Multi-layer packaging film

Abstract

A multi-layer packaging film, comprising: (a) a printed outer layer, (b) a product-side inner layer, and (c) a laminate layer between the printed outer layer and the product-side inner layer.

Description

[0001] Related Applications

[0002] This international patent application is a continuation of prior U.S. non - provisional patent application Ser. No. 16 / 943,866, filed Jul. 30, 2021. The entire content of the U.S. prior document is incorporated herein by reference, and in case of any disclosure or definition inconsistent with the present specification, the disclosure or definition herein shall prevail. Technical Field

[0003] The present invention generally relates to polymeric materials and multilayer films formed therefrom. In some embodiments, the present invention relates to biodegradable and / or compostable multilayer polymeric films for packaging applications. Background Art

[0004] Snack foods (including, but not limited to, potato chips, crackers, and cookies) are typically packaged in sealed disposable bags. Conventional bags may include multilayer polymeric films bonded or laminated together to provide a finished product with a desired combination of strength properties, barrier properties (e.g., for moisture, oxygen, oils, etc.), and good printability for product packaging graphics.

[0005] In the past, most or all of the film layers in conventional snack food bags were mainly composed of petroleum - based polymers such as polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET). Although these polymers can provide excellent strength, barrier, and / or printability characteristics to the film structure, they are not easily degraded or decomposed after disposal (either in landfills or through home composting techniques). Thus, the film structures and bags made from these polymers may remain in landfills for hundreds of years after disposal. Summary of the Invention

[0006] The scope of the present invention is defined solely by the appended claims and is not affected to any degree by the statements in this summary of the invention.

[0007] As an introduction, a first multilayer packaging film according to the present invention comprises: (a) a printed outer layer, (b) a product - side inner layer comprising a core layer and a barrier layer, and (c) a laminate layer between the printed outer layer and the product - side inner layer. The printed outer layer comprises: (i) polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), cellophane, paper, or a combination thereof, (ii) graphic elements, and (iii) an optional first nucleating agent. The core layer comprises PHA and a second nucleating agent.

[0008] The second multi-layer packaging film according to the present invention comprises: (a) a printed outer layer (b), a product-side inner layer, and (c) a laminated layer between the printed outer layer and the product-side inner layer. The printed outer layer comprises: (i) PHA, PLA, PBAT, PBS, cellophane, paper, or a combination thereof, (ii) graphic elements, and (iii) an optional first nucleating agent. The product-side inner layer comprises: (i) a shielding layer, (ii) a core layer, and (iii) a third layer between the shielding layer and the core layer, wherein each of the core layer and the third layer comprises PHA and a second nucleating agent. The laminated layer comprises an adhesive, an extrusion lamination resin, or a combination thereof. Description of the Drawings

[0009] Figure 1 A schematic diagram showing a first representative multi-layer packaging film according to the present invention is shown.

[0010] Figure 2 A schematic diagram showing a second representative multi-layer packaging film according to the present invention is shown.

[0011] Figure 3 A schematic diagram showing a third representative multi-layer packaging film according to the present invention is shown.

[0012] Figure 4 A schematic diagram showing a fourth representative multi-layer packaging film according to the present invention is shown.

[0013] Figure 5 A schematic diagram showing a fifth representative multi-layer packaging film according to the present invention is shown.

[0014] Figure 6 A schematic diagram showing a sixth representative multi-layer packaging film according to the present invention is shown. Figure 1 A schematic diagram showing a first representative multi-layer packaging film according to the present invention is shown.

[0015] Figure 7 A schematic diagram showing a seventh representative multi-layer packaging film according to the present invention is shown.

[0016] Figure 8 A schematic diagram showing an eighth representative multi-layer packaging film according to the present invention is shown.

[0017] Figure 9 A schematic diagram showing a ninth representative multi-layer packaging film according to the present invention is shown.

[0018] Figure 10 A schematic diagram showing a tenth representative multi-layer packaging film according to the present invention is shown.

[0019] Figure 11 A schematic diagram showing an eleventh representative multi-layer packaging film according to the present invention is shown.

[0020] Figure 12 A schematic diagram showing a twelfth representative multilayer packaging film according to the present invention. Detailed implementation

[0021] A biodegradable multilayer packaging film structure suitable for packaging potato chips and other snack foods has been discovered and described herein. In some embodiments, the biodegradable multilayer packaging film according to the present invention is at least partially compostable (and, in some embodiments, at least partially home compostable).

[0022] In this specification and in the appended claims, the following definitions will be understood:

[0023] As used herein, the term "biodegradable" refers to a plastic or polymeric material that is at least partially biodegradable by organisms (microorganisms) in anaerobic and aerobic environments (as determined by ASTM D5511), in soil environments (as determined by ASTM D5988), in freshwater environments (as determined by ASTM D5271 (EN29408)), or in marine environments (as determined by ASTM D6691). The biodegradability of biodegradable plastics can also be determined using ASTM D6868, ASTM D6400, and European EN 13432.

[0024] As used herein, the term "compostable" refers to a biodegradable material that can be decomposed only into carbon dioxide, water, inorganic compounds, and / or biomass, leaving no visible or toxic residues. In some embodiments, when determined by ASTM D6400 for industrial or home compostability, the multilayer packaging film according to the present invention is "compostable".

[0025] It should be understood that the elements and features of the various representative embodiments described below can be combined in different ways to produce new embodiments that also fall within the scope of the present invention.

[0026] As an overview, the multilayer packaging film according to the present invention includes: (a) a printed outer layer, (b) a product-side inner layer, and (c) a laminated layer between the printed outer layer and the product-side inner layer. In some embodiments, the printed outer layer includes a biopolymer and graphic elements, the product-side inner layer includes a core layer and a shielding layer, and the laminated layer includes an adhesive.

[0027] The polymeric materials used to form the printed outer layer, the product-side inner layer, and / or the laminated layer of the multilayer packaging film according to the present invention can exist as homopolymers, copolymers, terpolymers, and / or blends thereof.

[0028] In some embodiments, the printed outer layer comprises: (i) polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), cellophane, paper, or a combination thereof, (ii) graphic elements, and (iii) an optional first nucleating agent. In some embodiments, the printed outer layer further comprises polybutylene succinate adipate (PBSA), polycaprolactone (PCL), or a combination thereof. In some embodiments, particularly but not exclusively in embodiments where one or more layers contain polyhydroxyalkanoate (PHA), a nucleating agent may also be present. In some embodiments, the printed outer layer comprises both PHA and an optional first nucleating agent. In some embodiments, the graphic elements of the printed outer layer include text, images, or a combination thereof.

[0029] In some embodiments, the laminated layer comprises an adhesive, and in some embodiments, the adhesive comprises a compostable water-based adhesive, a compostable solvent-based adhesive, a compostable solvent-free adhesive, a non-compostable water-based adhesive, a non-compostable solvent-based adhesive, a non-compostable solvent-free adhesive, or a combination thereof. In some embodiments, the laminated layer comprises an extrusion lamination resin. Representative extrusion lamination resins for use in accordance with the present invention include (but are not limited to) PLA-based extrusion lamination resins, PHA-based extrusion lamination resins, PBSA-based extrusion lamination resins, PBAT-based extrusion lamination resins, PCL-based extrusion lamination resins, starch-based extrusion lamination resins, or a combination thereof.

[0030] In some embodiments, the product-side inner layer comprises: (i) a core layer and (ii) a shielding layer. In other embodiments, the product-side inner layer further comprises: (iii) a sealant layer.

[0031] In some embodiments, the core layer of the product-side inner layer further comprises a biodegradable polymer selected from PLA, PBS, PBSA, PGA, poly(lactic-co-glycolic acid) (PLGA), PBAT, and combinations thereof. In some embodiments, the core layer of the product-side inner layer comprises PHA and a second nucleating agent. In some embodiments, the core layer of the product-side inner layer further comprises PLA, PBSA, or a combination thereof. In some embodiments, the core layer of the product-side inner layer further comprises PLA.

[0032] The second nucleating agent of the core layer and the optional first nucleating agent of the printed outer layer can be the same or different. In some embodiments, each of the second nucleating agent and the optional first nucleating agent is independently selected from: (1) a compound having an orthorhombic crystal structure, (2) a compound having a hexagonal crystal structure, (3) a compound having a tetragonal crystal structure, (4) an allotrope having at least one orthorhombic, hexagonal or tetragonal crystal form, (5) a polymorphic compound having at least one orthorhombic, hexagonal or tetragonal crystal form, and (6) combinations thereof. In some embodiments, each of the second nucleating agent and the optional first nucleating agent is independently selected from erythritol, pentaerythritol, dipentaerythritol, anatase, wulfenite, aragonite, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, sulfur, selenium, phosphorus, benzamide, and combinations thereof.

[0033] In some embodiments, the core layer of the product-side inner layer further comprises a filler selected from inorganic fillers, bio-based fillers, or combinations thereof. Representative inorganic fillers for use in accordance with the present invention include (but are not limited to) alkali metal carbonates, alkaline earth metal carbonates, alkali metal sulfates, alkaline earth metal sulfates, or combinations thereof. In some embodiments, the inorganic filler for use in accordance with the present invention is selected from sodium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum sulfate, magnesium oxide, calcium oxide, aluminum oxide, mica, talc, silica, clay, glass beads, titanium dioxide, aluminum hydroxide, zeolites, and combinations thereof. In some embodiments, the inorganic filler comprises calcium carbonate. Representative bio-based fillers for use in accordance with the present invention include (but are not limited to) wheat straw, soybean meal, rice husk, oat husk, or combinations thereof.

[0034] In some embodiments, the product-side inner layer is formed by a method comprising co-extruding at least a first composition and a second composition, the first composition forming the core layer and the second composition forming the shielding layer. In some embodiments, the shielding layer of the product-side inner layer is provided in the form of a coating, whereas in other embodiments, the shielding layer of the product-side inner layer is formed by a co-extrusion method. In some embodiments, the shielding layer comprises a metal (e.g., aluminum, aluminum oxide, or combinations thereof), microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, graphene, a water-based primer coating, a solvent-based primer coating, a polyurethane-based primer coating, a polyacrylate-based primer coating, polyglycolide (PGA), a phenoxy resin, magnetic nanoparticles, an epoxy resin microencapsulated amine, a silica deposition layer, or combinations thereof. In some embodiments, the shielding layer comprises aluminum, aluminum oxide, or combinations thereof.

[0035] In some embodiments, the product-side inner layer further includes at least a third layer in addition to the core layer and the shielding layer, and the method of forming the product-side inner layer further includes co-extruding at least a third composition that forms the third layer. In other embodiments, the product-side inner layer further includes at least a fourth layer, and the method of forming the product-side inner layer further includes co-extruding at least a fourth composition that forms the fourth layer.

[0036] In some embodiments, the shielding layer of the product-side inner layer includes a metal, and the product-side inner layer further includes a third layer between the shielding layer and the core layer.

[0037] In some embodiments, the third layer of the product-side inner layer includes polyvinyl alcohol (PVA), modified cellulose acetate, polysaccharides, PGA, PHA, PLA, PBSA, PBS, or a combination thereof. In some embodiments, the third layer of the product-side inner layer further includes PHA, PLA, or a combination thereof. In some embodiments, the third layer of the product-side inner layer includes PHA, PLA, or a combination thereof, and the core layer of the product-side inner layer further includes PLA.

[0038] In some embodiments, the shielding layer of the product-side inner layer includes a metal, the product-side inner layer further includes a third layer and a fourth layer, and the core layer is between the third layer and the fourth layer. In some embodiments, the fourth layer includes polyvinyl alcohol (PVA), modified cellulose acetate, polysaccharides, PGA, PHA, PLA, PBSA, PBS, or a combination thereof. In some embodiments, the fourth layer includes PHA, PLA, or a combination thereof.

[0039] In some embodiments, the fourth layer includes a sealant layer, and in some embodiments, the sealant layer includes PHA, PLA, PBSA, or a combination thereof. In other embodiments, the fourth layer includes a primer coating, and in some embodiments, the primer coating is between the shielding layer of the product-side inner layer and the third layer. In some embodiments, the primer coating is water-based, in other embodiments, the primer coating is solvent-based, in other embodiments, the primer coating is polyurethane-based, in other embodiments, the primer coating is polyacrylate-based, in other embodiments, the primer coating is polysaccharide-based, in other embodiments, the primer coating is nanocellulose-based, in other embodiments, the primer coating is polyglycolic acid (PGA)-based, and in other embodiments, the primer coating is polyvinyl alcohol (PVOH)-based. In some embodiments, the fourth layer includes a silica deposition layer, and in some embodiments, the silica deposition layer is between the shielding layer and the third layer. In some embodiments, the fourth layer includes an e-beam top coating, and in some embodiments, the e-beam top coating is between the laminate layer and the shielding layer.

[0040] The packaging article according to the present invention, including (but not limited to) food packaging and beverage packaging, contains a multi-layer packaging film of the type described herein.

[0041] In some embodiments, a portion of the film structure is formed and cut to provide a blank for a generally rectangular food packaging pouch or bag. A first set of generally parallel edges of the blank are overlapped and sealed along a seam to form a tubular sleeve. A food product can be inserted into the sleeve, and then the ends of the sleeve can be sealed to provide the final packaged food product. In some embodiments, the method can be automated by using a vertical or horizontal form-fill-seal ("FFS") packaging machine. Food products that can be packaged according to the present invention include (but are not limited to) snack chips such as potato chips, tortilla chips, pretzels, candies, and the like.

[0042] As can be appreciated from the above description and as described more fully below with reference to Figures 1 - 12 The multi-layer food packaging film structure according to the present invention includes at least a shielding web and a printed web. The shielding web surface is adhered or laminated to the printed web by an adhesive layer or an extrusion laminate layer disposed between the shielding web surface and the printed web.

[0043] In some embodiments, both the shielding web and the printed web are biodegradable and / or compostable. More specifically, each individual layer of the multi-layer film structure is biodegradable and / or compostable.

[0044] In some embodiments, the barrier web is composed of at least 3 film layers. For example, the barrier web can at least include a barrier web core layer having a first side and a second side, a barrier web surface layer adhered or laminated to the first side of the web core layer, and a packaging sealant layer adhered or laminated to the second side of the web core layer.

[0045] The composition of each individual layer of the barrier web can be slightly different, as described below. However, in some embodiments, each individual layer of the barrier web is biodegradable and / or home compostable.

[0046] As described above, the barrier web core layer is a film layer having a first side and a second side. The thickness of the core layer is from about 0.2 mils to about 2.0 mils.

[0047] The composition of the core layer includes at least two different biodegradable polymers, a nucleating agent, and a chain extender. Optionally, the core layer can further include fillers, plasticizers, anti-caking agents, and / or impact modifiers.

[0048] In some embodiments, the barrier web core layer includes polyhydroxyalkanoate as the first biodegradable polymer. The core layer is generally composed of about 10 wt% to about 90 wt% of polyhydroxyalkanoate. In some embodiments, the core layer is composed of about 30 wt% to about 85 wt% of polyhydroxyalkanoate.

[0049] In some embodiments, the barrier web core layer further includes a second biodegradable polymer selected from polybutylene succinate, polybutylene succinate-co-butylene adipate, polylactic acid, cellulose acetate, and mixtures thereof. The amount of this second biodegradable polymer is about 30 wt% to about 90 wt% of the core layer.

[0050] In some embodiments, the barrier web core layer can include about 30 wt% to about 70 wt% of polybutylene succinate, or about 30 wt% to about 70 wt% of polybutylene succinate-co-butylene adipate, or about 10 wt% to about 60 wt% of polylactic acid.

[0051] In some embodiments, the nucleating agent is present in the core layer in an amount of about 0.1 wt% to about 5 wt%. In some embodiments, the core layer nucleating agent can be selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or similar nucleating agents and combinations thereof.

[0052] In some embodiments, the amount of chain extender in the core layer is from about 0.01 wt% to about 1.0 wt%. Chain extenders suitable for the core layer include (but are not limited to) organic peroxyacids, inorganic peroxyacids, epoxy-functionalized reagents, and / or similar chain extenders and combinations thereof.

[0053] In some embodiments, the core layer may optionally further include a filler material. Materials suitable for the filler are selected from calcium carbonate, talc, nanoclay, nanocellulose, hemp fiber, kaolin, carbon black, wollastonite, glass fiber, carbon fiber, graphite fiber, mica, silica, dolomite, barium sulfate, magnetite, halloysite, zinc oxide, titanium dioxide, montmorillonite, feldspar, asbestos, boron, steel, carbon nanotubes, cellulose fiber, flax, cotton, starch, polysaccharide, aluminum hydroxide, magnesium hydroxide, chitin, and / or similar materials and combinations thereof.

[0054] In some embodiments, the amount of filler in the core layer of the shielding web can be up to about 50 wt%. In some embodiments, the core layer consists of about 5 wt% to about 40 wt% of the filler.

[0055] In some embodiments, the core layer may further include an optional plasticizer material. Materials suitable for the plasticizer include (but are not limited to) sebacate esters, citrate esters, fatty acid esters of adipic acid, succinic acid, and glucaric acid, lactate esters, alkyl diesters, citrate esters, alkyl methyl esters, dibenzoate esters, propylene carbonate, caprolactone diols having a number average molecular weight of 200 - 10,000 g / mol, polyethylene glycols having a number average molecular weight of 400 - 10,000 g / mol, esters of vegetable oils, long-chain alkyl acids, adipate esters, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 ester, HALLGREEN R-8010 ester, polyhydroxyalkanoate copolymers containing monomer residues of hydroxy fatty acid esters other than hydroxybutyrate esters in an amount of at least 18 mol%, and / or similar materials, and combinations thereof.

[0056] In some embodiments, the amount of plasticizer in the core layer of the shielding web can be up to about 50 wt%. In some embodiments, the core layer consists of about 5 wt% to about 15 wt% of the plasticizer.

[0057] In some embodiments, the core layer may further include up to 20 wt% of an impact modifier. In some embodiments, the core layer includes about 5 wt% to about 15 wt% of the impact modifier.

[0058] In addition, in some embodiments, the core layer may include up to 50 wt% of one or more additives selected from polyvinyl alcohol, polyvinyl acetate, polyvinyl laurate, ethylene vinyl acetate, a butanediol vinyl alcohol copolymer sold by Mitsubishi under the trade name G-POLYMER, polybutylene adipate terephthalate (PBAT), a biodegradable and compostable polymer sold by BASF under a trade name, polyglycolic acid, polycaprolactone, furan dicarboxylic acid-based polyesters, thermoplastic starch, cellulose, nanocellulose, dextran, and / or similar additives and combinations thereof.

[0059] In some embodiments, the barrier web further includes a polymeric surface layer adhesively or laminated to a first side of the web core layer. The surface layer has a thickness of from about 0.2 to about 2.0 mils. In some embodiments, the surface layer includes at least two different biodegradable polymers and a nucleating agent. In some embodiments, the barrier web surface layer includes a polyhydroxyalkanoate as the first biodegradable polymer. In some embodiments, the surface layer consists of from about 10 wt% to about 90 wt% of the polyhydroxyalkanoate. In some embodiments, the surface layer consists of from about 40 wt% to about 90 wt% of the polyhydroxyalkanoate.

[0060] In some embodiments, the barrier web surface layer further includes a second biodegradable polymer selected from polybutylene succinate, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-butylene terephthalate, polycaprolactone, polylactic acid, polyglycolic acid, cellulose acetate, and mixtures thereof. In some embodiments, the amount of the second biodegradable polymer is from about 30 wt% to about 90 wt% of the core layer.

[0061] In some embodiments, the barrier web surface layer may include from about 40 wt% to about 90 wt% of polybutylene succinate, or from about 40 wt% to about 90 wt% of polybutylene succinate-co-butylene adipate, or from about 30 wt% to about 70 wt% of polylactic acid.

[0062] In some embodiments, the surface layer nucleating agent is present in an amount of from about 0.1 wt% to about 5 wt%. In some embodiments, the surface layer nucleating agent is selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or similar nucleating agents and combinations thereof.

[0063] In some embodiments, the shielding web further includes a sealant layer adhesively or laminated to a second side of the web core layer. In some embodiments, the sealant layer has a thickness of from about 0.2 to about 2.0 mils. In some embodiments, the sealant layer includes at least one biodegradable polymer and a nucleating agent.

[0064] In some embodiments, at least one biodegradable polymer in the sealant layer may be selected from polyhydroxyalkanoates, polybutylene succinate, polybutylene succinate-co-butylene adipate, polylactic acid, polycaprolactone, polyglycolic acid, polybutylene adipate-co-butylene terephthalate, cellulose acetate, and / or similar polymers, and combinations thereof. In some embodiments, the amount of the biodegradable polymer in the sealant layer is from about 30 wt% to about 100 wt%.

[0065] In some embodiments, the shielding web sealant layer may include from about 30 wt% to about 100 wt% of polyhydroxyalkanoates, or from about 10 wt% to about 100 wt% of polybutylene succinate, or from about 10 wt% to about 100 wt% of polybutylene succinate-co-butylene adipate, or from about 10 wt% to about 100 wt% of polylactic acid.

[0066] In some embodiments, the shielding web sealant layer further includes a nucleating agent, which in some embodiments is present in an amount of from about 0.1 wt% to about 3 wt%. In some embodiments, the sealant layer nucleating agent is selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or similar nucleating agents and combinations thereof.

[0067] In some embodiments, the sealant layer may further include from about 0.1 to about 4.0 wt% of an anti-caking agent, such as an amide material or a large particle size filler.

[0068] In some embodiments, the various layers of the shielding web may be joined together by lamination or by using an adhesive. As used herein, an adhesive includes aqueous and / or organic solvents that evaporate substantially over time, as well as tackifiers and other components. After the adhesive dries, only the non-solvent portion remains and the non-solvent portion is used to bind the various layers of the shielding web together. In contrast, in lamination, an extruded polymer film having little or no solvent is disposed between two layers of the web to bind the layers together.

[0069] As described above, the film structure according to the present invention further includes a printed web. Similar to the shielding web, in some embodiments, the printed web is biodegradable and / or home compostable.

[0070] In some embodiments, the printed web has a first side and a second side, and the desired packaging graphics can be printed on either side of the printed web. Thus, the printed web can be printed on its outer side or, conversely, on its inner side.

[0071] In some embodiments, the printed web consists of: (1) about 10 wt% to about 90 wt% of polyhydroxyalkanoate; (2) about 30 wt% to about 90 wt% of at least one biodegradable polymer selected from polybutylene succinate, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-butylene terephthalate, polycaprolactone, polylactic acid, cellulose acetate, and mixtures thereof; (3) about 0.1 wt% to about 3 wt% of a nucleating agent; and (4) optionally, up to about 15 wt% of a plasticizer.

[0072] In some embodiments, the printed web may include about 30 wt% to about 100 wt% of polyhydroxyalkanoate, or about 30 wt% to about 70 wt% of polybutylene succinate, or about 30 wt% to about 70 wt% of polybutylene succinate-co-butylene adipate, or about 40 wt% to about 70 wt% of polylactic acid. In some embodiments, the printed web may include from 10 wt% up to 100 wt% of cellulose acetate.

[0073] In some embodiments, the nucleating agent for the printed web may be selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or similar nucleating agents and combinations thereof.

[0074] In some embodiments, the printed web may optionally further comprise from about 5 wt% to about 30 wt% plasticizer. Plasticizers suitable for the printed web include, but are not limited to, sebacates, citrates, fatty acid esters of adipic, succinic and glucaric acids, lactates, alkyl diesters, citrates, alkyl methyl esters, dibenzoates, propylene carbonate, caprolactone diols having a number average molecular weight of 200 - 10,000 g / mol, polyethylene glycols having a number average molecular weight of 400 - 10,000 g / mol, esters of vegetable oils, long chain alkyl acids, adipates, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM - 8830 ester, HALLGREEN R - 8010 ester, polyhydroxyalkanoate copolymers comprising monomer residues of hydroxy fatty acid esters other than hydroxybutyrate esters in an amount of at least 18 mol%, and / or similar plasticizers, and combinations thereof.

[0075] In some embodiments, the surface layer of the shielding web is adhered or laminated to the printed web by an adhesive layer or an extrusion laminate layer disposed between the surface layer of the shielding web and the printed web.

[0076] Suitable adhesives can be water - based, organic solvent - based adhesives, or solvent - free adhesives (e.g., polyurethanes). Suitable laminating materials can be blends of biodegradable polymers (including reactive blends). Representative biodegradable polymers for extrusion lamination include, but are not limited to, polycaprolactone and poly(butylene adipate terephthalate) (PBAT). During the lamination process, the polymer resin is melted in an extruder and passed through a die sandwiched between the printed web and the shielding web to bond the two webs together.

[0077] In each of the plurality of layers described above, the polyhydroxyalkanoate polymer can be a homopolymer consisting of only a single type of monomer residue. In some embodiments, the polyhydroxyalkanoate polymer is a copolymer consisting of two or more different types of monomer residues. In some embodiments, the polyhydroxyalkanoate polymer can be a terpolymer consisting of at least 3 different types of monomer residues.

[0078] For example, in some embodiments, the at least one polyhydroxyalkanoate polymer is a copolymer consisting of from about 75 to about 99.9 mol% monomer residues of 3 - hydroxybutyrate and from about 0.1 to about 25 mol% monomer residues of a second 3 - hydroxy fatty acid ester having 5 to 12 carbon atoms.

[0079] In other embodiments, the at least one polyhydroxyalkanoate polymer is a terpolymer composed of monomer residues of from about 75 to about 99.9 mol% of 3-hydroxybutyrate, monomer residues of from about 0.1 to about 25 mol% of 3-hydroxyhexanoate, and monomer residues of from about 0.1 to about 25 mol% of a third 3-hydroxy fatty acid ester having 5 to 12 carbon atoms.

[0080] In some embodiments, the at least one polyhydroxyalkanoate polymer has a weight average molecular weight of from about 50,000 Daltons to about 7.5 million Daltons, and in some embodiments, has a weight average molecular weight of from about 300,000 Daltons to about 3 million Daltons.

[0081] Reference will now be made to the attached Figures 1 - 12 to describe a representative construction of an exemplary multilayer packaging film according to the present invention.

[0082] Figure 1 Shown is a multilayer packaging film 2 according to a first embodiment of the present invention. The multilayer packaging film 2 has at least a three-layer structure, which includes a printed outer layer 4, a product-side inner layer 8, and a laminate layer 6 interposed between the printed outer layer 4 and the product-side inner layer 8. The printed outer layer 4 includes: (i) polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), cellophane, paper, or a combination thereof, (ii) graphic elements, and (iii) an optional first nucleating agent. The product-side inner layer 8 includes: (i) a core layer and (ii) a shielding layer. The core layer includes PHA and a second nucleating agent.

[0083] Figure 2 Shown is a multilayer packaging film 10 according to a second embodiment of the present invention. The multilayer packaging film 10 has at least a three-layer structure, which includes a printed outer layer 12, a product-side inner layer 16, and a laminate layer 14 interposed between the printed outer layer 12 and the product-side inner layer 16. The printed outer layer 12 includes graphic elements 18 and a biopolymer 20 (e.g., a PHA-containing blend). The laminate layer 14 includes an adhesive 22. The product-side inner layer 16 includes a shielding layer 24 (e.g., metal), a core layer 28 (e.g., a PHA / PLA blend), a third layer 26 (e.g., a PHA-containing surface layer), and a fourth layer 30 (e.g., a PHA-containing sealant layer).

[0084] Figure 3Shows a multilayer packaging film 32 according to a third embodiment of the present invention. This embodiment corresponds to a double-layer composite reverse printing structure. The multilayer packaging film 32 has at least a three-layer structure, which includes a printed outer layer 34, a product-side inner layer 38, and a composite layer 36 between the printed outer layer 34 and the product-side inner layer 38. The printed outer layer 34 includes a transparent film 40 (e.g., PHA blend) and reverse printing 42. The composite layer 36 includes an adhesive 44. The product-side inner layer 38 includes a shielding layer 46 (e.g., metal), a core layer 52 (e.g., PHA / PLA blend), a third layer 50 (e.g., PHA / PLA-containing surface layer), a fourth layer 54 (e.g., PHA-containing sealant), and a primer coating 48.

[0085] Figure 4 Shows a multilayer packaging film 56 according to a fourth embodiment of the present invention. This embodiment corresponds to a double-layer composite surface printing structure. The multilayer packaging film 56 has at least a three-layer structure, which includes a printed outer layer 58, a product-side inner layer 62, and a composite layer 60 between the printed outer layer 58 and the product-side inner layer 62. The printed outer layer 58 includes surface printing 64 and an opaque film or paper (e.g., PHA blend) 66. Figure 4 The shown multilayer packaging film 56 and Figure 3 The respective printed outer layers (58 and 34 respectively) of the shown multilayer packaging film 32 are different in construction. The composite layer 60 includes an adhesive 68. The product-side inner layer 62 includes a shielding layer 70 (e.g., metal), a core layer 76 (e.g., PHA / PLA blend), a third layer 74 (e.g., PHA / PLA-containing surface layer), a fourth layer 78 (e.g., PHA-containing sealant), and a primer coating 72.

[0086] Figure 5 Shows a multilayer packaging film 80 according to a fifth embodiment of the present invention. This embodiment corresponds to a double-layer composite extrusion lamination structure. The multilayer packaging film 80 has at least a three-layer structure, which includes a printed outer layer 82, a product-side inner layer 86, and a composite layer 84 between the printed outer layer 82 and the product-side inner layer 86. The printed outer layer 82 includes printing 88 and a biopolymer (e.g., PHA blend) 90. The composite layer 84 includes extrusion lamination 92. The product-side inner layer 86 includes a shielding layer 94 (e.g., metal), a core layer 100 (e.g., PHA / PLA blend), a third layer 98 (e.g., PHA / PLA-containing surface layer), a fourth layer 102 (e.g., PHA-containing sealant), and a primer coating 96.

[0087] Figure 5Shows a multilayer packaging film 80 according to a sixth embodiment of the present invention. This embodiment corresponds to a double-layer co-extrusion laminated structure. The multilayer packaging film 80 has at least a three-layer structure, which includes a printed outer layer 82, a product-side inner layer 86, and a laminated layer 84 between the printed outer layer 82 and the product-side inner layer 86. The printed outer layer 82 includes a print 88 and a biopolymer (e.g., PHA blend) 90. The laminated layer 84 includes an extrusion laminate 92. The product-side inner layer 86 includes a shielding layer 94 (e.g., metal), a core layer 100 (e.g., PHA / PLA blend), a third layer 98 (e.g., PHA / PLA-containing surface layer), a fourth layer 102 (e.g., PHA-containing sealant), and a primer coating 96.

[0088] Figure 6 Shows a multilayer packaging film 104 according to a sixth embodiment of the present invention. This embodiment corresponds to a double-layer co-structure with an electron beam topcoat above the metal. The multilayer packaging film 104 has at least a three-layer structure, which includes a printed outer layer 106, a product-side inner layer 110, and a laminated layer 108 between the printed outer layer 106 and the product-side inner layer 110. The printed outer layer 106 includes a print 112 and a biopolymer (e.g., PHA blend) 114. The laminated layer 108 includes an adhesive 116. The product-side inner layer 110 includes a shielding layer 120 (e.g., metal), a core layer 126 (e.g., PHA / PLA blend), a third layer 124 (e.g., PHA / PLA-containing surface layer), a fourth layer 128 (e.g., PHA-containing sealant), a primer coating 122, and an electron beam topcoat 118 between the adhesive 116 and the shielding layer 120.

[0089] Figure 7 Shows a multilayer packaging film 130 according to a seventh embodiment of the present invention. This embodiment corresponds to a double-layer co-structure with a shielding surface layer. The multilayer packaging film 130 has at least a three-layer structure, which includes a printed outer layer 132, a product-side inner layer 136, and a laminated layer 134 between the printed outer layer 132 and the product-side inner layer 136. The printed outer layer 132 includes a transparent film 138 (e.g., PHA blend) and a reverse print 140. The laminated layer 134 includes an adhesive 142. The product-side inner layer 136 includes a shielding layer 146 (e.g., metal), a core layer 148 (e.g., PHA blend), a third layer 146 (e.g., shielding surface layer), and a fourth layer 150 (e.g., PHA-containing sealant).

[0090] Figure 8Shows a multi-layer packaging film 152 according to the eighth embodiment of the present invention. This embodiment corresponds to a double-layer laminate structure containing a silica primer layer. The multi-layer packaging film 152 has at least a three-layer structure, which includes a printed outer layer 154, a product-side inner layer 158, and a laminate layer 156 between the printed outer layer 154 and the product-side inner layer 158. The printed outer layer 154 includes a transparent film 160 (e.g., PHA blend) and a reverse print 162. The laminate layer 156 includes an adhesive 164. The product-side inner layer 158 includes a shielding layer 166 (e.g., metal), a core layer 172 (e.g., PHA / PLA blend), a third layer 170 (e.g., PHA / PLA-containing surface layer), a fourth layer 174 (e.g., PHA-containing sealant), and a silica deposition layer 168.

[0091] Figure 9 Shows a multi-layer packaging film 176 according to the ninth embodiment of the present invention. This embodiment corresponds to a three-layer laminate structure. The multi-layer packaging film 176 has at least a four-layer structure, which includes a printed outer layer 178, a product-side inner layer 182, a laminate layer 180 between the printed outer layer 178 and the product-side inner layer 182, and a sealant film layer 184. The printed outer layer 178 includes a transparent film 186 (e.g., PHA blend) and a reverse print 188. The laminate layer 180 includes an adhesive 190. In some embodiments, the laminate layer 180 is an extrusion laminate layer. The product-side inner layer 182 includes a shielding layer 192 (e.g., metal), a core layer 196 (e.g., PHA blend), and a third layer 194 (e.g., shielding surface layer). The sealant film layer 184 includes a sealant 198 (e.g., PHA-containing sealant), a sealant film 202, and an adhesive 200 between the sealant 198 and the sealant film 202.

[0092] Figure 10 Shows a multi-layer packaging film 204 according to the tenth embodiment of the present invention. This embodiment corresponds to a single-film structure. The multi-layer packaging film 204 has at least a structure including a surface print 208 and a product-side inner layer 206. The product-side inner layer 206 includes a shielding layer 212 (e.g., metal), a core layer 218 (e.g., PHA / PLA blend), a third layer 216 (e.g., PHA / PLA surface layer), a sealant 220 (e.g., PHA sealant), an electron beam topcoat 210, and a primer coat 214.

[0093] Figure 11Shows a multilayer packaging film 222 according to the eleventh embodiment of the present invention. This embodiment corresponds to a double-layer composite alternating structure. The multilayer packaging film 222 has a structure including at least a surface print 226, a product-side inner layer 224, and a sealant film layer 240. The product-side inner layer 224 includes a shielding layer 228 (e.g., metal), a core layer 234 (e.g., PHA blend), a third layer 232 (e.g., PHA-containing surface layer), a fourth layer 236 (e.g., PHA-containing surface layer), and a primer coating 230 between the shielding layer 228 and the third layer 232. An adhesive 238 is inserted between the fourth layer 236 and the sealant film layer 240.

[0094] Figure 12 Shows a multilayer packaging film 242 according to the twelfth embodiment of the present invention. This embodiment corresponds to a double-layer composite alternating structure. The multilayer packaging film 242 has a structure including at least a surface print 246, a product-side inner layer 244, and a sealant film layer 260. The product-side inner layer 244 includes a shielding layer 248 (e.g., metal), a core layer 254 (e.g., PHA blend), a third layer 252 (e.g., PHA blend-containing surface layer), a fourth layer 256 (e.g., PHA blend-containing surface layer), and a primer coating 250 between the shielding layer 248 and the third layer 252. An adhesive 258 is between the fourth layer 256 and the sealant film layer 260.

[0095] The other characteristics and advantages of the present invention can be described by the embodiments described in any one of the following listed clauses. It should be understood that any embodiment described herein can be used in combination with any other embodiment described herein, as long as the embodiments are not contradictory to each other.

[0096] 1. A multilayer packaging film, comprising: a printed outer layer, comprising: (i) polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), cellophane, paper, or a combination thereof, (ii) graphic elements, and (iii) an optional first nucleating agent; a product-side inner layer, comprising (i) a core layer and (ii) a shielding layer; and a laminate layer between the printed outer layer and the product-side inner layer; wherein the core layer comprises PHA and a second nucleating agent.

[0097] 2. The multilayer packaging film according to clause 1, wherein the printed outer layer further comprises polybutylene adipate succinate (PBSA), polycaprolactone (PCL), or a combination thereof.

[0098] 3. The multilayer packaging film according to any one of clauses 1-2, wherein the core layer further comprises a filler selected from inorganic fillers, bio-based fillers, or a combination thereof.

[0099] 4. The multilayer packaging film according to any one of clauses 1-3, wherein the inorganic filler comprises an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal sulfate, an alkaline earth metal sulfate, or a combination thereof.

[0100] 5. The multilayer packaging film according to any one of clauses 1-4, wherein the inorganic filler is selected from sodium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum sulfate, magnesium oxide, calcium oxide, aluminum oxide, mica, talc, silica, clay, glass beads, titanium dioxide, aluminum hydroxide, zeolite, and combinations thereof.

[0101] 6. The multilayer packaging film according to any one of clauses 1-5, wherein the inorganic filler comprises calcium carbonate.

[0102] 7. The multilayer packaging film according to any one of clauses 1-6, wherein the bio-based filler comprises wheat straw, soybean meal, rice husk, oat husk, or a combination thereof.

[0103] 8. The multilayer packaging film according to any one of clauses 1-7, wherein the laminate layer comprises an adhesive.

[0104] 9. The multilayer packaging film according to any one of clauses 1-8, wherein the adhesive comprises a compostable water-based adhesive, a compostable solvent-based adhesive, a compostable solvent-free adhesive, a non-compostable water-based adhesive, a non-compostable solvent-based adhesive, a non-compostable solvent-free adhesive, or a combination thereof.

[0105] 10. The multilayer packaging film according to any one of clauses 1-9, wherein the laminate layer comprises an extrusion laminate resin.

[0106] 11. The multilayer packaging film according to any one of clauses 1-10, wherein the extrusion laminate resin comprises a PLA-based extrusion laminate resin, a PHA-based extrusion laminate resin, a PBSA-based extrusion laminate resin, a PBAT-based extrusion laminate resin, a PCL-based extrusion laminate resin, a starch-based extrusion laminate resin, or a combination thereof.

[0107] 12. The multilayer packaging film according to any one of clauses 1-11, wherein the second nucleating agent and the optional first nucleating agent are the same or different.

[0108] 13. The multilayer packaging film according to any one of clauses 1-12, wherein each of the second nucleating agent and the optional first nucleating agent is independently selected from (1) a compound having an orthorhombic crystal structure, (2) a compound having a hexagonal crystal structure, (3) a compound having a tetragonal crystal structure, (4) an allotrope having at least one orthorhombic, hexagonal, or tetragonal crystal form, (5) a polymorphic compound having at least one orthorhombic, hexagonal, or tetragonal crystal form, and (6) combinations thereof.

[0109] 14. The multilayer packaging film according to any one of clauses 1-13, wherein each of the second nucleating agent and the optional first nucleating agent is independently selected from erythritol, pentaerythritol, dipentaerythritol, anatase, wulfenite, aragonite, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenic acid amide, erucic acid amide, stearamide, oleamide, polyhydroxybutyrate, sulfur, selenium, phosphorus, benzamide, and combinations thereof.

[0110] 15. The multilayer packaging film according to any one of clauses 1-14, wherein the printed outer layer comprises PHA and a first nucleating agent.

[0111] 16. The multilayer packaging film according to any one of clauses 1-15, wherein the product-side inner layer further comprises (iii) a sealant layer.

[0112] 17. The multilayer packaging film according to any one of clauses 1-16, wherein the core layer further comprises PLA, PBSA, or a combination thereof.

[0113] 18. The multilayer packaging film according to any one of clauses 1-17, wherein the barrier layer comprises a metal, microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, graphene, an aqueous basecoat, a solvent basecoat, a polyurethane basecoat, a polyacrylate basecoat, polyglycolide (PGA), a phenoxy resin, magnetic nanoparticles, an epoxy resin microencapsulated amine, a silica deposition layer, or a combination thereof.

[0114] 19. The multilayer packaging film according to any one of clauses 1-18, wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

[0115] 20. The multilayer packaging film according to any one of clauses 1-19, wherein the method of forming the product-side inner layer comprises coextruding at least a first composition and a second composition, the first composition forming the core layer and the second composition forming the barrier layer.

[0116] 21. The multilayer packaging film according to any one of clauses 1-20, wherein the product-side inner layer further comprises at least a third layer, and wherein the method further comprises coextruding at least a third composition, the third composition forming the third layer.

[0117] 22. The multilayer packaging film according to any one of clauses 1-21, wherein the product-side inner layer further comprises at least a fourth layer, and wherein the method further comprises coextruding at least a fourth composition, the fourth composition forming the fourth layer.

[0118] 23. The multi-layer packaging film according to any one of clauses 1-22, wherein the shielding layer comprises a metal, and wherein the product-side inner layer further comprises a third layer between the shielding layer and the core layer.

[0119] 24. The multi-layer packaging film according to any one of clauses 1-23, wherein the core layer further comprises a biodegradable polymer selected from PLA, PBS, PBSA, PGA, poly(lactic acid-co-glycolic acid) (PLGA), PBAT, and combinations thereof.

[0120] 25. The multi-layer packaging film according to any one of clauses 1-24, wherein the core layer further comprises PLA.

[0121] 26. The multi-layer packaging film according to any one of clauses 1-25, wherein the third layer comprises polyvinyl alcohol (PVA), modified cellulose acetate, polysaccharides, PGA, PHA, PLA, PBSA, PBS, or combinations thereof.

[0122] 27. The multi-layer packaging film according to any one of clauses 1-26, wherein the third layer comprises PHA, PLA, or combinations thereof.

[0123] 28. The multi-layer packaging film according to any one of clauses 1-27, wherein the third layer comprises PHA, PLA, or combinations thereof, and wherein the core layer further comprises PLA.

[0124] 29. The multi-layer packaging film according to any one of clauses 1-28, wherein the shielding layer comprises a metal, wherein the product-side inner layer further comprises a third layer and a fourth layer, and wherein the core layer is between the third layer and the fourth layer.

[0125] 30. The multi-layer packaging film according to any one of clauses 1-29, wherein the fourth layer is a sealant layer.

[0126] 31. The multi-layer packaging film according to any one of clauses 1-30, wherein the sealant layer comprises PHA, PLA, PBSA, or combinations thereof.

[0127] 32. The multi-layer packaging film according to any one of clauses 1-31, wherein the product-side inner layer shielding layer further comprises a fourth layer, and wherein the fourth layer comprises a primer coating.

[0128] 33. The multi-layer packaging film according to any one of clauses 1-32, wherein the primer coating is between the shielding layer and the third layer.

[0129] 34. The multi-layer packaging film according to any one of clauses 1-33, wherein the primer coating is water-based.

[0130] 35. The multilayer packaging film according to any one of clauses 1-33, wherein the primer coating is solvent-based.

[0131] 36. The multilayer packaging film according to any one of clauses 1-33, wherein the primer coating is polyurethane-based.

[0132] 37. The multilayer packaging film according to any one of clauses 1-33, wherein the primer coating is polyacrylate-based.

[0133] 38. The multilayer packaging film according to any one of clauses 1-37, wherein the product-side inner layer further comprises a fourth layer, and wherein the fourth layer comprises a silica deposition layer.

[0134] 39. The multilayer packaging film according to any one of clauses 1-38, wherein the silica deposition layer is between the shielding layer and the third layer.

[0135] 40. The multilayer packaging film according to any one of clauses 1-39, wherein the product-side inner layer further comprises a fourth layer, and wherein the core layer is between the third layer and the fourth layer.

[0136] 41. The multilayer packaging film according to any one of clauses 1-40, wherein the fourth layer comprises PVA, modified cellulose acetate, polysaccharide, PGA, PHA, PLA, PBSA, PBS, or a combination thereof.

[0137] 42. The multilayer packaging film according to any one of clauses 1-41, wherein the fourth layer comprises PHA, PLA, or a combination thereof.

[0138] 43. The multilayer packaging film according to any one of clauses 1-42, wherein the product-side inner layer further comprises a fourth layer, wherein the fourth layer comprises an electron beam topcoat, and wherein the electron beam topcoat is between the laminate layer and the shielding layer.

[0139] 44. The multilayer packaging film according to any one of clauses 1-43, wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

[0140] 45. The multilayer packaging film according to any one of clauses 1-44, wherein the graphic element comprises text, an image, or a combination thereof.

[0141] 46. A multilayer packaging film, comprising: a printed outer layer, comprising: (i) PHA, PLA, PBAT, PBS, cellophane, paper, or a combination thereof, (ii) graphic elements, and (iii) an optional first nucleating agent; a product-side inner layer, comprising (i) a barrier layer, (ii) a core layer, and (iii) a third layer between the barrier layer and the core layer, wherein each of the core layer and the third layer comprises PHA and a second nucleating agent; and a laminating layer, comprising an adhesive, an extrusion laminating resin, or a combination thereof, wherein the laminating layer is between the printed outer layer and the product-side inner layer.

[0142] 47. The multilayer packaging film according to clause 46, wherein the core layer and / or the third layer further independently comprises a filler selected from mineral fillers, bio-based fillers, and combinations thereof.

[0143] 48. The multilayer packaging film according to any one of clauses 46 - 47, wherein the core layer further comprises a biodegradable polymer selected from PLA, PBS, PBSA, PGA, PLGA, PBAT, and combinations thereof.

[0144] 49. A packaging article, comprising the multilayer packaging film according to any one of clauses 1 - 48.

[0145] 50. The packaging article according to clause 49, wherein the packaging article is food packaging.

[0146] 51. The packaging article according to clause 49, wherein the packaging article is snack food packaging.

[0147] 52. The packaging article according to clause 49, wherein the packaging article is beverage packaging.

[0148] 53. Multilayer food packaging film structure, which comprises: a biodegradable barrier web, which comprises a barrier web core layer having a first side and a second side, a barrier web surface layer adhered or laminated to the first side of the web core layer, and a packaging sealant layer adhered or laminated to the second side of the web core layer; and a biodegradable printed web having a first side and a second side, and ink printed on at least one of the first and second sides of the printed web, the printed web comprising: (1) from about 10 wt% to about 90 wt% of polyhydroxyalkanoate; (2) from about 30 wt% to about 90 wt% of at least one biodegradable polymer selected from polybutylene succinate, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-butylene terephthalate, polycaprolactone, polylactic acid, cellulose acetate and mixtures thereof; (3) from about 0.1 wt% to about 5 wt% of a nucleating agent; and (4) optionally, up to about 15 wt% of a plasticizer; wherein the barrier web surface layer is adhered or laminated to the printed web through an adhesive layer or an extrusion lamination layer disposed between the barrier web surface layer and the printed web.

[0149] 54. The film structure according to clause 53, wherein the barrier web surface layer comprises (1) from about 10 wt% to about 90 wt% of polyhydroxyalkanoate; (2) from about 30 wt% to about 90 wt% of at least one biodegradable polymer selected from polybutylene succinate, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-butylene terephthalate, polycaprolactone, polylactic acid, polyglycolic acid, cellulose acetate and mixtures thereof; and (3) from about 0.1 wt% to about 5 wt% of a nucleating agent.

[0150] 55. The film structure according to clause 54, wherein the surface layer comprises from about 40 wt% to about 90 wt% of polyhydroxyalkanoate.

[0151] 56. The film structure according to clause 54, wherein the surface layer comprises from about 40 wt% to about 90 wt% of polybutylene succinate.

[0152] 57. The film structure according to clause 54, wherein the surface layer comprises from about 40 wt% to about 90 wt% of polybutylene succinate-co-butylene adipate.

[0153] 58. The film structure according to clause 54, wherein the surface layer comprises from about 30 wt% to about 70 wt% of polylactic acid.

[0154] 59. The film structure according to clause 54, wherein the surface layer nucleating agent is selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate and mixtures thereof.

[0155] 60. The membrane structure according to Clause 53, wherein the shielding web core layer comprises: (1) about 10 wt% to about 90 wt% of polyhydroxyalkanoate; (2) about 30 wt% to about 90 wt% of at least one biodegradable polymer selected from polybutylene succinate, polybutylene adipate succinate, polylactic acid, cellulose acetate, and mixtures thereof; (3) about 0.1 wt% to about 5 wt% of a nucleating agent; (4) about 0.01 wt% to about 1.0 wt% of a chain extender; (5) optionally, up to about 50 wt% of a filler; (5) optionally, up to about 15 wt% of a plasticizer; and (6) optionally, up to about 20 wt% of an impact modifier.

[0156] 61. The membrane structure according to Clause 60, wherein the core layer comprises about 30 wt% to about 85 wt% of polyhydroxyalkanoate.

[0157] 62. The membrane structure according to Clause 60, wherein the core layer comprises about 30 wt% to about 70 wt% of polybutylene succinate.

[0158] 63. The membrane structure according to Clause 60, wherein the core layer comprises about 30 wt% to about 70 wt% of polybutylene succinate-co-butylene adipate.

[0159] 64. The membrane structure according to Clause 60, wherein the core layer comprises about 10 wt% to about 60 wt% of polylactic acid.

[0160] 65. The membrane structure according to Clause 60, wherein the core layer nucleating agent is selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and mixtures thereof.

[0161] 66. The membrane structure according to Clause 60, wherein the core layer filler is selected from calcium carbonate, talc, nanoclays, nanocellulose, hemp fiber, kaolin, carbon black, wollastonite, glass fiber, carbon fiber, graphite fiber, mica, silica, dolomite, barium sulfate, magnetite, halloysite, zinc oxide, titanium dioxide, montmorillonite, feldspar, asbestos, boron, steel, carbon nanotubes, cellulose fiber, flax, cotton, starch, polysaccharides, aluminum hydroxide, magnesium hydroxide, chitin, and mixtures thereof.

[0162] 67. The membrane structure according to Clause 60, wherein the core layer comprises about 5 wt% to about 40 wt% of a filler.

[0163] 68. The membrane structure according to Clause 8, wherein the core layer comprises about 5 wt% to about 30 wt% of a plasticizer.

[0164] 69. The membrane structure according to clause 60, wherein the core layer comprises a plasticizer selected from the group consisting of sebacates, citrates, fatty acid esters of adipic acid, succinic acid and glucaric acid, lactates, alkyl diesters, citrates, alkyl methyl esters, dibenzoates, propylene carbonate, caprolactone diols having a number average molecular weight of 200-10,000 g / mol, polyethylene glycols having a number average molecular weight of 400-10,000 g / mol, vegetable oil esters, long-chain alkyl acids, adipates, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 ester, HALLGREEN R-8010 ester, polyhydroxyalkanoate copolymers comprising monomer residues of hydroxy fatty acid esters other than hydroxybutyrate esters in an amount of at least 18 mol% and mixtures thereof.

[0165] 70. The membrane structure according to clause 60, wherein the core layer comprises a chain extender selected from organic peroxyacids, inorganic peroxyacids, epoxy-functionalized reagents or mixtures thereof.

[0166] 71. The membrane structure according to clause 60, wherein the core layer comprises from about 5 wt% to about 15 wt% of an impact modifier.

[0167] 72. The membrane structure according to clause 60, wherein the core layer further comprises up to 50 wt% of one or more additives selected from polyvinyl alcohol, polyvinyl acetate, polyvinyl laurate, ethylene vinyl acetate, G-POLYMER, polybutylene adipate terephthalate (PBAT), Ecoflex, polyglycolic acid, polycaprolactone, furandicarboxylic acid-based polyesters, thermoplastic starch, cellulose, nanocellulose, dextran and mixtures thereof.

[0168] 73. The membrane structure according to clause 53, wherein the shielding web sealant layer comprises: (1) from about 30 wt% to about 100 wt% of at least one biodegradable polymer selected from polyhydroxyalkanoates, polybutylene succinate, polybutylene succinate-co-butylene adipate, polylactic acid, polycaprolactone, polyglycolic acid, polybutylene adipate-co-butylene terephthalate, cellulose acetate and mixtures thereof; and (2) from about 0.1 wt% to about 5 wt% of a nucleating agent.

[0169] 74. The membrane structure according to clause 73, wherein the sealant layer comprises from about 30 wt% to about 90 wt% of polyhydroxyalkanoate.

[0170] 75. The membrane structure according to clause 73, wherein the sealant layer comprises from about 10 wt% to about 100 wt% of polybutylene succinate.

[0171] 76. The membrane structure according to clause 73, wherein the sealant layer comprises from about 10 wt% to about 100 wt% of poly(butylene succinate-co-butylene adipate).

[0172] 77. The membrane structure according to clause 73, wherein the sealant layer comprises from about 10 wt% to about 100 wt% of polylactic acid.

[0173] 78. The membrane structure according to clause 73, wherein the nucleating agent for the sealant layer is selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenic acid amide, erucic acid amide, stearamide, oleamide, polyhydroxybutyrate, and mixtures thereof.

[0174] 79. The membrane structure according to clause 53, wherein the printed web comprises (1) from about 10 wt% to about 90 wt% of polyhydroxyalkanoate; (2) from about 30 wt% to about 70 wt% of at least one biodegradable polymer selected from poly(butylene succinate), poly(butylene succinate-co-butylene adipate), polylactic acid, polycaprolactone, polyglycolic acid, poly(butylene adipate-co-butylene terephthalate), cellulose acetate, and mixtures thereof; and (3) from about 0.1 wt% to about 5 wt% of a nucleating agent; and (4) optionally, up to about 50 wt% of a plasticizer.

[0175] 80. The membrane structure according to clause 79, wherein the printed web comprises from about 30 wt% to about 70 wt% of polyhydroxyalkanoate.

[0176] 81. The membrane structure according to clause 79, wherein the printed web comprises from about 30 wt% to about 70 wt% of poly(butylene succinate).

[0177] 82. The membrane structure according to clause 79, wherein the printed web comprises from about 30 wt% to about 70 wt% of poly(butylene succinate-co-butylene adipate).

[0178] 83. The membrane structure according to clause 79, wherein the printed web comprises from about 40 wt% to about 70 wt% of polylactic acid.

[0179] 84. The membrane structure according to clause 79, wherein the nucleating agent for the printed web is selected from erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenic acid amide, erucic acid amide, stearamide, oleamide, polyhydroxybutyrate, and mixtures thereof.

[0180] 85. The membrane structure according to clause 79, wherein the printed web comprises from about 5 wt% to about 30 wt% of a plasticizer.

[0181] 86. The membrane structure according to clause 79, wherein the printing web plasticizer is selected from sebacates, citrates, fatty acid esters of adipic acid, succinic acid and glucaric acid, lactates, alkyl diesters, citrates, alkyl methyl esters, dibenzoates, propylene carbonate, caprolactone diols having a number average molecular weight of 200-10,000 g / mol, polyethylene glycols having a number average molecular weight of 400-10,000 g / mol, vegetable oil esters, long-chain alkyl acids, adipates, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 ester, HALLGREEN R-8010 ester, polyhydroxyalkanoate copolymers having monomer residues of hydroxy fatty acid esters other than hydroxybutyrate esters at least 18 mol% and mixtures thereof.

[0182] It should be understood that in some embodiments, the use of the indefinite article "a" in relation to an element (e.g., "printing outer layer", "product side inner layer", "core layer", "shielding layer", "laminated layer", etc.) does not exclude the presence of multiple such elements.

[0183] The above detailed description and the drawings have been provided by way of explanation and illustration, and they are not intended to limit the scope of the appended claims. Various variations of the preferred embodiments of the invention described herein will be apparent to those skilled in the art and are still within the scope of the appended claims and their equivalents.

[0184] It should be understood that the elements and features recited in the appended claims can be combined in different ways to yield new claims that are also within the scope of the invention. Thus, although the following appended dependent claims depend only on a single independent or dependent claim, it should be understood that alternatively, these dependent claims can depend on any previous claim (whether independent or dependent) in an alternative form, and these new combinations will be understood to form a part of this specification.

Claims

1. A multi-layer packaging film, comprising: A printed outer layer, which comprises: (i) polyhydroxyalkanoate (PHA) and a first nucleating agent, (ii) a material selected from polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), cellophane, paper, or a combination thereof, and (iii) graphic elements; A product-side inner layer, which comprises: (i) a core layer and (ii) a shielding layer, the core layer comprising polyhydroxyalkanoate (PHA), a second nucleating agent, and a biodegradable polymer selected from polylactide (PLA), polybutylene succinate (PBS), polybutylene adipate succinate (PBSA), polyglycolic acid (PGA), poly(lactic-co-glycolic acid) (PLGA), polybutylene adipate terephthalate (PBAT), and combinations thereof, the shielding layer comprising metal, microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, graphene, an aqueous basecoat coating, a solvent basecoat coating, a polyurethane basecoat coating, a polyacrylate basecoat coating, polyglycolide (PGA), a phenoxy resin, magnetic nanoparticles, an epoxy microencapsulated amine, a silica deposition layer, or a combination thereof; and A lamination layer, which is interposed between the printed outer layer and the product-side inner layer, the lamination layer comprising an adhesive or an extrusion lamination resin; Wherein each of the first nucleating agent and the second nucleating agent is independently selected from erythritol, pentaerythritol, dipentaerythritol, anatase, wulfenite, aragonite, an artificial sweetener, a stearate, sorbitol, mannitol, inositol, a polyester wax, nanoclay, behenic acid amide, erucic acid amide, stearamide, oleamide, polyhydroxybutyrate, sulfur, selenium, phosphorus, benzamide, and combinations thereof.

2. The multi-layer packaging film according to claim 1, wherein the printed outer layer further comprises polybutylene adipate succinate (PBSA), polycaprolactone (PCL), or a combination thereof.

3. The multi-layer packaging film according to claim 1, wherein the core layer further comprises a filler selected from inorganic fillers, bio-based fillers, or a combination thereof.

4. The multi-layer packaging film according to claim 3, wherein the inorganic filler comprises an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal sulfate, an alkaline earth metal sulfate, or a combination thereof.

5. The multi-layer packaging film according to claim 3, wherein the inorganic filler is selected from sodium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum sulfate, magnesium oxide, calcium oxide, aluminum oxide, mica, talc, silica, clay, glass beads, titanium dioxide, aluminum hydroxide, zeolite, and combinations thereof.

6. The multi-layer packaging film according to claim 3, wherein the inorganic filler comprises calcium carbonate.

7. The multi-layer packaging film according to claim 3, wherein the bio-based filler comprises wheat straw, soybean meal, rice husk, oat husk, or a combination thereof.

8. The multi-layer packaging film according to claim 1, wherein the lamination layer comprises an adhesive.

9. The multilayer packaging film according to claim 8, wherein the adhesive comprises a compostable water-based adhesive, a compostable solvent-based adhesive, a compostable solvent-free adhesive, or a combination thereof.

10. The multilayer packaging film according to claim 1, wherein the laminated layer comprises an extruded laminated resin.

11. The multilayer packaging film according to claim 10, wherein the extruded laminated resin comprises a PLA-based extruded laminated resin, a PHA-based extruded laminated resin, a PBSA-based extruded laminated resin, a PBAT-based extruded laminated resin, a PCL-based extruded laminated resin, a starch-based extruded laminated resin, or a combination thereof.

12. The multilayer packaging film according to claim 1, wherein the first nucleating agent and the second nucleating agent are the same or different.

13. The multi-layer packaging film according to claim 1, wherein the product-side inner layer further comprises: (iii) A sealant layer.

14. The multilayer packaging film according to claim 1, wherein the core layer further comprises PLA, PBSA, or a combination thereof.

15. The multilayer packaging film according to claim 1, wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

16. The multi-layer packaging film according to claim 1, wherein the method for forming the inner layer on the product side comprises: Coextrude at least a first composition and a second composition, wherein the first composition forms the core layer and the second composition forms the shielding layer.

17. The multilayer packaging film according to claim 16, wherein the product-side inner layer further comprises at least a third layer, and wherein the method further comprises coextruding at least a third composition, and the third composition forms the third layer.

18. The multilayer packaging film according to claim 17, wherein the product-side inner layer further comprises at least a fourth layer, and wherein the method further comprises coextruding at least a fourth composition, and the fourth composition forms the fourth layer.

19. The multilayer packaging film according to claim 1, wherein the shielding layer contains metal, and wherein the product-side inner layer further comprises a third layer between the shielding layer and the core layer.

20. The multilayer packaging film according to claim 1, wherein the core layer further comprises PLA.

21. The multilayer packaging film according to claim 19, wherein the third layer comprises polyvinyl alcohol (PVA), modified cellulose acetate, polysaccharide, PGA, PHA, PLA, PBSA, PBS, or a combination thereof.

22. The multilayer packaging film according to claim 19, wherein the third layer comprises PHA, PLA, or a combination thereof.

23. The multilayer packaging film according to claim 19, wherein the third layer comprises PHA, PLA, or a combination thereof, and wherein the core layer further comprises PLA.

24. The multilayer packaging film according to claim 19, wherein the shielding layer comprises metal, wherein the product-side inner layer further comprises a third layer and a fourth layer, and wherein the core layer is between the third layer and the fourth layer.

25. The multilayer packaging film according to claim 24, wherein the fourth layer is a sealant layer.

26. The multilayer packaging film according to claim 25, wherein the sealant layer comprises PHA, PLA, PBSA, or a combination thereof.

27. The multi-layer packaging film according to claim 19, wherein the product-side inner layer shielding layer further comprises a fourth layer, and wherein the fourth layer comprises a primer coating.

28. The multi-layer packaging film according to claim 27, wherein the primer coating is between the shielding layer and the third layer.

29. The multi-layer packaging film according to claim 27, wherein the primer coating is water-based.

30. The multi-layer packaging film according to claim 27, wherein the primer coating is solvent-based.

31. The multi-layer packaging film according to claim 27, wherein the primer coating is polyurethane-based.

32. The multi-layer packaging film according to claim 27, wherein the primer coating is polyacrylate-based.

33. The multi-layer packaging film according to claim 19, wherein the product-side inner layer further comprises a fourth layer, and wherein the fourth layer comprises a silica deposition layer.

34. The multi-layer packaging film according to claim 33, wherein the silica deposition layer is between the shielding layer and the third layer.

35. The multi-layer packaging film according to claim 19, wherein the product-side inner layer further comprises a fourth layer, and wherein the core layer is between the third layer and the fourth layer.

36. The multi-layer packaging film according to claim 35, wherein the fourth layer comprises PVA, modified cellulose acetate, polysaccharide, PGA, PHA, PLA, PBSA, PBS, or a combination thereof.

37. The multi-layer packaging film according to claim 35, wherein the fourth layer comprises PHA, PLA, or a combination thereof.

38. The multi-layer packaging film according to claim 19, wherein the product-side inner layer further comprises a fourth layer, wherein the fourth layer comprises an electron beam top coating, and wherein the electron beam top coating is between the laminate layer and the shielding layer.

39. The multi-layer packaging film according to claim 19, wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

40. The multi-layer packaging film according to claim 1, wherein the graphic elements comprise text, images, or a combination thereof.

41. A multi-layer packaging film, comprising: A printed outer layer, comprising: (i) PHA and a first nucleating agent, (ii) a material selected from PLA, PBAT, PBS, cellophane, paper, or a combination thereof, and (iii) graphic elements; The inner layer on the product side, which includes: (i) a shielding layer, (ii) a core layer, and (iii) a third layer between the shielding layer and the core layer, the shielding layer includes metal, microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, graphene, water-based primer coating, solvent-based primer coating, polyurethane-based primer coating, polyacrylate-based primer coating, polyglycolic acid (PGA), phenoxy resin, magnetic nanoparticles, epoxy microencapsulated amine, silica deposition layer or a combination thereof, the core layer includes PHA, a second nucleating agent, and a biodegradable polymer selected from PLA, PBS, polybutylene adipate-co-butylene terephthalate (PBSA), PGA, poly(lactic-co-glycolic acid) (PLGA), PBAT or a combination thereof, the third layer includes PHA and the second nucleating agent; and A laminated layer, which includes an adhesive, an extrusion lamination resin or a combination thereof, wherein the laminated layer is between the printed outer layer and the inner layer on the product side; wherein each of the first nucleating agent and the second nucleating agent is independently selected from erythritol, pentaerythritol, dipentaerythritol, anatase, wulfenite, aragonite, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester wax, nanoclay, behenic acid amide, erucic acid amide, stearamide, oleamide, polyhydroxybutyrate, sulfur, selenium, phosphorus, benzamide and combinations thereof.

42. The multilayer packaging film according to claim 41, wherein the core layer and / or the third layer further independently includes a filler selected from mineral fillers, bio-based fillers and combinations thereof.

43. The multilayer packaging film according to claim 41, wherein the core layer further includes a biodegradable polymer selected from PLA, PBS, PBSA, PGA, PLGA, PBAT and combinations thereof.

44. A packaging article, comprising the multilayer packaging film according to claim 1.

45. The packaging article according to claim 44, wherein the packaging article is food packaging.

46. A packaging article, comprising the multilayer packaging film according to claim 41.

47. The packaging article according to claim 46, wherein the packaging article is snack food packaging.

48. The packaging article according to claim 46, wherein the packaging article is beverage packaging.

Images