WO2009119942A1 - Halogen-free flame retardant composition for cable and cable using the same - Google Patents

Halogen-free flame retardant composition for cable and cable using the same Download PDF

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Publication number
WO2009119942A1
WO2009119942A1 PCT/KR2008/003699 KR2008003699W WO2009119942A1 WO 2009119942 A1 WO2009119942 A1 WO 2009119942A1 KR 2008003699 W KR2008003699 W KR 2008003699W WO 2009119942 A1 WO2009119942 A1 WO 2009119942A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
flame retardant
halogen
weight
cable
Prior art date
Application number
PCT/KR2008/003699
Other languages
English (en)
French (fr)
Inventor
Do-Hyun Park
Hyun-Joo Hwang
Original Assignee
Ls Cable Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ls Cable Ltd. filed Critical Ls Cable Ltd.
Priority to CN2008801283227A priority Critical patent/CN101981109A/zh
Priority to JP2011501702A priority patent/JP2011519383A/ja
Publication of WO2009119942A1 publication Critical patent/WO2009119942A1/en

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Classifications

    • 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
    • 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
    • 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
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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

Definitions

  • the present invention relates to a halogen-free flame retardant composition for a cable and a cable manufactured using the same, and in particular, to a halogen-free flame retardant composition that does not include a halogen component but a mixed resin of an ethylene-based copolymer resin and a polyolefin-based resin as a base resin, a flame retardant and a flame retarding aid to exhibit high tensile strength and meet the flame retardance requirements, and an insulating cable manufactured using the same.
  • a cable for power supply, control or signalling used in ships has a woven layer surrounding a bedding structure that surrounds a center conductor so as to prevent deformation caused by tensile force and lateral pressure that may be applied to the cable at the time of installation, and the woven layer is made of galvanized iron wires, galvanized steel wires or copper coated iron wires.
  • a halogen-free flame retardant cable according to IEC (International Electrotechnical Commission) standards should have a woven layer inside or outside thereof when it is used in dangerous places or places required for explosion proof.
  • IEC International Electrotechnical Commission
  • the woven layer is formed through a separate step in a cable manufacturing process, thereby increasing the unit cost of production, and in the case that wires are woven irregularly in a woven layer forming step, a faulty product may be manufactured. And, the woven layer increases the total weight of a cable, which limits applications required for light weight.
  • An object of the present invention is to provide a halogen-free polymer composition that can provide not only flame retardance but also functions and properties of both of a bedding structure and a woven structure surrounding a center conductor of a cable and meet various physical properties required for an insulator.
  • a halogen-free flame retardant composition according to the present invention comprises 100 parts by weight of a base resin including 60 to 90 weight% of an ethylene-based copolymer resin and 10 to 40 weight% of a polyolefin-based resin; 50 to 160 parts by weight of a flame retardant relative to 100 parts by weight of the base resin; and 1 to 30 parts by weight of a flame retarding aid relative to 100 parts by weight of the base resin.
  • An insulating cable according to the present invention includes a center conductor; an insulating layer coating the center conductor; and a bedding layer surrounding the center conductor coated with the insulating layer, wherein the bedding layer is formed using the above-mentioned halogen-free flame retardant composition.
  • FIG. 1 is a schematic cross-sectional view of a conventional insulating cable.
  • FIG. 2 is a schematic cross-sectional view of an insulating cable according to the present invention. Best Mode for Carrying out the Invention
  • a halogen-free flame retardant composition has a tensile strength of 1.5 kgf/mnf or more at normal temperature, and the composition includes 100 parts by weight of a base resin including 60 to 90 weight% of an ethylene-based copolymer resin and 10 to 40 weight% of a polyolefin-based resin, 50 to 160 parts by weight of a flame retardant relative to 100 parts by weight of the base resin, and 1 to 30 parts by weight of a flame retarding aid relative to 100 parts by weight of the base resin.
  • the ethylene-based copolymer resin of the base resin is included less than the above-mentioned minimum, it is not preferable because capacity of filling a large amount of flame retardant is reduced to remarkably decrease elongation.
  • the ethylene-based copolymer resin is included more than the above- mentioned maximum, it is not preferable because proportion of a crystalline resin is reduced, thereby failing to ensure tensile strength and shock resistance corresponding to a woven layer of a conventional insulating cable and to meet thermal deformation resistance at 8O 0 C and high temperature ageing characteristics at 15O 0 C.
  • a content limitation of the polyolefin-based resin has a contrary reason to a content limitation of the ethylene-based copolymer resin.
  • the polyolefin-based resin is included less than the above-mentioned minimum, it is not preferable because proportion of a crystalline resin is reduced, thereby failing to ensure tensile strength and shock resistance corresponding to a woven layer of a conventional insulating cable and to meet thermal deformation resistance at 8O 0 C and high temperature ageing characteristics at 15O 0 C.
  • the polyolefin-based resin is included more than the above-mentioned maximum, it is not preferable because capacity of filling a large amount of flame retardant is remarkably reduced to decrease elongation, and a large amount of resin having a high melting temperature is used, which increases an extruding process temperature, resulting in decomposition of the flame retardant.
  • the ethylene-based copolymer resin of the base resin is any one selected from the group consisting of an ethylene vinyl acetate copolymer resin, an ethylene methyl acrylate copolymer resin, an ethylene ethyl acrylate copolymer resin, and an ethylene butyl acrylate copolymer resin, or mixtures thereof, however the present invention is not limited in this regard. More preferably, the ethylene-based copolymer resin has a specific gravity of 0.93 g/cnf to 0.96 g/cnf, a melting temperature of 67 0 C to 102 0 C, and a melting index of 0.3 g/10min to 10 g/10min.
  • the melting index is less than the above-mentioned minimum, it is not preferable because elongation and extrusion is reduced, and in the case that the melting index is more than the above-mentioned maximum, it is not preferable because tensile strength and heat resistance is reduced.
  • the polyolefin-based resin of the base resin is any one selected from the group consisting of a low density polyethylene (LDPE) resin, a linear low density polyethylene (LLDPE) resin, a middle density polyethylene (MDPE) resin, a high density polyethylene (HDPE) resin, a polypropylene resin, and a polyester resin, or mixtures thereof, however the present invention is not limited in this regard. More preferably, a material selected as the polyolefin-based resin has a maleic anhydride.
  • the flame retardant is included less than the above-mentioned minimum, it is not preferable because flame retardance is insufficient, and in the case that the flame retardant is more than the above-mentioned maximum, it is not preferable because flame retardance is not increased in proportion to an excessive amount of flame retardant but tensile strength characteristics are reduced due to the excessive amount of flame retardant.
  • the flame retardant is any one selected from the group consisting of a mixture of magnesium hydroxide and hydro- magnesite, a composite of huntite and hydromagnesite, and aluminium hydroxide, or mixtures thereof, however the present invention is not limited in this regard.
  • the flame retardant may be a metal hydroxide surface-treated with any one selected from the group consisting of vinylsilane, stearic acid, oleic acid, aminopolysiloxane, and polymer resin, or mixtures thereof.
  • the metal hydroxide is any one selected from the group consisting of a mixture of magnesium hydroxide and hydromagnesite, a composite of huntite and hydromagnesite, and aluminium hydroxide, or mixtures thereof, however the present invention is not limited in this regard.
  • the flame retarding aid is included less than the above-mentioned minimum, it is not preferable because improvement in flame retardance is not realized, and in the case that the flame retarding aid is more than the above-mentioned maximum, it is not preferable because an amount of a flame retardant should be reduced to prevent reduction in mechanical properties, resulting in reduced flame retardance or heat resistance.
  • the flame retarding aid is any one selected from the group consisting of a red phosphorous-based compound, a silicon-based compound, a boron-based compound, and carbon powder, or mixtures thereof, however the present invention is not limited in this regard.
  • the halogen-free flame retardant composition may further include 0.1 to 15 parts by weight of an antioxidant relative to 100 parts by weight of the base resin, and the antioxidant is any one selected from the group consisting of hindered phenol-based, phosphate-based, imidazole-based and thio-based, or mixtures thereof.
  • the antioxidant is included less than the above-mentioned minimum, it is not preferable because a small amount of antioxidant results in insufficient heat resistance, and in the case that the antioxidant is more than the above-mentioned maximum, it is not preferable because an excessive amount of antioxidant results in reduced flame retardance and mechanical properties.
  • the above-mentioned halogen-free flame retardant composition according to the present invention has a tensile strength of 1.50 kg/mirf or more at normal temperature and an oxygen index of 28% or more.
  • the composition can be used to form a bedding structure and a woven structure of iron wires or copper wires in an insulating wire or cable, or an inner sheath layer of an electrical wire.
  • Each sample was tested according to the following methods to measure various properties including characteristics at normal temperature such as tensile strength and elongation, thermal deformation rate, oxygen index and high temperature ageing, and measurement results are shown in the following Table 2.
  • characteristics at normal temperature such as tensile strength and elongation, thermal deformation rate, oxygen index and high temperature ageing, and measurement results are shown in the following Table 2.
  • Each sample was tested according to IEC 60811-1-1 standards to measure characteristics at normal temperature when a tension test speed is 250 mm/min, and tensile strength of 1.5 kgf/mnf or more and elongation of 125% is considered suitable for products.
  • Each sample was tested according to IEC 60811 standards to measure a thermal deformation rate after being left at 8O 0 C for 4 hours, a thermal deformation rate of 50% or less is considered suitable for products.
  • Each sample was tested according to ASTM D 2863 standards to measure an oxygen index, and an oxygen index of 28% or more is considered suitable for products.
  • Each sample was tested according to IEC 811 standards to measure high temperature ageing after being left at 15O 0 C for 1 hour, and no cracking is considered suitable for products.
  • a sheath layer of an insulating cable that surrounds a center conductor was formed using each composition prepared according to Table 1, and the cable having the sheath layer was tested to measure flame retardance and tensile strength, and measurement results are shown in Table 2.
  • the cable was tested according to IEC 332-3 Cat.A to measure flame retardance, and determined whether or not it is suitable for products.
  • the tensile strength of the cable was determined according to whether or not the performance of an insulator was deteriorated and whether or not an outer coating was damaged when the cable was drawn.
  • the examples 1 to 6 used a mixture of ethylene copolymer resin having a melting temperature of 67 0 C to 102 0 C and a crystalline polyethylene resin, and met the tensile strength and elongation requirements of the present invention, i.e. tensile strength of 1.5 kgf/mnf or more at normal temperature and elongation of 125% or more. Accordingly, a cable having an insulator formed using the composition according to the present invention has tensile strength suitable for an installation environment. Meanwhile, because a crystalline polyethylene resin is included in a base resin, the examples 1 to 6 passed a thermal deformation test using a cutter blade at 8O 0 C and a high temperature ageing test at 15O 0 C.
  • the examples 1 to 6 used a resin having a high melting temperature and a high thermal decomposition temperature, and thus when a cable having an insulator formed using the flame retardant composition of the present invention is tested according to flame retardance test, a polymer resin of the flame retardant material does not melt down, but stands against flame and high ambient temperature, thereby preventing flame from propagating to the insulator of the cable, and thus the cable has flame retardant characteristics.
  • the comparative examples 1 to 3 used only an ethylene copolymer resin having a low melting temperature and a low thermal decomposition temperature, and thus in case that the resin is exposed to flame of 600 0 C or more, the resin is melted down and flow-in of oxygen is promoted, resulting in rapid combustion. As a result, the comparative examples 1 to 3 failed the flame retardance test. And, the comparative examples 1 to 3 used a low crystalline copolymer resin, and thus did not meet the tensile strength requirements of the present invention. Accordingly, cables having insulators formed using the compositions according to the comparative examples 1 to 3 did not meet the tensile strength requirements for installation.
  • the comparative examples 1 to 3 used only a resin having a melting temperature of 100 0 C or less, and thus, after a thermal deformation test using a cutter blade at 8O 0 C according to IEC 60811, they did not meet the required thermal deformation rate of 50%, and as a result, the insulators were broken. And, because the melting temperature is low, the samples were broken after a high temperature ageing test at 15O 0 C, and therefore, the comparative examples 1 to 3 were not considered suitable for products.
  • an insulating cable according to the present invention is manufactured, in which a bedding layer surrounding a center conductor coated with an insulating layer is formed using the above-mentioned halogen-free flame retardant composition.
  • FIG. 1 is a schematic cross-sectional view of a conventional insulating cable.
  • the conventional insulating cable includes a center conductor 11 and an insulating layer 12 surrounding the center conductor 11.
  • the insulating layer 12 is made of an ethylene propylene rubber, polyethylene or polyolefin.
  • a bedding layer 13 surrounds a plurality of conductors 11 having each insulating layer 12.
  • a woven layer 14 surrounds the bedding layer 13, and is made of copper plated with copper or tin.
  • a sheath layer 15 surrounds the woven layer 14, and is mainly formed using a flame retardant composition according to IEC 60332-3 Cat.A.
  • the woven layer 14 stands against the tensile force, and in case of fire, the bedding layer 15 suppresses flame propagation caused by the woven layer 14 to minimize damage of the insulating layer 12 and maintain electrical characteristics of the cable.
  • the bedding layer 15 suppresses flame propagation caused by the woven layer 14 to minimize damage of the insulating layer 12 and maintain electrical characteristics of the cable.
  • the woven layer 14 is simply removed from the conventional insulating cable, the above-mentioned problem is not solved, but a critical fault may occur to suitability for products.
  • the present invention removes a woven layer of a conventional insulating cable, and instead forms a bedding layer using a halogen-free flame retardant composition having a tensile strength of 1.5kgf/mnf or more at normal temperature and an oxygen index of 28% or more, resulting in light weight and flexibility of a cable.
  • an insulating cable according to the present invention does not have a woven layer, as shown in FIG. 2.
  • FIG. 2 is a schematic cross-sectional view of an insulating cable according to the present invention.
  • the insulating cable includes a center conductor 21 and an insulating layer 22 surrounding the center conductor.
  • a bedding layer 23 surrounds a plurality of conductors 21 having each insulating layer 22, and a sheath layer 24 surrounds the bedding layer 23.
  • the present invention can prepare a halogen-free flame retardant composition, and forms a bedding layer or a sheath layer of an insulating cable using the halogen-free flame retardant composition.
  • An insulating cable according to the present invention has a tensile strength of 1.5kgf/mnf or more at normal temperature, and thus meets the required suitability for products without a woven layer of a conventional insulating cable.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Insulated Conductors (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Insulating Materials (AREA)
PCT/KR2008/003699 2008-03-28 2008-06-26 Halogen-free flame retardant composition for cable and cable using the same WO2009119942A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2008801283227A CN101981109A (zh) 2008-03-28 2008-06-26 电缆用无卤素阻燃组合物和使用其的电缆
JP2011501702A JP2011519383A (ja) 2008-03-28 2008-06-26 非ハロゲン系難燃材製造用組成物及びこれを用いて製造された絶縁電線

Applications Claiming Priority (2)

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KR10-2008-0028892 2008-03-28
KR1020080028892A KR100947169B1 (ko) 2008-03-28 2008-03-28 비할로겐계 난연재 제조용 조성물 및 이를 이용하여 제조된절연전선

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KR (1) KR100947169B1 (ja)
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CN102190828A (zh) * 2010-03-03 2011-09-21 Ls电线有限公司 耐热变形性绝缘树脂组合物及使用该组合物的电缆
US20110278039A1 (en) * 2011-07-25 2011-11-17 King Abdulaziz City for Science and Technology (KACST) Eco friendly crosslinked flame retardant composition for wire and cable
CN102746550A (zh) * 2012-06-12 2012-10-24 安徽华海特种电缆集团有限公司 一种低烟无卤环保型阻燃船用控制电缆料及其制备方法
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US8992681B2 (en) 2011-11-01 2015-03-31 King Abdulaziz City For Science And Technology Composition for construction materials manufacturing and the method of its production
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US9982118B2 (en) 2011-10-28 2018-05-29 Fujikura Ltd. Flame retardant resin composition and cable using same
CN112210157A (zh) * 2020-09-29 2021-01-12 上海凯波电缆特材股份有限公司 一种无卤阻燃聚烯烃护套料及其制备方法
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CN105237885A (zh) * 2015-10-29 2016-01-13 宁波一舟塑胶有限公司 一种高填充低烟无卤阻燃聚烯烃电缆料及其制备方法
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