JP2015096577A - Resin composition for electric wire coating material and electric wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an electric wire coating material containing a fluorine resin and a non-fluorine-based thermoplastic resin and enabling an electric wire coating material excellent in heat resistance, electrical insulation properties and mechanical properties to be formed by extrusion molding, and an electric wire having a coating material excellent in heat resistance, electrical insulation properties and mechanical properties.SOLUTION: The resin composition for an electric wire coating material is provided which can be melt-molded and contains a fluorine resin (A) having a melting point of 260 to 320°C, a thermoplastic resin (B) having a melting point of 280 to 420°C excluding the fluorine resin (A), and at least one kind of compound selected from a group consisting of melamines, a cyanuric acid derivative and an isocyanuric acid derivative (C) with the amount of the compound (C) of 0.01 pts.mass or more and less than 1 pts.mass based on total 100 pts.mass of the fluorine resin (A) and the thermoplastic resin (B).

Description

  The present invention relates to a resin composition for a wire covering material and an electric wire.

  As a resin constituting a coating material for an electric wire that requires heat resistance, a fluororesin having excellent heat resistance and electrical insulation may be used. However, a wire covering material made of a fluororesin has a problem that mechanical properties at high temperatures are insufficient.

As an electric wire covering material that solves the problem, for example, as shown below, a material obtained by blending a fluororesin with a non-fluorine-based thermoplastic resin having excellent mechanical properties has been proposed.
(1) A polyaryletherketone and a fluororesin, wherein the fluororesin is tetrafluoroethylene and CF ₂ = CF—Rf ¹ (where Rf ¹ is a trifluoromethyl group or a C 1-5 perfluoroalkoxy group) A wire coating material having a polyaryletherketone / fluororesin melt viscosity ratio of 0.3 to 5.0 (Patent Document 1).
(2) a fluororesin having at least one functional group selected from the group consisting of a carbonyl group, an olefin group and an amino group, a non-fluorinated thermoplastic resin having a reactive functional group, a carbonyl group, a carboxy group, and a haloformyl And a polyfunctional compound having at least one reactive functional group selected from the group consisting of a group, an amide group, an olefin group, an amino group, an isocyanate group, a hydroxy group and an epoxy group (Patent Document 2) ).

International Publication No. 2013/088968 JP 2010-180365 A

However, since the wire covering material (1) is limited in both the fluororesin and the non-fluorinated thermoplastic resin and the melt viscosity ratio is also limited, the usable resin is considerably limited. The degree of freedom of design is extremely low.
As a use of the thermoplastic resin composition of (2), Patent Document 2 mentions a wire coating material as one of many uses. However, when the present inventors tried to produce an electric wire by extruding the thermoplastic resin composition (2) around the core wire, the melt viscosity of the thermoplastic resin composition (2) was increased and stabilized. The wire could not be manufactured.

  The present invention relates to a resin composition for a wire covering material, which includes a fluororesin and a non-fluorinated thermoplastic resin, and can form a wire covering material excellent in heat resistance, electrical insulation, and mechanical properties by extrusion molding; and heat resistance Provided is an electric wire having a coating material excellent in properties, electrical insulation and mechanical properties.

  The resin composition for an electric wire coating material of the present invention can be melt-molded, and includes 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. And the fluororesin (A)), and at least one compound (C) selected from the group consisting of melamines, cyanuric acid derivatives and isocyanuric acid derivatives, and the amount of the compound (C) is It is 0.01 mass part or more and less than 1 mass part with respect to a total of 100 mass parts of the said fluororesin (A) and the said thermoplastic resin (B).

The fluororesin (A) preferably 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.
The fluororesin (A) has a carbonyl group-containing group, and the carbonyl group-containing group is a hydrocarbon group containing a carbonyl group between carbon atoms, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, and an acid anhydride. It is preferably at least one selected from the group consisting of physical residues.
The content of the functional group is preferably 10 to 60000 with respect to 1 × 10 ⁶ carbon atoms in the main chain of the fluororesin (A).

The volume ratio ((A) / (B)) between the fluororesin (A) and the thermoplastic resin (B) is 99/1 to 20/80, and the thermoplastic resin (B) is in the form of fine particles. It is preferable that it is contained in the resin composition for wire coating materials.
The thermoplastic resin (B) is preferably at least one selected from the group consisting of polyamideimide, polyaryletherketone and thermoplastic polyimide.
The electric wire of the present invention is obtained by coating the core wire with the resin composition for electric wire covering material of the present invention.

According to the resin composition for an electric wire covering material of the present invention, an electric wire covering material that includes a fluororesin and a non-fluorinated thermoplastic resin and is excellent in heat resistance, electrical insulation, and mechanical properties can be formed by extrusion molding.
The electric wire of the present invention has a coating material excellent in heat resistance, electrical insulation, and mechanical properties.

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.
“L / D” means a value obtained by dividing the screw length L by the screw diameter D.
“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-containing group” means a group containing a carbonyl group (—C (═O) —) in the structure.

<Resin composition for wire covering material>
The resin composition for an electric wire coating material of the present invention can be melt-molded, and includes 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. And the fluororesin (A)), and at least one compound (C) selected from the group consisting of melamines, cyanuric acid derivatives and isocyanuric acid derivatives. An additive may be included as necessary.

(Fluororesin (A))
Examples of the melt-moldable fluororesin include known ones such as tetrafluoroethylene / fluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, poly Examples thereof include vinylidene fluoride, polychlorotrifluoroethylene, an ethylene / chlorotrifluoroethylene copolymer, and a fluororesin having a functional group (I) described later introduced therein.

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 heat resistance of the wire covering material containing the fluororesin (A) is excellent. 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 for electric wire coating materials 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. If the MFR of the fluororesin (A) is not less than the lower limit of the above range, the moldability of the resin composition for an electric wire covering material containing the fluororesin (A) and the surface smoothness of the electric wire covering material containing the fluororesin (A) , Excellent appearance. 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 electric wire coating material containing a fluororesin (A).

  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) preferably 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 compatibility between the fluororesin (A) and 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.

The functional group (I) is preferably a carbonyl group-containing group from the viewpoint of compatibility between the fluororesin (A) and 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 hydrocarbon group containing 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 preferable from the viewpoint of heat resistance of the wire covering material 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 an alkoxy having 1 to 8 carbon atoms from the viewpoint of the heat resistance of the wire coating material containing the fluororesin (A) and the moldability of the resin composition for the wire coating material containing the fluororesin (A). Group is preferred, and methoxy group or ethoxy group is particularly preferred.

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 content of functional group (I) is more than the lower limit of the said range, the compatibility of a fluororesin (A) and a thermoplastic resin (B) will become more excellent. If content of functional group (I) is below the upper limit of the said range, high compatibility with a fluororesin (A) and a thermoplastic resin (B) will be obtained.

  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 the compatibility between the fluorine-containing copolymer (A1) and the thermoplastic resin (B) is preferable. From the standpoint of superiority, NAH is preferred.

As the fluorine-containing monomer forming the structural unit (a3), the heat resistance of the wire coating material containing the fluorine-containing copolymer (A1) and the resin composition for the wire coating material containing the fluorine-containing copolymer (A1) From the viewpoint of moldability, 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 also referred to as CTFE), hexafluoropropylene (hereinafter also referred to as HFP), etc. (excluding TFE), CF ₂ = CFOR ^F1 (where R ^F1 is between carbon atoms) have an oxygen atom is a good perfluoroalkyl group having 1 to 10 carbon ^{_{atoms.), CF 2 = CFOR F2}} SO 2 X 1 ( provided ^{that, R F2} is TansoHara Having an oxygen atom a perfluoroalkylene group which may having 1 to 10 carbon atoms between, ^{X 1} is a halogen atom or a hydroxyl ^{_{group.), CF 2 = CFOR F3}} CO 2 X 2 ( provided ^{that, R F3} is carbon A perfluoroalkylene group having 1 to 10 carbon atoms which may have an oxygen atom between the atoms, 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 (where 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, and q is an integer of 2 to 10) X ⁴ is a hydrogen atom or a fluorine atom.), Perfluoro (2-methylene-4-methyl-1,3-dioxolane) and the like.

As the fluorine-containing monomer, from the viewpoint of the heat resistance of the wire coating material containing the fluorine-containing copolymer (A1) and the moldability of the resin composition for the wire coating material containing the fluorine-containing copolymer (A1), VdF , CTFE, HFP, CF ₂ = CFOR ^F1 and CH ₂ = CX ³ (CF ₂ ) _q X ⁴ are preferred, and CF ₂ = CFOR ^F1 and HFP are more preferred.

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. CF ₂ = CFOCF ₂ CF from the viewpoint of the heat resistance of the wire coating material containing the fluorinated copolymer (A1) and the moldability of the resin composition for the wire coating material containing the fluorinated copolymer (A1). ₂ CF ₃ (hereinafter also referred to as PPVE) is preferable.

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. The heat resistance of the wire coating material including the fluorinated copolymer (A1) and the fluorinated copolymer (A1) from the viewpoint of formability of the wire coating material resin composition _{comprising, CH 2 = CH (CF 2} ) 4 F or _{CH 2 = CH (CF 2)} , 2 F are preferred.

  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 electric wire coating material 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) and The compatibility with the thermoplastic resin (B) is more excellent. If the content of the structural unit (a3) is within the above range, the wire covering material resin composition containing the fluorine-containing copolymer (A1) is excellent in moldability, and the electric wire containing the fluorine-containing copolymer (A1). The mechanical properties of the coating material are 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-fluorinated monomer, from the viewpoint of the heat resistance of the wire coating material containing the fluorine-containing copolymer (A1) and the moldability of the resin composition for the wire coating material containing the fluorine-containing copolymer (A1), Non-fluorine-containing compounds having one polymerizable carbon-carbon double 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.
As the non-fluorinated monomer, from the viewpoint of the heat resistance of the wire coating material containing the fluorine-containing copolymer (A1) and the moldability of the resin composition for the wire coating material containing the fluorine-containing copolymer (A1), Ethylene, propylene and vinyl acetate are preferred, and ethylene is 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 wire covering material 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 for an electric wire covering material 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, the kneadability with the fluororesin (A) is excellent.

  A thermoplastic resin (B) will not be specifically limited if melting | fusing point is 280-420 degreeC. As the thermoplastic resin (B), from the viewpoint of dispersibility of the thermoplastic resin (B) in the resin composition for wire coating materials, polyetherimide (hereinafter also referred to as PEI), polyaryletherketone (polyethylene). Ether ether ketone (hereinafter also referred to as PEEK) and the like, aromatic polyester, polyamideimide (hereinafter also referred to as PAI), and thermoplastic polyimide (hereinafter also referred to as TPI) are preferable, and PAI, PEEK, and TPI are more preferable. preferable. A thermoplastic resin (B) may be used individually by 1 type, and may use 2 or more types together.

  The volume ratio ((A) / (B)) between the fluororesin (A) and the thermoplastic resin (B) is preferably 99/1 to 20/80, more preferably 99/1 to 25/75, and 97 / 3-30 / 70 is more preferable and 97 / 3-40 / 60 is particularly preferable. If (A) / (B) is within the above range, the thermoplastic resin (B) can be sufficiently dispersed as fine particles in the resin composition for wire coating materials, and as a result, the high temperature of the resin composition for wire coating materials can be increased. In addition to improving the rigidity of the wire, there is a tendency that the weld line of the obtained electric wire is reduced. When the fluororesin (A) has a functional group (I), the compatibility between the fluororesin (A) and the thermoplastic resin (B) is excellent, and the average dispersed particle size of the thermoplastic resin (B) tends to be smaller. .

The average dispersed particle size of the thermoplastic resin (B) in the resin composition for wire covering materials is preferably 0.0001 to 8 μm, more preferably 0.0001 to 3 μm, and further preferably 0.0001 to 0.5 μm. When the average dispersed particle size of the thermoplastic resin (B) is within the above range, the resin composition for wire coating material has improved rigidity at high temperatures, and the weld line of the resulting wire tends to be reduced.
The average dispersed particle size of the thermoplastic resin (B) in the resin composition for electric wire coating materials is determined by observing a cut surface of a press-molded product of the resin composition for electric wire coating materials with a microscope.

(Compound (C))
The compound (C) is at least one selected from the group consisting of melamines, cyanuric acid derivatives and isocyanuric acid derivatives.
A compound (C) may be used individually by 1 type, and may use 2 or more types together.

Examples of melamines include melamine, homologues of melamine, melamine or a salt of the homologue and an acid, and the like.
Examples of homologues of melamine include melam, melem and the like, which are deammonium condensation products of melamine.
Examples of the salt of melamine or its homologue and acid include melamine polyphosphate, melam polyphosphate, melem polyphosphate, and a salt of melamine, melam and melem and polyphosphoric acid represented by the following formula (1) (hereinafter referred to as polyphosphoric acid). And melamine cyanurate (a salt of melamine and isocyanuric acid) represented by the following formula (2). In the formula, n is an integer of 1 or more.

In the cyanuric acid derivative, a hydrogen atom of cyanuric acid is substituted with another atom or group.
Examples of the cyanuric acid derivative include triallyl cyanurate, trimethylmethacrylic cyanurate, and trimethylacrylic cyanurate.

The isocyanuric acid derivative is obtained by replacing the hydrogen atom of isocyanuric acid with another atom or group.
Examples of the isocyanuric acid derivatives include triallyl isocyanurate, trimethyl methacryl isocyanurate, trimethylacryl isocyanurate, and isocyanuric acid derivatives represented by the following formula (3).

  As the compound (C), from the viewpoint of the dispersibility of the thermoplastic resin (B) in the resin composition for a wire coating material and the heat resistance of the wire coating material containing the compound (C), melamine polyphosphate, melam, melem , Melamine cyanurate and isocyanuric acid derivatives represented by the formula (3) are preferred.

  The molecular weight of the compound (C) is preferably 100 to 3000. If the molecular weight of a compound (C) is more than the said lower limit, it will be excellent in the thermal stability of a compound (C). If the molecular weight of the compound (C) is not more than the above upper limit, the dispersibility with respect to the fluororesin (A) will be good, and the mechanical properties, chemical resistance and electrical properties of the wire coating material will be good.

  The amount of the compound (C) is 0.01 parts by mass or more and less than 1 part by mass with respect to 100 parts by mass in total of the fluororesin (A) and the thermoplastic resin (B), and 0.02 to 0.8 A mass part is preferable and 0.05-0.5 mass part is more preferable. If the amount of the compound (C) is equal to or more than the lower limit, the dispersibility of the thermoplastic resin (B) in the resin composition for an electric wire coating material and the heat resistance of the electric wire coating material containing the compound (C) are good. Become. If the amount of the compound (C) is not more than the above upper limit value, the heat resistance of the wire covering material will be good. Moreover, the coating | covering material of an electric wire can be formed by extrusion molding. When the amount of the compound (C) is 1 part by mass or more, the melt viscosity of the resin composition for wire covering materials is not stable, and it is difficult to stably perform extrusion molding.

(Additive)
The resin composition for wire covering materials may contain an additive as long as the effect of the present invention is not impaired.
Examples of the additive include an inorganic filler, a pigment, and other additives.

The resin composition for a wire coating material preferably contains an inorganic filler having a low dielectric constant and dielectric loss tangent from the viewpoint of improving the electrical properties of the wire coating material.
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 the resin composition for wire covering materials.

(Method for producing resin composition for wire covering material)
The resin composition for an electric wire coating material of the present invention can be produced by a method of melt-kneading a fluororesin (A), a thermoplastic resin (B), a compound (C), and an additive as necessary.
Examples of the apparatus used for melt kneading include known kneaders such as an extruder. The extruder is preferably a twin screw type.
The melt kneading temperature is set according to the type of the thermoplastic resin (B), and is preferably 280 ° C. or higher and lower than 450 ° C., and more preferably 300 to 430 ° C. When the melt kneading temperature is 280 ° C. or higher, the compatibility between the fluororesin (A) and the thermoplastic resin (B) is improved in the presence of the compound (C), and the thermoplastic resin (B) is used for the wire coating material. It becomes easy to disperse as fine particles in the resin composition.
The residence time in the extruder is preferably from 10 seconds to 30 minutes.
The screw rotation speed is preferably 50 rpm or more and 1500 rpm or less.

(Function and effect)
In the resin composition for wire covering materials of the present invention described above, since the specific compound (C) is contained, the compatibility between the fluororesin (A) and the thermoplastic resin (B) is improved, and the thermoplasticity is increased. The resin (B) can be dispersed as fine particles in the resin composition for wire coating materials. Therefore, in the obtained wire covering material, electrical insulation derived from the fluororesin (A) and mechanical properties derived from the thermoplastic resin (B) can be achieved at a high level.
In addition, the resin composition for a wire coating material of the present invention described above includes not only a fluororesin (A) having good heat resistance and a thermoplastic resin (B) having good heat resistance, but also heat resistance. Since the compound (C) which further improves the property is included, the heat resistance of the obtained wire covering material is excellent.
Moreover, in the resin composition for electric wire coating materials of the present invention described above, since the amount of the compound (C) is kept low, when the resin composition for electric wire coating materials is extruded to produce an electric wire. Moreover, the melt viscosity of the resin composition for a wire coating material is unlikely to increase, and the wire can be manufactured stably.

<Wire>
The electric wire of the present invention has a core wire and a covering material made of the resin composition for an electric wire covering material of the present invention that covers the periphery of the core wire.
The diameter of the electric wire is preferably 20 μm to 5 mm.
The thickness of the covering material is preferably 5 μm to 2 mm.
The diameter of the core wire is preferably 10 μm to 3 mm.
As a material of the core wire, copper is preferable. The core wire may be plated with tin, silver or the like.

The electric wire of the present invention can be produced by a method in which the resin composition for an electric wire covering material of the present invention is melted and extruded around a core wire from a die outlet to form a covering material around the core wire.
Examples of the electric wire manufacturing apparatus include an extruder provided with an electric wire die cross head.

  Applications of the electric wire of the present invention include applications that require mechanical characteristics (rigidity, strength, etc.) at high temperatures in addition to the characteristics specific to fluororesins, such as aircraft cables, high-voltage cables, communication cables, electricity A heater electric wire etc. are mentioned.

  In the electric wire of the present invention described above, since the core wire is coated with the resin composition for electric wire covering material of the present invention, the covering material is excellent in heat resistance, electrical insulation and mechanical properties.

  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.

(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)
Mass (g) of fluororesin (A) or thermoplastic resin (B) flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 372 ° C. and 49 N for 10 minutes using a melt indexer (manufactured by Techno Seven) ) And measured as MFR (g / 10 min).

(Average dispersed particle size)
The resin composition for wire covering material to be measured was frozen and then cut in liquid nitrogen, and the cut surface was observed with a scanning electron microscope (manufactured by Hitachi High Technology, FE-SEM). The diameters of five particulate substances at a magnification of 3000 were measured using the length measurement function attached to the FE-SEM, and the average dispersed particle diameter was calculated from the average value. In addition, about each particulate matter, it confirmed that it was a fluororesin (A) or a thermoplastic resin (B) by the elemental analysis using an energy dispersive X-ray analyzer (EDX).

(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 ) as a monomer for forming the structural unit (a3), Perfluoropropyl vinyl ether, manufactured by Asahi Glass Co., Ltd.).
(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). It melt | dissolved and the polymerization initiator solution was prepared.
NAH was dissolved in AK225cb at a concentration of 0.3% by mass to prepare a NAH solution.

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, which 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 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.

(Thermoplastic resin (B))
PAI: Polyamidoimide (manufactured by Solvay Advanced Polymers, TORLON (registered trademark) 400TF, melting point: 292 ° C., MFR: 18.4 g / 10 min).
PEEK: polyetheretherketone (manufactured by Solvay Advanced Polymers, KetaSpire (registered trademark) KT-820NT, melting point: 340 ° C., MFR: 17.3 g / 10 min).

(Compound (C))
Compound (C-1): Melamine, melam, melem polyphosphate (manufactured by Nissan Chemical Industries, PHOSMEL (registered trademark) -200FINE, specific gravity: 1.81).
Compound (C-2): Melamine cyanurate (Nissan Chemical Industries, specific gravity: 1.52).
Compound (C-3): Isocyanuric acid derivative represented by formula (3) (manufactured by Shikoku Chemicals).

Example 1
In a twin-screw extruder (screw diameter: 15 mm), the fluorine-containing copolymer (A1-1) and PEEK are made to have a fluorine-containing copolymer (A1-1) / PEEK = 90/10 (volume ratio). The compound (C-1) was further added to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the fluorine-containing copolymer (A1-1) and PEEK, and the screw rotation Number: 200 rpm, Cylinder temperature: Melt-kneaded under the conditions of 330-380 ° C. to obtain a resin composition (D-1) for wire coating materials. The average dispersed particle diameter of PEEK in the resin composition for electric wire coating materials (D-1) was 0.3 μm.

(Example 2)
A resin composition (D-2) for a wire coating material was obtained in the same manner as in Example 1 except that the compound (C-2) was used instead of the compound (C-1). The average dispersed particle size of PEEK in the resin composition for electric wire coating materials (D-2) was 0.5 μm.

(Example 3)
A resin composition (D-3) for a wire coating material was obtained in the same manner as in Example 1 except that the compound (C-3) was used instead of the compound (C-1). The average dispersed particle size of PEEK in the resin composition for electric wire coating materials (D-3) was 0.5 μm.

Example 4
In a twin-screw extruder (screw diameter: 15 mm), the fluorine-containing copolymer (A1-1) and PEEK are made to have a fluorine-containing copolymer (A1-1) / PEEK = 70/30 (volume ratio). The compound (C-1) was further added to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the fluorine-containing copolymer (A1-1) and PEEK, and the screw rotation Number: 200 rpm, Cylinder temperature: Melted and kneaded under conditions of 330 to 380 ° C. to obtain a resin composition for wire coating material (D-4). The average dispersed particle diameter of PEEK in the resin composition for electric wire coating materials (D-4) was 2.1 μm.

(Example 5)
In a twin-screw extruder (screw diameter: 15 mm), the fluorine-containing copolymer (A1-1) and PEEK are made to have a fluorine-containing copolymer (A1-1) / PEEK = 50/50 (volume ratio). The compound (C-1) was further added to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the fluorine-containing copolymer (A1-1) and PEEK, and the screw rotation Number: 200 rpm, Cylinder temperature: Melted and kneaded under conditions of 330 to 380 ° C. to obtain a resin composition for wire coating material (D-5). The average dispersed particle diameter of PEEK in the resin composition for electric wire coating materials (D-5) was 2.2 μm.

(Example 6)
An electric wire manufacturing apparatus having the following configuration was prepared.
Extruder: MSK-25 Extruder, manufactured by IK Corporation
Screw: IKG, full flight, L / D = 24, φ30mm,
Electric wire die cross head: manufactured by Unitech Co., Ltd., maximum conductor diameter: 3 mm, maximum die hole diameter: 20 mm,
Electric wire take-up machine, winder: manufactured by Holy Seisakusho.
As the core wire, manufactured by Yasuda Kogyo Co., Ltd. (kneaded wire, core wire diameter: 1.8 mm, configuration: 37 / 0.26 mm (1 layer: 7 right twists, 2 layers: 12 left twists, 3 layers: 18 right twists) )).

  Using the electric wire manufacturing apparatus, the outer die inner diameter: 13.9 mm, the nipple die outer diameter: 5.9 mm, the line speed: 20 m / min, the coating material thickness: 0.5 mm, the molding temperature: 340 ° C. 2 kg of the resin composition for electric wire covering material (D-1) obtained in Example 1 was extruded around the core wire to obtain an electric wire having a covered electric wire diameter of 2.8 mm. During the production of the electric wire, no sudden increase in melt viscosity of the resin composition for electric wire coating material (D-1) was observed, and the electric wire could be obtained stably.

(Comparative Example 1)
Except not using a compound (C-1), it carried out similarly to Example 1, and obtained the resin composition for electric wire coating materials (D-6). The average dispersed particle diameter of PEEK in the resin composition for electric wire coating materials (D-6) was 2.0 μm.

(Comparative Example 2)
Except not using a compound (C-1), it carried out similarly to Example 4, and obtained the resin composition for electric wire coating materials (D-7). The average dispersed particle size of PEEK in the resin composition for electric wire coating materials (D-7) was 9.6 μm.

(Comparative Example 3)
Except not using a compound (C-1), it carried out similarly to Example 5, and obtained the resin composition (D-8) for wire coating materials. The fluorine-containing copolymer (A1-1) was dispersed in the resin composition for electric wire coating material (D-8). The average dispersed particle size of the fluorinated copolymer (A1-1) in the resin composition for electric wire coating material (D-8) was 12.0 μm.

(Comparative Example 4)
In a twin-screw extruder (screw diameter: 15 mm), the fluorine-containing copolymer (A1-1) and PEEK are made to have a fluorine-containing copolymer (A1-1) / PEEK = 90/10 (volume ratio). Further, the compound (C-1) was added so as to be 1 part by mass with respect to 100 parts by mass of the total amount of the fluorine-containing copolymer (A1-1) and PEEK, and the screw rotation speed: It was melt-kneaded under the conditions of 200 rpm and cylinder temperature: 330 to 380 ° C. to obtain a resin composition for wire coating material (D-9). The average dispersed particle diameter of PEEK in the resin composition for electric wire coating materials (D-9) was 0.2 μm.

(Comparative Example 5)
Using the same wire manufacturing apparatus as in Example 6, outer die inner diameter: 13.9 mm, nipple die outer diameter: 5.9 mm, line speed: 20 m / min, coating material thickness: 0.5 mm, molding temperature: 340 ° C. Under the conditions, 2 kg of the resin composition for wire covering material (D-9) obtained in Comparative Example 4 was extruded around the core wire, and an attempt was made to obtain an electric wire having a covered wire diameter of 2.8 mm. However, an electric wire could not be stably obtained due to a sudden rise in melt viscosity of the resin composition for electric wire coating material (D-9).

(Example 7)
In a twin-screw extruder (screw diameter: 15 mm), the fluorinated copolymer (A1-1) and PAI are adjusted so that the fluorinated copolymer (A1-1) / PAI = 90/10 (volume ratio). The compound (C-1) was further added to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the fluorine-containing copolymer (A-1) and PAI, and the screw rotation Number: 200 rpm, Cylinder temperature: Melt-kneaded under the conditions of 340 ° C. to obtain a resin composition for wire coating material (D-10). The average dispersed particle diameter of PAI in the resin composition for electric wire coating materials (D-10) was 0.2 μm.

(Comparative Example 6)
Except not using a compound (C-1), the resin composition for electric wire coating materials (D-11) was obtained like Example 7. The average dispersed particle diameter of PAI in the resin composition for electric wire coating materials (D-11) was 2.8 μm.

  The resin composition for an electric wire covering material of the present invention is useful as an electric wire covering material that requires mechanical properties (rigidity, strength, etc.) at high temperatures in addition to the characteristics specific to a fluororesin.

Claims (7)

A fluororesin (A) that can be melt-molded and has a melting point of 260 to 320 ° C .;
A thermoplastic resin (B) having a melting point of 280 to 420 ° C. (excluding the fluororesin (A));
And at least one compound (C) selected from the group consisting of melamines, cyanuric acid derivatives and isocyanuric acid derivatives,
For the wire coating material, the amount of the compound (C) is 0.01 parts by mass or more and less than 1 part by mass with respect to 100 parts by mass in total of the fluororesin (A) and the thermoplastic resin (B). Resin composition.   The resin composition for an electric wire coating material according to claim 1, wherein the fluororesin (A) 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.   The fluororesin (A) has a carbonyl group-containing group, and the carbonyl group-containing group is a hydrocarbon group containing a carbonyl group between carbon atoms, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, and an acid anhydride. The resin composition for an electric wire coating material according to claim 2, which is at least one selected from the group consisting of physical residues. The resin composition for an electric wire coating material according to claim 3, wherein the content of the functional group is 10 to 60000 per 1 × 10 ⁶ carbon atoms of the main chain of the fluororesin (A).   The volume ratio ((A) / (B)) between the fluororesin (A) and the thermoplastic resin (B) is 99/1 to 20/80, and the thermoplastic resin (B) is in the form of fine particles. The resin composition for electric wire coating | covering materials as described in any one of Claims 1-4 contained in the resin composition for electric wire coating | covering materials.   The resin for electric wire coating materials according to any one of claims 1 to 5, wherein the thermoplastic resin (B) is at least one selected from the group consisting of polyamideimide, polyaryletherketone, and thermoplastic polyimide. Composition.   The electric wire formed by coat | covering the core wire with the resin composition for electric wire coating materials as described in any one of Claims 1-6.