WO1998052747A1 - Film d'emballage barriere, a couches multiples - Google Patents

Film d'emballage barriere, a couches multiples Download PDF

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Publication number
WO1998052747A1
WO1998052747A1 PCT/AU1998/000366 AU9800366W WO9852747A1 WO 1998052747 A1 WO1998052747 A1 WO 1998052747A1 AU 9800366 W AU9800366 W AU 9800366W WO 9852747 A1 WO9852747 A1 WO 9852747A1
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WO
WIPO (PCT)
Prior art keywords
layers
copolymer
packaging film
multilayer
barrier packaging
Prior art date
Application number
PCT/AU1998/000366
Other languages
English (en)
Inventor
Stamatis Ginossatis
John J. Aprea
Original Assignee
Sporos S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sporos S.A. filed Critical Sporos S.A.
Priority to NZ501636A priority Critical patent/NZ501636A/xx
Priority to AU76298/98A priority patent/AU745038B2/en
Priority to EP98923916A priority patent/EP0986464A4/fr
Priority to JP54970698A priority patent/JP2001525743A/ja
Publication of WO1998052747A1 publication Critical patent/WO1998052747A1/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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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

  • This invention relates to multilayer barrier packaging films.
  • This invention has particular application to such films for use in fabricating bags for packaging primal and sub- primal meat cuts and processed meats.
  • films in accordance with the present invention may find use in other packaging applications such as packaging air or moisture sensitive compositions generally such as curable putties and sealants, other foodstuffs such as tofu, or the like.
  • the meat packaging industry may be commonly divided into three segments, being fresh meats, frozen meats and processed meats.
  • Fresh and processed meats are of inherently short shelf life compared to frozen storage.
  • Processed meats and red meats are routinely packed in airtight plastic film packs to aid cold storage.
  • the primal and sub-primal meat cuts are large cuts of meat. They are smaller than a side of beef, for example, but larger than the ultimate cut which is sold at retail to the consumer.
  • a primal cut comprises the entire section of a side beef, such as the rib section or the rump roast section, while a sub-primal cut comprises only a portion of such a section.
  • Primal and sub-primal cuts are prepared at the slaughter house and are then shipped to a retail meat store, or to an institution such as a hospital, hotel or restaurant, where they are butchered into small cuts of meat suitable for the individual consumer.
  • the processed meat industry takes various portions of the animal carcasses and processes these portions under varying conditions to produce finished meat products which may be used directly by the consumer.
  • Products may include ham, smoked picnics, smoked butts, corned beef, turkey breast and various sausage products such as frankfurters, smoked sausage links, bologna, salami and the like. These products may be packaged in consumer portions or they may be packaged in bulk for shipment to a retail meat store, restaurant or hotel. Bulk shipments may include such items as ham chunks, cooked turkey breasts, bologna chubs, long bologna for delicatessen sale, rings of bologna, corned beef brisket, smoked picnics, smoked butts and linked products such as smoked sausage.
  • fresh red meat cuts such as roast or rib sections, and bulk processed meats are prepared for shipment or storage, they are usually packaged in such a way that air (ie oxygen) is prevented from contacting the meat and moisture is prevented from leaving the meat. This is done in order to minimize spoilage and discoloration during shipping and handling.
  • One desirable way to package fresh red meats and processed meats so as to protect them from contact with air and from moisture loss is to shrink package them with a packaging material that has good oxygen and moisture vapour barrier properties.
  • One such shrink packaging material that has good oxygen and moisture vapour barrier properties is polyvinylidene chloride film. Vinylidene chloride-vinyl chloride copolymers are commonly referred to as PVDC.
  • PVDC vinylidene chloride-vinyl chloride copolymer film
  • it must be plasticized in order for the film to have adequate abrasion resistance and flexibility at storage temperature of, for example, 30°F to 50°F.
  • plasticizer sufficient to provide the requisite low temperature properties to the PVDC monolayer film has a significant adverse effect on the barrier properties of the film.
  • a film having barrier properties which are better than those of the 38 to 50 micron monolayer PVDC film previously used for shrink packaging meat is to employ a multilayer film, one layer of which is vinylidene chloride-vinyl chloride copolymer having a minimum amount of plasticizer.
  • the other layer or layers of such multilayer films are selected so as to provide the requisite low temperature properties and abrasion resistance which are lacking in the vinylidene chloride-vinyl chloride layer containing little or no plasticizer.
  • the film must be heat sealable in order to be able to fabricate bags from the film and in order to heat seal the open ends of the fabricated bags after insertion of the meat product.
  • the heat sealed seams of the bags must not pull apart during the heat shrinking operation, and the film must resist puncturing by sharp bone edges during the heat shrinking operation.
  • multilayer films one layer of which is a vinylidene chloride-vinyl chloride copolymer and at least one other layer of which is an ethylene-vinyl acetate copolymer.
  • such films are proposed in McFedries, Jr, et al.
  • multilayer films comprising a core layer of a vinylidene chloride copolymer, wherein the vinylidene chloride copolymer is a copolymer of a vinylidene chloride monomer and a vinyl chloride monomer, are known, for example as disclosed in Brax et al, US Pat Nos 3,741,253 and 4,278,738, Baird et al US Pat No 4,112,181 and Lustig et al Canadian Pat No 982,983.
  • Multilayer films comprising a very low density polyethylene which is a linear copolymer of ethylene and higher alpha olefin containing from 3 to 8 carbon atoms, having a density below about 0.91g/cm ⁇ and a secant modulus below about 140,000kPa are also known and disclosed in Lustig et al US Pat No 4,976,898.
  • Kuo US Pat No 5,491,019 discloses multilayer films comprising "ethylene alpha-olefin copolymer", or "ethylene/ ⁇ - olefin copolymer” which is defined as such heterogeneous materials as linear low density polyethylene (LLDPE), and very low and ultra low density polyethylene (VLDPE and ULDPE); and homogeneous polymers such as metallocene catalyzed polymers such as EXACTTM materials supplied by Exxon, and TAFMERTM materials supplied by Mitsui Petrochemical Corporation.
  • LLDPE linear low density polyethylene
  • VLDPE and ULDPE very low and ultra low density polyethylene
  • homogeneous polymers such as metallocene catalyzed polymers such as EXACTTM materials supplied by Exxon, and TAFMERTM materials supplied by Mitsui Petrochemical Corporation.
  • These materials generally include copolymers of ethylene with one or more comonomers selected from C4 to CIO alpha-olefins such as butene-1 ( ie 1-butene), hexene-1, octene-1, etc in which the molecules of the copolymers comprise long chains with relatively few side chain branches or cross-linked structures.
  • This molecular structure is to be contrasted with conventional low or medium density polyethylene ' s which are more highly branched than their respective counterparts.
  • LLDPE as used herein, has a density usually in the range of from about 0.91 grams per cubic centimetre to about 0.94 grams per cubic centimetre.
  • ethylene/alpha-olefin copolymers such as the long chain branched homogeneous ethylene/alpha-olefin copolymers available from the Dow Chemical Company, known as AFFINITYTM resins, are also included as another type of ethylene alpha-olefin copolymer useful in the present invention.
  • Bernstein et al US Pat Nos 4,391,862 and 4,352,844 disclose co-extruding first and second polymeric layers, irradiating the co-extruded layers, joining a third layer to the second polymeric layer, and then stretching the multilayer film.
  • Bieler et al US Pat No 4,318,763 teaches that the seals of the bags made of multilayer film may be strengthened by cross-linking the seal area of the bag by irradiation.
  • the barrier layer aforementioned references describe a single barrier layer of PVDC.
  • US Patent 4542075 discloses a multilayer laminate film including two barrier layers of vinylidene chloride copolymer spaced apart by a non barrier layer, by virtue of the collapse of a melt blown layflat tube, which in its layflat configuration is laminated to an irradiatively crosslinked polyethylene.
  • a further disadvantage is the need for tacky coatings or layers to promote self-welding of the interior layflat surface of the layflat tubes.
  • the disclosure indicates no exact measure of the barrier layer thickness and so presumes an industry- standard PVDC copolymer thickness for each barrier layer of 0.5-1.0 mil (approx 12.5 - 25 micron).
  • US Patent 5529833 discloses a multilayer laminated film having one oxygen barrier layer and an oxygen scavenging layer in a conventional construction, or two oxygen barrier layers where the inner oxygen barrier layer acts as a spacer between the product and an obligatory oxygen scavenging layer.
  • the oxygen barrier layers are specified in accordance with the usual parameters for such layers in laminated films, in terms of the thickness of PVDC copolymer used as each barrier layer or layers, of 0.5 mil (12.5 micron approx ) .
  • this invention in one aspect resides broadly in a multilayer barrier packaging film including an irradiated biaxially orientated coextrusion of at least four layers including at least two layers of a thermoplastic polymer or copolymer and at least two relatively thin thermoplastic polymer oxygen barrier layers.
  • the thickness of barrier layer is less than industry-standard.
  • the industry-standard thickness for a PVDC copolymer barrier layer is in the order 0.5-1.0 mil (approx 12.5 - 25 micron).
  • the total thickness of the barrier layers being selected is less than the thickness of a single barrier layer of the barrier layer material required to give a selected rate of oxygen transmission.
  • the layers may be formed up in the laminate with adhesive, tie layers or further polymer layers in between, or may be formed up adjacent in the laminate. Adhesive and tie layer composites include those that are well known in the art.
  • the packaging film includes outer layers of a thermoplastic polymer or copolymer and at least two core thermoplastic polymer oxygen barrier layers. More preferably, the core barrier layers are separated by at least one layer of a thermoplastic polymer or copolymer. Additional polymer layers may be included by coextrusion, coating, lamination, or a combination thereof.
  • the barrier layers are selected from copolymers of vinylidene dichloride (PVDC), certain polyamides, ethylene-vinyl alcohol copolymers (EVOH), polyethylene terephthalate ( PET ) , polyvinyl chloride ( PVC ) , and especially EVOH copolymers, polyamides and copolymers of vinylidene dichloride with minor proportions of vinyl, acrylic, or other unsaturated monomers.
  • PVDC vinylidene dichloride
  • EVOH ethylene-vinyl alcohol copolymers
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • each said layer having a finished thickness of at least 2.5 microns to provide physical integrity.
  • the multilayer film has a first outer layer of a thermoplastic polymer or copolymer, a first core layer of a barrier film including vinylidene chloride-methyl acrylate copolymer, a second core layer of a thermoplastic polymer or copolymer, a third core layer of a barrier film including vinylidene chloride-methyl acrylate copolymer, and a second outer layer of a thermoplastic polymer or copolymer. More specifically, EVA, LLDPE, VLDPE and blends of these materials may be used in the first and second outer layer and in the second core layer.
  • the multilayer film is preferably made by coextrusion of the layers, and then it is biaxially stretched. After biaxial stretching, the multilayer film may be irradiated to a dosage level of between 1 megarad and 10 megarads and heat-sealed in the form of a bag.
  • the bag has improved storage stability characteristics.
  • a biaxially oriented laminate having outer heat shrinkable layers and at least 2 PVDC barrier layers each having a thickness of at least 2.5 ⁇ and having a total thickness of PVDC of less than 12.5 ⁇ , and having an oxygen transmission of less than 25. lcc/sq . m/24hr/atm.
  • a heat-shrinkable multilayer film having a first outer layer of a polymer or copolymer, a first core layer of a barrier film including vinylidene chloride-methyl acrylate copolymer, a second core layer of a thermoplastic polymer or copolymer, a third core layer of a barrier film including vinylidene chloride-methyl acrylate copolymer, and a second outer layer of a polymer or copolymer wherein the multilayer film has been biaxially stretched and then irradiated to a dosage level of between about 1 megarad and about 10 megarads, when employed to make bags for packaging primal and sub-primal meat cuts and processed meats, such a film provides bags having improved physical characteristics, whereby the bags when stored provide better shelf life, are more abuse resistant, have the ability to withstand high sealing temperatures, and greater seal strength than those of the prior art.
  • this invention relates to an irradiated multilayer film suitable for use in the manufacture of bags for packaging primal and sub-primal meat cuts and processed meats.
  • This invention also relates to such film including an irradiated five-layer film wherein the outer layers of the film comprise ethylene-vinyl acetate copolymers, and the first and third core layer comprises copolymers of vinylidene chloride and methyl acrylate and the second core layer comprises a thermoplastic polymer or copolymer, and to the process for manufacturing such film.
  • blends of polymers and copolymers may be substituted into the first and second outer layer and the second core layer.
  • DETAILED DESCRIPTION OF THE INVENTION refers to a monomer which is copolymerized with at least one different monomer in a copolymerisation reaction, the result of which is a copolymer.
  • polymer refers to the product of a polymerization reaction, and is inclusive of homopolymers, copolymers, terpolymers, etc.
  • copolymer refers to polymers formed by the polymerization reaction of at least two different monomers.
  • copolymer includes the copolymerisation reaction product of ethylene and an alpha-olefin, such as 1-hexene.
  • copolymer is also inclusive of, for example, the copolymerisation of a mixture of ethylene, propylene, 1- hexene, and 1-octene.
  • a copolymer identified in terms of a plurality of monomers refers to a copolymer in which the first listed monomer copolymerizes in a higher weight percent than the second listed monomer, and, for copolymers which are terpolymers, the first monomer copolymerizes in a higher weight percent than the second monomer, and the second monomer copolymerizes in a higher weight percent than the third monomer, etc.
  • heteropolymer refers to polymerization reaction products of relatively wide variation in molecular weight and relatively wide variation in composition distribution, ie polymers made, for example, using conventional Ziegler-Natta catalysts. Such polymers typically contain a relatively wide variety of chain lengths and comonomer percentages.
  • ethylene alpha-olefin copolymer and “ethylene/alpha-olefin copolymer” refer to such heterogeneous materials as linear low density polyethylene ( LLDPE ) , and very low and ultra low density polyethylene (VLDPE and ULDPE ) ; and homogeneous polymers such as metallocene catalyzed polymers such as EXACTTM materials supplied by Exxon, and TAFMERTM materials supplied by Mitsui Petrochemical Corporation.
  • LLDPE linear low density polyethylene
  • VLDPE and ULDPE very low and ultra low density polyethylene
  • homogeneous polymers such as metallocene catalyzed polymers such as EXACTTM materials supplied by Exxon, and TAFMERTM materials supplied by Mitsui Petrochemical Corporation.
  • These materials generally include copolymers of ethylene with one or more comonomers selected from C4 to CIO alpha-olefins such as butene-1 ( ie 1-butene), hexene-1, octene-1, etc in which the molecules of the copolymers comprise long chains with relatively few side chain branches or cross-linked structures.
  • This molecular structure is to be contrasted with conventional low or medium density polyethylenes which are more highly branched than their respective counterparts.
  • LLDPE as used herein, has a density usually in the range of from about 0.91 grams per cubic centimetre to about 0.94 grams per cubic centimetre.
  • ethylene/alpha-olefin copolymers such as the long chain branched homogeneous ethylene/alpha-olefin copolymers available from the Dow Chemical Company, known as AFFINITYTM resins, are also included as another type of ethylene alpha- olefin copolymer useful in the present invention.
  • polyolefin refers to any polymerized olefin, which can be linear, branched, cyclic, aliphatic, aromatic, substituted, or unsubstituted.
  • heat-shrinkable multilayer film having: a first outer layer of,
  • T h e blend (b) of said two ethylene-vinyl acetate copolymers has a vinyl acetate content of from about 3 to about 18 weight percent, and preferably from about 10 to about 15 weight percent, based on the weight of said copolymers.
  • the first ethylene-vinyl acetate copolymer can be a single ethylene-vinyl acetate copolymer or a blend of at least two ethylene-vinyl acetate copolymers having melt indices and vinyl acetate contents within the aforementioned ranges;
  • thermoplastic polymer or copolymer which could be a blend of the first and second outer layers
  • first and third core layer including a vinylidene chloride methyl acrylate copolymer containing from about 5 weight percent to about 15 weight percent methyl acrylate, based on the weight of said copolymer.
  • the heat shrinkable multilayer film of this invention can be produced by known techniques.
  • the film may be produced by a four or more layer die with at least two of the inner layers designed for the extrusion of PVDC. Each layer of the die is connected to an extruder.
  • the extruders feeding the PVDC are specifically designed to melt and pump PVDC.
  • the preferred method is by coextruding the multiple layers into a primary tube, followed by biaxially stretching the tube by known techniques to form a heat shrinkable film.
  • the "double bubble" technique disclosed in Pahlke US Pat No 3456044 is suitable for use in producing the film of this invention.
  • a primary tube is prepared, cooled, reheated and the tube is simultaneously stretched in the machine direction (MD) by operating longitudinally spaced nip rolls at different speeds, and in the transverse direction (TD) by inflating air inside the tube.
  • MD machine direction
  • TD transverse direction
  • Suitable stretch ratios are from about 2 to about 6, of which about 3 to 5 is preferred.
  • the heat shrinkable multilayer film of this invention may also be formed into a primary tube by known techniques such as by co-extruding at least the core layer and the first and second outer layer on each side of the core layer to form a primary tube.
  • this process is described in Canadian Patent No. 982923.
  • coating lamination may be used, wherein a first outer tubular layer is extruded and thereafter the core and second outer tubular layers are sequentially coated onto the outer surface of the first tubular layer and the core layer to form the composite primary tube.
  • the first outer and core outer layer may themselves be coextruded, and the second outer layer thereafter coated onto the outside surface of the core layer. Coating lamination procedures are described in Brax et al. US Patent 3741253.
  • the multilayer film may then irradiated to a dosage level of between about 1 megarad and about 10 megarads, such as by passing it through an electron beam irradiation unit.
  • the multilayer film may then be employed to manufacture heat-shrinkable bags useful in packaging primal and sub-primal meat cuts and processed meats .
  • the first outer layer of the multilayer film is an ethylene-vinyl acetate copolymer containing from about 9 to about 15 weight percent of vinyl acetate, based on the weight of the copolymer, said copolymer having a melt index of between about 0.1 and about 1.0 decigram per minute, and it may be selected from the group consisting of
  • the first and third core layers of the multilayer film of this invention comprises a vinylidene chloride-methyl acrylate copolymer containing at least 85 weight percent of vinylidene chloride, based upon the weight of the vinylidene chloride copolymer.
  • the remainder of the vinylidene chloride copolymer is methyl acrylate. More preferably, the vinylidene chloride-methyl acrylate copolymer will contain at least about 85 weight percent, and not more than about 95 weight percent, of polymerized vinylidene chloride because when the vinylidene chloride copolymer contains less than about 85 weight percent vinylidene chloride, the methyl acrylate content would be greater than the maximum amount approved by the Food and Drug Administration for food contact uses, which is 15 percent by weight of the copolymer. If the vinylidene chloride content is more than 95 weight percent, the vinylidene chloride copolymer is generally not extrudable.
  • the vinylidene chloride copolymer may contain but is not limited to less than 5 weight percent plasticizer, the percentage being based on the total weight of the blend of copolymer and all additives including plasticizer, in order to maximize the barrier properties of the thin film.
  • the levels may be higher than 5% for equivalent or better barrier properties than a multilayer film containing only one layer of vinylidene chloride copolymer.
  • plasticizers such as dibutyl sebacate and epoxidized soybean oil can be used.
  • the second outer layer of the multilayer film of this invention comprises an ethylene-vinyl acetate copolymer selected from the group consisting of
  • the multilayer film of this invention will generally have a total thickness of from about 38 microns to about 90 microns, and preferably of from about 44 microns to about 75 microns, because when the thickness of the multilayer film is more than 75 microns, no improvement in performance is gained except for extreme applications. When the thickness of the multilayer film is less than 44 microns, the bag will have diminished puncture resistance.
  • the first outer layer will normally have a thickness of from about 20 microns to about 33 microns
  • the first and third core layers will normally have a thickness of from about 2.5 microns to about 5.0 microns
  • the second core layer will normally have a thickness of from about 9.0 microns to about 33 microns
  • the second outer layer will normally have a thickness of from about 10 microns to about 20 microns.
  • the thickness of the first outer layer which is the inner layer of the bag, should be within the aforementioned range because the sealing and processability properties of the film layer would otherwise be diminished.
  • the thickness of the first and third core layers should be within the above- indicated range because the film would provide inadequate barrier properties if the individual core layer thickness is less than about 2.5 microns.
  • the upper limit of 5.0 microns for the individual core layers is primarily due to economic considerations.
  • the thickness of the second outer layer which is the outer layer of the bag, is selected within the aforementioned range to provide an abuse cover over the barrier layer.
  • the thickness of the second core layer is selected in order to provide a total thickness of the multilayer film in the range of from about 44 microns to about 75 microns.
  • the multilayer film of this invention is irradiated to a dosage level of between about 1 megarad and about 10 megarads, and preferably between about 2 megarads and about 5 megarads, by any suitable method such as by employing an electron beam. It has been found that the irradiation energy applied to the multilayer film herein is important. That is, when the energy level is below the indicated range, sufficient cross-linking is not obtained so as to improve the heat sealing characteristics of the multilayer film or to have any enhanced effect upon the toughness properties of the film.
  • bags suitable for the shrink packaging of primal and sub-primal meat cuts and processed meats are provided from the aforedescribed multilayer film.
  • the bags may be produced from the five-layer film of this invention by heat sealing.
  • the film of this invention is produced in the form of tubular film, bags can be produced therefrom by heat sealing one end of a length of the tubular film or by sealing both ends of the tube; then slitting one edge to form the bag mouth.
  • the film of this invention is made in the form of flat sheets, bags can be formed therefrom by heat sealing three edges of two superimposed sheets of film.
  • the surfaces which are heat sealed to each other to form seams are the said first outer layers of the films of the invention.
  • the inner surface of the tube ie the surface which will be heat sealed to itself, will be the said first outer layer of the film.
  • Shrinkage values were obtained by measuring unrestrained shrink at 90 °C for five seconds.
  • VDC-VC Copolymer To demonstrate the significant reduction in oxygen transmission rate obtained when a three layer film with a single core layer of vinylidene chloride vinyl chloride copolymer containing about 85 weight percent vinylidene chloride and about 15 weight percent vinyl chloride (VDC-VC Copolymer); is compared to a five layer film with first and third core layer of vinylidene chloride vinyl chloride copolymer containing about 85 weight percent vinylidene chloride and about 15 weight percent vinyl chloride (VDC-VC Copolymer), the first and third layers being separated by a second core layer of a polymer or copolymer, with the combined thickness of the first and third layers approximately equal to the thickness of the single core layer of the three layer film the following samples were prepared.
  • Biaxially stretched three-layer films had been prepared by a "double bubble" process similar to that disclosed in US Pat No 3,456,044 by co-extruding the following compositions through a multilayer die, biaxially stretching the co-extruded primary tube, and then irradiating the biaxially stretched tube were used in the tests. These films are shown as A, B, and C on Table 1.
  • the composition of the films tested were three layers having an inner and an outer layer of ethylene-vinyl acetate copolymer containing and a four layer of comprised of vinylidene chloride-methyl acrylate copolymer.
  • biaxially stretched monolayer PVDC films were prepared by the well known double bubble process. These films are labeled as C, D, E, F, G, & H on Table 1. Surprisingly, when these single layer films were combined into multiple layers separated only by glycerin the same benefits of more than one barrier layer were realized as with the multilayer structures A, B, & C. These tests also indicate that this benefit is greater than would be anticipated simply by an increase in gauge alone as is shown in Table 1. TABLE 1
  • Table 1 indicates the oxygen transmission rates for eight different films labelled A, B, C, D, E, F, G, H.
  • Test 1 is the oxygen transmission rate with the base film A.
  • Tests 2 through 6 were with the film separated and re combined as described earlier.
  • Tests 2, 3, 5 & 6 are with two barrier layers and indicate about a 14% to 19% reduction in oxygen transmission rate per micron of PVDC thickness.
  • Test 4 indicates that a single layer of PVDC with the outer layer removed still has the same barrier properties as the base film in test 1.
  • test 5 has the same reduction in oxygen transmission rate as compared to tests 2 & 3 even though the two PVDC layers are separated only by glycerin whereas test 2 & 3 have a total of 80u and 40u of EVA separating the two layers of PVDC respectively. This indicates that the EVA has essentially no resistance to the flow of oxygen.
  • Test 7 & 12 is the oxygen transmission rate with the base film B.
  • Tests 8, 9, 10, 11, 13 & 14 were with the film separated and re combined as described earlier.
  • Tests 9, 10 & 14 are with two barrier layers and indicate about a 16% to 20% reduction in oxygen transmission rate per micron of PVDC thickness.
  • Test 8, 11 & 13 indicates that a single layer of PVDC with the outer layer removed still has about the same barrier properties as the base in film tests 7 & 12.
  • Comparison of test 13 to tests 7 & 12 indicates that the glycerin has no resistance to the flow of oxygen within the experimental accuracy of the test.
  • Tests 15 through 18 were 1, 2, 3 & 4 layers of the same film C separated only by glycerin. The oxygen transmission was reduced when an additional layer of PVDC was added however the decrease was significantly less when the 4th layer was added as compared to the 3rd layer. This suggests that there is some limit beyond which the additional layers will provide minimum benefit.
  • Tests 19, 20 & 21 were 1, 2 & 3 layers of the same film D separated only by glycerin as was done with film C. Again the benefit of multiple layers of PVDC is shown.
  • Tests 22 through 30 were with 4 different films E, F, G & H each with a single layer at a different measured thickness. The purpose of these tests was to demonstrate that the oxygen transmission rate is constant for different thickness of PVDC. The change in rate with respect to an increase in film thickness ranged from a reduction in rate of 5.49% for film E to an increase in rate of 12.45% for film H. Films F & G had a slight reduction in rate. These results support the contention that for a given PVDC formulation the oxygen transmission rate is constant and not a function of the thickness over the range of thicknesses tested.
  • novel film compositions of this invention have been shown to possess physical properties required for use in packaging primal and sub-primal meat cuts and processed meats, while additionally having a significantly reduced oxygen transmission rate which will result in improved shelf life of the product being packaged.
  • various conventional additives such as slip agents, antiblock agents, and pigments may be incorporated in the films of the present invention in accordance with conventional practice.

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  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film d'emballage barrière à couches multiples, à utiliser dans la fabrication de sacs destinés à l'emballage de grosses pièces de viande et de viandes traitées. Le film à couches multiples présente une première couche extérieure en copolymère ou polymère thermoplastique, une première couche centrale constituée d'un film barrière comprenant un copolymère chlorure de vinylidène- acrylate de méthyle, une deuxième couche centrale constituée de copolymère ou polymère thermoplastique, une troisième couche centrale constituée d'un film barrière comprenant un copolymère chlorure de vinylidène-acrylate de méthyle et une deuxième couche extérieure en polymère ou copolymère thermoplastique. Plus spécifiquement, EVA, un polymère basse densité linéaire (lLLDPE) un polymère très basse densité linéaire (VLDPE) et des mélanges de ces matériaux peuvent être utilisés dans la première et la deuxième couche extérieure et dans la deuxième couche centrale. Le film multicouche est de préférence fabriqué par co-extrusion des couches, après quoi il est étiré biaxialement. Après l'étirement biaxial, ledit film multicouches peut être irradié selon un dosage compris entre 1 mégarad et 10 mégarads et thermosoudé de sorte qu'il forme un sac, lequel présente des caractéristiques de stabilité au stockage améliorées.
PCT/AU1998/000366 1997-05-16 1998-05-15 Film d'emballage barriere, a couches multiples WO1998052747A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NZ501636A NZ501636A (en) 1997-05-16 1998-05-15 Multilayer barrier packaging film including a coextrusion of at least four layers
AU76298/98A AU745038B2 (en) 1997-05-16 1998-05-15 Multilayer barrier packaging film
EP98923916A EP0986464A4 (fr) 1997-05-16 1998-05-15 Film d'emballage barriere, a couches multiples
JP54970698A JP2001525743A (ja) 1997-05-16 1998-05-15 多層バリヤー包装フィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPO6840A AUPO684097A0 (en) 1997-05-16 1997-05-16 Multilayer barrier packaging film
AUPO6840 1997-05-16

Publications (1)

Publication Number Publication Date
WO1998052747A1 true WO1998052747A1 (fr) 1998-11-26

Family

ID=3801131

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1998/000366 WO1998052747A1 (fr) 1997-05-16 1998-05-15 Film d'emballage barriere, a couches multiples

Country Status (6)

Country Link
EP (1) EP0986464A4 (fr)
JP (1) JP2001525743A (fr)
AU (1) AUPO684097A0 (fr)
NZ (1) NZ501636A (fr)
WO (1) WO1998052747A1 (fr)
ZA (1) ZA984056B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2828435A1 (fr) * 2001-08-13 2003-02-14 Linpac Plastics Pontivy Sa Film multicouche thermoretractable
EP2992049A4 (fr) * 2013-03-08 2016-11-30 Bilcare Ltd Film polymère multicouche
DE102017107060A1 (de) * 2017-04-03 2018-10-04 Rkw Se Steigerung der Reißfestigkeit einer mehrschichtigen Folie
CN112874084A (zh) * 2021-02-03 2021-06-01 洛阳晟鹏新材料科技有限公司 一种用于包装低温肉制品的pvdc高阻隔共挤拉伸膜及其制备方法

Citations (3)

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AU2944077A (en) * 1976-10-08 1979-05-24 W.R. Grace & Co. Polymeric film laminates and use thereof for food packages
US5225288A (en) * 1990-08-10 1993-07-06 E. I. Du Pont De Nemours And Company Solvent blockers and multilayer barrier coatings for thin films
EP0692374A1 (fr) * 1994-07-13 1996-01-17 W.R. Grace & Co.-Conn. Feuille rétractable résistant à l'usure

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US4828891A (en) * 1987-02-02 1989-05-09 Viskase Corporation Four-layer puncture resistant film
CA2062083C (fr) * 1991-04-02 2002-03-26 Drew Ve Speer Compositions, systemes et methodes pour eliminer l'oxygene
AU685406B2 (en) * 1993-01-29 1998-01-22 Bemis Company, Inc. Heat shrinkable film structures with improved sealability and toughness

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AU2944077A (en) * 1976-10-08 1979-05-24 W.R. Grace & Co. Polymeric film laminates and use thereof for food packages
US5225288A (en) * 1990-08-10 1993-07-06 E. I. Du Pont De Nemours And Company Solvent blockers and multilayer barrier coatings for thin films
EP0692374A1 (fr) * 1994-07-13 1996-01-17 W.R. Grace & Co.-Conn. Feuille rétractable résistant à l'usure

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI WORLD PATENT INF 1 January 1900 (1900-01-01), "Laminated gas barrier film - comprises vinylideneÜ chloride resin film contg. UV absorbent formed on transparent plastics film", XP002940738, Database accession no. 1988-122077 *
DATABASE WPI WORLD PATENT INF 1 January 1900 (1900-01-01), "Laminated oriented film having good flexibility - prepd by laminating polyester layers to opposing sides of thermoplastic elastomer layer", XP002940740, Database accession no. 1995-196615 *
DATABASE WPI WORLD PATENT INF 1 January 1900 (1900-01-01), "Mfr. of packaging material useful as container for chemicals - comprises laminating a heat seal resin layer to a gas barrier layer through a hot melt resin layer", XP002940739, Database accession no. 1994-313338 *
DATABASE WPI WORLD PATENT INF 1 January 1900 (1900-01-01), "PropyleneÜ resin laminates for container for food - formed by coating sheets with 1-30 micron layer of polyvinylidene chloride and heat adhering", XP002940737, Database accession no. 1991-078427 *
See also references of EP0986464A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2828435A1 (fr) * 2001-08-13 2003-02-14 Linpac Plastics Pontivy Sa Film multicouche thermoretractable
WO2003016052A1 (fr) * 2001-08-13 2003-02-27 Linpac Plastics Pontivy S.A. Film multicouche thermoretractable
EP2992049A4 (fr) * 2013-03-08 2016-11-30 Bilcare Ltd Film polymère multicouche
DE102017107060A1 (de) * 2017-04-03 2018-10-04 Rkw Se Steigerung der Reißfestigkeit einer mehrschichtigen Folie
CN112874084A (zh) * 2021-02-03 2021-06-01 洛阳晟鹏新材料科技有限公司 一种用于包装低温肉制品的pvdc高阻隔共挤拉伸膜及其制备方法
CN112874084B (zh) * 2021-02-03 2023-08-22 洛阳晟鹏新材料科技有限公司 一种用于包装低温肉制品的pvdc高阻隔共挤拉伸膜及其制备方法

Also Published As

Publication number Publication date
EP0986464A1 (fr) 2000-03-22
ZA984056B (en) 1998-12-28
JP2001525743A (ja) 2001-12-11
EP0986464A4 (fr) 2000-05-31
NZ501636A (en) 2000-05-26
AUPO684097A0 (en) 1997-06-12

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