KR20180110960A - ROS-inhibiting, UV-screening composite particles and the use thereof - Google Patents

Abstract

The present invention relates to a composite powder for blocking ultraviolet (UV) and an application thereof. Specifically, according to the present invention, it is possible to bring significant synergistic effects by ability of inhibiting active oxygen induced from photoreactions, and also to secure remarkability to effects of blocking ultraviolet in addition to enhanced UV scattering characteristics. Accordingly, the composite powder can be applied to various forms such as a cosmetic material for blocking UV, and a paint material requiring excellent blocking effects for a broader UV range.

Description

(ROS-inhibiting, UV-screening composite particles and the use thereof)

The present invention relates to a composite powder for ultraviolet shielding having an active oxygen-suppressing function and a use thereof.

The ultraviolet rays have a wavelength shorter than visible light and are invisible to the human eye and have a wavelength range of 10 to 400 nm. It has lower permeability than ordinary X-rays or gamma rays but has a higher energy than visible light or infrared rays. Therefore, it acts as a cause of sunburn, pigmentation, photo aging and the like in human skin. It also raises.

The ultraviolet rays are classified into short-wave ultraviolet (UV) (200-280 nm), long-wave ultraviolet (UVB), and long ultraviolet (UVA) Most of the short-wave ultraviolet rays with high energy are absorbed by the ozone layer and disappear without reaching the surface. However, the medium-wave ultraviolet ray is known as a light ray which can penetrate to the epidermal basal layer and the upper part of the epidermis and cause skin cancer by causing sunlight such as erythema and edema and pigmentation such as freckles, and the long wave ultraviolet ray has the longest wavelength It is known as an aging ray that causes photo aging by promoting the generation of wrinkles by reducing the elasticity of the skin by reaching the dermal layer of the skin through the rays. Thus, the need for sunscreen agents has long been recognized in order to protect the skin from ultraviolet rays that cause various skin damages, and as a result, various types of ultraviolet screening products have been introduced.

Conventional ultraviolet screening agents are classified into organic ultraviolet screening agents and inorganic ultraviolet screening agents according to the mechanism of protecting the skin from ultraviolet rays.

The organic ultraviolet screening agent has a mechanism of absorbing ultraviolet rays and converting ultraviolet rays into heat through a chemical reaction and discharging the ultraviolet rays. Representative examples thereof include ethylhexylmethoxycinnamate, ethylhexylsalicylate, octocrylene, butylmethoxydibenzoyl Methane, bis-ethylhexyloxyphenol methoxyphenyltriazine, and diethylaminohydroxybenzoylhexylbenzoate. However, these organic sunscreens are known to be absorbed into the skin and cause problems such as skin irritation and skin toxicity, and their use has been limited.

On the other hand, the inorganic ultraviolet blocking agent has a mechanism of blocking ultraviolet rays from penetrating into skin by reflecting and scattering ultraviolet rays, and representative examples thereof include titanium dioxide and zinc oxide. However, such an inorganic UV-blocking agent is difficult to disperse and dissolve in a formulation, may exhibit a white turbidity phenomenon upon application to the skin or may cause a poor feeling (for example, a foreign body sensation), has a high polarity and a high specific gravity, And there is a problem that it precipitates.

To overcome the shortcomings of these sunscreens, various studies have been attempted.

For example, as a method of surface treatment for improving usability and improving cohesion of titanium dioxide and zinc oxide, a method of surface modification of a titanium alloy by a plasma induced grafting technique in Non-Patent Document 1, -Methacryloyloxyethylphosphorylcholine is reacted with methacryloyloxyethylphosphorylcholine.

In order to improve the cohesion of titanium dioxide and zinc oxide, a method of enclosing them in the PMMA microparticles (Non-Patent Document 2) has been reported. As a method for improving the disadvantage caused by the photocatalytic activity of titanium dioxide, aluminum oxide Al ₂ O ₃ ) and silicon oxide (SiO ₂ ) on the surface of titanium dioxide have been reported.

In addition, the inorganic blocker made small at the nano level is also likely to cause problems such as skin irritation and skin toxicity by adhering to the skin or penetrating into the stratum corneum to generate reactive oxygen species (ROS) There is controversy about the hazard of the use of inorganic blockers of size.

Therefore, there is a pressing need for an excellent sunscreen agent that maintains high safety and excellent ultraviolet shielding effect and does not cause cloudiness.

Accordingly, the present inventors have made efforts to solve the problems of conventional ultraviolet screening agents, in particular, inorganic ultraviolet screening agents. As a result of having tried to solve the problems of conventional ultraviolet screening agents, especially inorganic ultraviolet screening agents, It was confirmed that the present invention provides a remarkable effect on the inhibitory activity of active oxygen.

Furthermore, it is possible to improve ultraviolet shielding ability by scattering ultraviolet rays transmitted through the porous core, which is not shielded by coating the surface of the porous core with the organic-inorganic hybrid multilayer structure, and to provide a synergistic effect on the inhibition of active oxygen Of course, it is confirmed that the whitening phenomenon due to the high refractive index of the conventional inorganic UV blocking agent can be minimized, and excellent optical stability can be realized, thus completing the present invention.

 Colloids and Surfaces B: Biointerfaces 2009, 74 (1), pp. 96-102.  Colloid & Polym Science 2002, 280, pp. 584-588

It is an object of the present invention to provide a porous ultraviolet shielding composite powder comprising a organic-inorganic hybrid multilayer structure.

It is still another object of the present invention to solve the problems such as skin irritation caused by the effective removal of active oxygen generated from the photoreaction, chemical modification of active ingredient by active oxygen, And to provide a cosmetic composition for protecting against ultraviolet rays.

Another object of the present invention is to provide a multilayer film excellent in active oxygen scavenging ability and excellent in ultraviolet shielding ability and a method for effectively removing free radicals using the same.

In order to achieve the above-mentioned object, the present invention provides a porous core comprising: a porous core; And a coating layer formed on the surface of the porous core. At this time, the coating layer of the ultraviolet shielding composite powder is formed by alternately stacking an organic layer containing an antioxidant and an inorganic layer containing inorganic fine particles.

In addition, the present invention provides a cosmetic composition for blocking ultraviolet rays comprising the composite powder.

The present invention also provides a multi-layer film in which an antioxidant and inorganic fine particles are alternately stacked, and a method for removing active oxygen using the same.

INDUSTRIAL APPLICABILITY According to the present invention, the ability to inhibit reactive oxygen generated from a photoreaction is excellent, and the ultraviolet blocking effect can be imparted with remarkable UV scattering characteristics.

According to the present invention, particles having improved dispersion stability can be provided by introducing a porous structure to greatly reduce the specific gravity, and an inorganic sunscreen agent such as titanium dioxide (TiO ₂ ) having photocatalytic activity, which can induce skin irritation and skin aging Thereby preventing skin from being in direct contact with the skin, thereby providing excellent safety to the skin and providing a soft and light feel.

Also, the multilayer composite powder according to the present invention provides cosmetic composition for ultraviolet ray shielding which can impart synergy to ultraviolet shielding ability and effectively improve whitening phenomenon by the light scattering effect derived from the morphology of the porous core, thereby providing improved transparency can do.

Further, according to the present invention, the composite powder and multilayer film in the form of a multilayer film is a novel ultraviolet shielding material with antioxidative low irritation, which can effectively inhibit active oxygen as well as remarkably improved ultraviolet shielding ability, It is expected that it can be applied as a mode.

FIG. 1 is a schematic view of a composite powder surface according to the present invention and a method for removing reactive oxygen generated from a photoreaction. FIG.
FIG. 2 is a scanning electron microscopic photograph of the composite powder prepared in Examples 1 to 4 of the present invention. FIG.
3 is a UV-VIS absorption graph of the composite powder prepared in Examples 1 to 4 (number of coating layers; n) of the present invention.
Figure 4 is a composite powder (PMMA / (TA / TiO _{2) 4)} and Comparative Example 1 (PMMA powder) and Comparative Example 2 (porous PMMA microspheres) and Comparative Example 3 (TiO ₂ nano prepared in Example 4 of the present invention; (SPF) of O / W sunscreen using an ultraviolet barrier (SPF).
FIG. 5 shows the results of measurement of the supercritical radical suppressing ability of the composite powder prepared in Example 4. FIG. 5 (a) shows the absorption spectrum (for 640 nm ), And Fig. 5 (b) shows the concentration of the superoxide radical induced from the photoreaction.
FIG. 6 shows the results of measurement of the ability of the composite powder prepared in Example 4 to inhibit hydroxy radicals. FIG. 6 (a) shows the fluorescence intensity due to the chemical bond between the hydroxy radical and the terephthalic acid , And Fig. 6 (b) shows the concentration of the hydroxy radicals induced from the photoreaction.
7 is a scanning electron microscopic photograph of the composite powders prepared in Examples 5 to 6 of the present invention.
8 is a graph showing the results of measurement of the superoxide radical inhibition ability of the composite powder prepared in Examples 5 to 6. Fig. 8a shows the absorption spectrum (680 nm) of formazan formed by the superoxide radical induced from the photoreaction, And Fig. 8 (b) shows the concentration of the superoxide radical induced from the photoreaction.
FIG. 9 shows the results of measurement of the ability of the composite powder prepared in Examples 5 to 6 to inhibit hydroxy radicals. FIG. 9 (a) shows the fluorescence intensity due to the chemical bond between the hydroxy radical and terephthalic acid , And Fig. 9 (b) shows the concentration of hydroxy radicals induced from the photoreaction.
FIG. 10 is a photograph showing the result of confirming long-term toxicity safety and protection against ultraviolet rays in a mouse model of the composite powder prepared in Example 4 and confirming skin damage through immunohistochemical staining.

The composite powder for ultraviolet shielding according to the present invention and its application will be described below. However, unless otherwise defined in the technical terms and scientific terms used herein, those skilled in the art will understand In the following description, well-known functions and constructions that may unnecessarily obscure the gist of the present invention will not be described.

Conventionally, a technique of enclosing an ultraviolet screening agent using particles of a porous or hollow structure is already known. However, in the prior art, when the ultraviolet screening agent is an organic ultraviolet screening agent, it can not completely solve the problem of inducing skin irritation. When the ultraviolet screening agent is an inorganic ultraviolet screening agent, it does not have a porous structure, I had a limit that I could not contribute.

In order to solve the above problems, the present inventors have devised a composite powder in which the structure of a porous core is maintained and a coating layer of a multi-layered organic-inorganic hybrid coating is introduced into the surface of the composite core.

As described above, the composite powder according to the present invention improves the dispersibility in the formulation with a low specific gravity, thereby enabling formulation in various forms. In addition, the light scattering effect derived from the morphology of the multi-layered composite powder effectively improves opacity and gives improved transparency.

Further, the composite powder according to the present invention does not inhibit the UV scattering property of the porous core and uniformly introduces the inorganic ultraviolet screening agent such as TiO _{2 with} excellent tackiness, thereby improving the ultraviolet shielding ability as well as the soft focus effect A correction effect of the skin tone can be expected.

Specifically, the composite powder according to the present invention comprises a porous core; And a coating layer formed on the surface of the porous core. At this time, the coating layer is formed by alternately stacking an organic layer containing an antioxidant and an inorganic layer containing inorganic microfine particles, and by including a plurality of coating layers alternately stacked, the effect according to the present invention described above can be further doubled.

The term "porous core" in the present invention is not particularly limited as long as it has pores formed on the surface of the particles. For example, gel, precipitated, fumed, dry, ground, calcined, hydrous, or the like. Also, the porous core may have a porosity of 20 to 90 vol% expressed in volume percentage (vol%). Here, the porosity refers to a ratio of the total volume of pores to the total volume of the porous core.

The term "inorganic fine particles" in the present invention is a material uniformly coated on the surface of the porous core, and may be a metal oxide having ultraviolet shielding property. A non-limiting example the metal oxide is cerium oxide (CeO _2), iron oxide _{(Fe 2 O 3, Fe 3} O 4), zirconium oxide (ZrO _2), silica (SiO _2), titanium dioxide (TiO _2), iridium dioxide (IrO ₂ ), zinc oxide (ZnO), and the like.

The core of the composite powder according to an embodiment of the present invention has a porous structure capable of scattering light. Therefore, the UV scattering property of the core and the ultraviolet ray shielding effect by the inorganic fine particles (for example, inorganic UV blocking agents such as TiO ₂ ) introduced into the surface combine with each other, so that a broader range of ultraviolet rays can be blocked. In addition, the composite powder according to the present invention can improve the dispersibility in the formulation with a low specific gravity and can minimize the whitening phenomenon by the light scattering effect derived from the morphology of the porous core.

The porous core of the composite powder according to an embodiment of the present invention is not limited as long as it has pores on its surface, and may be porous organic polymer particles or the like.

For example, the polymeric material of the porous organic polymer particles may be at least one selected from the group consisting of an acrylic polymer, a vinyl polymer, an epoxy polymer, a polyolefin polymer, a polyurethane polymer, a polyamide polymer, a polyester polymer, a polyimide polymer, A polyether-based polymer, a polysiloxane-based polymer, a fluorine-based polymer, a polysaccharide polymer, and the like.

If the surface of the porous organic polymer particles does not contain a polar moiety capable of forming a hydrogen bond, it may be desirable to introduce a polar moiety capable of forming a hydrogen bond through an additional surface treatment. The additional surface treatment may be performed by a known treatment method such as an organic oxidizing agent, an inorganic oxidizing agent, a plasma, ultraviolet-ozone irradiation, electron beam irradiation, and the like. The polymer material of the porous organic polymer particle is not limited to a specific material in that a polar residue capable of forming a hydrogen bond such as a carboxylic acid group or a carbonyl group can be introduced on the surface of the nonpolar polymer particle through the surface treatment.

The polar residues present on the surface of the porous organic polymer can interact with the hydroxyl group contained in the antioxidant through hydrogen bonding or the like and the antioxidant selectively binds to the surface of the porous organic polymer Can be bound to form an organic layer.

One form of the porous core may be spherical particles having an average diameter within a range that does not impart a sense of physical sensation to the feeling, and may preferably have an average diameter of 5 to 15 占 퐉, more preferably 5 to 10 占 퐉 And may have an average diameter.

Also, the porous core may have a specific surface area in the range of 1 to 200 m < 2 > / g. In the range satisfying the specific surface area, the average pore diameter of the porous core may be 1 to 500 nm, 300 nm, more preferably 10 to 200 nm.

In one embodiment, when the composite powder of the present invention is applied to a skin, the porous core of the composite powder may be preferably selected from the biocompatible polymers of the organic polymers described above. As a non-limiting example, the biocompatible polymer may be selected from the group consisting of polyglycolide (PGA), polylactide (PLA), poly (lactide-co-glycolide) (PLGA), polymethylmethacrylate (PMMA), a poly (metha) acrylate copolymer, an ethylene-co-vinyl acetate (EVA) Polymeric particles selected from the group consisting of polystyrene, polystyrene, polycaprolactone (PCL), polyorthoester, polyphosphagene, alginate, collagen, chitosan, and the like.

The above-mentioned porous organic polymer particles can easily control the volume and size of the pores in the particles by controlling the concentration and type of the porogen forming the pores for introducing the porous structure into the surface of the particles.

The composite powder according to one embodiment of the present invention is an inorganic fine particle which is an inorganic UV-blocking agent and uniformly adheres to the surface of the porous core with excellent adhesiveness. This is realized by the organic layer, and the organic layer includes an antioxidant.

At this time, the antioxidant forms a very thin organic layer of several nanometers at the surface of the porous core to help maintain the porosity of the porous core (see FIG. 1). Also, since the organic layer can form a strong metal-ligand charge complex with the subsequent inorganic microparticles, inorganic microparticles can be introduced into the surface of the porous core with improved tackiness.

The antioxidant contained in the organic layer of the composite powder according to an embodiment of the present invention is not limited as long as it has two or more hydroxyl groups and may be preferably selected from polyphenol compounds and phenol compounds.

In one embodiment, the antioxidant according to one aspect of the present invention is selected from the group consisting of catechol, DL-3,4-dihydroxyphenylalanine, 3,4-Dihydroxy-DL-phenylalanine, catecholamine, Thiamine, dopamine, polydodamine, phloroglucinol, caffeophosphoric acid, dihydrocapphophosphoric acid, ferulic acid, protocatechuic acid, chlorogenic acid, isochlorogenetic acid, gentisic acid, homogentisic acid, gallic acid, hexahydroxy diphenic acid, , Rosmarinic acid, lisosporamic acid, quercumin, polyhydroxylated coumarin, polyhydroxylated lignans, neoligans, silymarin, apigenol, ruteolol, quercetin, kerceragin, keratagatine, , Myringine, rhametine, genistein, maerine, goshi pheten, chemperol, rutin, naringin, naringenine, hesperitin, hesperidin, diosmin, diosmecid, amentoflavone, pisetin, Rutigenin, hesperidin, methyl chalcone, taxi poles Ol, silica blank, Christine silica, silica other than di, catechin, epicatechin, Gallo catechin, catechin gallate salts, Gallo catechin gallate salts, epicatechin to catechin gallate salts, catechin gallate salts, epi going to go epi, glucosidase ground; There may be mentioned proanthocyanidin, propyl gallate, isoamyl octyl gallate, dodecyl gallate, penta-O-galloylglucose, tannic acid, galantanin, elagantinin, shikisan acid, salicylic acid and resveratrol.

According to one aspect of the present invention, skin irritation and side effects added thereto can be minimized by effectively inhibiting ultraviolet light blocking ability as well as active oxygen generated through photoreaction after UV absorption. Further, according to the present invention, it is possible to prevent direct contact with the inorganic microfine particle according to the present invention, which acts as an inorganic ultraviolet screening agent such as TiO ₂ , and to prevent the phenomenon that inorganic microfine particles are evenly applied to the surface of the porous core, So that the feeling of use thereof is greatly improved.

That is, the composite powder according to the present invention is a material of a multi-layer structure of organic-inorganic hybrid type in which an antioxidant and inorganic fine particles are alternately coated with a tacky coating on a porous core, and can be stably dispersed in a formulation to realize an enhanced ultraviolet shielding ability Of course, by effectively inhibiting the active oxygen generated by the photoreaction by the ultraviolet blocking, the ultraviolet blocking effect can be maximized.

As shown in the following reaction formula, an inorganic ultraviolet blocking agent such as TiO ₂ disposed at the outermost part of the composite powder absorbs ultraviolet rays to form electrons and holes (1). The hole may react with water to form a hydroxyl radical, which is active oxygen. (2) The electron may react with oxygen to form a superoxide radical, which is active oxygen.

Thus, the composite powder according to the present invention is excellent in radical scavenging ability for removing active oxygen derived from the above-mentioned reaction formula, and effectively prevents problems such as skin aging and tissue damage caused thereby. That is, according to the present invention, an anti-aging function as well as a high UV blocking effect can be additionally provided.

In addition, the conventional organic ultraviolet screening agents have a problem in that their activity is lowered due to the active oxygen generated from the inorganic ultraviolet screening agent as well as the troublesomeness required to be over time because of low light stability. However, according to the present invention, it is expected that effective oxygen scattering and blocking as well as active oxygen in a formulation are blocked, thereby solving the problems in using an organic UV screening agent and achieving remarkably improved synergy in ultraviolet screening ability .

The inorganic fine particles in accordance with one aspect of the present invention should not be limited if the inorganic UV filters used in the art, preferably from cerium oxide (CeO _2), iron oxide _{(Fe 2 O 3, Fe 3} O 4), zirconium oxide (ZrO ₂ ), Silica (SiO ₂ ), titanium dioxide (TiO ₂ ), iridium dioxide (IrO ₂ ) and zinc oxide (ZnO). In order to realize a further improved ultraviolet shielding ability, Zinc, and the like, but is not limited thereto.

At this time, the inorganic fine particles may have an average particle size of 1 to 100 nm. The form thereof is not limited, but may have various forms such as a spherical shape, a rod shape, a plate shape, and the like.

For example, when the inorganic fine particles have a rod shape, (Length ratio of long axis (L ¹ ) / short axis (L ² )) of the major axis and minor axis may be 2 or more, preferably 2 to 8, but is not limited thereto.

In another example, when the inorganic fine particles are in the form of a plate, the aspect ratio (ratio of particle diameter d / thickness t) may be 2 or more, preferably 2 to 40, but is not limited thereto. At this time, the particle size of the plate-like inorganic fine particles may be 2 to 100 mn and the thickness may be 1 to 20 nm, but is not limited thereto.

Hereinafter, a method for producing a composite powder according to an embodiment of the present invention will be described.

According to one aspect of the present invention, there is provided a composite powder comprising: forming an organic layer using an antioxidant in a porous core; And forming an inorganic layer using the inorganic fine particles in the organic layer.

The method for producing a composite powder according to the present invention is capable of easily adjusting the content of the inorganic fine particles with an accurate amount as well as introducing the antioxidant and the inorganic fine particles into the porous core with a strong adhesive force, The process time can be significantly shortened.

Also, the step of forming the coating layer including the organic layer produced by the above-mentioned method and the inorganic layer formed on the organic layer may be repeated one or more times to provide a coating layer having a multilayer structure. , Synergy can be imparted to the desired effect.

Specifically, a method for producing a composite powder according to an embodiment of the present invention includes: a first step of dissolving an antioxidant in a first solution, adding a porous core to prepare a dispersion, and stirring the antioxidant to form an organic layer coated with an antioxidant; Separating and washing the porous core in which the organic layer is formed by charging a second solution into the dispersion of the first stage; Adding a porous core and inorganic fine particles having the organic layer formed thereon to a first solution to prepare a dispersion liquid and stirring the inorganic liquid to form an inorganic layer coated with inorganic fine particles; And (4) separating and washing the porous core having the inorganic layer formed on one surface of the organic layer by injecting the second solution into the dispersion of the three steps.

In one embodiment, the organic layer formed by the above method may be prepared by combining two or more hydroxy groups contained in the antioxidant with the porous core, that is, the carbonyl group of the porous acrylic polymer microparticles through hydrogen bonding or the like to maintain the porosity of the porous acrylic polymer micropart Is formed on the surface. Further, the antioxidant contained in the organic layer forms a strong metal-ligand charge complex with the inorganic fine particles contained in the inorganic layer formed on one side of the organic layer, thereby forming strong bonds with the inorganic fine particles to the porous core Can be introduced into the surface of the substrate.

According to this effect, the composite powder according to the present invention can introduce the antioxidant and the inorganic fine particles into the surface of the porous core with strong adhesive force, and can be prepared by appropriately controlling the content of each component as desired.

In addition, in the method for producing a composite powder according to an embodiment of the present invention, when the organic-inorganic hybrid multilayer structure is formed by repeating the steps 1 to 4 twice or more, synergism is imparted to the desired effect In the present invention.

In the step 1, the dispersion is prepared by dissolving an antioxidant in a first solution and then adding a porous core in a solid phase to a solution prepared by dissolving the antioxidant in the first solution, It may be manufactured. At this time, it is needless to say that the order of introduction of the respective components does not affect the properties of the dispersion liquid and can be produced in various forms.

The first solution is not limited as long as it is a solvent capable of dissolving the antioxidant, preferably water (H ₂ O). In this case, the amount of the first solution is not limited, but preferably the volume ratio (w / v) of the organic solvent to the sum of the weight of the antioxidant and the porous core is 0.001 to 1 g / mL, Do not.

In the step 2, the second solution may include one or more selected from low-alcohol-based solvents having 1 to 4 carbon atoms, but is not limited thereto. At this time, the amount of the second solution to be used is not limited, but may be preferably 10 to 200 parts by volume based on the first solution 100.

In addition, in the second and fourth steps, the coated porous cores obtained in each step can be separated and washed by performing centrifugation in the range of 1000 g to 10,000 g after the second solution is introduced. In this way, the process time can be significantly shortened as compared with the inorganic fine particle coating using the conventional layered self-assembling method.

In addition, the method for producing a composite powder according to an embodiment of the present invention may further include a conventional washing step, a drying step, and the like after forming the coating layer including the organic layer and the inorganic layer.

As described above, it is needless to say that the weight ratio of the antioxidant and the inorganic fine particles and the thickness of the coating layer of the composite powder according to an embodiment of the present invention can be appropriately controlled.

For example, the coating layer may contain the antioxidant and the inorganic fine particles at a weight ratio of 0.1: 99.9 to 20: 80.

The thickness of the coating layer of the composite powder according to an embodiment of the present invention is not limited as long as it does not cause a foreign body or whitish phenomenon, and may be formed preferably in the range of 100 to 1,000 nm, more preferably 100 to 500 nm. The coating layer may be formed in a multi-layer structure in order to enhance the effect of the present invention.

For example, the organic and inorganic layers of the composite powder according to an embodiment of the present invention can be alternately laminated to different thicknesses or thicknesses, preferably from 10 to 100 nm, more preferably from 20 to 80 nm .

In one embodiment, it has been found that the composite powder prepared by repeating the step of forming the coating layer 4 times exhibits remarkably improved ultraviolet shielding ability and active oxygen inhibition ability as compared with the composite powder obtained by repeating this three times . However, in the case of repeatedly performing 5 or more times, it is preferable to perform the coating layer up to 4 times in the present invention, It goes without saying that it also belongs to an aspect of the present invention.

In one non-limiting embodiment, the porous core may be a porous acrylic polymer microparticle prepared by the following method.

The porous acrylic polymer microparticles may be prepared by (a) dissolving an acrylic polymer and a polymeric nonionic surfactant in an organic solvent; (b) injecting the mixed solution of step (a) into an aqueous solution containing a water-soluble polymer to emulsify the mixed solution; (c) heating the resultant of step (b) to evaporate the organic solvent; And (d) washing and drying the porous acrylic polymer particles settled after evaporation.

The mixed solution of the step (a) is introduced into the aqueous solution containing the water-soluble polymer in step (b), and then the polymeric nonionic surfactant having the property of being dissolved in water while being emulsified is moved into the aqueous solution, To form a porous structure on the acrylic polymer particles, and ultimately to produce porous acrylic polymer microspheres.

In the step (a), the amount of the acrylic polymer and the polymeric nonionic surfactant to be used is not limited, and preferably 7: 3, 6: 4, 5: 5, 4: 6.

The polymer type nonionic surfactant may be a block copolymer of polyalkylene oxide having different repeating units, and specifically may be a block copolymer of polyethylene oxide and polypropylene oxide. As a non-limiting example, the polymeric nonionic surfactant may be a block copolymer of the Pluronic family.

The organic solvent is not limited as long as it is a solvent capable of dissolving the acrylic polymer and the polymeric nonionic surfactant. Preferably, the organic solvent is at least one selected from methylene chloride, n-hexanone, methylisopropyl ketone, toluene, isoamyl alcohol, It can be used every day. At this time, the volume ratio (w / v) of the organic solvent to the total weight of the acrylic polymer and the polymeric nonionic surfactant is preferably 0.001 to 1 g / mL, but is not limited thereto.

In the step (b), the water-soluble polymer is not limited as long as it is capable of emulsifying the mixed solution of step (a), preferably polyvinyl alcohol, poly (vinyl alcohol-vinyl acetate) copolymer, polyacrylic acid, poly Acrylate-acrylic acid) copolymer, hydroxypropyl cellulose, polyvinyl pyrrolidone, polyvinyl methyl ether, polyethyleneimine and the like.

The amount of the water-soluble polymer to be used is not limited, and preferably 0.01 to 10% by weight based on water (H ₂ O).

In the step (b), the stirring conditions of the emulsion are not limited, but it is preferable to stir at 1,000 to 10,000 rpm in order to realize the desired average diameter.

As described above, the composite powder according to the present invention is excellent in feeling of use, ultraviolet shielding effect, and excellent ability to inhibit active oxygen, so that it can be used in various aspects for ultraviolet shielding. Hereinafter, the cosmetic composition using the composite powder according to the present invention will be described, but its use is not limited thereto.

The present invention provides a cosmetic composition for UV screening comprising the above composite powder.

The cosmetic composition according to an embodiment of the present invention employs a composite powder including a coating layer having a plurality of layers such as an organic layer and an inorganic layer, thereby effectively improving skin irritation and various side effects resulting from the photoreaction, And an excellent effect in inhibiting aging.

Further, the cosmetic composition according to one embodiment of the present invention is excellent in sebum adsorption power with a high specific surface area, and can provide excellent effects to cosmetics for controlling sebum due to sebum control and soft focus effect due to irregular reflection of light have.

Furthermore, the cosmetic composition according to an embodiment of the present invention lowers the absorption of light in the visible light region by the diffused reflection effect of light to minimize the whitening phenomenon which is a problem of inorganic fine particles such as TiO ₂ , So that it is possible to effectively suppress the entanglement between the inorganic fine particles and to realize the enhanced ultraviolet shielding ability.

The cosmetic composition according to an embodiment of the present invention is excellent in blocking effect of UVA region as well as UVB, excellent in the ability to inhibit active oxygen induced by photoreaction, and provides sufficient stability for use as a cosmetic composition.

In the cosmetic composition according to an embodiment of the present invention, the amount of the composite powder to be used is not limited, and may be, for example, 0.1 to 20% by weight based on the total weight of the composition. In this case, it may be included in the range of 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, in view of imparting superior ultraviolet shielding ability, but is not limited thereto.

The cosmetic composition may be prepared in various forms conventionally prepared in the art. For example, it may be formulated into a solution, a suspension, an emulsion, a paste, a gel, a cream, a lotion, a powder or the like, and preferably a suspension, an emulsion, a cream, a lotion or a powder.

For example, the cosmetic composition according to the present invention may further include an ultraviolet screening agent, and the ultraviolet screening agent may be an organic ultraviolet screening agent. The organic ultraviolet screening agent may be selected from a benzoyl compound, a benzoate compound, a benzophenone compound, a triazine compound, a cinnamate compound, a salicylate compound, a sulfate compound and a cyanate compound. As a non-limiting example, the organic sunscreen agents include diethylaminohydroxybenzoylhexylbenzoate, homosalate, ethylhexylsalicylate, phenylbenzimidazolesulfonic acid, octocrylene, ethylhexylmethoxycinnamate , Ethylhexyl palmitate, butylmethoxydibenzoylmethane, 4-methylbenzylidene camphor, isoamyl-p-methoxy cinnamate, and bis-ethylhexyloxyphenol methoxyphenyltriazine. The amount of the ultraviolet screening agent to be used is not particularly limited, but it may be 1 to 25% by weight, preferably 5 to 20% by weight, based on the total weight of the composition.

The cosmetic composition of the present invention may contain, within the range of not lowering the formulation stability and skin safety, a surfactant, an antioxidant, a stabilizer, a pH adjuster, a preservative, a bactericide, A perfume or a pearl agent, and the like.

The present invention provides a multilayer film in which antioxidants and inorganic fine particles having alternate forms from the above-mentioned composite powder are alternately laminated.

The multilayer film according to an embodiment of the present invention may be formed on the surface of the porous support, and the porous support may be a porous core as described above, that is, a porous organic polymer particle or the like.

The present invention also provides a method for removing active oxygen using the above-described composite powder or multilayer film. The method of removing active oxygen according to the present invention is as shown in the above reaction formula and the following FIG.

In the method for removing active oxygen according to an embodiment of the present invention, the active oxygen is not limited. For example, a hydroxy radical, a peroxy radical, and a superoxide radical.

The mechanism for the removal of active oxygen according to one embodiment of the present invention is as follows. The catechol or galloyl group contained in the antioxidant may be a hydroxyl radical, a peroxy radical, a superoxide radical, or the like through H atom transfer or single electron transfer And the radicals formed in the catechol or galloyl group can be removed by stabilizing through intra-molecular hydrogen bonding with the hydroxy groups contained in the catechol or gallyl group .

In one embodiment, the method of removing the active oxygen according to the present invention are superoxide ^radicals-may be a method of removing (O ₂ ·).

The concentration of the superoxide radical before / after the UV irradiation can be measured through nitroblue tetrazolium analysis. At this time, the concentration of the superoxide radical formed by the UV irradiation and the concentration of the superoxide radical removed by the composite powder or the multilayer film according to the present invention after the UV irradiation were measured by measuring the absorption (680 nm) of the formazan formed by the superoxide radical So that the concentration of the anion can be quantified.

In one embodiment, the method for removing active oxygen according to the present invention may be a method for removing a hydroxy radical (HO).

The concentration of the hydroxy radical before / after the UV irradiation can be measured through terephthalic acid analysis. At this time, the concentration of the hydroxy radical formed by the UV irradiation and the concentration of the hydroxy radical removed by the composite powder or the multi-layer film after the UV irradiation according to the present invention are increased by the fluorescence increased when the terephthalic acid and the hydroxy radical are chemically bonded 430 nm) can be measured and quantified.

Thus, according to the present invention, ultraviolet shielding ability is remarkably superior to that of conventional inorganic ultraviolet screening agents, and effective inhibition and removal of active oxygen generated from these ultraviolet screening agents can prevent skin aging, tissue damage It is expected that the functional materials and functional coating methods that can solve various side effects of the coatings can be applied to various industries.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto in any sense.

Unless otherwise stated herein, all temperatures are in degrees Celsius. Also, unless otherwise stated herein, the temperature is carried out at 20 DEG C and at atmospheric pressure (1 atm).

(Assessment Methods)

1. Evaluation of physical properties of composite powder

The morphology of the composite powder prepared in the following examples and the powder prepared in the comparative examples was measured by a scanning electron microscope (SEM, S-4800, Hitachi), and the particle size (D ₅₀ ) Scanning electron microscopic photographs confirmed more than 100 microspheres directly measured.

Also, their specific surface areas were measured using a BET analyzer (AUTOSORB-1, Quantachrome).

Their optical properties were measured by a UV-Vis spectrometer (UV-1800, Shimadzu), and the amount of tannic acid coated on the porous PMMA microparticles was determined using the absorption spectrum of the tannic acid solution before and after coating with tannic acid. At this time, the decrease of the concentration of the tannic acid solution after the tannic acid coating decreases the absorption of the UV region by the tannic acid than before the coating.

After coating TiO ₂ nanoparticles with the naked eye, the color of the porous PMMA microparticles showed yellow color as titanium and tannic acid form metal-ligand exchange complexes. From the scanning electron microscopic photographs, it was confirmed that the TiO ₂ nanoparticles The appearance and appearance of the TiO ₂ nanoparticles according to the number of coatings of the TiO ₂ nanoparticles were confirmed.

The amount of TiO ₂ nanoparticle inorganic fine particles in the powder was analyzed by thermogravimetry analysis (TGA, TG 209 F3, Netzsch).

The properties of the composite powder were evaluated by the above-described method, and the results are shown in Table 1, Fig. 2 and Fig.

2. Evaluation of active oxygen inhibition ability of composite powder

Superoxide radical (O ₂ · ^-) over the concentration measured with the hydroxyl radical (· OH) was evaluated for inhibitory ability of the radicals formed by the TiO _2.

At this time, the concentration of the superoxide radical was measured by nitroblue tetrazolium analysis, and the concentration of the anion was quantitatively analyzed by measuring the absorption (680 nm) of the formazan formed by the superoxide radical. Potassium peroxide (Sigma-Aldrich) was used to draw the calibration curve of the superoxide radical. To prepare the superoxide radicals, 28.2 mg of potassium peroxide and 105.8 mg of 18-crown-6 (Sigma-Aldrich) were dissolved in 2 mL of deionized water with air removed at room temperature for 4 hours. After stirring, And centrifuged at 13,500 rpm. The supernatant of the centrifuged aqueous solution contained a superoxide radical, which was serially diluted to 1/2, 1/4 and 1/8 concentrations. 140 ㎕ of superoxide radical solution was reacted with 140 ㎕ of 1 mg mL ^-1 NBT aqueous solution at room temperature for 10 minutes. The absorbance of the reacted aqueous solution was measured with a microplate reader (CLARIO star, BMG Labtech, Ortenberg, Germany) in the range of 220-800 nm. The composite powder dispersion 500 ㎕ align the concentration of 0.3 mg mL ^-1 of the TiO ₂ in 5 mL vial 1 mg mL ^-1 solution NBT 500 ㎕ and mixed, and exposed for 20 minutes to 8 W UV lamp. The aqueous solution exposed to UV was centrifuged at 12,000 rpm for 5 minutes. After removing the supernatant, 540 μl of dimethylsulfoxide and 460 μl of 2 M potassium hydroxide were added to dissolve the formazan. After centrifugation at 12,000 rpm for another 5 min, the supernatant was measured for absorbance with a microplate reader at 220-800 nm.

The concentration of hydroxy radicals was measured by terephthalic acid analysis and the concentration of hydroxy radicals was quantitatively analyzed by fluorescence measurement when terephthalic acid was chemically bound to the hydroxy radical. Terephthalic acid was dissolved in 2 mM sodium hydroxide, and 500 μl of a composite powder dispersion having a concentration of 0.3 mg mL ^-1 in a 5 mL vial mixed with TiO ₂ was mixed with a 1 mM terephthalic acid aqueous solution. Exposed. The fluorescence intensity of the UV-irradiated aqueous solution was measured with a microplate reader. The measured excitation wavelength was 320 nm and the emission wavelength range was 350-600 nm. A calibration curve was drawn with purified 2-hydroxyterephthalic acid for quantification of the hydroxy radicals.

The results are shown in Figs. 5 to 6 and Figs. 8 to 9 below.

3. Formulation Evaluation

The O / W sunscreen was prepared using the composite powders prepared in the following examples and the powder prepared in the comparative examples, and one embodiment is shown in Table 3 below.

SPF clinical trials were conducted in vitro for each O / W sunscreen. Each O / W sunscreen was coated on a sandblasted PMMA plate of 47 mm × 47 mm × 1.5 mm with 1.2 mg cm ^{- 2} , irradiated with ultraviolet light, and measured with UV Transmittance Analyzer 5 times using Labsphere 's UV Transmittance Analyzer. At this time, the higher the SPF and PA values, the higher the UV blocking power (the SPF of O / W sunscreen is 31.1).

In order to evaluate the spreading, absorbency, softness and whiteness of each O / W sunscreen, 19 panelists (20-19years old) were subjected to a sensory evaluation (0-100 points) , And the mean value of 90 points or more is excellent, 80-89 points are excellent, 70-79 points are excellent, 60-69 points are normal, and less than 60 points are poor.

The results are shown in Table 2 and Figs. 3 to 4 below.

In the evaluation of skin stability for each O / W sunscreen, mouse skin was irradiated for 1 minute in ultraviolet UVB region (320 - 290 nm) and skin was collected 3 days later and H & E staining (hematoxylin and eosin stainning) Respectively.

The results are shown in FIG.

(Example 1)

Step 1.

600 mL of a 0.5% (w / v) polyvinyl alcohol (PVA, 88% hydrolyzed, weight average 146,000 ~ 186,000) solution was prepared. 200 mg of polymethyl methacrylate (PMMA, molecular weight 50,000) and 200 mg of Pluronic F-127 were placed in a 20 mL beaker and 4 mL of methylene chloride (MC) Respectively. Then, the lid of the 20 mL beaker was closed, sealed with Teflon tape, and completely dissolved by stirring. The solution was put into a 0.5% (w / v) PVA solution that had been prepared in advance, and emulsified at 5000 rpm for 10 minutes using a homogenizer (high-speed stirrer). The emulsion was placed in a beaker or a crystalizing dish, immediately transferred to a fume hood, stirred at 300 rpm or more for 3 hours at 37 ° C, and the organic solvent was evaporated. The emulsion was precipitated by centrifugation at 1,000 g for 20 minutes. After removing the supernatant, 10 mL of distilled water was added to redisperse the supernatant, and the supernatant was added to a 50 mL tube. After centrifugation, 10 mL of distilled water was added again to remove the remaining pluronic from the supernatant-removed tube, and the supernatant was washed and placed in the same 50 mL tube. And centrifuged at 1,000 g for 10 min. The supernatant was removed and redispersed and washed again with 50 mL of distilled water. The washing process was repeated twice. The PMMA microparticles (weight average molecular weight: 50,000) were obtained by completely removing moisture through freeze-drying.

Step 2.

200 mg of the porous PMMA microparticles (weight average molecular weight: 50,000) obtained in the above step 1 were dispersed in 38 ml of distilled water. 20 mg of tannic acid (Sigma-Aldrich No. 403040) was dissolved in 2 ml of distilled water, and the mixture was put into a prepared porous PMMA microparticle dispersion. The mixture was stirred for 5 minutes using a vortex mixer. 20 ml of ethanol was added to the reaction solution, followed by centrifugation at 1,000 g for 5 minutes. After removing the supernatant, 20 ml of distilled water and 10 ml of ethanol were mixed and re-dispersed in a 50 ml tube and centrifuged at 1,000 g for 5 minutes. In order to remove tannic acid remaining after centrifugation, a step of re-dispersing and centrifuging the solution mixed with distilled water and ethanol was repeated twice and dried to obtain PMMA / TA (yield:> 90 %).

Step 3.

The tannic acid-coated porous PMMA microparticles (PMMA / TA) obtained in the step 2 were dispersed in 20 ml of distilled water. 20 mg of TiO2 nanoparticles dispersed in 20 ml of distilled water was added to a dispersion in which porous tannic acid-coated PMMA microparticles were dispersed, and the mixture was stirred for 3 hours using a magnetic stirrer. Then, 20 ml of ethanol was added to the reaction solution, followed by centrifugation at 1,000 g for 5 minutes. After removing the supernatant, 20 ml of distilled water and 10 ml of ethanol were mixed and re-dispersed in a 50 ml tube and centrifuged at 1,000 g for 5 minutes. After the centrifugation, the solution containing the mixture of distilled water and ethanol was added to redisperse and centrifuged twice and dried to obtain PMMA / TA / TiO ₂ (yield:> 90%).

The composite powder obtained by the above method was used to carry out a related evaluation with the above evaluation method.

(Example 2)

Step 2 and Step 3 of Example 1 were repeated twice (yield: > 90%).

The composite powder obtained by the above method was used to carry out a related evaluation with the above evaluation method.

(Example 3)

Step 2 and Step 3 of Example 1 were repeated three times (yield: > 90%).

The composite powder obtained by the above method was used to carry out a related evaluation with the above evaluation method.

 (Example 4)

Step 2 and Step 3 of Example 1 were repeated four times (yield: > 90%).

The composite powder obtained by the above method was used to carry out a related evaluation with the above evaluation method.

(Example 5)

100 mg of the porous PMMA microparticles (weight average molecular weight: 50,000) obtained in the step 1 of Example 1 were dispersed in 10 mL of ethanol and dispersed for 1 hour using a shaking incubator. The solution was precipitated by centrifugation at 900 g for 10 minutes and then the supernatant was removed. Then, 20 mg of polydodamine dissolved in 10 mL of distilled water was added. To the reaction, 0.2 mL of 0.1 M sodium hydroxide solution was added, and the mixture was stirred at 37 ^° C for 1 hour using a magazine incubator. The reaction solution was centrifuged at 900 g for 10 minutes. After removing the supernatant, 10 mL of distilled water was added to remove residual polydopamine and sodium hydroxide, followed by redispersion and centrifugation three times and dried to obtain PMMA / pD.

PMMA / pD / TiO ₂ (yield: > 90%) was obtained by performing Step 3 of Example 1 once using the porous PMMA microparticles (PMMA / pD) coated with the obtained polydodamine.

(Example 6)

100 mg of the porous PMMA microparticles (weight average molecular weight: 50,000) obtained in the step 1 of Example 1 were dispersed in 9 mL of distilled water. 100 mg of ascorbic acid was dissolved in 1 mL of distilled water, and the mixture was added to the prepared porous PMMA microparticle dispersion. The mixture was stirred for 24 hours using a shaking incubator. The reaction solution was centrifuged at 900 g for 10 minutes. Thereafter, to remove residual ascorbic acid after removing the supernatant, 10 mL of distilled water was added to redisperse and centrifuged twice, and dried to obtain PMMA / AA.

Step 3 of Example 1 was performed once using porous PMMA microparticles (PMMA / AA) coated with the obtained ascorbic acid to obtain PMMA / AA / TiO ₂ (yield:> 90%).

(Comparative Example 1)

A non-treated PMMA powder (weight average molecular weight: 50,000) was used to carry out the related evaluation by the above evaluation method.

(Comparative Example 2)

A non-treated porous PMMA microparticle (weight average molecular weight: 50,000) was used to carry out a related evaluation using the evaluation method described above.

(Comparative Example 3)

Untreated TiO ₂ nanoparticles were used to carry out the related evaluation by the above evaluation method.

(Comparative Example 4)

Step 1 and Step 2 of Example 1 were carried out to obtain PMMA / TA powder (yield: > 90%).

The composite powder obtained by the above method was used to carry out a related evaluation with the above evaluation method.

(Comparative Example 5)

200 mg of porous PMMA microparticles (weight average molecular weight: 50,000) were dispersed in 20 ml of distilled water. 20 mg of TiO ₂ nanoparticles dispersed in 20 ml of distilled water was added to the dispersion in which the porous PMMA microparticles were dispersed, and the mixture was stirred for 3 hours using a magnetic stirrer. Then, 20 ml of ethanol was added to the reaction solution, followed by centrifugation at 1,000 g for 5 minutes. After removing the supernatant, 20 ml of distilled water and 10 ml of ethanol were mixed and re-dispersed in a 50 ml tube and centrifuged at 1,000 g for 5 minutes. After the centrifugation, a solution obtained by mixing distilled water and ethanol was added and redispersion and centrifugation were repeated twice and dried to obtain PMMA / TiO2 powder (yield:> 75%).

The composite powder obtained by the above method was used to carry out a related evaluation with the above evaluation method.

As shown in Table 1, the specific surface area of the composite powder according to the present invention increased significantly as the TiO ₂ fine particle coating layer was formed. This can be attributed to the mesopores formed by TiO ₂ particles. Further, it can be confirmed that the composite powder according to the present invention can impart remarkably improved tackiness by introducing an antioxidant between the porous core and the inorganic fine particles.

In addition, it was found that the absorbance increased remarkably by the combination of, as well as increase in absorbance by the TiO2 nanoparticles tannic acid and TiO ₂ nano-particles, as a result, the number of coating is increased, make the ultraviolet absorbance difference in the number of coatings.

However, the powder according to Comparative Examples 4 and 5 showed insignificant increase in absorbance. This is interpreted in accordance with the TiO ₂ does not coat evenly distributed and the member or core of porous TiO _2. In particular, in the case of Comparative Example 5, TiO ₂ showed a low adhesion to the porous core, indicating that the introduction amount of TiO ₂ was low.

In the case of Example 4 according to the present invention, the porous PMMA microparticles prepared by four times of coating of tannic acid coating and TiO ₂ nanoparticles through TGA analysis were subjected to TiO ₂ Analysis of the mass ratio of the nanoparticles, the nano-TiO ₂ particles were able to confirm that accounts for about 30% of the total mass, which is a TiO ₂ In It can be seen that most of the nanoparticles are coated on the porous PMMA microspheres.

In addition, in the case of Example 4 according to the present invention, it was confirmed that the specific surface area was improved as compared with Example 3, and thus the absorbance against ultraviolet light was remarkably improved. Thus, the composite powder according to the present invention exhibits remarkably improved SPF boosting effect as compared to untreated PMMA powder (Comparative Example 1), untreated porous PMMA microparticles (Comparative Example 2) and untreated TiO ₂ (Comparative Example 3) (See FIG. 4). Particularly, in the case of the composite powder according to the present invention as compared to the untreated TiO ₂ (Comparative Example 3), the secondary aggregation phenomenon of TiO ₂ is effectively suppressed and uniformly dispersed, which is remarkable in its effect.

Also, as shown in FIG. 1, the composite powder according to the present invention can remove active oxygen generated from a photoreaction, and its effect is shown in FIGS. 5 to 6 and FIGS. 8 to 9.

The results shown in FIG. 5 or 8 show that the activity of the composite powder (PMMA / TA / TiO ₂ , PMMA / pD / TiO ₂ and PMMA / AA / TiO ₂ ) Was measured by nitroblue tetrazolium analysis.

As a result of measurement of the absorption (680 nm) of the formazan formed by the superoxide radical using the composite powder according to the present invention, that is, Examples 4 to 6, it was confirmed that it was greatly suppressed to about 50% level compared to TiO ₂ .

The results shown in FIG. 6 or 9 were obtained by confirming the inhibitory activity of hydroxy radicals, another active oxygen species of the composite powder according to the present invention, by analyzing fluorescence when hydroxy radicals and terephthalic acid are chemically bonded.

Composite powder according to the present invention, i.e., Examples 4 to 6 using the result of measuring the inhibitory ability of the hydroxy radical, in the case of Example 4, the hydroxyl radical production is the comparative example 3 (TiO ₂₎ compared to up to about 3% (See Fig. 6). In addition, in Example 5 and Example 6, it was confirmed that the amount of hydroxy radicals produced was about 0.1% and about 0.6%, respectively, compared with Comparative Example 3 (TiO ₂ ) (see FIG. 9).

The results shown in FIG. 10 are the result of confirming the protection ability against ultraviolet rays using H & E staining (hematoxylin and eosin staining) of mouse skin as a skin stability evaluation of sunscreen containing the composite powder according to the present invention.

(Yellow arrow) and inflammation in the dermis (black arrow) were observed in the case of treating the sunscreen containing TiO ₂ (Comparative Example 3), while the sun cream containing the composite powder according to the present invention was treated (Example 4), this phenomenon did not appear and ultraviolet rays were effectively blocked, and excellent skin safety as a cosmetic raw material was confirmed.

That is, the composite powder according to the present invention has a remarkably excellent ability to inhibit active oxygen, effectively inhibiting active oxygen generated through photoreaction after UV absorption, and thus can solve various side effects such as skin aging and tissue damage caused by active oxygen I expect to be there.

As shown in Table 2, it was confirmed that the sunscreen containing the composite powder according to the present invention had an ultraviolet shielding effect of SPF 50 or more and a maximum of 161% higher than SPF of O / W sunscreen, which is a non-additive group.

Further, as a result of sensory evaluation such as feelings of use as cosmetics for each O / W sunscreen, the sunscreen manufactured according to Example 4 showed no difference or better evaluation in spreadability, absorbency and softness, and whiteness It can be confirmed that it is remarkably improved as compared with the case of using untreated TiO ₂ . Therefore, it can be confirmed that the present invention provides a technique capable of effectively improving the SPF and maintaining the wettability, the absorbency and the softness while suppressing the whitish phenomenon.

In summary, according to the present invention, it is possible to improve the transparency by improving the whitening phenomenon by the light scattering effect derived from the morphology of the composite powder in the form of a multilayered film, and to form a uniform and thin film with a smooth spreadability, Blocking effect can be provided at the same time.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the technical scope of the present invention is not limited to the disclosed exemplary embodiments. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (18)

Porous cores; And
And a coating layer formed on the surface of the porous core, wherein the coating layer is formed by alternately laminating an inorganic layer including an organic layer containing an antioxidant and inorganic fine particles. The method according to claim 1,
Wherein the porous core is a porous organic polymer particle. 3. The method of claim 2,
Wherein the porous core has an average pore diameter of 1 to 500 nm. The method according to claim 1,
Wherein the antioxidant is selected from a polyphenolic compound and a phenol compound. The method according to claim 1,
Wherein the inorganic fine particles are spherical, rod-like or plate-like. 6. The method of claim 5,
Wherein the inorganic fine particles are selected from cerium oxide, iron oxide, zirconium oxide, silica, titanium dioxide, iridium dioxide and zinc oxide. The method according to claim 1,
Wherein the weight ratio of the antioxidant to the inorganic fine particles in the coating layer is 0.1: 99.9 to 20: 80. The method according to claim 1,
Wherein the coating layer has a multilayer structure in which the organic layer and the inorganic layer are alternately laminated in two or more layers. The method according to claim 1,
Wherein the thickness of the coating layer is 100 to 1,000 nm. The method according to claim 1,
Wherein the thickness of the organic layer and the inorganic layer is 10 to 100 nm. A cosmetic composition comprising the ultraviolet shielding composite powder according to claim 1. Antioxidant and inorganic fine particles alternately laminated. 13. The method of claim 12,
Wherein the multilayered film is formed on the surface of the porous support. 14. The method of claim 13,
Wherein the porous support is a porous organic polymer particle. 13. The method of claim 12,
Wherein the antioxidant is selected from a polyphenolic compound and a phenolic compound. 13. The method of claim 12,
Wherein the inorganic fine particles are selected from cerium oxide, iron oxide, zirconium oxide, silica, titanium dioxide, iridium dioxide, and zinc oxide. A method for removing active oxygen using the multilayer film according to claim 12. 18. The method of claim 17,
Wherein the active oxygen is selected from a hydroxy radical, a peroxy radical, and a superoxide radical.

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