JP2018193367A - Ultraviolet light-shielding clay mineral-metal oxide composite powder, method for producing the same, and ultraviolet light-shielding composition containing composite powder - Google Patents

Abstract

To provide a method for producing ultraviolet light-shielding clay mineral-metal oxide composite powder.SOLUTION: After producing spray solution by mixing metal oxide nanoparticles or precursor substance of metal oxide which are capable of shielding ultraviolet light into clay mineral suspension in which clay mineral particles are dispersed, the spray solution is sprayed and dried, and thus clay mineral-metal oxide composite powder is produced. Metal oxide has a band gap that absorbs light in an ultraviolet region and transmits light in a visible light region. In the case of applying such clay mineral-metal oxide composite powder to an ultraviolet light-shielding composition, not only direct contact between metal oxide nanoparticles and a human body can be drastically reduced, but also impregnation of metal oxide nanoparticles into a human body can be fundamentally prevented, so that human body stability of the composition can be significantly improved.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a clay mineral-metal oxide composite powder capable of blocking ultraviolet light, a method for producing the same, and an ultraviolet blocking composition containing the composite powder.

  Ultraviolet rays irradiated from the sun act as a main cause of inducing erythema, edema, freckles, skin cancer and the like on the skin, and recently, research on skin diseases caused by ultraviolet rays has been actively promoted. At the same time, recognition has been expanded as a basic cosmetic product in which an ultraviolet blocking agent is indispensable, and research on dedicated products that can maintain the ultraviolet blocking effect has been actively promoted.

  In such UV blocking products, inorganic UV blocking agents such as titanium dioxide and zinc oxide are often used in order to have a high SPF value. Such UV blocking oxides are in the form of nanoparticles. When applied to an ultraviolet blocking composition, not only skin toxicity can occur, but also the problem of nanoparticles penetrating into the skin can occur.

  An object of the present invention is not only to significantly reduce the direct contact between the metal oxide nanoparticles harmful to the human body and the human body when applied to the composition, but also the metal oxide nanoparticles penetrate into the human body. An object of the present invention is to provide a method for producing a UV-blocking clay mineral-metal oxide composite powder that can fundamentally prevent this.

  Another object of the present invention is to provide a clay mineral-metal oxide composite powder for shielding ultraviolet rays produced by the production method.

  Another object of the present invention is to provide an ultraviolet blocking composition containing the ultraviolet blocking clay mineral-metal oxide composite powder.

  According to an embodiment of the present invention, a method for producing a UV-blocking clay mineral-metal oxide composite powder includes: a metal oxide nanoparticle capable of blocking UV rays in a clay mineral suspension in which clay mineral particles are dispersed; A first stage of mixing an oxide precursor material to produce a spray solution; and a second stage of spray drying the spray solution, wherein the metal oxide absorbs light in an ultraviolet region, and is in a visible light region. The light can have a band gap to transmit.

  In one embodiment, the clay mineral particles may have a layered structure in which crystal units formed by combining a silicate plate and an alumina sheet are stacked.

  In one embodiment, the clay mineral particles may have an average thickness of about 1 to 15 nm and an average diameter of about 4 to 200 μm.

In one embodiment, the metal oxide may include one or more selected from the group consisting of titanium dioxide (TiO ₂ ), zinc oxide (ZnO), cerium oxide (CeO), and the like.

  In one example, the metal oxide nanoparticles may have an average diameter of about 5 to 100 nm.

  In one embodiment, the metal oxide precursor material is selected from the group consisting of an organic acid salt, a halogen salt, an inorganic acid salt, an alkoxy salt, a sulfide salt, and an amide salt containing a metal contained in the metal oxide. One or more of them may be included.

  In one embodiment, the second step may be performed using a spray drying apparatus. In this case, the spray drying apparatus to be applied is coupled to a first chamber having a first internal space and an upper end of the first chamber, and sprays the spray solution into the first internal space in the form of droplets. A nozzle, a tank for storing the spray solution, a solution injection pipe connecting the nozzle, and a pump for generating a pressure for injecting the spray solution stored in the storage tank through the nozzle by applying pressure to the solution injection pipe A spray unit comprising: a gas supply pipe for supplying a dry gas to the first internal space; a gas injection unit comprising a heater for heating the dry gas moving through the gas supply pipe; and a lower end of the first chamber The first clay mineral-metal falling to the bottom of the first chamber in the clay mineral-metal oxide composite powder formed through drying of the spray droplets A first recovery unit for storing and recovering the compound composite powder; a second chamber having a second internal space connected to the first internal space; and a lower end of the second chamber; A second recovery unit for storing and recovering a second clay mineral-metal oxide composite powder that moves and falls into the second chamber by the dry gas in the metal oxide composite powder; And a suction unit for discharging the dry gas cooled from the space to the outside.

  An ultraviolet blocking clay mineral-metal oxide composite powder according to an embodiment of the present invention includes plate-like clay mineral particles aggregated with each other and metal oxide nanoparticles attached to the surface of the clay mineral particles. Can do.

  In one embodiment, the aggregate of the plate-like clay mineral particles may have a porous structure having a groove on the surface and pores inside, and the metal oxide nanoparticles have a surface forming the groove and the surface. It can be attached to the surface forming the pores.

  In one embodiment, the clay mineral-metal oxide composite powder may have an average diameter of about 4 to 100 μm.

  In one embodiment, the metal oxide nanoparticles may be included at 5-50% by weight of the clay mineral particles.

  The ultraviolet blocking composition according to the embodiment of the present invention is contained in an amount of 1 to 50% by weight based on the total weight of the composition, and the plate-like clay mineral particles aggregated with each other and the metal adhered to the surface of the clay mineral particles. Ultraviolet-blocking clay mineral-metal oxide composite powder containing oxide nanoparticles, a wax component contained in an amount of 1 to 15% by weight based on the total composition weight, and 1 to 90% based on the total composition weight % Oil component can be included.

  In one embodiment, the ultraviolet blocking composition may be pasty, creamy, gelled or solid.

  According to the present invention, a clay mineral-metal oxide composite powder for ultraviolet blocking can be produced by a simple method. When this is applied to an ultraviolet blocking composition, the metal oxide nanoparticles adhere not only to the outer surface of the clay mineral particle aggregate, but also to the surface forming the grooves and the surface forming the internal pores. Therefore, not only can the direct contact between the metal oxide nanoparticles and the human body be remarkably reduced, but also the penetration of the metal oxide nanoparticles into the human body can be fundamentally prevented.

FIG. 3 is a procedure diagram for explaining a method for producing a UV-blocking clay mineral-metal oxide composite powder according to an embodiment of the present invention. It is a figure for demonstrating the spray-drying apparatus for manufacturing the said clay mineral-metal oxide composite powder.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
While the invention is amenable to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and will herein be described in detail. However, this is not intended to limit the invention to the specific forms of disclosure, but is to be understood to include all modifications, equivalents or alternatives that fall within the spirit and scope of the invention. It is. In the description of the drawings, like reference numerals have been used for like components. In the accompanying drawings, the dimensions of the structures are shown enlarged from the actual size for the sake of clarity of the present invention.

  The terms first, second, etc. can be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, the first component can be named as the second component without departing from the scope of the present invention, and the second component can be named as the first component as well.

  The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as “comprising” or “having” are intended to indicate the presence of features, steps, actions, components, parts or combinations thereof as described in the specification. It should be understood that the existence or additional possibilities of one or more other features or steps, operations, components, parts or combinations thereof are not excluded in advance.

  Unless otherwise noted, all terms used herein, including technical or scientific terms, are the same as commonly understood by one of ordinary skill in the art to which this invention belongs. It has meaning. Terms such as those defined in commonly used dictionaries should be construed as having a meaning consistent with the meaning possessed in the context of the related art and are ideal unless explicitly defined herein. Or overly interpreted as a formal meaning.

  FIG. 1 is a procedural diagram for explaining a method for producing a UV-blocking clay mineral-metal oxide composite powder according to an embodiment of the present invention, and FIG. 2 shows the clay mineral-metal oxide composite powder. It is a figure for demonstrating the spray-drying apparatus for manufacturing.

  Referring to FIGS. 1 and 2, the method for producing a UV-blocking clay mineral-metal oxide composite powder according to an embodiment of the present invention uses a UV-ray to a clay mineral suspension in which plate-like clay mineral particles are dispersed. It includes a first step S110 for preparing a spray solution by mixing metal oxide nanoparticles that can be blocked or a precursor material of the metal oxide, and a second step S120 for spray-drying the spray solution.

  In the first step S110, the clay mineral particles are formed of a clay mineral having a layered structure in which crystal units formed by combining a silicate plate and an alumina sheet are stacked. Can do. For example, the clay mineral particles may be a mineral of a smectite group, such as bentonite, montmorillonite, beidellite, nontronite, etc., a hydrotalcite group of minerals. , And can be formed of minerals of the vermiculite group.

  The clay mineral particles may have a plate shape having an upper surface and a lower surface parallel to each other. In one embodiment, the clay mineral particles may have an average thickness of about 1 to 15 nm and an average diameter of about 4 to 200 μm.

The metal oxide may be a material having a band gap that can absorb light in the ultraviolet region and block visible light in order to block ultraviolet rays. For example, the metal oxide may include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), cerium oxide (CeO), etc., which are materials having a band gap of about 3.2 eV.

  The solvent for the clay mineral suspension is not particularly limited. For example, water, an organic solvent, or the like can be used as the solvent for the clay mineral suspension.

  In one embodiment, the metal oxide nanoparticles can be mixed with the clay mineral suspension to produce the spray solution. The metal oxide nanoparticles may have a size smaller than the clay mineral particles. For example, the metal oxide nanoparticles can have an average diameter of about 5 to 100 nm. The shape of the metal oxide nanoparticles is not particularly limited. For example, the metal oxide nanoparticles may have a spherical shape.

In another embodiment, the metal oxide precursor material may be mixed with the clay mineral suspension to produce the spray solution. The metal oxide precursor material may include a metal salt including a metal contained in the metal oxide, for example, an organic acid salt, a halogen salt, an inorganic acid salt, an alkoxy salt, a sulfide salt, an amide salt, or the like. . Specifically, the metal salt includes acetate, chloride, acetylacetonate, nitrate, methoxide, ethoxide, butoxide, isopropoxide, sulfide, oxytriisopropoxide, (ethyl or cetylethyl) hexanoate, butanoate, ethylamide, amide, and the like. One or more selected may be included. For example, when the metal oxide for blocking ultraviolet rays is titanium dioxide (TiO ₂ ), the titanium dioxide precursor material may be titanium tetraisopropoxide or titanium tetrabutoxide. One or more selected from titanium alkoxide and the like can be used. As another example, when the metal oxide for blocking UV rays is zinc oxide (ZnO), the zinc oxide precursor may be zinc acetate dihydrate, zinc acetylacetonate mono One or more selected from hydrate (zinc acetate hydrate monohydrate), zinc nitrate hexahydrate (zinc nitrate hexahydrate) and the like can be used.

  In another embodiment, the metal oxide nanoparticles and the metal oxide precursor material may be mixed together with the clay mineral suspension to produce the spray solution.

  In the second step, the spray solution may be sprayed in the form of fine droplets using a nozzle, and the solvent contained in the droplets may be evaporated using a high temperature gas. As the solvent evaporates, the clay mineral particles and the metal oxide nanoparticles contained in the droplets aggregate to form the clay mineral-metal oxide composite powder.

  In one embodiment, the second step may be performed using a spray drying apparatus 100 as shown in FIG. For example, the spray drying apparatus 100 may include a first chamber 110, a spray unit 120, a gas injection unit 130, a first recovery unit 140, a second chamber 150, a second recovery unit 160, and a suction unit 170.

  The first chamber 110 may include a first internal space extending in the vertical direction. If the first internal space is provided, the structure of the first chamber 110 is not particularly limited.

  The spray unit 120 is coupled to an upper end of the first chamber 110 and sprays the spray solution into the first internal space in the form of droplets, a storage tank 10 for storing the spray solution, and the nozzle 121. And a pump 123 that applies pressure to the solution injection pipe 122 and injects the spray solution stored in the storage tank 10 through the nozzle 121.

  The gas injection unit 130 may include a gas supply pipe 131 that supplies a dry gas to the first internal space and a heater 132 that heats the dry gas that moves through the gas supply pipe. The gas supply pipe 131 of the gas injection unit 130 may be directly connected to the first internal space and supply the heated high-temperature dry gas directly to the first internal space. The hot dry gas may be supplied to the first internal space through the nozzle 121 connected to a pipe 122.

  If the solvent of the droplet sprayed from the nozzle 121 can be evaporated, the kind of the high-temperature drying gas is not particularly limited. On the other hand, when the spray solution includes the precursor material of the metal oxide, the high temperature dry gas may be heated to a high temperature that can decompose the precursor material of the metal oxide.

  The first recovery unit 140 may be coupled to a lower end of the first chamber 110, and may pass through the clay mineral-metal oxide composite powder formed through drying of the spray droplets to the second chamber 150. A relatively large powder falling by gravity without moving can be accommodated and recovered. For example, the first recovery unit 140 may include a first container having an internal space opened in an upper direction.

  The second chamber 150 may include a second internal space that is connected to the first internal space and extends in a vertical direction. If the second internal space is provided, the structure of the second chamber 150 is not particularly limited.

  The second recovery unit 160 is coupled to the lower end of the second chamber 150 and moves to the second chamber 150 by the dry gas in the clay mineral-metal oxide composite powder. Small powder can be accommodated and collected. For example, the second collection unit 160 may include a second storage container having an internal space opened in an upper direction.

  The suction unit 170 can discharge the cooled dry gas from the second internal space to the outside. The suction unit 170 can discharge the dry gas to the outside through the upper end of the second chamber 150.

  When the clay mineral-metal oxide composite powder is manufactured using the spray drying apparatus 100 as described above, the composite powder can be separated and recovered according to size.

  Meanwhile, the clay mineral-metal oxide composite powder produced according to the present invention includes plate-like clay mineral particles aggregated spherically and metal oxide nanoparticles attached to the surface of the clay mineral particles. be able to. For example, the plate-like clay mineral particles are aggregated into a porous structure having surface grooves and internal pores, and the metal oxide nanoparticles are not only the outer surface of the plate-like clay mineral particle aggregate, It can be attached to the surface forming the groove and the surface forming the pores.

  The clay mineral-metal oxide composite powder may have an average diameter of about 4 to 100 μm. In each clay mineral-metal oxide composite powder, the metal oxide nanoparticles may be included in an amount of about 5 to 50% by weight of the clay mineral particles.

  An ultraviolet blocking composition according to an embodiment of the present invention may include the clay mineral-metal oxide composite powder, a wax component, and an oil component.

  The clay mineral-metal oxide composite powder may be included in an amount of about 1 to 50% by weight based on the total composition weight. Since the clay mineral-metal oxide composite powder has been described in detail above, a duplicate description thereof will be omitted.

  The wax component may be included in an amount of about 1 to 15% by weight based on the total composition weight. The wax component may contain one or more selected from wax, gelling agent, solid emulsifier and the like. Examples of the wax include plant waxes such as candelilla wax, carnauba wax and rice wax, animal waxes such as bead wax and lanolin, mineral waxes such as ozokerite and ceresin wax, paraffin wax, microcrystalline wax, One or more selected from petroleum-based waxes such as polyethylene wax can be included. Examples of the gelling agent include dextrin palmitate, dextrin palmitate / ethylhexanoate, dextrin myristate, glyceryl behenate, polyglyceryl-6-octatearate, glyceryl behenate / eicosadioate, polyglyceryl-10 -It may contain one or more selected from behenate / eicosadioate, stearoylinulin and the like. Examples of the solid emulsifier include glyceryl stearate, PEG-40-stearate, polyglyceryl-3-methylglucose distearate, methylglucose sesquistearate, alkyl glucoside, cetearyl glucoside, sorbitan oliveate, cetearyl oliveate 1 type or more chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, etc. can be included.

  The oil component may be included in an amount of about 1 to 90% by weight based on the total composition weight. The oil components include hydrocarbon oils such as hydrogenated polydecene, squalane, mineral oil, capric / capric triglycerides, neopentyl glycol dicaprate, neopentyl glycol diheptanoate, neopentyl glycol diethyl hexanoate, 2 -Estyl oils such as octyldodecyl myristate, isopropyl myristate, cetyl 2-ethylhexanoate, octyldodecanol, hexylcanol, glyceryl triethylhexanoate, vegetable oils such as olive oil, jojoba oil, macadamia oil , One or more selected from silicone oil such as cyclomethicone and dimethicone.

  Further, the ultraviolet blocking composition is one or more additives selected from emulsion stabilizers, nonionic surfactants, silicone polymers, extender pigments, fragrances, preservatives, bactericides, oxidation stabilizers, water and the like. Can further be included.

  Meanwhile, the ultraviolet blocking composition according to the embodiment of the present invention may be pasty, creamy, gelled or solid.

  In the ultraviolet blocking composition according to the embodiment of the present invention, the metal oxide nanoparticles are attached not only to the outer surface of the clay mineral particle aggregate, but also to the surface forming the groove portion and the surface forming the internal pores. Since the clay mineral-metal oxide composite powder is used as an ultraviolet blocking agent, not only can the direct contact between the metal oxide nanoparticles and the human body be remarkably reduced, but the metal oxide nanoparticles can be contained inside the human body. Since it can be fundamentally prevented from penetrating into the body, the stability of the human body can be remarkably improved.

  The foregoing has been described with reference to the preferred embodiments of the present invention. However, those skilled in the art can use the invention without departing from the spirit and scope of the present invention described in the following claims. It should be understood that various modifications and changes can be made to the present invention.

100: Spray drying device
110 ... first chamber 120 ... spray unit
130: Gas injection unit 140: First recovery unit
150 ... second chamber 160 ... second recovery unit 170 ... suction unit

Claims (13)

A first step of preparing a spray solution by mixing metal oxide nanoparticles capable of blocking ultraviolet light or a precursor material of the metal oxide into a clay mineral suspension in which clay mineral particles are dispersed;
A second stage of spray drying the spray solution;
The method for producing an ultraviolet blocking clay mineral-metal oxide composite powder, wherein the metal oxide has a band gap that absorbs light in an ultraviolet region and transmits light in a visible light region.   The UV blocking material according to claim 1, wherein the clay mineral particles have a layered structure in which crystal units formed by combining a silica sheet and an alumina sheet are laminated. A method for producing a clay mineral-metal oxide composite powder.   [2] The method according to claim 1, wherein the clay mineral particles have an average thickness of 1 to 15 nm and an average diameter of 4 to 200 [mu] m. Method. _2. The ultraviolet blocking material according to claim 1, wherein the metal oxide includes at least one selected from the group consisting of titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and cerium oxide (CeO). A method for producing a clay mineral-metal oxide composite powder.   [5] The method according to claim 4, wherein the metal oxide nanoparticles have an average diameter of 5 to 100 nm.   The metal oxide precursor material includes at least one selected from the group consisting of an organic acid salt, a halogen salt, an inorganic acid salt, an alkoxy salt, a sulfide salt, and an amide salt containing a metal contained in the metal oxide. The method for producing an ultraviolet blocking clay mineral-metal oxide composite powder according to claim 4, comprising: The second stage is performed using a spray drying device,
The spray dryer is
A first chamber comprising a first internal space;
A nozzle coupled to the upper end of the first chamber and spraying the spray solution in the form of droplets into the first internal space, a tank for storing the spray solution, and a solution injection pipe connecting the nozzle and the solution injection pipe A spray unit comprising a pump that generates pressure to apply pressure to the spray tank to spray the spray solution stored in the storage tank through the nozzle;
A gas injection unit comprising a gas supply pipe for supplying a dry gas to the first internal space and a heater for heating the dry gas moving through the gas supply pipe;
A first clay mineral-metal oxide coupled to a lower end of the first chamber and falling to a lower portion of the first chamber in the clay mineral-metal oxide composite powder formed through drying of the spray droplets A first collection unit for containing and collecting the composite powder;
A second chamber comprising a second internal space connected to the first internal space;
The second clay mineral-metal oxide composite powder, which is coupled to the lower end of the second chamber and moves down to the second chamber by the dry gas in the clay mineral-metal oxide composite powder and falls. A second recovery unit for recovering,
The method for producing a UV-blocking clay mineral-metal oxide composite powder according to claim 1, further comprising an inhalation unit that discharges the dried gas cooled from the second internal space to the outside. Plate-like clay mineral particles agglomerated together,
An ultraviolet blocking clay mineral-metal oxide composite powder comprising metal oxide nanoparticles adhered to the surface of the clay mineral particles. The aggregate of the plate-like clay mineral particles has a porous structure having a groove on the surface and internal pores,
[9] The clay mineral-metal oxide composite powder for ultraviolet blocking according to claim 8, wherein the metal oxide nanoparticles are attached to a surface forming the groove and a surface forming the pores.   [9] The clay mineral-metal oxide composite powder for blocking ultraviolet rays according to claim 8, wherein the clay mineral-metal oxide composite powder has an average diameter of 4 to 100 [mu] m.   [9] The clay mineral-metal oxide composite powder for UV-blocking according to claim 8, wherein the metal oxide nanoparticles are contained in an amount of 5 to 50% by weight of the clay mineral particles. UV-blocking clay mineral-metal comprising plate-like clay mineral particles aggregated with each other and 1 to 50% by weight based on the total composition weight and metal oxide nanoparticles attached to the surface of the clay mineral particles An oxide composite powder;
A wax component contained in an amount of 1 to 15% by weight based on the total composition weight;
An ultraviolet blocking composition comprising 1 to 90% by weight of an oil component based on the total composition weight. [13] The ultraviolet blocking composition according to claim 12, wherein the ultraviolet blocking composition is in the form of a paste, cream, gel, or solid.