WO2022092717A1 - Biodegradable resin composition containing polyvinyl alcohol and method for manufacturing same - Google Patents

Biodegradable resin composition containing polyvinyl alcohol and method for manufacturing same Download PDF

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WO2022092717A1
WO2022092717A1 PCT/KR2021/014921 KR2021014921W WO2022092717A1 WO 2022092717 A1 WO2022092717 A1 WO 2022092717A1 KR 2021014921 W KR2021014921 W KR 2021014921W WO 2022092717 A1 WO2022092717 A1 WO 2022092717A1
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weight
parts
biodegradable resin
biodegradable
resin composition
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French (fr)
Korean (ko)
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임유정
임재윤
박정현
박현규
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한화솔루션 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • the present invention relates to a biodegradable resin composition and a method for producing the same, and more particularly, to include polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) to improve biodegradability. It's about technology.
  • PBAT polybutylene adipate terephthalate
  • PVA polyvinyl alcohol
  • plastics Due to its excellent physical properties and cheap and light characteristics, plastics have been developed with various polymers centered on plastics beyond the limits of natural materials and have built a modern scientific civilization. Plastics are characterized by being strong, light, tough, and not easily decomposing, and due to these properties, they are used in a variety of ways, from industrial materials to disposable materials. Research has been conducted for a long time to further improve the toughness and durability of synthetic resins such as plastics, and these efforts are still ongoing.
  • environmental pollution by plastic waste is becoming a serious problem, for example, due to the detection of highly toxic dioxins and leakage of environmental hormones, not only the social demand for eco-friendly plastics, but also the legal regulations of each country on the use of non-degradable plastics. standards are also getting tighter. In order to solve this problem, the development of biodegradable polymers is being treated as a very important matter, and it is attracting attention as an important field in the plastics industry.
  • degradable plastics refer to plastics whose chemical structure is significantly changed for a certain period of time under specific environmental conditions according to the American Society for Testing and Materials (ASTM) in the United States, and the change in properties can be measured by standard test methods. It can be divided into collapsible and biodegradable plastics.
  • the photodegradable plastic refers to a plastic that is decomposed by light in the form of photooxidation or ketone photolysis.
  • photodegradable plastic is decomposed by light, there is a disadvantage in that it is not decomposed when buried in the ground where light is blocked.
  • Biodegradable plastics are partially degradable plastics manufactured by adding a certain amount of biodegradable substances such as starch to general non-degradable resins (polyethylene, polypropylene, etc.). The term plastic is used to separate them.
  • the biodegradable plastic generally refers to a plastic in which the plastic itself is completely decomposed into water and carbon dioxide or water and methane gas by microorganisms present in nature, such as bacteria, algae, and mold.
  • biodegradable plastics or biodegradable plastics were mainly used, but recently, the development of biodegradable plastics is being treated as an important issue. It is not only distinguished from the existing petroleum-based plastics by using natural plant resources from the raw material side, but also can provide cleanliness that is completely decomposed into water and carbon dioxide only by microorganisms in nature, so the global trend is also that biodegradable plastics are becoming mainstream. It is being developed while
  • thermoplastic film composition comprising a polymer blend of an immiscible polymer component.
  • the composition comprises a plasticized natural polymer, a polyolefin, a biodegradable polymer and a compatibilizer in the same polymer molecule.
  • the plasticized natural component and the biodegradable polymer component form the majority phase and the petroleum-based olefin polymer forms the minor phase.
  • the composition can be prepared into a film comprising a renewable natural polymer component.
  • Korean Patent Application Laid-Open No. 10-2017-0075052 (i) biodegradable resin (ii) starch in which at least one of the hydroxyl groups (-OH groups) of the glucose unit is hydrophobized with silane (iii) biodegradable polymer
  • a resin composition for a mulching film comprising any one or two or more compatibilizers selected from the group consisting of a graft copolymer grafted with maleic anhydride (MA), an epoxidized oil, and a polyfunctional compound having an epoxy group and the film are disclosed. Accordingly, the processability and mulching functionality of the film can be improved, and the tensile strength and tensile elongation of the film are improved.
  • Patent Document 1 Korean Patent Publication No. 10-2018-0023037 (2018.03.06)
  • Patent Document 2 Korean Patent Publication No. 10-2017-0075052 (2017.07.03)
  • An object of the present invention is to solve all of the above problems.
  • An object of the present invention is to improve the compatibility of a biodegradable resin composition and thereby improve the degradability of polyethylene.
  • An object of the present invention is to provide a film including the biodegradable resin composition, and to be applied to various fields such as industrial, food, agricultural, and the like.
  • an aspect of the present invention is
  • a biodegradable resin composition comprising polyethylene, a biodegradable resin, polybutylene adipate terephthalate (PBAT), and polyvinyl alcohol (PVA).
  • PBAT polybutylene adipate terephthalate
  • PVA polyvinyl alcohol
  • the polyethylene comprises a polymer selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), ethylene vinyl copolymer (EVA), and combinations thereof. may be doing
  • the biodegradable resin is thermoplastic starch (TPS), polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), It may include a material selected from the group consisting of polyhydroxybutyrate (PHB), cellulose, chitin, and combinations thereof.
  • the thermoplastic starch may include at least one selected from rice starch, wheat starch, corn starch, sweet potato starch, potato starch, tapioca starch, cassava starch, and modified starches thereof.
  • the weight average molecular weight of the polyethylene may be 100,000 to 1,000,000.
  • the polybutylene adipate terephthalate may have a weight average molecular weight of 10,000 to 100,000.
  • the biodegradable resin composition may have a melting temperature of 100° C. to 130° C., and a melt index of 0.01 to 10 g/10 min at 2.16 kg at 190° C. based on ASTM D1238.
  • the content of the biodegradable resin is 10 parts by weight to 600 parts by weight
  • the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 500 parts by weight
  • the content of alcohol (PVA) may be 10 parts by weight to 30 parts by weight.
  • the content of the biodegradable resin is 40 parts by weight to 100 parts by weight
  • the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 50 parts by weight
  • the content of alcohol (PVA) may be 10 parts by weight to 30 parts by weight.
  • the content of the biodegradable resin is 60 parts by weight to 70 parts by weight
  • the content of the polybutylene adipate terephthalate (PBAT) is 30 parts by weight to 45 parts by weight
  • the content of alcohol (PVA) may be 10 parts by weight to 25 parts by weight.
  • biodegradable film comprising the biodegradable resin composition.
  • the biodegradable film may have a weight change of -15% or more compared to the weight before embedding after being buried in soil for 4 weeks, and the weight change amount may be expressed by Equation 1 below.
  • Weight change (weight of biodegradable film after burying for 4 weeks - weight of biodegradable film before burial) / (weight of biodegradable film after burying for 4 weeks) X 100
  • the weight change amount is a negative value, which means that -15% or more increases to a negative value.
  • the biodegradable film may have a thickness change of -12% or more compared to the thickness before embedding after 4 weeks of burying in soil, and the thickness change may be expressed by Equation 2 below.
  • Thickness change (thickness of biodegradable film after 4 weeks of burying - thickness of biodegradable film before burial) / (thickness of biodegradable film after 4 weeks of burying) X 100
  • the thickness change amount is a negative value, meaning that -12% or more increases to a negative value.
  • the film may be applicable to at least any one or more selected from industrial films, food films, agricultural films, and daily life films.
  • biodegradable resin composition prepared by a melt blending method, including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA).
  • PBAT polybutylene adipate terephthalate
  • PVA polyvinyl alcohol
  • the melt blending may be performed at 160°C to 210°C.
  • the melt blending may be performed by using at least one selected from an extruder, a kneader, a Brabender plastic coder, a mixing roll, and a mixer.
  • the extruder may be one or more selected from a single screw extruder, a twin screw extruder, a single screw and a twin screw extruder.
  • the biodegradable resin composition according to the present invention improves compatibility by providing a combination of four components including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol, thereby improving the degradability of polyethylene provides the effect of
  • a film comprising the biodegradable resin composition according to the present invention
  • it can be applied to various fields such as industrial, food, agricultural, etc., and provides excellent biodegradability to contribute to solving environmental problems.
  • FIG. 1 is a photograph comparing the degradability of a film including a biodegradable resin composition according to an experimental example of the present invention.
  • FIG. 2 is a graph showing the change in weight for each period of a film including a biodegradable resin composition according to an experimental example of the present invention.
  • LLDPE 45% by weight of LLDPE (M2010EA from Hanwha Chemical), 20% by weight of PBAT (SOLPOL-1000 from GIOSOLTEC), 30% by weight of TPS (Bionyl from Daesang), and 5% by weight of polyvinyl alcohol (PVA) were mixed in Table 1 A mixture of the same composition was prepared.
  • the prepared mixture was put in an extruder and heated at a mixing zone temperature of 190° C. to prepare a biodegradable resin composition, and then directly extruded to prepare a blown film.
  • the blown film processing conditions were a screw 40mm ⁇ , a die 75mm ⁇ , a die gap 2mm, and the screw speed was 180rpm.
  • a biodegradable film was prepared in the same manner as in Example 1, except that 45 wt% of LLDPE, 15 wt% of PBAT, 30 wt% of TPS, and 10 wt% of PVA were mixed.
  • a film was prepared in the same manner as in Example 1, except that 45 wt% of LLDPE, 25 wt% of PBAT, and 30 wt% of TPS were mixed.
  • a film was prepared in the same manner as in Example 1, except that 45% by weight of LLDPE, 10% by weight of PBAT, 30% by weight of TPS, and 15% by weight of PVA were mixed.
  • a film was prepared in the same manner as in Example 1, except that 45% by weight of LLDPE, 5% by weight of PBAT, 30% by weight of TPS, and 20% by weight of PVA were mixed.
  • Films according to Examples and Comparative Examples having a composition ratio according to Table 1 were buried in soil, and changes in weight and thickness ratio before and after embedding were observed.
  • a constant temperature and moisture content that can activate the growth of microorganisms are important, and a temperature of 58°C and a moisture content of 50% were maintained by using a thermo-hygrostat under standard composting conditions.
  • compatibility is improved by providing a resin composition comprising four components of polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA), and it is adjusted to an appropriate content range. When included, it was confirmed that it had the effect of improving the decomposition property of polyethylene.
  • PBAT polybutylene adipate terephthalate
  • PVA polyvinyl alcohol
  • a film comprising the biodegradable resin composition according to the present invention can be applied to various fields such as industrial, food, agricultural, etc., and can be expected to contribute to solving environmental problems by providing excellent biodegradability.
  • the first aspect of the present application is a first aspect of the present application.
  • a biodegradable resin composition comprising polyethylene, a biodegradable resin, polybutylene adipate terephthalate (PBAT), and polyvinyl alcohol (PVA).
  • PBAT polybutylene adipate terephthalate
  • PVA polyvinyl alcohol
  • biodegradable resin composition according to the first aspect of the present application will be described in detail.
  • biodegradable means a plastic that is decomposed into water and CO 2 or CH 4 by microorganisms such as bacteria, algae, and mold. It may mean that the molecular weight is reduced by cutting the main chain of the polymer as well as the physical breakdown of the molded product such as plastic.
  • the biodegradable resin composition is a biodegradable resin through a compound combination of four components, including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) A composition may be provided.
  • PBAT polybutylene adipate terephthalate
  • PVA polyvinyl alcohol
  • the polyethylene is inexpensive and has excellent mechanical properties and processability, but is a major cause of environmental pollution in the environment due to its recalcitrance. Therefore, in the present invention, in order to improve biodegradability while maintaining excellent mechanical properties and processability of polyethylene, it may be provided including biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA). there is.
  • biodegradable resin polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA).
  • the polyethylene is high density polyethylene (HDPE, High Density Polyethylene), very low density polyethylene (VLDPE, Very-low-density polyethylene), low density polyethylene (LDPE, Low Density Polyethylene), medium density polyethylene (MDPE) , Medium Density Polyethylene), Linear Low Density Polyethylene (LLDPE, Linear Low Density Polyethylene), Ethylene-Vinyl Acetate copolymer (EVA, Ethylene-Vinyl Acetate copolymer) and combinations thereof. It may contain a polymer selected from the group consisting of. Preferably, linear low-density polyethylene (LLDPE) is provided to provide excellent impact resistance and durability.
  • HDPE High Density Polyethylene
  • VLDPE Very-low-density polyethylene
  • LDPE Low Density Polyethylene
  • MDPE medium density polyethylene
  • LLDPE Medium Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • EVA Ethylene-Vinyl
  • the polyethylene has a weight average molecular weight of hundreds of thousands to millions, and a weight average molecular weight of 100,000 to 1,000,000, preferably 100,000 to 300,000.
  • the biodegradable resin is thermoplastic starch (TPS), polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polyglycolic acid (PGA), polyhyde It may include a material selected from the group consisting of hydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), cellulose, chitin, and combinations thereof, preferably including thermoplastic starch (TPS) it could be
  • the polylactic acid, polycaprolactone, polybutylene succinate and polyglycolic acid correspond to aliphatic polyesters, and they are excellent in biodegradability by microorganisms and provide properties such as biocompatibility. there is.
  • polyglycolic acid it has excellent mechanical properties such as high strength and high heat resistance, and is particularly widely used in medical applications.
  • the polyhydroxyalkanoate corresponds to polyester and may be characterized by excellent biodegradability and excellent degradability under any conditions such as aerobic, anaerobic, and composting conditions.
  • polyhydroxybutyrate is a natural polyester that belongs to polyhydroxyalkanoate and is a homopolymer in which D-3-hydroxy-butyric acid is linearly linked, and a very diverse As an energy store synthesized by bacteria in cells, it may provide a biological function such as starch or glycogen.
  • the cellulose, chitin and natural polymer-based polymers may be provided as eco-friendly materials due to their excellent biodegradability, easy supply, and non-toxic properties.
  • the thermoplastic starch refers to a granular material obtained from plants and composed of two components, amylose and amylopectin, for example, rice starch, wheat starch, corn starch, sweet potato starch, potato starch, It may be provided including at least one selected from tapioca starch, cassava starch, and modified starches thereof.
  • Modified starch may be provided such as ⁇ -starch, acid-treated starch, oxidized starch, cationic starch, ester starch, ether starch, etc. in which starch is physically or chemically treated.
  • the starch it has excellent biodegradability, is composed of amylose and amylopectin, and the glucose of amylose contains a hydroxy (-OH) group, so it has hydrophilicity and hydrogen bonding.
  • polybutylene adipate terephthalate in the case of the polybutylene adipate terephthalate (PBAT), it may be a biodegradable resin and at the same time provide a compatibilizer role.
  • polyolefin has a problem of compatibility because its chemical properties are non-polar and have poor kneading properties with polar thermoplastic starch. Therefore, by introducing the polybutylene adipate terephthalate (PBAT), compatibility can be improved and excellent biodegradability of polyethylene, which is a base resin, can be provided at the same time.
  • the polybutylene adipate terephthalate may have a weight average molecular weight of 10,000 to 100,000, preferably 20,000 to 50,000.
  • the polyvinyl alcohol (PVA), like the polybutylene adipate terephthalate (PBAT), may be a biodegradable resin and at the same time provide a compatibilizer role. Therefore, by introducing polyvinyl alcohol (PVA) having both a friend and a hydrophobic group, compatibility can be improved and excellent biodegradability of polyethylene, which is a base resin, can be provided at the same time.
  • the polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) should each be included in an appropriate amount in the biodegradable resin composition, and when included outside the appropriate content range, the function of the biodegradable resin composition is reduced may be lowered. This will be described in more detail below.
  • the melting temperature of the biodegradable resin composition is 100 ° C to 130 ° C, and the melt index of the resin composition is 0.01 to 10 g/10 min at 2.16 Kg of 190 ° C based on ASTM D1238.
  • the melting temperature may be measured by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), which are commonly measured methods, and the melt index (MI) may be measured by ASTM D1238 there is.
  • the content of the biodegradable resin may be 10 parts by weight to 600 parts by weight, preferably 40 parts by weight to 100 parts by weight, more preferably may be in an amount of 60 parts by weight to 70 parts by weight.
  • the polyethylene and the biodegradable resin may be included in a weight ratio of 45:30.
  • the content of the biodegradable resin is more than 600 parts by weight, there may be a limit in providing excellent mechanical properties and processability that can be provided by conventional plastics because the content of polyethylene is relatively small, and specifically, tensile strength (Tensile) Strength), elongation (Elongation) and drop impact strength may be reduced.
  • the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 500 parts by weight
  • the content of the polyvinyl alcohol (PVA) is 10 It may be in an amount of from 10 parts by weight to 30 parts by weight, preferably, 10 parts by weight to 50 parts by weight of polybutylene adipate terephthalate (PBAT), and more preferably 30 parts by weight of polybutylene adipate terephthalate (PBAT).
  • polyvinyl alcohol (PVA) may be 10 parts by weight to 25 parts by weight.
  • the polyethylene, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) may be included in a weight ratio of 45: 15 to 20: 5 to 10.
  • the content of the polybutylene adipate terephthalate (PBAT) is less than 10 parts by weight or the content of the polyvinyl alcohol (PVA) is less than 10 parts by weight
  • the biodegradation effect by this is It may be insignificant, and when the content of polybutylene adipate terephthalate (PBAT) exceeds 500 parts by weight or the content of polyvinyl alcohol (PVA) exceeds 30 parts by weight, problems may occur in compatibility with polyethylene and processability. there is.
  • biodegradable film comprising the biodegradable resin composition according to the first aspect of the present application.
  • the film can be applied to at least one selected from an industrial film, a food film, an agricultural film, and a household film, and the mechanical properties provided by conventional plastics are improved while providing Biodegradability may be provided.
  • excellent decomposition properties of the film can be confirmed. Therefore, after using the film, it can be composted in a facility with certain conditions (Compost). In addition, even if it is unavoidably burned, the amount of heat generated is low, so that the emission of harmful substances such as dioxins can be minimized.
  • the biodegradable film has a weight change of -15% or more compared to the weight before embedding after 4 weeks of burying in the soil, and the weight change may be expressed by Equation 1 below.
  • Weight change (weight of biodegradable film after burying for 4 weeks - weight of biodegradable film before burial) / (weight of biodegradable film after burying for 4 weeks) X 100
  • the amount of change in weight is a negative value, and it may mean that -15% or more increases to a negative value.
  • the weight change may be preferably -18% or more, and more preferably about -19% to -20%.
  • the biodegradable film has a thickness change of -12% or more compared to the thickness before embedding after 4 weeks of burying in soil, and the thickness change may be expressed by Equation 2 below.
  • Thickness change (thickness of biodegradable film after 4 weeks of burying - thickness of biodegradable film before burial) / (thickness of biodegradable film after 4 weeks of burying) X 100
  • the thickness change amount is a negative value, and -12% or more may mean that a negative value increases.
  • the thickness variation may be preferably -13% or more, and more preferably about -13% to -15%.
  • the thickness of the film may be provided as 20 to 40 ⁇ m, preferably may be provided as 30 ⁇ m.
  • the third aspect of the present application is
  • biodegradable resin composition prepared by a melt blending method, including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA).
  • PBAT polybutylene adipate terephthalate
  • PVA polyvinyl alcohol
  • the content of the biodegradable resin may be 10 parts by weight to 600 parts by weight, preferably 40 parts by weight to 100 parts by weight, more preferably may be in an amount of 60 parts by weight to 70 parts by weight.
  • the polyethylene and the biodegradable resin may be included in a weight ratio of 45:30.
  • the content of the biodegradable resin is more than 600 parts by weight, there may be a limit in providing excellent mechanical properties and processability that can be provided by conventional plastics because the content of polyethylene is relatively small, and specifically, tensile strength (Tensile) Strength), elongation (Elongation) and drop impact strength may be reduced.
  • the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 500 parts by weight
  • the content of the polyvinyl alcohol (PVA) is 10 It may be in an amount of from 10 parts by weight to 30 parts by weight, preferably, 10 parts by weight to 50 parts by weight of polybutylene adipate terephthalate (PBAT), and more preferably 30 parts by weight of polybutylene adipate terephthalate (PBAT).
  • polyvinyl alcohol (PVA) may be 10 parts by weight to 25 parts by weight.
  • the polyethylene, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) may be included in a weight ratio of 45: 15 to 20: 5 to 10.
  • the content of the polybutylene adipate terephthalate (PBAT) is less than 10 parts by weight or the content of the polyvinyl alcohol (PVA) is less than 10 parts by weight
  • the biodegradation effect by this is It may be insignificant, and when the content of polybutylene adipate terephthalate (PBAT) exceeds 500 parts by weight or the content of polyvinyl alcohol (PVA) exceeds 30 parts by weight, problems may occur in compatibility with polyethylene and processability. there is.
  • the melt blending is provided using at least one selected from an extruder, a kneader, a Brabender Plasticorder, a mixing roll, and a mixer.
  • the extruder may be provided by using any one or more selected from a single screw extruder, a twin screw extruder, a single screw and a twin screw extruder, and preferably by using a twin screw extruder, excellent kneading performance and Easy processability can be provided.
  • the process may be performed by optimizing process conditions according to various raw materials to be input in the melt blending.
  • the melting temperature may be provided in a range of 100°C to 300°C, preferably 160°C to 210°C, and the rotation speed of the extruder screw is provided in a range of 40rpm to 700rpm, preferably 100rpm to 200rpm. .
  • the biodegradable resin composition according to the present invention improves compatibility by providing a combination of four components including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol, thereby improving the degradability of polyethylene provides the effect of
  • a film comprising the biodegradable resin composition according to the present invention
  • it can be applied to various fields such as industrial, food, agricultural, etc., and provides excellent biodegradability to contribute to solving environmental problems.

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Abstract

The present invention relates to a biodegradable resin composition, and to a method for manufacturing same and, more particularly, to a technique which has improved biodegradability by means of containing polyethylene, a biodegradable resin, polybutylene adipate terephthalate (PBAT), and polyvinyl alcohol (PVA).

Description

폴리비닐알코올을 포함하는 생분해성 수지 조성물 및 그 제조방법Biodegradable resin composition containing polyvinyl alcohol and manufacturing method thereof
본 발명은 생분해성 수지 조성물 및 그 제조방법에 관한 것으로, 보다 자세하게는 폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)를 포함하여, 생분해성을 향상시킨 기술에 관한 것이다.The present invention relates to a biodegradable resin composition and a method for producing the same, and more particularly, to include polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) to improve biodegradability. It's about technology.
플라스틱(plastic)은 뛰어난 물성과 함께 값싸고 가벼운 특성으로 인하여 천연소재가 가지는 한계를 벗어나 플라스틱을 중심으로 다양한 고분자물질이 개발되어 현대과학 문명을 구축해왔다. 플라스틱은 강하고 가볍고 질기며, 쉽게 분해되지 않는다는 점이 특성이 있으며 이러한 성질로 인해 산업용 소재에서부터 일회용 소재에 이르기까지 다양하게 사용되고 있다. 플라스틱과 같은 합성수지의 강인성 및 내구성을 더욱 향상시키기 위해 오랜 기간 연구가 되어오고 있으며, 이러한 노력은 지금도 계속되고 있다. 그러나, 날로 심각해지는 플라스틱 폐기물에 의한 환경오염이 문제되고 있고, 예를 들어, 맹독성 다이옥신의 검출 환경호르몬의 누출 등으로 인해 친환경 플라스틱에 대한 사회적인 요구뿐만 아니라 비분해성 플라스틱 사용에 대한 각국의 법률적인 규제의 기준도 점점 더 강화되고 있다. 이를 해결하기 위해 생분해성 고분자 개발이 매우 중요한 사항으로 다루어지고 있으며, 플라스틱 공업에서도 중요한 분야로 주목받고 있다.Due to its excellent physical properties and cheap and light characteristics, plastics have been developed with various polymers centered on plastics beyond the limits of natural materials and have built a modern scientific civilization. Plastics are characterized by being strong, light, tough, and not easily decomposing, and due to these properties, they are used in a variety of ways, from industrial materials to disposable materials. Research has been conducted for a long time to further improve the toughness and durability of synthetic resins such as plastics, and these efforts are still ongoing. However, environmental pollution by plastic waste is becoming a serious problem, for example, due to the detection of highly toxic dioxins and leakage of environmental hormones, not only the social demand for eco-friendly plastics, but also the legal regulations of each country on the use of non-degradable plastics. standards are also getting tighter. In order to solve this problem, the development of biodegradable polymers is being treated as a very important matter, and it is attracting attention as an important field in the plastics industry.
일반적으로 분해성 플라스틱은 미국 ASTM(American Society for Testing and Materials)에 따르면 특정 환경 조건에서 일정기간 동안 화학적 구조가 상당히 변화되어 그 성질 변화를 표준 시험방법으로 측정할 수 있는 플라스틱을 말하며, 광분해성, 생붕괴성, 생분해성 플라스틱으로 나눌 수 있다.In general, degradable plastics refer to plastics whose chemical structure is significantly changed for a certain period of time under specific environmental conditions according to the American Society for Testing and Materials (ASTM) in the United States, and the change in properties can be measured by standard test methods. It can be divided into collapsible and biodegradable plastics.
보다 자세하게는 광분해성 플라스틱이란, 광산화 또는 케톤 광분해 등의 형태로 빛에 의해 분해되는 플라스틱을 말한다. 그러나, 광분해성 플라스틱은 빛에 의해 분해되므로 빛이 차단된 땅속에 매립 시 분해가 되지 않는 단점이 있다. 생붕괴성 플라스틱이란, 비분해성의 일반적인 범용수지(폴리에틸렌, 폴리프로필렌 등)에 전분 같은 생분해성 물질을 일정량 첨가하여 제조한 부분 분해성 플라스틱으로 국내의 경우 생분해성 플라스틱과의 혼동을 피하기 위해 생붕괴성 플라스틱이란 용어를 사용하여 별도로 구분하고 있다. 생분해성 플라스틱이란, 일반적으로 플라스틱 자체가 박테리아 조류 곰팡이와 같은 자연계에 존재하는 미생물에 의해 물과 이산화탄소 또는 물과 메탄가스로 완전히 분해되는 플라스틱을 말한다.More specifically, the photodegradable plastic refers to a plastic that is decomposed by light in the form of photooxidation or ketone photolysis. However, since photodegradable plastic is decomposed by light, there is a disadvantage in that it is not decomposed when buried in the ground where light is blocked. Biodegradable plastics are partially degradable plastics manufactured by adding a certain amount of biodegradable substances such as starch to general non-degradable resins (polyethylene, polypropylene, etc.). The term plastic is used to separate them. The biodegradable plastic generally refers to a plastic in which the plastic itself is completely decomposed into water and carbon dioxide or water and methane gas by microorganisms present in nature, such as bacteria, algae, and mold.
예전에는 광분해성 플라스틱 또는 생붕괴성 플라스틱이 주로 사용되었지만 최근에는 생분해성 플라스틱에 대한 개발이 중요한 사항으로 다루어지고 있다. 이는 원료면에서부터 천연의 식물자원을 사용하여 기존의 석유계 플라스틱과 구별될 뿐만 아니라, 자연계 내에서 미생물에 의해 물과 이산화탄소만으로 완전 분해되는 청정성을 제공할 수 있으므로 세계적인 추세도 생분해성 플라스틱이 주류를 이루면서 개발되고 있다.In the past, photodegradable plastics or biodegradable plastics were mainly used, but recently, the development of biodegradable plastics is being treated as an important issue. It is not only distinguished from the existing petroleum-based plastics by using natural plant resources from the raw material side, but also can provide cleanliness that is completely decomposed into water and carbon dioxide only by microorganisms in nature, so the global trend is also that biodegradable plastics are becoming mainstream. It is being developed while
예를 들어, 한국 공개특허공보 제10-2018-0023037호는 비혼화성인 폴리머 성분의 폴리머 블렌드를 포함하는 열가소성 필름 조성물을 개시한다. 상기 조성물은 가소화된 천연 폴리머, 폴리올레핀, 생분해성 폴리머 및 동일한 폴리머 분자에 상용화제를 포함한다. 가소화된 천연 성분 및 생분해성 폴리머 성분이 다수 상을 페트롤륨-베이스 올레핀 폴리머가 소수상을 형성한다. 또한, 상기 조성물은 재생 가능한 천연 폴리머 성분을 포함하는 필름으로 제조가능함을 언급하고 있다.For example, Korean Patent Application Laid-Open No. 10-2018-0023037 discloses a thermoplastic film composition comprising a polymer blend of an immiscible polymer component. The composition comprises a plasticized natural polymer, a polyolefin, a biodegradable polymer and a compatibilizer in the same polymer molecule. The plasticized natural component and the biodegradable polymer component form the majority phase and the petroleum-based olefin polymer forms the minor phase. It is also noted that the composition can be prepared into a film comprising a renewable natural polymer component.
다른 예를 들어, 한국 공개특허공보 제10-2017-0075052호 (i) 생분해성 수지 (ii) 글루코오스 단위의 수산기(-OH기) 중 적어도 하나가 실란으로 소수화 처리된 전분 (iii) 생분해성 고분자에 무수말레산(Maleic anhydride, MA)을 그라프트시킨 그라프트 공중합체, 에폭시화된 오일 및 에폭시기를 갖는 다관능성 화합물로 이루어진 군에서 선택된 어느 하나 또는 둘 이상의 상용화제를 포함하는 멀칭필름용 수지 조성물과 그 필름에 관하여 개시하고 있다. 이에 필름의 가공성 및 멀칭 기능성을 개선시킬 수 있으며, 필름의 인장강도 및 인장신율이 향상된 것을 특징으로 한다.For another example, Korean Patent Application Laid-Open No. 10-2017-0075052 (i) biodegradable resin (ii) starch in which at least one of the hydroxyl groups (-OH groups) of the glucose unit is hydrophobized with silane (iii) biodegradable polymer A resin composition for a mulching film comprising any one or two or more compatibilizers selected from the group consisting of a graft copolymer grafted with maleic anhydride (MA), an epoxidized oil, and a polyfunctional compound having an epoxy group and the film are disclosed. Accordingly, the processability and mulching functionality of the film can be improved, and the tensile strength and tensile elongation of the film are improved.
상기 특허들의 경우, 대부분 2 성분의 수지를 포함하여 완전한 생분해성을 보여주기는 어려운 점에서 다소 한계가 있다. 이에, 보다 나은 물성과 동시에 우수한 생분해성을 제공하기 위해 개발 연구는 여전히 필요하다. 본 발명 역시 이러한 요구를 만족하기 위하여 오랜 연구 끝에 완성하였다.In the case of the above patents, there are some limitations in that it is difficult to show complete biodegradability including most of the two-component resins. Therefore, development research is still needed to provide better physical properties and excellent biodegradability. The present invention was also completed after a long research in order to satisfy these requirements.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌 1) 한국 공개특허공보 제10-2018-0023037호 (2018.03.06)(Patent Document 1) Korean Patent Publication No. 10-2018-0023037 (2018.03.06)
(특허문헌 2) 한국 공개특허공보 제10-2017-0075052호 (2017.07.03)(Patent Document 2) Korean Patent Publication No. 10-2017-0075052 (2017.07.03)
본 발명은 상술한 문제점을 모두 해결하는 것을 목적으로 한다.An object of the present invention is to solve all of the above problems.
본 발명의 목적은 생분해성 수지 조성물의 상용성을 향상시키고 이에 폴리에틸렌의 분해성을 향상시키는 것이다. An object of the present invention is to improve the compatibility of a biodegradable resin composition and thereby improve the degradability of polyethylene.
본 발명의 목적은 상기 생분해성 수지 조성물을 포함한 필름을 제공하여, 공업용, 식품용, 농업용 등 다양한 분야에 적용하게 하는 것이다.An object of the present invention is to provide a film including the biodegradable resin composition, and to be applied to various fields such as industrial, food, agricultural, and the like.
전술한 기술적 과제를 달성하기 위한 기술적 수단으로서, 본 발명의 일 측면은, As a technical means for achieving the above-described technical problem, an aspect of the present invention is
폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)을 포함하는 생분해성 수지 조성물을 제공한다.Provided is a biodegradable resin composition comprising polyethylene, a biodegradable resin, polybutylene adipate terephthalate (PBAT), and polyvinyl alcohol (PVA).
상기 폴리에틸렌은 고밀도폴리에틸렌(HDPE), 저밀도폴리에틸렌(LDPE), 중간밀도폴리에틸렌(MDPE), 선형저밀도폴리에틸렌(LLDPE), 에틸렌비닐공중합체(EVA) 및 이들의 조합들로 이루어진 군으로부터 선택되는 폴리머를 포함하는 것일 수 있다.The polyethylene comprises a polymer selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), ethylene vinyl copolymer (EVA), and combinations thereof. may be doing
상기 생분해성 수지는 열가소성 전분(TPS), 폴리락트산(PLA), 폴리카프로락톤(PCL), 폴리부틸렌석시네이트(PBS), 폴리글리콜산(PGA), 폴리하이드록시알카노에이트(PHA), 폴리하이드록시부틸레이트(PHB), 셀룰로오스, 키틴 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있다.The biodegradable resin is thermoplastic starch (TPS), polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), It may include a material selected from the group consisting of polyhydroxybutyrate (PHB), cellulose, chitin, and combinations thereof.
상기 열가소성 전분은 쌀전분, 밀전분, 옥수수전분, 고구마전분, 감자전분, 타피오카전분, 카사바전분 및 이들의 변성 전분에서 선택되는 적어도 어느 하나 이상을 포함하는 것일 수 있다.The thermoplastic starch may include at least one selected from rice starch, wheat starch, corn starch, sweet potato starch, potato starch, tapioca starch, cassava starch, and modified starches thereof.
상기 폴리에틸렌의 중량평균분자량은 100,000 내지 1,000,000인 것일 수 있다.The weight average molecular weight of the polyethylene may be 100,000 to 1,000,000.
상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 중량평균분자량은 10,000 내지 100,000인 것일 수 있다.The polybutylene adipate terephthalate (PBAT) may have a weight average molecular weight of 10,000 to 100,000.
상기 생분해성 수지 조성물의 용융온도는 100℃ 내지 130℃이며, 용융지수는 ASTM D1238기준으로 190℃의 2.16Kg에서 0.01 내지 10g/10min인 것일 수 있다.The biodegradable resin composition may have a melting temperature of 100° C. to 130° C., and a melt index of 0.01 to 10 g/10 min at 2.16 kg at 190° C. based on ASTM D1238.
상기 폴리에틸렌 100 중량부에 대하여, 상기 생분해성 수지의 함량은 10 중량부 내지 600 중량부이고, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 10 중량부 내지 500 중량부이며, 상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 30 중량부인 것일 수 있다.Based on 100 parts by weight of the polyethylene, the content of the biodegradable resin is 10 parts by weight to 600 parts by weight, the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 500 parts by weight, and the polyvinyl The content of alcohol (PVA) may be 10 parts by weight to 30 parts by weight.
상기 폴리에틸렌 100 중량부에 대하여, 상기 생분해성 수지의 함량은 40 중량부 내지 100 중량부이고, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 10 중량부 내지 50 중량부이며, 상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 30 중량부인 것일 수 있다.Based on 100 parts by weight of the polyethylene, the content of the biodegradable resin is 40 parts by weight to 100 parts by weight, the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 50 parts by weight, and the polyvinyl The content of alcohol (PVA) may be 10 parts by weight to 30 parts by weight.
상기 폴리에틸렌 100 중량부에 대하여, 상기 생분해성 수지의 함량은 60 중량부 내지 70 중량부이고, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 30 중량부 내지 45 중량부이며, 상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 25 중량부인 것일 수 있다.Based on 100 parts by weight of the polyethylene, the content of the biodegradable resin is 60 parts by weight to 70 parts by weight, the content of the polybutylene adipate terephthalate (PBAT) is 30 parts by weight to 45 parts by weight, the polyvinyl The content of alcohol (PVA) may be 10 parts by weight to 25 parts by weight.
또한, 본 발명의 다른 일 측면은,In addition, another aspect of the present invention,
상기 생분해성 수지 조성물을 포함하는 생분해성 필름을 제공한다.It provides a biodegradable film comprising the biodegradable resin composition.
상기 생분해성 필름은 토양에 4주 매립 후, 매립 전 무게에 비해 무게 변화량이 -15% 이상인 것이고, 상기 무게 변화량은 하기 식 1로 표시되는 것일 수 있다.The biodegradable film may have a weight change of -15% or more compared to the weight before embedding after being buried in soil for 4 weeks, and the weight change amount may be expressed by Equation 1 below.
[식 1][Equation 1]
무게 변화량 = (4주 매립 후 생분해성 필름의 무게 - 매립 전 생분해성 필름의 무게) / (4주 매립 후 생분해성 필름의 무게) X 100Weight change = (weight of biodegradable film after burying for 4 weeks - weight of biodegradable film before burial) / (weight of biodegradable film after burying for 4 weeks) X 100
상기 식 1에서, 무게 변화량은 음의 값으로서 상기 -15% 이상은 음의 값으로 커짐을 의미하는 것이다.In Equation 1, the weight change amount is a negative value, which means that -15% or more increases to a negative value.
상기 생분해성 필름은 토양에 4주 매립 후, 매립 전 두께에 비해 두께 변화량이 -12% 이상인 것이고, 상기 두께 변화량은 하기 식 2로 표시되는 것일 수 있다.The biodegradable film may have a thickness change of -12% or more compared to the thickness before embedding after 4 weeks of burying in soil, and the thickness change may be expressed by Equation 2 below.
[식 2][Equation 2]
두께 변화량 = (4주 매립 후 생분해성 필름의 두께 - 매립 전 생분해성 필름의 두께) / (4주 매립 후 생분해성 필름의 두께) X 100Thickness change = (thickness of biodegradable film after 4 weeks of burying - thickness of biodegradable film before burial) / (thickness of biodegradable film after 4 weeks of burying) X 100
상기 식 2에서, 두께 변화량은 음의 값으로서 상기 -12% 이상은 음의 값으로 커짐을 의미하는 것이다.In Equation 2, the thickness change amount is a negative value, meaning that -12% or more increases to a negative value.
상기 필름은 공업용 필름, 식품용 필름, 농업용 필름, 생활용 필름에서 선택되는 적어도 어느 하나 이상에 적용이 가능한 것일 수 있다.The film may be applicable to at least any one or more selected from industrial films, food films, agricultural films, and daily life films.
또한, 본 발명의 또 다른 일 측면은,In addition, another aspect of the present invention,
폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)을 포함하여, 용융블렌딩방법으로 제조되는 생분해성 수지 조성물의 제조방법을 제공한다.It provides a method for preparing a biodegradable resin composition prepared by a melt blending method, including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA).
상기 용융블렌딩은 160℃ 내지 210℃에서 진행되는 것일 수 있다.The melt blending may be performed at 160°C to 210°C.
상기 용융블렌딩은 압출기, 니더, 브라벤더 플라스티코더, 믹싱롤 및 혼합기에서 선택되는 적어도 어느 하나 이상을 사용하는 것일 수 있다.The melt blending may be performed by using at least one selected from an extruder, a kneader, a Brabender plastic coder, a mixing roll, and a mixer.
상기 압출기는 일축 압출기, 이축 압출기, 일축 스크류 및 이축 스크류 압출기에서 선택된 어느 하나 이상을 사용하는 것일 수 있다.The extruder may be one or more selected from a single screw extruder, a twin screw extruder, a single screw and a twin screw extruder.
본 발명에 따른 생분해성 수지 조성물은 폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올을 포함한 4 성분의 조합으로 제공하여 상용성을 향상시키고, 이에 폴리에틸렌의 분해성을 향상시키는 효과를 제공한다. The biodegradable resin composition according to the present invention improves compatibility by providing a combination of four components including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol, thereby improving the degradability of polyethylene provides the effect of
본 발명에 따른 생분해성 수지 조성물을 포함하는 필름의 경우, 공업용, 식품용, 농업용 등 다양한 분야에 적용이 가능하며, 우수한 생분해성을 제공하여 환경문제 해결에 기여하는 효과를 제공한다.In the case of a film comprising the biodegradable resin composition according to the present invention, it can be applied to various fields such as industrial, food, agricultural, etc., and provides excellent biodegradability to contribute to solving environmental problems.
도 1은 본 발명의 일 실험예에 따른 생분해성 수지 조성물을 포함하는 필름의 분해성을 비교한 사진이다.1 is a photograph comparing the degradability of a film including a biodegradable resin composition according to an experimental example of the present invention.
도 2는 본 발명의 일 실험예에 따른 생분해성 수지 조성물을 포함하는 필름의 기간별 무게 변화량을 나타낸 그래프이다.2 is a graph showing the change in weight for each period of a film including a biodegradable resin composition according to an experimental example of the present invention.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
실시예Example 1. 생분해성 필름의 제조 1. Preparation of biodegradable film
LLDPE(한화케미칼社 M2010EA) 45 중량%, PBAT(GIOSOLTEC社 SOLPOL-1000) 20 중량%, TPS(대상社 바이오닐) 30 중량% 및 폴리비닐알코올(PVA) 5 중량%를 혼합하여 하기의 표 1과 같은 조성의 혼합물을 제조하였다.45% by weight of LLDPE (M2010EA from Hanwha Chemical), 20% by weight of PBAT (SOLPOL-1000 from GIOSOLTEC), 30% by weight of TPS (Bionyl from Daesang), and 5% by weight of polyvinyl alcohol (PVA) were mixed in Table 1 A mixture of the same composition was prepared.
제조된 상기 혼합물을 압출기에 넣고 190℃의 믹싱존 온도에서 가열하여 생분해성 수지 조성물이 제조되었고, 곧바로 압출하여 블로운 필름(blown film)을 제조하였다. 이 때, 상기 블로운 필름 가공 조건은 스크류(screw)가 40mmΦ, 다이(die)가 75mmΦ, 다이 갭(die gap)이 2mm이었고, Screw의 속도는 180rpm이었다.The prepared mixture was put in an extruder and heated at a mixing zone temperature of 190° C. to prepare a biodegradable resin composition, and then directly extruded to prepare a blown film. At this time, the blown film processing conditions were a screw 40mmΦ, a die 75mmΦ, a die gap 2mm, and the screw speed was 180rpm.
실시예Example 2. 생분해성 필름의 제조 2. Preparation of biodegradable films
상기 실시예 1에서 LLDPE 45 중량%, PBAT 15 중량%, TPS 30 중량% 및 PVA 10 중량%를 혼합한 것을 제외하고는 동일한 방법을 통해 생분해성 필름을 제조하였다.A biodegradable film was prepared in the same manner as in Example 1, except that 45 wt% of LLDPE, 15 wt% of PBAT, 30 wt% of TPS, and 10 wt% of PVA were mixed.
비교예comparative example 1. 필름의 제조 1. Preparation of film
상기 실시예 1에서 LLDPE 45 중량%, PBAT 25 중량% 및 TPS 30 중량%를 혼합한 것을 제외하고는 동일한 방법을 통해 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that 45 wt% of LLDPE, 25 wt% of PBAT, and 30 wt% of TPS were mixed.
비교예comparative example 2. 필름의 제조 2. Preparation of film
상기 실시예 1에서 LLDPE 45 중량%, PBAT 10 중량%, TPS 30 중량% 및 PVA 15 중량%를 혼합한 것을 제외하고는 동일한 방법을 통해 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that 45% by weight of LLDPE, 10% by weight of PBAT, 30% by weight of TPS, and 15% by weight of PVA were mixed.
비교예comparative example 3. 필름의 제조 3. Preparation of film
상기 실시예 1에서 LLDPE 45 중량%, PBAT 5 중량%, TPS 30 중량% 및 PVA 20 중량%를 혼합한 것을 제외하고는 동일한 방법을 통해 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that 45% by weight of LLDPE, 5% by weight of PBAT, 30% by weight of TPS, and 20% by weight of PVA were mixed.
[표 1][Table 1]
Figure PCTKR2021014921-appb-I000001
Figure PCTKR2021014921-appb-I000001
실험예. 생분해성 필름의 생분해 효과 측정experimental example. Measurement of the biodegradation effect of biodegradable films
상기 표 1에 따른 조성비를 갖는 실시예와 비교예에 따른 필름을 토양에 매립하여 매립 전후 무게 및 두께율 변화를 관찰하였다. 매립된 조건은 미생물의 증식이 활성화 될 수 있는 일정한 온도와 함수량이 중요하며, 표준 퇴비 조건 하에 항온항습기를 활용하여 온도 58℃및 함수율 50% 로 유지하였다.Films according to Examples and Comparative Examples having a composition ratio according to Table 1 were buried in soil, and changes in weight and thickness ratio before and after embedding were observed. In the buried condition, a constant temperature and moisture content that can activate the growth of microorganisms are important, and a temperature of 58°C and a moisture content of 50% were maintained by using a thermo-hygrostat under standard composting conditions.
또한, 매립한 날로부터 2주 및 4주 후에 실험을 진행하였다. 이후, 필름의 무게 변화 및 두께율 변화에 대하여 도 1 및 2에 나타내었다. In addition, the experiment was conducted after 2 and 4 weeks from the date of embedding. Thereafter, the change in weight and thickness ratio of the film are shown in FIGS. 1 and 2 .
본 발명에 따른 실시예 및 비교예에 따른 결과인 도 1 및 2를 참조하면, 본 발명에 따른 실시예 1 및 2의 경우, 비교예 1 내지 3에 비하여 필름의 무게 변화량이 약 -19%로 월등히 높음을 확인할 수 있으며, 두께 변화율은 약 -13.7% 이상으로 우수한 생분해 효과를 가짐을 확인할 수 있었다.1 and 2, which are results according to Examples and Comparative Examples according to the present invention, in Examples 1 and 2 according to the present invention, the weight change of the film was about -19% compared to Comparative Examples 1 to 3 It can be confirmed that it is very high, and the thickness change rate is about -13.7% or more, confirming that it has an excellent biodegradation effect.
따라서, 본 발명의 경우 폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)의 4 성분을 포함한 수지 조성물을 제공하여 상용성을 향상시키고, 이를 적절함량 범위로 포함할 경우 폴리에틸렌의 분해성이 향상되는 효과를 가짐을 확인할 수 있었다.Therefore, in the present invention, compatibility is improved by providing a resin composition comprising four components of polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA), and it is adjusted to an appropriate content range. When included, it was confirmed that it had the effect of improving the decomposition property of polyethylene.
또한, 본 발명에 따른 생분해성 수지 조성물을 포함하는 필름의 경우, 공업용, 식품용, 농업용 등 다양한 분야에 적용이 가능하며, 우수한 생분해성을 제공하여 환경문제 해결에 기여함을 기대할 수 있다.In addition, in the case of a film comprising the biodegradable resin composition according to the present invention, it can be applied to various fields such as industrial, food, agricultural, etc., and can be expected to contribute to solving environmental problems by providing excellent biodegradability.
이상, 도면을 참조하여 바람직한 실시예와 함께 본 발명에 대하여 상세하게 설명하였으나, 이러한 도면과 실시예로 본 발명의 기술적 사상의 범위가 한정되는 것은 아니다. 따라서, 본 발명의 기술적 사상의 범위 내에서 다양한 변형예 또는 균등한 범위의 실시예가 존재할 수 있다. 그러므로 본 발명에 따른 기술적 사상의 권리범위는 청구범위에 의해 해석되어야 하고, 이와 동등하거나 균등한 범위 내의 기술 사상은 본 발명의 권리범위에 속하는 것으로 해석되어야 할 것이다.Above, the present invention has been described in detail with preferred embodiments with reference to the drawings, but the scope of the technical idea of the present invention is not limited to these drawings and examples. Accordingly, various modifications or equivalent ranges of embodiments may exist within the scope of the technical spirit of the present invention. Therefore, the scope of the technical idea according to the present invention should be interpreted by the claims, and the technical idea within the equivalent or equivalent scope should be interpreted as belonging to the scope of the present invention.
이하, 본 발명을 더욱 상세하게 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 의해 본 발명이 한정되지 않으며 본 발명은 후술할 청구범위의 의해 정의될 뿐이다.Hereinafter, the present invention will be described in more detail. However, the present invention may be embodied in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.
덧붙여, 본 발명에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 발명의 명세서 전체에서 어떤 구성요소를 '포함'한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' any component means that other components may be further included, rather than excluding other components, unless otherwise stated.
본원의 제 1 측면은,The first aspect of the present application is
폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)을 포함하는 생분해성 수지 조성물을 제공한다.Provided is a biodegradable resin composition comprising polyethylene, a biodegradable resin, polybutylene adipate terephthalate (PBAT), and polyvinyl alcohol (PVA).
이하, 본원의 제 1 측면에 따른 생분해성 수지 조성물을 상세히 설명하도록 한다.Hereinafter, the biodegradable resin composition according to the first aspect of the present application will be described in detail.
우선, 본원의 일 구현예에 있어서, 생분해성(Biodegradable)이란, 박테리아, 조류, 곰팡이와 같은 미생물에 의해 물과 CO2 또는 CH4로 분해되는 플라스틱을 의미한다. 플라스틱 등의 성형 제품의 물리적 와해뿐만 아니라 고분자의 주쇄 절단에 의한 분자량 감소가 일어나는 것을 의미하는 것일 수 있다.First, in one embodiment of the present application, biodegradable means a plastic that is decomposed into water and CO 2 or CH 4 by microorganisms such as bacteria, algae, and mold. It may mean that the molecular weight is reduced by cutting the main chain of the polymer as well as the physical breakdown of the molded product such as plastic.
본원의 일 구현예에 있어서, 상기 생분해성 수지 조성물은 폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)를 포함하여 4 성분의 컴파운드 조합을 통한 생분해성 수지 조성물이 제공되는 것일 수 있다.In one embodiment of the present application, the biodegradable resin composition is a biodegradable resin through a compound combination of four components, including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) A composition may be provided.
본원의 일 구현예에 있어서, 상기 폴리에틸렌은 비용이 저렴하고 기계적 물성과 가공성이 우수하지만 난분해성으로 인해 환경에 있어서 환경오염의 주원인이 문제가 된다. 따라서, 본 발명에서는 폴리에틸렌의 우수한 기계적 물성과 가공성을 유지하면서 생분해성을 향상하기 위하여, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)을 포함하여 제공되는 것일 수 있다.In one embodiment of the present application, the polyethylene is inexpensive and has excellent mechanical properties and processability, but is a major cause of environmental pollution in the environment due to its recalcitrance. Therefore, in the present invention, in order to improve biodegradability while maintaining excellent mechanical properties and processability of polyethylene, it may be provided including biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA). there is.
본원의 일 구현예에 있어서, 상기 폴리에틸렌은 고밀도폴리에틸렌(HDPE, High Density Polyethylene), 초저밀도폴리에틸렌(VLDPE, Very-low-density polyethylene), 저밀도폴리에틸렌(LDPE, Low Density Polyethylene), 중간밀도폴리에틸렌(MDPE, Medium Density Polyethylene), 선형저밀도폴리에틸렌(LLDPE, Linear Low Density Polyethylene), 에틸렌비닐공중합체(EVA, Ethylene-Vinyl Acetate copolymer) 및 이들의 조합들로 이루어진 군으로부터 선택되는 폴리머를 포함하는 것일 수 있다. 바람직하게는 선형저밀도폴리에틸렌(LLDPE)이 제공되어 우수한 내충격성과 내구성 등을 제공할 수 있다.In one embodiment of the present application, the polyethylene is high density polyethylene (HDPE, High Density Polyethylene), very low density polyethylene (VLDPE, Very-low-density polyethylene), low density polyethylene (LDPE, Low Density Polyethylene), medium density polyethylene (MDPE) , Medium Density Polyethylene), Linear Low Density Polyethylene (LLDPE, Linear Low Density Polyethylene), Ethylene-Vinyl Acetate copolymer (EVA, Ethylene-Vinyl Acetate copolymer) and combinations thereof. It may contain a polymer selected from the group consisting of. Preferably, linear low-density polyethylene (LLDPE) is provided to provide excellent impact resistance and durability.
본원의 일 구현예에 있어서, 상기 폴리에틸렌의 중량평균분자량은 수십만 내지 수백만으로 제공되며, 중량평균분자량은 100,000 내지 1,000,000으로 제공될 수 있고, 바람직하게는 100,000 내지 300,000으로 제공되는 것일 수 있다.In one embodiment of the present application, the polyethylene has a weight average molecular weight of hundreds of thousands to millions, and a weight average molecular weight of 100,000 to 1,000,000, preferably 100,000 to 300,000.
본원의 일 구현예에 있어서, 상기 생분해성 수지는 열가소성 전분(TPS), 폴리락트산(PLA), 폴리카프로락톤(PCL), 폴리부틸렌석시네이트(PBS), 폴리글리콜산(PGA), 폴리하이드록시알카노에이트(PHA), 폴리하이드록시부틸레이트(PHB), 셀룰로오스, 키틴 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것일 수 있으며, 바람직하게는 열가소성 전분(TPS)을 포함하는 것일 수 있다. In one embodiment of the present application, the biodegradable resin is thermoplastic starch (TPS), polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polyglycolic acid (PGA), polyhyde It may include a material selected from the group consisting of hydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), cellulose, chitin, and combinations thereof, preferably including thermoplastic starch (TPS) it could be
본원의 일 구현예에 있어서, 상기 폴리락트산, 폴리카프로락톤, 폴리부틸렌석시네이트 및 폴리글리콜산은 지방족 폴리에스터에 해당하며 이들은 미생물에 의한 생분해성이 우수하고 생체적합성 등의 특성을 제공하는 것일 수 있다. 특히, 폴리글리콜산의 경우, 고강도 및 고내열성 등의 기계적 물성이 우수하여 의료용에서 특히 많이 활용되고 있다. In one embodiment of the present application, the polylactic acid, polycaprolactone, polybutylene succinate and polyglycolic acid correspond to aliphatic polyesters, and they are excellent in biodegradability by microorganisms and provide properties such as biocompatibility. there is. In particular, in the case of polyglycolic acid, it has excellent mechanical properties such as high strength and high heat resistance, and is particularly widely used in medical applications.
본원의 일 구현예에 있어서, 상기 폴리하이드록시알카노에이트는 폴리에스테르에 해당하고 우수한 생분해성과 호기, 혐기, 퇴비 조건 등의 어떤 조건이라도 분해성이 우수한 것이 특징인 것일 수 있다. 또한, 폴리하이드록시부틸레이트는 천연 폴리에스터로 폴리하이드록시알카노에이트에 속하며 D-3-하이드록시-부틸릭산(D-3-hydroxy-butyric acid)이 직선상으로 연결된 단일 중합체이며, 매우 다양한 세균들이 세포 내에 합성하는 에너지 저장물로서 녹말(starch) 또는 글리코겐(glycogen)과 같은 생물학적 기능을 제공하는 것일 수 있다. In one embodiment of the present application, the polyhydroxyalkanoate corresponds to polyester and may be characterized by excellent biodegradability and excellent degradability under any conditions such as aerobic, anaerobic, and composting conditions. In addition, polyhydroxybutyrate is a natural polyester that belongs to polyhydroxyalkanoate and is a homopolymer in which D-3-hydroxy-butyric acid is linearly linked, and a very diverse As an energy store synthesized by bacteria in cells, it may provide a biological function such as starch or glycogen.
본원의 일 구현예에 있어서, 상기 셀룰로오스, 키틴과 천연고분자계 고분자의 경우, 생분해도가 우수하고 공급이 용이하며 무독성 같은 특성으로 인해 친환경 소재로 제공될 수 있다.In one embodiment of the present application, the cellulose, chitin and natural polymer-based polymers may be provided as eco-friendly materials due to their excellent biodegradability, easy supply, and non-toxic properties.
본원의 일 구현예에 있어서, 상기 열가소성 전분은 식물로부터 얻어지며, 아밀로스와 아밀로펙틴 두 성분으로 이루어지는 과립상의 물질을 의미하는 것으로 예를 들어서, 쌀전분, 밀전분, 옥수수전분, 고구마전분, 감자전분, 타피오카전분, 카사바전분 및 이들의 변성 전분에서 선택되는 적어도 어느 하나 이상을 포함하여 제공되는 것일 수 있다. 변성 전분이라 함은 전분에 물리적 또는 화학적 처리를 한 α-전분, 산처리전분, 산화전분, 양성전분, 에스테르전분, 에테르전분 등과 같이 제공될 수 있다. 상기 전분의 경우 생분해성이 우수하고 아밀로스와 아밀로펙틴을 구성되고 아밀로스의 글루코스에는 하이드록시(-OH)기를 포함하고 있어 친수성과 수소결합을 포함하고 있다.In one embodiment of the present application, the thermoplastic starch refers to a granular material obtained from plants and composed of two components, amylose and amylopectin, for example, rice starch, wheat starch, corn starch, sweet potato starch, potato starch, It may be provided including at least one selected from tapioca starch, cassava starch, and modified starches thereof. Modified starch may be provided such as α-starch, acid-treated starch, oxidized starch, cationic starch, ester starch, ether starch, etc. in which starch is physically or chemically treated. In the case of the starch, it has excellent biodegradability, is composed of amylose and amylopectin, and the glucose of amylose contains a hydroxy (-OH) group, so it has hydrophilicity and hydrogen bonding.
본원의 일 구현예예 있어서, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 경우, 생분해성 수지이면서 동시에 상용화제 역할을 제공하는 것일 수 있다. 통상적으로 폴리올레핀은 화학적 성질이 비극성으로 극성을 갖는 열가소성 전분과의 혼련성이 적어 상용성이 문제되었다. 따라서, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)를 도입함으로써 상용성을 향상시키면서 Base 수지인 폴리에틸렌의 우수한 생분해성을 동시에 제공할 수 있다. In one embodiment of the present application, in the case of the polybutylene adipate terephthalate (PBAT), it may be a biodegradable resin and at the same time provide a compatibilizer role. In general, polyolefin has a problem of compatibility because its chemical properties are non-polar and have poor kneading properties with polar thermoplastic starch. Therefore, by introducing the polybutylene adipate terephthalate (PBAT), compatibility can be improved and excellent biodegradability of polyethylene, which is a base resin, can be provided at the same time.
본원의 일 구현예에 있어서, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 중량평균분자량은 10,000 내지 100,000으로 제공되며, 바람직하게는 20,000 내지 50,000으로 제공되는 것일 수 있다. In one embodiment of the present application, the polybutylene adipate terephthalate (PBAT) may have a weight average molecular weight of 10,000 to 100,000, preferably 20,000 to 50,000.
본원의 일 구현예에 있어서, 상기 폴리비닐알코올(PVA)은 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)와 마찬가지로, 생분해성 수지이면서 동시에 상용화제 역할을 제공하는 것일 수 있다. 따라서, 친구성과 소수성기를 동시에 보유한 폴리비닐알코올(PVA)을 도입함으로써 상용성을 향상시키면서 Base 수지인 폴리에틸렌의 우수한 생분해성을 동시에 제공할 수 있다. 한편, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)은 각각 상기 생분해성 수지 조성물에 적절함량으로 포함되어야 하며, 상기 적절함량 범위를 벗어나 포함될 경우 생분해성 수지 조성물의 기능이 저하되는 것일 수 있다. 이에 대하여는 하기에 더욱 자세히 설명하도록 한다.In one embodiment of the present application, the polyvinyl alcohol (PVA), like the polybutylene adipate terephthalate (PBAT), may be a biodegradable resin and at the same time provide a compatibilizer role. Therefore, by introducing polyvinyl alcohol (PVA) having both a friend and a hydrophobic group, compatibility can be improved and excellent biodegradability of polyethylene, which is a base resin, can be provided at the same time. On the other hand, the polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) should each be included in an appropriate amount in the biodegradable resin composition, and when included outside the appropriate content range, the function of the biodegradable resin composition is reduced may be lowered. This will be described in more detail below.
본원의 일 구현예에 있어서, 상기 생분해성 수지 조성물의 용융온도는 100℃ 내지 130℃이며 상기 수지 조성물의 용융지수는 ASTM D1238기준으로 190℃의 2.16Kg에서 0.01 내지 10 g/10min으로 제공되는 것일 수 있다. 상기 용융 온도는 통상적으로 측정되는 방법인 시차 열량계(DSC, Differential Scanning Calorimetry) 또는 동적 점탄성(DMA, dynamic mechanical analysis)로 측정될 수 있고, 상기 용융지수(MI)는 ASTM D1238에 의해 측정되는 것일 수 있다.In one embodiment of the present application, the melting temperature of the biodegradable resin composition is 100 ° C to 130 ° C, and the melt index of the resin composition is 0.01 to 10 g/10 min at 2.16 Kg of 190 ° C based on ASTM D1238. can The melting temperature may be measured by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), which are commonly measured methods, and the melt index (MI) may be measured by ASTM D1238 there is.
본원의 일 구현예에 있어서, 상기 폴리에틸렌 100 중량부에 대하여, 상기 생분해성 수지의 함량은 10 중량부 내지 600 중량부인 것일 수 있으며, 바람직하게 40 중량부 내지 100 중량부인 것일 수 있고, 더욱 바람직하게는 60 중량부 내지 70 중량부인 것일 수 있다. 본원의 일 실시예에 따르면, 상기 폴리에틸렌 및 생분해성 수지는 45:30의 중량비율로 포함되는 것일 수 있다. 이때, 상기 폴리에틸렌 100 중량부에 대하여, 상기 생분해성 수지의 함량이 10 중량부 미만일 경우 경제적인 부분에서 불리할 수 있으며, 상대적으로 폴리에틸렌의 함량이 너무 많아 생분해성 분해 효과에 문제가 발생할 수 있다. 또한, 상기 생분해성 수지의 함량이 600 중량부 초과일 경우 상대적으로 폴리에틸렌의 함량이 너무 적어 통상의 플라스틱이 제공할 수 있는 우수한 기계적 물성 및 가공성 제공에 한계가 있을 수 있으며, 구체적으로 인장 강도(Tensile Strength), 연신율(Elongation) 및 낙하충격 강도 등이 감소하는 문제가 발생할 수 있다.In one embodiment of the present application, based on 100 parts by weight of the polyethylene, the content of the biodegradable resin may be 10 parts by weight to 600 parts by weight, preferably 40 parts by weight to 100 parts by weight, more preferably may be in an amount of 60 parts by weight to 70 parts by weight. According to an embodiment of the present application, the polyethylene and the biodegradable resin may be included in a weight ratio of 45:30. At this time, with respect to 100 parts by weight of the polyethylene, when the content of the biodegradable resin is less than 10 parts by weight, it may be disadvantageous in an economical part, and the content of the polyethylene is too large, which may cause a problem in the biodegradable decomposition effect. In addition, when the content of the biodegradable resin is more than 600 parts by weight, there may be a limit in providing excellent mechanical properties and processability that can be provided by conventional plastics because the content of polyethylene is relatively small, and specifically, tensile strength (Tensile) Strength), elongation (Elongation) and drop impact strength may be reduced.
본원의 일 구현예에 있어서, 상기 폴리에틸렌 100 중량부에 대하여, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 10 중량부 내지 500 중량부이고, 상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 30 중량부인 것일 수 있으며, 바람직하게 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)은 10 중량부 내지 50 중량부일 수 있고, 더욱 바람직하게 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)은 30 중량부 내지 45 중량부, 폴리비닐알코올(PVA)은 10 중량부 내지 25 중량부인 것일 수 있다. 본원의 일 실시예에 따르면, 상기 폴리에틸렌, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)은 45: 15 내지 20: 5 내지 10의 중량비율로 포함되는 것일 수 있다. 이때, 상기 폴리에틸렌 100 중량부에 대하여, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량이 10 중량부 미만이거나, 상기 폴리비닐알코올(PVA)의 함량이 10 중량부 미만일 경우 그에 의한 생분해 효과가 미미할 수 있으며, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량이 500 중량부 초과이거나, 폴리비닐알코올(PVA)의 함량이 30 중량부 초과일 경우 폴리에틸렌과의 상용성 및 가공성에서 문제가 발생할 수 있다.In one embodiment of the present application, based on 100 parts by weight of the polyethylene, the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 500 parts by weight, and the content of the polyvinyl alcohol (PVA) is 10 It may be in an amount of from 10 parts by weight to 30 parts by weight, preferably, 10 parts by weight to 50 parts by weight of polybutylene adipate terephthalate (PBAT), and more preferably 30 parts by weight of polybutylene adipate terephthalate (PBAT). to 45 parts by weight, polyvinyl alcohol (PVA) may be 10 parts by weight to 25 parts by weight. According to an embodiment of the present application, the polyethylene, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) may be included in a weight ratio of 45: 15 to 20: 5 to 10. At this time, based on 100 parts by weight of the polyethylene, when the content of the polybutylene adipate terephthalate (PBAT) is less than 10 parts by weight or the content of the polyvinyl alcohol (PVA) is less than 10 parts by weight, the biodegradation effect by this is It may be insignificant, and when the content of polybutylene adipate terephthalate (PBAT) exceeds 500 parts by weight or the content of polyvinyl alcohol (PVA) exceeds 30 parts by weight, problems may occur in compatibility with polyethylene and processability. there is.
본원의 제 2 측면은,The second aspect of the present application is
상기 본원의 제 1 측면에 따른 생분해성 수지 조성물을 포함하는 생분해성 필름을 제공한다.It provides a biodegradable film comprising the biodegradable resin composition according to the first aspect of the present application.
본원의 제 1 측면과 중복되는 부분들에 대해서는 상세한 설명을 생략하였으나, 본원의 제 1 측면에 대해 설명한 내용은 제 2 측면에서 그 설명이 생략되었더라도 동일하게 적용될 수 있다.Although a detailed description of the overlapping parts of the first aspect of the present application is omitted, the description of the first aspect of the present application may be equally applied even if the description thereof is omitted in the second aspect.
이하, 본원의 제 2 측면에 따른 생분해성 필름을 상세히 설명한다.Hereinafter, the biodegradable film according to the second aspect of the present application will be described in detail.
본원의 일 구현예에 있어서, 상기 필름은 공업용 필름, 식품용 필름, 농업용 필름, 생활용 필름에서 선택되는 적어도 어느 하나 이상에 적용이 가능하며, 기존에 플라스틱이 제공하는 기계적 물성은 그대로 제공하면서, 향상된 생분해성이 제공 가능한 것일 수 있다. 이와 관련하여, 후술할 도 1 및 2를 참고하면, 상기 필름의 우수한 분해성을 확인할 수 있다. 따라서, 필름의 사용 후, 일정 조건을 갖춘 시설(Compost)에서 퇴비화할 수 있다. 또한, 부득이 연소시키더라도 발생 열량이 낮아서 다이옥신 등 유해물질의 방출을 최소화할 수 있다. In one embodiment of the present application, the film can be applied to at least one selected from an industrial film, a food film, an agricultural film, and a household film, and the mechanical properties provided by conventional plastics are improved while providing Biodegradability may be provided. In this regard, with reference to FIGS. 1 and 2 to be described later, excellent decomposition properties of the film can be confirmed. Therefore, after using the film, it can be composted in a facility with certain conditions (Compost). In addition, even if it is unavoidably burned, the amount of heat generated is low, so that the emission of harmful substances such as dioxins can be minimized.
본원의 일 구현예에 있어서, 상기 생분해성 필름은 토양에 4주 매립 후, 매립 전 무게에 비해 무게 변화량이 -15% 이상인 것이고, 상기 무게 변화량은 하기 식 1로 표시되는 것일 수 있다.In one embodiment of the present application, the biodegradable film has a weight change of -15% or more compared to the weight before embedding after 4 weeks of burying in the soil, and the weight change may be expressed by Equation 1 below.
[식 1][Equation 1]
무게 변화량 = (4주 매립 후 생분해성 필름의 무게 - 매립 전 생분해성 필름의 무게) / (4주 매립 후 생분해성 필름의 무게) X 100Weight change = (weight of biodegradable film after burying for 4 weeks - weight of biodegradable film before burial) / (weight of biodegradable film after burying for 4 weeks) X 100
이때, 상기 식 1에서, 무게 변화량은 음의 값으로서 상기 -15% 이상은 음의 값으로 커짐을 의미하는 것일 수 있다. 한편, 상기 무게 변화량은 바람직하게 -18% 이상인 것일 수 있으며, 더욱 바람직하게는 약 -19% 내지 -20%인 것일 수 있다.In this case, in Equation 1, the amount of change in weight is a negative value, and it may mean that -15% or more increases to a negative value. On the other hand, the weight change may be preferably -18% or more, and more preferably about -19% to -20%.
본원의 일 구현예에 있어서, 상기 생분해성 필름은 토양에 4주 매립 후, 매립 전 두께에 비해 두께 변화량이 -12% 이상인 것이고, 상기 두께 변화량은 하기 식 2로 표시되는 것일 수 있다.In one embodiment of the present application, the biodegradable film has a thickness change of -12% or more compared to the thickness before embedding after 4 weeks of burying in soil, and the thickness change may be expressed by Equation 2 below.
[식 2][Equation 2]
두께 변화량 = (4주 매립 후 생분해성 필름의 두께 - 매립 전 생분해성 필름의 두께) / (4주 매립 후 생분해성 필름의 두께) X 100Thickness change = (thickness of biodegradable film after 4 weeks of burying - thickness of biodegradable film before burial) / (thickness of biodegradable film after 4 weeks of burying) X 100
이때, 상기 식 2에서, 두께 변화량은 음의 값으로서 상기 -12% 이상은 음의 값으로 커짐을 의미하는 것일 수 있다. 한편, 상기 두께 변화량은 바람직하게 -13% 이상인 것일 수 있으며, 더욱 바람직하게는 약 -13% 내지 -15%인 것일 수 있다.In this case, in Equation 2, the thickness change amount is a negative value, and -12% or more may mean that a negative value increases. On the other hand, the thickness variation may be preferably -13% or more, and more preferably about -13% to -15%.
본원의 일 구현예에 있어서, 상기 필름의 두께는 20 내지 40㎛으로 제공될 수 있고, 바람직하게는 30㎛로 제공될 수 있다.In one embodiment of the present application, the thickness of the film may be provided as 20 to 40㎛, preferably may be provided as 30㎛.
본원의 제 3 측면은,The third aspect of the present application is
폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)을 포함하여, 용융블렌딩방법으로 제조되는 생분해성 수지 조성물의 제조방법을 제공한다.It provides a method for preparing a biodegradable resin composition prepared by a melt blending method, including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA).
본원의 제 1 측면 및 제 2 측면과 중복되는 부분들에 대해서는 상세한 설명을 생략하였으나, 본원의 제 1 측면 및 제 2 측면에 대해 설명한 내용은 제 3 측면에서 그 설명이 생략되었더라도 동일하게 적용될 수 있다.Although detailed descriptions of parts overlapping with the first and second aspects of the present application are omitted, the descriptions of the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect. .
이하, 본원의 제 3 측면에 따른 생분해성 수지 조성물의 제조방법을 상세히 설명한다.Hereinafter, the manufacturing method of the biodegradable resin composition according to the third aspect of the present application will be described in detail.
본원의 일 구현예에 있어서, 상기 폴리에틸렌 100 중량부에 대하여, 상기 생분해성 수지의 함량은 10 중량부 내지 600 중량부인 것일 수 있으며, 바람직하게 40 중량부 내지 100 중량부인 것일 수 있고, 더욱 바람직하게는 60 중량부 내지 70 중량부인 것일 수 있다. 본원의 일 실시예에 따르면, 상기 폴리에틸렌 및 생분해성 수지는 45:30의 중량비율로 포함되는 것일 수 있다. 이때, 상기 폴리에틸렌 100 중량부에 대하여, 상기 생분해성 수지의 함량이 10 중량부 미만일 경우 경제적인 부분에서 불리할 수 있으며, 상대적으로 폴리에틸렌의 함량이 너무 많아 생분해성 분해 효과에 문제가 발생할 수 있다. 또한, 상기 생분해성 수지의 함량이 600 중량부 초과일 경우 상대적으로 폴리에틸렌의 함량이 너무 적어 통상의 플라스틱이 제공할 수 있는 우수한 기계적 물성 및 가공성 제공에 한계가 있을 수 있으며, 구체적으로 인장 강도(Tensile Strength), 연신율(Elongation) 및 낙하충격 강도 등이 감소하는 문제가 발생할 수 있다.In one embodiment of the present application, based on 100 parts by weight of the polyethylene, the content of the biodegradable resin may be 10 parts by weight to 600 parts by weight, preferably 40 parts by weight to 100 parts by weight, more preferably may be in an amount of 60 parts by weight to 70 parts by weight. According to an embodiment of the present application, the polyethylene and the biodegradable resin may be included in a weight ratio of 45:30. At this time, with respect to 100 parts by weight of the polyethylene, when the content of the biodegradable resin is less than 10 parts by weight, it may be disadvantageous in an economical part, and the content of the polyethylene is too large, which may cause a problem in the biodegradable decomposition effect. In addition, when the content of the biodegradable resin is more than 600 parts by weight, there may be a limit in providing excellent mechanical properties and processability that can be provided by conventional plastics because the content of polyethylene is relatively small, and specifically, tensile strength (Tensile) Strength), elongation (Elongation) and drop impact strength may be reduced.
본원의 일 구현예에 있어서, 상기 폴리에틸렌 100 중량부에 대하여, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 10 중량부 내지 500 중량부이고, 상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 30 중량부인 것일 수 있으며, 바람직하게 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)은 10 중량부 내지 50 중량부일 수 있고, 더욱 바람직하게 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)은 30 중량부 내지 45 중량부, 폴리비닐알코올(PVA)은 10 중량부 내지 25 중량부인 것일 수 있다. 본원의 일 실시예에 따르면, 상기 폴리에틸렌, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)은 45: 15 내지 20: 5 내지 10의 중량비율로 포함되는 것일 수 있다. 이때, 상기 폴리에틸렌 100 중량부에 대하여, 상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량이 10 중량부 미만이거나, 상기 폴리비닐알코올(PVA)의 함량이 10 중량부 미만일 경우 그에 의한 생분해 효과가 미미할 수 있으며, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량이 500 중량부 초과이거나, 폴리비닐알코올(PVA)의 함량이 30 중량부 초과일 경우 폴리에틸렌과의 상용성 및 가공성에서 문제가 발생할 수 있다.In one embodiment of the present application, based on 100 parts by weight of the polyethylene, the content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 500 parts by weight, and the content of the polyvinyl alcohol (PVA) is 10 It may be in an amount of from 10 parts by weight to 30 parts by weight, preferably, 10 parts by weight to 50 parts by weight of polybutylene adipate terephthalate (PBAT), and more preferably 30 parts by weight of polybutylene adipate terephthalate (PBAT). to 45 parts by weight, polyvinyl alcohol (PVA) may be 10 parts by weight to 25 parts by weight. According to an embodiment of the present application, the polyethylene, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA) may be included in a weight ratio of 45: 15 to 20: 5 to 10. At this time, based on 100 parts by weight of the polyethylene, when the content of the polybutylene adipate terephthalate (PBAT) is less than 10 parts by weight or the content of the polyvinyl alcohol (PVA) is less than 10 parts by weight, the biodegradation effect by this is It may be insignificant, and when the content of polybutylene adipate terephthalate (PBAT) exceeds 500 parts by weight or the content of polyvinyl alcohol (PVA) exceeds 30 parts by weight, problems may occur in compatibility with polyethylene and processability. there is.
본원의 일 구현예에 있어서, 상기 용융블렌딩은 압출기, 니더(Kneader), 브라벤더 플라스티코더(Brabender Plasticorder), 믹싱롤(Mixing Roll) 및 혼합기에서 선택되는 적어도 어느 하나 이상을 사용하여 제공되는 것일 수 있다.In one embodiment of the present application, the melt blending is provided using at least one selected from an extruder, a kneader, a Brabender Plasticorder, a mixing roll, and a mixer. can
본원의 일 구현예에 있어서, 상기 압출기는 일축 압출기, 이축 압출기, 일축 스크류 및 이축 스크류 압출기에서 선택된 어느 하나 이상을 사용하여 제공되는 것일 수 있으며, 바람직하게는 이축 압출기를 사용하여 제공됨으로써 우수한 혼련성과 용이한 가공성을 제공할 수 있다.In one embodiment of the present application, the extruder may be provided by using any one or more selected from a single screw extruder, a twin screw extruder, a single screw and a twin screw extruder, and preferably by using a twin screw extruder, excellent kneading performance and Easy processability can be provided.
본 발명의 일 실시예에 따르면, 상기 용융 블렌딩에서 투입하게 되는 각종 원료 물질에 따라서 공정 조건을 최적화시켜 공정을 진행할 수 있다. 용융 온도는 100℃ 내지 300℃가 제공될 수 있으며, 바람직하게는 160℃ 내지 210℃가 제공되며, 압출기 스크류의 회전 속도는 40rpm 내지 700rpm으로 제공되며, 바람직하게는 100rpm 내지 200rpm으로 제공될 수 있다.According to an embodiment of the present invention, the process may be performed by optimizing process conditions according to various raw materials to be input in the melt blending. The melting temperature may be provided in a range of 100°C to 300°C, preferably 160°C to 210°C, and the rotation speed of the extruder screw is provided in a range of 40rpm to 700rpm, preferably 100rpm to 200rpm. .
본 발명에 따른 생분해성 수지 조성물은 폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올을 포함한 4 성분의 조합으로 제공하여 상용성을 향상시키고, 이에 폴리에틸렌의 분해성을 향상시키는 효과를 제공한다. The biodegradable resin composition according to the present invention improves compatibility by providing a combination of four components including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol, thereby improving the degradability of polyethylene provides the effect of
본 발명에 따른 생분해성 수지 조성물을 포함하는 필름의 경우, 공업용, 식품용, 농업용 등 다양한 분야에 적용이 가능하며, 우수한 생분해성을 제공하여 환경문제 해결에 기여하는 효과를 제공한다.In the case of a film comprising the biodegradable resin composition according to the present invention, it can be applied to various fields such as industrial, food, agricultural, etc., and provides excellent biodegradability to contribute to solving environmental problems.

Claims (18)

  1. 폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)을 포함하는 생분해성 수지 조성물.A biodegradable resin composition comprising polyethylene, a biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA).
  2. 제1항에 있어서,According to claim 1,
    상기 폴리에틸렌은 고밀도폴리에틸렌(HDPE), 저밀도폴리에틸렌(LDPE), 중간밀도폴리에틸렌(MDPE), 선형저밀도폴리에틸렌(LLDPE), 에틸렌비닐공중합체(EVA) 및 이들의 조합들로 이루어진 군으로부터 선택되는 폴리머를 포함하는 것인 생분해성 수지 조성물.The polyethylene comprises a polymer selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), ethylene vinyl copolymer (EVA), and combinations thereof. A biodegradable resin composition that does.
  3. 제1항에 있어서,According to claim 1,
    상기 생분해성 수지는 열가소성 전분(TPS), 폴리락트산(PLA), 폴리카프로락톤(PCL), 폴리부틸렌석시네이트(PBS), 폴리글리콜산(PGA), 폴리하이드록시알카노에이트(PHA), 폴리하이드록시부틸레이트(PHB), 셀룰로오스, 키틴 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것인 생분해성 수지 조성물.The biodegradable resin is thermoplastic starch (TPS), polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), A biodegradable resin composition comprising a material selected from the group consisting of polyhydroxybutyrate (PHB), cellulose, chitin, and combinations thereof.
  4. 제3항에 있어서,4. The method of claim 3,
    상기 열가소성 전분은 쌀전분, 밀전분, 옥수수전분, 고구마전분, 감자전분, 타피오카전분, 카사바전분 및 이들의 변성 전분에서 선택되는 적어도 어느 하나 이상을 포함하는 것인 생분해성 수지 조성물.The thermoplastic starch is a biodegradable resin composition comprising at least one selected from rice starch, wheat starch, corn starch, sweet potato starch, potato starch, tapioca starch, cassava starch, and modified starches thereof.
  5. 제1항에 있어서,According to claim 1,
    상기 폴리에틸렌의 중량평균분자량은 100,000 내지 1,000,000인 것인 생분해성 수지 조성물.The weight average molecular weight of the polyethylene is a biodegradable resin composition of 100,000 to 1,000,000.
  6. 제1항에 있어서,According to claim 1,
    상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 중량평균분자량은 10,000 내지 100,000인 것인 생분해성 수지 조성물.The weight average molecular weight of the polybutylene adipate terephthalate (PBAT) is 10,000 to 100,000 biodegradable resin composition.
  7. 제1항에 있어서,According to claim 1,
    상기 생분해성 수지 조성물의 용융온도는 100℃ 내지 130℃이며, 용융지수는 ASTM D1238기준으로 190℃의 2.16Kg에서 0.01 내지 10g/10min인 것인 생분해성 수지 조성물.The biodegradable resin composition has a melting temperature of 100°C to 130°C, and a melt index of 0.01 to 10g/10min at 2.16Kg of 190°C based on ASTM D1238.
  8. 제1항에 있어서,According to claim 1,
    상기 폴리에틸렌 100 중량부에 대하여,Based on 100 parts by weight of the polyethylene,
    상기 생분해성 수지의 함량은 10 중량부 내지 600 중량부이고,The content of the biodegradable resin is 10 parts by weight to 600 parts by weight,
    상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 10 중량부 내지 500 중량부이며,The content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 500 parts by weight,
    상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 30 중량부인 것인 생분해성 수지 조성물.The content of the polyvinyl alcohol (PVA) is 10 parts by weight to 30 parts by weight of the biodegradable resin composition.
  9. 제1항에 있어서,According to claim 1,
    상기 폴리에틸렌 100 중량부에 대하여,Based on 100 parts by weight of the polyethylene,
    상기 생분해성 수지의 함량은 40 중량부 내지 100 중량부이고,The content of the biodegradable resin is 40 parts by weight to 100 parts by weight,
    상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 10 중량부 내지 50 중량부이며,The content of the polybutylene adipate terephthalate (PBAT) is 10 parts by weight to 50 parts by weight,
    상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 30 중량부인 것인 생분해성 수지 조성물.The content of the polyvinyl alcohol (PVA) is 10 parts by weight to 30 parts by weight of the biodegradable resin composition.
  10. 제1항에 있어서,According to claim 1,
    상기 폴리에틸렌 100 중량부에 대하여,Based on 100 parts by weight of the polyethylene,
    상기 생분해성 수지의 함량은 60 중량부 내지 70 중량부이고,The content of the biodegradable resin is 60 parts by weight to 70 parts by weight,
    상기 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)의 함량은 30 중량부 내지 45 중량부이며,The content of the polybutylene adipate terephthalate (PBAT) is 30 parts by weight to 45 parts by weight,
    상기 폴리비닐알코올(PVA)의 함량은 10 중량부 내지 25 중량부인 것인 생분해성 수지 조성물.The content of the polyvinyl alcohol (PVA) is 10 parts by weight to 25 parts by weight of the biodegradable resin composition.
  11. 제1항에 따른 생분해성 수지 조성물을 포함하는 생분해성 필름.A biodegradable film comprising the biodegradable resin composition according to claim 1.
  12. 제11항에 있어서,12. The method of claim 11,
    상기 생분해성 필름은 토양에 4주 매립 후, 매립 전 무게에 비해 무게 변화량이 -15% 이상인 것이고,The biodegradable film has a weight change of -15% or more compared to the weight before embedding after 4 weeks of burying in the soil,
    상기 무게 변화량은 하기 식 1로 표시되는 것인 생분해성 필름:The weight change is a biodegradable film that is represented by the following formula 1:
    [식 1][Equation 1]
    무게 변화량 = (4주 매립 후 생분해성 필름의 무게 - 매립 전 생분해성 필름의 무게) / (4주 매립 후 생분해성 필름의 무게) X 100Weight change = (weight of biodegradable film after burying for 4 weeks - weight of biodegradable film before burial) / (weight of biodegradable film after burying for 4 weeks) X 100
    (상기 식 1에서, 무게 변화량은 음의 값으로서 상기 -15% 이상은 음의 값으로 커짐을 의미함.)(In Equation 1, the amount of change in weight is a negative value, meaning that -15% or more increases to a negative value.)
  13. 제11항에 있어서,12. The method of claim 11,
    상기 생분해성 필름은 토양에 4주 매립 후, 매립 전 두께에 비해 두께 변화량이 -12% 이상인 것이고,The biodegradable film has a thickness change of -12% or more compared to the thickness before burying after 4 weeks of burying in the soil,
    상기 두께 변화량은 하기 식 2로 표시되는 것인 생분해성 필름:The thickness variation is a biodegradable film that is represented by the following formula 2:
    [식 2][Equation 2]
    두께 변화량 = (4주 매립 후 생분해성 필름의 두께 - 매립 전 생분해성 필름의 두께) / (4주 매립 후 생분해성 필름의 두께) X 100Thickness change = (thickness of biodegradable film after 4 weeks of burying - thickness of biodegradable film before burial) / (thickness of biodegradable film after 4 weeks of burying) X 100
    (상기 식 2에서, 두께 변화량은 음의 값으로서 상기 -12% 이상은 음의 값으로 커짐을 의미함.)(In Equation 2, the thickness variation is a negative value, meaning that -12% or more increases to a negative value.)
  14. 제11항에 있어서,12. The method of claim 11,
    상기 필름은 공업용 필름, 식품용 필름, 농업용 필름, 생활용 필름에서 선택되는 적어도 어느 하나 이상에 적용이 가능한 생분해성 필름.The film is a biodegradable film that can be applied to at least one selected from industrial film, food film, agricultural film, and daily life film.
  15. 폴리에틸렌, 생분해성 수지, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리비닐알코올(PVA)을 포함하여, 용융블렌딩방법으로 제조되는 생분해성 수지 조성물의 제조방법.A method for producing a biodegradable resin composition prepared by a melt blending method, including polyethylene, biodegradable resin, polybutylene adipate terephthalate (PBAT) and polyvinyl alcohol (PVA).
  16. 제15항에 있어서,16. The method of claim 15,
    상기 용융블렌딩은 160℃ 내지 210℃에서 진행되는 것인 생분해성 수지 조성물의 제조방법.The melt blending method for producing a biodegradable resin composition that proceeds at 160 ℃ to 210 ℃.
  17. 제15항에 있어서,16. The method of claim 15,
    상기 용융블렌딩은 압출기, 니더, 브라벤더 플라스티코더, 믹싱롤 및 혼합기에서 선택되는 적어도 어느 하나 이상을 사용하는 것인 생분해성 수지 조성물의 제조방법.The melt blending is a method for producing a biodegradable resin composition by using at least one selected from an extruder, a kneader, a Brabender plastic coder, a mixing roll, and a mixer.
  18. 제17항에 있어서,18. The method of claim 17,
    상기 압출기는 일축 압출기, 이축 압출기, 일축 스크류 및 이축 스크류 압출기에서 선택된 어느 하나 이상을 사용하는 것인 생분해성 수지 조성물의 제조방법.The extruder is a method for producing a biodegradable resin composition using at least one selected from a single screw extruder, a twin screw extruder, a single screw and a twin screw extruder.
PCT/KR2021/014921 2020-11-02 2021-10-22 Biodegradable resin composition containing polyvinyl alcohol and method for manufacturing same WO2022092717A1 (en)

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