A multilayer plastic film, useful for packaging a cook-in foodstuff

Abstract: A multilayer, preferably biaxially oriented, film suitable for processing and/or packaging cook-in foods such as ham, roast beef and poultry having an excellent combination of oxygen barrier, heat seal and optical properties comprising at least five essential sequential layers with a first layer of a copolymer of propene and at least one C 2 -C 8 α-olefin having a propene content of at least 60 wt. % and preferably having a melting point <140°C; a second layer of (1)a first copolymer of ethylene and at least one C 4 -C 8 α-olefin (0.900 to 0.915 g/cm 3 ρ), and <1.0 dg/min. M.I.), (2) a second copolymer of ethylene with from 4 to 18%, preferably 4 to 12%, of a vinyl ester or alkyl acrylate, (3) an anhydride-modified third copolymer of ethylene with at least one α-olefin, a vinyl ester or an alkyl acrylate, and (4)optionally a fourth copolymer of ethylene and at least one C 3 -C 8 α-olefin (<0.900 g/cm 3 ρ; and <85°C m.p.); a third EVOH layer; a fourth layer like the second layer; and a fifth layer of a first copolymer of ethylene with at least one C 4 -C 8 α-olefin (0.900 to 0.915 g/cm 3 ρ, and <1.0 dg/min. M.I.), and a second copolymer of ethylene with from 4 to 18%, preferably 4 to 12%, of a vinyl ester or alkyl acrylate, and optionally a third copolymer of ethylene and at least one C 3 -C 8 α-olefin (<0.900 g/cm 3 ρ and <85°C m.p.).

Description: Background of the Invention The invention relates to the art of packaging, e.g. cook-in foods for example ham, beef, and turkey breasts. Acronyms used herein are listed below. A colon (:) indicates components to the left and right of the colon are blended. A slash "/" indicates that components to the left and right of the slash are in different layers and the relative position of layers. Acronyms include: PP -Polypropylene homopolymer PE -Polyethylene (an ethylene homopolymer and/or copolymer of a major portion of ethylene with one or more α-olefins) EVA -Copolymer of ethylene with vinyl acetate PVDC -Polyvinylidene chloride (also copolymers of vinylidene chloride, especially with vinyl chloride) EVOH -Hydrolyzed ethylene vinyl acetate copolymer EAA -Copolymer of ethylene with acrylic acid Trademarks used herein include: Attane® (The Dow Chemical Company, Midland, Michigan, U.S.A.); Escorene® and Exact® (Exxon Chemical Co. of Houston, Texas, U.S.A.); Capron Xtraform™ (Allied Chemical Co. of Morristown, New Jersey, U.S.A.); Plexar® (Quantum Chemical Co., Cincinnati, Ohio, U.S.A.); EVAL™ (EVAL Company of America, Lisle, Illinois, U.S.A.); and TAFMER® (Mitsui Petrochemical Industries, Ltd., Tokyo, Japan). Various films have been commercialized for packaging meats, cheeses and cook-in foodstuffs. Three to six layer films are common. Typical structures include: PP/Adhesive/Nylon, EVA/PVDC/EVA:PE, PE:EVA/PVDC/PE:EVA, Ionomer/EVA/Adhesive/EVOH/Adhesive/EVA, PE:EVA/PE:Adhesive:EVA/EVOH/ PE:Adhesive:EVA/PE:EVA, Nylon/ EVA/Adhesive/EVOH/Adhesive/EVA, C 3 C 2 copolymer/ EVA/ Adhesive/EVOH/ Adhesive/ EVA, and variations thereof where polyethylene copolymers are blended into one or more of the EVA layers. Some packaging films are heat shrinkable at 90°C and others are not. Some are irradiatively crosslinked and/or corona treated or not. Some of the nonshrinking films have an oxygen barrier comprising one or more layers of nylon or EVOH or a blend of EVOH with nylon. Known nonshrinking films include structures of the type EVA:PE/Nylon, EVA:PE/Nylon/EVOH/Nylon/EVA:PE, EVA:PE/ PVDC/ Nylon, EVA:PE/ EVOH/ Nylon, and EVA:PE/Nylon/ EVA. The nonshrinking EVOH containing films generally have a relatively thick EVOH containing layer, generally greater than 0.5 mil (12.7 microns). Thin EVOH barrier layer, multilayer heat shrinkable, oriented films have been taught in U.S. Patent No. 5,382,470 and U.S. application serial number 08/191,886; filed February 3, 1994. Of the foregoing nonshrinking films, those containing EVOH have a typical oxygen permeability of less than 70 cm 3 /m 2 . and often less than 10 cm 3 /m 2 , at 1 atm, 0% relative humidity and 23°C, and are considered high barrier films. The term "barrier" as used herein means a physical barrier to gaseous oxygen molecules. Values should be measured in accordance with ASTM standard D-1434. Also known are films suitable for packaging foodstuffs that are heat shrinkable at 90°C which contain nylon or a blend of EVOH and nylon. Axially stretched, especially biaxially stretched, films which are "heat shrinkable" as that term is used herein have at least 10% unrestrained shrinkage at 90°C (10% in both the machine direction (M.D.) and transverse direction (T.D.) for biaxially stretched films). Known films include: Ionomer/PE/Nylon, Ionomer/ EVA/ Nylon, EAA/ Nylon:EVOH/Ionomer, and PE/ EVOH:Nylon/ PE. Some EVOH containing heat shrinkable films have an oxygen permeability in the high barrier range. EVOH use in multilayer structures frequently leads to poor optical properties, e.g. high haze, and to film structures which are difficult to process and orient. EVOH is very stiff. EVOH layers often delaminate or crack during processing and orientation exhibiting lines, streaks, and undesirable optical properties. Commercial bags are made by transversely sealing a tubular stock of either monolayer or multilayer film. A common seal used in manufacturing bags is a hot bar seal. In making a hot bar seal, adjacent thermoplastic layers are held together by opposing bars of which at least one is heated to cause the adjacent thermoplastic layers to fusion bond by application of heat and pressure across the area to be sealed. For example, bags may be manufactured from a tube stock by making one seal transverse to the tube. This seal may also be referred to as a bottom seal. Once the bottom seal is applied, the tube stock may be transversely cut to form the mouth of the bag. Once a food product such as meat or poultry is inserted into the bag, the package is typically evacuated and the bag'mouth sealed. For example, a bag mouth may be hot bar sealed or it may be sealed by another common heat seal known as an impulse seal. An impulse seal is made by application of heat and pressure using opposing bars similar to the hot bar seal except that at least one of these bars has a covered wire or ribbon through which electric current is passed for a very brief time period (hence the name "impulse") to cause the adjacent film layers to fusion bond. Following the impulse of heat the bars are cooled (e.g. by circulating coolant) while continuing to hold the bag inner surfaces together to achieve adequate sealing strength. One problem of impulse heat sealing is that the seal area often becomes extruded during sealing. This thins the film in the seal area and reduces the strength of the seal or in extreme situations, allows the thinned film to be too easily severed or pulled apart. Those skilled in the art refer to severely extruded seals as "burn through" seals. Thus, a "burn through" seal does not have adequate strength or integrity to seal in or protect the packaged product. One attempt to solve this "burn through" problem is to irradiate the film prior to manufacture of the bag. Irradiation of a multilayer film causes various layers to crosslink. Under controlled conditions, crosslinking by irradiation raises and may also broaden the temperature range for heat sealing, and may enhance puncture resistance. Disadvantageously, if the heat sealing layer of the thermoplastic film is crosslinked too heavily, the highly crosslinked layer is more difficult to melt or fusion bond. This makes it difficult to achieve strong seals, particularly by impulse sealing. A strong continuous seal prevents unwanted egress and ingress of gaseous, liquid or solid materials between the bag exterior and interior. This is particularly necessary when the food-containing package is made of heat shrinkable film and is to be cooked in steam or hot water and/or immersed in hot water to shrink the film against the packaged food since such shrinkage increases the stress on these seals. Thus, there is a continuing need for multilayer films which can be made into bags havin strong seals especially when formed by hot bar sealing o impulse sealing. Such films should provide strong seals abl to withstand a range of temperatures and also be able t produce such seals over a wide sealing temperature rang without burn through. A wide sealing temperature sealing range is desirable because it allows the production of strong integral seals under variations in sealing temperatures, times and pressure. Another heat sealing problem is inadvertent folding Normally, a heat seal is made by applying heat and pressure across two sheets or portions of film e.g. the two opposing sides of a flattened tube. However, if the area to be sealed is inadvertently folded, a section of film having four or six sheets is pressed between the opposing sealer bars. In such situations it is desirable to seal the film without burn through. A wider impulse heat sealing temperature rang indicates a greater latitude in sealing through folds than a narrower range. Summary of the Invention According to the present invention there is provided a multilayer packaging film having at least five layers arranged in sequence and in contact with one another. An article such as a foodstuff, especially ham, may be packaged in the film. The first layer comprises at least 50% by weight of a copolymer of propene and at least one α-olefin selected from the group consisting of ethylene, butene-1, methylpentene-1, hexene-1, octene-1 and mixtures thereof having a propene content of at least 60 wt. %. The second layer is comprised of a blend of (i)at least 10% of a first copolymer of ethylene and at least one C 4 -C 8 α-olefin having a copolymer density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min., and (ii)at least 10% of a second copolymer of ethylene with from 4 to 18% of a vinyl ester or alkyl acrylate, and (iii)at least 10% of an anhydride-modified third copolymer of ethylene with at least one α-olefin, a vinyl ester or an alkyl acrylate, and optionally from 0 to 30% of a fourth copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less than 85°C. The second layer may also optionally contain a propene copolymer as described above for the first layer. The third layer is a core layer which comprises at least 80, preferably at least 90, weight percent EVOH copolymer having an ethylene content of about 38 mole percent or higher. In a preferred embodiment this third layer may have a thickness of about 0.05 to 0.3 mil (1.7-7.62 microns),and preferably 0.14 to 0.2 mil (4.1-5.1 microns). The fourth layer may be the same or different from the second layer but is comprised of a blend of resins as described above for the second layer. The fifth layer comprises a blend of (i)at least 30% of a first copolymer of ethylene with at least one C 4 -C 8 α-olefin having a copolymer density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min.; (ii) at least 10% of a second copolymer of ethylene with from 4 to 18% of a vinyl ester or alkyl acrylate; and (iii) optionally from 0 to 30% of a third copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less of less than 85°C. Preferably, the inventive film will be heat sealable having at least one layer which is crosslinked, preferably by irradiation. In a highly useful embodiment of the invention, the film will be heat shrinkable at temperature such as 90°C or lower, and may have shrinkage values in one or both of the MD and TD directions of at least about 20%, and advantageously e.g. for packaging cook-in foods such as ham or poultry breasts may be at least 30%. The invention also provides a process for making a biaxially stretched, heat shrinkable, heat sealable, delamination resistant multilayer oxygen barrier film, as set out in claim 22. Films of the invention are useful to process and/or package articles, especially foodstuffs such as ham, beef, poultry, or processed meat which may be cooked in the film. It is an advantage of the invention that it can provide a multilayer film having one or more of the desirable properties of low oxygen permeability, low permeability to water vapor, and controllable meat adhesion. It is another advantage of the invention that it can provide a multilayer film containing EVOH which is delamination resistant has high shrinkage values at 90°C or less. It is another advantage of the invention that it can provide a film capable of forming high strength fusion bonds sufficient to withstand the cook-in process with intact seals and film layers. It is an advantage of the invention that it can provide irradiatively crosslinked, multilayer film having an EVOH core layer having a broad impulse heat sealing voltage range. Another advantage of the invention is that it can provide a film with propene containing, meat adhering and heat sealing barrier layers. Another advantage of the invention is that it can provide a film with good optical properties. The above and other benefits and advantages of the invention will be apparent from the disclosure below which is exemplary and nonlimiting. It is not necessary that each and every advantage listed above be found in all embodiments of the invention. It is sufficient that the invention may be usefully employed. Detailed Description of the Invention The present invention may be used for holding a foodstuff during cooking and/or for packaging for sale after a pasteurization or cooking period. The present invention is particularly well adapted to processing and packaging pasteurizable foods, and has particular utility in packaging cook-in hams. "Cook-in" is the term used to indicate a film or bag in which a foodstuff is pasteurized or cooked. Some of the benefits of the inventive multilayer film include: relatively low permeability to oxygen and water vapor; high delamination resistance and an unexpectedly good combination of delamination resistance especially at elevated temperatures simulating cook-in conditions and orientability resulting in good low temperature heat shrinkability; resistance to degradation by food acids, salts and fat; high shrinkage values at low temperatures (90°C or lower); residual shrink force which forms and maintains a compact product; controllable meat adhesion; good to excellent heat sealability especially over a broad voltage range on commercial sealers; low levels of extractables with compliance with governmental regulations for food contact; low haze; high gloss; does not impart off tastes or odors to packaged food; good tensile strength; a surface which is printable; high heat seal strength and a long lasting seal especially at cook-in temperatures; and good machinability. A preferred embodiment of the invention has low O 2 and low water vapor permeabilities in combination with high meat adhesion which prevents undesirable cook-out of liquid during processing, good heat sealability and high shrinkage values at low temperature (90°C or less). In an especially preferred embodiment, the inventive film has at least 20% (more preferably about 30% or higher) shrinkage values in at least one direction at 90°C or less, and preferably at least 25% in both directions. The inventive films may be used as packaging for food and non-food articles. The inventive article must have five essential layers termed the first layer, the second layer, the third layer, the fourth layer, and the fifth layer. The first layer and fifth layer are disposed on opposing sides of the third layer and are preferably attached thereto by the second and fourth adhesive layers, respectively. In tube or bag form these layers comprise the wall. This wall in cross-section has the first layer comprising an outer layer disposed closest to the tube's interior surface with the fifth layer being an opposing outer layer typically disposed closest the exterior surface. By "flatwidth" is meant the transverse width of a flattened tubular film. The flatwidth is also equal to ½ of the circumference of the tubular film. The invention in all of its preferred embodiments comprises or utilizes a multilayer thermoplastic polymeric flexible film of 10 mils (254 microns) or less. The film has a propene-based copolymer first layer for food contact, and which provides heat sealability, an EVOH gas barrier third layer and an outer abuse resistant fifth layer. The second and fourth adhesive layers utilize a combination of high molecular weight, low molecular weight, highly branched and substantially linear polymers to produce a surprisingly orientable film having high delamination resistance even under cook-in conditions. Such films will preferably have a thickness of about 2-3 mils (50.8-76.2 microns), although suitable films for packaging foodstuffs as thick as 4 mils (101.6 microns) or as thin as 1 mil (25.4 microns) may be made. Typically, films will be between about 1.5-3 mil (38.1-76.2 microns). Suitable films of the present invention may have low haze and high gloss e.g. less than 20% haze and a gloss greater than 50 Hunter Units(H.U.) at 45°. Advantageously, some preferred embodiments of the present invention may have haze values of less than 10-12% and preferably less than 6%, and very high gloss values e.g. greater than 65 Hunter Units and preferably greater than 75 H.U.. Tubular films having more than five layers may be constructed with additional intermediate or surface layers. The first layer is predominantly comprised of propylene copolymers having a propylene(propene) content of 60 wt.% or more. The second layer of this film is generally an unusually thick adhesive layer. In addition to providing delamination resistance between the adjacent EVOH layer and the opposing layer, the second layer also eases orientation and facilitates formation of a biaxially stretched film having high shrinkage values (30% or higher) particularly at low temperatures (90°C or lower) in combination with optical properties which are superior to many prior art films. In a preferred embodiment, the EVOH core layer (third layer) directly adheres to the second and fourth layers which function as adhesive layers and in turn are optionally directly adhered respectively to either (or preferably both) the interior(first) and exterior(fifth) layers. The core layer may optionally have processing aids or plasticizers. Nylon may optionally be incorporated in amounts up to 20 wt. %. Typical layer thicknesses for the essential layers of the inventive heat shrinkable film may be about 5-40% first (typically interior surface) layer, 25-70% second (adhesive) layer, 3-13% third (core) layer, 1-35% fourth (adhesive) layer and 10-50% fifth (exterior) layer, although films with differing layer ratio thicknesses are possible. In the present invention, the thickness of the first layer need not be great, but for an advantageous combination of ease of processing and seal performance this layer will preferably be from 0.1 - 1.2 mils thick. It is important that this heat sealable layer be continuous, e.g. over the interior surface of the tube, and that it be extruded at a sufficient thickness to allow heat sealing (if desired). Preferably, the first layer is an outer heat sealing layer which allows the film to be formed into bags. By the term "heat sealing layer" is meant a layer which is heat sealable to itself, (i.e., capable of fusion bonding as set out hereinabove) to prevent gas or liquid leakage therethrough when exposed to above or below ambient temperatures during processing of food within the tube. For use in cook-in applications the heat seals should withstand elevated temperatures up to about 160-180°F(71-82°C) or higher for extended periods of time e.g. up to 4 to 12 hours in heated humidified air, steam or submersion in heated water. Also, the bond interface of the heat seal must have the physical strength to withstand the tension resulting from stretching or shrinking of the film about a food body sealed within the tube while subject to the pasteurization or cook-in temperatures and conditions. Unless otherwise indicated in the present application, percentages of materials used in individual layers are based upon the weight of the indicated layer. The percentage of comonomer content of a particular polymer is based upon the weight of the indicated polymer. Suitable propene copolymer resins for use in the first layer have a propene content of at least 60 weight percent, optionally at least 80 wt.%. Optionally and preferably these copolymers will have a content of at least 90 wt.% propene. Copolymerized with propene will be at least one α-olefin selected from the group consisting of ethylene, butene-1, hexene-1, methylpentene-1, octene-1 and mixtures thereof in an amount up to 40 wt.%. Preferred are bipolymers of propene and ethene (C 3 C 2 copolymers) as well as C 3 C 4 bipolymers and C 3 C 2 C 4 terpolymers. Most preferred are C 3 C 2 copolymers especially bipolymers. A preferred C 3 C 2 copolymer may have a propene content of at least 90% and optionally at least 95% wt.%. Preferred propene copolymers have a melting point between about 126°C to 145°C, more preferably between about 129°C to 136°C. Preferred are random copolymers of propylene. A preferred copolymer is commercially available from Solvay & Cie as a bioriented film grade resin under the trademark Eltex P KS 409. This resin is reportedly a random copolymer of propylene and ethylene having a melting point of less than 136°C, a density (p) of about 0.895 g/cm 3 , a Vicat softening point of about 120°C (ASTM 1525 (1 Kg)) and a melt index at 230°C and 2.16 Kg of about 5 dg/min. The first layer of the inventive film comprises a propene copolymer and has controllable meat adhesion. The meat adhering attribute of the film may be controlled by the absence, presence, and/or extent of surface energy treatment e.g., by corona discharge. Films of the present invention whose first surface layer is not corona treated will have a typical surface energy of at least 29 dynes per cm and typically less than 33. Corona treatment of the first layer can raise the surface energy to levels of at least 33 dynes/cm, preferably at least 34 dynes/cm. Most preferably, levels of from about 35 to 38 dynes/cm will be usefully employed to produce films of the invention having high meat adhesion. Films that have high meat adhesion lessen cook-out of meat juices which, if not prevented, may lead to loss of product weight. Also, cook-out can produce an undesirable package appearance for applications where the processing/ packaging film is intended to be left on the product for post-processing sale and use. However, inventive films with low meat adhesion find utility in cook and strip applications where the film is typically removed from the encased foodstuff directly after cooking or pasteurization. The product after removal of the film is further processed or repackaged. Low meat adhesion films of the invention typically have a surface energy of less than 33 dynes/cm.. The core layer functions as a controlled gas barrier, and provides the necessary O 2 barrier for preservation of the article to be packaged. It should also provide good optical properties when stretch oriented, including low haze. It is desirable that the thickness of the core layer be less than about 0.45 mil (10.16 microns) and greater than about 0.05 mil (1.27 microns) to provide the desired combination of the performance properties sought. These include, for example, oxygen permeability, shrinkage values especially at low temperatures, ease of orientation, delamination resistance, and optical properties. Suitable thicknesses are less than 15% e.g. from 3 to 13% of the total film thickness. Preferably, the thickness of the core layer will also be less than about 10% of the total thickness of the multilayer film. The core layer which comprises EVOH will control the oxygen permeability of the film. For perishable food packaging, the oxygen (O 2 ) permeability desirably should be minimized. Typical films will have an O 2 permeability of less than about 20 cm 3 /m 2 for a 24 hour period at 1 atmosphere, 0% relative humidity and 23°C, and preferably less than 15 cm 3 /m 2 , more preferably less than 10 cm 3 /m 2 . EVOH suitable for use in the core layer is commercially available in resin form with various percentages of ethylene and there is a direct relationship between ethylene content and melting point. In the practice of this invention, the EVOH component of the core layer preferably has a melting point of about 175°C or lower. This is characteristic of commercially available EVOH materials having an ethylene content of about 38 mole % or higher. With increasing ethylene content the melting point is lowered. A melting point of about 158°C corresponds to an ethylene content of 48 mole %. Preferred EVOH materials will have an ethylene content of 44 mole %. EVOH copolymers having higher ethylene contents may be employed and it is expected that processability and orientation would be facilitated, however gas permeabilities, particularly with respect to oxygen may become undesirably high for certain packaging applications which are sensitive to product degradation in the presence of oxygen. The amount of EVOH in the core layer may be adjusted by blending in nylon to vary orientation parameters or the gas permeability, e.g. O 2 , of the films of the invention. The thickness of the core layer may also be varied from about 0.05 to about 0.30 mils (1.3-7.62 microns). Also, while it is preferred that the core layer consist essentially of EVOH, the present invention recognizes the possibility that up to 20% by weight nylon may be present. Also, other additives including polymers may be blended into the core layer in minor amounts to purposefully affect core layer properties such as gas permeability or moisture resistance. When blending the EVOH of the oxygen barrier layer with nylon, nylon 6/66 is the preferred polyamide in the blend. Nylon 6/66 is a copolymer of nylon 6 and nylon 66. Nylon 6 is polyepsilon caprolactam. Nylon 66 is the polymer derived from adipic acid and hexamethylene diamine. The properties of various nylon 6/66 copolymers may differ significantly. For example, the melting temperature decreases as the nylon 66 content is increased from 5% to 20 mole %. Other nylons such as type 6,12 are not suitable for use in the polymer blend of the oxygen barrier layer. With other nylons, numerous gels develop in the core layer and in some instances cracks develop. These numerous gels and cracks are undesirable in films for commercial use to package foodstuffs and indicate potential weak spots in the film integrity and permeability properties. A preferred nylon is a nylon 6/66 copolymer having a melting point of about 195°C, which has a reported nylon 6 component content of about 85 mole % and a nylon 66 component content of about 15 mole %(trademark CAPRON XTRAFORM™ 1539F). The core layer must be at least 80 % by weight EVOH and optionally may contain from 0-20 wt. % of nylon. Use of greater amounts of nylon (e.g. greater than 10% and particularly greater than 20%) results in undesirably high oxygen permeability. The second and fourth adhesive layers are disposed on either side of the core layer and provide good interlayer adhesion characteristics to the multilayer structure. Either or both of these layers may also contribute to the shrinkability and/or optical properties of the inventive film. The composition of each of the second and fourth layers comprises at least 10% of a first copolymer of ethylene and at least one C 4 -C 8 α-olefin, said copolymer having a density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min.. This first copolymer is a very low density polyethylene. The expression very low density polyethylene ("VLDPE") sometimes called ultra low density polyethylene ("ULDPE"), as used herein refers to substantially linear polyethylenes having densities below about 0.915 g/cm 3 and, possibly as low as 0.86 g/cm 3 , and having at least one melting point of at least 90°C. This expression does not include ethylene alpha olefin copolymers of densities below about 0.90 g/cm 3 with elastomeric properties and referred to as elastomers. Some elastomers are also referred to by at least one manufacturer as "ethylene alpha olefin plastomers", but other manufacturers have characterized VLDPE as an ethylene α-olefin with plastomeric properties. However, as hereinafter explained, ethylene alpha-olefin elastomers or plastomers may be advantageously used in the practice of this invention as a minor constituent in certain layers of this multilayer film. VLDPE does not include linear low density polyethylenes (LLDPE) which have densities in the range of 0.915 - 0.930 gm/cm 3 , but it is contemplated that LLDPE may optionally be blended into one or more of the layers. VLDPE's as the term is used herein may be made by a variety of processes including solution or fluidized bed processes using a variety of catalysts including traditional Ziegler-Natta, single-site constrained geometry or metallocene catalysts. VLDPE comprises copolymers (including terpolymers) of ethylene with alpha-olefins, usually 1-butene, 1-hexene or 1-octene, and in some instances terpolymers, as for example of ethylene, 1-butene and 1-hexene. A process for making VLDPEs is described in EP 120,503. The composition of each of the second and fourth adhesive layers also comprises at least 10% of a second copolymer of ethylene with from 4 to 18% of a vinyl ester or alkyl acrylate. The preferred second copolymer is an ethylene vinyl acetate copolymer. The expression "ethylene vinyl acetate copolymer" (EVA) as used herein refers to a copolymer formed from ethylene and vinyl acetate monomers wherein the ethylene derived units (monomer units) in the copolymer are present in major amounts (by weight) and the vinyl acetate derived units (monomer units) in the copolymer are present in minor, by weight, amounts. The second and fourth adhesive layers also comprise at least 10% of an anhydride-modified third copolymer of ethylene with at least one α-olefin, a vinyl ester or an alkyl acrylate, and from 0 to 30% of a fourth copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less of less than 85°C. The optional fourth component is often referred to as a "plastomer". The composition of the second adhesive layer may be identical or different from that of the fourth adhesive layer within the parameters of the above defined structure. Also, the optional fourth polymer and other ingredients not required by this invention may also be present in one or both layers, and the relative thicknesses of each layer may vary. Beneficially the second layer will often be thicker than the fourth layer to provide good moisture barrier properties in addition to good shrinkability. The first copolymer of either or both of the second and fourth layers may comprise from 10 to 70% of each respective layer. The second copolymer of either or both of the second and fourth layers may comprise from 10 to 40% of each respective layer. The third copolymer of either or both of the second and fourth layers may comprise from 10 to 60% of each respective layer. The fourth copolymer of either or both of the second and fourth layers may comprise at least 10% of each respective layer. The fifth layer provides mechanical strength, shrinkability, abrasion resistance and resists burn through during heat sealing. This fifth layer is typically sufficiently thick to provide support, heat shrinkability, and impart strength to the packaging film wall in order to withstand the shrinking operation, handling pressures, abrasion, and packaging with a foodstuff. As an outer surface layer of the film, the fifth layer provides a desirable glossy appearance. It also may provide a water vapor barrier which resists moisture permeation. High moisture barrier properties are desirable to avoid weight loss and undesirable drying of the enclosed food product. The fifth layer comprises at least 30%, preferably at least 40% of a first copolymer of ethylene with a minor proportion of one or more C 4 -C 8 alpha-olefins. This first copolymer has a density of from 0.900 g/cm 3 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min. and is often termed a VLDPE. The fifth layer further comprises at least 10 wt.% of a second copolymer of ethylene with from 4 to 18% (based on the weight of the second copolymer) of a vinyl ester or alkyl acrylate. Preferably, this second copolymer comprises EVA. Optionally, included in this fifth layer is from 0 to 30% of a third copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less than 85°C. This third copolymer is often termed a "plastomer" and may also have a average molecular weight distribution ( M w / M n )less than 3, e.g. about 2. Processing aids such as slip agents, anti-block agents and the like may also be incorporated into the fifth layer as well as into other layers. Such processing aids are typically used in amounts less than 10% and preferably less than 5% of the layer weight. A preferred processing aid for use in the outer layer of the film is a fluoroelastomer. The above ingredients are admixed together and extruded to provide a uniformly blended layer having good strength, processability, high shrinkage characteristics and good optical properties including high gloss. Addition of the third copolymer, in particular, contributions to good optical and shrink properties. Advantageously, the fifth layer may consist essentially of the first and second copolymers with or without the third copolymer and with or without a minor amount (<10%) of processing aid. The multilayer film of the invention may be made by conventional processes including e.g. slot cast or blown film processes, but preferably will be made by an orientation process, especially under conditions to produce a film which is heat shrinkable at 90°C or less. A packaged foodstuff having a heat shrinkable film enclosure according to the invention will advantageously cling to the foodstuff even after opening. Non-shrink bags have a tendency to fall away or separate from the sides of the enclosed product once the vacuum is broken. Once the film separates from the enclosed article surface, oxygen comes into contact with the article surface and product defects on susceptible products, such as ham, may occur. Some prior art films and bags are nonshrink bags which suffer from this defect thereby causing spoilage and waste when used to package perishable foodstuffs. The five layer film of this invention may be manufactured by coextrusion of all layers simultaneously for example as described in U.S. Patent No. 4,448,792 (Schirmer) or by a coating lamination procedure such as that described in U.S. Patent No. 3,741,253 (Brax et al.) to form a relatively thick primary multilayer extrudate either as a flat sheet or, preferably, as a tube. This sheet or tube is oriented by stretching at orientation temperatures which are generally below the melting points for the predominant resin comprising each layer oriented. Stretch orientation may be accomplished by various known methods e.g. tentering, or trapped bubble or double bubble, as described for example in U.S. Patent No. 3,456,044 (Pahlke). Stretch orientation can be in one direction but preferred films are biaxially stretched in both the transverse direction (TD) and machine direction (MD). Stretch oriented films are "heat shrinkable' in that at least 10% unrestrained shrinkage at 90°C in at least one direction and preferably at least 10% shrink in both the machine direction (M.D.) and transverse direction (T.D.) for biaxially stretched films. Heat shrinkable multilayer films of the present invention preferably will have at least 20% shrink at 90°C in at least one direction (preferably both directions). At least 30% shrink at 90°C in at least one direction is most preferred. Beneficially the film may have at least 10% shrink at 74°C in both machine and transverse directions and preferably at least 15% (more preferably at least about 20%)in at least one direction at 74 °C. The general annealing process by which biaxially stretched heat shrinkable films are heated under controlled tension to reduce or eliminate shrinkage values is well known in the art. If desired, films of the present invention may be annealed to produce lower shrinkage values as desired for the particular temperature. The stretch ratio during orientation should be sufficient to provide a film with a total thickness of between about 1.0 and 4.0 mils. The MD stretch ratio is typically 2½-6 and the TD stretch ratio is also typically 2½-6. An overall stretch ratio (MD stretch multiplied by TD stretch) of about 6¼x-36x is suitable. The preferred method for forming the multilayer film is coextrusion of a primary tube which is then biaxially oriented in a manner similar to that broadly described in the aforementioned U.S. Patent No. 3,456,044. As disclosed in this patent, the primary tube leaving the extrusion die is inflated by admission of a volume of air, cooled, collapsed, and then preferably oriented by reinflating to form a secondary tube termed a "bubble" with reheating to the film's orientation (draw) temperature range. Machine direction (MD) orientation is produced by pulling or drawing the film tube e.g. by utilizing a pair of rollers traveling at different speeds and transverse direction (TD) orientation is obtained by radial bubble expansion. The oriented film is set by rapid cooling. In the following examples, all five layers were coextruded as a primary tube which was cooled upon exiting the die. This primary tube was then reheated to the draw temperature (also called the orientation temperature) for biaxial orientation. In some preferred embodiments of the invention it is preferred to crosslink the entire film to broaden the heat sealing range. This is preferably done by irradiation with an electron beam at dosage levels of at least about 2 megarads (MR) and preferably in the range of 3 to 8 MR, although higher dosages may be employed. Irradiation may be done on the primary tube or after biaxial orientation. The latter, called post-irradiation, is preferred and described in U.S. Patent No. 4,737,391 (Lustig et al.). Alternatively, crosslinking may be achieved by addition of a chemical crosslinking agent. The following examples illustrate the present invention. Experimental results and reported properties are based on the following test methods or substantially similar test methods unless noted otherwise. Tensile Strength: ASTM D-882, Method A % Elongation: ASTM D-882. Method A Haze: ASTM D-1003-52 Gloss: ASTM D-2457, 45° angle 1% Secant Modulus: ASTM D-882, Method A Oxygen Gas Transmission Rate (O 2 GTR): ASTM D-3985-81 Water Vapor Transmission Rate (WVTR): ASTM F 1249-90 Elmendorf Tear Strength: ASTM D-1992 Gauge: ASTM D-2103 Melt Index: ASTM D-1238, Condition E (190°C)(except for propene-based (>50% C 3 content)polymers tested at Condition L(230°C)) Melting point: ASTM D-3418, DSC (5°C/min heating rate) Surface Energy (Wetting Tension):ASTM D-2578-84 Shrinkage Values: Shrinkage values are defined to be values obtained by measuring unrestrained shrink of a 10 cm square sample completely immersed in water at 90°C (or the indicated temperature if different) for five seconds. Four test specimens are cut into squares of 10 cm length in the machine direction by 10 cm. length in the transverse direction. After immersion, the distance between the ends of the shrunken specimen (both MD and TD) is measured and recorded as percent shrinkage. The values of four specimens are averaged for the M.D. and TD shrinkage values. As used herein the term "heat shrinkable film at 90°C" means a film having an unrestrained shrinkage value of at least 10% in at least one direction. Shrink Force: The shrink force of a film is that force or stress required to prevent shrinkage of the film. Four film samples were cut 1" (2.54 cm) wide by 7" (17.8 cm) long in the machine direction and 1" (2.54 cm) wide by 7" (17.8 cm) long in the traverse direction. The average thickness was determined and recorded. Each film sample was secured between two clamps spaced 10 cm apart. One clamp is in a fixed position and the other is connected to a strain gauge transducer. The secured film sample and clamps were then immersed in a silicone oil bath maintained at a constant, elevated temperature for a period of five seconds. During this time, the force in grams at the elevated temperature was recorded then the sample was removed from the bath and allowed to cool to room temperature whereupon the force in grams at room temperature was also recorded. The shrink force for the sample was then determined by the formula: Shrink Force (g/mil) = F/T wherein F is the force in grams and T is the average thickness of the film samples in mils. Impulse Seal Range: The impulse sealing range test determines acceptable voltage ranges for impulse sealing plastic films. A Sentinel Model 12-12AS laboratory sealer manufactured by Packaging Industries Group, Inc., Hyannis Massachusetts, U.S.A. was used. This impulse sealer is equipped with a replacement sealing ribbon for a Multivac AG100 brand packaging machine (available from Koch Supplies of Kansas City, Missouri). Two 4 inch wide (T.D.) samples are cut. The impulse sealer controls except for impulse voltage are set at the following conditions: 0.5 seconds impulse time (upper ribbon only) 2.2 seconds cooling time 50 psi (345 kPa) jaw pressure 0.3 gallon per minute (1 liter per minute) of cooling (about 75°F (22°C)) water flow One sample is folded in half. This folding simulates folding which may inadvertently occur during conventional bag sealing operations. The folded sample of tubular film which now has four sheets or portions of film (hereinafter referred to as "sheet portions") is placed into the sealer and by trial and error the minimum voltage to seal the bottom two sheet portions to each other was determined. The maximum voltage is determined by placing two sheet portions in the sealer and activating the seal bar. The film sample is manually pulled with about 0.5 lbs. of force and the voltage which does not cause burn through or significant distortion of the seal is determined. Seal Strength Test: Five samples of film are cut 1 inch (2.54 cm) wide and at least 5 inches (77 cm) long with a 1 inch (2.54 cm) wide seal portion centrally and transversely disposed. Opposing end portions of a film sample are secured in opposing clamps in a temperature controlled chamber of an Instron 4501 Universal Testing Instrument. The film is snug fit between the clamps without stretching prior to beginning the test. The test door is closed and the chamber is heated to the test temperature at which time the instrument is activated to pull the film via the clamps traverse to the seal at a uniform rate of 5 inches (127 cm) per minute until failure of the film (breakage of film or seal, or delamination and loss of film integrity). The lbs. at break are measured and recorded. The test is repeated for five samples and the average reported. Unless otherwise indicated, the impulse seals tested for seal strength were made using the equipment described in the impulse seal range test description above with controls similarly set but having a cooling time of about 8 seconds. The hot bar seals of various tested films were made similar to one another using settings of 500°F (260°C) and 0.5 seconds dwell time. Seal Creep: The Seal Creep to Failure Test is designed to be an accelerated cook-in simulation to determine resistance to seal failure and/or loss of film integrity of a processing film over time. Five samples of ½ inch (12.7mm) wide film is cut from sealed films perpendicular to the seal so that each film sample contains a ½ inch wide seal with 5 inches of film on either side of the seal. Each sample is 10 inches (25.4 cm) long with a seal in the middle. The opposing portions of a film sample containing a centrally disposed seal are securely attached to respective flat plate clamps which extend over the % inch width of the film end. The top film clamp is attached to a fixture while the opposing bottom clamp has an attached weight (for a total weight of about 1 lb. (454 g). The weighted clamp and lower film portion including the seal area are submersed into a circulating bath of temperature controlled water set at 165°F (74°C). The film seal area is positioned about 2-3 inches below the surface of the water and the film strip with attached weight is perpendicular to the surface of the water. Upon submersion, the film and weight are observed and the time noted at which the weight drops signifying film seal failure and/or loss of film integrity. The film and weight are observed continuously for the first 15 minutes and then checked at least every 15 minutes thereafter up to a total test period of 180 minutes. The average for five test samples is reported. Minimum and maximum values measured for the set may also be reported. The following examples illustrate the invention. In all the following examples, unless otherwise indicated, the films were produced generally utilizing the apparatus and method described in U.S. Pat. No. 3,456,044 (Pahlke) which describes a coextrusion type of double bubble method and in further accordance with the detailed description above. All percentages are by weight unless indicated otherwise. Examples 1-6 In Examples 1-3, three biaxially stretched, heat shrinkable, five layered films of the present invention were made. The layers were coextruded and biaxially stretched according to a tubular orientation process. For Examples 1-3, one extruder was used for each layer. The resins were coextruded from an annular die to produce a multilayer primary tube having a first/second/third/fourth/fifth layer thickness ratio of about 16:43:11:9:21. The extruded primary tube was cooled by spraying with cold tap water. The cooled primary tube was flattened to neck down the primary tube to a flattened tube of about 4⅛ inches (10.5cm) flatwidth. The cooled flattened primary tube was reheated, biaxially stretched, and cooled. The cooled biaxially stretched and oriented film was flattened and was wound on a reel. The machine direction (M.D.) draw or orientation ratio was about 3.7:1 to 3.8:1 and the transverse direction (T.D.) bubble or orientation ratio was about 2.8:1 to 2.9:1 for all the films. The draw point or orientation temperature was below the predominant melting point for each layer oriented and above that layer's glass transition point. Draw point temperature, bubble heating and cooling rates and orientation ratios are generally adjusted to maximize bubble stability and throughput for the desired amount of stretching or orientation. The resultant films of Examples 1-3 having an average gauge of 2.5 to 2.7 (See Table 2) were biaxially oriented and had an excellent appearance. Examples 4 and 5 were made by irradiating at a level of 4 Mrad by electron beam after orientation and according to methods well known in the art to cause crosslinking, especially of the polymeric second and fourth adhesive layers and the outer (fifth) polymeric layer. These examples (4 and 5) were also corona treated to make the first layer have adherability to proteinaceous foodstuffs such as meat. This property termed "meat adhesion" is important for applications where it is desirable to retain juices within the meat during cooking or pasteurization while in the bag. This is called preventing "cook-out" in which pockets of fat and juices can form causing an undesirable appearance, loss of juices and loss of weight. In other applications (often termed "cook and strip")it is desirable to be able to easily remove the bag from a product following cooking or pasteurization; and in these applications the film is not corona treated and the inner layer advantageously does not adhere to the enclosed foodstuff e.g. meat. In these applications a worker may easily remove the bag after processing for further processing, repackaging for retail sale or for use. For all of the Examples 1-3, the first layer (which was the interior surface of the tubular film) comprised a random copolymer of propene and ethene having a DSC melting point of 133°C, a reported density of 0.896 g/cm 2 , a melt index of 5 g/10 min., and which is commercially available under the trademark Eltex P KS 409 from Solvay & Cie of Brussels, Belgium. In examples 1, 2,and 3, the first layer comprised, respectively, 100%, 90%, and 80% by weight of the propene-ethene random copolymer, and 0%, 10%, and 20% by weight of an LLDPE-based adhesive. The LLDPE-based adhesive was an extrudable rubber-modified, anhydride-modified linear low density polyethylene based tie layer resin (Plexar® PX380) having the following reported properties: 0.912 g/cm 3 ρ; 1.5 dg/min. M.I., 98°C Vsp, shout 125°C m.p.. The fifth layer of Examples 1-3 (which was the exterior surface of the tube) contained an ethylene-α-olefin copolymer of very low density polyethylene sold under the trademark Attane XU 61509.32 which is a copolymer of ethylene and octene-1 reportedly having a melt index of about 0.5 dg/min and a density of about 0.912 g/cm 3 , with a Vicat softening point of 95°C and a melting point of about 122°C. Also in the fifth layer was a copolymer of ethylene and vinyl acetate (EVA) as a component of the blend of resins. This EVA (trademark Escorene LD 701.06)has the following reported properties: 10.5% vinyl acetate content; 0.93 g/cm 3 density; 0.19 dg/min. melt index; and a melting point of about 97°C. In Examples 1, 2 and 3, the fifth (outer) layer compositions were identical and comprised 70.6% of the ethylene-α-olefin copolymer which was blended with 25% of the EVA copolymer and 4.4% by weight of a slip processing aid sold under the trademark Ampacet 100031 by Ampacet Corp. of Tarrytown, New York, U.S.A. For Examples 1-3, the second and fourth (intermediate) layers were each identical blends comprising 17.5% of the same EVA copolymer used in the fifth layer with 42.5% of the same very low density polyethylene used in the fifth layer, and 40% of the same extrudable rubber-modified, anhydride-modified linear low density polyethylene based tie layer adhesive resin (Plexar® PX380) used in the first layer. The second and fourth layers of each of Examples 1-3 were identical to one another except that the fourth layers of examples 1-3 were all thinner than the corresponding second layers. For Examples 1-3, each core layer comprised a 90:10 percent by weight blend of a saponified ethylene-vinyl acetate copolymer (EVOH) with a nylon. A premix was formed by blending 90% EVOH with 10% nylon. This premixed blend was then added to an extruder hopper for extrusion as the core layer. The EVOH was a commercially available copolymer (EVAL E105A) and had the following reported properties: an ethylene content of 44 percent by weight, a melt index of 5.5 dg/min, a density of 1.14 and a melting point of 165°C. The nylon was a commercially available nylon 6/66 copolymer (CAPRON XTRAFORM 1539F) and had a reported nylon 6 content of 85 mole % and nylon 66 content of 15 mole % with a DSC melting point of about 195°C, and a density of 1.13 g/cm 3 . Comparative Example 6 is not of the invention, but is a prior art example of a commercial film used for cook-in packaging of e.g. hams. The comparative film of Example 6 is believed to be a six layer film of the structure C 3 -α-olefin copolymer/EVA/Adhesive/EVOH (44 mole% ethylene)/Adhesive/EVA. All of the examples including the comparative example are heat shrinkable at 90°C. Example 6 is believed to have a composition and layer thicknesses of about 0.5 mil for the 1st (C 3 copolymer)layer; 0.6 mil for the combined 2nd (EVA) layer and 3rd (adhesive) layer; 0.2 mil for the 4th (EVOH)layer; and combined 1.2 mils for the 5th (adhesive) and 6th (EVA) layer. Layer formulations of Example 1-5 are reported in Table 1. Physical properties of the films of Examples 1-6 were measured and are reported in Tables 2-4. The results in Table 2 demonstrate that five layer films according to the present invention have good physical properties. The elongation at break, tensile strength, unrestrained shrink, and shrink force properties of Examples 1-5 of the invention are comparable to commercially available six layer films for packaging cook-in foods as exemplified by comparative Example 6. Although comparative Example 6 has slightly better unrestrained shrink values than the films of the Examples 1-5, all of the inventive films have adequate and excellent unrestrained shrink values for many utilities including packaging of foodstuffs. The elongation at break and tensile strength values of the Examples 4 and 5 are generally as good or better than those reported for the comparative film of Example 6. For packaging articles, the reported elongation at break values for the example films of the invention have very good extensibility which is adequate to accommodate any stretching encountered under typical packaging and process conditions. The shrinkage values for Examples 1-5 are good for a film containing EVOH. The transverse direction values are all greater than 30% at 90°C and shrinkage at lower temperatures of 74°C are similar to the 74°C shrinkage values for comparative Example 6. The present invention is capable of producing films with even higher shrinkage values in both directions at the test temperatures. Therefore the inventive films may have desirably high shrinkage values which may be greater than 20% in either or both directions at 90°C and beneficially may be greater than 30%. High shrinkage especially at 90°C or lower is an advantage in packaging articles to provide close contact between the film and the enclosed article surface which prevents or lessens damage which may be caused by contact with oxygen or by movement of the article within the package. A further advantage is that good shrinkage values may be obtained at a lower temperature thereby using a shrinking process which has lower energy requirements. The shrink forces of Examples 1-5, hold the film in close contact with the enclosed article not only during possible processing subsequent to packaging e.g. pasteurization, but also at room temperature. Films having a high residual shrink force such as in Example 1-5 of the invention have continued close contact between film and article even after opening to maintain its protective functions. Referring now to Table 3, the inventive films of Examples 4 and 5 demonstrate lower modulus values indicating a softer film yet having superior tear strength to the tested commercially available comparative film sample and similar puncture resistance values. The oxygen barrier properties of the test films are all excellent for applications requiring low permeability (a high barrier) to oxygen. Examples 1 and 4, which have an unblended first layer that consists essentially of a propene copolymer, have superior low haze and high gloss relative to the blended structures of Examples 2, 3 and 5. Comparative Example 6 is also believed to have an unblended first layer, however, the comparative example has a much hazier and less glossy appearance than examples having an unblended first layer. Referring now to Table 4, the film samples of Examples 4 and 5 were corona treated whereas Examples 1-3 were not. The surface energy values obtained for the films of Examples 1 and 3 indicate films suitable for cook and strip applications or for use where meat adhesion is not a desired property. The surface energy value for comparative Example 6 suggests corona treatment. The impulse seal range for the crosslinked Examples 4-5 are all sufficiently broad for use and sealing by commercially available sealing equipment including hot bar or impulse sealers. The seal creep to failure and seal strength data demonstrate strong seals and superior resistance to delamination relative to the comparative example. The first set of seal strength data demonstrate that impulse seals of the inventive films may be made over a range of voltages from 40-49 volts which are unexpectedly superior at elevated temperatures to the prior art film of comparative Example 6. The second set of seal strength data examines hot bar seals made at 500°F (260°C) and 0.5 seconds dwell time relative to the factory seal on the commercially available bag of Example 6. Again the inventive films show unexpectedly high and superior seal strength. Surprisingly, the seal creep at failure test demonstrates the dramatic superiority of the hot bar seals of the films of the present invention to the comparative example factory seal at a typical cook-in temperature of 165°F (74°C). The unexpectedly good seal strength, particularly under simulated cook-in temperatures and conditions, is believed to be due to the particular inventive formulation-structure combination employed in the multilayer film. The films of examples 4 and 5 were formed into bags for processing and packaging cook-in food. These bags along with bags of comparative example 6 were stuffed with ground meat and cooked at 165°F (74°C) in steam heat for eight hours followed by chilling overnight. The films of examples 4 and 5 were as good or better than the comparative example demonstrating good purge control, high delamination resistance, good meat adhesion, and good seal strength. None of the tested films of examples 4 and 5 delaminated during either thermal processing or after film removal from the cook-in product. None of the films of examples 4 and 5 exhibited seal failure over the 8 hour cook period or after chilling overnight. Bags of examples 4 and 5 were also subjected to a more severe cook procedure of stuffing and cooking at a temperature of 180°F (82°C) in steam heat for 8 hours to further test the heat seals and none of these bags showed seal failure. Examples 7-10 A five layer tubular film (Example 7) was made by a biaxial stretching orientation process. This process was similar to Examples 1-3, except as noted below. Example 8 is the film of Example 7 which has been irradiated by electron beam to a level of about 4 Mrad. Example 9 is the irradiated film of example 8 which has also been corona treated. Example 10 is a comparative example (not of the invention) which is further described below. These examples demonstrate the effect of irradiation and corona treatment to, respectively, cross-link and surface treat(incorporate polar groups into) the film. It also demonstrates use of a core layer which consists essentially of EVOH and use of a sealing layer using a higher melting point propene copolymer. In all of the examples below, a core layer of 100 wt.% EVOH (EVAL E105A) was used having an ethylene content of 44 mole %. The films of Examples 7-9 each had an inner heat sealable layer of 100% by weight propylene-ethylene copolymer (trademark FINA 7371 from FINA Oil and Chemical Co., Dallas, Texas, U.S.A.). The copolymer properties were reported as: about 143°C melting point(m.p.) (measured by differential scanning calorimetry (DSC)); 3.5 g/10 minutes for melt index(M.I.) (at 230°C/2.16Kg); a density(ρ) of 0.9 g/cm 3 . For Examples 7-9, the second and fourth (intermediate) layers were each identical blends comprising 17% of the same EVA copolymer with 53% of the same very low density polyethylene used in Example 1, and 30% of an extrudable anhydride-modified linear low density polyethylene based tie layer adhesive resin (Plexar® PX 360) (2 dg/min. M.I.; 0.925 g/cm 3 ρ; and about 125°C m.p.. The fifth layer of Examples 7-9 (which was the exterior surface of the tube) contained 73.1 weight % of the very low density polyethylene ATTANE XU 61509.32. Blended in the fifth layer was 22.5 wt.% of EVA(LD 701.06) and 4.4 wt.% of the Example 1 fluoroelastomer. As in Examples 1-5, the first(inner) and fifth(outer) layers were connected to opposing sides of a third(core) layer (which comprises EVOH) by second and third (intermediate) layers which act in part as adhesive layers. The EVOH core layer controlled the permeability of the film with regard to gases such as oxygen. Examples 7-9 have a five layer structure which, if one refers to the Plexar resin containing layers as Adhesive (Ad) layers, may generally be identified as 100% C 3 C 2 (inner layer) /Ad/100% EVOH /Ad/73.1% EVA:22.5% VLDPE: 4.4% Proc. Aid. This film has 1st to 5th layer thicknesses of 8.3%/63.7%/8.4%/3%/16.6%(the combined measured 4th and 5th layers were 19.6% with the 4th layer believed to be about 3%). For Example 10 the layers and their composition were identical to example 7 except that a higher melt index ethylene α-olefin VLDPE was substituted for the ATTANE (XU61509.32). The higher melt index VLDPE used in the first, second and fourth layers of Example 10 was an ATTANE XU 61520.01. This VLDPE is an ethylene-octene-1 copolymer reported to have a density of 0.912 g/cm 3 a M.I. of 1.0 dg/min. and a melting point about 123°C. Example 10 extruded very poorly and could not be made into a tubular film. The absence in the formulation of at least 10% of the copolymer of ethylene and at least one C 4 -C 8 α-olefin having less than 1.0 dg/min M.I. and a density of 0.900 to 0.915 g/cm 3 produced an unstable primary tube having poor dimensional stability and insufficient melt strength to make a tubular biaxially stretched film and no film was made. Various properties of the films of Examples 7-9 were measured and are reported in Tables 5 and 6 below. SEAL STRENGTH EX. NO. lbs/inch (Kg/cm) at 160°F at 170°F at 180°F at 190°F 7 ND ND ND ND 8 6.80 5.40 4.68 5.25 (1.2) (0.97) (0.84) (0.94) 9 5.16 4.57 4.07 3.52 (0.92) (0.82) (0.73) (0.63) Referring to Tables 5 and 6, strong, oxygen barrier films were made having very low haze and high gloss values. The surface energy values reflect that Example 9 has been corona treated to provide a surface capable of high meat adhesion. The impulse seal range is peculiarly high and off the test scale. This is believed due to a combination of sealing through a relatively thick (i.e. >2.6 mil (66 µ))film and use of a high melting point propene copolymer to form the first (sealing) layer. Good 90°C and 74°C shrinkage values are demonstrated with good shrink force values at elevated and room temperatures. Hot bar seals of Examples 8 and 9 demonstrate unexpectedly strong seals over a wide range of elevated temperatures. Examples 11-16 Five layer tubular films designated here as Examples 11,12, and 14-16 were made by a biaxial stretching orientation process. This process was similar to Examples 1-3, except as noted below. The layer formulations are listed in Table 7. The resins used were the same as Examples 1-3, except that the second, fourth and fifth layers all included a resin designated in Table 7 as "Plastomer". This plastomer was a copolymer of ethylene and at least one C 3 -C 8 α-olefin with <0.900 g/cm 3 ρ; and <85°C m.p.. The plastomer resin used was a predominantly ethylene copolymerized with butene-1 monomer (about 0.885 g/cm 3 ρ; 0.5 dg/min M.I.; and 68°C m.p. (TAFMER A0585X). Examples 11 and 12 were similarly made but to slightly different flatwidths. Both films were irradiated by electron beam to about 4 Mrad; neither film was corona treated. Examples 14-16 were irradiated to 4, 5, and 6 Mrad, respectively. Examples 14-16 were all corona treated. Example 13 is comparative (not of the invention) and is further described below. These examples demonstrate the effect of irradiation and corona treatment to, respectively, cross-link and surface treat(incorporate polar groups) the film. The effects of: the optional plastomer component; a core layer which consists essentially of EVOH; and a sealing layer using a preferred low m.p. propene copolymer on properties is shown. In the examples below, a core layer of 100 wt.% EVOH was used (44 mole % C 2 content). As in Examples 1-5, the first(inner) and fifth(outer) layers were connected to opposing sides of a third(core) layer (which comprises EVOH) by second and fourth (intermediate) adhesive layers. The EVOH layer controlled the gas permeability of the film to oxygen. Examples 11, 12, and 14-16 each has a 100% C 3 C 2 inner layer and a relative layer thickness (1st to 5th layers) of 11.8/43.1/7.3/3/34.8 % (the combined 4th & 5th layers were measured at 37.8% ; the 4th layer is believed to be ∼3%). Comparative example 13 is a prior art film believed to have a 6 layer structure as described for comparative example 6, except not corona treated. Properties of the films of Examples 11-16 are reported in Tables 8, 9, and 10 below. Referring now to Tables 8, 9, and 10, the films of Examples 11-12 and 14-16 have very good physical properties typically as good or better than those measured for comparative Example 13. The comparative film had slightly higher shrinkage values, but the values for all films were good for commercial applications. Surprisingly, relative to comparative commercial film example 13, the inventive films all demonstrate much improved tear strength; a better appearance including lower haze, higher gloss; and better resistance to hot water punctures. All films demonstrate suitable oxygen barrier properties. The surface energy measurements indicate suitable high meat adhesion properties for Examples 14-16, and that comparative Example 13 was not corona treated. Example 13 and non-corona treated Examples 11-12 are suitable for use in cook and strip process applications. Examples 14-16 all had similar flatwidths of about 240 mm. Impulse seal ranges of films 14-16 were determined to be desirably broad and sufficient for commercial heat sealing operations. The maximum voltage for impulse seals using a one second dwell time was measured for Examples 14-16. The results indicate that higher irradiation levels raise the maximum burn-through resistance. For comparison, the one second dwell time, maximum impulse seal voltage was measured for comparative Example 6 and a maximum 39 volts was obtained. The seal strengths of hot bar seals made at 500°F with a 0.5 second dwell time for Examples 11 and 12 are unexpectedly superior to the factory seals of comparative film of Example 13. The seal strengths of the impulse seals of examples 14-16 are surprisingly and unexpectedly superior to those measured for example 6. Examples 17-23 Five layer tubular films designated here as Examples 17-22 were made by a biaxial stretching orientation process similar to Examples 1-3. The layer formulations of the film examples are listed in Table 11. In examples 17-19 the resins used in layers 2-5 were the same as used in Examples 1-3, except that the second, fourth and fifth layers all included a resin designated in Table 11 as "Plastomer". The plastomer resin used was a copolymer of ethylene and at least one C 3 -C 8 α-olefin; <0.900 g/cm 3 ρ; and <85°C m.p.. The particular resin used was a copolymer predominantly of ethylene with a minor proportion of butene-1; about 0.888 g/cm 3 ρ, 0.8 dg/min. M.I.; and 68°C m.p.(Exact 9036). Reportedly, this plastomer has a narrow molecular weight distribution ( M w / M n ) of about 2. Examples 17-19 were similar films except that the first layer composition varied. In Example 17, the first layer (inner surface layer of the tube) was made of 100 wt.% of a propylene terpolymer. This C 3 C 2 C 4 terpolymer was available from Sumitomo Chemical Company, Ltd. of Tokyo, Japan (trademark Excellen WS 709N) and reportedly had minor proportions of ethylene (1.5%) and butene-1 (14.7%); 8 dg/min. (230°C/2.16Kg) M.I.; and about 133-134°C m.p.. Example 18 was similar to example 17 except the first layer substituted a C 3 C 4 bipolymer having a reported melt index of 6.5 dg/min.(at 230°C/2.16 Kg); about 131°C m.p.; and a butene-1 content of 14% by weight. This copolymer was available from Shell Oil Company, Atlanta, Georgia, U.S.A. under the trademark CEFOR SRD4-141. In Example 19, the first layer of Example 18 was modified to comprise a blend of 70 wt.% of the noted C 3 C 4 polymer with 30 wt.% of an anhydride-modified LLDPE adhesive(Plexar PX 360) (2 dg/min M.I.; 0.925 ρ; about 125°C m.p.. Examples 17-19 were each irradiated at 4 Mrad and the first layer surface was corona treated. Examples 20 and 21 are comparative examples (not of the invention) which are further described below. Examples 17-23 demonstrate variation of first and second layer compositions as well as the effect of addition of an optional plastomer component to the film. The effect on certain properties of irradiation and corona treatment to, respectively, cross-link and surface treat(incorporate polar groups) the film is evidenced. Examples 17-19 demonstrate use of a core layer which consists essentially of a blend of EVOH and nylon 6/66 copolymer and use of a sealing layer using a preferred low melting point propene copolymer. In each of examples 17-19 and 22-23, a core layer of EVOH (EVALCA E 105A) was used having a C 2 content of 44 mole %; 5.5 dg/min. M.I.; and about 165°C m.p.. In each example 20-21, a core layer of EVOH (EVALCA E 151B) was used having a C 2 content of 44 mole %; 1.6 dg/min. M.I.; and about 165°C m.p.. Examples 20 and 21 each used C 3 C 2 copolymer in the first layer; VLDPE, EVA and processing aid in the fifth layer; and adhesive in the second and fourth layers as described for Examples 1-3. The second and fourth layers of Examples 20 and 21 used different EVA resins. The second and fourth layers of example 20 used 60% of an EVA copolymer (EVA A) (ESCORENE LD317.09) having a 6.1 wt.% vinyl acetate (VA) content; 0.928 g/cm 3 ρ; 0.3 dg/min M.I.; and 102°C m.p., in combination with 40% adhesive. The second and fourth layers of Example 21 used a blend of 55% of EVA A and 15% of LD701 EVA (EVA B) as in the fifth layer; and 30% of adhesive. As in Examples 1-5, the first(inner) and fifth (outer) layers connect to opposing sides of a third EVOH (core) layer by second and third (intermediate) layers which act in part as adhesive layers. Examples 17-22 each was a 5 layer tubular film an with an inner layer containing propene copolymer. These films were biaxially stretched to a machine direction (M.D.) orientation (draw) ratio of about 3½:1 and to a transverse direction (T.D.) orientation ratio of about 3:1. The relative (1st to 5th) layer thicknesses of the extruded primary and any resultant film of examples 17-19 are believed to be 14.1%/49.7%/9.6%/7.2%/19.4%. For examples 20-23, the thicknesses are believed to be 12.8%/51.3%/6.4%/3%/26.6%. Comparative Examples 20-21 are five layer films (biaxially stretched as for examples 17-19)having the formulations indicated in Table 11. Example 22 is an inventive film similar to Example 14, except not irradiated or corona treated. Comparative Example 23 (not of the invention) is identical to Example 22 except that the first layer was modified by substituting 100 wt.% of polypropylene homopolymer (§)(Escorene® § 4092) for the propene copolymer of Example 22. The § had an about 0.90 g/cm 3 ρ; and a 2.3 dg/min M.I. (condition L). Comparing the examples, the inventive film of Example 22 extruded and processed very well forming a stable orientation bubble resulting in a biaxially stretched film of good appearance. Example 22 had an average gauge of 2.11 mil (53.6 µ); a flatwidth of 15 7/8 inches (40 cm) and an M.D./T.D. shrinkage value at 90°C of 30%/39%. Attempts to process the formulation of Example 23 into a biaxially stretched film failed. The polypropylene homopolymer layer appeared to be very hard. Although a primary tube extruded well, attempts at biaxially stretch orienting film from the primary tube resulted in a bubble break as the first layer composition was changed to polypropylene homopolymer. Subsequent attempts to form a stable bubble from primary tubes of the test formulation failed due to bubble rupture during inflation. This demonstrates the unsuitability and undesirability of § homopolymer as the main or sole constituent of a film layer, especially the first layer. Various properties of the films of Examples 17-22 were measured and are reported in Tables 12-14 below. Referring now to Tables 11-14, Examples 17-19 demonstrate that the films produced have useful properties for packaging articles. The examples demonstrate that the first layer may utilize bipolymers and terpolymers, and the core layer may include a nylon polymer such as nylon 6/66 copolymer. Propene polymers suitable for use have at least 60 wt.% of propene polymerized with various amounts of one or more α-olefin comonomers. Preferably, the melting point of such propene-based polymers is less than 140°C. Addition of adhesive to the first layer of example 19 produced a film with suitable properties but the optical properties and tear strength were not as good as for examples 17 and 18. Comparative examples 20 and 21 demonstrate inferior impulse seal strength compared to examples 4-6 and 14-16 of the invention. This inferior impulse seal strength is believed to be due to the absence in the second and fourth layers of at least 10 wt.% of a C 2 copolymer with at least one C 4 -C 8 α-olefin which has a copolymer density of 0.900 to <0.915 g/cm 3 ; <1.0 dg/min. M.I.; and at least 90°C m.p.. Films, bags and packages of the present invention may also employ combinations of characteristics as described in one or more of the claims including dependent claims which follow this specification and where not mutually exclusive, the characteristics and limitations of each claim may be combined with characteristics or limitations of any of the other claims to further describe the invention. The above examples serve only to illustrate the invention and its advantages, and they should not be interpreted as limiting since further modifications of the disclosed invention will be apparent to those skilled in the art in view of this teaching. All such modifications are deemed to be within the scope of the invention as defined by the following claims.

Claims: A multilayer packaging film having at least five layers arranged in sequence and in contact with one another comprising: a first layer comprising at least 50% by weight of a copolymer of propene and at least one α-olefin selected from the group consisting of ethylene, butene-1, methylpentene-1, hexene-1, octene-1 and mixtures thereof having a propene content of at least 60 wt. %; second and fourth layers each comprising 10% to 70% by weight of a first copolymer of ethylene and at least one C 4 -C 8 α-olefin, said copolymer having a density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min., and 10% to 40% by weight of a second copolymer of ethylene with from 4 to 18% by weight of a vinyl ester or alkyl acrylate, and 10% to 60% by weight of an anhydride-modified third copolymer of ethylene with at least one α-olefin, a vinyl ester or an alkyl acrylate, and from 0 to 30% by weight of a fourth copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point of less than 85°C; a third layer comprising at least 80% by weight EVOH copolymer having an ethylene content of at least 38 mole%; and a fifth layer comprising at least 30% by weight of a first copolymer of ethylene with at least one C 4 -C 8 α-olefin, said first copolymer having a density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min., and at least 10% of a second copolymer of ethylene with from 4 to 18% of a vinyl ester or alkyl acrylate, and from 0 to 30% of a third copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less of less than 85°C. A film according to claim 1, wherein said first layer comprises C 3 C 2 random copolymer having a melting point less than 140°C. A film according to claim 1 or 2, wherein said surface energy of said first layer is from 35 to 38 dynes per cm. A film according to any of claims 1 to 3, wherein said first copolymer of said second, fourth and fifth layers comprises an ethylene-α-olefin copolymer having at least 80% by weight of its polymeric units derived from ethylene. A film according to any of claims 1 to 4, wherein said fourth copolymer of said second and fourth layers comprises at least 10% by weight of each of said layers. A film according to any of claims 1 to 5, wherein said second layer of said multilayer film has a thickness that is 25 to 70% of the total thickness of said multilayer film thickness. A film according to any of claims 1 to 6, wherein said second layer of said film further comprises a copolymer of propene and at least one α-olefin selected from the group consisting of ethylene, butene-1, methylpentene-1, hexene-1, octene-1 and mixtures thereof having a propene content of at least 60 wt. %. A film according to any of claims 1 to 7, wherein said third layer of said multilayer film has from 3 to 13% of the total film thickness. A film according to any of claims 1 to 8, wherein said EVOH copolymer has a melting point of about 175°C or less. A film according to any of claims 1 to 9, wherein said third layer comprises at least 10% by weight nylon 6/66 copolymer. A film according to any of claims 1 to 9, wherein said third layer further comprises nylon 6/66 copolymer having a melting point of about 195°C. A film according to any of claims 1 to 11, wherein said third copolymer of said fifth layer comprises at least 10% by weight of said layer. A film according to any of claims 1 to 12, wherein said EVOH has an ethylene content of at least 44 mole percent. A film according to any of claims 1 to 13, wherein said first copolymer of said fifth layer comprises at least 40 to 75% by weight; and said second copolymer comprises at least 10 to 40% by weight of said layer. A film according to any of claims 1 to 14, wherein said film is heat shrinkable at 90°C. A film according to claim 15, wherein said film has a shrinkage value of at least 20% at 90°C in both machine and transverse directions. A film according to any of claims 1 to 16, wherein at least one of said layers further comprises polypropylene, propylene ethylene copolymer, ionomer, nylon, polyethylene, ethylene vinyl ester, polyolefin, LLDPE, LMDPE, LDPE, HDPE, elastomer, plastomer, or blends of one or more thereof. A film according to any of claims 1 to 17, wherein said film has an oxygen transmission rate of less than 20 cm 3 /m 2 at 24 hours at 1 atmosphere, 0% relative humidity and at about 73°F(∼23°C). A film according to any of claims 1 to 18, wherein said film fifth layer is crosslinked. A film according to any of claims 1 to 19, wherein said film has a haze value of less than 12%. A film according to any of claims 1 to 20, wherein said film has a gloss at 45° which is greater than 65 H.U.. A process for making a biaxially stretched, heat shrinkable, heat sealable, delamination resistant multilayer oxygen barrier film comprising: (a) coextruding in a tubular form, around a volume of air, melt plastified polymeric resins forming a primary tube having at least five, first through fifth, sequential concentric layers in contact with one another including: (i) a first layer comprising at least 50% by weight of a copolymer of propene and at least one α-olefin selected from the group consisting of ethylene, butene-1, methylpentene-1, hexene-1, oxtene-1 and mixtures thereof having a propene content of at least 60 wt. %; (ii) second and fourth layers comprising at least 10% by weight of a first copolymer of ethylene and at least one C 4 -C 8 α-olefin, said copolymer having a density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min., and at least 10% by weight of a second copolymer of ethylene with from 4 to 18% by weight of a vinyl ester or alkyl acrylate, and at least 10% by weight of an anhydride-modified third copolymer of ethylene with at least one α-olefin, a vinyl ester or an alkyl acrylate, and from 0 to 30% by weight of a fourth copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less of less than 85°C; (iii) a third layer comprising at least 80% by weight EVOH copolymer having an ethylene content of at least 38 mole%; and (iv) a fifth layer comprising at least 30% by weight of a first copolymer of ethylene with at least one C 4 -C 8 α-olefin, said first copolymer having a density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min., and at least 10% by weight of a second copolymer of ethylene with from 4 to 18% by weight of a vinyl ester or alkyl acrylate, and from 0 to 30% by weight of a third copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less of less than 85°C; wherein said third layer has ≤ 13% of the total thickness of the primary tube, said second layer has 25-70% of the total thickness of the primary tube, and said fourth layer has 1-35% of the total thickness of the primary tube; (b)cooling and collapsing said primary tube; (c)reheating said primary tube to an orientation (draw) temperature; (d) simultaneously biaxially stretching said primary tube forming an expanded, biaxially stretched, secondary tube having a continuous core layer less than 3.3 µm (0.13 mil) in thickness; and (e) rapidly cooling said stretched film thereby forming a heat shrinkable film. A process according to claim 22, further comprising heat sealing a portion of said first layer to itself or to an outermost layer of said film forming a heat seal, wherein said film has an average seal creep at failure time in excess of 60 minutes at 165°F (74°C). A multilayer packaging film comprising a heat sealing layer of at least 90% propylene-ethylene random copolymer having a melting point less than 140°C; a core layer having a thickness between about 1.3 µm (0.05) to about 3.3 µm (0.13 mils) comprising about 0-20 wt.% of nylon 6/66 copolymer and about 80-100 wt.% of an EVOH copolymer having an ethylene content of at least about 38 mole percent; an outer protective layer of at least 30% by weight of a first copolymer of ethylene with between 5 to 20% of by weight of at least one C 4 -C 8 α-olefin, said first copolymer having a density of from 0.900 to 0.915 g/cm 3 and a melt index of less than 1.0 dg/min., and at least 10% by weight of a second copolymer of ethylene with from 4 to 18% by weight of a vinyl ester or alkyl acrylate, and from 10 to 30% by weight of a third copolymer of ethylene and at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less of less than 85°C ; and first and second adhesive layers; wherein said core layer is between said first and second adhesive layers with (1) said first adhesive layer being adhered to a first surface of said core layer, said first adhesive layer being located between said heat sealing layer and said core layer, and (2) said second adhesive layer being adhered to an opposing second surface of said core layer, said second adhesive layer being located between said outer protective layer and said core layer, and said adhesive layers comprising at least 10% by weight of a first copolymer of ethylene with between 5 to 20% by weight of at least one C 4 -C 8 α-olefin, said first copolymer having a density of from 0.900 to less than 0.915 g/cm 3 and a melt index of less than 1.0 dg/min., and at least 10% by weight of a second copolymer of ethylene with from 4 to 18% by weight of a vinyl ester or alkyl acrylate, and at least 10% by weight of an anhydride-modified third copolymer of ethylene with at least one α-olefin, a vinyl ester or an alkyl acrylate, and from 10 to 30% by weight of a fourth copolymer of ethylene and between 5 to 25% by weight of at least one C 3 -C 8 α-olefin having a density less than 0.900 g/cm 3 and a melting point less of less than 85°C; and wherein at least one of said layers is crosslinked.

Inventors: IDLAS SCOTT ALLAN, IDLAS, SCOTT ALLAN
Applicants: CURWOOD INC, CURWOOD, INC.
Application year: 1997
Main classification: B32B27
IPC codes: B32B27, A23B4, B65D30, B32B37, B65D65