Biodegradable PVC substitutes

Abstract

This disclosure provides a plastisol composition comprising about 1 to about 49 weight percent of at least one polyhydroxyalkanoate. The plastisol composition also comprises about 51 to about 99 weight percent of at least one plasticizer, the at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof. Also disclosed are screen printing inks comprising plastisol.

Description

Technical Field

[0001] The present disclosure relates to biodegradable polymer compositions. More specifically, the present disclosure relates to biodegradable polymer compositions comprising poly(hydroxyalkanoate) that can be used to form plastisols and flexible molded articles.

Background Art

[0002] Polyvinyl chloride (PVC) is widely used in the plastics industry due to its unique physical and conversion properties. In particular, PVC is used to produce highly flexible polymer compositions, such as plastisols. Typically, such flexible PVC is highly plasticized with phthalate-based plasticizers, which disrupt chain interactions, which reduces the overall crystallinity and increases flexibility. Different levels of plasticizers are used for various applications, and the levels specify the degree of softness and flexibility.

[0003] However, the use of PVC also includes several drawbacks from the perspectives of health and environment. PVC is known to release toxic by-products into the environment, particularly vinyl chloride. Vinyl chloride has been determined to be a carcinogen. Also, the end-of-life disposal of PVC-based products is also a problem because PVC shows little or no biodegradation when buried in landfill sites or leaked into the marine environment.

[0004] Furthermore, phthalate-based plasticizers typically used with PVC are also known to be endocrine disruptors.

[0005] Therefore, it is desirable to provide alternative polymer compositions that can be used for the production of plastisols and other flexible articles instead of plasticized PVC compositions. Preferably, these compositions are biodegradable and / or non-toxic. In particular, the plastisol compositions are PVC-free.

[0006] Furthermore, it is desirable to provide an ink incorporating the above-mentioned plastisol composition, such as a screen printing ink. In addition, it is desirable to provide a molded article formed from the plastisol composition, such as a fishing lure.

[0007] Furthermore, it is desirable to provide a process for forming molded articles from the above-mentioned plastisol composition. [Overview of the Initiative]

[0008] The above and other needs are met by the polyhydroxyalkanoate (PHA)-based plastisols provided in this disclosure.

[0009] In a first embodiment, the present disclosure provides compositions for plastisols. According to one embodiment, the plastisol composition comprises about 1 to about 49 weight percent of at least one polyhydroxyalkanoate. The plastisol composition also comprises about 51 to about 99 weight percent of at least one plasticizer, the at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof.

[0010] According to a particular embodiment, the composition preferably comprises about 1 to about 40 weight percent of at least one polyhydroxyalkanoate and about 60 to about 99 weight percent of at least one plasticizer, wherein the at least one plasticizer is selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof.

[0011] In certain embodiments, the composition more preferably comprises at least one polyhydroxyalkanoate in about 1 to about 10 weight percent.

[0012] In some cases, a single form of plasticizer may be used in the composition. For example, the composition may contain only a citrate ester, such as triethyl citrate, as the plasticizer. Alternatively, the composition may contain only a triglyceride, such as triacetin, as the plasticizer.

[0013] In other embodiments, the composition may include a combination of plasticizers. According to some embodiments, the composition preferably contains at least one citrate ester in about 60 to about 80 weight percent. More preferably, the composition also contains at least one triglyceride in about 10 to about 35 weight percent.

[0014] In certain embodiments, the composition more preferably comprises about 60 to about 80 weight percent triethyl citrate. More preferably, the composition also comprises about 10 to about 35 weight percent triacetin.

[0015] In some cases, the composition preferably comprises at least one epoxidized vegetable oil selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized coconut oil, epoxidized soybean oil, and mixtures thereof. More preferably, the composition comprises epoxidized soybean oil.

[0016] According to a particular embodiment, the composition also preferably comprises at least 0.01 to about 0.5 weight percent of a crosslinking agent, the crosslinking agent being selected from the group consisting of organic peroxides, epoxides, carbodiimides, oxazolines, and mixtures thereof.

[0017] In some embodiments, the composition also preferably comprises about 0.01 to about 1 weight percent of at least one nucleating agent, the at least one nucleating agent selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, and mixtures thereof.

[0018] According to a particular embodiment, the composition also preferably comprises about 0.1 to about 20 weight percent of at least one biopolymer, the at least one biopolymer being selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, phenylbenzimidazole sulfonic acid, and mixtures thereof.

[0019] In some cases, at least one polyhydroxyalkanoate preferably comprises a polyhydroxyalkanoate copolymer, the polyhydroxyalkanoate copolymer comprising about 0.5 to about 25 mole percent monomer repeating units, the monomer repeating units being selected from the group consisting of 4-hydroxybutyrate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, 3-hydroxydecanoate, and mixtures thereof.

[0020] In some embodiments, at least one polyhydroxyalkanoate preferably comprises one or more poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P3HB-co-P3HHx) copolymers, each P3HB-co-P3HHx copolymer containing about 2 to about 15 mole percent of monomer repeating units of 3-hydroxyhexanoate.

[0021] According to certain embodiments, the composition is preferably phthalate-free.

[0022] In certain embodiments, the composition may also comprise at least one nucleating agent in an amount of about 0.05% to about 1.0% by weight, the at least one nucleating agent being selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clay, sorbitol, and mixtures thereof. More preferably, the composition may comprise at least one nucleating agent in an amount of about 0.10% to about 0.20% by weight.

[0023] In some embodiments, the composition may also comprise at least one filler in an amount of about 0.5% to about 20% by weight, the at least one filler being selected from the group consisting of aragonite, clay, calcium carbonate, cellulose, nanocellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starch, diatomaceous earth, titanium dioxide, nanoclay, mica, and mixtures thereof. More preferably, the composition may comprise at least one filler in an amount of about 1.0% to about 5.0% by weight.

[0024] According to certain embodiments, the composition may also comprise at least one rheological modifier in an amount of about 0.01% to about 1.0% by weight, the at least one rheological modifier being selected from the group consisting of organic peroxides, carbodiimides, oxazolines, epoxides, and mixtures thereof. More preferably, the composition may comprise at least one rheological modifier in an amount of about 0.1% to about 0.5% by weight.

[0025] According to some embodiments, the composition may also contain about 0.5% to about 20% by weight of natural or synthetic fibers. More preferably, the composition may contain about 1.0% to about 5.0% by weight of fibers.

[0026] In a second embodiment, the disclosure also provides an ink suitable for screen printing. According to one embodiment, the ink comprises at least one pigment and a plastisol composition, e.g., the above-described plastisol composition. Thus, the plastisol composition then comprises about 1 to about 49 weight percent of at least one polyhydroxyalkanoate and about 51 to about 99 weight percent of at least one plasticizer, the at least one plasticizer being selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof.

[0027] In certain embodiments, the pigment is preferably an inorganic pigment. However, in other embodiments, the pigment is preferably an organic pigment.

[0028] According to certain embodiments, the ink also preferably includes at least one additive selected from the group consisting of fillers, rheology modifiers, stabilizers, and mixtures thereof.

[0029] In some cases, the plastisol composition is preferably present in the ink in an amount of about 70 to about 99 weight percent of the ink.

[0030] In certain embodiments, the plastisol composition of the ink more preferably includes at least one polyhydroxyalkanoate in an amount of about 1 to about 10 weight percent.

[0031] According to some embodiments, the plastisol composition of the ink preferably includes at least one citrate ester in an amount of about 60 to about 80 weight percent. More preferably, the plastisol composition also includes at least one triglyceride in an amount of about 10 to about 35 weight percent.

[0032] In certain embodiments, the plastisol composition of the ink more preferably includes about 60 to about 80 weight percent of triethyl citrate. Still more preferably, the plastisol composition also includes about 10 to about 35 weight percent of triacetin.

[0033] In a further embodiment, the disclosure also provides coated articles. According to one embodiment, a coated article comprises at least a first surface and a coating applied over at least a portion of the first surface. The coating is applied by immersing the first surface in a plastisol composition. The plastisol comprises about 1 to about 49 weight percent of at least one polyhydroxyalkanoate and about 51 to about 99 weight percent of at least one plasticizer, the at least one plasticizer being selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof. More preferably, the plastisol comprises about 1 to about 40 weight percent of at least one polyhydroxyalkanoate and about 60 to about 99 weight percent of at least one plasticizer.

[0034] In a particular embodiment, the article is preferably a hand tool, and the coating forms a hand grip.

[0035] In another embodiment, the present disclosure provides a fishing lure. According to one embodiment, the fishing lure comprises a plastisol composition comprising the above-described plastisol composition, i.e., at least one polyhydroxyalkanoate in about 1 to about 49 weight percent and at least one plasticizer in about 51 to about 99 weight percent, wherein the at least one plasticizer is selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof, and a soft plastic fishing bait molded from the plastisol composition.

[0036] The fishing lure also includes at least one hook attached to a soft plastic fishing bait, and at least one weight attached to the soft plastic fishing bait.

[0037] In some cases, the fishing bait composition may also contain at least one attractant in an amount of about 0.1% to about 5.0% by weight, the at least one attractant being selected from the group consisting of glitter flakes, liquid colorants, powder pigments, fish scent attractants, and mixtures thereof. More preferably, the composition may contain at least one attractant in an amount of about 0.5% to about 2.0% by weight.

[0038] In yet another embodiment, the disclosure provides a process for producing a molded article. According to one embodiment, the process includes mixing at least one polyhydroxyalkanoate with at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof to form a slurry containing about 1 to about 49 weight percent of at least one polyhydroxyalkanoate and about 51 to about 99 weight percent of at least one plasticizer. The process also includes heating the slurry to a temperature of at least about 85°C to form a molten mixture. The molten mixture is then injected into a mold. The mixture is then cooled in the mold to form a solidified molded article. Finally, the molded article is removed from the mold. [Modes for carrying out the invention]

[0039] This disclosure provides polyhydroxyalkanoate (PHA)-based plastisol compositions, preferably biodegradable and free of phthalate-based compounds. This disclosure also provides inks for screen printing comprising the plastisol composition, and coated articles, wherein the coating comprises the plastisol composition.

[0040] The plastisol composition comprises at least one polyhydroxyalkanoate and at least one plasticizer, the at least one plasticizer being selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof.

[0041] The amount of at least one polyhydroxyalkanoate is generally about 1 to about 49 weight percent of the composition, preferably about 1 to about 40 weight percent of the composition. More preferably, at least one polyhydroxyalkanoate constitutes about 1 to about 10 weight percent of the composition.

[0042] At least one polyhydroxyalkanoate may be a homopolymer, copolymer, or terpolymer. In some cases, at least one polyhydroxyalkanoate may comprise a mixture of polyhydroxyalkanoate homopolymers, polyhydroxyalkanoate copolymers, and / or polyhydroxyalkanoate terpolymers.

[0043] In certain embodiments, at least one polyhydroxyalkanoate preferably comprises a polyhydroxyalkanoate copolymer. For example, at least one polyhydroxyalkanoate may comprise a polyhydroxyalkanoate copolymer comprising about 0.5 to about 25 mole percent of monomer repeating units, the monomer repeating units being selected from the group consisting of 4-hydroxybutyrate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, 3-hydroxydecanoate, and mixtures thereof. More preferably, at least one polyhydroxyalkanoate comprises one or more poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P3HB-co-P3HHx) copolymers, and even more preferably, each of these copolymers comprises about 2 to about 15 mole percent of monomer repeating units of 3-hydroxyhexanoate.

[0044] The plastisol composition also comprises about 51 to about 99 weight percent of at least one plasticizer, the at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof. Preferably, the plastisol composition comprises about 60 to about 99 weight percent of at least one plasticizer.

[0045] Suitable epoxidized vegetable oils that can be used in the composition as plasticizers include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized coconut oil, epoxidized soybean oil, and mixtures thereof. In some embodiments of the present disclosure, the epoxidized vegetable oil is particularly preferred to be epoxidized soybean oil.

[0046] Suitable examples of citrate esters that can be used in compositions as plasticizers include triethyl citrate, tributyl citrate, acetyltriethyl citrate, and acetyltributyl citrate. The preferred citrate ester is triethyl citrate.

[0047] In some embodiments, a preferred triglyceride plasticizer may be triacetin.

[0048] Generally, the amount of plasticizer in the composition is about 51 to about 99 weight percent of the composition, more preferably about 60 to about 99 weight percent of the composition.

[0049] In some cases, the composition may contain only a single plasticizer in an amount of about 60 to about 99 percent by weight. For example, the composition may contain only a citrate ester, such as triethyl citrate, or only a triglyceride, such as triacetin.

[0050] In other embodiments, the composition may comprise a combination of plasticizers. For example, in some embodiments, the plastisol composition may comprise about 60 to about 80 weight percent of at least one citrate ester. The composition may also comprise about 10 to about 35 weight percent of at least one triglyceride.

[0051] As described above, the preferred citrate ester may be triethyl citrate, and the preferred triglyceride may be triacetin. Therefore, in certain embodiments, the plastisol composition may contain a combination of these two plasticizers. For example, the plastisol composition may contain about 60 to about 80 weight percent of triethyl citrate and about 10 to about 35 weight percent of triacetin.

[0052] In addition to polyhydroxyalkanoates and plasticizers, plastisol compositions may also contain a variety of other additives.

[0053] In certain embodiments, the composition may also comprise at least one nucleating agent in an amount of about 0.05% to about 1.0% by weight, the at least one nucleating agent being selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clay, sorbitol, and mixtures thereof. More preferably, the composition may comprise at least one nucleating agent in an amount of about 0.10% to about 0.20% by weight.

[0054] In some embodiments, the composition may also comprise at least one filler in an amount of about 0.5% to about 20% by weight, the at least one filler being selected from the group consisting of aragonite, clay, calcium carbonate, cellulose, nanocellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starch, diatomaceous earth, titanium dioxide, nanoclay, mica, and mixtures thereof. More preferably, the composition may comprise at least one filler in an amount of about 1.0% to about 5.0% by weight.

[0055] According to certain embodiments, the composition may also comprise at least one rheological modifier in an amount of about 0.01% to about 1.0% by weight, the at least one rheological modifier being selected from the group consisting of organic peroxides, carbodiimides, oxazolines, epoxides, and mixtures thereof. More preferably, the composition may comprise at least one rheological modifier in an amount of about 0.1% to about 0.5% by weight.

[0056] According to some embodiments, the composition may also contain about 0.5% to about 20% by weight of natural or synthetic fibers. More preferably, the composition may contain about 1.0% to about 5.0% by weight of fibers.

[0057] According to a particular embodiment, the composition also preferably comprises about 0.1 to about 20 weight percent of at least one biopolymer, the at least one biopolymer being selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, phenylbenzimidazole sulfonic acid, and mixtures thereof.

[0058] In general, the plastisol compositions according to this disclosure are biodegradable as determined by ASTM D6691. More preferably, each component of the plastisol composition is individually biodegradable as determined by ASTM D6691.

[0059] Furthermore, generally speaking, the composition is preferably little to no phthalates or phthalates-free. In some embodiments, the composition contains less than 1 weight percent of a phthalate-based compound. In more preferred embodiments, the composition is phthalate-free.

[0060] Advantageously, the plastisol compositions according to this disclosure are highly flexible and moldable. Therefore, the plastisol compositions can be used in many applications as a substitute for polyvinyl chloride (PVC)-based plastisols. In addition to eliminating the need for PVC itself, phthalate-based plasticizers, typically used with PVC, are avoided. Furthermore, as described above, the plastisol compositions according to this disclosure are biodegradable.

[0061] The above-described plastisol compositions may be prepared by a process comprising a first step of mixing at least one polyhydroxyalkanoate, as previously considered, with at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures, as previously considered, to form a slurry. This slurry is generally made from about 1 to about 49 weight percent of at least one polyhydroxyalkanoate and about 51 to about 99 weight percent of at least one plasticizer.

[0062] In addition, any other optional additives may be mixed into the slurry, and these additives include crosslinking agents, nucleating agents, additional biopolymers, and release agents.

[0063] This slurry is heated to a temperature of at least about 85°C (preferably about 105°C to about 125°C) to form a molten plastisol composition. This plastisol composition can then be molded to form various articles, such as flexible fishing lures.

[0064] For example, a fishing lure may be provided by this disclosure, comprising a soft plastic fishing bait molded from the above composition, at least one hook attached to the soft plastic fishing bait, and at least one weight attached to the soft plastic fishing bait.

[0065] In some cases, the fishing bait composition may also contain at least one attractant in an amount of about 0.1% to about 5.0% by weight, the at least one attractant being selected from the group consisting of glitter flakes, liquid colorants, powder pigments, fish scent attractants, and mixtures thereof. More preferably, the composition may contain at least one attractant in an amount of about 0.5% to about 2.0% by weight.

[0066] Advantageously, the soft plastic fishing baits (and lures containing such baits) and other flexible molded articles provided by this disclosure are biodegradable and do not contain PVC or phthalate-based compounds. Therefore, such baits and lures will biodegrade when lost in water and will not present environmental hazards associated with materials such as PVC and phthalate-based compounds.

[0067] Alternatively, the plastisol composition may be used as a coating or incorporated into an ink formulation, as described below.

[0068] In addition to the plastisol composition itself, the disclosure also provides an ink suitable for screen printing. Generally, this ink comprises at least one pigment and the above-mentioned plastisol composition.

[0069] Therefore, screen printing inks contain at least one pigment. In some embodiments, the pigment is preferably an inorganic pigment. However, in other embodiments, the pigment is preferably an organic pigment. Examples of pigments suitable for screen printing inks include Direct Blue 1, indigo dye, rhodamine, disperse red, cadmium green, carbon black, and titanium white. The amount of pigment in the ink is typically about 1% to about 30% by weight of the ink.

[0070] Screen printing inks also contain the plastisol mentioned above. The amount of plastisol in the ink is typically about 70 to 99 percent by weight.

[0071] Again, the plastisol composition comprises about 1 to about 49 weight percent of at least one polyhydroxyalkanoate and about 51 to about 99 weight percent of at least one plasticizer, wherein the at least one plasticizer is selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof. Preferably, the plastisol composition comprises about 1 to about 40 weight percent of at least one polyhydroxyalkanoate and about 60 to about 99 weight percent of at least one plasticizer.

[0072] In a particular embodiment, the plastisol composition of the ink more preferably comprises about 1 to about 10 weight percent of at least one polyhydroxyalkanoate.

[0073] In certain preferred embodiments, the plastisol composition may comprise a combination of plasticizers. For example, in some embodiments, the plastisol composition may comprise about 60 to about 80 weight percent of at least one citrate ester. This composition may also comprise about 10 to about 35 weight percent of at least one triglyceride.

[0074] Furthermore, a preferred citrate ester may be triethyl citrate, and a preferred triglyceride may be triacetin. Therefore, in certain embodiments, the plastisol composition may comprise a combination of these two plasticizers. For example, the plastisol composition may comprise about 60 to about 80 weight percent of triethyl citrate and about 10 to about 35 weight percent of triacetin.

[0075] In certain embodiments, the ink also preferably comprises at least one additive selected from the group consisting of fillers, rheological modifiers, stabilizers, and mixtures thereof.

[0076] In further embodiments, the disclosure also provides coated articles. According to one embodiment, a coated article includes at least a first surface and a coating applied over at least a portion of the first surface. The coating is applied by immersing the first surface in a plastisol composition.

[0077] In a particular preferred embodiment, the article is preferably a hand tool, such as a wrench, pliers, screwdriver, file, stone file, chisel, or hammer. The coating is applied across the handle of the tool to form a soft grip surface across the handle.

[0078] The above-described plastisol composition may be used for immersion coating of tool handles or other surfaces to be coated. As previously discussed, this plastisol comprises about 1 to about 40 weight percent of at least one polyhydroxyalkanoate and about 60 to about 99 weight percent of at least one plasticizer, the at least one plasticizer being selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof.

[0079] Embodiment This disclosure is further illustrated by the following embodiments. Embodiment 1. A composition for a plastisol, wherein the composition is Approximately 1 to approximately 49 weight percent of at least one polyhydroxyalkanoate, A composition comprising at least one plasticizer in an amount of approximately 51 to approximately 99 percent by weight, wherein the at least one plasticizer is selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof. Embodiment 2. The composition according to Embodiment 1, wherein the composition comprises about 1 to about 40 weight percent of at least one polyhydroxyalkanoate and about 60 to about 99 weight percent of at least one plasticizer. Embodiment 3. The composition according to Embodiment 1, wherein the composition comprises at least one polyhydroxyalkanoate in an amount of about 1 to about 10 weight percent. Embodiment 4. The composition according to any of the prior embodiments, wherein at least one plasticizer is a citrate ester. Embodiment 5. The composition according to any of the prior embodiments, wherein at least one plasticizer is a triglyceride. Embodiment 6. The composition according to any one of Embodiments 1 to 3, wherein the composition comprises about 60 to about 80 percent by weight of at least one citrate ester. Embodiment 7. The composition according to Embodiment 6, wherein the composition further comprises about 10 to about 35 weight percent of at least one triglyceride. Embodiment 8. The composition according to any one of Embodiments 1 to 3, wherein the composition comprises about 60 to about 80 weight percent of triethyl citrate. Embodiment 10. The composition according to Embodiment 8, wherein the composition further comprises about 10 to about 35 weight percent of triacetin. Embodiment 11. The composition according to any one of Embodiments 1 to 3, wherein the composition comprises at least one epoxidized vegetable oil selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized coconut oil, epoxidized soybean oil, and mixtures thereof. Embodiment 12. The composition according to any one of Embodiments 1 to 3, wherein the composition comprises epoxidized soybean oil. Embodiment 13. The composition according to any of the prior embodiments, further comprising about 0.01 to about 0.5 weight percent of at least a crosslinking agent, wherein at least the crosslinking agent is selected from the group consisting of organic peroxides, epoxides, carbodiimides, oxazolines, and mixtures thereof. Embodiment 14. The composition according to any of the prior embodiments, further comprising about 0.01 to about 1 weight percent of at least one nucleating agent, wherein the at least one nucleating agent is selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, and mixtures thereof. Embodiment 15. The composition according to any of the prior embodiments, further comprising about 0.1 to about 20 weight percent of at least one biopolymer, wherein the at least one biopolymer is selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, phenylbenzimidazole sulfonic acid, and mixtures thereof. Embodiment 16. A composition according to any of the prior embodiments, wherein at least one polyhydroxyalkanoate comprises a polyhydroxyalkanoate copolymer, the polyhydroxyalkanoate copolymer comprises about 0.5 to about 25 mole percent of monomer repeating units, the monomer repeating units being selected from the group consisting of 4-hydroxybutyrate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, 3-hydroxydecanoate, and mixtures thereof. Embodiment 17. A composition according to any of the prior embodiments, wherein at least one polyhydroxyalkanoate comprises one or more poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P3HB-co-P3HHx) copolymers, and each P3HB-co-P3HHx copolymer comprises about 2 to about 15 mole percent of monomer repeating units of 3-hydroxyhexanoate. Embodiment 18. The composition according to any of the prior embodiments, wherein the composition is phthalate-free. Embodiment 19. The composition according to any of the prior embodiments, further comprising about 0.05% to about 1.0% by weight of at least one nucleating agent, wherein the at least one nucleating agent is selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clay, sorbitol, and mixtures thereof. Embodiment 20. The composition according to any of the prior embodiments, further comprising about 0.5% to about 20% by weight of at least one filler, wherein the at least one filler is selected from the group consisting of aragonite, clay, calcium carbonate, cellulose, nanocellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starch, diatomaceous earth, titanium dioxide, nanoclay, mica, and mixtures thereof. Embodiment 21. The composition according to any of the prior embodiments, further comprising about 0.01% to about 1.0% by weight of at least one rheological modifier, wherein the at least one rheological modifier is selected from the group consisting of organic peroxides, carbodiimides, oxazolines, epoxides, and mixtures thereof. Embodiment 22. The composition according to any of the prior embodiments, further comprising about 0.5% to about 20% by weight of natural or synthetic fibers. Embodiment 23. An ink for screen printing, At least one pigment, An ink comprising a plastisol composition described in any of the prior embodiments. Embodiment 24. The ink according to Embodiment 23, wherein the pigment is an inorganic pigment. Embodiment 25. The ink according to Embodiment 23, wherein the pigment is an organic pigment. Embodiment 26. The ink according to any one of Embodiments 23 to 25, wherein the ink further comprises at least one additive selected from the group consisting of fillers, rheological modifiers, stabilizers, and mixtures thereof. Embodiment 27. The ink according to any one of Embodiments 23 to 26, wherein the plastisol composition is present in the ink in an amount of about 70 to about 99 percent by weight of the ink. Embodiment 28. A coated article comprising at least a first surface and a coating applied over at least a portion of the first surface, The coating is applied by immersing the first surface in a plastisol composition, and the plastisol composition is Approximately 1 to approximately 49 weight percent of at least one polyhydroxyalkanoate, A coated article comprising at least one plasticizer in an amount of approximately 51 to approximately 99 percent by weight, wherein the at least one plasticizer is selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof. Embodiment 29. The coated article according to Embodiment 28, wherein the plastisol composition comprises about 1 to about 40 weight percent of at least one polyhydroxyalkanoate and about 60 to about 99 weight percent of at least one plasticizer. Embodiment 30. A coated article according to Embodiment 28 or 29, wherein the article is a hand tool and the coating forms a hand grip. Embodiment 31. A fishing lure, A soft plastic fishing bait molded from the composition described in any of Embodiments 1 to 22, A soft plastic fishing bait with at least one hook attached, A fishing lure, including at least one weight attached to a soft plastic fishing bait. Embodiment 32. The fish-lure lure according to Embodiment 31, wherein the composition further comprises at least one attractant in an amount of about 0.1% to about 5.0% by weight, the at least one attractant being selected from the group consisting of glitter flakes, liquid colorants, powder pigments, fish scent attractants, and mixtures thereof. Embodiment 33. A process for manufacturing a molded article, A step of mixing at least one polyhydroxyalkanoate with at least one plasticizer selected from the group consisting of epoxidized vegetable oil, citrate ester, triglyceride, and mixtures thereof to form a slurry containing about 1 to about 49 weight percent of at least one polyhydroxyalkanoate and about 51 to about 99 weight percent of at least one plasticizer, The steps include heating the slurry to a temperature of at least about 85°C to form a molten mixture, The steps include injecting the mixture into a mold, The steps include cooling the mixture in the mold to form a solidified molded article, A process including the step of removing a molded article from a mold. [Examples]

[0080] The following non-limiting embodiments illustrate various additional aspects of the present invention. Unless otherwise indicated, temperatures are in degrees Celsius, and percentages are by weight based on the dry weight of the formulation. Example 1 In this example, a plastisol solution was prepared using two different forms of poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P3HB-co-P3HHx) copolymer, triethyl citrate, and triacetin. The compositions are shown in Table 1 below. The components were first combined using a Silverson mixer via high-shear mixing. This mixture was left overnight to fully plasticize the polyhydroxyalkanoate polymer. The mixture was heated to 110°C to transition from an opaque to a transparent mixture. This transparent mixture was then injected into a mold and cooled for 5 minutes to form a solid part. The plastisol solution for Example 2 was prepared in the same manner as in Example 1, except that the Example 2 composition shown in Table 1 below was used. The resulting molded part was a softer solid compared to Example 1. Example 3. A plastisol solution was prepared in the same manner as in Example 1, except that the Example 3 composition shown in Table 1 below was used. The resulting molded part was a softer solid compared to both Examples 1 and 2. [Table 1] Example 4. A plastisol solution was prepared in the same manner as in Example 1, except that the Example 4 composition shown in Table 2 below was used. The plastisol solution was heated to 110°C, injected into a mold, and cooled for 5 minutes to form a solid part. Example 5. A plastisol solution was prepared in the same manner as in Example 1, except that the composition of Example 4 shown in Table 2 below was used. The plastisol solution was heated to 110°C, injected into a mold, and cooled for 5 minutes to form a solid part. The resulting molded part was a softer solid compared to Example 4. Example 6. A plastisol solution was prepared in the same manner as in Example 1, except that the composition of Example 4 shown in Table 2 below was used. The plastisol solution was heated to 110°C, injected into a mold, and cooled for 5 minutes to form a solid part. The resulting molded part was a softer solid compared to Examples 4 and 5. [Table 2] Example 7. A plastisol solution was prepared using the formulation from Example 4. Dry pigment and glitter were added to the solution, and then the solution was heated to a plastisol concentration of 0.067 g pigment / mL. The colored solution was then heated to 110°C, injected into a mold, and cooled for 5 minutes to form a colored solid part.

[0081] The foregoing description of preferred embodiments of the Disclosure is provided for illustrative and explanatory purposes only. It is not intended to be exhaustive or to limit the Disclosure to any specific form disclosed. Obvious modifications or changes are possible in light of the above teachings. These embodiments are selected and described in an effort to provide the best illustration of the principles of the Disclosure and their practical applications, thereby enabling those skilled in the art to utilize the Disclosure in various embodiments and with various modifications to suit a particular intended use.

Claims

1. A composition for a plastisol, wherein the composition is Approximately 1 to approximately 49 weight percent of at least one polyhydroxyalkanoate, A composition comprising at least one plasticizer in an amount of about 51 to about 99 percent by weight, wherein the at least one plasticizer is selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof.

2. The composition according to claim 1, wherein the composition comprises about 1 to about 10 weight percent of the at least one polyhydroxyalkanoate.

3. The composition according to claim 1, wherein the composition comprises at least one citrate ester in an amount of about 60 to about 80 percent by weight.

4. The composition according to claim 3, wherein the composition further comprises about 10 to about 35 weight percent of at least one triglyceride.

5. The composition according to claim 1, wherein the composition comprises about 60 to about 80% by weight of triethyl citrate.

6. The composition according to claim 5, wherein the composition further comprises about 10 to about 35 weight percent of triacetin.

7. The composition according to claim 1, wherein the composition comprises at least one epoxidized vegetable oil selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized coconut oil, epoxidized soybean oil, and mixtures thereof.

8. The composition according to claim 1, wherein the composition comprises epoxidized soybean oil.

9. The composition according to claim 1, wherein the composition further comprises about 0.01 to about 0.5 weight percent of at least a crosslinking agent, the at least crosslinking agent being selected from the group consisting of organic peroxides, epoxides, carbodiimides, oxazolines, and mixtures thereof.

10. The composition according to claim 1, further comprising about 0.01 to about 1 weight percent of at least one nucleating agent, wherein the at least one nucleating agent is selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, and mixtures thereof.

11. The composition according to claim 1, further comprising about 0.1 to about 20 weight percent of at least one biopolymer, wherein the at least one biopolymer is selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, phenylbenzimidazole sulfonic acid, and mixtures thereof.

12. The composition according to claim 1, wherein the at least one polyhydroxyalkanoate comprises a polyhydroxyalkanoate copolymer, the polyhydroxyalkanoate copolymer comprises about 0.5 to about 25 mole percent of monomer repeating units, and the monomer repeating units are selected from the group consisting of 4-hydroxybutyrate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, 3-hydroxydecanoate, and mixtures thereof.

13. The composition according to claim 1, wherein the at least one polyhydroxyalkanoate comprises one or more poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P3HB-co-P3HHx) copolymers, each P3HB-co-P3HHx copolymer comprising about 2 to about 15 mole percent of monomer repeating units of 3-hydroxyhexanoate.

14. The composition according to claim 1, wherein the composition is phthalate-free.

15. Ink for screen printing, At least one pigment, An ink comprising the plastisol composition described in claim 1.

16. The ink according to claim 15, wherein the pigment is an inorganic pigment.

17. The ink according to claim 15, wherein the pigment is an organic pigment.

18. The ink according to claim 15, wherein the ink further comprises at least one additive selected from the group consisting of fillers, rheological modifiers, stabilizers, and mixtures thereof.

19. The ink according to claim 15, wherein the plastisol composition is present in the ink in an amount of about 70 to about 99% by weight of the ink.

20. A coated article comprising at least a first surface and a coating applied over at least a portion of the first surface, The coating is applied by immersing the first surface in a plastisol composition, and the plastisol composition is Approximately 1 to approximately 49 weight percent of at least one polyhydroxyalkanoate, A coated article comprising at least one plasticizer in an amount of about 51 to about 99 percent by weight, wherein the at least one plasticizer is selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof.

21. The coated article according to claim 20, wherein the article is a hand tool and the coating forms a hand grip.

22. It is a fishing lure, A soft plastic fishing bait molded from the composition described in claim 1, At least one hook attached to the aforementioned soft plastic fishing bait, A fishing lure comprising at least one weight attached to the aforementioned soft plastic fishing bait.

23. A process for manufacturing molded articles, A step of mixing at least one polyhydroxyalkanoate with at least one plasticizer selected from the group consisting of epoxidized vegetable oil, citrate ester, triglyceride, and mixtures thereof to form a slurry containing about 1 to about 49 weight percent of the at least one polyhydroxyalkanoate and about 51 to about 99 weight percent of the at least one plasticizer, The steps include heating the slurry to a temperature of at least about 85°C to form a molten mixture, The steps include injecting the mixture into a mold, The steps include: cooling the mixture in the mold to form a solidified molded article; A process comprising the step of removing the molded article from the mold.

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