Polybutylene succinate (PBS) resin vaporization promoter and composition containing same

Abstract

According to one embodiment of the present invention, a polybutylene succinate (PBS)-based resin is contained in an amount of 10% by mass or more and less than 100% by mass based on the total mass of the composition, and the vaporization degree (V) of the vaporized carbon dioxide (CO2) is measured after 12 weeks at 30°C. 10w The present invention relates to a composition having a vaporization rate of 20% or more, and a vaporization accelerator for PBS-based resin that accelerates the vaporization of PBS-based resin. The vaporization accelerator for PBS-based resin can significantly accelerate the vaporization of PBS-based resin having a low vaporization rate at room temperature, i.e., 30°C, and improve the biodegradability of PBS-based resin. Therefore, a composition containing the same can be used in various fields and can effectively contribute to environmental conservation while exhibiting excellent physical properties.

Description

[Technical field]

[0001] The present invention relates to a vaporization promoter that promotes the vaporization of a polybutylene succinate (PBS) resin, and a composition containing the same. [Background technology]

[0002] Currently, commercialized general-purpose plastics have excellent physical properties, and demand is increasing due to stable supply and price. However, problems arise regarding the disposal of waste plastics throughout their lifespan. These plastics do not decompose under natural conditions such as in the ocean or soil, and therefore are a cause of serious environmental pollution.

[0003] In order to solve these environmental pollution problems, biodegradable plastics have been actively researched in recent years.

[0004] Biodegradable plastics are materials that can be broken down by microorganisms in nature into low molecular weight substances and ultimately into water and carbon dioxide, or water and methane gas.

[0005] A polymer resin typically used as such a biodegradable plastic is polylactic acid (PLA) resin. Recently, active research has been conducted on the use of polybutylene succinate (PBS)-based resins, such as polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and polybutylene succinate terephthalate (PBST), which have a better decomposition rate and moldability than PLA resin.

[0006] However, these PBS-based resins actually take a long time to decompose. Complete biodegradation is particularly difficult in natural environments such as the ocean and soil, and there is a limit to how quickly they can be decomposed at room temperature. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made to solve the above-mentioned problems of the conventional technology.

[0008] The present invention aims to provide a vaporization promoter for polybutylene succinate (PBS)-based resin, which increases the vaporization degree of polybutylene succinate (PBS)-based resin that has a low vaporization degree at room temperature of 30°C, and increases the biodegradation effect (speed) of the polybutylene succinate (PBS)-based resin even at room temperature, and a composition containing the same. [Means for solving the problem]

[0009] According to one aspect of the present invention, there is provided a composition containing a polybutylene succinate (PBS)-based resin in an amount ranging from 10% by mass to less than 100% by mass based on the total mass of the composition, and when a cumulative amount of carbon dioxide (CO2) generated over a period of 12 weeks at 30°C is measured in accordance with ISO 14855, the composition has a vaporization rate (V) represented by the following formula 1: 10w ) is 20% or more.

[0010] [ka]

[0011] In formula 1, (CO2) S is the cumulative amount (g) of carbon dioxide (CO2) generated in the test container containing the compost and 14.3% by mass of the sample based on the total dry mass of the sample and compost, and (CO2) B is the cumulative amount of carbon dioxide (CO2) generated in the inoculum container containing only compost (g), and (CO2) THV is the theoretical cumulative amount of carbon dioxide (CO2) generated in the test vessel and is expressed by the following formula 2.

[0012] [ka]

[0013] In Equation 2, Cw is the mass of organic carbon (g) contained in the sample.

[0014] In one embodiment, the composition may further include a vaporization enhancer for polybutylene succinate (PBS) based resins.

[0015] In another embodiment, the mass ratio of the polybutylene succinate (PBS) resin to the vaporization promoter for the polybutylene succinate (PBS) resin can be 10:90 to 90:10.

[0016] In another embodiment, the composition has a vaporization enhancement improvement (ΔVID 10W ) may be 0.1% or more.

[0017] [ka]

[0018] In Equation 3, V 10w is as defined above, and V THV10w is expressed by the following equation 4.

[0019] [ka]

[0020] In formula 4, x is the mass percentage of the polybutylene succinate (PBS) resin contained in the composition based on the total mass of the composition.

[0021] In another embodiment, the vaporization promoter for polybutylene succinate (PBS)-based resins can satisfy at least one of the following properties: a glass transition temperature (Tg) of -45°C to 80°C, a crystallization temperature (Tc) of 60°C to 120°C, and a melting temperature (Tm) of 100°C to 170°C.

[0022] In another embodiment, the polybutylene succinate (PBS) based resin comprises at least one selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and polybutylene succinate terephthalate (PBST), and the vaporization enhancer for the polybutylene succinate (PBS) based resin comprises a resin comprising repeat units derived from 4-hydroxybutyrate (4-HB) monomer and repeat units derived from one or more monomers selected from the group consisting of 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvalerate (3-HV), 3-hydroxyhexanoate (3-HH), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate (6-HH).

[0023] In another embodiment, a vaporization enhancer for a polybutylene succinate (PBS) based resin can include a resin including repeat units derived from 3-hydroxybutyrate (3-HB) monomers and repeat units derived from 4-hydroxybutyrate (4-HB) monomers.

[0024] In another embodiment, the resin can contain repeat units derived from 3-hydroxybutyrate (3-HB) monomers in an amount ranging from 1 mol % to 80 mol %, based on the total number of moles of repeat units derived from 3-hydroxybutyrate (3-HB) monomers and repeat units derived from 4-hydroxybutyrate (4-HB) monomers.

[0025] In another aspect of the invention, a vaporization enhancer is provided for polybutylene succinate (PBS) based resins, including resins that include repeat units derived from 3-hydroxybutyrate (3-HB) monomers and repeat units derived from 4-hydroxybutyrate (4-HB) monomers.

[0026] In one embodiment, the molar ratio of repeat units derived from 3-hydroxybutyrate (3-HB) monomers to repeat units derived from 4-hydroxybutyrate (4-HB) monomers contained in the resin can be 40:60 to 99:1. Effect of the Invention

[0027] The composition according to one embodiment of the present invention includes a polybutylene succinate (PBS)-based resin having a low vaporization rate at room temperature of 30°C, and when the cumulative amount of carbon dioxide (CO2) generated over a 12-week period is measured, the vaporization rate is above a certain level, thereby achieving excellent biodegradation effects at room temperature.

[0028] Furthermore, the vaporization promoter for polybutylene succinate (PBS) resin of the present invention can significantly promote the vaporization of polybutylene succinate (PBS) resin having a low vaporization degree at room temperature of 30°C.

[0029] Therefore, the composition and the vaporization promoter for polybutylene succinate (PBS)-based resin have excellent physical properties and can be used in various fields to effectively protect the environment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] Hereinafter, the present invention will be described in detail with reference to the embodiments. Note that the embodiments are not limited to those described below. Rather, various modifications are possible within the scope of the present invention.

[0031] In this specification, when a part is referred to as "comprising" certain elements, it should be understood that other elements may be included, without excluding other elements, unless specifically stated otherwise.

[0032] Furthermore, all numbers expressing physical characteristics, dimensions, and the like of elements used in this disclosure should be understood as being modified by the term "about" unless otherwise specified.

[0033] The present invention provides a method for easily biodegrading a compostable material at room temperature (e.g., 25±5°C) by applying the cumulative amount of carbon dioxide produced under aerobic composting conditions, CO2, to the compostable material, even if the compostable material contains a polybutylene succinate (PBS)-based resin, which is difficult to biodegrade at room temperature (e.g., 25±5°C). 10w The present invention relates to a composition (a vaporizable composition or a biodegradable composition) in which the vaporization promoter for polybutylene succinate (PBS)-based resin is controlled to a specific range or higher, and a vaporization promoter for polybutylene succinate (PBS)-based resin contained in the composition, which will be described in detail below.

[0034] [Composition] The composition according to one embodiment of the present invention contains a polybutylene succinate (hereinafter referred to as "PBS")-based resin in an amount ranging from 10% by mass to less than 100% by mass based on the total mass of the composition, and has a vaporization rate (V) represented by the following formula 1 when the cumulative amount of carbon dioxide generated (CO2) is measured over 12 weeks at 30°C in accordance with ISO 14855. 10w ) is 20% or more.

[0035] [ka]

[0036] In formula 1, (CO2) S is the cumulative amount (g) of carbon dioxide (CO2) generated in a test vessel containing compost and a sample (composition sample) in an amount of 14.3 mass% based on the total dry mass of the sample and compost, and (CO2) B is the cumulative amount of carbon dioxide (CO2) (g) generated in the inoculum container containing only compost, and (CO2) THV is the theoretical cumulative amount (g) of carbon dioxide (CO2) generated in a test vessel (test vessel (a+b)) containing compost (a) and sample (b) in an amount of 14.3 mass% of the total dry mass of sample (b) and compost (a) (dry mass of sample + dry mass of compost), and is expressed by the following formula 2.

[0037] [ka]

[0038] In Equation 2, Cw is the mass (g) of organic carbon (carbon element) contained in the sample (a sample amounting to 14.3% by mass of the total mass (x+y) of the dry mass of the sample (x) and the dry mass of the compost (y)). Specifically, Cw is the carbon element content (g) measured when elemental analysis of the sample is performed.

[0039] In addition, (CO2) S and (CO2) B The mass of compost used for the measurement of moisture content can be the same. Furthermore, the dry mass of compost can be calculated by LOD (loss on drying), which is a thermogravimetric measurement principle of moisture. That is, the difference in mass loss when the compost is dried can be measured, and the dry mass can be calculated using moisture analysis using a drying oven or a halogen moisture analyzer (HMA).

[0040] Here, the vaporization rate (V 10w ) is not the degree of biodegradation (biodegradation effect) of a composition breaking down into small pieces or molecules, but is the value measured when the composition breaks down into low molecular weight substances and finally completely breaks down into carbon dioxide and vaporizes.

[0041] Specifically, the vaporization rate (V 10w ) is a value obtained by measuring the cumulative amount of carbon dioxide (CO2) generated, which is the final decomposition product of the composition, according to the ISO 14855 notification provisions (specifically, the aerobic biodegradability evaluation method of ISO 14855-1), and applying the measured cumulative amount of carbon dioxide (CO2) generated to formulas 1 and 2, and can be an index of the biodegradability of the composition at room temperature of 30°C.

[0042] The composition according to one embodiment of the present invention may further include a vaporization promoter for polybutylene succinate (PBS)-based resin (hereinafter, referred to as "vaporization promoter for PBS-based resin"). Specifically, the composition further including the vaporization promoter for PBS-based resin has a vaporization degree (V) represented by Formula 1. 10w) may be 20% or more. More specifically, the vaporization degree (V 10w ) can be an indicator of the biodegradability of a composition containing a PBS-based resin and a vaporization promoter for a PBS-based resin.

[0043] That is, the vaporization rate (V 10w ) was used as an evaluation group. A composition sample containing a PBS-based resin and a vaporization promoter for PBS-based resin in a specific content ratio was mixed with compost and placed in a test container, and the cumulative amount (g) of carbon dioxide (CO2) generated from the composition sample was measured over a period of 12 weeks at 30°C under aerobic compost conditions using a measurement evaluation device (ECHO respirometer device). S ) was measured, and as a control group, the cumulative amount (g) of carbon dioxide (CO2) generated in an inoculum source container containing only compost without the composition sample under the same conditions as the evaluation group was measured ((CO2) B ) was calculated, and the cumulative amount (g) of carbon dioxide (CO2) generated in the evaluation group and the control group was calculated as CO 2S and CO 2B The difference between the theoretical cumulative amount (g) of carbon dioxide (CO2) generated was calculated as shown in Equation 2 ((CO2) THV ) and convert it to a percentage.

[0044] The composition according to one embodiment of the present invention includes a PBS-based resin, and has a vaporization rate (V) of 1.0% when the cumulative amount of carbon dioxide (CO2) generated over a 12-week period is measured. 10w ) is at a certain level or higher, and therefore, even if it contains a PBS-based resin having a low vaporization rate, it can exhibit excellent biodegradation effects under aerobic composting conditions at a room temperature of 30° C. The pressure condition under aerobic composting conditions can be normal pressure.

[0045] Specifically, the vaporization degree (V 10w) can be, for example, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 48% or more, 50% or more, 55% or more, 60% or more, or 65% or more (e.g., 20% to 80%, 25% to 75%, 30% to 70%, or 40% to 69%).

[0046] On the other hand, (CO2) in Eq. S can be, for example, 5 g or more, 10 g or more, 20 g or more, 30 g or more, 35 g or more, 40 g or more, 45 g or more, 50 g or more, 55 g or more, or 60 g or more. S can be, for example, 65 g or less, 63 g or less, 60 g or less, 58 g or less, or 55 g or less.

[0047] (CO2) in Equation 1 S and (CO2) B The difference between the net carbon dioxide (CO2) and the net carbon dioxide (CO2) can be, for example, 1 g or more, 2 g or more, 3 g or more, 5 g or more, or 10 g or more. S and (CO2) B The difference from can be, for example, 80 g or less, 70 g or less, 60 g or less, 50 g or less, 40 g or less, or 30 g or less.

[0048] (CO2) in Equation 1 THV refers to the theoretical maximum cumulative amount (g) of carbon dioxide (CO2) generated when the sample (composition sample) is completely oxidized (when 100% of the organic carbon contained in the sample is converted to carbon dioxide (CO2)) in the test container containing the compost and sample, and can be expressed by Equation 2. That is, (CO2) THV is the product of the mass of organic carbon (carbon atoms) contained in the sample (Cw) and the ratio (44 / 12) of the molecular weight of carbon dioxide (44) to the atomic weight of carbon atom (12). (CO2) THV can be, for example, 5 g or more, 6 g or more, 7 g or more, 10 g or more, 15 g or more, 20 g or more, 30 g or more, 40 g or more, or 50 g or more. THVcan be, for example, 80 g or less, 70 g or less, 60 g or less, 55 g or less, 50 g or less, 45 g or less, or 42 g or less.

[0049] On the other hand, the composition according to one embodiment of the present disclosure has a vaporization promotion improvement degree (ΔVID 10W ) may be 0.1% or more:

[0050] [ka]

[0051] In Equation 3, V 10w is defined above, and V THV10w is expressed by the following equation 4.

[0052] [ka]

[0053] In formula 4, x is the mass percentage of the PBS-based resin contained in the composition based on the total mass of the composition. Meanwhile, in formula 4, 3% is the vaporization degree (V) calculated by formula 1 when the cumulative amount of carbon dioxide (CO2) generated over 12 weeks at 30°C is measured in accordance with ISO 14855 for a composition composed of 100 mass% PBS-based resin (a composition containing only PBS-based resin). 10w ) (%), and 97% refers to the degree of vaporization (V) calculated by formula 1 when the cumulative amount of carbon dioxide (CO2) generated over 12 weeks at 30°C is measured in accordance with ISO 14855 for a composition consisting of 100% by mass of the vaporization accelerator for PBS-based resin (a composition containing only the vaporization accelerator for PBS-based resin). 10w ) (%).

[0054] Evaporation promotion improvement degree (ΔVID 10w ) is the measured vaporization degree of the composition (V 10w ) to calculate the theoretical vaporization degree (V THV10w ) and the value obtained by subtracting (V 10w -VTHV10w ) and can be an indicator of the degree to which the vaporization of PBS-based resin is promoted by the vaporization promoter for PBS-based resin.

[0055] Evaporation promotion improvement degree (ΔVID 10W ) can be, for example, 0.2% or more, 0.3% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 1% or more, 2% or more, 3% or more, 5% or more, 10% or more, 12% or more, 13% or more, 15% or more, 20% or more, 22% or more, 23% or more, 24% or more, 25% or more, 30% or more, 33% or more, or 35% or more. Furthermore, the evaporation promotion improvement degree (ΔVID 10W ) can be, for example, 50% or less, 48% or less, 46% or less, 45% or less, 43% or less, 40% or less, or 38% or less.

[0056] This evaporation promotion improvement degree (ΔVID 10W ) may vary depending on the content and physical properties of the PBS-based resin contained in the composition, or may vary depending on the content, components, or physical properties of the vaporization promoter for the PBS-based resin contained in the composition.

[0057] On the other hand, in formula 3, the theoretical vaporization degree of the composition (V THV10w ) may vary depending on the content (mass) of the PBS-based resin and the vaporization promoter for the PBS-based resin contained in the composition. Specifically, the theoretical vaporization degree (V THV10w ) can be, for example, 1% or more, 2% or more, 3% or more, 5% or more, 6% or more, 7% or more, 8% or more, 10% or more, 15% or more, or 20% or more, and can be 90% or less, 80% or less, 70% or less, 65% or less, 55% or less, 45% or less, 40% or less, or 35% or less.

[0058] When the composition according to one embodiment of the present invention is compared with cellulose (a representative standard biodegradable material) in terms of vaporization degree, the vaporization degree (V) is equal to or higher than that of cellulose. 10w ).

[0059] Specifically, the composition according to one embodiment of the present invention contains a PBS-based resin having a low vaporization rate at room temperature of 30° C., and the vaporization rate (V) was measured when the cumulative amount of carbon dioxide (CO2) generated over a period of 12 weeks was measured. 10w ) is above a certain level (e.g., 20% or more), it exhibits excellent biodegradability at room temperature.

[0060] Therefore, the composition according to one embodiment of the present invention can be used in various fields to effectively protect the environment as well as providing excellent physical properties.

[0061] Each component of the composition according to one embodiment of the present invention will be described in detail below.

[0062] Polybutylene succinate (PBS) resin A composition according to one embodiment of the present invention may include a PBS-based resin.

[0063] PBS-based resins are representative polycondensed aliphatic polyesters or aliphatic-aromatic polyesters, and are heat-resistant polymers having a relatively high melting point compared to other polyesters synthesized from dihydric alcohols and diacids.

[0064] Specifically, the PBS-based resin can be synthesized by an esterification reaction between 1,4-butanediol (1,4-BDO) and succinic acid, and a transesterification reaction (polycondensation reaction) of the oligomer obtained by the esterification reaction.

[0065] The PBS-based resin may include at least one selected from the group consisting of polybutylene succinate (PBS), a binary copolymer of 1,4-butanediol (1,4-BDO) and succinic acid, polybutylene succinate adipate (PBSA), a ternary copolymer of 1,4-butanediol (1,4-BDO), succinic acid, and adipic acid, and polybutylene succinate terephthalate (PBST), a quaternary copolymer of 1,4-butanediol (1,4-BDO), succinic acid, adipic acid, and terephthalic acid or dimethyl terephthalate.

[0066] The PBS-based resin may have a mass average molecular weight (Mw) of about 100,000 to 500,000 g / mol, about 120,000 to 500,000 g / mol, about 150,000 to 450,000 g / mol, about 150,000 to 430,000 g / mol, or about 150,000 to 400,000 g / mol. The mass average molecular weight (Mw) may be measured by gel permeation chromatography (GPC).

[0067] The composition according to one embodiment of the present invention may include the PBS-based resin in an amount of 10% by mass or more and less than 100% by mass based on the total mass of the composition.

[0068] Specifically, the composition may contain the PBS resin in an amount of 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, and less than 100% by mass, 98% by mass or less, 95% by mass or less, 93% by mass or less, 92% by mass or less, or 90% by mass or less, based on the total mass of the composition. For example, the composition may contain the PBS resin in an amount of 10% by mass to 99% by mass, 20% by mass to 97% by mass, 30% by mass to 95% by mass, 40% by mass to 93% by mass, 50% by mass to 92% by mass, 60% by mass to 91% by mass, or 70% by mass to 90% by mass, based on the total mass of the composition.

[0069] When the cumulative amount of carbon dioxide (CO2) generated in a composition consisting of 100% by mass of PBS-based resin was measured over a period of 12 weeks at 30°C in accordance with ISO 14855, the vaporization rate (V) calculated by Equation 1 was 10w ) can be very low.

[0070] Therefore, the composition according to one embodiment of the present invention further contains a vaporization promoter for PBS-based resin, which will be described later, and thereby promotes the vaporization of the PBS-based resin, which has a low degree of vaporization at room temperature, thereby further improving the biodegradation effect.

[0071] Vaporization promoter for polybutylene succinate (PBS) resins The composition according to one embodiment of the present invention may further include a vaporization promoter for the PBS-based resin.

[0072] The vaporization promoter for PBS-based resin of the present invention can function as a promoter capable of promoting the vaporization of PBS-based resin having a low vaporization degree at room temperature of 30°C.

[0073] The composition according to one embodiment of the present invention may contain a vaporization promoter for PBS-based resin in an amount of more than 0 mass%, 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, or 30 mass% or more, and less than 100 mass%, 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, or 30 mass% or less, based on the total mass of the composition. For example, the composition may contain a vaporization promoter for PBS-based resin in an amount of 1 mass% to 90 mass%, 3 mass% to 80 mass%, 5 mass% to 70 mass%, 7 mass% to 60 mass%, 8 mass% to 50 mass%, 9 mass% to 40 mass%, or 10 mass% to 30 mass%, based on the total mass of the composition.

[0074] When the content of the vaporization promoter for the PBS-based resin satisfies the above range, the vaporization of the PBS-based resin is efficiently promoted, and the composition according to one embodiment of the present invention can exhibit excellent biodegradation effect at room temperature of 30° C. even when the composition contains the PBS-based resin in an amount of 10% by mass or more, 20% by mass or more, 40% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.

[0075] The vaporization promoter for PBS-based resins can include polyhydroxyalkanoate (hereinafter referred to as "PHA") resins. PHA resins have specific physical properties (e.g., specific crystal structures, components derived from specific monomers, etc.), and therefore can efficiently promote the vaporization of PBS-based resins.

[0076] While PHA resin has similar physical properties to synthetic resins such as polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), and polybutylene succinate adipate (PBSA), PHA resin is completely biodegradable and has excellent biocompatibility.

[0077] Specifically, PHA resin is a natural thermoplastic polyester polymer that accumulates in microbial cells.In addition, since PHA resin has biodegradability, PHA resin can be composted and can eventually be decomposed into carbon dioxide, water and organic waste without generating toxic waste.In particular, PHA resin is biodegradable in soil and sea.Therefore, when the composition according to one embodiment of the present invention includes PHA resin, it is biodegradable under all environmental conditions such as soil and sea, and is environmentally friendly.

[0078] For example, when the cumulative amount of carbon dioxide (CO2) generated in a composition composed of 100% by mass of PHA resin was measured at 30°C for 12 weeks in accordance with ISO 14855, the vaporization rate (V) calculated by Equation 1 was 10w ) can be, for example, 90% or more, 91% or more, 91.5% or more, 92% or more, 93.5% or more, 95% or more, or 97% or more, and shows an extremely excellent biodegradation effect at room temperature.

[0079] PHA resins can be formed by enzyme-catalyzed polymerization of one or more monomers in living cells.

[0080] Specifically, the PHA resin can be a copolymerized polyhydroxyalkanoate resin (hereinafter referred to as a "PHA copolymer"), more specifically, a copolymer in which repeat units derived from two or more different monomers are randomly distributed within the polymer chain. Furthermore, the PHA resin can include isomers. For example, the PHA resin can include structural isomers, enantiomers, or geometric isomers. Specifically, the PHA resin can include structural isomers.

[0081] Specific examples of monomers that can be used to prepare PHA include 2-hydroxybutyrate, lactic acid, glycolic acid, 3-hydroxybutyrate (hereinafter referred to as "3-HB"), 3-hydroxypropionate (hereinafter referred to as "3-HP"), 3-hydroxyvalerate (hereinafter referred to as "3-HV"), 3-hydroxyhexanoate (hereinafter referred to as "3-HH"), 3-hydroxyheptanoate (hereinafter referred to as "3-HHep"), 3-hydroxyoctanoate (hereinafter referred to as "3 -HO"), 3-hydroxynonanoate (hereinafter referred to as "3-HN"), 3-hydroxydecanoate (hereinafter referred to as "3-HD"), 3-hydroxydodecanoate (hereinafter referred to as "3-HDd"), 4-hydroxybutyrate (hereinafter referred to as "4-HB"), 4-hydroxyvalerate (hereinafter referred to as "4-HV"), 5-hydroxyvalerate (hereinafter referred to as "5-HV"), and 6-hydroxyhexanoate (hereinafter referred to as "6-HH"). The PHA resin may contain repeating units derived from one or more monomers selected from the above.

[0082] Specifically, the PHA resin can include repeat units (at least one repeat unit) derived from one or more monomers selected from the group consisting of 3-HB, 4-HB, 3-HP, 3-HV, 3-HH, 4-HV, 5-HV, and 6-HH.

[0083] More specifically, the PHA resin can include repeat units derived from 4-HB monomers, i.e., the PHA resin can be a PHA copolymer that includes repeat units derived from 4-HB monomers.

[0084] The PHA resin can be a PHA copolymer that contains repeat units derived from 4-HB monomers and further contains repeat units derived from monomers different from the 4-HB monomers, or further contains repeat units derived from two, three, four, five, six or more monomers that are different from one another (two or more repeat units that are different from one another).

[0085] Specifically, the vaporization promoter for PBS-based resin according to the embodiment of the present invention may include a repeating unit derived from a 4-HB monomer, and may include a resin (PHA copolymer) including a repeating unit (at least one repeating unit) derived from at least one monomer selected from the group consisting of a 3-HB monomer, a 3-HP monomer, a 3-HV monomer, a 3-HH monomer, a 4-HV monomer, a 5-HV monomer, and a 6-HH monomer. More specifically, the vaporization promoter for PBS-based resin may include a resin (PHA copolymer) including a repeating unit derived from a 3-HB monomer (hereinafter referred to as a "3-HB repeating unit") and a repeating unit derived from a 4-HB monomer (hereinafter referred to as a "4-HB repeating unit"). For example, it may include a poly-3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter referred to as a "P3-HB-co-4-HB") copolymer.

[0086] According to one embodiment of the present invention, in order to promote the vaporization of the PBS-based resin while increasing the biodegradability of the composition in soil and sea, it may be important to adjust the content ratio of 3-HB repeat units and 4-HB repeat units contained in the PHA resin.

[0087] For example, in a PHA resin containing 3-HB repeating units and 4-HB repeating units, the molar ratio of the 3-HB repeating units to the 4-HB repeating units can be 20:80 to 99:1, 30:70 to 99:1, 40:60 to 99:1, 50:50 to 95:5, 50:50 to 94:6, 50:50 to 92:8, 55:45 to 92:8, or 55:45 to 90:10. When the molar ratio of the 3-HB repeating units to the 4-HB repeating units satisfies the above range, it can be more advantageous in achieving the biodegradation effect targeted in the present invention.

[0088] Specifically, the content of the 4-HB repeat unit may be 1 mol% to 80 mol%, 2 mol% to 70 mol%, 3 mol% to 60 mol%, 5 mol% to 50 mol%, 8 mol% to 45 mol%, or 10 mol% to 45 mol% based on the total number of moles (moles) of the 3-HB repeat unit and the 4-HB repeat unit. Also, the content of the 4-HB repeat unit may be 1 mol% to 80 mol%, 2 mol% to 70 mol%, 3 mol% to 60 mol%, 5 mol% to 50 mol%, 8 mol% to 45 mol%, or 10 mol% to 45 mol% based on the total mass of the 3-HB repeat unit and the 4-HB repeat unit.

[0089] Furthermore, in PHA resins containing at least one 4-HB repeat unit, the crystallinity of the PHA resin can be adjusted according to the content of the 4-HB repeat unit. That is, the PHA resin can be a PHA copolymer with controlled crystallinity. In particular, the PHA resin can be classified as a semi-crystalline PHA (scPHA) copolymer or an amorphous PHA (aPHA) copolymer according to the content of the 4-HB repeat unit.

[0090] The crystallinity-adjusted PHA resin can have its crystallinity or amorphousness adjusted by increasing the disorder of its molecular structure. Specifically, the crystallinity and amorphousness can be determined by the type of monomer, the ratio of repeating units derived from the monomer, or the type and / or content of isomers.

[0091] Specifically, the PHA resin can be an amorphous PHA (aPHA) copolymer containing 4-HB repeat units. When the vaporization promoter for PBS-based resin contains such an amorphous PHA (aPHA) copolymer, the vaporization of the PBS-based resin can be more efficiently promoted.

[0092] On the other hand, the PHA resin can have a glass transition temperature (Tg) of, for example, -45°C to 80°C, -35°C to 80°C, -30°C to 80°C, -25°C to 75°C, -20°C to 70°C, -35°C to 5°C, -25°C to 5°C, -35°C to 0°C, -25°C to 0°C, -30°C to -10°C, -35°C to -15°C, -35°C to -20°C, -20°C to 0°C, -15°C to 0°C, or -15°C to -5°C.

[0093] The crystallization temperature (Tc) of the PHA resin may not be measured, for example, or may be, for example, 60°C to 120°C, 70°C to 120°C, 75°C to 120°C, 75°C to 115°C, 75°C to 110°C, or 90°C to 110°C.

[0094] The melting temperature (Tm) of the PHA resin may not be measured, for example, or may be, for example, 100°C to 170°C, 105°C to 160°C, 110°C to 150°C, 115°C to 155°C, or 120°C to 140°C.

[0095] The PHA resin may have a mass average molecular weight (Mw) of, for example, 10,000 g / mol to 1,200,000 g / mol. Specifically, the mass average molecular weight of the PHA resin may be 50,000 g / mol to 1,200,000 g / mol, 100,000 g / mol to 1,200,000 g / mol, 50,000 g / mol to 1,000,000 g / mol, 100,000 g / mol to 1,000,000 g / mol, or 200,000 g / mol to 1,200,000 g / mol. 0,000 g / mol, 250,000 g / mol to 1,150,000 g / mol, 300,000 g / mol to 1,100,000 g / mol, 350,000 g / mol to 1,000,000 g / mol, 350,000 g / mol to 950,000 g / mol, 100,000 g / mol to 900,000 g / mol, 200 ,000g / mol~800,000g / mol, 200,000g / mol~700,000g / mol, 250,000g / mol~650,000g / mol, 200,000g / mol~400,000g / mol, 300,000g / mol~800,000g / mol, 300,000g / mol~600,000g / mol The molecular weight of the carboxyl group can be, for example, 500,000 g / mol to 1,200,000 g / mol, 500,000 g / mol to 1,000,000 g / mol, 550,000 g / mol to 1,050,000 g / mol, 550,000 g / mol to 900,000 g / mol, or 600,000 g / mol to 900,000 g / mol.

[0096] On the other hand, the composition according to one embodiment of the present invention may contain a PBS-based resin and a vaporization promoter for the PBS-based resin in a specific content ratio. Specifically, the content ratio (mass ratio) of the PBS-based resin and the vaporization promoter for the PBS-based resin may be, for example, 10:90 to 99:1, 20:80 to 98:2, 30:70 to 95:5, 45:55 to 94:6, 50:50 to 93:7, 55:45 to 90:10, 60:40 to 90:10, 65:35 to 90:10, or 70:30 to 90:10. When the content ratio (mass ratio) of the PBS-based resin and the vaporization promoter for the PBS-based resin satisfies the above range, the vaporization of the PBS-based resin can be significantly promoted.

[0097] Additives The composition according to one embodiment of the present invention may further comprise at least one additive selected from the group consisting of antioxidants, compatibilizers, extenders, nucleating agents, melt strength enhancers and slip agents.

[0098] The content of the additives can be adjusted according to the desired effect and use of the composition. The content of the additives can be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 1.5 mass% or more, or 2 mass% or more, and 30 mass% or less, 28 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, or 5 mass% or less, based on the total mass of the composition.

[0099] As the additives, known additives can be used depending on the desired effects and applications.

[0100] Aspects of the invention The present disclosure will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited to these examples. EXAMPLES

[0101] Example 1 As shown in Table 1 below, a composition was prepared by mixing PBS resin (MITSUBISHI, BioPBS™) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Cheil Jedang, Korea) as a vaporization promoter for PBS-based resin in a mass ratio of 70:30.

[0102] Example 2 As shown in Table 1 below, a composition was prepared by mixing PBS resin (MITSUBISHI, BioPBS™) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Cheil Jedang, Korea) as a vaporization promoter for PBS-based resin in a mass ratio of 80:20.

[0103] Example 3 As shown in Table 1 below, a composition was prepared by mixing PBS resin (MITSUBISHI, BioPBS™) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Cheil Jedang, Korea) as a vaporization promoter for PBS-based resin in a mass ratio of 90:10.

[0104] Comparative Example 1 As shown in Table 1 below, a composition composed of 100% by weight of PBS resin (MITSUBISHI, BioPBS™) was prepared.

[0105] Comparative Example 2 As shown in Table 1 below, a composition composed of 100 mass % polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, scPHA) (CJ, Korea) was prepared as a vaporization promoter for PBS-based resin.

[0106] Comparative Example 3 As shown in Table 1 below, a composition was prepared by mixing PBAT, i.e., poly(butylene adipate-co-terephthalate) resin, and PHA (polyhydroxyalkanoate) resin (P3-HB-co-4-HB, aPHA) (CJ, Korea) as a vaporization promoter for the PBAT resin in a mass ratio of 70:30.

[0107] The contents and physical properties of the compositions obtained in the examples and comparative examples are shown in Table 1 below.

[0108] [Table 1]

[0109] Evaluation example Evaluation example 1: Degree of vaporization The cumulative amount of carbon dioxide generated under aerobic composting conditions was measured in accordance with ISO 14855, and the degree of evaporation (V 10W ) was calculated.

[0110] Specifically, as an evaluation group, each of the composition samples of the examples and comparative examples was collected so that the total dry mass of the composition sample and compost was 14.3 mass% and mixed with compost (Abnexo Co., Ltd.) to prepare a test vessel containing the mixture. In this case, the initial moisture content of the compost was measured by LOD moisture measurement using an HMA or a drying oven. Additional moisture was added to adjust the final moisture content to 50%, and the dry mass was adjusted. Furthermore, in accordance with the ISO 14855 notification regulations, a mixture was prepared by uniformly mixing 20 g of a dry composition sample (moisture content 0%) and 240 g of compost with a moisture content of 50% (dry mass 120 g) to adjust the sample:compost ratio to 1:6.

[0111] Furthermore, as a control, an inoculum source container containing only compost without containing any composition sample was prepared.

[0112] After that, after 12 weeks at 30°C, normal pressure and aerobic conditions, the carbon dioxide generated in each container was captured using an ECHO respirometer device and titrated with an NIR (near infrared sensor) through a system within this device to measure the cumulative amount of carbon dioxide generated from each container.

[0113] Using the measured cumulative amount of generated carbon dioxide, the vaporization degree (V) is calculated using the following formula 1. 10w ) was calculated.

[0114] [ka]

[0115] In formula 1, (CO2) S is the cumulative amount (g) of carbon dioxide (CO2) generated in a test container containing 14.3% by mass of the sample and compost based on the total dry mass of the sample and compost, and (CO2) B is the cumulative amount of carbon dioxide (CO2) (g) generated in the inoculum container containing only compost, and (CO2) THVis the theoretical cumulative amount of carbon dioxide (CO2) generated in the test vessel and is expressed by the following formula 2.

[0116] [ka]

[0117] In Equation 2, Cw is the mass (g) of organic carbon contained in the sample. Specifically, Cw is the content (g) of carbon element contained in the sample.

[0118] Evaluation example 2: Improvement in evaporation promotion The degree of vaporization promotion improvement (ΔVID) was measured to measure the degree to which the vaporization of PBS-based resin was promoted by the vaporization promoter for PBS-based resin. 10W ) was evaluated.

[0119] Specifically, the vaporization degree (V 10W ) and the theoretical vaporization degree (V THV10w ) and the evaporation promotion improvement degree (ΔVID 10W The theoretical vaporization degree V THV10w was calculated according to the following formula 4:

[0120] [ka]

[0121] In Equation 3, V 10w is as defined in Evaluation Example 1, and V THV10w is expressed by the following formula 4.

[0122] [ka]

[0123] In formula 4, x is the mass percentage of the PBS-based resin contained in the composition based on the total mass of the composition.

[0124] In Comparative Example 3, the evaporation promotion improvement degree (ΔVID 10W When calculating x in Equation 4, x is the mass percentage of the PBAT resin contained in the composition based on the total mass of the composition.

[0125] [Table 2]

[0126] [Table 3]

[0127] Referring to Table 3 above, when the cumulative amount of carbon dioxide (CO2) generated over a period of 12 weeks at 30°C was measured, the vaporization degree (V) of the compositions of Examples 1 to 3 actually evaluated was 10W In particular, in Examples 1 to 3, which used compositions containing a PBS-based resin and a vaporization promoter for the PBS-based resin, the vaporization degree (V) of Comparative Example 1, which used a composition composed of 100 mass % of the PBS-based resin, was 20% or more. 10w ) against the evaporation promotion improvement degree (ΔVID 10w ) has increased significantly by more than 30%.

[0128] On the other hand, in Comparative Example 3 in which the PHA resin was used together with the PBAT resin as a vaporization promoter for the PBS-based resin according to the present invention, the vaporization promotion improvement degree (ΔVID 10W ) was a negative value, indicating that the PHA resin specifically promoted the vaporization of the PBS-based resin.

Claims

1. A composition containing a polybutylene succinate (PBS)-based resin in an amount ranging from 10% by mass to less than 100% by mass based on the total mass of the composition, the composition being characterized in that the carbon dioxide (CO) generated over a period of 12 weeks at 30° C. is measured in accordance with ISO 14855. ２ When the cumulative amount of vaporization (V) is measured, the vaporization degree (V １０Ｗ ) is 20% or more. 【Chemistry 1】 In formula 1, (CO ２ ) Ｓ is the amount of carbon dioxide (CO) generated in a test vessel containing compost and 14.3% by mass of the sample based on the total dry mass of the sample and the compost. ２ ) is the cumulative amount (g) of (CO ２ ) Ｂ is the amount of carbon dioxide (CO) generated in an inoculum container containing only compost. ２ ) is the cumulative amount (g) of (CO ２ ) ＴＨＶ is the carbon dioxide (CO ２ ) is a theoretical cumulative amount of 100% by mass spectrometry, and is represented by the following formula 2: 【Chemistry 2】 In Equation 2, Cw is the mass (g) of organic carbon contained in the sample.

2. The composition of claim 1 further comprising a vaporization promoter for polybutylene succinate (PBS) based resins.

3. The composition according to claim 2, wherein the mass ratio of the polybutylene succinate (PBS)-based resin to the vaporization promoter for the polybutylene succinate (PBS)-based resin is 10:90 to 90:

10.

4. The evaporation promotion improvement degree (ΔVID １０Ｗ 3. The composition according to claim 2, wherein the content of 0.1% or more of 【Chemistry 3】 In formula 3, V １０ｗ is as defined in claim 1, V ＴＨＶ１０ｗ is represented by the following formula 4: 【Chemistry 4】 In formula 4, x is the mass percentage of the polybutylene succinate (PBS) resin contained in the composition based on the total mass of the composition.

5. The composition of claim 2, wherein the vaporization promoter for polybutylene succinate (PBS)-based resins satisfies at least one of the following characteristics: A glass transition temperature (Tg) of −45° C. to 80° C. A crystallization temperature (Tc) of 60°C to 120°C, and Melting temperature (Tm) between 100°C and 170°C.

6. The polybutylene succinate (PBS)-based resin includes at least one selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and polybutylene succinate terephthalate (PBST); 3. The composition of claim 2, wherein the vaporization promoter for polybutylene succinate (PBS) based resins comprises a resin containing a repeat unit derived from a 4-hydroxybutyrate (4-HB) monomer and a repeat unit derived from at least one monomer selected from the group consisting of 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvalerate (3-HV), 3-hydroxyhexanoate (3-HH), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV), and 6-hydroxyhexanoate (6-HH).

7. The composition of claim 6, wherein the vaporization promoter for polybutylene succinate (PBS) based resin comprises a resin containing repeat units derived from the 3-hydroxybutyrate (3-HB) monomer and repeat units derived from the 4-hydroxybutyrate (4-HB) monomer.

8. 8. The composition of claim 7, wherein the resin comprises repeat units derived from the 3-hydroxybutyrate (3-HB) monomer in an amount ranging from 1 mol % to 80 mol %, based on the total number of moles of repeat units derived from the 4-hydroxybutyrate (4-HB) monomer.

9. A vaporization promoter for polybutylene succinate (PBS)-based resins, comprising a resin containing a repeat unit derived from a 3-hydroxybutyrate (3-HB) monomer and a repeat unit derived from a 4-hydroxybutyrate (4-HB) monomer.

10. The vaporization promoter for polybutylene succinate (PBS)-based resins according to claim 9, wherein the molar ratio of the repeating units derived from the 3-hydroxybutyrate (3-HB) monomer to the repeating units derived from the 4-hydroxybutyrate (4-HB) monomer is 40:60 to 99:1.

Images