KR20190071484A - Method for Preparing Chitosan Nanoparticles and Functional cosmetics Composition for adsorption of pollutant Comprising the Chitosan Nanoparticles - Google Patents

Abstract

The present invention relates to a method of preparing chitosan nanoparticles, and a functional cosmetic composition comprising the chitosan nanoparticles and reducing fine dusts or chemicals on the skin. The method of preparing chitosan nanoparticles comprises the following steps: (a) dissolving chitosan in an aqueous organic acid solution; (b) adding an aqueous sodium pyrophosphate solution to the aqueous chitosan solution prepared in step (a); and (c) removing the supernatant from the aqueous solution prepared in step (b) by centrifugation, and freeze-drying the same. The method of the present invention enables production of chitosan nanoparticles in a more stable form by an extremely simple process. Further, the chitosan nanoparticles of the present invention can significantly reduce the fine dusts or chemicals on the skin, and thus may be used as a functional cosmetic composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for preparing chitosan nanoparticles, and a cosmetic composition for adsorbing pollutants including chitosan nanoparticles,

The present invention relates to a process for producing chitosan nanoparticles and functional cosmetic compositions for reducing fine dust or chemicals containing chitosan nanoparticles prepared by the process.

Chitosan is a β-1,4-linked pyranose unit of glucosamine. The chitosan has a molecular weight of more than 5,000 and has a polysaccharide family of multivalent cations. Biomolecules can be extracted from fisheries including crustaceans such as crab shells and shrimp, and squid. In terms of its molecular structure, it has a structure similar to cellulose, which is a type of polysaccharide. It has excellent biocompatibility, Has been applied to the pharmaceutical industry since it does not occur. Recently, after being certified as a food by the US FDA, chitosan has been applied as an important biological industry and biomedical materials in the 21st century. In particular, chitosan having a specific molecular weight within a range of 20,000 to 100,000 is known to have a strong physiological activity, so it is expected to be applicable to the fields of health food, food and beverage, cosmetics, healthcare and pharmaceuticals .

In addition, chitosan has been known to have the effect of stimulating absorption through intestinal epithelial cells of drugs such as insulin (Artursson, P., Lindmark, T., Davis, SS, Illum, chitosan on the permeability of monolayer of intestinal epithelial cells (Caco-2) ", Pharm. Res. 11, 13581361). Li, Y., Zhao, H., Zheng, J., Xu, Y., < RTI ID = 0.0 > , H., Wei, G., Hao, J., Cui, F., 2002, "Bioadhesive polysaccharide in protein delivery system: chitosan nanoparticles improve the intestinal absorption of insulin in vivo", Int. J. Pharm. 249, 13147 ).

In the prior art (J. Korean Fish. Soc. 32 (3), 247-251, 1999), the calcium absorption promotion effect of chitosan oligosaccharides prepared using an ultrafiltration membrane enzyme reactor is disclosed, Complex. In addition, although the synthesis of hydrophilic chitosan-polyethylene oxide nanoparticles for protein transport has been described in the prior art (Journal of Applied Polymer Science, Vol. 63, 125-132, 1997) .

On the other hand, Korean Patent No. 10-0661125 discloses chitosan microparticles and a method for producing the chitosan microparticles. In this patent document, a chitosan solution is prepared by dissolving solid chitosan in a solvent, adding thereto a surfactant containing a sulfate group A method of forming nano-sized fine particles and then neutralizing them to prepare fine-sized chitosan nanoparticles is described. However, in the above patent documents, it is not suitable for use in food compositions or the like by using a sulfate group-containing surfactant which is harmful to the human body when producing chitosan nanoparticles.

Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

The present inventors have studied to find a method for producing nanoparticles of chitosan through a simple process without using a surfactant detrimental to the human body. As a result, it has been found that sodium pyrophosphate, which is conventionally used as a food additive and harmless to humans, Was used as a gelling agent to prepare nanoparticles of chitosan. Further, the present inventors have completed the present invention by confirming that the chitosan nanoparticles thus prepared can be used as functional cosmetic compositions for significantly reducing fine dust or chemical substances in the skin.

Accordingly, an object of the present invention is to provide a method for producing chitosan nanoparticles.

Another object of the present invention is to provide a functional cosmetic composition because it significantly reduces chitosan nanoparticles and fine dust or chemicals in the skin.

The objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention, there is provided a process for preparing a chitosan nanoparticle comprising the steps of: (a) dissolving chitosan in an aqueous solution of an organic acid; (b) adding an aqueous solution of sodium pyrophosphate to the aqueous chitosan solution prepared in step (a); And (c) centrifuging the aqueous solution prepared in step (b) to remove the supernatant and freeze-drying the supernatant.

The present inventors have studied to find a method for producing nanoparticles of chitosan through a simple process without using a surfactant detrimental to the human body. As a result, it has been found that sodium pyrophosphate, which is conventionally used as a food additive and harmless to humans, Was used as a gelling agent to prepare nanoparticles of chitosan.

Hereinafter, the present invention will be described in detail with reference to the respective steps.

Step (a): dissolving chitosan in an aqueous solution of an organic acid

The chitosan used in the production of chitosan nanoparticles in the present invention is not particularly limited, but chitosan having a viscosity of 10 cps and a deacetylation degree of 80% or more is preferably used in powder form.

To dissolve insoluble chitosan, an aqueous solution of chitosan is prepared by dissolving chitosan in an aqueous solution of organic acid. Preferably, the organic acid is selected from the group consisting of lactic acid, acetic acid, propionic acid, formic acid, ascorbic acid and tartaric acid, But is not limited thereto. Most preferably, the organic acid is acetic acid.

The concentration of chitosan in the aqueous solution of chitosan is not limited to a specific range, but is preferably 0.1-0.5% (W / V).

Step (b): adding an aqueous solution of sodium pyrophosphate to the aqueous chitosan solution prepared in step (a)

In the production process of the present invention, there is a technical feature to use sodium pyrophosphate as a gelling agent. The pyrophosphate acts as a gelling agent for promoting the gelation reaction of chitosan in the aqueous chitosan solution of the present invention. Pyrophosphoric acid is a compound that exists in the form of a sodium salt of the formula:

Sodium pyrophosphate has traditionally been used in a variety of applications including sea food, meat, poultry, and food preservatives for pets, and the United States Food and Drug Administration Has recognized sodium pyrophosphate as a safe compound in the human body.

Step (c): The aqueous solution prepared in the step (b) is centrifuged to remove the supernatant, followed by lyophilization

The aqueous chitosan solution to which the aqueous solution of sodium pyrophosphate is added is stirred to be well mixed. Conditions for stirring are not particularly limited, but according to one specific embodiment of the present invention, the mixture is stirred at 37 DEG C and 300 rpm for 30 minutes. Centrifugation is carried out using a conventional centrifugal separator and centrifugation is carried out at 15,000 rpm for 30 minutes. After centrifugation, the supernatant is removed and lyophilized to prepare chitosan nanoparticle powder.

According to another aspect of the present invention, there is provided a chitosan nanoparticle produced by the above method. The chitosan nanoparticles prepared by the method of the present invention have a particle size of 20 nm - 1 탆 and can be used as an additive in the production of foods, beverages, medicines and cosmetics.

According to still another aspect of the present invention, there is provided a method of producing a chitosan nanoparticle comprising: (a) preparing chitosan nanoparticles by the method; And (b) significantly reduces the heavy metals, fine dusts, or chemicals of the skin, thereby providing a functional cosmetic composition.

The present inventors have found that chitosan nanoparticles prepared by the method of the present invention can significantly reduce heavy metals, fine dusts, or chemicals in the skin. This effect is presumed to be caused by a mechanism for promoting desorption of contaminants when the skin is cleaned by chelate bonding or ionic bonding with amino groups and carboxyl groups present in the chitosan nanoparticles of the present invention with heavy metals or chemicals.

According to a preferred embodiment of the present invention, the concentration of the chitosan nanoparticles contained in the functional cosmetic composition of the present invention is 0.05-5 wt%. When the concentration of the chitosan nanoparticles is less than 0.05 wt%, the effect of promoting the adsorption of heavy metals or contaminants is weak. When the chitosan nanoparticles are contained in an amount exceeding 5 wt%, the amount of the heavy metal Or the promoting effect of adsorbing contaminants is difficult to obtain, which is not economical.

The functional cosmetic composition of the present invention includes components that are ordinarily added in the course of the manufacture of cosmetics and includes, for example, tablets, tablets, , Phenoxyethanol, and chlorphenesin.

According to a preferred embodiment of the present invention, the form of the functional cosmetic composition of the present invention includes, but is not limited to, a dry powder form, a cream form, a jelly form, a serum form, an essence form or a mask pack form.

According to the method for producing chitosan nanoparticles of the present invention, safer form of chitosan nanoparticles can be prepared by using sodium pyrophosphate, which has been conventionally used as a food additive, as a gelling agent, which is harmless to the human body . Further, according to the production method of the present invention, chitosan nanoparticles can be produced by a simple method, which is very economical. When the functional cosmetic composition is prepared from the chitosan nanoparticles produced by the method of the present invention, the chitosan nanoparticles combine with heavy metals or chemical substances to induce the chitosan nanoparticles to have a stable form, thereby remarkably eliminating contaminants during skin cleansing.

FIG. 1 shows the results of measurement of the size distribution of chitosan nanoparticles prepared by the method of the present invention with a Zetasizer Nano analyzer (Malvern). According to these results, the average particle size of the chitosan nanoparticles is 151 nm.
FIG. 2 shows the results of SEM (Scanning Electron Microscopy) analysis of chitosan nanoparticles prepared by the method of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Preparation of Chitosan Emulsion Aqueous Solution

The chitosan used in the present invention was chitosan powder having a viscosity of 10 cps and a deacetylation degree of 80% or more by using chitosan chitosan powder. The chitosan was dissolved in 5% acetic acid aqueous solution at 37 ° C for 1 hour with stirring to 0.1-0.5% (w / v).

Preparation of chitosan nanoparticles

An aqueous 0.05% (w / v) sodium pyrophosphate solution was slowly added to the aqueous chitosan solution prepared above and stirred at 37 ° C for 30 minutes at 300 rpm. Subsequently, the mixture was centrifuged at 15,000 rpm for 30 minutes using a centrifuge, and the supernatant was removed and lyophilized for 24 hours to prepare chitosan nanoparticle powder. The size and shape of the nanoparticles were analyzed using Malvern Zetasizer Nano analyzer and SEM (Scanning electron Microscopy).

FIG. 1 shows the results of measurement of the size distribution of chitosan nanoparticles prepared by the method of the present invention with a Zetasizer Nano analyzer (Malvern). According to these results, the average particle size of the chitosan nanoparticles is 151 nm.

FIG. 2 shows the results of SEM (Scanning Electron Microscopy) analysis of chitosan nanoparticles prepared by the method of the present invention.

Measurement of lead binding ability of chitosan nanoparticles

The calcium binding performance of the chitosan nanoparticles prepared by the above method was measured.

The chitosan nanoparticle powder prepared by the method of the present invention was added to the grape juice in an amount of 0.1-0.5% (w / w), and the mixture was stirred for 18 hours. The mixture was centrifuged and the supernatant was collected by ICP (Inductively Coupled Plasma Emission Spectroscopy) And the lead concentration was measured. The measurement results are shown in Table 1 below.

Sample number Composition of additives Lead concentration (ppm) Lead Bonding Ratio (%) 0 Lead aqueous solution 50ml (control group) 78.4 - One Lead aqueous solution 50 ml + Chitosan nanoparticles 0.1% (w / w) 68.8 12.5 2 Lead aqueous solution + chitosan nanoparticle 0.3% (w / w) 65.4 16.2 3 Lead aqueous solution + chitosan nanoparticle 0.5% (w / w) 61.1 22.1

From the results in Table 1, it can be seen that as the content of chitosan nanoparticles increases, the concentration of lead decreases and the binding rate of lead increases. Accordingly, the chitosan nanoparticles of the present invention can increase the binding rate with lead, thereby stably maintaining the lead, thereby improving the desorption rate from the skin.

Sample number Composition of additives Cadmium concentration (ppm) Lead cadmium
Bonding rate (%) 0 Cadmium aqueous solution 50ml (control group) 95.5 - One Cadmium aqueous solution 50 ml + chitosan nanoparticles 0.1% (w / w) 55.7 41.7 2 Cadmium aqueous solution 50 ml + chitosan nanoparticles 0.3% (w / w) 52.4 45.1 3 Cadmium aqueous solution 50 ml + chitosan nanoparticle 0.5% (w / w) 53.2 44.3

 From the results in Table 2, it can be seen that as the content of chitosan nanoparticles increases, the concentration of cadmium decreases and the binding ratio of cadmium increases. Accordingly, the chitosan nanoparticles of the present invention can increase the binding rate with cadmium, thereby stably maintaining cadmium, thereby improving the desorption rate from the skin.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (5)

A method for producing chitosan nanoparticles comprising the steps of:
(a) dissolving chitosan in an aqueous solution of an organic acid;
(b) adding an aqueous solution of sodium pyrophosphate to the aqueous chitosan solution prepared in step (a); And
(c) centrifuging the aqueous solution prepared in the step (b) to remove the supernatant, followed by freeze-drying. The method of claim 1, wherein the organic acid is selected from the group consisting of lactic acid, acetic acid, propionic acid, formic acid, ascorbic acid, and tartaric acid. ≪ / RTI > wherein the chitosan nanoparticles are selected from the group consisting of: The method according to claim 1, wherein the aqueous chitosan solution prepared in step (a) has a chitosan concentration of 0.1-0.5% (W / V). A chitosan nanoparticle produced by the method according to any one of claims 1 to 3, wherein the chitosan nanoparticle has a particle size of 20 nm to 1 占 퐉. (a) chitosan nanoparticles prepared by the method of any one of claims 1 to 3; And (b) a functional cosmetic composition that significantly reduces heavy metals, fine dust, or chemicals in the skin.

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