WO2011102533A1 - Sheathed electrical cable for motor vehicle - Google Patents

Sheathed electrical cable for motor vehicle Download PDF

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Publication number
WO2011102533A1
WO2011102533A1 PCT/JP2011/053880 JP2011053880W WO2011102533A1 WO 2011102533 A1 WO2011102533 A1 WO 2011102533A1 JP 2011053880 W JP2011053880 W JP 2011053880W WO 2011102533 A1 WO2011102533 A1 WO 2011102533A1
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WO
WIPO (PCT)
Prior art keywords
fire
parts
weight
electrical cable
retardant
Prior art date
Application number
PCT/JP2011/053880
Other languages
French (fr)
Other versions
WO2011102533A8 (en
Inventor
Kousuke Kougo
Original Assignee
Yazaki Corporation
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Publication date
Application filed by Yazaki Corporation filed Critical Yazaki Corporation
Publication of WO2011102533A1 publication Critical patent/WO2011102533A1/en
Publication of WO2011102533A8 publication Critical patent/WO2011102533A8/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C08L9/04—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a sheathed electrical cable for motor vehicle having an insulation sheath formed with a fire-retardant resin composition.
  • a fire-retardant resin composition of an insulation sheath of a sheathed electrical cable does not generate a halogen gas, which is harmful to a human body and a. cause of corrosion.
  • a conventional fire-retardant resin composition contains a fire-retardant additive such as magnesium hydroxide (for example, see JP 2009-40947 A, JP 2008-169273 A) .
  • the conventional fire-retardant resin composition contains a large amount of the fire-retardant additive such as magnesium hydroxide to attain the fire-retardancy
  • the large amount of the fire-retardant additive largely reduces a variety of mechanical properties such as wear resistance.
  • Demand for the fire-retardancy of the electrical cable insulation increases year by year.
  • the conventional insulation sheath of the electrical cable contains 60-90 parts by weight of magnesium hydroxide. However, this amount does not satisfy the fire-retardancy of the electrical cable.
  • the increase of the amount of the fire- retardant additive further reduces the mechanical properties.
  • An object of the present invention is to provide a sheathed electrical cable for a motor vehicle having a satisfactory fire-retardancy, while keeping a variety of mechanical properties such as a wear resistance, without generating a halogen-based gas.
  • a sheathed electrical cable for motor vehicle has a conductor and an insulation sheath covering the conductor, the insulation sheath being made of a fire-retardant resin composition containing 100 parts by weight of a base resin and 70-200 parts by weight of a metal hydrate fire- retardant additive, wherein the base resin contains (A) 70- 90 parts by weight of a polypropylene resin and (B) 30-10 parts by weight of an olefin or a styrene thermoplastic elastomer, and the metal hydrate fire-retardant additive is halogen free, and surface-treated with a fatty acid including unsaturated bond or with a silane treatment agent (A)
  • the polypropylene resin is, for example, propylene homopolymer, block copolymer of crystalline polyolefin and amorphous rubber, and copolymer of ethylene/propylene/butene .
  • the crystalline polyolefin is, for example, homopolymer or nonelastomer copolymer of ethylene, propylene, butene-1, hexene-1, and 4- methylpentene-1. It is preferable that the polypropylene resin contains a number of kinds. Among them, it is necessary to contain a polypropylene resin modified with maleic acid, that is, modified polypropylene resin.
  • the modified polypropylene resin can be manufactured with melt process or solution process.
  • the modified amount is 0.5-6.0 wt%, more preferably, 2-3 wt%.
  • the amount of the maleic acid modified resin is 5-30 parts by mass, preferably, 15- 20 parts by mass.
  • polypropylene resin other than the maleic acid modified resin has elastic coefficient of 1,000-2,000 Pa.
  • the olefin thermoplastic elastomer is, for example, a mixture of non-crystalline polyolefin and amorphous olefin copolymer rubber, propylene/ethylene random copolymer, propylene-a-olefin random copolymer, and propylene/ethylene-oc-olefin random copolymer.
  • the amorphous rubber is, for example, ethylene/propylene copolymer rubber (EPM) , ethylene/l-butene copolymer rubber (EB ) , ethylene/propylene/butene copolymer rubber, and ethylene/propylene/non-conjugated diene copolymer rubber.
  • Styrene thermoplastic elastomer besides the amorphous rubbers is block copolymer or random copolymer containing aromatic series vinyl polymer block (hard segment) and conjugated diene polymer block (soft segment) .
  • the aromatic series vinyl compound is oc-alkyl substitute styrene (e.g., styrene, oc-methylstyrene, ⁇ -ethylstyrene . , o-methyl-p- methylstyrene) , and nuclear alkyl substitute styrene (e . g .
  • the conjugated diene compound is, for example, butadiene, isoprene, and methylpentadiene .
  • the other rubber component is, for example, styrene-butadiene rubber (SBR) , nitrile rubber, and butyl rubber (IIR) .
  • the metal hydrate fire-retardant additive is magnesium hydroxide, aluminum hydroxide and calcium hydroxide, and metal hydroxide such as hydrotalcite, talc, or clay, surface-treated with the fatty acid including the unsaturated bond or with the silane treatment agent.
  • the fatty acid including the unsaturated bond is oleic acid, linolenic acid, crotonic acid, mitoleic acid, palmitoleic acid, elaidic acid, vaccenic acid, linoleic acid, eleostearic acid, stearidonic acid, gadoleic acid, eicosapentaenoic acid, erucic acid, clupanodonic acid, docosahexaenoic acid, and nervonic acid.
  • the silane treatment agent for surface-treating the magnesium hydroxide, the aluminum hydroxide, the calcium hydroxide, and the metal hydroxide such as hydrotalcite, talc, or clay is vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( ⁇ - methoxyethoxy) silane, ⁇ -(3,4- epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - glycidoxypropyltrimethoxysilane .
  • the surface coating treatment on the metal hydroxide particles with the silane treatment agent is achieved with the conventional wet process or dry process.
  • the wet process includes the steps of preparing a slurry of the magnesium hydroxide particles, adding a liquid or emulsion silane treatment agent to the slurry, and mechanically mixing the mixed slurry up to a temperature of about 100 degrees C.
  • the dry process includes the steps of stirring the magnesium hydroxide particles with a mixer, adding the liquid, emulsion, or solid silane treatment agent to the particles, and fully mixing with heat or without heat.
  • the present invention can contain fire-retardant additive, fire-retardant auxiliary agent, anti-oxidizing agent, metal inactive agent, anti-aging agent, lubricant, filler and reinforcing material, UV absorbent, stabilization agent, plasticizing material, pigment, dye, coloring agent, antistatic agent, and effervescent agent as long as they are not hindrance to the advantageous effects of the present invention.
  • FIG. 1 shows compounding ratios, and ⁇ evaluation results of fire-retardancy, elongation property and wear resistance of Examples 1-11;
  • FIG. 2 shows compounding ratios, and evaluation results of fire-retardancy, elongation property and wear resistance of Examples 12-15;
  • FIG. 3 shows compounding ratios, and evaluation results of fire-retardancy, elongation property and wear resistance of Comparative Examples 1-12;
  • FIG. 4 is a sectional view of a sheathed electrical cable of the present invention.
  • FIG. 4 is a sectional view of an embodiment of a fire-. retardant electrical cable 1 of the present invention.
  • the fire-retardant electrical cable 1 has a plurality of conductors 2, and an insulation sheath 3, which is made of a fire-retardant resin composition, covering ' the conductors 2. It is apparent that the electrical cable 1 may include a single conductor 2.
  • the fire-retardant resin composition of the present invention contains 100 parts by weight of a base resin and 70-200 parts by weight of a metal hydrate fire-retardant additive.
  • the base resin contains (A) 70-90 parts by weight of a polypropylene resin and (B) 30-10 parts by weight of an olefin or a styrene thermoplastic elastomer.
  • the metal hydrate fire-retardant additive is . a halogen-free metal hydrate surface-treated with a fatty acid containing an unsaturated bond or a silane treatment agent. All resins utilized here are non-cross linking type.
  • the polypropylene resin is, for example, propylene homopolymer, block copolymer of crystalline polyolefin and amorphous rubber, and copolymer of ethylene/propylene/butene .
  • the crystalline polyolefin is, for example, homopolymer or nonelastomer copolymer of ethylene, propylene, butene-1, hexene-1, and 4- methylpentene-1. It , is preferable, that the polypropylene resin contains a number of kinds. Among them, it is necessary to contain a polypropylene resin modified with maleic acid, that is, modified polypropylene resin.
  • the modified polypropylene resin can be manufactured with melt process or solution process.
  • the modified amount is 0.5-6.0 wt%, more preferably, 2-3 wt%.
  • the amount of the maleic acid modified resin is 5-30 parts by mass, preferably, 15- 20 parts by mass. When the amount of the maleic acid modified resin is less than the lower limit, wear resistance is reduced. When the amount of the maleic acid modified resin is more than the upper limit, elongation property is reduced. Also, it is suitable that polypropylene resin other than the maleic acid modified resin has elastic coefficient of 1,000-2,000 MPa.
  • the olefin thermoplastic elastomer is, for example, a mixture of non-crystalline polyolefin and amorphous olefin copolymer rubber, propylene/ethylene random copolymer propylene-a-olefin random copolymer, and propylene/ethylene-a-olefin random copolymer.
  • the amorphous rubber is, ' for example, ethylene/propylene copolymer rubber (EPM) , ethylene/l-butene copolymer rubber (EB ) , ethylene/propylene/butene copolymer rubber, and ethylene/propylene/non-conjugated diene copolymer rubber (EPDM) .
  • Styrene thermoplastic elastomer is block copolymer or random copolymer containing aromatic series vinyl polymer block (hard segment) and conjugated diene polymer block (soft segment) .
  • the aromatic series vinyl compound is a- alkyl substitute styrene (e.g., styrene, a-methylstyrene, a-ethylstyrene, a-methyl-p-methylstyrene) , and nuclear alkyl substitute styrene (e.g., o-methylstyrene, m- methylstyrene, p-methylstyrene, 2 , 4-dimethylstyrene, ethylstyrene, 2 , 4 , 6-trimethylstyrene, o-t-butylstyrene, p- t-butylstyrene, p-cyclohexylstyrene
  • the conjugated diene compound is, for example, butadiene, isoprene, and methylpentadiene .
  • the other rubber component is, for example, styrene-butadiene rubber (SBR) , nitrile rubber, and butyl rubber (IIR) .
  • the metal hydrate fire-retardant additive is magnesium hydroxide or aluminum hydroxide surface-treated with the fatty acid containing the unsaturated bond such as oleic acid, linolenic acid and the like, or surface-treated with the silane treatment agent.
  • the resin composition of the present invention has a high fire-retardancy, and also high mechanical properties such as wear resistance and elongation property.
  • the fire- retardant resin composition is thus utilized for the insulation sheath of the electrical cable 1 of the motor vehicle because of a high reliability.
  • the embodiment of the sheathed electrical cable 1 of the present invention has the insulation sheath 3 with a thickness of 0.2-0.9 mm, which gives the improved wear resistance for use in the motor vehicle.
  • the electrical cable 1 having the insulation sheath 3 with the thickness of 0.2-0.9 mm corresponds to the product names of CHFUS- 0.13 ⁇ 1.5sq, HFSS-0.35 ⁇ 2f, and HF-3 ⁇ 8sq.
  • the insulation sheath 3 with the thickness more than 0.9 mm increases its own volume and reduces the fire-retardancy. The increase of the thickness reduces heat absorption of the conductors 2 when the insulation sheath 3 burns.
  • the thick insulation sheath 3 retards the heat transfer to the central conductors 2.
  • the standard electrical cable 1 for motor vehicle usually has the insulation sheath 3 with the thickness of more than 0.2 mm.
  • the insulation sheath 3 with the thickness less than 0.2 mm exposes the conductors 2 when the insulation sheath 3 wears out, and is thus not adapted for the electrical cable of the motor vehicle.
  • the polypropylene resin was a polypropylene homopolymer of PS201A (Product of SunAllomer Ltd.).
  • the modified polypropylene resin is Umex 1010 (Product of Sanyo Chemical Industries Ltd.).
  • the metal hydrate fire-retardant additive was KISUMA-5P (Product of Kyowa Chemical Industry Co., Ltd.).
  • a supplemental agent (MD-1024: Product name of Ciba Specialty Chemicals) for metal and (E) An anti-oxidizing agent (Irganox 1010: Product name of Ciba Specialty Chemicals) may be added.
  • the evaluation of the fire-retardancy had the following steps of extrusion-forming the fire-retardant resin composition around the conductor, cutting the sheathed electrical cable for motor vehicle by a length of 600 mm, holding the sheathed electrical cable in a no-wind tank with an angle of 45 degrees, exposing a portion distant about 200 mm ⁇ 5 mm from an upper end of the sample cable to a reducing flame of a Bunsen burner for 15 seconds, gently removing the flame, and measuring a time when the flame of the electrical cable disappears.
  • the target value is at most 70 seconds. When the measured time is within 70 seconds, the electrical cable is evaluated as "acceptable, denoted by a circle", and the measured time is more than 70 seconds, the electrical cable is evaluated as "not acceptable, denoted by X".
  • the evaluation of the elongation property was achieved in accordance with JIS B 7721.
  • the evaluation had the following steps of cutting the sheathe electrical cable by 150 mm, removing the conductors from the sheathed electrical cable to form a cylindrical shaped test piece of the insulation layer, indicating marks spaced 50 mm each other, attaching each end to an associated chuck of a tension tester at a room temperature, pulling the insulation sheath by 25-500 mm/min, and measuring a distance between the marks.
  • the insulation sheath is evaluated as "acceptable, denoted by the circle” when the extension is at least 500 percents and "not acceptable, denoted by X" when the extension is less than 500 percents.
  • the evaluation of wear resistance was achieved with the scrape wear resistance tester.
  • the evaluation had the following steps of mounting the sheathed electrical cable of about 1 m on a sample holder, holding the electrical cable with a clamp, preparing a plunge having a piano wire of 0.45 mm, abutting the plunge to the end of the sheathed electrical cable, press-reciprocating the plunge with a total load of 7 N to the sheathed electrical cable by a distance of 14 mm, measuring a reciprocating cycle until the piano wire of the plunge reaches the conductors of the electrical cable due to the wear of the insulation layer.
  • the insulation sheath is evaluated "acceptable, denoted by the circle” when the cycle is at least 300 and "not acceptable, denoted by X" when the cycle is less than 300.
  • FIGS. 1-3 show the respective parts by weight of the associated compounding of Examples 1-11 and Comparative Examples 1-13. Each compounding material is melt-mixed at a temperature of 200 degrees C and extrude-formed with an extruder to form the sheathed electrical cable as shown in FIG. 4.
  • the test examples (Examples and Comparative Examples) of the sheathed electrical cables are the same as the standard CHFUS-l.Osq and HFSS-2f. All of Examples 1-12 and Comparative Examples 1-6 contain 1 part by weight of the anti-oxidant agent.
  • FIGS. 1-3 also show the test results of the fire-retardancy, the elongation property and the wear resistance.
  • Examples 1-12 contain 100 parts by weight of the base resin (A+B) and 70-200 parts by weight of the metal hydrate fire-retardant additive (C) .
  • the base resins (A+B) contain (A) 70-90 parts by weight of polypropylene and (B) 30-10 parts by weight of olefin or styrene thermoplastic elastomer.
  • the metal hydrate fire-retardant additive is magnesium hydroxide surface-treated with oleic acid.
  • Comparative Examples 1-6 contain 100 parts by weight of the base resin (A+B) , and 65 or 205 parts by weight of the metal hydrate fire-retardant additive (C) .
  • the base resins (A+B) contain (A) 70-90 parts by weight of polypropylene and (B) 30-10 parts by weight of olefin thermoplastic or styrene thermoplastic elastomer.
  • the metal hydrate fire-retardant additive (C) is magnesium hydroxide surface-treated with oleic acid.
  • the fire- retardant resin compositions containing 100 parts by weight of the base resin and 70-200 parts by weight of the metal hydrate fire-retardant additive satisfy the required properties.
  • Examples 1-3 indicates that Examples 1-4 containing 70 parts by weight of the metal hydrate fire-retardant additive provided good results about the fire-retardancy, the elongation property and the wear resistance. Comparative Examples 1-3 containing 65 parts by weight of the metal hydrate fire-retardant additive were not acceptable (X) with respect to the fire-retardancy. Accordingly, it is preferably to contain at least 70 parts by weight of the metal hydrate fire-retardant additive in the fire-retardant resin composition.
  • Comparison between Examples 10-12 and Comparative Examples 4-6 indicates that the fire-retardant resin compositions containing 200 parts by weight of the metal hydrate fire-retardant additive provided good results about the fire-retardancy, the elongation property and the wear resistance, and that Comparative Example 4 was not acceptable (X) about the elongation property and the wear resistance and Comparative Examples 5, 6 were not acceptable (X) about the wear resistance. Accordingly, it is preferably to contain at most 200 parts by weight of the metal hydrate fire-retardant additive in the fire-retardant resin composition.
  • the fire-retardant resin composition includes the base resin and the metal hydrate fire-retardant additive.
  • the metal hydrate fire-retardant additive is magnesium hydroxide or aluminum hydroxide single or combination surface-treated with the fatty acid including the unsaturated boding such as oleic acid or linolenic acid, or with the silane treatment agent.
  • the resultant fire- retardant resin compositions provide the required fire- retardancy while keeping the variety of mechanical properties such as the wear resistance and the elongation property.
  • the present invention provides a highly reliable sheathed electrical cable for motor vehicle having a fire- retardancy while keeping a mechanical property such as a wear resistance.

Abstract

The present invention is to provide a sheathed electrical cable for motor vehicle having a f ire-retardancy as well as a mechanical property such as a wear resistance. An insulation sheath of the electrical cable is made of a f ire-retardant resin composition containing 100 parts by weight of a base resin and 70-200 parts by weight of a metal hydrate f ire-retardant additive. The base resin contains (A) 70-90 parts by weight of a polypropylene resin and (B) 30-10 parts by weight of an olefin or a styrene thermoplastic elastomer, and the metal hydrate fire- retardant additive is halogen free, and surface-treated with a fatty acid including unsaturated bond or with a silane treatment agent.

Description

DESCRIPTION
SHEATHED ELECTRICAL CABLE FOR MOTOR VEHICLE Technical Field
The present invention relates to a sheathed electrical cable for motor vehicle having an insulation sheath formed with a fire-retardant resin composition. Related Art
It is requested that a fire-retardant resin composition of an insulation sheath of a sheathed electrical cable does not generate a halogen gas, which is harmful to a human body and a. cause of corrosion. A conventional fire-retardant resin composition contains a fire-retardant additive such as magnesium hydroxide (for example, see JP 2009-40947 A, JP 2008-169273 A) .
The conventional fire-retardant resin composition contains a large amount of the fire-retardant additive such as magnesium hydroxide to attain the fire-retardancy The large amount of the fire-retardant additive largely reduces a variety of mechanical properties such as wear resistance. Demand for the fire-retardancy of the electrical cable insulation increases year by year. The conventional insulation sheath of the electrical cable contains 60-90 parts by weight of magnesium hydroxide. However, this amount does not satisfy the fire-retardancy of the electrical cable. The increase of the amount of the fire- retardant additive further reduces the mechanical properties.
Disclosure of the Invention
An object of the present invention is to provide a sheathed electrical cable for a motor vehicle having a satisfactory fire-retardancy, while keeping a variety of mechanical properties such as a wear resistance, without generating a halogen-based gas.
According to a "first object of the present invention, a sheathed electrical cable for motor vehicle, has a conductor and an insulation sheath covering the conductor, the insulation sheath being made of a fire-retardant resin composition containing 100 parts by weight of a base resin and 70-200 parts by weight of a metal hydrate fire- retardant additive, wherein the base resin contains (A) 70- 90 parts by weight of a polypropylene resin and (B) 30-10 parts by weight of an olefin or a styrene thermoplastic elastomer, and the metal hydrate fire-retardant additive is halogen free, and surface-treated with a fatty acid including unsaturated bond or with a silane treatment agent (A) The polypropylene resin is, for example, propylene homopolymer, block copolymer of crystalline polyolefin and amorphous rubber, and copolymer of ethylene/propylene/butene . The crystalline polyolefin is, for example, homopolymer or nonelastomer copolymer of ethylene, propylene, butene-1, hexene-1, and 4- methylpentene-1. It is preferable that the polypropylene resin contains a number of kinds. Among them, it is necessary to contain a polypropylene resin modified with maleic acid, that is, modified polypropylene resin. The modified polypropylene resin can be manufactured with melt process or solution process. The modified amount is 0.5-6.0 wt%, more preferably, 2-3 wt%. The amount of the maleic acid modified resin is 5-30 parts by mass, preferably, 15- 20 parts by mass. When the amount of the maleic acid modified resin is less than the lower limit, wear resistance is reduced. When the amount of the maleic acid modified resin is more than the upper limit, elongation property is reduced. Also, it is suitable that polypropylene resin other than the maleic acid modified resin has elastic coefficient of 1,000-2,000 Pa.
(B) The olefin thermoplastic elastomer is, for example, a mixture of non-crystalline polyolefin and amorphous olefin copolymer rubber, propylene/ethylene random copolymer, propylene-a-olefin random copolymer, and propylene/ethylene-oc-olefin random copolymer. The amorphous rubber is, for example, ethylene/propylene copolymer rubber (EPM) , ethylene/l-butene copolymer rubber (EB ) , ethylene/propylene/butene copolymer rubber, and ethylene/propylene/non-conjugated diene copolymer rubber. Styrene thermoplastic elastomer besides the amorphous rubbers is block copolymer or random copolymer containing aromatic series vinyl polymer block (hard segment) and conjugated diene polymer block (soft segment) . The aromatic series vinyl compound is oc-alkyl substitute styrene (e.g., styrene, oc-methylstyrene, ά-ethylstyrene., o-methyl-p- methylstyrene) , and nuclear alkyl substitute styrene (e . g . , o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4- dimethylstyrene, ethylstyrene, 2, 4, 6-trimethylstyrene, o-t- butylstyrene, p-t-butylstyrene, p-cyclohexylstyrene) . The conjugated diene compound is, for example, butadiene, isoprene, and methylpentadiene . The other rubber component is, for example, styrene-butadiene rubber (SBR) , nitrile rubber, and butyl rubber (IIR) .
(C) The metal hydrate fire-retardant additive is magnesium hydroxide, aluminum hydroxide and calcium hydroxide, and metal hydroxide such as hydrotalcite, talc, or clay, surface-treated with the fatty acid including the unsaturated bond or with the silane treatment agent.
The fatty acid including the unsaturated bond is oleic acid, linolenic acid, crotonic acid, mitoleic acid, palmitoleic acid, elaidic acid, vaccenic acid, linoleic acid, eleostearic acid, stearidonic acid, gadoleic acid, eicosapentaenoic acid, erucic acid, clupanodonic acid, docosahexaenoic acid, and nervonic acid. The silane treatment agent for surface-treating the magnesium hydroxide, the aluminum hydroxide, the calcium hydroxide, and the metal hydroxide such as hydrotalcite, talc, or clay, is vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( β- methoxyethoxy) silane, β-(3,4- epoxycyclohexyl) ethyltrimethoxysilane, γ- glycidoxypropyltrimethoxysilane .
The surface coating treatment on the metal hydroxide particles with the silane treatment agent (silane coupling agent) is achieved with the conventional wet process or dry process. The wet process includes the steps of preparing a slurry of the magnesium hydroxide particles, adding a liquid or emulsion silane treatment agent to the slurry, and mechanically mixing the mixed slurry up to a temperature of about 100 degrees C. The dry process includes the steps of stirring the magnesium hydroxide particles with a mixer, adding the liquid, emulsion, or solid silane treatment agent to the particles, and fully mixing with heat or without heat.
In addition to the above essential components, the present invention can contain fire-retardant additive, fire-retardant auxiliary agent, anti-oxidizing agent, metal inactive agent, anti-aging agent, lubricant, filler and reinforcing material, UV absorbent, stabilization agent, plasticizing material, pigment, dye, coloring agent, antistatic agent, and effervescent agent as long as they are not hindrance to the advantageous effects of the present invention. Brief Description of the Drawings
FIG. 1 shows compounding ratios, and ■ evaluation results of fire-retardancy, elongation property and wear resistance of Examples 1-11;
FIG. 2 shows compounding ratios, and evaluation results of fire-retardancy, elongation property and wear resistance of Examples 12-15;
FIG. 3 shows compounding ratios, and evaluation results of fire-retardancy, elongation property and wear resistance of Comparative Examples 1-12; and
FIG. 4 is a sectional view of a sheathed electrical cable of the present invention.
Best Mode for Carrying out the Invention
Embodiments of a sheathed electrical cable for motor vehicle of the present invention are explained in detail below.
Sheathed Electrical. Cable for Motor Vehicle:
FIG. 4 is a sectional view of an embodiment of a fire-. retardant electrical cable 1 of the present invention. The fire-retardant electrical cable 1 has a plurality of conductors 2, and an insulation sheath 3, which is made of a fire-retardant resin composition, covering' the conductors 2. It is apparent that the electrical cable 1 may include a single conductor 2.
Fire-Retardant Resin Composition:
The fire-retardant resin composition of the present invention contains 100 parts by weight of a base resin and 70-200 parts by weight of a metal hydrate fire-retardant additive. The base resin contains (A) 70-90 parts by weight of a polypropylene resin and (B) 30-10 parts by weight of an olefin or a styrene thermoplastic elastomer. The metal hydrate fire-retardant additive is . a halogen-free metal hydrate surface-treated with a fatty acid containing an unsaturated bond or a silane treatment agent. All resins utilized here are non-cross linking type.
The polypropylene resin is, for example, propylene homopolymer, block copolymer of crystalline polyolefin and amorphous rubber, and copolymer of ethylene/propylene/butene . The crystalline polyolefin is, for example, homopolymer or nonelastomer copolymer of ethylene, propylene, butene-1, hexene-1, and 4- methylpentene-1. It , is preferable, that the polypropylene resin contains a number of kinds. Among them, it is necessary to contain a polypropylene resin modified with maleic acid, that is, modified polypropylene resin. The modified polypropylene resin can be manufactured with melt process or solution process. The modified amount is 0.5-6.0 wt%, more preferably, 2-3 wt%. The amount of the maleic acid modified resin is 5-30 parts by mass, preferably, 15- 20 parts by mass. When the amount of the maleic acid modified resin is less than the lower limit, wear resistance is reduced. When the amount of the maleic acid modified resin is more than the upper limit, elongation property is reduced. Also, it is suitable that polypropylene resin other than the maleic acid modified resin has elastic coefficient of 1,000-2,000 MPa.
The olefin thermoplastic elastomer is, for example, a mixture of non-crystalline polyolefin and amorphous olefin copolymer rubber, propylene/ethylene random copolymer propylene-a-olefin random copolymer, and propylene/ethylene-a-olefin random copolymer. The amorphous rubber is, ' for example, ethylene/propylene copolymer rubber (EPM) , ethylene/l-butene copolymer rubber (EB ) , ethylene/propylene/butene copolymer rubber, and ethylene/propylene/non-conjugated diene copolymer rubber (EPDM) .
Styrene thermoplastic elastomer is block copolymer or random copolymer containing aromatic series vinyl polymer block (hard segment) and conjugated diene polymer block (soft segment) . The aromatic series vinyl compound is a- alkyl substitute styrene (e.g., styrene, a-methylstyrene, a-ethylstyrene, a-methyl-p-methylstyrene) , and nuclear alkyl substitute styrene (e.g., o-methylstyrene, m- methylstyrene, p-methylstyrene, 2 , 4-dimethylstyrene, ethylstyrene, 2 , 4 , 6-trimethylstyrene, o-t-butylstyrene, p- t-butylstyrene, p-cyclohexylstyrene) . The conjugated diene compound is, for example, butadiene, isoprene, and methylpentadiene . The other rubber component is, for example, styrene-butadiene rubber (SBR) , nitrile rubber, and butyl rubber (IIR) .
The metal hydrate fire-retardant additive is magnesium hydroxide or aluminum hydroxide surface-treated with the fatty acid containing the unsaturated bond such as oleic acid, linolenic acid and the like, or surface-treated with the silane treatment agent.
The resin composition of the present invention has a high fire-retardancy, and also high mechanical properties such as wear resistance and elongation property. The fire- retardant resin composition is thus utilized for the insulation sheath of the electrical cable 1 of the motor vehicle because of a high reliability.
The embodiment of the sheathed electrical cable 1 of the present invention has the insulation sheath 3 with a thickness of 0.2-0.9 mm, which gives the improved wear resistance for use in the motor vehicle. The electrical cable 1 having the insulation sheath 3 with the thickness of 0.2-0.9 mm corresponds to the product names of CHFUS- 0.13~1.5sq, HFSS-0.35~2f, and HF-3~8sq. The insulation sheath 3 with the thickness more than 0.9 mm increases its own volume and reduces the fire-retardancy. The increase of the thickness reduces heat absorption of the conductors 2 when the insulation sheath 3 burns. The thick insulation sheath 3 retards the heat transfer to the central conductors 2. The standard electrical cable 1 for motor vehicle usually has the insulation sheath 3 with the thickness of more than 0.2 mm. The insulation sheath 3 with the thickness less than 0.2 mm exposes the conductors 2 when the insulation sheath 3 wears out, and is thus not adapted for the electrical cable of the motor vehicle.
Examples :
Examples and Comparative Examples of the present invention are explained by referring to FIGS. 1-3.
Materials Utilized for Examples and Comparative Examples:
(A) Polypropylene resin
The polypropylene resin was a polypropylene homopolymer of PS201A (Product of SunAllomer Ltd.). The modified polypropylene resin is Umex 1010 (Product of Sanyo Chemical Industries Ltd.).
(B) The olefin or the styrene thermoplastic elastomer was Q200f (Product of SunAllomer Ltd.).
(C) ,The metal hydrate fire-retardant additive was KISUMA-5P (Product of Kyowa Chemical Industry Co., Ltd.).
Beside the above materials,
(D) A supplemental agent (MD-1024: Product name of Ciba Specialty Chemicals) for metal and (E) An anti-oxidizing agent (Irganox 1010: Product name of Ciba Specialty Chemicals) may be added.
Evaluation:
The evaluation of the fire-retardancy had the following steps of extrusion-forming the fire-retardant resin composition around the conductor, cutting the sheathed electrical cable for motor vehicle by a length of 600 mm, holding the sheathed electrical cable in a no-wind tank with an angle of 45 degrees, exposing a portion distant about 200 mm ± 5 mm from an upper end of the sample cable to a reducing flame of a Bunsen burner for 15 seconds, gently removing the flame, and measuring a time when the flame of the electrical cable disappears. The target value is at most 70 seconds. When the measured time is within 70 seconds, the electrical cable is evaluated as "acceptable, denoted by a circle", and the measured time is more than 70 seconds, the electrical cable is evaluated as "not acceptable, denoted by X".
The evaluation of the elongation property was achieved in accordance with JIS B 7721. The evaluation had the following steps of cutting the sheathe electrical cable by 150 mm, removing the conductors from the sheathed electrical cable to form a cylindrical shaped test piece of the insulation layer, indicating marks spaced 50 mm each other, attaching each end to an associated chuck of a tension tester at a room temperature, pulling the insulation sheath by 25-500 mm/min, and measuring a distance between the marks. The insulation sheath is evaluated as "acceptable, denoted by the circle" when the extension is at least 500 percents and "not acceptable, denoted by X" when the extension is less than 500 percents.
The evaluation of wear resistance was achieved with the scrape wear resistance tester. The evaluation had the following steps of mounting the sheathed electrical cable of about 1 m on a sample holder, holding the electrical cable with a clamp, preparing a plunge having a piano wire of 0.45 mm, abutting the plunge to the end of the sheathed electrical cable, press-reciprocating the plunge with a total load of 7 N to the sheathed electrical cable by a distance of 14 mm, measuring a reciprocating cycle until the piano wire of the plunge reaches the conductors of the electrical cable due to the wear of the insulation layer. The insulation sheath is evaluated "acceptable, denoted by the circle" when the cycle is at least 300 and "not acceptable, denoted by X" when the cycle is less than 300.
Embodiments of the present invention are explained below, and Examples and Comparative Examples are compared. FIGS. 1-3 show the respective parts by weight of the associated compounding of Examples 1-11 and Comparative Examples 1-13. Each compounding material is melt-mixed at a temperature of 200 degrees C and extrude-formed with an extruder to form the sheathed electrical cable as shown in FIG. 4. The test examples (Examples and Comparative Examples) of the sheathed electrical cables are the same as the standard CHFUS-l.Osq and HFSS-2f. All of Examples 1-12 and Comparative Examples 1-6 contain 1 part by weight of the anti-oxidant agent. FIGS. 1-3 also show the test results of the fire-retardancy, the elongation property and the wear resistance.
Examples 1-11:
Examples 1-12 contain 100 parts by weight of the base resin (A+B) and 70-200 parts by weight of the metal hydrate fire-retardant additive (C) . The base resins (A+B) contain (A) 70-90 parts by weight of polypropylene and (B) 30-10 parts by weight of olefin or styrene thermoplastic elastomer. The metal hydrate fire-retardant additive is magnesium hydroxide surface-treated with oleic acid.
Comparative Examples 1-13:
Comparative Examples 1-6 contain 100 parts by weight of the base resin (A+B) , and 65 or 205 parts by weight of the metal hydrate fire-retardant additive (C) . The base resins (A+B) contain (A) 70-90 parts by weight of polypropylene and (B) 30-10 parts by weight of olefin thermoplastic or styrene thermoplastic elastomer. The metal hydrate fire-retardant additive (C) is magnesium hydroxide surface-treated with oleic acid.
Referring to FIGS. 1-3, it is apparent that the fire- retardant resin compositions containing 100 parts by weight of the base resin and 70-200 parts by weight of the metal hydrate fire-retardant additive satisfy the required properties.
Comparison between Examples 1-4 and Comparative
Examples 1-3 indicates that Examples 1-4 containing 70 parts by weight of the metal hydrate fire-retardant additive provided good results about the fire-retardancy, the elongation property and the wear resistance. Comparative Examples 1-3 containing 65 parts by weight of the metal hydrate fire-retardant additive were not acceptable (X) with respect to the fire-retardancy. Accordingly, it is preferably to contain at least 70 parts by weight of the metal hydrate fire-retardant additive in the fire-retardant resin composition.
Comparison between Examples 10-12 and Comparative Examples 4-6 indicates that the fire-retardant resin compositions containing 200 parts by weight of the metal hydrate fire-retardant additive provided good results about the fire-retardancy, the elongation property and the wear resistance, and that Comparative Example 4 was not acceptable (X) about the elongation property and the wear resistance and Comparative Examples 5, 6 were not acceptable (X) about the wear resistance. Accordingly, it is preferably to contain at most 200 parts by weight of the metal hydrate fire-retardant additive in the fire-retardant resin composition.
The fire-retardant resin composition includes the base resin and the metal hydrate fire-retardant additive. The metal hydrate fire-retardant additive is magnesium hydroxide or aluminum hydroxide single or combination surface-treated with the fatty acid including the unsaturated boding such as oleic acid or linolenic acid, or with the silane treatment agent. The resultant fire- retardant resin compositions provide the required fire- retardancy while keeping the variety of mechanical properties such as the wear resistance and the elongation property.
Industrial Applicability
The present invention provides a highly reliable sheathed electrical cable for motor vehicle having a fire- retardancy while keeping a mechanical property such as a wear resistance.

Claims

Claims
1. A sheathed electrical cable for motor vehicle, having a conductor and an insulation sheath covering the conductor, the insulation sheath being made of a fire-retardant resin composition containing 100 parts by weight of a base resin and 70-200 parts by weight of a metal hydrate fire- retardant additive,
wherein the base resin contains (A) 5-30 parts by weight of a modified polypropylene resin and 40-85 parts by weight of a polypropylene resin and (B) 30-10 parts by weight of an olefin or a styrene thermoplastic elastomer, and the metal hydrate fire-retardant additive is halogen free, and surface-treated with, a fatty acid including unsaturated bond or with a silane treatment agent.
2. The sheathed electrical cable as claimed in claim 1, wherein the insulation sheath has a thickness of 0.2-0.9 mm.
PCT/JP2011/053880 2010-02-16 2011-02-16 Sheathed electrical cable for motor vehicle WO2011102533A1 (en)

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JP2010031374A JP2013020699A (en) 2010-02-16 2010-02-16 Insulation wire for motor car
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Citations (9)

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Publication number Priority date Publication date Assignee Title
JP2002138173A (en) * 2000-11-01 2002-05-14 Sumitomo Wiring Syst Ltd Heat-resistant and flame-retardant resin composition
JP2002140940A (en) * 2000-11-01 2002-05-17 Sumitomo Wiring Syst Ltd Insulated wire
JP2002167480A (en) * 2000-12-01 2002-06-11 Sumitomo Wiring Syst Ltd Olefin-based resin composition and covered electric wire
JP2002212354A (en) * 2001-01-19 2002-07-31 Sumitomo Wiring Syst Ltd Olefinic resin composition, method for producing the same and electric cable coated therewith
JP2004075992A (en) * 2002-06-18 2004-03-11 Furukawa Electric Co Ltd:The Flame-retardant resin composition, its production method and insulated electric wire coated with the same
JP2005239755A (en) * 2004-02-24 2005-09-08 Fujikura Ltd Nonhalogen flame-retardant/heat-resistant resin composition and insulated wire using the same
JP2006199923A (en) * 2004-12-22 2006-08-03 Furukawa Electric Co Ltd:The Flame-retardant resin composition and molded product using the same
JP2008195933A (en) * 2007-01-19 2008-08-28 Mitsubishi Chemicals Corp Flexible propylene resin composition
JP2009161703A (en) * 2008-01-10 2009-07-23 Yazaki Corp Polyolefinic resin composition and covered electric wire

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002138173A (en) * 2000-11-01 2002-05-14 Sumitomo Wiring Syst Ltd Heat-resistant and flame-retardant resin composition
JP2002140940A (en) * 2000-11-01 2002-05-17 Sumitomo Wiring Syst Ltd Insulated wire
JP2002167480A (en) * 2000-12-01 2002-06-11 Sumitomo Wiring Syst Ltd Olefin-based resin composition and covered electric wire
JP2002212354A (en) * 2001-01-19 2002-07-31 Sumitomo Wiring Syst Ltd Olefinic resin composition, method for producing the same and electric cable coated therewith
JP2004075992A (en) * 2002-06-18 2004-03-11 Furukawa Electric Co Ltd:The Flame-retardant resin composition, its production method and insulated electric wire coated with the same
JP2005239755A (en) * 2004-02-24 2005-09-08 Fujikura Ltd Nonhalogen flame-retardant/heat-resistant resin composition and insulated wire using the same
JP2006199923A (en) * 2004-12-22 2006-08-03 Furukawa Electric Co Ltd:The Flame-retardant resin composition and molded product using the same
JP2008195933A (en) * 2007-01-19 2008-08-28 Mitsubishi Chemicals Corp Flexible propylene resin composition
JP2009161703A (en) * 2008-01-10 2009-07-23 Yazaki Corp Polyolefinic resin composition and covered electric wire

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