Volatile promoters for polylactic acid resins and similar components.

Abstract

DEPCT68 One form of this disclosure involves: an element containing at least 10%. It contains less than 100% by weight of polylactic acid (PLA) resin, based on... The total weight of the components and the evaporation rate (V10W) must be 50% or more as specified. This is achieved by measuring the cumulative amount of carbon dioxide (CO2) produced after 10 weeks. At 30 degrees Celsius; and polylactic acid (PLA) resin evaporation enhancer for evaporation promotion. Polylactic acid (PLA) resin volatile organic compounds (VOCs) promoters can... It significantly accelerates the evaporation of polylactic acid (PLA) resins with low evaporation levels. At room temperature of 30 degrees Celsius, this improves the biodegradation of polylactic acid. (PLA);

Description

Polylactic acid resin vaporization accelerator and composition containing the same

[0001] The present invention relates to a vaporization promoter that promotes vaporization of a polylactic acid resin and a composition containing the same.

[0002] Currently commercialized general-purpose plastics have excellent physical properties and are experiencing increasing demand due to stable supply and price. However, the problem of waste plastic disposal has arisen in all aspects of life, and they are becoming a factor in causing serious environmental pollution because they do not decompose in natural environments such as the ocean and soil.

[0003] To solve these environmental pollution problems, research on biodegradable plastics has been actively conducted recently.

[0004] The above biodegradable plastic refers to a material that is broken down into low-molecular substances by microorganisms existing in nature, and ultimately broken down into water and carbon dioxide, or water and methane gas.

[0005] Among these biodegradable plastics, polylactic acid resin, which is a representative example, is a biodegradable thermoplastic polyester with great potential to replace traditional petrochemical polymers. It is the most widely studied renewable polymer material to date, and its use is being actively developed.

[0006] Although the above polylactic acid resin has the property of being able to rapidly decompose and regenerate carbon dioxide (CO2) under specific composting conditions, there is a problem in that the specific composting conditions required for the polylactic acid resin to decompose and generate carbon dioxide are very demanding.

[0007] Specifically, polylactic acid resin is very difficult to biodegrade under room temperature conditions because it naturally decomposes under high temperatures of over 50℃ and high humidity of about 40%, and in soil with many microorganisms, ultimately generating carbon dioxide. In addition, it takes a long time to decompose in natural conditions such as the ocean and soil.

[0008] To solve this problem, an artificial biodegradation environment can be created, but maintaining the above-mentioned specific composting (biodegradation) conditions incurs high costs and requires sufficient oxygen supply, so there are still significant limitations in improving the decomposition rate of polylactic acid resin.

[0009] [Prior Art Literature]

[0010] [Patent Document]

[0011] (Patent Document 1) Korean Patent Publication No. 2014-0112200

[0012] The present invention has been invented to solve the problems of the above-described prior art.

[0013] The present invention aims to provide a polylactic acid (PLA) resin vaporization accelerator capable of improving the vaporization rate of polylactic acid (PLA) resin having a low vaporization rate at room temperature of 30°C, thereby accelerating the biodegradation effect (speed) of polylactic acid (PLA) resin even at room temperature, and a composition including the same.

[0014] According to one aspect of the present invention, a polylactic acid (PLA) resin is included in an amount of 10 wt% or more and less than 100 wt% based on the total weight of the composition, and when the cumulative amount of carbon dioxide (CO2) generated after 10 weeks at 30°C is measured in accordance with ISO 14855, the vaporization degree (V) is expressed by the following equation 1 10w ) provides a composition having 50% or more of:

[0015] [Formula 1]

[0016]

[0017] In the above equation 1,

[0018] (CO2) S Carbon dioxide (CO2) in a test vessel containing 14.3 wt% of the sample based on the total dry weight of the compost and the sample and the compost. is the cumulative amount (g),

[0019] (CO2) B Carbon dioxide (CO2) in the inoculum container containing only compost is the cumulative amount (g),

[0020] (CO2) THV is the theoretical carbon dioxide (CO2) in the above test vessel. As the cumulative amount (g), it is expressed by the following equation 2,

[0021] [Formula 2]

[0022]

[0023] In the above equation 2,

[0024] Cw is the mass (g) of organic carbon contained in the sample.

[0025] In one embodiment, the composition may further comprise a polylactic acid (PLA) resin vaporization accelerator.

[0026] In another embodiment, the weight ratio of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator may be 10:90 to 90:10.

[0027] In another embodiment, the composition has an improvement in vaporization acceleration (ΔVID) as represented by the following formula 3 10W ) may be more than 1%:

[0028] [Formula 3]

[0029] ΔVID 10W (%) = V 10w - V THV10w

[0030] In the above equation 3,

[0031] V 10wis as defined above,

[0032] V THV10w is expressed by the following equation 4,

[0033] [Formula 4]

[0034]

[0035] In the above equation 4,

[0036] x is the weight percentage of polylactic acid (PLA) resin included in the composition based on the total weight of the composition.

[0037] In another embodiment, the polylactic acid (PLA) resin vaporization accelerator may satisfy one or more of the following properties:

[0038] Glass transition temperature (Tg) of -45℃ to 80℃,

[0039] A crystallization temperature (Tc) of 60°C to 120°C, and

[0040] Melting temperature (Tm) of 100°C to 170°C.

[0041] In another embodiment, the polylactic acid (PLA) resin vaporization accelerator may include a resin comprising repeating units derived from a 3-hydroxybutyrate (3-HB) monomer and repeating units derived from a 4-hydroxybutyrate (4-HB) monomer.

[0042] In another embodiment, the polylactic acid (PLA) resin vaporization accelerator may include repeating units derived from the 4-hydroxybutyrate (4-HB) monomer in an amount of 1 mol% to 80 mol% based on the total moles of repeating units derived from the 3-hydroxybutyrate (3-HB) monomer and repeating units derived from the 4-hydroxybutyrate (4-HB) monomer.

[0043] According to another aspect of the present invention, a polylactic acid (PLA) resin vaporization accelerator comprising a resin comprising a repeating unit derived from a 3-hydroxybutyrate (3-HB) monomer and a repeating unit derived from a 4-hydroxybutyrate (4-HB) monomer can be provided.

[0044] In one embodiment, the molar ratio of the repeating unit derived from the 3-hydroxybutyrate (3-HB) monomer and the repeating unit derived from the 4-hydroxybutyrate (4-HB) monomer may be 40:60 to 99:1.

[0045] A composition according to one embodiment of the present invention includes a polylactic acid (PLA) resin having a low vaporization rate at room temperature of 30°C, and when measuring the cumulative amount of carbon dioxide (CO2) generated after 10 weeks, the vaporization rate is higher than a specific range, so that an excellent biodegradation effect can be realized at room temperature.

[0046] In addition, the polylactic acid (PLA) resin vaporization accelerator according to one embodiment of the present invention can significantly accelerate vaporization of polylactic acid (PLA) resin having a low vaporization rate at room temperature of 30°C.

[0047] Therefore, the above composition and the polylactic acid (PLA) resin vaporization accelerator can be utilized in various fields and can effectively act for environmental conservation along with excellent physical properties.

[0048] Figure 1 shows the vaporization rate (V) over time at room temperature of 30°C of the compositions of Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention. 10w ) is a graph showing the

[0049] Hereinafter, the invention will be described in detail through examples. It should be noted that the examples are not limited to the contents disclosed below and may be modified in various ways as long as the gist of the invention remains unchanged.

[0050] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0051] In addition, all numerical ranges indicating the physical properties, dimensions, etc. of the components described in this specification should be understood to be modified by the term “about” in all cases unless otherwise specified.

[0052] The present invention applies the cumulative amount of carbon dioxide (CO2) generated under aerobic composting conditions to calculate the vaporization rate (V). 10w ) is controlled to appear above a certain range, and relates to a composition (vaporization composition, or biodegradable composition) that can be biodegraded well at room temperature even if it includes polylactic acid (PLA) resin that is difficult to biodegrade at room temperature (e.g., 25±5 ℃), and a polylactic acid resin vaporization accelerator included in the composition, which will be specifically described as follows.

[0053]

[0054] [Composition]

[0055] A composition according to one embodiment of the present invention comprises polylactic acid (PLA) resin in an amount of 10 wt% or more and less than 100 wt% based on the total weight of the composition, and when measuring the cumulative amount of carbon dioxide (CO2) generated after 10 weeks at 30°C according to ISO 14855, the vaporization degree (V) is expressed by the following equation 1 10w ) is more than 50%:

[0056] [Formula 1]

[0057]

[0058] In the above equation 1,

[0059] (CO2) SCarbon dioxide (CO2) in a test vessel containing compost and a sample (composition sample) of 14.3 wt% based on the total dry weight of the compost. is the cumulative amount (g),

[0060] (CO2) B Carbon dioxide (CO2) in the inoculum container containing only compost is the cumulative amount (g),

[0061] (CO2) THV is the theoretical carbon dioxide (CO2) in the test vessel (test vessel (a+b) containing compost (a) and sample (b) corresponding to 14.3 wt% of the total dry weight of the sample and compost). As the cumulative amount (g), it is expressed by the following equation 2,

[0062] [Formula 2]

[0063]

[0064] In the above equation 2,

[0065] Cw is the mass (g) of organic carbon (carbon element) contained in the sample (sample corresponding to 14.3 wt% of the combined dry weight (x) of the sample and the dry weight (y) of the compost (x+y). Specifically, Cw refers to the content (g) of carbon element measured when the sample was subjected to elemental analysis.

[0066] Above (CO2) S and the above (CO2) B The weight of the compost used for measurement may be the same. Furthermore, the dry weight of the compost can be calculated using the Loss on Drying (LOD) principle, which measures the thermal gravimetric measurement of moisture. That is, the difference in weight loss during drying of the compost can be measured, and the dry weight can be confirmed through moisture analysis using a drying oven or a halogen moisture analyzer (HMA).

[0067] The above vaporization rate (V 10w) is a value measured when the composition is decomposed into low molecular weight substances and finally completely decomposed into carbon dioxide and vaporized, rather than the degree of biodegradation (biodegradation effect) in which the composition is decomposed into small pieces or molecules.

[0068] Specifically, the above vaporization rate (V 10w ) is a value calculated by measuring the cumulative amount of carbon dioxide (CO2), which is the final decomposition product of the composition, according to the ISO 14855 notification (specifically, ISO 14855-1 Aerobic Biodegradability Evaluation Method), and applying the measured cumulative amount of carbon dioxide (CO2) to the above equations 1 and 2, which can be an indicator of the degree of biodegradation of the composition at room temperature of 30°C.

[0069] The composition according to one embodiment of the present invention may further include a polylactic acid (PLA) resin vaporization accelerator. Specifically, the composition further including the polylactic acid (PLA) resin vaporization accelerator has a vaporization degree (V) represented by the above formula 1. 10w ) may be 50% or more. More specifically, the vaporization rate (V 10w ) may be an indicator indicating the degree of biodegradation of the composition including the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator.

[0070] That is, the above vaporization rate (V 10w ) is a composition sample containing the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator in a specific content ratio as an evaluation group, mixed with compost and placed in a test container, and then, using a measurement evaluation device (Respirometer equipment from ECHO Corporation), the cumulative carbon dioxide (CO2) generation amount (g) of the composition sample ((CO2)) is measured for 10 weeks under aerobic compost conditions at 30°C. S ) and carbon dioxide (CO2) in the inoculum container containing only compost without mixing the composition sample as a control group. Cumulative emissions (g) ((CO2)B ) was obtained under the same conditions as the above evaluation group, and then the carbon dioxide (CO2) of the above evaluation group and the above comparison group (CO2) which is the cumulative amount generated (g) S and (CO2) B Find the difference and use this as the theoretical carbon dioxide (CO2) represented by the above equation 2. Cumulative emissions (g) ((CO2) THV ) may be converted into a percentage.

[0071] According to one embodiment of the present invention, when measuring the cumulative amount of carbon dioxide (CO2) generated after 10 weeks while including polylactic acid (PLA) resin, the composition has a vaporization rate (V) above a certain range. 10w ), it can exhibit excellent biodegradation effect at room temperature even if it contains polylactic acid (PLA) resin with low vaporization rate at room temperature of 30℃ and aerobic composting conditions. In the above aerobic composting conditions, the pressure condition can be normal pressure.

[0072] Specifically, the composition according to one embodiment of the present invention has the vaporization rate (V 10w ) may be, for example, 50.1% or more, 50.2% or more, 50.4% or more, 55% or more, 60% or more, 63% or more, 65% or more, 70% or more, 72% or more, or 75% or more.

[0073] Meanwhile, in the above formula 1, the (CO2) S For example, it may be 35g or more, 40g or more, 45g or more, 50g or more, 55g or more, or 60g or more.

[0074] In the above formula 1, the (CO2) S Wow (CO2) B The difference refers to the actual cumulative amount of carbon dioxide (CO2) generated from the sample (composition sample) itself, and may be, for example, 5 g or more, 10 g or more, 10 g to 60 g, 15 g to 50 g, or 15 g to 40 g.

[0075] In the above formula 1, the (CO2) THV refers to the theoretical maximum cumulative amount (g) of carbon dioxide (CO2) generated when the sample is completely oxidized (when the organic carbon contained in the sample is 100% converted to carbon dioxide (CO2)) in a test container containing compost and a sample (composition sample), and can be expressed by the above equation 2. That is, the above (CO2) THV It may be the product of the mass (Cw) of organic carbon (carbon atom) contained in the sample and the ratio (44 / 12) of the molecular weight of carbon dioxide (44) and the atomic weight of carbon atom (12). The (CO2) THV For example, it may be 10g or more, 15g or more, 20g or more, 20g to 60g, 25g to 50g, or 30g to 45g.

[0076] Meanwhile, the composition according to one embodiment of the present invention has an improvement in vaporization promotion (ΔVID) represented by the following formula 3 10W ) may be more than 1%:

[0077] [Formula 3]

[0078] ΔVID 10W (%) = V 10w - V THV10w

[0079] In the above equation 3,

[0080] V 10w is as defined above,

[0081] V THV10w is expressed by the following equation 4,

[0082] [Formula 4]

[0083]

[0084] In the above formula 4, x is the weight % of polylactic acid (PLA) resin included in the composition based on the total weight of the composition.

[0085] In the above formula 4, 3.6% is the vaporization rate (V) calculated by the formula 1 when measuring the cumulative amount of carbon dioxide (CO2) generated after 10 weeks at 30°C in a composition (PLA only composition) composed of 100 wt% of polylactic acid (PLA) resin according to ISO 14855. 10w ) and 93.5% is a composition consisting of 100 wt% of polylactic acid (PLA) resin vaporization accelerator (PLA resin vaporization accelerator alone) when measuring the cumulative amount of carbon dioxide (CO2) generated after 10 weeks at 30°C according to ISO 14855, the vaporization degree (V) calculated by the above equation 1 10w )am.

[0086] The above vaporization promotion improvement (ΔVID 10W ) is the vaporization rate (V) of the actually measured composition 10w ) in the theoretical composition of vaporization (V THV10w ) minus (V) 10w - V THV10w ) value, which may be an indicator of the degree to which polylactic acid (PLA) resin is accelerated in vaporization by a polylactic acid (PLA) resin vaporization accelerator.

[0087] The above vaporization promotion improvement (ΔVID 10W ) can be, for example, 2% or more, 3% or more, 5% or more, 10% or more, 15% or more, 20% or more, 22% or more, 23% or more, 24% or more, 25% or more, 26% or more, 28% or more, or 30% or more.

[0088] This improvement in vaporization promotion (ΔVID 10W ) may vary depending on the content or physical properties of the polylactic acid (PLA) resin included in the composition, or may vary depending on the content, component, or physical properties of the polylactic acid (PLA) resin vaporization accelerator included in the composition.

[0089] Specifically, when the content ratio (weight ratio) of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator included in the composition according to one embodiment of the present invention is 50:50, the vaporization acceleration improvement (ΔVID 10W ) can be, for example, 25% or more, 26% or more, 27% or more, or 28% or more.

[0090] In addition, when the content ratio (weight ratio) of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator is 75:25, the vaporization acceleration improvement (ΔVID 10W ) can be, for example, 20% or more, 22% or more, 23% or more, or 24% or more.

[0091] Meanwhile, in the above formula 3, the vaporization rate (V) of the theoretical composition THV10w ) may vary depending on the content (weight) of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator included in the composition. Specifically, the vaporization rate (V THV10w ) can be, for example, 10% or more, 15% or more, 20% or more, 20% to 60%, 25% to 55%, or 25% to 50%.

[0092] More specifically, when the content ratio (weight ratio) of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator included in the composition according to one embodiment of the present invention is 50:50, the vaporization degree (V) of the theoretical composition THV10w ) can be, for example, 20% or more, 30% or more, 40% or more, 20% to 60%, 30% to 55%, or 35% to 55%.

[0093] In addition, when the content ratio (weight ratio) of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator is 75:25, the vaporization degree (V) of the theoretical composition THV10w) can be, for example, 10% or more, 15% or more, 20% or more, 20% to 60%, 20% to 50%, or 20% to 40%.

[0094] The composition according to one embodiment of the present invention has a vaporization degree (V) that is equivalent to or higher than the vaporization degree of cellulose, which is a representative standard biodegradable material. 10w ) can be expressed.

[0095] Specifically, a composition according to one embodiment of the present invention comprises a polylactic acid (PLA) resin having a low vaporization rate at room temperature of 30°C, and has a vaporization rate (V) when measuring the cumulative amount of carbon dioxide (CO2) generated after 10 weeks. 10w ) is higher than a certain range (e.g., 50% or more), so it can exhibit excellent biodegradation effect at room temperature.

[0096] Therefore, the composition according to one embodiment of the present invention can be utilized in various fields and effectively contribute to environmental conservation along with excellent physical properties.

[0097]

[0098] Hereinafter, each component of the composition according to one embodiment of the present invention will be described in detail.

[0099]

[0100] polylactic acid (PLA) resin

[0101] A composition according to one embodiment of the present invention may include polylactic acid (PLA) resin in an amount of 10 wt% or more and less than 100 wt% based on the total weight of the composition.

[0102] The above polylactic acid (PLA) resin is based on biomass, unlike petroleum-based resins, so it can utilize renewable resources and has environmentally friendly properties as it is biodegraded by moisture and microorganisms when landfilled.

[0103] Such polylactic acid (PLA) resin can be obtained through L-lactic acid, D-lactic acid, D,L-lactic acid, or a combination thereof. Specifically, the polylactic acid (PLA) resin can be a random copolymer of L-lactic acid and D-lactic acid.

[0104] The polylactic acid (PLA) resin may have a weight average molecular weight (Mw) of, for example, 10,000 to 1,000,000 g / mol, 30,000 to 500,000 g / mol, 100,000 to 300,000 g / mol, or 100,000 to 200,000 g / mol. The weight average molecular weight (Mw) may be measured by gel permeation chromatography (GPC).

[0105] The polylactic acid (PLA) resin may have a melting temperature (Tm) of 100°C to 300°C, 110°C to 280°C, 120°C to 250°C, or 120°C to 200°C.

[0106] The above polylactic acid (PLA) resin may have a glass transition temperature (Tg) of 30°C to 100°C, 30°C to 80°C, 40°C to 80°C, or 45°C to 70°C.

[0107] According to one embodiment of the present invention, the composition may include the polylactic acid (PLA) resin in an amount of 10 wt% or more and less than 100 wt%, based on the total weight of the composition. Specifically, the composition may include the polylactic acid (PLA) resin in an amount of 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, or 70 wt% or more, based on the total weight of the composition, and may include less than 100 wt%, 98 wt% or less, 95 wt% or less, 90 wt% or less, 85 wt% or less, or 80 wt% or less. For example, the composition may include the polylactic acid (PLA) resin in an amount of 10 wt% or more and less than 100 wt%, 10 wt% to 95 wt%, 30 wt% to 95 wt%, 40 wt% to 90 wt%, or 50 wt% to 80 wt%, based on the total weight of the composition.

[0108] When the content of the polylactic acid (PLA) resin included in the composition according to one embodiment of the present invention is 100 wt%, the vaporization rate at room temperature of 30°C is very low, so it may be difficult to obtain the desired biodegradation effect. Specifically, when the composition composed of 100 wt% of the polylactic acid (PLA) resin is measured for the cumulative amount of carbon dioxide (CO2) generated after 10 weeks at 30°C according to ISO 14855, the vaporization rate (V) calculated by Equation 1 10w ) may be, for example, 5% or less, 4.5% or less, 4.0% or less, 3.6% or less, 3.0% or less, or 2.7% or less, so the biodegradation effect at room temperature may be very minimal.

[0109] Accordingly, a composition according to one embodiment of the present invention can improve the biodegradation effect by further including a polylactic acid (PLA) resin vaporization accelerator described below, thereby accelerating vaporization of polylactic acid (PLA) resin having a low vaporization rate at room temperature.

[0110]

[0111] Polylactic acid (PLA) resin vaporization accelerator

[0112] A composition according to one embodiment of the present invention may further include a polylactic acid (PLA) resin vaporization accelerator.

[0113] The above polylactic acid (PLA) resin vaporization accelerator can act as an accelerator that can accelerate vaporization of polylactic acid (PLA) resin having a low vaporization rate at room temperature of 30°C.

[0114] A composition according to one embodiment of the present invention may include the polylactic acid (PLA) resin vaporization accelerator in an amount of more than 0 wt%, 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 30 wt% or more, or 40 wt% or more, based on the total weight of the composition, and may include the polylactic acid (PLA) resin vaporization accelerator in an amount of less than 100 wt%, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, or 50 wt% or less. For example, the composition may include the polylactic acid (PLA) resin vaporization accelerator in an amount of from more than 0 wt% to less than 100 wt%, from more than 0 wt% to 90 wt%, from more than 0 wt% to 70 wt%, from 5 wt% to 90 wt%, from 5 wt% to 80 wt%, from 10 wt% to 70 wt%, from 20 wt% to 60 wt%, from 25 wt% to 60 wt%, or from 30 wt% to 50 wt%, based on the total weight of the composition.

[0115] When the content of the polylactic acid (PLA) resin vaporization accelerator satisfies the above range, vaporization of the polylactic acid (PLA) resin is efficiently accelerated, so that the composition according to one embodiment of the present invention can exhibit an excellent biodegradation effect at room temperature of 30°C even when the composition includes 10 wt% or more, 30 wt% or more, 50 wt% or more, or 70 wt% or more of the polylactic acid (PLA) resin.

[0116] The above polylactic acid (PLA) resin vaporization accelerator may include a polyhydroxyalkanoate (hereinafter referred to as "PHA") resin. The PHA resin has specific physical properties (e.g., specific crystal structure, components derived from specific monomers, etc.) and can efficiently promote vaporization of the polylactic acid (PLA) resin.

[0117] The above PHA resin has similar properties to synthetic resins such as petroleum-based resins such as polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), and polybutylene succinate adipate (PBSA), while exhibiting complete biodegradability and also having excellent biocompatibility.

[0118] Specifically, the PHA resin is a thermoplastic natural polyester polymer that accumulates in microbial cells, and is biodegradable, allowing composting, and can ultimately be decomposed into carbon dioxide, water, and organic waste without generating toxic waste. In particular, since the PHA resin can be biodegraded in soil and the ocean, when a composition according to an embodiment of the present invention includes the PHA resin, it can be biodegraded in any environmental conditions such as soil and the ocean, making it environmentally friendly. For example, when a composition composed of 100 wt% of the PHA resin is measured for the cumulative amount of carbon dioxide (CO2) generated after 10 weeks at 30°C according to ISO 14855, the vaporization rate (V) calculated by Equation 1 10w ) exhibits, for example, 90% or more, 91% or more, 91.5% or more, or 92% or more, so the biodegradation effect at room temperature is very excellent.

[0119] The above PHA resin can be formed by enzyme-catalyzed polymerization of one or more monomers within a living cell.

[0120] Specifically, the PHA resin may be a copolymerized polyhydroxyalkanoate resin (hereinafter referred to as a “PHA copolymer”), and more specifically, may be a copolymer in which repeating units derived from two or more different monomers are randomly distributed in a polymer chain. In addition, the PHA resin may include isomers. For example, the PHA resin may include structural isomers, enantiomers, or geometric isomers. Specifically, the PHA resin may include structural isomers.

[0121] Monomers that can be used in the production of the above PHA resin are specifically 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 The PHA resin may be selected from the group consisting of 4-hydroxybutyrate (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'), or 6-hydroxyhexanoate (hereinafter referred to as '6-HH'), and the PHA resin may include repeating units derived from one or more monomers selected from these.

[0122] Specifically, the PHA resin may include repeating units (one or more repeating units) 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.

[0123] More specifically, the PHA resin may comprise a repeating unit derived from a 4-HB monomer. That is, the PHA resin may be a PHA copolymer comprising a repeating unit derived from a 4-HB monomer. The PHA resin may be a PHA copolymer comprising a repeating unit derived from a 4-HB monomer, and further comprising a repeating unit derived from one monomer different from the 4-HB monomer, or further comprising a repeating unit derived from two, three, four, five, six or more monomers that are different from each other (two or more different repeating units).

[0124] A polylactic acid (PLA) resin vaporization accelerator according to one embodiment of the present invention may include a resin (PHA copolymer) comprising a repeating unit derived from a 4-HB monomer and a repeating unit (one or more repeating units) derived from one or more monomers 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 polylactic acid (PLA) resin vaporization accelerator 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'), and may include, for example, a poly 3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter referred to as 'P3-HB-co-4-HB') copolymer.

[0125] According to one embodiment of the present invention, in order to promote vaporization of polylactic acid (PLA) resin while increasing biodegradability of the composition in soil and the ocean, it may be important to control the content ratio of the 3-HB repeating unit and the 4-HB repeating unit included in the PHA resin.

[0126] For example, in the PHA resin including the 3-HB repeating unit and the 4-HB repeating unit, the molar ratio of the 3-HB repeating unit and the 4-HB repeating unit may 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 unit and the 4-HB repeating unit satisfies the above range, it may be more advantageous in realizing the biodegradation effect desired in the present invention.

[0127] Specifically, the content of the 4-HB repeating 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 moles of the 3-HB repeating unit and the 4-HB repeating unit.

[0128] Meanwhile, the crystallinity of the PHA resin containing at least one 4-HB repeating unit can be controlled depending on the content of the 4-HB repeating unit. That is, the PHA resin can be a PHA copolymer with controlled crystallinity. Specifically, the PHA resin can be classified into a semi-crystalline PHA (scPHA) copolymer or an amorphous PHA (aPHA) copolymer depending on the content of the 4-HB repeating unit.

[0129] The above PHA resin with controlled crystallinity may have controlled crystallinity and amorphousness by increasing irregularity in the molecular structure, and specifically, crystallinity and amorphousness may be determined depending on the type of monomer, the ratio of repeating units derived from the monomer, or the type and / or content of isomers.

[0130] Specifically, the PHA resin may be an amorphous PHA (aPHA) copolymer containing the 4-HB repeating unit, and the amorphous PHA (aPHA) copolymer may more efficiently promote vaporization of the polylactic acid (PLA) resin by including the polylactic acid (PLA) resin vaporization accelerator.

[0131] Meanwhile, the PHA resin may 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.

[0132] The PHA resin may have a crystallization temperature (Tc), for example, that may not be measured, or may be from 60°C to 120°C, from 70°C to 120°C, from 75°C to 120°C, from 75°C to 115°C, from 75°C to 110°C, or from 90°C to 110°C.

[0133] The PHA resin may have a melting temperature (Tm), for example, that may not be measured, or may be from 100°C to 170°C, from 105°C to 160°C, from 110°C to 150°C, from 115°C to 155°C, or from 120°C to 140°C.

[0134] The above PHA resin may have a weight average molecular weight (Mw) of, for example, 10,000 g / mol to 1,200,000 g / mol. Specifically, the weight average molecular weight of the PHA resin is 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, 200,000 g / mol to 1,200,000 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, 200,000 g / mol to 800,000 g / mol, 200,000 g / mol to 700,000 g / mol, 250,000 g / mol to 650,000 g / mol, 200,000 g / mol to 400,000 g / mol, 300,000 g / mol to 800,000 g / mol, 300,000 g / mol to 600,000 g / mol, 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, It may be 550,000 g / mol to 900,000 g / mol, or 600,000 g / mol to 900,000 g / mol.

[0135]

[0136] Meanwhile, a composition according to one embodiment of the present invention may include the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator in a specific content ratio. Specifically, the content ratio (weight ratio) of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator may be, for example, 10:90 to 90:10, 15:85 to 90:10, 20:80 to 90:10, 25:75 to 90:10, 30:70 to 90:10, 40:60 to 90:10, 45:55 to 85:15, 50:50 to 85:15, 50:50 to 80:20, 50:50 to 75:25, or 50:50 to 70:30. When the content ratio (weight ratio) of the polylactic acid (PLA) resin and the polylactic acid (PLA) resin vaporization accelerator satisfies the above range, vaporization of the polylactic acid (PLA) resin can be significantly accelerated.

[0137]

[0138] additives

[0139] A composition according to one embodiment of the present invention may further include one or more additives selected from the group consisting of an antioxidant, a compatibilizer, a weighting agent, a nucleating agent, a melt strength enhancer, and a slip agent.

[0140] The content of the additive may be adjusted depending on the desired effect and use of the composition. For example, the content of the additive may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 1.5 wt% or more, or 2 wt% or more, and 30 wt% or less, 28 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 8 wt% or less, or 5 wt% or less, based on the total weight of the composition.

[0141] The above additives may be commonly known additives depending on the desired effect and use.

[0142] The above contents are explained in more detail with the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples of the present invention is not limited to these examples.

[0143]

[0144] <Example>

[0145] Example 1

[0146] As shown in Table 1 below, a composition was prepared by mixing polylactic acid (PLA) resin (Nature Works, 4032D) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Corporation, Korea) as a polylactic acid (PLA) resin vaporization accelerator at a weight ratio of 50:50.

[0147]

[0148] Example 2

[0149] As shown in Table 1 below, a composition was prepared by mixing polylactic acid (PLA) resin (Nature Works, 4032D) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Corporation, Korea) as a polylactic acid (PLA) resin vaporization accelerator at a weight ratio of 75:25.

[0150]

[0151] Example 3

[0152] As shown in Table 1 below, a composition was prepared by mixing polylactic acid (PLA) resin (Nature Works, 2003D) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Corporation, Korea) as a polylactic acid (PLA) resin vaporization accelerator at a weight ratio of 50:50.

[0153]

[0154] Example 4

[0155] As shown in Table 1 below, a composition was prepared by mixing polylactic acid (PLA) resin (Nature Works, 2003D) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Corporation, Korea) as a polylactic acid (PLA) resin vaporization accelerator in a weight ratio of 70:30.

[0156]

[0157] Example 5

[0158] As shown in Table 1 below, a composition was prepared by mixing polylactic acid (PLA) resin (Nature Works, 2003D) and polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, aPHA) (CJ Corporation, Korea) as a polylactic acid (PLA) resin vaporization accelerator at a weight ratio of 60:40.

[0159]

[0160] Comparative Example 1

[0161] A composition consisting of 100 wt% polylactic acid (PLA) resin (Nature Works, 4032D) was used as shown in Table 1 below.

[0162]

[0163] Comparative Example 2

[0164] A composition consisting of 100 wt% of polyhydroxyalkanoate (PHA) resin (P3-HB-co-4-HB, scPHA) (CJ Corporation, Korea) used as a polylactic acid (PLA) resin vaporization accelerator as shown in Table 1 below was used.

[0165]

[0166] Comparative Example 3

[0167] As shown in Table 1 below, a composition was prepared by mixing polylactic acid (PLA) resin (Nature Works, 4032D) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) (Tianan, China) as a polylactic acid (PLA) resin vaporization accelerator at a weight ratio of 50:50.

[0168]

[0169] Control example 1

[0170] Cellulose, a standard biodegradable material, was used.

[0171]

[0172] The contents and properties of the compositions obtained in the above examples and comparative examples are summarized in Table 1 below. In this case, the Tg and Tm of Comparative Example 1 in Table 1 below are measured values ​​of the Tg and Tm of the PLA resin used in Comparative Example 1.

[0173]

[0174] ClassificationPLA resin: Weight ratio of PLA resin vaporization acceleratorPLA resin product nameComposition and properties of PLA resin vaporization accelerator (PHA resin)3-HB repeating unit (weight %)4-HB repeating unit (weight %)Tg(℃)Tm(℃)Tc(℃)Example 150:504032D5545-30--Example 275:255545-30--Example 350:502003D91.48.6-1799.55-Example 470:306931-16 and 57151-Example 560:406931-16 and 58152-Comparative example 1100:0---57.25167.43-Comparative example 20:1009010-5145101 Comparative Example 350:50 Use of PHBV as a PLA resin vaporization accelerator

[0175]

[0176] Evaluation example

[0177] Evaluation Example 1: Vaporization rate

[0178] The cumulative amount of carbon dioxide generated under aerobic composting conditions is measured according to ISO 14855 to determine the vaporization rate (V). 10w ) was measured.

[0179] Specifically, as an evaluation group, each of the composition samples of the above examples and comparative examples was taken at 14.3 wt% based on the total dry weight of the composition sample and compost, and a test container containing the resulting mixture was prepared by mixing it with compost (AB Nexo Co., Ltd.). At this time, the initial moisture content of the compost was confirmed through LOD moisture measurement using HMA or a drying oven, and additional moisture was added thereto to adjust the final moisture content to 50% to match the dry weight. In addition, the mixture was prepared by uniformly mixing 20 g of a dry composition sample (moisture content 0%) into 240 g of compost (dry weight: 120 g) whose moisture content was adjusted to 50% in order to adjust the sample:compost = 1:6 ratio based on the ISO 14855 notification regulations.

[0180] Additionally, as a control group, an inoculum container containing only compost without the above composition sample was prepared.

[0181] Afterwards, after 10 weeks under conditions of 30℃, atmospheric pressure, and aerobic conditions, the carbon dioxide generated from each container was captured using ECHO's Respirometer equipment, and the accumulated amount of carbon dioxide generated from each container was measured by titrating it with an NIR (Near infrared) sensor through the system within the equipment.

[0182] Using the accumulated amount of carbon dioxide measured, the vaporization rate (V) expressed by Equation 1 below is 10w ) was produced:

[0183] [Formula 1]

[0184]

[0185] In the above equation 1,

[0186] (CO2) S Carbon dioxide (CO2) in a test vessel containing 14.3 wt% of the sample based on the total dry weight of the compost and the sample and the compost. is the cumulative amount (g),

[0187] (CO2) B Carbon dioxide (CO2) in the inoculum container containing only compost is the cumulative amount (g),

[0188] (CO2) THV is the theoretical carbon dioxide (CO2) in the above test vessel. As the cumulative amount (g), it is expressed by the following equation 2,

[0189] [Formula 2]

[0190]

[0191] In the above equation 2,

[0192] 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.

[0193]

[0194] Evaluation Example 2: Improvement in vaporization promotion

[0195] To determine the degree to which polylactic acid (PLA) resin is accelerated by a polylactic acid (PLA) resin accelerator, the improvement in vaporization acceleration (ΔVID) was measured. 10W ) was evaluated.

[0196] Specifically, the above vaporization promotion improvement (ΔVID 10W ) is the vaporization rate (V) of Evaluation Example 1 10w ) and theoretical vaporization rate (V THV10w ) was used to calculate the theoretical vaporization rate (V THV10w ) was calculated by the following equation 4:

[0197] [Formula 4]

[0198]

[0199] In the above equation 4,

[0200] x is the weight percentage of polylactic acid (PLA) resin included in the composition based on the total weight of the composition.

[0201]

[0202] The results obtained in the above evaluation examples 1 and 2 are summarized in Table 2, Table 3 and Figure 1 below.

[0203]

[0204] Total mass of the sample (g) Mass of organic carbon contained in the sample (C w , g)CO2 conversion constant (44 / 12) Control example 1 (cellulose) 20.08.723.67Example 120.010.583.67Example 220.010.283.67Example 320.010.573.67Example 420.010.323.67Example 520.010.443.67Comparative example 120.0103.67Comparative example 220.011.143.67Comparative example 320.010.573.67

[0205] Classification (CO2) S (g)(CO2) B (g)(CO2) S - (CO2) B (g) Theoretical cumulative CO2 emissions at 100% conversion ((CO2) THV , g) Actual vaporization rate after 10 weeks (V in Equation 1) 10w , %)Theoretical vaporization rate after 10 weeks (V in Equation 4) THV10w , %) Improvement in vaporization promotion (ΔVID in Equation 3) 10W , %) Control Example 1 (Cellulose) 54.55 231.426 23.13 2.07 2.3 -- Example 1 61.11 631.426 29.73 8.87 6.64 8.628.1 Example 2 50.43 831.426 19.03 7.75 0.426 124.3 Example 3 66.63 736.878 29.83 8.87 6.84 8.628.2 Example 4 61.83 0 37.85 0 23.98 37.96 3.23 0.57 32.63 Example 5 65.50 0 37.85 0 27.65 38.37 2.139.56 32.54 Comparative Example 132.76231.4261.336.73.63.60Comparative example 269.63031.42638.240.893.593.50Comparative example 354.79136.87817.938.846.248.6-2.4

[0206] As can be seen from Table 3 and Figure 1 above, when measuring the cumulative amount of carbon dioxide (CO2) generated after 10 weeks at 30°C, the vaporization degree (V) of the compositions of Examples 1 to 5 actually evaluated 10w ) were all more than 50%, and it was found that all of them achieved the vaporization level of cellulose, a representative standard biodegradable material. Specifically, the compositions of Examples 1 to 5 had a vaporization level (V ) higher than that of Comparative Example 1, which used a composition composed of 100 wt% of polylactic acid (PLA) resin. 10w ) is significantly improved to 3.6% of the vaporization rate (V 10w ) was shown.

[0207] In addition, the vaporization rate (V) of Comparative Example 1 using a composition consisting of 100 wt% of polylactic acid (PLA) resin 10w ), in the case of Examples 1 to 5 using a composition including a polylactic acid (PLA) resin and a polylactic acid (PLA) resin vaporization accelerator, the vaporization acceleration improvement (ΔVID 10W ) was significantly improved by more than 5%, specifically, more than 20%.

[0208] In particular, the composition of Example 1, which includes polylactic acid (PLA) resin and polylactic acid (PLA) resin vaporization accelerator in a weight ratio of 50:50, has a theoretical cumulative carbon dioxide (CO2) generation amount ((CO2)) when completely oxidized (100% conversion). THV ) is 38.8g, and assuming that the polylactic acid (PLA) resin does not vaporize at room temperature, the cumulative amount of carbon dioxide (CO2) generated by the polylactic acid (PLA) resin is the above (CO2) THV It was predicted to be 19.4g, half of the value, but the amount of carbon dioxide (CO2) actually generated after 10 weeks (CO2) S - (CO2) B) was 29.7g, and it was found that the vaporization of polylactic acid (PLA) resin was accelerated by the polylactic acid (PLA) resin vaporization accelerator, which was an effect of promoting vaporization. That is, the amount of carbon dioxide (CO2) actually generated ((CO2) S - (CO2) B ) and predicted (CO2) THV It was predicted that the excess amount of about 10g, which is half the value, was the amount of carbon dioxide (CO2) generated by the polylactic acid (PLA) resin whose vaporization was promoted by the polylactic acid (PLA) resin vaporization accelerator.

[0209] From the above results, it was confirmed that the polylactic acid (PLA) resin vaporization accelerator not only has a high vaporization rate on its own, but can also significantly promote the vaporization of polylactic acid (PLA) resin.

[0210] Meanwhile, the composition of Comparative Example 3, in which PHBV was mixed with polylactic acid (PLA) resin at a weight ratio of 50:50 as a polylactic acid (PLA) resin vaporization accelerator, was confirmed to have no vaporization accelerating effect, and thus it was confirmed that the PHA resin of the present invention, which has specific properties, exhibits special properties by being applied as a polylactic acid (PLA) resin vaporization accelerator.

Claims

DEPCT681. Composition, which includes polylactic acid (PLA) resin in an amount ranging from 10% by weight to less than 100% by weight based on the total weight of the composition, when the cumulative amount of carbon dioxide (CO2) generated over 10 weeks at 30°C according to ISO14855, the degree of evaporation (V10w) represented by the following Equation 1 is 50% or more: [Equation 1]V10w(%)=(Equation)x100. In Equation 1, (CO2)S is the cumulative amount (grams) of carbon dioxide (CO2) generated in the test container containing compost and sample in an amount of 14.3%. By weight, based on the total dry weight of the sample and compost, (CO2)B is the cumulative amount (grams) of carbon dioxide (CO2) generated in the inoculation vessel containing compost alone, and (CO2)THV is the theoretical cumulative amount of carbon dioxide (CO2) generated in the test vessel and is represented by the following Equation 2, [Equation 2](CO2)THV(grams)=Cwx(Equation). In Equation 2, Cw is the mass (grams) of organic carbon present in the sample.

2. Components of claim 1, which are further included with the volatility enhancer for polylactic acid (PLA) resin. 3.Composition of Reputation 2, where the weight ratio of polylactic acid (PLA) resin and evaporation promoter for polylactic acid (PLA) resin is 10:90 to 90:

104. Composition of Reputation 2, where the degree of improvement in evaporation promoter (DeltaVID10W) is 1% or more as represented by the following Equation 3: [Equation 3] DeltaVID10W(%) = V10W - VTHV10w. In Equation 3, V10w is as defined in Reputation 1, and VTHV10w is represented by the following Equation 4: [Equation 4] VTHV10w(%) = 3.6% x (Equation) + 93.5% x (Equation) (Equation 4) x is the percentage by weight of polylactic acid (PLA) resin contained in the composition, based on the total weight of that composition.

5. The composition of claim 2, whereby the evaporation promoter for polylactic acid (PLA) resin is in accordance with at least one of the following characteristics: glass transition temperature (Tg) of -45°C to 80°C, crystallization temperature (Tc) of 60°C to 120°C, and melting temperature (Tm) of 100°C to 170°C. 6.The composition of claim 2, in which the volatility promoter for polylactic acid (PLA) resins consists of a resin which is composed of repeating units derived from 4-hydroxybutyrate (4-HB) monomer; and repeating units derived from at least one monomer selected from a 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, in which the volatility promoter for polylactic acid (PLA) resins consists of a resin which is composed of repeating units derived from 4-hydroxybutyrate (4-HB) monomer; and repeating units derived from at least one monomer selected from a group consisting of 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvalerate (3-HV), 3-hydroxyhexanoate (3-HH). Polylactic acid (PLA) resins are composed of repeating units derived from 3-hydroxybutyrate (3-HB) monomer; and repeating units derived from 4-hydroxybutyrate (4-HB) monomer.

8. Composition of claim 7, in which the volatility promoter for polylactic acid (PLA) resins is composed of repeating units derived from 4-hydroxybutyrate (4-HB) monomer in amounts ranging from 1% by mol to 80% by mol based on the total moles of repeating units derived from 3-hydroxybutyrate (3-HB) monomer and repeating units derived from 4-hydroxybutyrate (4-HB) monomer.9.Volatile promoter for polylactic acid (PLA) resins, which consists of repeating units derived from 3-hydroxybutyrate (3-HB) monomer; and repeating units derived from 4-hydroxybutyrate (4-HB) monomer10. Volatile promoter for polylactic acid (PLA) resins of claim 9, where the molar ratio of repeating units derived from 3-hydroxybutyrate (3-HB) monomer to repeating units derived from 4-hydroxybutyrate (4-HB) monomer is 40:60 to 99:1;.

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