KR102269990B1 - Uv blocking composite structure and method of preparing the same - Google Patents

Abstract

Disclosed are a composite structure for blocking UV rays including a porous silica structure and a method for manufacturing the composite structure for blocking UV rays. The UV-blocking composite structure includes a porous silica structure, so that when used as a UV-blocking agent, the feeling of use can be improved, the cloudiness phenomenon can be solved, and particles with improved dispersion stability can be provided by greatly reducing the specific gravity due to the porous structure. have. In addition, since it does not contain a separate polymer, it is possible to avoid the microplastic issue, which has recently become a problem.
In addition, in the composite structure, scattering occurs due to silica to increase absorption of ultraviolet and visible light, and since the silica surrounds the metal oxide nanoparticles, active oxygen caused by the photoreaction between the metal oxide nanoparticles and the ultraviolet rays It has an inhibitory effect and can prevent direct contact between the metal oxide nanoparticles and the skin.

Description

Composite structure for UV blocking and manufacturing method thereof {UV BLOCKING COMPOSITE STRUCTURE AND METHOD OF PREPARING THE SAME}

The present invention relates to a composite structure for blocking ultraviolet rays including a porous silica structure and a method for manufacturing the composite structure for blocking ultraviolet rays.

Ultraviolet light is a light having a shorter wavelength than visible light, and has a wavelength range of 10 to 400 nm as a region invisible to the human eye. Although the permeability is lower than general X-rays or gamma rays, it has higher energy than visible or infrared rays, so it causes sunburn, pigmentation, and photoaging of human skin. also cause

The ultraviolet rays are classified into short wave 　 ultraviolet rays (UVC; 200-280 nm), medium wave 　 ultraviolet rays (UVB; 290-300 nm), and long wave 　 ultraviolet rays (UVA; 320-400 nm) according to their wavelength, and the shortest wavelength among them is Most of the high-energy short-wave 　 ultraviolet rays are absorbed by the ozone layer and are lost without reaching the surface. However, the medium wave 　 ultraviolet rays are known as rays that can cause skin cancer by penetrating to the basal layer of the epidermis and the upper dermis and causing sunburns such as erythema and edema and pigmentation such as freckles. It is known as an aging light that causes photoaging by reaching the dermis layer of the skin with light and reducing the elasticity of the skin to promote wrinkle formation. As described above, in order to protect the skin from UV rays that cause various skin damage, the need for UV blocking agents has been recognized for a long time, and as a result, various types of UV blocking products have been released.

Conventional sunscreens are divided into organic sunscreens and inorganic sunscreens according to the mechanism of protecting the skin from ultraviolet rays.

The organic sunscreen absorbs ultraviolet rays and converts them into heat through a chemical reaction to emit them. Representative examples of these include ethylhexylmethoxycinnamate, ethylhexylsalicylate, octocrylene, butylmethoxydibenzoyl Methane, bis-ethylhexyloxyphenol methoxyphenyltriazine, diethylaminohydroxybenzoylhexylbenzoate, etc. are mentioned. However, the use of these organic sunscreens is limited as it is known that they can be absorbed into the skin and cause problems such as skin irritation and skin toxicity.

On the other hand, the inorganic sunscreen has a mechanism of blocking UV rays from penetrating into the skin by reflecting and scattering UV rays, and typical examples thereof include titanium dioxide and zinc oxide. However, these inorganic 　 ultraviolet ray blocking agents are difficult to disperse and dissolve in the formulation, and when applied to the skin, may show a clouding phenomenon or cause a poor feeling of use (eg, foreign body feeling), and have high polarity and high specific gravity and thus easily aggregate in cosmetic formulations. It has a problem of sedimentation.

Currently, in order to overcome the shortcomings of these 　 UV blocking agents, various studies are being attempted.

As one of these studies, there is an inorganic blocking agent made as small as a nano level, but the inorganic blocking agent also adheres to the skin or penetrates the stratum corneum to generate reactive oxygen species (ROS), causing problems such as skin irritation and skin toxicity. There is controversy about the harmfulness of the use of inorganic blocking agents with a nanoscale size because it is highly likely to cause

Therefore, there is an urgent need in the market for an excellent UV blocker that does not cause white turbidity while still maintaining high safety and excellent UV blocking effect.

Accordingly, the present inventors have tried to solve the problems of conventional UV blocking agents, especially inorganic UV blocking agents. As a result, when metal oxide nanoparticles are placed in a porous silica structure, not only the above configuration but also the UV blocking effect, as well as the light between the inorganic UV blocking agent and UV light The present invention was completed by confirming that it provides a remarkable effect on the inhibitory ability of active oxygen induced from the reaction. In addition, the invention is expected to be a very meaningful invention since it does not include a separate polymer, and thus the microplastic issue, which has become a problem recently, can also be avoided.

In this regard, Korean Patent Registration No. 10-1806847 discloses a titanium dioxide-alpha-bisabolol complex having ultraviolet blocking and whitening effects, a method for preparing the same, and a use thereof.

The present invention has been devised to solve the above-described problem, and an embodiment of the present invention provides a composite structure for blocking ultraviolet rays including a porous silica structure.

In addition, another embodiment of the present invention provides a sunscreen composition comprising the composite structure for blocking ultraviolet rays.

In addition, another embodiment of the present invention provides a method of manufacturing a composite structure for blocking ultraviolet rays using a porous polymer structure.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.

As a technical means for achieving the above-described technical problem, an aspect of the present invention is

porous silica structure; and a plurality of metal oxide nanoparticles located inside or on the surface of the structure, wherein silica forming the structure surrounds the nanoparticles.

The composite structure for blocking ultraviolet rays may be characterized in that it does not include a separate polymer.

The metal oxide nanoparticles are titanium dioxide (TiO ₂ ), cerium oxide (CeO ₂ ), zirconium dioxide (ZrO ₂ ), iron oxide (Fe ₂ O ₃ ), iridium dioxide (IrO ₂ ), zinc oxide (ZnO) and their It may include a material selected from the group consisting of combinations.

The size of the UV-blocking composite structure may be 3 μm to 15 μm.

The shape of the composite structure for blocking ultraviolet rays may be characterized in that it is spherical, oval, rod-shaped or plate-shaped.

The porosity of the porous silica structure may be characterized in that 30 vol% to 70 vol%.

The specific surface area of the porous silica structure may be 1 m ² /g to 500 m ² /g.

The porous silica structure may have an average pore diameter of 1 nm to 500 nm.

The metal oxide nanoparticles may have a size of 1 nm to 100 nm.

The content of the porous silica structure may be 100 parts by weight to 1000 parts by weight based on 100 parts by weight of the metal oxide nanoparticles.

The composite structure for blocking ultraviolet rays may be characterized in that it has an active oxygen removal ability.

The active oxygen may be a hydroxy radical, a peroxy radical or a superoxide radical.

In addition, another aspect of the present invention,

It provides a sunscreen composition comprising the composite structure for blocking ultraviolet rays.

In addition, another aspect of the present invention,

coating the porous polymer structure with an antioxidant; coating the metal oxide nanoparticles on the porous polymer structure coated with the antioxidant; coating silica on the porous polymer structure by adding a silica precursor to the porous polymer structure coated with the metal oxide nanoparticles; and heat-treating the silica-coated porous polymer structure to remove the porous polymer structure and the antioxidant.

The porous polymer structure is an acryl-based polymer, a vinyl-based polymer, an epoxy-based polymer, a polyolefin-based polymer, a polyurethane-based polymer, a polyamide-based polymer, a polyester-based polymer, a polyimide-based polymer, a polycarbonate-based polymer, a polyether-based polymer, and a polysiloxane-based polymer. It may include a material selected from the group consisting of polymers, fluorine-based polymers, polysaccharide polymers, and combinations thereof.

The antioxidant may be a polyphenol-based compound or a phenol-based compound.

The heat treatment may be performed at 700° C. to 1,200° C. for 10 minutes to 60 minutes.

The manufacturing method of the composite structure for blocking ultraviolet rays comprises the steps of coating metal oxide nanoparticles on the porous polymer structure coated with the antioxidant; Thereafter, the step of further coating the antioxidant on the porous polymer structure coated with the metal oxide nanoparticles; may further include.

According to an embodiment of the present invention, the composite structure for UV blocking includes a porous silica structure, so that when used as a UV blocking agent, the feeling of use can be improved, the cloudiness phenomenon can be solved, and the dispersion is improved by greatly reducing the specific gravity due to the porous structure It is possible to provide particles with stability. In addition, since it does not contain a separate polymer, it is possible to avoid the microplastic issue, which has recently become a problem.

In addition, in the composite structure, scattering occurs due to silica to increase absorption of ultraviolet and visible light, and since the silica surrounds the metal oxide nanoparticles, active oxygen caused by the photoreaction between the metal oxide nanoparticles and the ultraviolet rays It has an inhibitory effect and can prevent direct contact between the metal oxide nanoparticles and the skin.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic view showing a manufacturing process of a composite structure for blocking ultraviolet rays according to an embodiment of the present invention.
2 is an SEM photograph showing each structure generated during the manufacturing process in manufacturing the composite structure for UV blocking according to an embodiment of the present invention.
3 is a graph showing a result of measuring the absorbance of a structure according to an experimental example of the present invention.
4 is a graph showing a thermogravimetric analysis result of a structure according to an experimental example of the present invention.
5 is a graph showing the result of measuring the fluorescence intensity of the structure according to an experimental example of the present invention.
6 is a graph showing the hydroxyl radical concentration of a structure according to an experimental example of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention may be embodied in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' any component means that other components may be further included, rather than excluding other components, unless otherwise stated.

The first aspect of the present application is

porous silica structure; and a plurality of metal oxide nanoparticles located inside or on the surface of the structure, wherein silica forming the structure surrounds the nanoparticles.

Hereinafter, the UV-blocking composite structure according to the first aspect of the present application will be described in detail.

In one embodiment of the present application, the composite structure for blocking ultraviolet rays may include only a porous silica structure and metal oxide nanoparticles, and may not include a separate polymer. Therefore, there is an effect of avoiding the microplastic issue, which has recently been a problem when manufacturing a sunscreen composition using the composite structure. On the other hand, the composite structure for blocking ultraviolet rays may include a plurality of metal oxide nanoparticles located inside or on the surface of the porous silica structure, and the silica forming the structure may be characterized in that it surrounds the nanoparticles. . In this case, when the silica surrounds the nanoparticles, it may mean that they are coated, and it is preferable that the silica surrounds the entire nanoparticles, but does not exclude a form surrounding a part.

In one embodiment of the present application, the porous silica structure may have a characteristic of scattering light because it has a porous shape. Therefore, the UV scattering properties of the porous silica structure and the UV blocking effect of a plurality of metal oxide nanoparticles located inside or on the surface of the structure may be combined to block a wider range of UV rays. In addition, the composite structure for UV blocking may improve dispersibility in the formulation with a low specific gravity, and may minimize the cloudiness phenomenon due to the light scattering effect induced in the morphology of the porous silica structure.

In one embodiment of the present application, the metal oxide nanoparticles may be metal oxide nanoparticles having UV blocking properties, for example, titanium dioxide (TiO ₂ ), cerium oxide (CeO ₂ ), zirconium dioxide (ZrO _{2 )} ), iron oxide (Fe ₂ O ₃ ), iridium dioxide (IrO ₂ ), zinc oxide (ZnO) and a material selected from the group consisting of combinations thereof, preferably the metal oxide nanoparticles are titanium It may be a dioxide (TiO _{2 ).}

In one embodiment of the present application, the size of the composite structure for UV blocking may be 3 μm to 15 μm, preferably 5 μm to 10 μm. In addition, the shape of the composite structure for blocking ultraviolet rays may be characterized in that it is spherical, oval, rod-shaped or plate-shaped. Therefore, the size of the composite structure for UV blocking may have a different meaning depending on the shape as described above, and for example, if it is spherical, it means the diameter of a sphere, and if it is oval, it may be the diameter of the major axis or the diameter of the minor axis. , may be the length of the major axis or the minor axis in the case of a rod type, and may mean a particle diameter or thickness in the case of a plate type. The size range of the composite structure for blocking ultraviolet rays may be an average size range of a range that does not impart a foreign feeling to the feeling when used as a sunscreen, and the shape of the composite structure for blocking ultraviolet rays may be preferably a spherical or oval shape. .

In one embodiment of the present application, the porosity of the porous silica structure may be expressed in units of volume percentage (vol%), and the porosity may be 30 vol% to 70 vol%. In this case, the porosity may mean a ratio of the total volume of the pores to the total volume of the porous silica structure. On the other hand, if the porosity is less than 30 vol%, the porosity is too low, so it may not be possible to achieve the effect of improving the feeling of use as a porous structure, solving the cloudiness phenomenon, and providing particles with improved dispersion stability with a low specific gravity, exceeding 70 vol% In this case, the porosity may be too high to maintain the shape of the structure.

In one embodiment of the present application, the specific surface area of the porous silica structure may be 1 m ² /g to 500 m ² /g. Meanwhile, in the specific surface area range, the average pore diameter of the porous silica structure may be 1 nm to 500 nm, preferably 1 nm to 300 nm, and more preferably 10 nm to 200 nm. have. If the average pore diameter of the porous silica structure in the specific surface area range is less than 1 nm, the pore size may be too small to exhibit the properties as a porous structure well, and if it exceeds 500 nm, the pore size is too large of the structure It may not be able to maintain its shape.

In one embodiment of the present application, the size of the metal oxide nanoparticles may be 1 nm to 100 nm, and the shape is not limited, but, for example, may be spherical, oval, rod-shaped or plate-shaped. have. On the other hand, when the metal oxide nanoparticles are rod-shaped, the length ratio of the major axis and the minor axis (length ratio of the major axis (L ¹ )/short axis (L ² )) may be 2 or more, preferably 2 to 8. In addition, when the metal oxide nanoparticles are plate-shaped, the aspect ratio (ratio of particle diameter (d)/thickness (t)) may be 2 or more, preferably 2 to 40. In this case, the particle diameter of the plate-shaped metal oxide nanoparticles may be 2 to 100 nm, and the thickness may be 1 to 20 nm.

In one embodiment of the present application, the content of the porous silica structure may be 100 parts by weight to 1000 parts by weight based on 100 parts by weight of the metal oxide nanoparticles. When the content of the porous silica structure is less than 100 parts by weight relative to 100 parts by weight of the metal oxide nanoparticles, the silica forming the porous silica structure does not surround the metal oxide nanoparticles well, and the effect due to the silica coating of the metal oxide nanoparticles That is, the effect of inhibiting active oxygen caused by the photoreaction between the metal oxide nanoparticles and ultraviolet rays and the effect of preventing direct contact between the metal oxide nanoparticles and the skin may not be achieved, and when it exceeds 1000 parts by weight Since the content of the silica structure is too large, the UV blocking effect of the metal oxide nanoparticles itself may not be expressed.

In one embodiment of the present application, the UV-blocking composite structure may be characterized in that it has an ability to remove active oxygen, and the active oxygen may be a hydroxy radical, a peroxy radical or a superoxide radical. That is, the UV-blocking composite structure effectively suppresses not only UV-blocking ability, but also active oxygen generated through a photoreaction after UV absorption as shown in Reaction Formula 1, thereby minimizing skin irritation and side effects added thereto. have.

[Scheme 1]

MO ₂ + hv → MO ₂ (h ⁺ + e ^- )

h ⁺ + H ₂ O → OH + H ⁺

e ^- + O ₂ → O ₂ ^-

In this case, M in Scheme 1 may be titanium, cerium, zirconium, iron, iridium, or zinc. Specifically, the composite structure for UV blocking has a form in which silica forming the structure surrounds the metal oxide nanoparticles, thereby preventing direct contact between the metal oxide nanoparticles and the skin, thereby preventing active oxygen generated from the metal oxide nanoparticles. It may be to prevent contact with the skin. That is, the UV blocking composite structure has excellent radical removal ability contained in the active oxygen, and can effectively prevent problems such as skin aging and tissue damage caused by this, and thus not only UV blocking effect but also anti-aging effect may be what you have

In addition, the metal oxide nanoparticles are evenly positioned inside or on the surface of the porous silica structure to minimize agglomeration in the formulation, thereby greatly improving the feeling of use. In addition, in the case of conventional organic sunscreens, there is a problem in that the activity is lowered by active oxygen caused by the inorganic sunscreen as well as the inconvenience of having to reapply over time because of low photostability. However, the composite structure for UV blocking of the present invention effectively scatters and blocks UV rays as well as blocks active oxygen in the formulation, thereby solving the problem of using an organic UV blocking agent and remarkably improved synergy in UV blocking ability. it may be achievable

The second aspect of the present application is

It provides a sunscreen composition comprising the composite structure for blocking ultraviolet rays of the first aspect of the present application.

Although detailed descriptions of parts overlapping with the first aspect of the present application are omitted, the contents described with respect to the first aspect of the present application may be equally applied even if the description thereof is omitted in the second aspect.

Hereinafter, the sunscreen composition according to the second aspect of the present application will be described in detail.

In one embodiment of the present application, the sunscreen composition may include a composite structure for blocking ultraviolet rays, and the composite structure for blocking ultraviolet rays includes a porous silica structure; and a plurality of metal oxide nanoparticles located inside or on the surface of the structure, and the silica forming the structure may surround the nanoparticles. The composite structure for blocking ultraviolet rays may include only a porous silica structure and metal oxide nanoparticles, and may not include a separate polymer. Therefore, there is an effect of avoiding the microplastic issue, which has recently been a problem when manufacturing a sunscreen composition using the composite structure. On the other hand, the composite structure for blocking ultraviolet rays may include a plurality of metal oxide nanoparticles located inside or on the surface of the porous silica structure, and the silica forming the structure may be characterized in that it surrounds the nanoparticles. . In this case, when the silica surrounds the nanoparticles, it may mean that they are coated, and it is preferable that the silica surrounds the entire nanoparticles, but does not exclude a form surrounding a part.

In one embodiment of the present application, the porous silica structure may have a characteristic of scattering light because it has a porous shape. Therefore, the UV scattering properties of the porous silica structure and the UV blocking effect of a plurality of metal oxide nanoparticles located inside or on the surface of the structure may be combined to block a wider range of UV rays. In addition, the composite structure for UV blocking may improve dispersibility in the formulation with a low specific gravity, and may minimize the cloudiness phenomenon due to the light scattering effect induced in the morphology of the porous silica structure.

In one embodiment of the present application, the UV-blocking composite structure may be characterized in that it has an ability to remove active oxygen, and the active oxygen may be a hydroxy radical, a peroxy radical or a superoxide radical. That is, the UV-blocking composite structure effectively suppresses not only UV-blocking ability, but also active oxygen generated through a photoreaction after UV absorption as shown in Reaction Formula 1, thereby minimizing skin irritation and side effects added thereto. have.

[Scheme 1]

MO ₂ + hv → MO ₂ (h ⁺ + e ^- )

h ⁺ + H ₂ O → OH + H ⁺

e ^- + O ₂ → O ₂ ^-

In this case, M in Scheme 1 may be titanium, cerium, zirconium, iron, iridium, or zinc. Specifically, the composite structure for UV blocking has a form in which silica forming the structure surrounds the metal oxide nanoparticles, thereby preventing direct contact between the metal oxide nanoparticles and the skin, thereby preventing active oxygen generated from the metal oxide nanoparticles. It may be to prevent contact with the skin. That is, the UV blocking composite structure has excellent radical removal ability contained in the active oxygen, and can effectively prevent problems such as skin aging and tissue damage caused by this, and thus not only UV blocking effect but also anti-aging effect may be what you have

In addition, the metal oxide nanoparticles are evenly positioned inside or on the surface of the porous silica structure to minimize agglomeration in the formulation, thereby greatly improving the feeling of use. In addition, in the case of conventional organic sunscreens, there is a problem in that the activity is lowered by active oxygen caused by the inorganic sunscreen as well as the inconvenience of having to reapply over time because of low photostability. However, the composite structure for UV blocking of the present invention effectively scatters and blocks UV rays as well as blocks active oxygen in the formulation, thereby solving the problem of using an organic UV blocking agent and remarkably improved synergy in UV blocking ability. it may be achievable

In one embodiment of the present application, the content of the composite structure for blocking ultraviolet rays may be 0.1 wt% to 20 wt%, preferably 0.1 wt% to 10 wt%, more preferably 0.1 wt% to 20 wt% based on the total weight of the sunscreen composition It may be 0.1 wt% to 5 wt%.

In one embodiment of the present application, the sunscreen composition lowers absorption of light in the visible ray region due to the diffuse reflection effect of light to minimize the cloudiness phenomenon, which is a problem of inorganic fine particles such as metal oxide nanoparticles, as well as antioxidant Since it is manufactured using an antioxidant, the metal oxide nanoparticles are uniformly applied to the porous silica structure by strong bonding with the antioxidant, thereby implementing improved UV blocking ability. In addition, the sunscreen composition has excellent blocking effect in the UVB as well as UVA region, has excellent inhibition of active oxygen caused by photoreaction, and can provide sufficient stability for use as a sunscreen.

In one embodiment of the present application, the sunscreen composition may further include an organic solvent, silicone oil, fiber, emulsifier, moisturizer, plasticizer or purified water.

In one embodiment of the present application, the organic solvent may be alcohol, glycol, silicone oil, natural oil, vegetable oil, nut oil or mineral oil. The organic solvent serves as a solvent for dispersing the UV-blocking composite structure. In addition, the organic solvent can disperse the UV-blocking composite structure, and any organic solvent suitable for preparing a cosmetic composition having a good spreadability can be used without any particular limitation.

In one embodiment of the present application, the silicone oil may be dimethicone, cetyldimethicone, cyclopentasiloxane, cyclohexasiloxane or stearyldimethicone. The silicone oil can form an oil phase in emulsifying a cosmetic, and serves to improve the feeling of use.

In one embodiment of the present application, the textile material may be used, such as VGL silk. The textile agent serves to improve the feeling of use of the sunscreen composition.

In one embodiment of the present application, the emulsifier may be a PEG silicone emulsifier, a nonionic W / O emulsifier, a cationic emulsifier or an anionic emulsifier. The emulsifier allows each component of the sunscreen composition according to the present invention to be emulsified. In addition, it serves to improve the stability of the formulation by trapping the particles in the emulsion particles of the oil phase.

In one embodiment of the present application, the moisturizing agent is 1,2-hexanediol, glycerin, propylene glycol, butylene glycol, polyethylene glycol, sorbitol or polyol such as trehalose, amino acid, urea, lactate or PCA-Na natural moisturizing agent A high molecular weight moisturizer such as factor (NMF), hyaluronate, chondroitin sulfate, or hydrolyzed collagen may be used. The moisturizer may increase the moisturizing power of the sunscreen composition according to the present invention and at the same time serve as a preservative.

In one embodiment of the present application, the plasticizer may be DPG (Dipropylene glycol) or the like.

In one embodiment of the present application, the sunscreen composition contains oils, waxes, surfactants, thickeners, pigments, cosmetic additives, powders, sugars, antioxidants, buffers, Components commonly formulated in cosmetic compositions such as various extracts, stabilizers, preservatives and fragrances can be appropriately blended.

In one embodiment of the present application, the fats and oils include vegetable oils such as colostrum oil, rosehip oil, castor oil or olive oil, animal oils such as mink oil or squalene, mineral oil such as liquid paraffin or vaseline, silicone oil or myristine Synthetic oils, such as acid isopropyl, etc. can be used.

In one embodiment of the present application, as the waxes, vegetable wax such as carnauba wax, candelilla wax or jojoba oil, animal wax such as beeswax or lanolin may be used.

In one embodiment of the present application, the surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant.

In one embodiment of the present application, the thickener may be, for example, a water-soluble polymer.

In one embodiment of the present application, as the water-soluble polymer, plant-based (polysaccharide-based) natural polymers such as guar gum, locust bean gum, quince seed, carrageenan, galactan, gum arabic, tragacanth, pectin, mannan or starch , xanthan gum, textlan, succinol glucan, cadran or hyaluronic acid, such as microbial (polysaccharide) natural polymer, gelatin, casein, albumin or collagen, etc. animal (protein) natural polymer, methyl cellulose, ethyl cellulose , hydroxy, ethyl cellulose, hydroxypropyl cellulose, cellulose-based semi-synthetic polymers such as carboxymethyl cellulose or methyl hydroxypropyl cellulose, starch-based semi-synthetic polymers such as soluble starch, carboxymethyl starch or methyl starch, alginic acid propylene glycol ester or alginic acid Alginic acid-based semi-synthetic polymers such as salts, other polysaccharide derivative semi-synthetic polymers, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, carboxyvinyl polymer or vinyl-based synthetic polymers such as sodium polyacrylate, polyethylene oxide, ethylene oxide Alternatively, other synthetic polymers such as propylene oxide block copolymers, and inorganic materials such as betnite, laponite, micro-dispersed silicon oxide, colloidal alumina, etc. may be used.

In one embodiment of the present application, the dye may be, for example, a synthetic dye or a natural dye, and the synthetic dye is a water-soluble/oil-soluble dye such as FD&C Yellow No 6 or FD&C Red No 4, iron oxide or ultramarine. Inorganic pigments, organic pigments such as D&C Red No 30 or D&C Red No 36, lakes such as FD&C Yellow No 6 Al lake, etc. may be used, and the natural pigments are β-carotene, β-apo-8-carotene, lilo. Carotenoid pigments such as pin, capxanthin, vixin, crosine, or candaxanthin; flavonoid pigments such as sisonin, lamanin, ninocyanine, carsamine, saprole yellow, rutin, guercetin, or cacao pigment; Flavin-based pigments such as riboflavin, quinone-based pigments such as laccaic acid, carminic acid (cochinyl), kermesic acid, arizarin, cycorin, arkanine or nicinochrome, porphyrin-based pigments such as chlorophyll or hemoglobin; Diketone-based pigments such as chromin (dameric), betacyanidin-based pigments such as betanin, and the like may be used.

In one embodiment of the present application, the cosmetic additive, for example, vitamin, plant extract or animal extract may be used, and the vitamin is retinol (vitamin A), tocopherol (vitamin E) or ascorbic acid (vitamin X), etc. Can be used, and the plant extract is menthol (mint), azulene (chamomile), allantoin (wheat), caffeine (coffee), licorice extract, cinnamon extract, green tea extract, lavender extract or lemon extract, etc. may be used, and the As the animal extract, placenta (cow placenta), royal jelly (bee secretion), snail extract (mucus secretion), etc. may be used.

In one embodiment of the present application, the sunscreen composition may further include an organic sunscreen, and the organic sunscreen is, for example, a benzoyl compound, a benzoate compound, a benzophenone compound, or a triazine-based compound. It may include a material selected from the group consisting of compounds, cinamate compounds, salicylate compounds, sulfate compounds, silonic acid compounds, and combinations thereof, and more particularly preferably diethylaminohydroxy Benzoylhexylbenzoate, homosalate, ethylhexylsalicylate, phenylbenzimidazole sulfonic acid, octocrylene, ethylhexylmethoxycinnamate, ethylhexyl palmitate, butylmethoxydibenzoylmethane, 4-methylbenzylidene It may include a material selected from the group consisting of camphor, isoamyl-p-methoxycinnamate, bis-ethylhexyloxyphenol methoxyphenyltriazine, and combinations thereof. In this case, the content of the organic sunscreen may be 1 wt% to 25 wt%, preferably 5 wt% to 20 wt%, based on the total weight of the sunscreen composition.

The third aspect of the present application is

coating the porous polymer structure with an antioxidant; coating the metal oxide nanoparticles on the porous polymer structure coated with the antioxidant; coating silica on the porous polymer structure by adding a silica precursor to the porous polymer structure coated with the metal oxide nanoparticles; and heat-treating the silica-coated porous polymer structure to remove the porous polymer structure and the antioxidant.

Although detailed descriptions of parts overlapping with the first and second aspects of the present application are omitted, the descriptions of the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect. .

Hereinafter, the sunscreen composition according to the third aspect of the present application will be described in detail with reference to FIG. 1 .

First, in one embodiment of the present application, the method of manufacturing the composite structure for blocking ultraviolet rays comprises the step of coating an antioxidant on the porous polymer structure.

In one embodiment of the present application, the porous polymer structure is not particularly limited as long as pores are formed on the surface of the particles, for example, a gel type, a precipitated type, a fumed type, a dry type, a ground It can be used in any of the possible forms among a type, a calcined type, and a hydrous type. In terms of type, the porous polymer structure may be a porous organic polymer particle, for example, acrylic polymer, vinyl polymer, epoxy polymer, polyolefin polymer, polyurethane polymer, polyamide polymer, polyester polymer, It may include a material selected from the group consisting of a polyimide-based polymer, a polycarbonate-based polymer, a polyether-based polymer, a polysiloxane-based polymer, a fluorine-based polymer, a polysaccharide polymer, and combinations thereof. More specifically, the porous polymer structure may be preferably a biocompatible polymer, for example, polymethylmethacrylate (PMMA), polyglycolide (PGA), polylactide (polylactide; PLA) , poly(lactide-co-glycolide) copolymer (poly(lactide-co-glycolide); PLGA), poly(metha)acrylate copolymer, ethylene-vinyl acetate copolymer ( poly(ethylene-co-vinyl acetate; EVA), polystyrene, polycaprolactone (PCL), polyorthoester, polyphosphagene, alginate, collagen, chitosan and combinations thereof It may include a material selected from the group consisting of.

In one embodiment of the present application, the porous polymer structure may be manufactured through the following manufacturing method. That is, the method of manufacturing the porous polymer structure is acrylic polymer, vinyl polymer, epoxy polymer, polyolefin polymer, polyurethane polymer, polyamide polymer, polyester polymer, polyimide polymer, polycarbonate polymer, polyether Dissolving a polymer-based polymer, polysiloxane-based polymer, fluorine-based polymer or polysaccharide polymer and a polymer-type nonionic surfactant in an organic solvent; emulsifying the mixed solution into an aqueous solution containing a water-soluble polymer; evaporating the organic solvent by heating the emulsified product; and washing and drying the submerged porous polymer structure after evaporation. At this time, the mixed solution is added to the aqueous solution containing the water-soluble polymer and then emulsified while the polymer-type nonionic surfactant having a property of being well soluble in water moves into the aqueous solution, and according to the direction of movement, the above-described acrylic polymer, etc. A porous structure may be formed on the particles, and a porous polymer structure may be finally prepared.

In one embodiment of the present application, the amount of the polymer-type nonionic surfactant used is not limited, and the amount of the polymer-type nonionic surfactant is preferably 40 parts by weight to 150 parts by weight relative to 100 parts by weight of the acrylic polymer, etc. It may be parts by weight.

In one embodiment of the present application, 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. In addition, preferably, the polymer-type nonionic surfactant may be a block copolymer of the Pluronic series.

In one embodiment of the present application, the organic solvent is not limited as long as it is a solvent capable of dissolving the acrylic polymer and the polymer-type nonionic surfactant, preferably methylene chloride, n-hexanone, methyl isopropyl ketone, toluene, iso It may include a material selected from the group consisting of amyl alcohol and combinations thereof. In this case, the volume ratio (w/v) of the organic solvent to the sum of the weight of the acrylic polymer and the like of the polymer type nonionic surfactant may be 0.001 to 1 g/mL.

In one embodiment of the present application, the water-soluble polymer is not limited as long as it can emulsify the mixed solution, preferably polyvinyl alcohol, poly(vinyl alcohol-vinyl acetate) copolymer, polyacrylic acid, poly(acrylate- acrylic acid) copolymer, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinylmethyl ether, polyethyleneimine, and combinations thereof. At this time, the amount of the water-soluble polymer is not limited, and may be preferably used in an amount of 0.01 wt% to 10 wt% based on water.

In one embodiment of the present application, the stirring conditions of the emulsification in the emulsifying step are not limited, but may preferably be stirred at 1,000 rpm to 10,000 rpm in order to realize a desired average diameter.

In one embodiment of the present application, the size of the porous polymer structure may be 3 μm to 15 μm, preferably 5 μm to 10 μm. In addition, the shape of the porous polymer structure may be characterized in that the spherical, elliptical, rod-shaped or plate-shaped. Therefore, the size of the porous polymer structure may have a different meaning depending on the shape as described above. For example, if it is spherical, it means the diameter of a sphere, and if it is oval, it may be the diameter of the major axis or the diameter of the minor axis, and the rod. In the case of the shape, it may be the length of the major axis or the minor axis, and in the case of the plate shape, it may mean the particle size or thickness. Meanwhile, the shape of the porous polymer structure may be preferably spherical or oval.

In one embodiment of the present application, the porosity of the porous polymer structure may be expressed in units of volume percentage (vol%), and the porosity may be 30 vol% to 70 vol%. In this case, the porosity may mean a ratio of the total volume of the pores to the total volume of the porous polymer structure.

In one embodiment of the present application, the specific surface area of the porous polymer structure may be 1 m ² /g to 500 m ² /g. Meanwhile, in the specific surface area range, the average pore diameter of the porous polymer structure may be 1 nm to 500 nm, preferably 1 nm to 300 nm, and more preferably 10 nm to 200 nm. have.

In one embodiment of the present application, when the surface of the porous polymer structure does not include a polar moiety capable of forming hydrogen bonds, it may be preferable to introduce a polar moiety capable of forming hydrogen bonds through additional surface treatment. have. The additional surface treatment may be performed through a known treatment method such as an organic oxidizing agent, an inorganic oxidizing agent, plasma, ultraviolet-ozone irradiation, or electron beam irradiation. The polymer material of the porous polymer structure is not limited to a specific material in that a polar moiety capable of forming a hydrogen bond, such as a carboxylic acid group or a carbonyl group, can be introduced on the surface of the non-polar polymer structure through the surface treatment. On the other hand, the polar moiety present on the surface of the porous polymer structure may interact with a hydroxyl group included in the antioxidant, such as through hydrogen bonding, as described later, and the antioxidant selectively binds to the surface of the porous polymer structure. Alternatively, it may be bound to form an organic layer.

In one embodiment of the present application, the antioxidant may help to maintain the porosity of the porous polymer structure by forming a very thin organic layer of several nanometers on the surface of the porous polymer structure. In addition, since the organic layer can form a strong bond by forming a metal-ligand charge complex with metal oxide nanoparticles to be described later, metal oxide nanoparticles with improved adhesion to the surface of the porous polymer structure. can be introduced.

In one embodiment of the present application, the antioxidant includes two or more hydroxyl groups, and may be a polyphenol-based compound or a phenol-based compound, and the polyphenol-based compound or phenol-based compound is, for example, tannic acid, Catechol, DL-3,4-dihydroxyphenylalanine, DL-DOPA (3,4-Dihydroxy-DL-phenylalanin), catecholamine, 3-hydroxytyramine, dopamine, polydopamine, phloroglucinol, caffeic acid, Dihydrocaffeic acid, ferulic acid, protocatechuic acid, chlorogenic acid, isochlorogenic acid, gentic acid, homogentic acid, gallic acid, hexahydroxydiphenic acid, ellagic acid, rosmarinic acid, lysospermic acid, curcumin, polyhydroxy acid Sylated coumarin, polyhydroxylated lignan, neolignan, silymarin, apigenol, luteolol, quercetin, quercetagine, quercetagetin, chrysine, myricetin, ramnetin, genistein, morin, gocifetin kaempferol, rutin, naringin, naringenin, hesperitin, hesperidin, diosmin, diosmoside, amentoflavone, 　fisetin, vitexin, isoliquirtigenin, hesperidin, methylchalcone, taxipolyol, silybin, sily Christine, silidianine, catechin, epicatechin, gallocatechin, catechin molt, gallocatechin molly, epicatechin molly, epigallocatechin molly, epigallocatechin, glucogalin; group consisting of proanthocyanidin, propyl moles, isoamyloctyl moles, dodecyl moles, penta-O-galoyl glucose, gallotannins, ellagitannins, shikimic acid, salicylic acid, resveratrol and combinations thereof It may be one comprising a material selected from.

In one embodiment of the present application, in the coating of the antioxidant on the porous polymer structure, two or more hydroxyl groups included in the antioxidant are bonded to a functional group such as a carbonyl group of the porous polymer structure through hydrogen bonding, etc. to maintain porosity. It may be coated.

Next, in one embodiment of the present application, the method of manufacturing the composite structure for blocking ultraviolet rays includes the step of coating the metal oxide nanoparticles on the porous polymer structure coated with the antioxidant.

In one embodiment of the present application, the metal oxide nanoparticles form a strong bond by forming a metal-ligand charge complex with the antioxidant, and may be coated on the porous polymer structure with improved adhesion. have.

In one embodiment of the present application, the content of the metal oxide nanoparticles may be 4 parts by weight to 1,000 parts by weight based on 1 part by weight of the antioxidant.

Next, in one embodiment of the present application, the method of manufacturing the composite structure for blocking ultraviolet rays further comprises the step of further coating the antioxidant on the porous polymer structure coated with the metal oxide nanoparticles; may further include.

In one embodiment of the present application, the description of the antioxidant is the same as described in; coating the antioxidant on the porous polymer structure. However, in this step, additional coating of an antioxidant may be performed to coat silica, which will be described later, on the porous polymer structure with improved adhesion.

Next, in one embodiment of the present application, the method for preparing the composite structure for blocking ultraviolet rays comprises the steps of coating silica on the porous polymer structure by adding a silica precursor to the porous polymer structure further coated with the antioxidant; do.

In one embodiment of the present application, the silica may be coated on the porous polymer structure with improved adhesion by forming a strong bond by forming a metal-ligand charge complex with the antioxidant. In this case, the silica may be to coat not only the porous polymer structure, but also the already coated metal oxide nanoparticles.

In one embodiment of the present application, the content of the silica may be 1 to 10 parts by weight based on 100 parts by weight of the porous polymer structure.

Next, in one embodiment of the present application, the method for manufacturing the composite structure for blocking UV light is heat-treated on the silica-coated porous polymer structure to remove the porous polymer structure and the antioxidant.

In one embodiment of the present application, the heat treatment may be performed at 700° C. to 1,200° C. for 10 minutes to 60 minutes, and preferably at 800° C. to 1,000° C. for 20 minutes to 40 minutes. The porous polymer structure and the antioxidant may be removed through the heat treatment, and thus, the manufactured composite structure for UV protection may include only the porous silica structure and a plurality of metal oxide nanoparticles. At this time, when the heat treatment is performed below the temperature and time range, the porous polymer structure and the antioxidant may not be removed, and when performed above the temperature and time range, the conditions in which the porous polymer structure and the antioxidant are removed have already been achieved It may be inefficient because That is, since the manufactured composite structure for UV blocking does not contain a separate polymer, it is possible to avoid the microplastic issue, which has been a problem recently. Meanwhile, since the porous polymer structure is removed through the heat treatment, the silica coated thereon may exist as a porous silica structure in a shape similar to that of the porous polymer structure. In addition, a plurality of metal oxide nanoparticles are positioned inside or on the surface of the porous silica structure, and the silica forming the structure may surround the nanoparticles.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Example 1. Preparation of a composite structure for blocking UV rays

1. TiO ₂ -Preparation of tannin-PMMA microspheres

100 mg of porous polymethylmethacrylate microspheres (PMMA, Sunjin Chemical Co., Ltd, Suwon, Republic of Korea) were dispersed in 20 mL of non-ionized water in a 50 mL falcon tube. For tannin coating, 20 mg of tannic acid (Sigma-Aldrich, St. Louis, MO, USA) was dissolved in 10 mL of non-ionized water using a 15 mL falcon tube, and then added to the falcon tube in which PMMA microspheres were dispersed. After stirring with a vortex mixer for 5 minutes, it was transferred to a 50 mL beaker and stirred with a magnetic bar at room temperature for 30 minutes. After stirring, the mixture was washed twice using a solution in which non-ionized water and ethanol were mixed in a 2:1 ratio, and centrifugation was performed at 1,000 xg, 3 minutes. After washing, the precipitated microspheres were again dispersed in 20 mL of non-ionized water in a 100 mL spherical flask. 20 mg of water-dispersed TiO ₂ nanoparticles (UV-TITAN M040, Sachtleben, Duisburg, Germany) were well dispersed in 10 mL of non-ionized water in a 15 mL falcon tube, and then added to the flask in which the microspheres were dispersed. Then, using an oil bath, the mixture was stirred at 80°C for 3 hours using a magnetic bar. After stirring, the mixture was washed twice using a solution in which non-ionized water and ethanol were mixed in a 2:1 ratio, and centrifugation was performed at 1,000 x g, 3 minutes.

2. Silica-TiO ₂ -Preparation of PMMA microspheres

In order to perform silica coating on the TiO ₂ -tannin-PMMA microspheres prepared in 1., tannin coating was performed under the same conditions as in 1. using tannic acid on the precipitated microspheres. After drying the tannin-coated microspheres using a vacuum oven, 100 mg was dispersed in 5 mL of ethanol in a 10 mL vial. Then, 200 uL of TEOS (tetraethyl orthosilicate, Sigma-Aldrich, St. Louis, MO, USA) was added and stirred at room temperature using a magnetic bar for 30 minutes. After stirring, 200 uL of ammonia solution (ammonia solution, Sigma-Aldrich, St. Louis, MO, USA) and 1 mL of non-ionized water were additionally added, and the mixture was stirred at room temperature for 30 minutes using a magnetic bar. After silica coating was finished, washing was performed twice under the same conditions as in 1.

3. Composite structure for UV protection (silica-TiO) ₂ Preparation of nanostructures)

_{In order to remove the polymer microspheres and tannins contained in the silica-TiO 2} -PMMA microspheres prepared in step 2., heat treatment was performed at 900 degrees Celsius for 30 minutes to obtain _{a silica-TiO 2 nanostructure.}

Example 2. Preparation of a composite structure for blocking UV rays

A composite structure for UV protection was prepared in the same manner as in Example 1, except that the amount of TEOS added in Example 1 2 was 100 uL.

comparative example. water dispersion TiO ₂ nanoparticles

Water-dispersed TiO ₂ nanoparticles without a separate treatment were prepared.

Experimental Example 1. Measurement of structure and absorbance of a composite structure for UV protection

In order to confirm the structure of tannin -PMMA microspheres (b), the silica microspheres -PMMA -TiO ₂ (c) and silica -TiO ₂ nanostructures (d) - Example 1 TiO ₂ nano-particles of (a), TiO ₂ SEM images were taken using an electron microscope (Hitachi S-4800, Tokyo, Japan), which are shown in FIG. 2 , respectively.

TiO ₂ nanoparticles, as the measurement results shown in (a) of FIG. 2 has been able to check that it has the size of a nano size, size of the silica nanostructures -TiO ₂ (d) is a TiO ₂ - Tannin -PMMA microspheres (b ), _{it was confirmed that the silica-TiO 2} -PMMA microspheres were formed somewhat smaller than (c). This was analyzed to be because the polymer microspheres and tannins were removed through the high-temperature heat treatment process.

In addition, TiO ₂ nano-particles in Example 1, TiO ₂ - Tannin -PMMA microspheres, silica, and silica microspheres -PMMA -TiO ₂ -TiO ₂ nanostructures each absorption characteristics analyzed via UV-VIS / NIR Spectrophotometer (Lambda 1050, Perkin Elmer, Waltham, MA, USA), which is shown in FIG. 3 . The results also carried out as shown in Example 1. 3 The composite structure of sunscreen prepared in the comparative example to compare with TiO ₂ nanoparticles exhibits a similar absorbance value in terms of an excellent sun protection case (silica -TiO ₂ nanostructures) effect was able to confirm that it has

In addition, PMMA microspheres in Example 1, TiO ₂ - Tannin -PMMA microspheres, silica, and silica microspheres -PMMA -TiO ₂ -TiO ₂ nanostructures each analyzed by the thermogravimetric analysis component (TGA, TG209 F1 Libra, NETZSCH , Selb, Germany), and the results are shown in FIG. 4 . As shown in Figure 4 TiO ₂ - Tannin -PMMA For microspheres and silica -TiO ₂ -PMMA microspheres exhibits a weight of 13.3% and 14.4% respectively was confirmed that the residual weight increase of about 1% at the time of silica coating , Silica-TiO _{2 In} the case of nanostructures, there was no change in weight, so it was confirmed that all polymers (PMMA and tannins) were removed.

Experimental Example 2. Measurement of Hydroxyl Radical Inhibition Efficacy of Composite Structure for UV Protection

_{To measure the concentration of hydroxyl radicals generated by TiO 2} in the UV blocking composite structures of Examples 1 and 2 and Comparative Examples, terephthalic acid (TAc, Sigma-Aldrich, St. Louis, MO, USA) was This method was used. To increase the solubility of terephthalic acid, it was dissolved in 4 mM NaOH (Junsei Chemical, Tokyo, Japan). 500 μL of 0.1 mg/mL TiO _{2 and} 500 μL of 1 mM terephthalic acid were mixed in a 10 mL glass vial. The aqueous solution in the vial was exposed to an 8 W UV lamp for 20 min. After the aqueous solution exposed to UV was centrifuged at 12,000 rpm for 5 minutes, the supernatant was fluorescence measured in a microplate reader (Microplate reader, CLARIO star, BMG Labtech, Ortenberg, Germany). Measurement conditions were measured at an excitation wavelength of 320 nm and an emission wavelength band of 350-600 nm, and the results are shown in FIG. 5 . In addition, 2-hydroxyterephthalic acid (2-HTAc, Tokyo Chemical Industry, Tokyo, Japan) was used to draw a calibration curve for the calculation of the hydroxyl radical concentration, and the results are shown in Fig. 6 is shown .

As shown in FIGS. 5 and 6, in the case of the UV-blocking composite structure prepared in Examples 1 and 2, it can be confirmed that it exhibits significantly lower fluorescence intensity and hydroxyl radical concentration compared to the _{water-dispersed TiO 2 nanoparticles of Comparative Example.} there was. In addition, in the case of Example 1 containing more silica, it was confirmed that the hydroxyl radical inhibitory effect was more excellent than that of Example 2. It was confirmed that the composite structure for UV protection according to the present invention exhibited a hydroxyl radical inhibitory effect without including a separate polymer as it showed a similar hydroxyl radical inhibitory effect when compared with the data included with tannin and PMMA. .

Claims (18)

porous silica structure; and
a plurality of metal oxide nanoparticles located inside the structure;
including,
Silica forming the structure surrounds the entire nanoparticle,
The porous silica structure includes pores formed by removing the porous polymer structure, and the porosity is 30 vol% to 70 vol%.
According to claim 1,
The composite structure for blocking UV rays, characterized in that it does not contain a separate polymer.
According to claim 1,
The metal oxide nanoparticles are titanium dioxide (TiO ₂ ), cerium oxide (CeO ₂ ), zirconium dioxide (ZrO ₂ ), iron oxide (Fe ₂ O ₃ ), iridium dioxide (IrO ₂ ), zinc oxide (ZnO) and their Composite structure for UV protection comprising a material selected from the group consisting of combinations.
According to claim 1,
The size of the composite structure for blocking UV rays is 3 μm to 15 μm.
According to claim 1,
The shape of the composite structure for blocking UV rays is a composite structure for blocking UV, characterized in that it is a spherical shape, an oval shape, a rod shape, or a plate shape.
delete According to claim 1,
The porous silica structure has a specific surface area of 1 m ² /g to 500 m ² /g.
According to claim 1,
The porous silica structure has an average pore diameter of 1 nm to 500 nm.
According to claim 1,
The composite structure for UV blocking, characterized in that the size of the metal oxide nanoparticles is 1 nm to 100 nm.
According to claim 1,
The amount of the porous silica structure is 100 parts by weight to 1000 parts by weight based on 100 parts by weight of the metal oxide nanoparticles.
According to claim 1,
The UV-blocking composite structure is a UV-blocking composite structure, characterized in that it has an active oxygen removal ability.
12. The method of claim 11,
The active oxygen is a hydroxy radical, a peroxy radical or a superoxide radical for blocking UV rays.
A sunscreen composition comprising the composite structure for UV blocking of claim 1.
coating the porous polymer structure with an antioxidant;
coating the metal oxide nanoparticles on the porous polymer structure coated with the antioxidant;
coating silica on the porous polymer structure by adding a silica precursor to the porous polymer structure coated with the metal oxide nanoparticles; and
removing the porous polymer structure and the antioxidant by heat-treating the silica-coated porous polymer structure;
A method of manufacturing a composite structure for UV blocking of claim 1 comprising a.
15. The method of claim 14,
The porous polymer structure is an acrylic polymer, a vinyl-based polymer, an epoxy-based polymer, a polyolefin-based polymer, a polyurethane-based polymer, a polyamide-based polymer, a polyester-based polymer, a polyimide-based polymer, a polycarbonate-based polymer, a polyether-based polymer, and a polysiloxane-based polymer. A method of manufacturing a composite structure for UV blocking comprising a material selected from the group consisting of polymers, fluorine-based polymers, polysaccharide polymers, and combinations thereof.
15. The method of claim 14,
The antioxidant is a polyphenol-based compound or a method for producing a composite structure for blocking ultraviolet rays that is a phenol-based compound.
15. The method of claim 14,
The heat treatment is a method of manufacturing a composite structure for UV protection that is performed for 10 minutes to 60 minutes at 700 ℃ to 1,200 ℃.
15. The method of claim 14,
The manufacturing method of the composite structure for blocking ultraviolet rays comprises the steps of coating metal oxide nanoparticles on the porous polymer structure coated with the antioxidant; Since the,
The method of manufacturing a composite structure for UV blocking further comprising; further coating an antioxidant on the porous polymer structure coated with the metal oxide nanoparticles.

Images