KR102587591B1 - Biodegradable composition and application products using the composition - Google Patents

Abstract

The present invention relates to a biodegradable resin composition, and more specifically, to a biodegradable resin composition that not only has excellent mechanical properties but can also be easily biodegraded in various soil environments, thereby significantly reducing the burden on the environment, and the composition. It is about the applied products used.

Description

Biodegradable resin composition and application products using the composition {Biodegradable composition and application products using the composition}

The present invention relates to a biodegradable resin composition, and more specifically, to a biodegradable resin composition that not only has excellent mechanical properties but can also be easily biodegraded in various soil environments, thereby significantly reducing the burden on the environment, and the composition. It is about the applied products used.

In general, polymer products using petroleum-based resins are widely used in daily life. However, currently known polymer products using petroleum-based resins are likely to cause environmental problems by emitting hazardous substances when disposed of. To solve this environmental pollution problem, research on biodegradable plastics has been actively conducted recently.

Biodegradable plastic is a polymer that polymerizes monomers produced through biological processes, and is decomposed into low-molecular-weight substances by microorganisms existing in nature, and finally decomposes into water and carbon dioxide or methane gas. Representative materials include biodegradable resins, including polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT), which are attracting attention as a means of replacing petroleum-based resins. However, there are disadvantages in that it is difficult to biodegrade in various soil environments or requires a long period of time under certain conditions to be biodegraded, and in particular, there is a limit to complete biodegradation. In order to overcome these problems, research on biodegradable resins that can be applied to various fields is needed.

Moreover, due to the recent spread of Corona (COVID-19), various fields such as disposable products such as disposable containers, packaging plastic, straws, and cold cups, electronic product packaging materials such as air caps and electronic product trays, and marine and fishery products such as buoys and fishing nets are being used in various fields. The need for the use of biodegradable resin is emerging.

However, in order to apply biodegradable plastic to various purposes, it must not only have excellent biodegradability in various soil environments but also realize satisfactory physical properties, and in particular, it must realize strength, impact resistance, flexibility, transparency, etc. depending on the intended use. .

To this end, products using a mixture of polylactic acid and polybutylene adipate have been mainly developed recently, but due to the lack of compatibility between the two materials, not only are the desired physical properties and flexibility not secured, but satisfactory Even biodegradable resin formulations have not been implemented.

Recently, research is underway to apply polyhydroxyalkanoate (PHA), which shows excellent biodegradability even in the ocean. PHA has the characteristics of rubber, showing improved flexibility and improved impact strength when applied.

Domestic Patent Publication No. 10-2021-0095003

Based on numerous research results, the present inventors have secured biodegradability that satisfies biodegradability in various soil environments as well as physical properties such as strength, impact resistance, flexibility, and transparency depending on the use, while including PLA-based resin, and also secured manufacturing convenience. did. In addition, there are many difficulties in using PHA alone due to its low moldability and physical properties, but the present invention was completed by developing a resin composition that can compensate for this.

Therefore, the purpose of the present invention is to provide a biodegradable resin composition that can be easily molded into a product of a desired shape by a general product molding method by controlling the type and content of the components, and an applied product using the composition.

The object of the present invention is not limited to the object mentioned above, and even if not explicitly mentioned, the object of the invention that can be recognized by a person of ordinary skill in the art from the description of the detailed description of the invention described later may also naturally be included. .

In order to achieve the object of the present invention described above, first, the present invention is 0.1 to 50 parts by weight of polyhydroxyalkanoate (PHA)-based resin per 100 parts by weight of base resin containing polylactic acid (PLA)-based resin, 1 type. Provided is a biodegradable resin composition containing 0.1 to 10 parts by weight of the above chain extender.

In a preferred embodiment, the base resin is polybutylene adipate-co-terephthalate (PBAT), polycaprolactone, polyglycolic acid, polybutylene succinate (PBS), and polybutylene. Succinate adipate (Poly(butylene succinate-co-butylene adipate, PBSA), polybutylene succinate-terephthalate (PBST), polybutylene adipate, polyhydroxy butyrate (PHB), poly-3 -hydroxyvalerate (poly-3-hydroxyvalerate, PBV), polyhydroxybutyratevalerate (PHBV), poly-3-hydroxybutyrate-co-3-hydroxyvalerate (poly-(3-hydroxy butyrate-co-3-hydroxyvalerate), poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (poly-(3-hydroxybutyrate -co-3-hydroxyhexanoate), one or more selected from the group consisting of Includes more.

In a preferred embodiment, the PHA-based resin contains two or more different repeating units in the polymer chain, and the different repeating units are irregularly distributed.

In a preferred embodiment, the repeating unit is 2-hydroxybutyrate, lactic acid, glycolic acid, 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvale Late (3-HV), 3-hydroxyhexanoate (3-HH), 3-hydroxyheptanoate (3-HHep), 3-hydroxyoctanoate (3-HO), 3-hydroxy Nonanoate (3-HN), 3-hydroxydecanoate (3-HD), 3-hydroxydodecanoate (3-HDd), 4-hydroxybutyrate (4-HB), 4-hydroxy It is one or more selected from the group consisting of valerate (4-HV), 5-hydroxyvalerate (5-HV), and 6-hydroxyhexanoate (6-HH).

In a preferred embodiment, the PHA-based resin has a glass transition temperature (Tg) of -45°C to 80°C, a crystallization temperature (Tc) of 70 to 120°C, a melting temperature (Tm) of 100 to 170°C, and a molecular weight of 10,000. g/mol ~ 1,200,000 g/mol.

In a preferred embodiment, at least one of the chain extenders is an epoxy functional compound consisting of a di- or polyfunctional terminal epoxide.

In a preferred embodiment, the epoxy functional compound is a compound containing 2 to 9 or less epoxy groups aligned at the ends of the molecular chain or side chain.

In a preferred embodiment, at least one of the chain extenders is hexamethylene diisocyanate (HDI), hexanediol diglycidyl ether (1,6-hexanediol diglycidyl ether), diacyl peroxide, peroxy ketal, Peroxyester, dialkyl peroxide and hydrogen peroxide, ethylene glycol, propylene glycol, 1,4-butanediol, glycerine trimethylolpropane, pentaelsritol, oxypropylated ethylene diamine, hexamethylenediamine, m-phenylenediamine, diethanol. Amine, triethanolamine, benzoyl peroxide, lauroyl peroxide, 1,3- or 1,4-bis(tert-butylperoxyisopropyl)benzene, n-butyl-4,4'-di(tert-butylperoxy) ) Valerate, t-butyl peroxybenzoate, 1,1-di-t-butylperoxy-2,4-di-t-butylcyclohexane, 2,5-dimethyl-2,5-di-(t -Butylperoxy)hexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane.

In a preferred embodiment, graphite, native copper, sulfur, quartz, orthosite, plagioclase, biotite, olivine, hornblende, calcite, malachite, aragonite, phosphate, apatite, apatite, magnetite, hematite, barite, chalcopyrite, pyrite, galena. , fluorite, bentonite, kaolin, talc, talcum powder, calcium carbonate, chalk powder, egg shell, gypsum, carbon black, iron oxide, dolomite, calcium chloride, barium sulfate, silicon dioxide, wollastonite, silicate, mica, emery, silica, silicon, talc. , 0.1 to 60% by weight of one or more fillers selected from the group consisting of zeolite, starch, glass fiber, etc., based on the total weight of the biodegradable resin composition.

In a preferred embodiment, one or more additives selected from the group consisting of antioxidants, compatibilizers, weighting agents, nucleating agents, melt strength increasers, polymerization initiators, and slip agents are added in an amount of 0.1 weight based on the total weight of the biodegradable resin composition. % to 30% by weight.

Additionally, the present invention provides a biodegradable resin application product composed of any of the biodegradable resin compositions described above.

In a preferred embodiment, the biodegradable resin application product has a tensile strength of 30 MPa or more and a biodegradability of 90% or more compared to the standard material.

In a preferred embodiment, the applied product is one or more selected from the group consisting of cold cups, buttons, golf tees, disposable containers, packaging vinyl, trays, and sheets.

In addition, the present invention includes the steps of putting any of the above-described biodegradable resin compositions uniformly mixed into an extrusion molding machine, melting them, and then extruding them into a thread shape; Cutting the manufactured thread shape to produce pellets; and manufacturing a biodegradable resin application product by putting the pellets into a molder or extruder.

In a preferred embodiment, the molding machine or extruder is any selected from the group consisting of extrusion molding machine, injection molding machine, blow molding machine, pressure molding machine, calendaring, rotational molding, casting, T-die extruder, blown film extruder, and thermoforming machine. It is one.

The above-described biodegradable resin composition of the present invention and applied products using the composition not only secured commercially usable mechanical properties, flexibility, and moldability by controlling the types and contents of the components, but also satisfied biodegradability in various soil environments. It can demonstrate excellent eco-friendliness.

These technical effects of the present invention are not limited to the scope mentioned above, and even if not explicitly mentioned, the effects of the invention that can be recognized by a person of ordinary skill in the art from the description of the specific contents for implementing the invention described later. Of course it is included.

Figure 1 is a photograph for confirming the moldability of a product manufactured with a biodegradable composition according to embodiments of the present invention.

The terms used in the present invention are merely used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the description of the invention, but are intended to indicate the presence of one or more other It should be understood that this does not exclude in advance the presence or addition of features, numbers, steps, operations, components, parts, or combinations thereof.

Terms such as first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, a first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component without departing from the scope of the present invention.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless clearly defined in the present invention, should not be interpreted in an idealized or excessively formal sense. No.

When interpreting a component, it is interpreted to include the margin of error even if there is no separate explicit description. In particular, when terms of degree such as "about", "substantially", etc. are used, they may be interpreted as being used at or close to that value when manufacturing and material tolerances inherent in the stated meaning are presented. .

In the case of a description of a temporal relationship, for example, if a temporal relationship is described as ‘after’, ‘after’, ‘after’, ‘before’, etc., ‘immediately’ or ‘directly’ Even non-consecutive cases are included unless ' is used.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to the attached drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like reference numerals used to describe the invention throughout the specification represent like elements.

The technical feature of the present invention is a biodegradable resin composition that exhibits excellent biodegradability in a general soil environment by controlling the type and content of the components, and secures not only the mechanical properties necessary for commercialization but also the moldability that can be easily molded using general molding methods. and application products containing the same.

In other words, existing biodegradable resin products have limitations in that they require a long period of time under specific conditions in the biodegradation process to be decomposed, or in particular, when they contain PLA-based resin, biodegradation occurs only when specific conditions are met, and PLA-based resin or polybutylene This is because adipate resins also have the problem of lack of compatibility. In order to solve this problem, the present invention introduces a polyhydroxyalkanoate (PHA)-based resin and uses a chain extender to improve physical properties such as strength, impact resistance, flexibility, and transparency depending on the application, as well as in various soil environments. In addition to ensuring biodegradability, manufacturing convenience was also secured. However, since PHA also has low moldability and physical properties when used alone, it is difficult to use alone, so it was focused on the need for blending with other materials that can complement this.

Therefore, the biodegradable resin composition of the present invention contains 0.1 to 50 parts by weight of polyhydroxyalkanoate (PHA)-based resin and 0.1 part by weight of one or more chain extenders per 100 parts by weight of base resin containing polylactic acid (PLA)-based resin. Contains to 10 parts by weight.

Here, the base resin may be composed only of polylactic acid (PLA)-based resin, or may further include a known biodegradable resin, as one embodiment, polybutylene adipate-co-terephthalate (PBAT). ), polycaprolactone, polyglycolic acid, polybutylene succinate (PBS), polybutylene adipate, polyhydroxy butyrate (PHB), poly-3-hydroxyvalerate ,PBV), polyhydroxybutyratevalerate (PHBV), poly-3-hydroxybutyrate-co-3-hydroxyvalerate (poly-(3-hydroxy butyrate-co-3-hydroxyvalerate), poly- It may further include one or more selected from the group consisting of 3-hydroxybutyrate-co-3-hydroxyhexanoate (poly-(3-hydroxybutyrate -co-3-hydroxyhexanoate).

The PLA-based resin included in the base resin of the present invention may be polylactic acid (PLA) or a polylactic acid-based biodegradable polymer containing polylactic acid.

As is known, polylactic acid (PLA)-based resin is a biodegradable thermoplastic plastic, has high strength and thermoplasticity, is excellent in biodegradability and compatibility with the human body, but has the characteristic of being easily brittle or easily hydrolyzed. , In the present invention, a certain amount of polyhydroxyalkanoate (PHA)-based resin and one or more types of chain linking agents were used to maximize the advantages and minimize the disadvantages of the PLA-based resin. Therefore, the content of PHA-based resin and chain extender improves physical stability and/or excellent biodegradability and/or excellent moldability and/or stability depending on the type and content of PLA-based resin and/or other biodegradable resin contained in the base resin. /or can be adjusted to implement improved flexibility, etc.

Polyhydroxyalkanoate (PHA)-based resin is a biological polyester resin that can contain over 100 different types of monomers because it is formed by fermenting one or more monomer units within living cells. The PHA-based resin used in the present invention may be a homopolymer in which all monomer units, that is, repeating units, are the same, or it may be a copolymer with two or more different repeating units. In particular, when the PHA-based resin of the present invention is a copolymer containing two or more different repeating units in the polymer chain, in one embodiment, the different repeating units may be irregularly distributed.

In the present invention, when the PHA-based resin is a homopolymer or copolymer, the repeating units included in the PHA-based resin of the present invention are 2-hydroxybutyrate, lactic acid, glycolic acid, 3-hydroxybutyrate (3-HB), 3- Hydroxypropionate (3-HP), 3-hydroxyvalerate (3-HV), 3-hydroxyhexanoate (3-HH), 3-hydroxyheptanoate (3-HHep), 3 -Hydroxyoctanoate (3-HO), 3-hydroxynonanoate (3-HN), 3-hydroxydecanoate (3-HD), 3-hydroxydodecanoate (3-HDd) , 4-hydroxybutyrate (4-HB), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate (6-HH). It may be one or more types selected from the group.

By selecting the above-described monomer types and controlling the ratio of monomer units in a given PHA homopolymer and/or copolymer, a wide range of material properties can be achieved, such as the biodegradability of the present invention comprising a PHA-based resin. In order to improve the biodegradability of the resin composition in soil and the ocean, and to realize excellent physical properties such as improved optical, thermal, and mechanical properties, the PHA-based resin has a glass transition temperature (Tg) of -45℃ ~ 80℃, and crystallization. The type and content of repeating units included in the PHA resin can be adjusted so that the temperature (Tc) is 70 to 120℃, the melting temperature (Tm) is 100 to 170℃, and the molecular weight is 10,000g/mol to 1,200,000g/mol. You can.

In the present invention, the PHA-based resin can be used in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the base resin. The content of the PHA-based resin is determined experimentally. If it is less than 0.1 part by weight, the absolute content is small and has little effect on physical stability or biodegradability. There was a problem that it did not reach 50 parts by weight, and if it exceeded 50 parts by weight, the crystallinity was low and softness was provided, causing a problem of lower tensile strength and hardness. As a result, biodegradable resin compositions containing an excessive amount of PHA-based resin were unsuitable for product molding. or productivity has decreased.

A chain extender is a molecule with at least two reactive groups that can bind polymer chains together, and can act as a component that affects the mechanical properties and biodegradability of biodegradable applications made of the biodegradable resin composition of the present invention. In other words, functional sites, such as the epoxy functional group of a chain extender, combine with the hydroxyl group (-OH) and/or carboxyl group (-COOH) group of a base resin such as PBAT or PLA to help connect the ends of the polymer, thereby increasing strength. In addition to this, the polymers produced in this way enable improved physical properties and processability through an increase in molecular weight, and also affect the biodegradability of biodegradable polymers.

The chain extender used in the present invention may be a functional compound containing at least one functional group such as epoxy, diol, diamine, triol, tetraol, polyamine, etc. In particular, two different types of chain extender can be used at the same time, and it has its technical characteristics. That is, through the examples and experimental examples described below, the present invention shows that when two types of chain extenders with different structures are used simultaneously, block (or graft) copolymers are formed, and compatibility between PLA and PHA phases is improved, thereby improving physical properties. This is because it has been confirmed that this happens.

In one embodiment, the epoxy functional compound used as a chain extender in the present invention is selected from the group consisting of di- and polyfunctional terminal epoxides or a group modified with ethylene oxide containing ethylene oxide and containing isocyanate at the other terminal. One or more epoxy-functional, styrene-acrylic polymers (e.g. ^JONCRYL ADR-4368 (BASF) or MP-40 (Kaneka), etc.), acrylic and/or polyolefin copolymers and glycidyl incorporated as side chains. oligomers containing groups (e.g. ^LOTADER® (Arkema), poly(ethylene-glycidyl methacrylate-co-methacrylate), etc.) and epoxidized oils (e.g. epoxidized soybean oil, olive oil, linseed oil) , palm oil, peanut oil, coconut oil, seaweed oil, cod liver oil or mixtures thereof, such as Merginat ^ㄾ ESBO (Hobum, Hamburg, Germany) and EDENOL ^ㄾ B 316 ( (Cognis, Düsseldorf, Germany). In particular, when using an epoxy functional compound as a chain extender in the present invention, 2 to 9 or less epoxy, etc. aligned at the ends of the molecular chain or side chain. Compounds containing can be used.

As another embodiment, functional compounds other than the epoxy functional compound used as a chain extender in the present invention include hexamethylene diisocyanate (HDI), hexanediol diglycidyl ether (1,6-hexanediol diglycidyl ether), Diacyl peroxide, peroxyketal, peroxyester, dialkyl peroxide, hydrogen peroxide, ethylene glycol, propylene glycol, 1,4-butanediol, glycerine trimethylolpropane, pentaelsritol, oxypropylated ethylene diamine, hexamethylenediamine, m-phenylenediamine, diethanolamine, triethanolamine, benzoyl peroxide, lauroyl peroxide, 1,3- or 1,4-bis(tert-butylperoxyisopropyl)benzene, n-butyl-4,4' -di(tert-butylperoxy)valerate, t-butyl peroxybenzoate, 1,1-di-t-butylperoxy-2,4-di-t-butylcyclohexane, 2,5-dimethyl- Any selected from the group consisting of 2,5-di-(t-butylperoxy)hexane, and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane. It could be one.

In the biodegradable resin composition of the present invention, the chain extender may be used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the biodegradable resin. In other words, if the content of the chain extender in the resin composition is less than 0.1 parts by weight, the absolute content is small and the chain extension rate is low, and if it exceeds 10 parts by weight, a trade-off phenomenon occurs and there is no significant change in physical properties, which only increases production costs. It may be desirable to use it within the above range because it may result in negative results.

If necessary, the present invention may further include a filler. The filler used in the present invention is used for the purpose of a conventional filler (i.e., serves as a filler between polymer chains to improve the viscosity characteristics of the resin required in the molding process). Unlike its function (or improving the mechanical properties of the final molded product), it acts as a component that contributes to the biodegradability of biodegradable resin products made of biodegradable resin compositions.

Among the characteristics of fillers, factors that affect this excellent biodegradability may include the type, size, and surface treatment of the filler.

Fillers that can be used in the present invention are not all known fillers, but include barite, calcium carbonate, graphite, native copper, sulfur, quartz, orthosite, plagioclase, biotite, olivine, hornblende, calcite, malachite, aragonite, phosphate, apatite, Hard apatite, magnetite, hematite, chalcopyrite, pyrite, galena, fluorite, bentonite, kaolin, talc, talcum powder, chalk powder, eggshell, gypsum, carbon black, iron oxide, dolomite, calcium chloride, barium sulfate, silicon dioxide, wollastonite, silicate, It may be one or more selected from the group consisting of mica, diamond, silica, silicon, talc, zeolite, starch, and glass fiber. In particular, if the filler used in the present invention has the characteristics of a standard mixing amount of 0.01 to 100%, an expansion rate of 0.01 to 3, and a condensation expansion rate of 0.001 to 3, it can contribute to ensuring excellent biodegradability.

Looking at how the size of the filler affects biodegradability, in biodegradable resin application products made of the biodegradable resin composition of the present invention, the filler is filled between biodegradable polymer chains, so as the size of the filler increases, the distance between layers increases, thereby improving biodegradability. It can be seen that as the size becomes smaller, biodegradability decreases because it does not affect the interlayer distance. Accordingly, the size of the filler may be 1 nm to 30 μm, considering the action and compatibility of the filler. If the size of the filler is less than 1 nm, dispersion is difficult and economic feasibility is low. If it exceeds 30 μm, there may be problems with poor compatibility, quality, and physical properties in film molding of 30 μm or less.

In addition, when the surface of the filler is treated, it penetrates more smoothly between polymer chains and improves dispersibility and compatibility, thereby improving physical properties and facilitating biodegradation.

In the biodegradable resin composition of the present invention, the filler may be included in an amount of 0.1 to 60 parts by weight based on the total weight of the biodegradable resin composition. If the content of the filler is less than 0.1 part by weight, there is a problem that the low content does not serve as a nucleating agent, and 60 If the weight part is exceeded, there may be a problem that molding is difficult due to a lack of base matrix due to excessive filler injection.

As such, the decomposition rate of biodegradable resin application products made of the biodegradable resin composition of the present invention is influenced to some extent by the content of the chain extender, but the type and content of repeating units contained in the PHA-based resin and the type of base resin. and content, and the chain extender affects the physical properties of biodegradable resin application products. In particular, when two different types of chain extenders are used simultaneously, the final product has excellent physical properties and product quality. Biodegradable resin application products can be produced.

Next, the biodegradable resin application product of the present invention is composed of a biodegradable resin composition having any of the above-described compositions, and is not limited as long as it is a product requiring biodegradability, but one embodiment includes disposable containers, packaging vinyl, and cold storage. It may be one or more selected from the group consisting of a cup and a tray.

In addition, the biodegradable resin application product of the present invention has a tensile strength of more than 30 MPa and a biodegradability of more than 90% compared to the standard material, and has excellent properties that can be commercialized.

Next, the method for manufacturing biodegradable resin applied products of the present invention includes the steps of putting the biodegradable resin composition of the above-described composition uniformly mixed in an extrusion molding machine, melting it, and extruding it to form a thread shape; Cutting the manufactured thread shape to produce pellets; and manufacturing a biodegradable resin application product by putting the pellets into a molder or extruder. Here, melting of the biodegradable resin composition can be performed at 100 to 230°C, and dehumidifying drying can be performed at 40 to 100°C.

Conventionally, in order to manufacture biodegradable resin applied products, there was a disadvantage that new equipment had to be introduced or modified due to differences in screw type and extrusion line length compared to existing molding machines. However, the method for manufacturing biodegradable resin applied products of the present invention According to the results, by using a biodegradable resin composition having the above-described composition, it was possible to secure production speed and quality even by using existing equipment.

Examples 1 to 9

Biodegradable resin compositions 1 to 9 were prepared by uniformly mixing the ingredients shown in Table 1 below at the indicated amounts using a Henschel mixer.

Composition ingredients Example One 2 3 4 5 6 7 8 9 PLA 100 100 100 100 100 100 100 100 100 PHAs 40 40 0.1 50 40 40 40 40 20 Chain extender 1 0.3 0 0.3 0.3 0.3 9.7 0.3 5 0.3 Chain extender 2 0 0.3 0.3 0.3 0.3 0.3 9.7 5 0.3 Filler (CaCO ₃ ) 0 0 0 0 0 0 0 0 45

Here, the base resin PLA is a product of Nature Works (4032D, MI 7g/10min, @210℃). PHA-based resin is a product of CJ Co., Ltd. (MI 4g/10min, @190℃). Chain extender 1 is a product of BASF (JONCRYL ADR 4370S), chain extender 2 is a product of TOKYO Chemical (hexamethylene diisocyanate, HDI), and filler is a product of Omya (CaCO ₃ ).

Examples 10 to 18

The biodegradable resin compositions 1 to 9 obtained in Examples 1 to 9 were melted and extruded using a twin-screw extruder from Steer to produce thread shapes, and then the thread shapes were cut with a pelletizer to produce pellets. Afterwards, the pellets prepared with biodegradable resin compositions 1 to 9 were dehumidified and dried at 60°C for 8 hours, and then cold cups 1 to 9, which were biodegradable resin application products, were manufactured using a sheet molding machine. Here, product molding was performed at a processing temperature of 100 to 230°C, especially 180°C.

Comparative Examples 1 to 7

Comparative Example Compositions 1 to 7 were prepared by uniformly mixing the ingredients shown in Table 2 below in the indicated amounts.

Composition ingredients Comparative example One 2 3 4 5 6 7 PLA 100 100 100 100 100 100 100 PHAs 200 0 80 40 40 40 20 Chain extender 1 0.3 0.2 0.3 0 15 0.3 0.3 Chain extender 2 0.3 0.1 0.3 0 0.3 15 0.3 filler
(CaCO ₃ ) 80

Here, the base resin PLA is a product of Nature Works (4032D, MI 7g/10min, @210℃). PHA-based resin is a product of CJ Co., Ltd. (MI 4g/10min, @190℃). Chain extender 1 is a product of BASF (JONCRYL ADR 4370S), chain extender 2 is a product of TOKYO Chemical (hexamethylene diisocyanate, HDI), and filler is a product of Omya (CaCO ₃ ).

Comparative Examples 8 to 14

Comparative Example Products 1 to 7 were prepared by using Comparative Example Compositions 1 to 7 obtained in Comparative Examples 1 to 7 in the same manner as Example 9.

Experiment example

For biodegradable resin application products 1 to 9 manufactured in Examples 10 to 18 and Comparative Example products 1 to 7 manufactured in Comparative Examples 8 to 14, specimens were prepared as follows to measure physical properties, and the results are shown in Table 3 shown in The manufactured product was aged at room temperature for 24 hours, then a specimen was manufactured and the physical properties were measured.

1. Tensile strength & elongation

The measurement specimen was manufactured in accordance with KS M 3001: 2001 Type 1, and was measured at a measurement speed of 500 mm/min. The measuring equipment was measured based on KS M 3001:2001 by attaching a 5kN load cell to the Instron 3369 model.

2. Biodegradable

The biodegradability indicates the rate of decomposition compared to a standard material (e.g., cellulose) during the same period, and the Ministry of Environment of the Republic of Korea defines a material as biodegradable when the biodegradability is 90% or more compared to the standard material. Specifically, the decomposition degree measured according to the EL 724 standard is more than 90%.

O: 90% or more

X: less than 90%

3. Flexibility

When force is applied to the product as a whole, the product has resilience without whitening.

O: 90% or more

X: less than 90%

4. Formability

The molding type was confirmed with a blow film molding machine and a casting (T-die) film molding machine. The molding temperature is 190°C, and the thickness is about 50 microns. If it has a good quality surface, it is marked as O, and if it does not, it is marked as X.

From Table 3, the biodegradable resin products 1 to 9 obtained in Examples 10 to 18 not only have a tensile strength of 30 MPa or more and a biodegradability of 90% or more compared to the standard material, but are also suitable for use as shown in Figure 1. It has excellent moldability, and as a result of testing biodegradability according to the above-mentioned method, it can be seen that all of them are easily biodegradable even in various soil environments, so the decomposition time can be adjusted by adjusting the type and content of the components depending on the use.

On the other hand, Comparative Example Composition 1 had a problem in that it was impossible to mold because the absolute content of PLA was small compared to the PHA content. Comparative Example Product 2 prepared with Comparative Example Composition 2 does not contain PHA, so there is a problem that a somewhat high temperature is required for biodegradation and the decomposition time takes a rather long time, and the product has low flexibility and is not marketable. Could know. Comparative Example Product 3 prepared with Comparative Example Composition 3 had a problem in that it contained an excessive amount of PHA, making molding impossible. Comparative Example Product 4 prepared with Comparative Example Composition 4 did not contain a chain extender, so when extruded at the above-mentioned high temperature, the biodegradable resin partially decomposed and the final product suffered from problems such as unevenness or surface roughness. There was a problem of poor marketability. It can be confirmed that Comparative Example Product 5 and Comparative Example Product 6 manufactured with Comparative Example Composition 5 and Comparative Example Composition 6 are not marketable due to poor surface, decomposition, and reduced flexibility of the product due to excessive addition of chain extender 1 or 2. there was. Comparative Example Product 7 manufactured with Comparative Example Composition 7 had a problem in that molding was impossible due to excessive addition of CaCO ₃ .

Although the present invention has been illustrated and described with preferred embodiments as discussed above, it is not limited to the above-described embodiments and is intended to be used by those skilled in the art without departing from the spirit of the invention. Various changes and modifications will be possible.

Claims (15)

30 to 50 parts by weight of polyhydroxyalkanoate (PHA)-based resin per 100 parts by weight of base resin containing polylactic acid (PLA)-based resin; and
Contains one or more chain extenders;
The chain extender includes at least two types of chain extenders having different structures, and at least one of the chain extenders is an epoxy functional compound consisting of a di- or polyfunctional terminal epoxide, based on the total weight of the resin composition. A biodegradable resin composition characterized in that it contains 0.1 to 0.5% by weight.
According to claim 1,
The base resin is polybutylene adipate-co-terephthalate (PBAT), polycaprolactone, polyglycolic acid, polybutylene succinate (PBS), polybutylene succinate adipate (Poly (butylene succinate-co-butylene adipate, PBSA), polybutylene succinate-terephthalate (PBST), polybutylene adipate, polyhydroxy butyrate (PHB), poly-3-hydroxyvalerate ( poly-3-hydroxyvalerate, PBV), poly hydroxybutyrate valerate (PHBV), poly-(3-hydroxybutyrate-co-3- hydroxyvalerate) and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (poly-(3-hydroxybutyrate -co-3-hydroxyhexanoate). A biodegradable resin composition.
According to claim 1,
The PHA-based resin is a biodegradable resin composition characterized in that it contains two or more different repeating units in the polymer chain, and the different repeating units are irregularly distributed.
According to claim 3,
The repeating unit is 2-hydroxybutyrate, lactic acid, glycolic acid, 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvalerate (3-HV) , 3-hydroxyhexanoate (3-HH), 3-hydroxyheptanoate (3-HHep), 3-hydroxyoctanoate (3-HO), 3-hydroxynonanoate (3- HN), 3-hydroxydecanoate (3-HD), 3-hydroxydodecanoate (3-HDd), 4-hydroxybutyrate (4-HB), 4-hydroxyvalerate (4-HV) ), a biodegradable resin composition characterized in that it is at least one selected from the group consisting of 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate (6-HH).
According to claim 1,
The PHA-based resin has a glass transition temperature (Tg) of -45°C to 80°C, crystallization temperature (Tc) of 70 to 120°C, melting temperature (Tm) of 100 to 170°C, and molecular weight of 10,000 g/mol to 1,200,000 g. A biodegradable resin composition characterized in that /mol.
delete According to claim 1,
The epoxy functional compound is a biodegradable resin composition, characterized in that it is a compound containing 2 to 9 or less epoxy groups aligned at the ends of the molecular chain or side chain.
According to claim 1,
At least one of the chain extenders is hexamethylene diisocyanate (HDI), hexanediol diglycidyl ether (1,6-hexanediol diglycidyl ether), diacyl peroxide, peroxy ketal, peroxy ester, di peroxide Alkyl, hydrogen peroxide, ethylene glycol, propylene glycol, 1,4-butanediol, glycerine trimethylolpropane, pentaelsritol, oxypropylated ethylene diamine, hexamethylenediamine, m-phenylenediamine, diethanolamine, triethanolamine, peroxide Benzoyl, lauroyl peroxide, 1,3- or 1,4-bis(tert-butylperoxyisopropyl)benzene, n-butyl-4,4'-di(tert-butylperoxy)valerate, t- Butyl peroxybenzoate, 1,1-di-t-butylperoxy-2,4-di-t-butylcyclohexane, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane , and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane.
According to claim 1,
Graphite, native copper, sulfur, quartz, orthosite, plagioclase, biotite, olivine, hornblende, calcite, malachite, aragonite, phosphate, apatite, apatite, magnetite, hematite, barite, chalcopyrite, pyrite, galena, fluorite, bentonite, kaolinite. , talc, talcum powder, calcium carbonate, chalk powder, eggshell, gypsum, carbon black, iron oxide, dolomite, calcium chloride, barium sulfate, silicon dioxide, wollastonite, silicate, mica, emery, silica, silicon, talc, zeolite, starch and glass. A biodegradable resin composition further comprising 0.1 to 60% by weight of at least one filler selected from the group consisting of fibers, based on the total weight of the biodegradable resin composition.
According to any one of claims 1 to 5 or 7 to 9,
One or more additives selected from the group consisting of antioxidants, compatibilizers, weighting agents, nucleating agents, melt strength increasers, polymerization initiators, and slip agents are added in an amount of 0.1% to 30% by weight based on the total weight of the biodegradable resin composition. A biodegradable resin composition comprising:
A biodegradable resin application product comprising the biodegradable resin composition of any one of claims 1 to 5 and 7 to 9.
According to claim 11,
The biodegradable resin application product is characterized by a tensile strength of 30 MPa or more and a biodegradability of 90% or more compared to standard materials.
According to claim 11,
The applied product is a biodegradable resin applied product characterized in that it is one or more selected from the group consisting of cold cups, buttons, golf tees, disposable containers, packaging vinyl, trays, and sheets. Putting the uniformly mixed biodegradable resin composition of any one of claims 1 to 5 and 7 to 9 into an extrusion molding machine, melting it, and extruding it to form a thread shape;
Cutting the manufactured thread shape to produce pellets; and
A method of manufacturing a biodegradable resin application product comprising: manufacturing a biodegradable resin application product by putting the pellets into a molder or extruder.
According to claim 14,
The molding machine or extruder is any one selected from the group consisting of an extrusion molding machine, injection molding machine, blow molding machine, pressure molding machine, calendering, rotation molding, casting, T-die extruder, blown film extruder, and thermoforming machine. Manufacturing method for biodegradable resin applied products.