WO2017078430A1 - Composition isolante présentant une excellente reprise de la forme originale et d'excellentes propriétés mécaniques, et câble portant une couche isolante formée à partir de cette composition - Google Patents

Composition isolante présentant une excellente reprise de la forme originale et d'excellentes propriétés mécaniques, et câble portant une couche isolante formée à partir de cette composition Download PDF

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Publication number
WO2017078430A1
WO2017078430A1 PCT/KR2016/012597 KR2016012597W WO2017078430A1 WO 2017078430 A1 WO2017078430 A1 WO 2017078430A1 KR 2016012597 W KR2016012597 W KR 2016012597W WO 2017078430 A1 WO2017078430 A1 WO 2017078430A1
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insulation
composition
cable
weight
conductor
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PCT/KR2016/012597
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English (en)
Korean (ko)
Inventor
고창모
김종완
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엘에스전선 주식회사
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Priority claimed from KR1020160145611A external-priority patent/KR20170053581A/ko
Publication of WO2017078430A1 publication Critical patent/WO2017078430A1/fr

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation

Definitions

  • the present invention relates to a cable having an insulating composition excellent in circular recovery and mechanical properties and an insulating layer formed therefrom. Specifically, the present invention not only suppresses deformation under the conditions of high temperature and high pressure during chemical crosslinking of the sheath layer, but also has excellent circular recovery after deformation, and also has excellent mechanical properties in conflict with this, and further excellent in water resistance.
  • FIG. 1 schematically illustrates a cross-sectional structure of one embodiment of a typical cable
  • FIG. 2 schematically illustrates a cross-sectional structure of another embodiment of a typical cable.
  • the cable comprises a conductor (10, 10 ') through which a current flows, an insulating layer (20, 20') surrounding the conductor (10, 10 '), and the cable from external pressure or impact. It may include a sheath layer (30, 30 ') and the like.
  • the sheath layer (30, 30 ') must have a certain level or more of mechanical properties to protect the cable from external pressure or impact, and on the insulating layer (20, 20') to implement such mechanical properties It is usually crosslinked after extrusion.
  • the cross-linking method of the sheath layer 30, 30 ' is irradiation crosslinking to crosslink the resin by ultraviolet irradiation, silane crosslinking (water crosslinking) to crosslink the resin in water using a silane compound, and organic peroxide under high temperature and high pressure. Chemical crosslinking to crosslink the resin using a crosslinking agent.
  • irradiation crosslinking has a problem in that crosslinking does not proceed uniformly to the inside of the sheath layers 30 and 30 'due to the low transmittance of the irradiation beam when the sheath layers 30 and 30' are thick.
  • the silane crosslinking (water crosslinking) takes a long time, and when the crosslinking reaction proceeds in water, side reactions may occur due to moisture absorption of the sheath layers 30 and 30 ', and a silane graft reaction to the resin may occur. If the silane graft reaction is too difficult to control the scorch occurs, or if the silane graft reaction is less than the standard cross-linking degree often occurs, it may be difficult to apply the mass production.
  • the chemical crosslinking method is widely applicable and relatively easy to manufacture the raw material, while the deformation of the insulating layer (20, 20 ') under the conditions of high temperature and high pressure for the crosslinking reaction, that is 150 ⁇ 230 °C and 6 ⁇ 20 bar This may occur, resulting in poor withstand voltage.
  • the deformation may be more severe due to mutual crushing of the insulating layers 20' surrounding each conductor 10 '.
  • a resin having a low strain at high temperature and high pressure and excellent circular recovery after deformation as a basic resin for forming the insulating layers 20 and 20 ', but has a low temperature and high pressure strain and a circular recoverability.
  • This superior resin cannot be applied to an insulating layer that typically requires a tensile strength of 10 MPa and a high tensile strength of 12.5 MPa.
  • an additive is added to improve the tensile strength of the insulating layers 20 and 20 ', the water resistance of the insulating layers 20 and 20' may be greatly reduced.
  • the high temperature and high strain rate is excellent and the circular recovery is excellent, and also has the excellent mechanical properties that can be applied to the insulating layer which requires a high tensile strength of the product specification of 12.5 MPa, further improved insulation composition and insulation formed therefrom There is an urgent need for cables with layers.
  • An object of the present invention is to provide an insulation composition having a low high temperature and high strain rate and excellent circular recovery and a cable having an insulation layer formed therefrom.
  • an object of the present invention is to provide a cable having an insulating composition and an insulating layer formed therefrom, which has an elasticity for achieving low high temperature and high strain rate and excellent circular recovery, and which has excellent mechanical properties in conflict with it.
  • An insulation composition for forming the insulation layer of a cable comprising at least one conductor and an insulation layer surrounding each conductor, the insulation composition comprising an olefin-based copolymer as a base resin, wherein the insulation layer formed from the insulation composition is The resulting high temperature and high strain is less than 95%, providing an insulating composition.
  • a is the initial (insulation outer diameter-conductor outer diameter)
  • b is pressurizing the cable at 160 °C for 1 hour to compress the insulating layer so that the outer diameter of each of the insulating layer to (conductor outer diameter + c), and the cable is cooled to room temperature while maintaining the pressure, It is the minimum value of (insulated outer diameter-outer diameter of conductor) measured under the condition that pressure is removed.
  • c is the pressure (insulation outer diameter-conductor outer diameter) at the time of pressing the insulating layer formed from the said insulating composition on the said conditions.
  • c is an insulation composition, characterized in that 0.5a to 0.8a.
  • the insulation layer provides an insulation composition, characterized in that the tensile strength is 12.5 MPa or more.
  • two conductors having a cross-sectional area of 0.75 mm2 are united so that a specified value is obtained by applying a 60 Hz sinusoidal alternating voltage to a conductor sock end of a cable specimen having a total conductor diameter of 1.107 mm and an insulating layer formed from the insulating composition and having a thickness of 0.5 mm. It provides an insulating composition, characterized in that the breakdown does not occur for a specified time of 5 minutes after slowly rising to 1.5 kV.
  • the olefin copolymer has a melting point of 50 to 100 ° C. and a melt index of 1 to 8 g / min.
  • the olefin copolymer provides an insulation composition, characterized in that it comprises a copolymer of ethylene and other ⁇ -olefins.
  • the olefin copolymer provides an insulating composition, characterized in that it comprises an ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, or a combination thereof.
  • the base resin based on 100 parts by weight of the base resin, characterized in that it further comprises 30 to 250 parts by weight of one or more fillers selected from the group consisting of clay, talc, calcium carbonate, magnesium hydroxide, aluminum hydroxide, silica and zinc borate. , To provide an insulation composition.
  • the filler provides an insulating composition, characterized in that the surface is hydrophobically modified by at least one selected from the group consisting of alkyl silanes, vinyl silanes and fatty acids.
  • the cable specimens were based on the initial tan ⁇ of the insulation layer.
  • the increase rate of tan ⁇ of the insulating layer after immersion in a 75 ° C. water bath for 14 days was 50% or less, and the cable specimen was immersed in water at a specified temperature of 90 ⁇ 1 ° C., so that the insulating layer temperature became constant.
  • an insulation composition characterized in that the high temperature insulation resistance measured after charging for 1 minute by applying a DC voltage is 1.3 M ⁇ -km or more.
  • the filler provides an insulation composition, characterized in that the particle size (D 50 ) is 0.6 to 6 ⁇ m.
  • the base resin based on 100 parts by weight of the base resin, characterized in that it further comprises 0.3 to 3 parts by weight of a silane coupling agent having a viscosity of 1 to 20 cps at 25 °C, provides an insulation composition.
  • the content of the silane coupling agent is 1/10 or more of the filler content, provides an insulation composition.
  • the base resin based on 100 parts by weight of the base resin, characterized in that it further comprises 60 parts by weight or less of one or more processing oils selected from the group consisting of alkyl ester oil, paraffin oil and paraffin wax, provides an insulation composition.
  • dicumyl peroxide based on 100 parts by weight of the base resin, dicumyl peroxide, benzoyl peroxide, aryl peroxide, t- butyl cumyl peroxide, di (t- butyl peroxy isopropyl) benzene, 2,5-dimethyl-2, It further comprises 1 to 10 parts by weight of at least one crosslinking agent selected from the group consisting of 5-di (t-butyl peroxy) hexane and di-t-butyl peroxide, an insulation composition is provided.
  • phenol-based, zinc-based, quinone-based, sulfur-based or phosphorus-based antioxidant based on 100 parts by weight of the base resin, phenol-based, zinc-based, quinone-based, sulfur-based or phosphorus-based antioxidant, characterized in that it further comprises 1 to 10 parts by weight.
  • At least one conductor At least one conductor; An insulation layer surrounding each of the conductors and formed from the insulation composition; And a sheath layer surrounding the insulation layer as a whole.
  • the insulating composition according to the present invention is formed from a resin having low high temperature high pressure strain and excellent circular recoverability, the strain of the insulating layer is minimized even under conditions of high temperature and high pressure during chemical crosslinking of the sheath layer, and is insulated by circular recovery after deformation. It shows an excellent effect that the strength is maintained.
  • the insulating composition according to the present invention exhibits an excellent effect of improving the mechanical properties while maintaining the high temperature and high strain rate and circular recovery of the insulating layer by including a specific additive in addition to the resin in a specific blending ratio.
  • the insulating composition according to the present invention exhibits an excellent effect that the water resistance is not lowered by an additive for improving mechanical properties.
  • Figure 1 schematically shows a cross-sectional structure of one embodiment of a typical cable.
  • Figure 2 schematically shows the cross-sectional structure of another embodiment of a typical cable.
  • the present invention relates to an insulating composition for forming an insulating layer of a cable.
  • the insulation composition may include an olefin resin as a basic resin.
  • the olefin resin is preferably a copolymer of ethylene with other ⁇ -olefins, such as ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, or their Combinations.
  • the copolymer of ethylene and an ⁇ -olefin may have a melting point of 50 to 100 ° C. and a melt index of 1 to 8 g / min.
  • the cable having one or more conductors and an insulation layer formed from the insulation composition respectively surrounding the conductors may have a high temperature and high strain rate of the insulation layer defined by Equation 1 below.
  • a is the initial (insulation outer diameter-conductor outer diameter)
  • b is pressurizing the cable at 160 °C for 1 hour to compress the insulating layer so that the outer diameter of each of the insulating layer to (conductor outer diameter + c), and the cable is cooled to room temperature while maintaining the pressure, It is the minimum value of (insulated outer diameter-outer diameter of conductor) measured under the condition that pressure is removed.
  • c is a pressure (insulation outer diameter-conductor outer diameter) when the insulating layer formed from the insulating composition is pressed under the above conditions, and c is, for example, 0.5a to 0.8a, and is typically 0.75a.
  • the insulating composition may be formed of the insulating layer formed from the insulating composition when chemically crosslinking the sheath layer at a high temperature of 150 to 230 ° C. and a high pressure of 6 to 20 bar when the high temperature and high pressure strain of the insulating layer defined by Equation 1 is less than 95%.
  • the deformation is suppressed and the circular recovery property after deformation is excellent to maintain the insulation strength of the insulating layer.
  • the insulation composition may further include a filler, a silane coupling agent, a processing oil, a crosslinking agent, an antioxidant, and the like in addition to the basic resin.
  • the filler may further improve the mechanical properties and extrudability of the insulation composition, for example, selected from the group consisting of clay, talc, calcium carbonate, magnesium hydroxide, aluminum hydroxide, silica, zinc borate, etc. It may include more than one species, and the surface may be modified hydrophobicly by alkyl silane, vinyl silane, fatty acid, etc. to improve compatibility with the base resin.
  • the cable specimens were based on the initial tan ⁇ of the insulation layer.
  • the increase rate of tan ⁇ of the insulating layer after immersion in a 75 ° C. water bath for 14 days was 50% or less, and the cable specimen was immersed in water at a specified temperature of 90 ⁇ 1 ° C., so that the insulating layer temperature became constant.
  • the high temperature insulation resistance measured after charging for 1 minute by applying a DC voltage is 1.3 M ⁇ -km or more can be achieved excellent water resistance.
  • the surface of the filler is not modified to be hydrophobic and the compatibility with the base resin is lowered, the tensile strength, electrical properties, circular recovery of the insulating layer may be lowered, and further, the water resistance of the insulating layer may be lowered.
  • the filler is adjusted to a particle diameter (D 50 ) of 0.6 to 6 ⁇ m or less can be suppressed from agglomeration in the resin, thereby improving the surface roughness during the extrusion of the cable.
  • the filler may be included in an amount of 30 to 250 parts by weight based on 100 parts by weight of the base resin. If the content of the filler is less than 30 parts by weight, the surface roughness of the appearance may be reduced during cable extrusion, whereas if it is more than 250 parts by weight, mechanical properties such as elongation of the insulating layer may be lowered and flexibility may be reduced.
  • the silane coupling agent performs a function of further improving the compatibility of the filler and the base resin, and may have, for example, both functional groups such as vinyl and alkyl and functional groups of silane.
  • the silane coupling agent may have a viscosity of 1 to 20 cps at 25 °C to smoothly perform the function of further improving the compatibility of the filler and the base resin.
  • the content of the silane coupling agent may be 0.3 to 3 parts by weight based on 100 parts by weight of the base resin, and preferably about 1/10 or more of the filler content.
  • the content of the silane coupling agent is less than 0.3 parts by weight, the compatibility of the filler and the base resin may be insufficient, whereas when the content of the silane coupling agent is more than 3 parts by weight, the elongation rate, flexibility, and the like of the insulating layer may be reduced.
  • the processing oil further functions to further improve the extrudability of the cable and to improve the compatibility of the base resin with the additive.
  • the processed oil may include, for example, alkyl ester oil, paraffin oil, paraffin wax, or a combination thereof, and may be included in an amount of 60 parts by weight or less based on 100 parts by weight of the base resin. When the content of the processing oil exceeds 60 parts by weight, the mechanical strength of the insulating layer may be lowered.
  • the crosslinking agent may be added for crosslinking of the base resin included in the insulating composition and may improve mechanical properties of the insulating layer through crosslinking of the base resin.
  • the crosslinking agent is, for example, dicumyl peroxide, benzoyl peroxide, aryl peroxide, t-butyl cumyl peroxide, di (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t Organic peroxide-based crosslinking agents such as -butyl peroxy) hexane, di-t-butyl peroxide, or a combination thereof, and may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the base resin.
  • the content of the crosslinking agent When the content of the crosslinking agent is less than 1 part by weight, the mechanical strength of the insulating layer may be insufficient, whereas when the content of the crosslinking agent is greater than 10 parts by weight, the extrudeability such as scorch is generated by early crosslinking during extrusion of the insulating layer. Deterioration or cross-linking by-products may lower the electrical properties of the insulating layer.
  • the antioxidant is added to prevent deterioration due to oxidation of the insulating layer, for example, phenol-based, zinc-based, quinone-based, sulfur-based, phosphorus-based, etc. may be used, 100 parts by weight of the base resin It may be included in 1 to 10 parts by weight as a standard.
  • the insulating composition according to the present invention includes a filler, a silane coupling agent, a processing oil, a crosslinking agent, an antioxidant, and the like in addition to the base resin to maintain the high temperature and high strain rate and circular recovery of the base resin. It shows an excellent effect that can achieve the desired tensile strength of 12.5 MPa or more of the formed insulating layer.
  • the present invention consists of a conductive material capable of flowing current, for example, a metal such as copper or aluminum to provide a current flow path, an insulating layer surrounding the conductor and formed by the above-described insulating composition, the insulating layer
  • the present invention relates to a cable including a sheath layer for enclosing the shield and protecting the cable from external shock or pressure.
  • Each insulation composition was prepared after kneading in an open roll at 80 ° C. with the components and blending ratios as shown in Table 1 below, and extruded onto a conductor to be crosslinked by pressurized heating at 170 ° C. for 20 minutes to IEC-60811-1-1.
  • a cable specimen (conductor: 0.75 sq two total outer diameters of 1.107 mm; insulation layer: thickness 0.5 mm) was prepared.
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Resin a 70 30 70 70 90 Resin b 30 70 30 70 Resin c 30 30 10 100 Filler a 60 60 60 60 60 60 60 Filler b 60 Silane coupling agent One One One One One One One One One One Processing oil 5 5 5 5 5 5 5 5 5 5 5 Antioxidant 6 6 6 6 6 6 6 Crosslinking agent 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
  • Resin a Ethylene copolymer (ethylene content: 40-71 wt%)
  • Resin b ethylene-propylene copolymer
  • Resin c ethylene homopolymer
  • Filler a calcined clay (aluminosilicate) surface treated with vinylsilane (particle diameter (D 50 ) ⁇ 2.2 ⁇ m)
  • Filler b calcined clay (aluminosilicate) without surface treatment (particle diameter (D 50 ) ⁇ 2.2 ⁇ m)
  • Processing oil paraffin oil
  • Antioxidants zinc oxide (ZnO) and trimellitatequinoline (TMQ)
  • the tensile strength and elongation of the insulation specimens separated from the cable specimens of each of the Examples and Comparative Examples were measured at a tensile rate of 250 mm / min at room temperature (about 25 ° C).
  • This test method was developed by devising a method of measuring the strain due to heating pressure on an insulated cable by modifying the compressive permanent shrinkage test method specified in Clause 11 of KS M 6518 Physical Test Method of Vulcanized Rubber. The high temperature, high pressure strain of the specimen was evaluated.
  • the initial (insulation outer diameter-outer diameter of the conductor) of each of the cable specimens of Examples and Comparative Examples was measured, and using a press at 160 ° C. so that the cable outer diameter was ⁇ initial (insulation outer diameter-outer diameter of the conductor) * 0.75 ⁇ .
  • the press is cooled to room temperature and left to stand for at least 1 hour while maintaining pressurization to completely cool the specimen, and remove the specimen from the press to remove the pressurization and then remove the minimum value of (insulated outer diameter-conductor outer diameter).
  • the high temperature high pressure strain according to the above formula (1) was calculated.
  • f is the frequency of the measurement power supply
  • R is the scale ( ⁇ ) of the inductive variable resistor when the bridge is in equilibrium.
  • dielectric tangent tantan may be expressed as an absolute value.
  • the cables of Examples 1 and 2 according to the present invention are both less than 95% of the high temperature and high pressure strain of the insulating layer, so that deformation is suppressed even under high temperature and high pressure environments applied during chemical crosslinking of the sheath layer. It is excellent in the original recovery after deformation and can maintain the dielectric strength during chemical crosslinking of the sheath layer. The shape of the insulating layer was maintained, and the results of the breakdown voltage test were also good.
  • the tensile strength of the insulating layer is 12.5 MPa or more can be used as a cable that requires a high tensile strength of the product specification of 12.5 MPa, and even after immersion, the tan ⁇ increase rate is low and the high temperature insulation resistance value is high, so that the insulating layer has excellent water resistance. Confirmed.
  • Comparative Example 1 since the surface of the filler is not hydrophobically modified, the compatibility with the base resin is lowered, the tensile strength of the insulating layer is lowered, the tan ⁇ is significantly increased after immersion, and the high temperature insulation resistance is considerably decreased, so that the insulating layer has high water resistance. It was confirmed that this was greatly reduced.
  • Comparative Examples 2 to 5 including the ethylene homopolymer as the base resin, was almost completely deformed at high temperature and pressure, it was confirmed that the high temperature and high pressure strain significantly decreased.
  • the circular shape of the insulating layer was not maintained on the cable and was deformed into a completely crushed shape, so that the electrical insulation of the inner conductor was not maintained.
  • the result of the withstand voltage test was bad and the resistance value was nearly 0 at the time of the high temperature insulation resistance test. It became.

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  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition isolante présentant une excellente reprise de la forme originale et d'excellentes propriétés mécaniques, et un câble portant une couche isolante formée à partir de cette composition. En particulier, la présente invention concerne : une composition isolante, qui supprime une déformation dans des conditions de température élevée et de tension élevée pendant la réticulation chimique d'une couche de gaine, présente une excellente reprise de la forme originale après déformation et présente simultanément d'excellentes propriétés mécaniques, qui sont en relation de compromis avec la reprise de la forme originale, et en outre, présente une excellente résistance à l'eau ; et un câble portant une couche isolante formée à partir de cette composition.
PCT/KR2016/012597 2015-11-06 2016-11-03 Composition isolante présentant une excellente reprise de la forme originale et d'excellentes propriétés mécaniques, et câble portant une couche isolante formée à partir de cette composition WO2017078430A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20150155579 2015-11-06
KR10-2015-0155579 2015-11-06
KR1020160145611A KR20170053581A (ko) 2015-11-06 2016-11-03 원형회복성 및 기계적 특성이 우수한 절연 조성물 및 이로부터 형성된 절연층을 갖는 케이블
KR10-2016-0145611 2016-11-03

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WO2017078430A1 true WO2017078430A1 (fr) 2017-05-11

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR860700178A (ko) * 1984-05-03 1986-03-31 케이블용 절연체 조성물
KR100286531B1 (ko) * 1998-06-23 2001-04-16 권문구 고압 내열 배전 가공선
KR20050110407A (ko) * 2004-05-18 2005-11-23 엘에스전선 주식회사 내열변형 및 내 컷스루우 수지 조성물 및 이를 이용한절연재료와 전선
KR20050117068A (ko) * 2004-06-09 2005-12-14 엘에스전선 주식회사 연소시 흘러내림이 없고 저발연성이 우수한 난연 조성물및 이를 이용한 전선

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR860700178A (ko) * 1984-05-03 1986-03-31 케이블용 절연체 조성물
KR100286531B1 (ko) * 1998-06-23 2001-04-16 권문구 고압 내열 배전 가공선
KR20050110407A (ko) * 2004-05-18 2005-11-23 엘에스전선 주식회사 내열변형 및 내 컷스루우 수지 조성물 및 이를 이용한절연재료와 전선
KR20050117068A (ko) * 2004-06-09 2005-12-14 엘에스전선 주식회사 연소시 흘러내림이 없고 저발연성이 우수한 난연 조성물및 이를 이용한 전선

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