JP6135541B2 - Method for producing fluororesin composition, method for producing molded product, and method for producing electric wire - Google Patents

Description

  The present invention relates to a method for producing a fluororesin composition, and a molded article and an electric wire using the fluororesin composition obtained by the production method.

Fluoropolymer is excellent in heat resistance, flame resistance, chemical resistance, weather resistance, non-adhesiveness, low friction, low dielectric properties, wire coating materials, chemical plant corrosion resistant piping materials, agricultural greenhouse materials, kitchen appliances It is used in a wide range of fields such as release coating materials.
In addition, melt molding of tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (hereinafter also referred to as “PFA”), ethylene / tetrafluoroethylene copolymer (hereinafter also referred to as “ETFE”) or the like is possible. A compounding technique by melt-kneading a fluororesin and another thermoplastic resin has attracted attention. For example, polymer blends of fluoropolymers and engineering plastics give the engineering plastics physical properties unique to fluororesins such as chemical resistance, toughness, and slidability, or impart high strength and rigidity peculiar to engineering plastics to fluoropolymers Development of polymer alloys for the purpose has been actively conducted.
However, since the fluororesin has a low surface energy and a small intermolecular force, it has low affinity with most other thermoplastic resins. Therefore, a polymer alloy of a fluororesin and another thermoplastic resin has a problem that physical properties peculiar to fluororesins and physical properties peculiar to other thermoplastic resins are not sufficiently exhibited.

Various studies have been made to solve the above problems.
For example, Patent Document 1 proposes melt blending a fluororesin and polyetherketoneketone at a specific ratio for the purpose of improving toughness at room temperature, heat distortion temperature and / or permeability.
In Patent Document 2, for the purpose of improving the mechanical strength and elongation of a molded product, and uniformly dispersing a polymer having a high fluorine content and a non-fluorine polymer, a carboxylic acid group or a derivative thereof, a sulfonic acid group or It has been proposed to use a fluorine-containing compound having a derivative as a functional group as a compatibilizing agent.
Patent Document 3 includes a hydrogen atom bonded to a carbon atom of the main chain for the purpose of increasing the compatibility between a fluorine-containing polymer and a non-fluorine polymer and combining the properties of each polymer, and grafting. Can be polymerized by reactive blending of non-fluorinated polymers such as engineering plastics and fluorine-containing resins that can be grafted onto the fluorine-containing resins and graftable compounds having functional groups that impart adhesiveness. Has been proposed.

However, the effect of improving mechanical properties such as toughness and mechanical strength by the methods of Patent Documents 1 to 3 is still not sufficient.
For example, in the method of Patent Document 1, since the affinity between the fluororesin and the polyaryl ketone is insufficient, the excellent physical properties are not sufficiently exhibited, and the effect of improving the mechanical properties is not sufficient. Further, the obtained composition has a problem in moldability, for example, when the melt molding such as extrusion molding is performed, the resin is partially detached and the surface of the molded product becomes rough.
In the method of Patent Document 2, a low molecular weight compatibilizing agent having low heat resistance and chemical resistance is used, so that the effect of improving mechanical properties, heat resistance, chemical resistance and the like is not sufficient.
In the method of Patent Document 3, since the thermal stability of the fluororesin that can be grafted is low, and the reactivity and affinity between the fluororesin and the non-fluorine polymer are low, the effect of improving mechanical properties is improved. Not enough. There is also a problem in formability.

Japanese Patent Laid-Open No. 11-158340 JP-A-11-209548 JP-A-9-118802

  An object of the present invention is to provide a method for producing a fluororesin composition that exhibits excellent mechanical properties when melt-molded, a molded product excellent in mechanical properties, and an electric wire having a coating layer excellent in mechanical properties. To do.

The present invention has the following aspects.
[1] Melting melt-moldable fluororesin (A) having a melting point of 260 ° C. or higher and a thermoplastic resin (B) not containing fluorine atoms and having a water absorption of 0.1% or higher Kneading to obtain a fluororesin composition,
A method for producing a fluororesin composition, wherein the thermoplastic resin (B) before melt-kneading has a water content of 1000 ppm by mass or more.
[2] The volume ratio ((A) :( B)) of the fluororesin (A) and the thermoplastic resin (B) is 0.1: 99.9 to 50:50, A method for producing a fluororesin composition.
[3] The content of the carbonyl group in the fluororesin (A) is 10 to 60000 with respect to 1 × 10 ⁶ main chain carbon atoms of the fluororesin (A). [1] or [2] The manufacturing method of the fluororesin composition.
[4] The thermoplastic resin (B) is at least one selected from the group consisting of polysulfone, polyethersulfone, polyaryl ketone, polyarylate, polyamideimide, and polyetherimide. [3] A method for producing a fluororesin composition.
[5] The method for producing a fluororesin composition according to [1] to [4], wherein the thermoplastic resin (B) is polyetheretherketone.
[6] Carbonization in which the fluororesin (A) has a structural unit (a) based on one or both of tetrafluoroethylene and chlorotrifluoroethylene, and one or both of a carboxy group and an acid anhydride group A structural unit (b) based on a hydrogen monomer and a structural unit (c) based on a fluorine monomer (excluding tetrafluoroethylene and chlorotrifluoroethylene);
The structural unit (a) is 50 to 99.89 mol% with respect to the total molar amount of the structural unit (a), the structural unit (b), and the structural unit (c), and the structural unit (b ) Is 0.01 to 5 mol%, and the structural unit (c) is 0.1 to 49.99 mol%, [1] to [5].
[7] A method for producing a molded product , comprising producing a fluororesin composition by the method for producing a fluororesin composition according to [1] to [6] and melt-molding the obtained fluororesin composition.
[8] The method for producing a molded product according to [7], wherein the molded product is a sliding member.
[9] [1] to produce a fluororesin composition by the method for producing a fluororesin composition according to any one of [6], by melting the resulting fluororesin composition, extruded around the core An electric wire manufacturing method for forming a coating layer covering the surface of the core wire.

The fluororesin composition obtained by the method for producing a fluororesin composition of the present invention exhibits excellent mechanical properties when melt-molded.
The molded product of the present invention is excellent in mechanical properties.
The coating layer of the electric wire of the present invention is excellent in mechanical properties.

In the present specification, the water absorption rate of the thermoplastic resin (B) is determined by a test based on Method A of JIS K7209: 2000 (Plastic—How to determine water absorption rate). Note that JIS K7209: 2000 was created by translating ISO 62: 1999 without changing the technical contents and the format of the standard form.
The moisture content of the thermoplastic resin (B) is determined by an infrared moisture meter. Detailed measurement conditions are as shown in the Examples.

The volume ratio ((A) :( B)) between the component (A) and the component (B) is obtained by the following procedure.
The volume (cm ³ ) is calculated by dividing the mass w (g) of each of the components (A) and (B) to be melt-kneaded (put into the kneader) by the specific gravity d (g / cm ³ ). Then, the ratio thereof is calculated from the volume (cm ³ ) of each of the component (A) and the component (B).
Specific gravity is a value at 23 ° C. The specific gravity of each of the component (A) and the component (B) can be measured by an underwater substitution (suspension) method.

The “structural unit” in the present specification means a unit based on the 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 unsaturated bond, that is, a polymerization-reactive carbon-carbon double bond. “Fluorine monomer” means a monomer having a fluorine atom in the molecule, and “non-fluorine monomer” means a monomer having no fluorine atom in the molecule.

≪Method for producing fluororesin composition≫
The method for producing the fluororesin composition of the present invention comprises a meltable fluororesin (A) (hereinafter also referred to as “component (A)”) having a melting point of 260 ° C. or higher and a fluorine atom. A step of obtaining a fluororesin composition by melting and kneading a thermoplastic resin (B) (hereinafter also referred to as “component (B)”) having a water absorption rate of 0.1 or more without containing (hereinafter referred to as “melt kneading”). Process "), and
The water content of the component (B) before melt kneading is 1000 ppm by mass or more.

<(A) component>
(A) Melting | fusing point of a component is 260 degreeC or more, 260-330 degreeC is preferable, 260-320 degreeC is more preferable, 280-310 degreeC is especially preferable.
When the melting point of the component (A) is not less than the lower limit of the above range, excellent mechanical properties are exhibited when the resulting fluororesin composition is melt-molded. For example, a molded product obtained by melt-molding the fluororesin composition and a coating layer formed by melting the fluororesin composition and extruding it around a core wire have excellent mechanical properties. The fluororesin composition obtained as it is below the upper limit of the above range is excellent in moldability.
(A) Melting | fusing point of a component can be adjusted with the kind and content rate of a structural unit which comprise (A) component, molecular weight, etc. For example, the melting point tends to increase as the proportion of the structural unit (a) described later increases.

The component (A) can be melt-molded. “Melting is possible” means exhibiting melt fluidity.
As an index indicating the melt fluidity, there is a melt flow rate (hereinafter referred to as “MFR”).
The MFR of the component (A) is preferably 2 g / 10 minutes or more, more preferably 3 g / 10 minutes or more, further preferably 6 g / 10 minutes or more, and particularly preferably 10 g / 10 minutes or more. When the MFR is 2 g / 10 min or more, melt molding can be easily performed, and the moldability of the obtained fluororesin composition is improved.
The MFR of the component (A) is preferably 300 g / 10 min or less, more preferably 100 g / 10 min or less, still more preferably 60 g / 10 min or less, and 50 g / 10 min or less in terms of excellent mechanical strength. Particularly preferred.

In this specification, the MFR of the component (A) is a value measured at 372 ° C. under a load of 49 N.
The MFR is a measure of the molecular weight. When the MFR is large, the molecular weight is low, and when the MFR is small, the molecular weight is large. The molecular weight of component (A), and hence MFR, can be adjusted by the production conditions of component (A). For example, if the polymerization time is shortened during polymerization of the monomer, the MFR tends to increase.

The component (A) has a carbonyl group. By having a carbonyl group, the compatibility between the component (A) and the component (B) is improved.
A carbonyl group may be contained in the main chain terminal group of (A) component, may be contained in a side group, and may be contained in both of them.
The component (A) preferably has a group consisting of a combination of a carbonyl group and another group or atom (hereinafter also referred to as a carbonyl group-containing group).
The carbonyl group-containing group is not particularly limited as long as it contains a carbonyl group (—C (═O) —) in the structure. For example, a group containing a carbonyl group between carbon atoms of a hydrocarbon group, Examples thereof include a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, and an acid anhydride residue.
As said hydrocarbon group, a C2-C10 alkylene group etc. are mentioned, for example. In addition, carbon number of this alkylene group is carbon number in the state which does not contain a carbonyl group. The alkylene group may be linear or branched.
The haloformyl group is represented by —C (═O) —X (where X is a halogen atom). As a halogen atom in a haloformyl group, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable. That is, the haloformyl group is preferably a fluoroformyl group (also referred to as “carbonyl fluoride group”).
The alkoxy group in the alkoxycarbonyl group may be linear or branched and is preferably an alkoxy group having 1 to 8 carbon atoms, particularly preferably a methoxy group or an ethoxy group.
(A) The carbonyl group containing group contained in a component may be 1 type, and 2 or more types may be sufficient as it.

The content of the carbonyl group in the component (A) is preferably 10 to 60000, more preferably 100 to 50000, and particularly preferably 300 to 5000 with respect to 1 × 10 ⁶ main chain carbon atoms of the component (A). preferable. If the content of the carbonyl group is not less than the lower limit of the above range, the affinity with the component (B) is excellent, and if it is not more than the upper limit, the melt processability and thermal stability are excellent.
The main chain is a main carbon chain of the chain compound, and generally refers to a portion corresponding to a trunk having the maximum number of carbon atoms. The number of main chain carbon atoms of the component (A) is preferably 2000 to 50000, more preferably 3000 to 30000, and further preferably 5000 to 25000.
The content of the carbonyl group in the component (A) can be measured by methods such as infrared absorption spectrum analysis and nuclear magnetic resonance (NMR) analysis. For example, as described in Japanese Patent Application Laid-Open No. 2007-314720, using a method such as infrared absorption spectrum analysis, the ratio (mol) of structural units having a carbonyl group to the total of all structural units constituting the component (A) %) And the content of the carbonyl group can be calculated from the ratio.

In addition to the carbonyl group, the component (A) may have at least one functional group selected from the group consisting of an epoxy group, an amide group, a hydroxyl group, and an amino group.
The component (A) may have these functional groups at side groups, at the main chain ends, or at both of them.

As the component (A), the structural unit (a) based on one or both of tetrafluoroethylene (hereinafter also referred to as “TFE”) and chlorotrifluoroethylene (hereinafter also referred to as “CTFE”); Containing a structural unit (b) based on a hydrocarbon monomer having one or both of a carboxy group and an acid anhydride residue, and a structural unit (c) based on a fluoromonomer (excluding TFE and CTFE) (Hereinafter also referred to as “component (A1)”) is preferable.
By using the component (A1) as the component (A), it is excellent in molding processability and thermal stability.

Examples of the hydrocarbon monomer having either one or both of a carboxy group and an acid anhydride residue for obtaining the structural unit (b) (hereinafter also referred to as “AM monomer”) include itaconic acid, citraconic acid, 5- Dicarboxylic acids such as norbornene-2,3-dicarboxylic acid and maleic acid, itaconic anhydride (hereinafter also referred to as “IAH”), citraconic anhydride (hereinafter also referred to as “CAH”), 5-norbornene-2, Examples thereof include 3-carboxylic acid anhydrides (hereinafter also referred to as “NAH”) and acid anhydrides of dicarboxylic acids such as maleic anhydride. Among these, IAH, CAH, and NAH are preferable.
AM monomer may be used individually by 1 type, and may use 2 or more types together.

As the fluorine monomer (excluding TFE and CTFE) for obtaining the structural unit (c), vinyl fluoride, vinylidene fluoride (hereinafter also referred to as “VdF”), trifluoroethylene, hexafluoropropylene (hereinafter referred to as “VFE”). , Also referred to as “HFP”), CF ₂ = CFOR ¹ (wherein R ¹ is a C 1-10 perfluoroalkyl group which may contain an oxygen atom), CF ₂ = CFOR ² SO ₂ X ¹ (R ² is a C 1-10 perfluoroalkylene group which may contain an oxygen atom, X ¹ is a halogen atom or a hydroxyl group), CF ₂ = CFOR ³ CO ₂ X ² (where, R ³ is a C 1-10 perfluoroalkylene group which may contain an oxygen atom, and X ² is a hydrogen atom or a C 1-3 alkyl group. 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, 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. .
These monomers may be used individually by 1 type, and may use 2 or more types together.

The fluorine monomer for obtaining the structural unit (c) is preferably at least one selected from the group consisting of VdF, HFP, CF ₂ = CFOR ¹ , and CH ₂ = CX ³ (CF ₂ ) _q X ⁴ , CF ₂ = CFOR ¹ and CH ₂ = CX ³ (CF ₂ ) at least one selected from the group consisting of _q X ⁴ is more preferable.
CF ₂ = CFO ¹ includes 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, and the like. Among them, CF ₂ = CFOCF ₂ CF ₂ CF ₃ is preferable.
CH ₂ = The ^{_{CX 3 (CF 2) q X}} 4, CH 2 = CH (CF 2) 2 F, CH 2 = CH (CF 2) 3F, CH 2 = CH (CF 2) 4 F, CH 2 = Examples thereof include CF (CF ₂ ) ₃ H, CH ₂ ═CF (CF ₂ ) ₄ H, and among them, CH ₂ ═CH (CF ₂ ) ₄ F or CH ₂ ═CH (CF ₂ ) ₂ F is preferable.

(A1) As a content rate of structural unit (a)-(c) in a component, with respect to the total molar amount of structural unit (a), structural unit (b), and structural unit (c), structural unit ( It is preferable that a) is 50 to 99.89 mol%, the structural unit (b) is 0.01 to 5 mol%, and the structural unit (c) is 0.1 to 49.99 mol%. More preferably, (a) is 50 to 99.4 mol%, the structural unit (b) is 0.5 to 49.9 mol%, and the structural unit (c) is 0.1 to 3 mol%, It is particularly preferable that the structural unit (a) is 50 to 98.9 mol%, the structural unit (b) is 1 to 49.9 mol%, and the structural unit (c) is 0.1 to 2 mol%.
When the content ratio of each structural unit is within this range, excellent mechanical strength is exhibited when the resulting fluororesin composition is melt-molded. It also has excellent heat resistance and chemical resistance.

The component (A1) may contain a structural unit (d) based on a non-fluorine monomer (excluding an AM monomer) in addition to the structural units (a), (b), and (c) described above. .
Non-fluorine monomers for obtaining the structural unit (d) include olefins having 2 to 3 carbon atoms such as ethylene (hereinafter also referred to as “E”), propylene (hereinafter also referred to as “P”), and vinyl acetate. (Hereinafter also referred to as “VOA”) and the like. These monomers may be used individually by 1 type, and may use 2 or more types together.
As the non-fluorine monomer for obtaining the structural unit (d), E, P and VOA are preferable, and E is particularly preferable.
When the component (A1) contains the structural unit (d), “the structural unit (a) + the structural unit (b) + the structural unit (c)” with respect to the total molar amount of all the structural units constituting the component (A1). The proportion of the total molar amount is preferably 40 mol% or more, more preferably 45 mol% or more, and most preferably 50 mol% or more.

Preferred examples of the component (A1) include TFE / IAH / CF ₂ ═CFOCF ₂ CF ₂ CF ₃ copolymer, TFE / CAH / CF ₂ ═CFOCF ₂ CF ₂ CF ₃ copolymer, and TFE / IAH / HFP copolymer. Polymer, TFE / CAH / HFP copolymer, TFE / IAH / VdF copolymer, TFE / CAH / VdF copolymer, TFE / IAH / CH ₂ ═CH (CF ₂ ) ₄ F / E copolymer, TFE / CAH / CH ₂ ═CH (CF ₂ ) ₄ F / E copolymer, TFE / IAH / CH ₂ ═CH (CF ₂ ) ₂ F / E copolymer, TFE / CAH / CH ₂ ═CH (CF ₂ ) ₂ F / E copolymer, CTFE / IAH / CH ₂ ═CH (CF ₂ ) ₄ F / E copolymer, CTFE / CAH / CH ₂ ═CH (CF ₂ ) ₄ F / E copolymer, CTFE / IA _{/ CH 2 = CH (CF 2} ) 2 F / E _{copolymer, CTFE / CAH / CH 2 =} CH (CF 2) 2 F / E copolymer.

The component (A1) may have a functional group such as an alkoxycarbonyl group, an alkoxycarbonyloxy group, a hydroxyl group, a carboxy group, or a carbonyl fluoride group as a main chain terminal group.
When the main chain terminal group is present, in melt-kneading, compatibility with the component (B) is increased, and improvement in moldability such as increase in mechanical strength and critical shear rate can be expected.
The main chain terminal group can be introduced by using a predetermined radical polymerization initiator or chain transfer agent used in the production of the fluororesin.
Examples of the radical polymerization initiator include tertiary butyl peroxypivalate and perfluoroptyroyl peroxide.
Examples of the chain transfer agent include chain transfer agents having a functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxy group, and a carbonyl fluoride group. Specific examples include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, and propylene glycol.

The component (A) may be used as long as the desired fluororesin is commercially available, and may be produced from various raw material compounds by an appropriate method such as polymerization.
As a manufacturing method of the fluororesin which has a carbonyl group containing group, the following (1)-(4) etc. are mentioned, for example. (A) As a manufacturing method of a component, the method of (1) is preferable.
As a manufacturing method of a fluororesin, the following (1)-(4) etc. are mentioned, for example.
(1) A method of using a monomer (for example, AM monomer) having a carbonyl group-containing group when producing a fluororesin by a polymerization reaction.
(2) A method for producing a fluororesin by a polymerization reaction using a radical polymerization initiator or a chain transfer agent having a carbonyl group-containing group.
(3) A fluorocarbon resin having a thermal decomposition site that generates a carbonyl group-containing group by thermal decomposition is heated, and the fluororesin is partially thermally decomposed to generate a carbonyl group-containing group, thereby producing a carbonyl group-containing group. A method for obtaining a fluororesin having
(4) A method of introducing a carbonyl group-containing group into the fluororesin by graft polymerization of a monomer having a carbonyl group-containing group onto a fluororesin having no carbonyl group-containing group.
(A) As a manufacturing method of a component, the method of (1) is preferable.

When the component (A) is produced by polymerization, the polymerization method is not particularly limited, and for example, a method using a radical polymerization initiator is used.
As a radical polymerization initiator, the temperature at which the half-life is 10 hours is preferably 0 to 100 ° C, and more preferably 20 to 90 ° C. Specific examples include azo compounds such as azobisisobutyronitrile, non-fluorine diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide and lauroyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate, tert - butyl peroxypivalate, tert- butylperoxy isobutyrate, tert- butyl peroxy ester peroxy acetate, _{etc., 2} (where _{(Z (CF 2) r COO} ), Z represents a hydrogen atom, a fluorine atom or a chlorine atom , R is an integer of 1 to 10.) Fluorine-containing diacyl peroxide such as a compound represented by formula (I), inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate.

Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, aqueous media, and appropriate organic solvents as required. Suspension polymerization, and emulsion polymerization using an aqueous medium and an emulsifier. Preferably, it is solution polymerization.
The polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, 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 order to introduce a carbonyl group into the component (A), when an AM monomer is used for the polymerization, the concentration of the AM monomer during the polymerization is preferably 0.01 to 5 mol% with respect to the total of all monomers, It is more preferable to set it as 0.1-3 mol%, and it is especially preferable to set it as 0.1-1 mol%. When the concentration of the AM monomer is within the above range, the polymerization rate is good, and the obtained component (A) is rich in reactivity with the component (B). If the concentration of the AM monomer is too high, the polymerization rate tends to decrease.
During the polymerization, as the AM monomer is consumed in the polymerization, it is preferable to supply the consumed amount into the polymerization tank continuously or intermittently to maintain the AM monomer concentration within the above range.

During the polymerization, a chain transfer agent can be used to control the MFR.
Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Hydrocarbons such as pentane, hexane, and cyclohexane are listed.
When a chain transfer agent having a functional group such as an ester group, carbonate group, hydroxyl group, carboxy group, or carbonyl fluoride group is used as the chain transfer agent, the functional group is preferably introduced into the component (A). Such chain transfer agents include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, and propylene glycol.

<Thermoplastic resin (B)>
The component (B) is a thermoplastic resin that does not contain a fluorine atom and has a water absorption rate of 0.1% or more.
The water absorption rate of the component (B) is preferably from 0.1% to less than 1.0%, more preferably from 0.1% to less than 0.5%, and even more preferably from 0.1% to less than 0.3%.
When the water absorption of the component (B) is 0.1% or more, excellent mechanical properties are exhibited when the obtained fluororesin composition is melt-molded. Moreover, the said fluororesin composition is excellent also in a moldability. When the water absorption of the component (B) is less than 1.0%, the moldability is excellent.

(B) As for melting | fusing point of component, 240 degreeC or more is preferable, 260-420 degreeC is more preferable, 280-400 degreeC is especially preferable.
When the melting point of the component (B) is equal to or higher than the lower limit of the above range, excellent mechanical properties are exhibited when the resulting fluororesin composition is melt-molded, and it is obtained when the melting point of the component is not higher than the upper limit of the above range. The fluororesin composition is excellent in moldability.

The MFR of the component (B) is preferably 1 to 300 g / 10 minutes, more preferably 3 to 100 g / 10 minutes, and particularly preferably 5 to 50 g / 10 minutes.
When the MFR of the component (B) is not less than the lower limit of the above range, the processability of the resulting fluororesin composition is excellent, and if it is not more than the upper limit of the above range, the mechanical properties of the obtained fluororesin composition Excellent.
In this specification, the MFR of the component (B) is a value measured under a load of 49 N at 372 ° C., like the MFR of the component (A).

Specific examples of the component (B) include polysulfone, polyethersulfone, polyaryl ketone, polyarylate, polyamideimide, polyetherimide, thermoplastic polyimide, and the like. Specific examples of the polyaryl ketone include polyether ketone, polyether ether ketone, polyether ketone ketone and the like. The water absorption of these thermoplastic resins is 0.1% or more and less than 1.0%. These may be used alone or in combination of two or more.
As the component (B), polyaryl ketones, polyamide imides, polyether imides, and thermoplastic polyimides are preferable in terms of mechanical strength and heat resistance, and polyether ether ketones are particularly preferable in terms of excellent mechanical strength.
As the component (B), if a desired compound is commercially available, it may be used, or may be produced from various raw material compounds by known methods.

<Other ingredients>
You may make a fluororesin composition contain other components other than (A) component and (B) component in the range which does not impair the effect of this invention as needed. Examples of other components include additives such as fillers, plasticizers, flame retardants, and compatibilizers.

Examples of the filler include a polymer filler and an inorganic filler.
As the polymer filler, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone, phenoxy resin, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, polyamide 6, polyamide 66, Polyamide 11, polyamide 12, polyamide 610, polyphenylene oxide, polyphenylene sulfide, polytetrafluoroethylene, acrylonitrile / butadiene / styrene copolymer (ABS), polymethyl methacrylate (PMMA), polypropylene, polyethylene, polybutadiene, butadiene-styrene copolymer Polymer, ethylene-propylene copolymer, ethylene-propylene-diene rubber (EPDM), styrene Butadiene block copolymer, butadiene - acrylonitrile copolymer, acrylic rubber, styrene - maleic anhydride copolymer, styrene - phenyl maleimide copolymer and the like.
Examples of the inorganic filler include CaCO ₃ , SiO ₂ , TiO ₂ , BaSO ₄ , ZnO, Al (OH) ₃ , Mg (OH) ₂ , talc, mica, carbon black, and carbon nanotube.
Examples of the plasticizer and flame retardant include phthalic acid ester, adipic acid ester, and phosphoric acid ester.
These additives may be used alone or in combination of two or more.
When the additive is contained in the fluororesin composition, the content of the additive is preferably 1 to 30% by volume with respect to the total amount of the component (A) and the component (B).
As a method for blending the additive, a method of kneading together with the component (A) and the component (B) in the melt-kneading step, the one previously kneaded with either the component (A) or the component (B) Examples thereof include a method of kneading the component (A) or the component (B).

<Melting and kneading process>
In the melt-kneading step, the water content of component (B) is measured, and the water content of 1000 ppm by mass or more is melt-kneaded with component (A).
(B) As for the moisture content of a component, 1500-20000 mass ppm is preferable, 2000-15000 mass ppm is more preferable, 3000-10000 mass ppm is especially preferable.
When the water content of the component (B) before melt kneading is 1000 ppm by mass or more, the compatibility between the component (A) and the component (B) during melt kneading is excellent, and the resulting fluororesin composition is melt molded. Excellent mechanical properties are manifested. For example, a molded product obtained by melt-molding the fluororesin composition or a coating layer formed by melting the fluororesin composition and extruding it around a core wire has the toughness (tensile elongation etc.) of the component (A) and (B) The mechanical properties (tensile strength, etc.) of the components are sufficiently combined and excellent in mechanical properties. Further, the physical properties of the component (A) other than toughness and the physical properties of the component (B) other than mechanical strength are sufficiently expressed. Moreover, this fluororesin composition is also excellent in moldability. On the other hand, when the water content is less than 1000 ppm by mass, the compatibility between the component (A) and the component (B) is not improved during melt kneading, and the mechanical strength is not improved.
From the viewpoint of compatibility, the upper limit of the water content is not particularly limited. However, if it exceeds 20000 ppm by mass, excessive water content may occur during melt-kneading, and the thermal decomposition of component (B) may occur preferentially.

Specifically, the water content of the component (B) before melt kneading is the water content at the time when it is put into a kneader used for melt kneading.
The water content of the component (B) before melt kneading is measured, and if it is a desired water content, it can be directly used for melt kneading.
When the moisture content of the component (B) is less than the desired moisture content, the moisture content is increased and used for melt kneading when the desired moisture content is reached. As a method for increasing the moisture content, (B) a method for maintaining the component in a high humidity environment, (A) and / or (B) a method of injecting a small amount of moisture before kneading, during melt kneading For example, a method of adding a small amount of water from the sub-feeder.
When the water content of the component (B) is higher than the desired water content, the water content is reduced and subjected to melt-kneading when the desired water content is reached. Examples of the method for reducing the water content include a method of keeping the component (B) in a low humidity environment, a method of drying with hot air in an arbitrary time, and the like.

The melt-kneading step can be performed by supplying the component (A) and the component (B) to a kneader at an arbitrary volume ratio and kneading at a predetermined kneading temperature.
The volume ratio ((A) :( B)) between the component (A) and the component (B) is preferably 0.1: 99.9-50: 50, and 0.1: 99.9-40 : 60 is more preferable, 0.1: 99.9 to 30:70 is more preferable, 0.1: 99.9 to 20:80 is particularly preferable, and 0.1: 99.9 to 10:90 is most preferable. .
(A): If (B) is in the above range, the compatibility between the component (A) and the component (B) during melt-kneading is excellent, and the resulting fluororesin composition is excellent in mechanical properties. Moreover, the moldability is also good, and appearance defects are less likely to occur when the fluororesin composition is melt-molded. For example, a molded product obtained by melt-molding the fluororesin composition or a coating layer formed by melting the fluororesin composition and extruding it around a core wire has high surface smoothness or reduced weld lines. It will be excellent. On the other hand, when (A) :( B) is out of the above range, the affinity between the (A) component and the (B) component is lowered, and the effect of improving the mechanical strength and moldability may be insufficient. . In particular, when the proportion of component (A) is greater than the upper limit of the above range, when the resulting fluororesin composition is melt-molded, component (A) bleeds out from component (B) and aggregates on the resin surface. There is a risk of causing molding defects and appearance defects.

As a method for supplying the component (A) and the component (B) to the kneader, the method of previously mixing the component (A) and the component (B) and supplying the mixture to the kneader, the component (A) and the component (B) ) And the like.
As the kneader, an apparatus usually used for melt kneading can be used, and examples thereof include a lab plast mill kneader (manufactured by Toyo Seiki Co., Ltd.). Kneading can be performed, for example, under the conditions of a screw speed of 20 to 100 rpm and a kneading time of 5 to 10 minutes.

The kneading temperature is usually a temperature equal to or higher than the higher melting point of the melting point of the component (A) and the melting point of the component (B), and typically the melting point of the component (A) and the melting point of the component (B). Of these, the melting point is higher than the higher melting point, and is lower than the lower thermal decomposition temperature of the thermal decomposition temperature of the component (A) and the thermal decomposition temperature of the component (B).
The kneading temperature is preferably 280 to 420 ° C, more preferably 300 to 400 ° C, and particularly preferably 320 to 380 ° C. When the kneading temperature is within the above range, the compatibility between the component (A) and the component (B) at the time of melt kneading is excellent, and the effect of improving mechanical properties and moldability is high. On the other hand, when the kneading temperature exceeds the upper limit of the above range, the thermal decomposition of the component (A) is accelerated, the heat resistance is lowered, and the compatibility with the component (B) may be lowered. When the kneading temperature is less than the lower limit of the above range, the compatibility between the component (A) and the component (B) at the time of melt kneading is poor, and the mechanical properties are sufficient when the resulting fluororesin composition is melt-molded. May not develop.

By kneading the component (A) and the component (B) as described above, a fluororesin composition containing the component (A) and the component (B) is obtained.
The obtained fluororesin composition can be melt-molded and formed into a molded product by melt-molding. The obtained molded product is excellent not only in toughness and mechanical strength but also in chemical resistance and abrasion resistance specific to fluororesin.

≪Molded product≫
The molded article of the present invention is obtained by melt-molding a fluororesin composition obtained by the above-described method for producing a fluororesin composition.
The melt molding of the fluororesin composition can be performed by a normal melt molding method. For example, methods by injection molding, extrusion molding, blow molding, press molding, transfer molding, calendar molding, and the like can be mentioned.
The melt molding apparatus used for melt molding of the fluororesin composition may be any apparatus that is usually used for melt molding. Examples thereof include a melt hot press machine “hot press duplex type” (manufactured by Tester Sangyo Co., Ltd.). .
In addition, manufacture of a molded article can be performed continuously with manufacture of the above-mentioned fluororesin composition.

  The application of the molded article of the present invention is not particularly limited, and can be used for various applications. Specific examples include, but are not limited to, sliding members, tube materials, insulating films, pump parts, rollers, gears, bearing members, and the like. Since the molded article of the present invention is excellent in mechanical properties such as toughness and mechanical strength, it is preferably used for applications requiring mechanical properties, and a sliding member is particularly preferable.

≪Wire≫
The electric wire of the present invention is obtained by melting the fluororesin composition obtained by the above-described method for producing a fluororesin composition and extruding the core wire around the core wire to form a coating layer that covers the surface of the core wire. And a coating layer made of the fluororesin composition that covers the surface thereof.
The core wire is not particularly limited, and examples thereof include various plating wires such as copper, copper alloy, aluminum and aluminum alloy, tin plating, silver plating, and nickel plating, stranded wires, superconductors, and plating wires for semiconductor element leads.
The coating of the core wire with the fluororesin composition can be performed by a known electric wire extrusion molding method using an extruder.

<Effect>
As described above, the compatibility between the component (A) and the component (B) during melt-kneading is increased by melt-kneading the component (A) and the component (B) having a water content of 1000 ppm or more. When the obtained fluororesin composition is melt-molded, excellent mechanical properties are exhibited. For example, a molded product obtained by melt-molding the fluororesin composition, or a coating layer formed by melting the fluororesin composition and extruding it around a core wire has the toughness of component (A) and the mechanical strength of component (B). It is excellent in mechanical properties that have a sufficient balance. Further, in addition to toughness and mechanical strength, excellent physical properties of the fluororesin and other thermoplastic resins are sufficiently exhibited. Moreover, this fluororesin composition is excellent also in the moldability at the time of performing melt molding.

Conventionally, in engineering plastics having a high water absorption rate, hydrolysis occurs due to the influence of moisture. Therefore, it is essential to perform preliminary drying before melt molding or before melt kneading with other materials.
In particular, polycarbonate, nylon, polysulfone, polyethersulfone, polyaryl ketone, polyarylate, polyamideimide, polyetherimide and the like are strongly influenced by hydrolysis. For example, polyaryl ketones are highly resistant to hydrolysis in molded articles, but readily undergo hydrolysis during molding. Therefore, in these engineering plastics, even if pre-drying is performed, if the raw material storage time of the hopper when the raw material is charged into the extruder becomes long, moisture is absorbed during that time, resulting in defective molding and poor physical properties. Is known to come out.
It is also known that problems occur in polymer alloys of these engineering plastics and other materials (for example, fluororesins).
However, in the present invention, surprisingly, even when an engineering plastic containing a large amount of moisture is used, molding defects and physical properties do not occur at the time of melt kneading with the component (A), and excellent mechanical properties and moldability are obtained. Is obtained.

  Several mechanisms are conceivable for the present invention to achieve the above effects. When the component (B) containing water specified above is melt-kneaded, the presence of water causes partial hydrolysis starting from the functional group of the component (B), and active radicals at the main chain or terminal. A reactive functional site and a functional group having polarity such as a carboxy group are generated. The interface between the component (A) and the component (B) is obtained by binding to the functional group of the component (A), or by interacting with the active site thermally decomposed from the functional group as a starting point, or by interaction with the bond or polarity. It is considered that the tension can be lowered and the compatibility is improved, and as a result, an excellent mechanical property can be obtained.

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.
In the examples, ppm indicates ppm by mass.
Of Examples 1 to 7 described later, Examples 1 and 2 are examples, and Examples 3 to 7 are comparative examples.
The raw materials and measurement methods used in each example are shown below.

<Raw material>
(A) -1: TFE / NAH / PPVE copolymer (melting point: 300 ° C., MFR: 17.2 g / 10 minutes) obtained in Production Example 1 described later.
PFA-1: TFE / perfluoro (alkyl vinyl ether) copolymer (melting point 303 ° C., MFR 15.2 g / 10 min), manufactured by Asahi Glass Co., Ltd., product name “Fluon PFA 73PT”.
(B) -1: Polyetheretherketone (water absorption 0.14%, melting point 340 ° C., MFR 17.3 g / 10 min), product name “KetaSpire (registered trademark) KT-820NT” manufactured by Solvay Advanced Polymers.

<Measurement method>
(Composition of fluorine-containing resin)
The composition of the fluorine-containing resin (molar ratio of each structural unit) was calculated from data measured by melt NMR analysis, fluorine content analysis, and infrared absorption spectrum analysis.

(Content of carbonyl group in fluorine-containing resin)
The ratio of the structural unit based on the monomer (NAH) which has a carbonyl group in a fluororesin was calculated | required by the following infrared absorption spectrum analysis.
The fluorine-containing resin was press-molded to obtain a 200 μm film. In the infrared absorption spectrum, any absorption peak in the structural unit based on NAH in the fluororesin appears at 1778 cm ⁻¹ . The absorbance of the absorption peak was measured, and the proportion (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 said ratio to a (mol%), the number of main-chain carbonyl groups to the number 1 × 10 ⁶ carbon atoms, a fluorine-containing resin is calculated as [a × ¹⁰ 6/100] Pieces.

(Melting point (℃))
The melting point (Tm) of the resin or composition was determined by differential scanning calorimetry (DSC). Specifically, using a thermal analyzer “EXSTAR DSC7020” (manufactured by Seiko Instruments Inc.), record the melting peak when the temperature is raised at a rate of 10 ° C./min, and correspond to the maximum value that is the top peak. The temperature (° C.) to be used was the melting point.

(MFR (g / 10 min))
Measures the mass (g) of resin that flows out from a nozzle with a diameter of 2 mm and a length of 8 mm in 10 minutes under a load of 49 N (5 kg) at 372 ° C. using a melt indexer manufactured by Techno Seven. The value was defined as MFR (g / 10 min).

(Tensile strength, tensile elongation (strength: MPa, elongation:%))
The sample shape is a micro dumbbell (thickness 1 mm) conforming to ASTM D1822, under a constant temperature and humidity environment controlled at a temperature of 23 ± 2 ° C. and a humidity of 50% ± 10%, using a strograph manufactured by Toyo Seiki Co., Ltd. A tensile strength / elongation test was performed under the conditions of a distance between marked lines of 7.6 mm and a tensile speed of 200 m / min. The stress at the maximum point load is the tensile strength, and the ratio of the sample length at break to the initial sample length is the tensile elongation.

(Moisture content (ppm))
The moisture content of the thermoplastic resin (B) was measured by the following procedure.
Using an infrared moisture meter “FD610” (manufactured by Kett Scientific Laboratory Co., Ltd.), the moisture content was determined from the mass reduction rate before and after the test under the conditions of a drying temperature of 140 ° C., a time stationary mode of 10 minutes, and a material mass of 100 g It was measured.

(Water absorption rate (%))
The water absorption rate of the thermoplastic resin (B) was measured according to the procedure defined by Method A of JIS K7209 (Plastic water absorption rate and boiling water absorption rate test method). Specifically, the thermoplastic resin (B) was press molded into a square plate having a side of 50 ± 1 mm and a thickness of 3 ± 0.2 mm, and this was used as a test piece. The test piece was subjected to condition adjustment in which it was dried for 24 hours in a thermostat kept at 50 ± 2 ° C., and then the mass M1 of the test piece was measured. Thereafter, the test piece was placed in a container containing water kept at 23 ± 2 ° C., and after 24 hours, the test piece was taken out of the water, and the mass M2 of the test piece was measured. From the result, the value calculated according to the following formula was taken as the water absorption rate.
Water absorption rate = (M2-M1) / M1 × 100

<Production Example 1: Production of (A) -1>
TFE (monomer of structural unit (a)), NAH (monomer of structural unit (b)), and CF ₂ ═CFO (CF ₂ ) ₃ F (perfluoropropyl vinyl ether, hereinafter also referred to as “PPVE”. Structural unit (c) )) Was polymerized as follows to obtain a fluororesin (A1-1).
First, 369 kg of 1,3-dichloro-1,1,2,2,3-pentafluoropropane “AK225cb” (manufactured by Asahi Glass Co., Ltd.) (hereinafter also referred to as “AK225cb”) and 30 kg of PPVE (manufactured by Asahi Glass Co., Ltd.) ) Was previously deaerated and placed in a polymerization tank having an internal volume of 430 L.
The temperature in the polymerization tank was raised to 50 ° C., and the pressure was increased to 0.89 MPa / G by feeding TFE into the polymerization tank. As a polymerization initiator, 0.36 mass% of (perfluorobutyryl) peroxide / AK225cb solution was fed into the polymerization tank in a total of 3 L at a rate of 6.25 mL per minute for polymerization.
During the polymerization, in order to maintain the inside of the polymerization tank at 0.89 MPa / G, TFE (manufactured by Asahi Glass Co., Ltd.) was fed into the polymerization tank. At the same time, when the TFE was 100 mol%, 0.1 mol% of NAH (manufactured by Hitachi Chemical Co., Ltd.) was fed into the polymerization tank.
8 hours after the start of the polymerization, when 32 kg of TFE was charged, the temperature in the polymerization tank was lowered to room temperature, and the pressure was reduced to normal pressure to obtain a slurry containing (A) -1.
(A) -1 and AK225cb in the obtained slurry were subjected to solid-liquid separation, and then the collected solid was dried at 150 ° C. for 15 hours to obtain 33 kg of granular (A) -1.
The specific gravity of (A) -1 was 2.15.
The copolymer composition of (A) -1 is (structural unit based on TFE) :( structural unit based on NAH) :( structural unit based on PPVE) = 97.9: 0.1: 2.0 (molar ratio) Met.
The content of the carbonyl group in (A) -1 was 1000 with respect to 1 × 10 ⁶ main chain carbon atoms of the fluororesin.
The melting point of (A) -1 was 300 ° C.
The MFR of (A) -1 was 17.2 g / 10 min at a measurement temperature of 372 ° C.

<Examples 1-2>
Using a lab plast mill kneader (manufactured by Toyo Seiki Co., Ltd.), (A) -1 and (B) -1 having a water content of 2000 ppm or 5000 ppm at a mixing ratio (volume%) shown in Table 1 Was melt kneaded to obtain a fluororesin composition.
At this time, the melt-kneading was carried out at a kneading temperature of 370 ° C. and a screw rotation speed of 30 rpm under kneading conditions for 10 minutes.
The water content of (B) -1 was adjusted by holding in a high humidity environment.

Next, the obtained fluororesin composition was preliminarily dried at 200 ° C. for 3 hours, and then used at a temperature of 370 ° C. and 10 MPa using a melt hot press “Hot Press Duplex” (manufactured by Tester Sangyo Co., Ltd.). Then, press molding was performed under the condition of a press time of 5 minutes, and a press molded product having a size of 80 mm × 80 mm and a thickness of 1.0 ± 0.05 mm was obtained.
A sample piece for a tensile strength / elongation test was obtained from the press-molded product, and a tensile strength / elongation test was performed under the condition of 23 ° C. to obtain a tensile strength (MPa) and a tensile elongation (%). The results are shown in Table 1.

<Example 3>
(B) -1 was preliminarily dried at 200 ° C. for 3 hours before kneading to obtain a fluororesin composition in the same manner as in Examples 1 and 2 except that the moisture content was 20 ppm. Strength and tensile elongation were determined. The results are shown in Table 1.

<Example 4>
A fluororesin composition was obtained in the same manner as in Example 2 except that PFA-1 was used in place of (A) -1, and press-molded to determine tensile strength and tensile elongation. The results are shown in Table 1.

<Example 5>
A fluororesin composition was obtained in the same manner as in Example 3 except that PFA-1 was used in place of (A) -1, and press-molded to determine tensile strength and tensile elongation. The results are shown in Table 1.

<Example 6>
A fluororesin composition was obtained in the same manner as in Example 2 except that only (B) -1 was used without using (A) -1, and the tensile strength and tensile elongation were determined. The results are shown in Table 1.

<Example 7>
A fluororesin composition was obtained in the same manner as in Example 3 except that only (B) -1 was used without using (A) -1, and the tensile strength and tensile elongation were determined. The results are shown in Table 1.

As shown in the above results, the press-molded products of the fluororesin compositions obtained in Examples 1 and 2 had a high tensile strength, a high tensile elongation, and excellent mechanical properties.
From the comparison with Examples 1 and 2 and Example 3 similar to Examples 1 and 2 except that (B) -1 was used in a state with a water content of 20 ppm, the component (B) was in a state with a water content of 1000 ppm or more. It has been confirmed that the use leads to an improvement in tensile strength and tensile elongation, particularly tensile elongation.
Comparing Examples 2 to 3 with Examples 4 to 5 similar to Examples 2 to 3 except that PFA-1 was used in place of (A) -1, the mechanical properties between Examples 4 and 5 were compared. The difference, particularly the difference in tensile elongation, was small compared to the difference in mechanical properties between Example 2 and Example 3. From this, it has been confirmed that the fact that the fluororesin contains a carbonyl group leads to improvement in mechanical properties in combination with the component (B) having a water content of 1000 ppm or more.
When Examples 1-2 and Examples 6-7 which used (B) -1 independently were contrasted, Examples 6-7 were inferior in tensile strength compared with Examples 1-2. In particular, Example 6 in which the moisture content of (B) -1 was the same as Example 2 at 5000 ppm was inferior to Examples 1 and 2 in tensile strength.

The fluororesin composition of the present invention can be melt-molded and exhibits excellent mechanical properties when melt-molded.
Therefore, according to the present invention, various extruded products including tube materials, bearings, gears, electronic equipment, injection molded products such as spacers, rollers, and cams, and other molded products containing fluororesins for various uses, A material useful for an electric wire having a coating layer containing a fluororesin can be provided.
Furthermore, the present invention does not require preliminary drying of the raw material, and can solve problems in the case of using engineering plastics having a high water absorption rate, such as deterioration of physical properties due to moisture and molding defects. That is, it is known that engineering plastics and the like having a high water absorption rate have a problem that moisture causes a decrease in physical properties such as mechanical properties and a decrease in moldability. This is a result of the above-described Examples 6-7. You can also check from. However, in the present invention, even when an engineering plastic having a high moisture content is used, the resulting fluororesin composition has excellent mechanical properties and moldability.

Claims (9)

Melting and kneading a melt-moldable fluororesin (A) having a melting point of 260 ° C. or higher and a thermoplastic resin (B) not containing a fluorine atom and having a water absorption of 0.1% or more Having a step of obtaining a fluororesin composition,
A method for producing a fluororesin composition, wherein the thermoplastic resin (B) before melt-kneading has a water content of 1000 ppm by mass or more.   2. The fluorine according to claim 1, wherein the volume ratio ((A) :( B)) of the fluororesin (A) to the thermoplastic resin (B) is 0.1: 99.9 to 50:50. A method for producing a resin composition. The fluororesin of Claim 1 or 2 whose content of the carbonyl group in the said fluororesin (A) is 10-60,000 with respect to 1 * 10 < ⁶ > main chain carbon number of the said fluororesin (A). A method for producing the composition.   The thermoplastic resin (B) is at least one selected from the group consisting of polysulfone, polyethersulfone, polyaryl ketone, polyarylate, polyamideimide, and polyetherimide. A method for producing the fluororesin composition according to claim 1.   The manufacturing method of the fluororesin composition as described in any one of Claims 1-4 whose said thermoplastic resin (B) is polyetheretherketone. The fluororesin (A) is a hydrocarbon monomer having a structural unit (a) based on one or both of tetrafluoroethylene and chlorotrifluoroethylene, and one or both of a carboxy group and an acid anhydride group. And a structural unit (c) based on a fluorine monomer (excluding tetrafluoroethylene and chlorotrifluoroethylene),
The structural unit (a) is 50 to 99.89 mol% with respect to the total molar amount of the structural unit (a), the structural unit (b), and the structural unit (c), and the structural unit (b ) Is 0.01 to 5 mol%, and the structural unit (c) is 0.1 to 49.99 mol%, The method for producing a fluororesin composition according to any one of claims 1 to 5 . The manufacturing method of the molded article which manufactures a fluororesin composition by the manufacturing method of the fluororesin composition as described in any one of Claims 1-6, and melt-molds the obtained fluororesin composition. The manufacturing method of the molded product according to claim 7, wherein the molded product is a sliding member. To produce a fluororesin composition by the method for producing a fluororesin composition according to any one of claims 1 to 6, to melt the resulting fluororesin composition, extruded around the core wire, the core wire An electric wire manufacturing method for forming a coating layer covering a surface.