WO2014126404A1 - Power cable - Google Patents

Power cable Download PDF

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Publication number
WO2014126404A1
WO2014126404A1 PCT/KR2014/001199 KR2014001199W WO2014126404A1 WO 2014126404 A1 WO2014126404 A1 WO 2014126404A1 KR 2014001199 W KR2014001199 W KR 2014001199W WO 2014126404 A1 WO2014126404 A1 WO 2014126404A1
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WO
WIPO (PCT)
Prior art keywords
power cable
weight
propylene copolymer
semiconducting layer
layer
Prior art date
Application number
PCT/KR2014/001199
Other languages
French (fr)
Korean (ko)
Inventor
유익현
김현석
남진호
조영은
김웅
조호숙
이원석
정현정
김형준
Original Assignee
엘에스전선 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020130015629A external-priority patent/KR102003567B1/en
Priority claimed from KR1020130045408A external-priority patent/KR102018922B1/en
Priority claimed from KR1020130054720A external-priority patent/KR102038709B1/en
Application filed by 엘에스전선 주식회사 filed Critical 엘에스전선 주식회사
Publication of WO2014126404A1 publication Critical patent/WO2014126404A1/en

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    • 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
    • H01B3/44—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 vinyl resins; acrylic resins
    • H01B3/441—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 vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00—Power cables
    • H01B9/02—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
    • H01B9/027—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients composed of semi-conducting layers

Definitions

  • the present invention relates to a power cable.
  • the present invention is recyclable, environmentally friendly, excellent in heat resistance and mechanical strength, and at the same time, flexibility, flexibility, impact resistance, cold resistance, installation property, workability, and workability in trade-off with these physical properties.
  • the present invention relates to a power cable having an excellent semiconducting layer.
  • a general power cable includes a conductor and an insulation layer surrounding the conductor, and in the case of a medium voltage, high voltage or ultra high voltage cable, an inner semiconducting layer between the conductor and the insulation layer, an outer semiconducting layer surrounding the insulation layer, and an outer semiconducting layer A sheath layer may be further included.
  • the inner semiconducting layer is disposed between the conductor and the insulating layer to suppress partial discharge at the interface with the conductor and to eliminate the air layer between the conductor and the insulating layer
  • the outer semiconducting layer is It performs the function of applying the electric field to the shielding function of the cable and the insulator.
  • conductive particles and the like are dispersed in an insulating polymer resin to realize semiconducting characteristics.
  • the insulating layer, the inner semiconducting layer and the outer semiconducting layer are usually formed from a composition comprising a base resin of the same series for excellent adhesion to each other.
  • crosslinked polyolefin-based polymers such as polyethylene, ethylene / propylene elastic copolymer (EPR) and ethylene / propylene / diene copolymer (EPDM) have been generally used as the base resin constituting the insulating or semiconductive material. This is because such conventional crosslinked resins maintain excellent flexibility and satisfactory electrical and mechanical strength even at high temperatures.
  • the crosslinked polyethylene (XLPE) or the like which has been used as the base resin constituting the insulating or semiconducting material, has a crosslinked form, the lifespan of a cable or the like including an insulating layer or a semiconductive layer made of a resin such as the crosslinked polyethylene is increased. At this time, the resin constituting the insulating layer or the semiconducting layer is impossible to recycle and cannot be disposed of by incineration, which is not environmentally friendly.
  • non-crosslinked high density polyethylene (HDPE) or low density polyethylene (LDPE) is a recycling of the resin constituting the insulating layer or the semi-conductive layer when the life of the cable or the like including an insulating layer or a semi-conducting layer prepared therefrom.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • Korean Unexamined Patent Publication Nos. 10-2011-0084544, 10-2009-0037945, 10-2007-0086013 and the like disclose various insulating or semiconductive materials including a polypropylene resin, They are very insufficient to satisfy the stiffness, flexibility, flexibility, impact resistance, cold resistance, laying resistance, workability, etc. of the resins in trade-off.
  • the present invention has a semiconducting layer made of a semiconducting material capable of simultaneously satisfying heat resistance and mechanical strength and flexibility, flexibility, impact resistance, cold resistance, laying resistance, workability, and the like in a trade-off. It is an object to provide a power cable.
  • an object of the present invention is to provide a power cable having an outer semiconducting layer made of a semiconducting material that is easy to control the adhesion with an insulating layer to have sufficient adhesiveness with the insulating layer and is easy to peel off from the insulating layer. It is done.
  • a power cable comprising a conductor, an inner semiconducting layer surrounding the conductor, an insulating layer surrounding the inner semiconducting layer, an outer semiconducting layer surrounding the insulating layer, and a sheath layer surrounding the outer semiconducting layer, wherein the inner semiconducting layer is And a base resin comprising a heterophasic propylene copolymer comprising two or more kinds of propylene copolymers having different phases, and 30 to 70 parts by weight of conductive particles based on 100 parts by weight of the base resin.
  • the insulating layer provides a power cable, which is formed from a non-crosslinked insulating composition comprising a polypropylene resin as the base resin.
  • the outer semiconducting layer includes a heterophasic propylene copolymer including two or more kinds of propylene copolymers different in phase and an olefin copolymer including a polar monomer, and the total of the heterophasic propylene copolymer and the olefin copolymer
  • a power cable formed from a semiconductive composition comprising a base resin of 13 to 17% by weight of the polar monomer, and 30 to 70 parts by weight of conductive particles, based on 100 parts by weight of the base resin, by weight. do.
  • the polar monomer also provides a power cable, characterized in that it comprises a vinyl ester monomer, a vinyl-unsaturated carboxylic acid monomer, a (meth) acrylate, an alkyl (meth) acrylate, or a combination thereof.
  • the olefin copolymer provides an electric power cable, characterized in that it comprises an ethylene butyl acrylate (EBA) resin.
  • EBA ethylene butyl acrylate
  • the semiconductive composition for forming the inner semiconducting layer provides a power cable, characterized in that it further comprises 0.1 to 5 parts by weight of the metal inactive additive.
  • the metal inactive additive provides a power cable, characterized in that it has a molecular structure of the chelate ligand (chelate legand) form two or more coordination bonds with one metal atom.
  • the metal inactive additive has at least two Lewis-base sites (electron donor) in the molecular structure, the Lewis base is characterized in that the amine group, amide group or carboxyl group To provide a power cable.
  • the metal inactive additives are N, N'-bis (salicylidene) -1,2-propanediamine, 1,2-bis (3,5-di-t-butyl-4-hydroxycinnamoyl) hydrazine Or N, N'-1,2-ethane diylbis- (N- (carboxymethyl) glycine).
  • the solubility of the metal-inert additive in paraffin oil at 20 ° C. is 0.01 g / 100 ml or less.
  • the heterophasic propylene copolymer included in the inner semiconductive layer, the outer semiconducting layer, or both base resins provides a power cable, wherein the propylene copolymer elastomer is dispersed in the propylene homopolymer matrix.
  • the content of the propylene copolymer elastomer characterized in that 65 to 75% by weight, based on the total weight of the heterophasic propylene copolymer, provides a power cable.
  • heterophasic propylene copolymer provides a power cable, characterized in that all of the following conditions a) to h) are satisfied.
  • melt flow rate (MFR) of 0.5 to 1.0 g / 10 min (measured under a load of 2.16 kg at 230 ° C. according to ISO 1133),
  • tensile stress at break is 10 MPa or more (measured at a tensile speed of 250 mm / min),
  • e) flexural modulus is from 90 to 300 MPa
  • the power cable according to the present invention uses non-crosslinked polypropylene having excellent heat resistance as the base resin of the insulating layer and the semiconducting layer, and thus has an excellent effect of being environmentally friendly and requiring no crosslinking process and having low manufacturing cost.
  • the power cable according to the present invention is not only excellent in heat resistance and mechanical strength, but also excellent in satisfying the flexibility, flexibility, impact resistance, cold resistance, installation properties, workability, etc., which are at a trade-off with them. Effect.
  • the power cable according to the present invention is easy to control the adhesion of the outer semiconducting layer to the insulating layer, the adhesive strength of the insulating layer and the semiconducting layer is sufficient and at the same time partially peel off the outer semiconducting layer at the end of the cable from the insulating layer during electrical construction It is easy to make it, and workability, workability, etc. are excellent effect.
  • FIG. 1 is a cross-sectional view schematically showing the cross-sectional structure of a power cable according to the present invention.
  • FIG. 2 is a longitudinal sectional view schematically showing a cross-sectional structure of a power cable according to the present invention.
  • FIG. 1 and 2 show an embodiment of a power cable according to the invention.
  • the power cable according to the present invention is a conductor (1) made of a conductive material such as copper, aluminum, an insulating layer (3) made of an insulating polymer, the conductor (1) and the insulating layer Located between (3) to suppress partial discharge at the interface with the conductor (1), to eliminate the air layer between the conductor (1) and the insulating layer (3), to mitigate local electric field concentration, etc.
  • An inner semiconducting layer (2) to play a role, an outer semiconducting layer (4) to play a localized field concentration relaxation role to apply an even electric field to the insulator, and a sheath layer (5) to protect the cable. have.
  • Standards of the conductor 1, the insulating layer 3, the semiconducting layers 2 and 4, the sheath layer 5, and the like may vary according to the use of the cable, the transmission voltage, and the like.
  • the materials constituting the entire layers 2 and 4 and the sheath layer 5 may be the same or different.
  • the insulating layer (3), semiconductive layers (2, 4) and sheath layer (5) may be prepared from a composition containing a polymer resin of the same series as a base resin in order to secure sufficient adhesion to each other. .
  • the insulating layer 3 can be made from a non-crosslinked insulating composition comprising a polyolefin resin, preferably a polypropylene resin.
  • the polypropylene resin may include a propylene homopolymer, a propylene copolymer, a heterophasic propylene copolymer including two or more different propylene copolymers having different phases, or a combination thereof, and the propylene copolymer may include a random propylene copolymer, It is a block propylene copolymer, or a combination thereof, Preferably it is a random propylene copolymer.
  • the polypropylene resin may comprise a blend of a random propylene copolymer and a heterophasic propylene copolymer.
  • the heterophasic propylene copolymer may be a dispersion of a propylene copolymer elastomer in a resin matrix composed of a propylene homopolymer, wherein the composition consists of a combination of the random propylene copolymer and the heterophasic propylene copolymer.
  • the content of the random propylene copolymer may be 20 to 60% by weight.
  • the weight ratio of the propylene random copolymer and the heterophasic propylene copolymer is less than 2: 8
  • mechanical strength such as tensile strength of the insulating layer 3 formed may be insufficient
  • the insulating layer ( 3) flexibility, bendability, impact resistance, cold resistance, etc. may be insufficient.
  • the non-crosslinked insulating composition has a flexural modulus of 200 to 700 MPa, a melting point (Tm) of 150 to 160 ° C (measured by differential scanning calorimetry (DSC)), and a melting enthalpy of 30 to 90 J / g ( Differential scanning calorimetry (DSC), and xylene solubility (measured according to D5492-10 by adding 2 g of resin to xylene at 135 ° C.) may be 19 to 36%.
  • the non-crosslinked insulating composition may have insufficient flexibility, flexibility, impact resistance, cold resistance, installation property, and workability when the flexural modulus exceeds 700 MPa, and the heat resistance of the cable when the melting point (Tm) is less than 150 ° C. Or the like may be insufficient.
  • the resin when the xylene solubility is more than 36%, the resin is excessively low isotacticity (isotacticity) may be insufficient mechanical strength, if less than 19%, the resin is excessively high stereoregularity, flexibility, flexibility, Impact resistance, cold resistance and the like may be lowered.
  • the non-crosslinked insulating composition forming the insulating layer 3 includes non-crosslinked polypropylene, which is environmentally friendly, such as recyclable, and at the same time, the above-described configuration provides flexibility, flexibility, It can satisfy impact resistance, cold resistance, laying resistance, workability, etc.
  • the semiconducting layers 2,4 may be prepared from a semiconductive composition comprising a heterophasic propylene copolymer comprising two or more kinds of propylene copolymers different in phase and conductive particles.
  • the heterophasic propylene copolymer may be a heterophasic propylene copolymer in which the propylene copolymer elastomer is uniformly dispersed in the propylene homopolymer matrix.
  • the content of the propylene copolymer elastomer may be about 65 to 75 wt% based on the total weight of the heterophasic propylene copolymer.
  • the semiconductive composition forming the semiconductive layers 2 and 4 includes an uncrosslinked polypropylene resin as a base resin
  • the semiconducting composition is environmentally friendly, such as recycling, and at the same time, heat resistance, mechanical strength, and flexibility, flexibility, and resistance to a conflict therewith. It can meet impact resistance, cold resistance, installability, workability and so on.
  • the semiconducting composition forming the inner semiconducting layer 2 among the semiconducting layers 2 and 4 is an inert metal which is an additive which deactivates the metallic material flowing from the conductor 1 of the power cable to the inner semiconducting layer 2. It may further include an additive.
  • the metallic material for example, transition metal ion atoms such as copper ions
  • an additional coordinate bond may be formed in addition to the ionic bond by a given ion order.
  • an additive having a molecular structure in the form of a chelate legand forming two or more coordination bonds with one metal atom is preferable.
  • the metal inactive additive preferably has at least two Lewis-base sites serving as electron donors in the molecular structure, and the Lewis bases preferably have functional groups such as amines, amides, and carboxyls. Do.
  • the metal inactive additive has a solubility in insulating oil such as paraffin oil of 0.01 g / 100 ml (gram of solute dissolved in 100 ml of solvent at 20 ° C) or less.
  • insulating oil such as paraffin oil of 0.01 g / 100 ml (gram of solute dissolved in 100 ml of solvent at 20 ° C) or less.
  • the metal inactive activator is preferably N, N'-bis (salicylidene) -1,2-propanediamine (N, N'-bis (salicylidene) -1,2-propanediamine), 1 , 2-bis (3,5-di-t-butyl-4-hydroxycinnamoyl) hydrazine (1,2-bis (3,5-di-tert-butyl-4-hydroxycinnamoyl) hydrazine), N, N '-1,2-ethane diylbis- (N- (carboxymethyl) glycine) is N, N'-1,2-ethane diylbis- (N- (carboxymethyl) glycine).
  • the metal inactive additive may be 0.1 to 5 parts by weight based on 100 parts by weight of the base resin of the semiconductive composition.
  • the desired effect that is, the anti-deterioration effect of the internal semiconducting layer 2 due to deactivation of the metal material flowing from the conductor 1 cannot be achieved, and more than 5 parts by weight.
  • bleaching may occur due to compatibility problems with the base resin after extrusion.
  • the semiconductive composition forming the outer semiconducting layer 4 of the semiconducting layers 2 and 4 may include an olefin copolymer including a polar monomer in addition to the heterophasic propylene copolymer.
  • the content of the heterophasic propylene copolymer in the resin composition including the heterophasic propylene copolymer and the olefin copolymer including the polar monomer may be 10 to 30% by weight, the heterophasic propylene copolymer and the The content of the polar monomer may be 13 to 17% by weight, based on the total weight of the olefin cyclopolymer including the polar monomer.
  • the content of the heterophasic propylene copolymer is less than 10% by weight or the content of the polar monomer is more than 17% by weight, the adhesion between the outer semiconducting layer 4 and the insulating layer 3 may be insufficient.
  • the content of the heterophasic propylene copolymer is more than 30% by weight or the content of the polar monomer is less than 13% by weight, peelability of the outer semiconducting layer 4 from the insulating layer 3 may be insufficient. .
  • the olefin monomer forming the olefin copolymer may be, for example, ethylene, propene, butene, pentene, hexene, octene, decene, dodecene and the like.
  • the polar monomer forming the olefin copolymer means a monomer having a negative charge partially or wholly.
  • Such polar monomers include, for example, vinyl ester monomers such as vinyl acetate and vinyl versatate; Vinyl-unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, maleic acid and itaconic acid; (Meth) acrylate or alkyl (meth) acrylate, wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, isobornyl, hexyl, heptyl, n-octyl, 2- Ethylhexyl, decyl, undecyl, dodecyl, lauryl, cetyl or stearyl) monomers and the like, and the olefin copolymer may preferably be ethylene butyl acrylate (EBA).
  • EBA ethylene butyl acrylate
  • the outer semiconducting layer 4 having the above-described configuration may have a peel force of about 3 to 15 N, which is a force required to peel off from the insulating layer 3.
  • the outer semiconducting layer 4 has a specific blending ratio of the olefin copolymer including the heterophasic propylene copolymer and the polar monomer, and a specific content of the polar monomer included in the olefin copolymer. This satisfies both the sufficient adhesive force with the insulating layer 3 and the sufficient peeling property from the insulating layer 3, and allows the outer semiconducting layer 4 to be peeled from the insulating layer 3 during electrical construction. In this case, it is possible to avoid remaining of the outer semiconducting layer 4 on the insulating layer 3.
  • the semiconducting composition forming the semiconducting layers 2 and 4 further includes the conductive particles to control the electrical conductivity of the semiconducting layers 2 and 4.
  • the conductive particles there is no particular limitation on the conductive particles, and for example, carbon black such as furnace black, acetylene black, or the like, or graphite, graphene or the like may be used.
  • the conductive particles such as carbon black are not particularly limited in shape, and may be, for example, spherical, plate-shaped, rod-shaped, or tubular.
  • the surface area of the conductive particles may be 20 m 2 / g or more, for example, 40 to 1,200 m 2 / g, and preferably, the volume resistance of the expandable polymeric material may be less than 500 ⁇ m, more preferably less than 20 ⁇ m. have.
  • the conductive particles content such as carbon black may be 30 to 70 parts by weight based on 100 parts by weight of the base resin of the semiconductive composition.
  • the conductive particle content, such as carbon black is less than 30 parts by weight, it may be difficult to implement the desired semiconducting properties, and when it is more than 70 parts by weight, extrusion may be disadvantageous.
  • the semiconductive composition forming the semiconducting layers 2 and 4 may further include other additives such as antioxidants and lubricants.
  • the antioxidant may be an amine, dialkyl ester, thioester, phenol-based antioxidant, and the like, for example, [3- [3- (3,5-di-t-butyl-4-hydroxy Oxyphenyl) propanoyloxy] -2,2-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoyloxymethyl] propyl], 3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propanoate, thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 3,5-bis (1,1- Dimethylethyl) -4-hydroxybenzenepropionic acid octadecyl ester, propionic acid, 3,3'thiobis-1,1 'dioctade
  • the lubricant may be, for example, a polypropylene wax or polyethylene wax having a number average molecular weight (Mn) of 1,000 to 10,000.
  • Mn number average molecular weight
  • the content of each of the other additives such as the antioxidant and the lubricant may be 0.2 to 3 parts by weight based on 100 parts by weight of the base resin of the semiconductive composition.
  • Each sample sheet was prepared according to the examples and comparative examples formed from the composition consisting of the components and contents as shown in Table 1 below. Specifically, an insulating sheet and a semiconducting sheet having a width of about 13 mm, a thickness of about 1 mm, and a length of about 130 mm were prepared, respectively, and then overlaid and pressed at a temperature of 200 ° C. to prepare a final sample sheet. Units of the content described in Table 1 below are parts by weight.
  • Resin 1 Propylene copolymer (8: 2 blend of heterophasic resin in which propylene copolymer elastomer particles of 1 ⁇ m or less are dispersed in a propylene homopolymer matrix and random propylene-ethylene copolymer (ethylene content: 3% by weight))
  • Resin 2 Ethylene vinyl acetate resin (28% by weight of vinyl acetate) (Manufacturer: Lotte Chemical; Product Name: VC590)
  • Resin 3 Ethylene vinyl acetate resin (19% by weight of vinyl acetate) (Manufacturer: Lotte Chemical; Product Name: VS430)
  • Resin 4 Ethylene butyl acrylate resin (Butyl acrylate 17 wt%) (Manufacturer: DuPont; Product name: 3217AC)
  • Resin 5 Random propylene-ethylene copolymer (ethylene content: 3 wt%)
  • Resin 6 heterophasic propylene copolymer in which propylene copolymer elastomer particles of 1 ⁇ m or less are dispersed in a propylene homopolymer matrix
  • the peel force required to peel the outer semiconducting layer from the insulating layer in the sample sheet of Examples 1 to 4 according to the present invention is in the range of 3 to 15 N
  • the insulating layer and the outer It exhibits sufficient adhesion between the semiconducting layers, exhibits excellent workability, workability, and the like, which are required for electrical construction, and finds black spots, which are residues of the outer semiconducting layer, on the insulating layer upon peeling of the outer semiconducting layer from the insulating layer. It wasn't.
  • the sample sheets according to Comparative Examples 1 and 2 contain an excessive amount of polar monomer in the resin forming the outer semiconducting layer, so that the adhesion between the insulating layer and the outer semiconducting layer is insufficient, and the sample sheet according to Comparative Example 3 is polar in the resin.
  • the excessive amount of the monomer the excessively sticky heterophasic propylene copolymer is contained, so that the external semiconducting layer is difficult to peel off from the insulating layer, thereby reducing workability and workability required for electrical construction of the cable. After peeling, black spots which are residues of the outer semiconducting layer were found on the insulating layer.
  • conductor 2 inner semiconducting layer
  • insulation layer 4 outer semiconducting layer

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  • Organic Insulating Materials (AREA)
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Abstract

The present invention relates to a power cable. Specifically, the present invention relates to a power cable having a semi-conductive layer, which can be reused and is thus environment-friendly, has excellent heat resistance and mechanical strength, and is excellent in flexibility, bendability, impact resistance, cold resistance, spreading property, construction property, and workability, which are in a trade-off relation with the properties of heat resistance and mechanical strength.

Description

전력 케이블Power cable
본 발명은 전력 케이블에 관한 것이다. 구체적으로, 본 발명은 재활용이 가능하여 환경 친화적이고, 내열성 및 기계적 강도가 우수한 동시에, 이들 물성과 상충관계(trade-off)에 있는 유연성, 굴곡성, 내충격성, 내한성, 포설성, 시공성, 작업성 등이 우수한 반도전층을 갖는 전력 케이블에 관한 것이다.The present invention relates to a power cable. Specifically, the present invention is recyclable, environmentally friendly, excellent in heat resistance and mechanical strength, and at the same time, flexibility, flexibility, impact resistance, cold resistance, installation property, workability, and workability in trade-off with these physical properties. The present invention relates to a power cable having an excellent semiconducting layer.
일반적인 전력케이블은 도체와 이를 감싸는 절연층을 포함하고, 중전압, 고전압 또는 초고전압 케이블의 경우 상기 도체와 절연층 사이에 내부 반도전층, 상기 절연층을 감싸는 외부 반도전층, 상기 외부 반도전층을 감싸는 쉬스층 등을 추가로 포함할 수 있다.A general power cable includes a conductor and an insulation layer surrounding the conductor, and in the case of a medium voltage, high voltage or ultra high voltage cable, an inner semiconducting layer between the conductor and the insulation layer, an outer semiconducting layer surrounding the insulation layer, and an outer semiconducting layer A sheath layer may be further included.
여기서, 상기 내부 반도전층은 상기 도체와 상기 절연층 사이에 배치되어 도체와의 계면에서의 부분방전을 억제하고 상기 도체와 상기 절연층 사이의 공기층을 없애주는 기능을 수행하고, 상기 외부 반도전층은 케이블의 차폐기능 및 절연체에 균등한 전계가 걸리도록 하는 기능을 수행한다. 상기 내부 반도전층 및 상기 외부 반도전층은 반도전 특성을 구현하기 위해 절연성 고분자 수지에 전도성 입자 등이 분산되어 있다.Here, the inner semiconducting layer is disposed between the conductor and the insulating layer to suppress partial discharge at the interface with the conductor and to eliminate the air layer between the conductor and the insulating layer, and the outer semiconducting layer is It performs the function of applying the electric field to the shielding function of the cable and the insulator. In the inner semiconductive layer and the outer semiconducting layer, conductive particles and the like are dispersed in an insulating polymer resin to realize semiconducting characteristics.
상기 절연층, 상기 내부 반도전층 및 상기 외부 반도전층은 서로간의 우수한 접착력을 위해 통상 동일한 계열의 베이스 수지를 포함하는 조성물로부터 형성된다.The insulating layer, the inner semiconducting layer and the outer semiconducting layer are usually formed from a composition comprising a base resin of the same series for excellent adhesion to each other.
최근, 증가하는 전력 수요에 따라 고용량 케이블의 개발이 요구되고 있으며 이를 위해서는 기계적, 전기적 특성이 우수한 절연층 또는 반도전층을 제조하기 위한 절연 또는 반도전 재료가 필요한 상황이 되었다.In recent years, the development of high capacity cables is required in accordance with the increasing power demand, which requires an insulating or semiconductive material for producing an insulating layer or a semiconducting layer having excellent mechanical and electrical properties.
종래 상기 절연 또는 반도전 재료를 구성하는 기재 수지로서 폴리에틸렌, 에틸렌/프로필렌 탄성 공중합체(EPR), 에틸렌/프로필렌/디엔 공중합체(EPDM) 등의 폴리올레핀계 고분자를 가교시킨 것이 일반적으로 사용되어 왔다. 이러한 종래의 가교 수지는 심지어 고온하에서도 우수한 유연성 및 만족스런 전기적·기계적 강도 등을 유지하기 때문이다.Conventionally, crosslinked polyolefin-based polymers such as polyethylene, ethylene / propylene elastic copolymer (EPR) and ethylene / propylene / diene copolymer (EPDM) have been generally used as the base resin constituting the insulating or semiconductive material. This is because such conventional crosslinked resins maintain excellent flexibility and satisfactory electrical and mechanical strength even at high temperatures.
그러나, 절연 또는 반도전 재료를 구성하는 기재 수지로 사용되어 온 상기 가교 폴리에틸렌(XLPE) 등은 가교 형태이기 때문에 상기 가교 폴리에틸렌 등의 수지로 제조된 절연층 또는 반도전층을 포함하는 케이블 등의 수명이 다하면 상기 절연층 또는 반도전층을 구성하는 수지의 재활용이 불가능하고 소각에 의해 폐기할 수밖에 없어 환경 친화적이지 않다.However, since the crosslinked polyethylene (XLPE) or the like, which has been used as the base resin constituting the insulating or semiconducting material, has a crosslinked form, the lifespan of a cable or the like including an insulating layer or a semiconductive layer made of a resin such as the crosslinked polyethylene is increased. At this time, the resin constituting the insulating layer or the semiconducting layer is impossible to recycle and cannot be disposed of by incineration, which is not environmentally friendly.
또한, 쉬스층의 재료로서 폴리비닐클로라이드(PVC)를 사용하는 경우 이를 상기 절연 또는 반도전 재료를 구성하는 가교 폴리에틸렌(XLPE) 등으로부터 분리하는 것이 곤란하여, 소각시 유독성 염소화 물질이 생성되는 등 환경 친화적이지 않은 단점이 있다.In addition, when polyvinyl chloride (PVC) is used as the material of the sheath layer, it is difficult to separate it from crosslinked polyethylene (XLPE) or the like constituting the insulating or semiconductive material, so that toxic chlorinated substances are produced upon incineration. There is a disadvantage that is not friendly.
한편, 비가교 형태의 고밀도 폴리에틸렌(HDPE) 또는 저밀도 폴리에틸렌(LDPE)은 이로부터 제조된 절연층 또는 반도전층을 포함하는 케이블 등의 수명이 다하면 상기 절연층 또는 상기 반도전층을 구성하는 수지의 재활용이 가능한 등 환경 친화적이나, 가교 형태의 폴리에틸렌(XLPE)에 비해 내열성이 열등하여 낮은 운전온도로 인해 그 용도가 매우 제한적인 단점이 있다.On the other hand, non-crosslinked high density polyethylene (HDPE) or low density polyethylene (LDPE) is a recycling of the resin constituting the insulating layer or the semi-conductive layer when the life of the cable or the like including an insulating layer or a semi-conducting layer prepared therefrom. Environmentally friendly as possible, but the heat resistance is inferior to the crosslinked polyethylene (XLPE) due to the low operating temperature has its disadvantages of very limited use.
고분자 자체의 용융점이 160℃ 이상으로 가교하지 않고도 내열성이 우수하여 환경 친화적인 폴리프로필렌 수지를 기재 수지로 사용하는 것을 고려해 볼 수 있다. 다만, 상기 폴리프로필렌 수지는 이의 높은 강성(rigidity)에 의한 불충분한 유연성, 굴곡성(flexibility) 등으로 인해, 이로부터 제조되는 절연층 또는 반도전층을 포함하는 케이블의 포설 작업시 작업성이 떨어지고 그 용도가 제한되는 문제가 있다.It is possible to consider using an environmentally friendly polypropylene resin as a base resin having excellent heat resistance without crosslinking at 160 ° C. or higher of the polymer itself. However, the polypropylene resin has poor workability due to insufficient rigidity due to its high rigidity, flexibility, and the like, resulting in poor workability when laying a cable including an insulating layer or a semiconducting layer manufactured therefrom. There is a problem that is limited.
이와 관련하여, 한국공개특허공보 제10-2011-0084544호, 제10-2009-0037945호, 제10-2007-0086013호 등에는 폴리프로필렌 수지를 포함하는 다양한 절연 또는 반도전 재료가 개시되어 있으나, 이들은 상충관계(trade-off)에 있는 수지의 강성과 유연성, 굴곡성, 내충격성, 내한성, 포설성, 작업성 등을 동시에 만족시키기에는 매우 불충분하다.In this regard, Korean Unexamined Patent Publication Nos. 10-2011-0084544, 10-2009-0037945, 10-2007-0086013 and the like disclose various insulating or semiconductive materials including a polypropylene resin, They are very insufficient to satisfy the stiffness, flexibility, flexibility, impact resistance, cold resistance, laying resistance, workability, etc. of the resins in trade-off.
따라서, 환경친화적이고, 내열성 및 기계적 강도, 그리고 이와 상충관계(trade-off)에 있는 유연성, 굴곡성, 내충격성, 내한성, 포설성, 작업성 등을 동시에 만족시킬 수 있고, 나아가 절연층과의 접착력 조절이 용이하여 충분한 접착력을 발휘할 수 있는 재료로부터 제조되는 반도전층을 갖는 전력 케이블이 요구되고 있는 실정이다.Therefore, environmentally friendly, heat resistance and mechanical strength, and flexibility, flexibility, impact resistance, cold resistance, laying resistance, workability, etc. in the trade-off can be satisfied at the same time, furthermore, adhesion to the insulating layer There is a need for a power cable having a semiconducting layer made from a material that can be easily adjusted to exhibit sufficient adhesion.
본 발명은 수명이 다한 후 재활용이 가능한 등 환경 친화적이고, 가교를 위한 공정이 불필요하여 제조비용이 저렴한 반도전 재료로 이루어진 반도전층을 갖는 전력 케이블을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a power cable having a semiconducting layer made of a semiconducting material which is environmentally friendly, such as being recycled after end of life, and does not require a process for crosslinking and is low in manufacturing cost.
또한, 본 발명은 내열성 및 기계적 강도 및 이와 상충관계(trade-off)에 있는 유연성, 굴곡성, 내충격성, 내한성, 포설성, 작업성 등을 동시에 만족시킬 수 있는 반도전 재료로 이루어진 반도전층을 갖는 전력 케이블을 제공하는 것을 목적으로 한다.In addition, the present invention has a semiconducting layer made of a semiconducting material capable of simultaneously satisfying heat resistance and mechanical strength and flexibility, flexibility, impact resistance, cold resistance, laying resistance, workability, and the like in a trade-off. It is an object to provide a power cable.
나아가, 본 발명은 절연층과의 접착력 조절이 용이하여 상기 절연층과의 접착성이 충분한 동시에 상기 절연층으로부터의 박리가 용이한 반도전 재료로 이루어진 외부 반도전층을 갖는 전력 케이블을 제공하는 것을 목적으로 한다.Furthermore, an object of the present invention is to provide a power cable having an outer semiconducting layer made of a semiconducting material that is easy to control the adhesion with an insulating layer to have sufficient adhesiveness with the insulating layer and is easy to peel off from the insulating layer. It is done.
상기 과제를 해결하기 위해, 본 발명은,In order to solve the above problems, the present invention,
도체, 상기 도체를 감싸는 내부 반도전층, 상기 내부 반도전층을 감싸는 절연층, 상기 절연층을 감싸는 외부 반도전층, 및 상기 외부 반도전층을 감싸는 쉬스층을 포함하는 전력 케이블에 있어서, 상기 내부 반도전층은, 상이 다른 2종 이상의 프로필렌 공중합체를 포함하는 헤테로상 프로필렌 공중합체를 포함하는 기재 수지 및, 상기 기재 수지 100 중량부를 기준으로, 전도성 입자 30 내지 70 중량부를 포함하는 반도전성 조성물로부터 형성되고, 상기 절연층은 기재 수지로서 폴리프로필렌 수지를 포함하는 비가교 절연 조성물로부터 형성되는, 전력 케이블을 제공한다.A power cable comprising a conductor, an inner semiconducting layer surrounding the conductor, an insulating layer surrounding the inner semiconducting layer, an outer semiconducting layer surrounding the insulating layer, and a sheath layer surrounding the outer semiconducting layer, wherein the inner semiconducting layer is And a base resin comprising a heterophasic propylene copolymer comprising two or more kinds of propylene copolymers having different phases, and 30 to 70 parts by weight of conductive particles based on 100 parts by weight of the base resin. The insulating layer provides a power cable, which is formed from a non-crosslinked insulating composition comprising a polypropylene resin as the base resin.
여기서, 상기 외부 반도전층은, 상이 다른 2종 이상의 프로필렌 공중합체를 포함하는 헤테로상 프로필렌 공중합체 및 극성 단량체를 포함하는 올레핀 공중합체를 포함하고, 상기 헤테로상 프로필렌 공중합체와 상기 올레핀 공중합체의 총 중량을 기준으로, 상기 극성 단량체의 함량이 13 내지 17 중량%인 기재 수지 및, 상기 기재 수지 100 중량부를 기준으로, 전도성 입자 30 내지 70 중량부를 포함하는 반도전성 조성물로부터 형성되는, 전력 케이블을 제공한다.Here, the outer semiconducting layer includes a heterophasic propylene copolymer including two or more kinds of propylene copolymers different in phase and an olefin copolymer including a polar monomer, and the total of the heterophasic propylene copolymer and the olefin copolymer Provided is a power cable formed from a semiconductive composition comprising a base resin of 13 to 17% by weight of the polar monomer, and 30 to 70 parts by weight of conductive particles, based on 100 parts by weight of the base resin, by weight. do.
또한, 상기 극성 단량체는 비닐 에스테르 단량체, 비닐-불포화 카르복시산 단량체, (메트)아크릴레이트, 알킬(메트)아크릴레이트, 또는 이들의 배합을 포함하는 것을 특징으로 하는, 전력 케이블을 제공한다.The polar monomer also provides a power cable, characterized in that it comprises a vinyl ester monomer, a vinyl-unsaturated carboxylic acid monomer, a (meth) acrylate, an alkyl (meth) acrylate, or a combination thereof.
그리고, 상기 올레핀 공중합체는 에틸렌 부틸 아크릴레이트(EBA) 수지를 포함하는 것을 특징으로 하는, 전력 케이블을 제공한다.And, the olefin copolymer provides an electric power cable, characterized in that it comprises an ethylene butyl acrylate (EBA) resin.
한편, 상기 내부 반도전층을 형성하는 반도전성 조성물은 금속비활성 첨가제 0.1 내지 5 중량부를 추가로 포함하는 것을 특징으로 하는, 전력 케이블을 제공한다.On the other hand, the semiconductive composition for forming the inner semiconducting layer provides a power cable, characterized in that it further comprises 0.1 to 5 parts by weight of the metal inactive additive.
여기서, 상기 금속비활성 첨가제는 하나의 금속원자와 2개 이상의 배위결합을 이루는 킬레이트 리간드(chelate legand) 형태의 분자구조를 가지는 것을 특징으로 하는, 전력 케이블을 제공한다.Here, the metal inactive additive provides a power cable, characterized in that it has a molecular structure of the chelate ligand (chelate legand) form two or more coordination bonds with one metal atom.
또한, 상기 금속비활성 첨가제는 분자구조 내에 전자주개(electron donor) 역할을 하는 루이스 염기 사이트(Lewis-base site)를 2곳 이상 보유하고, 상기 루이스 염기는 아민기, 아미드기 또는 카르복실기인 것을 특징으로 하는, 전력 케이블을 제공한다.In addition, the metal inactive additive has at least two Lewis-base sites (electron donor) in the molecular structure, the Lewis base is characterized in that the amine group, amide group or carboxyl group To provide a power cable.
그리고, 상기 금속비활성 첨가제는 N,N'-비스(살리실리덴)-1,2-프로판디아민, 1,2-비스(3,5-디-t-부틸-4-하이드록시신나모일)히드라진 또는 N,N'-1,2-에탄 디일비스-(N-(카르복시메틸)글리신인 것을 특징으로 하는, 전력 케이블을 제공한다.In addition, the metal inactive additives are N, N'-bis (salicylidene) -1,2-propanediamine, 1,2-bis (3,5-di-t-butyl-4-hydroxycinnamoyl) hydrazine Or N, N'-1,2-ethane diylbis- (N- (carboxymethyl) glycine).
나아가, 상기 금속비활성 첨가제의 파라핀 오일에 대한 20℃에서의 용해도가 0.01g/100㎖ 이하인 것을 특징으로 하는, 전력 케이블을 제공한다.Furthermore, it provides a power cable, characterized in that the solubility of the metal-inert additive in paraffin oil at 20 ° C. is 0.01 g / 100 ml or less.
한편, 상기 내부 반도전층, 상기 외부 반도전층, 또는 이들 모두의 기재 수지에 포함된 헤테로상 프로필렌 공중합체는 프로필렌 단독중합체 매트릭스 내에 프로필렌 공중합체 엘라스토머가 분산된 것을 특징으로 하는, 전력 케이블을 제공한다.Meanwhile, the heterophasic propylene copolymer included in the inner semiconductive layer, the outer semiconducting layer, or both base resins provides a power cable, wherein the propylene copolymer elastomer is dispersed in the propylene homopolymer matrix.
여기서, 상기 프로필렌 공중합체 엘라스토머의 함량은, 상기 헤테로상 프로필렌 공중합체의 총 중량을 기준으로, 65 내지 75 중량%인 것을 특징으로 하는, 전력 케이블을 제공한다.Here, the content of the propylene copolymer elastomer, characterized in that 65 to 75% by weight, based on the total weight of the heterophasic propylene copolymer, provides a power cable.
그리고, 상기 헤테로상 프로필렌 공중합체는 아래 조건 a) 내지 h)를 모두 만족하는 것을 특징으로 하는, 전력 케이블을 제공한다.In addition, the heterophasic propylene copolymer provides a power cable, characterized in that all of the following conditions a) to h) are satisfied.
a) 밀도가 0.86 내지 0.90 g/㎤(ISO 11883에 따라 측정됨),a) density between 0.86 and 0.90 g / cm 3 (measured according to ISO 11883),
b) 용융 유속(MFR)이 0.5 내지 1.0 g/10분(ISO 1133에 따라 230℃에서 2.16kg의 하중하에 측정),b) melt flow rate (MFR) of 0.5 to 1.0 g / 10 min (measured under a load of 2.16 kg at 230 ° C. according to ISO 1133),
c) 파단시 인장응력이 10 MPa 이상(250mm/분의 인장속도로 측정),c) tensile stress at break is 10 MPa or more (measured at a tensile speed of 250 mm / min),
d) 파단시 인장변형율이 500 % 이상(250mm/분의 인장속도로 측정),d) a tensile strain of at least 500% at break (measured at a tensile speed of 250 mm / min),
e) 굴곡 모듈러스(flexural modulus)가 90 내지 300 MPae) flexural modulus is from 90 to 300 MPa
f) Vicat 연화점이 55 ℃ 이상(규격 A50에 따라 50℃/h 및 10N에서 측정),f) Vicat softening point of at least 55 ° C (measured at 50 ° C / h and 10 N according to standard A50),
g) 쇼어 D 경도가 28 이상, 및g) Shore D hardness is at least 28, and
h) 용융점이 160 내지 165 ℃h) melting point of 160 to 165 캜
본 발명에 따른 전력 케이블은 그 자체로서 내열성이 우수한 비가교 폴리프로필렌을 절연층 및 반도전층의 기재 수지로 사용함으로써, 환경 친화적인 동시에 가교를 위한 공정이 불필요하여 제조비용이 저렴한 우수한 효과를 나타낸다.The power cable according to the present invention uses non-crosslinked polypropylene having excellent heat resistance as the base resin of the insulating layer and the semiconducting layer, and thus has an excellent effect of being environmentally friendly and requiring no crosslinking process and having low manufacturing cost.
또한, 본 발명에 따른 전력 케이블은 내열성과 기계적 강도가 우수할 뿐만 아니라, 이들과 상충관계(trade-off)에 있는 유연성, 굴곡성, 내충격성, 내한성, 포설성, 작업성 등을 동시에 만족시키는 우수한 효과를 나타낸다.In addition, the power cable according to the present invention is not only excellent in heat resistance and mechanical strength, but also excellent in satisfying the flexibility, flexibility, impact resistance, cold resistance, installation properties, workability, etc., which are at a trade-off with them. Effect.
나아가, 본 발명에 따른 전력 케이블은 절연층에 대한 외부 반도전층의 접착력 조절이 용이하여 상기 절연층과 상기 반도전층의 접착력이 충분한 동시에 전기시공시 케이블 말단의 외부 반도전층을 절연층으로부터 부분적으로 박리시키는 것이 용이하여 시공성, 작업성 등이 우수한 효과를 나타낸다.Furthermore, the power cable according to the present invention is easy to control the adhesion of the outer semiconducting layer to the insulating layer, the adhesive strength of the insulating layer and the semiconducting layer is sufficient and at the same time partially peel off the outer semiconducting layer at the end of the cable from the insulating layer during electrical construction It is easy to make it, and workability, workability, etc. are excellent effect.
도 1은 본 발명에 따른 전력 케이블의 단면구조를 개략적으로 도시한 횡단면도이다.1 is a cross-sectional view schematically showing the cross-sectional structure of a power cable according to the present invention.
도 2는 본 발명에 따른 전력 케이블의 단면구조를 개략적으로 도시한 종단면도이다.2 is a longitudinal sectional view schematically showing a cross-sectional structure of a power cable according to the present invention.
이하, 본 발명의 바람직한 실시예들을 상세히 설명하기로 한다. 그러나, 본 발명은 여기서 설명된 실시예들에 한정되지 않고 다른 형태로 구체화될 수도 있다. 오히려, 여기서 소개되는 실시예들은 개시된 내용이 철저하고 완전해질 수 있도록, 그리고 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 제공되어지는 것이다. 명세서 전체에 걸쳐서 동일한 참조번호들은 동일한 구성요소들을 나타낸다.Hereinafter, preferred embodiments of the present invention will be described in detail. However, the invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and to fully convey the spirit of the present invention to those skilled in the art. Like numbers refer to like elements throughout.
도 1 및 2는 본 발명에 따른 전력 케이블의 실시예를 도시한 것이다.1 and 2 show an embodiment of a power cable according to the invention.
도 1 및 2에 도시된 바와 같이, 본 발명에 따른 전력 케이블은 구리, 알루미늄 등의 전도성 물질로 이루어진 도체(1), 절연성 고분자로 이루어진 절연층(3), 상기 도체(1)와 상기 절연층(3) 사이에 위치하여 도체(1)와의 계면에서의 부분방전을 억제하고, 상기 도체(1)와 상기 절연층(3) 사이의 공기층을 없애주며, 국부적인 전계집중을 완화시켜 주는 등의 역할을 수행하는 내부 반도전층(2), 절연체에 균등한 전계가 걸리도록 하는 국부적인 전계집중완화 역할을 수행하는 외부 반도전층(4), 케이블 보호를 위한 쉬스층(5) 등을 포함할 수 있다.1 and 2, the power cable according to the present invention is a conductor (1) made of a conductive material such as copper, aluminum, an insulating layer (3) made of an insulating polymer, the conductor (1) and the insulating layer Located between (3) to suppress partial discharge at the interface with the conductor (1), to eliminate the air layer between the conductor (1) and the insulating layer (3), to mitigate local electric field concentration, etc. An inner semiconducting layer (2) to play a role, an outer semiconducting layer (4) to play a localized field concentration relaxation role to apply an even electric field to the insulator, and a sheath layer (5) to protect the cable. have.
상기 도체(1), 절연층(3), 반도전층(2,4), 쉬스층(5) 등의 규격은 케이블의 용도, 송전압 등에 따라 다양할 수 있으며, 상기 절연층(3), 반도전층(2,4), 쉬스층(5)을 구성하는 재료는 동일하거나 상이할 수 있다. 바람직하게는, 상기 절연층(3), 반도전층(2,4) 및 쉬스층(5)은 서로간의 충분한 접착력을 확보하기 위해 동일한 계열의 고분자 수지를 베이스 수지로 포함하는 조성물로부터 제조될 수 있다.Standards of the conductor 1, the insulating layer 3, the semiconducting layers 2 and 4, the sheath layer 5, and the like may vary according to the use of the cable, the transmission voltage, and the like. The materials constituting the entire layers 2 and 4 and the sheath layer 5 may be the same or different. Preferably, the insulating layer (3), semiconductive layers (2, 4) and sheath layer (5) may be prepared from a composition containing a polymer resin of the same series as a base resin in order to secure sufficient adhesion to each other. .
상기 절연층(3)은 폴리올레핀 수지, 바람직하게는 폴리프로필렌 수지를 포함하는 비가교 절연 조성물로부터 제조될 수 있다. 상기 폴리프로필렌 수지는 프로필렌 단독중합체, 프로필렌 공중합체, 상이 다른 2종 이상의 프로필렌 공중합체를 포함하는 헤테로상 프로필렌 공중합체 등 또는 이들의 배합물을 포함할 수 있고, 상기 프로필렌 공중합체는 랜덤 프로필렌 공중합체, 블록 프로필렌 공중합체, 또는 이들의 배합물이고, 바람직하게는 랜덤 프로필렌 공중합체이다.The insulating layer 3 can be made from a non-crosslinked insulating composition comprising a polyolefin resin, preferably a polypropylene resin. The polypropylene resin may include a propylene homopolymer, a propylene copolymer, a heterophasic propylene copolymer including two or more different propylene copolymers having different phases, or a combination thereof, and the propylene copolymer may include a random propylene copolymer, It is a block propylene copolymer, or a combination thereof, Preferably it is a random propylene copolymer.
바람직하게는, 상기 폴리프로필렌 수지는 랜덤 프로필렌 공중합체와 헤테로상 프로필렌 공중합체의 배합물을 포함할 수 있다. 더욱 바람직하게는, 상기 헤테로상 프로필렌 공중합체는 프로필렌 단독중합체로 이루어진 수지 매트릭스 내에 프로필렌 공중합체 엘라스토머가 분산된 것일 수 있고, 여기서, 상기 랜덤 프로필렌 공중합체와 상기 헤테로상 프로필렌 공중합체의 배합물로 이루어진 조성물에서 상기 랜덤 프로필렌 공중합체의 함량은 20 내지 60 중량%일 수 있다.Preferably, the polypropylene resin may comprise a blend of a random propylene copolymer and a heterophasic propylene copolymer. More preferably, the heterophasic propylene copolymer may be a dispersion of a propylene copolymer elastomer in a resin matrix composed of a propylene homopolymer, wherein the composition consists of a combination of the random propylene copolymer and the heterophasic propylene copolymer. In the content of the random propylene copolymer may be 20 to 60% by weight.
상기 프로필렌 랜덤 공중합체와 상기 헤테로상 프로필렌 공중합체의 중량비가 2:8 미만인 경우 형성되는 절연층(3)의 인장강도 등의 기계적 강도가 불충분할 수 있는 반면, 6:4 초과인 경우 절연층(3)의 유연성, 굴곡성, 내충격성, 내한성 등의 불충분할 수 있다.When the weight ratio of the propylene random copolymer and the heterophasic propylene copolymer is less than 2: 8, mechanical strength such as tensile strength of the insulating layer 3 formed may be insufficient, whereas when the ratio is greater than 6: 4, the insulating layer ( 3) flexibility, bendability, impact resistance, cold resistance, etc. may be insufficient.
상기 비가교 절연 조성물은 굴곡 모듈러스(flexural modulus)가 200 내지 700 MPa이고, 용융점(Tm)이 150 내지 160℃(시차주사열량계(DSC)로 측정)이며, 용융엔탈피가 30 내지 90 J/g(시차주사열량계(DSC)로 측정)이고, 자일렌 용해도(135℃의 자일렌(xylene)에 2g의 수지를 첨가하여 D5492-10에 준하여 측정)가 19 내지 36 %일 수 있다.The non-crosslinked insulating composition has a flexural modulus of 200 to 700 MPa, a melting point (Tm) of 150 to 160 ° C (measured by differential scanning calorimetry (DSC)), and a melting enthalpy of 30 to 90 J / g ( Differential scanning calorimetry (DSC), and xylene solubility (measured according to D5492-10 by adding 2 g of resin to xylene at 135 ° C.) may be 19 to 36%.
상기 비가교 절연 조성물은 굴곡 모듈러스가 700 MPa를 초과하는 경우 케이블의 유연성, 굴곡성, 내충격성, 내한성, 포설성, 작업성 등이 불충분할 수 있고, 용융점(Tm)이 150℃ 미만인 경우 케이블의 내열성 등이 불충분할 수 있다.The non-crosslinked insulating composition may have insufficient flexibility, flexibility, impact resistance, cold resistance, installation property, and workability when the flexural modulus exceeds 700 MPa, and the heat resistance of the cable when the melting point (Tm) is less than 150 ° C. Or the like may be insufficient.
또한, 상기 자일렌 용해도가 36 %를 초과하는 경우 수지의 입체규칙성(isotacticity)이 과도하게 낮아 기계적 강도가 불충분할 수 있고, 19 % 미만인 경우 수지의 입체규칙성이 과도하게 높고 유연성, 굴곡성, 내충격성, 내한성 등이 저하될 수 있다.In addition, when the xylene solubility is more than 36%, the resin is excessively low isotacticity (isotacticity) may be insufficient mechanical strength, if less than 19%, the resin is excessively high stereoregularity, flexibility, flexibility, Impact resistance, cold resistance and the like may be lowered.
상기 절연층(3)을 형성하는 비가교 절연 조성물은 비가교 폴리프로필렌을 포함하므로 재활용이 가능한 등 환경 친화적인 동시에, 상기 기술한 구성에 의해 내열성과 기계적 강도 및 이와 상충관계에 있는 유연성, 굴곡성, 내충격성, 내한성, 포설성, 작업성 등을 충족시킬 수 있다.The non-crosslinked insulating composition forming the insulating layer 3 includes non-crosslinked polypropylene, which is environmentally friendly, such as recyclable, and at the same time, the above-described configuration provides flexibility, flexibility, It can satisfy impact resistance, cold resistance, laying resistance, workability, etc.
본 발명에 있어서, 상기 반도전층(2,4)은 상이 다른 2종 이상의 프로필렌 공중합체를 포함하는 헤테로상 프로필렌 공중합체 및 전도성 입자를 포함하는 반도전성 조성물로부터 제조될 수 있다. 바람직하게는, 상기 헤테로상 프로필렌 공중합체는 프로필렌 단독중합체 매트릭스 내에 프로필렌 공중합체 엘라스토머가 균일하게 분산된 헤테로상 프로필렌 공중합체일 수 있다. 여기서, 상기 프로필렌 공중합체 엘라스토머의 함량은 상기 헤테로상 프로필렌 공중합체의 총 중량을 기준으로 약 65 내지 75 중량%일 수 있다.In the present invention, the semiconducting layers 2,4 may be prepared from a semiconductive composition comprising a heterophasic propylene copolymer comprising two or more kinds of propylene copolymers different in phase and conductive particles. Preferably, the heterophasic propylene copolymer may be a heterophasic propylene copolymer in which the propylene copolymer elastomer is uniformly dispersed in the propylene homopolymer matrix. Herein, the content of the propylene copolymer elastomer may be about 65 to 75 wt% based on the total weight of the heterophasic propylene copolymer.
상기 반도전층(2,4)을 형성하는 반도전성 조성물은 비가교 폴리프로필렌 수지를 기재 수지로 포함하므로 재활용이 가능한 등 환경 친화적인 동시에, 내열성과 기계적 강도 및 이와 상충관계에 있는 유연성, 굴곡성, 내충격성, 내한성, 포설성, 작업성 등을 충족시킬 수 있다.Since the semiconductive composition forming the semiconductive layers 2 and 4 includes an uncrosslinked polypropylene resin as a base resin, the semiconducting composition is environmentally friendly, such as recycling, and at the same time, heat resistance, mechanical strength, and flexibility, flexibility, and resistance to a conflict therewith. It can meet impact resistance, cold resistance, installability, workability and so on.
상기 반도전층(2,4) 중 내부 반도전층(2)을 형성하는 반도전성 조성물은 상기 전력 케이블의 도체(1)로부터 상기 내부 반도전층(2)으로 유입되는 금속성 물질을 비활성화시키는 첨가제인 금속비활성 첨가제를 추가로 포함할 수 있다. 상기 금속성 물질, 예를 들어, 구리 이온과 같은 전이금속 이온 원자의 경우 상대적으로 큰 원자반경으로 인하여 주어진 이온차수에 의한 이온결합 이외에 추가적인 배위결합(coordinate bond)을 이룰 수 있으므로, 이러한 큰 원자반경을 가지는 전이금속 이온의 비활성화를 위해선 하나의 금속원자와 2개 이상의 배위결합을 이루는 킬레이트 리간드(chelate legand) 형태의 분자구조를 가지는 첨가제가 바람직하다.The semiconducting composition forming the inner semiconducting layer 2 among the semiconducting layers 2 and 4 is an inert metal which is an additive which deactivates the metallic material flowing from the conductor 1 of the power cable to the inner semiconducting layer 2. It may further include an additive. In the case of the metallic material, for example, transition metal ion atoms such as copper ions, due to the relatively large atomic radius, an additional coordinate bond may be formed in addition to the ionic bond by a given ion order. In order to deactivate the transition metal ion, an additive having a molecular structure in the form of a chelate legand forming two or more coordination bonds with one metal atom is preferable.
상기 금속비활성 첨가제는 분자구조 내에 전자주개(electron donor) 역할을 하는 루이스 염기 사이트(Lewis-base site)를 2곳 이상 보유한 것이 바람직하며, 상기 루이스 염기는 아민, 아미드, 카르복실 등의 관능기가 바람직하다.The metal inactive additive preferably has at least two Lewis-base sites serving as electron donors in the molecular structure, and the Lewis bases preferably have functional groups such as amines, amides, and carboxyls. Do.
또한, 상기 금속비활성 첨가제는 파라핀 오일 등의 절연유에 대한 용해도가 0.01g/100㎖(20℃에서 용매 100㎖에 용해된 용질의 그람) 이하인 것이 바람직하다. 전력 케이블에 있어서 상기 금속비활성 첨가제가 포함된 내부 반도전층(2)과 맞닿아 있는 절연층(3)에 파라핀계 절연유를 사용하는 경우, 상기 금속비활성 첨가제의 상기 파라핀계 절연유에 대한 용해도가 크면, 상기 금속비활성 첨가제가 바깥으로 용출되거나 절연층(3)으로 이행될 수 있어, 상기 금속비활성 첨가제의 본래 특성구현에 어려움이 있을 수 있다.In addition, it is preferable that the metal inactive additive has a solubility in insulating oil such as paraffin oil of 0.01 g / 100 ml (gram of solute dissolved in 100 ml of solvent at 20 ° C) or less. When using a paraffinic insulating oil in the insulating layer (3) in contact with the inner semiconducting layer (2) containing the metal inactive additive in the power cable, if the solubility of the metal inactive additive in the paraffinic insulating oil is large, Since the metal inactive additive may be eluted outwards or transferred to the insulating layer 3, it may be difficult to realize the original characteristics of the metal inactive additive.
이러한 관점에서, 상기 금속비활성 참가제는 바람직하게는 N,N'-비스(살리실리덴)-1,2-프로판디아민(N,N'-bis(salicylidene)-1,2-propanediamine), 1,2-비스(3,5-디-t-부틸-4-하이드록시신나모일)히드라진(1,2-bis(3,5-di-tert-butyl-4-hydroxycinnamoyl)hydrazine), N,N'-1,2-에탄 디일비스-(N-(카르복시메틸)글리신(N,N'-1,2-ethane diylbis-(N-(carboxymethyl)glycine)이다.In this respect, the metal inactive activator is preferably N, N'-bis (salicylidene) -1,2-propanediamine (N, N'-bis (salicylidene) -1,2-propanediamine), 1 , 2-bis (3,5-di-t-butyl-4-hydroxycinnamoyl) hydrazine (1,2-bis (3,5-di-tert-butyl-4-hydroxycinnamoyl) hydrazine), N, N '-1,2-ethane diylbis- (N- (carboxymethyl) glycine) is N, N'-1,2-ethane diylbis- (N- (carboxymethyl) glycine).
상기 금속비활성 첨가제는 상기 반도전성 조성물의 기재 수지 100 중량부를 기준으로 0.1 내지 5 중량부일 수 있다. 상기 금속비활성 첨가제의 함량이 0.1 중량부 미만인 경우 목적한 효과, 즉 도체(1)로부터 유입되는 금속 물질의 비활성화에 의한 내부 반도전층(2)의 열화방지 효과를 달성할 수 없고, 5 중량부 초과인 경우 압출 후 기재 수지와의 상용성 문제로 인한 백화현상이 유발될 수 있다.The metal inactive additive may be 0.1 to 5 parts by weight based on 100 parts by weight of the base resin of the semiconductive composition. When the content of the metal inactive additive is less than 0.1 parts by weight, the desired effect, that is, the anti-deterioration effect of the internal semiconducting layer 2 due to deactivation of the metal material flowing from the conductor 1 cannot be achieved, and more than 5 parts by weight. In the case of bleaching may occur due to compatibility problems with the base resin after extrusion.
상기 반도전층(2,4) 중 외부 반도전층(4)을 형성하는 반도전성 조성물은 상기 헤테로상 프로필렌 공중합체 이외에 극성 단량체를 포함하는 올레핀 공중합체를 포함할 수 있다. 여기서, 상기 헤테로상 프로필렌 공중합체와 상기 극성 단량체를 포함하는 올레핀 공중합체가 포함된 수지 조성물에서 상기 헤테로상 프로필렌 공중합체의 함량은 10 내지 30 중량%일 수 있고, 상기 헤테로상 프로필렌 공중합체와 상기 극성 단량체를 포함하는 올레핀 공주합체의 총 중량을 기준으로, 상기 극성 단량체의 함량은 13 내지 17 중량%일 수 있다.The semiconductive composition forming the outer semiconducting layer 4 of the semiconducting layers 2 and 4 may include an olefin copolymer including a polar monomer in addition to the heterophasic propylene copolymer. Here, the content of the heterophasic propylene copolymer in the resin composition including the heterophasic propylene copolymer and the olefin copolymer including the polar monomer may be 10 to 30% by weight, the heterophasic propylene copolymer and the The content of the polar monomer may be 13 to 17% by weight, based on the total weight of the olefin cyclopolymer including the polar monomer.
여기서, 상기 헤테로상 프로필렌 공중합체의 함량이 10 중량% 미만이거나 상기 극성 단량체의 함량이 17 중량% 초과인 경우 상기 외부 반도전층(4)과 상기 절연층(3) 사이의 접착력이 불충분할 수 있는 반면, 상기 헤테로상 프로필렌 공중합체의 함량이 30 중량% 초과이거나 상기 극성 단량체의 함량이 13 중량% 미만인 경우 상기 절연층(3)으로부터의 상기 외부 반도전층(4)의 박리성이 불충분할 수 있다.Here, when the content of the heterophasic propylene copolymer is less than 10% by weight or the content of the polar monomer is more than 17% by weight, the adhesion between the outer semiconducting layer 4 and the insulating layer 3 may be insufficient. On the other hand, when the content of the heterophasic propylene copolymer is more than 30% by weight or the content of the polar monomer is less than 13% by weight, peelability of the outer semiconducting layer 4 from the insulating layer 3 may be insufficient. .
상기 올레핀 공중합체를 형성하는 올레핀 단량체는 예를 들어 에틸렌, 프로펜, 부텐, 펜텐, 헥센, 옥텐, 데센, 도데센 등일 수 있다. 또한, 상기 올레핀 공중합체를 형성하는 상기 극성 단량체는 부분적으로 또는 전체적으로 음전하를 갖는 단량체를 의미한다. 이러한 극성 단량체는 예를 들어 비닐 아세테이트, 비닐 버사테이트 등의 비닐 에스테르 단량체; 메타크릴산, 아크릴산, 말레산, 이타콘산 등의 비닐-불포화 카르복시산 단량체; (메트)아크릴레이트 또는 알킬(메트)아크릴레이트(여기서, 알킬은 메틸, 에틸, 프로필, n-부틸, sec-부틸, tert-부틸, 펜틸, 이소보닐, 헥실, 헵틸, n-옥틸, 2-에틸헥실, 데실, 운데실, 도데실, 라우릴, 세틸 또는 스테아릴이다) 단량체 등일 수 있고, 상기 올레핀 공중합체는 바람직하게는 에틸렌 부틸 아크릴레이트(EBA)일 수 있다.The olefin monomer forming the olefin copolymer may be, for example, ethylene, propene, butene, pentene, hexene, octene, decene, dodecene and the like. In addition, the polar monomer forming the olefin copolymer means a monomer having a negative charge partially or wholly. Such polar monomers include, for example, vinyl ester monomers such as vinyl acetate and vinyl versatate; Vinyl-unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, maleic acid and itaconic acid; (Meth) acrylate or alkyl (meth) acrylate, wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, isobornyl, hexyl, heptyl, n-octyl, 2- Ethylhexyl, decyl, undecyl, dodecyl, lauryl, cetyl or stearyl) monomers and the like, and the olefin copolymer may preferably be ethylene butyl acrylate (EBA).
앞서 기술한 구성의 외부 반도전층(4)은 상기 절연층(3)으로부터 박리하는데 소요되는 힘인 박리력이 약 3 내지 15 N일 수 있다.The outer semiconducting layer 4 having the above-described configuration may have a peel force of about 3 to 15 N, which is a force required to peel off from the insulating layer 3.
본 발명의 전력 케이블에 있어서, 상기 외부 반도전층(4)은 상기 헤테로상 프로필렌 공중합체와 상기 극성 단량체를 포함하는 올레핀 공중합체의 특정 배합비, 그리고 상기 올레핀 공중합체에 포함된 상기 극성 단량체의 특정 함량에 의해 상기 절연층(3)과의 충분한 접착력과 상기 절연층(3)으로부터의 충분한 박리성을 모두 만족할 수 있고, 전기시공시 상기 외부 반도전층(4)을 상기 절연층(3)으로부터 박리시키는 경우 상기 절연층(3) 상에 상기 외부 반도전층(4)의 잔존물이 잔존하는 것을 회피할 수 있다.In the power cable of the present invention, the outer semiconducting layer 4 has a specific blending ratio of the olefin copolymer including the heterophasic propylene copolymer and the polar monomer, and a specific content of the polar monomer included in the olefin copolymer. This satisfies both the sufficient adhesive force with the insulating layer 3 and the sufficient peeling property from the insulating layer 3, and allows the outer semiconducting layer 4 to be peeled from the insulating layer 3 during electrical construction. In this case, it is possible to avoid remaining of the outer semiconducting layer 4 on the insulating layer 3.
상기 반도전층(2,4)을 형성하는 반도전성 조성물은 상기 반도전층(2,4)의 전기전도도를 조절하기 위해 상기 전도성 입자를 추가로 포함한다. 상기 전도성 입자에 대한 특별한 제한은 없고, 예를 들어, 퍼니스 블랙(furnace black), 아세틸렌 블랙 등과 같은 카본블랙, 또는 그래파이트, 그래핀 등이 사용될 수 있다.The semiconducting composition forming the semiconducting layers 2 and 4 further includes the conductive particles to control the electrical conductivity of the semiconducting layers 2 and 4. There is no particular limitation on the conductive particles, and for example, carbon black such as furnace black, acetylene black, or the like, or graphite, graphene or the like may be used.
상기 카본블랙 등의 전도성 입자는 그 형상에 대한 특별한 제한은 없고, 예를 들어, 구형, 플레이트형, 막대형, 튜브형 등일 수 있다. 또한 상기 전도성 입자의 표면적은 20㎡/g 이상, 예를 들어, 40 내지 1,200 ㎡/g일 수 있고, 바람직하게는, 발포성 중합물질의 체적저항이 500 Ωm 미만, 더욱 바람직하게는 20 Ωm 미만일 수 있다.The conductive particles such as carbon black are not particularly limited in shape, and may be, for example, spherical, plate-shaped, rod-shaped, or tubular. In addition, the surface area of the conductive particles may be 20 m 2 / g or more, for example, 40 to 1,200 m 2 / g, and preferably, the volume resistance of the expandable polymeric material may be less than 500 Ωm, more preferably less than 20 Ωm. have.
특히, 상기 카본블랙 등의 전도성 입자 함량은 상기 반도전성 조성물의 기재 수지 100 중량부를 기준으로 30 내지 70 중량부일 수 있다. 상기 카본블랙 등의 전도성 입자 함량이 30 중량부 미만인 경우 목적한 반도전 특성을 구현하기 어려울 수 있고, 70 중량부 초과인 경우 압출가공이 불리할 수 있다.In particular, the conductive particles content such as carbon black may be 30 to 70 parts by weight based on 100 parts by weight of the base resin of the semiconductive composition. When the conductive particle content, such as carbon black, is less than 30 parts by weight, it may be difficult to implement the desired semiconducting properties, and when it is more than 70 parts by weight, extrusion may be disadvantageous.
상기 반도전층(2,4)을 형성하는 반도전성 조성물은 산화방지제, 활제 등의 기타 첨가제를 추가로 포함할 수 있다. 상기 산화방지제는 아민계, 디알킬에스테르계, 티오에스테르계, 페놀계 산화방지제 등을 사용할 수 있고, 예를 들어, [3-[3-(3,5-디-t-부틸-4-하이드록시페닐)프로파노일옥시]-2,2-비스[3-(3,5-디-t-부틸-4-하이드록시페닐)프로파노일옥시메틸]프로필], 3-(3,5-디-3차 부틸-4-하이드록시페닐)프로파노에이트, 티오디에틸렌 비스(3,5-디-3차 부틸-4-하이드록시하이드로신나메이트), 3,5-비스(1,1-디메틸에틸)-4-하이드록시벤젠프로피온산 옥타데실 에스테르, 프로피온산, 3,3'티오비스-1,1'디옥타데실 에스테르 등일 수 있다.The semiconductive composition forming the semiconducting layers 2 and 4 may further include other additives such as antioxidants and lubricants. The antioxidant may be an amine, dialkyl ester, thioester, phenol-based antioxidant, and the like, for example, [3- [3- (3,5-di-t-butyl-4-hydroxy Oxyphenyl) propanoyloxy] -2,2-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoyloxymethyl] propyl], 3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propanoate, thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 3,5-bis (1,1- Dimethylethyl) -4-hydroxybenzenepropionic acid octadecyl ester, propionic acid, 3,3'thiobis-1,1 'dioctadecyl ester, and the like.
또한, 상기 활제는 예를 들어 수평균 분자량(Mn)이 1,000 내지 10,000인 폴리프로필렌 왁스 또는 폴리에틸렌 왁스일 수 있다. 상기 산화방지제, 활제 등의 기타 첨가제 각각의 함량은 상기 반도전성 조성물의 기재 수지 100 중량부를 기준으로 0.2 내지 3 중량부일 수 있다.In addition, the lubricant may be, for example, a polypropylene wax or polyethylene wax having a number average molecular weight (Mn) of 1,000 to 10,000. The content of each of the other additives such as the antioxidant and the lubricant may be 0.2 to 3 parts by weight based on 100 parts by weight of the base resin of the semiconductive composition.
[실시예]EXAMPLE
1. 제조예1. Preparation
아래 표 1에 나타난 바와 같은 구성 성분 및 함량으로 구성된 조성물로부터 형성된 실시예 및 비교예에 따른 각각의 샘플 시트를 제조했다. 구체적으로, 폭 약 13 mm, 두께 약 1 mm, 길이 약 130 mm의 절연 시트 및 반도전 시트를 각각 제조한 후 이들을 겹쳐놓고 200℃의 온도에서 프레스하여 최종 샘플 시트를 제조했다. 아래 표 1에 기재된 함량의 단위는 중량부이다.Each sample sheet was prepared according to the examples and comparative examples formed from the composition consisting of the components and contents as shown in Table 1 below. Specifically, an insulating sheet and a semiconducting sheet having a width of about 13 mm, a thickness of about 1 mm, and a length of about 130 mm were prepared, respectively, and then overlaid and pressed at a temperature of 200 ° C. to prepare a final sample sheet. Units of the content described in Table 1 below are parts by weight.
표 1
실시예 1 실시예 2 실시예 3 실시예 4 비교예 1 비교예 2 비교예 3
절연층 수지1 100 100 100 100 100 100 100
외부반도전층 수지2 0 0 0 0 0 0 61
수지3 87.5 85 0 0 90 90 0
수지4 0 0 90 85 0 0 0
수지5 0 0 0 0 10 0 0
수지6 12.5 15 10 15 0 10 39
전도성입자 60 60 60 60 60 60 60
극성단량체 함량 16.625 16.15 15.3 14.45 17.1 17.1 17.08
Table 1
Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3
Insulation layer Resin 1 100 100 100 100 100 100 100
Outer semiconducting layer Resin 2 0 0 0 0 0 0 61
Resin 3 87.5 85 0 0 90 90 0
Resin 4 0 0 90 85 0 0 0
Resin 5 0 0 0 0 10 0 0
Resin 6 12.5 15 10 15 0 10 39
Conductive particles 60 60 60 60 60 60 60
Polar monomer content 16.625 16.15 15.3 14.45 17.1 17.1 17.08
- 수지 1 : 프로필렌 공중합체(프로필렌 단독중합체 매트릭스 내에 1㎛ 이하의 프로필렌 공중합체 엘라스토머 입자가 분산된 헤테로상 수지와 랜덤 프로필렌-에틸렌 공중합체(에틸렌 함량 : 3 중량%)의 8:2 배합물)Resin 1: Propylene copolymer (8: 2 blend of heterophasic resin in which propylene copolymer elastomer particles of 1 µm or less are dispersed in a propylene homopolymer matrix and random propylene-ethylene copolymer (ethylene content: 3% by weight))
- 수지 2 : 에틸렌비닐아세테이트 수지(비닐아세테이트 28 중량%)(제조사 : 롯데케미칼; 제품명 : VC590)Resin 2: Ethylene vinyl acetate resin (28% by weight of vinyl acetate) (Manufacturer: Lotte Chemical; Product Name: VC590)
- 수지 3 : 에틸렌비닐아세테이트 수지(비닐아세테이트 19 중량%)(제조사 : 롯데케미칼; 제품명 : VS430)Resin 3: Ethylene vinyl acetate resin (19% by weight of vinyl acetate) (Manufacturer: Lotte Chemical; Product Name: VS430)
- 수지 4 : 에틸렌부틸아크릴레이트 수지(부틸아크릴레이트 17 중량%)(제조사 : 듀퐁; 제품명 : 3217AC)Resin 4: Ethylene butyl acrylate resin (Butyl acrylate 17 wt%) (Manufacturer: DuPont; Product name: 3217AC)
- 수지 5 : 랜덤 프로필렌-에틸렌 공중합체(에틸렌 함량 : 3 중량%)Resin 5: Random propylene-ethylene copolymer (ethylene content: 3 wt%)
- 수지 6 : 프로필렌 단독중합체 매트릭스 내에 1㎛ 이하의 프로필렌 공중합체 엘라스토머 입자가 분산된 헤테로상 프로필렌 공중합체Resin 6: heterophasic propylene copolymer in which propylene copolymer elastomer particles of 1 µm or less are dispersed in a propylene homopolymer matrix
- 전도성 입자 : 카본블랙Conductive Particles: Carbon Black
2. 박리력 평가2. Peel force evaluation
인장시험기(UTM)를 이용하여 250 mm/min의 속도로 실시예 및 비교예에 따른 각각의 샘플 시트에서 절연층으로부터 외부 반도전층을 박리하는데 소요되는 힘, 즉 박리력을 각각 5회 측정하여 평균값을 산정했고, 박리 후 절연층에 잔존하는 외부 반도전층인 흑점의 존재여부를 확인했고, 그 결과는 아래 표 2에 나타난 바와 같다. 아래 표 2에 기재된 박리력의 단위는 뉴튼(N)이다.Using a tensile tester (UTM) at the rate of 250 mm / min in each sample sheet according to the Examples and Comparative Examples, the force required to peel the outer semiconducting layer from the insulating layer, that is, the peel force is measured five times each average value Was calculated, and the presence of dark spots, which are external semiconducting layers remaining in the insulating layer after peeling, was confirmed, and the results are shown in Table 2 below. The unit of peel force described in Table 2 below is Newton (N).
표 2
실시예 1 실시예 2 실시예 3 실시예 4 비교예 1 비교예 2 비교예 3
박리력 3.409 4.808 10.509 15 1.341 2.65 25.141
흑점 없음 없음 없음 없음 없음 없음 있음
TABLE 2
Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3
Peel force 3.409 4.808 10.509 15 1.341 2.65 25.141
black spot none none none none none none has exist
상기 표 2에 기재된 바와 같이, 본 발명에 따른 실시예 1 내지 4의 샘플 시트에서 절연층으로부터 외부 반도전층을 박리하는데 소요되는 박리력이 3 내지 15 N의 범위에 있으므로, 상기 절연층과 상기 외부 반도전층 사이의 충분한 접착력을 나타내는 동시에, 전기시공시 요구되는 우수한 작업성, 시공성 등을 나타내며, 상기 절연층으로부터 상기 외부 반도전층의 박리시 상기 절연층 상에 상기 외부 반도전층의 잔존물인 흑점이 발견되지 않았다.As shown in Table 2, since the peel force required to peel the outer semiconducting layer from the insulating layer in the sample sheet of Examples 1 to 4 according to the present invention is in the range of 3 to 15 N, the insulating layer and the outer It exhibits sufficient adhesion between the semiconducting layers, exhibits excellent workability, workability, and the like, which are required for electrical construction, and finds black spots, which are residues of the outer semiconducting layer, on the insulating layer upon peeling of the outer semiconducting layer from the insulating layer. It wasn't.
반면, 비교예 1 및 2에 따른 샘플 시트는 외부 반도전층을 형성하는 수지 내에 극성 단량체가 과량 포함되어 있어 절연층과 외부 반도전층의 접착력이 불충분하고, 비교예 3에 따른 샘플 시트는 수지 내에 극성 단량체가 과량 포함되어 있음에도 불구하고 끈적이는 성질이 강한 헤테로상 프로필렌 공중합체가 과량 포함되어 있으므로, 상기 절연층으로부터 상기 외부 반도전층의 박리가 어려워 케이블의 전기시공시 요구되는 작업성, 시공성 등이 저하되고, 박리 후 상기 절연층 상에 상기 외부 반도전층의 잔존물인 흑점이 발견되었다.On the other hand, the sample sheets according to Comparative Examples 1 and 2 contain an excessive amount of polar monomer in the resin forming the outer semiconducting layer, so that the adhesion between the insulating layer and the outer semiconducting layer is insufficient, and the sample sheet according to Comparative Example 3 is polar in the resin. In spite of the excessive amount of the monomer, the excessively sticky heterophasic propylene copolymer is contained, so that the external semiconducting layer is difficult to peel off from the insulating layer, thereby reducing workability and workability required for electrical construction of the cable. After peeling, black spots which are residues of the outer semiconducting layer were found on the insulating layer.
본 명세서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술분야의 당업자는 이하에서 서술하는 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경 실시할 수 있을 것이다. 그러므로 변형된 실시가 기본적으로 본 발명의 특허청구범위의 구성요소를 포함한다면 모두 본 발명의 기술적 범주에 포함된다고 보아야 한다.Although the present specification has been described with reference to preferred embodiments of the invention, those skilled in the art may variously modify and change the invention without departing from the spirit and scope of the invention as set forth in the claims set forth below. Could be done. Therefore, it should be seen that all modifications included in the technical scope of the present invention are basically included in the scope of the claims of the present invention.
[부호의 설명][Description of the code]
1 : 도체 2 : 내부 반도전층1: conductor 2: inner semiconducting layer
3 : 절연층 4 : 외부 반도전층3: insulation layer 4: outer semiconducting layer
5 : 쉬스층5: sheath layer

Claims (12)

  1. 도체, 상기 도체를 감싸는 내부 반도전층, 상기 내부 반도전층을 감싸는 절연층, 상기 절연층을 감싸는 외부 반도전층, 및 상기 외부 반도전층을 감싸는 쉬스층을 포함하는 전력 케이블에 있어서,A power cable comprising a conductor, an inner semiconducting layer surrounding the conductor, an insulating layer surrounding the inner semiconducting layer, an outer semiconducting layer surrounding the insulating layer, and a sheath layer surrounding the outer semiconducting layer,
    상기 내부 반도전층은, 상이 다른 2종 이상의 프로필렌 공중합체를 포함하는 헤테로상 프로필렌 공중합체를 포함하는 기재 수지 및, 상기 기재 수지 100 중량부를 기준으로, 전도성 입자 30 내지 70 중량부를 포함하는 반도전성 조성물로부터 형성되고,The inner semiconducting layer may include a base resin including a heterophasic propylene copolymer including two or more different propylene copolymers having different phases, and 30 to 70 parts by weight of conductive particles based on 100 parts by weight of the base resin. Formed from
    상기 절연층은 기재 수지로서 폴리프로필렌 수지를 포함하는 비가교 절연 조성물로부터 형성되는, 전력 케이블.And the insulating layer is formed from a non-crosslinked insulating composition comprising a polypropylene resin as the base resin.
  2. 제1항에 있어서,The method of claim 1,
    상기 외부 반도전층은, 상이 다른 2종 이상의 프로필렌 공중합체를 포함하는 헤테로상 프로필렌 공중합체 및 극성 단량체를 포함하는 올레핀 공중합체를 포함하고, 상기 헤테로상 프로필렌 공중합체와 상기 올레핀 공중합체의 총 중량을 기준으로, 상기 극성 단량체의 함량이 13 내지 17 중량%인 기재 수지 및, 상기 기재 수지 100 중량부를 기준으로, 전도성 입자 30 내지 70 중량부를 포함하는 반도전성 조성물로부터 형성되는, 전력 케이블.The outer semiconducting layer comprises a heterophasic propylene copolymer comprising two or more different propylene copolymers different in phase and an olefin copolymer comprising a polar monomer, wherein the total weight of the heterophasic propylene copolymer and the olefin copolymer On the basis, the power cable is formed from a semiconductive composition comprising a base resin having a content of the polar monomer of 13 to 17% by weight, and 30 to 70 parts by weight of conductive particles based on 100 parts by weight of the base resin.
  3. 제2항에 있어서,The method of claim 2,
    상기 극성 단량체는 비닐 에스테르 단량체, 비닐-불포화 카르복시산 단량체, (메트)아크릴레이트, 알킬(메트)아크릴레이트, 또는 이들의 배합을 포함하는 것을 특징으로 하는, 전력 케이블.Wherein said polar monomer comprises a vinyl ester monomer, a vinyl-unsaturated carboxylic acid monomer, a (meth) acrylate, an alkyl (meth) acrylate, or a combination thereof.
  4. 제3항에 있어서,The method of claim 3,
    상기 올레핀 공중합체는 에틸렌 부틸 아크릴레이트(EBA) 수지를 포함하는 것을 특징으로 하는, 전력 케이블.Wherein said olefin copolymer comprises ethylene butyl acrylate (EBA) resin.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 4,
    상기 내부 반도전층을 형성하는 반도전성 조성물은 금속비활성 첨가제 0.1 내지 5 중량부를 추가로 포함하는 것을 특징으로 하는, 전력 케이블.The semiconducting composition forming the inner semiconducting layer further comprises 0.1 to 5 parts by weight of the metal inactive additive.
  6. 제5항에 있어서,The method of claim 5,
    상기 금속비활성 첨가제는 하나의 금속원자와 2개 이상의 배위결합을 이루는 킬레이트 리간드(chelate legand) 형태의 분자구조를 가지는 것을 특징으로 하는, 전력 케이블.The metal inactive additive is characterized in that it has a molecular structure of the chelate ligand (chelate legand) form two or more coordination bonds with one metal atom, power cable.
  7. 제6항에 있어서,The method of claim 6,
    상기 금속비활성 첨가제는 분자구조 내에 전자주개(electron donor) 역할을 하는 루이스 염기 사이트(Lewis-base site)를 2곳 이상 보유하고, 상기 루이스 염기는 아민기, 아미드기 또는 카르복실기인 것을 특징으로 하는, 전력 케이블.The metal inactive additive has at least two Lewis base sites serving as electron donors in the molecular structure, and the Lewis bases are amine groups, amide groups or carboxyl groups. Power cable.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 금속비활성 첨가제는 N,N'-비스(살리실리덴)-1,2-프로판디아민, 1,2-비스(3,5-디-t-부틸-4-하이드록시신나모일)히드라진 또는 N,N'-1,2-에탄 디일비스-(N-(카르복시메틸)글리신인 것을 특징으로 하는, 전력 케이블.The metal inactive additive may be N, N'-bis (salicylidene) -1,2-propanediamine, 1,2-bis (3,5-di-t-butyl-4-hydroxycinnamoyl) hydrazine or N And N'-1,2-ethane diylbis- (N- (carboxymethyl) glycine).
  9. 제6항에 있어서,The method of claim 6,
    상기 금속비활성 첨가제의 파라핀 오일에 대한 20℃에서의 용해도가 0.01g/100㎖ 이하인 것을 특징으로 하는, 전력 케이블.A power cable, characterized in that the solubility at 20 ° C. of paraffin oil of the metal inactive additive is 0.01 g / 100 ml or less.
  10. 제1항 내지 제4항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 4,
    상기 내부 반도전층, 상기 외부 반도전층, 또는 이들 모두의 기재 수지에 포함된 헤테로상 프로필렌 공중합체는 프로필렌 단독중합체 매트릭스 내에 프로필렌 공중합체 엘라스토머가 분산된 것을 특징으로 하는, 전력 케이블.The heterophasic propylene copolymer contained in the base semiconducting layer, the outer semiconducting layer, or both base resins is characterized in that the propylene copolymer elastomer is dispersed in the propylene homopolymer matrix.
  11. 제10항에 있어서,The method of claim 10,
    상기 프로필렌 공중합체 엘라스토머의 함량은, 상기 헤테로상 프로필렌 공중합체의 총 중량을 기준으로, 65 내지 75 중량%인 것을 특징으로 하는, 전력 케이블.The content of the propylene copolymer elastomer, characterized in that 65 to 75% by weight based on the total weight of the heterophasic propylene copolymer, power cable.
  12. 제1항 내지 제4항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 4,
    상기 헤테로상 프로필렌 공중합체는 아래 조건 a) 내지 h)를 모두 만족하는 것을 특징으로 하는, 전력 케이블.The heterophasic propylene copolymer is characterized in that all of the following conditions a) to h), power cable.
    a) 밀도가 0.86 내지 0.90 g/㎤(ISO 11883에 따라 측정됨),a) density between 0.86 and 0.90 g / cm 3 (measured according to ISO 11883),
    b) 용융 유속(MFR)이 0.5 내지 1.0 g/10분(ISO 1133에 따라 230℃에서 2.16kg의 하중하에 측정),b) melt flow rate (MFR) of 0.5 to 1.0 g / 10 min (measured under a load of 2.16 kg at 230 ° C. according to ISO 1133),
    c) 파단시 인장응력이 10 MPa 이상(250mm/분의 인장속도로 측정),c) tensile stress at break is 10 MPa or more (measured at a tensile speed of 250 mm / min),
    d) 파단시 인장변형율이 500 % 이상(250mm/분의 인장속도로 측정),d) a tensile strain of at least 500% at break (measured at a tensile speed of 250 mm / min),
    e) 굴곡 모듈러스(flexural modulus)가 90 내지 300 MPae) flexural modulus is from 90 to 300 MPa
    f) Vicat 연화점이 55 ℃ 이상(규격 A50에 따라 50℃/h 및 10N에서 측정),f) Vicat softening point of at least 55 ° C (measured at 50 ° C / h and 10 N according to standard A50),
    g) 쇼어 D 경도가 28 이상, 및g) Shore D hardness is at least 28, and
    h) 용융점이 160 내지 165 ℃h) melting point of 160 to 165 캜
PCT/KR2014/001199 2013-02-14 2014-02-13 Power cable WO2014126404A1 (en)

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