KR20050113449A - Complex polyethylene regin having composition meterial - Google Patents
Complex polyethylene regin having composition meterial Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
본 발명은 관체성형에 적합한 강성수지, 즉 복합 폴리에틸렌 수지 조성물에 관한것으로, 보다 상세하게는 (A) 폴리에틸렌 36.0∼78.0중량％, (B) 유리섬유 3.0∼15.0중량％, (C) 탄산칼슘 5.0∼15.0％, (D) 상용화재로서 스테린산아연 0.2∼0.6중량％ 및 유기실란계화합물 0.4∼0.7중량％를 포함하는 관체성형에 적합한 강성수지 조성물에 관한 것이며, 본 발명은 강도 및 내열성이 향상된 폴리에틸렌 수지 조성물을 제공하는데 그 특징이 있다.The present invention relates to a rigid resin suitable for tubular molding, i.e., a composite polyethylene resin composition, more specifically, (A) 36.0-78.0 wt% polyethylene, (B) 3.0-15.0 wt% glass fiber, (C) calcium carbonate 5.0 The present invention relates to a rigid resin composition suitable for tubular molding comprising -15.0%, (D) 0.2-0.6% by weight of zinc sterate and 0.4-0.7% by weight of an organosilane compound as a compatibilizer, and the present invention provides improved strength and heat resistance. It is characterized by providing a polyethylene resin composition.
Description
본 발명은 관체성형에 적합한 강성수지(복합폴리에틸렌수지)에 관한 것으로 보다 상세하게는 폴리에틸렌, 유리섬유, 탄산칼슘, 상용화재를 포함하는 관체성형에 적합한 강성수지 조성물에 관한 것이다.The present invention relates to a rigid resin (composite polyethylene resin) suitable for tubular molding, and more particularly, to a rigid resin composition suitable for tubular molding including polyethylene, glass fiber, calcium carbonate, and a commercially available material.
폴리에틸렌 수지는 물성, 내약품성, 성형성이 뛰어나 수도관, 하수관, 산업자재등의 공업적 이용범위가 매우 넓은 소재이다. 그러나 폴리에틸렌은 화학구조상 무극성을 나타내어 2차 가공성, 특히 도장성 및 타소재와의 접착성이 열세하고 결정성 구조로인하여 치수 안정성이 미흡하여 강성, 내열성 또는 유사한 용도로 경쟁적으로 적용되는 폴리스티렌, 스티렌 아크릴로니트릴 공중합체등의 수지보다 많이 열세하다. 이러한 이유로 하수관 및 압력관등 산업용 자재로 폴리에틸렌 수지에 무기충진제 또는 타수지를 배합시킨 소재의 개발방법이 제시되고 있다.Polyethylene resin is excellent in physical properties, chemical resistance, and moldability, and is a material having a wide range of industrial applications such as water pipes, sewage pipes, and industrial materials. Polyethylene and styrene acrylic, however, exhibit a non-polar nature in terms of chemical structure, which is inferior to secondary processability, especially paintability and adhesion to other materials, and poor dimensional stability due to crystalline structure. It is inferior to resin, such as a ronitrile copolymer. For this reason, a method of developing a material in which an inorganic filler or a resin is mixed with polyethylene resin as an industrial material such as a sewer pipe and a pressure pipe has been proposed.
한편, 강도 및 내열성 그리고 그 밖의 기계적 물성을 향상시키기 위해서 폴리에틸렌 수지에 무기충진제로 유리섬유, 카본등과 같은 침상형 충진재와 탄산칼슘, 알루미나 등과 같은 구상형 충진재등을 이용한다. Meanwhile, in order to improve strength, heat resistance and other mechanical properties, needle-like fillers such as glass fiber and carbon and spherical fillers such as calcium carbonate and alumina are used as inorganic fillers in polyethylene resins.
특히, 유리섬유가 충전된 폴리에틸렌 수지는 고강도 및 고내열성을 갖는다. 또한 유리섬유는 높은 이축율(aspect ratio)의 섬유상 구조로 인해 판상형 또는 구상형 충진재에 비해 기계적물성향상 효과가 매우 뛰어나다.In particular, polyethylene resins filled with glass fibers have high strength and high heat resistance. In addition, the glass fiber has an excellent mechanical property improvement effect compared to the plate-shaped or spherical filler due to the high biaxial rate (fiber) structure.
물성향상을 구현하기 위해 사용되는 구상형 충진재의 하나인 탄산칼슘(CaCO3)을 폴리에틸렌 수지 조성물에 적용함으로써 고강도 및 고내열성을 갖게 할 수 있다. 따라서 유리섬유, 탄산칼슘 적용시 상용성 문제만 해결된다면 일반적인 기계적 물성의 향상과 더불어 유리섬유가 지니고 있는 강인성, 내마모성과 탄산칼슘의 강인성등의 특성을 동시에 확보할 수 있다.By applying calcium carbonate (CaCO 3 ), which is one of spherical fillers used to implement physical properties, to a polyethylene resin composition, high strength and high heat resistance may be provided. Therefore, if the compatibility problem is solved when glass fiber and calcium carbonate are applied, it is possible to secure properties such as toughness, abrasion resistance, and calcium carbonate toughness that glass fiber has in addition to general mechanical properties.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로 폴리에틸렌과 유리섬유, 탄산칼슘을 혼합하고 이들의 상용화를 발현시키기 위하여 상용화재를 부가하여 혼합시킴으로써 강도 및 내열성이 향상된 관체성형에 적합한 강성수지(복합폴리에틸렌 수지)조성물을 제공함을 목적으로 한다.The present invention is to solve the problems as described above, by mixing polyethylene and glass fiber, calcium carbonate and adding a commercialization material to express their commercialization, the rigid resin suitable for tubular molding with improved strength and heat resistance (composite polyethylene) Resin) composition.
즉, 본 발명은 폴리에틸렌 36.0∼78.0중량％, 유리섬유3.0∼15.0중량％, 탄산칼슘5.0∼15.0중량％ 및 상용화재로써 스테린산아연 0.2∼0.6중량％, 유기실란계화합물 0.4∼0.7중량％로 구성된 폴리에틸렌 조성물에 관한 것이다. In other words, the present invention is 36.0-78.0% polyethylene, 3.0-15.0% glass fiber, 5.0-15.0% calcium carbonate, 0.2-0.6% zinc stearate, 0.4-0.7% organic organocompound compound It relates to a constructed polyethylene composition.
이하, 본 발명을 보다 상세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail.
본 발명에서 제조된 강성수지(복합폴리에틸렌) 조성물의 각 구성 성분을 보다 상세히 설명하면 다음과 같다.Referring to each component of the rigid resin (composite polyethylene) composition prepared in the present invention in more detail as follows.
본 발명의 (A) 성분인 폴리에틸렌 수지는 용융지수(MI)가 0.945∼0.970이고 Cr계가 바람직 하다.The polyethylene resin which is the component (A) of the present invention has a melt index (MI) of 0.945 to 0.970 and preferably a Cr system.
미만인 경우에는 제품의 성형성이 양호하지 못하고 생산성이 저하되며 제품이 요구하는 강도를 맞추기 어려운 반면 초과할 경우에는 성형성이 양호하지 못하며 충격강도가 급격히 저하된다.If it is less than the moldability of the product is not good, productivity is lowered, it is difficult to meet the strength required by the product, while if exceeded, the moldability is not good and the impact strength is sharply lowered.
본 발명의 (B) 성분인 유리섬유는 무기 충진재로서 평균 입경이 6∼16㎛이고, 바람직하게는 8∼14㎛이며 길이가 1∼17㎛인 것의 사용이 가능하며 함량은 3.0∼15중량％가 바람직하다.Glass fiber as the component (B) of the present invention is an inorganic filler having an average particle diameter of 6 to 16 µm, preferably 8 to 14 µm, and a length of 1 to 17 µm, with a content of 3.0 to 15 wt%. Is preferred.
유리섬유의 입경이 5㎛미만인 경우에는 혼합하는 동안에 깨지게 되어 강성 발현 효과가 미흡해지며 16㎛를 초과할 경우에는 기계적 강도를 얻을 수 없음과 동시에 성형품의 변형이 악화되어 외관 상태가 불량해진다.If the glass fiber has a particle diameter of less than 5 µm, it is broken during mixing, and the effect of stiffness is inadequate. If it exceeds 16 µm, the mechanical strength cannot be obtained and the deformation of the molded article is deteriorated, resulting in poor appearance.
본 발명에서의 유리섬유 길이는 특정 길이로의 제한없이 상업적으로 쉽게 구할수 있는 것이라면 사용이 가능하며 혼련 작업성 측면에서 통상 1∼10㎛ 정도 길이의 쵸핑된 스트랜드(Shopped Strand)의 사용이 바람직 하다.The glass fiber length in the present invention can be used as long as it can be easily obtained commercially without limitation to a specific length, and in terms of kneading workability, it is preferable to use a shopping strand of about 1 to 10 μm in length. .
본 발명에서의 유리섬유 함량이 3.0중량％ 미만일때는 강성 발현의 효과가 미흡하고, 인장, 굴곡탄성이 미흡하게 되며 16중량％ 이상 초과할 수 있으나 탄산칼슘의 영향력으로 성형력이 저하되거나 휨 현상등이 유발되어 외관상태가 양호하지 못하게 된다.When the glass fiber content of the present invention is less than 3.0% by weight, the effect of rigid expression is insufficient, the tensile and flexural elasticity is insufficient and may be more than 16% by weight, but the molding force is reduced or warpage phenomenon under the influence of calcium carbonate. This causes a poor appearance.
본 발명의 (C) 성분은 탄산칼슘(CaCo3)으로서 상업적으로 쉽게 구할 수 있는 것이라면 사용이 가능하고 혼련 작업성의 측면에서 1∼5㎛인 것의 사용이 가능하며 함량은 5.0∼15.0중량％가 바람직하다. 본 발명에서 탄산칼슘(CaCo3) 함량이 5.0중량％ 미만일 경우 강성 발현의 효과가 미흡하며 15.0중량％ 이상 초과할 경우 유리섬유의 영향력으로 강성 발현이 미흡하게 된다.Component (C) of the present invention is calcium carbonate (CaCo 3 ) can be used as long as it can be easily obtained commercially, in terms of kneading workability can be used of 1 to 5㎛, the content is preferably 5.0 to 15.0% by weight Do. In the present invention, when the calcium carbonate (CaCo 3 ) content is less than 5.0% by weight, the effect of rigid expression is insufficient, and when more than 15.0% by weight, the rigid expression is insufficient due to the influence of glass fiber.
본 발명의 (D) 성분은 폴리에틸렌/유리섬유/탄산칼슘 블렌드의 혼련성 향상을 위한 상용화재로서 스테린산아연 그 함량은 0.2∼0.6중량％ 가 바람직하며 0.2중량％ 미만일때는 수지와의 계면 접착력을 충분히 유지할 수 없어 물성 향상에 효과가 없으며 0.6중량％ 를 초과할 경우에는 투입량을 증가시켜도 더 이상의 물성향상 효과를 기대하기가 어렵다.Component (D) of the present invention is a commercially available material for improving the kneading properties of polyethylene / glass fiber / calcium carbonate blend, and the content of zinc stearate is preferably 0.2 to 0.6% by weight, and when the content is less than 0.2% by weight, the interface adhesive force with resin If it is not sufficiently maintained, there is no effect on improving the physical properties, and if it exceeds 0.6% by weight, it is difficult to expect a further improvement of physical properties even if the input amount is increased.
유기실란계화합물은 그 종류가 특별히 제한되지 않으며 본 발명에서는 한 개 또는 두개의 아미노기를 포함하는 아미노실란계 화합물이 바람직하다. 적정량은 0.4∼0.7중량％ 이며 보다 바람직하게는 0.5∼0.7중량％이다. 상기 범위를 벗어날 경우 물성 향상을 기대할 수 없다.The type of organosilane compound is not particularly limited, and in the present invention, an aminosilane compound containing one or two amino groups is preferable. A proper amount is 0.4 to 0.7 weight%, More preferably, it is 0.5 to 0.7 weight%. If it is out of the above range can not be expected to improve the physical properties.
본 발명의 강성수지(복합폴리에틸렌) 조성물에 있어서 보강재, 충진재, 카본, 내열안정재, 내후안정재, 대전방지재, 활재, 슬립재, 핵재, 난연재, 안료, 염료등과 같은 통상의 각종 첨가제가 본 발명의 특징에 어긋나지 않은 범위 내에서 첨가 될 수 있으며 그 구체적인 예로 탈크, 탄소섬유, 클레이, 실리카, 알루미나, 카본블랙, 수산화마그네슘, 제올라이트, 황산, 바륨 등이 있다.In the rigid resin (composite polyethylene) composition of the present invention, conventional additives such as reinforcing materials, fillers, carbon, heat resistant stabilizers, weathering stabilizers, antistatic materials, lubricants, slip materials, nuclear materials, flame retardants, pigments, dyes, etc. It may be added within a range not contrary to the characteristics of the invention and specific examples thereof include talc, carbon fiber, clay, silica, alumina, carbon black, magnesium hydroxide, zeolite, sulfuric acid, barium and the like.
본 발명의 수지 조성물을 제조하는 방법에 있어서 단축 또는 이축 압출기를 사용한 혼련이 바람직하며 보편적으로 알려진 폴리에틸렌 수지 조성물을 제조하는 가공조건을 이용하고 폴리에틸렌 융점 이상에서의 배합이 가능하다. 단, 무기 충진재인 유리섬유, 탄산칼슘의 형상을 충분히 유지시키기 위하여 압출기 도중에서의 동시 또는 개별투입이 필수적이다.In the method for producing the resin composition of the present invention, kneading using a single screw or twin screw extruder is preferable, and mixing at a polyethylene melting point or higher is possible using processing conditions for producing a generally known polyethylene resin composition. However, simultaneous or separate injection during the extruder is essential in order to sufficiently maintain the shape of the inorganic filler glass fiber and calcium carbonate.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하나, 이러한 실시 예들은 단지 설명의 목적을 위한 것으로 본 발명의 보호 범위를 제한하여 해석되어서는 아니된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the protection scope of the present invention.
〈실시 예 및 비교 예〉<Example and Comparative Example>
동일 방향으로 회전하는 단축 압출기에 표1에서 나타낸 배합비로 폴리에틸렌, 유리섬유, 탄산칼슘 및 스테린산아연, 유기실란계 화합물을 배합하고 이를 100중량부에 대하여 0.7중량부로 산화 방지제 및 장기 내열 안정재를 투입한 후 용융 혼합시키고 압출하여 펠렛(Pellet) 상의 블렌드(Blend)물을 제조하고 80℃에서 진공 건조시켰으며, PE 이중벽 하수관 제조장치로 200m/m를 생산하였다. In a single-screw extruder rotating in the same direction, polyethylene, glass fiber, calcium carbonate, zinc stearate, and organosilane-based compound are blended at 0.7 parts by weight based on 100 parts by weight of an antioxidant and a long-term heat stabilizer. Then melt blended and extruded to produce blends on pellets, dried in vacuo at 80 ° C., and produced 200 m / m with PE double wall sewer pipe making equipment.
다만, 실시예 1,2 및 비교예 1,2에서는 혼련시의 온도를 220℃로 조절하고 비교예3,4에서는 230℃로 조절하였다. 상기의 블렌드를 제품으로 생산하여 평가하고 그 결과를 표1에 나타내었다.However, in Examples 1 and 2 and Comparative Examples 1 and 2, the temperature during kneading was adjusted to 220 ° C., and in Comparative Examples 3 and 4, 230 ° C. The blend was produced as a product and evaluated, and the results are shown in Table 1.
실시예 1에서는 유리섬유, 탄산칼슘의 도입이 물성 향상에 중요한 역할을 하여 유리섬유가 도입되지 않은 비교예 1의 탄산칼슘의 강화 폴리에틸렌 보다 강성 및 인장강도가 높게 나왔다.In Example 1, the introduction of glass fiber and calcium carbonate played an important role in improving physical properties, resulting in higher stiffness and tensile strength than the reinforced polyethylene of calcium carbonate of Comparative Example 1, in which glass fiber was not introduced.
실시예 2의 경우는 유리섬유가 도입되지 않은 비교2 경우보다 강도 및 인장강도가 높게 나왔으며 폴리에틸렌으로 만든 비교4의 경우와 물성의 차이가 많이 나타났다.In the case of Example 2, the strength and tensile strength were higher than those in Comparative 2, in which glass fiber was not introduced, and the physical properties were significantly different from those of Comparative 4 made of polyethylene.
측정방법How to measure
1) 강성(Stifness)1) Stiffness
ASTM D 2412 방법으로 상온에서 측정하였다.It was measured at room temperature by the ASTM D 2412 method.
2) 인장강도(Tensile strength)2) Tensile strength
ASTM D 638 방법으로 상온에서 측정하였다.It was measured at room temperature by the ASTM D 638 method.
3) 굴곡탄성율(Flexural modulus)3) Flexural modulus
ASTM D 790 방법으로 상온에서 측정하였다.It was measured at room temperature by the ASTM D 790 method.
이상 살펴본 바와 같이 본 발명에 의한 조성물은 관체를 성형함에 있어 강성 및 인장강도가 높아 수지재 관체 특히 수도관, 하수관등의 제작에 적합한 것으로 관체성형분야에 널리 사용될 수 있으며, 더 나아가서는 산업자재등의 공업적 이용범위가 매우 넓다 할 것이다. As described above, the composition according to the present invention has high rigidity and tensile strength in forming a pipe, and is suitable for the production of resin pipes, in particular, water pipes, sewer pipes, and the like. The industrial scope of use will be very wide.
Claims (2)
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| CN112549482A (en) * | 2020-12-02 | 2021-03-26 | 荆州亮诚科技股份有限公司 | Production method of ratproof silicon core pipe |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112549482A (en) * | 2020-12-02 | 2021-03-26 | 荆州亮诚科技股份有限公司 | Production method of ratproof silicon core pipe |
| CN112549482B (en) * | 2020-12-02 | 2022-04-29 | 荆州亮诚科技股份有限公司 | Production method of ratproof silicon core pipe |
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