WO2010024602A2 - Polypropylene-based flame-resistant resin composition for cable insulation material with superior mechanical properties - Google Patents

Polypropylene-based flame-resistant resin composition for cable insulation material with superior mechanical properties Download PDF

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Publication number
WO2010024602A2
WO2010024602A2 PCT/KR2009/004783 KR2009004783W WO2010024602A2 WO 2010024602 A2 WO2010024602 A2 WO 2010024602A2 KR 2009004783 W KR2009004783 W KR 2009004783W WO 2010024602 A2 WO2010024602 A2 WO 2010024602A2
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Prior art keywords
resin composition
polypropylene resin
resin
retardant
polypropylene
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PCT/KR2009/004783
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French (fr)
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WO2010024602A3 (en
Inventor
Do-Hoon Chang
Sun-Keun Kim
In-Ha Kim
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Ls Cable Ltd.
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Publication of WO2010024602A2 publication Critical patent/WO2010024602A2/en
Publication of WO2010024602A3 publication Critical patent/WO2010024602A3/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
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    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
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    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • 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
    • 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
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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    • 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
    • C08K2003/222—Magnesia, i.e. magnesium oxide
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    • 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
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate
    • 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
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    • C08K2003/387—Borates
    • 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
    • C08L23/06—Polyethene
    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

  • the present invention relates to a polypropylene-based flame-retardant resin composition that exhibits excellent harmony of mechanical properties such as abrasion resistance, flexibility and so on.
  • the present invention relates to a flame- retardant insulating resin composition comprising polypropylene, rubber, a polar modified resin and an inorganic flame-retardant, and to an electric cable using the same.
  • a polypropylene resin is one of all- purpose plastics, and excellent in processability, chemical resistance, weather resistance, mechanical strength.
  • the polypropylene resin is widely used in domestic electric products, building materials, interior materials, vehicle components and so on, and its application range is expanded to coating materials of electric cables.
  • a polyethylene resin has good flame-re- tardancy.
  • the polyethylene resin is crosslinked, the necessary levels of flame re- tardancy and mechanical strength can be obtained.
  • the crosslinked polyethylene resin cannot be recycled.
  • the polypropylene resin has heat resistance (of the predetermined level for class C type cables) and mechanical strength without crosslinking, and can be recycled.
  • the present invention provides a polypropylene-based flame- retardant insulating resin composition.
  • the insulating resin composition comprises a base resin including 10 to 99 weight% of a polypropylene resin that satisfies the predetermined levels of abrasion resistance, flexibility and elasticity, and 1 to 90 weight% of an adjuvant resin; and 50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the base resin.
  • the adjuvant resin is at least one polymer resin selected from the group consisting of a rubber and a polyolefin grafted with a polar functional group.
  • the polypropylene resin satisfies the following levels of abrasion resistance and flexibility.
  • a specimen made solely from the polypropylene resin has an abraded depth of 0.001 to 0.2 mm measured by a scrape test, a bending elasticity of 90 to 180 kgf/mm 2 measured by a three-point bending test, and a storage modulus of 500 to 3,000 MPa measured by dynamic mechanical analysis.
  • the rubber of the adjuvant resin may be at least one selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-ethylacrylate (EEA), styrene-butadiene-styrene (SBS) rubber, styrene-ethylene-butadiene-styrene (SEBS) copolymer, ethylene- propylene-diene monomer (EPDM) rubber, ethylene glycol dimethacrylate (EGDM) rubber, ethylene-butylacrylate (EBA) copolymer and polyolefin elastomer (POE).
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • EVA ethylene-vinyl acetate copolymer
  • EMA ethylene-methyl acrylate
  • ESA styren
  • the polar modified resin of the adjuvant resin may be at least one selected from the group consisting of modified polypropylene, modified polyethylene and modified polyolefin elastomers that are grafted with a polar material to contain a polar functional group.
  • the grafting polar material may be selected from the group consisting of maleic anhydride, anhydrous maleic acid, silane and fatty acid.
  • the insulating resin composition comprises a reactor-made thermoplastic polypropylene resin (a reactor-made thermoplastic polyolefin elastomer (RTPO) in which polyolefin is polypropylene), and 50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the reactor-made thermoplastic polypropylene resin.
  • RTPO reactor-made thermoplastic polyolefin elastomer
  • the reactor-made thermoplastic polypropylene resin satisfies the predetermined levels of abrasion resistance, flexibility and elasticity when evaluated in the same way as the polypropylene resin according to an aspect of the present invention.
  • the reactor-made thermoplastic polypropylene resin has an abrasion resistance of 0.03 to 0.5 mm measured by a scrape test, a bending elasticity of 80 to 120 kgf/mm 2 measured by a three-point bending test and a storage modulus of 400 to 2,000 MPa measured by dynamic mechanical analysis.
  • the reactor-made thermoplastic polypropylene resin may be an ethylene-propylene rubber (EPR), an ethylene-propylene-diene monomer (EPDM) rubber or a reactor-made thermoplastic polyolefin elastomer (RTPO).
  • EPR ethylene-propylene rubber
  • EPDM ethylene-propylene-diene monomer
  • RTPO reactor-made thermoplastic polyolefin elastomer
  • the present invention provides a flame-retardant cable comprising an insulation coating layer formed using the insulating resin compositions according to the present invention.
  • Molded products manufactured using the insulating resin composition of the present invention exhibit excellent harmony of mechanical properties such as flame re- tardancy, abrasion resistance, tensile strength and elongation at break, and have a minimum occurrence of stress whitening on bending.
  • the insulating cable of the present invention exhibiting excellent harmony of properties is useful as a flame- retardant cable installed in the inner space of mechanisms holding the potential risk of fire, in particular, a heat-resistant cable of class C or higher rating for vehicles, ships, airplanes or space ships. Best Mode for Carrying out the Invention
  • the present invention has an object of providing a polypropylene-based insulation material for an electric cable, which is recyclable, heat-resistant, flame-retardant and low in hazard.
  • the inventors took notice of polypropylene satisfying the predetermined levels of mechanical properties, such as tensile strength, elongation, abrasion resistance and flexibility. In the end, they found that an insulation material comprising polypropylene exhibits harmony of mechanical properties and has excellent flame retardancy, even though an environmentally friendly inorganic flame-retardant is added.
  • the present invention provides a polypropylene-based insulating resin composition
  • a base resin including 10 to 99 weight% of a polypropylene resin that satisfies the predetermined levels of abrasion resistance, flexibility and elasticity; and 1 to 90 weight% of an adjuvant resin, and 50 to 200 parts by weight of a flame-retardant based on 100 parts by weight of the base resin.
  • the polypropylene resin is not limited to a specific type if it is a polymer satisfying the predetermined levels of abrasion resistance, flexibility and elasticity as mentioned below.
  • the polypropylene resin usable in the present invention may be a homopolymer of propylene, or a random or block copolymer or a terpolymer of propylene and an olefin monomer such as ethylene or the like.
  • the copolymer or terpolymer may be produced by polymerizing 70 mole% or more of a propylene monomer and an olefin monomer.
  • the polypropylene resin may be a mixed resin of polypropylene molecules satisfying said predetermined levels of mechanical properties.
  • the polypropylene resin may include various types of polypropylene-based resins, but to reduce or eliminate stress whitening, a polypropylene random copolymer is preferred.
  • the polypropylene resin of the present invention may be mixtures of the exemplary polymers.
  • the polypropylene resin has a melt flow index of about 0.2 to
  • the polypropylene resin also has a density of about 0.85 to 0.95 g/cm 3 and an average molecular mass of about 150,000 to 600,000. If the melt flow index of the polypropylene resin is less than 0.2 g/10 minutes, the composition has a low flowability, failing to improve productivity, and compatibility with other components reduces, resulting in insufficient mixing, which causes a reduction in mechanical strength. If the melt flow index of the polypropylene resin is more than 10 g/10 minutes, sufficient mechanical strength cannot be obtained due to a low molecular weight.
  • the object of the present invention is to provide a polypropylene-based flame-retardant insulating cable with excellent mechanical properties such as abrasion resistance, flexibility and so on, and a polypropylene-based insulating resin composition for said cable.
  • the polypropylene resin of the present invention should have the following properties.
  • the polypropylene resin of the present invention should satisfy an abrasion resistance of 0.001 to 0.2 mm by a scrape test performed on a specimen made solely from the polypropylene resin, except other components.
  • the scrape test is performed on a specimen made solely from the polypropylene resin, said scrape test comprising moving back and forth in the plane of the surface of said specimen, a needle having a diameter of 0.45+0.01 mm under a load of 1500 g vertically applied against said surface, and measuring how much the surface of the specimen is scraped.
  • the abraded depth is an index of abrasion resistance.
  • the scrape test is carried out at room temperature, unless otherwise stated.
  • the polypropylene resin having an abrasion resistance of 0.001 to 0.2 mm satisfies a suitable level of abrasion resistance for vehicle cable or the like, and has a high molecular weight. That is, when the abrasion resistance of the polypropylene resin is 0.001 to 0.2 mm, excellent base mechanical properties, a high melt strength and a good processability with a flame- retardant can be obtained. If the abraded depth measured by the scrape test is more than the maximum limit, flowability increases and compatibility with a flame-retardant deteriorates upon melting. On the contrary, if the abraded depth is less than the minimum limit, the composition becomes brittle and its flexibility reduces, and thus is not suitable as a material for an electric cable.
  • the polypropylene resin of the present invention has a flexural modulus of 90 to
  • the flexural modulus is an index of flexibility of the polypropylene resin.
  • the insulating resin composition and the polypropylene resin of the composition should have a proper flexural modulus.
  • the three-point bending test is performed on a specimen made solely from the polypropylene resin except other components and having 12 mm width x 2 mm thickness x 120 mm length, according to ASTM D 790 specifications.
  • the flexural modulus of the polypropylene resin is in the range of 90 to 180 kgf/ mm 2 , a high flexibility required for a vehicle cable is obtained, stress whitening reduces and work efficiency increases in the manufacture of a harness. If the flexural modulus is less than the minimum limit, work efficiency decreases in the manufacture of a harness. If the flexural modulus is more than the maximum limit, the composition becomes brittle and fragile, and stress whitening increases.
  • the polypropylene resin of the present invention has a storage modulus of 500 to 3,000 MPa measured by dynamic mechanical analysis.
  • the storage modulus is an index of mechanical properties of the polypropylene resin.
  • the dynamic mechanical analysis is performed on a specimen of 15 mm x 5 mm x 1 mm using a dynamic mechanical analyzer, DMA 2980 of TA Instruments, in a tension mode at -100 to 200 0 C under conditions of a temperature ramp rate of 2 °C/min, frequency of 1 Hz and an amplitude of 0.03%.
  • a value measured at 25 0 C is selected as storage modulus of the polypropylene resin.
  • the insulating resin composition of the present invention comprises a rubber and/or a modified resin containing a polar functional group.
  • the polypropylene resin, the rubber and/or the polar functional group constitute a base resin of the composition according to the present invention.
  • the rubber and/or the polar modified resin will be generally referred to as an adjuvant resin.
  • the rubber and the polar modified resin improve resistance to stress whitening and the mechanical properties of the polypropylene-based copolymer resin such as tensile strength and elongation at break.
  • the base resin includes 10 to 99 weight% of the polypropylene resin and 1 to 90 weight% of the adjuvant resin.
  • the rubber is a typical one used in the art.
  • the rubber usable in the present invention is not limited to a specific type, and includes a synthetic rubber and other synthetic elastomers.
  • the rubber includes low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene- vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate (EEA), styrene-butadiene-styrene (SBS) rubber, styrene-ethylene-butadiene-styrene (SEBS) copolymer, ethylene-propylene-diene monomer (EPDM) rubber, ethylene glycol dimethacrylate (EGDM) rubber, ethylene-butyl acrylate (EBA) copolymer and polyolefin elastomer (POE), however the present invention is not limited in this regard.
  • LDPE low density polyethylene
  • LLDPE
  • the polyolefin elastomer as the rubber is not limited to a specific type, but is preferably an ethylene-alpha olefin copolymer or a propylene-alpha olefin copolymer so as to increase resistance to stress whitening.
  • the ethylene-alpha olefin or propylene- alph aolefin copolymer includes, for example, ethylene-butene, ethylene-octene, ethylene -propylene and propylene-butene copolymers. Because the propylene-alpha olefin copolymer has a good compatibility with the polypropylene resin component, the propylene-alpha olefin copolymer is more preferred.
  • the rubber may occupy up to 90 weight% of the base resin.
  • the content of the rubber is in this range, flexibility of the whole composition improves and filling performance of an inorganic flame-retardant increases, and consequently the composition exhibits flame retardancy and mechanical strength.
  • the content of the rubber exceeds the maximum limit, heat resistance is reduced as the melting temperature of the mixture drops.
  • the polar modified resin is a polymer, in which a resin having a low polarity and a high compatibility with the polypropylene resin, such as polyolefin, is grafted with a polar functional group.
  • the polar modified resin of the present invention mediates compatibility between the inorganic flame-retardant and the polymer resin so that the inorganic flame-retardant particles having a high polarity can be uniformly dispersed in the matrix of the polypropylene resin having a low polarity without agglomeration.
  • the mediation of the polar modified resin suppresses dewetting caused by rupture on an interface between the inorganic flame-retardant and the base resin.
  • the modified rubber grafted with the polar functional group brings about a remarkable reduction in stress whitening when bent.
  • the polar modified resin usable in the present invention is preferably modified polypropylene, modified polyethylene and/or modified polyolefin elastomers.
  • the polar modified resin is obtained by grafting a polymer resin with a polar material capable of providing a polar functional group.
  • the polar material is selected from the group consisting of maleic anhydride, anhydrous maleic acid, silane and fatty acid.
  • the polar modified resin may occupy up to 80 weight% of the base resin.
  • the polar modified resin exhibit sufficient performance as a compatibilizer with a flame-retardant to uniformly disperse the flame-retardant even through an excessive amount of flame-retardant is added. And, filler loading and freezing resistance improve, and consequently flame retardancy and mechanical properties of the whole composition improve.
  • the content of the polar modified resin is more than the maximum limit, flame retardancy and mechanical properties of the whole composition deteriorate.
  • a flame-retardant insulating resin composition comprises a reactor-made thermoplastic polypropylene resin satisfying the predetermined levels of abrasion resistance, flexibility and elasticity.
  • the reactor-made thermoplastic polypropylene resin (a reactor- made thermoplastic polyolefin elastomer in which polyolefin is polypropylene) is a thermoplastic polymer polymerized from monomers including propylene, which exhibits rubber characteristics.
  • the reactor-made thermoplastic polypropylene resin may be a copolymer of at least one monomer including polypropylene (about 30 to 70 mole% of a propylene monomer) and a reactive functional group, or a polypropylene resin grafted with a reactive functional group.
  • the reactor-made thermoplastic polypropylene resin may be mixtures of at least two types of reactor-made thermoplastic polypropylene resins that satisfy the predetermined levels of abrasion resistance, flexibility and elasticity.
  • the reactor-made thermoplastic polypropylene resin may be a reactor-made thermoplastic polyolefin, in which olefin is propylene or the like.
  • the reactor-made thermoplastic polypropylene resin of the present invention improves flexibility of the insulating resin composition.
  • the reactor-made thermoplastic polypropylene resin is defined as mentioned above, and is not limited to a specific type if it satisfies the predetermined level of mechanical property.
  • the reactor-made thermoplastic polypropylene resin usable in the present invention includes an ethylene-propylene rubber (EPR), ethylene- propylene-diene monomer (EPDM) rubber, reactor-made thermoplastic polyolefin (RTPO) polymerized from monomers including propylene, and so on.
  • EPR ethylene-propylene rubber
  • EPDM ethylene- propylene-diene monomer
  • RTPO reactor-made thermoplastic polyolefin
  • the propylene monomer is preferably used in an amount of 30 to 70 mole% when polymerizing the EPR, EPDM, RTPO and so on.
  • the reactor-made thermoplastic polypropylene resin used in the insulating resin composition of the present invention should satisfy the predetermined levels of abrasion resistance, flexibility and elasticity. At this time, the abrasion resistance, flexibility and elasticity are evaluated by the same test method as in the polypropylene-based insulating resin composition according an aspect of the present invention. The test is not performed on a specimen made from the whole composition, but a specimen made solely from the reactor-made thermoplastic polypropylene resin.
  • the reactor- made thermoplastic polypropylene resin should have an abrasion resistance of 0.03 to 0.5 mm measured by a scrape test, a bending elasticity of 80 to 120 kgf/mm 2 measured by a three-point bending test, and a storage modulus of 400 to 2,000 MPa measured by dynamic mechanical analysis.
  • the abrasion resistance of the reactor- made thermoplastic polypropylene resin is in this range, a high abrasion resistance required for a vehicle cable or the like is obtained, and a high molecular weight leads to good basic properties, a high melt strength and excellent processability with a flame-retardant. If the abrasion resistance by the scrape test is more than the maximum limit, flowability increases and compatibility with a flame-retardant deteriorates upon melting. If the abrasion resistance is less than the minimum limit, the composition becomes brittle and less flexible, and thus is not suitable as a material for an electric cable.
  • the flexural modulus of the reactor-made thermoplastic polypropylene resin when the flexural modulus of the reactor-made thermoplastic polypropylene resin is in this range, a high flexibility required for a vehicle cable is obtained, stress whitening reduces and work efficiency increases in the manufacture of a harness. If the flexural modulus is less than the minimum limit, work efficiency decreases in the manufacture of a harness. If the flexural modulus is more than the maximum limit, the composition becomes brittle and fragile, and stress whitening increases. Furthermore, when the storage modulus of the reactor-made thermoplastic polypropylene resin is in this range, excellent mechanical properties exhibit. If the storage modulus is less than the minimum limit, mechanical properties deteriorate. On the contrary, if the storage modulus is more than the maximum limit, the composition becomes brittle and less flexible.
  • the insulating resin composition of the present invention comprises 50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the base resin or polypropylene resin satisfying the predetermined levels of abrasion resistance, flexibility and elasticity.
  • the inorganic flame-retardant used in the polypropylene-based or reactor- made thermoplastic polypropylene-based insulating resin composition of the present invention is metal hydroxide or metal oxide.
  • the inorganic flame- retardant may be magnesium oxide, magnesium hydroxide, aluminium hydroxide, calcium hydroxide, hydromagnesite (Mg 5 (COs) 4 (OH) 2 ) or mixtures thereof, however the present invention is not limited in this regard.
  • the inorganic flame-retardant may be used without surface coating, or may be surface-coated with (vinyl) silane, amino silane, stearic acid, olefin-based polymer, siloxane-based polymer or polymer materials capable of surface coating.
  • 50 to 200 parts by weight of the inorganic flame-retardant is preferably included based on 100 parts by weight of the base resin or polypropylene resin.
  • the content of the flame-retardant is set in consideration of flame retardancy and mechanical properties of the composition according to the present invention and compatibility with other component. If the content of the flame-retardant is less than the minimum limit, flame-retardant effect does not exhibit. If the content of the flame-retardant is more than the maximum limit, mechanical properties deteriorate.
  • the insulating resin composition of the present invention may further comprise at least one secondary flame-retardant to further improve flame retardancy.
  • the secondary flame-retardant may selected from red phosphorus, antimony trioxide, melamine cyanurate (MC), clay, zinc borate, magnesium oxide (MgO), calcium carborate (CaCO 3 ) and so on.
  • An ordinary person skilled in the art may select a proper type of flame-retardant and its content depending on the end use.
  • the inorganic flame-retardant of the present invention is included at an amount of about 50 to 200 parts by weight based on 100 parts by weight of the base resin or polypropylene resin, flame-retardant effect exhibits.
  • the insulating resin composition of the present invention may further comprise
  • the additive may include an antioxidant, a copper antioxidant, a UV absorber, a heat stabilizer, a lubricant, an antiblocking agent, an antistatic agent, wax, a coupling agent, pigment, a processing aid, and so on.
  • an antioxidant e.g., an antioxidant, a copper antioxidant, a UV absorber, a heat stabilizer, a lubricant, an antiblocking agent, an antistatic agent, wax, a coupling agent, pigment, a processing aid, and so on.
  • various types of additives may be used depending on the purpose of use. If the content of the additive is less than the minimum limit, the effect of the additive does not exhibit. If the content of the additive is more than the maximum limit, the mechanical properties of the whole composition may deteriorate.
  • the processing aid is a dispersant, a Teflon-based processing aid and/or a silicone-based processing aid.
  • the dispersant is at least one selected from the group consisting of stearate salt, stearic acid ester, wax and silane.
  • the insulating resin composition of the present invention has a minimum occurrence of stress whitening and a high flame retardancy while not having deterioration in mechanical properties such as tensile strength or elongation, and thus can be used as a coating material of various cables.
  • the composition of the present invention can be prepared by a well-known method in the art, and the preparing method is not limited to a specific one. At this time, the composition may prepared using a kneader, Banbury an open-roll and so on.
  • the polypropylene-based or reactor- made thermoplastic polypropylene-based insulating resin composition may be prepared at 0 to 22O 0 C using a twin-screw extruder. Mode for the Invention
  • Tables 1 and 2 show the elements and contents of each composition according to examples and comparative examples and the mechanical properties of the used polypropylenes.
  • Comparative PP 1 1) :K283 from GS Caltex in South Korea, a propylene-ethylene random copolymer (90 mole% of propylene monomer and 10 mole% of ethylene monomer) having a melt flow index of 12 g/10 minutes and a density of 0.890 g/cm 3 .
  • Comparative PP 2 2) K483 from GS Caltex in South Korea, a propylene-ethylene block copolymer (88 mole% of propylene monomer and 12 mole% of ethylene monomer) having a melt flow index of 18 g/10 minutes and a density of 0.860 g/cm 3 .
  • Comparative PP 3 3) HK744 from GS Caltex in South Korea, a homopropylene having a melt flow index of 25 g/10 minutes and a density of 0.840 g/cm 3 .
  • compositions were mix-milled into a sheet form by a twin-screw extruder at about 160 to 170 0 C for 10 to 20 minutes, compression-molded by an electric heat press at 17O 0 C for 10 minutes and cooled down to manufacture a polypropylene specimen.
  • a scrape test was performed on a specimen made solely from the polypropylene resin, said scrape test comprising moving back and forth 50 to 60 times a minute in the plane of the surface of said specimen, a needle having a diameter of 0.45+0.01 mm over a distance of 10 mm under a load of 1500 g vertically applied against said surface, and determining the abraded depth of the surface of the specimen as abrasion re- sistance.
  • Table 2 shows the evaluation results of properties of the polypropylene or reactor- made thermoplastic polypropylene specimens. [77] Table 2 [Table 2] [Table ]
  • Table 3 shows the evaluation results of properties of the cable manufactured using the flame -retardant resin composition of the present invention.
  • the cables of examples 1 to 4 had coating layers formed from the polypropylene-based insulating resin com- position, and the cable of example 5 had a coating layer formed from the reactor-made thermoplastic polypropylene-based insulating resin composition.
  • the cables of examples had all better mechanical properties than those of comparative examples. Specifically, the cables of examples exhibited higher tensile strength and elongation than those of comparative examples, and had a significant reduction in stress whitening.
  • an abraded depth of a cable of example having a lowest abrasion resistance was about one third as much as that of a cable of comparative example having a highest abrasion resistance.
  • the cables of examples exhibited even higher flexural modulus than those of comparative examples.
  • the polypropylene-based flame-retardant resin composition exhibits excellent harmony of mechanical properties and is useful for an electric cable installed in narrow spaces where much vibration occurs.

Abstract

Disclosed are a polypropylene-based flame-retardant insulating resin composition that has abrasion resistance and flexibility and is suitable for cables used in, in particular, vehicles, and an electric cable using the same. The composition comprises a polypropylene resin or reactor-made thermoplastic polypropylene resin that satisfies the predetermined ranges of abrasion resistance by a scrape test, bending elasticity by a three-point bending test and storage modulus by dynamic mechanical analysis. The composition also comprises an inorganic flame-retardant, and optionally further comprises a rubber and a modified resin containing a polar functional group.

Description

POLYPROPYLENE-BASED FLAME-RESISTANT RESIN COMPOSITION FOR CABLE INSULATION MATERIAL WITH SUPERIOR MECHANICAL PROPERTIES
The present invention relates to a polypropylene-based flame-retardant resin composition that exhibits excellent harmony of mechanical properties such as abrasion resistance, flexibility and so on. In particular, the present invention relates to a flame-retardant insulating resin composition comprising polypropylene, rubber, a polar modified resin and an inorganic flame-retardant, and to an electric cable using the same.
Cables installed in narrow and high fire-risk spaces, for example, in the inner space of sophisticated mechanisms in vehicles, ships, airplanes and so on, should have flexibility, heat resistance and flame retardancy. For example, class C type cables used in engines or underwood motors, according to ISO 6722, i.e., international standards for vehicle cable, requires a high heat resistance, for example, a maximum allowable temperature of 125 OC or higher. Conventionally, a flame-retardant coating layer is formed from a halogen-containing resin, such as polyvinylchloride (PVC). PVC has excellent flame retardancy, however, when it burns, corrodes facilities and generates gas hazardous to human health. Due to the safety and environment problems, use of PVC is increasingly prohibited. Moreover, attempts have been steadily made to develop a substitute for PVC.
Meanwhile, as environmental regulations on recycling become more strict, the vehicle cable industries attempt to develop a recyclable coating material for an electric cable more actively. For example, to prevent contamination and resource waste that may occur during disposal of cars out of service, the European Union (EU) adopted the End-of-Life Vehicle (ELV) directive. The aim of this directive is to increase the rate of re-use and recovery to 95% in terms of average weight per vehicle/year by 2015. With the current trend, the Korean vehicle industry walks in step with other developed countries. Currently, metal materials used in vehicles are almost wholly recycled. However, taking into consideration that the length of cables used in a car is generally about 2 km, it is important to recycle a greater amount of plastic materials of cables or the like so as to reach the target recycling rate.
Accordingly, the cable manufacturers have steadily studied to develop a plastic material that is free of halogen and exhibits excellent flame retardancy and the desired levels of mechanical and chemical properties. A polypropylene resin is one of all-purpose plastics, and excellent in processability, chemical resistance, weather resistance, mechanical strength. Thus, the polypropylene resin is widely used in domestic electric products, building materials, interior materials, vehicle components and so on, and its application range is expanded to coating materials of electric cables. When compared with the polypropylene resin, a polyethylene resin has good flame-retardancy. When the polyethylene resin is crosslinked, the necessary levels of flame retardancy and mechanical strength can be obtained. However, the crosslinked polyethylene resin cannot be recycled. On the other hand, the polypropylene resin has heat resistance (of the predetermined level for class C type cables) and mechanical strength without crosslinking, and can be recycled.
However, flame retardancy of the polypropylene resin dose not reach the required level. To attain the required level of flame retardacy, the polypropylene resin is added with a large amount of an inorganic flame-retardant, which is environmentally friendly, such as metal hydroxide. However, as the content of the inorganic flame-retardant increases, molded products including the inorganic flame-retardant has deterioration in mechanical properties such as moldability, tensile strength and abrasion resistance. And, when an electric cable is bent, stress whitening occurs.
Cables installed in narrow spaces such as vehicles or ships and holding the potential risk of fire should have flexibility and flame retardancy in addition to excellent mechanical strength for resisting continuous vibration and friction. The deterioration in properties caused by the inorganic flame-retardant hinders the use of a polypropylene-based flame-retardant cable.
Under this circumstance, there is still a need for a polypropylene-based flame-retardant cable that has abrasion resistance, flexibility heat resistance and is capable of preventing stress whitening.
It is an object of the present invention to improving the properties of a polypropylene-based flame-retardant resin composition by use of a polypropylene (PP) compound with excellent abrasion resistance and flexibility so that the composition has excellent abrasion resistance and flexibility against bending deformation and a minimum occurrence of stress whitening.
To achieve the object, the present invention provides a polypropylene-based flame-retardant insulating resin composition.
According to an aspect of the present invention, the insulating resin composition comprises a base resin including 10 to 99 weight% of a polypropylene resin that satisfies the predetermined levels of abrasion resistance, flexibility and elasticity, and 1 to 90 weight% of an adjuvant resin; and 50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the base resin. Here, the adjuvant resin is at least one polymer resin selected from the group consisting of a rubber and a polyolefin grafted with a polar functional group. The polypropylene resin satisfies the following levels of abrasion resistance and flexibility. That is, a specimen made solely from the polypropylene resin has an abraded depth of 0.001 to 0.2 mm measured by a scrape test, a bending elasticity of 90 to 180 kgf/mm2 measured by a three-point bending test, and a storage modulus of 500 to 3,000 MPa measured by dynamic mechanical analysis.
In the present invention, the rubber of the adjuvant resin may be at least one selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-ethylacrylate (EEA), styrene-butadiene-styrene (SBS) rubber, styrene-ethylene-butadiene-styrene (SEBS) copolymer, ethylene-propylene-diene monomer (EPDM) rubber, ethylene glycol dimethacrylate (EGDM) rubber, ethylene-butylacrylate (EBA) copolymer and polyolefin elastomer (POE). And, the polar modified resin of the adjuvant resin may be at least one selected from the group consisting of modified polypropylene, modified polyethylene and modified polyolefin elastomers that are grafted with a polar material to contain a polar functional group. The grafting polar material may be selected from the group consisting of maleic anhydride, anhydrous maleic acid, silane and fatty acid.
According to another aspect of the present invention, the insulating resin composition comprises a reactor-made thermoplastic polypropylene resin (a reactor-made thermoplastic polyolefin elastomer (RTPO) in which polyolefin is polypropylene), and 50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the reactor-made thermoplastic polypropylene resin. At this time, the reactor-made thermoplastic polypropylene resin satisfies the predetermined levels of abrasion resistance, flexibility and elasticity when evaluated in the same way as the polypropylene resin according to an aspect of the present invention. That is, the reactor-made thermoplastic polypropylene resin has an abrasion resistance of 0.03 to 0.5 mm measured by a scrape test, a bending elasticity of 80 to 120 kgf/mm2 measured by a three-point bending test and a storage modulus of 400 to 2,000 MPa measured by dynamic mechanical analysis.
In the present invention, the reactor-made thermoplastic polypropylene resin may be an ethylene-propylene rubber (EPR), an ethylene-propylene-diene monomer (EPDM) rubber or a reactor-made thermoplastic polyolefin elastomer (RTPO).
According to yet another aspect, the present invention provides a flame-retardant cable comprising an insulation coating layer formed using the insulating resin compositions according to the present invention.
Molded products manufactured using the insulating resin composition of the present invention exhibit excellent harmony of mechanical properties such as flame retardancy, abrasion resistance, tensile strength and elongation at break, and have a minimum occurrence of stress whitening on bending. The insulating cable of the present invention exhibiting excellent harmony of properties is useful as a flame-retardant cable installed in the inner space of mechanisms holding the potential risk of fire, in particular, a heat-resistant cable of class C or higher rating for vehicles, ships, airplanes or space ships.
Hereinafter, the present invention will be described in detail. The present invention has an object of providing a polypropylene-based insulation material for an electric cable, which is recyclable, heat-resistant, flame-retardant and low in hazard. The inventors took notice of polypropylene satisfying the predetermined levels of mechanical properties, such as tensile strength, elongation, abrasion resistance and flexibility. In the end, they found that an insulation material comprising polypropylene exhibits harmony of mechanical properties and has excellent flame retardancy, even though an environmentally friendly inorganic flame-retardant is added.
According to an aspect, the present invention provides a polypropylene-based insulating resin composition comprising a base resin including 10 to 99 weight% of a polypropylene resin that satisfies the predetermined levels of abrasion resistance, flexibility and elasticity; and 1 to 90 weight% of an adjuvant resin, and 50 to 200 parts by weight of a flame-retardant based on 100 parts by weight of the base resin.
In the present invention, the polypropylene resin is not limited to a specific type if it is a polymer satisfying the predetermined levels of abrasion resistance, flexibility and elasticity as mentioned below. For example, the polypropylene resin usable in the present invention may be a homopolymer of propylene, or a random or block copolymer or a terpolymer of propylene and an olefin monomer such as ethylene or the like. The copolymer or terpolymer may be produced by polymerizing 70 mole% or more of a propylene monomer and an olefin monomer. Alternatively, the polypropylene resin may be a mixed resin of polypropylene molecules satisfying said predetermined levels of mechanical properties. At this time, the polypropylene resin may include various types of polypropylene-based resins, but to reduce or eliminate stress whitening, a polypropylene random copolymer is preferred. And, the polypropylene resin of the present invention may be mixtures of the exemplary polymers.
Meanwhile, preferably the polypropylene resin has a melt flow index of about 0.2 to 10 g/10 minutes to satisfy the predetermined levels of abrasion resistance, flexibility and elasticity according to the present invention. Preferably, the polypropylene resin also has a density of about 0.85 to 0.95 g/cm3 and an average molecular mass of about 150,000 to 600,000. If the melt flow index of the polypropylene resin is less than 0.2 g/10 minutes, the composition has a low flowability, failing to improve productivity, and compatibility with other components reduces, resulting in insufficient mixing, which causes a reduction in mechanical strength. If the melt flow index of the polypropylene resin is more than 10 g/10 minutes, sufficient mechanical strength cannot be obtained due to a low molecular weight.
As mentioned above, the object of the present invention is to provide a polypropylene-based flame-retardant insulating cable with excellent mechanical properties such as abrasion resistance, flexibility and so on, and a polypropylene-based insulating resin composition for said cable. To achieve the object, the polypropylene resin of the present invention should have the following properties.
The polypropylene resin of the present invention should satisfy an abrasion resistance of 0.001 to 0.2 mm by a scrape test performed on a specimen made solely from the polypropylene resin, except other components.
The scrape test is performed on a specimen made solely from the polypropylene resin, said scrape test comprising moving back and forth in the plane of the surface of said specimen, a needle having a diameter of 0.45±0.01 mm under a load of 1500 g vertically applied against said surface, and measuring how much the surface of the specimen is scraped. The abraded depth is an index of abrasion resistance. The scrape test is carried out at room temperature, unless otherwise stated.
In the insulating resin composition of the present invention, the polypropylene resin having an abrasion resistance of 0.001 to 0.2 mm satisfies a suitable level of abrasion resistance for vehicle cable or the like, and has a high molecular weight. That is, when the abrasion resistance of the polypropylene resin is 0.001 to 0.2 mm, excellent base mechanical properties, a high melt strength and a good processability with a flame-retardant can be obtained. If the abraded depth measured by the scrape test is more than the maximum limit, flowability increases and compatibility with a flame-retardant deteriorates upon melting. On the contrary, if the abraded depth is less than the minimum limit, the composition becomes brittle and its flexibility reduces, and thus is not suitable as a material for an electric cable.
And, the polypropylene resin of the present invention has a flexural modulus of 90 to 180 kgf/mm2 measured by a three-point bending test. The flexural modulus is an index of flexibility of the polypropylene resin. For a high-flexibility vehicle cable, the insulating resin composition and the polypropylene resin of the composition should have a proper flexural modulus.
The three-point bending test is performed on a specimen made solely from the polypropylene resin except other components and having 12 mm width × 2 mm thickness × 120 mm length, according to ASTM D 790 specifications.
If the flexural modulus of the polypropylene resin is in the range of 90 to 180 kgf/mm2, a high flexibility required for a vehicle cable is obtained, stress whitening reduces and work efficiency increases in the manufacture of a harness. If the flexural modulus is less than the minimum limit, work efficiency decreases in the manufacture of a harness. If the flexural modulus is more than the maximum limit, the composition becomes brittle and fragile, and stress whitening increases.
Furthermore, the polypropylene resin of the present invention has a storage modulus of 500 to 3,000 MPa measured by dynamic mechanical analysis. The storage modulus is an index of mechanical properties of the polypropylene resin.
The dynamic mechanical analysis is performed on a specimen of 15 mm × 5 mm × 1 mm using a dynamic mechanical analyzer, DMA 2980 of TA Instruments, in a tension mode at -100 to 200 OC under conditions of a temperature ramp rate of 2 oC/min, frequency of 1 Hz and an amplitude of 0.03%. A value measured at 25 oC is selected as storage modulus of the polypropylene resin.
When the storage modulus of the polypropylene resin is in the range of 500 to 3,000 MPa, excellent mechanical properties exhibit. If the storage modulus is less than the minimum limit, mechanical properties deteriorate. If the storage modulus is more than the maximum limit, the composition becomes brittle and less flexible.
The insulating resin composition of the present invention comprises a rubber and/or a modified resin containing a polar functional group. The polypropylene resin, the rubber and/or the polar functional group constitute a base resin of the composition according to the present invention. Hereinafter, the rubber and/or the polar modified resin will be generally referred to as an adjuvant resin. In the insulating resin composition of the present invention, the rubber and the polar modified resin improve resistance to stress whitening and the mechanical properties of the polypropylene-based copolymer resin such as tensile strength and elongation at break. In the present invention, the base resin includes 10 to 99 weight% of the polypropylene resin and 1 to 90 weight% of the adjuvant resin.
In the present invention, the rubber is a typical one used in the art. The rubber usable in the present invention is not limited to a specific type, and includes a synthetic rubber and other synthetic elastomers. For example, the rubber includes low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate (EEA), styrene-butadiene-styrene (SBS) rubber, styrene-ethylene-butadiene-styrene (SEBS) copolymer, ethylene-propylene-diene monomer (EPDM) rubber, ethylene glycol dimethacrylate (EGDM) rubber, ethylene-butyl acrylate (EBA) copolymer and polyolefin elastomer (POE), however the present invention is not limited in this regard.
The polyolefin elastomer as the rubber is not limited to a specific type, but is preferably an ethylene-alpha olefin copolymer or a propylene-alpha olefin copolymer so as to increase resistance to stress whitening. The ethylene-alpha olefin or propylene-alph aolefin copolymer includes, for example, ethylene-butene, ethylene-octene, ethylene-propylene and propylene-butene copolymers. Because the propylene-alpha olefin copolymer has a good compatibility with the polypropylene resin component, the propylene-alpha olefin copolymer is more preferred.
In the insulating resin composition of the present invention, the rubber may occupy up to 90 weight% of the base resin. When the content of the rubber is in this range, flexibility of the whole composition improves and filling performance of an inorganic flame-retardant increases, and consequently the composition exhibits flame retardancy and mechanical strength. However, if the content of the rubber exceeds the maximum limit, heat resistance is reduced as the melting temperature of the mixture drops.
In the present invention, the polar modified resin is a polymer, in which a resin having a low polarity and a high compatibility with the polypropylene resin, such as polyolefin, is grafted with a polar functional group. The polar modified resin of the present invention mediates compatibility between the inorganic flame-retardant and the polymer resin so that the inorganic flame-retardant particles having a high polarity can be uniformly dispersed in the matrix of the polypropylene resin having a low polarity without agglomeration. The mediation of the polar modified resin suppresses dewetting caused by rupture on an interface between the inorganic flame-retardant and the base resin. As a result, the modified rubber grafted with the polar functional group brings about a remarkable reduction in stress whitening when bent.
The polar modified resin usable in the present invention is preferably modified polypropylene, modified polyethylene and/or modified polyolefin elastomers. The polar modified resin is obtained by grafting a polymer resin with a polar material capable of providing a polar functional group. Preferably, the polar material is selected from the group consisting of maleic anhydride, anhydrous maleic acid, silane and fatty acid.
The modification of a polymer resin with maleic anhydride is well known to an ordinary person skilled in the art, and its detailed description is herein omitted. However, it is preferred to use 0.3 to 1.5 weight% of maleic anhydride based on weight of a polymer resin to be modified. For excellent mechanical properties, it is helpful to use the same polypropylene-based elastomer as that of the base resin in consideration of compatibility with the base resin component.
In the insulating resin composition of the present invention, the polar modified resin may occupy up to 80 weight% of the base resin. When the content of the polar modified resin is in this range, the polar modified resin exhibit sufficient performance as a compatibilizer with a flame-retardant to uniformly disperse the flame-retardant even through an excessive amount of flame-retardant is added. And, filler loading and freezing resistance improve, and consequently flame retardancy and mechanical properties of the whole composition improve. However, if the content of the polar modified resin is more than the maximum limit, flame retardancy and mechanical properties of the whole composition deteriorate.
According to another aspect of the present invention, a flame-retardant insulating resin composition comprises a reactor-made thermoplastic polypropylene resin satisfying the predetermined levels of abrasion resistance, flexibility and elasticity. In the present invention, the reactor-made thermoplastic polypropylene resin (a reactor-made thermoplastic polyolefin elastomer in which polyolefin is polypropylene) is a thermoplastic polymer polymerized from monomers including propylene, which exhibits rubber characteristics. For example, the reactor-made thermoplastic polypropylene resin may be a copolymer of at least one monomer including polypropylene (about 30 to 70 mole% of a propylene monomer) and a reactive functional group, or a polypropylene resin grafted with a reactive functional group. The reactor-made thermoplastic polypropylene resin may be mixtures of at least two types of reactor-made thermoplastic polypropylene resins that satisfy the predetermined levels of abrasion resistance, flexibility and elasticity. And, the reactor-made thermoplastic polypropylene resin may be a reactor-made thermoplastic polyolefin, in which olefin is propylene or the like. The reactor-made thermoplastic polypropylene resin of the present invention improves flexibility of the insulating resin composition.
The reactor-made thermoplastic polypropylene resin is defined as mentioned above, and is not limited to a specific type if it satisfies the predetermined level of mechanical property. For example, the reactor-made thermoplastic polypropylene resin usable in the present invention includes an ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer (EPDM) rubber, reactor-made thermoplastic polyolefin (RTPO) polymerized from monomers including propylene, and so on. Here, the propylene monomer is preferably used in an amount of 30 to 70 mole% when polymerizing the EPR, EPDM, RTPO and so on.
The reactor-made thermoplastic polypropylene resin used in the insulating resin composition of the present invention should satisfy the predetermined levels of abrasion resistance, flexibility and elasticity. At this time, the abrasion resistance, flexibility and elasticity are evaluated by the same test method as in the polypropylene-based insulating resin composition according an aspect of the present invention. The test is not performed on a specimen made from the whole composition, but a specimen made solely from the reactor-made thermoplastic polypropylene resin. That is, the reactor-made thermoplastic polypropylene resin should have an abrasion resistance of 0.03 to 0.5 mm measured by a scrape test, a bending elasticity of 80 to 120 kgf/mm2 measured by a three-point bending test, and a storage modulus of 400 to 2,000 MPa measured by dynamic mechanical analysis.
When the abrasion resistance of the reactor-made thermoplastic polypropylene resin is in this range, a high abrasion resistance required for a vehicle cable or the like is obtained, and a high molecular weight leads to good basic properties, a high melt strength and excellent processability with a flame-retardant. If the abrasion resistance by the scrape test is more than the maximum limit, flowability increases and compatibility with a flame-retardant deteriorates upon melting. If the abrasion resistance is less than the minimum limit, the composition becomes brittle and less flexible, and thus is not suitable as a material for an electric cable. And, when the flexural modulus of the reactor-made thermoplastic polypropylene resin is in this range, a high flexibility required for a vehicle cable is obtained, stress whitening reduces and work efficiency increases in the manufacture of a harness. If the flexural modulus is less than the minimum limit, work efficiency decreases in the manufacture of a harness. If the flexural modulus is more than the maximum limit, the composition becomes brittle and fragile, and stress whitening increases. Furthermore, when the storage modulus of the reactor-made thermoplastic polypropylene resin is in this range, excellent mechanical properties exhibit. If the storage modulus is less than the minimum limit, mechanical properties deteriorate. On the contrary, if the storage modulus is more than the maximum limit, the composition becomes brittle and less flexible.
The insulating resin composition of the present invention comprises 50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the base resin or polypropylene resin satisfying the predetermined levels of abrasion resistance, flexibility and elasticity.
Preferably, the inorganic flame-retardant used in the polypropylene-based or reactor-made thermoplastic polypropylene-based insulating resin composition of the present invention is metal hydroxide or metal oxide. For example, the inorganic flame-retardant may be magnesium oxide, magnesium hydroxide, aluminium hydroxide, calcium hydroxide, hydromagnesite (Mg5(CO3)4(OH)2) or mixtures thereof, however the present invention is not limited in this regard. The inorganic flame-retardant may be used without surface coating, or may be surface-coated with (vinyl) silane, amino silane, stearic acid, olefin-based polymer, siloxane-based polymer or polymer materials capable of surface coating. As mentioned above, 50 to 200 parts by weight of the inorganic flame-retardant is preferably included based on 100 parts by weight of the base resin or polypropylene resin. The content of the flame-retardant is set in consideration of flame retardancy and mechanical properties of the composition according to the present invention and compatibility with other component. If the content of the flame-retardant is less than the minimum limit, flame-retardant effect does not exhibit. If the content of the flame-retardant is more than the maximum limit, mechanical properties deteriorate.
The insulating resin composition of the present invention may further comprise at least one secondary flame-retardant to further improve flame retardancy. The secondary flame-retardant may selected from red phosphorus, antimony trioxide, melamine cyanurate (MC), clay, zinc borate, magnesium oxide (MgO), calcium carborate (CaCO3) and so on. An ordinary person skilled in the art may select a proper type of flame-retardant and its content depending on the end use. When the inorganic flame-retardant of the present invention is included at an amount of about 50 to 200 parts by weight based on 100 parts by weight of the base resin or polypropylene resin, flame-retardant effect exhibits.
And, the insulating resin composition of the present invention may further comprise 0.1 to 10 parts by weight of an additive based on 100 parts by weight of the base resin or polypropylene resin. The additive may include an antioxidant, a copper antioxidant, a UV absorber, a heat stabilizer, a lubricant, an antiblocking agent, an antistatic agent, wax, a coupling agent, pigment, a processing aid, and so on. Although all exemplary additives are not herein specified, various types of additives may be used depending on the purpose of use. If the content of the additive is less than the minimum limit, the effect of the additive does not exhibit. If the content of the additive is more than the maximum limit, the mechanical properties of the whole composition may deteriorate. According to an aspect of the present invention, the processing aid is a dispersant, a Teflon-based processing aid and/or a silicone-based processing aid. According to another aspect of the present invention, the dispersant is at least one selected from the group consisting of stearate salt, stearic acid ester, wax and silane.
As mentioned above, the insulating resin composition of the present invention has a minimum occurrence of stress whitening and a high flame retardancy while not having deterioration in mechanical properties such as tensile strength or elongation, and thus can be used as a coating material of various cables. The composition of the present invention can be prepared by a well-known method in the art, and the preparing method is not limited to a specific one. At this time, the composition may prepared using a kneader, Banbury an open-roll and so on. The polypropylene-based or reactor-made thermoplastic polypropylene-based insulating resin composition may be prepared at 0 to 220OC using a twin-screw extruder.
Hereinafter, the present invention will be described in detail through examples and exemplary production method. Prior to the description, it should be understood that the terms used in the specification and appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.
To compare the mechanical properties of the flame-retardant resin composition of the present invention with those of the conventional composition, resin compositions were prepared according to examples and comparative examples. Specifically, the elements of the composition were mix-milled into a sheet form by a twin-screw extruder at about 160 to 170 OC for 10 to 20 minutes, compression-molded by an electric heating press at 170 OC for 10 minutes, and cooled down.
Tables 1 and 2 show the elements and contents of each composition according to examples and comparative examples and the mechanical properties of the used polypropylenes.
Table 1
Examples Comparative examples
1 2 3 4 5 1 2 3 4
Polypropylene 1* 50 - - 25 - - -
Polypropylene 2** - 50 - - - -
Polypropylene 3*** 50 25
Polypropylene 4**** 100
Rubber † 40 40 40 40 40 30 40 40
Polar modified resin ‡ 10 10 10 10 10 20 10 10
Inorganic flame-retardant§ 100 100 100 100 100 100 100 100 100
Antioxidant§§ 5 5 5 5 5 5 5 5 5
Comparative PP 11) - - - - 50 50
Comparative PP 22) - - - - 50
Comparative PP 33) 50
ELEMENT ANALYSIS OF TABLE 1
Polypropylene of examples
* R274J from GS Caltex in South Korea, a propylene-ethylene random copolymer (94 mole% of propylene monomer and 6 mole% of ethylene monomer) having a melt flow index of 1.9 g/10 minutes and a density of 0.900 g/cm3. Abrasion resistance: 0.02 mm, Flexural modulus: 160 kgf/mm2, Storage modulus: 2800 MPa
** B724J from GS Caltex in South Korea, a propylene-ethylene block copolymer (94 mole% of propylene monomer and 6 mole% of ethylene monomer) having a melt flow index of 1.4 g/10 minutes and a density of 0.900 g/cm3. Abrasion resistance: 0.04 mm, Flexural modulus: 120 kgf/mm2, Storage modulus: 2400 MPa
*** H724J from GS Caltex in South Korea, a homopropylene having a melt flow index of 1.2 g/10 minutes and a density of 0.900 g/cm3. Abrasion resistance: 0.05 mm, Flexural modulus: 100 kgf/mm2, Storage modulus: 1900 MPa
**** V243G from GS Caltex in South Korea, a reactor-made thermoplastic polypropylene resin (40 mole% of propylene monomer and 60 mole% of ethylene monomer) having a melt flow index of 3.4 g/10 minutes and a density of 0.900 g/cm3. Abrasion resistance: 0.1 mm, Flexural modulus: 85 kgf/mm2, Storage modulus: 1500 MPa
† Engage 8150 from Dow Elastomers in U.S.A, ethylene-octene copolymer (39 weight% of octane monomer) having a melt flow index of 0.5 g/10 minutes
‡ Fusabond 226D from DuPont in U.S.A, a linear low density polyethylene (LLDPE) grafted with maleic anhydride (0.90 weight% of maleic anhydride) having a melt flow index: 1.5 g/10 minutes
§ Magnifin H5 non-coated magnesium hydroxide from Albemarle in Germany
§§ Irganox 1010 phenol-based antioxidant from Ciba in Switzerland
Polypropylene of comparative examples
Comparative PP 11): K283 from GS Caltex in South Korea, a propylene-ethylene random copolymer (90 mole% of propylene monomer and 10 mole% of ethylene monomer) having a melt flow index of 12 g/10 minutes and a density of 0.890 g/cm3. Abrasion resistance: 0.1 mm, Flexural modulus: 40 kgf/mm2, Storage modulus: 1300 MPa
Comparative PP 22): K483 from GS Caltex in South Korea, a propylene-ethylene block copolymer (88 mole% of propylene monomer and 12 mole% of ethylene monomer) having a melt flow index of 18 g/10 minutes and a density of 0.860 g/cm3. Abrasion resistance: 0.12 mm, Flexural modulus: 30 kgf/mm2, Storage modulus: 1100 MPa
Comparative PP 33): HK744 from GS Caltex in South Korea, a homopropylene having a melt flow index of 25 g/10 minutes and a density of 0.840 g/cm3. Abrasion resistance: 0.20 mm, Flexural modulus: 10 kgf/mm2, Storage modulus: 900 MPa
To evaluate abrasion resistance, flexibility and elasticity of the polypropylene resin or reactor-made thermoplastic polypropylene resin used in examples and comparative examples, the following tests were performed on a specimen made solely from the polypropylene resin or reactor-made plastic polypropylene resin.
Manufacture of polypropylene specimen
The elements of the composition were mix-milled into a sheet form by a twin-screw extruder at about 160 to 170 OC for 10 to 20 minutes, compression-molded by an electric heat press at 170 OC for 10 minutes and cooled down to manufacture a polypropylene specimen.
Measurement of abrasion resistance
A scrape test was performed on a specimen made solely from the polypropylene resin, said scrape test comprising moving back and forth 50 to 60 times a minute in the plane of the surface of said specimen, a needle having a diameter of 0.45±0.01 mm over a distance of 10 mm under a load of 1500 g vertically applied against said surface, and determining the abraded depth of the surface of the specimen as abrasion resistance.
Measurement of flexural modulus
A three-point bending test was performed on a specimen of 12 mm width × 2 mm thickness × 120 mm length according to ASTM D 790 specifications to measure how flexible the specimen is. The flexibility was determined as flexural modulus (kgf/mm2) of the specimen. The measurement results are shown in Table 2.
Measurement of storage modulus
Dynamic mechanical analysis was performed on a specimen of 15 mm × 5 mm × 1 mm using DMA (Dynamic Mechanical Analyzer) under conditions of a temperature ramp rate of 2 oC/min, frequency of 1 Hz and an amplitude of 0.03%, to measure the storage modulus of the specimen.
Table 2 shows the evaluation results of properties of the polypropylene or reactor-made thermoplastic polypropylene specimens.
Table 2
Abrasion resistance(mm) Flexural modulus (kgf/mm2) Storage modulus (MPa)
Polypropylene 1 0.02 160 2800
Polypropylene 2 0.04 120 2400
Polypropylene 3 0.05 100 1900
Polypropylene 4 0.1 85 1500
Comparative PP 1 0.3 70 400
Comparative PP 2 0.45 54 300
Comparative PP 3 0.65 40 230
To evaluate the performance of the resin compositions of examples and comparative examples, prepared according to Tables 1 and 2, the compositions were compression-molded into a sheet form. The sheet was manufactured into a cable specimen. The cable specimen was evaluated in aspects of mechanical properties such as tensile strength, elongation at break, stress whitening on bending and flexibility. A method for manufacturing a cable specimen from a flame-retardant resin composition for cable coating is well known to an ordinary person skilled in the art, and its detailed description is herein omitted. The mechanical properties were evaluated as follows.
Measurement of tensile strength
A cable specimen was manufactured according to ASTM D 638 standard test method for tensile properties of plastics, known as one of U.S. standard guides for materials. The tensile strength and elongation at break in the cable specimen was measured by a universal testing machine. That is, tensile strength [Pa] = maximum load [N] / initial cross-sectional area of a specimen [m2], and elongation [%] = extended length of a specimen at break / initial length of the specimen. The evaluation results are shown in Table 3.
Measurement of stress whitening on bending
When an insulating material for an electric cable is bent under conditions of a resin thickness of 1 mm and a bend radius of 5 mm, stress whitening can be actually observed by naked eyes. To measure stress whitening under the same conditions, the prepared coating material composition was compression-molded to manufacture a specimen of 1 mm thickness, and the specimen was bent with a bend radius of 5 mm. Stress whitening on bending was observed by naked eyes. Additionally, a cylindrical specimen of 2 mm diameter was manufactured using a capillary viscometer and bent with the same bend radius. Then, stress whitening on bending was observed by naked eyes. The measurement results are shown in Table 3.
Table 3
Classification Examples Comparative examples
1 2 3 4 5 1 2 3 4
Tensile strength(MPa) 27 23 18 21 17 12 11 8 6
Elongation(%) 640 680 720 510 820 480 300 270 530
Stress whitening None Slight whitening None Slight whitening None Severe whitening Slight whitening Severe whitening None
Abrasion resistance(mm) 0.08 0.09 0.1 0.095 0.14 0.38 0.5 0.53 0.73
Flexural modulus(kgf/mm2) 120 98 85 110 80 70 61 43 32
Table 3 shows the evaluation results of properties of the cable manufactured using the flame-retardant resin composition of the present invention. The cables of examples 1 to 4 had coating layers formed from the polypropylene-based insulating resin composition, and the cable of example 5 had a coating layer formed from the reactor-made thermoplastic polypropylene-based insulating resin composition. The cables of examples had all better mechanical properties than those of comparative examples. Specifically, the cables of examples exhibited higher tensile strength and elongation than those of comparative examples, and had a significant reduction in stress whitening. In particular, an abraded depth of a cable of example having a lowest abrasion resistance was about one third as much as that of a cable of comparative example having a highest abrasion resistance. And, the cables of examples exhibited even higher flexural modulus than those of comparative examples.
Therefore, it is found that the polypropylene-based flame-retardant resin composition exhibits excellent harmony of mechanical properties and is useful for an electric cable installed in narrow spaces where much vibration occurs.
As such, the preferred embodiments of the present invention were described hereinabove. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

Claims (17)

  1. An insulating resin composition, comprising:
    a base resin including:
    10 to 99 weight% of a polypropylene resin; and
    1 to 90 weight% of an adjuvant resin; and
    50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the base resin,
    wherein the adjuvant resin is at least one polymer resin selected from the group consisting of a rubber and a polar modified resin,
    wherein the polypropylene resin has an abrasion resistance of 0.001 to 0.2 mm measured by a scrape test,
    wherein the polypropylene resin has a bending elasticity of 90 to 180 kgf/mm2 measured by a three-point bending test,
    wherein the polypropylene resin has a storage modulus of 500 to 3,000 MPa measured by dynamic mechanical analysis,
    wherein the scrape test is performed on a specimen made solely from the polypropylene resin, said scrape test comprising moving back and forth 50 to 60 times a minute in the plane of the surface of said specimen, a needle having a diameter of 0.45±0.01 mm over a distance of 10 mm under a load of 1500 g vertically applied against said surface; and determining the abraded depth of the surface of the specimen as abrasion resistance,
    wherein the three-point bending test is performed on a specimen made solely from the polypropylene resin according to ASTM D 790 specifications, and
    wherein the dynamic mechanical analysis is made on a specimen made solely from the polypropylene resin at a temperature ramp rate of 2 oC/min, frequency of 1 Hz and an amplitude of 0.03%.
  2. The insulating resin composition according to claim 1,
    wherein the polypropylene resin is a homopolymer of propylene or a propylene-olefin copolymer polymerized from a reaction mixture containing 70 mole% or more of the propylene monomer,
    said copolymer being at least one selected from the group consisting of a block copolymer, a random copolymer and a terpolymer of propylene.
  3. The insulating resin composition according to claim 1,
    wherein the inorganic flame-retardant is at least one selected from magnesium oxide, magnesium hydroxide, aluminium hydroxide, calcium hydroxide and hydromagnesite (Mg5(CO3)4(OH)2).
  4. The insulating resin composition according to claim 3,
    wherein the inorganic flame-retardant is surface-coated with at least one selected from the group consisting of stearic acid, oleic acid, fatty acid, amino silane and vinyl silane.
  5. The insulating resin composition according to claim 3,
    wherein the flame-retardant further includes 1 to 20 parts by weight of at least one secondary flame-retardant selected from the group consisting of talc, melamine cyanurate, red phosphorus, magnesium oxide, zinc borate, antimony trioxide.
  6. The insulating resin composition according to claim 1,
    wherein the rubber of the adjuvant resin is at least one selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate (EEA), styrene-butadiene-styrene (SBS) rubber, styrene-ethylene-butadiene-styrene (SEBS) copolymer, ethylene-propylene-diene monomer (EPDM) rubber, ethylene glycol dimethacrylate (EGDM) rubber, ethylene-butyl acrylate (EBA) copolymer and polyolefin elastomer (POE),
    wherein the polar modified resin is at least one selected from the group consisting of a modified polypropylene, a modified polyethylene and a modified polyolefin elastomer that are grafted with a polar material, and
    wherein the grafting polar material is selected from the group consisting of maleic anhydride, anhydrous maleic acid, silane and fatty acid.
  7. The insulating resin composition according to claim 6,
    wherein the polyolefin elastomer is at least one selected from the group consisting of ethylene-butene, ethylene-octene, ethylene-propylene and propylene-butene.
  8. The insulating resin composition according to claim 6,
    wherein the polar modified resin is polyolefin modified with maleic anhydride.
  9. The insulating resin composition according to claim 1, further comprising:
    0.1 to 10 parts by weight of an additive based on 100 parts by weight of the polypropylene resin or base resin, the additive being at least one selected from the group consisting of an antioxidant, a processing aid, a copper antioxidant and a halogen scavenger.
  10. The insulating resin composition according to claim 9,
    wherein the processing aid is a dispersant, a Teflon-based processing aid and a silicone-based processing aid.
  11. The insulating resin composition according to claim 10,
    wherein the dispersant is at least one selected from the group consisting of stearate salt, stearic acid ester, wax and silane.
  12. An insulating resin composition, comprising:
    a reactor-made thermoplastic polypropylene resin; and
    50 to 200 parts by weight of an inorganic flame-retardant based on 100 parts by weight of the reactor-made thermoplastic polypropylene resin,
    wherein the reactor-made thermoplastic polypropylene resin has an abrasion resistance of 0.03 to 0.5 mm measured by a scrape test,
    wherein the reactor-made thermoplastic polypropylene resin has a bending elasticity of 80 to 120 kgf/mm2 measured by a three-point bending test,
    wherein the reactor-made thermoplastic polypropylene resin has a storage modulus of 400 to 2,000 MPa measured by dynamic mechanical analysis,
    wherein the scrape test is performed on a specimen made solely from the reactor-made thermoplastic polypropylene resin, said scrape test comprising moving back and forth 50 to 60 times a minute in the plane of the surface of said specimen, a needle having a diameter of 0.45±0.01 mm over a distance of 10 mm under a load of 1500 g vertically applied against said surface; and determining the abraded depth of the surface of the specimen as abrasion resistance,
    wherein the three-point bending test is performed on a specimen made solely from the reactor-made thermoplastic polypropylene resin according to ASTM D 790 specifications, and
    wherein the dynamic mechanical analysis is made on a specimen made solely from the reactor-made thermoplastic polypropylene resin at a temperature ramp rate of 2 oC/min, frequency of 1 Hz and an amplitude of 0.03%.
  13. The insulating resin composition according to claim 12,
    wherein the reactor-made thermoplastic polypropylene resin is at least one selected from ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer (EPDM) rubber and reactor-made thermoplastic polyolefin (RTPO) polymerized from monomers including propylene.
  14. The insulating resin composition according to claim 12,
    wherein the inorganic flame-retardant is at least one selected from the group consisting of magnesium oxide, magnesium hydroxide, aluminium hydroxide, calcium hydroxide and hydromagnesite (Mg5(CO3)4(OH)2).
  15. The insulating resin composition according to claim 12,
    wherein the inorganic flame-retardant is surface-coated with at least one selected from the group consisting of stearic acid, oleic acid, fatty acid, amino silane and vinyl silane.
  16. The insulating resin composition according to claim 12,
    wherein the inorganic flame-retardant further includes 1 to 20 parts by weight of at least one secondary flame-retardant selected from the group consisting of talc, melamine cyanurate, red phosphorus, magnesium oxide, zinc borate, antimony trioxide.
  17. An insulating cable, comprising:
    a metal conductor bundle; and
    an insulation coating layer surrounding the metal conductor bundle,
    wherein the insulation coating layer is formed from the insulating resin composition defined in any one of claims 1 to 16.
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