CROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to and the benefit of U.S. App. No. 63/429,887 filed December 2, 2022, the entire contents of which are hereby incorporated by reference in their entirety.

FIELD OF DISCLOSURE

[0002] The present disclosure is related to containers comprising a polyhydroxyalkanoate surface having a fluorinated carbon or a diamond-liked carbon material deposited thereon. The surface treatments typically involve plasma-based deposition techniques.

BACKGROUND

[0003] Biodegradable resins attracted attention as environmentally friendly resins because the resins turn into substances that originally exist in nature due to actions such as hydrolysis under the environment and microbial metabolism and are resins that are widely used and expected to be more widely used in the future. These resins may have strength comparable to general-purpose plastics but often have gas transmission rates that are insufficient for their use in many containers as the product being contained is not in a controlled environment. In particular, polyhydroxyalkanoate (PHA) based containers are difficult to manufacture, have poor tensile strengths, and often do not result in appropriate shelf lives of food products or consumer packaged goods contained therein due to migration of various materials into and out of the food product.

[0004] It is therefore an object of this disclosure to provide PHA based containers that can appropriately control the environment for any product contained therein is exposed to and be suitable for mass production. Furthermore, these containers offer these properties without significant impediment to the biodegradability afforded by the PHA.

SUMMARY

[0005] In accordance with the foregoing objectives and others, the present disclosure provides PHA surface treatments which enhance the barrier properties of PHA based thermoplastic resins. These surface treatments are particularly suitable for containers made from these PHA based thermoplastic resins affording them the ability to be used in a wide variety of industries such as the food and beverage industry and consumer packaged goods industry such that the surface of the container is the surface exposed to a food, beverage (alcohol or non-alcohol), or consumer packaged good (e.g., beauty, personal care, haircare, skincare, cleaning, pharmaceutical, nutraceutical, household, tobacco, cannabis. CBD, THC) product. In particular embodiments, the containers of the present disclosure are bottles, wherein the inner surface of the bottle is surface treated as described herein. In some embodiments, the container (and the surface) are chosen for wine, spirits, beer, carbonated soft drinks, juices, water and/or oil (e.g., oil comprising one or more cannabinoids such as CBD and/or THC).

[0006] The containers for a product having a surface to be exposed to the product; wherein the container may have a surface is formed from a thermoplastic resin composition surface treated with a fluorinated hydrocarbon; and the thermoplastic resin composition comprises a polyhydroxyalkanoate (PHA) polymer.

[0007] In some embodiments, the surface is surface treated with a plasma surface treatment formed from the fluorinated hydrocarbon. For example, the surface may be surface treated with a plasma formed from a fluorinated hydrocarbon selected from hydrofluorocarbons such as a C1-C5 alkane substituted with fluorine (e.g.. fluoromethane, difluoromethane, trifluoromethane, fluoroethane, difluoroethane, trifluoroethane such as 1,1,1 -trifluoroethane, tetrafluoroethane such as 1,1,1,2-tetrafluoroethane, pentafluoroethane such as 1, 1,1, 2,2- pentafluoroethane, fluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluorpropane such as 1,1,1,3,3-pentafluoropropane. hexafluoropropane such as

1.1.1.3.3.3-hexafluoropropane or 1,1,1,2,3,3-hexafluoropropane or 1.1.2.2,3,3- hexafluoropropane, heptafluoropropane such as 1,1,1, 2,2,3, 3, 3 -heptafluoropropane, fluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, pentafluorobutane such as

1.1.1.3.3-pentafluorobutane, hexafluorobutane, heptafluorobutane, octafluorobutane, nonafluorobutane, fluoropentane, difluoropentane. trifluoropentane, tetrafluoropentane, pentafluoropentane, hexafluoropropane, heptafluoropropane, octafluoropropane, nonafluoropropane, decafluoropropane such as 1,1,1,2,2,3,4,5,5,5-decafluoropropane) or a hydrofluoroolefins (FHO) such as C2-C5 mono unsaturated alkane substituted with fluorine (e.g., fluoroethene, difluorethene, trifluoroethene, fluropropene, difluoropropene, trifluoropropene, tetrafluropropene such as 2,3,3,3-tetrafluoropropene, 1, 3,3,3- tetrafluoropropene, pentafluoropropene, fluorobutene, difluorobutene, trifluorobutene, tetraflurobutene, pentafluorobutene, hexafluorobutene such as l,l,l,4,4,4-hexafluoro-2-butene including cis-l,l,l,4,4,4-hexafluoro-2-butene or trans-l,l,l,4,4,4-hexafluoro-2-butene, heptafluorobutene, fluropentene. difluoropentene. trifluoropentene, tetrafluoropentene. pentafluoropentene, hexafluoropentene. heptafluoropentene, octoafluoropentene, nonafluoropentene) and mixtures thereof. In some embodiments, the surface is surface treated with a plasma formed from a fluorinated hydrocarbon selected from 1,1,1,2-tetrafluoroethane, 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, and combinations thereof.

[0008] The surface may, for example, be treated with a plasma surface treatment comprising a plasma formed from a noble gas (e.g., He, Ne, Ar) and/or oxygen (O2) and/or nitrogen (N2) and/or from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene) and/or the fluorinated hydrocarbon, or combinations thereof. In some embodiments, the surface may be surface treated with a first plasma formed from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene) followed by a second plasma formed from the fluorinated hydrocarbon. In some embodiments, the surface is surface treated with a first plasma formed from a noble gas followed by a second plasma formed from the fluorinated hydrocarbon. In various implementations, the surface is surface treated with a first plasma formed from a noble gas, a second plasma formed from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene), and a third plasma formed from the fluorinated hydrocarbon.

[0009] Any phase of the plasma treatment as defined by the components in the source gas (e.g., a noble gas (e.g.. He, Ne, Ar) and/or hydrogen (H2) and/or oxygen (O2) and/or nitrogen (N2) and/or from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene) and/or the fluorinated hydrocarbon phase) may have a gas pressure (or partial pressure) of less than (or from 0. 1 to) 200 m bar (e.g., 1 mbar to 200 mbar, 1 mbar to 150 mbar, 1 mbar to 120 mbar, 20 mbar to 200 mbar, 20 mbar to 100 mbar. less than 10 mbar, 0.1 mbar to 10 mbar). For example, in some embodiments, each phase of the plasma treatment (e.g., a noble gas (e.g.. He, Ne, Ar) and/or hydrogen (H2) and/or oxygen (O2) and/or nitrogen (N2) and/or from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene) and/or the fluorinated hydrocarbon phase) may independently have a gas pressure of less than (or from 0. 1 to) 200 m bar (e.g., 1 mbar to 200 mbar, 1 mbar to 150 mbar. 1 mbar to 120 mbar, 20 mbar to 200 mbar, 20 mbar to 100 mbar). In some embodiments, a phase or all phases of the surface treatment (e.g., a noble gas (e.g., He, Ne, Ar) and/or hydrogen (H2) and/or oxygen (O2) and/or nitrogen (N2) and/or from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene) and/or the fluorinated hydrocarbon phase) may occur for less than (or from 1 s to) 60 s (e.g., less than 45 s, less than 30 s, less than 20 s, from 5 s to 60 s, from 5 s to 45 s, from 5 to 30 s from 10 s to 20 s). In some embodiments, each phase of the surface treatment (e.g.. anoble gas (e.g., He. Ne, Ar) and/or hydrogen (H2) and/or oxygen (O2) and/or nitrogen (N2) and/or from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene) and/or the fluorinated hydrocarbon phase) may independently occur for less than (or from 0. 1 s to) 60 s (e.g., less than 45 s, less than 30 s, less than 20 s, less than 15 s, less than 10 s, less than 5 s, from 1 s to 20 s, from 1 s to 10 s, from 1 to 5 s, from 10 s to 20 s).

[0010] The present disclosure also provides containers for a product having a surface to be exposed to the product; wherein the container may have a diamond like or amorphous diamond like coating on the surface; and the thermoplastic resin composition comprises a polyhydroxyalkanoate (PHA) polymer. In some embodiments, the diamond like carbon (DLC) layer is formed with a plasma surface treatment formed from an organic compound source gas. For example, the organic compound source gas is an aliphatic hydrocarbon, an aromatic hydrocarbon, an oxygencontaining hydrocarbon, a nitrogen-containing hydrocarbon and mixtures thereof. In some embodiments, the organic compound source gas comprises (or is) benzene, toluene, o-xylene, m-xylene, p-xylene, a C6-C12 cycloalkane (e.g., cyclohexane), a C2-C10 alkene (e.g., C2-C6 alkene, C2-C4 alkene, ethylene, propylene, butylene), or C2-C10 alkyne (e.g., C2-C6 alkyne, C2- C4 alkyne, acetylene, ally lene, butyne, 1 -butyne), or combinations thereof. In particular embodiments, the organic compound source gas is acetylene. In some embodiments, the surface is surface treated with a first plasma formed from a noble gas followed by a second plasma formed from the organic compound source gas (e.g., acetylene) to produce the diamond like or amorphous diamond like layer.

[0011] The plasma surface treatment (e.g., a plasma deposition phase with a noble gas (e.g., He. Ne, Ar) and/or oxygen (O2) and/or nitrogen (N2) and/or the organic compound source gas) may have a gas pressure of less than (or from 0.1 to) 200 m bar (e.g., 1 mbar to 200 mbar, 1 mbar to 150 mbar, 1 mbar to 120 mbar, 20 mbar to 200 mbar, 20 mbar to 100 mbar) in order to produce a diamond like or amorphous diamond like coating. For these coatings, the RF voltage and/or RF frequency, and or pressure may be chosen to induce DLC formation such as choosing lower pressures to increase the density of the carbon during deposition. For example, the organic material may have a pressure of from 0.1 x 10' ³ Pa to 1 x 10 ² Pa (e.g. , 1 x 10‘ ² to 10 Pa). In some embodiments, each phase of the plasma treatment (e.g. , a plasma deposition phase with a noble gas (e.g., He, Ne, Ar) and/or oxygen (O2) and/or nitrogen (N2) and/or the organic compound source gas) independently has a gas pressure of less than (or from 0. 1 to) 200 m bar (e.g., 1 mbar to 200 mbar, 1 mbar to 150 mbar, 1 mbar to 120 mbar, 20 mbar to 200 mbar, 20 mbar to 100 mbar) or from 0. 1 x 10‘ ³ Pa to N 10 ² Pa (e.g., I x l0’ ² to 10 Pa).

[0012] In some embodiments, a phase or all phases of the surface treatment (e.g., a plasma deposition phase with a noble gas (e.g., He, Ne, Ar) and/or hydrogen (H2) and/or oxygen (O2) and/or nitrogen (N2) and/or the organic compound source gas) occurs for less than (or from 0. 1 s to) 60 s (e.g., less than 45 s, less than 30 s, less than 20 s, from 5 s to 60 s, from 5 s to 45 s, from 5 to 30 s from 10 s to 20 s). In various implementations, each phase of the surface treatment (e.g.. a noble gas (e.g.. He, Ne, Ar) and/or hydrogen (H2) and/or oxygen (O2) and/or nitrogen (N2) and/or from a C1-C5 unsubstituted alkane and/or a C2-C5 unsubstituted alkene (e.g., acetylene) and/or the fluorinated hydrocarbon phase) independently occurs for less than (or from 1 s to) 60 s (e.g., less than 45 s, less than 30 s, less than 20 s, less than 15 s, less than 10 s, less than 5 s, from 1 s to 20 s, from 1 s to 10 s. from 1 to 5 s, from 10 s to 20 s). In some embodiments, the diamond like carbon layer or amorphous diamond like carbon layer is less than (or from 10 nm to) 250 nm (e.g., less than 200 nm, less than 150 nm, less than 100 nm, less than 50 nm, from 10 nm to 200 nm, from 30 nm to 180 nm, from 50 nm to 160 nm, from 60 nm to 150 nm, from 1 to 50 nm, from 10 to 40 nm).

[0013] In some embodiments, the polyhydroxyalkanoate polymer may comprise a hydroxyhexanoic acid (e.g.. 3 -hydroxy hexanoic acid) monomeric unit (e.g., less than 20% hydroxyhexanoic acid, less than 15% hydroxyhexanoic acid, less than 10% hydroxyhexanoic acid, less than 8% hydroxyhexanoic acid, from 0.1 % to 15% hydroxyhexanoic acid, from 0.1% to 10% hydroxyhexanoic acid, from 0.1% to 8% hydroxyhexanoic acid, from 1% to 15% hydroxyhexanoic acid, from 1% to 10% hydroxyhexanoic acid, from 1% to 8% hydroxyhexanoic acid, from 3% to 15% hydroxyhexanoic acid, from 3% to 10%, from 3% to 8%). In particular embodiments, the polyhydroxyalkanoate polymer comprises a hydroxybutyric acid (e.g., 3 -hydroxy butyric acid) monomeric unit (e.g., at least (or up to 100%) 90% by mole hydroxybutyric acid such as 3-hydroxybutyric acid, at least 95% by mole hydroxybutyric acid such as 3-hydroxybutyric acid, at least 99% by mole hydroxybutyric acid such as 3-hydroxybutyric acid, a homopolymer, a homopolymer of hydroxybutyric acid). In some embodiments, the polyhydroxyalkanoate polymer is a copolymer. For example, the copolymer may comprise hydroxybutyric acid (e.g., 3-hydroxybutyric acid) and hydroxyhexanoic acid (e.g.. 3-hydroxyhexanoic acid) monomeric units. For example, the copolymer may comprise less than 15% (e.g., less than 10%, less than 8%, from 0.1% to 15%, from 0.1% to 10%, from 0.1% to 8%, from 1% to 15%, from 1% to 10%, from 1% to 8%, from 3% to 15%, from 3% to 10%, from 3% to 8%) hydroxyhexanoic acid monomeric units by mole as a monomeric unit. In some embodiments, the thermoplastic resin composition comprises a mixture of a polyhydroxy alkanoate copolymer and a polyhydroxy alkanoate polymer. For example, the mixture may be less than 50% (e.g., less than 40%, less than 30%, less than 20%, less than 10%, from 1% to 50%, from 3% to 50%, from 1% to 40%. from 3% to 40% from 1% to 20%, from 3% to 20%) of the polyhydroxy alkanoate polymer by weight based on the mixture (the weight of the polyhydroxyalkanoate copolymer and the polyhydroxyalkanoate polymer). In some embodiments, the polyhydroxyalkanoate polymer comprises at least 99% by mole of a single monomeric unit (e.g., at least 99% by mole hydroxybutyric acid such as 3- hydroxybutyric acid, a homopolymer, a homopolymer of hydroxybutyric acid). In various implementations, the thermoplastic resin composition further comprises one or more biodegradable polymers (e.g., polyethylene succinate), poly(butylene succinate), poly(propylene succinate), poly(ethylene adipate), poly(butylene adipate), poly(propylene adipate), poly(butylene terephthalate), poly(propylene terephthalate), poly(ethylene succinate- co-adipate), poly(propylene succinate-co-adipate). poly(butylene succinate-co-adipate), poly(propylene succinate-co-adipate), poly(ethylene succinate-co-terephthalate), poly(propylene succinate-co-terephthalate), poly(butylene succinate-co-terephthalate), poly(propylene succinate-co-terephthalate), poly(caprolactone), poly(lactic acid), cellulose esters (such as cellulose acetate), nanocellulose, thermoplastic starch, and mixtures thereof). Furthermore, the thermoplastic resin may comprise a nucleating agent (e.g., pentaerythritol).

[0014] Typically, the container is to house a food or beverage or consumer packaged good product. Generally, the product being contained within the containers of the present disclosure may be a food or beverage product (e.g., wine, beer, spirits, ready to drink cocktail, juice, carbonated beverage product such as seltzer, noncarbonated beverage such as water, combinations thereof), or a consumer packaged good such as a product comprising one or more cannabinoids (e.g., an oil), a beauty product, haircare, skincare, cosmetics product, dietary supplements, pharmaceutical product, or a cleaning product. In particular embodiments, the container is a bottle. These containers may be a molded article formed from molding (e.g., by injection molding, injection stretch blow molding, injection blow molding, extrusion blow molding, thermoforming or combinations thereof) the thermoplastic resin composition and surface treating the surface with the fluorinated hydrocarbon or depositing a diamond like coating or amorphous diamond like coating on the surface. In various implementations, the container is a molded article formed from mixing a first thermoplastic resin composition and a second thermoplastic resin composition, wherein the first thermoplastic resin composition and the second thermoplastic resin compositions have different degrees of crystallinity, extruded, and surface treated with the fluorinated hydrocarbon. For example, the first thermoplastic resin may have a tensile modulus greater than 1000 MPa (e.g., greater than 1500 MPa, greater than 1800 MPa, from 1000 MPa to 2500 MPa from 1000 MPa to 2000 MPa, from 1500 MPa to 2000 MPa. from 1700 to 1900 MPa, from 1800 to 1850 MPa) and the second thermoplastic resin has a tensile modulus less than 1000 MPa (e.g., less than 800 MPa, less than 600 MPa, less than 500 MPa, from 100 to 1000 MPa, from 200 to 600 MPa, from 200 MPa to 500 MPa, from 400 MPa to 500 MPa, from 450 MPa to 490 MPa) as measured by ISO527. In some embodiments, the first thermoplastic resin has a melting point less than 150°C (e.g., from 140°C to 150°C) and the second thermoplastic resin has a melting point greater than 150°C (e.g., 150°C to 160°C) as measured by differential scanning calorimetry run from 30°C to 200°C by 10°C/min. In various implementations, the weight ratio of the first thermoplastic resin to the second thermoplastic resin is from 10: 1 to 1: 10 (e.g., 9: 1 to 1:9, 5: 1 to 1:5, 4: 1 to 1:4, 3: 1 to 1 :3, 2: 1 to 1 :2, 3:2 to 2:3. 2: 1 to 5: 1).

[0015] These treatments may augment the surface properties of the surface and alter the transmission rates of various materials through the container. In some embodiments, the container has altered barrier properties as compared to an otherwise identical container without the fluorinated hydrocarbon treatment or diamond like layer or amorphous diamond like layer (an untreated container). The altered barrier properties (e.g., increased oxygen barrier strength, increased CO2 barrier strength, increased water barrier strength, increased migration prevention such as preventing contaminants and other materials from entering the container and/or preventing contained components from leaving the sealed container) may be selected from one or more of: a) an oxygen transmission rate that is less than 10% (e.g., less than 5%, less than 3%, from 0.1% to 10%, from 0.1% to 5%, from 0.1% to 3%) of the oxygen transmission rate of an otherwise identical untreated container (e.g., as measured by ASTM F-1927 at 18°C, 21% O2, and <50% ambient relative humidity such as 0% RH, 10% RH, 20% RH, 30% RH, 40% RH or 50%RH); b) a CO2 transmission rate that is less than 30% (e.g., less than 20%) of the CO2 transmission rate of an otherwise identical untreated container (e.g., as measured with ASTM F2476-20 or F2476-05); c) an H2O transmission rate that is less than 75% (e.g., less than 60%, less than 50%) of the H2O transmission rate of an otherwise identical untreated container (e.g., as measured with ASTM Fl 249-06); d) when initially pressurized to 70-90 psi CO2 the CO2 partial pressure in a sealed container (e.g., a bottle having a cap such as a screw cap) is maintained at more than 60 psi (e.g., more than 65 psi, more than 70 psi) for more than (or up to 1 year) 1 day (e.g., at least a week, at least two weeks, at least a month, at least, two months, at least three months, at least six months, at least a year, from 10 days to a year, from 10 days to six months, from 10 days to three months); and e) when initially containing a liquid having from 25-40 ppm O2 in a sealed container (e.g., a bottle having a cap such as a screw cap), the O2 in the liquid is maintained at more than 15 ppm (e.g., more than 20 ppm, more than 25 ppm) for more than (or up to 3 years or 2 years) 1 day (e.g., at least a week, at least two weeks, at least a month, at least, two months, at least three months, at least six months, at least a year, at least from 10 days to a year, from 10 days to 2 years, from 10 days to 3 years, from 10 days to six months, from 10 days to three months).

In various implementations, and particularly for containers involving solid products such as dietary supplements, the altered barrier properties (e.g., increased oxygen barrier strength, increased CO2 barrier strength, increased water barrier strength) may be selected from one or more of: a) an oxygen transmission rate that is less than 10% (e.g., less than 5%, less than 3%, from 0.1% to 10%, from 0.1% to 5%, from 0.1% to 3%) of the oxygen transmission rate of an otherwise identical untreated container (e.g., as measured by ASTM F-1927 at 18°C, 21% O2, and <50% ambient relative humidity' such as 0% RH, 10% RH, 20% RH, 30% RH, 40% RH or 50%RH); b) a CO2 transmission rate that is less than 30% (e.g., less than 20%) of the CO2 transmission rate of an otherwise identical untreated container (e.g., as measured with ASTM F2476-20 or F2476-05); c) an H2O transmission rate that is less than 75% (e.g., less than 60%, less than 50%) of the H2O transmission rate of an otherwise identical untreated container (e.g., as measured with ASTM Fl 249-06); and d) the O ₂ in the container starting from initial sealing (e.g., with a sealing atmosphere of from 0.01% to 75% O ₂ by weight of the sealing atmosphere held at vacuum, atmospheric, or positive pressure with respect to atmospheric pressure at 25°C) of a product (e.g., a solid product) changes by less than 10% by weight or less than 5% by weight or less than 1% by weight more than (or up to 3 years or 2 years) 1 day (e g., at least a week, at least two weeks, at least a month, at least, two months, at least three months, at least six months, at least a year, at least from 10 days to a year, from 10 days to 2 years, from 10 days to 3 years, from 10 days to six months, from 10 days to three months).

In some embodiments, the treated container has an oxygen transmission rate of less than (or from 0.1 to) 10 cc/m ² or less than 5 cc/m ² or less than 2 cc/m ² or less than 1 cc/m ²

DETAILED DESCRIPTION

[0016] Detailed embodiments of the present disclosure are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the disclosure that may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments of the disclosure is intended to be illustrative, and not restrictive.

[0017] All terms used herein are intended to have their ordinary meaning in the art unless otherwise provided. All concentrations are in terms of percentage by weight of the specified component relative to the entire weight of the topical composition, unless otherwise defined.

[0018] As used herein, "a" or “an” shall mean one or more. As used herein when used in conjunction with the word “comprising,” the words “a” or “an” mean one or more than one. As used herein “another” means at least a second or more.

[0019] As used herein, all ranges of numeric values include the endpoints and all possible values disclosed between the disclosed values. The exact values of all half integral numeric values are also contemplated as specifically disclosed and as limits for all subsets of the disclosed range. For example, a range of from 0.1% to 3% specifically discloses a percentage of 0.1%, 1%, 1.5%, 2.0%, 2.5%, and 3%. Additionally, a range of 0.1 to 3% includes subsets of the original range including from 0.5% to 2.5%, from 1% to 3%, from 0. 1% to 2.5%, etc. It will be understood that the sum of all weight % of individual components will not exceed 100%. [0020] By “consist essentially” it is meant that the ingredients include only the listed components along with the normal impurities present in commercial materials and with any other additives present at levels which do not affect the operation of the embodiments disclosed herein, for instance at levels less than 5% by weight or less than 1% or even 0.5% by weight.

[0021] The present disclosure provides containers for a product having a surface to be exposed to the product; wherein the surface is formed from a thermoplastic resin composition surface treated with a fluorinated hydrocarbon; and the thermoplastic resin composition comprises a polyhydroxyalkanoate (PHA) polymer.

[0022] The present disclosure also provides containers for a product having a surface to be exposed to the product; wherein the surface is formed from a thermoplastic resin composition surface treated with a fluorinated hydrocarbon; and the thermoplastic resin composition comprises a polyhydroxyalkanoate (PHA) polymer. Typically, these diamond-like carbon layers refer to a carbonaceous material having carbon atoms as the majority element, with a substantial amount (e.g.. more than 80%) of such carbon atoms bonded in distorted tetrahedral coordination. Diamond-like carbon (DLC) can typically be formed by PVD processes, although CVD or other processes could be used such as vapor deposition processes. In particular embodiments, the DLC layer is formed by a plasma enhanced chemical vapor deposition (PECVD) process. Notably, a variety of other elements can be included in the DLC material as either impurities, or as dopants, including without limitation, hydrogen, sulfur, phosphorous, boron, nitrogen, silicon, tungsten. These layers may be amorphous diamond which often refers to a type of diamond-like carbon having carbon atoms as the majority element, with a majority (e.g., more than 50%) amount of such carbon atoms bonded in distorted tetrahedral coordination. In one aspect, the amount of carbon in the amorphous diamond can be at least 90%, with at least 20% of such carbon being bonded in distorted tetrahedral coordination. One or more layers (and particularly multilayer surface treatments involving fluorinated hydrocarbons) may also be amorphous carbon layers. The amorphous carbon layers generally do not have any crystal structure as found in diamond and graphite. Those layers having a diamond like carbon type structure are usually characterized by the presence of their sp ³ bonds as determined by conventional techniques, e.g. high resolution electron energy loss spectroscopy (HREELS).

[0023] Similarly, the degree of crystallinity of the PHA based substrate may correlate to the fraction of the polymer that exists in an orderly state, having a lattice structure. In certain embodiments, one phase of the multiphase 3-hydroxybutyrate copolymer is between 0 to 5% crystallinity, for example the degree of crystallinity in percent is 0 or is minimally observed to be less than 1%. In various embodiments, the degree of crystallinity of one phase of the multiphase 3-hydroxy butyrate copolymer polymer is below 3%, for example, below 2% or below 1% or ranges or numbers calculated between these percentages such as 2.5%. The degree of crystallinity calculated for the compositions of the invention is minimal and can be determined by various methods, for example, density calculations, x-ray and electron diffraction, differential scanning calorimetry', infrared absorption (FTIR), or Raman spectroscopy.

[0024] Thermoplastic Substrates

[0025] In general, the thermoplastic substrate of the present disclosure comprises a thermoplastic substrate comprising a polyhydroxyalkanoate which has been surface treated. The polyhy droxy alkanoate (or PHA or poly(hydroxy alkanoate)) of the poly meric composition used to form the substrate in the container may comprise homopolymers or copolymers, including terpolymers, or mixtures thereof.

[0026] In some embodiments, the polyhydroxyalkanoate comprises one or more monomer units having the structure: wherein R is independently at each occurrence alkyl (e.g.. C ₁ -C ₈ alkyl), x is an integer from 1- 10 (e.g., 1-8), and n is, independently at each occurrence, from 1-5000 (e.g., from 100- 1000). In some embodiments, the polyhydroxyalkanoate is a homopolymer. In some embodiments it is a co polymer (e.g., a polymer comprising having two monomeric units having the structure, a polymer comprising having three monomeric units having the structure). In various implementations, the polyhydroxyalkanoate may be a polymer (e.g., monomer, co-polymer) with monomeric units independently having the structure -|C(O)-R ₁ - C(O)-O-R ₂ -O]- wherein R ₁ is alkylene (e.g., C _2-8 alky lene ethylene, propylene, butylene, pentylene) or arylene (e.g., phenylene) and R ₂ is C _2-8 alkylene (e.g., ethylene, propylene, butylene, pentylene). In various implementations, the polyhydroxyalkanoate comprises one or more monomeric units selected from hydroxypropionate (e.g., 3-hydroxypropionate), hydroxybutyrate (e.g., 4-hydroxy butyrate), hydroxyvalerate (e.g., 5-hydroxyvalerate), hydroxy hexanoate (e.g., 3-hydroxyhexanoate) and optionally one or more monomeric units selected from ethylene succinate, butylene succinate, propylene succinate, ethylene adipate, butylene adipate, propylene adipate, butylene terephthalate, or propylene terephthalate. For example, the polyhydroxyalkanoate (used or produced alone or in a blend) may be poly(hydroxypropionate), poly(3-hydroxypropionate), poly(hydroxybutyrate). poly(4- hydroxybutyrate), poly(hydroxy valerate), poly(5-hydroxy valerate), poly(hydroxyhexanoate), poly(3-hydroxyhexanoate), poly(ethylene succinate), poly(butylene succinate), poly(propylene succinate), poly(ethylene adipate), poly(butylene adipate), poly(propylene adipate), poly(butylene terephthalate), poly(propylene terephthalate), poly(hydroxyoctanoate), poly(3-hydroxy octanoate), poly(hydroxypropionate-co-3-hydroxypropionate), poly(hydroxypropionate-co-hydroxybutyrate), poly(hydroxypropionate-co-4- hydroxybutyrate), poly(hydroxypropionate-co-hydroxy valerate), poly(hydroxypropionate-co- 5-hydroxy valerate), poly(hydroxypropionate-co-hydroxyhexanoate), poly(hydroxypropionate-co-3-hydroxyhexanoate), poly(hydroxypropionate-co-ethylene succinate), poly(hydroxypropionate-co-butylene succinate), poly(hydroxypropionate-co- propylene succinate), poly(hydroxypropionate-co-ethylene adipate), poly(hydroxypropionate- co-butylene adipate), poly(hydroxypropionate-co-propylene adipate), poly(hydroxypropionate-co-butylene terephthalate), poly(hydroxypropionate-co-propylene terephthalate), poly(3-hydroxypropionate-co-hydroxybutyrate), poly(3-hydroxypropionate- co-4-hydroxybutyrate), poly(3-hydroxypropionate-co-hydroxy valerate). poly(3- hydroxypropionate-co-5-hydroxyvalerate), poly(3-hydroxypropionate-co-hydroxyhexanoate), poly(3-hydroxypropionate-co-3-hydroxyhexanoate), poly(3-hydroxypropionate-co-ethylene succinate), poly(3-hydroxypropionate-co-butylene succinate), poly(3-hydroxypropionate-co- propylene succinate), poly(3-hydroxypropionate-co-ethylene adipate), poly(3- hydroxypropionate-co-butylene adipate). poly(3-hydroxypropionate-co-propylene adipate), poly(3-hydroxypropionate-co-butylene terephthalate), poly(3-hydroxypropionate-co- propylene terephthalate), poly(hydro\ybutyrate-co-4-hydro\ybutyrate). poly(hydroxybutyrate-co-hydroxy valerate), poly(hydroxybutyrate-co-5-hydroxy valerate), poly(hydroxybutyrate-co-hydroxyhexanoate), poly(hydroxybutyrate-co-3- hydroxyhexanoate), poly(hydroxybutyrate-co-ethylene succinate), poly(hydroxybutyrate-co- butylene succinate), poly(hydroxybutyrate-co-propylene succinate), poly(hydroxybutyrate-co- ethylene adipate), poly(hydro\ybutyrate-co-butylene adipate), poly(hydroxybutyrate-co- propylene adipate), poly(hydroxybutyrate-co-butylene terephthalate), poly(hydroxybutyrate- co-propylene terephthalate). poly(hydroxyvalerate-co-5-hydroxy valerate). poly(hydroxyvalerate-co-hydroxyhexanoate), poly(hydroxyvalerate-co-3-hydroxyhexanoate), poly(hydroxyvalerate-co-ethylene succinate). poly(hydroxyvalerate-co-butylene succinate), poly(hydroxyvalerate-co-propylene succinate), poly(hydroxyvalerate-co-ethylene adipate), poly(hydroxyvalerate-co-butylene adipate), poly(hydroxyvalerate-co-propylene adipate), poly(hydroxyvalerate-co-butylene terephthalate), poly(hydroxyvalerate-co-propylene terephthalate), poly(5-hydroxyvalerate-co-hydroxyhexanoate), poly(5-hydroxyvalerate-co-3- hydroxyhexanoate), poly(5-hydroxyvalerate-co-ethylene succinate), poly(5-hydroxyvalerate- co-butylene succinate), poly(5-hydroxyvalerate-co-propylene succinate), poly(5- hydroxyvalerate-co-ethylene adipate). poly(5-hydroxyvalerate-co-butylene adipate), poly(5- hydroxyvalerate-co-propylene adipate), poly(5-hydroxyvalerate-co-butylene terephthalate), poly(5-hydroxyvalerate-co-propylene terephthalate), poly(hydroxyhexanoate-co-3- hydroxyhexanoate), poly(hydroxyhexanoate-co-ethylene succinate), poly(hydroxyhexanoate- co-butylene succinate), poly(hydroxyhexanoate-co-propylene succinate), poly(hydroxyhexanoate-co-ethylene adipate). poly(hydroxyhexanoate-co-butylene adipate), poly(hydroxyhexanoate-co-propylene adipate). poly(hydroxyhexanoate-co-butylene terephthalate), poly(hydroxyhexanoate-co-propylene terephthalate), poly(3- hydroxyhexanoate-co-ethylene succinate), poly(3-hydroxyhexanoate-co-butylene succinate), poly(3-hydroxyhexanoate-co-propylene succinate), poly(3-hydroxyhexanoate-co-ethylene adipate), poly(3-hydroxyhexanoate-co-butylene adipate), poly(3-hydroxyhexanoate-co- propylene adipate), poly(3-hydroxyhexanoate-co-butylene terephthalate), poly(3- hydroxyhexanoate-co-propylene terephthalate), poly(ethylene succinate-co-butylene succinate), poly(ethylene succinate-co-propylene succinate), poly (ethylene succinate-co- ethylene adipate), poly(ethylene succinate-co-butylene adipate), poly(ethylene succinate-co- propylene adipate), poly(ethylene succinate-co-butylene terephthalate), poly(ethylene succinate-co-propylene terephthalate), poly(butylene succinate-co-propylene succinate), poly(butylene succinate-co-ethylene adipate), poly(butylene succinate-co-butylene adipate), poly(butylene succinate-co-propylene adipate), poly(butylene succinate-co-butylene terephthalate), poly(butylene succinate-co-propylene terephthalate), poly (propylene succinate- co-ethylene adipate), poly(propylene succinate-co-butylene adipate), poly(propylene succinate-co-propylene adipate), poly(propylene succinate-co-butylene terephthalate), poly(propylene succinate-co-propylene terephthalate), poly(ethylene adipate-co-butylene adipate), poly(ethylene adipate-co-propylene adipate), poly(ethylene adipate-co-butylene terephthalate), poly(ethylene adipate-co-propylene terephthalate), polyputylene adipate-co- propylene adipate), poly(butylene adipate-co-butylene terephthalate), poly(butylene adipate- co-propylene terephthalate), poly(propylene adipate-co-butylene terephthalate), poly(propylene adipate-co-propylene terephthalate), polyputylene terephthalate-co-propylene terephthalate), polypydroxypropionate-co-hydroxy octanoate), poly(3-hydroxypropionate-co- hydroxy octanoate), poly(hydroxybutyrate-co-hydroxy octanoate), poly(4-hydroxybutyrate-co- hydroxy octanoate), poly(hydroxyvalerate-co-hydroxy octanoate), poly (5 -hydroxy valerate-co- hydroxy octanoate), poly(hydroxyhexanoate-co-hydroxy octanoate), poly(3- hy droxyhexanoate-co-hydroxy octanoate), poly(ethylene succinate-co-hydroxyoctanoate), polyputylene succinate-co-hydroxyoctanoate), poly(propylene succinate-co- hydroxyoctanoate), polypthylene adipate-co-hydroxyoctanoate), polyputylene adipate-co- hydroxyoctanoate), poly(propylene adipate-co-hydroxyoctanoate). polyputylene terephthalate-co-hydroxy octanoate), poly(propylene terephthalate-co-hydroxyoctanoate), poly(hydroxypropionate-co-3-hydroxy octanoate), poly(3-hydroxypropionate-co-3- hydroxy octanoate), polypydroxybutyrate-co-3-hydroxyoctanoate), poly(4-hydroxybutyrate- co-3-hydroxy octanoate). polypydroxyvalerate-co-3-hydroxy octanoate). poly(5- hydroxyvalerate-co-3-hydroxyoctanoate), polypydroxyhexanoate-co-3-hydroxyoctanoate), poly(3-hydroxyhexanoate-co-3-hydroxyoctanoate), polypthylene succinate-co-3- hydroxy octanoate), polyputylene succinate-co-3-hydroxyoctanoate), poly(propylene succinate-co-3 -hydroxy octanoate), poly (ethylene adipate-co-3-hydroxyoctanoate), polyputylene adipate-co-3-hydroxyoctanoate), poly(propylene adipate-co-3- hydroxyoctanoate), polyputylene terephthalate-co-3-hydroxyoctanoate), poly (propylene terephthalate-co-3-hydroxy octanoate), or poly(hydroxyoctanoate-co-3-hydroxy octanoate).

[0027] In various implementations, the polyhydroxyalkanoate comprises one or more monomeric units selected from hydroxy propionate (e.g., 3-hydroxypropionate), hydroxybutyrate (e.g., 4-hydroxy butyrate), hydroxyvalerate (e.g., 5 -hydroxy valerate), hydroxy hexanoate (e.g., 3-hydroxyhexanoate) polypydroxypropionate), poly(3- hy droxypropionate), polypydroxybutyrate), poly (4-hydroxy butyrate), polypydroxyvalerate), poly(5-hydroxy valerate), polypydroxyhexanoate), poly(3-hydroxyhexanoate), polypydroxy octanoate), poly(3-hydroxy octanoate), poly(hydroxybutyrate-co-4- hy droxybutyrate), polypydroxybutyrate-co-hydroxy valerate), poly(hydroxybutyrate-co-5- hydroxy valerate), polypydroxybutyrate-co-hydroxyhexanoate), poly(hydroxybutyrate-co-3- hydroxyhexanoate), poly(5-hydroxyvalerate-co-hydroxyhexanoate), poly(5-hydroxyvalerate- co-3-hydroxyhexanoate), poly(hydroxyhexanoate-co-3-hydroxyhexanoate), poly(hydroxybutyrate-co-3-hydroxy octanoate), poly(4-hydroxybutyrate-co-3- hydroxy octanoate), poly(hydroxyvalerate-co-3-hydroxyoctanoate), poly(5-hydroxyvalerate- co-3-hydroxy octanoate), poly(hydroxyhexanoate-co-3-hydroxyoctanoate), poly(3- hydroxyhexanoate-co-3-hydroxy octanoate).

[0028] In certain embodiments, the polyhydroxyalkanoate (or PHA or poly(hydroxyalkanoate)), may be a copolymer made up of from 75 to 99.9 mole percent monomer residues of 3-hydroxy butyrate and from 0.1 to 25 mole percent monomer residues of a second 3-hydroxyalkanoate having from 5 to 12 carbon atoms. In other embodiment, the poly(hydroxyalkanoates) are preferably a terpolymer made up from 75 to 99.9 mole percent monomer residues of 3-hydroxybutyrate and from 0.1 to 25 mole percent monomer residues of 3-hydroxyhexanoate, and from 0.1 to 25 mole percent monomer residues of a third 3- hydroxyalkanoate having from 5 to 12 carbon atoms. In certain embodiments, the poly(hydroxyalkanoates) and the at least one biodegradable polymer are preferably reacted with each other in a transesterification. In some embodiments, the poly(hydroxyalkanoates) and the at least one biodegradable polymer are preferably reacted with each other in a reactive extrusion process. In certain embodiments, the poly(hydroxyalkanoates) of the polymeric composition preferably have a weight average molecular weight from 50.000 Daltons to 7.5 million Daltons, and more preferably have a weight average molecular weight from 300,000 Daltons to 3.0 million Daltons.

[0029] In some embodiments, the poly(hydroxyalkanoates) in the composition may be made up of a mixture of a first copolymer and a second copolymer. For example, the first copolymer includes from 90 to 99.9 mole percent monomer residues of 3-hydroxybutyrate and from 0.1 to 10 mole percent monomer residues of a second 3-hydroxyalkanoate having from 5 to 12 carbon atoms. The second copolymer includes at least 70 mole percent monomer residues of 3-hydroxybutyrate and monomer residues of the second 3-hydroxyalkanoate having from 5 to 12 carbon atoms in amount which at least 6 mole percent less than the amount of the second 3- hydroxyalkanoate in the first polymer.

[0030] In various aspects, the present disclosure relates to a biodegradable polymer composition (e.g., for use in forming a container without the surface as described herein), which may comprise a blend of a biodegradable polymer (e.g. , a biodegradable polymer having one or more monomeric units (e.g., monomer, co-polymer) independently having the structure — [C(O)—R ₁ — C(O)— O— R ₂ — O]— wherein R ₁ is C ₂ -C ₆ alkylene (e.g., ethylene, propylene, butylene, pentylene) or arylene (e.g.. phenylene) and R ₂ is C ₂ -C ₆ alkylene (e.g., ethylene. propylene, butylene, pentylene), a succinate copolymer, poly(ethylene succinate), poly(butylene succinate), poly(propylene succinate), poly(ethylene adipate). poly(butylene adipate), poly(propylene adipate), poly(butylene terephthalate), poly(propylene terephthalate), poly(ethylene succinate-co-adipate), poly(propylene succinate-co-adipate), polyputylene succinate-co-adipate), poly(propylene succinate-co-adipate), poly(ethylene succinate-co- terephthalate), poly(propylene succinate-co-terephthalate), polyputylene succinate-co- terephthalate), poly(propylene succinate-co-terephthalate), polyputylene adipate-co- terephthalate) (PBAT), poly(caprolactone), poly(lactic acid) (PLA), cellulose esters (such as cellulose acetate), polyvinyl alcohol (PVOH), thermoplastic starch, and mixtures thereof); and a polyhydroxyalkanoate such a 3-hydroxybutyrate (3HB) copolymer, wherein the 3HB copolymer may optionally contain at least one other monomer selected from the group consisting of 4-hydroxybutyrate, 5 -hydroxy valerate, 3 -hydroxy hexanoate and 3-hydroxy- octanoate, wherein the 3HB copolymer has at least 90% renewable carbon content as measured by ASTM D6866, and further wherein: the content of the 3HB copolymer in the polymer composition is from 1% to 40% by weight of the composition, and the biodegradation rate of the polymer composition is at least two times faster than the biodegradation rate of a reference composition containing no 3HB copolymer. In some embodiments, the biodegradable polymer composition is a bionanocomposite such as a composition comprising an inorganic material (e.g., clay, silicate) mixed with polymer. In some embodiments, the inorganic material is a layered silicate nanoclays such as montmorillonite (MMT) or kaolinite, zinc oxide (ZnO-NPs), titanium dioxide (TiO ₂ -NPs), and silver nanoparticles (Ag-NPs). Suitable bionanocomposite materials may be found in, for example, A. Youssef, et al., Carbohydrate Polymers 193.1 (2018): 19-27, which is hereby incorporated by reference in its entirety, and particularly in relation to inorganic nanomaterials for incorporation into polymer matrices for the formation of bionanocomposite.

[0031] In specific embodiments, the 3HB copolymer is poly-3-hydroxybutyrate-co-4- hydroxybutyrate. For example, the content of 4-hydroxybutyrate in the 3HB copolymer is 35% to 65% by weight of the 3HB copolymer, 45% to 55% by weight of the 3HB copolymer, or 50% to 60% by weight of the 3HB copolymer.

[0032] In certain embodiments, the 3-hydroxybutyrate copolymer has a molecular weight of 500,000 to 1,500,000 Daltons as measured by gel permeation chromatography, and a glass transition temperature as measured by differential scanning calorimetry of from -5 to -50 °C. In other example embodiments, the 3-hydroxybutyrate copolymer has a molecular weight of 550,000 to 750,000 Daltons as measured by gel permeation chromatography, and a glass transition temperature as measured by differential scanning calorimetry of -10 to -30 °C.

[0033] In example embodiments, the 3HB copolymer is poly-3-hydroxybutyrate-co-4- hydroxybutyrate, and the content of 3HB copolymer in the composition is 5-95% by weight of the composition.

[0034] In various example embodiments of the polymer composition defined herein, the 3HB copolymer is a poly-3-hydroxybutyrate-co-4-hydro\ybutyrate having the content of 4- hydroxybutyrate (4HB) from 30% to 50% by weight of the copolymer.

[0035] In example embodiments, the biodegradation rate of the polymer composition defined herein is at least 3, at least 5. at least 10, or at least 20 times faster than the biodegradation rate of a reference composition containing no 3HB copolymer.

[0036] In certain example embodiments, the polymer composition further comprises a third biodegradable polymer.

[0037] In example embodiments, the 3HB copolymer is poly-3-hydroxybutyrate-co-4- hydroxybutyrate, and wherein the content of 4-hydroxybutyrate in the 3HB copolymer is 30% to 65% by weight of the 3HB copolymer, 30% to 50% by weight of the 3HB copolymer, 30% to 45% by weight of the 3HB copolymer, 30% to 40% by weight of the 3HB copolymer. 45% to 65% by weight of the 3HB copolymer.

[0038] In example embodiments, the 3HB copolymer is poly-3-hydroxybutyrate-co-4- hydroxybutyrate. and wherein the 3HB copolymer comprises an amorphous rubber phase having no melting point. In example embodiments of the polymer composition defined herein, the 3HB copolymer is poly-3-hydroxybutyrate-co-4-hydro\ybutyrate. and wherein the content of the 3HB copolymer in the composition is 5% to 50% by weight of the composition, or 10% to 40% by weight of the composition.

[0039] The present disclosure includes a method of preparing polymer composition followed by subsequent surface treatment, the method comprising melt-blending a blend, the blend comprising: a biodegradable polymer (e.g., a biodegradable polymer having one or more monomeric units (e.g., monomer, co-polymer) independently having the structure -[C(O)-R ₁ - C(O)— O— R ₂ — O]— wherein R ₁ is C ₂ -C ₆ alkylene (e.g., ethylene, propylene, buty lene, pentylene) or arylene (e.g., phenylene) and R ₂ is C ₂ -C ₆ alkylene (e.g., ethylene, propylene, butylene, pentylene), a succinate copolymer, poly(ethylenelleynnee succinate), poly(butylene succinate). poly(propylene succinate), poly(ethylene adipate), poly(butylene adipate), poly(propylene adipate), poly(butylene terephthalate), poly(propylene terephthalate), poly(ethylene succinate- co-adipate), poly(propylene succinate-co-adipate), poly(butylene succinate-co-adipate), poly(propylene succinate-co-adipate), poly(ethylene succinate-co-terephthalate), poly(propylene succinate-co-terephthalate), poly(butylene succinate-co-terephthalate), poly(propylene succinate-co-terephthalate), poly(bu yt lenene adipate-co-terephalate), poly(caprolactone), poly(lactic acid), cellulose esters (such as cellulose acetate), nanocellulose, thermoplastic starch, and mixtures thereof); and a polyhydroxyalkanoate such a 3- hydroxy butyrate (3HB) copolymer, wherein the 3HB copolymer contains at least one other monomer selected from the group consisting of 4-hydroxybutyrate, 5-hydroxyvalerate. 3- hydroxyhexanoate and 3-hydroxy-octanoate, wherein the 3HB copolymer has at least 90% renewable carbon content as measured by ASTM D6866, and further wherein the content of the 3HB copolymer in the polymer composition is from 1% to 40% by weight of the composition, and the biodegradation rate of the polymer composition is at least two times faster than the biodegradation rate of a reference composition containing no 3HB copolymer. These polymers may be combined by, for example, injection molding, injection blow molding, injection stretch blow molding, extrusion blow molding, thermoforming combinations of these polymers. Furthermore, these compositions may be a nanocomposite. For example, the PHA polymer and/or blend may comprise one or more inorganic particulars (e.g., silica, clay) added during processing. In some embodiments, the inorganic material is a layered silicate nanoclays such as montmorillonite (MMT) or kaolinite, zinc oxide (ZnO-NPs), titanium dioxide (TiO2- NPs), and silver nanoparticles (Ag-NPs).

[0040] The biodegradable polymer blend thermoplastic composition may include compositions of polybutylene-succinate (PBS) or polybutylene-succinate-adipate (PBSA) and a bio based copolymer of 3-hydroxybutyrate (3HB) incorporating one or more comonomers selected from 4-hydroxybutyrate (4HB), 5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HH) and 3 -hydroxy octanoate (3HO) with the blend having a renewable carbon content of at least 1% by weight with improved properties such as tensile toughness, tear strength and faster biodegradation rates as compared to PBS or PBSA polymers that do not contain bio based 3- hydroxybutyrate copolymers.

[0041] In certain aspects, the present disclosure may pertain to biodegradable compositions comprising a blend of the polymer polybutylene-succinate and a bio based 3-hydroxybutyrate copolymer comprising one or more monomers selected from 4-hydroxybutyrate, 5- hydroxyvalerate, 3-hydroxyhexanoate and 3-hydroxyoctanoate which are incorporated into the copolymer at 25% to 85% weight percent, impart to the copolymer a glass transition temperature of -15 °C. to -50 °C., have a weight average molecular weight as measured by gel permeation chromatography (GPC) of at least 500,000 g/mole and provide a renewable carbon content of the biodegradable blend of at least 5% by weight of the composition. The blend may have a percent by weight 3 -hydroxy butyrate copolymer of 1-40%.

[0042] Pure poly-4-hydroxybutyrate (P4HB) homopolymer is a mostly amorphous, rubbery polymer at room temperature with a significantly lower glass transition temperature (T _g =-60 °C.) than that of many pure polymers. When 3-hydroxbutyrate is combined with 4- hydroxybulyrale in a copolymer, where the %4HB>25% by weight, the copolymer retains its rubbery properties (T _g = -15 °C. to -50 °C.). Similar rubbery' behavior is observed when 3- hydroxybutyrate is combined with other comonomers such 5 -hydroxy valerate, 3- hydroxyhexanoate or 3-hydroxyoctanoate. When the rubbery PHA copolymer is blended with other polymers, it readily forms a separate rubber phase which imparts a toughening effect on the overall polymer blend. Because of this property and its proven biodegradability' in various environments, it is a beneficial material for improving not only the toughness properties but also enhancing the overall biodegradability of the blend.

[0043] Physical properties and rheological properties of polymeric materials depend on the molecular weight and distribution of the polymer. “Molecular weight” is calculated in a number of different ways. Unless otherwise indicated, “molecular weight” refers to weight average molecular weight. For example, a number average molecular weight (Mn) represents the arithmetic mean of the distribution and is the sum of the products of the molecular weights of each fraction, multiplied by its mole fraction. The weight average molecular weight (M _w ) is the sum of the products of the molecular weight of each fraction, multiplied by its weight fraction. M _w is generally greater than or equal to M _n .

[0044] The weight average molecular weight of the 3-hydroxybutyrate copolymer used in the compositions of the invention ranges between 600,000 to 2,000,000 Daltons as measured by light scattering and GPC with polystyrene standards. In particular embodiments the molecular weight is 500,000 to 750,000 or 700,000 to 1,500,000 Daltons. [0063] Polyhydroxyalkanoates (PHAs) are biological polyesters synthesized by' a broad range of natural and genetically engineered bacteria as well as genetically engineered plant crops (Braunegg et al., (1998), J. Biotechnology 65: 127-161; Madison and Huisman. 1999, Microbiology and Molecular Biology Reviews, 63:21-53: Poirier, 2002. Progress in Lipid Research 41 : 131-155). These polymers are biodegradable thermoplastic materials, produced from renewable resources, with the potential for use in a broad range of industrial applications (Williams & Peoples, CHEMTECH 26:38-44 (1996)).

[0045] In certain embodiments, the starting PHA can be a copolymer (containing two or more different monomer units) in which the different monomers are randomly distributed in the polymer chain. Examples of PHA copolymers include poly 3 -hydroxy butyrate-co-3- hydroxypropionate (hereinafter referred to as PHB3HP). poly 3-hydroxybutyrate-co-4- hydroxybutyrate (hereinafter referred to as P3HB4HB). poly 3-hydroxy butyrate-co-4- hydroxyvalerate (hereinafter referred to as PHB4HV), poly 3-hydroxybutyrate-co-3- hydroxyvalerate (hereinafter referred to as PHB3HV), poly 3-hydro\ybutyrate-co-3- hy dr oxy hexanoate (hereinafter referred to as PHB3HH) and poly 3-hydroxybutyrate-co-5- hydroxyvalerate (hereinafter referred to as PHBSHV).

[0046] By selecting the monomer types and controlling the ratios of the monomer units in a given PHA copolymer, a wide range of matenal properties can be achieved. The PHA can have more than two different monomer units (e.g., three different monomer units, four different monomer units, five different monomer units, six different monomer units). An example of a PHA having 4 different monomer units would be PHB-co-3HH-co-3HO-co-3HD or PHB-co- 3-HO-co-3HD-co-3HDd (these types of PHA copolymers are hereinafter referred to as PHB3HX). Typically, where the PHB3HX has 3 or more monomer units the 3HB monomer is at least 70% by weight of the total monomers, preferably 85% by weight of the total monomers, most preferably greater than 90% by weight of the total monomers for example 92%, 93%, 94%, 95%. 96% by weight of the copolymer and the HX comprises one or more monomers selected from 3HH, 3HO, 3HD, 3HDd.

[0047] The 3 -hydroxy butyrate copolymers (P3HB3HP. P3HB4HB, P3HB3HV, P3HB4HV, P3HB5HV, P3HB3HHP, hereinafter referred to as PHB copolymers) containing 3- hydroxybutyrate and at least one other monomer are often employed as the PHA component in the present disclosure. Reference to these materials by these their material properties is as follows. Type 1 PHB copolymers typically have a glass transition temperature (T _g ) in the range of 6 °C. to -10 °C., and a melting temperature T _m of between 80 °C. to 180 °C. as measured by differential scanning calorimetry (DSC). Type 2 PHB copolymers typically have a T _g of -20 °C. to -50 °C. and T _m of 55 °C. to 90 °C. The PHA compositions of the present disclosure may include a mixture of a Type 1 and Type 2 PHBs. The Type 2 PHB copolymers may have two monomer units and have a majority of their monomer units being 3 -hydroxy butyrate monomer by weight in the copolymer, for example, greater than or equal to 45% 3-hydroxybutyrate monomer. Type 2 PHB copolymers have a 3HB content of between 95% and 55% by weight of the copolymer, for example 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50% and 45% by weight of the copolymer.

[0048] The PHA may include PHB4HB which is a Type 2 PHB copolymer where the 4HB content is in the range of 20% to 70% by weight of the copolymer and preferably in the range of 25% to 65% by weight of the copolymer for example: 25% 4HB; 30% 4HB; 35% 4HB; 40% 4HB; 45% 4HB; 50% 4HB; 55% 4HB; 60% 4HB; 65% 4HB by weight of the copolymer. The PHA may include PHBSHV which is a Type 2 PHB copolymer where the 5HV content is in the range of 20% to 70% by weight of the copolymer and preferably in the range of 25% to 65% by weight of the copolymer for example: 25% 5HV; 30% 5HV; 35% 5HV; 40% 5HV; 45% 5HV; 50% 5HV; 55% 5HV; 60% 5HV; 65% 5HV by weight of the copolymer. The PHA may include PHB3HH which is a Type 2 PHB copolymer where the 3HH is in the range of 35% to 95% by weight of the copolymer and preferably in the range of 40% to 80% by weight of the copolymer for example: 40% 3HH; 45% 3HH; 50% 3HH; 55% 3HH, 60% 3HH; 65% 3HH: 70% 3HH; 75% 3HH; 80% 3HH by weight of the copolymer. The PHA may include PHB3HX which is a Type 2 PHB copolymer where the 3HX content is comprised of 2 or more monomers selected from 3HH, 3HO, 3HD and 3HDd and the 3HX content is in the range of 30% to 95% by weight of the copolymer and preferably in the range of 35% to 90% by weight of the copoly mer for example: 35% 3HX; 40% 3HX; 45% 3HX; 50% 3HX; 55% 3HX 60% 3HX: 65% 3HX; 70% 3HX; 75% 3HX; 80% 3HX; 85% 3HX; 90% 3HX by weight of the copolymer.

[0049] The PHAs for use in the methods, compositions and containers described in this invention may be selected from Type 2 PHB4HB copolymers having a %4HB content of 40- 65%. Useful processes for producing the PHB copolymer PHB3HH have been described (Lee et al., 2000, Biotechnology and Bioengineering 67:240-244; Park et al., 2001, Biomacromolecules 2:248-254). Processes for producing the PHB copolymers PHB3HX have been described by Matsusaki et al. (Biomacromolecules 2000, 1 :17-22) each of which are hereby incorporated by reference in their entirety, and particularly in relation to processes for producing PHA materials.

[0050] Forming the container substrate may occur through the combination of various biodegradable and/or compostable compositions as described herein. In various implementations, the container is made from a first polymeric material (or thermoplastic resin composition) and an additional material such as a nucleating agent and/or a filler, which are mixed to form a first mixture. This first polymeric material may have a degree of crystallinity of greater than 30%. The first mixture and a second compostable polymeric material may then be mixed to form a second mixture. The second compostable polymeric material may have a degree of crystallinity of from 15% to 45%. The second mixture may be melted and extruded to form an extrudate. The extrudate may be cooled to form the biodegradable substrate for subsequent surface treatment. The final material may have a degree of crystallinity of 5% to 30%.

[0051] In certain implementations, a polymer having at least 20 mole percent of hydroxyalkanoate repeat units is crystalized by admixing the polymer and a nucleating agent having a crystal structure similar to the PHA crystal structure. An exemplary nucleating is pentaerythritol, mixed at a first temperature, which may be from 5 °C. to 15 °C. above the melting point of the polymer; and cooling the polymer to a second temperature, which may be in a temperature range between the glass transition temperature and the melting point of the polymer. In some embodiments, the first temperature is from 100 °C. to 190 °C. In various implementations, the second temperature is from 50 °C. to 90 °C (e.g., from 8 to 20 seconds).

[0052] PHAs can be extracted from sources including, but not limited to, single-celled organisms, such as bacteria or fungi, and higher organisms, such as plants. These sources, together with the PHAs that are biosynthesized, are generally referred to as biomass. While biomass can comprise wild-type organisms, they also can comprise genetically engineered species specifically designed for the production of particular PHAs of interest to the grower.

[0053] In general, a PHA may be formed by enzymatic polymerization of one or more monomer units inside a living cell. Over 100 different types of monomers have been incorporated into the PHA polymers (Steinbuchel and Valentin, 1995, FEMS Microbiol. Lett. 128:219-228. Examples of monomer units incorporated in PHAs for this invention include 2- hydroxybutyrate, glycolic acid, 3-hydroxybutyrate (hereinafter referred to as 3HB), 3- hydroxypropionate (hereinafter referred to as 3HP), 3-hydroxyval erate (hereinafter referred to as 3HV), 3-hydroxyhexanoate (hereinafter referred to as 3HH), 3-hydroxyheptanoate (hereinafter referred to as 3HH), 3-hydroxyoctanoate (hereinafter referred to as 3HO), 3- hydroxynonanoate (hereinafter referred to as 3HN), 3-hydroxy decanoate (hereinafter referred to as 3HD), 3-hydroxydodecanoate (hereinafter referred to as 3HDd), 4-hydroxybutyrate (hereinafter referred to as 4HB), 4-hydroxyvalerate (hereinafter referred to as 4HV). 5- hydroxyvalerate (hereinafter referred to as 5HV). and 6-hydroxyhexanoate (hereinafter referred to as 6HH). 3 -hydroxy acid monomers incorporated into PH As are the (D) or (R) 3- hydroxyacid isomer with the exception of 3HP which does not have a chiral center. For compositions included herein, the PHA composition may not include poly(lactic acid). In some embodiments, the compositions do include poly(lactic acid).

[0054] In certain example embodiments, the 3HB copolymer is prepared by culturing a recombinant host with a renewable feedstock to produce a bio based poly-3-hydroxybutyrate- co-4-hydroxybutyrate biomass. The source of the renewable feedstock can be selected from glucose, fructose, sucrose, arabinose, maltose, lactose, xylose, glycerol, ethanol, methanol, fatty acids, vegetable oils, sargassum, and biomass derived synthesis gas or a combination thereof. Useful microbial strains for producing PHAs, include Alcaligenes eutrophus (renamed as Ralstonia eutropha), Alcaligenes latus, or species from the genus Azotobacter, Aeromonas , Comamonas. Pseudomonads, and genetically engineered organisms including genetically engineered microbes such as those engineered from the genus Pseudomonas, Ralstonia, and Escherichia (e.g., Escherichia coli). Bacteria that are useful to produce PHAs include any genetically engineered bacteria that can produce PHAs, as well as bacteria that naturally produce PHAs. Examples of such bacteria include those disclosed in NOVEL BIODEGRADABLE MICROBIAL POLYMERS, E.A. Dawes, ed., NATO ASI Series, Series E: Applied Sciences-Vol. 186, Kluwer Academic Publishers (1990); U.S. Pat. No. 5,292,860 to Kanegafuchi Kagaku Kogyo Kabushiki Kaisha, issued Mar. 8, 1994, and U.S. Pat. No. 11,225.676 which are hereby incorporated by reference in its entirety and particularly in relation to PHA production. In one embodiment, the bacterium is Alcaligenes eutrophus, Escherichia coli, Ralstonia eutropha, Protonemas extorquens, Methylobacterium exiorquens, Pseudornanas putida, Pseudomonas resinovorans , Pseudomonas oleovorans. Pseudomonas aeruginosa, Pseudomonas syringae, Pseudomonas fluorescens, Sphaerotiliis natans, Agrobacterium, Rhodobacter sphaeroides, Actinobacillus, or Azotobacter vinelandii.

[0055] Plants useful as biomass organisms include any genetically engineered plant designed to produce PHAs. Such plants include agricultural crops such as cereal grains, oilseeds and tuber plants; other plants include avocado, barley, beet, broad bean, buckwheat, carrot, coconut, copra, com (maize), cottonseed, gourd, lentil, lima bean, millet, inung bean, oat, palm, pea, peanut, potato, pumpkin, rapeseed (e.g., canola), rice, sorghum, soybean, sugatheet, sugar cane, sunflower, sweet potato, tobacco, wheat, and yam. Such genetically altered fruit-bearing plants useful in the process of the present disclosure include, but are not limited to, apple, apricot, banana, cantaloupe, cherry, grape, kumquat, tangerine, tomato, and watermelon. The plants can be genetically engineered to produce PHAs pursuant to the methods disclosed in Poirier, Y., D. E. Dennis, K. Klomparens and C. Somerville, "Polyhydroxybutyrate. a biodegradable thermoplastic, produced in transgenic plants” Science 256 (1992): 520-523; and/or U.S. Pat. No. 5,650,555, which are each incorporated by reference in their entirety. In one embodiment, the plants are soybean, potato, com, or coconut plants that are genetically engineered to produce PHAs; in another embodiment, the plant is soybean. In particular embodiments, the plant is a palm tree.

[0056] During the extraction, the biomass may be combined with a solvent. For example, details regarding the conditions for extracting PHAs from a biomass are available in U.S. Pat. No. 5,942,597, U.S. Pat. No. 5,918,747, U.S. Pat. No. 5,899,339, U.S. Pat. No. 5,849,854, and U.S. Pat. No. 5,821,299. which are hereby incorporated by reference in their entirety. PHAs obtained or extracted by any available method may be crystallized using the crystallization methods as disclosed herein.

[0057] In particular, mixing filler together with pentaerythntol as the nucleating agent, the crystallization speed of polyhydroxyalkanoate may be significantly improved, the bloom of the nucleating agent and the like can be suppressed, the surface smoothness of the obtained molded body can be improved, and the mold transferability can be improved by the improvement of the surface smoothness, which has led to the completion of the present invention. The container may be made of this material, or this material may be combined with another material having a different amount (e.g., less) filler and/or nucleating agent (e.g., pentaerythritol) to prepare surfaces appropriate for surface treatment and container (e.g., bottle) production.

Additional Components

[0058] The material properties of the PHA substrate may be altered by incorporating a nucleating agent into one of more thermoplastic compositions used to create the substrate. The nucleating agent may be selected from the group consisting of erythritols, pentaerythritol, dipentaerythritols, artificial sweeteners, stearates, polysaccharides, sorbitols, mannitols, inositols, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, thymine, cyanuric acid, cytosine, adenine, uracil, guanine, boron nitride and mixtures thereof. In some embodiments, the polymeric composition includes a plasticizer (e.g.. less than (or from 0.1% to) 15% plasticizer by weight. This plasticizer may be selected from the group consisting of sebacates, citrates, fatty 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 from 200-10,000 g/mol, poly(ethylene 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, polymeric plasticizers, poly(hydroxy alkanoates) copolymers comprising at least 18 mole percent monomer residues of hydroxy alkanoates other than hydroxybutyrate, and mixtures thereof. In certain implementations, the polymeric composition includes from 5 weight percent to 15 weight percent of the plasticizer. The polymeric composition may also include up to (or from 0.1% to) 50 weight percent of a filler. This filler may be selected from the group consisting of calcium carbonate, talc, nano clays, nanocellulose, hemp fibers, kaolin, carbon black, wollastonite, glass fibers, carbon fibers, graphite fibers, mica, silica, dolomite, barium sulfate, magnetite, halloysite, zinc oxide, titanium dioxide, montmorillonite, feldspar, asbestos, boron, steel, carbon nanotubes, cellulose fibers, flax, cotton, starch, polysaccharides, aluminum hydroxide, magnesium hydroxide, modified starches, chitins and chitosans, alginates, gluten, zein, casein, collagen, gelatin, polysaccharides, guar gum, xanthan gum, succinoglycan. natural rubbers; rosinic acid, lignins, natural fibers, jute, kenaf, hemp, ground nut shells, wood flour, and mixtures thereof, and mixtures thereof. In some embodiments, the polymeric composition includes from 5 weight percent to 40 weight percent of the filler. According to some embodiments, the polymeric composition preferably also includes up to 20 weight percent of an impact modifier. This impact modifier may be selected from the group consisting of acrylic-based resins and emulsions, isosorbide derivatives, natural rubbers, aliphatic polyesters, or mixtures thereof. In various implementations, the polymeric composition may include from 5 weight percent to 15 weight percent of the impact modifier. In certain aspects, further additives may also be included in the polymeric composition. In some instances, the composition also includes up to 50 weight percent of one or more additives selected from the group consisting of poly(vinyl alcohols), poly(vinyl acetate), poly(vinyl laurate), poly(ethylene vinyl acetate), poly(glycolic acid), furandicarboxylic acid-based polyesters, cellulose, nanocellulose, glucans, and mixtures thereof. However, these materials may inhibit the biodegradability of the films. The use of these materials may be limited such that the biodegradable of the resultant container would be considered biodegradable, for example, as measured be the various ASTM protocols described herein.

[0059] An optional nucleating agent may be added to the compositions of the invention to aid in its crystallization. Nucleating agents for various polymers are simple substances, metal compounds including composite oxides, for example, carbon black, calcium carbonate, synthesized silicic acid and salts, silica, zinc white, clay, kaolin, basic magnesium carbonate, mica, talc, quartz powder, diatomite, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, metal salts of organophosphates, and boron nitride; low-molecular organic compounds having a metal carboxylate group, for example, metal salts of such as octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, benzoic acid, p-tert-butylbenzoic acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid, and isophthalic acid monomethyl ester; high-molecular organic compounds having a metal carboxylate group, for example, metal salts of such as: carboxyl-group-containing polyethylene obtained by oxidation of polyethylene; carboxyl-group-containmg polypropylene obtained by oxidation of polypropylene; copolymers of olefins, such as ethylene, propylene and butene-1, with acrylic or methacrylic acid; copolymers of styrene with acrylic or methacrylic acid; copolymers of olefins with maleic anhydride; and copolymers of styrene with maleic anhydride; high-molecular organic compounds, for example: alpha-olefins branched at their 3-position carbon atom and having no fewer than 5 carbon atoms, such as 3,3 dimethylbutene-1,3-methylbutene-1,3- methylpentene-1,3-methylhexene-1, and 3,5,5-trimethylhexene-1; polymers of vinylcycloalkanes such as vinylcyclopentane, vinylcyclohexane, and vinylnorbomane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; poly(glycolic acid); cellulose; cellulose esters; and cellulose ethers; phosphoric or phosphorous acid and its metal salts, such as diphenyl phosphate, diphenyl phosphite, metal salts of bis(4-tert- butylphenyl) phosphate, and methylene bis-(2,4-tert-butylphenyl)phosphate; sorbitol derivatives such as bis(p-methylbenzylidene) sorbitol and bis(p-ethylbenzylidene) sorbitol; and thioglycolic anhydride, p-toluenesulfonic acid and its metal salts. The above nucleating agents may be used either alone or in combinations with each other. In particular embodiments, the nucleating agent is cyanuric acid. In certain embodiments, the nucleating agent can also be another polymer (e.g., polymeric nucleating agents such as PHB).

[0060] In certain embodiments, a polymer composition defined herein can comprise a nucleating agent selected from one or more of carbon black, cyanuric acid, an erythritol such as pentaerythritol, uracil, thymine, mica talc, silica, boron nitride, barium nitride, clay, calcium carbonate, synthesized silicic acid and salts, metal salts of organophosphates, and kaolin.

[0061] Some nucleating agents may offer process temperature flexibility. For example, nucleating agents useful for polymer-process temperatures near or above 180 °C, which might compromise the nucleating efficiency of other nucleating agents. Process temperatures near 180 °C. are useful, for example, for the crystallization of PHAs, which can have a melting temperature of around 170 °C.

[0062] The nucleating agent can be contacted with the polymer by standard melt mixing methods including melt blending, solution blending, dry mixing, extrusion mixing, injection molding, pelletizing, blow molding, extrusion sheet forming, inflation forming, contour extrusion forming, vacuum pressure forming, blown film processing, extrusion coating, fiber spinning, or any combination thereof. In one embodiment, mixing the nucleating agent with the polymer will disperse the nucleating agent throughout the polymer material.

[0063] The nucleating agent may be selected (or milled to desirable size from a larger particle size) such that the particle size of the nucleating agent is similar in size to that of the polymer. Without being limited by theory, it is believed that where the particle size of the nucleating agent and polymer are similar, that better dispersion and corresponding better crystallization of the polymer results. An example of milling technology for this procedure is a pin mill. In some embodiments, the PHA polymer is contacted with a nucleating agent that has a similar cry stal structure to PHA or allotropic character at a first temperature, which is from 5 °C. to 15 °C. above the melting point of the polymer. At a temperature that is 5 °C. to 15 °C. above the melting point of the polymer, the majority of the polymer is likely molten. Mixing in this temperature window may allow uniform crystallization throughout the polymer material. In some embodiments, the polymer has a melting point of from 80 °C. to 160 °C. In another embodiment, the polymer has a melting point of from 100 °C. to 150 °C.

[0064] The present disclosure may include substrates having at least 20 mole percent of hydroxyalkanoate repeat units, comprising admixing the polymer and a compound with a crystal structure similar to the PHA crystal structure, such as pentaerythritol, providing heterogeneous nucleation sites. The present disclosure also provides a composition comprising a polymer having at least 20 mol percent of hydroxyalkanoate repeat units, and a compound that has allotropic character, such as sulfur and selenium. In some aspects, the polymeric composition may include at least a polymer and a nucleating agent, in an amount from 0.01% to 20% by weight of the polymer. The polymer including at least 20 mole percent hydroxyalkanoate repeat units. The nucleating agent is selected from the group consisting of (1) compounds having an orthorhombic cry stal structure, (2) compounds having a hexagonal crystal structure, (3) compounds having a tetragonal crystal structure, (4) allotropic elements having at least one crystalline form which is orthorhombic, hexagonal, or tetragonal, (5) polymorphic compounds having at least one crystalline form which is orthorhombic, hexagonal. or tetragonal, and (6) mixtures thereof. In certain embodiments, the may be selected from the group consisting of pentaerythritol, dipentaerythritol, anatase, wulfenite, aragonite, sulfur, selenium, phosphorous, benzamide, and mixtures thereof. For example, the nucleating agent may be pentaerythritol.

[0065] In certain embodiments, the nucleating agent is present in an amount from 0.5% to 5% by weight of the polymer. For example, the container may be formed from a thermoplastic resin composition comprising (or consisting of) an aliphatic polyester resin composition including polyhydroxyalkanoate (A), pentaerythritol (B), and filler (C). In particular embodiments, the amount of filler (C) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyhydroxy alkanoate (A). In some embodiments, the amount of pentaerythritol (B) is 0.05 to 20 parts by weight with respect to 100 parts by weight of the polyhydroxyalkanoate (A). In specific embodiments, the filler (C) is an inorganic filler. The inorganic filler may include at least one inorganic filler selected from silicate, carbonate, sulfate, phosphate, oxide, hy droxide, nitride, and carbon black. In some embodiments the filler comprises an organic filler selected from a woody material and an organic fiber. In some embodiments, the inorganic material is a layered silicate nanoclays such as montmorillonite (MMT) or kaolinite, zinc oxide (ZnO-NPs), titanium dioxide (TiO2-NPs), and silver nanoparticles (Ag-NPs). In specific embodiments, the aliphatic polyester resin composition further includes a plasticizer (D). The amount of plasticizer (D) may be from 1 to 30 parts by weight with respect to 100 parts by weight of the polyhydroxyalkanoate (A). The plasticizer (D) may be a modified glycerin-based compound. For example, the modified glycerin-based compound may include at least one selected from glycerol diacetate monolaurate, glycerol diacetate monooleate, glycerol monoacetate monostearate, glycerol diacetate monocaprylate, glycerol diacetate monodecanoate, and glycerol triacetate.

[0066] Each composition ratio as a repeating unit in the PHA (A) copolymer resin can be characterized by gas chromatography, for example, in the following manner. Two milliliters of a sulfuric acid/methanol mixed solution (15/85 (weight ratio)) and 2 mL of chloroform are added to 20 mg of dried PHA, and the mixture is hermetically sealed and heated at 100 °C. for 140 minutes to obtain a methyl ester as a PHA degradation product. After cooled, the methyl ester is neutralized by adding 1.5 g of sodium hydrogen carbonate little by little, and the mixture may be allowed to stand until the generation of carbon dioxide is stopped. Four milliliters of diisopropyl ether is added to and well mixed with the mixture, and then the monomer unit composition of the PHA degradation product in the supernatant is analyzed by capillary gas chromatography. In this way. each composition ratio in the copolymer resin may be determined.

[0067] In certain embodiments, the compositions include one or more surfactants. Surfactants are generally used to de-dust, lubricate, reduce surface tension, and/or densify. Examples of surfactants include, but are not limited to mineral oil, castor oil, and soybean oil. One mineral oil surfactant is Drakeol 34, available from Penreco (Dickinson, Tex., USA). Maxsperse W-6000 and W-3000 solid surfactants are available from Chemax Polymer Additives (Piedmont, S.C., USA). Non-ionic surfactants with HLB values ranging from 2 to 16 can be used, examples being TWEEN-20, TWEEN-65, Span-40 and Span 85.

[0068] Anionic surfactants include: aliphatic carboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid; fatty acid soaps such as sodium salts or potassium salts of the above aliphatic carboxylic acids; N-acyl-N-methylglycine salts, N-acyl- N-methyl-beta-alanme salts. N-acylglutamic acid salts, polyoxyethylene alkyl ether carboxylic acid salts, acylated peptides, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, naphthalenesulfonic acid salt-formalin polycondensation products, melaminesulfonic acid salt-formalin polycondensation products, dialkylsulfosuccinic acid ester salts, alky l sulfosuccinate disalts, polyoxyethylene alkylsulfosuccinic acid disalts, alkylsulfoacetic acid salts, (alpha-olefmsulfonic acid salts, N-acylmethyltaurine salts, sodium dimethyl 5- sulfoisophthalate, sulfated oil, higher alcohol sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid salts, secondary higher alcohol ethoxy sulfates, polyoxyethylene alkyl phenyl ether sulfuric acid salts, monogly sulfate, sulfuric acid ester salts of fatty acid alkylolamides, polyoxyethylene alkyl ether phosphoric acid salts, polyoxyethylene alkyl phenyl ether phosphoric acid salts, alkyl phosphoric acid salts, sodium alkylamine oxide bistridecylsulfosuccinates, sodium dioctylsulfosuccinate, sodium dihexylsulfosuccinate, sodium dicyclohexylsulfosuccinate, sodium diamylsulfosuccinate. sodium diisobutylsulfosuccinate, alkylamine guanidine polyoxyethanol, disodium sulfosuccinate ethoxylated alcohol half esters, disodium sulfosuccinate ethoxylated nonylphenol half esters, disodium isodecylsulfosuccinate, disodium N-octadecylsulfosuccinamide, tetrasodium N-(1 ,2- dicarboxyethyl)-N-octadecylsulfosuccinamide, disodium mono- or didodecyldiphenyl oxide disulfonates, sodium diisopropylnaphthalenesulfonate, and neutralized condensed products from sodium naphthalenesulfonate. [0069] One or more lubricants can also be added to the compositions and methods of the invention. Lubricants are normally used to reduce sticking to hot processing metal surfaces and can include polyethylene, paraffin oils, and paraffin waxes in combination with metal stearates. Other lubricants include stearic acid, amide waxes, ester waxes, metal carboxylates, and carboxylic acids. Lubricants are normally added to polymers in the range of 0.1 percent to 1 percent by weight, generally from 0.7 percent to 0.8 percent by weight of the compound. Solid lubricants are warmed and melted before or during processing of the blend.

[0070] In some embodiments, the thermoplastic resin can optionally include one or more oxygen barrier materials. An oxygen barrier material can be a component or material configured to improve (that is, decrease) an oxygen transmission rate (OTR) of the container. By decreasing the OTR of a food packaging container, the one or more oxygen barrier materials can increase the ability of the container to maintain food freshness, shelf life, or longevity. An oxygen barrier material can be compostable or non-compostable. Some non-limiting examples of a suitable compostable oxygen barrier material include ethylene vinyl alcohol (EVOH), poly glutamic acid, polyvinyl alcohol (PVOH), poly (butylene adipate co-terephthalate) (PBAT), and poly glycolic acid. In some embodiments, the oxygen barrier material includes an extrusion grade vinyl alcohol. In some embodiments, the a biodegradable polymer (e.g., a biodegradable polymer having one or more monomeric units (e.g., monomer, co-polymer) independently having the structure -[C(O)-R ₁ -C(O)-O-R ₂ -O]- wherein R ₁ is C ₂ -C ₆ alkylene (e.g., ethylene, propylene, butylene, pentylene) or arylene (e.g., phenylene) and R ₂ is C ₂ -C ₆ alkylene (e.g., ethylene, propylene, butylene, pentylene), a succinate copolymer, poly(ethylene succinate), poly(butylene succinate), poly(propylene succinate), poly(ethylene adipate), poly(butylene adipate), poly (propylene adipate), polyputylene terephthalate), poly(propylene terephthalate), poly(ethylene succinate-co-adipate), poly(propylene succinate-co-adipate), polyputylene succinate-co-adipate), poly(propylene succinate-co-adipate). poly(ethylene succinate-co-terephthalate), poly(propylene succinate-co-terephthalate), polyputylene succinate-co-terephthalate), poly(propylene succinate-co-terephthalate), polyputylene adipate-co- terephthalate) (PBAT), poly (caprolactone), poly(lactic acid), cellulose esters (such as cellulose acetate), polyvinyl alcohol (PVOH). thermoplastic starch, and mixtures thereof) In some embodiments, the oxygen barrier material includes an alcohol copolymer, alcohol, and acetate. For example, the oxygen barrier material can include butenediol-vinyl-alcohol copolymer, methanol, and methyl acetate (such as G polymer OKS-8049P). In some embodiments, the thermoplastic resin includes 1% to 50% by weight of one or more oxygen barrier materials, which may include one or more compostable oxygen barrier materials. In some embodiments, the thermoplastic resin includes 2.5% to 32.5% of one or more oxygen barrier materials, which may include one or more compostable oxygen barrier materials. In some embodiments, the thermoplastic resin includes 5% to 15% of one or more oxygen barrier materials, which may include one or more compostable oxygen barrier materials. In some embodiments, each of the one or more oxygen barrier materials within the thermoplastic resin are compostable oxygen barrier material

[0071] Surface Treatment

[0072] The present disclosure involves the surface treatment of polhydroxyalkanoates such as PHBH in order to make surface suitable for various containers such as food and beverage containers (e.g., containers such as bottles which may contain an alcoholic beverage including beer, hard seltzer, beverage comprising spirits such as a ready to drink cocktail; or nonalcoholic beverages such as carbonated soft drinks, juices, or water; or combinations thereol) and consumer packaged goods (e.g. personal care products, beauty products, tobacco, cannabis, oils comprising one or more cannabinoids).

[0073] Surface treatment may occur through a variety of methodologies such as physical vapor deposition (PVD), chemical-vapor deposition (CVD), plasma based surface treatments such as plasma vapor deposition or plasma-enhanced chemical vapor deposition (PECVD). Examples of physical vapor deposition method include a vacuum vapor deposition method, an ion plating method and a sputtenng method, and examples of the chemical vapor deposition method include plasma CVD utilizing plasma, thermal CVD, photo CVD, and catalytic chemical vapor deposition (Cat-CVD), in which a raw material gas is subjected to catalytic decomposition with a heated catalyst. The one or more layers from the surface treatment may be formed by a deposition method involving a vacuum. In these embodiments, the surface of the container to be treated may be exposed to a vacuum by the removal of air from the space nearly defined by the surface. For example, in embodiments, where the container is a bottle, the vacuum may be created on the interior of the bottle where liquid or product ty pically is kept.

[0074] Emptying of the air initially may result in a pressure prior to treatment of. for example, 0.001 mbar to 1 mbar such as less than 0. 1 mbar. Next, a flow of gas or gaseous mixture may be introduced into the vacuum. This introduction should increase the pressure inside the container, such as to values between 0.002 mbar and 10 mbar. In some treatment methods, electrical or electromagnetic energy may be applied to the introduced gas, which, in plasma based deposition techniques, brings the gas or gaseous mixture to a plasma state if certain conditions of pressure and power density of the energy are met.

[0075] For example, the energies used for the creation of the plasma may be derived from a direct current voltage (DC), from a high frequency (HF), from a radiofrequency (13.46 MHz, 13.56 MHz, 2.45 GHz, and their harmonics for example) or from microwaves (915 MHz, 2,450 MHz). In some embodiments, the space densities of power that are implemented are from 0.01 W/cm ³ to 10 W/cm ³ (e.g., from 0. 1 W/cm ³ to 3 W/cm ³ , from 0.01 W/cm ³ to 1 W/cm ³ ). Applied power may be, for example, from 400-1500 W with a gas pressure of from 0.5-20 mtorr. The frequencies that may be used are those, industrial, of 40 kHz, 13.56 MHz and 2,450 MHz. These energies and frequencies may be attenuated for deposition of the desired layer material. For example, depending on the type of plasma (e.g., radiofrequency as compared to microwave as shown in Averkin, et al., Russian Microelectronics 32.5 (2003): 292-300, which is hereby incorporated by reference in its entirety and particularly in relation to plasma generation schemes and comparisons) and/or plasma energy and/or frequency applied to an organic source gas such as acetylene, the deposited material may be amorphous or have a diamond like structure. In some embodiments, a precursor gas (e.g., noble gas (e.g., He, Ne. Ar) and/or oxygen (O ₂ ) and/or nitrogen (N ₂ ) and/or from a C ₁ -C ₅ unsubstituted alkane and/or a C ₂ -C ₅ unsubstituted alkene (e.g., acetylene) and/or the fluorinated hydrocarbon, or combinations thereof) may be transformed into a plasma state by a combination of excitations such as a main (or first) excitation involving electromagnetic radiation (e.g.. micro wave radiation such as microwave radiation having a frequency from 300 MHz to 3000 MHz, from 915 MHz to 2450 MHz) and a second excitation involving an electrical discharge. For example, the electrical discharge (e.g.. of the second excitation) may be an alternating electrical discharge which may have a frequency of from 1 KHz to 15 MHz (e.g., from 10 KHz to 200 KHz). In some embodiments, the first and second excitations overlap (or occur simultaneously). Suitable plasma coating processes for use with the present disclosure may be found in WO 2020/148487, which is hereby incorporated by reference in its entirety and particularly in relation to the combination of excitations related to plasma generation and devices and coatings therefor. The plasma source may be. for example, an inductively coupled plasma (ICP) source, RF helicon source, or microwave source (e.g., electron cyclotron resonance (ECR), surface waves). [0076] Typically, the plasma state then has the effect of bringing said gas or gaseous mixture to a state involving ionization of its contents which result in a variety of excitations and decompositions of the plasma source gas as it is deposited onto the surface. Furthermore, the high energy plasma state may induce alteration of the surface being treated. The particles derived from these excitation and decomposition mechanisms may then either recombine among themselves to result in more-or-less unstable particles which may then condense on the polymer surface which is immersed in this plasma mixture, or likewise condense on the polymer PHA surface. How and if decomposition occurs is highly dependent on the structure of the surface being altered. The present invention is partially premised on the use of polyhydroxy alkanoates such as PHBH as a plasma surface and that such surface treatments are able to produce barrier properties suitable for containers, and, in particular, food or beverage containers such as bottles (e.g. containers such as bottles which may contain an alcoholic beverage including beer, hard seltzer, beverage comprising spirits such as a ready to drink cocktail; or non-alcoholic beverages such as carbonated soft drinks, juices, or water; or combinations thereof), and consumer packaged goods containers such as those used in personal care, healthcare (e.g., pharmaceutical), beauty, personal care, household (e.g., cleaning), tobacco, or cannabis products, while maintaining their integrity for use and biodegradability.

[0077] Deposition parameters may be altered in order to affect various properties such as barrier attenuation, material state (e.g, amorphous, diamond-like, or amorphous diamond), and layer thickness. For example, layer thickness is often associated with the time of application of the plasma phase. Therefore, after a sufficient plasma phase time which may be, for example, for less than (or from 1 s to) 60 s (e.g., less than 45 s, less than 30 s, less than 20 s, from 5 s to 60 s, from 5 s to 45 s, from 5 to 30 s from 10 s to 20 s). This time may be measured as the time between plasma generation (e.g., application of electromagnetic energy of the source gas) and plasmas end (e.g., application of electromagnetic energy to a source gas is stopped).

[0078] The flow of the gas or gaseous mixture may also be stopped, and then the chamber is brought back to atmospheric pressure or a subsequent plasma treatment may occur (e g., by using another source gas). In some embodiments, before bringing the chamber back to atmospheric pressure, a second deposit cycle is carried out by reproduction according to the cycle described previously from a new gas or gaseous mixture. In another embodiments, several cycles are carried out with different gases or gaseous mixtures thus making it possible to coat the polymer surface with as many layers. In various implementations, the first cycle may be a step for preparation of the polymer surface which cleans and prepares the polyhydroxyalkanoate surface such as, for example, by application of a noble gas or noble gas and hydrogen mixture. For example, the preparation of the polymer surface is conducted by using, preferentially, a plasma of argon or argon+hydrogen (H ₂ ) mixture.

[0079] In various implementations, the plasma source gas may comprise carbon dioxide which may increase the number of oxidized sites on the polymer PHA surface favorable for obtaining of better performance characteristics such as oxygen barrier deposits. The CO ₂ partial pressures for these source gas mixtures may be, for example, from 0.01 mbar to 5 mbar (e.g., from 0.05 mbar to 1 mbar).

[0080] In various implementations, a first layer of hydrogenated amorphous carbon or diamond like carbon is created from acetylene. In some embodiments, a second layer is deposited over the acetylene created surface of fluorinated amorphous carbon. This may be created, for example, a C ₁ -C ₅ alkane substituted with fluorine (e.g.. fluoromethane, difluoromethane, trifluoromethane, fluoroethane, difluoroethane, trifluoroethane such as 1.1.1 - trifluoroethane, tetrafluoroethane such as 1,1,1,2-tetrafluoroethane, pentafluoroethane such as 1,1,1,2,2-pentafluoroethane, fluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluorpropane such as 1,1,1,3,3-pentafluoropropane, hexafluoropropane such as 1,1,1,3,3,3-hexafluoropropane or 1,1,1,2,3,3-hexafluoropropane or

1.1.2.2.3.3 -hexafluoropropane, heptafluoropropane such as 1, 1,1, 2, 2, 3,3,3- heptafluoropropane, fluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, pentafluorobutane such as 1,1,1,3,3-pentafluorobutane, hexafluorobutane, heptafluorobutane, octafluorobutane, nonafluorobutane. fluoropentane, difluoropentane, trifluoropentane, tetrafluoropentane, pentafluoropentane, hexafluoropropane, heptafluoropropane, octafluoropropane, nonafluoropropane, decafluoropropane such as 1, 1,1, 2, 2, 3, 4, 5,5,5- decafluoropropane) or a hydrofluoroolefins (FHO) such as C ₂ -C ₅ mono unsaturated alkane substituted with fluorine (e.g., fluoroethene, difluorethene, trifluoroethene, fluropropene, difluoropropene. trifluoropropene, tetrafluropropene such as 2.3,3,3-tetrafluoropropene,

1.3.3.3-tetrafluoropropene, pentafluoropropene, fluorobutene, difluorobutene, trifluorobutene, tetraflurobutene, pentafluorobutene, hexafluorobutene such as 1,1,1,4,4,4-hexafluoro-2-butene including cis-1,1,1,4,4,4-hexafluoro-2-butene or trans-1,1,1,4,4,4-hexafluoro-2-butene, heptafluorobutene. fluropentene. difluoropentene, trifluoropentene, tetrafluoropentene, pentafluoropentene, hexafluoropentene, heptafluoropentene, octoafluoropentene, nonafluoropentene) and mixtures thereof. In some embodiments, the fluorinated amorphous carbon layer is created from a fluorinated hydrocarbon selected from 1,1,1,2-tetrafluoroethane (also referred to R-134a or HFC-134a), 2,3,3,3-tetrafluoropropene (also referred to as R-1234yf or HFO-1234yf), 1,3,3,3-tetrafluoropropene (also referred to as HFO-1234ze or R-1234ze, and combinations thereof. In some embodiments, the source gas comprises R1234 and/or R1234A. It will be understood that in any inconsistency between chemical structure and refrigerant designation name (e.g., R-1234yf), both compounds will be considered embraced within the scope of the disclosure for use as suitable precursor gases.

[0081] Suitable source gas materials may be, for example, aliphatic hydrocarbons having 1- 9 carbon atoms, halogenated aliphatic hydrocarbons having 1-9 carbon atoms and aliphatic alcohols having 1-3 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane. isobutane, n-pentane, isopentane, neopentane, and the like. Among halogenated hydrocarbons and fluorinated hydrocarbons they include, for example, methylfluoride, perfluoromethane, ethyl fluoride, 1,1 -difluoroethane (HFC-152a), 1,1,1 -trifluoroethane (HFC- 430a), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane, perfluoroethane, 2,2- difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, perfluorobutane, perfluorocyclobutane. Partially hydrogenated chlorocarbon and chlorofluorocarbons for use in this disclosure include methyl chloride, methylene chloride, ethyl chloride, 1,1,1- trichlorethane, 1,1 -di chloro- 1 -fluoroethane (HCFC-141b), 1-chloro-1,1 -difluoroethane (HCFC-142b), l,l-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1-chloro-1,2,2,2- tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane. Aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol.

[0082] Plasma-polymerized fluorocarbon films can be formed by plasma-enhanced chemical vapor deposition (PE-CVD), also known as glow-discharge decomposition, using an alternating current (AC) or direct cunent (DC) power source. The AC supply may operate in the radio frequency or the micro wave range. Selection of PE-CVD processing parameters, such as power source type or frequency, system pressure, feed gas flow rates, inert diluent gas addition, substrate temperature, and reactor configuration, to optimize product properties. The fluorocarbon outermost layer may be prepared in a number of ways. The outermost layer may be a single layer of uniform composition or a single layer of graduated composition. In the case of a graduated layer composition, the fluorine content may be lowest in the area closest to the substrate and highest in the area furthest from the substrate. Lower fluorine content in the material closest to the substrate improves adhesion to the PHA substrate, while higher fluorine content at the fdm surface may increase barrier properties (e.g., decrease transmission of a gas such as O2, CO2, H2O through the layer having increased fluorine content). That is, the outermost layer can have a concentration gradient of fluorine which varies from 0 atomic percent closest to said substrate up to, for example, 20 to 65 atomic percent at the outermost surface. The graduated structure can be made by varying the composition of the feed gas during the deposition of the layer. In some embodiments, the atomic percent of fluorine on the surface of the outermost layer should be between 20 and 65 atomic percent. The atomic percent of the surface of the layer can be determined using X-Ray Photoelectron Spectroscopy (XPS). In these experiments, the XPS may provide an analysis depth of 5 nm in order to characterize the surface.

[0083] There are a wide variety of feed gases that may be used to prepare the plasma coatings on the PHA sources which typically include at least one source of fluorine and/or carbon. Sources of fluorine include but are not limited m alkane fluorides, alky l metal fluorides, ary l fluorides, styrene fluorides, alkene fluorides, fluorine substitutes silane and the like. Examples include hexafluoroethane: tetrafluoroethylene; pentafluoroethane; octafluoropropane; 2H- heptafluoropropane; IH-heptafluoropropane; hexafluoropropylene; 1,1, 1,3, 3, 3- hexafluoropropane; 1,1,1,2,2,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane; 2- (trifluoromethyl)- 1,1,1,3,3,3-hexafluoropropane; 3, 3, 3 -trifluoropropyne; 1, 1,1, 3,3- pentafluoropropane; 1.1.1.3.3-pentafluoropropene; 1.1.1.2,2-pentafluoropropane; 3,3,3- trifluoropropyne; decafluorobutane; octafluorobutene; hexafluoro-2-butyne; 1, 1,1, 4,4,4- hexafluorobutane; 1,1,1 ,4,4,4-hexafluoro-2-butene; perfluoro(t-buty l)acetylene; dodecafluoropentane; decafluoropentene; hexafluoro acetone; 3,3,4,4,4-pentafluorobutene-1; perfluoroheptane; perfluoroheptene; perfluorohexane; 1H,1H,2H-perfluorohexene; perfluoro- 2,3,5-trimethyl-hexene-2; perfluoro-2,3,5-trimethylhexene-3; perfluoro-2,4,5- trimethylhexene-2; 3,3,4,4,5,5,5-heptafluoro-1-pentene; decafluoropentene; perfluoro-2- methylpentene; perfluoro-2-methyl-2-pentene, perfluoro-4-methyl-2-pentene, perfluorobenzene, perfluorotoluene, perfluorostyrene, hexafhorosilane, dimethylaluminum fluoride, trimethyltin fluoride, and diethyltin difluoride. The fluorine compounds need not always be in a gaseous phase at room temperature and atmospheric pressure but can be in a liquid or solid phase insofar as they can be vaporized on melting, evaporation, or sublimation, for example, by heating or in a vacuum. Sources of carbon include the fluorocarbons listed above and also include saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. This list includes, but is not limited to, the following: methane, ethane, propane, butane, pentane, hexane, heptane, octane, isobutane, isopentane, neopentane, isohexane, neohexane, dimethylbutane, methylhexane, ethylpentane, dimethylpentane, tributane, methylheptane, dimethylhexane, trimethylpentane, isononane and the like; ethylene, propylene, isobutylene, butene, pentene, methylbutene, heptene, tetramethylethylene, hexene, octene, allene, methyl-allene, butadiene, pentadiene, hexadiene, cyclopentadiene, ocimene, alloocimene, myrcene, hexatriene, acetylene, diacetylene, methylacetylene, butyne, pentyne, hexyne, heptyne, octyne, and the like; cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, limonene, terpinolene, phellandrene, sylvestrene, thujene, carene, pinene, bomylene, camphene, fenchene, cyclofenchene, tricyclene, bisabolene, zingiberene, curcumene, humalene, cadinenesesquibenihene, selinene. caryophyllene, santalene, cedrene, camphorene, phyllocladene, podocarprene, mirene. and the like; benzene, toluene, xylene, hemimellitene, pseudocumene, mesitylene, prehnitene, isodurene, durene, pentamethyl-benzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, lettalin, anthracene, phenanthrene, and the like. The hydrocarbon compounds also need not always be in a gaseous phase at room temperature and atmospheric pressure but can be in a liquid or solid phase insofar as they can be vaporized on melting, evaporation, or sublimation, for example, by heating or in a vacuum. Hydrogen may also be incorporated into the films in the form of the hydrogen (H ₂ ) present in the hydrocarbon feed gas. Pure hydrogen may also be used as an additional feed gas. The presence of hydrogen is not required in the materials of this invention but may be included at levels up to 25% without loss of desirable properties. Oxygen may also be incorporated into the films from the feed gas or from atmospheric oxygen gained through reaction with free radicals present on the substrate as it is removed from the reactor. Oxygen should constitute no more than 20%, preferably less than 10%. more preferably less than 1% of the material.

[0084] Exemplary source gases are provided in Tables 1-3 which also include the global warming potential (GWP) for each potential source gas (or component of the source gas) as compared to CO ₂ . In some embodiments, the source gas has a GWP of less than (or from 1 to) 1000 or less than 500 or less than 100. Table 1

Table 2

Table 3

[0085] It will be understood that in the event of any inconsistency between code, substance name, chemical name, or chemical formula in Table 1-3, each compound will be considered disclosed.

[0086] The vapor-deposited layer (a) may be formed by a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method while the details of the formation method are described later. Examples of the physical vapor deposition method include a vacuum vapor deposition method, an ion plating method and a sputtering method, and examples of the chemical vapor deposition method include plasma CVD utilizing plasma, thermal CVD, photo CVD, MOCVD and a catalytic chemical vapor deposition (Cat-CVD) method, in which a raw material gas is subjected to catalytic decomposition with a heated catalyst. The vapor-deposited layer (a) is preferably formed by a physical vapor deposition method, and particularly a vacuum vapor deposition method, thereby providing a uniform thin film having high gas barrier performance.

[0087] The vapor-deposited barrier film of the present invention may contain multiple vapor deposited layers. In various embodiments, the vapor-deposited barrier film is a multilayer vapor deposited film (e.g., an amorphous carbon layer with a fluorinated layer disposed thereon, a multilayer vapor deposited film prepared by two or more plasma treatments selected from plasma treatment of the substrate with a noble gas source gas (e.g., Argon), plasma treatment of the substrate with a hydrocarbon (e.g., acetylene) source gas, plasma treatment of the substrate with a fluorinated hydrocarbon source gas). In some embodiments, the multilayer vapor deposited film is produced from a first plasma treatment with a neutral (e.g.. N ₂ ) and/or noble gas source gas (e.g., Argon), a second plasma treatment with a hydrocarbon (e.g., acetylene) source gas, and a third plasma treatment with a fluorinated hydrocarbon source gas. Examples of the multilayer vapor-deposited layer include such a multilay er vapor-deposited layer that contains a vapor-deposited layer formed by a physical vapor deposition method (which may be hereinafter referred to as a PVD layer) and a vapor-deposited layer formed by a chemical vapor deposition method (which may be hereinafter referred to as a CVD layer), in which at least one layer of the PVD layer is the vapor-deposited layer (a). The vapor-deposited layers may have the same composition or different compositions. In particular, a structure containing a PVD layer and a CVD layer that are formed alternately, for example, a structure containing a PVD layer, a CVD layer and a PVD layer in this order, in which at least one layer of the PVD layers is the vapor-deposited layer (a), is preferred. By forming a CVD layer on a PVD layer, defects and the like formed in the PVD layer are filled, and thus the gas barrier performance and the interlayer adhesion may be enhanced. The thickness of a PVD layer may be from 0.1 to 500 nm (e.g., from 5 to 100 nm from 10 to 100 nm, from 10 to 50 nm).

[0088] The surface roughness of the PVD layer (which is measured by AFM) is preferably approximately 5 nm or less for exhibiting the barrier performance since the vapor-deposited particles may be accumulated densely. In this case, when the thickness of a layer is less than 20 nm, the vapor-deposited particles may fill the open gaps present in the depressions among the vapor-deposited particles but cover only thinly the bumps of the vapor-deposited particles (or partially expose them), and thereby the adhesion between the layers may be further enhanced. [0089] Examples of a surface treatment formed by a plasma CVD method include a layer formed of at least one selected from a metal, a metal oxide, a metal nitride and the like, which are obtained by plasma decomposition of an organic compound. Alternatively, in the methods of manufacturing a gas barrier film coated PHA container according to the present invention, where the PHA container is heated by a resistance wire type electric heater to dry said plastic container before flowing said dry gas inside said plastic container or at the same time said dry gas is flowed, or before blowing the inside of said plastic container with said heated dry gas or at the same time blowing with said heated dry gas is carried out. By simultaneously carrying out heating with a resistance wire type electric heater when vacuum drying or drying with heated dry gas before the container is coated, the drying efficiency may be increased.

[0090] Further, the surface treatment may include the steps of heating a plastic container by microwaves, and then blowing the inside of said plastic container with a dry gas to fill the inside of the container with the dry gas to dry said plastic container, or heating the PHA container by microwaves to dry said plastic container at the same time the inside of the plastic container is blown with dry gas to fill the inside of the container with the dry gas; and replacing the gas inside said plastic container with a source gas or a gas which includes a source gas. converting a source gas to plasma, and forming a gas barrier film on the inner surface of said plastic container by a CVD method. In the case where container heating by microwaves is carried out simultaneously, dry gas may be used in place of heated dry gas. In some embodiments, the surface treatment for the container may include the steps of heating a plastic container by a resistance wire type electric heater, and then blowing the inside of said plastic container with a dry gas to fill the inside of the container with the dry gas to dry said plastic container, or heating said plastic container by a resistance wire type electric heater to dry said plastic container at the same time the inside of the plastic container is blown with dry gas to fill the inside of the container with the dry gas; and replacing the gas inside said plastic container with a source gas or a gas which includes a source gas, converting said source gas to plasma, and forming a gas barrier film on the inner surface of said plastic container by a CVD method. In the case where container heating by a resistance wire type electric heater is carried out simultaneously, dry gas may be used in place of heated dry gas.

[0091] Typically, the period of time required from the time the replacement of the gas inside said plastic container with the source gas or the gas which includes the source gas is begun until the vacuum is opened after a gas barrier film is formed on the inner surface of said plastic container is 10 seconds or less. The dry gas or said heated dry gas may be, for example, dehumidified air, carbon dioxide gas or nitrogen gas. and the dew point is preferably -20 °C. or lower.

[0092] The surface treatment plasma process which ty pically forms a gas barrier film on the inner surface of a dry gas filled container obtained by the preparing method may comprise (1) a replacing process which replaces the gas inside the plastic container with a source gas or a gas which includes a source gas, and (2) a gas barrier film forming process which converts the source gas to plasma and forms a gas barrier film on the inner surface of the plastic container by a CVD method.

[0093] Either the supply of a high frequency or the supply of microwaves forming a high frequency may be used in order to convert the source gas to plasma. There may be a capacitive coupling method and an inductive coupling method in high frequency discharging. Exemplary apparatuses capable of performing these treatments are equipped with film forming chambers which function as external electrodes, source gas introduction means which introduce a source gas that will be converted to plasma to the inside of each plastic container housed in the film forming chambers, and high frequency supply means which supply a high frequency to each external electrode of the film forming chambers, and is an apparatus wherein a high frequency is supplied to the external electrodes to convert the source gas to plasma inside the plastic containers, w hereby a gas barrier film is formed on the inner surface of the plastic containers.

[0094] The source gas for forming DLC films (in particular DLC with this apparatus) may comprise aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons or the like which form a gas or liquid at normal temperature. In particular, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane or the like having a carbon number of 6 or higher is preferred. In the case of being used in containers with a surface exposed to certain products, such as those surfaces exposed to food, beverages (alcoholic beverages such as beer, wine, hard seltzer, ready to drink cocktails, and beverages comprising spirits; non-alcohol beverages such as carbonated soft drinks, carbonated drinks, juices, water; combinations thereof), or consumer packaged goods including beauty products, personal care products, natural and dietary supplements products, cleaning products, tobacco products, cannabis products, from the viewpoint of hygiene, aliphatic hydrocarbons, especially ethylene t pe hydrocarbons such as ethylene, propylene or butylene, or acetylene type hydrocarbons such as acetylene, allylene or 1 -butyne may be chosen for production of the DLC fdm. These materials may be used separately or as a gas mixture of two or more types. Further, these gases may be used in a way in which they are diluted by a noble gas such as argon or helium. Further, a Si-containing hydrocarbon gas is used as a source gas for forming a Si- containing DLC film.

[0095] The high frequency power source for these apparatuses typically generates high frequency energy for converting source gas to plasma inside the plastic container. The frequency of the high frequency power source may be from 1 kHz to 1000 MHz, in particular for DLC formation. By application of RF output (e.g., 13.56 MHz) to the electrodes in the presence of source gas, a plasma may be generated between the external electrode and the internal electrode. The automatic matching device may carry out impedance matching according to the inductance L and the capacitance C in order to minimize the reflected waves from the entire electrode supplying output. The fixed matching device typically converts the impedance of the coaxial cable to the impedance of plasma. In this way. hydrocarbon plasma is generated inside the container on the surface comprising a PHA thermoplastic resin (e.g., bottle), and a DLC film is formed on the inner surface of the PHA container. The film may be formed in several seconds (e.g, less than 10, less than 5, less than 2, less than 1). Following film formation or at an appropriate film thickness, the RF output from the high frequency supply means may be stopped, and the plasma is extinguished to complete the formation of the DLC film. In some embodiments, a vacuum valve may be closed and the supply of source gas is stopped to the interior of the container.

[0096] The upper limit of the thickness of the plasma films is typically 5,000 nm (e.g., 500 nm, 100 nm). Meanwhile, the lower limit may be 0.1 nm (e.g., 0.5 nm). If the thickness is in the above-mentioned range, the film should provide the appropriate adhesion and gas-barrier properties described herein. The thickness of the plasma film (or any layer thereof) may be from 0.1 to 5,000 nm (e.g, from 0.1 to 500 nm from 0.1 to 100 nm). The formation of the plasma CVD thin film may be carried out under reduced pressure which often increases the density of the film. These low pressures are particularly helpful for DLC or amorphous DLC formation. The pressure or partial pressure of the source gas (e.g., noble gas, neutral gas, acetylene) may be, for example, the range of 0.1 x 10 ^-3 to 1 x 10 ² Pa (e.g., 1 x 10 ^-2 to 10 Pa). The plasma CVD thin film may also be subjected to a cross-linking treatment by electron beam irradiation to enhance water resistance and durability.

[0097] The source gas may be introduced into the container, where a plasma is generated from the source gas with an apparatus for generating low temperature plasma of direct current (DC) plasma, low frequency plasma, radio frequency (RF) plasma, pulse wave plasma, tripolar plasma, microwave plasma, downstream plasma, columnar plasma, plasma-assisted epitaxy, or the like. The ratio of the pressure in the carbon deposition step to the pressure in a fluorinated carbon deposition step may be, for example, 10 to 1 x 10 ⁷ (e.g., 1 x 10 ² to 1 x 10 ⁶ , 1 x 10 ² to 1 x 10 ⁵ ). In some embodiments, the ratio of the pressure in the fluorinated carbon deposition step to the pressure in the carbon deposition step may be, for example, 10 to 1 x 10 ⁷ (e.g., 1 x 10 ² to 1 x 10 ⁶ , 1 x 10 ² to 1 x 10 ⁵ ).

[0098] In the case where a DLC film is formed, for example, aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons and the like which form a gas or liquid at room temperature are used as a source gas. In particular, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane and the like having a carbon number of 6 or higher are preferred. In the case of being used in containers for food or the like, from the viewpoint of hygiene, aliphatic hydrocarbons, especially ethylene type hydrocarbons such as ethylene, propylene or butylene or the like, or acetylene type hydrocarbons such as acetylene, allylene or l -butyne are preferred. These materials may be used separately or as a gas mixture or two or more types. Further, these gases may be used in a way in which they are diluted by a noble gas such as argon or helium. Further, in the case where a silicon-containing DLC film is formed, a Si-containing hydrocarbon gas is used.

[0099] Containers

[00100] The present disclosure provides a product package for a consumer goods product, wherein the product package includes at least one biodegradable package portion which comprises the aforementioned polymeric composition. In certain embodiments, the biodegradable package portion is preferably formed a method selected from the group consisting of injection molding, compression molding, thermoforming, cast and blown film formation, extrusion coating, extrusion blow molding, injection blow molding, injection stretch blow molding, and extrusion profiling. In particular embodiments, the biodegradable package (or a portion thereof) is formed from an injection molding process such as injection blow molding or injection stretch blow molding.

[00101] A compostable material for use as the substrate in the containers described herein may comprise a polymeric PHA material and a nucleating agent such that the compostable material may have a degree of crystallinity of 5% to 40%. In some embodiments, the material has a degree of crystallinity of 10% to 35%. In some embodiments, the material has a degree of crystallinity of 15% to 30%. In some embodiments, the material has a degree of crystallinity of 15% to 25%. The degree of crystallinity of the material may affect the thermal and mechanical properties of the material. For example, in some embodiments, a degree of crystallinity above 35% crystallinity may prevent the material 100 from being pliable enough for further processing (such as thermoforming), which can be undesirable. In some cases where the degree of crystallinity is too high (for example, above 40%), the material 100 must be re- melted and re-processed, which can be undesirable. In some cases, a degree of crystallinity below 10% crystallinity may require long processing times (for example, for thermoforming) in order to produce a suitable finished product, such as a compostable food packaging container. Long processing times can be undesirable yvith respect to manufacturability.

[00102] The degree of crystallinity of the container can be roughly characterized by the portion of the material in which the compostable polymeric material has crystallized in comparison to the entire material. The compostable polymeric material can in some cases crystallize on its own during cooling, so some of the crystallized portions are in regions of the material without the nucleating agent. The presence of the nucleating agent can accelerate crystallization, so some of the crystallized portions may be localized near nucleating agent dispersals in the polymeric material. The crystallized portions of the material may include spherulite structures, which can be formed by a controlled crystallization (cooling) process. The degree of crystallinity of the material 100 can be calculated as % crystallinity by dividing the amount of the cry stalline phase by the total amount of the material and multiplying by 100 as determined by differential scanning calorimetry (DSC). For the fabrication of useful articles, the compositions described herein are processed preferably at a temperature above the crystalline melting point of the polymers but below the decomposition point of any of the ingredients (e.g., the additives described above, with the exception of some branching agents) of the polymeric composition. While in heat plasticized condition, the polymeric composition is processed into a desired shape, and subsequently cooled to set the shape and induce crystallization. Such shapes can include, but are not limited to, a fiber, filament, film, sheet, rod, tube, bottle, or other shape. Such processing may be performed using any technique, such as, but not limited to, extrusion, injection molding, injection stretch molding, extrusion blow molding, compression molding, blowing or blow molding (e.g., blown film, blowing of foam), calendaring, rotational molding, casting (e.g., cast sheet, cast film), or thermoforming. Thermoforming is a process that uses films or sheets of thermoplastic. The polymeric composition is processed into a film or sheet. The sheet of polymer is then placed in an oven and heated. When soft enough to be formed it is transferred to a mold and formed into a shape.

[00103] Blow molding, which is similar to thermoforming and is often used to produce deep draw products such as bottles and similar products with deep interiors, also benefits from the increased elasticity and melt strength and reduced sag of the polymer compositions described herein.

[00104] In some embodiments, the present packaging material may be used for food packaging, beverage packaging, or consumer packaged good packaging. The packaging ty pically provides physical protection for the product (e.g.. including but not limited to food, beverage such as wine, smoking product such as a smoking product comprising one or more cannabinoids, beauty product, personal care product, pharmaceutical product, cleaning product); the product in the package may require protection from, among other things, shock, vibration, compression, temperature, moisture content fluctuation, oxygen content fluctuation, and/or bacteria. The packaging may take the form of trays, bags, boxes, cans, cartons, pallets, or bottles. In some embodiments, the packaging material may have improved barrier resistance for permeants such as oxygen, water, CO2, such that the shelflife of any food contained within the packaging may be increased (e.g., as compared to material without a coating as described herein).

[00105] The present disclosure may include blend compositions formed from a molding process such as those with a combination of a biodegradable polymer (e.g.. a biodegradable polymer having one or more monomeric units (e.g., monomer, co-polymer) independently having the structure -[C(O)-R ₁ -C(O)-O-R ₂ -O]- wherein R ₁ is C ₂ -C ₆ alkylene (e.g., ethylene, propylene, buty lene, pentylene) or arylene (e.g., phenylene) and R ₂ is C ₂ -C ₆ alkylene (e.g., ethylene, propylene, butylene, pentylene), a succinate copolymer, poly(ethylene succinate), poly(butylene succinate), poly(propylene succinate), poly(ethylene adipate), poly(butylene adipate), poly(propylene adipate), polyputylene terephthalate), poly(propylene terephthalate), poly(ethylene succinate-co-adipate), poly(propylene succinate-co-adipate), poly(butylene succinate-co-adipate), poly(propylene succinate-co-adipate), poly(ethylene succinate-co- terephthalate), poly(propylene succinate-co-terephthalate), polyputylene succinate-co- terephthalate), poly(propylene succinate-co-terephthalate), polyputylene adipate-co- terephthalate) (PBAT), poly(caprolactone), poly(lactic acid), cellulose esters (such as cellulose acetate), nanocellulose, polyvinyl alcohol (PVOH), thermoplastic starch, and mixtures thereof)/PHA copolymer compositions. The disclosure also includes methods of preparing the blends having improved tensile toughness and elongation as well as tear, impact strength and faster biodegradation rates as compared to the pure biodegradable polymer. In some embodiments, the blend comprises a PHA (e.g., PHBH) and one or more biodegradable polymers selected from PBS, PBS A, PBAT, and PVOH. The temperatures experienced by a polymer during processing can cause a drop in melt strength due to thermal degradation, which can in turn cause difficulties in processing the polymer(s). Increased melt strength is therefore useful in that it allows the polymers to be processed across a broader temperature range. A broader processing window is especially important in certain polymer applications, such as in the production of blown film (i.e., in preventing or reducing bubble collapse), or cast film extrusion, thermoformed articles (i.e., preventing or reducing sheet sag during thermoforming), profile extruded articles (i.e., preventing or reducing sag), non-woven fibers, monofilament, etc.

[00106] Articles made from the compositions described herein such as those produced by combining multiple PHA compositions with different crystallinities or those produced by combining a PHA composition with another biodegradable polymer may exhibit greater tensile toughness and elongation while exhibiting an increased biodegradability. Without wishing to be bound by theory, the increased toughness and elongation may be due to the high molecular weight of 3-hydroxybutyrate copolymer while the increases in biodegradability are due to the chemical composition of the copolymer. The increases in tensile toughness can be 10 to 40 fold greater as compared to an otherwise identical composition not having the 3-hydroxybutyrate monomeric units. The increases in elongation can be 10 to 60 fold greater. Tensile toughness increase can be 10-20, 20-30 or 25-35 fold. Additionally, elongation increase can be 20-30, 30- 40 or 45-60 fold through these combination strategies. Increases in biodegradation rate can be 2 fold, 3 fold, 4 fold or 10 fold. The material properties of the blend required for processing as well as the desired biodegradability rate can therefore be designed into the blend by varying the composition of the 3-hydroxybutyrate copolymer and the copolymer’s overall concentration in the blend. Furthermore, coupling these processing techniques with the surface treatments of the present disclosure may result in biodegradable containers with sufficient barrier properties for food containment.

[00107] Prior to surface treatment, the container may be molded such as blow molded, injection molded, extrusion molded, injection blow molded, extrusion blow molded, injection stretch blow molded, or combinations thereof. Molded articles can additionally be made from the blend compositions described herein. Polymers used for injection molded parts are first fed into a heated barrel and melted. As is typical in extrusion blow molding, these polymers may be extruded into a mold cavity such as a tube, sealed within the cavity, inflated with air expand to the shape of the cavity, and cooled to form an extrusion blow molded container. In some embodiments, the polymer may be mixed and forced into a closed mold cavity under pressure to create the part (e.g.. through injection, through extrusion). The part may be cooled and so hardens to the configuration of the cavity. After cooling, the mold generally opens, and the part may then be ejected and sometimes subjected to further finishing steps (e.g., the surface treatment of the present disclosure). In some embodiments, the container may be made by injection stretch blow molding prior to the surface treatment. Generally, these processes involve a single or two stage process where one or more thermoplastic resin compositions of the present disclosure are first injection molded to form a preform. While still hot, the preform may be moved to a second blow molding station (e.g., in the same machine) where the preform is stretched (e.g., in length using a core rod) and/or inflated inside of a cold mold which may cause the thermoplastic resin to take the shape of the mold cavity. In some implementations, the preform may be cooled, later reheated, and stretched and blow molded in a separate machine. In some embodiments, the container may be formed from injection blow molding. In these processes, the polymers (or polymer compositions including blends) of the present disclosure may be injected into a mold. The heated polymer composition may be forced into a core pin, which may rotate around a molding station and/or be inflated to the mold geometry and subsequently cooled. In some embodiments, the container produced from these processes (e.g., bottle) may have a weight of from 15g to 35g.

[00108] Whether the container-making process such as bottle making process is an injection stretch blow molding process where the injected preliminary products are typically referred to as “preforms” or an injection blow molding process where the injected products are typically called “parisons,” the hot melt generally begins to cool the instant it enters an injection cavity because such cavities are relatively much colder than the distribution manifolds and injection nozzles through which the melt travels on its way to the injection cavities. If melt enters some of the cavities of a set of multiple cavities at a slightly different time than others and/or at a different rate, the melt in some cavities will cool at different rates than others, and some will not have as much time to cool down as others before the preforms are pulled out of the injection mold for the next stage in the process. This can have very significant consequences in the quality and consistency of the finished products. Balancing the relative temperature of the melt and mold (particularly within an appropriate tolerance for mass production) can result in increased and more consistent container (e.g., bottle) products. In some embodiments, the polymer (or polymer blend) may be heated to a temperature offrom 135°C to 165°C (e.g.. from 135°C to 150°C, from 135°C to 145°C) in order to form a melt to place in the mold cavity. The mold cavity may be kept at a temperature of from 30°C-50°C (e.g., with water). The dryer temperature may be kept at. for example, 75°C to 100°C. Leveraging the properties of the PHA polymers, and PHA polymer blends (e.g., blends in a weight ratio of PHA compositions with different crystallinities of PHA1:PHA2 of from 10: 1 to 1 : 10), the extruder RPM may be, for example from 5-7 RPM. In various implementations, these blends may be molded with an extruder load of from 35%-40%, an RPM of from 5-7 RPM, a melt pressure of from 950 psi to 2000 psi (e.g., from 1000 psi to 1200 psi).

[00109] This disclosure describes containers that may be generally compostable and may provide for a suitable shelf life for the product contained therein, such as food packaging containers that provide a suitable shelf life of the packaged food and beverages or consumer packaged good products including beauty, personal care, cleaning, pharmaceutical, nutraceutical, household, tobacco, cannabis, CBD, or THC products. Containers comprising compostable or biodegradable material may include an organic or inorganic material configured to chemically or physically break down or decompose under aerobic and/or anaerobic conditions, such as in a municipal or industrial composting or digesting facility . For example, in some embodiments, a container of the present disclosure may contain 90% to 100% or 99% to 100% compostable and/or biodegradable material(s). The container may, for example, have aerobic (e.g., compost) biodegradability characterized by more than 70% or more than 80% or more than 90% after 28 days as measured at 58°C according to ISO14855 (compost). In some embodiments, the container may have aerobic compostability of more than 60% or more than 70% at 25°C according to ISO14851 (activated sludge). In some embodiments, the container may have anaerobic compostability (e.g., biogas) of more than 60% or more than 70% or more than 80% or more than 90% or more than 95% or more than 99% at 35°C according to ISO14853 (aqueous phase). In some embodiments, the container may have anaerobic compostability (e.g., biogas) of more than 60% or more than 70% at 52°C according to ISO15985 (solid phase). In various implementations, the container may be biodegraded in sea water to form H ₂ O and CO ₂ (e.g., as characterized by a biochemical oxygen demand (BOD) test and/or a chemical oxygen demand (COD) test at, for example, 27°C, and with a, for example freeze grinded powder of the container, having a BOD/COD result greater than 50% after 10 days or after 15 days or after 20 days or after 25 days or after 30 days or after 35 days or after 40 days or after 45 days or after 50 days). Typically, the containers of the present disclosure are compostable and/or biodegradable as described herein. Although not preferred, a container of the present disclosure (e.g., food container, beverage container, consumer packaged good container) may include one or more generally non-compostable or non-biodegradable materials. However, in most embodiments, if present, the non-compostable or non-biodegradable materials are present in small amounts such as less than 1% by weight or less than 0.1% by weight of the container. In some embodiments, the packaging container may be constructed of a sheet material having one or more layers. For example, the sheet material may have an internal layer sandwiched between two external layers, and two bonding layers coupling the internal layer with each external layer. In some embodiments, the sheet material may be extruded, co-extruded. or laminated. In some embodiments, the sheet matenal may be extruded, co-extruded, or laminated using a single screw extruder or a multi-screw extruder (e.g., twin screw extruder). The resulting container may be industrial and/or home compostable while still providing a suitable barrier for the packaged food. By providing compostable materials as food packaging containers for particular products, consumers of such products may produce that is less harmful to the environment, degrades quicker than non-compostable products in landfills and/or natural environments (e.g., the ocean).

[00110] The container may comprise these the polymer compositions as disclosed herein. The container can further comprise a foam, woven fibers, nonwoven fibers, a thermoformed part, or an injection molded part.

[00111] The subject matter described in this disclosure can be implemented in particular embodiments so as to realize certain product characteristics. For example, the compostable material can have a suitable degree of crystallinity that allows for the material (for example, in sheet form) to be quickly thermoformed (or another forming, manufacturing, or conversion process). The compostable material can have a heat deflection temperature (HDT) that is higher than the HDT of traditional food packaging material. The compostable material can be microwavable, such that the compostable material can be exposed to microwave energy and retain its thermal and mechanical properties and without deforming. A microwavable material can have a high heat resistance and adequate stiffness at elevated temperatures. Optionally, the outer surface of a container made of a microwaveable material remains sufficiently cool such that the container can be safely handled. In some embodiments, the compostable material is substantially free of impact modifier (for example, does not include an impact modifier) but still has suitable ductility and/or strength. In some embodiments, the compostable material is visually transparent or translucent.

[00112] Biodegradable and/or Compostable

[00113] The containers are generally made of a biodegradable polymeric composition. In one embodiment, this polymeric composition includes at least (1) from 5 weight percent to 95 weight percent poly(hydroxyalkanoates); (2) from 5 weight percent to 95 weight percent of at least one biodegradable polymer selected from the group consisting of poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate-co-terephthalate), poly (caprolactone), poly (lactic acid), cellulose esters (such as cellulose acetate) thermoplastic starch, and mixtures thereof; and (3) from 0.1 weight percent to 5 weight percent of a nucleating agent. In certain embodiments, the polymeric composition preferably includes from 35 weight percent to 90 weight percent poly(hydroxyalkanoates). For example, the polymeric composition includes from 40 weight percent to 70 weight percent poly (hydroxy alkanoates). In some embodiments, the polymeric composition may include from 5 weight percent to 50 weight percent poly(butylene succinate). More preferably, the polymeric composition includes from 10 weight percent to 30 weight percent poly (butylene succinate). In various implementations, the polymeric composition preferably includes from 5 weight percent to 50 weight percent poly(butylene succinate-co-adipate). More preferably, the polymeric composition includes from 10 weight percent to 30 weight percent poly(butylene succinate-co- adipate). In some instances, the polymeric composition preferably includes from 10 weight percent to 70 weight percent poly(lactic acid). In various implementations, the polymeric composition includes from 20 weight percent to 60 weight percent poly(lactic acid). In some embodiments, the polymeric composition preferably includes from 5 weight percent to 50 weight percent cellulose esters, such as cellulose acetate. For example, the polymeric composition may include from 10 weight percent to 30 weight percent cellulose esters.

[00114] Preferably, the polymeric composition is biodegradable and/or compostable. More particularly the polymeric composition is both biodegradable and compostable. Biodegradable compositions generally undergo biodegradation by living organisms (microbes) in anaerobic and aerobic environments (as determined by ASTM D5511), in soil environments (as determined by ASTM 5988), in freshwater environments (as determined by ASTM D5271 (EN 29408)), or in marine environments (as determined by ASTM D6691). The biodegradability of biodegradable plastics can also be determined using ASTM D6868 and European EN 13432. In some embodiments, the containers of the present disclosure are also " compostable”, as determined by ASTM D6400 for industrial or home compostability. Each of the protocols are incorporated herein by reference in their entirety and in particular to how to identify biodegradable and compostable materials.

[00115] In embodiments, the renewable carbon content of the polymer composition of the invention as measured by ASTM D6866 is at least 1% by weight of the composition, at least 20% by weight of the composition, at least 40% by weight of the composition, at least 80% by weight of the composition, at least 95% by weight of the composition, at least 99% by weight of the composition, or is 100% by weight of the composition.

[00116] In example embodiments, the renewable carbon content of the 3HB copolymer is at least 95% by weight of the copolymer, at least 97% by weight of the copolymer, at least 98% by weight of the copolymer, at least 99% by weight of the copolymer, or at least 100% by weight of the copolymer.

[00117] Biodegradability can be measured using a respirometry-type test. For biodegradation testing in soil, one places a polymer sample (a film or ground powder) into a container with aerobically active microorganisms, water and soil. The container is closed and then maintained at a standard temperature (20-35 °C). Over the course of several days or months, the microorganisms then digest the sample thereby using up the oxygen as well as producing carbon dioxide. Measurement of the rate of CO ₂ generation over time allows the determination of the rate of biodegradation. For respirometry testing, the media can be soil, fresh water, salt water, compost or sludge. Anaerobic microbes can also be used. In this case, the amount of methane produced is measured and used to determine the biodegradation rate.

[00118] The biodegradation rate by gravimetric methods. In this case, a polymer film is buried in soil or other media containing active aerobic microorganisms and water. The weight loss of the polymer film over time is then measured and used to determine the disintegration rate. Several organizations certify the biodegradability of polymers under different standards and conditions. These include Vincotte. D1N-CERTCO and European Bioplastics. These are all European-based certifications for industrial composting, home composting, soil, fresh water and sea water biodegradation. The requirements standard utilized for composting, soil and water biodegradation is EN 13432 while the test method utilized is EN 14995. For sea water biodegradation, the requirement standard is ASTM D7081 and the test method is ASTM D6691. In the US, Biodegradable Products Institute (BPI) certifies for industrial composting using the standards ASTM D6400 (plastics) and D6868 (paper coatings). The Australian Bioplastics Association has also set up biodegradation certificates for home and industrial compositing following the standards AS4736-2006 and AS5810-2010.

[00119] As various changes can be made in the above-described subject matter without departing from the scope and spirit of the present disclosure, it is intended that all subject matter contained in the above description, or defined in the appended claims, be interpreted as descriptive and illustrative of the present disclosure. Many modifications and variations of the present disclosure are possible in light of the above teachings. Accordingly, the present description is intended to embrace all such alternatives, modifications and variances which fall within the scope of the appended claims.

[00120] All documents cited or referenced herein and all documents cited or referenced in the herein cited documents, together with any manufacturer’s instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated by reference, and may be employed in the practice of the disclosure.