WO2015132930A1 - Fluorine-containing elastomer composition, and insulated wire and cable using same - Google Patents

Fluorine-containing elastomer composition, and insulated wire and cable using same Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
copolymer
tetrafluoroethylene
elastomer composition
mass
Prior art date
Application number
PCT/JP2014/055774
Other languages
French (fr)
Japanese (ja)
Inventor
敦郎 矢口
正信 中橋
Original Assignee
日立金属株式会社
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 日立金属株式会社 filed Critical 日立金属株式会社
Priority to PCT/JP2014/055774 priority Critical patent/WO2015132930A1/en
Priority to JP2016506034A priority patent/JP6164357B2/en
Publication of WO2015132930A1 publication Critical patent/WO2015132930A1/en

Links

Images

Classifications

    • 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

Landscapes

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

Abstract

Provided are: a fluorine-containing elastomer composition that has excellent toughness, workability, and heat resistance; and an insulated wire and cable using the same. An insulated wire (10) comprises, on an outer periphery of a conductor (1), an insulating layer (2) composed of a fluorine-containing elastomer composition that includes a fluororesin component including a tetrafluoroethylene-α-olefin copolymer having 2 to 4 carbon atoms (first fluorine-containing copolymer) and an ethylene modified with maleic acid-tetrafluoroethylene copolymer (second fluorine-containing copolymer), polyethylene, and a cross-linking agent, the ratio by mass of the first fluorine-containing copolymer to the second fluorine-containing copolymer being 90:10 to 30:70, the content of the polyethylene being 10 to 50 parts by mass with respect to 100 parts by mass of the fluororesin component.

Description

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Fluorine-containing elastomer composition, and insulated wire and cable using the same
　本発明は、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に関する。 The present invention relates to a fluorine-containing elastomer composition, and an insulated wire and cable using the same.
　電線及びケーブルは、絶縁層やシースといった被覆層に樹脂組成物を用いている。用いる樹脂は、電線及びケーブルの用途により異なる。例えば、耐熱性、耐薬品性、電気絶縁性、可とう性などを必要とする用途には、テトラフルオロエチレン－αオレフィン共重合体やエチレン－テトラフルオロエチレン共重合体などが用いられている。 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. For example, tetrafluoroethylene-α-olefin copolymers and ethylene-tetrafluoroethylene copolymers are used for applications that require heat resistance, chemical resistance, electrical insulation, flexibility, and the like.
　被覆層に用いる樹脂組成物としてテトラフルオロエチレン－αオレフィン共重合体のみを用いた場合、強靭性に問題がある。そこで、当該問題を解決するべく、テトラフルオロエチレン－プロピレン系共重合体にエチレン－テトラフルオロエチレン－フルオロオレフィン共重合体及びエチレン－アクリル酸エステル共重合体をブレンドした樹脂組成物が提案されている(特許文献１参照)。 When only a tetrafluoroethylene-α olefin copolymer is used as the resin composition used for the coating layer, there is a problem in toughness. In order to solve the problem, a resin composition in which an ethylene-tetrafluoroethylene-fluoroolefin copolymer and an ethylene-acrylic acid ester copolymer are blended with a tetrafluoroethylene-propylene copolymer has been proposed. (See Patent Document 1).
特開平５－７８５３９号公報Japanese Patent Laid-Open No. 5-78539
　しかしながら、エチレン－テトラフルオロエチレン系共重合体等のフッ素樹脂は融点が高く、押出成形時の温度を３００℃近くまで上げる必要があり、その結果、押出加工時に発泡を生じることで外観が悪くなるといった加工性低下の問題がある。 However, 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.
　一方、特許文献１で用いられているエチレン－アクリル酸エステル共重合体は、一般的なエチレン系共重合体に比較して高融点であり、比較的、耐熱性が良好であるが、融点の低い樹脂をフッ素樹脂に添加すると、フッ素系ポリマーの特徴である耐熱性が損なわれる問題が出てくる。 On the other hand, 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. When a low resin is added to the fluororesin, there arises a problem that the heat resistance characteristic of the fluoropolymer is impaired.
　そこで、本発明の目的は、強靭性、加工性及び耐熱性に優れた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を提供することにある。 Therefore, 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.
　本発明は、上記目的を達成するために、下記［１］～［５］の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を提供する。 In order to achieve the above object, the present invention provides the following fluorine-containing elastomer compositions [1] to [5], and insulated wires and cables using the same.
［１］テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体（第１の含フッ素共重合体）及びマレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体（第２の含フッ素共重合体）を含むフッ素樹脂成分と、ポリエチレンと、架橋助剤とを含有し、前記第１の含フッ素共重合体と、前記第２の含フッ素共重合体との配合質量比（第１の含フッ素共重合体：第２の含フッ素共重合体）は、９０：１０～３０：７０であり、前記ポリエチレンの配合量は、前記フッ素樹脂成分１００質量部に対して１０～５０質量部である含フッ素エラストマー組成物。
［２］前記フッ素樹脂成分１００質量部に対して１００質量部以下の無機充填剤をさらに含有する前記［１］に記載の含フッ素エラストマー組成物。
［３］導体と、前記導体の外周に被覆された、前記［１］又は前記［２］に記載の含フッ素エラストマー組成物からなる絶縁層とを備えた絶縁電線。
［４］前記［１］又は前記［２］に記載の含フッ素エラストマー組成物からなるシースを備えたケーブル。
［５］前記［３］に記載の絶縁電線を備えたケーブル。 [1] Tetrafluoroethylene-α-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.
[2] The fluorine-containing elastomer composition according to [1], further containing 100 parts by mass or less of an inorganic filler with respect to 100 parts by mass of the fluororesin component.
[3] 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.
[4] A cable including a sheath made of the fluorine-containing elastomer composition according to [1] or [2].
[5] A cable comprising the insulated wire according to [3].
　本発明によれば、強靭性、加工性及び耐熱性に優れた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を提供することができる。 According to the present invention, it is possible to provide a fluorine-containing elastomer composition excellent in toughness, workability and heat resistance, and an insulated wire and cable using the same.
本発明の実施の形態に係る絶縁電線の一例を示す横断面図である。It is a cross-sectional view which shows an example of the insulated wire which concerns on embodiment of this invention. 本発明の実施の形態に係るケーブルの一例を示す横断面図である。It is a cross-sectional view showing an example of a cable according to an embodiment of the present invention.
〔含フッ素エラストマー組成物〕
　本発明の実施の形態に係る含フッ素エラストマー組成物は、テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体（第１の含フッ素共重合体）及びマレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体（第２の含フッ素共重合体）を含むフッ素樹脂成分と、ポリエチレンと、架橋助剤とを含有し、前記第１の含フッ素共重合体と、前記第２の含フッ素共重合体との配合質量比（第１の含フッ素共重合体：第２の含フッ素共重合体）は、９０：１０～３０：７０であり、前記ポリエチレンの配合量は、前記フッ素樹脂成分１００質量部に対して１０～５０質量部である。 [Fluorine-containing elastomer composition]
A fluorine-containing elastomer composition according to an embodiment of the present invention includes tetrafluoroethylene-α-olefin copolymer having 2 to 4 carbon atoms (first fluorine-containing copolymer) and ethylene modified with maleic acid. A fluororesin component containing a tetrafluoroethylene copolymer (second fluorinated copolymer), polyethylene, and a crosslinking aid, the first fluorinated copolymer, and the second The blending mass ratio of the above-mentioned 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 The amount is 10 to 50 parts by mass with respect to 100 parts by mass of the fluororesin component.
（フッ素樹脂成分：第１及び第２の含フッ素共重合体）
　本発明の実施の形態に係る含フッ素エラストマー組成物は、第１及び第２の含フッ素共重合体を含むフッ素樹脂成分を含有している。 (Fluorine resin component: first and second fluorine-containing copolymers)
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.
Ａ．第１の含フッ素共重合体
　第１の含フッ素共重合体は、テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体である。テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体における炭素数２～４のα－オレフィンとしては、プロピレン又はブテン－１を単独で、若しくはエチレン、プロピレン、ブテン－１及びイソブテンから選ばれる２種以上を組合せて用いることが好ましく、プロピレンを単独で又は他のものと組合わせて用いることが特に好ましい。 A. First fluorinated copolymer The first fluorinated copolymer is a tetrafluoroethylene-α-olefin copolymer having 2 to 4 carbon atoms. As the α-olefin having 2 to 4 carbon atoms in the tetrafluoroethylene-α-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.
　テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体は、主成分であるテトラフルオロエチレン及び炭素数２～４のα－オレフィンと共重合可能な成分をさらに共重合させたものであってもよい。例えば、炭素数２～４のα－オレフィンとしてプロピレンを用いた場合、主成分のテトラフルオロエチレン及びプロピレンと共重合可能な成分、例えばイソブチレン、アクリル酸、アクリル酸アルキルエステル、フッ化ビニル、フッ化ビニリデン、ヘキサフルオロプロペン、クロロエチルビニルエーテル、クロロトリフルオロエチレン、パーフルオロアルキルビニルエーテル等を適宜、共重合させたものであってもよい。 Tetrafluoroethylene-α-olefin copolymer having 2 to 4 carbon atoms is obtained by further copolymerizing tetrafluoroethylene as a main component and a component copolymerizable with α-olefin having 2 to 4 carbon atoms. There may be. For example, when propylene is used as the α-olefin having 2 to 4 carbon atoms, 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.
　テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体、例えば、テトラフルオロエチレン－プロピレン系共重合体は、耐熱性、成型性等の観点からテトラフルオロエチレンとプロピレンとの含有モル比(テトラフルオロエチレン／プロピレン)が９５／５～３０／７０であることが好ましく、９０／１０～４５／５５であることが更に好ましい。また、適宜加えられる主成分以外の成分の含有量としては、主成分に対して、５０モル％以下が好ましく、３０モル％以下が更に好ましい。プロピレン以外の炭素数２～４のα－オレフィンを用いた場合のテトラフルオロエチレンとの含有モル比、主成分以外の成分の含有量も上記プロピレンを用いた場合と同様である。 Tetrafluoroethylene-α-olefin copolymer having 2 to 4 carbon atoms, such as tetrafluoroethylene-propylene copolymer, 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. Moreover, as 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. In the case of using an α-olefin having 2 to 4 carbon atoms other than propylene, 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.
　本実施の形態で用いるテトラフルオロエチレン－プロピレン系共重合体等のテトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体は、押出時の自己発熱抑制の観点から、１００℃におけるムーニー粘度が２００ＭＬ以下であることが好ましく、５０ＭＬ以下であることがより好ましい。 Tetrafluoroethylene-α-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.
Ｂ．第２の含フッ素共重合体
　第２の含フッ素共重合体は、マレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体である。マレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体には、ポリマの側鎖にグラフトするマレイン酸グラフトエチレン－テトラフルオロエチレン系共重合体と、ポリマの主鎖に共重合するマレイン酸共重合エチレン－テトラフルオロエチレン系共重合体がある。耐熱性（伸び残率）の観点から、エチレン－テトラフルオロエチレン系共重合体がマレイン酸で変性されたものである必要がある。マレイン酸による変性量は、エチレン－テトラフルオロエチレン系共重合体量の０．１～５質量％であることが好ましい。マレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体を使用することで、ポリエチレンを添加することによるフッ素系ポリマーの特徴である耐熱性が損なわれる問題を解決することができる。 B. Second fluorinated copolymer 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. By using an ethylene-tetrafluoroethylene copolymer modified with maleic acid, it is possible to solve the problem that the heat resistance characteristic of a fluorine polymer due to the addition of polyethylene is impaired.
　第２の含フッ素共重合体としてのマレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体は、主成分であるエチレン及びテトラフルオロエチレンと共重合可能な成分をさらに共重合させたものであってもよい。エチレン及びテトラフルオロエチレン以外の第３成分としては、例えばフルオロオレフィンを用いることができる。 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. As the third component other than ethylene and tetrafluoroethylene, for example, a fluoroolefin can be used.
　フルオロオレフィンとしては、例えばクロロトリフルオロエチレン、フッ化ビニリデン、トリフルオロエチレンなどが挙げられるが、これらに限られるものではない。 Examples of the fluoroolefin include, but are not limited to, chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, and the like.
　マレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体は、耐熱性等の観点からエチレンとテトラフルオロエチレンとの含有モル比(エチレン／テトラフルオロエチレン)が１０／９０～４０／６０であることが好ましい。また、適宜加えられる主成分以外の第３成分の含有量としては、主成分に対して、２０モル％以下が好ましく、１０モル％以下が更に好ましい。 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.
　本実施の形態で用いるマレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体は、押出時の自己発熱抑制の観点から、メルトフローレート（２９７℃, ４９Ｎ）が１０以上であることが好ましく、融点が２４０℃以下であることが更に好ましい。 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.
　上記第１の含フッ素共重合体と、上記第２の含フッ素共重合体との配合質量比（第１の含フッ素共重合体：第２の含フッ素共重合体）は、９０：１０～３０：７０である必要がある。第１の含フッ素共重合体：第２の含フッ素共重合体＝８０：２０～４０：６０であることが好ましく、７０：３０～５０：５０であることがより好ましい。上記第１の含フッ素共重合体の質量比が９０より多い場合、強靭性（カットスルー特性）が不十分であり、上記第２の含フッ素共重合体の質量比が７０より多い場合においては、強靭性（引張伸び特性）が悪化する。 The blending mass ratio of the first fluorine-containing copolymer to the second fluorine-containing copolymer (first fluorine-containing copolymer: 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. When 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.
（ポリエチレン）
　本発明の実施の形態に係る含フッ素エラストマー組成物は、押出加工時における発泡等の発生を抑える目的で、上記フッ素樹脂成分に加え更にポリエチレンを含有している。 (polyethylene)
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.
　本実施の形態で用いるポリエチレンとしては、低密度から高密度まで様々な種類のポリエチレンの中でどの種類を用いてもよい。 As the polyethylene used in the present embodiment, any of various types of polyethylene from low density to high density may be used.
　前述のエチレン－テトラフルオロエチレン系共重合体の融点は２５０℃程度であり、押出成型は場合により、３００℃程度の高温を必要とする。その際に、樹脂や充填剤が吸湿していた水分により発泡が発生し、電線の機械的強度が低下する問題がある。押出温度を低下させた場合でも、樹脂の自己発熱のため発泡を防ぐことができない。 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.
　上記の理由から、押出成型により電線を製造する際には発泡により線速が制限される。線速を増加させるためには、押出機のスクリュー回転数を増加させる必要がある。それに伴い自己発熱による温度上昇が激しくなり、発泡が生じるためである。 For the above reasons, when an electric wire is manufactured by extrusion molding, the wire speed is limited by foaming. In order to increase the linear velocity, it is necessary to increase the screw speed of the extruder. This is because the temperature rise due to self-heating becomes intense and foaming occurs.
　本実施の形態においては、所定量のポリエチレンを添加することで、樹脂組成物全体の粘度を低下させ、それに伴い自己発熱を抑えることができるため、発泡を抑制し、加工性を向上することができる。 In the present embodiment, by adding a predetermined amount of polyethylene, 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.
　本実施の形態におけるポリエチレンの配合量は、上記フッ素樹脂成分の総量１００質量部に対して、１０～５０質量部である必要がある。２０～４０質量部であることが好ましい。１０質量部に満たない場合においては、成形時に発泡が発生し、加工性が悪化する。また、５０質量部より多い場合においては、強靭性（カットスルー特性）が悪化する。 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.
（その他のポリマー）
　本発明の実施の形態に係る含フッ素エラストマー組成物は、エチレン－酢酸ビニル共重合体、エチレン－αオレフィン共重合体等を必要に応じて含有することもできる。 (Other polymers)
The fluorine-containing elastomer composition according to the embodiment of the present invention may contain an ethylene-vinyl acetate copolymer, an ethylene-α olefin copolymer, and the like as necessary.
（架橋助剤）
　本発明の実施の形態に係る含フッ素エラストマー組成物は、架橋反応性を高めるために、架橋助剤を含有している。 (Crosslinking aid)
The fluorine-containing elastomer composition according to the embodiment of the present invention contains a crosslinking aid in order to increase the crosslinking reactivity.
　架橋助剤としては、トリアリルイソシアヌレート、トリアリルシアヌレート、トリアリルトリメリテート、テトラアリルピロメリテート等のアリル型化合物が特に好ましい。 As the crosslinking aid, allyl compounds such as triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate and tetraallyl pyromellitate are particularly preferred.
　本実施の形態における架橋助剤の配合量は、上記フッ素樹脂成分の総量１００質量部に対して、０．１～３質量部であることが好ましく、０．５～２質量部であることがより好ましい。 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.
（無機充填剤）
　本発明の実施の形態に係る含フッ素エラストマー組成物は、無機充填剤を更に含有していることが好ましい。 (Inorganic filler)
The fluorine-containing elastomer composition according to the embodiment of the present invention preferably further contains an inorganic filler.
　無機充填剤としては、炭酸カルシウム、シリカ、タルク、クレーなどが挙げられるが、これらに限られるものではない。 Examples of inorganic fillers include, but are not limited to, calcium carbonate, silica, talc, and clay.
　本実施の形態における無機充填剤の配合量は、耐熱性の観点から、上記フッ素樹脂成分の総量１００質量部に対して、１００質量部以下であることが好ましく、８０質量部以下であることがより好ましく、５０質量部以下であることが更に好ましい。 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.
　テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体、ポリエチレン、架橋助剤、及び無機充填剤から構成される樹脂組成物にマレイン酸で変性されたエチレン－テトラフルオロエチレン共重合体を添加することにより、ポリマーと無機充填剤の密着性が向上し、耐熱性が向上する。 Tetrafluoroethylene-ethylene-tetrafluoroethylene copolymer modified with maleic acid in a resin composition comprising a C2-C4 α-olefin copolymer, polyethylene, a crosslinking aid, and an inorganic filler By adding, the adhesion between the polymer and the inorganic filler is improved, and the heat resistance is improved.
（その他の添加剤）
　本発明の実施の形態に係る含フッ素エラストマー組成物には、上記添加剤に加え、適宜、その他の充填剤、難燃剤、架橋剤、滑剤、酸化防止剤、可塑剤などを添加してもよい。 (Other 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. .
〔絶縁電線〕
　本発明の実施形態に係る絶縁電線は、導体と、導体の外周に被覆された、本発明の実施形態に係る上記含フッ素エラストマー組成物からなる絶縁層とを備えたことを特徴とする。 [Insulated wire]
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.
　図１は、本発明の実施の形態に係る絶縁電線の一例を示す横断面図である。
　図１に示すように、本実施の形態に係る絶縁電線１０は、汎用の材料、例えば、純銅や錫めっき銅等からなる導体１と、導体１の外周に被覆された絶縁層２とを備える。導体１は、図１のように１本である場合に限られず、複数本であってもよい。 FIG. 1 is a cross-sectional view showing an example of an insulated wire according to an embodiment of the present invention.
As shown in FIG. 1, 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.
　絶縁層２は、本発明の実施の形態に係る上記の含フッ素エラストマー組成物から構成され、電子線照射等により架橋されている。 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.
　本実施の形態においては、絶縁体を、単層で構成してもよく、また、多層構造とすることもできる。さらに、必要に応じて、セパレータ、編組等を施してもよい。 In the present embodiment, 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.
〔ケーブル〕
　本発明の実施形態に係るケーブルは、本発明の実施形態に係る上記含フッ素エラストマー組成物を被覆材料（絶縁層及び／又はシース）として使用したことを特徴とする。 〔cable〕
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).
　図２は、本発明の実施の形態に係るケーブルの一例を示す横断面図である。
　図２に示すように、本実施の形態に係るケーブル２０は、導体１に絶縁層２を被覆した絶縁電線３本を紙等の介在４と共に撚り合わせた三芯撚り線と、三芯撚り線の外周に施された押え巻きテープ５と、その外周に押出被覆されたシース３とを備える。絶縁電線は単芯でもよく、三芯以外の多芯撚り線であってもよい。 FIG. 2 is a cross-sectional view showing an example of a cable according to the embodiment of the present invention.
As shown in FIG. 2, 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.
　絶縁層２及びシース３は、本発明の実施の形態に係る上記の含フッ素エラストマー組成物から構成され、電子線照射等により架橋されている。絶縁体２、シース３のどちらかだけが上記の含フッ素エラストマー組成物から構成されていてもよいが、両方であることが好ましい。 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.
　本実施の形態においては、シースを、単層で構成してもよく、また、多層構造とすることもできる。さらに、必要に応じて、セパレータ、編組等を施してもよい。 In the present embodiment, the sheath may be composed of a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.
〔本発明の実施の形態の効果〕
　本発明の実施の形態によれば、強靭性、加工性及び耐熱性に優れた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を提供することができる。
　また、高価なフッ素系ポリマーと比較し、非常に安価であるポリエチレンをブレンドすることで、含フッ素エラストマー組成物の製造コストを下げることが可能となる。 [Effect of the embodiment of the present invention]
According to the embodiment of the present invention, it is possible to provide a fluorine-containing elastomer composition excellent in toughness, workability and heat resistance, and an insulated wire and cable using the same.
Moreover, it becomes possible to reduce the manufacturing cost of a fluorine-containing elastomer composition by blending polyethylene which is very inexpensive as compared with an expensive fluorine-based polymer.
　以下に、本発明を実施例に基づいて更に詳しく説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
　図１の構造の絶縁電線１０を下記の通りの方法で製造し、評価を行なった。 1 The insulated wire 10 having the structure of FIG. 1 was manufactured by the following method and evaluated.
(含フッ素エラストマー組成物の作製)
　表１～２に記載される所定量の各配合剤を１８０℃で投入し、その後２６０℃まで昇温させながら、ニーダーを用いて溶融混練し、各実施例及び比較例の含フッ素エラストマー組成物を作製した。用いた配合剤は、表３に示す通りである。 (Preparation of fluorine-containing elastomer composition)
A predetermined amount of each compounding agent described in Tables 1 and 2 was added at 180 ° C., and then melted and kneaded using a kneader while raising the temperature to 260 ° C., and the fluorine-containing elastomer compositions of each Example and Comparative Example Was made. The compounding agents used are as shown in Table 3.
(絶縁電線の製造)
　次に、作製した含フッ素エラストマー組成物を７５ｍｍ押出機(〔設定温度〕シリンダー：２６０℃、ヘッド：２７０℃、ダイス：２７０℃)を用い、外径０．９ｍｍの錫めっき銅撚線導体上に厚さ０．４ｍｍに押出被覆した。この際の線速は１００ｍ/ｍｉｎとした。次に、これに対し１０Ｍｒａｄの電子線を照射して架橋させ、各実施例及び比較例の絶縁電線を製造した。 (Manufacture of insulated wires)
Next, on the tin-plated copper stranded wire conductor having an outer diameter of 0.9 mm, the produced fluorine-containing elastomer composition was used with a 75 mm extruder ([set temperature] cylinder: 260 ° C., head: 270 ° C., die: 270 ° C.). The film was extrusion coated to a thickness of 0.4 mm. The linear velocity at this time was 100 m / min. Next, this was irradiated with a 10 Mrad electron beam for crosslinking to produce insulated wires of the examples and comparative examples.
(絶縁電線の評価)
　製造した絶縁電線について、下記の試験・評価を行なった。表１～２に評価結果を示す。 (Evaluation of insulated wires)
The manufactured insulated wires were subjected to the following tests and evaluations. Tables 1 and 2 show the evaluation results.
１．引張試験：機械特性（強靭性）の評価
＜評価方法＞
　製造した絶縁電線から錫めっき銅撚線を引き抜き、チューブ形状とした各サンプルの引張強度、引張伸びを測定した。引張強度は１５ＭＰａ以上を、引張伸びは１５０％以上を合格（○）とし、１５ＭＰａ未満、１５０％未満を不合格（×）とした。 1. 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).
２．熱老化試験：耐熱性の評価
＜評価方法＞
　製造した絶縁電線から錫めっき銅撚線を引き抜き、チューブ形状とした各サンプルを２５０℃で１６８時間保持し、その後、上記１．記載の通りの引張試験を実施した。サンプルの引張強度、引張伸びを測定し、初期値（上記１．での測定値）に対する引張強度残率、引張伸び残率を求めた。引張強度残率、引張伸び残率ともに、５０％以上を合格（○）とし、５０％未満を不合格（×）とした。 2. Thermal aging test: Evaluation of heat resistance <Evaluation method>
The tin-plated copper stranded wire was pulled out from the manufactured insulated wire, and each sample made into a tube shape was held at 250 ° C. for 168 hours. Tensile tests were performed as described. The tensile strength and tensile elongation of the sample were measured, and the tensile strength residual ratio and tensile elongation residual ratio relative to the initial values (measured values in 1 above) were determined. For both the tensile strength residual rate and the tensile elongation residual rate, 50% or more was regarded as acceptable (◯), and less than 50% was regarded as unacceptable (x).
３．加工性評価
　成形後の絶縁電線断面を観察し、発泡の有無を確認した。発泡が無かったものを合格（○）とし、発泡が有ったものを不合格（×）とした。 3. Processability evaluation The cross section of the insulated wire after molding was observed to confirm the presence or absence of foaming. Those without foaming were judged as acceptable (◯), and those with foaming were judged as unacceptable (x).
４．カットスルー試験：強靭性の評価
＜評価方法＞
　９０度の金属エッジの上に絶縁電線を置き、２００℃で３００ｇの荷重を加えて１０分間、エッジと絶縁電線の導体とが導通しなければ合格（○）とし、導通したものを不合格（×）とした。 4). 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).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の規定する範囲内である実施例１～４においては、強靭性、加工性及び耐熱性の全てが合格であった。 In Examples 1 to 4 which are within the range defined by the present invention, all of toughness, workability and heat resistance were acceptable.
　比較例１においては、テトラフルオロエチレン－プロピレン共重合体の量が多く、カットスルー特性が不十分であった。 In Comparative Example 1, the amount of tetrafluoroethylene-propylene copolymer was large and the cut-through characteristics were insufficient.
　比較例２においては、マレイン酸で変性されたエチレン－テトラフルオロエチレン共重合体の量が多く、引張伸びが不十分であった。 In Comparative Example 2, the amount of the ethylene-tetrafluoroethylene copolymer modified with maleic acid was large, and the tensile elongation was insufficient.
　比較例３においては、エチレン－テトラフルオロエチレン共重合体がマレイン酸で変性されていないため、耐熱性が不十分であった。 In Comparative Example 3, since the ethylene-tetrafluoroethylene copolymer was not modified with maleic acid, the heat resistance was insufficient.
　比較例４においては、ポリエチレン量が少なく、絶縁電線に発泡が生じたため不合格であった。 Comparative Example 4 was rejected because the amount of polyethylene was small and foaming occurred in the insulated wire.
　比較例５においては、ポリエチレン量が多く、カットスルー特性が不十分であった。 In Comparative Example 5, the amount of polyethylene was large and the cut-through characteristics were insufficient.
　なお、本発明は、上記実施の形態及び実施例に限定されず種々に変形実施が可能である。 In addition, this invention is not limited to the said embodiment and Example, Various deformation | transformation implementation is possible.
１０：絶縁電線、２０：ケーブル
１：導体、２：絶縁層
３：シース、４：介在、５：押さえ巻きテープ 10: Insulated wire, 20: Cable 1: Conductor, 2: Insulating layer 3: Sheath, 4: Intervening, 5: Pressing tape

Claims (5)

  1. 　テトラフルオロエチレン－炭素数２～４のα－オレフィン系共重合体（第１の含フッ素共重合体）及びマレイン酸で変性されたエチレン－テトラフルオロエチレン系共重合体（第２の含フッ素共重合体）を含むフッ素樹脂成分と、ポリエチレンと、架橋助剤とを含有し、
    　前記第１の含フッ素共重合体と、前記第２の含フッ素共重合体との配合質量比（第１の含フッ素共重合体：第２の含フッ素共重合体）は、９０：１０～３０：７０であり、
    　前記ポリエチレンの配合量は、前記フッ素樹脂成分１００質量部に対して１０～５０質量部である含フッ素エラストマー組成物。     Tetrafluoroethylene-α-olefin copolymer having 2 to 4 carbon atoms (first fluorine-containing copolymer) and ethylene-tetrafluoroethylene copolymer modified with maleic acid (second fluorine-containing copolymer) Polymer) containing a fluororesin component, polyethylene, and a crosslinking aid,
    The blending mass ratio of the first fluorine-containing copolymer to the second fluorine-containing copolymer (first fluorine-containing copolymer: second fluorine-containing copolymer) is 90:10 to 30:70,
    The amount of the polyethylene blended is 10 to 50 parts by mass with respect to 100 parts by mass of the fluororesin component.
  2. 　前記フッ素樹脂成分１００質量部に対して１００質量部以下の無機充填剤をさらに含有する請求項１に記載の含フッ素エラストマー組成物。 The fluorine-containing elastomer composition according to claim 1, further comprising 100 parts by mass or less of an inorganic filler with respect to 100 parts by mass of the fluororesin component.
  3. 　導体と、前記導体の外周に被覆された、請求項１又は請求項２に記載の含フッ素エラストマー組成物からなる絶縁層とを備えた絶縁電線。 An insulated wire comprising a conductor and an insulating layer made of the fluorine-containing elastomer composition according to claim 1 or 2, which is coated on an outer periphery of the conductor.
  4. 　請求項１又は請求項２に記載の含フッ素エラストマー組成物からなるシースを備えたケーブル。 A cable comprising a sheath made of the fluorine-containing elastomer composition according to claim 1.
  5. 　請求項３に記載の絶縁電線を備えたケーブル。 A cable comprising the insulated wire according to claim 3.
PCT/JP2014/055774 2014-03-06 2014-03-06 Fluorine-containing elastomer composition, and insulated wire and cable using same WO2015132930A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2014/055774 WO2015132930A1 (en) 2014-03-06 2014-03-06 Fluorine-containing elastomer composition, and insulated wire and cable using same
JP2016506034A JP6164357B2 (en) 2014-03-06 2014-03-06 Fluorine-containing elastomer composition, and insulated wire and cable using the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/055774 WO2015132930A1 (en) 2014-03-06 2014-03-06 Fluorine-containing elastomer composition, and insulated wire and cable using same

Publications (1)

Publication Number Publication Date
WO2015132930A1 true WO2015132930A1 (en) 2015-09-11

Family

ID=54054765

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/055774 WO2015132930A1 (en) 2014-03-06 2014-03-06 Fluorine-containing elastomer composition, and insulated wire and cable using same

Country Status (2)

Country Link
JP (1) JP6164357B2 (en)
WO (1) WO2015132930A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831654A (en) * 2021-11-23 2021-12-24 山东方明药业集团股份有限公司 Lining layer material of flexible composite pipe
CN116082730A (en) * 2022-11-01 2023-05-09 广州敬信高聚物科技有限公司 Irradiation crosslinking type composition containing ECTFE and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10316821A (en) * 1997-05-20 1998-12-02 Kurabe Ind Co Ltd Fluorine-containing elastomer composition
JP2008097882A (en) * 2006-10-06 2008-04-24 Sumitomo Electric Fine Polymer Inc Gasket, sealed secondary battery, and electrolytic capacitor
JP2011165485A (en) * 2010-02-10 2011-08-25 Hitachi Cable Ltd Insulated wire
JP2013004264A (en) * 2011-06-15 2013-01-07 Swcc Showa Cable Systems Co Ltd Heat-resistant electric wire
JP2013170259A (en) * 2012-02-22 2013-09-02 Asahi Glass Co Ltd Fluorine-containing elastomer composition and crosslinked article of the same
JP2014006969A (en) * 2012-06-21 2014-01-16 Swcc Showa Cable Systems Co Ltd Heat-resistant flame-retardant insulated wire

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11316821A (en) * 1998-05-01 1999-11-16 Canon Inc Method and device for information processing
JP4070006B2 (en) * 2002-05-14 2008-04-02 株式会社クラベ Fluorine-containing elastomer composition
JP6194842B2 (en) * 2014-04-07 2017-09-13 日立金属株式会社 Fluorine-containing elastomer composition, and insulated wire and cable using the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10316821A (en) * 1997-05-20 1998-12-02 Kurabe Ind Co Ltd Fluorine-containing elastomer composition
JP2008097882A (en) * 2006-10-06 2008-04-24 Sumitomo Electric Fine Polymer Inc Gasket, sealed secondary battery, and electrolytic capacitor
JP2011165485A (en) * 2010-02-10 2011-08-25 Hitachi Cable Ltd Insulated wire
JP2013004264A (en) * 2011-06-15 2013-01-07 Swcc Showa Cable Systems Co Ltd Heat-resistant electric wire
JP2013170259A (en) * 2012-02-22 2013-09-02 Asahi Glass Co Ltd Fluorine-containing elastomer composition and crosslinked article of the same
JP2014006969A (en) * 2012-06-21 2014-01-16 Swcc Showa Cable Systems Co Ltd Heat-resistant flame-retardant insulated wire

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831654A (en) * 2021-11-23 2021-12-24 山东方明药业集团股份有限公司 Lining layer material of flexible composite pipe
CN116082730A (en) * 2022-11-01 2023-05-09 广州敬信高聚物科技有限公司 Irradiation crosslinking type composition containing ECTFE and application thereof
CN116082730B (en) * 2022-11-01 2023-11-03 广州敬信高聚物科技有限公司 Irradiation crosslinking type composition containing ECTFE and application thereof

Also Published As

Publication number Publication date
JPWO2015132930A1 (en) 2017-03-30
JP6164357B2 (en) 2017-07-19

Similar Documents

Publication Publication Date Title
JP2015003985A (en) Fluorine-containing elastomer composition, and insulated electric wire and insulated cable each using the same
JP6810888B2 (en) Manufacturing method of fluorine-containing elastomer coated insulated wire
JP6194842B2 (en) Fluorine-containing elastomer composition, and insulated wire and cable using the same
JP6164357B2 (en) Fluorine-containing elastomer composition, and insulated wire and cable using the same
JP5388158B2 (en) Fluorine-containing elastomer covered wire
JP2016017123A (en) Fluorine-containing elastomer composition, and insulated wire and cable using the same
JP6311502B2 (en) Fluorine-containing elastomer composition, and insulated wire and cable using the same
JP5176510B2 (en) Fluorine-containing elastomer covered wire
JP5454666B2 (en) Fluorine-containing elastomer covered wire
JPH09288915A (en) Fluorine-containing-elastomer-covered wire or cable
JP2009245927A (en) Composition for manufacturing high thermal-resistance insulated material and high thermal resistance insulated wire manufactured using this
JP2021187970A (en) Resin composition, resin coating material, wire harness for automobile, and method for manufacturing wire harness for automobile
JP2000030535A (en) Wire and cable covered with fluorine containing elastomer and manufacture thereof
JPH09288914A (en) Insulated wire for heating apparatus
KR102240636B1 (en) Fluororesin composition with excellent flexibility, and cable having a dielectric layer made from the same
JP3321969B2 (en) Fluororesin-coated wires and Fluororesin-coated shielded wires
KR20160022037A (en) Fluororesin composition with excellent wear-resistance, and low voltage cable having a dielectric layer made from the same
JP2011249268A (en) Fluorine-containing elastomer covered electric wire and manufacturing method of the same
KR100930438B1 (en) Insulator composition for electric wire with excellent flexibility, flame retardancy and wear resistance and electric wire using the same
JP2013041838A (en) Fluorine-containing elastomer coated wire
JP2019087399A (en) Insulated electric wire
WO2001018824A1 (en) Dual layer system suitable for use as electrical insulation for wires and other conductors
JP6575777B2 (en) Electrical wire
JP2015160873A (en) Fluorine-containing elastomer composition and wire prepared using the same
JPH10334739A (en) Wire/cable covered with elastomer and its manufacture

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14884603

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016506034

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14884603

Country of ref document: EP

Kind code of ref document: A1