KR102416189B1 - Method of keep-freshness packaging film with high supportable mesoporous silica for enhancement of the oxygen and water-vapor transmission rate - Google Patents

Abstract

The present invention relates to a method for preparing a freshness keeping packaging film containing high supportable mesoporous silica which includes (step 1) a step of preparing a polyethylene chip and a master batch containing a composite in which an antibacterial functional natural material is supported on mesoporous silica as a molten mixture; and (step 2) a step of forming the molten mixture with an extruder, stretching the same into a film, cooling the film, and winding the film on a roll, wherein the mesoporous silica has a specific surface area of 850 ㎡/g or more.

Description

Method of manufacturing a keep-freshness packaging film with high supportable mesoporous silica for enhancement of the oxygen and water-vapor transmission rate

The present invention relates to a method of manufacturing a packaging film containing high-supporting mesoporous silica having improved oxygen permeability and moisture permeability.

In order to prevent damage, deterioration, and corruption caused by external shocks that may occur in the distribution process of the product, the product is packaged and distributed with packaging materials such as paper, film, and plastic. In particular, agricultural and fishery products, such as vegetables, fruits, fish, and meat, which are susceptible to deterioration and spoilage, have a problem in that the value of the products may decrease rapidly depending on the environment and storage period of the distribution process. In addition, among agricultural and fishery products, especially post-ripe fruits such as apples, bananas, strawberries, and tomatoes, and wet aquatic feeds such as fish feed, even after sterilization, the distribution and storage period is only one week. As a result, the sales time is only 3 to 6 days at room temperature. Due to such a short distribution and storage period, there is a problem that the disposal of agricultural and fishery products past the expiration date causes economic loss. According to 2013 data from the Health Industry Promotion Agency, the cost of food discarded beyond the expiration date is estimated to be 950 billion won for consumers and 590 billion won for manufacturers. In addition, according to a study by the US GMA, 39% of all fresh foods are discarded due to the expiration of the expiration date stated on the label. In addition, it is estimated that the loss cost of processed foods that are discarded past the consumption period due to the short distribution and storage period is over 1.3 trillion won. Therefore, it is necessary to develop a new packaging film that can reduce enormous economic loss, and can further increase the storage period and safety of agricultural and livestock products by extending the distribution and storage period.

Accordingly, product development of a freshness-retaining packaging film that can prevent a decrease in the value of agricultural and fishery products due to deterioration and spoilage during the distribution process is being developed. The presently known technology of packaging film (Registration Patent Publication No. 10-2015-0128987) forms a package with an antibacterial film obtained through polymerization of a compound, and when an object to be packaged is sealed, the surface facing the object to be packaged It can exhibit the effect of maintaining the freshness of the packaged product by inhibiting the growth of bacteria. Another packaging film technology (Registration Patent Publication No. 10-1030231) is a low-carbon, eco-friendly, freshness retention film packaging material by compounding poly-L-lactic acid and inorganic nano particles and forming pores by laser or mechanical punching to increase oxygen permeability. that can be used as

The above technology has problems such as a high manufacturing cost due to a complicated production process, or a decrease in physical properties of the film by using additional micro-punching. Therefore, it is necessary to develop a packaging film that maintains freshness that can overcome this problem and can maximize the storage period and stability by better maintaining the freshness of livestock and fishery products and processed foods using the same.

Republic of Korea Patent Publication No. 10-2015-0128987 (2014.03.13) Republic of Korea Patent Publication No. 10-1030231 (2010.10.06)

In order to solve the above problems, the present invention is a highly supported mesoporous silica with improved oxygen permeability and moisture permeability that can maximize the storage period and stability by maintaining the freshness of livestock and marine products and processed foods using the same. An object of the present invention is to provide a method for manufacturing a packaging film containing freshness. In addition, it is possible to reduce the manufacturing cost by simplifying the production process compared to the prior art, and to provide a method of manufacturing a packaging film containing freshness retention mesoporous silica with improved oxygen permeability and moisture permeability that exhibits superior mechanical properties. do.

An aspect of the present invention for achieving the above object is (step 1) preparing a master batch and a polyethylene chip comprising a composite in which an antibacterial functional natural material is supported on mesoporous silica as a molten mixture; and

(Step 2) forming the molten mixture with an extruder, stretching it into a film, cooling the film, and winding the film on a roll; including;

The mesoporous silica relates to a method of manufacturing a packaging film containing high-supporting mesoporous silica, characterized in that it has a specific surface area of 850 m 2 /g or more.

In one aspect, the complex may be characterized in that 15 to 50% by weight of the antibacterial functional natural material is included in the total weight of the complex.

In one aspect, the master batch may be characterized in that 15 to 25% by weight of the complex in which the antibacterial functional natural material is supported on mesoporous silica is included.

In addition, another aspect of the present invention is a film comprising a polyethylene and a composite in which an antibacterial functional natural material is supported on mesoporous silica,

The film contains 0.001 to 10% by weight of the composite, and has an oxygen permeability of 10,000 to 15,000 cm ³ /(m ² ·24hr·atm), and a moisture permeability of 10 to 25 g/(m ² ·day). It relates to a freshness retention packaging film containing high support mesoporous silica.

In another aspect, the film may be characterized in that the antibacterial activity calculated according to Equation 1 below is 95% or more.

[Formula 1]

Antibacterial activity (%) = (A-B)/A × 100

(In the above formula, A is the average number of colonies of the control group (CFU/ml), and B is the average number of colonies of the test sample (CFU/ml).

In addition, another aspect of the present invention relates to a packaging material comprising the above-described high-supporting mesoporous silica-containing freshness packaging film.

The manufacturing method of the high-supporting mesoporous silica-containing freshness packaging film according to the present invention can further reduce the manufacturing cost of the freshness retention packaging film by simplifying the production process compared to the prior art, and can exhibit better mechanical properties. In addition, the manufactured high-supporting mesoporous silica-containing freshness packaging film contains antibacterial and functional natural substances, so it has an excellent antibacterial action, and has excellent oxygen permeability and moisture permeability. Freshness can be better maintained, which can further increase shelf life and stability.

1 is a perspective schematic view showing an apparatus for preparing a master batch for a freshness retention packaging film of the present invention.
2 is a thermogravimetric (TGA) analysis graph of Examples and Comparative Examples;
3 is an analysis result of the antibacterial inhibition efficiency of Examples and Comparative Examples.
4 is a comparative graph of storage evaluation of Examples and Comparative Examples.
5 is a comparison chart of chromaticity changes of post-ripening crops (bananas) of Examples and Comparative Examples.

Hereinafter, a method for manufacturing a freshness retention packaging film containing high support mesoporous silica having improved oxygen permeability and moisture permeability according to the present invention will be described in detail. The drawings introduced below are provided as examples so that the spirit 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. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

Agricultural and fishery products, such as vegetables, fruits, fish, and meat, which are susceptible to deterioration and spoilage, have a problem in that the value of the products may decrease rapidly depending on the environment and storage period of the distribution process. A freshness-retaining packaging film product has been developed that can prevent the decline in the value of agricultural and fishery products due to deterioration and spoilage during the distribution process. However, the prior art has problems such as a high manufacturing cost due to a complicated production process, or a decrease in physical properties of the film by using additional micro-punching.

Therefore, the inventors of the present invention contain an antibacterial functional natural substance, which has an excellent antibacterial action, exhibits more excellent tensile strength, and exhibits better oxygen permeability and moisture permeability, so that it is possible to maintain better freshness, thereby further increasing the storage period and stability of food. After repeated research to develop a method for manufacturing freshness packaging film that can reduce manufacturing costs compared to conventional technology, the production process of freshness packaging film manufacturing is simplified and antibacterial functional natural substances are supported on mesoporous silica. It has been found that the above object can be achieved when a film is produced using a master batch containing the composite, and thus the present invention has been completed.

The preparation of the packaging film containing high-supporting mesoporous silica with improved oxygen permeability and moisture permeability according to the present invention should precede ceramic-polymer complexation through preparation of a high content master batch.

First, an apparatus for manufacturing a master batch for a packaging film containing high carrying capacity mesoporous silica containing freshness of the present invention will be described in detail with reference to FIG. 1 .

An apparatus for manufacturing a food packaging film containing high-supporting mesoporous silica according to the present invention includes a ceramic quantitative feeder (1-1), a polymer quantitative feeder (1-2), a twin screw (2), and a heating unit (3). ), a water tank (4), a master batch (M/B) cooling device (5) using compressed air, a cooling water thermometer (6), and a pelletizer (7).

The quantitative feeder of the apparatus for manufacturing a food packaging film containing supported mesoporous silica of the present invention is for supplying high-supported mesoporous silica and polymer pellets in a quantitative manner, and a ceramic quantitative supplying device (1-1), and A polymer metering unit (1-2) is provided, and it is operated as a set of two, and the individual revolution per minute (RPM) can be adjusted. A separate stirrer (not shown) may be included to prevent defective supply caused by development.

In addition, the twin screw (2) is wrapped with a heat wire that is precisely controlled, has a design optimized for the complexation of the high carrying capacity mesoporous silica and the polymer, and the temperature of the heating part (3) during injection is 180 ° C or less can be maintained automatically.

In addition, the M/B cooling device 5 using the water tank 4 and compressed air circulates cooling water at about 10 ° C. 6) is included.

In addition, the pelletizer 7 may be configured to process the produced composite injection molding to a predetermined size to produce pellets having a size of about 1.5 mm.

In the case of manufacturing a master batch for a packaging film containing freshness retention mesoporous silica in the above apparatus, the production process is simplified compared to the conventional technology, thereby further lowering the manufacturing cost of the packaging film maintaining freshness.

Next, a method of manufacturing a packaging film containing freshness retention mesoporous silica with high supportability will be described in detail.

(Step 1) preparing a molten mixture of a master batch and a polyethylene chip including a composite in which an antibacterial functional natural material is supported on mesoporous silica; and

(Step 2) forming the molten mixture with an extruder, stretching it into a film, cooling the film, and winding the film on a roll; including;

The mesoporous silica may be characterized in that it has a specific surface area of 850 m 2 /g or more, more preferably 850 to 1300 m 2 /g.

The first step is a) manufacturing a mesoporous silica and supporting an antibacterial functional natural material on the mesoporous silica to prepare a complex in which the antibacterial functional natural material is supported on the mesoporous silica;

b) pulverizing and heating the composite and polyethylene chips to prepare a molten mixture;

c) discharging the molten mixture as an injection product; and

d) cutting the injection-molded product to prepare a master batch; may include. A master batch may be prepared by complexing the mesoporous silica with a polymer such as low density polyethylene (LDPE), high density polyethylene (HDPE), or polypropylene (PP). According to the polymer used in the packaging film, it is preferable that the complex conditions should be controlled, but if necessary, a plurality of polymers may be combined to form a complex. In addition, the mesoporous silica may be prepared through a hydrothermal method in which a surfactant and a silica precursor are reacted at a high temperature using water as a solvent. More preferably, the mesoporous silica is characterized in that it is prepared under neutral conditions. More specifically, it proceeds to a process of mixing a surfactant with water and then adding a silica precursor. The surfactant and water are carried out under stirring at 30-50° C., preferably 35-45° C. so that the surfactant can be dissolved. It is carried out under stirring for 24 to 48 hours, preferably 36 to 48 hours so that mixing can be achieved well. Thereafter, a silica precursor is added to allow hydrolysis of the surfactant and the silica precursor, and the reaction of the silica precursor is carried out at 30-50° C., preferably at 35-45° C., under stirring for 24 hours. Then, by stopping the stirring and aging under heating and pressure conditions, mesoporous silica can be produced. That is, the aging step under heating and pressurization conditions is to make the silica outer wall more uniform in the hydrothermal synthesis reaction, and can make the mesoporous silica stable. In this regard, according to a preferred embodiment of the present invention, the aging process is particularly preferably performed by sealing the inside using a large-capacity equipment of 100 to 500L, and the pressure naturally increases during the temperature increase process. In the aging step, the temperature, that is, the hydrothermal synthesis temperature, may be preferably set at 110 to 130°C, particularly preferably around 120°C. In addition, a representative example of the surfactant is a poly(alkylene oxide) block copolymer, for example, polyethylene oxide-block-(polypropylene oxide)-polyethylene oxide, and BASF's product name Pluronic P123 may be used. In addition, various silica precursors widely known in the art may be used as the silica precursor, but tetraethyl orthosilicate (TEOS) is preferably used. On the other hand, for the production of mesoporous silica, it is sufficient if the surfactant is dissolved in an aqueous solution to form micelles, that is, a concentration greater than or equal to the critical micelle concentration (CMC). In consideration of the above points, the silica precursor may be used in a ratio of 0.01 to 0.02 moles based on 1 mole of the surfactant. In addition, the mesoporous silica may be powdered to a particle size of 10 μm or less, preferably in a particle size of 1 to 10 μm. When the particle size of the mesoporous silica exceeds 10 μm, agglomeration may occur during preparation of the master batch, which is not preferable. More preferably, the mesoporous silica may be surface-modified to improve dispersibility to increase miscibility with polyethylene chips. The mesoporous silica may be surface-modified by immersion in a reaction solvent in which a silane coupling agent is dissolved in an organic solvent and stirring, and the coupling agent may be contained in an organic solvent in an amount of 1 to 5% by weight compared to the mesoporous silica. When the content of the silane coupling agent is less than 1% by weight compared to the mesoporous silica, the surface of the mesoporous silica is not sufficiently modified, and when it exceeds 5% by weight, the surface modification effect according to the weight is insignificant, so it is not preferable. Moreover, it is preferable that stirring time is 1 to 5 hours, and stirring temperature is 100-150 degreeC. When the stirring time or stirring temperature is less than the above range, the surface of the mesoporous silica is not sufficiently modified, and when it exceeds the above range, the effect of surface modification according to time or temperature is insignificant, which is not preferable. At this time, the organic solvent is dichloromethane, tetrahydrofuran (THF), ethanol (ethanol), methanol (methanol), acetone (acetone), dimethylformamide (dimethylformamide; DMF), dimethyl sulfoxide (dimethylsulfoxide) ; DMSO) and may be at least one selected from the group consisting of dioxane (dioxane). In addition, the silane coupling agent is bis [3-triethoxysilylpropyl] tetrasulfide (triethoxysilylpropyl tetrasulfide; TESPT), mercaptopropyl triethoxysilane (mercaptopropyl triethoxysilane), aminopropyltriethoxysilane (aminopropyltriethoxysilane), chloro chloropropyl triethoxysilane, vinyltriethoxysilane, methacryloxytpropyl triethoxysilane, methacryloxypropyl triethoxysilane, glycidoxypropyl tri It may be at least one selected from the group consisting of ethoxysilane (glycidoxypropyl triethoxysilane), isocyanatopropyl triethoxysilane (isocyanatopropyl triethoxysilane), and cyanatopropyl triethoxysilane (cyanatopropyl triethoxysilane).

In addition, in order to impart antibacterial functionality to the mesoporous silica, an antibacterial functional natural material may be loaded before complexation with a polymer. Separately from the preparation of mesoporous silica as described above, an aqueous solution of an antibacterial and functional natural substance is prepared. In this case, the antibacterial functional natural material may be any one or two or more selected from the group consisting of bisabolol, chitin, chitosan, propolis, lysozyme, hinokichiol, and polyphenols. In addition, the amount of water used in preparing the antibacterial functional natural substance precursor aqueous solution is not particularly limited, and the loading amount can be adjusted by adjusting the concentration of the antibacterial functional natural substance precursor aqueous solution. It may be used in the same amount as the pore volume of the mesoporous silica used in the subsequent step of supporting the antibacterial functional natural material precursor on the mesoporous silica support. By supporting the aqueous solution of the antibacterial functional natural material precursor prepared as described above on the solid powdery mesoporous silica, a complex in which the antibacterial functional natural material is supported on the mesoporous silica can be prepared. In this case, the process of supporting the antibacterial functional natural material precursor may be performed in a manner known in the art.

Next, the master batch and polyethylene chips including the composite in which the antibacterial functional natural material is supported on mesoporous silica are filmed through conventional melt extrusion molding, and then the thickness of the film can be stretched to 30 to 70 μm. The stretched film may exhibit a tensile strength of 25 to 28 MPa.

As such, the manufacturing method of the high-supporting mesoporous silica-containing freshness packaging film according to the present invention can further reduce the manufacturing cost of the freshness packaging film by simplifying the production process compared to the conventional technology, and exhibit better mechanical properties. . In addition, the prepared freshness packaging film containing mesoporous silica has excellent oxygen permeability and moisture permeability. can be further increased.

As a specific example, the complex may be characterized in that 15 to 50% by weight of the antibacterial functional natural material, preferably 20 to 50% by weight, more preferably 30 to 50% by weight of the total weight of the complex. When the antibacterial functional natural material in the total weight of the complex is less than 15% by weight, when a freshness maintenance packaging film is manufactured using the master batch containing the complex, the antibacterial property of the film is not excellent, and the antibacterial functional natural material is 50 in the total weight of the complex When the content is more than % by weight, the tensile strength of the film may decrease when a freshness-maintaining packaging film is manufactured using the master batch including the composite.

In addition, the master batch may be characterized in that it contains 15 to 25% by weight of a complex in which an antibacterial functional natural material is supported on mesoporous silica.

In the case of the master batch, when the amount of the complex in which the antibacterial functional natural material is supported on mesoporous silica is less than 15% by weight, the improvement of oxygen permeability and moisture permeability is insignificant when manufacturing a freshness packaging film using the master batch containing the complex, When the composite is more than 25% by weight, dispersibility is lowered when manufacturing a freshness packaging film using a master batch including the composite, which may affect a decrease in the tensile strength of the film.

In addition, another aspect of the present invention is a film comprising a polyethylene and a composite in which the aforementioned antibacterial functional natural material is supported on mesoporous silica, and the film is 0.001 to 10% by weight, preferably 0.01 to 10% by weight, more preferably contains 0.1 to 10% by weight of the composite, and has an oxygen permeability of 10,000 to 15,000, preferably 11,000 to 15,000, more preferably 12,000 to 15,000 cm ³ /(m ² ·24hr·atm), and a moisture permeability of 10 to 25 , preferably from 12 to 25, more preferably from 15 to 25 g/(m ² ·day).

In another aspect, the film may be characterized in that the antibacterial activity calculated according to Equation 1 below is 95% or more.

[Formula 1]

Antibacterial activity (%) = (A-B)/A × 100

(In the above formula, A is the average number of colonies of the control group (CFU/ml), and B is the average number of colonies of the test sample (CFU/ml).

At this time, since the complex in which the antibacterial functional natural material is supported on mesoporous silica is the same as described above, a redundant description will be omitted.

A film containing a composite in which an antibacterial functional natural material is supported on mesoporous silica by satisfying the above range is very excellent in oxygen permeability, moisture permeability, and antibacterial activity, so that it is possible to suppress browning of fresh food and inhibit microbial growth, etc. Since it can exhibit a very good freshness retention function, the storage period and stability of fresh food can be further improved.

In addition, another aspect of the present invention relates to a packaging material comprising the above-described high-supporting mesoporous silica-containing freshness packaging film.

In this case, since the high-supporting mesoporous silica-containing freshness-maintaining packaging film is the same as described above, a redundant description will be omitted.

The packaging material including the film also has excellent oxygen permeability, moisture permeability, and antibacterial activity, so it can exhibit very good freshness maintenance functions such as inhibiting browning of fresh food and inhibiting microbial growth, so that the storage period and stability of fresh food can be improved even better.

Hereinafter, a method of manufacturing a packaging film containing high-supporting mesoporous silica having improved oxygen permeability and moisture permeability according to the present invention will be described in more detail through Examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention. In addition, the unit of additives not specifically described in the specification may be weight %.

[Example 1]

1-1. Manufacture of a complex in which antibacterial and functional natural substances are supported on mesoporous silica.

2135 g of Pluronic P123 and 80 L of water were mixed and stirred at about 40° C. for about 48 hours, and then 4534 g of tetraethyl orthosilicate (TEOS) was added and stirred at 40° C. for about 24 hours. After silica particles were generated, the solution became opaque, the stirring was stopped, and the mixture was heated to 120° C. and aged for 8 hours. Then, the aged silica particles were naturally cooled at room temperature and then washed with water. The washed silica particles were dried in a dryer for 24 hours and then calcined at 550° C. for 6 hours to prepare mesoporous silica. 15% by weight of bisabolol, an antibacterial functional natural material, was added to the mesoporous silica to prepare a composite in which the antibacterial functional natural material was supported on the mesoporous silica.

1-2. Manufacture of master batch for packaging film containing freshness retention mesoporous silica with high supportability.

In order to control the content of the complex in which the antibacterial and functional natural substances are supported on the mesoporous silica in the master batch to be constant at 10 wt%, a polyethylene chip (a polymer quantitative feeder (1-2)) and an antibacterial functional natural substance are supported on the mesoporous silica. After measuring the input rate of the composite (ceramic metering feeder (1-1)), it proceeded. In this case, as the polyethylene chip, a low-density polyethylene chip having a melt index of 24.0 g/10 min (190° C., 2.16 kg) and a density of 0.915 g/cm 3 was used. For the production of a master batch for a packaging film that maintains freshness, polyethylene chips and mesoporous silica are pelletized using a pelletizer (speed 4.3 Hz) from a twin-screw screw rotating simultaneously at a temperature of 130 ° C and a speed of 100 rpm. A master batch for a freshness retention packaging film was prepared.

1-3. Manufacture of freshness-retaining packaging film containing high-supporting mesoporous silica.

A freshness packaging film was prepared by mixing 1 wt% of the master batch for the freshness packaging film prepared above and a polyethylene chip. %, and the thickness of the film was stretched to 50 μm.

[Examples 2 to 13, and Comparative Examples 1 to 5]

As shown in Table 1 below, the specific surface area of the mesoporous silica in the composite in which the antibacterial functional natural material was supported on the mesoporous silica, the amount of the antibacterial functional natural material added, and the amount of the supported complex added during the preparation of the master batch and the film were different. Other than that, it proceeded in the same manner as in Example 1.

[Comparative Example 6]

As shown in Table 2 below, mesoporous silica and an antibacterial functional natural material were added to a polyethylene chip to prepare a master batch for a freshness maintenance packaging film. A freshness maintenance packaging film was prepared by mixing the master batch for the freshness retention packaging film prepared above with a polyethylene chip. It proceeded in the same manner as in Example 1 except that the amount of addition was changed.

[Comparative Example 7]

As shown in Table 3 below, an antibacterial functional natural material was added to the mesoporous silica to prepare a composite in which the antibacterial functional natural material was supported on the mesoporous silica. A freshness-retaining packaging film was prepared by mixing a composite in which the antibacterial functional natural material prepared above was supported on mesoporous silica and a polyethylene chip. It proceeded in the same manner as in Example 1 except that the amount of addition was changed.

[Comparative Example 8]

A film made of polyethylene was used.

[Characteristic evaluation method]

1) Measurement of specific surface area

The specific surface area of the mesoporous silica prepared above was measured through a Quantachrome Nova e-4000 Bruner-EmmetTeller (Surface area range: 0.01 to 2000 m ² /g; Adsorption and desorption isotherm; Pore diameter range: 3.5 to 500 nm) device, The results are shown in Table 1 below.

2) Thermogravimetric (TGA) analysis: To analyze the mesoporous silica content of Examples and Comparative Examples, thermogravimetric analysis (TGA) was performed according to ASTM E1131 test standard. Thermogravimetric analysis was performed from 25° C. to 700° C. at a rate of 10° C./min in a nitrogen atmosphere using Q500 TA equipment, and the results are shown in FIG. 2 .

3) Tensile strength (MPa) analysis: The tensile strength of Examples and Comparative Examples was measured at a test speed of 500 mm/min using equipment (DUT-3000CM model of Daekyung Engineering Co., Ltd.) conforming to ASTM D882 standard, and the results were It is shown in Table 4 below.

4) Oxygen permeability (ml/(m2·day)) analysis: The oxygen permeability of Examples and Comparative Examples was measured using C230 (Labthink Co.) equipment according to ASTM D3985 standard at a temperature of 23°C and a humidity of 50% RH for 30 minutes using a masking technique. During the period, the amount of oxygen passing through an area of 1.131 cm 2 of the specimen was measured a total of 6 times, and the average value is shown in Table 4 below.

5) Moisture permeability (g/(㎡·day)) analysis: The moisture permeability of Examples and Comparative Examples was measured using W3/031 (Labthink) equipment according to ASTM F1249 standard, humidity 90%RH, temperature 38℃, Test interval 60 min Under the condition, the amount of moisture passing through an area of 33.18 cm 2 was measured a total of 5 times, and the average value is shown in Table 4 below.

6) Antibacterial inhibition evaluation: Antibacterial inhibition was evaluated according to ASTM E2149-13a test standard, and Staphylococcus aureus (S. Aureus) specified in the standard was used as the test strain. First, Staphylococcus aureus (S. aureus, ATCC 8739) and Escherichia coli (E. coli, ATCC 6538) used for antimicrobial evaluation were obtained from Liofilchem and used.

Antimicrobial activity evaluation of Examples and Comparative Examples was performed according to the standard test method of ASTM E2149 (shake flask test) against S. aureus and E. coli bacteria, respectively. To prepare the test solution, S. aureus and E. coli bacteria were cultured in LB medium (Luria-Bertani broth) at 37° C. for 18 hours, and diluted to about 1.5 × 10 ⁵ CFU/ml in Phosphate-Buffered Saline (PBS) solution. where CFU represents colony forming units. The test sample was treated with the test solution, and incubated for 18 hours at 37° C. and 200 rpm in a shaking incubator. The cultured test solution was spread on an agar plate and incubated in an incubator at 37° C. for 24 hours. Antibacterial activity was calculated as the colony reduction rate by comparing the number of colonies grown on the agar plate, and the formula is as follows. Antibacterial activity (%) measurement results are shown in Table 4 and Figure 2 below.

In the above, the antibacterial activity (%) = (A-B) / A × 100.

(In the above formula, A is the average number of colonies of the control group (CFU/ml), and B is the average number of colonies of the test sample (CFU/ml).

7) Storage and freshness maintenance evaluation: Basic laboratory condition control was performed for storage evaluation of post-ripened fruits (bananas), and if necessary, environmental conditions were controlled with a dehumidifier and temperature control device to maintain a normal room temperature environment. The influence of factors was minimized. Before the start of storage evaluation of Examples and Comparative Examples, an environment similar to room temperature was created by using a thermostat and a dehumidifier to control the environment of the place where the evaluation is to be performed. The target film was cut to a size of 25 cm in width and 35 cm in length, a single variety of banana was put, and controlled compressed air was put in a quantity and sealed with a hot wire. The sealed samples were photographed at the same location at intervals of 72 hours, and the L (whiteness) value of Hunters through a colorimeter was measured and compared with the average value. Examples and comparisons according to the degree of browning of a single variety of banana The freshness maintenance function of the example was measured, and the results are shown in FIGS. 3 and 4 .

support complex masterbatch film Specific surface area (m2/g) Antibacterial substances (wt%) Supported composite (wt%) Supported composite (wt%) Example 1 1000 15 10 0.1 Example 2 15 Example 3 25 Example 4 30 10 Example 5 15 Example 6 25 Example 7 45 10 Example 8 15 Example 9 25 Example 10 25 0.5 Example 11 0.1 Example 12 5 Example 13 9 Comparative Example 1 800 45 25 5 Comparative Example 2 1000 5 Comparative Example 3 45 5 Comparative Example 4 40 Comparative Example 5 15

masterbatch film mesoporous
Silica (wt%) Antibacterial substances (wt%) Polymer (wt%) Antibacterial substances (wt%) Comparative Example 6 16.5 13.5 70 2.25

film support complex Polymer (wt%) mesoporous
Silica (wt%) Antibacterial substances (wt%) Comparative Example 7 2.75 2.25 95

Tensile strength (MPa) oxygen permeability
{cm ³ /(m ² ·24hr·atm)} moisture permeability
{g/(m ² day)} Antibacterial activity (%) ^** Example 1 25.1 10,300 12 95 Example 2 25.3 10,500 13 95 Example 3 25.5 10,800 13.5 96 Example 4 25 11,000 14 95 Example 5 25.3 11,200 14.5 95 Example 6 25.4 11,500 15 96 Example 7 25.7 11,700 15 95 Example 8 25.9 11,800 16.5 96 Example 9 26 12,000 17 97 Example 10 26.2 12,200 18 98 Example 11 26.5 12,700 19.5 98 Example 12 27.7 14,500 23 99.9 Example 13 26.5 14,000 20 99 Comparative Example 1 22.6 5,200 8.5 80 Comparative Example 2 21.3 7,600 8.7 70 Comparative Example 3 23.1 8,900 9.2 85 Comparative Example 4 19.5 8,200 9 91 Comparative Example 5 17.2 7,300 7.5 93 Comparative Example 6 24.1 11,500 18.5 92 Comparative Example 7 21 10,000 13.9 94.5 Comparative Example 8 28.1 3,800 8.3 - Antibacterial activity (%) ^** is [(b - a)/b] × 100
a: After 24 hours of the test group (Examples 1 to 13 and Comparative Examples 1 to 7), the average number of colonies (CFU / ml)
b: After 24 hours of Comparative Example 8, the average number of colonies (CFU / ml)

As can be seen from Table 4, in the case of Examples 1 to 13, oxygen permeability of 10,300 to 14,500 {cm3/(m2·24hr·atm)} and moisture permeability of 12 to 23 {g/(m2·day) )} and an antibacterial activity (%) of 95 to 99.9. On the other hand, in the case of Comparative Examples 1 to 8, oxygen permeability of 3,800 to 11,500 {cm ³ /(m ² ·24hr·atm)} and moisture permeability of 7.5 to 18.5 {g/(m ² ·day)} and 70 to 94.5 It can be seen that the properties of Examples 1 to 13 are excellent because it shows the antibacterial activity (%) of

In particular, in the case of Example 12, the oxygen permeability {cm ³ /(m ² ·24hr) by adding 45% by weight of the antibacterial material in the supporting complex, 25% by weight of the supporting complex in the master batch, and 0.5% by weight of the supporting complex in the film ·atm)} is 14,500, moisture permeability {g/(m ² ·day)} is 23, and antibacterial activity (%) is 99,9, indicating the most excellent values. In addition, in Example 12, compared to Comparative Example 8, the decrease in tensile strength (MPa) due to the addition of the supporting composite was the lowest, and the oxygen permeability {cm ³ /(m ² ·24hr·atm)} was higher than that of Comparative Examples 1 to 8 It can be seen that the maximum is as high as 10,700. This is because, during the preparation of the master batch, which is the raw material of the film, the space through which oxygen can move is widened by widening the gap between the polymer chains as the composite supported on the mesoporous silica having a high specific surface area is added between the polyethylene matrices. In addition, the moisture permeability {g/(m ² ·day)} was higher than that of Comparative Examples 1 to 8 by up to 14.7, and the antibacterial activity (%) was higher than that of Comparative Examples 1 to 8 by up to 29.9.

In addition, as described in Figure 3, in the case of unpackaged bananas, Hunter's L (whiteness) value was reduced to less than 90% on the 3rd day and less than 50% on the 9th day, and in Comparative Example 8, storage 6 The L (whiteness) value of Hunters decreased to less than 90% on the first day and to less than 50% on the 15th day of storage. On the other hand, in the case of Example 12, it can be seen that the L (whiteness) value of Hunters was maintained at 90% or more even on the 6th day of storage, and a very high value than that of Comparative Example 8 could be maintained even on the 15th day. When the food is stored in Example 12 through the degree of decrease in the L (whiteness) value of Hunters over the course of storage, the freshness of the food can be maintained more excellently, and the storage period can be further increased, so deterioration, and spoilage It may mean that it is effective in preventing the decrease in the value of agricultural, livestock and fishery products caused by

In addition, as shown in FIG. 4 , severe deterioration occurred from the 3rd day in the case of unpackaged, and in the case of Comparative Example 8, rapid deterioration started from the 3rd day of storage. On the other hand, the banana stored in Example 12 had a low degree of noticeable deterioration until the 9th day of storage, and the degree of deterioration was low until the 15th day of storage. When storing the banana in Example 12, it can be seen that a low degree of deterioration is maintained for a long period of time. As a result of visually observing the bananas at 72-hour intervals at room temperature for 15 days, it was confirmed that the freshness maintenance function of Example 12 was very good, and when food was stored in Example 12, the freshness of the food could be maintained even better, so the storage period Since this can further increase, it may mean that it is effective in preventing the decline in the value of agricultural and fishery products due to deterioration and corruption.

From this, when 45 wt% of the antibacterial material in the support complex, 25 wt% of the support complex in the master batch, and 0.5 wt% of the support complex in the film are added, the oxygen permeability of the packaging film maintaining freshness {cm ³ /(m) ² ·24hr·atm)}, it was clearly confirmed that moisture permeability {g/(m ² ·day)}, and antibacterial activity (%) could be most excellently increased.

Although the present invention has been described with reference to specific matters and limited examples as described above, these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention belongs to Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims fall within the scope of the spirit of the present invention.

1-1: Ceramic metering feeder
1-2: polymer quantitative feeder
2: 2-axis screw
3: heating part
4: water tank
5: Master batch (M/B) cooling device using compressed air
6: Cooling water thermometer
7: Pelletizer

Claims (6)

(Step 1) preparing a molten mixture of a master batch and a polyethylene chip including a composite in which an antibacterial functional natural material is supported on mesoporous silica; and
(Step 2) forming the molten mixture with an extruder, stretching it into a film, cooling the film and winding it on a roll; includes;
The film contains 0.001 to 10% by weight of the composite, and has an oxygen permeability of 10,000 to 15,000 cm ³ /(m ² ·24hr·atm), and a moisture permeability of 10 to 25 g/(m ² ·day). with
The mesoporous silica is characterized in that it has a specific surface area of 850 to 1300 m / g,
The composite is a method of manufacturing a packaging film containing high-supporting mesoporous silica, characterized in that it contains 30 to 50% by weight of an antibacterial functional natural material based on the total weight of the composite.
delete The method of claim 1,
The master batch is a method of manufacturing a packaging film containing high carrying capacity mesoporous silica, characterized in that it contains 15 to 25% by weight of a complex in which an antibacterial functional natural material is supported on mesoporous silica.
A film containing polyethylene and a composite in which an antibacterial functional natural material is supported on mesoporous silica,
The film contains 0.001 to 10% by weight of the composite, and has an oxygen permeability of 10,000 to 15,000 cm ³ /(m ² ·24hr·atm), and a moisture permeability of 10 to 25 g/(m ² ·day). with
The mesoporous silica is characterized in that it has a specific surface area of 850 to 1300 m / g,
The composite is a high-supporting mesoporous silica-containing freshness packaging film, characterized in that 30 to 50% by weight of an antibacterial functional natural material is included in the total weight of the composite.
5. The method of claim 4,
The film is a high-supporting mesoporous silica-containing freshness packaging film, characterized in that the antibacterial activity calculated according to the following formula 1 is 95% or more.
[Formula 1]
Antibacterial activity (%) = (AB)/A × 100
(In the above formula, A is the average number of colonies of the control group (CFU/ml), and B is the average number of colonies of the test sample (CFU/ml).
A packaging material comprising the freshness retention packaging film containing the high-supporting mesoporous silica of claim 4 or 5.

Images