KR20210054103A - Tracking resistant insulation composition and high voltage cable comprising the same - Google Patents

Tracking resistant insulation composition and high voltage cable comprising the same Download PDF

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KR20210054103A
KR20210054103A KR1020190139633A KR20190139633A KR20210054103A KR 20210054103 A KR20210054103 A KR 20210054103A KR 1020190139633 A KR1020190139633 A KR 1020190139633A KR 20190139633 A KR20190139633 A KR 20190139633A KR 20210054103 A KR20210054103 A KR 20210054103A
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insulating composition
metal hydroxide
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김상범
김준엽
최병권
정영섭
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한국생산기술연구원
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    • H—ELECTRICITY
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Abstract

The present invention relates to an insulation composition including a tracking-resistant insulation agent introduced into a surface of polydimethylsiloxane, a high voltage cable with improved tracking-resistant properties manufactured by including the insulation composition, and a manufacturing method thereof. As the insulation strength of an insulator itself is improved, heat-resistant properties and the tacking-resistant properties are improved. Therefore, the service life can be extended, thereby confirming the high industrial use value.

Description

내트래킹성 절연 조성물 및 이를 포함하는 고전압 케이블{Tracking resistant insulation composition and high voltage cable comprising the same}Tracking resistant insulation composition and high voltage cable comprising the same

본 발명은 폴리디메틸실록산을 표면에 도입한 내트래킹제를 포함하는 절연 조성물 및 상기 절연 조성물을 포함하여 제조된 내트래킹성이 향상된 고전압 케이블과 이의 제조방법에 관한 것이다. The present invention relates to an insulating composition comprising a tracking agent in which polydimethylsiloxane is introduced into a surface, and to a high voltage cable with improved tracking resistance and a method of manufacturing the same.

전세계적으로 전력에너지 (electric energy) 수요는 2050년까지 지속적으로 증가하는 추세이며, 이러한 전력 수요 증가는 대규모 전력계통 송전과 계통 간 송전망 연계가 확대되어야 가능할 것으로 전망되고 있으며, 제품 중심 제조업에서 디지털 설비/네트워크 기술/소프트웨어가 결합된 시스템화 되고 있어 전력 송배전 분야에서도 단순 전력기기 제조에서 디지털로 접목시킨 제품개발이 필요하게 되었다.Globally, the demand for electric energy continues to increase until 2050, and this increase in electric power demand is expected to be possible only when the large-scale power system transmission and the connection of the transmission network between the grids are expanded. /Network technology/software are being combined into a system, so in the field of power transmission and distribution, it is necessary to develop a product that combines digitally from simple power device manufacturing.

최근 국내 옥외용 전력케이블의 송전용량을 증대시키고자 하는 요구가 증가되고 있고 이같이 송전용량을 증가시키기 위해서는 대규격의 케이블을 사용하거나 또는 송전 손실을 줄이는 방법 등이 검토될 수 있으나, 이러한 방법들은 비현실적이며 비용이 많이 소모되어 경제성이 떨어지게 되는 단점을 가진다.Recently, the demand to increase the transmission capacity of the domestic outdoor power cable is increasing, and in order to increase the transmission capacity in this way, the use of a large standard cable or a method of reducing transmission loss may be considered, but these methods are impractical. It has a drawback in that it is costly and economical is deteriorated.

전력(electric power)은 전압(voltage)과 전류(current)의 곱에 비례하기 때문에 전력을 송전할 때 전압을 높이면 전류가 적게 되어 케이블 비용이 경감되며, 똑같은 굵기의 케이블이면 보다 많은 전력을 보낼 수 있게 된다. 대용량과 장거리 송전이 요구되는 대형 전력계통에서는 전력손실의 감소, 건설용지 문제, 송전용량의 증대 등의 면에서 볼 때 송전전압을 높이는 고압송전이 필수적이라고 할 수 있다.Since electric power is proportional to the product of voltage and current, increasing the voltage when transmitting power reduces the current and reduces the cable cost, and a cable of the same thickness can send more power. There will be. In large power systems that require large-capacity and long-distance transmission, it can be said that high-voltage transmission to increase the transmission voltage is essential in terms of reduction of power loss, construction site problems, and increase in transmission capacity.

고압으로 송전하기 위해서는 고압에 충분히 견딜 수 있는 송전선로나 변압기(transformer), 차단기(breaker) 등의 연결기기에 대한 절연 기술(insulation technology)이 필요하며, 코로나(corona) 잡음(noise)이나, 전파장애(radio disturbance), 통신유도장애 등의 문제점도 제기되고 있으나 이들에 대한 보완 기술이 지속적으로 개발되고 있어서 이들에 대한 문제점도 점차 해결되고 있다.In order to transmit at high voltage, insulation technology is required for transmission lines that can sufficiently withstand high voltages, connected devices such as transformers and breakers, and corona noise or radio wave disturbances. Problems such as radio disturbance and communication-induced disturbance have also been raised, but the problems for them are gradually being solved as complementary technologies are continuously developed.

종래의 가공 배전 케이블은 내열 가교 폴리에틸렌(cross-linked polyethylene) 절연층(insulation layer), 내열 반도전층(heat resistance semi-conductive layer), 강심 알루미늄(aluminium) 도체(conductor)로 구성된다.Conventional overhead distribution cables are composed of a heat-resistant cross-linked polyethylene insulation layer, a heat resistance semi-conductive layer, and a steel core aluminum conductor.

폴리에틸렌 가교 방식(cross-linking type)은 유기 과산화물(organic peroxide) 혹은 실란(silane)을 등이 있다. 폴리에틸렌 수지(resin)는 이와 같이 가교 과정(process)을 통하여 선형인 분자구조(linear molecular structure)가 3차원적인 망상구조를 가지는 가교 폴리에틸렌 수지가 되며, 취약한 물성의 고분자를 보다 안정된 구조로 전환시키거나 원하는 물성으로 개질할 수 있다. The polyethylene cross-linking type includes organic peroxide or silane. Polyethylene resin becomes a crosslinked polyethylene resin having a three-dimensional network structure with a linear molecular structure through the crosslinking process, and converts a polymer of weak physical properties to a more stable structure. It can be modified to desired physical properties.

요컨대, 이런 가교 가능한 고분자 수지(polymer resin)를 이용하여 케이블의 절연 재질로 사용할 경우 열가소성 재료(thermoplastic material)로 절연(insulation)하는 것 보다 내열성, 내용매성, 내화학성은 물론 내구성까지 향상시킬 수 있고 난연성이 향상되는 특징을 가진다.In short, when using such a crosslinkable polymer resin as an insulation material for cables, heat resistance, solvent resistance, chemical resistance, as well as durability can be improved rather than insulation with a thermoplastic material. It has a feature of improving flame retardancy.

하지만 송전 시에는 도체에서 열이 발생하게 되며, 종래의 가교 폴리에틸렌 절연 케이블(cable)은 저밀도폴리에틸렌(low density polyethylene)을 사용하여 가교한 것으로 가교 폴리에틸렌 재료의 최고 허용온도가 90℃인 관계로 인하여 송전 시 전류량의 제한이 있었다. 이러한 가교 폴리에틸렌 재료의 사용 온도 제한은 가교 폴리에틸렌 재료의 구조에 기인하는 것으로, 가교 폴리에틸렌의 결정 용융온도인 약 110℃ 이상이 되면 전력 케이블의 절연층으로 동작하기 위해 필요한 가교 폴리에틸렌의 물성이 급격하게 저하되게 되어 절연재료로서의 기능이 현저히 저하된다.However, during transmission, heat is generated from the conductor, and the conventional crosslinked polyethylene insulated cable is crosslinked using low density polyethylene, and the maximum allowable temperature of the crosslinked polyethylene material is 90℃. There was a limit on the amount of current at the time. The use temperature limit of this crosslinked polyethylene material is due to the structure of the crosslinked polyethylene material, and when the crystal melting temperature of the crosslinked polyethylene reaches about 110°C or higher, the properties of the crosslinked polyethylene required to operate as an insulating layer of a power cable are sharply deteriorated. As a result, the function as an insulating material is significantly deteriorated.

또한 알루미늄 도체(conductor)는 케이블의 대부분을 차치하고 있는 구리 도체에 이어 케이블의 재료로 전도성이 크고 가볍고 동일한 무게의 동에 비해 2배의 전류를 통할 수 있어 아주 경제적인 금속(metal)으로 알려져 있으나 전도율은 구리의 60% 정도여서 동일한 전력을 송전 시 높은 발열문제를 야기 시키고 상기 가교 폴리에틸렌의 열노화(thermal aging)를 증가시키는 문제점을 갖고 있다.In addition, aluminum conductors are known as very economical metals because they have a high conductivity, light weight, and can pass twice as much current as copper of the same weight, as a material for cables following copper conductors that dominate most of the cables. Since the conductivity is about 60% of copper, it causes a high heat generation problem when transmitting the same power and has a problem of increasing thermal aging of the crosslinked polyethylene.

따라서 산업계에서는 가공성, 내열성, 내후성, 내트래킹성을 겸비하는 가교형 폴리올레핀 컴파운드 및 고전압용 전력선의 개발 요구가 계속되어 왔다. Therefore, in the industry, there has been a demand for the development of crosslinked polyolefin compounds and high voltage power lines that combine workability, heat resistance, weather resistance, and tracking resistance.

001. 한국등록특허 제10-2020066호001. Korean Patent Registration No. 10-2020066 002. 미국등록특허 제4330493호002. US Patent No. 4330493

본 발명자들은 전선 표면에 열적,전기적 스트레스가 증가하면 그곳의 절연재료는 탄화하게 되며 케이블 길이 방향으로 탄화가 계속 진행되어 또 다른 지점에서 절연체를 파괴시키는 트래킹 현상이 발생되고 케이블 표면이 오염되어 있을 경우 부착된 물질들도 같이 탄화되면서 트래킹 현상을 촉진하게 되며 심지어는 발생된 아크로 인하여 유발된 불꽃이 이 통로를 따라 번지면서 화재가 발생하는 문제점을 해결하고자 내트래킹성/내열성 등이 향상된 고전압 케이블을 예의 연구노력한 결과, 폴리디메틸실록산이 표면에 도입된 내트래킹제를 첨가한 절연체를 포함하는 고전압 케이블이 기존의 케이블과 비교하여 인장강도, 절연파괴전압, 내오염도 및 내트래킹성이 향상됨을 확인하고 본 발명을 완성하였다. The inventors of the present invention believe that when the thermal and electrical stress on the surface of the wire increases, the insulating material therein is carbonized, and the carbonization continues in the length of the cable, causing a tracking phenomenon that destroys the insulator at another point, and the cable surface is contaminated. Attached substances are also carbonized to promote the tracking phenomenon, and even high voltage cables with improved tracking/heat resistance are used to solve the problem of fires as the sparks caused by the generated arc spread along this passage. As a result of the research efforts, it was confirmed that high-voltage cables containing insulators with a tracking agent added to the surface of polydimethylsiloxane improved tensile strength, insulation breakdown voltage, contamination resistance, and tracking resistance compared to conventional cables. The invention was completed.

본 발명의 제1양태는The first aspect of the present invention

폴리올레핀계 수지 100 중량부 기준으로, 폴리디메틸실록산을 표면에 도입한 내트래킹제 35 내지 60 중량부를 포함하는 절연 조성물로서,An insulating composition comprising 35 to 60 parts by weight of a tracking agent in which polydimethylsiloxane is introduced into the surface, based on 100 parts by weight of a polyolefin-based resin,

상기 내트래킹제는 금속수산화물 100 중량부 기준으로, 비닐실란 2 내지 30 중량부 및 히드로겐 실록산 중합체 2 내지 30 중량부의 배합물로 형성된 폴리디메틸실록산으로 표면개질된 금속수산화물인 것인, 내트래킹성이 향상된 절연 조성물을 제공한다.The tracking resistance is a metal hydroxide surface-modified with polydimethylsiloxane formed of a mixture of 2 to 30 parts by weight of vinylsilane and 2 to 30 parts by weight of a hydrogen siloxane polymer, based on 100 parts by weight of metal hydroxide. Provides an improved insulating composition.

본 발명의 상기 '내트래킹제'는 절연재료가 고압 전압하에서 전도로가 형성되어서 파손하는 것에 견디는 능력을 향상시키는 물질로서, 종래 기술과 달리 폴리디메틸실록산을 도입함으로써 내열향상 및 내오염성을 부여할 수 있다. 폴리디메틸실록산을 도입하기 위해서는 금속수산화물을 비닐실란으로 표면개질하여야 한다.The'tracking agent' of the present invention is a material that improves the ability of the insulating material to withstand damage due to the formation of a conduction path under high voltage, and unlike the prior art, the introduction of polydimethylsiloxane provides improved heat resistance and fouling resistance. I can. In order to introduce polydimethylsiloxane, the surface of the metal hydroxide must be modified with vinyl silane.

예컨대, 상기 내트래킹제는 폴리올레핀계 수지 100 중량부 기준으로 35 내지 60 중량부를 포함할 수 있다. 35 중량부 미만인 경우 절연 조성물의 내전압 특성이 감소될 수 있으며, 60 중량부 초과인 경우 용융혼련성이 떨어지는 문제가 있다. For example, the anti-tracking agent may include 35 to 60 parts by weight based on 100 parts by weight of the polyolefin-based resin. If it is less than 35 parts by weight, the dielectric strength of the insulating composition may be reduced, and if it is more than 60 parts by weight, there is a problem in that the melt-kneading property is inferior.

상기 내트래킹제의 입자 직경은 1 내지 100 μm 인 것일 수 있으나, 이에 제한되지 않는다. 구체적으로 10 내지 60 μm일 수 있다.The particle diameter of the anti-tracking agent may be 1 to 100 μm, but is not limited thereto. Specifically, it may be 10 to 60 μm.

상기 '금속수산화물'은 수산화철, 수산화칼슘, 수산화마그네슘, 수산화알루미늄, 수산화철, 수산화칼슘, 수산화마그네슘, 수산화알루미늄으로 이루어진 군에서 어느 하나 이상인 것일 수 있으나, 이에 제한되지 않는다. The'metal hydroxide' may be any one or more from the group consisting of iron hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide, but is not limited thereto.

상기 '비닐실란'은 폴리디메틸실록산 도입위해 사용되는 것 뿐만 아니라, 폴리올레핀 수지와 내트래킹제 간의 계면접착력을 향상시키기 위해 필요하다. 상기 비닐실란은 트리메톡시비닐실란, 트리에톡시비닐실란, 트라이아이소프로폭시비닐실란, 클로로다이메틸비닐실란으로 이루어진 군에서 어느 하나 이상인 것일 수 있으나, 이에 제한되지 않는다. The'vinylsilane' is not only used to introduce polydimethylsiloxane, but is required to improve the interfacial adhesion between the polyolefin resin and the anti-tracking agent. The vinylsilane may be any one or more from the group consisting of trimethoxyvinylsilane, triethoxyvinylsilane, triisopropoxyvinylsilane, and chlorodimethylvinylsilane, but is not limited thereto.

예컨대, 상기 비닐실란은 금속수화물 100 중량부 기준으로 2 내지 30의 중량부로 포함될 수 있다. 2 중량부 미만인 경우 폴리올레핀과 내트래킹제 간의 계면접착력이 떨어지는 문제가 있으며, 30 중량부 초과인 경우 경제성이 떨어지는 문제가 있다. For example, the vinylsilane may be included in an amount of 2 to 30 parts by weight based on 100 parts by weight of metal hydrate. If it is less than 2 parts by weight, there is a problem that the interfacial adhesion between the polyolefin and the tracking agent is deteriorated, and if it is more than 30 parts by weight, there is a problem that the economy is poor.

상기 '히드로겐 실록산 중합체'는 구체적으로 금속수화물 100 중량부 기준으로 2 내지 30 중량부로 포함될 수 있다. Specifically, the'hydrogen siloxane polymer' may be included in an amount of 2 to 30 parts by weight based on 100 parts by weight of metal hydrate.

본 발명의 상기 '폴리올리핀계 수지'는 상기 폴리올레핀계 수지는 폴리에틸렌, 폴리프로필렌, 에틸렌/프로필렌 공중합체로 이루어진 군에서 어느 하나 이상인 것일 수 있으나, 이에 제한되지 않는다. 구체적으로, 저밀도 폴리에틸렌이나, 중밀도 폴리에틸렌, 선상 저밀도 폴리에틸렌, 에틸렌 공중합체, 폴리프로필렌 일 수 있다. In the'polyolefin-based resin' of the present invention, the polyolefin-based resin may be one or more from the group consisting of polyethylene, polypropylene, and ethylene/propylene copolymer, but is not limited thereto. Specifically, it may be low-density polyethylene, medium-density polyethylene, linear low-density polyethylene, ethylene copolymer, or polypropylene.

본 발명의 상기 절연 조성물에는 '유기과산화물' 가교제를 추가로 포함할 수있다. 폴리올레핀 수지는 가교 과정을 통하여 선형인 분자구조를 3차원적인 망상구조를 가지게 되며, 안정성을 향상시킬 수 있다. 구체적으로, 유기과산화물은 절연 조성물 100 중량부 기준으로 0.5 내지 2 중량부일 수 있다. 유기과산화물이 0.5 중량부 미만일 경우 절연조성물의 가교도가 떨어지고 2 중량부 초과일 경우 가교외의 부반응을 일으킬 수 있는 문제가 있다. 유기과산화물에는 디큐밀 퍼옥사이드나, 벤조일퍼옥사이드, 2,5-비스(터트-아밀페록시)-2,5-디메틸헥산, 2,5-비스(터트-부틸페록시) 2,5-디메틸헥산, 3,6-비스(터트-부틸페록시)-3,6-디메틸옥탄, 2,7-비스(터트-부틸페록시)-2,7-디메틸옥탄, 2,5-비스(터트-부틸페록시)-2,5-디시클로헥실헥산, 퍼부틸 퍼옥사이드로 이루어진 군에서 선택된 어느 하나 이상일 수 있으나, 이에 제한되지 않는다. The insulating composition of the present invention may further include an'organic peroxide' crosslinking agent. The polyolefin resin has a three-dimensional network structure with a linear molecular structure through a crosslinking process, and stability can be improved. Specifically, the organic peroxide may be 0.5 to 2 parts by weight based on 100 parts by weight of the insulating composition. If the organic peroxide is less than 0.5 parts by weight, the degree of crosslinking of the insulating composition is lowered, and if it exceeds 2 parts by weight, there is a problem that side reactions other than crosslinking may occur. Organic peroxides include dicumyl peroxide, benzoyl peroxide, 2,5-bis(tert-amylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy) 2,5-dimethyl Hexane, 3,6-bis(tert-butylperoxy)-3,6-dimethyloctane, 2,7-bis(tert-butylperoxy)-2,7-dimethyloctane, 2,5-bis(tert-) It may be one or more selected from the group consisting of butylperoxy)-2,5-dicyclohexylhexane, and perbutyl peroxide, but is not limited thereto.

본 발명의 상기 절연 조성물에는 산화방지제, 자외선안정제, 활제, 폴리올레핀 왁스, 분산제 및 방열제를 추가로 포함할 수 있다. The insulating composition of the present invention may further include an antioxidant, an ultraviolet stabilizer, a lubricant, a polyolefin wax, a dispersant, and a heat dissipating agent.

상기 '산화방지제'는 절연체 복합체의 장기 라디컬(radical) 안정성을 부여하며 부틸히드록시톨루엔이나, 펜타에리띠오톨테트라킥스(3-(3,5-디-터트-부틸-4-히드록시페닐)프로피오네이트, 트리스(2,4-디터트-부틸페닐)포스파이트, 비스(2,4-디-터트-부틸페닐)펜타에리띠오톨리포스파이트, 디라우릴 티오디프로피오네이트, 디스테알릴펜타에리띠리틸 디포스파이트, 테트라키스(2,4-디-터트-부틸펜틸)[1,1-비페닐]-4,4‘-디일비스포스포니트 등일 수 있다. 이 때 상기 산화방지제가 폴리올레핀 수지 100 중량부 기준 0.4 내지 0.7 중량부일 수 있다. 0.4 미만일 경우 장기 라디칼 안정성이 떨어지고 0.7 중량부 초과할 경우 경제성이 떨어진다. The'antioxidant' imparts long-term radical stability of the insulator composite, and butylhydroxytoluene, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, tris(2,4-ditert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerytholiphosphite, dilauryl thiodipropionate, diste Allylpentaerythrityl diphosphite, tetrakis(2,4-di-tert-butylpentyl)[1,1-biphenyl]-4,4'-diylbisphosphonit, etc. In this case, the antioxidant. May be 0.4 to 0.7 parts by weight based on 100 parts by weight of the polyolefin resin, if it is less than 0.4, long-term radical stability is poor, and if it exceeds 0.7 parts by weight, economical efficiency is poor.

상기 '자외선 안정제'는 태양광의 자외선을 흡수하는 역할을 하며 폴리(4-히드록시-2,2,6,6-테트라메틸-1-피퍼리딘에탄올-얼트-1,4-부탄디오닉 액시드, 2-히드록시-4-n-옥토시벤조페논, 2-(2-히드록시-5-t-옥틸페닐)-벤조트리아졸, 2-(2H-벤조트리아졸-2-일)-4,6-비스 (1-메틸-1-페닐에틸)페놀, 2-(5-클로로-2H-벤조트리아졸-2-일6-(1,1-디메틸에틸)-4-메틸페놀 등이 단독 내지 혼합하여 폴리올레핀 수지 100 중량부 기준 0.2 내지 0.4 중량부가 사용된다. 이 때 상기 자외선안정제가 0.2 중량부 미만일 경우 자외선 흡수성이 떨어지고 0.4 중량부 초과할 경우 경제성이 떨어진다. The'ultraviolet stabilizer' serves to absorb the ultraviolet rays of sunlight and poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol-alt-1,4-butanedioic acid , 2-hydroxy-4-n-octocybenzophenone, 2-(2-hydroxy-5-t-octylphenyl)-benzotriazole, 2-(2H-benzotriazol-2-yl)-4 ,6-bis(1-methyl-1-phenylethyl)phenol, 2-(5-chloro-2H-benzotriazol-2-yl6-(1,1-dimethylethyl)-4-methylphenol, etc. are solely used. And 0.2 to 0.4 parts by weight based on 100 parts by weight of the polyolefin resin are used in this case, when the ultraviolet stabilizer is less than 0.2 parts by weight, ultraviolet absorption is poor, and when the ultraviolet stabilizer exceeds 0.4 parts by weight, economic efficiency is poor.

상기 '활제'는 용융혼련 시 폴리올레핀 수지의 열안정성 및 분산성을 증대시키는 역할을 하며 마그네슘 알루미늄 히드록시카보네이트나 알루미늄 마그네슘 징크 히드록시카보네이트, 알루미늄 마그네슘 징크 히드록시카보네이트 등이 폴리올레핀 수지 100 중량부 기준 0.8 내지 1.3 중량부가 사용된다. 이 때 상기 활제가 0.8 중량부 미만일 경우 용융혼련시 안정성 및 분산성이 떨어지고 1.3 중량부 이상을 첨가할 경우 외부로 이행된다. The'lubricating agent' serves to increase the thermal stability and dispersibility of the polyolefin resin during melt kneading, and magnesium aluminum hydroxy carbonate, aluminum magnesium zinc hydroxy carbonate, aluminum magnesium zinc hydroxy carbonate, etc. are 0.8 based on 100 parts by weight of the polyolefin resin. To 1.3 parts by weight are used. At this time, when the lubricant is less than 0.8 parts by weight, stability and dispersibility are poor during melt-kneading, and when 1.3 parts by weight or more is added, the lubricant is transferred to the outside.

상기 '분산제'는 무기물의 분산성을 향상시키는 역할을 하며 소디움 스테아레이트나, 포타슘 스테아레이트, 칼슘 스테아레이트, 마그네숨 스테아레이트, 징크 스테아레이트나 알류미늄 스테아레이트 등이 단독 내지 혼합되어 폴리올레핀 수지 100 중량부 기준 0.2 내지 0.4 중량부가 사용되나 이에 제한되지 않는다. 이 때 분산제가 0.2 중량부 미만일 경우 분산성이 떨어지고 0.4 중량부 초과할 경우절연 조성물 표면으로 이행 (migration) 된다. The'dispersant' serves to improve the dispersibility of inorganic substances, and sodium stearate, potassium stearate, calcium stearate, magnesum stearate, zinc stearate, aluminum stearate, etc., are singly or mixed together to form 100 weight of polyolefin resin. 0.2 to 0.4 parts by weight based on parts are used, but are not limited thereto. At this time, when the dispersant is less than 0.2 parts by weight, dispersibility is poor, and when it exceeds 0.4 parts by weight, it migrates to the surface of the insulating composition.

상기 '폴리올레핀 왁스'는 폴리올레핀 수지에 가요성을 부여하며 저밀도폴리에틸렌 왁스나 고밀도폴리에틸렌 왁스, 폴리프로필렌 왁스, 산화폴리에틸렌 왁스 등을 단독 내지 혼합하여 폴리올레핀 수지 100 중량부 기준 1.2 내지 1.9 중량부 사용되나 이에 제한되지 않는다. 이 때 상기 폴리올레핀 왁스가 1.2 중량부 미만일 경우 폴리올레핀수지의 가요성이 떨어지고 1.9 중량부 초과할 경우 내구성이 떨어진다. The'polyolefin wax' imparts flexibility to the polyolefin resin, and 1.2 to 1.9 parts by weight based on 100 parts by weight of the polyolefin resin are used, but limited thereto It doesn't work. In this case, when the amount of the polyolefin wax is less than 1.2 parts by weight, the flexibility of the polyolefin resin is deteriorated, and when it exceeds 1.9 parts by weight, the durability is deteriorated.

상기 '자외선차단 안료'는 카본블랙이나 흑연, 카본나노튜브 등이 폴리올레핀 수지 100 중량부 기준 0.6 내지 1.0 중량부 사용되나 이에 제한되지 않는다. 이 때 상기 자외선차단 안료가 0.6 중량부 미만일 경우 색상이 발현되지 않고 1.0 중량부 초과할 경우 분산성이 떨어진다. In the'ultraviolet ray blocking pigment', 0.6 to 1.0 parts by weight of carbon black, graphite, carbon nanotubes, etc. are used based on 100 parts by weight of the polyolefin resin, but is not limited thereto. At this time, when the amount of the sunscreen pigment is less than 0.6 parts by weight, color is not expressed, and when the amount exceeds 1.0 part by weight, dispersibility is inferior.

본 발명의 제2양태는 The second aspect of the present invention

도체; 상기 제1양태의 절연 조성물로부터 형성된 절연체; 및 반도전 탄성체 순서로 압출한 것을 포함하는 고전압 케이블을 제공한다.Conductor; An insulator formed from the insulating composition of the first aspect; And it provides a high voltage cable comprising the extrusion in the order of the semiconducting elastomer.

본 발명의 케이블 구성 순서는 종래기술이 도체, 내부 반도체층, 절연체, 외부 반도체층으로 구성되는 것과 비교해 반도체층 사이에 내부 절연체층을 두지 않으면서도, 종래기술보다 우수한 내트래킹성을 가지며 절연파괴전압이 향상될 수 있다.The cable construction sequence of the present invention has superior tracking resistance and insulation breakdown voltage compared to the conventional technology without having an internal insulator layer between the semiconductor layers compared to the conventional technology consisting of a conductor, an inner semiconductor layer, an insulator, and an outer semiconductor layer. This can be improved.

본 발명의 상기 '도체'는 구리선나 알루미늄선, 은선, 니켈선 등의 금속선이나 주석도금선, 은도금선, 니켈도금선 등의 금속 도금선, 주석-구리합금선, 알루미늄-구리 합금선 등의 합금선 등을 단선(solid)으로 사용하거나 집합(twist) 또는 연선(combine)하여 사용가능하나, 이에 제한되지 않는다.The'conductor' of the present invention is a metal wire such as a copper wire, an aluminum wire, a silver wire, a nickel wire, a tin-plated wire, a silver-plated wire, a metal-plated wire such as a nickel-plated wire, a tin-copper alloy wire, and an aluminum-copper alloy wire. An alloy wire or the like may be used as a solid, or may be used by twisting or combining, but is not limited thereto.

본 발명의 상기 '반도전 탄성체'는 105 내지 108 Ω인 3 내지 5 mm 크기일 수 있으나, 이에 제한되지 않는다. The'semiconductor elastic body' of the present invention may have a size of 3 to 5 mm, which is 10 5 to 10 8 Ω, but is not limited thereto.

상기 '탄성체'는 가교형 반도전 조성물의 매트릭스(matrix)상을 이루며 폴리에틸렌이나 에틸렌프로필렌 공중합체(ethylene propylene copolymer)나 에틸렌 비닐아세테이트 공중합체(ethylene vinyl acetate copolymer), 에틸렌 아크릭 액시드 공중합체(ethylene acrylic acid copolymer), 에틸렌 옥텐 공중합체(ethylene octene copolymer), 에틸렌 에틸 아크릴레이트 공중합체(ethylene ethyl acrylate copolymer) 등의 에틸렌 공중합체(ethylene copolymer), 폴리프로필렌 (polypropylene)이 바람직하나 이외에도 천연고무(natural rubber), 니드릴부타디엔 고무(nitrile butadiene rubber), 클로로프렌 고무(chloroprene rubber) 등의 고분자 탄성체가 단독 내지 혼합사용도 가능하나 이에 제한되지 않는다. The'elastomer' forms a matrix of a crosslinked semiconducting composition, and is a polyethylene or ethylene propylene copolymer, an ethylene vinyl acetate copolymer, or an ethylene acrylic acid copolymer. Acrylic acid copolymer), ethylene octene copolymer, ethylene ethyl acrylate copolymer, and other ethylene copolymers, polypropylene are preferable. rubber), nitrile butadiene rubber, and chloroprene rubber may be used alone or in combination, but are not limited thereto.

본 발명의 제3양태는 The third aspect of the present invention

제2양태의 고전압 케이블의 제조방법으로서, 표면개질된 내트래킹제를 제조하는 제1단계; 상기 내트래킹제를 배합하여 가교된 절연체를 제조하는 제2단계; 가교된 폴리올레핀을 제조하는 제3단계; 가교된 반도전 탄성체를 제조하는 제4단계; 및 도체를 외부에 상기 제1 내지 제4단계에서 제조된 것을 압출가류하는 제5단계를 포함하는 것인 고전압 케이블 제조방법을 제공한다. A method of manufacturing a high voltage cable of a second aspect, comprising: a first step of preparing a surface-modified tracking agent; A second step of preparing a crosslinked insulator by blending the anti-tracking agent; A third step of preparing a crosslinked polyolefin; A fourth step of preparing a crosslinked semiconducting elastomer; And a fifth step of extruding and curing the conductors manufactured in the first to fourth steps to the outside.

상기 내트래킹제를 제조하는 제1단계는 상기 제1단계는 ⅰ)히드로겐 실록산 중합체 제조하는 단계; ⅱ)금속수산화물에 비닐기를 도입하여 비닐실란으로 표면개질된 금속수산화물을 제조하는 단계; 및 ⅲ)상기 히드로겐 실록산, 비닐실란으로 표면개질된 금속수산화물 및 촉매를 반응시켜 비닐실란 표면개질된 금속수산화물에 폴리디메틸실록산을 도입하는 단계로 이루어진 것일 수 있으나, 이에 제한되지 않는다. The first step of preparing the anti-tracking agent includes: i) preparing a hydrogen siloxane polymer; Ii) preparing a surface-modified metal hydroxide with vinylsilane by introducing a vinyl group into the metal hydroxide; And iii) reacting the metal hydroxide surface-modified with the hydrogen siloxane and vinylsilane and a catalyst to introduce polydimethylsiloxane to the metal hydroxide surface-modified with vinylsilane, but is not limited thereto.

예컨대, 상기 표면개질된 금속수산화물에 폴리디메틸실록산을 도입하는 ⅲ)단계는 히드로겐 실록산 100 중량부 기준 비닐실란으로 표면개질된 금속수산화물 1000 내지 4000 중량부 및 촉매 0.01 내지 1 중량부를 배합하여 반응기 온도를 80 내지 140℃로 상승시키고 100 내지 1,000 RPM의 속도로 60 내지 180분간 교반한 다음 여과하여 40 내지 120℃의 온도에서 수행하는 것일 수 있으나, 이에 제한되지 않는다. For example, step iii) of introducing polydimethylsiloxane to the surface-modified metal hydroxide comprises 1000 to 4000 parts by weight of a metal hydroxide surface-modified with vinylsilane and 0.01 to 1 part by weight of a catalyst based on 100 parts by weight of hydrogen siloxane, and the reactor temperature It may be increased to 80 to 140°C, stirred at a rate of 100 to 1,000 RPM for 60 to 180 minutes, and then filtered to perform at a temperature of 40 to 120°C, but is not limited thereto.

상기 제2단계는 산화방지제, 자외선안정제, 활제, 폴리올레핀 왁스, 분산제 및 방열제를 추가로 포함하여 수행하는 것일 수 있으며, 가교제인 유기과산화물을 혼합하여 가교된 절연체를 제조할 수 있다.The second step may be performed by additionally including an antioxidant, an ultraviolet stabilizer, a lubricant, a polyolefin wax, a dispersant, and a heat dissipating agent, and a crosslinked insulator may be prepared by mixing an organic peroxide as a crosslinking agent.

상기 제3단계는 3 내지 5 mm 크기의 저밀도 폴리에틸렌이나, 중밀도 폴리에틸렌, 선상 저밀도 폴리에틸렌 및 에틸렌 공중합체 등의 폴리올레핀 수지 펠렛 10,000 중량부와 유기과산화물 95 내지 150 중량부를 투여하여 60 내지 100℃의 온도에서 10 내지 60분간 혼련하여 가교된 폴리올레핀을 제조할 수 있다. In the third step, 10,000 parts by weight of polyolefin resin pellets such as 3 to 5 mm-sized low-density polyethylene, medium-density polyethylene, linear low-density polyethylene, and ethylene copolymer, and 95 to 150 parts by weight of organic peroxide are administered at a temperature of 60 to 100°C. It can be kneaded in 10 to 60 minutes to prepare a crosslinked polyolefin.

상기 제4단계는 고분자 탄성체(elastomer) 100 중량부 기준 카본블랙(carbon black), 탄소나노튜브(carbon nanotube), 흑연(graphite) 및 그라핀(graphene) 등의 도전성충진제 5 내지 20 중량부, 산화방지제(antioxidant) 0.4 내지 0.7 중량부 및 분산제 0.2 내지 0.4 중량부를 순차적으로 투입하고 100 내지 140℃의 온도에서 10 내지 60분 동안 혼련 한 덩어리 반죽을 일축이나 이축 압출기로 이송시켜 압출성형을 면저항이 105 내지 108 Ω인 3 내지 5 mm 크기의 반도전 탄성체 펠렛를 제조한다. 이후, 상기 반도전 탄성체의 100 중량부 기준 유기과산화물 0.9 내지 1.5 중량부를 투여하여 60 내지 100℃의 온도에서 10 내지 60분간 혼련하여 가교형 반도전 탄성체 펠렛을 제조하는 것일 수 있으나, 이에 제한되지 않는다. In the fourth step, 5 to 20 parts by weight of conductive fillers such as carbon black, carbon nanotube, graphite and graphene based on 100 parts by weight of a polymer elastomer, and oxidation. 0.4 to 0.7 parts by weight of an antioxidant and 0.2 to 0.4 parts by weight of a dispersant are sequentially added, and the kneaded dough is transferred to a single-screw or twin-screw extruder for 10 to 60 minutes at a temperature of 100 to 140°C. To prepare a semiconducting elastomer pellet having a size of 3 to 5 mm of 5 to 10 8 Ω. Thereafter, 0.9 to 1.5 parts by weight of an organic peroxide based on 100 parts by weight of the semiconducting elastic body may be administered and kneaded for 10 to 60 minutes at a temperature of 60 to 100°C to prepare a crosslinked semiconducting elastomer pellet, but is not limited thereto. .

상기 제5단계는 상기 제4단계에서 제조된 반도전 탄성체 펠렛을 제1호퍼(hopper)에 상기 제3단계에서 제조된 가교형 폴리올레핀 펠렛을 제2호퍼에, 상기 2단계에서 제조된 가교형 절연체 펠렛을 제3호퍼에 투여한다. 이때 호퍼의 순서는 임의로 정한것이다. 이후, 공압출 다이(co-extrusion die)가 부착되어 있는 압출기의 헤드(head)에 금속선(metal wire)이나 금속 도금선(metal plated wire), 합금선(metal alloy wire으)로 이루어진 도체(conductor)를 통과시키면서 온도조건이 실린더(cylinder) 1은 100 내지 120℃, 실린더 2는 100 내지 120℃, 실린더 3은 105 내지 125℃, 압출헤드(extrusion head) 110 내지 130℃, 압출다이(extrusion die)는 110 내지 130℃의 온도조건으로 10 내지 40 ㎏/hr 의 속도로 압출하여 80 내지 120℃와 10 내지 20 기압으로 유지되는 가류관(continuous vulcanization pipe)을 20 내지 50 m/min 의 속도로 통과시켜 고전압 케이블을 제조하는 압출가류할 수 있으나, 이에 제한되지 않는다. In the fifth step, the semiconducting elastomer pellet prepared in the fourth step is placed in a first hopper, the crosslinked polyolefin pellet prepared in the third step is placed in a second hopper, and the crosslinked insulator prepared in the second step The pellet is administered to the third hopper. At this time, the order of the hopper is arbitrarily determined. Then, a conductor made of metal wire, metal plated wire, or metal alloy wire to the head of the extruder to which the co-extrusion die is attached. ), the temperature condition is 100 to 120°C for cylinder 1, 100 to 120°C for cylinder 2, 105 to 125°C for cylinder 3, 110 to 130°C for extrusion head, extrusion die ) Is a continuous vulcanization pipe maintained at 80 to 120°C and 10 to 20 atmospheres by extruding at a rate of 10 to 40 kg/hr under a temperature condition of 110 to 130°C at a speed of 20 to 50 m/min. Extrusion vulcanization to produce a high-voltage cable by passing through, but is not limited thereto.

본 발명은 폴리디메틸실록산이 표면에 도입된 내트래킹제를 첨가한 절연체를 포함하는 케이블로서, 송전용량을 증가시키는 경우에도, 우수한 트랙킹 억제특성을 갖으며 가공성, 내열성, 내후성이 뛰어난 절연 컴파운드 및 고전압 케이블을 용이하게 제조할 수 있음을 확인하여 고전압에도 견딜수 있는 수명이 연장된 산업상 유용한 케이블로 널리 사용될 수 있음을 확인하였다. The present invention is a cable comprising an insulator to which a tracking agent is added to which polydimethylsiloxane is introduced, and has excellent tracking inhibiting properties even when the power transmission capacity is increased, and an insulating compound and high voltage with excellent workability, heat resistance, and weather resistance. It was confirmed that the cable could be easily manufactured, and it was confirmed that it can be widely used as an industrially useful cable with an extended lifespan that can withstand high voltages.

도 1은 본 발명의 실시예에 따른 고전압 케이블 제조방법의 순서도이다. 1 is a flowchart of a method of manufacturing a high voltage cable according to an embodiment of the present invention.

이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. These examples are for explaining the present invention more specifically, and the scope of the present invention is not limited by these examples.

실시예 1. 표면개질된 내트래킹제가 첨가된 절연체를 포함한 고전압 케이블Example 1. High-voltage cable including an insulator to which a surface-modified tracking agent was added

1.1 히드로겐 실록산 중합체의 제조1.1 Preparation of hydrogen siloxane polymer

교반기, 온도조절기, 드로핑 훤넬 및 질소 공급기가 장착된 반응기에 229.55 g의 옥타메틸클로테트라실록산, 1.92 g의 데카메틸 테트라실란 및 0.27 g의 폴리디메틸실록산 오일을 투여하고 반응기 온도를 150℃로 유지시키면서 3시간 동안 반응을 진행시킨다. 반응이 완료되면 반응기 온도를 90℃로 낮추고 1.62 g의 폴리디메틸실록산 오일 및 0.032 g의 포스포니트리릭 클로라이드, 0.031 g의 포타슘 실라노레이트를 상기 반응용액에 투여하여 1시간 동안 50 RPM의 속도로 교반한다. 교반이 끝난 후에 상기 혼합용액에 2.23 g의 메틸히드록실옥산을 투여하고 4시간 동안 50 RPM의 속도로 교반하여 220 g의 히드로겐 실록산 중합체를 제조하였다.To a reactor equipped with a stirrer, temperature controller, dropping horn and nitrogen supply, 229.55 g of octamethylclotetrasiloxane, 1.92 g of decamethyl tetrasilane and 0.27 g of polydimethylsiloxane oil were added and the reactor temperature was maintained at 150°C. While allowing the reaction to proceed for 3 hours. Upon completion of the reaction, the reactor temperature was lowered to 90°C, and 1.62 g of polydimethylsiloxane oil, 0.032 g of phosphonitrilic chloride, and 0.031 g of potassium silanorate were added to the reaction solution at a rate of 50 RPM for 1 hour. Stir. After the stirring was completed, 2.23 g of methylhydroxyloxane was added to the mixed solution and stirred at a speed of 50 RPM for 4 hours to prepare 220 g of a hydrogen siloxane polymer.

1.2 비닐기로 표면 개질된 금속수산화물의 제조: 내트래킹제의 제조1.2 Preparation of surface-modified metal hydroxide with vinyl group: Preparation of anti-tracking agent

온도조절기와 교반기가 장착된 20 L 반응기에 메탄올 10,000 g과, 트리에톡시비닐실란 200 g을 첨가하여 100 RPM의 속도로 30분간 교반한 다음 알루미늄 히드록사이드 4,200 g을 투여하고 200 RPM의 속도로 60분간 교반한 다음 여과하여 80℃의 온도에서 건조하여 트리에톡시비닐실란으로 표면처리된 알루미늄 히드록사이드를 제조하였다. To a 20 L reactor equipped with a temperature controller and a stirrer, 10,000 g of methanol and 200 g of triethoxyvinylsilane were added, stirred for 30 minutes at a rate of 100 RPM, and then 4,200 g of aluminum hydroxide was added, and at a rate of 200 RPM. After stirring for 60 minutes, it was filtered and dried at 80° C. to prepare aluminum hydroxide surface-treated with triethoxyvinylsilane.

1.3 폴리디메틸실록산을 비닐기 표면개질된 금속수산화물 표면에 도입: 표면개질된 내트래킹제 제조1.3 Introduction of polydimethylsiloxane to the surface of a vinyl group surface-modified metal hydroxide: Preparation of a surface-modified anti-tracking agent

온도조절기와 교반기가 장착된 20 L 반응기에 톨루엔 10,000 g과 히드로겐 실록산 중합체 220 g, 트리에톡시비닐실란으로 표면처리된 알루미늄 히드록사이드 4,300 g, 백금촉매 0.5g을 첨가하여 500 RPM의 속도로 교반하면서 반응기 온도를 80℃로 상승시켜 120분간 교반한 다음 여과하여 100℃에서 건조하여 폴리디메틸실록산이 도입된 알루미늄 히드록사이드 5,400 g을 제조하였다.To a 20 L reactor equipped with a temperature controller and a stirrer, 10,000 g of toluene, 220 g of a hydrogen siloxane polymer, 4,300 g of aluminum hydroxide surface-treated with triethoxyvinylsilane, and 0.5 g of a platinum catalyst were added at a speed of 500 RPM. While stirring, the reactor temperature was raised to 80° C., stirred for 120 minutes, filtered, and dried at 100° C. to prepare 5,400 g of aluminum hydroxide into which polydimethylsiloxane was introduced.

1.4 절연체의 제조1.4 Preparation of insulators

100 L 니더에 고밀도 폴리에틸렌 수지 10,000 g, 폴리디메틸실록산이 도입된 알루미늄 히드록사이드 4,400 g, 펜타에리띠오톨테트라킥스(3-(3,5-디-터트-부틸-4-히드록시페닐)프로피오네이트 50 g, 폴리(4-히드록시-2,2,6,6-테트라메틸-1-피퍼리딘에탄올-얼트-1,4-부탄디오닉 액시드 30 g, 마그네슘 알루미늄 히드록시카보네이트 100g, 저밀도폴리에틸렌 왁스, 140 g, 징크 스테아레이트 30 g, 카본블랙 80 g을 순차적으로 투여하여 140℃에서 30분간 용융혼련한 한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3 내지 5 mm 크기의 고밀도 폴리에틸렌 절연 조성물 펠렛을 제조하였다.10,000 g of high-density polyethylene resin in a 100 L kneader, 4,400 g of aluminum hydroxide with polydimethylsiloxane introduced, pentaerythritol tetrakix (3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro 50 g of cypionate, 30 g of poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol-alt-1,4-butanedioic acid, 100 g of magnesium aluminum hydroxycarbonate, Low-density polyethylene wax, 140 g, zinc stearate 30 g, and carbon black 80 g are sequentially administered and melt-kneaded at 140°C for 30 minutes and transferred to a twin-screw extruder to a high density of 3 to 5 mm in size. Polyethylene insulation composition pellets were prepared.

1.5 가교된 절연체의 제조1.5 Preparation of crosslinked insulator

100L 헨셀믹서에 제조된 고밀도 폴리에틸렌 절연 조성물 펠렛과 퍼부틸 퍼옥사이드 120 g을 투여하여 80℃에서 30분간 혼련하여 가교형 절연 조성물 펠렛을 제조하였다.The high-density polyethylene insulating composition pellets prepared in a 100L Henschel mixer and 120 g of perbutyl peroxide were added and kneaded at 80° C. for 30 minutes to prepare a crosslinked insulating composition pellet.

1.6 가교된 폴리올레핀의 제조1.6 Preparation of crosslinked polyolefin

20L 니더에 3 내지 5 mm 크기의 중밀도 폴리에틸렌 수지 10,000 g과 디큐밀 퍼옥사이드 120 g을 투여하여 80℃에서 30분간 혼련하고 가교형 중밀도 폴리에틸렌 펠렛을 제조하였다.To a 20L kneader, 10,000 g of a medium-density polyethylene resin having a size of 3 to 5 mm and 120 g of dicumyl peroxide were administered and kneaded at 80° C. for 30 minutes to prepare crosslinked medium-density polyethylene pellets.

1.7 가교된 반도전 탄성체의 제조1.7 Preparation of crosslinked semiconducting elastomer

20L 니더에 에틸렌프로필렌 공중합체 10,000 g과 도전성 카본블랙 1,500 g, 트리스(2,4-디터트-부틸페닐)포스파이트 52 g, 아연 스테아레이트 30 g을 순차적으로 투입하여 100℃에서 20분 동안 혼련 한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 표면저항이 106 Ω인 3 내지 5 mm 크기의 반도전 에틸렌프로필렌 공중합체펠렛을 제조하였다. 20 L 헨셀믹서에 제조된 반도전 에틸렌프로필렌 공중합체 펠렛과 디큐밀 퍼옥사이드 120 g을 투여하여 80℃에서 20분간 혼련하여 가교형 반도전 에틸렌프로필렌 공중합체 펠렛을 제조하였다.In a 20L kneader, 10,000 g of ethylene propylene copolymer, 1,500 g of conductive carbon black, 52 g of tris(2,4-ditert-butylphenyl) phosphite, and 30 g of zinc stearate were sequentially added and kneaded at 100°C for 20 minutes. One lump of dough was transferred to a twin screw extruder and subjected to extrusion molding to prepare semiconducting ethylene propylene copolymer pellets having a surface resistance of 10 6 Ω and a size of 3 to 5 mm. Semiconductive ethylene propylene copolymer pellets prepared in a 20 L Henschel mixer and 120 g of dicumyl peroxide were added and kneaded at 80° C. for 20 minutes to prepare cross-linked semiconducting ethylene propylene copolymer pellets.

1.8 압출가류를 통한 고전압 케이블의 제조1.8 Manufacture of high voltage cables through extrusion vulcanization

가교형 반도전 에틸렌프로필렌 공중합체 펠렛을 제1호퍼에 가교형 중밀도 폴리에틸렌 펠렛을 제2호퍼에, 고밀도 폴리에틸렌 절연 조성물 펠렛을 제3호퍼에 투여한 다음 직경이 각각 12Φ mm 및 15Φ mm, 18Φ mm 공압출 다이가 부착되어 있는 압출기의 헤드에 작경이 3Φ mm인 알루미늄선을 7연선 시킨 외경이 10Φ mm인 도체를 통과시키면서 실린더 1은 110℃, 실린더 2는 110℃, 실린더 3은 115℃, 압출헤드 120℃, 압출다이는 120℃의 온도조건으로 20 ㎏/hr의 속도로 압출하면서 110℃와 15기압으로 유지되는 가류관을 30 m/min의 속도로 통과시켜 고전압 케이블의 제조하였다.Cross-linked semiconducting ethylene propylene copolymer pellets were added to the first hopper, cross-linked medium-density polyethylene pellets were added to the second hopper, and the high-density polyethylene insulating composition pellets were administered to the third hopper, and the diameters were 12 Φ mm, 15 Φ mm, and 18 Φ mm, respectively. Cylinder 1 is 110℃, Cylinder 2 is 110℃, Cylinder 3 is 115℃, Extruded while passing a conductor with an outer diameter of 10Φ mm made of 7 strands of aluminum wire with a diameter of 3Φ mm to the head of the extruder with the coextrusion die attached. The head 120°C and the extrusion die were extruded at a rate of 20 kg/hr under a temperature condition of 120°C, and a high voltage cable was manufactured by passing a vulcanizing tube maintained at 110°C and 15 atm at a speed of 30 m/min.

실시예 2. 표면개질된 내트래킹제가 첨가된 절연체를 포함하는 고전압 케이블Example 2. High-voltage cable comprising an insulator to which a surface-modified tracking agent was added

상기 실시예 1.2의 반응용매를 메탄올에서 에탄올로 트리에톡시비닐실란을 트리메톡시비닐실란으로 변경하고; 실시예 1.3의 트리에톡시비닐실란으로 표면처리된 알루미늄을 트리메톡시비닐실란으로 표면처리된 알루미늄으로 변경하며; 실시예 1.4의 고밀도 폴리에틸렌 수지를 중밀도 폴리에틸렌 수지로 변경하는 것을 제외하고는 나머지 방식은 상기 실시예 1과 동일한 방식으로 고전압 케이블을 제조하였다. Changing the reaction solvent of Example 1.2 from methanol to ethanol and triethoxyvinylsilane to trimethoxyvinylsilane; Changing the aluminum surface-treated with triethoxyvinylsilane of Example 1.3 to aluminum surface-treated with trimethoxyvinylsilane; A high-voltage cable was manufactured in the same manner as in Example 1 except for changing the high-density polyethylene resin of Example 1.4 to a medium-density polyethylene resin.

비교예 1. 내트래킹제가 첨가된 절연체를 포함하는 고전압 케이블Comparative Example 1. High-voltage cable comprising an insulator added with a tracking agent

상기 실시예 1.3을 제외한 나머지 방식은 실시예 1과 동일한 방식으로 고전압 케이블을 제조하였다. 상기 방식으로 제조된 고전압케이블은 폴리디메틸실록산이 표면개질되지 않은 내트레킹제가 첨가되어 제조된 것이다. Except for Example 1.3, a high voltage cable was manufactured in the same manner as in Example 1. The high-voltage cable manufactured in the above manner is manufactured by adding a trekking agent in which polydimethylsiloxane is not surface-modified.

시험예 1. 케이블의 인장강도, 내트래킹성 및 절연파괴 전압 측정Test Example 1. Measurement of tensile strength, tracking resistance, and insulation breakdown voltage of cables

상기의 단계를 거쳐 제조된 절연 조성물 펠렛은 핫-프레스 (hot-press)를 이용하여 160℃의 온도에서 0.5 mm 두께의 시트 (sheet)로 제작하여 인장강도는 IEC 60811-1-1 규격의 dumb-bell 시편으로 제작하여 만능시험기를 이용하여 100 mm/분의 속도로 측정하였다. The insulating composition pellets manufactured through the above steps were manufactured into a 0.5 mm thick sheet at a temperature of 160°C using hot-press, and the tensile strength was dumb according to IEC 60811-1-1 standard. It was made into a -bell specimen and measured at a speed of 100 mm/min using a universal testing machine.

내트래킹성은 IEC 60587 “Electrical insulating materials used under severe ambient conditions -. Test methods for evaluating resistance”의 시험방법에 따라 진행하였다.Tracking resistance is IEC 60587 “Electrical insulating materials used under severe ambient conditions -. Test methods for evaluating resistance”.

압출된 고전압 케이블의 절연파괴 전압(breakdown voltage)은 고전압시험기를 이용하여 교류 전압을 상승시키면서 절연파괴가 일어나는 최대전압을 측정하였다.The breakdown voltage of the extruded high voltage cable was measured using a high voltage tester to measure the maximum voltage at which insulation breakdown occurs while increasing the AC voltage.

구분
division
 분산성
Dispersibility
 절연파괴전압
(kV) Insulation breakdown voltage
(kV) 인장강도
(MPa)The tensile strength
(MPa) 내오염도
Pollution resistance
 내트래킹성
Tracking resistance
 실시예1Example 1 우수Great 3232 17.817.8 우수Great 4.5 kV - 130분4.5 kV-130 min 실시예2Example 2 우수Great 3131 17.017.0 우수Great 4.5 kV - 120분4.5 kV-120 minutes 비교예1Comparative Example 1 양호Good 2828 15.215.2 보통usually 4.5 kV - 100분4.5 kV-100 minutes

상기 표 1은 절연 조성물 및 고전압케이블의 실시예와 비교예의 시험결과를 나타낸 것이다. 이를 통해, 본 발명의 고전압 케이블은 실시예1 및 2가 비교예보다 인장강도, 절연파괴전압, 내오염도, 내트래킹성이 향상됨을 확인할 수 있었다.Table 1 shows the test results of Examples and Comparative Examples of the insulating composition and the high voltage cable. Through this, it was confirmed that the high-voltage cables of the present invention have improved tensile strength, insulation breakdown voltage, contamination resistance, and tracking resistance than in Comparative Examples in Examples 1 and 2.

<결론><Conclusion>

본 발명에 따른 고전압 케이블용 내트래킹성 폴리올레핀 수지 및 고전압 케이블의 제조방법은 표면개질 된 금속산화물 내트래킹제를 기반으로 하는 옥외용 고전압 전력 케이블의 송전용량 증가 시 문제점으로 대두되는 열산화에 대한 안정성을 높이고 압출시 평활도가 향상되어 내트래킹성이 우수한 가교성 폴리올레핀 컴파운드는 물론 절연층의 자체적인 절연내력이 높고, 상기 절연층에 인가되는 전계가 효과적으로 완화되어 내열성이 향상되고 결과적으로 수명이 연장될 수 있는 고전압 케이블을 고가의 설비를 구비하지 않고 기존의 장비를 이용하여 경제적으로 용이하게 제조하는 효과가 있음을 확인할 수 있었다. The method of manufacturing a tracking-resistant polyolefin resin and a high-voltage cable for a high-voltage cable according to the present invention provides stability against thermal oxidation, which is a problem when increasing the transmission capacity of an outdoor high-voltage power cable based on a surface-modified metal oxide tracking agent. In addition to the crosslinkable polyolefin compound having excellent tracking resistance, as well as the crosslinkable polyolefin compound with improved smoothness during extrusion, the insulation layer's own dielectric strength is high, and the electric field applied to the insulation layer is effectively relieved, thereby improving heat resistance and consequently extending the lifespan. It was confirmed that there is an effect of economically and easily manufacturing a high-voltage cable with existing equipment using existing equipment without having expensive equipment.

Claims (12)

폴리올레핀계 수지 100 중량부 기준으로, 폴리디메틸실록산을 표면에 도입한 내트래킹제 35 내지 60 중량부를 포함하는 절연 조성물로서,
상기 내트래킹제는 금속수산화물 100 중량부 기준으로, 비닐실란 2 내지 30 중량부 및 히드로겐 실록산 중합체 2 내지 30 중량부의 배합물로 형성된 폴리디메틸실록산으로 표면개질된 금속수산화물인 것인, 내트래킹성이 향상된 절연 조성물.
An insulating composition comprising 35 to 60 parts by weight of a tracking agent in which polydimethylsiloxane is introduced into the surface, based on 100 parts by weight of a polyolefin-based resin,
The anti-tracking agent is a metal hydroxide surface-modified with polydimethylsiloxane formed of a mixture of 2 to 30 parts by weight of vinylsilane and 2 to 30 parts by weight of a hydrogen siloxane polymer based on 100 parts by weight of metal hydroxide. Improved insulation composition.
 제1항에 있어서,
상기 내트래킹제 입자 직경은 10 내지 60 μm 인 것인 절연 조성물.
The method of claim 1,
The insulating composition that the particle diameter of the tracking agent is 10 to 60 μm.
 제1항에 있어서,
상기 금속수산화물은 수산화철, 수산화칼슘, 수산화마그네슘, 수산화알루미늄으로 이루어진 군에서 어느 하나 이상인 것인 절연 조성물.
The method of claim 1,
The insulating composition of the metal hydroxide is any one or more from the group consisting of iron hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide.
 제1항에 있어서,
상기 비닐실란은 트리메톡시비닐실란, 트리에톡시비닐실란, 트라이아이소프로폭시비닐실란, 클로로다이메틸비닐실란으로 이루어진 군에서 어느 하나 이상인 것인 절연 조성물.
The method of claim 1,
The vinyl silane is any one or more from the group consisting of trimethoxy vinyl silane, triethoxy vinyl silane, triisopropoxy vinyl silane, and chlorodimethyl vinyl silane.
 제1항에 있어서,
상기 폴리올레핀계 수지는 폴리에틸렌, 폴리프로필렌, 에틸렌/프로필렌 공중합체로 이루어진 군에서 어느 하나 이상인 것인 절연 조성물.
The method of claim 1,
The insulating composition of the polyolefin-based resin is any one or more from the group consisting of polyethylene, polypropylene, and ethylene/propylene copolymer.
 제1항에 있어서,
상기 절연 조성물 100 중량부 기준으로 유기과산화물 가교제를 0.5 내지 2 중량부를 추가로 포함하는 것인 절연 조성물.
The method of claim 1,
The insulating composition further comprises 0.5 to 2 parts by weight of an organic peroxide crosslinking agent based on 100 parts by weight of the insulating composition.
 제1항에 있어서,
상기 절연 조성물에 산화방지제, 자외선안정제, 활제, 폴리올레핀 왁스, 분산제 및 방열제를 추가로 포함하는 것인 절연 조성물.
The method of claim 1,
The insulating composition further comprises an antioxidant, an ultraviolet stabilizer, a lubricant, a polyolefin wax, a dispersant and a heat dissipating agent in the insulating composition.
 도체; 상기 제1항 내지 7항 중 어느 한 항의 절연 조성물로부터 형성된 절연체; 및 반도전 탄성체 순서로 압출한 것을 포함하는 고전압 케이블.
Conductor; An insulator formed from the insulating composition of any one of claims 1 to 7; And a semiconducting elastomer extruded in order.
 제1항 내지 제7항 중 어느 한 항의 절연 조성물로부터 형성된 절연체를 포함하는 고전압 케이블의 제조방법으로서,
표면개질된 내트래킹제를 제조하는 제1단계; 상기 내트래킹제를 배합하여 가교된 절연체를 제조하는 제2단계; 가교된 폴리올레핀을 제조하는 제3단계; 가교된 반도전 탄성체를 제조하는 제4단계; 및 도체를 외부에 상기 제1 내지 제4단계에서 제조된 것을 압출가류하는 제5단계를 포함하여 수행하는 것인 고전압 케이블 제조방법.
A method of manufacturing a high voltage cable comprising an insulator formed from the insulating composition of any one of claims 1 to 7,
A first step of preparing a surface-modified anti-tracking agent; A second step of preparing a crosslinked insulator by blending the anti-tracking agent; A third step of preparing a crosslinked polyolefin; A fourth step of preparing a crosslinked semiconducting elastomer; And a fifth step of extruding and curing the conductors manufactured in the first to fourth steps to the outside.
 제9항에 있어서,
상기 제1단계는 ⅰ)히드로겐 실록산 중합체 제조하는 단계; ⅱ)금속수산화물에 비닐기를 도입하여 비닐실란으로 표면개질된 금속수산화물을 제조하는 단계; 및 ⅲ)상기 히드로겐 실록산, 비닐실란으로 표면개질된 금속수산화물 및 촉매를 반응시켜 비닐실란 표면개질된 금속수산화물에 폴리디메틸실록산을 도입하는 단계로 이루어진 것인, 고전압 케이블 제조방법.
The method of claim 9,
The first step is i) preparing a hydrogen siloxane polymer; Ii) preparing a surface-modified metal hydroxide with vinylsilane by introducing a vinyl group into the metal hydroxide; And iii) reacting the hydrogen siloxane and a metal hydroxide surface-modified with vinylsilane and a catalyst to introduce polydimethylsiloxane to the metal hydroxide surface-modified with vinylsilane.
 제10항에 있어서,
상기 ⅲ)단계는 히드로겐 실록산 100 중량부 기준 비닐실란으로 표면개질된 금속수산화물 1000 내지 4000 중량부 및 촉매 0.01 내지 1 중량부를 배합하여 수행하는 것인, 고전압 케이블 제조방법.
The method of claim 10,
The step iii) is performed by mixing 1000 to 4000 parts by weight of a metal hydroxide surface-modified with vinylsilane based on 100 parts by weight of hydrogen siloxane and 0.01 to 1 part by weight of a catalyst.
 제9항에 있어서,
상기 제2단계는 산화방지제, 자외선안정제, 활제, 폴리올레핀 왁스, 분산제 및 방열제를 추가로 포함하여 수행하는 것인, 고전압 케이블 제조방법.




The method of claim 9,
The second step is to be performed by further comprising an antioxidant, an ultraviolet stabilizer, a lubricant, a polyolefin wax, a dispersant and a heat dissipating agent.
KR1020190139633A 2019-11-04 2019-11-04 Tracking resistant insulation composition and high voltage cable comprising the same KR102354984B1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330493A (en) 1980-02-13 1982-05-18 Sumitomo Electric Industries, Ltd. Process for preparing a high voltage ignition cable having low electrostatic capacity
JP2000113738A (en) * 1998-10-06 2000-04-21 Sumitomo Electric Ind Ltd Power cable and its recycling method
JP2013234311A (en) * 2012-04-09 2013-11-21 Shin-Etsu Chemical Co Ltd Silicone rubber composition for use as high-voltage insulator and polymer insulator
KR20140109558A (en) * 2013-03-04 2014-09-16 엘에스전선 주식회사 Power cable with high fire retardance
KR102020066B1 (en) 2013-02-01 2019-09-10 엘에스전선 주식회사 Insulating wire having partial discharge resistance and high partial discharge inception voltage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330493A (en) 1980-02-13 1982-05-18 Sumitomo Electric Industries, Ltd. Process for preparing a high voltage ignition cable having low electrostatic capacity
JP2000113738A (en) * 1998-10-06 2000-04-21 Sumitomo Electric Ind Ltd Power cable and its recycling method
JP2013234311A (en) * 2012-04-09 2013-11-21 Shin-Etsu Chemical Co Ltd Silicone rubber composition for use as high-voltage insulator and polymer insulator
KR102020066B1 (en) 2013-02-01 2019-09-10 엘에스전선 주식회사 Insulating wire having partial discharge resistance and high partial discharge inception voltage
KR20140109558A (en) * 2013-03-04 2014-09-16 엘에스전선 주식회사 Power cable with high fire retardance

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