KR100545271B1 - Aerobic biodegradable-agriculture mulching film and the producing method thereof - Google Patents
Aerobic biodegradable-agriculture mulching film and the producing method thereof Download PDFInfo
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- KR100545271B1 KR100545271B1 KR1020050036627A KR20050036627A KR100545271B1 KR 100545271 B1 KR100545271 B1 KR 100545271B1 KR 1020050036627 A KR1020050036627 A KR 1020050036627A KR 20050036627 A KR20050036627 A KR 20050036627A KR 100545271 B1 KR100545271 B1 KR 100545271B1
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Classifications
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/21—Combinations with auxiliary equipment, e.g. with clocks or memoranda pads
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61H—PHYSICAL THERAPY APPARATUS, e.g. DEVICES FOR LOCATING OR STIMULATING REFLEX POINTS IN THE BODY; ARTIFICIAL RESPIRATION; MASSAGE; BATHING DEVICES FOR SPECIAL THERAPEUTIC OR HYGIENIC PURPOSES OR SPECIFIC PARTS OF THE BODY
- A61H23/00—Percussion or vibration massage, e.g. using supersonic vibration; Suction-vibration massage; Massage with moving diaphragms
- A61H23/02—Percussion or vibration massage, e.g. using supersonic vibration; Suction-vibration massage; Massage with moving diaphragms with electric or magnetic drive
- A61H23/0245—Percussion or vibration massage, e.g. using supersonic vibration; Suction-vibration massage; Massage with moving diaphragms with electric or magnetic drive with ultrasonic transducers, e.g. piezoelectric
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61H—PHYSICAL THERAPY APPARATUS, e.g. DEVICES FOR LOCATING OR STIMULATING REFLEX POINTS IN THE BODY; ARTIFICIAL RESPIRATION; MASSAGE; BATHING DEVICES FOR SPECIAL THERAPEUTIC OR HYGIENIC PURPOSES OR SPECIFIC PARTS OF THE BODY
- A61H2205/00—Devices for specific parts of the body
- A61H2205/02—Head
- A61H2205/022—Face
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- Health & Medical Sciences (AREA)
- Rehabilitation Therapy (AREA)
- Signal Processing (AREA)
- Epidemiology (AREA)
- Pain & Pain Management (AREA)
- Physical Education & Sports Medicine (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
본 발명은 생분해성 농업용 멀칭필름에 관한 것으로 특히 생분해성화합물을 폴리에틸렌 또는 폴리스틸렌 같은 합성수지류의 베이스폴리머(base polymer)에 혼합하여 압출한 필름으로서 생분해성화합물 뿐만아니라 베이스폴리머도 생분해할 수 있어서 토양의 바닥에 피복하여 사용하면 잡초의 생육을 억제하고 병충해를 예방할 수 있어서 농약사용을 현저하게 절감할 수 있으면서도 일정시간이 경과한 뒤에는 자연상태에서 미생물에 의해 분해되기 때문에 환경오염도 방지할 수 있는 친환경적인 생분해성 농업용 멀칭필름에 관한 것이다. The present invention relates to a biodegradable agricultural mulching film, in particular, a film extruded by mixing a biodegradable compound with a base polymer of synthetic resins such as polyethylene or polystyrene, which can biodegrade not only a biodegradable compound but also a base polymer. When coated on the floor, weeds can suppress weed growth and prevent pests, which can significantly reduce the use of pesticides, while being decomposed by microorganisms in a natural state after a certain period of time. It relates to a mulch film for sex agriculture.
생분해필름, 베이스폴리머, 생분해,멀칭필름 Biodegradable Film, Base Polymer, Biodegradable, Mulching Film
Description
본 발명은 생분해성 농업용 멀칭필름에 관한 것으로 특히 생분해성화합물을 폴리에틸렌 또는 폴리스틸렌과 같은 합성수지류의 베이스폴리머(base polymer)에 혼합하여 압출한 필름으로서 생분해성화합물 뿐만아니라 베이스폴리머도 생분해를 할 수 있어서 토양의 바닥에 피복하여 사용하면 잡초의 생육을 억제하고 병충해를 예방할 수 있어서 농약사용을 현저하게 절감할 수 있으면서도 일정시간이 경과한 뒤에는 자연상태에서 미생물에 의해 분해되기 때문에 환경오염도 방지할 수 있는 친환경적인 생분해성 농업용 멀칭필름에 관한 것이다. The present invention relates to a biodegradable agricultural mulching film, in particular, a film extruded by mixing a biodegradable compound with a base polymer of a synthetic resin such as polyethylene or polystyrene, so that not only the biodegradable compound but also the base polymer can be biodegraded. When applied to the bottom of soil, weeds can suppress the growth of weeds and prevent pests, and can significantly reduce the use of pesticides, while being decomposed by microorganisms in a natural state after a certain period of time, thereby preventing environmental pollution. Biodegradable agricultural mulching film.
벼농사의 형태는 크게 논벼 재배와 밭벼 재배로 나뉘는데 논에 물을 대고 농사를 짓는 논벼 재배가 여러 면에서 유리하기 때문에 벼농사의 대부분은 수도작(水稻作)이며 밭벼 재배는 극히 적은 실정이다. 또한, 수도작의 경우도, 못자리에서 육묘를 하여 논에 옮겨심는 육묘이앙재배와 논을 정지하고 물을 댄 후 바로 종자를 뿌리는 담수직파재배(湛水直播栽培), 그리고 논을 밭상태로 정지한 후 종자를 뿌리고 벼가 어느 정도 자란 후에 물을 대주는 건답직파재배(乾畓直播栽培)로 나뉘는데 한국에서는 이앙재배가 대부분이고 근년에 일부 간척지에서 담수직파재배가 소규모로 실시되고 있다. 이앙재배의 경우, 이앙후부터 추수까지 생육기별로 물대기와 물빼기를 반복하여 수분의 양을 조절하여야 하며, 잡초를 수시로 제거하고 병충해 방지를 위해서 각종 제초제와 살충제 등의 농약을 주기적으로 수차례에 걸쳐 적절하게 사용하여야 한다. 그러나, 최근 들어 농약의 인체 유해성이 보고 되면서, 농약을 사용한 농산물을 수요자들이 꺼려하게 되었고 수요자의 관심이 유기능 또는 친환경 농산물로 옮겨가면서 친환경농법의 필요성이 날로 증대하고 있다. 비단, 논농사 뿐만 아니라 각종 밭농사에서도 이와 같은 문제점은 여전히 존재한다. Rice farming is divided into two types of rice cultivation and field rice cultivation. Since rice cultivation is advantageous in many ways, the rice cultivation by watering the rice cultivation is advantageous in many respects. In addition, in the case of rice crops, seedlings are grown in ponds and planted in rice paddies, freshwater straight cultivation where seeds are seeded immediately after watering, and rice fields are stopped in a field state. It is divided into dry seed cultivation, which is seeded, and then watered after rice has grown to a certain extent. In Korea, most of the rice cultivation is cultivated, and in recent years, freshwater cultivation has been carried out on a small scale in some reclaimed lands. In the case of rice transplanting, the amount of water must be controlled by repeating the watering and draining for each growing season from the rice transplanting to the harvesting season.The pesticides such as various herbicides and insecticides are periodically removed several times to remove weeds and prevent pests. It must be used properly. However, recently, as the harmfulness of pesticides has been reported, consumers are reluctant to produce agricultural products using pesticides, and the demand for eco-friendly farming methods is increasing day by day as consumers' attention is shifted to organic or eco-friendly agricultural products. Silk, as well as paddy farming as well as various field farming, such problems still exist.
친환경 농법 중 한가지로, 멀칭농법이라는 것이 있는데, 멀칭이란 농작물을 재배할 때 토양의 표면을 덮어주는 자재 예컨대, 볏짚, 보릿짚, 목초 등으로 토양의 상면을 피복하여 잡초의 생육을 차단하고 병충해를 예방하며 농약사용을 절감하며, 토양침식을 방지하고 토양수분을 유지하는 목적으로 행하여지는 농법을 의미한다. 그러나, 이와 같은 농법은 밭농사에서 수작업으로 행해지고 있는 실정이며, 논농사에는 적용되지 않고 있다. 또한, 밭농사의 경우에는, 수작업으로 행해지기 때문에 생산성이 떨어져 그 실효성에 대해서도 의문이 제기되고 있다. One of the eco-friendly farming methods is called mulching farming. Mulching is a material that covers the surface of the soil when growing crops, such as rice straw, barley straw, grass, etc. to cover the top of the soil to block the growth of weeds and prevent pests. It means a farming method to reduce the use of pesticides, to prevent soil erosion and to maintain soil moisture. However, such a farming method is a situation which is performed manually by field farming and is not applied to paddy farming. Moreover, in the case of field farming, since it is performed by hand, productivity falls and the question of the effectiveness is also raised.
그리고, 이와 같은 문제점을 해결하기 위하여 생분해성 수지 필름을 밭농사나 논농사에 사용하고자 하는 시도가 없었던 것은 아니지만, 종래의 합성수지는 폴리프로필렌, 폴리에틸렌 또는 폴리스틸렌 등의 합성수지류를 베이스폴리머로하고 여기에 전분과 같은 자연성분을 혼합한 것이라 자연성분의 분해는 가능할지 몰라도 베이스폴리머 자체의 생분해는 불가능했기 때문에 토양에 피복하여 사용하면 추후 베이스폴리머가 분해되지 않아 환경오염을 유발하는 근본적인 문제점이 있었다. And, in order to solve such a problem, there was no attempt to use a biodegradable resin film for field farming or paddy farming. However, conventional synthetic resins are made of synthetic resins such as polypropylene, polyethylene, or polystyrene as a base polymer, and starch is added thereto. Since the natural components may be decomposed, but the decomposition of the natural components may be possible, the biodegradation of the base polymer itself is not possible, so that the base polymer is not decomposed after use to cover the soil, thereby causing environmental pollution.
본 발명은 앞서 본 종래기술의 문제점을 해결하기 위하여 안출된 것으로, 본 발명의 목적은 생분해성화합물와 베이스폴리머을 소정량 혼합하여 자외선의 조사로 외부에 노출되어 있거나 토양속에 매립되어 있어도 토양의 미생물등에 의해 자연 분해될 수 있어서 멀칭농법 등에 광범위하게 사용될 수 있는 생분해성 농업용 멀칭필름을 제공하는 것이다. The present invention has been made in order to solve the problems of the prior art, the object of the present invention is to mix a predetermined amount of a biodegradable compound and a base polymer by exposure to ultraviolet rays or even when exposed to the outside or embedded in the soil by the microorganisms of the soil It is to provide a biodegradable agricultural mulching film that can be naturally decomposed and can be widely used in mulching methods.
본 발명은 앞서 본 목적을 달성하기 위하여 다음과 같은 구성을 가진 실시예에 의해 구현된다. The present invention is implemented by the embodiment having the following configuration in order to achieve the above object.
본 발명의 제 1 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름은, 스테아린산, 중질탄산칼슘, 비닐케톤계공중합폴리머, 폴리에틸렌왁스, 젖당, 에틸아세테이트, 메틸메타크릴레이트, 가루우유, 이소부틸알콜, 벤젠과 LMPE를 혼합한 생분해성화합물에 플라스틱수지를 혼합가공한 후 압출하여 형성되는 것을 특징으로 한다.According to the first embodiment of the present invention, the eco-friendly biodegradable mulching film of the present invention, stearic acid, heavy calcium carbonate, vinyl ketone copolymer, polyethylene wax, lactose, ethyl acetate, methyl methacrylate, powdered milk, isobutyl The biodegradable compound mixed with alcohol, benzene and LMPE is mixed and processed to form a plastic resin, characterized in that formed by extrusion.
본 발명의 제 2 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름은, 제 1 실시예에 있어서, 상기 생분해성화합물은 스테아린산 1~4중량%, 중질탄산칼슘 30~55중량%, 비닐케톤계공중합폴리머 4~12중량%, 폴리에틸렌왁스 3~8중량%, 젖당 7~15중량%, 에틸아세테이트 1~5중량%, 메틸메타크릴레이트 1~7중량%, 가루우유 10~20중량%, 이소부틸알코올 1~5중량%, 벤젠 1~4중량%와 LMPE 2~7중량%로 이루 어진 것을 특징으로 한다.According to the second embodiment of the present invention, the eco-friendly biodegradable agricultural mulching film of the present invention, in the first embodiment, the biodegradable compound is 1 to 4% by weight stearic acid, 30 to 55% by weight heavy calcium carbonate, vinyl ketone Pore polymerization polymer 4-12 wt%, polyethylene wax 3-8 wt%, lactose 7-15 wt%, ethyl acetate 1-5 wt%, methyl methacrylate 1-7 wt%, powdered milk 10-20 wt%, It is characterized by consisting of 1 to 5% by weight of isobutyl alcohol, 1 to 4% by weight of benzene and 2 to 7% by weight of LMPE.
본 발명의 제 3 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름은, 제 2 실시예에 있어서, 상기 생분해성화합물은 스테아린산 2중량%, 중질탄산칼슘 45중량%, 비닐케톤계공중합폴리머 7.5중량%, 폴리에틸렌왁스 5중량%, 젖당 11.8중량%, 에틸아세테이트 2.5중량%, 메틸메타크릴레이트 3중량%, 가루우유 15.5중량%, 이소부틸알코올 1.8중량%, 벤젠 1.4중량%와 LMPE 4.5중량%로 이루어진 것을 특징으로 한다.According to a third embodiment of the present invention, the eco-friendly biodegradable agricultural mulching film of the present invention, in the second embodiment, the biodegradable compound is 2% by weight stearic acid, 45% by weight heavy calcium carbonate, vinyl ketone copolymer polymer 7.5 Wt%, polyethylene wax 5%, lactose 11.8%, ethyl acetate 2.5%, methyl methacrylate 3%, milk powder 15.5%, isobutyl alcohol 1.8%, benzene 1.4% and LMPE 4.5% Characterized in that consisting of.
본 발명의 제 4 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름은, 상기 제 3 실시예에 있어서, 상기 플라스틱수지는 LDPE, LLDPE,HDPE, PSP와 PP 어느 하나 또는 이들을 혼합한 것인 것을 특징으로 한다. According to the fourth embodiment of the present invention, the eco-friendly biodegradable agricultural mulching film of the present invention, in the third embodiment, wherein the plastic resin is one of LDPE, LLDPE, HDPE, PSP and PP, or a mixture thereof. It features.
본 발명의 제 5 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름은, 상기 제 4 실시예에 있어서, 상기 생분해성화합물 40중량%에 플라스틱수지로 LDPE 12중량%와 LLDPE 48중량%를 혼합하여 압출성형되는 것을 특징으로 한다.According to a fifth embodiment of the present invention, the eco-friendly biodegradable mulching film of the present invention, in the fourth embodiment, 40% by weight of the biodegradable compound is mixed with 12% by weight of LDPE and 48% by weight of LLDPE as a plastic resin It is characterized in that the extrusion.
본 발명의 제 6 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름 제조방법은, 제 1 실시예 내지 제 5 실시예의 친환경 생분해 농업용 멀칭필름을 제조하는 방법에 있어서, 상기 방법은 생분해성화합물을 생성하는 생분해성화합물생성단계와, 상기 생분해성화합물에 플라스틱수지를 혼합하여 친환경생분해 농업용 멀칭필름을 생성하는 필름생성단계로 이루어지며, According to a sixth embodiment of the present invention, the eco-friendly biodegradable agricultural mulching film manufacturing method of the present invention, in the method of manufacturing the eco-friendly biodegradable agricultural mulching film of the first embodiment to the fifth embodiment, the method comprises a biodegradable compound Comprising the biodegradable compound generating step and the film generating step of producing an eco-friendly biodegradable agricultural mulching film by mixing the plastic resin with the biodegradable compound,
상기 생분해성화합물생성단계는 스테아린산과 중질탄산칼슘과 메틸 메타크릴레이트를 110℃에서 혼합하는 제1단계와, 비닐케톤계공중합물, 폴리에틸렌왁스, 가 루우유, 이소부틸알콜과 벤젠을 40℃에서 혼합하는 제2단계와, 젖당과 에틸아세테이트를 40℃에서 혼합하는 제3단계와, 상기 제1단계, 제2단계와 제3단계를 통해 생성된 것을 90℃에서 다시 혼합한 후 LMPE를 첨가하여 압출기로 압출하는 제4단계로 이루어지고,The biodegradable compound generation step is a first step of mixing stearic acid, heavy calcium carbonate and methyl methacrylate at 110 ℃, vinyl ketone copolymer, polyethylene wax, powdered milk, isobutyl alcohol and benzene at 40 ℃ After mixing the second step of mixing, the third step of mixing the lactose and ethyl acetate at 40 ℃ and the first, second and third produced at 90 ℃ again by adding LMPE It consists of a fourth step of extruding with an extruder,
상기 필름생성단계는 상기 생분해성화합물생성단계에 의해 생성된 생분해성화합물과 플라스틱수지를 함께 압출기호퍼에 첨가하여 필름형상으로 성형하는 것을 특징으로 한다.The film producing step is characterized in that the biodegradable compound and the plastic resin produced by the biodegradable compound generating step is added to the extruder hopper to form a film.
본 발명의 제 7 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름 제조방법은, 제 6 실시예에 있어서, 상기 생분해성화합물생성단계의 제4단계는 압출기호퍼에서 180℃, 190℃와 210℃ 순으로 가열되면서 압출되는 것을 특징으로 한다. According to the seventh embodiment of the present invention, the eco-friendly biodegradable agricultural mulching film manufacturing method of the present invention, in the sixth embodiment, the fourth step of the biodegradable compound production step is 180 ℃, 190 ℃ and 210 in the extruder hopper It is characterized in that the extruded while heating in order.
본 발명의 제 8 실시예에 따르면, 본 발명의 친환경 생분해 농업용 멀칭필름 제조방법은, 제 7 실시예에 있어서, 상기 필름생성단계는 압출기호퍼에서 180~190℃, 190℃~210℃와 220℃순으로 가열되면서 압출되는 것을 특징으로 한다. According to an eighth embodiment of the present invention, the eco-friendly biodegradable agricultural mulching film manufacturing method of the present invention, in the seventh embodiment, the film generation step is 180 ~ 190 ℃, 190 ℃ ~ 210 ℃ and 220 ℃ in the extruder hopper It is characterized in that the extruded while being heated in sequence.
출원인은 이하에서 앞서 설명한 본 발명의 바람직한 실시예를 설명한다. Applicants describe preferred embodiments of the present invention described below.
본 발명의 친환경 생분해 농업용 멀칭필름은, 스테아린산, 중질탄산칼슘, 비닐케톤계공중합폴리머, 폴리에틸렌왁스, 젖당, 에틸아세테이트, 메틸메타크릴레이트, 가루우유, 이소부틸알콜, 벤젠과 LMPE를 혼합한 생분해성화합물에 플라스틱수지를 혼합가공한 후 압출하여 성형된다. 여기서, 폴리에틸렌왁스는 폴리에틸엔의 합성과정에서 부산물로 생성되는 고융점폴리에틸렌 왁스를 의미한다. 스테아린산, 폴리에틸렌왁스, 에틸 아세테이트, 이소부틸알콜과 벤젠은 가공첨가제로서 분자간의 결속력, 표면의 미려함 등과 같은 가공성 향상을 위해서 첨가된다. 비닐케톤계공중합폴리머는 매스트배치의 형태로 제공되며 자외선조사시 집광하여 필름의 산화를 촉진시키는 광민첨가제이다. 젖당, 메틸 메타아크릴레이트와 가루우유는 필름의 생분해를 촉진한다. 그리고, LMPE는 분자간의 결속력을 향상시키는 역할을 하고 플라스틱수지는 베이스폴리머로서 필름의 기계적 물성(인열강도, 인장강도 등)을 확보하기 위하여 첨가된다. 여기서 플라스틱수지는 LDPE, LLDPE,HDPE, PP, PSP, PE 중 어느 하나를 또는 이들을 소정량 혼합한 것이다. 그리고, LDPE는 Low Density Polyethylene의 약어로서 저밀도폴리에틸렌을,HDPE는 High Density Polyethylene의 약어로서 고밀도폴리에틸렌을, LLDPE는 Linear Low Density Polyethylene의 약어로서 선형저밀도폴리에틸렌을, PP는 Polypropylene의 약어로서 폴리프로필렌을, 그리고 PSP는 Polystyrene Paper의 약자이다. 또한, LMPE는 Low Molecular Polyethylene약자로서, 저분자 폴리에틸렌을 의미한다. 일반 HDPE,LDPE 등은 분자량이 10,000이상을 가지고 있으나, LMPE는 2000~2500의 저분자량으로 형성되어 있어 제품의 제조시 CaCo3 등의 원활한 융합작을 유도하게 되며, 구성은 Polyethylene wax로 되어 있다. Eco-friendly biodegradable mulching film of the present invention, stearic acid, heavy calcium carbonate, vinyl ketone copolymer copolymer, polyethylene wax, lactose, ethyl acetate, methyl methacrylate, powdered milk, isobutyl alcohol, benzene and LMPE mixed biodegradable The plastic resin is mixed with the compound and then extruded. Here, polyethylene wax refers to a high melting point polyethylene wax produced as a by-product during the synthesis of polyethylene. Stearic acid, polyethylene wax, ethyl acetate, isobutyl alcohol and benzene are added as processing additives to improve processability, such as intermolecular binding, surface beauty. Vinyl ketone copolymer polymerization polymer is provided in the form of a mass batch and is a light additive that promotes oxidation of the film by condensing upon ultraviolet irradiation. Lactose, methyl methacrylate and powdered milk promote biodegradation of the film. In addition, LMPE serves to improve the binding force between molecules and plastic resin is added as a base polymer to secure mechanical properties (tear strength, tensile strength, etc.) of the film. Here, the plastic resin is any one of LDPE, LLDPE, HDPE, PP, PSP, PE, or a predetermined amount thereof. LDPE stands for low density polyethylene as an abbreviation for Low Density Polyethylene, HDPE stands for high density polyethylene as an abbreviation for High Density Polyethylene, LLDPE stands for linear low density polyethylene as an abbreviation for Linear Low Density Polyethylene, PP is polypropylene as an abbreviation for Polypropylene, PSP stands for Polystyrene Paper. In addition, LMPE stands for Low Molecular Polyethylene, which means low molecular polyethylene. General HDPE and LDPE have a molecular weight of 10,000 or more, but LMPE is formed at a low molecular weight of 2000 ~ 2500 to induce a smooth fusion operation such as CaCo 3 when manufacturing a product, and the composition is made of polyethylene wax.
이하에서는, 앞서 본 실시예의 실험예를 살펴보도록 한다. Hereinafter, look at the experimental example of the present embodiment.
시료의 제작Preparation of Sample
스테아린산 2중량%, 중질탄산칼슘 45중량%와 메틸메타크릴레이트 3중량%를 고속혼합기(40KW, 1480RPM)에 넣고 내부 온도 110℃ 하에서 40분간 혼합하여 제1물질을 생성하고, 비닐케톤계공중합폴리머 7.5중량%, 폴리에틸렌왁스 5중량%, 가루우유 15.5중량%, 이소부틸알코올 1.8중량%와 벤젠 1.4중량%을 고속혼합기에 넣고 40℃하에서 30분간 혼합하여 제2물질을 생성하며, 젖당 11.8중량%, 에틸아세테이트 2.5중량%를 혼합기에 넣고 40℃하에서 20분간 혼합하여 제3물질을 생성한다. 2% by weight of stearic acid, 45% by weight of heavy calcium carbonate and 3% by weight of methyl methacrylate were added to a high speed mixer (40KW, 1480RPM) and mixed for 40 minutes under an internal temperature of 110 ° C to produce a first material, and a vinyl ketone copolymer polymer 7.5% by weight, 5% by weight of polyethylene wax, 15.5% by weight of powdered milk, 1.8% by weight of isobutyl alcohol and 1.4% by weight of benzene were added to a high speed mixer and mixed at 40 ° C. for 30 minutes to produce a second substance. 11.8% by weight of lactose 2.5% by weight of ethyl acetate was added to the mixer and mixed at 40 ° C. for 20 minutes to produce a third material.
그리고, 위 제1물질, 제2물질과 제3물질을 고속혼합기(40KW, 1300RPM)에 넣고 90℃하에서 30분간 혼합한 후 60분 후에 혼합기를 개방하여 얻어진 결정체에 LMPE 4.5중량%를 첨가하여 압출기호퍼(37KW)에 투입한다. 여기서, 압출기는 스큐류가 double식이며 그 길이/직경의 비는 28:1이상의 것으로 하며, heating bowl section 1~4까지는 180℃, section 5~8까지는 190℃, section 9~12까지는 210℃를 유지한다. 그리고, 압출기 토출 몰드의 후단에는 wire screen을 수평이동식으로 설치하여 설비가동중에는 이물질을 제거하게 하여 8시간 1회씩 교체하도록 하며, 압출기의 토출구 전면 disc에는 직경2.5mm인 30개의 hold를 통해 생분해성화합물을 토출시킨다. Then, the first material, the second material and the third material in a high-speed mixer (40KW, 1300RPM) and mixed for 30 minutes at 90 ℃ and after 60 minutes the LMPE 4.5wt% was added to the crystal obtained by opening the mixer extruder Put into hopper (37KW). Here, the extruder has a double skew type and its length / diameter ratio is 28: 1 or more, and the heating bowl is maintained at 180 ° C for sections 1-4, 190 ° C for sections 5-8, and 210 ° C for sections 9-12. do. In addition, the wire screen is installed horizontally at the rear end of the extruder ejection mold to remove foreign substances during the operation of the equipment so that they can be replaced once every 8 hours.The biodegradable compound is held through 30 hold diameters of 2.5mm on the front disc of the extruder. Discharge.
그리고, 토출된 생분해성화합물은 4개의 회전식 커터에 의해 두께 0.3~0.5mm 타원형으로 절단되어 송풍기의 풍력에 의해서 직경 300의 덕트를 통해 14m 이송된다. 그리고 이송되는 과정에서 냉각되어 생분해성화합물이 완성된다. Then, the discharged biodegradable compound is cut into an elliptical thickness of 0.3 ~ 0.5mm by four rotary cutters and is transported 14m through a duct 300 diameter by the wind power of the blower. And it is cooled in the transport process to complete the biodegradable compound.
이어서, 위 생분해성화합물 40중량%를 베이스폴리머로 LDPE 12중량%, LLDPE 48중량%와 함께 압출기 호퍼에 투입하고, heating bowl 180~190℃, heating tee 190℃~210℃, heating top 220℃을 유지하면서 두께 0.01~0.02mm인 친환경생분해 농업용 멀칭필름(시험예1)을 제작하였다.Subsequently, 40% by weight of the above biodegradable compound was added to the extruder hopper together with 12% by weight of LDPE and 48% by weight of LLDPE as a base polymer, followed by heating bowl 180-190 ° C, heating tee 190 ° C-210 ° C, and heating top 220 ° C. While maintaining a thickness of 0.01 ~ 0.02mm eco-friendly biodegradable agricultural mulching film (Test Example 1) was produced.
그리고, 베이스폴리머만을 달리하여 다음과 같은 시료를 추가 제작하였다. Then, the following sample was further produced by only changing the base polymer.
(1) 시험예2 내지 비교예 2(1) Test Example 2 to Comparative Example 2
앞서 본 생분해성화합물을 첨가하지 아니한 PP재질의 필름(비교예2), 생분해성화합물을 5중량% 첨가한 필름(시험예2)를 각각 제작하였다. PP film (Comparative Example 2) to which the present biodegradable compound was not added, and a film (Test Example 2) to which 5 wt% of the biodegradable compound was added were prepared.
(2) 시험예3 내지 비교예3(2) Test Example 3 to Comparative Example 3
앞서 본 생분해성화합물을 첨가하지 아니한 PSP재질의 필름(비교예3), 생분 해성화합물을 7중량% 첨가한 필름(시험예3)를 각각 제작하였다. The film of PSP material (Comparative Example 3) to which the present biodegradable compound was not added (Comparative Example 3) and the film to which 7 wt% of the biodegradable compound was added were prepared, respectively.
(3) 시험예4 내지 비교예4(3) Test Example 4 to Comparative Example 4
앞서 본 생분해성화합물을 첨가하지 아니한 PE재질의 필름(비교예4), 생분해성화합물을 5중량% 첨가한 필름(시험예4)를 각각 제작하였다. The PE film without the present biodegradable compound (Comparative Example 4) and the film with the biodegradable compound added 5% by weight (Test Example 4) were prepared, respectively.
실험1: 퇴비화조건에서 플라스틱의 호기성 생분해도 시험Experiment 1: Aerobic Biodegradability Test of Plastics in Composting Conditions
출원인은 한국화학시험연구원에 실험을 의뢰하였고 그 보고서 내용을 다음과 같이 정리하여 본다. Applicant requested the experiment from Korea Testing and Research Institute and summarizes the report as follows.
1. 재질성분분석1. Material Composition Analysis
(1) 재질시험시료(1) Material test sample
생분해도 시험을 실시하기 전에 시험하고자 하는 시료에 대하여 원소분석(N C H O)을 실시하였고 시험시료는 환경부 공고 제2004-110호 생분해성 합성수지 시험기관 지정·공고 중 플라스틱의 생분해도 시험 업무처리지침에 의거하여 위 시험예1의 시료를 절단하여 아래 그림1과 같이 준비하였다. Before conducting biodegradability test, elemental analysis (NCHO) was conducted on the sample to be tested, and the test sample was designated according to the Ministry of Environment's notification of biodegradable synthetic resin testing institute of 2004-110. By cutting the sample of Test Example 1 was prepared as shown in Figure 1 below.
<그림 1><Picture 1>
(2) 재질시험장비 및 방법(2) Material testing equipment and method
모델명 EA1110 Element Analyes System(CE Instrumnets Co., Italy)인 원소분석기를 사용한다. An element analyzer with model name EA1110 Element Analyes System (CE Instrumnets Co., Italy) is used.
원소성분 중 N,C,H는 재질시험시료 1mg정도를 1800℃에서 열분해 후 TCD검출기를 이용하여 분석하며, 나머지 성분인 O는 재질시험시료 1mg정도를 1000℃에서 열분해 후 TCD검출기를 이용하여 분석한다. N, C, H among the elemental components were analyzed by TCD detector after pyrolysis of 1mg of material test sample at 1800 ℃, and the remaining component O was analyzed by TCD detector after pyrolysis of 1mg of material test sample at 1000 ℃. do.
(3) 재질시험결과(3) Material test result
2. 생분해도 시험 2. Biodegradation test
(1) 생분해도시료(1) Biodegradable city materials
위 시험예1의 시료를 2×2cm크기로 절단하여 생분해도시험시료를 아래 그림 2와 같이 준비하였다. The sample of Test Example 1 was cut into 2 × 2 cm size to prepare a biodegradability test sample as shown in Figure 2 below.
<그림 2><Picture 2>
(2) 시험원리 및 방법(2) Test principle and method
생분해도시험시료를 한국산업규격 KSM 3100-1 "퇴비화조건에서 플라스틱의 호기성 생분해도 및 붕괴도 측정" 기준에 의거 호기적 퇴비화 과정 중 발생하는 이산화탄소의 양을 측정하여 유기성 화합물인 분해성 합성수지의 생분해도를 측정한다.The biodegradability test sample was measured by measuring the amount of carbon dioxide generated during the aerobic composting process according to the Korean Industrial Standard KSM 3100-1 "Measuring Aerobic Biodegradability and Disintegration Degree of Plastics in Composting Conditions". Measure
여기서, 퇴비는 생분해에 의해 얻어진 식물성 잔류물로 구성된 혼합물과 기타 유기물, 특정 무기 성분이 포함된 토양을 조절하는 유기물이다. 그리고, 퇴비화는 퇴비생성을 위한 호기화과정을 의미한다.Here, compost is an organic substance that controls a soil composed of a mixture of vegetable residues obtained by biodegradation and other organic substances and certain inorganic components. And, composting means aerobic process for composting.
시험원리는 퇴비에 시료와 표준물질을 넣어 고정한 후 퇴비화용기에 넣고 일정기간동안 퇴비화가 일어나도록 한다. 그리고, 퇴비화과정에서 발생되는 이산화탄소량을 연속적으로 또는 주기적으로 측정하여, 시료와 표준물질의 이론적 최대 이산화탄소 발생량과 실제 이산화탄소 발생량의 비율로 생분해도를 결정하게 된다. 여기서, 이론적 최대 이산화탄소발생량(ThCO2)은 시료 또는 표준물질의 총 유기탄소 함유량으로부터 계산되며, 총 유기탄소 함유량은 앞서 본 재질성분분석에 의해 결정되고, 이론적 최대 이산화탄소발생량은 다음과 같은 공식에 의해 연산된다. Principle of test is to put the sample and standard materials in the compost and fix it in the composting container. In addition, by measuring the amount of carbon dioxide generated in the composting process continuously or periodically, the degree of biodegradation is determined by the ratio between the theoretical maximum carbon dioxide generation amount and the actual carbon dioxide generation amount of the sample and the standard material. Here, the theoretical maximum carbon dioxide generation amount (ThCO 2 ) is calculated from the total organic carbon content of the sample or standard material, the total organic carbon content is determined by the material component analysis described above, and the theoretical maximum carbon dioxide generation amount is determined by the following formula. Is calculated.
ThCO2=MTOT×CTOT×12/44ThCO 2 = M TOT × C TOT × 12/44
MTOT:시험 시작시 퇴비에 첨가된 시험물질 중 총 건조고형분의 양(g)M TOT : Total dry solids (g) of test substances added to the compost at the beginning of the test.
CTOT:시험 물질의 총 건조고형분에 포함된 유기탄소의 비율(g/g)C TOT : percentage of organic carbon in the total dry solids of the test substance (g / g)
44: 이산화탄소의 분자량 12:탄소의 분자량44: molecular weight of carbon dioxide 12: molecular weight of carbon
그리고, 실제 발생된 이산화탄소의 량은 수산화칼륨과 바륨클로라이드 혼합수용액이 담긴 투명 유리관으로 앞서 본 각각의 퇴비화 용기에 1:1로 직결한 상태에서 발생되는 이산화탄소를 포집하여 측정하게 되며, 아래의 식에 의해 연산된다.이 모든 사실은 위 한국산업규격에 상세하게 설명되어 있어 더이상의 상세한 설명은 생략한다.In addition, the actual amount of carbon dioxide generated is measured by capturing carbon dioxide generated in a state of being directly connected to each composting vessel in a transparent glass tube containing potassium hydroxide and barium chloride mixed aqueous solution in a 1: 1 manner. All of these facts are described in detail in the above Korean Industrial Standards, and further explanations are omitted.
(mole 단위) (mole unit)
(mg 단위) in mg
그리고, 생분해도는 다음과 같은 공식에 의거 연산된다. And biodegradability is computed based on the following formula.
(CO2)t=t시간동안 시료 또는 표준물질로부터 발생된 이산화탄소의 누적량(CO 2 ) Cumulative amount of carbon dioxide generated from a sample or standard during t = t hours
(CO2)b=퇴비만 담기 용기에서 발생된 이산화탄소의 누적량(CO 2 ) b = the cumulative amount of carbon dioxide produced in the compost only container
Dt:t시간 동안의 생분해도 D t : Biodegradability during t hours
앞서 설명한 모든 내용은 한국산업규격 KSM 3100-1을 근거로 한 것이다. All the above descriptions are based on Korean Industrial Standard KSM 3100-1.
(3) 퇴비의 특성분석(3) Characterization of compost
퇴비는 상명대학교에서 제조하여 2개월간의 퇴비화기간을 거쳐서 준비되었으며 분석된 특성은 다음 표와 같다. Compost was prepared by Sangmyung University and prepared through a two-month composting period.
[표1:퇴비특성표]Table 1: Composting Table
여기서, 총건조고형분은 퇴비를 105℃에서 항량이 되도록 건조 후 얻은 고형분의 양이며, 휘발성고형분은 위 총건조고형분으로부터 550℃ 소각 후의 잔류물을 뺀 후 얻어진 고형분의 양이다. 휘발성 고형분량은 유기물 함유량의 지표이다. Here, the total dry solids is the amount of solids obtained after drying the compost to yield a constant amount at 105 ℃, volatile solids is the amount of solids obtained after subtracting the residue after incineration at 550 ℃ from the total dry solids. Volatile solids are an indicator of organic matter content.
위 표중 '비고'란에서 보는 바와 같이, 위 퇴비는 수분함유량, 산도, 고형분량, C/N비가 모두 기준 범위 이내이므로, 위 한국산업규격에서 요구하는 퇴비의 요건을 만족하는 것으로 판단된다. As shown in the 'remarks' column of the above table, the above-mentioned compost content of water, acidity, solids, and C / N ratio are all within the standard range, and therefore, it is considered that the compost requirements required by the Korean Industrial Standards are met.
(4) 시험예1과 표준물질의 생분해도 측정(4) Determination of Biodegradability of Test Example 1 and Standards
앞서 설명한 시험예1의 시료 3개를 위 퇴비와 함께 고정하여 3개의 퇴비화용기에 각각 넣고 59일간 관찰하였다. 또한, 20㎛이하인 TLC급 셀룰로오스를 표준물질로 하고 이를 위 퇴비와 함께 고정하여 퇴비화용기에 넣고 59일간 관찰하였다. 그리고, 시편이나 표준물질을 넣지 않은 퇴비만을 퇴비화용기에 넣고 59일간 관찰 하였다. 각각의 경우에 대하여, 이산화탄소발생량을 매일 측정하였고 3개의 퇴비회용기에서 발생되는 이산화탄소량의 평균값(CO2)Bmean을 위 공식에 근거하여 산출하고, 나아가 생분해도의 평균값(Dt)도 산출하여 그 결과를 아래 그래프로 나타내었다.Three samples of Test Example 1 described above were fixed together with gastric compost and placed in three composting containers, respectively, and observed for 59 days. In addition, TLC grade cellulose of 20 μm or less was used as a standard material, which was fixed with stomach compost and placed in a composting container for observation for 59 days. In addition, only the compost without the specimen or standard material was placed in the composting container and observed for 59 days. For each case, the average value of the CO2 that is measurement of the carbon dioxide emissions daily occurred in three manure per vessel (CO 2) calculated on the basis of Bmean in the formula above, and further the mean value (D t) of biodegradability is also calculated The results are shown in the graph below.
<그래프1 이산화탄소발생량> <Graph 1 Carbon Dioxide>
<그래프2 생분해도> <Graph 2 Biodegradation>
위 그래프1에 의하면, 시험예1을 고정한 퇴비의 이산화탄소발생량이 그렇지 않은 퇴비에 비해 많다는 사실을 확인할 수 있었고 시간이 경과함에 따라 이산화탄소발생량이 점진적으로 증가하여 생분해가 진행중임을 알 수 있었다. 또한, 그래프2에 의하면, 시험예1은 표준물질인 셀룰로오즈와 비교하여 이산화탄소발생량이나 생분해도가 낮긴하지만 셀룰로오즈와 같이 시간이 경과함에 따라 점차 증가하고 있어서 셀룰로오즈처럼 자연상태에서 생분해가 진행중임을 알 수 있다. According to the above graph 1, it can be seen that the amount of carbon dioxide generated in the compost fixing the test example 1 is higher than that of the other compost, and as time passes, the amount of carbon dioxide is gradually increased, indicating that biodegradation is in progress. In addition, according to Graph 2, although the amount of carbon dioxide generation or biodegradation is lower than that of cellulose, which is a standard substance, the test example 1 is gradually increasing as time passes, such as cellulose. .
그리고, 59일 시점에서 생분해도를 표준물질과 시편에 대하여 비교하여 보면 다음 표2와 같다. And, comparing the biodegradation of the standard material and the specimen at 59 days as shown in Table 2 below.
[표2:59일 지점에서의 생분해도 비교표]Table 2: Comparison Table of Biodegradability at 59 Days
위 표2에서 확인되다시피, 시험예1은 59일 시점에 38.1%의 생분해도를 보이며 그 생분해도가 표준물질인 셀룰로오즈의 52.4%에 달한다. As shown in Table 2 above, Test Example 1 showed a biodegradability of 38.1% at 59 days, and the biodegradability reached 52.4% of the standard cellulose.
실험2: MITI method에 의한 생분해도 측정Experiment 2: Determination of biodegradation by MITI method
(1) 실험방법(1) Experimental method
10여곳 이상의 오니, 퇴비 및 토양에서 채취하여 혼합한 후 합성배지를 1일 1회 공급하면서 10일 이상 배양하여 이를 접종미생물로 사용하였다. After collecting from more than 10 sludge, compost and soil, and mixed with the culture medium once a day for 10 days or more were used as inoculation microorganisms.
그리고, 접종미생물이 고분자를 분해하는 과정에서 소모하는 산소량을 Respirometer를 사용하여 측정하였다. In addition, the amount of oxygen consumed in the process of inoculating microorganisms during the decomposition of the polymer was measured using a respirometer.
본 실험에서도 표준물질로는 실험1에서와 동일한 셀룰로오스를 사용하였다. In this experiment, the same cellulose was used as the standard material as in Experiment 1.
(2) 실험결과(2) Experiment result
Respirometer로 측정한 산소소모량(mg/L)은 다음의 표3과 같다. Oxygen consumption measured by respirometer (mg / L) is shown in Table 3 below.
[표3: 소모 산소량][Table 3: Oxygen consumption]
위 표에 의하면, 시험예 2 내지 4는 표준물질에 비하여 산소소모량이 낮지만 비교예 2 내지 4에 비하여 현저히 높음을 확인할 수 있었다. According to the above table, Experimental Examples 2 to 4 was confirmed that the oxygen consumption is lower than the reference material, but significantly higher than Comparative Examples 2 to 4.
실험3: 옥외현장에서의 생분해도 측정Experiment 3: Determination of Biodegradability at Outdoor Site
(1)실험방법(1) Experimental method
비교예 2 내지 4와 시험예 1 내지 4를 하천과 토양에 30일동안 각각 침적시킨 후 생분해 정도를 무게감소율, SEM과 AFM을 이용해 시료 표면의 형태 변화를 측정하였으며, 나아가 토양이나 하천에 침적된 시료를 채취하여 현미경으로 관찰하여 박테리아의 서식 여부를 확인하였다.After Comparative Examples 2 to 4 and Test Examples 1 to 4 were deposited in rivers and soils for 30 days, the degree of biodegradation was measured by weight loss rate, SEM and AFM, and the change in the surface of the sample was measured. A sample was taken and observed under a microscope to confirm the presence of bacteria.
(2) 실험결과(2) Experiment result
1) 무게감소율1) weight loss rate
각각의 경우에 무게감소율을 계산하여 그 결과를 아래 표4에 도시하였다.In each case, the weight loss rate was calculated and the results are shown in Table 4 below.
[표4:무게감소율비교표][Table 4: Comparison of weight reduction rate]
위 표4에 기재된 바와 같이, 생분해성화합물을 첨가한 시험예1 내지 4가 첨가하지 않은 비교예 2 내지 4에 비해 무게감소율을 높음을 확인할 수 있었다. 특히,시험예 1은 생분해성화합물의 비율이 시험예 2 내지 3에 비해 높기 때문에 시험예2 내지 4에 비해 높은 무게감소율을 보여 주었고 육안으로도 생분해가 진행중임을 쉽게 확인할 수 있었다. As shown in Table 4 above, it was confirmed that the weight loss rate is higher than Comparative Examples 2 to 4 with the addition of the biodegradable compound was not added. In particular, Test Example 1 showed a high weight loss rate compared to Test Examples 2 to 4 because the ratio of the biodegradable compound is higher than Test Examples 2 to 3, it was easy to confirm that the biodegradation is in progress even with the naked eye.
2)SEM 및 AFM을 통한 시료 표면 거칠기의 변화2) change of surface roughness of sample through SEM and AFM
표면거칠기 변화는 편의상 비교예2와 시험예2만을 비교하였고 그 결과를 아래 도시하였다. The surface roughness change was compared with only Comparative Example 2 and Test Example 2 for convenience, and the results are shown below.
AFM 으로 측정한 비교예2와 시험예2의 3차원적인 표면 모양Three-dimensional surface shape of Comparative Example 2 and Test Example 2 measured by AFM
30일간의 침적후에는 토양이나 하천 모두에 있어서 시험예2의 시료표면이 비교예2에 비해 더욱 거칠어져 있음을 확인할 수 있다. After 30 days of immersion, it can be seen that the sample surface of Test Example 2 is rougher than that of Comparative Example 2 in both soil and rivers.
AFM상에서 측정한 비교예2와 시험예2의 평균거칠기값Average Roughness Values of Comparative Example 2 and Test Example 2 Measured on AFM
30일간의 침적후에는, 시험예2의 표면거칠기 수치가 비교예2에 비해 높음을 확인할 수 있다.After 30 days of immersion, it can be confirmed that the surface roughness value of Test Example 2 is higher than that of Comparative Example 2.
3)시료 표면의 현미경적 관찰3) Microscopic observation of sample surface
토양에 침적한 시료를 채취하여 비교예2와 시험예2의 시료 표면상에 존재하는 박테리아를 현미경적으로 관찰한 결과, 아래 그림에 도시된 바와 같이 시험예2 의 표면에 비교예2에 비해 많은 박테리아가 서식하면서 바이오필름(biofilm)을 형성하고 있음을 확인할 수 있다. As a result of microscopic observation of the bacteria present on the surface of the sample of Comparative Example 2 and Test Example 2, the sample deposited on the soil was found, compared to Comparative Example 2 on the surface of Test Example 2 as shown in the figure below. It can be seen that bacteria inhabit the biofilm.
<비교예2> <시험예2> <Comparative Example 2> <Test Example 2>
앞서 살펴 본 실험 1 내지 3에서 확인된 바와 같이, 시험예 1 내지 4는 비교예2 내지 3에 비해 이산화탄소발생량, 산소소모량, 표면거칠기나 박테리아의 서식정도가 높다는 점을 실험적으로 확인할 수 있었다. 특히 시험예1의 경우, 생분해도가 59일만에 38.1% 정도에 근접하는데, 이는 자연상태에서는 분해되지 않는 비교예 2 내지 4와 비교하여서는 놀라운 결과였다. As confirmed in the above Experiments 1 to 3, Experimental Examples 1 to 4 was confirmed experimentally that the carbon dioxide generation amount, oxygen consumption amount, surface roughness or the degree of habitat of bacteria is higher than Comparative Examples 2 to 3. In particular, in Test Example 1, the biodegradability was close to about 38.1% in 59 days, which was a surprising result compared to Comparative Examples 2 to 4 that do not decompose in the natural state.
본 발명은 생분해성화합물와 베이스폴리머을 소정량 혼합하여 자외선의 조사로 외부에 노출되어 있거나 토양속에 매립되어 있어도 토양의 미생물등에 의해 생분해성화합물뿐만 아니라 베이스폴리머까지도 생분해될 수 있어서 친환경적인 멀칭농법 등에 광범위하게 사용될 수 있다는 효과를 가진다. The present invention is mixed with a predetermined amount of a biodegradable compound and a base polymer, even if exposed to the outside by irradiation of ultraviolet rays or embedded in the soil, biodegradable compounds as well as the base polymer can be biodegradable by microorganisms of the soil, etc. Has the effect that it can be used.
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