KR102523047B1 - Highly flame resistant and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder - Google Patents
Highly flame resistant and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder Download PDFInfo
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Abstract
본 발명은 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치에 관한 것으로, 더욱 상세하게는 폴리올레핀계 고분자 수지, 난연제 혼합물 및 가공조제로 이루어지며, 상기 난연제 혼합물은 고분자 나노클레이 복합체, 폐 폴리올레핀 발포체 분말, 및 친환경 난연제로 이루어진다.
상기의 성분으로 이루어지는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치는 폴리올레핀계 수지와 혼합한 후에 발포성형의 과정을 거치면 난연성, 내열성 및 기계적 물성이 우수할 뿐만 아니라, 할로겐계 난연제 성분이 함유되지 않고 폐 폴리올레핀 발포체 분말이 함유된 난연제 혼합물이 사용되어 친환경적인 발포체를 제공한다.The present invention relates to a flame retardant and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder, and more particularly, to a polyolefin polymer resin, a flame retardant mixture, and a processing aid, wherein the flame retardant mixture is a polymer nanoclay composite. , waste polyolefin foam powder, and an environmentally friendly flame retardant.
The flame retardant and eco-friendly polyolefin nanocomposite master batch using the waste polyolefin foam powder composed of the above components is excellent in flame retardancy, heat resistance, and mechanical properties when mixed with polyolefin resin and subjected to foam molding, as well as halogen-based nanocomposite master batches. A flame retardant mixture containing no flame retardant component and containing waste polyolefin foam powder is used to provide an environmentally friendly foam.
Description
본 발명은 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치에 관한 것으로, 더욱 상세하게는 폴리올레핀계 수지와 혼합한 후에 발포성형의 과정을 거치면 난연성, 내열성 및 기계적 물성이 우수할 뿐만 아니라, 할로겐계 난연제 성분이 함유되지 않고 폐 폴리올레핀 발포체 분말이 함유된 난연제 혼합물이 사용되어 친환경적인 발포체를 제공하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치에 관한 것이다.The present invention relates to a highly flame retardant and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder, and more particularly, it has excellent flame retardancy, heat resistance and mechanical properties when it is mixed with a polyolefin resin and subjected to a foam molding process. In addition, it relates to a flame retardant and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder that provides an environmentally friendly foam by using a flame retardant mixture containing waste polyolefin foam powder without containing a halogen-based flame retardant component.
발포체는 전자기기 등의 내부 절연체, 완충재, 방진재, 차음재, 단열재, 혹은 식품 포장재, 의복용재, 건재 및 자동차나 가전 제품 등의 내장 부품이나 외장 부품용 등으로서 사용되고 있다.Foams are used as internal insulators, cushioning materials, dustproof materials, sound insulation materials, heat insulating materials, food packaging materials, clothing materials, building materials, and interior and exterior parts of automobiles and home appliances.
이러한 발포체에는, 부품으로서 조립될 때에 그 밀봉성 등을 확보한다고 하는 관점에서, 유연성, 쿠션성 및 단열성 등의 특성이 요구되며, 발포체의 재료로서는 폴리에틸렌이나 폴리프로필렌 등의 폴리올레핀계 수지 발포체가 알려져 있다.Such foams are required to have properties such as flexibility, cushioning properties, and thermal insulation properties from the viewpoint of securing their sealing properties when assembled as parts, and polyolefin-based resin foams such as polyethylene and polypropylene are known as foam materials.
상기의 성분으로 이루어지는 발포체는 발포의 배율을 높게 하거나, 폴리올레핀계 수지에 고무 성분 등을 배합하여 소재 자체를 부드럽게 하는 것이 행해지고 있는데, 통상의 폴리에틸렌이나 폴리프로필렌은 고온시에서의 장력, 즉 용융장력이 낮아 고발포 배율을 얻으려고 해도 발포시에 기포벽이 파괴되어 가스 빠짐이 발생하거나 기포의 합일(合一)이 발생하여 발포배율이 높아 부드러운 물성을 나타내는 발포체를 얻는 것이 곤란한 문제점이 있었다.Foams made of the above components are made to increase the expansion rate or to soften the material itself by blending a rubber component with a polyolefin resin. Even when trying to obtain a low foaming ratio, there was a problem in that it was difficult to obtain a foam exhibiting soft physical properties with a high foaming ratio because the cell wall was destroyed during foaming, resulting in gas escape or coalescence of cells.
종래 알려진 난연성 폴리올레핀 발포체로서 한국 공개특허 제10-1997-0042714호는 저밀도폴리에틸렌(LDPE)과 에틸렌비닐공중합체(EVA)만을 단독 혹은 블렌드한 수지에 난연제 및 기타 첨가제를 첨가하여 제조한 ASTM D 2863에 의한 한계산소지수(LOI) 26의 난연성 발포체를 개시한 바 있다. 또한, 일본 공개특허공보 특개2000-106041호는 전선케이블 피복용의 난연성 발포고무 조성물을 제시한 바 있으나, 상기에 나열된 발포체 및 난연성 발포고무 조성물은 난연성을 확보한 반면 발포율이 매우 낮은 문제점이 있었다.As a conventionally known flame retardant polyolefin foam, Korean Patent Publication No. 10-1997-0042714 is based on ASTM D 2863 prepared by adding a flame retardant and other additives to low density polyethylene (LDPE) and ethylene vinyl copolymer (EVA) alone or blended. A flame retardant foam having a limiting oxygen index (LOI) of 26 has been disclosed. In addition, Japanese Unexamined Patent Publication No. 2000-106041 has proposed a flame retardant foam rubber composition for covering wire and cable, but the foam and flame retardant foam rubber composition listed above have a problem in that the foaming rate is very low while securing flame retardancy. .
한편, 종래에는 발포수지층을 형성하기 위한 폴리올레핀을 이용하여 발포체를 제조하는 과정에서 스크랩이 다량 발생하며, 수명이 다한 발포체와 상기 스크랩은 재활용되지 못하고 폐기처분되어 환경오염을 유발하는 문제점이 있었다.On the other hand, conventionally, a large amount of scrap is generated in the process of manufacturing a foam using polyolefin for forming a foamed resin layer, and the foam and the scrap, whose lifespan has expired, are not recycled and disposed of, causing environmental pollution.
이에 본 발명자는 폴리올레핀계 수지와 혼합한 후에 발포성형의 과정을 거치면 난연성, 내열성 및 기계적 물성이 우수할 뿐만 아니라, 할로겐계 난연제 성분이 함유되지 않고 폐 폴리올레핀 발포체 분말이 함유된 난연제 혼합물이 사용되어 친환경적인 발포체를 제공하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 개발함으로써 본 발명을 완성하였다.Therefore, the inventors of the present invention have excellent flame retardancy, heat resistance, and mechanical properties when mixing with polyolefin resin and then undergoing foam molding, and use a flame retardant mixture containing waste polyolefin foam powder without halogen flame retardant components, which is environmentally friendly. The present invention was completed by developing a non-flammable and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder that provides a suitable foam.
본 발명의 목적은 폴리올레핀계 수지와 혼합한 후에 발포성형의 과정을 거치면 난연성, 내열성 및 기계적 물성이 우수할 뿐만 아니라, 할로겐계 난연제 성분이 함유되지 않고 폐 폴리올레핀 발포체 분말이 함유된 난연제 혼합물이 사용되어 친환경적인 발포체를 제공하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 제공하는 것이다.An object of the present invention is to use a flame retardant mixture having excellent flame retardancy, heat resistance and mechanical properties when mixed with polyolefin resin and then subjected to foam molding, and containing waste polyolefin foam powder without containing halogen-based flame retardant components. It is to provide a non-flammable and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder that provides an environmentally friendly foam.
본 발명의 목적은 폴리올레핀계 고분자 수지, 난연제 혼합물 및 가공조제로 이루어지며, 상기 난연제 혼합물은 고분자 나노클레이 복합체, 폐 폴리올레핀 발포체 분말, 및 친환경 난연제로 이루어지는 것을 특징으로 하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 제공함에 의해 달성된다.An object of the present invention is composed of a polyolefin-based polymer resin, a flame retardant mixture, and a processing aid, and the flame retardant mixture is flame retardant using waste polyolefin foam powder, characterized in that it consists of a polymer nanoclay composite, waste polyolefin foam powder, and an eco-friendly flame retardant. And it is achieved by providing an eco-friendly polyolefin-based nanocomposite masterbatch.
본 발명의 바람직한 특징에 따르면, 상기 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치는 폴리올레핀계 고분자 수지 100 중량부, 난연제 혼합물 100 내지 150 중량부 및 가공조제 0.1 내지 10 중량부로 이루어지는 것으로 한다.According to a preferred feature of the present invention, the flame retardant and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder contains 100 parts by weight of a polyolefin polymer resin, 100 to 150 parts by weight of a flame retardant mixture, and 0.1 to 10 parts by weight of a processing aid. to be made
본 발명의 더 바람직한 특징에 따르면, 상기 폴리올레핀계 고분자 수지는 폴리에틸렌, 에틸렌비닐아세테이트 및 폴리프로필렌으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the polyolefin-based polymer resin is made of at least one selected from the group consisting of polyethylene, ethylene vinyl acetate and polypropylene.
본 발명의 더욱 바람직한 특징에 따르면, 상기 난연제 혼합물은 고분자 나노클레이 복합체 10 내지 30 중량%, 폐 폴리올레핀 발포체 분말 10 내지 50 중량%, 및 친환경 난연제 30 내지 80 중량%로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the flame retardant mixture is composed of 10 to 30% by weight of the polymer nanoclay composite, 10 to 50% by weight of waste polyolefin foam powder, and 30 to 80% by weight of an environmentally friendly flame retardant.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 고분자 나노클레이 복합체는 고분자 수지 100 중량부, 나노클레이 1 내지 15 중량부 및 상용화제 1 내지 15 중량부로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the polymeric nanoclay composite is composed of 100 parts by weight of a polymer resin, 1 to 15 parts by weight of nanoclay, and 1 to 15 parts by weight of a compatibilizer.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 상용화제는 폴리에틸렌 그라프트 무수말레인산로 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the compatibilizer is composed of polyethylene graft maleic anhydride.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 폐 폴리올레핀 발포체 분말은 1 내지 10㎛의 입자크기를 나타내며, 폐 폴리올레핀 발포체를 액체질소, 밀링기, 또는 분쇄기로 파쇄하여 제조되는 것으로 한다.According to a further preferred feature of the present invention, the waste polyolefin foam powder has a particle size of 1 to 10 μm, and is prepared by crushing the waste polyolefin foam with liquid nitrogen, a mill, or a grinder.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 친환경 난연제는 무기금속 수산화물 100 중량부, 팽창흑연 30 내지 40 중량부, 인계난연제 60 내지 70 중량부 및 붕산아연 70 내지 90 중량부로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the environmentally friendly flame retardant is composed of 100 parts by weight of an inorganic metal hydroxide, 30 to 40 parts by weight of expanded graphite, 60 to 70 parts by weight of a phosphorus-based flame retardant, and 70 to 90 parts by weight of zinc borate.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 무기금속 수산화물은 수산화알루미늄 및 수산화마그네슘으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the inorganic metal hydroxide is made of at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 가공조제는 폴리에틸렌왁스 및 스테아르산으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the processing aid is made of polyethylene wax and stearic acid.
본 발명에 따른 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치는 폴리올레핀계 수지와 혼합한 후에 발포성형의 과정을 거치면 난연성, 내열성 및 기계적 물성이 우수할 뿐만 아니라, 할로겐계 난연제 성분이 함유되지 않고 폐 폴리올레핀 발포체 분말이 함유된 난연제 혼합물이 사용되어 친환경적인 발포체를 제공하는 탁월한 효과를 나타낸다.The flame retardant and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder according to the present invention has excellent flame retardancy, heat resistance and mechanical properties when mixed with polyolefin resin and subjected to foam molding, as well as halogen-based flame retardant A flame retardant mixture containing no components and waste polyolefin foam powder is used to show an excellent effect of providing an environmentally friendly foam.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a preferred embodiment of the present invention and the physical properties of each component will be described in detail, but this is to be explained in detail so that a person having ordinary knowledge in the art to which the present invention belongs can easily practice the invention, This is not meant to limit the technical spirit and scope of the present invention.
본 발명에 따른 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치는 폴리올레핀계 고분자 수지, 난연제 혼합물 및 가공조제로 이루어지며, 폴리올레핀계 고분자 수지 100 중량부, 난연제 혼합물 100 내지 150 중량부 및 가공조제 0.1 내지 10 중량부로 이루어지는 것이 바람직하다.The highly retardant and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder according to the present invention is composed of a polyolefin polymer resin, a flame retardant mixture and a processing aid, 100 parts by weight of the polyolefin polymer resin and 100 to 150 parts by weight of the flame retardant mixture It is preferably made of 0.1 to 10 parts by weight and processing aid.
상기 폴리올레핀계 고분자 수지는 본 발명에 따른 마스터뱃치가 폴리올레핀 수지와 혼합되었을때, 고른 분산성능을 나타낼 수 있도록 하는 역할을 하며, 폴리올레핀계 고분자 수지와 용융 혼합성이 좋은 성분이면 특별히 한정되지 않고 어떠한 것이든 사용가능하나 폴리에틸렌, 에틸렌비닐아세테이트 및 폴리프로필렌으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것이 바람직하다.The polyolefin-based polymer resin serves to ensure uniform dispersibility when the master batch according to the present invention is mixed with the polyolefin resin, and any component is not particularly limited as long as it has good melt-mixability with the polyolefin-based polymer resin. Any can be used, but it is preferably made of at least one selected from the group consisting of polyethylene, ethylene vinyl acetate and polypropylene.
상기 난연제 혼합물은 100 내지 150 중량부가 함유되며, 고분자 나노클레이 복합체 10 내지 30 중량%, 폐 폴리올레핀 발포체 분말 10 내지 50 중량%, 및 친환경 난연제 30 내지 80 중량%로 이루어지는 것이 바람직하다.The flame retardant mixture contains 100 to 150 parts by weight, preferably composed of 10 to 30% by weight of the polymer nanoclay composite, 10 to 50% by weight of waste polyolefin foam powder, and 30 to 80% by weight of an environmentally friendly flame retardant.
상기 고분자 나노클레이 복합체는 10 내지 30 중량%가 함유되며, 고분자 수지 100 중량부, 나노클레이 1 내지 15 중량부 및 상용화제 1 내지 15 중량부로 이루어지는데, 본 발명에 따른 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치에 내열성과 난연성을 부여하며, 할로겐계 성분이 사용되지 않아 친환경적인 특성을 부여하는 역할을 한다.The polymer nanoclay composite contains 10 to 30% by weight, and is composed of 100 parts by weight of polymer resin, 1 to 15 parts by weight of nanoclay, and 1 to 15 parts by weight of a compatibilizer. Flame retardancy and eco-friendliness It imparts heat resistance and flame retardancy to the polyolefin-based nanocomposite master batch, and plays a role in imparting eco-friendly characteristics as halogen-based components are not used.
상기 고분자 수지는 열가소성인 것을 사용할 수 있는데, 폴리올레핀으로 이루어지며, 상기 폴리올레핀으로는 폴리에틸렌, 에틸렌비닐아세티에트 및 폴리프로필렌으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것이 더욱 바람직하다.The polymer resin may be thermoplastic, and is made of polyolefin, and the polyolefin is more preferably made of at least one selected from the group consisting of polyethylene, ethylene vinyl acetate, and polypropylene.
상기 나노클레이는 1 내지 15 중량부가 함유되며, 상기 고분자 나노클레이 복합체의 내열성 및 난연성을 향상시키는 역할을 하는데, 통상적으로 사용되는 것이면 특별히 한정되지 않고 어떠한 것이든 사용가능하나, 구체적으로는 몬모릴로나이트, 헥토라이트, 벤토나이트, 버미큘라이트 및 볼콘스코이트 등이 사용될 수 있다. 상기 몬모릴로나이트는 유기화합물로 개질된 형태이며, 구체적으로는 Southern Clay Products사의 제품의 Cloisite 10A, Cloisite 15A, Cloisite 20A, Cloisite 25A, Cloisite 30B, Cloisite 93A 등을 사용할 수 있다.The nanoclay is contained in an amount of 1 to 15 parts by weight, and serves to improve the heat resistance and flame retardancy of the polymer nanoclay composite. As long as it is commonly used, it is not particularly limited and any one can be used, but specifically, montmorillonite, hecto Wright, bentonite, vermiculite, and volkonscoite and the like can be used. The montmorillonite is a form modified with an organic compound, and specifically, Cloisite 10A, Cloisite 15A, Cloisite 20A, Cloisite 25A, Cloisite 30B, Cloisite 93A, etc. manufactured by Southern Clay Products may be used.
또한, 상기 나노클레이가 함유되면 고분자 나노클레이 복합체는 분해 온도가 50% 이상 증가(50 내지 150℃ 증가)하여 본 발명에 따른 마스터뱃치의 내열성이 향상되며, 복합구조{Intercalation(삽입형) 구조 및 exfoliation(박리형) 구조가 공존함}로 챠 형성 극대화를 통한 난연성이 향상되고 화염전파 차단력이 향상된다.In addition, when the nanoclay is contained, the decomposition temperature of the polymer nanoclay composite increases by more than 50% (increased by 50 to 150 ° C), thereby improving the heat resistance of the master batch according to the present invention, and the composite structure {intercalation (insertion type) structure and exfoliation (peelable) structure coexists} improves flame retardancy through maximization of char formation and improves flame propagation blocking power.
상기 고분자 나노클레이 복합체는 종래 믹싱물이나 컴파운드에서의 구조와 달리 나노클레이 층간에 고분자가 삽입된 형태(삽입형, intercalation)와 나노클레이 층상구조가 박리되어 고분자 내에 존재하는 형태(박리형, exfoliation)로 제조되기 때문에, 난연성 및 차폐성이 향상된 마스터뱃치를 제공할 수 있다.Unlike the structure of conventional mixtures or compounds, the polymer nanoclay composite has a form in which a polymer is inserted between nanoclay layers (insertion type, intercalation) and a form in which the layered structure of nanoclay is exfoliated and exists in the polymer (exfoliation type, exfoliation) Since it is prepared, it is possible to provide a masterbatch with improved flame retardancy and shielding properties.
이때, 상기 나노클레이의 함량이 1 중량부 미만이면 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치의 압축강도와 같은 기계적 물성의 향상 효과가 미미하며, 상기 나노클레이의 함량이 15 중량부를 초과하게 되면 상기 고분자 수지에 대해 분산 효과가 저하되면서 나노클레이 성분 간의 뭉침현상이 발생하여 고분자 나노클레이 복합체의 물성이 저하될 수 있다.At this time, if the content of the nanoclay is less than 1 part by weight, the effect of improving the mechanical properties such as the compressive strength of the non-flammable and eco-friendly polyolefin nanocomposite master batch using the waste polyolefin foam powder is insignificant, and the content of the nanoclay is When the amount exceeds 15 parts by weight, the dispersing effect of the polymer resin is reduced, and agglomeration between the nanoclay components occurs, so that the physical properties of the polymer nanoclay composite may be deteriorated.
상기 상용화제는 1 내지 15 중량부가 혼합되며, 폴리에틸렌 그라프트 무수말레인산로 이루어지는데, 상기 고분자 수지와 나노클레이가 고르게 혼합될 수 있도록 하기 때문에, 균질한 물성을 나타내는 고분자 나노클레이 복합체를 제공하는 역할을 한다.The compatibilizer is mixed in an amount of 1 to 15 parts by weight and is composed of polyethylene graft maleic anhydride. Since the polymer resin and nanoclay can be mixed evenly, it serves to provide a polymer nanoclay composite exhibiting homogeneous physical properties do.
상기 상용화제의 함량이 1 중량부 미만이면 상기의 효과가 미미하며, 상기 상용화제의 함량이 15 중량부를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 지나치게 많은 양이 함유되는 것으로 고분자 나노클레이 복합체의 물성을 저하시킬 수 있다.If the content of the compatibilizer is less than 1 part by weight, the above effect is insignificant, and if the content of the compatibilizer exceeds 15 parts by weight, the above effect is not greatly improved and an excessively large amount is contained in the polymer nanoclay composite. may deteriorate its properties.
상기 고분자 나노클레이 복합체는 고분자 수지, 나노클레이, 및 상용화제를 혼합기에 투입하고, 200 RPM 이상의 고속, 바람직하게는 200 내지 500 RPM의 고속, 180 ℃ 이상의 고온, 바람직하게는 180 내지 220 ℃의 고온, 5 min 이하의 단시간, 바람직하게는 3 내지 5 min의 단시간으로 혼합하여 제조할 수 있다.The polymer nanoclay composite is prepared by adding a polymer resin, nanoclay, and a compatibilizer to a mixer, at a high speed of 200 RPM or higher, preferably at a high speed of 200 to 500 RPM, at a high temperature of 180 ° C or higher, and preferably at a high temperature of 180 to 220 ° C. , It can be prepared by mixing in a short time of 5 min or less, preferably in a short time of 3 to 5 min.
상기 폐 폴리올레핀 발포체 분말은 10 내지 50 중량%가 함유되며, 폐기 처분되는 폐 폴리올레핀 발포체를 재활용하기 때문에 친환경적인 효과를 나타내는 마스터뱃치를 제공하는 역할을 한다. 상기 폐 폴리올레핀 발포체 분말은 1 내지 10㎛의 입자크기를 나타내며, 폐 폴리올레핀 발포체를 액체질소로 파쇄하거나, 밀링기, 특히 고속밀링기로 파쇄하거나, 분쇄기로 분쇄하여 제조되는 것이 바람직하다.The waste polyolefin foam powder contains 10 to 50% by weight, and serves to provide a masterbatch that exhibits environmentally friendly effects because waste polyolefin foam that is disposed of is recycled. The waste polyolefin foam powder has a particle size of 1 to 10 μm, and is preferably prepared by crushing the waste polyolefin foam with liquid nitrogen, crushing with a milling machine, particularly a high-speed milling machine, or pulverizing the waste polyolefin foam with a pulverizer.
상기와 같이 액체질소, 밀링기, 또는 분쇄기를 통해 제조되는 폐 폴리올레핀 발포체 분말은 원물의 물리적 손상 및 탄화 등이 최소화되어 발포체가 갖는 물성이 유지될 뿐만 아니라, 다양한 입자크기로 제조가 용이한 효과를 나타낸다.As described above, the waste polyolefin foam powder produced through liquid nitrogen, a mill, or a grinder minimizes physical damage and carbonization of the original material, so that the physical properties of the foam are maintained, and it is easy to manufacture in various particle sizes. .
상기 폐 폴리올레핀 발포체 분말의 입자크기가 1㎛ 미만이면 쉽게 비산되어 작업장을 오염시키고, 뭉침현상으로 인해 상기 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 구성하는 성분들과 고르게 혼합되지 못하며, 상기 폐 폴리올레핀 발포체 분말의 입자크기가 10㎛를 초과하게 되면 상기 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 구성하는 성분들과의 혼합성이 저하된다.If the particle size of the waste polyolefin foam powder is less than 1 μm, it is easily scattered and contaminates the workplace, and due to aggregation, it is not evenly mixed with the components constituting the highly flammable and eco-friendly polyolefin nanocomposite master batch, and the waste When the particle size of the polyolefin foam powder exceeds 10 μm, mixing properties with the components constituting the highly retardant and eco-friendly polyolefin nanocomposite master batch are deteriorated.
상기 친환경 난연제는 30 내지 80 중량%가 함유되며, 상기 난연제 혼합물에 난연성능을 부여하여 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치가 제공될 수 있도록 하는 역할을 하는데, 무기금속 수산화물 100 중량부, 팽창흑연 30 내지 40 중량부, 인계난연제 60 내지 70 중량부 및 붕산아연 70 내지 90 중량부로 이루어지는 것이 바람직하다.The eco-friendly flame retardant contains 30 to 80% by weight, and serves to provide flame retardant performance to the flame retardant mixture to provide a highly retardant and eco-friendly polyolefin nanocomposite master batch using waste polyolefin foam powder. It is preferably composed of 100 parts by weight of metal hydroxide, 30 to 40 parts by weight of expanded graphite, 60 to 70 parts by weight of a phosphorus-based flame retardant, and 70 to 90 parts by weight of zinc borate.
상기 무기금속 수산화물은 친환경 난연제의 주재료가 되는 성분으로 친환경성과 우수한 난연성을 나타내어 본 발명에 따른 마스터뱃치에 난연성을 부여하는 역할을 하는데, 산화알루미늄 및 수산화마그네슘으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것이 바람직하다.The inorganic metal hydroxide is the main component of the eco-friendly flame retardant and exhibits eco-friendliness and excellent flame retardancy and serves to impart flame retardancy to the master batch according to the present invention. It is preferably composed of at least one selected from the group consisting of aluminum oxide and magnesium hydroxide. do.
상기 팽창흑연은 30 내지 40 중량부가 함유되며, 마스터뱃치에 단열성을 부여하는 역할을 하는데, 흑연을 물로 정제한 후 황산으로 처리하여 1차 팽창을 시킨 후 이를 다시 정제수로 정제하고 열을 가하면 2차 팽창하는데, 황산 및 열처리를 통하여 최초의 흑연은 수십 내지 수백 배로 팽창하는 과정을 통해 제조된다.The expanded graphite is contained in an amount of 30 to 40 parts by weight, and serves to impart insulation to the master batch. After purifying the graphite with water, treating it with sulfuric acid for primary expansion, purifying it again with purified water and applying heat, the second In order to expand, the first graphite is produced through a process of expanding to several tens to hundreds of times through sulfuric acid and heat treatment.
상기의 과정을 통해 제조되는 팽창흑연의 일반적인 제조방법을 살펴보면, 천연광산으로부터 흑연을 채굴한 후, 분쇄 및 수분급의 공정을 거쳐 흑연을 만들고, 이 흑연을 황산과 같은 강산을 이용하여 1차 팽창시키고 고온 및 알칼리 상태에서 소결한 후에 세정 공정을 거쳐 순도 99.5%의 흑연을 만들며, 이 세정된 흑연을 예열을 통하여 흑연을 팽창시켜 제조한다.Looking at the general manufacturing method of expanded graphite manufactured through the above process, after mining graphite from a natural mine, making graphite through a process of crushing and water supply, the graphite is first expanded using a strong acid such as sulfuric acid. After sintering at high temperature and in an alkaline state, graphite with a purity of 99.5% is made through a cleaning process, and the cleaned graphite is prepared by expanding graphite through preheating.
팽창흑연은 고상층을 형성하는 난연제로서 팽창된 카본층이 절연층으로 작용하여 열의 이동을 방해하는데, 비할로겐 타입의 저발연성 친환경 난연제이며, 흑연이 열처리에 의해 팽창되게 되면, 층을 이루는 면에 대하여 수직한 방향으로는 단열성이 우수한 특성을 나타낸다. 또한, 팽창흑연은 독성이 없고, 가벼우며, 할로겐 성분을 함유하지 않고, 물에 불용성이며, 유독가스를 발생하지 않는 등의 장점을 가지고 있다.Expanded graphite is a flame retardant that forms a solid layer, and the expanded carbon layer acts as an insulating layer to prevent heat transfer. In the direction perpendicular to the surface, it exhibits excellent thermal insulation properties. In addition, expanded graphite has advantages such as being non-toxic, light, not containing halogen components, insoluble in water, and not generating toxic gas.
상기 팽창흑연의 함량이 30 중량부 미만이면 난연성 및 단열성의 효과가 미미하며, 상기 팽창흑연의 함량이 40 중량부를 초과하게 되면 발포체의 기계적 물성이 저하될 수 있다.If the content of the expanded graphite is less than 30 parts by weight, the effects of flame retardancy and heat insulation are insignificant, and if the content of the expanded graphite exceeds 40 parts by weight, mechanical properties of the foam may be deteriorated.
상기 인계난연제는 60 내지 70 중량부가 함유되며, 인산 에스테르, 인산 에스테르의 올리고머, 무기 인 화합물, 폴리인산암모늄, 멜라민 폴리인산암모늄 및 인산암모늄으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는데, 마스터뱃치에 난연성을 부여하는 역할을 한다.The phosphorus-based flame retardant contains 60 to 70 parts by weight, and is composed of at least one selected from the group consisting of phosphoric acid esters, oligomers of phosphoric acid esters, inorganic phosphorus compounds, ammonium polyphosphate, melamine polyammonium phosphate, and ammonium phosphate. plays a role in giving
상기 인계난연제의 함량이 60 중량부 미만이면 난연효과가 미미하며, 상기 인계난연제의 함량이 70 중량부를 초과하게 되면 고분자 수지의 가공성 및 내충격성 등이 저하될 수 있다.If the content of the phosphorus-based flame retardant is less than 60 parts by weight, the flame retardant effect is insignificant, and if the content of the phosphorus-based flame retardant exceeds 70 parts by weight, processability and impact resistance of the polymer resin may be deteriorated.
상기 붕산아연은 70 내지 90 중량부가 함유되며, 고분자 수지와 난연제 혼합물을 구성하는 성분들의 결속력을 향상시키는 역할을 하는데, 상기 붕산아연의 함량이 70 중량부 미만이면 상기의 효과가 미미하며, 상기 붕산아연의 함량이 90 중량부를 초과하게 되면 본 발명을 통해 제조되는 마스터뱃치의 점도가 지나치게 증가하여 바람직하지 못하다.The zinc borate is contained in 70 to 90 parts by weight, and serves to improve the binding force of the components constituting the polymer resin and the flame retardant mixture. If the content of the zinc borate is less than 70 parts by weight, the above effect is insignificant, and the boric acid When the content of zinc exceeds 90 parts by weight, the viscosity of the masterbatch prepared through the present invention increases excessively, which is not preferable.
상기 가공조제는 0.1 내지 10 중량부가 함유되며, 폴리에틸렌왁스 및 스테아르산으로 이루어지는데, 폴리에틸렌 왁스와 스테아르산이 1:1의 중량부로 혼합되어 이루어지는 것이 바람직하며, 상기 폴리올레핀계 고분자 수지와 상기 난연제 혼합물이 고르게 혼합되도록 할 뿐만 아니라, 상기 폴리올레핀계 고분자 수지 및 본 발명을 통해 제조되는 마스터뱃치가 폴리올레핀계 수지와 혼합되는 경우에 폴리올레핀계 수지의 가공성을 향상시켜 다양한 형태로 성형할 수 있도록 하는 역할을 한다.The processing aid contains 0.1 to 10 parts by weight, and is composed of polyethylene wax and stearic acid. It is preferable that polyethylene wax and stearic acid are mixed in a weight part of 1:1, and the polyolefin-based polymer resin and the flame retardant mixture are evenly mixed. In addition to being mixed, when the polyolefin-based polymer resin and the master batch prepared through the present invention are mixed with the polyolefin-based resin, it serves to improve the processability of the polyolefin-based resin so that it can be molded into various shapes.
상기 가공조제의 함량이 0.1 중량부 미만이면 상기의 효과가 미미하며, 상기 가공조제의 함량이 10 중량부를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 본 발명을 통해 제조된 마스터뱃치가 적용된 성형품의 기계적 물성을 저하시킬 수 있다.If the content of the processing aid is less than 0.1 parts by weight, the above effect is insignificant, and if the content of the processing aid exceeds 10 parts by weight, the above effect is not greatly improved, and the molded article to which the master batch manufactured through the present invention is applied is applied. may deteriorate its mechanical properties.
이하에서는, 본 발명에 따른 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치의 제조방법 및 그 제조방법으로 제조된 마스터뱃치가 사용된 발포체의 물성을 실시예를 들어 설명하기로 한다.Hereinafter, a method for producing a highly flame retardant and eco-friendly polyolefin nanocomposite masterbatch using waste polyolefin foam powder according to the present invention and physical properties of the foam using the masterbatch prepared by the method will be described with examples. do.
<제조예 1> 고분자 나노클레이 복합체의 제조<Preparation Example 1> Preparation of polymer nanoclay composite
고분자 수지(폴리에틸렌) 100 중량부, 나노클레이(Cloisite 10A) 7 중량부 및 상용화제(폴리에틸렌 그라프트 무수말레인산) 7 중량부를 혼합기 또는 이축압출기에 투입하고, 고속 (>200 RPM), 고온 (>180 ℃), 단시간 (<5 min.) 하에서 고분자 나노복합체를 제조하였다.100 parts by weight of polymer resin (polyethylene), 7 parts by weight of nanoclay (Cloisite 10A), and 7 parts by weight of compatibilizer (polyethylene graft maleic anhydride) were put into a mixer or twin-screw extruder, and high speed (>200 RPM), high temperature (>180 RPM) ℃), a polymer nanocomposite was prepared under a short time (<5 min.).
<제조예 2> 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치의 제조<Preparation Example 2> Preparation of flame retardant and eco-friendly polyolefin nanocomposite master batch using waste polyolefin foam powder
폴리올레핀계 고분자 수지 100 중량부, 상기 제조예 1에서 제조한 고분자 나노클레이 복합체 20 중량%, 폐 폴리올레핀 발포체 분말 30 중량% 및 친환경 난연제{무기금속 수산화물(수산화마그네슘) 100 중량부, 팽창흑연 35 중량부, 인계난연제(암모늄폴리포스페이트) 65 중량부 및 붕산아연 80 중량부} 50 중량%가 혼합된 난연제 혼합물 125 중량부, 가공조제(폴리에틸렌 왁스와 스테아르산의 1: 1 혼합물) 2.5 중량부를 혼합기에 투입하고, 120±5 ℃에서 혼합한 후, 일축 압출기에서 압출성형 및 펠렛화하고, 냉각하여 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 제조하였다.100 parts by weight of polyolefin-based polymer resin, 20% by weight of polymer nanoclay composite prepared in Preparation Example 1, 30% by weight of waste polyolefin foam powder, and eco-friendly flame retardant {inorganic metal hydroxide (magnesium hydroxide) 100 parts by weight, 35 parts by weight of expanded graphite 65 parts by weight of a phosphorus-based flame retardant (ammonium polyphosphate) and 80 parts by weight of zinc borate} 125 parts by weight of a flame retardant mixture in which 50% by weight was mixed, and 2.5 parts by weight of a processing aid (a 1: 1 mixture of polyethylene wax and stearic acid) were added to the mixer And, after mixing at 120 ± 5 ℃, extruded and pelletized in a single screw extruder, and cooled to prepare a highly flammable and eco-friendly polyolefin nanocomposite master batch using waste polyolefin foam powder.
<제조예 3> 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치의 제조<Preparation Example 3> Preparation of flame retardant and eco-friendly polyolefin nanocomposite master batch using waste polyolefin foam powder
상기 제조예 2와 동일하게 진행하되, 상기 제조예 1을 통해 제조된 고분자 나노클레이 복합체, 폐 폴리올레핀 발포체 분말 및 친환경 난연제로 이루어진 난연제 혼합물 100 중량부 및 가공조제 0.5 중량부 혼합하여 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 제조하였다.Proceed in the same manner as in Preparation Example 2, but by mixing 100 parts by weight of a flame retardant mixture composed of the polymer nanoclay composite prepared in Preparation Example 1, waste polyolefin foam powder, and an eco-friendly flame retardant, and 0.5 part by weight of a processing aid to obtain waste polyolefin foam powder. A high-resistance and eco-friendly polyolefin-based nanocomposite masterbatch was prepared.
<제조예 4> 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치의 제조<Preparation Example 4> Preparation of flame retardant and eco-friendly polyolefin nanocomposite master batch using waste polyolefin foam powder
상기 제조예 2와 동일하게 진행하되, 상기 제조예 1을 통해 제조된 고분자 나노클레이 복합체, 폐 폴리올레핀 발포체 분말 및 친환경 난연제로 이루어진 난연제 혼합물 150 중량부 및 가공조제 10 중량부 혼합하여 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 제조하였다.Proceed in the same manner as in Preparation Example 2, but by mixing 150 parts by weight of a flame retardant mixture composed of the polymer nanoclay composite prepared in Preparation Example 1, waste polyolefin foam powder, and an eco-friendly flame retardant, and 10 parts by weight of a processing aid to obtain waste polyolefin foam powder. A high-resistance and eco-friendly polyolefin-based nanocomposite masterbatch was prepared.
<실시예 1> <Example 1>
폴리에틸렌 100 중량부에 상기 제조예 2를 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치 120 중량부, 110~120℃의 온도에서 제조된 발포제 마스터뱃치 (폴리에틸렌 75% : 발포제(아조디카본아마이드) 25%) 160중량부 및 110~120℃에서 혼합하여 제조한 가교제 마스터뱃치 (폴리에틸렌 96% : 가교제(다이큐밀퍼옥사이드) 4%) 25 중량부를 압출기에 투입하여 약 120℃의 온도에서 시트형태로 압출하고, 시트형태로 압출된 압출물을 발포로에 투입하여 180~210℃의 온도에서 약 20분 동안 가교 및 발포한 후에 상온으로 냉각하고 절단하여 고난연성 및 친환경성 폴리올레핀 발포체를 제조하였다.100 parts by weight of polyethylene 120 parts by weight of flame retardant and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder prepared in Preparation Example 2, foaming agent masterbatch prepared at a temperature of 110 to 120 ° C (polyethylene 75% : Blowing agent (azodicarbonamide) 25%) 160 parts by weight and a crosslinking agent masterbatch prepared by mixing at 110 ~ 120 ℃ (polyethylene 96%: crosslinking agent (dicumyl peroxide) 4%) 25 parts by weight is put into the extruder to about It is extruded in the form of a sheet at a temperature of 120 ° C, and the extruded product extruded in the form of a sheet is put into a foaming furnace, crosslinked and foamed at a temperature of 180 ~ 210 ° C for about 20 minutes, then cooled to room temperature and cut to produce high-resistance and eco-friendly A polyolefin foam was prepared.
<실시예 2> <Example 2>
상기 실시예 1과 동일하게 진행하되, 상기 제조예 3을 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 사용하여 고난연성 및 친환경성 폴리올레핀 발포체를 제조하였다.In the same manner as in Example 1, a highly retardant and eco-friendly polyolefin foam was prepared using a non-flammable and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder prepared in Preparation Example 3.
<실시예 3><Example 3>
상기 실시예 1과 동일하게 진행하되, 상기 제조예 4를 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 사용하여 고난연성 및 친환경성 폴리올레핀 발포체를 제조하였다.In the same manner as in Example 1, a highly retardant and eco-friendly polyolefin foam was prepared using a highly flammable and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder prepared in Preparation Example 4.
<실시예 4> <Example 4>
에틸렌비닐아세테이트 100 중량부에 상기 제조예 2를 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치 120 중량부, 110~120℃의 온도에서 제조된 발포제 마스터뱃치 (에틸렌비닐아세테이트 75% : 발포제(아조디카본아마이드) 25%) 160 중량부, 110~120℃에서 혼합하여 제조한 가교제 마스터뱃치 (에틸렌비닐아세테이트 96%: 가교제(다이큐밀퍼옥사이드) 4%) 25 중량부를 압출기에 투입하여 약 120℃의 시트형태로 압출하고, 시트형태로 압출된 압출물을 발포로에 투입하여 180~210℃의 온도에서 20분 동안 가교 및 발포한 후에 상온으로 냉각하고 절단하여 고난연성 및 친환경성 폴리올레핀 발포체를 제조하였다.100 parts by weight of ethylene vinyl acetate 120 parts by weight of a highly retardant and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder prepared in Preparation Example 2, a foaming agent masterbatch prepared at a temperature of 110 to 120 ° C. (Ethylene Vinyl acetate 75%: foaming agent (azodicarbonamide) 25%) 160 parts by weight, crosslinking agent masterbatch prepared by mixing at 110-120 ° C (ethylene vinyl acetate 96%: crosslinking agent (dicumyl peroxide) 4%) 25 weight The part is put into an extruder and extruded into a sheet at about 120 ° C, and the extruded product extruded in a sheet form is put into a foaming furnace, crosslinked and foamed at a temperature of 180 to 210 ° C for 20 minutes, cooled to room temperature, cut, and solidified. A flame retardant and environmentally friendly polyolefin foam was prepared.
<실시예 5><Example 5>
상기 실시예 4와 동일하게 진행하되, 상기 제조예 3을 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 사용하여 고난연성 및 친환경성 폴리올레핀 발포체를 제조하였다.In the same manner as in Example 4, a highly retardant and eco-friendly polyolefin foam was prepared using a highly flammable and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder prepared in Preparation Example 3.
<실시예 6><Example 6>
상기 실시예 4와 동일하게 진행하되, 상기 제조예 4를 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치를 사용하여 고난연성 및 친환경성 폴리올레핀 발포체를 제조하였다.In the same manner as in Example 4, a highly retardant and eco-friendly polyolefin foam was prepared using a highly flammable and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder prepared in Preparation Example 4.
상기 제조예 2 내지 4를 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치 및 상기 실시예 1 내지 6을 통해 제조된 고난연성 및 친환경성 폴리올레핀 발포체의 유해성분 함유 여부를 측정하여 아래 표 1에 나타내었다.Whether or not the highly retardant and eco-friendly polyolefin nanocomposite masterbatch using the waste polyolefin foam powder prepared in Preparation Examples 2 to 4 and the highly retardant and eco-friendly polyolefin foam prepared in Examples 1 to 6 contain harmful ingredients was measured and shown in Table 1 below.
{단, 유해성분 함유 여부는 IEC 62321을 이용하여 6대 유해물질의 함유여부를 확인하는 방법을 이용하였다.}{However, the IEC 62321 was used to determine whether or not the harmful ingredients were contained.}
상기 표 1에 나타낸 것처럼, 본 발명의 제조예 2 내지 4를 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치 및 상기 실시예 1 내지 6을 통해 제조된 고난연성 및 친환경성 폴리올레핀 발포체는 유해성분이 함유되지 않아 친환경적인 것을 알 수 있었다.As shown in Table 1, the highly retardant and eco-friendly polyolefin nanocomposite master batch using the waste polyolefin foam powder prepared through Preparation Examples 2 to 4 of the present invention and the high retardancy and It was found that the eco-friendly polyolefin foam is environmentally friendly because it does not contain harmful components.
상기 제조예 2 내지 4를 통해 제조된 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치의 난연성 및 건조감량을 측정하여 아래 표 2에 나타내었다.The flame retardancy and loss on drying of the non-flammable and eco-friendly polyolefin nanocomposite master batch using the waste polyolefin foam powder prepared in Preparation Examples 2 to 4 were measured and are shown in Table 2 below.
{단, 난연성은 KSM ISO 4589-2의 측정방법을 이용하였으며, 건조감량은 KSM 0009:2010의 측정방법을 이용하였다.}{However, the measurement method of KSM ISO 4589-2 was used for flame retardancy, and the measurement method of KSM 0009:2010 was used for loss on drying.}
또한, 상기 실시예 1 내지 6을 통해 제조된 고난연성 및 친환경성 폴리올레핀 발포체의 난연성, 단열성 및 내충격성을 측정하여 아래 표 3에 나타내었다.In addition, the flame retardancy, heat insulation and impact resistance of the highly flame retardant and eco-friendly polyolefin foams prepared in Examples 1 to 6 were measured and shown in Table 3 below.
{단, 난연성은 KSM ISO 4589-2의 측정방법을 이용하였으며, 단열성은 KSL 9016의 측정방법을 이용하였고, 내충격성은 실시예 1 내지 6을 통해 제조된 폴리올레핀 발포체를 가로 150mm×세로150mm×두께0.9mm로 절단하여 시편화하고 JIS P8134(1976)의 측정방법을 이용하였다.}{However, the flame retardancy was measured by KSM ISO 4589-2, the insulation by KSL 9016, and the impact resistance of the polyolefin foam prepared in Examples 1 to 6 was 150 mm × 150 mm × thickness 0.9 It was cut into mm to make a specimen, and the measurement method of JIS P8134 (1976) was used.}
상기 표 3에 나타낸 것처럼, 본 발명의 실시예 1 내지 6을 통해 제조된 고난연성 및 친환경성 폴리올레핀 발포체는 난연성, 단열성 및 내충격성이 우수한 것을 알 수 있다.As shown in Table 3, it can be seen that the flame retardant and eco-friendly polyolefin foams prepared in Examples 1 to 6 of the present invention have excellent flame retardancy, heat insulation and impact resistance.
또한, 폐 폴리올레핀 발포체 분말이 함유되어, 단열성과 내충격성이 우수한 것을 알 수 있다.In addition, it can be seen that the waste polyolefin foam powder is contained, and thus the heat insulating properties and impact resistance are excellent.
따라서, 본 발명에 따른 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치는 폴리올레핀계 수지와 혼합한 후에 발포성형의 과정을 거치면 난연성, 단열성, 내열성 및 기계적 물성이 우수할 뿐만 아니라, 할로겐계 성분이 함유되지 않고 폐 폴리올레핀 발포체 분말이 함유된 난연제 혼합물이 사용되어 친환경적인 발포체를 간단한 공정으로 제조할 수 있다.Therefore, the flame retardant and eco-friendly polyolefin nanocomposite master batch using the waste polyolefin foam powder according to the present invention has excellent flame retardancy, heat insulation, heat resistance and mechanical properties when mixed with polyolefin resin and subjected to foam molding. , A flame retardant mixture containing waste polyolefin foam powder without halogen components is used, so that an environmentally friendly foam can be produced by a simple process.
Claims (8)
상기 난연제 혼합물은 고분자 나노클레이 복합체 10 내지 30 중량%, 폐 폴리올레핀 발포체 분말 10 내지 50 중량%, 및 친환경 난연제 30 내지 80 중량%로 이루어지며,
상기 고분자 나노클레이 복합체는 고분자 수지 100 중량부, 나노클레이 1 내지 15 중량부 및 상용화제 1 내지 15 중량부로 이루어지며,
친환경 난연제는 무기금속 수산화물 100 중량부, 팽창흑연 30 내지 40 중량부, 인계난연제 60 내지 70 중량부 및 붕산아연 70 내지 90 중량부로 이루어지는 것을 특징으로 하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치.100 parts by weight of a polyolefin polymer resin, 100 to 150 parts by weight of a flame retardant mixture, and 0.1 to 10 parts by weight of a processing aid,
The flame retardant mixture consists of 10 to 30% by weight of the polymer nanoclay composite, 10 to 50% by weight of waste polyolefin foam powder, and 30 to 80% by weight of an eco-friendly flame retardant,
The polymer nanoclay composite is composed of 100 parts by weight of polymer resin, 1 to 15 parts by weight of nanoclay, and 1 to 15 parts by weight of a compatibilizer,
The eco-friendly flame retardant is composed of 100 parts by weight of inorganic metal hydroxide, 30 to 40 parts by weight of expanded graphite, 60 to 70 parts by weight of phosphorus-based flame retardant, and 70 to 90 parts by weight of zinc borate. based nanocomposite masterbatch.
상기 폴리올레핀계 고분자 수지는 폴리에틸렌, 에틸렌비닐아세테이트 및 폴리프로필렌으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치.The method of claim 1,
The polyolefin-based polymer resin is a high-resistance and eco-friendly polyolefin-based nanocomposite master batch using waste polyolefin foam powder, characterized in that it consists of at least one selected from the group consisting of polyethylene, ethylene vinyl acetate and polypropylene.
상기 폐 폴리올레핀 발포체 분말은 1 내지 10㎛의 입자크기를 나타내며, 폐 폴리올레핀 발포체를 액체질소, 밀링기, 또는 분쇄기로 파쇄하여 제조되는 것을 특징으로 하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치.
The method of claim 1,
The waste polyolefin foam powder has a particle size of 1 to 10 μm, and is prepared by crushing the waste polyolefin foam with liquid nitrogen, a mill, or a grinder. Complex Masterbatch.
상기 무기금속 수산화물은 산화알루미늄 및 수산화마그네슘으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 폐 폴리올레핀 발포체 분말을 이용한 고난연성 및 친환경성 폴리올레핀계 나노복합 마스터뱃치.The method of claim 1,
The inorganic metal hydroxide is a high-resistance and eco-friendly polyolefin-based nanocomposite masterbatch using waste polyolefin foam powder, characterized in that it consists of at least one selected from the group consisting of aluminum oxide and magnesium hydroxide.
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