EP2117010A1 - Isolierende harzzusammensetzung und draht/kabel damit - Google Patents

Isolierende harzzusammensetzung und draht/kabel damit Download PDF

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Publication number
EP2117010A1
EP2117010A1 EP08721240A EP08721240A EP2117010A1 EP 2117010 A1 EP2117010 A1 EP 2117010A1 EP 08721240 A EP08721240 A EP 08721240A EP 08721240 A EP08721240 A EP 08721240A EP 2117010 A1 EP2117010 A1 EP 2117010A1
Authority
EP
European Patent Office
Prior art keywords
cable
resin composition
insulation
electric wire
relative permittivity
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP08721240A
Other languages
English (en)
French (fr)
Other versions
EP2117010A4 (de
Inventor
Masahiro Minowa
Junichi Nishioka
Minoru Okashita
Masaaki Ueda
Tomoo Ooishi
Nahoko Tanaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SWCC Corp
Original Assignee
SWCC Showa Cable Systems Co Ltd
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.)
Filing date
Publication date
Application filed by SWCC Showa Cable Systems Co Ltd filed Critical SWCC Showa Cable Systems Co Ltd
Publication of EP2117010A1 publication Critical patent/EP2117010A1/de
Publication of EP2117010A4 publication Critical patent/EP2117010A4/de
Withdrawn legal-status Critical Current

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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
    • 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
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers

Definitions

  • the present invention relates to a resin composition for insulation useful as an insulator material or the like for a high voltage cable for X-ray apparatus which connects the X-ray tube of an x-ray apparatus and a high voltage generator, and to an electric wire/cable using the same.
  • the high voltage cable for X-ray apparatus for connecting the X-ray tube of the x-ray apparatus and the high voltage generator is demanded that it has a small outer diameter, light weight, good flexibility, easiness of handling, small electrostatic capacitance of a high voltage insulator, followability to the repeated application of a high voltage, and the like.
  • such a known high voltage cable for X-ray apparatus is formed by stranding two low-voltage insulated conductors and one or two bare conductors, forming an inner semiconductive layer on the stranded conductors, and sequentially forming thereon a high voltage insulator, an outer semiconductive layer, a shielding layer and a sheath.
  • a high voltage insulator an EP rubber (ethylene-propylene rubber) which is flexible and has relatively good electrical characteristics is generally used (see, for example, patent Reference 1).
  • the high voltage insulator may be formed to have a large thickness, but there is a problem that the cable has a large diameter.
  • a material for the high voltage insulator a material having a relative permittivity lower than that of an existing EP rubber (a relative permittivity of about 3.0), for example, crosslinked polyethylene, polyethylene and the like having a relative permittivity of about 2.3 may be used. But, since such insulator materials having a low relative permittivity have large hardness, there is a problem that flexibility of the cable is impaired.
  • a high voltage cable for X-ray apparatus used for a medical CT (computerized tomography) apparatus is required to have heat resistance against heat generation of the X-ray tube, but there is a problem that polyethylene is poor in heat resistance and its application to such usage becomes difficult.
  • the present invention has been made in view of the above circumstances and provides a resin composition for insulation, which is useful as a high voltage insulator material or the like for a high voltage cable for X-ray apparatus and capable of decreasing the electrostatic capacitance of an insulator without increasing a diameter of the cable and without decreasing flexibility and heat resistance, and an electric wire/cable using the same.
  • a resin composition for insulation of the present invention contains a polyolefin as a base polymer, wherein (a) an ash content is 20% by mass or below, (b) a relative permittivity is 2.8 or below, and (c) a type A durometer hardness is 90 or below.
  • An electric wire/cable of the present invention has a coating formed of the above-described resin composition for insulation.
  • the ash content is 10% by mass or below
  • the relative permittivity is 2.6 or below
  • the type A durometer hardness is 80 or below.
  • a tensile strength retention is 80% or more and an elongation retention is 80% or more after heat aging (100°C, 96 hours).
  • a gel fraction is 60% or more.
  • the polyolefin contains an ethylene-propylene rubber.
  • the electric wire/cable is a cable for high-voltage electronics.
  • the present invention can decrease the electrostatic capacitance of the insulator without increasing the diameter of the cable or reducing the flexibility and heat resistance.
  • the individual components composing the resin composition for insulation of the invention and the physical properties of the composition are described below.
  • the physical properties were measured by the following method.
  • polyolefin used as a base polymer of the resin composition for insulation according to the invention are ethylene-propylene rubbers such as ethylene-propylene copolymer (EPM) and ethylene-propylene-diene copolymer (EPDM), polyethylenes such as low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ultralow-density polyethylene (VLDPE) and linear low-density polyethylene (LLDPE), polypropylene (PP), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer (EVA), polyisobutylene and the like.
  • EPM ethylene-propylene copolymer
  • EPDM ethylene-propylene-diene copolymer
  • polyethylenes such as low-dens
  • ethylene copolymerized with ⁇ -olefine or cyclic olefin such as propylene, butene, pentene, hexane or octane by a metallocene catalyst can also be used. They are used alone or as a mixture.
  • the polyolefin is preferably an ethylene-propylene rubber such as an ethylerie-propylene copolymer (EPM), an ethylene-propylene-diene copolymer (EPDM) or the like, and another polyolefin is preferably used as a component used together with the ethylene-propylene rubber.
  • EPM ethylerie-propylene copolymer
  • EPDM ethylene-propylene-diene copolymer
  • the polyolefin is more preferably an ethylene-propylene rubber alone, and even more preferably an ethylene-propylene-diene copolymer (EPDM) alone.
  • EPDM ethylene-propylene-diene copolymer
  • MITSUI EPT trade name, manufactured by MITSUI CHEMICALS, INC.
  • Esprene EPDM trade name, manufactured by SUMITOMO CHEMICAL Co., LTD.
  • the resin composition for insulation according to the invention is coated or formed and has a polymer component crosslinked.
  • a polymer component crosslinked there are a chemical cross-linking method by which a resin composition for insulation is previously added with a cross-linking reagent, formed and crosslinked, an electron beam cross-linking method applying electron beam irradiation, and the like.
  • the cross-linking reagents used to perform the chemical cross-linking method are dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy) valerate, benzoyl oxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide
  • a cross-linking degree is preferably 60% or more at a gel fraction, more preferably 80% or more, and most preferably 85% or more. If the gel fraction is less than 60%, the heat resistance becomes insufficient. For example, when the resin composition of the invention used as the insulator material for the high voltage cable for X-ray apparatus used for the medical CT apparatus, there is a possibility that heat resistance durable to the heat generation of the X-ray tube cannot be obtained.
  • the gel fraction may be measured according to the testing method for degree of cross-linking specified in JIS C 3005.
  • the resin composition for insulation according to the invention may be further blended with inorganic fillers (for example, talc, calcium carbonate, clay, silica, magnesium hydroxide, etc.), processing aids, cross-linking aids, flame retardants, antioxidants, ultraviolet absorbers, coloring agents, softening agents, plasticizers, lubricants, and other additives in a range not inhibiting the effects of the invention, if necessary.
  • inorganic fillers for example, talc, calcium carbonate, clay, silica, magnesium hydroxide, etc.
  • processing aids for example, talc, calcium carbonate, clay, silica, magnesium hydroxide, etc.
  • cross-linking aids for example, flame retardants, antioxidants, ultraviolet absorbers, coloring agents, softening agents, plasticizers, lubricants, and other additives in a range not inhibiting the effects of the invention, if necessary.
  • the resin composition for insulation of the invention has (a) an ash content of 20% by mass or below, preferably 10% by mass or below, more preferably 5% by mass or below, and most preferably 3% by mass or below. If the ash content exceeds 20% by mass, a relative permittivity increases, and the electrostatic capacitance of the insulator cannot be decreased.
  • the resin composition for insulation of the invention has (b) a relative permittivity of 2.8 or below, preferably 2.6 or below, and more preferably 2.4 or below. If the relative permittivity exceeds 2.8, the electrostatic capacitance of the insulator cannot be decreased without involving an increase of the diameter of the cable.
  • the resin composition for insulation of the invention has (c) a type A durometer hardness of 90 or below, preferably 80 or below, and more preferably 70 or below. If the type A durometer hardness exceeds 90, flexibility and ease in handling of the cable are degraded.
  • the resin composition for insulation of the invention has a tensile strength retention and an elongation retention after (d) heat aging (100°C, 96 hours) each of preferably 80% or more, and more preferably 90% or more. If either the tensile strength retention or the elongation retention after the heat aging (100°C, 96 hours) is less than 80%, the heat resistance becomes insufficient, and thus it becomes difficult to apply to the insulator material for the high voltage cable for X-ray apparatus, which is used for the medical CT apparatus.
  • the resin composition for insulation of the invention can be produced easily by kneading homogeneously the above-described individual components by an ordinary kneader such as a Banbury mixer, a tumbler, a pressurizing kneader, a kneading extruder, a mixing roller or the like.
  • an ordinary kneader such as a Banbury mixer, a tumbler, a pressurizing kneader, a kneading extruder, a mixing roller or the like.
  • the obtained composition is coated on the outer periphery of the conductor directly or via another coating by extruding or wound in a tape shape to produce the electric wire/cable of the invention.
  • the composition is preferably crosslinked after coating or after forming.
  • FIG. 1 is a transverse sectional view showing a high voltage cable for x-ray apparatus of an embodiment of the electric wire/cable of the invention.
  • 1 denotes a low-voltage core
  • the low-voltage core 1 is composed of, for example, a conductor 1a having a cross-sectional area of 1.8 mm 2 which is formed by concentric stranding of 19 tin-coated annealed copper wires having a diameter of 0.35 mm, and an insulator 1b having a thickness of, for example, 0.25 mm which is formed of, for example, a fluorine resin such as polytetrafluoroethylene, and formed on the conductor 1a.
  • a conductor 1a having a cross-sectional area of 1.8 mm 2 which is formed by concentric stranding of 19 tin-coated annealed copper wires having a diameter of 0.35 mm
  • an insulator 1b having a thickness of, for example, 0.25 mm which is formed of, for example, a fluorine resin such as polytetrafluoroethylene, and formed on the conductor 1a.
  • 2 denotes a high-voltage core, which is composed of a bare conductor 2a having a cross-sectional area of 1.25 mm 2 which is formed by, for example, concentric stranding of 50 tin-coated annealed copper wires having a diameter of 0.18 mm.
  • a semiconductive coating may be formed on the bare conductor 2a, if necessary.
  • the inner semiconductive layer 3 and the outer semiconductive layer 5 are formed by, for example, winding a semiconductive tape formed of a nylon substrate, a polyester substrate or the like and/or extrusion coating of a general-purpose semiconductive ethylene-propylene rubber, and the high voltage insulator 4 is formed by extrusion coating of the above-described resin composition for insulation.
  • the inner semiconductive layer 3 is determined to have an outer diameter of, for example, 5.0 mm, and the high voltage insulator 4 and the outer semiconductive layer 5 each are coated to have, for example, a thickness of 4.4 mm and 0.2 mm.
  • the outer semiconductive layer 5 has thereon, for example, a shielding layer 6 having a thickness of 0.3 mm composed of a braid of tin-coated annealed copper wires, and additionally has thereon, for example, a sheath 7 having a thickness of 1.0 mm formed by extrusion coating of a vinyl chloride resin.
  • the above-configured high voltage cable for X-ray apparatus has the high voltage insulator 4 formed of the resin composition for insulation having a relative permittivity of 2.8 or below and a type A durometer hardness of 90 or below. Therefore, the electrostatic capacitance of the high voltage insulator 4 can be made smaller than that of the conventional high voltage insulator, the cable flexibility does not become low, and the cable outer diameter can be made to be substantially the same as the conventional cable.
  • a cable for high-voltage electronics suitable as a high voltage cable for X-ray apparatus can be provided without increasing the thickness of the high voltage insulator (i.e. without increasing the cable outer diameter). If it is sufficient by having the same electrostatic capacitance as the conventional electrostatic capacitance, the outer diameter of the high voltage insulator can be decreased within a range not affecting the insulation performance. Namely, the cable can be reduced to have a small diameter and a light weight, and a cable for high-voltage electronics which is good in flexibility and easy to handle can be provided.
  • Examples of the cables for high-voltage electronics include a high voltage cable for X-ray apparatus used for the X-ray apparatus and a high-voltage DC cable used for the high-voltage DC circuit of an electron beam welding device, an electric discharge machining device, an electrostatic coating device, a vacuum deposition device and the like.
  • FIG. 2 and FIG. 3 each are transverse sectional views showing a high voltage cable for X-ray apparatus of another embodiment of the electric wire/cable of the invention.
  • the high voltage cable for X-ray apparatus shown in FIG. 2 is configured in the same manner as the high voltage cable for X-ray apparatus shown in FIG. 1 except that the core portion 8 is configured by stranding two low-voltage cores 1 and one high-voltage core 2 (the drawing shows an example that a semiconductive coating 2b is formed on the bare conductor 2a).
  • the high voltage cable for X-ray apparatus shown in FIG. 3 is an example of a so-called single core cable, which has a structure that the core portion 8 is formed of the conductor 2a only, and the inner semiconductive layer 3, the high voltage insulator 4, the outer semiconductive layer 5, the shielding layer 6 and the sheath 6 are sequentially formed on the conductor 2a.
  • the electrostatic capacitance of the high voltage insulator 4 can be made smaller than that of the conventional cable, the cable flexibility is not lowered, and the cable outer diameter can be made substantially the same as that of the conventional cable.
  • a cable for high-voltage electronics suitable as a high voltage cable for X-ray apparatus can be provided without increasing the thickness of the high voltage insulator (i.e. without increasing the cable outer diameter). If it is sufficient by having the same electrostatic capacitance as the conventional one, the outer diameter of the high voltage insulator can be decreased within the range not affecting the insulation performance. Namely, the cable can be reduced to have a small diameter and a light weight, and a cable for high-voltage electronics which is good in flexibility and easy to handle can be provided.
  • Examples 1 to 7, Comparative Examples 1 to 3 As a base polymer, EPDM (manufactured by MITSUI CHEMICALS, INC., trade name MITSUI EPT1045), as an inorganic filler, talc (manufactured by TAKEHARA KAGAKU KOGYO CO., LTD., trade name Hytron), as a softening agent, a process oil (manufactured by Idemitsu Kosan Co., Ltd., trade name Diana Process Oil PW-90) and as a cross-linking reagent, dicumyl peroxide (manufactured by NOF CORPORATION, trade name PERCUMYL D), which is one type of organic peroxide, were used. They were kneaded homogeneously at the ratios shown in Table 1 by a mixing roll and extruded into a sheet form.
  • EPDM manufactured by MITSUI CHEMICALS, INC., trade name MITSUI EPT1045
  • talc manufactured by
  • test sheets were crosslinked by application of heat and pressure by a press machine under conditions of 170°C x 30 minutes and a pressure of 19 MPa to produce test sheets.
  • the test sheets were produced in two types having thickness of 0.5 mm and 2 mm.
  • test sheets were evaluated by measuring an ash content, a gel fraction, a type A durometer hardness, a relative permittivity, and also a tensile strength retention and elongation retention after heat aging (100°C, 96 hours).
  • the test sheet having thickness of 2 mm was used in only the heat aging test. The results are shown in the lower half columns of Table 1.
  • EPDM MITSUI EPT1045
  • silica manufactured by TOSOH SILICA CORPORATION, trade name Nip Seal VN3
  • a process oil Diana Process Oil PW-90
  • a cross-linking reagent dicumyl peroxide (PERCUMYL D) which is one type of organic peroxide, were used. They were kneaded homogeneously at the ratios shown in Table 2 by a mixing roll and extruded into a sheet form.
  • test sheets were crosslinked by application of heat and pressure by a press machine under conditions of 170°C x 30 minutes and a pressure of 19 MPa to produce test sheets.
  • the test sheets were produced in two types having thickness of 0.5 mm and 2 mm.
  • test sheets were evaluated by measuring an ash content, a gel fraction, a type A durometer hardness, a relative permittivity, and also a tensile strength retention and elongation retention after heat aging (100°C, 96 hours).
  • the test sheet having a thickness of 2 mm was used in only the heat aging test. The results are shown in the lower half columns of Table 2.
  • Comparative Examples 4 to 6 having an ash content of exceeding 20% by mass had a relative permittivity of 3.0 or more even when silica was used as an inorganic filler
  • Examples 8 to 13 having an ash content of 20% by mass or below, a type A durometer hardness of 90 or below and a relative permittivity of 2.8 or below had a type A durometer hardness of 90 or below and a relative permittivity of 2.8 or below.
  • Examples 8 to 13 had both low hardness required to provide the cable with flexibility and a low relative permittivity required to achieve a cable having both a small diameter and a low electrostatic capacitance.
  • Examples 8 to 13, in which a tensile strength retention and elongation retention after heat aging (100°C, 96 hours) were 80% or more and a gel fraction was 60% or more, also had good heat resistance.
  • the resin composition for insulation of the invention can be used extensively for an electrical insulating material and a sheath material of various kinds of electric wires/cables such as power cables, cables for high-voltage electronics, cables for control, cables for communications, cables for instrumentation, cables for signals, cables for moving and the like, and also for usages requiring electrical insulation such as electric wire/cable attachments such as plugs.
  • the resin composition for insulation of the invention has a small relative permittivity and excellent flexibility, it is useful as an insulator material of a cable for high-voltage electronics, such as a high voltage cable for X-ray apparatus, a high-voltage DC cable, and the like.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
EP08721240A 2007-03-06 2008-03-04 Isolierende harzzusammensetzung und draht/kabel damit Withdrawn EP2117010A4 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007055864 2007-03-06
PCT/JP2008/053820 WO2008108355A1 (ja) 2007-03-06 2008-03-04 絶縁用樹脂組成物およびこれを用いた電線・ケーブル

Publications (2)

Publication Number Publication Date
EP2117010A1 true EP2117010A1 (de) 2009-11-11
EP2117010A4 EP2117010A4 (de) 2012-06-27

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EP08721240A Withdrawn EP2117010A4 (de) 2007-03-06 2008-03-04 Isolierende harzzusammensetzung und draht/kabel damit

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EP (1) EP2117010A4 (de)
JP (1) JPWO2008108355A1 (de)
WO (1) WO2008108355A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9165697B2 (en) 2012-11-20 2015-10-20 Hitachi Metals, Ltd. Peroxide crosslinked resin composition and electric wire and cable using same
EP2584568A4 (de) * 2010-06-18 2017-05-17 Swcc Showa Cable Systems Co., Ltd. Kabel für elektronische hochspannungsvorrichtungen
CN106971768A (zh) * 2017-05-13 2017-07-21 中天科技装备电缆有限公司 一种新能源汽车内部用高压电缆及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5438332B2 (ja) * 2009-02-05 2014-03-12 昭和電線ケーブルシステム株式会社 高電圧電子機器用ケーブル

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4138889A1 (de) * 1991-01-30 1992-08-13 Felten & Guilleaume Energie Roentgenleitung
JP3053233B2 (ja) * 1991-02-22 2000-06-19 三菱電線工業株式会社 耐放射線性組成物
JPH07330990A (ja) * 1994-06-08 1995-12-19 Sumitomo Electric Ind Ltd 電力ケーブル機器用ゴム材料
JPH0822717A (ja) * 1994-07-05 1996-01-23 Fujikura Ltd 電気絶縁組成物
DE19641396B4 (de) * 1996-09-27 2007-08-16 Pirelli Cavi E Sistemi S.P.A. Vernetzbare Isoliermischung für elektrische Kabel und Leitungen
JP2002245866A (ja) 2001-02-20 2002-08-30 Hitachi Cable Ltd レントゲンケーブル
JP2002363361A (ja) * 2001-06-04 2002-12-18 Fujikura Ltd 透明性樹脂組成物および透明性絶縁シート
JP2007055864A (ja) 2005-08-26 2007-03-08 National Institute Of Advanced Industrial & Technology 圧電磁器組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2584568A4 (de) * 2010-06-18 2017-05-17 Swcc Showa Cable Systems Co., Ltd. Kabel für elektronische hochspannungsvorrichtungen
US9165697B2 (en) 2012-11-20 2015-10-20 Hitachi Metals, Ltd. Peroxide crosslinked resin composition and electric wire and cable using same
CN106971768A (zh) * 2017-05-13 2017-07-21 中天科技装备电缆有限公司 一种新能源汽车内部用高压电缆及其制备方法

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WO2008108355A1 (ja) 2008-09-12
JPWO2008108355A1 (ja) 2010-06-17
EP2117010A4 (de) 2012-06-27

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