WO2012081756A1

WO2012081756A1 - Co-extruded, antimicrobial vacuum-packing film having a seven-layer structure and a production method therefor

Info

Publication number: WO2012081756A1
Application number: PCT/KR2010/009217
Authority: WO
Inventors: 김일용; 장영욱; 김금자
Original assignee: 주식회사 롤팩
Priority date: 2010-12-15
Filing date: 2010-12-22
Publication date: 2012-06-21
Also published as: KR20120066952A

Abstract

The present invention relates to an antimicrobial vacuum-packing film having a seven-layer structure which has an antimicrobial performance, and to a method for producing the same. Provided is an antimicrobial vacuum-packing film having a seven-layer structure, being an antimicrobial vacuum-packing film for packing an article, wherein the packing film comprises seven layers; the outermost layer of the packing film is formed from a polyamide resin; the innermost layer, which comes into contact with the article, is formed from a polyethylene resin; and the innermost layer includes selenium particles having a particle size of between 5 and 10 nm or at least one organic antimicrobial agent selected from the group consisting of antimicrobial organic monomeric compounds represented by chemical formula 1, antimicrobial homopolymers represented by chemical formula 2 having a weight-average molecular weight of between 10,000 and 1,000,000, and antimicrobial acrylic copolymers represented by chemical formula 3 having a weight-average molecular weight of between 10,000 and 1,000,000. Also provided is a film production method of the co-extrusion type. The present invention imparts an antimicrobial function to a vacuum packing film that has outstanding oxygen and water-vapour blocking properties, and, by so doing, the invention allows relatively long-term food storage and thus makes it possible to reduce the use of packing film and so possible to reduce the amount of use of naphtha which is a basic raw ingredient in film production, and also makes it possible to reduce the amount of use of petroleum as an energy source required for production and so possible to obtain an environmentally-friendly effect.

Description

【Specification】

Title of the Invention

Coextruded antimicrobial vacuum packaging film of 7 layer structure and manufacturing method thereof

TECHNICAL FIELD

The present invention relates to a nanocomposite antibacterial vacuum packaging film that is environmentally friendly, has high antibacterial activity, has improved antibacterial activity, and a method for producing the same. More specifically, an antimicrobial inorganic particle or antimicrobial organic monomer compound, antimicrobial homopolymer or antimicrobial acrylic copolymer polymer having a nano size (~ 1 (? ⁹ m) is uniformly dispersed in a polyethylene matrix, Film and a method for producing the film.

BACKGROUND ART [0002]

Recently, the plastic film in the form of an envelope is mainly used for storing foods such as meat, meat products, fish, and cereals for a long period of time. Such a plastic film is known to have a multilayer structure including, for example, seven layers including nylon (polyamide) for imparting oxygen and water vapor barrier properties to prevent decay of articles such as foods to be stored. However, these packaging films block the inflow of oxygen and do not provide antibacterial properties, so they are inadequate to inhibit the formation of harmful bacteria and microorganisms. Foods that are sensitive to microorganisms or medical products that require high storage conditions In the case of storing articles, it is necessary to prevent corruption of articles to be stored and deterioration thereof. For this purpose, it is required to form an antimicrobial vacuum film having antimicrobial ability by uniformly dispersing nano-sized antimicrobial substance in the film in contact with the article. As such antimicrobial vacuum film, Most of them are made by mixing silver particles of nanometer or micrometer size with polymer resin, and most of them are made of only a single layer, not a multilayer film, or products having a two-layer structure laminated by lamination . Thus, until now, silver, which is mainly used as an additive for imparting an antimicrobial function, has its own toxicity, and technical limitations such as reduction of the antibacterial power due to elution of the antimicrobial substance have been continuously pointed out. In addition, silver has a problem of low cost because of its high price. Furthermore, when a resin composition is extruded for processing a plastic film from a resin composition containing silver to form a film, agglomerate ions are generated in the silver foil ream bundle which imparts an antimicrobial activity to the film, And the appearance of the entire film is somewhat dark. In addition, the silver contained in the vacuum packaging material until now is in contact with the water, and silver ions (Ag +) are formed in the liquid crystal atmosphere. When the thickness of the film increases, silver is not distributed only on the surface, Because it is uniformly distributed A significant amount of the added silver is not able to exhibit the desired antimicrobial activity. In order to obtain sufficient antimicrobial activity, it is required to increase the amount of silver. In this case, not only the price of the product is increased but also the transparency of the film is drastically lowered, which hinders obtaining a high quality product.

DISCLOSURE OF THE INVENTION

[Problem to be solved]

In the case of imparting an antimicrobial activity to a vacuum packed film, it is possible to significantly extend the shelf life of the packaged product, thereby reducing the amount of packaging material used and ultimately contributing to the reduction of carbon emissions, which is a global concern. can do . Accordingly, the present invention greatly improves the storage function of the packaging film by developing a film having environmentally friendly and sustainable antibacterial activity, maximizing the packaging period to maximize the loss due to the corruption of the article and the overall usage of the plastic packaging film And to provide an antimicrobial vacuum packaging film having active antimicrobial activity by improving existing vacuum packaging films having superior oxygen and water vapor barrier properties. The present invention also provides an antimicrobial agent for antimicrobial activity contained in a vacuum packaging film having an antimicrobial activity. The antimicrobial agent is not self-toxic by using a component other than silver, To provide a vacuum packaging film excellent in antibacterial activity. Further, the present invention provides a method for producing such an antibacterial vacuum packaging film. MEANS FOR SOLVING THE PROBLEMS

The present invention relates to a coextruded antimicrobial vacuum packaging film for packaging an article, wherein the packaging film is composed of seven layers, the outermost layer of the packaging film is formed of a polyamide resin, and the innermost layer in contact with the article is a polyethylene resin Wherein the innermost layer comprises selenium particles having a particle size of 5 to 10 nm or an antimicrobial organic monomer compound represented by the formula (1), an antimicrobial homopolymer represented by the formula (2) having a weight average molecular weight of 10, 000-1, And an antibacterial acrylic copolymer represented by the following formula (3) having a weight average molecular weight of 10, 000-1, 000, 000, and an organic antimicrobial agent selected from the group consisting of .

Preferably, the antimicrobial vacuum packaging film has four resin layers alternately arranged from the outside to the inside of the packaging film, the polyamide resin and the polyethylene resin, and the adhesive resin layer formed between the respective resin layers . More preferably, the polyamide resin may be nylon 6 or nylon 66, and the polyethylene may be low density polyethylene (LDPE) or linear low density polyethylene (LLDPE). In addition, it is preferable that the adhesive resin layer is formed of maleic anhydride modified VLDPE.

The selenium particles are contained in an amount of 30 ppm to 40 ppm of the innermost layer weight The organic antimicrobial agent is preferably contained in an amount of 0.5-5% by weight of the weight of the resin layer. The present invention relates to a method for producing an antimicrobial vacuum packaging film having a seven-layer structure, wherein the packaging film is produced by melt co-extruding a resin in an extruder using a pneumatic actuator including seven extruders, The selenium particles or the antibacterial organic monomer compound represented by the formula (1), the antibacterial activity represented by the formula (2) having a weight average molecular weight of 10, 000-1, 000, 000, A polyethylene matrix resin comprising at least one organic antimicrobial selected from the group consisting of a homopolymer and an antibacterial acrylic copolymer of formula 3 having a weight average molecular weight of 10, 000-1, 000, 000 is melt-extruded, From the extruder forming the outermost layer of the film, a polyamide resin is melt-extruded, The present invention provides a method for producing an antibacterial vacuum packaging film.

The polyethylene matrix resin forming the innermost layer of the packaging film may be a polyethylenic main resin; And a polyethylene master batch in which a polyethylene resin containing selenium particles or an organic antimicrobial agent is pelletized.

More preferably, the polyethylene matrix resin comprises 100 parts by weight of a polyethylene resin; And a polyethylene masterbatch comprising 25 to 45 parts by weight of a polyethylene masterbatch comprising 100 to 200 ppm of selenium particles or 20 to 50 parts by weight of an organic antimicrobial agent based on 100 parts by weight of the polyethylene resin forming the polyethylene masterbatch To 10 parts by weight. On the other hand, the polyethylene master batch containing the selenium particles comprises 30-40 parts by weight of selenium particles, 17-35 parts by weight of stearic acid, 30-60 parts by weight of water, and 25-40 parts by weight of alcohol 25-40 parts by weight, based on 100 parts by weight of the polyethylene resin forming the polyethylene master batch, And 35 parts by weight of a maleic anhydride, followed by preparing a polyethylene resin composition for forming a polyethylene master batch by coalescing with a polyethylene resin containing maleic anhydride in an upper silver salt; Heating the polyethylene resin composition to produce a polyethylene resin coated with the selenium particles; And extruding and pelleting the polyethylene resin coated with the selenium particles into a twin screw extruder to produce a polyethylene master batch containing the selenium particles,

Wherein the polyethylene masterbatch containing the organic antibacterial agent is prepared by mixing 20 to 50 parts by weight of an organic antimicrobial agent with respect to 100 parts by weight of a polyethylene resin forming a polyethylene masterbatch to prepare a polyethylene resin composition for forming a polyethylene masterbatch; And extruding and pelletizing the polyethylene resin composition comprising the organic antimicrobial agent into a twin screw extruder to produce a polyethylene master batch containing an organic antimicrobial agent.

In the seven extruders, the antimicrobial vacuum packaging film of the seven-layer structure is formed by alternately forming four resin layers of a polyamide resin and a polyethylene resin from the outside to the inside of the film, And co-extruding each resin to form a stratum.

The polyamide resin is preferably nylon 6 or nylon 66, and the polyethylene resin may be a low density polyethylene (LDPE) or a linear low density polyethylene (LLDPE) . Further, the adhesion resin layer may be a maleic anhydride modification

VLDPECMaleic anhydride modi fi ed VLDPE). 【Effects of the Invention】

The antibacterial vacuum packaging film provided by the present invention can be preserved for a longer period of time by adding antimicrobial properties while maintaining the low permeability of oxygen and water vapor. This can reduce the overall use of the packaging film, thereby reducing the use of fossil fuels and, ultimately, reducing carbon emissions. Further, the present invention can obtain a high-quality vacuum packaging film by using a low-cost antimicrobial agent other than silver, while being harmless to the human body and reducing the cost of product production.

BRIEF DESCRIPTION OF THE DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a layer structure and constituent materials of a seven-layered antimicrobial vacuum packaging film provided by the present invention. FIG.

Fig. 2 is a schematic view of a co-extrusion apparatus for producing the film of Fig. FIGS. 3 to 10 are photographs showing the distribution of nano-sized salen particles according to the content of selenium in the innermost layer according to Example 1 in contact with an article to be packaged in the vacuum packaging film of the present invention measured by FE-SEM to be. Figs. 3, 5, 7 and 9 are photographs of the surface of the innermost layer of the vacuum packaging film, and Figs. 4, 6, 8 and 10 show the positions of selenium particles in the innermost layer It is a photograph of the time.

Figs. 11 and 12 are photographs showing the antimicrobial activity of the present invention as compared with the vacuum packaging film containing no selenium particles. The antibacterial activity of the antibacterial activity of the anti- Fig. 11 shows the result of the antibacterial test on Staphylococcus aureus, and Fig. 12 shows the results of the antibacterial test on E. coli.

FIG. 13 is a photograph showing the antibacterial test result of an antibacterial vacuum packaging film containing an antibacterial agent according to ASTM G22 modified method. FIG.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the present invention will be described in detail. The vacuum packaging film of the present invention is preferably composed of seven layers. The component constituting each layer is not necessarily limited to, but is preferably composed of poly (ethylene terephthalate) or polyamide. The polyethylenic resin is excellent in moisture barrier property to prevent the permeation of moisture into the container of the packaging film, and the polyamide resin has excellent oxygen barrier property, thereby preventing the inflow of oxygen into the packaging container. Allows long-term storage of oxygen-sensitive products. The order of the triple layers in the packaging film is not particularly limited, but the outermost layer of the temporary packaging film is formed of a polyamide resin and is in contact with the article to be packaged It is preferable that the innermost layer is formed on the basis of a polyethylene resin. Since the polyamide resin has excellent oxygen barrier properties, it is possible to block the penetration of oxygen into the container formed of the packaging film by forming the outermost layer using such a polyamide resin. Such a polyamide resin is not particularly limited as long as it has the above-mentioned oxygen barrier property, and it is more preferable to use nylon 6 or nylon 6,6. On the other hand, the polyethylene resin is excellent in the moisture barrier property as described above, so that moisture can be prevented from penetrating into the inside of the packaging container, and the heat sealing property of the polyethylene resin is excellent. It is preferable for sealing. Therefore, it is preferable that the innermost portion of the packaging material is formed of a polyethylene resin having excellent thermal adhesiveness. The polyethylene resin is not particularly limited, but a low density polyethylene (LDPE) or a linear low density polyethylene (LLDPE) can be used, and in the polyethylene resin used as the innermost layer, LLDPE is most preferably used for thermal adhesiveness. As described above, the order of forming the vacuum packaging film of the present invention is such that the innermost layer is made of a polyethylene resin and the outermost layer is made of a polyethylene resin If the intermediate layer is not particularly limited, it is most preferred that the polyamide resin, such as ethylene layer / polyamide layer toward the outermost layer to the poly-ethylene layer / ^"polyamide layer / polyester from the innermost layer to be formed alternately. What is formed in this manner is more effective in effectively blocking moisture and oxygen from the outside. In addition, during the packaging of the article, micro-oxygen may be contained in the inside of the package, and such oxygen may cause oxidation of the article to be packaged, thereby causing deterioration of the article. Therefore, if necessary, oxygen scavenging ability may be imparted to the polyamide resin layer having excellent oxygen barrier properties in order to remove such oxygen, so that a resin layer mainly composed of polyamide is formed on the adjacent layer of the innermost layer . The polyamide resin having such an oxygen capturing ability is not particularly limited, and any of those known in the art can be applied. In the present invention, the polypropylene resin layer forming the innermost layer of the vacuum packaging film may contain an antimicrobial agent for imparting an antimicrobial activity. Suitable antimicrobial agents in the present invention include nanometric sized salernium particles. The above-mentioned salernium particles preferably have a nanometer size, and more preferably have a particle size of 10-100 nm. If the particle size is less than 10 nm, the selenium particles are expensive and the final product is poor in hardness, and uniform dispersion of the particles in the resin composition may be difficult. As the haze increases and loses its value as a product, Size. On the other hand, since the selenium particles are an inorganic substance, it is preferable that the selenium particles are treated with stearic acid for uniform dispersion in the polyethylene resin.

The antimicrobial agent of the present invention includes the following antimicrobial organic monomer compounds of formula (1), antimicrobial homopolymers of formula (2) having a weight average molecular weight of 10, 000-1, 000, 000, An organic antimicrobial agent such as an antibacterial acrylic copolymer having a weight average molecular weight may be masterbatch and used interchangeably.

(1)

In Formula 1, R is a polymerization and a functional group and a light path to a saturated or unsaturated hydrocarbon of C ₁₅₀ containing the interactive reactive functional group, ¾ and ¾ are each independently with or simultaneously hydrogen, a halogen atom, an amine or (广(: ₂₀ and the alkyl group, ¾ and R4 are each independently or simultaneously hydrogen, a hydroxy group, C1 ~ C ₂₀ alkoxide, a halogen atom or - (a: an alkyl group of _20, ¾ is hydrogen, Cr o alkyl, cyclo propyl, or C广C ₂₀ aromatic hydrocarbons, and ¾ contains hydrogen, sodium, potassium or a polymerizable functional group, or Is that group of CrC ₁₅₀ not included, ¾, R ₉ and R ₁₀ is a carbon or nitrogen, each independently or simultaneously, R _u is hydrogen, primary, secondary or tertiary amine, a halogen atom or (^ - (: ₂₀ alkyl group.

(2)

In Formula 2, R and Re-Ru are as defined in Formula 1, and X is a positive integer satisfying the molecular weight.

(3)

HCH ^ X

R and R, and Re-Ru are the same as defined in the above formula (1). The salen particle used as the antimicrobial agent or the antimicrobial oil represented by the formula (1) The monomeric monomer compound, the antimicrobial homopolymer represented by the formula (2) or the antibacterial acrylic copolymer represented by the formula (3) has antimicrobial properties and is not self-toxic unlike silver, and the price is about 1/5 Because it is very inexpensive, it is very suitable for application in the present invention. In the present invention, the selenium particles contained in the innermost layer are preferably contained in an amount of 30 to 40 ppm of the weight of the innermost layer of the polyethylene resin layer, and the organic antibacterial agent is contained in an amount of 0.5 to 5 wt. It is preferable that it is included in the content. When the content of the antimicrobial agent is less than the lower limit, the antimicrobial activity can not be obtained. When the upper limit is exceeded, the haze of the film increases and the raw material is supplied to the extruder the antimicrobial activity of the antimicrobial resin can be obtained at the upper limit of the range. Therefore, the additional use of the antimicrobial resin only increases the cost of using the antimicrobial agent, It does not. Therefore, it is preferable that the content is in the above range. The antimicrobial vacuum packaging film of the present invention has a seven-layer structure. As described above, in the antibacterial vacuum packaging film of the present invention, the polyamide resin layer and the polyethylene resin layer are alternately located, and the adhesive layer is located between the resin layers. The adhesive layer is for firmly adhering two resin layers having different properties and is not particularly limited as long as it can adhere the polyamide resin and the polyethylene resin. Maleic anhydride modified polyene (VLDPE), and the maleic anhydride modified ultralow density polyethylene can be obtained from an ethylene-butylene copolymer or the like. By doing so, the antimicrobial vacuum packaging film of the present invention has a seven-layer structure including an adhesive layer between four resin layers. As shown in Fig. 1, the antimicrobial vacuum packaging film of the present invention has an antimicrobial vacuum packaging film in the order of the outermost layer to the innermost layer. As shown in Fig. 1, the polyamide layer / adhesive layer / polyethylene layer / Layer / adhesive layer / polyethylene layer containing antimicrobial agent. Hereinafter, a method for producing the antibacterial vacuum packaging film of the present invention will be described. The antimicrobial vacuum packaging film having the seven-layer structure of the present invention is produced by coextrusion. Conventionally, it is manufactured by a lamination method, and usually has a two- or three-layer structure. However, by applying the co-extrusion method as in the present invention, all layers can be simultaneously extruded and manufactured. In order to produce a 7-layer film using a conventional lamination method, a pre-manufactured film was unwound, an adhesive was applied, or extrusion coating was applied to a heat-bonding resin layer and then rewinding was repeated several times. By performing such a complicated process, there is a large loss of work material and time. However, since the coextrusion method can be carried out at a time, the work can be simplified and the economical efficiency can be improved. FIG. 2 schematically shows an extrusion apparatus suitable for producing the antibacterial vacuum packaging film of the present invention. A method of producing the seven-layer film of the present invention by co-extrusion and blow molding will be schematically described. Although not shown in detail in FIG. 2, seven extruders are connected to a die, and the molten polymer resin necessary for each layer is simultaneously extruded from the extruder by screws in the extruder, The film can be formed by continuous inflow into the die and airing, as in the case of air bubbles, from bottom to top. The extruder forming the innermost layer of the co-extruder may contain salen particles or an antimicrobial organic monomer compound of formula (1), an antimicrobial homopolymer of formula (2), or an antimicrobial acrylic copolymer high molecular compound of formula (3). Among the antimicrobial agents, the inorganic particles, salenium particles, are preliminarily mixed with polyethylenic resin to form a master batch, then the obtained master batch is mixed with a polyethylene resin as a main component, and the master batch is uniformly dispersed in a polyethylene resin And the innermost layer can be formed by on-extrusion. Thus, after making the master batch of the selenium and polyethylene, the polyethylene resin , It is preferable to extrude nano-sized selenium particles uniformly in LLDPE. In case of directly mixing selenium particles with LLDPE in a co-extruder, nano-sized selenium particles Is not uniformly distributed. The masterbatch comprising the selenium particles can be prepared by mixing selenium particles in a solution containing stearic acid, water and alcohols at room temperature, simulating the resulting mixture with polyethylene, heating ^at 70-100 ^° C To remove water and alcohol. By doing so, the selenium particles treated with stearic acid can be obtained, and the obtained selenium particles can be uniformly dispersed in the polyethylene resin, so that the selenium particles can be attached to the polyethylene resin. The master batch can be produced by extruding the polyethylene resin with the selenium particles thus obtained in a twin screw extruder and pelletizing the same. The master batch thus obtained is co-extruded with the polyethylene resin forming the innermost layer of the vacuum packaging film and co-extruded, whereby the innermost layer can be formed. The stearic acid, water and alcohols are added to 100 parts by weight of the polyethylene resin, 15-25 parts by weight of stearic acid, 30-60 parts by weight of water and 25-35 parts by weight of alcohol. The selenium particles are added to 100 parts by weight of the solution Can contain about 100-200ppm. Is the content which can be present in 30 to 40 ppm in the finally obtained film when the selenium particles are contained within the above range. Therefore, when the content of selenium is less than lOOppm, it is impossible to provide a layered antibacterial activity to the final film. When the content of selenium exceeds 200ppm, a large amount of the selenium particles are contained in the masterbatch obtained therefrom. The effect of the antimicrobial activity is not so great. Instead, the haze of the film is greatly increased. In addition, feeding of the raw material during the extruding operation is not easily performed in the extruder. In addition, it is preferable that stearic acid is contained in an amount of 15-25 parts by weight per 100 parts by weight of the polyethylene resin as an agent for binding selenium particles to the polyethylene resin. On the other hand, water and alcohol serve as a solvent, and the content thereof is not particularly limited. However, when the content is less than the lower limit and is contained in a content lower than the lower limit, there is a problem in uniformly coating the selenium particles with the polyethylene resin When the upper limit is exceeded, the solution is too thin and it is burdened to remove the pellets from the solution. It is preferable to limit the range to the above range. On the other hand, the polyethylene resin may be the same as the main resin forming the innermost layer of the seven-layer antimicrobial vacuum packaging film of the present invention, preferably LLDPE. Further, the polyethylene resin may contain maleic anhydride in an amount of from 0.1 to 3 wt% More preferably polyethylene. By using maleic anhydride as a compatibilizer so that polarized selenium particles have affinity to nonpolar polyethylenes, the selenium particles are uniformly coated on the polyethylene. By heating the polyethylenic resin composition having the above components, water and alcohols are evaporated and removed, so that the selenium particles can be adhered to the polyethylene resin. In this case, the heating temperature is not particularly limited, and any temperature capable of removing water and alcohol can be appropriately selected. The solvent and water-and-alcohol-removed poly (ethylene oxide) resin composition can be prepared by extruding a poly (ethylene terephthalate) resin composition using a twin screw extruder commonly used for preparing a master batch to pelletize the master batch. The master batch obtained by the present invention is a master batch of selenium particle-polyethylenes containing 100-200 ppm of selenium per 100 parts by weight of polyethylene resin. The selenium particle-polyetylene master batch prepared as described above was mixed with a polyethylene resin, which is a main resin, and extruded into an extruder and melt-extruded through a T-die to form the innermost layer of the 7-layer antimicrobial vacuum packaging film of the present invention can do. In preparing the innermost layer, the selenium particle-adhered polyethylene masterbatch may be used in an amount of 25-45 parts by weight per 100 parts by weight of the polyethylene resin used as the main resin It is preferable to be common. In this case, a sufficient antibacterial activity can be imparted to the antibacterial vacuum packaging film of the present invention. More preferably, the selenium particle-polyethylene master batch prepared as described above is mixed with a polyethylene resin as a main resin, and the resulting mixture is introduced into an extruder forming an innermost layer of a co-extrusion apparatus for producing an antimicrobial vacuum packaging film having a seven-layer structure, , A suitable resin for forming each layer of a film having a seven-layer structure is put in each extruder, and then they are melt-extruded by a T-die at the same time, An antibacterial vacuum packaging film can be produced. Specifically, as shown in FIG. 1, the outermost layer and the fifth layer from the outside of the film are made of a polyamide resin layer of nylon 6 or nylon 6, 6 to give oxygen barrier properties, and a third layer The inner layer is made of a polyethylene resin layer of polyethylenes or linear polyethylenes for imparting water vapor barrier properties and heat sealing properties and a polyamide resin layer and a polyurethane resin layer are formed in the second, By inserting a polymer adhesive layer (ie layer) for bonding the polyethylene resin layer, a vacuum film having excellent oxygen and water vapor barrier properties and further having an antibacterial activity can be produced. On the other hand, as the antimicrobial agent, besides the selenium particle, the antimicrobial organic monomer compound represented by the formula (1), the antimicrobial homopolymer represented by the formula (2) And an antibacterial acrylic copolymer represented by the following general formula (3). Such an organic antimicrobial agent is commonly used to prepare a master batch with polyethylene resin, which is the main resin forming the innermost layer of the antimicrobial vacuum packaging film of the seven-layer structure of the present invention, as in the case of using the above-mentioned selenium particles. The preparation of the masterbatch can be achieved by uniformly dispersing the mixture of the organic antimicrobial agent and the polyethylene resin and extruding it in a twin screw extruder to pellet the master batch. At this time, it is preferable that the organic antibacterial agent is contained in an amount of 20 to 50 parts by weight based on 100 parts by weight of the polyethylene resin. By thus obtaining the antimicrobial agent content, the antimicrobial agent can be uniformly distributed on the final polyethylene resin layer, so that the stratified antimicrobial activity can be obtained. Therefore, if the content of the organic antibacterial agent is less than 20 parts by weight, the antimicrobial activity can not be obtained. If the content exceeds 50 parts by weight, further antibacterial activity can not be obtained. The organic antimicrobial agent-polyethylene master batch prepared as described above is mixed with a polyethylene resin as a main resin, and the mixture is put into an extruder and melt-extruded through a T-die to form the innermost layer of the 7-layer antimicrobial vacuum packaging film of the present invention . In preparing the innermost layer, the polyethylene masterbatch containing the organic antimicrobial agent is preferably contained in an amount of 3 to 10 parts by weight based on 100 parts by weight of the polyethylene resin. Within this range, the antimicrobial vacuum packaging film of the present invention, It is possible to provide a stratified antimicrobial activity in the innermost layer. The antibacterial vacuum packaging film of the present invention can obtain a vacuum packaging film excellent in environmentally friendly antimicrobial activity which can greatly reduce the amount of packaging film used for preserving food and the amount of carbon dioxide generated by the incineration treatment of the used packaging film In addition, it is possible to manufacture an antimicrobial vacuum packaging film by using a salenium or acrylic copolymer in place of silver nanoparticles which may be harmful to the human body, thereby solving the problem of human harm caused by the antibacterial component. Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples are only illustrative of the present invention and are not intended to limit the present invention. Example

Example 1

300 ppm of selenium particles were uniformly dispersed in 100 parts by weight of a solution containing 20 parts by weight of stearic acid, 50 parts by weight of water and 30 parts by weight of alcohol at room temperature. The obtained solution was mixed with 100 parts by weight of polyethylene (LLDPE, product name: MPE XP5300, Melt Index 2.4) containing 1 wt% of maleic anhydride and then heated at 120 ^° C to obtain water and The alcohol was removed. A polyethylenic resin having selenium particles adhered thereto by stearic acid thus obtained was extruded by a twin screw extruder and pelletized to prepare a salernium particle-LLDPE master batch. The obtained master batch was mixed with the same LLDPE as the one forming the innermost layer. At this time, the masterbatch was contained at 35, 25, 20 and 17 parts by weight based on 100 parts by weight of LLDPE.

In order to produce a seven-layer vacuum packaging film, a nylon 6-66 copolymer and a third resin layer were provided in the first extruder to provide a first resin layer (outermost layer) among co-extruding devices having seven extruders The master batch and the linear low density polyethylene mixture were fed into a seventh extruder which provided a nylon 6 and a seventh resin layer (innermost layer) in a fifth extruder which provided a low density polyethylene and a crab five resin layer in a third extruder, Fourth, and sixth extruders provided with the second, fourth, and sixth adhesive layers, respectively, and then the respective resins were melt-extruded by a T-die and subjected to a blow molding method , An antimicrobial vacuum packaging film having a seven-layer structure as shown in Fig. 1 was prepared. The thickness of each layer obtained is as follows.

First resin layer (A layer): 11 /?? Third resin layer (C layer): 16 /?

Fifth resin layer (E layer): 1 seventh resin layer (G layer): 17 / im

(B, !, respectively) and E layer of crab 2, 4 and 6: 7 / im The content of selenium particles in the innermost layer of the obtained vacuum packaging film was measured according to the weight of the masterbatch. As a result, it was found that the content of selenium in the resin layer (G layer) constituting the innermost layer of the antibacterial vacuum packaging film The content of rhenium contained 35 parts by weight of masterbatch, the content of salenium was 37.5ρρπι, the content of masterbatch was 25 parts by weight, the content of salenium was 30 ppm, and the content of masterbatch was 20 parts by weight, 25 · 1ρρηη, and the selenium content of the master batch containing 17 wt% was 21.5 ppm. 3 to 10 show whether the selenium particles are uniformly dispersed in the innermost layer of the obtained vacuum packaging film using FE-SEM. FIGS. 3, 5, 7 and 9 are photographs of the surface of the innermost layer of the vacuum packaging film, and FIGS. 4, 6, 8 and 10 are photographs showing the positions of selenium particles in the innermost layer. As described above, the antimicrobial activity test was performed according to the content of selenium in the resin in the cervix 7 to test the antibacterial activity. The antimicrobial activity of the selenium-containing antimicrobial vacuum packaging film was determined according to JIS Z 28 as follows.

- As a used strain, Staphylococcus aureus ATCC 6538P (strain

1) and Escherichia coli ATCC 8739 (strain 2) were used.

- Stoacher 400 P0LY-BAG was used as the standard coating film.

- The test strain was incubated for 24 hours under the conditions of 35 ^° C and 5% RH ^at 1 ^° C. Respectively.

- The surface area of the sample is 25oif, and the antimicrobial activity value S, the reduction rate (¾) and the proliferation value (F), which show the antibacterial performance, are calculated by the following equations.

The antibacterial activity (S) = log (M _b / M _c ),

Reduction rate (%) = {(M _b - M _c ) / M _b } x i00

Proliferation value (F) = log (M _b / M _a )

However, where ^ represents viable cell count immediately after the test bacteria inoculated in a standard sample pyeonggyunreul, M _b represents an average of the number of viable cells after 24 hours culture of the reference samples, M _c is the average of the number of viable cells after 24 hours culture of the antibacterial samples . Table 1 shows the test results of the packaging film for a packaging film having a selenium content of 30 pptn having a selenium content of 37.5 ppm contained in the innermost layer.

[Table 1]

As can be seen from the above Table 1, the selenium content in the innermost layer

The antibacterial activity value (S) was 6.1 and the reduction rate was 99.9% in the packing film with 37.5ppm. In the packaging film with 30ppm selenium content, the antibacterial activity value (S) was 6.1 and the reduction rate was 99.9% Showed excellent antimicrobial activity against strains 1 and 2. On the other hand, in the packaging film having the selenium content of 25.1 ppm contained in the innermost layer, the antimicrobial activity value (S) was 5.9 and the reduction rate was 98.9% in the packaging film, and the antibacterial activity value (S) in the packaging film having the selenium content of 21.5 ppm was 5.7 And the rate of decrease was 97.9%, indicating that the antibacterial activity against strains 1 and 2 was low. Therefore, it was confirmed that the antimicrobial activity was excellent when the content of salenium contained in the innermost layer of the packaging film was 30 ppm or more. Example 2

A master batch comprising 20 parts by weight of an antibacterial acrylic copolymer represented by the formula (3) in 100 parts by weight of a matrix of LLDPE (product name MPE XP5300, Melt Index 2.4, marketed by Daelim Industrial) BCA-502MB, the product name of the company, was mixed. At this time, the masterbatch was contained in 1, 3, 5 and 7 parts by weight based on 100 parts by weight of the LLDPE.

A vacuum packaging film having a seven layer structure was prepared by coextruding the resin of each layer by a co-extrusion method using a co-extrusion apparatus having seven extruders. A specific method for producing a vacuum packaging film was performed in the same manner as described in Example 1 above. The antimicrobial activity of the prepared vacuum packed film was evaluated by using Escherichia coli LB broth, LB agar plates, Nutrient broth, and Nutrient agar plates were used as the medium, and Escherichia coli (strain 1) and Sahnonel la typhimurium (strain 2) Halosone) measurement was carried out in accordance with AST 占 G22 as follows. . The test strain is inoculated into a culture tube containing 3 m of LB, and then the tube cap is placed on the culture tube and incubated at 37 ^° C with shaking at 150 rpm for 24 hours. The obtained culture solution 100 is inoculated into a culture tube containing LB, and then cultured in the same manner repeatedly 2 to 3 times.

Shake the prepared inoculum vortexing uniformly, then inoculate the LB plate using a micropipette. Immerse the glass rod in 10OT ethanol, remove it, sterilize the flame, and cool. The strains inoculated with the glass membrane are spread and spread evenly over the medium.

Test samples are spray dried with 70% ethane and dried. Place each test sample in the middle of the inoculated medium with the sterilized tweezers. In the case of a coating test sample, the coated side is allowed to reach the inoculated medium. Press the test sample slightly so that the sample is well in contact with the discharge surface. Incubate for 2 days at 37 ^° C in an incubator.

The test sample is taken in four directions from the side to the clear zone line where the cells do not grow, and the average value (mm) is obtained. And those having an average value of 1.5 or more were evaluated as having excellent antimicrobial activity. The evaluation results according to this embodiment are shown in Table 2 and Fig. Table 2 shows the average value (mm) of the test sample in four directions from the side to the clear zone line where the bacteria did not grow from the side, and Fig. 13 shows the results of the ASTM G22 modified Method , Which is a photograph showing the results of the antibacterial test. [Table 2]

When the content of the BCA-502MB masterbatch used in the preparation of the innermost layer of the antibacterial vacuum packaging film was 1 part by weight, no inhibition zone was generated for the strain 1, and thus it was confirmed that there was no antibacterial activity there was. In addition, the inhibition band of 0.5 was produced for strain 2, and the antimicrobial activity was evaluated to be low. When the content of the BCA-502MB masterbatch used for preparing the innermost layer of the antibacterial vacuum packaging film was 3 parts by weight, it was confirmed that the antibacterial vacuum packaging film produced an inhibition band of 1.75D dish for the strain 1, indicating that it was antibacterial. In addition, it was confirmed that the strain 2 had antimicrobial activity by generating a restraint of 2.75. When the content of the BCA-502MB masterbatch used in the preparation of the innermost layer of the antibacterial vacuum packaging film was 5 parts by weight, it was confirmed that there was an antibacterial property by producing 2.25 억제 inhibition against the strain 1. In addition, for strain 2, a restraint of 3.72 < RTI ID = 0.0 > However, it was confirmed that there was antibacterial activity. When the content of the BCA-502MB masterbatch used in the preparation of the innermost layer of the antibacterial vacuum packaging film was 7 parts by weight, it was confirmed that the antibacterial vacuum packaging film produced an inhibition band of 3.751 thrice against the strain 1, indicating that it was antibacterial. In addition, for strain 2, a restraining band of 5.50 tors was produced, and it was confirmed that there was antibacterial activity.

Claims

Claims 1. An antibacterial vacuum packaging film for packaging an article, wherein the packaging film is composed of seven layers, the outermost layer of the packaging film being formed of a polyamide resin, Wherein the innermost layer is formed of a polyethylene resin, and the innermost layer is selected from the group consisting of salen particles having a particle size of 5 to 10 nm or an antimicrobial organic monomer compound represented by the formula (1), a compound represented by the formula (2) having a weight average molecular weight of 10,000 to 1,000, Antimicrobial vacuum packaging with a seven-layer structure comprising at least one organic antimicrobial selected from the group consisting of an antimicrobial homopolymer and an antimicrobial acrylic copolymer of formula (3) having a weight average molecular weight of 10, 000-1, 000, 000. film.

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

R is a d to C ₁₅₀ saturated or unsaturated hydrocarbon comprising a polymerizable functional group and a photocurable reactive functional group,

Ri and R < ₂ > are each independently or simultaneously a hydrogen, a halogen element, an amine or an alkyl group having 1 to ₂₀ carbon atoms,

An alkyl group of _20,: ¾ and ¾ are each independently or simultaneously hydrogen, a hydroxy group, C1 ~ C ₂₀ Al koksa Id, a halogen atom or (in:广(

¾ is hydrogen, (^ - (: an aromatic hydrocarbon of the _20-alkyl, cyclo propyl or d ^{^} Czo of, ¾ is - (not including hydrogen, sodium, potassium, or the polymerizable functional group or containing or: an alkyl group of _150,

And R < ₉ > and Rio are each independently or simultaneously carbon or nitrogen,

Rii is hydrogen, a primary, secondary or tertiary amine, a halogen element or an alkyl group of d-Czo,

X is a positive integer satisfying the above-mentioned molecular weight.

[Claim 2]

The antibacterial vacuum packaging film according to claim 1, wherein the antibacterial vacuum packaging film comprises Wherein the resin layer comprises four resin layers alternately arranged with a polyamide resin and a polyethylene resin, and an adhesive resin layer formed between the respective resin layers.

Claim 31

The coextruded antimicrobial vacuum packaging film according to claim 1 or 2, wherein the polyamide resin is nylon 6 or nylon 66.

[4]

The coextruded antimicrobial vacuum packaging film of claim 1 or 2, wherein said polyethylene is low density polyethylene (LDPE) or linear low density polyethylene (LLDPE).

[Claim 5]

The coextruded antibacterial vacuum packaging film according to claim 2, wherein the adhesive resin layer is formed of maleic anhydride modified VLDPE (VLDPE).

[Claim 6]

The coextruded antibacterial vacuum packaging film according to claim 1 or 2, wherein the saccharide particles are contained in an amount of 30 ppm to 40 ppm of the innermost layer weight.

7.

The coextruded antibacterial vacuum packaging film according to claim 1 or 2, wherein the organic antibacterial agent is contained in an amount of 0.5-5% by weight of the weight of the resin layer.

8. A method for producing an antimicrobial vacuum packaging film having a seven-layer structure, wherein the packaging film is produced by melt co-extruding a resin in an extruder using a pneumatic actuator including seven compressors,

From the extruder forming the innermost layer of the packaging film in contact with the article to be packed, the selenium particles or the antimicrobial organic monomer compound represented by the formula (1), having a weight average molecular weight of 10, 000-1, 000, 000 A polyimide comprising at least one organic antimicrobial agent selected from the group consisting of an antimicrobial single incremental compound represented by the general formula (2) and an antibacterial acrylic copolymer represented by the general formula (3) having a weight average molecular weight of 10, 000-1, Wherein the tile matrix resin is melt-extruded and the polyamide resin is melt-extruded from an extruder forming the outermost layer of the packaging film.

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

R is a d to C ₁₅₀ saturated or unsaturated hydrocarbon comprising a polymerizable functional group and a photocurable semi-functional group,

Ri and R ₂ are each independently or simultaneously a hydrogen, a halogen element, an amine or an alkyl group of C ₁ -C ₂₀ ,

And ¾, and R4 are each independently or simultaneously, represents a hydrogen, hydroxy group, C1 ~ C ₂₀ Al koksa Id of, a halogen atom or a C2 ~ d _0,

¾ is hydrogen, d-Czo-alkyl, cyclo propyl, or (in:广(: an aromatic hydrocarbon of _20, is an alkyl group of ¾ Crdso does not contain a hydrogen, sodium, potassium, or the polymerizable functional group or containing or,

Rg and o are each independently or simultaneously carbon or nitrogen, R < 1 > is hydrogen, a primary, secondary or tertiary amine, a halogen atom or an alkyl group of d-Czo, and X is a positive integer satisfying the above molecular weight.

[Claim 9]

9. The polyethylene matrix resin according to claim 8, wherein the polyethylene matrix resin forming the innermost layer of the packaging film comprises a polyethylene main resin; And a polyethylene masterbatch obtained by pelletizing a polyethylene resin containing salen particles or an organic antimicrobial agent.

[Claim 10]

10. The method of claim 9, wherein the polyethylene matrix resin comprises:

100 parts by weight of a polyethylene main resin; And

To 100 parts by weight of the polyethylene resin forming the polyethylene master batch, 3 to 10 parts by weight of a polyethylene masterbatch comprising 25 to 45 parts by weight of a polyethylene masterbatch containing 100 to 200 ppm of selenium particles or 20 to 50 parts by weight of an organic antibacterial agent Wherein the antimicrobial vacuum packaged film has a thickness of about 5 mm.

Claim 111

The polyethylene masterbatch according to claim 9, wherein 30 to 40 parts by weight of selenium particles are contained in an amount of 17 to 35 parts by weight of stearic acid, 30 to 60 parts by weight of water Preparing a polyethylene resin composition for forming a polyethylene master batch by dispersing the mixture in a solution containing 25 to 35 parts by weight of allyl alcohol and maleic anhydride at room temperature; Heating the polyethylene resin composition to produce a polyethylene resin coated with the selenium particles; And

And a step of extruding and pelletizing the polyethylene resin coated with the selenium particles with a twin screw extruder to prepare a polyethylene master batch containing selenium particles. Gt;

Claim 12

The polyethylene master batch according to claim 9, wherein 20 to 50 parts by weight of an organic antimicrobial agent is mixed with 100 parts by weight of a polyethylene resin forming the polyethylene masterbatch to prepare a polyethylene masterbatch composition for forming a polyethylene masterbatch Lt; / RTI >

And extruding and pelletizing the polyetylene resin composition containing the organic antimicrobial agent with a twin screw extruder to prepare a polyetylene master batch containing an organic antimicrobial agent. Structure antimicrobial anti - foaming film. ·

[13]

[Claim 9] The method of claim 8, wherein the seven extruders have the seven-layered antimicrobial vacuum packaging film in which four resin layers of a polyamide resin and a polyethylene resin are alternately formed from the outside to the inside of the film, Wherein each resin is pneumatically delivered so that an adhesive resin layer is formed between the layers.

14.

14. The method of producing an antimicrobial vacuum packaging film according to any one of claims 8 to 13, wherein the three polyamide resins are nylon 6 or nylon 66.

15.

14. The method for producing an antimicrobial vacuum packaging film according to any one of claims 8 to 13, wherein the polyethylene resin is low density polyethylene (LDPE) or linear low density polyethylene (LLDPE).

Claim 16

14. The method of claim 13, wherein the adhesive resin layer is formed of maleic anhydride modified VLDPE (VLDPE).