WO2013190832A1 - Fil isolé ignifuge résistant à la chaleur - Google Patents

Fil isolé ignifuge résistant à la chaleur Download PDF

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Publication number
WO2013190832A1
WO2013190832A1 PCT/JP2013/003794 JP2013003794W WO2013190832A1 WO 2013190832 A1 WO2013190832 A1 WO 2013190832A1 JP 2013003794 W JP2013003794 W JP 2013003794W WO 2013190832 A1 WO2013190832 A1 WO 2013190832A1
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Prior art keywords
mass
parts
heat
flame
resistant
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Ceased
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PCT/JP2013/003794
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English (en)
Japanese (ja)
Inventor
真利子 斉藤
道朝 藤田
昌啓 箕輪
伸明 光地
岡下　稔
喜直 児玉
利明 森
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SWCC Corp
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SWCC Showa Cable Systems Co Ltd
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Priority to CN201380011266.XA priority Critical patent/CN104205248B/zh
Publication of WO2013190832A1 publication Critical patent/WO2013190832A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • 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
    • 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 four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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—Polyethylene

Definitions

  • the present invention relates to an insulated wire excellent in heat resistance, flame retardancy and workability.
  • insulated wires that have both heat resistance and flame resistance in applications such as gas appliances and motor wires for microwave ovens.
  • a heat resistance of 130 to 150 ° C. based on the technical standards of electrical appliances and flame retardancy that passes the UL vertical combustion test (VW-1).
  • a coating material which uses a composition in which a specific flame retardant is combined with an ethylene copolymer (see, for example, Patent Document 1).
  • a specific flame retardant is combined with an ethylene copolymer (see, for example, Patent Document 1).
  • Patent Document 1 a coating material which uses a composition in which a specific flame retardant is combined with an ethylene copolymer.
  • an electric wire using a fluoro rubber represented by a tetrafluoroethylene-propylene copolymer as an insulating material is known.
  • Fluororubber is excellent in heat resistance, oil resistance, chemical resistance, aging resistance, weather resistance, electrical insulation, and the like, and an electric wire using this has high heat resistance.
  • fluororubber has strong adhesiveness in an uncrosslinked state, and there is a possibility that the shape of the coating may change or the appearance may be damaged when the coatings come into contact with each other, such as when wound on a drum in an uncrosslinked state. It was. For this reason, it is necessary to carry out the (extrusion) molding step and the crosslinking step continuously, and there is a problem in workability.
  • fluororubber since fluororubber is very expensive, it has been used for coating special wires used in harsh high-temperature environments exceeding 200 ° C, such as wiring wires around engines such as automobiles. It was limited.
  • the object of the present invention is to provide an insulated wire having both heat resistance and flame retardancy, good workability, and low price.
  • the heat-resistant and flame-retardant insulated wire of one embodiment of the present invention is based on 100 parts by mass of a base polymer comprising (A) 50 to 90% by mass of a tetrafluoroethylene-propylene copolymer and (B) 10 to 50% by mass of a polyolefin. (C) 1 to 30 parts by mass of ethylenebis (pentabromophenyl), and (D) a coating made of an electrically insulating composition containing 10 to 50 parts by mass of antimony trioxide.
  • an insulated wire having both heat resistance and flame retardancy, good workability, and low price is provided.
  • an electrically insulating composition used for the heat-resistant and flame-retardant insulated wire of the present invention (hereinafter also simply referred to as an insulated wire) will be described.
  • This composition is based on (A) tetrafluoroethylene-propylene copolymer and (B) polyolefin, and contains (C) ethylene bis (pentabromophenyl) and (D) antimony trioxide.
  • the (A) tetrafluoroethylene-propylene copolymer is typically a polymer having a basic skeleton represented by the following formula, and can be obtained, for example, by low-temperature emulsion polymerization of tetrafluoroethylene and propylene.
  • n and m each represent an integer of 1 or more
  • This tetrafluoroethylene-propylene copolymer contains, as a third component, a copolymerizable monomer such as ethylene, isobutylene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, vinyl fluoride, vinylidene fluoride, An appropriate amount of one or more of hexafluoropropene, chloroethyl vinyl ether, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and the like may be contained.
  • the tetrafluoroethylene-propylene copolymer may be used alone or in combination of two or more.
  • Examples of commercially available tetrafluoroethylene-propylene copolymers used as the component (A) include AFLAS ⁇ ⁇ ⁇ 150CS manufactured by Asahi Glass Co., Ltd. (specific gravity: 1.55, fluorine content: 57%, Mooney viscosity ML1 + 10 ( 100 ° C): 140, Mooney viscosity ML1 + 10 (121 ° C): 100), AFLASAF150C (specific gravity: 1.55, Mooney viscosity ML1 + 10 (100 ° C):> 160), AFLAS 150E (specific gravity: 1.55, Mooney) Viscosity ML1 + 10 (100 ° C.): 60, Mooney viscosity ML1 + 10 (121 ° C.): 45) (above, trade name) and the like.
  • polyolefin examples include polyethylene such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), very low density polyethylene (VLDPE), and linear low density polyethylene (LLDPE).
  • Ethylene / unsaturated carboxylic acid ester copolymer copolymerized with saturated carboxylic acid ester ethylene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, Examples thereof include ethylene / vinyl ester copolymers obtained by copolymerizing vinyl esters such as vinyl salicylate and vinyl cyclohexanecarboxylate; and isobutylene / isoprene copolymers.
  • polypropylene not only a homopolymer of propylene, but also a random copolymer or block copolymer with ethylene, a copolymer with a small amount of ⁇ -olefin, and the like can be used.
  • ⁇ -olefin examples include 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like.
  • a non-conjugated polyene may be further copolymerized with the propylene / ⁇ -olefin copolymer.
  • non-conjugated polyene examples include dicyclopentadiene, 1,4-hexadiene, ethylidene norbornene, and vinyl norbornene. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • low-density polyethylene, linear low-density polyethylene, and ethylene / ethyl acrylate copolymer are preferable as the polyolefin, and ethylene / ethyl acrylate copolymer is more preferable from the viewpoint of excellent heat resistance.
  • Examples of commercially available ethylene / ethyl acrylate copolymers include Lexpearl EEA A1150 (density: 0.932 g / cm 3 , MFR: 0.8 g / 10 min, manufactured by Nippon Polyethylene Co., Ltd.) Amount: 15% by mass, melting point (DSC method) 100 ° C., oxygen index 10.0;
  • the mixing ratio of the component (A) and the component (B) in the base polymer of the composition is (A) a tetrafluoroethylene-propylene copolymer of 50 to 90% by mass and (B) a polyolefin of 10 to 50% by mass.
  • proportion of the component (A) is less than 50% by mass, not only the heat resistance is lowered, but also the mechanical properties and weather resistance are lowered.
  • (A) component exceeds 90 mass%, workability will fall.
  • the adhesiveness in an uncrosslinked state increases, and cost reduction becomes difficult.
  • (A) tetrafluoroethylene-propylene copolymer is 55 to 85% by mass
  • (B) polyolefin is 15 to 45% by mass, and more preferably (A) tetrafluoroethylene-propylene copolymer is 65% by mass. 75% by mass, and (B) polyolefin is 25-35% by mass.
  • Ethylene bis (pentabromophenyl) is a compound represented by the following formula known as a brominated flame retardant.
  • Specific examples of commercially available products that are preferably used as the component (C) include SAYTEX 8010 (trade name, manufactured by ALBEMARLE).
  • the blending amount of this (C) ethylene bis (pentabromophenyl) is 1 to 30 parts by weight, preferably 2 parts per 100 parts by weight of the total amount of the aforementioned component (A) and component (B) of the base polymer. -15 parts by mass, more preferably 3-7 parts by mass. When the blending amount is less than 1 part by mass, sufficient flame retardancy cannot be obtained, and when it exceeds 30 parts by mass, the mechanical properties may be deteriorated.
  • At least one brominated flame retardant other than ethylenebis (pentabromophenyl) can be used in combination as long as the effects of the present invention are not impaired.
  • the brominated flame retardant used in combination include ethylene bistetrabromophthalimide, decabromodiphenyl oxide, and tetradecabromodiphenoxybenzene.
  • Antimony trioxide is a component that acts as a flame retardant aid.
  • 10-50 parts by mass of antimony trioxide is blended with respect to 100 parts by mass of the total amount of the base polymer component described above. The amount is preferably 15 to 35 parts by mass, and more preferably 15 to 25 parts by mass. When the blending amount is less than 10 parts by mass, sufficient flame retardancy cannot be obtained, and when it exceeds 50 parts by mass, the mechanical properties are deteriorated.
  • An inorganic filler can be blended with the electrically insulating composition for the purpose of improving mechanical properties such as tensile strength.
  • the inorganic filler include calcium carbonate, fused silica, crystalline silica, talc, clay, alumina, zirconia, mica, titanium white, bengara, silicon carbide, boron nitride, silicon nitride, and aluminum nitride.
  • calcium carbonate and talc are preferable from the viewpoint of heat resistance. They also have the advantage that light color formulation is possible.
  • the calcium carbonate both heavy calcium carbonate and light calcium carbonate can be used.
  • the blending amount is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the total amount of the base polymer components described above.
  • the electrical insulating composition includes additives such as processing aids, dispersants, colorants, anti-aging agents, and lubricants that are generally blended in this type of composition. As long as it does not inhibit, it can be blended as necessary.
  • polyethylene wax, sodium stearate and the like can be blended in an amount of 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the polymer component.
  • an aliphatic hydrocarbon resin mixture or the like as a dispersant can be blended in an amount of 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the polymer component.
  • flame retardants and flame retardant aids other than the brominated flame retardants and antimony trioxide described above can be blended within a range that does not impair the effects of the present invention.
  • flame retardants and flame retardant aids include metal hydrates such as magnesium hydroxide and aluminum hydroxide, nitrogen flame retardants such as guanidine and melamine, and phosphorus flame retardants such as ammonium phosphate and red phosphorus.
  • flame retardants, phosphorus-nitrogen flame retardants, and boric acid compounds such as zinc borate.
  • the electrical insulating composition used in the present invention is usually crosslinked after molding (coating).
  • the crosslinking method is not particularly limited, and any method such as chemical crosslinking using a crosslinking agent or crosslinking by radiation such as an electron beam can be used.
  • a crosslinking agent used for the chemical crosslinking an organic peroxide is preferable.
  • 1,3-bis- (t-butylperoxyisopropyl) benzene or the like is used.
  • a crosslinking aid such as triallyl isocyanurate together with such a crosslinking agent.
  • the organic peroxide is preferably blended in an amount of 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the polymer component, and the crosslinking assistant is 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the polymer component. It is preferable to blend 10.0 parts by weight.
  • the electrically insulating composition comprises (A) a tetrafluoroethylene-propylene copolymer, (B) a polyolefin, (C) ethylenebis (pentabromophenyl) and (D) antimony trioxide, and if necessary.
  • Additives such as component (C), component (D) and component (E), processing aids, and dispersants are mixed in advance when kneading each component (A) and component (B). Also good.
  • the insulated wire of the present invention is produced by extrusion-coating the electrically insulating composition obtained as described above directly on the conductor or through another coating and crosslinking. Since the composition has low tackiness in an uncrosslinked state, even if the coating is wound around a drum while being in an uncrosslinked state, the coatings are not strongly adhered to each other. Therefore, the crosslinking step may be performed as a separate step from the extrusion coating step, or may be performed continuously in a single step.
  • the material of the conductor, the outer diameter, the presence / absence of twisting, and the like are not particularly limited and are appropriately selected depending on the application.
  • FIG. 1 is a cross-sectional view showing a heat-resistant and flame-retardant insulated wire according to an embodiment of the present invention.
  • reference numeral 11 denotes a conductor made of one or more tin-plated annealed copper wires or the like.
  • the insulator 12 is formed by extrusion-coating the above-described electrically insulating composition and crosslinking.
  • the insulated wire of this embodiment is comprised so that the following requirements may be satisfied.
  • the electric wire as a whole has flame retardancy that passes the VW-1 vertical combustion test (UL 1581).
  • the tensile strength after thermal aging (180 ° C., 336 hours) of the insulator 12 is 4.0 MPa or more, and the tensile elongation is 50% or more.
  • the tensile strength and the tensile elongation are values measured according to JIS C 3005.
  • the insulated wire of this embodiment can have both heat resistance of 130 to 150 ° C. based on the technical standards of electrical appliances and flame resistance that passes the UL vertical combustion test (VW-1).
  • VW-1 UL vertical combustion test
  • the cross-linking process is not limited as in the case of electric wires using conventional fluororubber, and an increase in price is also suppressed.
  • FEPM tetrafluoroethylene-propylene copolymer
  • Product name AFLAS 150CS manufactured by Asahi Glass Co., Ltd.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • Hi-Zex 5305E EEA ethylene / ethyl acrylate copolymer
  • Ethylene bis (pentabromophenyl) Product name SAYTEX 8010 manufactured by ALBEMARLE Heavy calcium carbonate: Shiraishi Calcium Co., Ltd.
  • Example 1 50 parts by mass of FEPM, 50 parts by mass of LDPE, 2.0 parts by mass of ethylene bis (pentabromophenyl), 30 parts by mass of antimony trioxide and 30 parts by mass of heavy calcium carbonate were sufficiently kneaded using an open roll to electrically insulate composition A product was prepared.
  • the above electrically insulating composition was extrusion coated to a thickness of 0.33 mm on a copper stranded wire conductor having a cross-sectional area of 0.3 mm 2 formed by collectively twisting 12 tin-plated annealed copper wires having a diameter of 0.18 mm, and accelerated An insulator was formed by irradiating an electron beam of 200 kGy with an electron beam irradiation apparatus having a voltage of 800 kV to produce an insulated wire having an outer diameter of 1.38 mm.
  • Examples 2 to 9 Comparative Examples 1 to 9 An electrical insulating composition was prepared in the same manner as in Example 1 except that the composition of the electrical insulating composition was changed as shown in Table 1. Further, in the same manner as in Example 1 using these compositions. Insulated wires were manufactured.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
PCT/JP2013/003794 2012-06-21 2013-06-18 Fil isolé ignifuge résistant à la chaleur Ceased WO2013190832A1 (fr)

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Application Number Priority Date Filing Date Title
CN201380011266.XA CN104205248B (zh) 2012-06-21 2013-06-18 耐热阻燃绝缘电线

Applications Claiming Priority (2)

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JP2012139775A JP5425973B2 (ja) 2012-06-21 2012-06-21 耐熱難燃絶縁電線
JP2012-139775 2012-06-21

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JP2015199806A (ja) * 2014-04-07 2015-11-12 日立金属株式会社 含フッ素エラストマー組成物、並びにこれを用いた絶縁電線及びケーブル
JP2022152951A (ja) * 2021-03-29 2022-10-12 古河電気工業株式会社 難燃性ポリオレフィン樹脂組成物及びこれを用いた配線材
USD982304S1 (en) 2022-06-24 2023-04-04 Blakely Ventures, LLC Shoe last
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CN110475816B (zh) * 2017-03-31 2022-01-28 索尔维特殊聚合物意大利有限公司 制造固化的零件的方法
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JP6575777B2 (ja) * 2018-02-14 2019-09-18 日立金属株式会社 電線
JP6730359B2 (ja) * 2018-04-03 2020-07-29 日立金属株式会社 絶縁電線
CN108586866A (zh) * 2018-04-19 2018-09-28 苏州耐思特塑胶有限公司 一种阻燃型电缆料的制备方法及其应用
JP6583518B1 (ja) * 2018-11-28 2019-10-02 横浜ゴム株式会社 コンベヤベルト用ゴム組成物及びコンベヤベルト
CN114752137B (zh) * 2022-03-22 2023-08-29 金发科技股份有限公司 一种阻燃聚烯烃材料及其制备方法和应用

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JP5425973B2 (ja) 2014-02-26

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