WO2012081756A1 - Film co-extrudé d'emballage sous vide antimicrobien possédant une structure à sept couches et procédé de fabrication associé - Google Patents

Film co-extrudé d'emballage sous vide antimicrobien possédant une structure à sept couches et procédé de fabrication associé Download PDF

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Publication number
WO2012081756A1
WO2012081756A1 PCT/KR2010/009217 KR2010009217W WO2012081756A1 WO 2012081756 A1 WO2012081756 A1 WO 2012081756A1 KR 2010009217 W KR2010009217 W KR 2010009217W WO 2012081756 A1 WO2012081756 A1 WO 2012081756A1
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Prior art keywords
antimicrobial
polyethylene
resin
weight
packaging film
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PCT/KR2010/009217
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English (en)
Korean (ko)
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김일용
장영욱
김금자
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주식회사 롤팩
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Publication of WO2012081756A1 publication Critical patent/WO2012081756A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • 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.
  • 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.
  • 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.
  • nylon polyamide
  • 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.
  • an antimicrobial vacuum film having antimicrobial ability by uniformly dispersing nano-sized antimicrobial substance in the film in contact with the article.
  • 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 .
  • 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.
  • silver has a problem of low cost because of its high price.
  • 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.
  • 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
  • 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 .
  • 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 .
  • the polyamide resin may be nylon 6 or nylon 66
  • the polyethylene may be low density polyethylene (LDPE) or linear low density polyethylene (LLDPE).
  • 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,
  • 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
  • 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.
  • 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.
  • 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,
  • 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.
  • 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
  • the polyethylene resin may be a low density polyethylene (LDPE) or a linear low density polyethylene (LLDPE)
  • the adhesion resin layer may be a maleic anhydride modification
  • VLDPECMaleic anhydride modi fi ed VLDPE VLDPECMaleic anhydride modi fi ed VLDPE.
  • 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.
  • 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. 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. 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
  • 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
  • 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.
  • 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.
  • the polyamide 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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 sagruium particles.
  • the above-mentioned sagruium 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.
  • 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
  • 3 ⁇ 4 and 3 ⁇ 4 are each independently with or simultaneously hydrogen, a halogen atom, an amine or ( ⁇ (: 20 and the alkyl group, 3 ⁇ 4 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, 3 ⁇ 4 is hydrogen, Cr o alkyl, cyclo propyl, or C ⁇ C 20 aromatic hydrocarbons, and 3 ⁇ 4 contains hydrogen, sodium, potassium or a polymerizable functional group, or Is that group of CrC 150 not included, 3 ⁇ 4, 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.
  • R and Re-Ru are as defined in Formula 1, and X is a positive integer satisfying the molecular weight.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the polyethylene resin 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.
  • 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.
  • water and alcohol serve as a solvent, and the content thereof is not particularly limited.
  • 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.
  • the selenium particles are uniformly coated on the polyethylene.
  • water and alcohols are evaporated and removed, so that the selenium particles can be adhered to the polyethylene resin.
  • 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.
  • 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.
  • 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.
  • 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,
  • a polymer adhesive layer ie layer
  • 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.
  • 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.
  • 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 .
  • 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
  • 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 sagruium 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.
  • 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.
  • 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 37.5 ⁇ , 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 ⁇ 1 ⁇ , and the selenium content of the master batch containing 17 wt% was 21.5 ppm.
  • FIGS. 3, 5, 7 and 9 are photographs of the surface of the innermost layer of the vacuum packaging film
  • FIGS. 4, 6, 8 and 10 are photographs showing the positions of selenium particles in the innermost layer.
  • 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.
  • 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 (3 ⁇ 4) 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 ),
  • 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.
  • 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.
  • 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.
  • 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.
  • LLDPE product name MPE XP5300, Melt Index 2.4, marketed by Daelim Industrial
  • 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 ⁇ G22 as follows. .
  • 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.
  • 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.

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Abstract

La présente invention concerne un film d'emballage sous vide antimicrobien qui possède une structure à sept couches qui présente des performances antimicrobiennes, et un procédé de fabrication associé. La présente invention concerne un film d'emballage sous vide antimicrobien qui possède une structure à sept couches, qui est un film d'emballage sous vide antimicrobien pour emballer un article, le film d'emballage comprenant sept couches ; la couche la plus extérieure du film d'emballage est formée à partir d'une résine polyamide ; la couche la plus intérieure, qui entre en contact avec l'article, est formée à partir d'une résine polyéthylène ; et la couche la plus intérieure comprend des particules de sélénium qui possèdent une dimension des particules entre 5 et 10 nm ou au moins un agent antimicrobien organique sélectionné parmi le groupe constitué de composés monomères organiques antimicrobiens représentés par la formule chimique 1, de homopolymères antimicrobiens représentés par la formule chimique 2 qui possèdent un poids moléculaire moyen pondéral entre 10 000 et 1 000 000, et de copolymères acryliques antimicrobiens représentés par la formule chimique 3 qui possèdent un poids moléculaire moyen pondéral entre 10 000 et 1 000 000. La présente invention concerne également un procédé de fabrication de film du type à co-extrusion. La présente invention fournit une fonction antimicrobienne à un film d'emballage sous vide qui possède d'excellentes propriétés de blocage d'oxygène et de vapeur d'eau, et, ainsi, la présente invention permet un stockage alimentaire relativement à long terme et ainsi permet de réduire l'utilisation de film d'emballage et ainsi permet de réduire la quantité d'utilisation de naphta qui est un ingrédient brut de base dans la fabrication de film, et permet également de réduire la quantité d'utilisation de pétrole en tant que source d'énergie nécessaire pour la fabrication et ainsi permet d'obtenir un effet écologique.
PCT/KR2010/009217 2010-12-15 2010-12-22 Film co-extrudé d'emballage sous vide antimicrobien possédant une structure à sept couches et procédé de fabrication associé WO2012081756A1 (fr)

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WO2019152557A1 (fr) 2018-01-30 2019-08-08 Modernatx, Inc. Compositions et procédés destinés à l'administration d'agents à des cellules immunitaires
CN110154367A (zh) * 2019-06-01 2019-08-23 安庆市康明纳包装有限公司 一种节能环保热封袋及其加工工艺
CN112318891A (zh) * 2020-09-29 2021-02-05 厦门长塑实业有限公司 一种高阻隔抗菌尼龙复合薄膜及其制备方法
CN113681993A (zh) * 2021-08-26 2021-11-23 浙江大汇新材料有限公司 一种用于船舶果蔬运输的保鲜抑菌透气包装膜及其制备方法
WO2022020811A1 (fr) 2020-07-24 2022-01-27 Strand Therapeutics, Inc. Nanoparticule de nanoparticule lipidique comprenant des nucléotides modifiés
CN114834102A (zh) * 2022-04-08 2022-08-02 中国农业科学院农产品加工研究所 一种抑制生鲜肉腐败菌的热收缩包装膜及其制备方法
CN115257107A (zh) * 2022-07-25 2022-11-01 湖北航天化学技术研究所 一种具有抗菌功能的高阻隔pe膜及其制备方法
WO2022233880A1 (fr) 2021-05-03 2022-11-10 Curevac Ag Séquence d'acide nucléique améliorée pour l'expression spécifique de type cellulaire
EP4186518A1 (fr) 2016-05-18 2023-05-31 ModernaTX, Inc. Polynucleotides codant l'interleukine-12 (il12) et leurs utilisations

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4186518A1 (fr) 2016-05-18 2023-05-31 ModernaTX, Inc. Polynucleotides codant l'interleukine-12 (il12) et leurs utilisations
WO2019152557A1 (fr) 2018-01-30 2019-08-08 Modernatx, Inc. Compositions et procédés destinés à l'administration d'agents à des cellules immunitaires
CN110154367A (zh) * 2019-06-01 2019-08-23 安庆市康明纳包装有限公司 一种节能环保热封袋及其加工工艺
WO2022020811A1 (fr) 2020-07-24 2022-01-27 Strand Therapeutics, Inc. Nanoparticule de nanoparticule lipidique comprenant des nucléotides modifiés
CN112318891A (zh) * 2020-09-29 2021-02-05 厦门长塑实业有限公司 一种高阻隔抗菌尼龙复合薄膜及其制备方法
CN112318891B (zh) * 2020-09-29 2022-09-13 厦门长塑实业有限公司 一种高阻隔抗菌尼龙复合薄膜及其制备方法
WO2022233880A1 (fr) 2021-05-03 2022-11-10 Curevac Ag Séquence d'acide nucléique améliorée pour l'expression spécifique de type cellulaire
CN113681993A (zh) * 2021-08-26 2021-11-23 浙江大汇新材料有限公司 一种用于船舶果蔬运输的保鲜抑菌透气包装膜及其制备方法
CN113681993B (zh) * 2021-08-26 2023-05-30 浙江大汇新材料有限公司 用于船舶果蔬运输的保鲜抑菌透气包装膜及其制备方法
CN114834102A (zh) * 2022-04-08 2022-08-02 中国农业科学院农产品加工研究所 一种抑制生鲜肉腐败菌的热收缩包装膜及其制备方法
CN115257107A (zh) * 2022-07-25 2022-11-01 湖北航天化学技术研究所 一种具有抗菌功能的高阻隔pe膜及其制备方法
CN115257107B (zh) * 2022-07-25 2023-07-21 湖北航天化学技术研究所 一种具有抗菌功能的高阻隔pe膜及其制备方法

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