KR100546008B1 - Manufacturing method and composition of polyethylene-based composition containing glass fiber - Google Patents
Manufacturing method and composition of polyethylene-based composition containing glass fiber Download PDFInfo
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- KR100546008B1 KR100546008B1 KR1020030047908A KR20030047908A KR100546008B1 KR 100546008 B1 KR100546008 B1 KR 100546008B1 KR 1020030047908 A KR1020030047908 A KR 1020030047908A KR 20030047908 A KR20030047908 A KR 20030047908A KR 100546008 B1 KR100546008 B1 KR 100546008B1
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Abstract
본 발명은 건축자재나 배관자재에 혼합하여 사용되는 조성물에 관한 것으로서, 상세하게는 65kg 내지 70kg의 고밀도 폴리에틸렌(HDPE)과, 폴리에틸렌과 말레인산 및 개시제를 혼합한 후 공중합하여 형성된 공중합체 말레인산 변성 폴리에틸렌 3kg 내지 5kg을 혼합시켜 베이스조성물을 형성시키는 단계와; 상기 베이스조성물과 실리카, 알루미늄, 칼슘, 마그네슘, 티타늄, 나트륨, 붕소 산화물을 화학적 조성으로 갖는 유리섬유 30kg 내지 35kg을 혼합시켜 폴리에틸렌계 조성물을 형성시키는 단계와; 상기 폴리에틸렌계 조성물에 자외선안정제를 첨가시키는 단계와; 상기 자외선안정제가 첨가된 폴리에틸렌계 조성물을 210℃ 내지 230℃에서 압출성형시키는 단계와; 상기 압출성형된 조성물을 냉각처리하여 펠릿형으로 절단시키는 단계;를 포함하여 구성되는 것을 특징으로 하는 유리섬유가 함유된 폴리에틸렌계 조성물의 제조방법을 기술적 요지로 한다. 또한 65kg 내지 70kg의 고밀도 폴리에틸렌(HDPE)과, 폴리에틸렌과 말레인산 및 개시제를 혼합한 후 공중합하여 형성된 공중합체 말레인산 변성 폴리에틸렌 3kg 내지 5kg을 혼합시켜 형성된 베이스조성물과, 상기 베이스조성물에 실리카, 알루미늄, 칼슘, 마그네슘, 티타늄, 나트륨, 붕소 산화물을 화학적 조성으로 갖는 유리섬유 30kg 내지 35kg을 혼합시켜 형성된 폴리에틸렌계 조성물과, 상기 폴리에틸렌계 조성물에 자외선안정제를 첨가하여 210℃ 내지 230℃에서 압출성형하고, 냉각처리 후 절단하여 형성되는 것을 특징으로 하는 유리섬유가 함유된 폴리에틸렌계 조성물을 또 다른 기술적 요지로 한다. 이에 따라 고강도와 고인성, 내화학성, 내후성, 환경친화적 특징을 갖는 조성물을 제조하여, 배관자재나 건축자재에 첨가하여 널리 사용할 수 있으며, 재생품에도 첨가하여 사용할 수 있으므로 원가를 절감하고 국가산업 전반에 이바지할 수 있는 이점이 있다. The present invention relates to a composition used by mixing in building materials or piping materials, and in detail, 3 kg of copolymer maleic acid-modified polyethylene formed by mixing after copolymerizing a high density polyethylene (HDPE) of 65kg to 70kg, polyethylene, maleic acid and an initiator Mixing 5 kg to form a base composition; Mixing the base composition with 30 kg to 35 kg of glass fibers having a chemical composition of silica, aluminum, calcium, magnesium, titanium, sodium, and boron oxide to form a polyethylene-based composition; Adding an ultraviolet stabilizer to the polyethylene composition; Extruding the polyethylene-based composition to which the ultraviolet stabilizer is added at 210 ° C. to 230 ° C .; Cooling the extruded composition is cut into pellets; and a method for producing a polyethylene-based composition containing a glass fiber, characterized in that it comprises a. In addition, 65kg to 70kg of high-density polyethylene (HDPE), a copolymer formed by mixing polyethylene and maleic acid and an initiator and copolymerized 3kg to 5kg of maleic acid-modified polyethylene, and silica, aluminum, calcium, Polyethylene-based composition formed by mixing 30kg to 35kg of glass fiber having magnesium, titanium, sodium, and boron oxide as a chemical composition, and an ultraviolet stabilizer was added to the polyethylene-based composition, followed by extrusion molding at 210 ° C to 230 ° C, and after cooling treatment Another technical gist of the polyethylene-based composition containing glass fibers, which is formed by cutting. As a result, a composition having high strength, high toughness, chemical resistance, weather resistance, and environmentally friendly characteristics can be manufactured and added to piping materials and construction materials, and can be widely used for recyclable materials. There is an advantage that can contribute.
고밀도폴리에틸렌 유리섬유 개시제 말레인산 자외선안정제 압출성형 디알킬과산화물HDPE glass fiber initiator maleic acid UV stabilizer extrusion molding dialkyl peroxide
Description
도 1 - 본 발명에 따른 유리섬유가 함유된 폴리에틸렌계 조성물의 제조방법에 대한 블럭도.1-a block diagram of a method for producing a polyethylene-based composition containing a glass fiber according to the present invention.
본 발명은 건축자재나 배관자재에 혼합하여 사용되는 조성물에 관한 것으로서, 고밀도 폴리에틸렌에 유리섬유를 혼합하여 고강도와 고인성, 내화학성, 환경친화적인 특징을 갖는 조성물의 제조방법과 그 조성물에 관한 것이다.The present invention relates to a composition used by mixing in a building material or a piping material, and relates to a method for producing a composition having a high strength, high toughness, chemical resistance, and environment-friendly characteristics by mixing glass fiber with high density polyethylene, and a composition thereof. .
일반적으로 건축자재로는 콘크리트가, 배관자재로는 PVC(polyvinyl chloride)가 주로 사용되어져 왔다. 콘크리트는 시멘트, 모래, 자갈 등을 물로 혼합하여 거푸집에서 응고시켜 형성되는 것으로, 충격이나 진동 등에 의해 손상되는 경우가 많으며, 배관자재로 널리 쓰이는 PVC(polyvinyl chloride)는 가공시에 유해가스가 발생하여 인체와 환경에 치명적인 문제점을 초래하고 있다.In general, concrete has been used as a building material, polyvinyl chloride (PVC) has been mainly used as a piping material. Concrete is formed by mixing cement, sand, gravel, etc. with water to solidify in the formwork, and is often damaged by impact or vibration.PVC (polyvinyl chloride), which is widely used as piping material, generates harmful gases during processing. It is causing fatal problems to human body and environment.
이를 개선하기 위해 종래에는 콘크리트에 철심 등의 금속재를 내부에 삽입하여 함께 응고시켜 강도를 높여 사용하여 왔다. 그러나 이는 콘크리트가 파손된 경 우에는 그대로 외부에 철심 등이 노출되어 매우 위험하며, 수분 등에 쉽게 부식되어 콘크리트 파손을 조기에 초래하고, 심미성에도 심각한 지장을 초래하고 있다.In order to improve this, conventionally, metals such as iron cores are inserted into concrete to solidify together and used to increase strength. However, when concrete is damaged, iron cores are exposed to the outside, which is very dangerous. Corrosion is easily caused by moisture, causing concrete breakage early and seriously impairing aesthetics.
그리고 배관자재로서 PVC를 대신하여, 폴리에틸렌계열의 수지가 대체제로 사용되고 있으나, 상기 폴리에틸렌은 환경친화적이나 물리적 강도와 온도변화에 따른 내열강도에 취약해서 배관재로 사용되는 데에는 문제점이 있다. 또한 버진그레이드(virgin grade)일 때에만 배관자재로서의 압축강도와 인장강도를 만족시켜 주므로 생산과정에서 발생할 수 있는 재생품은 거의 폐기처분 처리되고 있는 실정이다.And in place of PVC as a pipe material, polyethylene-based resin is used as a substitute, but the polyethylene is environmentally friendly, but vulnerable to heat resistance according to physical strength and temperature change, there is a problem in being used as a pipe material. In addition, only the virgin grade satisfies the compressive strength and the tensile strength as piping materials, so the regenerated products that can be produced during the production process are almost disposed of.
본 발명은 상기 문제점을 해결하기 위해 안출된 것으로서, 고밀도 폴리에틸렌에 유리섬유를 혼합하여 고강도와 고인성, 내화학성, 내후성, 환경친화적 특징을 갖는 조성물의 제조방법과 그 조성물의 제공을 목적으로 한다.The present invention has been made to solve the above problems, an object of the present invention is to provide a method for preparing a composition having a high strength and high toughness, chemical resistance, weather resistance, environmentally friendly by mixing a glass fiber in high-density polyethylene.
상술한 바와 같은 목적달성을 위한 본 발명은, 65kg 내지 70kg의 고밀도 폴리에틸렌(HDPE)과, 폴리에틸렌과 말레인산 및 개시제를 혼합한 후 공중합하여 형성된 공중합체 말레인산 변성 폴리에틸렌 3kg 내지 5kg을 혼합시켜 베이스조성물을 형성시키는 단계와; 상기 베이스조성물과 실리카, 알루미늄, 칼슘, 마그네슘, 티타늄, 나트륨, 붕소 산화물을 화학적 조성으로 갖는 유리섬유 30kg 내지 35kg을 혼합시켜 폴리에틸렌계 조성물을 형성시키는 단계와; 상기 폴리에틸렌계 조성물에 자외선안정제를 첨가시키는 단계와; 상기 자외선안정제가 첨가된 폴리에틸렌계 조성물을 210℃ 내지 230℃에서 압출성형시키는 단계와; 상기 압출성형된 조성물을 냉각처리하여 펠릿형으로 절단시키는 단계;를 포함하여 구성되는 것을 특징으로 하는 유리섬유가 함유된 폴리에틸렌계 조성물의 제조방법을 기술적 요지로 한다.The present invention for achieving the above object, 65kg to 70kg of high-density polyethylene (HDPE), copolymers formed by mixing polyethylene and maleic acid and the initiator and copolymerized by mixing 3kg to 5kg of maleic acid-modified polyethylene to form a base composition Making a step; Mixing the base composition with 30 kg to 35 kg of glass fibers having a chemical composition of silica, aluminum, calcium, magnesium, titanium, sodium, and boron oxide to form a polyethylene-based composition; Adding an ultraviolet stabilizer to the polyethylene composition; Extruding the polyethylene-based composition to which the ultraviolet stabilizer is added at 210 ° C. to 230 ° C .; Cooling the extruded composition is cut into pellets; and a method for producing a polyethylene-based composition containing a glass fiber, characterized in that it comprises a.
상기 베이스조성물을 형성시키는 단계는, 개시제가 디알킬과산화물로 형성되는 것을 특징으로 하는 것이 바람직하다.Forming the base composition, it is preferable that the initiator is formed of a dialkyl peroxide.
또한 65kg 내지 70kg의 고밀도 폴리에틸렌(HDPE)과, 폴리에틸렌과 말레인산 및 개시제를 혼합한 후 공중합하여 형성된 공중합체 말레인산 변성 폴리에틸렌 3kg 내지 5kg을 혼합시켜 형성된 베이스조성물과, 상기 베이스조성물에 실리카, 알루미늄, 칼슘, 마그네슘, 티타늄, 나트륨, 붕소 산화물을 화학적 조성으로 갖는 유리섬유 30kg 내지 35kg을 혼합시켜 형성된 폴리에틸렌계 조성물과, 상기 폴리에틸렌계 조성물에 자외선안정제를 첨가하여 210℃ 내지 230℃에서 압출성형하고, 냉각처리 후 절단하여 형성되는 것을 특징으로 하는 유리섬유가 함유된 폴리에틸렌계 조성물을 또 다른 기술적 요지로 한다.In addition, 65kg to 70kg of high-density polyethylene (HDPE), a copolymer formed by mixing polyethylene and maleic acid and an initiator and copolymerized 3kg to 5kg of maleic acid-modified polyethylene, and silica, aluminum, calcium, Polyethylene-based composition formed by mixing 30kg to 35kg of glass fiber having magnesium, titanium, sodium, and boron oxide as a chemical composition, and an ultraviolet stabilizer was added to the polyethylene-based composition, followed by extrusion molding at 210 ° C to 230 ° C, and after cooling treatment Another technical gist of the polyethylene-based composition containing glass fibers, which is formed by cutting.
상기 베이스조성물은, 개시제가 디알킬과산화물로 형성되는 것을 특징으로 하는 것이 바람직하다.The base composition is preferably characterized in that the initiator is formed of a dialkyl peroxide.
이에 따라 고강도와 고인성, 내화학성, 내후성, 환경친화적 특징을 갖는 조성물을 제조하여, 배관자재나 건축자재에 첨가하여 널리 사용할 수 있으며, 재생품에도 첨가하여 사용할 수 있으므로 원가를 절감하고 국가산업 전반에 이바지할 수 있는 이점이 있다.As a result, a composition having high strength, high toughness, chemical resistance, weather resistance, and environmentally friendly characteristics can be manufactured and added to piping materials and construction materials, and can be widely used for recyclable materials. There is an advantage that can contribute.
이하에서는 본 발명의 바람직한 실시예를 첨부된 도면을 참조하여 상세히 설명하고자 한다. 도 1은 본 발명에 따른 유리섬유가 함유된 폴리에틸렌계 조성물의 제조방법에 대한 블럭도이다.Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in detail. 1 is a block diagram of a method for producing a polyethylene-based composition containing a glass fiber according to the present invention.
우선 베이스조성물을 형성하기 위해서 고밀도 폴리에틸렌(HDPE, high density polyethylene)과 말레인산(maleate) 변성 폴리에틸렌을 혼합시킨다.First, high density polyethylene (HDPE) and maleate modified polyethylene are mixed to form a base composition.
상기 고밀도 폴리에틸렌은 분자량이 수천에서 수백만까지 분포하는 매우 큰 분자량을 갖는 것으로, 저밀도 폴리에틸렌(LDPE)에 비해 충격강도, 인열강도, 내환경응력균열성, 신율 등 물리적 특성은 향상된다. 또한 고밀도 폴리에틸렌은 구조적으로 결정도가 높고 3차수소(tertiary H)의 수가 매우 적기 때문에 산화에 대한 안정성이 뛰어나다.The high-density polyethylene has a very large molecular weight, which has a molecular weight ranging from thousands to millions, and physical properties such as impact strength, tear strength, environmental stress crack resistance, and elongation are improved compared to low density polyethylene (LDPE). In addition, high-density polyethylene is structurally high in crystallinity and has a very small number of tertiary H, which is excellent in oxidation stability.
상기 말레인산 변성 폴리에틸렌(PE graft copolymer)은 폴리에틸렌을 베이스로 하여 극성을 갖는 무수 말레인산 모노머(monomer)를 공중합 성분으로 하여 화학적으로 결합시킨 공중합체(copolymer)이다. 또한 상기 말레인산 변성 폴리에틸렌은 디알킬과산화물을 개시제로 첨가하여 사용하는 것이 바람직하다. 이는 상기 말레인산과 폴리에틸렌의 중합을 촉진하기 위한 것이다. 상기 말레인산 변성 폴리에틸렌은 금속이나 다른 플라스틱과의 접착성이 우수하여, 주로 폴리에틸렌과 다른 플라스틱과의 접착층으로 사용되어 지고 있다.The maleic acid-modified polyethylene (PE graft copolymer) is a copolymer chemically bonded with a polyethylene-based maleic anhydride monomer (polymer) as a copolymerization component. In addition, the maleic acid-modified polyethylene is preferably used by adding a dialkyl peroxide as an initiator. This is to promote the polymerization of the maleic acid and polyethylene. The maleic acid-modified polyethylene has excellent adhesion to metals and other plastics, and is mainly used as an adhesive layer between polyethylene and other plastics.
따라서 상기 고밀도 폴리에틸렌 65kg 내지 70kg에 상기 말레인산 변성 폴리에틸렌 3kg 내지 5kg을 혼합하여 베이스조성물로서 사용하게 되면, 상기 말레인산 변성 폴리에틸렌으로 인해 상기 고밀도 폴리에틸렌의 접착성을 향상시켜 혼합될 유리섬유와의 결합력을 향상시키는 역할을 하게 된다.Therefore, when used as a base composition by mixing 3kg to 5kg of the maleic acid-modified polyethylene to 65kg to 70kg of the high-density polyethylene, by improving the adhesiveness of the high-density polyethylene due to the maleic acid-modified polyethylene to improve the bonding strength with the glass fiber to be mixed It will play a role.
다음으로 상기 고밀도 폴리에틸렌과 상기 말레인산 변성 폴리에틸렌의 혼합 으로 형성된 베이스조성물에 유리섬유 30kg 내지 35kg을 혼합하여 폴리에틸렌계 조성물을 형성한다.Next, 30 kg to 35 kg of glass fibers are mixed with the base composition formed by mixing the high density polyethylene and the maleic acid-modified polyethylene to form a polyethylene-based composition.
상기 유리섬유(glass fiber)는 실리카, 알루미늄, 칼슘, 마그네슘, 티타늄, 나트륨, 붕소 산화물을 화학적 조성으로 가지며, 그 조성비는 다음과 같다.The glass fiber has a chemical composition of silica, aluminum, calcium, magnesium, titanium, sodium, boron oxide, the composition ratio is as follows.
상기 도표에서 도시된 바와 같은 조성비에 의하면, 상기 유리섬유는 무알카리 글래스(glass)로서 전기절연성, 내열성, 내풍화성이 우수하고, 강도가 뛰어나다. 특히 B2O3(산화붕소)가 투입되어 인장강도를 높여주고, 유리섬유의 표면경도를 높여준다. 또한 건축자재나 배관자재에 혼합하여 사용할 경우에, 단열보온성을 향상시키고, 고온에서는 점도를 낮게 해서 가공을 편리하게 해주며, 화학적 내구성을 향상시켜주고, 불연성이며 흡수성이 작다. 상기 유리섬유의 물리적 특성은 다음과 같다.According to the composition ratio as shown in the table, the glass fiber is alkali-free glass (glass) is excellent in electrical insulation, heat resistance, weathering resistance, and excellent strength. In particular, B 2 O 3 (boron oxide) is added to increase the tensile strength and to increase the surface hardness of the glass fiber. In addition, when mixed with building materials and piping materials, the thermal insulation insulation is improved, and at high temperatures, the viscosity is lowered, so that the processing is convenient, the chemical durability is improved, nonflammable, and the water absorption is small. Physical properties of the glass fiber is as follows.
다음으로 상기 고밀도 폴리에틸렌, 상기 말레인산 변성 폴리에틸렌과 유리섬유를 혼합한 폴리에틸렌계 조성물에 자외선안정제를 첨가한다. 상기 자외선안정제는 자외선에 의한 변색이나 분해를 방지하여 제품의 내후성을 개선하기 위한 것이다. 일반적으로 벤조페논계나 벤조트리아졸계, 힌다드아민계 광안정제(HALS)가 있으며, 이를 단독으로 사용하거나 함께 사용할 수 있다.Next, an ultraviolet stabilizer is added to the polyethylene composition in which the high density polyethylene, the maleic acid-modified polyethylene, and glass fibers are mixed. The ultraviolet stabilizer is to improve the weather resistance of the product by preventing discoloration or decomposition by ultraviolet rays. Generally, there are benzophenone-based, benzotriazole-based, and hindered amine-based light stabilizers (HALS), which may be used alone or in combination.
상기 폴리에틸렌계 조성물에 자외선 안정제를 첨가한 후, 210℃ 내지 230℃에서 트윈 스크류에 의해 분당 3m 내지 4m로 가는 섬유 형태로 압출성형시킨다. 이렇게 압출성형되어 가는 섬유 형태로 된 폴리에틸렌계 조성물은 냉각수 또는 에어에 의해 냉각처리되고 건축자재나 배관자재에 잘 섞이도록 하기 위하여 펠릿(pellet) 형태로 절단하게 된다.After adding the UV stabilizer to the polyethylene-based composition, it is extruded in the form of fibers from 3m to 4m per minute by twin screws at 210 ℃ to 230 ℃. The extruded fiber-like polyethylene composition is cut into pellets in order to be cooled by cooling water or air and mixed well with building materials or piping materials.
상기와 같이 형성된 펠릿형의 유리섬유가 함유된 폴리에틸렌계 조성물을, 사용자의 용도에 따라 건축자재나 배관자재에 다양하게 첨가하여 고강도와 고인성, 내화학성, 내후성, 환경친화적인 자재를 공급하게 된다.The polyethylene-based composition containing the pellet-type glass fiber formed as described above is variously added to building materials and piping materials according to the user's use to supply high strength, high toughness, chemical resistance, weather resistance, and environmentally friendly materials. .
또한 재생 원재료만을 사용할 경우에는 물리적 특성이 크게 저하되므로, 재생품에 상기 조성물을 첨가하여 사용하므로써 압축강도, 인장강도, 내열성을 높이고, 뒤틀림이 방지되어, 폐기 처분되는 재생품도 다시 사용할 수 있다.In addition, when only the recycled raw material is used, the physical properties are greatly reduced, and thus, by adding the composition to the regenerated product, the compressive strength, the tensile strength and the heat resistance are increased, the warpage is prevented, and the recycled product which is disposed of and disposed of can be used again.
이하에서는 고밀도 폴리에틸렌에 유리섬유를 부피비 30% 정도 첨가한 경우에 물성을 테스트한 데이터이다.The following is the data test when the glass fiber is added to the high density polyethylene by about 30% by volume.
상기 도표에 도시된 바와 같이 고밀도 폴리에틸렌에 유리섬유를 부피비 30% 정도 첨가한 경우에 고강도, 고인성, 내화학성 등이 우수한 것을 알 수 있다.As shown in the table, when the glass fiber is added to the high density polyethylene by about 30% by volume, it can be seen that high strength, high toughness, chemical resistance, and the like are excellent.
상기 구성에 의한 본 발명은, 고강도와 고인성, 내화학성, 내후성, 환경친화적 특징을 갖는 유리섬유가 함유된 폴리에틸렌계 조성물을 제조하여, 배관자재나 건축자재에 첨가하여 널리 사용할 수 있는 효과가 있다.The present invention by the above configuration has the effect of producing a polyethylene-based composition containing a glass fiber having high strength, high toughness, chemical resistance, weather resistance, environmentally friendly characteristics, can be added to piping materials or building materials and widely used. .
또한 재생품에 본 발명에 따른 유리섬유가 함유된 폴리에틸렌계 조성물을 첨가하여 사용하므로서, 재생품의 압축강도, 인장강도, 내열성을 높이고, 뒤틀림을 방지하여, 폐기 처분되는 재생품도 다시 사용할 수 있으므로 원가가 절감되어 국가산업 전반에 이바지 할 수 있는 효과가 있다.In addition, by using the polyethylene-based composition containing the glass fiber according to the present invention to the regenerated product, it increases the compressive strength, tensile strength, heat resistance of the regenerated product, and prevents warping, so that the regenerated product that is disposed of can be reused, thereby reducing the cost. There is an effect that can contribute to the overall national industry.
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| PCT/KR2004/000150 WO2005005524A1 (en) | 2003-07-14 | 2004-01-29 | Method for fabricating polyethylene composition having glass fiber |
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