NZ625510B2

NZ625510B2 - Multilayer films

Info

Publication number: NZ625510B2
Application number: NZ625510A
Authority: NZ
Inventors: Roya Khalil; Nicholas John Mccaffrey; Brendan Morris; Nicholas Roy Oakley
Original assignee: Plantic Technologies Limited
Priority date: 2011-12-22
Filing date: 2012-05-23
Publication date: 2015-03-03

Abstract

Disclosed is a multilayer film with two types of layers. The multilayer film comprises at least one starch layer comprising a modified starch; and at least one other layer having a water vapour permeability coefficient less than 1 g.mm/m2.24hr.atm measured at 38°C and 90% relative humidity. The total thickness of the at least one starch layer is greater than 30% of the total thickness of the multilayer film and the modified starch has a degree of substitution less than 1.5. l thickness of the at least one starch layer is greater than 30% of the total thickness of the multilayer film and the modified starch has a degree of substitution less than 1.5.

Description

MULTILAYER FILMS FIELD OF THE ION The present invention relates to ayer films having a starch based layer and to methods of their preparation. The films find particular, although not exclusive, use in the packaging of foodstuffs.

OUND TO THE INVENTION Multilayer films find widespread use as a packaging material in the food industry. In such application not only does the packaging material have to contain the foodstuff, it must also preserve the product. Foods are by their nature perishable and the properties of the packaging material will greatly impact the useful shelf life of a given foodstuff. Chemical changes, such as oxidation, and microbiological growth can be accelerated in the presence of oxygen.

Accordingly, controlling the oxygen content in a package or the rate of oxygen ingress into a package is often one of the most critical attributes of barrier packaging.

Multilayer barriers are usually constructed with a polar polymer as an internal layer which is covered with apolar polymer. The former acts as a gas barrier, and the latter as a hobic skin having a low water vapour transmission rate to prevent fast water absorption in the internal layer. Polyolefin 2O skin layers covering a polar polymer layer are commonly ed, for example, a polyethylene skin covering a polyethylene—vinyl alcohol copolymer (PE-EVOH).

EVOH copolymers show good oxygen barrier ties at low humidity, typically in the range of O to 60%. However, their gas barrier property deteriorates dramatically under high humidity conditions when the humidity is in the range of 75 to 90%. In fact, due to the polar nature of EVOH, such films generally exhibit poor moisture r. Therefore, EVOH is typically laminated with polyolefins on both sides to provide barrier properties for practical packaging ations in order to protect the EVOH from humidity effects. However, over time sufficient moisture may permeate the polyolefin hydrophobic skin such that the oxygen r properties of the EVOH layer will be mised.

EVOH materials also require the use of on promoters and/or tie- iayer resins in order for them to bond adequately to polyolefin substrates. Without such tie resins, EVOH materials tend to peel off easily from the polyolefin substrate resulting in loss of barrier properties and poor ance.

A further disadvantage of EVOH is that it is relatively expensive.

Additionally, from a renewable standpoint, EVOH is fully derived from fossil fuels.

It would be desirable to provide a multilayer film that has excellent barrier properties, particularly at high humidity and which utilises inexpensive, renewable materials.

Y OF THE INVENTION According to a first aspect there is ed a multilayer film sing: (a) at least one starch layer comprising a modified starch; and (b) at least one other layer having a water vapour permeability coefficient less than 1 g.mm/m2.24hr.atm measured at 38°C and 90% ve humidity; and wherein the total thickness of the at least one starch layer is greater than 20% of the total ess of the multilayer film and wherein the modified starch has a degree of substitution less than 1.5.

Preferably the water vapour permeability coefficient of the at least one other layer is less than 0.5 g.mm/m2.24hr.atm measured at 38°C and 90% relative humidity, more preferably less than 0.2 g.mm/m2.24hr.atm measured at 38°C and 90% relative humidity. 2O Preferably the total thickness of the at least one starch layer is greater than % of the total ess of the multilayer film, more preferably greater than 40% of the total thickness of the multilayer film, even more preferably greater than 50% of the total thickness of the multilayer film. in some embodiments the total thickness of the at least one starch layer is r than 60% of the total thickness of the multilayer film.

The multilayer film has a low oxygen permeability coefficient (OPC). In some embodiments, the multilayer film has an OPC less than 0.6 cm3 mm/m2.24h.atm at 50% relative humidity (RH). Preferably the multilayer film has an OPC of less than 0.3 cm3 mm/m2.24h.atm at 50% RH and more preferably an 3O OPC of less than 0.2 cm3 mm/m2.24h.atm at 50% RH. Most preferably, the multilayer film has an OPC of less than 0.1 cm3 mm/m2.24h.atm at 50% RH and particulary preferably the ayer film has an OPC of less than 0.05 cm3 mm/m2.24h.atm at 50% RH.

In some embodiments, the ayer film has an OPC less than 1.2 cm3 mm/m2.24h.atm at 75% relative humidity (RH). Preferably the multilayer film has an OPC of less than 0.6 cm3 mm/m2.24h.atm at 75% RH and more preferably an OPC of less than 0.2 cm3 mm /m2.24h.atm at 75% RH. Most ably, the multilayer film has an OPC of less than 0.1 cm3 mm/m2.24h.atm at 75% RH and particulary preferably the multilayer film has an OPC of less than 0.05 cm3 mm/m2.24h.atm at 75% RH.

In some embodiments, the OPC remains below 0.05 cm3 mm/m2.24h.atm at 50% RH, for extended s of time. Preferably the OPC remains below 0.05 cm3 mm/m2.24h.atm at 50% RH for at least ten days, more preferably the OPC remains below 0.05 cm3 mm/m2.24h.atm at 50% RH for 20 days, most preferably the OPO remains below 0.05 cm3 mm/m2.24h.atm at 50% RH for thirty days. In a particularly preferred embodiment the OPC remains below 0.05 cm3 mm/m2.24h.atm at 50% RH for thirty days.

Accordingly, the multilayer films have an enhanced performance in respect of oxygen barrier properties over long periods of time. While not wishing to be bound by theory it is ered that the high moisture ty of the at least one starch layer acts to extend the lifetime of the oxygen barrier effect, even when moisture levels within the at least one starch layer are relatively high. 2O Such longevity in t of gas barrier performance is clearly desirable in extending the shelf life of packaged perishable foodstuffs.

Advantageously, from a renewable perspective the multilayer film contains a high proportion of biodegradable starch.

The thickness of the multilayer film and of each layer within the multilayer film may vary depending on the exact nature of the end use application.

Preferably, the total thickness of the multilayer film is between 10 and 1000 microns. In one embodiment the total thickness of the multilayer film is n and 100 microns, more preferably n 20 and 80 microns. In another embodiment the total thickness of the multilayer film is between 100 and 1000 3O s more preferably between 200 and 800 microns.

In some embodiments, the total thickness of the at least one starch layer is between 5 and 600 microns. In one embodiment, the total thickness of the at least one starch layer is between 5 and 50 microns, ably between 10 and 40 microns. In other embodiments, the total thickness of the at least one starch layer is n 100 and 600 microns, preferably between 150 and 450 microns.

In some embodiments, the total thickness of the at least one other layer is between 5 and 400 microns. In one embodiment, the total thickness of the at least one other layer is between 5 and 25 microns preferably between 10 and 20 microns. in another embodiment, the total thickness of the at least one other layer is between 30 and 400 microns, preferably between 30 and 300 microns.

In a preferred embodiment the at least one starch layer has a total ess between 100 and 600 micron and the at least one other layer has a total thickness between 10 and 400 micron. In another preferred embodiment the at least one starch layer has a total thickness between 100 and 400 micron and the at least one other layer has a total thickness n 40 and 250 micron.

In another preferred embodiment the at least one starch layer has a total thickness between 10 and 60 micron and the at least one other layer has a total thickness between 5 and 40 micron.

Other Layer The other layer(s) may be chosen to impart certain physical and tic properties to finished multilayer film. These properties may include, for example, antifog, strength, heat sealability, colour, or clarity. In some embodiments particularly preferred other layers are those having a low water vapour transmission rate.

In some embodiments the at least one other layer comprises a polyolefin, polyethylene terephthalate, nylon, nylchloride and polyvinylidene dichloride or mixtures thereof. In one ment each of the other layers may comprise a mixture of components. In other embodiments one or more of the other layers may consist of multiple layers of different materials. In further embodiments each of the other layers may comprise different materials.

In some embodiments le efins for the preparation of the polyolefin film layer are selected from the group consisting of ethylene homopolymers, ene homopolymers, interpolymers of ethylene and ene and interpolymers of ethylene or propylene with one or more C4-C1o d- olefins, cyclic olefin polymers and copolymers, lly orientated polypropylene, and mixtures thereof.

In some embodiments suitable polyolefins are selected from copolymers of ethylene or propylene and one or more ci-olefins. Both high density hylenes and linear low density polyethylenes may be preferably utilised.

Suitable linear low density polyethylenes (LLDPE) include copolymers of ethylene and c-olefins (about 5 to about 15 wt.%). Alpha-olefins include 1-butene, 1-hexene, 1-octene, and the like, and mixtures thereof. The density of LLDPE is within the range of about 0.865 to about 0.925 g/cm3 Suitable high density polyethylenes (HDPE) include ne homopolymers and copolymers of ethylene and ins (about 0.1 to about 10 wt. %). Suitable alpha-olefins include 1-butene, 1-hexene, 1—octene, and the like, and mixtures thereof. The density of HDPE is preferably from about 0.940 to about 0.970 g/cms.

Suitable cyclic olefin polymers and copolymers include polymers of norbornene or tetracyclododecene and copolymers of norbornene or tetracyclododecene with one or more d-olefins. Examples are cyclic olefin polymers are Topas (Ticona) and Apel (Mitsui).

In some embodiments blends of polyoleiins and other polymers may be advantageously employed. Cast opylene (cPP) or biaxially oriented polyprOpylene (BOPP) may be chosen for improved strength and low WVTR.

Polyethylene terephthalate (PET) may be chosen for strength and ability.

In other ments ed polyoleiins, such as d polyolefins, may be utilised. A preferred grafted polyolefin is a maleic anhydride d pclyolefin.

Starch Layer The multilayer film comprises at least one starch layer comprising a modified starch, wherein the modified starch has a degree of tution less than 1.5. The degree of substitution defines the average number of substituents per anhydroglucose unit. Accordingly, by definition, the maximum possible degree of substitution of starch is 3.0. 3O In one embodiment the at least one starch layer comprises a high amylose starch. Preferably, the amount of high amylose starch is between 5 and 80% by weight based on the total weight of the starch layer. in another embodiment the modified starch is chemically ed so as to replace hydroxyl functionality with functionality selected from the group consisting of ethers and esters and mixtures thereof. Preferred esters comprise heptanoate or lower homologues. Particularly preferred esters include acetate.

In a further embodiment the modified starch is ed to e a hydroxyalkyl C245 group or modified by reaction with an ide of a carboxylic acid. Preferably the modified starch is modified to include a hydroxy C2-4 group.

More preferably the modified starch is modified to include a hydroxy propyl group.

In a yet further embodiment the at least one starch layer comprises a water e polymer. Preferably, the starch layer comprises 1 to 20% by weight of a water soluble polymer, more preferably from 4 to 12% by weight of a water soluble polymer. Exemplary, but non-limiting, water soluble polymers are selected from the group consisting of polyvinylacetate, polyvinyl alcohol or mixtures thereof. Polyvinyl alcohol is a particularly preferred water e polymer.

In some embodiments the at least one starch layer may comprise water, preferably up to 20% by weight water, more preferably up to 12% by weight water. In some embodiments the water may serve as a plasticiser.

In some embodiments the re content of the at least one starch layer is generally the equilibrium moisture content at the environmental %RH. For example, the equilibrium re content ranges from about 4% at low %RH to more than 15% at high %RH.

In a still yet further embodiment the at least one starch layer comprises one or more polyol plasticisers, preferably up to 20% by weight of one or more polyol plasticisers, more preferably up to 12% by weight of one or more polyol plasticisers. Exemplary, but non-limiting, polyol plasticisers are selected from the group consisting of sorbitol, glycerol, maititol, xylitol, and mixtures thereof.

In another embodiment the at least one starch layer may also comprise up to 50% by weight of natural unmodified .

In some embodiments the at least one starch layer comprises mixtures of starches and/or ed es, for example, mixtures of high and low amylose , wherein one or more of the starch components may be ed.

In a further embodiment the at least one starch layer comprises a lubricant.

Preferred lubricants are C1222 fatty acids and/or 012-22 fatty acid salts. Preferably, the 012.22 fatty acid and/or a 012.22 fatty acid salt are present in an amount up to % by weight.

In some embodiments the at least one starch layer comprises one or more nanomaterials. Preferably, the terials are exfoliated within a starch nanocomposite. Exemplary nanomaterials include clays and modified clays particulariy ‘hydrophobically modified layered silicate clays'. Preferred clays include montmorillonite, ite, beidelite, mica, hectorite, saponite, nontronite, sauconite, vermiculite, ledikite, magadite, kenyaite, stevensite, volkonskoite or a mixture thereof.

A ‘hydrophobically modified layered silicate clay’ or ‘hydrophobic clay’ is preferably a clay ed by ge with a surfactant comprising long chain alkyl groups such as a long chain alkylammonium ion, for e, mono- or di- C12-ng alkylammonium ion, wherein polar substituents such as hydroxyl or yl are not ed to the long chain alkyl. Examptes of le clays include CLOISITE® 20A or CLOISITE® 25A from Southern Clay Products lnc.

In some embodiments the starch layer and/or the other layer may comprise colourants.

Adhesive In some embodiments the at least one other layer may be fixed to the at least one starch layer through use of a suitable adhesive. This assists in minimising slip and therefore maintaining excellent r performance.

Numerous suitable adhesives would be readily apparent to those having skill in the present art. Preferably the adhesive is selected so as to chemically bond to the at least one starch layer. Preferred adhesives comprise one or more polyurethanes.

Advantageously, the use of an adhesive overcomes or ses the need for modified or grafted other layers to be utilised as tie layers. Accordingly, for example, standard film polyethylene grades may be successfully ed as polyolefin other layers in the multi-layer film. This is desirable from a cost consideration.

Other suitable adhesives include EVA copolymers, acrylic copolymers and terpolymers, ionomers, metallocene derived polyethylene, ethylene acrylic ester terpolymers and ne vinyl acetate terpolymers.

Those d in the art will be familiar with other adhesive lamination technology that would be suitable for adhering various types of plastics, including heat activated and UV activated systems. Exemplary adhesives include, polyurethane, epoxy, nylon, acrylic and acrylate.

Method of Preparation of the Multilayer Film The multilayer film can be made by a variety of ses. The multilayer film can be made by co-extrusion, coating, and other laminating processes. The film can also be made by casting or blown film processes.

Coextrusion tends to use tie layers, and utilises modified other layers, such as modified ed) polyolefins. Coextrusion is generally able to achieve thinner overall gauges. Lamination is more suitable for thicker multilayer films utilising an adhesive.

In one embodiment a three layer film is provided comprising an inner starch layer and two outer polyolefin . In other embodiments adhesive layers may be employed between the starch layer and the polyolefin layers thus yielding a five layer film.

Applications It should be understood by those with skill in the art that a three or five layer film is only one of many le embodiments that s starch and other layers. The number of layers and their relative thicknesses may be adjusted depending on the function or e of the film.

Additionally, further film layers sing other materials commonly utilised in barrier film applications may be envisaged. Exemplary further film layers include metallised films, non-polymer films and the like.

The multilayer film has many uses including grocery bags, stretch-wraps, food packaging films, package containers, package lids where low water vapour and oxygen transmission rates are required.

Accordingly, in a further aspect there is provided a use of a multilayer film according to any of the entioned embodiments in packaging, preferably in packaging foodstuffs.

In a yet further aspect there is provided an article of manufacture sing the multilayer film according to any one of the aforementioned embodiments. A preferred article of manufacture is a food package, such as containers, lids, bags, h-wraps and films.

Throughout this specification, use of the terms “comprises" or “comprising” or grammatical variations thereon shall be taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features. integers, steps, components or groups thereof not specifically mentioned.

DETAILED DESCRIPTION OF THE ION It will now be convenient to be the invention with reference to particular ments and examples. These embodiments and examples are illustrative only and should not be construed as limiting upon the scope of the invention. It will be understood that variations upon the described invention as would be apparent to the d addressee are within the scope of the invention.

Similarly, the present invention is capable of finding application in areas that are not explicitly recited in this document and the fact that some applications are not specifically bed should not be considered as a limitation on the overall applicability of the invention.

Polyolefins Suitable LLDPE, HDPE and polypropylene can be produced by a Ziegler, single-site, or any other olefin polymerization catalyst. Ziegler catalysts and co— catalysts are well known in the art. Metallocene single-site catalysts are transition metal compounds that contain cyclopentadienyl (Cp) or Cp derivative ligands. For example, US. Pat. No. 4,542,199, teaches the preparation of metallocene catalysts. Non-metallocene single-site catalysts containing heteroatomic s, e.g., boraaryl, pyrrolyl, azaborolinyl or quinolinyl are also well known in the art.

The HDPE can also be multimodal. By "multimodal" it is meant that the polymer comprises at least two components, one of which has a relatively low molecular weight, the other a relatively high molecular . The odal polyethylene can be produced by rization using conditions that create a multimodal r product. This can be lished by using a catalyst system with two or more different catalytic sites or by using two or multi-stage polymerization processes with different process conditions in the different stages (e.g. ent temperatures, pressures, rization media, hydrogen partial pressures, etc). odal HDPE may be produced by a multistage ethylene polymerization, using a series of rs, with mer addition in only one of the reactors.

Modified Starch A red modified starch component is hydroxypropylated amylose starch. Other substituents may be hydroxyethyi or hydroxybutyl to form hydroxyether substitutions, or anhydrides such as maleic phthalic or octenyl succinic anhydride can be used to produce ester derivatives. The degree of substitution (the average number of hydroxyl groups in a unit that are tuted) is ably 0.05 to 1.5. A preferred starch is a high amylose maize starch.

Another preferred starch is a high amylose tapioca starch. A preferred modified starch component is a hydroxypropylated high amylose starch (for example ECOFILM® marketed by National Starch and Chemical Company, or Gelose® A939 marketed by Penford).

The other starch component, if utilised, is any commercially available . This may be derived from, for example, wheat, maize, tapioca, potato, rice, oat, arrowroot, and pea sources. These starches may also be chemically modified.

Water Soluble Polymer The water soluble polymer component of the starch layer is preferably compatible with starch, water soluble, biodegradable and has a low melting point ible with the processing temperatures for starch. Polyvinyl alcohol is a preferred polymer but polymers of ethylene-vinyl alcohol, ethylene vinyl acetate or blends with nyl alcohol may be used. A preferred concentration range 4 to 12% by weight, more preferably 8% - 12%.

Plasticiser A range of plasticisers and humectants are useful additions to the starch layer, in order to aid processing and control and ize the mechanical properties of the barrier al, in particular in reducing dependency on moisture t and relative humidity. The desired plasticiser content depends primarily on the required processing behaviour during a xtrusion process and subsequent blowing or stretching processes as well as on the required mechanical properties of the end product.

Cost and food contact are important issues in choosing the appropriate plasticizer. The red plasticizer is a mixture of s, in particular sorbitol, and one or more other polyols particularly glycerol, maltitol, ol and l, although erythritol, ethylene glycol and diethylene glycol are also le. The plasticizer plays a triple role: 1. it provides le rheology for the extrusion compounding process and for the lamination process, 2. it positively affects the mechanical properties of the product and, 3. it may act as an anti-retrogradation or anti—crystallizing agent.

The preferred plasticizer content is up to 20% by weight of the starch layer ing on the particular application and co-extrusion or lamination process.

Sorbitol, glycerol and maltitol blends are particularly suitable for modifying the ical properties of the formulation, as is xylitol and blends of xylitol with sorbitol and glycerol. The larger the number of OH groups, the more ive the plasticiser is in reducing crystallisation. Sorbitol, maltitol and xylitol are particularly good humectants. Glycerol helps dissolve polyvinylalcohol during sing.

Crystallisation is observed when sorbitol is used on its own. Some polyols (sorbitol and ol in particular) may exhibit migration to the surface, where either an opaque crystalline film may form in the case of ol, or an oily film in the case of glycerol. Blending various polyols inhibits this effect to varying degrees. Stabilisation may be enhanced with the addition of glycerol monostearate and sodium stearoyl lactylate as emulsifiers. Furthermore, synergistic effects with salt result in stronger effects on mechanical properties.

Other Plasticizers Polyethylene glycol compounds may be used as emulsifying agents, plasticizers or humectants. Polyethylene oxide and polyethylene glycol alternately or er may also provide an increased water resistance, to prevent ng which may result in delamination in multi-layer structures (MLS).

An alternative plasticiser is epoxidized linseed oil or epoxidized soybean oil. Being hydrophobic these additives may improve moisture sensitivity of the material. These plasticisers, preferably stablilized with an emulsifying system, aid processing but do not result in a significant further reduction in Young's modulus.

Other plasticizers more commonly used in the PVC industry may be suitable. including tributyl citrate, 2,2,4 trimethyl-l,3-pentanediol diisobutyrate, and acetyl tri-ethyl citrate.

One may use up to 20% of a humectant or water binding agent or gelling agent which may act as a (co)plasticiser such as carrageenan, xanthan gum, gum arabic, guar gum or gelatine. Other humectants may be used such as sugar or e. Biopolymers such as eenan, typically used in food products as thickeners and partially soluble in cold water, fully soluble in hot water, are suitable to tailor mechanical properties. By binding water these components may have a significant plasticizing function. Gelatine may be added to improve the ical properties and reduce moisture sensitivity. n Gum has a high water holding capacity and also acts as an emulsifier and in starch compositions has an anti-retrogradation effect. Gum Arabic may also be used as a iser and film former, and the hydrophilic carbohydrate and hydrophobic protein enable its hydrocolloid emulsification and stabilization properties. Guar gum has similar anticrystallisation effects in starch compositions. Another suitable humectant is glyceryl triacetate.

Fatty acid and/or fatty acid salt Fatty acids and/or fatty acid salts may be used as lubricants. The starch layer preferably comprises between 0.1 to 1.5% by weight of a 012-22 fatty acid and/or a 012-22 fatty acid salt. The fatty acid and/or fatty acid salt component is more preferably present in concentrations of 0.6 to 1%. Stearic acid is a particularly preferred component. Sodium and potassium salts of stearic acid may also be used. Cost can be a factor in the choice of this component but , myristic, palmitlc, linoleic and behenic acids are all suitable.

Adhesive Polyurethane based adhesives are particularly suitable for fixing the other layer to the starch layer. The polyurethane ve may be prepared in situ through reaction of one or more isocyanates with the starch layer. Through reaction of the surface hydroxyl functions of the starch with isocyanate, urethane functions are . red isocyanates are diisocyanates. Those skilled in the art would be able to select suitable isocyanates from the wide range lly employed in the art of ethane synthesis.

Alternatively, the polyurethane adhesive may comprise one or more polyols. Such two component systems comprising diisocyanate and polyol are well known in the art.

The adhesives may or may not contain solvent. The solvent may be organic or water based.

Exemplary isocyanates include methylene diphenyl diisocyanate and toluene yanate. Exemplary s include polyether polyols such as polyethylene glycol or opylene glycol and ter polyols such as adipate based s.

EXAMPLES OTR was measured using ASTM F 1927-98 and WVTR was measured using ASTM F 1249-01. All component weights are sed on a dry basis.

Example 1 A starch film was prepared by extrusion processing of a mixture of 88.5% by weight ed starch (ECOFILM®, National Starch and Chemical Company), 9% by weight polyvinylalcohol (Elvanol® 71 —30), 2% by weight Cloisite 20A (Southern Clay Products) and 0.5% stearic acid and casting into a 300 pm sheet.

This was then adhesively ted on each side to 100 pm HDPE film using MOR Free PU adhesive (Rohm and Haas). The lamination was performed on a standard laminating machine.

Samples were conditioned for 2 weeks at 50% and 75 % RH (for OTR) and 38°C / 90% RH (for WVTR) and measured after equilibration.

Tables 1 and 2 collect the results.

TABLE 1 Nomlnal % oi Oxygen Transmission Rate Specimen thickness starch layer (ems/m224h at 23°C, 1 atm pure thickness (micron) oxygen) 50% RH PE/Starch/PE _—_O——_——005 75% RH_=— TABLE 2 Nominal % cl Water Vapour Transmission Specimen thickness starch layer Rate thickness (micron) (g/m2.24h at 38°C, 90%RH) Examples 2 & 3 A starch film was prepared by extrusion processing of a mixture of 88.5% by weight modified starch (ECOFILM®, National Starch and Chemical Company), 9% by weight polyvinylalcohol (Elvanol® 71 —30), 2% by weight Cloisite 20A (Southern Clay Products) and 0.5% c acid and casting into a 150 pm sheet.

This was then adhesively laminated on each side to 50 pm (Example 2) or 35 pm (Example 3) HDPE using a polyurethane ve system from Specialty 1O Adhesives and Coatings. The lamination was performed on a standard laminating machine.

Samples were conditioned for 2 weeks at 50% and 75 % RH (for OTR) and 38°C / 90% RH (for WVTR) and measured after bration.

Table 3 collects the results.

TABLE 3 Water Vapour Nominal % Oxygen Transmission Rate Transmission Rate of starch (cm3/m2.24h) (g/m2.24h at 38°C, layer 90%RH) thickness 75% RH Thickness 23°C n) PE/Starch/PE PE/Starch/PE Example 4 A starch film was prepared by ion processing of a mixture of 90.5% by weight modified starch (ECOFILM®, National Starch and Chemical Company), 9% by weight polyvinylalcohol ol® 71 -30) and 0.5% by weight stearic acid and casting into a 350 um sheet. This was then adhesively laminated on each side to 50 um HDPE using a polyurethane adhesive system from lty Adhesives and Coatings. The lamination was performed on a standard laminating Samples were conditioned for 2 weeks at 50% and 75 % RH (for OTR) and 38°C / 90% RH (for WVTR) and ed after equilibration.

Table 4 collects the s.

TABLE 4 Water Vapour Transmission Rate Nominal % Oxygen Transmission Rate of starch cm3/m2.24h g/m2.24h at 38°C, ”Y" 90%RH thickness 50% RH, Thickness 75% RH, Thickness Thickness WVTFi 23°C (micron) 23°C (micron) (micron) Example 5 A starch film was prepared by extrusion processing of a mixture of 90.5% by weight modified starch (ECOFILM®, National Starch and Chemical Company), 9% by weight polyvinyialcohol ( Elvanol ® 71-30) and 0.5% by weight stearic acid and casting into a 350 pm sheet. This was then vely laminated to 50 pm HDPE on one side, and an 80 pm polypropylene film on the other side using a polyurethane adhesive system from Specialty Adhesives and Coatings. The lamination was performed on a standard laminating machine.

The results are collected in Table 5.

TABLE 5 Water Vapour Transmission Oxygen Transmission Rate Ftate l «y cm3/m2.24h orsiamho 4h at 38°C, "W 90%RH thickness Thickness Thickness Thickness (micron) (micron) (micron) PE/Slarch/PP iaung Not measured Not measured permeanl ative Example 1 A starch film was ed by extrusion processing of a mixture of 88.5% by weight modified starch (ECOFILM®, National Starch and Chemical Company), 9% by weight polyvinylalcohol (Elvano|® 71 -30), 2% by weight Cloisite 20A (Southern Clay Products) and 0.5% stearic acid and casting into a 290 pm sheet.

Samples were conditioned for 2 weeks at 50% and 75 % RH, and OTR measured after equilibration. The results are collected in Table 6.

TABLE6 Oxygen Transmission Rate Specimen thickness cm3/m2.24h at 23°C, 1 atm pure oxygen micron 0.21 283 50% RH 0.21 Starch Sheet Comparative Example 2 A starch film was prepared by extrusion processing of 100% by weight modified starch (ECOFILM®, National Starch and Chemical Company), and casting into a 300 pm sheet. s were conditioned for 2 weeks at 50% and 75 % RH (for OTR) and 38°C / 90% RH (for WVTR) and measured after equilibration.

Table 7 shows the results.

TABLE 7 Water Vapour Oxygen Transmission Rate Transmission Rate cm3/m2.24h g/m2.24h at 38°C, 90%FIH 50% RH. Thickness 75% RH. Thickness Thickness 23°C (micron) 23°C (micron) n) 050 1 30 Starchsmet _“—_—— m————— Summary of Examples Table 8 collects the OTFi and OPV (oxygen permeation value) for each of the Examples. The OPV are normalised to 1 mm thick samples, based on the core starch layer thickness only.

TABLE 8 Core Skin Example ess Thickness OTR (50 %FIH) OPV (50% RH) OTR (75% RH) OPV (75% RH) micron micron cm’lm.24h cm.mmlm.24h.atm cm"/m224h cm’.mm/m24h.atm It is evident from the results that the multilayer films of Examples 1 to 5 show excellent barrier performance. It is noted that where the core starch layer is approximately 300 micron thick, OTR is ntially reduced in samples having outer layers, retative the performance of a starch layer alone. Thinner starch core layers have low OTR at high (75%) RH relative to starch alone. Starch layers alone, in the e of outer layers, indicate very high WVTR.

Claims

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

1. A multilayer film comprising: (a) at least one starch layer comprising a modified starch; and (b) at least one other layer having a water vapour permeability coefficient less than 1 g.mm/m2.24hr.atm measured at 38°C and 90% relative humidity; and wherein the total thickness of the at least one starch layer is greater than 30% of the total thickness of the multilayer film and n the modified starch has a degree of substitution less than 1.5.

2. The multilayer film according to claim 1 wherein the water vapour permeability coefﬁcient of the at least one other layer is less than 0.5 2.24hr.atm.

3. The multilayer film according to claim 1 wherein the water vapour permeability coefficient of the at least one other layer is less than 0.2 g.mm/m2.24hr.atm.

4. The multilayer film according to any one of claims 1 to 3 wherein the total ess of the at least one starch layer is greater than 40% of the total thickness of the multilayer film.

5. The multilayer film according to any one of claims 1 to 4 wherein the total thickness of the at least one starch layer is greater than 50% of the total ess of the multilayer film.

6. The multilayer film ing to any one of claims 1 to 5 wherein the at least one other layer comprises a efin, polyethylene terephthalate, nylon, polyvinylchloride and polyvinylidene dichloride or mixtures thereof.

7. The multilayer film according to claim 6 wherein the polyolefin is selected from the group consisting of ethylene homopolymers, propylene homopolymers, interpolymers of ethylene and propylene and interpolymers of ethylene or propylene with one or more C4-C10 a—olefins, cyclic olefin rs and copolymers, biaxially orientated polypropylene, chemically modified polyoleﬁns and mixtures thereof.

8. The multilayer film according to claim 6 n the polyolefin is selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, biaxially orientated polypropylene and mixtures thereof.

9. The multilayer film according to any one of claims 1 to 8 comprising an inner starch layer and two outer polyolefin layers.

10. The ayer film according to any one of claims 1 to 9 wherein the at least one starch layer is fixed to the at least one other layer by an adhesive.

11. The multilayer film according to claim 10 wherein the adhesive ses a polyurethane and/or polyurethane urea.

12. The multilayer film according to any one of claims 1 to 11 wherein the film has an oxygen permeability coefﬁcient (OPC) less than 0.6 cm3 mm/m2.24h.atm at 50% RH.

13. The multilayer film according to any one of claims 1 to 12 wherein the film has an oxygen permeability coefficient (OPC) less than 0.3 cm3 mm/m2.24h.atm at 50% RH.

14. The multilayer film according to any one of claims 1 to 13 n the film has an oxygen permeability coefficient (OPC) less than 0.1 cm3 mm/m2.24h.atm at 50% RH.

15. The multilayerfilm ing to any one of claims 1 to 14 wherein the film has an oxygen bility coefficient (OPC) less than 0.05 cm3 mm/m2.24h.atm at 50% RH.

16. The multilayer film according to any one of claims 1 to 15 wherein the total thickness of the multilayerfilm is between 10 and 1000 micron.

17. The multilayer ﬁlm according to any one of claims 1 to 16 wherein the at least one starch layer has a total ess between 100 and 600 micron and the at least one other layer has a total thickness between 10 and 400 micron.

18. The multilayer film according to any one of claims 1 to 16 wherein the at least one starch layer has a total thickness between 10 and 60 micron and the at least one other layer has a total thickness n 5 and 40 micron.

19. The multilayer film according to any one of claims 1 to 18 wherein the modified starch comprises a high amylose starch.

20. The multilayer film according to any one of claims 1 to 19 wherein the modified starch is chemically modified so as to replace hydroxyl functionality with functionality selected from the group consisting of ethers and esters and es thereof.

21. The multilayer film according to any one of claims 1 to 20 wherein the modified starch is chemically modified to include a hydroxyalkyl 02-6 group or ed by reaction with an anhydride of a ylic acid.

22. The multilayer film according to any one of claims 1 to 21 wherein the at least one starch layer r comprises at least one water soluble polymer.

23. The multilayer film ing to claim 22 wherein the at least one water soluble polymer is selected from the group consisting of polwinyl alcohol and polyvinyl acetate and mixtures f.

24. The multilayer film according to any one of claims 1 to 23 wherein the at least one starch layer further comprises at least one plasticiser.

25. The multilayer film according to claim 24 wherein the at least one plasticiser comprises one or more polyols.

26. The multilayer film according to any one of claims 1 to 25 wherein the at least one starch layer ses one or more nanomaterials.

27. The multilayer film ing to claim 26 wherein the nanomaterial includes clays and modiﬁed clays.

28. The multilayer film according to claim 27 wherein the ed clay is a hydrophobically modified layered silicate clay.

29. The ayer film according to claim 28 wherein the hydrophobically modified layered silicate clay is a clay modified with a surfactant comprising long chain alkyl groups wherein polar substituents are not attached to the long chain alkyl.

30. A method of making the multilayer film of any one of claims 1 to 29 wherein the method comprises at least one of the steps of co-extrusion, g, casting or film blowing.

31. Use of a multilayer film according to any one of claims 1 to 29 in packaging.

32. Use of a multilayerfilm ing to claim 31 in packaging foodstuffs.

33. An article of manufacture comprising the multilayer film according to any one of claims 1 to 29.

34. The article according to claim 33 wherein the article is a package.