KR20220108238A - Antibacterial cosmetic container - Google Patents

Abstract

The present invention relates to an antibacterial cosmetic container capable of reducing an amount of residue on an inner wall of cosmetic contents by including a water-repellent oil-repellent layer and allowing the cosmetic contents to easily flow down from the inner wall; being easily recycled; and providing excellent antibacterial activity for harmful microorganisms. The cosmetic container according to the present invention comprises: an antibacterial resin layer including an antibacterial agent and polymer resin; and a water-repellent oil-repellent layer including the antibacterial resin layer formed on an inner surface. The water-repellent oil-repellent layer is formed by stacking mixtures including 10-30 parts by weight of a fluorine-containing copolymer, 70-90 parts by weight of a solvent, and a porous ceramic filling agent on the inner surface of the antibacterial resin layer.

Description

Antibacterial cosmetic container

The present invention relates to an antibacterial cosmetic container, which is provided with a water and oil repellent layer so that the cosmetic contents easily flow down from the inner wall by gravity, thereby reducing the residual amount of cosmetic contents on the inner wall, making it easy to recycle and excellent against harmful microorganisms It relates to a cosmetic container exhibiting antibacterial activity.

In general, packaging containers are used for the purpose of protecting contents safely by preventing loss, contamination, deformation, etc. of contents in natural environments such as temperature, humidity, light, microorganisms, etc. when manufacturing, transporting, and storing contents. They are being replaced by plastic containers to secure competitiveness.

However, unlike containers made of glass or metal, plastic containers are permeable, so the contents are easily changed, and contamination by microorganisms can be easily induced. Although chemical materials are added together, various studies on how to impart antibacterial properties to the packaging container itself as part of an effort to remove or reduce preservatives and preservatives as the harmfulness of preservatives or preservatives is emerging and consumer anxiety is increasing is in progress

On the other hand, in general, cosmetics are provided with a cosmetic container having a structure that can be opened and closed with a cover and a container body, or a bottle-shaped container body having a certain depth and a pump coupled to the upper part of the container body to pump and discharge the contents. It is stored in a cosmetic container with a structure that can be used, and only when applying makeup, a certain amount of cosmetics is taken out of the container or discharged.

However, when the existing cosmetic container accommodates and stores the cosmetic contents in mucus having a formulation such as skin lotion or cream, the cosmetic contents remain on the inner wall of the cosmetic container, so the contents cannot be used without leaving the cosmetic container or use it. The disadvantage is that it is cumbersome to do.

In addition, such cosmetic containers also have problems such as residues remaining in the container, requiring washing for recycling, and various methods to supplement this problem are being researched and developed.

For example, Korean Patent No. 10-1925865, which is document 1, relates to a plastic molded body, a container body, a push button installed on a stopper and for discharging the contents of the container body, the push button is coupled to the upper part of the body, and the body It includes a double pump for sucking and discharging the contents of the container body at the bottom and pressurizing the air inside the container body, the double pump includes: a contents suction unit for sucking the contents inside the container body and discharging to the outside; Including an air pressurizing unit for introducing air from the outside of the container body and increasing the air pressure by injecting the air into the upper space of the container body, the content suction part and the air pressurizing part of the dual pump are partition walls Disclosed is a pump container having a container inner wall residue removal means for pushing the container inner wall residue downward to prevent it from remaining.

However, the pump container having a structure as disclosed in Document 1 is made up of many components and combinations thereof in order to remove the residue remaining on the inner wall of the container, so the structure is very complicated and manufacturing is cumbersome. Research on ways to complement it is needed.

Korean Patent Registration No. 10-1149435 (Announcement Date: 2012.05.24)

The present invention has been devised to solve the problems of the prior art as described above, and an object of the present invention is to provide technical contents about a cosmetic container that can be easily recycled because it can greatly reduce the residual amount of cosmetic content adhered to the inner wall.

In addition, an object of the present invention is to provide technical details regarding a method for manufacturing a cosmetic container having excellent antibacterial activity against harmful microorganisms such as bacteria as well as mold.

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

In order to achieve the technical problem as described above, the present invention, an antimicrobial resin layer comprising an antibacterial agent and a polymer resin; and a water and oil repellent layer formed on the inner surface of the antimicrobial resin layer, wherein the water and oil repellent layer is a mixture comprising 10 to 30 parts by weight of a fluorinated copolymer, 70 to 90 parts by weight of a solvent, and a porous ceramic filler. It provides a cosmetic container, characterized in that formed by laminating on the inner surface of the antimicrobial resin layer.

In addition, the antibacterial agent is silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), titanium dioxide (TiO ₂ ), chitosan, silver (Ag) supported zirconium phosphate, silver (Ag) supported Calcium phosphate, silver (Ag) supported apatite phosphate, silver (Ag) supported silica gel, activated carbon, shell powder, egg shell powder, phytoncide, propolis, xylitol, capsaicin, curcumin, berberine, allicin, acacetin, carvacrol, mastic , catechin, genton, robinin, chitosan and may include one or more selected from the group consisting of composite antibacterial beads containing nanocellulose.

In addition, the polymer resin is polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate resin, polyvinyl chloride (polyvinyl chloride), polystyrene (polystylene), poly Polycarbonate, acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, methyl methacrylate butadiene styrene copolymer, polylactic acid resin ( poly lactic acid), nylon resin (nylon), polyvinylidene chloride, poly acetal, polyacrylate, poly methyl methacrylate, fluoropolymer , polyurethane, polyester elastomer, melamine, urea, polyamide, polyphenylene sulfide, ethylene vinylacetate, poly It may include at least one selected from the group consisting of vinyl acetate, natural rubber, and synthetic rubber.

In addition, the cosmetic container according to a preferred embodiment of the present invention may further include a gas barrier barrier layer formed on the outer surface of the antimicrobial resin layer.

In addition, the porous ceramic filler includes a modified zeolite, and the modified zeolite is prepared by: (1) mixing 5 to 50 parts by weight of natural zeolite powder and 100 parts by weight of water to prepare a suspension; (2) mixing 10 to 100 parts by weight of a mixed alcohol containing ethanol and 1,2-hexanediol in a weight ratio of 1:1 to the suspension, and reacting for 0.5 to 6 hours to prepare a mixture containing a pretreatment zeolite ; (3) obtaining a pre-treated zeolite from the mixture and then drying at a temperature of 80 to 200° C. for 6 to 24 hours to obtain a hydrophobic zeolite; (4) 10 to 100 parts by weight of the hydrophobic zeolite is mixed with 100 parts by weight of water to prepare a mixture containing the hydrophobic zeolite, and 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyl trichlorosilane are included in the prepared mixture 10 to 100 parts by weight of the mixture, reacted at 40 to 70° C. for 1 to 12 hours, to prepare a modified zeolite in which fluorine silane is introduced to the surface may be used.

The cosmetic container according to the present invention forms a structure in which the cosmetic contents easily flow down from the inner wall by gravity, so that all cosmetic contents can be used, and it is easy to clean as well as to be recyclable. In addition, it exhibits excellent antibacterial activity and can safely protect the contents for a long time.

1 is a conceptual diagram showing a cosmetic container according to the present invention.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement them. However, since the description of the present invention is merely an embodiment for structural or functional description, the scope of the present invention should not be construed as being limited by the embodiment described in the text. That is, since the embodiment may have various changes and may have various forms, it should be understood that the scope of the present invention includes equivalents capable of realizing the technical idea. In addition, since the object or effect presented in the present invention does not mean that a specific embodiment should include all of them or only such effects, it should not be understood that the scope of the present invention is limited thereby.

The meaning of the terms described in the present invention should be understood as follows.

Terms such as “first” and “second” are for distinguishing one component from another, and the scope of rights should not be limited by these terms. For example, a first component may be termed a second component, and similarly, a second component may also be termed a first component. When a component is referred to as being “connected to” another component, it may be directly connected to the other component, but it should be understood that other components may exist in between. On the other hand, when it is mentioned that a certain element is "directly connected" to another element, it should be understood that the other element does not exist in the middle. On the other hand, other expressions describing the relationship between elements, that is, "between" and "between" or "neighboring to" and "directly adjacent to", etc., should be interpreted similarly.

The singular expression is to be understood as including the plural expression unless the context clearly dictates otherwise, and terms such as "comprises" or "have" refer to the specified feature, number, step, action, component, part or these It is intended to indicate that a combination exists, and it should be understood that it does not preclude the possibility of the existence or addition of one or more other features or numbers, steps, operations, components, parts, or combinations thereof.

All terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. Terms defined in a commonly used dictionary should be interpreted as having the meaning consistent with the context of the related art, and cannot be interpreted as having an ideal or excessively formal meaning unless explicitly defined in the present invention.

Hereinafter, the present invention will be described in detail.

1 is a conceptual diagram showing a cosmetic container 100 according to the present invention.

Referring to Figure 1, the cosmetic container 100 according to the present invention, an antibacterial resin layer 101 comprising an antibacterial agent and a polymer resin; and a water-and-oil-repellent layer 103 formed on the inner surface of the antimicrobial resin layer 101; has a structure including; can be safely stored for a long time.

Looking at the structure of the cosmetic container 100 according to the present invention, the antibacterial resin layer 101 can be formed by molding an antibacterial resin composition containing an antibacterial agent and a polymer resin into the shape of a container, and the cosmetic contents including the antibacterial agent To form a cosmetic container 100 that can safely accommodate and store.

The antibacterial agent is silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), titanium dioxide (TiO ₂ ), chitosan, silver (Ag)-supported ceramic powder (zirconium phosphate, calcium phosphate, apatite phosphorus) Phosphate, silica gel), activated carbon, shell powder, egg shell powder, phytoncide, propolis, xylitol, capsaicin, curcumin, berberine, allicin, acacia Antibacterial substances such as acacetin, carvacrol, mastic, catechin, xantone, robinin, or mixtures thereof can be used, and when blended in a polymer resin It is possible to effectively inhibit the reproduction of harmful microorganisms such as E. coli, mold, and the like. Preferably, the antibacterial agent may include a complex antibacterial bead that does not easily lose antibacterial properties even at high temperatures by complexing chitosan and nano cellulose, and the content of the complex antibacterial beads will be described in more detail below.

The antimicrobial resin layer 101 may be formed by using a polymer resin as a binder, and the polymer resin is polyethylene, polypropylene, polyethylene terephthalate, or polybutylene terephthalate. ) Resin, polyvinyl chloride, polystyrene, polycarbonate, acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, methyl meta acrylate butadiene styrene copolymer, poly lactic acid, nylon resin, polyvinylidene chloride, poly acetal, polyacrylate , poly methyl methacrylate, fluoropolymer, polyurethane, polyester elastomer, melamine, urea, polyamide, poly Phenylene sulfide (polyphenylene sulfide), ethylene vinyl acetate (ethylene vinylacetate), polyvinyl acetate (polyvinylacetate), natural rubber, synthetic rubber, or a mixture thereof may be used.

The antimicrobial resin composition can be prepared by mixing the antimicrobial agent in the polymer resin, and may contain the antimicrobial agent in a ratio of 0.1 to 20 parts by weight relative to 100 parts by weight of the polymer resin. And, when it exceeds 20 parts by weight, there is a possibility that mechanical properties may be deteriorated.

As such, the cosmetic container 100 has an antimicrobial resin layer 101 containing an antimicrobial agent therein, thereby providing excellent antibacterial properties, thereby reducing the use of preservatives such as chemicals known to be harmful to the human body, or You can avoid using it and extend the shelf life of the product.

However, in FIG. 1 , a bottle-shaped cosmetic container 100 that can be utilized as a pump-type cosmetic container 100 or an airless cosmetic container 100 is illustrated, but it is not limited to such a structure and has various container-shaped structures. can be implemented as

In addition, the antimicrobial resin layer 101 may be molded using a mold with irregularities or pre-treated by a pretreatment method such as sandblasting to have an uneven surface to have a surface roughness of 0.1 to 10 μm, whereby, The water and oil repellency provided by the water and oil repellent layer 103 can be further improved, and the adhesive force of each layer laminated on the surface of the antimicrobial resin layer can be improved.

Meanwhile, the cosmetic container 100 according to the present invention has a structure including a water and oil repellent layer 103 formed on the inner surface of the antimicrobial resin layer 101 .

The water and oil repellent layer 103 provides water and oil repellency to the cosmetic container 100 so that the cosmetic contents carried in the inner receiving space of the cosmetic container 100 do not adhere to the inner wall surface of the container, so that it is lowered by gravity. By forming a structure to easily flow down, it is possible to use the cosmetic contents thoroughly, and as a result, it is possible to simplify the washing process for recycling the cosmetic container 100 because the residual amount of the cosmetic contents is low. It makes it possible to improve recyclability, and cosmetics containing a highly viscous oil component such as silicone oil emollient can also be easily stored.

The water and oil repellent layer 103 is a coating mixture comprising 10 to 30 parts by weight of a fluorinated copolymer (or, a fluorinated polymer copolymer), 65 to 90 parts by weight of a solvent, and 2 to 20 parts by weight of a porous ceramic filler. It may be formed by coating or laminating on the inner surface of the resin layer 101 .

The fluorinated copolymer has excellent bonding strength so that it is possible to uniformly form a water-and-oil-repellent layer 103 having uniform water repellency and oil repellency over the entire surface on the inner surface of the antimicrobial resin layer 101, and thereby, Alternatively, it is possible to form a structure in which the cosmetic contents including the oily component do not adhere to the inner wall surface of the cosmetic container 100 and flow down by gravity.

Specifically, the fluorinated copolymer is, perfluoroalkylethyl acrylate, benzyl methacrylate, polyfluorooctyl methacrylate, 2-N,N-diethylamino Ethyl methacrylate (2-N,N-diethylaminoethyl methacrylate), 2-hydroxyethyl methacrylate, 2,2'-ethylenedioxydiethyl dimethacrylate (2,2'-ethylenedioxydiethyl) dimethacrylate) or a copolymer including one or more monomers thereof may be used.

Specifically, perfluoroalkyl acrylates such as 2-(perfluorohexyl)ethyl methacrylate, etc., impart water and oil repellency to the inner wall of the cosmetic container so that the cosmetic contents flow down by gravity from the inner wall of the container. . The perfluoroalkyl acrylate can be mixed in a ratio of 60 to 80 parts by weight, and when the content of the perfluoroalkyl acrylate is less than 60 parts by weight, it is difficult to implement a water-oil-repellent layer with uniform water and oil repellency, and 80 parts by weight If it is exceeded, there is a risk that the bonding strength may decrease.

Benzyl methacrylate gives flexibility to the water and oil repellent layer so that the water repellent and oil repellent layer is not easily separated from the antibacterial resin layer even when an external impact or shape change of the antibacterial resin layer is applied. A water-oil-repellent layer is formed. Benzyl methacrylate may be mixed in a ratio of 10 to 30 parts by weight, and when the content is less than 10 parts by weight, there is a risk of reduced flexibility, and when it exceeds 30 parts by weight, the bonding strength of the water and oil repellent layer may be reduced.

2-Hydroxyethyl methacrylate increases the bonding strength of the water and oil repellent layer and strongly binds the modified zeolite, which is a filler, so that the water and oil repellent layer is strongly bonded to the antimicrobial resin layer, and may be mixed in a ratio of 1 to 10 parts by weight. When the content of 2-hydroxyethyl methacrylate is less than 1 part by weight, there is a fear that bonding strength may be lowered.

Ethylene glycol diglycidyl ether serves to improve mechanical properties by crosslinking each of the above-described monomers, and may be mixed in a ratio of 1 to 10 parts by weight. When the content of ethylene glycol diglycidyl ether is less than 1 part by weight, the mechanical properties of the water and oil repellent layer may be deteriorated, and there is a risk that the water and oil repellent layer may be easily damaged by friction or external impact. It is difficult to expect further improvement in physical properties.

Preferably, the fluorinated copolymer comprises 70 parts by weight of 2-(perfluorohexyl)ethyl methacrylate, 20 parts by weight of benzyl methacrylate, 5 parts by weight of 2-hydroxyethyl methacrylate, and ethylene glycol di A mixture containing 5 parts by weight of glycidyl ether may be used.

The fluorinated copolymer may be mixed in a ratio of 10 to 30 parts by weight, and when the content of the fluorinated copolymer is less than 10 parts by weight, there is a risk of lowering the mechanical properties of the water and oil repellent layer 103, and more than 30 parts by weight If this is done, there is a risk that the water-repellent and oil-repellent performance may be deteriorated.

The solvent serves to uniformly mix the fluorinated copolymer and the porous ceramic filler, and may be mixed in a proportion of 65 to 90 parts by weight. As the solvent, toluene, xylene, methyl ethyl ketone, alcohol, water, or a mixture thereof may be used, and preferably, a mixture containing ethanol and water may be used.

As the porous ceramic filler, those having an average particle size of 0.1 to 20 μm may be used, and sufficient mechanical properties are provided to the water and oil repellent layer 103 , and a fine concavo-convex structure is formed on the surface of the water and oil repellent layer 103 to provide water repellency and It plays a role in improving oil repellency and has a porous structure such as zeolite, silica, illite, bentonite, kaolinite, zeolite, elvan, sericite, attapulgite, aluminosilicate, activated carbon, sepiolite, smectite, calcium carbonate, shell, Egg shells or mixtures thereof may be used.

Preferably, the porous ceramic filler may include a modified zeolite that can further improve water and oil repellency while exhibiting antibacterial activity, and the modified zeolite has a large amount of fine pores on the surface, and fluorine silane The surface is modified with the compound to form a fine concave-convex structure on the surface of the five layers, thereby improving water and oil repellency performance.

The modified zeolite is prepared by mixing 5 to 50 parts by weight of zeolite powder and 100 parts by weight of water to prepare a suspension, and 10 to 100 mixed alcohols containing ethanol and 1,2-hexanediol in a weight ratio of 1:1 in the prepared suspension. After mixing parts by weight, reacting for 2 hours, obtaining a pre-treated zeolite from the reacted mixture, and then drying at a temperature of 80 to 200° C. for 6 to 24 hours, hydrophobic zeolite can be obtained. 10 to 100 parts by weight of the hydrophobic zeolite as described above is mixed with 100 parts by weight of water to prepare a suspension, and then 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyltrichlorosilane in the prepared suspension 10 to 100 parts by weight of the mixture may be mixed and reacted at 40 to 70° C. for 1 to 12 hours to prepare a modified zeolite having fluorine silane introduced to the surface.

In the mixture as described above, a fine concave-convex structure is formed by the porous ceramic powder present on the surface, and only a very limited area is in contact with the protrusion of the water-repellent and oil-repellent surface with low surface energy due to the fluorinated copolymer covering the surface. This makes it possible to form the water-oil-repellent layer 103 having excellent water-repellent and oil-repellent performance to prevent adhesion of both the water-based component and the oil-based component by greatly lowering the surface tension.

Meanwhile, the modified zeolite may be prepared using natural zeolite powder, but a surface-treated and modified zeolite prepared by hydrophobically treating the surface-treated zeolite and then reacting it with perfluorodecyl trichlorosilane may also be used.

Specifically, the surface-treated zeolite is prepared by (1) mixing 30 to 70 parts by weight of zeolite powder with 100 parts by weight of water and 0.1 to 5 parts by weight of sodium chloride to prepare a suspension; (2) electrolyzing the suspension to surface-treat the zeolite powder;

The surface-treated zeolite may be prepared by mixing zeolite powder with water to prepare a suspension, mixing the zeolite powder with water and then stirring so that water is sufficiently absorbed into the zeolite powder, and 30 to 100 parts by weight of zeolite powder relative to 100 parts by weight of water The parts can be mixed to prepare a suspension.

As described above, when the suspension containing the zeolite powder is supplied to the electrolysis device and then a voltage is applied, the water contained in the suspension is electrolyzed to form hydrogen gas and oxygen gas to generate excess bubbles, and the zeolite powder Excessive formation of air bubbles even in the water absorbed in the zeolite powder makes it possible to form a large amount of pores on the surface of the zeolite powder. The reaction surface area that can be reacted can be widened, and modified zeolite can be easily manufactured by using such surface-treated zeolite powder particles. This can be formed to further improve water-repellent and oil-repellent performance.

The surface-treated zeolite surface-treated as described above is reacted with ethanol and 1,2-hexanediol in the same manner as for the preparation of the modified zeolite to prepare a hydrophobic zeolite, and then surface-treated by reacting with fluorodecyl trichlorosilane. and modified zeolites.

In addition, the cosmetic container 100 according to the present invention may be configured to additionally include a gas barrier barrier layer 105 formed on the outer surface of the antimicrobial resin layer 101, and the gas barrier barrier layer 105 It inhibits gas permeation and serves to safely protect the cosmetic contents contained therein.

Specifically, the gas barrier barrier layer 105 may be formed by coating a coating composition containing polyvinylidene chloride, polyvinyl alcohol, an ethylene vinyl alcohol copolymer, or a mixture thereof, preferably, ethylene vinyl alcohol. The first coating composition comprising 5 to 15 parts by weight of the resin, 85 to 95 parts by weight of a mixed solvent mixed with isopropanol and water in a weight ratio of 3:7 and 0.5 to 3 parts by weight of polyethyleneimine can be coated to prevent transmission of ultraviolet rays A barrier layer 105 for gas blocking can be formed. In particular, the first coating composition may further include a colorant.

The cosmetic container 100 according to the present invention may be configured to further include a UV blocking layer 107 formed on the outer surface of the antimicrobial resin layer 101 , and the UV blocking layer 107 is provided on the cosmetic container 100 . It can be configured to prevent deterioration of cosmetic contents accommodated and stored inside the cosmetic container 100 by providing UV protection performance.

In addition, the UV blocking layer 107 is coated with a coating composition comprising 5 to 15 parts by weight of polyvinyl butyral, 80 to 90 parts by weight of an acrylic monomer, 0.1 to 1 parts by weight of a photoinitiator, and 0.5 to 5 parts by weight of a UV absorber. may be formed, and may be formed to a thickness of 5 to 30 μm. The ultraviolet absorber is 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-ditertiarybutylphenyl)-benzotriazole, etc. A sol-based compound may be used.

On the other hand, the cosmetic container 100 according to the present invention includes a composite antibacterial bead on the antimicrobial resin layer 101, and the composite antibacterial bead may be prepared by the following method.

The method for producing a composite antibacterial bead according to a preferred embodiment of the present invention comprises the steps of: (a) mixing 1 to 50 parts by weight of chitosan powder with 50 to 99 parts by weight of an acidic solvent to prepare a chitosan solution; (b) mixing 1 to 50 parts by weight of nano-cellulose with 50 to 99 parts by weight of a solvent to prepare a nano-cellulose solution; (c) preparing a mixed solution by mixing the chitosan solution and the nano-cellulose solution in a weight ratio of 10:1 to 1:10, respectively; and (d) preparing a composite antibacterial bead using the mixed solution.

In the step (a), as a step of preparing a chitosan solution, chitosan powder may be mixed with an acidic solvent to prepare a chitosan solution.

Chitosan is produced by deacetylating chitin, a natural high-molecular polysaccharide present in the shell of crustaceans such as crab, shrimp, and crayfish, the skeleton of molluscs such as squid, the exoskeleton of insects, and the cell wall of fungi such as mold, yeast, and mushrooms. , It is a copolymer in which D-glucosamine is β-(1→4) glycosidic bond.

Chitosan has no possibility of depletion, is harmless to the human body, has antibacterial properties that inhibit the growth of harmful microorganisms, has excellent adsorption properties to adsorb harmful components, biocompatibility and moldability, and is not soluble in water or alkaline environment, but in acidic conditions. It exhibits easily soluble properties.

Chitosan powder can be used by deacetylating chitin powder prepared by pulverizing chitin. For example, chitin powder is introduced into sodium hydroxide (NaOH) and deacetylated for 30 to 420 minutes. Those having a particle size of 10 to 2,000 μm may be used.

When the average particle size of the chitosan powder is less than 10 μm, it is difficult to improve the mechanical properties because the amount of nano-cellulose introduced is small, and when it exceeds 2,000 μm, the surface area is reduced and there is a fear that the antibacterial activity may be lowered.

In addition, the chitosan solution may be prepared by mixing chitosan powder and an acidic solvent, and 1 to 50 parts by weight of chitosan powder may be prepared by mixing 50 to 99 parts by weight of an acidic solvent.

The acidic solution for preparing the chitosan solution is hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, phosphoric acid, carbonic acid, nitrous acid, citric acid, lactic acid, sorbic acid, benzoic acid, ascorbic acid, succinic acid, or It can be prepared by using a mixture thereof, and a pH of 3 to 6 can be used, and an acidic aqueous solution containing them can be used.

Preferably, the chitosan solution may be prepared by mixing 1 to 5 parts by weight of chitosan and 100 parts by weight of an aqueous acetic acid solution, and an aqueous acetic acid solution having a hydrogen ion concentration of pH 3 to 6 may be used.

Looking at the characteristics of chitosan in detail, the antibacterial properties of chitosan are expressed by the cationized amino group (NH ₃ ⁺ ) of the chitosan backbone, and the negative charges of sialic acid and phospholipids constituting the cell wall of microorganisms are An ionic bond with the amino group of cationized chitosan is created, and as a result, the cell membrane tissue on the opposite side of the contact surface is destroyed by the polarization of the phospholipid in the cell membrane, thereby exposing the protoplasm in the cell to kill the microorganism, and the cation of chitosan is the cell DNA may inhibit the synthesis of RNA and proteins. Thus, as long as the ammonium cation of chitosan can contact the microorganism, the antimicrobial effect persists.

In addition, the antibacterial properties of chitosan are expressed by selectively binding chitosan to trace metal elements to induce toxin production and act as a chelating agent to inhibit the growth of microorganisms.

As described above, chitosan, which exhibits antibacterial properties, swells easily when in contact with water because some of the amino groups are protonated in water and actually generates a membrane potential, and contains an excessive amount of hydroxyl groups. However, when in contact with water, mechanical properties are greatly reduced, and there is a problem in that antibacterial properties are lost when processing a high-temperature mechanical molding process such as extrusion due to insufficient heat resistance. By introducing it, it is possible to manufacture composite antibacterial beads with improved heat resistance and mechanical properties along with antibacterial properties.

In the step (b), nano-cellulose may be mixed with a solvent to prepare a nano-cellulose solution.

Nano cellulose is a natural polymer with high crystallinity, excellent physical strength, heat resistance, transparency, and biodegradability. And, it is possible to improve the physicochemical properties of chitosan by strengthening or protecting the chitosan tissue bond.

Specifically, nanocellulose has a structure in which a hydroxyl group (-OH) is introduced at the 2nd carbon position of the pyranose ring, in the case of chitin, an N-acetyl group (-CHCO), and in the case of chitosan, an amino group It has a structure in which (-NH) is introduced and has a molecular structure similar to that of chitosan, and the tensile modulus of elasticity is similar to that of steel or kevlar because cellulose chains are combined to form a bundle, the density is small, and the specific surface area is large. As a bio-based material with

Nano cellulose may be prepared using a variety of conventional cellulose raw materials used for producing the same, but preferably, rice straw, barley straw, corn stalk, cotton stalk, sugar cane, bamboo, kenaf, cotton Those manufactured using cellulose raw materials including linter, wood, or mixtures thereof may be used, and nano-cellulose manufactured using such cellulose raw materials is a safe natural material that does not adversely affect the human body even when ingested.

In addition, nano-cellulose can introduce nano-cellulose having an average width of 2 to 300 nm and an average length of 100 to 2,000 nm, and when the width and length of the nano-cellulose are out of the above range, A problem that uniform introduction is difficult may occur.

The nano cellulose is manufactured by adding chemical treatment by acid hydrolysis to nanofiber cellulose (cellulose nanofibril, CNF) prepared through mechanical treatment of a cellulose raw material using a high-pressure homogenizer or a milling machine, etc. It may include one nanocrystalline cellulose (cellulose nanocrystal, CNC), cellulose derived from bacteria, or a mixture thereof.

Specifically, the nanofiber cellulose may have a width of 2 to 300 nm, a length of 700 to 2,000 nm, and an aspect ratio of 5 to less than 50, and the nanocrystalline cellulose has a width of 2 to 20 nm, a length of 100 to 600 nm, an aspect ratio of 1 to 5 may be used, and preferably, nanocrystalline cellulose may be introduced.

In this step, 1 to 50 parts by weight of nanocellulose can be mixed with 50 to 99 parts by weight of a solvent to prepare a nanocellulose solution, and when the content of nanocellulose is less than 1 part by weight, it is difficult to expect a sufficient effect of improving physical properties, When it exceeds, there is a problem that the viscosity is greatly increased due to the formation of hydrocolloids, making it difficult to complex with chitosan, and preferably, 1 to 5 parts by weight of nanocrystalline cellulose is mixed with 100 parts by weight of ethanol to prepare a nanocellulose solution. have.

The nano-cellulose is not soluble in general solvents and water due to complex hydrogen bonding and high crystallinity, and can be prepared using a solvent capable of uniformly dispersing the nano-cellulose.

The nano-cellulose solution is ethanol, methanol, butanol, propanol, isopropanol, acetic acid (acetate), acetone (acetone) or a mixture thereof using nano-cellulose as a solvent A uniformly dispersed nano-cellulose solution can be prepared.

In the step (c), the chitosan solution and the nano-cellulose solution are mixed to prepare a mixed solution.

In this step, a mixed solution can be prepared by mixing the chitosan solution and the nano-cellulose solution in a weight ratio of 10:1 to 1:10, respectively, and when it is out of the above range, it is difficult to expect an additional effect of improving physical properties due to the introduction of the nano-cellulose.

When the content of the nano-cellulose solution in the mixed solution is low, it is difficult to expect a sufficient effect of improving physical properties, and when the content exceeds the content, it is difficult to expect additional improvement in physical properties, and there is a problem that uniform dispersion of the nano-cellulose becomes difficult.

In this step, the chitosan solution and the nano-cellulose solution may be mixed and then continuously stirred or vibration may be supplied so that the nano-cellulose is uniformly introduced into the porous tissue of the chitosan.

In the step (d), as a step of preparing a composite antibacterial bead using a mixed solution, an amide bond and an ester bond are formed in chitosan and nanocellulose to cure the chitosan and nanocellulose to prepare a composite antibacterial bead.

In this step, a mixed solution containing chitosan and nano cellulose, such as a method of dropping a coagulating solution to a mixed solution, a method of dropping a mixed solution into a coagulating solution, a method of mixing a coagulating solution with a mixed solution and molding using a molding device, etc. Composite antibacterial beads can be prepared using various conventional methods that can be used to prepare beads.

According to a preferred embodiment of the present invention, in this step, the mixed solution is added dropwise to the coagulating solution to coagulate the chitosan and nano cellulose contained in the mixed solution to prepare a reaction solution containing the composite antibacterial beads in a wet state, and By drying the reaction solution, a composite antibacterial bead can be obtained.

In addition, according to a preferred embodiment of the present invention, in this step, the coagulating solution is added dropwise to the mixed solution to coagulate the chitosan and nano cellulose contained in the mixed solution to prepare a reaction solution containing the composite antibacterial beads in a wet state, By drying the prepared reaction solution, it is possible to obtain a composite antibacterial bead.

The coagulation solution that can be used for the manufacture of complex antibacterial beads is sodium hydroxide (NaOH), sodium bicarbonate (NaHCO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), hydrogen carbonate An aqueous solution containing potassium (KHCO ₃ ), ammonium hydroxide, calcium chloride (CaCl ₂ ), calcium hydroxide (CaOH ₂ ), ammonia (NH ₃ ), magnesium hydroxide (MgOH ₂ ) or a mixture thereof may be used.

The coagulation solution may use an alkaline aqueous solution containing them at a concentration of 0.1 to 5 M to promote coagulation, and when the coagulation solution concentration is less than 0.1 M, the coagulation time of chitosan and nano cellulose is consumed for a long time, and the strength of the composite antibacterial beads There is a risk of lowering, and when it exceeds 5M, composite beads of non-uniform particle size may be generated.

In addition, in this step, the composite antibacterial beads can be prepared using only the mixed solution and the coagulating solution as described above, but the composite antibacterial beads with improved mechanical properties by additionally introducing a curing agent, a curing accelerator, or a mixture thereof to the coagulating solution can also be manufactured.

The curing agent induces an amide bond and an ester bond to promote crosslinking of chitosan and nano-cellulose, thereby suppressing the swelling and solubility of the composite antibacterial beads and improving mechanical properties at the same time.

The curing agent is sodium tripolyphosphate, β-glycerophosphate, glyoxal, 1-butyl-3-methylimidazolium chloride, glue Taraldehyde (glutaraldehyde), epichlorohydrin (epichlorohydrin), diisocyanate (diisocyanate), ethyldimethylaminopropyl carbodiimide (1-ethyl-3 (3-dimethyl aminopropyl) carbodiimide), hydroxysuccinimide (N- hydroxysuccinimide), ethylene diamine, dimethylaminopropyl ethylcarbodiimide hydrochloride, hydroxybenzotriazole, diisopropylcarbodiimide, or mixtures thereof may be used. have. Preferably, the crosslinking agent may use a component that is not toxic to the human body, and sodium tripolyphosphate or a derivative thereof may be introduced.

The curing accelerator promotes the amide bond of chitosan and nano-cellulose to further improve the mechanical properties of the composite antibacterial bead, and the curing accelerator is triethoxysilane, tetraethoxysilane, lauroyl chloride (lauroyl chloride) or a mixture thereof may be used.

The curing agent and curing accelerator affect the cross-linking of chitosan and nano-cellulose, so that the strength and biodegradability of the composite antibacterial bead can be adjusted according to the amount added.

The curing agent and the curing accelerator may each be introduced in a ratio of 0.1 to 10 parts by weight relative to 100 parts by weight of the coagulation solution, and when the content is less than 0.1 parts by weight, it is difficult to expect sufficient physical property improvement, and when it exceeds 10 parts by weight, the composite antibacterial beads Although the mechanical properties can be further improved, the pores formed on the surface are lost and there is a fear that the antibacterial properties may be lowered.

In addition, in this step, it is also possible to prepare a composite antibacterial bead with improved heat resistance and antibacterial activity by additionally introducing a metal oxide to the coagulation solution, and the metal oxide may include zinc oxide, titanium dioxide, copper oxide, or a mixture thereof. By introducing 0.1 to 5 parts by weight of a metal oxide relative to 100 parts by weight of the coagulating solution, the metal oxide is introduced into the tissue of the composite antibacterial bead to enhance antibacterial properties and at the same time to prepare a composite antibacterial bead with improved heat resistance.

And, in this step, it is possible to prepare a reaction solution in which the beads in a wet state are formed, and further include the step of heat-treating the prepared reaction solution, whereby the composite antibacterial beads with further improved mechanical properties can be prepared.

To this end, in this step, the heat treatment may be performed by heating the reaction solution containing the composite antibacterial beads in a wet state at a temperature of 80 to 150 ° C. for 1 to 12 hours, and through such heat treatment, chitosan and nano cellulose cross-linking can be further promoted.

In addition, in this step, a reaction solution containing the composite antibacterial beads in a wet state is prepared, and then the prepared reaction solution is dried by a drying method such as room temperature drying, heat drying, vacuum drying and freeze drying to prepare a composite antibacterial bead. and, preferably, it is possible to prepare a composite antibacterial bead having a porous structure using a freeze-drying method.

In this step, the particle size can be controlled according to the diameter of the outlet of the syringe or needle used to drip the mixed solution or the coagulating solution, and the composite antibacterial beads having an average particle size of 0.01 to 10 mm can be prepared.

In addition, in this step, it can be configured to further include the step of preparing the composite antibacterial beads and then impregnating the composite antibacterial beads with the propolis extract, whereby the pretreatment composite antibacterial beads with improved antibacterial activity can be prepared have.

The propolis extract is prepared by pulverizing a propolis mass to prepare a pulverized product, mixing 100 parts by weight of the prepared pulverized product with 30 to 50 parts by weight of water to prepare a reaction mixture, and heating the prepared reaction mixture to a temperature of 55 to 70° C. It is carried out by heating for 6 to 12 hours, removing the supernatant at intervals of 20 to 60 minutes, removing the suspended components contained in the propolis by mixing the same amount of water as the amount of the removed supernatant, and removing the suspended components. A water-soluble propolis extract prepared by mixing 100 parts by weight of the extract with 40 parts by weight of a surfactant, polysorbate, and 100 to 500 parts by weight of water, and then mixing 10 parts by weight of amino acids may be used.

The composite antibacterial beads prepared by the method as described above exhibit excellent antibacterial properties by introducing nano cellulose into the tissues of chitosan, and the physicochemical properties are improved to show stable antibacterial activity for a long time, excellent biodegradability, and when ingested. As it does not cause adverse effects on the human body, it can be used as an antibacterial additive in the manufacture of food, cosmetics, and plastic molded products.

The cosmetic container 100 according to the present invention as described above has a transparent or opaque structure, and a pump-type cosmetic container, cover, and container body having a pump cap and container body for discharging cosmetic contents by pumping. A cosmetic container for cream forming a structure to open the cover to take out the cosmetic contents, a cap and a container body provided with a dropper for sucking the cosmetic contents so that the cosmetic contents can be dispensed by pressurization It can form a container body such as a dropper-type cosmetic container of have.

In particular, since cosmetic content does not remain on the inner wall, cosmetics can be used without leaving behind, so cosmetics containing highly viscous oil ingredients such as silicone oil emollient can be easily stored as well as cosmetic content remaining on the inner wall. can be easily removed through washing, thereby simplifying the washing process and promoting recycling of the cosmetic container 100 .

Therefore, it is possible to safely store and accommodate cosmetic contents of various formulations such as essence, cream, serum, toner, lotion, skin, oil, ampoules, and the like.

In addition, the cosmetic container 100 according to the present invention is molded using a molding method such as injection molding, extrusion molding, in-mold molding, multi-layer blow molding, etc. to include an antimicrobial resin layer, and a cosmetic container having a container-shaped structure is manufactured. and the manufactured cosmetic container can be used as a container body of a pump-type cosmetic container, a cream cosmetic container, and a dropper-type cosmetic container, but is not limited thereto.

In particular, the water and oil repellent layer 103, the barrier layer 105 for gas blocking, and the UV blocking layer 107 can be formed by coating with various conventional coating methods such as spray spraying, dipping, brushing, and the like, respectively.

Hereinafter, the present invention will be described in more detail by way of examples.

The presented examples are only specific examples of the present invention, and are not intended to limit the scope of the present invention.

<Example 1>

(1) Preparation of chitosan solution

Chitosan having a deacetylation degree of 85% and an average molecular weight (Mw) of 550,000 to 600,000 was ground and sieved to prepare a chitosan powder having an average particle size of 100 μm. 6 parts by weight of the prepared chitosan powder was mixed with 200 parts by weight of an acetic acid aqueous solution having a pH of 4 to prepare a colloidal chitosan solution.

(2) Preparation of nano-cellulose solution

6 parts by weight of nanocrystalline cellulose having an average particle size of 100 to 120 nm was mixed with 200 parts by weight of ethanol, and stirred at 150 to 200 rpm for 2 hours to uniformly disperse the nanocrystalline cellulose to prepare a cellulose solution in a suspension state.

Nanocrystalline cellulose was prepared by the following method and used as shown in FIG. 2 .

First, 50 mL of 6M phosphoric acid (H ₃ PO ₄ ) is mixed with a raw material mixture in which 20 parts by weight of bamboo-derived cellulose fiber pulverized product is mixed with 150 parts by weight of deionized water, and heated at 100 ° C. for 5 hours to obtain cellulose fibers was hydrolyzed to prepare a suspension containing a hydrolyzate of cellulose. The prepared suspension was centrifuged at 3,000 rpm for 15 minutes to remove the supernatant, and washed repeatedly 5 times with deionized water. Cellulose hydrolyzate was dissolved in deionized water, and then subjected to high pressure homogenization treatment at high pressure (1000 bar) for 180 minutes and filtered to obtain a filtrate containing nanocrystalline cellulose, and the obtained filtrate was dried to obtain nanocrystalline cellulose (thickness 10 to 20 nm, length 100 to 120 nm).

(3) Preparation of mixed solution

As shown in Table 1 below, the chitosan solution (CS) and the nano cellulose solution (NSS) were mixed in a weight ratio of 10:1, 5:1, 3:1, 1:1 and 1:2, respectively, and 150 to 200 A mixed solution was prepared by stirring at rpm for 2 hours, and the prepared mixed solution was reacted for 3 hours. That is, chitosan and nanocrystalline cellulose were mixed and reacted in a weight ratio of 10:1, 5:1, 3:1, 1:1 and 1:2, respectively.

(4) Preparation of composite antibacterial beads

The prepared mixed solution was supplied to a syringe pump, supplied to a syringe pump, and the mixed solution was dropped into 1M sodium hydroxide aqueous solution through a syringe provided in the syringe pump to prepare a reaction solution containing beads in a wet state, and prepared The mixed solution was freeze-dried at -20 °C to prepare composite antibacterial beads having an average particle size of 300 to 350 µm.

<Example 2>

Composite antibacterial beads in the same manner as in Example 1, except that 2 parts by weight of sodium tripolyphosphate as a curing agent was mixed with respect to 100 parts by weight of sodium hydroxide aqueous solution to prepare a first mixed coagulation solution, and the prepared first mixed coagulant was used. was prepared.

<Example 3>

A second mixed coagulation solution was prepared by mixing 2 parts by weight of sodium tripolyphosphate as a curing agent and 1 part by weight of tetraethoxysilane as a curing accelerator with respect to 100 parts by weight of an aqueous sodium hydroxide solution, except for using the prepared second mixed coagulating solution prepared a composite antibacterial bead in the same manner as in Example 1.

<Example 4>

In the same manner as in Example 1-3, a reaction solution containing beads in a wet state was prepared, the prepared reaction solution was heat-treated at 90 ° C. for 4 hours, and the heat-treated mixed solution was freeze-dried at -20 ° C. Beads (Example 4-1) were prepared.

In addition, in the same manner as in Example 2-3, a reaction solution containing beads in a wet state was prepared, the prepared reaction solution was heat-treated at 90 ° C. for 4 hours, and the heat-treated mixed solution was freeze-dried at -20 ° C. A composite antibacterial bead (Example 4-2) was prepared.

In addition, in the same manner as in Example 3-3, a reaction solution containing beads in a wet state was prepared, the prepared reaction solution was heat-treated at 90 ° C. for 4 hours, and the heat-treated mixed solution was freeze-dried at -20 ° C. A composite antibacterial bead (Example 4-3) was prepared.

<Example 5>

The complex antibacterial beads prepared by the method according to Example 4-3 were mixed with a water-soluble propolis mixed solution containing 10 parts by weight of water-soluble propolis powder and 90 parts by weight of distilled water, and then stirred for 3 hours to prepare a complex antibacterial bead reaction, , the prepared composite antibacterial bead reactant was dried to prepare a pre-treated composite antibacterial bead.

The water-soluble propolis powder is prepared by pulverizing a propolis mass to prepare a pulverized product, mixing 100 parts by weight of the prepared pulverized product with 50 parts by weight of water to prepare a reaction mixture, and heating the prepared reaction mixture at a temperature of 65° C. for 10 hours. 100 parts by weight of the propolis extract from which the suspended components were removed, the suspended components contained in the propolis were removed by heating for A water-soluble propolis powder prepared by mixing and diluting 40 parts by weight of polysorbate as a surfactant and 500 parts by weight of water and then mixing 10 parts by weight of L-arginine and drying was used.

<Example 6>

100 parts by weight of high-density polyethylene (HDPE) and 5 parts by weight of the composite antibacterial beads prepared by the method according to Example 4-3 to prepare an antimicrobial resin composition, and injection molding the prepared antimicrobial resin composition A container body for a cosmetic container was manufactured. A cosmetic container specimen was prepared by coating a coating mixture on the inner surface of the prepared container body to form a water and oil repellent layer having a thickness of 10 μm. The coating mixture is a fluorinated copolymer, 2-(perfluorohexyl)ethyl methacrylate 70 parts by weight, benzyl methacrylate 20 parts by weight, 2-hydroxyethyl methacrylate 5 parts by weight, ethylene glycol diglyceryl A mixture containing 20 parts by weight of a fluorinated copolymer containing 5 parts by weight of cidyl ether, 60 parts by weight of ethanol, 5 parts by weight of a zeolite powder (porous ceramic powder) having an average particle size of 1 to 3 μm, and 15 parts by weight of water is used. did.

<Example 7>

A cosmetic container having a structure in which a water and oil repellent layer and an antibacterial resin layer were formed was prepared in the same manner as in Example 6, except that the modified zeolite powder was used as the porous ceramic powder.

The modified zeolite powder is prepared by mixing 20 parts by weight of natural zeolite powder and 100 parts by weight of water to prepare a suspension, and 50 parts by weight of a mixed alcohol containing ethanol and 1,2-hexanediol in a weight ratio of 1:1 is mixed with the prepared suspension. and reacted for 2 hours to prepare a mixture containing pre-treated zeolite. A pre-treated zeolite was obtained from the prepared mixture, and then dried at a temperature of 120° C. for 8 hours to prepare a hydrophobic zeolite. 50 parts by weight of the prepared hydrophobic zeolite was mixed with 100 parts by weight of water to prepare a suspension, and then 50 parts by weight of a mixture comprising 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyltrichlorosilane in the prepared suspension The mixture was mixed and reacted at 65° C. for 3 hours to prepare a modified zeolite in which fluorine silane was introduced onto the surface.

<Comparative Example 1>

Antibacterial beads were prepared using the chitosan solution prepared in the same manner as in Example 1, except that the nano-cellulose solution was not introduced.

<Comparative Example 2>

After manufacturing the container body for the cosmetic container, the fluorinated copolymer on the inner surface of the container body contains 70 parts by weight of 2-(perfluorohexyl)ethyl methacrylate, 20 parts by weight of benzyl methacrylate, and 2-hydroxyethyl A coating mixture containing 5 parts by weight of methacrylate, 20 parts by weight of a fluorinated copolymer containing 5 parts by weight of ethylene glycol diglycidyl ether, and 60 parts by weight of ethanol, that is, a coating mixture containing no porous ceramic powder A cosmetic container specimen was prepared in the same manner as in Example 6 except for coating.

<Experimental Example 1>

(1) Measurement of solubility of composite antibacterial beads

The dry weight (W ₀ ) of the composite antibacterial beads prepared by the method according to Examples and Comparative Examples was measured, and the composite antibacterial beads were immersed in 5% acetic acid aqueous solution (volume ratio 5:95) and then washed three times with deionized water. , and dried at 100 ° C. for 12 hours to measure the weight (W _S ) after drying, and evaluate the solubility by measuring the contents of dissolved chitosan and nano cellulose using the following formula 1, and the results are shown in Table 2 below. . For solubility evaluation, the solubility (unit: %) of each sample prepared at 3-hour intervals was evaluated. For solubility evaluation, a mixture obtained by separately mixing chitosan powder and nano-cellulose powder was immersed in a 5% aqueous acetic acid solution and evaluated as a control.

[Equation 1]

S ₀ = (W ₀ - W _S ) / W ₀ × 100

As shown in Table 2, as a result of measuring the solubility of the composite antibacterial beads in an acidic solution, in the case of the composite antibacterial beads of Example 1 in which chitosan and nanocellulose were complexed compared to Comparative Example 1 prepared by dropping chitosan beads, nanocellulose was It was confirmed that the physical and chemical properties were improved as the solubility was greatly reduced by forming a strong network with chitosan.

In particular, it was confirmed that physical properties were further improved when a curing agent was added alone or a curing agent and a curing aid were mixed and cross-linked, and physical and chemical properties were improved even through heat treatment as in Example 4.

(2) Measurement of swelling degree of composite antibacterial beads

Bead swelling degree (S _w ) prepared by the method according to Examples and Comparative Examples was calculated and shown in Table 3 below. The degree of swelling (S _w ) was measured by measuring the dry weight (W ₀ ) of each prepared bead, immersing each bead in distilled water at room temperature (25 ℃) for 12 hours, and then immersing the weight (W _t ) was measured, It was calculated according to Equation 2 below.

[Equation 2]

S _w = (W _t - W ₀ ) / W ₀ × 100

As shown in Table 3, as a result of measuring the swelling degree of the composite antibacterial beads in an acidic solution, as in Example 1, as the content of nano-cellulose increased, a strong network was formed due to the complexation of chitosan and nano-cellulose, and the degree of swelling was greatly reduced. It was confirmed that the physicochemical properties of the composite antibacterial beads were improved even through the addition of a curing agent and curing accelerator and heat treatment.

(3) Strength evaluation of composite antibacterial beads

The compressive strength of the composite antibacterial beads prepared by the methods according to Examples and Comparative Examples was evaluated, and the results are shown in Table 4 below.

Compressive strength evaluation was performed by preparing a spherical bead specimen with a diameter of 5 mm, and the compressive strength (unit: kgf/cm ² ) was measured using a universal test analyzer, and the results are shown in Table 4.

As shown in Table 4, as a result of evaluating the compressive strength of the prepared composite antibacterial beads, it was determined that the strength of the composite antibacterial beads was greatly improved by the introduction of nano-cellulose, which formed a dense network structure in which chitosan and nano-cellulose were used.

In particular, it was confirmed that mechanical properties were further improved when a curing agent was introduced, and it was confirmed that physical properties could be improved even through heat treatment. It was confirmed that the mechanical properties could be further improved.

Through the above results, the composite antibacterial beads with improved mechanical properties do not deform even at high extrusion temperatures when used in molding plastic containers, films, sheets, etc. It was confirmed that it could be formed.

(4) Evaluation of antibacterial properties of composite antibacterial beads

The antibacterial properties of the composite antibacterial beads prepared by the methods according to Examples and Comparative Examples were evaluated. Antibacterial evaluation is based on JIS Z 2801:2000, a gram-negative strain Escherichia coli ATCC 8739 as the target strain, the initial number of bacteria 1.1 × 10 ⁶ cfu / mL to prepare a culture solution, and add beads to the prepared culture solution After incubation at a temperature of 35 ° C. for a certain period of time, after incubation for 24 hours at a relative humidity of 90%, the number of bacteria (unit: cfu/mL) was measured, and the results are shown in Table 5 below.

As a result of evaluating the antibacterial activity of the composite antibacterial beads prepared by the methods according to Examples and Comparative Examples, it was confirmed that the prepared beads had an excellent antibacterial effect at a level of 99.9% against E. coli, and due to the introduction of propolis, It was confirmed that the antibacterial properties were further improved.

(5) Antimicrobial persistence evaluation

The antimicrobial persistence of the composite antibacterial beads prepared by the methods according to Examples and Comparative Examples was evaluated. Antibacterial persistence evaluation was performed using a Gram ^- positive bacterium, Staphylococcus aureus ATCC 6538, as a target strain in accordance with KS K 0693:2001. After culturing to become , complex antibacterial beads were introduced into the culture medium and cultured to measure the reduction rate (unit: %) of the number of bacteria after 18 hours of incubation and 3 months of culture, and the results are shown in Table 6 below.

As a result of evaluating the antimicrobial persistence of the composite antibacterial beads prepared by the methods according to Examples and Comparative Examples, the mechanical properties of the composite antibacterial beads prepared by introducing a crosslinking agent and a crosslinking accelerator, respectively, were improved, even when in contact with the culture medium for a long time. On the other hand, it was confirmed that excellent antibacterial persistence, as in Examples 1-3 and 4-1, in the case of composite antibacterial beads prepared without using them, decomposition is promoted by biodegradability, so it is difficult to maintain antibacterial persistence for a long time. was able to confirm

(6) biodegradability evaluation

The biodegradability of the composite antibacterial beads prepared by the methods according to Examples and Comparative Examples was evaluated, and the results are shown in Table 7 below.

Biodegradability evaluation is performed by immersing the composite antibacterial bead sample in a buffer solution similar to body fluid for a certain time, measuring the weight of the composite antibacterial bead sample before immersion and the weight of the composite antibacterial bead sample after immersion, and then checking the weight reduction rate. did.

To this end, 2 g of a composite antibacterial bead sample having an average particle size of 500 μm was immersed in 50 mL of a phosphate buffered saline (PBS) buffer in which 40 mg of lysozyme was dissolved and reacted at room temperature for 30 days, Every 5 days, 5 mL of phosphate buffered saline in which lysozyme was dissolved in the same amount was added to maintain the enzyme activity, and the biodegradability of the composite antibacterial beads prepared in an environment similar to body fluid was evaluated. After 30 days have elapsed, the phosphate buffered saline is removed, the residual sample is washed and dried to obtain an undecomposed composite antibacterial bead sample, and the weight of the obtained sample is measured and immersed in phosphate buffered saline in which lysozyme is dissolved. The biodegradability was evaluated by comparing the weight with the whole complex antibacterial bead sample and measuring the weight reduction rate (unit: %).

As in Comparative Example 1, in the case of beads not introduced with nanocrystalline cellulose, it could be confirmed that the weight reduction rate was 98.3%, indicating rapid biodegradability, whereas, as in the composite antibacterial bead sample of Example 1, nanocrystalline cellulose and It can be confirmed that the weight reduction rate is greatly reduced by the complexation, and as in Example 2, the addition of a curing agent and a curing accelerator promotes crosslinking to control biodegradability, and heat treatment promotes crosslinking to control biodegradability. there was.

(7) Cytotoxicity evaluation

Cytotoxicity was evaluated to confirm the human safety of the composite antibacterial beads prepared by the method according to the example, and the results are shown in Table 8 below.

For cytotoxicity evaluation, NIH3T3 cells were dispensed in a 96-well plate so as to be 1 × 10 ⁴ cells per well, incubated for 8 to 12 hours, and then a composite antibacterial bead sample was added to each well so as to become 10 μg/mL 24 incubated for hours.

The cultured samples were obtained and the cell viability was confirmed by performing a CCK assay (cell counting kit assay), and the results are shown in Table 7 below. Cell viability was evaluated for each treatment group based on the cell viability (unit: %) of the control group (100%).

As a result of evaluating the cytotoxicity of the manufactured composite bead sample, the manufactured composite antibacterial bead does not show cytotoxicity, so it is not harmful to the human body even when ingested orally. was judged to be high.

<Experimental Example 2>

(1) Measurement of contact angle

The inner surface contact angle was measured using the cosmetic container specimen prepared by the method according to Examples 6 and 7. The contact angle was measured by a static method using a camera, and in order to evaluate the water repellency and oil repellency, respectively, the water contact angle and the hexadecane contact angle were measured, respectively, and the results are shown in Table 9 below. At this time, a cosmetic container containing only an antibacterial resin layer without forming a water and oil repellent layer was used as a control.

As shown in Table 9, it was confirmed that the water and oil repellent layer formed on the surface of the cosmetic container had high water repellency and oil repellency. In particular, it was confirmed that, when the modified zeolite was used, the water repellency and oil repellency were further improved, so that the properties of the water and oil repellent layer could be further improved.

Accordingly, it was confirmed that the cosmetic contents including the hydrophilic or hydrophobic component can form a structure that easily flows down from the inner wall surface.

(2) Measurement of the angle of fall

The drop angle was measured using the cosmetic container specimen prepared by the method according to Examples 6 and 7. Drop angle measurement is a method of measuring the angle at which dimethicone starts to flow by dropping 1 mL of dimethicone on the surface while placing the cosmetic container specimen in a horizontal state on the ground, and then tilting the cosmetic container specimen. was evaluated, and the results are shown in Table 9 above.

As shown in Table 9, it was confirmed that the water-oil-repellent layer formed on the surface of the cosmetic container has excellent oil repellency, so that it is possible to form a structure that allows the silicone oil component to easily flow down even in a state where the drop angle is very low.

The detailed description of the preferred embodiments of the present invention disclosed as described above is provided to enable any person skilled in the art to make and practice the present invention. Although the above has been described with reference to preferred embodiments of the present invention, it will be understood by those skilled in the art that various modifications and changes can be made to the present invention without departing from the scope of the present invention. For example, a person skilled in the art may use each configuration described in the above-described embodiments in a way that is combined with each other. Accordingly, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

The present invention may be embodied in other specific forms without departing from the spirit and essential characteristics of the present invention. Accordingly, the above detailed description should not be construed as restrictive in all respects but as exemplary. The scope of the present invention should be determined by a reasonable interpretation of the appended claims, and all modifications within the equivalent scope of the present invention are included in the scope of the present invention. The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. In addition, claims that are not explicitly cited in the claims may be combined to form an embodiment, or may be included as new claims by amendment after filing.

100: cosmetic container
101: antibacterial resin layer
103: water and oil repellent layer
105: barrier layer for gas barrier
107: UV blocking layer

Claims (5)

An antimicrobial resin layer comprising an antimicrobial agent and a polymer resin; and a water and oil repellent layer formed on the inner surface of the antimicrobial resin layer;
The water and oil repellent layer,
An antibacterial cosmetic container, characterized in that it is formed by laminating a mixture comprising 10 to 30 parts by weight of a fluorinated copolymer, 70 to 90 parts by weight of a solvent, and a porous ceramic filler on the inner surface of the antimicrobial resin layer. According to claim 1,
The antibacterial agent is silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), titanium dioxide (TiO ₂ ), chitosan, silver (Ag) supported zirconium phosphate, silver (Ag) supported calcium phosphate , silver (Ag) supported apatite phosphate, silver (Ag) supported silica gel, activated carbon, shell powder, egg shell powder, phytoncide, propolis, xylitol, capsaicin, curcumin, berberine, allicin, acacetin, carvacrol, mastic, catechin Antibacterial cosmetic container, characterized in that it contains one or more selected from the group consisting of complex antibacterial beads comprising , genton, robinin, chitosan and nanocellulose. According to claim 1,
The polymer resin is polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate resin, polyvinyl chloride (polyvinyl chloride), polystyrene (polystylene), polycarbonate ( polycarbonate, acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, methylmathacrylate butadiene styrene copolymer, polylactic acid resin acid), nylon resin (nylon), polyvinylidene chloride, poly acetal, polyacrylate, poly methyl methacrylate, fluoropolymer, poly Urethane, polyester elastomer, melamine, urea, polyamide, polyphenylene sulfide, ethylene vinylacetate, polyvinyl acetate (polyvinylacetate), natural rubber, antibacterial cosmetic container comprising at least one selected from the group consisting of synthetic rubber. According to claim 1,
Antibacterial cosmetic container, characterized in that it further comprises a gas barrier barrier layer formed on the outer surface of the antimicrobial resin layer. According to claim 1,
The porous ceramic filler comprises a modified zeolite,
The modified zeolite is
(1) preparing a suspension by mixing 5 to 50 parts by weight of zeolite powder and 100 parts by weight of water; (2) mixing 10 to 100 parts by weight of a mixed alcohol containing ethanol and 1,2-hexanediol in a weight ratio of 1:1 to the suspension, and reacting for 0.5 to 6 hours to prepare a mixture containing pretreatment zeolite ; (3) obtaining a pre-treated zeolite from the mixture and then drying at a temperature of 80 to 200° C. for 6 to 24 hours to obtain a hydrophobic zeolite; (4) 10 to 100 parts by weight of the hydrophobic zeolite is mixed with 100 parts by weight of water to prepare a mixture containing the hydrophobic zeolite, and 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyl trichlorosilane are included in the prepared mixture 10 to 100 parts by weight of the mixture, and reacted at 40 to 70° C. for 1 to 12 hours to prepare a modified zeolite having fluorine silane introduced to the surface.

Images