KR102632438B1 - Packaging container with antibacterial and antiseptic effect and method for fabricating the same - Google Patents

Abstract

The packaging container with antibacterial and preservative effects according to the present invention contains a natural antibacterial material, and the natural antibacterial material is included in an adhesive layer that can be molded at room temperature rather than mixed with a general polymer resin, thereby preventing destruction of the natural antibacterial material due to high temperature. It has the advantage of further increasing antibacterial properties.
In addition, in order to demonstrate the antibacterial power of the natural antibacterial material contained in the adhesive layer, a stretch blow molding method is applied during molding to form pores in the inner layer, which has the advantage of maintaining high antibacterial properties without damaging the mechanical properties of the container.

Description

Packaging container with antibacterial and antiseptic effect and method for fabricating the same}

The present invention relates to a packaging container with antibacterial and preservative effects and a method of manufacturing the same. In detail, it has a multi-layered structure, and each layer is provided with an inorganic antibacterial material and an organic antibacterial material to protect against harmful microorganisms such as mold and bacteria as well as bacteria. It relates to a packaging container with excellent antibacterial and antifungal activity and a method of manufacturing the same.

[National research and development project that supported this invention]
[Assignment identification number] D2020142
[Ministry name] Gyeonggi-do
[Research management agency] Gyeonggi Province Economic and Science Promotion Agency
[Research Project Name] Gyeonggi-do Technology Development Project Company-led General
[Research project name] Development of packaging using naturally derived preservative composite materials
[Host organization] CPRS&T Co., Ltd.
[Research period] 2020.09.01 ~ 2021.08.31
In general, cosmetics such as lotions, cosmetic creams, beauty essences, etc. contain abundant nutrients to provide nutrition to the skin. Therefore, if a cosmetic container is opened to use cosmetics and a certain period of time passes, there is a risk that the cosmetics, which are rich in nutrients, may grow and deteriorate due to contact with the air. Also, as cosmetics come into contact with hands while using cosmetics, the cosmetics come in contact with the hands. There was a problem that cosmetics were deteriorated due to contamination with bacteria and were discarded before they were all used. Therefore, cosmetics are manufactured by mixing a small amount of antibacterial substances to prevent them from deteriorating during use. Although small amounts of antibacterial substances are known to have little effect on the human body, antibacterial substances are used to prevent unknown risks in advance. The emergence of cosmetic containers that allow cosmetics containing no substances to be safely stored and used is expected.

In the past, glass was used as a container to store cosmetics, but it is currently being replaced by containers made of plastic, polypropylene, etc., which are light and easy to manufacture.

However, in plastic containers, some of the resin components are dissolved and eluted by organic acids such as lactic acid generated during the storage of cosmetics, which may cause chemical changes and cause environmental hormones. When storing cosmetics for a long period of time, there is a risk of off-odor and discoloration in the container. This can be caused.

Polypropylene material is generally used in sealed containers, is easy to process, and has excellent moisture resistance, transparency, gloss, and heat resistance. There is no problem with the polypropylene material itself, but additives such as pigments and plasticizers added for molding contain environmental hormones or heavy metals, so there is a possibility that environmental hormones may be detected when exposed to a harmful environment.

In addition, technology has been introduced to use metal components with antibacterial properties directly in polymer resin or by supporting them on a support, but this has the disadvantages of low persistence and high toxicity due to the large amount of dissolution during use, and the use of inorganic powders such as silver and copper is not recommended. It does not exhibit excellent antibacterial properties per unit weight.

Recently, as consumer awareness of health and eco-friendliness has improved and interest in well-being and environmental hormones has increased, consumer interest in safe cosmetic storage containers is increasing, and hygiene is also very important as storage containers come in direct contact with cosmetics. It is considered to be. Accordingly, there is a need for research on the development of antibacterial containers that are convenient to use as cosmetic storage containers and can reduce safety and hygiene issues.

Republic of Korea Registration Office No. 20-0393915 (August 18, 2005)

The present invention was developed to solve the above problems, and in a multi-layer packaging container in which an inner layer and an outer layer and an adhesive layer connecting them exist between the inner layer and the outer layer, the adhesive layer exhibits melting and adhesive properties even at low or room temperature. The purpose is to provide a packaging container with antibacterial and preservative effects that maximizes antibacterial properties by including an adhesive component and a natural antibacterial component and at the same time including inorganic antibacterial particles in the inner layer, and a method of manufacturing the same.

Another object of the present invention is to introduce inorganic antibacterial particles into the composition forming the inner layer, and to form pores in the inner layer by stretching and blow molding the composition forming each layer, and to provide a packaging container with antibacterial and preservative effects that further enhances antibacterial properties; The purpose is to provide a manufacturing method.

The present invention relates to a packaging container with antibacterial and preservative effects and a method of manufacturing the same.

One aspect of the present invention includes an outer layer formed of a polymer resin; an adhesive layer laminated on one side of the base layer and containing a natural antibacterial agent and an adhesive composition; and an inner layer formed on one surface of the adhesive layer and containing inorganic antibacterial particles and a polymer resin, wherein the protective layer has pores capable of gas permeation.

In the present invention, the polymer resin includes one or more selected from polyolefin, polyester, polyamide, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyacrylic, and polyvinyl chloride,

The natural antibacterial agents include propolis, pine oil, allicin, gallic acid, chitosan, citric acid, ascorbic acid, proanthocyanidin, coffee acid, gallic acid, ferulic acid, chalcone, catechin, flavanone, flavone, It is characterized in that it contains one or more selected from flavonol, berberine, naringin, kaempferol and quercetin.

In addition, the natural antibacterial agent is characterized in that it is supported on one or a plurality of porous materials selected from silica, clay, zeolite, and activated carbon.

In the present invention, the adhesive composition is a polyurethane adhesive prepared from a mixture containing a bifunctional polyol, an aliphatic diisocyanate, and an amine-based chain extender,

The inorganic antibacterial particles are any one selected from silver oxide, copper oxide, nickel oxide, chromium oxide, cobalt oxide, zinc oxide, shell, titanium dioxide, zeolite, silica, calcium phosphate, zirconium phosphate, elvan, biotite, white jade, and sapphire. It is characterized by plurality.

In addition, the shell is characterized by removing organic matter by immersing it in an aqueous solution of one or more basic substances selected from sodium hydroxide, calcium hydroxide, aluminum hydroxide, potassium hydroxide, magnesium hydroxide, sodium bicarbonate, and ammonia.

In addition, the inner layer is characterized by a porosity of 20 to 80% by volume.

Another aspect of the present invention is,

a) Preparing an outer layer composition comprising one or more polymer resins selected from polyolefin, polyester, polyamide, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyacrylic, and polyvinyl chloride. ;

b) polyurethane adhesives prepared from mixtures containing bifunctional polyols, aliphatic diisocyanates and amine-based chain extenders and propolis, pine oil, allicin, gallic acid, chitosan, citric acid, ascorbic acid, chalcone, Preparing an adhesive layer composition containing one or more natural antibacterial agents selected from catechin, flavanone, flavone, flavonol, proanthocyanidin, caffeic acid, gallic acid, ferulic acid, kaempferol, and quercetin;

c) preparing an inner layer composition comprising the polymer resin and one or more inorganic antibacterial agents selected from shell, titanium dioxide, zeolite, silica, calcium phosphate, zirconium phosphate, elvanite, biotite, white jade, and sapphire;

d) The base layer composition, adhesive layer composition, and protective layer composition are each put into an extruder, and then stretched and blown in a multilayer blow molding machine to form an inner layer using the inner layer composition, a middle layer being formed with the adhesive composition, and an outer layer being formed using the above-mentioned adhesive composition. manufacturing a multilayer container formed from the outer layer composition;

It relates to a method of manufacturing a packaging container with antibacterial and preservative effects, comprising:

At this time, the natural antibacterial agent is characterized in that it is supported on one or a plurality of porous materials selected from silica, clay, zeolite, and activated carbon.

The packaging container with antibacterial and preservative effects according to the present invention contains a natural antibacterial material, and the natural antibacterial material is included in an adhesive layer that can be molded at room temperature rather than mixed with a general polymer resin, thereby preventing destruction of the natural antibacterial material due to high temperature. It has the advantage of further increasing antibacterial properties.

In addition, in order to demonstrate the antibacterial power of the natural antibacterial material contained in the adhesive layer, a stretch blow molding method is applied during molding to form pores in the inner layer, which has the advantage of maintaining high antibacterial properties without damaging the mechanical properties of the container.

Figure 1 shows a cross section of a multilayer container manufactured according to an embodiment of the present invention.
Figure 2 shows the results of bacterial growth 6 days after inoculating the multilayer container prepared in Example 1 and the control group with the strain, (a) and (b) showing the results of bacterial growth of type A and type B toner, respectively. , and (c) is the result of bacterial growth in the control toner.

Hereinafter, the packaging container with antibacterial and preservative effects and its manufacturing method according to the present invention will be described in more detail through examples and comparative examples. However, the specific examples introduced below are provided as examples so that the idea of the present invention can be sufficiently conveyed to those skilled in the art.

Therefore, the present invention is not limited to the specific examples presented below and may be embodied in other forms. The specific examples presented below are only described to clarify the spirit of the present invention, and the present invention is not limited thereto.

At this time, if there is no other definition in the technical and scientific terms used, they have meanings commonly understood by those skilled in the art to which this invention pertains, and the following description will not unnecessarily obscure the gist of the present invention. Descriptions of possible notification functions and configurations are omitted.

Additionally, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.

In addition, the drawings introduced below are provided as examples so that the idea of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. Additionally, like reference numerals refer to like elements throughout the specification.

Additionally, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the component is not limited by the term. When a component is described as being “connected,” “coupled,” or “connected” to another component, that component may be directly connected or connected to that other component, but there is another component between each component. It will be understood that elements may be “connected,” “combined,” or “connected.”

In the present invention, antibacterial property includes all concepts such as sterilization, sterilization, sterilization, bacteriostatic, disinfection, preservative and hygiene, and refers to sterilization and sterilization that kills microorganisms by inhibiting the occurrence and growth of microorganisms, and mainly prevents the growth of bacteria in the container contents. It is used to suppress.

In the present invention, the antibacterial container is for accommodating and packaging food consumed by humans, cosmetics applied to the body, household goods, etc., and particularly includes a container accommodating cosmetics.

In the present invention, the cosmetics are products used in a similar way, such as applying, rubbing, or spraying on all parts of the body, such as skin or body hair, to add charm and brighten the appearance, and include skins, lotions, lip cloths, lipsticks, It may include rouge, blusher, mascara, cream, menu cure, twin cake, essence, perfume, pomade, hair oil, hair protectant, etc. Additionally, the household goods are used to clean the body and may include, for example, skin or body hair.

In the present invention, the antibacterial container is used to prevent the growth of fungi or bacteria due to contact with oxygen and to suppress rancidity caused by the long-term storage of the above-mentioned cosmetics or household goods.

Normally, bacteria include anaerobic bacteria that do not require oxygen for growth, such as tetanus bacteria and chlorostridium bacteria, and so-called facultative anaerobic bacteria such as Escherichia coli and staphylococci that can grow in places with or without oxygen, but tuberculosis bacteria, Aerobic bacteria such as diphtheria and Bacillus subtilis require oxygen along with the water present in the contents and any ingredients that can serve as food. Since the oxygen is obtained instantaneously from the outside after opening the lid, repeated opening and closing is required for use. It is essential that cosmetic containers have antibacterial properties. Additionally, in most sealed containers, trace amounts of oxygen may be obtained through the walls of the container. Therefore, some materials with excellent oxygen barrier properties must be introduced as materials that make up the container.

However, most general antibacterial materials introduce inorganic particles such as silver nanoparticles, and although it is possible to secure some good antibacterial properties by using a composition containing silver nanoparticles, it is difficult to believe that perfect antibacterial properties can be secured. Of course, if the silver nanoparticle component is prescribed in excessive amounts, perfect antibacterial properties can be secured, but since transparency and economic feasibility are poor, other additional alternatives are needed.

The present invention was developed to solve the above-mentioned shortcomings. The layer in direct contact with the contents contains an appropriate amount of inorganic particles rather than an excessive amount to ensure antibacterial properties, and at the same time, natural antibacterial substances are introduced into the middle layer to overcome the disadvantages of inorganic particles. It is characterized by securing natural antibacterial properties, transparency, and economic feasibility, and by applying a polymer resin with excellent transparency and oxygen barrier properties to the outer layer, not only satisfactory antibacterial properties, but also transparency and economic feasibility are secured at the same time.

Specifically, the antibacterial container 100 includes an outer layer 110 formed of polymer resin as shown in FIG. 1; an adhesive layer 120 laminated on one side of the base layer and containing a natural antibacterial agent and an adhesive composition; and an inner layer 130 formed on one side of the adhesive layer and containing inorganic antibacterial particles and a polymer resin, wherein micropores are formed in the inner layer to increase the antibacterial properties of the natural antibacterial agent provided in the adhesive layer. It is characterized by

The outer layer 110 is provided to block direct contact between the contents and oxygen, and is based on a polymer resin, but may further include other components as needed. Specifically, a colorant may be further included to perform a light blocking function, and it is also good to mix a polymer that can block oxygen with a polymer resin, for example, an ethylene-vinyl alcohol copolymer. These components may be provided in the form of separate layers, and may be formed using known materials that can perform the above-mentioned functions.

The adhesive layer 120 is responsible for adhesion between the outer layer and the inner layer and at the same time complements the antibacterial properties of the inorganic antibacterial particles of the inner layer, which will be described later. As described above, in the case of inorganic antibacterial agents such as silver and copper, the antibacterial activity per unit weight is Since it is not effective, to compensate for this, an organic antibacterial agent can be mixed with an adhesive component to form a layer.

However, organic antibacterial agents are weak to heat and are easily destroyed when mixed with polymer resins, making it difficult to exhibit antibacterial properties. Therefore, these shortcomings can be resolved by applying low-temperature melt adhesives that can be melted and molded at low temperatures and have excellent adhesion.

The inner layer 130 is a layer in direct contact with the contents and can secure antibacterial properties by containing inorganic antibacterial particles along with a polymer resin. However, when the adhesive layer is completely shielded, it is difficult to properly express the antibacterial properties of the organic antibacterial agent provided, so the particle size of the inorganic antibacterial particles can be brought to a certain range to form pores through stretching.

Hereinafter, each component will be described in more detail. In the present invention, the polymer resin included in the container serves to block oxygen from the outside and prevent the contents from coming out, and is the main component that constitutes the outer and inner layers.

The polymer resin is not limited to any type as long as it is a polymer resin capable of stretch molding and heat treatment, and examples of such resins include polyolefin, polyester, polyamide, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, and polyacrylic resin. and polyvinyl chloride.

At this time, examples of the olefin resin include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and linear ultra-low-density polyethylene, polypropylene, ethylene-propylene copolymer, or mixtures thereof, and more preferably polyethylene terelene. These include phthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, and polyarylate.

In addition, examples of the polyester include aliphatic polyesters such as polycaprolactone and polylactide, amorphous polyesters such as polyethylene terephthalate glycol, and aromatic polyesters such as polyethylene terephthalate, polybutylene naphthalate, and polyethylene naphthalate. It may include, among these, amorphous polyester with excellent transparency and oxygen barrier properties (e.g., APET PACUR 9921 from Eastman Chemical, PETG SKYGREEN S2008 from SK Chemicals), polyethylene naphthalate (e.g., NOPLA KE911 from Kolon), and polyethylene naphthalate. Based copolymers (e.g. NOPLA KE531 from Kolon) or mixtures thereof are preferred.

In addition, the above polyamides include, for example, crystalline aliphatic polyamides such as polyamide 6, polyamide 6/6, polyamide 11, polyamide 12, polyamide 6/10, terephthalic acid, isophthalic acid, and hexamethylenediamine. Examples include amorphous copolyamides such as copolymers, aromatic polyamides such as polymethoxylene adipamide, etc., but amorphous copolyamides with excellent transparency and oxygen barrier properties (e.g., Grivory G21 from Grivory-ems), aromatic polyamides, etc. Amides (e.g. Nylon-MXD6 from Mitsubishi Gas Chemical) or mixtures thereof are better.

Additionally, the composition containing the polymer resin may further include one or more additives. Such additives include, for example, antioxidants, heat stabilizers, ultraviolet stabilizers, lubricants, processing aids, drying agents, pigments, dyes, foaming agents, flame retardants, etc., and other additives commonly used in the art within the range that do not impair the purpose of the invention. May contain various additives.

As described above, the adhesive composition contains a natural antibacterial agent to exhibit antibacterial properties, and at the same time may contain an adhesive component that can exhibit adhesiveness at room temperature to prevent the natural antibacterial agent from being destroyed at high temperatures.

In general, antibacterial ingredients derived from natural substances such as propolis or allicin are created to protect plants and insects from external bacteria or predation. For example, propolis is a mixture of resins collected by bees from tree buds or sap. It protects itself from harmful microorganisms and has antioxidant, antibiotic, antiviral, antifungal, antiprotozoal, antitumor, and anti-inflammatory effects. Allicin In the case of garlic, it is a substance produced by itself and has a spicy taste to protect against animal predation and injury, and has a sterilizing effect against mold and bacteria.

However, these natural substances are quite weak at high temperatures. In particular, allicin is easily destroyed when exposed to high temperatures for just one minute, and the destroyed allicin no longer exhibits antibacterial effects.

The problem is that in the case of the above-mentioned polymer resin, it must be maintained in a molten state in order to be molded into a container shape. The melting temperature varies depending on the polymer resin, but is at least 100°C or higher, so when the natural antibacterial agent is mixed with the polymer resin, it is rescued by the high temperature. may be destroyed and lose its antibacterial effect.

The present invention was developed to solve the above problems, and the natural antibacterial agent is provided in an adhesive layer that is an intermediate layer rather than an inner or outer layer containing the polymer resin, and the adhesive constituting the adhesive layer has moldability or adhesion even at room temperature. As it is composed of ingredients that can express antibacterial properties, it is characterized by preventing destruction of the molecular structure due to high temperature and exhibiting excellent antibacterial properties.

In the present invention, the adhesive may include a polyurethane adhesive prepared from a mixture containing a difunctional polyol, an aliphatic diisocyanate, and an amine-based chain extender.

Examples of the above bifunctional polyol include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane- 1,4-diol, butene-1,4-diol, butene-1,4-diol, pentane-1,5-diol and their positional isomers, hexane-1,6-diol, octane-1,8-diol , 1,4-bishydroxymethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, trimethylolethane, hexane- 1,2,6-triol, butane-1,2,4-triol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.

Additionally, apart from the difunctional polyol, one or more aliphatic polyester polyols may be further included to increase meltability at low temperatures. Examples of such aliphatic polyester polyols include those polyols based on linear dicarboxylic acids and/or their derivatives, such as anhydrides, esters or acid chlorides, and aliphatic or cycloaliphatic, linear or branched polyols. Examples of suitable dicarboxylic acids include adipic acid, succinic acid, sebacic acid, and dodecane dicarboxylic acid, and these may be included alone or in combination of two or more.

The aliphatic diisocyanate is preferably an aliphatic isocyanate having 4 to 20 carbon atoms, such as tetramethylene diisocyanate, pentamethylene 1,5-diisocyanate, hexamethylene diisocyanate (1,6-diisocyanate) anatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, etc., and these can be used alone or in a mixture of two or more.

The amine-based chain extender is a diamine, monoamine, or a mixture thereof, for example, aliphatic, alicyclic primary or secondary monoamine ethylamine, diethylamine, isomeric propyl- and butylamine, and higher linear Includes aliphatic monoamines and cycloaliphatic monoamines such as cyclohexylamine. Other examples may include aminoalcohols, i.e. compounds having amino and hydroxy groups in one molecule, such as ethanolamine, N-methylethanolamine, diethanolamine or 2-propanolamine.

Polyurethane-based adhesives polymerized with the above ingredients have a melting temperature in the range of 30°C to 50°C, as measured by differential scanning calorimetry at a heating rate of 20 K/min according to DIN 65467, when containing the above-mentioned natural antibacterial agents. Even moldability and adhesiveness can be achieved without destroying the molecular structure of the antibacterial agent.

The natural antibacterial agent is added to prevent microbial growth and subsequent deterioration of the container contents, and may include substances that can simultaneously secure safety and antibacterial properties compared to existing preservatives.

In general, existing preservatives such as parabens are widely used in foods, cosmetics, and medicines, but these organic antibacterial agents can cause skin allergies when in contact with the human body, and they themselves have been reported to have the potential to act as environmental hormones. It is becoming.

The present invention is intended to solve these shortcomings, and is characterized by including a natural antibacterial agent in the adhesive layer to prevent deterioration of the contents and suppress the reproduction of a large number of strains without irritating the skin.

The natural antibacterial agent has a wide antibacterial spectrum without having any effect on the content by ensuring color, odor, stability, etc., and is not limited to the type as long as it can be manufactured into various formulations.

Examples of the above natural antibacterial agents include propolis, pine oil, allicin, gallic acid, chitosan, citric acid, ascorbic acid, proanthocyanidin, caffeic acid, gallic acid, ferulic acid, chalcone, catechin, Examples include flavanones, flavones, flavonols, berberine, naringin, kaempferol, and quercetin, and these can be used alone or in combination of two or more. The above-mentioned natural antibacterial agents have excellent antibacterial effects against Gram-positive bacteria, Gram-negative bacteria, and fungi, and can be easily obtained from cheap raw materials. It also has a wide antibacterial spectrum and has the advantage of being able to be manufactured in various forms.

More preferably, the natural antibacterial agent is propolis. The propolis contains Bactoster Alexin as its main ingredient, which is a powerful non-toxic antibacterial substance that inhibits the synthesis of peptide bridges of peptidoglycan, a cell wall component. To explain this in more detail, in the final stage of biosynthesis of the peptidoglycan layer, a component of the cell wall of bacteria, a protein transferase (transpeptidase) connects the glycoprotein outside the cell membrane. By inhibiting the action of this enzyme, bacterial growth and differentiation occur. is suppressed and killed. Due to these characteristics, the Bactoster Alexin is not toxic to the human body, and has a perfect sterilization property of more than 99.99% within 30 seconds, including general bacteria, food poisoning bacteria, and viruses.

The above natural antibacterial agent may be applied by mixing with a polymer, but it is preferable to apply it by supporting it on one or more carriers to further increase heat resistance and stability of form. In this case, destruction of the antibacterial agent can be prevented even at high temperatures, and even better antibacterial properties can be achieved by concentrating the natural antibacterial agent components within the sphere.

The carrier is an adsorbent commonly used in separation processes, adsorption and desorption, gas storage, etc., and has micropores (pore size < 2 ㎚), mesopores (mesopore (2 ㎚ < pore size < 50 ㎚)), and macropores inside. It can be used regardless of its type as long as it has pores such as macropores (pore size > 50 nm).

The carrier may include, for example, silica, clay, zeolite, and activated carbon. In addition, metal oxides such as titanium oxide, aluminum oxide, and zirconium oxide may be used. Additionally, the above carriers may be used alone or in combination of two or more.

The method of supporting the natural antibacterial agent on a carrier is not limited in the present invention. For example, the natural antibacterial agent and the carrier are mixed in a solvent capable of dissolving the antibacterial agents, such as water, ethanol, or acetone, and then continuously stirred. At this time, if necessary, the pH of the mixture can be adjusted to the range of 7 to 8, the temperature of the mixture can be adjusted to 20 to 40 ° C., and the mixing time can be carried out for 6 to 24 hours.

In the present invention, the composition forming the adhesive layer may include 0.01 to 50 parts by weight of a carrier containing the natural antibacterial agent based on 100 parts by weight of the polyurethane-based adhesive. If the carrier is added below the above range, it is difficult to properly develop the desired antibacterial properties, and if the carrier is added above the above range, the transparency or adhesive strength of the adhesive layer may be reduced.

In the present invention, the inorganic antibacterial particle refers to an inorganic compound containing a metal or metal ion with antibacterial properties, such as silver, zinc, copper, etc., and has excellent stability because it is in a solid form, and can be used in the stretching process to be described later. It acts as an impurity and acts as a factor that forms pores in the inner layer.

Examples of the inorganic antibacterial particles may be the same or similar to the carrier, and specifically include zeolite, synthetic zeolite, metal oxide, zirconium phosphate, calcium phosphate, calcium zinc phosphate, ceramic, soluble glass powder, silica alumina, titanium zeolite, It may include apatite, calcium carbonate, etc. The above inorganic antibacterial particles may be used alone or in a mixture of two or more.

Additionally, similar to the organic antibacterial agent described above, the inorganic antibacterial particles may further carry one or more antibacterial ingredients using the antibacterial particles as a carrier. Specifically, the inorganic antibacterial particles can be introduced through ion exchange or adsorption of metal ions such as silver, copper, manganese, zinc, etc.

More preferably, the inorganic antibacterial particle may be one in which one or more antibacterial ingredients are supported on zeolite. The zeolite is a crystalline aluminosilicate with multiple pores. Zeolite is an inorganic polymer material formed by three-dimensional connection of silicon (Si) and aluminum (Al) through oxygen atoms, and has a fine crystal size of usually 1㎛. They are structurally characterized by having nanopores of various shapes and sizes of 0.3 to 10 nm depending on the type.

Zeolite has a loose bond between each atom in its crystal structure, so its internal nanopores are usually filled with water molecules. Even if this moisture is released at high heat, the skeleton remains intact, allowing it to adsorb other fine particles. Due to its numerous nano-sized pores, zeolite has an excellent role as a cation exchanger and adsorbs foreign substances, so it can adsorb and remove heavy metals and bacteria.

The zeolite can be divided into A-type zeolite, In the present invention, all of the above materials may be used.

In addition, the antibacterial ingredient can have excellent sterilizing and antibacterial properties by mainly adsorbing metal ions, more specifically, a large number of silver ions (Ag ⁺ ). The sterilizing and antibacterial action of silver ions (Ag ⁺ ) is expressed through oligodynamic action. The microcopper action, also called trace sterilizing action, strongly binds the colloid to the sulfurhydryl group (-SH) in the cell protoplasm. Therefore, when bacteria or fungi pass through the surface of the antibacterial ingredient by inhibiting the redox system, the antibacterial ingredient disrupts the metabolic function of the microorganism, resulting in the death of the microorganism within a few hours.

In addition to silver, the trace copper action includes metals such as copper, lead, mercury, copper, cobalt, and tin. Among them, copper, silver, and platinum are commonly used because they kill pathogens relatively quickly and are non-toxic unlike other metals. . This has a deodorizing and deodorizing effect by removing bacteria that cause odor.

In addition, the inorganic antibacterial particles may be substituted with various components in addition to the carrier carrying the metal ion as described above, and more preferably, the inorganic antibacterial particles may be chitosan.

The chitosan is the main component of the shell of insects and crustaceans, such as oysters, abalone, scallops, cockles, mussels, short necked clams, and clams. It can also be obtained from shells of clams such as bar clams, especially oyster shells. In particular, when using oyster shells, most discarded shells can be recycled, thereby reducing the occurrence of marine pollutants.

The composition of oyster shells varies slightly depending on the cultivation method and period of storage, but calcium carbonate is approximately 95% by weight, and the remainder is composed of organic matter such as protein, fat, and chitin. Chitin is a major component of the exoskeleton of crustaceans and is a type of mucopolysaccharide in which N-Acetyl-D-glucosamine is bonded at β-1, 4. When chitin is deacetylated, chitosan is formed. do. Chitin and chitosan are not only non-toxic, but are also natural polymer cations that are involved in the synthesis and decomposition of living organisms and do not cause environmental pollution. Recently, these materials have been widely used in various industrial fields as potential resources, such as environmental wastewater coagulants, heavy metal adsorbents, and protein recovery agents. In addition, the function as a natural antibacterial agent using chitin and chitosan-based derivatives is also emerging as one of the applications of chitosan. In this regard, Sudarshan et al. reported that chitosan derivatives such as chitosan lactate and chitosan hydroglutamate are excellent antibacterial substances against general E. coli.

In the present invention, the oyster shell is added in powder form, but it is better to remove organic matter and salt attached to the surface as described above. At this time, the oyster shell is first immersed in a tank containing distilled water for 4 to 6 hours and the removal operation is repeated 2 to 3 times to completely remove salt, and then immersed again in an aqueous solution of basic material to remove organic matter, especially protein, on the surface. do.

In the present invention, the basic substance is not limited to the type as long as it can dissolve protein. For example, it includes sodium hydroxide, calcium hydroxide, aluminum hydroxide, potassium hydroxide, magnesium hydroxide, sodium bicarbonate, and ammonia, and these can be used alone or Two or more can be mixed and used.

It is preferable to mix the basic substance with water to a concentration of 1 to 10% by weight and then immerse the oyster shell in the water. At this time, it is preferable to finely grind the oyster shells using a grinding device such as a planetary mill to increase the protein dissolution effect. In addition, the basic material solution is preferably stirred at 80 to 100° C. and 50 to 200 rpm for 1 to 5 hours after adding the oyster shell powder.

In addition, after removing the protein, the oyster shell is added to 100 parts by weight of 30 to 40% hydrochloric acid, 80 to 120 parts by weight, 60 to 80 parts by weight to 100 parts by weight of 60 to 65% nitric acid, and 100 parts by weight of mixed inorganic acid of hydrochloric acid and nitric acid. It is preferable to gradually add 60 to 100 parts by weight while stirring and then neutralize by shaking and dissolving for 12 to 36 hours.

The particle size of the inorganic antibacterial particles is not limited, but it is preferable that the average particle diameter is in the range of 0.5 to 2㎛ for the formation of pores in the inner layer, which will be described later. If the average particle diameter of the inorganic antibacterial particles is less than the above range, the desired physical properties cannot be obtained due to poor kneading during composition manufacturing, and if it exceeds the above range, the physical strength of the inner layer may decrease and the occurrence of defects may increase.

In addition, the amount of the inorganic antibacterial particles added is not limited, but it is preferable to add 1 to 30 parts by weight based on 100 parts by weight of the polymer resin constituting the inner layer. If it is less than the above range, the antibacterial properties and breathability of the inner layer may not be properly expressed, and if it exceeds the above range, the mixability and physical strength of the inner layer may decrease.

The manufacturing method of the antibacterial container according to the present invention can be manufactured by a conventionally known manufacturing method. However, in the above-described multi-layer structure, in order to form pores in the inner layer, a composition is prepared for each layer and molded, and then the molded preform is It can be manufactured by stretch blow molding.

Specifically, the manufacturing method of the antibacterial container is,

a) Preparing an outer layer composition comprising one or more polymer resins selected from polyolefin, polyester, polyamide, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyacrylic, and polyvinyl chloride. ;

b) polyurethane adhesives prepared from mixtures containing bifunctional polyols, aliphatic diisocyanates and amine-based chain extenders and propolis, pine oil, allicin, gallic acid, chitosan, citric acid, ascorbic acid, chalcone, Preparing an adhesive composition containing one or more natural antibacterial agents selected from catechin, flavanone, flavone, flavonol, proanthocyanidin, caffeic acid, gallic acid, ferulic acid, kaempferol, and quercetin;

c) preparing a protective layer composition comprising the polymer resin and one or more inorganic antibacterial agents selected from shell, titanium dioxide, zeolite, silica, calcium phosphate, zirconium phosphate, elvanite, biotite, white jade, and sapphire;

d) The base layer composition, adhesive layer composition, and protective layer composition are each put into an extruder, and then stretched and blown in a multilayer blow molding machine to form an inner layer using the inner layer composition, a middle layer being formed with the adhesive composition, and an outer layer being formed using the above-mentioned adhesive composition. manufacturing a multilayer container formed from the outer layer composition;

may include.

In the present invention, steps a) to c) are steps of preparing a composition by mixing the components constituting each layer, particularly the inorganic antibacterial particles included in the inner layer, the polyurethane-based low-temperature melt adhesive constituting the adhesive layer, and the outer layer. Each layer can be manufactured by mixing the polymer resin and other additives differently depending on the composition of each layer.

In particular, the composition constituting the outer layer may further include a polymer resin or inorganic particles that can increase gas barrier properties to block oxygen penetration.

Preferred barrier polymer resins as described above include polyamide resins obtained by polycondensation of a diamine component mainly composed of xylylenediamine with a terminal amino group concentration of less than 40 eq/10 ⁶ g and a dicarboxylic acid component. In the case of inorganic particles, it is preferable to add additional layered silicates such as mica, vermiculite, and smectite.

In the case of the barrier polymer resin or inorganic particles as described above, it is preferable to include 1 to 5 parts by weight of each based on 100 parts by weight of the polymer resin constituting the outer layer because it can satisfy both mechanical properties and gas barrier properties.

It is preferable to prepare a masterbatch by mixing the components that make up each layer, especially components that are not properly mixed in some cases, such as antibacterial particles, with a small amount of polymer resin and pelletizing them.

In step d), as described above, a multi-layered preform can be manufactured and then stretched by blow molding. At this time, the multi-layer preform can be manufactured by a molding method commonly known in the art, for example, a co-extrusion method in which each component is stored in each cylinder and co-extruded, and a co-injection method in which the components are simultaneously injected into a mold. Examples include a molding method, a sequential injection molding method in which the components are sequentially injected into a mold, and a compression molding method in which a coextrudate of the components is compressed and molded.

The molded multilayer preform can be molded by a stretch blow method commonly performed in the industry, and it is preferably performed by the cold Parison method or the hot Parison method, especially without completely cooling the molded multilayer preform. Molding using the hot Parison method of stretch blow molding is preferable because pore formation in the inner layer can be more active.

In addition, the multi-layer preform can be uniaxially or biaxially stretched to form a container, and if necessary, it is better to proceed with stretching while heating the preform to 80 to 150 ° C. using hot products, infrared heaters, high-frequency induction heating, etc. .

The multilayer preform is supplied into a generally known stretch blow molding machine, fixed in a mold, stretched in the axial direction by pushing a stretch bar, and simultaneously stretched in the circumferential direction by blowing fluid. At this time, the interface formed between the inorganic antibacterial particles contained in the inner layer and the polymer resin is destroyed during the stretching process, forming pores around the particles.

The stretch ratio of the multilayer preform is not limited. For example, it is better to decide based on the difference in refractive index of the polymer resin constituting each layer, the average particle size of the inorganic antibacterial particles contained in the inner layer, the amount added, etc. The range is not limited, but in the range of 1 to 4 times in the axial direction. Stretching is preferable because it reduces the occurrence of haze and allows pores to be formed in the inner layer.

The porosity of the inner layer of the container manufactured through stretching as described above is not limited, but it is preferable that the porosity satisfies 20 to 80% by volume. If the porosity is less than the above range, the antibacterial properties of the natural antibacterial material provided in the adhesive layer are not properly expressed, and if it exceeds the above range, the mechanical properties of the container may decrease.

The thickness of each layer of the multi-layer packaging container according to the present invention is not limited, and may be different depending on the purpose of the container. Specifically, the container preferably has a thickness of each layer of 500 ㎛ or less, especially in the range of 200 to 300 ㎛. At this time, the thickness refers to the thickness of the thinnest part constituting the container.

Hereinafter, the multilayer antibacterial container according to the present invention will be described in more detail through examples and comparative examples. However, the following examples are only examples to explain preferred embodiments of the present invention, and the present invention is not limited to the following examples.

The physical properties of the specimens prepared through the following examples were measured as follows.

(antibacterial)

First, a water toner prepared with the composition ratio shown in Table 1 below was prepared, and then the prepared water toner was added to the specimens prepared through each example. Next, in order to evaluate the antibacterial activity, the antibacterial performance of the packaging container was evaluated using a method based on JIS Z 2801:2006. Specifically, two types of test bacteria were tested: bacteria (Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 65380), and Pseudomonas aeruginosa (ATCC2 9027)) and fungi (Aspergillus niger (ATCC 9642) and Candida albicans (ATCC 90028)). However, the test bacteria were mixed for each type and inoculated into the water toner at a concentration of 10 ⁵ CFU/ml. In addition, a general container was used as a control, and the bacteriostatic reduction rate was calculated by measuring the number of viable bacteria 6 days after inoculation at room temperature (25°C).

award Raw material name Moisturizing toner (A)
Antibacterial and preservative container storage
(weight%) Moisturizing toner (B)
Antibacterial and preservative container storage
(weight%) Control group moisture toner
General container storage
(weight%) A water 10 10 10 A Ethylenediaminetetraacetic Acid(EDTA-2Na) - - 0.02 A Carbopol Ultrez 10 0.15 0.15 0.15 A Carbopol Ultrez 10 0.05 0.05 0.05 B water 81.79 84.79 77.77 B Dipropylene Glycol(DPG-FG) 3 - 7 B Niacinamide 2 2 2 B TREHALOSE 0.1 0.1 0.1 B DES(Diethoxyethyl Succinate) 0.4 0.4 0.4 C water One One One C Tromethamine 0.16 0.16 0.16 D GPI-25
(PYROTER GPI-25)
Amino acid-derived surfactant 0.3 0.3 0.3 D Vitamin E 0.02 0.02 0.02 D OLOLA FREE-1072W
(Combined flavor?) 0.03 0.03 0.03 D antiseptic - - - E SC Fluid TN
(modified silicone) One One One

(Hayes)

After sampling the side area of 20 × 20 mm of the container manufactured through the following examples, the cloudiness (%) was measured three times in accordance with ASTM D 1004 and the average value was calculated.

(tensile strength)

Based on ASTM D 638, type 1 dumbbell-shaped test pieces were used, and the test speed was 10 mm/min, with 5 samples.

(porosity)

Using a differential heat analyzer (model name: DSC-7, PerkinElmer, USA), melt the sample at a temperature increase rate of 5°C/min, measure the heat of fusion, calculate the degree of crystallinity from this, and calculate the theoretical density from the relationship between density and degree of crystallinity. was calculated. Porosity was calculated based on the difference between theoretical density and apparent density.

(Example 1)

First, to prepare a carrier containing a natural antibacterial substance, 30 parts by weight of propolis and 50 parts by weight of mesoporous silica were added to 100 parts by weight of ethanol. After stirring this at room temperature (20°C) for 6 hours, solid-liquid separation was performed to prepare a carrier.

Next, to prepare the adhesive, two types of polyester polyols (polyester polyol 1: OH 50 mg·KOH/g, Tg -61°C, melt temperature 49°C; polyester polyol 2: OH 66 mg·KOH/ g, Tg -63°C, melting temperature 26°C) were mixed at a weight ratio of 1:1, and then 4 parts by weight of 1,4-butanediol and 50 parts by weight of isophorone diisocyanate were added at a temperature of 60°C. After dissolving the mixture in acetone, Na-diaminosulfonate was mixed therewith. Then, the solvent was removed to complete the polyurethane adhesive (Tg -61°C, melt temperature 43°C).

Then, the composition containing the above ingredients was molded into a multi-layer preform with a three-layer composition using a co-injection molding machine. At this time, the composition of each layer is sequentially from the inner layer: 100 parts by weight of polypropylene, 10 parts by weight of silver ion adsorption zeolite, 10 parts by weight of oyster shell angle (each with an average particle diameter of 1㎛) / 100 parts by weight of polyurethane adhesive, 20 parts by weight of carrier / poly It was 100 parts by weight of propylene. The molded multilayer preform was subjected to biaxial stretch blow molding at a magnification of 3 times to form a container with a three-layer structure.

(Example 2)

A container was manufactured in the same manner as in Example 1, except that the contents of zeolite and oyster shell shell contained in the inner layer were each 20 parts by weight.

(Example 3)

The container was manufactured in the same manner as in Example 1, except that the particle size of the inorganic antibacterial particles was set to 5 ㎛.

(Comparative Example 1)

In Example 1, when manufacturing the container, the carrier carrying the natural antibacterial material was mixed with the inner layer composition instead of the adhesive layer (inner layer: 100 parts by weight of polypropylene, 10 parts by weight of anion-adsorbing zeolite, 10 parts by weight of oyster shell shell, 20 parts by weight of carrier) ) The container was manufactured in the same manner except that.

(Comparative Example 2)

A container was manufactured in the same manner as in Example 1, except that a heat-melt adhesive (HMPSA, Kolon, softening point 100°C) was used instead of a polyurethane-based adhesive as a component of the adhesive layer when manufacturing the container.

(Comparative Example 3)

A container was manufactured in the same manner as in Example 1, except that no support was added when manufacturing the container.

(Comparative Example 4)

A container was manufactured in the same manner as in Example 1, except that inorganic antibacterial particles were not added when manufacturing the container.

(Comparative Example 5)

A container was manufactured in the same manner as in Example 1, except that stretching was not performed during manufacturing the container.

Mixed strains Moisturizing toner Probiotic count
(CFU/ml) Bacteriostatic reduction rate
(%) bacteria Type A <20 99.9% Type B <20 99.9% control group Not measurable Not measurable fungus Type A <20 99.9% Type B <20 99.9% control group Not measurable Not measurable

Table 2 and Figure 2 show the bacteriostatic reduction rate measured when toner was added to the container manufactured in Example 1 and the control group. As shown in Figures 2 (a) and (b), the bacteriostatic reduction rate was measured in the container manufactured according to the present invention. It can be seen that the stored toner showed little growth even though it was inoculated with bacteria, whereas the control toner (c) was deteriorated due to bacterial growth.

porosity
(%) Bacteriostatic reduction rate
(%) Haze
(%) tensile strength
(MPa) Example 1 67 99.9 5.5 16.5 Example 2 86 99.9 17.4 11.4 Example 3 93 99.9 19.6 9.7 Comparative Example 1 91 81.5 5.6 9.9 Comparative Example 2 67 80.8 5.6 17.2 Comparative Example 3 61 78.5 3.9 18.1 Comparative Example 4 13 Not measurable 3.7 22.5 Comparative Example 5 2 Not measurable 3.6 17.8

As shown in Table 3 above, it can be seen that the container manufactured according to the present invention exhibits antibacterial properties and also exhibits mechanical properties such as haze and tensile strength above a certain level. However, in Example 2, where the content of inorganic particles in the inner layer was increased, or Example 3, where the particle size was increased, porosity and haze increased, and it can be seen that the tensile strength was lowered due to the formation of pores.

In addition, Comparative Example 1, in which the carrier was mixed with the inner layer forming composition, or Comparative Example 2, in which a heat-melt adhesive was used, had a negative effect on the bacteriostatic reduction rate because the natural antibacterial substances were destroyed at high temperatures, and Comparative Example 3 in which the carrier was not added also had a negative effect on the bacteriostatic reduction rate. It can be seen that it is inferior compared to this example. Here, it can be seen that Comparative Example 4, in which inorganic particles were not added, or Comparative Example 5, in which no stretching was performed, had a lower amount of antibacterial particles compared to the Example and was not properly exposed, so it hardly exhibited antibacterial properties.

The above description is merely an illustrative explanation of the technical idea of the present invention, and various modifications and variations will be possible to those skilled in the art without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but are for illustrative purposes, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention shall be interpreted in accordance with the claims below, and all technical ideas within the equivalent scope shall be construed as being included in the scope of rights of the present invention.

100: packaging container
110: outer layer
120: Adhesive layer
130: inner layer

Claims (10)

An outer layer formed of polymer resin;
an adhesive layer laminated on one side of the outer layer and containing a natural antibacterial agent and an adhesive composition; and
an inner layer formed on one side of the adhesive layer and containing inorganic antibacterial particles and a polymer resin; Includes,
The adhesive composition of the adhesive layer is a polyurethane adhesive prepared from a mixture containing a bifunctional polyol, an aliphatic polyester polyol, an aliphatic diisocyanate, and an amine-based chain extender,
The natural antibacterial agent of the adhesive layer is propolis, and the carrier supported on the porous body of silica containing the natural antibacterial agent is included in an amount of 0.01 to 50 parts by weight relative to 100 parts by weight of the polyurethane adhesive,
The inorganic antibacterial particles of the inner layer have an average particle diameter of 0.5 to 2㎛, and contain 10 parts by weight of silver ion adsorbing zeolite and 10 parts by weight of shells relative to 100 parts by weight of the polymer resin of the inner layer,
A packaging container characterized in that the multilayer preform including the outer layer, the adhesive layer, and the inner layer is stretched by a stretch blow molding machine, and the interface formed between the inorganic antibacterial particles of the inner layer and the polymer resin is broken during the stretching process to form pores. According to clause 1,
The polymer resin is a packaging container characterized in that it contains one or more selected from polyolefin, polyester, polyamide, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyacrylic, and polyvinyl chloride. delete delete delete delete According to clause 1,
The shell is immersed in an aqueous solution of one or more basic substances selected from sodium hydroxide, calcium hydroxide, aluminum hydroxide, potassium hydroxide, magnesium hydroxide, sodium bicarbonate and ammonia to remove organic matter. A packaging container, characterized in that. According to clause 1,
A packaging container characterized in that the inner layer has a porosity of 20 to 80% by volume. delete delete