Bismuth oxycarbonate and polymer composite material for filtering ultraviolet irradiation

Abstract

The present invention relates to a composite material, wherein the following formula (I):(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 more to a composite material of bismuth oxycarbonate and a polymer for use in filtering ultraviolet irradiation.

[0002] The present invention also relates to compositions, particularly cosmetic compositions, and especially compositions comprising a composite material of bismuth oxycarbonate particles and a polymer, particularly cosmetic compositions.

[0003] Keratin is exposed to sunlight every day.

[0004] It is known that light exposure with wavelengths of 280 nm to 400 nm causes browning of the human epidermis. However, light with wavelengths of 280 to 320 nm (referred to as UV-B rays) is detrimental to the formation of a natural tan. This exposure can also induce a decline in the biomechanical properties of the epidermis, which manifests as the appearance of wrinkles and leads to premature skin aging.

[0005] Furthermore, UV-A rays, which have wavelengths of 320-400 nm, are known to penetrate deeper into the skin than UV-B rays. UV-A rays promote rapid and persistent pigmentation of the skin. Under normal conditions, even short periods of daily exposure to UV-A rays can also cause damage to collagen and elastin fibers, which manifests as alterations to the skin's microstructure, the appearance of wrinkles, and uneven pigmentation (i.e., liver spots, uneven skin tone, etc.).

[0006] Furthermore, prolonged exposure to sunlight dries out and weakens hair.

[0007] Therefore, protecting keratinous substances, especially human keratinous substances such as skin, is of paramount importance. [Background technology]

[0008] To counteract these undesirable effects, it is common practice to incorporate organic and / or inorganic anti-UV-A screening agents and / or anti-UV-B screening agents into compositions intended to provide sun protection.

[0009] Many photoprotective cosmetic compositions for the skin have been proposed to date. They generally contain organic UV-screening agents and / or inorganic UV-screening agents, which act by absorbing, reflecting, or scattering UV radiation according to their own chemical properties and physical properties. They generally include oil-soluble organic UV-screening agents and / or water-soluble organic UV-screening agents combined with metal oxide dyes, such as titanium dioxide (TiO2) or zinc oxide (ZnO).

[0010] Conventional organic shading agents must possess acceptable cosmetic properties, good solubility in conventional solvents, particularly oils, and good photostability both alone and in combination. They must also be colorless or have a cosmetically acceptable tint to consumers. These organic shading agents are commonly used as mixtures, and such combinations of shading agents may limit the range of formulations.

[0011] In addition, the use of inorganic UV-screening agents for sun protection is now a very important consumer expectation, leading consumers to consider mineral sunscreens safer.

[0012] TiO2 and ZnO are the most commonly used mineral UV-screening agents.

[0013] However, one of the main drawbacks of such mineral light-blocking agents is that, when applied to the skin, they cause a whitening effect, which is undesirable as a cosmetic and generally not well-liked by users.

[0014] This effect becomes even more pronounced when the concentration of mineral shielding agents in the composition is high, which limits their concentration in sunscreen formulations.

[0015] While it is certainly possible to use reduced amounts of one or more mineral shielding agents to circumvent this problem, the resulting composition, although producing a film with acceptable transparency on the skin, no longer provides adequate protection in the UV region, thus greatly limiting the usefulness of such an option.

[0016] Furthermore, in addition to significant whitening, the use of large quantities of these UV-blocking agents can cause discomfort after application to the skin, particularly roughness and dryness when the product is used in large quantities and regularly.

[0017] Consumers are increasingly seeking products that are effective, very easy to administer, comfortable for extended periods, and possess satisfying sensory characteristics. [Overview of the Initiative] [Problems that the invention aims to solve]

[0018] Therefore, there remains a need for inorganic UV-screening agents that provide efficient light protection without the drawbacks mentioned above.

[0019] In particular, there remains a demand for inorganic UV-screening agents that efficiently block UV rays, especially UV-A and UV-B rays, while having high transmittance to visible light, not causing whitening of applied keratin materials, and possessing good cosmetic properties.

[0020] In particular, there remains a need for mineral UV-screening agents other than titanium dioxide or zinc oxide, which must exhibit comparable effectiveness, be transparent, cause a rough and dry feeling on the skin, and be easy to formulate, especially at high concentrations.

[0021] This invention is particularly directed towards proposing novel mineral UV-screening agents that can meet these expectations. [Means for solving the problem]

[0022] Therefore, according to a first aspect of the present invention, the present invention is a composite material, a) The following equation (I) (BiO) 2-x (CO3), -0.4 <x<0.6である、 At least one particle of bismuth oxycarbonate and its solvate, for example, its hydrate. Here, the maximum average dimension of the particles is less than 400 nm; and, b) At least one polymer This relates to the above-mentioned composite materials, including the above-mentioned materials.

[0023] Preferably, the present invention is applied using a composite material, a) The following equation (I) (BiO) 2-x (CO3), -0.4 <x<0.6である、 At least one particle of bismuth oxycarbonate and its solvate, for example, its hydrate. Here, the maximum average dimension of the particles is less than 400 nm; and, b) At least one polymer selected from polyethylene glycol, polyethyleneamine, polypropylene glycol, polyvinyl alcohol, polyacrylic acid and its salts, polymethacrylic acid and its salts, polymethyl methacrylate, polyvinyl sulfonate, polystyrene sulfonate, polylactic acid and its salts, polycaprolactone, polyglycolic acid, polyacetate, poly(lactic acid-coglycolic acid), cellulose and its derivatives, alginic acid and its salts, carrageenan, starch, pectin, inulin, dextran and its derivatives, xanthan gum, urban, lignosulfonate and its salts, chitin and chitosan, pullulan, polyvinyl alcohol and polyhydroxystearic acid, and / or copolymers thereof, or combinations thereof. This relates to the above-mentioned composite materials, including the above-mentioned materials.

[0024] Preferably, the present invention relates to a composite material, a) The following equation (I) (BiO) 2-x (CO3), -0.4 <x<0.6である、 At least one particle of bismuth oxycarbonate and its solvate, for example, its hydrate. Here, the maximum average dimension of the particles is less than 400 nm; and, b) At least one polymer selected from natural hydrophilic and / or lipophilic and / or amphiphilic and anionic and / or cationic and / or neutral polysaccharides, preferably selected from natural hydrophilic anionic and / or cationic and / or neutral polysaccharides, more preferably selected from neutral or anionic polysaccharides, more preferably selected from carrageenan, chitosan, dextran sulfate, (d)starch phosphate, pullulan and their carboxylic acids, preferably carboxylic acids containing 1 to 30 carbon atoms, more preferably 8 to 20 carbon atoms, in an esterified (or acetylated) form, such as myristoyl pullulan and urban. This relates to the above-mentioned composite materials, including the above-mentioned materials.

[0025] In particular, the bismuth oxycarbonate particles are of the following formula (BiO)2(CO3), and their solvates, such as their hydrates.

[0026] Combinations of bismuth oxide with polymers, such as alginates, chitosan, and polyvinyl alcohol, have already been proposed in various fields other than sun protection of keratin materials, such as radiopaqueness for embolization (US. 8012454, European Patent No. EP1531874, US. 7947073), medical devices (US. 6387978), and suppression of hyperacidity (US. 3257275, US. 6024987A). However, these documents do not mention anything about UV shielding, nor do they describe composite materials containing bismuth oxide according to the present invention.

[0027] Preferably, the mass ratio of one or more bismuth oxycarbonate particles to polymer b) is in the range of 0.01 to 50, preferably 0.2 to 15, more preferably 0.3 to 10, and more preferably 0.5 to 8.5.

[0028] Preferably, the average size of the maximum dimensions of the composite material particles according to the present invention is 1 μm or less, more preferably 500 nm or less, and even more preferably 450 nm or less.

[0029] In particular, the bismuth oxycarbonate particles are tubular, plate-shaped and / or rod-shaped, preferably plate-shaped and / or rod-shaped.

[0030] Preferably, the one or more polymers b) are selected from polyethylene glycol, polyethyleneamine, polypropylene glycol, polyvinyl alcohol, polyacrylic acid and its salts, polymethacrylic acid and its salts, polymethyl methacrylate, polyvinyl sulfonate, polystyrene sulfonate, polylactic acid and its salts, polycaprolactone, polyglycolic acid, polyacetate, poly(lactic acid-coglycolic acid), cellulose and its derivatives, alginic acid and its salts, carrageenan, starch, pectin, inulin, dextran and its derivatives, xanthan gum, urban, lignosulfonate and its salts, chitin and chitosan, pullulan, polyvinyl alcohol and polyhydroxystearic acid, and / or copolymers thereof, or combinations thereof.

[0031] In particular, the one or more polymers b) are selected from sodium lignosulfonate, calcium lignosulfonate, polyanethol sulfonate, sodium alginate, carboxymethylcellulose, hydroxyethylcellulose, dextran sulfate salt, carrageenan, chitosan, myristoyl pullulan, polyvinyl alcohol, and / or copolymers thereof, or combinations thereof. More particularly, the molar ratio of the number of moles of one or more coating compounds to the number of moles of one or more core compounds is in the range of 0.0001 to 20, preferably in the range of 0.005 to 15, more preferably in the range of 0.01 to 10, and even more preferably in the range of 0.05 to 5.

[0032] Surprisingly, as will be evident from the following examples, the inventors have discovered that composite materials according to the present invention have excellent efficacy in filtering ultraviolet irradiation, particularly UV-B rays, and high transparency in the visible range, thereby giving compositions containing them cosmetic properties that satisfy consumers.

[0033] In the present invention, the term “composite material” means a heterogeneous particulate solid material comprising at least two immiscible components, wherein the components are bonded together through physical and / or chemical interactions.

[0034] In the present invention, the term "high transparency in the visible range" means particles that have transmittance to light rays of 400 to 780 nm.

[0035] In the present invention, the term "efficiency for filtering ultraviolet irradiation" means particles having a threshold absorbance in the UV range of greater than 0.25, preferably 0.30 or higher, and more preferably 0.35 or higher, in a dispersion medium containing the particles at a mass fraction of 0.005%. The higher the threshold absorbance, the higher the efficiency for filtering UV irradiation.

[0036] UV-B irradiation refers to the wavelength range of 280-320 nm. UV-A radiation refers to the wavelength range of 320-400 nm. Visible light refers to the wavelength range of 400-780 nm.

[0037] Therefore, in the present invention, the term "UV shielding agent" is intended to refer to any compound that screens ultraviolet (UV) radiation in the wavelength range of 280 nm to 400 nm. Furthermore, the term "UV-B shielding agent" is intended to refer to any compound that screens ultraviolet (UV) radiation in the wavelength range of 280 nm to 320 nm. The term "UV-A shielding agent" is intended to refer to any compound that screens ultraviolet (UV) radiation in the wavelength range of 320 nm to 400 nm.

[0038] In the present invention, the term "fatty substance" means an organic compound that is immiscible with water at room temperature (25°C) and atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1%, and more preferably less than 0.1%). In addition, the fatty substance is miscible in any proportion in organic solvents, such as halogenated solvents, chloroform or dichloromethane, lower alcohols, such as ethanol, or aromatic solvents, such as benzene or toluene, under the same temperature and pressure conditions.

[0039] The terms "organic salt or inorganic salt" more preferably refer to: i) hydrochloric acid: HCl, ii) hydrobromic acid: HBr, iii) sulfuric acid: H2SO4; iv) alkyl sulfonic acid: Alk-S(O)2OH (e.g., methanesulfonic acid and ethanesulfonic acid), v) aryl sulfonic acid: Ar-S(O)2OH (e.g., benzenesulfonic acid and toluenesulfonic acid), vi) citric acid, vii) succinic acid, viiii) tartaric acid, ix) lactic acid, x) alkoxysulfinic acid: Alk-OS(O)OH (e.g., methoxysulfinic acid and ethoxysulfinic acid), xi) aryloxysulfinic acid: tolueneoxysulfinic acid and phenoxysulfinic acid, xii) phosphoric acid: H3PO 4; xiii) Acetic acid: CH3C(O)OH; xiv) Trifluoroacetic acid: CF3SO3H; and xv) Tetrafluoroboric acid: HBF4, as well as salts derived from these, and "acidic" amino acids, such as glutamates and aspartates.

[0040] The term “organic base salt or inorganic base salt” means a salt of a base or alkaline agent as defined below: alkali metal hydroxides, e.g., sodium hydroxide and potassium hydroxide, aqueous ammonia, amines or alkanolamines, or salts of “basic” amino acids, e.g., lysine or arginine.

[0041] The term "cationic counterion" means a cation or cationic group derived from an organic or inorganic base salt that cancels out the anionic charge of at least one component of the composition according to the present invention. More preferably, the cationic counterion is i) an alkali metal, e.g., sodium, potassium, preferably Na+; ii) an alkaline earth metal, e.g., calcium; iii) an ammonia: R4N + Here, R may be the same or different, and may be a hydrogen atom or a (C1-C6) alkyl group substituted with one or more hydroxyl groups, preferably R represents a hydrogen atom or a (C1-C4) alkyl group, such as methyl.

[0042] This effectiveness of the composite material according to the present invention is, to the best of the inventors' knowledge, being characterized for the first time. The use of a composite material of bismuth oxycarbonate particles and polymer in a cosmetic composition intended for effective filtering of UV irradiation, particularly UV-B irradiation, has not been previously proposed.

[0043] The composite materials according to the present invention are intended, in particular, to protect keratinous substances, especially skin and hair, from UV irradiation, especially in cosmetic compositions in the fields of sun protection, hair care or treatment, and cosmetics.

[0044] Accordingly, in another view, the present invention also relates to a non-therapeutic cosmetic use of a composite material according to the present invention for filtering UV irradiation, preferably UV-B irradiation, and further comprises at least applying a composition comprising a composite material according to the present invention to a keratin substance.

[0045] The present invention also relates to a non-therapeutic cosmetic method for filtering UV irradiation, preferably UV-B irradiation, which comprises at least applying a composition comprising a composite material containing bismuth oxycarbonate and a polymer, as described above, to a keratin substance.

[0046] The present invention also relates to a method for preparing composite materials according to the present invention.

[0047] The term "keratinous substance" means, in particular, skin, and includes the scalp, lips, and keratin fibers (e.g., hair, eyelashes, eyebrows), especially skin and / or hair, preferably skin.

[0048] The phrase "at least one" is synonymous with "one or more."

[0049] The words "...~...", "...~...", "...~...", and "...~...", unless otherwise specified, should be understood to include their limits.

[0050] Other features, variations, and advantages of compositions according to the present invention will become clearer by reading the following description and examples. [Brief explanation of the drawing]

[0051] [Figure 1] Figure 1 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of composite materials A1, A2, B1, and B2 at 0.005 mass% in water. [Figure 2] Figure 2 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of composite materials C1, C2, C3, and C4 at 0.005 mass% in water. [Figure 3] Figure 3 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of composite materials D, E1, E2, F1, and F2 at 0.005 mass% in water. [Figure 4] Figure 4 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for a dispersion of composite material G, H1, and H2 at 0.005 mass% in water. [Figure 5] Figure 5 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for a dispersion of composite materials I, J1, and J2 at 0.005 mass% in water. [Figure 6] Figure 6 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of composite materials K, L1, and L2 at a concentration of 0.005 mass% in water. [Figure 7] Figure 7 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for a dispersion of composite materials M, N1, N2, O1, and O2 at 0.005 mass% in water. [Figure 8] Figure 8 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of composite materials P1, P2, Q1, and Q2 at 0.005 mass% in water. [Figure 9] Figure 9 shows the absorbance spectra obtained by UV-Vis spectrophotometer for a dispersion of composite materials S1, S2, and R at a concentration of 0.005 mass% in a water / propylene glycol / Tween 20 mixture. [Figure 10] Figure 10 shows the absorbance spectrum obtained by UV-Vis spectrophotometer for a dispersion of composite material T at a concentration of 0.005 mass% in a water / propylene glycol / Tween 20 mixture. [Figure 11] Figure 11 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of Alfa Aesar Bismutite and composite material U at a concentration of 0.005 mass% in water. [Figure 12] Figure 12 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for a dispersion of composite materials V and W at 0.005 mass% in water. [Figure 13] Figure 13 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of composite materials X, Y, and Z at 0.005 mass% in water. [Figure 14] Figure 14 shows the absorbance spectrum obtained by UV-Vis spectrophotometer for a dispersion of composite material AA at a concentration of 0.005 mass% in a water / propylene glycol / Tween 20 mixture. [Figure 15]Figure 15 shows the absorbance spectrum obtained by a UV-Vis spectrophotometer for a dispersion of composite material DD at 0.005 mass% in water. [Figure 16] Figure 16 shows the absorbance spectra obtained by UV-Vis spectrophotometer for a dispersion of composite material I and EE (t=0 and t=48 hours) and sodium lignosulfonate at 0.005 mass% in water. [Figure 17] Figure 17 shows the absorbance spectra obtained by a UV-Vis spectrophotometer for dispersions of composite material D and FF (t=0 and t=48, t=48 at T=45°C) at a concentration of 0.005 mass% in water. [Figure 18] Figure 18 shows the absorbance spectrum obtained by UV-Vis spectrophotometer for a dispersion of composite material HH at a concentration of 0.005 mass% in a water / propylene glycol / polysorbate 20 mixture (mass fractions of 49.85 / 49.85 / 0.30, respectively). [Figure 19] Figure 19 shows the absorbance spectrum obtained by UV-Vis spectrophotometer for a dispersion of composite material II at a concentration of 0.005 mass% in a water / propylene glycol / polysorbate 20 mixture (mass fractions of 49.85 / 49.85 / 0.30, respectively). [Figure 20] Figure 20 shows the absorbance spectrum obtained by UV-Vis spectrophotometer for a dispersion of composite material JJ at 0.005 mass% in a water / propylene glycol / polysorbate 20 mixture (mass fractions of 49.85 / 49.85 / 0.30, respectively). [Figure 21] Figure 21 shows the absorbance spectrum obtained by a UV-Vis spectrophotometer for composition A1.1 diluted in deionized water at a concentration of 0.005 wt% of composite material A1. [Modes for carrying out the invention]

[0052] The present invention relates to a composite material, a) the following formula (I): (BiO) 2-x(CO3) (where -0.4 < x < 0.6), at least one particle of bismuth oxycarbonate and its solvates, such as its hydrates, wherein the maximum average dimension of the particle is less than 400 nm; and b) the above composite material containing at least one polymer.

[0053] Composite material

[0054] As described above, the composite material comprises: a) at least one bismuth oxycarbonate and b) at least one polymer.

[0055] According to certain embodiments, the mass ratio of one or more bismuth oxycarbonate particles a) to one or more polymers is 0.01 to 50, preferably 0.2 to 15, more preferably 0.3 to 10, even more preferably 0.5 to 8.5.

[0056] The term "average size" or "average dimension" is intended to refer to the number average value of the dimensions of the composite material or the particle. The dimensions of the composite material or the particle can be determined by transmission electron microscopy, such as transmission electron microscopy using a Hitachi HT 7700 microscope, especially at an acceleration voltage of 100 kV, by scanning electron microscopy, or by measuring the specific surface area by the BET method, or by using a laser particle size analyzer. Preferably, the dimensions of the particle are determined by transmission electron microscopy, such as transmission electron microscopy using a Hitachi HT 7700 microscope, especially at an acceleration voltage of 100 kV, or by scanning electron microscopy.

[0057] Preferably, the measurement is performed on the smallest individualized or individuable object.

[0058] The average value can be calculated by analyzing images acquired using software such as ImageJ software (CASchneider, WSRasband, KWEliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat.Methods.9 (2012)671~675).

[0059] The average dimension is selected from the average length L, average width l, average thickness e, or average diameter d.

[0060] The terms “average size of the maximum dimensions” or “maximum average dimensions” of the composite material or particles are intended to refer to the maximum average dimensions of the surface (e.g., face) that can be measured between two points facing each other in the diametrical direction on an individual particle. In the context of this invention, this dimension is defined as the maximum Feret diameter.

[0061] The "length" L of the composite material or particle is the maximum dimension that can be observed in an image taken perpendicular to the plane on which the composite material or particle is placed.

[0062] The "width" l and "thickness" e of the composite material or particles are the lengths of the major and minor axes of the smallest ellipse in which the median cross section of the composite material or particles can be inscribed.

[0063] The "diameter" d of a composite material or particle is the maximum dimension that can be observed along a line passing through the center of a circle or sphere.

[0064] The composite material according to the present invention may have various shapes or structures.

[0065] The composite material according to the present invention may be spherical, cubic, plate-like, cylindrical, or tubular.

[0066] The shape of the composite material will depend, in particular, on the method and operating conditions for its manufacture.

[0067] In particular, composite materials according to the present invention may take the form of tubes, plates, sheets, rods, spheres, flowers, pom-poms, threads, filaments, fibers, needles, cubes, or any combination thereof.

[0068] The composite materials according to the present invention may also aggregate in the form of superstructures. For example, plates, tubes and / or rods can aggregate in the form of spheres, flowers or pom-poms.

[0069] According to one particular embodiment, the composite material according to the present invention is in the form of a sphere.

[0070] In 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.

[0071] Therefore, the composite material in the form of a plate, rod, or tube differs, in particular, from the form of a sphere or fiber, or from the form of a flower, pom-pom, thread, filament, needle, or cube.

[0072] It should be understood that the composite materials according to the present invention can be used in the form of a mixture. In particular, the composite materials according to the present invention can be used in a mixture of plates and / or rods and / or tubes in any proportion.

[0073] Similarly, a composite material in spherical form can consist of a polymer matrix and bismutite platelets, i.e., two forms represented within the same composite. Furthermore, it is possible to achieve a film form containing bismutite particles by freeze-drying.

[0074] In a preferred embodiment, the composite material used in accordance with the present invention is mainly or exclusively in the form of a sheet.

[0075] In the form of a "plate," the composite material has a length greater than its width and a width greater than its thickness.

[0076] According to a preferred embodiment, the composite material is mainly or exclusively in the form of a rod.

[0077] The composite material in the form of a "rod" has a solid cylindrical shape with a length L greater than its diameter d, or a prism shape with a solid polygonal base, preferably a triangle or hexagon, and the diameter d of the circle circumscribing the base of this polygon is smaller than the length L of the prism.

[0078] According to a preferred embodiment, the composite material is mainly or exclusively in the form of a tube.

[0079] In the form of a "tube," the composite material has a hollow cylindrical shape, and its length L is greater than its diameter d.

[0080] In the present invention, the phrase "primarily in the form of plates / rods / tubes" is intended to mean that at least 50 percent (% by number), particularly at least 70 percent (% by number), or at least 90 percent (% by number), of the composite material are in the form of plates / rods / tubes, respectively.

[0081] One or more bismuth oxycarbonate particles a) and one or more polymers b) may be arranged in different ways within the composite material.

[0082] 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.

[0083] Therefore, they may include at least one coating as one or more layers surrounding a core that is chemically distinct from the coating.

[0084] The coating may be formed in one or more layers.

[0085] The core of the composite material is a) bismuth oxycarbonate of the following formula (I) (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and at least contains one or more particles of its solvate, such as its hydrate, where the maximum average dimension of the particles is less than 400 nm.

[0086] According to a specific embodiment, the core of the composite material may be composed of at least one polymer b).

[0087] The composite material may contain the bismuth oxycarbonate particles a) defined above in the core and / or in one or more layers forming the coating.

[0088] According to a specific embodiment, the material contains at least one bismuth oxycarbonate particle a) defined above in the core.

[0089] According to another specific embodiment, the material contains the bismuth oxycarbonate particle a) defined above in the coating.

[0090] According to one embodiment, the one or more polymers b) can cover the front or part of at least one bismuth oxycarbonate particle a).

[0091] According to another embodiment, the one or more polymers b) can be completely or partially coated by at least one bismuth oxycarbonate particle a).

[0092] In particular, the mass ratio of one or more bismuth oxycarbonate particles a) to the polymer is in the range of 0.01 to 50, preferably 0.2 to 15, more preferably 0.3 to 10, still more preferably 0.5 to 8.5.

[0093] According to certain embodiments, the composite material according to the invention comprises at least one layer surrounding the core.

[0094] Thus, according to certain embodiments, the composite material according to the invention comprises a) a core comprising at least one particle of a bismuth oxycarbonate of the following formula (I): (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvates, such as its hydrates, with a maximum average dimension of the particles of less than 400 nm, the surface of the core being continuous or discontinuous, and b) a coating comprising at least one polymer.

[0095] According to a first variant of the invention, the composite material according to the invention comprises a coating (also called a shell or envelope), the coating being continuous (i.e. surrounding the entire surface of the core).

[0096] According to a second variant of the invention, the composite material according to the invention also comprises a coating (also known as a shell or envelope), the coating being discontinuous (i.e. surrounding the core surface discontinuously).

[0097] Preferably, 10% to 90%, more preferably 10% to 70%, even more preferably 30% to 50% of the core surface is covered by the coating.

[0098] According to one embodiment, the coating comprises a multilayer coating, i.e. one or more inner layers and outer layers, in other words a plurality of layers that completely or partially overlap, where each layer may be continuous or discontinuous.

[0099] In a multilayer coating, the term "inner layer" means a layer that is not an outer layer. This is a layer deposited directly on the core or any intermediate layer between the core and the outer layer.

[0100] In a multilayer coating, the term "outer layer" means a layer that forms the outermost layer of the 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 has no coating.

[0101] In a multilayer coating formed from two layers, the inner layer is the layer adjacent to the core, and the outer layer is the layer adjacent to the inner layer and not adjacent to the core.

[0102] In a multilayer coating consisting of two layers, the inner layer is the layer adjacent to the core and one or more intermediate layers between the layer adjacent to the core and the outer layer.

[0103] One or more 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.

[0104] Each layer may be composed of a single compound or a mixture of a plurality of compounds.

[0105] In particular, one or more layers may extend concentrically with respect to the core.

[0106] In particular, the composite material according to the present invention has a double layer surrounding the core, namely an inner layer and an outer layer.

[0107] According to a preferred embodiment, the composite material according to the present invention has at least one layer, preferably at least one layer containing at least one polymer.

[0108] According to a preferred embodiment, the composite material according to the present invention a) a core containing at least one particle of bismuth oxycarbonate of the following formula (I): (BiO) 2-x (CO3) (where -0.4 < x < 0.6) and its solvates, such as its hydrates, wherein the maximum average dimension of the particles is less than 400 nm; and, surrounding the core continuously or discontinuously and b) at least one layer containing at least one polymer comprising.

[0109] Preferably, the composite material according to the invention a) the following formula (I): (BiO) 2-x (CO3) formula (I) (where -0.4 < x < 0.6), at least one particle of bismuth oxycarbonate and its solvates, such as its hydrates, and the maximum average dimension of the particles is less than 400 nm; and, a single layer adjacent to the core and b) containing at least one polymer comprising.

[0110] According to a particular embodiment, the composite material according to the invention a) the following formula (I): (BiO) 2-x (CO3) (where -0.4 < x < 0.6), at least one particle of bismuth oxycarbonate and its solvates, such as its hydrates, and the maximum average dimension of the particles is less than 400 nm, an inner layer adjacent to the core and containing at least one inorganic compound c) different from the bismuth oxycarbonate particles a), an outer layer adjacent to the inner layer and containing b) at least one polymer comprising.

[0111] According to a particular embodiment, the composite material according to the invention a) the following formula (I): (BiO) 2-x (CO3) (where -0.4 < x < 0.6), at least one particle of bismuth oxycarbonate and its solvates, such as its hydrates, and the maximum average dimension of the particles is less than 400 nm, an inner layer adjacent to the core and containing at least one inorganic compound c) different from the bismuth oxycarbonate particles a), an outer layer adjacent to the inner layer and containing b) at least one polymer, and the outer layer optionally has the following formula (I): (BiO)2-x (CO3) (where -0.4 < x < 0.6), and at least one particle of its solvate, such as its hydrate, may be included, where the maximum average dimension of the particle is less than 400 nm, the outer layer contains.

[0112] a) Bismuth oxycarbonate particles

[0113] The bismuth oxycarbonate particles a) according to the present invention have the following formula (I): (BiO) 2-x (CO3) (where -0.4 < x < 0.6), and its solvate, such as its hydrate. The value of x can be determined, among other things, by elemental analysis.

[0114] Preferably, x is equal to 0, and the empirical formula of the bismuth oxycarbonate particles a) is (BiO)2(CO3), and its solvate, such as its hydrate.

[0115] The bismuth oxycarbonate particles a) according to the present invention may be crystalline or amorphous.

[0116] According to one embodiment of the present invention, the bismuth oxycarbonate particles a) are amorphous.

[0117] According to a preferred embodiment of the present invention, the bismuth oxycarbonate particles a) are crystalline.

[0118] It will be understood that the bismuth oxycarbonate particles a) can be composed of a mixture of a plurality of bismuth oxycarbonate particles having different empirical formulas and / or different shapes.

[0119] Therefore, the bismuth oxycarbonate particles a) may be a mixture of amorphous particles and crystalline particles.

[0120] In the case of the present invention, the term "crystalline" means that the atoms forming the bismuth oxycarbonate particles are arranged in an ordered manner. In other words, crystalline bismuth oxycarbonate particles are organized substances.

[0121] In contrast, "amorphous" refers to particles in which the atoms are arranged disorderly. The atoms of such particles show no organization at the microscopic level.

[0122] Preferably, the crystalline particles required according to the present invention have the crystal phase of natural ore bismutite, which is referred to as layered and which is composed of layers of [Bi2O2] 2+ and layers of [CO3] 2- alternately overlapping.

[0123] Such particles crystallize in the orthorhombic system of the space group Imm2.

[0124] The bismutite crystal structure of bismuth oxycarbonate may have the following lattice parameters: a = 3.865 Å; b = 3.862 Å; c = 13.675 Å and V lattice = 0.204 nm 3 . This specific atomic arrangement enables the growth of anisotropic objects in particular.

[0125] Particles are considered "anisotropic" when the elongation factor R between its length L and its thickness e, i.e., R = L / e, is greater than 2.

[0126] According to the present invention, the maximum average dimension of the bismuth oxycarbonate particles a) of the crystallized or amorphous, preferably crystallized, following empirical formula: (BiO) 2-x (CO3) (where -0.4 < x < 0.6) is less than 400 nm.

[0127] Preferably, the maximum average dimension of the particles is less than 300 nm.

[0128] According to the present invention, bismuth oxycarbonate particles of the following empirical formula (BiO) 2-x (CO3) (where -0.4 < x < 0.6) can be of any shape.

[0129] The shape of the particles depends, inter alia, on the process and operating conditions for producing them.

[0130] According to one embodiment, the particles a) have the same morphology.

[0131] In particular, when the composition contains particles a) having the same morphology, the composite material according to the present invention consists of particles in the form of plates or sheets or rods or spheres or flowers or pompons or threads or filaments or fibers or needles or cubes, preferably in the form of plates or rods.

[0132] According to one embodiment, the particles a) have different morphologies.

[0133] In particular, when the composite material contains particles a) of different morphologies, the composite material according to the present invention contains one or more particles selected from the form of tubes, plates, sheets, rods, spheres, flowers, pompons, threads, filaments, fibers, needles, cubes, or any combination thereof.

[0134] The particles according to the present invention may also aggregate in the form of superstructures. For example, plates, tubes and / or rods may aggregate in the form of spheres, flowers or pompons.

[0135] According to a preferred embodiment, the particles according to the present invention are plate-like and / or rod-like.

[0136] Thus, particles in the form of plates or rods or tubes are significantly different, inter alia, from the form of spheres or fibers, flowers, pompons, threads, filaments, needles or cubes.

[0137] Needless to say, 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 in a mixture of any proportion of plate-like particles and / or rod-like particles and / or tubular particles, especially in a mixture of any proportion of plate-like particles and / or rod-like particles.

[0138] According to a preferred embodiment, the particles used in accordance with the present invention are mainly or exclusively in the form of plates.

[0139] A "plate-like" particle has a length greater than its width and a width greater than its thickness.

[0140] In particular, when the particles are in the form of a plate, the bismuth oxycarbonate particles a) are, An average length L in the range of 15 to 300 nm, particularly in the range of 30 to 250 nm, preferably in the range of 50 to 200 nm, more preferably in the range of 70 to 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, more preferably in the range of 50 to 120 nm; The average thickness e is 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, here, e <l<Lである。

[0141] According to one embodiment, the bismuth oxycarbonate particles are mainly or exclusively in the form of rods, or comprise particles in the form of rods.

[0142] The "rod" shaped particles have a solid cylindrical shape with a length L greater than its diameter d, or a prism shape with a solid polygonal base, preferably triangular or hexagonal, and the diameter d of the circle circumscribing the base of this polygon is smaller than the length L of the prism.

[0143] In particular, when the particles are in the form of rods, whether cylindrical or prismatic, the bismuth oxycarbonate particles are, An average length L in the range of 30 to 300 nm, particularly in the range of 50 to 250 nm, preferably in the range of 70 to 230 nm, more preferably in the range of 70 to 140 nm; The average diameter 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. We have such that L > d.

[0144] According to one embodiment, the bismuth oxycarbonate particles of the present invention include particles in the form of tubes.

[0145] A "tubular" particle has a hollow cylindrical shape, and its length L is greater than its diameter d.

[0146] In particular, when the particles are in the form of tubes, the bismuth oxycarbonate particles are, An average length L in the range of 10 to 300 nm, particularly in the range of 20 to 250 nm, preferably in the range of 40 to 200 nm, more preferably in the range of 60 to 200 nm; The average diameter d is in the range of 2 to 30 nm, particularly in the range of 3 to 20 nm, preferably in the range of 5 to 15 nm. We have such that L > d.

[0147] In the present invention, "primarily in the form of plates / rods" is intended to mean that at least 50% by number of the particles, particularly at least 70% by number, or at least 90% by number, are in the form of plates / rods, respectively.

[0148] Doping of particle a)

[0149] According to a particular embodiment, the bismuth oxycarbonate particles a) may be doped.

[0150] In particular, the bismuth oxycarbonate particles may be doped with one or more chemical elements that can be inserted into the structure or that can partially replace existing elements.

[0151] The particles can be doped by substitution of all or part of the cations and / or all or part of the anions.

[0152] According to a particular embodiment, the dope is partially related to the inserted cation or the substituted cation in place of bismuth, up to a maximum of 20% of the composition in terms of bismuth.

[0153] According to this modified example, the degree of doping is particularly in the range of 0.005% to 15%, preferably 0.05% to 12%, more preferably 0.1% to 10%, and even more preferably 0.5% to 6%.

[0154] In particular, the bismuth oxycarbonate particles may 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).

[0155] Preferably, the bismuth oxycarbonate particles may be doped with cations derived from elements selected from titanium, vanadium, manganese, iron, copper, zinc, lanthanum, and / or cerium atoms; more preferably with cations derived from elements selected from manganese, iron, and / or cerium atoms; and even more preferably with cations derived from manganese or iron atoms.

[0156] According to a modification of one embodiment, the bismuth oxycarbonate particles are doped with manganese-derived cations, the degree of doping being particularly in the range of 0.5% to 2%.

[0157] According to a variation of another embodiment, the bismuth oxycarbonate particles are doped with iron-derived cations, the degree of doping being particularly in the range of 0.5% to 2%.

[0158] According to another specific embodiment, the dope is partially related to the inserted anion or a substituted anion in place of a carbonate group, up to a maximum of 20% of the composition in terms of carbonate groups.

[0159] According to this modified example, 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%.

[0160] In particular, the bismuth oxycarbonate particles are anions derived from elements selected from fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), and iodine (I), and / or polyatomic anions, in particular sulfate ions (SO4). 2- ), sulfonate ion (S(=O)2-O - ), sulfite ions (SO3 2- ), phosphate ion (PO4 3- ) and / or iodate ions (IO3 - They may be doped with polyatomic anions selected from ).

[0161] Preferably, the bismuth oxycarbonate particles are S 2- , SO3 2- SO4 2- Cl - and / or I - And, more preferably, SO3 2- SO4 2- and / or Cl - So, more Cl - or SO42- And it's okay to dope it.

[0162] According to a modification of one embodiment, the bismuth oxycarbonate particles are doped with anions derived from chlorine atoms, the degree of doping being particularly in the range of 0.01% to 0.1%.

[0163] According to a variation of another embodiment, the bismuth oxycarbonate particles are doped with anions derived from iodine atoms, the degree of doping being particularly in the range of 0.003% to 0.01%.

[0164] According to a variation of another embodiment, the bismuth oxycarbonate particles are doped with sulfate ions, the degree of doping being particularly in the range of 0.005% to 0.1%.

[0165] According to a variation of another embodiment, the bismuth oxycarbonate particles consist of cations, preferably cations derived from elements selected from titanium, vanadium, manganese, iron, copper, zinc, lanthanum, and / or cerium atoms, more preferably cations derived from elements selected from manganese, iron, and / or cerium atoms, and even more preferably cations derived from elements selected from manganese or iron atoms, and anions, preferably anions derived from elements selected from fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), and iodine (I), and / or polyatomic anions, particularly sulfate ions (SO4). 2- ), sulfonate ion (S(=O)2-O - ), sulfite ions (SO3 2- ), phosphate ion (PO4 3- ) and / or iodate ions (IO3 - A polyatomic anion selected from ) and fuferS 2- , SO3 2- SO4 2- Cl - and / or I - And even better, SO3 2- SO4 2- and / or Cl- And, in particular, Cl - , I - or SO4 2- And then you get doped.

[0166] In a preferred embodiment, the bismuth oxycarbonate particles required according to the present invention are not doped.

[0167] According to another preferred embodiment, the bismuth oxycarbonate particles are doped.

[0168] According to another preferred embodiment, the bismuth oxycarbonate particles required according to the present invention are a mixture of doped and undoped particles.

[0169] Method for preparing the bismuth oxycarbonate particles a)

[0170] The bismuth oxycarbonate particles a) can be obtained through any preparation process known to those skilled in the art.

[0171] For example, the synthesis of these bismuth oxycarbonate particles is described in the following document by Ni et al. (Fabrication, modification and application of (BiO)2CO3-based photocatalysts: A review, Applied Surface Science, 365, 2016, 314~335).

[0172] In particular, the bismuth oxycarbonate particles can be prepared via a solvothermal route, an electrochemical route, by co-precipitation, or by reflux, preferably via a solvothermal route or by reflux.

[0173] According to a modification of the first embodiment, the bismuth oxycarbonate particles are obtained via a solvent-thermal pathway, particularly by synthesizing bismuth nitrate with various carbonating agents, such as sodium carbonate, ammonium carbonate, or urea, in a polar protic solvent in the presence of a polyol. Such synthesis makes it possible to obtain plate-like and / or rod-like bismuth oxycarbonate particles, the maximum dimensions of which are in the range of 50 to 300 nm.

[0174] The solvothermal synthesis of particles is particularly relevant to the following literature by Cheng, G. et al. (Shape-controlled solvothermal synthesis of bismuth subcarbonate nanomaterials, J.Solid State Chem. 183, 1878~1883 (2010)); the following literature by Ruan, M. et al. (Facile Green Synthesis of Highly Monodisperse Bismuth Subcarbonate Micropompons Self-assembled by Nanosheets: Improved Photocatalytic Performance, Acta Physico-Chimica Sinica, 33, 2017, 1033~1042); the following literature by Quin et al. (Template-Free Fabrication of Bi2O3 and (BiO)2CO3 Nanotubes and Their Application in Water Treatment, Chem.Eur.J., 18, 2012, 16491~16497); and the following literature by Cheng, G. et al. (Shape-controlled solvothermal synthesis of Bismuth subcarbonate nanomaterials, J. Solid State Chem., 183, 2010, 1878-1883); the following document by Liu, YY et al. (Preparation, electronic structure, and photocatalytic properties of Bi2O2CO3 nanosheet, Appl. Surf. Sci., 257, 2010, 172-175); the following document by Zheng et al. (Synthetic Bi2O2CO3 nanostructures: Novel photocatalyst with controlled special surface exposed, Journal of Molecular Catalysis A: Chemical, 2010, 317 (1-2), 34-40); Liu, SQ et al.This is described in the following literature by [author's name] (The effects of citrate ion on morphology and photocatalytic activity of flower-like Bi2O2CO3, Ceram.Int., 40, 2014, 2343~2348); or in the following literature 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, 654~658).

[0175] The electrochemical synthesis of particles is described in particular in the following document by Hu, Y. et al. (Simple hydrolysis route to synthesize Bi2O2CO3 nanoplate from Bi nanopowder and its photocatalytic application, Materials Letters, 170, 2016, 72-75).

[0176] The synthesis of particles by coprecipitation is particularly well-documented in the following paper by Chen, XY et al. (Controlled synthesis of bismuth oxo nanoscale crystals (BiOCl,BiOCl) 12 O 17 Cl2, α-Bi2O3, and (BiO)2CO 3) This is described in "by solution-phase methods," J. Solid State Chem., 180, 2007, 2510-2516).

[0177] The synthesis of particles by reflux is described in particular in the following document by Chen et al. (Fabrication of bismuth subcarbonate nanotube arrays from bismuth citrate, Chem.Commun., 2006, 2265~2267).

[0178] According to a preferred embodiment, the bismuth oxycarbonate particles required according to the present invention are obtained via a solvothermal pathway, for example, via a solvothermal pathway according to the method described by Chen et al., or by reflux, for example, by reflux according to the method described by Chen et al.

[0179] According to a preferred embodiment, the bismuth oxycarbonate particles required according to the present invention are obtained via a preparation process 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.

[0180] If the particles used in accordance with the present invention are doped, one or more additional agents containing doping elements may be added.

[0181] In particular, one or more bismuth(III) complexes are 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.

[0182] The one or more bismuth(III) complexes may also be obtained from bismuth minerals, such as elemental bismuth and / or bismuth oxide and / or bismuth sulfide.

[0183] Preferably, the one or more bismuth(III) complexes are bismuth(III) nitrate and its hydrate form with the following formula: Bi(NO3)3·xH2O, and more preferably, bismuth nitrate pentahydrate with the following formula: Bi(NO3)3·5H2O.

[0184] In particular, one or more carbonating agents are selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, (NH4)2CO3, LiHCO3, NaHCO3, KHCO3, RbHCO3, CsHCO3, (NH4)HCO3, urea (NH2)2CO and urea derivatives, CO2, preferably from Na2CO3, K2CO3, (NH2)2CO, (NH4)2CO3, and more preferably from (NH2)2CO and / or (NH4)2CO3.

[0185] Polyols are compounds containing multiple hydroxyl functional groups. These polyols may be selected from, in particular, glycols, especially ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol; short-chain or long-chain glycol polymers, e.g., polyethylene glycol, polypropylene glycol, polybutylene glycol; glycerol and its derivatives; or sugars, e.g., glucose, fructose, sucrose, xylitol, mannitol, e.g., D-mannitol, sorbitol, or maltitol.

[0186] According to one embodiment, the bismuth oxycarbonate particles required according to the present invention are obtained through a preparation process using a polyol or a mixture of polyols.

[0187] According to a modification of the first embodiment, the one or more polyols may also be used as solvents. Thus, the bismuth oxycarbonate particles can be obtained, for example, by the process described below.

[0188] Solution A is formed by dissolving a bismuth(III) complex in a polyol or a mixture of polyols at a concentration of preferably 0.001 to 0.5 M. Solution B is formed by partially or completely dissolving a carbonating agent in a polyol or a mixture of polyols, or in a polyol or a mixture of polyols different from the one used in Solution A, at an amount of preferably 1 to 100 equivalents relative to bismuth.

[0189] In the case of cation doping, the dopant is preferably incorporated into solution A. In the case of anionic doping, the dopant is preferably incorporated into solution B.

[0190] In the case of doping with one or more cationic and / or one or more anionic, one or more cationic dopants are preferably incorporated into solution A, and one or more anionic dopants are preferably incorporated into solution B. Subsequently, solution A is added to solution B at room temperature. If the polyol or the polyol mixture is not a liquid at room temperature, all solids are mixed.

[0191] Next, the resulting mixture is heated at 90–250°C for a reaction time of 10 minutes to 48 hours. If the desired reaction temperature is above the boiling point of the solvent, solubilothermal synthesis is performed using an autoclave.

[0192] Preferably, the reaction temperature is 95°C to 200°C and the reaction time is 1 to 24 hours, and more preferably, the reaction temperature is 100°C to 180°C and the reaction time is 2 to 16 hours.

[0193] The resulting particles are separated from the reaction medium by centrifugation and then washed by a continuous cycle of dispersion and centrifugation.

[0194] After drying under vacuum at a temperature of 40°C to 60°C, a white powder is obtained.

[0195] When one or more polyols are used as a solvent, the resulting bismuth oxycarbonate particles are in the form of plates, preferably plates with an average thickness e of 2 to 15 nm, and / or tubes.

[0196] According to a variation of another embodiment, the one or more polyols are used not only as a solvent but also only as an additive. In this case, the bismuth oxycarbonate particles can be obtained, for example, by following the process described below.

[0197] Solution A is formed by dissolving a bismuth complex preferably at a concentration of 0.001 to 0.5 M and one or more polyols preferably at a total polyol concentration of 0.01 to 5 M in a solvent, preferably in a polar solvent. Solution B is formed by partially or completely dissolving a carbonate agent preferably in an amount of 1 to 100 equivalents relative to the bismuth complex in the same or a different polar solvent as Solution A (a polar solvent miscible with the solvent of Solution A), preferably in the same polar solvent as Solution A.

[0198] In the case of cation doping, the dopant is preferably incorporated into solution A. In the case of anionic doping, the dopant is preferably incorporated into solution B.

[0199] In the case of doping with one or more cations and / or one or more anions, one or more cationic dopants are preferably incorporated into solution A, and one or more anionic dopants are preferably incorporated into solution B.

[0200] Next, solution A is added to solution B at room temperature. The resulting mixture is heated at 90°C to 250°C for 10 minutes to 48 hours. Solventricular synthesis is performed using an autoclave when the desired reaction temperature is above the boiling point of the solvent.

[0201] Preferably, the reaction temperature is 90°C to 150°C, and the reaction time is 4 to 16 hours.

[0202] The resulting particles are separated from the reaction medium by centrifugation and then washed by a continuous cycle of dispersion and centrifugation.

[0203] After drying under vacuum at a temperature of 40°C to 60°C, a white powder is obtained.

[0204] When one or more polyols are used solely as additives, the one or more polyols are particularly selected from ethylene glycol, propylene glycol, glycerol, and / or sugars, preferably sugars, more preferably D-mannitol.

[0205] According to this modification, the synthesis process also uses a solvent different from the polyol, or a mixture of solvents other than the polyol. 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 combinations thereof, and the solvent is more preferably water.

[0206] In particular, when one or more polyols are selected as additives and water is selected as the solvent, the bismuth oxycarbonate particles are preferably obtained in the form of plates and / or rods.

[0207] polymer b)

[0208] A composite material according to the present invention comprises at least one polymer b).

[0209] The one or more polymers b) are natural and / or synthetic, hydrophilic and / or hydrophobic and / or amphiphilic, anionic and / or cationic and / or zwitterionic and / or nonionic (or referred to as "neutral"). Preferably, the one or more polymers b) are nonionic, anionic or cationic, more preferably nonionic or anionic.

[0210] In particular, the one or more polymers b) are selected from polymers having a molecular weight of 1000 to 20,000,000 Da, preferably 5000 to 10,000,000 Da, even more preferably 7000 to 3,000,000 Da.

[0211] The one or more polymers b) are in a crosslinked and / or non-crosslinked form, preferably in a non-crosslinked form.

[0212] The one or more polymers b) may be silicone polymers or non-silicone polymers.

[0213] According to a particular embodiment, the one or more polymers b) are at least one silicone polymer or comprise at least one silicone polymer.

[0214] Examples of silicone polymers b) include dimethicone copolyol, in particular mixtures of cyclomethicone and dimethicone copolyol, especially those sold under the trade name DC 5225 C by the company Dow Corning, and alkyldimethicone copolyol, in particular laurylmethicone copolyol, especially those sold under the trade name Dow Corning 5200 Formulation Aid by the company Dow Corning, cetyl dimethicone copolyol, and mixtures of cetyl dimethicone copolyol, polyglycerol (4 moles) isostearate and hexyl laurate are mentioned. 登録商標 and those sold under the trade name Dow Corning 5200 Formulation Aid by the company Dow Corning, cetyl dimethicone copolyol, and mixtures of cetyl dimethicone copolyol, polyglycerol (4 moles) isostearate and hexyl laurate are mentioned.

[0215] According to a preferred embodiment, the one or more polymers b) do not contain silicon.

[0216] According to a preferred embodiment, the weight average molecular weight Mw of the one or more polymers b) is 2000 or more.

[0217] The term "anionic polymer" refers to a polymer containing one or more anionic groups, particularly carboxyls, carboxylates, sulfates, sulfonic acids, sulfonates, phosphates, phosphonic acids, and phosphonates, preferably a polymer containing one or more anionic groups selected from carboxylates and / or sulfonates and / or sulfates. Anionic derivatives can be chlorinated in the form of alkali metal salts or alkaline earth metal salts, preferably sodium salts or calcium salts.

[0218] The term "cationic polymer" means a polymer containing one or more cationic groups that carry an electric charge regardless of pH, or one or more cationic groups that can be cationized. Preferably, the cationic polymer b) has an amino group.

[0219] The term "nonionic polymer" refers to a polymer that does not have charged groups or groups that can become charged by changes in pH.

[0220] In particular, the one or more polymers b) can be selected from polyphenols and their salts, polyphenol sulfonates and their salts, polysaccharides and their salts, polyacids and their salts, polyols, polyamides, polyamines and their salts, polyesters, polyhydroxyalkanoates, polyureas, polyurethanes, polyethers, polyethylenes, polypropylenes, polystyrenes, proteins, and / or copolymers thereof and / or combinations thereof.

[0221] The one or more polymers b) are cyclic or acyclic (they do not contain any rings in their structure).

[0222] One or more cyclic polymers (b) are aromatic (containing at least one aromatic ring) or non-aromatic.

[0223] Examples of aromatic cyclic polymers (b) include lignosulfonic acids, lignosulfonates, polystyrene sulfonates, polystyrene sulfonates, anionic polyanethole derivatives, particularly polyanethole sulfonates, and combinations thereof.

[0224] According to a particular embodiment, the one or more polymers b) are selected from polystyrene sulfonates, polystyrene sulfonates, and in particular polystyrene sulfonates of alkali metal or alkaline earth metal salts (particularly sodium or calcium).

[0225] According to one embodiment, the one or more polymers b) are selected from lignosulfonic acid or lignosulfonate salts of alkali metals or alkaline earth metals (particularly sodium or calcium).

[0226] According to one embodiment, the one or more polymers b) are selected from anionic polyanethole derivatives, particularly polyanethole sulfonates of alkali metals or alkaline earth metals (particularly sodium or calcium, particularly sodium).

[0227] Preferably, the one or more non-aromatic cyclic polymers b) are selected from polysaccharides, which may be anionic, cationic, or nonionic.

[0228] Preferably, the one or more polymers b) are selected from natural hydrophilic and / or lipophilic and / or amphiphilic and anionic and / or cationic and / or neutral polysaccharides.

[0229] More preferably, the one or more polymers used are natural hydrophilic and / or lipophilic and / or amphiphilic and anionic and / or cationic and / or neutral polysaccharides, in particular natural hydrophilic anionic and / or cationic and / or neutral polysaccharides, and more preferably, the one or more polymers used are neutral or anionic polysaccharides.

[0230] Non-limiting representative examples of these polysaccharides include, inter alia, carrageenan, chitosan, dextran sulfate, (di) starch phosphate, pullulan, and their forms esterified (or acetylated) with carboxylic acids (preferably containing 1 to 30 carbon atoms, more preferably 8 to 20 carbon atoms), such as myristoyl pullulan and ulvan, may be mentioned.

[0231] According to a particular embodiment, the one or more polymers b) of the present invention represent a combination of polymers (b), one of which is a polysaccharide or a salt thereof, its α or β anomer, its optical isomer in L- or D-configuration, and its solvate, such as its hydrate.

[0232] According to a particular embodiment, the one or more polymers b) of the present invention represent a single polysaccharide or a salt thereof, its α or β anomer, its optical isomer in L-form or D-configuration, and its solvate, such as its hydrate.

[0233] In particular, the non-aromatic cyclic polymer b) is selected from anionic polysaccharides and from sulfated polysaccharides, phosphated polysaccharides, and polysaccharide carboxylates.

[0234] The polysaccharide may optionally be acetylated. The degree of acetylation can range from 1 wt% to 40 wt% (weight content of acetyl units relative to the total weight of the polymer).

[0235] According to a preferred embodiment, the polymer b) is selected from polysaccharides having a weight average molecular weight in the range of 1000 to 20000000 Da, preferably 5000 to 10000000 Da, even more preferably 7000 to 3000000 Da.

[0236] Among the phosphated polysaccharides, phosphate starches, such as hydroxypropyl corn diphosphate starch, may be mentioned.

[0237] Among these sulfated polysaccharides, urban, dextran sulfate, carrageenan, and especially lambda-carrageenan, fucoidan, urban, dextran sulfate, and combinations thereof may be mentioned.

[0238] Advantageously, the degree of polysaccharide sulfation can be in the range of 1% to 90% by weight relative to the weight of one or more polysaccharides. Preferably, this degree of sulfation can be in the range of 2% to 85% by weight.

[0239] In particular, the sulfated polysaccharide b) may also be selected from ulvans, which are sulfated polysaccharides derived from algae, especially red algae or green algae.

[0240] The term "urban" can be derived from numerous species of the genus *ulva*, including *Ulva lactuca*, *Ulva rigida*, *Ulva armoricana*, *Ulva rotundata*, and *Ulvaria obscura*, as well as several species of the genus *enteromorphs*, particularly *Enteromorpha compressa*, *Enteromorpha intestinalis*, and *Enteromorpha ramulosa*.

[0241] Urban mainly contains rhamnose, glucuronic acid, glucose, galactose, and xylose, as well as sulfate groups. Urban may also contain galacturonic acid, idronic acid, and mannose in varying amounts.

[0242] Urban generally has a polysaccharide sulfated degree in the range of 1% to 30% by weight, more preferably 10% to 20% by weight, relative to the weight of the polysaccharide.

[0243] The relative proportion of sugars in urban varies depending on the location, species, and time of harvesting of urban. For the production of urban by extraction from urban, the extraction process described in Carbohydrate Research 274 (1995) 251-261 or Hydrobiolologia 326 / 327;473-480, 1996 may be referenced.

[0244] According to a particular embodiment, the one or more polymers b) are at least one urban or comprise at least one urban.

[0245] In particular, the sulfated polysaccharide b) may also be selected from dextran sulfate derived from dextran.

[0246] Dextran is a complex branched glucan (a polysaccharide derived from glucose condensation) and originally originates from wine. IUPAC defines dextran as "a branched poly-α-D-glucoside of microbial origin, whose glycosidic bonds are mainly C-1→C-6." The length of the dextran chain varies (3 to 2000 kilodaltons).

[0247] The main polymer chain is composed of α-1,6 glycosidic bonds between glucose monomers and has branching via α-1,3 bonds. This characteristic branching structure distinguishes dextran from dextrin, which is a linear glucose polymer linked by α-1,4 or α-1,6 bonds.

[0248] In particular, dextran sulfate, sold by the company PK Chemicals under the trade name "Dextran Sulfate 10 Sodium Salt CG," may be used.

[0249] Among the polysaccharide carboxylates (b), alginates may be mentioned.

[0250] Alginates are obtained from brown algae, such as kelp or wakame. The alginate is preferably sodium alginate or calcium alginate.

[0251] Alginates are polysaccharides derived from mannuronate or mannuronic acid (some of which are optionally acetylated) and guluronate or guluronic acid. The linkage is beta-1-4 type.

[0252] According to a particular embodiment, the one or more polymers b) of the present invention are selected from nonionic polymers, particularly nonionic polysaccharides.

[0253] Examples of nonionic polysaccharides include starch and pullulan, and pullulan in particular.

[0254] According to one embodiment, the one or more polymers b) according to the present invention are nonionic polymers, particularly nonionic polysaccharides, more preferably polysaccharides, wherein the polysaccharide may be modified in the presence of at least one aliphatic, cyclic or acyclic, linear or branched, saturated or unsaturated, aromatic or non-aromatic hydrocarbon chain, the hydrocarbon chain comprising 2 to 30 carbon atoms, a) halogen atoms, e.g., chlorine or bromine atoms, b) (hetero)aryl, e.g., phenyl or furyl, c) (hetero)cycloalkyl, e.g., anhydride, epoxide or dithiolane, d) RX (wherein R is i) cycloalkyl, e.g., cyclohexyl, and / or ii) (di)alkylamino and / or optionally, one or more heteroatoms, or a') heteroatoms, e.g., O, S, N(Ra) and Si(Rb)(Rc), b') S(O)r, (thio) It may be substituted with one or more atoms or groups from carbonyl, or a combination of c')a') and b'), for example, a group selected from (thio)esters, (thio)amides, (thio)ureas, and sulfonamides, where r is 1 or 2, Ra represents a hydrogen atom or a (C1-C4) alkyl or aryl(C1-C4) alkyl group, for example benzyl, preferably Ra represents a hydrogen atom, and Rb and Rc may be the same or different, representing a (C1-C4) alkyl or (C1-C4) alkoxy group.

[0255] Modified polysaccharides may include, in particular, natural gums that have been modified physically, chemically, or enzymatically, such as those obtained from secretions of trees or shrubs, algae, seeds or tubers, fungi, bacteria, animal organisms, or other living organisms.

[0256] In particular, this natural gum is Gum arabic (a branched polysaccharide composed of galactose, arabinose, rhamnose, and glucuronic acid); Ghatti gum (polymers derived from arabinose, galactose, mannose, xylose, and glucuronic acid); Karaya gum (polymers derived from galacturonic acid, galactose, rhamnose, and glucuronic acid); Tragacanth gum (polymer of galacturonic acid, galactose, fucose, xylose, and arabinose); Agar (polymer derived from galactose and anhydrous galactose); Alginate (polymer of mannuronic acid and glucuronic acid); Carrageenan and furcerellans (polymers of galactose sulfate and anhydrous galactose sulfate); Guar gum (a polymer of mannose and galactose); Locust bean gum (a polymer of mannose and galactose); Fenugreek gum (a polymer of mannose and galactose); Tamarind gum (a polymer of galactose, xylose, and glucose); Konjac gum (a polymer of glucose and mannose); Xanthan gum (polymer of glucose, mannose acetate, mannose / pyruvic acid, and glucuronic acid) or dehydroxanthan gum; Gellan gum (a polymer of partially acylated glucose, rhamnose, and glucuronic acid); Scleroglucan gum (glucose polymer); Cellulose (glucose polymer); Starch (glucose polymer); Inulin; and, pectin It can be selected from the following.

[0257] In particular, these modified polysaccharides are derived from i) gum arabic; ii) ghatti gum; iii) karaya gum; iv) tragacanth gum; v) agar; vi) alginate; vii) carrageenan and furcereran; viiii) guar gum; ix) locust bean gum; x) fenugreek gum; xi) tamarind gum; xii) konjac gum; xiii) xanthan gum or dehydroxanthan gum; xiv) gellan gum; xv) scleroglucan gum; xvi) cellulose; xvii) starch; xviii) inulin; and xix) pectin.

[0258] The botanical origin of starch molecules (xvii) can be cereals or tubers. Therefore, the starch can be selected from, for example, maize starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch, and pea starch.

[0259] The starch may be modified chemically or physically, and in particular, by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, and heat treatment.

[0260] Nonionic modified polysaccharides may be modified physically or chemically. A particularly noteworthy physical treatment is temperature.

[0261] The chemical processes that may be mentioned include esterification, etherification, amidation, oxidation, metathesis, and addition reactions.

[0262] According to a particular embodiment, the modified polysaccharide is a polysaccharide ether known as an alkyl polysaccharide, wherein the alkyl portion comprises 2 to 30 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.

[0263] Preferably, the alkyl polysaccharides according to the present invention are derived from cellulose, guar, or a combination thereof.

[0264] According to a particular embodiment, the modified polysaccharide is alkylcellulose, and its linear or branched alkyl residues contain 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.

[0265] The alkylcellulose is a cellulose alkyl ether containing a chain formed from β-anhydroglucose units linked together via acetal bonds. Each anhydroglucose unit has three substitutable hydroxyl groups, some or all of which may react according to the following reactions: Cell-OM+R-Hal → Cell-OR+MHal Here, Hal represents a halogen atom, for example Cl; M represents a cationic counterion, for example alkali metal Na or alkali metal K, or alkaline earth metal, preferably alkali metal, for example Na; Cell represents a polysaccharide moiety, for example cellulose, where R represents a linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 2 to 3 carbon atoms, for example a methyl group or an ethyl group; and MHal represents the resulting salt, for example sodium chloride.

[0266] Advantageously, the alkylcellulose is selected from ethylcellulose and propylcellulose.

[0267] According to a particular embodiment, the polysaccharide ether is a guar gum (viii) modified by substituting hydroxyl hydrogens with alkyl guar, in other words, linear or branched alkyl groups containing 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, for example 2 carbon atoms.

[0268] The alkyl guar polymer used in accordance with the present invention is preferably ethyl guar.

[0269] Ethyl guar is known by the INCI name C1-C5 alkylgalactomannan.

[0270] Alkylated guar gums (having C1-C6 alkyl groups) include ethyl guar and are described in particular in European Patent Application EP708114 and document RD9537807 (October 1995), as are their manufacturing methods.

[0271] According to a particular embodiment, the modified polysaccharide is a polysaccharide ester, and in particular an ester obtained by the reaction of at least one polysaccharide, such as dextrin, with at least one saturated or unsaturated linear or branched acid containing 2 to 30 carbon atoms, particularly 10 to 30 carbon atoms.

[0272] According to a particular embodiment of the present invention, one or more modified polysaccharides are selected from polysaccharide monoalkyl esters or polysaccharide polyalkyl esters.

[0273] Among the monoalkyl or polyalkyl esters of sugars or polysaccharides suitable for use in the present invention, alkyl or polyalkyl esters of dextrin or inulin may be mentioned.

[0274] In particular, it is a monoester or polyester of dextrin (derived from starch xvii) and at least one fatty acid (e.g., RC(O)-OH), and in particular corresponds to the following formula (XVIII): [ka] Here, in equation (XVIII), n is an integer greater than or equal to 2, preferably in the range of 3 to 200, particularly in the range of 20 to 150, and especially in the range of 25 to 50. R1, R2, and R3 may be the same or different, and are selected from hydrogen atoms or acyl groups (RC(O)-), where the R group is a linear or branched saturated or unsaturated hydrocarbon group containing 7 to 29, particularly 7 to 21, especially 11 to 19, more preferably 13 to 17, or 15 carbon atoms, where at least one of R1, R2, or R3 is not a hydrogen atom.

[0275] In particular, R1, R2, and R3 represent hydrogen atoms or acyl groups (RC(O)-), where R is a hydrocarbon part as defined above, and at least two of parts R1, R2, or R3 are not hydrogen atoms.

[0276] All of the parts R1, R2, or R3 may represent the same or different acyl groups (RC(O)), and the acyl groups are in particular the same.

[0277] In particular, the aforementioned n is advantageously in the range of 25 to 50, and especially equal to 38 in the general formula of the sugar ester that can be used in the present invention.

[0278] In particular, when parts R1, R2, or R3, which may be the same or different, represent an acyl group (RC(O)) derived from an aliphatic carboxylic acid RC(O)OH, the carboxylic acid is preferably caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, isobutyric acid, isovaleric acid, 2-ethylbutyric acid, ethylmethylacetic acid, isoheptanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, and Selected from sotridecanoic acid, isomyristateic acid, isopalmitic acid, isostearic acid, isoarachidonic acid, isohexanoic acid, 10-hydroxy-2-decenoic acid, dodecenoic acid, tetradecenoic acid, myristoleic acid, hexadecenoic acid, palmitoleic acid, oleic acid, elaidic acid, asclepic acid, gondoleic acid, eicosenoic acid, sorbic acid, linoleic acid, linolenic acid, punicic acid, stearidonic acid, arachidonic acid, stearolic acid, and combinations thereof.

[0279] Preferably, at least one dextrin palmitate is used as the fatty acid ester of dextrin. This ester may be used alone or in a mixture with other esters.

[0280] Preferably, the fatty acid ester of dextrin has a degree of substitution of 2.5 or less, particularly in the range of 1.5 to 2.5, preferably in the range of 2 to 2.5, based on one glucose unit. The weight-average molecular weight of the dextrin ester can be particularly 10,000 to 150,000 Da, particularly 12,000 to 100,000 Da, and even more so 15,000 to 80,000 Da.

[0281] Preferably, one or more modified polysaccharides of the present invention are dextrin esters, more preferably dextrin palmitate.

[0282] Dextrin esters, especially dextrin palmitate, are produced by Chiba Flour Milling Co., Ltd. under the Rheopearl KL2 brand. 登録商標 MKL2 登録商標 , TL 登録商標 or KL 登録商標 It is commercially available under the name of [name].

[0283] According to a particular embodiment, the modified polysaccharide is a modified dextrin, preferably a dextrin ester, more preferably a saturated or unsaturated, linear or branched C2 of dextrin. 12 ~C 24 It is a fatty acid ester.

[0284] Preferably, the dextrin ester is saturated or unsaturated, linear or branched C 14 ~C 24 The esters are selected from fatty acid esters, such as myristic acid, palmitic acid, or combinations thereof.

[0285] According to a particular embodiment, the dextrin ester is dextrin palmitate, for example, Rheopearl KL2 sold by Chiba Flour Milling Co., Ltd. 登録商標and Rheopearl TL2 登録商標 , as well as dextrin myristate, for example, Rheopearl MKL2 by Chiba Flour Milling Co., Ltd. 登録商標 Products sold under the reference name of TT2 登録商標 Select from dextrin palmitate / ethylhexanoate sold under the reference name , dextrin palmitate / hexyldecanoate sold under the reference name Rheopearl WX, or a combination thereof.

[0286] According to a particular embodiment, the modified polysaccharide is modified inulin, preferably an inulin ester, and more preferably inulin and saturated or unsaturated, linear or branched C 12 ~C 24 It is an ester with a fatty acid.

[0287] Preferably, the inulin ester is saturated or unsaturated, linear or branched C 14 ~C 24 The fatty acids are selected from esters of myristic acid, palmitic acid, or stearic acid, preferably stearic acid, or a combination thereof.

[0288] According to a particular embodiment, the inulin ester is stearoyl inulin, for example, Rheopearl ISK2, sold by Chiba Flour Milling Co., Ltd. 登録商標 and Rheopearl ISL2 登録商標 It is something under the name of, or a combination thereof.

[0289] According to one embodiment, the modified polysaccharide is modified cellulose, preferably a cellulose ester, more preferably cellulose and saturated or unsaturated, linear or branched C2-C2. 24 It is an ester with an acid.

[0290] Preferably, the cellulose ester is saturated or unsaturated, linear or branched C2-C2. 10Preferably, acids of C2-C6, particularly C2-C4, are selected from, for example, acetic acid, butyric acid, or a combination thereof.

[0291] According to a particular embodiment, the cellulose ester is cellulose acetate butyrate, for example, Eastman Cellulose Acetate Butyrate, sold by Eastman Chemical. 登録商標 It is under the name of [name].

[0292] According to a particular embodiment, the one or more polymers b) are nonionic polymers, particularly nonionic polysaccharides, more preferably hydrophobic chains, such as alkylcarbamate groups, particularly C8-C 18 Selected from inulin modified with alkylcarbamates, more preferably laurylcarbamates.

[0293] Examples of such compounds include, among others, the product marketed by the company Creachem under the name Inutec SL1.

[0294] Among these polysaccharide esters, pullulan esters may also be mentioned. Pullulan is a polysaccharide composed of maltotriose units.

[0295] According to one embodiment, the modified polysaccharide is a polysaccharide ester. The term "polysaccharide ester" means a polysaccharide in which at least one hydroxyl group is esterified with an acid to form an ester group -OC(O)-R or -C(O)-OR (wherein R refers to a saturated or unsaturated portion having 2 to 30 carbon atoms, particularly 11 to 19 carbon atoms, preferably 12 to 17 carbon atoms, for example 13 carbon atoms).

[0296] In particular, the polysaccharide ester is myristoyl pullulan.

[0297] According to a particular embodiment, the one or more polymers b) comprises at least one cationic modified polysaccharide.

[0298] Preferably, the chemical or physical treatment to obtain at least one cationic group is applied to guar gum, locust bean gum, starch and cellulose.

[0299] The cationic group can be of primary, secondary, tertiary or quaternary amine type, preferably quaternary, and contains an aliphatic chain of C6 - C 30 and contains an aliphatic chain of C6 - C.

[0300] According to certain embodiments, one or more modified polysaccharides b) are selected from quaternized (poly) hydroxyethyl cellulose modified with a group containing at least one aliphatic chain (or fatty chain), for example, an alkyl group, an arylalkyl group, an alkylaryl group or a combination thereof containing at least 8 carbon atoms.

[0301] The alkyl moiety possessed by the quaternized cellulose or hydroxyethyl cellulose preferably contains 8 - 30 carbon atoms.

[0302] The aryl moiety preferably refers to a phenyl group, a benzyl group, a naphthyl group, or an anthryl group. Examples of quaternized alkyl hydroxyethyl cellulose containing a C8 - C 30 fatty chain can be products sold by the company Dow Corning, Quatrisoft LM 200 登録商標 , Quatrisoft LM-X 529-18-A 登録商標 , Quatrisoft LM-X 529-18-B 登録商標 (C 12 alkyl) and Quatrisoft LM-X 529-8 登録商標 (C 18 alkyl), as well as products sold by the company Croda, Crodacel QM 登録商標 , Crodacel QL 登録商標 (C 12 alkyl) and Crodacel QS 登録商標 (C 18(alkyl), as well as the product sold by the company Dow Corning, Softcat SL 100 登録商標 are included.

[0303] According to certain embodiments, one or more of the modified polysaccharides b) are selected from guar gums modified with C1-C 20 (poly)hydroxyalkylammonium groups, preferably C1-C6 (poly)hydroxyalkyl groups.

[0304] By way of example, among others, mention may be made of the halide groups of hydroxymethyltrimonium, hydroxyethyltrimonium, hydroxypropyltrimonium, hydroxybutyltrimonium, preferably the halide of hydroxypropyltrimonium, preferably chloride.

[0305] Such cationic guar gums modified with hydroxyalkylammonium groups are, for example, sold by the company Solvay under the names Cationic Jaguar 登録商標 C-14S Guar Hydroxypropyltrimonium Chloride,F Jaguar 登録商標 C-13S Guar Hydroxypropyltrimonium Chloride,F Jaguar 登録商標 C-17 Guar Hydroxypropyltrimonium Chloride,Jaguar 登録商標 Excel Guar Hydroxypropyltrimonium Chloride,Jaguar 登録商標 C-500 STD Guar Hydroxypropyltrimonium Chloride,Jaguar 登録商標 C-162 Hydroxypropyl Guar Hydroxypropyltrimonium Chloride,Jaguar 登録商標 Optima Guar Hydroxypropyltrimonium Chloride, and Jaguar 登録商標It is sold under the trade name LS Hydroxypropyl Guar Hydroxypropyltrimonium Chloride.

[0306] According to a particular embodiment, the cationic non-aromatic cyclic polymer b) is in particular a polysaccharide having an amine group, such as chitosan.

[0307] Preferably, the amine group is a primary, secondary, or tertiary amine, preferably a primary amine.

[0308] The term "polysaccharides having an amine group" also means their organic or inorganic salts, their α or β anomers, their L- or D-configured optical isomers, and their solvates, such as their hydrates.

[0309] According to a particular embodiment, one or more polysaccharides having one or more amine groups are selected from those having C5-C7 sugar units, and organic or inorganic salts thereof, α or β anomers thereof, L- or D-configured optical isomers thereof, and solvates thereof, such as hydrates thereof.

[0310] More specifically, the one or more polysaccharides having one or more amine groups contain one or more C6 sugar units having one or more amine groups. These one or more polysaccharides having amine groups are referred to as polyhexosamines.

[0311] According to a particular embodiment, the sugar units of a polysaccharide having one or more amine groups are in a β (beta) anomeric configuration and / or a D configuration.

[0312] According to a particular embodiment, the sugar units of a polysaccharide having one or more amine groups are bonded between the C1 carbon atom of one sugar unit and the C4 carbon atom of the other sugar unit (denoted as (1→4)), for example, a polysaccharide having the amine group of formula (B) below, and its organic or inorganic salt, its α or β anomer, its L- or D-configured optical isomer, and its solvate, for example, its hydrate: [ka] Here, in equation (B), Part of each sugar unit R a , R b and R c They may be the same or they may be different; n is an integer greater than or equal to 2, and in particular, between 3 and 3000 (including both ends); R a , R b and R c These may be the same or different, and represent i) a hydroxyl group, ii) a (C1-C4) alkoxy group (wherein the alkyl group may be optionally substituted, in particular by one or more hydroxyl groups), iii) a carboxyl group, and iv) an NR1R2 group (wherein R1 and R2 are as previously defined, in particular R1 and R2 are selected from a hydrogen atom and -C(O)-R'1 (wherein R'1 is as previously defined)), preferably R1 and R2 represent i) a hydrogen atom or ii) -C(O)-R'1 (wherein R'1 represents a (C1-C4) alkyl group, for example methyl). Here, a portion R of at least one sugar unit a , R b or R c At least one of them represents an NR1R2 group, and at least one of the sugar units is R a , R b or R c At least one of them represents an NH2 group; preferably, at least one sugar unit R a The NR1R2 group (where R1 represents a hydrogen atom, and R2 is selected from i) a hydrogen atom, or ii) a -C(O)-R'1 group, R b and R c The symbol represents a hydroxyl group, where at least one of the NR1R2 groups of at least one sugar unit represents an NH2 group.

[0313] More specifically, the present invention comprises one or more polysaccharides having one or more amine groups, those of the following formula (B1), their organic or inorganic salts, their α or β anomers, their L- or D-configured optical isomers, and their solvates, such as their hydrates. [ka] Here, in equation (B1), R' represents a hydrogen atom or a (C1-C4) alkylcarbonyl group, such as an acetyl group CH3-C(O)-; R'' represents a hydrogen atom, or an (C1-C4) alkyl group that may optionally be substituted with a carboxyl group, such as -CH(CO2H)-CH3; n is an integer greater than or equal to 2, especially between 3 and 3000 (including both ends); Here, in the polysaccharide (B1), at least one has an NH2 amino group, and at least one other sugar unit has at least one N(H)-R' (wherein R' represents a (C1-C4) alkylcarbonyl group, for example, acetyl CH3-C(O)-).

[0314] Preferably, the sugar unit of formula (B) or formula (B1) is in the D configuration and is also referred to as D-glucopyran.

[0315] In particular, the unit of formula (B) or formula (B1) is a β (beta) anomeric configuration.

[0316] According to a particular embodiment, the polysaccharide of the present invention is selected from the compound of formula (B2) below, its organic or inorganic salt, and its solvate, for example, its hydrate. [ka] Here, in equation (B2), R a , R b and R c This is as defined in (B) above; Part of each sugar unit R a , R b and Rc Each of them may be the same or different; n is an integer greater than or equal to 2, particularly in the range of 3 to 3000 (including both ends), more preferably in the range of 5 to 2500, and more preferably in the range of 10 to 2300; Here, in the polysaccharide (B2), a portion R of at least one sugar unit a , R b or R c At least one of them represents an NR1R2 group, and at least one of the NR1R2 groups of the sugar unit represents an NH2 group; Preferably, at least one sugar unit is R representing aminoNH2. a It has a group and at least one other sugar unit represents -N(H)-R' (wherein R' represents a (C1-C4) alkylcarbonyl group, e.g., acetyl CH3-C(O)-). a It has a base.

[0317] Preferably, the one or more polysaccharides having one or more amine groups are selected from chitin, chitosan and their derivatives, and are preferably chitosan.

[0318] More specifically, one or more polysaccharides having one or more amine groups are selected from those of the following formula (B3), their organic or inorganic salts, and their solvates, such as their hydrates: [ka] Here, in equation (B3), R1 and R2 are as defined in formula (B), formula (B1), or formula (B2) above; and, n is an integer greater than or equal to 2, particularly 3 to 3000 (including both ends), more preferably 5 to 2500, and more preferably 10 to 2300; Here, in the polysaccharide of formula (B3), at least one sugar unit has an amino group NH2, and at least one other sugar unit has N(H)-R' (wherein R' represents a (C1-C4) alkylcarbonyl group, for example, acetyl CH3-C(O)-).

[0319] More specifically, the one or more polysaccharides having one or more amine groups of the present invention are selected from chitosan of the following formula (B4), its organic or inorganic salt, and its solvate, for example, its hydrate: [ka] Here, in equation (B4), R'1 represents a (C1-C4) alkyl group, such as methyl; n is an integer greater than or equal to 2, especially between 3 and 3000 (including both ends); p is greater than 0 and in the range up to 0.5, preferably 0.05 to 0.3, better 0.1 to 0.20, for example 0.15, where m + p is equal to 1; Here, in chitosan, at least one sugar unit has an amino group NH2, and at least one other sugar unit has an N(H)-R'1 group (wherein R' represents a (C1-C4) alkylcarbonyl group, for example, acetyl CH3-C(O)-).

[0320] For example, when m=0.7 and p=0.3, this means that 70% of the amine groups are free (unsubstituted) and 30% of the amino groups are N-(C1~C4) alkylcarbonyl groups, particularly N-acetyl groups, corresponding to the chitosan polymer of the following formula: [ka] Here, n is as previously defined.

[0321] In particular, the polysaccharide having one or more amine groups of the present invention is selected from chitosan chlorinated with an organic acid, preferably chlorinated with a monocarboxylic acid defined by formula (I) below, or with a polycarboxylic acid defined by formula (II) below, and more preferably chlorinated with a carboxylic acid of formula (I), such as lactic acid.

[0322] Formula (I) is RC(O)-OH(wherein (R is a (hetero)aryl group, e.g., phenyl, (hetero)aryl(C1-C4)alkyl group, e.g., benzyl, or (C1-C 30 ) Alkyl alkyl groups, or unsaturated C2-C 30 Represented by a portion (i.e., including at least one ethylene unsaturated bond, preferably one ethylene unsaturated bond), where the alkyl group or unsaturated C2-C 30 The portion may be optionally interrupted and / or optionally substituted, preferably substituted with one or more hydroxyl groups, but not necessarily substituted with one or more amino portions, R preferably represents an optionally interrupted and / or optionally substituted with one, two or three hydroxyl groups (C1-C6) alkyl group, preferably R represents a (C1-C4) alkyl group, such as methyl or ethyl, in particular the organic monocarboxylic acid (I) is selected from acetic acid, glycolic acid and lactic acid, preferably from acetic acid and lactic acid, and the polycarboxylic acid is of the following formula (II): [ka] In formula (II), A represents a saturated or unsaturated, cyclic or acyclic, aromatic or non-aromatic polyvalent hydrocarbon-based group containing 1 to 30 carbon atoms, the polyvalent hydrocarbon-based group may optionally be interrupted by one or more heteroatoms, such as oxygen, and / or optionally substituted with one or more hydroxyl groups, in particular, where t represents an integer from 1 to 5 (inclusive).

[0323] Preferably, A represents a divalent (C1-C6) alkylene group that is not substituted with at least one amino moiety, although it may optionally be substituted with one or more hydroxyl groups, where t is 1, 2, or 3.

[0324] Preferably, the polycarboxylic acid of formula (II) is selected from tartaric acid, succinic acid, fumaric acid and citric acid (more preferably tartaric acid, succinic acid, fumaric acid and citric acid), and amino acids that have more carboxylic acid moieties than amino groups (e.g., gamma-carboxyglutamic acid, aspartic acid, glutamic acid, especially gamma-carboxyglutamic acid; especially salts of monocarboxylic acids other than pyrrolidone carboxylic acid, ethoxylated stearic acid and linoleic acid of 100OE and 500OE).

[0325] According to a particular embodiment, one or more polysaccharides having one or more amine groups are selected from a mixture of one or more polysaccharides having one or more amine groups, one of which is chitosan or its organic or inorganic salt, preferably its organic salt, and more preferably lactic acid, its α or β anomer, its L- or D-configured optical isomer, and its solvates, such as its hydrate.

[0326] According to a particular embodiment, the one or more polysaccharides having one or more amine groups is a single polysaccharide having one or more amine groups, and is selected in particular from chitosan or a mixture of its organic or inorganic salts, more preferably its organic salt, more preferably its lactate, its α or β anomer, L- or D-configured optical isomer, and its solvates, such as its hydrate.

[0327] According to a particular embodiment, the one or more polysaccharides having one or more amine groups is a single polysaccharide having one or more amine groups, and is particularly selected from chitosan or its organic or inorganic salt, more preferably its organic salt, preferably its lactate, its α or β anomer, its L- or D- configuration optical isomer, and its solvates, such as its hydrate.

[0328] According to one embodiment, the acyclic polymer b) is selected from nonionic polymers. In particular, polymer b) may be selected from alkyl esters or ethers of polyols (e.g., glycerol). A possible example of a glycerol ester is polyglyceryl isostearate, e.g., Isolan GI 34 by Evonik Company. 登録商標 This includes products sold under the name of [product name]. It also includes polyoxyalkylene, more preferably polyoxyethylene and / or polyoxypropylene, fatty acid esters of glycerol (e.g., stearate ester of polyethylene glycol, called INCI name PEG-100 stearate), and polyoxyalkylene, particularly polyoxyethylene and / or polyoxypropylene, fatty acid esters that may optionally be combined with glycerol fatty acid esters (e.g., PEG-100 stearate / glyceryl stearate mixtures).

[0329] The nonionic acyclic polymer (b) may also refer to oxyalkylene, particularly oxyethylene, and / or oxypropylene, fatty alcohol ethers.

[0330] According to another embodiment, the nonionic acyclic polymer b) may be selected from polyesters, particularly polyhydroxy acids, especially C8-C30 polyhydroxy acids, such as polyhydroxystearic acid.

[0331] According to one embodiment, the nonionic acyclic polymer b) may be selected from a (co)polymer P having at least one unit of formula (II) below and optionally at least one unit of formula (III) below. [ka] Here, in equation (II), q represents an integer greater than or equal to 2, and R aR represents a hydrogen atom or a linear or branched (C1-C4) alkyl group. Preferably, a This represents a hydrogen atom. [ka] Here, in equation (III), t represents an integer greater than or equal to 2; R represents a linear or branched, saturated or unsaturated, aromatic or non-aromatic, cyclic or acyclic hydrocarbon chain containing 1 to 10 carbon atoms, preferably R represents a (C1-C6) alkyl group, particularly a methyl group; and, R a R represents a hydrogen atom or a linear or branched (C1-C4) alkyl group, preferably R a represents a hydrogen atom; Preferably, the one or more (co)polymers P are copolymers.

[0332] According to a preferred embodiment, the one or more (co)polymers P comprise at least one unit of formula (II) and at least one unit of formula (III).

[0333] According to a preferred embodiment, the one or more (co)polymers P have a mass-average molecular weight in the range of 1,000 g / mol to 1,000,000 g / mol, preferably 5,000 g / mol to 500,000 g / mol, and more preferably 10,000 g / mol to 300,000 g / mol.

[0334] According to a particular embodiment, the one or more (co)polymers P defined above refer specifically to polyvinyl alcohol (PVA).

[0335] In particular, the one or more (co)polymers P may be partially or completely hydrolyzed polyvinyl alcohol (PVA), in particular the products sold by Kuraray Ltd. under the reference name Kuraray Poval, in particular the POVAL series, or products sold by Sigma-Aldrich (see, for example, https: / / www.sigmaaldrich.com / FR / en / search / poly(vinyl-alcohol)?focus=products&page=1&perpage=30&sort=relevance&term=poly%28vinyl%20alcohol%29&type=product).

[0336] That is especially true, Average molecular weight M between 89,000 and 98,000 w It contains poly(vinyl alcohol) that has been more than 99% hydrolyzed; Average molecular weight M between 30,000 and 70,000 w It contains 87% to 90% hydrolyzed poly(vinyl alcohol); Average molecular weight M between 13,000 and 23,000 w It contains 87% to 89% hydrolyzed poly(vinyl alcohol); Average molecular weight M of 9000-10000 w It contains 80% hydrolyzed poly(vinyl alcohol); Average molecular weight M: 146,000-186,000 w It contains poly(vinyl alcohol) that has been more than 99% hydrolyzed; Average molecular weight M between 85,000 and 124,000 w It contains poly(vinyl alcohol) that has been more than 99% hydrolyzed; Average molecular weight M between 31,000 and 50,000 w It contains 98% to 99% hydrolyzed poly(vinyl alcohol); Average molecular weight M between 31,000 and 50,000 w It contains 87% to 89% hydrolyzed poly(vinyl alcohol); Average molecular weight M between 85,000 and 124,000 wIt contains 87% to 89% hydrolyzed poly(vinyl alcohol); Average molecular weight M: 146,000-186,000 w It contains 87% to 89% hydrolyzed poly(vinyl alcohol); Average molecular weight M between 13,000 and 23,000 w It contains 98% hydrolyzed poly(vinyl alcohol); Average molecular weight M of 130,000 w It contains 99% hydrolyzed poly(vinyl alcohol); Completely hydrolyzed poly(vinyl alcohol); 4-88 Emprove by Sigma-Aldrich 登録商標 Poly(vinyl alcohol) sold under the reference name Essential; 8-88 Emprove by Sigma-Aldrich 登録商標 Essential (CAS No. 9002-89-5, M w Poly(vinyl alcohol) sold under the reference name (which is equal to 67000); or, 40-88 Emprove by Sigma-Aldrich 登録商標 Poly(vinyl alcohol) sold under the reference name Essential It can be a poly(vinyl alcohol) selected from among the following.

[0337] Preferably, the one or more (co)polymers according to the present invention may be prepared from partially hydrolyzed poly(vinyl alcohol), more preferably 88% hydrolyzed.

[0338] In particular, this is the 8-88 Emprove by the company Sigma-Aldrich. 登録商標 It may be polyvinyl alcohol sold under the reference name Essential.

[0339] According to a particular embodiment, the one or more polymers b) are selected from acyclic polymers, preferably from anionic acyclic polymers.

[0340] For example, at least one C8~C 30 Preferably C8~C 24 , polymers b) selected from amino acids modified with a hydrocarbon-based chain, and salts thereof, in particular acyl glutamic acid (INCI name: acyl glutamate), for example acyl glutamate, in particular stearoyl glutamic acid (INCI name: sodium stearoyl glutamate), more preferably sodium stearoyl glutamate (INCI name: sodium stearoyl glutamate).

[0341] Such compounds are marketed by Ajinomoto Co., Inc. under the names Amisoft, particularly Amisoft CA, Amisoft LA, Amisoft HS 11 PF, Amisoft MK-11, Amisoft LK-11, and Amisoft CK-11, or by the company Cognis under the name Eumulgin SG.

[0342] According to a particular embodiment, the one or more polymers b) are selected from polyamino and hydrocarbon acyclic polymers, and do not contain any silicon atoms.

[0343] In particular, the polyamino polymer is derived from a diamino polymer, more preferably from a polyetherdiamine, and especially from a polymer of the formula H2N-ALK-O-[ALK'-O] mPolyether diamines of the form -ALK''-NH2 (wherein ALK, ALK', and ALK'' may be the same or different, representing linear or branched (C1-C6) alkylene groups, and m represents an integer of 0 or more), such as 4,7,10-trioxa-1,13-tridecanediamine, or compounds known by the reference name Jeffamine from Huntsman Company, more preferably α,ω-diaminopolyethylene glycol and / or polypropylene glycol (having amine functional groups at the ends of the chain), such as products marketed under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000, and ED-2003.

[0344] In particular, one or more of the polyamino polymers may be selected from triamino polymers, i.e., triamino polymers comprising three primary and / or secondary amine groups, preferably primary (NH2).

[0345] More specifically, they are selected from polyethertriamines, in particular from polyethertriamines of ALK'''[(O-ALK')m-NH2]3 (wherein ALK' is as previously defined, and ALK''' represents a linear or branched trivalent (C1-C6) alkylene group, and m represents an integer of 0 or more).

[0346] Triamino compounds, or (poly)amino compounds, include in particular polyethertriamines, especially α,ω-diaminopolyethylene glycol and / or polypropylene glycol (having amine functional groups at the ends of the chain), such as the product marketed under the name Jeffamine T-403.

[0347] According to a particular embodiment, one or more (poly)amino compounds comprise more than three primary and / or secondary amine groups, preferably primary (NH2).

[0348] In particular, one or more of the (poly)amino compounds are selected from poly(meth)acrylates or poly(meth)acrylamides having primary or secondary amine groups in their side chains, and more preferably from poly(3-aminopropyl)methacrylamide and poly(2-aminoethyl)methacrylate.

[0349] According to a particular embodiment, one or more polyamino compounds are Poly((C2~C5)alkyleneimines), preferably polyethyleneimines and polypropyleneimines, particularly poly(ethyleneimines), especially those sold by Aldrich Chemical Company under the reference name 408700, or those sold by Aldrich Chemical Company under the reference name 408727 (e.g., MW=25000), or those sold by BASF under the trade name Lupasol (molecular weight 1200~30000). Poly(allylamine), in particular, a product sold by Aldrich Chemical under the reference name 479136, Polyvinylamines and their copolymers, in particular copolymers with vinylamides, especially vinylamine / vinylformamide copolymers, Polyamino acids containing an NH2 group, such as polylysine, in particular, products sold by JNC Corporation (formerly Chisso Corporation), Aminodextran, in particular, is a product sold by the company CarboMer Inc. Aminopolyvinyl alcohol, in particular, products sold by the company CarboMer Inc. Acrylamide (C1-C6) alkylamine copolymers, particularly those based on acrylamidopropylamine, and those combinations Selected from.

[0350] As amino polymers, α,ω-diaminopolytetrahydrofuran (or polytetramethylene glycol) and α,ω-diaminopolybutadiene may also be mentioned.

[0351] According to a particular embodiment, the (poly)amino compound is selected from hyperbranched polymers containing at least one amino group, and dendrimers having at least one amino group, particularly polyamidoamine PAMAM dendrimers having an ethylenediamine core and terminal amine functional groups.

[0352] According to a particular embodiment, the one or more polymers b) are selected from polyamino acids, preferably from proteins.

[0353] Preferably, the protein is of plant origin. As an example of polymer b) selected from plant proteins, soy protein may be mentioned.

[0354] The one or more acyclic polymers b) may be anionic, cationic, or nonionic, preferably anionic, more preferably anionic, and in particular have a carboxyl group, a carboxylate group, a sulfate group, a sulfonic acid group, a sulfonate group, a phosphate group, a phosphoric acid group, or a phosphonate group, and are preferably selected from carboxylates and carboxylic acids.

[0355] According to a particular embodiment, the acyclic polymer b) is anionic and, in particular, has a carboxyl group or a carboxylate group of an alkali metal or alkaline earth metal, such as sodium, and is selected from homopolymers or copolymers of methacrylic acid.

[0356] The (meth)acrylic acid copolymer is particularly a copolymer of (meth)acrylic acid and alkyl (poly)ether (meth)acrylate, and more particularly a copolymer of (meth)acrylic acid and POE / POP (meth)acrylate, for example, polyether polycarbonate, sodium salt in aqueous solution, for example, sold by Arkema-Coatex under the name RSY 15007 Cosmetic Version.

[0357] According to a preferred embodiment, the one or more polymers b) are Lignosulfonic acid, lignosulfonate, polystyrene sulfonate, polystyrene sulfonate, anionic polyanethole derivatives, especially polyanethole sulfonate, and combinations thereof. Alkyl esters or ethers of polyols, especially glycerols, Anionic polysaccharides, preferably selected from sulfated polysaccharides, particularly urban, dextran sulfate, carrageenan and combinations thereof, and polysaccharide carboxylates, particularly alginates. Cationic polysaccharides, preferably selected from polysaccharides having an amine group, particularly chitosan, A modified polysaccharide, particularly a polysaccharide ester, preferably a pullulan ester, is selected from modified polysaccharides, Poly((C2~C5)alkyleneimines), preferably polyethyleneimines and polypropyleneimines, particularly poly(ethyleneimines), Polyamino acids, preferably polyamino acids selected from proteins, An anionic acyclic polymer having a carboxyl group or a carboxylate of an alkali metal or alkaline earth metal, such as sodium, selected from homopolymers or copolymers of (meth)acrylic acid, preferably polysodium methacrylate, and copolymers of (meth)acrylic acid and alkyl (poly)ether (meth)acrylate, particularly copolymers of (meth)acrylic acid and POE / POP (meth)acrylate, and, those combinations Selected from.

[0358] According to a more preferred embodiment, the one or more polymers b) are Lignosulfonates, in particular alkali metal or alkaline earth metal lignosulfonates, such as sodium lignosulfonate or calcium lignosulfonate. Carrageenan, Chitosan, Alginates, in particular, alkali metal or alkaline earth metal alginates, such as sodium alginate, Dextran, particularly alkali metal or alkaline earth metal dextran, and alkali metal or alkaline earth metal dextran sulfate, such as dextran sodium sulfate. Polyhydroxystearic acid, Starch and its derivatives, in particular its phosphate derivatives, such as hydroxypropylcorn phosphate distarch, Pullulan and its ester derivatives, in particular C1-C 30 Preferably C 10 ~C 20 carboxylic acids, ester derivatives of, for example, myristoyl pullulan, Polyvinyl alcohol, Proteins that may be hydrolyzed, for example, hydrolyzed soy protein, and those combinations Selected from.

[0359] In a more preferred embodiment, the one or more polymers b) are Lignosulfonate, Carrageenan, Chitosan, Alginates, such as sodium alginate, Dextran, for example, dextran sulfate sodium, Polyhydroxystearic acid, Starch and its derivatives, for example, hydroxypropylcorn phosphate distarch, Pullulan and its ester derivatives, for example, myristoyl pullulan, Polyvinyl alcohol, Proteins, such as hydrolyzed soy protein, and those combinations Selected from.

[0360] Inorganic compounds c)

[0361] In certain embodiments, the composite material according to the present invention may also comprise at least one inorganic compound c) different from the bismuth oxycarbonate particles a).

[0362] The one or more inorganic compounds c) are amorphous or crystalline, hydrated or unhydrated forms of oxides, hydroxides or oxyhydroxides of alkali metals or alkaline earth metals, in particular sodium, potassium, magnesium and calcium, or transition metals, in particular titanium, aluminum, manganese, iron, copper, niobium and tantalum, or lanthanides, in particular cerium, or poor metals, in particular zinc, indium and bismuth.

[0363] Inorganic oxides can also exist as amorphous or crystalline, hydrated or unhydrated forms of metalloid oxides, hydroxides, or oxyhydroxides.

[0364] In particular, the inorganic compound c) is a silicon oxide or hydroxide or oxyhydroxide, for example, silicon dioxide SiO2, lithium and / or sodium and / or potassium and / or ammonium and / or calcium and / or magnesium and / or aluminum and / or titanium and / or iron and / or zinc and / or bismuth silicates, aluminum and / or calcium and / or magnesium and / or sodium and / or titanium and / or iron and / or zinc and / or bismuth borosilicates.

[0365] In particular, the inorganic compound c) may be an amorphous or crystalline, hydrated or ahydrated inorganic carbide, sulfide, or nitride, such as silicon carbide, iron sulfide, copper sulfide, and zinc sulfide, or, for example, boron nitride and silicon nitride.

[0366] Examples of metal oxides that may be mentioned include Al2O3, Al(OH)3, SiO2, TiO2, MnO, MnO2, FeO(OH), Fe3O4, Fe2O3, Cu(OH)2, Cu2O, CuO, Zn(OH)2, ZnO, Nb2O5, In(OH)3, In2O3, Ce2O3, CeO2, Ta2O5, WO3, Bi2O3, or combinations thereof in hydrated or unhydrated forms.

[0367] Preferably, a hydrated or unhydrated form of Al2O3 (e.g., Al(OH)3), a hydrated or unhydrated form of SiO2, TiO2, or ZnO, or a combination thereof, more preferably a hydrated or unhydrated form of Al2O3 (e.g., Al(OH)3), or a hydrated or unhydrated form of SiO2, TiO2, or ZnO, or a combination thereof, and even more preferably a hydrated or unhydrated form of Al2O3 (e.g., Al(OH)3), or SiO2, or a combination thereof is used.

[0368] In a preferred embodiment, the composite material according to the present invention does not contain any inorganic compound c) other than the bismuth oxycarbonate particles a).

[0369] According to another preferred embodiment, the composite material according to the present invention comprises only one inorganic compound c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic oxides, more preferably selected from silica, alumina, titanium dioxide and zinc oxide, and better selected from silica.

[0370] According to another preferred embodiment, the composite material according to the present invention comprises only one inorganic compound c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic hydroxides or inorganic oxyhydroxides, more preferably selected from inorganic hydroxides, more preferably selected from Al(OH)3, Zn(OH)2, In(OH)3 or a combination thereof, even more preferably selected from Al(OH)3, Zn(OH)2, and better selected from Al(OH)3.

[0371] Preferably, the composite material according to the invention comprises one or more inorganic compounds c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic oxides, more preferably selected from zinc oxide, titanium oxide, silicon oxide and / or aluminum oxide, preferably selected from silicon oxide and / or aluminum oxide, which may optionally be hydrated.

[0372] Preferably, the composite material according to the invention comprises one or more inorganic compounds c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic oxides, more preferably selected from Al(OH)3, SiO2, TiO2 and ZnO, even more preferably selected from Al(OH)3 or SiO2.

[0373] Method for preparing the composite material

[0374] The composite material according to the invention can in particular be obtained via the manufacturing processes described below.

[0375] In particular, the composite material according to the invention as defined above can be obtained in one or more steps.

[0376] The composite material can in particular be obtained conventionally via various processes, in particular a process in which the bismuth oxycarbonate particles a) are brought into contact with a solution comprising at least one polymer b) in a solvent or solvent mixture A.

[0377] In particular, the method for preparing the composite material according to the invention is the following formula (I): (BiO) 2-x (CO3) formula (I) (where -0.4 < x < 0.6) bismuth oxycarbonate a) and its solvates, such as its hydrates, particles, where the maximum average dimension of the particles is less than 400 nm; optionally, one or more precursors intended to form one or more inorganic compounds c) different from the bismuth oxycarbonate particles; one or more polymers b) as defined above; Optionally, one or more additives; and, Optionally, one or more solvents Includes.

[0378] In a particular embodiment, a method for preparing a composite material according to the present invention may include one or more separation steps.

[0379] In particular, one or more precursors intended to form one or more inorganic compounds c) different from the bismuth oxycarbonate particles a) are selected from organic or inorganic compounds that enable the acquisition of particles of bismuth oxycarbonate a) and inorganic compound c) by chemical reaction or physical adsorption.

[0380] In particular, the one or more precursors are As mentioned above, inorganic compound c), Inorganic metal precursors of chemical elements and their hydrates, especially dissolved metal oxides, particularly sodium silicate and sodium aluminate, halides and their hydrates, nitrates and their hydrates, carbonates and their hydrates, sulfonates and their hydrates, sulfates and their hydrates, phosphates and their hydrates, Organometallic precursors and their hydrates, particularly alkoxides and their hydrates, carboxylates and their hydrates, lactates and their hydrates, or citrates and their hydrates, those combinations It can be selected from the following.

[0381] The one or more precursors intended to form the one or more by-product inorganic compounds c) may also be selected from oxidizing 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.

[0382] According to a preferred embodiment, a method for preparing a composite material according to the present invention does not use precursors intended to form one or more inorganic compounds c) that are different from the bismuth oxycarbonate particles a).

[0383] According to a preferred embodiment, a method for preparing a composite material according to the present invention uses at least one precursor intended to form one or more of the inorganic compounds c) different from the bismuth oxycarbonate particles a), preferably a precursor selected from sodium silicate and sodium aluminate.

[0384] According to a particular embodiment, a method for preparing a composite material according to the present invention uses at least one solvent.

[0385] The selection of one or more solvents can depend, inter alia, on one or more precursors and additives used in the method.

[0386] In particular, the one or more solvents can be selected from polar or non-polar, protic or aprotic solvents.

[0387] According to a particular embodiment, a method for preparing a composite material according to the present invention uses at least one additive.

[0388] In particular, the one or more additives can be selected from acids, in particular mineral acids such as hydrochloric acid or sulfuric acid, and bases, preferably inorganic bases such as sodium hydroxide or potassium hydroxide.

[0389] According to a particular embodiment, the present invention is a method for preparing the composite material as defined above, (i) preparing at least one particle of bismuth oxycarbonate particles a) of the following formula (I): (BiO) 2-x (CO3) formula (I) (where -0.4 < x < 0.6) and at least one particle of its solvate, such as its hydrate, the maximum average dimension of the particle being less than 400 nm and optionally dispersed in at least one solvent or solvent mixture A; (ii) preparing a solution of at least one polymer b) which may be in a solvent or solvent mixture B; (iii) bringing the at least one particle a) or dispersion (i) into contact with the solution (ii) to form the composite material; (iv) Separating the composite material This is directed towards the above method which includes at least the following steps.

[0390] Preferably, step (i) does not use solvent A.

[0391] In one embodiment, the one or more solvents in steps (i) and (ii) may be the same or different.

[0392] In particular, the one or more solvents A and / or B are selected from nonpolar aprotic solvents, polar protic solvents, and more preferably water, alcohols, polyols, and combinations thereof.

[0393] In particular, when the one or more polymers b) are hydrophilic and / or amphiphilic, the solvent or solvent mixture B is polar, and when the polymers are hydrophobic and / or amphiphilic, the solvent or solvent mixture B is nonpolar.

[0394] In particular, when the one or more polymers b) are hydrophilic and / or amphiphilic, the solvent or solvent mixture B is polar and protic, preferably selected from water, polyols and / or combinations thereof, and more preferably water.

[0395] In particular, when the one or more polymers b) are hydrophobic and / or amphiphilic, the solvent or solvent mixture B is nonpolar and preferably selected from volatile and non-volatile oils or organic solvents.

[0396] Preferably, the mixture (iii) is stirred continuously for a period of 5 minutes to 24 hours under atmospheric pressure, particularly at a temperature in the range of 20°C to 200°C, especially in open air or under an inert atmosphere.

[0397] In particular embodiments, a method for preparing a composite material according to the present invention may include one or more steps of separation, particularly separation by centrifugation and / or filtration, particularly separation by ultrafiltration, and / or separation by freeze-drying and / or separation by atomization.

[0398] According to a particular embodiment, a method for preparing the composite material also includes a centrifugal separation step.

[0399] In particular, according to this embodiment, the method for preparing the composite material is also, Optionally, a step of adding a solvent or solvent mixture S in which the one or more polymers b) do not dissolve, i.e., allowing the polymers b) to precipitate from the solvent or solvent mixture S at a temperature in the range of 0°C to room temperature, thereby precipitating the composite material; Preferably, at least one centrifugal separation step at 4000 rpm to 14000 rpm, particularly for a period of 1 minute to 1 hour; and, Preferably, at least one step of washing using the solvent or solvent mixture S; At least one step of separating the composite material, which is optionally dried in an oven, preferably at a temperature of 50°C, and especially under vacuum (pressure equal to 10 mmHg). Includes.

[0400] According to a particular embodiment, a method for preparing the composite material also includes a filtration step, particularly an ultrafiltration step.

[0401] In particular, according to this embodiment, the method for preparing the composite material is also, Optionally, a step of adding a solvent or solvent mixture S, The step of separating the composite material from the solvent mixture by filtration, particularly by ultrafiltration, using a membrane, preferably having a pore size in the range of 1 nm to 1 μm, and more preferably 1 to 100 nm. Optionally, at least one centrifugal separation step; Optionally, at least one washing step; and, At least one step of separating the composite material, optionally drying it in an oven, preferably at a temperature of 50°C, and especially under vacuum (at a pressure equal to 10 mmHg). Includes.

[0402] According to a particular embodiment, a method for preparing the composite material also includes a freeze-drying step.

[0403] In particular, according to this embodiment, a method for preparing the composite material also includes the step of freeze-drying the mixture, after optionally evaporating one or more solvents if the reaction medium contains multiple solvents, particularly at a temperature in the range of 0°C to -180°C.

[0404] According to a particular embodiment, a method for preparing the composite material also includes an atomization step.

[0405] In particular, according to this embodiment, a method for preparing the composite material also includes a step of atomizing the mixture. In particular, the atomization temperature is preferably below the lowest characteristic transition temperature of the polymer b) or all of the polymers b) constituting the mixture, where “transition” refers to a potential glass transition and / or potential melting and / or potential decomposition, and the atomization temperature is higher than the lowest boiling point of one or more solvents of the mixture. Preferably, the atomization temperature is in the range of 80°C to 250°C, more preferably 100°C to 200°C, and even more preferably 100°C to 180°C.

[0406] Cosmetic composition

[0407] The composite materials according to the present invention can be used particularly in compositions, and especially in cosmetic compositions.

[0408] Accordingly, the present invention also relates to compositions comprising at least one composite material as defined above, particularly cosmetic compositions.

[0409] According to a preferred embodiment, the present invention also relates to compositions, in particular cosmetic compositions, i) At least one composite material as defined above; ii) at least one aqueous phase and / or at least one fatty phase; and, iii) 1) UV shielding agents different from i) of the composite material; 2) colorants; 3) cosmetic surfactants for caring for keratinic substances; 4) surfactants; 5) thickeners; and at least one compound selected from combinations thereof. The present invention relates to the above composition comprising at least the above.

[0410] The composite material may be present in the composition, preferably in the cosmetic composition, in an amount ranging from 0.5% to 70% by weight, preferably 1% to 50% by weight, and more preferably 2% to 40% by weight, relative to the total weight of the composition.

[0411] aqueous phase

[0412] A composition according to the present invention, in particular a cosmetic composition, may contain at least one aqueous phase.

[0413] The aqueous phase may include water and, optionally, a water-soluble solvent.

[0414] In this invention, the term "water-soluble solvent" refers to a compound that is liquid at room temperature and miscible with water (more than 50% by weight miscible with water at 25°C and atmospheric pressure).

[0415] The water-soluble solvent that can be used in compositions according to the present invention may also be volatile.

[0416] Among the water-soluble solvents that can be used in compositions according to the present invention, in particular 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 may be mentioned.

[0417] Among the water-soluble solvents that can be used in compositions according to the present invention, polyols may be mentioned in particular. In the present invention, the term "polyol" means any organic molecule containing at least two free hydroxyl groups.

[0418] Suitable polyols for use in the present invention are linear, branched, or cyclic, saturated, or unsaturated alkyl-type compounds having at least two -OH functional groups, particularly at least three -OH functional groups, on the alkyl chain.

[0419] Polyols that are advantageously suitable for preparing compositions according to the present invention are, in particular, polyols containing 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms.

[0420] Advantageously, the polyol may be selected from, for example, pentaerythritol, trimethylolpropane, caprylyl glycol, glycerol, polyglycerol, for example, glycerol oligomers (e.g., diglycerol), polyethylene glycol, polypropylene glycol, and combinations thereof.

[0421] fat phase

[0422] A composition according to the present invention, in particular a cosmetic composition, may also contain at least one fatty phase, in particular an oily phase.

[0423] In the present invention, the term "fatty phase" means a phase comprising at least one fatty substance and all lipid-soluble and lipophilic components used to prepare the composition of the present invention.

[0424] Preferably, the fatty phase includes at least one oil, in particular an oil for cosmetic use.

[0425] The term "oil" refers to a non-aqueous compound that is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg) and is immiscible with water.

[0426] The fatty phase may contain at least one volatile or non-volatile hydrocarbon oil and / or fatty substance.

[0427] Non-volatile hydrocarbon oils include, in particular, plant-derived hydrocarbon oils, synthetic ethers containing 10 to 40 carbon atoms, linear or branched hydrocarbons of mineral or synthetic origin, synthetic esters, fatty alcohols that are liquid at room temperature and have branched and / or unsaturated carbon chains containing 12 to 26 carbon atoms, C12 to C22 high fatty acids, carbonates, and combinations thereof.

[0428] Among volatile hydrocarbon oils, those containing 8 to 16 carbon atoms can be particularly mentioned.

[0429] Non-volatile silicone oils may include, in particular, non-volatile polydimethylsiloxane (PDMS) and phenyl silicone. Volatile silicone oils may include, for example, volatile linear or cyclic silicone oils.

[0430] In addition, volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and combinations thereof, may be used.

[0431] The oily phase may contain oil and other fatty substances mixed with or dissolved in the oil. Other fatty substances that may be present in the oily phase may be, for example, fatty acids, waxes, gums, paste-like compounds, or combinations thereof.

[0432] 1) Additional UV shielding agent

[0433] According to a particular embodiment, a composition according to the present invention comprises 1) at least one additional UV shielding agent which is required according to the present invention and is different from the composite material defined above.

[0434] In the present invention, the term "UV shielding agent different from the composite material" is intended to refer to any UV shielding agent whose chemical properties are required in accordance with the present invention and which are different from the chemical properties of the composite material as defined above.

[0435] The composite material according to the present invention may be used alone, or 1) in combination with other UV-screening agents selected from other UV-screening agents, particularly organic UV-screening agents and / or inorganic UV-screening agents.

[0436] Accordingly, the cosmetic composition may also include one or more additional UV-screening agents selected from hydrophilic, lipophilic, or insoluble organic UV-screening agents and / or mineral UV-screening agents different from the composite materials according to the present invention.

[0437] The term "hydrophilic UV shielding agent" refers to any cosmetic or dermatological organic or inorganic compound used to filter UV irradiation, which may be completely dissolved in molecular form in a liquid aqueous phase, or may be a colloidal suspension (e.g., in micelle form) in a liquid aqueous phase.

[0438] The term "lipophilic UV shielding agent" refers to any cosmetic or dermatological organic or inorganic compound used to filter UV irradiation, which may be completely dissolved in molecular form in the liquid lipid phase, or may be a colloidal suspension (e.g., in micelle form) in the liquid lipid phase.

[0439] The term "insoluble UV shielding agent" refers to any cosmetic or dermatological organic or inorganic compound for filtering UV irradiation, which has a solubility in water of less than 0.5% by weight, and is an organic solvent, such as liquid paraffin, fatty alcohol benzoic acid esters, and fatty acid triglycerides (e.g., Miglyol 812). 登録商標This refers to the above-mentioned cosmetic or dermatological organic or inorganic compounds having a solubility of less than 0.5% by weight in the majority of the solution. This solubility is determined at 70°C and defined as the amount of product in the solvent in equilibrium with excess solid in the suspension after returning to room temperature. This solubility can be easily evaluated in the laboratory.

[0440] The additional organic UV shielding agent is, in particular, Cinnamic compounds, particularly ethylhexyl methoxycinnamate, Anthranilate compounds, especially menthyl anthranilate, Salicylic compounds, particularly homosalate 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-diphenyl acrylate compounds, particularly octocrylene, Triazine compounds, particularly phenylene bis-diphenyl triazine, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, and diethylhexyl butamido triazone, Benzotriazole compounds, particularly drometrizole trisiloxane, Benzalmalonate compounds, in particular those compounds described in U.S. Patent No. US5624663, especially polysilicone-15, Benzimidazole derivatives, particularly phenylbenzimidazole sulfonic acid, Imidazolin compounds, particularly ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate, Bis-benzazolyl compounds, for example, those compounds described in European Patent No. EP0669323 and U.S. Patent No. US2463264, in particular Disodium Phenyl Dibenzimidazole Tetra-sulfonate, Para-aminobenzoic compounds, particularly PABA, ethylhexyl dimethyl PABA, and PEG-25 PABA, Methylenebis(hydroxyphenylbenzotriazole) compounds, for example, those compounds described in U.S. Patent No. US5237071, U.S. Patent No. US5166355, UK Patent No. GB2303549, German Patent No. DE19726184, and European Patent No. EP0893119, in particular methylenebis-benzotriazoll=tetramethylbutylphenol, Benzooxazole compounds, for example, those compounds described in European Patent No. EP0832642, European Patent No. EP1027883, European Patent No. EP1300137 and German Patent No. DE10162844, 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, those compounds described in International Publication No. WO93 / 04665, Dimers derived from α-alkylstyrene, for example, those compounds described in German Patent No. DE19855649, 4,4-diarylbutadiene compounds, for example, those compounds described in European Patent No. EP0967200, German Patent No. DE19746654, German Patent No. DE19755649, European Patent No. EP1008586, European Patent No. EP1133980 and European Patent No. EP0133981, in particular 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, and those combinations Selected from.

[0441] These additional inorganic UV-screening agents are generally mineral UV-screening agents, and are particularly selected from metal oxides.

[0442] The metal oxide can be selected from, in particular, titanium oxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, and combinations thereof.

[0443] The metal oxide particles may or may not be coated.

[0444] The coated particles are, more preferably, silica-coated titanium oxide particles, silica and iron oxide-coated titanium oxide particles, silica and alumina-coated titanium oxide particles, alumina-coated titanium oxide particles, alumina and aluminum stearate-coated titanium oxide particles, silica, alumina and alginate-coated titanium oxide particles, alumina and aluminum laurate-coated titanium oxide particles, iron oxide and iron stearate-coated titanium oxide particles, zinc oxide and zinc stearate-coated titanium oxide particles, silica and alumina-coated and silicone-treated titanium oxide particles, silica-coated and silicone-treated titanium oxide particles, alumina-coated and silicone-treated titanium oxide particles, triethanolamine-coated titanium oxide particles, stearic acid-coated titanium oxide particles, sodium hexametaphosphate (sodium Titanium dioxide particles coated with hexametaphosphate, or TiO2 coated with octyltrimethylsilane, TiO2 treated with polydimethylsiloxane, anatase / rutile TiO2 treated with polydimethylhydrogenosiloxane, TiO2 coated with triethylhexanoin, TiO2 coated with aluminum stearate, and TiO2 coated with alumina, TiO2 coated with aluminum stearate, TiO2 coated with alumina, and TiO2 coated with silicone, TiO2 coated with lauroyl lysine, or C 9~15This is TiO2 coated with fluoroalcohol phosphate and aluminum hydroxide.

[0445] The metal oxide may optionally be doped.

[0446] In this regard, TiO2 particles doped with at least one transition metal, such as iron, zinc, or manganese, and more particularly manganese, can be mentioned.

[0447] 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 containing caprylic / capric triglycerides. The oily dispersion of titanium dioxide particles may further contain one or more dispersants, such as sorbitan esters or polyoxyalkylened glycerol fatty acid esters. More preferably, an oily dispersion of manganese-doped TiO2 particles in caprylic / capric triglycerides may be mentioned in the presence of tri-PPG-3 myristyl ether citrate, polyglyceryl-3 polyricinoleate, and sorbitan isostearate.

[0448] Furthermore, mixtures of metal oxides may be mentioned, in particular mixtures of titanium dioxide and cerium dioxide (including equal weight mixtures of silica-coated titanium dioxide and cerium dioxide), as well as mixtures of titanium dioxide coated with alumina, silica, and silicone and zinc dioxide, or mixtures of titanium dioxide coated with alumina, silica, and glycerol and zinc dioxide.

[0449] 2) Coloring agents

[0450] According to a particular embodiment, a composition according to the present invention comprises 2) at least one coloring agent.

[0451] Generally, the term "colorant" is understood to refer to any compound that can color a composition, that is, any compound that absorbs in the visible spectrum and appears to have a color, such as yellow, orange, red, purple, blue, or green, to the human eye.

[0452] Preferably, a composition according to the present invention comprises at least one dye.

[0453] The term "pigment" should be understood to mean white or colored inorganic or organic particles that are insoluble in liquid lipophilic and hydrophilic phases and are intended to color and / or opaque compositions containing them, and to be distinct from composite materials according to the present invention. More specifically, the pigment is little to no soluble in aqueous-alcohol media.

[0454] The pigments that can be used are selected from organic and / or mineral pigments known in the art, in particular 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 ibid, “Pigments, Inorganic, 1. General”, 2009 Wiley-VCH Verlag GmbH & Co.KGaA,Weinheim10.1002 / 14356007.a20_243.pub3).

[0455] These dyes may be in the form of a dye powder or paste. These dyes may or may not be coated.

[0456] The pigments may be selected from, for example, mineral pigments, organic pigments, lakes, pigments with special effects (e.g., nacres or glitter flakes), and combinations thereof.

[0457] The pigment may be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in the Ullmann Encyclopedia. Among the mineral pigments useful in this invention, iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydroxide, ferric blue, and titanium dioxide may be mentioned.

[0458] The dye may be an organic dye.

[0459] The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in the Ullmann Encyclopedia.

[0460] The organic dye can be selected from, in particular, nitroso compounds, nitro compounds, azo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, phthalocyanine compounds, metal complex compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, or quinophthalone compounds.

[0461] Preferably, one or more dyes suitable for use in the present invention are selected from carbon black, iron oxides, particularly red, brown or black iron oxides, and iron oxide-coated mica, triarylmethane dyes, particularly blue and purple triarylmethane dyes (e.g., Blue 1 Lake), azo dyes, particularly red azo dyes (e.g., D&C Red 7), and alkali metal salts of lithol red (e.g., calcium salts of lithol red B). More preferably, one or more dyes used are selected from red iron oxides and azo dyes, particularly red azo dyes, such as D&C Red 7.

[0462] One or more colorants may be present in a composition according to the present invention in an amount ranging from 0.001% to 10% by weight, preferably 0.005% to 5% by weight, relative to the total weight of the composition.

[0463] According to a particular embodiment of the present invention, the amount of pigment is in the range of 0.5% to 40%, preferably 1% to 20%, relative to the weight of the composition of the present invention containing them.

[0464] 3) Cosmetic surfactants

[0465] According to a particular embodiment, a composition according to the present invention comprises 3) at least one cosmetic active agent for caring for keratinous substances, preferably for caring for skin.

[0466] In particular, the cosmetic surfactant may be at least one hydrophilic surfactant and / or one lipophilic surfactant, and is preferably hydrophilic.

[0467] The term "hydrophilic surfactant" refers to a water-soluble or water-dispersible surfactant that can form hydrogen bonds.

[0468] Examples of cosmetic surfactants3) may include, for example, moisturizers, decolorizers, exfoliating agents, moisturizers, anti-aging agents, matting agents, wound healing agents, antibacterial agents, vitamins and their derivatives or precursors, antioxidants, free radical scavengers; anti-stain agents; self-tanning agents; anti-glycation agents; sedatives; deodorants; essential oils; NO synthase inhibitors; agents for stimulating and / or preventing the breakdown of polymers in the dermis or epidermis; agents for stimulating fibroblast proliferation; agents for stimulating keratinocyte proliferation; muscle relaxants; cooling agents; astringents; pigmentation 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 combinations thereof.

[0469] The one or more activators are, in particular, Vitamins and their derivatives, in particular 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), Moisturizers or moisturizing ingredients, such as urea, hydroxyurea, glycerol, polyglycerol, glyceryl glucoside, diglyceryl glucoside, polyglyceryl glucoside, xylityl glucoside, and plant extracts (especially tea, mint, orchid, soybean, and aloe vera plant extracts), honey, and especially glycerol; C-glycoside compounds, and preferably hydroxypropyl tetrahydropyrantriol (INCI name) (or proxylan); Antioxidant compounds; Anti-aging agents, such as hyaluronic acid compounds, particularly sodium hyaluronate; salicylic acid compounds, especially 5-n-octanoylsalicylic acid (capryloylsalicylic acid), adenosine, and sodium salts of (3-hydroxy-2-pentylcyclopentyl)acetic acid; Keratin-dissolving agents, for example, lactic acid or glycolic acid; and, those combinations It can be selected from the following.

[0470] Such activators may be present in the composition of the present invention in an amount ranging from 0.05% to 10% by weight, preferably 1.0% to 8.0% by weight, relative to the total weight of the composition.

[0471] 4) Surfactants

[0472] According to a particular embodiment, a composition according to the present invention comprises 4) at least one surfactant.

[0473] The surfactant may be selected from nonionic, anionic, cationic, and amphoteric surfactants, as well as combinations thereof. For definitions of the emulsifying properties and functions of surfactants, refer to Kirk-Othmer's Encyclopedia of Chemical Technology, Volume 22, pages 333-432, 3rd Edition, 1979, Wiley, in particular pages 347-377 of this reference, which discuss anionic, amphoteric, and nonionic surfactants.

[0474] Examples of amphoteric surfactants suitable for use in the present invention are selected from betaines, preferably alkyl betaines, particularly lauryl betaine, N-alkylamide betaine and its derivatives, particularly cocamidopropyl betaine, lauramidopropyl betaine, and N-disodium N-carboxyethoxyethyl N-cocoylamidoethyl aminoacetate, sultaines, particularly cocoyl amidopropyl hydroxy sultaine, and combinations thereof.

[0475] Nonionic surfactants can be selected from, in particular, alkyl and polyalkyl esters of poly(ethylene oxide), oxyalkylened alcohols, alkyl and polyalkyl ethers of poly(ethylene oxide), optionally polyoxyethylene-treated alkyl and polyalkyl esters of sorbitan, optionally polyoxyethylene-treated alkyl and polyalkyl ethers of sorbitan, especially alkyl and polyalkyl esters of sucrose, optionally polyoxyethylene-treated alkyl and polyalkyl esters of glycerol, optionally polyoxyethylene-treated alkyl and polyalkyl ethers of glycerol, gemini surfactants, cetyl alcohol, stearyl alcohol, and combinations thereof.

[0476] The anionic surfactants include alkyl ether sulfates, carboxylates, amino acid derivatives, sulfonates, isethionates, taurates, sulfosuccinates, alkyl sulfoacetates, phosphates and alkyl phosphates, polypeptides, and C 10 ~C 30 , especially C 16 ~C 25 The fatty acids, particularly metal stearates and behenates, and combinations thereof, can be selected.

[0477] The cationic surfactant is alkylimidazolidinium, for example isostearyl ethylimidonium ethosulfate, an ammonium salt, for example, (C 12-30 -alkyl)tri(C 1-4 -Alkyl)ammonium chlorides, such as N,N,N-trimethyl-1-docosaminonium chloride (or behentrimonium chloride), may be selected.

[0478] The silicone-based surfactant can be selected from dimethicone copolyol or silicone elastomer.

[0479] A composition according to the present invention may contain a surfactant in an amount of 0.01% to 2.0% by weight, preferably 0.05% to 1.5% by weight, and more preferably 0.1% to 1.0% by weight, based on the total weight of the composition.

[0480] 5) Thickening agents

[0481] In a particular embodiment, a composition according to the present invention comprises 5) at least one thickening agent (also known in some cases as a gelling agent or viscosity modifier).

[0482] The thickening agent may be synthetic, natural, or of natural origin, preferably natural or of natural origin.

[0483] Such thickeners may more preferably be selected from natural polymers, or polymers of natural origin, particularly polymers of plant origin.

[0484] These thickeners are preferably hydrophilic, i.e., soluble or dispersible in water.

[0485] Advantageously, the one or more thickeners include modified or natural polysaccharides, particularly modified or unmodified starches, fructans, gellans, glucans, amylose, amylopectin, glycogen, pullulan, dextran, cellulose and its derivatives, particularly methylcellulose, hydroxyalkylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, mannan, xylan, lignin, araban, galactoane, galacturonan, alginate-based compounds, chitin, chitosan, glucuronoxylan, arabinoxylan, xyloglucan, glucomannan, pectic acid and pectin, arabinogalactan, carrageenan, agar, glycosaminoglycans, gum arabic, sclerotium gum, tragacanth gum, ghatti gum Selected from: gum), karaya gum, locust bean gum, konjac gum, galactomannan (e.g., guar gum) and its nonionic derivatives, particularly hydroxypropyl guar and its ionic derivatives, biopolysaccharide gums of microbial origin, particularly scleroglucan or xanthan gum, mucopolysaccharides, carboxyvinyl polymers, polyacrylamide, polymers and copolymers of 2-acrylamide-2-methylpropanesulfonic acid, optionally crosslinked and / or neutralized, water-soluble or water-dispersible silicone derivatives, such as acrylic silicones, polyether silicones and cationic silicones, and combinations thereof.

[0486] One or more of these thickening agents may be present in a composition according to the present invention in an amount of 0.05% to 5.0% by weight, particularly 0.3% to 4.0% by weight, and more preferably 0.4% to 2.5% by weight, based on the total weight of the composition.

[0487] Adjuvants

[0488] The compositions according to the present invention may also contain at least one auxiliary agent that is common in the cosmetics field, 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, defoaming agents, fillers, trace elements, propellants, and combinations thereof.

[0489] Those skilled in the art will understand that they should take care to select this or any one or more additional compounds and / or their amounts such that the advantageous properties of the compositions according to the present invention are not adversely affected, or substantially adversely affected, by the intended additions.

[0490] Those skilled in the art will understand that they should take care to select this or any one or more additional compounds and / or their amounts such that the advantageous properties of the particles according to the present invention are not adversely affected, or substantially adversely affected, by the assumed additions.

[0491] As described above, the composition according to the present invention may be a cosmetic, and is preferably a cosmetic.

[0492] Compositions according to the present invention are generally suitable for topical application to the skin and therefore generally include a physiologically acceptable medium, i.e., a medium compatible with the skin.

[0493] It is preferable that the medium is acceptable as a cosmetic, that is, has a desirable color, scent, and feel, and does not cause any unacceptable discomfort such as stinging or tightness that would prevent the user from applying the composition.

[0494] Dosage form of the composition

[0495] A composition containing particles according to the present invention, particularly a cosmetic composition, can be prepared according to techniques well known to those skilled in the art.

[0496] The composition may be in any conventional dosage form depending on the intended use, and the process involves topical application, i.e., application to the surface of the target keratinous substance.

[0497] The cosmetic composition may be in the form of an aqueous or aqueous-alcohol gel.

[0498] They may be in the form of simple or complex emulsions (O / W, W / O, O / W / O, W / O / W), such as cream, milk, or gel cream.

[0499] They may also be in anhydrous form, for example, in the form of oil.

[0500] The term "anhydrous composition" means a composition having a water content of less than 5% by weight, or less than 2% by weight, or better, less than 1% by weight, and in particular a composition that does not contain water, where water is not added during the preparation of the composition but corresponds to residual water provided by the mixed components.

[0501] The cosmetic composition can be used, for example, as a makeup product.

[0502] The cosmetic composition may be used, for example, as a facial and / or body care and / or sun protection product, and may have the appearance of a white or colored cream, ointment, milk, cream gel, lotion, serum, paste, or foam, having a liquid to semi-liquid viscosity and being more or less oily. The cosmetic composition may optionally be applied to the skin in aerosol form. The cosmetic composition may also be in solid form, for example, in the form of a stick.

[0503] The cosmetic composition may be in the form of a product for caring for the skin or semi-mucous membranes, for example, a protective or cosmetic care composition for the face, lips, hands, feet, anatomical folds, or body (e.g., day cream, night cream, day serum, night serum, makeup remover cream, makeup base, protective or care body milk, after-sun milk, skincare or scalp care lotion, gel or foam, serum, mask, or aftershave composition).

[0504] The composition can be applied by hand or using an applicator.

[0505] In particular, the cosmetic composition has an SPF of more than 5, preferably more than 10.

[0506] In the present invention, the term "SPF" refers to a sunscreen protection factor that measures the level of protection from UV rays. The SPF value corresponds to the ratio of the minimum time required to obtain an erythematogenic tan with the sunscreen composition to the minimum time required to obtain a tan without the sunscreen composition. More specifically, 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, 127~133 (May / June 1989).

[0507] SPF (Sun Protection Factor) is calculated using Labsphere 登録商標 The results can be evaluated in vitro using a spectrophotometer. "Sheet" refers to the material to which the sunscreen composition is applied. Polymethyl methacrylate (PMMA) sheets have proven ideal for this protocol.

[0508] The sun protection factor (SPF) of the composition may 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)”.

[0509] The term "UVAPF" refers to an index that characterizes the protective effect from UV-A irradiation. In particular, this index could be measured in vivo using the PPD (Persistent Pigment Darkening) method. PPD measures skin tone observed 2-4 hours after exposure to UV-A irradiation. This method has been adopted by the Japan Cosmetic Industry Association (JCIA) as the official test procedure for UV-A labeling of products since 1996 and is frequently used by testing laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin. Measurement standards for the efficacy of UVA protection issued on 21 November 1995 and in force since 1 January 1996). UV-A protective effect is also measured in Labsphere 登録商標 The material can be evaluated in vitro using a spectrophotometer. The sheet is the material to which the sunscreen composition is applied. In this protocol, polymethyl methacrylate (PMMA) sheets have proven ideal. The ISO 24443 protocol describes such an in vitro method.

[0510] Cosmetic use and method

[0511] The present invention also relates to a non-therapeutic cosmetic use of a composite material according to the present invention for filtering UV irradiation, preferably UV-B irradiation, the above non-therapeutic cosmetic use comprising applying a composition comprising at least one of the aforementioned composite materials to a keratinous substance.

[0512] The present invention also relates to a non-therapeutic cosmetic method for filtering UV irradiation, particularly UV-B irradiation, comprising applying a composition comprising at least one of the aforementioned composite materials to a keratin substance for the above-mentioned non-therapeutic cosmetic use.

[0513] According to yet another aspect of the present invention, the present invention also relates to the non-therapeutic cosmetic use of a cosmetic composition comprising at least one of the previously defined composite materials for preventing the appearance of darker / or more pigmented marks that give uneven skin color to the skin, particularly on the face, neck, arms, hands and / or shoulders.

[0514] The present invention is also directed toward a non-therapeutic cosmetic method for inhibiting the darkening of keratinous substances, in particular human keratinous substances, e.g., skin, and / or keratinous fibers, in particular human keratinous fibers, e.g., hair, and / or improving the color of skin or the tone and / or uniformity of keratinous fibers, the method comprising applying to the surface of the keratinous substances and / or keratinous fibers at least one cosmetic composition comprising at least one composite material as defined above.

[0515] The present invention also relates to the non-therapeutic cosmetic use of a cosmetic composition comprising at least one composite material as defined above, and is directed toward the above-mentioned non-therapeutic cosmetic method for preventing premature aging of keratinous substances, particularly human keratinous substances, for example, particularly skin, in particular the skin of the face, neck, arms, hands and / or shoulders.

[0516] The present invention is also directed toward a non-therapeutic cosmetic method for preventing and / or treating signs of aging of keratinous material, in particular human keratinous material, in particular skin, the above-mentioned non-therapeutic cosmetic method comprising applying to the surface of the keratinous material at least one cosmetic composition comprising at least one composite material as defined above.

[0517] According to one aspect of the present invention, the present invention relates to a previously defined composite material for use as an agent for filtering UV irradiation, particularly UV-B irradiation.

[0518] In the present invention, the words “prevent” or “prevent” mean at least partially reducing the risk of a given phenomenon, for example, signs of aging of keratinous substances, particularly human keratinous substances, particularly skin, or the occurrence of darker and / or more pigmented spots appearing on the keratinous substances, particularly human keratinous substances, particularly skin, which give uneven skin tone and / or cause premature aging of the skin.

[0519] In the detailed description of the invention and the examples, percentages are weight percentages or molar percentages. The components are mixed in an order and under conditions readily determined by those skilled in the art.

[0520] The present invention will be illustrated by the following embodiments, and these embodiments, of course, do not limit the present invention.

[0521] Examples

[0522] Example 1: Preparation of bismuth oxycarbonate particles according to the present invention

[0523] The bismuth oxycarbonate particles 1 and 2 are synthesized according to the preparation methods described in Examples 1.A and 1.B, which are described later.

[0524] The morphology of the 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. Next, 5 μL of the dispersion was placed on an observation grid (made of copper with a carbon surface layer) and dried in the air.

[0525] Observations are performed using a Hitachi HT 7700 transmission electron microscope with an accelerating voltage of 100kV. Average dimensions are obtained by measuring particle dimensions through image analysis using ImageJ software (CASchneider, WSRasband, KWEliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat. Methods. 9 (2012) 671~675).

[0526] Example 1.A: Synthesis of the bismuth oxycarbonate particles 1

[0527] A solution of bismuth nitrate pentahydrate: Bi(NO3)3·5H2O (0.40M) and D-mannitol (2M) was prepared in 800 mL of water and stirred until the reagents were completely dissolved. Next, 160 mL of ammonium carbonate solution (2.1 equivalents relative to bismuth) was added. A white solid precipitate formed. After 30 minutes, this mixture was then transferred to a Teflon® autoclave reactor and heated at 150°C for 12 hours. Bismuth oxycarbonate particles were separated by centrifugation, washed three times with water, and then oven-dried at 60°C.

[0528] The bismuth oxycarbonate particles 1 are plate-like particles having the following average dimensions: Average length L: 85nm Average width l:52nm Average thickness e: 28nm

[0529] Example 1.B: Synthesis of the bismuth oxycarbonate particles 2

[0530] A solution of bismuth nitrate pentahydrate: Bi(NO3)3·5H2O (0.40 M) and D-mannitol (0.87 M) was prepared in 800 mL of water and stirred until the reagents were completely dissolved. Next, 160 mL of ammonium carbonate solution (2.1 equivalents relative to bismuth) was added. A white solid precipitate formed. This mixture was then transferred to a Teflon® autoclave reactor and heated at 125°C for 7.5 hours. Product 2 was separated by centrifugation, washed three times with water, and then oven-dried at 60°C.

[0531] The bismuth oxycarbonate particles 2 are plate-like particles having the following average dimensions: Average length L: 86nm Average width l:53nm Average thickness e: 28nm

[0532] Example 2: Synthesis of composite materials according to the present invention

[0533] Example 2.A1: Synthesis of bismuth oxycarbonate / carrageenan composite material by atomization at a mass ratio of 1.66

[0534] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0535] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight at room temperature. The resulting white dispersion is then atomized at 150°C with a pump speed of 15%, a suction speed of 80%, and two nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0536] Composite material A1 is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0537] Example 2.A2: Synthesis of bismuth oxycarbonate / carrageenan composite material by atomization at a mass ratio of 0.5

[0538] A solution of carrageenan (INCI name CARRAGEENAN) (2g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The viscous medium is then cooled to room temperature.

[0539] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this viscous solution, and the suspension is sonicated for 15 minutes, then stirred overnight at room temperature. The resulting white dispersion is then atomized at 150°C with a pump speed of 15%, a suction speed of 80%, and four nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0540] Composite material A2 is separated in the form of a white-brown powder and then characterized by a UV / Vis spectrophotometer.

[0541] Example 2.B1: Synthesis of bismuth oxycarbonate / carrageenan composite material by freeze-drying at a mass ratio of 1.66

[0542] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0543] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then freeze-dried.

[0544] Composite material B1 is isolated in the form of a white solid and then characterized by a UV / Vis spectrophotometer.

[0545] Example 2.B2: Synthesis of bismuth oxycarbonate / carrageenan composite material by freeze-drying at a mass ratio of 4.16

[0546] A solution of carrageenan (INCI name CARRAGEENAN) (0.24 g) in 100 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0547] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then freeze-dried.

[0548] Composite material B2 is isolated in the form of a white solid and then characterized by a UV / Vis spectrophotometer.

[0549] Example 2.C1: Synthesis of bismuth oxycarbonate / carrageenan composite material by centrifugation at a mass ratio of 1.66

[0550] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0551] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then centrifuged. The pellets are washed with ethanol and then centrifuged again. The resulting solid is oven-dried under vacuum at 50°C.

[0552] The composite material C1 is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0553] Example 2.C2: Synthesis of bismuth oxycarbonate / carrageenan composite material by precipitation / centrifugation at a mass ratio of 1.66

[0554] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0555] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then precipitated with four times the volume of ethanol, and then centrifuged. The resulting solid is oven-dried under vacuum at 50°C.

[0556] The composite material C2 is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0557] Example 2.C3: Synthesis of bismuth oxycarbonate / carrageenan composite material by precipitation / centrifugation at a mass ratio of 1.66

[0558] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0559] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then precipitated with four times the volume of ethanol, and then centrifuged. The resulting solid is oven-dried under vacuum at 50°C.

[0560] Composite material C3 is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0561] Example 2.C4: Synthesis of bismuth oxycarbonate / carrageenan composite material by precipitation / centrifugation at a mass ratio of 1.66

[0562] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0563] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then precipitated with 10 times the volume of ethanol, and then centrifuged. The resulting solid is oven-dried under vacuum at 50°C.

[0564] The composite material C4 is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0565] Example 2.D: Synthesis of bismuth oxycarbonate / carrageenan composite material by atomization at a mass ratio of 1.66

[0566] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0567] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then atomized at 150°C with a pump speed of 15%, a suction speed of 80%, and five nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0568] Composite material D is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0569] Example 2.E1: Synthesis of bismuth oxycarbonate / carrageenan composite material by freeze-drying at a mass ratio of 1.66

[0570] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0571] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then freeze-dried.

[0572] Composite material E1 is isolated in the form of a white solid and then characterized by a UV / Vis spectrophotometer.

[0573] Example 2.E2: Synthesis of bismuth oxycarbonate / carrageenan composite material by freeze-drying at a mass ratio of 4.16

[0574] A solution of carrageenan (INCI name CARRAGEENAN) (0.24 g) in 100 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0575] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then freeze-dried.

[0576] Composite material E2 is isolated in the form of a white solid and then characterized by a UV / Vis spectrophotometer.

[0577] Example 2.F1: Synthesis of bismuth oxycarbonate / carrageenan composite material by centrifugation at a mass ratio of 1.66

[0578] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0579] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then centrifuged, washed with ethanol, and centrifuged again. The resulting solid is oven-dried under vacuum at 50°C.

[0580] The composite material F1 is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0581] Example 2. F2: Synthesis of bismuth oxycarbonate / carrageenan composite material by precipitation / centrifugation at a mass ratio of 1.66

[0582] A solution of carrageenan (INCI name CARRAGEENAN) (0.6g) in 100mL of water is stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0583] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then precipitated with four times the volume of ethanol, and then centrifuged. The resulting solid is oven-dried under vacuum at 50°C.

[0584] The composite material F2 is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0585] Example 2.G: Synthesis of bismuth oxycarbonate / calcium lignosulfonate composite material by atomization at a mass ratio of 0.71

[0586] A solution of calcium lignosulfonate (DP25228, sold by Borregaard) (1.4g) in 100mL of water is stirred until the polymer is completely dissolved.

[0587] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting light beige dispersion is then atomized at 120°C with a pump speed of 15%, a suction speed of 80%, and five nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0588] Composite material G is separated in the form of a beige powder and then characterized by a UV / Vis spectrophotometer.

[0589] Example 2. Synthesis of bismuth oxycarbonate / calcium lignosulfonate composite material by freeze-drying at a mass ratio of H1: 0.71

[0590] A solution of calcium lignosulfonate (DP25228, sold by Borregaard) (1.4g) in 100mL of water is stirred until the polymer is completely dissolved.

[0591] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The light beige dispersion is then freeze-dried.

[0592] The composite material H1 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0593] Example 2. Synthesis of bismuth oxycarbonate / calcium lignosulfonate composite material by freeze-drying at a mass ratio of H2:1.78

[0594] A solution of calcium lignosulfonate (DP25228, sold by Borregaard) (0.56 g) in 100 mL of water is stirred until the polymer is completely dissolved.

[0595] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The light beige dispersion is then freeze-dried.

[0596] The composite material H2 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0597] Example 2.I: Synthesis of bismuth oxycarbonate / sodium lignosulfonate composite material by atomization at a mass ratio of 0.71

[0598] A solution of sodium lignosulfonate (DP25230, sold by Borregaard) (1.4g) in 100mL of water is stirred until the polymer is completely dissolved.

[0599] 1 g of bismuth oxycarbonate particles according to Example 1B are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The light beige dispersion is then atomized at 120°C with a pump speed of 15%, a suction speed of 80%, and five nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0600] Composite material I is separated in the form of a beige powder and then characterized by a UV / Vis spectrophotometer.

[0601] Example 2.J1: Synthesis of bismuth oxycarbonate / sodium lignosulfonate composite material by freeze-drying at a mass ratio of 0.71

[0602] A solution of sodium lignosulfonate (DP25230, sold by Borregaard) (1.4g) in 100mL of water is stirred until the polymer is completely dissolved.

[0603] According to Example 1B, 1 g of bismuth oxycarbonate particles were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The light beige dispersion was then freeze-dried.

[0604] The composite material J1 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0605] Example 2. J2: Synthesis of bismuth oxycarbonate / sodium lignosulfonate composite material by freeze-drying at a mass ratio of 1.78

[0606] A solution of sodium lignosulfonate (DP25230, sold by Borregaard) (0.56 g) in 100 mL of water is stirred until the polymer is completely dissolved.

[0607] According to Example 1B, 1 g of bismuth oxycarbonate particles were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The light beige dispersion was then freeze-dried.

[0608] The composite material J2 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0609] Example 2. Synthesis of bismuth oxycarbonate / chitosan composite material by atomization at a K:mass ratio of 0.6

[0610] A solution of chitosan (Kiosmetine-CSG, sold by Kitozyme) (1.64 g) in 100 mL of water is adjusted to pH 4 with lactic acid, and then stirred until the polymer is completely dissolved.

[0611] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting light beige dispersion is then atomized at 160°C with a pump speed of 15%, a suction speed of 80%, and five nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0612] Composite material K is separated in the form of a beige powder and then characterized by a UV / Vis spectrophotometer.

[0613] Example 2. L1: Synthesis of bismuth oxycarbonate / chitosan composite material by freeze-drying at a mass ratio of 0.6

[0614] A solution of chitosan (Kiosmetine-CSG, sold by Kitozyme) (1.64 g) in 100 mL of water is adjusted to pH 4 with lactic acid, and then stirred until the polymer is completely dissolved.

[0615] According to Example 1B, 1 g of bismuth oxycarbonate particles were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The light beige dispersion was then freeze-dried.

[0616] The composite material L1 is separated in the form of a beige powder and then characterized by a UV / Vis spectrophotometer.

[0617] Example 2. L2: Synthesis of bismuth oxycarbonate / chitosan composite material by freeze-drying at a mass ratio of 1.51

[0618] A solution of chitosan (Kiosmetine-CSG, sold by Kitozyme) (0.66g) in 100mL of water is adjusted to pH 4 with lactic acid, and then stirred until the polymer is completely dissolved.

[0619] According to Example 1B, 1 g of bismuth oxycarbonate particles were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The light beige dispersion was then freeze-dried.

[0620] The composite material L2 is separated in the form of a beige powder and then characterized by a UV / Vis spectrophotometer.

[0621] Example 2. Synthesis of bismuth oxycarbonate / sodium alginate composite material by atomization at a mass ratio of M: 1.06

[0622] A solution of sodium alginate (0.94 g) in 100 mL of water is heated to 40°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0623] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then atomized at 160°C with a pump speed of 15%, a suction speed of 80%, and two nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0624] The composite material M is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0625] Example 2. N1: Synthesis of bismuth oxycarbonate / sodium alginate composite material by freeze-drying at a mass ratio of 1.06

[0626] A solution of sodium alginate (0.94 g) in 100 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0627] One g of bismuth oxycarbonate particles according to Example 1A is added to the solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then freeze-dried.

[0628] Composite material N1 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0629] Example 2. Synthesis of bismuth oxycarbonate / sodium alginate composite material by freeze-drying at a N2:mass ratio of 2.7

[0630] A solution of sodium alginate (0.37 g) in 100 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0631] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then freeze-dried.

[0632] The composite material N2 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0633] Example 2. O1: Synthesis of bismuth oxycarbonate / sodium alginate composite material by separation (centrifugation) at a mass ratio of 1.06

[0634] A solution of sodium alginate (0.94 g) in 100 mL of water is stirred until the polymer is completely dissolved. Then, the medium is cooled to room temperature.

[0635] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then centrifuged, washed with ethanol, and centrifuged again. The resulting solid is oven-dried under vacuum at 50°C.

[0636] The composite material O1 is separated in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0637] Example 2. Synthesis of bismuth oxycarbonate / sodium alginate composite material by centrifugation at an O2:mass ratio of 1.06

[0638] A solution of sodium alginate (0.94 g) in 100 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0639] 1 g of bismuth oxycarbonate particles according to Example 1A are added to the solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then heated at 55°C for 1 hour and 30 minutes, then returned to room temperature, then centrifuged, washed with ethanol, and centrifuged again. The resulting solid is oven-dried under vacuum at 50°C.

[0640] The composite material O2 is separated in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0641] Example 2. P1: Synthesis of bismuth oxycarbonate / dextran sulfate sodium composite material by atomization at a mass ratio of 0.9

[0642] A solution of 1.1 g of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) in 100 mL of water is stirred until the polymer is completely dissolved.

[0643] 1 g of bismuth oxycarbonate particles according to Example 1B are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The white dispersion is then atomized at 120°C with a pump speed of 15%, a suction speed of 80%, and four nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0644] The composite material P1 is separated in the form of a beige powder and then characterized by a UV / Vis spectrophotometer.

[0645] Example 2. P2: Synthesis of bismuth oxycarbonate / dextran sulfate sodium composite material by atomization at a mass ratio of 8.33.

[0646] A solution of 0.12 g of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) in 100 mL of water is stirred until the polymer is completely dissolved.

[0647] 1 g of bismuth oxycarbonate particles according to Example 1B are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The white dispersion is then atomized at 120°C with a pump speed of 15%, a suction speed of 80%, and two nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0648] The composite material P2 is separated in the form of a beige powder and then characterized by a UV / Vis spectrophotometer.

[0649] Example 2. Q1: Synthesis of bismuth oxycarbonate / dextran sodium sulfate composite material by freeze-drying at a mass ratio of 0.9

[0650] A solution of 1.1 g of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) in 100 mL of water is stirred until the polymer is completely dissolved.

[0651] 1 g of bismuth oxycarbonate particles according to Example 1B are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The white dispersion is then freeze-dried.

[0652] The composite material Q1 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0653] Example 2. Q2: Synthesis of bismuth oxycarbonate / dextran sulfate sodium composite material by freeze-drying at a mass ratio of 2.27

[0654] A solution of 0.44 g of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) in 100 mL of water is stirred until the polymer is completely dissolved.

[0655] 1 g of bismuth oxycarbonate particles according to Example 1B are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The white dispersion is then freeze-dried.

[0656] The composite material Q2 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0657] Example 2. Synthesis of bismuth oxycarbonate / polyvinyl alcohol composite material by atomization at a mass ratio of R: 0.84

[0658] A solution of polyvinyl alcohol (Mowiol 8-88, sold by Sigma Aldrich) (1.19 g) in 100 mL of water is stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0659] 1 g of bismuth oxycarbonate particles according to Example 1B are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then atomized at 120°C with a pump speed of 15%, a suction speed of 80%, and three nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0660] The composite material R is separated in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0661] Example 2.S1: Synthesis of bismuth oxycarbonate / polyvinyl alcohol composite material by freeze-drying at a mass ratio of 0.84

[0662] A solution of polyvinyl alcohol (Mowiol 8-88, sold by Sigma Aldrich) (1.19 g) in 100 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0663] One g of bismuth oxycarbonate particles according to Example 1B were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was then freeze-dried.

[0664] The composite material S1 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0665] Example 2.S2: Synthesis of bismuth oxycarbonate / polyvinyl alcohol composite material by freeze-drying at a mass ratio of 2.12

[0666] A solution of polyvinyl alcohol (Mowiol 8-88, sold by Sigma Aldrich) (0.47 g) in 100 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0667] One g of bismuth oxycarbonate particles according to Example 1B were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was then freeze-dried.

[0668] The composite material S2 is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0669] Example 2. Synthesis of bismuth oxycarbonate / polyhydroxystearic acid composite material by precipitation / centrifugation at a mass ratio of T:2.12

[0670] 0.84 g of polyhydroxystearic acid (INCI name: POLYHYDROXYSTEARIC ACID) in 50 mL of acetone is heated to 50°C and then stirred until the polymer is completely dissolved.

[0671] A suspension of 1 g of bismuth oxycarbonate particles in 50 mL of acetone according to Example 1B is sonicated for 15 minutes, then added to a polymer solution at 50°C, and then stirred overnight at room temperature. The resulting white dispersion is then centrifuged. The pellets are washed with acetone and then centrifuged again. The resulting solid is oven-dried under vacuum at 50°C. The resulting white dispersion is then freeze-dried.

[0672] The composite material T is separated in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0673] Example 2. Synthesis of a bismuth oxycarbonate / dextran sulfate sodium composite material by freeze-drying at a mass ratio of U: 0.9 (not according to the present invention)

[0674] A solution of 1.1 g of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) in 100 mL of water is stirred until the polymer is completely dissolved.

[0675] One g of bismuth oxycarbonate particles (500 nm in length, 50 nm in width) not conforming to the present invention were added to the solution. The suspension was sonicated for 15 minutes, and then stirred overnight. The white dispersion was then freeze-dried.

[0676] The composite material U is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0677] Example 2. Synthesis of a bismuth oxycarbonate / pregelatinized hydroxypropyl corn phosphate distarch composite material by freeze-drying at a mass ratio of V:1.1

[0678] A solution of pregelatinized hydroxypropyl starch phosphate (INCI name: HYDROXYPROPYL STARCH PHOSPHATE) (0.93 g) in 100 mL of water is heated to 95°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0679] One g of bismuth oxycarbonate particles according to Example 1A were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was freeze-dried.

[0680] Composite material V is separated in a downy, beige solid form and characterized by a UV / Vis spectrophotometer.

[0681] Example 2. Synthesis of bismuth oxycarbonate / pregelatinized hydroxypropyl corn phosphate distarch composite particles by freeze-drying at a W:mass ratio of 2.7.

[0682] A solution of pregelatinized hydroxypropyl starch phosphate (INCI name: HYDROXYPROPYL STARCH PHOSPHATE) (0.37 g) in 100 mL of water is heated to 95°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0683] One g of bismuth oxycarbonate particles according to Example 1A were added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was freeze-dried.

[0684] The composite material W is separated in a downy, beige solid form and characterized by a UV / Vis spectrophotometer.

[0685] Example 2.X: Synthesis of bismuth oxycarbonate / pullulan composite particles by atomization at a mass ratio of 0.71

[0686] A solution of pullulan (sold by Hayashibara) (1.4g) in 100mL of water is stirred until the polymer is completely dissolved.

[0687] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then atomized at 130°C with a pump speed of 15%, a suction speed of 80%, and two nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0688] Composite material X is separated in the form of a white powder and characterized by a UV / Vis spectrophotometer.

[0689] Example 2. Synthesis of bismuth oxycarbonate / pullulan composite particles by freeze-drying at a mass ratio of Y: 0.71

[0690] A solution of pullulan (sold by Hayashibara) (1.4g) in 100mL of water is stirred until the polymer is completely dissolved.

[0691] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is freeze-dried.

[0692] Composite material Y is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0693] Example 2. Z: Synthesis of bismuth oxycarbonate / pullulan composite particles with a mass ratio of 1.78 by freeze-drying.

[0694] A solution of pullulan (sold by Hayashibara) (0.56g) in 100mL of water is stirred until the polymer is completely dissolved.

[0695] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is freeze-dried.

[0696] Composite material Z is separated in the form of a downy white solid and characterized by a UV / Vis spectrophotometer.

[0697] Example 2.AA: Synthesis of bismuth oxycarbonate / myristoyl pullulan composite particles by centrifugation at a mass ratio of 0.71

[0698] A solution of myristoyl pullulan (sold by Katakura Chikkarin) (1.4g) in 100mL of water is stirred until the polymer is completely dissolved.

[0699] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is centrifuged, washed with ethanol, and centrifuged again. The resulting solid is oven-dried under vacuum at 50°C.

[0700] The composite material AA is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0701] Example 2. Synthesis of bismuth oxycarbonate / hydrolyzed soy protein composite particles by atomization at a DD:mass ratio of 2.

[0702] A solution of 0.5g of hydrolyzed soy protein (INCI name: Hydrolyzed soy protein) in 100mL of water is stirred until the polymer is completely dissolved.

[0703] 1 g of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight. The resulting white dispersion is then atomized at 150°C with a pump speed of 15%, a suction speed of 80%, and 9 nozzles (device model: BUCHI B-290 Mini Spray Dryer).

[0704] The composite material DD is separated in the form of a white powder and then characterized by a UV / Vis spectrophotometer.

[0705] Example 2. Combination of bismuth oxycarbonate particles and sodium lignosulfonate polymer at a mass ratio of EE:0.71

[0706] A solution of sodium lignosulfonate (DP25230, sold by Borregaard) (14 mg) in 10 mL of water is stirred until the polymer is completely dissolved.

[0707] 10 g of bismuth oxycarbonate particles according to Example 1B are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight.

[0708] The product EE is characterized by a UV / Vis spectrophotometer.

[0709] Example 2. Combination of bismuth oxycarbonate particles and carrageenan polymer at a mass ratio of FF:1.66

[0710] A solution of carrageenan (INCI name: CARRAGEENAN) (6 mg) in 10 mL of water is heated to 80°C and stirred until the polymer is completely dissolved. The medium is then cooled to room temperature.

[0711] 10 mg of bismuth oxycarbonate particles according to Example 1A are added to this solution, and the suspension is sonicated for 15 minutes, then stirred overnight.

[0712] The product FF is characterized by a UV / Vis spectrophotometer.

[0713] Example 2. Synthesis of composite material bismuth oxycarbonate / ethyl acetate polymer by centrifugation at an HH:mass ratio of 1.06

[0714] A solution of ethyl acetoacetate polymer (INCI name: Ethyl acetoacetate) (0.935 g) in 100 ml of ethyl acetate is stirred until the polymer is completely dissolved.

[0715] One g of bismuth oxycarbonate particles obtained according to Example 1B were added to the solution, and the dispersion was sonicated for 15 minutes, then stirred overnight at room temperature. The resulting white dispersion was then evaporated under vacuum at 40°C, and the resulting solid was redispersed in 40 ml of ethyl acetate. The dispersion was then centrifuged and washed twice with ethyl acetate. The resulting solid was dried in an oven at 50°C.

[0716] The composite material HH is separated as a white powder and characterized by a UV / Vis spectrophotometer.

[0717] Example 2.II: Synthesis of composite material bismuth oxycarbonate / ethyl acetate by centrifugation at a mass ratio of 2.66

[0718] A solution of 0.376 g of ethyl acetoacetate polymer (INCI name: Ethyl acetoacetate) in 100 ml of ethyl acetate is stirred until the polymer is completely dissolved.

[0719] One g of bismuth oxycarbonate particles obtained according to Example 1B was added to the solution, and the dispersion was sonicated for 15 minutes, then stirred overnight at room temperature. The resulting white dispersion was centrifuged and washed twice with ethyl acetate. The resulting solid was oven-dried at 50°C.

[0720] Composite material II is separated as a white powder and characterized by a UV / Vis spectrophotometer.

[0721] Example 2. Synthesis of bismuth oxycarbonate / PHN polymer composite material by centrifugation at a JJ:mass ratio of 0.85

[0722] 1.17 g of PHN polymer (Polyhydroxy Nonanoate) in 100 ml of acetone is stirred until the polymer is completely dissolved.

[0723] One g of bismuth oxycarbonate particles obtained according to Example 1B were added to the polymer solution, and the dispersion was sonicated for 15 minutes, then stirred overnight at room temperature. The white dispersion was centrifuged, and the resulting solid was oven-dried at 50°C.

[0724] The composite material JJ is separated as a white powder and characterized by a UV / Vis spectrophotometer.

[0725] Example 2: Overview of synthesis conditions for substances A to JJ

[0726] Table 1 below summarizes all the products prepared in Examples 2.A1 to 2.JJ.

[0727] [Table 1] JPEG2026522434000012.jpg252170JPEG2026522434000013.jpg32170

[0728] Example 3: Absorbance spectra of bismuth oxycarbonate composite material and combination product

[0729] Absorbance spectra of the composite material according to the present invention and the composite material prepared according to Example 2 were obtained using a UV-Vis spectrophotometer.

[0730] The absorbance spectra were obtained by UV-Vis spectrophotometer for composite materials R, S1, S2, and T, as well as AA, HH, II, and JJ, for 0.005 mass% dispersions of the composites in water with individual mass fractions of 49.85 / 49.85 / 0.30, or in a water / propylene glycol / polysorbate 20 (Tween 20) mixture.

[0731] The quartz cell used for absorbance measurement had a side length of 1 cm. The spectrophotometer used was a Genesys 10S from Thermo Fischer Scientific.

[0732] Preparation of dispersions

[0733] An aqueous dispersion of a bismuth oxycarbonate / polymer composite material containing 0.1% by mass of bismuth oxycarbonate is subjected to sonication for 2 to 15 minutes, and then stirred with a magnetic stirrer for 16 hours. The suspension is then diluted with 0.005% by mass of bismuth oxycarbonate and stirred again with a magnetic stirrer for 20 minutes, after which absorbance measurement is performed.

[0734] UV irradiation filtering is considered effective in UV absorbance measurements that exceed a predetermined threshold. In particular, composite materials with a UV absorbance threshold greater than 0.25 are considered effective for filtering UV irradiation in a dispersion medium containing the composite material at a mass fraction of 0.005%.

[0735] The absorbance spectra are shown in Figures 1 to 20.

[0736] The results are summarized in Table 2 below.

[0737] [Table 2] JPEG2026522434000015.jpg158170

[0738] The composite material according to the present invention exhibits good absorbance of UV rays, resulting in efficient shielding of UV rays, particularly in the UV-B region. In contrast, the comparative composite material exhibits low absorbance and does not provide sufficient shielding across the entire UV range.

[0739] The absorbance spectrum also shows that the composite material according to the present invention has high transparency in the visible range of 400 to 780 nm.

[0740] Example 4: Dynamics of absorbance of composite materials consisting of bismuth oxycarbonate particles and polymer, and composite materials combining bismuth oxycarbonate particles and the same polymer in the same mass ratio.

[0741] The dynamics of absorbance in composite materials consisting of bismuth oxycarbonate particles and polymers, and composite materials combining bismuth oxycarbonate particles and the same polymer in the same mass ratio, were investigated for dispersions containing 0.005 mass% bismuth oxycarbonate in water at 45°C for t=0 and t=48 hours.

[0742] The absorbance spectrum was acquired by a UV-Vis spectrophotometer according to the protocol described in Example 3 and is shown in Figures 16 and 17.

[0743] The results are summarized in Table 3 below.

[0744] [Table 3]

[0745] The composite material according to the present invention exhibits good absorbance of UV rays at t=0 and t=48 hours, and at 45°C, resulting in efficient shielding of UV rays, particularly in the UV-B region. In contrast, the comparative product does not adequately shield the entire UV region.

[0746] Example 5: Preparation of aqueous composition A1.1 according to the present invention

[0747] A solution of sodium lauryl ether sulfate (commercially available from Solvay, Rhodapex ESB 30HA1 MB) is prepared in water to a concentration of 1% by weight by stirring until completely dissolved. It is then diluted with water to a concentration of 0.1% by weight.

[0748] Next, the composite material A1 synthesized according to Example 2.A1 is added to a diluted solution of sodium lauryl ether sulfate at a concentration of 0.1% by weight.

[0749] The mixture is homogenized by magnetic stirring at 600 rpm for 5 minutes, then ultrasonically treated in an ultrasonic chamber (Prolabo TP 680 / DH) at 100% power, continuous mode for 15 minutes. Finally, it is placed under magnetic stirring at 600 rpm for 16 hours.

[0750] The composition obtained as a dispersion is referred to as A1.1.

[0751] Example 6: Absorbance spectrum of aqueous composition A1.1 according to the present invention

[0752] The dispersion A1.1 according to Example 5 was diluted by adding deionized water so that the final concentration in composite material A1 was 0.005% by weight, then placed under magnetic stirring at 600 rpm for 20 minutes, and subsequently absorbance measurements were performed.

[0753] The quartz cell used for absorbance measurement was 1 cm thick. The absorbance spectrum was acquired using a UV-2600 UV-Vis spectrophotometer (Shimadzu Corporation). Baseline determination was performed beforehand on a quartz cell filled with water.

[0754] If the measured UV absorbance exceeds a predetermined threshold, the filtration of UV rays is considered efficient. In particular, a composition containing 0.005 wt% of composite material A1 according to Example 2.A1 is considered to efficiently filter UV rays if their maximum absorbances in the UV region exceed 0.25.

[0755] The absorbance spectrum of composition A1.1 according to the present invention is shown in Figure 21.

[0756] The absorbance values ​​are reported in Table 4 below.

[0757] [Table 4]

[0758] Composition A1.1 according to the present invention exhibits good absorbance in the UV region, particularly in the UV-B region, and consequently shows efficient filtration of UV rays.

[0759] The absorbance spectrum also shows that composition A1.1 according to the present invention has high transparency in the visible range of 400 to 780 nm.

Claims

1. It is a composite material, a) The following formula (I) (BiO) 2-x (CO 3 ), in the equation, -0.4 < x < 0.6, At least one particle of bismuth oxycarbonate and its solvate, for example, its hydrate. Here, the maximum average dimension of the particles is less than 400 nm; and, b) At least one polymer The composite material, including the above.

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 1 μm or less, more preferably 500 nm or less, and even more preferably 450 nm or less.

3. The composite material according to claim 1 or 2, wherein the mass ratio of one or more bismuth oxycarbonate particles a) to one or more polymers b) is in the range of 0.01 to 50, preferably 0.2 to 15, more preferably 0.3 to 10, and more preferably 0.5 to 8.

5.

4. The following equation (I) (BiO) 2-x (CO 3 ), in the equation, -0.4 < x < 0.6, A core comprising at least one particle of bismuth oxycarbonate and its solvate, for example, its hydrate, Here, the maximum average dimension of the particles is less than 400 nm; and, The core is surrounded by a continuous or discontinuous layer and b) at least one layer comprising at least one polymer A composite material according to any one of claims 1 to 3, including the above.

5. The composite material according to any one of claims 1 to 4, wherein the molar ratio of the number of moles of one or more coating compounds to the number of moles of one or more core compounds is in the range of 0.0001 to 20, preferably in the range of 0.005 to 15, more preferably in the range of 0.01 to 10, and even more preferably in the range of 0.05 to 5.

6. The composite material according to any one of claims 1 to 5, wherein the bismuth oxycarbonate particles are crystalline.

7. The bismuth oxycarbonate particles are, (BiO) 2 (WHAT 3 ) The composite material according to any one of claims 1 to 6, comprising and a solvate thereof, for example, a hydrate thereof.

8. The composite material according to any one of claims 1 to 7, wherein the bismuth oxycarbonate particles are tubular, plate-shaped and / or rod-shaped, preferably plate-shaped and / or rod-shaped.

9. The composite material according to any one of claims 1 to 8, wherein the one or more polymers b) are nonionic, anionic, or cationic, preferably nonionic or anionic, and more particularly selected from polyethylene glycol, polyethyleneamine, polypropylene glycol, polyvinyl alcohol, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, polymethyl methacrylate, polyvinyl sulfonate, polystyrene sulfonate, polylactic acid and salts thereof, polycaprolactone, polyglycolic acid, polyacetate, poly(lactic acid-coglycolic acid), cellulose and derivatives thereof, alginic acid and salts thereof, carrageenan, starch, pectin, inulin, dextran and derivatives thereof, xanthan gum, urban, lignosulfonate and salts thereof, chitin and chitosan, pullulan, polyvinyl alcohol and polyhydroxystearic acid, and / or copolymers thereof, or combinations thereof.

10. The one or more polymers b) mentioned above, Lignosulfonic acid, lignosulfonate, polystyrene sulfonate, polystyrene sulfonate, anionic polyanethole derivatives, especially polyanethole sulfonate, and combinations thereof. Alkyl esters or ethers of polyols, especially glycerols, Anionic polysaccharides, preferably sulfated polysaccharides, particularly urban, dextran sulfate, carrageenan and combinations thereof, and anionic polysaccharides selected from polysaccharide carboxylates, particularly alginates. Cationic polysaccharides, preferably polysaccharides having an amine group, particularly chitosan, selected from cationic polysaccharides, Modified polysaccharides, particularly polysaccharide esters, preferably pullulan esters, are selected from modified polysaccharides, Poly((C 2 ~C 5 )) alkyleneimine), preferably polyethyleneimine and polypropyleneimine, especially poly(ethyleneimine), selected from poly((C 2 ~C 5 )) alkyleneimine, Polyamino acids, preferably polyamino acids selected from proteins, An anionic acyclic polymer having a carboxyl group or an alkali metal or alkaline earth metal, such as sodium, and selected from homopolymers or copolymers of (meth)acrylic acid, preferably selected from polysodium methacrylate and copolymers of (meth)acrylic acid and alkyl (poly)ether (meth)acrylate, particularly selected from copolymers of (meth)acrylic acid and POE / POP (meth)acrylate, and those combinations A composite material according to any one of claims 1 to 9, selected from the following.

11. The one or more polymers b) mentioned above, Lignosulfonates, in particular alkali metal or alkaline earth metal lignosulfonates, such as sodium lignosulfonate or calcium lignosulfonate. Carrageenan, Chitosan, Alginates, in particular, alkali metal or alkaline earth metal alginates, such as sodium alginate, Dextran, particularly alkali metal or alkaline earth metal dextran and alkali metal or alkaline earth metal dextran sulfate, such as dextran sodium sulfate. Polyhydroxystearic acid, Starch and its derivatives, in particular its phosphate derivatives, such as hydroxypropylcorn phosphate distarch, Pullulan and its ester derivatives, in particular, C 1 ~C 30 Preferably C 10 ~C 20 Carboxylic acids, ester derivatives of, for example, myristoyl pullulan, Polyvinyl alcohol, Proteins that may be hydrolyzed, such as hydrolyzed soy protein, and those combinations A composite material according to any one of claims 1 to 10, selected from the above.

12. The one or more polymers b) mentioned above are selected from polysaccharides, and in particular, Anionic polysaccharides, preferably sulfated polysaccharides, particularly urban, dextran sulfate, carrageenan and combinations thereof, and anionic polysaccharides selected from polysaccharide carboxylates, particularly alginates. Cationic polysaccharides, preferably polysaccharides having an amine group, particularly chitosan, selected from cationic polysaccharides, Modified polysaccharides, particularly polysaccharide esters, preferably pullulan esters, are selected from modified polysaccharides, A composite material according to any one of claims 1 to 9, selected from the following.

13. A method for preparing a composite material according to any one of claims 1 to 12, (i) The following equation (I) (BiO) 2-x (CO 3 ), in the equation, -0.4 < x < 0.6, To prepare at least one particle of bismuth oxycarbonate and its solvate, for example, its hydrate, wherein the maximum average size of the particle is less than 400 nm, and the particle may be dispersed in at least one solvent or solvent mixture A; (ii) Prepare a solution of at least one polymer b) which may be present in a solvent or solvent mixture B; (iii) bringing the at least one particle a) or dispersion (i) into contact with the solution (ii) to form the composite material; (iv) Separating the composite material The method comprising at least the step of:

14. The method for preparation according to claim 13, wherein the one or more solvents A and / or B are selected from nonpolar aprotic solvents and polar protic solvents, more preferably from water, alcohols, polyols and mixtures thereof.

15. A method for preparation according to claim 13 or 14, further comprising one or more steps of separation, particularly separation by centrifugation and / or separation by filtration, particularly separation by ultrafiltration and / or separation by freeze-drying and / or separation by atomization.

16. A composition comprising at least one composite material according to any one of claims 1 to 12, particularly a cosmetic composition.

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; and, iii) 1) UV shielding agent different from the composite material i); 2) coloring agent; 3) cosmetic surfactant for caring for keratinous substances; 4) surfactant; 5) thickener; and at least one compound selected from combinations thereof. The composition according to claim 16, comprising at least the following:

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

19. A 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, the non-therapeutic cosmetic use comprising at least applying a composition containing the composite material according to any one of claims 1 to 12 to a keratin substance.

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

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