Nucleating agent for biodegradable resin and biodegradable resin composition comprising same

Abstract

The present disclosure relates to: a nucleating agent for a biodegradable resin; a biodegradable resin composition comprising same; and a biodegradable molded article manufactured from the biodegradable resin composition, wherein the nucleating agent for a biodegradable resin includes a guanidine-based compound.

Description

Nucleating agent for biodegradable resin and biodegradable resin composition containing the same

[0001] The present disclosure relates to a crystallization nucleating agent for controlling the crystallization rate of a biodegradable resin and a biodegradable resin composition comprising said crystallization nucleating agent.

[0002] Petroleum-based synthetic plastics are causing problems such as the formation of microplastics, environmental pollution, and the generation of large amounts of waste. In particular, these synthetic plastics are difficult to recycle, increase soil acidity, and pose a significant threat to marine ecosystems.

[0003] To address these issues, biodegradable products using polyhydroxyalkanoate (PHA) resin, a plant-derived aliphatic polyester, are attracting attention. Specifically, since the aforementioned polyhydroxyalkanoate resin is an environmentally friendly material that is naturally biodegradable, it can alleviate the problem of waste plastic disposal.

[0004] However, biodegradable resins such as polyhydroxyalkanoate resins do not have sufficient crystallization characteristics, which can lead to problems such as reduced productivity and mechanical properties of products made using biodegradable resins. For example, if a product made using polyhydroxyalkanoate resin is a film, it is difficult to apply it to a production line for film production because the crystallization rate (solidification rate) is slow, and production efficiency decreases due to the long cooling time. In addition, if a certain amount of time elapses (e.g., during storage), secondary crystallization of the polyhydroxyalkanoate resin may occur, and changes in its properties may occur over time.

[0005] Therefore, there is a need to develop a crystallization nucleating agent that can more efficiently control the crystallization rate of biodegradable resins, such as polyhydroxyalkanoate resins, thereby enabling the production of products with excellent mechanical properties and improved productivity during manufacturing.

[0006] To solve the aforementioned conventional problems, the objective of the present disclosure is to provide a crystallization nucleating agent for biodegradable resins that optimizes the crystallization rate of biodegradable resins, such as polyhydroxyalkanoate resins, thereby improving productivity (processability) when manufacturing products (e.g., molded articles) using biodegradable resins and maintaining the product's mechanical properties in an excellent state even after a certain period of time.

[0007] Another object of the present disclosure is to provide a biodegradable resin composition comprising a crystallization nucleating agent for the biodegradable resin and a biodegradable molded article prepared from the biodegradable resin composition.

[0008] To achieve the above objectives, the present disclosure provides a crystallization nucleation agent for a biodegradable resin comprising a guanidine-based compound.

[0009] According to one embodiment, the guanidine-based compound may include one or more selected from the group consisting of guanidine-based anhydride, guanidine-based hydrate, guanidine-based ester compound and guanidine-based salt.

[0010] According to another embodiment, the guanidine-based compound may include one or more selected from the group consisting of creatine anhydride, creatine hydrate (e.g., creatine monohydrate), creatine methyl ester, creatine ethyl ester, creatine citrate, creatine nitrate, creatine phosphate disodium salt, and guanidinoacetic acid.

[0011] The present disclosure also provides a biodegradable resin composition comprising a crystallization nucleating agent for the biodegradable resin; and a polyhydroxyalkanoate (PHA) resin.

[0012] According to one embodiment, the polyhydroxyalkanoate (PHA) resin may include a 3-hydroxybutyrate (3HB) unit (A).

[0013] According to another embodiment, the polyhydroxyalkanoate (PHA) resin may further include one or more units (B) selected from the group consisting of 3-hydroxyhexanoate (3HH) units, 3-hydroxypropionate (3HP) units, 3-hydroxyvalerate (3HV) units, 4-hydroxybutyrate (4HB) units, 4-hydroxyhexanoate (4HH) units, 4-hydroxypropionate (4HP) units, 4-hydroxyvalerate (4HV) units, 5-hydroxyvalerate (5-HV) units, and 6-hydroxyhexanoate (6-HH) units.

[0014] According to another embodiment, based on the total number of moles of units contained in the polyhydroxyalkanoate (PHA) resin, the content of the unit (A) may be 75 to 99.5 mole%.

[0015] According to another embodiment, the polyhydroxyalkanoate (PHA) resin may be poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB-co-3HH) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-co-4HB).

[0016] According to another embodiment, the content of the crystallization nucleating agent for the biodegradable resin may be 0.01 to 3 parts by weight per 100 parts by weight of the polyhydroxyalkanoate (PHA) resin.

[0017] According to another embodiment, the biodegradable resin composition may further include one or more biodegradable resins selected from the group consisting of polybutylene adipate-co-terephthalate (PBAT) resin, polylactic acid (PLA) resin, polybutylene succinate (PBS) resin, polybutylene succinate-co-adipate (PBSA) resin, polyglycolic acid (PGA) resin, and polycaprolactone (PCL) resin.

[0018] According to another embodiment, the content of the biodegradable resin may be 1 to 100 parts by weight per 100 parts by weight of the polyhydroxyalkanoate (PHA) resin.

[0019] According to another embodiment, the biodegradable resin composition may further include one or more inorganic materials selected from the group consisting of talc, calcium carbonate, silica, wollastonite, and titanium dioxide.

[0020] According to another embodiment, the content of the inorganic material may be greater than 0 to 50 parts by weight per 100 parts by weight of the polyhydroxyalkanoate (PHA) resin.

[0021] According to another embodiment, the biodegradable resin composition has an isothermal crystallization time (t) according to Formula 1 below. 1 / 2@60℃ When comparing ) with a biodegradable resin composition not containing the above-mentioned nucleating agent, the isothermal crystallization time (t 1 / 2@60℃ This can be shortened by more than 0.2 minutes:

[0022] [Equation 1]

[0023] t 1 / 2@60℃ = t1- t2

[0024] t1 is the reference time at which isothermism begins to be maintained at 60 ℃, which is 0 minutes, and

[0025] t2 is the time (in minutes) taken for crystallization to occur after heating the biodegradable resin composition to 185 ℃ at a rate of 10 ℃ / min and then cooling it to 60 ℃ at a rate of 65 ℃ / min while maintaining 60 ℃, and is measured using a differential scanning calorimeter (DSC).

[0026] According to another embodiment, when the crystallization temperature measured from a heat flow curve obtained by heating the biodegradable resin composition to 185°C at a rate of 10°C / min and then cooling it to 30°C at a rate of 10°C / min using a differential scanning calorimeter (DSC) is compared with the biodegradable resin composition that does not contain the crystallization nucleating agent, the crystallization temperature may be increased by 10°C or more.

[0027] Meanwhile, the present disclosure provides a biodegradable molded article manufactured from the above biodegradable resin composition.

[0028] The crystallization nucleating agent for biodegradable resin according to the present disclosure includes a specific compound that affects the crystallization process of the biodegradable resin, thereby enabling faster improvement of the slow crystallization rate of the biodegradable resin, and as a result, the solidification rate during the molding process of the biodegradable resin (e.g., injection molding, extrusion molding, etc.) can be made faster than conventional methods.

[0029] Accordingly, the present disclosure can provide a biodegradable molded article with significantly improved productivity (processability) and mechanical properties by manufacturing the biodegradable molded article using a biodegradable resin composition comprising a crystallization nucleating agent for the biodegradable resin.

[0030] The invention will be described in detail below through examples. The examples are not limited to those disclosed below and may be modified in various forms as long as the essence of the invention is not altered.

[0031] The term "comprising" as used in this specification is intended to specify certain characteristics, regions, steps, processes, elements, and / or components, and, unless specifically stated otherwise, does not exclude the presence or addition of other characteristics, regions, steps, processes, elements, and / or components.

[0032] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification shall be understood to be modified by the term "about" in all cases unless otherwise specified.

[0033] Where numerical values ​​with upper and lower limits are described in this specification to exemplify the size, physical properties, etc. of a component, it can be understood that numerical ranges combining these upper and lower limits are also included within the exemplary scope of this disclosure.

[0034] In this specification, singular expressions may be interpreted to include singular or plural forms as interpreted in context unless otherwise specified.

[0035]

[0036] The present disclosure relates to a crystallization nucleating agent for a biodegradable resin, a biodegradable resin composition comprising said crystallization nucleating agent, and a biodegradable molded article using (including) said composition, and is described in detail as follows.

[0037] In the present disclosure, "biodegradable resin" refers to a resin that can be decomposed by the action of microorganisms in a natural environment. Additionally, in the present disclosure, "nucleating agent" refers to an additive that helps the biodegradable resin efficiently form crystals.

[0038] In this disclosure, the term "unit" may mean a constitutional unit, a structural unit, a repeating unit, a monomer, or a mer unit.

[0039]

[0040] A crystallization nucleating agent for biodegradable resins according to the present disclosure comprises a guanidine-based compound.

[0041] The above guanidine-based compound is not particularly limited as long as it is a compound containing the structure of HN=C(NH2)2 or -C(NH2)2 within the molecule (specifically, a compound having a guanidine structure or a compound having a guanidino structure). By including the above structure, the guanidine-based compound efficiently provides crystal nuclei, thereby promoting the crystallization of the biodegradable resin and enabling the finer of the grain structure. Accordingly, the guanidine-based compound can significantly increase the crystallization rate of the biodegradable resin, thereby providing a biodegradable resin composition and a biodegradable molded article with improved productivity and mechanical properties.

[0042] According to the present disclosure, the guanidine-based compound may include one or more selected from the group consisting of guanidine-based anhydrides, guanidine-based hydrates, guanidine-based ester compounds and guanidine-based salts, but is not limited thereto.

[0043] Specifically, the guanidine-based compound may include one or more selected from the group consisting of creatine anhydride, creatine hydrate, creatine methyl ester, creatine ethyl ester, creatine citrate, creatine nitrate, creatine phosphate disodium salt, and guanidinoacetic acid.

[0044] Since the above guanidine-based compound includes the above compounds, it is possible to provide a biodegradable resin composition and a biodegradable molded article with excellent productivity and mechanical properties even if the composition of the biodegradable resin varies.

[0045] The nucleating agent for biodegradable resins according to the present disclosure has excellent compatibility with commonly known nucleating agents and can be used together. For example, the nucleating agent for biodegradable resins can be used mixed with an inorganic material (e.g., talc) which is a commonly known nucleating agent.

[0046] The biodegradable resin to which the crystallization nucleating agent for the biodegradable resin according to the present disclosure can be applied is not particularly limited as long as it is a biodegradable resin that is commonly known. For example, the biodegradable resin may include one or more selected from the group consisting of polyhydroxyalkanoate (PHA) resin, polybutylene adipate-co-terephthalate (PBAT) resin, polylactic acid (PLA) resin, polybutylene succinate (PBS) resin, polybutylene succinate-co-adipate (PBSA) resin, polyglycolic acid (PGA) resin, and polycaprolactone (PCL) resin.

[0047] Preferably, the biodegradable resin may be a PHA resin or a resin mixed with a PHA resin and a PBAT resin.

[0048] For example, the above-mentioned biodegradable resin may be a PHA resin, and accordingly, the crystallization nucleating agent for the above-mentioned biodegradable resin may be a crystallization nucleating agent for the PHA resin.

[0049]

[0050] A biodegradable resin composition according to the present disclosure comprises a crystallization nucleating agent for biodegradable resins; and a polyhydroxyalkanoate (PHA) resin.

[0051] The crystallization nucleating agent for the biodegradable resin included in the biodegradable resin composition according to the present disclosure is an additive that increases the crystallization rate of the PHA resin by providing crystal nuclei to the PHA resin when the PHA resin is cooled after melting, thereby changing the crystallization form. Since the description of such a crystallization nucleating agent for the biodegradable resin is the same as described above, a detailed description is omitted.

[0052] According to the present disclosure, the content of the crystallization nucleating agent for the biodegradable resin included in the biodegradable resin composition may be 0.01 to 3 parts by weight per 100 parts by weight of the PHA resin. Specifically, the content of the crystallization nucleating agent for the biodegradable resin may be 0.03 to 2.8 parts by weight, 0.04 to 2.5 parts by weight, 0.05 to 2.3 parts by weight, 0.06 to 2 parts by weight, 0.07 to 1.8 parts by weight, 0.08 to 1.5 parts by weight, 0.09 to 1.3 parts by weight, 0.1 to 1 part by weight, 0.1 to 0.8 parts by weight, 0.1 to 0.6 parts by weight, or 0.1 to 0.45 parts by weight, but is not limited thereto. When the content of the crystallization nucleating agent for the above-mentioned biodegradable resin is within the above range, crystallization characteristics can be improved without degrading the mechanical properties of the biodegradable resin, such as PHA resin, thereby providing a biodegradable molded product with excellent mechanical properties and productivity.

[0053] The PHA resin included in the biodegradable resin composition according to the present disclosure is a natural aliphatic polyester resin that accumulates within microbial cells. Such PHA resin can be completely decomposed into carbon dioxide, water, organic waste, etc., in soil and / or oceans, and thus can have excellent biodegradability without generating microplastics.

[0054] The above PHA resin can be obtained through cell disruption of microorganisms using mechanical or physical methods, or through cell disruption of microorganisms using non-mechanical or chemical methods. For example, the above PHA resin can be obtained through an enzyme-catalyzed polymerization process of one or more monomers present in living microorganism cells.

[0055] Specifically, the PHA resin may include one or more units selected from the group consisting of 3-hydroxybutyrate (3HB) units, 3-hydroxyhexanoate (3HH) units, 3-hydroxypropionate (3HP) units, 3-hydroxyvalerate (3HV) units, 4-hydroxybutyrate (4HB) units, 4-hydroxyhexanoate (4HH) units, 4-hydroxypropionate (4HP) units, 4-hydroxyvalerate (4HV) units, 5-hydroxyvalerate (5-HV) units, and 6-hydroxyhexanoate (6-HH) units. For example, the above PHA resin may be a polymer obtained by polymerizing one or more monomers selected from the group consisting of 3-hydroxybutyrate (3HB), 3-hydroxyhexanoate (3HH), 3-hydroxypropionate (3HP), 3-hydroxyvalerate (3HV), 4-hydroxybutyrate (4HB), 4-hydroxyhexanoate (4HH), 4-hydroxypropionate (4HP), 4-hydroxyvalerate (4HV), 5-hydroxyvalerate (5-HV), and 6-hydroxyhexanoate (6-HH). Additionally, the above PHA resin may be a homopolymer or a copolymer such as a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.

[0056] More specifically, according to the present disclosure, the PHA resin may include a 3-hydroxybutyrate (3HB) unit (A).

[0057] Additionally, according to the present disclosure, the PHA resin may further include one or more units (B) selected from the group consisting of 3-hydroxyhexanoate (3HH) units, 3-hydroxypropionate (3HP) units, 3-hydroxyvalerate (3HV) units, 4-hydroxybutyrate (4HB) units, 4-hydroxyhexanoate (4HH) units, 4-hydroxypropionate (4HP) units, 4-hydroxyvalerate (4HV) units, 5-hydroxyvalerate (5-HV) units, and 6-hydroxyhexanoate (6-HH) units. Preferably, the PHA resin may further include the 3-hydroxyhexanoate (3HH) unit (B-1) or the 4-hydroxybutyrate (4HB) unit (B-2) as a unit (B).

[0058] The content of the unit (A) included in the above PHA resin is not particularly limited, but may be 75 to 99.5 mol% based on the total number of moles of the unit included in the above PHA resin. Specifically, the content of the unit (A), which is the 3HB unit, may be 77 to 99.3 mol%, 80 to 99 mol%, 82 to 98.8 mol%, 83 to 98.5 mol%, 84 to 98.3 mol%, 90 to 99 mol%, or 93 to 98 mol%, but is not limited thereto.

[0059] The content of the unit (B) included in the above PHA resin is not particularly limited, but may be 0.5 to 25 mol% based on the total number of moles of the unit included in the above PHA resin. Specifically, the content of the unit (B), which is the 3HH unit or the 4HB unit, may be 0.7 to 23 mol%, 1 to 20 mol%, 1.2 to 18 mol%, 1.5 to 17 mol%, 1.7 to 16 mol%, 1 to 10 mol%, or 2 to 7 mol%, but is not limited thereto.

[0060] When the content of the above unit (A) and / or the above unit (B) is within the above range, the crystallization characteristics by the crystallization nucleating agent for the biodegradable resin are specifically controlled, thereby providing a biodegradable molded article with excellent productivity and mechanical properties.

[0061] Specifically, when the unit (B) included in the PHA resin is a 3HH unit, its content may be 0.5 to 25 mol% based on the total number of moles of units included in the PHA resin. Specifically, the content of the unit (B-1) which is a 3HH unit may be 1 to 23 mol%, 1.5 to 20 mol%, 2 to 19 mol%, 2.5 to 18 mol%, 3 to 17 mol%, 3 to 16 mol%, or 3 to 15 mol%, but is not limited thereto.

[0062] In addition, if the unit (B) included in the PHA resin is a 4HB unit, its content may be 1 to 25 mol% based on the total number of moles of units included in the PHA resin. Specifically, the content of the unit (B-2) which is a 4HB unit may be 1 to 23 mol%, 1.5 to 20 mol%, 2 to 18 mol%, 2 to 17 mol%, 2 to 16 mol%, 1 to 10 mol%, or 2 to 7 mol%, but is not limited thereto.

[0063] For example, the above PHA resin is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB-co-3HH), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB-co-3HV), poly(3-hydroxybutyrate-co-3-hydroxypropionate) (P3HB-co-3HP), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-co-4HB), poly(3-hydroxybutyrate-co-4-hydroxyhexanoate) (P3HB-co-4HH), poly(3-hydroxybutyrate-co-4-hydroxyvalerate) (P3HB-co-4HV), or It may be a copolymer resin such as poly(3-hydroxybutyrate-co-4-hydroxypropionate) (P3HB-co-4HP), and may be a resin composed of the copolymer resin alone or a mixture of two or more copolymer resins.

[0064] Specifically, according to the present disclosure, the PHA resin may be poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB-co-3HH) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-co-4HB).

[0065] When the above PHA resin is the above P3HB-co-4HB, the above PHA resin may be composed of one type of P3HB-co-4HB with a specified 4HB unit (4HB unit content), or may be a resin mixed with two types of P3HB-co-4HB with different 4HB units (4HB unit content).

[0066] Specifically, the above PHA resin may be a semicrystalline PHA resin (scPHA) containing 3HB units, an amorphous PHA resin (aPHA) containing 3HB units, or a resin mixed with these (scPHA+aPHA).

[0067] When the above PHA resin is a resin mixed with scPHA and aPHA, the mixing ratio of these resins (scPHA:aPHA) may be a weight ratio of 50:50 to 95:5, a weight ratio of 53:47 to 90:10, a weight ratio of 55:45 to 88:12, or a weight ratio of 70:30 to 87:13, but is not limited thereto.

[0068] When the above PHA resin is scPHA, the content of units other than 3HB units (e.g., 4HB units) included in the above PHA resin (scPHA) may be 1 to 23 mol%, 1.3 to 20 mol%, 1.5 to 18 mol%, 1.8 to 10 mol%, or 2 to 7 mol% based on the total molar amount of units included in the above PHA resin, but is not limited thereto. Also, when the above PHA resin is aPHA, the content of units other than 3HB units (e.g., 4HB units) included in the above PHA resin (aPHA) may be 20 to 50 mol%, 22 to 47 mol%, 24 to 45 mol%, 26 to 43 mol%, or 27 to 40 mol% based on the total molar amount of units included in the above PHA resin, but is not limited thereto.

[0069] Meanwhile, the weight-average molecular weight (Mw) of the above PHA resin may be 100,000 g / mol or more, 200,000 g / mol or more, 400,000 g / mol or more, or 500,000 g / mol or more, and may also be 1,000,000 g / mol or less, 900,000 g / mol or less, 800,000 g / mol or less, or 700,000 g / mol or less. Specifically, the weight-average molecular weight (Mw) of the PHA resin may be 100,000 to 1,000,000 g / mol, 200,000 to 900,000 g / mol, 300,000 to 800,000 g / mol, 400,000 to 750,000 g / mol, or 450,000 to 700,000 g / mol. When the weight-average molecular weight (Mw) of the PHA resin is within the above range, a biodegradable resin composition with excellent moldability can be provided.

[0070] According to the present disclosure, the biodegradable resin composition may further include a conventionally known biodegradable resin in addition to the PHA resin. Specifically, the biodegradable resin composition may further include one or more biodegradable resins selected from the group consisting of polybutylene adipate-co-terephthalate (PBAT) resin, polylactic acid (PLA) resin, polybutylene succinate (PBS) resin, polybutylene succinate-co-adipate (PBSA) resin, polyglycolic acid (PGA) resin, and polycaprolactone (PCL) resin. As the biodegradable resin composition further includes the biodegradable resin, a biodegradable molded article with improved mechanical properties can be provided.

[0071] The content of the biodegradable resin included in the above biodegradable resin composition is not particularly limited, but may be 1 to 100 parts by weight per 100 parts by weight of the PHA resin. Specifically, the content of the biodegradable resin may be 5 to 90 parts by weight, 7 to 80 parts by weight, 10 to 70 parts by weight, 13 to 60 parts by weight, or 15 to 50 parts by weight, but is not limited thereto.

[0072] According to the present disclosure, the biodegradable resin composition may further include commonly known inorganic materials. Specifically, the biodegradable resin composition may further include one or more inorganic materials selected from the group consisting of talc, calcium carbonate, silica, wollastonite, and titanium dioxide. As the biodegradable resin composition further includes the inorganic material acting as a crystallization nucleating agent, the crystallization rate is further improved, thereby providing a biodegradable molded article with improved mechanical properties and productivity.

[0073] The content of the inorganic material included in the above biodegradable resin composition is not particularly limited, but may be greater than 0 to 50 parts by weight per 100 parts by weight of the PHA resin. Specifically, the content of the inorganic material may be 2 to 45 parts by weight, 5 to 40 parts by weight, 7 to 35 parts by weight, 10 to 30 parts by weight, or 12 to 25 parts by weight, but is not limited thereto.

[0074] In addition, the above-mentioned biodegradable resin composition may further include commonly known additives. Specifically, the additives may be one or more selected from the group consisting of antioxidants, compatibilizers, slip agents, melt strength enhancers, UV absorbers, crosslinking agents, organic pigments, and inorganic pigments, but are not limited thereto. The content of such additives can be appropriately controlled within a range that does not affect the physical properties of the biodegradable resin composition and the biodegradable molded article.

[0075] The biodegradable resin composition according to the present disclosure may be in a state where the nucleating agent for the biodegradable resin and the PHA resin are physically or chemically compounded. Specifically, the biodegradable resin composition may be a biodegradable resin pellet obtained by melt-kneading a composition raw material containing the nucleating agent for the biodegradable resin and the PHA resin, extruding it in the form of a strand, cooling (solidifying) it in a water bath, and then cutting and drying it.

[0076] The above melt mixing can be carried out using a commonly known single-screw extruder or a twin-screw extruder. During the melt mixing, the barrel temperature of the extruder may be 150 to 190 ℃, 153 to 188 ℃, or 155 to 185 ℃, and the die temperature may be 165 to 190 ℃, 165 to 185 ℃, or 170 to 185 ℃, but is not limited thereto.

[0077] The temperature of the above water bath is not particularly limited, but may be 45 to 70 ℃, 50 to 65 ℃, 55 to 60 ℃, or 60 to 65 ℃ in order to allow sufficient crystallization of the PHA resin to occur.

[0078] The biodegradable resin composition according to the present disclosure may be manufactured in the form of pellets and then processed into various forms through commonly known molding methods (e.g., injection molding, extrusion molding, compression molding, vacuum molding, pressure molding, blow molding, etc.). Specifically, the biodegradable resin composition according to the present disclosure may be processed into forms such as films, sheets, straws, containers, cups, spoons, forks, knives, trays, fishing nets, or bottles.

[0079] The biodegradable resin composition according to the present disclosure may exhibit a rapid crystallization rate by including a crystallization nucleating agent for the biodegradable resin.

[0080] Specifically, the biodegradable resin composition is subjected to an isothermal crystallization time (t) according to Formula 1 below. 1 / 2@60℃ When comparing the isothermal crystallization time (t) with a biodegradable resin composition not containing the above-mentioned nucleating agent, 1 / 2@60℃ ) can be shortened by 0.2 minutes or more. For example, the isothermal crystallization time (t) of a biodegradable resin composition containing the above-mentioned crystallization nucleating agent 1 / 2@60℃ )(A) and isothermal crystallization time (t) of a biodegradable resin composition not containing the above-mentioned nucleating agent 1 / 2@60℃ When )(B) are each calculated and compared according to the following Formula 1, the isothermal crystallization time (t) of the biodegradable resin composition containing a crystallization nucleating agent according to the present disclosure 1 / 2@60℃ )(A) may be shortened (faster) by 0.2 minutes or more, 0.3 minutes or more, 0.4 minutes or more, 0.5 minutes or more, 0.6 minutes or more, 1 minute or more, or 2 minutes or more (specifically, 0.2 to 3 minutes, 0.3 to 2.5 minutes, 0.4 to 2.3 minutes, or 1 to 2.1 minutes), but is not limited thereto.

[0081] [Equation 1]

[0082] t 1 / 2@60℃ = t1- t2

[0083] t1 is the reference time at which isothermism begins to be maintained at 60 ℃, which is 0 minutes, and

[0084] t2 is the time (in minutes) taken for crystallization to occur after heating the biodegradable resin composition to 185 ℃ at a rate of 10 ℃ / min and then cooling it to 60 ℃ at a rate of 65 ℃ / min while maintaining 60 ℃, and is measured using a differential scanning calorimeter (DSC).

[0085] Specifically, the above t1 refers to the time at which the temperature of the biodegradable resin composition is maintained at 60°C, and the above t2 refers to the time taken until the biodegradable resin composition reaches the peak point of crystallization.

[0086] In addition, the above biodegradable resin composition has an isothermal crystallization time (t) according to Formula 1. 1 / 2@60℃ )(A) may be -0.1 min or less, specifically -0.14 min or less, -0.18 min or less, -0.2 min or less, -0.23 min or less, -0.25 min or less, -0.27 min or less, -0.30 min or less, -0.32 min or less, -0.34 min or less, or -0.36 min or less (e.g., -0.4 to -0.1 min, -0.38 to -0.2 min, or -0.36 to -0.25 min), but is not limited thereto. The above isothermal crystallization time (t 1 / 2@60℃ ) is a measure for determining how fast the crystallization rate is based on the temperature at which crystallization of the PHA resin can occur (e.g., 60°C), and the biodegradable resin composition according to the present disclosure has the isothermal crystallization time (t 1 / 2@60℃ ) is controlled to -0.1 min or less, allowing for a fast crystallization rate without degradation of mechanical properties.

[0087] Meanwhile, according to the present disclosure, the crystallization temperature measured from a heat flow curve obtained by heating the biodegradable resin composition to 185°C at a rate of 10°C / min and then cooling it to 30°C at a rate of 10°C / min using a differential scanning calorimeter (DSC) can be increased by 10°C or more when compared to a biodegradable resin composition that does not contain the crystallization nucleating agent. For example, when comparing the crystallization temperature (a) of a biodegradable resin composition containing the above-mentioned nucleating agent and the crystallization temperature (b) of a biodegradable resin composition not containing the above-mentioned nucleating agent through differential scanning calorimetry (DSC) analysis, the crystallization temperature (a) of the biodegradable resin composition containing the above-mentioned nucleating agent according to the present disclosure may be increased to 11°C or higher, 13°C or higher, 15°C or higher, 16°C or higher, 17°C or higher, 18°C ​​or higher, 19°C or higher, or 20°C or higher (specifically, 10 to 40°C, 12 to 35°C, 14 to 30°C, 15 to 25°C, or 16 to 20°C), but is not limited thereto.

[0088] Additionally, according to the present disclosure, the crystallization temperature (a) measured from a heat flow curve obtained by heating the biodegradable resin composition to 185°C at a rate of 10°C / min and then cooling it to 30°C at a rate of 10°C / min using a differential scanning calorimeter (DSC) may be 100°C or higher. Specifically, the crystallization temperature (Tc)(a) of the biodegradable resin composition may be 105°C or higher, 110°C or higher, 115°C or higher, 120°C or higher, or 125°C or higher (e.g., 100 to 130°C, 103 to 125°C, 107 to 120°C, or 110 to 118°C), but is not limited thereto.

[0089] The above isothermal crystallization time (t 1 / 2@60℃When comparing the crystallization temperature between the above and the biodegradable resin compositions, it is assumed that the components constituting each biodegradable resin composition are identical except for whether or not they include a crystallization nucleating agent according to the present disclosure.

[0090] Meanwhile, the above biodegradable resin composition may have a tensile strength of 10 to 50 MPa, 15 to 48 MPa, 20 to 43 MPa, or 25 to 40 MPa as measured according to ASTM D638, but may vary depending on the type and characteristics of the resin or experimental conditions.

[0091] In addition, the above biodegradable resin composition may have an elongation of 5 to 380%, 10 to 350%, 20 to 300%, or 30 to 250% as measured according to ASTM D638, but may vary depending on the type and characteristics of the resin or experimental conditions.

[0092] In addition, the above biodegradable resin composition has an impact strength of 1 to 60 kJ / m² as measured according to ASTM D256. 2 , 1 to 50 kJ / m 2 , 2 to 25 kJ / m 2 , 3 to 20 kJ / m 2 , or 3.5 to 10 kJ / m² 2 This may be the case, but it may vary depending on the type and characteristics of the resin or experimental conditions.

[0093]

[0094] The biodegradable molded article according to the present disclosure is manufactured from the biodegradable resin composition described above. The biodegradable molded article is manufactured by molding (processing) the biodegradable resin composition described above, and can exhibit excellent biodegradability and mechanical properties while showing improved productivity.

[0095] The method of molding the above biodegradable resin composition is not particularly limited as long as it is a commonly known method, and specifically, examples include injection molding, extrusion molding, compression molding, vacuum molding, pressure molding, or blow molding.

[0096] The biodegradable molded article obtained through the above molding may specifically be a film, sheet, straw, container, cup, spoon, fork, knife, tray, fishing net, or bottle, but is not limited thereto.

[0097] The present disclosure will be explained more specifically through the following examples. However, the scope of the present disclosure is not limited by these examples.

[0098]

[0099] [Test Example 1] Crystallization Characteristics

[0100] Crystallization temperature (Tc) and isothermal crystallization time (t) of the biodegradable resin composition using differential scanning calorimetry (DSC) 1 / 2@60℃ ... was measured. Specifically, the crystallization temperature (Tc) was determined from a heat flow curve obtained by heating the biodegradable resin composition to 185 ℃ at a rate of 10 ℃ / min and then cooling it to 30 ℃ at a rate of 10 ℃ / min. In addition, the isothermal crystallization time was calculated according to Equation 1 below by heating the biodegradable resin composition to 185 ℃ at a rate of 10 ℃ / min, then rapidly cooling it to 60 ℃ at a rate of 65 ℃ / min, and determining the time required for crystallization to occur (the time required to reach the peak point of crystallization) while maintaining the temperature at 60 ℃.

[0101] [Equation 1]

[0102] t 1 / 2@60℃ = t1- t2

[0103] t1 is the reference time at which isothermism begins to be maintained at 60 ℃, which is 0 minutes, and

[0104] t2 is the time taken to crystallize (the time taken to reach the peak point of crystallization) (minutes) after heating the biodegradable resin composition to 185 ℃ at a rate of 10 ℃ / min and then cooling it to 60 ℃ at a rate of 65 ℃ / min (rapid cooling), while maintaining the temperature at 60 ℃, and is measured using a differential scanning calorimeter (DSC).

[0105]

[0106] [Test Example 2] Mechanical properties

[0107] The mechanical properties of the biodegradable resin composition were verified according to ASTM standards. Specifically, specimens were prepared by injection molding the biodegradable resin composition according to the following ASTM standards, and the tensile strength and elongation of the specimens were measured according to ASTM D638, and the impact strength of the specimens was measured according to ASTM D256.

[0108] - ASTM D638: Dumbbell-type specimen, length 165 mm, thickness 3.2 mm, gauge length 50 mm

[0109] - ASTM D256: Cross-sectional area 63.5 mm × 12.7 mm, thickness 6.4 mm

[0110]

[0111] [Example 1]

[0112] Polyhydroxyalkanoate (PHA) resin and a nucleating agent were mixed and fed into the hopper of a twin-screw extruder (L / D 40, 19 mm, STEER, India). P3HB-co-4HB (scPHA with 96.4 mol% of 3HB units, 3.6 mol% of 4HB units, and Mw of 560 kDa (CJ CheilJedang, S1000P)) was used as the PHA resin, and creatine monohydrate (CAS # 6020-87-7) was used as the nucleating agent, and the content (amount of input) of the nucleating agent was adjusted as shown in Table 1 below.

[0113] Next, the above twin-screw extruder was operated at a barrel temperature of 155 to 175 ℃ and a screw of 200 rpm, and a biodegradable resin composition was prepared by crystallizing the extruded material from the die in a 60 ℃ water bath and then drying it.

[0114]

[0115] [Examples 2 to 6]

[0116] A biodegradable resin composition was prepared through the same process as in Example 1, except that the content (amount added) of the crystallization agent was adjusted as shown in Table 1 below.

[0117]

[0118] [Comparative Example 1]

[0119] A biodegradable resin composition was prepared through the same process as in Example 1, except that no crystallization agent was added.

[0120]

[0121] The crystallization characteristics and mechanical properties of the biodegradable resin composition were confirmed according to Test Examples 1 and 2 above, and the results are shown in Table 1 below.

[0122]

[0123] Composition, Crystallization Characteristics, Mechanical Properties, sc, PHA (parts by weight), Nucleating Agent (parts by weight, phr), Tc (°C), t 1 / 2@60℃ (min) Tensile Strength (MPa) Elongation (%) Impact Strength (kJ / m² 2 Comparative Example 1 100099.380.1934.7229.014.37 Example 1 1000.1115.75 -0.2538.7825.534.11 Example 2 1000.2117.78 -0.3238.6220.363.72 Example 3 1000.3120.18 -0.3238.8016.053.69 Example 4 1000.5119.41 -0.3439.1916.653.77 Example 5 1000.7120.23 -0.3438.5218.233.60 Example 61001.0121.64-0.3637.6917.063.50

[0124] Referring to Table 1 above, compared to the biodegradable resin composition of Comparative Example 1 in which no crystallization nucleating agent was added, the biodegradable resin compositions of Examples 1 to 6 in which a crystallization nucleating agent according to the present disclosure were added have secured mechanical properties and exhibit a high crystallization temperature (Tc) of 100°C or higher, and an isothermal crystallization time (t 1 / 2@60℃ It can be confirmed that the crystallization rate has increased as it shows -0.2 minutes or less. In particular, it can be seen that even when a small amount of the crystallization nucleating agent is used at 0.1 parts by weight, the crystallization rate is improved, and when used at 0.2 parts by weight or more, the crystallization rate increases significantly.

[0125]

[0126] [Examples 7 and 8]

[0127] Polyhydroxyalkanoate (PHA) resin and a nucleating agent were mixed and fed into the hopper of a twin-screw extruder (L / D 40, 19 mm, STEER, India). P3HB-co-4HB (scPHA with 96.4 mol% of 3HB units, 3.6 mol% of 4HB units, and Mw of 733 kDa (CJ CheilJedang, S1000P)) was used as the PHA resin, and guanidinoacetic acid (CAS # 352-97-6) was used as the nucleating agent, and the content (amount of input) of the nucleating agent was adjusted as shown in Table 2 below.

[0128] Next, the above twin-screw extruder was operated at a barrel temperature of 155 to 175 ℃ and a screw of 200 rpm, and a biodegradable resin composition was prepared by crystallizing the extruded material from the die in a 60 ℃ water bath and then drying it.

[0129]

[0130] [Comparative Example 2]

[0131] A biodegradable resin composition was prepared through the same process as in Example 7, except that no crystallization nucleating agent was added.

[0132]

[0133] The crystallization characteristics and mechanical properties of the biodegradable resin composition were confirmed according to Test Examples 1 and 2 above, and the results are shown in Table 2 below.

[0134]

[0135] Composition, Crystallization Characteristics, Mechanical Properties, sc, PHA (parts by weight), Nucleating Agent (parts by weight, phr), Tc (°C), t 1 / 2@60℃ (min) Tensile Strength (MPa) Elongation (%) Impact Strength (kJ / m² 2 Comparative Example 2100089.110.5234.8721.434.27 Example 71000.1102.790.1235.8023.755.68 Example 81000.7107.300.0034.7324.644.97

[0136] Referring to Table 2 above, compared to the biodegradable resin composition of Comparative Example 2 in which no nucleating agent was added, the biodegradable resin compositions of Examples 7 and 8 in which a nucleating agent according to the present disclosure was added have secured mechanical properties and exhibit a high crystallization temperature (Tc) of 100°C or higher, and an isothermal crystallization time (t 1 / 2@60℃ It can be confirmed that the crystallization rate is accelerated by shortening the crystallization period. In particular, even when using a small amount of crystallization nucleating agent (0.1 parts by weight), the effect of improving the crystallization rate can be confirmed.

[0137]

[0138] [Examples 9 and 10]

[0139] A biodegradable resin composition was prepared through the same process as in Example 1, except that scPHA and aPHA were used as the above-mentioned 4HB unit-controlled PHA resin (P3HB-co-4HB), and the contents of scPHA, aPHA, and the nucleating agent were controlled as shown in Table 3 below. At this time, P3HB-co-4HB (CJ CheilJedang, S1000P), in which the 3HB unit was 96.4 mol%, the 4HB unit was 3.6 mol%, and the Mw was 560 kDa, was used as scPHA, and P3HB-co-4HB (CJ CheilJedang, A1000P), in which the 3HB unit was 70 mol%, the 4HB unit was 30 mol%, and the Mw was 600 kDa, was used as aPHA.

[0140]

[0141] [Comparative Examples 3 and 4]

[0142] A biodegradable resin composition was prepared through the same process as in Example 9, except that scPHA and aPHA were used as the above 4HB unit-controlled PHA resin (P3HB-co-4HB) and their contents were controlled as shown in Table 3 below, and a crystallization nucleating agent was not added.

[0143]

[0144] The crystallization characteristics and mechanical properties of the biodegradable resin composition were confirmed according to Test Examples 1 and 2 above, and the results are shown in Table 3 below.

[0145]

[0146] Composition Crystallization Characteristics Mechanical Characteristics 4HB Unit Total Content scph PHA (parts by weight) a PHA (parts by weight) Nucleating Agent (parts by weight, phr) Tc (°C) t 1 / 2@60℃ (min) Tensile Strength (MPa) Elongation (%) Impact Strength (kJ / m² 2Comparative Example 13.6 moles % 1000099.380.1934.7229.014.37 Example 53.6 moles % 100000.7120.23-0.3438.5218.233.60 Comparative Example 37 moles % 8713093.410.3230.8142.889.52 Example 97 moles % 87130.7118.26-0.3132.5722.763.74 Comparative Example 415 moles % 5743088.810.4517.57399.9970.52 Example 1015 moles % 57430.7113.37-0.1416.92263.256.11

[0147] Referring to Table 3 above, the biodegradable resin compositions of Examples 9 and 10, which use two types of PHA resins with different 4HB unit contents, have mechanical properties similar to the biodegradable resin composition of Example 5, which uses one type of PHA resin, upon the addition of a crystallization nucleating agent according to the present disclosure, and have a high crystallization temperature (Tc) and an isothermal crystallization time (t 1 / 2@60℃ It can be confirmed that the crystallization rate is accelerated as the length is shortened. In addition, the biodegradable resin compositions of Examples 9 and 10 show lower elongation and impact strength compared to the biodegradable resin compositions of Comparative Examples 3 and 4, which may indicate that dimensional stability has been improved due to the accelerated effect during post-curing (e.g., crystallization progress after injection molding of the specimen).

[0148]

[0149] [Example 11]

[0150] A biodegradable resin composition was prepared through the same process as in Example 1, except that P3HB-co-3HH, in which the 3HH unit is 6 mol%, was used as the PHA resin and the content was adjusted as shown in Table 4 below.

[0151]

[0152] [Comparative Example 5]

[0153] A biodegradable resin composition was prepared through the same process as in Example 11, except that no crystallization nucleating agent was added.

[0154]

[0155] The crystallization characteristics and mechanical properties of the biodegradable resin composition were confirmed according to Test Examples 1 and 2 above, and the results are shown in Table 4 below.

[0156]

[0157] Composition Crystallization Characteristics Mechanical Properties P3HB-CO-3HH (parts by weight) Nucleating agent (parts by weight, phr) Tc (°C)t 1 / 2@60℃ (min) Tensile Strength (MPa) Elongation (%) Impact Strength (kJ / m² 2 Comparative Example 5 1000 72.29 1.77 34.38 23.9 33.69 Example 1 11000 0.71 17.53 - 0.27 33.09 22.8 83.97

[0158] Referring to Table 4 above, the biodegradable resin composition of Example 11, which uses a PHA resin with a composition different from that of Example 1, has improved mechanical properties compared to the biodegradable resin composition of Comparative Example 5, in which a nucleating agent according to the present disclosure is not added, as the nucleating agent is added, and exhibits a high crystallization temperature (Tc) and an isothermal crystallization time (t 1 / 2@60℃ It can be confirmed that the crystallization rate has increased as the ) has been significantly shortened.

[0159]

[0160] [Example 12]

[0161] A polyhydroxyalkanoate (PHA) resin, a crystallization nucleating agent, and an inorganic material were mixed and fed into the hopper of a twin-screw extruder (L / D 40, 19 mm, STEER, India). P3HB-co-4HB (scPHA with 96.4 mol% of 3HB units, 3.6 mol% of 4HB units, and Mw of 560 kDa (CJ CheilJedang, S1000P)) was used as the PHA resin, creatine monohydrate (CAS # 6020-87-7) was used as the crystallization nucleating agent, and talc was used as the inorganic material. The content (input amount) of the inorganic material and the crystallization nucleating agent was adjusted as shown in Table 5 below.

[0162] Next, a biodegradable resin composition was prepared through the same process as in Example 1.

[0163]

[0164] [Comparative Example 6]

[0165] A biodegradable resin composition was prepared through the same process as in Example 12, except that no crystallization nucleating agent was added.

[0166]

[0167] The crystallization characteristics and mechanical properties of the biodegradable resin composition were confirmed according to Test Examples 1 and 2 above, and the results are shown in Table 5 below.

[0168]

[0169] Composition Crystallization Characteristics Mechanical Characteristics sc PHA (parts by weight) Talc (parts by weight, phr) Nucleating agent (parts by weight, phr) Tc (°C) t 1 / 2@60℃ (min) Tensile Strength (MPa) Elongation (%) Impact Strength (kJ / m² 2 Comparative Example 6 100250102.640.1436.3217.044.36 Example 12 100250.87117.11-0.3237.0511.513.47

[0170] Referring to Table 5 above, the biodegradable resin composition of Example 12, in which a nucleating agent according to the present disclosure is added along with talc used as a nucleating agent, has a higher crystallization temperature (Tc) and an isothermal crystallization time (t) compared to the biodegradable resin composition of Comparative Example 6, in which only talc is added. 1 / 2@60℃ It can be confirmed that the crystallization rate has been significantly accelerated due to the greatly shortened curing time. In addition, the biodegradable resin composition of Example 12 shows lower elongation and impact strength compared to the biodegradable resin composition of Comparative Example 6, which may indicate that dimensional stability has been improved due to the accelerated effect during post-curing.

[0171]

[0172] [Example 13]

[0173] Polyhydroxyalkanoate (PHA) resin, biodegradable resin, crystallization nucleating agent, inorganic material, and additives were mixed and fed into the hopper of a twin-screw extruder (L / D 40, 19 mm, STEER, India). P3HB-co-4HB (scPHA with 96.4 mol% 3HB units, 3.6 mol% 4HB units, and Mw of 560 kDa (CJ CheilJedang, S1000P)) was used as the PHA resin, PBSA resin (KingFa, KB500SF) was used as the biodegradable resin, creatine monohydrate (CAS # 6020-87-7) was used as the crystallization nucleating agent, talc was used as the inorganic material, and EBS (Kao, KAOWAX EB-FF) was used as the additive, and the content (input amount) of the biodegradable resin, the inorganic material, the crystallization nucleating agent, and the additive was adjusted as shown in Table 6 below.

[0174] Next, a biodegradable resin composition was prepared through the same process as in Example 1.

[0175]

[0176] [Comparative Example 7]

[0177] A biodegradable resin composition was prepared through the same process as in Example 13, except that no crystallization nucleating agent was added.

[0178]

[0179] The crystallization characteristics of the biodegradable resin composition were confirmed according to Test Example 1 above, and the results are shown in Table 6 below.

[0180]

[0181] Composition Crystallization Characteristics scPHA(parts by weight)PBSA(parts by weight, phr)Talc(parts by weight, phr)Nucleating agent(parts by weight, phr)EBS(parts by weight, phr)Tc (°C)t 1 / 2@60℃ (min) Comparative Example 7 100331500.596.670.23 Example 13 10033151.00.5111.27-0.13

[0182] Referring to Table 6 above, the biodegradable resin composition of Example 13, in which PHA resin and biodegradable resin (PBSA) are used together, has a high crystallization temperature (Tc) and an isothermal crystallization time (t) as a nucleating agent according to the present disclosure is added. 1 / 2@60℃ It can be confirmed that the crystallization rate has increased as the ) is shortened.

[0183] Meanwhile, when the actual product, cutlery, is manufactured through an injection molding process that includes cooling the biodegradable resin composition of Example 13 to 60°C, it was confirmed that the cutlery was successfully released from the injection mold even when cooling was performed at the same time applied during actual product manufacturing due to the rapid crystallization rate. This supports the fact that when a product is manufactured using a biodegradable resin composition containing a crystallization nucleating agent according to the present disclosure, the cooling time and / or release time can be controlled, thereby improving product productivity.

Claims

1. A crystallization nucleating agent for biodegradable resins comprising a guanidine-based compound.

2. In Paragraph 1, A crystallization nucleating agent for biodegradable resins, wherein the above-mentioned guanidine-based compound comprises one or more selected from the group consisting of guanidine-based anhydrides, guanidine-based hydrates, guanidine-based ester compounds, and guanidine-based salts.

3. In Paragraph 1, A crystallization nucleating agent for biodegradable resins, wherein the above-mentioned guanidine-based compound comprises one or more selected from the group consisting of creatine anhydride, creatine hydrate, creatine methyl ester, creatine ethyl ester, creatine citrate, creatine nitrate, creatine phosphate disodium salt, and guanidinoacetic acid.

4. A crystallization nucleating agent for the biodegradable resin of claim 1; and A biodegradable resin composition comprising a polyhydroxyalkanoate (PHA) resin.

5. In Paragraph 4, A biodegradable resin composition in which the above polyhydroxyalkanoate (PHA) resin comprises 3-hydroxybutyrate (3HB) units (A).

6. In Paragraph 5, A biodegradable resin composition comprising one or more units (B) selected from the group consisting of 3-hydroxyhexanoate (3HH) units, 3-hydroxypropionate (3HP) units, 3-hydroxyvalerate (3HV) units, 4-hydroxybutyrate (4HB) units, 4-hydroxyhexanoate (4HH) units, 4-hydroxypropionate (4HP) units, 4-hydroxyvalerate (4HV) units, 5-hydroxyvalerate (5-HV) units, and 6-hydroxyhexanoate (6-HH) units.

7. In Paragraph 6, A biodegradable resin composition having a content of 75 to 99.5 mol% of the unit (A) based on the total molar amount of the unit contained in the polyhydroxyalkanoate (PHA) resin.

8. In Paragraph 6, A biodegradable resin composition in which the above polyhydroxyalkanoate (PHA) resin is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB-co-3HH) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-co-4HB).

9. In Paragraph 4, A biodegradable resin composition having a content of a crystallization nucleating agent for the biodegradable resin of 0.01 to 3 parts by weight per 100 parts by weight of the polyhydroxyalkanoate (PHA) resin.

10. In Paragraph 4, A biodegradable resin composition further comprising one or more biodegradable resins selected from the group consisting of polybutylene adipate-co-terephthalate (PBAT) resin, polylactic acid (PLA) resin, polybutylene succinate (PBS) resin, polybutylene succinate-co-adipate (PBSA) resin, polyglycolic acid (PGA) resin, and polycaprolactone (PCL) resin.

11. In Paragraph 10, A biodegradable resin composition having a content of 1 to 100 parts by weight per 100 parts by weight of the polyhydroxyalkanoate (PHA) resin.

12. In Paragraph 4, A biodegradable resin composition further comprising one or more inorganic materials selected from the group consisting of talc, calcium carbonate, silica, wollastonite, and titanium dioxide.

13. In Paragraph 12, A biodegradable resin composition having a content of the above-mentioned inorganic material of more than 0 to 50 parts by weight per 100 parts by weight of the above-mentioned polyhydroxyalkanoate (PHA) resin.

14. In Paragraph 4, Isothermal crystallization time (t) according to Equation 1 below 1 / 2@60℃ When comparing ) with a biodegradable resin composition not containing the above-mentioned nucleating agent, the isothermal crystallization time (t 1 / 2@60℃ Biodegradable resin composition with a reduction of ) by 0.2 minutes or more: [Equation 1] t 1 / 2@60℃ = t1- t2 t1 is the reference time at which isothermism begins to be maintained at 60 ℃, which is 0 minutes, and t2 is the time (in minutes) taken for crystallization to occur after heating the biodegradable resin composition to 185 ℃ at a rate of 10 ℃ / min and then cooling it to 60 ℃ at a rate of 65 ℃ / min while maintaining 60 ℃, and is measured using a differential scanning calorimeter (DSC).

15. In Paragraph 4, A biodegradable resin composition in which the crystallization temperature measured from a heat flow curve obtained by heating to 185 ℃ at a rate of 10 ℃ / min using a differential scanning calorimeter (DSC) and then cooling to 30 ℃ at a rate of 10 ℃ / min is increased by 10 ℃ or more when compared to a biodegradable resin composition not containing the crystallization nucleating agent.

16. A biodegradable molded article manufactured from the biodegradable resin composition of claim 4.