WO2024257813A1 - Alliage de cuivre, et matériau résistif pour résistance, résistance, matériau pour élément chauffant ainsi qu'élément chauffant mettant en œuvre cet alliage de cuivre - Google Patents

Alliage de cuivre, et matériau résistif pour résistance, résistance, matériau pour élément chauffant ainsi qu'élément chauffant mettant en œuvre cet alliage de cuivre Download PDF

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WO2024257813A1
WO2024257813A1 PCT/JP2024/021380 JP2024021380W WO2024257813A1 WO 2024257813 A1 WO2024257813 A1 WO 2024257813A1 JP 2024021380 W JP2024021380 W JP 2024021380W WO 2024257813 A1 WO2024257813 A1 WO 2024257813A1
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mass
copper alloy
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copper
resistance
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Japanese (ja)
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紳悟 川田
司 高澤
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/05—Alloys based on copper with manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C13/00—Resistors not provided for elsewhere
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material

Definitions

  • the present invention relates to copper alloy materials and resistance materials for resistors, resistors, materials for heating elements, and heating elements that use the same.
  • Cu-Mn-Ni alloys are widely used as copper-based resistance materials for resistors. It is known that this Cu-Mn-Ni alloy has a high volume resistivity ⁇ and a small absolute value of the temperature coefficient of resistance (TCR) due to its high manganese content.
  • TCR temperature coefficient of resistance
  • T in the formula indicates the test temperature (° C.)
  • T 0 indicates the reference temperature (° C.)
  • R indicates the resistance value ( ⁇ ) at the test temperature T
  • R 0 indicates the resistance value ( ⁇ ) at the reference temperature T 0 .
  • Non-Patent Document 1 describes an alloy symbolized as GCM44, which contains Mn in the range of 10.0 mass% to 13.0 mass%, Ni in the range of 1.0 mass% to 4.0 mass%, the total amount of Cu+Mn+Ni is 98.0 mass% or more, and has an electrical resistance (volume resistivity ⁇ ) of 44 [ ⁇ cm].
  • Such conventional copper alloys are used in resistors as well as heater wires and other heating elements, and are characterized by a small temperature dependency of electrical resistance in operating environments below 100°C, for example, and therefore a small positive temperature coefficient of resistance (TCR).
  • TCR temperature coefficient of resistance
  • the resistance value decreases significantly, and the temperature coefficient of resistance (TCR) of the copper alloy becomes a large negative number.
  • TCR temperature coefficient of resistance
  • copper alloys used in resistors and heating elements are preferably ones with a high volume resistivity ⁇ in order to improve the precision of the resistors, but if the resistance value is made higher than necessary, the power consumption of the resistor or heating element increases, and in particular, there is a problem in that the energy loss due to heat generation increases. Therefore, there has been a demand for copper alloys that can be used in resistors and heating elements and have an appropriate volume resistivity ⁇ in a range that can reduce energy loss due to heat generation.
  • the copper alloys used in heating elements can achieve the desired resistance value and heat generation amount by changing the cross-sectional area, but if the resistance value is larger than necessary, the cross-sectional area of the heating element must be increased, which can reduce the workability of the heating element and increase its weight.
  • the temperature coefficient of resistance (TCR) is a large positive number as described above, the resistance value increases within the operating temperature range, creating problems with temperature control, so there was a demand for copper alloys with an appropriate volume resistivity ⁇ and a small absolute value of the temperature coefficient of resistance (TCR).
  • the object of the present invention is therefore to provide a copper alloy material having a volume resistivity in a desired range, a small absolute value of the thermoelectromotive force against copper, and a temperature coefficient of resistance that is zero or a negative number with a small absolute value over a wide temperature range from room temperature (e.g., 20°C) to high temperature (e.g., 150°C), as well as a resistance material for resistors, resistors, materials for heating elements, and heating elements using the same.
  • the inventors have discovered that by using an alloy composition containing Mn: 7.0% by mass to 17.0% by mass, Ni: 0.1% by mass to 3.0% by mass, and Al: 1.0% by mass to 5.0% by mass, with the remainder being Cu and unavoidable impurities, it is possible to obtain a copper alloy material that has a volume resistivity ⁇ in the desired range, a small absolute value of the thermoelectromotive force (EMF) against copper, and a temperature coefficient of resistance that is 0 or a negative number and has a small absolute value over a wide temperature range from room temperature (e.g., 20°C) to high temperature (e.g., 150°C), and have thus completed the present invention.
  • EMF thermoelectromotive force
  • the gist of the present invention is as follows.
  • the copper alloy material according to (1) or (2) above, wherein the alloy composition further contains Co: 0.01 mass% or more and 1.30 mass% or less.
  • the present invention can provide copper alloy materials having a volume resistivity in a desired range, a small absolute value of the thermoelectromotive force against copper, and a temperature coefficient of resistance that is zero or a negative number with a small absolute value over a wide temperature range from room temperature (e.g., 20°C) to high temperature (e.g., 150°C), as well as resistance materials for resistors, resistors, materials for heating elements, and heating elements using the same.
  • FIG. 2 is a schematic diagram for explaining a method for determining the thermoelectromotive force (EMF) against copper for the test materials of the present invention and the comparative example.
  • EMF thermoelectromotive force
  • the copper alloy material according to the present invention has an alloy composition containing Mn: 7.0% by mass to 17.0% by mass, Ni: 0.1% by mass to 3.0% by mass, and Al: 1.0% by mass to 5.0% by mass, with the remainder being Cu and unavoidable impurities.
  • Mn is contained in the range of 7.0 mass% to 17.0 mass%
  • Ni is contained in the range of 0.1 mass% to 3.0 mass%
  • Al is contained in the range of 1.0 mass% to 5.0 mass%, so that the absolute value of the copper thermoelectromotive force (EMF) generated between temperature environments of 0°C and 80°C (hereinafter, sometimes simply referred to as "copper thermoelectromotive force”) is smaller than that in the case where Al is not contained, so that it is possible to improve the precision of resistors even in high-temperature environments, and also to improve the performance of heating elements.
  • EMF copper thermoelectromotive force
  • the copper alloy material of the present invention has a volume resistivity ⁇ in a range useful as a resistance material or heating element material with small energy loss due to heat generation, and the absolute value of the copper thermoelectromotive force (EMF) can be reduced.
  • EMF copper thermoelectromotive force
  • the temperature coefficient of resistance (hereinafter, sometimes simply referred to as "temperature coefficient of resistance”) in a wide temperature range from room temperature (e.g., 20°C) to high temperature (e.g., 150°C). More specifically, by containing Mn in the range of 7.0 mass% to 17.0 mass% and Al in the range of 1.0 mass% to 5.0 mass%, the temperature coefficient of resistance (TCR) can be set to 0 or a small absolute value in the temperature range from 20°C to 150°C, including higher temperatures.
  • the copper alloy material is used as a resistance material for resistors, etc.
  • the adverse effects of the high temperature coefficient of resistance of the conductor metal joined to the copper alloy material can be reduced.
  • the conductor metal is copper
  • the temperature coefficient of resistance of copper is large at about 4000 ppm/°C, so that the resistance value differs depending on the temperature change of the conductor. Even when using such metals, by combining them with the copper alloy material of the present invention, it is possible to reduce the adverse effects on the resistance value caused by temperature changes in the conductor.
  • the copper alloy described in the above-mentioned non-patent document 1 is described as having an average temperature coefficient of +50 ⁇ 10 ⁇ 6 [° C. ⁇ 1 ] in the temperature range from 23° C. to 100° C. with respect to the temperature dependence of electrical resistance.
  • the copper alloy described in the non-patent document 1 has a large drop in electrical resistance at high temperatures close to 150° C., and therefore has a large negative temperature coefficient of resistance (TCR) in the temperature range from 20° C. to 150° C., including the higher temperature range, and is therefore prone to errors in resistance values, particularly in the high temperature range.
  • TCR negative temperature coefficient of resistance
  • the copper alloy material according to the present invention can have a temperature coefficient of resistance (TCR) of 0 or a negative number with a small absolute value in a wide temperature range from room temperature (e.g., 20° C.) to high temperature (e.g., 150° C.).
  • TCR temperature coefficient of resistance
  • the copper alloy material according to the present invention has a volume resistivity ⁇ in the desired range, a small absolute value of the thermoelectromotive force (EMF) against copper, and a temperature coefficient of resistance (TCR) that is 0 or a negative number with a small absolute value, and it is also possible to provide a copper alloy material, as well as a resistance material for resistors, resistors, materials for heating elements, and heating elements using the same.
  • EMF thermoelectromotive force
  • TCR temperature coefficient of resistance
  • the alloy composition of the copper alloy material of the present invention contains, as essential components, Mn: 7.0 mass% or more and 17.0 mass% or less, Ni: 0.1 mass% or more and 3.0 mass% or less, and Al: 1.0 mass% or more and 5.0 mass% or less.
  • Mn 7.0 mass% or more and 17.0 mass% or less
  • Mn manganese
  • TCR temperature coefficient of resistance
  • the Mn content is preferably 7.0 mass % or more, more preferably 9.0 mass % or more, and further preferably 10.0 mass % or more.
  • the resistance temperature coefficient The effect of making the TCR negative is largely due to the increase in the Mn content.
  • the Mn content is 17.0 mass% or less, and in particular, 14.0 mass% More specifically, the Mn content in the alloy composition is preferably in the range of 7.0 mass % to 14.0 mass %. In particular, in the case where the first optional additional component described later is not contained, the Mn content is preferably 14.0 mass % or less from the viewpoint of further reducing the absolute value of the thermal electromotive force (EMF) against copper.
  • EMF copper thermoelectromotive force
  • TCR temperature coefficient of resistance
  • Ni 0.1% by mass or more and 3.0% by mass or less
  • Ni (nickel) is an element that reduces the absolute value of the thermoelectromotive force (EMF) against copper.
  • Mn adjusts the thermoelectromotive force (EMF) against copper, which becomes a large negative number, in the positive direction.
  • Ni is contained in an amount of 0.1 mass% or more.
  • the Ni content exceeds 3.0 mass%, the aluminum and compound described later are formed. Therefore, the effect of reducing the absolute value of the thermal electromotive force (EMF) against copper cannot be sufficiently obtained. For this reason, the Ni content is set to be within the range of 0.1 mass % to 3.0 mass %. It is.
  • Al is an element that reduces the absolute value of the temperature coefficient of resistance (TCR). To achieve this effect, it is preferable to contain 1.0 mass % or more of Al. If the content of the alloy exceeds 5.0 mass %, it is easy for the alloy to form a compound with Mn or Ni, and therefore the effect of reducing the absolute value of the temperature coefficient of resistance (TCR) and the absolute value of the thermal electromotive force (EMF) against copper is reduced. Therefore, the Al content is set to be in the range of 1.0 mass % or more and 5.0 mass % or less.
  • the alloy composition of the copper alloy material of the present invention may further contain, as a first optional added component, one or both of Co: 0.01 mass% or more and 1.30 mass% or less and Fe: 0.01 mass% or more and 0.30 mass% or less.
  • the alloy composition of the copper alloy material of the present invention includes, in addition to the above-mentioned Mn, Ni, and Al, a first optional additive component of Co (cobalt) in an amount of 0.01 mass % or more and 1.30 mass % or less. It is preferable that the content of the amine is within the range of 1 to 50% by weight.
  • Co does not easily form compounds with other elements and does not easily precipitate, it can stably reduce the absolute value of the thermoelectromotive force (EMF) against copper even when used for a long period of time as a resistance material, etc.
  • the effect of containing Co is similar to the effect of containing Ni, but the amount of addition required to reduce the absolute value of the thermoelectromotive force (EMF) against copper is smaller than that of Ni.
  • the amount of Ni added required to obtain the desired thermoelectromotive force (EMF) against copper is reduced, so that the generation of compounds of Ni and Al can be suppressed, and as a result, the electrical performance of the copper alloy material can be improved.
  • the content of Co exceeds 1.30 mass%, the characteristics of the copper alloy material tend to vary greatly. Therefore, the Co content is preferably 1.30 mass% or less.
  • the Co content may be 0.80 mass% or less. Therefore, the Co content is preferably in the range of 0.01 mass% to 1.30 mass%, and more preferably in the range of 0.10 mass% to 1.30 mass%.
  • the alloy composition of the copper alloy material of the present invention further contains, as a first optional additive component, Fe (iron) in the range of 0.01 mass% to 0.30 mass%, in addition to the above-mentioned Co. is preferred.
  • Fe is an element that reduces the absolute value of the electromotive force (EMF) against copper. To exert this effect, it is preferable that Fe is contained in an amount of 0.01 mass% or more. In the copper alloy material of the present invention, the same effect as Co can be obtained by adding Fe, and adding Fe is particularly effective from the viewpoint of reducing costs. However, when Fe is contained as the first optional added component, since Fe is an element that easily forms compounds with other elements and easily precipitates, changes in electrical properties such as volume resistivity and electromotive force against copper (EMF) may occur when used for a long period of time as a resistance material, etc.
  • EMF electromotive force
  • the Fe content is preferably 0.30 mass% or less, and more preferably 0.15 mass% or less. Therefore, the Fe content is preferably in the range of 0.01 mass% to 0.30 mass% or less, and more preferably 0.01 mass% to 1.50 mass% or less.
  • the Fe content is less than the Co content, and in this case the Fe content may be 0.
  • the alloy composition of the copper alloy material of the present invention may further contain, as a second optional added component, one or more components selected from the group consisting of Sn: 0.01 mass% or more and 2.00 mass% or less, Zn: 0.01 mass% or more and 3.00 mass% or less, Cr: 0.01 mass% or more and 0.50 mass% or less, Ag: 0.01 mass% or more and 0.50 mass% or less, Mg: 0.01 mass% or more and 0.50 mass% or less, Si: 0.01 mass% or more and 0.50 mass% or less, and P: 0.01 mass% or more and 0.50 mass% or less.
  • Sn 0.01 mass% or more and 2.00 mass% or less
  • Zn 0.01 mass% or more and 3.00 mass% or less
  • Cr 0.01 mass% or more and 0.50 mass% or less
  • Ag 0.01 mass% or more and 0.50 mass% or less
  • Mg 0.01 mass% or more and 0.50 mass% or less
  • Si 0.01 mass% or more and 0.50 mass% or less
  • P 0.
  • Sn (tin) is a component that can be used to adjust the volume resistivity ⁇ . To achieve this effect, it is preferable to contain 0.01 mass % or more of Sn. On the other hand, the Sn content is By making the content of C 2.00 mass % or less, it is possible to make it difficult for the productivity of the copper alloy material to decrease.
  • Zn 0.01% by mass or more and 3.00% by mass or less
  • Zn (zinc) is a component that can be used to adjust the volume resistivity ⁇ . To achieve this effect, it is preferable to contain Zn in an amount of 0.01 mass % or more.
  • the Zn content is However, the content of the ferrite core is set to 3.00 mass % or less since it may adversely affect the stability of electrical properties such as volume resistivity ⁇ , temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) over a long period of time. It is preferred.
  • Cr 0.01% by mass or more and 0.50% by mass or less
  • Cr chromium
  • Cr is a component that can be used to adjust the volume resistivity ⁇ . To achieve this effect, it is preferable to contain 0.01 mass % or more of Cr.
  • the Cr content is However, the content of ZnO is set to 0.50 mass % or less because it may adversely affect the stability of electrical properties such as volume resistivity ⁇ , temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) over a long period of time. It is preferred.
  • Silver (Ag) is a component that can be used to adjust the volume resistivity ⁇ . To achieve this effect, it is preferable to contain 0.01 mass % or more of Ag. On the other hand, the Ag content is However, the content of ZnO is set to 0.50 mass % or less because it may adversely affect the stability of electrical properties such as volume resistivity ⁇ , temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) over a long period of time. It is preferred.
  • Mg 0.01% by mass or more and 0.50% by mass or less
  • Mg magnetium
  • Mg is a component that can be used as a deoxidizer during casting. To achieve this effect, it is preferable to contain 0.01 mass% or more of Mg.
  • the Mg content is However, the content of ZnO is set to 0.50 mass % or less because it may adversely affect the stability of electrical properties such as volume resistivity ⁇ , temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) over a long period of time. It is preferred.
  • Silicon (Si) is a component that can be used as a deoxidizer during casting. To achieve this effect, it is preferable to contain 0.01 mass% or more of silicon. On the other hand, the Si content is However, the content of ZnO is set to 0.50 mass % or less because it may adversely affect the stability of electrical properties such as volume resistivity ⁇ , temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) over a long period of time. It is preferred.
  • P 0.01% by mass or more and 0.50% by mass or less
  • P (phosphorus) is a component that can be used as a deoxidizer during casting. To achieve this effect, it is preferable to contain P at 0.01 mass% or more.
  • the P content is However, the content of ZnO is set to 0.50 mass % or less because it may adversely affect the stability of electrical properties such as volume resistivity ⁇ , temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) over a long period of time. It is preferred.
  • the second optional components composed of one or more components selected from the group consisting of Sn, Zn, Cr, Ag, Mg, Si, and P are preferably contained in a total amount of 0.01 mass% or more.
  • the content of these second optional components may adversely affect the stability of electrical performance such as volume resistivity ⁇ , temperature coefficient of resistance (TCR), and copper thermoelectromotive force (EMF) over a long period of time, and also reduces the manufacturability of the copper alloy material, so that the content of these second optional components is preferably 3.00 mass% or less in total.
  • the remainder is composed of Cu (copper) and inevitable impurities.
  • the "unavoidable impurities" referred to here are generally those present in raw materials in copper-based products or those inevitably mixed in during the manufacturing process, and are essentially unnecessary impurities that are allowed because they are in small amounts and do not affect the properties of copper-based products.
  • components that can be cited as inevitable impurities include nonmetallic elements such as sulfur (S), carbon (C), and oxygen (O), and metallic elements such as antimony (Sb).
  • the upper limit of the content of these components can be 0.05% by mass for each of the above components, and 0.10% by mass for the total amount of the above components.
  • the shape of the copper alloy material of the present invention is not particularly limited, and can be various shapes such as plate, wire, rectangular wire, ribbon, tube, etc., but from the viewpoint of facilitating the hot or cold processing step described later, it is preferable to be a plate, a bar, a strip, or a wire.
  • the rolling direction can be the stretching direction.
  • any one of the wire drawing direction, drawing direction, and extrusion direction can be the stretching direction.
  • the copper alloy material of the present invention preferably has a metal structure with an average crystal grain size of 40 ⁇ m or less.
  • the average crystal grain size of the crystals contained in the metal structure of the copper alloy material 40 ⁇ m or less the yield strength of the alloy can be increased, and the copper alloy material can be made less likely to break.
  • the average crystal grain size of the crystals is measured in a plane perpendicular to the stretching direction when the crystals are not formed equiaxed and there is anisotropy in the size of the crystal grains due to processing such as rolling or wire drawing along the stretching direction.
  • the measurement of the average grain size in this specification can be performed in accordance with the grain size test method for drawn copper products described in JIS H0501. More specifically, a test material is prepared by embedding the copper alloy material in resin so that the cross section is exposed, and then the cross section perpendicular to the stretching direction is polished, and then wet-etched using an aqueous chromic acid solution, and the exposed grains are observed with a scanning electron microscope (SEM) to measure the grain size (or grain size). In particular, when measuring the average grain size on a surface perpendicular to the stretching direction, a test material is prepared by embedding the copper alloy material in resin so that the cross section perpendicular to the stretching direction is exposed.
  • SEM scanning electron microscope
  • the above-mentioned copper alloy material can be realized by controlling a combination of an alloy composition and a manufacturing process, and the manufacturing process is not particularly limited. Among them, the following method can be mentioned as an example of a manufacturing process that can obtain the above-mentioned copper alloy material.
  • a copper alloy material having substantially the same alloy composition as the copper alloy material described above is sequentially subjected to at least a casting step [step 1], a homogenization heat treatment step [step 2], a hot working step [step 3], a cold working step [step 4], and an annealing step [step 5].
  • the casting step [step 1] the copper alloy material is melted in an inert gas atmosphere or in a vacuum to produce an ingot.
  • the heating temperature is set to a range of 750°C to 900°C, and the holding time at the heating temperature is set to a range of 10 minutes to 10 hours.
  • the annealing step [step 5] the heating temperature is set to a range of 600°C to 800°C, and the holding time at the heating temperature is set to a range of 1 minute to 2 hours.
  • Step 1 In the casting process [Step 1], a copper alloy material having the above-mentioned alloy composition is melted in an inert gas atmosphere or in a vacuum using a high-frequency melting furnace, and then cast into an ingot of a predetermined shape (e.g., 30 mm thick, 50 mm wide, and 300 mm long).
  • a predetermined shape e.g., 30 mm thick, 50 mm wide, and 300 mm long.
  • the alloy composition of the copper alloy material may not necessarily be completely identical to that of the copper alloy material produced due to the adhesion or volatilization of additives in the melting furnace in each manufacturing process, but it has substantially the same alloy composition as that of the copper alloy material.
  • the homogenization heat treatment step [step 2] is a step of performing a homogenizing heat treatment on the ingot after the casting step [step 1].
  • the conditions of the heat treatment in the homogenization heat treatment step [step 2] are preferably a heating temperature in the range of 750°C to 900°C and a holding time at the heating temperature in the range of 10 minutes to 10 hours from the viewpoint of suppressing the coarsening of crystal grains.
  • the hot working step [step 3] is a step of producing a hot-rolled material by hot rolling or wire drawing the ingot that has been subjected to homogenization heat treatment until it has a predetermined thickness or dimensions.
  • the hot working step [step 3] includes both a hot rolling step and a hot drawing (wire drawing) step.
  • the conditions of the hot working step [step 3] are preferably a working temperature in the range of 750°C to 900°C, which may be the same as the heating temperature in the homogenization heat treatment step [step 2].
  • the working rate in the hot working step [step 3] is preferably 10% or more.
  • the "processing rate” is a value obtained by subtracting the cross-sectional area after processing such as rolling or wire drawing from the cross-sectional area before processing, dividing the result by the cross-sectional area before processing, and multiplying the result by 100, and expressed as a percentage, and is expressed by the following formula.
  • [Processing rate] ⁇ ([Cross-sectional area before processing] - [Cross-sectional area after processing]) / [Cross-sectional area before processing] ⁇ x 100 (%)
  • the hot-rolled material after the hot working step [step 3] is preferably cooled.
  • the means for cooling the hot-rolled material is not particularly limited, but from the viewpoint of preventing the crystal grains from becoming coarse, it is preferable to use a means for increasing the cooling rate as much as possible, and it is preferable to use a means such as water cooling to achieve a cooling rate of 10°C/sec or more.
  • facing may be performed on the cooled hot-rolled material to remove the surface.
  • the conditions for facing may be any conditions that are normally used, and are not particularly limited.
  • the amount of material removed from the surface of the hot-rolled material by facing can be adjusted appropriately based on the conditions of the hot working step [step 3], and can be, for example, about 0.5 mm to 4 mm from the surface of the hot-rolled material.
  • the cold working step [step 4] is a step in which the hot-rolled material after the hot working step [step 3] is subjected to cold rolling, wire drawing, and other processing at an arbitrary processing rate according to the plate thickness, wire diameter, and dimensions of the product.
  • the cold working step [step 4] includes both a cold rolling step and a cold drawing (wire drawing) step.
  • the conditions for rolling and wire drawing in the cold working step [step 4] can be set according to the size of the hot-rolled material. In particular, from the viewpoint of promoting the generation of uniform crystal grains by recrystallization in the annealing step [step 5] described later, it is preferable to set the total processing rate in the cold working step [step 4] to 50% or more.
  • the annealing step [step 5] is a step of annealing in which the cold-rolled material after the cold working step [step 4] is subjected to a heat treatment to recrystallize it.
  • the conditions of the heat treatment are that the heating temperature is in the range of 500° C. to 800° C., and the holding time at the heating temperature is in the range of 1 minute to 2 hours.
  • the heating temperature is less than 600° C. or If the holding time is less than 1 minute, it becomes difficult to recrystallize the copper alloy material.
  • the heating temperature exceeds 800° C. or the holding time exceeds 2 hours the crystal grains become coarse, , the absolute values of the temperature coefficient of resistance (TCR) and the thermal electromotive force (EMF) relative to copper tend to become large.
  • the cold working step [step 4] and the annealing step [step 5] may be repeated one or more times on the cold rolled material after the annealing step [step 5].
  • a second cold working step and annealing step may be performed on the cold rolled material after the annealing step [step 5]. This allows the copper alloy material to become a plate, bar, strip, or wire material having a desired shape, and coarse crystal grains are less likely to form, so that a copper alloy material exhibiting the desired characteristics in terms of volume resistivity, temperature coefficient of resistance, and thermoelectromotive force against copper can be obtained.
  • the copper alloy material of the present invention can be in the form of a sheet material or a bar material, strip material such as a ribbon material, or wire material such as a rectangular wire material or a round wire material, and is extremely useful as a resistor material for resistors used in resistors, for example, shunt resistors and chip resistors. That is, the resistor material is preferably made of the above-mentioned copper alloy material. In addition, resistors such as shunt resistors or chip resistors preferably have a resistor material made of the above-mentioned copper alloy material.
  • the copper alloy material of the present invention has a relatively large resistance value, it is also suitable as a heater material for a heater used in a heater, for example, a heater wire. That is, the heater material is preferably made of the above-mentioned copper alloy material. In addition, a heater such as a heater wire preferably has a heater material made of the above-mentioned copper alloy material.
  • a casting step [step 1] was carried out in which a copper alloy material having the alloy composition shown in Table 1 was melted and cast to obtain an ingot having a thickness of 30 mm.
  • This ingot was subjected to a homogenization heat treatment step [step 2] in which heat treatment was performed at a heating temperature of 800°C and a holding time of 5 hours, and then a hot working step [step 3] in which the ingot was rolled in the longitudinal direction at a temperature of 800°C so that the total working ratio was 67%, to obtain a hot-rolled material having a thickness of 10 mm. Thereafter, the ingot was cooled to room temperature by water cooling, and then face-milled to remove the oxide film formed on the surface.
  • the hot-rolled material was subjected to a cold-working process [Step 4] in which it was rolled in the longitudinal direction at a total processing rate of 90%, to obtain a cold-rolled material with a thickness of 1 mm.
  • the cold-rolled material was subjected to an annealing process [Step 5] in which it was heated at a temperature of 500°C to 750°C for 1 minute to perform heat treatment.
  • a second cold working step [step 4] was performed in which the material was rolled in the longitudinal direction at a total working rate of 70%, resulting in a cold-rolled material with a thickness of 0.3 mm.
  • a second annealing step [step 5] was performed in which heat treatment was performed at a heating temperature in the range of 500°C to 750°C for a holding time of 1 minute to 2 hours. In this way, copper alloy sheets with adjusted grain size were produced as in Examples 1 to 13 and 19 of the present invention and Comparative Examples 1 to 5.
  • a casting step [step 1] was carried out in which a copper alloy material having the alloy composition shown in Table 1 was melted and cast to obtain an ingot having a diameter of 30 mm.
  • This ingot was subjected to a homogenization heat treatment step [step 2] in which heat treatment was performed at a heating temperature of 800°C and a holding time of 5 hours, and then a hot working step [step 3] in which the ingot was extruded at a temperature of 800°C so that the total working ratio was 67% to obtain a hot-rolled rod having a diameter of 10 mm. Thereafter, the ingot was cooled to room temperature by water cooling, and then face-milled to remove the oxide film formed on the surface.
  • Step 4 a cold working process
  • Step 5 an annealing process
  • the round wire material was heat treated at a heating temperature in the range of 500°C to 750°C for a holding time of 1 minute to 2 hours.
  • Examples 16 to 18 of the present invention The rod material obtained in the same manner as in Examples 14 and 15 of the present invention after the hot working process [Step 3] was drawn with a rectangular die having a curvature radius of 0.1 mm at the four corners to obtain a total working rate of 96.3%.
  • the cold working process [Step 4] was performed to draw the rod material, and a rectangular wire material having a thickness of 1 mm and a width of 3 mm was obtained.
  • the rectangular wire material was subjected to an annealing process [Step 5] in which the heat treatment was performed at a heating temperature in the range of 500°C to 750°C for a holding time of 1 minute to 2 hours. In this way, the copper alloy wire material of Examples 16 to 18 of the present invention with adjusted crystal grain size was produced.
  • the copper alloy materials (copper alloy sheets and copper alloy wires) according to the above-mentioned examples of the present invention and comparative examples were used to carry out the following characteristic evaluations.
  • the evaluation conditions for each characteristic were as follows.
  • the polished test material was wet etched using an aqueous chromic acid solution, and the exposed crystal grains were observed in three fields of view at a magnification of 50 to 2000 times according to the average crystal grain size using a scanning electron microscope (SEM) (manufactured by Shimadzu Corporation, model number: SSX-550), and the crystal grain size was measured by the cutting method of the grain size test method for drawn copper products described in JIS H 0501, and the average crystal grain size was calculated as the average value of the crystal grain sizes in the three fields of view.
  • SEM scanning electron microscope
  • the volume resistivity ⁇ was measured by measuring the voltage using the four-terminal method in accordance with the method specified in JIS C2525 at a room temperature of 20°C with a distance between the voltage terminals of 200 mm and a measurement current of 100 mA, and the volume resistivity ⁇ [ ⁇ cm] was calculated from the obtained value.
  • the measured volume resistivity ⁇ was 40 ⁇ cm or more and 60 ⁇ cm or less, it was evaluated as " ⁇ " because it had a volume resistivity ⁇ in an excellent range for a resistance material or a material for a heating element with little energy loss due to heat generation.
  • the volume resistivity ⁇ was 25 ⁇ cm or more and less than 40 ⁇ cm, it was evaluated as " ⁇ ” because it was excellent in terms of little energy loss due to heat generation and had a volume resistivity ⁇ in a good range for a resistance material or a heating element material.
  • volume resistivity ⁇ When the volume resistivity ⁇ was more than 60 ⁇ cm and 70 ⁇ cm or less, it was evaluated as " ⁇ " because it was excellent as a resistance material or a heating element material and had a volume resistivity ⁇ in a good range for little energy loss due to heat generation. On the other hand, when the volume resistivity ⁇ was less than 25 ⁇ cm, it was evaluated as " ⁇ ” because it was poor as a resistance material or a heating element material. Furthermore, when the volume resistivity ⁇ exceeded 70 ⁇ cm, the energy loss due to heat generation was large and the product was evaluated as " ⁇ ". In this example, the evaluation was performed with " ⁇ " and " ⁇ " as pass levels. The results are shown in Table 2.
  • thermoelectromotive force EMF
  • Inventive Examples 1 to 13 and 19 and Comparative Examples 1 to 5 in which plate materials were obtained, the obtained plate materials having a thickness of 0.3 mm were cut to a width of 3 mm and a length of 1000 mm to prepare test materials.
  • Inventive Examples 14 and 15 in which round wire materials were obtained, and Inventive Examples 16 to 18, in which rectangular wire materials were obtained, the obtained round wires or rectangular wires were cut to a length of 1000 mm to prepare test materials.
  • the copper thermoelectromotive force (EMF) of the test material was measured according to JIS C2527. More specifically, as shown in FIG. 2, the copper thermoelectromotive force (EMF) of the test material 1 was measured by using a fully annealed pure copper wire having a diameter of 1 mm or less as the standard copper wire 2, immersing a temperature measuring junction P1 , in which one end of the test material 1 and the standard copper wire 2 were connected, in hot water kept warm in a thermostatic bath 41 at 80° C., and measuring the electromotive force by a voltage measuring device 43 when the reference junctions P21 and P22 , in which the other ends of the test material 1 and the standard copper wire 2 were connected to copper wires 31 and 32, respectively, were immersed in ice water at 0° C. kept cold in a freezing point device 42. The obtained electromotive force was divided by the temperature difference of 80° C. to obtain the copper thermoelectromotive force EMF ( ⁇ V/° C.).
  • thermoelectric electromotive force (EMF) against copper When the absolute value of the measured thermoelectric electromotive force (EMF) against copper was 0.6 ⁇ V/°C or less, the absolute value of the thermoelectric electromotive force (EMF) against copper was sufficiently small and was evaluated as " ⁇ " as an excellent resistance material. When the absolute value of the thermoelectric electromotive force (EMF) against copper was more than 0.6 ⁇ V/°C and less than 1.0 ⁇ V/°C, the absolute value of the thermoelectric electromotive force (EMF) against copper was small and the material was evaluated as " ⁇ " as a good resistance material.
  • thermoelectric electromotive force (EMF) against copper when the absolute value of the thermoelectric electromotive force (EMF) against copper was greater than 1.0 ⁇ V/°C, the absolute value of the thermoelectric electromotive force (EMF) against copper was large and the material was evaluated as " ⁇ " as a poor resistance material.
  • EMF thermoelectric electromotive force
  • the temperature coefficient of resistance (TCR) was measured by a four-terminal method according to the method specified in JIS C2526, with a voltage terminal distance of 200 mm and a measurement current of 100 mA, and the voltage was measured when the temperature of the test material was heated to 150 ° C., and the resistance value R 150 ° C. [m ⁇ ] at 150 ° C. was obtained from the obtained value. Next, the voltage was measured when the temperature of the test material was cooled to 20 ° C., and the resistance value R 20 ° C. [m ⁇ ] at 20 ° C. was obtained from the obtained value. Then, from the obtained resistance values R 150 ° C. and R 20 ° C.
  • the copper alloy materials of Examples 1 to 19 of the present invention have alloy compositions within the appropriate range of the present invention, and the three evaluation results regarding volume resistivity ⁇ , copper thermoelectromotive force (EMF), and temperature coefficient of resistance (TCR) were all rated as “ ⁇ ” or “ ⁇ ”, and the overall evaluation was also rated as “ ⁇ ” or " ⁇ ".
  • the copper alloy materials of Examples 1 to 19 of the present invention were all evaluated as " ⁇ " or " ⁇ ” in the overall evaluation, and therefore had a volume resistivity ⁇ in the desired range, a small absolute value of the thermoelectromotive force (EMF) against copper, and a temperature coefficient of resistance over a wide temperature range from room temperature (e.g., 20°C) to high temperature (e.g., 150°C) that was either 0 or a negative number with a small absolute value.
  • room temperature e.g. 20°C
  • high temperature e.g. 150°C
  • the copper alloy materials of Comparative Examples 1 to 5 all had alloy compositions outside the appropriate range of the present invention. Therefore, the copper alloy materials of Comparative Examples 1 to 5 were rated as "X" in at least one of the volume resistivity ⁇ , copper thermoelectromotive force (EMF), and temperature coefficient of resistance (TCR).
  • Test material 2 Standard copper wire 31, 32 Copper wire 41 Constant temperature chamber 42 Freezing point device 43 Voltage measuring device P1 Temperature measuring junction P21 , P22 Reference junction

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Abstract

L'invention fournit un alliage de cuivre qui présente une résistivité transversale contenue dans une plage prédéfinie, et qui est tel que la valeur absolue de sa force force thermo-électromotrice vis-à-vis du cuivre est faible, et que son coefficient de température de résistance dans une large plage de température allant de température normale (par exemple 20°C) à température élevée (par exemple 150°C), est égal à 0 ou à un nombre négatif et a une faible valeur absolue. L'invention fournit également un matériau résistif pour résistance, une résistance, un matériau pour élément chauffant ainsi qu'un élément chauffant qui mettent en œuvre cet alliage de cuivre.　L'alliage de cuivre de l'invention présente une composition qui comprend ７,０% en masse ou plus à １７,０% en masse ou moins de Mn, ０,１% en masse ou plus à ３,０% en masse ou moins de Ni et １,０% en masse ou plus à ５,０% en masse ou moins de Al, le reste étant constitué de Cu et des impuretés inévitables. Le matériau résistif pour résistance et le matériau pour élément chauffant de l'invention, sont configurés à partir de cet alliage de cuivre. En outre, la résistance de l'invention possède le matériau résistif pour résistance. Enfin, l'élément chauffant de l'invention possède le matériau pour élément chauffant.
PCT/JP2024/021380 2023-06-14 2024-06-12 Alliage de cuivre, et matériau résistif pour résistance, résistance, matériau pour élément chauffant ainsi qu'élément chauffant mettant en œuvre cet alliage de cuivre Pending WO2024257813A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP7779434B1 (ja) * 2025-04-21 2025-12-03 株式会社デンソー 銅合金板材の製造方法
JP7836452B1 (ja) 2024-12-27 2026-03-26 株式会社神戸製鋼所 銅合金材料、抵抗体および抵抗器

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Publication number Priority date Publication date Assignee Title
JPS59143035A (ja) * 1983-02-01 1984-08-16 Mitsubishi Heavy Ind Ltd 防汚金属材料
JPH059627A (ja) * 1991-07-09 1993-01-19 Furukawa Electric Co Ltd:The 易加工高力銅合金とその製造方法
JPH0525568A (ja) * 1991-07-22 1993-02-02 Furukawa Electric Co Ltd:The 易加工高力銅合金とその製造方法
JP2016069724A (ja) * 2014-09-29 2016-05-09 日立金属株式会社 Ｃｕ合金材およびその製造方法
CN109971992A (zh) * 2019-03-11 2019-07-05 中南大学 高抗变色低成本金色青铜合金及制备方法
JP7214931B1 (ja) * 2021-06-28 2023-01-30 古河電気工業株式会社 銅合金材ならびにそれを用いた抵抗器用抵抗材料および抵抗器

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59143035A (ja) * 1983-02-01 1984-08-16 Mitsubishi Heavy Ind Ltd 防汚金属材料
JPH059627A (ja) * 1991-07-09 1993-01-19 Furukawa Electric Co Ltd:The 易加工高力銅合金とその製造方法
JPH0525568A (ja) * 1991-07-22 1993-02-02 Furukawa Electric Co Ltd:The 易加工高力銅合金とその製造方法
JP2016069724A (ja) * 2014-09-29 2016-05-09 日立金属株式会社 Ｃｕ合金材およびその製造方法
CN109971992A (zh) * 2019-03-11 2019-07-05 中南大学 高抗变色低成本金色青铜合金及制备方法
JP7214931B1 (ja) * 2021-06-28 2023-01-30 古河電気工業株式会社 銅合金材ならびにそれを用いた抵抗器用抵抗材料および抵抗器

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7836452B1 (ja) 2024-12-27 2026-03-26 株式会社神戸製鋼所 銅合金材料、抵抗体および抵抗器
JP7779434B1 (ja) * 2025-04-21 2025-12-03 株式会社デンソー 銅合金板材の製造方法
JP7782746B1 (ja) * 2025-04-21 2025-12-09 株式会社デンソー 抵抗器の製造方法

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