MULTILAYER OXYGEN BARRIER PACKAGING FILM

Abstract: A thermoplastic multilayer packaging film which has: (a) an oxygen barrier core layer comprising ethylene-vinyl alcohol copolymer; (b) two outer layers; and (c) two adhesive layers each of which disposed between the core layer (a) and each of the two outer layers (b), characterized in that at least one of the outer layers (b) comprises a blend of three components A, B, and C, wherein Component A is a homogeneous or heterogeneous ethylene- alpha -olefin copolymer with density comprised between 0.915 g/cc and 0.925 g/cc, Component B is a homogeneous or heterogeneous ethylene- alpha -olefin copolymer with density >/= 0.925 g/cc, and Component C is a homogeneous or heterogeneous ethylene- alpha -olefin copolymer with density </= 0.915 g/cc. The use of modified homogeneous ethylene- alpha -olefin copolymers with a density of from about 0.900 g/cc and about 0.908 g/cc as adhesive layers to improve the interlayer adhesion and the sealability properties of films with a core layer comprising an ethylene-vinyl alcohol copolymer or a polyamide and outer layers comprising an ethylene- alpha -olefin copolymer is also described.

Description: MULTILAYER OXYGEN-BARRIER PACKAGING FILM The present invention refers to a multilayer, heat-shrinkable film endowed with very good optical and mechanical properties, excellent gas- barrier properties and improved heat-sealability characteristics particularly suitable for packaging food products. Multilayer, thermoplastic films are being used for packaging various, food and non food, items because they protect the item itself from the environment during storage and distribution. Furthermore, for the end consumer, presenting the product packaged in a transparent thermoplastic film that allows him to visibly inspect the package content, is a sort of assurance of the quality of the product that renders it even more attractive. Optical characteristics are therefore essential for a thermoplastic film for packaging. Other properties are also necessary, such as for instance good mechanical properties that allow to keep the package unaltered until it is offered to the customer/consumer. A shrink feature is also conveniently imparted to a thermoplastic film by orientation or stretching of the film, either mono-axially or biaxially, during film manufacture. This shrink feature allows the film to shrink or, if restrained, create shrink tension within the film upon exposure to heat. In a typical process the thick structure which is extruded through either a round or a flat extrusion die is quickly quenched, then it is heated to a suitable temperature, called the orientation temperature, which is higher than the T g of all the resins used in the film itself but lower than the melting temperature T m of at least one of said materials, and stretched in either or both directions. Furthermore, for food packaging it is often necessary that the film has oxygen barrier characteristics to avoid product oxidation or degradation during its shelf-life. In addition to these properties also good heat-sealability properties are required. It is in fact essential, particularly for oxygen-barrier films used in applications where the contained product is to be kept either under vacuum or under a modified atmosphere, that the seal(s) that close the package have a remarkable strength and as a consequence thereof that the package has a remarkable tightness. Several different materials have been used to decrease the oxygen permeability of thermoplastic films. Among these materials a very good gas-barrier material is EVOH (ethylene-vinyl alcohol copolymer) and there are several "barrier" thermoplastic films comprising an EVOH layer described in the patent literature. As an example EP-B-87080 describes films comprising a core layer of EVOH, two skin layers of a blend of EVA (ethylene-vinyl acetate copolymer) and an ethylene-α-olefin copolymer, and two adhesive or tie layers, between the core and the skin layers, characterised by a specific composition of the skin layer blends. EP-B-92,897 and its divisional application EP-A-346,944 cite a series of films with a varying number of layers and comprising a core layer containing i.a. EVOH, and skin layers, that are the same or different and that generally comprise blends of low density ethylene-α-olefin copolymer and EVA. EP-B-217,596 describes an oriented and cross-linked multilayer film comprising a core layer comprising EVOH, two inner tie layers and two skin layers of a ternary blend of a low density ethylene-α-olefin copolymer, a medium density ethylene-α-olefin copolymer and EVA. EP-A-236,099 describes multilayer films comprising a core layer comprising EVOH, two inner tie layers and two skin layers comprising a polymer material or a blend of polymer materials. Among the specific examples, films are described with outer layers of low density ethylene-α- olefin copolymer, polypropylene or ethylene-propylene copolymer, blends of low density ethylene-α-olefin copolymer and very low density ethylene- α-olefm copolymer, blends of polypropylene and ethylene-propylene copolymer, and blends of low density ethylene-α-olefin copolymer, medium density ethylene-α-olefin copolymer, and EVA. In the prior art films the different materials employed for the skin layers are suitably combined with the aim at improving as much as possible the film characteristics, particularly those characteristics that are needed for the specific application foreseen. As an example the use of a low density ethylene-α-olefm copolymer provides for fair heat-sealability and remarkable oil resistance properties; the use of EVA improves the shrinkability and the sealability properties; the use of propylene homo- and/or co-polymer increases the stiffness of the structure; etc.. It is however known that a resin that improves a specific property worsens the others and therefore the research efforts in this field actually tend to reach an optimum balance of these properties. More particularly the film characteristics that still need to be improved, in a way that however should not negatively affect the other characteristics such as optical, mechanical, barrier and shrinkability properties, are the sealability properties. DEFINITIONS As used herein the term "film" refers to a flat or tubular flexible structure of thermoplastic material having a thickness up to about 120 μ. Generally, for the purposes of the present invention, said structure will have a thickness of up to about 60 μ and typically up to about 35 μ. As used herein the phrase "core layer" or "inner layer" refer to any film layer having its two principal surfaces adhered to other layers of the multilayer film. The term "oxygen barrier core layer" is intended to refer to such a core layer having the primary function of reducing the oxygen permeability of the film. As used herein the phrase "outer layer" or "skin layer" refer to any film layer of a multilayer film having only one of its principal surfaces directly adhered to another layer of the film. As used herein, the phrase "heat-sealing" or "heat-sealant" layer, as applied to multilayer films, refers to an outer layer which is involved in the sealing of the film to itself, to another film layer of the same or another film, and/or to another article which is not a film. As used herein the terms "adhesive layer" or "tie layer" refer to any inner layer having the primary purpose of adhering two layers to one another. As used herein the phrase "directly adhered" as applied to film layers is defined as adhesion of the subject film layer to the object film layer, without a tie layer, an adhesive or other layer in-between. In contrast, as used herein, the word "between", as applied to a film layer expressed as being between two other specified layers, includes both direct adherence of the subject layer to the two other layers it is between, as well as a lack of direct adherence to either or both of the two other layers the subject layer is between, i.e. one or more additional layers can be present between the subject layer and one or more of the layers the subject layer is between. As used herein the term "heat-shrinkable" film refers to a film drawn mono-axially or biaxially that upon heating for 5s at a temperature of 120°C shows a % free shrink of at least 10 in at least one direction. As used herein the term "homopolymer" is used with reference to a polymer resulting from the polymerization of a single monomer, i.e. a polymer consisting essentially of a single type of repeating unit. For the purposes of the present invention the term "co-polymer" refers to a product of a polymerization reaction involving two or more different comonomers. The term "polyolefin" refers to a thermoplastic resin obtained by polymerization of an olefin or by copolymerization of two or more olefins or of one or more olefins with other comonomers, wherein the olefin units are anyway present in larger amounts than any possibly present comonomer. Suitable examples of "polyolefins" are polyethylene, ethylene-α-olefin copolymers either heterogeneous or homogeneous, ethylene-vinyl acetate copolymers, ethylene-acrylic acid or methacrylic acid copolymers, etc. The term "modified polyolefin" means a polyolefin characterised by the presence of functional groups such as typically anhydride or carboxy groups. Examples of said modified polyolefins are graft copolymers of maleic acid or anhydride onto ethylene-α-olefin or ethylene-vinyl acetate copolymers, polymerisation products of these with other polar monomers, blends thereof etc.. The term "EVOH" or the phrase "ethylene-vinyl alcohol copolymer" refer to saponified or hydrolysed products of ethylene-vinyl ester copolymers, generally of ethylene-vinyl acetate copolymers, wherein the ethylene content is typically comprised between 20 and 60 % by mole and preferably between 28 and 49 % by mole and the degree of saponification is higher than 90 and preferably higher than 95 %. The term "polyamide" as used herein refers to high molecular weight polymers having amide linkages along the molecular chain. Such term encompasses both polyamides and co-polyamides with aliphatic and/or aromatic repeating units, either crystalline, semi-crystalline or amorphous. For the purposes of the present invention, the phrase "ethylene-α-olefin copolymer" is used to identify the copolymerization products of ethylene with one or more α-olefins, e.g. butene-1 , hexene-1 , methyl-4-pentene-1 , octene-1 , as well as the blends thereof. Furthermore said phrase comprises both heterogeneous and homogeneous ethylene-α-olefin copolymers. As used herein the phrase "heterogeneous ethylene-α-olefin copolymer" refers to those polymerization reaction products characterised by a relatively wide variation in molecular weight and composition distribution. Such heterogeneous polymers typically contain a relatively wide variety of chain lengths and comonomer percentages. In particular for these products the molecular distribution, expressed as M w /M n wherein M w is the average molecular weight by weight and M n is the average molecular weight by number, is higher than 3. These heterogeneous polymers are typically prepared by using the conventional Ziegler-Natta catalysts in heterogeneous phase. Depending on the density these copolymers are generally indicated by the abbreviations LMDPE (linear medium density polyethylene - that conventionally designates heterogeneous ethylene-α-olefin copolymers having a density > 0.925 g/cc), LLDPE (linear low density polyethylene - that conventionally designates heterogeneous ethylene-α-olefin copolymers having a density of from 0.915 g/cc to 0.925 g/cc), and VLDPE (very low density polyethylene - that conventionally designates heterogeneous ethylene-α-olefϊn copolymers having a density < 0.915 g/cc). As used herein the phrase "homogeneous ethylene-α-olefin copolymers" refers to polymerization reaction products of relatively narrow molecular weight distribution and relatively narrow composition distribution. Such homogeneous polymers structurally differ from the heterogeneous ones in that they exhibit a relatively even sequencing of comonomers within a chain, the mirroring of sequence distribution in all chains and the similarity of length of all chains. Furthermore, with only few exceptions (such as the homogeneous linear ethylene-α-olefin copolymers named TAFMER™ that are manufactured by Mitsui Petrochemical Corporation using homogeneous Ziegler-Natta catalysts) said homogeneous polymers are characterised by the fact that they are generally prepared using "metallocene", or "single-site", or "constrained- geometry" catalysts. There are some methods generally known in this field to identify and classify homogeneous polymers, such as the molecular weight distribution ( M,,), and the Composition Distribution Breath Index (CDBI). The molecular weight distribution, also known as polydispersity, may be determined by gel permeation chromatography. The homogeneous ethylene-α-olefin copolymers useful in the present invention generally have a (M w /M n ) of less than about 3. The CDBI of such homogeneous ethylene-α-olefm copolymers will generally be greater than about 60 % and generally higher than 70 %. The CDBI is defined as the weight percent of the polymer molecules having a comonomer content within 50 percent (i.e. plus or minus 50%) of the median total molar comonomer content. The CDBI of a polyethylene homopolymer, which does not contain a comonomer, is by definition 100 %. The CDBI is readily calculated from data obtained from techniques known in the art, such as for example Temperature Rising Elution Fractionation (TREF) as described for instance by Wild et al. in Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p.441 (1982). Processes of preparation of homogeneous ethylene-α-olefin copolymers are disclosed in WO-A-9403414, US-A-5,206,075, US-A- 5,241 ,031 , WO-A-9303093, US-A-5,272,236, US-A-5,278,272, etc.. Homogeneous ethylene-α-olefin copolymers, obtained by using "metallocene" catalysts are actually commercialised by Exxon Chemical Company under the trade name EXACT™, by BASF as LUFLEXEN™, and by Dow as AFFINITY™ or ENGAGE™ resins. DESCRIPTION OF THE INVENTION It has now been found that it is possible to get a gas-barrier film with optical and gas-barrier properties at least comparable to those of the known films containing EVOH, and having remarkably improved mechanical and heat-sealability properties, by using in the film sealing layer a three component blend of ethylene-α-olefin copolymers of suitably selected different densities. A first object of the present invention is therefore a multi-layer thermoplastic film comprising (a) a core layer comprising an ethylene-vinyl alcohol copolymer, (b) two outer layers, and (c) two adhesive layers each of which disposed between the core layer (a) and each of the two outer layers (b), characterized in that at least one of the outer layers comprises a three component blend of Components A, B, and C, wherein Component A is a homogeneous or heterogeneous ethylene-α-olefin copolymer having a density of from 0.915 g/cc to 0.925 g/cc, Component B is a homogeneous or heterogeneous ethylene-α-olefin copolymer having a density > 0.925 g/cc, and Component C is a homogeneous or heterogeneous ethylene-α- olefin copolymer having a density < 0.915 g/cc. According to the present invention only one of the outer layers (the outer layer that will be used as the sealing layer) needs to comprise a three component blend as defined above. The other outer layer might therefore have a different composition and comprise a single polymer or a blend of polymers typically selected from ethylene homo- and co¬ polymers, e.g. polyethylene, homogeneous or heterogeneous ethylene-α- olefin copolymers, EVA, etc.. In a preferred embodiment of the present invention however both outer layers (b) comprise a ternary blend of Components A, B, and C, as defined above. The films according to the present invention comprise at least five layers. Films with a higher number of layers, either symmetrical or unsymmetrical, are obtained when one or more additional layers are present between the adhesive layers (c) and the outer layers (b) and/or between the core oxygen barrier layer (a) and the adhesive layers (c). In a preferred embodiment of the present invention adhesive layers (c) directly adhere to the core layer (a). When, in said preferred embodiment, the surface of each of the adhesive layers (c) that does not adhere to the core layer (a), directly adheres to the outer layer (b), the film, according to a most preferred embodiment, will contain five layers. Films according to said preferred embodiment may also contain a higher number of layers if one or more additional layers are positioned between the adhesive layers (c) and the outer layers (b). As an example, 6- or, preferably, 7-layer films according to said preferred embodiment may comprise additional layer(s) between the adhesive layers (c) and the outer layers (b) made with recycle material from the scrap of the same film, possibly blended with a compatibilizer. In another preferred embodiment of the present invention, the film will comprise two polyamide comprising layers (d), each one of which directly adhering to one of the two surfaces of the core layer (a). In said embodiment therefore the film according to the present invention is a 7- layer film, when each of the adhesive layers (c) directly adheres to each of the polyamide comprising layers (d) as well as to each one of the outer layers (b). It may also comprise more than 7 layers when additional layers, such as layers made with recycle material, are present between the adhesive layers (c) and the outer layers (b). The thickness of the film according to the present invention will vary depending on the end use thereof. It will generally be in the range of from 12 to 80 μ, and preferably of from 14 to 60 μ. For use as a packaging film, the thickness will be comprised generally between 12 and 35 μ, and preferably between 14 and 26 μ, while for use in the manufacture of bags the thickness will be comprised generally between 35 and 65 μ, and preferably between 40 and 60 μ. As for the outer layers (b), Component A is the component that is present in the highest percent (by weight) in the blend. Typically said Component A is present in a percent by weight of from about 35 to about 80, preferably in a percent by weight of from about 40 to about 70 and even more preferably in a percent by weight of from about 45 to about 65. Component B and Component C are present in the blend in lower amount with respect to Component A. Typically said Components, each independently, are present in amounts comprised between about 10 and about 35 % by weight, preferably between about 15 and about 30 and even more preferably between about 20 and about 25 % by weight. When amounts lower than 10 % are employed for Component B the film that is thus obtained has impaired mechanical properties. It has been found that the modulus of films wherein Component B is absent in the outer layers is remarkably lower than that of the same films containing at least 10 % of said Component in the outer layers. The use of Component C in amounts lower than 10 % on the other hand remarkably decrease the film shrink and heat-sealability properties. Optimum ratios between the various components in the ternary blend are, e.g., 50:25:25, 40:30:30, 60:20:20, 60:25:15, and 50:30:20 (Component A : Component B : Component C). The thickness of the outer layers is not critical and depends on the overall film thickness and on the number of different layers therein. When used as a film for packaging, a suitable thickness for each outer layer is comprised between 3 and 12 μ, while when used for the manufacture of bags for packaging, a suitable thickness is from 8 to 20 μ. Said outer layers may contain, and generally at least one of them does contain, additives, such as for instance those conventional additives that are used in small amounts to improve resin processability or the properties of the end film. Examples of said additives are antioxidant agents, slip and anti-block agents, UV absorbers, antimicrobial agents, pigments, anti-fog agents or compositions, cross-linking agents or cross¬ link inhibitors, oxygen scavenging agents or compositions, etc.. The density of Component A is preferably comprised between 0.918 g/cc and 0.922 g/cc, while for Component B it is preferably higher than 0.928 g/cc and generally comprised between 0.928 and 0.938 g/cc and for Component C it is preferably lower than 0.912 g/cc and even more preferably lower than 0.905 g/cc. Typically Component C has a density of from 0.895 g/cc to 0.912 g/cc, and preferably of from 0.898 g/cc to 0.905 g/cc. The Melt Flow Index of these copolymers may vary widely, as an example from about 0.2 g/10' to about 10 g/10' or even more. Preferred MFI's are however comprised between about 0.5 g/10' and about 5.0 g/10', and preferably between about 0.8 g/10' and about 3.0 g/10'. The use of copolymers with low MFI increases the structure mechanical resistance but negatively affects resin processability. In a preferred aspect of the present invention Component B is a heterogeneous ethylene-α-olefin copolymer; in an even more preferred aspect also Component A is a heterogeneous ethylene-α-olefin copolymer. As for Component C, in a preferred aspect of the present invention said component is a homogeneous ethylene-α-olefin copolymer, since the use of either a homogeneous or a heterogeneous copolymer brings about a widening of the sealability window that however is higher in case a homogeneous copolymer is used. The sealability window represents in practice the temperature range within which it is possible to seal the film obtaining a substantially constant seal strength above a fixed acceptable lower limit. Since it is often difficult and sometimes also impossible to maintain the sealing bars at the same temperature, it is in practice necessary to have a sealing window as wide as possible to guarantee that almost all the obtained seals, in spite of the possible and frequent temperature fluctuations of the sealing bars, have an acceptable seal strength. Furthermore, it happens frequently that the thermoplastic film plies to be sealed together do not lie absolutely flat on one another but some wrinkling occurs in one or both the film plies. To guarantee a seal of a suitable strength in all packages it is therefore necessary to increase the temperature of the sealing bars and/or increase the sealing time with respect to the theoretical value. A narrow sealing window will therefore create problems because the temperature reached by the film in those areas where there are no wrinkles can cause the thermoplastic material to melt, the film to be cut by the pressure of the sealing bars, and the material to be deteriorated with a consequent remarkable loss in productivity. It has now been found that by simply replacing in a prior art film, such as that described in EP-B-217,596, the ethylene-vinyl acetate copolymer in the ternary blend of the outer layers with Component C, it is possible to enlarge the sealing window by at least 10°C. By using as Component C a homogeneous ethylene-α-olefin copolymer, said enlargement of the sealing window reaches 20°C. In a preferred embodiment of the present invention, the film is an oriented and heat-shrinkable film. Preferably it has a free shrink, measured at 120°C, of at least 20% in at least one direction, more preferably of at least 30 % in at least one direction and even more preferably of at least 40 % in at least one direction. In a most preferred embodiment the film of the present invention has a free shrink, measured at 120°C, of at least 20 % in both directions, more preferably at least 30 % in both directions and even more preferably of at least 40 % in both directions. The oxygen-barrier core layer, comprises EVOH. Examples of EVOH that may well be employed in the production of films according to the present invention are EVAL™ EC F151A or EVAL™ EC F101A, marketed by Marubeni. A single EVOH or a blend of two or more EVOHs can be employed. Also a blend of one or more EVOHs with one or more polyamides may be employed. In this case, suitable polyamides are those commonly indicated as nylon 6, nylon 66, nylon 6/66, nylon 12, nylon 6,12, and the like. A preferred polyamide is nylon 6/12, a copolymer of caprolactam with laurolactam, such as GRILON™ CF 6S or GRILON™ W8361 manufactured and marketed by EMS. In general in order to improve processability, particularly when a heat- shrinkable film is desired, a blend of EVOH with a varying amount of one or more polyamides is preferably employed. Generally, if a high oxygen barrier is needed, the amount of polyamide blended with EVOH will not be higher than 30 %. It is however possible to increase this amount when a limited oxygen barrier is desired. As an example for the packaging of respiring foods, such as vegetables and cheese, where in general a fair permeability to CO 2 is desired and it is not necessary to have a high oxygen barrier, it is possible to use blends of EVOH with polyamides wherein the polyamide(s) are employed in an amount of up to 85 % by weight on the overall weight of the core layer blend. The thickness of the barrier layer may vary, depending in general on the overall thickness of the film and on its use, between 2 and 10 μ. Preferably it will be comprised however between 2.5 and 5 μ. The adhesive layers (c) may generally be of a modified polyolefin as indicated above and as known in the field. Examples of said conventional modified polyolefins are for instance BYNEL™ CXA 4104 or BYNEL™ CXA 4105 marketed by DuPont, PLEXAR™ 169 marketed by Quantum, or some ADMER™ resins by Mitsui. It has however been found that when modified polyolefins based on homogeneous ethylene-α-olefin copolymers with a density of between about 0.880 g/cc and about 0.908 g/cc are employed in the adhesive layers, the bond between the layers is remarkably high and there are no delamination problems. Furthermore it has been found unexpectedly that by using said materials, and preferably by using modified polyolefins based on homogeneous ethylene-α-olefin copolymers with a density of between about 0.900 g/cc and about 0.908 g/cc, in at least one of the adhesive layers, a remarkable increase of the seal strength is obtained and as a consequence thereof an increase of the hot and cold seal resistance. Examples of said adhesives are ADMER™ AT 1093E (density = 0.903 g/cc and MFI = 1.3 g/10') and ADMER™ AT 1094E (density = 0.906 g/cc and MFI = 1.5 g/10') manufactured by Mitsui. Also the thickness of the adhesive layers may vary depending on the overall film thickness and on the type of resin employed. In general adhesive layers having a thickness of from about 2 to about 8 μ, and preferably of from about 2.5 to about 6 μ, are employed. It has finally been found that said unexpected improvements in the seal strength are obtained in all films comprising an ethylene-α-olefin copolymer in the sealing layer. It is therefore a further object of the present invention a method to improve the seal strength in a package made from a film comprising a core layer comprising EVOH or a polyamide and a sealing layer comprising an ethylene-α-olefin copolymer, said method comprising adhering the core layer to the sealing layer by means of an adhesive layer comprising a modified homogeneous ethylene-α-olefin copolymer with a density of between about 0.900 g/cc and about 0.908 g/cc. It is finally a further additional object of the present invention a film endowed with improved sealability properties comprising a core layer comprising EVOH or polyamide, two outer layers comprising an ethylene- α-olefin copolymer, and adhesive layers between the core layer and the outer layers characterised in that at least one of said adhesive layers comprises a modified homogeneous ethylene-α-olefin copolymer with a density of between about 0.900 g/cc and about 0.908 g/cc. In a preferred aspect both adhesive layers comprise a modified homogeneous ethylene-α-olefin copolymer with a density of between about 0.900 g/cc and about 0.908 g/cc. The films according to the present invention are typically obtained by coextrusion of the resins and/or blends of resins of the various layers through a round or flat extrusion die, quickly followed by quenching at room temperature. Alternatively, the film according to the present invention may be prepared by extrusion coating, wherein one or more layers are coated, still by extrusion, on top of a first extruded or co¬ extruded tube or sheet. If a heat-shrinkable film is desired, the thus obtained thick tube or sheet is heated to the orientation temperature, generally comprised between about 110 C C and about 125°C, by passing it through a hot air tunnel or an IR oven and stretched mono- or bi-axially. When a round extrusion die is employed, stretching is generally carried out by the trapped bubble technique. In this technique the inner pressure of a gas such as air is used to expand the diameter of the thick tubing obtained from the extrusion to give a larger bubble transversely stretched, and the differential speed of the nip rolls that hold the bubble is used to get the longitudinal stretching. Generally stretching is in a ratio of at least 3 in each direction. Alternatively, when a flat die is used in the extrusion, if a heat-shrinkable film is desired, orientation is carried out by means of a tenter frame. Longitudinal stretching is generally obtained by passing the film on at least two couples of conveying rolls wherein the second set rotates at a speed higher than that of the first set. The transverse orientation is on the other hand obtained by blocking the film side edges by means of a series of clips that travel onto two continuous chains that gradually diverge with the advancing of the film. Alternatively to said sequential stretching, either longitudinal first and then transversal or transversal first and then longitudinal, stretching may also be simultaneous in both directions. In case of stretching by tenter-frame the stretching ratios are generally higher than with the trapped bubble method. In a preferred embodiment of the present invention the film is cross¬ linked. Cross-linking may be achieved either by irradiation or chemically. Preferably cross-linking is achieved by irradiation that involves submitting the film to a suitable radiation dosage of high energy electrons, generally comprised between about 10 and about 120 KGrays, and preferably from about 20 to about 90 KGrays. If a heat-shrinkable film is desired, irradiation is preferably but not necessarily performed before orientation. If only some of the layers of the films need to be irradiated, the extrusion coating technique can be used and the irradiation step carried out on the primary tube or sheet, or the broad beam irradiation system can be used. When the whole film is cross-linked by electron-beam irradiation, it may be advantageous to make use of cross-linking controlling agents which can be added to the different layers in different amounts to control the degree of cross-linking in each layer. Suitable cross-linking controlling agents are for instance those described in EP-A-333,294. Alternatively, chemical cross-linking of the resins can be achieved by the addition of suitable cross-linking agents, e.g. peroxides, to the resins to be cross-linked. It is also possible to combine chemical cross-linking and irradiation, as an example when the cross-linking agents added to the resins need some irradiation to trigger the cross-linking reaction. The films according to the present invention may optionally be subjected to other types of energetic radiation treatments which may have different aims. As an example the film may be subjected to a corona discharge treatment to improve the print receptivity characteristics of the film surface. In case of oriented heat-shrinkable films, it may sometimes be desirable to selectively reduce the shrink force of the thus obtained film, at least in the transverse direction, without appreciably reducing the % free shrink. This can be useful for instance when the film is used as a tray wrapping or a tray lidding. It has in fact been found that with most of the commercial trays it is advisable to use films having a shrink force in the transverse direction lower than 0.05 kg/cm to avoid tray distortion. In such a case the desired reduction in shrink force may be achieved by subjecting the film obtained by the above general method to a heat treatment under strictly controlled conditions. In particular such a heat treatment involves heating the film to a temperature of from 65 to 95°C for a time of from 0.1 to 7.5 seconds and then cooling it down to a temperature below room temperature, preferably below 20°C, in less than 5 seconds. When a cross-linked film is desired, such a heat-treatment may be carried out, after orientation, either before or after cross-linking. The Examples that follow are only aimed at better illustrating some representative embodiments of the present invention but in no way they should be interpreted as a limitation to the scope thereof. Density is measured by ASTM D 792. The indicated melting points, if not otherwise indicated, are determined by DSC analysis following ASTM D 3418 (2 nd heating - 0°C/min). Melt Flow Index is measured according to ASTM D-1238, Condition E, at 190°C and is reported as grams per 10 minutes. In order to evaluate the films according to the present invention the following tests have been used : % unrestrained free shrink : the % free shrink, i.e., the irreversible and rapid reduction, as a percent, of the original dimensions of a sample subjected to a given temperature under conditions where nil restraint to inhibit shrinkage is present, has been measured according to ASTM method D 2732, by immersing for 5 seconds specimens of the films (100- mm by 100-mm) into a bath of hot oil at 120°C. The % free shrink has been measured in both the longitudinal (machine) and transverse directions. The percent free shrink is defined, for each direction, as Unrestrained linear shrinkage, % = [(L 0 -Lf)/L 0 ] x 100 wherein L 0 is the initial length of side and Lf is the length of side after shrinking. Shrink tension : the shrink force, which is the force released by the material during the heating/shrinking process, when referred to the film thickness unit is indicated as shrink tension. It does not exist a standard method to evaluate it. It has therefore been measured by the following internal method : specimens of the films (2.54 cm x 14.0 cm) are cut in the longitudinal and transverse direction and clamped between two jaws, one of which is connected to a load cell. The two jaws keep the specimen in the centre of a channel into which an impeller blows heated air and three thermocouples measure the temperature. The signal supplied by the thermocouples is amplified and sent to an output connected to the "X" axis of a X/Y recorder. The signal supplied by the load cell is amplified and sent to an output connected to the "Y" axis of the XY recorder. The impeller starts blowing hot air and the force released by the sample is recorded in grams. The temperature is increased at a rate of 2°C/s. As the temperature increases the pen draws on the X/Y recorder the measured profile of the shrink force versus the temperature thus producing a curve of the shrink force (expressed in g) versus temperature (°C). By dividing the values thus recorded and multiplied by 10~ 3 , by the specimen width (expressed in cm), the shrink force (in Kg/cm) is obtained. By further diving it by the thickness (in cm) of the sample, it is obtained the shrink tension, in kg/cm 2 , at the temperature considered. Haze : haze is defined as the percentage of transmitted light which is scattered forward while passing through the sample and is measured by ASTM D 1003 (Method A). Gloss : the film gloss, i.e. the surface reflectance of a specimen is measured according to ASTM D 2457 - 90 at a 60° angle. Tensile strength : a measure of the force required, under constant elongation, to break a specimen of the film, has been evaluated by ASTM D 882. Elongation : a measure of the percent extension required to break a specimen of the film, has been evaluated by ASTM D 882. Modulus : it has also been evaluated by ASTM D 882 - Method A (these last three tests relate to the mechanical properties of the film) Bond : the load necessary to separate two layers of a structure in a partially delaminated sample, 25 mm wide and 100 mm long, is measured and given as an indication of the interlayer adhesion. In the specific case the bond between the core layer (a) and the tie layer (c) has been measured. Broadening of the sealing window : The broadening of the sealing window has been evaluated using a Omori S5150J Horizontal Form-Fill- Seal machine equipped with a heat sealing bar. The temperature of the sealing bar has been varied, starting from an average value of 140°C, by decreasing it stepwise by 10°C at the time. The strength of the seal has been evaluated on batches of 50 packages per each sealing temperature and it has thus been determined the lowest sealing temperature that still provides for an effective seal. Then the temperature of the sealing bar has been increased stepwise by 10°C at the time starting from the average value of 140°C, and the highest sealing temperature, i.e. the highest temperature at which the seal does not cut the film, has been determined on batches of 50 packages per each sealing temperature. Leaker rate : the improved heat-sealing performance of the films according to the present invention has been evaluated by means of a simple technique of leak detection (Dopack system test) based on ASTM D 3078-84. In particular this test method evaluates the incidence of "leakers", i.e. seal defects such as pinholes which develop at or near the seal through which gases escape from or enter into the package. For each film, one hundred samples are randomly taken from a production of 600 packs obtained on the same packaging machine under the same packaging conditions. Groups of four packs are then tested by immersing them in a plastic cylinder filled with water, closing the container, drawing the vacuum and creating a difference in pressure of 0.3 bar. In the presence of pinholes, air which has been trapped within the package will escape giving raise to small bubbles that can be easily detected and localised. The number of pinholes or "leakers" that is then determined is called "leaker rate". These characteristics have been evaluated on a llapak Delta 2000SB HFFS machine with impulse sealing using Teflon™ coated sealing wires, a sealing temperature of 170°C, a line speed of 55 packages per minute (corresponding to 18 m/min) and sealing pressure of 2.6 bar (Condition A) or 3.0 bar (Condition B). These sealing conditions are more drastic than the standard sealing conditions and allow to better discriminate the sealing behaviour of the tested structures. Hot Tack : the hot seal strength has been evaluated by a laboratory method that simulates what happens on a packaging plant. It is measured by means of a dynamometer equipped with hot bars (Hot Tack Tester by Top Wave) set as on an industrial packaging machine (in the present case : 2.6 bar sealing pressure, 100 ms impulse time, and 250 ms cooling time) wherein the sealing temperature is varied. Then the strength of the seal, in N/mm 2 , is evaluated on 25 mm wide samples and the sealing temperature range within which the seal strength is above a given threshold is determined. Example 1 (i) A symmetrical five layer structure was extruded, irradiated at about 70 KGrays and biaxially oriented out of hot air at about 116°C. The resultant 25 μ thick film had a layer ratio of about 3/1/1/1/3 and the following general structure : A1 +B1 +C1 /D/E/D/A1 +B1 +C1 wherein A1 is a heterogeneous ethylene-α-olefin copolymer with d = 0.920 g/cc and MFI = 1.0 g/10' (Dowlex™ 2045E by Dow) B1 is a heterogeneous ethylene-α-olefin copolymer with d = 0.935 g/cc and MFI = 2.6 g/10' (Dowlex™ SC2102 by Dow) C1 is a heterogeneous ethylene-α-olefin copolymer with d = 0.902 g/cc and MFI = 3.0 g/10' (Teamex™ 1000F by DSM) The A1+B1+C1 blend has 46.6 % of A1 , 25 % of B1 , 25 % of C1 , 3% of an anti-fog composition, and about 0.4 % of silica; D is a homogeneous ethylene-α-olefin copolymer (Taf er™ like) with d = 0.906 g/cc and MFI = 1.5 g/10', modified with maleic anhydride (m.p. 120°C) (ADMER™ AT1094E by Mitsui), and E is a blend of 90 % of an ethylene-vinyl alcohol copolymer (EVAL™ EC F151A from Marubeni) and 10 % of a nylon 6,12 (GRILON™ CF 6S from EMS). (ii) The obtained film has been submitted to a heat treatment that is carried out on a processing unit consisting of the sequence of 6 stainless steel Gross Equatherm heated rollers and two cooled rollers, 16-cm in diameter and 203-cm in length, disposed in such a way that the contact time of the film web with each roller was 0.26 s and the total heating time 1.56 s. The temperature (°C) in the three heating zones, each comprising two rollers, was 68.5 - 68.5 - 65.3°C respectively while that in the cooling zone was 20°C. This heat treatment modifies the shrink properties of the film and in particular it substantially reduces the maximum shrink force in the transverse direction of the film leaving almost unaltered the % free shrink. This treatment does not modify the film sealing properties. Example 2 (i) A symmetrical five layer structure was extruded, irradiated at about 80 KGrays and biaxially oriented out of hot air at about 116°C. The resultant 25 μ thick film had a layer ratio of about 3/1/1/1/3 and the following general structure : A1 +B1 +C2/D/E/D/A1 +B1 +C2 wherein A1 and B1 are as defined in Example 1 and C2 is a homogeneous ethylene-α-olefin copolymer with d = 0.902 g/cc and MFI = 1.0 g/10' (m.p. 100°C) (AFFINITY™ PL1880 by Dow). The A1 +B1+C2 blend contains 46.6 % of A1 , 25 % of B1 , 25 % of C2, 3% of an anti-fog composition, and about 0.4 % of silica; D and E are as in Example 1. (ii) The obtained film has been submitted to a heat treatment as in part (ii) of Example 1. Example 3 (i) A symmetrical five layer structure was extruded, irradiated at about 60 KGrays and biaxially oriented out of hot air at about 116°C. The resultant 25 μ thick film had a layer ratio of about 3/1/1/1/3 and the following general structure : A1 +B1 +F1 /D/E/D/A1 +B1 +F1 wherein A1 and B1 are as defined in Examples 1 and 2, and F1 is an ethylene-vinyl acetate copolymer (about 4 % VA). The A1+B1+F1 blend contains 46.6 % of A1 , 25 % of B1 , 25 % of F1 , 3% of an anti-fog composition, and about 0.4 % of silica; D and E are as in Examples 1 and 2. (ii) The obtained film has been submitted to a heat treatment as described in part (ii) of Example 1 wherein however the temperature of the heating zones was 80 - 80 - 75°C respectively. Table I below reports the characteristics of the films of Examples 1 , 2, and 3. While it can be noted that the mechanical, optical, and shrink characteristics of the films of Examples 1 and 2 are comparable to those of the film of Example 3 that differs therefrom in the composition of the skin layers containing an ethylene-vinyl acetate copolymer instead of Component C, the sealability characteristics of the films of Examples 1 and 2 are remarkably better than those of the film of Example 3, both in terms of width of the sealing window and in terms of leakers rate. Table I Film of Ex. no. Modulus (L-T 1 ) 5500-4500 5500-4500 5300-4400 (kg/cm * ) Tensile strength 800-650 800-650 800-650 (L-T) (kg/cm 2 ) Elongation 110-140 110-150 110-150 (L-T) (%) Free shrink 65-56 64-56 60-56 (L-T) (%) Shrink force 0.06-0.035 0.06-0.035 0.06-0.04 (L-T) (kg/cm) Haze 5.1 5.5 Gloss (%) 120 121 122 Bond (g/25 mm) 190 190 190 Leakers rate (%) Condition A 7 9 13 Condition B 0 0 10 Sealing window 120-160 120-170 130-160 (°C) Hot tack 15 15 10 <°C) Example 4 1 L = longitudinal, T = transversal The film of Example 4 has been obtained by following the procedure described in Example 1 but using for the outer layers a blend of two components : A1 and C1 containing 71.6 % of A1 and 25 % of C1 , 3 % of an antifog composition and about 0.4 % of silica. Table II that follows reports the mechanical characteristics of the films of Examples 1 , 2, and 4. The worsening of the mechanical properties and particularly of modulus and elongation of the film of Example 4 with respect to the films of Examples 1 and 2, that differ therefrom only for the presence of Component B1 in the outer layers, is apparent. Table II Film of Example no. Modulus (L-T) (kg/cm ) 5500-4500 5500-4500 4500-3900 Tensile strength (L-T) (kg/cm ) 800-650 800-650 800-650 Elongation (L-T) (%) 110-140 110-150 120-180 Example 5 The film of Example 5 has been obtained by following substantially the same procedure described in Example 1 i) but replacing C1 with C3, a homogeneous ethylene-α-olefin copolymer with d = 0.915 g/cc and MFI = 1.0 g/10' (m.p. 108°C) (AFFINITY™ FM1570 by Dow). Example 6 The film of Example 6 has been obtained by following substantially the same procedure described in Example 1 i) but replacing C1 with C4, a homogeneous ethylene-α-olefin terpolymer with d = 0.900 g/cc and MFI = 1.2 g/10' (m.p. 94 °C) (EXACT™ 3033 by Exxon). Example 7 The film of Example 7 has been obtained by following substantially the same procedure described in Example 1 i) but replacing C1 with C5, a homogeneous ethylene-α-olefin terpolymer with d = 0.902 g/cc and MFI = 2.0 g/10' (m.p. 96 °C) (EXACT™ 9042 by Exxon). Example 8 The film of Example 8 has been obtained by following substantially the same procedure described in Example 1 i) but replacing C1 with C6, a heterogeneous ethylene-α-olefin copolymer with d = 0.912 g/cc and MFI = 3.2 g/10' (ATTANE™ 4202 by Dow). Table III below compares the sealability properties, in terms of leakers rate (Condition A), of the films of Examples 5, 6, and 7. Table III Film of Example no. 5 6 7 Leakers rate (%) 2 8 1 Examples 9-12 In the following Examples the influence of the resins used in the tie layers of a film otherwise identical has been evaluated. By following the procedure of Example 1 i) and replacing resin D with the materials indicated in following Table IV as D1 to D4, the films of Examples 9 to 12 have been obtained. For each of these films in the same Table it is reported the bond between the core layer and the tie layer. By using modified polyolefins based on homogeneous ethylene-α-olefin copolymers with density < 0.910 g/cc in the tie layers a significant increase in bond is obtained. Table IV Film of Example no. Resin employed in the tie layer Bond (g/25 mm) D1 = maleic anhydride modified homo- 140 geneous ethylene-α-olefin copolymer (d = 0.903 g/cc - MFI = 1.3 g/10' - ADMER™ AT1093E by MITSUI) 10 D2 = maleic anhydride modified homo- 110 geneous ethylene-α-olefin copolymer (d = 0.905 g/cc - MFI = 1.5 g/10' - ADMER™ AT1072E by MITSUI) 11 D3 = maleic anhydride modified ethyl- 80 ene-α-olefin copolymer (d = 0.910 g/cc MFI = 2.7 g/10' -ADMER™ NF520E by MITSUI) 12 D4 = maleic anhydride modified ethyl- 90 ene-α-olefin copolymer (d = 0.911 g/cc MFI = 1 .3g/10' -ADMER™ AT1073 by MITSUI) Comparative Example 13 The film of this Comparative Example has been obtained by following substantially the same procedure as in Example 3 with the only difference that D has been replaced with D5, a maleic anhydride modified heterogeneous ethylene-α-olefin copolymer with d = 0.920 g/cc (BYNEL™ CXA4104 by DuPont). Following Table V reports both the bond between the core layer and the adhesive layer and the leakers rate of the film of Comparative Example 13 as well as of that of Example 3. It can thus be noticed that in the film of Example 3 there is an increase in the adhesion between the layers and also, unexpectedly, a remarkable improvement of the sealability, in terms of leakers rate. Table V Film of Example 3 Comparative Example 13 Bond (g/25 mm) 190 85 Leakers rate (%) Condition A 13 60 Condition B 10 20 The above comparison shows that using a modified polyolefin based on a homogeneous ethylene-α-olefin copolymer with a density of from about 0.900 g/cc to about 0.908 g/cc, particular advantages in terms of sealability are obtained not only when the outer layers comprise a ternary blend as in the preferred films of the present invention but also when the outer layers in general contain an ethylene-α-olefin copolymer. Example 14 The film of Example 14 is obtained by following substantially the same procedure as in Example 1 i) but increasing the % of A1 from 46.5 to 56.5 and decreasing the % of B1 and C1 from 25 to 20 %. Example 15 The film of Example 15 is obtained by following substantially the same procedure of Example 5 but changing the amount of A1 , B1 , and C5 in the outer layer as follows : A1 46.5 %, B1 35 %, and C5 15 %. Example 16 The film of Example 16 is obtained by following substantially the procedure of the foregoing Example but replacing D with D1 as defined in Example 9.

Claims: Claims 1) A thermoplastic multilayer packaging film comprising (a) an oxygen barrier core layer comprising ethylene-vinyl alcohol copolymer; (b) two outer layers, and (c) two adhesive layers each of which disposed between the core layer (a) and each of the two outer layers (b), characterized in that at least one of the outer layers comprises a blend of three components A, B, and C, wherein Component A is a homogeneous or heterogeneous ethylene-α-olefin copolymer with density comprised between 0.915 g/cc and 0.925 g/cc, Component B is a homogeneous or heterogeneous ethylene-α-olefin copolymer with density > 0.925 g/cc, and Component C is a homogeneous or heterogeneous ethylene-α-olefin copolymer with density < 0.915 g/cc. 2) The film of claim 1 wherein each of the adhesive layers (c) directly adheres to the core layer (a). 3) The film of claim 1 wherein polyamide comprising layers (d) directly adhere to core layer (a). 4) The film of claim 3 wherein each of the adhesive layers (c) directly adheres to the surface of each of the polyamide comprising layers (d) that does not directly adhere to the core layer (a). 5) The film of claims 1 , 2, or 4 wherein both outer layers (b) comprise a blend of three components A, B, and C. 6) The film of claim 1 wherein Component A is present in the higher weight percent in the ternary blend of the outer layer (b). 7) The film of claim 6 wherein Component A is present in the outer layer (b), in an amount of from about 35 to about 80 % by weight, preferably from about 40 to about 70 %, and even more preferably from about 45 to about 65 %, based on the weight of the ternary blend. 8) The film of claim 6 wherein Component B and Component C, each independently, are present in the outer layer (b) in an amount of from about 10 to about 35 % by weight, preferably from about 15 to about 30 %, and even more preferably from about 20 to about 25 %, based on the weight of the ternary blend. 9) The film of claim 1 wherein the density of Component A is comprised between about 0.918 g/cc and about 0.922 g/cc. 10) The film of claim 1 wherein the density of Component B is higher than about 0.928 g/cc, and preferably is comprised between about 0.928 g/cc and 0.938 g/cc. 11) The film of claim 1 wherein the density of Component C is comprised between about 0.895 g/cc and about 0.912 g/cc, and preferably between about 0.898 g/cc and about 0.905 g/cc. 12) The film of claim 1 wherein Component A is a heterogeneous ethylene- α-olefin copolymer. 13) The film of claim 1 wherein Component B is a heterogeneous ethylene- α-olefin copolymer. 14) The film of claim 1 wherein Component C is a homogeneous ethylene- α-olefin copolymer. 15) The film of claim 1 which is heat-shrinkable. 16) The film of claim 15 characterised in that it has a % free shrink, at 120°C, of at least 20 % in at least one direction, preferably of at least 30 % in at least one direction, and even more preferably of at least 40 % in at least one direction. 17) The film of claim 2 characterised in that it has five layers wherein the surface of each of the adhesive layers (c) that does not adhere to the core layer (a), directly adheres to the outer layer (b). 18) The film of claim 2 characterised in that it comprises one or more additional layers between the adhesive layers (c) and the outer layers (b). 19) The film of claim 18 wherein said additional layers comprise recycle material from the same film optionally blended with a compatibilizer. 20) The film of claims 1 , 2, or 4 characterised in that the adhesive layers (c) comprise modified homogeneous ethylene-α-olefin copolymers with a density of from about 0.880 g/cc and about 0.908 g/cc. 21 ) The film of claim 1 further characterised in that it is cross-linked. 22) The film of claim 21 wherein cross-linking is achieved by irradiation. 23) Thermoplastic multilayer film with improved sealability properties comprising a core layer comprising an ethylene-vinyl alcohol copolymer or a polyamide, outer layers comprising an ethylene-α-olefin copolymer, and adhesive layers between the core layer and the outer layers, characterised in that at least one of said adhesive layers comprises a modified homogenous ethylene-α-olefin copolymer with a density of from about 0.900 g/cc and about 0.908 g/cc. 24) The film of claim 23 wherein the core layer comprises an ethylene- vinyl alcohol copolymer. 25) The film of claims 23 or 24 wherein both adhesive layers comprise a modified homogenous ethylene-α-olefin copolymer with a density of from about 0.900 g/cc and about 0.908 g/cc. 26) A method of improving the seal strength in a package made from a thermoplastic multilayer film comprising a core layer comprising EVOH or a polyamide and a sealing layer comprising an ethylene-α-olefin copolymer, which method comprises adhering the core layer to the sealing layer by means of an adhesive layer comprising a modified homogenous ethylene-α-olefin copolymer with a density of from about 0.900 g/cc and about 0.908 g/cc.

Inventors: CIOCCA PAOLO, FORLONI ROBERTO, CIOCCA, PAOLO, FORLONI, ROBERTO
Applicants: CIOCCA PAOLO, FORLONI ROBERTO, GRACE W R & CO, CIOCCA, PAOLO, FORLONI, ROBERTO, W.R.GRACE & CO.-CONN.
Application year: 1997
Main classification: B32B27
IPC codes: B32B27