KR920004784B1 - Black color crosslinked resin composition for electric line and its preparing method - Google Patents

Black color crosslinked resin composition for electric line and its preparing method Download PDF

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KR920004784B1
KR920004784B1 KR1019890007873A KR890007873A KR920004784B1 KR 920004784 B1 KR920004784 B1 KR 920004784B1 KR 1019890007873 A KR1019890007873 A KR 1019890007873A KR 890007873 A KR890007873 A KR 890007873A KR 920004784 B1 KR920004784 B1 KR 920004784B1
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black
weight
power cable
resin composition
carbon black
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KR910000900A (en
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이승형
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한양화학 주식회사
박원배
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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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Abstract

The black crosslinked resin composition for an insulating cable comprises: 100 wt. pts. of polyethylene as a base resin; 0.5-3.0 wt. pts. of the crosslinking agent; 0.3-0.8 wt. pts. of carbon black; 0.1-0.8 wt. pts. of antioxidant; 0.2-0.8 wt. pts. of wax; and 0.003-0.08 wt. pts. of the surface treating agent. Pref. the carbon black has 90-110 m2/g of the surface area, 20-30 nm of particle size, 0.010-0.016 g/cm2 of the density and pH 4.0. Pref. the base resin is polyolefin resin having olefin as main component.

Description

전선용 흑색 가교수지 조성물Black crosslinked resin composition for electric wire

제 1 도는 본 발명의 실시예 1의 카본 분산도를 나타낸 확대사진(X200).1 is an enlarged photograph (X200) showing a carbon dispersion degree of Example 1 of the present invention.

제 2 도는 본 발명의 실시예 2의 카본 분산도를 나타낸 확대사진(X200).2 is an enlarged photograph (X200) showing a carbon dispersion degree of Example 2 of the present invention.

제 3 도는 비교예 1의 카본 분산도를 나타낸 확대사진(X200).Figure 3 is an enlarged photograph (X200) showing the carbon dispersion degree of Comparative Example 1.

제 4 도는 비교예 2의 카본 분산도를 나타낸 확대사진(X200).Figure 4 is an enlarged photograph (X200) showing the carbon dispersion degree of Comparative Example 2.

본 발명은 옥외용 고압전력케이블 절연용의 가교가능한 전선용 흑색 가교수지 조성물에 관한 것이다.The present invention relates to a black crosslinkable resin composition for crosslinkable wires for high voltage power cable insulation for outdoor use.

좀더 상세히 설명하면, 베이스수지인 폴리에틸렌에 가교제, 카본블랙, 산화방지제, 왁스 및 표면처리제인 고급지방산을 함유하는 옥외용 고압전력 케이블(6.6KV 및 22KV급) 절연용 가교가능한 흑색 수지 조성물에 관한 것으로, 상기 첨가제중 내후성 증진제인 카본블랙 마스터배치 제조시 카본블랙을 고급지방산으로 표면처리하고 왁스를 활제로 사용, 옥외용 고압전력 케이블 절연시 압출가공성이 우수할 뿐 아니라, 베이스수지내 카본블랙 분산도를 향상시켜 내후성 및 기계적 특성이 뛰어난 절연체를 얻을 수 있는 것이다.More specifically, the present invention relates to a crosslinkable black resin composition for insulation of high-voltage power cables (6.6KV and 22KV grades) for outdoor use, which contains a crosslinking agent, carbon black, antioxidant, wax, and a surface treating agent in polyethylene as a base resin. When manufacturing carbon black masterbatch which is a weathering enhancer among the above additives, carbon black is surface treated with high grade fatty acid and wax is used as lubricant. It is not only excellent in extrudability when insulating high voltage cable for outdoor use, but also improves carbon black dispersion in base resin. It is possible to obtain an insulator excellent in weather resistance and mechanical properties.

옥외용 전력케이블이란 지중선 케이블과 가공선의 중간형태의 전선으로 실외에 사용되는 전선을 통칭하는 것으로, 지중선이 도체, 절연체, 차폐층 및 피복층 등을 갖춘 완벽한 형태의 전력케이블이라면, 옥외용 전선은 가공선 즉, 도체만으로 이루어진 전선(나선)에 절연체와 피복체의 두 기능을 갖춘 한층의 재료만을 씌운 간단한 구조의 전선이다. 옥외용 전선은 600Volt급 저전압 용도가 전부이다.The outdoor power cable is a wire between the underground cable and the overhead line, which is a wire used for outdoor use. If the underground cable is a complete power cable having conductors, insulators, shielding layers, and sheathing layers, the outdoor wire is a overhead line, It is a simple wire structure in which a wire made of only a conductor is covered with only one material having two functions of an insulator and a sheath. All outdoor wires are for 600Volt low voltage applications.

이것은 6.6KV 및 22KV급 이상의 고전압에 사용되는 옥외용 전선은, 상기 용도로 수요가 많지 않고, 고전압 용도의 경우 단순히 한층만의 재료로서는 고전압계에서의 전기적 신뢰성(내전압특성)과 내후수명 양자에 대한 신뢰성을 동시에 보장할 수 없기 때문이다.This is because outdoor wires used for high voltages of 6.6KV and 22KV or higher are not in demand for the above-mentioned applications, and in the case of high voltage applications, they are simply materials for electrical reliability (withstand voltage characteristics) and weather resistance of both high voltage meters. This cannot be guaranteed at the same time.

그러나 한국의 경우, 미국 및 유럽 여러나라들과 다른 상황에 있다. 미국이나 유럽의 경우 600volt급 옥외용 전선은 흑색고충진 가교콤파운드(10∼30% 카본블랙 함유)를 피복한 옥외용 전선으로 그 수요가 많지만 한국의 경우 대부분 PVC피복전선이 사용되고 있는 실정이다.However, in Korea, the situation is different from those in the US and Europe. In the United States and Europe, 600 volt outdoor wires are coated with black high-filling crosslinking compound (containing 10-30% carbon black), which are in high demand. However, in Korea, PVC-coated wires are mostly used.

반면 6.6KV 및 220KV급의 고전압 흑색가교 폴리에틸렌으로 절연된 옥외용 전선은 국내에서 대량으로 사용되고 있고, 그 이유는 이 케이블이 가공선 용도로 사용되고 있기 때문이다.On the other hand, outdoor wires insulated with 6.6KV and 220KV high-voltage black crosslinked polyethylene are used in large quantities in Korea because the cables are used for overhead wires.

일반적으로 가공선의 경우 피복이 필요치 않으나, 한국의 경우 산악지대가 많고 국토가 협소하여 인구가 밀집되어 있는 지역이 많아 고압가공선이 지나가는 구간에 수목접촉으로 인한 산불발생과 인명피해 사고를 고려 가공선의 절연에 요구되었다.In general, overhead lines are not required, but in Korea, there are many mountainous areas and a narrow area of land, and there are many areas with high population density. Was required.

이같이 절연된 가공선을 옥외용 고압(6.6KV 및 22KV급) 전력케이블이라 불리며, 옥외에서 사용되는 고압케이블이므로 케이블의 수명이 통상적으로 30년이상 장기간 신뢰성을 요구한다는 면에서 케이블 절연체의 내후성과 내산화성이 우수해야만 한다.The insulated overhead wire is called outdoor high voltage (6.6KV and 22KV) power cable, and since it is a high voltage cable used outdoors, the weather resistance and oxidation resistance of the cable insulator are generally required for long life over 30 years. Must be excellent

케이블의 노화방지를 위한 내후성 증진제로 일반적으로 카본블랙이 사용되나, 일반통신케이블 피복용에 사용되는 카본블랙과는 특성이 다른 즉, 22KV라는 고전압하에서의 절연목적과 내후성 목적을 동시에 이루어야 하기 때문에 카본블랙의 선정에 있어 세심한 주의가 요구된다.Carbon black is generally used as a weathering enhancer to prevent the aging of cables.However, carbon black is different from carbon black, which is used for coating general communication cables. Careful attention is required in the selection of the.

이는 카본블랙이 절연체의 전기적 특성을 최대한 저해하지 않아야 하기 때문이다. 베이스수지에 카본블랙을 함유시키는 경우, 적정 카본블랙 함량에서 크기가 작고, 구조가 작으며 또한, 이들 카본블랙의 베이스수지내 분산성이 우수할수록 22KV급 고전압케이블 절연용 조성물의 전기특성을 저하시키지 않는다.This is because carbon black should not inhibit the electrical properties of the insulator as much as possible. When carbon black is contained in the base resin, the smaller the size, the smaller the structure, and the better the dispersibility of the carbon black in the base resin, the lower the electrical characteristics of the 22KV class high voltage cable insulation composition. Do not.

특히, 고전압하에서는 카본분산이 절대적으로 양호해야 한다. 이는 미분산 카본블랙 덩어리가 케이블 절연피복체의 내전압특성에 치명적인 영향을 주기 때문이다.In particular, under high voltage, carbon dispersion should be absolutely good. This is because the undispersed carbon black lump has a fatal effect on the breakdown voltage characteristics of the cable insulation coating.

또한, 케이블 제조시나 포설후 절연체의 물성을 저하시키는 절연체의 산화를 억제하기 위해 산화방지제의 선택 및 처방도 중요하다. 이는 베이스수지의 산화로 인한 절연체 물성저하 억제기능을 산화방지제가 가지기 때문이다.In addition, the selection and prescription of antioxidants are also important in order to inhibit oxidation of the insulator, which degrades the properties of the insulator during cable manufacture or after installation. This is because the antioxidant has a function of suppressing the deterioration of insulator properties due to the oxidation of the base resin.

또한, 산화방지제의 용융온도에 따른 선택이 상당히 중요하다. 이는 각기 선택된 조성물의 구성원 재료들을 콤파운딩 할 때, 조성물들의 혼련이 원활하게 될 수 있게 하기 때문이다.In addition, the choice of antioxidant depending on the melting temperature is of great importance. This is because, when compounding the member materials of each selected composition, the kneading of the compositions can be facilitated.

이외에 옥외용 전압케이블 절연용 조성물에는 고압하 절연목적으로 물성의 증가를 위해 가교제가 함유되며, 고전압 케이블의 제조시 가교제가 분해되지 않는 조건(130℃ 이하)에서 압출가공을 해야 한다. 이같은 한계성이 존재하기 때문에 옥외용 고압케이블 절연용 조성물의 압출가공성이 나쁠 경우 압출선속증가의 제한으로 케이블 제조원가가 높아지며, 선속을 높이기 위해 압출기 온도를 높일 경우에는 스코치 현상(국부적인 가교현상)에 발생하게 되어 케이블 절연체의 물성을 저하시키게 된다.In addition, the outdoor voltage cable insulation composition contains a crosslinking agent to increase the physical properties for insulation under high pressure, and must be extruded under the condition that the crosslinking agent is not decomposed when the high voltage cable is manufactured (below 130 ° C). Due to such limitations, if the extrusion processability of the outdoor high voltage cable insulation composition is bad, the cable manufacturing cost is increased due to the increase of the extrusion flux, and when the extruder temperature is increased to increase the flux, the scorch phenomenon (local crosslinking phenomenon) may occur. This lowers the physical properties of the cable insulator.

상기 언급한 옥외용 고압전력 케이블 절연용 가교가능 흑색수지 조성물의 문제점 해결을 위해 본 발명자는 예의 노력한 결과, 적정 가교제, 카본블랙, 산화방지제의 조합과 카본블랙의 베이스수지내 분산도 향상 및 최종 조성물의 압출가공성을 높이기 위해 카본블랙 마스터배치 제조시, 고급지방산을 표면처리제로 사용하고, 왁스를 활제로 사용, 옥외용 고압케이블 절연시 내후성과 기계적특성 및 압츨가공특성이 우수한 절연체를 제조할 수 있는 전선용 흑색 가교수지 조성물을 안출하게 되었다.In order to solve the problems of the above-mentioned crosslinkable black resin composition for outdoor high voltage power cable insulation, the present inventors have made diligent efforts to improve the dispersion of the base composition of the base composition of carbon black with a combination of a suitable crosslinking agent, carbon black, and antioxidant. When manufacturing carbon black masterbatch to improve extrusion processability, use high quality fatty acid as surface treatment agent, use wax as lubricant, and use for electric wire that can manufacture insulator with excellent weatherability, mechanical property and press-cutting property when insulating high voltage cable for outdoor use A black crosslinked resin composition was devised.

본 발명에서 사용한 고급지방산은 카본블랙의 표면처리로 카본블랙의 베이스수지내 분산도를 높여주며, 왁스는 활제로서의 기능을 가져 최종 전선용 흑색가교 가능 조성물의 압출가공성을 우수하게 한다.The higher fatty acid used in the present invention improves the dispersion degree of the carbon black in the base resin by surface treatment of the carbon black, and the wax has a function as a lubricant to provide excellent extrusion processability of the black crosslinkable composition for the final electric wire.

본 발명에 사용된 가교제는 옥외용 고압전력 케이블 절연시 절연체를 가류관에서 가교시켜 고압하에서의 절연목적을 위한 물성증가를 위해 첨가하는 첨가제로서 1, 1-Bis-t-butyl peroxy-3, 3, 5-tri-methylcyclo hexane, Decumyl peroxide, 2, 5-Dimethyl-2, 5-di-t-butyl peroxyl hexyne-3, T-butyl peroxy benzoate, n-Butyl-4, 4-bis-t-butyl peroxy valerate, Di-t-butyl peroxide, Di-t-butyl peroxy di-isopropyl benzene, 2, 5-Dimethyl-2, 5-di-t-butyl peroxy hexane 등으로서 옥외용 전력 케이블 수지조성물에 최종적으로 함유되는 양은 베이스수지 100중량부에 대해서 0.5∼3.0중량부이다.The crosslinking agent used in the present invention is an additive which is added to increase the physical properties for insulation purposes under high pressure by crosslinking the insulator in the vulcanization tube when the outdoor high voltage cable is insulated. 1, 1-Bis-t-butyl peroxy-3, 3, 5 -tri-methylcyclo hexane, Decumyl peroxide, 2, 5-Dimethyl-2, 5-di-t-butyl peroxyl hexyne-3, T-butyl peroxy benzoate, n-Butyl-4, 4-bis-t-butyl peroxy valerate , Di-t-butyl peroxide, Di-t-butyl peroxy di-isopropyl benzene, 2, 5-Dimethyl-2, 5-di-t-butyl peroxy hexane, etc. It is 0.5-3.0 weight part with respect to 100 weight part of resin.

본 발명에 사용된 카본블랙은 케이블 절연체의 내후성 충진제이며, 표면적 90∼110㎡/g, 입자크기 20∼30㎚, 고정카본함량 97∼99%, 밀도 0.010∼0.016g/㎤, pH 4.0 이하인 카본블랙으로서 카본블랙 마스터배치 제조시, 사용량은 마스터배치 전 중량의 5∼15wt%이며, 옥외용 전력케이블 수지 조성물에 최종적으로 함유되는 양은 베이스수지 100중량부에 대해 0.3∼0.8중량이다.Carbon black used in the present invention is a weatherproof filler of cable insulator, and has a surface area of 90 to 110 m 2 / g, particle size of 20 to 30 nm, fixed carbon content of 97 to 99%, density of 0.010 to 0.016 g / cm 3, and pH 4.0 or less. When producing a carbon black masterbatch as black, the amount used is 5 to 15 wt% of the weight before the masterbatch, and the amount finally contained in the outdoor power cable resin composition is 0.3 to 0.8 weight based on 100 parts by weight of the base resin.

본 발명에 사용된 산화방지제는 케이블가공시나 포설후, 직접 또는 간접으로 받게되는 케이블 절연체의 산화를 억제하는 기능을 가지는 것으로서, 1차 산화방지제는 용융온도가 125℃ 이하 또는 그 이상인 페놀계 산화방지제로서, Octadecy 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate, Pentaerythrityl-tetarakis[3-(3, 5-di-tert-butyl-4-hydroxy-phenyl)-propionate], Thiodiethylene bis-(3, 5-di-tert-butyl-4-hydroxy)-hydrocinnamate, 2, 2-Thio-bis(b-t-butyl-p-cresol), 4, 4-Thio-vis(6-t-butyl-m-cresol) 등이고 2차 산화방지제로서는 에스테르계 산화방지제로 예를들면 Di(tri-decyl) thiodipropionate 등을 사용할 수 있고, 상기 1차 및 2차 산화방지제를 조합하여 사용할 수 있으며 2차 산화방지제 단독으로 사용할 수도 있다.The antioxidant used in the present invention has a function of inhibiting oxidation of the cable insulator which is directly or indirectly received during or after cable processing, and the primary antioxidant is a phenolic antioxidant having a melting temperature of 125 ° C. or lower or higher. For example, Octadecy 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate, Pentaerythrityl-tetarakis [3- (3, 5-di-tert-butyl-4-hydroxy-phenyl) -propionate], Thiodiethylene bis- (3, 5-di-tert-butyl-4-hydroxy) -hydrocinnamate, 2, 2-Thio-bis (bt-butyl-p-cresol), 4, 4-Thio-vis (6-t-butyl-m-cresol) As the secondary antioxidant, for example, Di (tri-decyl) thiodipropionate may be used as an ester antioxidant, and may be used in combination with the primary and secondary antioxidants, or may be used alone as a secondary antioxidant. .

상기 산화방지제의 최종 베이스수지에 첨가되는 양은 1차 및 2차 산화방지제를 조합하여 사용하는 경우 1차 산화방지제가 베이스수지 100중량부에 대해 0.1∼0.5중량부, 2차 산화방지제 0.1∼0.3중량부가 적당하며, 1차 산화방지제만 사용하는 경우 0.1∼0.5중량부가 최적의 효과를 나타낸다.The amount of the antioxidant added to the final base resin is 0.1 to 0.5 parts by weight based on 100 parts by weight of the primary antioxidant, 0.1 to 0.3 parts by weight of the secondary antioxidant when the primary and secondary antioxidants are used in combination The addition is appropriate, and 0.1 to 0.5 parts by weight is optimal when only the primary antioxidant is used.

본 발명에 사용된 활제의 기능을 가진 왁스는 카본블랙의 마스터배치 제조시 카본블랙 유동성을 높여 마스터배치 제조시 사용되는 담체내의 카본블랙 분산 및 분배성을 증진시키는데 기여하고, 용융점이 담체보다 낮아 먼저 용융되므로서 파우더 형태의 카본블랙의 외부를 코팅시켜 담체에 부착시키게 하여 마스터배치 제조시 사용되는 배치타입믹서(반버리믹서) 외부로 카본블랙이 유출되는 것을 막아주는 역할도 겸한다.The wax having the function of the lubricant used in the present invention increases carbon black fluidity when preparing the master batch of carbon black, thereby contributing to enhancing the carbon black dispersion and distribution in the carrier used in the production of the masterbatch. It also serves to prevent carbon black from leaking out of the batch-type mixer (Banbury mixer) used in the manufacture of the master batch by coating the outside of the powdered carbon black to the carrier by melting.

또한, 활제로서의 역할을 수행하여 최종 조성물의 압출가공성을 높여주어 케이블가공시 경제적 잇점을 가지게 한다.In addition, it serves as a lubricant to increase the extrudability of the final composition to have an economic advantage in cable processing.

상기 물질에 알맞은 왁스류로는 밀도 0.915∼0.920g/㎤, 60∼120℃ 연화점을 가져야 하며, 특히 80∼110℃ 범위의 연화점을 가지는 입자상(0.5mm 이하)의 왁스가 좋으며, 종류로는 폴리올레핀 왁스인 평균분자량 1,500∼8,000 범위의 저분자량 폴리에틸렌, 저분자량 폴리프로필렌 및 저분자량 비닐 아세테이트 공중합체이며, 카본블랙 마스터배치 제조시 왁스사용량은 카본블랙 마스터배치 제조시 마스터배치 전중량에 대해 5∼10wt%이다.Waxes suitable for the material should have a density of 0.915 to 0.920 g / cm 3 and a softening point of 60 to 120 ° C. Particularly, waxes in the form of particles (0.5 mm or less) having a softening point in the range of 80 to 110 ° C are preferable. Low molecular weight polyethylene, low molecular weight polypropylene, and low molecular weight vinyl acetate copolymers in the range of 1,500 to 8,000 average molecular weights of waxes. Wax usage in the production of carbon black masterbatches is 5-10 wt.% Based on the total weight of the master batch in the production of carbon black masterbatches. %to be.

상기 범위이하에서는 카본블랙 분산의 효과를 얻을 수 없고, 상기 범위이상에서는 최종수지 조성물로 케이블절연체 제조시 압출특성에 있어 압출맥동현상을 유발하여 케이블 제조시 압출선속에 이상이 초래될 수 있다.In the above range, the effect of carbon black dispersion may not be obtained, and in the above range, an extrusion pulsation may be induced in the extrusion characteristics in the manufacture of the cable insulator with the final resin composition, thereby causing an abnormality in the extrusion line during the manufacture of the cable.

본 발명에 사용된 카본블랙 표면처리제는 고급지방산으로서 카본블랙 마스터배치 제조시 카본블랙의 담체내 분산도를 향상시켜 최종수지 조성물 제조시 카본블랙 농축물을 베이스 수지와 렛다운(Let-down)할 때, 베이스수지내 카본블랙 분산도를 높여주는 기능을 수행한다.The carbon black surface treatment agent used in the present invention is a higher fatty acid, which improves the dispersibility of the carbon black in the carrier when preparing the carbon black masterbatch, so that the carbon black concentrate may be let-down when the final resin composition is prepared. At the same time, it serves to increase the carbon black dispersion in the base resin.

상기 목적에 알맞는 고급지방산으로는 카르복시기를 하나 가지는 쇄식화합물이며, 탄소원자 10∼18의 고급지방산으로서 종류로는 라이릴에시드, 파미틱 에시드, 올레익에시드, 스테아릭에시드, 캐프릭에시드, 미리스틱에시드 및 라이노레익에시드 등으로서, 사용량은 카본블랙 마스터배치 제조시 카본블랙 100중량부에 대해 1∼10중량부이다.The higher fatty acid suitable for the above purpose is a chain compound having one carboxyl group, and the higher fatty acid having 10 to 18 carbon atoms may be lyryl acid, pharmic acid, oleic acid, stearic acid, capric acid, or the like. As the stick acid and the rhino-leak acid, etc., the amount used is 1 to 10 parts by weight based on 100 parts by weight of carbon black in the production of the carbon black masterbatch.

본 발명에 있어 카본블랙 마스터배치 제조시 사용할 수 있는 담체는 옥외용 전력 케이블절연용 흑색수지 조성물을 만들기 위해 사용되는 베이스수지와의 상용성이 좋아야 하며, 분자량 15,000∼30,000, 용융점 90∼115℃인 폴리올레핀계 수지인 저밀도 폴리에틸렌(밀도 0.919∼0.926g/㎤, MI 0.5∼3.0g/10min.)이 좋으며, 카본블랙 마스터배치 제조시 사용량은 전 중량의 70∼85wt%이다.In the present invention, the carrier that can be used in manufacturing the carbon black masterbatch should have good compatibility with the base resin used to make the black resin composition for the insulation of power cables for outdoor use, and has a molecular weight of 15,000 to 30,000 and a melting point of 90 to 115 ° C. Low-density polyethylene (density 0.919 to 0.926 g / cm 3, MI 0.5 to 3.0 g / 10 min.), Which is a system resin, is preferable, and the amount of the carbon black master batch used is 70 to 85 wt% based on the total weight.

본 발명에 있어 옥외용 전력케이블 절연피복용 콤파운드의 베이스수지로 사용할 수 있는 베이스수지로는 올레핀을 주성분으로 하는 폴리올레핀계 수지, 예를들면 에틸렌과 탄소원자 4 이상의 α-올레핀으로부터 중합된 밀도 0.917∼0.931g/㎤, MI 0.3∼3.0g/min, 범위의 저밀도 폴리에틸렌, 선형저밀도 폴리에틸렌, 중밀도 폴리에틸렌 등이 옥외용 고압전력케이블(6.6KV 및 22KV급) 절연용 가교가능한 흑색수지 조성물의 베이스수지로 사용할 수 있다.In the present invention, the base resin that can be used as the base resin of the insulation coating compound for outdoor power cables is a density of 0.917 to 0.931 polymerized from a polyolefin resin having olefin as a main component, for example, ethylene and α-olefin having 4 or more carbon atoms. Low density polyethylene, linear low density polyethylene, and medium density polyethylene in the range of g / cm3, MI 0.3 ~ 3.0g / min, etc. can be used as the base resin of the crosslinkable black resin composition for insulation of high voltage power cables (6.6KV and 22KV class) for outdoor use. have.

본 발명에 있어 상기 전술한 베이스수지와 첨가제로 옥외용 고압전력케이블 절연용 가교가능 흑색수지 조성물을 다음과 같은 실시예와 비교예를 통하여 구체적인 제조방법 및 그 효과를 상술한다.In the present invention, the cross-linkable black resin composition for insulation of the high-voltage power cable for outdoor use with the above-described base resin and additives will be described in detail through the following examples and comparative examples, and a detailed manufacturing method and effects thereof.

그러나, 다음의 예가 본 발명의 범주를 한정하는 것은 아니다.However, the following examples do not limit the scope of the present invention.

[실시방법][Method of implementation]

1. 옥외용 고압전력케이블 절연용 흑색가교수지 제조방법1. Manufacturing method of black crosslinked resin for insulation of high voltage power cable for outdoor

1단계 : 60∼70℃로 유지되는 헨실믹서에 카본블랙과 용융된 고급지방산을 넣어 10∼20분간 교속교반 하면서 카본블랙을 표면처리한다.Step 1: Carbon black and molten higher fatty acid are added to a hexyl mixer maintained at 60 to 70 ° C., and the carbon black is surface treated while stirring for 10 to 20 minutes.

2단계 : 카본블랙 마스터배치 제조 가열매체가 100∼140℃로 유지되는 배치타입 혼련기(반버리믹서)에 담체인 저밀도 폴리에틸렌 수지를 넣고, 용융시킨 후 상기 표면처리된 카본블랙 및 왁스를 넣어 160∼190℃온도에서 30분간 혼련한다. 이 혼련물에 산화방지제를 다시 첨가하여 15분간 혼련을 더하여 최종 카본블랙 마스터배치(산화방지제 포함)를 제조한다.Step 2: Carbon Black Master Batch Preparation A low density polyethylene resin as a carrier is placed in a batch type kneader (Banbury mixer) in which the heating medium is maintained at 100 to 140 ° C., followed by melting. It knead | mixes for 30 minutes at -190 degreeC temperature. An antioxidant was added to this kneaded material and kneaded for 15 minutes to prepare a final carbon black masterbatch (including antioxidant).

3단계 : 최종 전선용 흑색가교수지 조성물 제조 베이스수지인 폴리에틸렌, 카본블랙 마스터배치 및 가교제를 1축 또는 2축 연속 혼련기에서 가교제가 분해되지 않는 130℃ 이하온도에서 혼련 및 압출제립화하여 최종 전선용 흑색가교수지 조성물을 제조한다.Step 3: Preparation of black crosslinked resin composition for final wire The final wire was kneaded and extruded at a temperature of 130 ° C. or less at which the crosslinking agent was not decomposed in a single- or two-axis continuous kneader, which is a polyethylene, carbon black masterbatch, and a crosslinking agent. A black crosslinkable resin composition is prepared.

2. 옥외용 고압(22.9KV ACSR-OC)전력케이블 제조조건2. Manufacturing conditions for high voltage (22.9KV ACSR-OC) power cable for outdoor use

·기기 : 스크류경 : 150ψ/L/D=20/CV LineInstrument: Screw diameter: 150ψ / L / D = 20 / CV Line

·선재 : 22.9KV, 58 Square, ACSR-OCWire rod: 22.9KV, 58 Square, ACSR-OC

·작업조건Working condition

- 압출기온도(℃) : C1/C2/C3/C4/Nock/Die=110/118/120/122/122/120-Extruder temperature (℃): C 1 / C 2 / C 3 / C 4 / Nock / Die = 110/118/120/122/122/120

- 수지온도(℃) : 128-Resin temperature (℃): 128

- 스크류 RPM : 20Screw RPM: 20

- 스크류 냉각수 온도(℃) : 97Screw coolant temperature (℃): 97

- 가류관 압력(kg/㎠) : 6.5(가스 가교방식)-Vortex pipe pressure (kg / ㎠): 6.5 (gas crosslinking method)

- 가류관 온도(℃) : 380-Cavitation pipe temperature (℃): 380

-가류관 길이 : 60m(가교)/60m(냉각)-Vortex pipe length: 60m (bridge) / 60m (cooling)

[실시예 1]Example 1

상기 실시방법에서 제시한 방법에 의해 1단계에서 60℃로 유지되는 헨실믹서에 표면적 96㎡/g, 입자크기 25nm 및 pH 4.0인 카본블랙(케보트사, Rogal 400)을 넣고, 카본블랙 100중량부에 대해 표면처리제인 고급지방산, 올레익에시드 3중량부를 용융시켜 넣어 1,200∼1,500rpm에서 20분간 교반시키면서 카본블랙의 건조와 더불어 카본블랙을 표면처리한다.The carbon black (Kebot, Rogal 400) having a surface area of 96 m 2 / g, a particle size of 25 nm, and a pH of 4.0 was added to a hexyl mixer maintained at 60 ° C. in the first step by the method proposed in the above method. 3 parts by weight of a higher fatty acid and oleic acid, which are surface treatment agents, are melted and then the carbon black is surface-treated with drying of carbon black while stirring at 1,200-1,500 rpm for 20 minutes.

2단계에서 배치타입믹서(반버리믹서)에 담체인 저밀도 폴리에틸렌(밀도 0.920gLow density polyethylene (density 0.920 g) as a carrier in batch type mixer (Banbury mixer) in 2 stages

/㎤, 멜트인덱스 2.0g/10min : 한양화학주식회사, LDPE 830) 100중량부에 대해 상기 표면처리된 카본블랙 12중량부 및 폴리에틸렌 왁스(밀도 0.916g/㎤ : 라이온케미칼, LC-201N) 4중량부를 넣고 혼련한 후, 카봅블랙 마스터배치 100중량부에 대해 1차 산화방지제(시바가이기사, Irganox 1076)와 2차 산화방지제(시바가이기사, Irganox 802)를 각각 3.5 및 2.5중량부를 넣고 혼련으로 최종 카본블랙(산화방지제 포함) 마스터배치를 제조한다.12 parts by weight of the surface treated carbon black and polyethylene wax (density 0.916 g / cm 3: Lion Chemical, LC-201N) with respect to 100 parts by weight of the melt index 2.0g / 10min: Hanyang Chemical Co., Ltd., LDPE 830) After mixing and kneading, the mixture was kneaded with 3.5 and 2.5 parts by weight of the primary antioxidant (Shibagaiki Co., Irganox 1076) and the secondary antioxidant (Shibagaiki Co., Irganox 802) with respect to 100 parts by weight of Kabob Black Masterbatch. Prepare the final carbon black (including antioxidant) masterbatch.

3단계에서 베이스수지(LDPE 830) 100중량부에 대해 가교제인 디쿠밀퍼옥사이드 2중량부 및 상기 1, 2단계에서 제조한 카본블랙 마스터배치 5.5중량부를 1축 연속혼련기에서 130℃ 이하에서 혼련 및 압축하여 최종 전선용 흑색 가교수지를 제조, 상술한 옥외용 고압케이블 제조조건에서 케이블 절연체를 제조하고, 특성평가를 실시하였다. 실시결과는 [표 1]에 나타내었다.2 parts by weight of dicumyl peroxide, a crosslinking agent, and 5.5 parts by weight of carbon black masterbatch prepared in steps 1 and 2, were kneaded at 130 ° C. or lower in a single screw continuous kneader in 100 parts by weight of the base resin (LDPE 830) in step 3. The black crosslinked resin for the final electric wire was produced by compression, and the cable insulator was manufactured under the above-described conditions for manufacturing the high voltage cable for outdoor use, and the characteristics were evaluated. The results are shown in [Table 1].

아울러, 카본분산효과를 알아 보기 위해 현미경(X200) 촬영을 실시하여 그 결과를 제 1 도에 나타내었는바 후술하는 비교예 1, 2의 사전과 비교해 볼 때 고르게 분산되어 있음을 알 수 있다.In addition, a microscope (X200) was taken to examine the carbon dispersing effect, and the results are shown in FIG. 1, which shows that it is evenly dispersed when compared with the dictionary of Comparative Examples 1 and 2 described later.

[실시예 2]Example 2

실시예 1과 동일하나 표면처리제로 올레익에시드 대신 스테아릭에시드를 사용하여 최종 전선용 흑색가교수지를 제조, 상술한 옥외용 고압케이블 제조조건에서 케이블 절연체를 제조하고 특성평가를 실시하였다. 실시결과는 [표 1]에 나타내었다.In the same manner as in Example 1, stearic acid was used instead of oleic acid as the surface treatment agent to prepare black crosslinked resin for the final wire, and a cable insulator was manufactured under the above-described outdoor high voltage cable manufacturing conditions and evaluated. The results are shown in [Table 1].

아울러 카본분산효과를 알아보기 위해 현미경(X200) 촬영을 실시하여 그 결과를 제 2 도에 나타내었다. 그 결과는 실시예 1과 마찬가지로 고르게 분산되어 있음을 알 수 있다.In addition, the microscope (X200) was taken to examine the carbon dispersion effect and the results are shown in FIG. The results can be seen to be evenly distributed as in Example 1.

[비교예 1]Comparative Example 1

실시예 1의 1단계인 카본블랙 표면처리제를 행하지 않았다. 최종 흑색가교수지의 조성(카본블랙, 왁스, 산화방지제, 가교제)은 실시예 1과 동일하다. 특성평가결과는 [표 1]에 나타내었으며, 아울러 카본 분산효과를 알아보기 위해 현미경(X200) 촬영을 실시하여 그 결과를 제 3 도에 도시하였다.The carbon black surface treatment agent which is the first step of Example 1 was not performed. The composition of the final black crosslinked resin (carbon black, wax, antioxidant, crosslinking agent) is the same as in Example 1. The results of the characteristic evaluation are shown in [Table 1], and the results of the microscopic (X200) imaging were performed to examine the carbon dispersion effect, and the results are shown in FIG. 3.

[비교예 2]Comparative Example 2

실시예 1과 동일하며, 2단계에서 카본블랙 마스터배치 제조시 왁스를 제외하였다. 제거된 왁스양은 담체량의 증가로 대치하였으며, 최종 수지의 조성은 실시예 1과 동일하다. 특성평가결과는 [표 1]에 나타내었으며, 아울러 카본분산결과를 알아 보기 위해 현미경(X200) 촬영을 실시하여 그 결과를 제 4 도에 도시하였다.Same as Example 1, except in the second step to prepare a carbon black masterbatch wax. The amount of wax removed was replaced by an increase in the amount of carrier, and the composition of the final resin was the same as in Example 1. The results of the characteristic evaluation are shown in [Table 1], and the results of the microscopic (X200) imaging were performed to check the carbon dispersion results.

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

*인장강도는 제조된 케이블 절연체로부터 시편을 채취하여 시험하였다. 시험방법 : ASTM D 638Tensile strength was tested by taking specimens from the manufactured cable insulators. Test Method: ASTM D 638

＊1. 카본분산 시험방법 : ASTM D 3015-72(제1 내지 4 도 참조)*One. Carbon Dispersion Test Method: ASTM D 3015-72 (See FIGS. 1 to 4)

＊2. 자외선 흡광계수 시험방법 : ASTM D 3349-74*2. Ultraviolet Absorption Coefficient Test Method: ASTM D 3349-74

＊3. 압출가공특성 : 실시방법 2. 참조＊ 3. Extrusion processing characteristics: see Method 2.

Claims (16)

베이스수지인 폴리에틸렌 100중량부에 대해 가교제 0.5∼3.0중량부, 카본블랙 0.3∼0.8중량부, 산화방지제 0.1∼0.8중량부, 왁스 0.2∼0.8중량부 및 표면처리제 0.003∼0.08중량부가 함유된 옥외용 고압 전력 케이블절연용 흑색가교 수지 조성물.Outdoor high pressure containing 0.5 to 3.0 parts by weight of crosslinking agent, 0.3 to 0.8 parts by weight of carbon black, 0.1 to 0.8 parts by weight of antioxidant, 0.2 to 0.8 parts by weight of wax and 0.003 to 0.08 parts by weight of surface treatment agent, based on 100 parts by weight of polyethylene, the base resin. Black crosslinking resin composition for power cable insulation. 제 1 항에 있어서, 카본블랙은 표면적 90∼110㎡/g 입자크기 20∼30nm, 밀도, 0.010∼0.016g/㎤ 및 pH 4.0 이하인 카본블랙인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.The black crosslinkable resin for outdoor high voltage power cable insulation according to claim 1, wherein the carbon black is carbon black having a surface area of 90 to 110 m 2 / g particle size of 20 to 30 nm, a density of 0.010 to 0.016 g / cm 3, and a pH of 4.0 or less. Composition. 제 1 항에 있어서, 베이스수지가 올레핀을 주성분으로 하는 폴리올레핀계 수지로서 에틸렌과 탄소원자 4이상의 α-올레핀으로부터 중합된 밀도 0.917∼0.931g/㎤, MI 0.3∼3.0g/10min, 범위의 저밀도 폴리에틸렌, 선형저밀도 폴리에틸렌 또는중밀도 폴리에틸렌인 것을 특징으로 하는 옥외용 고압전력케이블 절연용 흑색가교 수지 조성물.The low density polyethylene according to claim 1, wherein the base resin is a polyolefin resin mainly composed of olefins and polymerized from ethylene and an α-olefin having 4 or more carbon atoms, and has a density of 0.917 to 0.931 g / cm 3, MI 0.3 to 3.0 g / 10 min. Black crosslinked resin composition for outdoor high voltage power cable insulation, characterized in that the linear low density polyethylene or medium density polyethylene. 제 1 항에 있어서, 가교제가 1, 1-Bis-t-butyl peroxy-3, 3, 5-tri-methyl cyclo hexane, Decumyl peroxide, 2, 5-Dimethyl-2, 5-di-t-butyl peroxyl hexyne-3, T-butyl peroxy benzoate, n-Butyl-4, 4-bis-t-butyl peroxy valerate, Di-t-butyl peroxide Di-t-butyl peroxy di-isopropyl benzene 또는 2, 5-Dimethyl-2, 5-di-t-butyl peroxy hexane인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.The method of claim 1, wherein the crosslinker is 1, 1-Bis-t-butyl peroxy-3, 3, 5-tri-methyl cyclo hexane, Decumyl peroxide, 2, 5-Dimethyl-2, 5-di-t-butyl peroxyl hexyne-3, T-butyl peroxy benzoate, n-Butyl-4, 4-bis-t-butyl peroxy valerate, Di-t-butyl peroxide Di-t-butyl peroxy di-isopropyl benzene or 2, 5-Dimethyl-2 Black crosslinkable resin composition for outdoor high voltage power cable insulation, characterized in that 5-di-t-butyl peroxy hexane. 제 1 항에 있어서, 산화방지제가 1차 산화방지제만으로 또는 1차 산화방지제 및 2차 산화방지제로 구성되며, 상기 1차 산화방지제로는 페놀계류가 사용되며, 상기 2차 산화방지제로는 에스테르류가 사용되는 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.The method of claim 1, wherein the antioxidant is composed of only primary antioxidants or primary and secondary antioxidants, phenol-based is used as the primary antioxidant, esters as the secondary antioxidant Black crosslinkable resin composition for outdoor high voltage power cable insulation, characterized in that it is used. 제 5 항에 있어서, 1차 산화방지제로 Octadecyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate, Pentaerythrityl-tetarakis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)-propionate], Thiodiethylene-bis-(3, 5-di-tert-butyl-4-hydroxy)-hydrocinnamate, 2-2-Thio-bis(b-t-butyl-p-cresol) 또는 4, 4-Thio-bis(6-t-butyl-m-cresol)이고, 2차 산화방지제가 Di(tri-decyl)thiodipropionate인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.The method of claim 5, wherein the primary antioxidant is Octadecyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate, Pentaerythrityl-tetarakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate] , Thiodiethylene-bis- (3, 5-di-tert-butyl-4-hydroxy) -hydrocinnamate, 2-2-Thio-bis (bt-butyl-p-cresol) or 4, 4-Thio-bis (6- t-butyl-m-cresol), and black crosslinkable resin composition for outdoor high voltage power cable insulation, wherein the secondary antioxidant is Di (tri-decyl) thiodipropionate. 제 1 항 또는제 5 항에 있어서, 1차산화방지제만을 사용하는 경우 베이스수지 100중량부에 대해 0.1∼0.5중량부 함유되는 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.The black crosslinkable resin composition for outdoor high-voltage power cable insulation according to claim 1 or 5, wherein 0.1 to 0.5 parts by weight is contained with respect to 100 parts by weight of the base resin when only the primary antioxidant is used. 제 1 항에 있어서, 왁스로 밀도가 0.915∼0.920g/㎤, 연화점 60∼120℃, 평균분자량 1,500∼8,000범위인 저분자량 폴리에틸렌, 저분자량 폴리프로필렌 또는 저분자량 비닐아세테이트 공중합체인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색 가교수지 조성물.The method of claim 1, wherein the wax is a low molecular weight polyethylene, a low molecular weight polypropylene or a low molecular weight vinyl acetate copolymer having a density of 0.915 to 0.920 g / cm 3, a softening point of 60 to 120 ° C., and an average molecular weight of 1,500 to 8,000. Black crosslinked resin composition for high voltage power cable insulation. 제 1 항에 있어서, 표면처리제로 카르복시기를 하나가지는 쇄식 화합무리고, 탄소원자수가 10∼18인 고급지방산인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.The black crosslinkable resin composition for outdoor high-voltage power cable insulation according to claim 1, wherein the compound is a chain compound having one carboxyl group as a surface treatment agent and a high fatty acid having 10 to 18 carbon atoms. 제 9 항에 있어서, 표면처리제가 라이릴액시드, 파미틱에시드, 올레익에시드, 스테아릭에시드, 캐프릭애시드, 미리스틱에시드 또는 라이노제익에시드인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.10. The black crosslinking resin for outdoor high voltage power cable insulation according to claim 9, wherein the surface treatment agent is lyryl acid, pharmic acid, oleic acid, stearic acid, capric acid, mystic acid or rhino-acid acid. Composition. 옥외용 고압 전력 케이블 절연용 흑색 가교수지 조성물을 제조하는데 있어서, (가) 카본블랙을 용융된 고급지방산으로 표면처리하고, (나) 담체로서 폴리에틸렌수지를 용융시키고, 상기 표면처리된 카본블랙과 활제로서의 폴리올레핀왁스 및 산화방지제를 가하여 카본블랙 마스터 배치를 제조하고, (다) 베이스 수지인 폴리에틸렌수지, 상기 카본블랙 마스터 배치 및 가교제를 가하여 혼련압출하는 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색 가교수지 조성물을 제조하는 방법.In preparing black crosslinked resin composition for outdoor high voltage power cable insulation, (A) surface treatment of carbon black with molten higher fatty acid, (B) melt polyethylene resin as carrier, and the surface treated carbon black and lubricant Carbon black master batch is prepared by adding polyolefin wax and antioxidant, and (c) black crosslinked resin composition for insulation of high voltage power cable for outdoor use, which is kneaded and extruded by adding polyethylene resin as base resin, carbon black master batch and crosslinking agent. How to prepare. 제 11 항에 있어서, 카본블랙에 표면적 90∼100㎡/g, 입자크기 20∼30nm, 고정카본함량 97∼99%, 밀도 0.010∼0.016g/㎤, pH 4.0 이하이며, 그 사용량이 카본블랙 마스터배치 전중량의 5∼15wt%인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색 가교수지 조성물.12. The carbon black has a surface area of 90 to 100 m 2 / g, particle size of 20 to 30 nm, fixed carbon content of 97 to 99%, density of 0.010 to 0.016 g / cm 3, and pH 4.0 or less, and the amount of the carbon black used is carbon black master. Black crosslinking resin composition for outdoor high voltage power cable insulation, characterized in that 5-15wt% of the total weight of the batch. 제 11 항에 있어서, 고급지방산이 카르복시기를 하나 가지고 있는 쇄식화합물이고, 탄소원자 10∼18이며, 그 사용량이 카본블랙 100중량부에 대해 1∼10중량부인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색 가교수지 조성물.12. The outdoor high-voltage power cable insulation according to claim 11, wherein the higher fatty acid is a chain compound having one carboxyl group, has 10 to 18 carbon atoms, and the amount thereof is 1 to 10 parts by weight based on 100 parts by weight of carbon black. Black crosslinked resin composition. 제 11 항에 있어서, 담체로서의 폴리에틸렌 수지가 밀도 0.919∼0.926g/㎤, MI 0.5∼3.0g/10min, 용융점 90∼115℃ 및 평균분자량 15,000∼30,000인 저밀도 폴리에틸렌이며, 그 사용량은 카본블랙 마스터배치 전중량의 70∼5wt%인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색 가교수지 조성물.The polyethylene resin as a carrier according to claim 11 is a low density polyethylene having a density of 0.919 to 0.926 g / cm 3, MI 0.5 to 3.0 g / 10 min, a melting point of 90 to 115 ° C., and an average molecular weight of 15,000 to 30,000, the amount of which is used as a carbon black masterbatch. Black crosslinked resin composition for outdoor high voltage power cable insulation, characterized in that the total weight of 70 ~ 5wt%. 제 11 항에 있어서, 사용된 왁스가 밀도 0.915∼0.920g/㎤, 연화점 80∼110℃ 및 평균분자량 1,500∼8,000의 저분자량 폴리에틸렌, 저분자량 폴리프로필렌 또는 저분자량 비닐 아세테이트 공중합체이며, 그 사용량이 카본블랙 마스터배치의 전중량에 대해 5∼10wt%인 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색 가교수지 조성물.The method of claim 11, wherein the wax used is a low molecular weight polyethylene, a low molecular weight polypropylene or a low molecular weight vinyl acetate copolymer having a density of 0.915 to 0.920 g / cm 3, a softening point of 80 to 110 ° C., and an average molecular weight of 1,500 to 8,000. Black crosslinked resin composition for outdoor high voltage power cable insulation, characterized in that 5 to 10wt% with respect to the total weight of the carbon black masterbatch. 제 11 항에 있어서, 산화방지제가 1차 산화방지제만으로 또는 1차 산화방지제 및 2차 산화방지제로 구성되며, 상기 1차 산화방지제로 페놀류계, 상기 2차 산화방지제로 에스테르류가 사용되며, 상기 1차 산화방지제만 사용될 경우 베이스수지 100중량부에 대해 0.1∼0.5중량부 첨가되며, 상기 1차 및 2차 산화방지제가 사용될 경우 베이스수지 100중량부에 대해 1차 산화방지제가 0.1∼0.5중량부, 2차 산화방지제가 0.1∼0.3중량부가 첨가되는 것을 특징으로 하는 옥외용 고압 전력케이블 절연용 흑색가교수지 조성물.12. The antioxidant according to claim 11, wherein the antioxidant is composed of only primary antioxidants or primary and secondary antioxidants, and phenols and esters are used as the primary antioxidants. When only the primary antioxidant is used, 0.1 to 0.5 parts by weight based on 100 parts by weight of the base resin is added, and when the primary and secondary antioxidants are used, the primary antioxidant is 0.1 to 0.5 parts by weight based on 100 parts by weight of the base resin. , Black crosslinkable resin composition for outdoor high voltage power cable insulation, characterized in that the secondary antioxidant is added 0.1 to 0.3 parts by weight.
KR1019890007873A 1989-06-08 1989-06-08 Black color crosslinked resin composition for electric line and its preparing method KR920004784B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009021050A3 (en) * 2007-08-06 2009-04-23 Gen Cable Technologies Corp Tree resistant insulation compositions
KR101412639B1 (en) * 2012-11-12 2014-07-01 세지케미칼(주) Semiconductive compouind for extra high voltage power cable including ethylene α-olefin copolymer and carbon nanotube and method of manufacturing thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009021050A3 (en) * 2007-08-06 2009-04-23 Gen Cable Technologies Corp Tree resistant insulation compositions
US8283391B2 (en) 2007-08-06 2012-10-09 General Cable Technologies Corporation Tree resistant insulation compositions
CN102604181B (en) * 2007-08-06 2014-08-13 通用电缆技术公司 Tree resistant insulation compositions
KR101412639B1 (en) * 2012-11-12 2014-07-01 세지케미칼(주) Semiconductive compouind for extra high voltage power cable including ethylene α-olefin copolymer and carbon nanotube and method of manufacturing thereof

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