3, SiO2, TiO2, ZnO and mixtures thereof are used, even more preferably, hydrated or non-hydrated forms of Al2O3, Al(OH)3, SiO2 and mixtures thereof are used.

[0204] According to a preferred embodiment, the composite material according to the present invention does not contain any inorganic compound c) different from the bismuth oxycarbonate particles a) and its solvates, such as its hydrates.

[0205] According to another preferred embodiment, the composite material according to the present invention contains the bismuth oxycarbonate particles a) and an inorganic compound c) different from its solvates, such as its hydrates, preferably an inorganic oxide, more preferably silica, alumina, titanium dioxide and zinc oxide, and even more preferably only one selected from silica.

[0206] According to another preferred embodiment, the composite material according to the present invention contains the bismuth oxycarbonate particles a) and an inorganic compound c) different from its solvates, such as its hydrates, preferably 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 more preferably only one selected from Al(OH)3.

[0207] Preferably, the composite material according to the present invention contains one or more inorganic oxides c) selected from, preferably from inorganic oxides different from the bismuth oxycarbonate particles a) and its solvates, such as its hydrates, more preferably from zinc oxide, titanium dioxide, silicon oxide and / or aluminum oxide, preferably from silicon oxide and / or aluminum oxide, and they are optionally hydrated.

[0208] According to a specific embodiment, when one or more inorganic compounds c) are present, the average size of the maximum dimension of the composite material particles is between 0.005 and 10 μm, preferably between 0.01 and 1 μm.

[0209] Method for preparing the composite material The composite material according to the present invention can specifically be obtained through the preparation method described below.

[0210] In particular, the composite material according to the invention can be obtained by chemically grafting or physically adsorbing one kind of an organic compound b) containing a carboxyl group and / or its salt 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 containing the bismuth oxycarbonate particles a) defined above, and its solvates, such as its hydrates and an inorganic compound c).

[0211] Particles containing the bismuth oxycarbonate particles defined above, and its solvates, such as its hydrates and one or more inorganic compounds c) can be prepared in one or more steps.

[0212] In particular, the composite material according to the invention can be obtained in one or more steps.

[0213] In particular, the method for preparing the composite material according to the invention - the bismuth oxycarbonate of the empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, particles a), wherein the maximum average dimension of the particles is less than 400 nm, particles a) - optionally, one or more precursors intended to form an inorganic compound c) different from the bismuth oxycarbonate particles and its solvates, such as its hydrates - one or more organic compounds b) containing a carboxyl group defined above and / or one kind of its salt - optionally one or more additives, and - optionally one or more solvents are used.

[0214] According to a particular embodiment, the method for preparing the composite material according to the invention may include one or more separation steps.

[0215] In particular, precursors intended to form inorganic compounds c) different from the bismuth oxycarbonate particles a) and its solvates, such as its hydrate, are selected from organic or inorganic compounds that result from chemical reactions or physical adsorption of particles of bismuth oxycarbonate a) and its solvates, such as its hydrate, as well as particles of inorganic compound c).

[0216] In particular, the precursor is - As previously mentioned inorganic compound 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.

[0217] 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.

[0218] According to a preferred embodiment, the method for preparing the composite material according to the present invention does not use a precursor to form the bismuth oxycarbonate particles a) and an inorganic compound c) different therefrom, such as its solvate or hydrate.

[0219] According to a preferred embodiment, the method for preparing the 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) and its solvates, such as its hydrates, and the precursor is preferably selected from sodium silicate and sodium aluminate. According to a specific embodiment, the method for preparing the composite material according to the present invention uses at least one solvent.

[0220] The choice of solvent can depend particularly on the precursors and additives used in the method.

[0221] In particular, the solvent can be selected from polar or non-polar, protic or aprotic solvents. Preferably, the solvent used is a protic polar solvent, particularly selected from water, alcohols, polyols and mixtures thereof.

[0222] Preferably, the solvent used is water.

[0223] According to a specific embodiment, the method for preparing the composite material according to the present invention uses at least one additive.

[0224] In particular, the additive can be selected from acids, particularly mineral acids such as hydrochloric acid or sulfuric acid, and bases, preferably mineral bases such as sodium hydroxide or potassium hydroxide.

[0225] One of the organic compound b) containing the carboxyl group defined above and / or its salt can be used as a pure substance or a mixture. Therefore, oils, such as natural oils containing one or more organic compounds b) containing the carboxyl group defined above, specifically several organic compounds b) containing the carboxyl group and / or one of its salts, can be used.

[0226] According to a specific embodiment, the present invention is directed to a method for preparing the composite material defined above, (i) empirical formula (BiO) 2-x(CO3) (where -0.4 < x < 0.6), bismuth oxycarbonate a), and its solvates, such as its hydrates, in a dispersion where the maximum average size of the particles is less than 400 nm, in at least one solvent, particularly prepared in an amount ranging from 0.05 g / L to 500 g / L. (ii) A solution of at least one organic compound b) containing a carboxyl group and / or one of its salts, optionally as a mixture with at least one solvent, particularly prepared in an amount ranging from 0.05 g / L to 500 g / L. (iii) Contacting the dispersion (i) and the solution (ii) to form a composite material. (iv) Isolating the composite material. including.

[0227] Particularly, the solvents in steps (i) and (ii) may be the same or different, preferably selected from protic polar solvents, more preferably from water, alcohol, polyol, and mixtures thereof, and even more preferably the solvent is water.

[0228] According to a particular embodiment, the dispersion medium (i) can be heated to a temperature of preferably 70 °C for refluxing.

[0229] According to a particular embodiment, when the solvent or mixture of solvents in step (i) contains water, the pH can be adjusted to be between 5 and 10, preferably between 6 and 8, for example, preferably by adding an inorganic base, such as a hydroxide of an alkali metal or alkaline earth metal, such as sodium hydroxide.

[0230] According to a particular embodiment, the solution (ii) can be heated to a temperature of preferably 80 °C before mixing in step (iii) for refluxing.

[0231] According to a particular embodiment, in step (iii), the molar ratio of one of the organic compounds b) and / or salts thereof containing a carboxyl group / bismuth oxycarbonate a) and its solvate, for example, its hydrate, is in the range of 0.0001 to 20, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

[0232] According to a particular embodiment, step (iii) is carried out with stirring.

[0233] According to a particular embodiment, step (iii) is performed for a period of time ranging from 1 minute to 24 hours, preferably from 20 minutes to 8 hours.

[0234] According to a preferred embodiment, step (iii) is carried out at a temperature in the range of 70°C to 80°C.

[0235] According to a particular embodiment, the pH in step (iii) is adjusted to 6.5 by adding, for example, an acid, preferably an inorganic acid, such as sulfuric acid.

[0236] According to certain embodiments, a cooling step can be performed between steps (iii) and (iv).

[0237] According to a particular embodiment, step (iv) can be carried out by centrifugal separation.

[0238] According to a particular embodiment, following step (iv), a washing step is performed, specifically in a continuous cycle, optionally a drying step, for example by oven drying, at a temperature in the range of 40°C to 100°C, optionally under vacuum (pressure less than 100 mbar).

[0239] According to certain embodiments, the present invention relates to a method for preparing a previously defined composite material, (a) Particles a) of bismuth oxycarbonate of the experimental formula (BiO)2-x(CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, 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 in the range of 0.05 g / L to 500 g / L, (b) Preparing an aqueous sodium silicate solution, (c) Contacting said dispersion (a) and said solution (b) to form particles of bismuth oxycarbonate and silica, (d) Isolating the particles of bismuth oxycarbonate and silica, (e) Dispensing the particles of bismuth oxycarbonate and silica (d) in at least one solvent, particularly in an amount in the range of 0.05 g / L to 500 g / L, (f) Optionally preparing a solution of at least one organic compound (b) containing a carboxyl group and / or a salt thereof as a mixture with at least one solvent, particularly in an amount in the range of 0.05 g / L to 500 g / L, (g) Contacting said dispersion (e) and said solution (f) to form a composite material, (h) Isolating said composite material comprising.

[0240] According to a particular embodiment, the preparation method includes a firing step (d') before step (e).

[0241] According to a particular embodiment, the firing 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.

[0242] Particularly, the solvents in steps (a), (e) and (f) may be the same or different, preferably selected from protic polar solvents, more preferably from water, alcohols, polyols and mixtures thereof, and even more preferably the solvent is water.

[0243] 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.

[0244] 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.

[0245] According to a particular embodiment, the pH of step (c) is adjusted to a pH in the range of 3 to 11, particularly 5 to 8, preferably 6 to 7, specifically in order to form silica.

[0246] According to a particular embodiment, step (c) is carried out with stirring.

[0247] 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.

[0248] According to a preferred embodiment, step (c) is carried out at a temperature below 100°C.

[0249] According to certain embodiments, step (d) can be carried out by centrifugal separation. According to certain embodiments, a washing step is carried out following step (d), specifically in a continuous cycle, optionally by an oven drying step, at a temperature in the range of 40°C to 100°C, optionally under vacuum (pressure less than 100 mbar). According to certain embodiments, the dispersion medium (e) can be heated to a temperature of preferably 70°C for reflux.

[0250] According to a particular embodiment, the pH in step (e) is adjusted to a pH in the range of 3 to 10 by adding, for example, sodium hydroxide or sulfuric acid.

[0251] 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.

[0252] According to a specific embodiment, the molar ratio of the carboxyl group-containing organic compound b) and / or its salt in step (g) to the particles of bismuth oxycarbonate and silica is in the range of 0.0001 to 20, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

[0253] According to a specific embodiment, step (g) is carried out with stirring.

[0254] According to a specific embodiment, step (g) is carried out for a time in the range of 1 minute to 24 hours, preferably 20 minutes to 8 hours.

[0255] According to a preferred embodiment, step (g) is carried out at a temperature in the range of 70 °C to 80 °C.

[0256] According to a specific embodiment, the pH in step (g) is adjusted to 6.5, for example, by adding sulfuric acid.

[0257] According to a specific embodiment, a cooling step can be carried out between step (g) and step (h).

[0258] According to a specific embodiment, step (h) can be carried out by centrifugation. According to a specific embodiment, a washing step is carried out following step (h), specifically in a continuous cycle, optionally by oven drying, for example, at a temperature in the range of 40 °C to 100 °C, optionally under vacuum (pressure less than 100 mbar).

[0259] According to a specific embodiment, the present invention is directed to a method for preparing the composite material defined above, (1) Experimental formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6) of 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 in the range of 0.05 g / L to 500 g / L (2) A step of preparing an aluminum salt solution in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L. (3) The step of bringing the dispersion (1) and the solution (2) into contact, (3') Optionally, a step of isolating the mixture obtained from step (3), (3'')Optionally, the mixture isolated from step (3') is subjected to a calcination step to obtain particles of bismuth oxycarbonate and alumina. (3''')Optionally, the step of dispersing the bismuth oxycarbonate and alumina particles (3') in at least one solvent, particularly in an amount ranging from 0.05 g / L to 500 g / L. (4) A step of preparing a solution of at least one organic compound b) containing a carboxyl group and / or a salt thereof as a mixture with at least one solvent of any choice, particularly in an amount ranging from 0.05 g / L to 500 g / L. (5) The step of bringing the mixture obtained as a result of step (3) into contact with the solution (4) to form a composite material. (6) Step of isolating the composite material Includes.

[0260] 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, and particularly for a time in the range of 15 minutes to 2 hours.

[0261] In particular, the solvents in steps (1), (2), and (4) may be the same or different, and are preferably selected from protic polar solvents, more preferably from water, alcohols, polyols, and mixtures thereof, with water being the most preferred solvent.

[0262] According to a particular embodiment, the bismuth oxycarbonate and its solvate, for example, its hydrate, are present in the dispersion (1) at a concentration 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.

[0263] 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 in the range of 50°C to 100°C, for a time in particular in the range of 1 minute to 24 hours, preferably in the range of 20 minutes to 2 hours.

[0264] 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, sodium hydroxide.

[0265] 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, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

[0266] According to a particular embodiment, the pH in step (3) is adjusted to a pH in the range of 6 to 8 by adding, for example, sodium hydroxide.

[0267] According to a particular embodiment, step (3) is carried out while stirring.

[0268] 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.

[0269] According to a preferred embodiment, step (3) is carried out at a temperature in the range of 60°C to 70°C.

[0270] 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.

[0271] According to a particular embodiment, the molar ratio of one of the organic compounds b) containing a carboxyl group and / or a salt thereof / bismuth oxycarbonate particles and its solvate, for example, its hydrate, in step (5) is in the range of 0.0001 to 20, more preferably 0.01 to 5, and even more preferably 0.05 to 3.

[0272] According to a particular embodiment, step (5) is carried out while stirring.

[0273] According to a particular embodiment, step (5) is carried out for a period of time ranging from 1 minute to 24 hours, preferably from 20 minutes to 8 hours.

[0274] According to a preferred embodiment, step (5) is carried out at a temperature in the range of 70°C to 80°C.

[0275] According to a particular embodiment, the pH in step (5) is adjusted to 6.5, for example, by adding sulfuric acid.

[0276] According to certain embodiments, a cooling step can be performed between steps (5) and (6).

[0277] According to a particular embodiment, step (6) can be carried out by centrifugal separation. According to a particular embodiment, following step (6), a washing step is carried out, 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).

[0278] Cosmetic composition The composite material according to the present invention can be used in compositions, particularly in cosmetic compositions.

[0279] Therefore, the present invention also relates to compositions comprising at least one of the previously defined composite materials, specifically cosmetic compositions.

[0280] 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) 1) UV shielding agents different from composite materials i), 2) colorants, 3) cosmetic surfactants for caring for keratin substances, 4) surfactants, 5) thickeners, and mixtures thereof at least one compound selected from This also relates to compositions containing, specifically cosmetic compositions.

[0281] The composite material may be present in the composition, preferably a cosmetic composition, in an amount ranging from 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.

[0282] aqueous phase The composition according to the present invention, specifically a cosmetic composition, may contain at least one aqueous phase.

[0283] The aqueous phase may include water and, optionally, a water-soluble solvent.

[0284] In the present invention, the term "water-soluble solvent" refers to a compound that is liquid at room temperature and is miscible with water (more than 50% by mass miscible with water at 25°C and atmospheric pressure).

[0285] The water-soluble solvents that can be used in the compositions according to the present invention may also be volatile.

[0286] 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.

[0287] Among the water-soluble solvents that can be used in the compositions according to the present invention, polyols are specifically mentioned. For the purposes of the present invention, the term "polyol" means any organic molecule containing at least two free hydroxyl groups.

[0288] Polyols suitable for use in the present invention may be linear, branched, or cyclic alkyl compounds, saturated or unsaturated, having at least two -OH functional groups, and particularly at least three -OH functional groups, on the alkyl chain.

[0289] Polyols that are advantageously suitable for formulation of the composition according to the present invention are, specifically, those containing 2 to 32 carbon atoms, and preferably 3 to 16 carbon atoms.

[0290] 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.

[0291] 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.

[0292] 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 components used in the formulation of the composition of the present invention.

[0293] Preferably, the fatty phase includes at least one type of oil, specifically a cosmetic oil.

[0294] The term "oil" refers to a water-immiscible, non-aqueous compound that is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg).

[0295] The fatty phase may contain at least one volatile or non-volatile hydrocarbon oil and / or fatty substance.

[0296] 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 Examples of higher fatty acids, carbonates, and mixtures thereof can be particularly cited.

[0297] Examples of volatile hydrocarbon oils include hydrocarbon oils containing 8 to 16 carbon atoms.

[0298] 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.

[0299] Volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof, can also be used.

[0300] 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.

[0301] 1) UV shielding agent According to a particular embodiment, the composition according to the present invention is 1) At least one UV shielding agent obtained by the present invention, which is different from the composite material defined above. Includes.

[0302] For the purposes of this invention, the term "UV shielding agent other than composite material" is intended to refer to any UV shielding agent that is obtained by this invention and has different chemical properties from those of the composite material defined above.

[0303] Therefore, the composite material according to the present invention can be used alone or in combination with other UV shielding agents selected particularly from organic and / or inorganic UV shielding agents.

[0304] Therefore, the cosmetic composition may also contain one or more additional UV shielding agents1) 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.

[0305] The term "hydrophilic UV shielding agent" means any organic or inorganic compound for cosmetic or skin use, for filtering UV irradiation, which can be completely dissolved in molecular form in a liquid aqueous phase, or which can be a colloidal suspension (e.g., in micelle form) in a liquid aqueous phase.

[0306] 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.

[0307] 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 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.

[0308] Additional organic UV shielding agents, specifically, - Cinnamic acid 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 methylenebisbenzotriazoltetramethylbutylphenol, - 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 You can choose from these.

[0309] Inorganic UV shielding agents are generally mineral-based UV shielding agents, and are particularly selected from metal oxides.

[0310] The metal oxides can be specifically selected from titanium oxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, and mixtures thereof.

[0311] The metal oxide particles may or may not be coated.

[0312] 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.

[0313] Metal oxides can be optionally doped.

[0314] In this regard, we can cite TiO2 particles doped with at least one transition metal, such as iron, zinc, or manganese, or more specifically, manganese.

[0315] 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 also mentioned. 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.

[0316] 2) Coloring agents According to a particular embodiment, the composition according to the present invention is 2) At least one coloring agent Includes.

[0317] Generally, the term "colorant" is intended 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.

[0318] Preferably, the composition according to the present invention comprises at least one pigment.

[0319] 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.

[0320] The pigments that can be used are specifically selected from organic and / or mineral pigments known in the art, specifically 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, "Pigments, Inorganic, 1. General," 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a20_243.pub3).

[0321] 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.

[0322] Pigments may also be mineral pigments. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's Encyclopedia. Among the mineral pigments useful in the present invention are iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, Prussian blue, and titanium dioxide.

[0323] The pigment can be an organic pigment.

[0324] The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's Encyclopedia.

[0325] 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.

[0326] Preferably, suitable pigments 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.

[0327] 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.

[0328] 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.

[0329] 3) Cosmetic surfactants According to a particular embodiment, the composition according to the present invention is 3) The product contains at least one cosmetic surfactant for caring for keratin substances, preferably for skin care. In particular, the cosmetic surfactant may be at least one hydrophilic surfactant and / or one lipophilic surfactant, preferably a hydrophilic surfactant.

[0330] The term "hydrophilic surfactant" refers to a water-soluble or water-dispersible surfactant that has the ability to form hydrogen bonds.

[0331] Examples of cosmetic surfactants3) 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 preventing 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.

[0332] 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 glycoside, diglyceryl glycoside, polyglyceryl glucoside, xylityl glycoside 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.

[0333] 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.

[0334] 4) Surfactants According to a particular embodiment, the composition according to the present invention is 4) At least one surfactant Includes.

[0335] 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.

[0336] 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.

[0337] 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.

[0338] 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.

[0339] Cationic surfactants include alkylimidazolidinium, for example isostearylethylimonium ethosulfate, ammonium salts, for example (C 12 ~C 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.

[0340] 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.

[0341] The thickener may be synthetic, natural, or of natural origin, preferably natural or of natural origin.

[0342] Such thickeners can be selected more specifically from natural polymers or polymers of natural origin, particularly those of plant origin.

[0343] These thickeners are preferably hydrophilic, i.e., soluble or dispersible in water.

[0344] Advantageously, thickeners include modified or natural polysaccharides, particularly modified or unmodified starches, fructans, geran, 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, gum arabic, and sucrose. The materials are selected from galactomannans and their nonionic derivatives, such as clerotium gum, tragacanth gum, ghati gum, karaya gum, locust bean gum, konjac gum, and guar gum, particularly hydroxypropyl guar and its ionic derivatives; biopolysaccharide gums derived from microorganisms, particularly scleroglucan or xanthan gum; mucopolysaccharides; carboxyvinyl polymers; polyacrylamides; optionally crosslinked and / or neutralized polymers and copolymers of 2-acrylamide-2-methylpropanesulfonic acid; water-soluble or water-dispersible silicone derivatives, such as silicone acrylates, polyether silicones, and cationic silicones; and mixtures thereof.

[0345] 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.

[0346] 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.

[0347] Needless to say, those skilled in the art will select these, or any optional additional compounds, and / or their quantities, 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 additions.

[0348] Needless to say, those skilled in the art will select these, or any optional additional compounds, and / or their quantities, with care such that the advantageous properties of the particles according to the present invention are not, or substantially, adversely affected by the intended additions.

[0349] As mentioned above, the composition according to the present invention may be for cosmetic use, and is preferably for cosmetic use.

[0350] 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.

[0351] Preferably, it is a medium that is acceptable as a cosmetic, that is, a medium that has a pleasant color, scent and feel, and does not produce any unacceptable discomfort, such as a stinging pain or tightness, that would cause the user to want to avoid applying the composition.

[0352] 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.

[0353] 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.

[0354] 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.

[0355] This composition can also be in an anhydrous form, for example, in the form of an oil.

[0356] 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, where this water is not added during the preparation of the composition but corresponds to residual water resulting from the mixed raw materials.

[0357] The cosmetic composition can be used, for example, as a makeup product.

[0358] Cosmetic compositions, for example, may be used as facial and / or body care and / or UV protection products, with a consistency ranging from liquid to semi-liquid, and may have the appearance of creams, ointments, milks, cream gels, lotions, serums, pastes, or foams, which are oily white or colored to varying degrees. Cosmetic compositions may optionally be applied to the skin in aerosol form. They may also be in solid form, such as a stick.

[0359] 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).

[0360] The composition can be applied by hand or using an applicator.

[0361] In particular, the cosmetic composition has an SPF of 5 or more, and preferably 10 or more.

[0362] For the purposes of this invention, the term "SPF" refers to the ultraviolet protection index, which 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).

[0363] 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)".

[0364] The term "UVAPF" refers to an index that characterizes protection from UVA irradiation. In particular, this index could be measured in vivo using the PPD (Persistent Immediate Darkening) method. "PPD" measures the skin color observed 2–4 hours after exposure to UVA light. This method has been adopted by the Japan Cosmetic Industry Association (JCIA) as the official test procedure for UVA 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). UVA 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.

[0365] 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 irradiation.

[0366] 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.

[0367] In yet another aspect thereof, the present invention also relates to non-therapeutic cosmetic uses of cosmetic compositions comprising at least one of the previously defined composite materials for preventing the appearance of darker and / or more intense colored traces that give uneven color to the skin, particularly the face, neck, arms, hands and / or shoulders.

[0368] 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.

[0369] 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.

[0370] 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.

[0371] In one aspect thereof, the present invention relates to a previously defined composite material for use as an agent for filtering UV irradiation, particularly UV-B irradiation. For the purposes of the present invention, the terms “prevent” or “prevent” mean at least partially reducing the risk of the occurrence of certain phenomena, such as signs of keratin aging, 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.

[0372] 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.

[0373] 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]

[0374] (Example 1) Preparation of bismuth oxycarbonate particles according to the present invention Bismuth oxycarbonate particles 1 and 2 are synthesized according to the preparation methods described in Examples 1.A and 1.B below.

[0375] 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.

[0376] 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 (CASchneider, WS Rasband, KWEliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat. Methods.9 (2012) pp. 671-675).

[0377] (Example 1.A) Synthesis of bismuth oxycarbonate particles 1 A solution of bismuth nitrate pentahydrate Bi(NO3)3·5H2O (0.40 M) and D-mannitol (2 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. After 30 minutes, this mixture is then transferred to a Teflon autoclave and heated at 150°C for 12 hours. Bismuth oxycarbonate particles 1 are isolated by centrifugation, washed three times with water, and then oven-dried at 60°C.

[0378] Bismuth oxycarbonate particles 1 are small plates having the following average dimensions: Average length L: 85nm Average width l: 52nm Average thickness e: 28nm

[0379] (Example 1.B) Synthesis of bismuth oxycarbonate particles 2 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 2 is isolated by centrifugation, washed three times with water, and then oven-dried at 60°C.

[0380] Bismuth oxycarbonate particles 2 are small plates with the following average dimensions: Average length L: 86nm Average width l: 53nm Average thickness e: 28nm

[0381] (Example 2) Synthesis of composite materials according to the present invention (Example 2.A) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material A In Example 1, the bismuth oxycarbonate particles from A were stirred in 100 g / L of water at room temperature for 45 minutes. The temperature of the medium was then raised to 70°C. A 0.5 M aqueous sodium aluminate solution was added dropwise in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate was equal to 0.065. After the addition was complete, the reaction medium was stirred at 70°C for 1 hour. The pH was adjusted to 8 by adding sulfuric acid. An aqueous sodium stearate solution heated to 80°C was added dropwise to the reaction medium at a concentration of 30 g / L in an amount such that the molar ratio of sodium stearate to bismuth oxycarbonate was equal to 0.1. The mixture was stirred at 70°C for 1 hour. The pH was adjusted to 6.5 using sulfuric acid. After cooling, composite material A was isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0382] Composite material A is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0383] (Example 2.B) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material B In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature for 45 minutes. The temperature of the medium is then raised to 70°C. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate is equal to 0.065. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. A sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount such that the molar ratio of sodium stearate to bismuth oxycarbonate is equal to 0.3. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material B is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0384] Composite material B is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0385] (Example 2.C) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material C In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature for 45 minutes. The temperature of the medium is then raised to 70°C. The pH is adjusted to 8 using sodium hydroxide. Next, a 0.5 M aqueous sodium aluminate solution is added dropwise in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate is equal to 0.065. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. An aqueous sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount such that the molar ratio of sodium stearate to bismuth oxycarbonate is equal to 0.1. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material C is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0386] Composite material C is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0387] (Example 2.D) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material D In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature for 45 minutes. The temperature of the medium is then raised to 70°C. The pH is adjusted to 8 using sodium hydroxide. Next, a 0.5 M aqueous sodium aluminate solution is added dropwise in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate is equal to 0.065. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. An aqueous sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount such that the molar ratio of sodium stearate to bismuth oxycarbonate is equal to 0.3. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material D is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0388] Composite material D is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0389] (Example 2.E) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material E In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature for 45 minutes. The temperature of the medium is then raised to 70°C. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate is equal to 0.13. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. A sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount such that the molar ratio of sodium stearate to bismuth oxycarbonate is equal to 0.1. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material E is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0390] Composite material E was obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0391] (Example 2.F) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material F The bismuth oxycarbonate particles from Example 1.A are stirred in water at a concentration of 100 g / L at room temperature for 45 minutes. Then the temperature of the medium is raised to 70°C. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.13 for the sodium aluminate / bismuth oxycarbonate molar ratio.

[0392] Once the addition is complete, stir the reaction medium at 70°C for 1 hour. Adjust the pH to 8 by adding sulfuric acid. Add 30 g / L of aqueous sodium stearate solution heated to 80°C to the reaction medium in an amount equal to 0.3 of sodium stearate / bismuth oxycarbonate. Stir the mixture at 70°C for 1 hour. Adjust the pH to 6.5 using sulfuric acid. After cooling, isolate composite material F by centrifugation, wash three times with water, and then oven dry at 50°C.

[0393] Composite material F is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0394] (Example 2.G) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material G Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 1 hour. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.13 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. A sodium stearate aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount equal to 0.1 for the sodium stearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material G is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0395] Composite material G is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0396] (Example 2.H) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material H In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.13 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. A sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount equal to 0.1 for the sodium stearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material H is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0397] Composite material H is obtained in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0398] (Example 2.I) Synthesis of Bismuth Oxycarbonate-Aluminum Hydroxide-Sodium Stearate Composite Material I Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.13 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. An aqueous sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount equal to 0.3 for the sodium stearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material I is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0399] Composite material I is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0400] (Example 2.J) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material J In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.33 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. An aqueous sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount equal to 0.1 for the sodium stearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material J is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0401] Composite material J is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0402] (Example 2.K) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material K Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.33 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. A sodium stearate aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount equal to 0.3 for the sodium stearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material K is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0403] Composite material K was obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0404] (Example 2.L) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material L Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.33 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. An aqueous sodium stearate solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount equal to 0.1 for the sodium stearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material L is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0405] The composite material L is obtained in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0406] (Example 2.M) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium stearate composite material M In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.33 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. A sodium stearate aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount equal to 0.3 for the sodium stearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material M is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0407] The composite material M is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0408] (Example 2.N) Synthesis of bismuth oxycarbonate-sodium stearate composite material N Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A sodium stearate aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L, such that the molar ratio of sodium stearate to bismuth oxycarbonate is equal to 0.1. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material N is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0409] Composite material N was obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0410] (Example 2.0) Synthesis of bismuth oxycarbonate-sodium stearate composite material O Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A sodium stearate aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L, such that the molar ratio of sodium stearate to bismuth oxycarbonate is equal to 0.3. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material O is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0411] The composite material O was obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0412] (Example 2.P) Synthesis of bismuth oxycarbonate-oleic acid composite material P Bismuth oxycarbonate particles according to Example 1.A are stirred in 100 g / L of water at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. An aqueous oleic acid solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L, in an amount such that the molar ratio of oleic acid to bismuth oxycarbonate is equal to 0.3. The pH of the reaction medium is adjusted to remain within the range of 7.5 to 9 using sodium hydroxide solution as usual, and then adjusted to a pH equal to 10 at the end of the addition. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material P is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0413] The composite material P is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0414] (Example 2.Q) Synthesis of Bismuth Oxycarbonate-Monosodium Lauroyl Glutamate Composite Material Q Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A 30 g / L aqueous solution of monosodium lauroyl glutamate heated to 80°C is added dropwise to the reaction medium in an amount equal to 0.3, such that the molar ratio of monosodium lauroyl glutamate to bismuth oxycarbonate is equal to 0.3. The pH of the reaction medium is adjusted to remain within the range of 7.5 to 9 using sodium hydroxide solution as usual, and then adjusted to a pH equal to 10 at the end of the addition. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material Q is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0415] The composite material Q is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0416] (Example 2.R) Synthesis of bismuth oxycarbonate-caprylic acid composite material R Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using a sodium hydroxide solution. A caprylic acid aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L, in an amount such that the molar ratio of caprylic acid to bismuth oxycarbonate is equal to 0.3. The pH of the reaction medium is adjusted to 9.7 by adding 2N NaOH dropwise to the reaction medium. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, the composite material R is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0417] The composite material R is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0418] (Example 2.S) Synthesis of bismuth oxycarbonate-capryloyl salicylic acid composite material S Bismuth oxycarbonate particles according to Example 1.A are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using a sodium hydroxide solution. A capryloyl salicylic acid aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L, in an amount such that the molar ratio of capryloyl salicylic acid to bismuth oxycarbonate is equal to 0.3. The pH of the reaction medium is adjusted to 9.7 by adding 2N NaOH dropwise to the reaction medium. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material S is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0419] The composite material S is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0420] (Example 2.T) Synthesis of bismuth oxycarbonate-3-[2-(2-methoxyethoxy)ethoxy]propanoic acid composite material T The bismuth oxycarbonate particles from Example 1.A were stirred in 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 a sodium hydroxide solution.

[0421] An aqueous solution of 3-[2-(2-methoxyethoxy)ethoxy]propanoic acid heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L, in an amount such that the molar ratio of 3-[2-(2-methoxyethoxy)ethoxy]propanoic acid to bismuth oxycarbonate is equal to 0.3. The pH of the reaction medium is adjusted to 9.7 by adding 2N NaOH dropwise to the reaction medium. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, the composite material T is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0422] The composite material T is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0423] (Example 2.U) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium oleate composite material U In Example 1.A, bismuth oxycarbonate particles are stirred in water at a concentration of 100 g / L at room temperature. The temperature of the medium is then maintained at 70°C for 30 minutes. The pH is adjusted to 8 using a sodium hydroxide solution. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate is equal to 0.065. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. An aqueous oleic acid solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L in an amount such that the molar ratio of oleic acid to bismuth oxycarbonate is equal to 0.3. The pH of the reaction medium is adjusted to 9.7 by adding 2N NaOH dropwise to the reaction medium. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material U is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0424] The composite material U was obtained in the form of a viscous white paste and characterized by a UV / Vis spectrophotometer.

[0425] (Example 2.V) Synthesis of Bismuth Oxycarbonate-Silica-Sodium Stearate Composite Material V Bismuth oxycarbonate particles from Example 1.B are stirred in 40 mL of distilled water. The temperature of the medium is raised to 80°C while stirring. At this temperature, 3.32 mL of 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 cooled to room temperature. Product X, 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.

[0426] Product X was isolated in the form of a white powder and characterized by UV / Vis spectrophotometrics and Fourier transform infrared spectroscopy.

[0427] Next, product X is stirred in water at a concentration of 100 g / L at room temperature. Then, the temperature of the medium is maintained at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide solution. A sodium stearate aqueous solution heated to 80°C is added dropwise to the reaction medium at a concentration of 30 g / L, in an amount such that the molar ratio of sodium stearate to bismuth silica oxycarbonate is equal to 0.3. The reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, the composite material V is isolated by centrifugation, washed three times with water, and then oven-dried at 50°C.

[0428] Composite material V is obtained in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0429] (Example 2.Y) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium isostearate composite material Y The bismuth oxycarbonate particles obtained in Example 1.A are dispersed in water at a concentration of 100 g / L and heated at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.065 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. In parallel, isostearic acid [CAS# 54680-48-7] is stirred in water at a concentration of 30 g / L and heated at 80°C. The pH is adjusted to 10 using sodium hydroxide, and this solution is added dropwise to the reaction medium in an amount equal to 0.3 for the sodium isostearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material Y is isolated by centrifugation, washed twice with water, and then oven-dried at 50°C.

[0430] Composite material Y is obtained as a white powder and characterized by UV / Vis spectrophotometric analysis.

[0431] (Example 2.Z) Synthesis of bismuth oxycarbonate-sodium isostearate composite material Z The bismuth oxycarbonate particles obtained in Example 1.A were dispersed in water at a concentration of 100 g / L and heated at 70°C for 30 minutes. The pH was adjusted to 8 using sodium hydroxide. In parallel, isostearic acid [CAS# 30399-84-9] was stirred in water at a concentration of 30 g / L and heated to 80°C. The pH was adjusted to 10 using sodium hydroxide, and this solution was added dropwise to the reaction medium in an amount equal to 0.3 for the molar ratio of sodium isostearate to bismuth oxycarbonate. The mixture was stirred at 70°C for 1 hour. The pH was adjusted to 6.5 using sulfuric acid. After cooling, composite material Z was isolated by centrifugation, washed twice with water, and then oven-dried at 50°C.

[0432] Composite material Z was obtained as a white viscous paste and characterized by UV / Vis spectrophotometric analysis.

[0433] (Example 2.AA) Synthesis of bismuth oxycarbonate-aluminum hydroxide-sodium isostearate composite material AA In Example 1.A, the bismuth oxycarbonate particles obtained were dispersed in water at a concentration of 100 g / L and heated at 70°C for 30 minutes. The pH was adjusted to 8 using sodium hydroxide. A 0.5 M aqueous sodium aluminate solution was added dropwise in an amount such that the molar ratio of sodium aluminate to bismuth oxycarbonate was equal to 0.065. After the addition was complete, the reaction medium was stirred at 70°C for 1 hour. The pH was adjusted to 8 by adding sulfuric acid. In parallel, isostearic acid [CAS# 30399-84-9] was stirred in water at a concentration of 30 g / L and heated at 80°C. The pH was adjusted to 10 using sodium hydroxide, and this solution was added dropwise to the reaction medium in an amount such that the molar ratio of sodium isostearate to bismuth oxycarbonate was equal to 0.3. The mixture was stirred at 70°C for 1 hour. The pH was adjusted to 6.5 using sulfuric acid. After cooling, composite material AA is isolated by centrifugation, washed twice with water, and then oven-dried at 50°C.

[0434] Composite material AA was obtained in the form of a white viscous paste and characterized by UV / Vis spectrophotometry.

[0435] (Example 2.AB) Synthesis of bismuth oxycarbonate-titanium dioxide-sodium stearate composite material AB Disperse 2g of bismuth oxycarbonate particles (2) according to Example 1.B in 190mL of 2-propanol. Add 2.5mL of sodium hydroxide aqueous solution (5 × 10⁻⁶). -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. Isolate the composite material AC by centrifugation, wash it twice with ethanol, and dry it under vacuum (P < 100 mbar) at 60°C.

[0436] Product AC is dispersed in water at a concentration of 100 g / L and heated at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. In parallel, a sodium stearate solution is stirred in water at a concentration of 30 g / L and heated to 80°C. This solution is added dropwise to the reaction medium in an amount equal to 0.3 for the molar ratio of sodium stearate to bismuth oxycarbonate. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, composite material AB is isolated by centrifugation, washed twice with water, and then dried in an oven at 50°C.

[0437] The composite material AB is obtained as a white powder and characterized by UV / Vis spectrophotometric analysis.

[0438] (Example 2.AD) Synthesis of bismuth oxycarbonate-zinc oxide-sodium stearate composite material AD 1 g of bismuth oxycarbonate particles according to Example 1.B 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. Next, the resulting medium is 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 under vacuum at 50°C for 1 hour. Next, 500 mg of the dried solid is placed in an alumina crucible and heated in a muffle furnace for 1 hour to a maximum of 200°C (heating rate 10°C / min). After cooling to room temperature, the intermediate material AE, bismuth oxycarbonate-zinc oxide, is obtained as a whitish powder.

[0439] Product AE is dispersed in water at a concentration of 100 g / L and heated at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. In parallel, a sodium stearate solution is stirred in water at a concentration of 30 g / L and heated to 80°C. This solution is added dropwise to the reaction medium in an amount equal to 0.3 for the molar ratio of sodium stearate to bismuth oxycarbonate. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, the composite material AD is isolated by centrifugation, washed twice with water, and then oven-dried at 50°C.

[0440] The composite material AD was obtained as a white powder and characterized by UV / Vis spectrophotometric analysis.

[0441] (Example 2.AF) Synthesis of Bismuth Oxycarbonate-Aluminum Hydroxide-3-[2-(2-Methoxyethoxy)ethoxy]propanoic Acid Composite Material AF The bismuth oxycarbonate particles obtained according to Example 1.A are dispersed in water at a concentration of 100 g / L and heated at 70°C for 30 minutes. The pH is adjusted to 8 using sodium hydroxide. A 0.5 M aqueous sodium aluminate solution is added dropwise in an amount equal to 0.065 for the sodium aluminate / bismuth oxycarbonate molar ratio. After the addition is complete, the reaction medium is stirred at 70°C for 1 hour. The pH is adjusted to 8 by adding sulfuric acid. In parallel, 3-[2-(2-methoxyethoxy)ethoxy]propanoic acid is stirred in water at a concentration of 30 g / L and heated at 80°C. The pH is adjusted to 10 using sodium hydroxide, and this solution is added dropwise to the reaction medium in an amount equal to 0.3 for the sodium isostearate / bismuth oxycarbonate molar ratio. The mixture is stirred at 70°C for 1 hour. The pH is adjusted to 6.5 using sulfuric acid. After cooling, the composite material AF is isolated by centrifugation, washed twice with water, and then oven-dried at 50°C.

[0442] The composite material AF is obtained as a white powder and characterized by UV / Vis spectrophotometric analysis.

[0443] (Example 3) Absorption spectrum of the bismuth oxycarbonate composite material according to the present invention According to the present invention, the absorption spectrum of the composite material prepared according to Example 2 was generated using UV-Vis spectrophotometric analysis.

[0444] The absorption spectrum was obtained by UV-Vis spectrophotometric spectroscopy using a 0.005 mass% dispersion of the complex in isododecane.

[0445] The quartz cell used for absorbance measurement has a side length of 1 cm. The spectrophotometer used is a Thermo Fischer Scientific Genesys 10S.

[0446] Dispersions of composite materials A-V and Y-AF, which consist of bismuth oxycarbonate and organic compounds containing carboxyl groups, are sonicated at 0.05% by mass for 1 minute, then stirred with a magnetic stirrer for 10 minutes. They are then sonicated again for 1 minute, diluted to 0.005% by mass, sonicated again, and stirred again with a magnetic stirrer for 5 hours. Immediately before absorbance measurement, the sample is sonicated for 1 minute.

[0447] 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.

[0448] The absorption spectra are shown in Figures 1 to 28.

[0449] The results are listed in order in Table 1 below.

[0450] [Table 1]

[0451] The composite material according to the present invention exhibits good absorption of UV light and, as a result, efficient shielding of UV light.

[0452] 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.

[0453] (Example 4) Absorption spectra of composite material D from Example 2.D and composite material O from Example 2.O in various solvents The UV-visible absorbance spectra of composite material D according to Example 2.D and composite material O according to Example 2.O are measured in various solvents i). The measurements are performed using a dispersion of composite material D or composite material O at a concentration of 0.005% by mass in solvent i).

[0454] Preparation of dispersions of composite material D and composite material O The composite material D or O synthesized according to Example 2.D or 2.O, respectively, is added to solvent i) at a concentration of 0.1% by mass.

[0455] 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.

[0456] The resulting dispersions are referred to as Dn and On in Table 2 below.

[0457] [Table 2]

[0458] Each of the dispersions D1, O1, and O2 prepared according to the protocol described above is diluted by adding an additional solvent i) to reach a final concentration of composite material D or O of 0.005% by mass, and then subjected to magnetic stirring at 600 rpm for 20 minutes before performing absorbance measurement.

[0459] 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).

[0460] If the measured UV absorbance value exceeds a predetermined threshold, the filtering of UV light is considered efficient. In particular, when composite materials D and O from Examples 2.D and 2.O are dispersed in solvent i) at a concentration of 0.005% by mass, UV light is considered to be efficiently filtered if the maximum absorbance measured in the UV range exceeds 0.25.

[0461] The absorption spectra of dispersions D1, O1, and O2 are shown in Figures 29 to 31.

[0462] The absorbance values ​​are reported in Table 3 below.

[0463] [Table 3]

[0464] The dispersions D1, O1, and O2 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.

[0465] The absorbance values ​​also indicate that the dispersions D1, O1, and O2 according to the present invention have high transparency in the visible range between 400 nm and 780 nm.

[0466] (Example 5) Preparation of compositions D2, D3, D4, D5, D6, D7, O3, O4, O5, O6, O7, O8, and O9 according to the present invention A solution of the polymer or surfactant (ii) is prepared by stirring in solvent (i) at a concentration of 1% by mass until completely dissolved. Then, it is further diluted with additional solvent (i) to a concentration of 0.1% by mass.

[0467] During the polymer or surfactant solution preparation steps for compositions D2, D5, O3, and O5, polyhydroxystearic acid was heated to 50°C prior to its introduction at the desired concentration in water.

[0468] Composite material D synthesized according to Example 2.D, or composite material O synthesized according to Example 2.O, is added to a polymer or surfactant solution ii) diluted with solvent i) at a concentration of 0.1% by mass.

[0469] 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.

[0470] The compositions obtained as dispersions are referred to as Dn and On in Table 4 below.

[0471] [Table 4]

[0472] (Example 6) Absorption spectra of compositions D2, D3, D4, D5, D6, D7, O3, O4, O5, O6, O7, O8, and O9 according to the present invention Each of the compositions D2-D7 and O3-O9 according to Example 5 was diluted by adding solvent i) so that the final concentration of composite material D or O reached 0.005% by mass, and then subjected to magnetic stirring at 600 rpm for 20 minutes before performing absorbance measurement.

[0473] 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).

[0474] If the measured UV absorbance value exceeds a predetermined threshold, the filtering of UV light is considered efficient. In particular, compositions containing 0.005% by mass of composite material D according to Example 2.D, or composite material O according to Example 2.O, are considered to efficiently filter UV light if their maximum absorbance in the UV range exceeds 0.25.

[0475] The absorbance values ​​obtained for compositions D2, D3, D4, D5, D6, D7, O3, O4, O5, O6, O7, O8, and O9 according to the present invention are reported in Table 5 below.

[0476] [Table 5]

[0477] (Example 7) Preparation of aqueous compositions D8, O10, and O11 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.

[0478] During the preparation of the surfactant solutions for compositions D8 and O10, lauryl glucoside (Plantacare 1200UP, aqueous solution from BASF) was heated at 50°C until a homogeneous solution was obtained, and then introduced into water at a concentration of 1% by mass.

[0479] During the preparation step of the surfactant solution for composition O11, 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 O as described below herein.

[0480] Composite material D synthesized according to Example 2.D, or composite material O synthesized according to Example 2.O, is added to a surfactant solution ii) diluted in water at a concentration of 0.1% by mass.

[0481] 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.

[0482] The compositions obtained as dispersions are referred to as Dn and On in Table 6 below.

[0483] [Table 6]

[0484] (Example 8) Absorption spectra of aqueous compositions D8, O10, and O11 according to the present invention Each of the compositions D8, O10, and O11 according to Example 7 was diluted by adding deionized water so that the final concentration of composite material D or O reached 0.005% by mass, and then subjected to magnetic stirring at 600 rpm for 20 minutes before performing absorbance measurement.

[0485] 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.

[0486] If the measured UV absorbance exceeds a predetermined threshold, the filtering of UV light is considered efficient. In particular, compositions containing 0.005% by mass of composite material D according to Example 2.D, or composite material O according to Example 2.O, are considered to efficiently filter UV light if their maximum absorbance in the UV range exceeds 0.25.

[0487] The absorbance spectra of aqueous compositions D8, O10, and O11 according to the present invention are shown in Figures 32 to 34.

[0488] The absorbance values ​​are reported in Table 7.

[0489] [Table 7]

[0490] The aqueous compositions D8, O10, and O11 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.

[0491] The absorption spectra also show that compositions D8, O10, and O11 according to the present invention have high transparency in the visible range between 400 and 780 nm.

Claims

1. a) Empirical formula (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 the particles is less than 400 nm, particles and b) At least one organic compound containing a carboxyl group and / or a salt thereof 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 of the composite material, which is in the range of 0.005 μm to 10 μm, preferably 0.01 μm to 1 μm.

3. The composite material according to claim 1 or 2, comprising the bismuth oxycarbonate particles a) and one or more inorganic compounds c) other than the solvates thereof, for example, the hydrate thereof, preferably inorganic oxides, more preferably selected from zinc oxide, titanium oxide, silicon oxide and / or aluminum oxide, preferably silicon oxide and / or aluminum oxide, and optionally hydrated.

4. - At least the empirical formula (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), bismuth oxycarbonate particles a), and solvates thereof, for example particles of its hydrate, wherein the maximum average dimension of said particles is less than 400 nm, and a core - A layer surrounding the core, either continuously or discontinuously, comprising b) at least one organic compound containing a carboxyl group and / or one of its salts, A composite material according to any one of claims 1 to 3, comprising:

5. - At least the empirical formula (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), bismuth oxycarbonate a), and its solvates, for example, particles of its hydrate, and a core containing particles having a maximum average dimension of less than 400 nm - An inner layer adjacent to the core, comprising the bismuth oxycarbonate particles a) and at least one inorganic compound c) different therefrom, such as its solvate, - An outer layer adjacent to the inner layer, comprising at least one organic compound containing a carboxyl group and / or one of its salts. 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 one or more organic compounds and / or salts thereof containing the carboxyl group are selected from fatty acids, preferably linear or branched fatty acids having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms.

12. The composite material according to any one of claims 1 to 11, wherein one or more organic compounds containing the carboxyl group and / or one of their salts is selected from stearic acid, oleic acid, lauroyl glutamic acid, capryloyl salicylic acid, 3-[2-(2-methoxyethoxy)ethoxy]propanoic acid, or one of their salts, and mixtures thereof.

13. One or more of the organic compounds b) containing a carboxyl group and / or a salt thereof, with the empirical formula (BiO) 2-x (CO 3 )(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, directly on the surface of the particles a), or with the empirical formula (BiO) 2-x (CO 3 (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, particles a), and a step of chemically grafting or physically adsorbing onto the surface of particles containing an inorganic compound c) different from the bismuth oxycarbonate particles a) and its solvates, such as its hydrates, a method for preparing the composite material according to any one of claims 1 to 12.

14. A method for preparing a composite material according to any one of claims 1 to 12, (i) Empirical formula (BiO) 2-x (CO 3 )(where -0.4 < x < 0.6), bismuth oxycarbonate and its solvates, such as its hydrate 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 in the range of 0.05 g / L to 500 g / L (ii) A step of preparing a solution of at least one organic compound b) containing a carboxyl group and / or a salt thereof as a mixture with at least one solvent, in an amount particularly in the range of 0.05 g / L to 500 g / L. (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 Methods that include...

15. The preparation method according to claim 14, wherein the solvents in steps (i) and (ii) are the same or different, preferably selected from protic polar solvents, more preferably from water, alcohol, polyol and mixtures thereof, and even more preferably the solvent is water.

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 the composition according to any one of claims 1 to 12 to a keratinous substance, particularly the composition according to any one of claims 16 to 18.

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, particularly the composition according to any one of claims 16 to 18, to a keratinous substance.

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