Multilayer packaging film

Abstract

A multilayer packaging film comprising: (a) an outer printed layer; (b) an inner product-side layer; and (c) a laminate layer interposed between the outer printed layer and the inner product-side layer.

Description

[Technical Field]

[0001] Related Applications This international patent application is a continuation of the earlier U.S. non-provisional patent application Ser. No. 16 / 943,866, filed July 30, 2021. The entire contents of the U.S. priority document are incorporated herein by reference, except to the extent that there is a conflicting disclosure or definition from this specification, in which case the disclosure or definition herein shall be deemed to control.

[0002] The present teachings generally relate to polymeric materials and multilayer films formed therefrom. In some embodiments, the present teachings relate to biodegradable and / or compostable multilayer polymeric films for use in packaging applications. [Background technology]

[0003] Snack foods, including but not limited to potato chips, crackers, and cookies, are typically packaged in sealed disposable bags. Conventional bags may include multiple layers of polymeric films that are glued or laminated together to provide a finished product with a desired combination of strength properties, barrier properties (e.g., with respect to moisture, oxygen, grease, etc.), and good printability for product packaging graphics.

[0004] Until now, most or all of the film layers in conventional snack food bags have been composed primarily of petroleum-based polymers such as polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET). While these polymers may provide good strength, barrier properties, and / or printability to the film structure, such polymers do not readily degrade or break down after disposal—either in landfills or through home composting techniques. As a result, film structures and bags made from such polymers may persist in landfills for centuries after disposal. Summary of the Invention

[0005] The scope of the present invention is defined solely by the appended claims and is not affected in any way by the statements in this Summary.

[0006] A first multilayer packaging film according to the present teachings includes (a) an outer printed layer, (b) an inner product-side layer including a core layer and a barrier layer, and (c) a laminate layer interposed between the outer printed layer and the inner product-side layer. The outer printed layer includes (i) polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutyl succinate (PBS), cellophane, paper, or a combination thereof, (ii) a graphic element, and (iii) an optional first nucleating agent. The core layer includes PHA and a second nucleating agent.

[0007] A second multilayer packaging film according to the present teachings includes (a) an outer printed layer, (b) an inner product-side layer, and (c) a laminate layer interposed between the outer printed layer and the inner product-side layer. The outer printed layer includes (i) PHA, PLA, PBAT, PBS, cellophane, paper, or a combination thereof, (ii) a graphic element, and (iii) an optional first nucleating agent. The inner product-side layer includes (i) a barrier layer, (ii) a core layer, and (iii) a third layer interposed between the barrier layer and the core layer, each of the core layer and the third layer including a PHA and a second nucleating agent. The laminate layer includes an adhesive, an extrusion laminating resin, or a combination thereof. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram of a first exemplary multilayer packaging film in accordance with the present teachings.

[0009] [Figure 2] FIG. 2 is a diagram of a second exemplary multilayer packaging film in accordance with the present teachings.

[0010] [Figure 3]FIG. 3 is a diagram of a third exemplary multilayer packaging film in accordance with the present teachings.

[0011] [Figure 4] FIG. 4 is a diagram of a fourth exemplary multilayer packaging film in accordance with the present teachings.

[0012] [Figure 5] FIG. 5 is a diagram of a fifth exemplary multilayer packaging film in accordance with the present teachings.

[0013] [Figure 6] Figure 6 is a diagram of a sixth exemplary multilayer packaging film in accordance with the present teachings. Figure 1 is a diagram of a first exemplary multilayer packaging film in accordance with the present teachings.

[0014] [Figure 7] FIG. 7 is a diagram of a seventh exemplary multilayer packaging film in accordance with the present teachings.

[0015] [Figure 8] FIG. 8 is a diagram of an eighth exemplary multilayer packaging film in accordance with the present teachings.

[0016] [Figure 9] FIG. 9 is a diagram of a ninth exemplary multilayer packaging film in accordance with the present teachings.

[0017] [Figure 10] FIG. 10 is a diagram of a tenth exemplary multilayer packaging film in accordance with the present teachings.

[0018] [Figure 11] FIG. 11 is a diagram of an eleventh exemplary multilayer packaging film in accordance with the present teachings.

[0019] [Figure 12] FIG. 12 is a diagram of a twelfth exemplary multilayer packaging film in accordance with the present teachings. DETAILED DESCRIPTION OF THE INVENTION

[0020] Biodegradable multilayer packaging film structures suitable for packaging chips and other snack foods have been discovered and are described herein. In some embodiments, the biodegradable multilayer packaging films according to the present teachings are at least partially compostable (and in some embodiments, at least partially home compostable).

[0021] Throughout this specification and the appended claims, the following definitions shall be understood.

[0022] As used herein, the term "biodegradable" means a plastic or polymer that is at least partially subject to biodegradation by living organisms (microorganisms) in anaerobic and aerobic environments (as determined by ASTM D5511), soil environments (as determined by ASTM D5988), freshwater environments (as determined by ASTM D5271 (EN 29408)), or 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.

[0023] As used herein, the term "compostable" refers to a biodegradable material that can be broken down exclusively into carbon dioxide, water, inorganic compounds, and / or biomass, without leaving any visible or toxic residue. In some embodiments, a multilayer packaging film according to the present teachings is "compostable" industrially or domestically as determined by ASTM D6400.

[0024] It will be understood that elements and features of the various exemplary embodiments described below can be combined in different ways to create new embodiments that also fall within the scope of the present teachings.

[0025] By way of introduction, a multilayer packaging film according to the present teachings includes (a) an outer printed layer, (b) an inner product-side layer, and (c) a laminate layer interposed between the outer printed layer and the inner product-side layer. In some embodiments, the outer printed layer includes a biopolymer and a graphic element, the inner product-side layer includes a core layer and a barrier layer, and the laminate layer includes an adhesive.

[0026] The polymeric materials used to form the outer print layer, inner product-side layer, and / or laminate layer of the multilayer packaging film according to the present teachings can be present as homopolymers, copolymers, terpolymers, and / or blends thereof.

[0027] In some embodiments, the outer print layer comprises (i) polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutyl succinate (PBS), cellophane, paper, or a combination thereof, (ii) a graphic element, and (iii) an optional first nucleating agent. In some embodiments, the outer print layer further comprises polybutylene succinate adipate (PBSA), polycaprolactone (PCL), or a combination thereof. In some embodiments, particularly but not limited to embodiments in which one or more layers comprise polyhydroxyalkanoate (PHA), a nucleating agent may also be present. In some embodiments, the outer print layer comprises both a PHA and an optional first nucleating agent. In some embodiments, the graphic element of the outer print layer comprises text, an image, or a combination thereof.

[0028] In some embodiments, the laminate layer comprises an adhesive (which in some embodiments includes a compostable water-based adhesive, a compostable solvent-based adhesive, a compostable non-solvent-based adhesive, a non-compostable water-based adhesive, a non-compostable solvent-based adhesive, a non-compostable non-solvent-based adhesive, or a combination thereof). In some embodiments, the laminate layer comprises an extrusion lamination resin. Exemplary extrusion lamination resins for use with the present teachings 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 combinations thereof.

[0029] In some embodiments, the inner product side layer comprises (i) a core layer and (ii) a barrier layer, hi other embodiments, the inner product side layer further comprises (iii) a sealant layer.

[0030] In some embodiments, the core layer of the inner product side layer further comprises a biodegradable polymer selected from the group consisting of PLA, PBS, PBSA, PGA, poly(lactic-co-glycolic acid) (PLGA), PBAT, and combinations thereof. In some embodiments, the core layer of the inner product side layer comprises PHA and a second nucleating agent. In some embodiments, the core layer of the inner product side layer further comprises PLA, PBSA, or a combination thereof. In some embodiments, the core layer of the inner product side layer further comprises PLA.

[0031] The second nucleating agent of the core layer and any first nucleating agent of the outer printed layer can be the same or different. In some embodiments, the second nucleating agent and any first nucleating agent are each independently selected from the group consisting of: (1) compounds having an orthorhombic crystal structure, (2) compounds having a hexagonal crystal structure, (3) compounds having a tetragonal crystal structure, (4) allotropes having at least one orthorhombic, hexagonal, or tetragonal crystal form, (5) polymorphic compounds having at least one orthorhombic, hexagonal, or tetragonal crystal form, and (6) combinations thereof. In some embodiments, each of the second nucleating agent and any first nucleating agent is independently selected from the group consisting of 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.

[0032] In some embodiments, the core layer of the inner product-side layer further comprises a filler selected from the group consisting of an inorganic filler, a bio-based filler, or a combination thereof. Exemplary inorganic fillers for use with the present teachings include, but are not limited to, alkali metal carbonates, alkaline earth metal carbonates, alkali metal sulfates, alkaline earth metal sulfates, or a combination thereof. In some embodiments, the inorganic filler for use with the present teachings is selected from the group consisting of sodium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum sulfate, magnesium oxide, calcium oxide, alumina, mica, talc, silica, clay, glass spheres, titanium dioxide, aluminum hydroxide, zeolite, and a combination thereof. In some embodiments, the inorganic filler comprises calcium carbonate. Exemplary bio-based fillers for use with the present teachings include, but are not limited to, wheat straw, soybean flakes, rice hulls, oat hulls, or a combination thereof.

[0033] In some embodiments, the inner product-side layer is formed via a process that includes co-extruding at least a first composition and a second composition, with the first composition forming the core layer and the second composition forming the barrier layer. In some embodiments, the barrier layer of the inner product-side layer is provided as a coating, while in other embodiments, the barrier layer of the inner product-side layer is formed via a co-extrusion process. In some embodiments, the barrier layer includes a metal (e.g., aluminum, aluminum oxide, or a combination 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), phenoxy resin, magnetic nanoparticles, epoxy-microencapsulated amine, a silica deposition layer, or a combination thereof. In some embodiments, the barrier layer includes aluminum, aluminum oxide, or a combination thereof.

[0034] In some embodiments, the inner product-side layer further comprises at least a third layer in addition to the core layer and the barrier layer, and the process for forming the inner product-side layer further comprises co-extruding at least a third composition, with the third composition forming the third layer. In other embodiments, the inner product-side layer further comprises at least a fourth layer, and the process for forming the inner product-side layer further comprises co-extruding at least a fourth composition, with the fourth composition forming the fourth layer.

[0035] In some embodiments, the barrier layer of the inner product side layer comprises a metal, and the inner product side layer further comprises a third layer interposed between the barrier layer and the core layer.

[0036] In some embodiments, the third layer of the inner product side layer comprises poly(vinyl alcohol) (PVA), modified cellulose acetate, polysaccharide, PGA, PHA, PLA, PBSA, PBS, or a combination thereof. In some embodiments, the third layer of the inner product side layer comprises PHA, PLA, or a combination thereof. In some embodiments, the third layer of the inner product side layer comprises PHA, PLA, or a combination thereof, and the core layer of the inner product side layer further comprises PLA.

[0037] In some embodiments, the barrier layer of the inner product side layer comprises a metal, the inner product side layer further comprises a third layer and a fourth layer, and the core layer is interposed between the third layer and the fourth layer. In some embodiments, the fourth layer comprises PVA, modified cellulose acetate, polysaccharide, PGA, PHA, PLA, PBSA, PBS, or a combination thereof. In some embodiments, the fourth layer comprises PHA, PLA, or a combination thereof.

[0038] In some embodiments, the fourth layer comprises a sealant layer, and in some embodiments, the sealant layer comprises PHA, PLA, PBSA, or a combination thereof. In other embodiments, the fourth layer comprises a primer coating, and in some embodiments, the primer coating is interposed between the barrier layer of the inner product side layer and the third layer. In some embodiments, the primer coating is water-based, in other embodiments, the primer coating is solvent-based, in further embodiments, the primer coating is polyurethane-based, and in further embodiments, the primer coating is polyacrylate-based. In further embodiments, the primer coating is polysaccharide-based, in further embodiments, the primer coating is nanocellulose-based, in further embodiments, the primer coating is polyglycolic acid (PGA)-based, and in further embodiments, the primer coating is polyvinyl alcohol (PVOH)-based. In some embodiments, the fourth layer comprises a silica deposition layer, and in some embodiments, the silica deposition layer is interposed between the barrier layer and the third layer. In some embodiments, the fourth layer comprises an e-beam top coating, and in some embodiments, the e-beam top coating is interposed between the laminate layer and the barrier layer.

[0039] Packaging articles according to the present teachings include, but are not limited to, food packages and beverage packages, and include multilayer packaging films of the type described herein.

[0040] 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 this sleeve, and both ends of the sleeve are sealed to provide the final packaged food product. In some embodiments, this process can be automated by using a vertical or horizontal form, fill, and seal ("FFS") packaging machine. Food products that can be packaged according to the present disclosure include, but are not limited to, snack chips such as potato chips, corn chips, pretzels, and confectioneries.

[0041] As is apparent from the above description, and as described more fully below with reference to Figures 1-12, a multilayer food packaging film structure according to the present teachings includes at least a barrier web and a print web. The barrier web skin layer is adhered or laminated to the print web by an adhesive layer or extrusion laminate layer disposed between the barrier web skin layer and the print web.

[0042] In some embodiments, both the barrier web and the printed web are biodegradable and / or compostable. More particularly, each individual layer of the multilayer film structure is biodegradable and / or compostable.

[0043] In some embodiments, the barrier web is comprised of at least three film layers. For example, the barrier web may include at least a barrier web core layer having a first side and a second side, a barrier web skin 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.

[0044] The composition of each layer of the barrier web may vary slightly, as described below, however, in some embodiments, each layer of the barrier web is biodegradable and / or home compostable.

[0045] 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 to about 2.0 mils.

[0046] The composition of the core layer includes at least two different biodegradable polymers, a nucleating agent, and a chain extender. Optionally, the core layer may include a filler, a plasticizer, an antiblocking agent, and / or an impact modifier.

[0047] In some embodiments, the barrier web core layer comprises a polyhydroxyalkanoate as the first biodegradable polymer. The core layer is generally composed of about 10 to about 90 weight percent polyhydroxyalkanoate. In some embodiments, the core layer is composed of about 30 to about 85 weight percent polyhydroxyalkanoate.

[0048] In some embodiments, the barrier web core layer also comprises a second biodegradable polymer selected from the group consisting of polybutylene succinate, polybutylene succinate-co-butylene adipate, polylactic acid, cellulose acetate, and mixtures thereof, in an amount of from about 30 weight percent to about 90 weight percent of the core layer.

[0049] In some embodiments, the barrier web core layer may comprise from about 30 weight percent to about 70 weight percent polybutylene succinate, or from about 30 weight percent to about 70 weight percent polybutylene succinate-co-butylene adipate, or from about 10 weight percent to about 60 weight percent polylactic acid.

[0050] In some embodiments, the nucleating agent is present in the core layer in an amount from about 0.1 weight percent to about 5 weight percent. In some embodiments, the core layer nucleating agent may be selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or the like, and combinations thereof.

[0051] In some embodiments, the amount of chain extender in the core layer is from about 0.01 weight percent to about 1.0 weight percent. Suitable chain extenders for the core layer include, but are not limited to, organic peroxyacids, inorganic peroxyacids, epoxy functionalizing reagents, and / or the like, and combinations thereof.

[0052] In some embodiments, the core layer may also optionally include a filler. Suitable materials for the filler are selected from the group consisting of 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, polysaccharides, aluminum hydroxide, magnesium hydroxide, chitin, and the like, and / or the like, and combinations thereof.

[0053] In some embodiments, the amount of filler in the barrier web core layer may be up to about 50 weight percent, hi some embodiments, the core layer is comprised of from about 5 weight percent to about 40 weight percent filler.

[0054] In some embodiments, the core layer may also include an optional plasticizer material. Suitable plasticizer materials include, but are not limited to, sebacate, citrate, fatty esters of adipic, succinic, and glucaric acids, lactate, alkyl diesters, citrate, alkyl methyl esters, dibenzoate, propylene carbonate, caprolactone diols having a number average molecular weight of 200 to 10,000 g / mol, poly(ethylene) glycols having a number average molecular weight of 400 to 10,000 g / mol, esters of vegetable oils, long chain alkyl acids, adipate, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 esters, HALLGREEN R-8010 esters, polyhydroxyalkanoic acid copolymers containing at least 18 mole percent of monomer residues of hydroxyalkanoic acids other than hydroxybutyric acid, and / or the like, and combinations thereof.

[0055] In some embodiments, the amount of plasticizer in the barrier web core layer can be up to about 50 weight percent, hi some embodiments, the core layer is comprised of about 5 weight percent to about 15 weight percent plasticizer.

[0056] In some embodiments, the core layer may also include up to 20 weight percent impact modifier. In some embodiments, the core layer includes from about 5 weight percent to about 15 weight percent impact modifier.

[0057] Additionally, in some embodiments, the core layer may contain up to 50 weight percent of one or more additives selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, polyvinyl laurate, ethylene vinyl acetate, butenediol 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 the trade name ECOFLEX, poly(glycolic acid), polycaprolactone, furandicarboxylic acid-based polyesters, thermoplastic starch, cellulose, nanocellulose, glucan, and / or the like, and combinations thereof.

[0058] In some embodiments, the barrier web also includes a polymeric skin layer adhered or laminated to the first side of the web core layer. The skin layer has a thickness of about 0.2 to about 2.0 mils. In some embodiments, the skin layer includes at least two different biodegradable polymers and a nucleating agent. In some embodiments, the barrier web skin layer includes a polyhydroxyalkanoate as the first biodegradable polymer. In some embodiments, the skin layer is comprised of about 10 weight percent to about 90 weight percent polyhydroxyalkanoate. In some embodiments, the skin layer is comprised of about 40 weight percent to about 90 weight percent polyhydroxyalkanoate.

[0059] In some embodiments, the barrier web skin layer also comprises a second biodegradable polymer selected from the group consisting of polybutylene succinate, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-butylene terephalate, polycaprolactone, polylactic acid, polyglycolic acid, cellulose acetate, and mixtures thereof. In some embodiments, the amount of this second biodegradable polymer is from about 30 weight percent to about 90 weight percent of the core layer.

[0060] In some embodiments, the barrier web skin layer may comprise from about 40 weight percent to about 90 weight percent polybutylene succinate, or from about 40 weight percent to about 90 weight percent polybutylene succinate-co-butylene adipate, or from about 30 weight percent to about 70 weight percent polylactic acid.

[0061] In some embodiments, the skin layer nucleating agent is present in an amount from about 0.1 weight percent to about 5 weight percent. In some embodiments, the skin layer nucleating agent is selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or the like, and combinations thereof.

[0062] In some embodiments, the barrier web further comprises a sealant layer adhered or laminated to the second side of the web core layer. In some embodiments, the sealant layer has a thickness of about 0.2 to about 2.0 mils. In some embodiments, the sealant layer comprises at least one biodegradable polymer and a nucleating agent.

[0063] In some embodiments, the at least one biodegradable polymer in the sealant layer may be selected from polyhydroxyalkanoates, polybutylene succinates, polybutylene succinate-co-butylene adipates, polylactic acids, polycaprolactones, polyglycolic acids, polybutylene adipates-co-butylene terephthalates, cellulose acetates, and / or the like, and combinations thereof. In some embodiments, the amount of biodegradable polymer in the sealant layer is from about 30 weight percent to about 100 weight percent.

[0064] In some embodiments, the barrier web sealant layer can comprise from about 30 weight percent to about 100 weight percent polyhydroxyalkanoate, or from about 10 weight percent to about 100 weight percent polybutylene succinate, or from about 10 weight percent to about 100 weight percent polybutylene succinate-co-butylene adipate, or from about 10 weight percent to about 100 weight percent polylactic acid.

[0065] In some embodiments, the barrier web sealant layer also includes a nucleating agent, which in some embodiments is present in an amount from about 0.1 weight percent to about 3 weight percent, hi some embodiments, the sealant layer nucleating agent is selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or the like, and combinations thereof.

[0066] In some embodiments, the sealant layer may also include about 0.1 weight percent to about 4.0 weight percent of an antiblock agent, such as an amide material or a large particle size filler.

[0067] In some embodiments, the individual layers of the barrier web may be joined together by either lamination or the use of an adhesive. As used herein, an adhesive comprises an aqueous and / or organic solvent, as well as a pressure-sensitive adhesive and other components, that substantially evaporates over time. After the adhesive dries, only the non-solvent portion remains, serving to bond the individual layers of the barrier web together. In contrast, in lamination, an extruded polymer film with little or no solvent is placed between two layers of the web to bond the layers together.

[0068] As mentioned above, film structures according to the present teachings also include a printed web. Like the barrier web, the printed web, in some embodiments, is biodegradable and / or home compostable.

[0069] In some embodiments, the print web has a first side and a second side, and the desired packaging graphics may be printed on either side of the print web. Thus, the print web may be printed on its outside or reverse printed on its inside.

[0070] In some embodiments, the print web is composed of: (1) about 10 weight percent to about 90 weight percent polyhydroxyalkanoate; (2) about 30 weight percent to about 90 weight percent at least one biodegradable polymer selected from the group consisting of polybutylene succinate, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-butylene terephthalate, polycaprolactone, polylactic acid, cellulose acetate, and mixtures thereof; (3) about 0.1 weight percent to about 3 weight percent nucleating agent; and (4) optionally, up to about 15 weight percent plasticizer.

[0071] In some embodiments, the print web may comprise from about 30 weight percent to about 100 weight percent polyhydroxyalkanoate, or from about 30 weight percent to about 70 weight percent polybutylene succinate, or from about 30 weight percent to about 70 weight percent polybutylene succinate-co-butylene adipate, or from about 40 weight percent to about 70 weight percent polylactic acid. In some embodiments, the print web may comprise from 10 weight percent to 100 weight percent cellulose acetate.

[0072] In some embodiments, the nucleating agent for the print web may be selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and / or the like, and combinations thereof.

[0073] In some embodiments, the print web may optionally further comprise about 5 to about 30 weight percent of a plasticizer. Suitable plasticizers for the print web include, but are not limited to, sebacate, citrate, fatty esters of adipic, succinic, and glucaric acid, lactate, alkyl diesters, citrate, alkyl methyl esters, dibenzoate, propylene carbonate, caprolactone diols having a number average molecular weight of 200 to 10,000 g / mol, poly(ethylene) glycols having a number average molecular weight of 400 to 10,000 g / mol, esters of vegetable oils, long chain alkyl acids, adipates, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 esters, HALLGREEN R-8010 esters, polyhydroxyalkanoic acid copolymers containing at least 18 mole percent monomer residues of hydroxyalkanoic acids other than hydroxybutyric acid, and / or the like, and combinations thereof.

[0074] In some embodiments, the barrier web skin layer is adhered or laminated to the print web by an adhesive layer or an extrusion laminate layer disposed between the barrier web skin layer and the print web.

[0075] Suitable adhesives can be either water-based, organic solvent-based, or solvent-free (e.g., polyurethane). Suitable laminating materials can also be blends of biodegradable polymers (including reactive blends). Exemplary biodegradable polymers for extrusion lamination include, but are not limited to, polycaprolactone and polybutylene adipate terephthalate (PBAT). In the lamination process, the polymer resin is melted in an extruder and passed through a die sandwiched between the print web and the barrier web, bonding the two webs.

[0076] In each of the various layers described above, the polyhydroxyalkanoate polymer may be a homopolymer, consisting of only one type of monomer residue. In some embodiments, the polyhydroxyalkanoate polymer is a copolymer, consisting of two or more different types of monomer residue. In some embodiments, the polyhydroxyalkanoate polymer may be a terpolymer, consisting of at least three different types of monomer residue.

[0077] For example, in some embodiments, at least one polyhydroxyalkanoate polymer is a copolymer consisting of about 75 to about 99.9 mole percent of monomer residues of 3-hydroxybutyrate and about 0.1 to about 25 mole percent of monomer residues of a second 3-hydroxyalkanoate having 5 to 12 carbon atoms.

[0078] In other embodiments, the at least one polyhydroxyalkanoate polymer is a terpolymer composed of from about 75 to about 99.9 mole percent monomer residues of 3-hydroxybutyrate, from about 0.1 to about 25 mole percent monomer residues of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3-hydroxyalkanoate having 5 to 12 carbon atoms.

[0079] 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, from about 300,000 Daltons to about 3 million Daltons.

[0080] A representative configuration of an exemplary multilayer packaging film according to the present teachings will now be described with reference to FIGS.

[0081] A first embodiment of a multilayer packaging film 2 in accordance with the present teachings is shown in FIG. 1. The multilayer packaging film 2 has a three-layer structure including at least an outer printed layer 4, an inner product-side layer 8, and a laminate layer 6 interposed between the outer printed layer 4 and the inner product-side layer 8. The outer printed layer 4 includes (i) polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutyl succinate (PBS), cellophane, paper, or a combination thereof, (ii) a graphic element, and (iii) an optional first nucleating agent. The inner product-side layer 8 includes (i) a core layer and (ii) a barrier layer. The core layer includes a PHA and a second nucleating agent.

[0082] A second embodiment of a multilayer packaging film 10 in accordance with the present teachings is shown in Figure 2. The multilayer packaging film 10 has a three-layer structure including at least an outer printed layer 12, an inner product-side layer 16, and a laminate layer 14 interposed between the outer printed layer 12 and the inner product-side layer 16. The outer printed layer 12 includes a graphic element 18 and a biopolymer 20 (e.g., a PHA-containing blend). The laminate layer 14 includes an adhesive 22. The inner product-side layer 16 includes a barrier layer 24 (e.g., metal), a core layer 28 (e.g., a PHA / PLA blend), a third layer 26 (e.g., a PHA-containing skin), and a fourth layer 30 (e.g., a PHA-containing sealant layer).

[0083] A third embodiment of a multilayer packaging film 32 according to the present teachings is shown in FIG. 3 . This embodiment corresponds to a bi-laminate (bi-lam) reverse print structure. The multilayer packaging film 32 has a three-layer structure including at least an outer print layer 34, an inner product-side layer 38, and a laminate layer 36 interposed between the outer print layer 34 and the inner product-side layer 38. The outer print layer 34 includes a transparent film 40 (e.g., a PHA blend) and a reverse print 42. The laminate layer 36 includes an adhesive 44. The inner product-side layer 38 includes a barrier layer 46 (e.g., metal), a core layer 52 (e.g., a PHA / PLA blend), a third layer 50 (e.g., a PHA / PLA-containing skin), a fourth layer 54 (e.g., a PHA-containing sealant), and a primer coating layer 48.

[0084] A fourth embodiment of a multilayer packaging film 56 according to the present teachings is shown in FIG. 4. This embodiment corresponds to a bilaminate surface-printed structure. The multilayer packaging film 56 has a three-layer structure including at least an outer printed layer 58, an inner product-side layer 62, and a laminate layer 60 interposed between the outer printed layer 58 and the inner product-side layer 62. The outer printed layer 58 includes a surface print 64 and an opaque film or paper (e.g., a PHA blend) 66. The multilayer packaging film 56 shown in FIG. 4 differs from the multilayer packaging film 32 shown in FIG. 3 in the configuration of each of the outer printed layers (58 and 34, respectively). The laminate layer 60 includes an adhesive 68. The inner product-side layer 62 includes a barrier layer 70 (e.g., metal), a core layer 76 (e.g., a PHA / PLA blend), a third layer 74 (e.g., a PHA / PLA-containing skin), a fourth layer 78 (e.g., a PHA-containing sealant), and a primer coating layer 72.

[0085] A fifth embodiment of a multilayer packaging film 80 in accordance with the present teachings is shown in FIG. 5 . This embodiment corresponds to a bilaminate extrusion laminate structure. The multilayer packaging film 80 has a three-layer structure including at least an outer printed layer 82, an inner product-side layer 86, and a laminate layer 84 interposed between the outer printed layer 82 and the inner product-side layer 86. The outer printed layer 82 includes a print 88 and a biopolymer (e.g., a PHA blend) 90. The laminate layer 84 includes an extrusion laminate 92. The inner product-side layer 86 includes a barrier layer 94 (e.g., metal), a core layer 100 (e.g., a PHA / PLA blend), a third layer 98 (e.g., a PHA / PLA-containing skin), a fourth layer 102 (e.g., a PHA-containing sealant), and a primer coating layer 96.

[0086] A sixth embodiment of a multilayer packaging film 80 in accordance with the present teachings is shown in FIG. 5 . This embodiment corresponds to a bilaminate extrusion laminate structure. The multilayer packaging film 80 has a three-layer structure including at least an outer printed layer 82, an inner product-side layer 86, and a laminate layer 84 interposed between the outer printed layer 82 and the inner product-side layer 86. The outer printed layer 82 includes a print 88 and a biopolymer (e.g., a PHA blend) 90. The laminate layer 84 includes an extrusion laminate 92. The inner product-side layer 86 includes a barrier layer 94 (e.g., metal), a core layer 100 (e.g., a PHA / PLA blend), a third layer 98 (e.g., a PHA / PLA-containing skin), a fourth layer 102 (e.g., a PHA-containing sealant), and a primer coating layer 96.

[0087] A sixth embodiment of a multilayer packaging film 104 in accordance with the present teachings is shown in FIG. 6. This embodiment corresponds to a bilaminate structure including an electron beam topcoat on metal. The multilayer packaging film 104 has a three-layer structure including at least an outer print layer 106, an inner product-side layer 110, and a laminate layer 108 interposed between the outer print layer 106 and the inner product-side layer 110. The outer print layer 106 includes a print 112 and a biopolymer (e.g., a PHA blend) 114. The laminate layer 108 includes an adhesive 116. The inner product side layer 110 includes a barrier layer 120 (e.g., metal), a core layer 126 (e.g., a PHA / PLA blend), a third layer 124 (e.g., a PHA / PLA-containing skin), a fourth layer 128 (e.g., a PHA-containing sealant), a primer coating layer 122, and an e-beam topcoat 118 interposed between the adhesive 116 and the barrier layer 120.

[0088] A seventh embodiment of a multilayer packaging film 130 in accordance with the present teachings is shown in FIG. 7 . This embodiment corresponds to a bilaminate structure including a barrier skin layer. The multilayer packaging film 130 has a three-layer structure including at least an outer printed layer 132, an inner product-side layer 136, and a laminate layer 134 interposed between the outer printed layer 132 and the inner product-side layer 136. The outer printed layer 132 includes a transparent film 138 (e.g., a PHA blend) and a reverse print 140. The laminate layer 134 includes an adhesive 142. The inner product-side layer 136 includes a barrier layer 146 (e.g., metal), a core layer 148 (e.g., a PHA blend), a third layer 146 (e.g., a barrier skin), and a fourth layer 150 (e.g., a PHA-containing sealant).

[0089] An eighth embodiment of a multilayer packaging film 152 according to the present teachings is shown in FIG. 8 . This embodiment corresponds to a bilaminate structure including a silica primer layer. The multilayer packaging film 152 has a three-layer structure including at least an outer printed layer 154, an inner product-side layer 158, and a laminate layer 156 interposed between the outer printed layer 154 and the inner product-side layer 158. The outer printed layer 154 includes a transparent film 160 (e.g., a PHA blend) and a reverse print 162. The laminate layer 156 includes an adhesive 164. The inner product-side layer 158 includes a barrier layer 166 (e.g., metal), a core layer 172 (e.g., a PHA / PLA blend), a third layer 170 (e.g., a PHA / PLA-containing skin), a fourth layer 174 (e.g., a PHA-containing sealant), and a silica deposition layer 168.

[0090] A ninth embodiment of a multilayer packaging film 176 according to the present teachings is shown in FIG. 9 . This embodiment corresponds to a tri-lam structure. The multilayer packaging film 176 has a four-layer structure including at least an outer print layer 178, an inner product-side layer 182, a laminate layer 180 interposed between the outer print layer 178 and the inner product-side layer 182, and a sealant film layer 184. The outer print layer 178 includes a transparent film 186 (e.g., a 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 inner product-side layer 182 includes a barrier layer 192 (e.g., metal), a core layer 196 (e.g., a PHA blend), and a third layer 194 (e.g., a barrier skin). The sealant film layer 184 includes a sealant 198 (eg, a PHA-containing sealant), a sealant film 202 , and an adhesive 200 interposed between the sealant 198 and the sealant film 202 .

[0091] A tenth embodiment of a multilayer packaging film 204 according to the present teachings is shown in FIG. 10. This embodiment corresponds to a mono-film structure. The multilayer packaging film 204 has a structure including at least a surface print 208 and an inner product-side layer 206. The inner product-side layer 206 includes a barrier layer 212 (e.g., metal), a core layer 218 (e.g., a PHA / PLA blend), a third layer 216 (e.g., a PHA / PLA skin), a sealant 220 (e.g., a PHA sealant), an e-beam topcoat 210, and a primer coating 214.

[0092] An eleventh embodiment of a multilayer packaging film 222 in accordance with the present teachings is shown in FIG. 11 . This embodiment corresponds to a bilaminate alternate structure. The multilayer packaging film 222 has a structure including at least a surface print 226, an inner product-side layer 224, and a sealant film layer 240. The inner product-side layer 224 includes a barrier layer 228 (e.g., metal), a core layer 234 (e.g., a PHA blend), a third layer 232 (e.g., a PHA-containing skin), a fourth layer 236 (e.g., a PHA-containing skin), and a primer coating 230 interposed between the barrier layer 228 and the third layer 232. An adhesive 238 is interposed between the fourth layer 236 and the sealant film layer 240.

[0093] A twelfth embodiment of a multilayer packaging film 242 in accordance with the present teachings is shown in FIG. 12. This embodiment corresponds to a bilaminate alternating structure. The multilayer packaging film 242 has a structure including at least a surface print 246, an inner product-side layer 244, and a sealant film layer 260. The inner product-side layer 244 includes a barrier layer 248 (e.g., metal), a core layer 254 (e.g., a PHA blend), a third layer 252 (e.g., a PHA blend-containing skin), a fourth layer 256 (e.g., a PHA blend-containing skin), and a primer coating 250 sandwiched between the barrier layer 248 and the third layer 252. An adhesive 258 is sandwiched between the fourth layer 256 and the sealant film layer 260.

[0094] Additional features and advantages of the present teachings may be described by the embodiments defined in any of the following enumerated clauses: It will be understood that any of the embodiments described herein can be used in conjunction with any other embodiment described herein to the extent that the embodiments are not mutually exclusive.

[0095] 1. A multilayer packaging film comprising: (i) an outer printed layer comprising polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutylsuccinate (PBS), cellophane, paper, or a combination thereof, (ii) a graphic element, and (iii) an optional first nucleating agent; an inner product-side layer comprising (i) a core layer and (ii) a barrier layer; and a laminate layer interposed between the outer printed layer and the inner product-side layer; wherein the core layer comprises a PHA and a second nucleating agent.

[0096] 2. The multilayer packaging film of clause 1, wherein the outer printed layer further comprises polybutylene succinate adipate (PBSA), polycaprolactone (PCL), or a combination thereof.

[0097] 3. The multilayer packaging film of any one of clauses 1-2, wherein the core layer further comprises a filler selected from the group consisting of an inorganic filler, a bio-based filler, or a combination thereof.

[0098] 4. The multilayer packaging film of 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.

[0099] 5. The multilayer packaging film of any one of clauses 1-4, wherein the inorganic filler is selected from the group consisting of sodium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum sulfate, magnesium oxide, calcium oxide, alumina, mica, talc, silica, clay, glass spheres, titanium dioxide, aluminum hydroxide, zeolite, and combinations thereof.

[0100] 6. The multilayer packaging film of any one of clauses 1 to 5, wherein the inorganic filler comprises calcium carbonate.

[0101] 7. The multilayer packaging film of any one of clauses 1-6, wherein the bio-based filler comprises wheat straw, soy flakes, rice husks, oat hulls, or combinations thereof.

[0102] 8. The multilayer packaging film of any one of clauses 1 to 7, wherein the laminate layer comprises an adhesive.

[0103] 9. The multilayer packaging film of 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.

[0104] 10. The multilayer packaging film of any one of clauses 1-9, wherein the laminate layer comprises an extruded laminate resin.

[0105] 11. The multilayer packaging film of any one of clauses 1-10, wherein the extrusion laminating resin comprises a PLA-based extrusion laminating resin, a PHA-based extrusion laminating resin, a PBSA-based extrusion laminating resin, a PBAT-based extrusion laminating resin, a PCL-based extrusion laminating resin, a starch-based extrusion laminating resin, or a combination thereof.

[0106] 12. The multilayer packaging film of any one of clauses 1 to 11, wherein the second nucleating agent and the optional first nucleating agent are the same or different.

[0107] 13. The multilayer packaging film of any one of clauses 1-12, wherein each of the second nucleating agent and the optional first nucleating agent is independently selected from the group consisting of: (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 crystal form of an orthorhombic, hexagonal, or tetragonal crystal, (5) a polymorphic compound having at least one crystal form of an orthorhombic, hexagonal, or tetragonal crystal, and (6) combinations thereof.

[0108] 14. The multilayer packaging film of any one of clauses 1-13, wherein each of the second nucleating agent and any first nucleating agent is independently selected from the group consisting of 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.

[0109] 15. The multilayer packaging film of any one of clauses 1 to 14, wherein the outer printed layer comprises a PHA and a first nucleating agent.

[0110] 16. The multilayer packaging film of any one of clauses 1-15, wherein the inner product-side layer further comprises (iii) a sealant layer.

[0111] 17. The multilayer packaging film of any one of clauses 1-16, wherein the core layer further comprises PLA, PBSA, or a combination thereof.

[0112] 18. The multilayer packaging film of any one of clauses 1-17, wherein the barrier layer comprises a metal, 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), phenoxy resin, magnetic nanoparticles, epoxy-microencapsulated amine, a silica deposition layer, or a combination thereof.

[0113] 19. The multilayer packaging film of any one of clauses 1-18, wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

[0114] 20. The multilayer packaging film of any one of clauses 1-19, wherein the inner product side layer is formed via a process 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 barrier layer.

[0115] 21. The multilayer packaging film of any one of clauses 1-20, wherein the inner product-side layer further comprises at least a third layer, and wherein the process further comprises co-extruding at least a third composition, wherein the third composition forms the third layer.

[0116] 22. The multilayer packaging film of any one of clauses 1-21, wherein the inner product-side layer further comprises at least a fourth layer, and the process further comprises co-extruding at least a fourth composition, wherein the fourth composition forms the fourth layer.

[0117] 23. The multilayer packaging film of any one of clauses 1 to 22, wherein the barrier layer comprises a metal and the internal product side layer further comprises a third layer interposed between the barrier layer and the core layer.

[0118] 24. The multilayer packaging film of any one of clauses 1-23, wherein the core layer further comprises a biodegradable polymer selected from the group consisting of PLA, PBS, PBSA, PGA, poly(lactic-co-glycolic acid) (PLGA), PBAT, and combinations thereof.

[0119] 25. The multilayer packaging film of any one of clauses 1 to 24, wherein the core layer further comprises PLA.

[0120] 26. The multilayer packaging film of any one of clauses 1-25, wherein the third layer comprises poly(vinyl alcohol) (PVA), modified cellulose acetate, polysaccharide, PGA, PHA, PLA, PBSA, PBS, or a combination thereof.

[0121] 27. The multilayer packaging film of any one of clauses 1-26, wherein the third layer comprises PHA, PLA, or a combination thereof.

[0122] 28. The multilayer packaging film of any one of clauses 1-27, wherein the third layer comprises PHA, PLA, or a combination thereof, and the core layer further comprises PLA.

[0123] 29. The multilayer packaging film of any one of clauses 1 to 28, wherein the barrier layer comprises a metal, the inner product side layer further comprises a third layer and a fourth layer, and the core layer is interposed between the third layer and the fourth layer.

[0124] 30. The multilayer packaging film of any one of clauses 1 to 29, wherein the fourth layer is a sealant layer.

[0125] 31. The multilayer packaging film of any one of clauses 1-30, wherein the sealant layer comprises PHA, PLA, PBSA, or a combination thereof.

[0126] 32. The multilayer packaging film of any one of clauses 1-31, wherein the inner product-side barrier layer further comprises a fourth layer, the fourth layer comprising a primer coating.

[0127] 33. The multilayer packaging film of any one of clauses 1 to 32, wherein the primer coating is interposed between the barrier layer and the third layer.

[0128] 34. The multilayer packaging film of any one of clauses 1 to 33, wherein the primer coating is water-based.

[0129] 35. The multilayer packaging film of any one of clauses 1 to 33, wherein the primer coating is solvent-based.

[0130] 36. A multilayer packaging film according to any one of clauses 1 to 33, wherein the primer coating is polyurethane-based.

[0131] 37. A multilayer packaging film according to any one of clauses 1 to 33, wherein the primer coating is polyacrylate-based.

[0132] 38. The multilayer packaging film of any one of clauses 1-37, wherein the inner product-side layer further comprises a fourth layer, the fourth layer comprising a silica deposition layer.

[0133] 39. A multilayer packaging film according to any one of clauses 1 to 38, wherein the silica deposition layer is interposed between the barrier layer and the third layer.

[0134] 40. A multilayer packaging film as described in any one of clauses 1 to 39, wherein the internal product side layer further comprises a fourth layer, and the core layer is interposed between the third layer and the fourth layer.

[0135] 41. The multilayer packaging film of 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.

[0136] 42. The multilayer packaging film of any one of clauses 1-41, wherein the fourth layer comprises PHA, PLA, or a combination thereof.

[0137] 43. The multilayer packaging film of any one of clauses 1 to 42, wherein the inner product-side layer further comprises a fourth layer, the fourth layer comprising an electron beam top coating, the electron beam top coating being interposed between the laminate layer and the barrier layer.

[0138] 44. The multilayer packaging film of any one of clauses 1 to 43, wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

[0139] 45. The multilayer packaging film of any one of clauses 1 to 44, wherein the graphic element comprises text, an image, or a combination thereof.

[0140] 46. ​​A multilayer packaging film comprising: (i) an outer print layer comprising PHA, PLA, PBAT, PBS, cellophane, paper, or a combination thereof, (ii) a graphic element, and (iii) an optional first nucleating agent; (i) a barrier layer, (ii) a core layer, and (iii) an inner product-side layer comprising a third layer interposed between the barrier layer and the core layer, each of the core layer and the third layer comprising PHA and a second nucleating agent; and (ii) a laminate layer interposed between the outer print layer and the inner product-side layer, the laminate layer comprising an adhesive, an extrusion laminating resin, or a combination thereof.

[0141] 47. The multilayer packaging film of clause 46, wherein the core layer and / or the third layer independently further comprise a filler selected from the group consisting of mineral fillers, bio-based fillers, and combinations thereof.

[0142] 48. The multilayer packaging film of any one of clauses 46-47, wherein the core layer further comprises a biodegradable polymer selected from the group consisting of PLA, PBS, PBSA, PGA, PLGA, PBAT, and combinations thereof.

[0143] 49. A packaging article comprising a multilayer packaging film according to any one of clauses 1 to 48.

[0144] 50. A packaging article according to clause 49, wherein the packaging article is a food package.

[0145] 51. The packaging article of clause 49, wherein the packaging article is a snack food package.

[0146] 52. A packaging article according to clause 49, wherein the packaging article is a beverage package.

[0147] 53. A biodegradable barrier web comprising: a barrier web core layer having a first side and a second side; a barrier web skin 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 an ink printed on at least one of the first and second sides, wherein the printed web comprises: (1) about 10 weight percent to about 90 weight percent polyhydroxyalkanoate; (2) about 30 weight percent to about 90 weight percent polybutylene succinate, ... (3) at least one biodegradable polymer selected from the group consisting of poly(ethylene succinate-co-butylene adipate), poly(butylene adipate-co-butylene terephthalate), polycaprolactone, poly(lactic acid), cellulose acetate, and mixtures thereof; (4) from about 0.1 weight percent to about 5 weight percent of a nucleating agent; and (5) optionally, up to about 15 weight percent of a plasticizer; wherein the barrier web skin layer is adhered or laminated to the print web by an adhesive layer or extrusion lamination layer disposed between the barrier web skin layer and the print web.

[0148] 54. The film structure of clause 53, wherein the barrier web skin layer comprises: (1) about 10 weight percent to about 90 weight percent polyhydroxyalkanoate; (2) about 30 weight percent to about 90 weight percent of at least one biodegradable polymer selected from the group consisting of polybutylene succinate, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-butylene terephthalate, polycaprolactone, polylactic acid, polyglycolic acid, cellulose acetate, and mixtures thereof; and (3) about 0.1 weight percent to about 5 weight percent of a nucleating agent.

[0149] 55. The film structure of clause 54, wherein the skin layer comprises from about 40 weight percent to about 90 weight percent polyhydroxyalkanoate.

[0150] 56. The film structure of clause 54, wherein the skin layer comprises from about 40 weight percent to about 90 weight percent polybutylene succinate.

[0151] 57. The film structure of clause 54, wherein the skin layer comprises from about 40 weight percent to about 90 weight percent polybutylene succinate-co-butylene adipate.

[0152] 58. The film structure of clause 54, wherein the skin layer comprises about 30 weight percent to about 70 weight percent polylactic acid.

[0153] 59. The film structure of clause 54, wherein the nucleating agent of the skin layer is selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and mixtures thereof.

[0154] 60. The film structure of clause 53, wherein the barrier web core layer comprises: (1) about 10 weight percent to about 90 weight percent polyhydroxyalkanoate; (2) about 30 weight percent to about 90 weight percent of at least one biodegradable polymer selected from the group consisting of polybutylene succinate, polybutylene succinate adipate, polylactic acid, cellulose acetate, and mixtures thereof; (3) about 0.1 weight percent to about 5 weight percent nucleating agent; (4) about 0.01 weight percent to about 1.0 weight percent chain extender; (5) optionally, up to about 50 weight percent filler; (5) optionally, up to about 15 weight percent plasticizer; and (6) optionally, up to about 20 weight percent impact modifier.

[0155] 61. The film structure of clause 60, wherein the core layer comprises from about 30 weight percent to about 85 weight percent polyhydroxyalkanoate.

[0156] 62. The film structure of clause 60, wherein the core layer comprises about 30 weight percent to about 70 weight percent polybutylene succinate.

[0157] 63. The film structure of clause 60, wherein the core layer comprises about 30 weight percent to about 70 weight percent polybutylene succinate-co-butylene adipate.

[0158] 64. The film structure of clause 60, wherein the core layer comprises about 10 weight percent to about 60 weight percent polylactic acid.

[0159] 65. The film structure of clause 60, wherein the nucleating agent of the core layer is selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and mixtures thereof.

[0160] 66. The film structure of clause 60, wherein the filler of the core layer is selected from the group consisting of 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, polysaccharides, aluminum hydroxide, magnesium hydroxide, chitin, and mixtures thereof.

[0161] 67. The film structure of clause 60, wherein the core layer comprises about 5 weight percent to about 40 weight percent filler.

[0162] 68. The film structure of clause 8, wherein the core layer comprises about 5 weight percent to about 30 weight percent plasticizer.

[0163] 69. The film structure of clause 60, wherein the core layer comprises a plasticizer selected from the group consisting of sebacate, citrate, fatty esters of adipic, succinic, and glucaric acids, lactate, alkyl diester, citrate, alkyl methyl ester, dibenzoate, propylene carbonate, caprolactone diol having a number average molecular weight of 200 to 10,000 g / mol, poly(ethylene) glycol having a number average molecular weight of 400 to 10,000 g / mol, esters of vegetable oils, long chain alkyl acids, adipate, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 ester, HALLGREEN R-8010 ester, polyhydroxyalkanoate copolymers containing at least 18 mole percent of monomer residues of hydroxyalkanoates other than hydroxybutyrate, and mixtures thereof.

[0164] 70. The film structure of clause 60, wherein the core layer comprises a chain extender selected from the group consisting of organic peroxyacids, inorganic peroxyacids, epoxy functionalizing reagents, or mixtures thereof.

[0165] 71. The film structure of clause 60, wherein the core layer comprises about 5 weight percent to about 15 weight percent of an impact modifier.

[0166] 72. The film structure of clause 60, wherein the core layer further comprises up to 50 weight percent of one or more additives selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, polyvinyl laurate, ethylene vinyl acetate, G-POLYMER, polybutylene adipate terephthalate (PBAT), Ecoflex, poly(glycolic acid), polycaprolactone, furandicarboxylic acid-based polyesters, thermoplastic starch, cellulose, nanocellulose, glucan, and mixtures thereof.

[0167] 73. The film structure of clause 53, wherein the barrier web sealant layer comprises: (1) about 30 weight percent to about 100 weight percent of at least one biodegradable polymer selected from the group consisting of polyhydroxyalkanoate, polybutylene succinate, polybutylene succinate-co-butylene adipate, polylactic acid, polycaprolactone, polyglycolic acid, polybutylene adipate-co-butylene terephthalate, cellulose acetate, and mixtures thereof; and (2) about 0.1 weight percent to about 5 weight percent of a nucleating agent.

[0168] 74. The film structure of clause 73, wherein the sealant layer comprises from about 30 weight percent to about 90 weight percent polyhydroxyalkanoate.

[0169] 75. The film structure of clause 73, wherein the sealant layer comprises from about 10 weight percent to about 100 weight percent polybutylene succinate.

[0170] 76. The film structure of clause 73, wherein the sealant layer comprises from about 10 weight percent to about 100 weight percent polybutylene succinate-co-butylene adipate.

[0171] 77. The film structure of clause 73, wherein the sealant layer comprises about 10 weight percent to about 100 weight percent polylactic acid.

[0172] 78. The film structure of clause 73, wherein the nucleating agent of the sealant layer is selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and mixtures thereof.

[0173] 79. The film structure of clause 53, wherein the printing web comprises: (1) about 10 weight percent to about 90 weight percent polyhydroxyalkanoate; (2) about 30 weight percent to about 70 weight percent of at least one biodegradable polymer selected from the group consisting of polybutylene succinate, polybutylene succinate-co-butylene adipate, polylactic acid, polycaprolactone, polyglycolic acid, polybutylene adipate-co-butylene terephthalate, cellulose acetate, and mixtures thereof; (3) about 0.1 weight percent to about 5 weight percent nucleating agent; and (4) optionally, up to about 50 weight percent plasticizer.

[0174] 80. The film structure of clause 79, wherein the print web comprises from about 30 weight percent to about 70 weight percent polyhydroxyalkanoate.

[0175] 81. The film structure of clause 79, wherein the printing web comprises from about 30 weight percent to about 70 weight percent polybutylene succinate.

[0176] 82. The film structure of clause 79, wherein the print web comprises from about 30 weight percent to about 70 weight percent polybutylene succinate-co-butylene adipate.

[0177] 83. The film structure of clause 79, wherein the print web comprises about 40 weight percent to about 70 weight percent polylactic acid.

[0178] 84. The film structure of clause 79, wherein the nucleating agent of the printing web is selected from the group consisting of erythritol, pentaerythritol, dipentaerythritol, artificial sweeteners, stearates, sorbitol, mannitol, inositol, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, and mixtures thereof.

[0179] 85. The film structure of clause 79, wherein the print web comprises from about 5 weight percent to about 30 weight percent plasticizer.

[0180] 86. The film structure of clause 79, wherein the plasticizer of the printing web is selected from the group consisting of sebacate, citrate, fatty esters of adipic, succinic and glucaric acids, lactate, alkyl diesters, citrate, alkyl methyl esters, dibenzoate, propylene carbonate, caprolactone diols having a number average molecular weight of 200 to 10,000 g / mol, poly(ethylene) glycols having a number average molecular weight of 400 to 10,000 g / mol, esters of vegetable oils, long chain alkyl acids, adipate, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 esters, HALLGREEN R-8010 esters, polyhydroxyalkanoate copolymers containing at least 18 mole percent of monomer residues of hydroxyalkanoates other than hydroxybutyrate, and mixtures thereof.

[0181] It will be understood that the use of the indefinite articles "a" and "an" with respect to an element (e.g., "outer printed layer," "inner product-side layer," "core layer," "barrier layer," "laminate layer," etc.) does not exclude the presence of a plurality of such elements in some embodiments.

[0182] The foregoing detailed description and accompanying drawings have been provided for purposes of explanation and illustration and are not intended to limit the scope of the appended claims. Many variations in the presently preferred embodiments illustrated herein will be apparent to those skilled in the art and will fall within the scope of the appended claims and their equivalents.

[0183] It will be understood that the elements and features recited in the appended claims may be combined in different ways to create new claims which are also within the scope of the invention. Thus, although the dependent claims appended below may depend only on a single independent or dependent claim, such dependent claims may alternatively depend on any preceding claim, whether independent or dependent, and such new combinations will be understood to form part of this specification.

Claims

1. (i) an outer print layer comprising polyhydroxyalkanoate (PHA), polylactide (PLA), polybutylene adipate terephthalate (PBAT), polybutyl succinate (PBS), cellophane, paper, or a combination thereof, (ii) a graphic element, and (iii) a first nucleating agent; (i) a core layer and (ii) an inner product side layer comprising a barrier layer; and a laminate layer interposed between the outer printed layer and the inner product-side layer; the core layer comprises PHA, a second nucleating agent, and a biodegradable polymer selected from the group consisting of PLA, PBS, polybutylene succinate adipate (PBSA), polyglycolide (PGA), poly(lactic-co-glycolic acid) (PLGA), PBAT, and combinations thereof; the barrier layer comprises a metal, microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, graphene, a water-based primer coating, a solvent-based primer coating, a polyurethane-based primer coating, an acrylate-based primer coating, PGA, a phenoxy resin, magnetic nanoparticles, an epoxy-microencapsulated amine, a silica deposition layer, or a combination thereof; the laminate layer comprises an adhesive or an extrusion lamination resin; each of the first nucleating agent and the second nucleating agent is independently selected from the group consisting of 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; Multi-layer packaging film.

2. 10. The multilayer packaging film of claim 1, wherein the outer print layer further comprises polybutylene succinate adipate (PBSA), polycaprolactone (PCL), or a combination thereof.

3. 10. The multilayer packaging film of claim 1, wherein the core layer further comprises a filler selected from the group consisting of an inorganic filler, a bio-based filler, or a combination thereof.

4. 4. The multilayer packaging film of 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. 4. The multilayer packaging film of claim 3, wherein the inorganic filler is selected from the group consisting of sodium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum sulfate, magnesium oxide, calcium oxide, alumina, mica, talc, silica, clay, glass spheres, titanium dioxide, aluminum hydroxide, zeolite, and combinations thereof.

6. The multilayer packaging film of claim 3 , wherein the inorganic filler comprises calcium carbonate.

7. 4. The multilayer packaging film of claim 3, wherein the bio-based filler comprises wheat straw, soybean flakes, rice hulls, oat hulls, or combinations thereof.

8. The multilayer packaging film of claim 1 , wherein the laminate layer comprises an adhesive.

9. 9. The multilayer packaging film of 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 of claim 1 , wherein the laminate layer comprises an extruded laminate resin.

11. 11. The multilayer packaging film of claim 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.

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

13. 2. The multilayer packaging film of claim 1, wherein the outer print layer comprises: (i) PHA and PLA, PBAT, PBS, cellophane, paper, or a combination thereof; (ii) the graphic element; and (iii) the first nucleating agent.

14. The multilayer packaging film of claim 1 , wherein the inner product-side layer further comprises: (iii) a sealant layer.

15. 10. The multilayer packaging film of claim 1, wherein the core layer further comprises PLA, PBSA, or a combination thereof.

16. The multilayer packaging film of claim 1 , wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

17. 10. The multilayer packaging film of claim 1, wherein the inner product-side layer is formed via a process 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 barrier layer.

18. 20. The multilayer packaging film of claim 17, wherein the inner product side layer further comprises at least a third layer, and the process further comprises coextruding at least a third composition, wherein the third composition forms the third layer.

19. 20. The multilayer packaging film of claim 18, wherein the inner product side layer further comprises at least a fourth layer, and the process further comprises coextruding at least a fourth composition, wherein the fourth composition forms the fourth layer.

20. 10. The multilayer packaging film of claim 1, wherein the barrier layer comprises a metal, and the inner product-side layer further comprises a third layer interposed between the barrier layer and the core layer.

21. 21. The multilayer packaging film of claim 20, wherein the core layer further comprises PLA.

22. 21. The multilayer packaging film of claim 20, wherein the third layer comprises poly(vinyl alcohol) (PVA), modified cellulose acetate, polysaccharides, PGA, PHA, PLA, PBSA, PBS, or combinations thereof.

23. 21. The multilayer packaging film of claim 20, wherein the third layer comprises PHA, PLA, or a combination thereof.

24. 21. The multilayer packaging film of claim 20, wherein the third layer comprises PHA, PLA, or a combination thereof, and the core layer further comprises PLA.

25. 21. The multilayer packaging film of claim 20, wherein the barrier layer comprises a metal, the inner product side layer further comprises a third layer and a fourth layer, and the core layer is interposed between the third layer and the fourth layer.

26. 26. The multilayer packaging film of claim 25, wherein the fourth layer is a sealant layer.

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

28. 21. The multilayer packaging film of claim 20, wherein the inner product side layer further comprises a fourth layer, the fourth layer comprising a primer coating.

29. 30. The multilayer packaging film of claim 28, wherein the primer coating is interposed between the barrier layer and the third layer.

30. 30. The multilayer packaging film of claim 28, wherein the primer coating is water-based.

31. 30. The multilayer packaging film of claim 28, wherein the primer coating is solvent-based.

32. 30. The multilayer packaging film of claim 28, wherein the primer coating is polyurethane-based.

33. 30. The multilayer packaging film of claim 28, wherein the primer coating is polyacrylate-based.

34. 21. The multilayer packaging film of claim 20, wherein the inner product side layer further comprises a fourth layer, the fourth layer comprising a silica deposition layer.

35. 35. The multilayer packaging film of claim 34, wherein the silica deposition layer is interposed between the barrier layer and the third layer.

36. 21. The multilayer packaging film of claim 20, wherein the inner product side layer further comprises a fourth layer, and the core layer is interposed between the third layer and the fourth layer.

37. 37. The multilayer packaging film of claim 36, wherein the fourth layer comprises PVA, modified cellulose acetate, polysaccharides, PGA, PHA, PLA, PBSA, PBS, or combinations thereof.

38. 37. The multilayer packaging film of claim 36, wherein the fourth layer comprises PHA, PLA, or a combination thereof.

39. 21. The multilayer packaging film of claim 20, wherein the inner product side layer further comprises a fourth layer, the fourth layer comprising an electron beam top coating, the electron beam top coating being interposed between the laminate layer and the barrier layer.

40. 21. The multilayer packaging film of claim 20, wherein the metal comprises aluminum, aluminum oxide, or a combination thereof.

41. The multilayer packaging film of claim 1 , wherein the graphic element comprises text, an image, or a combination thereof.

42. an outer print layer comprising: (i) PHA, PLA, PBAT, PBS, cellophane, paper, or a combination thereof; (ii) a graphic element; and (iii) a first nucleating agent; an inner product side layer including (i) a barrier layer, (ii) a core layer, and (iii) a third layer interposed between the barrier layer and the core layer; and a lamination layer interposed between the outer print layer and the inner product-side layer, the lamination layer comprising an adhesive, an extrusion lamination resin, or a combination thereof; Including, the barrier layer comprises a metal, microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, graphene, a water-based primer coating, a solvent-based primer coating, a polyurethane-based primer coating, an acrylate-based primer coating, polyglycolide (PGA), a phenoxy resin, magnetic nanoparticles, an epoxy-microencapsulated amine, a silica deposition layer, or a combination thereof; the core layer comprises PHA, a second nucleating agent, and a biodegradable polymer selected from the group consisting of PLA, PBS, PBSA, PGA, PLGA), PBAT, and combinations thereof; the third layer comprises a PHA and a second nucleating agent; 1. A multilayer packaging film, wherein each of the first nucleating agent and the second nucleating agent is independently selected from the group consisting of 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.

43. 43. The multilayer packaging film of claim 42, wherein the core layer and / or the third layer independently further comprise a filler selected from the group consisting of a mineral filler, a bio-based filler, and combinations thereof.

44. 43. The multilayer packaging film of claim 42, wherein the core layer further comprises a biodegradable polymer selected from the group consisting of PLA, PBS, PBSA, PGA, PLGA, PBAT, and combinations thereof.

45. A packaging article comprising the multilayer packaging film of claim 1.

46. 46. ​​The packaging article of claim 45, wherein the packaging article is a food package.

47. 43. A packaging article comprising the multilayer packaging film of claim 42.

48. 48. The packaging article of claim 47, wherein the packaging article is a snack food package.

49. 48. The packaging article of claim 47, wherein the packaging article is a beverage package.

50. 43. The multilayer packaging film of claim 42, wherein the outer print layer comprises: (i) PHA and PLA, PBAT, PBS, cellophane, paper, or a combination thereof; (ii) a graphic element; and (iii) a first nucleating agent.

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