KR102354919B1 - Mothod of manufacturing Antibacterial packaging film using modified zeolite and Antibacterial packaging film manufactured by the method - Google Patents

Abstract

A method of manufacturing an antibacterial film for food packaging comprises: a step of preparing a pre-treated modified zeolite powder by mixing natural zeolite with an amine solution; a step of preparing a modified zeolite mixture by mixing a nanocellulose solution with the modified zeolite powder; a step of preparing a composition for a master batch by mixing and stirring the modified zeolite mixture, loess soil, soybean extract, tetrabutyl ammonium, and zinc oxide into a plastic resin raw material; a step of extruding the composition for a master batch with an extruder; a step of preparing a master batch by cooling and cutting the extruded extrudate; and a step of preparing a film for packaging by supplying the master batch to the extruder. The antibacterial film for food packaging using the modified zeolite according to the present invention has an excellent effect of inhibiting the growth of microorganisms in food when the packaged food is stored, can maintain the freshness of food for a long time by slowing the progress of spoilage, has an excellent effect of inhibiting bacterial spoilage, and has an effect of reducing the objection of consumers by implementing the antibacterial effect by using a natural material rather than an artificial additive.

Description

Method of manufacturing an antibacterial film for food packaging that maintains freshness and prevents bacterial spoilage using modified zeolite, and an antibacterial film for food packaging manufactured therefrom

The present invention relates to a method for manufacturing an antibacterial film for food packaging that maintains freshness and prevents bacterial spoilage using a modified zeolite, and an antibacterial film for food packaging prepared therefrom. It is excellent and relates to a method for manufacturing an antibacterial film for food packaging, which is excellent in maintaining freshness and inhibiting bacterial spoilage, which can maintain the freshness of food by slowing the progress of spoilage, and an antibacterial film for food packaging manufactured therefrom.

The most important topic in the food industry is to develop a technology that can keep the food fresh for a long time by extending the shelf life of the food. In other words, food, which is essential for human life, is more important than any other product, and developing a technology that can preserve its quality for a long time is the most important in the field of food-related technology.

In the past, to solve such food spoilage and deterioration problems, artificial additives such as preservatives were directly added to food or added to food packaging containers to extend the shelf life of food. However, these preservatives are harmful to the human body. Since it is a substance, it inevitably adversely affects the health of the user and also adversely affects the taste and flavor of food.

Accordingly, as one of the food packaging methods to replace the conventional method of extending the storage period of food by adding artificial additives, a method for improving a food packaging film using a natural material is being studied. As such, an antibacterial packaging film is being developed as one of the methods for improving the preservation period and freshness of food without using conventional artificial additives. In the antibacterial packaging film, substances with many antibacterial properties such as loess, elvan, biotite, white jade, sapphire, zeolite and silver nano are added to the material of plastic resin to suppress the growth of mold bacteria in the packaging of foods such as fruits, vegetables, and cheese. A method of adding an effect is used.

In order to solve this problem, the present inventors confirmed that there is an excellent effect when using the modified zeolite and completed the present invention.

Korean Patent Publication No. 10-2019-0045514 (published on: 2019.05.03.) Korean Patent Registration No. 10-1924813 (Registration Date: 2018.11.28.)

The present invention has been devised to solve the above problems, and an object of the present invention is to maintain the freshness of food for a long time and to prevent bacterial spoilage by having an excellent effect of inhibiting the growth of microorganisms in food and very slow the progress of spoilage. An object of the present invention is to provide a method for producing an excellent antibacterial film that can be suppressed.

In addition, another object of the present invention is to provide an antibacterial film for food packaging that can reduce consumer rejection by implementing an antibacterial effect by using a natural material rather than a conventional artificial additive.

These and other objects and advantages of the present invention will become more apparent from the following description of preferred embodiments.

In order to achieve the above object, the method of manufacturing an antibacterial film for food packaging for maintaining freshness and preventing bacterial spoilage using the modified zeolite of the present invention for achieving the above object includes the steps of preparing a modified zeolite powder pretreated by mixing a natural zeolite with an amine solution; preparing a modified zeolite mixture by mixing a nanocellulose solution with the modified zeolite powder; preparing a composition for a master batch by mixing and stirring the modified zeolite mixture, loess soil, soybean extract, tetrabutyl ammonium and zinc oxide into a plastic resin raw material; extruding the composition for the master batch with an extruder; Cooling and cutting the extruded extrudate to prepare a masterbatch; It characterized in that it comprises; supplying the masterbatch to an extruder to produce a packaging film.

In addition, the master batch composition further comprises a curing agent, a curing accelerator, or a mixture thereof, wherein the modified zeolite powder has a weight mixing ratio of the natural zeolite powder and the amine solution of 1:8 to 1:12 , The amine solution is characterized in that m-phenylenediamine.

In addition, preparing the composition for the master batch includes 5 to 15 parts by weight of the modified zeolite mixture, 0.5 to 5 parts by weight of the loess, 1 to 2 parts by weight of the soybean extract, and the tetrabutyl ammonium based on 100 parts by weight of the plastic resin. 0.2 to 1 part by weight and 1 to 3 parts by weight of the zinc oxide are mixed.

Another invention is achieved by an antibacterial film for food packaging produced by the above-described manufacturing method.

According to the present invention, when food packaged with an antibacterial film for food packaging using modified zeolite is stored, the effect of inhibiting the growth of microorganisms in food is excellent and the degree of spoilage is very slow, so that the freshness of food can be maintained for a long time, and bacterial spoilage can be prevented. It has an excellent effect of suppressing it.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a flowchart of a method for manufacturing an antibacterial film for food packaging using a modified zeolite according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Terms and words used in this specification are terms selected in consideration of the function of the embodiment, and the meaning of the terms may vary according to the intention or custom of the invention. Therefore, the terms used in the examples to be described below, when specifically defined in the present specification, follow the definition, and when there is no specific definition, it should be interpreted as a meaning commonly recognized by those skilled in the art.

1 is a flowchart of a method for manufacturing an antibacterial film for food packaging using a modified zeolite according to an embodiment of the present invention.

1, the antibacterial film for food packaging using the modified zeolite according to the present invention includes modified zeolite powder, nano cellulose solution, loess, soybean extract, tetrabutyl ammonium, zinc oxide and plastic resin. The manufacturing method of the antibacterial film for food packaging using the modified zeolite containing such a substance is as follows.

A modified zeolite powder is prepared by mixing natural zeolite with an amine solution, and a nano-cellulose solution is mixed with the modified zeolite powder to prepare a modified zeolite mixture. The modified zeolite mixture is preferably used in an amount of 5 to 15 parts by weight, more preferably 9 to 12 parts by weight, based on 100 parts by weight of the plastic resin. When it is less than 5 parts by weight, the microbial growth inhibitory effect is insignificant, and when it exceeds 15 parts by weight, the physical properties of the plastic resin are deteriorated, and the microbial growth inhibitory effect may also be reduced.

The modified zeolite powder may have an average particle size of 10 to 2,000 μm. When the average particle size of the modified zeolite powder is less than 10 μm, it is difficult to improve mechanical properties because the amount of nano-cellulose introduced is small, and when it exceeds 2,000 μm, the surface area is reduced and there is a fear that the antibacterial activity may be lowered.

In addition, the antibacterial property of the modified zeolite is that a plurality of amine groups are introduced on the surface and a porous structure is formed, so that the zeolite selectively binds to trace metal elements to inhibit toxin production and inhibit the growth of microorganisms. ) and is expressed as

The modified zeolite exhibiting antibacterial properties as described above lacks heat resistance and, when subjected to a high-temperature mechanical molding process, has a problem in that the porous structure is lost and the antibacterial properties are lowered. An antibacterial film with improved mechanical properties can be prepared.

As the modified zeolite is pretreated by mixing natural zeolite powder with an amine solution, it is preferable to use a modified zeolite powder having an amine group introduced thereto.

The natural zeolite is an inorganic antibacterial agent, and is generally an aluminosilicate having a three-dimensionally grown skeletal structure. These natural zeolites are powdered by a general pulverization method and then dried.

Specifically, the modified zeolite powder is obtained by mixing 5 to 100 parts by weight of a natural zeolite powder with 100 parts by weight of an amine solution, reacting for 0.5 to 12 hours, and then obtaining a reacted zeolite powder, and at a temperature of 50 to 150 ℃ 0.1 to It can be prepared by heat treatment for 6 hours, and the amine solution may be a mixture of 1 to 10 parts by weight of the amine compound and 100 parts by weight of water. The modified zeolite powder preferably has a weight mixing ratio of 1:8 to 1:12 of the natural zeolite powder and the amine solution, and when the weight mixing ratio of the amine solution is less than 1:8, the effect of introducing an amine group is small, 1: When it exceeds 12, it is difficult to use as a composition for master batches.

The amine compound is m-phenylenediamine, p-phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3 -Chloro-1,4-phenylenediamine or a mixture thereof may be included, and preferably, m-phenylenediamine may be used. The amine compound includes two or more amine groups to introduce an amine group to the surface of the zeolite powder, and the introduced amine group forms an amide bond with the carboxyl group of the nanocellulose to form an antibacterial film that exhibits excellent mechanical properties even at high temperatures. have.

Preferably, the modified zeolite powder is prepared by mixing 5 parts by weight of m-phenylenediamine and 95 parts by weight of water to prepare an amine solution, 100 parts by weight of the prepared amine solution is mixed with 50 parts by weight of natural zeolite powder, and reacted for 2 hours Then, the amine solution is removed to obtain a zeolite reactant, and a product prepared by heat-treating the obtained zeolite reactant at a temperature of 80° C. for 0.5 hours may be used.

The nano cellulose is a natural polymer, has high crystallinity, excellent physical strength, heat resistance, transparency, and biodegradability. It is possible to improve the physicochemical properties of the zeolite by strengthening or protecting the zeolite tissue bond.

Specifically, nanocellulose has a structure in which a hydroxyl group (-OH) is introduced at the 2nd carbon position of a pyranose ring, an N-acetyl group (-CHCO) in the case of chitin, and an amino group in the case of zeolite It has a structure in which (-NH) is introduced and has a molecular structure similar to that of zeolite, and the cellulose chains are combined to form a bundle so that the tensile modulus of elasticity is similar to that of steel or kevlar, the density is small, and the specific surface area is large. As a bio-based material with

Nano cellulose may be prepared using a variety of conventional cellulose raw materials used for manufacturing it, but preferably, rice straw, barley straw, corn stalk, cotton stalk, sugar cane, bamboo, kenaf, cotton Those manufactured using cellulose raw materials including linter, wood, or mixtures thereof may be used, and nano-cellulose manufactured using such cellulose raw materials is a safe natural material that does not adversely affect the human body even when ingested.

In addition, nano-cellulose can introduce nano-cellulose having an average width of 2 to 300 nm and an average length of 100 to 2,000 nm, and when the width and length of the nano-cellulose are out of the above ranges, A problem that uniform introduction is difficult may occur.

The nano cellulose is manufactured by adding chemical treatment by acid hydrolysis to nanofiber cellulose (cellulose nanofibril, CNF) prepared through mechanical treatment of a cellulose raw material using a high-pressure homogenizer or a milling machine, etc. It may include one nanocrystalline cellulose (cellulose nanocrystal, CNC), cellulose derived from bacteria, or a mixture thereof.

Specifically, the nanofiber cellulose may have a width of 2 to 300 nm, a length of 700 to 2,000 nm, and an aspect ratio of 5 to less than 50, and the nanocrystalline cellulose has a width of 2 to 20 nm, a length of 100 to 600 nm, an aspect ratio of 1 to 5 may be used, and preferably, nanocrystalline cellulose may be introduced. Since nanocrystalline cellulose acid hydrolyzed by sulfuric acid has a low crystal region acquisition rate, it is more preferable to use nanocrystalline cellulose in which electron beam irradiation is performed together with acid treatment. By removing the amorphous region through electron beam irradiation, the capture rate of the crystalline region can be increased, and environmental pollution during manufacturing can be reduced by reducing the amount of sulfuric acid used.

The nano-cellulose solution can be prepared by mixing 1 to 50 parts by weight of nano cellulose with 50 to 99 parts by weight of a solvent. In this case, there is a problem that the viscosity is greatly increased due to the formation of hydrocolloids, making it difficult to complex with zeolite.

The nano-cellulose is insoluble in general solvents and water due to complex hydrogen bonding and high crystallinity, and can be prepared using a solvent capable of uniformly dispersing the nano-cellulose.

The nano-cellulose solution is ethanol, methanol, butanol, propanol, isopropanol, acetic acid (acetate), acetone (acetone) or a mixture thereof using nano-cellulose as a solvent A uniformly dispersed nano-cellulose solution can be prepared. Preferably, 1 to 5 parts by weight of nanocrystalline cellulose may be mixed with 100 parts by weight of ethanol to prepare a nano-cellulose solution.

Next, the modified zeolite mixture, loess soil, soybean extract, tetrabutyl ammonium and zinc oxide are mixed with a plastic resin raw material and stirred to prepare a composition for a master batch.

In addition, the loess according to the present invention exhibits antibacterial, deodorizing or sterilizing functions inherent in itself, thereby suppressing the generation of harmful substances and maintaining the freshness of stored food for a certain period of time. It is used because far-infrared rays are emitted from loess to remove toxins, purify, remove heavy metals, deodorize, antibacterial, dehumidify, and purify air, and have strong decomposition and adsorption effects. This loess is preferably crushed after calcining at a high temperature, for example, 600 to 900 °C. In addition, it is preferable to use loess in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the plastic resin.

In addition, the soybean extract according to the present invention is the most nutritious and easily digestible food among legumes, and is made from soybeans, which are the most abundant in protein and one of the most inexpensive protein sources. Since these soybeans are starch-free, they are a very good source of protein for diabetics. In addition, the soybean extract is preferably used in an amount of 1 to 2 parts by weight based on 100 parts by weight of the plastic resin.

The soybean extract is obtained by pulverizing dried soybeans with 1,3-butylene glycol and

It can be obtained by supercritical extraction using a solvent mixed with ethanol, and a separate purification process is unnecessary.

Tetrabutyl ammonium according to the present invention is a phase transfer catalyst, which helps to effectively mix organic materials in plastic resins and other compositions. As such, in order to help the organic material to be effectively mixed in the plastic resin, tetrabutyl ammonium is preferably used in an amount of 0.2 to 1 part by weight based on 100 parts by weight of the plastic resin.

Zinc oxide according to the present invention is used in a composition for a master batch to impart antibacterial and sterilizing power, and has excellent antifungal and deodorizing properties. Such zinc oxide imparts antibacterial and sterilizing power through a mechanism to kill and remove it by inhibiting the metabolism of viruses or bacteria. In particular, nano-sized zinc oxide has a surface effect that bulk materials do not have due to its increased specific surface area. It acts as an antibacterial agent against harmful bacteria such as bacteria.

The zinc oxide powder preferably has an average particle diameter of 100 to 150 nm. Here, the average particle diameter means the cumulative average particle diameter corresponding to 50% by volume in the cumulative distribution curve of the particle size in which the total volume is 100%. For example, it may be measured with a particle size analyzer, or may be measured from a TEM or SEM photograph. As another method, after measuring using a measuring device using dynamic light-scattering, data analysis is performed to count the number of particles for each size range, and from this, the average particle diameter can be easily calculated can be obtained

At this time, if the average particle diameter of the zinc oxide contained in the master batch composition is less than 100 nm, there is no problem in using the dispersant-added master batch composition within a relatively short period such as 1 month, but when the storage period is increased There may be a problem in that the zinc oxide particles are concentrated in a specific part.

In addition, the zinc oxide is less harmful to the human body, and unlike titanium and the like, it can exhibit an antibacterial effect irrespective of sunlight. In addition, zinc (Zinc Pyrithione) may be included in the composition for the master batch, and zinc pyrithione is an antifungal agent that was developed and widely used in the 1930s, and is in the form of a white powder. Although zinc pyrithione has excellent antibacterial activity, there is a problem in that it is easily discolored when used in order to impart antibacterial properties to the resin. In order to prevent the zinc pyrithione from being decomposed or discolored by heat, it is preferable not to exceed the melting point of the synthetic resin excessively.

1 to 3 parts by weight of zinc oxide according to the present invention is used based on 100 parts by weight of the plastic resin. At this time, if the content of the zinc oxide powder is less than 1 part by weight, the antibacterial effect of the antibacterial film is less improved. can occur.

The plastic resin used in the composition for the master batch may be any one or more of polyolefin, polyethylene terephthalate, polyamide, acrylonitrile-butadiene-styrene copolymer, and preferably polyethylene or low-density polyethylene (LDPE). have.

The polyolefin-based resin is a resin having a high molecular weight by polymerization of a monomer having a double bond in the molecule. Examples of the monomer having a double bond in the molecule include an ethylene monomer used in the production of polyethylene, and propylene used in the production of polypropylene. Monomers, styrene monomers used in the production of polystyrene, vinyl chloride used in the production of polyvinyl chloride, etc. can be enumerated, which can be collectively referred to as vinyl monomers, which can be easily understood by those skilled in the art. Representative examples of such polyolefin-based resins include polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-propylene copolymer, and the like. Also, copolymers obtained by copolymerizing two or more monomers may have various composition ratios and structural structures according to their intended physical properties. can have diversity.

Polyethylene terephthalate (PET) is a saturated polyester obtained by condensation polymerization of terephthalic acid and ethylene glycol. It is a crystalline plastic and has excellent heat resistance, rigidity, electrical properties, and oil resistance. has a character Also, because it belongs to crystalline plastics, it has good resistance to oils such as diesel oil. However, since there is an ester bond in the molecular chain, the molded product tends to change when immersed in acid or alkali over a high temperature and for a long time.

In addition, antioxidants may be added to the plastic resin according to the present invention.

The antioxidant is preferably used in an amount of 0.5 to 1 part by weight of phenyl-β-naphthylamine per 100 weight of the plastic resin in order to prevent oxidation of the composition for master batch. Examples of such antioxidants include sorbitol, glycerin, hydroquinone, Irganox 1010 and Irgafos 168 (Basf), which are commonly used, but it can be seen that these conventional antioxidants have little effect when applied in the present invention. there was. That is, the inventors of the present invention applied these conventional antioxidants and analyzed through experiments. As a result, it was confirmed that phenyl-β-naphthylamine was the most excellent in the present invention.

An antibacterial film having improved mechanical properties may be prepared by additionally introducing a curing agent, a curing accelerator, or a mixture thereof to the master batch composition.

The curing agent induces amide bonds and ester bonds to promote crosslinking of zeolite and nano-cellulose, thereby suppressing the solubility of the antibacterial film and improving mechanical properties at the same time.

The curing agent is sodium tripolyphosphate, β-glycerophosphate, glyoxal, 1-butyl-3-methylimidazolium chloride, glue Taraldehyde (glutaraldehyde), epichlorohydrin (epichlorohydrin), diisocyanate (diisocyanate), ethyldimethylaminopropyl carbodiimide (1-ethyl-3 (3-dimethyl aminopropyl) carbodiimide), hydroxysuccinimide (N- hydroxysuccinimide), ethylene diamine, dimethylaminopropyl ethylcarbodiimide hydrochloride, hydroxybenzotriazole, diisopropylcarbodiimide, or a mixture thereof may be used. have. Preferably, the crosslinking agent may use a component that is not toxic to the human body, and sodium tripolyphosphate or a derivative thereof may be introduced.

The curing accelerator promotes amide bonding between zeolite and nano-cellulose to further improve the mechanical properties of the antibacterial film, and the curing accelerator is triethoxysilane, tetraethoxysilane, lauroyl chloride ( lauroyl chloride) or a mixture thereof may be used.

The curing agent and curing accelerator affect the cross-linking of zeolite and nano-cellulose, so that the strength and degradability of the antibacterial film can be adjusted according to the amount added.

The curing agent and curing accelerator may each be introduced in a ratio of 0.1 to 10 parts by weight relative to 100 parts by weight of the plastic resin, and when the content is less than 0.1 parts by weight, it is difficult to expect sufficient physical property improvement, and when it exceeds 10 parts by weight, the antibacterial film Mechanical properties may be further improved, but there is a fear that antibacterial properties may be lowered.

In this case, additives that can be added to the plastic resin to constitute the masterbatch include a plasticizer, a lubricant, or a heat stabilizer. The plasticizer includes dioctyl adipate (DOA, Dioctyl Adipate) or dioctyl phthalate (DOP, Dioctyl Phthalate), and the lubricant is soybean oil and the like that can facilitate molding into a film, and the heat stabilizer is Bisorganotin-based stabilizers such as di-n-octyl tin bis (isooctyl thioglycolic acid ester) may be used to prevent thermal decomposition.

Then, the mixed and stirred composition for the master batch is extruded by an extruder.

Next, the extruded material extruded in the extruder is cooled and cut to prepare a polyethylene masterbatch, and then the prepared polyethylene masterbatch is supplied to the extruder to prepare a packaging film.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through Examples and Comparative Examples. However, these examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

<Example>

[Examples 1 to 3]

The components and composition ratios shown in Table 1 were mixed while stirring for 10 minutes at a stirring speed of 2,000 rpm at room temperature using a high-speed powder mixer, and then the mixed composition was mixed with an extruder (length 2.8 m, diameter 10 cm single screw screw mounted). One die hole diameter 2mm), extruded under the condition of 130 ± 5℃, cooled the extrudate in cold water at 20℃, cut it to prepare a polyethylene masterbatch, and then fed the prepared masterbatch to the extruder to have a thickness of 20 An antibacterial film having a thickness of ㎛ was prepared and used as Examples 1 to 3, respectively.

Classification (parts by weight) Example 1 Example 2 Example 3 polyethylene resin 100 100 100 Modified zeolite mixture 10 7 11 ocher 2.0 2.5 2.3 Soybean Extract 1.0 1.6 1.2 tetrabutyl ammonium 0.2 0.4 0.5 zinc oxide 2.0 3.0 2.0 Phenyl-β-naphthylamine 0.5 0.5 0.7 dioctyl adipate 0.1 0.1 0.1 di-n-octyltinbis 0.1 0.2 0.1

[Comparative Examples 1 to 5]

An antibacterial film having a thickness of 20 μm was prepared in the same manner as in Example 1, except that a polyethylene masterbatch was prepared using the components and composition ratios shown in Table 2 below. In addition, the natural zeolite and nano cellulose used in Comparative Example 2 are mixtures in which the zeolite is not modified.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polyethylene resin (weight) 100 100 100 100 100 Modified zeolite mixture - - - 1.0 40.0 natural zeolite - 5.0 7.0 - - nano cellulose 10 7.0 - - - ocher - 2.0 - 2.0 0.1 Soybean Extract 0.5 4.0 3.0 1.4 1.6 tetrabutyl ammonium 2 0.6 2 0.1 0.3 zinc oxide - 0.2 7.0 3.0 1.0 Phenyl-β-naphthylamine 0.3 0.5 0.3 0.5 0.7 dioctyl adipate 0.1 0.1 0.2 0.1 0.1 di-n-octyltinbis 0.1 0.2 0.1 0.1 0.3

Using the films according to Examples 1 to 3 and Comparative Examples 1 to 5, physical properties were measured through the following experimental examples, and the results are shown in Table 1 below.

[Experimental Example 1]

Experimental Example 1 is to confirm the effect of extending the shelf life of food using the films according to Examples 1 to 3 and Comparative Examples 1 to 5. For this purpose, the effect of mackerel fillet on microbial growth during storage was investigated. After packing the mackerel fillets with good freshness with films according to Examples 1 to 3 and Comparative Examples 1 to 5, and storing them at 10° C., the growth pattern of microorganisms according to time was investigated. The initial number of microorganisms was 1.2 x E2/g. Here, "E2" stands for "10 ² ".

division 5 days 10 days 15th 20 days Example 1 2.4 x E2/g 8.4 x E2/g 6.5 x E4/g 5.6 x E6/g Example 2 3.1 x E2/g 1.8 x E3/g 0.4 x E5/g 1.5 x E7/g Example 3 2.7 x E2/g 1.2 x E3/g 8.2 x E4/g 8.7 x E6/g Comparative Example 1 5.4 x E4/g 3.4.x E6/g x E9/g x E14/g Comparative Example 2 4.3 x E4/g 0.4 x E6/g x E8/g x E13/g Comparative Example 3 6.4 x E4/g 4.1 x E6/g x E9/g x E15/g Comparative Example 4 2.8 x E3/g 3.5 x E5/g x E8/g x E12/g Comparative Example 5 1.8 x E3/g 2.2 x E5/g x E7/g x E10/g

As can be seen in Table 3, in the case of a sample packaged with an antibacterial film for food packaging according to an embodiment of the present invention, the number of microorganisms reaches 5.6 x E6/g to 1.5 x E7/g after 20 days of storage, so that it is suitable for edible use. Although it was at an unsuitable level, in the case of the films according to Comparative Examples 1 to 5, the number of microorganisms reached 2.2 x E5/g to 4.1 x E6/g after about 10 days, reaching a level unsuitable for human consumption. In addition, it was confirmed that the microbial growth inhibitory effect was excellent when the modified zeolite mixture of Comparative Examples 4 to 5 was included, rather than when each mixture of the natural zeolite and nano-cellulose according to Comparative Examples 1 to 3 was included, and preferably When 10 parts by weight of the modified zeolite was contained, it was confirmed that the best results were obtained.

Therefore, it can be seen that the antimicrobial film for food packaging according to the present invention exhibits a very excellent microbial growth inhibitory effect compared to the film according to the comparative example.

[Experimental Example 2]

In Experimental Example 2, commercially available cherry tomatoes were packaged with films according to Examples 1 to 3 and Comparative Examples 1 to 3, and then stored in a thermostat at 20° C. and 30° C. for 5 days, 7 days and 10 days. Then, the degree of decay of the cherry tomatoes was visually observed, and the results are shown in Table 4 below. The symbols in Table 4 below visually check the degree of decay, and "○" means good condition, "△" means slightly decayed state, and "X" means "corrupted state".

division 20℃ 30℃ 5 days 7 days 10 days 5 days 7 days 10 days Example 1 ○ ○ ○ ○ ○ △ Example 2 ○ ○ △ ○ △ △ Example 3 ○ ○ △ ○ △ △ Comparative Example 1 △ X X X X X Comparative Example 2 △ △ X △ X X Comparative Example 3 △ X X X X X

As can be seen in Table 4, in the case of cherry tomatoes packaged with an antibacterial film for food packaging according to Examples 1 to 3 of the present invention and stored for about 7 days in a thermostat at 20° C., the freshness even after about 7 days has elapsed. It is maintained as it is and it can be seen that it is slightly rotten when 10 days have elapsed, and in the case of cherry tomatoes stored for about 5 days in a thermostat at 30℃, the freshness is maintained even after about 5 days, and about 7 days. It can be seen that a little spoilage when elapsed, but in the case of the antibacterial film for food packaging according to Comparative Examples 1 to 3, it can be seen that a lot of decay proceeds in 7 days in a thermostat at 20°C and 5 days in a thermostat at 30°C.

Therefore, as shown in Tables 3 and 4, the results of the above experimental examples, the antibacterial film for food packaging according to the present invention has an excellent effect of inhibiting the growth of microorganisms in food, and it can maintain the freshness of food for a long time by slowing the progress of spoilage, It can be seen that it has an excellent effect to suppress bacterial decay.

In this specification, only a few examples among the various embodiments performed by the present inventors are described, but the technical spirit of the present invention is not limited or limited thereto, and it is of course that it may be modified and variously implemented by those skilled in the art.

S1: preparing modified zeolite powder
S2: Preparing the nano-cellulose mixture
S3: Step of preparing a composition for a master batch
S4: Extruding the composition for the master batch with an extruder
S5: Cooling and cutting the extrudate to prepare a masterbatch
S6: supplying the masterbatch to an extruder to produce a packaging film

Claims (5)

In the manufacturing method of the antibacterial film for food packaging,
preparing a pre-treated modified zeolite powder by mixing natural zeolite with an amine solution;
preparing a modified zeolite mixture by mixing a nano-cellulose solution with the modified zeolite powder;
preparing a composition for a master batch by mixing and stirring the modified zeolite mixture, loess soil, soybean extract, tetrabutyl ammonium and zinc oxide into a plastic resin raw material;
extruding the composition for the master batch with an extruder;
Cooling and cutting the extruded extrudate to prepare a masterbatch;
Manufacturing the antibacterial film for food packaging comprising; supplying the masterbatch to an extruder to produce a packaging film.
The method of claim 1,
Method for producing an antibacterial film for food packaging, characterized in that it further comprises a curing agent, a curing accelerator, or a mixture thereof in the composition for the master batch.
The method of claim 1,
The modified zeolite powder has a weight mixing ratio of the natural zeolite powder and the amine solution of 1:8 to 1:12, and the amine solution is m-phenylenediamine.
The method of claim 1,
The step of preparing the composition for the master batch includes 5 to 15 parts by weight of the modified zeolite mixture, 0.5 to 5 parts by weight of the loess, 1 to 2 parts by weight of the soybean extract, 0.2 to 0.2 to tetrabutyl ammonium based on 100 parts by weight of the plastic resin. 1 part by weight and 1 to 3 parts by weight of the zinc oxide are mixed.
An antibacterial film for food packaging manufactured by the manufacturing method according to any one of claims 1 to 4.

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