WO2015182106A1 - Vehicle-mounted electrical wire and cable - Google Patents

Vehicle-mounted electrical wire and cable Download PDF

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Publication number
WO2015182106A1
WO2015182106A1 PCT/JP2015/002617 JP2015002617W WO2015182106A1 WO 2015182106 A1 WO2015182106 A1 WO 2015182106A1 JP 2015002617 W JP2015002617 W JP 2015002617W WO 2015182106 A1 WO2015182106 A1 WO 2015182106A1
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Prior art keywords
parts
mass
resin composition
vehicle
ethylene
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PCT/JP2015/002617
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French (fr)
Japanese (ja)
Inventor
伸明 光地
道朝 藤田
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昭和電線ケーブルシステム株式会社
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Priority to CN201580025881.5A priority Critical patent/CN106463206B/en
Publication of WO2015182106A1 publication Critical patent/WO2015182106A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/378—Thiols containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • 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
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • 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
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame

Definitions

  • the present invention relates to an in-vehicle electric wire / cable excellent in flexibility and heat resistance.
  • HEV Hybrid Electric Vehicle
  • Electric wires and cables used for HEV are required to have high heat resistance due to the positional relationship between the engine and the motor. Specifically, heat resistance that satisfies the required characteristics of ISO 6722, Class D or more of the automotive electric wire standard is required. Moreover, since wiring is performed in a narrow space at the same time, excellent flexibility is required.
  • Fluorine resins and silicone resins are also used for some automotive applications as having excellent heat resistance.
  • fluororesins are very hard and cause problems in the routing.
  • a silicone resin has flexibility, since it is low in strength, defects are likely to occur during routing.
  • in-vehicle electric wire / cable having sufficiently high heat resistance and sufficiently high flexibility has not been obtained yet.
  • in-vehicle electric wires and cables are also required to have characteristics such as mechanical strength, wear resistance, and flame retardance as described above.
  • the present invention has been made to solve the problems of the prior art, and has high heat resistance and high flexibility, and further has excellent mechanical strength, wear resistance, flame retardancy, and the like. ⁇
  • the purpose is to provide cables.
  • an ethylene-based copolymer including an ethylene / ethyl acrylate copolymer has two specific antioxidants and a specific bromine-based copolymer. It has been found that by using a resin composition combined with a flame retardant as a coating material, an electric wire / cable having both high heat resistance and high flexibility can be obtained, and the present invention has been completed.
  • the in-vehicle electric wire / cable according to the first aspect of the present invention has 2.0 to 9 as an antioxidant with respect to 100 parts by mass of an ethylene-based copolymer containing an ethylene / ethyl acrylate copolymer on the outer periphery of the conductor.
  • a coating comprising a crosslinked product of a resin composition containing 15.0 to 35.0 parts by mass of 1,2-bis (tetrabromophthalimide) ethane as a flame retardant is provided.
  • the resin composition in the flame-retardant electric wire / cable according to the first aspect, may be pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] is 3.0 to 7.0 parts by mass, 2-mercaptobenzimidazole is 3.0 to 7.0 parts by mass, 1,2-bis (tetrabromophthalimide) It contains 25.0-35.0 parts by mass of ethane.
  • the resin composition in the in-vehicle electric wire / cable of the first aspect or the second aspect, is used as a flame retardant aid with respect to 100 parts by mass of the ethylene-based copolymer. It contains 0 to 25.0 parts by mass of antimony trioxide.
  • the resin composition is metal-free relative to 100 parts by mass of the ethylene-based copolymer.
  • the activator 2.0 to 8.0 parts by mass of 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and / or polyphenylene oxide is included.
  • the resin composition is a dispersant with respect to 100 parts by mass of the ethylene-based copolymer. As a result, it contains 5.0 to 15.0 parts by mass of zinc oxide.
  • the ethylene copolymer is an ethylene / ethyl acrylate copolymer. It is.
  • a seventh aspect of the present invention is a vehicle-mounted electric wire / cable according to any one of the first to sixth aspects, having heat resistance that passes the automotive electric wire standard ISO 6722 Class D.
  • the in-vehicle electric wire / cable of the present invention can have high heat resistance and high flexibility.
  • the resin composition used in the present invention comprises an ethylene copolymer containing at least an ethylene / ethyl acrylate copolymer as a base polymer, and contains an antioxidant and a flame retardant.
  • Ethylene copolymers other than the base polymer ethylene / ethyl acrylate copolymer include ethylene, methyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, acrylic acid-2 -Ethylene / unsaturated carboxylic acid ester copolymer obtained by copolymerizing unsaturated carboxylic acid ester such as ethylhexyl, methyl methacrylate, ethyl methacrylate, isobutyl acrylate, dimethyl maleate and diethyl maleate; ethylene and vinyl acetate , Ethylene vinyl ester copolymerized with vinyl esters such as vinyl propionate, vinyl butyrate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate Copolymer; ethylene is copo
  • ethylene / unsaturated carboxylic acid copolymer ethylene / propylene copolymer, ethylene / propylene / diene copolymer, isobutylene / isoprene copolymer, and the like.
  • ethylene copolymers are used together with an ethylene / ethyl acrylate copolymer.
  • ethylene copolymers used in combination with ethylene / ethyl acrylate copolymers ethylene / methyl acrylate copolymers (EMA), ethylene / methyl methacrylate copolymers, ethylene / ethyl methacrylate copolymers Ethylene / (meth) acrylic acid ester copolymers such as coalescence are preferred. It is particularly preferable to use an ethylene / ethyl acrylate copolymer alone as the ethylene copolymer from the viewpoint of obtaining high heat resistance and high flexibility, which are the objects of the present invention.
  • EMA ethylene / methyl acrylate copolymers
  • Ethylene / (meth) acrylic acid ester copolymers such as coalescence
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 2-mercaptobenzimidazole are used as an antioxidant.
  • 1,2-bis (tetrabromophthalimide) ethane is used as a flame retardant.
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is known as a phenolic antioxidant.
  • examples of commercially available products include Irganox 1010 (trade name) manufactured by BASF.
  • the pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is 2.0 to 9.0 parts by mass with respect to 100 parts by mass of the base copolymer ethylene copolymer. Blended. When the blending amount is less than 2.0 parts by mass, the effect of addition is small, and heat resistance and flexibility cannot be improved.
  • This component is preferably blended in an amount of 3.0 to 7.0 parts by weight, more preferably 3.5 to 6.5 parts by weight, per 100 parts by weight of the ethylene copolymer.
  • the other 2-mercaptobenzimidazole used as an antioxidant is known as a sulfur-based antioxidant.
  • Examples of commercially available products include NOCRACK MB (trade name) manufactured by Ouchi Shinsei Chemical Co., Ltd. Etc.
  • the 2-mercaptobenzimidazole is blended in an amount of 2.0 to 8.0 parts by mass with respect to 100 parts by mass of the base copolymer ethylene copolymer.
  • the blending amount is less than 2.0 parts by mass, the effect of addition is small, and heat resistance and flexibility cannot be improved.
  • This compound is preferably blended in an amount of 3.0 to 7.0 parts by weight, more preferably 3.5 to 6.5 parts by weight based on 100 parts by weight of the ethylene copolymer.
  • 1,2-bis (tetrabromophthalimide) ethane used as a flame retardant is known as a brominated flame retardant, and as a commercial product, for example, Cytex 8010 (product of Albemarle Japan) Name).
  • This 1,2-bis (tetrabromophthalimide) ethane is blended in an amount of 15.0 to 35.0 parts by mass with respect to 100 parts by mass of the base copolymer ethylene-based copolymer. If the blending amount is less than 15.0 parts by mass, the effect by addition is small, sufficient flame retardancy cannot be obtained, and heat resistance also decreases. Moreover, when a compounding quantity exceeds 35.0 mass parts, there exists a possibility that mechanical strength may fall.
  • This compound is preferably blended in an amount of 25.0-35.0 parts by weight, more preferably 27.0-33.0 parts by weight, per 100 parts by weight of the ethylene copolymer.
  • the resin composition used in the present invention contains the above two kinds of antioxidants and the above one kind of flame retardant as essential components, but other antioxidants and flame retardants also have the effects of the present invention. It can be used as long as it does not inhibit.
  • antioxidants and flame retardants include thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert.
  • the flame retardants that can be used in combination include nitrogen-based flame retardants such as guanidine and melamine; phosphorus-based flame retardants such as ammonium phosphate and red phosphorus; phosphorus-nitrogen flame retardants; boric acid compounds such as zinc borate Calcium carbonate; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, calcium hydroxide, and barium hydroxide are exemplified.
  • the resin composition used in the present invention includes a flame retardant aid for the purpose of enhancing flame retardancy, and a metal deactivator for the purpose of preventing deterioration due to metal ions such as copper, Moreover, a dispersing agent can be mix
  • antimony trioxide is preferably blended in an amount of 15.0 to 25.0 parts by weight, more preferably 17.0 to 23.0 parts by weight, based on 100 parts by weight of the ethylene copolymer of the base polymer.
  • metal deactivator 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and polyphenylene oxide are preferably used alone or in combination.
  • the metal deactivator is preferably blended in an amount of 2.0 to 8.0 parts by weight, more preferably 3.0 to 6.0 parts by weight with respect to 100 parts by weight of the ethylene copolymer of the base polymer. .
  • the dispersing agent is preferably zinc oxide.
  • Zinc oxide is preferably blended in an amount of 5.0 to 15.0 parts by weight, more preferably 6.0 to 12.0 parts by weight, based on 100 parts by weight of the ethylene copolymer of the base polymer.
  • an ultraviolet absorber In the resin composition used in the present invention, an ultraviolet absorber, a filler, a processing aid, a lubricant, a crosslinking aid, which are generally blended in this type of resin composition within a range not impairing the effects of the present invention.
  • Additives such as colorants and coloring agents can be blended.
  • UV absorber examples include 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4. -Hydroxybenzoate and the like.
  • filler examples include fused silica, crystalline silica, alumina, zirconia, talc, clay, mica, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, silicon nitride, and aluminum nitride.
  • processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, and salts or esters thereof.
  • Examples of the lubricant include hydrocarbons, fatty acids, fatty acid amides, esters, and alcohols.
  • crosslinking aid examples include 1,3,5-triallyl isocyanurate (TAIC) and trimethylolpropane triacrylate (TMPT).
  • TAIC 1,3,5-triallyl isocyanurate
  • TMPT trimethylolpropane triacrylate
  • Each of the above additives may be used alone or in combination of two or more.
  • the resin composition used in the present invention is composed of the above-described ethylene copolymer, antioxidant, flame retardant, and the above-described various components that are blended as necessary. It can be easily prepared by uniform mixing using a conventional kneader such as a kneader, a kneading extruder, or a mixing roller.
  • a conventional kneader such as a kneader, a kneading extruder, or a mixing roller.
  • the in-vehicle electric wire / cable of the present invention is manufactured by coating the resin composition directly on a conductor or through another coating, or by winding a tape-shaped one.
  • the material of the conductor, the outer diameter, the presence or absence of twisting, etc. are not particularly limited, and are appropriately selected depending on the application.
  • the composition is crosslinked after coating or molding.
  • the crosslinking method is not particularly limited, and a chemical crosslinking method in which a crosslinking agent is added to the resin composition in advance and crosslinked after coating or molding, or an electron beam crosslinking method by electron beam irradiation can be used. .
  • crosslinking agent used in the chemical crosslinking method examples include 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 the like tert- butyl cumy
  • the degree of cross-linking is preferably 40 to 80%, more preferably 50 to 70% in terms of gel fraction.
  • the gel fraction is measured based on the crosslinking degree test method defined in JIS C3005.
  • FIG. 1 is a cross-sectional view showing an embodiment of an in-vehicle electric wire / cable of the present invention.
  • symbol 1 has shown the copper twisted wire conductor of outer diameter about 3 mm, for example.
  • the insulator 2 having a thickness of, for example, 0.7 mm is formed by extrusion-coating the above-described resin composition and then crosslinking.
  • EEA Product name manufactured by Nippon Polyethylene Co., Ltd. REXPEARL EEA A1150 (EA content 15% by mass, MFR 0.8 g / 10 min) EVA: Product name Evaflex V5274 manufactured by Mitsui DuPont Polychemical Co., Ltd. (VA content 17% by mass, MFR 0.8 g / 10 min)
  • Antioxidant (1) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate]; BASF brand name Irganox 1010
  • Antioxidant (2) 2-mercaptobenzimidazole
  • Product name NOCRACK MB made by Ouchi Shinsei Chemical Co., Ltd.
  • Antioxidant (3) Tetrakis [methylene-3- (dodecylthio) propionate] methane; ADEKA product name ADK STAB AO-412S Dispersant: 1 type of zinc oxide Lubricant (1): Product name High Wax 110P, manufactured by Mitsui Chemicals, Inc.
  • Lubricant (2) Zinc stearate Flame retardant: 1,2-bis (tetrabromophthalimide) ethane; Albemarle Japan Co., Ltd.
  • Product name Cytex 8010 Flame retardant aid Antimony trioxide Nippon Seiko Co., Ltd.
  • Example 1 EEA 100.0 parts by mass, antioxidant (1) 2.5 parts by mass, antioxidant (2) 2.5 parts by mass, dispersant 10.0 parts by mass, lubricant (1) 2.0 parts by mass, lubricant ( 2) 0.5 parts by weight, flame retardant 15.2 parts by weight, flame retardant aid 20.0 parts by weight, metal deactivator (1) 4.0 parts by weight, and crosslinking aid (1) 2.0 parts by weight Parts were uniformly kneaded with a mixing roll to obtain a resin composition. Next, the above resin composition was extrusion coated on a copper twisted wire conductor having an outer diameter of about 3 mm and crosslinked by electron beam irradiation (dose 30 Mrad) to produce an insulated wire having an outer diameter of about 4.4 mm.
  • dose 30 Mrad electron beam irradiation
  • Examples 2 to 9, Comparative Examples 1 to 5 Except that the composition of the resin composition was changed as shown in Table 1, a flame retardant resin composition was prepared in the same manner as in Example 1, and further, an insulated wire was manufactured using these compositions.
  • Examples 1 to 9 all have mechanical strength, thermal deformation, flexibility (workability), flame retardancy, insulation, heat resistance, wear resistance, and resistance to resistance. Good results were obtained in chemical properties. Further, the antioxidant (1) (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) is added in an amount of 3.0 to 7.0 parts by mass, and the antioxidant (2 ) (2-mercaptobenzimidazole) in an amount of 3.0 to 7.0 parts by mass and brominated flame retardant (1,2-bis (tetrabromophthalimide) ethane) in an amount of 25.0 to 35.0 parts by mass. Better results were obtained in mechanical strength and abrasion resistance.
  • the antioxidant (1) penentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
  • the antioxidant (2 ) (2-mercaptobenzimidazole
  • the in-vehicle electric wire / cable of the present invention has both high heat resistance and high flexibility, and is therefore suitable as an electric wire / cable used in a high temperature environment such as an engine room of an automobile.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

　A vehicle-mounted electrical wire and cable, in which the outer periphery of a conductor is provided with a covering containing 2.0-9.0 parts by mass of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 2.0-8.0 parts by mass of 2-mercaptobenzimidazole as antioxidants, and comprising a cross-linking body of a resin composition containing 15.0-35.0 parts by mass of 1,2-bis(tetrabromophthalimide)ethane as a flame retardant, the above amounts being given with respect to 100 parts by mass of an ethylene copolymer containing an ethylene-ethyl acrylate copolymer.

Description

車載用電線・ケーブルAutomotive wires and cables
　本発明は、柔軟性および耐熱性に優れる車載用電線・ケーブルに関する。 The present invention relates to an in-vehicle electric wire / cable excellent in flexibility and heat resistance.
　近年、環境保護に対する関心の高まりから、モータを併用したＨＥＶ（Hybrid Electric Vehicle）が急速に普及している。ＨＥＶに用いる電線・ケーブルでは、エンジンとモータの位置関係から高い耐熱性が要求される。具体的には、自動車用電線規格のＩＳＯ ６７２２のＣｌａｓｓ Ｄ以上の要求特性を満たす耐熱性が要求される。また、同時に狭いスペースに配線されるため、柔軟性に優れることが要求される。 In recent years, HEV (Hybrid Electric Vehicle) combined with a motor is rapidly spreading due to the growing interest in environmental protection. Electric wires and cables used for HEV are required to have high heat resistance due to the positional relationship between the engine and the motor. Specifically, heat resistance that satisfies the required characteristics of ISO 6722, Class D or more of the automotive electric wire standard is required. Moreover, since wiring is performed in a narrow space at the same time, excellent flexibility is required.
　従来、このような高い耐熱性と高い柔軟性が要求される用途に用いる電線・ケーブルの被覆材には、架橋により耐熱性を高めたポリ塩化ビニルやポリエチレンが一般に使用されてきた（例えば、特許文献１参照。）。しかしながら、これらの樹脂は架橋によって耐熱性が高められているとはいえ、十分とまでは言えない。 Conventionally, polyvinyl chloride and polyethylene whose heat resistance has been improved by crosslinking have been generally used for wire / cable coating materials used in applications requiring such high heat resistance and high flexibility (for example, patents). Reference 1). However, although these resins have improved heat resistance by crosslinking, they cannot be said to be sufficient.
　また、一部の自動車用途で、耐熱性に優れるとして、フッ素樹脂やシリコーン樹脂が使用されている。しかしながら、フッ素樹脂は非常に硬く、配策に問題を生ずる。また、シリコーン樹脂は柔軟性を有するものの、強度が小さいため、配策の際に欠陥が生じやすい。 Fluorine resins and silicone resins are also used for some automotive applications as having excellent heat resistance. However, fluororesins are very hard and cause problems in the routing. Moreover, although a silicone resin has flexibility, since it is low in strength, defects are likely to occur during routing.
　このように十分に高い耐熱性と十分に高い柔軟性を持つ車載用電線・ケーブルは未だ得られていない。そして、車載用電線・ケーブルには、耐熱性および柔軟性のほか、上述のように機械的強度や耐摩耗性、難燃性などの特性も要求される。 Thus, an in-vehicle electric wire / cable having sufficiently high heat resistance and sufficiently high flexibility has not been obtained yet. In addition to heat resistance and flexibility, in-vehicle electric wires and cables are also required to have characteristics such as mechanical strength, wear resistance, and flame retardance as described above.
特開２０１３－１５５２６９号公報JP 2013-155269 A
　本発明はこのような従来技術の課題を解決するためになされたもので、高い耐熱性と高い柔軟性を有し、さらに機械的強度、耐摩耗性、難燃性などにも優れる車載用電線・ケーブルを提供することを目的とする。 The present invention has been made to solve the problems of the prior art, and has high heat resistance and high flexibility, and further has excellent mechanical strength, wear resistance, flame retardancy, and the like.・ The purpose is to provide cables.
　本発明者らは、上記の目的を達成するため鋭意研究を重ねた結果、エチレン・アクリル酸エチル共重合体を含むエチレン系共重合体に、特定の２種の酸化防止剤と特定の臭素系難燃剤を組み合わせて添加した樹脂組成物を被覆材料として用いることにより、高い耐熱性と高い柔軟性を併せ持つ電線・ケーブルが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an ethylene-based copolymer including an ethylene / ethyl acrylate copolymer has two specific antioxidants and a specific bromine-based copolymer. It has been found that by using a resin composition combined with a flame retardant as a coating material, an electric wire / cable having both high heat resistance and high flexibility can be obtained, and the present invention has been completed.
　本発明の第１の態様である車載用電線・ケーブルは、導体外周に、エチレン・アクリル酸エチル共重合体を含むエチレン系共重合体１００質量部に対し、酸化防止剤として２．０～９．０質量部のペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］および２．０～８．０質量部の２－メルカプトベンゾイミダゾールを含有し、難燃剤として１５．０～３５．０質量部の１，２－ビス（テトラブロモフタルイミド）エタンを含有する樹脂組成物の架橋体からなる被覆を備えるものである。 The in-vehicle electric wire / cable according to the first aspect of the present invention has 2.0 to 9 as an antioxidant with respect to 100 parts by mass of an ethylene-based copolymer containing an ethylene / ethyl acrylate copolymer on the outer periphery of the conductor. Containing 0.0 part by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 2.0 to 8.0 parts by weight of 2-mercaptobenzimidazole, A coating comprising a crosslinked product of a resin composition containing 15.0 to 35.0 parts by mass of 1,2-bis (tetrabromophthalimide) ethane as a flame retardant is provided.
　本発明の第２の態様は、第１の態様の難燃性電線・ケーブルにおいて、前記樹脂組成物は、エチレン系共重合体１００質量部に対し、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］を３．０～７．０質量部、２－メルカプトベンゾイミダゾールを３．０～７．０質量部、１，２－ビス（テトラブロモフタルイミド）エタンを２５．０～３５．０質量部含有するものである。 According to a second aspect of the present invention, in the flame-retardant electric wire / cable according to the first aspect, the resin composition may be pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] is 3.0 to 7.0 parts by mass, 2-mercaptobenzimidazole is 3.0 to 7.0 parts by mass, 1,2-bis (tetrabromophthalimide) It contains 25.0-35.0 parts by mass of ethane.
　本発明の第３の態様は、第１の態様または第２の態様の車載用電線・ケーブルにおいて、前記樹脂組成物が、エチレン系共重合体１００質量部に対し、難燃助剤として１５．０～２５．０質量部の三酸化アンチモンを含有するものである。 According to a third aspect of the present invention, in the in-vehicle electric wire / cable of the first aspect or the second aspect, the resin composition is used as a flame retardant aid with respect to 100 parts by mass of the ethylene-based copolymer. It contains 0 to 25.0 parts by mass of antimony trioxide.
　本発明の第４の態様は、第１の態様乃至第３の態様のいずれかの態様の車載用電線・ケーブルにおいて、前記樹脂組成物が、エチレン系共重合体１００質量部に対し、金属不活性剤として２．０～８．０質量部の２’，３－ビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニル］ヒドラジンおよび／またはポリフェニレンオキサイドを含むものである。 According to a fourth aspect of the present invention, in the in-vehicle electric wire / cable according to any one of the first to third aspects, the resin composition is metal-free relative to 100 parts by mass of the ethylene-based copolymer. As the activator, 2.0 to 8.0 parts by mass of 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and / or polyphenylene oxide is included.
　本発明の第５の態様は、第１の態様乃至第４の態様のいずれかの態様の車載用電線・ケーブルにおいて、前記樹脂組成物が、エチレン系共重合体１００質量部に対し、分散剤として５．０～１５．０質量部の酸化亜鉛を含むものである。 According to a fifth aspect of the present invention, in the in-vehicle electric wire / cable according to any one of the first to fourth aspects, the resin composition is a dispersant with respect to 100 parts by mass of the ethylene-based copolymer. As a result, it contains 5.0 to 15.0 parts by mass of zinc oxide.
　本発明の第６の態様は、第１の態様乃至第５の態様のいずれかの態様の車載用電線・ケーブルにおいて、前記エチレン系共重合体は、エチレン・アクリル酸エチル共重合体であるものである。 According to a sixth aspect of the present invention, in the in-vehicle electric wire / cable according to any one of the first to fifth aspects, the ethylene copolymer is an ethylene / ethyl acrylate copolymer. It is.
　本発明の第７の態様は、第１の態様乃至第６の態様のいずれかの態様の車載用電線・ケーブルにおいて、自動車用電線規格ＩＳＯ ６７２２ Ｃｌａｓｓ Ｄに合格する耐熱性を有するものである。 A seventh aspect of the present invention is a vehicle-mounted electric wire / cable according to any one of the first to sixth aspects, having heat resistance that passes the automotive electric wire standard ISO 6722 Class D.
　本発明の車載用電線・ケーブルによれば、高い耐熱性と高い柔軟性を有することができる。 The in-vehicle electric wire / cable of the present invention can have high heat resistance and high flexibility.
本発明の車載用電線・ケーブルの一実施形態を示す横断面図である。It is a cross-sectional view which shows one Embodiment of the vehicle-mounted electric wire and cable of this invention.
　以下、本発明の実施の形態について説明する。 Hereinafter, embodiments of the present invention will be described.
　まず、本発明の車載用電線・ケーブルに使用される樹脂組成物について説明する。 First, the resin composition used for the in-vehicle electric wire / cable of the present invention will be described.
　本発明において使用される樹脂組成物は、少なくともエチレン・アクリル酸エチル共重合体を含むエチレン系共重合体をベースポリマーとし、酸化防止剤および難燃剤を含有するものである。 The resin composition used in the present invention comprises an ethylene copolymer containing at least an ethylene / ethyl acrylate copolymer as a base polymer, and contains an antioxidant and a flame retardant.
　ベースポリマーのエチレン・アクリル酸エチル共重合体以外のエチレン系共重合体としては、エチレンに、アクリル酸メチル、アクリル酸イソプロピル、アクリル酸イソブチル、アクリル酸ｎ－ブチル、アクリル酸イソオクチル、アクリル酸‐２‐エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、アクリル酸イソブチル、マレイン酸ジメチル、マレイン酸ジエチルなどの不飽和カルボン酸エステルを共重合させたエチレン・不飽和カルボン酸エステル共重合体；エチレンに、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、パーサティック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、サリチル酸ビニル、シクロヘキサンカルボン酸ビニルなどのビニルエステルを共重合させたエチレン・ビニルエステル共重合体；エチレンに、アクリル酸、メタクリル酸、エタクリル酸、マレイン酸、フマル酸、イタコン酸、無水マレイン酸、無水イタコン酸、マレイン酸モノメチル、マレイン酸モノエチルなどの不飽和カルボン酸を共重合させたエチレン・不飽和カルボン酸共重合体；エチレン・プロピレン共重合体、エチレン・プロピレン・ジエン共重合体、イソブチレン・イソプレン共重合体などが挙げられる。これらのエチレン系共重合体のうちの１種以上が、エチレン・アクリル酸エチル共重合体とともに使用される。 Ethylene copolymers other than the base polymer ethylene / ethyl acrylate copolymer include ethylene, methyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, acrylic acid-2 -Ethylene / unsaturated carboxylic acid ester copolymer obtained by copolymerizing unsaturated carboxylic acid ester such as ethylhexyl, methyl methacrylate, ethyl methacrylate, isobutyl acrylate, dimethyl maleate and diethyl maleate; ethylene and vinyl acetate , Ethylene vinyl ester copolymerized with vinyl esters such as vinyl propionate, vinyl butyrate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate Copolymer; ethylene is copolymerized with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleate, monoethyl maleate, etc. And ethylene / unsaturated carboxylic acid copolymer; ethylene / propylene copolymer, ethylene / propylene / diene copolymer, isobutylene / isoprene copolymer, and the like. One or more of these ethylene copolymers are used together with an ethylene / ethyl acrylate copolymer.
　エチレン・アクリル酸エチル共重合体と併用するエチレン系共重合体としては、なかでも、エチレン・アクリル酸メチル共重合体（ＥＭＡ）、エチレン・メタクリル酸メチル共重合体、エチレン・メタクリル酸エチル共重合体などのエチレン・（メタ）アクリル酸エステル共重合体が好ましい。エチレン系共重合体としてエチレン・アクリル酸エチル共重合体を単独使用することが、本発明の目的である高い耐熱性と高い柔軟性を得る観点からは特に好ましい。 Among the ethylene copolymers used in combination with ethylene / ethyl acrylate copolymers, ethylene / methyl acrylate copolymers (EMA), ethylene / methyl methacrylate copolymers, ethylene / ethyl methacrylate copolymers Ethylene / (meth) acrylic acid ester copolymers such as coalescence are preferred. It is particularly preferable to use an ethylene / ethyl acrylate copolymer alone as the ethylene copolymer from the viewpoint of obtaining high heat resistance and high flexibility, which are the objects of the present invention.
　本発明で使用される樹脂組成物には、酸化防止剤として、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］、および２－メルカプトベンゾイミダゾールが使用され、また、難燃剤として１，２－ビス（テトラブロモフタルイミド）エタンが使用される。 In the resin composition used in the present invention, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 2-mercaptobenzimidazole are used as an antioxidant. In addition, 1,2-bis (tetrabromophthalimide) ethane is used as a flame retardant.
　酸化防止剤として使用される２種のうち、一方のペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］は、フェノール系酸化防止剤として知られるもので、市販品としては、例えば、ＢＡＳＦ社製のイルガノックス１０１０（商品名）などが挙げられる。このペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］は、ベースポリマーのエチレン系共重合体１００質量部に対し、２．０～９．０質量部配合される。配合量が２．０質量部未満では、添加による効果が小さく、耐熱性、柔軟性を向上させることができない。また、配合量が９．０質量部を超えると、効果はさほど変わらず、非経済的となる。本成分は、エチレン系共重合体１００質量部に対し、３．０～７．０質量部配合することが好ましく、３．５～６．５質量部配合することがより好ましい。 Of the two types used as antioxidants, one pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is known as a phenolic antioxidant. Examples of commercially available products include Irganox 1010 (trade name) manufactured by BASF. The pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is 2.0 to 9.0 parts by mass with respect to 100 parts by mass of the base copolymer ethylene copolymer. Blended. When the blending amount is less than 2.0 parts by mass, the effect of addition is small, and heat resistance and flexibility cannot be improved. Moreover, when a compounding quantity exceeds 9.0 mass part, an effect will not change so much and it will become uneconomical. This component is preferably blended in an amount of 3.0 to 7.0 parts by weight, more preferably 3.5 to 6.5 parts by weight, per 100 parts by weight of the ethylene copolymer.
　酸化防止剤として使用される他方の２－メルカプトベンゾイミダゾールは、硫黄系酸化防止剤として知られるもので、市販品としては、例えば、大内新興化学工業（株）製のノクラックＭＢ（商品名）などが挙げられる。この２－メルカプトベンゾイミダゾールは、ベースポリマーのエチレン系共重合体１００質量部に対し、２．０～８．０質量部配合される。配合量が２．０質量部未満では、添加による効果が小さく、耐熱性、柔軟性を向上させることができない。また、配合量が８．０質量部を超えると、効果はさほど変わらず、非経済的となる。この化合物は、エチレン系共重合体１００質量部に対し、３．０～７．０質量部配合することが好ましく、３．５～６．５質量部配合することがより好ましい。 The other 2-mercaptobenzimidazole used as an antioxidant is known as a sulfur-based antioxidant. Examples of commercially available products include NOCRACK MB (trade name) manufactured by Ouchi Shinsei Chemical Co., Ltd. Etc. The 2-mercaptobenzimidazole is blended in an amount of 2.0 to 8.0 parts by mass with respect to 100 parts by mass of the base copolymer ethylene copolymer. When the blending amount is less than 2.0 parts by mass, the effect of addition is small, and heat resistance and flexibility cannot be improved. Moreover, when a compounding quantity exceeds 8.0 mass parts, an effect will not change so much and it will become uneconomical. This compound is preferably blended in an amount of 3.0 to 7.0 parts by weight, more preferably 3.5 to 6.5 parts by weight based on 100 parts by weight of the ethylene copolymer.
　また、難燃剤として使用される１，２－ビス（テトラブロモフタルイミド）エタンは、臭素系難燃剤として知られるもので、市販品としては、例えば、アルベマール日本（株）製のサイテックス８０１０（商品名）などが挙げられる。この１，２－ビス（テトラブロモフタルイミド）エタンは、ベースポリマーのエチレン系共重合体１００質量部に対し、１５．０～３５．０質量部配合される。配合量が１５．０質量部未満では、添加による効果が小さく、十分な難燃性が得られず、耐熱性も低下する。また、配合量が３５．０質量部を超えると、機械的強度が低下するおそれがある。この化合物は、エチレン系共重合体１００質量部に対し、２５．０～３５．０質量部配合することが好ましく、２７．０～３３．０質量部配合することがより好ましい。 Further, 1,2-bis (tetrabromophthalimide) ethane used as a flame retardant is known as a brominated flame retardant, and as a commercial product, for example, Cytex 8010 (product of Albemarle Japan) Name). This 1,2-bis (tetrabromophthalimide) ethane is blended in an amount of 15.0 to 35.0 parts by mass with respect to 100 parts by mass of the base copolymer ethylene-based copolymer. If the blending amount is less than 15.0 parts by mass, the effect by addition is small, sufficient flame retardancy cannot be obtained, and heat resistance also decreases. Moreover, when a compounding quantity exceeds 35.0 mass parts, there exists a possibility that mechanical strength may fall. This compound is preferably blended in an amount of 25.0-35.0 parts by weight, more preferably 27.0-33.0 parts by weight, per 100 parts by weight of the ethylene copolymer.
　本発明で使用される樹脂組成物は、上記２種の酸化防止剤と上記１種の難燃剤を必須成分とするものであるが、それら以外の酸化防止剤および難燃剤も本発明の効果を阻害しない範囲で使用することができる。
　そのような併用可能な酸化防止剤としては、例えば、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート、Ｎ，Ｎ’－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオンアミド）、テトラキス－［メチレン－３－（３′，５′－ジ－ｔｅｒｔ－ブチル－４′－ヒドロキシフェニル）プロピオネート］メタン、ビス［２－メチル－４－（３－ｎ－アルキルチオプロピオニルオキシ）－５－ｔｅｒｔ－ブチルフェニル］スルフィド、２－メルカプトメチルベンゾイミダゾール、４－メルカプトメチルベンゾイミダゾール、５－メルカプトメチルベンゾイミダゾールなどが挙げられる。
　また、併用可能な難燃剤としては、グアニジン系、メラミン系などの窒素系難燃剤；リン酸アンモニウム、赤燐などのリン系難燃剤；リン－窒素系難燃剤；ホウ酸亜鉛などのホウ酸化合物；炭酸カルシウム；水酸化マグネシウム、水酸化アルミニウム、水酸化ジルコニウム、水酸化カルシウム、水酸化バリウムなどの金属水酸化物などが例示される。 The resin composition used in the present invention contains the above two kinds of antioxidants and the above one kind of flame retardant as essential components, but other antioxidants and flame retardants also have the effects of the present invention. It can be used as long as it does not inhibit.
Examples of such an antioxidant that can be used in combination include thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert. -Butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), tetrakis- [methylene-3 -(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl] sulfide 2-mercaptomethylbenzimidazole, 4-mercaptomethylbenzimidazole, 5-mercapto Examples include methylbenzimidazole.
The flame retardants that can be used in combination include nitrogen-based flame retardants such as guanidine and melamine; phosphorus-based flame retardants such as ammonium phosphate and red phosphorus; phosphorus-nitrogen flame retardants; boric acid compounds such as zinc borate Calcium carbonate; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, calcium hydroxide, and barium hydroxide are exemplified.
　本発明で使用される樹脂組成物には、以上の各成分の他、難燃性を高める目的で難燃助剤を、銅などの金属イオンによる劣化を防止する目的で金属不活性剤を、また、分散性を高める目的で分散剤を、本発明の効果を阻害しない範囲で配合することができる。 In addition to the above components, the resin composition used in the present invention includes a flame retardant aid for the purpose of enhancing flame retardancy, and a metal deactivator for the purpose of preventing deterioration due to metal ions such as copper, Moreover, a dispersing agent can be mix | blended in the range which does not inhibit the effect of this invention in order to improve a dispersibility.
　本発明の電線・ケーブルに高い耐熱性を付与する観点からは、難燃助剤として三酸化アンチモンの使用が好ましい。三酸化アンチモンは、ベースポリマーのエチレン系共重合体１００質量部に対し、１５．０～２５．０質量部配合することが好ましく、１７．０～２３．０質量部配合することがより好ましい。 From the viewpoint of imparting high heat resistance to the electric wire / cable of the present invention, it is preferable to use antimony trioxide as a flame retardant aid. Antimony trioxide is preferably blended in an amount of 15.0 to 25.0 parts by weight, more preferably 17.0 to 23.0 parts by weight, based on 100 parts by weight of the ethylene copolymer of the base polymer.
　金属不活性剤としては、２’，３－ビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニル］ヒドラジンおよびポリフェニレンオキサイドをそれぞれ単独または混合して使用することが好ましい。金属不活性剤は、ベースポリマーのエチレン系共重合体１００質量部に対し、２．０～８．０質量部配合することが好ましく、３．０～６．０質量部配合することがより好ましい。 As the metal deactivator, 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and polyphenylene oxide are preferably used alone or in combination. . The metal deactivator is preferably blended in an amount of 2.0 to 8.0 parts by weight, more preferably 3.0 to 6.0 parts by weight with respect to 100 parts by weight of the ethylene copolymer of the base polymer. .
　分散剤は、酸化亜鉛が好ましい。酸化亜鉛はベースポリマーのエチレン系共重合体１００質量部に対し、５．０～１５．０質量部配合することが好ましく、６．０～１２．０質量部配合することがより好ましい。 The dispersing agent is preferably zinc oxide. Zinc oxide is preferably blended in an amount of 5.0 to 15.0 parts by weight, more preferably 6.0 to 12.0 parts by weight, based on 100 parts by weight of the ethylene copolymer of the base polymer.
　本発明で使用される樹脂組成物には、本発明の効果を阻害しない範囲で、この種の樹脂組成物に一般に配合されている、紫外線吸収剤、充填剤、加工助剤、滑剤、架橋助剤、着色剤などの添加剤を配合することができる。 In the resin composition used in the present invention, an ultraviolet absorber, a filler, a processing aid, a lubricant, a crosslinking aid, which are generally blended in this type of resin composition within a range not impairing the effects of the present invention. Additives such as colorants and coloring agents can be blended.
　紫外線吸収剤としては、例えば、２－（２′－ヒドロキシ－４′－ｎ－オクトキシフェニル）ベンゾトリアゾール、２，４－ジ－ｔｅｒｔ－ブチルフェニル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゾエートなどが挙げられる。 Examples of the ultraviolet absorber include 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4. -Hydroxybenzoate and the like.
　充填剤としては、例えば、溶融シリカ、結晶シリカ、アルミナ、ジルコニア、タルク、クレー、マイカ、炭酸カルシウム、チタンホワイト、ベンガラ、炭化珪素、窒化ホウ素、窒化珪素、窒化アルミなどが例示される。 Examples of the filler include fused silica, crystalline silica, alumina, zirconia, talc, clay, mica, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, silicon nitride, and aluminum nitride.
　加工助剤としては、リシノール酸、ステアリン酸、パルチミン酸、ラウリン酸や、これらの塩またはエステル類などが挙げられる。 Examples of processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, and salts or esters thereof.
　滑剤としては、例えば、炭化水素系、脂肪酸系、脂肪酸アミド系、エステル系、アルコール系などが挙げられる。 Examples of the lubricant include hydrocarbons, fatty acids, fatty acid amides, esters, and alcohols.
　架橋助剤としては、１，３，５－トリアリルイソシアヌレート（ＴＡＩＣ）、トリメチロールプロパントリアクリレート（ＴＭＰＴ）などが挙げられる。 Examples of the crosslinking aid include 1,3,5-triallyl isocyanurate (TAIC) and trimethylolpropane triacrylate (TMPT).
　上記各添加剤は、いずれも１種を単独で使用してもよく、２種以上を混合して使用してもよい。 Each of the above additives may be used alone or in combination of two or more.
　本発明で使用される樹脂組成物は、上記したようなエチレン系共重合体、酸化防止剤、難燃剤、並びに、必要に応じて配合される上述した各種成分を、バンバリーミキサ、タンブラー、加圧ニーダ、混練押出機、ミキシングローラなどの通常の混練機を用いて均一に混合することにより容易に調製することができる。 The resin composition used in the present invention is composed of the above-described ethylene copolymer, antioxidant, flame retardant, and the above-described various components that are blended as necessary. It can be easily prepared by uniform mixing using a conventional kneader such as a kneader, a kneading extruder, or a mixing roller.
　本発明の車載用電線・ケーブルは、上記樹脂組成物を、導体上に直接もしくは他の被覆を介して押出被覆するか、あるいはテープ状に成形したものを巻き付けることにより製造される。導体の材質や外径、撚り合せの有無などは特に限定されるものではなく、用途によって適宜選択される。組成物は、被覆後もしくは成形後、架橋される。架橋法は特に限定されるものではなく、予め架橋剤を樹脂組成物に添加しておき、被覆後または成形後に架橋させる化学架橋法や、電子線照射による電子線架橋法などを用いることができる。 The in-vehicle electric wire / cable of the present invention is manufactured by coating the resin composition directly on a conductor or through another coating, or by winding a tape-shaped one. The material of the conductor, the outer diameter, the presence or absence of twisting, etc. are not particularly limited, and are appropriately selected depending on the application. The composition is crosslinked after coating or molding. The crosslinking method is not particularly limited, and a chemical crosslinking method in which a crosslinking agent is added to the resin composition in advance and crosslinked after coating or molding, or an electron beam crosslinking method by electron beam irradiation can be used. .
　化学架橋法を行う場合に用いる架橋剤としては、ジクミルパーオキサイド、ジ－ｔｅｒｔ－ブチルパーオキサイド、２，５－ジメチル－２，５－ジ－（ｔｅｒｔ－ブチルパーオキシ）ヘキサン、２，５－ジメチル－２，５－ジ－（ｔｅｒｔ－ブチルパーオキシ）ヘキシン－３、１，３－ビス（ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ｎ－ブチル－４，４－ビス（ｔｅｒｔ－ブチルパーオキシ）バレレート、ベンゾイルオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシイソプロピルカーボネート、ジアセチルパーオキサイド、ラウロイルパーオキサイド、ｔｅｒｔ－ブチルクミルパーオキサイドなどが挙げられる。 Examples of the crosslinking agent used in the chemical crosslinking method include 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 the like tert- butyl cumyl peroxide.
　架橋の度合いは、ゲル分率で４０～８０％が好ましく、５０～７０％がより好ましい。ゲル分率が４０％未満であると、熱変形性や機械的強度が低下する。またゲル分率が８０％を超えると、柔軟性、耐熱性、配策性が低下する。なお、このゲル分率は、ＪＩＳ Ｃ ３００５に規定の架橋度試験方法に基づき測定される。 The degree of cross-linking is preferably 40 to 80%, more preferably 50 to 70% in terms of gel fraction. When the gel fraction is less than 40%, the heat deformability and mechanical strength are lowered. On the other hand, when the gel fraction exceeds 80%, flexibility, heat resistance, and routeability deteriorate. The gel fraction is measured based on the crosslinking degree test method defined in JIS C3005.
　図１は、本発明の車載用電線・ケーブルの一実施形態を示す横断面図である。 FIG. 1 is a cross-sectional view showing an embodiment of an in-vehicle electric wire / cable of the present invention.
　図１において、符号１は、例えば外径約３ｍｍの銅撚線導体を示している。この導体１上には、前述した樹脂組成物を押出被覆した後、架橋することによって、例えば厚さ０．７ｍｍの絶縁体２が形成されている。 In FIG. 1, the code | symbol 1 has shown the copper twisted wire conductor of outer diameter about 3 mm, for example. On this conductor 1, the insulator 2 having a thickness of, for example, 0.7 mm is formed by extrusion-coating the above-described resin composition and then crosslinking.
　本実施形態の車載用電線・ケーブルにおいては、エチレン系共重合体をベースポリマーとし、このベースポリマーに特定の２種の酸化防止剤と特定の難燃剤を特定の割合で配合した樹脂の架橋体からなる被覆を備えている。したがって、高い耐熱性、具体的には、自動車用電線規格のＩＳＯ ６７２２のＣｌａｓｓ Ｄの要求特性を満たす耐熱性を有するとともに、高い柔軟性を具備することができる。 In the in-vehicle electric wire / cable of the present embodiment, a cross-linked resin in which an ethylene copolymer is used as a base polymer, and two specific antioxidants and a specific flame retardant are blended in a specific ratio with the base polymer. A coating consisting of Therefore, it has high heat resistance, specifically, heat resistance satisfying the required characteristics of Class IV D of ISO 6722 of the automotive electric wire standard and high flexibility.
　次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。実施例および比較例で用いた成分は以下の通りである。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The components used in Examples and Comparative Examples are as follows.
　ＥＥＡ：
　　　　日本ポリエチレン（株）製　商品名 ＲＥＸＰＥＡＲＬ ＥＥＡ Ａ１１５０
　　　　（ＥＡ含量 １５質量％、ＭＦＲ ０．８ｇ／１０分）
　ＥＶＡ：
　　　　三井・デュポン・ポリケミカル（株）製　商品名 エバフレックス Ｖ５２７４
　　　　（ＶＡ含量 １７質量％、ＭＦＲ ０．８ｇ／１０分）
　ＬＤＰＥ（１）：
　　　　宇部興産（株）製　商品名 ＵＢＥＣ１３０
　ＬＤＰＥ（２）：
　　　　住友化学（株）製　商品名 スミカセンＥＰ ＣＵ５００３
　酸化防止剤（１）：
　　　　ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－
　　　　ヒドロキシフェニル）プロピオナート］；
　　　　ＢＡＳＦ社製　商品名 イルガノックス１０１０
　酸化防止剤（２）：
　　　　２－メルカプトベンゾイミダゾール；
　　　　大内新興化学工業（株）製　商品名 ノクラックＭＢ
　酸化防止剤（３）：
　　　　テトラキス［メチレン－３－（ドデシルチオ）プロピオネート］メタン；
　　　　ＡＤＥＫＡ社製　商品名 アデカスタブＡＯ－４１２Ｓ
　分散剤：酸化亜鉛１種
　滑剤（１）：
　　　　三井化学（株）製　商品名 ハイワックス１１０Ｐ
　滑剤（２）：ステアリン酸亜鉛
　難燃剤：
　　　　１，２－ビス（テトラブロモフタルイミド）エタン；
　　　　アルベマール日本（株）製　商品名 サイテックス８０１０
　難燃助剤：
　　　　三酸化アンチモン
　　　　日本精鉱（株）製　商品名 パトックスＭ
　金属不活性剤（１）：
　　　　ポリフェニレンオキサイド
　　　　ＡＤＥＫＡ社製　商品名 アデカスタブＣＤＡ－６
　金属不活性剤（２）：
　　　　２’，３－ビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニ
　　　　ル）プロピオニル］ヒドラジン
　　　　ＢＡＳＦ社製　商品名 イルガノックスＭＤ１０２４
　架橋助剤（１）：
　　　　１，３，５－トリアリルイソシアヌレート（ＴＡＩＣ）
　架橋助剤（２）：
　　　　トリメチロールプロパントリアクリレート（ＴＭＰＴ） EEA:
Product name manufactured by Nippon Polyethylene Co., Ltd. REXPEARL EEA A1150
(EA content 15% by mass, MFR 0.8 g / 10 min)
EVA:
Product name Evaflex V5274 manufactured by Mitsui DuPont Polychemical Co., Ltd.
(VA content 17% by mass, MFR 0.8 g / 10 min)
LDPE (1):
Product name UBEC130 manufactured by Ube Industries, Ltd.
LDPE (2):
Product name Sumikasen EP CU5003 manufactured by Sumitomo Chemical Co., Ltd.
Antioxidant (1):
Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionate];
BASF brand name Irganox 1010
Antioxidant (2):
2-mercaptobenzimidazole;
Product name NOCRACK MB made by Ouchi Shinsei Chemical Co., Ltd.
Antioxidant (3):
Tetrakis [methylene-3- (dodecylthio) propionate] methane;
ADEKA product name ADK STAB AO-412S
Dispersant: 1 type of zinc oxide Lubricant (1):
Product name High Wax 110P, manufactured by Mitsui Chemicals, Inc.
Lubricant (2): Zinc stearate Flame retardant:
1,2-bis (tetrabromophthalimide) ethane;
Albemarle Japan Co., Ltd. Product name Cytex 8010
Flame retardant aid:
Antimony trioxide Nippon Seiko Co., Ltd. Brand name Patox M
Metal deactivator (1):
Polyphenylene oxide ADEKA product name ADK STAB CDA-6
Metal deactivator (2):
2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine BASF Corporation trade name Irganox MD1024
Crosslinking aid (1):
1,3,5-triallyl isocyanurate (TAIC)
Crosslinking aid (2):
Trimethylolpropane triacrylate (TMPT)
（実施例１）
　ＥＥＡ１００．０質量部、酸化防止剤（１）２．５質量部、酸化防止剤（２）２．５質量部、分散剤１０．０質量部、滑剤（１）２．０質量部、滑剤（２）０．５質量部、難燃剤１５．２質量部、難燃助剤２０．０質量部、金属不活性剤（１）４．０質量部、および架橋助剤（１）２．０質量部をミキシングロールにより均一に混練して樹脂組成物を得た。
　次いで、外径約３ｍｍの銅撚線導体上に上記樹脂組成物を押出被覆し、電子線照射（線量３０Ｍｒａｄ）により架橋させて、外径約４．４ｍｍの絶縁電線を製造した。 Example 1
EEA 100.0 parts by mass, antioxidant (1) 2.5 parts by mass, antioxidant (2) 2.5 parts by mass, dispersant 10.0 parts by mass, lubricant (1) 2.0 parts by mass, lubricant ( 2) 0.5 parts by weight, flame retardant 15.2 parts by weight, flame retardant aid 20.0 parts by weight, metal deactivator (1) 4.0 parts by weight, and crosslinking aid (1) 2.0 parts by weight Parts were uniformly kneaded with a mixing roll to obtain a resin composition.
Next, the above resin composition was extrusion coated on a copper twisted wire conductor having an outer diameter of about 3 mm and crosslinked by electron beam irradiation (dose 30 Mrad) to produce an insulated wire having an outer diameter of about 4.4 mm.
（実施例２～９、比較例１～５）
　樹脂組成物の組成を表１に示すように変えた以外は、実施例１と同様にして、難燃性樹脂組成物を調製し、さらに、これらの組成物を用いて絶縁電線を製造した。 (Examples 2 to 9, Comparative Examples 1 to 5)
Except that the composition of the resin composition was changed as shown in Table 1, a flame retardant resin composition was prepared in the same manner as in Example 1, and further, an insulated wire was manufactured using these compositions.
　上記各実施例および各比較例で得られた絶縁電線について、下記に示す方法で各種特性を測定・評価した。
［機械的強度（引張強さ）］
　ＪＡＳＯ（日本自動車技術会規格） Ｄ ６１８にしたがい、長さ１５０ｍｍの絶縁電線から内部の導体を引き抜いて作製した環状の試験片について、引張速度５００ｍｍ／分および標点距離５０ｍｍの条件で引張強さ（ＭＰａ）を測定し、下記の基準で評価した。
　Ａ：２０ＭＰａ以上
　Ｂ：１０ＭＰａ以上２０ＭＰａ未満
　Ｃ：１０ＭＰａ未満
［熱変形性］
　ＩＳＯ ６７２２にしたがい、電線を２００ｇの荷重を加えた状態で１５０℃に４時間放置し、冷却後、塩水に１０分間浸漬した後、１ｋｖ×１分の耐電圧試験を行い、絶縁破壊が起きなかった場合を「合格」、絶縁破壊が起きた場合を「不合格」と評価した。
［柔軟性（作業性）]
　絶縁電線を曲げたときに、反発することなく、曲げ形状を保持することができ、かつ、電線被覆に、曲げによるしわや亀裂の発生がない場合を「合格」、そうでないものを「不合格」と評価した。 About the insulated wire obtained by each said Example and each comparative example, various characteristics were measured and evaluated by the method shown below.
[Mechanical strength (tensile strength)]
In accordance with JASO (Japan Automobile Manufacturers Association Standard) D 618, an annular test piece produced by pulling out an internal conductor from an insulated wire having a length of 150 mm has a tensile strength of 500 mm / min and a gauge distance of 50 mm. (MPa) was measured and evaluated according to the following criteria.
A: 20 MPa or more B: 10 MPa or more and less than 20 MPa C: less than 10 MPa [thermal deformability]
In accordance with ISO 6722, the wire was left at 150 ° C. for 4 hours with a load of 200 g, cooled, immersed in salt water for 10 minutes, then subjected to a withstand voltage test of 1 kv × 1 minute, and no dielectric breakdown occurred. The case where the dielectric breakdown occurred was evaluated as “failed”.
[Flexibility (workability)]
When an insulated wire is bent, the bent shape can be maintained without being repelled, and the wire covering is free of wrinkles and cracks due to bending. ".
［難燃性］
　ＩＳＯ ６７２２に規定される４５度傾斜燃焼試験を行い、７０秒で消火し、かつ絶縁体が５０ｍｍ以上残った場合を「合格」とし、７０秒で消火しなかった場合を「不合格」と評価した。
［絶縁性］
　ＩＳＯ ６７２２に準拠して、電線を塩水に４時間浸漬させた後、１ｋｖ×３０分および５ｋＶ×５分の耐電圧試験を行い、絶縁破壊が起きなかった場合を「合格」、絶縁破壊が起きた場合を「不合格」と評価した。
［耐熱性］
　ＩＳＯ ６７２２に規定される長期および短期過負荷の各加熱試験を行い、ＩＳＯ ６７２２ クラスＤの規格を満たした場合を「合格」、ＩＳＯ ６７２２ クラスＤの規格を満たさなかった場合を「不合格」と評価した。 [Flame retardance]
The 45 degree inclined combustion test specified in ISO 6722 is conducted, the fire is extinguished in 70 seconds, and the case where the insulator remains 50 mm or more is regarded as “pass”, and the case where the fire is not extinguished in 70 seconds is evaluated as “fail”. did.
[Insulation]
In accordance with ISO 6722, after immersing the wire in salt water for 4 hours, a withstand voltage test was performed at 1 kv × 30 minutes and 5 kV × 5 minutes. The case was evaluated as “Fail”.
[Heat-resistant]
Each of the long-term and short-term overload heating tests specified in ISO 6722 is conducted, and the case where the ISO 6722 class D standard is satisfied is “pass”, and the case where the ISO 6722 class D standard is not satisfied is “fail”. evaluated.
［耐摩耗性］
　ＪＡＳＯ Ｄ６１８に規定されるテープ摩耗試験を行い、導体が露出するまでのテープ長さ（摩耗テープ長さ）を測定し、下記の基準で評価した。
　Ａ：５００ｍｍ以上
　Ｂ：４５０ｍｍ以上５００ｍｍ未満
　Ｃ：４５０ｍｍ未満
［耐薬品性］
　ＩＳＯ ６７２２に準拠し、規定されている１１種の薬品（エンジンクーラント、エンジンオイル、塩水、ウィンドウオッシャー液、ガソリン、ディーゼル、エタノール、パワステアリングオイル、オートマチックトランスミッションオイル、ブレーキオイル、バッテリー液）について、それぞれ規定温度で規定時間、絶縁電線を浸漬した後、巻付け試験を行って破断なきことを確認し、その後、１ｋｖ×１分の耐電圧試験を行った。その結果、１１種の全ての薬品で絶縁破壊が起きなかった場合を「合格」、１種の薬品でも絶縁破壊が起きた場合を「不合格」と評価した。 [Abrasion resistance]
The tape wear test specified in JASO D618 was performed, and the tape length (wear tape length) until the conductor was exposed was measured and evaluated according to the following criteria.
A: 500 mm or more B: 450 mm or more and less than 500 mm C: less than 450 mm [chemical resistance]
Each of 11 types of chemicals (engine coolant, engine oil, salt water, window washer fluid, gasoline, diesel, ethanol, power steering oil, automatic transmission oil, brake oil, battery fluid) specified in accordance with ISO 6722 After immersing the insulated wire at a specified temperature for a specified time, a winding test was performed to confirm that there was no breakage, and then a withstand voltage test of 1 kv × 1 minute was performed. As a result, the case where dielectric breakdown did not occur with all 11 types of chemicals was evaluated as “pass”, and the case where dielectric breakdown occurred even with one type of chemical was evaluated as “failed”.
　これらの結果を表１および表２に示す。各表には、個々の特性に対する評価の結果とともに総合評価も併せ示した。 These results are shown in Tables 1 and 2. Each table also shows the overall evaluation as well as the results of the evaluation of individual characteristics.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１および表２から明らかなように、実施例１～９はいずれも機械的強度、熱変形性、柔軟性（作業性）、難燃性、絶縁性、耐熱性、耐摩耗性、および耐薬品性において、良好な結果が得られた。
　また、酸化防止剤（１）（ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］）を３．０～７．０質量部、酸化防止剤（２）（２－メルカプトベンゾイミダゾール）を３．０～７．０質量部、臭素系難燃剤（１，２－ビス（テトラブロモフタルイミド）エタン）を２５．０～３５．０質量部含有することにより、機械的強度、耐摩耗性において、より良好な結果が得られた。 As is clear from Tables 1 and 2, Examples 1 to 9 all have mechanical strength, thermal deformation, flexibility (workability), flame retardancy, insulation, heat resistance, wear resistance, and resistance to resistance. Good results were obtained in chemical properties.
Further, the antioxidant (1) (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) is added in an amount of 3.0 to 7.0 parts by mass, and the antioxidant (2 ) (2-mercaptobenzimidazole) in an amount of 3.0 to 7.0 parts by mass and brominated flame retardant (1,2-bis (tetrabromophthalimide) ethane) in an amount of 25.0 to 35.0 parts by mass. Better results were obtained in mechanical strength and abrasion resistance.
　本発明の車載用電線・ケーブルは、高い耐熱性と高い柔軟性を併せ持つことから、自動車のエンジンルームなどの高温環境下で使用する電線・ケーブルなどとして好適である。 The in-vehicle electric wire / cable of the present invention has both high heat resistance and high flexibility, and is therefore suitable as an electric wire / cable used in a high temperature environment such as an engine room of an automobile.
　１…導体、２…絶縁体。 1 ... conductor, 2 ... insulator.

Claims (7)

  1. 　導体外周に、エチレン・アクリル酸エチル共重合体を含むエチレン系共重合体１００質量部に対し、酸化防止剤として２．０～９．０質量部のペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］および２．０～８．０質量部の２－メルカプトベンゾイミダゾールを含有し、難燃剤として１５．０～３５．０質量部の１，２－ビス（テトラブロモフタルイミド）エタンを含有する樹脂組成物の架橋体からなる被覆を備えることを特徴とする車載用電線・ケーブル。 On the outer periphery of the conductor, 2.0 to 9.0 parts by mass of pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] and 2.0 to 8.0 parts by weight of 2-mercaptobenzimidazole, and 15.0 to 35.0 parts by weight of 1,2- A vehicle-mounted electric wire / cable comprising a coating made of a crosslinked product of a resin composition containing bis (tetrabromophthalimide) ethane.
  2. 　前記樹脂組成物は、エチレン系共重合体１００質量部に対し、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］を３．０～７．０質量部、２－メルカプトベンゾイミダゾールを３．０～７．０質量部、１，２－ビス（テトラブロモフタルイミド）エタンを２５．０～３５．０質量部含有することを特徴とする請求項１記載の車載用電線・ケーブル。 The resin composition contains 3.0 to 7.0 parts by mass of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] with respect to 100 parts by mass of the ethylene copolymer. 2. The composition according to claim 1, further comprising 3.0 to 7.0 parts by mass of 2-mercaptobenzimidazole and 25.0 to 35.0 parts by mass of 1,2-bis (tetrabromophthalimide) ethane. In-vehicle electric wires and cables.
  3. 　前記樹脂組成物は、エチレン系共重合体１００質量部に対し、難燃助剤として１５．０～２５．０質量部の三酸化アンチモンを含有することを特徴とする請求項１または２記載の車載用電線・ケーブル。 3. The resin composition according to claim 1, wherein the resin composition contains 15.0 to 25.0 parts by mass of antimony trioxide as a flame retardant aid with respect to 100 parts by mass of the ethylene copolymer. In-vehicle wires and cables.
  4. 　前記樹脂組成物は、エチレン系共重合体１００質量部に対し、金属不活性剤として２．０～８．０質量部の２’，３－ビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニル］ヒドラジンおよび／またはポリフェニレンオキサイドを含むことを特徴とする請求項１乃至３のいずれか１項記載の車載用電線・ケーブル。 The resin composition is used in an amount of 2.0 to 8.0 parts by weight of 2 ′, 3-bis [3- (3,5-di-tert- 4. The vehicle-mounted electric wire / cable according to claim 1, further comprising butyl-4-hydroxyphenyl) propionyl] hydrazine and / or polyphenylene oxide. 5.
  5. 　前記樹脂組成物は、エチレン系共重合体１００質量部に対し、分散剤として５．０～１５．０質量部の酸化亜鉛を含むことを特徴とする請求項１乃至４のいずれか１項記載の車載用電線・ケーブル。 5. The resin composition according to claim 1, wherein the resin composition contains 5.0 to 15.0 parts by mass of zinc oxide as a dispersant with respect to 100 parts by mass of the ethylene-based copolymer. In-vehicle electric wires and cables.
  6. 　前記エチレン系共重合体は、エチレン・アクリル酸エチル共重合体であることを特徴とする請求項１乃至５のいずれか１項記載の車載用電線・ケーブル。 The vehicle-mounted electric wire / cable according to any one of claims 1 to 5, wherein the ethylene copolymer is an ethylene / ethyl acrylate copolymer.
  7. 　自動車用電線規格ＩＳＯ ６７２２ Ｃｌａｓｓ Ｄに合格する耐熱性を有することを特徴とする請求項１乃至６のいずれか１項記載の車載用電線・ケーブル。 The in-vehicle electric wire / cable according to any one of claims 1 to 6, wherein the electric wire / cable for in-vehicle use has heat resistance that passes the automotive electric wire standard ISO 6722 Class D.
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