KR102586655B1 - Antibacterial cosmetic container - Google Patents

Abstract

The present invention relates to an antibacterial cosmetic container, which is equipped with a water-repellent and oil-repellent layer to allow the cosmetic contents to easily flow down from the inner wall, thereby reducing the residual amount of the cosmetic contents on the inner wall, making it easy to recycle, and exhibiting excellent antibacterial activity against harmful microorganisms. This is about the cosmetic container it represents.
A cosmetic container according to the present invention includes an antibacterial resin layer containing an antibacterial agent and a polymer resin; And the antibacterial resin layer includes a water- and oil-repellent layer formed on the inner surface, wherein the water- and oil-repellent layer is a mixture containing 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 is characterized by being formed by lamination on the inner surface of an antibacterial resin layer.

Description

Antibacterial cosmetic container}

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

In general, packaging containers are used to protect the contents safely by preventing loss, contamination, or deformation in natural environments such as temperature, humidity, light, and microorganisms when manufacturing, transporting, and storing the contents. Recently, the price To ensure competitiveness, they are being replaced by plastic containers.

However, unlike containers made of glass or metal, plastic containers are permeable, so the contents can easily deteriorate and become contaminated with microorganisms. Therefore, preservatives and preservatives are used to store the contents stably for a long time. Chemical materials are added together, but as the harmfulness of preservatives or preservatives has emerged and consumer anxiety has increased, various studies have been conducted on methods of imparting antibacterial properties to the packaging container itself in an effort to remove or reduce preservatives and preservatives. is in progress.

Meanwhile, cosmetics are generally equipped with a cosmetic container having a structure that can be opened and closed with a cover and a container body, or a container body in the form of a bottle with a certain depth, and a pump coupled to the top of the container body to pump and discharge the contents. It is stored in a cosmetics container with a structure that can be used, and only when applying makeup, a certain amount of cosmetics is used or discharged from the cosmetic container.

However, when existing cosmetic containers contain and store mucus-like cosmetic contents 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 completely used from the cosmetic container. The downside is that it is cumbersome to do.

In addition, such cosmetic containers have problems such as residue remaining in the container and requiring washing for recycling, and various methods to supplement this 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 the stopper to discharge the contents of the container body, a push button coupled to the upper part of the body, and a body It includes a double pump at the bottom that suctions and discharges the contents of the container body and pressurizes the air inside the container body, wherein the double pump includes a contents suction part that suctions the contents inside the container body and discharges them to the outside; It is composed of a double portion including an air pressurizing part that introduces air from the outside of the container body and increases air pressure by injecting the air into the upper space inside the container body, and the contents suction part and the air pressurizing part of the double pump are partition walls. A pump container has been disclosed that is characterized in that it is separated into a container, and is provided with a means for removing the inner wall of the container, which pushes the inner wall of the container to the bottom so that it does not remain.

However, the pump container having the structure disclosed in Document 1 is made up of many components and their combinations to remove residues remaining on the inner wall of the container, and has a very complicated structure and has the problem of being cumbersome to manufacture. Research is needed on ways to supplement this.

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

The present invention was devised to solve the problems of the prior art as described above, and aims to provide technical details on a cosmetic container that can be easily recycled by significantly reducing the amount of remaining cosmetic content adhering to the inner wall.

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

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 will be clearly understood by those skilled in the art from the description below. It could be.

In order to achieve the technical problem described above, the present invention includes an antibacterial resin layer containing an antibacterial agent and a polymer resin; and a water and oil repellent layer formed on the inner surface of the antibacterial resin layer, wherein the water and oil repellent layer is a mixture containing 10 to 30 parts by weight of a fluorinated copolymer, 70 to 90 parts by weight of a solvent and a porous ceramic filler. A cosmetic container is provided, which is formed by laminating an antibacterial resin layer on the inner surface.

In addition, the antibacterial agent includes silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), titanium dioxide (TiO ₂ ), chitosan, silver (Ag) supported zirconium phosphate, and 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, zenthone, robinin, chitosan, and nanocellulose.

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

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

In addition, the porous ceramic filler includes modified zeolite, which includes the steps of (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 mixed alcohol containing ethanol and 1,2-hexanediol in a weight ratio of 1:1 with the suspension and reacting for 0.5 to 6 hours to prepare a mixture containing pretreated zeolite ; (3) obtaining a pretreated zeolite from the mixture and then drying it 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 the prepared mixture includes 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyl trichlorosilane. A product prepared by a method comprising the step of mixing 10 to 100 parts by weight of the mixture and reacting at 40 to 70° C. for 1 to 12 hours to prepare a modified zeolite with fluorine silane introduced to the surface can be used.

The cosmetic container according to the present invention has a structure in which the cosmetic contents easily flow down from the inner wall by gravity, allowing all the cosmetic contents to be used, and is not only easy to clean but also easy to recycle. 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.

Below, with reference to the attached drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, since the description of the present invention is only an example for structural and functional explanation, the scope of the present invention should not be construed as limited by the examples described in the text. In other words, since the embodiments can be modified in various ways and can take various forms, the scope of rights of the present invention should be understood to include equivalents that can realize the technical idea. In addition, the purpose or effect presented in the present invention does not mean that a specific embodiment must include all or only such effects, so the scope of the present invention should not be understood as limited thereby.

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

Terms such as “first” and “second” are used to distinguish one component from another component, and the scope of rights should not be limited by these terms. For example, a first component may be named a second component, and similarly, the second component may also be named a first component. When a component is referred to as being “connected” to another component, it should be understood that it may be directly connected to the other component, but that other components may also exist in between. On the other hand, when a component is referred to as being “directly connected” to another component, it should be understood that there are no other components in between. Meanwhile, other expressions that describe the relationship between components, such as "between" and "immediately between" or "neighboring" and "directly neighboring" should be interpreted similarly.

Singular expressions should be understood to include plural expressions, unless the context clearly indicates otherwise, and terms such as “comprise” or “have” refer to the specified features, numbers, steps, operations, components, parts, or them. It is intended to specify the existence of a combination, and should be understood as not excluding in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

All terms used herein, unless otherwise defined, have the same meaning as commonly understood by a person of ordinary skill in the field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as consistent with the meaning they have in the context of the related technology, and cannot be interpreted as having an ideal or excessively formal meaning unless clearly defined in the present invention.

Hereinafter, the present invention will be described in detail.

Figure 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 includes an antibacterial resin layer 101 containing an antibacterial agent and a polymer resin; and a water- and oil-repellent layer 103 formed on the inner surface of the antibacterial resin layer 101, which can reduce the amount of residue on the inner wall, making it easy to recycle, and exhibits excellent antibacterial activity against harmful microorganisms, so it can be used in cosmetics. It can be stored safely 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 the container, and contains the cosmetic contents, including the antibacterial agent. It is possible to form a cosmetic container 100 that can safely accommodate and store.

Antibacterial agents include silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), titanium dioxide (TiO ₂ ), chitosan, and silver (Ag)-supported ceramic powder (zirconium phosphate, calcium phosphate, apatite). phosphate, silica gel), activated carbon, shell powder, eggshell powder, phytoncide, propolis, xylitol, capsaicin, curcumin, berberine, allicin, aca Antibacterial substances such as acetin, carvacrol, mastic, catechin, xantone, robinin, or mixtures thereof can be used, and when mixed with polymer resin, It can effectively inhibit the growth of harmful microorganisms such as E. coli and mold. Preferably, the antibacterial agent may include composite antibacterial beads that combine chitosan and nanocellulose and do not easily lose antibacterial properties even at high temperatures. Details regarding the composite antibacterial beads will be described in more detail below.

The antibacterial resin layer 101 can be formed using a polymer resin as a binder, and the polymer resin is polyethylene, polypropylene, polyethylene terephthalate, and polybutylene terephthalate. ) Resin, polyvinyl chloride, polystyrene, polycarbonate, acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, methyl meta Crylate butadiene styrene copolymer, polylactic acid, nylon, polyvinylidene chloride, polyacetal, polyacrylate. , poly methyl methacrylate, fluoropolymer, polyurethane, polyester elastomer, melamine resin, urea, polyamide, poly Phenylene sulfide, ethylene vinylacetate, poly vinylacetate, natural rubber, synthetic rubber, or mixtures thereof can be used.

The antibacterial resin composition can be manufactured by mixing an antibacterial agent in a polymer resin, and may contain an antibacterial agent in a ratio of 0.1 to 20 parts by weight relative to 100 parts by weight of the polymer resin. If the content of the antibacterial agent is less than 0.1 part by weight, there is a risk of deteriorating antibacterial properties. And, if it exceeds 20 parts by weight, there is a risk that mechanical properties may deteriorate.

In this way, the cosmetic container 100 can provide excellent antibacterial properties by providing an antibacterial resin layer 101 containing an antibacterial agent inside, thereby reducing the use of preservatives such as chemicals known to be harmful to the human body. You can avoid using it and extend the shelf life of the product.

However, in Figure 1, a bottle-shaped cosmetic container 100 that can be used as a pump-type cosmetic container 100 or an airless cosmetic container 100 is shown, but is not limited to this structure and can be used in various container-shaped structures. It can be implemented as:

In addition, the antibacterial resin layer 101 may be molded using a mold with irregularities, or may be pretreated with a pretreatment method such as sandblasting to form an uneven surface to have a surface roughness of 0.1 to 10 ㎛, thereby producing a The water and oil repellent performance provided by the water and oil repellent layer 103 can be further improved, and the adhesion of each layer laminated on the surface of the antibacterial 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 antibacterial resin layer 101.

The water- and oil-repellent layer 103 provides water-repellent and oil-repellent properties to the cosmetic container 100, preventing the cosmetic contents contained in the internal accommodation space of the cosmetic container 100 from adhering to the inner wall of the container and moving downward by gravity. By forming a structure that allows the cosmetics to flow easily, the contents of the cosmetics can be used without any residue. As a result, the cleaning process for recycling the cosmetics container 100 can be simplified because the residual amount of the cosmetics contents is low. It improves recyclability, and cosmetics containing highly viscous oil ingredients such as silicone oil emollients can also be easily stored.

The water and oil repellent layer 103 is a coating mixture containing 10 to 30 parts by weight of a fluorinated copolymer (or 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 can be formed by coating or laminating the inner surface of the resin layer 101.

The fluorine-containing copolymer has excellent adhesion and enables the formation of a water- and oil-repellent layer 103 having uniform water and oil repellency over the entire surface of the inner surface of the antibacterial resin layer 101. As a result, Alternatively, a structure may be formed so that the cosmetic contents containing oily ingredients do not adhere to the inner wall of the cosmetic container 100 but flow down by gravity.

Specifically, the fluorinated copolymer includes perfluoroalkyl acrylate, benzyl methacrylate, polyfluorooctyl methacrylate, and 2-N,N-diethylamino. Ethyl methacrylate (2-N,N-diethylaminoethyl methacrylate), 2-hydroxyethyl methacrylate, 2,2'-ethylenedioxydiethyl dimethacrylate) or a copolymer containing one or more types of monomers thereof can be used.

Specifically, perfluoroalkyl acrylates such as 2-(perfluorohexyl)ethyl methacrylate provide water and oil repellent properties to the inner wall of the cosmetic container, allowing the cosmetic contents to flow down from the inner wall of the container by gravity. . Perfluoroalkyl acrylate can be mixed at a ratio of 60 to 80 parts by weight. If the content of perfluoroalkyl acrylate is less than 60 parts by weight, it is difficult to create a water- and oil-repellent layer with uniform water and oil repellent performance, and 80 parts by weight is used. 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, forming a structure in which the water- and oil-repellent layer does not easily separate from the antibacterial resin layer even when an external impact or shape deformation of the antibacterial resin layer is applied, creating a uniform thickness of the foot. Allow a water-oil layer to form. Benzyl methacrylate can be mixed in a ratio of 10 to 30 parts by weight. If the content is less than 10 parts by weight, there is a risk that flexibility may be reduced, and if the content exceeds 30 parts by weight, there is a risk that the bonding strength of the water-repellent and oil-repellent layer may be reduced.

2-Hydroxyethyl methacrylate increases the adhesion of the water- and oil-repellent layer and strongly bonds the modified zeolite, which is a filler, so that the water- and oil-repellent layer is strongly bonded to the antibacterial resin layer. It can be mixed at a ratio of 1 to 10 parts by weight. If the content of 2-hydroxyethyl methacrylate is less than 1 part by weight, there is a risk that the bonding strength may decrease.

Ethylene glycol diglycidyl ether serves to improve mechanical properties by crosslinking each of the above-mentioned monomers, and can be mixed at a ratio of 1 to 10 parts by weight. If the content of ethylene glycol diglycidyl ether is less than 1 part by weight, there is a risk that the mechanical properties of the water and oil repellent layer may deteriorate and the water and oil repellent layer may be easily damaged by friction, external shock, etc., and if it exceeds 10 parts by weight, the water and oil repellent layer may be easily damaged. It is difficult to expect further improvement in physical properties.

Preferably, the fluorinated copolymer contains 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 dihydrogen. A mixture containing 5 parts by weight of glycidyl ether can be used.

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

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

The porous ceramic filler may have an average particle size of 0.1 to 20 ㎛, and provides sufficient mechanical properties to the water and oil repellent layer 103, and forms a fine uneven structure on the surface of the water and oil repellent layer 103 to provide water and oil repellent properties. It plays a role in improving oil repellent performance and contains porous structures such as zeolite, silica, illite, bentonite, kaolinite, zeolite, elvanite, sericite, attapulgite, alominosilicate, activated carbon, sepiolite, smectite, calcium carbonate, shell, Egg shells or mixtures thereof can be used.

Preferably, the porous ceramic filler may include a modified zeolite that exhibits antibacterial activity and further improves water and oil repellent performance, and the modified zeolite has a large amount of finely structured pores formed on the surface, and the fluorine silane The surface is modified with a compound to form a fine uneven structure on the surface of the five layers, improving water and oil repellent performance.

The modified zeolite is prepared by mixing 5 to 50 parts by weight of zeolite powder and 100 parts by weight of water, and the prepared suspension is mixed with 10 to 100 parts of alcohol containing ethanol and 1,2-hexanediol in a weight ratio of 1:1. Parts by weight are mixed, reacted for 2 hours, pretreated zeolite is obtained from the reaction mixture, and then dried at a temperature of 80 to 200 ° C. for 6 to 24 hours to obtain hydrophobic zeolite. A suspension was prepared by mixing 10 to 100 parts by weight of the hydrophobic zeolite as described above with 100 parts by weight of water, and then the prepared suspension was mixed with 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyltrichlorosilane. Modified zeolite with fluorine silane introduced to the surface can be prepared by mixing 10 to 100 parts by weight of the mixture and reacting at 40 to 70 ° C. for 1 to 12 hours.

The mixture as described above has a fine uneven structure formed by the porous ceramic powder present on the surface, and only a very limited area is in contact with the protrusions of the water- and oil-repellent surface with low surface energy due to the fluorine-containing copolymer covering the surface. As a result, the surface tension is greatly reduced, making it possible to form a water- and oil-repellent layer 103 with excellent water- and oil-repellent performance that prevents the adhesion of both water-based and oil-based components.

Meanwhile, the modified zeolite can be manufactured using natural zeolite powder, but surface-treated and modified zeolite prepared by hydrophobicizing surface-treated zeolite and then reacting it with perfluorodecyl trichlorosilane can also be used.

Specifically, the surface-treated zeolite includes the steps of (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; a product prepared by a method including the following can be used.

The surface-treated zeolite is prepared by mixing zeolite powder with water, and the zeolite powder and water can be mixed and then stirred to ensure that the 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. A suspension can be prepared by mixing the parts.

When the suspension containing zeolite powder is supplied to the electrolysis device as described above and then voltage is applied, the water contained in the suspension is electrolyzed to form hydrogen gas and oxygen gas, which can generate excessive bubbles, and the zeolite powder Excessive bubbles are formed in the water absorbed into the zeolite powder, resulting in the formation of a large number of pores on the surface of the zeolite powder. As a result, the surface area of the surface-treated zeolite powder particles is greatly increased, so that the surface modifier to be described later comes into contact with the zeolite powder particles. The reaction surface area can be expanded, and modified zeolite can be easily manufactured using surface-treated zeolite powder particles. Surface-treated zeolite has additional pores, which improves antibacterial activity and has fine irregularities on the surface. This formation can further improve water and oil repellency performance.

The surface-treated zeolite as described above is reacted with ethanol and 1,2-hexanediol to prepare hydrophobic zeolite in the same manner as the above-described modified zeolite production method, and then subjected to surface treatment by reacting with fluorodecyl trichlorosilane. And modified zeolite can be produced.

In addition, the cosmetic container 100 according to the present invention can be configured to additionally include a gas blocking barrier layer 105 formed on the outer surface of the antibacterial resin layer 101, and the gas blocking barrier layer 105 It plays a role in safely protecting the cosmetic contents contained within by suppressing the penetration of gas.

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

The cosmetic container 100 according to the invention can be configured to additionally include a UV-blocking layer 107 formed on the outer surface of the antibacterial resin layer 101, and the UV-blocking layer 107 is attached to 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 blocking performance.

In addition, the UV blocking layer 107 is coated with a coating composition containing 5 to 15 parts by weight of polyvinyl butyral, 80 to 90 parts by weight of acrylic monomer, 0.1 to 1 part by weight of photoinitiator, and 0.5 to 5 parts by weight of ultraviolet absorber. It can be formed to a thickness of 5 to 30 ㎛. The ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-ditertibutylphenyl)-benzotriazole, and benzotriazole. Sol-based compounds can be used.

Meanwhile, the cosmetic container 100 according to the present invention includes composite antibacterial beads in the antibacterial resin layer 101, and the composite antibacterial beads can be manufactured by the following method.

A method for producing composite antibacterial beads according to a preferred embodiment of the present invention includes 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) preparing a nanocellulose solution by mixing 1 to 50 parts by weight of nanocellulose with 50 to 99 parts by weight of a solvent; (c) preparing a mixed solution by mixing the chitosan solution and the nanocellulose solution at a weight ratio of 10:1 to 1:10, respectively; and (d) preparing composite antibacterial beads using the mixed solution.

The step (a) is a step of preparing a chitosan solution, and the chitosan solution can be prepared by mixing chitosan powder with an acidic solvent.

Chitosan is manufactured by deacetylating chitin, a natural polymer polysaccharide present in the outer shell of crustaceans such as crabs, shrimp, and crayfish, the skeleton of molluscs such as squid, the exoskeleton of insects, and the cell walls of fungi such as molds, yeasts, and mushrooms. , D-glucosamine is a β-(1→4) glycosidic copolymer.

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

Chitosan powder can be prepared 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 to give an average Those with a particle size of 10 to 2,000 ㎛ can be used.

If the average particle size of the chitosan powder is less than 10 ㎛, it is difficult to improve the mechanical properties due to the small amount of nanocellulose introduced, and if it exceeds 2,000 ㎛, there is a risk that the antibacterial activity may decrease due to the decrease in surface area.

Additionally, the chitosan solution can be prepared by mixing chitosan powder and an acidic solvent, and can be prepared by mixing 1 to 50 parts by weight of chitosan powder with 50 to 99 parts by weight of an acidic solvent.

Acidic solutions for preparing chitosan solutions include 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 using a mixture of these and has a pH of 3 to 6, and an acidic aqueous solution containing them can be used.

Preferably, the chitosan solution can 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 can 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 that make up the cell walls of microorganisms are An ionic bond is created with the amino group of cationized chitosan, and as a result, the cell membrane tissue on the other side of the contact surface is destroyed due to the polarization of phospholipids in the cell membrane, exposing the protoplasm within the cell and killing microorganisms, and the positive ions of chitosan destroy cell DNA. It can react with and inhibit the synthesis of RNA and proteins. Therefore, the antimicrobial effect persists as long as the ammonium cations of chitosan can contact microorganisms.

In addition, the antibacterial properties of chitosan are expressed by acting as a chelating agent that selectively binds to trace amounts of metal elements, causing toxin production and inhibiting the growth of microorganisms.

Chitosan, which exhibits antibacterial properties as described above, actually generates a membrane potential as some of its amino groups are protonated in water, and it contains an excessive amount of hydroxyl groups, so it swells easily when in contact with water, but it does not dissolve because most of the hydrogen bonds between molecular chains are not broken. It is insoluble, but when in contact with water, mechanical properties are greatly reduced, and due to insufficient heat resistance, there is a problem of loss of antibacterial properties when processing high temperature mechanical molding processes such as extrusion. Therefore, in the present invention, nanocellulose is added to chitosan. By introducing this, it is possible to manufacture composite antibacterial beads with improved heat resistance and mechanical properties along with antibacterial properties.

In step (b), a nanocellulose solution can be prepared by mixing nanocellulose with a solvent.

Nano cellulose is a natural polymer that has high crystallinity, excellent physical strength, heat resistance, and transparency, and is biodegradable. It is also introduced into the chitosan tissue to form a network to protect bonds from separation. The physicochemical properties of chitosan can be improved by strengthening or protecting chitosan tissue bonding.

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, so it has a molecular structure similar to chitosan. The cellulose chains are combined to form a bundle, so the tensile elastic modulus is similar to that of steel or Kevlar, the density is low, and the specific surface area is large. As a bio-based material, it can be introduced into the tissues of chitosan to improve the physicochemical properties of chitosan.

Nanocellulose can be manufactured using various common cellulose raw materials used to manufacture it, but is preferably made from rice straw, barley straw, corn stalks, cotton stalks, sugar cane, bamboo, kenaf, and cotton. Products manufactured using cellulose raw materials including linter, wood, or mixtures thereof can be used, and nanocellulose manufactured using such cellulose raw materials is a safe natural material that does not adversely affect the human body even when ingested.

In addition, nanocellulose can be introduced with an average width of 2 to 300 nm and an average length of 100 to 2,000 nm, and if the width and length of nanocellulose are outside the above range, the nanofiber cellulose Problems may arise such as difficulty in uniform introduction.

The nanocellulose is manufactured by adding chemical treatment by acid hydrolysis to cellulose nanofibril (CNF), which is manufactured by mechanically processing cellulose raw materials using a high-pressure homogenizer or milling machine. It may include cellulose nanocrystal (CNC), bacterial cellulose, or mixtures thereof.

Specifically, the nanofibrous cellulose may be used with 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 may have a width of 2 to 20 nm and a length of 100 nm. to 600 nm and an aspect ratio of 1 to 5 can be used, and preferably, nanocrystalline cellulose can be introduced.

In this step, a nanocellulose solution can be prepared by mixing 1 to 50 parts by weight of nanocellulose with 50 to 99 parts by weight of a solvent. If the content of nanocellulose is less than 1 part by weight, it is difficult to expect a sufficient improvement in physical properties, and 50 parts by weight is used. If it is exceeded, there is a problem that the viscosity increases significantly due to the formation of hydrocolloid, making complexation with chitosan difficult. Preferably, a nanocellulose solution can be prepared by mixing 1 to 5 parts by weight of nanocrystalline cellulose with 100 parts by weight of ethanol. there is.

The nanocellulose is insoluble in general solvents and water due to complex hydrogen bonds and high crystallinity, and can be manufactured using a solvent that can evenly disperse nanocellulose.

The nanocellulose solution uses ethanol, methanol, butanol, propanol, isopropanol, acetate, acetone, or mixtures thereof as a solvent to produce nanocellulose. A uniformly dispersed nanocellulose solution can be prepared.

In step (c), a mixed solution is prepared by mixing the chitosan solution and the nanocellulose solution.

In this step, the mixed solution can be prepared by mixing the chitosan solution and the nanocellulose solution at a weight ratio of 10:1 to 1:10, respectively. If the weight ratio is outside the above range, it is difficult to expect additional physical property improvement effects due to the introduction of nanocellulose.

If the content of the nanocellulose solution in the mixed solution is low, it is difficult to expect sufficient improvement in physical properties. If the content is excessive, it is difficult to expect additional improvement in physical properties, and uniform dispersion of nanocellulose becomes difficult.

In this step, the chitosan solution and nanocellulose solution can be mixed and then continuously stirred or vibration can be provided to uniformly introduce nanocellulose into the porous structure of chitosan.

In step (d), a composite antibacterial bead is prepared using a mixed solution. The composite antibacterial bead can be manufactured by curing the chitosan and nanocellulose by forming an amide bond and an ester bond in the chitosan and nanocellulose.

In this step, a mixed solution containing chitosan and nanocellulose is prepared, such as a method of dropping the coagulating liquid into the mixed solution, a method of dropping the mixed solution into the coagulating liquid, or a method of mixing the coagulating liquid with the mixed solution and molding it using a molding device. Complex antibacterial beads can be manufactured using a variety of common methods for manufacturing beads.

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

In addition, according to a preferred embodiment of the present invention, in this step, the coagulating liquid is added dropwise to the mixed solution to coagulate the chitosan and nanocellulose contained in the mixed solution to prepare a reaction solution containing composite antibacterial beads in a wet state, Complex antibacterial beads can be obtained by drying the prepared reaction solution.

Coagulating solutions that can be used to manufacture composite antibacterial beads include sodium hydroxide (NaOH), sodium bicarbonate (NaHCO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), and 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 can be used.

The coagulating solution can be an alkaline aqueous solution containing these substances at a concentration of 0.1 to 5M to promote coagulation. If the concentration of the coagulating solution is less than 0.1M, the coagulation time of chitosan and nanocellulose is long and the strength of the composite antibacterial bead is reduced. There is a risk of deterioration, and if it exceeds 5M, composite beads with non-uniform particle sizes may be generated.

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

The curing agent promotes crosslinking of chitosan and nanocellulose by inducing amide bonds and ester bonds, suppressing the swelling and solubility of the composite antibacterial beads and simultaneously improving mechanical properties.

Hardeners include sodium tripolyphosphate, β-glycerophosphate, glyoxal, 1-butyl-3-methylimidazolium chloride, and glue. Glutaraldehyde, epichlorohydrin, diisocyanate, 1-ethyl-3(3-dimethyl aminopropyl) carbodiimide, hydroxysuccinimide (N- hydroxysuccinimide, ethylene diamine, dimethylaminopropyl ethylcarbodiimide hydrochloride, hydroxybenzotriazole, diisopropylcarbodiimide, or mixtures thereof can be used. there is. Preferably, the cross-linking agent may be 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 nanocellulose to further improve the mechanical properties of the composite antibacterial bead, and the curing accelerator includes triethoxysilane, tetraetoxysilane, and lauroyl chloride. (lauroyl chloride) or a mixture thereof can be used.

The curing agent and curing accelerator can affect the crosslinking of chitosan and nanocellulose and adjust the strength and biodegradability of the composite antibacterial bead depending on the added content.

The curing agent and curing accelerator may each be introduced at a ratio of 0.1 to 10 parts by weight relative to 100 parts by weight of the coagulating liquid. If the content is less than 0.1 part by weight, it is difficult to expect sufficient improvement in physical properties, and if the content exceeds 10 parts by weight, composite antibacterial beads The mechanical properties can be further improved, but there is a risk that the antibacterial properties may decrease due to the loss of pores formed on the surface.

In addition, in this step, composite antibacterial beads with improved heat resistance and antibacterial activity can be manufactured by additionally introducing metal oxide into the coagulating 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 metal oxide relative to 100 parts by weight of coagulating solution, the metal oxide can be introduced into the structure of the composite antibacterial bead to enhance antibacterial properties and produce composite antibacterial beads with improved heat resistance.

In addition, this step may further include preparing a reaction solution in which wet beads are formed and heat-treating the prepared reaction solution, thereby producing composite antibacterial beads with further improved mechanical properties.

For this purpose, in this step, heat treatment can be performed by heating the reaction solution containing wet composite antibacterial beads at a temperature of 80 to 150 ° C for 1 to 12 hours. Through this heat treatment, chitosan and nanocellulose crosslinking can be further promoted.

In addition, in this step, a reaction solution containing wet composite antibacterial beads is prepared, and then the prepared reaction solution is dried using drying methods such as room temperature drying, heat drying, vacuum drying, and freeze drying to prepare composite antibacterial beads. Preferably, composite antibacterial beads with a porous structure can be manufactured using a freeze-drying method.

In this step, the particle size can be controlled according to the outlet diameter of the syringe or needle used to drop the mixed solution or coagulant, and composite antibacterial beads with an average particle size of 0.01 to 10 mm can be manufactured.

In addition, this step can be configured to further include the step of preparing the composite antibacterial beads and then impregnating the composite antibacterial beads into the propolis extract, whereby pretreated composite antibacterial beads with improved antibacterial activity can be manufactured. there is.

The propolis extract is prepared by pulverizing propolis lumps, mixing 100 parts by weight of the 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. This is carried out by heating for 6 to 12 hours, the supernatant is removed at intervals of 20 to 60 minutes, the suspended components contained in the propolis are removed by mixing the same amount of water as the amount of the removed supernatant, and the suspended components are removed from the propolis. A water-soluble propolis extract prepared by diluting 100 parts by weight of the extract with 40 parts by weight of polysorbate, a surfactant, and 100 to 500 parts by weight of water, and then mixing 10 parts by weight of amino acids can be used.

The composite antibacterial beads manufactured by the above-described method exhibit excellent antibacterial properties by introducing nanocellulose into the chitosan tissue, and have improved physicochemical properties, showing stable antibacterial activity for a long time, excellent biodegradability, and when ingested. Since it does not cause any adverse effects on the human body, it can be used as an antibacterial additive in the manufacture of food, cosmetics, and plastic molded products.

As described above, the cosmetic container 100 according to the present invention has a transparent or opaque structure and is a pump-type cosmetic container, cover, and container body having a structure including a pump cap and container body for discharging the cosmetic contents by pumping. A cosmetic container for cream that is provided with a structure that allows the cosmetic contents to be dispensed by opening the cover, a cap provided with a dropper for sucking the cosmetic contents so that the cosmetic contents can be dispensed by pressurization, and a container body. It can form a container body such as a dropper-type cosmetic container, and can also be used as a tube-type cosmetic container. It includes an antibacterial resin layer (101) and a water- and oil-repellent layer (103) to safely protect the cosmetic contents for a long time. there is.

In particular, cosmetics containing highly viscous oil ingredients such as silicone oil emollients can be easily stored as cosmetics can be used without any residue remaining on the internal walls. In addition, cosmetics contents remaining on the internal walls can be easily stored. can be easily removed through washing, thereby simplifying the cleaning process and promoting recycling of the cosmetic container 100.

Therefore, cosmetic contents of various formulations such as essence, cream, serum, toner, lotion, skin, oil, ampoule, etc. can be safely stored and accommodated.

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 manufacture a cosmetic container that includes an antibacterial resin layer and has a container-shaped structure. The manufactured cosmetic container can be used as a container body for 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 gas blocking barrier layer 105, and the ultraviolet ray blocking layer 107 can each be formed by coating using various conventional coating methods such as spraying, dipping, and brushing.

Hereinafter, the present invention will be described in more detail through 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 with a degree of deacetylation of 85% and an average molecular weight (Mw) of 550,000 to 600,000 was ground and sieved to prepare chitosan powder with an average particle size of 100 ㎛. A colloidal chitosan solution was prepared by mixing 6 parts by weight of the prepared chitosan powder with 200 parts by weight of acetic acid aqueous solution at pH 4.

(2) Preparation of nanocellulose solution

6 parts by weight of nanocrystalline cellulose with 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 prepare a cellulose solution in which the nanocrystalline cellulose was uniformly dispersed and in a suspension state.

Nanocrystalline cellulose was prepared as follows and used as shown in Figure 2.

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

(3) Preparation of mixed solution

As shown in Table 1 below, chitosan solution (CS) and nanocellulose solution (NSS) were mixed at a weight ratio of 10:1, 5:1, 3:1, 1:1, and 1:2, respectively, and dissolved in a weight ratio of 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 at weight ratios of 10:1, 5:1, 3:1, 1:1, and 1:2, respectively.

(4) Manufacturing of composite antibacterial beads

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

<Example 2>

A first mixed coagulant was prepared by mixing 2 parts by weight of sodium tripolyphosphate, a curing agent, with 100 parts by weight of an aqueous sodium hydroxide solution, and the composite antibacterial beads were prepared in the same manner as in Example 1, except that the prepared first mixed coagulant was used. was manufactured.

<Example 3>

A second mixed coagulant was prepared by mixing 2 parts by weight of sodium tripolyphosphate, a curing agent, and 1 part by weight of tetraethoxysilane, a curing accelerator, with 100 parts by weight of aqueous sodium hydroxide solution, except that the prepared second mixed coagulant was used. prepared composite antibacterial beads in the same manner as in Example 1.

<Example 4>

A reaction solution containing wet beads was prepared in the same manner as in Example 1-3, 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. to produce a complex antibacterial agent. Beads (Example 4-1) were prepared.

In addition, a reaction solution containing wet beads was prepared in the same manner as in Example 2-3, 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. Composite antibacterial beads (Example 4-2) were prepared.

In addition, a reaction solution containing wet beads was prepared in the same manner as in Example 3-3, 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. Composite antibacterial beads (Example 4-3) were prepared.

<Example 5>

Composite 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 composite antibacterial bead reactant. , the prepared composite antibacterial bead reaction product was dried to prepare pretreated composite antibacterial beads.

Water-soluble propolis powder is prepared by pulverizing propolis lumps, mixing 100 parts by weight of the 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. The suspended components contained in the propolis are removed by heating for a while, removing the supernatant at intervals of 30 to 40 minutes, mixing the same amount of water as the amount of the removed supernatant, and 100 parts by weight of the propolis extract from which the floating components have been removed. Water-soluble propolis powder prepared by mixing 40 parts by weight of polysorbate, a surfactant, and 500 parts by weight of water, diluted, mixed with 10 parts by weight of L-arginine, and dried was used.

<Example 6>

An antibacterial resin composition was prepared by mixing 100 parts by weight of high-density polyethylene (HDPE) and 5 parts by weight of composite antibacterial beads prepared by the method according to Example 4-3, and the prepared antibacterial resin composition was injection molded. A container body for cosmetic containers was manufactured. A cosmetic container specimen was manufactured by coating the inner surface of the manufactured container body with the coating mixture to form a water- and oil-repellent layer with a thickness of 10 ㎛. The coating mixture contains 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 digly. Use 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 zeolite powder (porous ceramic powder) with an average particle size of 1 to 3 ㎛, and 15 parts by weight of water. did.

<Example 7>

A cosmetic container with a water- and oil-repellent layer and an antibacterial resin layer was manufactured in the same manner as in Example 6, except that modified zeolite powder was used as a porous ceramic powder.

For the modified zeolite powder, a suspension was prepared by mixing 20 parts by weight of natural zeolite powder and 100 parts by weight of water, and 50 parts by weight of a mixed alcohol containing ethanol and 1,2-hexanediol in a weight ratio of 1:1 was mixed with the prepared suspension. and reacted for 2 hours to prepare a mixture containing pretreated zeolite. Pretreated zeolite was obtained from the prepared mixture and then dried at a temperature of 120°C for 8 hours to prepare hydrophobic zeolite. A suspension was prepared by mixing 50 parts by weight of the prepared hydrophobic zeolite with 100 parts by weight of water, and then 50 parts by weight of a mixture containing 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyltrichlorosilane was added to the prepared suspension. They were mixed and reacted at 65°C for 3 hours to prepare modified zeolite with fluorine silane introduced to 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 nanocellulose solution was not introduced.

<Comparative Example 2>

After manufacturing the container body for cosmetic containers, the fluorinated copolymer on the inner surface of the container body is 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. Cosmetic container specimens were manufactured in the same manner as in Example 6, except for coating.

<Experimental Example 1>

(1) Measurement of solubility of complex antibacterial beads

The dry weight (W ₀ ) of the composite antibacterial beads prepared by the method according to the Examples and Comparative Examples was measured, the composite antibacterial beads were immersed in a 5% acetic acid aqueous solution (volume ratio 5:95), and then washed three times with deionized water. , dried at 100°C for 12 hours, the weight ( _WS ) after drying was measured, and the solubility was evaluated by measuring the content of soluble chitosan and nanocellulose using Equation 1 below, and the results are shown in Table 2 below. . Solubility evaluation was performed by evaluating the solubility (unit: %) of each sample prepared at 3-hour intervals. To evaluate solubility, a mixture of chitosan powder and nanocellulose powder separately immersed in a 5% acetic acid aqueous solution was 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, which was a composite of chitosan and nanocellulose, compared to Comparative Example 1, which was manufactured by dropping chitosan beads, the nanocellulose was It was confirmed that by forming a strong network with chitosan, the solubility was greatly reduced and the physical and chemical properties were improved.

In particular, it was confirmed that the physical properties were further improved when crosslinking was performed by adding the curing agent alone or by adding a mixture of the curing agent and curing aid, and it was confirmed that the physical and chemical properties were also improved through heat treatment as in Example 4.

(2) Measurement of swelling of composite antibacterial beads

The swelling degree (S _w ) of beads manufactured 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°C) for 12 hours, and then measuring the weight (W _t ) after immersion. 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 nanocellulose increased, a strong network was formed due to the complexation of chitosan and nanocellulose, and the swelling degree decreased significantly. It was confirmed that the physical and chemical properties of the composite antibacterial beads were improved 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 manufactured by the method according to Examples and Comparative Examples was evaluated, and the results are shown in Table 4 below.

Compressive strength evaluation was performed by manufacturing spherical bead specimens 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 introduction of nanocellulose resulted in chitosan and nanocellulose forming a dense network structure, greatly improving the strength of the composite antibacterial beads.

In particular, it was confirmed that mechanical properties were further improved when a hardener was introduced, and that physical properties could also be improved through heat treatment. When a curing accelerator was additionally introduced, amide bonding was promoted by silane. It was confirmed that 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 when molding plastic containers, films, sheets, etc., and have excellent uniformity of physical properties, making them an antibacterial agent with excellent processing suitability. It was confirmed that it could be formed.

(4) Antibacterial evaluation of composite antibacterial beads

The antibacterial properties of composite antibacterial beads prepared by the method according to Examples and Comparative Examples were evaluated. For the antibacterial evaluation, according to JIS Z 2801:2000 , prepare a culture medium with an initial bacterial count of ^1.1 Then, the culture was cultured at a temperature of 35°C for a certain period of time, and then cultured 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 manufactured by the method according to the Examples and Comparative Examples, it was confirmed that the prepared beads had an excellent antibacterial effect at the level of 99.9% against E. coli, and the introduction of propolis It was confirmed that antibacterial properties were further improved.

(5) Antibacterial persistence evaluation

The antibacterial persistence of composite antibacterial beads prepared by the method according to Examples and Comparative Examples was evaluated. Antibacterial persistence evaluation was conducted in accordance with KS K 0693:2001 using Staphylococcus aureus ATCC 6538, a gram-positive bacterium, as the target strain. The strain was inoculated into the culture medium and the strain in the culture medium was 1.1 × ¹⁰⁶ cfu/mL. After culturing, complex antibacterial beads were introduced into the culture medium and cultured. The number of bacteria after 18 hours of culture and the reduction rate (unit: %) of the number of bacteria after 3 months of culture were measured. The results are shown in Table 6 below.

As a result of evaluating the antibacterial persistence of the composite antibacterial beads manufactured by the method according to the Examples and Comparative Examples, the mechanical properties of the composite antibacterial beads manufactured by introducing a cross-linking agent and a cross-linking accelerator were improved, even when contacted with the culture medium for a long period of time. While it was confirmed to exhibit excellent antibacterial persistence, in the case of composite antibacterial beads manufactured without using them as in Examples 1-3 and 4-1, decomposition is promoted due to biodegradability, making it difficult to maintain antibacterial persistence for a long period of time. was able to confirm.

(6) Biodegradability evaluation

The biodegradability of composite antibacterial beads prepared by the method 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 period of 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.

For this purpose, 2 g of composite antibacterial bead sample with an average particle size of 500 ㎛ was immersed in 50 mL of phosphate buffered saline (PBS) buffer solution 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 solution with the same amount of lysozyme dissolved in it was added to maintain enzyme activity, and the biodegradability of composite antibacterial beads prepared in an environment similar to body fluids was evaluated. After 30 days, the phosphate-buffered saline solution was removed, the remaining sample was washed and dried to obtain a non-decomposed composite antibacterial bead sample, the weight of the obtained sample was measured, and immersed in phosphate-buffered saline solution in which lysozyme was dissolved. Biodegradability was evaluated by comparing the weight with the total composite antibacterial bead sample and measuring the weight reduction rate (unit: %).

As in Comparative Example 1, it was confirmed that beads without nanocrystalline cellulose showed rapid biodegradability with a weight reduction rate of 98.3%, whereas, as in the composite antibacterial bead sample of Example 1, beads containing nanocrystalline cellulose and It can be confirmed that the weight loss rate is greatly reduced by compositing, and as in Example 2, the addition of a curing agent and curing accelerator promotes crosslinking and adjusts biodegradability, and heat treatment also promotes crosslinking and adjusts biodegradability. there was.

(7) Cytotoxicity evaluation

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

For ^cytotoxicity evaluation, NIH3T3 cells were distributed in a 96-well plate at 1 It was cultured for some time.

The cultured sample was obtained and a CCK assay (cell counting kit assay) was performed to confirm cell viability. The results are shown in Table 7 below. At this time, untreated NIH3T3 cells were used as an untreated control, The cell survival rate for each treatment group was evaluated using the cell survival rate (unit: %) of the control group as a standard (100%).

As a result of evaluating the cytotoxicity of the manufactured composite bead sample, the manufactured composite antibacterial beads do not show cytotoxicity and are not harmful to the human body even when ingested orally. They are biodegradable after a certain period of time and can be discharged outside the human body, making them safe for the human body. It was judged to be high.

<Experimental Example 2>

(1) Contact angle measurement

The inner contact angle was measured using cosmetic container specimens manufactured by the method according to Examples 6 and 7. The contact angle was measured using a static method using a camera. To evaluate water repellency and oil repellency, water contact angle and 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 and oil repellency. In particular, it was confirmed that when modified zeolite was used, water repellency and oil repellency were further improved and the properties of the water and oil repellent layer could be further improved.

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

(2) Fall angle measurement

The falling angle was measured using cosmetic container specimens manufactured by the method according to Examples 6 and 7. The falling angle measurement is a method of placing a cosmetic container specimen horizontally on the ground, dropping 1 mL of dimethicone on the surface, then tilting the cosmetic container specimen and measuring the angle when the dimethicone starts to flow. It was evaluated, and the results are shown in Table 9 above.

As shown in Table 9, it was confirmed that the water- and oil-repellent layer formed on the surface of the cosmetic container had excellent oil repellency, forming a structure that allows the silicone oil component to easily flow even when the falling angle is very low.

A detailed description of preferred embodiments of the invention disclosed above is provided to enable any person skilled in the art to make or practice the invention. Although the present invention has been described above with reference to preferred embodiments, those skilled in the art will understand 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 by combining them 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 features of the present invention. Accordingly, the above detailed description should not be construed as restrictive in all respects and should be considered illustrative. The scope of the present invention should be determined by reasonable interpretation of the appended claims, and all changes 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 do not have an explicit reference relationship in the patent claims can be combined to form an embodiment or included as a new claim through amendment after filing.

100: cosmetic container
101: Antibacterial resin layer
103: Water and oil repellent layer
105: Barrier layer for blocking gases
107: UV blocking layer

Claims (5)

An antibacterial resin layer containing an antibacterial agent containing a chitosan solution and nanocellulose and a high-density polyethylene resin; And a water- and oil-repellent layer formed on the inner surface of the antibacterial resin layer,
The water and oil repellent layer is,
It is formed by laminating a mixture containing 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 antibacterial resin layer,
The porous ceramic filler includes 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 mixed alcohol containing ethanol and 1,2-hexanediol in a weight ratio of 1:1 with the suspension and reacting for 0.5 to 6 hours to prepare a mixture containing pretreated zeolite ; (3) obtaining a pretreated zeolite from the mixture and then drying it 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 the prepared mixture includes 100 parts by weight of ethanol and 10 to 50 parts by weight of perfluorodecyl trichlorosilane. An antibacterial cosmetic container, characterized in that it is manufactured by a method comprising the step of mixing 10 to 100 parts by weight of the mixture and reacting at 40 to 70 ° C. for 1 to 12 hours to prepare a modified zeolite with fluorine silane introduced to the surface.
According to paragraph 1,
The antibacterial agent includes silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), titanium dioxide (TiO ₂ ), chitosan, silver (Ag) supported zirconium phosphate, and silver (Ag) supported calcium phosphate. , silver (Ag) supported apatite phosphate, silver (Ag) supported silica gel, activated carbon, shell powder, eggshell powder, phytoncide, propolis, xylitol, capsaicin, curcumin, berberine, allicin, acacetin, carvacrol, mastic, catechin. , an antibacterial cosmetic container comprising at least one selected from the group consisting of complex antibacterial beads including zentone, robinin, chitosan, and nanocellulose. According to paragraph 1,
The polymer resin includes polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate resin, polyvinyl chloride, polystyrene, and polycarbonate ( polycarbonate), acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, methylmathacrylate butadiene styrene copolymer, polylactic acid resin (poly lactic) acid, nylon resin, polyvinylidene chloride, poly acetal, polyacrylate, poly methyl methacrylate, fluoropolymer, poly urethane, polyester elastomer, melamine, urea, polyamide, polyphenylene sulfide, ethylene vinylacetate, polyvinylacetate An antibacterial cosmetic container comprising at least one selected from the group consisting of (poly vinylacetate), natural rubber, and synthetic rubber. According to paragraph 1,
An antibacterial cosmetic container further comprising a gas blocking barrier layer formed on the outer surface of the antibacterial resin layer. delete