KR101244778B1 - Inorganic antibacterial material using metal ion substituted inorganic carrier containing metal hydroxide, method for preparing said inorganic antibacterial material and articles comprising said inorganic antibacterial material - Google Patents

Abstract

An inorganic antimicrobial agent is provided that includes an inorganic carrier substituted with metal ions and metal hydroxide nanoparticles supported on the inorganic carrier substituted with the metal ions.

Description

Inorganic antibacterial material using metal ion substituted inorganic carrier containing metal hydroxide, method for preparing said inorganic antibacterial material and articles comprising said inorganic antibacterial material}

The present invention relates to an inorganic antimicrobial agent, a method for producing the same, and an article including the inorganic antimicrobial agent, wherein the metal hydroxide nanoparticles are supported, and an inorganic carrier substituted with metal ions. In addition, the present invention relates to an inorganic antimicrobial agent having excellent functions of releasing far infrared rays and anions and maintaining food freshness and deodorizing function.

One of the requirements of food packaging is that the packaged food is preserved in that state for a long time. Since food is caused by chemical, physical, and biological changes due to various factors, it is common to lose the value of food as a food during the preservation period, and temperature, humidity, air, and microorganisms are the main factors.

Food packaging vinyl made of a commonly used polyethylene resin is a problem that various bacteria and molds such as E. coli adhere to the surface of the product and multiply in the process used to package the product. In addition, due to humidity and microorganisms, food packaging vinyl is considered to be unsuitable for storing food for a long time, as a result of deterioration of nutritional value and generation of toxic components.

Paper, plastic film, metal, glass, wood and the like have been proposed as an alternative to food packaging vinyl, but it has a disadvantage that it is not as easy to use as vinyl products.

As another alternative, a product for providing antimicrobial properties to food packaging vinyl has been developed, and in particular, a method of providing antimicrobial properties with an inorganic antimicrobial agent is used.

Conventionally, metals such as zinc, copper, and silver have been known to exhibit antimicrobial activity, and many studies have been conducted to reliably and continuously use the antimicrobial activity of these antimicrobial metals.

Nano-particles of these antimicrobial metals have been developed for simple mixing and processing with resins. The antimicrobial vinyl packaging material produced by this method has a temporary antimicrobial activity because the metal particles are easily separated, and the separated metal nanoparticles cause environmental pollution. Not only that, but recently there has been a debate about the human safety of metal nanoparticles.

Recently, an inorganic antimicrobial agent that combines antimicrobial metal ions with an inorganic carrier such as zeolite and ceramics has been attracting attention. These inorganic antimicrobial agents are added to a polyethylene resin or the like and mixed to provide a resin to which antimicrobial activity is imparted. However, when these inorganic antimicrobials are added to the resin, the compatibility with the resin is greatly reduced, resulting in the aggregation of the inorganic antimicrobial agent locally, resulting in a decrease in the antimicrobial activity of the resin and the inability to reproduce the antimicrobial activity. . As a result, a larger amount of inorganic antimicrobial agent is incorporated into the resin in order to enhance the antibacterial activity, which causes other problems such as discoloration of the resin, deterioration of physical properties, and cost increase.

On the other hand, food packaging vinyl should have a different function from the general packaging. The possibility of microbial expression inside the packaging film should be suppressed, and the food inside the package will continue to breathe, so this breathing should be controlled to remain fresh for a long time.

Moisture generated in the respiratory action of the food and transpiration caused by the moisture in the cell tissue changes the humidity in the package to a very humid condition, so it has the effect of suppressing the counterfeiting or loss of moisture caused by food dehydration. This excess may cause the growth of decaying bacteria or increase the divergence of ethylene gas inside the package, thereby promoting aging, and thus the humidity control function is also an important function of the packaging material itself.

Agricultural foods release ethylene gas as it matures. Ethylene gas is recognized as a plant hormone because it affects the growth and development of almost all plants. The most representative effect of ethylene on plants is to promote the aging of tissues. For agricultural products that require freshness, ethylene must be absorbed and removed.

In order to remove ethylene gas, inorganic minerals such as porous calcite, zeolite, and silica, potassium permanganate, bromine compounds, and activated carbon materials have been used to exchange ethylene gas, and mung bean protein, cypress extract (hinokichiol), etc., also inhibit ethylene formation. It has been known as a substance. However, since many factors are involved in maintaining the freshness of agricultural products and conditions for the types of agricultural products are different, recently, new functions have been pursued through a combination of various leading maintenance functions.

In recent years, research on the development of functional food packaging materials has been actively conducted. This includes functionalities such as freshness maintenance, selective permeability, microwaveability, high barrier properties, antimicrobial activity, absorption and hygroscopicity, and is particularly attracting attention as a freshness maintenance packaging material. Packaging materials having adsorption functions for ethylene, ammonia, and the like are mainly used for vegetables and fruits, and these are also used according to kinds of vegetables, fruits, and foods.

In the case of Japan, which is leading in the development of functional packaging films, far-infrared-related ceramics have been put to practical use in the biomedical system for treatment, and it is considered that far-infrared rays will affect fruit vegetables based on the good effect on the physiological metabolism of living organisms. It is known that a polypropylene film in which a polypropylene material is filled with CaCO ₃ , zeolite and ceramics has been developed.

Products filled with polyethylene materials to provide inorganic materials include functional films containing silver ion-substituted zeolites, antifog films using surfactants, antimicrobial films containing cyclodextrins containing aryl isocyanates, and cypress extracts. (Hinokichiol), a mustard extract, a film using a flavor component of garlic as a natural antimicrobial agent, ethylene adsorption film, various products such as the situation to produce products according to the characteristics of agricultural products. However, such functional packaging film may have a lower reproducibility of leading maintenance function depending on the surrounding environment, so a more advanced product level is required.

One aspect of the present invention is to provide an inorganic antimicrobial agent that exhibits a stable antimicrobial activity over a long period of time.

Another aspect of the present invention is to provide a method for preparing the inorganic antibacterial agent.

Another aspect of the present invention is to provide a thermoplastic resin composition including the inorganic antimicrobial agent having excellent antimicrobial activity, excellent dispersibility in processing, and less discoloration and deterioration of the resin.

Another aspect of the present invention is to provide a packaging material prepared from the thermoplastic resin composition.

Another aspect of the invention is to provide an article comprising said inorganic antimicrobial agent.

One aspect of the invention is an inorganic carrier substituted with metal ions; Metal hydroxide nanoparticles supported on the inorganic carrier substituted with the metal ions and made of aluminum hydroxide, zirconium hydroxide or a combination thereof; And a sodium silicate coating layer on which the metal hydroxide nanoparticles are supported and formed on an inorganic carrier substituted with metal ions.

The content of the metal hydroxide nanoparticles may be 1 to 20 parts by weight based on 100 parts by weight of the metal ion-substituted inorganic carrier.

The metal ion may be one or more selected from the group consisting of zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium and thallium.

The inorganic carrier may be at least one selected from the group consisting of zeolite, calcium phosphate, zirconium phosphate and liquid glass.

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The metal hydroxide nanoparticles and the inorganic carrier may be physically combined.

The diameter of the metal hydroxide nanoparticles may be 1 to 100 nm.

According to another aspect of the present invention, aluminum chloride, aluminum sulfate, aluminum nitrate, zirconium chloride, zirconium sulfate, zirconium nitrate, or one or more combinations thereof and water are mixed with an inorganic carrier substituted with a metal ion thereto, followed by mixing Preparing a solution; Adding and adding sodium hydroxide to the mixed solution while adjusting the pH to 7 to 8; Adding sodium silicate and sulfuric acid to the mixed solution to which sodium hydroxide is further added; Leaving the mixed solution containing sodium silicate and sulfuric acid to form a precipitate; And recovering the precipitate by filtration, washing, and drying processes.

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In each of the above, the step of preparing or mixing the mixed solution may be carried out by stirring for 1 to 2 hours at 10 to 200 rpm while maintaining the room temperature with respect to the mixed solution.

Another aspect of the present invention is 0.5 to 56% by weight of the inorganic antimicrobial agent; And it provides a thermoplastic resin composition comprising 44 to 99.5% by weight thermoplastic resin.

Another aspect of the present invention provides a food packaging material, a semiconductor component packaging material, or an electronic product packaging material manufactured using the thermoplastic resin composition.

Another aspect of the invention provides an article comprising said inorganic antimicrobial agent.

The article can be made from fiber, paper, rubber, wood, glass or metal It may be any one selected from the products.

The inorganic antimicrobial agent can maintain a long-term antimicrobial effect, plastic products using the thermoplastic resin composition comprising the inorganic antimicrobial agent is less discoloration and deterioration, excellent processability and low price, when used as a food packaging material for a long time In addition to the effect of showing the stable antibacterial activity, it is excellent in the far infrared and anion release effect, and has the effect of removing gaseous components that promote the ripening and aging of foods such as ethylene gas, amine gas can maintain the freshness of food for a long time.

1 is a photograph taken to compare the preservation state after a certain period of time the leek stored in the film prepared in one embodiment and Comparative Example of the present invention.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention provides an inorganic antimicrobial agent comprising an inorganic carrier substituted with metal ions and metal hydroxide nanoparticles supported on the inorganic carrier substituted with the metal ions.

The metal hydroxide may be aluminum hydroxide, zirconium hydroxide or a combination thereof.

The metal ion may be one or more selected from the group consisting of zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium and thallium.

The inorganic carrier may be at least one selected from the group consisting of zeolite, calcium phosphate, zirconium phosphate and liquid glass.

Scheme 1 below shows that an inorganic carrier in which a metal is ion-exchanged to the inorganic carrier to be substituted with metal ions is formed.

(Scheme 1)

M + Z → MZ

Wherein M is zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium or thallium, and Z is an inorganic carrier which may be zeolite, calcium phosphate, zirconium phosphate or liquid glass.

The inorganic antimicrobial agent of the present invention may include one or more inorganic carriers substituted with metal ions formed by Scheme 1.

The aluminum hydroxide nanoparticles are physically bonded to the inorganic carrier and supported on the metal ion-substituted inorganic carrier.

Since the inorganic antimicrobial agent of the present invention exhibits excellent far-infrared and anion-releasing effects due to the metal hydroxide in the form of nanoparticles, the food packaging material has an effect of removing gaseous components that promote aging and aging of foods such as ethylene gas and amine gas. The application can maintain food freshness for much longer than conventional food packaging materials.

Preferably, the diameter of the metal hydroxide nanoparticles is 1 to 100 nm, and is suitable for loading on the inorganic carrier in the above range. More preferably, the diameter of the metal hydroxide nanoparticles is 1 to 10 nm.

Preferably, the content of the metal hydroxide nanoparticles may be 1 to 20 parts by weight based on 100 parts by weight of the metal ion-substituted inorganic carrier. When included in the content of the above range, it is possible to further increase the antimicrobial, far-infrared and anion-releasing effect of the original metal ion-substituted inorganic carrier by the effect of the metal hydroxide of the nano-particle size by being supported only in the pores of the metal ion-substituted inorganic carrier. have.

The inorganic antimicrobial agent may further include a sodium silicate coating layer. The coating layer may be further formed by supporting the metal hydroxide nanoparticles, and surface-treating the inorganic carrier substituted with metal ions with sodium silicate such as soluble glass.

By forming the coating layer with sodium silicate as described above, the metal ions are prevented from being easily separated from the inorganic carrier, thereby preventing the metal ions from being separated from the inorganic carrier, and as a result, the antimicrobial effect of the inorganic antimicrobial agent can be effectively It can be maintained.

Preferably, the thickness of the coating layer may be 0.01 ㎛ to 0.5 ㎛. When the thickness of the coating layer is formed in the above range, the antimicrobial effect of the inorganic antimicrobial agent, far infrared rays and anion release effect can be stabilized, and the binding of the metal ions can be stabilized, so that the antibacterial activity can be stably maintained for a long time.

Preferably, the content of sodium silicate may be 1 to 10 parts by weight based on 100 parts by weight of the metal ion-substituted inorganic carrier. When included in the content of the above range, the antimicrobial activity can be most stably maintained, and also excellent in terms of coating stability.

In another embodiment of the present invention, aluminum chloride, aluminum sulfate, aluminum nitrate, zirconium chloride, zirconium sulfate, zirconium nitrate, or one or more combinations thereof and water are mixed with an inorganic carrier substituted with metal ions thereto. Preparing a mixed solution; Adding and adding sodium hydroxide to the mixed solution while adjusting the pH to 7 to 8; Leaving the mixed solution further added with sodium hydroxide to form a precipitate; And it provides an inorganic antimicrobial manufacturing method comprising the step of recovering the precipitate by filtration, washing and drying process.

The inorganic antimicrobial agent of the present invention can be produced by the above production method.

After further adding sodium hydroxide and mixing, the method may further include adding sodium silicate and sulfuric acid to the mixed solution to which the sodium hydroxide is further added, followed by stirring, and further adding the sodium silicate and sulfuric acid. Leaving the mixed solution to form a precipitate.

For example, each raw material added to the mixed solution is 40 to 80 mass% of water, 5 to 15 mass% of aluminum chloride, aluminum sulfate, aluminum nitrate, zirconium chloride, zirconium sulfate, zirconium nitrate, or one or more combinations thereof, and inorganic. The antimicrobial agent may be added in the order of 5 to 20 mass%, sodium hydroxide 5 to 10 mass%, sodium silicate 4.99 to 10 mass% and sulfuric acid 0.01 to 5 mass%.

In the above production method, the mixed solution prepared by mixing each raw material may be mixed by stirring for 1 to 2 hours at a low speed while maintaining at room temperature.

For example, dilute an aqueous solution of sodium chloride and the like, and By reacting at a low temperature at room temperature, particles of the metal hydroxide may be adjusted to 1 to 10 nm in size.

For example, after each raw material is added, the raw materials are completely dissolved and mixed with stirring at a low speed of about 10 to 200 rpm at a low speed of about 10 to 200 rpm after adding each raw material, and the resulting precipitate is recovered and purified with purified water. After washing several times, it may be dried to prepare the inorganic antimicrobial agent of the present invention. When aluminum chloride is used as a raw material, it is sufficiently washed with purified water until no chlorine ions remain.

The inorganic antimicrobial agent may be used in addition to the thermoplastic resin, and the dispersibility of the inorganic antimicrobial agent is excellent when forming a product by molding the thermoplastic resin composition including the inorganic antimicrobial agent.

In another embodiment, the present invention provides a thermoplastic resin composition comprising 0.5 to 56% by weight of the inorganic antimicrobial agent and 44 to 99.5% by weight of thermoplastic resin. The thermoplastic resin composition may include, for example, 0.5 to 10 wt% of an inorganic antibacterial agent and 90 to 99.5 wt% of a thermoplastic resin.

The inorganic antimicrobial agent of the present invention is excellent in dispersibility when mixed with the thermoplastic resin, and excellent in processability of the thermoplastic resin composition including the same, and also the thermoplastic resin composition is less discoloration and deterioration of the resin, processability to the packaging material Also, it is excellent in price and inexpensive, and can be suitably used especially as a food packaging material. When the food is stored in a food packaging material prepared from the thermoplastic resin composition including the inorganic antimicrobial agent, it exhibits an excellent effect on deodorization as well as maintaining freshness even during long-term storage. As such, it has various functions such as antibacterial, far-infrared and anion radiation, freshness maintenance and deodorization when applied as a food packaging material, and can be used for packaging all foods such as fruits, vegetables, meat, fish, fermented foods and processed foods.

When the content of the inorganic antimicrobial agent in the thermoplastic resin composition is lower than the above range, the antimicrobial activity, far-infrared and anion release effect, deodorizing effect, and the like may be lowered in quality, and when the content ratio is higher than the above range, the food packaging material product The transparency of the resin may be degraded and the workability may be poor, resulting in poor quality.

The thermoplastic resin is, for example, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), Ethylene vinyl acetate (EVA), natural and synthetic rubber, etc. may be used, but is not limited thereto, and the thermoplastic resin and the inorganic antimicrobial agent may be mixed and processed to prepare a plastic product.

The thermoplastic resin composition may contain various additives as necessary, and may include fillers, antioxidants, thermal stabilizers, light stabilizers, ultraviolet absorbers, plasticizers, antistatic agents, flame retardants, mold release agents, foaming agents, nucleating agents, lubricants, antiseptics, water drops, and the like. One or more additives, such as an inhibitor, a metal inactivator, and a pigment, can be added, but is not limited to this.

In order to uniformly disperse the thermoplastic resin and the inorganic antimicrobial powder of the present invention, the inorganic antimicrobial agent is preferably first masterized. Since the inorganic antimicrobial agent is in a powder form, particle size separation may occur due to a difference in particle diameter when mixed with a thermoplastic resin pellet. By dispersing it in a thermoplastic resin in advance by making a masterbatch, the pellet is formed into a pellet having a particle size substantially the same as that of the thermoplastic resin pellet. Particle size separation can be prevented.

For example, first, 1 to 80% by weight of the inorganic antimicrobial powder is mixed with 20 to 99% by weight of the thermoplastic resin, and then stirred at a stirring speed of 40 to 80 rpm at a temperature of about 160 to 200 ° C, and the dispersed mixture is about 40 to Masterbatch by cold extrusion at a temperature of 60 ℃. Subsequently, the thermoplastic resin composition may be prepared by mixing 5 to 70 wt% of the masterbatched pellet containing inorganic antibacterial agent with 30 to 95 wt% of the thermoplastic resin.

The thermoplastic resin composition prepared as described above may be manufactured into various types of plastic products such as vinyl, film, container, paper pack, laminate film, pouch, wrap, inner and outer wrapping paper through a process such as extrusion, injection, stretching.

The thermoplastic resin composition is less discoloration and deterioration of the resin as well as excellent workability and low price can be used in various applications.

The inorganic antimicrobial agent of the present invention can exhibit a stable antimicrobial activity over a long period of time, and also has an excellent effect of releasing far-infrared rays and anions, and has an excellent effect of removing gaseous components that promote aging and aging of foods such as ethylene gas and amine gas. The thermoplastic resin composition including the inorganic antimicrobial agent of the present invention can be used for various purposes, such as food packaging materials, so that the freshness can be maintained for a long time and the deodorizing function is excellent. In particular, vinyl, vinyl gloves, rubber gloves, baby products, medical supplies, water purifiers, vacuum cleaners, refrigerators, air conditioners, ovens, washing machines, dishwashers, etc., for packaging and storing fermented foods such as fruits, vegetables, meat, fish, milk, etc. It is very useful to be used in plastic products requiring antimicrobial, such as cutlery, automobile, filter, feeding bottle.

In addition, the thermoplastic resin composition including the inorganic antimicrobial agent of the present invention may be usefully used for applications such as semiconductor packaging materials, electronics packaging materials and the like.

The inorganic antimicrobial agent of the present invention may be prepared and used to be included in products such as fiber, paper, rubber, wood, glass, metal products. For example, a method of processing the inorganic antimicrobial agent on the fiber is possible by a known method and is not particularly limited, but for example, a fiber product containing an inorganic antimicrobial agent by an injection method, a dipping method, or the like. Can be prepared.

Hereinafter, the present invention will be described in detail by examples. However, the following examples are illustrative of the present invention, and the content of the present invention is not limited by the examples.

50 g of aluminum chloride (AlCl ₃ ) was added to 500 g of water, and stirred at 50 rpm for 1 hour at room temperature. Then, 200 g of zeolite substituted with Ag and Zn metal ions (B & C Co., Ltd., C and C) was added thereto at 50 rpm at room temperature. After stirring for 2 hours, sodium hydroxide solution (NaOH solution, 10w / w%) was added thereto again and the mixture was stirred at 50 rpm for 2 hours while maintaining the pH at room temperature. The mixed solution which mixed each said raw material was left to stand at room temperature. After standing, a precipitate was formed, and the mixed solution was filtered through a filter to recover the precipitate, and then washed several times with purified water until no chlorine ions remained, followed by drying at 60 ° C. for 5 hours, and then again at 200 ° C. Drying for a time gave an inorganic antimicrobial powder.

50 g of aluminum chloride (AlCl ₃ ) was added to 500 g of water, and stirred at 50 rpm for 1 hour at room temperature. Then, 200 g of zeolite substituted with Ag and Zn metal ions (Bactecide, manufactured by C & C) was added thereto, and the mixture was heated at 50 rpm at room temperature. After stirring for an hour, sodium hydroxide solution (NaOH solution, 10w / w%) was added thereto, followed by stirring at 50 rpm for 2 hours while maintaining the pH at room temperature. Then, 30 g of sodium silicate (Na ₄ O ₄ Si) was added thereto and stirred at 50 rpm for 2 hours at room temperature. Then, 5 g of sulfuric acid solution (H ₂ SO ₄ solution, 10w / w%) was added to 50 rpm at room temperature. Stirred for 2 hours. The mixed solution which mixed each said raw material was left to stand at room temperature. After standing, a precipitate was formed, and the mixed solution was filtered through a filter to recover the precipitate, and then washed several times with purified water until no chlorine ions remained, followed by drying at 60 ° C. for 5 hours, and then again at 200 ° C. Drying for a time gave an inorganic antimicrobial powder.

To 70% by weight of the melted polyethylene (LDPE) resin was added 30% by weight of the inorganic antimicrobial powder prepared in Example 1. Thereafter, the mixture was stirred and dispersed at 60 rpm at 180 ° C., and then cooled and extruded at 60 ° C., thereby cutting to prepare a masterbatch in pellet form.

15% by weight of the masterbatch prepared by the above method and 85% by weight of polyethylene (LDPE) resin were put into an extruder and melted at 200 ° C., and then extruded into a cylindrical shape from a concentric circular disk at the tip of the extruder, and at the same time installed in the center of the disk. The extruded film was expanded in the transverse direction by drawing air into the pipe and then stretched longitudinally with two rolls on top to produce a film having a thickness of 0.08 mm.

30 wt% of the inorganic antibacterial powder prepared in Example 2 was added to 70 wt% of the molten polyethylene (LDPE) resin. Thereafter, the mixture was stirred and dispersed at 60 rpm at 180 ° C., and then cooled and extruded at 60 ° C., thereby cutting to prepare a masterbatch in pellet form.

15 wt% of the masterbatch prepared by the above method and 85 wt% of polyethylene (LDPE) resin were added to an extruder to prepare a film having a constant thickness in the same manner as in Example 3.

10 wt% of the masterbatch and 90 wt% of polyethylene (LDPE) resin prepared in the same manner as in Example 3 were put in an extruder to prepare a film having a thickness of 0.08 mm in the same manner as in Example 3.

8 wt% of the masterbatch and 92 wt% of polyethylene (LDPE) resin prepared in the same manner as in Example 3 were put in an extruder to prepare a film having a thickness of 0.08 mm in the same manner as in Example 3.

(Comparative Example 1)

To the melted polyethylene (LDPE) resin 70% by weight was added 30% by weight of silver-zn-Zeolite inorganic antibacterial powder (BACTECIDE, C & C). Thereafter, the mixture was stirred and dispersed at 60 rpm at 180 ° C., and then cooled and extruded at 60 ° C., thereby cutting to prepare a masterbatch in pellet form.

15 wt% of the masterbatch prepared by the above method and 85 wt% of polyethylene (LDPE) resin were added to an extruder to prepare a film having a thickness of 0.08 mm in the same manner as in Example 3.

(Comparative Example 2)

100 wt% polyethylene (LDPE) resin was added to the extruder to prepare a film having a thickness of 0.08 mm in the same manner as in Example 3.

(Experimental Example 1)

Antibacterial test

The specimens prepared in Examples 3 to 6 and Comparative Examples 1 and 2 were prepared with specimens of 2 cm x 2 cm. In addition, after repeated washing 10 times in accordance with JIS 103 method to prepare a specimen of the same size.

E. coli (Escherichia Coli ATCC 25922) and Staphylococcus aureus ATCC 6538 were used as test strains, and the cultures were prepared by incubating the bacteria for 16 hours in a 36 ° C. incubator.

Dilute each test strain culture solution 20,000 times to the prepared specimens, add 1 ml to the specimens, and store at 25 ° C for 24 hours. This was incubated for 48 hours in a sterilized agar medium and examined by the wet plate culture method to measure the number of viable cells. And the sterilization rate (%) was calculated according to the following formula, the results are shown in Table 1, 2. Table 1 shows the results measured on the prepared specimens, and Table 2 shows the results after washing the specimens 10 times with water.

Sterilization Rate (%) = [(Viable Count of Diluent-Viable Count after 24 Hours Storage)] × 100

Classification Strain Example Comparative example 3 4 5 6 One 2 Escherichia coli 99.9 99.9 99.9 99.9 99.6 10 ^-2 Staphylococcus 99.9 99.9 99.9 99.9 99.6 10 ^-2

Classification Strain Example Comparative example 3 4 5 6 One 2 Escherichia coli 98.1 99.9 99.9 99.9 95.3 10 ^-2 Staphylococcus 97.7 99.9 99.9 99.9 95.8 10 ^-2

As shown in Table 1, the film produced in Examples 3 to 6 has a greater reduction rate for E. coli or Staphylococcus aureus than the films prepared in Comparative Examples 1 and 2. Therefore, it can be seen that the excellent antibacterial effect in Examples 3 to 6. On the other hand, the general film (Comparative Example 2) rather increased bacteria.

As shown in Table 2, in the antimicrobial activity test measured after each wash of the film 10 times, all the films prepared in Examples 4 to 6 have the same antimicrobial activity as the film before washing, the film prepared in Example 3 Although the antimicrobial activity was somewhat reduced compared to the film, it showed that the relatively good antimicrobial activity was maintained, and in the case of the film prepared in Comparative Example 1, the antimicrobial activity was decreased.

Through this result, it can be seen that the food packaging film molded from the thermoplastic resin composition of the present invention will maintain excellent antimicrobial effect even after repeated prolonged use.

(Experimental Example 2)

Far Infrared Emissivity and Radiation Energy

The films prepared in Examples 3 to 6 and Comparative Examples 1 to 2 were 5 to 4 black compared to the black body (emissivity 100%) using an FT-IR spectrometer at 40 ° C. according to the KFIA-FI-1005 method. Far-infrared emissivity and radiation energy of 20 ㎛ were measured and the results are shown in Table 3.

division Example Comparative example 3 4 5 6 One 2 Emissivity 0.878 0.897 0.884 0.882 0.850 - Radiation Energy ^* 3.53 × 10 ² 3.61 × 10 ² 3.56 × 10 ² 3.55 × 10 ² 3.42 × 10 ² -

* Radiation energy unit: W / m ² · ㎛ · 40 ℃

As shown in Table 3, it can be seen that the higher the inorganic antibacterial content in Examples 3 to 6, the higher the far-infrared emissivity and the radiation energy, the higher the result compared to Comparative Example 1.

Experimental Example 3

Food preservation test

Each sample was prepared by preparing a container in the form of an envelope using the films prepared in Example 3 and Comparative Example 2, and storing the sweet potato and the leek in the same place and conditions, respectively. The freshness of was determined. Judgment was made with good and poor criteria as shown in Table 4 below, the results are shown in Table 5. In addition, Figure 1 is a photograph of the leek after storage for 7 days in each packaging material.

Freshness standards Contents Good A number of good judged by relative evaluation Malfunction A large number of bad judgments were made by relative evaluation

division After 7 days 15 days later sweet potato Example 3 Good Good Comparative Example 2 Good Malfunction chives Example 3 Good Good Comparative Example 2 Malfunction Malfunction

The sweet potatoes and leeks stored in the container prepared in Example 3 remained almost circular, but the sweet potatoes stored in the container prepared in Comparative Example 2 began to wither after 7 days, and the leeks began to wither after 3 days. Later, all were badly corrupted. Therefore, it can be seen that the food packaging material using the inorganic antimicrobial agent of the present invention has an excellent effect on maintaining freshness during long-term storage of the stored food.

Experimental Example 4

Deodorization test of preserved food

Healthy people with normal sense of smell after opening the film prepared in Examples 3 to 6 and Comparative Examples 1 and 2 at the same place and conditions 7 days and 15 days after storage of the leek in the same manner as in Experiment 3 The odor detected by phosphorus was evaluated by the direct sensory method based on the criteria as shown in Table 6 below.

Odor score standard Contents 0 Odorless Odor not detected One Detection I don't know what it smells, but it smells bad 2 Normal odor Odor to know what the smell is 3 Strong odor Strong odor

division Example Comparative example 3 4 5 6 One 2 After 7 days 0 0 0 0 0 2 15 days later 0 0 0 0 One 3

The leek stored in the plastic packaging made of the films of Examples 3 to 6 did not occur odor after 7 days, the vinyl packaging made of the film of Comparative Example 2 had a bad smell, Examples 3 to 6 of The odor did not occur after 15 days in the vinyl packaging made of the film, a slight odor occurred in the vinyl packaging made of the film of Comparative Example 1, very severe odor occurred in the vinyl packaging made of the film of Comparative Example 2 Occurred. Therefore, it can be seen that the food packaging material using the inorganic antimicrobial agent of the present invention has an excellent effect on deodorization as well as maintaining freshness during long-term storage of the stored food.

Claims (14)

Inorganic carriers substituted with metal ions;
Metal hydroxide nanoparticles supported on the inorganic carrier substituted with the metal ions and made of aluminum hydroxide, zirconium hydroxide or a combination thereof; And
Inorganic antimicrobial agent comprising; a sodium silicate coating layer on the inorganic carrier, the metal hydroxide nanoparticles are supported, and substituted with metal ions. The method of claim 1,
The content of the metal hydroxide nanoparticles is an inorganic antimicrobial agent, characterized in that 1 to 20 parts by weight based on 100 parts by weight of the metal ion-substituted inorganic carrier. The method of claim 1,
The metal ion is an inorganic antimicrobial agent, which is an ion of at least one metal selected from the group consisting of zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium and thallium. The method of claim 1,
The inorganic carrier is at least one selected from the group consisting of zeolite, calcium phosphate, zirconium phosphate and liquid glass. The method of claim 1,
Inorganic antimicrobial agent, characterized in that the metal hydroxide nanoparticles and the inorganic carrier are physically bonded The method of claim 1,
Inorganic antimicrobial agent, characterized in that the diameter of the metal hydroxide nanoparticles 1 to 100 nm Preparing a mixed solution by mixing water with aluminum chloride, aluminum sulfate, aluminum nitrate, zirconium chloride, zirconium sulfate, zirconium nitrate, or one or more combinations thereof and adding an inorganic carrier substituted with metal ions thereto;
Adding and adding sodium hydroxide to the mixed solution while adjusting the pH to 7 to 8;
Adding sodium silicate and sulfuric acid to the mixed solution to which sodium hydroxide is further added;
Leaving the mixed solution containing sodium silicate and sulfuric acid to form a precipitate; And
A method for producing the inorganic antimicrobial agent according to claim 1, comprising recovering the precipitate by filtration, washing and drying processes. The method of claim 7, wherein
The preparing or mixing of each of the mixed solutions is a method for preparing an inorganic antimicrobial agent by mixing for 1 to 2 hours at 10 to 200 rpm while maintaining the room temperature with respect to the mixed solution. 0.5 to 56% by weight of the inorganic antibacterial agent according to any one of claims 1 to 6; And
Thermoplastic resin composition comprising 44 to 99.5% by weight thermoplastic resin. A food packaging material, a semiconductor component packaging material, or an electronic product packaging material manufactured using the thermoplastic resin composition of claim 9 An article comprising the inorganic antibacterial agent according to any one of claims 1 to 6. The article of claim 11, wherein the article is made from fibers, paper, rubber, wood, glass, metal. Article characterized in that any one of the product selected
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