WO2008126971A1 - Polymer nano particle containing uv blocking material and method for preparing the same - Google Patents
Polymer nano particle containing uv blocking material and method for preparing the same Download PDFInfo
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- WO2008126971A1 WO2008126971A1 PCT/KR2007/006038 KR2007006038W WO2008126971A1 WO 2008126971 A1 WO2008126971 A1 WO 2008126971A1 KR 2007006038 W KR2007006038 W KR 2007006038W WO 2008126971 A1 WO2008126971 A1 WO 2008126971A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/733—Alginic acid; Salts thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/88—Polyamides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
Definitions
- the present invention relates to UV-blocking material-containing polymer nanoparticles and a preparation method thereof, and more particularly to UV- blocking material-containing polymer nanoparticles, which are biocompatible and, at the same time, non-toxic to the human body, and have improved dispersibility, as well as a preparation method thereof.
- UV radiation from sunlight is a main factor causing skin diseases, including erythema, edema, freckles, skin cancer, etc. Recently, many studies on skin diseases caused by UV radiation have been actively conducted, and many therapeutic means for protecting the skin from such UV radiation have been suggested.
- UV light is a part of the invisible solar radiation having a wavelength of 200-400 nm.
- UV light originating from solar radiation that reaches the earth's surface through the upper atmosphere can be subdivided into UV-A, UV-B and UV-C.
- UV-A has a wavelength of 320-400 nm and penetrates the dermis of the skin to cause skin cancer and skin aging
- UV-B has a wavelength of 290-320 nm and is absorbed just above the dermis to cause sunburn and inflammation.
- UV-C has a wavelength of 200-290 nm and is fatal to organisms, but is almost completely absorbed by the ozone layer.
- inorganic UV-scattering agents In order to block UV light, inorganic UV-scattering agents, organic UV-absorbing agents and the like have been used.
- the organic UV-absorbing agents mainly absorb medium-wavelength UV-B light and convert the absorbed light to energy, thus protecting the skin, and the inorganic UV-scattering agents mainly refract long-wavelength UV-A due to the inorganic materials to scatter the UV light.
- the organic UV-absorbing agents are used in limited amounts due to the toxicity of the organic materials. For this reason, the inorganic UV-scattering agents have been mainly used, and among them, titanium dioxide and zinc oxide have been typically used.
- the ratio of atoms forming the particle surface to atoms present inside the particles increases to increase the surface area of the particles, thus increasing the UV-blocking ability of the particles.
- the particles easily penetrate cells and adversely affect cells due to active oxygen on the surface thereof or can possibly penetrate the central nervous system.
- the titanium dioxide nanoparticles are not classified as new materials, are treated in the same manner as the particles of existing materials regardless of the size thereof, and are not regulated in any way.
- biocompatible polymers include water-soluble polysaccharides (carbohydrates) and polypeptides, water-soluble synthetic polymers, such as poly(ethylene glycol) and poly(vinylpyrrolidone), and chain type polyesters, which are insoluble in water, but are biodegradable.
- the water-soluble polymers include cationic polymers, which contain amine groups or the like and are dissolved in acidic solutions to carry cations, anionic polymers, which contain carboxyl groups or the like and are dissolved in basic solutions to carry anions, and nonionic polymers, which contain hydroxyl group or the like and are well soluble in water.
- water-soluble biocompatible polymers include: cationic chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine, poly-L-arginine, and polydimethylaminoethyl methacrylate; anionic hyaluronic acid, poly-gamma-glutamic acid, alginate and carboxymethylcellulose; and nonionic glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol and polyvinyl alkyl ether.
- polymers, which are insoluble in water, but are biodegradable, and thus are widely used as biocompatible polymers include polylactic acid, polyglycolic acid, polylactic- gly colic acid, polycaprolactone and the
- Chitosan that is a biocompatible polymer, is a naturally occurring amino- polysaccharide. It is a homopolymer of D- glucosamine obtained by deacetylating chitin, which is contained in the shell of crabs and shrimps, the bone of cuttlefishes, and the cell wall of microorganisms, including fungi, mushrooms and bacteria. The main function thereof in organisms is to form an exoskeleton, which protects the living body from the external environment and maintains the homeostasis of the body. Chitosan was less studied compared to the cellulose of plants, but recently, studies in terms of waste disposal problems and resource recycling, are being actively conducted.
- Chitosan has excellent biocompatibility and can be easily obtained from chitin which is abundantly found in nature. Thus, studies on the use of chitosan as blood-dialysis membranes, antithrombotic materials, surgical sutures and artificial skins have been actively conducted. Also, because chitosan has an amino group, unlike cellulose, studies on the synthesis of various derivatives of chitosan using the same for the industrial use thereof are being conducted.
- Patent Laid-Open Publication No. 1998-0150271 discloses an active component of a cosmetic composition or UV-blocking material-containing chitosan microspheres and a cosmetic composition containing the same.
- the micrometer- sized UV-blocking material has a surface area smaller than that of a nanometer- sized material, it has a low UV-blocking ability and is difficult to disperse due to the size thereof.
- patents relating to UV-blocking effects include Korean Patent Laid-Open Publication No. 1998-0053377, entitled “UV-blocking cosmetic composition", Korean Patent Laid-Open Publication No.
- the present inventors have made many efforts to develop UV- blocking material-containing polymer nanoparticles, which are biocompatible and non-toxic, and, as a result, have found that a polymer such as chitosan is biocompatible, can improve the dispersibility of a UV-blocking material, and can increase the size of nanoparticles so as to fundamentally prevent skin penetration of the UV-blocking material, thereby completing the present invention.
- UV-blocking material- containing polymer nanoparticles which are biocompatible and, at the same time, have improved dispersibility, and a preparation method thereof.
- Another object of the present invention is to provide a UV-blocking agent containing said polymer nanoparticles.
- the present invention provides a method for preparing UV-blocking material-containing polymer nanoparticles, the method comprising the steps of: (a) adding, to a polymer solution, a solution containing a UV-blocking material dispersed therein, and stirring the mixed solution; and (b) adding a crosslinker solution to the mixed solution to obtain UV-blocking material-containing polymer nanoparticles.
- the present invention provides UV-blocking material- containing polymer nanoparticles, which are prepared by the above-described method and have a particle size of 10-500 nm.
- the present invention provides a UV-blocking agent comprising said UV-blocking material-containing polymer nanoparticles.
- FIG. l is a graphic diagram showing the size distribution of titanium dioxide nanoparticles.
- FIG. 2 is a graphic diagram showing the size distribution of titanium dioxide-containing chitosan nanoparticles.
- FIG. 3 is a scanning electron micrograph of titanium dioxide-containing chitosan nanoparticles according to the present invention.
- FIG. 4 is a transmission electron micrograph of titanium dioxide-containing chitosan nanoparticles according to the present invention.
- FIG. 5 is a transmission electron micrograph of zinc oxide-containing chitosan nanoparticles according to the present invention.
- FIG. 6 is a graphic diagram showing the size distribution of titanium dioxide-containing poly-L-lysine nanoparticles according to the present invention. In FIG. 6, 1 : titanium dioxide; and 2: titanium dioxide-containing poly-L-lysine nanoparticles.
- FIG. 7 is a graphic diagram showing the size distribution of titanium dioxide-containing alginate nanoparticles according to the present invention.
- 1 titanium dioxide
- 2 titanium dioxide-containing alginate nanoparticles.
- FIG. 8 is a graphic diagram showing the comparison of UV transmittance between chitosan and titanium dioxide-containing chitosan nanoparticles according to the present invention.
- 1 chitosan
- 2 titanium dioxide-containing chitosan nanoparticles.
- the present invention relates to a method for preparing UV- blocking material-containing polymer nanoparticles, the method comprising the steps of: (a) adding, to a polymer solution, a solution containing a UV-blocking material dispersed therein, and stirring the mixed solution; and (b) adding a crosslinker solution to the mixed solution to obtain UV-blocking material- containing polymer nanoparticles.
- the polymer is preferably biocompatible chitosan.
- Chitosan is substituted with NH 2 depending on the degree of deacetylation of chitin having a functional group, NHCOCH 3 and is dissolved in acidic conditions, so that the NH 2 of the chitosan is converted to NH 3 + .
- This can bind to a negatively charged material.
- sodium triphosphate having five hydroxyl groups is used as a crosslinker, and the crosslinking of chitosan with sodium triphosphate increases the size of titanium dioxide particles.
- chitosan reacts with sodium triphosphate at a suitable ratio, it forms particles, and when the ratio between chitosan and sodium triphosphate is controlled, the size of the particles is changed.
- the volume ratio between the chitosan solution, the sodium triphosphate solution and the titanium dioxide solution is 2-10: 1 : 0.01-1, and the solutions are mixed and allowed to react to form crosslinks therebetween, thus preparing UV-blocking material-containing chitosan nanoparticles according to the present invention.
- the polymer is not limited only to chitosan, and any polymer may be used, as long as it is a biocompatible polymer.
- the biocompatible polymer include water-soluble polysaccharides (carbohydrates) and polypeptides, water-soluble synthetic polymers, such as poly(ethylene glycol) and poly(vinyl pyrrolidone), and chain type polyesters, which are insoluble in water, but are biodegradable.
- the water-soluble polymers include cationic polymers, which contain amine groups or the like and are dissolved in acidic solutions to carry cations, anionic polymers, which contain carboxyl groups or the like and are dissolved in basic solutions to carry anions, and nonionic polymers, which contain hydroxyl groups or the like and are well soluble in water.
- water-soluble biocompatible polymers include: cationic chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine, poly-L- arginine, and polydimethylaminoethyl methacrylate; anionic hyaluronic acid, poly-gamma-glutamic acid, alginate and carboxymethylcellulose; and nonionic glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol and polyvinyl alkyl ether.
- polymers, which are insoluble in water, but are biodegradable, and thus are widely used as biocompatible polymers include polylactic acid, polyglycolic acid, polylactic- gly colic acid, polycaprolactone and
- the polymer according to the present invention preferably contains one or more selected from the group consisting of chitosan, gelatin, collagen, poly-L- lysine, poly-L-histidine, poly-L-arginine, hyaluronic acid, poly-gamma-glutamic acid, alginate, carboxymethyl cellulose, glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol, polyvinyl alkyl ether, polydimethylamonoethyl methacrylate, polylactic acid, polyglycolic acid, polylactic-glycolic acid and polycaprolactone.
- the polymer according to the present invention preferably contains: one or more selected from the group consisting of chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine and poly-L-arginine; and one or more selected from the group consisting of hyaluronic acid, poly-gamma-glutamic acid, alginate, carboxymethyl cellulose, glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol, polyvinyl alkyl ether, polydimethylaminoethylmethacrylate, polylactic acid, polyglycolic acid, polylactic-glycolic acid and polycaprolactone.
- hyaluronic acid poly-gamma-glutamic acid,
- any UV-blocking material may be used without limitation, as long as it is generally used in the art.
- inorganic powder such as titanium dioxide, magnesium silicate, magnesium oxide, zinc oxide or kaolin
- a chemical UV-blocking material selected among dioxybenzone, a lawsone/dehydroxyacetone mixture, methyl anthranilate, benzophenone-4, octyl salicylate, triethanolamine salicylate, cinoxate, oxybenzone, octocrylene, digalloyl trioleate, amyl p-dimethylbenzoate, diethanolamine p-ethoxycinnamate, p-aminobenzoate, glyceryl PABA, ethyldihydroxypropyl PABA, octyldimethyl PABA, 2-phenylbenzimidazole-5- sulphonic acid, homos
- the crosslinker is preferably one selected from the group consisting of sodium triphosphate, sodium citrate, sodium oxalate, sodium pyrophosphate, sodium sulfate, sodium tartrate, sodium malate, sodium malonate, methylene sodium diphosphate, potassium citrate, potassium oxalate, potassium pyrophosphate, potassium sulfate, potassium tartrate, potassium malate, potassium malonate, epichlorohydrin, epibromohydrin and triethylenetetramine.
- polyvinylpyrrolidone is preferably added to the mixed solution of step (b).
- the polyvinylpyrrolidone is added in order to improve the dispersibility of inorganic particles, and in addition to the polyvinylpyrrolidone, a polyvinyl copolymer, gelatin, starch, polyvinyl alkyl ether, polyvinyl alcohol, hydroxyethylcellulose, carboxymethylcellulose, polyethylene glycol, polydimethylaminoethyl methacrylate or the like, which are used to improve the dispersibility of inorganic particles in the art, may also be used.
- the concentrations of the polymer solution, the UV- blocking material solution and the crosslinker solution are preferably 0.001-5% (w/v), 0.01-30% (w/v) and 0.001-3% (w/v), respectively, and more preferably 0.01-3% (w/v), 0.1-20% (w/v) and 0.01-2% (w/v), respectively.
- the polymer solution, the crosslinker solution and the UV-blocking material solution are preferably used at a volume ratio of 2-10: 1 : 0.01-1.
- the UV-blocking material-containing polymer nanoparticles prepared according to the present invention, had a particle size of 10-500 nm, and these nanoparticles showed an excellent UV-blocking effect, because they scattered UV light, such the UV light could not be transmitted therethrough.
- the present invention relates to UV-blocking material- containing polymer nanoparticles, which are prepared according to the above- described method and have a particle size of 10-500 nm, and a UV-blocking agent containing said polymer nanoparticles.
- UV-blocking agent using the UV-blocking material-containing polymer nanoparticles according to the present invention can be easily carried out by those skilled in the art using various methods known in the art.
- Example 1 Preparation of titanium dioxide-containing chitosan nanoparticles
- chitosan was dissolved in 1.5%(w/v) acetic acid solution, and the solution was stirred at low temperature for 2 hours, and then filtered through a paper filter to remove undissolved chitin.
- Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acidic solution at a concentration of 10%(w/v) were washed with acetic acid in a centrifuge, and then 10 ⁇ JL of the titanium dioxide nanoparticle solution was added to 4 ml of the above-prepared chitosan solution and stirred.
- Titanium dioxide nanoparticles prepared according to the prior known method, and the titanium dioxide-containing chitosan nanoparticles, prepared according to the above-described method, were measured using a particle size analyzer, and the measurement results were compared. As a result, as shown in FIG. 1, the original size of the titanium dioxide particles was not shown, the titanium dioxide particles were agglomerated due to the cohesion thereof and had a size distribution of 90-535 nm.
- the particle size of the titanium dioxide-containing chitosan nanoparticles prepared according to the above-described method was measured.
- the titanium dioxide-containing chitosan nanoparticles had a size distribution of 145-335 nm.
- the cohesion of the titanium dioxide nanoparticles was reduced to improve the dispersibility thereof, and the size of the smallest nanoparticles was increased from 90 nm to 145 nm, suggesting that the nanoparticles were coated with chitosan (see FIG. 3 and FIG. 4).
- chitosan was dissolved in 1.5%(w/v) acetic acid solution, and the solution was stirred at low temperature for 2 hours and filtered through a paper filter to remove undissolved chitin.
- a solution of zinc acetate dissolved in 2-propanol was allowed to react with 4 ml of a solution of sodium hydroxide dissolved in 2-propanol in a 70 ° C water bath.
- Propanol was removed from the synthesized zinc oxide nanoparticle solution, and the remaining nanoparticles were dispersed in 1.5% acetic acid.
- Example 3 Titanium dioxide-containing polv-L-lvsine nanoparticles
- Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acidic solution at a concentration of 10% (w/v) were centrifuged, and then washed with distilled water. Then, 10 ⁇ Jt of the washed solution was added to 4 ml of 0.1%(w/v) poly-L-lysine (Sigma Aldrich Inc.) and stirred. 1 ml of 0.01% sodium triphosphate solution was added thereto, and the mixed solution was stirred for 20 minutes, thus obtaining titanium dioxide-containing poly-L-lysine nanoparticles. The size of the obtained titanium dioxide-containing poly-L- lysine nanoparticles was measured using a particle size analyzer (FIG. 6).
- the titanium dioxide-containing poly-L-lysine nanoparticles 2 prepared according to the above-described method had improved dispersibility compared to the agglomerated titanium dioxide 1, and thus the size of the nanoparticles was increased.
- Example 4 Preparation of titanium dioxide-containing chitosan-alginate nanoparticles Alginate sodium salt (Sigma Aldrich Inc.) was dissolved in distilled water at a concentration of 0.001% (w/v), and chitosan was dissolved in 1.5% acetic acid at a concentration of 0.1% (w/v). Also, 0.001% (w/v) calcium carbonate solution was prepared. Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acid solution at a concentration of 10% (w/v/) were centrifuged, and then washed with distilled water, and 10 ⁇ i of the obtained solution was added to 4 ml of the 0.1% (w/v) chitosan solution.
- Alginate sodium salt Sigma Aldrich Inc.
- Example 5 Titanium dioxide-containing alginate nanoparticles
- Alginate sodium salt (Sigma Aldrich Inc.) was dissolved in distilled water at a concentration of 0.1% (w/v), and 0.001% (w/v) calcium carbonate solution was prepared. Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acidic solution at a concentration of 10% (w/v) were centrifuged, and then washed with distilled water. Then, 10 ⁇ i of the obtained titanium dioxide nanoparticle solution was added to 4 ml of the 0.1%(w/v) alginate solution, and 1 ml of the 0.001% calcium carbonate solution was added thereto. Then, the mixed solution was stirred at 1200 rpm for 20 minutes, thus obtaining titanium dioxide-containing alginate nanoparticles. The size of the obtained titanium dioxide-containing alginate particles was measured using a particle size analyzer (FIG. 7).
- the titanium dioxide-containing alginate nanoparticles (2) prepared according to the above-described method had improved dispersibility compared to the agglomerated titanium dioxide (1), and thus the size of the nanoparticles was increased.
- Example 6 UV-blocking effect of titanium dioxide-containing chitosan nanoparticles
- the UV-blocking effect of the titanium dioxide-containing chitosan nanoparticles prepared in Example 1 was measured using a UV/VIS spectrophotometer. For this purpose, each of a solution containing the titanium dioxide-containing chitosan nanoparticles and a chitosan solution was placed in a cell, and the light transmittance of each solution was measured at a wavelength of 200-1100 nm.
- the present invention provides UV-blocking material- containing polymer nanoparticles, which are biocompatible and, at the same time, non-toxic.
- the UV-blocking material- containing nanoparticles can be prepared to have a size which cannot penetrate the skin.
- the UV-blocking material-containing nanoparticles according to the present invention have a small surface, thus resulting in a high UV-blocking ability, are non-toxic to the human body, and have improved dispersibility.
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Abstract
Disclosed herein are UV-blocking material-containing polymer nanoparticles and a preparation method thereof. More specifically, disclosed are UV-blocking material-containing polymer nanoparticles, which are biocompatible and, at the same time, non-toxic to the human body, and have improved dispersibility, as well as a preparation method thereof. The UV-blocking material-containing nanoparticles are non-toxic to the human body, because they are prepared to have a size which cannot penetrate the skin. Also, the nanoparticles have improved dispersibility, because they contain a biocompatible polymer.
Description
POLYMER NANO PARTICLE CONTAINING UV BLOCKING MATERIALAND METHOD FOR PREPARING THE SAME
TECHNICAL FIELD
The present invention relates to UV-blocking material-containing polymer nanoparticles and a preparation method thereof, and more particularly to UV- blocking material-containing polymer nanoparticles, which are biocompatible and, at the same time, non-toxic to the human body, and have improved dispersibility, as well as a preparation method thereof.
BACKGROUND ART
UV radiation from sunlight is a main factor causing skin diseases, including erythema, edema, freckles, skin cancer, etc. Recently, many studies on skin diseases caused by UV radiation have been actively conducted, and many therapeutic means for protecting the skin from such UV radiation have been suggested.
In general, UV light is a part of the invisible solar radiation having a wavelength of 200-400 nm. Particularly, UV light originating from solar radiation that reaches the earth's surface through the upper atmosphere can be subdivided into UV-A, UV-B and UV-C. UV-A has a wavelength of 320-400 nm and penetrates the dermis of the skin to cause skin cancer and skin aging, UV-B has a wavelength of 290-320 nm and is absorbed just above the dermis to cause sunburn and inflammation. Also, UV-C has a wavelength of 200-290 nm and is fatal to organisms, but is almost completely absorbed by the ozone layer.
In order to block UV light, inorganic UV-scattering agents, organic UV-absorbing agents and the like have been used. The organic UV-absorbing agents mainly absorb medium-wavelength UV-B light and convert the absorbed light to energy, thus protecting the skin, and the inorganic UV-scattering agents mainly refract long-wavelength UV-A due to the inorganic materials to scatter the UV light. However, the organic UV-absorbing agents are used in limited amounts due to the toxicity of the organic materials. For this reason, the inorganic UV-scattering agents have been mainly used, and among them, titanium dioxide and zinc oxide have been typically used.
As the size of titanium dioxide particles decreases, the ratio of atoms forming the particle surface to atoms present inside the particles increases to increase the surface area of the particles, thus increasing the UV-blocking ability of the particles. However, when the particle size decreases to the nanometer scale, the particles easily penetrate cells and adversely affect cells due to active oxygen on the surface thereof or can possibly penetrate the central nervous system. Also, the titanium dioxide nanoparticles are not classified as new materials, are treated in the same manner as the particles of existing materials regardless of the size thereof, and are not regulated in any way.
Meanwhile, biocompatible polymers include water-soluble polysaccharides (carbohydrates) and polypeptides, water-soluble synthetic polymers, such as poly(ethylene glycol) and poly(vinylpyrrolidone), and chain type polyesters, which are insoluble in water, but are biodegradable. The water-soluble polymers include cationic polymers, which contain amine groups or the like and are dissolved in acidic solutions to carry cations, anionic polymers, which contain carboxyl groups or the like and are dissolved in basic solutions to carry anions, and nonionic polymers, which contain hydroxyl group or the like and are well soluble in water. Typical examples of the water-soluble biocompatible polymers include: cationic chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine,
poly-L-arginine, and polydimethylaminoethyl methacrylate; anionic hyaluronic acid, poly-gamma-glutamic acid, alginate and carboxymethylcellulose; and nonionic glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol and polyvinyl alkyl ether. Also, polymers, which are insoluble in water, but are biodegradable, and thus are widely used as biocompatible polymers, include polylactic acid, polyglycolic acid, polylactic- gly colic acid, polycaprolactone and the like.
Chitosan, that is a biocompatible polymer, is a naturally occurring amino- polysaccharide. It is a homopolymer of D- glucosamine obtained by deacetylating chitin, which is contained in the shell of crabs and shrimps, the bone of cuttlefishes, and the cell wall of microorganisms, including fungi, mushrooms and bacteria. The main function thereof in organisms is to form an exoskeleton, which protects the living body from the external environment and maintains the homeostasis of the body. Chitosan was less studied compared to the cellulose of plants, but recently, studies in terms of waste disposal problems and resource recycling, are being actively conducted.
Chitosan has excellent biocompatibility and can be easily obtained from chitin which is abundantly found in nature. Thus, studies on the use of chitosan as blood-dialysis membranes, antithrombotic materials, surgical sutures and artificial skins have been actively conducted. Also, because chitosan has an amino group, unlike cellulose, studies on the synthesis of various derivatives of chitosan using the same for the industrial use thereof are being conducted.
In the prior art relating to UV-blocking agents containing chitosan, Korean Patent
Publication No. 1998-0150271 discloses an active component of a cosmetic composition or UV-blocking material-containing chitosan microspheres and a
cosmetic composition containing the same. However, because the micrometer- sized UV-blocking material has a surface area smaller than that of a nanometer- sized material, it has a low UV-blocking ability and is difficult to disperse due to the size thereof. Also, patents relating to UV-blocking effects include Korean Patent Laid-Open Publication No. 1998-0053377, entitled "UV-blocking cosmetic composition", Korean Patent Laid-Open Publication No. 1995-0003088, entitled "UV-blocking composition", etc., but the development of technology relating either to improving dispersibility using nanoparticles or to nanoparticles, which contain a polymer such as biocompatible chitosan and are non-toxic in vivo, is insufficient.
Accordingly, the present inventors have made many efforts to develop UV- blocking material-containing polymer nanoparticles, which are biocompatible and non-toxic, and, as a result, have found that a polymer such as chitosan is biocompatible, can improve the dispersibility of a UV-blocking material, and can increase the size of nanoparticles so as to fundamentally prevent skin penetration of the UV-blocking material, thereby completing the present invention.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide UV-blocking material- containing polymer nanoparticles, which are biocompatible and, at the same time, have improved dispersibility, and a preparation method thereof.
Another object of the present invention is to provide a UV-blocking agent containing said polymer nanoparticles.
To achieve the above objects, in one aspect, the present invention provides a method for preparing UV-blocking material-containing polymer nanoparticles, the method comprising the steps of: (a) adding, to a polymer solution, a solution
containing a UV-blocking material dispersed therein, and stirring the mixed solution; and (b) adding a crosslinker solution to the mixed solution to obtain UV-blocking material-containing polymer nanoparticles.
In another aspect, the present invention provides UV-blocking material- containing polymer nanoparticles, which are prepared by the above-described method and have a particle size of 10-500 nm.
In still another aspect, the present invention provides a UV-blocking agent comprising said UV-blocking material-containing polymer nanoparticles.
Other features and aspects of the present invention will be apparent from the following detailed description and the appended claims.
BRIEF DESCRIPTION OF DRAWINGS
FIG. l is a graphic diagram showing the size distribution of titanium dioxide nanoparticles.
FIG. 2 is a graphic diagram showing the size distribution of titanium dioxide-containing chitosan nanoparticles.
FIG. 3 is a scanning electron micrograph of titanium dioxide-containing chitosan nanoparticles according to the present invention.
FIG. 4 is a transmission electron micrograph of titanium dioxide-containing chitosan nanoparticles according to the present invention.
FIG. 5 is a transmission electron micrograph of zinc oxide-containing chitosan nanoparticles according to the present invention.
FIG. 6 is a graphic diagram showing the size distribution of titanium dioxide-containing poly-L-lysine nanoparticles according to the present invention. In FIG. 6, 1 : titanium dioxide; and 2: titanium dioxide-containing poly-L-lysine nanoparticles.
FIG. 7 is a graphic diagram showing the size distribution of titanium dioxide-containing alginate nanoparticles according to the present invention. In FIG. 7, 1 : titanium dioxide; and 2: titanium dioxide-containing alginate nanoparticles.
FIG. 8 is a graphic diagram showing the comparison of UV transmittance between chitosan and titanium dioxide-containing chitosan nanoparticles according to the present invention. In FIG. 8, 1 : chitosan; and 2: titanium dioxide-containing chitosan nanoparticles.
DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS
In one aspect, the present invention relates to a method for preparing UV- blocking material-containing polymer nanoparticles, the method comprising the steps of: (a) adding, to a polymer solution, a solution containing a UV-blocking material dispersed therein, and stirring the mixed solution; and (b) adding a crosslinker solution to the mixed solution to obtain UV-blocking material- containing polymer nanoparticles.
In the present invention, the polymer is preferably biocompatible chitosan.
Chitosan is substituted with NH2 depending on the degree of deacetylation of chitin having a functional group, NHCOCH3 and is dissolved in acidic conditions, so that the NH2 of the chitosan is converted to NH3 +. This can bind to a
negatively charged material. In the present invention, sodium triphosphate having five hydroxyl groups is used as a crosslinker, and the crosslinking of chitosan with sodium triphosphate increases the size of titanium dioxide particles. When chitosan reacts with sodium triphosphate at a suitable ratio, it forms particles, and when the ratio between chitosan and sodium triphosphate is controlled, the size of the particles is changed. In the present invention, the volume ratio between the chitosan solution, the sodium triphosphate solution and the titanium dioxide solution is 2-10: 1 : 0.01-1, and the solutions are mixed and allowed to react to form crosslinks therebetween, thus preparing UV-blocking material-containing chitosan nanoparticles according to the present invention.
In the present invention, the polymer is not limited only to chitosan, and any polymer may be used, as long as it is a biocompatible polymer. Examples of the biocompatible polymer include water-soluble polysaccharides (carbohydrates) and polypeptides, water-soluble synthetic polymers, such as poly(ethylene glycol) and poly(vinyl pyrrolidone), and chain type polyesters, which are insoluble in water, but are biodegradable. The water-soluble polymers include cationic polymers, which contain amine groups or the like and are dissolved in acidic solutions to carry cations, anionic polymers, which contain carboxyl groups or the like and are dissolved in basic solutions to carry anions, and nonionic polymers, which contain hydroxyl groups or the like and are well soluble in water. Typical examples of the water-soluble biocompatible polymers include: cationic chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine, poly-L- arginine, and polydimethylaminoethyl methacrylate; anionic hyaluronic acid, poly-gamma-glutamic acid, alginate and carboxymethylcellulose; and nonionic glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol and polyvinyl alkyl ether. Also, polymers, which are insoluble in water, but are biodegradable, and thus are widely used as
biocompatible polymers, include polylactic acid, polyglycolic acid, polylactic- gly colic acid, polycaprolactone and the like.
That is, the polymer according to the present invention preferably contains one or more selected from the group consisting of chitosan, gelatin, collagen, poly-L- lysine, poly-L-histidine, poly-L-arginine, hyaluronic acid, poly-gamma-glutamic acid, alginate, carboxymethyl cellulose, glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol, polyvinyl alkyl ether, polydimethylamonoethyl methacrylate, polylactic acid, polyglycolic acid, polylactic-glycolic acid and polycaprolactone.
Alternatively, the polymer according to the present invention preferably contains: one or more selected from the group consisting of chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine and poly-L-arginine; and one or more selected from the group consisting of hyaluronic acid, poly-gamma-glutamic acid, alginate, carboxymethyl cellulose, glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol, polyvinyl alkyl ether, polydimethylaminoethylmethacrylate, polylactic acid, polyglycolic acid, polylactic-glycolic acid and polycaprolactone.
In the present invention, any UV-blocking material may be used without limitation, as long as it is generally used in the art. For example, inorganic powder, such as titanium dioxide, magnesium silicate, magnesium oxide, zinc oxide or kaolin, can be added as a physical UV-blocking material according to the dispersion technology known in the art, and a chemical UV-blocking material, selected among dioxybenzone, a lawsone/dehydroxyacetone mixture, methyl
anthranilate, benzophenone-4, octyl salicylate, triethanolamine salicylate, cinoxate, oxybenzone, octocrylene, digalloyl trioleate, amyl p-dimethylbenzoate, diethanolamine p-ethoxycinnamate, p-aminobenzoate, glyceryl PABA, ethyldihydroxypropyl PABA, octyldimethyl PABA, 2-phenylbenzimidazole-5- sulphonic acid, homosalate, drometrizole, butyl methoxydibenzoylmethane, octyl triazone, 3-(4-methylbenzylidene)camphor, and derivatives thereof, can be added according to the emulsifϊcation technology known in the art, and then formed into nanoparticles.
In the present invention, the crosslinker is preferably one selected from the group consisting of sodium triphosphate, sodium citrate, sodium oxalate, sodium pyrophosphate, sodium sulfate, sodium tartrate, sodium malate, sodium malonate, methylene sodium diphosphate, potassium citrate, potassium oxalate, potassium pyrophosphate, potassium sulfate, potassium tartrate, potassium malate, potassium malonate, epichlorohydrin, epibromohydrin and triethylenetetramine.
In the present invention, polyvinylpyrrolidone is preferably added to the mixed solution of step (b). The polyvinylpyrrolidone is added in order to improve the dispersibility of inorganic particles, and in addition to the polyvinylpyrrolidone, a polyvinyl copolymer, gelatin, starch, polyvinyl alkyl ether, polyvinyl alcohol, hydroxyethylcellulose, carboxymethylcellulose, polyethylene glycol, polydimethylaminoethyl methacrylate or the like, which are used to improve the dispersibility of inorganic particles in the art, may also be used.
In the present invention, the concentrations of the polymer solution, the UV- blocking material solution and the crosslinker solution are preferably 0.001-5% (w/v), 0.01-30% (w/v) and 0.001-3% (w/v), respectively, and more preferably 0.01-3% (w/v), 0.1-20% (w/v) and 0.01-2% (w/v), respectively.
In the present invention, the polymer solution, the crosslinker solution and the
UV-blocking material solution are preferably used at a volume ratio of 2-10: 1 : 0.01-1.
It was observed that the UV-blocking material-containing polymer nanoparticles, prepared according to the present invention, had a particle size of 10-500 nm, and these nanoparticles showed an excellent UV-blocking effect, because they scattered UV light, such the UV light could not be transmitted therethrough.
In another aspect, the present invention relates to UV-blocking material- containing polymer nanoparticles, which are prepared according to the above- described method and have a particle size of 10-500 nm, and a UV-blocking agent containing said polymer nanoparticles.
Preparing the UV-blocking agent using the UV-blocking material-containing polymer nanoparticles according to the present invention can be easily carried out by those skilled in the art using various methods known in the art.
Examples
Hereinafter, the present invention will be described in further detail with reference to examples. It will be apparent to one skilled in the art that these examples are for illustrative purpose only and are not construed to limit the scope of the present invention.
Example 1 : Preparation of titanium dioxide-containing chitosan nanoparticles
To prepare 0.1% (w/v) chitosan solution, chitosan was dissolved in 1.5%(w/v) acetic acid solution, and the solution was stirred at low temperature for 2 hours, and then filtered through a paper filter to remove undissolved chitin. Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acidic solution at a
concentration of 10%(w/v) were washed with acetic acid in a centrifuge, and then 10 μJL of the titanium dioxide nanoparticle solution was added to 4 ml of the above-prepared chitosan solution and stirred. Then, 1 ml of 0.1%(w/v) sodium triphosphate solution and 300 μi of polyvinylpyrrolidone solution were added thereto, and the mixed solution was stirred for 20 minutes, thus obtaining titanium dioxide-containing chitosan nanoparticles.
Titanium dioxide nanoparticles, prepared according to the prior known method, and the titanium dioxide-containing chitosan nanoparticles, prepared according to the above-described method, were measured using a particle size analyzer, and the measurement results were compared. As a result, as shown in FIG. 1, the original size of the titanium dioxide particles was not shown, the titanium dioxide particles were agglomerated due to the cohesion thereof and had a size distribution of 90-535 nm.
Meanwhile, the particle size of the titanium dioxide-containing chitosan nanoparticles prepared according to the above-described method was measured. As a result, as shown in FIG. 2, the titanium dioxide-containing chitosan nanoparticles had a size distribution of 145-335 nm. Thus, it could be seen that, when the titanium dioxide nanoparticles were treated with chitosan, the cohesion of the titanium dioxide nanoparticles was reduced to improve the dispersibility thereof, and the size of the smallest nanoparticles was increased from 90 nm to 145 nm, suggesting that the nanoparticles were coated with chitosan (see FIG. 3 and FIG. 4).
Example 2: Preparation of zinc oxide-containing chitosan nanoparticles
To prepare 0.1%(w/v) chitosan solution, chitosan was dissolved in 1.5%(w/v) acetic acid solution, and the solution was stirred at low temperature for 2 hours and filtered through a paper filter to remove undissolved chitin.
To synthesize zinc oxide nanoparticles, 46 ml of a solution of zinc acetate dissolved in 2-propanol was allowed to react with 4 ml of a solution of sodium hydroxide dissolved in 2-propanol in a 70 °C water bath. Propanol was removed from the synthesized zinc oxide nanoparticle solution, and the remaining nanoparticles were dispersed in 1.5% acetic acid. To the 0.1%(w/v) chitosan solution, 1 ml of the zinc oxide nanoparticle solution and 1 ml of 0.1%(w/v) sodium triphosphate solution were added, and the mixed solution was stirred for 20 minutes, thus obtaining zinc oxide-containing chitosan nanoparticles (FIG. 5).
Example 3: Titanium dioxide-containing polv-L-lvsine nanoparticles
Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acidic solution at a concentration of 10% (w/v) were centrifuged, and then washed with distilled water. Then, 10 μJt of the washed solution was added to 4 ml of 0.1%(w/v) poly-L-lysine (Sigma Aldrich Inc.) and stirred. 1 ml of 0.01% sodium triphosphate solution was added thereto, and the mixed solution was stirred for 20 minutes, thus obtaining titanium dioxide-containing poly-L-lysine nanoparticles. The size of the obtained titanium dioxide-containing poly-L- lysine nanoparticles was measured using a particle size analyzer (FIG. 6).
As a result, as shown in FIG. 6, the titanium dioxide-containing poly-L-lysine nanoparticles 2 prepared according to the above-described method had improved dispersibility compared to the agglomerated titanium dioxide 1, and thus the size of the nanoparticles was increased.
Example 4: Preparation of titanium dioxide-containing chitosan-alginate nanoparticles
Alginate sodium salt (Sigma Aldrich Inc.) was dissolved in distilled water at a concentration of 0.001% (w/v), and chitosan was dissolved in 1.5% acetic acid at a concentration of 0.1% (w/v). Also, 0.001% (w/v) calcium carbonate solution was prepared. Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acid solution at a concentration of 10% (w/v/) were centrifuged, and then washed with distilled water, and 10 μi of the obtained solution was added to 4 ml of the 0.1% (w/v) chitosan solution. Then, 1 ml of the 0.001% (w/v) alginate solution was added thereto, and the mixed solution was stirred for 10 minutes. Then, 1 ml of the 0.01% (w/v) calcium carbonate solution was added thereto, and the mixed solution was stirred for 20 minutes, thus obtaining titanium dioxide- containing chitosan-alginate composite nanoparticles.
Example 5: Titanium dioxide-containing alginate nanoparticles
Alginate sodium salt (Sigma Aldrich Inc.) was dissolved in distilled water at a concentration of 0.1% (w/v), and 0.001% (w/v) calcium carbonate solution was prepared. Titanium dioxide nanoparticles (Sigma Aldrich Inc.) dispersed in an acidic solution at a concentration of 10% (w/v) were centrifuged, and then washed with distilled water. Then, 10 μi of the obtained titanium dioxide nanoparticle solution was added to 4 ml of the 0.1%(w/v) alginate solution, and 1 ml of the 0.001% calcium carbonate solution was added thereto. Then, the mixed solution was stirred at 1200 rpm for 20 minutes, thus obtaining titanium dioxide-containing alginate nanoparticles. The size of the obtained titanium dioxide-containing alginate particles was measured using a particle size analyzer (FIG. 7).
As a result, as shown in FIG. 7, the titanium dioxide-containing alginate nanoparticles (2) prepared according to the above-described method had improved dispersibility compared to the agglomerated titanium dioxide (1), and thus the size of the nanoparticles was increased.
Example 6: UV-blocking effect of titanium dioxide-containing chitosan nanoparticles
The UV-blocking effect of the titanium dioxide-containing chitosan nanoparticles prepared in Example 1 was measured using a UV/VIS spectrophotometer. For this purpose, each of a solution containing the titanium dioxide-containing chitosan nanoparticles and a chitosan solution was placed in a cell, and the light transmittance of each solution was measured at a wavelength of 200-1100 nm.
As a result, as shown in FIG. 8, with respect to transmittance in the UV-A wavelength range (320-400 nm) and the UV-B wavelength range (290-320 nm), UV light was transmitted through chitosan, and thus chitosan had little or no UV- blocking effect. In comparison with this, the titanium dioxide-containing chitosan nanoparticles prepared in Example 1 had a very excellent UV-blocking effect, because they scattered UV light, such that the UV light could not be transmitted therethrough
INDUSTRIAL APPLICABILITY
As described in detail above, the present invention provides UV-blocking material- containing polymer nanoparticles, which are biocompatible and, at the same time, non-toxic. According to the present invention, the UV-blocking material- containing nanoparticles can be prepared to have a size which cannot penetrate the skin. Thus, the UV-blocking material-containing nanoparticles according to the present invention have a small surface, thus resulting in a high UV-blocking ability, are non-toxic to the human body, and have improved dispersibility.
Although the present invention has been described in detail with reference to the specific features, it will be apparent to those skilled in the art that this description
is only for a preferred embodiment and does not limit the scope of the present invention. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.
Claims
1. A method for preparing UV-blocking material-containing polymer nanoparticles, the method comprising the steps of:
(a) adding, to polymer solution, a solution containing a UV-blocking material dispersed therein, and stirring the mixed solution; and
(b) adding a crosslinker solution to the mixed solution to obtain UV- blocking material-containing polymer nanoparticles.
2. The method for preparing UV-blocking material-containing polymer nanoparticles according to claim 1, wherein the polymer contains one or more selected from the group consisting of chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine, poly-L-arginine, hyaluronic acid, poly-gamma-glutamic acid, alginate, carboxymethyl cellulose, glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol, polyvinyl alkyl ether, polydimethylaminoethyl methacrylate, polylactic acid, polyglycolic acid, polylactic-glycolic acid and polycaprolactone.
3. The method for preparing UV-blocking material-containing polymer nanoparticles according to claim 1, wherein the polymer contains: one or more selected from the group consisting of chitosan, gelatin, collagen, poly-L-lysine, poly-L-histidine and poly-L-arginine; and one or more selected from the group consisting of hyaluronic acid, poly-gamma-glutamic acid, alginate, carboxymethyl cellulose, glycogen, amylose, dextran, polyacrylic acid, polymethacrylic acid, pullulan, beta-glucan, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyethylene glycol, polyvinyl alcohol, polyvinyl alkyl ether, polydimethylaminoethylmethacrylate, polylactic acid, ployglycolic acid, polylactic-glycolic acid and polycaprolactone.
4. The method for preparing UV-blocking material-containing polymer nanoparticles according to claim 1, wherein said UV-blocking material is selected from the group consisting of titanium dioxide, magnesium silicate, magnesium oxide, zinc oxide, kaolin, dioxybenzone, a lawsone/dehydroxyacetone mixture, methyl anthranilate, benzophenone-4, octyl salicylate, triethanolamine salicylate, cinoxate, oxybenzone, octocrylene, digalloyl trioleate, amyl p-dimethylbenzoate, diethanolamine p-ethoxycinnamate, p-aminobenzoate, glyceryl PABA, ethyldihydroxypropyl PABA, octyldimethyl PABA, 2-phenylbenzimidazole-5- sulphonic acid, homosalate, drometrizole, butyl methoxydibenzoylmethane, octyl triazone, 3-(4-methylbenzylidene)camphor, and derivatives thereof.
5. The method for preparing UV-blocking material-containing polymer nanoparticles according to claim 1, wherein the particle size of said UV-blocking material-containing polymer nanoparticles is 10-500 nm.
6. The method for preparing UV-blocking material- containing polymer nanoparticles according to claim 1, wherein the crosslinker is selected from the group consisting of sodium triphosphate, sodium citrate, sodium oxalate, sodium pyrophosphate, sodium sulfate, sodium tartrate, sodium malate, sodium malonate, methylene sodium diphosphate, potassium citrate, potassium oxalate, potassium pyrophosphate, potassium sulfate, potassium tartrate, potassium malate, potassium malonate, epichlorohydrin, epibromohydrin and triethylenetetramine.
7. The method for preparing UV-blocking material-containing polymer nanoparticles according to claim 1, wherein one or more selected from the group consisting of polyvinylpyrrolidone, a polyvinyl copolymer, gelatin, starch, polyvinyl alkyl ether, polyvinyl alcohol, hydroxyethylcellulose, carboxymethylcellulose, polyethylene glycol, and polydimethylaminoethyl methacrylate is added to the mixed solution of step (b).
8. The method for preparing UV-blocking material-containing polymer nanoparticles according to claim 1, wherein the concentrations of the polymer solution, the UV-blocking material solution and the crosslinker solution are 0.001-5% (w/v), 0.01-30% (w/v) and 0.001-3% (w/v), respectively.
9. The method for preparing UV-blocking material-containing polymer nanoparticles according to claim 1, wherein the polymer solution, the crosslinker solution and the UV-blocking material solution are used at a volume ratio of 2- 10: 1 : 0.01-1.
10. UV-blocking material-containing polymer nanoparticles, which are prepared by the method of any one claim among claims 1-9 and have a particle size of 10- 500 nm.
11. A UV-blocking agent containing the polymer nanoparticles of claim 10.
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