Biodegradable PVC substitute

Abstract

The present disclosure provides a plastisol composition comprising from about 1% to about 49% by weight of at least one polyhydroxyalkanoate. The plastisol composition also includes from about 51% to about 99% by weight of at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrate esters, triglycerides, and mixtures thereof. A screen printing ink comprising the plastisol is also disclosed.

Description

Technical Field

[0001] This disclosure relates to biodegradable polymer compositions. More specifically, this disclosure relates to biodegradable polymer compositions comprising poly(hydroxyalkanoates) that can be used to form plastisol and flexible molded articles. Background Technology

[0002] Polyvinyl chloride (PVC) is widely used in the plastics industry due to its unique physical and conversion properties. Specifically, PVC is used to produce highly flexible polymer compositions, such as plastisols. Typically, this type of flexible PVC is highly plasticized using phthalate-based plasticizers, which disrupt interchain interactions, reduce overall crystallinity, and enhance flexibility. Different applications use different amounts of plasticizer, and the amount determines the softness and flexibility.

[0003] However, from a health and environmental perspective, the use of PVC also presents numerous drawbacks. It is well known that PVC releases toxic byproducts into the environment, especially vinyl chloride, which has been identified as a carcinogen. Furthermore, the disposal of PVC-based products presents problems, as PVC hardly biodegrades when landfilled or leaked into the marine environment.

[0004] In addition, phthalate-based plasticizers, which are commonly used with PVC, are also considered endocrine disruptors.

[0005] Therefore, there is a need to provide alternative polymer compositions that can be used to replace plasticized PVC compositions in the production of plastisol and other flexible articles. Preferably, these compositions will be biodegradable and / or non-toxic. In particular, plastisol compositions should be PVC-free.

[0006] Ink comprising the above-described plastisol composition, such as screen printing ink, is also required. Furthermore, molded articles formed from the plastisol composition, such as fish bait, are also required.

[0007] In addition, it is desirable to provide a method for forming molded articles from the above-described plastisol composition. Summary of the Invention

[0008] According to this disclosure, a plastisol based on polyhydroxyalkanoate (PHA) satisfies the above and other requirements.

[0009] In one aspect, this disclosure provides a composition for plastisol. According to one embodiment, the plastisol composition comprises about 1% to about 49% by weight of at least one polyhydroxyalkanoate. The plastisol composition further comprises about 51% to about 99% by weight of at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof.

[0010] According to certain embodiments, the composition preferably comprises about 1% to about 40% by weight of at least one polyhydroxyalkanoate; and about 60% to about 99% by weight of at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides and mixtures thereof.

[0011] In some embodiments, the composition more preferably comprises about 1% to about 10% by weight of at least one polyhydroxyalkanoate.

[0012] In some cases, a single form of plasticizer may be used in the composition. For example, the composition may contain only citrate esters (e.g., triethyl citrate) as plasticizers. Alternatively, the composition may contain only triglycerides (e.g., triacetylglycerol) as plasticizers.

[0013] In other embodiments, the composition may comprise a combination of various plasticizers. According to some embodiments, the composition preferably comprises about 60% to about 80% by weight of at least one citrate ester. More preferably, the composition further comprises about 10% to about 35% by weight of at least one triglyceride.

[0014] In some embodiments, the composition more preferably contains about 60% to about 80% by weight of triethyl citrate. Still more preferably, the composition further contains about 10% to about 35% by weight of triacetylglycerol.

[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 some embodiments, the composition preferably further comprises about 0.01% to about 0.5% by weight of at least one crosslinking agent selected from the group consisting of organic peroxides, epoxides, carbodiimides, oxazolines, and mixtures thereof.

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

[0018] According to some embodiments, the composition also preferably contains about 0.1% to about 20% by weight of at least one biopolymer selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene adipate, polybutylene terephthalate, phenylbenzimidazole sulfonic acid, and mixtures thereof.

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

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

[0021] According to some embodiments, the composition is preferably free of phthalates.

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

[0023] In some embodiments, the composition may further comprise from about 0.5% to about 20% by weight of at least one filler 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 from about 1.0% to about 5.0% by weight of at least one filler.

[0024] According to some embodiments, the composition may further comprise about 0.01% to about 1.0% by weight of at least one rheology modifier selected from the group consisting of organic peroxides, carbodiimides, oxazolines, epoxides, and mixtures thereof. More preferably, the composition may comprise about 0.1% to about 0.5% by weight of at least one rheology modifier.

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

[0026] In a second aspect, this disclosure also provides an ink suitable for screen printing. According to one embodiment, the ink comprises at least one pigment and a plastisol composition, such as the plastisol composition described above. Thus, the plastisol composition further comprises about 1% to about 49% by weight of at least one polyhydroxyalkanoate and about 51% to about 99% by weight of at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof.

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

[0028] According to some embodiments, the ink preferably also contains 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% by weight of the ink.

[0030] In some embodiments, the plastisol composition of the ink more preferably contains about 1% to about 10% by weight of at least one polyhydroxyalkanoate.

[0031] According to some embodiments, the plastisol composition of the ink preferably contains about 60% to about 80% by weight of at least one citrate. More preferably, the plastisol composition further contains about 10% to about 35% by weight of at least one triglyceride.

[0032] In some embodiments, the plastisol composition of the ink more preferably contains about 60% to about 80% by weight of triethyl citrate. Still more preferably, the plastisol composition further contains about 10% to about 35% by weight of triacetylglycerol.

[0033] On the other hand, this disclosure also provides a coated article. According to one embodiment, the coated article includes at least a first surface and a coating applied to at least a portion of the first surface. The coating is applied by immersion coating the first surface in a plastisol composition. The plastisol contains about 1% to about 49% by weight of at least one polyhydroxyalkanoate and about 51% to about 99% by weight of at least one plasticizer, said plasticizer being selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof. More preferably, the plastisol contains about 1% to about 40% by weight of at least one polyhydroxyalkanoate and about 60% to about 99% by weight of at least one plasticizer.

[0034] In some embodiments, the article is preferably a hand tool, and the coating forms a handle.

[0035] On the other hand, this disclosure provides a fish bait. According to one embodiment, the fish bait comprises a soft plastic fish bait molded from the above-described plastisol composition, wherein the plastisol composition contains about 1% to about 49% by weight of at least one polyhydroxyalkanoate and about 51% to about 99% by weight of at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof.

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

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

[0038] In another aspect, this disclosure provides a method for manufacturing a molded article. According to one embodiment, the method includes the steps of: mixing at least one polyhydroxyalkanoate with at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof to form a slurry comprising about 1% to about 49% by weight of at least one polyhydroxyalkanoate and about 51% to about 99% by weight of at least one plasticizer. The method further includes the steps of: heating the slurry to a temperature of at least about 85°C to form a molten mixture; then injecting the molten mixture into a mold; then cooling the mixture within the mold to form a solidified molded article; and finally removing the molded article from the mold. Detailed Implementation

[0039] This disclosure provides a plastisol composition based on polyhydroxyalkanoates (PHAs), preferably biodegradable and free of phthalates. This disclosure also provides an ink for screen printing comprising the plastisol composition; and a coated article wherein the coating comprises the plastisol composition.

[0040] The plastisol composition contains at least one polyhydroxyalkanoate and also contains at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof.

[0041] The amount of at least one polyhydroxyalkanoate is typically from about 1% to about 49% by weight of the composition, and preferably from about 1% to about 40% by weight of the composition. More preferably, the at least one polyhydroxyalkanoate accounts for about 1% to about 10% by weight of the composition.

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

[0043] In some embodiments, at least one polyhydroxyalkanoate preferably comprises a polyhydroxyalkanoate copolymer. For example, at least one polyhydroxyalkanoate may comprise a polyhydroxyalkanoate copolymer containing about 0.5 mol% to about 25 mol% of a monomer repeating unit 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 contains about 2 mol% to about 15 mol% of a 3-hydroxyhexanoate monomer repeating unit.

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

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

[0046] Examples of suitable citrate esters that can be used as plasticizers in compositions include triethyl citrate, tributyl citrate, acetylated triethyl citrate, and acetylated tributyl citrate. Preferred citrate ester is triethyl citrate.

[0047] In some embodiments, the preferred triglyceride plasticizer may be triacetylglycerol.

[0048] Typically, the amount of plasticizer in the composition is from about 51% by weight to about 99% by weight, and more preferably from about 60% by weight to about 99% by weight.

[0049] In some cases, the composition may contain only about 60% to about 99% by weight of a single plasticizer. For example, the composition may contain only citrate esters, such as triethyl citrate, or only triglycerides, such as triacetylglycerol.

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

[0051] As described above, the preferred citrate ester can be triethyl citrate, and the preferred triglyceride can be triacetylglycerol. Therefore, in some embodiments, the plastisol composition may comprise a combination of these two plasticizers. For example, the plastisol composition may comprise about 60% to about 80% by weight of triethyl citrate and about 10% to about 35% by weight of triacetylglycerol.

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

[0053] In some embodiments, the composition may further comprise about 0.05% to about 1.0% by weight of at least one nucleating agent, said 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 about 0.10% to about 0.20% by weight of at least one nucleating agent.

[0054] In some embodiments, the composition may further comprise from about 0.5% to about 20% by weight of at least one filler 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 further comprise from about 1.0% to about 5.0% by weight of at least one filler.

[0055] According to some embodiments, the composition may further comprise about 0.01% to about 1.0% by weight of at least one rheology modifier selected from the group consisting of organic peroxides, carbodiimides, oxazolines, epoxides, and mixtures thereof. More preferably, the composition may comprise about 0.1% to about 0.5% by weight of at least one rheology modifier.

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

[0057] According to some embodiments, the composition preferably also contains about 0.1% to about 20% by weight of at least one biopolymer, the biopolymer being selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene adipate, polybutylene terephthalate, phenylbenzimidazole sulfonic acid, and mixtures thereof.

[0058] Overall, according to this disclosure, the plastisol composition is biodegradable as determined by ASTM D6691. More preferably, each component in the plastisol composition is individually biodegradable as determined by ASTM D6691.

[0059] It is generally preferred that the composition contains little or no phthalates. In some embodiments, the composition contains less than 1% by weight of phthalate compounds. In more preferred embodiments, the composition is free of phthalate compounds.

[0060] Advantageously, according to this disclosure, the plastisol composition exhibits high flexibility and moldability. Therefore, this plastisol composition can be used as a substitute for polyvinyl chloride (PVC)-based plastisols in many applications. In addition to eliminating the need for PVC itself, it also avoids phthalate plasticizers typically used with PVC. Furthermore, as mentioned above, the plastisol composition according to this disclosure is biodegradable.

[0061] The above-described plastisol composition can be prepared by a method comprising: a first step of mixing at least one polyhydroxyalkanoate as described above with at least one plasticizer selected from epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof to form a slurry. The slurry typically consists of about 1% to about 49% by weight of at least one polyhydroxyalkanoate and about 51% to about 99% by weight of at least one plasticizer.

[0062] Any other optional additives can be incorporated into the slurry, including crosslinking agents, nucleating agents, additional biopolymers, release agents, etc.

[0063] The 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 into various articles, such as flexible fish bait.

[0064] For example, according to this disclosure, a fish bait may be provided, which consists of a soft plastic fish bait molded from the above composition, at least one fish hook attached to the soft plastic fish bait, and at least one weight attached to the soft plastic fish bait.

[0065] In some cases, the bait composition may also contain about 0.1% to about 5.0% by weight of at least one attractant, said attractant being selected from the group consisting of glitter powder, liquid colorant, powder pigment, fish-scented attractant, and mixtures thereof. More preferably, the composition may contain about 0.5% to about 2.0% by weight of at least one attractant.

[0066] Advantageously, the soft plastic fish baits (and lures containing such fish baits) and other flexible molded articles provided according to this disclosure are biodegradable and free of PVC or phthalate compounds. Therefore, such fish baits and lures biodegrade when lost in water bodies and do not pose environmental hazards associated with materials such as PVC and phthalate compounds.

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

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

[0069] Therefore, the screen printing ink contains 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 dioxide. The amount of pigment in the ink is typically from about 1% to about 30% by weight of the ink.

[0070] Screen printing inks also include the aforementioned plastisol. The amount of plastisol in the ink is typically from about 70% to about 99% by weight of the ink.

[0071] Similarly, the plastisol composition further comprises about 1% to about 49% by weight of at least one polyhydroxyalkanoate and about 51% to about 99% by weight of at least one plasticizer, the plasticizer being selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof. Preferably, the plastisol composition comprises about 1% to about 40% by weight of at least one polyhydroxyalkanoate and about 60% to about 99% by weight of at least one plasticizer.

[0072] In some embodiments, the plastisol composition of the ink more preferably contains about 1% to about 10% by weight of at least one polyhydroxyalkanoate.

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

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

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

[0076] On the other hand, this disclosure also provides coated articles. According to one embodiment, the coated article includes at least a first surface and a coating applied to at least a portion of the first surface. The coating is applied by immersion coating the first surface in a plastisol composition.

[0077] In some preferred embodiments, the article is preferably a hand tool, such as a wrench, pliers, screwdriver, file, rasp, chisel, or hammer. The coating is applied to the handle of the tool to form a soft gripping surface.

[0078] The above-described plastisol composition can be used for dip coating of tool handles or other surfaces to be coated. As described above, the plastisol contains about 1% to about 40% by weight of at least one polyhydroxyalkanoate and about 60% to about 99% by weight of at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides, and mixtures thereof.

[0079] Implementation

[0080] The present invention is further illustrated by the following embodiments:

[0081] Implementation Method 1. A composition for plastisol, comprising:

[0082] At least one polyhydroxyalkanoate comprising about 1% by weight to about 49% by weight; and

[0083] About 51% to about 99% by weight of at least one plasticizer, wherein the plasticizer is selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides and mixtures thereof.

[0084] Embodiment 2. The composition according to Embodiment 1, wherein the composition comprises about 1% to about 40% by weight of at least one polyhydroxyalkanoate and about 60% to about 99% by weight of at least one plasticizer.

[0085] Embodiment 3. The composition according to Embodiment 1, wherein the composition comprises about 1% to about 10% by weight of at least one polyhydroxyalkanoate.

[0086] Embodiment 4. The composition according to any of the foregoing embodiments, wherein the at least one plasticizer is composed of a citrate ester.

[0087] Embodiment 5. The composition according to any of the foregoing embodiments, wherein the at least one plasticizer is composed of triglycerides.

[0088] Embodiment 6. The composition according to any one of Embodiments 1 to 3, wherein the composition comprises about 60% to about 80% by weight of at least one citrate ester.

[0089] Embodiment 7. The composition according to Embodiment 6, wherein the composition further comprises about 10% to about 35% by weight of at least one triglyceride.

[0090] Embodiment 8. The composition according to any one of Embodiments 1-3, wherein the composition comprises about 60% to about 80% by weight of triethyl citrate.

[0091] Example 10. The composition according to Example 8, wherein the composition further comprises about 10% by weight to about 35% by weight of triacetylglycerol.

[0092] Embodiment 11. The composition according to any one of Embodiments 1-3, 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.

[0093] Embodiment 12. The composition according to any one of Embodiments 1-3, wherein the composition comprises epoxidized soybean oil.

[0094] Embodiment 13. The composition according to any one of the foregoing embodiments, wherein the composition further comprises about 0.01% by weight to about 0.5% by weight of at least one crosslinking agent selected from the group consisting of organic peroxides, epoxides, carbodiimides, oxazolines, and mixtures thereof.

[0095] Embodiment 14. The composition according to any one of the foregoing embodiments, wherein the composition further comprises about 0.01% by weight to about 1% by weight of at least one nucleating agent selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, and mixtures thereof.

[0096] Embodiment 15. The composition according to any one of the foregoing embodiments, wherein the composition further comprises about 0.1% to about 20% by weight of at least one biopolymer selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene adipate, polybutylene terephthalate, phenylbenzimidazole sulfonic acid, and mixtures thereof.

[0097] Example 16. The composition according to any one of the preceding embodiments, wherein the at least one polyhydroxyalkanoate comprises a polyhydroxyalkanoate copolymer, the polyhydroxyalkanoate copolymer comprising about 0.5 mol% to about 25 mol% of a monomer repeating unit selected from the group consisting of 4-hydroxybutyrate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, 3-hydroxydecanoate and mixtures thereof.

[0098] Embodiment 17. The composition according to any one of the preceding embodiments, wherein the at least one polyhydroxyalkanoate comprises one or more poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P3HB-co-P3HHx) copolymers, wherein each P3HB-co-P3HHx copolymer comprises about 2 mol% to about 15 mol% of a monomer repeating unit of 3-hydroxyhexanoate.

[0099] Embodiment 18. The composition according to any one of the foregoing embodiments, wherein the composition is free of phthalates.

[0100] Embodiment 19. The composition according to any one of the foregoing embodiments further comprises about 0.05% by weight to about 1.0% by weight of at least one nucleating agent, said nucleating agent being selected from the group consisting of pentaerythritol, dipentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clay, sorbitol and mixtures thereof.

[0101] Embodiment 20. The composition according to any one of the foregoing embodiments further comprises about 0.5% by weight to about 20% by weight of at least one filler 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.

[0102] Embodiment 21. The composition according to any one of the foregoing embodiments further comprises about 0.01% by weight to about 1.0% by weight of at least one rheology modifier, said rheology modifier being selected from the group consisting of organic peroxides, carbodiimides, oxazolines, epoxides and mixtures thereof.

[0103] Embodiment 22. The composition according to any one of the foregoing embodiments further comprises about 0.5% by weight to about 20% by weight of natural or synthetic fibers.

[0104] Embodiment 23. An ink for screen printing, comprising:

[0105] At least one pigment; and

[0106] The plastisol composition according to any one of the foregoing embodiments.

[0107] Embodiment 24. The ink according to Embodiment 23, wherein the pigment is an inorganic pigment.

[0108] Embodiment 25. The ink according to Embodiment 23, wherein the pigment is an organic pigment.

[0109] 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, rheology modifiers, stabilizers and mixtures thereof.

[0110] 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% by weight of the ink.

[0111] Embodiment 28. A coated article comprising at least a first surface and a coating applied to at least a portion of the first surface.

[0112] The coating is applied by dip-coating a first surface in a plastisol composition, wherein the plastisol composition comprises:

[0113] At least one polyhydroxyalkanoate comprising about 1% by weight to about 49% by weight; and

[0114] About 51% to about 99% by weight of at least one plasticizer, said plasticizer being selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides and mixtures thereof.

[0115] Embodiment 29. The coated article according to Embodiment 28, wherein the plastisol composition comprises about 1 to about 40% by weight of at least one polyhydroxyalkanoate and about 60 to about 99% by weight of at least one plasticizer.

[0116] Embodiment 30. The coated article according to Embodiment 28 or 29, wherein the article is a hand tool and the coating forms a handle.

[0117] Implementation Method 31. A fish bait, comprising:

[0118] Soft plastic fish bait molded from the composition of any one of embodiments 1-22;

[0119] At least one hook attached to the soft plastic bait; and

[0120] At least one weight attached to the soft plastic bait.

[0121] Embodiment 32. The fish bait according to Embodiment 31, wherein the composition further comprises about 0.1% by weight to about 5.0% by weight of at least one attractant selected from the group consisting of glitter powder, liquid colorant, powder pigment, fish-scented attractant and mixtures thereof.

[0122] Implementation Method 33. A method for manufacturing a molded article, comprising the following steps:

[0123] Mix at least one polyhydroxyalkanoate and at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides and mixtures thereof to form a slurry comprising about 1% to about 49% by weight of the at least one polyhydroxyalkanoate and about 51% to about 99% by weight of the at least one plasticizer;

[0124] The slurry is heated to a temperature of at least about 85°C to form a molten mixture;

[0125] The mixture is injected into the mold;

[0126] The mixture is cooled within a mold to form a solidified molded article; and

[0127] Remove the molded article from the mold.

[0128] Example

[0129] The following non-limiting examples illustrate various additional aspects of the invention. Unless otherwise stated, temperatures are in degrees Celsius, and percentages are based on the dry weight of the formulation by weight.

[0130] Example 1. In this example, a plastisol solution was prepared using a combination of two different forms of poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P3HB-co-P3HHx) copolymer, triethyl citrate, and glyceryl triacetate. Its composition is shown in Table 1 below. First, the components were mixed using a Silverson mixer via high-shear mixing. The mixture was allowed to stand overnight to allow the polyhydroxybutyrate polymer to fully plasticize. The mixture was then heated to 110°C, causing it to change from opaque to transparent. This transparent mixture was then poured into a mold and cooled for 5 minutes to form a solid part.

[0131] Example 2. A plastisol solution was prepared in the same manner as in Example 1, but using the composition of Example 2 as shown in Table 1 below. The resulting molded part was softer than the solid of Example 1.

[0132] Example 3. A plastisol solution was prepared in the same manner as in Example 1, but using the composition of Example 3 shown in Table 1 below. The resulting molded part was softer than the solids of Examples 1 and 2.

[0133]

[0134] Example 4. A plastisol solution was prepared in the same manner as in Example 1, but using the composition of Example 4 as shown in Table 2 below. The plastisol solution was heated to 110°C, poured into a mold, and cooled for 5 minutes to form a solid part.

[0135] Example 5. A plastisol solution was prepared in the same manner as in Example 1, but using the composition of Example 4 as shown in Table 2 below. The plastisol solution was heated to 110°C, poured into a mold, and cooled for 5 minutes to form a solid part. The resulting molded part was softer than the solid part of Example 4.

[0136] Example 6. A plastisol solution was prepared in the same manner as in Example 1, but using the composition of Example 4 as shown in Table 2 below. The plastisol solution was heated to 110°C, poured into a mold, and cooled for 5 minutes to form a solid part. The resulting molded part was softer than the solid parts of Examples 4 and 5.

[0137]

[0138] Example 7. A plastisol solution was prepared using the formulation of Example 4. Dry pigment and glitter powder were added to the solution prior to heating to a concentration of 0.067 g pigment per mL of plastisol. The colored solution was then heated to 110°C, poured into a mold, and cooled for 5 minutes to form a colored solid part.

[0139] The foregoing description of preferred embodiments of this disclosure is for illustrative purposes only. This disclosure is not exhaustive or intended to limit it to the precise forms disclosed. Obvious modifications or variations are possible in light of the foregoing teachings. These embodiments were chosen and described to best illustrate the principles of the invention and its practical application, thereby enabling those skilled in the art to utilize this disclosure in various embodiments and modifications to suit a particular intended use.

Claims

1. A composition for plastisol, comprising: At least one polyhydroxyalkanoate comprising about 1% to about 49% by weight; and About 51% to about 99% by weight of at least one plasticizer, said plasticizer being selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides and mixtures thereof.

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

3. The composition of claim 1, wherein the composition comprises about 60% to about 80% by weight of at least one citrate ester.

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

5. The composition of 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% by weight of triacetylglycerol.

7. The composition of 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% by weight of at least one crosslinking agent selected from the group consisting of organic peroxides, epoxides, carbodiimides, oxazolines, and mixtures thereof.

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

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

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

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

14. The composition of claim 1, wherein the composition is free of phthalates.

15. An ink for screen printing, comprising: At least one pigment; and The plastisol composition according to 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 of claim 15, wherein the ink further comprises at least one additive selected from the group consisting of fillers, rheology modifiers, stabilizers, and mixtures thereof.

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

20. A coated article comprising at least a first surface and a coating applied to at least a portion of the first surface. The coating is applied by dip-coating the first surface in a plastisol composition, wherein the plastisol composition comprises: At least one polyhydroxyalkanoate comprising about 1% to about 49% by weight; and About 51% to about 99% by weight of at least one plasticizer, said plasticizer being selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides and mixtures thereof.

21. The coated article of claim 20, wherein the coated article is a hand tool and the coating forms a handle.

22. A type of fish bait, comprising: Soft plastic fish bait molded from the composition of claim 1; At least one fishhook attached to the soft plastic bait; as well as At least one weight attached to the soft plastic bait.

23. A method for manufacturing a molded article, comprising the following steps: Mix at least one polyhydroxyalkanoate and at least one plasticizer selected from the group consisting of epoxidized vegetable oils, citrates, triglycerides and mixtures thereof to form a slurry comprising about 1% to about 49% by weight of the at least one polyhydroxyalkanoate and about 51% to about 99% by weight of the at least one plasticizer; The slurry is heated to a temperature of at least about 85°C to form a molten mixture; The mixture is injected into the mold; The mixture is cooled within the mold to form a solidified molded article; as well as Remove the molded product from the mold.

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