JP2015095363A - Wire or cable, production method thereof and insulation tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wire or cable which is excellent in heat resistance and mechanical characteristics and is suppressed in occurrence of detachment in the boundary between layers in a sheath and in the boundary between the sheath and a core, a method of producing the wire or cable and an insulation tape suitable for production of the wire or cable.SOLUTION: A wire or cable (electric wire 1) has a core 10 and a sheath 20, and the sheath 20 has, in order from the side of the core 10, a first layer 22 containing a fluororesin (A) which is melt-moldable and has at least one functional group selected from carbonyl-containing groups, a hydroxy group, epoxy groups and isocyanate groups and a melting point of 260-320°C and a second layer 24 containing a thermoplastic resin (B) of a melting point of 280-420°C other than the fluororesin (A).

Description

  The present invention relates to a wire or cable having a core and a sheath, a manufacturing method thereof, and an insulating tape for forming the sheath.

  As a resin constituting a sheath of a wire or cable that requires heat resistance, a fluororesin (polytetrafluoroethylene (hereinafter also referred to as PTFE)) having excellent heat resistance and electrical insulation may be used. However, a sheath made of a fluororesin has a problem that mechanical properties at high temperatures are insufficient.

As wires or cables for solving the problem, for example, the following have been proposed.
(1) An inner layer made of PTFE excellent in heat resistance and electrical insulation, an intermediate layer made of polyaryletherketone excellent in heat resistance and mechanical properties, and PTFE excellent in heat resistance, electrical insulation and chemical resistance A wire or cable in which an insulating tape composed of an outer layer is wound around a core (Patent Document 1).
(2) A fluororesin layer made of PTFE or the like excellent in heat resistance and electrical insulation, a first layer made of silicone dispersed in mica with excellent heat resistance, and a polyaryletherketone excellent in heat resistance and mechanical properties A wire or cable in which an insulating tape made of a second layer made of is wound around a core, and the insulating tape is covered with an outer layer made of PTFE or the like (Patent Document 2).

However, the wires or cables of (1) and (2) have the following problems.
(I) Since a fluororesin such as PTFE has insufficient adhesion to other materials, peeling is likely to occur at the interface between layers in the sheath or at the interface between the sheath and the core.
(Ii) When a fluororesin such as PTFE that cannot be melt-molded is used as the resin constituting at least one layer of the sheath, a wire or cable is coextruded or sequentially extruded around the core with the resin constituting the sheath It cannot be manufactured. Therefore, it is necessary to manufacture an insulating tape including a layer made of a fluororesin such as PTFE that cannot be melt-molded, wrap the insulating tape around the core, and further sinter to manufacture a wire or cable. It takes.

Special table 2012-531024 Special table 2013-533812 gazette

  The present invention is a wire or cable that is excellent in heat resistance and mechanical properties and hardly peels off at the interface between layers or between the sheath and the core; a resin that forms the sheath around the core of the wire or cable And a method of coextrusion or sequential extrusion, or a method of winding an insulating tape around a core; and an insulating tape suitable for manufacturing the wire or cable.

  The present invention is the wire or cable of [1] to [4], the method of manufacturing the wire or cable of [5] to [11], and the insulating tape of [12] to [15].

  [1] A wire or cable having a core and a sheath covering the core, and the sheath can be melt-molded in order from the core side, and includes a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. A first layer containing a fluororesin (A) having at least one functional group selected from the group consisting of a fluororesin (A) having a melting point of 260 to 320 ° C., and a thermoplastic resin (B having a melting point of 280 to 420 ° C. ) (Excluding the fluororesin (A)) and a second layer containing the wire or cable.

[2] The fluororesin (A) has a carbonyl group-containing group, and the carbonyl group-containing group has a carbonyl group between carbon atoms, a divalent hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, The wire or cable of [1], which is at least one selected from the group consisting of an alkoxycarbonyl group and an acid anhydride residue.
[3] The wire or cable according to [1] or [2], wherein the content of the functional group is 10 to 60000 per 1 × 10 ⁶ carbon atoms in the main chain of the fluororesin (A).
[4] The wire or cable according to any one of [1] to [3], wherein the sheath further includes a third layer containing the fluororesin (A) as an outermost layer.

[5] A method for producing the wire or cable of any one of [1] to [3], wherein the first resin composition containing the fluororesin (A) around the core, and the thermoplastic A method for producing a wire or cable, wherein the sheath is formed by co-extruding or sequentially extruding a second resin composition containing a resin (B) such that the first resin composition is on the core side.
[6] A method for producing a wire or cable according to [4], wherein a first resin composition including the fluororesin (A) and the thermoplastic resin (B) are included around the core. 2 and the third resin composition containing the fluororesin (A) such that the first resin composition is on the core side and the third resin composition is the outermost layer. A method of manufacturing a wire or cable, wherein the sheath is formed by coextrusion or sequential extrusion.
[7] The melt flow rate of the fluororesin (A) used in the third resin composition measured under a load of 372 ° C. and 49 N is 0.5 to 15 g / 10 minutes, A method of manufacturing a wire or cable.

[8] A method of manufacturing the wire or cable of any one of [1] to [3], wherein a first tape containing the fluororesin (A) is wound around the core, and the first tape A method for manufacturing a wire or a cable, wherein the sheath is formed by winding a second tape containing the thermoplastic resin (B) on a tape.
[9] A method for producing the wire or cable of [4], wherein a first tape containing the fluororesin (A) is wound around the core, and the heat is applied on the first tape. A method for manufacturing a wire or cable, wherein a second tape containing a plastic resin (B) is wound, and a third tape containing the fluororesin (A) is wound on the second tape to form the sheath.

[10] A method for producing the wire or cable according to any one of [1] to [3], wherein the first layer containing the fluororesin (A) and the thermoplastic resin (B) around the core And the second layer including the second layer is wound so that the first layer is on the core side to form the sheath.
[11] A method for producing the wire or cable of [4], wherein a first layer containing the fluororesin (A) and a second layer containing the thermoplastic resin (B) around the core And a third layer containing the fluororesin (A) are wound in order so that the first layer is on the core side and the third layer is the outermost layer to form the sheath A method of manufacturing a wire or cable.

  [12] A fluororesin that can be melt-molded and has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group, and has a melting point of 260 to 320 ° C. An insulating tape having a first layer containing (A) and a second layer containing a thermoplastic resin (B) having a melting point of 280 to 420 ° C. (excluding the fluororesin (A)). .

[13] The fluororesin (A) has a carbonyl group-containing group, and the carbonyl group-containing group has a carbonyl group between carbon atoms, a divalent hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, The insulating tape according to [12], which is at least one selected from the group consisting of an alkoxycarbonyl group and an acid anhydride residue.
[14] The insulating tape according to [12] or [13], wherein the content of the functional group is 10 to 60000 per 1 × 10 ⁶ carbon atoms in the main chain of the fluororesin (A).
[15] The insulating tape according to any one of [12] to [14], further including a third layer containing the fluororesin (A).

The wire or cable of the present invention is excellent in heat resistance and mechanical properties, and hardly peels off at the interface between the layers of the sheath or at the interface between the sheath and the core.
According to the method for producing a wire or cable of the present invention, a wire or cable that has excellent heat resistance and mechanical properties and is less likely to be peeled off at the interface between layers of the sheath or at the interface between the sheath and the core is sheathed around the core. Can be produced by a method of co-extrusion or sequential extrusion of resin, or a method of winding an insulating tape around a core.
The insulating tape of the present invention is excellent in heat resistance and mechanical characteristics, and is an insulating tape suitable for the production of a wire or cable that hardly causes peeling at the interface between layers or the interface between the sheath and the core.

It is sectional drawing which shows an example of the electric wire which is one aspect | mode of the wire or cable of this invention. It is sectional drawing which shows the other example of the electric wire which is 1 aspect of the wire or cable of this invention. It is a perspective view which shows an example of the insulating tape of this invention. It is a perspective view which shows the other example of the insulating tape of this invention.

The following definitions of terms apply throughout this specification and the claims.
“Melt moldable” means exhibiting melt fluidity.
“Showing melt fluidity” means that the melt flow rate of the fluororesin measured under a load of 372 ° C. and 49 N is 0.1 g / 10 min or more.
“Sintering” means that the sheath is heat-treated at a temperature equal to or higher than the lowest melting point among the melting points of the respective resins constituting the sheath, and the respective layers of the sheath or the sheath and the core are fused.
“Annealing treatment” means that the sheath is heat-treated at a temperature lower than the lowest melting point among the melting points of each resin constituting the sheath to improve the mechanical strength, wear resistance, etc. of the sheath.
The “screw L / D ratio” means a value obtained by dividing the screw length L by the screw diameter D.
“Screw C / R” is a compression ratio, and means a ratio of the volume per pitch of the groove portion of the supply portion and the volume per pitch of the groove portion of the metering portion in the screw.
“Structural unit” means a unit derived from a monomer formed by polymerization of the monomer. The structural unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
The “carbonyl group-containing group” means a group having a carbonyl group (—C (═O) —) in the structure.

<Wire or cable>
The wire or cable of the present invention has a core and a sheath covering the core. Examples of the wire or cable of the present invention include electric wires and optical fibers.

  FIG. 1 is a cross-sectional view showing an example of an electric wire which is an embodiment of the wire or cable of the present invention. The electric wire 1 includes an electric conductor 10 (core) and a sheath 20 that covers the electric conductor 10. The sheath 20 has a first layer 22 containing a fluororesin (A) and a second layer 24 containing a thermoplastic resin (B) in this order from the electric conductor 10 side.

  FIG. 2 is a cross-sectional view showing another example of an electric wire which is an embodiment of the wire or cable of the present invention. The electric wire 2 includes an electric conductor 10 (core) and a sheath 20 that covers the electric conductor 10. The sheath 20 includes, in order from the electric conductor 10 side, a first layer 22 containing a fluororesin (A), a second layer 24 containing a thermoplastic resin (B), and a third layer containing a fluororesin (A). Layer 26.

(core)
Examples of the core material include metals, polymers, carbon fibers, and ceramics. When the wire or cable of the present invention is an electric wire, the core is an electric conductor (copper, aluminum, silver, steel, etc.) made of metal. The electrical conductor may be a monofilament or a multifilament.

(sheath)
The sheath can be melt-molded in order from the core side, and has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group, and has a melting point of 260 to 320. A first layer containing a fluororesin (A) having a temperature of ° C and a second layer containing a thermoplastic resin (B) having a melting point of 280-420 ° C (excluding the fluororesin (A)); At least. If necessary, the outermost layer may further include a third layer containing the fluororesin (A).

(First layer)
A 1st layer is excellent in heat resistance, electrical insulation, and adhesiveness by including the fluororesin (A) mentioned later. In addition, since the coefficient of friction is low, even if a large stress is applied to the wire or cable, it is difficult to damage the core.
The proportion of the fluororesin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the first layer. The upper limit of the ratio of the fluororesin (A) is 100% by mass.

  The thickness of the first layer is preferably 12 to 100 μm, and more preferably 25 to 75 μm. When the thickness of the first layer is 12 μm or more, the characteristics (heat resistance, electrical insulation) of the first layer can be sufficiently exhibited. If the thickness of the first layer is 100 μm or less, the wire or cable can be made compact and lightweight.

(Second layer)
By including the thermoplastic resin (B) described later, the second layer is excellent in heat resistance and mechanical properties (such as tensile strength and wear resistance).
The proportion of the thermoplastic resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the first layer. The upper limit of the ratio of the thermoplastic resin (B) is 100% by mass.

  The thickness of the second layer is preferably 12 to 100 μm, and more preferably 25 to 75 μm. If the thickness of the second layer is 12 μm or more, the characteristics (heat resistance, mechanical characteristics) of the second layer can be sufficiently exhibited. If the thickness of the second layer is 100 μm or less, the wire or cable can be made compact and lightweight.

(Third layer)
A 3rd layer is excellent in heat resistance, chemical resistance, electrical insulation, and adhesiveness by containing the fluororesin (A) mentioned later. The fluororesin (A) contained in the third layer may be the same as or different from the fluororesin (A) contained in the first layer.
The proportion of the fluororesin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the first layer. The upper limit of the ratio of the fluororesin (A) is 100% by mass.

  The thickness of the third layer is preferably 12 to 100 μm, and more preferably 25 to 75 μm. If the thickness of the third layer is 12 μm or more, the characteristics (heat resistance, chemical resistance, electrical insulation) of the third layer can be sufficiently exhibited. If the thickness of the third layer is 100 μm or less, the wire or cable can be made compact and lightweight.

(Fluororesin (A))
The melting point of the fluororesin (A) is 260 to 320 ° C, preferably 265 to 320 ° C, particularly preferably 280 to 315 ° C. When the melting point of the fluororesin (A) is not less than the lower limit of the above range, the sheath containing the fluororesin (A) has excellent heat resistance. If melting | fusing point of a fluororesin (A) is below the upper limit of the said range, it is excellent in the moldability of the resin composition containing a fluororesin (A).
The melting point of the fluororesin (A) can be adjusted by the type, content ratio, molecular weight, etc. of the constituent units constituting the fluororesin (A). For example, the melting point tends to increase as the proportion of the structural unit (a1) described later increases.

The melt flow rate (hereinafter referred to as MFR) of the fluororesin (A) measured under a load of 372 ° C. and 49 N is preferably 0.1 to 1000 g / 10 minutes, and preferably 0.5 to 100 g / 10 minutes. More preferably, 1 to 30 g / 10 min is more preferable, and 5 to 20 g / 10 min is particularly preferable. When the MFR of the fluororesin (A) is at least the lower limit of the above range, the moldability of the resin composition containing the fluororesin (A), the surface smoothness of the sheath containing the fluororesin (A), and the appearance are excellent. If MFR of a fluororesin (A) is below the upper limit of the said range, it will be excellent in the mechanical characteristic of the sheath containing a fluororesin (A).
Moreover, the sheath containing a fluororesin (A) has low scrape wear. Therefore, from the viewpoint of improving the scrape wear of the sheath, the MFR of the fluororesin (A) is preferably 0.5 to 15 g / 10 minutes, more preferably 1 to 15 g / 10 minutes, and more preferably 5 to 13 g / 10 minutes. Is more preferable.

  MFR is a measure of the molecular weight of the fluororesin (A). When the MFR is large, the molecular weight is small, and when the MFR is small, the molecular weight is large. The molecular weight (MFR) of the fluororesin (A) can be adjusted according to the production conditions of the fluororesin (A). For example, if the monomer polymerization time is shortened, the MFR tends to increase.

The fluororesin (A) has at least one functional group (hereinafter referred to as functional group (I)) selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. By having the functional group (I), the adhesion between the layer containing the fluororesin (A) and the layer containing the thermoplastic resin (B) is improved. This is presumably because the functional group (I) causes some kind of interaction (chemical reaction or the like) with the functional group (carbonyl group or the like) of the thermoplastic resin (B).
The functional group (I) is present at one or both of the main chain end and the side chain of the fluororesin (A). The functional group (I) may be one type or two or more types.

As the functional group (I), a carbonyl group-containing group is preferable from the viewpoint of adhesion between the layer containing the fluororesin (A) and the layer containing the thermoplastic resin (B). A carbonyl group-containing group is a group containing a carbonyl group (—C (═O) —) in the structure. Examples of the carbonyl group-containing group include a divalent hydrocarbon group having a carbonyl group between carbon atoms, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, and an acid anhydride residue.
Examples of the hydrocarbon group include alkylene groups having 2 to 8 carbon atoms.
The haloformyl group is represented by —C (═O) —X (where X is a halogen atom). Examples of the halogen atom in the haloformyl group include a fluorine atom and a chlorine atom, and a fluorine atom is preferred from the viewpoint of the heat resistance of the sheath containing the fluororesin (A). That is, the haloformyl group is preferably a fluoroformyl group (also referred to as a carbonyl fluoride group).
The alkoxy group in the alkoxycarbonyl group is preferably an alkoxy group having 1 to 8 carbon atoms from the viewpoint of the heat resistance of the sheath containing the fluororesin (A) and the moldability of the resin composition containing the fluororesin (A). Or an ethoxy group is particularly preferable.

The content of the functional group (I) in the fluororesin (A) is preferably 10 to 60000, more preferably 100 to 50000, with respect to 1 × 10 ⁶ carbon atoms in the main chain of the fluororesin (A). Preferably, 100 to 10,000 are more preferable, and 300 to 5000 are particularly preferable. If the content of the functional group (I) is not less than the lower limit of the above range, the adhesion between the layer containing the fluororesin (A) and the layer containing the thermoplastic resin (B) will be more excellent. . If the content of the functional group (I) is not more than the upper limit of the above range, high adhesion between the layer containing the fluororesin (A) and the layer containing the thermoplastic resin (B) at a low melting temperature. can get.

  The content of the functional group (I) can be measured by a method such as nuclear magnetic resonance (NMR) analysis or infrared absorption spectrum analysis. For example, the ratio of the structural unit having the functional group (I) in all the structural units constituting the fluororesin (A) using a method such as infrared absorption spectrum analysis as described in JP-A-2007-314720. (Mol%) is obtained, and the content of the functional group (I) can be calculated from the ratio.

  The fluororesin (A) is a cyclic hydrocarbon monomer having a structural unit (a1) based on tetrafluoroethylene (hereinafter also referred to as TFE), an acid anhydride residue, and a polymerizable carbon-carbon double bond. The fluorine-containing copolymer (A1) having the structural unit (a2) based on the body and the structural unit (a3) based on the fluorine-containing monomer (excluding TFE) is preferable. Here, the acid anhydride residue of the structural unit (a2) corresponds to the functional group (I).

  The fluorine-containing copolymer (A1) may have a functional group (I) as a main chain terminal group. As the functional group (I) as the main chain terminal group, an alkoxycarbonyl group, a carbonate group, a hydroxy group, a carboxy group, a fluoroformyl group, an acid anhydride residue and the like are preferable. The functional group can be introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent and the like used in the production of the fluorine-containing copolymer (A1).

  Examples of the cyclic hydrocarbon monomer forming the structural unit (a2) include itaconic anhydride (hereinafter also referred to as IAH), citraconic anhydride (hereinafter also referred to as CAH), and 5-norbornene-2,3-dicarboxylic acid. Examples thereof include acid anhydrides (hereinafter also referred to as NAH) and maleic anhydride. A cyclic hydrocarbon monomer may be used individually by 1 type, and may use 2 or more types together.

  As the cyclic hydrocarbon monomer, a fluorine-containing copolymer having an acid anhydride residue can be used without using a special polymerization method required when maleic anhydride is used (see JP-A-11-193312). One or more selected from the group consisting of IAH, CAH, and NAH is preferable from the viewpoint that the polymer (A1) can be easily produced, and includes a layer containing the fluorinated copolymer (A1) and a thermoplastic resin (B). NAH is preferable from the viewpoint of more excellent adhesion between the layers.

As the fluorine-containing monomer forming the structural unit (a3), from the viewpoint of the heat resistance of the sheath containing the fluorine-containing copolymer (A1) and the moldability of the resin composition containing the fluorine-containing copolymer (A1). , A fluorine-containing compound having one polymerizable carbon-carbon double bond is preferable. For example, fluoroolefin (vinyl fluoride, vinylidene fluoride (hereinafter, also referred to as VdF)), trifluoroethylene, chlorotrifluoroethylene (hereinafter, referred to as “fluorine olefin”). , CTFE.), Hexafluoropropylene (hereinafter also referred to as HFP), etc.) (excluding TFE), CF ₂ = CFOR ^f1 (where R ^f1 has an oxygen atom between carbon atoms) also a good perfluoroalkyl group having 1 to 10 carbon ^{_{atoms.), CF 2 = CFOR f2}} SO 2 X 1 ( provided ^that the ^{R f2} is oxygen atom between carbon atoms A good perfluoroalkylene group having 1 to 10 carbon atoms and, ^{X 1} is a halogen atom or a hydroxyl ^{_{group.), CF 2 = CFOR f3}} CO 2 X 2 ( ^where the ^{R f3} represents an oxygen atom between carbon atoms A perfluoroalkylene group having 1 to 10 carbon atoms that may be present, and X ² is a hydrogen atom or an alkyl group having 3 or less carbon atoms.), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ , P is 1 or 2.), CH ₂ = CX ³ (CF ₂ ) _q X ⁴ (where X ³ is a hydrogen atom or a fluorine atom, q is an integer of 2 to 10, and X ⁴ is A hydrogen atom or a fluorine atom), perfluoro (2-methylene-4-methyl-1,3-dioxolane) and the like.

The fluorine-containing monomer includes VdF, CTFE, HFP, CF from the viewpoint of the heat resistance of the sheath containing the fluorine-containing copolymer (A1) and the moldability of the resin composition containing the fluorine-containing copolymer (A1). _At least one selected from the group consisting of ₂ = CFOR ^f1 and CH ₂ = CX ³ (CF ₂ ) _q X ⁴ is preferable, and CF ₂ = CFOR ^f1 and HFP are more preferable.

As CF ₂ = CFOR ^f1 , CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F, etc. From the viewpoint of the heat resistance of the sheath containing the fluorine-containing copolymer (A1) and the moldability of the resin composition containing the fluorine-containing copolymer (A1), CF ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter, Also referred to as PPVE).

As CH ₂ = CX ³ (CF ₂ ) _q X ⁴ , CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ = CF (CF ₂ ) ₃ H, CH ₂ = CF (CF ₂ ) ₄ H, and the like, and the heat resistance of the sheath containing the fluorinated copolymer (A1) and the resin containing the fluorinated copolymer (A1) From the viewpoint of moldability of the composition, CH ₂ ═CH (CF ₂ ) ₄ F or CH ₂ ═CH (CF ₂ ) ₂ F is preferable.

  In the fluorine-containing copolymer (A1), the structural unit (a1) is 50 to 99.89 mol% with respect to the total molar amount of the structural unit (a1), the structural unit (a2), and the structural unit (a3). And the structural unit (a2) is 0.01 to 5 mol%, the structural unit (a3) is preferably 0.1 to 49.99 mol%, and the structural unit (a1) is 50 to 99.4. More preferably, the structural unit (a2) is 0.1 to 3 mol%, the structural unit (a3) is 0.5 to 49.9 mol%, and the structural unit (a1) is 50 It is particularly preferable that the content is ˜98.9 mol%, the structural unit (a2) is 0.1 to 2 mol%, and the structural unit (a3) is 1 to 49.9 mol%.

If content of each structural unit is in the said range, it will be excellent in the heat resistance of the sheath containing a fluorine-containing copolymer (A1), chemical resistance, and the elasticity modulus in high temperature. In particular, when the content of the structural unit (a2) is within the above range, the amount of the acid anhydride residue of the fluorine-containing copolymer (A1) becomes an appropriate amount, and the fluorine-containing copolymer (A1) Adhesiveness between the layer containing and the layer containing the thermoplastic resin (B) is more excellent. When the content of the structural unit (a3) is within the above range, the moldability of the resin composition containing the fluorinated copolymer (A1) is excellent, and the mechanical properties of the sheath containing the fluorinated copolymer (A1) Is better.
The content of each structural unit can be calculated by melting NMR analysis, fluorine content analysis and infrared absorption spectrum analysis of the fluorine-containing copolymer (A1).

When the fluorinated copolymer (A1) is composed of the structural unit (a1), the structural unit (a2), and the structural unit (a3), the content of the structural unit (a2) is the same as that of the structural unit (a1) and the structural unit. 0.01 mol% with respect to the total molar amount of the unit (a2) and the structural unit (a3) means that the content of the acid anhydride residue in the fluorinated copolymer (A1) is fluorinated copolymer. This corresponds to 100 per 1 × 10 ⁶ carbon atoms in the main chain of (A1). The content of the structural unit (a2) is 5 mol% based on the total molar amount of the structural unit (a1), the structural unit (a2), and the structural unit (a3) in the fluorine-containing copolymer (A1). This corresponds to a content of acid anhydride residues of 50000 per 1 × 10 ⁶ carbon atoms in the main chain of the fluorine-containing copolymer (A1).

  The fluorine-containing copolymer (A1) is a dicarboxylic acid formed by hydrolysis of a part of a cyclic hydrocarbon monomer (itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc. .) May be included. When it has a structural unit based on dicarboxylic acid, content of this structural unit shall be contained in content of a structural unit (a2).

The fluorinated copolymer (A1) is a structural unit based on a non-fluorinated monomer (excluding the cyclic hydrocarbon monomer) in addition to the structural units (a1) to (a3). a4) may be included.
As the non-fluorine-containing monomer, polymerizable carbon-carbon dioxide is used from the viewpoint of the heat resistance of the sheath containing the fluorine-containing copolymer (A1) and the moldability of the resin composition containing the fluorine-containing copolymer (A1). Non-fluorine-containing compounds having one heavy bond are preferred, and examples thereof include olefins having 3 or less carbon atoms (ethylene, propylene, etc.), vinyl esters (vinyl acetate, etc.) and the like. A non-fluorine-containing monomer may be used individually by 1 type, and may use 2 or more types together.
Non-fluorinated monomers include ethylene, propylene, and vinyl acetate from the viewpoint of the heat resistance of the sheath containing the fluorinated copolymer (A1) and the moldability of the resin composition containing the fluorinated copolymer (A1). Are preferred, with ethylene being particularly preferred.

When the fluorinated copolymer (A1) has the structural unit (a4), the content of the structural unit (a4) is 100 mol in total of the structural unit (a1), the structural unit (a2), and the structural unit (a3). Is preferably 5 to 90 mol, more preferably 5 to 80 mol, and still more preferably 10 to 65 mol.
Of the total 100 mol% of all the structural units of the fluorinated copolymer (A1), the total of the structural units (a1) to (a3) is preferably 60 mol% or more, more preferably 65 mol% or more, and 68 mol. % Or more is more preferable. A preferable upper limit is 100 mol%.

Preferable specific examples of the fluorine-containing copolymer (A1) include TFE / PPVE / NAH copolymer, TFE / PPVE / IAH copolymer, TFE / PPVE / CAH copolymer, TFE / HFP / IAH copolymer. , TFE / HFP / CAH copolymer, TFE / VdF / IAH copolymer, TFE / VdF / CAH copolymer, TFE / CH ₂ ═CH (CF ₂ ) ₄ F / IAH / ethylene copolymer, TFE / _{CH 2 = CH (CF 2)} 4 F / CAH / ethylene _{copolymer, TFE / CH 2 = CH (} CF 2) 2 F / IAH / ethylene _{copolymer, TFE / CH 2 = CH (} CF 2) 2 F / CAH / ethylene copolymer and the like.

A fluororesin (A) can be manufactured by a conventional method.
As a manufacturing method of a fluororesin (A), the following method is mentioned, for example, The method of (1) is preferable.
(1) A method of using a monomer having a functional group (I) when the fluororesin (A) is produced by a polymerization reaction.
(2) A method for producing a fluororesin (A) by a polymerization reaction using a radical polymerization initiator having a functional group (I) or a chain transfer agent.
(3) A fluororesin having no functional group (I) is heated, and the fluororesin is partially thermally decomposed to generate reactive functional groups (carbonyl groups, etc.). How to get.
(4) A method of introducing a functional group (I) into a fluororesin by graft polymerization of a monomer having the functional group (I) onto a fluororesin having no functional group (I).

When the fluororesin (A) is produced by a polymerization reaction, the polymerization method is preferably a polymerization method using a radical polymerization initiator from the viewpoint of controlling the MFR of the fluororesin (A).
Examples of the polymerization method include bulk polymerization; solution polymerization using an organic solvent; suspension polymerization using an aqueous medium and an appropriate organic solvent as necessary; emulsion polymerization using an aqueous medium and an emulsifier. From the viewpoint of control of MFR in A), solution polymerization is preferred.

As the radical polymerization initiator, an initiator having a 10-hour half-life temperature of 0 to 100 ° C is preferable, and an initiator having a 20 to 90 ° C is more preferable.
Specific examples of radical polymerization initiators include azo compounds (such as azobisisobutyronitrile), non-fluorinated diacyl peroxides (such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide), and peroxydicarbonates (diisopropyl). Peroxydicarbonate and the like), peroxyesters (tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, etc.), fluorine-containing diacyl peroxide ((Z (CF ₂ ) _r COO) ₂ (however, , Z is a hydrogen atom, a fluorine atom or a chlorine atom, r is an integer of 1 to 10)), inorganic peroxide (potassium persulfate, sodium persulfate, ammonium persulfate, etc.) etc And the like.

In the polymerization, it is also preferable to use a chain transfer agent in order to control the melt viscosity of the fluororesin (A).
Chain transfer agents include alcohol (methanol, ethanol, etc.), chlorofluorohydrocarbon (1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, etc. ) And hydrocarbons (pentane, hexane, cyclohexane, etc.).

As at least one of the radical polymerization initiator and the chain transfer agent, as described above, a compound having the functional group (I) may be used. Thereby, functional group (I) can be introduce | transduced into the principal chain terminal of the fluororesin (A) manufactured.
Examples of the radical polymerization initiator having a functional group (I) include di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, tert-butyl peroxyisopropyl carbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, and di-2. -Ethylhexyl peroxydicarbonate and the like.
Examples of the chain transfer agent having the functional group (I) include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

Examples of the organic solvent used in the solution polymerization include perfluorocarbon, hydrofluorocarbon, chlorohydrofluorocarbon, and hydrofluoroether. As for carbon number, 4-12 are preferable.
Examples of the perfluorocarbon include perfluorocyclobutane, perfluoropentane, perfluorohexane, perfluorocyclopentane, and perfluorocyclohexane.
Examples of the hydrofluorocarbon include 1-hydroperfluorohexane.
Examples of the chlorohydrofluorocarbon include 1,3-dichloro-1,1,2,2,3-pentafluoropropane.
Examples of the hydrofluoroether include methyl perfluorobutyl ether and 2,2,2-trifluoroethyl 2,2,1,1-tetrafluoroethyl ether.

The polymerization temperature is preferably 0 to 100 ° C, and more preferably 20 to 90 ° C.
The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa.
The polymerization time is preferably 1 to 30 hours.

  In the case of polymerizing the fluorinated copolymer (A1), the concentration of the cyclic hydrocarbon monomer is preferably 0.01 to 5 mol%, and preferably 0.1 to 3 mol, out of 100 mol% of all monomers. % Is more preferable, and 0.1 to 2 mol% is more preferable. When the concentration of the cyclic hydrocarbon monomer is within the above range, the polymerization rate during production becomes appropriate. When the concentration of the cyclic hydrocarbon monomer is too high, the polymerization rate tends to decrease. As the cyclic hydrocarbon monomer is consumed during the polymerization, the consumed amount is continuously or intermittently supplied into the polymerization tank, and the concentration of the cyclic hydrocarbon monomer is maintained within the above range. Is preferred.

(Thermoplastic resin (B))
The melting point of the thermoplastic resin (B) is 280 to 420 ° C, preferably 280 to 400 ° C, more preferably 285 to 400 ° C. When the melting point of the thermoplastic resin (B) is 280 ° C. or higher, the heat resistance of the sheath containing the thermoplastic resin (B) is excellent. When the melting point of the thermoplastic resin (B) is 420 ° C. or lower, the moldability of the resin composition containing the thermoplastic resin (B) is excellent.

  The MFR of the thermoplastic resin (B) measured under a load of 372 ° C. and 49 N is preferably 0.5 to 200 g / 10 minutes, more preferably 1 to 100 g / 10 minutes, and further 3 to 50 g / 10 minutes. preferable. When the MFR of the thermoplastic resin (B) is within the above range, it becomes possible to produce a wire or cable by a coextrusion method.

  A thermoplastic resin (B) will not be specifically limited if melting | fusing point is 280-420 degreeC. As the thermoplastic resin (B), polyetherimide (hereinafter also referred to as PEI), poly from the point of adhesion between the layer containing the fluororesin (A) and the layer containing the thermoplastic resin (B). Aryl ether ketone (polyether ether ketone (hereinafter also referred to as PEEK)), aromatic polyester, polyamideimide (hereinafter also referred to as PAI), and thermoplastic polyimide (hereinafter also referred to as TPI) are preferable, PAI, PEEK and TPI are more preferable. A thermoplastic resin (B) may be used individually by 1 type, and may use 2 or more types together.

(Additive)
Each layer which comprises a sheath may contain the additive in the range which does not impair the effect of this invention as needed.
Examples of the additive include an inorganic filler, a pigment, and other additives.

Each layer constituting the sheath preferably contains an inorganic filler having a low dielectric constant and dielectric loss tangent from the viewpoint of improving the electrical characteristics of the sheath.
Examples of the inorganic filler include silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium hydroxide, magnesium hydroxide, Aluminum hydroxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, Examples thereof include glass beads, silica-based balloons, carbon black, carbon nanotubes, carbon nanohorns, graphite, carbon fibers, glass balloons, carbon burns, wood powder, zinc borate and the like. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

The inorganic filler may be porous or non-porous. A porous material is preferable in that the dielectric constant and dielectric loss tangent are lower.
The inorganic filler may be subjected to a surface treatment with a surface treatment agent (such as a silane coupling agent or a titanate coupling agent) in order to improve dispersibility in the fluororesin (A).
When the inorganic filler is included, the content of the inorganic filler is preferably 0.1 to 100% by mass and more preferably 0.1 to 60% by mass with respect to 100% by mass of each layer constituting the sheath.

(Other embodiments)
The wire or cable of the present invention has a core and a sheath, and the sheath has a first layer containing a specific fluororesin (A) in this order from the core side, and a thermoplastic resin having a specific melting point of 280 to 420 ° C. What is necessary is just to have a 2nd layer containing resin (B), and it is not limited to the thing of the example of illustration.
For example, an optical fiber whose core is made of plastic may be used. Moreover, the cable which coat | covered what bundled the several core with the sheath may be sufficient.

(Function and effect)
In the wire or cable of the present invention described above, the sheath includes, in order from the core side, the first layer containing the specific fluororesin (A) excellent in heat resistance, electrical insulation, and adhesion, and heat resistance. And a second layer containing a specific thermoplastic resin (B) excellent in mechanical properties (tensile strength, wear resistance, etc.), and thus excellent in heat resistance and mechanical properties, Peeling hardly occurs at the interface between the sheath and the core.

<Wire or cable manufacturing method>
Examples of the method for producing the wire or cable of the present invention include the following methods (α) to (γ).

Method (α):
Around the core, a first resin composition containing a fluororesin (A), a second resin composition containing a thermoplastic resin (B), and a third resin containing a fluororesin (A) as necessary When the first resin composition is on the core side and the third resin composition is used, the resin composition is coextruded or sequentially extruded so that the third resin composition is the outermost layer. How to form.

Method (β):
A first tape containing a fluororesin (A) is wound around the core, a second tape containing a thermoplastic resin (B) is wound on the first tape, and a second tape is wound if necessary. A method of forming a sheath by winding a third tape containing a fluororesin (A) on top.

Method (γ):
Around the core, a first layer containing a fluororesin (A), a second layer containing a thermoplastic resin (B), and a third layer containing a fluororesin (A) if necessary A method of forming a sheath by wrapping an insulating tape having a sheath when the first layer is on the core side and the third layer is the outermost layer when the third layer is provided.

(Method (α))
In the method (α), the first resin composition, the second resin composition, and if necessary, the third resin composition are melted and extruded simultaneously or sequentially to form two or three layers around the core. This is a method of forming a sheath. After forming the sheath, an annealing treatment may be performed as necessary.
Examples of the apparatus used for the method (α) include a known electric wire manufacturing extruder and an optical fiber manufacturing extruder.

The first resin composition contains a fluororesin (A). The 1st resin composition may contain the additive in the range which does not impair the effect of this invention as needed.
The proportion of the fluororesin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the first resin composition. The upper limit of the ratio of the fluororesin (A) is 100% by mass.

The second resin composition contains a thermoplastic resin (B). The 2nd resin composition may contain the additive in the range which does not impair the effect of this invention as needed.
The proportion of the thermoplastic resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the second resin composition. The upper limit of the ratio of the thermoplastic resin (B) is 100% by mass.

The third resin composition contains a fluororesin (A). The 3rd resin composition may contain the additive in the range which does not impair the effect of this invention as needed. The third resin composition may be the same as or different from the first resin composition.
The proportion of the fluororesin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the third resin composition. The upper limit of the ratio of the fluororesin (A) is 100% by mass.

(Method (β))
In the method (β), a first tape is wound around the core, a second tape is wound on the first tape, and a third tape is wound on the second tape as necessary to sheath. It is a method of forming. Normally, each tape is sintered as each tape is wound, or all tapes are sintered together after the third tape is wound. After forming the sheath, an annealing treatment may be performed as necessary.
Each tape can be manufactured by a known molding method.

The first tape contains a fluororesin (A). The 1st tape may contain the additive in the range which does not impair the effect of the present invention as needed.
The proportion of the fluororesin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the first tape. The upper limit of the ratio of the fluororesin (A) is 100% by mass.

The second tape contains a thermoplastic resin (B). The 2nd tape may contain the additive in the range which does not impair the effect of the present invention as needed.
The proportion of the thermoplastic resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the second tape. The upper limit of the ratio of the thermoplastic resin (B) is 100% by mass.

The third tape contains a fluororesin (A). The 3rd tape may contain the additive in the range which does not impair the effect of the present invention as needed. The third tape may be the same as or different from the first tape.
The proportion of the fluororesin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, out of 100% by mass of the third tape. The upper limit of the ratio of the fluororesin (A) is 100% by mass.

(Method (γ))
In the method (γ), an insulating tape having a first layer, a second layer, and, if necessary, a third layer in order around the core, the first layer on the core side, and the third layer Is used, the sheath is wound so that the third layer becomes the outermost layer. Usually, after winding an insulating tape, the tape is sintered. After forming the sheath, an annealing treatment may be performed as necessary.

FIG. 3 is a cross-sectional view showing an example of the insulating tape of the present invention. The insulating tape 30 has a first layer 32 containing a fluororesin (A) and a second layer 34 containing a thermoplastic resin (B) in this order.
FIG. 4 is a cross-sectional view showing another example of the insulating tape of the present invention. The insulating tape 30 has a first layer 32 containing a fluororesin (A), a second layer 34 containing a thermoplastic resin (B), and a third layer 36 containing a fluororesin (A) in this order. .

The first layer, the second layer, and the third layer that constitute the insulating tape are the same as the first layer, the second layer, and the third layer that constitute the sheath, and a description thereof will be omitted.
The insulating tape can be produced by a known method such as a coextrusion method.

(Wrapping)
When winding the tape, it is preferable that the tape is wound in a spiral shape so that 25 to 65%, more preferably 40 to 55% overlaps with the tape one round before. The overlap angle is preferably 45 to 55 ° with respect to the axial direction of the core.

(Sintering)
The sintering temperature is equal to or higher than the lowest melting point among the melting points of the resins constituting the sheath. The sintering temperature is preferably 420 ° C. or lower.
The sintering time is preferably 30 seconds to 2 minutes, more preferably 60 to 90 seconds.

(Annealing process)
The temperature of the annealing treatment is a temperature lower than the lowest melting point among the melting points of the respective resins constituting the sheath. The annealing temperature is preferably 170 ° C. or higher.
The annealing treatment time is preferably 12 to 24 hours.

(Function and effect)
In the manufacturing method of the wire or cable of the present invention described above, as the resin constituting the first layer of the sheath, a specific fluororesin (A) excellent in heat resistance, electrical insulation and adhesion is used. As the resin constituting the second layer of the sheath, a specific thermoplastic resin (B) having excellent heat resistance and mechanical properties (tensile strength, wear resistance, etc.) is used, so that the heat resistance and mechanical properties are improved. It is possible to manufacture a wire or cable that is excellent and hardly peels off at the interface between the layers of the sheath or at the interface between the sheath and the core.
In addition, since the melt-moldable fluororesin (A) and the thermoplastic resin (B) are used, the resin constituting the sheath can be manufactured by co-extrusion or sequential extrusion around the core.

  Moreover, in the insulating tape of the present invention described above, the first layer containing a specific fluororesin (A) excellent in heat resistance, electrical insulation and adhesion, heat resistance, mechanical properties (tensile strength) And a second layer containing a specific thermoplastic resin (B) excellent in wear resistance, etc., and therefore, a wire or cable that hardly peels off at the interface between the layers of the sheath or at the interface between the sheath and the core It is an insulating tape suitable for.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Examples 1 and 2 are examples, and examples 3 and 4 are reference examples.

(Copolymerization composition)
The copolymer composition of the fluororesin (A) was determined by melt NMR analysis, fluorine content analysis, and infrared absorption spectrum analysis.

(Content of functional group (I))
The proportion of structural units based on the monomer (NAH) having the functional group (I) in the fluororesin (A) was determined by infrared absorption spectrum analysis.
The fluororesin (A) was press molded to obtain a 200 μm film. In the infrared absorption spectrum, an absorption peak derived from a structural unit based on NAH in the fluororesin (A) appears at 1778 cm ⁻¹ . The absorbance of the absorption peak was measured, and the ratio (mol%) of the structural unit based on NAH was determined using the molar absorption coefficient of NAH of 20810 mol ⁻¹ · L · cm ⁻¹ .
When the ratio is a (mol%), the number of functional groups (I) (acid anhydride residues) relative to 1 × 10 ⁶ carbon atoms in the main chain of the fluororesin (A) is [a × 10 ⁶ / 100] pieces.

(Melting point)
Using a differential scanning calorimeter (DSC device, manufactured by Seiko Instruments Inc.), record the melting peak when the fluororesin (A) or the thermoplastic resin (B) is heated at a rate of 10 ° C./min. The temperature (° C.) corresponding to was taken as the melting point.

(MFR)
Using a melt indexer (manufactured by Techno Seven Co., Ltd.), a fluororesin (A) or a thermoplastic resin (B) flowing out for 10 minutes (unit time) from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 372 ° C. and 49 N ) (G) was measured, and the value was defined as MFR (g / 10 min).

(Scrape wear)
The wire was cut into a length of 2 m, and a scrape wear test was performed under the following conditions by a test method based on ISO6722-1 using a product name “magnet wire wear tester (reciprocating type)” manufactured by Yasuda Seiki Co., Ltd.
Needle diameter: 0.45 ± 0.01 mm,
Needle material: SUS316 (conforms to JIS G 7602),
Wear distance: 15.5 ± 1 mm
Wear rate: 55 ± 5 times / minute,
Load: 7N,
Test environment: 23 ± 1 ° C.
The abrasion resistance is expressed by the number of times of reciprocation of the needle required until the sheath is exposed from the electric conductor due to the reciprocation of the needle. If the wear resistance (number of times) is large, the wear resistance of the sheath of the wire is excellent.

(Fluororesin (A))
NAH (anhydrous mixed acid, manufactured by Hitachi Chemical Co., Ltd.) as a monomer for forming the structural unit (a2), PPVE (CF ₂ = CFOCF ₂ CF ₂ CF ₃₎ , perfluoro as a monomer for forming the structural unit (a3) Propyl vinyl ether, manufactured by Asahi Glass Co., Ltd.) was prepared.
(Perfluorobutyryl) peroxide at a concentration of 0.36% by mass in 1,3-dichloro-1,1,2,2,3-pentafluoropropane (AK225cb, manufactured by Asahi Glass Co., Ltd.) (hereinafter referred to as AK225cb). A dissolved polymerization initiator solution was prepared.
An NAH solution in which NAH was dissolved in AK225cb at a concentration of 0.3% by mass was prepared.

369 kg of AK225cb and 30 kg of PPVE were charged into a polymerization tank equipped with a stirrer having an inner volume of 430 L that had been degassed in advance. After the inside of the polymerization tank was ripened and heated to 50 ° C., and further charged with 50 kg of TFE, the pressure in the polymerization tank was increased to 0.89 MPa / G.
Polymerization was carried out while continuously adding 3 L of the polymerization initiator solution to the polymerization tank at a rate of 6.25 mL / min. TFE was continuously charged so that the pressure in the polymerization tank during the polymerization reaction was maintained at 0.89 MPa / G. The NAH solution was continuously charged in an amount corresponding to 0.1 mol% with respect to the number of moles of TFE charged during the polymerization.
Eight hours after the start of polymerization, when 32 kg of TFE was charged, the temperature in the polymerization tank was lowered to room temperature, and the pressure was purged to normal pressure. The obtained slurry was solid-liquid separated from AK225cb and dried at 150 ° C. for 15 hours to obtain 33 kg of a fluorinated copolymer (A1-1).

The specific gravity of the fluorine-containing copolymer (A1-1) was 2.15.
The copolymer composition of the fluorine-containing copolymer (A1-1) is TFE-based structural unit / NAH-based structural unit / PPVE-based structural unit = 97.9 / 0.1 / 2.0 (mol%). there were.
The content of the functional group (I) (acid anhydride residue) in the fluorinated copolymer (A1-1) is 1 × 10 ⁶ carbon atoms in the main chain of the fluorinated copolymer (A1-1). The number was 1000.
The melting point of the fluorinated copolymer (A1-1) was 300 ° C.
The MFR of the fluorinated copolymer (A1-1) was 17.6 g / 10 minutes.

Furthermore, the fluorine-containing copolymer (A1-2) was obtained by heat-treating the fluorine-containing copolymer (A1-1) at 260 ° C. for 24 hours.
The melting point of the fluorinated copolymer (A1-2) was 305 ° C.
The MFR of the fluorinated copolymer (A1-2) was 11.0 g / 10 min.

(Thermoplastic resin (B))
PEEK film (Victrex, APTIV (registered trademark) Films, thickness: 50 μm, melting point: 340 ° C., MFR: 26.5 g / 10 min).

(1st tape, 3rd tape)
The fluorine-containing copolymer (A1-1) was extruded using a 30 mmφ single-screw extruder having a 750 mm wide coat hanger die to obtain a fluororesin film having a thickness of 50 μm. The fluororesin film was slit to a width of 4.0 mm to obtain a first tape. The fluororesin film was slit to a width of 6.5 mm to obtain a third tape.
The screw L / D ratio of the extruder was 24 and the screw C / R was 3. The molding conditions were as follows.
Cylinder temperature: C1 = 300 ° C., C2 = 320 ° C., C3 = 340 ° C.,
Adapter temperature: 340 ° C
Head temperature: 340 ° C.
Die temperature: 340 ° C.
Screw rotation speed: 10rpm,
Take-up speed: 5 m / min.

  The first tape and the third tape using the fluorinated copolymer (A1-2) were also obtained by the same method as described above.

(Second tape)
The PEEK film was slit to a width of 6.0 mm to obtain a second tape.

(Example 1)
The first film using the fluorine-containing copolymer (A1-1) around the electric conductor (core wire diameter: φ1.8 mm, material: tin-plated annealed copper) for electric wires is spirally formed with an overlap angle of 45 to 55 °. I wrapped it. On top of the first film, the second film was spirally wound in the opposite direction to the first film with an overlap angle of 45-55 °. On the 2nd film, the 3rd film using a fluorine-containing copolymer (A1-1) was wound helically in the same direction as the 1st film with the overlap angle of 45-55 degree. Each film wound around the electric conductor was sintered at 400 ° C. for a residence time of 60 to 90 seconds to obtain an electric wire.

(Example 2)
A first film using a fluorine-containing copolymer (A1-2) around an electric conductor (core wire diameter: φ1.8 mm, material: tin-plated annealed copper) for electric wires is spirally formed with an overlap angle of 45 to 55 °. I wrapped it. On top of the first film, the second film was spirally wound in the opposite direction to the first film with an overlap angle of 45-55 °. On the 2nd film, the 3rd film using a fluorine-containing copolymer (A1-2) was wound helically in the same direction as a 1st film with the overlap angle of 45-55 degree. Each film wound around the electric conductor was sintered at 400 ° C. for a residence time of 60 to 90 seconds to obtain an electric wire.

(Example 3)
The fluororesin (A1-1) was pelletized with a twin screw extruder (Technobel).
A fluororesin (A1-1) was extruded around the electric wire conductor (core wire diameter: φ1.8 mm, stranded wire) under the following conditions to obtain an electric wire having an electric wire diameter of φ2.8 mm and a sheath thickness of 0.5 mm.
Cylinder temperature: 350-390 ° C,
Die temperature: 390 ° C,
Take-up speed: 10-30 m / min.
When the scrape wear test was conducted, the wear resistance was 3274 times.

(Example 4)
An electric wire was obtained in the same manner as in Example 3 except that the fluororesin (A1-1) was changed to the fluorinated copolymer (A1-2).
When the scrape abrasion test was conducted, the abrasion resistance was 16954 times.

  The wire or cable of the present invention is a wire, optical fiber, especially drilling or mining, commercial or military aerospace and marine applications, and automobiles that require heat resistance, electrical insulation, and mechanical properties at high temperatures. It is useful as electric wires, optical fibers, etc. used in railways and mass transit.

DESCRIPTION OF SYMBOLS 1 Electric wire 2 Electric wire 10 Electric conductor 20 Sheath 22 1st layer 24 2nd layer 26 3rd layer 30 Insulation tape 32 1st layer 34 2nd layer 36 3rd layer

Claims (15)

A wire or cable having a core and a sheath covering the core;
The sheath is in order from the core side,
A fluororesin (A) which can be melt-molded and has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, and has a melting point of 260 to 320 ° C. A first layer comprising:
And a second layer containing a thermoplastic resin (B) having a melting point of 280 to 420 ° C. (excluding the fluororesin (A)).   The fluororesin (A) has a carbonyl group-containing group, and the carbonyl group-containing group has a carbonyl group between carbon atoms, a divalent hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group. The wire or cable according to claim 1, wherein the wire or cable is at least one selected from the group consisting of acid anhydride residues. The wire or cable according to claim 1 or 2, wherein the content of the functional group is 10 to 60000 with respect to 1 x 10 ⁶ carbon atoms in the main chain of the fluororesin (A).   The wire or cable according to any one of claims 1 to 3, wherein the sheath further includes a third layer containing the fluororesin (A) in an outermost layer. A method for producing the wire or cable according to any one of claims 1 to 3,
Around the core, a first resin composition containing the fluororesin (A) and a second resin composition containing the thermoplastic resin (B), the first resin composition being the core A method of manufacturing a wire or cable, wherein the sheath is formed by coextrusion or sequential extrusion so as to be on the side. A method of manufacturing a wire or cable according to claim 4,
Around the core, a first resin composition containing the fluororesin (A), a second resin composition containing the thermoplastic resin (B), and a third resin containing the fluororesin (A) Manufacturing a wire or cable, wherein the sheath is formed by co-extrusion or sequential extrusion with a resin composition such that the first resin composition is on the core side and the third resin composition is the outermost layer. Method.   The wire according to claim 6, wherein a melt flow rate of the fluororesin (A) used in the third resin composition, measured under a load of 372 ° C and 49 N, is 0.5 to 15 g / 10 min. Or the manufacturing method of a cable. A method for producing the wire or cable according to any one of claims 1 to 3,
A first tape containing the fluororesin (A) is wound around the core,
A method of manufacturing a wire or a cable, wherein the sheath is formed by winding a second tape containing the thermoplastic resin (B) on the first tape. A method of manufacturing a wire or cable according to claim 4,
A first tape containing the fluororesin (A) is wound around the core,
Wrapping the second tape containing the thermoplastic resin (B) on the first tape,
A method of manufacturing a wire or cable, wherein the sheath is formed by winding a third tape containing the fluororesin (A) on the second tape. A method for producing the wire or cable according to any one of claims 1 to 3,
An insulating tape having a first layer containing the fluororesin (A) and a second layer containing the thermoplastic resin (B) around the core, and the first layer is on the core side A method of manufacturing a wire or a cable, wherein the sheath is formed by winding the wire in the manner described above. A method of manufacturing a wire or cable according to claim 4,
An insulation having a first layer containing the fluororesin (A), a second layer containing the thermoplastic resin (B), and a third layer containing the fluororesin (A) in order around the core. A method of manufacturing a wire or a cable, wherein the sheath is formed by winding a tape so that the first layer is on the core side and the third layer is an outermost layer. A fluororesin (A) which can be melt-molded and has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, and has a melting point of 260 to 320 ° C. A first layer comprising:
And a second layer containing a thermoplastic resin (B) having a melting point of 280 to 420 ° C. (excluding the fluororesin (A)).   The fluororesin (A) has a carbonyl group-containing group, and the carbonyl group-containing group has a carbonyl group between carbon atoms, a divalent hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group. The insulating tape according to claim 12, which is at least one selected from the group consisting of acid anhydride residues. 14. The insulating tape according to claim 12, wherein the content of the functional group is 10 to 60000 per 1 × 10 ⁶ carbon atoms in the main chain of the fluororesin (A).   The insulating tape according to any one of claims 12 to 14, further comprising a third layer containing the fluororesin (A).

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