Composite material of bismuth subcarbonate and polymer for filtering ultraviolet radiation

Abstract

A composite of bismuthyl carbonate and a polymer for filtering ultraviolet radiation. The present invention relates to a composite material comprising at least one bismuthyl carbonate particle of formula (I) (BiO) 2-x (CO3) and solvates thereof (e.g. Hydrates thereof), where-0.4 lt; xlt; 0.6, the maximum average size of said particles being less than 400 nm, and at least one polymer; relates to processes for their preparation, and also to cosmetic compositions and uses of said composites.

Description

Technical Field

[0001] This invention relates to the field of sun protection, and more specifically to a composite material of bismuth oxycarbonate and a polymer for its use in filtering ultraviolet radiation.

[0002] The present invention also relates to compositions, particularly cosmetic compositions, especially composites comprising bismuth oxycarbonate particles and polymers.

[0003] Keratin materials are exposed to sunlight every day.

[0004] It is known that light radiation with wavelengths between 280 nm and 400 nm is sufficient to tan the human skin. However, rays with wavelengths between 280 nm and 320 nm (known as UV-B rays) are detrimental to the development of natural tanning. This exposure can also easily cause damage to the biomechanical properties of the epidermis, reflected in the appearance of wrinkles, leading to premature aging of the skin.

[0005] It is also known that UV-A rays, with wavelengths between 320 nm and 400 nm, penetrate deeper into the skin than UV-B rays. UV-A rays promote rapid and lasting pigmentation of the skin. Under normal conditions, daily exposure to UV-A radiation (even for short periods) can also lead to damage to collagen and elastin fibers, which is reflected through changes in skin microrelief, wrinkles, and the appearance of uneven pigmentation (i.e., age spots, uneven skin tone, etc.).

[0006] In addition, prolonged exposure to sunlight can dry out hair and make it brittle.

[0007] Therefore, protecting keratin materials, especially human keratin materials such as skin, is crucial. Existing technology

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

[0009] To date, numerous photoprotective cosmetic compositions for the skin have been proposed. These typically contain organic and / or inorganic UV-blocking agents that function through the absorption, reflection, or scattering of UV radiation, depending on their chemical and physical properties. They often contain combinations of oil-soluble and / or water-soluble organic UV-blocking agents combined with metal oxide pigments, such as titanium dioxide (TiO2) or zinc oxide (ZnO).

[0010] Conventional organic opacifiers must possess acceptable cosmetic properties, both individually and in combination, good solubility in common solvents (especially oils), and good photostability. They must also be colorless or have a color that is cosmetically acceptable to consumers. These organic opacifiers are often used in mixtures, and such combinations of opacifiers can limit the range of formulations.

[0011] Furthermore, the use of inorganic UV-blocking agents for light protection is now a highly important expectation among consumers, as they perceive mineral sunscreens as safer.

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

[0013] However, one of the main drawbacks of these mineral masking agents is that they cause a whitening effect on the skin once applied, which is undesirable in terms of cosmetics and is generally not favored by users.

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

[0015] To avoid this problem, a reduced amount of one or more inorganic shielding agents can certainly be used, but the resulting composition (which will of course result in a film with acceptable transparency on the skin) will no longer provide adequate protection in the UV range, which greatly limits the practicality of this option.

[0016] In addition to significant whitening, the use of large amounts of these UV-masking agents after application to the skin results in an unpleasant sensation and significantly causes a feeling of roughness and dryness on the skin when the product is used extensively and regularly.

[0017] Consumers are increasingly seeking products that are effective, easy to apply, provide longer-lasting comfort, and have satisfying sensory properties. Summary of the Invention

[0018] Therefore, there is still a need for inorganic UV-masking agents that provide effective light protection without the aforementioned drawbacks.

[0019] In particular, there is still a need for inorganic UV shielding agents that can effectively block UV rays (especially in the UV-A and UV-B range, and especially UV-B rays), have high transparency to visible light, do not cause whitening of the keratin materials to which they are applied, and have good cosmetic properties.

[0020] There is still a particular need for mineral UV shielding agents other than titanium dioxide or zinc oxide, which have proven to be equally effective, transparent, do not cause a rough and dry feeling on the skin, and are easy to formulate, especially at high concentrations.

[0021] The present invention particularly relates to the proposal of novel mineral UV-screening agents that can meet these expectations. Summary of the Invention Thus, according to its first aspect, the present invention relates to a composite material comprising: a) at least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of the particles is less than 400 nm; and b) at least one polymer.

[0023] Preferably, the present invention relates to a composite material comprising: a) at least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of the particles is less than 400 nm; and [[ID=((20))]] b) at least one polymer selected from polyethylene glycol, polyvinylamine, 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, polyacetoacetate, poly(lactic-co-glycolic acid), cellulose and its derivatives, alginic acid and its salts, carrageenan, starch, pectin, inulin, dextran and its derivatives, xanthan gum, ulvan, lignosulfonate and its salts, chitin and chitosan, pullulan, polyvinyl alcohol and polyhydroxystearic acid, and / or its copolymers, or mixtures thereof.

[0024] Preferably, the present invention relates to a composite material comprising: a) at least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of the particles is less than 400 nm; and b) 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, and even more preferably selected from carrageenan, chitosan, dextran sulfate, (di) starch phosphate, pullulan, and their forms esterified (or acetylated) by carboxylic acids, which preferably contain 1 to 30 carbon atoms, more particularly 8 to 20 carbon atoms, such as myristoyl pullulan and ulvan.

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

[0026] Combinations of bismuth oxide with polymers such as alginate, chitosan, and polyvinyl alcohol have been proposed in various fields beyond sun protection using keratin materials, such as for radiation impermeability in embolization (US8012454, EP 1531874, US 7947073), in medical devices (US 6387978), or for combating hyperacidity (US3257275, US 6024987A). However, these documents do not mention the field of 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 a) to polymer b) is in the range of 0.01 to 50, preferably 0.2 to 15, more preferably 0.3 to 10, and even more preferably 0.5 to 8.5.

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

[0029] In particular, the bismuth oxycarbonate particles are in the form of tubes, plates, and / or rods, preferably in the form of plates and / or rods.

[0030] Preferably, polymer (b) is 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, polyacetoacetate, poly(lactic-co-glycolic acid), cellulose and its derivatives, alginate and its salts, carrageenan, starch, pectin, inulin, dextran and its derivatives, xanthan gum, ulva polysaccharide, lignosulfonate and its salts, chitin and chitosan, pullulan, polyvinyl alcohol and polyhydroxystearic acid, and / or copolymers thereof, or mixtures thereof.

[0031] Specifically, polymer (b) is selected from sodium lignosulfonate, calcium lignosulfonate, polyaniline sulfonate, sodium alginate, carboxymethyl cellulose, hydroxyethyl cellulose, dextran sulfate salt, carrageenan, chitosan, myristoyl pullulan, polyvinyl alcohol and / or copolymers thereof, or mixtures thereof. More specifically, the molar ratio between the molar number of the coating compound (one or more) and the molar number of the core compound (one or more) 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, and as shown in the examples below, the inventors have found that the composite materials according to the invention have excellent effectiveness in shielding against ultraviolet radiation (especially UV-B rays), and high transparency in the visible light range, and enable the provision of cosmetic properties that satisfy consumers to compositions containing them.

[0033] For the purposes of this invention, the term "composite material" refers to a heterogeneous particulate solid material comprising at least two immiscible components, the components being linked by physical and / or chemical interactions.

[0034] For the purposes of this invention, the term "high transparency in the visible light range" refers to particles having high transmittance between 400 and 780 nm.

[0035] For the purposes of this invention, the term "efficiency in filtering ultraviolet radiation" refers to a threshold absorbance in the UV range of particles in a dispersion medium containing the particles at a mass fraction of 0.005%, preferably greater than or equal to 0.30, and even more preferably greater than or equal to 0.35. The higher the threshold absorbance, the greater the efficiency in filtering UV radiation.

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

[0037] Therefore, for the purposes of this invention, the term "UV shielding agent" is intended to refer to any compound that shields ultraviolet (UV) radiation in a wavelength range extending from 280 nm to 400 nm. The term "UV-B shielding agent" is intended to refer to any compound that shields ultraviolet (UV) radiation in a wavelength range extending from 280 nm to 320 nm. The term "UV-A shielding agent" is intended to refer to any compound that shields ultraviolet (UV) radiation in a wavelength range extending from 320 nm to 400 nm.

[0038] For the purposes of this invention, the term "fatty substance" refers to an organic compound that is immiscible in water at room temperature (25°C) and atmospheric pressure (760 mmHg) (solubility less than 5%, preferably less than 1%, and even more preferably less than 0.1%); in addition, under the same temperature and pressure conditions, fatty substances are particularly miscible in all proportions in organic solvents, such as halogenated solvents (e.g., chloroform or dichloromethane), lower alcohols (e.g., ethanol), or aromatic solvents (e.g., benzene or toluene).

[0039] The term “organic or inorganic acid salt” more specifically means salts selected from those derived from: i) hydrochloric acid (HCl), ii) hydrobromic acid (HBr), iii) sulfuric acid (H2SO4), iv) alkyl sulfonic acids: Alk-S(O)2OH, such as methanesulfonic acid and ethanesulfonic acid; v) aryl sulfonic acids: Ar-S(O)2OH, such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-OS(O)OH, such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids, such as toluenesulfinic acid and phenoxysulfinic acid; xii) phosphoric acid (H3PO4); xiii) acetic acid (CH3C(O)OH); xiv) trifluoromethanesulfonic acid (CF3SO3H); and xv) tetrafluoroborate (HBF4); and salts of “acidic” amino acids, such as glutamate and aspartate.

[0040] The term “organic or inorganic base salt” refers to a salt of a base or basic reagent as defined below, such as an alkali metal hydroxide (e.g., sodium hydroxide or potassium hydroxide), ammonia, an amine or an alkanolamine, or a salt of a “basic” amino acid such as lysine or arginine.

[0041] The term "cationic counterion" refers to a cation or cationic group derived from an organic or mineral alkali salt that balances the anionic charge of at least one component of the composition according to the invention; more specifically, the cation counterion is selected from i) alkali metals, such as sodium, potassium, preferably Na. + ii) Alkaline earth metals such as calcium; iii) Ammonium compounds with the radical R, R4N + The R can be the same or different, representing a hydrogen atom or an (C1-C6) alkyl group optionally substituted with one or more hydroxyl groups; preferably, R represents a hydrogen atom or a (C1-C4) alkyl group, such as methyl.

[0042] To the knowledge of the inventors, this effect of the composite material according to the invention is characterized for the first time. The use of a composite material of bismuth oxycarbonate particles and polymers in cosmetic compositions intended for effective shielding against UV radiation, particularly UV-B radiation, has never been proposed before.

[0043] The composite materials according to the invention are particularly designed to protect keratin materials (especially skin and hair) from UV radiation, especially in cosmetic compositions used in the fields of sun protection, hair care or treatment, and makeup.

[0044] Therefore, according to another aspect, the present invention also relates to the non-therapeutic cosmetic use of the composite material according to the invention for filtering UV radiation, preferably UV-B radiation, which at least includes applying a composition comprising the composite material according to the invention to a keratin material.

[0045] The present invention also relates to a non-therapeutic cosmetic method for filtering UV radiation (preferably UV-B radiation), the method comprising at least applying a composition comprising a composite material containing bismuth oxycarbonate and a polymer as defined above to a keratin material.

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

[0047] The term "keratin material" specifically refers to skin (including scalp and lips) and keratin fibers (e.g., hair, eyelashes, eyebrows), especially skin and / or hair, with skin being preferred.

[0048] The term "at least one" is equivalent to "one or more".

[0049] Unless otherwise stated, the terms “between … and …”, “including … and …”, “formed by … and …”, and “the range is … and …” should be understood to include the limit.

[0050] Other features, variations and advantages of the compositions according to the invention will become clearer upon reading the specification and the following examples. Attached Figure Description

[0051] [ Figure 1 [Describes the absorption spectra obtained by UV-Vis spectrophotometry for dispersions of composite materials A1, A2, B1, and B2 in water at 0.005% by mass.]

[0052] [ Figure 2 This describes the absorption spectra obtained by UV-Vis spectrophotometry of the dispersions of composite materials C1, C2, C3, and C4 in water at a mass percentage of 0.005%.

[0053] [ Figure 3 [Describes the absorption spectra obtained by UV-Vis spectrophotometry for the dispersions of composite materials D, E1, E2, F1, and F2 in water at 0.005% by mass.]

[0054] [ Figure 4This describes the absorption spectra obtained by UV-Vis spectrophotometry for the dispersions of composite materials G, H1, and H2 in water at a mass percentage of 0.005%.

[0055] [ Figure 5 [Describes the absorption spectra of the dispersions of composite materials I, J1, and J2 in water at 0.005% by mass, obtained by UV-Vis spectrophotometry.]

[0056] [ Figure 6 This describes the absorption spectra obtained by UV-Vis spectrophotometry for the dispersions of composite materials K, L1, and L2 in water at 0.005% by mass.

[0057] [ Figure 7 This describes the absorption spectra obtained by UV-Vis spectrophotometry for a dispersion of composite materials M, N1, N2, O1, and O2 in water at 0.005% by mass.

[0058] [ Figure 8 This describes the absorption spectra obtained by UV-Vis spectrophotometry for dispersions of composite materials P1, P2, Q1, and Q2 in water at a mass percentage of 0.005%.

[0059] [ Figure 9 [Describes the absorption spectra obtained by UV-Vis spectrophotometry of the dispersions of composite materials S1, S2 and R in a water / propylene glycol / Tween 20 mixture at 0.005% by mass.]

[0060] [ Figure 10 The absorption spectrum of composite material T in a water / propylene glycol / Tween 20 mixture, obtained by UV-Vis spectrophotometry, is described.

[0061] [ Figure 11 [Describes the absorption spectra obtained by UV-Vis spectrophotometry for a dispersion of Alfa Aesar bismuthite and composite material U in water at 0.005% by mass.]

[0062] [ Figure 12 This describes the absorption spectra obtained by UV-Vis spectrophotometry for a dispersion of composite materials V and W in water at 0.005% by mass.

[0063] [ Figure 13 This describes the absorption spectra obtained by UV-Vis spectrophotometry for a dispersion of composite materials X, Y, and Z in water at a mass percentage of 0.005%.

[0064] [ Figure 14The absorption spectrum of the composite material AA in a water / propylene glycol / Tween 20 mixture, obtained by UV-Vis spectrophotometry, is described.

[0065] [ Figure 15 This describes the absorption spectrum obtained by UV-Vis spectrophotometry of a dispersion of composite material DD in water at 0.005% by mass.

[0066] [ Figure 16 The absorption spectra of the dispersions of composite materials I and EE (at t = 0 h and t = 48 h) and sodium lignosulfonate (at 0.005% by mass in water) obtained by UV-Vis spectrophotometry are described.

[0067] [ Figure 17 [Describes the absorption spectra of dispersions of composite materials D and FF obtained by UV-Vis spectrophotometry at t=0h and t=48h, where t=48h is at T=45℃ and in water at 0.005% by mass.]

[0068] [ Figure 18 The absorption spectra of composite material HH obtained by UV-Vis spectrophotometry in a water / propylene glycol / polysorbate 20 mixture (with corresponding mass fractions of 49.85 / 49.85 / 0.30) at 0.005% by mass are described.

[0069] [ Figure 19 The absorption spectrum of composite material II in a water / propylene glycol / polysorbate 20 mixture (with corresponding mass fractions of 49.85 / 49.85 / 0.30) is described by UV-Vis spectrophotometry.

[0070] [ Figure 20 The absorption spectrum of composite material JJ obtained by UV-Vis spectrophotometry in a water / propylene glycol / polysorbate 20 mixture (with corresponding mass fractions of 49.85 / 49.85 / 0.30) at 0.005% by mass is described.

[0071] [ Figure 21 The absorption spectrum of composition A1.1 obtained by UV-Vis spectrophotometry after dilution in deionized water (to 0.005 wt% of composite material A1) is described. Detailed Implementation

[0072] This invention relates to a composite material comprising a) at least one bismuth oxycarbonate particle of formula (I)(BiO). 2-x(CO3) and its solvates, such as its hydrates, where -0.4 < x < 0.6, the maximum average size of said particles being less than 400 nm; and b) at least one polymer.

[0073] Composite material As described above, the composite material comprises a) at least one bismuth oxycarbonate particle and b) at least one polymer.

[0074] According to a specific embodiment, the mass ratio of (one or more) bismuth oxycarbonate particles a) to (one or more) polymers is from 0.01 to 50, preferably from 0.2 to 15, more preferably from 0.3 to 10, and even more preferably from 0.5 to 8.5.

[0075] The terms "mean size" or "mean dimension" are intended to represent the number average of the sizes of the composite material or the particles. The size of the composite material or the particles can be determined by transmission electron microscopy (e.g., 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 via the BET method, or using a laser particle size analyzer. Preferably, the size of the particles is determined by transmission electron microscopy (e.g., using a Hitachi HT 7700 microscope, especially at an acceleration voltage of 100 kV) or by scanning electron microscopy.

[0076] Preferably, measurements are made on the smallest individualized or individuable objects.

[0077] The number average can be calculated by analyzing images obtained using software such as ImageJ software (C.A. Schneider, W.S. Rasband, K.W. Eliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat. Methods. 9(2012) 671–675).

[0078] The average size is selected from the average length L, the average width l, the average thickness e, or the average diameter d.

[0079] The terms "average size of the maximum size" or "maximum average size" of the composite material or the particles are intended to represent the maximum average size of a surface (such as a face) that can be measured between two diametrically opposed points on a single particle. In the context of the present invention, this size is defined as the maximum Féret diameter.

[0080] The “length” L of a composite material or particle is the maximum size that can be observed in an image taken in a direction perpendicular to the plane in which the composite material or particle is located.

[0081] The “width” l and “thickness” e of the composite material or particle are the lengths of the major and minor axes of the smallest possible ellipse, which can incline the mid-section of the composite material or particle.

[0082] The "diameter" d of a composite material or particle is the largest dimension that can be observed along a line passing through the center of a circle or sphere.

[0083] The composite materials according to the present invention can have various shapes and structures.

[0084] The composite material according to the invention can be particularly spherical, cubic, sheet-like, cylindrical, or tubular.

[0085] The shape of the composite material will depend significantly on the method and operating conditions used to prepare it.

[0086] In particular, the composite material according to the invention can be in the form of tubes, sheets, plates, rods, spheres, flowers, pom-poms, threads, filaments, fibers, needles, cubes, or any mixture thereof.

[0087] The composite materials according to the invention can also be aggregated in the form of superstructures. For example, sheets, tubes and / or rods can be aggregated in the form of spheres, flowers or pom-poms.

[0088] According to one particular embodiment, the composite material according to the invention is in the form of a sphere.

[0089] According to a particular embodiment, the composite material according to the invention is in the form of a tube, sheet, and / or rod. Even more preferably, the composite material according to the invention is in the form of a sheet and / or rod.

[0090] Therefore, composite materials in the form of sheets, rods, or tubes are distinctly different from those in the form of spheres, fibers, flowers, pom-poms, threads, filaments, needles, or cubes.

[0091] It should be understood that the composite material according to the invention can be used in the form of a mixture. In particular, the composite material according to the invention can be used in any proportion of a mixture of sheets and / or rods and / or tubes.

[0092] Similarly, spherical composite materials can consist of a polymer matrix and bismutite flakes, exhibiting two morphologies within the same composite. The morphology of films containing bismutite particles can also be achieved through freeze-drying.

[0093] According to a preferred embodiment, the composite material used according to the present invention is mainly or only in the form of a sheet.

[0094] A composite material in the form of a "sheet" has a length greater than its width, and a width greater than its thickness.

[0095] According to a preferred embodiment, the composite material is mainly or only in the form of a rod.

[0096] A composite material in the form of a "rod" has the form of a solid cylinder, and its length L is greater than its diameter d, or has the form of a prism, the base of which is solid and polygonal, preferably triangular or hexagonal, and the diameter d of the circle circumscribing the polygonal base is less than the length L of the prism.

[0097] According to a preferred embodiment, the composite material is mainly or only in the form of a tube.

[0098] A composite material in the form of a "tube" has the form of a hollow cylinder, and its length L is greater than its diameter d.

[0099] For the purposes of the present invention, the term "mainly in the form of a sheet / rod / tube" is intended to mean that at least 50% by number, particularly at least 70% by number, or even at least 90% by number of the composite material is in the form of a sheet / rod / tube, respectively.

[0100] (One or more) bismuth oxycarbonate particles a) and (one or more) polymers b) can be arranged in the composite material in different ways.

[0101] According to one embodiment, the composite material can have at least one core and at least one coating as one or more layers surrounding the core.

[0102] Thus, they can comprise at least one coating as one or more layers surrounding a core that is chemically different from the coating.

[0103] The coating can be formed by one layer or multiple layers.

[0104] The core of the composite material can consist of at least a) particles of bismuth oxycarbonate of the formula (I) (BiO) 2-x (CO3) and its solvates (such as its hydrates), where -0.4 < x < 0.6, and the maximum average size of the particles is less than 400 nm.

[0105] According to a particular embodiment, the core of the composite material can consist of at least one polymer b).

[0106] The composite material can contain bismuth oxycarbonate particles a) as defined above in the core and / or in the (one or more) layers forming the coating.

[0107] According to a particular embodiment, the material contains, in the core, at least one bismuth oxycarbonate particle a) as defined above.

[0108] According to another particular embodiment, the material contains, in the coating, bismuth oxycarbonate particle a) as defined above.

[0109] According to one embodiment, the (one or more) polymer b) may cover all or part of at least one bismuth oxycarbonate particle a).

[0110] According to another embodiment, the (one or more) polymer b) may be covered, completely or partially, with at least one bismuth oxycarbonate particle a).

[0111] In particular, the mass ratio of the (one or more) bismuth oxycarbonate particles a) to the polymer is from 0.01 to 50, preferably from 0.2 to 15, more preferably from 0.3 to 10, and even more preferably from 0.5 to 8.5.

[0112] According to a particular embodiment, the composite material according to the invention contains at least one layer surrounding the core.

[0113] Thus, according to a particular embodiment, the composite material according to the invention comprises a core which contains at least a) at least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) and its solvates, such as its hydrates, where -0.4 < x < 0.6, the maximum average size of the particles being less than 400 nm, the core being covered, continuously or discontinuously, on its surface with a coating which contains b) at least one polymer.

[0114] According to a first variant of the invention, the composite material according to the invention comprises a coating, also called a shell or envelope, which is continuous, i.e. surrounding the entire surface of the core.

[0115] According to a second variant of the invention, the composite material according to the invention comprises a coating, also called a shell or envelope, which is discontinuous, i.e. surrounding the surface of the core discontinuously.

[0116] Preferably, 10% to 90%, more particularly 10% to 70%, and even more particularly 30% to 50% of the surface of the core is covered with the coating.

[0117] According to one embodiment, the coating is a multilayer coating, i.e. comprising one or more inner layers and outer layers, in other words, several layers which are completely or partially superimposed, each layer being able to be continuous or discontinuous.

[0118] In a multilayer coating, the term "inner layer" means any layer which is not an outer layer. This can be a layer directly superimposed on the core, or any intermediate layer between the core and the outer layer.

[0119] In a multi-layer coating, the term "outer layer" refers to the layer that forms the last layer of the coating and 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.

[0120] In a multi-layer coating formed of two layers, the inner layer is the layer adjacent to the core, and the outer layer is the layer adjacent to the inner layer and not adjacent to the core.

[0121] In a multi-layer coating composed of more than two layers, the inner layer is the layer adjacent to the core and the (one or more) intermediate layers between the layer adjacent to the core and the outer layer.

[0122] The (one or more) inner layers of the multi-layer coating forming the composite material and the single outer layer of the composite material can be formed of the same or different compounds.

[0123] Each layer can be composed of a single compound or a mixture of compounds.

[0124] In particular, the (one or more) layers can extend concentrically with respect to the core.

[0125] In particular, the composite material according to the present invention has a double layer around the core, in other words, an inner layer and an outer layer.

[0126] According to a preferred embodiment, the composite material according to the present invention has at least one layer, preferably containing at least b) at least one polymer.

[0127] According to a preferred embodiment, the composite material according to the present invention comprises: a core that contains at least a) at least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of the particles is less than 400 nm; and at least one layer that continuously or discontinuously surrounds the core and contains b) at least one polymer.

[0128] Preferably, the composite material according to the present invention comprises: - a core that contains at least a) at least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) (formula (I)), and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of the particles is less than 400 nm, - a single layer that is adjacent to the core and contains b) at least one polymer.

[0129] According to a specific embodiment, the composite material according to the present invention comprises: - A core, which contains at least a) particles of at least one bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) (formula (I)), and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of said particles is less than 400 nm, - An inner layer adjacent to said core, which contains at least one inorganic compound c) different from said bismuth oxycarbonate particles a), - An outer layer adjacent to said inner layer, and which contains b) at least one polymer.

[0130] According to a particular embodiment, the composite material according to the invention comprises: - A core, which contains at least a) particles of at least one bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) (formula (I)) and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of said particles is less than 400 nm, - An inner layer adjacent to said core, which contains at least one inorganic compound c) different from said bismuth oxycarbonate particles a), - An outer layer adjacent to said inner layer, and which contains b) at least one polymer and optionally a) particles of at least one bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) (formula (I)) and its solvates, such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of said particles is less than 400 nm.

[0131] a) Bismuth oxycarbonate particles The bismuth oxycarbonate particles a) according to the invention have the formula (I) (BiO) 2-x (CO3), and its solvates, such as its hydrate, where -0.4 < x < 0.6. The value of x can be determined particularly by elemental analysis.<​​​​​​​​​​​​​​

[0137] Thus, the bismuth oxycarbonate particles a) can be a mixture of amorphous particles and crystalline particles.

[0138] For the purposes of the present invention, the term "crystalline" means that the atoms forming the bismuth oxycarbonate particles are arranged in an ordered manner. In other words, crystalline bismuth oxycarbonate particles are organized materials.

[0139] In contrast, "amorphous" particles are those in which the atoms are disordered. The atoms of such particles do not exhibit any organization at the microscopic level.

[0140] Preferably, the crystalline particles required according to the present invention have the crystal phase of the natural ore bismutite, which is called layered and which has [Bi2O2] 2+ and [CO3] 2- alternating layers.

[0141] Such particles crystallize in the orthorhombic system with a space group of Imm P212121.

[0142] The bismutite crystal structure of bismuth oxycarbonate can have the following lattice parameters: a = 3.865 Å; b = 3.862 Å; c = 13.675 Å and V 晶格 = 0.204 nm 3 . This specific atomic arrangement is particularly capable of enabling the growth of anisotropic objects. [[ID=2​​​​​​​​​​​​​​​​​​​​​​In particular, when the composition contains particles a) having the same morphology, the composite material according to the invention is composed of particles in the form of sheets or plates or rods or spheres or flowers or pom-poms or threads or filaments or fibers or needles or cubes, preferably in the form of sheets or rods.

[0150] According to one implementation scheme, particle a) has a different morphology.

[0151] In particular, when the composite material contains particles with different morphologies (a), the composite material according to the invention contains one or more particles selected from the following forms: tubes, sheets, plates, rods, spheres, flowers, pom-poms, threads, filaments, fibers, needles, cubes, or any mixture thereof.

[0152] The particles according to the invention can also be aggregated in the form of superstructures. For example, sheets, tubes and / or rods can be aggregated in the form of spheres, flowers or pom-poms.

[0153] According to a preferred embodiment, the particles according to the invention are in the form of sheets and / or rods.

[0154] Therefore, particles in the form of sheets, rods, or tubes are distinctly different from those in the form of spheres, fibers, flowers, pom-poms, threads, filaments, needles, or cubes.

[0155] Needless to say, the particles according to the invention can be used in the form of mixtures. In particular, the particles according to the invention can be used in mixtures of sheets and / or rods and / or tubes in any proportion, especially in mixtures of sheets and / or rods in any proportion.

[0156] According to a preferred embodiment, the particles used in the present invention are primarily or only in the form of thin sheets.

[0157] Particles in the form of "sheets" have a length greater than their width and a width greater than their thickness.

[0158] In particular, when they are in sheet form, bismuth oxycarbonate particles a) have: - The average length L ranges from 15 to 300 nm, particularly from 30 to 250 nm, preferably from 50 to 200 nm, and more preferably from 70 to 150 nm; - The average width l ranges from 10 to 250 nm, particularly from 20 to 200 nm, preferably from 30 to 150 nm, and more preferably from 50 to 120 nm; - The average thickness e ranges from 2 to 120 nm, particularly from 5 to 100 nm, preferably from 10 to 80 nm, and more preferably from 20 to 50 nm; and -where e <l<L。

[0159] According to one implementation, bismuth oxycarbonate particles are mainly or only in rod form or contain particles in rod form.

[0160] The "bar" form of the particle has a solid cylindrical form with a length L greater than its diameter d, or it has a prism form with a solid and polygonal base, preferably triangular or hexagonal, and the diameter d of the circle circumscribed in the polygonal base is less than the length L of the prism.

[0161] In particular, when they are in rod form, whether cylindrical or prismatic, bismuth oxycarbonate particles have: - The average length L ranges from 30 to 300 nm, particularly from 50 to 250 nm, preferably from 70 to 230 nm, and more preferably from 70 to 140 nm; - The average diameter d ranges from 15 to 150 nm, particularly from 20 to 130 nm, preferably from 25 to 120 nm, more preferably from 25 to 100 nm, and even more preferably from 25 to 60 nm. -Where L>d.

[0162] According to one embodiment, the bismuth oxycarbonate particles of the present invention comprise particles in the form of tubes.

[0163] The "tube"-shaped particles are hollow cylinders with a length L greater than their diameter d.

[0164] In particular, when they are in the form of tubes, bismuth oxycarbonate particles have: - The average length L ranges from 10 to 300 nm, particularly from 20 to 250 nm, preferably from 40 to 200 nm, and more preferably from 60 to 200 nm; - The average diameter d ranges from 2 to 30 nm, particularly from 3 to 20 nm, and preferably from 5 to 15 nm; and -Where L>d.

[0165] For the purposes of this invention, "mainly in the form of sheets / rods" is intended to mean that at least 50% of the particles, particularly at least 70% of the particles, or even at least 90% of the particles, are in the form of sheets / rods.

[0166] Doping of particle a) According to a specific implementation scheme, bismuth oxycarbonate particles a) can be doped.

[0167] In particular, bismuth oxycarbonate particles can be doped with one or more chemical elements that can be inserted into the structure or partially replace existing elements.

[0168] Particles can be doped by replacing all or some of the cations and / or all or some of the anions.

[0169] According to a particular embodiment, the doping portion involves an inserted cation or a bismuth-substituted cation, reaching a limit of 20% of the composition based on bismuth.

[0170] According to this variant, the doping level ranges particularly from 0.005% to 15%, preferably from 0.05% to 12%, more preferably from 0.1% to 10%, and even more preferably from 0.5% to 6%.

[0171] Specifically, bismuth oxycarbonate particles may be doped with cations derived from the following elements: 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).

[0172] 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, more preferably selected from manganese, iron and / or cerium, and even more preferably selected from manganese or iron.

[0173] According to one embodiment variation, the bismuth oxycarbonate particles are doped with manganese-derived cations, and the doping level ranges specifically from 0.5% to 2%.

[0174] According to another embodiment variant, the bismuth oxycarbonate particles are doped with iron-derived cations, and the doping level is particularly in the range of 0.5% to 2%.

[0175] According to another specific embodiment, the doping involves, or involves entirely, the inserted anion or the anion that replaces the carbonate group, reaching a limit of 20% of the composition based on carbonate.

[0176] According to this variant, the doping level ranges particularly from 0.001% to 1%, preferably from 0.002% to 0.5%, more preferably from 0.003% to 0.2%, and even more preferably from 0.005% to 0.1%.

[0177] Specifically, the bismuth oxycarbonate particles may be doped with anions derived from elements selected from fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), and iodine (I), and / or doped with polyatomic anions, particularly sulfate ions (SO4 ions). 2- ), sulfonate ions (S(=O)2-O) - ), sulfite ions (SO3) 2-), phosphate ions (PO4) 3- ) and / or iodate ions (IO3) - ).

[0178] Preferably, the bismuth oxycarbonate particles may be doped with S. 2- SO3 2- SO4 2- Cl - and / or I - More preferably, it is doped with SO3 2- SO4 2- and / or Cl - And more preferably doped with Cl - or SO4 2 .

[0179] According to one embodiment variation, the bismuth oxycarbonate particles are doped with anions derived from chlorine, and the doping level ranges particularly from 0.01% to 0.1%.

[0180] According to another embodiment variant, the bismuth oxycarbonate particles are doped with anions derived from iodine, and the doping level is particularly 0.003% to 0.01%.

[0181] According to another embodiment variant, the bismuth oxycarbonate particles are doped with sulfate ions, and the doping level ranges particularly from 0.005% to 0.1%.

[0182] According to another embodiment variant, the bismuth oxycarbonate particles are doped with cations, said cations preferably derived from elements selected from titanium, vanadium, manganese, iron, copper, zinc, lanthanum and / or cerium, more preferably manganese, iron and / or cerium, and even more preferably manganese or iron, and are doped with anions, said anions preferably derived from elements selected from fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), iodine (I) and / or doped with polyatomic anions, particularly selected from sulfate ions (SO4). 2- ), sulfonate ions (S(=O)2-O) - ), sulfite ions (SO3) 2- ), phosphate ions (PO4) 3- ) and / or iodate ions (IO3) - More preferably, doped with S 2- SO3 2- SO4 2- Cl - and / or I - Even better, it may contain SO3. 2- SO4 2- and / or Cl - And it is particularly preferred to be doped with Cl. - I -or SO4 2- .

[0183] According to a preferred embodiment, the bismuth oxycarbonate particles required according to the present invention are undoped.

[0184] According to another preferred embodiment, the bismuth oxycarbonate particles required according to the invention are doped.

[0185] According to another preferred embodiment, the bismuth oxycarbonate particles required according to the invention are a mixture of doped and undoped particles.

[0186] Method for preparing bismuth oxycarbonate particles a) Bismuth oxycarbonate particles a) can be obtained by any preparation method known to those skilled in the art.

[0187] For example, the synthesis of bismuth oxycarbonate particles is described in the article by Ni et al. (Fabrication, modification and application of (BiO)2CO3-based photocatalysts: A review, Applied SurfaceScience, 365, 2016, 314–335).

[0188] Specifically, bismuth oxycarbonate particles can be prepared via a solvothermal route, via an electrochemical route, via coprecipitation, or under reflux, preferably via a solvothermal route or under reflux.

[0189] According to a variant of the first embodiment, bismuth oxycarbonate particles are obtained via a solvothermal route, particularly from bismuth nitrate and various carbonating agents (e.g., sodium carbonate, ammonium carbonate, or urea), in the presence of a polyol and in a polar protic solvent. Such synthesis allows for the production of bismuth oxycarbonate particles in the form of flakes and / or rods, with a maximum size ranging from 50 to 300 nm.

[0190] The solvothermal synthesis of the particles is particularly described in Cheng, G et al. (Shape-controlled solvothermal synthesis of bismuth subcarbonate nanomaterials, J. Solid State Chem. 183, 1878–1883 (2010)); Ruan, M.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); 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); Cheng, G. et al. (Shape-controlled solvothermal synthesis of bismuth subcarbonate nanomaterials, J. Solid State Chem., 183, 2010, 1878–1883); Liu, Y.Y. et al. (Preparation, electronic structure, and photocatalytic properties of Bi2O2CO3 nanosheet, Appl. Surf. Sci., 257, 2010, 172–175); 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, S.Q.et al. (The effects of citrate ion on morphology and photocatalyticactivity of flower-like Bi2O2CO3, Ceram. Int., 40, 2014, 2343–2348); or Chen, R. et al. (Bismuth subcarbonate nanoparticles fabricated by water-in-oilmicroemulsion-assisted hydrothermal process exhibit anti-. Helicobacter pylori In the article (properties, Mater. Res. Bull., 45, 2010, 654–658).

[0191] The electrochemical synthesis of the particles is particularly described in the article 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).

[0192] The synthesis of particles via coprecipitation is particularly described in Chen, XY et al. (Controlled synthesis of bismuth oxo nanoscale crystals (BiOCl, Bi 12 O 17 In the article "Cl2, α-Bi2O3, and (BiO)2CO3) by solution-phase methods, J. Solid State Chem., 180, 2007, 2510–2516".

[0193] The synthesis of particles via refluxing is particularly described in the article by Chen et al. (Fabrication of bismuth subcarbonate nanotube arrays from bismuth citrate, Chem. Commun., 2006, 2265–2267).

[0194] According to a preferred embodiment, the bismuth oxycarbonate particles required according to the invention are obtained via a solvothermal route, for example, according to the method described by Cheng et al., or under reflux, for example, according to the method described by Chen et al.

[0195] According to a preferred embodiment, the bismuth oxycarbonate particles required according to the present invention are obtained by a preparation method using one or more bismuth(III) complexes, one or more carbonating agents, one or more polyols, and optionally one or more polar solvents other than polyols.

[0196] When the particles used according to the present invention are doped, one or more additional reagents comprising doping elements may be added.

[0197] In particular, (one or more) bismuth(III) complexes are selected from bismuth nitrate and its hydrated form, bismuth citrate and its hydrated form, bismuth sulfate and its hydrated form, and bismuth chloride and its hydrated form.

[0198] (One or more) bismuth(III) complexes can also be obtained from bismuth minerals such as elemental bismuth and / or bismuth oxides and / or bismuth sulfides.

[0199] Preferably, the (one or more) bismuth(III) complex is bismuth(III) nitrate of the formula Bi(NO3)3·xH2O and its hydrated form, and more preferably bismuth nitrate pentahydrate of the formula Bi(NO3)3·5H2O.

[0200] 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 selected from Na2CO3, K2CO3, (NH2)2CO, (NH4)2CO3, and more preferably selected from (NH2)2CO and / or (NH4)2CO3.

[0201] Polyols are compounds containing multiple hydroxyl functional groups. They can be particularly selected from glycols, especially ethylene glycol, propylene glycol, butylene glycol, pentanediol, and hexanediol; short-chain or long-chain glycol polymers, such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; glycerol and its derivatives; or sugars, such as glucose, fructose, sucrose, xylitol, mannitols such as D-mannitol, sorbitol, or maltitol.

[0202] According to one embodiment, the bismuth oxycarbonate particles required according to the invention are obtained by a preparation method using polyols or mixtures of polyols.

[0203] According to a variant of the first embodiment, one or more polyols can also be used as solvents. Bismuth oxycarbonate particles can then be obtained, for example, according to the method described below.

[0204] Solution A is formed by the dissolution of a bismuth(III) complex, preferably in a polyol or polyol mixture at a concentration of 0.001 to 0.5 M. Solution B is formed by the partial or complete dissolution of a carbonating agent (preferably 1 to 100 equivalents relative to bismuth) in a polyol or polyol mixture or in a polyol or polyol mixture different from that used in solution A.

[0205] When the solution is doped with cations, it is preferable to incorporate the dopant into solution A. When the solution is doped with anions, it is preferable to incorporate the dopant into solution B.

[0206] In cases where one or more cations and / or one or more anions are doped, the (one or more) cationic dopant is preferably incorporated into solution A, and the (one or more) anionic dopant is preferably incorporated into solution B. Solution A is then added to solution B at room temperature. If the polyol or mixture of polyols is not liquid at room temperature, all solids are mixed.

[0207] The resulting mixture is then heated between 90 and 250 °C for a reaction time between 10 minutes and 48 hours. If the desired reaction temperature is greater than or equal to the boiling point of the solvent, a solvothermal synthesis is performed using an autoclave.

[0208] Preferably, the reaction temperature is between 95°C and 200°C, and the reaction time is between 1 and 24 hours; more preferably, the reaction temperature is between 100°C and 180°C, and the reaction time is between 2 and 16 hours.

[0209] The particles obtained by centrifugation are separated from the reaction medium and washed by continuous dispersion and centrifugation cycles.

[0210] After drying under vacuum at a temperature between 40°C and 60°C, a white powder is obtained.

[0211] When one or more polyols are used as solvents, the obtained bismuth oxycarbonate particles are in the form of flakes, preferably having an average thickness e between 2 and 15 nm, and / or in the form of tubes.

[0212] According to another embodiment variant, one or more polyols are used only as additives and not as solvents. Bismuth oxycarbonate particles can then be obtained, for example, according to the method described below.

[0213] 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 0.01 to 5 M based on the total concentration of the polyols) in a solvent, preferably a polar solvent. Solution B is formed by partially or completely dissolving a carbonating agent (preferably 1 to 100 equivalents relative to the bismuth complex) in a polar solvent (miscible with the solvent from A), said polar solvent being the same as or different from that of solution A, preferably the same.

[0214] When the solution is doped with cations, it is preferable to incorporate the dopant into solution A. When the solution is doped with anions, it is preferable to incorporate the dopant into solution B.

[0215] In the case of doping with one or more cations and / or one or more anions, the (one or more) cationic dopant is preferably incorporated into solution A, and the (one or more) anionic dopant is preferably incorporated into solution B.

[0216] Solution A is then added to solution B at room temperature. The resulting mixture is then heated between 90°C and 250°C for 10 minutes to 48 hours. If the desired reaction temperature is greater than or equal to the boiling point of the solvent, solvothermal synthesis is performed using an autoclave.

[0217] Preferably, the reaction temperature is between 90°C and 150°C, and the reaction time is between 4 and 16 hours.

[0218] The particles obtained by centrifugation are separated from the reaction medium and washed by continuous dispersion and centrifugation cycles.

[0219] After drying under vacuum at a temperature between 40°C and 60°C, a white powder is obtained.

[0220] When (one or more) polyols are used only as additives, they may be selected in particular from ethylene glycol, propylene glycol, glycerol and / or sugars, preferably sugars, and more preferably D-mannitol.

[0221] According to this variant, the synthesis method also uses a solvent different from that of the polyol, or a mixture of solvents different from that of 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 mixtures thereof, and the solvent is even more preferably water.

[0222] In particular, when only one or more polyols are selected as additives and water as solvent, bismuth oxycarbonate particles are preferably obtained in the form of flakes and / or rods.

[0223] polymer b) The composite material according to the present invention comprises at least one polymer b).

[0224] (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 "neutral"). Preferably, (one or more) polymers b) are nonionic, anionic or cationic, more preferably nonionic or anionic.

[0225] In particular, (one or more) polymers b) are selected from polymers having a molecular weight between 1,000 and 20,000,000 Da, preferably between 5,000 and 10,000,000 Da, and even more preferably between 7,000 and 3,000,000 Da.

[0226] (one or more) polymers b) are in cross-linked and / or non-cross-linked form, preferably non-cross-linked.

[0227] (a or more) polymers b) can be silicone polymers or non-silicone polymers.

[0228] According to a particular implementation, (one or more) polymers b) are or contain at least one silicone polymer.

[0229] As an example of silicone polymer b), polydimethylsiloxane copolyols can be mentioned, particularly mixtures of cyclomethylsiloxane and polydimethylsiloxane copolyols (especially those produced by Dow Corning under the name DC 5225 C). ® (for sale), and alkyl polydimethylsiloxane copolyols (especially lauryl polymethylsiloxane copolyols, particularly sold by Dow Corning under the name Dow Corning 5200 Formulation Aid), cetyl polydimethylsiloxane copolyols, and mixtures of cetyl polydimethylsiloxane copolyols, polyglycerol (4 mol) isostearate and hexyl laurate.

[0230] According to a preferred embodiment, (one or more) polymers b) do not contain silicon atoms.

[0231] According to a preferred embodiment, the weight-average molar mass Mw of (one or more) polymers b) is greater than or equal to 2000.

[0232] The term "anionic polymer" refers to a polymer containing one or more anionic groups, particularly carboxyl groups, carboxylates, sulfates, sulfonic acids, sulfonates, phosphates, phosphonic acids, and phosphonates, preferably selected from carboxylates and / or sulfonates and / or sulfates. Anionic derivatives may be formed as salts of alkali metals or alkaline earth metals (preferably sodium or calcium).

[0233] The term "cationic polymer" refers to a polymer containing one or more cationic groups that carry a charge (regardless of pH) or that is cationizable. Preferably, cationic polymer b) contains amino groups.

[0234] The term "nonionic polymer" refers to a polymer that does not have any charged groups or radicals, but can become charged by changing the pH.

[0235] In particular, (one or more) polymers b) may be selected from polyphenols and their salts, polyphenol sulfonates and their salts, polysaccharides and their salts, polybasic acids and their salts, polyols, polyamides, polyamines and their salts, polyesters, polyhydroxyalkanoates, polyureas, polyurethanes, polyethers, polyethylene, polypropylene, polystyrene, proteins and / or copolymers thereof and / or mixtures thereof.

[0236] (a) or (b) polymers are cyclic or acyclic (containing no rings in their structure).

[0237] (a) One or more cyclic polymers (b) may be aromatic (containing at least one aromatic ring) or non-aromatic.

[0238] Examples of aromatic cyclic polymers (b) include lignin sulfonic acid, lignin sulfonates, sulfonated polystyrene, polystyrene sulfonates, anionic polyaniline derivatives, and especially polyaniline sulfonates and mixtures thereof.

[0239] According to a particular embodiment, the polymer (one or more) b) is selected from sulfonated polystyrene, polystyrene sulfonates, especially alkali metal or alkaline earth metal salts, particularly sodium or calcium polystyrene sulfonates.

[0240] According to one embodiment, the polymer(b) is selected from lignin sulfonates or lignin sulfonates of alkali metals or alkaline earth metals, particularly sodium or calcium.

[0241] According to one embodiment, the polymer (one or more) b) is selected from anionic polyaniline derivatives, particularly alkali metal or alkaline earth metal, particularly sodium or calcium, particularly sodium polyaniline sulfonates.

[0242] Preferably, the (one or more) non-aromatic cyclic polymers b) are selected from polysaccharides, which may be anionic, cationic or nonionic.

[0243] Preferably, the polymer (one or more) b) is selected from natural hydrophilic and / or lipophilic and / or amphiphilic and anionic and / or cationic and / or neutral polysaccharides.

[0244] More preferably, the polymer(s) used are natural hydrophilic and / or lipophilic and / or amphiphilic and anionic and / or cationic and / or neutral polysaccharides, and particularly natural hydrophilic anionic and / or cationic and / or neutral polysaccharides. More preferably, the polymer(s) used are neutral or anionic polysaccharides.

[0245] As non-limiting representatives of these polysaccharides, carrageenan, chitosan, dextran sulfate, (ii) starch phosphate, pullulan, and their carboxylic acid esterification (or acetylation) forms, preferably containing 1 to 30 carbon atoms, more particularly 8 to 20 carbon atoms, such as myristoyl pullulan and ulmoides polysaccharide.

[0246] According to a specific embodiment, the (one or more) polymers b) of the present invention represent a mixture of polymers b), one of which is a polysaccharide or its salt, its α or β end-group isomer, its L- or D-configuration optical isomer, and its solvates, such as its hydrates.

[0247] According to specific embodiments, the polymer (b) of the present invention represents a single polysaccharide or its salt, its α or β end-group isomer, its L- or D-configuration optical isomer, and its solvates, such as its hydrates.

[0248] Specifically, the non-aromatic cyclic polymer b) is selected from anionic polysaccharides, and is selected from sulfated polysaccharides, phosphorylated polysaccharides and polysaccharide carboxylates.

[0249] The polysaccharide can be acetylated at will. The degree of acetylation can be from 1% by weight to 40% by weight (the weight content of acetyl units relative to the total weight of the polymer).

[0250] According to a preferred embodiment, polymer b) is selected from polysaccharides having a weight-average molecular weight in the range of 1,000 to 20,000,000 Da, preferably 5,000 to 10,000,000 Da, and even more preferably 7,000 to 3,000,000 Da.

[0251] Phosphorylated starches, such as hydroxypropyl corn distarch phosphate, can be mentioned among phosphorylated polysaccharides.

[0252] Among sulfated polysaccharides, Ulva polysaccharide, dextran sulfate, carrageenan, especially λ carrageenan, fucoidan, Ulva polysaccharide, dextran sulfate and mixtures thereof may be mentioned.

[0253] Advantageously, the degree of polysaccharide sulfation can range from 1% by weight to 90% by weight relative to the weight of (one or more) polysaccharides. Preferably, the degree of sulfation can range from 2% by weight to 85% by weight.

[0254] In particular, sulfated polysaccharide b) can also be selected from Ulva polysaccharide, which is a sulfated polysaccharide derived from algae (especially red or green algae).

[0255] Ulva polysaccharides can be obtained from many Ulva species, among which Ulva (…) is mentioned. Ulva lactuca ), hard stone water ( Ulva rigida ), Amoricana Ulva ( Ulva armoricana ), round stone water shield ( Ulva Rotundata ) and dark algae ( Ulvaria obscura ), and several other enteromorph species, especially *Ulva prolifera* (*Ulva prolifera*). Enteromorpha compressa ), intestinal lichen ( Enteromorpha intestinalis ) and Enteromorpha ( Enteromorpha ramulosa ).

[0256] Ulva polysaccharides mainly consist of rhamnose, glucuronic acid, glucose, galactose, and xylose, as well as sulfate groups. They may also contain varying amounts of galacturonic acid, iduronic acid, and mannose.

[0257] Ulva polysaccharides typically have a polysaccharide sulfation degree of 1% to 30% by weight relative to the weight of the polysaccharide, and more particularly 10% to 20% by weight.

[0258] The relative sugar content of Ulva polysaccharides varies depending on the harvest location, species, and harvest time (one year later). For the extraction of Ulva polysaccharides from Ulva, refer to the extraction methods described in Carbohydrate Research 274 (1995) 251-261 or Hydrobiologia 326 / 327; 473-480, 1996.

[0259] According to a specific implementation scheme, (one or more) polymers b) are or contain at least one ulnauroides polysaccharide.

[0260] In particular, sulfated polysaccharide b) can also be selected from dextran-derived dextran sulfate esters.

[0261] Dextran is a complex branched glucan (a polysaccharide derived from glucose condensation), originally derived from wine. The IUPAC defines dextran as "a branched poly-α-D-glucan of microbial origin, whose glycosidic bonds are predominantly C-1→C-6." The dextran chain varies in length (from 3 to 2000 kilodaltons).

[0262] The main polymer chain consists of α-1,6 glycosidic bonds between glucose monomers, with branched chains containing α-1,3 bonds. This characteristic branching distinguishes dextran from dextrin, a linear glucose polymer linked by α-1,4 or α-1,6 bonds.

[0263] Specifically, dextran sulfate, marketed by PK Chemicals under the trade name Dextran Sulfate 10 SodiumSalt CG, can be used.

[0264] In polysaccharide carboxylates (b), alginate can be mentioned.

[0265] Alginate is obtained from brown algae (such as kelp or bladderwrack). Sodium alginate or calcium alginate is preferred.

[0266] Alginate is a polysaccharide derived from mannuronate or mannuronic acid (some of which are optionally acetylated) and guluronate or guluronic acid. The linkage is of the β1-4 type.

[0267] According to a specific implementation scheme, the polymer (b) of the present invention is selected from nonionic polymers, particularly nonionic polysaccharides.

[0268] Examples of nonionic polysaccharides include starch and pullulan, especially pullulan.

[0269] According to one embodiment, the polymer (one or more) according to the invention b) is selected from nonionic polymers, particularly nonionic polysaccharides, and more specifically, is a polysaccharide modified by the presence of at least one aliphatic, cyclic or acyclic, linear or branched, saturated or unsaturated, aromatic or non-aromatic hydrocarbon-based chain containing 2 to 30 carbon atoms, optionally substituted by one or more atoms or groups selected from: a) halogens, such as chlorine or bromine; b) (hetero)aryl, such as phenyl or furanyl; c) (hetero)cycloalkyl, such as acid anhydrides, epoxides or dithiolanes; d) RX groups, wherein R represents a group selected from: i) cycloalkyl (e.g., cyclohexyl) and / or ii) (di)alkylamino, and / or optionally interrupted by one or more heteroatoms or groups selected from: a') heteroatoms, such as O, S, N(Ra) and Si(Rb)(Rc); b') S(O)r, (thio)carbonyl; c') Or a combination of a') and b'), such as (thio)ester, (thio)amide, (thio)urea, sulfonamide, where r is 1 or 2, Ra represents a hydrogen atom, or a (C1-C4)alkyl or aryl (C1-C4)alkyl group (e.g., benzyl), preferably Ra represents a hydrogen atom, and Rb and Rc, which may be the same or different, represent (C1-C4)alkyl or (C1-C4)alkoxy groups.

[0270] As for modified polysaccharides, those obtained from natural gums, such as those derived from tree or shrub exudates, algae, seeds or tubers, fungi, bacteria, animal organisms or plants, have been physically modified (through chemical reactions or enzymatic processes).

[0271] Specifically, natural rubber can be selected from: - Gum arabinose (a branched polysaccharide composed of galactose, arabinose, rhamnose, and glucuronic acid); - Ghatti gum (a polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid); -Guardian gum (a polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid); -Astragalus gum (a polymer of galacturonic acid, galactose, fucose, xylose and arabinose); - Agar (a polymer derived from galactose and dehydrated galactose); - Alginate (a polymer of mannulic acid and glucuronic acid); - Carrageenan and furcellaran (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 (a polymer of glucose, mannose acetate, mannose / pyruvate 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.

[0272] Specifically, the modified polysaccharides are derived from: i) gum arabic; ii) gum arabic; iii) gum arabic; iv) gum tragacanth; v) agar; vi) alginate; vii) carrageenan and red algae gum; viii) guar gum; ix) locust bean gum; x) fenugreek gum; xi) tamarind gum; xii) konjac gum; xii) xanthan gum or dehydroxanthan gum; xiv) gellan gum; xv) scleroglucan gum; xvi) cellulose; xvii) starch; xviii) inulin; and xx) pectin.

[0273] The plant source of starch molecules (xvii) can be grains or tubers. Therefore, starch is selected from, for example, corn starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch, and pea starch.

[0274] Starch can be chemically or physically modified, particularly through one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, and heat treatment.

[0275] Nonionic modified polysaccharides can be modified physically or chemically. Temperature is a physical treatment that deserves special mention.

[0276] Chemical treatments that may be mentioned include esterification, etherification, amidation, oxidation, metathesis, and addition reactions.

[0277] According to a specific embodiment, the modified polysaccharide is a polysaccharide ether called alkyl polysaccharide, wherein the alkyl group contains 2 to 30 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms.

[0278] Preferably, the alkyl polysaccharide according to the invention is derived from cellulose or guar gum or a mixture thereof.

[0279] According to the specific implementation plan, the modified polysaccharide is alkyl cellulose, whose straight-chain or branched alkyl residues contain 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.

[0280] Alkyl cellulose is a cellulose alkyl ether comprising a chain of β-dehydrated glucose units linked together via acetal bonds. Each dehydrated glucose unit exhibits three replaceable hydroxyl groups, all or some of which can react according to the following reaction: Cell-OM + R-Hal → Cell-OR + MHal Hal represents a halogen, such as Cl; M represents a cationic counterion, such as an alkali metal, Na or K, or an alkaline earth metal, preferably an alkali metal, such as Na; Cell represents a polysaccharide group, such as cellulose; R represents a straight-chain or branched alkyl group containing 1 to 10 carbon atoms, preferably 2 to 3 carbon atoms, such as methyl or ethyl; and Mhal is the resulting salt, such as sodium chloride.

[0281] Advantageously, alkyl cellulose is selected from ethyl cellulose and propyl cellulose.

[0282] According to a specific implementation, the polysaccharide ether is alkyl guar gum, in other words, guar gum modified by replacing the hydroxyl hydrogen with a straight-chain or branched alkyl group (viii), wherein the alkyl group contains 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, for example 2 carbon atoms.

[0283] The alkyl guar polymer used in this invention is preferably ethyl guar gum.

[0284] Ethyl guar gum is known under the INCI name (C1-C5 alkyl galactomannan).

[0285] Alkylated guar gum (having C1-C6 alkyl groups), including ethyl guar gum, is specifically described in patent application EP 708114 and document RD9537807 (October 1995), as well as the methods for preparing it.

[0286] According to a specific embodiment, the modified polysaccharide is a polysaccharide ester, particularly an ester obtained by reacting at least one polysaccharide (e.g., dextrin) with at least one saturated or unsaturated straight-chain or branched-chain acid (which comprises 2 to 30 carbon atoms, particularly 10 to 30 carbon atoms).

[0287] According to a specific embodiment of the present invention, (one or more) modified polysaccharides are selected from polysaccharide monoalkyl esters or polyalkyl esters.

[0288] Among the monoalkyl or polyalkyl esters of sugars or polysaccharides applicable to the present invention, alkyl or polyalkyl esters of dextrin or inulin may be mentioned.

[0289] Of particular note are monoesters or polyesters of dextrin (derived from starch xvii) and at least one fatty acid (e.g., RC(O)-OH), specifically corresponding to the following formula (XVIII): [Chemical Formula 1] 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.

[0290] -R1, R2 and R3, which may be the same or different, are selected from hydrogen or acyl groups (RC(O)-), wherein group R is a straight or branched, saturated or unsaturated hydrocarbon-based group containing 7 to 29, particularly 7 to 21, particularly 11 to 19, more particularly 13 to 17 or even 15 carbon atoms. It should be understood that at least one of said groups R1, R2 or R3 is different from hydrogen.

[0291] Specifically, R1, R2, and R3 represent hydrogen atoms or acyl groups (RC(O)-), where R is a hydrocarbon-based group as previously defined, provided that at least two of the groups R1, R2, or R3 are different from hydrogen.

[0292] All groups R1, R2, and R3 may represent the same or different acyl groups (RC(O)), and the acyl groups are particularly identical.

[0293] In particular, the n mentioned above is advantageously in the range of 25 to 50, and is especially equal to 38 in the general formula of sugar esters that can be used in the present invention.

[0294] It is worth noting that when groups R1, R2, and / or R3 (which may be the same or different) represent acyl groups (RC(O)) (which are derived from fatty carboxylic acids RC(O)OH), the carboxylic acid is preferably selected from octanoic 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, isodecanic acid, isotriadecanoic acid, isomalmitic acid, isostearic acid, isoarachidic acid, isohexanoic acid, decenoic acid, dodecenoic acid, tetradecenoic acid, myristoleic acid, hexadecenoic acid, palmitoleic acid, oleic acid, transoleic acid, asclepinic acid, gondoleic acid, eicosenoic acid, sorbic acid, linoleic acid, linolenic acid, linolenic acid, punicic acid, octadecanotic tetraenoic acid, arachidonic acid, and stearylene acid, and mixtures thereof.

[0295] Preferably, at least one dextrin palmitate is used as a fatty acid ester of dextrin. This ester can be used alone or as a mixture with other esters.

[0296] Preferably, the fatty acid esters of dextrin have a degree of substitution of less than or equal to 2.5 based on one glucose unit, particularly in the range of 1.5 to 2.5, and more preferably 2 to 2.5. The weight-average molecular weight of the dextrin esters can be particularly 10,000 to 150,000 Da, particularly 12,000 to 100,000 Da, and even 15,000 to 80,000 Da.

[0297] Preferably, the modified polysaccharide (one or more) of the present invention is a dextrin ester, more preferably a dextrin palmitate.

[0298] Dextrin esters, especially dextrin palmitate, are known by the name Rheopearl KL2. ® MKL2 ® TL ® or KL ® Available from the company Chiba Flour.

[0299] According to the specific implementation plan, the modified polysaccharide is a modified dextrin, preferably a dextrin ester, and more particularly, a saturated or unsaturated, straight-chain or branched C-chain dextrin. 12 -C 24 Fatty acid esters.

[0300] Preferably, the dextrin ester is selected from saturated or unsaturated, straight-chain or branched C-type esters. 14 -C 24 Esters of fatty acids (such as myristic acid, palmitic acid, or mixtures thereof).

[0301] According to a specific implementation scheme, the dextrin ester is selected from dextrin palmitate, such as Rheopearl KL2 sold by Chiba Flour.® and Rheopearl TL2 ® And dextrin myristate, for example, from Chiba Flour under the reference name Rheopearl MKL2 ® The product for sale is referred to as Rheopearl TT2. ® Dextrin palmitate / ethylhexanoate sold under the reference name Rheopearl WX, dextrin palmitate / hexyl decanoate, or mixtures thereof.

[0302] According to the specific implementation plan, the modified polysaccharide is modified inulin, preferably inulin ester, and more particularly inulin with saturated or unsaturated, straight-chain or branched C-type polysaccharides. 12 -C 24 Fatty acid esters.

[0303] Preferably, inulin esters are selected from saturated or unsaturated, straight-chain or branched, C 14 -C 24 Esters of fatty acids (such as myristic acid, palmitic acid or stearic acid, preferably stearic acid or mixtures thereof).

[0304] According to the specific implementation plan, inulin ester is stearoyl inulin, for example, the reference name Rheopearl ISK2. ® and Rheopearl ISL2 ® Sold by Chiba Flour, or mixtures thereof.

[0305] According to one embodiment, the modified polysaccharide is modified cellulose, preferably a cellulose ester, and more particularly cellulose with saturated or unsaturated, straight-chain or branched C2-C bonds. 24 Esters of acids.

[0306] Preferably, the cellulose ester is selected from saturated or unsaturated, straight-chain or branched C2-C esters. 10 Preferably, C2-C6, especially C2-C4 acids, such as acetic acid, butyric acid or mixtures thereof.

[0307] According to a specific implementation, the cellulose ester is cellulose acetate butyrate, such as the reference name Eastman Cellulose Acetate Butyrate sold by Eastman Chemical. ® .

[0308] According to a particular embodiment, (one or more) polymers b) are selected from nonionic polymers, particularly nonionic polysaccharides, and more particularly with hydrophobic chains (e.g., alkyl urethane groups, especially C8-C). 18 Inulin modified with alkyl carbamates, and more particularly lauryl carbamates.

[0309] As an example of such compounds, the product sold by the company Creachem under the name Inutec SL1 is particularly noteworthy.

[0310] Pullulan esters can also be mentioned among polysaccharide esters. Pullulan is a polysaccharide composed of maltotriose units.

[0311] According to one embodiment, the modified polysaccharide is a polysaccharide ester. The term "polysaccharide ester" refers to a polysaccharide in which at least one hydroxyl group is esterified to form an ester group -OC(O)-R or -C(O)-OR, wherein R represents a saturated or unsaturated group with 2 to 30 carbon atoms, particularly 11 to 19 carbon atoms, preferably 12 to 17 carbon atoms, for example 13 carbon atoms.

[0312] In particular, the polysaccharide ester is myristoyl pullulan polysaccharide.

[0313] According to a specific implementation, (one or more) polymers b) contain at least one cationic modified polysaccharide.

[0314] Preferably, the chemical or physical treatment to obtain at least one cationic group is applied to guar gum, locust bean gum, starch, and cellulose.

[0315] The cationic group can be of the primary, secondary, tertiary, or quaternary amine type, preferably a quaternary amine, and includes C6-C. 30 Aliphatic chains.

[0316] According to the specific implementation scheme, (one or more) modified polysaccharides b) are selected from quaternized (poly)hydroxyethyl cellulose modified with a group including at least one aliphatic chain (or fatty chain), such as alkyl, arylalkyl, alkylaryl groups or mixtures thereof including at least 8 carbon atoms.

[0317] The alkyl groups carried by quaternized cellulose or hydroxyethyl cellulose preferably include 8 to 30 carbon atoms.

[0318] The aryl group preferably represents a phenyl, benzyl, naphthyl, or anthracene group. It can be indicated by the presence of C8-C. 30 Examples of quaternized alkyl hydroxyethyl cellulose with fatty chains include Quatrisoft LM 200, a product marketed by Dow Corning. ® Quatrisoft LM-X 529-18-A ® Quatrisoft LM-X 529-18-B ® (C 12 Alkyl) and Quatrisoft LM-X529-8 ® (C 18Alkyl groups), and Crodacel QM, a product sold by the company Croda. ® Crodacel QL ® (C 12 Alkyl) and Crodacel QS ® (C 18 Alkyl groups) and Softcat SL 100, a product sold by the company Dow Corning. ® .

[0319] According to the specific implementation plan, (one or more) modified polysaccharides b) are selected from C1-C 20 Guar gum modified with (poly)hydroxyalkylammonium groups, preferably C1-C6 (poly)hydroxyalkyl groups.

[0320] By way of example, halide groups of hydroxymethyltrimethylammonium, hydroxyethyltrimethylammonium, hydroxypropyltrimethylammonium and hydroxybutyltrimethylammonium may be specifically mentioned, preferably hydroxypropyltrimethylammonium halide, preferably chloride.

[0321] This type of cationic guar gum, modified with hydroxyalkylammonium groups, is, for example, produced by Solvay under the trade name Cationic Jaguar. ® C-14S Guar Hydroxypropyltrimonium Chloride, F Jaguar ® C-13SGuar Hydroxypropyltrimonium Chloride, F Jaguar ® C-17 GuarHydroxypropyltrimonium Chloride, Jaguar ® Excel Guar HydroxypropyltrimoniumChloride, Jaguar ® C-500 STD Guar Hydroxypropyltrimonium Chloride, Jaguar ® C-162Hydroxypropyl Guar Hydroxypropyltrimonium Chloride, Jaguar ® Optima GuarHydroxypropyltrimonium Chloride and Jaguar ® LS Hydroxypropyl GuarHydroxypropyltrimonium Chloride for sale.

[0322] According to the specific implementation plan, cationic non-aromatic cyclic polymers b) particularly polysaccharides with amine groups, such as chitosan.

[0323] Preferably, the amine group is a primary, secondary, or tertiary amine, with a primary amine being preferred.

[0324] The term “polysaccharide with an amine group” also refers to its organic or inorganic acid salts, its α or β-terminal isomers, its L- or D-configuration optical isomers, and its solvates, such as its hydrates.

[0325] According to the specific implementation, the polysaccharide(s) containing one or more amine groups is selected from those containing C5-C7 sugar units, as well as their organic or inorganic acid salts, their α or β terminal isomers, their L- or D-configuration optical isomers, and their solvates such as their hydrates.

[0326] More specifically, polysaccharides with one or more amine groups contain C6 sugar units with one or more amine groups; these polysaccharides with one or more amine groups are then referred to as polyhexosamines.

[0327] According to a specific implementation scheme, the sugar unit of a polysaccharide with one or more amine groups has a β (beta) anomeric configuration and / or a D configuration.

[0328] According to a specific implementation scheme, the sugar units of a polysaccharide with one or more amine groups are linked together between the C1 carbon atom of one sugar unit and the C4 carbon atom of another sugar unit, denoted as (1→4), such as the polysaccharide with one or more amine groups of formula (B), as well as its organic or inorganic acid salts, its α or β terminal isomers, its L- or D-configuration optical isomers, and its solvates, such as its hydrates: [Chemical Formula 2] In equation (B): -The R group in each sugar unit a R b and R c They can be the same or different; -n is an integer greater than or equal to 2, especially between 3 and 3000 (inclusive); -R a R b and R cThese may be the same or different, representing i) a hydroxyl group, ii) a (C1-C4) alkoxy group, wherein the alkyl group may optionally be substituted, particularly substituted by one or more hydroxyl groups, iii) a carboxyl group, and iv) a group NR1R2, wherein R1 and R2 are as previously defined, particularly R1 and R2 are selected from hydrogen atoms 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, such as methyl; wherein the group R of at least one sugar unit a R b Or R c At least one of the groups NR1R2 in the sugar unit represents an NH2 group; preferably, at least one of the groups NR1R2 in the sugar unit represents an NH2 group. a The symbol NR1R2 represents the group NR1R2, where R1 represents a hydrogen atom and R2 is selected from i) a hydrogen atom or ii) the group -C(O)-R'1, and R b and R c The group represents a hydroxyl group, wherein at least one of the groups NR1R2 of the sugar unit represents an NH2 group.

[0329] More specifically, the polysaccharides of the present invention, having one or more amine groups, have the following formula (B1), and their organic or inorganic acid salts, their α or β-terminal isomers, their L- or D-configuration optical isomers, and their solvates, such as their hydrates: [Chemical Formula 3] In equation (B1): -R' represents a hydrogen atom or a (C1-C4) alkyl carbonyl group, such as acetyl CH3-C(O)-; -R'' represents a hydrogen atom or a (C1-C4) alkyl group, which may optionally be replaced by a carboxyl group such as -CH(CO2H)-CH3; -n is an integer greater than or equal to 2, especially between 3 and 3000 (inclusive); It should be understood that in the polysaccharide (B1), at least one sugar unit has an NH2 amino group, and at least one other sugar unit has at least one group N(H)-R', where R' represents a (C1-C4) alkyl carbonyl group, such as acetyl CH3-C(O)-.

[0330] Preferably, the sugar unit of formula (B) or (B1) has a D configuration, also known as D-glucose pyranose.

[0331] In particular, the units of formula (B) or (B1) have a β (beta) end group configuration.

[0332] According to specific embodiments, the polysaccharides of the present invention are selected from compounds of the following formula (B2), their organic or inorganic acid salts, and their solvates, such as their hydrates: [Chemical Formula 4] In equation (B2): -R a R b and R c As previously defined for (B); -The R group in each sugar unit a R b and R c They can be the same or different; -n is an integer greater than or equal to 2, particularly between 3 and 3000 (inclusive), and more particularly between 5 and 2500, preferably between 10 and 2300; In the polysaccharide (B2), at least one sugar unit has a group R. a R b Or R c At least one of the groups NR1R2 in the sugar unit represents an NH2 group; preferably, at least one sugar unit has a group R representing an amino group NH2. a And at least one other sugar unit carries a group R representing -N(H)-R'. a , where R' represents a (C1-C4) alkyl carbonyl group, such as acetyl CH3-C(O)-.

[0333] Preferably, the polysaccharide(s) containing one or more amine groups is selected from chitin and chitosan and their derivatives, with chitosan being preferred.

[0334] More specifically, the polysaccharides (one or more) containing amine groups are selected from those of formula (B3), their organic or inorganic acid salts, and their solvates, such as their hydrates: [Chemical Formula 5] In equation (B3): -R1 and R2 are as defined in equation (B), (B1) or (B2); and -n is an integer greater than or equal to 2, particularly between 3 and 3000 (inclusive), and more particularly between 5 and 2500, preferably between 10 and 2300; In the polysaccharide of formula (B3), at least one sugar unit has an amino group NH2, and at least one other sugar unit has a group N(H)-R', where R' represents a (C1-C4) alkyl carbonyl group, such as acetyl CH3-C(O)-.

[0335] More specifically, the polysaccharides of the present invention, which have one or more amine groups, are selected from chitosan of formula (B4), their organic or inorganic acid salts, and their solvates, such as their hydrates: [Chemical Formula 6] In equation (B4): -R'1 indicates a (C1-C4) alkyl group, such as methyl; -n is an integer greater than or equal to 2, especially between 3 and 3000 (inclusive); -p is greater than 0 and ranges at most 0.5, preferably 0.05 to 0.3, and still more preferably 0.1 to 0.20, for example 0.15, where m+p equals 1; In chitosan, at least one sugar unit has an amino group NH2, and at least one other sugar unit has a group N(H)-R'1, where R' represents a (C1-C4) alkyl carbonyl group, such as acetyl CH3-C(O)-.

[0336] For example, when m = 0.7 and p = 0.3, this means that 70% of the amino groups are free (unsubstituted) and 30% of the amino groups are N-(C1-C4) alkyl carbonyl groups, especially N-acetyl groups, corresponding to the chitosan polymer of the following formula: [Chemical Formula 7] Where n is as defined above.

[0337] In particular, the polysaccharides of the present invention having one or more amine groups are selected from chitosan, and are salted using organic acids, preferably monocarboxylic acids of formula (I) as defined below or polycarboxylic acids of formula (II) as defined below, and even more preferably carboxylic acids of formula (I) such as lactic acid.

[0338] Formula (I) is represented by formula RC(O)-OH, where R represents a (hetero)aryl group such as phenyl, (hetero)aryl (C1-C4)alkyl group such as benzyl, or (C1-C4)alkyl group. 30 )alkyl groups or unsaturated C2-C 30 Groups (i.e., including at least one degree of olefinic unsaturation, preferably one degree of olefinic unsaturation), said alkyl groups or unsaturated C2-C 30The group may optionally be interrupted and / or optionally substituted, preferably substituted with one or more hydroxyl groups and not substituted with one or more amino groups, R preferably represents a (C1-C6) alkyl group, which may optionally be interrupted and / or optionally substituted with one, two or three hydroxyl groups; 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, more particularly from acetic acid and lactic acid, and polycarboxylic acids of the following formula (II): [Chemical Formula 8] 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, optionally interrupted by one or more heteroatoms (e.g., oxygen) and / or optionally substituted, particularly substituted by one or more hydroxyl groups; and t represents an integer between 1 and 5 (including end values).

[0339] Preferably, A represents a divalent (C1-C6) alkylene group, which is optionally substituted, particularly substituted by one or more hydroxyl groups and not substituted by at least one amino group, and t is 1, 2 or 3.

[0340] Preferably, the polycarboxylic acid of formula (II) is selected from tartaric acid, succinic acid, fumaric acid and citric acid, and more specifically from tartaric acid, succinic acid and fumaric acid, as well as citric acid, and amino acids comprising more carboxylic acid groups than amino groups, such as γ-carboxyglutamic acid, aspartic acid, glutamic acid, especially γ-carboxyglutamic acid; in particular, the salt of the monocarboxylic acid is different from the salts of pyrrolidone carboxylic acid, 100 OE and 500 OE ethoxylated stearic acid and linoleic acid.

[0341] According to a specific embodiment, the polysaccharide (one or more) with amine groups is selected from a mixture of polysaccharides (one or more) with amine groups, one of which is chitosan or its organic or inorganic acid salt, preferably its organic acid salt, and more specifically selected from lactic acid, its α or β-terminal isomers, its L- or D-configuration optical isomers, and its solvates, such as its hydrates.

[0342] According to a specific implementation, the polysaccharide with one or more amine groups is a single polysaccharide with one or more amine groups, particularly chitosan or a mixture of its organic or inorganic acid salts, or more particularly its organic acid salts, more particularly selected from its lactate, its α or β-terminal isomers, its L- or D-configuration optical isomers and its solvates, such as its hydrates.

[0343] According to a specific embodiment, the polysaccharide with one or more amine groups is a single polysaccharide with one or more amine groups, particularly chitosan or its organic or inorganic acid salts, or more particularly its organic acid salts, preferably selected from its lactate, its α or β-terminal isomers, its L- or D-configuration optical isomers and its solvates, such as its hydrates.

[0344] According to one embodiment, the acyclic polymer b) is selected from nonionic polymers. Specifically, polymer b) may be selected from alkyl esters or ethers of polyols (e.g., glycerol). Examples of glycerol esters that may be mentioned include polyglycerol isostearate, for example, produced by Evonik under the name Isolan GI 34. ® Products for sale. Also mentioned are polyoxyalkylenated (more particularly polyoxyethylene and / or polyoxypropylene) glycerol fatty acid esters, such as polyethylene glycol stearate with the INCI name PEG-100, polyoxyalkylenated (more particularly polyoxyethylene and / or polyoxypropylene) fatty acid esters, optionally in combination with fatty acid esters of glycerol, such as PEG-100 stearate / glycerol stearate mixtures.

[0345] Nonionic acyclic polymers (b) can also represent oxidized olefinic, particularly oxidized ethyleneic and / or oxidized propyleneic fatty alcohol ethers.

[0346] According to another embodiment, the nonionic acyclic polymer b) can be selected from polyesters, especially from polyhydroxy acids, particularly C8-C30 polyhydroxy acids, such as polyhydroxystearic acid.

[0347] According to one embodiment, the nonionic acyclic polymer b) may be selected from (co)polymer P having at least one unit of formula (II) and optionally at least one unit of formula (III).

[0348] [Chemical Formula 9] In equation (II): -q represents an integer greater than or equal to 2, and -R a Represents a hydrogen atom or a straight-chain or branched (C1-C4) alkyl group; preferably, R a Represents a hydrogen atom; [Chemical Formula 10] In equation (III): -t represents an integer greater than or equal to 2; -R represents a straight-chain or branched chain containing 1 to 10 carbon atoms, saturated or unsaturated, aromatic or non-aromatic, cyclic or acyclic, hydrocarbon-based chain; preferably, R represents a (C1-C6) alkyl group, particularly methyl; and -R a Represents a hydrogen atom or a straight-chain or branched (C1-C4) alkyl group; preferably, R a Represents a hydrogen atom; Preferably, (one or more) copolymers P are copolymers.

[0349] According to a preferred embodiment, (one or more) copolymers P comprises at least one unit of formula (II) and at least one unit of formula (III).

[0350] According to a preferred embodiment, (one or more) copolymers P have a mass average molecular weight 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.

[0351] According to a specific implementation, the (one or more) (co)polymer P as defined above specifically represents poly(vinyl alcohol) (PVA).

[0352] In particular, (one or more)copolymers P can be partially or fully hydrolyzed poly(vinyl alcohol) (PVA), especially those sold by Kuraray under the reference name Kuraray Poval, particularly the POVAL range, or those 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).

[0353] Specifically, it can be selected from the following poly(vinyl alcohol): - Poly(vinyl alcohol) with an average molecular weight (Mw) of 89,000-98,000 and greater than 99% hydrolysis; - Poly(vinyl alcohol) with an average molecular weight (Mw) of 30,000 to 70,000 and 87% to 90% hydrolysis; -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis rate of 13,000-23,000 and a content of 87% to 89%; -Has an average molecular weight M w It is 9000-10000, 80% hydrolyzed poly(vinyl alcohol); -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis rate of 146,000-186,000 and greater than 99% hydrolysis; -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis rate of 85,000-124,000 and greater than 99% hydrolysis; -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis rate of 31,000-50,000 and a content of 98% to 99%; -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis content of 31,000-50,000 and 87% to 89%; -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis rate of 85,000-124,000 and a content of 87% to 89%; -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis rate of 146,000-186,000 and a content of 87% to 89%; -Has an average molecular weight M w Poly(vinyl alcohol) with a concentration of 13,000-23,000 and 98% hydrolysis; -Has an average molecular weight M w Poly(vinyl alcohol) with a hydrolysis rate of 130,000 and greater than 99%; - Completely hydrolyzed poly(vinyl alcohol); - Sigma-Aldrich sells poly(vinyl alcohol) with the reference name 4-88 Emprove® Essential; Sigma-Aldrich sells poly(vinyl alcohol) with the reference name 8-88 Emprove® Essential (CAS No. 9002-89-5, M). w (equal to 67000); or -Sigma-Aldrich sells poly(vinyl alcohol) with the reference name 40-88 Emprove® Essential.

[0354] Preferably, the (one or more) (co)polymers according to the present invention can be prepared from partially hydrolyzed poly(vinyl alcohol), more preferably 88% hydrolyzed.

[0355] Specifically, this could be from Sigma-Aldrich under the reference name 8-88 Emprove. ®Essential sells poly(vinyl alcohol).

[0356] According to the specific implementation scheme, (one or more) polymers b) are selected from acyclic polymers, preferably from anionic acyclic polymers.

[0357] For example, polymers selected from the following (b) can be mentioned, using at least one C8-C 30 C8-C is preferred. 24 Hydrocarbon-based chain-modified amino acids and their salts, particularly acylglutamic acid (INCI name: acylglutamic acid) or its salts (e.g., acylglutamate), especially stearoylglutamic acid or its salts, and more particularly sodium stearoylglutamate (INCI name).

[0358] These compounds are marketed by Ajinomoto under the name Amisoft, and in particular by the reference names AmisoftCA, Amsoft LA, Amisoft HS 11 PF, Amisoft MK-11, Amisoft LK-11, and Amisoft CK-11, or by Cognis under the name Eumulgin SG.

[0359] According to a particular embodiment, polymer (b) is selected from polyamino and hydrocarbon-based acyclic polymers. Such polymers do not contain any silicon atoms.

[0360] In particular, the polyamine polymer can be selected from diamine polymers, and more specifically, from polyether diamines, especially those of the formula H2N-ALK-O-[ALK'-O]. m -ALK''-NH2, where ALK, ALK', and ALK'' may be the same or different, representing a straight-chain or branched (C1-C6) alkylene group, and m represents an integer greater than or equal to 0, such as 4,7,10-trioxa-1,13-tetanediamine or compounds known from Huntsman Corporation under the reference name Jeffamine, and more specifically α,ω-diamino polyethylene glycol and / or polypropylene glycol (having amine functionality at the chain end), such as products sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000, and ED-2003.

[0361] In particular, (one or more) polyamine polymers may be selected from triamine polymers, i.e., containing three primary and / or secondary amine groups, preferably primary amine groups (NH2).

[0362] More specifically, they are selected from polyether triamines, particularly those having the formula ALK'''[(O-ALK')m-NH2]3, where ALK' is as defined previously and ALK''' represents a straight-chain or branched trivalent (C1-C6) alkylene group, and m represents an integer greater than or equal to 0.

[0363] As triamino compounds, (poly)amino compounds can be specifically mentioned as polyether triamines, and in particular α,ω-diamino polyethylene glycol and / or polypropylene glycol (which have amine functionality at the chain ends), such as the product sold under the name Jeffamine T-403.

[0364] According to a specific embodiment, (one or more) (poly)amino compounds include more than three primary and / or secondary amine groups, preferably primary amine groups (NH2).

[0365] In particular, (one or more) (poly)amino compounds are selected from poly(meth)acrylates or poly(meth)acrylamides having lateral primary or secondary amine functionalization, and more specifically from poly(3-aminopropyl)methacrylamide and poly(2-aminoethyl)methacrylates.

[0366] According to a specific implementation scheme, (one or more) polyamine compounds are selected from: - Poly((C2-C5)alkylene imides), and preferably selected from polyethyleneimine and polypropyleneimine, especially poly(ethyleneimine), particularly those marketed by Aldrich Chemical Company under reference number 408700 or by Aldrich Chemical Company under reference number 408727 (example MW = 25000) or by BASF under the trade name Lupasol, especially those having a molecular weight between 1200 and 30000. - Poly(allylamine), particularly products sold by Aldrich Chemical under reference number 479136. - Polyethyleneamine and its copolymers, especially copolymers with vinylamide, particularly vinylamine / vinylformamide copolymers, - Polyamino acids containing NH2 groups, such as polylysine, especially products sold by JNC Corporation (formerly Chisso). -Aminodextran, especially products sold by CarboMer Inc. -Amino polyvinyl alcohol, especially products sold by CarboMer Inc. - Copolymers based on acrylamide-based (C1-C6) alkylamines, particularly those based on acrylamide-based propylamine, and - Its mixture.

[0367] As amino polymers, α,ω-diaminopolytetrahydrofuran (or polytetramethylene glycol) and α,ω-diaminopolybutadiene may also be mentioned.

[0368] According to a specific embodiment, the (poly)amino compound is selected from hyperbranched polymers containing at least one amino group and dendritic polymers having at least one amino group, particularly polyamidoamine (PAMAM) dendritic polymers having ethylenediamine core and terminal amine functionality.

[0369] According to a specific embodiment, (one or more) polymers b) are selected from polyamino acids and preferably from proteins.

[0370] Preferably, the protein is of plant origin. Soy protein can be mentioned as an example of polymer b) selected from plant proteins.

[0371] (one or more) Acyclic polymers b) can be anionic, cationic or nonionic, preferably anionic, more preferably anionic, especially having carboxyl, carboxylate, sulfate, sulfonic acid, sulfonate, phosphate, phosphonic acid or phosphonate groups, preferably selected from carboxylate and carboxylic acid groups.

[0372] According to the specific implementation scheme, the acyclic polymer b) is anionic, particularly a carboxyl group or a carboxylate of an alkali metal or alkaline earth metal such as sodium, and is selected from homopolymers or copolymers of (meth)acrylic acid.

[0373] (Meth)acrylic acid copolymers, particularly copolymers of (meth)acrylic acid with alkyl (poly)ether (meth)acrylates, especially copolymers of (meth)acrylic acid and POE / POP (meth)acrylates, such as polyether polycarbonate, sodium salts in aqueous solutions, are sold by Arkema-Coatex under the name RSY 15007 Cosmetic Version.

[0374] According to a preferred embodiment, (one or more) polymers b) are selected from: - Lignosulfonic acid, lignin sulfonates, sulfonated polystyrene, polystyrene sulfonates, anionic polyaniline derivatives, especially polyaniline sulfonates, and mixtures thereof. - Alkyl esters or ethers of polyols (especially glycerol), - Anionic polysaccharides, preferably selected from sulfated polysaccharides, especially Ulva polysaccharides, dextran sulfate, carrageenan, and mixtures thereof, as well as polysaccharide carboxylates, especially alginates. - Cationic polysaccharides, preferably selected from polysaccharides with amine groups, especially chitosan. - Modified polysaccharides, particularly those selected from polysaccharide esters, and preferably pullulan esters. - Poly((C2-C5)alkylene imides), preferably selected from polyethyleneimine and polypropyleneimine, especially poly(ethyleneimine), - Polyamino acids, preferably proteins, - An anionic acyclic polymer containing a carboxyl group or a carboxylate of an alkali metal or alkaline earth metal such as sodium, and selected from homopolymers or copolymers of (meth)acrylic acid, preferably sodium polymethacrylate and copolymers of (meth)acrylic acid with alkyl (poly)ether (meth)acrylates, particularly copolymers of (meth)acrylic acid and POE / POP (meth)acrylates. - Its mixture.

[0375] According to a more preferred embodiment, (one or more) polymers b) are selected from: - Lignosulfonates, especially alkali metal or alkaline earth metal ligninsulfonates, such as sodium ligninsulfonate or calcium ligninsulfonate. - Carrageenan, -Chitosan, - Alginates, especially alkali metal or alkaline earth metal alginates, such as sodium alginate. - Dextran, especially alkali metal or alkaline earth metal dextran, and alkali metal or alkaline earth metal dextran sulfates, such as sodium dextran sulfate. - Polyhydroxystearic acid, - Starch and its derivatives, especially its phosphorylated derivatives, such as hydroxypropyl corn distarch phosphate, Pullulan and its ester derivatives, especially C1-C 30 C is preferred 10 -C 20 Carboxylic acids, such as myristoyl pullulan, -Polyvinyl alcohol, - Optional hydrolyzed proteins, such as optional hydrolyzed soy protein, and - Its mixture.

[0376] According to even more preferred embodiments, (one or more) polymers b) are selected from: -Lignin sulfonate, - Carrageenan, -Chitosan, - Alginate, such as sodium alginate - Dextran, such as sodium dextran sulfate, - Polyhydroxystearic acid, - Starch and its derivatives, such as hydroxypropyl corn distarch phosphate, Pullulan and its ester derivatives, such as myristoyl pullulan, -Polyvinyl alcohol, - Proteins, such as optionally hydrolyzed soy protein, and - Its mixture.

[0377] Inorganic compounds c) According to a specific embodiment, the composite material according to the present invention may further comprise at least one inorganic compound c) different from the bismuth oxycarbonate particles a).

[0378] (one or more) Inorganic compounds c) may be in amorphous or crystalline, hydrated or dehydrated forms of oxides or hydroxides or hydroxyoxides of alkali metals or alkaline earth metals (especially sodium, potassium, magnesium and calcium) or transition metals (especially titanium, aluminum, manganese, iron, copper, niobium and tantalum) or lanthanides (especially cerium) or depleted metals (especially zinc, indium and bismuth).

[0379] Inorganic oxides can also refer to amorphous or crystalline, hydrated or non-hydrated metalloid oxides or hydroxides or hydroxy oxides.

[0380] In particular, the inorganic compound c) may be an amorphous or crystalline, hydrated or dehydrated form of silicon oxide or silicon hydroxide or silicon hydroxyl oxide (including clay), such as silicon dioxide SiO2, silicates of 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, and borosilicates of aluminum and / or calcium and / or magnesium and / or sodium and / or titanium and / or iron and / or zinc and / or bismuth.

[0381] In particular, the inorganic compound c) can be an inorganic carbide, sulfide, or nitride, such as silicon carbides, sulfides of iron, copper, and zinc, or nitrides of boron and silicon in amorphous or crystalline, hydrated or dehydrated form.

[0382] As metal oxides, the following hydrated or non-hydrated forms can be mentioned: Al2O3, Al(OH)3, SiO2, TiO2, MnO, MnO2, FeO(OH), Fe3O4, Fe2O3, Cu(OH)2, Cu2O, CuO, Zn(OH)2, ZnO, Nb2O5, In(OH)3, In2O3, Ce2O3, CeO2, Ta2O5, WO3, Bi2O3 and mixtures thereof.

[0383] Preferably, the hydrated or non-hydrated form of Al2O3, such as Al(OH)3, hydrated or non-hydrated forms of SiO2, TiO2, ZnO, and mixtures thereof, is used; more preferably, the hydrated or non-hydrated form of Al2O3, such as Al(OH)3, or the hydrated or non-hydrated forms of SiO2, TiO2, ZnO, and mixtures thereof, is used; and even more preferably, the hydrated or non-hydrated form of Al2O3, such as Al(OH)3, or SiO2, and mixtures thereof, is used.

[0384] According to a preferred embodiment, the composite material according to the present invention does not contain any inorganic compound c) other than the bismuth oxycarbonate particles a).

[0385] According to another preferred embodiment, the composite material according to the invention contains only one inorganic compound c) that is different from the bismuth oxycarbonate particles a), preferably selected from inorganic oxides, and more preferably selected from silicon dioxide, aluminum oxide, titanium dioxide and zinc oxide, and even more preferably selected from silicon dioxide.

[0386] According to another preferred embodiment, the composite material according to the invention contains only one inorganic compound c) different from the bismuth oxycarbonate particles a), preferably selected from inorganic hydroxides or inorganic hydroxy oxides, more preferably selected from inorganic hydroxides, even more preferably selected from Al(OH)3, Zn(OH)2, In(OH)3 or mixtures thereof, even more preferably selected from Al(OH)3, Zn(OH)2, and even more preferably Al(OH)3.

[0387] 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, and more preferably selected from oxides of zinc, titanium, silicon and / or aluminum, preferably selected from oxides of silicon and / or aluminum, which are optionally hydrated.

[0388] 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, and even more preferably selected from Al(OH)3 or SiO2.

[0389] Methods for preparing composite materials The composite material according to the invention can be obtained, in particular, by the preparation method described below.

[0390] In particular, the composite material according to the invention, as previously defined, can be obtained in one or more steps.

[0391] Composite materials can generally be obtained in particular by various methods, especially by bringing bismuth oxycarbonate particles a) into contact with a solution comprising at least one polymer b) in a solvent or solvent mixture A.

[0392] In particular, the method for preparing a composite material according to the invention uses: - particles a) of bismuth oxycarbonate, which are of formula (I) (BiO) 2-x (CO3) (formula (I)) and its solvates, such as its hydrate, where -0.4 < x < 0.6, the maximum average size of said particles being less than 400 nm; - optionally one or more precursors of (one or more) inorganic compounds c) intended to form other than the bismuth oxycarbonate particles; - one or more polymers b) as defined above; - optionally one or more additives; and - optionally one or more solvents.

[0393] According to a particular embodiment, the method for preparing a composite material according to the invention may include one or more separation steps.

[0394] In particular, the (one or more) precursors of (one or more) inorganic compounds c) intended to form other than the bismuth oxycarbonate particles a) are selected from organic or inorganic compounds which make it possible to obtain bismuth oxycarbonate particles (a) and inorganic compound c) by chemical reaction or physical adsorption.

[0395] In particular, the (one or more) precursors may be selected from: - inorganic compound c) as described above, - inorganic metal precursors of chemical elements and their hydrates, especially dissolved metal oxides (especially sodium silicate or sodium aluminate), halides and their hydrates, nitrates and their hydrates, carbonates and their hydrates, sulfonates and their hydrates, sulfates and their hydrates, phosphates and their hydrates, - organometallic precursors and their hydrates, especially alcoholates and their hydrates, carboxylates and their hydrates, lactates and their hydrates, or citrates and their hydrates, and - mixtures thereof.

[0396] The (one or more) precursors intended to form the auxiliary (one or more) inorganic compound c) may also be selected from oxidizing precursors, especially air, hydrogen peroxide, peroxides and their hydrates, and / or sulfiding agents, especially hydrogen sulfide, alkali metal sulfides and their hydrates, and / or nitriding agents.

[0397] According to a preferred embodiment, the method for preparing the composite material according to the invention does not use a precursor that is intended to form (one or more) inorganic compounds c) different from the bismuth oxycarbonate particles a).

[0398] According to a preferred embodiment, the method for preparing the composite material according to the invention uses at least one precursor that is intended to form (one or more) inorganic compounds c) different from the bismuth oxycarbonate particles a), and is preferably selected from sodium silicate and sodium aluminate.

[0399] According to a specific embodiment, the method for preparing the composite material according to the invention uses at least one solvent.

[0400] The selection of the (one or more) solvents can in particular depend on the (one or more) precursors and additives used in the method.

[0401] In particular, the (one or more) solvents can be selected from polar or non-polar, protic or aprotic solvents.

[0402] According to a specific embodiment, the method for preparing the composite material according to the invention uses at least one additive.

[0403] In particular, the (one or more) additives can be selected from acids, especially inorganic acids such as hydrochloric acid or sulfuric acid, and bases, preferably inorganic bases such as sodium hydroxide or potassium hydroxide.

[0404] According to a specific embodiment, the invention relates to a method for preparing a composite material as previously defined, the method comprising at least the following steps: (i) providing at least one particle a) of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) (formula (I)) and its solvates, such as its hydrates, where -0.4 < x < 0.6, the maximum average size of the particles being less than 400 nm, optionally dispersed in at least one solvent or solvent mixture A; (ii) providing a solution of at least one polymer b), optionally 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 a composite material; (iv) separating the composite material.

[0405] Preferably, step (i) does not use solvent A.

[0406] According to one embodiment, the (one or more) solvents of steps (i) and (ii) can be the same or different.

[0407] In particular, solvent A and / or B is selected from nonpolar aprotic solvents, polar protic solvents, more preferably water, alcohols, polyols and mixtures thereof.

[0408] Specifically, when polymer (b) is hydrophilic and / or amphiphilic, solvent or solvent mixture B is polar, and when polymer (b) is hydrophobic and / or amphiphilic, solvent or solvent mixture B is nonpolar.

[0409] In particular, when polymer (one or more) is hydrophilic and / or amphiphilic, the solvent or solvent mixture B is polar and proton, and is preferably selected from water, polyols and / or mixtures thereof, and more preferably water.

[0410] In particular, when polymer (one or more) is hydrophobic and / or amphiphilic, the solvent or solvent mixture B is nonpolar and preferably selected from volatile and nonvolatile oils or organic solvents.

[0411] Preferably, the mixture (iii) is stirred at atmospheric pressure for 5 minutes to 24 hours, especially at a temperature of 20°C to 200°C, and especially in open air or in an inert atmosphere.

[0412] According to a particular embodiment, a method for preparing the composite material according to the invention may include one or more separation steps, particularly by centrifugation and / or by filtration, particularly ultrafiltration, and / or by lyophilization and / or by atomization.

[0413] According to a specific implementation, the method for preparing the composite material also includes a centrifugation step.

[0414] Specifically, according to this embodiment, the method for preparing the composite material further includes: - Optionally, the step of adding a solvent or solvent mixture S, wherein (one or more) polymers b) are insoluble, i.e., polymers b) precipitate from the solvent or solvent mixture S at a temperature of 0°C to room temperature, to precipitate the composite material; - At least one centrifugation step, preferably between 4000 rpm and 14000 rpm, particularly for a duration of 1 minute to 1 hour; and -Optionally at least one washing step, preferably using a solvent or solvent mixture S; - Optionally, at least one drying step, especially in an oven, preferably at a temperature of 50°C, and especially under vacuum (pressure equal to 10 mmHg), is used to separate the composite material.

[0415] According to a specific implementation, the method for preparing the composite material also includes a filtration step, particularly an ultrafiltration step.

[0416] Specifically, according to this embodiment, the method for preparing the composite material further includes: -Optional step of adding solvent or solvent mixture S, - The step of separating the composite material from the solvent mixture by filtration (especially by ultrafiltration) on a membrane preferably having a pore size in the range of 1 nm to 1 μm, or even better, 1 to 100 nm.

[0417] - Choose at least one centrifugation step; - Choose at least one washing step; and -Optional drying step, especially in an oven, preferably at a temperature of 50°C, and especially under vacuum (pressure equal to 10 mmHg), to separate the composite material.

[0418] According to a specific implementation scheme, the method for preparing the composite material also includes a freeze-drying step.

[0419] In particular, according to this embodiment, the method for preparing the composite material further includes the step of optionally freeze-drying the mixture after one or more solvents have evaporated when the reaction medium contains a variety of solvents, especially at a temperature of 0°C to -180°C.

[0420] According to a specific implementation scheme, the method for preparing the composite material also includes an atomization step.

[0421] Specifically, according to this embodiment, the method for preparing the composite material further includes a step of atomizing the mixture. Specifically, the atomization temperature is preferably less than or equal to the lowest characteristic transition temperature of polymer b) or all polymers b) constituting the mixture, where "transition" refers to a potential glass transition and / or potential melting and / or potential degradation, and is greater than the lowest boiling point of one or more solvents in the mixture. Preferably, the atomization temperature is from 80°C to 250°C, more preferably from 100°C to 200°C, and even more preferably from 100°C to 180°C.

[0422] Cosmetic Composition The composite material according to the invention can be used in compositions, particularly in cosmetic compositions.

[0423] Therefore, the present invention also relates to compositions comprising at least one composite material as defined above, particularly cosmetic compositions.

[0424] According to a preferred embodiment, the present invention also relates to a composition, particularly a cosmetic composition, comprising at least: i) at least one composite material as defined above; ii) at least one aqueous phase and / or at least one fatty phase; and iii) at least one compound selected from: 1) a UV-masking agent different from composite material i); 2) a colorant; 3) a cosmetic surfactant for use in keratin materials; 4) a surfactant; 5) a thickener; and mixtures thereof.

[0425] The composite material may be present in the composition, preferably in a cosmetic composition, at an amount of 0.5% to 70% by weight, preferably 1% to 50% by weight, still more preferably 2% to 40% by weight relative to the total weight of the composition.

[0426] Aqueous phase The compositions according to the present invention, particularly cosmetic compositions, may contain at least one aqueous phase.

[0427] The aqueous phase may contain water and, optionally, a water-soluble solvent.

[0428] In this invention, the term "water-soluble solvent" refers to a compound that is a liquid at room temperature and is miscible with water (miscible with more than 50% by weight in water at 25°C and atmospheric pressure).

[0429] The water-soluble solvent that can be used in the compositions according to the present invention can also be volatile.

[0430] Among the water-soluble solvents that can be used in the compositions according to the invention, lower monohydric alcohols containing 1 to 5 carbon atoms, such as ethanol and isopropanol, C2-C 32 Polyols, C3 and C4 ketones and C2-C4 aldehydes.

[0431] Polyols are particularly mentioned among water-soluble solvents that can be used in the compositions according to the invention. For the purposes of this invention, the term "polyol" refers to any organic molecule comprising at least two free hydroxyl groups.

[0432] The polyols applicable to this invention can be straight-chain, branched or cyclic, saturated or unsaturated alkyl-type compounds, having at least two -OH functional groups on the alkyl chain, and particularly at least three -OH functional groups.

[0433] Polyols advantageously suited for formulating compositions according to the invention are polyols containing 2 to 32 carbon atoms, and preferably 3 to 16 carbon atoms.

[0434] Advantageously, the polyol may be selected from, for example, pentaerythritol, trimethylolpropane, caprylylglycol, glycerol, polyglycerol (e.g., glycerol oligomers, such as diglycerol), polyethylene glycol, polypropylene glycol, and mixtures thereof.

[0435] Fat phase The compositions according to the invention, particularly cosmetic compositions, may also contain at least one fatty phase, especially an oil phase.

[0436] For the purposes of this invention, the term "fatty phase" refers to a phase comprising at least one fatty substance and all fat-soluble and lipophilic components used to formulate the compositions of this invention.

[0437] Preferably, the fatty phase comprises at least one oil, particularly a cosmetic oil.

[0438] 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.

[0439] The aliphatic phase may contain at least one volatile or non-volatile hydrocarbon-based oil and / or fatty substance.

[0440] As non-volatile hydrocarbon-based oils, specific examples include plant-derived hydrocarbon-based oils, synthetic ethers containing 10 to 40 carbon atoms, straight-chain 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, and C 12 -C 22 Higher fatty acids, carbonates, and mixtures thereof.

[0441] As volatile hydrocarbon-based oils, hydrocarbon-based oils containing 8 to 16 carbon atoms can be specifically mentioned.

[0442] Non-volatile silicone oils may be specifically selected from non-volatile polydimethylsiloxanes (PDMSs) and phenyl silicones. As volatile silicone oils, examples include volatile linear or cyclic silicone oils.

[0443] Volatile fluorinated oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecylfluorohexane, dodecafluoropentane, and mixtures thereof, can also be used.

[0444] The oil phase may also contain other fatty substances that are mixed with or dissolved in the oil. Another type of fatty substance that may be present in the oily phase may be, for example, fatty acids, waxes, gums, paste compounds, or mixtures thereof.

[0445] 1) Additional UV-masking agent According to a particular embodiment, the composition according to the invention comprises 1) at least one additional UV-masking agent, which is different from the composite material required according to the invention and defined above.

[0446] For the purposes of this invention, the term "UV-masking agent different from the composite material" is intended to mean any UV-masking agent whose chemical properties differ from those of the composite material as required by and defined above according to this invention.

[0447] The composite material according to the invention can thus be used alone or in combination with 1) other UV-masking agents (particularly selected from organic and / or inorganic UV-masking agents).

[0448] Therefore, the cosmetic composition may also contain one or more additional UV-blocking agents different from the composite material according to the present invention, selected from hydrophilic, lipophilic or insoluble organic UV-blocking agents and / or mineral UV-blocking agents.

[0449] The term "hydrophilic UV shielding agent" refers to any cosmetic or dermatological organic or inorganic compound used to filter UV radiation, which can be completely dissolved in a liquid aqueous phase in molecular form, or which can be in a colloidal suspension (e.g., in micelle form) in a liquid aqueous phase.

[0450] The term "lipophilic UV shielding agent" refers to any cosmetic or dermatological organic or inorganic compound used to shield against UV radiation, which can be completely dissolved in a liquid fat phase in molecular form, or which can be in a colloidal suspension (e.g., in micelle form) in a liquid fat phase.

[0451] The term "insoluble UV shielding agent" refers to any cosmetic or dermatological organic or inorganic compound used to filter UV radiation, having a solubility of less than 0.5% by weight in water and less than 0.5% by weight in most organic solvents such as liquid paraffin, fatty alcohol benzoates, and fatty acid triglycerides (e.g., Miglyol 812®). This solubility, determined at 70°C, is defined as the amount of product dissolved in the solvent after returning to room temperature, in equilibrium with the excess solids of the suspension. It can be readily evaluated in a laboratory setting.

[0452] Additional organic UV-masking agents are particularly selected from: - Cinnamic acid compounds, especially ethylhexyl methoxycinnamate, - Anthranilic ester compounds, especially menthyl anthranilic acid, - Salicylic acid compounds, especially homosalate and ethylhexyl salicylate, - Benzoylmethane compounds, especially butylmethoxydibenzoylmethane. - Benzyl camphor compounds, particularly 3-benzyl camphor, 4-methylbenzyl camphor, benzyl camphor sulfonic acid, and terephthalimide dicamphor sulfonic acid. - Benzophenone compounds, especially hydroxybenzophenone and n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, - β,β-diphenyl acrylate compounds, especially octocrylene. - Triazine compounds, particularly phenylene bis-diphenyltriazine, bis-ethylhexyloxyphenol methoxyphenyltriazine, ethylhexyltriazinone and diethylhexylbutyramide triazinone.

[0453] - Benzotriazole compounds, especially cresoltrazol trisiloxane, - Benzyl malonate compounds, especially those mentioned in patent US 5624663, particularly Polysilicone-15. - Benzimidazole derivatives, especially phenylbenzimidazole sulfonic acid, - Imidazoline compounds, particularly ethylhexyl dimethoxybenzyl dioxazoline propionate, - Bibenzoazole compounds, such as those described in patents EP 0669323 and US 2463264, particularly disodium phenyldibenzimidazole tetrasulfonate. - Para-aminobenzoic acid compounds, especially PABA, ethylhexyldimethylPABA, and PEG-25 PABA, - Methylene bis(hydroxyphenylbenzotriazole) compounds, such as those described in patent applications US 5237071, US5166355, GB 2303549, DE 19726184 and EP 0893119, particularly methylene bis-benzotriazole tetramethylbutylphenol. - Benzooxazole compounds, such as those described in patent applications EP 0832642, EP 1027883, EP 1300137 and DE10162844, particularly 2,4-bis-[5-1-(dimethylpropyl)benzooxazole-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine, - Polymer masking agents and silicone masking agents, such as those specifically described in patent application WO 93 / 04665. - α-alkylstyrene-derived dimers, such as those described in patent application DE 19855649, - 4,4-Diarylbutadiene compounds, such as those described in patent applications EP 0967200, DE 19746654, DE19755649, EP 1008586, EP 1133980 and EP 0133981, particularly 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, and - Its mixture.

[0454] The additional inorganic UV shielding agent is typically a mineral UV shielding agent, particularly selected from metal oxides.

[0455] The metal oxide may be selected in particular from titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, and mixtures thereof.

[0456] The metal oxide particles may be coated or uncoated.

[0457] The coated particles are more specifically titanium dioxide particles, coated with silicon dioxide, coated with silicon dioxide and iron oxide, coated with silicon dioxide and aluminum oxide, coated with aluminum oxide, coated with aluminum oxide and aluminum stearate, coated with silicon dioxide, aluminum oxide and alginate, coated with aluminum oxide and aluminum laurate, coated with iron oxide and iron stearate, coated with zinc oxide and zinc stearate, coated with silicon dioxide and aluminum oxide and treated with silicone, coated with silicon dioxide, aluminum oxide and aluminum stearate and treated with silicone, coated with silicon dioxide and treated with silicone, coated with aluminum oxide and treated with silicone, coated with... TiO2 coated with triethanolamine, stearic acid, sodium hexametaphosphate, or octyltrimethylsilane, polydimethylsiloxane, anatase / rutile TiO2, triethylhexanoin, aluminum stearate and alumina, aluminum stearate, alumina and silicone, lauroyl lysine, or C 9-15 Fluoro-oyl phosphate and TiO2 of aluminum hydroxide.

[0458] The metal oxide may be optionally doped.

[0459] 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.

[0460] The doped particles can be in the form of a dispersion, preferably an oily dispersion. The oil present in the oily dispersion is preferably selected from triglycerides, including those of decanoic acid / caprylic acid. The oily dispersion of titanium dioxide particles may additionally contain one or more dispersants, such as sorbitan esters or polyoxyethylene glycerol fatty acid esters. More particularly noteworthy is the oily dispersion of manganese-doped TiO2 particles in decanoic acid / caprylic acid triglycerides in the presence of tri-PPG-3 myristyl ether citrate, polyglycerol-3 polyricinoleate, and dehydrated sorbitan isostearate.

[0461] Mixtures of metal oxides may also be mentioned, particularly mixtures of titanium dioxide and cerium dioxide, including equal weight mixtures of titanium dioxide and cerium dioxide coated with silica, and mixtures of titanium dioxide and zinc dioxide coated with alumina, silica and silicone or coated with alumina, silica and glycerol.

[0462] 2) Coloring agents According to a particular embodiment, the composition according to the invention comprises 2) at least one colorant.

[0463] Generally, the term "colorant" is understood to mean any compound that can color a composition, that is, any compound that absorbs in the visible spectrum (and thus appears to the human eye as having colors such as yellow, orange, red, purple, blue, or green).

[0464] Preferably, the composition according to the invention comprises at least one pigment.

[0465] The term "pigment" should be understood to refer to white or colored mineral or organic particles that are insoluble in both the lipophilic and hydrophilic phases of a liquid, and are intended to color and / or make the composition containing them opaque, and which are different from the composite materials according to the invention. More specifically, pigments are practically insoluble or non-soluble in water-alcohol media.

[0466] The pigments that can be used are particularly selected from organic and / or mineral pigments known in the art, especially those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry (Ullmann's Encyclopedia of Industrial Chemistry “Pigmentorganics”, 2005 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim 10.1002 / 14356007.a20371) and, ibid., “Pigments, Inorganic, 1. General”, 2009 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim 10.1002 / 14356007.a20_243.pub3.

[0467] These pigments can be in the form of pigment powder or paste. They can be coated or uncoated.

[0468] Pigments can be selected from, for example, mineral pigments, organic pigments, lakes, pigments with special effects (such as mother-of-pearl or glitter), and mixtures thereof.

[0469] The pigment can be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the section on inorganic pigments in Ullmann's encyclopedia. Among the mineral pigments that can be used in this invention, iron oxides, chromium oxides, manganese violet, ultramarine, chromium hydrate, iron blue, and titanium oxide may be mentioned.

[0470] The pigment may be an organic pigment.

[0471] The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's encyclopedia.

[0472] Organic pigments can be selected in particular from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex types, isoindolineone, isoindoline, quinacridone, pyrene, perylene, diketopyrrolopyrrole, sulfide indigo, dioxazine, triphenylmethane, or quinoline phthalone compounds.

[0473] Preferably, the pigment(s) suitable for use in this invention are selected from carbon black, iron oxides (especially red, brown or black iron oxides), and mica coated with iron oxide, triarylmethane pigments (especially blue and purple triarylmethane pigments, such as Blue 1 Lake), azo pigments (especially red azo pigments, such as D&C Red 7), and alkali metal salts of Lithol Red (such as calcium salts of Lithol Red B); more preferably, the pigment(s) used are selected from red iron oxides and azo pigments, especially red azo pigments such as D&C Red 7.

[0474] The colorant(s) may be present in the composition according to the invention in an amount of 0.001% to 10% by weight and preferably 0.005% to 5% by weight relative to the total weight of the composition.

[0475] According to a particular embodiment of the invention, the amount of pigment is 0.5% to 40% and preferably 1% to 20% by weight relative to the composition of the invention containing them.

[0476] 3) Cosmetic surfactants According to a specific embodiment, the composition according to the invention comprises 3) at least one cosmetic surfactant for caring for keratin materials, preferably for caring for the skin.

[0477] In particular, the cosmetic surfactant may be at least one hydrophilic surfactant and / or one lipophilic surfactant, which is preferably hydrophilic.

[0478] The term "hydrophilic surfactant" refers to a water-soluble or water-dispersible surfactant that can form hydrogen bonds.

[0479] As a cosmetic active agent 3), it may refer to, for example, moisturizers, bleaching agents, desquamating agents, humectants, anti-aging agents, matting agents, healing promoters, antibacterial agents, vitamins and their derivatives or precursors, antioxidants, free radical scavengers, anti-pollution agents, self-tanning agents, anti-glycation agents, calming agents, deodorants, essential oils, NO synthase inhibitors, agents for stimulating the synthesis of macromolecules in the dermis or epidermis and / or for preventing their degradation, agents for stimulating fibroblast proliferation, agents for stimulating keratinocyte proliferation, muscle relaxants, refreshing agents, tightening agents, propigmenting agents, keratolytic agents, slimming agents, agents acting on cellular energy metabolism, insect repellents, substance P antagonists or CRGP antagonists, agents for preventing hair loss, and mixtures thereof.

[0480] The active agent(s) may in particular be selected from: - Vitamins and their derivatives, especially their esters, such as nicotinamide (3-pyridinecarboxamide), nicotinamide (vitamin B3), tocopherol (vitamin E) and its esters (e.g., tocopheryl acetate), ascorbic acid and its derivatives (vitamin C), and retinol (vitamin A). - Humectants or moisturizers, such as urea, hydroxyurea, glycerin, polyglycerol, glyceryl glucoside, diglyceryl glucoside, polyglyceryl glucoside, xylosyl glucoside and plant extracts (especially tea, peppermint, orchid, soybean, aloe vera), honey, and especially glycerin; - C-glycoside compounds, preferably hydroxypropyltetrahydropyranotriol (INCI name) (or bosene); - Antioxidant compounds; - Anti-aging active agents, such as hyaluronic acid compounds, and especially sodium hyaluronate, salicylic acid compounds, and especially 5-n-octanoyl salicylic acid (octanoyl salicylic acid), adenosine, and sodium salts of (3-hydroxy-2-pentylcyclopentyl)acetic acid; - Exfoliating agents, such as lactic acid or glycolic acid; and - Its mixture.

[0481] Such active agents may be present in the compositions according to the invention in an amount of 0.05% to 10% by weight and preferably 1.0% to 8.0% by weight relative to the total weight of the composition.

[0482] 4) Surfactants According to a particular embodiment, the composition according to the invention comprises 4) at least one surfactant.

[0483] The surfactant may be selected from nonionic, anionic, cationic, and amphoteric surfactants, and mixtures thereof. For the definition of emulsifying properties and the function of surfactants, refer to Kirk-Othmer's Encyclopedia of Chemical Technology, Vol. 22, pp. 333-432, 3rd edition, 1979, Wiley, and for anionic, amphoteric, and nonionic surfactants, especially pp. 347-377 of that reference.

[0484] Examples of amphoteric surfactants suitable for use in this invention are particularly selected from betaines, preferably from alkyl betaines, especially lauryl betaine, N-alkylamido betaine, and their derivatives, particularly cocamidopropyl betaine, lauramide propyl betaine, and N-disodium N-carboxyethoxyethyl N-cocamidoethyl aminoacetate; sulfobetaine, especially cocamidopropyl hydroxysulfobetaine; and mixtures thereof.

[0485] Nonionic surfactants may be selected in particular from alkyl and polyalkyl esters of poly(ethylene oxide), oxidized olefin alcohols, alkyl and polyalkyl ethers of poly(ethylene oxide), optionally polyethyleneimine-modified alkyl and polyalkyl esters of sorbitol, optionally polyethyleneimine-modified alkyl and polyalkyl ethers of sorbitol, especially alkyl and polyalkyl esters of sucrose, optionally polyethyleneimine-modified alkyl and polyalkyl esters of glycerol, and optionally polyethyleneimine-modified alkyl and polyalkyl ethers of glycerol, gemini surfactants, cetyl alcohol, stearyl alcohol, and mixtures thereof.

[0486] Anionic surfactants can be selected from alkyl ether sulfates, carboxylates, amino acid derivatives, sulfonates, hydroxyethyl sulfonates, taurines, sulfosuccinates, alkyl sulfonates, phosphates and alkyl phosphates, peptides, C 10 -C 30 And especially C 16 -C 25 Metal salts of fatty acids (especially metal stearates and behenates) and mixtures thereof.

[0487] Cationic surfactants can be selected from alkyl imidazoline, such as isostearyl ethyl imidazoline ethyl sulfate, and ammonium salts such as (C 12-30 alkyl)-tri(C 1-4 Alkyl) ammonium halides, such as N,N,N-trimethyl-1-docodecyl ammonium chloride (or behenyltrimethyl ammonium chloride).

[0488] The silicone surfactant can be selected from polydimethylsiloxane copolyol or silicone elastomer.

[0489] The composition according to the invention may contain 0.01% to 2.0% by weight of surfactant relative to the total weight of the composition, preferably 0.05% to 1.5% by weight, more preferably 0.1% to 1.0% by weight.

[0490] 5) Thickener According to a particular embodiment, the composition according to the invention comprises 5) at least one thickener, sometimes also referred to as a gelling agent or viscosity modifier. The thickener may be synthetic, natural, or of natural origin, preferably natural or of natural origin.

[0491] Such thickeners can be more specifically selected from natural polymers or polymers of natural origin, especially plant-derived polymers.

[0492] These thickeners are preferably hydrophilic, that is, soluble or dispersible in water.

[0493] Advantageously, the thickener (one or more) is selected from modified or natural polysaccharides, particularly modified or unmodified starch, fructan, gellan gum, dextran, amylose, amylopectin, glycogen, pullulan, dextran, cellulose and its derivatives, particularly methylcellulose, hydroxyalkylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, mannan, xylan, lignin, arabinogalactan, galactan, polygalacturonic acid, alginate-based compounds, chitin, chitosan, glucuronic acid xylan, arabinogalactan, xyloglucan, glucomannan, pectic acid and pectin, arabinogalactan, Carrageenan, agar, glycosaminoglucan, gum arabic, sclerotium gum, tragacanth gum, Indian gum, black privet gum, locust bean gum, konjac gum, galactomannan such as guar gum and its nonionic derivatives, especially hydroxypropyl guar gum and its ionic derivatives, microbial-derived biopolysaccharide gums, especially stearin or xanthan gum, mucopolysaccharides, carboxyvinyl polymers, polyacrylamide, polymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid, optionally crosslinked and / or neutralized, water-soluble or water-dispersible silicone derivatives, such as acrylic silicone, polyether silicone and cationic silicone, and mixtures thereof.

[0494] The thickener(s) may be present in the composition according to the invention in an amount of 0.05% to 5.0% by weight, particularly 0.3% to 4.0% by weight, and more particularly 0.4% to 2.5% by weight relative to the total weight of the composition.

[0495] adjuvant The compositions according to the invention may also contain at least one adjuvant commonly used 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, emollients, sweeteners, defoamers, fillers, trace elements, propellants and mixtures thereof.

[0496] It should be understood that those skilled in the art will carefully select such or such optional (one or more) additional compounds and / or their amounts so that the advantageous properties of the compositions according to the invention are not or substantially not adversely affected by the intended addition.

[0497] It should be understood that those skilled in the art will carefully select such or such optional (one or more) additional compounds and / or their amounts so that the advantageous properties of the particles according to the invention are not or substantially not adversely affected by the intended addition.

[0498] As previously stated, the compositions according to the present invention can be cosmetics, and are preferably cosmetics.

[0499] The compositions according to the invention are generally suitable for topical application to the skin and thus generally contain a physiologically acceptable medium, i.e., a skin-compatible medium.

[0500] Preferred media are cosmetically acceptable media, i.e., media with a pleasant color, smell and feel that do not cause any unacceptable discomfort (i.e., stinging or tightness) that might cause a user to be unwilling to apply the composition.

[0501] Presentation form of the composition Compositions containing particles according to the invention, especially cosmetic compositions, can be prepared using techniques known to those skilled in the art.

[0502] Depending on the target application, they can be in any conventional presentation form and are suitable for local application, i.e., application to the surface of the keratin material under consideration.

[0503] The cosmetic compositions may be in the form of aqueous or water-alcohol gels. They may be in the form of simple or complex emulsions (O / W, W / O, O / W / O, or W / O / W), such as creams, emulsions, or gel-creams.

[0504] They can also be in anhydrous form, such as in oil form.

[0505] The term "anhydrous composition" refers to a composition containing less than 5% by weight of water, or even less than 2% by weight of water, more preferably less than 1% by weight of water, and especially anhydrous, wherein the water is not added during the preparation of the composition, but corresponds to the residual water provided by the mixed components.

[0506] The cosmetic composition can be used, for example, as a color cosmetic product.

[0507] The cosmetic composition can be used, for example, as a facial and / or body care and / or sun protection product having a liquid to semi-liquid consistency, and can have a more or less oily appearance as a white or colored cream, ointment, emulsion, cream-gel, lotion, serum, paste, or foam. It can optionally be applied to the skin in aerosol form. It can also be in solid form, such as a stick.

[0508] The cosmetic composition may be in the form of a product for caring for the skin or semi-mucous membrane, such as 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, makeup base, protective or care body lotion, after-sun lotion, skin care or scalp care lotion, gel or foam, serum, mask, or aftershave composition).

[0509] The composition can be applied by hand or using an applicator.

[0510] In particular, the cosmetic composition has an SPF of greater than 5 and preferably greater than 10.

[0511] For the purposes of this invention, the term "SPF" refers to the sun protection factor, which measures the level of protection against UV rays. The SPF value corresponds to the ratio between the shortest time required to obtain (erythematous) sunburn with a sunscreen composition and the shortest time required to obtain said sunburn without using a sunscreen composition. More specifically, the term "SPF" is defined in the article "A new substrate to measures unscreen protection factors across the ultraviolet spectrum", J. Soc. Cosmet. Chem., 40, 127-133 (May / June 1989).

[0512] SPF (Sun Protection Factor) can be evaluated in vitro using a Labsphere® spectrophotometer. A sheet is a material on which the sun protection composition is applied. Poly(methyl methacrylate) (PMMA) sheets have proven ideal for this method. The SPF of the composition can also be evaluated in vivo according to ISO 24444 “Cosmetics - Sun protection test methods - in vivo determination of the Sun Protection Factor (SPF) (2010)”.

[0513] The term "UV-APF" refers to an index characterizing protection against UV-A radiation. Specifically, it is possible to measure this index in vivo using the PPD (Persistent Pigment Darkening) method: PPD measures skin color observed 2 to 4 hours after exposure to UV-A rays. This method has been adopted by the Japan Cosmetic Industry Association (JCIA) since 1996 as the official testing procedure for UV-A labeling of products and is commonly used by testing laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin. Measurement standards for the efficacy of UV-A protection, promulgated November 21, 1995, and effective January 1, 1996). UV-A protection can also be evaluated in vitro using a Labsphere® spectrophotometer. Sheets are materials on which the sunscreen composition is applied. Polymethyl methacrylate (PMMA) sheets have proven ideal for this purpose. ISO 24443 describes such in vitro methods.

[0514] Cosmetic Uses and Methods The present invention also relates to the non-therapeutic cosmetic use of the composite material according to the invention for filtering UV radiation, preferably UV-B radiation, comprising applying at least one composition comprising at least one composite material as defined above onto a keratin material.

[0515] The present invention also relates to a non-therapeutic cosmetic method for shielding against UV radiation, particularly UV-B radiation, comprising applying a composition containing at least one composite material as defined above onto a keratin material.

[0516] According to another aspect, the present invention also relates to the non-therapeutic cosmetic use of cosmetic compositions comprising at least one previously defined composite material for preventing the appearance of darker and / or more intense spots on the skin, particularly on the face, neck, arms, hands and / or shoulders, that cause uneven skin color.

[0517] The present invention also relates to a non-therapeutic cosmetic method for limiting the darkening of keratin materials (particularly human keratin materials such as skin) and / or keratin fibers (particularly human keratin fibers such as hair) and / or for improving skin color and / or the color and / or uniformity of keratin fibers, comprising applying at least one cosmetic composition comprising at least one previously defined composite material to the surface of said keratin material and / or said keratin fibers.

[0518] The present invention also relates to cosmetic compositions comprising at least one previously defined composite material for non-therapeutic cosmetic use in preventing premature aging of keratin materials, particularly human keratin materials such as skin, especially the skin of the face, neck, arms, hands and / or shoulders.

[0519] The present invention also relates to a non-therapeutic cosmetic method for preventing and / or treating signs of aging in keratin materials (particularly human keratin materials such as skin), comprising applying at least one cosmetic composition comprising at least one previously defined composite material to the surface of the keratin material.

[0520] According to one aspect, the present invention relates to a previously defined composite material used as a reagent for filtering UV radiation, particularly UV-B radiation.

[0521] For the purposes of this invention, the terms “preventing” or “prevention” refer to at least a partial reduction in the risk of a given phenomenon, such as signs of aging of keratin materials (particularly human keratin materials such as skin) or the appearance of darker and / or more intense spots on said keratin materials (particularly human keratin materials such as skin) that cause uneven skin color and / or premature aging of the skin.

[0522] In the specification and examples, percentages are weight percentages or molar percentages. These components are mixed in an order and under conditions readily determined by those skilled in the art.

[0523] The invention will now be described with the aid of the following embodiments, which are given by way of non-limiting description of the invention. Example

[0524] Example 1: Preparation of bismuth oxycarbonate particles according to the present invention Bismuth oxycarbonate particles 1 and 2 were synthesized according to the preparation methods described in Examples 1.A and 1.B below.

[0525] The morphology of bismuth oxycarbonate particles was determined by direct observation using transmission electron microscopy. 1 to 5 mg of dried particles were dispersed in 10 mL of anhydrous ethanol and treated in an ultrasonic bath for two minutes. Subsequently, 5 μL of the dispersion was placed on an observation grid (copper with a carbon surface layer) and dried in ambient air.

[0526] Observations were performed using a Hitachi HT 7700 transmission electron microscope at an accelerating voltage of 100 kV. The average size of the particles was obtained by measuring the particle size using image analysis with ImageJ software (CA Schneider, WSRasband, KW Eliceiri, NIH Image to ImageJ: 25 years of image analysis, Nat.Methods. 9 (2012) 671–675).

[0527] Example 1.A: Synthesis of bismuth oxycarbonate particles 1 A solution of bismuth nitrate pentahydrate Bi(NO3)3·5H2O (0.40 M) and D-mannitol (2 M) was prepared in 800 mL of water and stirred until the reagents were completely dissolved. Then, 160 mL of ammonium carbonate solution (2.1 equivalents relative to bismuth) was added. A white solid precipitate formed. After 30 minutes, the mixture was transferred to a Teflon autoclave reactor and heated at 150 °C for 12 hours. Bismuth oxycarbonate particles 1 were separated by centrifugation and washed three times with water before drying at 60 °C.

[0528] Bismuth oxycarbonate particles 1 are thin sheets with the following average dimensions: Average length L: 85nm Average width l: 52nm Average thickness e: 28nm Example 1.B: Synthesis of Bismuth Oxycarbonate Particles 2 A solution of bismuth nitrate pentahydrate Bi(NO3)3·5H2O (0.40 M) and D-mannitol (0.87 M) was prepared in 800 mL of water and stirred until the reagents were completely dissolved. Then, 160 mL of ammonium carbonate solution (2.1 equivalents relative to bismuth) was added. A white solid precipitate formed. The mixture was then transferred to a Teflon autoclave reactor and heated at 125 °C for 7.5 h. Product 2 was separated by centrifugation, washed three times with water, and then dried at 60 °C.

[0529] Bismuth oxycarbonate particles 2 are thin sheets with the following average dimensions: Average length L: 86nm Average width l: 53nm Average thickness e: 28nm Example 2: Synthesis of the composite material according to the present invention Example 2.A1: Synthesized by atomization of bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0530] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight at room temperature. A white dispersion was then atomized at 150°C with a pumping rate of 15%, a suction rate of 80%, and two nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0531] Composite material A1 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0532] Example 2.A2: Synthesized by atomization of bismuth oxycarbonate / carrageenan composite material at a mass ratio of 0.5. Heat the carrageenan (INCI name: CARRAGEENAN) (2 g) solution in 100 ml of water to 80°C and stir until the polymer is completely dissolved. Then cool the viscous medium to room temperature.

[0533] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the viscous solution, and the suspension was sonicated for 15 minutes and then stirred overnight at room temperature. A white dispersion was then obtained by atomization at 150°C, with a pumping rate of 15%, a suction rate of 80%, and four nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0534] Composite material A2 was separated as an off-white powder and characterized by UV / Vis spectrophotometry.

[0535] Example 2.B1: Synthesized by freeze-drying of a bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0536] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was then freeze-dried.

[0537] Composite material B1 was separated in the form of a white solid and characterized by UV / Vis spectrophotometry.

[0538] Example 2.B2: Synthesized by freeze-drying of a bismuth oxycarbonate / carrageenan composite material at a mass ratio of 4.16. The solution of carrageenan (INCI name: CARRAGEENAN) (0.24 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0539] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was then freeze-dried.

[0540] Composite material B2 was separated in the form of a white solid and characterized by UV / Vis spectrophotometry.

[0541] Example 2.C1: Synthesized by centrifugation of a bismuth oxycarbonate / carrageenan composite at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0542] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was then centrifuged. The precipitate was washed with ethanol and centrifuged again. The resulting solid was dried under vacuum at 50°C.

[0543] The composite material C1 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0544] Example 2.C2: Synthesized by precipitation / centrifugation of bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0545] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was precipitated with 4 volumes of ethanol and then centrifuged. The resulting solid was dried under vacuum at 50°C.

[0546] The composite material C2 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0547] Example 2.C3: Synthesized by precipitation / centrifugation of bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0548] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was precipitated with 4 volumes of ethanol and then centrifuged. The resulting solid was dried under vacuum at 50°C.

[0549] The composite material C3 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0550] Example 2.C4: Synthesized by precipitation / centrifugation of bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0551] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was precipitated with 10 volumes of ethanol and then centrifuged. The resulting solid was dried under vacuum at 50°C.

[0552] The composite material C4 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0553] Example 2.D: Synthesis by atomization of bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0554] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. A white dispersion was then obtained by atomization at 150°C, wherein the pumping rate was 15%, the suction rate was 80%, and there were 5 nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0555] Composite material D was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0556] Example 2.E1: Synthesized by freeze-drying of a bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. The solution of carrageenan (INCI name: CARRAGEENAN) (0.6 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0557] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was then freeze-dried.

[0558] The composite material E1 was separated in the form of a white solid and characterized by UV / Vis spectrophotometry.

[0559] Example 2.E2: Synthesized by freeze-drying of a bismuth oxycarbonate / carrageenan composite material at a mass ratio of 4.16. The solution of carrageenan (INCI name: CARRAGEENAN) (0.24 g) in 100 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0560] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was then freeze-dried.

[0561] The composite material E2 was separated in the form of a white solid and was characterized by UV / Vis spectrophotometry.

[0562] Example 2.F1: Synthesized by centrifugation of a bismuth oxycarbonate / carrageenan composite at a mass ratio of 1.66. Stir the carrageenan (INCI name: CARRAGEENAN) (0.6 g) solution in 100 ml of water until the polymer is completely dissolved. Then cool the medium to room temperature.

[0563] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was then centrifuged, washed with ethanol, and centrifuged again. The resulting solid was dried under vacuum at 50°C.

[0564] The composite material F1 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0565] Example 2.F2: Synthesized by precipitation / centrifugation of bismuth oxycarbonate / carrageenan composite material at a mass ratio of 1.66. Stir the carrageenan (INCI name: CARRAGEENAN) (0.6 g) solution in 100 ml of water until the polymer is completely dissolved. Then cool the medium to room temperature.

[0566] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was precipitated with 4 volumes of ethanol and then centrifuged. The resulting solid was dried under vacuum at 50°C.

[0567] The composite material F2 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0568] Example 2.G: Synthesized by atomization of a bismuth oxycarbonate / calcium lignosulfonate composite material at a mass ratio of 0.71. Stir the solution of calcium lignosulfonate (DP25228, sold by Borregaard) (1.4g) in 100ml of water until the polymer is completely dissolved.

[0569] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting light beige dispersion was then atomized at 120°C with a pumping rate of 15%, a suction rate of 80%, and five nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0570] Composite material G was separated in the form of beige powder and characterized by UV / Vis spectrophotometry.

[0571] Example 2.H1: Synthesized by freeze-drying of a bismuth oxycarbonate / calcium lignosulfonate composite material at a mass ratio of 0.71. Stir the solution of calcium lignosulfonate (DP25228, sold by Borregaard) (1.4g) in 100ml of water until the polymer is completely dissolved.

[0572] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The light beige dispersion was then lyophilized.

[0573] The composite material H1 was separated in the form of a downy white solid and was characterized by UV / Vis spectrophotometry.

[0574] Example 2.H2: Synthesized by freeze-drying of a bismuth oxycarbonate / calcium lignosulfonate composite material at a mass ratio of 1.78. Stir the solution of calcium lignosulfonate (DP25228, sold by Borregaard) (0.56 g) in 100 ml of water until the polymer is completely dissolved.

[0575] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The light beige dispersion was then lyophilized.

[0576] The composite material H2 was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0577] Example 2.I: Synthesis by atomization of a bismuth oxycarbonate / sodium lignosulfonate composite material at a mass ratio of 0.71. Stir the solution of sodium lignosulfonate (DP25230, sold by Borregaard) (1.4 g) in 100 ml of water until the polymer is completely dissolved.

[0578] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting light beige dispersion was then atomized at 120°C with a pumping rate of 15%, a suction rate of 80%, and five nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0579] Composite material I was separated as a beige powder and characterized by UV / Vis spectrophotometry.

[0580] Example 2.J1: Synthesized by freeze-drying of a bismuth oxycarbonate / sodium lignosulfonate composite material at a mass ratio of 0.71. Stir the solution of sodium lignosulfonate (DP25230, sold by Borregaard) (1.4 g) in 100 ml of water until the polymer is completely dissolved.

[0581] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The light beige dispersion was then lyophilized.

[0582] Composite material J1 was separated in the form of a fluffy white solid and characterized by UV / Vis spectrophotometry.

[0583] Example 2.J2: Synthesized by freeze-drying of a bismuth oxycarbonate / sodium lignosulfonate composite material at a mass ratio of 1.78. Stir the solution of sodium lignosulfonate (DP25230, sold by Borregaard) (0.56g) in 100ml of water until the polymer is completely dissolved.

[0584] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The light beige dispersion was then lyophilized.

[0585] Composite material J2 was separated in the form of a fluffy white solid and characterized by UV / Vis spectrophotometry.

[0586] Example 2.K: Synthesized by atomization of a bismuth oxycarbonate / chitosan composite material at a mass ratio of 0.6. Adjust the pH of the chitosan (Kiosmetine-CSG sold by Kitozyme) (1.64 g) solution in 100 ml of water to 4 with lactic acid, and then stir until the polymer is completely dissolved.

[0587] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting light beige dispersion was then atomized at 160°C with a pumping rate of 15%, a suction rate of 80%, and five nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0588] The composite material K was separated in the form of beige powder and characterized by UV / Vis spectrophotometry.

[0589] Example 2.L1: Synthesized by freeze-drying of bismuth oxycarbonate / chitosan composite material at a mass ratio of 0.6. Adjust the pH of the chitosan (Kiosmetine-CSG sold by Kitozyme) (1.64 g) solution in 100 ml of water to 4 with lactic acid, and then stir until the polymer is completely dissolved.

[0590] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The light beige dispersion was then lyophilized.

[0591] The composite material L1 was separated in the form of beige powder and characterized by UV / Vis spectrophotometry.

[0592] Example 2.L2: Synthesized by freeze-drying of bismuth oxycarbonate / chitosan composite material at a mass ratio of 1.51. Adjust the pH of the chitosan (Kiosmetine-CSG sold by Kitozyme) (0.66 g) solution in 100 ml of water to 4 with lactic acid, and then stir until the polymer is completely dissolved.

[0593] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The light beige dispersion was then lyophilized.

[0594] The composite material L2 was separated in the form of beige powder and characterized by UV / Vis spectrophotometry.

[0595] Example 2.M: Synthesized by atomization of a bismuth oxycarbonate / sodium alginate composite material at a mass ratio of 1.06. The solution of sodium alginate (0.94 g) in 100 ml of water was heated to 40 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0596] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. A white dispersion was then obtained by atomization at 160°C, wherein the pumping rate was 15%, the suction rate was 80%, and there were 2 nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0597] The composite material M was separated in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0598] Example 2.N1: Synthesized by freeze-drying of a bismuth oxycarbonate / sodium alginate composite material at a mass ratio of 1.06. The solution of sodium alginate (0.94 g) in 100 ml of water was heated to 80 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0599] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was then freeze-dried.

[0600] The composite material N1 was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0601] Example 2. N2: Synthesized by freeze-drying of a bismuth oxycarbonate / sodium alginate composite material at a mass ratio of 2.7. The solution of sodium alginate (0.37 g) in 100 ml of water was heated to 80 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0602] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was then freeze-dried.

[0603] The composite material N2 was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0604] Example 2.O1: Synthesized by separation (centrifugation) of bismuth oxycarbonate / sodium alginate composite material at a mass ratio of 1.06. The solution of sodium alginate (0.94 g) in 100 ml of water was stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0605] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was then centrifuged, washed with ethanol, and centrifuged again. The resulting solid was dried under vacuum at 50°C.

[0606] The composite material O1 was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0607] Example 2. O2: Synthesized by centrifugation of a bismuth oxycarbonate / sodium alginate composite material at a mass ratio of 1.06. The solution of sodium alginate (0.94 g) in 100 ml of water was heated to 80 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0608] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was heated at 55°C for 1 h 30, then allowed to return to room temperature, centrifuged, washed with ethanol, and centrifuged again. The resulting solid was dried under vacuum at 50°C.

[0609] The composite material O2 was separated in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0610] Example 2.P1: Synthesized by atomization of a bismuth oxycarbonate / sodium dextran sulfate composite material at a mass ratio of 0.9. Stir the solution of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) (1.1 g) in 100 ml of water until the polymer is completely dissolved.

[0611] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, the suspension was sonicated for 15 minutes, and then stirred overnight. The white dispersion was then atomized at 120°C with a pumping rate of 15%, a suction rate of 80%, and four nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0612] The composite material P1 was separated in the form of beige powder and characterized by UV / Vis spectrophotometry.

[0613] Example 2.P2: Synthesized by atomization of a bismuth oxycarbonate / sodium dextran sulfate composite material at a mass ratio of 8.33. Stir the solution of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) (0.12 g) in 100 ml of water until the polymer is completely dissolved.

[0614] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, the suspension was sonicated for 15 minutes, and then stirred overnight. A white dispersion was then atomized at 120°C with a pumping rate of 15%, a suction rate of 80%, and two nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0615] The composite material P2 was separated in the form of beige powder and characterized by UV / Vis spectrophotometry.

[0616] Example 2.Q1: Synthesized by lyophilization of a bismuth oxycarbonate / sodium dextran sulfate composite material at a mass ratio of 0.9. Stir the solution of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) (1.1 g) in 100 ml of water until the polymer is completely dissolved.

[0617] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, the suspension was sonicated for 15 minutes, and then stirred overnight. The white dispersion was then freeze-dried.

[0618] The composite material Q1 was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0619] Example 2.Q2: Synthesized by lyophilization of a bismuth oxycarbonate / sodium dextran sulfate composite material at a mass ratio of 2.27. Stir the solution of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) (0.44 g) in 100 ml of water until the polymer is completely dissolved.

[0620] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, the suspension was sonicated for 15 minutes, and then stirred overnight. The white dispersion was then freeze-dried.

[0621] The composite material Q2 was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0622] Example 2.R: Synthesized by atomization of a bismuth oxycarbonate / polyvinyl alcohol composite material at a mass ratio of 0.84. A solution of polyvinyl alcohol (Mowiol 8-88, sold by Sigma Aldrich) (1.19 g) in 100 ml of water was heated to 80 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0623] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. A white dispersion was then obtained by atomization at 120°C, wherein the pumping rate was 15%, the suction rate was 80%, and there were 3 nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0624] The composite material R was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0625] Example 2.S1: Synthesized by freeze-drying of a bismuth oxycarbonate / polyvinyl alcohol composite material at a mass ratio of 0.84. A solution of polyvinyl alcohol (Mowiol 8-88, sold by Sigma Aldrich) (1.19 g) in 100 ml of water was heated to 80 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0626] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. A white dispersion was obtained by freeze-drying.

[0627] The composite material S1 was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0628] Example 2.S2: Synthesized by freeze-drying of a bismuth oxycarbonate / polyvinyl alcohol composite material at a mass ratio of 2.12. A solution of polyvinyl alcohol (Mowiol 8-88, sold by Sigma Aldrich) (0.47 g) in 100 ml of water was heated to 80 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0629] 1 g of bismuth oxycarbonate particles according to Example 1B was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. The resulting white dispersion was then lyophilized.

[0630] The composite material S2 was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0631] Example 2.T: Synthesized by precipitation / centrifugation of bismuth oxycarbonate / polyhydroxystearic acid composite material at a mass ratio of 2.12. Heat the solution of polyhydroxystearic acid (INCI name: POLYHYDROXYSTEARIC ACID) (0.84 g) in 50 ml of acetone to 50 °C and stir until the polymer is completely dissolved.

[0632] A suspension of 1 g of bismuth oxycarbonate particles according to Example 1B in 50 ml of acetone was sonicated for 15 minutes, then added to the polymer solution at 50°C, and stirred overnight at room temperature. The resulting white dispersion was then centrifuged. The precipitate was washed with acetone and centrifuged again. The resulting solid was dried under vacuum at 50°C. The resulting white dispersion was then lyophilized.

[0633] The composite material T was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0634] Example 2.U: Synthesized by lyophilization of a bismuth oxycarbonate / sodium dextran sulfate composite material that does not conform to the present invention at a mass ratio of 0.9. Stir the solution of sodium dextran sulfate (Dextralip 10C, sold by Safic-Alcan) (1.1 g) in 100 ml of water until the polymer is completely dissolved.

[0635] 1 g of bismuth oxycarbonate particles (500 nm in length and 50 nm in width) that do not conform 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 lyophilized.

[0636] The composite material U was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0637] Example 2.V: Synthesized by freeze-drying of a bismuth oxycarbonate / pregelatinized hydroxypropyl corn distarch phosphate composite at a mass ratio of 1.1. A solution of pregelatinized hydroxypropyl corn distarch phosphate (INCI name: HYDROXYPROPYL STARCHPHOSPHATE) (0.93 g) in 100 ml of water was heated to 95 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0638] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. A white dispersion was obtained by freeze-drying.

[0639] Composite material V was separated in the form of a fluffy beige solid and characterized by UV / Vis spectrophotometry.

[0640] Example 2.W: Synthesized by lyophilization of bismuth oxycarbonate / pregelatinized hydroxypropyl corn distarch phosphate composite particles at a mass ratio of 2.7. A solution of pregelatinized hydroxypropyl corn distarch phosphate (INCI name: HYDROXYPROPYL STARCHPHOSPHATE) (0.37 g) in 100 ml of water was heated to 95 °C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0641] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. A white dispersion was obtained by freeze-drying.

[0642] The composite material W was separated in the form of a fluffy beige solid and characterized by UV / Vis spectrophotometry.

[0643] Example 2.X: Synthesis by atomization of bismuth oxycarbonate / pullulan polysaccharide composite particles at a mass ratio of 0.71 Stir the solution of pullulan (sold by HAYASHIBARA) (1.4g) in 100ml of water until the polymer is completely dissolved.

[0644] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. A white dispersion was then obtained by atomization at 130°C, wherein the pumping rate was 15%, the suction rate was 80%, and there were 2 nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0645] Composite material X was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0646] Example 2.Y: Synthesized by lyophilization of bismuth oxycarbonate / pullulan polysaccharide composite particles at a mass ratio of 0.71. Stir the solution of pullulan (sold by HAYASHIBARA) (1.4g) in 100ml of water until the polymer is completely dissolved.

[0647] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. A white dispersion was obtained by freeze-drying.

[0648] Composite material Y was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0649] Example 2.Z: Synthesis by lyophilization of bismuth oxycarbonate / pullulan polysaccharide composite particles at a mass ratio of 1.78. Stir the solution of pullulan (sold by HAYASHIBARA) (0.56 g) in 100 ml of water until the polymer is completely dissolved.

[0650] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. A white dispersion was obtained by freeze-drying.

[0651] Composite material Z was separated in the form of a fluffy white solid and was characterized by UV / Vis spectrophotometry.

[0652] Example 2. Synthesis of AA by centrifugation of bismuth oxycarbonate / myristoyl pullulan polysaccharide complex particles at a mass ratio of 0.71. Stir the solution of myristoyl pullulan (sold by Katakura Chikkarin) (1.4 g) in 100 ml of isododecane until the polymer is completely dissolved.

[0653] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes, then stirred overnight. The resulting white dispersion was centrifuged, washed with ethanol, and centrifuged again. The resulting solid was dried under vacuum at 50°C.

[0654] The composite material AA was separated in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0655] Example 2.DD: Synthesized by atomization of bismuth oxycarbonate / hydrolyzed soybean protein composite particles at a mass ratio of 2. Stir the soy protein (INCI name: hydrolyzed soy protein) (0.5g) in 100ml of water until the polymer is completely dissolved.

[0656] 1 g of bismuth oxycarbonate particles according to Example 1A was added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight. A white dispersion was then obtained by atomization at 150°C, wherein the pumping rate was 15%, the suction rate was 80%, and there were 9 nozzles (equipment type: BUCHI B-290 mini spray dryer).

[0657] The composite material DD was separated as a white powder and characterized by UV / Vis spectrophotometry.

[0658] Example 2.EE: A combination of bismuth oxycarbonate particles and sodium lignosulfonate polymer at a mass ratio of 0.71. Stir the solution of sodium lignosulfonate (DP25230, sold by Borregaard) (14 mg) in 10 ml of water until the polymer is completely dissolved.

[0659] 10g of bismuth oxycarbonate particles according to Example 1B were added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight.

[0660] The product EE was characterized by UV / Vis spectrophotometry.

[0661] Example 2.FF: A combination of bismuth oxycarbonate particles and carrageenan polymer at a mass ratio of 1.66. The carrageenan (INCI name: CARRAGEENAN) (6 mg) solution in 10 ml of water was heated to 80°C and stirred until the polymer was completely dissolved. The medium was then cooled to room temperature.

[0662] 10 mg of bismuth oxycarbonate particles according to Example 1A were added to the solution, and the suspension was sonicated for 15 minutes and then stirred overnight.

[0663] The product FF was characterized by UV / Vis spectrophotometry.

[0664] Example 2. HH: Synthesized by centrifugation of the composite bismuth oxycarbonate / ethyl acetoacetate polymer at a mass ratio of 1.06. Stir the solution of ethyl acetoacetate polymer (INCI name: Ethyl AcetoAcetate) (0.935 g) in 100 ml of ethyl acetate until the polymer is completely dissolved.

[0665] 1 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 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.

[0666] The HH composite material was separated in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0667] Example 2.II: Synthesis by centrifugation of the composite material bismuth oxycarbonate / ethyl acetoacetate at a mass ratio of 2.66. Stir the solution of ethyl acetoacetate (INCI name: Ethyl AcetoAcetate) (0.376 g) in 100 ml of ethyl acetate until completely dissolved.

[0668] 1 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 centrifuged and washed twice with ethyl acetate. The resulting solid was dried in an oven at 50°C.

[0669] The II composite material was separated in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0670] Example 2.JJ: Synthesized by centrifugation of the composite bismuth oxycarbonate / PHN polymer at a mass ratio of 0.85. Stir the solution of PHN polymer (Polyhydroxy Nonanoate) (1.17 g) in 100 ml of acetone until the polymer is completely dissolved.

[0671] 1 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 dried in an oven at 50°C.

[0672] The JJ composite material was separated in the form of a white powder and characterized by UV / Vis spectrophotometry.

[0673] Example 2: Summary of conditions for synthesizing materials A to JJ Table 1 below summarizes all the products prepared in Examples 2.A1 to 2.JJ. [Table 1] Complex or product method Bismuth oxycarbonate particles / polymer mass ratio A1 atomization (BiO)2CO3 / carrageenan 1.66 A2 atomization (BiO)2CO3 / carrageenan 0.5 B1 freeze-dried <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 B2 freeze-dried <![CDATA[(BiO)2CO3 / Carrageenan]]> 4.16 C1 Centrifugation <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 C2 Precipitation / Centrifugation <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 C3 Precipitation / Centrifugation <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 C4 Precipitation / Centrifugation <![CDATA[(BiO)2CO3 / carrageenan]]> 1.66 D atomization <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 E1 freeze-dried <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 E2 freeze-dried <![CDATA[(BiO)2CO3 / Carrageenan]]> 4.16 F1 Centrifugation <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 F2 Precipitation / Centrifugation <![CDATA[(BiO)2CO3 / Carrageenan]]> 1.66 G atomization <![CDATA[(BiO)2CO3 / Calcium lignosulfonate]]> 0.71 H1 freeze-dried <![CDATA[(BiO)2CO3 / Calcium lignosulfonate]]> 0.71 H2 freeze-dried <![CDATA[(BiO)2CO3 / Calcium lignosulfonate]]> 1.78 I atomization <![CDATA[(BiO)2CO3 / Sodium lignosulfonate]]> 0.71 J1 freeze-dried <![CDATA[(BiO)2CO3 / Sodium lignosulfonate]]> 0.71 J2 freeze-dried <![CDATA[(BiO)2CO3 / Sodium lignosulfonate]]> 1.78 K atomization <![CDATA[(BiO)2CO3 / chitosan]]> 0.6 L1 freeze-dried <![CDATA[(BiO)2CO3 / chitosan]]> 0.6 L2 freeze-dried <![CDATA[(BiO)2CO3 / chitosan]]> 1.51 M atomization <![CDATA[(BiO)2CO3 / sodium alginate]]> 1.06 N1 freeze-dried <![CDATA[(BiO)2CO3 / Sodium alginate]]> 1.06 N2 freeze-dried <![CDATA[(BiO)2CO3 / Sodium alginate]]> 2.7 O1 Centrifugation <![CDATA[(BiO)2CO3 / Sodium alginate]]> 1.06 O2 Centrifugation <![CDATA[(BiO)2CO3 / Sodium alginate]]> 1.06 P1 atomization <![CDATA[(BiO)2CO3 / Sodium Dextran Sulfate]]> 0.9 P2 atomization <![CDATA[(BiO)2CO3 / Sodium Dextran Sulfate]]> 8.33 Q1 freeze-dried <![CDATA[(BiO)2CO3 / Sodium Dextran Sulfate]]> 0.9 Q2 freeze-dried <![CDATA[(BiO)2CO3 / Sodium dextran sulfate]]> 2.27 R atomization <![CDATA[(BiO)2CO3 / polyvinyl alcohol]]> 0.84 S1 freeze-dried <![CDATA[(BiO)2CO3 / polyvinyl alcohol]]> 0.84 S2 freeze-dried <![CDATA[(BiO)2CO3 / polyvinyl alcohol]]> 2.12 T Precipitation / Centrifugation <![CDATA[(BiO)2CO3 / polyhydroxystearic acid]]> 2.12 U freeze-dried <![CDATA[(BiO)2CO3 / sodium dextran sulfate, where (BiO)2CO3 does not conform to the present invention]]> 0.9 V freeze-dried <![CDATA[(BiO)2CO3 / Pregelatinized Hydroxypropyl Corn Distarch Phosphate]]> 1.1 W freeze-dried <![CDATA[(BiO)2CO3 / Pre-gelatinized Hydroxypropyl Corn Distarch Phosphate]]> 2.7 X atomization <![CDATA[(BiO)2CO3 / Pullulan]]> 0.71 Y freeze-dried <![CDATA[(BiO)2CO3 / Pullulan]]> 0.71 Z freeze-dried <![CDATA[(BiO)2CO3 / Pullulan]]> 1.78 A Centrifugation <![CDATA[(BiO)2CO3 / Nyloyl pullulan]]> 0.71 DD atomization <![CDATA[(BiO)2CO3 / Hydrolyzed soy protein]]> 2 EE combination <![CDATA[(BiO)2CO3 + Sodium lignosulfonate]]> 0.71 FF combination <![CDATA[(BiO)2CO3 + carrageenan]]> 1.66 HH Centrifugation <![CDATA[(BiO)2CO3 / ethyl acetoacetate]]> 1.06 II Centrifugation <![CDATA[(BiO)2CO3 / ethyl acetoacetate]]> 2.66 JJ Centrifugation <![CDATA[(BiO)2CO3 / PHN polymer]]> 0.85

[0674] Example 3: Absorption spectra of bismuth oxycarbonate composite materials and combined products The ultraviolet-visible spectrophotometric absorption spectrum of the composite material prepared according to the present invention and in accordance with Example 2 has been generated.

[0675] For composites R, S1, S2 and T, as well as AA, HH, II and JJ, they were obtained by UV-Vis spectrophotometry as dispersions of the composites in water or in a mixture of water / propylene glycol / polysorbate 20 (Tween 20) (with corresponding mass fractions of 49.85 / 49.85 / 0.30).

[0676] The quartz cuvette used for absorbance measurement has a side length of 1 cm. The spectrophotometer used is a ThermoFisher Scientific Genesys 10S.

[0677] Preparation of dispersions An aqueous dispersion of the bismuth oxycarbonate / polymer composite containing 0.1% by mass of bismuth oxycarbonate was exposed to sonication for 2 to 15 minutes, followed by stirring with a magnetic stirrer for 16 hours. The suspension was then diluted to 0.005% by mass of bismuth oxycarbonate and stirred again with a magnetic stirrer for 20 minutes for absorbance measurement.

[0678] When the UV absorbance measurement value exceeds a predetermined threshold, the filtering of UV radiation is considered effective. Specifically, in a dispersion medium containing the composite material at a mass fraction of 0.005%, a composite material with a UV absorbance threshold greater than 0.25 is considered to effectively filter UV radiation.

[0679] The absorption spectrum is shown in Figures 1 to 20 .

[0680] The results are summarized in Table 2 below.

[0681] [Table 2]

[0682] The composite material according to the invention exhibits good UV absorption and thus effectively blocks UV rays, especially in the UV-B range. In contrast, the contrasting composite material exhibits low absorbance and does not provide adequate shielding across the entire UV range.

[0683] The absorption spectrum also shows that the composite material according to the invention has high transparency in the visible light range between 400 nm and 780 nm.

[0684] Example 4: Absorption kinetics of a composite material consisting of bismuth oxycarbonate particles and a polymer, and of a combination of bismuth oxycarbonate particles and the same polymer in the same mass ratio. The absorption kinetics of composite materials consisting of bismuth oxycarbonate particles and polymers, as well as combinations of bismuth oxycarbonate particles and the same polymer in the same mass ratio, were studied. A dispersion containing 0.005% by mass of bismuth oxycarbonate in water was investigated at 45 °C for t = 0 and t = 48 h.

[0685] The absorption spectrum was obtained by UV-Vis spectrophotometry according to the scheme described in Example 3, and... Figure 16 and 17 Presented in the middle.

[0686] The results are summarized in Table 3 below.

[0687] [Table 3]

[0688] The composite material according to the invention exhibits good UV radiation absorption at t=0 and t=48h and 45°C, and thus effectively blocks UV radiation, especially in the UV-B range. In contrast, the comparative product does not provide adequate blocking across the entire UV range.

[0689] Example 5: Preparation of the aqueous composition A1.1 according to the present invention Sodium lauryl ether sulfate (Rhodapex ESB 30HA1 MB, commercially available from Solvay) was prepared at 1% by weight in water and stirred until completely dissolved. It was then diluted in water to a concentration of 0.1% by weight. Composite material A1, synthesized according to Example 2.A1, was added to the diluted sodium lauryl ether sulfate solution at a concentration of 0.1% by weight. The mixture was homogenized by magnetic stirring at 600 rpm for 5 minutes, and then sonicated in an ultrasonic bath (Prolabo TP 680 / DH) at 100% power in continuous mode for 15 minutes. Finally, it was magnetically stirred at 600 rpm for 16 hours.

[0690] The resulting composition in dispersion form is called A1.1.

[0691] Example 6: Absorption spectrum of the aqueous composition A1.1 according to the present invention The dispersion A1.1 according to Example 5 was diluted with deionized water to a final concentration of 0.005% by weight in the composite material A1, and then magnetically stirred at 600 rpm for 20 minutes, followed by absorbance measurement. The quartz cuvettes used for absorbance measurement were 1 cm thick. Absorption spectra were acquired using a UV-2600 UV-Vis spectrophotometer (Shimadzu). Baseline determinations were performed beforehand on water-filled quartz cuvettes. When the measured ultraviolet absorbance is higher than a predetermined threshold, the UV ray filtering is considered effective. In particular, a composition containing 0.005% by weight of composite material Al according to Example 2.A1 is considered to effectively filter UV rays if its maximum absorbance in the UV range is higher than 0.25.

[0692] The absorption spectrum of composition A1.1 according to the present invention is in Figure 21 The information is provided in the text.

[0693] The absorbance values ​​are reported in Table 4 below.

[0694] [Table 4] absorbance Composition A1 absorbance at 220nm 0.63 absorbance at 300nm 0.74 absorbance at 400nm 0.34 absorbance at 620nm 0.08

[0695] Composition A1.1 according to the invention exhibits good absorption of UV rays and thus effectively filters UV rays, especially in the UVB range.

[0696] The absorption spectrum also shows that the composition A1.1 according to the invention has high transparency in the visible light range of 400 to 780 nm.

Claims

1. Composite materials, comprising: a) At least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) and its solvates such as its hydrate, where -0.4 < x < 0.6, and the maximum average size of the particles is less than 400 nm; and b) At least one polymer.

2. The composite material according to claim 1, characterized in that... The composite material has an average particle size of less than or equal to 1 μm, more preferably less than or equal to 500 nm, and even more preferably less than or equal to 450 nm.

3. In the composite material according to any one of the preceding claims, the mass ratio of one or more bismuth oxycarbonate particles a) to one or more polymers b) is 0.01 to 50, preferably 0.2 to 15, more preferably 0.3 to 10, and even more preferably 0.5 to 8.

5.

4. The composite material according to any one of the preceding claims, comprising: - Core, said core comprising at least a) at least one particle of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) and its solvates, such as its hydrates, where -0.4 < x < 0.6, the maximum average size of said particles being less than 400 nm; and - At least one layer, said layer continuously or discontinuously surrounding the core, and comprising b) at least one polymer.

5. In the composite material according to the preceding claim, the molar ratio between the number of moles of one or more coating compounds and the number of moles of one or more core compounds is 0.0001 to 20, preferably 0.005 to 15, more preferably 0.01 to 10, and even more preferably 0.05 to 5.

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

7. The composite material according to any one of the preceding claims, wherein the bismuth oxycarbonate particles are of formula (BiO)2(CO3) and its solvates, such as its hydrates.

8. The composite material according to any one of the preceding claims, wherein the bismuth oxycarbonate particles are in the form of tubes, sheets and / or rods, preferably in the form of sheets and / or rods.

9. The composite material according to any one of the preceding claims, wherein the one or more polymers b) are nonionic, anionic or cationic, preferably nonionic or anionic, and more specifically 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, polyacetoacetate, poly(lactic-co-glycolic acid), cellulose and its derivatives, alginate and its salts, carrageenan, starch, pectin, inulin, dextran and its derivatives, xanthan gum, ulva polysaccharide, lignin sulfonate and its salts, chitin and chitosan, pullulan, polyvinyl alcohol and polyhydroxystearic acid, and / or copolymers thereof, or mixtures thereof.

10. The composite material according to any one of the preceding claims, wherein the one or more polymers b) are selected from: - Lignosulfonic acid, lignin sulfonates, sulfonated polystyrene, polystyrene sulfonates, anionic polyaniline derivatives, especially polyaniline sulfonates, and mixtures thereof. - Alkyl esters or ethers of polyols (especially glycerol), - Anionic polysaccharides, preferably selected from sulfated polysaccharides, especially Ulva polysaccharide, dextran sulfate, carrageenan, and mixtures thereof, as well as polysaccharide carboxylates, especially alginates. - Cationic polysaccharides, preferably selected from polysaccharides with amine groups, especially chitosan. - Modified polysaccharides, particularly those selected from polysaccharide esters, and preferably pullulan esters. - Poly((C2-C5)alkylene imides), preferably selected from polyethyleneimine and polypropyleneimine, especially poly(ethyleneimine), - Polyamino acids, preferably proteins, - An anionic acyclic polymer containing a carboxyl group or a carboxylate of an alkali metal or alkaline earth metal such as sodium, and selected from homopolymers or copolymers of (meth)acrylic acid, preferably selected from sodium polymethacrylate and copolymers of (meth)acrylic acid with alkyl (poly)ether (meth)acrylates, particularly copolymers of (meth)acrylic acid and POE / POP (meth)acrylates, and - Its mixture.

11. The composite material according to any one of the preceding claims, wherein the one or more polymers b) are selected from: - Lignosulfonates, especially alkali metal or alkaline earth metal ligninsulfonates, such as sodium ligninsulfonate or calcium ligninsulfonate. - Carrageenan, -Chitosan, - Alginates, especially alkali metal or alkaline earth metal alginates, such as sodium alginate. - Dextran, especially alkali metal or alkaline earth metal dextran, and alkali metal or alkaline earth metal dextran sulfates, such as sodium dextran sulfate. - Polyhydroxystearic acid, - Starch and its derivatives, especially its phosphorylated derivatives, such as hydroxypropyl corn distarch phosphate, Pullulan and its ester derivatives, especially C1-C 30 C is preferred 10 -C 20 Carboxylic acids, such as myristoyl pullulan, -Polyvinyl alcohol, - Optional hydrolyzed proteins, such as optional hydrolyzed soy protein, and - Its mixture.

12. The composite material according to any one of claims 1 to 9, wherein the one or more polymers b) are selected from polysaccharides, particularly: - Anionic polysaccharides, preferably selected from sulfated polysaccharides, especially Ulva polysaccharide, dextran sulfate, carrageenan, and mixtures thereof, as well as polysaccharide carboxylates, especially alginates. - Cationic polysaccharides, preferably selected from polysaccharides with amine groups, especially chitosan. - Modified polysaccharides, particularly selected from polysaccharide esters, and preferably selected from pullulan polysaccharide esters.

13. A method for preparing a composite material according to any one of the preceding claims, comprising at least the following steps: (i) Provide at least one particle a) of bismuth oxycarbonate, which is of formula (I) (BiO) 2-x (CO3) of formula (I) and its solvates such as its hydrate, where -0.4 < x < 0.6, the maximum average size of the particles being less than 400 nm, optionally dispersed in at least one solvent or solvent mixture A; (ii) Provide a solution of at least one polymer b), optionally in a solvent or solvent mixture B; (iii) Contacting the at least one particle (a) or dispersion (i) with the solution (ii) to form a composite material; (iv) Separate the composite material.

14. The preparation method according to the preceding claim, wherein 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 mixtures thereof.

15. The preparation method according to any one of claims 13 and 14, further comprising one or more separation steps, particularly by centrifugation and / or by filtration, particularly ultrafiltration, and / or by lyophilization and / or by atomization.

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

17. The composition according to the preceding claim, comprising at least: 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) at least one compound selected from: 1) a UV-masking agent different from composite material i); 2) a colorant; 3) a cosmetic surfactant for use in keratin materials; 4) a surfactant; 5) a thickener; and mixtures thereof.

18. The composition according to any one of claims 16 and 17, wherein the composite material is present in an amount of 0.5% to 70% by weight, preferably 1% to 50% by weight, and still more preferably 2% to 40% by weight relative to the total weight of the composition.

19. The non-therapeutic cosmetic use of the composite material according to any one of claims 1 to 12, for filtering UV radiation, preferably UV-B radiation, comprising at least applying a composition comprising the composite material according to any one of claims 1 to 12 to a keratin material.

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

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