CN112793264A

CN112793264A - Food packaging film

Info

Publication number: CN112793264A
Application number: CN201911111856.5A
Authority: CN
Inventors: 吉伊特·班迪奥帕迪亚伊; 玛丽·科萨; 拉克希·K·莱卡拉卡拉; 莱斯莉·马普科; 姆福·莫特隆; 文森特·欧吉周; 苏普拉卡斯·辛哈·雷; 曼弗雷德·斯克里巴; 西菲索·斯科萨纳; 西姆菲韦·宗格
Original assignee: Council for Scientific and Industrial Research CSIR
Current assignee: Council for Scientific and Industrial Research CSIR
Priority date: 2019-11-14
Filing date: 2019-11-14
Publication date: 2021-05-14
Anticipated expiration: 2039-11-14
Also published as: CN112793264B

Abstract

The present invention provides a composite active flexible polymeric film for a container containing an acidic material. The membrane, upon contact with the acidic material, produces carbon dioxide gas that resides in the headspace of the vessel.

Description

Food packaging film

Technical Field

The present invention relates to food packaging films.

Background

The inventors are aware of the use of flexible films for packaging food products, such as wine and fruit juices. This package of liquid food is also typically packaged and supported in a Box, and is referred to as a "Bag-in-Box" (Bag-in-Box) package. Typically, the primary oxygen barrier is an aluminum film layer, however, this layer is easily damaged during shipping and is not recyclable and transparent, thereby preventing food from being visible through the film. The main purpose of the film is to extend the shelf life of the food as long as possible by limiting the exposure of the food to oxygen, light and microorganisms.

Description of the Related Art

The traditional function of a package is to package or contain food to limit the ingress of elements outside the package, which can lead to degradation and spoilage. U.S. patent application 2009/0324979A1 discloses Polyethylene (PE) -CaCO comprising as core and outer layer₃Multilayer film structure of [1 ]]. CaCO in this patent₃Coated with stearic acid or palmitic acid. Alternatively, after surface modification, in CaCO₃In the wet grinding of (2), a polyacrylate salt and/or a salt of an acrylic acid copolymer is used as a grinding aid. One or more layers of Ethyl Vinyl Acetate (EVA), Ethylene Ethyl Acetate (EEA), Ethylene Acrylic Acid (EAA) have been used as an inner layer to improve sealing. The authors state that in CaCO₃The water vapor transmission rate is reduced in the presence of (2). Furthermore, the surface roughening effect enhances printability and print register. Has shown the addition of CaCO₃The coefficient of friction is also reduced.

EP1439956A1 relates to having a high water contentTwo-way multilayer PE film of vapor transmission rate [2 ]]. The base layer (central layer) consisting of CaCO₃Of PE, CaCO₃As capture agent (captivating agent). This layer is sandwiched between a copolymer (ethylene-propylene copolymer or ethylene-propylene-butene terpolymer) or a hydrocarbon resin (e.g., terpene, styrene, and cyclopentadiene). The authors state that they may have unidirectional tear characteristics in the longitudinal direction and are useful for packaging foodstuffs such as confectionery.

US5011698 has disclosed the stretching of LLDPE (linear low density PE), CaCO by stretching in two directions₃And calcium stearate to produce breathable microporous films [3 ]]. Such microporous films are desirably disposable articles such as diapers, bed sheets and hospital gowns. LDPE (Low Density PE) -CaCO as described in US4298647₃Have also been used to prepare decorative sheets [4 ] that can be torn across]. US 4219453 has demonstrated that inorganic fillers (e.g. CaCO) containing ethylene polymers (which may be homopolymers and copolymers) in the presence of a mixture of stearic and palmitic acids (1: 1), zinc stearate and 2, 6-di-tert-butyl-p-glycerol (2,6-di-ter-butyl-p-cerol)₃) Exhibit improved mechanical strength (impact and tear). None of these disclosures report the use of polymer/CaCO₃The composite serves as an inner functional layer to generate CO in the headspace and in the packaged acidic liquid₂To suppress oxygen.

PA PNC/tie/PE is available from a report wherein Cloisite30B and Dellite 43B nanoclay are used to prepare PA PNC. LDPE-g-MA was used as tie layer [6 ]. This report can be found in the following positions: garofalo E, Scarfato P, incarnato l, "adjusting coextrusion process conditions and film layout to optimize the performance of multilayer nanocomposite films for food packaging" (polymer composite, 2017, DOI 10.1002/pc.24323).

Disclosure of Invention

It is an object of the present invention to provide a food packaging film having an improved shelf life.

The present invention provides a composite active flexible polymeric membrane for a container containing an acidic material, the membrane generating carbon dioxide gas upon contact with the acidic material, thereby residing in a headspace of the container.

The acidic material is typically an acidic food product such as wine and fruit juices. Typically, the container may be selected from bag-in-box containers.

The film may comprise one or more layers. In the case of more than one layer, the inner layer in contact with the acidic material is active and generates carbon dioxide gas.

At least one layer may be a barrier layer. The barrier layer provides a barrier to the fluid.

The active film or layer may be derived from an olefin or a biopolymer, preferably polyethylene. The active film or layer may also include a metal carbonate to form (polymer/MCO)₃) Composite, preferably polyethylene metal carbonate (PE/MCO)₃) And more preferably polyethylene calcium carbonate (PE/CaCO)₃) And (c) a complex.

MCO₃The particles can reach a size of several microns and are incorporated into the polymer. Preferably, MCO₃The particles may be between 1 and 10 microns, and more preferably about 5 microns.

Can select MCO₃To replenish the target product to be packaged by releasing an optimal amount of carbon dioxide.

Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE) and MCO₃The mixture of (a) may be produced by melt extrusion (melt extrusion) prior to the blown film process. The ratio of LLDPE to LDPE can be between 80:20 and 90: 10. The temperature of the remaining extrusion process zones, including the die, except the feed zone (set at 120 c), may be 160-180 c, in particular 160 c. The feed rate and screw speed were maintained at 3.5kg/h and 202rpm, respectively. It is to be appreciated that PE has good resistance to tartaric acid, malic acid, citric acid and lactic acid.

The inner layer may be produced by melt extrusion prior to the blown film process, and may be produced by mixing a Linear Low Density Polyethylene (LLDPE) and a Low Density Polyethylene (LDPE). The ratio of LLDPE to LDPE may be between 80:20 and 90:10, preferably 85: 15.

A batch of polyethylene or polyethylene mixture can be mixed with the polyethyleneMCO of selected weight₃Mixing the granules to obtain a certain weight percentage of MCO₃The weight percentage is between 15 and 35 wt%, preferably selected from 20 wt%, 25 wt% and 30 wt%.

The inner active layer of the film may be separated from the outer layer to form an active layer container or active layer pocket inside the outer layer.

Alternatively, multiple layers of the film may be laminated and may each include a different polymer or composite polymer.

The outer layer may be a composite passive barrier layer comprising nanoclay particles.

The composite passive barrier may be Polyamide (PA) based. Nanoclay particles may be mixed with PA and extruded to form a nanocomposite (PA PNC). The nanoclay may be bentonite, preferably montmorillonite. The particle size of the nanoclay may be between 50nm and 1 micron in width and length, and is preferably less than 500 nm. The nanoclay may be between one silicate layer having a thickness of about 1nm, or may constitute a stack of up to 10 layers having a thickness of 10nm, but preferably between 1 and 5 layers.

The membrane may include a PA layer on its operatively outer side and act as a physical barrier to gas permeation and not contact with food.

The film may include a suitable tie layer (tie layer), preferably a layer of polyacrylic acid (PAA) between the active barrier layer and the composite passive barrier layer.

In one embodiment, the PA PNC is prepared by a master batch dilution technique. The processing temperature of the different extrusion zones can be selected to be 120 ℃, 200 ℃, 260 ℃, 250 ℃, 245 ℃ and 240 ℃ (die). The feed rate and screw speed were 4.4kg/h and 156rpm, respectively. According to thermogravimetric analysis (TGA), the inorganic/silicate content of the masterbatch was 23 wt%. The PA PNC can then be prepared by diluting the masterbatch in pure (neat) PA, with the desired content of nanoclay. The inorganic content of the PA PNC (determined by TGA) was 7 wt%. Prior to processing, PA and nanoclay were dried at 60 ℃ overnight, and the processed samples were dried under the same conditions.

The layers may be separated, laminated or co-extruded.

The invention also extends to a container constructed from a film as described above.

The invention also extends to a method of constructing a membrane as described above.

The present invention is a novel film construction comprising an innovative use of PE/CaCO₃Composite inner layer and nano-clay based south Africa (Betsopa)^TM) The passive barrier of (a).

Drawings

Fig. 1 is a Scanning Electron Microscope (SEM) image captured on a freeze fracture cross section of a membrane as an example.

FIG. 2 is the CO over time₂Graphical representation of (volume) release.

Fig. 3 is a schematic view of different configurations and embodiments of a bag-in-box application.

Fig. 4 is a photograph of a typical vial displacement device for quantifying carbon dioxide released from a film containing a PE active layer that serves as an inner layer.

Detailed Description

The invention will now be described by way of example with reference to the accompanying drawings.

A mixture of Linear Low Density Polyethylene (LLDPE) and Low Density Polyethylene (LDPE) is produced by melt extrusion prior to the blown film process. The ratio of LLDPE to LDPE was 85: 15.

CaCO₃The particles are in the micron to nanometer size range, preferably about 5 microns. By mixing a mixture of LLDPE and LDPE with 20 wt.%, 25 wt.% and 30 wt.% CaCO before extrusion₃Mixing to obtain different CaCO₃The PE active composite material can be prepared by loading a film.

The temperature of the rest of the extrusion process zone (including the die) except the feeding zone (set at 120 ℃) is 160-180 ℃, and in particular, the temperature is 160 ℃. The feed rate and screw speed were maintained at 3.5kg/h and 202rpm, respectively. It is to be appreciated that PE has good resistance to tartaric acid, malic acid, citric acid and lactic acid.

Composite passive barrier nanoclay particles are mixed with PA and extruded to form a nanocomposite (PA PNC).

PA PNCs can be prepared by masterbatch dilution techniques and direct incorporation of nanoclays having specific loadings.

In one case, the PA PNC is prepared by a masterbatch dilution technique. The processing temperature of the different extrusion zones is 120 ℃, 200 ℃, 260 ℃, 250 ℃, 245 ℃ and 240 ℃ (die). The feed rate and screw speed were 4.4kg/h and 156rpm, respectively. According to thermogravimetric analysis (TGA), the inorganic/silicate content of the masterbatch was 23 wt%. The PA PNC can then be prepared by diluting the masterbatch in neat PA, with the desired content of nanoclay. The inorganic content of the PA PNC (determined by TGA) was 7 wt%. Prior to processing, PA and nanoclay were dried at 60 ℃ overnight, and the processed samples were dried under the same conditions.

A co-rotating twin-screw extruder was used for processing and the extruded samples were collected by a water bath (water bath) and then pelletized, the co-rotating twin-screw extruder having an L/D of 40 and a die diameter (die diameter) of 3 mm.

Each film is a monolayer coextruded blown film or a multilayer coextruded (co-extruded) blown film.

The main objects and advantages of the invention are: control of CO₂Is released from the PE active film, thereby increasing the shelf life of the fruit acid containing beverage by displacing dissolved oxygen in the liquid and creating a positive pressure.

With different concentrations of CaCO₃And a single layer PE active film of a neat PE film, indicates that the PE active agent film can release CO when contacted with a fruit acid (e.g., tartaric acid)₂。

The PE active layer is also integrated in the multilayer film by addition to the PA PNC, which provides a passive oxygen barrier.

Example 1

With 20% CaCO₃The single-layer PE active film of (example 1). The composition of the film and the key film processing parameters are listed in table 1. FIG. 1a showsScanning Electron Microscope (SEM) images captured on freeze-fractured cross-sections of the membrane are shown. The circular pattern represents dispersed CaCO₃And (3) granules. Embedded with CaCO₃The active membrane(s) generate CO when contacted with an acidic fluid for a period of time₂And eventually creates a positive pressure inside the bag/container and prevents the penetration of oxygen from the atmosphere. Of particular note, the inventors have found that CaCO can be incorporated₃The inherent sealing performance of PE is not affected.

Determination of CO by bottle-tube displacement (see appendix A) based on the reaction of tartaric acid solution with the membranes used in the experiment₂The amount of gas released. FIG. 2 shows the CO released over time₂(volume) graphical representation. It is clear that tartaric acid will permeate into the membrane over time, with CaCO in the membrane₃React and release CO₂. Neat PE films containing 85% LLDPE and 15% LDPE did not have this CO₂And (4) releasing the capacity. In most cases, visible changes are noticeable after about 4 days.

Example 2

Containing 25% of CaCO₃The monolayer PE active film of (example 2) shows CaCO in the particles₃Concentration to CO₂The effect of release of (a). The composition of the film and the key film processing parameters are listed in table 1. Figure 1b shows a SEM image captured on a freeze fracture cross section of the membrane. As is evident from the figure, the reactive sites follow the CaCO₃Is increased by the addition of (c). As a result, CO₂Increased release (see figure 2). Thus, it is contemplated that as CaCO₃Increased concentration, more CaCO₃The particles are useful for reacting with acids contained in food products.

Example 3

In a single-layer PE active film, CaCO₃Further increasing the concentration of (c) to 30% (example 3). The composition of the film and the key film processing parameters are listed in table 1. Figure 1c shows a SEM image captured on a freeze fracture cross section of the membrane. As is evident from the figure, the surface roughness follows CaCO₃Is increased and more bits are addedDots can be used for the target reaction. Subsequently, as shown in FIG. 2, CO₂The release of (a) is increased. Can pass through CaCO₃And/or controlling the contact area by process induced (process induced) porous structure formation.

Example 4

PE active (similar to example 2) composites were integrated in multilayer active-passive barrier films, where nanoclays dispersed in PA PNC prevent oxygen ingress by creating tortuosity (example 4). The composition of the film and the key film processing parameters are listed in table 1. Figure 1d shows a SEM image captured on a freeze fracture cross section of the membrane. In fig. 1d it can clearly be seen that there are multiple layers, the PE active layer having a thickness of about 32 μm. FIG. 2 shows CO evolution from the membrane₂The amount of (c). The reaction activity ratio of the multilayer structure comprises CaCO in different concentrations₃The reactivity of the monolayer film of (2) was low (examples 1 to 3). However, it slowly releases CO over time₂. Curve fitting using a 2 nd order polynomial to estimate CO released over 1, 3 and 6 months₂The amount of (c). 1. Estimated CO released from the membrane after 3, 6 months₂The amounts were 6, 22 and 146ppm, respectively. Such CO₂The concentration falls within the specified limits. For safety reasons, in the case of BIB packaging, the specified CO₂The amount of the (B) is less than 600-800 ppm. Above 600-800 ppm, when CO is present₂As the solution escapes, the temperature rises and the bag may expand.

The human palate (human palate) can feel about 1g/l of carbon dioxide, which produces a slight gush (spritz) of the tongue. Non-sparkling wine, semi-sparkling wine and CO suggested in sparkling wine₂The concentration (at 20 ℃) is less than 2g/l, 2-5 g/l and more than 6g/l respectively. According to the brewing method, the limit values of the carbon dioxide of the acacia longissimus wine, the aromatic white wine, the chardonnay dry white wine and the red wine are 1000-1100 ppm, 800ppm, less than 500ppm and less than or equal to 500ppm respectively. Generally, the recognized CO in red and white wines₂Is different. The standard maximum of red wine is about 400ppm, and the standard maximum of white wine is about 600-800 ppm.

Is higher thanCO of₂The concentration may be such that the shortening (crisper wine) has a lower dissolved oxygen, but a lower flavour intensity (flavour intensity). However, a small amount of CO₂Is helpful for preserving wine. Adding sulfur dioxide (SO) to wine during fermentation₂) Is a common practice to prolong the shelf life. SO (SO)₂Is itself a gas, but readily reacts with water and forms sodium bisulfite/sulfite. The formation of sulphite depends on the pH of the water. As the pH increases, it logically increases. This sulfite binds to anthocyanins and the phenolic molecules give the wine a red color. Thus, containing SO₂The red wine has lighter color. This reaction reduces the chance of reaction between the anthocyanin and dissolved oxygen. Anthocyanins react with dissolved oxygen to produce acetaldehyde, which gives the wine a brown color. Free SO after filling₂The content of (B) is usually 25 to 50 ppm. However, it decreases with time, leaving free SO after 9 months₂The content of (B) was 12 ppm. SO (SO)₂Can prevent wine oxidation, but can produce adverse allergic reaction. Since CO2 as a thick coating on the wine surface helps to prevent the growth of oxidative and spoilage organisms, CO is slowly released over time₂Can compensate SO₂And extend the shelf life of the wine. Furthermore, it can reduce the initial SO₂Concentration, thereby reducing health risks.

Typical properties of the multilayer active-passive barrier film are summarized in table 2. The typical oxygen permeability of the film was 1.49cc-mm/m at 0% RH²Day. When pure PA was used as an inactive barrier instead of PAPNC, the oxygen permeability decreased by about 51% compared to the comparative example. The transparency of the film was measured using a UV-Vis spectrometer and the transmission before and after exposure to moisture (37% RH, 24 hours at 30 ℃) was 89.47% and 89.02%, respectively. As shown in table 2, the substitution of PA PNC for PA did not have any effect on the transparency of the film. Overall, the multilayer active-passive barrier film also has better tensile properties than the comparative examples.

In any application, safe migration of nanoparticles from packaging films is critical. Tables 3 and 4 show the migration of the nanoclay component from the coextruded multilayer film (example 4 and comparative examples). Inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic spectrometry (GFAAS) have been used to quantify inorganic species (marked as Mg, Al and Si) migrating into type C mimics recommended for high alcohol content foods and beverages (following EU10/2011 regulatory procedures). While High Performance Liquid Chromatography (HPLC) in combination with MS has been used to quantify organic migration from typical membranes. The effect of the storage time of the membrane before exposure to the simulant was investigated. Table 3 lists the concentrations of Mg, Al and Si that migrated from the film into the simulant. It is noted that nanoclay is recognized as a class a material and safe in accordance with swiss regulations of the federal civil affairs department (FDHA), federal food safety and veterinary bureau (FSVO) annex 10 regulations for food-contact materials and items and 2017 for the permitted list of materials and related requirements for the production of packaging inks. For class B materials, the default specified migration limit is 0.01ppm [7 ]. Some results indicate that no nanoclay component is below the detection limit (BDL) or within the ppb concentration range. In addition, the presence of the porous active inner layer does not cause migration of the clay component into the food simulant.

The HPLC-MS results are summarized in Table 4. The tendency of the migration concentration of precursor ions in the surfactant used to modify the nanoclay to be very stable over storage time is not expected to result in an estimated 50 μ g.kg, according to the food contact material, enzyme, flavor and processing aid (CEF) panel^-1Or 0.05ppm of a dimethyl alkyl (C16-C18) amine, see the European food safety agency food contact materials, enzymes, flavors and processing aids group (CEF), the European food safety agency 2015, 13, 4285[8 ]]。

Figure 3 schematically shows different configurations and embodiments of the bag-in-box of the present invention.

Comparative example

The multilayer film consisted of a PE active layer and PA as a passive gas barrier layer (comparative example). The composition of the film and the key film processing parameters are listed in table 1. Typical oxygen permeability of the membrane is 3.07cc-mm/m at 0% RH²Day. Film clarity measurement Using UV-Vis spectrometerAnd the transmittance before and after exposure to a humid environment (37% RH, 24 hours at 30 ℃) was 88.88% and 88.17%, respectively. The tensile properties of the film are also reported in table 2 and the film exhibits similar properties in both the machine and transverse directions.

The membrane in the comparative example was used as a control to quantify the nanoclay component migrating from the membrane shown in example 4. Although the comparative examples did not contain nanoclay, some traces of Mg, Al, and Si were detected in the GFAAS. Such results may result from instrument error and/or sampled deionized water.

TABLE 1 composition of the film and Critical film processing parameters

TABLE 2 Properties of the multilayer film

TABLE 3 determination of bentonite nanoclay inorganic component migrating from multi-layer membranes by ICP-MS and GFAAS

LoD: detection limit _ BDL: below the detection limit of the instrument

TABLE 4 determination of surfactant precursor ions in migrates by HPLC method

Migration substance in contact with membrane	C₁₆C₁₆(ppm)	C₁₆C₁₈(ppm)	C₁₈C₁₈(ppm)
				Comparative example-preparation of	BDL	BDL	BDL
Example 4 preparation	1.93	0.0881	1.83
				Examples 4 to 3m	BDL	BDL	BDL
Examples 4 to 6m	0.0152	BDL	BDL

Appendix A

Experimental device for displacement of bottle tube

The most common acids in wine are tartaric acid, malic acid and citric acid, and the concentrations of these fruit acids in wine at harvest are 2.5-5 g/l, 1-4 g/l and less than 1g/l, respectively. Among them, tartaric acid is preferable because it is stable against degradation by microorganisms. Malic acid can degrade to lactic acid and citric acid can degrade to diacetyl and acetic acid and impart a buttery aroma to certain wines. Thus, in this study, 1% wine has been added due to the reaction of tartaric acid with the multilayer film active layerThe use of a solution of tartaric acid as a simulant for wine to study CO₂Is released. To determine CO₂A typical vial displacement testing apparatus is shown in fig. 1. The device is then placed in a stationary position where it is not easily interrupted, so that any movement of the droplet/bubble in the tube is due to a pressure change in the bag headspace. This movement of the bubbles is believed to be due to the tartaric acid solution and the PE/CaCO₃CO is released by reaction of the film lining₂. In a separate experiment (lime water test), CO has been confirmed₂Is released. The headspace remained constant at 2.2% regardless of the volume of the bag. The displacement (D) of the droplets/bubbles is then measured at different time intervals and the volume of the gas is estimated according to equation 1.

V＝πr²D.................................[1]

Where r is the inner diameter of the tube and D is the measured displacement.

Reference data

Roussel MD, Cara JF, Guy AR, Shaw LG, "calcium carbonate barrier films and uses thereof", 2009, US2009/0324979A 1.

Bader MJ, "multilayer white bi-directional polyethylene film with high water vapor transmission", 2004, EP1439956a 1.

Anton Jr MK, Hill DJ, "breathable microporous films and methods of making the same," 1991, US 5011698.

Cancio LV, Wu P-C, "cross-tearable decorative sheet", 1981, US 4298647.

Sakurai H, Moriguchi K, KatayamaY, "organic filler ═ incorporated ethylene polymer film", 1980, US 4219453.

Garofalo E, Scarfato P, Incarnato L, "adjusting coextrusion process conditions and film layout to optimize the properties of multilayer nanocomposite films for food packaging,", { polymer composite }, 2017, DOI 10.1002/pc.24323).

7. Swiss regulations under the federal civil affairs department (FDHA), federal food safety and veterinary bureau (FSVO) regulations of the federal civil affairs department (FDHA) annex 10 regarding materials and items in contact with food, and 2017 a list of allowed substances for the production of packaging inks and related requirements.

8. European food safety agency food contact materials, enzymes, flavours and processing aids panel (CEF), european food safety agency 2015, 13, 4285.

Claims

1. A composite active flexible polymeric membrane for a container containing an acidic material, wherein the membrane generates carbon dioxide gas when in contact with the acidic material and resides in the headspace of the container, the membrane comprising a polymer and metal carbonate composite layer.

2. The composite membrane of claim 1 comprising more than one layer and wherein the inner layer is reactive to produce carbon dioxide gas upon contact with the acidic material.

3. The composite film of claim 1 wherein at least one layer is a barrier layer.

4. The composite membrane of claim 1, wherein the active layer is derived from an olefin or a biopolymer.

5. The composite film of claim 1, wherein the active layer is derived from polyethylene.

6. The composite membrane of claim 1, wherein the active layer is a polyethylene metal carbonate (PE/MCO)₃) And (c) a complex.

7. The composite film of claim 1 wherein the active layer is polyethylene calcium carbonate (PE/CaCO)₃) And (c) a complex.

8. The composite film of claim 7, wherein the CaCO is₃Particles in the micrometer to nanometer size rangeAnd incorporated into the polymer.

9. The composite film of claim 5 wherein the active layer comprises Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE), and CaCO₃A mixture of (a).

10. The composite film of claim 5, wherein the film or layer is prepared by melt extrusion prior to a blown film process, as the case may be.

11. The composite film of claim 9 wherein the ratio of LLDPE to LDPE is selected to be in the range of 20:80 to 10: 90.

12. The composite film of claim 7, wherein CaCO₃The weight percentage of (A) is 15-35 weight percentage.

13. The composite membrane of claim 2 wherein the inner active layer of the membrane is spaced apart from the outer layer to form an active layer container or pouch inside the outer layer.

14. The composite film of claim 2 wherein the layers of the film are laminated and each comprise a different polymer or composite polymer.

15. The composite film of claim 13 wherein the outer layer is a composite passive barrier layer comprising nanoclay particles.

16. The composite film of claim 15, wherein the composite passive barrier layer is Polyamide (PA) based.

17. The composite membrane of claim 14, wherein the membrane comprises a suitable tie layer.

18. A container constructed from the film of claim 1.

19. A method of constructing a membrane according to claim 9, comprising the steps of: the temperature of the feed zone was set at 120 ℃ and the temperature of the remaining extrusion processing zone, including the die, was between 160 ℃ and 180 ℃, wherein the feed rate and screw speed were maintained at about 3.5kg/h and 202rpm, respectively.

20. The method of claim 19, wherein a batch of polyethylene or polyethylene blend is mixed with a selected weight of CaCO₃Mixing the granules to obtain a certain weight percentage of CaCO₃The weight percentage is between 15 and 35 weight percentages.

21. The method of claim 19, wherein nanoclay particles are mixed with the PA and extruded to form a nanocomposite (PNC).

22. The method of claim 21, wherein the PA PNC is prepared by a masterbatch dilution technique and the processing temperatures of the different extrusion zones are selected to be 120 ℃, 200 ℃, 260 ℃, 250 ℃, 245 ℃, 240 ℃ (die), with the feed rate and screw speed set to 4.4kg/h and 156rpm, respectively.