KR101449583B1 - Method for manufacture of Pipe from polyvinly chloride resin molding composion - Google Patents
Method for manufacture of Pipe from polyvinly chloride resin molding composion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
Description
본 발명은 폴리염화비닐수지 성형조성물 및 경질 폴리염화비닐수지관의 제조방법에 관한 것으로서, 보다 구체적으로는 폴리염화비닐수지의 중합도를 향상시키는 첨가제를 함유하는 폴리염화비닐수지 성형조성물을 이용하여 기계적 성질을 보다 향상시킨 경질 폴리염화비닐수지관(Polyvinly chloride Pipe)에 관한 것이다.The present invention relates to a polyvinyl chloride resin molding composition and a method for producing a rigid polyvinyl chloride resin tube, and more particularly, to a polyvinyl chloride resin molding composition using a polyvinyl chloride resin molding composition containing an additive for improving the degree of polymerization of a polyvinyl chloride resin, And more particularly to a rigid polyvinyl chloride pipe.
폴리염화비닐(Polyvinly chloride; PVC)수지는 열가소성 수지로서 가공이 용이하고, 폴리에틸렌 또는 금속재료에 비해 가격이 저렴하며 경량이면서 기밀성 및 내식성이 높고, 취급 및 운반이 용이한 특성 등으로 인하여 오래전부터 각종 용기, 포장필름, 전선배관, 상수관, 하수관 등의 재료로 매우 다양한 용도로 광범위하게 적용되고 있다.Polyvinyl chloride (PVC) resin is a thermoplastic resin that is easy to process, less expensive than polyethylene or metal materials, lightweight, high in airtightness and corrosion resistance, and easy to handle and transport. Containers, packaging films, electric wire piping, water pipes, sewer pipes, and the like.
일반적으로 폴리염화비닐(PVC)수지는 중합도가 높으면, 기계적 성질은 강하지만 겔링 온도가 높아지고, 가공 온도범위가 좁아 가공이 용이하지 않으며, 중합도가 낮은 PVC수지는 겔링이 용이하고, 흐름성이 좋은 특성이 있으나, 기계적 강도가 낮은 단점이 있으므로 폴리염화비닐관 제조 시 기계적 물성과 가공성을 고려하여 적당한 중합도를 가진 PVC 수지를 선택하야 한다. 또한 경질 PVC수지를 가공할 때에는 적절한 유동성 및 열안정성을 갖게 하기 위하여 다양한 첨가제가 사용되고 있으나, 제한적인 원료사용과 까다로운 배합 및 가공조건으로 인하여 품질 불량발생이 많아 그 양과 종류는 신중하게 선택하여야 하는 문제점이 있다.In general, polyvinyl chloride (PVC) resins have high mechanical properties but have a high gelation temperature and a narrow working temperature range, which is not easy to process. PVC resins having a low degree of polymerization are easy to gel, However, since the mechanical strength is low, PVC resin having proper polymerization degree should be selected in consideration of mechanical properties and processability in the production of polyvinyl chloride pipes. In addition, when processing hard PVC resin, various additives are used in order to have appropriate fluidity and thermal stability. However, due to the limited use of raw materials, strict mixing and processing conditions, there are many defects in quality, .
PVC수지 성형조성물의 물성 및 가공성 향상 등의 방법에 관한 선행기술로 예를 들면, 국내 등록특허공보 등록번호 10-0982196호에는 아크릴-염화비닐 공중합 수지에 분산제로 아크릴산 폴리에스터를 조합한 아크릴-염화비닐수지 조성물을 이용하여 제조한 파이프를 개시하고 있으며, 국내 등록특허공보 등록번호 10-1070584호에서는 폴리염화비닐, 염소화폴리염화비닐, 아크릴-염화비닐계 그라프트 공중합체 및 충격보강제 등을 조합하여 내충격성을 개선한 염화비닐수지 조성물을 개시하고 있다.For example, Korean Registered Patent Publication No. 10-0982196 discloses a method for improving the physical properties and processability of a PVC resin molding composition, such as acrylic-chlorinated vinyl chloride resin combined with acrylic acid polyester as a dispersing agent Discloses a pipe manufactured using a vinyl resin composition, and Korean Patent Registration No. 10-1070584 discloses a pipe made of a combination of polyvinyl chloride, chlorinated polyvinyl chloride, acrylic-vinyl chloride graft copolymer, impact modifier, and the like Discloses a vinyl chloride resin composition having improved impact resistance.
상기한 선행기술들은 염화비닐수지와 함께 이종의 수지 내지 충격보강제의 사용에 의해 내충격성등 물성을 개선하고 있는 기술로서, 폴리염화비닐수지관 가공시 배합수지의 점성증가로 인해 수지 매트릭스와 가공조제간의 충분한 혼합을 위해 분산제를 추가적으로 사용하여야 하는 등의 문제점이 있다.The prior art described above is a technique which improves physical properties such as impact resistance by using a different type of resin or an impact modifier together with a vinyl chloride resin. As the viscosity of the blended resin increases during the processing of the polyvinyl chloride resin tube, There is a problem that a dispersing agent should be additionally used to sufficiently mix the components.
또 국내 등록특허공보 등록번호 10-1167974호에는 PVC에 사카라이트에스테르 화합물을 함유하는 압출성 PVC 조성물을 개시하고 있으며, 국내 등록특허공보 10-1223915호에 염화비닐공중합수지 또는 염소화 염화비닐수지인 중합도 500 ~ 1000 염화비닐계수지와 유기주석계 안정제, 충격보강제, 가공조제 및 활제로 이루어진 고유동성 경질 염화비닐계 수지 조성물을 개시하고 있으며, 이들 선행기술은 염화비닐수지계수지에 열안정제 내지 활제를 사용하여 가공성을 개선하고 있는 기술이다.Korean Patent Registration No. 10-1167974 discloses an extrudable PVC composition containing a saccharite ester compound in PVC, and Korean Patent Publication No. 10-1223915 discloses a vinyl chloride copolymer resin or a chlorinated vinyl chloride resin having a degree of polymerization Discloses an ultra high molecular weight vinyl chloride resin composition comprising 500 to 1000 vinyl chloride resins, an organosilicate stabilizer, an impact modifier, a processing aid, and a lubricant. These prior arts use a heat stabilizer or a lubricant for the vinyl chloride resin It is a technology that improves processability.
본 발명은 폴리염화비닐수지은 폴리염화비닐수지의 중합도를 향상시키는 첨가제를 함유하는 폴리염화비닐수지 성형조성물에 의해 경질 폴리염화비닐수지관을 제작함으로써 인장강도 및 굴곡강도를 향상시키는 것을 확인하고 본 발명을 완성하였다.The present invention confirms that the polyvinyl chloride resin improves the tensile strength and flexural strength by producing a rigid polyvinyl chloride resin tube by using a polyvinyl chloride resin molding composition containing an additive for improving the degree of polymerization of the polyvinyl chloride resin, .
본 발명은 폴리염화비닐수지 성형조성물 및 이를 이용하여 경질 폴리염화비닐수지관(Polyvinly chloride Pipe)를 제조하는 방법의 제공에 목적이 있으며, 보다 구체적으로는 폴리염화비닐수지의 중합도를 향상시키는 첨가제를 함유하는 폴리염화비닐수지 성형조성물 및 이를 이용하여 기계적 성질 즉 굴곡강도, 인장강도 및 장기 내수압성를 향상시킨 경질 폴리염화비닐수지관의 제조방법을 제공하는 것을 목적으로 하는 것이다.The present invention relates to a polyvinyl chloride resin molding composition and a method for producing a rigid polyvinyl chloride pipe by using the same. More specifically, the present invention relates to an additive for improving the degree of polymerization of a polyvinyl chloride resin And a method of manufacturing a rigid polyvinyl chloride resin tube having improved mechanical strength, that is, flexural strength, tensile strength and long-term water pressure resistance, by using the same.
본 발명이 목적하고 있는 과제를 해결하기 위한 수단으로서 본 발명의 폴리염화비닐수지 성형조성물은 염화비닐수지 100중량부에 대하여, UV/EB(Ultra-violet/Electron beam)경화성수지 0.5 ~ 4중량부, 충격보강제 4 ~ 10중량부, 탄산칼슘 0.1 ~ 10중량부, 안정제 3 ~ 7중량부, 가공조제 0.1 ~ 5중량부로 조성된 폴리염화비닐수지 성형조성물로 이루어진다.As a means for solving the object of the present invention, the polyvinyl chloride resin molding composition of the present invention comprises 0.5 to 4 parts by weight of a UV / EB (Ultra-violet / Electron beam) curable resin per 100 parts by weight of a vinyl chloride resin 4 to 10 parts by weight of an impact modifier, 0.1 to 10 parts by weight of calcium carbonate, 3 to 7 parts by weight of a stabilizer, and 0.1 to 5 parts by weight of a processing aid.
상기 본 발명에 따른 폴리염화비닐수지는 일반적으로 관 내지 수도관 성형용으로 사용되는 폴리염화비닐수지이면 적당하고, 특별히 제한되지 않으며, 중합도가 너무 낮으면 인장강도나 경도가 떨어지게 되고, 반대로 중합도가 너무 높으면 가공성이 떨어지므로 중합도 700 ~ 1000의 폴리염화비닐수지를 사용하는 것이 바람직하다.The polyvinyl chloride resin according to the present invention is suitable as long as it is a polyvinyl chloride resin generally used for tube or water pipe forming and is not particularly limited. When the degree of polymerization is too low, the tensile strength and hardness are lowered. On the contrary, It is preferable to use a polyvinyl chloride resin having a polymerization degree of 700 to 1000 because the workability is poor.
상기 폴리염화비닐수지 성형조성물에 첨가되는 충격보강제는 수지에 탄성을 부여하여 내충격성을 보강하기 위하여 조합하는 성분이며, 메틸메타크릴레이트 부타디엔 스티렌 공중합체(MBS), 염소화폴리에틸렌(CPE), 에틸렌비닐아세테이트계(EVA) 및 아크릴계 보강제로부터 1 또는 2이상 성분을 혼합하여 사용하며, 또 열안정제, 가공조제는 PVC 성형체를 제조할 때 일반적으로 사용하는 첨가제로서, 특별히 제한하는 것은 아니다. 예를 들면, 안정제는 열에 대한 안정성을 높임으로써 착색, 분해를 방지하는 역할을 하는 성분으로, 본 발명에서는 활제가 포함된 Pb계, Ca-Zn계, Tin계의 복합안정제를 사용하여 가공시 마찰열의 발생을 억제하고, 이형을 용이하게 하며 또 가공조제는 수지의 겔링을 촉진하는 역할을 하는 성분으로 본 발명에서는 아크릴계 가공조제를 사용하며, 그 외에 본 발명에서는 필요에 따라 안료를 첨가할 수도 있다. The impact modifier added to the polyvinyl chloride resin molding composition is a component to be combined to reinforce the impact resistance by imparting elasticity to the resin. Examples of the impact modifier include methyl methacrylate butadiene styrene copolymer (MBS), chlorinated polyethylene (CPE), ethylene vinyl (EVA) and an acryl-based reinforcing agent, and the heat stabilizer and processing aid are not particularly limited as additives commonly used in the production of a PVC molded article. For example, stabilizers serve to prevent coloring and decomposition by increasing the stability to heat. In the present invention, Pb-based, Ca-Zn-based and Tin-based composite stabilizers containing a lubricant are used. And the processing aid serves to accelerate the gelling of the resin. In the present invention, an acrylic processing aid is used. In addition, a pigment may be added in the present invention if necessary .
본 발명에 따른 폴리염화비닐수지 성형조성물에 첨가하는 UV/EB경화성수지는 아래 [그림 1]에 나타낸 바와 같이 압출 가공 중에 열 또는 UV 의해 반응을 일으켜 고분자 사슬의 부분 가교 역할을 하는 첨가제로서 압출 가공 후, 폴리염화비닐수지의 중합도를 향상시켜 물성을 향상시킨다. The UV / EB curable resin added to the polyvinyl chloride resin molding composition according to the present invention is an additive that acts as a partial crosslinking of a polymer chain by causing a reaction by heat or UV during extrusion processing as shown in [Fig. 1] , The degree of polymerization of the polyvinyl chloride resin is improved to improve the physical properties.
[그림1][Figure 1]
본 발명은 UV/EB 경화성수지를 첨가함으로써 압출 가공이 용이한 중합도 700 ~ 1000의 폴리염화비닐수지를 사용하여, 최종적으로 중합도 1200 ~ 2000을 갖는 고중합도 폴리염화비닐관을 제조하는 것이 가능하기 때문에 기계적 성질의 개선을 위하여 높은 중합도의 폴리염화비닐수지를 성형원료로 사용하는 성형기술의 결점인 가공성이 용이하지 않은 문제를 해결함과 동시에 높은 중합도를 갖는 경질 폴리염화비닐수지관을 제작함으로써 인장강도, 굴곡강도 및 장기 내수압성을 향상시킨 경질 폴리염화비닐수지관을 제조하는 특징을 가지고 있다. Since the present invention makes it possible to produce a highly-polymerized polyvinyl chloride tube with a final polymerization degree of 1200 to 2000 using a polyvinyl chloride resin having a polymerization degree of 700 to 1000, which is easy to be extruded by adding a UV / EB-curable resin, A hard polyvinyl chloride resin pipe having a high degree of polymerization is prepared, and at the same time, a process for producing a rigid polyvinyl chloride resin pipe having a high degree of polymerization is made, And has a feature of producing a rigid polyvinyl chloride resin tube having improved flexural strength and long-term water pressure resistance.
상기 UV/EB 경화성수지는 낮은 계면활성을 갖는 비자극성 지방족 2관능성 아크릴계화합물이며, 구체적 화합물로는 프로폭실레이트 네오펜틸 글리콜 디아크릴레이트 (Propoxylated neopentyl glycol diacrylate ; PONPGDA)이며, 코팅제, 인쇄바니시, 잉크 등의 가교제(경화제)로 사용되고 있으며, 유럽특허 EP2078061 B1에 잉크젯트인쇄와 관련하여 가교(경화) 첨가제로 기재하고 있는 공지화합물이며, 상품명 Ebecryl™145(제조회사명; Allnex사, CYTEC사)로 시판되고 있다.The UV / EB curable resin is a non-polar aliphatic bifunctional acrylic compound having a low surface activity. Specific examples of the UV / EB curable resin include propoxylated neopentyl glycol diacrylate (PONPGDA), a coating agent, a printing varnish, (Trade name) manufactured by Allnex Co., Ltd., CYTEC Co., Ltd.), which is used as a crosslinking agent (curing agent) such as an ink for ink-jet printing in EP2078061 B1, .
상기 Ebecryl™145는 첨가량이 증가할수록 가교 빈도 증가로 인한 중합도 향상으로 기계적 물성이 증가되는 효과가 나타나지만, 가교도가 너무 높으면 가공성이 좋지 않으므로 상기한 바와 같이 폴리염화비닐수지 100중량부에 대하여 0.5 ~ 5 중량부로 조성되는 것이 바람직하다.As described above, EbecrylTM 145 improves the mechanical properties by increasing the degree of polymerization due to the increase in the crosslinking frequency. However, if the crosslinking degree is too high, the workability is not good. As described above, By weight.
그리고 본 발명의 또 다른 목적달성을 위한 과제의 해결수단으로서 본 발명에 따른 경질 폴리염화비닐수지관의 제조방법은 a)원료배합단계, b)원료배합단계에서 얻어진 원료혼련물의 냉각과정에 UV/EB 경화성수지를 배합하면서 냉각시켜 성형조성물을 얻는 1차 냉각단계, c)상기 성형조성물을 성형하는 압출성형단계, d)성형물에 UV를 조사하여 가교 및 경화시키는 경화단계 및 e)경화된 성형물을 냉각하는 2차 냉각단계로 이루어진다.The present invention also provides a process for producing a rigid polyvinyl chloride resin pipe according to the present invention, which comprises the steps of: a) mixing a raw material; b) cooling the raw material kneaded product obtained in the raw material blending step; C) an extrusion molding step for molding the molding composition; d) a curing step for crosslinking and curing the molded article by irradiating UV, and e) a curing step for curing the molded article And a second cooling step for cooling.
상기한 본 발명의 경질 폴리염화비닐수지관 제조과정은 통상적인 폴리염화비닐수지관의 제조공정과는 상이하게 수행되며, 압출다이(Die)에서 성형되어 나오는 반겔링 상태의 성형물을 2차 냉각단계 전에 UV조사에 의해 가교 및 경화시키는 가교단계가 추가되는 상이점이 있는 것이 특징이다.The process for producing the rigid polyvinyl chloride resin tube of the present invention is different from the conventional process for producing the polyvinyl chloride resin tube, and the mold of the semi-gelled state, which is molded in an extrusion die, And a crosslinking step in which crosslinking and curing are carried out by UV irradiation before is added.
상기 a)원료배합단계는 UV/EB경화성수지를 제외하고, 본 발명에 따라 폴리염화비닐수지, 충격보강제, 탄산칼슘, 안정제 및 가공조제를 일정비율로 조합한 원료성분을 배합하고 헨셀믹서기(수퍼믹서)에 의해 고속으로 혼련하는 과정에 마찰열이 발생함에 따라 혼련장치 내의 온도가 상승하여 수지를 연화시키면서 균일한 조성으로 혼합된 원료혼련물이 얻어지며, 혼련과정은 100 ~ 160℃의 온도범위에서 5 ~ 30분 동안 혼련하는 것이 바람직하고, 혼련온도 및 혼련시간이 상기 조건을 벗어나면, 온도가 지나치게 상승하여 의해 수지가 분해되거나 혼련이 불완전하여 성형물의 물성이 떨어진다.The raw material mixing step a), except for the UV / EB curable resin, is carried out by mixing the raw material components obtained by combining the polyvinyl chloride resin, the impact modifier, the calcium carbonate, the stabilizer, And the mixture is kneaded at a high speed by a Henschel mixer (super mixer). As the friction heat is generated, the temperature in the kneading apparatus rises to soften the resin, thereby obtaining a raw material kneaded product having a uniform composition. It is preferable to knead for 5 to 30 minutes at a temperature range of 160 to 160 DEG C. If the kneading temperature and the kneading time are out of the above range, the temperature is excessively increased to decompose the resin or incomplete kneading to deteriorate the physical properties of the molded article.
상기 b)1차 냉각단계는 원료성분과 함께 UV/EB 경화성수지를 배합할 경우 고속혼련으로 인하여 온도상승에 의해 폴리염화비닐이 과도하게 가교화되는 것을 방지하여 가교화를 최소화하면서 균일하게 혼련시키기 위하여 원료혼련물을 냉각시키는 과정에 UV/EB경화성수지(Ebecryl™145)를 폴리염화비닐수지 100중량부에 대하여 0.5 ~ 5 중량부로 배합하고, 40 ~ 60℃로 냉각하여 고형화된 성형조성물을 얻는 것으로 이루어지며, 40 ~ 60℃ 수준으로 온도를 낮추기 위해서 10 ~ 20분 정도의 시간이 소요된다.When the UV / EB curable resin is blended together with the raw material component in the b) primary cooling step, the polyvinyl chloride is prevented from being excessively crosslinked due to the temperature increase due to the high-speed kneading, thereby uniformly kneading the resin while minimizing the crosslinking In order to cool the raw material kneaded product, a UV / EB curable resin (Ebecryl (TM) 145) is added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the polyvinyl chloride resin and cooled to 40 to 60 캜 to obtain a solidified molding composition And it takes 10 to 20 minutes to lower the temperature to 40 to 60 ° C.
또 c)압출성형단계는 본 발명에 따른 상기 성형조성물을 압출하여 관(pipe)의 형태로 성형하는 공정이며, 압출성형기를 이용하여 압출한다.(C) The extrusion molding step is a step of extruding the molding composition according to the present invention into a pipe, and extruding it using an extrusion molding machine.
상기 압출성형단계는 성형조성물이 고형화된 상태이므로 연화시키기 위하여 가열하면서 공정을 수행하는 것으로 이루어지며, 본 발명의 상기 압출성형단계에서는 1차 냉각단계에서 투입된 UV/EB경화성수지(Ebecryl™145)가 열에 의해 분해되어 상기한 [그림 1]과 같이 폴리염화비닐수지를 가교시켜 고중합도의 폴리염화비닐관이 형성되며, 압출성형단계의 온도가 지나치게 높으면 UV/EB경화성수지(Ebecryl™145)의 분해가 빨라져 높은 가교도로 인한 가공성 저하를 초래할 수 있어 160 ~ 200℃ 온도로 가열하는 것이 바람직하고, 압출속도가 너무 느리거나 너무 빠를 경우에는 작업시간이 오래 걸리거나 성형물의 형태가 균일하지 못할 수 있으므로, 300 ~ 500kg/h의 속도로 압출하는 것이 바람직하다.In the extrusion molding step, the UV / EB curable resin (Ebecryl (TM) 145) added in the first cooling step is added in the extrusion molding step of the present invention As shown in [Figure 1], polyvinyl chloride resin is crosslinked by decomposition by heat to form a polyvinyl chloride tube of high polymerization degree. When the temperature of the extrusion step is too high, decomposition of UV / EB curable resin (Ebecryl ™ 145) It is preferable to heat to a temperature of 160 to 200 ° C. If the extrusion speed is too slow or too fast, it takes a long time to work or the shape of the molded product may not be uniform. Therefore, To 500 kg / h.
상기 d)경화단계는 본 발명의 특징적인 부분으로 상기 c)압출성형단계에서 성형되어 나온 반겔링 상태의 폴리염화비닐관 외부에 UV램프 등의 UV조사수단에 의해 UV조사를 통하여 UV/EB경화성수지(Ebecryl™145) 분해를 촉진시킴으로써 최종적으로 고중합도의 폴리염화비닐관을 형성시키는 단계이며, 상기 1차 냉각단계 및 압출성형단계를 통한 1차 가교와 경화단계의 UV조사에 의한 2차 가교 및 경화를 통해 고중합도를 갖는 폴리염화비닐관을 제조할 수 있다.The curing step is a characteristic part of the present invention. The curing step is a step of curing the UV / EB curable resin (c) by UV irradiation by UV irradiation means such as UV lamp on the outside of the polyglycidyl chloride tube, (Ebecryl ™ 145), thereby forming a polyvinyl chloride tube having a high polymerization degree. The secondary crosslinking and curing by UV irradiation in the primary crosslinking step and the curing step by the primary cooling step and the extrusion molding step, A polyvinyl chloride tube having a high degree of polymerization can be produced.
상기 e)2차 냉각단계는 최종공정인 마무리 공정으로 압출성형물을 냉각하고 필요한 크기로 절단하여 경질 폴리염화비닐수지관을 완성하는 것으로 이루어진다.The e) secondary cooling step consists of cooling the extrudate by a finishing process, which is the final process, and cutting the extrudate to a required size to complete the rigid polyvinyl chloride resin pipe.
본 발명에 따른 폴리염화비닐수지 성형조성물로 제조된 경질 폴리염화비닐수지관은 기계적 성질의 개선을 위하여 높은 중합도의 폴리염화비닐수지를 성형원료로 사용하여 성형하는 성형기술의 결점인 가공성이 용이하지 않은 문제를 해결함과 동시에 일반적으로 관 내지 수도관 성형용으로 사용되는 중합도 700 ~ 1000의 폴리염화비닐수지와 가교제를 성형원료로 사용하여, 열과 UV에 의한 가교에 의해 보다 높은 중합도를 갖는 경질 폴리염화비닐수지관을 제작하여 폴리염화비닐수지관의 기계적 성질을 향상시키는 효과를 나타낸다.The hard polyvinyl chloride resin tube made of the polyvinyl chloride resin molding composition according to the present invention is easy to process, which is a drawback of a molding technique for molding a polyvinyl chloride resin having a high polymerization degree as a molding material for the purpose of improving mechanical properties And at the same time, by using a polyvinyl chloride resin and a crosslinking agent having a degree of polymerization of 700 to 1000, which are generally used for pipes and pipes, as a molding material, they are crosslinked by heat and UV to form hard polychlorinated And the mechanical properties of the polyvinyl chloride resin pipe are improved by producing a vinyl resin pipe.
도 1은 본 발명에 따른 경질 폴리염화비닐수지관을 제조하는 개략적인 공정도.
도 2는 본 발명에 따른 성형조성물1과 성형조성물5를 GPC(Gel Permeation Chromatogrphy)를 이용하여 분자량을 측정하고 분자량증가를 나타낸 도표.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic process diagram for producing a rigid polyvinyl chloride resin tube according to the present invention. FIG.
2 is a graph showing the molecular weight increase and molecular weight increase of the molding composition 1 and the molding composition 5 according to the present invention using GPC (Gel Permeation Chromatography).
아래에서는 실시예 및 시험예를 통하여 본 발명에 따른 경질 폴리염화비닐수지 성형조성물로 폴리염화비닐수지관을 제조하는 방법에 대하여 보다 구체적으로 설명하기로 한다.Hereinafter, a method for producing a polyvinyl chloride resin tube using the molding composition for a rigid polyvinyl chloride resin according to the present invention will be described in more detail with reference to Examples and Test Examples.
<실시예><Examples>
아래 [표 1]에 제시한 배합비에 따라 조성되는 성형조성물1 내지 성형조성물5를 상수관의 성형조성물로 하고, 각각의 성형조성물은 공통적으로 Ebecryl™145를 (CYTEC사에서 구입) 제외하고 아래 [표 1]에 제시한 배합비에 따라(조성물2 내지 5에 사용된 배합에 안료(TiO) 1중량부 각각 첨가) 배합하고 헨셀믹서기로 20분 동안 혼련한 후, 성형조성물1을 제외하고, Ebecryl™145를 (CLTEC사에서 구입)투입과 함께, 15분간 Mixing하면서 50℃로 냉각하여 고형의 성형조성물2 내지 5를 제조하였다. The molding compositions 1 to 5 formed according to the compounding ratios shown in Table 1 below were used as molding compositions for a water pipe, Each The molding composition was commonly blended according to the blending ratio shown in Table 1 below (except that EbecrylTM 145 (purchased from CYTEC) was added (adding 1 part by weight of each pigment (TiO) to the blend used in the compositions 2 to 5) After kneading with a Henschel mixer for 20 minutes, except for the molding composition 1, Ebecryl ™ 145 (purchased from CLTEC) was added and the mixture was cooled to 50 ° C. while mixing for 15 minutes to prepare solid molding compositions 2 to 5 .
상기 성형조성물1 내지 5를 압출성형기에 각각 투입하고, 약 180℃로 가열한 후 400kg/h의 속도로 압출한 다음, UVLamp Power(2500W)를 사용하여 UV조사(irradiation)후, 냉각하여 경질 폴리염화비닐수지관을 제조하였다. Each of the molding compositions 1 to 5 was put in an extruder, heated at about 180 캜, extruded at a rate of 400 kg / h, irradiated with UV lamp power (2500 W) A vinyl chloride resin tube was prepared.
<시험예><Test Example>
상기 <실시예>에서 제작한 경질 폴리염화비닐수지관에 대해서 중합도 및 물성(인장강도 및 굴곡강도, 장기 내수압)을 시험하고, 그 결과를 아래 [표 2]에 나타내었다.Polymerization degree and physical properties (tensile strength, flexural strength, long-term water pressure) of the rigid polyvinyl chloride resin tube produced in the above Example were tested, and the results are shown in Table 2 below.
아래 [표 2]의 물성시험에 있어서 인장강도 및 장기 내수압 측정은 KSM 3401에 따라 측정하였으며, 굴곡강도는 ASTM D790(test speed:1.3mm/min)에 따라 측정하였다.The tensile strength and long-term water pressure were measured according to KSM 3401 in the physical properties test of Table 2 below, and the flexural strength was measured according to ASTM D790 (test speed: 1.3 mm / min).
중합도 측정은 Ubbelohde 점도계를 사용하여 25℃에서 상대점도를 측정한 후, 환원점도와 본성점도를 농도 0%로 외삽하여 구하였으며, 그 중 성형조성물1과 조성물5는 Waters 社의 GPC(Gel Permeation Chromatogrphy)를 이용하여 분자량을 측정하여 분자량 증가를 확인하였다[도 2 참조]. The degree of polymerization was determined by measuring the relative viscosity at 25 ° C using a Ubbelohde viscometer, and then extrapolated to a reduced viscosity and a native viscosity at a concentration of 0%. Among them, the molding compositions 1 and 5 were Gel Permeation Chromatography ) To determine the molecular weight increase (see FIG. 2).
그리고 장기 내수압 시험은 KSM 3401의 내압 크리프 시험 기준에 따라, 시험온도 60℃, 시험압력 16㎏f/㎠, 100관으로 측정하였다. 내압 크리프 시험은 100관 1m(길이)를 샘플링 하여, 관 내부에 물을 채워 60℃에서 16㎏f/㎠의 압력으로 지속적으로 힘을 가하여 관이 파열되는 시간을 기준으로 측정하였다.And long-term hydrostatic test in accordance with the internal pressure creep test standard of KSM 3401, test temperature 60 ℃, test pressure 16㎏ f / ㎠, was measured in the tube 100. Pressure-resistant creep test was determined based on the time at which to sample the tube 100 1m (length), filled with water to the tube interior at a pressure of 60 ℃ 16㎏ f / ㎠ continuously applies a force tube rupture.
상기 [표 1] 및 [표 2]에 나타난 바와 같이, 성형조성물에 Ebecryl™145(UV/EB경화성수지)가 첨가된 조성물들은 Ebecryl™145(UV/EB경화성수지) 첨가량의 증가할수록 중합도가 증가하였으며, [도 2]와 같이 GPC 데이타에서도 중합도 증가를 확인할 수가 있었다. 인장강도 및 굴곡강도, 장기 내수압성도 Ebecryl™145(UV/EB경화성수지)를 첨가한 성형조성물 2, 3, 4, 5가 우수하게 나타나는 것을 확인할 수 있으므로, 본 발명의 특징인 성형조성물에 첨가제로 Ebecryl™145(UV/EB경화성수지)를 첨가하여 중합도 개선과 함께 기계적 성질을 개선하는 효과를 달성하는 것을 확인할 수가 있다.As shown in [Table 1] and [Table 2], the compositions to which Ebecryl ™ 145 (UV / EB curable resin) was added to the molding composition increased in polymerization degree as the amount of Ebecryl ™ 145 (UV / EB curable resin) As shown in FIG. 2, the increase in polymerization degree was confirmed even in the GPC data. It can be confirmed that the molding compositions 2, 3, 4, and 5 to which the Ebecryl ™ 145 (UV / EB curable resin) is added exhibit excellent properties. Therefore, Ebecryl 占 145 (UV / EB-curable resin) was added to improve the polymerization degree and mechanical properties.
Claims (6)
b).상기 원료혼련물를 냉각하면서 상기 폴리염화비닐수지 100중량부에 대하여 UV/EB경화성수지인 프로폭실레이트 네오펜틸 글리콜 디아크릴레이트(Propoxylated neopentyl glycol diacrylate) 0.5 ~ 5중량부를 투입하고 혼련하여 성형조성물을 얻는 1차 냉각단계와,
c).성형조성물을 160 ~ 200℃로 가열한 후 압출하여 관형상으로 압출 성형하는 압출성형단계와,
d).압출되어 나오는 반 겔링 상태의 관형상의 성형물 외부로 UV를 조사하여 가교 및 경화시키는 경화단계 및
e).경화된 관형상의 성형물을 냉각하는 2차 냉각단계를 포함하는 것을 특징을 하는 경질 폴리염화비닐수지관의 제조방법. a) Polymerization degree 700 to 1000 A raw material for kneading 4 to 10 parts by weight of an impact modifier, 0.1 to 10 parts by weight of calcium carbonate, 3 to 7 parts by weight of a stabilizer, and 0.1 to 5 parts by weight of a processing aid, based on 100 parts by weight of a polyvinyl chloride resin A mixing step,
b) 0.5 to 5 parts by weight of propoxylated neopentyl glycol diacrylate, which is a UV / EB curable resin, is added to 100 parts by weight of the polyvinyl chloride resin while cooling the raw material kneaded product, A primary cooling step to obtain the composition,
c) an extrusion molding step of heating the molding composition to 160 to 200 占 폚, extruding the mixture into a tubular shape,
d) a curing step of irradiating UV light to the outside of the tubular moldings in an extruded semi-gelled state to crosslink and cure, and
and e) a second cooling step of cooling the cured tubular molding.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180045147A (en) * | 2016-10-25 | 2018-05-04 | 한국타이어 주식회사 | Sealant continuous manufacturing machine for tire |
| CN108912533A (en) * | 2018-06-15 | 2018-11-30 | 鹤山联塑实业发展有限公司 | A kind of pvc material and a kind of polychloroethylene pipes that novel anti-UV is modified |
| KR102621088B1 (en) | 2023-10-05 | 2024-01-03 | 황시현 | Rigid polyvinyl chloride pipe |
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| JP2935371B2 (en) | 1989-06-27 | 1999-08-16 | 大日本印刷株式会社 | Processing method of polyvinyl chloride resin products including electron beam irradiation process |
| KR20050096074A (en) * | 2004-03-29 | 2005-10-05 | 김학건 | A plastic pipe jointing tube that have strengthened and manufacturing method thereof |
| KR100909183B1 (en) * | 2009-03-17 | 2009-07-23 | 유영화학(주) | Pvc pipe including carcon fiber and manufacturing method of the same |
| KR20110054037A (en) * | 2003-05-21 | 2011-05-24 | 제트 코포레이션 | Thermoplastic powder material system for appearance models from 3d printing systems |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2935371B2 (en) | 1989-06-27 | 1999-08-16 | 大日本印刷株式会社 | Processing method of polyvinyl chloride resin products including electron beam irradiation process |
| KR20110054037A (en) * | 2003-05-21 | 2011-05-24 | 제트 코포레이션 | Thermoplastic powder material system for appearance models from 3d printing systems |
| KR20050096074A (en) * | 2004-03-29 | 2005-10-05 | 김학건 | A plastic pipe jointing tube that have strengthened and manufacturing method thereof |
| KR100909183B1 (en) * | 2009-03-17 | 2009-07-23 | 유영화학(주) | Pvc pipe including carcon fiber and manufacturing method of the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180045147A (en) * | 2016-10-25 | 2018-05-04 | 한국타이어 주식회사 | Sealant continuous manufacturing machine for tire |
| CN108912533A (en) * | 2018-06-15 | 2018-11-30 | 鹤山联塑实业发展有限公司 | A kind of pvc material and a kind of polychloroethylene pipes that novel anti-UV is modified |
| KR102621088B1 (en) | 2023-10-05 | 2024-01-03 | 황시현 | Rigid polyvinyl chloride pipe |
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