JP5907282B2 - Resin composition and molded product - Google Patents

Description

The present invention relates to a resin composition and a molded article.

In recent years, for the purpose of weight reduction and cost reduction, active studies have been made to convert metal parts into resins, and automobile parts, industrial parts or the like using thermoplastic resins such as polyamide resins, polycarbonate resins, polyacetal resins, etc. Electrical and electronic parts have been put into practical use. In sliding applications such as gears and bearing retainers, the replacement of metal sliding members with plastic sliding members is progressing, but the sliding members used under conditions such as high load, high temperature, and high speed rotation. The above-mentioned thermoplastic resin has insufficient slidability, and problems such as wear, melting, cracking and chipping may occur.

On the other hand, fluororesin has excellent properties such as slidability, heat resistance, chemical resistance, solvent resistance, weather resistance, flexibility, electrical properties, etc. Used in the field. The fluororesin is particularly excellent in slidability, and its low coefficient of friction is prominent among the resins. However, it is often inferior to physical heat resistance as indicated by mechanical properties and deflection temperature under load compared to crystalline heat-resistant thermoplastic resin, and dimensions compared to amorphous heat-resistant thermoplastic resin. In some cases, the stability is inferior, and the range of use is limited.

Under such circumstances, studies have been made to improve the slidability of the thermoplastic resin and to apply to a wider range of sliding members. For example, Patent Document 1 includes (A) 70 to 99% by mass of a polyaryl ketone resin and (B) 30 to 1% by mass of a fluororesin, and (B) an average particle of the fluororesin dispersed in the resin composition. A resin composition having a diameter of 0.1 to 30 μm has been proposed.

In addition to the purpose of improving the slidability, it is known to add a fluororesin to the thermoplastic resin. For example, in Patent Document 2, a fine powder of PEEK resin is mixed in a PFA resin aqueous dispersion at a PFA: PEEK weight ratio of 75:25 to 70:30, and this dispersion is roughened according to a conventional method. It is disclosed that a PFA-PEEK composite coating film having adhesion durability is formed by directly applying to a metallized metal surface and baking. Patent Document 3 discloses a thermoplastic resin containing a mixture of a polyaryl ketone resin and a thermoplastic fluororesin, wherein the continuous phase of the mixture is the thermoplastic fluororesin, and the dispersed phase is a polyaryl ketone resin. A composition is described.

JP 2006-274073 A JP-A-6-316686 JP 2010-189599 A

However, the resin compositions containing polyaryl ketone resins and fluororesins that have been developed so far have a problem of delamination during injection molding, and when polymolds are obtained by extrusion. There has been a problem of uneven thickness of the extrudate and foreign matter occurring due to the aggregation of the ketone resin particles, and in particular in the case of thin film molding, there has been a problem of problems such as tearing.
The present invention has been made in view of the above situation, has excellent electrical characteristics, friction characteristics, chemical resistance, can prevent delamination phenomenon during injection molding, and can extrude during extrusion molding. It is an object of the present invention to provide a resin composition capable of eliminating problems such as unevenness in thickness of a product and foreign matter, particularly tearing in the case of forming a thin film.

As a result of intensive studies on a resin composition capable of obtaining a good molded product by injection molding or extrusion molding, the present inventors have found that an aromatic polyetherketone resin is in the form of particles having a specific particle size in a specific fluororesin. The resin composition in which the mass ratio of the aromatic polyetherketone resin to the fluororesin is in a specific range is excellent in electrical characteristics, friction characteristics, chemical resistance, and delamination phenomenon during injection molding The present invention has found that there are no defects such as uneven thickness of the extrudate and foreign matter, particularly tearing when forming a thin film without agglomeration of aromatic polyetherketone resin particles during extrusion molding. It came to be completed.

That is, the present invention is a resin composition containing an aromatic polyether ketone resin (I) and a fluororesin (II), wherein the fluororesin (II) is tetrafluoroethylene and the following general formula (1):
CF ₂ = CF-Rf ¹ (1)
(Wherein Rf ¹ represents —CF ₃ or —ORf ² ; Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms) The aromatic polyetherketone resin (I) is dispersed in the form of particles in the fluororesin (II), and fluorine relative to the total mass of the aromatic polyetherketone resin (I) and the fluororesin (II). The mass ratio of the resin (II) is more than 50 mass% and 99 mass% or less, and the average dispersed particle size in the fluororesin (II) of the aromatic polyether ketone resin (I) is 1 μm or less. It is a resin composition characterized by these.

In the resin composition of the present invention, the melt viscosity ratio (I) / (II) between the aromatic polyether ketone resin (I) and the fluororesin (II) is preferably 1.0 to 5.0.

The fluororesin (II) preferably has a melt flow rate of 0.1 to 100 g / 10 minutes.

The aromatic polyether ketone resin (I) is preferably a polyether ether ketone.

The resin composition of the present invention is preferably a kneaded product obtained by melt-kneading the aromatic polyether ketone resin (I) and the fluororesin (II).

The present invention is also a molded article formed from the resin composition.

The molded article of the present invention is preferably used for electric wire coating.

The molded article of the present invention is preferably used for semiconductor parts.

The present invention also provides an insulated wire having a conductor (A) and an insulating layer (B) formed on the outer periphery of the conductor (A), wherein the insulating layer (B) is formed from the resin composition. It is also an electric wire.

The present invention is also a method for producing an insulated wire having a conductor (A) and an insulating layer (B), wherein the method comprises molding the resin composition and forming an insulating layer on the outer periphery of the conductor (A). It is also a manufacturing method of an insulated wire including the process of forming (B).

Since the resin composition of the present invention has the above-described configuration, it has excellent electrical characteristics, friction characteristics, and chemical resistance, can prevent delamination during injection molding, and can exhibit uneven thickness of the extrudate during extrusion molding. In addition, it is possible to eliminate defects such as tears in the case of forming a thin film and foreign matters.

The present invention is described in detail below.

The resin composition of the present invention contains an aromatic polyether ketone resin (I) and a fluororesin (II).

The aromatic polyether ketone resin (I) is preferably at least one selected from the group consisting of polyether ketone, polyether ether ketone, polyether ketone ketone and polyether ketone ether ketone ketone, More preferably, it is at least one selected from the group consisting of ether ketones and polyether ether ketones, and more preferably polyether ether ketones.

The aromatic polyether ketone resin (I) preferably has a melt viscosity of 0.10 to ^2.00 kNsm ⁻² at 60 sec ⁻¹ and 390 ° C. When the melt viscosity is in the above range, a decrease in strength in the resin composition of the present invention can be suppressed. A more preferred lower limit of the melt viscosity is 0.20 kNsm ^-2 . The upper limit with more preferable melt viscosity is 1.70 kNsm- ² , More preferably, it is 1.50 kNsm- ² .
The melt viscosity of the aromatic polyether ketone resin (I) is measured according to ASTM D3835.

The aromatic polyether ketone resin (I) preferably has a glass transition temperature of 130 ° C. or higher. More preferably, it is 135 degreeC or more, More preferably, it is 140 degreeC or more. When the glass transition temperature is in the above range, a resin composition having excellent heat resistance can be obtained. The glass transition temperature is measured by a differential scanning calorimetry (DSC) apparatus.

The aromatic polyether ketone resin (I) preferably has a melting point of 300 ° C. or higher. More preferably, it is 320 degreeC or more. When the melting point is in the above range, the heat resistance of the obtained molded product can be improved. The melting point is measured by a differential scanning calorimetry (DSC) apparatus.

The fluororesin (II) is tetrafluoroethylene (TFE) and the following general formula (1):
CF ₂ = CF-Rf ¹ (1)
(Wherein Rf ¹ represents —CF ₃ or —ORf ² ; Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms) It is a coalescence. As fluororesin (II), 1 type may be used and 2 or more types may be used. When Rf ¹ is —ORf ² , Rf ² is preferably a perfluoroalkyl group having 1 to 3 carbon atoms. By using the fluororesin (II), the resin composition of the present invention has excellent electrical characteristics, friction characteristics, and chemical resistance.

The perfluoroethylenically unsaturated compound represented by the general formula (1) is selected from the group consisting of hexafluoropropylene, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether) and perfluoro (propyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of hexafluoropropylene and perfluoro (propyl vinyl ether).

The fluororesin (II) is preferably a perfluoropolymer from the viewpoints of electrical characteristics, friction characteristics, and chemical resistance.

The fluororesin (II) is preferably composed of 87 to 99 mol% of TFE and 1 to 13 mol% of a perfluoroethylenically unsaturated compound represented by the general formula (1). More preferably, it is a fluororesin composed of 90 to 99 mol% of TFE and 1 to 10 mol% of a perfluoroethylenically unsaturated compound represented by the above general formula (1), and more preferably 93 to It is a fluororesin composed of 99 mol% of TFE and 1 to 7 mol% of a perfluoroethylenically unsaturated compound represented by the above general formula (1).

The fluororesin (II) preferably has a melt viscosity of 0.3 to 5.0 kNsm ^-2 at 60 sec ^-1 and 390 ° C. When the melt viscosity is in the above range, a decrease in strength in the resin composition of the present invention can be suppressed. The minimum with more preferable melt viscosity is 0.4 kNsm- ² , More preferably, it is 0.5 kNsm- ² . The upper limit with more preferable melt viscosity is 4.5 kNsm- ² , More preferably, it is 4.0 kNsm- ² .
The melt viscosity of the fluororesin (II) is measured according to ASTM D3835.

The fluororesin (II) preferably has a melt flow rate (MFR) measured under conditions of 372 ° C. and a load of 5000 g of 0.1 to 100 g / 10 minutes, and preferably 5 to 50 g / 10 minutes. More preferably, it is 10-50 g / 10min. When the MFR is in the above range, the injection moldability and extrusion moldability of the resin composition of the present invention are improved.
The MFR of the fluororesin (II) is measured using a melt indexer (manufactured by Toyo Seiki Seisakusho) in accordance with ASTM D3307-01.

The melting point of the fluororesin (II) is not particularly limited, but it is preferable in molding that the fluororesin (II) is already melted at a temperature at which the aromatic polyetherketone resin (I) used in molding is melted. The temperature is preferably not higher than the melting point of the aromatic polyether ketone resin (I). For example, the melting point of the fluororesin (II) is preferably 230 to 350 ° C.

The fluororesin (II) may be treated with fluorine gas by a known method or may be treated with ammonia.

In the resin composition of the present invention, the mass ratio of the fluororesin (II) to the total mass of the aromatic polyetherketone resin (I) and the fluororesin (II) is more than 50 mass% and 99 mass% or less. When the mass ratio of the aromatic polyetherketone resin (I) and the fluororesin (II) is in the above range, the resin composition of the present invention has excellent electrical characteristics, friction characteristics, and chemical resistance. If the content of the fluororesin (II) exceeds 99 by mass ratio with the aromatic polyetherketone resin (I), the strength of the resin composition of the present invention tends to decrease. There exists a tendency for the electrical property and chemical resistance in the resin composition of invention to fall. A more preferable range of the mass ratio of the fluororesin (II) to the total mass of the aromatic polyetherketone resin (I) and the fluororesin (II) is 55% by mass or more and 95% by mass or less. More preferably, it is 60 mass% or more and 90 mass%.

The resin composition of the present invention comprises a melt viscosity ratio (I) / (II) (aromatic polyetherketone resin (I) / fluororesin (II) of aromatic polyetherketone resin (I) and fluororesin (II). )) Is preferably 1.0 to 5.0. When the melt viscosity ratio (I) / (II) is in the above range, the aromatic polyetherketone resin (I) is dispersed in the fluororesin (II) in finer particles with an average dispersed particle size of 1 μm or less. It becomes possible to make it. The melt viscosity ratio (I) / (II) is more preferably greater than 1.0 and less than or equal to 5.0, more preferably 1.1 to 4.0, and 1.1 to 3.0. It is particularly preferred.

In the resin composition of the present invention, the aromatic polyether ketone resin (I) is dispersed in the form of particles in the fluororesin (II). When the resin composition is in such a form, the delamination phenomenon can be prevented at the time of injection molding, and at the time of extrusion molding, there are problems such as uneven thickness of the extrudate and foreign matter, particularly tearing when forming a thin film. Can be eliminated.

In the resin composition of the present invention, the average dispersed particle size of the aromatic polyetherketone resin (I) in the fluororesin (II) is 1 μm or less. When the average dispersed particle size of the aromatic polyetherketone resin (I) is 1 μm or less, it is possible to prevent the delamination phenomenon during injection molding when molding the resin composition, and during extrusion molding. It is possible to eliminate problems such as uneven thickness of the extrudate and foreign matter, particularly tearing when forming a thin film.
The average dispersed particle size of the aromatic polyetherketone resin (I) is preferably 0.7 μm or less, and more preferably 0.5 μm or less. More preferably, it is 0.3 μm or less.
The lower limit of the average dispersed particle size is not particularly limited, but may be 0.01 μm.

The average dispersed particle size of the aromatic polyetherketone resin (I) is obtained by observing the resin composition of the present invention with a confocal laser microscope or by using an ultrathin film from a press sheet prepared from the resin composition of the present invention. It can be obtained by cutting out a section, performing microscopic observation of the ultrathin section with a transmission electron microscope, and binarizing the obtained image with an optical analyzer.

The resin composition of the present invention contains an aromatic polyether ketone resin (I) and a fluororesin (II), but may contain other components as necessary. Although it does not specifically limit as said other component, Fibrous reinforcement materials, such as whisker, such as potassium titanate, glass fiber, asbestos fiber, carbon fiber, ceramic fiber, potassium titanate fiber, aramid fiber, and other high-strength fibers Inorganic fillers such as calcium carbonate, talc, mica, clay, carbon powder, graphite and glass beads; colorants; inorganic or organic fillers usually used such as flame retardants; stabilizers such as minerals and flakes; silicone oil Lubricants such as molybdenum disulfide; pigments; conductive agents such as carbon black; impact resistance improvers such as rubber; and other additives.

The production of the resin composition of the present invention is usually performed using a mixing machine such as a compounding mill, a Banbury mixer, a pressure kneader, and an extruder that are usually used to mix a resin composition such as a molding composition. It can be performed according to the conditions. Since the average dispersed particle size of the aromatic polyetherketone resin (I) can be reduced, the mixer is preferably a twin screw extruder, and the screw configuration of the twin screw extruder is preferably L / D = 35 or more, More preferably, L / D = 40 or more, and particularly preferably L / D = 45 or more. L / D is the effective length of the screw (L) / screw diameter (D).
From the above, the resin composition of the present invention is obtained by mixing the aromatic polyetherketone resin (I) and the fluororesin (II) with a twin screw extruder having a screw configuration with an L / D of 35 or more. It is preferable to be obtained.

Examples of the method for producing the resin composition of the present invention include a method in which the aromatic polyether ketone resin (I) and the fluororesin (II) are mixed in a molten state.
By thoroughly kneading the aromatic polyether ketone resin (I) and the fluororesin (II), the resin composition of the present invention having a desired dispersion state can be obtained. Since the dispersion state affects the moldability at the time of injection molding or extrusion molding, the kneading method should be selected appropriately.

As a method for producing the resin composition of the present invention, for example, the aromatic polyetherketone resin (I) and the fluororesin (II) are introduced into a mixer at an appropriate ratio, and the above-mentioned other components are added as desired. And a method of producing by melting and kneading the resin (I) and (II) above the melting point.
Thus, it is also preferable that the resin composition of the present invention is a kneaded product obtained by melt-kneading the aromatic polyether ketone resin (I) and the fluororesin (II). One of the forms.

The other components may be added to the aromatic polyether ketone resin (I) and the fluororesin (II) in advance and mixed, or the aromatic polyether ketone resin (I) and the fluororesin (II). You may add when mix | blending.

What is necessary is just to set suitably as the temperature at the time of the said melt-kneading according to the kind etc. of aromatic polyether ketone resin (I) and fluororesin (II) to be used, for example, it is preferable that it is 360-400 degreeC. The kneading time is usually 1 minute to 1 hour.

A molded article formed from the resin composition of the present invention is also one aspect of the present invention.

Molded articles formed from the resin composition of the present invention include CMP retainer rings, etching rings, silicon wafer carriers, IC chip trays and other semiconductor / liquid crystal manufacturing equipment parts, insulating films, small size in the electric / electronic / semiconductor field. Button battery, cable connector, aluminum electrolytic capacitor body case; in the automotive field, thrust washer, oil filter, auto air conditioner control unit gear, throttle body gear, motor coil wire covering, ABS parts, AT seal ring, MT shift Fork pads, bearings, seals, clutch rings; in the industrial field, compressor parts, cables for mass transport systems, conveyor belt chains, connectors for oilfield development machinery, pump parts for hydraulic drive systems (shafts) , Port plates, piston ball joints), gears, piston seal rings; in the aerospace field, aircraft cabin interior parts, fuel pipe protection materials; and food / beverage production equipment parts and medical equipment parts (sterilization equipment) , Gas / liquid chromatograph) and the like.
It does not specifically limit as a shape of the said molded article, For example, it can be set as various shapes, such as a sheet form; a film form; a rod form;

The molded product formed from the resin composition of the present invention can also be suitably used as a molded product for sliding members. Since the molded product for sliding members molded using the resin composition has a low coefficient of dynamic friction, it can be suitably used as a sliding member. Moreover, since it contains a fluororesin, it is excellent in chemical resistance, weather resistance, non-adhesiveness, water repellency, electrical properties and the like.
Although it does not specifically limit as said molded article for sliding members, For example, a sealing material, a gear, an actuator, a piston, a bearing, a bearing retainer, a bush, a switch, a belt, a bearing, a cam, a roller, a socket etc. are mentioned.

The above-mentioned bearing is a member that is installed on the outer periphery of the shaft and used in contact with the shaft, such as an inner ring of a rolling bearing, a sliding bearing, etc., and normally supports a shaft that rotates or linearly moves. And holds the acting load. The bearing can be used alone or in combination with other members. When used in combination with other members, for example, rolling bearings such as ball bearings, roller bearings, radial bearings, thrust bearings, etc .; sliding bearings such as perfect circle bearings, partial bearings, multi-face bearings; oilless bearings; air bearings; magnetic bearings, etc. Used for.

The gears are usually mounted on a rotating shaft and used for power transmission. For example, spur gears, helical gears, racks, internal gears, bevel gears, miter gears, screw gears, worm gears, drives A gear, an idle gear, etc. are mentioned.

The seal ring is usually attached to a shaft that rotates or moves in the axial direction, and serves to seal oil between a shaft of a transmission or a cylinder of a piston, for example. Such a seal ring can be used for various applications. For example, it can be used as a seal ring for an automatic transmission such as an automobile or an engine piston of an automobile, a ship, a construction vehicle, an industrial machine, or the like. it can.

Various conditions relating to the molding machine in the method for manufacturing a molded product are not particularly limited, and for example, conditions that are normally performed can be employed. Usually, the molding temperature is preferably a temperature equal to or higher than the melting point of the fluororesin (II) used. The molding temperature is preferably a temperature lower than the lower one of the decomposition temperature of the fluororesin (II) and the decomposition temperature of the aromatic polyether ketone resin (I). Such a molding temperature may be, for example, 250 to 400 ° C.

The molded product of the present invention is generally a thermoplastic resin composition such as injection molding, extrusion molding, press molding, blow molding, calendar molding, casting molding, etc., depending on the type, application, shape, etc. of the target molded product. It can shape | mold by the shaping | molding method currently used with respect. A molding method combining the above molding methods can also be employed. Furthermore, the resin composition of the present invention and another polymer may be combined and molded.
In particular, the resin composition of the present invention can prevent delamination during injection molding, and can eliminate defects such as uneven thickness of the extrudate and foreign matter, particularly tearing when thin film molding is performed during extrusion molding. Therefore, the molded article of the present invention is preferably molded by injection molding or extrusion molding.

Since the resin composition of the present invention can prevent delamination during injection molding, it can be suitably used for the production of semiconductor components such as wafer carriers, chuck arms, and CMP rings.

Semiconductor components such as wafer carriers, chuck arms, and CMP rings formed from the resin composition of the present invention have less strength reduction due to suppression of delamination during injection molding, and cracks, chips, etc. during use The characteristic that it is possible to suppress the troubles of is exhibited.

Moreover, since the resin composition of the present invention can eliminate problems such as uneven thickness of the extrudate and foreign matter, particularly tearing when thin film molding is performed during extrusion molding, it is preferably used for the production of an insulating layer of an insulated wire. Can do. In addition, when the molded product formed from the resin composition of the present invention is used for an insulating layer of an insulated wire, the insulating layer has excellent insulating properties, exhibits a low dielectric constant, and is easy to handle the wire. Will also be excellent. In addition, the insulating layer is excellent in heat resistance, mechanical strength, tensile elongation, and crack resistance, and the insulating layer does not peel from the conductor even when the insulated wire is used at a high temperature. Thus, the molded article formed from the resin composition of this invention can be used suitably for an electric wire coating | cover application as an insulating layer of an insulated wire.
That is, an insulated wire having a conductor (A) and an insulating layer (B) formed on the outer periphery of the conductor (A), wherein the insulating layer (B) is formed from the resin composition of the present invention. Is also one aspect of the present invention.
In addition, the insulated wire of this invention can be used suitably also for a thin wire with a thin thickness of an insulating layer (B).

In the insulated wire of the present invention, the insulating layer (B) formed on the outer periphery of the conductor (A) may be in contact with the conductor (A), or another layer between the conductor (A). For example, it may be formed through another resin layer. The insulating layer (B) is preferably in contact with the conductor (A), and in that case, an insulated wire in which the adhesion between the conductor (A) and the insulating layer (B) is strong can be obtained.

Although the film thickness of an insulating layer (B) is not restrict | limited in particular, For example, it is preferable that it is 1-100 micrometers. More preferably, it is 2-60 micrometers, More preferably, it is 3-40 micrometers. Further, it can be thinned to 30 μm or less. Reducing the thickness of the insulating layer (B) is advantageous in that it has excellent heat dissipation performance.

An insulating layer (B) can be obtained by forming the resin composition of this invention in the outer periphery of a conductor (A), and the insulated wire of this invention manufactures the resin composition of this invention mentioned above, for example. It can be manufactured by a manufacturing method including a step and a step of forming the insulating layer (B) on the outer periphery of the conductor (A) by molding the resin composition of the present invention.
That is, a method for producing an insulated wire having a conductor (A) and an insulating layer (B), the method comprising molding the resin composition of the present invention and forming an insulating layer ( A method for manufacturing an insulated wire including the step of forming B) is also one aspect of the present invention.

The method for forming the insulating layer (B) is not particularly limited, and a method usually used for forming the insulating layer can be adopted as the various conditions. Further, the insulating layer (B) may be formed directly on the conductor (A), or may be formed through another layer, for example, another resin layer.

The insulating layer (B) is formed by melting and extruding the resin composition on the surface of the conductor (A) or the surface of the resin layer of the conductor (A) on which another resin layer has been formed in advance. A resin composition is melt-extruded to produce a film, the film is slit to a predetermined size, and then the surface of the conductor (A) or the surface of the resin layer of the conductor (A) in which another resin layer is formed in advance. In addition, the film can be formed by a method of winding the film.

When the insulating layer (B) is formed by melt extrusion, it is usually preferable that the forming temperature is a temperature equal to or higher than the melting point of the fluororesin (II) used. The molding temperature is preferably a temperature lower than the lower one of the decomposition temperature of the fluororesin (II) and the decomposition temperature of the aromatic polyether ketone resin (I). Such a molding temperature may be, for example, 250 to 400 ° C. The molding temperature is more preferably 320 to 400 ° C.

The insulated wire of the present invention may be heated after forming the insulating layer (B). The heating may be performed at a temperature near the melting point of the fluororesin (II).

In the insulated wire of the present invention, the insulating layer (B) is formed on the outer periphery of the conductor (A). Another layer such as another resin layer may be provided between the conductor (A) and the insulating layer (B). Moreover, the insulated wire of this invention may have another layer, for example, another resin layer, in the outer periphery of an insulating layer (B).

The other resin layer is different from the insulating layer (B). The other resin layer is, for example, a layer made of at least one resin selected from the group consisting of aromatic polyetherketone resin, fluororesin, polyamideimide, polyetherimide, polyethersulfone, and polyphenylene sulfide. It is preferable.

The material for forming the conductor (A) is not particularly limited as long as the material has good conductivity, and examples thereof include copper, copper alloy, copper clad aluminum, aluminum, silver, gold, and galvanized iron.

The shape of the conductor is not particularly limited, and may be circular or flat. In the case of a circular conductor, the diameter of the conductor may be 0.3 to 2.5 mm.

The insulated wire of the present invention can be suitably used for wrapping wires, automotive wires, robot wires, and the like. Moreover, it can be used suitably also as a coil winding (magnet wire), and if the insulated wire of the present invention is used, it is difficult to cause damage in winding processing. The above winding is suitable for motors, rotating electrical machines, compressors, transformers, etc., requires high voltage, high current and high thermal conductivity, requires high-density winding processing, and is downsized. -It has the characteristics that it can sufficiently withstand the use with high output motors. Moreover, it is suitable also as an electric wire for power distribution, power transmission, or communication.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

<Measurement of melt viscosity>
The melt viscosity of the aromatic polyetherketone resin was measured at 60 sec ⁻¹ and 390 ° C. according to ASTM D3835.
The melt viscosity of the fluororesin was measured in accordance with ASTM D3835 at 60 sec ⁻¹ and 390 ° C.

<Measurement of MFR>
In accordance with ASTM D3307-01, using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the mass of the polymer flowing out per 10 minutes from a nozzle having an inner diameter of 2 mm and a length of 8 mm under a load of 372 ° C. and 5000 g (g / g 10 minutes) and MFR was measured.

<Production of press sheet molding>
Using the resin compositions produced in the examples and comparative examples, compression molding was carried out under conditions of 350 ° C. and 4 MPa using a hot press machine to produce a sheet having a thickness of 1 mm.

<Measurement of relative permittivity>
Aluminum was vapor-deposited in vacuum on both sides of the press sheet produced by the method described above to obtain a measurement sample. The capacitance and dielectric loss tangent at a frequency of 10 kHz were measured with a measurement sample using an LCR meter (ZM2353 manufactured by NF Circuit Design Block Co., Ltd.) at 25 ° C. in a dry air atmosphere. The relative dielectric constant was calculated from each obtained capacitance and the thickness of the press sheet.

<Evaluation of acid resistance>
An ASTM V type dumbbell was produced using the press sheet produced by the above-described method, and the dumbbell was immersed in sulfuric acid at 60 ° C. and 70% for one week. A tensile test was performed before and after the immersion, and the elongation retention ratio (%) after immersion in sulfuric acid was determined by comparing the elongation before and after immersion, and the acid resistance was evaluated. In other words, it can be said that the greater the elongation retention after immersion in sulfuric acid, the higher the acid resistance.

<Calculation of average dispersed particle size>
Using the press sheet produced by the method described above, trimming with a razor for trimming so that the tip is 1 mm square, and then fixing it to the sample holder of an ultramicrotome (Leica ULTRACUT S), the inside of the chamber After cooling to −80 ° C. with liquid nitrogen, an ultrathin section having a thickness of 90 nm was cut out.
The obtained ultrathin sections were collected with a platinum ring to which a 20% ethanol solution was attached, and attached to a copper sheet mesh (200A, φ3.0 mm, manufactured by Oken Shoji Co., Ltd.).
Then, the ultra-thin slice adhered to the copper sheet mesh was observed using a transmission electron microscope (H7100FA manufactured by Hitachi, Ltd.).
The negative film obtained by microscopic observation is converted into an electronic image by a scanner (GT-9400UF manufactured by EPSON), and an electronic image is binarized using an optical analysis device (LUZEX AP manufactured by Nireco). The average dispersed particle size was determined.

<Production of injection molded products>
The pellets of the resin composition produced in Examples and Comparative Examples are supplied to a hybrid injection molding machine (PNX60 manufactured by Nissei Plastic Industry Co., Ltd.), cylinder temperature 350 ° C., mold temperature 180 ° C., injection pressure 200 MPa, screw rotation speed. A flat plate having a length of 80 mm, a width of 80 mm, and a thickness of 3 mm was formed under the conditions of 120 rpm and a drying temperature of 240 ° C.

<Measurement of dynamic friction coefficient>
Using the injection-molded product produced by the above-described method, the measurement was performed according to the JIS K7218 A method using a ring-on-disk type rotary frictional wear tester (manufactured by Takachiho Seiki Co., Ltd.).

<Determination of delamination during injection molding>
The presence or absence of delamination of the injection molded product produced by the method described above was visually determined.
Judgment criteria:
○: No delamination phenomenon was observed.
X: Delamination phenomenon occurred.

<Determination of thickness unevenness during extrusion>
The pellets of the resin compositions produced in the examples and comparative examples were converted into T-die extruders for film forming (φ20 mm, L / D = 25, die width 150 mm, lip width 0.4 mm; Labyoplast Mill T manufactured by Toyo Seiki Seisakusho Co., Ltd. Die extrusion molding apparatus), and a film having a thickness of 50 μm was molded under conditions of a cylinder temperature of 370 ° C., a die temperature of 375 ° C., and a screw rotation speed of 25 rpm.
Thereafter, using a micrometer, the thickness of the formed film was measured at intervals of 20 mm in the width direction, and thickness unevenness was determined.
Judgment criteria:
○: Film thickness difference is less than ± 5% ×: Film thickness difference is ± 5% or more

<Determination of thickness unevenness during wire forming>
The pellets of the resin composition produced in the examples and comparative examples are supplied to an electric wire forming machine having a screw outer diameter of 30 mmφ, and a coated electric wire having a coating thickness of 0.1 mm having a copper round wire having an outer diameter of 1.0 mmφ as a core wire. Manufactured. Thereafter, using a micrometer, the thickness of the formed electric wire was measured at 300 mm intervals in the width direction, and the thickness unevenness of the electric wire coating was determined.
Judgment criteria:
○: The thickness difference of the wire coating is less than ± 5% ×: The thickness difference of the wire coating is ± 5% or more

In the examples and comparative examples, the following materials were used.
Aromatic polyetherketone resin (I-1): polyetheretherketone (melt viscosity; 1.19 kNsm ⁻² )
Aromatic polyether ketone resin (I-2): Polyether ether ketone (melt viscosity; 1.32 kNsm ⁻² )
Aromatic polyether ketone resin (I-3): Polyether ether ketone (melt viscosity; 0.31 kNsm ⁻² )
Fluororesin (II-1): Tetrafluoroethylene / hexafluoropropylene copolymer (trade name: NEOFLON NP101, manufactured by Daikin Industries, Ltd. Melt viscosity: 0.56 kNsm ^−2, MFR; 25 g / 10 min.)
Fluororesin (II-2): tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (trade name: NEOFLON AP201, manufactured by Daikin Industries, Ltd. Melt viscosity: 0.80 kNsm ^−2, MFR: 22 g / 10 min.)

<Example 1>
Aromatic polyetherketone resin (I-1) and fluororesin (II-1) are premixed at the ratio (parts by mass) shown in Table 1, and a twin screw extruder (φ15 mm, L / D = 60) is used. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 395 ° C. and a screw rotation speed of 300 rpm to produce a resin composition. Using the obtained resin composition, a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after immersion in sulfuric acid were measured. Moreover, when an ultra-thin section was cut out from the press sheet and the ultra-thin section was observed with a transmission electron microscope, the aromatic polyetherketone resin (I-1) was particulated in the fluororesin (II-1). The dispersion was confirmed, and the average dispersed particle size of the aromatic polyetherketone resin (I-1) was calculated with the press sheet. And by using the obtained resin composition, the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire molding are determined by the above determination method. Judged. The results are shown in Table 1.

<Example 2>
Aromatic polyetherketone resin (I-1) and fluororesin (II-1) are premixed at the ratio (parts by mass) shown in Table 1, and a twin screw extruder (φ15 mm, L / D = 60) is used. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 395 ° C. and a screw rotation speed of 300 rpm to produce a resin composition. Using the obtained resin composition, a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after immersion in sulfuric acid were measured. Moreover, when an ultra-thin section was cut out from the press sheet and the ultra-thin section was observed with a transmission electron microscope, the aromatic polyetherketone resin (I-1) was particulated in the fluororesin (II-1). The dispersion was confirmed, and the average dispersed particle size of the aromatic polyetherketone resin (I-1) was calculated with the press sheet. And by using the obtained resin composition, the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire molding are determined by the above determination method. Judged. The results are shown in Table 1.

<Example 3>
Aromatic polyetherketone resin (I-2) and fluororesin (II-1) are premixed at the ratio (parts by mass) shown in Table 1, and a twin screw extruder (φ15 mm, L / D = 60) is used. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 395 ° C. and a screw rotation speed of 300 rpm to produce a resin composition. Using the obtained resin composition, a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after immersion in sulfuric acid were measured. Moreover, when an ultra-thin section was cut out from the press sheet and the ultra-thin section was observed with a transmission electron microscope, the aromatic polyetherketone resin (I-2) was particulated in the fluororesin (II-1). The dispersion was confirmed, and the average dispersed particle size of the aromatic polyetherketone resin (I-2) was calculated with the press sheet. And by using the obtained resin composition, the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire molding are determined by the above determination method. Judged. The results are shown in Table 1.

<Example 4>
Aromatic polyetherketone resin (I-2) and fluororesin (II-1) are premixed at the ratio (parts by mass) shown in Table 1, and a twin screw extruder (φ15 mm, L / D = 60) is used. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 395 ° C. and a screw rotation speed of 300 rpm to produce a resin composition. Using the obtained resin composition, a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after immersion in sulfuric acid were measured. Moreover, when an ultra-thin section was cut out from the press sheet and the ultra-thin section was observed with a transmission electron microscope, the aromatic polyetherketone resin (I-2) was particulated in the fluororesin (II-1). The dispersion was confirmed, and the average dispersed particle size of the aromatic polyetherketone resin (I-2) was calculated with the press sheet. And by using the obtained resin composition, the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire molding are determined by the above determination method. Judged. The results are shown in Table 1.

<Example 5>
Aromatic polyetherketone resin (I-1) and fluororesin (II-2) are premixed at the ratio (parts by mass) shown in Table 1, and a twin screw extruder (φ15 mm, L / D = 60) is used. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 395 ° C. and a screw rotation speed of 300 rpm to produce a resin composition. Using the obtained resin composition, a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after immersion in sulfuric acid were measured. Moreover, when an ultrathin section was cut out from the press sheet and the ultrathin section was observed with a transmission electron microscope, the aromatic polyetherketone resin (I-1) was particulated in the fluororesin (II-2). The dispersion was confirmed, and the average dispersed particle size of the aromatic polyetherketone resin (I-1) was calculated with the press sheet. And by using the obtained resin composition, the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire molding are determined by the above determination method. Judged. The results are shown in Table 1.

<Example 6>
Aromatic polyetherketone resin (I-2) and fluororesin (II-2) are premixed at the ratio (parts by mass) shown in Table 1, and a twin screw extruder (φ15 mm, L / D = 60) is used. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 395 ° C. and a screw rotation speed of 300 rpm to produce a resin composition. Using the obtained resin composition, a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after immersion in sulfuric acid were measured. Moreover, when an ultra-thin section was cut out from the press sheet and the ultra-thin section was observed with a transmission electron microscope, the aromatic polyetherketone resin (I-2) was particulated in the fluororesin (II-2). The dispersion was confirmed, and the average dispersed particle size of the aromatic polyetherketone resin (I-2) was calculated with the press sheet. And by using the obtained resin composition, the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire molding are determined by the above determination method. Judged. The results are shown in Table 1.

<Comparative Example 1>
Using only the aromatic polyether ketone resin (I-1), a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after sulfuric acid immersion were measured. And only using aromatic polyetherketone resin (I-1), the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and when performing wire molding The thickness unevenness was determined by the above determination method.

<Comparative Example 2>
Using only the fluororesin (II-1), a press sheet was prepared by the above-described method, and the dynamic friction coefficient, relative dielectric constant, and elongation retention after sulfuric acid immersion were measured. And using only fluororesin (II-1), the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire forming are described above. Judgment was made by the judging method. The results are shown in Table 1.

<Comparative Example 3>
Aromatic polyetherketone resin (I-3) and fluororesin (II-2) are premixed at the ratio (parts by mass) shown in Table 1, and a twin screw extruder (φ15 mm, L / D = 60) is used. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 395 ° C. and a screw rotation speed of 300 rpm to produce a resin composition. Using the obtained resin composition, a press sheet was prepared by the above-described method, and the dynamic friction coefficient, the relative dielectric constant, and the elongation retention after immersion in sulfuric acid were measured. Moreover, when an ultra-thin section was cut out from the press sheet and the ultra-thin section was observed with a transmission electron microscope, the aromatic polyetherketone resin (I-3) was particulated in the fluororesin (II-2). The dispersion was confirmed, and the average dispersed particle size of the aromatic polyetherketone resin (I-3) was calculated with the press sheet. And by using the obtained resin composition, the presence or absence of delamination when performing injection molding, thickness unevenness when performing extrusion molding, and thickness unevenness when performing wire molding are determined by the above determination method. Judged. The results are shown in Table 1.

The resin composition of the present invention is excellent in electrical characteristics, friction characteristics, chemical resistance, and can prevent delamination during injection molding. Also, during extrusion molding, the thickness unevenness of the extrudate and foreign matter, particularly thin film molding. In this case, it is possible to eliminate problems such as tearing and the like, and since it is excellent in moldability, it can be suitably used as a molding material for various industrial uses including electric wire coating applications and semiconductor component applications.

Claims (10)

A resin composition comprising an aromatic polyether ketone resin (I) and a fluororesin (II),
The fluororesin (II) is tetrafluoroethylene and the following general formula (1):
CF ₂ = CF-Rf ¹ (1)
(Wherein Rf ¹ represents —CF ₃ or —ORf ² ; Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms) Coalesced,
Aromatic polyether ketone resin (I) is dispersed in the form of particles in fluororesin (II),
The mass ratio of the fluororesin (II) to the total mass of the aromatic polyetherketone resin (I) and the fluororesin (II) is more than 50 mass% and 99 mass% or less, and the aromatic polyetherketone resin (I ) In the fluororesin (II) has a mean dispersed particle size of 1 μm or less. The resin composition according to claim 1, wherein the resin composition has a melt viscosity ratio (I) / (II) of the aromatic polyether ketone resin (I) and the fluororesin (II) of 1.0 to 5.0. object. The resin composition according to claim 1 or 2, wherein the fluororesin (II) has a melt flow rate of 0.1 to 100 g / 10 min. 4. The resin composition according to claim 1, wherein the aromatic polyether ketone resin (I) is a polyether ether ketone. By melt-kneading the Fang aromatic polyether ketone resin (I) with fluorine resin (II), the resin composition comprising the step of obtaining the claims 1 to 4 resin composition wherein the kneaded product Manufacturing method . A molded article formed from the resin composition according to claim 1, 2, 3 or 4 . The molded product according to claim 6, wherein the molded product is used for electric wire coating. The molded product according to claim 6, wherein the molded product is used for a semiconductor component application. A conductor (A);
An insulated wire having an insulating layer (B) formed on the outer periphery of the conductor (A),
An insulated wire, wherein the insulating layer (B) is formed from the resin composition according to claim 1, 2, 3 or 4 . A method for producing an insulated wire having a conductor (A) and an insulating layer (B),
The manufacturing method includes forming a resin composition according to claim 1, 2, 3, or 4 and forming an insulating layer (B) on the outer periphery of the conductor (A). Production method.