JP2015086364A - Molded article, method for producing the same as well as electric wire and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a molded article which hardly causes a melt fracture on a surface of the molded articles even though a molded article is produced by extrusion-molding a resin composition containing a melt-moldable fluorine resin and a thermoplastic resin.SOLUTION: There is provided a method for producing a molded article which comprises: a step of melting a resin composition comprising a fluorine resin (A) which is melt-moldable 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 a melting point of 260 to 320°C and a thermoplastic resin (B) having a melting point of 280 to 420°C (provided that the fluorine resin is excluded); and a step of extruding the resin composition from a die and followed by molding, where the shear rate when the molten resin composition is extruded from the die is 10 to 350 s.

Description

  The present invention relates to a molded article and a manufacturing method thereof, and an electric wire and a manufacturing method thereof.

  Fluorine resin is excellent in heat resistance, flame resistance, chemical resistance, weather resistance, non-adhesiveness, low friction, low dielectric properties, etc., as represented by tetrafluoroethylene polymer. It is used in a wide range of fields, such as agricultural greenhouses, release coating materials for kitchen appliances, and heat-resistant and flame-resistant coating materials. In particular, a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (hereinafter also referred to as PFA) and an ethylene / tetrafluoroethylene copolymer (hereinafter also referred to as ETFE) are excellent in the above properties and can be melt-molded. Therefore, its uses and molding methods are diverse. Especially, since PFA is a perfluoro type fluororesin like polytetrafluoroethylene (hereinafter also referred to as PTFE), it has characteristics such as heat resistance and electrical characteristics comparable to PTFE.

However, a molded article made of a fluororesin has a problem that mechanical properties (rigidity, strength, etc.) at high temperatures are insufficient. As a molded article that solves the problem, a molded article made of a resin composition containing a melt-moldable fluororesin and a thermoplastic resin has been proposed. As the molded article, for example, the following are known.
(1) A sliding member such as a separation claw for peeling a copy paper from a fixing roll of a copying machine, which can be injection-molded, and selected from the group consisting of an acid anhydride group, a carboxy group, an acid halide group, and a carbonate group A sliding member comprising a resin composition containing an adhesive fluororesin having at least one functional group and a thermoplastic polyimide (Patent Document 1).
(2) Medical products comprising a resin composition containing a melt-moldable fluororesin (PFA, ETFE, etc.) and a polyaryl ketone (polyetheretherketone (hereinafter also referred to as PEEK), etc.) (Patent Document 2) .

JP 2012-113119 A JP 2010-189599 A

However, as a result of the study by the present inventors, when a resin composition containing a meltable fluororesin and a thermoplastic resin is melted and extruded and molded from a die, melt fracture tends to occur on the surface of the molded product. I understood it.
For example, when the resin composition is used as a coating material for electric wires and a coating layer is formed around the core wire, melt fracture occurs on the surface of the coating layer, resulting in poor appearance of the wires.

The present invention relates to a molded product in which melt fracture is unlikely to occur on the surface of the molded product, even though the molded product is produced by extrusion molding a resin composition containing a melt-moldable fluororesin and a thermoplastic resin. A manufacturing method is provided.
In addition, the present invention generates melt fracture on the surface of the coating layer despite the fact that a coating layer is formed by extruding a resin composition containing a melt-moldable fluororesin and a thermoplastic resin around the core wire. Provided is a method of manufacturing a wire that is difficult to perform.

The method for producing a molded article of the present invention is melt-moldable, 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 600. Melting a resin composition containing a fluororesin (A) having a temperature of 320 ° C. and a thermoplastic resin (B) having a melting point of 280 to 420 ° C. (excluding the fluororesin (A)); A method for producing a molded article that is extruded and molded, wherein a shear rate when the molten resin composition is extruded from the die is 10 to 350 s ⁻¹ .

The method for producing an electric wire of the present invention can be melt-molded, 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 resin composition containing a fluororesin (A) having a temperature of ° C and a thermoplastic resin (B) having a melting point of 280 to 420 ° C (excluding the fluororesin (A)) is melted, and the core wire is formed from the die. A method for producing an electric wire which is extruded around a core wire to form a coating layer around the core wire, and the shear rate when the molten resin composition is extruded from the die is 10 to 350 s ^−1. Features.

The fluororesin (A) has a carbonyl group-containing group, and the carbonyl group-containing group has a 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. 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 thermoplastic resin (B) is preferably at least one selected from the group consisting of polyamideimide, polyarylketone and thermoplastic polyimide.

  In the method for producing a molded article of the present invention, the thermoplastic resin (B) is a polyaryl ketone, and the resin composition contains the fluororesin (A) as fine particles having an average dispersed particle diameter of 10 μm or less. The composition is preferably heat-treated at a temperature in the range of 180 ° C. or higher and lower than the melting point of the polyaryl ketone, and then the resin composition is melted and extruded from a die.

  In the method for producing an electric wire of the present invention, the thermoplastic resin (B) is a polyaryl ketone, and the resin composition contains the fluororesin (A) as fine particles having an average dispersed particle diameter of 10 μm or less in the resin composition. The product is subjected to heat treatment at a temperature range of 180 ° C. or higher and lower than the melting point of the polyaryl ketone, and then the resin composition is melted and extruded from the die around the core wire to form a coating layer around the core wire. preferable.

The molded article of the present invention is obtained by the method for producing a molded article of the present invention.
The electric wire of the present invention is obtained by the electric wire manufacturing method of the present invention.

According to the method for producing a molded product of the present invention, the molded product is produced by extrusion molding a resin composition containing a melt-moldable fluororesin and a thermoplastic resin. Melt fracture is unlikely to occur.
Although the molded article of the present invention is obtained by extruding a resin composition containing a melt-moldable fluororesin and a thermoplastic resin, the melt fracture of the surface is suppressed.
According to the method for manufacturing an electric wire of the present invention, the surface of the coating layer is formed even though the resin composition containing a melt-moldable fluororesin and a thermoplastic resin is extruded around the core wire to form the coating layer. It is difficult for melt fracture to occur.
The electric wire of the present invention is obtained by extruding a resin composition containing a melt-moldable fluororesin and a thermoplastic resin around a core wire to form a coating layer. The melt fracture is suppressed.

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.
"Melt fracture" means that when a molten resin composition is pressurized and discharged from a narrow area, the fluid form is a shark on the surface (shark skin) in a high-speed region exceeding a certain limit. It means an abnormal phenomenon that exhibits a spiral (spiral ring), irregular shape, or intermittent shape.
“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.
“Monomer” means a compound having a polymerizable carbon-carbon double bond.

<Resin composition>
The resin composition used in the production method of the present invention is melt-moldable, 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. 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 (excluding the fluororesin (A)). An additive may be included as necessary.

(Fluororesin (A))
The melting point of the fluororesin (A) is 260 to 320 ° C, preferably 265 to 320 ° C, more preferably 280 to 315 ° C. When the melting point of the fluororesin (A) is 260 ° C. or more, the molded product containing the fluororesin (A) has excellent heat resistance. If melting | fusing point of a fluororesin (A) is 320 degrees C or less, it is excellent in the moldability of the resin composition containing a fluororesin (A).

  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 0.1 g / 10 min or more, the moldability of the resin composition containing the fluororesin (A), the surface smoothness and appearance of the molded product containing the fluororesin (A) are excellent. . When the MFR of the fluororesin (A) is 1000 g / 10 min or less, the molded article containing the fluororesin (A) is excellent in mechanical strength.

  MFR is a measure of the molecular weight of the fluororesin (A). When the MFR is large, the molecular weight is small, and when it 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 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 with the thermoplastic resin (B). A carbonyl group-containing group is a group having a carbonyl group (—C (═O) —) in the structure. Examples of the carbonyl group-containing group include a 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 preferable from the viewpoint of heat resistance of a molded article containing the fluororesin (A). That is, as the haloformyl group, a fluoroformyl group (also referred to as a carbonyl fluoride group) is preferable.
The alkoxy group in the alkoxycarbonyl group is an alkoxy group having 1 to 8 carbon atoms in terms of both the heat resistance of the molded product containing the fluororesin (A) and the moldability of the resin composition containing the fluororesin (A). Preferably, a methoxy group 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 content of functional group (I) is more than the lower limit of the said range, compatibility with a fluororesin (A) and a thermoplastic resin (B) will become still better. If content of functional group (I) is below the upper limit of the said range, high compatibility with a thermoplastic resin (B) will be obtained at low melting temperature.

  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 carboxyl 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 of easy production of the polymer (A1), and NAH is preferable from the viewpoint of more excellent compatibility with the thermoplastic resin (B).

As the fluorine-containing monomer forming the structural unit (a3), the heat resistance of the molded product containing the fluorine-containing copolymer (A1) and the moldability of the resin composition containing the fluorine-containing copolymer (A1) From the above, 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.) (however, 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.

As the fluorine-containing monomer, VdF, CTFE, HFP, from the viewpoint of the heat resistance of the molded product 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 CF 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. CF ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter referred to as the heat resistance of the molded product containing the fluorine-containing copolymer (A1) and the moldability of the resin composition containing the fluorine-containing copolymer (A1). , 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, including the heat resistance of the molded product containing the fluorinated copolymer (A1) and the fluorinated copolymer (A1). From the viewpoint of moldability of the resin composition, CH ₂ ═CH (CF ₂ ) ₄ F and CH ₂ ═CH (CF ₂ ) ₂ F are 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 the content of each structural unit is within the above range, the fluorine-containing copolymer (A1) is excellent in heat resistance and chemical resistance, and the molded product containing the fluorine-containing copolymer (A1) has an elastic modulus at high temperature. Excellent. In particular, when the content of the structural unit (a2) is within the above range, the amount of the acid anhydride residue contained in the fluorine-containing copolymer (A1) becomes an appropriate amount, which is in phase with the thermoplastic resin (B). It has better solubility. If the content of the structural unit (a3) is within the above range, the fluorinated copolymer (A1) is excellent in moldability, and the molded product containing the fluorinated copolymer (A1) has mechanical properties (stress crack resistance). Etc.).
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.
The non-fluorine-containing monomer is a carbon-carbon double from the viewpoint of the heat resistance of the molded product 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 bond are preferable, 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 acetic acid from the viewpoint of the heat resistance of the molded product containing the fluorinated copolymer (A1) and the moldability of the resin composition containing the fluorinated copolymer (A1). Vinyl is 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 the 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, a polymerization method using a radical polymerization initiator is preferable as the polymerization method from the viewpoint of controlling the melt flow rate 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 controlling the melt flow rate of 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, etc.), 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, and r is an integer of 1 to 10)), inorganic peroxides (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.

  When manufacturing a fluorine-containing copolymer (A1), 0.01-5 mol% is preferable among 100 mol% of all monomers, and the density | concentration of the said cyclic hydrocarbon monomer is 0.1-3 mol. % 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 molded product containing the thermoplastic resin (B) is excellent in heat resistance. 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, 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 improving dispersibility with the fluororesin (A), polyetherimide (hereinafter also referred to as PEI), polyaryl ketone (PEEK, etc.), aromatic polyester, polyamideimide ( Hereinafter, PAI) and thermoplastic polyimide (hereinafter also referred to as TPI) are preferable, and 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)
The resin composition in the present invention may contain an additive as long as it does not impair the effects of the present invention.
Examples of the additive include an inorganic filler, a pigment, and other additives.

The resin composition preferably contains an inorganic filler having a low dielectric constant and dielectric loss tangent from the viewpoint of improving the electrical characteristics of the molded product.
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. From the viewpoint of lower dielectric constant and dielectric loss tangent, it is preferably porous.
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).

(Ratio of each component)
The volume ratio ((A) / (B)) between the fluororesin (A) and the thermoplastic resin (B) is 99/1 to 60/40 from the viewpoint of dispersing the thermoplastic resin (B) as finer particles. Preferably, 99/1 to 70/30 is more preferable, 97/3 to 75/25 is more preferable, and 97/3 to 80/20 is particularly preferable. Further, when the fluororesin (A) has a reactive functional group, the fluororesin (A) is excellent in compatibility with the thermoplastic resin (B), and the average dispersed particle size of the thermoplastic resin (B) becomes smaller. Cheap.

  The volume ratio ((A) / (B)) between the fluororesin (A) and the thermoplastic resin (B) is preferably 1/99 to 40/60 from the viewpoint of dispersing the fluororesin (A) as finer particles. 1/99 to 30/70 are more preferable, 3/97 to 25/75 are more preferable, and 3/97 to 20/80 are particularly preferable.

The average dispersed particle size of the fluororesin (A) or the thermoplastic resin (B) in the resin composition is preferably 10 μm or less, and more preferably 8 μm or less. If the average dispersed particle size is 10 μm or less, the surface roughness of the molded product tends to be small.
The average dispersed particle size of the fluororesin (A) or the thermoplastic resin (B) in the resin composition is determined by observing the cut surface of a molded product made of the resin composition with a microscope.

  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 fluororesin (A).

(Production method of resin composition)
A resin composition can be manufactured by the method of melt-kneading a fluororesin (A), a thermoplastic resin (B), and an additive as needed.
Examples of the apparatus used for melt kneading include known kneaders (such as a twin-screw extruder, a single-screw extruder, a kneader, and a mixer), and the compatibility between the fluororesin (A) and the thermoplastic resin (B) is improved. From this point, an extruder is preferable, and a twin screw extruder is particularly preferable.

The melt kneading temperature is set according to the type of the thermoplastic resin (B), 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 melt kneading, and the fluororesin (A) or the thermoplastic resin (B) is used as a resin composition. It becomes easy to disperse in the product as fine particles, and the average dispersed particle size of the fluororesin (A) or the thermoplastic resin (B) is easily reduced to 10 μm or less. If the melt-kneading temperature is less than 450 ° C., there is a tendency that deterioration of the resin composition due to heat can be prevented.
The residence time in the extruder is preferably from 10 seconds to 30 minutes.
The screw rotation speed of the extruder is preferably 50 rpm or more and 1500 rpm or less.

<Method for producing molded product>
The method for producing a molded article of the present invention is a method in which the above-described resin composition is melted and extruded from a die hole (capillary, slit, etc.) for molding.
Examples of the apparatus used for extrusion include an extruder provided with a die.

(Shear rate)
Shear rate at which the molten resin composition is extruded from the die is 10～350S ^-1, preferably 12~320s ^-1, 15~300s ^-1 are more preferred. If the shear rate is 10 s ⁻¹ or more, the discharge amount is not reduced too much, and the productivity of the molded product is improved. Moreover, the residence time in an extruder becomes short and the thermal deterioration of a resin composition is suppressed. If the shear rate is 350 s ⁻¹ or less, melt fracture is unlikely to occur on the surface of the molded product.

The shear rate is calculated using a known formula (for example, see JIS K 7199: 1999) corresponding to a die provided in an apparatus used for extrusion molding.
For example, when a capillary die is used, the shear rate is calculated using the following equation (1).

Where R _S is the shear rate (s ⁻¹ ), Q is the volume flow rate (mm ³ / s), and r is the capillary inner diameter (mm).

  When using a slit die, the shear rate is calculated using the following equation (2).

Where R _S is the shear rate (s ⁻¹ ), Q is the volume flow rate (mm ³ / s), B is the slit width (mm), and H is the slit gap (mm).

  The volume flow rate is calculated using the following formula (3).

However, Q is volume flow volume (mm < ³ > / s), A is piston cross-sectional area (mm < ² >), D is piston diameter (mm), _RP is piston speed (mm / min).

(Melt viscosity)
The melt viscosity when the molten resin composition is extruded from the die is preferably 300 to 50000 Pa · s, more preferably 350 to 45000 Pa · s, and further preferably 400 to 40000 Pa · s. When the melt viscosity is 300 Pa · s or more, the moldability of the resin composition is excellent. If the melt viscosity is 50000 Pa · s or less, melt fracture is unlikely to occur on the surface of the molded product.

  The melt viscosity is calculated using the following formula (4).

Where μ is the melt viscosity (Pa · s), τ is the shear stress (Pa), and _RS is the shear rate (s ⁻¹ ).

The shear stress is calculated using a known formula (for example, see JIS K 7199: 1999) corresponding to a die provided in an apparatus used for extrusion molding.
For example, when a capillary die is used, the shear stress is calculated using the following equation (5).

  Where τ is the shear stress (Pa), P is the resin pressure (Pa), r is the capillary inner diameter (mm), and L is the capillary length (mm).

  Further, when a slit die is used, the shear stress is calculated using the following equation (6).

  Where τ is the shear stress (Pa), P is the resin pressure (Pa), B is the slit width (mm), H is the slit gap (mm), and L is the slit length (mm). It is.

  The resin pressure is calculated using the following formula (7).

  However, P is a resin pressure (Pa), F is a measurement load (N), D is a piston diameter (mm).

(Other conditions)
Molding temperature is set according to the kind of thermoplastic resin (B), 280 degreeC or more and less than 450 degreeC are preferable, and 300-430 degreeC is more preferable. When the molding temperature is 280 ° C. or higher, the heat resistance is excellent. If the molding temperature is lower than 450 ° C., the thermoplastic resin (B) tends to be prevented from deteriorating due to heat.

In the method for producing a molded article of the present invention, the resin is dried at about 120 to 150 ° C. for the purpose of volatilizing the moisture absorbed in the resin by drying, as is generally done in resin molding. May be.
Moreover, when the thermoplastic resin (B) is a polyaryl ketone, it is preferable to heat-treat the resin composition in a temperature range of 180 ° C. or higher and lower than the melting point of the polyaryl ketone. By performing the heat treatment, molding stability is improved. The reason why the molding stability is improved is not clear, but it is thought that the moldability is stabilized when the polyaryl ketone is crystallized around 200 ° C. In the heat treatment, it is more preferable that the resin composition contains the fluororesin (A) as fine particles having an average dispersed particle diameter of 10 μm or less. After heat treatment, the resin composition is preferably melted and extruded from a die.

(Function and effect)
In the manufacturing method of the molded article of the present invention described above, since the shear rate when the molten resin composition is extruded from the die is 10 to 350 s ⁻¹ , the melt-moldable fluororesin and the thermoplastic resin Although a resin composition containing a resin is extruded to produce a molded product, melt fracture is unlikely to occur on the surface of the molded product.

<Molded product>
The molded article of the present invention is obtained by the method for producing a molded article of the present invention.
The molded product is not particularly limited as long as it is a molded product obtained by extrusion molding.
Examples of the form of the molded product include tubes, films, fibers, and the like.
Applications of molded products include applications that require mechanical properties (rigidity, strength, etc.) at high temperatures in addition to the characteristics specific to fluororesins, such as medical products, machine parts, automotive parts, electrical / electronic parts, etc. Is mentioned.

  The surface roughness (Ra) of the molded product is preferably 2.00 μm or less, more preferably 1.50 μm or less, and even more preferably 1.20 μm or less. When the surface roughness (Ra) of the molded product is 2.00 μm or less, the surface appearance of the molded product is preferable and the wear resistance is excellent.

(Function and effect)
Since the molded product of the present invention described above is obtained by the method of manufacturing a molded product of the present invention, a resin composition containing a melt-moldable fluororesin and a thermoplastic resin is extruded. The melt fracture on the surface is suppressed despite being obtained.

<Manufacturing method of electric wire>
The method for producing an electric wire of the present invention is a method in which the above-described resin composition is melted and extruded around a core wire from a die discharge port to form a coating layer around the core wire.
Examples of the apparatus used for the production of the electric wire include an extruder provided with an electric wire die cross head.

(Shear rate)
Shear rate at which the molten resin composition is extruded from the die is 10～350S ^-1, preferably 12~320s ^-1, 15~300s ^-1 are more preferred. If the shear rate is 10 s ⁻¹ or more, the discharge amount is not reduced too much, and the productivity of the electric wire is improved. Moreover, the residence time in an extruder becomes short and the thermal deterioration of a resin composition is suppressed. If the shear rate is 350 s ⁻¹ or less, melt fracture is unlikely to occur on the surface of the coating layer.

The shear rate is calculated using a known formula corresponding to a die provided in an apparatus used for manufacturing an electric wire.
For example, the shear rate is calculated using the following formula (8).

Where R _S is the shear rate (s ⁻¹ ), Q is the volume flow rate (cm ³ / s), _DD is the outer die inner diameter (mm), and _DN is the nipple die outer diameter (mm) It is.

  The volume flow rate is calculated using the following formula (9).

However, Q is the volumetric flow rate _{^{(cm 3 / s), D}} W is the core diameter (mm), _{D C} is the wire diameter (mm), _{R L} is the line speed (m / min).

(Other conditions)
Molding temperature is set according to the kind of thermoplastic resin (B), 280 degreeC or more and less than 450 degreeC are preferable, and 300-430 degreeC is more preferable. When the molding temperature is 280 ° C. or higher, the heat resistance of the molded product is excellent. If the molding temperature is less than 450 ° C, the resin composition tends to be prevented from being deteriorated by heat.

In the method for producing an electric wire of the present invention, the resin may be dried at about 120 to 150 ° C. for the purpose of volatilizing moisture absorbed in the resin by drying, as in the method for producing a molded product of the present invention. Good.
Moreover, when the thermoplastic resin (B) is a polyaryl ketone, it is preferable to heat-treat the resin composition in a temperature range of 180 ° C. or higher and lower than the melting point of the polyaryl ketone. By performing the heat treatment, the molding stability is improved and it becomes easy to form a coating layer of the electric wire. The reason why the molding stability is improved is not clear, but it is thought that the moldability is stabilized when the polyaryl ketone is crystallized around 200 ° C. In the heat treatment, it is more preferable that the resin composition contains the fluororesin (A) as fine particles having an average dispersed particle diameter of 10 μm or less. After the heat treatment, the resin composition is preferably melted and extruded around a core wire from a die to form a coating layer around the core wire.

(Function and effect)
In the manufacturing method of the electric wire of the present invention described above, since the shear rate when the molten resin composition is extruded from the die is 10 to 350 s ⁻¹ , a melt-moldable fluororesin and thermoplastic resin In spite of the fact that a coating layer is formed by extruding a resin composition containing the above around the core wire, melt fracture is unlikely to occur on the surface of the coating layer.

<Wire>
The electric wire of the present invention is obtained by the electric wire manufacturing method of the present invention.
The diameter of the electric wire is preferably 20 μm to 5 mm.
The thickness of the coating layer 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.
Applications for electric wires include applications that require mechanical properties (rigidity, strength, etc.) at high temperatures in addition to the characteristics specific to fluororesins, such as aircraft cables, high-voltage cables, communication cables, electric heater cables, etc. Is mentioned.

  The surface roughness (Ra) of the coating layer is preferably 2.00 μm or less, more preferably 1.50 μm or less, and even more preferably 1.20 μm or less. When the surface roughness (Ra) of the coating layer is 2.00 μm or less, the surface appearance of the coating layer is preferable and the wear resistance is excellent.

(Function and effect)
Since the electric wire of the present invention described above is obtained by the method for producing an electric wire of the present invention, a resin composition containing a melt-moldable fluororesin and a thermoplastic resin is extruded around the core wire. In spite of being obtained by forming a coating layer, the melt fracture on the surface of the coating layer is suppressed.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.
Examples 1, 3, 6, 8, 11, 13, and 14 are examples, and examples 2, 4, 5, 7, 9, 10, and 12 are comparative 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 to a (mol%), the number of main-chain functional groups to the number 1 × 10 ⁶ carbon atoms, fluorine resin (A) (I) (acid anhydride group) is, [a × ¹⁰ 6/100 ] Pieces.

(Melting point)
Using a differential scanning calorimeter (DSC device, manufactured by Seiko Instruments Inc.), the melting peak when the fluororesin (A) is heated at a rate of 10 ° C./min is recorded, and the temperature corresponding to the maximum value (° C.) Was 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 to be measured was frozen in liquid nitrogen and then cut, and the cut surface was observed with a scanning electron microscope (manufactured by Hitachi High-Technologies, 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).

(Melt fracture)
The smoothness of the surface of the molded product or the surface of the coating layer of the electric wire was confirmed visually. Specifically, a 30 cm or longer strand or electric wire was arbitrarily cut into 30 cm to obtain a sample, and the presence or absence of irregularities or irregularities on the surface of the sample was confirmed.

(Surface roughness)
About the sample, the surface roughness (Ra) was measured on condition of the following using the surface roughness measuring device (The Kosaka Laboratory Co., Ltd. make, Surfcorder SE-30H).
Cut-off value (λc): 0.8 mm,
Driving speed: 0.1 mm / s,
Sample length: 8 mm.

(Fluororesin (A))
NAH (anhydrous mixed acid, manufactured by Hitachi Chemical Co., Ltd.) as a monomer that forms the structural unit (a2), PPVE (CF ₂ = CFOCF ₂ CF ₂ CF ₃₎ , perfluoropropyl vinyl ether, Asahi Glass as a monomer that forms the structural unit (a3) Prepared).
A polymerization initiator solution in which (perfluorobutyryl) peroxide was dissolved in AK225cb at a concentration of 0.36% by mass 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 1,3-dichloro-1,1,2,2,3-pentafluoropropane (AK225cb, manufactured by Asahi Glass Co., Ltd.) (hereinafter referred to as AK225cb) and 30 kg of PPVE were previously deaerated. A 430 L polymerization tank equipped with a stirrer was charged. 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 group) in the fluorine-containing copolymer (A1-1) is 1 × 10 ⁶ carbon atoms in the main chain of the fluorine-containing 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.

(Other fluoropolymers)
PFA: TFE / perfluoro (alkyl vinyl ether) copolymer (Asahi Glass Co., Ltd., Fluon (registered trademark) PFA 73PT, melting point: 305 ° C., MFR: 13.6 g / 10 min).

(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).

(Example 1, Example 2)
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). And melt-kneaded at a screw rotational speed of 200 rpm and a melt-kneading temperature of 340 ° C. to obtain a resin composition (C-1). The average dispersed particle diameter of PAI in the resin composition (C-1) was 2.8 μm.

Capillograph (manufactured by Toyo Seiki Co., Ltd., capillary length L: 10 mm, capillary inner diameter r: 1.0 mm, piston diameter D: 9.55 mm), molding temperature: 340 ° C., piston speed R _p : 1, 2, 3, 5 7.5, 10, 20, 30, 50, 75, 100, 200, 300 mm / min. The resin composition was extruded to obtain a strand for each piston speed. Using the above formula, the shear rate and melt viscosity at each piston speed were determined.

When the presence or absence of melt fracture on the surface of the strand was confirmed, no melt fracture was observed in the range of the shear rate of 12.16 to 243.2 s ⁻¹ (Example 1). When the surface roughness (Ra) of the strand in the range of the shear rate of 12.16 to 243.2 s ⁻¹ was measured, the maximum was 1.00 μm when the shear rate was 243.2 s ⁻¹ . The melt viscosity in the range of shear rate: 12.16-243.2 s ^{−1 was in} the range of 6466-1048 Pa · s.

On the other hand, at a shear rate of 364.8 s ⁻¹ or more (melt viscosity: 699 Pa · s or less) (Example 2), melt fracture occurred on the surface of the strand. Shear rate: The surface roughness (Ra) of the strand at 364.8 s ⁻¹ was 14.48 μm.

(Example 3, Example 4)
A strand was obtained for each piston speed in the same manner as in Examples 1 and 2 except that the molding temperature was changed to 370 ° C. Using the above formula, the shear rate and melt viscosity at each piston speed were determined.

No melt fracture was observed in the shear rate range of 12.16 to 243.2 s ⁻¹ (Example 3). Shear rate: The surface roughness (Ra) of the strand at 243.2 s ⁻¹ was 1.06 μm. The melt viscosity in the range of shear rate: 12.16 to 243.2 s ^{−1 was in} the range of 5030 to 860 Pa · s.

On the other hand, at a shear rate of 364.8 s ⁻¹ or more (melt viscosity: 573 Pa · s or less) (Example 4), melt fracture occurred on the surface of the strand. Shear rate: The surface roughness (Ra) of the strand at 364.8 s ⁻¹ was 11.08 μm.

(Example 5)
A resin composition (C-2) was obtained in the same manner as in Examples 1 and 2, except that PFA was used instead of the fluororesin (A-1).
A strand was obtained for each piston speed in the same manner as in Examples 3 and 4 except that the resin composition (C-2) was used instead of the resin composition (C-1). Using the above formula, the shear rate and melt viscosity at each piston speed were determined.

Melt fracture occurred on the surface of the strand at all shear rates. Shear rate: The surface roughness (Ra) of the strand at 243.2 s ⁻¹ was 2.22 μm.

(Example 6, Example 7)
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). And melt-kneaded at a screw speed of 200 rpm and a cylinder temperature of 330 to 380 ° C. to obtain a resin composition (C-3). The average dispersed particle size of PEEK in the resin composition (C-3) was 2.0 μm.

  A strand is obtained for each piston speed in the same manner as in Examples 1 and 2, except that the resin composition (C-3) is used instead of the resin composition (C-1) and the molding temperature is changed to 380 ° C. It was. Using the above formula, the shear rate and melt viscosity at each piston speed were determined.

When the presence or absence of melt fracture on the strand surface was confirmed, no melt fracture was observed in the range of the shear rate of 12.16 to 243.2 s ⁻¹ (Example 6). When the surface roughness (Ra) of the strand in the range of shear rate: 12.16 to 243.2 s ⁻¹ was measured, the maximum was 0.32 μm when the shear rate was 243.2 s ⁻¹ . The melt viscosity in the range of the shear rate: 12.16 to 243.2 s ^{−1 was in} the range of 2639 to 443 Pa · s.

On the other hand, in the case of shear rate: 364.8 s ⁻¹ (Example 7), unevenness and irregularities are observed on the surface of the strand, and in the case of shear rate: 608.0 s ⁻¹ or more (melt viscosity: 288 Pa · s or less), the surface of the strand Melt fracture occurred. Shear rate: The surface roughness (Ra) of the strand at 364.8 s ⁻¹ was 8.57 μm.

(Example 8)
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 D _W : 1.8 mm, configuration: 37 / 0.26 mm (1 layer: 7 right-handed strands, 2 layers: 12 left-handed strands, 3 layers: right-handed strands) 18))) were prepared.

Outer die inner diameter D _D : 13.9 mm, nipple die outer diameter D _N : 5.9 mm, line speed R _L : 10 to 60 m / min, coating layer thickness: 0.5 mm, molding temperature : Under the condition of 340 ° C., the resin composition (C-1) was extruded around the core wire, and an electric wire with a covered electric wire diameter D _C : 2.8 mm was obtained for each line speed.

When the shear rate at each line speed was determined using the above-described formula, the shear rate was in the range of 10 to 60 s ⁻¹ . In this range, no melt fracture was observed on the surface of the coating layer of the electric wire. Shear rate: the surface roughness of the coating layer in the range of 10~60s ^-1 (Ra) was measured, shear rate: For ^{60s -1} is the maximum was 1.06 .mu.m.

(Example 9)
Using the wire-producing device, outer die inner diameter _D D: 6.8 mm, nipple die outside diameter _D N: 5.9 mm, line speed _R L: 10 to 60 m / min, the coating layer thickness: 0.25 mm, the molding temperature : Under the condition of 340 ° C., the resin composition (C-1) was extruded around the core wire, and an electric wire with a covered electric wire diameter D _C : 2.3 mm was obtained for each line speed.

When the shear rate at each line speed was determined using the above-described equation, the shear rate was in the range of 562 to 3370 s ⁻¹ . In this range, melt fracture occurred on the surface of the coating layer of the electric wire. Shear rate: The surface roughness (Ra) of the coating layer at 562 s ⁻¹ was 5.16 μm.

(Example 10)
An electric wire was obtained in the same manner as in Example 8 except that the resin composition (C-2) was used instead of the resin composition (C-1). Wire forming was performed.
At all shear rates, melt fracture occurred on the surface of the coating layer. Shear rate: The surface roughness (Ra) of the coating layer at 20 s ⁻¹ was 5.18 μm.

(Example 11)
Outer die inner diameter D _D : 13.9 mm, nipple die outer diameter D _N : 5.9 mm, line speed R _L : 10 to 60 m / min, coating layer thickness: 0.5 mm, molding temperature : Under the condition of 380 ° C., the resin composition (C-3) was extruded around the core wire, and an electric wire with a covered electric wire diameter D _C : 2.8 mm was obtained for each line speed.

When the shear rate at each line speed was determined using the above-described formula, the shear rate was in the range of 10 to 60 s ⁻¹ . In this range, no melt fracture was observed on the surface of the coating layer of the electric wire. Shear rate: The surface roughness (Ra) of the coating layer at 20 s ⁻¹ was 0.42 μm.

(Example 12)
Using the wire-producing device, outer die inner diameter _D D: 6.8 mm, nipple die outside diameter _D N: 5.9 mm, line speed _R L: 10 to 60 m / min, the coating layer thickness: 0.25 mm, the molding temperature : Under the condition of 380 ° C., the resin composition (C-3) was extruded around the core wire, and an electric wire with a covered electric wire diameter D _C : 2.3 mm was obtained for each line speed.

When the shear rate at each line speed was determined using the above-described equation, the shear rate was in the range of 562 to 3370 s ⁻¹ . In this range, melt fracture occurred on the surface of the coating layer of the electric wire. Shear rate: The surface roughness (Ra) of the coating layer at 562 s ⁻¹ was 2.70 μm.

(Example 13)
In a twin-screw extruder (screw diameter: 15 mm), the fluorinated copolymer (A1-1) and PEEK are made to have a fluorinated copolymer (A1-1) / PEEK = 20/80 (volume ratio). And melt-kneaded at a screw rotation speed of 200 rpm and a cylinder temperature of 330 to 380 ° C. to obtain a resin composition (C-4). The average dispersed particle size of the fluorinated copolymer (A1-1) in the resin composition (C-4) was 4.0 μm. The resin composition (C-4) was heat-treated at a furnace temperature of 200 ° C. for 2 hours using a hot air circulating dryer (Maruya Kanagawa Seisakusho Co., Ltd.) to obtain a resin composition (C-5).

Using the wire-producing device, outer die inner diameter _D D: 10.5 mm, nipple die outside diameter _D N: 5.9 mm, line speed _R L: 5 to 10 m / min, the coating layer thickness: 0.5 mm, molding temperature : Under the condition of 380 ° C., the resin composition (C-5) was extruded around the core wire to obtain an electric wire having a covered electric wire diameter D _{C of} 2.8 mm for each line speed.

When the shear rate at each line speed was determined using the above-described formula, the shear rate was in the range of 17 to 35 s ⁻¹ . In this range, no melt fracture was observed on the surface of the coating layer of the electric wire. When the surface roughness (Ra) of the coating layer in the range of shear rate: 17 to 35 s ⁻¹ was measured, the maximum value was 0.51 μm when the shear rate was 35 s ⁻¹ .

(Example 14)
About the resin composition (C-4), the outer die inner diameter D _D : 10.5 mm, the nipple die outer diameter D _N : 5.9 mm, the line speed R _L : 5 to 10 m / min, the coating layer Under the conditions of thickness: 0.5 mm and molding temperature: 380 ° C., the resin composition (C-4) was extruded around the core wire to obtain an electric wire. However, although melt fracture was not observed on the surface of the coating layer of the electric wire, there was a problem that the discharge was not stable. Therefore, in the wire forming stably obtained, the shear rate at each line speed was determined using the above-described formula, and the shear rate was in the range of 17 to 35 s ⁻¹ . In this range, no melt fracture was observed on the surface of the coating layer of the electric wire. When the surface roughness (Ra) of the coating layer in the range of shear rate: 17 to 35 s ⁻¹ was measured, the maximum ^value was 1.08 μm when the shear rate was 35 s ⁻¹ .

  The molded article and the electric wire obtained by the production method of the present invention are useful for applications that require mechanical properties (rigidity, strength, etc.) at high temperatures in addition to the properties specific to fluororesins.

Claims (12)

A fluororesin (A) that is melt-moldable 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. ,
And a thermoplastic resin (B) having a melting point of 280 to 420 ° C. (excluding the fluororesin (A)), and a method for producing a molded article obtained by melting and extruding from a die. And
A method for producing a molded product, wherein a shear rate when the molten resin composition is extruded from the die is 10 to 350 s- ¹ . The fluororesin (A) has a carbonyl group-containing group,
The carbonyl group-containing group is at least one selected from the group consisting of a 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. The manufacturing method of the molded article of Claim 1. The method for producing a molded product 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 of the main chain of the fluororesin (A).   The method for producing a molded article according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is at least one selected from the group consisting of polyamideimide, polyaryl ketone and thermoplastic polyimide. . The thermoplastic resin (B) is a polyaryl ketone,
The resin composition containing the fluororesin (A) as fine particles having an average dispersed particle diameter of 10 μm or less in the resin composition is heat-treated at a temperature range of 180 ° C. or higher and lower than the melting point of the polyaryl ketone, and then the resin composition The method for producing a molded product according to claim 4, wherein the product is melted and extruded from a die.   The molded product obtained by the manufacturing method of the molded product as described in any one of Claims 1-5. A fluororesin (A) that is melt-moldable 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 resin composition containing a thermoplastic resin (B) having a melting point of 280 to 420 ° C. (excluding the fluororesin (A)) is melted and extruded around a core wire from a die. A method of manufacturing an electric wire for forming a coating layer,
The method for producing an electric wire, wherein a shear rate when the molten resin composition is extruded from the die is 10 to 350 s ⁻¹ . The fluororesin (A) has a carbonyl group-containing group,
The carbonyl group-containing group is at least one selected from the group consisting of a 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. The manufacturing method of the electric wire of Claim 7. The method for producing an electric wire according to claim 7 or 8, 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 method for producing an electric wire according to any one of claims 7 to 9, wherein the thermoplastic resin (B) is at least one selected from the group consisting of polyamideimide, polyaryl ketone, and thermoplastic polyimide. The thermoplastic resin (B) is a polyaryl ketone,
The resin composition containing the fluororesin (A) as fine particles having an average dispersed particle diameter of 10 μm or less in the resin composition is heat-treated at a temperature range of 180 ° C. or higher and lower than the melting point of the polyaryl ketone, and then the resin composition The manufacturing method of the electric wire according to claim 10, wherein an object is melted and extruded around a core wire from a die to form a coating layer around the core wire.   The electric wire obtained with the manufacturing method of the electric wire as described in any one of Claims 7-11.