WO2018169331A1

WO2018169331A1 - Antibacterial food packaging material containing metal nanoparticle and production method therefor

Info

Publication number: WO2018169331A1
Application number: PCT/KR2018/003060
Authority: WO
Inventors: 황혜진; 고석근; 윤지성
Original assignee: 주식회사 아이큐브글로벌; 신지영; 황혜진
Priority date: 2017-03-15
Filing date: 2018-03-15
Publication date: 2018-09-20
Also published as: KR101780166B1

Abstract

The present invention relates to a method for producing an antibacterial food packaging material containing a metal nanoparticle, and an antibacterial food packaging material produced thereby and, particularly, to a method for producing an antibacterial food packaging material, in which a metal nanoparticle, such as copper, brass, bronze, silver, and zinc, is uniformly dispersed in a thin polymer film, and the resulting film is laminated on a polymer film having excellent thermal and mechanical properties, and an antibacterial food packaging material produced thereby.

Description

Antimicrobial food packaging material containing metal nanoparticles and its manufacturing method

The present invention relates to a method for producing an antimicrobial food packaging material containing metal nanoparticles and an antimicrobial food packaging material prepared therefrom. Specifically, metal nanoparticles such as copper, brass, bronze, silver, and zinc are uniformly dispersed in a thin polymer film and laminated with a polymer film having excellent thermal and mechanical properties. Antimicrobial food packaging material.

Food packaging materials are intended to maintain the freshness of foods (may be referred to as "food"), such as meat, fish, vegetables, fruits, processed foods for a certain time, and to prevent contamination from various harmful external environments. When food is stored, the freshness of the food decreases with time, and the corruption of the food cannot be avoided due to the growth of mold and bacteria. Due to the increase in the number of single households and the development of eating culture, there is an increasing need to store food for a long time, which causes a large amount of food to be destroyed and disposed of.

Various measures for long preservation of food have been developed. The most common methods include freezing, dried meat, pickling salt, and adding spices, but these have the disadvantage of changing the taste of the food and taking a lot of energy for preservation.

Therefore, research and development of antimicrobial food packaging material that maintains the freshness of food for a long time and prevents decay by bacteria and mold have been actively progressed, and various antibacterial packaging materials have been invented.

Korean Unexamined Patent Publication No. 2002-0090657 discloses a method of adding a metal powder to a high temperature molten polymer to make a master chip and using the same for injection molding. Another method is to prepare an antimicrobial packaging material using various kinds of organic preservatives or gas additives such as chlorine diside, ethanol, sulfur dioxide, triclosan and wasabi extract.

However, the conventional method of adding a metal mineral to the polymer has a disadvantage in that the manufacturing process is complicated, the manufacturing cost increases, agglomeration of metal particles, etc., reduces the quality uniformity of the packaging material and impairs the reproducibility of the process. On the other hand, in the case of a packaging material containing an organic preservative, there is a problem that the high temperature stability is deteriorated and the efficacy of the organic preservative is destroyed when processing a film using a polymer.

Recently, there is an attempt to manufacture a polymer film containing metal nanoparticles.

There are various methods of manufacturing metal nanoparticles, and Korean Patent Laid-Open No. 2002-0090657 discloses a metal vapor condensation method in which a metal vapor is made at a high temperature by using an expensive organometallic compound and ejected at a low temperature to condense it. It introduces. There is a method of making a film by adding the metal powder thus prepared to a certain amount of hot melted polymer. However, the metal nanoparticles produced by the metal vapor condensation method are relatively coarse at 100 nm in size.

On the other hand, there is a method of adding metal nanoparticles to a polymer by making a solution of metal nanoparticles by a chemical method and gradually adding them to the molten polymer material while blowing out the solvents in the solution. Thereafter, the polymer solution containing the metal nanoparticles is used as a high concentration master chip, and there is a method of mixing during direct injection molding. However, in such a process, nanoparticles are not uniformly dispersed, and thus there is a disadvantage in that antimicrobial properties are not excellent even if a large amount of metal nanoparticles are added.

In the process of adding nanoparticles to the polymer chip by chemical reduction method, inflow of impurities such as reducing agent and dispersant in each solution cannot be avoided, and various dispersing agents and reducing agents according to the type of polymer are different, and the process itself is complex. There are disadvantages.

It is an object of the present invention to provide a method for economically manufacturing an antimicrobial food packaging material which is harmless to the human body and has excellent antimicrobial properties, which can maintain freshness for a long time, and prevent food corruption.

It is another object of the present invention to provide an antimicrobial food packaging material capable of preventing the corruption of food and maintaining the freshness for a long time.

The present invention to achieve the above object

(a) preparing a polymer chip having metal nanoparticles deposited thereon;

(b) preparing a metal nanoparticle-containing polymer film by using the polymer chip having the metal nanoparticles deposited thereon;

(c) preparing a polymer member having heat resistance, and

(D) provides a method for producing an antimicrobial food packaging material comprising the step of laminating the metal nanoparticle-containing polymer film and the polymer member.

The present invention is characterized in that the polymer chip in which the metal nanoparticles are deposited on the surface is manufactured by a vacuum deposition method in a vacuum deposition tank.

The vacuum evaporation method is characterized in that the metal vapor particles are generated to be attached directly to the polymer chip while stirring the polymer chip in the vacuum deposition tank provided with a metal deposition source and a stirring tank containing the polymer chip.

In another aspect, the present invention provides an antimicrobial food packaging material prepared by the above method.

The antimicrobial food packaging material manufacturing method of the present invention has an effect of easily manufacturing a food packaging material having both antimicrobial properties and heat resistance by a simple process of laminating a metal nanoparticle-containing film and a polymer member having heat resistance. Using a polymer chip on which metal nanoparticles are deposited, there is an effect that an antimicrobial food packaging material can be manufactured directly in an existing process system. According to the present invention, since the metal nanoparticles are directly attached to the polymer chip in the manufacturing process, there is no need for a separate dispersion process and a dispersant to disperse the metal nanoparticles. In addition, since an additive such as a reducing agent required in a chemical process is not used, a polymer chip to which metal nanoparticles are attached can be obtained without introducing impurities. In the present invention, the metal nanoparticles attached to the polymer chip have a fine size of 10 nm and exhibit high antibacterial activity. The present invention has the advantage of reducing the raw material cost of the material can be reduced by the metal used in the production of the packaging material by manufacturing a food packaging material in a manner of laminating with a general film after producing a thin film having antimicrobial properties. Antibacterial acts only on the surface of the packaging material in contact with the food, while the other surface is made of a member having heat resistance, thereby ensuring a thermal stability and providing a food packaging material capable of printing.

Figure 1 is a schematic diagram of a method for producing antimicrobial food packaging material of the present invention.

2 is a schematic diagram of a vacuum deposition apparatus for manufacturing a polymer chip on which metal nanoparticles are deposited.

3 is a photograph of a PP chip on which silver nanoparticles of the present invention are deposited.

4 is a photograph of a PP chip on which copper nanoparticles of the present invention are deposited.

5 is a transmission electron micrograph of silver (Ag) which is one of the additive metals of the present invention.

Figure 6 is an antimicrobial film photo made of a general film injection machine using the LLDPE chip deposited copper nanoparticles of the present invention.

Figure 7 is a photograph of the antimicrobial film made of a general film injection machine using the PP chip deposited copper nanoparticles of the present invention.

8 is a photograph of an antimicrobial food packaging material made by laminating a LLDPE film and a PET film containing copper nanoparticles.

FIG. 9 is a photograph of a film appearance after heating water using a microwave oven after putting water in an antimicrobial food packaging material made by laminating a LLDPE film and a PET film including copper nanoparticles.

10 is a photograph of the appearance after storage of one day after microwave treatment after putting 100 ℃ water in the antimicrobial food packaging material made by laminating a LLDPE film and a PET film containing copper nanoparticles.

11 is a photograph of the antimicrobial test results for staphylococcus aureus of the antimicrobial food packaging material produced according to the present invention.

12 is an antimicrobial test result photograph of E. coli of the antimicrobial food packaging material produced according to the present invention, the left is the result of the control sample and the right is the result of the test sample.

FIG. 13 is a photograph after 10 days of storing white rice in a general packaging material (left) and LLDPE packaging material (right) to which copper nanoparticles prepared according to the present invention are added.

FIG. 14 is a photograph after 10 days of storing apples in a general packaging material (left) and LLDPE packaging material (right) to which copper nanoparticles prepared according to the present invention are added.

15 is a photograph after 10 days after storing the tofu in a general packaging material (left) and LLDPE packaging material (right) to which copper nanoparticles prepared according to the present invention are added.

Figure 16 is a copper-added LLDPE packaging material prepared according to the present invention after heating the water in a microwave oven after the addition of banana ((a): initial photo) and the photograph observed after heating to 60 ℃ in a heating oven (( b)) and after removing it from the bag ((c)).

FIG. 17 is 100 ° C. water in a copper-added LLDPE packaging material prepared according to the present invention and stored for one day after microwave treatment, when banana is added ((a): initial photograph) and after heating to 60 ° C. in a heating oven. ((b)) Observed photographs and photographs taken out of the bag ((c)).

18 and 19 are results obtained by requesting the analysis of harmful substances as food packaging material from the analysis agency certified by the Food and Drug Administration.

The present invention

(a) preparing a polymer chip having metal nanoparticles deposited thereon;

(c) preparing a polymer member having heat resistance; and

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The present invention is to produce an antimicrobial food packaging material by laminating a polymer film containing metal nanoparticles having antimicrobial and sterilizing ability and a polymer member having heat resistance used as a conventional food packaging material. While the process for preparing the antimicrobial food packaging material of the present invention is simple compared to the prior art, the prepared food packaging material has the advantages of having both antimicrobial and bactericidal effects useful for preservation of food and thermal stability of existing packaging materials.

1 briefly illustrates a manufacturing process of the food packaging material according to the present invention.

The polymer chip in which the metal nanoparticles are deposited on the surface of the step (a) is preferably manufactured by a method in which the metal nanoparticles are vacuum deposited on the surface of the carrier using the polymer chip as a carrier in a vacuum deposition tank.

Hereinafter, the vacuum deposition process of the vacuum deposition apparatus of FIG. 2 will be described in more detail. Vacuum deposition is carried out in a vacuum deposition tank (1), a stirring tank (2) provided in the lower portion of the vacuum deposition tank, a screw (3) provided in the stirring tank and stirring a carrier, that is, a polymer chip, and in the vacuum deposition tank It can be made using a metal particle deposition apparatus which is provided on the top of the stirring tank and composed of a deposition source 4 for generating metal vapor particles. The vacuum deposition tank may adjust the degree of vacuum to 10 ^-4 to 1 torr using the vacuum pump (5). In the low vacuum of 10 ^-4 torr or less, the vapor particles for forming nanoparticles are thickly deposited on the carrier near the vapor source from which the vapor particles are generated, but as the carriers move away from the vapor source, the average free path of the vapor particles is reduced. The distance is shortened so that the vapor particles are not deposited on the carrier.

The scattering direction of the atomized metal vapor in the deposition source is preferably in the direction opposite to the carrier. Since the vaporization direction of the atomized vapor is opposite to the carrier, the metal vapor is scattered upwards, but the vacuum degree is 10 ^-4 to 1 torr, so that the collision between the metal vapor particles and the inert gas particles caused by the inert gas filled therein results in an average free path. The metal vapor particles are shortened and are deposited on a carrier, ie, a polymer chip, which is moved downward by gravity and is stirred to form nanoparticles on the surface of the polymer chip.

In the vacuum deposition, it is preferable to adjust the speed of the screw for stirring the polymer chip at 1 to 200 rpm. If the stirring speed is less than 1 rpm, the agitation is not sufficiently done, there is a problem that the metal vapor particles are not evenly attached to the surface of the polymer chip, when the stirring speed exceeds 200 rpm, the stirred polymer chip is scattered There is this.

The vacuum degree of the vacuum deposition tank is controlled by including an inert gas, and the inert gas may be argon (Ar), neon (Ne), N ₂ , O ₂ , CH _4, or the like.

Generating steam particles for forming nanoparticles using the deposition source may use a physical vapor deposition method, for example, thermal deposition such as resistance heating, plasma heating, induction heating, laser heating, dish, etc. DC sputtering, DC-RF sputtering, laser sputtering, electron beam deposition (E-Beam Evaproation), etc. are mentioned.

In the present invention, the deposition time may be 10 minutes to 20 hours. By adjusting the time it is possible to control the concentration of the metal particles on the polymer chip.

The vacuum deposition may control the growth of the nanoparticles by adjusting the vacuum degree of the deposition tank, the speed of the screw, the deposition time, the deposition power and the like to control the size and amount of metal nanoparticles deposited on the polymer chip.

The polymers used in the manufacture of the polymer chip on which the metal nanoparticles of the present invention are deposited may be used without any limitation on the polymer surface capable of injection molding, but are preferably thermoplastic polymers. More preferably, linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polysufone (PS), polycarbonete (PC), polyvinylchloride (PVC), ABS (Acrylonitrile-butadiene-styrene) and PET (Polyethyleneterephthalate) are used. The size of the polymer chip is not limited but is preferably 1 to 5mm, more preferably 2 to 3mm.

The metal nanoparticles may be used both of the nanoparticle surface of the metal having antibacterial and antiseptic properties, and preferably metals such as copper, silver, zinc, brass, and bronze may be used. The average size of the metal nanoparticles is 2 to 30 nm, preferably 2 to 10 nm. When the nanoparticles are formed in the size as described above, the aggregation phenomenon between the nanoparticles is prevented and well dispersed in the polymer melt to prepare a polymer film in which the metal nanoparticles are well dispersed.

The amount of the metal nanoparticles deposited in the polymer on which the metal nanoparticles are deposited is preferably 0.01 to 0.5% by weight.

That is, the nanoparticles made by the method of the present invention are 2 to 30 nm in size, more preferably 2 to 10 nm in size, and are smaller than nanoparticles prepared by the metal vapor condensation method, thereby increasing the surface area of the metal in a small amount. It is possible to, and do not require a separate solvent removal process by depositing the nanoparticles on the polymer without using a dispersant, a solvent, etc. like a chemical method.

In addition, in the prior art, due to insufficient dispersion of nanoparticles and agglomeration of process steps, it is necessary to add a large amount of antimicrobial agent, resulting in low price competitiveness and limited performance sustainability of food packaging materials. There was a disadvantage that can not be used in containers.

In contrast, the nanoparticles produced by the method of the present invention do not need a separate solvent removal process because they have high purity, excellent uniformity, and do not contain a solvent. It is less than the nanoparticles, so even a small amount of metal nanoparticles have the advantage of high antimicrobial properties.

Step (b) of the present invention is a step of obtaining a thin polymer film containing the nanoparticles by inserting the polymer chip deposited on the surface of the metal nanoparticles into the injection machine. Polymeric chips in which the nanoparticles of the present invention are deposited have an advantage that the existing packaging material manufacturing process and equipment can be used as they are.

The injection step may be used by mixing the polymer chip on which the metal nanoparticles are deposited on the surface and the polymer chip on which the metal nanoparticles are not deposited. At this time, the mixing ratio of the polymer chip on which the metal nanoparticles are deposited on the surface and the polymer chip on which the metal nanoparticles are not deposited is preferably 1:10 to 1: 1 by weight. That is, the present invention can easily prepare a polymer film in which the fine metal nanoparticles are evenly dispersed by uniformly mixing and melting and injecting the polymer chip having the metal nanoparticles deposited on the surface and the general polymer chip on which the metal nanoparticles are not deposited. Can be.

In this case, if the film is manufactured in a thin thickness, the surface area is increased relative to the volume, and even though a small amount of metal is added, many metals are exposed to the surface to provide a high antibacterial effect. The thickness of the film produced in step (b) is not limited, but a thin thickness of 0.05 mm or less, preferably 0.01 mm or less is preferred in order to expose the metal to the surface as much as possible. The temperature for melting the polymer chip may be 100 ° C. or more.

That is, if the thin polymer film to which the metal of step (b) is added is laminated to a general film to produce a food packaging material, it is possible to manufacture a product having a high antibacterial property and a suitable thickness and strength while using a minimum amount of metal.

On the other hand, when manufacturing a food packaging material with a polymer film containing metal nanoparticles in the present invention, the antimicrobial activity caused by contact with bacteria is a metal exposed on the surface and the particles inside do not directly contribute to the antimicrobial effect, In this case, the nanoparticles dispersed well inside are placed between the long chains of the polymers, which prevents partial movement of the polymers, thereby inhibiting the penetration and diffusion of oxygen, which is the main cause of food decay, and lowers the oxygen permeability. .

Step (c) of the present invention is to prepare a polymer member for general food packaging materials having heat resistance and mechanical strength. The polymer member is preferably PET, OPP, PVC, PS, nylon, HDPE and the like. The polymer member may be a thin polymer film or a thick film for a food tray. The thickness of the polymer member may be 0.05 to 0.5 mm depending on the required mechanical strength.

Step (d) of the present invention is a step of laminating the polymer film having the antibacterial and bactericidal function of step (b) and the polymer member having the heat resistance and the mechanical strength of step (c). The lamination may use a laminating method and may use a dry method or a tea die method. Two or more kinds of polymer films may be formed by pressing a roller by heating heat. At this time, it may be laminated using a separate adhesive and / or solvent or using PE. The polymer film layer including the metal nanoparticles of the manufactured food packaging material is a surface in direct contact with the food.

The food packaging material of this invention can further laminate a functional polymer member as needed. In this case as well, the surface directly contacting the food is a polymer film layer containing metal nanoparticles.

The present invention provides an antimicrobial food packaging material prepared through the above steps (a) to (d) and including a polymer nanoparticle-containing polymer film layer and a polymer member layer having heat resistance. The food packaging material of the present invention includes the metal nanoparticles in contact with the food can maintain the freshness of the food for a long time and give an antibacterial effect, the other side provides the heat resistance and mechanical strength required for the food packaging material.

The metal nanoparticle-containing polymer film layer of the food packaging material of the present invention is well dispersed in the metal nanoparticles, the film surface has a double effect of imparting even antibacterial power and the inside of the film to prevent oxygen permeation, which is the main culprit of food decay. On the other hand, when it is made into thin film, it is combined with the films that have excellent mechanical strength, heat resistance, and printability to prevent mechanical properties from falling off. Therefore, antibacterial sterilization, oxygen permeation prevention, mechanical property increase, thermal property increase, and excellent Provided is a food packaging material having printability.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1 Fabrication of LLDPE Polymer Chip and PP Polymer Chip with Metal Nanoparticles Deposited on Surface

1-1. A disk-type copper (Cu) or silver (Ag) target of 10 cm diameter and 1 cm thickness is attached to the DC sputtering cathode. After the LLDPE chip used as a packaging material was put into a stirring tank in the vacuum chamber, the vacuum chamber door was closed and vacuum evacuation was started. The weight of the injected polymer chip is 6.5 kg. A low vacuum of 1x10 ^-2 Torr was made using a rotary pump, and a high vacuum of 1x10 ^-5 Torr or less was made using an oil diffusion pump.

Ar gas was injected into the vacuum chamber at a high vacuum at a flow rate of 50 to 150 sccm and the polymer chip was stirred at a speed of 60 rpm. Ar gas injection is intended to create a plasma for deposition and polymer chip agitation is to ensure that the deposited particles are kept coarse and not coarse. When power is applied to DC power, plasma is generated and deposition of metal particles proceeds. The deposition time is 9 hours and the metal concentration is 0.3 wt% each.

1-2. A PP chip in which copper or silver was deposited was prepared in the same manner as in Example 1-1 using the PP chip (see FIGS. 3 and 4).

5 is a transmission electron micrograph of silver (Ag) which is one of the additive metals. As seen in the TEM picture of silver, its size is less than 20 nm, mostly around 10 nm, which is fine compared to the general electric explosion method (about 50 to 100 nm), one of the existing physical vapor deposition methods. Since the antimicrobial effect acts on the surface of metal particles, the larger the surface area, the higher the efficiency. In the present invention, when the fine metal nanoparticles of 10 nm size are uniformly dispersed in the polymer, the amount is smaller than the large mass of 50-100 nm size. In addition, the surface of the polymer can be evenly exhibited antimicrobial properties, making a high surface area is a cause of showing the high antibacterial properties of the packaging material.

Example 2 Preparation of Polymer Film Containing Metal Nanoparticles

2-1. A film having a thickness of 0.01 mm was prepared using a polymer chip in which LLDPE and copper LLDPE prepared in Example 1-1 were mixed at a weight ratio of 9: 1. Film manufacturing conditions are melted by heating to about 150-200 ℃ in a typical polymer film injection vessel and the film is injected to room temperature in the atmosphere (Fig. 6).

2-2. A film having a thickness of 0.01 mm was prepared using a polymer chip in which PP and copper (Cu) prepared in Example 1-2 were mixed at a weight ratio of 9: 1.

Example 3 Preparation of Food Packaging Material Laminated with PET Film

A PET film having a thickness of 12 μm was prepared and laminated with an LLDPE film including copper nanoparticles prepared in Example 2-1 to prepare an antimicrobial food packaging material.

The laminating method is to mix the adhesive and the EA solvent between the PET film and the antimicrobial LLDPE, pass the rollers, and then laminate to make one film (Fig. 8).

Example 4 Heat Resistance Test

4-1. After preparing a film container using the food packaging material prepared in Example 3, the water was added and the water was heated using a general microwave oven and the appearance of the film was observed. This is illustrated in FIG. 9.

As shown in the photo, the laminated PET film is stable at a high temperature, so the shape of the film container can be seen to be maintained even when the water inside the film becomes a high temperature. In addition, it can be seen that the polymer film to which the nanoparticles are added only warms the water inside without affecting the microwave like a general polymer.

4-2. 100 ℃ water was added to the film container prepared in Example 3 after the microwave treatment and stored after one day appearance is shown in Figure 10.

As shown in Figure 10 can be confirmed that there is no deformation in color or form even if stored for a long time at 100 ℃ water.

In general, when the use of an organic antimicrobial material or chemically added metal nanoparticles for antibacterial, the packaging material is easily deteriorated at a high temperature, and the original color is changed. In the case of the present invention, it can be confirmed that there is no deterioration as shown in FIGS. 9 and 10. .

Example 5 Antimicrobial Test

The antimicrobial test of the antimicrobial food packaging material of the present invention was conducted. After adding copper to the LLDEP polymer chip and melting it to produce a film, the antimicrobial test was performed using the film adhesion method (JIS Z 2801) and the results were shown.

The bacteria used for the test were Staphylococcus aureus and Escherichia coli, and the change patterns of the bacteria are shown in Table 1 and Table 2, respectively. The antimicrobial activity against bacteria was 4.6 for Staphylococcus aureus and 3.2 for Escherichia coli, which is higher than that of the standard 2.0.

	대조샘플Control sample	시험샘플Test sample
초기균수Initial bacterial count	1.3 X 10⁴ 1.3 X 10 ⁴	1.3 X 10⁴ 1.3 X 10 ⁴
24시간 후24 hours later	2.5 X 10⁴ 2.5 X 10 ⁴	< 0.63<0.63
항균활성치Antimicrobial activity	--	4.64.6

	대조샘플Control sample	시험샘플Test sample
초기균수Initial bacterial count	1.3 X 10⁴ 1.3 X 10 ⁴	1.4 X 10⁴ 1.4 X 10 ⁴
24시간 후24 hours later	1.3 X 10⁶ 1.3 X 10 ⁶	8.1 X 10² 8.1 X 10 ²
항균활성치Antimicrobial activity	--	3.23.2

11 is a bacterial growth picture of the control sample and the test sample for Staphylococcus aurea, Figure 12 is a bacterial growth picture of the control sample and the test sample for Escherichia coli. Both strains showed a decrease in strains in the test sample compared to the control sample. Example 6 Food Storage Capacity Test

6-1. After the white rice was stored at room temperature for 10 days in a general packaging material (left) and a copper-added LLDPE packaging material (right) manufactured according to the present invention, the resulting photograph is shown in FIG. 13.

As shown in the picture, the white rice stored in the general film is a fungus bacteria breeding from the initial 3-4 days after 10 days can be seen that the fungus bacteria are almost black, but when using the packaging material of the present invention white rice 10 days It can be seen that the fungi do not multiply and maintain the color of white rice even after elapsed.

6-2. 14 is a photograph of the result after storing the apple in a normal packaging material (left) and the copper-added LLDPE packaging material (right) manufactured according to the present invention at room temperature for 10 days. As shown in the picture, in the case of apples stored in a general film, the fungus bacteria grow from the first 3-4 days, and after 10 days, the fungus bacteria can be seen in many parts, but when the l packaging material of the present invention is used, the apples 10 It can be seen that after a period of time the fungi do not multiply and retain their color.

6-3. 15 is a photograph after 10 days at room temperature after storing the tofu in a general packaging material (left) and the copper-added LLDPE packaging material (right) manufactured according to the present invention. As shown in the picture, the tofu stored in the general film can be seen that the fungus bacteria have been propagated from the beginning 3-4 days, but when using the packaging material of the present invention, the tofu is seen to keep the fungus without propagation even after 10 days. Can be.

13, 14, and 15 of the decay field test results, the antimicrobial packaging material of the present invention has excellent antimicrobial properties compared to the general commercial packaging, it can be seen that it can maintain the freshness and delay the decay during food storage.

<Example 7> Rapid deterioration degree test

7-1. In the LLDPE packaging material containing copper of the present invention, water was added in the same manner as in Example 4-1, and water was heated using a general microwave oven, and then the degree of food rapid deterioration was tested using the packaging material. Figure 16 is immediately after putting the banana in the copper-added LLDPE packaging material produced according to the present invention ((a)) and after heating for 1 hour and 30 minutes at 60 ° C. in the heating oven ((b)) and the contents were taken out It is a photograph observing the change of ((c)).

In general packaging material, while the yellow color of the banana is changed to black in the rapid deterioration experiment, the packaging material of the present invention can be confirmed that there is no discoloration of the banana unlike the general packaging material. In other words, unlike ordinary organic antimicrobial material can be indirectly confirmed that the deterioration in water or microwave or copper nanoparticles are not eluted.

7-2. The LLDPE packaging material containing copper of the present invention was tested for the degree of food rapid deterioration by using the packaging material after one day of 100 ° C. water was added as in Example 4-2. Figure 17 is prepared in accordance with the present invention and immediately after putting the banana in the copper-added LLDPE packaging material after 100 days of water and microwave treatment and stored for 1 day (a) and heated to 60 ℃ in a heating oven for 1 hour 30 minutes It is a photograph observing the change of ((c)) after ((b)) and only the contents were taken out.

Unlike general packaging materials, the packaging materials of the present invention can be seen that the copper nanoparticles are not easily eluted even after 100 ℃ water storage for one day has antibacterial sterilization performance.

Example 8 Component Analysis

18 and 19 is a harmful ingredient analysis table of the food packaging material of the film received from an authorized agency. As shown in the analysis table, the packaging material of the present invention does not contain harmful metals and harmful organic compounds, or contains potassium permanganate, which is far below the standard value. Therefore, the packaging material does not contain harmful ingredients. It can be seen that in the process of making the packaging film, it can be produced very simply and easily without containing harmful ingredients.

The present invention has the effect of easily manufacturing a food packaging material having both antibacterial and heat resistance by a simple process of laminating a metal nanoparticle-containing film and a polymer member having heat resistance. Using a polymer chip on which metal nanoparticles are deposited, there is an effect that an antimicrobial food packaging material can be manufactured directly in an existing process system.

The antimicrobial food packaging material produced by the manufacturing method of the present invention is an excellent industrial applicability having both antibacterial and heat resistance.

Claims

(a) preparing a polymer chip having metal nanoparticles deposited thereon;

(b) preparing a metal nanoparticle-containing polymer film by using a polymer chip having the metal nanoparticles deposited on a surface thereof;

(c) preparing a polymer member having heat resistance; and

(D) manufacturing an antimicrobial food packaging material comprising the step of laminating the metal nanoparticle-containing polymer film and the polymer member.
The method of claim 1, wherein the polymer chip on which the metal nanoparticles are deposited is manufactured by a vacuum deposition method in a vacuum deposition tank.
The antimicrobial method of claim 2, wherein the vacuum deposition method generates metal vapor particles while directly attaching the polymer chip to the polymer chip while stirring the polymer chip in the vacuum deposition tank including the stirring chamber containing the polymer chip and the metal deposition source. Food Packaging Material Manufacturing Method
The method according to claim 1, wherein the step (b) is characterized in that the antimicrobial, characterized in that the mixture of the polymer chip on which the metal nanoparticles are deposited on the surface and the polymer chip on which the metal nanoparticles are not deposited in a 1:10 to 1: 1 weight ratio How to prepare food packaging materials
The polymer of the polymer chip on which the metal nanoparticles are deposited on the surface is linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), PS (Polysufone), PC (Polycarbonete), PVC (Polyvinylchloride), ABS (Acrylonitrile-butadiene-styrene), and PET (Polyethyleneterephthalate) PET manufacturing method characterized in that at least one member selected from the group consisting of.
The method of claim 1, wherein the metal is copper, silver, zinc, brass and bronze antimicrobial food packaging material manufacturing method characterized in that at least one member selected from the group consisting of.
The polymer member of the polymer member having heat resistance is selected from the group consisting of polyethylene terephthalate (PET), oriented polypropylene (OPP), polyvinylchloride (PVC), nylon, high-density polyethylene (HDPE) and polysufone (PS). Antimicrobial food packaging material manufacturing method characterized in that at least one
The method for producing an antimicrobial food packaging material according to claim 1, wherein the polymer member having functionality is further laminated at least one kind.
Prepared by the manufacturing method of claim 1

Antimicrobial food packaging material comprising a metal nanoparticle-containing polymer film layer and a polymer member layer having heat resistance