Biodegradable resin composition and biodegradable article manufactured using same

Abstract

The present disclosure relates to: a biodegradable resin composition; and a biodegradable article manufactured using same. The biodegradable resin composition comprises a polyhydroxyalkanoate (PHA) resin and a plasticizer, and exhibits a plasticizer absorption rate controlled to a specific range.

Description

Biodegradable resin composition and biodegradable article manufactured using the same

[0001] The present disclosure relates to a biodegradable resin composition used to manufacture a biodegradable article having desired hardness and permeability.

[0002] Biodegradable resins are emerging as an alternative to conventional petroleum-based synthetic resins. These biodegradable resins have a lower carbon footprint than petroleum-based synthetic resins and are designed to be reintegrated into the environment through composting and decomposition after use. This contrasts with the usage of petroleum-based synthetic resins, which often end up as waste. Therefore, consumer demand for eco-friendly and sustainable products is expected to increase in the future, and to meet both consumer demand and environmental regulations, application strategies for biodegradable resins are expected to be necessary.

[0003] One example of such applications is the use of biodegradable resins to manufacture fishing bait. Specifically, fishing is a popular hobby worldwide, widely known as an activity that allows people to enjoy nature and relieve stress. Many synthetic resin (plastic) products are used in this type of fishing, and the increase in fishing activity is also leading to a rise in the generation of synthetic resin waste. In particular, soft baits and hard baits are mostly composed of synthetic resins.

[0004] The above-mentioned synthetic resin baits, if lost or discarded in the water, become marine debris. This can pollute the marine ecosystem and harm various marine animals. Furthermore, if the baits are left in the water for extended periods, they can become microplastics, affecting not only marine animals but also humans, potentially leading to even greater environmental problems.

[0005] Therefore, it is necessary to develop a technology to manufacture biodegradable items such as bait using biodegradable resins that decompose well not only in soil but also in the ocean.

[0006] In order to solve the above-mentioned conventional problems, the object of the present disclosure is to provide a biodegradable resin composition that can be used to manufacture a biodegradable article having desired hardness and permeability while being biodegradable not only in soil but also in the ocean.

[0007] In addition, another object of the present disclosure is to provide a biodegradable article manufactured using the biodegradable resin composition.

[0008] The present disclosure provides a biodegradable resin composition comprising a polyhydroxyalkanoate (PHA) resin and a plasticizer, and having a plasticizer absorption rate of 20% or more as measured according to ASTM D3367-95.

[0009] According to one embodiment of the present disclosure, the polyhydroxyalkanoate (PHA) resin may include 50 to 99 wt% of repeating units (3HB) derived from 3-hydroxybutyrate based on the total weight of the polyhydroxyalkanoate (PHA) resin.

[0010] According to another embodiment of the present disclosure, the weight average molecular weight (Mw) of the polyhydroxyalkanoate (PHA) resin may be 100,000 to 1,000,000 g / mol.

[0011] According to another embodiment of the present disclosure, the plasticizer may include at least one selected from the group consisting of cashew nut shell liquid (CNSL), triethyl citrate (TEC), and acetyl tributyl citrate (ATBC).

[0012] According to another embodiment of the present disclosure, the polyhydroxyalkanoate (PHA) resin comprises 85 to 99 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, and the plasticizer may comprise the cashew nut shell oil.

[0013] According to another embodiment of the present disclosure, the polyhydroxyalkanoate (PHA) resin comprises 65 to 75 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, and the plasticizer may comprise at least one selected from the group consisting of the cashew nut shell oil, the triethyl citrate, and the acetyltributyl citrate.

[0014] According to another embodiment of the present disclosure, the mixing ratio of the polyhydroxyalkanoate (PHA) resin and the plasticizer may be a weight ratio of 30 to 85:15 to 70.

[0015] According to another embodiment of the present disclosure, the plasticizer absorption rate may be from 40 to 200%.

[0016] Meanwhile, the present disclosure provides a biodegradable article manufactured from the biodegradable resin composition.

[0017] According to one embodiment of the present disclosure, the polyhydroxyalkanoate (PHA) resin included in the biodegradable resin composition includes 65 to 75 wt% of a repeating unit derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, and the plasticizer included in the biodegradable resin composition includes at least one selected from the group consisting of cashew nut shell oil, triethyl citrate, and acetyltributyl citrate, and the Shore A hardness of the biodegradable article may be 0 to 25.

[0018] According to another embodiment of the present disclosure, the polyhydroxyalkanoate (PHA) resin included in the biodegradable resin composition includes 85 to 99 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, the plasticizer included in the biodegradable resin composition includes cashew nut shell oil, and the permeability of the biodegradable article may be 70 to 100%.

[0019] According to another embodiment of the present disclosure, the biodegradable article may be bait.

[0020] Since the biodegradable resin composition according to the present disclosure comprises a polyhydroxyalkanoate (PHA) resin and a biodegradable (eco-friendly) plasticizer and exhibits a controlled plasticizer absorption rate above a specific range, when a biodegradable article is manufactured using the same, a biodegradable article (e.g., bait) having a desired hardness and / or permeability and excellent biodegradability can be provided.

[0021] Hereinafter, the present disclosure will be described in detail. However, the present disclosure is not limited to the contents disclosed below, and may be modified in various forms as long as the gist of the invention is not changed.

[0022] The word "comprising" or "including" in this specification is intended to specify particular features, regions, steps, processes, elements and / or components, and does not exclude the presence or addition of other features, regions, steps, processes, elements and / or components, unless specifically stated to the contrary.

[0023] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification are to be understood as being modified by the term “about” in all cases unless otherwise specified.

[0024]

[0025] Polyhydroxyalkanoate (PHA) resins have properties similar to those of petroleum-based synthetic resins such as polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), and polybutylene succinate adipate (PBSA), while exhibiting excellent biodegradability not only in soil but also in the ocean.

[0026] Since the physical properties (e.g., hardness, permeability, etc.) of a biodegradable article manufactured using a biodegradable resin composition including the above polyhydroxyalkanoate (PHA) resin can be determined depending on the crystallinity, chemical structure, etc. of the polyhydroxyalkanoate (PHA) resin, it is necessary to control the crystallinity, chemical structure, etc. of the polyhydroxyalkanoate (PHA) resin in order to obtain a biodegradable article having the desired physical properties.

[0027] In particular, when the biodegradable article in the present disclosure is a bait, also called a lure, the bait manufactured using the biodegradable resin composition (specifically, the biodegradable resin composition for bait) must have the desired hardness and / or permeability to increase commercial viability.

[0028] Accordingly, the present disclosure aims to provide a biodegradable article having a desired hardness and / or permeability by controlling the crystallinity, chemical structure, etc. of a polyhydroxyalkanoate (PHA) resin through the degree of plasticization, and manufacturing a biodegradable article using a biodegradable resin composition containing the same.

[0029]

[0030] Biodegradable resin composition

[0031] The biodegradable resin composition of the present disclosure comprises a polyhydroxyalkanoate (PHA) resin; and a plasticizer, and has a plasticizer absorption rate of 20% or more as measured according to ASTM D3367-95. Hereinafter, each component included in the biodegradable resin composition of the present disclosure will be described in detail.

[0032]

[0033] polyhydroxyalkanoate (PHA) resin

[0034] The polyhydroxyalkanoate (PHA) resin included in the biodegradable resin composition of the present disclosure is a biodegradable resin having thermoplasticity accumulated within microbial cells. Specifically, the PHA resin is a resin obtained through cell disruption of a microbial cell using a mechanical or physical method, or a resin obtained through cell disruption of a microbial cell using a non-mechanical or chemical method, and may have various crystallinities and chemical structures depending on the type of repeating unit constituting the resin.

[0035] Specifically, the PHA resin is a polymer (copolymer) including a repeating unit derived from at least one selected from the group consisting of 3-hydroxybutyrate (3HB), 3-hydroxypropionate (3HP), 3-hydroxyvalerate (3HV), 3-hydroxyhexanoate (3HH), 4-hydroxybutyrate (4HB), 4-hydroxyvalerate (4HV), 4-hydroxyhexanoate (4HH), 5-hydroxyvalerate (5HV), and 6-hydroxyhexanoate (6HH). However, it is not limited to these.

[0036] The above PHA resin can be divided into a crystalline PHA resin (cPHA), a semi-crystalline PHA resin (scPHA), or an amorphous PHA resin (aPHA) depending on the type of the monomer and the content of the repeating unit derived therefrom. Specifically, the PHA resin can be classified into cPHA, scPHA, or aPHA by controlling its crystallinity depending on the content of the repeating unit derived from 3-hydroxybutyrate (3HB).

[0037] According to the present disclosure, the PHA resin may contain 50 to 99 wt% of repeating units (3HB repeating units) derived from 3-hydroxybutyrate (3HB) based on the total weight of the PHA resin. Specifically, the PHA resin may contain 52 to 98 wt%, 55 to 97 wt%, 60 to 96 wt%, 62 to 95 wt%, or 64 to 94 wt% of the 3HB repeating units based on the total weight of the PHA resin, but is not limited thereto. The total weight of the PHA resin means the sum of the weight of the repeating units derived from 3-hydroxybutyrate (3HB) and the weight of the repeating units derived from other monomer(s) constituting the PHA resin. As the content of the 3HB repeating unit included in the PHA resin is within the above range, the processability of the biodegradable resin composition is secured, and a biodegradable article having the desired hardness and / or permeability can be provided.

[0038] For example, the PHA resin may contain the 3HB repeating unit in an amount of 70 to 99 wt%, 75 to 98.5 wt%, 80 to 98 wt%, 82 to 97.5 wt%, 85 to 97 wt%, 87 to 96.5 wt%, 85 to 99 wt%, 90 to 96 wt%, 91 to 95.5 wt%, 91.5 to 95 wt%, 92 to 94 wt%, or 92.5 to 93.5 wt% based on the total weight of the PHA resin, and may be classified as a scPHA resin.

[0039] In addition, the PHA resin may contain the 3HB repeating unit in an amount of 50 to 85 wt%, 52 to 82 wt%, 54 to 80 wt%, 55 to 78 wt%, 60 to 76 wt%, 62 to 75 wt%, 63 to 74 wt%, 64 to 73 wt%, 65 to 72 wt%, 65 to 75 wt%, 66 to 71 wt%, or 68 to 70 wt% based on the total weight of the PHA resin, and this may be classified as an aPHA resin.

[0040] The scPHA resin has crystallinity, and thus has higher hardness and lower permeability than the aPHA resin, which does not have crystallinity. Accordingly, when the biodegradable article of the present disclosure is bait, the biodegradable resin composition containing the scPHA resin is suitable for producing hard bait, and the biodegradable resin composition containing the aPHA resin is suitable for producing soft bait.

[0041] According to the present disclosure, the PHA resin may contain 1 to 50 wt% of a repeating unit derived from 4-hydroxybutyrate (4HB) (4HB repeating unit) based on the total weight of the PHA resin. Specifically, the PHA resin may contain 2 to 48 wt%, 3 to 45 wt%, 4 to 40 wt%, 5 to 38 wt%, or 6 to 35 wt% of the 4HB repeating unit based on the total weight of the PHA resin, but is not limited thereto. When the content of the 4HB repeating unit included in the PHA resin is within the above range, the processability of the biodegradable resin composition is secured, and a biodegradable article having a desired hardness and / or permeability can be provided.

[0042] For example, the PHA resin may contain the 4HB repeating unit in an amount of 1 to 30 wt%, 1.5 to 25 wt%, 2 to 20 wt%, 2.5 to 18 wt%, 3 to 15 wt%, 3.5 to 13 wt%, 1 to 15 wt%, 4 to 10 wt%, 4.5 to 9 wt%, 5 to 8.5 wt%, 6 to 8 wt%, or 6.5 to 7.5 wt% based on the total weight of the PHA resin, and may be classified as a scPHA resin.

[0043] In addition, the PHA resin may contain the 4HB repeating unit in an amount of 15 to 50 wt%, 18 to 48 wt%, 20 to 46 wt%, 22 to 45 wt%, 24 to 40 wt%, 25 to 38 wt%, 26 to 37 wt%, 27 to 36 wt%, 28 to 35 wt%, 25 to 35 wt%, 29 to 34 wt%, or 30 to 32 wt% based on the total weight of the PHA resin, and this may be classified as an aPHA resin.

[0044] Such PHA resin may be poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-co-4HB). At this time, the content of the 3HB repeating unit included in the poly(3-hydroxybutyrate-co-4-hydroxybutyrate) may be, but is not limited to, 50 to 99 wt%, 52 to 98 wt%, 55 to 97 wt%, 60 to 96 wt%, 62 to 95 wt%, or 65 to 94 wt%, based on the total weight of poly(3-hydroxybutyrate-co-4-hydroxybutyrate).

[0045] Specifically, the PHA resin may be a semi-crystalline poly(3-hydroxybutyrate-co-4-hydroxybutyrate) comprising 70 to 99 wt%, 75 to 98.5 wt%, 80 to 98 wt%, 82 to 97.5 wt%, 85 to 97 wt%, 87 to 96.5 wt%, 85 to 99 wt%, 90 to 96 wt%, 91 to 95.5 wt%, 91.5 to 95 wt%, 92 to 94 wt%, or 92.5 to 93.5 wt% of the 3HB repeating unit. Alternatively, the PHA resin may be an amorphous poly(3-hydroxybutyrate-co-4-hydroxybutyrate) comprising 50 to 85 wt%, 52 to 82 wt%, 54 to 80 wt%, 55 to 78 wt%, 60 to 76 wt%, 62 to 75 wt%, 63 to 74 wt%, 64 to 73 wt%, 65 to 72 wt%, 65 to 75 wt%, 66 to 71 wt%, or 68 to 70 wt% of the 3HB repeating unit.

[0046] Additionally, the PHA resin may be a semi-crystalline poly(3-hydroxybutyrate-co-4-hydroxybutyrate) comprising 1 to 30 wt%, 1.5 to 25 wt%, 2 to 20 wt%, 2.5 to 18 wt%, 3 to 15 wt%, 3.5 to 13 wt%, 1 to 15 wt%, 4 to 10 wt%, 4.5 to 9 wt%, 5 to 8.5 wt%, 6 to 8 wt%, or 6.5 to 7.5 wt% of the 4HB repeating unit. Alternatively, the PHA resin may be an amorphous poly(3-hydroxybutyrate-co-4-hydroxybutyrate) comprising 15 to 50 wt%, 18 to 48 wt%, 20 to 46 wt%, 22 to 45 wt%, 24 to 40 wt%, 25 to 38 wt%, 26 to 37 wt%, 27 to 36 wt%, 28 to 35 wt%, 25 to 35 wt%, 29 to 34 wt%, or 30 to 32 wt% of the 4HB repeating unit.

[0047] According to the present disclosure, the PHA resin may have a weight average molecular weight (Mw) of 100,000 to 1,000,000 g / mol. Specifically, the weight average molecular weight (Mw) of the PHA resin may be, but is not limited to, 150,000 to 950,000 g / mol, 200,000 to 900,000 g / mol, 250,000 to 850,000 g / mol, 300,000 to 825,000 g / mol, 350,000 to 800,000 g / mol, 375,000 to 775,000 g / mol, or 400,000 to 750,000 g / mol. As the weight average molecular weight (Mw) of the above PHA resin is within the above range, the processability of the biodegradable resin composition is secured, and a biodegradable article having the desired hardness and / or permeability can be provided.

[0048] The content of the PHA resin may be, but is not limited to, 30 to 85 wt%, 33 to 83 wt%, 35 to 80 wt%, 38 to 75 wt%, 40 to 70 wt%, 43 to 65 wt%, 45 to 60 wt%, 47 to 55 wt%, 48 to 50 wt%, or 40 to 45 wt% based on the total weight of the biodegradable resin composition. When the content of the PHA resin is within the above range, the degree of plasticization of the biodegradable resin composition can be controlled to a required level, thereby providing a biodegradable article having biodegradability and desired hardness and / or permeability.

[0049]

[0050] plasticizer

[0051] The plasticizer included in the biodegradable resin composition of the present disclosure penetrates between the carbon chains present in the PHA resin and controls the attractive force between the carbon chains. The chemical structure of the PHA resin is changed by this plasticizer, which affects not only the processability of the biodegradable resin composition including the PHA resin, but also the physical properties such as hardness and permeability of the biodegradable article. Therefore, in order to obtain a biodegradable article having the desired hardness and / or permeability while ensuring the processability of the biodegradable resin composition, the plasticizer must smoothly penetrate into the PHA resin and the degree of plasticization of the PHA resin must be controlled.

[0052] The plasticizer in the present disclosure is a biodegradable (eco-friendly) plasticizer that can smoothly penetrate between carbon chains of the PHA resin, thereby controlling the degree of plasticization of the PHA resin to a required level.

[0053] Specifically, according to the present disclosure, the plasticizer may include at least one selected from the group consisting of cashew nut shell oil (CNSL), triethyl citrate (TEC), and acetyltributyl citrate (ATBC). As the plasticizer includes the component(s), the compatibility (compatibility) with the PHA resin is improved, thereby plasticizing the PHA resin to a required level.

[0054] The cashew nut shell oil (CNSL) is a phenolic lipid obtained as a by-product in the process of obtaining cashew tree fruits, and its main components are anacardic acid, cardanol, and / or cardol. The plasticizer comprising the cashew nut shell oil (CNSL) has high compatibility with the aPHA resin among the PHA resins, and thus the hardness of a biodegradable article manufactured from a biodegradable resin composition comprising the aPHA resin can be controlled to a required level. For example, when the plasticizer comprising the cashew nut shell oil (CNSL) is used, a biodegradable article (e.g., soft bait) having a shore A hardness of 25 or less (specifically, 0 to 25) can be obtained.

[0055] In addition, the plasticizer containing the cashew nut shell oil (CNSL) has high compatibility with the scPHA resin among the PHA resins, and thus can increase the permeability of a biodegradable article manufactured from a biodegradable resin composition containing the scPHA resin to a required level. For example, when the plasticizer containing the cashew nut shell oil (CNSL) is used, a biodegradable article (e.g., hard bait) having a permeability of 70% or more (specifically, 70 to 100%) can be obtained.

[0056] The above triethyl citrate (TEC) is a citric acid-based component extracted from lemons, and a plasticizer containing the same has high compatibility with the aPHA resin among the PHA resins, and thus can lower the hardness of a biodegradable article manufactured from a biodegradable resin composition containing the aPHA resin to a required level. For example, when a plasticizer containing the above triethyl citrate (TEC) is used, a biodegradable article (e.g., soft bait) having a shore A hardness of 10 or less can be obtained.

[0057] Specifically, according to the present disclosure, the PHA resin may be a scPHA resin comprising 85 to 99 wt% (specifically 87 to 99 wt%, 90 to 98 wt%, 91 to 96 wt%, 92 to 95 wt%, or 92.5 to 94 wt%) of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the PHA resin, wherein the plasticizer may comprise the cashew nut shell oil (CNSL).

[0058] In addition, the PHA resin may be a scPHA resin comprising 1 to 15 wt% (specifically 1 to 13 wt%, 2 to 10 wt%, 4 to 9 wt%, 5 to 8 wt%, or 6 to 7.5 wt%) of a repeating unit derived from 4-hydroxybutyrate (4HB) based on the total weight of the PHA resin, and in this case, the plasticizer may comprise the cashew nut shell oil (CNSL).

[0059] Meanwhile, according to the present disclosure, the PHA resin may be an aPHA resin comprising 65 to 75 wt% (specifically 66 to 78 wt%, 67 to 76 wt%, 68 to 74 wt%, 69 to 72 wt%, or 70 to 71 wt%) of a repeating unit derived from 3-hydroxybutyrate (3HB) based on the total weight of the PHA resin, and wherein the plasticizer may include at least one selected from the group consisting of the cashew nut shell oil (CNSL), the triethyl citrate (TEC), and the acetyltributyl citrate (ATBC).

[0060] In addition, the PHA resin may be an aPHA resin comprising 25 to 35 wt% (specifically 22 to 34 wt%, 24 to 33 wt%, 26 to 32 wt%, 28 to 31 wt%, or 29 to 30 wt%) of a repeating unit derived from 4-hydroxybutyrate (4HB) based on the total weight of the PHA resin, and wherein the plasticizer may comprise at least one selected from the group consisting of the cashew nut shell oil (CNSL), the triethyl citrate (TEC), and the acetyltributyl citrate (ATBC).

[0061] The content of the plasticizer may be, but is not limited to, 15 to 70 wt%, 17 to 67 wt%, 20 to 65 wt%, 25 to 72 wt%, 30 to 60 wt%, 35 to 67 wt%, 32 to 55 wt%, 30 to 50 wt%, 32 to 48 wt%, or 35 to 45 wt%, based on the total weight of the biodegradable resin composition. When the content of the plasticizer is within the above range, the degree of plasticization of the biodegradable resin composition can be controlled to a required level, thereby providing a biodegradable article having biodegradability and desired hardness and / or permeability.

[0062]

[0063] According to the present disclosure, the mixing ratio (a:b) of the PHA resin (a) and the plasticizer (b) is not particularly limited, but may be a weight ratio of 30 to 85:15 to 70. Specifically, the mixing ratio may be a weight ratio of 35 to 80:20 to 65, a weight ratio of 40 to 75:25 to 60, a weight ratio of 45 to 70:30 to 55, or a weight ratio of 50 to 60:40 to 50, but is not limited thereto. When the mixing ratio is within the above range, a biodegradable resin composition having an optimized degree of plasticization can be obtained, thereby providing a biodegradable article having excellent biodegradability and desired hardness and / or permeability.

[0064] For example, when the aPHA resin and the plasticizer including the cashew nut shell oil (CNSL) are mixed, the mixing ratio thereof may be a weight ratio of 35 to 75:25 to 65, or a weight ratio of 40 to 70:30 to 60.

[0065] In addition, when the scPHA resin and the plasticizer including the cashew nut shell oil (CNSL) are mixed, the mixing ratio thereof may be a weight ratio of 30 to 55:45 to 70, or a weight ratio of 35 to 50:50 to 65.

[0066] In addition, when the aPHA resin and the plasticizer including triethyl citrate (TEC) are mixed, the mixing ratio thereof may be a weight ratio of 35 to 50:50 to 65, or a weight ratio of 40 to 45:55 to 60.

[0067] In addition, when the aPHA resin and the plasticizer including acetyltributyl citrate (ATBC) are mixed, the mixing ratio thereof may be a weight ratio of 40 to 50:50 to 60, or a weight ratio of 45 to 50:50 to 55.

[0068]

[0069] Meanwhile, the biodegradable resin composition of the present disclosure may further include one or more additives selected from the group consisting of a slip improving agent, a nucleating agent, a compatibilizing agent, an antioxidant, a lubricant, and an antiblocking agent, as needed.

[0070] The above-mentioned slip improving agent may be an amide-based slip improving agent including at least one selected from the group consisting of erucamide, oleamide, behenamide, stearamide, stearyl stearamide, stearyl erucamide, and oleylpalmityl amide, but is not limited thereto.

[0071] The nucleating agent may specifically include, but is not limited to, one or more selected from the group consisting of talc, clay, calcium carbonate, sorbitol, mannitol, sodium benzoate, zinc glycerolate, aluminum hydroxy-bis(4-tert-butyl)benzoate, and 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate.

[0072] Specifically, the above-mentioned compatibilizer may include at least one selected from the group consisting of pentaerythritol tetraacrylate, trimethylolpropane triacrylate, triallyl isocyanurate, 1,4-benzoquinone, dipentaerythritol hexaacrylate, tripropylene glycol diacrylate, and 1,6-hexanediol diacrylate, but is not limited thereto.

[0073] Specifically, the antioxidants include 2,6-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2-tert-butyl-4-methoxyphenol (BHA), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 2-tert-butyl-6-(2-hydroxy-3-tert-butyl-5-methyl-benzyl)-4-methyl-phenol, 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, It may include at least one selected from the group consisting of 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and phosphorus compounds, but is not limited thereto.

[0074] The above-mentioned active agent may specifically include at least one selected from the group consisting of fatty acid amides, fatty acid esters, silicone compounds, fluorine compounds, and wax compounds, but is not limited thereto.

[0075] The above anti-blocking agent may specifically include, but is not limited to, one or more selected from the group consisting of silica, diatomaceous earth, kaolin, and talc.

[0076] The content of each of these additives can be appropriately set depending on the processability of the biodegradable resin composition and the physical properties of the biodegradable product.

[0077]

[0078] According to the present disclosure, a biodegradable resin composition comprising the PHA resin and the plasticizer has a plasticizer absorption rate of 20% or more as measured in accordance with ASTM D3367-95 after being plasticized at 40°C for 2 days. The plasticizer absorption rate refers to a value evaluated as a weight percentage of the plasticizer absorbed by the PHA resin. Specifically, the plasticizer absorption rate is an indicator indicating the degree of plasticization of the PHA resin due to penetration and absorption of the plasticizer between carbon chains present in the PHA resin. The biodegradable resin composition of the present disclosure exhibits a plasticizer absorption rate of 20% or more, thereby achieving provision of a biodegradable article having excellent processability and desired hardness and / or permeability. Specifically, the biodegradable resin composition of the present disclosure may have a plasticizer absorption rate of, but is not limited to, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 100% or more, 110% or more, 120% or more, 130% or more, 140% or more, 150% or more, 160% or more, 170% or more, or 180% or more (e.g., 20 to 200%, 40 to 200%, 75 to 170%, 95 to 150%, or 100 to 130%).

[0079] Meanwhile, the biodegradable resin composition is plasticized at 40°C for 2 days to maximize plasticization of the PHA resin and to determine the plasticizer absorption rate. Specifically, the temperature and time for maximizing plasticization (maximum plasticity imparted) of the PHA resin may be 40°C and 2 days, respectively.

[0080]

[0081] biodegradable products

[0082] The biodegradable article of the present disclosure is manufactured from the biodegradable resin composition described above. The biodegradable article can exhibit a hardness and / or permeability controlled within a specific range by being manufactured using the biodegradable resin composition described above.

[0083] According to the present disclosure, the biodegradable article may have a Shore A hardness of 0 to 25. Specifically, the Shore A hardness of the biodegradable article may be, but is not limited to, 0.1 to 24.5, 0.5 to 24, 0.7 to 23.5, 1 to 20, 1.2 to 15, 1.4 to 10, or 1.5 to 5. When the Shore A hardness is controlled within the above range, a biodegradable article having a desired Shore A hardness and introducing an aPHA resin can be efficiently provided.

[0084] Specifically, the aPHA resin described above is mainly used in the manufacture of soft baits, but the aPHA resin itself has a rather high hardness, so that the hardness needs to be controlled in order to be used in the manufacture of soft baits. To this end, by introducing the plasticizer described above, the degree of plasticization of the aPHA resin is controlled, and the plasticizer absorption rate of the biodegradable resin composition is optimized, so that the present disclosure can provide a soft bait having a desired Shore A hardness as a biodegradable article.

[0085] For example, the biodegradable article is manufactured from a biodegradable resin composition comprising a polyhydroxyalkanoate (PHA) resin and a plasticizer, wherein the polyhydroxyalkanoate (PHA) resin included in the biodegradable resin composition includes 65 to 75 wt% of a repeating unit derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, and the plasticizer included in the biodegradable resin composition may include at least one selected from the group consisting of cashew nut shell oil, triethyl citrate, and acetyltributyl citrate. Accordingly, the biodegradable article may exhibit a Shore A hardness of 0 to 25.

[0086] According to the present disclosure, the biodegradable article may have a permeability of 70 to 100%. Specifically, the permeability of the biodegradable article may be, but is not limited to, 73 to 100%, 75 to 99%, 77 to 98%, 80 to 97%, 81 to 95%, 82 to 93%, or 83 to 90%. When the permeability is controlled within the above range, a biodegradable article having a desired permeability and introducing a scPHA resin can be efficiently provided.

[0087] Specifically, the scPHA resin described above is mainly used in the production of hard baits. However, since the scPHA resin is a crystalline polymer, its permeability is somewhat low. Therefore, control of the permeability is required in order to use it in the production of hard baits. To this end, by introducing the plasticizer described above, the degree of plasticization of the scPHA resin is controlled, and the plasticizer absorption rate of the biodegradable resin composition is optimized. Accordingly, the present disclosure can provide a hard bait having a desired permeability as a biodegradable article.

[0088] For example, the biodegradable article is manufactured from a biodegradable resin composition comprising a polyhydroxyalkanoate (PHA) resin and a plasticizer, wherein the polyhydroxyalkanoate (PHA) resin included in the biodegradable resin composition comprises 85 to 99 wt% of a repeating unit derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, and the plasticizer included in the biodegradable resin composition may include cashew nut shell oil. Accordingly, the biodegradable article may exhibit a permeability of 70 to 100%.

[0089] According to the present disclosure, the biodegradable article may be bait, and specifically may be soft bait or hard bait.

[0090] In this way, the present disclosure enables control of the hardness and / or permeability of aPHA resin and scPHA resin, thereby enabling implementation of both soft bait and hard bait as biodegradable products.

[0091] The present disclosure is described in more detail through the following examples. However, the scope of the present disclosure is not limited to these examples.

[0092]

[0093] <Manufacture of biodegradable resin composition>

[0094] [Example 1]

[0095] A biodegradable resin composition was prepared by adding 10 g of polyhydroxyalkanoate (PHA) resin pellets (CJ CheilJedang, aPHA (P3HB-co-4HB; 4HB: 30.7 wt%, 3HB: 69.3 wt%; Mw: 594,000)) and 10 g of cashew nut shell oil (CNSL) as a plasticizer to a 100 ml beaker and plasticizing the mixture in an oven at 40°C for 2 days.

[0096]

[0097] [Examples 2 to 9]

[0098] A biodegradable resin composition was manufactured through the same process as Example 1, except that the plasticizer component and the mixing ratio of the PHA resin and the plasticizer were adjusted as shown in Table 1 below.

[0099]

[0100] [Examples 10 to 12]

[0101] A biodegradable resin composition was manufactured through the same process as Example 1, except that instead of aPHA, polyhydroxyalkanoate (PHA) resin pellets (CJ CheilJedang, scPHA (P3HB-co-4HB; 4HB: 7 wt%, 3HB: 93 wt%; Mw: 600,000)) were used and the mixing ratio of the PHA resin and the plasticizer was adjusted as shown in Table 2 below.

[0102]

[0103] [Comparative Examples 1 to 8]

[0104] A biodegradable resin composition was manufactured through the same process as Example 1, except that the plasticizer component and the mixing ratio of the PHA resin and the plasticizer were adjusted as shown in Table 1 below.

[0105]

[0106] [Comparative Example 9]

[0107] A biodegradable resin composition was prepared through the same process as Example 1, except that polyhydroxyalkanoate (PHA) resin pellets (CJ CheilJedang, scPHA (P3HB-co-4HB; 4HB: 7 wt%, 3HB: 93 wt%; Mw: 600,000)) were used alone instead of aPHA.

[0108]

[0109] [Test Example 1] Measurement of plasticizer absorption rate

[0110] The plasticizer absorption rate of the biodegradable resin composition obtained by plasticization was measured according to ASTM D3367-95, and the results are shown in Tables 1 and 2 below. Specifically, the ratio (Y / X) of the weight of the plasticizer absorbed in the biodegradable resin composition (specifically, the PHA resin) obtained through the plasticization process in an oven at 40°C for 2 days to the weight (X) of the PHA resin before plasticization was converted into a percentage to calculate the plasticizer absorption rate.

[0111]

[0112] [Test Example 2] Hardness Measurement

[0113] A biodegradable resin composition obtained by plasticization was hot pressed to produce a film-shaped specimen. When aPHA was applied as a PHA resin, the compression was performed at 120°C for 5 minutes, and when scPHA was applied, the compression was performed at 130°C for 10 minutes. The shore A hardness (value after 15 seconds) of the produced film-shaped specimen was measured using a Digital Professional Shore Hardness Tester (SAUTER) in accordance with ASTM D2240, and the results are shown in Tables 1 and 2 below.

[0114]

[0115] [Test Example 3] Transmittance Measurement

[0116] A biodegradable resin composition obtained by plasticization was hot pressed to produce a film-shaped specimen. When aPHA was applied as a PHA resin, the compression was performed at 120°C for 5 minutes, and when scPHA was applied, the compression was performed at 130°C for 10 minutes. The transmittance of the produced film-shaped specimen was measured using a Haze meter (NIPPON DENSHOKU), and the results are shown in Table 2 below.

[0117]

[0118] aPHA (4HB 30.7 wt%, 3HB 69.3 wt%, Mw 594,000) Plasticizer PHA: Plasticizer Mixing ratio (weight ratio) Plasticizer absorption rate (%) Shore A (15s) Example 1 aPHA Cashew nut shell oil (CNSL) 50:50 100 1.5 Example 2 aPHA Triethyl citrate (TEC) 50:50 100 6.3 Example 3 aPHA Acetyl tributyl citrate (ATBC) 50:50 48.8 23.5 Example 4 aPHA Cashew nut shell oil (CNSL) 70:30 43 22.1 Example 5 aPHA Cashew nut shell oil (CNSL) 60:40 67 18.9 Example 6 aPHA Cashew nut shell Oil (CNSL) 55:45813.7 Example 7aPHA Triethyl Citrate (TEC) 45:551221.5 Example 8aPHA Triethyl Citrate (TEC) 40:601501.7 Example 9aPHA Cashew Shell Oil (CNSL) 80:202535.6 Comparative Example 1aPHA Unused 100:0-67.8 Comparative Example 2aPHA Dioctyl Adipate (DOA) 50:504.965.4 Comparative Example 3aPHA Canola Oil 50:504.764.6 Comparative Example 4aPHA Castor Oil 50:508.664.3 Comparative Example 5aPHA Sunflower Oil 50:505.266.6 Comparative Example 6aPHA Olive oil 50:50 6.5 6.8 Comparative example 7aPHA Epoxidized soybean oil 50:50 9.4 6.3.8 Comparative example 8aPHA Fatty acid methyl ester 50:50 7.0 6.5 CNSL: Cardolite TEC: TCI ATBC: LEMON-FLEX DOA: Pyeonghwa Pharmaceutical Canola oil: Baekseol Castor oil: Sigma-Aldrich Sunflower oil: Sigma-Aldrich Olive oil: Baekseol Epoxidized soybean oil: Donggu Industrial Fatty acid methyl ester: Donggu Industrial

[0119] scPHA (4HB 7 wt%, 3HB 93 wt%, Mw 600,000) Plasticizer PHA: Plasticizer Mixing ratio (weight ratio) Plasticizer absorption rate (%) Shore A (15s) Permeability (%) Example 10 scPHA Cashew nut shell oil (CNSL) 50:50 100 82.7 8 0.1 Example 11 scPHA Cashew nut shell oil (CNSL) 35:65 186 41.6 8 4.0 Example 12 scPHA Cashew nut shell oil (CNSL) 60:40 67 84.6 7 5.6 Comparative example 9 scPHA Unused 100:0-93.5 2.2 CNSL: Cardolite

[0120] Referring to Table 1 and Table 2 above, it can be confirmed that the biodegradable resin compositions of Examples 1 to 12 according to the present disclosure exhibit a plasticizer absorption rate of 20% or more, whereas the biodegradable resin compositions of Comparative Examples 1 to 9 exhibit a plasticizer absorption rate of less than 10%.

[0121] Specifically, the biodegradable resin compositions of Examples 1 to 12 showed a plasticizer absorption rate of 45% or more based on the weight of the PHA resin before plasticization when CNSL, TEC, or ATBC was applied as a plasticizer, confirming that plasticization was efficiently achieved. In particular, when ATBC was plasticized and absorbed by 45% or more into aPHA, the shore A hardness was lowered from 67.8 (see Comparative Example 1) to 23.5, and when CNSL or TEC was plasticized and absorbed by 100% into aPHA, the shore A hardness was lowered to 10 or less, confirming that a biodegradable resin composition highly suitable for manufacturing soft bait was obtained.

[0122] On the other hand, it can be seen that the biodegradable resin composition of Comparative Example 2, to which DOA, a representative PVC plasticizer, was applied, and the biodegradable resin compositions of Comparative Examples 3 to 8, to which a plant-based or fatty acid-based plasticizer was applied, had a very low plasticizer absorption rate of less than 10%, which means that plasticization was insufficient and there was a limit to lowering the shore A hardness to 60 or less.

[0123] Meanwhile, the biodegradable resin compositions of Example 1 and Examples 4 to 9 were prepared by controlling the content of CNSL while applying CNSL to aPHA. Compared to the biodegradable resin composition of Comparative Example 1, when the content of CNSL is less than 30 wt%, the shore A hardness is 25 or more, and when the content of CNSL is 30 wt% or more, the shore A hardness is less than 25. Therefore, it can be seen that the desired shore A hardness can be secured by controlling the content of CNSL.

[0124] In addition, the biodegradable resin compositions of Examples 10 to 12 were obtained by controlling the content of CNSL while applying CNSL to scPHA. Compared to the biodegradable resin composition of Comparative Example 2, when the content of CNSL is 40 wt% or less, the transmittance is less than 80%, and when the content of CNSL is more than 40 wt%, the transmittance is 80% or more, indicating that the desired transmittance can be secured by controlling the content of CNSL.

[0125] In addition, the biodegradable resin compositions of Examples 2, 7 and 8 were obtained by controlling the content of TEC while applying TEC to aPHA. Compared to the biodegradable resin composition of Comparative Example 1, it can be seen that the compositions exhibit a high plasticizer absorption rate of 100% or more and a shore A hardness of 10 or less when the content of TEC is 50 wt% or more.

Claims

1. Containing polyhydroxyalkanoate (PHA) resin; and a plasticizer, A biodegradable resin composition having a plasticizer absorption rate of 20% or more as measured according to ASTM D3367-95.

2. In paragraph 1, A biodegradable resin composition, wherein the polyhydroxyalkanoate (PHA) resin comprises 50 to 99 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin.

3. In paragraph 1, A biodegradable resin composition, wherein the weight average molecular weight (Mw) of the polyhydroxyalkanoate (PHA) resin is 100,000 to 1,000,000 g / mol.

4. In paragraph 1, A biodegradable resin composition, wherein the plasticizer comprises at least one selected from the group consisting of cashew nut shell oil, triethyl citrate, and acetyltributyl citrate.

5. In paragraph 4, The above polyhydroxyalkanoate (PHA) resin contains 85 to 99 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, A biodegradable resin composition, wherein the plasticizer comprises the cashew nut shell oil.

6. In paragraph 4, The polyhydroxyalkanoate (PHA) resin contains 65 to 75 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, A biodegradable resin composition, wherein the plasticizer comprises at least one selected from the group consisting of the cashew nut shell oil, the triethyl citrate, and the acetyltributyl citrate.

7. In paragraph 1, A biodegradable resin composition in which the weight ratio of the polyhydroxyalkanoate (PHA) resin and the plasticizer is 30 to 85:15 to 70.

8. In paragraph 1, A biodegradable resin composition having a plasticizer absorption rate of 40 to 200%.

9. A biodegradable article manufactured from a biodegradable resin composition according to paragraph 1.

10. In paragraph 9, The polyhydroxyalkanoate (PHA) resin included in the biodegradable resin composition contains 65 to 75 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, The plasticizer included in the biodegradable resin composition includes at least one selected from the group consisting of cashew shell oil, triethyl citrate, and acetyltributyl citrate, A biodegradable article having a Shore A hardness of 0 to 25.

11. In paragraph 9, The polyhydroxyalkanoate (PHA) resin included in the biodegradable resin composition contains 85 to 99 wt% of repeating units derived from 3-hydroxybutyrate (3HB) based on the total weight of the polyhydroxyalkanoate (PHA) resin, The plasticizer included in the biodegradable resin composition includes cashew shell oil, A biodegradable article having a permeability of 70 to 100%.

12. In paragraph 9, A biodegradable article, wherein the above biodegradable article is bait.