WO2015132930A1 - Composition d'élastomère contenant du fluor, fil électrique et câble isolés l'utilisant - Google Patents

Composition d'élastomère contenant du fluor, fil électrique et câble isolés l'utilisant Download PDF

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Publication number
WO2015132930A1
WO2015132930A1 PCT/JP2014/055774 JP2014055774W WO2015132930A1 WO 2015132930 A1 WO2015132930 A1 WO 2015132930A1 JP 2014055774 W JP2014055774 W JP 2014055774W WO 2015132930 A1 WO2015132930 A1 WO 2015132930A1
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WO
WIPO (PCT)
Prior art keywords
fluorine
copolymer
tetrafluoroethylene
elastomer composition
mass
Prior art date
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PCT/JP2014/055774
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English (en)
Japanese (ja)
Inventor
敦郎 矢口
正信 中橋
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日立金属株式会社
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Publication date
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Priority to PCT/JP2014/055774 priority Critical patent/WO2015132930A1/fr
Priority to JP2016506034A priority patent/JP6164357B2/ja
Publication of WO2015132930A1 publication Critical patent/WO2015132930A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers

Definitions

  • the present invention relates to a fluorine-containing elastomer composition, and an insulated wire and cable using the same.
  • Wires and cables use resin compositions for coating layers such as insulation layers and sheaths.
  • the resin used varies depending on the application of the electric wire and cable.
  • tetrafluoroethylene- ⁇ -olefin copolymers and ethylene-tetrafluoroethylene copolymers are used for applications that require heat resistance, chemical resistance, electrical insulation, flexibility, and the like.
  • fluororesins such as ethylene-tetrafluoroethylene copolymers have a high melting point, and it is necessary to raise the temperature at the time of extrusion to nearly 300 ° C. As a result, the appearance deteriorates due to foaming during the extrusion process. There is a problem of workability deterioration.
  • the ethylene-acrylic acid ester copolymer used in Patent Document 1 has a higher melting point than a general ethylene copolymer and has relatively good heat resistance.
  • a low resin is added to the fluororesin, there arises a problem that the heat resistance characteristic of the fluoropolymer is impaired.
  • an object of the present invention is to provide a fluorine-containing elastomer composition excellent in toughness, workability and heat resistance, and an insulated wire and cable using the same.
  • the present invention provides the following fluorine-containing elastomer compositions [1] to [5], and insulated wires and cables using the same.
  • Tetrafluoroethylene- ⁇ -olefin copolymer having 2 to 4 carbon atoms (first fluorine-containing copolymer) and ethylene-tetrafluoroethylene copolymer modified with maleic acid (second A fluorine resin component containing a fluorine-containing copolymer), polyethylene, and a crosslinking aid, and a blending mass ratio of the first fluorine-containing copolymer and the second fluorine-containing copolymer
  • First fluorine-containing copolymer: second fluorine-containing copolymer is 90:10 to 30:70, and the blending amount of the polyethylene is 10 to 50 with respect to 100 parts by mass of the fluorine resin component.
  • the fluorine-containing elastomer composition which is a mass part.
  • An insulated wire comprising a conductor and an insulating layer made of the fluorine-containing elastomer composition according to [1] or [2], which is coated on an outer periphery of the conductor.
  • a fluorine-containing elastomer composition according to an embodiment of the present invention includes tetrafluoroethylene- ⁇ -olefin copolymer having 2 to 4 carbon atoms (first fluorine-containing copolymer) and ethylene modified with maleic acid.
  • the blending mass ratio of the above-mentioned fluorine-containing copolymer is 90:10 to 30:70, and the blending amount of the polyethylene is The amount is 10 to 50 parts by mass with respect to 100 parts by mass of the fluororesin component.
  • the fluorine-containing elastomer composition according to the embodiment of the present invention contains a fluorine resin component including the first and second fluorine-containing copolymers.
  • the first fluorinated copolymer is a tetrafluoroethylene- ⁇ -olefin copolymer having 2 to 4 carbon atoms.
  • ⁇ -olefin having 2 to 4 carbon atoms in the tetrafluoroethylene- ⁇ -olefin copolymer having 2 to 4 carbon atoms propylene or butene-1 may be used alone or from ethylene, propylene, butene-1 and isobutene. Two or more selected ones are preferably used in combination, and propylene is particularly preferably used alone or in combination with another.
  • Tetrafluoroethylene- ⁇ -olefin copolymer having 2 to 4 carbon atoms is obtained by further copolymerizing tetrafluoroethylene as a main component and a component copolymerizable with ⁇ -olefin having 2 to 4 carbon atoms. There may be.
  • the main component tetrafluoroethylene and a component copolymerizable with propylene such as isobutylene, acrylic acid, acrylic acid alkyl ester, vinyl fluoride, fluoride Vinylidene, hexafluoropropene, chloroethyl vinyl ether, chlorotrifluoroethylene, perfluoroalkyl vinyl ether or the like may be appropriately copolymerized.
  • Tetrafluoroethylene- ⁇ -olefin copolymer having 2 to 4 carbon atoms is a molar ratio of tetrafluoroethylene and propylene in terms of heat resistance, moldability, etc.
  • Tetrafluoroethylene / propylene is preferably 95/5 to 30/70, and more preferably 90/10 to 45/55.
  • content of components other than the main component added suitably, 50 mol% or less is preferable with respect to a main component, and 30 mol% or less is still more preferable.
  • the molar ratio to tetrafluoroethylene and the contents of components other than the main component are the same as in the case of using propylene.
  • Tetrafluoroethylene- ⁇ -olefin copolymer having 2 to 4 carbon atoms such as tetrafluoroethylene-propylene copolymer used in the present embodiment is Mooney at 100 ° C. from the viewpoint of suppressing self-heating during extrusion.
  • the viscosity is preferably 200 ML or less, and more preferably 50 ML or less.
  • the second fluorinated copolymer is an ethylene-tetrafluoroethylene copolymer modified with maleic acid.
  • the ethylene-tetrafluoroethylene copolymer modified with maleic acid includes a maleic acid grafted ethylene-tetrafluoroethylene copolymer grafted to the side chain of the polymer and a maleic acid copolymer copolymerized to the main chain of the polymer. There is a polymerized ethylene-tetrafluoroethylene copolymer. From the viewpoint of heat resistance (residual elongation), the ethylene-tetrafluoroethylene copolymer must be modified with maleic acid.
  • the amount of modification by maleic acid is preferably 0.1 to 5% by mass of the amount of the ethylene-tetrafluoroethylene copolymer.
  • the ethylene-tetrafluoroethylene copolymer modified with maleic acid as the second fluorine-containing copolymer is a copolymer obtained by further copolymerizing ethylene and tetrafluoroethylene, which are main components. There may be.
  • a fluoroolefin can be used as the third component other than ethylene and tetrafluoroethylene.
  • fluoroolefin examples include, but are not limited to, chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, and the like.
  • the ethylene-tetrafluoroethylene copolymer modified with maleic acid has a molar ratio of ethylene to tetrafluoroethylene (ethylene / tetrafluoroethylene) of 10/90 to 40/60 from the viewpoint of heat resistance and the like. It is preferable. Moreover, as content of the 3rd component other than the main component added suitably, 20 mol% or less is preferable with respect to a main component, and 10 mol% or less is still more preferable.
  • the ethylene-tetrafluoroethylene copolymer modified with maleic acid used in the present embodiment preferably has a melt flow rate (297 ° C., 49 N) of 10 or more from the viewpoint of suppressing self-heating during extrusion. More preferably, the melting point is 240 ° C. or lower.
  • the blending mass ratio of the first fluorine-containing copolymer to the second fluorine-containing copolymer is 90:10 to It must be 30:70.
  • First fluorine-containing copolymer: second fluorine-containing copolymer 80: 20 to 40:60 is preferable, and 70:30 to 50:50 is more preferable.
  • the mass ratio of the first fluorine-containing copolymer is more than 90, the toughness (cut-through characteristics) is insufficient, and when the mass ratio of the second fluorine-containing copolymer is more than 70, , Toughness (tensile elongation characteristics) deteriorates.
  • the fluorine-containing elastomer composition according to the embodiment of the present invention further contains polyethylene in addition to the fluororesin component for the purpose of suppressing the occurrence of foaming and the like during extrusion.
  • polyethylene used in the present embodiment any of various types of polyethylene from low density to high density may be used.
  • the melting point of the above-mentioned ethylene-tetrafluoroethylene copolymer is about 250 ° C., and extrusion molding sometimes requires a high temperature of about 300 ° C. At that time, there is a problem that foaming occurs due to moisture absorbed by the resin and the filler, and the mechanical strength of the electric wire is lowered. Even when the extrusion temperature is lowered, foaming cannot be prevented due to self-heating of the resin.
  • the viscosity of the entire resin composition can be reduced, and self-heating can be suppressed accordingly, so that foaming can be suppressed and workability can be improved. it can.
  • the blending amount of polyethylene in the present embodiment needs to be 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the fluororesin component. It is preferably 20 to 40 parts by mass. When the amount is less than 10 parts by mass, foaming occurs at the time of molding, and workability deteriorates. In addition, when the amount is more than 50 parts by mass, the toughness (cut-through characteristics) is deteriorated.
  • the fluorine-containing elastomer composition according to the embodiment of the present invention may contain an ethylene-vinyl acetate copolymer, an ethylene- ⁇ olefin copolymer, and the like as necessary.
  • the fluorine-containing elastomer composition according to the embodiment of the present invention contains a crosslinking aid in order to increase the crosslinking reactivity.
  • allyl compounds such as triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate and tetraallyl pyromellitate are particularly preferred.
  • the blending amount of the crosslinking aid in the present embodiment is preferably 0.1 to 3 parts by mass, and preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the total amount of the fluororesin component. More preferred.
  • the fluorine-containing elastomer composition according to the embodiment of the present invention preferably further contains an inorganic filler.
  • inorganic fillers include, but are not limited to, calcium carbonate, silica, talc, and clay.
  • the blending amount of the inorganic filler in the present embodiment is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, with respect to 100 parts by mass of the total amount of the fluororesin component from the viewpoint of heat resistance. More preferably, it is still more preferably 50 parts by mass or less.
  • Tetrafluoroethylene-ethylene-tetrafluoroethylene copolymer modified with maleic acid in a resin composition comprising a C2-C4 ⁇ -olefin copolymer, polyethylene, a crosslinking aid, and an inorganic filler
  • a resin composition comprising a C2-C4 ⁇ -olefin copolymer, polyethylene, a crosslinking aid, and an inorganic filler
  • additives In addition to the above additives, other fillers, flame retardants, crosslinking agents, lubricants, antioxidants, plasticizers, and the like may be added to the fluorine-containing elastomer composition according to the embodiment of the present invention as appropriate. .
  • An insulated wire according to an embodiment of the present invention includes a conductor and an insulating layer made of the fluorine-containing elastomer composition according to the embodiment of the present invention, which is coated on the outer periphery of the conductor.
  • FIG. 1 is a cross-sectional view showing an example of an insulated wire according to an embodiment of the present invention.
  • an insulated wire 10 according to the present embodiment includes a conductor 1 made of a general-purpose material, for example, pure copper or tin-plated copper, and an insulating layer 2 coated on the outer periphery of the conductor 1. .
  • the number of conductors 1 is not limited to one as shown in FIG. 1, and a plurality of conductors may be used.
  • the insulating layer 2 is composed of the above-described fluorine-containing elastomer composition according to the embodiment of the present invention, and is crosslinked by electron beam irradiation or the like.
  • the insulator may be formed of a single layer or may have a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.
  • the cable according to the embodiment of the present invention is characterized by using the above-mentioned fluorine-containing elastomer composition according to the embodiment of the present invention as a coating material (insulating layer and / or sheath).
  • FIG. 2 is a cross-sectional view showing an example of a cable according to the embodiment of the present invention.
  • the cable 20 according to the present embodiment includes a three-core stranded wire obtained by twisting together three insulated wires in which a conductor 1 is coated with an insulating layer 2 together with an interposition 4 such as paper.
  • the presser wound tape 5 is provided on the outer periphery, and the sheath 3 is extrusion-coated on the outer periphery.
  • the insulated wire may be a single core or a multi-core stranded wire other than a three-core wire.
  • the insulating layer 2 and the sheath 3 are made of the above-mentioned fluorine-containing elastomer composition according to the embodiment of the present invention, and are crosslinked by electron beam irradiation or the like. Only either the insulator 2 or the sheath 3 may be composed of the above-mentioned fluorine-containing elastomer composition, but both are preferable.
  • the sheath may be composed of a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.
  • the insulated wire 10 having the structure of FIG. 1 was manufactured by the following method and evaluated.
  • Tensile test Evaluation of mechanical properties (toughness) ⁇ Evaluation method> A tin-plated copper stranded wire was drawn from the manufactured insulated wire, and the tensile strength and tensile elongation of each sample in a tube shape were measured. The tensile strength was 15 MPa or more, and the tensile elongation was 150% or more as acceptable (O), and less than 15 MPa and less than 150% were unacceptable (x).
  • Cut-through test Evaluation of toughness ⁇ Evaluation method> Place an insulated wire on a 90-degree metal edge, apply a load of 300 g at 200 ° C, and pass for 10 minutes if the edge and the conductor of the insulated wire do not conduct. X).
  • Comparative Example 1 the amount of tetrafluoroethylene-propylene copolymer was large and the cut-through characteristics were insufficient.
  • Comparative Example 4 was rejected because the amount of polyethylene was small and foaming occurred in the insulated wire.
  • this invention is not limited to the said embodiment and Example, Various deformation

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)
  • Organic Insulating Materials (AREA)

Abstract

L'invention concerne : une composition d'élastomère contenant du fluor qui présente d'excellentes caractéristiques en termes de ténacité, d'aptitude au façonnage et de résistance à la chaleur ; un fil électrique et un câble isolés l'utilisant. Un fil électrique isolé (10) comporte, sur une périphérie externe d'un conducteur (1), une couche isolante (2) composée d'une composition d'élastomère contenant du fluor qui comprend un constituant de résine fluorée comprenant un copolymère de tétrafluoroéthylène-α-oléfine ayant 2 à 4 atomes de carbone (premier copolymère contenant du fluor) et un copolymère d'éthylène modifié par de l'acide maléique-tétrafluoroéthylène (deuxième copolymère contenant du fluor), un polyéthylène et un agent de réticulation. Le rapport en poids du premier copolymère contenant du fluor au deuxième copolymère contenant du fluor étant de 90:10 à 30:70, la teneur en polyéthylène étant de 10 à 50 parties en masse par rapport à 100 parties en masse du constituant résine fluorée.
PCT/JP2014/055774 2014-03-06 2014-03-06 Composition d'élastomère contenant du fluor, fil électrique et câble isolés l'utilisant WO2015132930A1 (fr)

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PCT/JP2014/055774 WO2015132930A1 (fr) 2014-03-06 2014-03-06 Composition d'élastomère contenant du fluor, fil électrique et câble isolés l'utilisant
JP2016506034A JP6164357B2 (ja) 2014-03-06 2014-03-06 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

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PCT/JP2014/055774 WO2015132930A1 (fr) 2014-03-06 2014-03-06 Composition d'élastomère contenant du fluor, fil électrique et câble isolés l'utilisant

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831654A (zh) * 2021-11-23 2021-12-24 山东方明药业集团股份有限公司 一种柔性复合管内衬层材料
CN116082730A (zh) * 2022-11-01 2023-05-09 广州敬信高聚物科技有限公司 一种含ectfe的辐照交联型组合物及其应用

Citations (6)

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Publication number Priority date Publication date Assignee Title
JPH10316821A (ja) * 1997-05-20 1998-12-02 Kurabe Ind Co Ltd 含フッ素エラストマー組成物
JP2008097882A (ja) * 2006-10-06 2008-04-24 Sumitomo Electric Fine Polymer Inc ガスケット、密閉型二次電池および電解コンデンサ
JP2011165485A (ja) * 2010-02-10 2011-08-25 Hitachi Cable Ltd 絶縁電線
JP2013004264A (ja) * 2011-06-15 2013-01-07 Swcc Showa Cable Systems Co Ltd 耐熱電線
JP2013170259A (ja) * 2012-02-22 2013-09-02 Asahi Glass Co Ltd 含フッ素エラストマー組成物およびその架橋物品
JP2014006969A (ja) * 2012-06-21 2014-01-16 Swcc Showa Cable Systems Co Ltd 耐熱難燃絶縁電線

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JPH11316821A (ja) * 1998-05-01 1999-11-16 Canon Inc 情報処理方法及び装置
JP4070006B2 (ja) * 2002-05-14 2008-04-02 株式会社クラベ 含フッ素エラストマー組成物
JP6194842B2 (ja) * 2014-04-07 2017-09-13 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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10316821A (ja) * 1997-05-20 1998-12-02 Kurabe Ind Co Ltd 含フッ素エラストマー組成物
JP2008097882A (ja) * 2006-10-06 2008-04-24 Sumitomo Electric Fine Polymer Inc ガスケット、密閉型二次電池および電解コンデンサ
JP2011165485A (ja) * 2010-02-10 2011-08-25 Hitachi Cable Ltd 絶縁電線
JP2013004264A (ja) * 2011-06-15 2013-01-07 Swcc Showa Cable Systems Co Ltd 耐熱電線
JP2013170259A (ja) * 2012-02-22 2013-09-02 Asahi Glass Co Ltd 含フッ素エラストマー組成物およびその架橋物品
JP2014006969A (ja) * 2012-06-21 2014-01-16 Swcc Showa Cable Systems Co Ltd 耐熱難燃絶縁電線

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831654A (zh) * 2021-11-23 2021-12-24 山东方明药业集团股份有限公司 一种柔性复合管内衬层材料
CN116082730A (zh) * 2022-11-01 2023-05-09 广州敬信高聚物科技有限公司 一种含ectfe的辐照交联型组合物及其应用
CN116082730B (zh) * 2022-11-01 2023-11-03 广州敬信高聚物科技有限公司 一种含ectfe的辐照交联型组合物及其应用

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