WO2022190656A2 - 絶縁電線及びその製造方法 - Google Patents
絶縁電線及びその製造方法 Download PDFInfo
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- WO2022190656A2 WO2022190656A2 PCT/JP2022/001811 JP2022001811W WO2022190656A2 WO 2022190656 A2 WO2022190656 A2 WO 2022190656A2 JP 2022001811 W JP2022001811 W JP 2022001811W WO 2022190656 A2 WO2022190656 A2 WO 2022190656A2
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- insulated wire
- less
- conductor
- mass
- filler
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Definitions
- the present disclosure relates to an insulated wire and a manufacturing method thereof.
- This application claims priority from Japanese Patent Application No. 2021-036490 filed on March 8, 2021. All the contents described in the Japanese patent application are incorporated herein by reference.
- insulated wires comprising a conductor and an insulating layer covering the conductor have been used in motors, transformers, and the like.
- the insulated wire of the present disclosure is An insulated wire comprising a conductor and an insulating layer covering the conductor,
- the insulating layer includes a resin and a first filler,
- the resin comprises polyimide,
- the first filler exists as primary particles or secondary particles in which a plurality of the primary particles are aggregated,
- the primary particles are silica or alumina,
- the secondary particles have a particle diameter of 0.03 ⁇ m or more and 5 ⁇ m or less, In the cross section of the insulated wire, the ratio of the total area of the secondary particles to the sum of the total area of the primary particles and the total area of the secondary particles is 50% or more.
- FIG. 1 is a cross-sectional photomicrograph illustrating one embodiment of an insulated wire of the present disclosure.
- FIG. 2 is a schematic cross-sectional (cross-sectional) view illustrating one aspect of the insulated wire of the present disclosure.
- FIG. 3 is a schematic cross-sectional (cross-sectional) view further illustrating one aspect of the insulated wire of the present disclosure.
- FIG. 4 is a schematic enlarged view of region IV in FIG.
- Patent Document 1 describes an insulated wire having at least two insulating layers on a conductor, in which at least one insulating layer (insulating layer A) contains inorganic compound particles, and an insulating layer A It is disclosed that the surge resistance of the insulated wire can be improved by setting the thickness of the insulated wire within a specific range.
- Patent Document 2 discloses a varnish containing silica fine particles having nano-sized hollows. It is described that the surge resistance of the insulated wire can be improved by manufacturing the insulated wire using the varnish.
- Patent Document 3 discloses a varnish containing a specific amount of phenyltrialkoxysilane. It is described that the surge resistance of the insulated wire can be improved by manufacturing the insulated wire using the varnish.
- an object of the present disclosure is to provide an insulated wire having excellent surge resistance.
- an insulated wire with excellent surge resistance can be provided.
- the insulated wire of the present disclosure is An insulated wire comprising a conductor and an insulating layer covering the conductor,
- the insulating layer includes a resin and a first filler,
- the resin comprises polyimide
- the first filler exists as primary particles or secondary particles in which a plurality of the primary particles are aggregated,
- the primary particles are silica or alumina
- the secondary particles have a particle diameter of 0.03 ⁇ m or more and 5 ⁇ m or less, In the cross section of the insulated wire, the ratio of the total area of the secondary particles to the sum of the total area of the primary particles and the total area of the secondary particles is 50% or more.
- the present disclosure can provide an insulated wire with excellent surge resistance.
- polyimide has excellent toughness. Therefore, the insulated wire of the present disclosure contains polyimide in the resin, and thus has excellent toughness.
- the ratio of the total area of the secondary particles having a particle diameter of 0.2 ⁇ m or more and 1 ⁇ m or less to the total area of the secondary particles is 30% or more. preferable. Thereby, the surge resistance of the insulated wire can be further enhanced.
- the ratio of the mass of the first filler to the mass of the insulating layer is preferably 5% or more and 30% or less. Thereby, the surge resistance of the insulated wire can be further enhanced.
- the polyimide is preferably a polymer of an acid dianhydride and a diamine compound. Thereby, the excellent surge resistance of the insulated wire and the excellent toughness of the insulating layer can be combined.
- the acid dianhydride is either one or both of pyromellitic dianhydride and 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and the diamine compound is 4, 4'-oxydianiline is preferred.
- the diamine compound is 4, 4'-oxydianiline is preferred.
- the acid dianhydride is composed of the pyromellitic dianhydride and the 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the pyromellitic dianhydride is 10 mol%. 50 mol % or more, and preferably 50 mol % or more and 90 mol % or less of the 3,3′,4,4′-biphenyltetracarboxylic dianhydride.
- ATF Automatic Transmission Fluid
- the insulated wire may come into contact with the ATF when used in a vehicle motor or the like.
- hydrolysis of the resin contained in the insulating layer forming the insulated wire is accelerated, and cracks may occur in the insulating layer.
- Polyimide generally has poor ATF resistance because it is susceptible to hydrolysis due to moisture in ATF.
- the acid dianhydride is composed of the pyromellitic dianhydride and the 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and the pyromellitic dianhydride is 10 mol % or more.
- ATF resistance the property of suppressing hydrolysis of the insulating layer caused by the contact of the insulated wire with ATF.
- the method for manufacturing an insulated wire of the present disclosure includes: A first step of preparing the conductor and an insulating varnish in the method for manufacturing the insulated wire; a second step of applying the insulating varnish to the outer peripheral surface of the conductor; a third step of baking the insulating varnish on the conductor, in this order;
- the first step includes an A step of preparing the conductor and a B step of preparing the insulating varnish,
- the insulating varnish is prepared by mixing a solvent, the first filler, and the resin or a resin precursor thereof, the solvent is N-methyl-2-pyrrolidone, N,N-dimethylacetamide, or a mixture thereof;
- the primary particles have a particle size of 0.01 ⁇ m or more and 0.1 ⁇ m or less. Thereby, it is possible to manufacture an insulated wire having excellent surge resistance.
- the third step is preferably performed under conditions of 300° C. to 700° C. and 0.1 minute to 5 minutes. This makes it possible to manufacture an insulated wire with better surge resistance.
- the resin solid content concentration in the insulating varnish is preferably 10% by mass or more and 40% by mass or less. This makes it possible to manufacture an insulated wire with better surge resistance.
- the mass ratio of the first filler to the mass of the resin solid content in the insulating varnish is preferably 5% or more and 35% or less. This makes it possible to manufacture an insulated wire with better surge resistance.
- this embodiment An embodiment of the present disclosure (hereinafter referred to as "this embodiment") will be described below. However, this embodiment is not limited to this.
- the notation of the form "A to B” means the upper and lower limits of the range (that is, from A to B). and the unit of B are the same.
- FIG. 2 is a schematic cross-sectional (cross-sectional) view illustrating one aspect of the insulated wire of the present disclosure.
- An insulated wire 10 (hereinafter sometimes simply referred to as an “insulated wire”) in the present disclosure includes a conductor 11 and an insulating layer 12 covering the conductor 11 (FIG. 2).
- “to cover” preferably covers the entire surface of the conductor 11, but as long as the effect of the present disclosure is exhibited, even if a part of the surface of the conductor 11 is not covered with the insulating layer 12, without departing from the scope of the disclosure.
- the insulated wire of the present disclosure may further include a base layer, an adhesion layer, a protective layer, a surface layer, a lubricating layer, and the like.
- the shape of the insulated wire is a linear body.
- a cross section of an insulated wire which will be described later, means a cross section that appears by cutting the insulated wire along a plane perpendicular to the longitudinal direction thereof.
- the cross-sectional shape of the insulated wire may be circular (including substantially circular) or flat.
- the insulated wire according to this embodiment includes the conductor as described above.
- Conductor means an electrical conductor.
- a metal having high electrical conductivity and high mechanical strength is preferable. Specific examples include copper, copper alloys, aluminum, aluminum alloys, nickel, silver, soft iron, steel, and stainless steel.
- the conductor may be a wire formed by forming these metals into a linear shape, a coated wire in which the surface of the wire is coated with another metal, or a stranded wire in which a plurality of wires are twisted together. There may be.
- Examples of the coated wire include, but are not limited to, nickel-coated copper wire, silver-coated copper wire, silver-coated aluminum wire, and copper-coated steel wire.
- the shape of the conductor is not particularly limited, and a round wire, square wire, etc. can be appropriately selected according to the intended use and electrical characteristics of the insulated wire. That is, in the cross section of the insulated wire, the cross-sectional shape of the conductor may be circular (including substantially circular) or rectangular. Also, the diameter or the length of the outer circumference of the conductor is not particularly limited, and can be appropriately selected according to the intended use and electrical properties of the insulated wire.
- the lower limit of the cross-sectional area of the conductor portion in the cross section of the insulated wire is preferably 0.01 mm 2 or more, more preferably 0.1 mm 2 or more, and the upper limit is preferably 40 mm 2 or less, more preferably 20 mm 2 or less. If the cross-sectional area of the conductor portion in the cross section of the insulated wire does not satisfy 0.01 mm 2 or more, the volume ratio of the insulating layer to the conductor increases, for example, the volumetric efficiency of the coil formed using the insulated wire decreases. There is a risk of If the cross-sectional area of the conductor portion in the cross section of the insulated wire exceeds 40 mm 2 or less, the copper loss due to eddy current increases, and the output efficiency of the coil may decrease.
- FIG. 3 is a schematic cross-sectional (cross-sectional) view further illustrating one aspect of the insulated wire of the present disclosure.
- the insulating layer 12 contains the resin 1 and the first filler (FIG. 3). Also, the insulating layer may further contain a curing agent, other additives, and a second filler.
- the curing agent has the function of curing the resin. Specifically, imidazole, triethylamine, titanium-based compounds, isocyanate-based compounds, blocked isocyanates, urea, melamine compounds, acetylene derivatives, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, aliphatic acid anhydrides, and aromatic group acid anhydrides.
- the titanium compound include tetrapropyl titanate, tetraisopropyl titanate, tetramethyl titanate, tetrabutyl titanate, tetrahexyl titanate, and the like.
- isocyanate-based compounds include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate, Aliphatic diisocyanates having 3 to 12 carbon atoms such as lysine diisocyanate; 1,4-cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), methylcyclohexane diisocyanate, isopropylidene Dicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanatomethylcyclohexane (hydrogenated XDI), hydrogen
- blocked isocyanate examples include diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-4,4'-diisocyanate, benzophenone-4,4 '-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, naphthylene-1,5-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, etc.
- MDI diphenylmethane-4,4'-diisocyanate
- diphenylmethane-3,3'-diisocyanate diphenylmethane-3,4'-diisocyanate
- Examples of the melamine compound include methylated melamine, butylated melamine, methylolated melamine, and butyrolated melamine.
- Examples of the acetylene derivative include ethynylaniline and ethynylphthalic anhydride.
- a nitrogen-containing compound such as a melamine compound is preferably used as the curing agent. This is because these curing agents have a high curing acceleration effect.
- the other additives mentioned above include antioxidants, UV inhibitors, and surface lubricity imparting agents.
- the second filler is a filler other than the first filler, and may contain one or more of such fillers.
- the thickness of the insulating layer is preferably 5 ⁇ m or more, and preferably 200 ⁇ m or less. If the thickness of the insulating layer is less than 5 ⁇ m, the insulating layer tends to be easily damaged, and the insulation of the conductor may become insufficient. If the thickness of the insulating layer exceeds 200 ⁇ m, the volume efficiency of the coil formed using the insulated wire tends to be low.
- the thickness of the insulation layer means the average thickness of the insulation layer in the cross section of the insulated wire. Specifically, a flat cross section is obtained by cross-sectional polishing at any five points in the longitudinal direction of the wire, and an image is taken with a microscope to measure the thickness of the insulating layer. An average value is calculated from the values obtained at each location, and this average value can be used as the thickness of the insulating layer.
- the resin includes polyimide.
- Polyimide is a polymer having imide bonds (--CONCO--) in its main chain. Polyimide is known to have excellent heat resistance. In addition, since polyimide has high toughness, even if the insulating layer contains secondary particles, which will be described later, the insulating layer can be prevented from breaking.
- Polyimide is preferably a polymer of an acid dianhydride and a diamine compound. In other words, the polyimide is preferably a polymer having a structure in which structural units derived from an acid dianhydride and structural units derived from a diamine compound are repeatedly bonded.
- the "acid dianhydride” is a structure in which two water molecules are eliminated from four carboxylic acid groups present in its own molecule (from two adjacent carboxylic acid groups in one molecule A compound having a structure in which two carboxylic acid group pairs exist, and one water molecule is eliminated from each carboxylic acid group pair.
- containing polyimide means that the resin may contain other resins than polyimide.
- Other resins include thermosetting resins such as polyvinyl formal resins, polyurethane resins, alkyl resins, epoxy resins, phenoxy resins, polyester resins, polyesterimide resins, polyesteramideimide resins, polyamideimide resins, and polyetherimide resins.
- Thermoplastic resins such as polyether ether ketone resins and polyether sulfone resins can be used.
- the acid dianhydride is, for example, pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (3,3′,4,4′ -Biphenyltetracarboxylic dianhydride (BPDA)), 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthal acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3 ,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane
- the diamine compounds include, for example, 4,4'-oxydianiline (ODA), m-phenylenediamine, silicone diamine, bis(3-aminopropyl) ether ethane, 3,3'- Diamino-4,4'dihydroxydiphenylsulfone (SO2 - HOAB), 4,4'diamino-3,3'dihydroxybiphenyl (HOAB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane (HOCF 3 AB), siloxane diamine, bis(3-aminopropyl) ether ethane, N,N-bis(3-aminopropyl) ether, 1,4-bis(3-aminopropyl) piperazine, isophorone diamine, 1 , 3′-bis(aminomethyl)cyclohexane, 3,3′-dimethyl-4,4′-diaminodicyclohexy
- the acid dianhydride is either one or both of pyromellitic dianhydride and 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and the diamine compound is 4,4′- Oxydianiline is preferred. According to this, since the interaction between polyimide molecules works strongly, it is possible to combine particularly excellent surge resistance and particularly excellent toughness of the insulating layer.
- the acid dianhydride is composed of pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride, and contains pyromellitic dianhydride at 10 mol% or more and 50 mol% or less. , 3,3′,4,4′-biphenyltetracarboxylic dianhydride in an amount of 50 mol % or more and 90 mol % or less. According to this, since the hydrolysis resistance can be improved, particularly excellent ATF resistance can be provided.
- the acid dianhydride is composed of pyromellitic dianhydride and 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and contains pyromellitic dianhydride at 10 mol % or more and 50 mol % or less. , 3,3′,4,4′-Biphenyltetracarboxylic dianhydride in an amount of 50 mol % or more and 90 mol % or less, after alkaline hydrolysis of the film component, 1 H NMR (proton nuclear magnetic resonance (Proton (Nuclear Magnetic Resonance)).
- the diamine compound is preferably composed of 4,4'-oxydianiline. According to this, since the hydrolysis resistance can be improved, particularly excellent ATF resistance can be provided.
- FIG. 3 is a schematic cross-sectional (cross-sectional) view further illustrating one aspect of the insulated wire of the present disclosure.
- FIG. 4 is a schematic enlarged view of region IV in FIG.
- the first filler is present as primary particles 2 or secondary particles 3 in which a plurality of primary particles are aggregated (Fig. 3).
- aggregated means a state in which particles larger than the primary particles 2 are formed by aggregation of a plurality of the primary particles 2, for example, in a beaded shape (FIG. 4).
- the state of contact between the primary particles in the secondary particles 3 may be a state in which they are merely in contact externally, or may be in a state of physical/chemical bonding or interaction such as Van der Waals force.
- the contact state is not particularly limited. Therefore, when observing the cross section of the insulated wire using a scanning electron microscope (SEM), if it is observed that two or more primary particles 2 are in contact with each other in the observation field, it is shall be interpreted as secondary particles 3.
- FIG. 1 is a micrograph of a cross section of an insulated wire. From FIG. 1, it is understood that in the insulating layer, the first filler exists as primary particles 2 or secondary particles 3 in which a plurality of primary particles are aggregated.
- distance between adjacent primary particles is 0.02 ⁇ m or less.
- distance between adjacent primary particles refers to two adjacent primary particles, connecting a point located on the outline of one primary particle and a point located on the outline of the other primary particle. It means the length of the shortest line segment (straight line).
- the primary particles are silica or alumina. Therefore, the secondary particles may be composed of either silica or alumina alone, or may be composed of both silica and alumina.
- the shape of the primary particles is not particularly limited. For example, any shape such as an irregular shape, a substantially spherical shape, a rugby ball shape, a polygonal shape, or the like may be used.
- the particle size of the primary particles is defined as the distance between the two most distant points on the outline of one primary particle in the cross section of the insulated wire. Moreover, the particle size of the primary particles means the average particle size. In addition, the particle size of the primary particles is determined by observing the cross section of the insulated wire using a scanning electron microscope (SEM), measuring the particle size of any 50 primary particles on the SEM image, and It is obtained by calculating the average value (average particle size) of the particle sizes of 50 primary particles.
- SEM scanning electron microscope
- the particle size of the primary particles is not particularly limited, it is preferably 0.01 ⁇ m or more and 0.1 ⁇ m or less.
- the secondary particles may be composed only of the primary particles, or may contain other components.
- the shape of the secondary particles is not particularly limited. For example, any shape such as an irregular shape, a substantially spherical shape, a rugby ball shape, a polygonal shape, or the like may be used.
- the particle diameter of the secondary particles 3 is defined as the distance D1 between the two most distant points on the outline of one secondary particle 3 in the cross section of the insulated wire (FIG. 4).
- the particle diameter of secondary particles means an average particle diameter.
- the particle diameter of the secondary particles is obtained by observing the cross section of the insulated wire using a scanning electron microscope (SEM), and after measuring the particle diameter of any 50 secondary particles on the SEM image. , is obtained by calculating the average value (average particle size) of the particle sizes of the 50 secondary particles.
- SEM scanning electron microscope
- the particle diameter of the secondary particles is 0.03 ⁇ m or more and 5 ⁇ m or less. As a result, volatilization of the resin can be physically suppressed, so excellent surge resistance and suitable toughness can be provided.
- the particle diameter of the secondary particles is preferably 0.1 ⁇ m or more, more preferably 0.15 ⁇ m or more, and even more preferably 0.2 ⁇ m or more. Also, the particle diameter of the secondary particles is preferably 3.0 ⁇ m or less, more preferably 1.5 ⁇ m or less, and even more preferably 1.0 ⁇ m or less.
- the particle diameter of the secondary particles is preferably 0.1 ⁇ m or more and 3.0 ⁇ m or less, more preferably 0.15 ⁇ m or more and 1.5 ⁇ m or less, and 0.2 ⁇ m or more and 1.0 ⁇ m or less. is more preferred.
- the ratio of the total area of the secondary particles to the sum of the total area of the primary particles and the total area of the secondary particles is desirably 50% or more.
- the "area of primary particles” means the area of primary particles other than the primary particles that constitute the secondary particles.
- the secondary particle area occupation ratio (%) is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more. Further, the secondary particle area occupation ratio (%) is preferably 90% or less.
- the secondary particle area occupation ratio (%) is more preferably 80% or less, and even more preferably 75% or less.
- the secondary particle area occupation ratio (%) is preferably 50% or more and 90% or less, more preferably 55% or more and 80% or less, and even more preferably 60% or more and 75% or less.
- the secondary particle area occupancy (%) is obtained by observing the cross section of the insulated wire using a scanning electron microscope (SEM), and calculating the total area of the primary particles and the total area of the secondary particles in a predetermined region. It is obtained by calculation using image processing software (“Winroof” manufactured by Mitani Shoji Co., Ltd.).
- the ratio of the total area of the secondary particles having a particle diameter of 0.2 ⁇ m or more and 1 ⁇ m or less to the total area of the secondary particles (hereinafter referred to as “particle diameter 0.2 to 1 ⁇ m (also referred to as “secondary particle area occupation ratio (%)”) is preferably 30% or more.
- the area occupation ratio (%) of secondary particles having a particle diameter of 0.2 to 1 ⁇ m is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more.
- the area occupation ratio (%) of secondary particles having a particle diameter of 0.2 to 1 ⁇ m is preferably 90% or less. As a result, it is possible to prevent the particle diameter of the particles from exceeding 5 ⁇ m due to excessive aggregation of the particles, and it is possible to avoid a decrease in the toughness of the insulating layer due to an increase in the particle diameter, so that the insulated wire is provided with suitable toughness. be able to.
- the area occupation ratio (%) of secondary particles having a particle diameter of 0.2 to 1 ⁇ m is more preferably 80% or less, further preferably 75% or less.
- the secondary particle area occupancy (%) with a particle diameter of 0.2 to 1 ⁇ m is preferably 50% or more and 90% or less, more preferably 55% or more and 80% or less, and 60% or more and 75% or less. is more preferable.
- the secondary particle area occupancy (%) with a particle size of 0.2 to 1 ⁇ m is obtained by observing the cross section of the insulated wire using a scanning electron microscope (SEM), and the area of the secondary particles occupying the area of the predetermined region. and the total area of secondary particles having a particle diameter of 0.2 ⁇ m or more and 1 ⁇ m or less using image processing software (“Winroof” manufactured by Mitani Shoji Co., Ltd.).
- the ratio of the mass of the first filler to the mass of the insulating layer is preferably 5% or more and 30% or less. According to this, it is possible to sufficiently combine excellent surge resistance and suitable toughness. When the ratio of the mass of the first filler to the mass of the insulating layer is less than 5%, it tends to be difficult to exhibit sufficient surge resistance. Moreover, when the ratio of the mass of the first filler to the mass of the insulating layer exceeds 30% or less, the flexibility of the insulating layer tends to deteriorate.
- the ratio of the mass of the first filler to the mass of the insulating layer is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.
- the ratio of the mass of the first filler to the mass of the insulating layer is preferably 30% or less, more preferably 26% or less, and even more preferably 23% or less. Further, the ratio of the mass of the first filler to the mass of the insulating layer is preferably 5% or more and 30% or less, more preferably 10% or more and 26% or less, and 15% or more and 23% or less. is more preferred.
- the ratio of the mass of the first filler to the mass of the insulating layer can be specified by measuring the residue of the insulating layer after heating (which is regarded as the weight of the filler) by thermogravimetry.
- the insulated wire according to the present disclosure has excellent surge resistance, electrical equipment using it can suppress dielectric breakdown caused by surges even when used under high voltage.
- electric devices include motors, transformers, and the like.
- the insulated wire according to the present disclosure can be manufactured by the following insulated wire manufacturing method, for example, from the viewpoint of manufacturing with high yield. That is, the method for manufacturing an insulated wire according to the present embodiment includes a step of preparing the conductor and insulating varnish (first step), a step of applying insulating varnish to the outer peripheral surface of the conductor (second step), and a step of baking the insulating varnish on the conductor (third step) in this order.
- the step of preparing the conductor and the insulating varnish (first step) includes a step of preparing the conductor (step A) and a step of preparing the insulating varnish (step B).
- the insulating varnish is prepared by mixing a solvent, the first filler, and the resin or a resin precursor thereof, and the solvent is N- characterized by being methyl-2-pyrrolidone, N,N-dimethylacetamide, or a mixture thereof.
- the primary particles have a particle diameter of 0.01 ⁇ m or more and 0.1 ⁇ m or less.
- the insulating varnish is obtained by mixing the solvent, the first filler, and the resin or its resin precursor under the conditions of a stirring time of 30 minutes or more and 180 minutes or less and a stirring speed of 20 rpm or more and 500 rpm or less. preferably prepared.
- the insulating varnish does not contain a silane coupling agent.
- the step of baking the insulating varnish on the conductor is preferably performed under the conditions of 300° C. or more and 700° C. or less and 0.1 minute or more and 5 minutes or less.
- the insulated wire obtained by performing the B step and the third step having such features can exhibit excellent surge resistance because it has the configuration described above.
- Each step included in the method for manufacturing an insulated wire according to this embodiment will be described in detail below.
- step A The step of preparing the conductor (step A) can be performed, for example, by obtaining a commercially available product. This step can also be carried out by obtaining a conductor by casting the metal described above as the material of the conductor, stretching it, drawing it into a wire, and further softening it.
- step B In the step of preparing the insulating varnish (step B), the resin described above as a material for the insulating layer, or a resin precursor thereof, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, or a mixture thereof (solvent) to obtain a resin solution, and disperse the first filler having a primary particle size of 0.01 ⁇ m or more and 0.1 ⁇ m or less in the resin solution.
- a polyimide precursor As a resin precursor, a polyimide precursor can be mentioned.
- the resin solid content concentration in the insulating varnish is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Moreover, the resin solid content concentration in the insulating varnish is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. The resin solid content concentration in the insulating varnish is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less.
- the "resin solid content concentration” means the resin concentration when the insulating varnish contains only the resin among the above resin and its resin precursor, and the insulating varnish contains only the resin precursor among the above resin and its resin precursor.
- the insulating varnish contains both the resin and its resin precursor, it means the concentration of the resin precursor, respectively.
- the ratio of the mass of the first filler to the mass of the resin solid content in the insulating varnish is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. Also, the ratio of the mass of the first filler to the mass of the resin solid content in the insulating varnish is preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less. Further, the mass ratio of the first filler to the mass of the resin solid content in the insulating varnish is preferably 5% or more and 35% or less, more preferably 10% or more and 30% or less, and even more preferably 15% or more and 25% or less. .
- the "mass of resin solid content” means the mass of the resin when the insulating varnish contains only the resin among the above resin and its resin precursor, and the insulating varnish is the resin precursor among the above resin and its resin precursor. If it contains only the resin precursor, it means the mass of the resin precursor, and if the insulating varnish contains both the resin and its resin precursor, it means the total mass of both.
- the insulating varnish includes the above-described N-methyl-2-pyrrolidone, N,N-dimethylacetamide, or a mixture thereof (solvent), a resin or a resin precursor thereof, a first filler, in addition to other solvents,
- solvent solvent
- the insulating varnish preferably does not contain a silane coupling agent.
- a known organic solvent can be used as the other solvent.
- polar organic solvents such as N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexaethylphosphoric acid triamide, and ⁇ -butyrolactone; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester-based organic solvents such as methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; ether-based organic solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol dimethyl ether, and tetrahydrofuran; hexane , heptane, benzene, toluene, and x
- the ratio is preferably 10% by mass or more and 50% by mass or less with respect to N-methyl-2-pyrrolidone, N,N-dimethylacetamide, or a mixture thereof.
- the above step B is preferably carried out by mixing the above components under the conditions of a stirring time of 30 minutes or more and 180 minutes or less and a stirring speed of 20 rpm or more and 500 rpm or less.
- the step of applying insulating varnish to the outer peripheral surface of the conductor is a step of applying the prepared varnish to the outer peripheral surface of the conductor.
- the coating method is not particularly limited, and conventionally known coating methods can be used. For example, when a coating die having openings is used, the varnish can be applied in a uniform thickness and the surface of the applied varnish can be made smooth.
- the step of baking the insulating varnish on the conductor is a step of forming an insulating layer by baking. Specifically, the varnished conductor is placed in a baking furnace to bake the varnish.
- the step of baking the insulating varnish onto the conductor (third step) is preferably performed under the conditions of 300° C. or higher and 700° C. or lower and 0.1 minute or longer and 5 minutes or shorter.
- an insulated wire including a conductor and an insulating layer covering the conductor is manufactured.
- the second step and the third step may be repeated until the insulating layer laminated on the surface of the conductor has a predetermined thickness.
- Insulated wires of Examples 1 to 7, Comparative Examples 1 and 2 were produced as follows. First, a conducting wire (metal type: tough pitch copper) with an average diameter of 1 mm was prepared (A process). Next, an acid dianhydride and a diamine compound shown in Table 1 were dissolved in N-methyl-2-pyrrolidone and reacted to obtain a polyimide precursor solution (resin solution) having a concentration of 25 wt %. Insulating varnish is obtained by dispersing a first filler that is silica and has a primary particle diameter of 0.03 ⁇ m in the resin solution at 20% by mass with respect to the polyimide precursor (resin solid content). prepared (step B).
- the insulating varnish was applied to the outer peripheral surface of the conductor using a coating die to manufacture a conductor coated with the insulating varnish (second step).
- the conductor coated with the insulating varnish was placed in a baking furnace and baked at 450° C. for 90 seconds (third step).
- an insulating layer having an insulating layer thickness ( ⁇ m) shown in Table 1 (measurement method is as described above) was formed, and an insulated wire was manufactured.
- Insulated wires of Examples 1 to 4, Example 7, Comparative Example 1, and Comparative Example 2 having the configurations shown in Table 1 were manufactured by performing the above steps.
- the mol% of the acid dianhydride is changed as shown in Table 1, and the first filler in the resin solution is 10 mass with respect to the polyimide precursor (resin solid content).
- the insulated wire of Example 5 was manufactured by performing the same steps as in Example 3, except that the insulated wire of Example 5 was dispersed in %. Further, in the above step B, the first filler is dispersed in the resin solution at 15% by mass with respect to the polyimide precursor (resin solid content), and the thickness ( ⁇ m) of the insulating layer (measurement method is as described above).
- the insulated wire of Example 6 was manufactured by performing the same steps as in Example 5, except that was changed as shown in Table 1.
- ⁇ Surge resistance test The insulated wires of Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to a surge resistance test in the following procedure. That is, according to the methods specified in JISC3003 and IEC60851-5, a stranded wire sample was produced by twisting two insulated wires and evaluated.
- the detailed test conditions are as follows. (Test conditions) ⁇ Waveform: Rectangular wave ⁇ Frequency: 20 kHz ⁇ Voltage: 1,500V ⁇ Temperature of atmosphere: 155°C
- the endurance time means the time until a short circuit occurs due to dielectric breakdown between two stranded wires (insulated wires) in the endurance test under the above test conditions. It means that the longer the endurance time, the better the surge resistance of the insulated wire.
- an insulated wire with an endurance time of 45 hours or longer is defined as having good surge resistance. The results of the tests are shown in Table 1.
- Example 1 to 7 and Comparative Examples 1 and 2 were subjected to an ATF resistance test in the following procedure. That is, the winding sample was immersed in ATF oil containing 0.5% by mass of water in a sealed SUS container, heated in an environment of 150 ° C. for 1000 hours in a sealed state, and then the winding sample was taken out and coated. The presence or absence of cracks was evaluated. The results are shown in Table 1.
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Description
導体と、該導体を被覆する絶縁層と、を備える絶縁電線であって、
該絶縁層は、樹脂と第1のフィラーとを含み、
該樹脂は、ポリイミドを含み、
該第1のフィラーは、一次粒子、または該一次粒子の複数が集合した二次粒子として存在し、
該一次粒子は、シリカまたはアルミナであり、
該二次粒子の粒子径は、0.03μm以上5μm以下であり、
該絶縁電線の横断面において、該一次粒子の面積の合計値と、該二次粒子の面積の合計値との和に対する、該二次粒子の面積の合計値の割合が50%以上である。
[本開示の効果]
最初に本開示の実施態様を列記して説明する。
[1]本開示の絶縁電線は、
導体と、該導体を被覆する絶縁層と、を備える絶縁電線であって、
該絶縁層は、樹脂と第1のフィラーとを含み、
該樹脂は、ポリイミドを含み、
該第1のフィラーは、一次粒子、または該一次粒子の複数が集合した二次粒子として存在し、
該一次粒子は、シリカまたはアルミナであり、
該二次粒子の粒子径は、0.03μm以上5μm以下であり、
該絶縁電線の横断面において、該一次粒子の面積の合計値と、該二次粒子の面積の合計値との和に対する、該二次粒子の面積の合計値の割合が50%以上である。
上記絶縁電線の製造方法であって、上記導体と絶縁ワニスとを準備する第1工程と、
上記導体の外周面に上記絶縁ワニスを塗布する第2工程と、
上記絶縁ワニスを上記導体に焼付ける第3工程と、をこの順で含み、
上記第1工程は、上記導体を準備するA工程と、上記絶縁ワニスを準備するB工程とを含み、
上記B工程において上記絶縁ワニスは、溶剤と上記第1のフィラーと上記樹脂またはその樹脂前駆体とを混合することにより調製され、
上記溶剤は、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、又はそれらの混合物であり、
上記第1のフィラーにおいて、上記一次粒子の粒子径が0.01μm以上0.1μm以下である。これにより、優れた耐サージ性を有する絶縁電線を製造することが可能である。
以下、本開示の一実施形態(以下「本実施形態」と記す。)について説明する。ただし、本実施形態はこれに限定されるものではない。本明細書において「A~B」という形式の表記は、範囲の上限下限(すなわちA以上B以下)を意味し、Aにおいて単位の記載がなく、Bにおいてのみ単位が記載されている場合、Aの単位とBの単位とは同じである。
図2は、本開示の絶縁電線の一態様を例示する模式断面(横断面)図である。本開示における絶縁電線10(以下、単に「絶縁電線」という場合がある。)は、導体11と、上記導体11を被覆する絶縁層12と、を備える(図2)。ここで、「被覆する」とは、導体11の表面の全面を被覆することが好ましいが、本開示の効果を示す限り導体11の表面の一部が絶縁層12によって被覆されていなくても本開示の範囲を逸脱するものではない。また、本開示の絶縁電線は、更に下地層、密着層、保護層、表面層、潤滑層などを含んでも良い。
本実施形態に係る絶縁電線は、上述のように導体を備える。導体とは、電気伝導体を意味する。導体の材料としては、導電率が高くかつ機械的強度の高い金属が好ましい。具体的には、銅、銅合金、アルミニウム、アルミニウム合金、ニッケル、銀、軟鉄、鋼、ステンレス鋼などが挙げられる。導体は、これらの金属を線状に形成した素線であってもよく、素線の表面を他の金属で被覆した被覆線であってもよく、複数の素線を撚り合わせた撚線であってもよい。上記被覆線としては、ニッケル被覆銅線、銀被覆銅線、銀被覆アルミニウム線、銅被覆鋼線などが挙げられるが、これらに限定されるものではない。
図3は、本開示の絶縁電線の一態様を更に例示する模式断面(横断面)図である。絶縁層12は、樹脂1と第1のフィラーとを含む(図3)。また、絶縁層は、更に硬化剤、その他の添加剤、第2のフィラーを含んでも良い。
上記樹脂は、ポリイミドを含む。ポリイミドは、主鎖中にイミド結合(-CONCO-)を有する高分子である。ポリイミドは、耐熱性に優れることが知られている。また、ポリイミドは、靱性が高い為、後述する二次粒子を絶縁層に含有しても、絶縁層の破断を防止することができる。ポリイミドは、酸二無水物とジアミン化合物との重合体であることが好ましい。換言すれば、ポリイミドは、酸二無水物に由来する構成単位とジアミン化合物に由来する構成単位とが繰り返し結合した構造を有するポリマーであることが好ましい。ここで、「酸二無水物」とは、自己の分子中に存在する4個のカルボン酸基から2個の水分子が脱離した構造(一分子中において隣接する2個のカルボン酸基からなるカルボン酸基ペアーが2組存在し、各カルボン酸基ペアーから水1分子が脱離した構造)の化合物を指す。また、「ポリイミドを含む」とは、樹脂がポリイミド以外の他の樹脂を含んでもよいことを意味する。他の樹脂としては、ポリビニルホルマール樹脂、ポリウレタン樹脂、アルキル樹脂、エポキシ樹脂、フェノキシ樹脂、ポリエステル樹脂、ポリエステルイミド樹脂、ポリエステルアミドイミド樹脂、ポリアミドイミド樹脂などの熱硬化性樹脂、およびポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルサルフォン樹脂などの熱可塑性樹脂が挙げられる。
図3は、本開示の絶縁電線の一態様を更に例示する模式断面(横断面)図である。図4は、図3の領域IVの模式的な拡大図である。上記第1のフィラーは、一次粒子2、または一次粒子の複数が集合した二次粒子3として存在する(図3)。ここで、「集合した」とは、上記一次粒子2の複数がたとえば数珠状に凝集することによって一次粒子2より大きな粒子が形成された状態を意味する(図4)。この場合、二次粒子3中における一次粒子間の接触の状態は、単に外観的に接触している状態であっても良いし、ファンデルワールス力等の相互作用や物理的/化学的結合を伴う状態であっても良く、その接触状態は特に限定されない。したがって、走査型電子顕微鏡(SEM(Scanning Electron Microscopy))を用いて絶縁電線の横断面を観察した場合に、観察視野において2以上の一次粒子2が接触しているように観察される場合、それを二次粒子3として解するものとする。図1は、絶縁電線の横断面の顕微鏡写真である。図1から、絶縁層において、第1のフィラーは、一次粒子2、または一次粒子の複数が集合した二次粒子3として存在することが理解される。
本開示に係る絶縁電線は、たとえば歩留まり良く製造する観点から、以下の絶縁電線の製造方法により製造することができる。すなわち本実施形態に係る絶縁電線の製造方法は、上記導体と絶縁ワニスとを準備する工程(第1工程)と、上記導体の外周面に絶縁ワニスを塗布する工程(第2工程)と、上記絶縁ワニスを導体に焼付ける工程(第3工程)と、をこの順で含む。また、上記導体と絶縁ワニスとを準備する工程(第1工程)は、導体を準備する工程(A工程)と、絶縁ワニスを準備する工程(B工程)とを含む。
(A工程)
上記導体を準備する工程(A工程)は、たとえば市販品を入手することによって実行できる。また導体の材料として上述した金属を鋳造し、延伸し、線状に伸線し、さらに軟化させることによって導体を得ることにより、本工程を実行することもできる。
上記絶縁ワニスを準備する工程(B工程)は、絶縁層の材料として上述した樹脂、またはその樹脂前駆体をN-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、又はそれらの混合物(溶剤)で溶解することにより樹脂溶液を得、当該樹脂溶液に一次粒子の粒子径が0.01μm以上0.1μm以下である第1のフィラーを分散させることにより実行できる。
上記導体の外周面に絶縁ワニスを塗布する工程(第2工程)は、調製されたワニスを導体の外周面に塗布する工程である。塗布方法は特に限定されず、従来公知の塗布方法を用いることができる。たとえば開口部を有する塗布ダイスを用いた場合、ワニスを均一な厚さで塗布することができるとともに、塗布されたワニスの表面を平滑にすることができる。
上記絶縁ワニスを導体に焼付ける工程(第3工程)は、焼き付け処理により絶縁層を形成する工程である。具体的には、ワニスが塗布された導体を焼き付け炉内に配置してワニスを焼き付ける。絶縁ワニスを導体に焼付ける工程(第3工程)は、300℃以上700℃以下、0.1分以上5分以下の条件で実行されることが好ましい。
以下のようにして、実施例1~実施例7、比較例1、比較例2の絶縁電線を製造した。まず、平均直径1mmの導線(金属種:タフピッチ銅)を準備した(A工程)。次いで、表1に示す酸二無水物とジアミン化合物とをN-メチル-2-ピロリドンに溶解しこれら両者を反応させることにより、25wt%濃度のポリイミド前駆体溶液(樹脂溶液)を得た。当該樹脂溶液に一次粒子の粒子径が0.03μmであり、且つ、シリカである第1のフィラーを、ポリイミド前駆体(樹脂固形分)に対して20質量%で分散させることにより、絶縁ワニスを準備した(B工程)。次いで、上記導体の外周面に塗布ダイスを用いて上記絶縁ワニスを塗布することにより、絶縁ワニスが塗布された導体を製造した(第2工程)。次いで、上記絶縁ワニスが塗布された導体を焼き付け炉内に配置し、450℃、90秒の条件で焼き付けを行った(第3工程)。当該第2工程と当該第3工程とを所定の回数繰り返すことで、表1に示す絶縁層の厚み(μm)(測定方法は上記の通り)を有する絶縁層を形成し、絶縁電線を製造した。以上の工程を実行することにより、表1に示した構成を有する実施例1~実施例4、実施例7、比較例1、比較例2の各絶縁電線を製造した。また、上記B工程において、酸二無水物のmol%が表1に示されるように変更されることと、樹脂溶液に第1のフィラーを、ポリイミド前駆体(樹脂固形分)に対して10質量%で分散させることとを除いては、実施例3と同様の工程を実行することにより、実施例5の絶縁電線を製造した。また、上記B工程において樹脂溶液に第1のフィラーを、ポリイミド前駆体(樹脂固形分)に対して15質量%で分散させることと、絶縁層の厚み(μm)(測定方法は上記の通り)が表1に示されるように変更されることとを除いては、実施例5と同様の工程を実行することにより、実施例6の絶縁電線を製造した。
実施例1~実施例7、比較例1、比較例2の絶縁電線について、絶縁層の質量に対する第1のフィラーの質量の割合は、上記の方法により求めた。得られた結果を表1の「絶縁層の質量に対する第1のフィラーの質量の割合(%)」の項に記す。
実施例1~実施例7、比較例1、比較例2の絶縁電線について、二次粒子面積占有率(%)および粒子径0.2~1μmの二次粒子面積占有率(%)は、上記の方法により求めた。得られた結果をそれぞれ表1の「二次粒子面積占有率(%)」の項、表1の「粒子径0.2~1μmの二次粒子面積占有率(%)」の項に記す。
実施例1~実施例7、比較例1、比較例2の絶縁電線について、以下の手順で耐サージ性試験を行った。すなわち、JISC3003およびIEC60851-5に規定された手法に則り、2本の絶縁電線を撚り合わせた撚線試料を製造して評価した。なお、詳細な試験の条件は以下の通りである。
(試験の条件)
・波形:矩形波
・周波数:20kHz
・電圧:1,500V
・雰囲気の温度:155℃
ここで、耐久時間とは、上記試験条件下の耐久試験において、2本の撚線の線(絶縁電線)間で絶縁破壊が起こり、ショートするまでの時間を意味する。耐久時間が長いほど、絶縁電線の耐サージ性に優れることを意味する。また、この試験において、耐久時間が45h以上の絶縁電線は、耐サージ性が良好であることと定義する。試験の結果を、表1に示す。
BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(3,3’、4,4’-Biphenyltetracarboxylic dianhydride)
ODA:4,4’-オキシジアニリン(4,4’-Oxydianiline)
表1の結果から、実施例1~実施例7の絶縁電線は、比較例1および比較例2の絶縁電線に比して、優れた耐サージ性を有することが分かった。なお、実施例1~実施例7、比較例1および比較例2の絶縁電線に用いられたフィラーは、シリカのみであったが、アルミナがシリカと同じく絶縁性が高い粒子であるという理由で、シリカをアルミナに置き換えた場合、および、シリカとアルミナとを組み合わせた場合においても、同様の効果を奏するものと予想される。
実施例1~実施例7、比較例1、比較例2の絶縁電線について、以下の手順で耐ATF性試験を行った。すなわち、SUS製密閉容器内で0.5質量%の水を含有させたATFオイル中に巻線サンプルを浸漬させ、密閉状態で150℃の環境下で1000h加熱した後、巻線サンプルを取り出し皮膜の割れ発生有無を評価した。結果を、表1に示す。
Claims (10)
- 導体と、前記導体を被覆する絶縁層と、を備える絶縁電線であって、
前記絶縁層は、樹脂と第1のフィラーとを含み、
前記樹脂は、ポリイミドを含み、
前記第1のフィラーは、一次粒子、または前記一次粒子の複数が集合した二次粒子として存在し、
前記一次粒子は、シリカまたはアルミナであり、
前記二次粒子の粒子径は、0.03μm以上5μm以下であり、
前記絶縁電線の横断面において、前記一次粒子の面積の合計値と、前記二次粒子の面積の合計値との和に対する、前記二次粒子の面積の合計値の割合が50%以上である、絶縁電線。 - 前記横断面において、前記二次粒子の面積の合計値に対する、粒子径が0.2μm以上1μm以下である前記二次粒子の面積の合計値の割合が30%以上である、請求項1に記載の絶縁電線。
- 前記絶縁層の質量に対する前記第1のフィラーの質量の割合は、5%以上30%以下である、請求項1又は請求項2に記載の絶縁電線。
- 前記ポリイミドは、酸二無水物とジアミン化合物との重合体である、請求項1から請求項3のいずれか1項に記載の絶縁電線。
- 前記酸二無水物は、ピロメリット酸二無水物および3,3’,4,4’-ビフェニルテトラカルボン酸二無水物のいずれか一方又は両方であり、
前記ジアミン化合物は、4,4’-オキシジアニリンである、請求項4に記載の絶縁電線。 - 前記酸二無水物は、前記ピロメリット酸二無水物と前記3,3’,4,4’-ビフェニルテトラカルボン酸二無水物とからなり、
前記ピロメリット酸二無水物を10mol%以上50mol%以下で含み、
前記3,3’,4,4’-ビフェニルテトラカルボン酸二無水物を50mol%以上90mol%以下で含む、請求項5に記載の絶縁電線。 - 請求項1から請求項6のいずれか1項に記載の絶縁電線の製造方法であって、
前記導体と絶縁ワニスとを準備する第1工程と、
前記導体の外周面に前記絶縁ワニスを塗布する第2工程と、
前記絶縁ワニスを前記導体に焼付ける第3工程と、をこの順で含み、
前記第1工程は、前記導体を準備するA工程と、前記絶縁ワニスを準備するB工程とを含み、
前記B工程において前記絶縁ワニスは、溶剤と前記第1のフィラーと前記樹脂またはその樹脂前駆体とを混合することにより調製され、
前記溶剤は、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、又はそれらの混合物であり、
前記第1のフィラーにおいて、前記一次粒子の粒子径が0.01μm以上0.1μm以下である、絶縁電線の製造方法。 - 前記第3工程は、300℃以上700℃以下、0.1分以上5分以下の条件で実行される、請求項7に記載の絶縁電線の製造方法。
- 前記絶縁ワニスにおける樹脂固形分濃度は、10質量%以上40質量%以下である、請求項7又は請求項8に記載の絶縁電線の製造方法。
- 前記絶縁ワニス中の樹脂固形分の質量に対する第1のフィラーの質量の割合は、5%以上35%以下である、請求項7から請求項9のいずれか1項に記載の絶縁電線の製造方法。
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