KR20030071175A - Biodegradable polyolefin resin composition containing elvan and a method for preparing the same - Google Patents
Biodegradable polyolefin resin composition containing elvan and a method for preparing the same Download PDFInfo
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Abstract
Description
본 발명은 토양 속에서 생붕괴 되는 맥반석을 함유하는 생붕괴성 폴리올레핀 수지 조성물 및 그 제조방법에 관한 것으로,The present invention relates to a biodegradable polyolefin resin composition and a method for producing the biodegradable polyvinyl stone in the soil,
특히, 전분과 폴리카프로락톤을 함유하는 생분해성 수지에 폴리올레핀 수지를 혼합하여 생붕괴성 폴리올레핀 수지의 기초 원료로 하고, 그 기초 원료에 맥반석을 첨가하여 생붕괴 후 토양과 폴리올레핀 수지의 비융화로 인한 생물의 생장 저하를 방지하며, 극성 단량체가 그라프트된 개질 폴리올레핀을 상용화제로 사용하여 수지의 가공물성의 저하를 막을 수 있도록 하는 맥반석을 함유하는 생붕괴성 폴리올레핀 수지 조성물 및 그 제조방법에 관한 것이다.In particular, a polyolefin resin is mixed with a biodegradable resin containing starch and polycaprolactone to form a basic raw material of a biodegradable polyolefin resin, and elvan is added to the basic raw material, resulting from incompatibility of soil and polyolefin resin after biodegradation. The present invention relates to a biodegradable polyolefin resin composition containing elvan, which prevents the growth of living organisms and prevents degradation of the processing properties of the resin by using a modified polyolefin grafted with a polar monomer as a compatibilizer.
일반적으로 생활 속에서 항상 접하고 있는 플라스틱 수지는 대중에 방치하거나 흙 속에 묻어두어도 자연 분해되지 않으므로 토양을 오염시키는 등의 문제점이있었으며, 기존의 플라스틱 수지를 강제 소각시키면 각종 오염물질이 배출되어 토양은 물론 대기환경까지 오염시키는 심각한 문제점이 발생되었다.In general, plastic resins that are always in contact with life are not decomposed naturally even if they are left in the public or buried in the soil, thus contaminating the soil.Forcible incineration of existing plastic resins causes various pollutants to be discharged. A serious problem has occurred that pollutes the atmosphere.
따라서 상기와 같은 통상적인 플라스틱 수지의 문제점을 해소하기 위하여 흙 속에 매립하면 일정기간 후 분해되는 생분해성 수지가 개발되어 사용되고 있으나, 초기에 개발된 생분해성 수지는 폴리올레핀 수지에 생분해성이 강한 전분을 단순 혼합하여 전분의 생분해로 인한 폴리올레핀 수지의 단순 붕괴를 유도하였던 것이다.Therefore, in order to solve the problems of the conventional plastic resins, biodegradable resins that are decomposed after a certain period of time have been developed and used when buried in the soil. The mixing caused a simple collapse of the polyolefin resin due to the biodegradation of the starch.
그러나, 상기와 같이 전분과 폴리올레핀 수지를 단순 혼합하여 개발된 생분해성 수지는 폴리올레핀의 가공물성 및 작업성이 저하되는 문제점이 있었을 뿐만 아니라, 생붕괴 후 잔류되는 폴리올레핀이 생물의 생장에 방해요인으로 작용되는 문제를 발생시켰다.However, the biodegradable resin developed by simply mixing starch and polyolefin resin as described above not only had a problem that the workability and workability of the polyolefin was deteriorated, but also the polyolefin remaining after biodegradation acted as a barrier to the growth of organisms. It caused a problem.
상기와 같은 전분과 폴리올레핀을 혼합한 생분해성 수지의 문제점들을 해소하기 위하여 전분과 폴리카프로락톤을 혼합하여 제조하는 생분해성 수지가 개발되었으나, 이와 같이 전분과 풀리카프로락톤을 혼합하여 제조하는 생분해성 수지는 뛰어난 생분해성 효과에 비하여 가공물성 저하로 인한 그 성형물의 활용도가 극히 제한되는 문제점이 있었다.In order to solve the problems of the biodegradable resin mixed with starch and polyolefin as described above, a biodegradable resin prepared by mixing starch and polycaprolactone was developed, but a biodegradable resin prepared by mixing starch and polycaprolactone in this way Compared to the excellent biodegradable effect, there was a problem that the utilization of the molding due to the reduction of the workability is extremely limited.
또한 생분해성 효과가 높은 폴리카프로락톤을 혼합한 생분해성 수지의 활용도를 높이기 위하여 전분과 폴리카프로락톤을 혼합한 생분해성 수지와 폴리올레핀 수지를 단순 혼합하여 성형물을 제조함으로서 가공물성을 향상시키는 방법도 개발되었으나, 이와 같이 전분과 폴리카프로락톤의 생분해성 수지에 폴리올레핀 수지를단순 혼합한 생분해성 수지는 성형물의 박리현상이 발생되었을 뿐만 아니라, 생붕괴 후에 생물의 생장을 저해하는 폴리올레핀 성분이 잔류하게 되는 문제점이 계속 발생하였다.In addition, in order to improve the utilization of the biodegradable resin mixed with polycaprolactone having a high biodegradable effect, a method of improving processability by developing a molded product by simply mixing biodegradable resin and polyolefin resin mixed with starch and polycaprolactone is also developed. However, the biodegradable resin obtained by simply mixing the polyolefin resin with the biodegradable resin of starch and polycaprolactone not only caused peeling of the molded product, but also remained a polyolefin component that inhibited the growth of the living body after biodegradation. This continued to happen.
그러므로 지금까지 개발된 생분해성 수지 제품들은 기존의 일반 플라스틱 수지로 만들 수 있는 제품들을 대체하기 위한 가공물성이 저하되어 제한적인 용도로 사용되었을 뿐만 아니라, 생분해 후의 잔류 폴리올레핀 성분으로 인하여 생물의 생장에 방해가 되고, 가공된 성형물이 얇게 분리되는 박리현상이 발생되는 등의 문제점이 있었던 것이다.Therefore, the biodegradable resin products developed so far have been used for a limited purpose because of reduced processing properties to replace products that can be made of conventional plastic resins, and also prevents the growth of living organisms due to residual polyolefin components after biodegradation. This is a problem such as peeling phenomenon occurs that the processed molding is thinly separated.
따라서, 본 발명의 목적은 전분과 폴리카프로락톤을 함유하는 생분해성 수지에 폴리올레핀 수지를 혼합하여 생붕괴성 폴리올레핀 수지의 기초 원료로 하고, 그 기초 원료에 맥반석을 첨가함으로서 생붕괴 후 토양과 폴리올레핀 수지의 비융화로 인한 생물의 생장 저하를 방지하며, 극성 단량체가 그라프트된 개질 폴리올레핀을 상용화제로 사용하여 수지의 가공물성의 저하를 막을 수 있도록 한 맥반석을 함유하는 생붕괴성 폴리올레핀 수지 조성물 및 그 제조방법을 제공함에 있다.Therefore, an object of the present invention is to mix the polyolefin resin with a biodegradable resin containing starch and polycaprolactone to form a basic raw material of biodegradable polyolefin resin, and by adding ganbanite to the basic raw material, soil and polyolefin resin after biodegradation Biodegradable polyolefin resin composition containing elvanite, which prevents the growth of organisms due to incompatibility, and prevents degradation of the processing properties of the resin by using modified polyolefin grafted with polar monomer as a compatibilizer. In providing a method.
이러한 본 발명의 목적은 폴리올레핀 합성수지 30 내지 50 중량%와, 전분과 폴리카프로락톤을 함유하는 생분해성 수지 30 내지 50중량%와, 극성 단량체가 그라프트된 개질 폴리올레핀 2.5 내지 7.5 중량%와를 계량하여 헨셀 믹서에서 혼합한 1차 혼합 조성물을 제조하고, 325메쉬 이상으로 분쇄된 맥반석 10 내지 20 중량%와,극성 단량체가 그라프트된 개질 폴리올레핀 2.5 내지 7.5 중량%와, 압출시의 폴리올레핀 수지의 산화를 방지하기 위한 폴리올레핀용 산화방지제 0.05 내지 0.5 중량%와, 압출 혼련시의 가공 작업성을 높이기 위한 폴리올레핀용 활제 0.1 내지 1.0 중량%와를 300 내지 500 RPM의 헨셀 믹서에서 3분 내지 15분간 혼합하여 조성한 2차 혼합 조성물을 제조하여 1차 혼합 조성물과 2차 혼합 조성물을 이축압출기에서 압출, 혼련할 수 있도록 폴리올레핀 수지의 조성물을 이룸으로서 달성될 수 있다.An object of the present invention is to measure Hensel by measuring 30-50 wt% of polyolefin synthetic resin, 30-50 wt% of biodegradable resin containing starch and polycaprolactone, and 2.5-7.5 wt% of modified polyolefin grafted with polar monomer. A primary mixed composition prepared by mixing in a mixer was prepared, and 10 to 20% by weight of gannetite pulverized to 325 mesh or more, 2.5 to 7.5% by weight of modified polyolefin grafted with polar monomer, and prevention of oxidation of the polyolefin resin during extrusion The secondary composition prepared by mixing 0.05 to 0.5% by weight of the polyolefin antioxidant and 0.1 to 1.0% by weight of the polyolefin lubricant to improve processing workability during extrusion kneading in a Henkel mixer at 300 to 500 RPM for 3 to 15 minutes. A mixture composition is prepared so that the primary and secondary mixture compositions can be extruded and kneaded in a twin screw extruder. This can be accomplished by forming a composition.
이하, 본 발명의 바람직한 실시예를 상세하게 설명하면 다음과 같다.Hereinafter, preferred embodiments of the present invention will be described in detail.
폴리올레핀 합성수지 30 내지 50 중량%와,30 to 50% by weight of polyolefin synthetic resin,
전분과 폴리카프로락톤을 함유하는 생분해성 수지 30 내지 50중량%와,30 to 50% by weight of a biodegradable resin containing starch and polycaprolactone,
극성 단량체가 그라프트된 개질 폴리올레핀 2.5 내지 7.5 중량%와를 계량하여 헨셀 믹서에서 혼합한 1차 혼합 조성물을 제조한다.2.5-7.5 wt% of the modified polyolefin grafted with polar monomer was weighed to prepare a primary mixed composition mixed in a Henschel mixer.
또한, 325메쉬 이상으로 분쇄된 맥반석 10 내지 20 중량%와,In addition, 10 to 20% by weight of ganguerite crushed to 325 mesh or more,
극성 단량체가 그라프트된 개질 폴리올레핀 2.5 내지 7.5 중량%와,2.5 to 7.5 wt% of a modified polyolefin grafted with a polar monomer,
압출시의 폴리올레핀 수지의 산화를 방지하기 위한 폴리올레핀용 산화방지제 0.05 내지 0.5 중량%와,0.05 to 0.5% by weight of an antioxidant for polyolefin for preventing oxidation of the polyolefin resin during extrusion,
압출 혼련시의 가공 작업성을 높이기 위한 폴리올레핀용 활제 0.1 내지 1.0 중량%와를 300 내지 500 RPM으로 회전하는 헨셀 믹서에서 3분 내지 15분간 혼합하여 2차 혼합 조성물을 제조한다.A secondary mixing composition is prepared by mixing 0.1 to 1.0% by weight of a lubricant for polyolefin with 3 to 15 minutes in a Henschel mixer rotating at 300 to 500 RPM to improve processing workability during extrusion kneading.
상기와 같이 조성된 1차 혼합 조성물과 2차 혼합 조성물은 먼저 상기 1차 혼합 조성물을 이축압출기에 투입하여 180℃ 내지 230℃에서 압출, 혼련을 시행하여 생분해성 수지와 폴리올레핀 합성수지를 혼련시킨다.The primary mixed composition and the secondary mixed composition prepared as described above are first introduced into the twin screw extruder and extruded and kneaded at 180 ° C. to 230 ° C. to knead the biodegradable resin and the polyolefin synthetic resin.
이어서 1차 혼합 조성물이 용융되기 시작하는 시점에서 2차 혼합 조성물을 이축압출기에 투입하여 압출, 혼련하며, 이후 이축압출기의 니딩존을 통과하여 상용화제로 인한 폴리올레핀 수지와 맥반석 간의 결합력을 증대시키고, 생붕괴성 수지의 가공물성을 높이는 것이 바람직하다.Subsequently, when the primary mixed composition starts to melt, the secondary mixed composition is introduced into a twin screw extruder to extrude and knead, and then passes through the kneading zone of the twin screw extruder to increase the binding force between the polyolefin resin and the elvan due to the compatibilizer, It is preferable to improve the process property of collapsible resin.
또한, 상기 혼련이 끝난 생붕괴성 수지는 스트랜드를 형성하여 냉각을 시키고, 냉각된 스트랜드는 펠렛타이징 공정을 거쳐 성형용 원료로 완성한다.In addition, the kneaded finished biodegradable resin forms a strand to be cooled, and the cooled strand is completed as a raw material for molding through a pelletizing process.
이때, 상기 압출, 혼련하는 이축압출기에는 진공펌프를 이용한 진공을 발생시켜 혼련중 발생될 수 있는 가스를 제거할 수 있도록 하는 것이 바람직하다.In this case, it is preferable to generate a vacuum using a vacuum pump to the extruded and kneaded twin screw extruder so as to remove a gas that may be generated during kneading.
이와 같은 본 발명은 폴리올레핀 합성수지 30 내지 50 중량%에 전분과 폴리카프로락톤을 함유하는 생분해성 수지 30 내지 50중량%을 헨셀 믹서에서 혼합하여 생붕괴성 수지의 1차 혼합 조성물을 제조한다.The present invention is prepared by mixing 30 to 50% by weight of biodegradable resin containing starch and polycaprolactone to 30 to 50% by weight of polyolefin synthetic resin in a Henschel mixer to prepare a primary mixed composition of biodegradable resin.
이때, 상용화제로 극성 단량체가 그라프트된 개질 폴리올레핀 2.5 내지 7.5 중량%을 계량하여 헨셀 믹서에 넣고 함께 혼합함으로서 후공정인 압출, 혼련 공정에서의 폴리올레핀 합성수지와 생분해성 수지의 혼련도를 높일 수 있게 된다.At this time, by measuring the 2.5 to 7.5% by weight of the modified polyolefin grafted polar monomer with a compatibilizer into a Henschel mixer and mixed together, it is possible to increase the kneading degree of the polyolefin synthetic resin and biodegradable resin in the post-process extrusion, kneading process. .
또한, 325메쉬 이상으로 분쇄된 맥반석 10 내지 20 중량%, 극성 단량체가 그라프트된 개질 폴리올레핀 2.5 내지 7.5 중량%, 압출시의 폴리올레핀 수지의 산화를 방지하기 위한 폴리올레핀용 산화방지제 0.05 내지 0.5 중량% 그리고 압출, 혼련시의 가공 작업성을 높이기 위한 폴리올레핀용 활제 0.1 내지 1.0 중량%를 300 내지 500 RPM으로 회전하는 헨셀 믹서에서 3분 내지 15분간 혼합하여 2차 혼합 조성물을 제조한다.In addition, 10 to 20% by weight of gannetite pulverized to 325 mesh or more, 2.5 to 7.5% by weight of modified polyolefin grafted with polar monomer, 0.05 to 0.5% by weight of antioxidant for polyolefin to prevent oxidation of polyolefin resin during extrusion, and 0.1 to 1.0% by weight of a polyolefin lubricant for improving processing workability during extrusion and kneading is mixed in a Henschel mixer rotating at 300 to 500 RPM for 3 to 15 minutes to prepare a secondary mixed composition.
이때, 상기 2차 혼합 조성물의 조성비율은 상기 1차 혼합 조성물의 중량%에 대한 중량%의 조성비율을 표시한 것이다.At this time, the composition ratio of the secondary mixed composition is to indicate the composition ratio of the weight percent to the weight percent of the primary mixed composition.
상기와 같이 조성된 1차 혼합 조성물과 2차 혼합 조성물은 이축압출기에서 압출, 혼련하여 성형용 원료로 제조한다.The primary mixed composition and the secondary mixed composition, prepared as described above, are extruded and kneaded in a twin screw extruder to prepare a raw material for molding.
즉, 상기와 같이 폴리올레핀 합성수지와 생분해성 수지에 극성 단량체가 그라프트된 개질 폴리올레핀을 상용화제로 첨가하여 혼합한 1차 혼합 조성물을 이축압출기에 투입하여 180℃ 내지 230℃에서 압출, 혼련을 시행하면 생분해성 수지와 폴리올레핀 합성수지의 혼련과정에서 극성 단량체가 그라프트된 개질 폴리올레핀인 상용화제는 폴리올레핀 합성수지와 생분해성 수지의 혼련도를 높이는 역할을 하게 된다.That is, as described above, the primary mixed composition in which a polyolefin synthetic resin and a biodegradable resin is modified by adding a modified polyolefin grafted with a polar monomer as a compatibilizer is added to a twin screw extruder and extruded and kneaded at 180 to 230 ° C. for biodegradation. The compatibilizer, which is a modified polyolefin in which the polar monomer is grafted in the kneading process of the resin and the polyolefin synthetic resin, serves to increase the kneading degree of the polyolefin resin and the biodegradable resin.
이어서 상기 1차 혼합 조성물이 이축압출기에서 용융되기 시작하는 시점에서 325메쉬 이상으로 분쇄된 맥반석과, 극성 단량체가 그라프트된 개질 폴리올레핀, 폴리올레핀용 산화방지제, 폴리올레핀용 활제를 계량, 혼합하여 조성된 2차 혼합 조성물을 이축압출기에 추가로 투입하여 압출, 혼련과정을 진행시킨다.Subsequently, when the primary mixed composition starts to be melted in a twin screw extruder, the calcite pulverized to 325 mesh or more, the modified polyolefin grafted with the polar monomer, the antioxidant for polyolefin, and the lubricant for polyolefin, were prepared. The tea mixture composition is further added to a twin screw extruder to proceed the extrusion and kneading process.
이때, 상기 2차 혼합 조성물에 혼합된 폴리올레핀용 산화방지제는 압출시의폴리올레핀 수지의 산화를 방지하게 되며, 폴리올레핀용 활제는 압출 혼련시의 가공 작업성을 높이게 된다.At this time, the antioxidant for polyolefin mixed in the secondary mixed composition prevents oxidation of the polyolefin resin during extrusion, and the lubricant for polyolefin increases processing workability during extrusion kneading.
상기와 같은 압출, 혼련과정에서는 용융되는 1차 혼합 조성물과 2차 혼합 조성물에서 가스가 발생될 수 있으나, 이와 같이 압출, 혼련과정에서 발생되는 가스는 이축압출기에 연결 설치된 진공펌프로 진공을 발생시켜 혼련중 발생될 수 있는 가스를 흡입 제거한다.In the extrusion and kneading process as described above, gas may be generated in the primary mixed composition and the secondary mixed composition which are melted. However, the gas generated in the extrusion and kneading process is generated by a vacuum pump connected to a twin screw extruder. Suction and remove gases that may be generated during kneading.
이와 같은 공정을 지나 용융된 조성물들이 이축압출기의 니딩존을 통과하면 상용화제로 인한 폴리올레핀 수지와 맥반석간의 결합력이 증대되고, 생붕괴성 수지의 가공물성이 높아지는 것이다.When the molten compositions pass through the kneading zone of the twin-screw extruder through such a process, the binding force between the polyolefin resin and the elvan due to the compatibilizer is increased, and the workability of the biodegradable resin is increased.
한편, 상기 혼련이 끝난 생붕괴성 수지는 스트랜드를 형성하여 냉각을 시키고, 냉각된 스트랜드는 펠렛타이징 공정을 거쳐 성형용 생붕괴성 수지 원료로 완성시킴으로서 생붕괴성 수지 원료를 사용하여 각종 성형물을 성형하면 성형물의 성형방법이나 구조에 관계없이 다양한 형상의 생붕괴성 수지 성형물을 성형할 수 있게 된다.Meanwhile, the kneaded finished biodegradable resin forms strands and is cooled, and the cooled strands are pelletized to complete the biodegradable resin raw materials for molding, thereby forming various moldings using the biodegradable resin raw materials. By molding, biodegradable resin moldings of various shapes can be molded regardless of the molding method or structure of the molding.
특히, 본 발명에 의한 생붕괴성 성형물의 용도를 다한 후에 별도의 폐기절차를 거치지 않고도 자연 생붕괴되어 환경파괴를 막을 수 있을 뿐만 아니라, 자연 붕괴된 후에는 원적외선방출 자연광물인 맥반석에 의하여 생붕괴 후의 폴리올레핀 합성수지로 인한 토양의 오염 및 생물의 생장을 저해하는 요소를 제거할 수 있게 된다.Particularly, after the use of the biodegradable molding according to the present invention, it is possible to prevent the natural destruction of the environment and environmental destruction without going through a separate disposal procedure. It is possible to remove the elements that inhibit soil contamination and biological growth due to the subsequent polyolefin resin.
상기에서와 같이 본 발명은 기존의 가공설비를 이용하여 생붕괴성 수지의 제조가 가능하고, 생분해성 수지를 첨가하여 발생되는 폴리올레핀 수지의 가공물성의 저하를 방지하여 성형물의 성형방법 및 구조에 제한을 받지 않고 다양한 형상의 성형물을 성형 할 수 있을 뿐만 아니라, 성형물의 용도를 다한 후에는 별도의 폐기절차를 거치지 않고도 자연 생붕괴되어 환경파괴를 막을 수 있고, 생붕괴성 수지에 첨가된 원적외선방출 자연광물인 맥반석으로 인하여 생붕괴 후 폴리올레핀 합성수지로 인한 토양의 오염 및 생물의 생장을 저해하는 요소를 제거할 수 있는 효과가 제공되는 것이다.As described above, the present invention enables the production of biodegradable resins using existing processing equipment, and prevents degradation of the processing properties of polyolefin resins generated by adding biodegradable resins, thereby limiting the molding method and structure of moldings. It can not only mold moldings of various shapes without receiving the material, but also after the use of the moldings, it can be naturally destroyed and prevented from being destroyed without going through a separate disposal procedure. Due to the mineral elvan, it is possible to remove the elements that inhibit soil contamination and growth of organisms due to polyolefin resin after biodegradation.
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