KR102599541B1 - Composition for mulching film with improved biodegradability in soil conditions after crop cultivation, manufacturing method thereof, and mulching film prepared therefrom - Google Patents
Composition for mulching film with improved biodegradability in soil conditions after crop cultivation, manufacturing method thereof, and mulching film prepared therefrom Download PDFInfo
- Publication number
- KR102599541B1 KR102599541B1 KR1020220116048A KR20220116048A KR102599541B1 KR 102599541 B1 KR102599541 B1 KR 102599541B1 KR 1020220116048 A KR1020220116048 A KR 1020220116048A KR 20220116048 A KR20220116048 A KR 20220116048A KR 102599541 B1 KR102599541 B1 KR 102599541B1
- Authority
- KR
- South Korea
- Prior art keywords
- mulching film
- composition
- modified thermoplastic
- thermoplastic starch
- biodegradable
- Prior art date
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Classifications
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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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0033—Additives activating the degradation of the macromolecular compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
- C08K5/1539—Cyclic anhydrides
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 생분해성 고분자 수지, 변성 열가소성 전분, CaCO3 및 무수말레산-그래프트(MAH-g)를 포함하는 멀칭필름용 조성물, 생분해성 멀칭 필름의 제조방법 및 이에 따라 제조한 생분해성 멀칭필름을 제공한다. 본 발명에 따르면 생분해성 고분자 수지에 변성 열가소성 전분 및 생분해촉진 첨가제를 적정비율로 혼합함으로써 작물재배후 토양조건에서 생분해성이 향상된 농업용 멀칭필름을 제조함으로써 멀칭필름의 수거, 회수 및 처리에 따른 사회적 비용을 절감시킬 수 있으며, 농촌 인력의 고령화, 농업의 기피 풍조 및 취농 인구의 감소로 인한 열악한 농업 환경의 개선과 생산성 향상성을 높일 수 있다.The present invention provides a composition for a mulching film containing a biodegradable polymer resin, modified thermoplastic starch, CaCO 3 and maleic anhydride-graft (MAH-g), a method for producing a biodegradable mulching film, and a biodegradable mulching film manufactured thereby. to provide. According to the present invention, an agricultural mulching film with improved biodegradability under soil conditions after crop cultivation is manufactured by mixing biodegradable polymer resin with modified thermoplastic starch and biodegradation-promoting additives in an appropriate ratio, thereby producing social costs resulting from collection, recovery, and processing of the mulching film. can be reduced, and the poor agricultural environment caused by the aging of the rural workforce, the trend of avoiding agriculture, and the decline in the farming population can be improved and productivity can be improved.
Description
본 발명은 작물재배후 토양조건에서 생분해성이 향상된 농업용 멀칭필름 컴파운드 및 이로부터 제조되는 생분해성 멀칭 필름에 관한 것이다.The present invention relates to an agricultural mulching film compound with improved biodegradability in soil conditions after crop cultivation and a biodegradable mulching film manufactured therefrom.
최근 농업인구 고령화에 따라 기존 멀칭필름을 설치 및 수거하는 방법으로는 노동력이 부족한 현황이다. 따라서, 농업용 폐비닐을 따로 수거할 필요가 없이 미생물에 의해 생분해되는 농업용 멀칭필름수요가 증가하고 있다. 그러나 기존 생분해성 멀칭필름의 경우 농지토양조건에서 생분해가 매우 느리게 진행되어 토양속에 잔류하는 문제가 발생해왔다. Recently, as the agricultural population has aged, there is a shortage of labor for installing and collecting existing mulching films. Therefore, the demand for agricultural mulching film that is biodegradable by microorganisms without the need to separately collect agricultural waste vinyl is increasing. However, in the case of existing biodegradable mulching films, biodegradation progresses very slowly under agricultural soil conditions, causing problems of remaining in the soil.
이에 특허출원 제10-2018-0129292호는 생분해 속도제어가 가능한 멀칭 필름용 수지 조성물 및 이를 이용한 생분해성 멀칭 필름을 개시한다. 상기 기술은 금속(Fe) 산화촉진제를 이용한 분해촉진제품으로 물리적분해(광분해에 의한 쪼개짐)를 촉진시키지만, 화학적분해(물, 이산화탄소 등에 의한 분해)를 촉진시키지 않고, 물리적으로 분해된 멀칭필름은 토양속에 일정기간 잔류하여 오히려 식물생장에 저해요소가 될 수 있다.Accordingly, Patent Application No. 10-2018-0129292 discloses a resin composition for mulching film capable of controlling the rate of biodegradation and a biodegradable mulching film using the same. The above technology is a decomposition promotion product using a metal (Fe) oxidation accelerator. It promotes physical decomposition (splitting by photodecomposition), but does not promote chemical decomposition (decomposition by water, carbon dioxide, etc.), and the physically decomposed mulching film is stored in soil. It may remain in the plant for a certain period of time and become an inhibitor to plant growth.
또한 특허출원 제10-2019-0100459호는 생분해성 방출 조절 비료, 이를 포함하는 생분해성 멀칭필름 및 그 제조방법을 개시한다. 상기 기술은 완효성비료를 첨가하여 생분해성이 향상시키고 생분해성이 KS M 3100-1 산업용퇴비화조건(58℃)에서 시험되어 실제 토양조건과는 거리가 있다.Additionally, Patent Application No. 10-2019-0100459 discloses a biodegradable release-controlled fertilizer, a biodegradable mulching film containing the same, and a method for manufacturing the same. The above technology improves biodegradability by adding slow-release fertilizer, and biodegradability is tested under KS M 3100-1 industrial composting conditions (58°C), which is far from actual soil conditions.
이에 본 발명에서는 실제 토양속에서 생분해성이 향상된 멀칭필름용 조성물, 이의 제조방법 및 이로부터 제조한 멀칭필름을 제공하고자 한다.Accordingly, the present invention seeks to provide a composition for a mulching film with improved biodegradability in actual soil, a manufacturing method thereof, and a mulching film manufactured therefrom.
상기 목적을 달성하기 위하여, 본 발명은 생분해성 고분자 수지, 변성 열가소성 전분, CaCO3 및 글리세린 또는 무수말레산-그래프트(MAH-g)를 포함하는 멀칭필름용 조성물을 제공한다.In order to achieve the above object, the present invention provides a composition for a mulching film containing a biodegradable polymer resin, modified thermoplastic starch, CaCO 3 and glycerin or maleic anhydride-graft (MAH-g).
또한, 본 발명은 전분분말을 가소화처리하여 변성 열가소성 전분을 제조하는 단계; 락트산 및 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)를 포함하는 락트산 마스터배치를 제조하는 단계; 상기 변성 열가소성 전분, 생분해성 고분자 수지, CaCO3, 무수말레산-그래프트(MAH-g) 및 락트산 마스터배치를 혼합, 용융 및 압출하여 생분해성 멀칭 컴파운드를 제조하는 단계; 및 상기 생분해성 멀칭 컴파운드를 블로운 필름 압출하여 생분해성 멀칭 필름을 제조하는 단계;를 포함하는 생분해성 멀칭 필름의 제조방법을 제공한다.In addition, the present invention includes the steps of plasticizing starch powder to produce modified thermoplastic starch; Preparing a lactic acid masterbatch comprising lactic acid and polybutylene adipate terephthalate (PBAT); Mixing, melting, and extruding the modified thermoplastic starch, biodegradable polymer resin, CaCO 3 , maleic anhydride-graft (MAH-g), and lactic acid masterbatch to prepare a biodegradable mulching compound; and manufacturing a biodegradable mulching film by extruding the biodegradable mulching compound into a blown film.
또한, 본 발명은 상기 제조방법에 따라 제조한 생분해성 멀칭필름을 제공한다.Additionally, the present invention provides a biodegradable mulching film manufactured according to the above manufacturing method.
본 발명에 따른 멀칭필름용 조성물은 생분해성 고분자 수지에 변성 열가소성 전분 및 생분해촉진 첨가제를 적정비율로 혼합함으로써 생분해성이 향상될 수 있다.The biodegradability of the composition for mulching film according to the present invention can be improved by mixing biodegradable polymer resin with modified thermoplastic starch and biodegradation-promoting additives in an appropriate ratio.
본 발명에 따르면 작물재배후 토양조건에서 생분해성이 향상된 농업용 멀칭필름을 제조함으로써 멀칭필름의 수거, 회수 및 처리에 따른 사회적 비용을 절감시킬 수 있으며, 농촌 인력의 고령화, 농업의 기피 풍조 및 취농 인구의 감소로 인한 열악한 농업 환경의 개선과 생산성 향상성을 높일 수 있다. 이 밖에도 농지의 황폐화를 예방할 수 있고, 농촌 인구의 고령화에 따른 노동력 부족 해소와 인건비 절감을 통한 농촌의 경제성을 확보할 수 있는 이점이 있다.According to the present invention, by manufacturing an agricultural mulching film with improved biodegradability in soil conditions after crop cultivation, it is possible to reduce social costs due to collection, recovery, and processing of mulching film, and to reduce the aging of the rural workforce, the trend of avoiding agriculture, and the population taking up farming. The reduction of can improve poor agricultural environments and increase productivity. In addition, it has the advantage of preventing the deterioration of farmland, resolving the labor shortage due to the aging of the rural population, and securing the economic feasibility of rural areas by reducing labor costs.
본 발명의 효과는 이상에서 언급한 효과로 한정되지 않는다. 본 발명의 효과는 이하의 설명에서 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 할 것이다.The effects of the present invention are not limited to the effects mentioned above. The effects of the present invention should be understood to include all effects that can be inferred from the following description.
도 1은 본 발명에 따른 변성 열가소성 전분(TPS) 나노입자가 분산된 멀칭필름을 모식적으로 나타낸 것이다.
도 2는 비교예에 따른 변성 열가소성 전분(TPS) 마이크로입자가 분산된 멀칭필름을 모식적으로 나타낸 것이다.
도 3은 비교예에 따른 멀칭필름에 분산된 변성 열가소성 전분(TPS) 마이크로입자를 전자현미경으로 촬영한 사진이다.
도 4는 본 발명에 따른 멀칭필름에 분산된 변성 열가소성 전분(TPS) 나노입자를 전자현미경으로 촬영한 사진이다.
도 5는 본 발명에 따른 생분해성 멀칭필름 제조 과정의 흐름도이다.Figure 1 schematically shows a mulching film in which modified thermoplastic starch (TPS) nanoparticles are dispersed according to the present invention.
Figure 2 schematically shows a mulching film in which modified thermoplastic starch (TPS) microparticles are dispersed according to a comparative example.
Figure 3 is a photograph taken with an electron microscope of modified thermoplastic starch (TPS) microparticles dispersed in a mulching film according to a comparative example.
Figure 4 is a photograph taken with an electron microscope of modified thermoplastic starch (TPS) nanoparticles dispersed in a mulching film according to the present invention.
Figure 5 is a flow chart of the biodegradable mulching film manufacturing process according to the present invention.
이하, 첨부한 도면을 참고로 하여 본 발명의 실시예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. Hereinafter, with reference to the attached drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention.
본 발명은 생분해성 고분자 수지, 변성 열가소성 전분, CaCO3, 및 글리세린 또는 무수말레산-그래프트(MAH-g)를 포함하는 멀칭필름용 조성물을 제공한다.The present invention provides a composition for a mulching film containing a biodegradable polymer resin, modified thermoplastic starch, CaCO 3 , and glycerin or maleic anhydride-graft (MAH-g).
본 발명의 일 실시예에 따르면, 상기 조성물은 조성물 전체 중량에 대하여 생분해성 고분자 수지 50 내지 80 중량%; 변성 열가소성 전분 5 내지 15 중량%; CaCO3 15 내지 25 중량%; 및 글리세린 5 내지 20 중량 또는 무수말레산-그래프트(MAH-g) 2 내지 10 중량%를 포함할 수 있다.According to one embodiment of the present invention, the composition includes 50 to 80% by weight of a biodegradable polymer resin based on the total weight of the composition; 5 to 15% by weight of modified thermoplastic starch; CaCO 3 15 to 25% by weight; And it may include 5 to 20% by weight of glycerin or 2 to 10% by weight of maleic anhydride-graft (MAH-g).
<생분해성 고분자 수지><Biodegradable polymer resin>
본 발명의 멀칭필름용 조성물은 생분해성 고분자 수지를 포함한다.The composition for mulching film of the present invention includes a biodegradable polymer resin.
상기 생분해성 고분자 수지의 함량은 상기 조성물 전체 중량에 대하여 50 내지 80 중량%, 바람직하게는 55~75 중량%, 보다 바람직하게는 60~70 중량%, 가장 바람직하게는 65 중량%일 수 있다. 상기 생분해성 고분자 수지의 함량이 50 중량% 미만이면 고분자 수지가 급격하게 분해되어 원하는 기간 동안 필름의 기능을 유지하지 못할 수 있다. 반대로 상기 생분해성 고분자 수지의 함량이 80 중량% 초과이면 생분해 속도가 느려져 작물 수확 후 로터리 작업에 문제가 생길 수 있다. The content of the biodegradable polymer resin may be 50 to 80% by weight, preferably 55 to 75% by weight, more preferably 60 to 70% by weight, and most preferably 65% by weight, based on the total weight of the composition. If the content of the biodegradable polymer resin is less than 50% by weight, the polymer resin may decompose rapidly and the function of the film may not be maintained for the desired period. Conversely, if the content of the biodegradable polymer resin exceeds 80% by weight, the biodegradation rate is slowed, which may cause problems in rotary work after crop harvesting.
본 발명의 일 실시예에 따르면, 상기 생분해성 고분자 수지는 폴리부틸렌 아디페이트 테레프탈레이트(PBAT), 폴리부틸렌숙시네이트(PBS), 폴리부틸렌아디페이트(PBA), 폴리부틸렌숙시네이트-아디페이트(PBSA), 폴리부틸렌숙시네이트-테레프탈레이트(PBST) 리히드록시부틸레이트-발레레이트(PHBV), 폴리카프로락톤(PCL) 및 폴리락트산(PLA)으로 이루어진 군 중에서 선택된 1종 이상의 생분해성 폴리에스터일 수 있다.According to one embodiment of the present invention, the biodegradable polymer resin is polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate- Biodegradable at least one selected from the group consisting of adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), and polylactic acid (PLA) It may be polyester.
본 발명의 일 실시예에 따르면, 상기 생분해성 고분자 수지는 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리락트산(PLA)가 1 : 0.1~0.4의 중량비, 바람직하게는 1 : 0.20~0.25의 중량비로 혼합된 것일 수 있다.According to one embodiment of the present invention, the biodegradable polymer resin contains polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) in a weight ratio of 1:0.1 to 0.4, preferably 1:0.20 to 0.25. It may be a mixture of .
본 발명에 있어서, 폴리락트산(PLA)가 상기 범위 미만으로 사용될 경우에 원하는 물성을 얻기 어려우며, 상기 범위를 초과할 경우에 복합수지의 가공성이 저하된다.In the present invention, when polylactic acid (PLA) is used in an amount less than the above range, it is difficult to obtain the desired physical properties, and if it exceeds the above range, the processability of the composite resin deteriorates.
<변성 열가소성 전분><Modified thermoplastic starch>
본 발명의 멀칭필름용 조성물은 생분해성 고분자 수지의 가공성을 높이고, 분해속도를 빠르게 하기 위해 변성 열가소성 전분(TPS)을 포함한다. The composition for mulching film of the present invention includes modified thermoplastic starch (TPS) to increase the processability of the biodegradable polymer resin and speed up the decomposition rate.
본 발명에서 전분은 옥수수전분, 감자전분, 고구마전분, 타피오카전분, 쌀전분, 밀전분, 이들의 변성전분류 또는 이들의 혼합물에서 선택될 수 있다. 전분은 생분해성이 뛰어나긴 하지만 수분량에 따라 물성변화가 심하고 열가소성이 적어 사용에 제약을 받으므로, 이러한 전분의 문제점을 극복하기 위하여 전분에 치환체를 도입하여 함수율을 낮추는 동시에 열가소성을 부여한 변성 전분을 사용한다.In the present invention, the starch may be selected from corn starch, potato starch, sweet potato starch, tapioca starch, rice starch, wheat starch, modified starches thereof, or mixtures thereof. Although starch has excellent biodegradability, its physical properties change significantly depending on the moisture content and its use is limited due to its low thermoplasticity. To overcome these problems with starch, modified starch is used to lower the moisture content by introducing substituents into starch and at the same time give thermoplasticity. do.
본 발명의 일 실시예에 따르면, 변성 열가소성 전분의 함량은 조성물 전체 중량에 대해서 5 내지 15 중량%인 것이 바람직하다. 변성 열가소성 전분의 함량이 15중량%를 초과하게 되면, 생분해성 고분자 수지와의 혼련성이 원활하지 않게 되어 필름 성형에 문제가 발생할 수 있고, 필름 성형 이후에도 물성의 저하 및 필름의 급격한 분해로 인하여, 원하는 기간 동안 필름의 기능을 유지하지 못할 수 있으므로 바람직하자 않다. 반면, 그 함량이 5중량%보다 적으면 제조되는 필림이 과도하게 연신되어 압출 성형이 불가해질 수 있다. 또한, 피복 후, 분해속도가 느려져 다음 파종시까지 필름의 분해가 이루이지지 않을 수 있으므로 이 역시 바람직하지 않다. According to one embodiment of the present invention, the content of modified thermoplastic starch is preferably 5 to 15% by weight based on the total weight of the composition. If the content of modified thermoplastic starch exceeds 15% by weight, the mixing ability with the biodegradable polymer resin may not be smooth, which may cause problems in film molding. Even after film molding, due to a decrease in physical properties and rapid decomposition of the film, This is not desirable because it may not maintain the function of the film for the desired period. On the other hand, if the content is less than 5% by weight, the produced film may be stretched excessively, making extrusion molding impossible. In addition, after coating, the decomposition rate becomes slow and decomposition of the film may not be achieved until the next sowing, which is also undesirable.
본 발명에서 사용되는 전분은 아밀로오스 및 아밀로펙틴으로 이루어진 천연의 중합체일 수 있다. 아밀로오스는 주로 100,000 내지 500,000 범위의 분자량을 갖는 선형 중합체인 한편, 아밀로펙틴은 수백만에 이르는 분자량을 갖는 고도로 분지화된 중합체일 수 있다. The starch used in the present invention may be a natural polymer composed of amylose and amylopectin. Amylose is primarily a linear polymer with a molecular weight ranging from 100,000 to 500,000, while amylopectin can be a highly branched polymer with a molecular weight in the millions.
본 발명의 일 실시예에 따르면, 상기 변성 열가소성 전분은 효소적 변성 열가소성 전분 및 화학적 변성 열가소성 전분으로 이루어진 군으로부터 선택되는 1종 이상의 전분 유도체일 수 있다.According to one embodiment of the present invention, the modified thermoplastic starch may be one or more starch derivatives selected from the group consisting of enzymatically modified thermoplastic starch and chemically modified thermoplastic starch.
상기 변성 열가소성 전분은 화학적 변성 열가소성 전분일 수 있다. 일례로 전분에 용융-가공성을 부여하기 위해 가소제를 사용할 수 있다. 전분은, 통상적으로, 과립의 내부에 더욱 수용성인 아밀로오스와 아밀로펙틴 사슬을 감싸는 피복 또는 외부막을 갖는 과립의 형태로 존재한다. 가열시, 가소제가 외부막을 연화 및 침투하여 내부 전분 사슬로 하여금 물을 흡수하여 팽윤되게 할 수 있다. 하나의 바람직한 예로서, 상기 가소제는 포도당, 자당, 과당, 라피노오스, 말토 덱스테로오스, 갈락토오스, 크실로오스, 말토오스, 유당, 만노오스 및 에리트로오스 등의 당류; 에리트리톨, 크실리톨, 말리톨, 만니톨, 글리세롤 및 소르비톨 등의 당 알코올류; 글리세린, 에틸렌 글리콜, 프로필렌 글리콜, 디프로필렌 글리콜, 부틸렌 글리콜 및 헥산 트리올 등의 폴리올류 등과 같은 다가 알코올 가소제를 포함할 수 있다.The modified thermoplastic starch may be chemically modified thermoplastic starch. For example, plasticizers can be used to impart melt-processability to starch. Starch typically exists in the form of granules with a sheath or outer membrane surrounding the more water-soluble amylose and amylopectin chains on the interior of the granules. When heated, the plasticizer can soften and penetrate the outer membrane, causing the inner starch chains to absorb water and swell. As a preferred example, the plasticizer includes sugars such as glucose, sucrose, fructose, raffinose, maltodexterose, galactose, xylose, maltose, lactose, mannose, and erythrose; sugar alcohols such as erythritol, xylitol, maltol, mannitol, glycerol, and sorbitol; It may contain polyhydric alcohol plasticizers such as polyols such as glycerin, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and hexane triol.
상기 변성 열가소성 전분은 효소적 변성 열가소성 전분일 수 있다. 효소적 변성 열가소성 전분은 화학적 첨가제가 아닌 효소를 사용하여 전분에 용융-가공성을 부여한 것이다. 일례로, 이소-아밀라아제 효소에 의해 아밀로펙틴구조(포도당고리 30개 내지 40개)의 전분을 아밀로오스(포도당고리 8개 내지 12개) 형태로 변환하여 변성된 아밀로오스 구조에 가공성을 부여하기 위해 아밀로수크레이스 효소를 첨가하여 아밀로오스 전분구조 말단에 지방산을 결합한 것일 수 있다.The modified thermoplastic starch may be enzymatically modified thermoplastic starch. Enzymatically modified thermoplastic starch is one that imparts melt-processability to starch using enzymes rather than chemical additives. For example, starch in the amylopectin structure (30 to 40 glucose rings) is converted to amylose (8 to 12 glucose rings) by iso-amylase enzyme to give processability to the modified amylose structure. It may be that fatty acid is bound to the end of the amylose starch structure by adding lace enzyme.
상기 변성 열가소성 전분은 300 nm 내지 500 nm의 평균 지름[d(0.5)]을 가지는 구형 나노입자일 수 있다.The modified thermoplastic starch may be spherical nanoparticles with an average diameter [d(0.5)] of 300 nm to 500 nm.
상기 평균 지름[d(0.5)]은 전체 입도 분포에서 50%일때의 크기, 중위수(Median)을 나타낸다.The average diameter [d(0.5)] represents the size and median at 50% of the entire particle size distribution.
상기 변성 열가소성 전분은 0.8 내지 1.3의 분포도(Span)를 가지는 균일한 입자일 수 있다.The modified thermoplastic starch may be uniform particles having a span of 0.8 to 1.3.
상기 분포도(Span)는 입자의 분포폭으로 {d(0.9)-d(0.1)}/d(0.5)으로 계산되며, 분포폭이 좁을수록 분포도는 작다.The distribution (Span) is the distribution width of the particles and is calculated as {d(0.9)-d(0.1)}/d(0.5). The narrower the distribution width, the smaller the distribution.
본 발명의 멀칭필름용 조성물은 필름가공시 블로킹현상 및 인장강도 저하를 방지 하기 위해 CaCO3를 포함한다.The composition for mulching film of the present invention contains CaCO 3 to prevent blocking phenomenon and decrease in tensile strength during film processing.
본 발명의 일 실시예에 따르면, CaCO3의 함량은 조성물 전체 중량에 대해서 15 내지 25 중량%인 것이 바람직하다. According to one embodiment of the present invention, the content of CaCO 3 is preferably 15 to 25% by weight based on the total weight of the composition.
본 발명의 멀칭필름용 조성물은 인장강도 및 연신율을 향상시키기 위해 무수말레산-그래프트(MAH-g)를 포함한다.The composition for mulching film of the present invention includes maleic anhydride-graft (MAH-g) to improve tensile strength and elongation.
본 발명의 일 실시예에 따르면, 글리세린의 함량은 조성물 전체 중량에 대해서 5 내지 20 중량%인 것이 바람직하다. According to one embodiment of the present invention, the content of glycerin is preferably 5 to 20% by weight based on the total weight of the composition.
본 발명의 일 실시예에 따르면, 무수말레산-그래프트(MAH-g)의 함량은 조성물 전체 중량에 대해서 2 내지 10 중량%인 것이 바람직하다. According to one embodiment of the present invention, the content of maleic anhydride-graft (MAH-g) is preferably 2 to 10% by weight based on the total weight of the composition.
본 발명의 멀칭필름용 조성물은 열가소성을 향상시키기 위해 글리세린을 포함할 수 있다.The composition for mulching film of the present invention may contain glycerin to improve thermoplasticity.
본 발명의 일 실시예에 따르면, 글리세린의 함량은 조성물 전체 중량에 대해서 5 내지 20 중량%인 것이 바람직하다. According to one embodiment of the present invention, the content of glycerin is preferably 5 to 20% by weight based on the total weight of the composition.
본 발명의 멀칭필름용 조성물은 생분해 촉진첨가제로서 락트산(LA) 및 이타콘산무수물(IA)로 이루어진 군 중에서 선택된 1종 이상을 더 포함할 수 있다.The composition for a mulching film of the present invention may further include at least one selected from the group consisting of lactic acid (LA) and itaconic anhydride (IA) as a biodegradation promoting additive.
상기 락트산(LA)은 분말상으로 조성물 전체 중량에 대하여 1 내지 2 중량% 포함되어 생분해를 촉진할 수 있다.The lactic acid (LA) is contained in powder form at 1 to 2% by weight based on the total weight of the composition and can promote biodegradation.
상기 이타콘산무수물(IA)은 조성물 전체 중량에 대하여 0.5 내지 1.0 중량% 포함되어 PLA 수지의 토양생분해를 촉진할 수 있다.The itaconic anhydride (IA) is included in an amount of 0.5 to 1.0% by weight based on the total weight of the composition and can promote soil biodegradation of PLA resin.
상기 조성물은 일반토양조건 180일(KS M ISO 17556) 생분해도(%)가 50%이상일 수 있다.The composition may have a biodegradability (%) of 50% or more under general soil conditions for 180 days (KS M ISO 17556).
본 발명의 다른 실시예는, 전분분말을 가소화처리하여 변성 열가소성 전분을 제조하는 단계; 락트산 및 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)를 포함하는 락트산 마스터배치를 제조하는 단계; 상기 변성 열가소성 전분, 생분해성 고분자 수지, CaCO3 및 무수말레산-그래프트(MAH-g)를 혼합, 용융 및 압출하여 생분해성 멀칭 컴파운드를 제조하는 단계; 및 상기 생분해성 멀칭 컴파운드를 블로운 필름 압출하여 생분해성 멀칭 필름을 제조하는 단계; 를 포함하는 생분해성 멀칭 필름의 제조방법을 제공한다.Another embodiment of the present invention includes the steps of plasticizing starch powder to produce modified thermoplastic starch; Preparing a lactic acid masterbatch comprising lactic acid and polybutylene adipate terephthalate (PBAT); Mixing, melting and extruding the modified thermoplastic starch, biodegradable polymer resin, CaCO 3 and maleic anhydride-graft (MAH-g) to prepare a biodegradable mulching compound; And manufacturing a biodegradable mulching film by extruding the biodegradable mulching compound into a blown film; It provides a method for manufacturing a biodegradable mulching film comprising.
본 발명에 따른 생분해성 멀칭 필름의 제조방법은 전분분말을 가소화처리하여 변성 열가소성 전분을 제조하는 단계를 포함한다.The method for producing a biodegradable mulching film according to the present invention includes the step of plasticizing starch powder to produce modified thermoplastic starch.
상기 가소화처리는 전분을 효소적 또는 화학적으로 변성하는 과정일 수 있다. The plasticization treatment may be a process of enzymatically or chemically modifying starch.
본 발명의 일 실시예에 따르면, 상기 가소화처리는 화학적 변성을 위해 전분 분말에 가소제를 처리하는 과정일 수 있다. 상기 가소제는 포도당, 자당, 과당, 라피노오스, 말토 덱스테로오스, 갈락토오스, 크실로오스, 말토오스, 유당, 만노오스 및 에리트로오스 등의 당류; 에리트리톨, 크실리톨, 말리톨, 만니톨, 글리세롤 및 소르비톨 등의 당 알코올류; 글리세린, 에틸렌 글리콜, 프로필렌 글리콜, 디프로필렌 글리콜, 부틸렌 글리콜 및 헥산 트리올 등의 폴리올류 등과 같은 다가 알코올 가소제를 포함할 수 있다.According to one embodiment of the present invention, the plasticization treatment may be a process of treating starch powder with a plasticizer for chemical modification. The plasticizer includes sugars such as glucose, sucrose, fructose, raffinose, maltodexterose, galactose, xylose, maltose, lactose, mannose, and erythrose; sugar alcohols such as erythritol, xylitol, maltol, mannitol, glycerol, and sorbitol; It may contain polyhydric alcohol plasticizers such as polyols such as glycerin, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and hexane triol.
본 발명의 일 실시예에 따르면, 상기 가소화처리는 효소적 변성을 위해 전분 분말에 효소를 처리하는 과정일 수 있다. 일례로, 이소-아밀라아제 효소에 의해 아밀로펙틴구조(포도당고리 30개 내지 40개)의 전분을 아밀로오스(포도당고리 8개 내지 12개) 형태로 변환하여 변성된 아밀로오스 구조에 가공성을 부여하기 위해 아밀로수크레이스 효소를 첨가하여 아밀로오스 전분구조 말단에 지방산을 결합시키는 과정일 수 있다.According to one embodiment of the present invention, the plasticization treatment may be a process of treating starch powder with an enzyme for enzymatic modification. For example, starch in the amylopectin structure (30 to 40 glucose rings) is converted to amylose (8 to 12 glucose rings) by iso-amylase enzyme to give processability to the modified amylose structure. This may be a process of adding a lacy enzyme to bind a fatty acid to the end of the amylose starch structure.
본 발명에 따른 생분해성 멀칭 필름의 제조방법은 락트산 및 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)를 포함하는 락트산 마스터배치를 제조하는 단계를 포함한다. 생분해 촉진첨가제인 락트산은 액체 상태이므로 직접 고분자 수지와 섞어서 사용하기가 어려울 뿐만 아니라, 고분자 수지와의 혼련성이 좋지 않다. 따라서, 락트산을 포함하는 마스터배치를 미리 제작하고, 컴파운드 제조시에 첨가한다. The method for producing a biodegradable mulching film according to the present invention includes preparing a lactic acid masterbatch containing lactic acid and polybutylene adipate terephthalate (PBAT). Lactic acid, a biodegradation promoting additive, is in a liquid state, so not only is it difficult to mix it directly with polymer resin, but it also has poor mixing properties with polymer resin. Therefore, a masterbatch containing lactic acid is prepared in advance and added when manufacturing the compound.
본 발명의 일 실시예에 따르면, 상기 마스터배치는 마스터배치의 전체 중량에 대하여 1∼2중량%의 락트산이 포함된 것일 수 있다. According to one embodiment of the present invention, the masterbatch may contain 1 to 2% by weight of lactic acid based on the total weight of the masterbatch.
상기 마스터배치는 PLA 수지의 토양생분해를 촉진하기 위하여 이타콘산 무수물(Itaconic anhydride)를 추가로 포함할 수 있다.The masterbatch may additionally contain itaconic anhydride to promote soil biodegradation of PLA resin.
본 발명의 일 실시예에 따르면, 상기 마스터배치는 마스터배치의 전체 중량에 대하여 0.5∼1.0중량%의 이타콘산 무수물(Itaconic anhydride)이 포함된 것일 수 있다.According to one embodiment of the present invention, the masterbatch may contain 0.5 to 1.0% by weight of itaconic anhydride based on the total weight of the masterbatch.
본 발명의 일 실시예에 따르면, 상기 생분해성 고분자 수지 수지는 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리락트산(PLA)가 1 :0.1~0.4의 중량비로 혼합된 것일 수 있다.According to one embodiment of the present invention, the biodegradable polymer resin may be a mixture of polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) at a weight ratio of 1:0.1 to 0.4.
본 발명의 다른 실시예는, 상기 제조방법에 따라 제조한 생분해성 멀칭필름을 제공한다.Another embodiment of the present invention provides a biodegradable mulching film manufactured according to the above manufacturing method.
본 발명의 멀칭필름은 종래와 같은 합성수지를 사용하지 않고, 변성 열가소성 전분 및 생분해성 고분자 수지를 포함하는 베이스 폴리머로 구성되어 빠른 속도로 자연 분해가 가능한 효과가 있다.The mulching film of the present invention does not use conventional synthetic resins, but is composed of a base polymer containing modified thermoplastic starch and biodegradable polymer resin, so it is capable of natural decomposition at a rapid rate.
이하, 본원 발명의 바람직한 실시예를 첨부한 도면과 같이 본원이 속하는 기술 분야에서 일반적인 지식을 가진 자가 쉽게 실시할 수 있도록 본원의 구현예 및 실시예를 상세히 설명한다. 특히 이것에 의해 본원 발명의 기술적 사상과 그 핵심 구성 및 작용이 제한을 받지 않는다. 또한, 본원 발명의 내용은 여러 가지 다른 형태의 장비로 구현될 수 있으며, 여기에서 설명하는 구현예 및 실시예에 한정되지 않는다.Hereinafter, as shown in the accompanying drawings showing preferred embodiments of the present invention, the embodiments and examples of the present invention will be described in detail so that those with general knowledge in the technical field to which the present invention pertains can easily implement them. In particular, the technical idea of the present invention and its core structure and operation are not limited by this. In addition, the content of the present invention can be implemented in various other types of equipment, and is not limited to the implementation examples and examples described herein.
[재료성분][Material ingredients]
전분 분말로는 감자에서 추출한 전분을 사용하였다.Starch extracted from potatoes was used as starch powder.
생분해성 고분자 수지는 수평균분자량(Mn)이 80,000~10,000 g/mol이고, 융점이 120~140℃인 폴리부틸렌에틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리락틱산(PLA)의 혼합물을 사용하였다.The biodegradable polymer resin was a mixture of polybutylene ethylene adipate terephthalate (PBAT) and polylactic acid (PLA) with a number average molecular weight (Mn) of 80,000 to 10,000 g/mol and a melting point of 120 to 140°C. .
<제조예 1> 변성 열가소성 전분의 제조<Preparation Example 1> Preparation of modified thermoplastic starch
전분 분말을 효소처리하여 변성 열가소성 전분을 제조하였다.Modified thermoplastic starch was prepared by treating starch powder with enzymes.
먼저 전분 분말을 이소-아밀라아제 효소로 처리하여 아밀로펙틴구조(포도당고리 30개 내지 40개)의 전분을 아밀로오스(포도당고리 8개 내지 12개) 형태로 변환시켰다. 그 다음 변성된 아밀로오스 구조에 아밀로수크레이스 효소를 첨가하여 아밀로오스 전분구조 말단에 지방산을 결합시켜 변성 열가소성 전분을 제조하였다.First, starch powder was treated with iso-amylase enzyme to convert starch of amylopectin structure (30 to 40 glucose rings) into amylose (8 to 12 glucose rings). Next, amylosucrese enzyme was added to the modified amylose structure to bind fatty acids to the ends of the amylose starch structure to prepare modified thermoplastic starch.
<제조예 2> 락트산 마스터배치의 제조<Preparation Example 2> Preparation of lactic acid masterbatch
락트산 및 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)를 포함하는 락트산 마스터배치를 제조하였다.A lactic acid masterbatch containing lactic acid and polybutylene adipate terephthalate (PBAT) was prepared.
락트산 1-10중량부 및 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 90-99중량부를 리본블렌더에서 배합한 후, 온도 170℃ 내지 210℃로 설정된 실린더에서 압출기로 용융압출하고 펠릿화하여, 락트산 마스터배치를 얻었다.1-10 parts by weight of lactic acid and 90-99 parts by weight of polybutylene adipate terephthalate (PBAT) are mixed in a ribbon blender, then melted and extruded with an extruder in a cylinder set at a temperature of 170°C to 210°C and pelletized to produce lactic acid master. Got the batch.
<제조예 3> 락트산 마스터배치의 제조<Preparation Example 3> Preparation of lactic acid masterbatch
이타콘산 무수물 1-5중량부를 더 첨가한 것을 제외하고는 제조예 2와 동일한 방법으로 락트산 마스터배치를 제조하였다.A lactic acid masterbatch was prepared in the same manner as Preparation Example 2, except that 1-5 parts by weight of itaconic anhydride was added.
<실시예 1> <Example 1>
생분해성 멀칭필름용 조성물의 제조Preparation of composition for biodegradable mulching film
상기 제조예 1에서 제조한 변성 열가소성 전분, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT), 폴리락트산(PLA), CaCO3, 무수말레산-그래프트(MAH-g)를 하기 표 1에 나타낸 혼합비율로 혼합하여 멀칭필름용 조성물을 제조하였다. The modified thermoplastic starch, polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), CaCO 3 , and maleic anhydride-graft (MAH-g) prepared in Preparation Example 1 were mixed at the mixing ratio shown in Table 1 below. A composition for a mulching film was prepared by mixing.
생분해성 멀칭필름의 제조Manufacturing of biodegradable mulching film
상기 멀칭필름용 조성물을 압출하여 펠렛 형태의 생분해 멀칭 컴파운드를 제조하였다. 이때, 압출기는 스크류 직경이 44 mm인 트윈 압출기를 사용하였으며, 압출속도는 300 rpm, 원료투입속도는 40 rpm, 배럴온도는 150 ℃로 하였다.The composition for the mulching film was extruded to prepare a biodegradable mulching compound in the form of pellets. At this time, a twin extruder with a screw diameter of 44 mm was used, the extrusion speed was 300 rpm, the raw material input speed was 40 rpm, and the barrel temperature was 150 ℃.
상기 생분해 멀칭 컴파운드를 필름 성형기(대륜기계㈜, 기종: 50 mm HD/PF FILM M/C)로 멀칭필름을 제조하였다. 이때, 필름 성형기의 배럴온도는 160 ℃로 하고, 다이 온도는 150 ℃로 하였다. 압출 속도는 500 rpm, 원료투입속도는 100 rpm, 롤속도는 200 rpm으로 하여 생분해성 멀칭필름을 제조하였다. 상기 생분해성 멀칭필름의 두께는 30 내지 70㎛로 제조하였다.A mulching film was manufactured from the biodegradable mulching compound using a film molding machine (Daeryun Machinery Co., Ltd., model: 50 mm HD/PF FILM M/C). At this time, the barrel temperature of the film molding machine was set to 160°C, and the die temperature was set to 150°C. A biodegradable mulching film was manufactured at an extrusion speed of 500 rpm, a raw material input speed of 100 rpm, and a roll speed of 200 rpm. The thickness of the biodegradable mulching film was manufactured to be 30 to 70㎛.
<비교예 1> <Comparative Example 1>
생분해성 멀칭필름용 조성물의 제조Preparation of composition for biodegradable mulching film
변성 열가소성 전분 및 무수말레산-그래프트(MAH-g)를 사용하지 않고, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT), 폴리락트산(PLA), CaCO3를 하기 표 1에 나타낸 혼합비율로 혼합하여 멀칭필름용 조성물을 제조하였다.Instead of using modified thermoplastic starch and maleic anhydride-graft (MAH-g), mulching was performed by mixing polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), and CaCO 3 at the mixing ratio shown in Table 1 below. A composition for film was prepared.
생분해성 멀칭필름의 제조Manufacturing of biodegradable mulching film
실시예 1과 동일한 방법으로 생분해성 멀칭필름을 제조하였다.A biodegradable mulching film was prepared in the same manner as Example 1.
<비교예 2><Comparative Example 2>
생분해성 멀칭필름용 조성물의 제조Preparation of composition for biodegradable mulching film
무수말레산-그래프트(MAH-g)를 사용하지 않고, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT), 폴리락트산(PLA), 화학적 TPS를 표 1에 나타낸 혼합비율로 혼합하여 멀칭필름용 조성물을 제조하였다.Without using maleic anhydride-graft (MAH-g), a composition for mulching film was prepared by mixing polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), and chemical TPS at the mixing ratio shown in Table 1. did.
생분해성 멀칭필름의 제조Manufacturing of biodegradable mulching film
실시예 1과 동일한 방법으로 생분해성 멀칭필름을 제조하였다.A biodegradable mulching film was prepared in the same manner as Example 1.
<비교예 3> <Comparative Example 3>
생분해성 멀칭필름용 조성물의 제조Preparation of composition for biodegradable mulching film
무수말레산-그래프트(MAH-g)를 사용하지 않고, 폴리부틸렌 아디페이트 테레프탈레이트(PBAT), 폴리락트산(PLA), 효소적 TPS를 하기 표 1에 나타낸 혼합비율로 혼합하여 멀칭필름용 조성물을 제조하였다.A composition for mulching film made by mixing polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), and enzymatic TPS in the mixing ratio shown in Table 1 below, without using maleic anhydride-graft (MAH-g). was manufactured.
생분해성 멀칭필름의 제조Manufacturing of biodegradable mulching film
실시예 1과 동일한 방법으로 생분해성 멀칭필름을 제조하였다.A biodegradable mulching film was prepared in the same manner as Example 1.
<실험예 1> 생분해도 평가<Experimental Example 1> Biodegradability evaluation
상기 실시예 1, 및 비교예 1 내지 3에서 제조한 멀칭필름을 2Х2cm 크기로 절단하여 얻은 시료를 KS M ISO 14855-1(퇴비화 조건에서의 플라스틱의 호기성 생분해도 측정방법)에 의해 90일 기준으로 표준시료(셀룰로오즈)와 시험시료의 발생된 이산화탄소의 양을 측정하여 하기 식에 의해 평가하여 그 결과를 하기 표 1 내지 표 3에 나타내었다. The samples obtained by cutting the mulching films prepared in Example 1 and Comparative Examples 1 to 3 into 2Х2cm pieces were analyzed for 90 days according to KS M ISO 14855-1 (Method for measuring aerobic biodegradability of plastics under composting conditions). The amount of carbon dioxide generated in the standard sample (cellulose) and the test sample was measured and evaluated using the formula below, and the results are shown in Tables 1 to 3 below.
생분해도(%) = (발생 이산화탄소의 양/이론적 이산화탄소의 양) x 100Biodegradability (%) = (amount of carbon dioxide generated/theoretical amount of carbon dioxide) x 100
또한, 일반토양조건인 KS M ISO 17556(이산화탄소 발생량 또는 산소소비량 측정)에 의해 180일 기준으로 표준시료(셀룰로오즈)와 시험시료의 발생된 이산화탄소의 양을 측정하여 하기 식에 의해 평가하여 그 결과를 하기 표 1 내지 표 3에 나타내었다.In addition, the amount of carbon dioxide generated in the standard sample (cellulose) and test sample was measured on a 180-day basis according to KS M ISO 17556 (measurement of carbon dioxide generation or oxygen consumption), which is a general soil condition, and evaluated by the formula below. Shown in Tables 1 to 3 below.
생분해도(%) = (발생 이산화탄소의 양/이론적 이산화탄소의 양) x 100Biodegradability (%) = (amount of carbon dioxide generated/theoretical amount of carbon dioxide) x 100
<실험예 2> 가공성 평가<Experimental Example 2> Processability evaluation
상기 실시예 1, 및 비교예 1 내지 3에서 제조한 멀칭필름의 가공성을 하기 식에 의해 평가하여 그 결과를 하기 표 1에 나타내었다. The processability of the mulching films prepared in Example 1 and Comparative Examples 1 to 3 was evaluated by the following equation, and the results are shown in Table 1 below.
수율(%)=[(완제품무게)/(투입원료무게)] x 100 Yield (%) = [(Weight of finished product)/(Weight of input raw materials)] x 100
(중량%)Furtherance
(weight%)
90일(KS M ISO 14855-1)Industrial composting conditions
90 days (KS M ISO 14855-1)
180일(KS M ISO 17556)General soil conditions
180 days (KS M ISO 17556)
(%)transference number
(%)
상기 표 1에 나타낸 바와 같이, TPS 및 MAH-g를 사용하지 않은 비교예 1의 경우 생분해도가 매우 낮았다. 또한, MAH-g를 사용하지 않은 비교예 2 내지 3의 경우에도 생분해도가 70% 미만으로 나타났다.As shown in Table 1, in Comparative Example 1, which did not use TPS and MAH-g, the biodegradability was very low. In addition, in Comparative Examples 2 to 3 where MAH-g was not used, biodegradability was found to be less than 70%.
반면, TPS 및 MAH-g를 사용한 실시예 1의 경우 70%를 넘은 생분해도를 나타냈다.On the other hand, Example 1 using TPS and MAH-g showed biodegradability exceeding 70%.
따라서, 이후 실시예1의 조성물에 대해 추가적인 실험을 진행하였다.Therefore, additional experiments were conducted on the composition of Example 1.
<실험예 3> 변성 열가소성 전분 입자의 평균입경[d(0.5)] 및 입자분포도[span]의 영향<Experimental Example 3> Effect of average particle diameter [d(0.5)] and particle distribution [span] of modified thermoplastic starch particles
변성 열가소성 전분 입자의 평균입경[d(0.5)] 및 입자분포도[span]의 영향을 실험하였다.The effects of the average particle size [d(0.5)] and particle distribution [span] of modified thermoplastic starch particles were tested.
실시예 1의 경우 변성 열가소성 전분 입자의 평균입경[d(0.5)]은 5.5㎛이고, 입자분포도[span]은 1.86이었다.In Example 1, the average particle diameter [d(0.5)] of the modified thermoplastic starch particles was 5.5㎛, and the particle distribution [span] was 1.86.
변성 열가소성 전분 입자의 평균입경[d(0.5)]이 1.1㎛이고, 입자분포도[span]가 1.31인 것을 제외하고는 실시예 1과 동일한 방법으로 멀칭필름을 제조하여 생분해도를 평가한 후 그 결과를 하기 표 2에 나타내었다.(실시예 2)A mulching film was prepared in the same manner as in Example 1, except that the average particle diameter [d(0.5)] of the modified thermoplastic starch particles was 1.1㎛ and the particle distribution [span] was 1.31, and biodegradability was evaluated. The results were as follows. is shown in Table 2 below. (Example 2)
변성 열가소성 전분 입자의 평균입경[d(0.5)]은 500nm이고, 입자분포도[span]은 1.02인 것을 제외하고는 실시예 1과 동일한 방법으로 멀칭필름을 제조하여 생분해도를 평가한 후 그 결과를 하기 표 2에 나타내었다.(실시예 3)Mulching film was prepared in the same manner as in Example 1, except that the average particle diameter [d(0.5)] of the modified thermoplastic starch particles was 500 nm and the particle distribution [span] was 1.02, biodegradability was evaluated, and the results were reported. It is shown in Table 2 below. (Example 3)
[D(0.5)]TPS average particle size
[D(0.5)]
[Span]TPS particle distribution chart
[Span]
90일(KS M ISO 14855-1) Industrial composting conditions
90 days (KS M ISO 14855-1)
180일(KS M ISO 17556)General soil conditions
180 days (KS M ISO 17556)
상기 표 2에 나타낸 바와 같이, TPS의 평균입경이 적어질수록 입자분포도가 낮아질수록 생분해도가 증가함을 확인할 수 있었다. 특히 TPS의 평균입경이 500nm이고 입자분포도가 1.02인 실시예3의 경우 84%를 넘는 생분해도를 나타내었다.As shown in Table 2 above, it was confirmed that as the average particle diameter of TPS decreases and the particle distribution decreases, biodegradability increases. In particular, Example 3, in which the average particle diameter of TPS was 500 nm and the particle distribution was 1.02, showed a biodegradability exceeding 84%.
<실험예 4> 생분해촉진 첨가제를 통한 생분해성 촉진<Experimental Example 4> Promotion of biodegradability through biodegradation promotion additives
생분해촉진 첨가제를 통한 생분해성 촉진 효과를 실험하였다.The effect of promoting biodegradation through biodegradation promoting additives was tested.
제조예 2에서 제조한 락트산 마스터배치를 첨가한 것을 제외하고는 실시예 3과 동일한 방법으로 멀칭필름을 제조한 후 생분해도를 평가하여 그 결과를 하기 표 3에 나타내었다.A mulching film was prepared in the same manner as in Example 3, except that the lactic acid masterbatch prepared in Preparation Example 2 was added, and then biodegradability was evaluated. The results are shown in Table 3 below.
제조예 3에서 제조한 락트산 마스터배치를 첨가한 것을 제외하고는 실시예 3과 동일한 방법으로 멀칭필름을 제조한 후 생분해도를 평가하여 그 결과를 하기 표 3에 나타내었다.A mulching film was prepared in the same manner as in Example 3, except that the lactic acid masterbatch prepared in Preparation Example 3 was added, and then biodegradability was evaluated. The results are shown in Table 3 below.
(중량%)Furtherance
(weight%)
90일(KS M ISO 14855-1) Industrial composting conditions
90 days (KS M ISO 14855-1)
180일(KS M ISO 17556)General soil conditions
180 days (KS M ISO 17556)
상기 표 3에 나타낸 바와 같이, 생분해촉진첨가제를 사용한 실시예 4 및 실시예 5의 경우 생분해촉진첨가제를 사용하지 않은 실시예 3의 경우보다 훨씬 높은 생분해도를 나타내었다. 특히 락트산과 이타콘산무수물을 함께 사용한 실시예 5의 경우 95%를 넘는 생분해도를 나타내었다.As shown in Table 3, Examples 4 and 5 using biodegradation-promoting additives showed much higher biodegradability than Example 3 without using biodegradation-promoting additives. In particular, Example 5, in which lactic acid and itaconic anhydride were used together, showed a biodegradability of over 95%.
한편, 본 발명은 기재된 실시례에 한정되는 것은 아니고, 적용 부위를 변경하여 사용하는 것이 가능하고, 본 발명의 사상 및 범위를 벗어나지 않고 다양하게 수정 및 변형을 할 수 있음은 이 기술 분야에서 통상의 지식을 가진 자에게는 자명하다. 따라서, 그러한 변형예 또는 수정예들은 본 발명의 특허청구범위에 속한다 해야 할 것이다.Meanwhile, the present invention is not limited to the described embodiments, and can be used by changing the application area, and various modifications and variations can be made without departing from the spirit and scope of the present invention. It is self-evident to those with knowledge. Accordingly, such variations or modifications should fall within the scope of the claims of the present invention.
Claims (16)
상기 생분해성 고분자 수지는 폴리부틸렌 아디페이트 테레프탈레이트 (PBAT) 및 폴리락트산(PLA)가 1 :0.1~0.4의 중량비로 혼합된 것이고,
상기 변성 열가소성 전분은 효소적 변성 열가소성 전분 및 화학적 변성 열가소성 전분으로 이루어진 전분 유도체이고,
상기 변성 열가소성 전분은 300 nm 내지 500 nm의 평균 지름을 가지는 구형 나노입자이고,
상기 변성 열가소성 전분은 0.8 내지 1.3의 분포도(Span)를 가지는 균일한 입자인,
멀칭필름용 조성물.Contains biodegradable polymer resin, modified thermoplastic starch, CaCO 3 , maleic anhydride-graft (MAH-g), and lactic acid (LA) and itaconic anhydride (IA) as biodegradation promoting additives,
The biodegradable polymer resin is a mixture of polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) at a weight ratio of 1:0.1 to 0.4,
The modified thermoplastic starch is a starch derivative composed of enzymatically modified thermoplastic starch and chemically modified thermoplastic starch,
The modified thermoplastic starch is a spherical nanoparticle having an average diameter of 300 nm to 500 nm,
The modified thermoplastic starch is a uniform particle having a span of 0.8 to 1.3.
Composition for mulching film.
상기 락트산(LA)은 분말상으로 조성물 전체 중량에 대하여 1 내지 2 중량% 포함되어 생분해를 촉진하는 것인 멀칭필름용 조성물.According to paragraph 1,
A composition for a mulching film wherein the lactic acid (LA) is contained in powder form at 1 to 2% by weight based on the total weight of the composition to promote biodegradation.
상기 이타콘산무수물(IA)은 조성물 전체 중량에 대하여 0.5 내지 1.0 중량% 포함되어 PLA 수지의 토양생분해를 촉진하는 것인 멀칭필름용 조성물.According to paragraph 1,
A composition for a mulching film wherein the itaconic anhydride (IA) is included in an amount of 0.5 to 1.0% by weight based on the total weight of the composition to promote soil biodegradation of the PLA resin.
상기 조성물은 일반토양조건 180일(KS M ISO 17556) 생분해도(%)가 50%이상인 것인 멀칭필름용 조성물.According to paragraph 1,
The composition is a composition for a mulching film having a biodegradability (%) of 50% or more under general soil conditions for 180 days (KS M ISO 17556).
락트산 및 폴리부틸렌 아디페이트 테레프탈레이트(PBAT)를 포함하는 락트산 마스터배치를 제조하는 단계;
상기 변성 열가소성 전분, 생분해성 고분자 수지, CaCO3, 무수말레산-그래프트(MAH-g) 및 락트산 마스터배치를 혼합, 용융 및 압출하여 생분해성 멀칭 컴파운드를 제조하는 단계; 및
상기 생분해성 멀칭 컴파운드를 블로운 필름 압출하여 생분해성 멀칭 필름을 제조하는 단계;
를 포함하는
제1항의 멀칭필름용 조성물을 이용하는 생분해성 멀칭 필름의 제조방법.Plasticizing starch powder to produce modified thermoplastic starch;
Preparing a lactic acid masterbatch comprising lactic acid and polybutylene adipate terephthalate (PBAT);
Mixing, melting, and extruding the modified thermoplastic starch, biodegradable polymer resin, CaCO 3 , maleic anhydride-graft (MAH-g), and lactic acid masterbatch to prepare a biodegradable mulching compound; and
Manufacturing a biodegradable mulching film by extruding the biodegradable mulching compound into a blown film;
containing
A method of producing a biodegradable mulching film using the composition for a mulching film of claim 1.
상기 마스터배치는 마스터배치의 전체 중량에 대하여 1∼2중량%의 락트산이 포함된 것인 제조방법.According to clause 12,
A manufacturing method in which the masterbatch contains 1 to 2% by weight of lactic acid based on the total weight of the masterbatch.
상기 마스터배치는 마스터배치의 전체 중량에 대하여 0.5∼1.0중량%의 이타콘산 무수물(Itaconic anhydride)이 포함된 것인 제조방법.According to clause 12,
A manufacturing method in which the masterbatch contains 0.5 to 1.0% by weight of itaconic anhydride based on the total weight of the masterbatch.
상기 생분해성 고분자 수지 수지는 폴리부틸렌 아디페이트 테레프탈레이트(PBAT) 및 폴리락트산(PLA)가 1 :0.1~0.4의 중량비로 혼합된 것인 제조방법.According to clause 12,
The biodegradable polymer resin is a manufacturing method in which polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) are mixed at a weight ratio of 1:0.1 to 0.4.
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| KR20140106882A (en) * | 2013-02-27 | 2014-09-04 | 일신화학공업 주식회사 | Biodegradable Resin Composition and Biodegradable Mulching Film Using of the Same |
| KR20170075052A (en) * | 2015-12-22 | 2017-07-03 | 롯데정밀화학 주식회사 | Resin composition for mulching film and biodegradable mulching film using the same |
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| KR20140106882A (en) * | 2013-02-27 | 2014-09-04 | 일신화학공업 주식회사 | Biodegradable Resin Composition and Biodegradable Mulching Film Using of the Same |
| KR20170075052A (en) * | 2015-12-22 | 2017-07-03 | 롯데정밀화학 주식회사 | Resin composition for mulching film and biodegradable mulching film using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116555066A (en) * | 2022-09-06 | 2023-08-08 | 中国科学院南京土壤研究所 | Efficient PBAT agricultural film degrading bacterium and application thereof |
| CN116555066B (en) * | 2022-09-06 | 2024-02-20 | 中国科学院南京土壤研究所 | Efficient PBAT agricultural film degrading bacterium and application thereof |
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