Tough monolayer shrink film for products containing moisture

Abstract: A blend of an ethylene-alpha olefin linear copolymer having a density of about 0.890 to about 0.915, an ethylene polymer selected from the group consisting of linear ethylene-alpha olefin copolymers having density of about 0.915 to about 0.940 and tubular low-density polyethylene, and a copolymer of ethylene with at least one copolymerized vinyl alkanoate, alkyl acrylate, or alkyl methacrylate provides a shrink film particularly useful for packaging e.g fish or poultry.

Description: BACKGROUND OF THE INVENTION This invention relates to polyolefin based shrink films which are particularly suitable for packaging solid foods with high water content. U.S. Patent 4,760,116 discloses a single layer heat shrinkable film consisting essentially of a blend of 99.5-98.5 weight % linear low or medium density polyethylene and 0.5-1.5 weight % of one or more copolymers of ethylene with a monomer selected from vinyl acetate and acrylic acids or esters, irradiated by a dosage of about 1 to 5 megarads. The films have a broad shrink temperature range and a low coefficient of friction when heated. U.S. Patent 4,671,987 discloses stretch wrap composite films of at least two layers. One outside layer is a tackified ethylene vinyl acetate copolymer; another outside layer is very low density polyethylene. A third, inside, layer is linear low density polyethylene. The layer of very low density polyethylene can be a blend with up to about 50 weight % polyethylene homopolymer, ethylene-vinyl acetate copolymer, linear low density polyethylene, and mixtures of these compounds. U.S. Patent 4,640,856 discloses a multilayer, thermoplastic shrink film having a substrate layer of very low density polyethylene and a gas barrier layer of vinylidene chloride copolymer or ethylene-vinyl alcohol, useful for packaging of meat. In certain applications, blends of VLDPE, LLDPE and/or EVA may be used to achieve desired properties. FR-2528054 discloses compositions for making films comprising 2 to 25 wt% of free radical polyethylene of density 0.91 to 0.94 and 75 to 98 wt% of a copolymer of ethylene and a C₄+ alpha olefin of density 0.905 to 0.940, the average proportion of α-olefin units being between 1 and 8 mole %. European patent application 0 236 099, discloses a multilayer film useful in food packaging which may be oriented to provide a shrinkable film with good oxygen barrier properties. Outer layers comprise a polymeric material or blend of polymeric materials, such as a blend of LLDPE (preferably about 70-80%) and VLDPE (preferably about 20-30%) or a blend of LLDPE with LMDPE and EVA. U.S. Patent 4,547,433 and U.S. Patent 4,495,249 disclose a heat shrinkable laminate film comprising a core layer of a gas barrier resin and an outer layer of a blend of an ethylene alpha olefin copolymer, density 0.900 - 0.950, with less than 80% of an ethylene vinyl acetate copolymer, crosslinked by ionizing irradiation. U.S. Patent 4,537,376 discloses a heat shrinkable multilayer film for packaging meat. A core layer comprises a vinylidene chloride-vinyl chloride copolymer. One outer layer comprises an ethylene vinyl acetate copolymer. Another outer layer comprises a blend of ethylene vinyl acetate copolymer (20-80%), propylene ethylene copolymer (10-40%), and 1-butene ethylene copolymer (10-40%). The blend composition can be used as a single layer film or as a component layer or layers in a multiple-ply film structure. Derwent Abstract 87-240136/34, citing Japanese application J62 164 744, published July 21, 1987, discloses a shrinkable film comprising (a) 30-70 parts ethylene alpha olefin copolymer having density of 0.86-0.94; (b) 30-70 parts ethylene vinyl acetate copolymer; (c) 3-15 parts ethylene ethyl acrylate copolymer; and (d) 0.5-10 parts polybutene. EP-0240705A discloses a mixture of (A) 90 to 50% by weight of a linear ethylene-α-olefin copolymer of density 0.90 to 0.93 and (B) 10 to 50% by weight of an ethylene polymer of density 0.87 to 0.91 which is less than that of (A) by at least 0.014. For many applications, particularly for packaging of fish and poultry products on trays, a shrink film with certain improved mechanical and shrinkage properties is desirable. The present invention provides such a film. The film of the present invention is strong, having an average tensile strength of at least about 69 MPa (10 kpsi) and an average elongation at break of at least 150%. The film has an average modulus of at least about 138 MPa (20 kpsi), which is sufficiently stiff to be handled readily by existing packaging machines. The film exhibits an area shrinkage of at least about 30% at 90°C and at least about 75% at 110°C, thus allowing the preparation of snugly packaged items. It exhibits a recovery of deformation after five minutes of at least about 88% and after 60 minutes of at least about 92%, thus permitting packages made with such film to resume their original shape after deformation by some extraordinary force, applied, for example, during handling. Films of the present invention are heat sealable, forming good seals around cold, wet products. Finally, such films have a pleasant soft "feel" desirable for many packaging applications. SUMMARY OF THE INVENTION The present invention provides a shrink film consisting essentially of a blend of: (a) 10 to 80 percent by weight of at least one ethylene-alpha olefin linear copolymer having a density of 0.890 to 0.915; (b) 15 to about 70 weight percent of at least one low-density polyethylene from a tubular reactor having a density of 0.920 to 0.925; (c) 0 to 25 weight percent of at least one copolymer of ethylene with at least one copolymerized vinyl alkanoate, alkyl acrylate, or alkyl methacrylate; and (d) 0 to 53 weight percent of at least one linear ethylene-alpha olefin copolymer having a density of 0.915 to 0.940. The present invention further provides a process of preparing a shrink film comprising: (a) melt blending the above composition; (b) extruding the melt blend in the form of a sheet; (c) cooling the molten polymer in the sheet to below its melting point; (d) maintaining the sheet of polymer at a temperature below its melting point but sufficiently high that it can be oriented by stretching; and (e) orienting the sheet of polymer in at least one direction. DETAILED DESCRIPTION OF THE INVENTION The present invention is a shrink film made from a blend of at least two, and preferably three components. The first required component is one or more ethylene-alpha olefin linear copolymer having a density of about 0.890 to about 0.915 g/cm³, preferably about 0.912 g/cm³. Such copolymers are known as ultra low density polyethylene (ULDPE) or very low density polyethylene, and are prepared by the copolymerization of ethylene with an alpha olefin, preferably of 4 to about 18 carbon atoms, more preferably 6 to 18 carbon atoms, and most preferably 1-octene. The polymerization is generally carried out at low to medium pressure (about 29-30 MPa) in the presence of a coordination catalyst, such as various organoaluminum, organotitanium, or organovanadium compounds. Titanium modified organoaluminum compounds are widely used. An ultralow density material is obtained by incorporating sufficiently large amounts of the comonomer to achieve the desired low density. Such materials are available commercially from Dow Chemical Company and from Union Carbide Corporation. The copolymer preferably has a melt index of about 0.5 to about 2.0 dg/min, most preferably near 1.0, as is normally desirable for polymers to be used for films. Comparable results can also be obtained by using materials with higher melt index followed by irradiation crosslinking. The ULDPE is present at 10 to 80 percent by weight of the blend, preferably about 40 to about 65 weight percent, and most preferably about 45 to about 60 weight percent. The ULDPE contributes many of the desirable properties to the film, i.e., shrinkage, recovery, and to some extent, tensile strength. The second required component of this invention is another ethylene polymer. It is branched, i.e. tubular, low-density polyethylene having a density of about 0.920 to about 0.925. The second component is a low-density polyethylene, preferably having a density of about 0.923. Specifically this component is usually a highly branched low density polyethylene prepared in a tubular reactor. A tubular reactor, like an autoclave, employs high pressures and produces resin in the density range of about 0.917 to about 0.928. In the tubular reactor, ethylene containing a free radical initiator is passed through a preheater where it is heated to 100-200°C. The mixture is passed through a tube where it heats to 250-300°C as polymerisation occurs, although some of the heat is removed by cooling. Pressure, temperature, and type of intitiator are all variables that affect the properties of the resin in a manner which is known to those skilled in the art. Tubular polymerization reactions are described, for example, in U.S. patents 2,870,130 and 2,839,515. The distinctions between tubular resins and ordinary resin made e.g. in a high-pressure autoclave process are subtle but important. Such high pressure tubular resins have some desirable properties that are similar to those of LLDPE (linear low density polyethylene, ie. the optional fourth component) and similar to those of ethylene vinyl acetate copolymer. The tubular resins exhibit low modulus, high elongation, and relatively high impact strength compared to similar autoclave resins, and have a soft feel similar to that of EVA. Tubular resins mix well with LLDPE and with ULDPE, producing clear films. Autoclave resins of similar gross properties produce a much hazier film. Resins from the tubular process also operate more smoothly in the film forming and packaging process of the present invention. The reasons for these observed differences are not clearly known, but are believed to arise from a higher degree of branching in the resins from the tubular process. The melt index of the branched LDPE is preferably about 1 to about 3 and most preferably about 1.9. The low density polyethylene comprising the second component is preferably present at about 25 to about 55 weight percent, and most preferably about 30 to about 45 weight percent. This ethylene polymer provides stiffness necessary for running the film on certain high speed packaging machines. When branched LDPE is used, that component also contributes to recovery and shrinkage. The third optional componet is at least one copolymer of ethylene with at least one copolymerized vinyl alkanoate, alkyl acrylate, or alkyl methacrylate. This polymer is preferably present in an amount of about 2 to about 22 percent, and most preferably about 5 to about 15 percent. Suitable comonomers include vinyl alkanoates such as vinyl acetate, propionate, or butyrate, and alkyl acrylates and methacrylates wherein the alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, pentyl, hexyl, 2-ethylhexyl, and the like. Minor amounts of a third comonomer such as CO or SO₂ can also be present. Preferably the comonomer is vinyl acetate; the preferred melt index of this component is about 0.1 to about 10. The comonomer comprises about 3 to about 20 weight percent of the Copolymer, preferably about 10 to about 15 weight percent. The optional fourth component is linear ethylene-α copolymer of the second component and is commonly referred to as linear low density polyethylene (LLDPE). It preferably has a density of about 0.920 to about 0.924 and is prepared by copolymerization of ethylene with an α olefin of preferably 4 to about 18 carbon atoms, more preferably 6-18 carbon atoms, and most preferably 1-octene. The polymerization is carried out in a well-known manner similar to that described for ultra low density polyethylene, except that the amount of comonomer is reduced to an appropriate extent. Such polymerization is described, for example in U.S. Patent 4,076,698. The copolymer, as above, preferably has a melt index of about 0.5 to about 2.0 dg/min, most preferably near 1.0. The addition of ethylene vinyl acetate (EVA) to the composition is believed to contribute to the recovery and shrinkage properties of the film. It also provides a feel of softness to the film which is desirable, and contributes to the heat sealability. Of course, mixed comonomers can be used in each of the copolymers of the present invention. For example, a ULDPE which includes both octene and hexene as comonomers could be suitable. Similarly, a terpolymer of ethylene with vinyl acetate and e.g. methyl acrylate could be suitable as the third polymeric component. Likewise each of the major components can itself be a blend of suitable polymers selected from the available polymers for that component. If desired, the film of the present invention can be crosslinked by e.g. irradiation to improve its properties, particularly to extend the upper operating temperature of the shrink tunnel. Therefore a preferred embodiment provides irradiation of the film with about 1 to about 5 megarads, and most preferably about 2 megarads, of ionizing radiation. In order for such crosslinking to be effective, the blend should contain some branched material such as EVA or branched LDPE. Films of the present invention are preferably used as monolayer films; however, they can equally well serve as one or more layers of a multiple layer film structure. In order to retain the excellent sealing properties, it is preferred that for such a multiple layer structure at least one surface layer is a composition of the present invention. In addition, other conventional additives can be employed in low amounts in films of this invention, such as fillers, slip agents, antiblock agents, antifog agents, and the like. Films of the present invention can be manufactured by conventional processes for preparing oriented film. Typically a sheet of film is extruded, most often in the form of a tube, which is then quenched. The sheet or tube is oriented by heating to a temperature below its melting point and stretching in at least one direction. Most commonly such orientation is accomplished by a combination of air pressure and mechanical stretching in the machine direction, in the conventional air bubble process. Further details of film manufacture are provided in the Examples which follow. The shrink film so prepared can be used in conventional packaging operations, which can include wrapping of meat, fish, or poultry items, optionally contained within a tray, heat sealing the film to itself to form a closed, air tight package by means of hot wires, hot bars, or crimping wheels, and heating the film briefly in a shrink tunnel to cause it to shrink securely around the contents. The resulting packages retain their seals even when the contents are wet, and maintain their shape well even when subjected to distortion during shipping and handling. Examples 1-9 and Comparative Examples C1-C4 Films were prepared in a semiworks unit ("SW") or in a commercial unit ("Coml"), as described below. Resin feed for each sample made by the semiworks unit was prepared by dry blending each of the three resin components together. Resin for samples prepared by the commercial unit was prepared by melt blending LLDPE, EVA, and any additives used, and thereafter dry blending this mixture with ULDPE. The ultra low density polyethylene (ULDPE) was Attane™ 4001, from Dow Chemical, having a density of 0.912 g/cm³ and a melt index of 1.0 dg/min. The EVA copolymer contained 12 percent by weight vinyl acetate moieties and had a density of 0.940 and a melt index of 0.35. The linear low density polyethylene (LLDPE) was Dowlex™ 2050A, from Dow Chemical, having a density of 0.921 and a melt index of 1.1. Samples were prepared by first extruding a single-layer tube through a typical circular die, using the parameters indicated in Table I for a semiworks unit or a commercial unit. Semiworks Commercial Extruder diameter, mm 50.8 203 Extruded tube diameter, mm 53 361 Tube speed, m/min 1.8 17.7 Bubble pressure, kPa 1.9-2.5 0.35 Film speed, m/min 7.3 71.3 Bubble diameter, m 0.318 1.80 The extruded tube was passed over an internal quenching mandrel maintained at 20°C. The tubing was reheated to a temperature below the melting point of the polymer (about 110-115°C). Simultaneously with the heating, the tube was stretched in the transverse direction (TD) by blowing air into the tubing, and in the machine direction (MD) by pulling the film with rollers running three to five times the tube speed. The air was introduced into the tube at a pressure sufficient to expand the tube to about five times its original diameter, producing a hoop stress in the expanded bubble of about 14 - 17 MPa (2000-2500 kpsi). Tensile strength, modulus, and elongation of the resulting films were measured by ASTM D882. Shrinkage was measured by ASTM D2732, and area shrinkage calculated from the expression 1-(1-MD shrink) x (1-TD shrink)) x 100%. Recovery from deformation was determined by placing a 25.4 mm (1 inch) wide sample of film in an Instron™, having its jaws set initially to a 254 mm (10 inch) gap. The sample was stretched to 292 mm (11.5 inches) at a rate of 25.4 mm per minute. Tension on the sample was maintained for 5 minutes and thereafter released. The length of the sample after 5 minutes and 60 minutes recovery time was measured, and the percent recovery was calculated. The results of these measurements, reported in Table II, show that for each of the Comparative Examples 1 to 9, all of the pertinent properties of the film were within or nearly within the desired region. Comparative Example C1, which uses an insufficient amount of EVA and is at the lower limit of ULDPE, exhibits insufficient shrinkage at both 90 and 110° and borderline low recovery of deformation at 5 minutes. Comparative Example C2, which lacks LLDPE, exhibits unacceptably low modulus. Comparative Examples C3 and C4, which lack ULDPE, exhibit low shrinkage and low or borderline recovery. Comparative Example 2 exhibits borderline shrinkage; it is at the lower limit of the present invention in terms of ULDPE content. Comparative Example 3 likewise exhibits borderline shrinkage and recovery; it is near the lower limit of the invention in terms of EVA content. Comparative Example 4 exhibits borderline recovery properties; it is near the upper limit of the invention in terms of EVA content. Examples 10-14 Samples were prepared and tested as indicated for Examples 1-9. The low density polyethylene used in these Examples was Dow LDPE 503, from Dow Chemical, a highly branched polymer believed to be-made in a tubular reactor, having a density of 0.923 and a melt index of 1.9. The results, reported in Table III, show that this highly branched LDPE can be substituted for all or part of the LLDPE and EVA. Example 10 is a Comparative Example Comparative Example C5. Packages were made on an FMC™ horizontal form and fill machine. A tube was formed from the film of Comparative Example C4 using heated wheels to form a seal between two edges along the length of the tube. Trays of chicken were pushed into the tube from the open end. The tube and tray were advanced and a hot knife bar cut the tube and sealed the trailing end. Packages so prepared exhibited gaps in the sealed area formed by the heated wheels in about every third package. Examples 15 and 16 Packages were made on a commercial scale from the film of Examples 7 and 8, respectively, using the process of Comparative Example C5. Observation of several thousand packages so prepared revealed no apparent defects or leaks in the seal areas. Examples 17-21 Tubes (but not packages) were prepared from the films of Examples 10-14. Tubes from the films of Examples 10, 11, and 12 exhibited good seals. Tubes from the films of Examples 13 and 14 exhibited about 1 seal defect every 6 meters (20 feet). Since a package typically requires about 30 cm (1 foot) of tube, this corresponds to about a 5% defect rate.

Claims: Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, GR, IT, LI, LU, NL, SE A shrink film consisting essentially of a blend of: (a) 10 to 80 percent by weight of at least one ethylene-alpha olefin linear copolymer having a density of 0.890 to 0.915; (b) 15 to about 70 weight percent of at least one low-density polyethylene from a tubular reactor, having a density of 0.920 to 0.925; (c) 0 to 25 weight percent of at least one copolymer of ethylene with at least one copolymerized vinyl alkanoate, alkyl acrylate, or alkyl methacrylate; and (d) 0 to 53 weight percent of at least one linear ethylene-alpha olefin copolymer having density of 0.915 to 0.940. The shrink film of claim 1 wherein the film is a single layer. The shrink film of claim 1 or 2 wherein the alpha olefin of copolymer (a) has 6 to 18 carbon atoms. The shrink film of claim 1 or 2 wherein the alpha olefin of copolymer (a) is 1-octene. The shrink film of claims 1, 2, 3 or 4 wherein copolymer (a) comprises about 40 to about 65 weight percent of the composition. The shrink film of claim 5 wherein copolymer (a) comprises about 45 to about 60 weight percent of the composition. The shrink film of any one of claims 1 to 6 wherein polymer (d) is a copolymer of ethylene with an alpha olefin having 4 to 18 carbon atoms. The shrink film of claim 7 wherein polymer (d) is a copolymer of ethylene with 1-octene. The shrink film of any one of claims 1 to 8 wherein polymer (b) comprises about 25 to about 55 weight percent of the composition. The shrink film of claim 9 wherein polymer (b) comprises about 30 to about 45 weight percent of the composition. The shrink film of any one of claims 1 to 10 wherein copolymer (c) is a copolymer of ethylene and vinyl acetate. The shrink film of claim 11 wherein the ethylene vinyl acetate copolymer of (c) contains about 3 to about 20 weight percent copolymerised vinyl acetate moieties. The shrink film of claim 11 wherein the ethylene vinyl acetate copolymer of (c) contains about 10 to about 15 weight percent copolymerized vinyl acetate moieties. The shrink film of any one of claims 1 to 13 wherein copolymer (c) comprises about 2 to about 22 weight percent of the composition. The shrink film of claim 14 wherein copolymer (c) comprises about 5 to about 15 weight percent of the composition. The shrink film of any one of claims 1 to 15 wherein the film is cross-linked to the degree induced by an irradiation dosage of about 1 to about 5 megarads of ionizing radiation. The shrink film of claims 1, 2 or 16 wherein the copolymer of (a) is a copolymer of ethylene with 1-octene, has a melt index of 0.5 to 2.0 and a density of 0.910 to 0.915, and is present at a level of 45 to 60 weight percent, the polymer of (b) is present at a level of 30 to 45 weight percent, and the copolymer of (c) is a copolymer of ethylene with 10 to 15 weight percent vinyl acetate and is present at a level of 5 to 15 weight percent. A process for preparing a shrink film comprising: (a) melt blending a composition of (i) 10 to 80 percent by weight of at least one ethylene-alpha olefin linear copolymer having a density of 0.890 to 0.915; (ii) 15 to about 70 weight percent of at least one low density polyethylene from a tubular reactor having a density of 0.920 to 0.925; (iii) 0 to 25 weight percent of at least one copolymer of ethylene and at least one vinyl alkanoate, alkyl acrylate, or alkyl methacrylate; and (iv) 0 to 53 weight percent of at least one linear ethylene-alpha olefin copolymer having density of 0.915 to 0.940; (b) extruding the melt blend in the form of a sheet; (c) cooling the molten polymer in the sheet to below its melting point; (d) maintaining the sheet of polymer at a temperature below its melting point but sufficiently high that it can be oriented by stretching; and (e) orienting the sheet of polymer in at least one direction. A multiple layer structure wherein at least one layer is the shrink film of any one of the preceding claims. Claims for the following Contracting State : ES A process for preparing a shrink film comprising: (a) melt blending a composition of; (i) 10 to 80 percent by weight of at least one ethylene-α olefin linear copolymer having a density of 0.890 to 0.915; (ii) 15 to about 70 weight percent of at least one low-density polyethylene from a tubular reactor having a density of 0.920 to 0.925; (iii) 0 to 25 weight percent of at least one copolymer of ethylene and at least one vinyl alkanoate, alkyl acrylate, or alkyl methacrylate; and (iv) 0 to 53 weight percent of at least one linear ethylene-α olefin copolymer having density of 0.915 to 0.940 (b) extruding the melt blend in the form of a sheet; (c) cooling the molten polymer in the sheet to below its melting point; (d) maintaining the sheet of polymer at a temperature below its melting point but sufficiently high that it can be oriented by stretching; and (e) orienting the sheet of polymer in at least one direction. The process of claim 1 wherein the film is a single layer. The process of claim 1 or 2 wherein the α olefin of copolymer (i) has 6 to 18 carbon atoms. The process of claim 1 or 2 wherein the α olefin of copolymer (i) is 1-octene. The process of claim 1, 2, 3 or 4 wherein the α olefin of copolymer (i) comprises about 40 to about 65 weight percent of the composition. The process of claim 5 wherein copolymer (i) comprises about 45 to about 60 weight percent of the composition. The process of any one of claims 1 to 6 wherein polymer (iv) is a copolymer of ethylene with an alpha olefin having 4 to 18 carbon atoms. The process of claim 7 wherein polymer (iv) is a copolymer of ethylene with 1-octene. The process of any one of claims 1 to 8 wherein polymer (ii) comprises about 25 to about 55 weight percent of the composition. The process of claim 9 wherein polymer (ii) comprises about 30 to about 45 weight percent of the composition. The process of any one of claims 1 to 10 wherein copolymer (iii) is a copolymer of ethylene and vinyl acetate. The process of claim 11 wherein the ethylene vinyl acetate copolymer of (iii) contains about 3 to about 20 weight percent copolymerized vinyl acetate moieties. The process of claim 11 wherein the ethylene vinyl acetate copolymer of (iii) contains about 10 to about 15 weight percent copolymerized vinyl acetate moieties. The process of any one of claims 1 to 13 wherein copolymer (iii) comprises about 2 to about 22 weight percent of the composition. The process of claim 14 wherein copolymer (iii) comprises about 5 to about 15 weight percent of the composition. The process of any one of claims 1 to 15 wherein the film is cross-linked to the degree induced by an irradiation dosage of about 1 to about 5 megarads of ionizing radiation. The process of claims 1, 2 or 16 wherein the copolymer of (i) is a copolymer of ethylene with 1-octene, has a melt index of 0.5 to 2.0 and a density of 0.910 to 0.915, and is present at a level of 45 to 60 weight percent, the polymer of (ii) is present at a level of 30 to 45 weight percent, and the copolymer of (iii) is a copolymer of ethylene with 10 to 15 weight percent vinyl acetate and is present at a level of 5 to 15 weight percent.

Inventors: ROBERTS RICHARD KENNETH, ROBERTS, RICHARD KENNETH
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1990
Main classification: C08L23
IPC codes: B29D7, B29L7, B65D65, B29C61, B29C55, C08L23, C08J5, B29K23