BIODEGRADABLE CONTAINER, METHOD FOR OBTAINING SAME AND USE THEREOF FOR CONTACT, TRANSPORT AND/OR STORAGE OF PERISHABLE PRODUCTS

Abstract

The present invention relates to a biodegradable container comprising a thermoformable structural layer with tear resistance and low cost, and optionally an adhesive barrier layer, an adhesive active layer and/or a layer in direct contact with the product, all of which are based on biodegradable polymers. Furthermore, the present invention relates to the method for obtaining same and to use thereof for contact, transport and/or storage of perishable products.

Claims

1. A biodegradable packaging, characterized in that it comprises a thermoformable structural layer (a) having a thickness between 0.015 mm and 10 mm which comprises a resin comprising: a polymer matrix containing polyhydroxyalkanoate at a percentage by weight of up to 75% with respect to the total resin, a second biodegradable polymer phase selected from polyurethanes, elastomeric polyhydroxyalkanoates, biodegradable thermoplastic elastomers, polycaprolactones, polylactic acid, and a combination thereof, at a percentage by weight of up to 50% with respect to the total resin, wherein the sum of the percentages by weight of the polymer matrix and of the second polymer phase does not exceed 100% in the resin; functional additives selected from a rigid mineral filler at a content of up to 60 parts for every 100 parts of resin, compatibilizing additives at a content of up to 10 parts for every 100 parts of resin, and a combination thereof.

2. The biodegradable packaging according to claim 1, wherein the thermoformable structural layer (a) further comprises a renewable and/or biodegradable rigid filler at a content of up to 40 parts for every 100 parts of resin as a functional additive.

3. The biodegradable packaging according to claim 1, wherein the thickness of the packaging is between 0.1 mm and 1 mm.

4. The biodegradable packaging according to claim 1, wherein the polymer matrix containing polyhydroxyalkanoate is selected from poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-valerate), polylactic acid, and a combination thereof.

5. The biodegradable packaging according to claim 4, wherein the polymer matrix containing polyhydroxyalkanoate of the thermoformable structural layer (a) is made of poly(3-hydroxybutyrate).

6. The biodegradable packaging according to claim 1, wherein the second biodegradable polymer phase contains poly(butylene adipate-co-terephthalate) (PBAT) and poly(3-hydroxybutyrate-co-valerate) (PHBV), and wherein the molar concentration of HV in PHBV is between 1 and 80.

7. The biodegradable packaging according to claim 6, wherein the molar concentration of HV in PHBV is between 7 and 60.

8. The biodegradable packaging according to claim 1, wherein the biodegradable rigid filler is selected from cellulose, lignocellulosic fillers, and a combination thereof.

9. The biodegradable packaging according to claim 1, wherein the mineral filler is selected from clays, calcium carbonate, hydrotalcites or double hydroxides, boron nitride, titanium dioxide, and a combination thereof, with or without being organomodified.

10. The biodegradable packaging according to claim 1, wherein the compatibilizing additives are selected from peroxides, isocyanurates, diisocyanates, acrylates, epoxy resins and compounds with epoxide functionality, phosphates, phosphites, polycarbodiimide, vegetable oils multi-functionalized with acrylate, epoxide or maleic groups, and a combination thereof.

11. The biodegradable packaging according to claim 1, which comprises a resin comprising a polymer matrix containing polyhydroxyalkanoate at a percentage by weight of 60% with respect to the polymeric total of the resin, a second biodegradable elastomeric polymer phase at a percentage by weight of 40% with respect to the polymeric total of the resin, a mineral filler containing calcium carbonate, with or without being organomodified, at a content of 20 parts for every 100 parts of resin, and a compatibilizing additive at a content of 2 parts for every 100 parts of resin.

12. The biodegradable packaging according to claim 1, which comprises a resin comprising a polymer matrix containing polyhydroxyalkanoate at a percentage by weight of 50% with respect to the total resin, a second biodegradable elastomeric polymer phase at a percentage by weight of 50% with respect to the total resin, a renewable and biodegradable filler containing cellulose at a content of 10 parts for every 100 parts of resin, a mineral filler containing calcium carbonate, with or without being organomodified, at a content of 20 parts for every 100 parts of resin, and a compatibilizing additive at a content of 2 parts for every 100 parts of resin.

13. The biodegradable packaging according to claim 1, further comprising a self-adhesive gas and vapor barrier layer (b), having a thickness between 0.1 μm and 100 μm, located on the structural layer (a) comprising a coating in the form of electrospun fibers of polymers and biopolymers with gas and vapor barrier properties.

14. The biodegradable packaging according to claim 13, wherein the composition of the self-adhesive gas and vapor barrier layer (b) is selected from polyhydroxyalkanoates, proteins, polysaccharides, lipids, polylactic acid, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, poly(vinylidene chloride), poly(lactic-co-glycolic acid) and poly(glycolic acid).

15. The biodegradable packaging according to claim 13, wherein the self-adhesive gas and vapor barrier layer (b) further comprises particles and/or sheets having a nanometric thickness at a percentage by weight of between 0.01% and 40% with respect to the polymeric total of the self-adhesive gas and vapor barrier layer (b).

16. The biodegradable packaging according to claim 1, further comprising a gas and vapor barrier layer obtained by casting (b) of cellulose nanocrystals, nanofibrillated cellulose, microfibrillated cellulose, bacterial nanocellulose, with or without being organomodified, and a combination thereof.

17. The biodegradable packaging according to claim 16, further comprising a self-adhesive layer, located between layers (a) and (b) and/or on layer (b), of electrospun fibers of polymers and biopolymers selected from polyhydroxyalkanoates, proteins, polysaccharides, lipids, polylactic acid, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, poly(vinylidene chloride), poly(lactic-co-glycolic acid) and poly(glycolic acid).

18. The biodegradable packaging according to claim 13, wherein the thermoformable structural layer (a) has received corona treatment to facilitate adhesion with the barrier layer (b).

19. The biodegradable packaging according to claim 13, further comprising at least one self-adhesive active layer (c) selected from a self-adhesive antimicrobial active layer (c), having a thickness between 0.1 μm and 100 μm, located on the self-adhesive gas and vapor barrier layer (b) consisting of an electrospun layer of biodegradable polymer, preferably polyhydroxyalkanoate, comprising an antimicrobial active agent, or a self-adhesive active layer (c), having a thickness between 0.1 μm and 100 μm, located on the self-adhesive gas and vapor barrier layer (b) consisting of an electrospun layer of biodegradable polymer, preferably polyhydroxyalkanoate, comprising at least one active agent selected from oxygen scavengers, moisture absorbers, flavor regulators, ethylene absorbers, and a combination thereof; and a combination thereof.

20. The biodegradable packaging according to claim 13, comprising a self-adhesive active layer (c) having a thickness between 0.1 μm and 100 μm, located on the self-adhesive gas and vapor barrier layer (b) consisting of an electrospun layer of biodegradable polymer, preferably polyhydroxyalkanoate, comprising an active agent selected from oxygen scavengers, moisture absorbers, flavor regulators, ethylene absorbers, an antimicrobial agent, and a combination thereof.

21. The biodegradable packaging according to claim 19, comprising a layer for direct contact with the packaged product (d), located on the self-adhesive active layer (c), having a thickness between 10 μm and 100 μm consisting of a layer of a biodegradable polymer, preferably polyhydroxyalkanoate.

22. A method of obtaining the packaging according to claim 21, comprising the following steps: i) manufacturing a thermoformable structural layer (a) by melt extrusion; ii) manufacturing a self-adhesive gas and vapor barrier layer (b) on the structure obtained in (i) by electrodynamic processes, aerodynamic processes or a combination of both; iii) manufacturing at least one self-adhesive active layer (c) on the structure obtained in (ii) selected from a self-adhesive antimicrobial active layer (c), having a thickness between 0.1 μm and 100 μm, located on the self-adhesive gas and vapor barrier layer (b) consisting of an electrospun layer of biodegradable polymer, preferably polyhydroxyalkanoate, comprising an antimicrobial active agent, or a self-adhesive active layer (c), having a thickness between 0.1 μm and 100 μm, located on the self-adhesive gas and vapor barrier layer (b) consisting of an electrospun layer of biodegradable polymer, preferably polyhydroxyalkanoate, comprising at least one active agent selected from oxygen scavengers, moisture absorbers, flavor regulators, ethylene absorbers, and a combination thereof; and a combination thereof; or a self-adhesive active layer having a thickness between 0.1 μm and 100 μm, located on the self-adhesive gas and vapor barrier layer (b) consisting of an electrospun layer of biodegradable polymer, preferably polyhydroxyalkanoate, comprising an active agent selected from oxygen scavengers, moisture absorbers, flavor regulators, ethylene absorbers, an antimicrobial agent, and a combination thereof; by electrodynamic processes, aerodynamic processes or a combination of both; iv) manufacturing a layer for direct contact with the product (d) on the structure obtained in (iii) by melt extrusion, electrodynamic processes, aerodynamic processes or a combination of electrodynamic processes and aerodynamic processes; and v) thermoforming the final structure obtained in step (iv).

23. The method according to claim 22, wherein steps (ii) and (iii) are carried out by an electrodynamic electro spinning process.

24. The method according to claim 22, wherein step (iv) is carried out by a casting or blow extrusion process.

25. The method according to claim 22, wherein step (iv) further comprises a step (iv′) between step (iv) and step (v) for thermal treatment at a temperature less than the melting temperature of the structural layer (a).

26. The biodegradable packaging according to claim 1, wherein the packaging is selected from the list consisting of trays, plates, films, bags, blisters, bottles, tubs, cutlery and knives, cups, coffee capsules and straws.

27. A biodegradable packaging according to claim 26 for contact with, transport and/or storage of perishable goods.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0119] FIG. 1 shows scanning electron microscopy (SEM) of PACKAGING 3, showing the good dispersion and adhesion of the mixture of the rigid and elastomeric polymer, as a result of the addition of the compatibilizing additive Joncryl ADR-4400.

[0120] FIG. 2 shows scanning electron microscopy (SEM) of PACKAGING 5, showing the good dispersion and adhesion of the mixture of the rigid and elastomeric polymer, compatibilizing additive and calcium carbonate.

[0121] FIG. 3 shows X-ray diffraction of PACKAGING 3 and PACKAGING 5, where it can be observed that the mineral acts as an anti-nucleating agent, reducing the crystallinity of the resin and preventing brittleness.

[0122] FIG. 4 shows a diagram of the process of obtaining the multilayer system of example PACKAGING 10 based on: monolayer structure of PHB composite (described in example PACKAGING 2), barrier layer of electrospun fibers of EVOH, active layer of electrospun fibers of PHBV20 containing cinnamaldehyde and a food contact layer.

EXAMPLES

[0123] The invention will be illustrated below by means of different packaging examples obtained by the inventors that demonstrate the effectiveness of the product of the invention.

Packaging 1:

[0124] A commercial-type polyhydroxyalkanoate (PHA), PHB 309, a biodegradable homopolyester produced and marketed by Biomer (Krailling, Germany), is used to manufacture the structural layer. The processing is performed in a D30 co-rotating twin-screw extruder by Construcciones Mecánicas Dupra, S.L. (Alicante, Spain). The screws have a diameter (D) of 25 mm and a length/diameter (L/D) ratio of 24. The equipment has 4 individual heating zones. The working conditions for processing were 185/180/175/170° C. and 40 rpm. The extruded strands, after passing through an annular die, are pelletized in an air knife. The resulting pellets are processed in a Haake Rheomex 252p single-screw extruder with a Maddock screw and a L/D of 25 coupled to a flat extrusion die prepared to obtain a film or films (of up to 250 microns) or sheets (over 250 microns) and calendered to form a reel with a controlled thickness. The resulting structural layer was obtained in the form of a sheet with an average thickness of 0.45 mm. All the samples were aged for 15 days at 25° C. and 40 relative humidity to ensure the complete development of the crystallinity of the material, before their physical characterization and thermoforming.

[0125] The mechanical properties study was carried out in tensile tests up to failure to determine tensile strength at break in MD direction (extrusion direction of the sheet) according to standard ASTM D638 (specimen Type IV) in an AGS-X 500N universal testing machine by Shimadzu Corp. (Kyoto, Japan). Tear resistance was determined according to standard UNE-EN ISO 6383 in materials in the form of film and with the geometry specified by the standard. The measurement consists of fixing to each of the two grippers one of the two strips resulting from the cut on the left end, pulling on them and recording the force needed for the cut to go through and reach the edge of the sample at the end opposite the start of the cut. The results which are shown correspond with the maximum force value needed for the crack to go through in the transverse direction with respect to the extrusion direction, divided by the thickness of the analyzed specimen. Typical tear resistance of a sheet of commercial material today of the type used to make trays (PET) under testing conditions similar to those used in the present invention is about 40 N/mm. The mechanical rigidity of a tray made of PP is typically 1300 MPa. This data was used as a reference to ensure tear resistance and minimum mechanical rigidity of the packaging developed in this invention.

[0126] The structural layer was thermoformed in the thermoforming machine (SB 53c, Illig, Helmut Roegele, Germany) at 600° C. for 30 seconds, and then a vacuum is applied, forcing the sheet to acquire the shape of the mold.

[0127] The results are shown in Table 1. This sample of Packaging 1 has a high elastic modulus and deficient tear resistance. Additionally, elongation at break is low and thermoformability is poor.

TABLE-US-00001 TABLE 1 Mechanical properties and thermoformability of PACKAGING 1-10. Elonga- Elastic tion Tear modulus at break resistance, Sample (MPa) (%) (N/mm) Thermoformability PACKAGING 2600  4.5  10.3  1 PACKAGING 2710  4.1  8.0  2 (low cost, made from waste) PACKAGING 1490  19.3  75.2    3 PACKAGING 1780  4.1  8.9  4 (low cost, made from waste) PACKAGING 1610  35.4  71.4    5 (very low cost) PACKAGING 1410  9.1  40.5  6 (very low cost, made from waste) PACKAGING 1400  91.5    68.6      7 (very low cost, made from waste) PACKAGING 2560  4.5  20  8 PACKAGING 2680  4  15  9 PACKAGING 2500  4.3  18  10 Note:    Excellent,  Good,  Fair,  Bad

Packaging 2:

[0128] To manufacture the structural layer, PHB 309, the same biopolymer used to obtain PACKAGING 1, is used as the base material. There are added to said material 10 g of lignocellulose originating from waste to reduce the cost for every 100 grams of PHB, i.e. at a concentration of 10 phr, wherein said lignocellulose has been supplied by Unió Coop (Tarragona, Spain) after the mechanical grinding and subsequent sieving of almond and hazelnut shell, and with a controlled grain size distribution below 200 micrometers. Likewise, DCP and TGIC, at 0.25 and 1 phr, respectively, are introduced to favor compatibility of the lignocellulose particles with the PHB matrix. Both reagents were acquired from Sigma Aldrich S.A (Madrid, Spain).

[0129] The entire mixture is processed in a twin-screw extruder and a sheet is obtained which is later thermoformed into a tray under the same conditions described for obtaining PACKAGING 1. The mechanical properties are determined subsequently after 15 days of aging under the same conditions applied in PACKAGING 1. Table 1 includes the obtained results. This structural layer has an elastic modulus greater than that of the packaging described in example PACKAGING 1, low elongation at break, lower tear resistance, but improved thermoformability.

Packaging 3:

[0130] To improve elongation at break, tear resistance and thermoformability of the structural layer described in example PACKAGING 1, there is added to the PHB base material (PHB 309, Biomer) 40% of a commercial biodegradable elastomer PBAT with commercial reference Ecoflex F blend C1200 and 2 phr of Joncryl ADR-4400, both by BASF S.A. (Barcelona, Spain).

[0131] All these additives are mixed under the same conditions used in PACKAGINGS 1 and 2, obtaining sheets with an average thickness of 0.45 mm. As described for the preceding examples, the obtained sheet is processed by thermoforming to generate a tray. Table 1 shows the mechanical results of the sheet and the thermoformability characteristics. This structural layer has an elastic modulus less than that of the packaging described in example PACKAGING 1, but high elongation at break, good tear resistance and good thermoformability. These good mechanical results are attributed to close interaction between both polymers favored by the use of the compatibilizing agent Joncryl ADR-4400, as can be observed in FIG. 1.

Packaging 4:

[0132] In another example, PHB (PHB 309, Biomer) is used as a base material and there is added to it 40% of a commercial biodegradable elastomer PBAT (Ecoflex F blend C1200, BASF) and 2 phr of Joncryl ADR-4400 (BASF). To improve the rigidity of the packaging with respect to the example described in PACKAGING 3, there are added 10 g of lignocellulose per 100 g of polymer resin (PHB/PBAT). The lignocellulose has been obtained/produced by Unió Coop (Tarragona, Spain), as described in example PACKAGING 2.

[0133] All these additives are mixed under the same conditions used in PACKAGINGS 1-3, obtaining sheets with an average thickness of 0.45 mm. As described for the preceding examples, the obtained sheet is processed by thermoforming to generate a tray. Table 1 shows the mechanical results of the sheet and the thermoformability characteristics. The obtained sheet has a rigidity (modulus of elasticity) greater than that of PACKAGING 3 described in the preceding example but lower elongation at break and tear resistance. The thermoformability is acceptable, but worse than PACKAGING 3.

Packaging 5:

[0134] In a new example, there are added to the PHB base material (PHB 309, Biomer) 40% of a commercial biodegradable elastomer PBAT (Ecoflex F blend C1200, BASF) and 2 phr of Joncryl ADR-4400 (BASF). To reduce the cost and balance the mechanical properties with respect to the packaging described in example PACKAGING 3 and example PACKAGING 4, there are added 20 g of calcium carbonate (Omya, Oftringen, Switzerland) for every 100 g of resin containing biopolymer, i.e. 20 phr.

[0135] All these additives are mixed under the same conditions used in PACKAGING 1-4, obtaining sheets with an average thickness of 0.45 mm. As described for the preceding examples, the obtained sheet is processed by thermoforming to generate a tray. Table 1 shows the mechanical results of the sheet and the thermoformability characteristics. This packaging has an elastic modulus and elongation at break greater than those of the packaging described in example PACKAGING 3 and excellent tear resistance. Thermoformability is good. This change in behavior is attributed to an anti-nucleating effect of carbonate due to the fact that it is well dispersed in the resin (see morphology in FIG. 2) and inhibits the development of the crystallinity of the PHB. FIG. 3 shows the X-ray diffraction patterns for Packaging 3 and 5 and it can be seen that the addition of calcium carbonate leads to a drop in total crystallinity of the sample.

Packaging 6:

[0136] In this example, there is added to the PHB base material 50% of a commercial biodegradable elastomer PBAT (Ecoflex F blend C1200, BASF) and 2 phr of Joncryl ADR-4400 (BASF). Likewise, there are added 10 g of lignocellulose and 20 g of calcium carbonate per 100 g of polymer resin (PHB/PBAT), i.e. 10 and 20 phr, respectively. The lignocellulose has been obtained/produced by Unió Coop (Tarragona, Spain), as described in example PACKAGING 2. The same calcium carbonate as that described in EXAMPLE 5 is used. It should be highlighted that this example did not present sufficient tear resistance when the resin contained 40% PBAT, as in the preceding cases. Therefore, the PBAT content was increased to 50%.

[0137] All these additives are mixed under the same conditions used in PACKAGING 1-5, obtaining sheets with an average thickness of 0.45 mm. As described for the preceding examples, the obtained sheet is processed by thermoforming to generate a tray. Table 1 shows the mechanical results of the sheet and the thermoformability characteristics. This packaging has an acceptable elastic modulus and elongation at break. Tear resistance and thermoformability are good.

Packaging 7:

[0138] To manufacture this packaging, PHB (PHB 309, Biomer) is used as the base material and there is added 12% of low-cost elastomeric PHBV obtained from waste produced, on a pilot plant scale, at NOVA University (Lisbon, Portugal). To obtain this biodegradable copolyester, mixed microbial cultures fed with fermented fruits obtained from fruit pulps supplied by SumolCompal S.A. (Portugal) obtained as industrial waste from the juice industry were used. The HV fraction in the copolymer is about 20 mol % (PHBV20). There is also incorporated 40% of commercial biodegradable elastomer PBAT (Ecoflex F blend C1200, BASF S.A.) and 2 phr of Joncryl ADR-4400 (BASF S.A.). Likewise, there are added 20 g of calcium carbonate per 100 g of polymer resin, i.e. 20 phr with respect to PHB/PH BV/PBAT.

[0139] All these additives are mixed under the same conditions used in PACKAGING 1-5, obtaining sheets with an average thickness of 0.45 mm. As described for the preceding examples, the obtained sheet is processed by thermoforming to generate a tray. Table 1 shows the mechanical results of the sheet and the thermoformability characteristics. This packaging has an acceptable elastic modulus and excellent elongation at break, tear resistance and thermoformability.

[0140] When 10 phr of microcellulose from waste are additionally added to this mixture, as in previous examples, the rigidity of the material (1650 MPa) increases while all the other properties remain within the range of acceptance, and therefore it can also be considered a material suitable for making an optimal packaging when it is needed to further reduce the cost and increase rigidity.

Packaging 8:

[0141] The purpose of this example is to show a bilayer tray according to the present invention with mechanical properties suitable for use as a packaging. The sheet obtained in example PACKAGING 1 is used as a structural layer, and a layer consisting of elastomeric electrospun fibers of PHBV20 derived from fruit waste is deposited on it by means of the electrospinning technique. The manner of obtaining PHBV20 was described in the example for Packaging 7.

[0142] To generate the fibers, a solution of 8% PHBV20 (weight/vol) in chloroform/butanol 75:25 (vol/vol) is prepared, with both solvents being obtained from Sigma Aldrich S.A. (Madrid, Spain), and stirred at room temperature for 24 h. To that end, a high-performance Fluidnatek® LE-10 pilot plant device manufactured by Bioinicia S.L. (Valencia, Spain) is used. The equipment is operated by means of a motorized needle injector, horizontally scanning a collector comprising a roller where the structural layer is arranged. Table 2 includes the conditions for processing by means of electrospinning PHBV20. This experiment is carried out under ambient conditions, i.e. 25° C. and 40% RH.

TABLE-US-00002 TABLE 2 Optimal conditions selected during electrospinning for PHBV20. Flow Needle- Concentration Voltage rate collector Time Sample (% by weight) (kV) (ml/h) distance (cm) (h) PHBV20 8 13 6 21.5 2

[0143] The resulting multilayer structure is subjected to thermoforming in the equipment under the conditions described in the preceding examples. The layers are sealed at the same time the tray is obtained, the bilayer packaging thus being formed. The layer of the electrospun film, after thermoforming, has a thickness of about 10 microns. The mechanical results were measured when the bilayer structure was subjected to an annealing process at 125° C. for 5 seconds to promote the formation of a film from the fibers by coalescence and therefore with adherence between layers.

[0144] Table 1 shows the mechanical results of the bilayer sheet and the thermoformability characteristics. This packaging has a high elastic modulus, low elongation at break, higher tear resistance than PACKAGING 1 and improved thermoformability. Therefore, the route for applying electrospun layers on the substrate leads to a material with higher tear resistance and better thermoformability.

Packaging 9:

[0145] The purpose of this example is to show a bilayer sheet according to the present invention with mechanical and barrier properties. The sheet obtained in example PACKAGING 2 is used as a structural layer, and a barrier layer consisting of electrospun fibers of PHBV/BNC is deposited on it by means of the electrospinning technique. To that end, commercial PHBV ENMAT™ Y1000P, produced by Tianan Biologic Materials (Ningbo, China) is used in the form of pellets, with an HV molar fraction in the copolymer of 3%.

[0146] To generate the fibers, a solution of 10% commercial PHBV in tetrafluoroethylene (TFE) is prepared, ≥99% purity, from Sigma Aldrich S.A. (Madrid, Spain). 10% of a BNC solution is incorporated to this solution. Bacterial cellulose was obtained from strains of Gluconacetobacter xylinus 735 (Spanish Type Culture Collection). The bacterial cellulose layer was cut into small pieces and boiled, several times, first in distilled water and after than in a solution of sodium hydroxide (NaOH) at 10% (vol/vol) to eliminate bacterial cells and the absorbed culture medium. Then the pH of the resulting solution was reduced to a value of 7 by boiling in distilled water on repeated occasions. Later, the pieces of bacterial cellulose were dried to eliminate all the absorbed water, and next, they were treated with a solution of sulfuric acid (H.sub.2SO.sub.4) in water at 50% (vol/vol) using a cellulose in acid ratio of about 7 g/l. Lastly, a white precipitate of the BNC was formed after 10 centrifugation cycles and washing with water. The BNC content in water was adjusted to 2%. Additionally, a surfactant Tween 80 (Sigma Aldrich S.A., Madrid, Spain) was added at 2 grams for every 100 grams of TFE to improve the processing of the suspension before electrospinning. Table 3 reflects the percentages used.

TABLE-US-00003 TABLE 3 Proportion of components in the PHBV/CNC solution BNC PHBV (g) solution (g) TFE (g) % of BNC in PHBV Tween (g) 10 10 100 2 2

[0147] Next, the prepared solution based on PHBV was electrospun onto the mentioned structural layer by means of the electrospinning technique. The process is performed by means of a high-performance Fluidnatek® LE-10 pilot plant device manufactured by Bioinicia S.L. (Valencia, Spain). The equipment is operated by means of a motorized needle injector, horizontally scanning a collector comprising a roller where the structural layer is arranged. Table 4 includes the conditions for processing by means of electrospinning PHBV. These experiments are carried out under ambient conditions, i.e. 25° C. and 40% RH.

TABLE-US-00004 TABLE 4 Optimal conditions selected during electrospinning for commercial PHBV. Flow Needle- Concentration Voltage rate collector Time Sample (% by weight) (kV) (ml/h) distance (cm) (h) PHBV 10 19 6 15 2

[0148] The resulting bilayer structure is then subjected to thermal treatment in a 4122 hot plate press by Carver, Inc. (Indiana, USA) at 160° C. for 5 seconds without pressure. The electrospun film, after annealing, has a thickness of about of 10 microns.

[0149] The bilayer sheet, with the layers already sealed, is subjected to thermoforming in the equipment under the conditions described in the preceding examples. The layer of the electrospun film, after thermoforming, has a thickness of about 10 microns.

[0150] Table 1 shows the mechanical results of the bilayer sheet and the thermoformability characteristics. As can be seen, this packaging has mechanical properties similar to those of PACKAGING 2, but with higher tear resistance.

[0151] As can be observed in Table 5, the barrier properties of the developed bilayer packaging are better in terms of an oxygen barrier compared to the monolayer packaging containing PHB described in EXAMPLE 2.

TABLE-US-00005 TABLE 5 Water vapor permeability (WVP), .sub.D-limonene permeability (LP) and oxygen permeability (OP) values of the obtained multilayer. The monolayer PHB values are included by way of control. WVP × 10.sup.17 LP × 10.sup.17 OP × 10.sup.21 (kg .Math. m.sup.−2 .Math. (kg .Math. m.sup.−2 .Math. (m.sup.3 .Math. m.sup.−2 .Math. Structure Pa.sup.−1 .Math. s.sup.−1) Pa.sup.−1 .Math. s.sup.−1) Pa.sup.−1 .Math. s.sup.−1) PACKAGING 0.72 ± 0.04 0.83 ± 0.08 0.32 ± 0.02 2 PACKAGING 0.60 ± 0.04 0.78 ± 0.08 <0.01* 9 *Not detectable in measurement equipment

Packaging 10:

[0152] The purpose of this example is to show a complete multilayer tray according to the present invention with mechanical, barrier and active properties. For this purpose, there is initially deposited on the structural layer described in example PACKAGING 2 a barrier layer of electrospun fibers of EVOH44 (Soarnol grade from Nippon Gohsei, Japan). Deposited on this bilayer structure, next, is another layer of electrospun fibers of elastomeric PHBV20 derived from fruit waste, as explained above, to which there is incorporated essential oil enriched in cinnamaldehyde in the solution before electrospinning (Cinnamomum, Sigma-Aldrich S.A., Madrid, Spain).

[0153] In the first electrospun layer of fibers of EVOH44, the solvents used are TFE, 99% purity, acquired from Sigma Aldrich S.A. (Madrid, Spain), and isopropanol, 99.5% purity, obtained from Acros Organics (Geel, Belgium). To generate the fibers, a solution of 6% EVOH44 in a mixture of isopropanol/water 70:30 (vol/vol) is prepared and stirred at 70° C. for 24 h. Then, the solution is processed by means of electrospinning using a Fluidnatek® LE-10 pilot plant device by Bioinicia S.L. (Valencia, Spain). Next, to confer active properties to the packaging, another layer, in this case of PHBV20, is electrospun onto the obtained structure. To that end, a solution of 8% PHBV20 in chloroform/butanol 75:25 (vol/vol) is prepared, being obtained from Sigma Aldrich S.A. (Madrid, Spain), and 10% cinnamaldehyde is incorporated to it. This mixture is stirred at room temperature for 24 h in a hermetically sealed packaging. Table 6 includes the conditions for processing each material. All the experiments were carried out under ambient conditions, i.e. 25° C. and 40% RH.

TABLE-US-00006 TABLE 6 Optimal conditions selected during electrospinning for the solution of EVOH and PHBV20 containing cinnamaldehyde. Needle- Flow collector Concentration Voltage rate distance Time Sample (% by weight) (kV) (ml/h) (cm) (h) EVOH44 6 15 5 16 2 PHBV20/ 8 12 6 15 1 cinnamaldehyde

[0154] The homogeneous deposition of fibers of PHBV20 with oregano essential oil on the surface of the layer of EVOH44 is thereby achieved. Lastly, there is incorporated a PHBV film with a thickness of 25 microns and having an HV content of 8 mol. % (PHBV8) with commercial reference BV301025 by Goodfellow Cambridge Ltd (Huntingdon, United Kingdom), allowed for contact with food and obtained by means of blow extrusion. The purpose of this monolayer film is to be in direct contact with the product to be packaged and prevent migrations from the rest of the layers onto the product, i.e. it acts as a food contact layer. FIG. 4 describes the process that is followed and the multilayer structure that is finally obtained.

[0155] To generate a final packaging with the desired properties, the multilayer structure is finally processed by thermoforming, following the same conditions described in the preceding examples. The layers are sealed at the same time the tray is obtained, the multilayer packaging thus being formed. In this case, the film is manually fixed to the frame of the thermoforming machine, but it could also be incorporated in the line in the form of a reel during thermoforming. The mechanical results were generated on the multilayer structure subjected to an annealing process for adhering the layers before testing.

[0156] Table 1 shows the mechanical results and the thermoformability characteristics of the obtained multilayer packaging. As can be seen, this packaging has mechanical properties and thermoformability similar to those of PACKAGING 2, but with higher tear resistance.

[0157] As can be observed in Table 7, the barrier properties of the developed bilayer packaging are better in terms of barrier compared to the monolayer packaging based on PHB described in example PACKAGING 2.

TABLE-US-00007 TABLE 7 Water vapor permeability (WVP), .sub.D-limonene permeability (LP) and oxygen permeability (OP) values of the obtained multilayer. The monolayer PHB values are included by way of control. WVP × 10.sup.17 LP × 10.sup.17 OP × 10.sup.21 (kg .Math. m.sup.−2 .Math. (kg .Math. m.sup.−2 .Math. (m.sup.3 .Math. m.sup.−2 .Math. Structure Pa.sup.−1 .Math. s.sup.−1) Pa.sup.−1 .Math. s.sup.−1) Pa.sup.−1 .Math. s.sup.−1) PACKAGING 0.72 ± 0.04 0.83 ± 0.08 0.32 ± 0.02 2 PACKAGING 0.10 ± 0.02 0.33 ± 0.08 <0.01* 10 *Not detectable in measurement equipment

[0158] Lastly, the antimicrobial activity of the final packaging was evaluated by means of Japanese industrial standard JIS Z 2801 (ISO 22196: 2007) against strains of S. aureus (ATCC 6538p) and strains of E. coli (ATCC 25922). To that end, a suspension of microorganisms was deposited on the face of the food contact layer in samples having sizes of 1.5×1.5 cm.sup.2 when open. They are incubated at 25° C. and at a relative humidity of 95% for 24 h. Then the bacteria are recovered with phosphate-buffered saline PBS, diluted 10 times and incubated at 37° C. for 24 h to quantify the number of viable bacteria by conventional plate count. The antimicrobial activity was evaluated at 1, 8 and 15 days. The antimicrobial activity (R) value is calculated by determining log.sub.10 (N.sub.0/N.sub.t), wherein N.sub.0 is the average number of viable bacteria cells in the untreated test piece after 24 h and N.sub.t is the average number of viable bacteria cells in the antimicrobial sample after 24 h. The results are included in Table 8.

TABLE-US-00008 TABLE 8 R values against E. coli and S. aureus of the developed multilayer structures (packaging) with cinnamaldehyde. PACKAGING 2 is used as a test control. PACKAGING PACKAGING 2 Log 10 Log Bacteria Days (CFU/ml) (CFU/ml) R S. aureus 1 6.80 ± 0.09 4.50 ± 0.11 2.3 ± 0.09 8 6.76 ± 0.21 4.06 ± 0.19 2.7 ± 0.23 15 6.89 ± 0.19 3.79 ± 0.15 3.1 ± 0.17 E. coli 1 6.69 ± 0.07 4.89 ± 0.55 1.8 ± 0.27 8 6.72 ± 0.33 4.62 ± 0.17 2.1 ± 0.31 15 6.79 ± 0.45 4.39 ± 0.19 2.4 ± 0.33

[0159] As can be seen, given its R values>2, the multilayer packaging described in the present invention presents a high biocidal effectiveness against bacteria present in foods. This is due to the capacity of efficiently releasing the cinnamaldehyde essential oil.