WO2020196792A1 - Copper alloy strip and method for manufacturing same, resistor resistance material using same, and resistor - Google Patents

Copper alloy strip and method for manufacturing same, resistor resistance material using same, and resistor Download PDF

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Publication number
WO2020196792A1
WO2020196792A1 PCT/JP2020/013833 JP2020013833W WO2020196792A1 WO 2020196792 A1 WO2020196792 A1 WO 2020196792A1 JP 2020013833 W JP2020013833 W JP 2020013833W WO 2020196792 A1 WO2020196792 A1 WO 2020196792A1
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Prior art keywords
mass
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copper alloy
alloy strip
kam
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PCT/JP2020/013833
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French (fr)
Japanese (ja)
Inventor
紳悟 川田
貴大 佐々木
俊太 秋谷
樋口　優
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to KR1020217028881A priority Critical patent/KR20210144681A/en
Priority to CN202080015486.XA priority patent/CN113454253B/en
Priority to JP2020542676A priority patent/JP6852228B2/en
Publication of WO2020196792A1 publication Critical patent/WO2020196792A1/en

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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
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • 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
    • C22C9/06—Alloys based on copper with nickel or cobalt 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
    • 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
    • H01C3/00—Non-adjustable metal resistors made of wire or ribbon, e.g. coiled, woven or formed as grids
    • 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

Definitions

  • the present invention relates to a copper alloy strip and a method for manufacturing the same, a resistor material for a resistor using the copper alloy strip, and a resistor.
  • a copper alloy strip suitable for producing a chip by pressing is particularly preferred.
  • the present invention relates to a copper alloy strip having little variation in the resistance value of the chip.
  • the metal material of the resistor used for the resistor is required to have a small temperature coefficient of resistance (TCR), which is an index thereof, so that the resistance of the resistor is stable even if the ambient temperature changes.
  • TCR temperature coefficient of resistance
  • the temperature coefficient of resistance represents the magnitude of the change in resistance value with temperature as a fraction (ppm) per 1 ° C.
  • TCR ( ⁇ 10-6 / K) ⁇ (RR 0). ) / that R 0 ⁇ ⁇ ⁇ 1 / ( T-T 0) ⁇ ⁇ 10 6 is represented by the formula.
  • T in the equation 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 . .. Since Cu-Mn-Ni alloys and Cu-Mn-Sn alloys have a very small TCR, they are widely used as alloy materials constituting resistance materials.
  • Patent Document 1 after rolling a copper alloy material at a high pressure reduction rate, residual strain can be removed by heating in a non-oxidizing atmosphere with hydrogen gas, and as a result, the temperature coefficient of resistance is lowered. It is disclosed that it can be done. However, even in the alloy material produced in this way, the strain still remains non-uniformly, and the resistance value may vary.
  • the present invention has been made in view of the above circumstances, and is a copper alloy strip suitable for producing chips by press working, and copper with little variation in resistance value generated between products and lots. It is an object of the present invention to provide a method for producing an alloy strip and a copper alloy strip thereof.
  • the copper alloy strip contains 3% by mass or more and 20% by mass or less of manganese, and the balance is a copper alloy strip having an alloy composition consisting of copper and unavoidable impurities. Therefore, when the average value of KAM measured by the backscattered electron diffraction method is 1 ° or more and less than 5 °, the product or a chip manufactured by pressing such a copper alloy strip is used. There is little variation in the resistance value that occurs between lots, and such a copper alloy strip is a copper alloy material that has substantially the same alloy composition as the alloy composition of the copper alloy strip, and has a high temperature of 800 ° C. or higher and 950 ° C. or lower.
  • One set process or more when the two heat treatment steps are one set process, the second cold rolling process in which cold processing is performed at a low processing rate of 5% or more and less than 50%, and the temperature rise rate of 200 ° C./min or more. It was found that it can be produced by a production method including a third heat treatment step of cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or more after reaching 200 ° C. or more and less than 400 ° C. and holding for 10 to 55 seconds.
  • the present invention has been completed based on the findings.
  • the gist structure of the present invention is as follows. (1) A copper alloy strip containing 3% by mass or more and 20% by mass or less of manganese and having an alloy composition in which the balance is copper and unavoidable impurities, and the average value of KAM measured by the backscattered electron diffraction method. A copper alloy strip, characterized in that the temperature is 1 ° or more and less than 5 °. (2) The ratio of the area where the KAM value is 1 ° or more and less than 4 ° to the entire area where KAM is measured by the backscattered electron diffraction method is 50% or more. The copper alloy strip described in 1).
  • the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured by the backscattered electron diffraction method is 3% or more and 25% or less.
  • the alloy composition is 0.01% by mass or more and 5% by mass or less of nickel, 0.01% by mass or more and 5% by mass or less of tin, 0.01% by mass or more and 5% by mass or less of zinc, 0.01.
  • the copper alloy strip according to any one of (1) to (4) above, which comprises the above.
  • One set step or more when the second heat treatment step of heating in a medium temperature range is one set step, a second cold working step of performing cold working at a low working rate of 5% or more and less than 50%, and 200 ° C./ It is characterized by including a third heat treatment step of reaching 200 ° C. or higher and lower than 400 ° C. at a heating rate of min or more, holding for 10 to 55 seconds, and then cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or higher.
  • a method for manufacturing copper alloy strips (7) A resistor material for a resistor using the copper alloy strip according to any one of (1) to (5) above. (8) A resistor having the resistance material according to (7) above.
  • a copper alloy strip suitable for producing chips by press working and a copper alloy strip having a small variation in resistance value between products and lots, and a copper alloy strip thereof.
  • a method of manufacturing can be provided.
  • the copper alloy strip according to the present invention is a copper alloy strip containing 3% by mass or more and 20% by mass or less of manganese and having an alloy composition in which the balance is copper and unavoidable impurities, and is measured by the backscattered electron diffraction method.
  • the average value of KAM produced is 1 ° or more and less than 5 °.
  • the copper alloy strip of the present invention contains 3% by mass or more and 20% by mass or less of manganese.
  • Manganese (Mn) is an essential component in the present invention. When the manganese content is in such a range, the temperature coefficient of resistance of the copper alloy material can be lowered. On the other hand, if the manganese content is less than 3% by mass, the effect of reducing the temperature coefficient of resistance cannot be sufficiently obtained. Further, when the manganese content is more than 20% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. From the viewpoint of the temperature coefficient of resistance, the manganese content is preferably 5% by mass or more.
  • ⁇ Arbitrary component of copper alloy strip > Further, in the alloy strip material of the present invention, as optional additive components, nickel of 0.01% by mass or more and 5% by mass or less, tin of 0.01% by mass or more and 5% by mass or less, 0.01% by mass or more and 5% by mass.
  • Nickel 0.01% by mass or more and 5% by mass or less
  • the content of nickel (Ni) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less. If the nickel content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the nickel content exceeds 5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the nickel content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of tin (Sn) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less. If the tin content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the tin content exceeds 5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the tin content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of iron (Fe) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less. If the iron content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the iron content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the iron content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of zinc (Zn) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less. If the zinc content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the zinc content is more than 5% by mass, the resistance value may vary due to the dezincification phenomenon.
  • the zinc content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of silicon (Si) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less. If the silicon content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the silicon content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the silicon content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of chromium (Cr) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the chromium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the chromium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the chromium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • zirconium 0.01% by mass or more and 0.5% by mass or less
  • the content of zirconium (Zr) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the zirconium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the zirconium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the zirconium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • titanium 0.01% by mass or more and 0.5% by mass or less
  • the content of titanium (Ti) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the titanium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the titanium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the titanium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of silver (Ag) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the silver content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the silver content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the silver content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of magnesium (Mg) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the magnesium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the magnesium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the magnesium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of cobalt (Co) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the cobalt content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the cobalt content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the cobalt content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the content of phosphorus (P) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less with respect to 100% by mass of the copper alloy strip. If the phosphorus content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the phosphorus content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range.
  • the phosphorus content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
  • the balance consists of Cu (copper) and unavoidable impurities.
  • the "unavoidable impurities” referred to here are generally those that are present in the raw materials of copper-based products and those that are unavoidably mixed in the manufacturing process, which are originally unnecessary, but are in trace amounts. It is an acceptable impurity because it does not affect the characteristics of copper-based products.
  • Examples of the components listed as unavoidable impurities include non-metal elements such as sulfur (S) and oxygen (O) and metal elements such as aluminum (Al) and antimony (Sb).
  • the upper limit of the content of these components may be 0.05% by mass for each of the above components and 0.20% by mass for the total amount of the above components.
  • the alloy strip of the present invention is characterized in that the average value of KAM measured by the backscattered electron diffraction method (EBSD method) is 1 ° or more and less than 5 °.
  • EBSD method backscattered electron diffraction method
  • the copper alloy strip has a very slight strain, and the strain generated by the press working is suppressed (offset) by this strain. It is possible to suppress variations in resistance values between products and lots.
  • the average value of KAM is less than 1 °, the copper alloy strip has little strain (after recrystallization), and strain is introduced by press working to introduce strain between products and lots. The resistance value varies. Further, when the average value of KAM is 5 ° or more, the resistance value fluctuates due to the influence of heat generated at the time of use or mounting, for example, and the resistance value may fluctuate between products and lots.
  • the ratio of the area where the KAM value is 1 ° or more and less than 4 ° to the entire area where KAM is measured by the backscattered electron diffraction method is preferably 50% or more.
  • the area where the KAM value is 1 ° or more and less than 4 ° occupies a small proportion it means that there are many less than 1 °, or there are many 4 ° or more, but if there are many less than 1 °, the distortion is There are many small states, and when there are many 4 ° or more, there are many high distortion regions, for example, it is easily affected by heat during mounting, the resistance value is greatly affected by slight temperature fluctuations and time minors, and variations are large. Become.
  • the ratio of the area where the KAM value is 1 ° or more and less than 4 ° is preferably 50% or more, and more preferably 50% or more and less than 70%.
  • the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured by the backscattered electron diffraction method is preferably 3% or more and 25% or less.
  • the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the total area where KAM is measured is 3% or more and 25% or less, which means that there is a region with poor ductility. Since this is the starting point of fracture during pressing, press working can be performed without increasing the amount of strain in the alloy, improving dimensional accuracy and more effectively suppressing variations in resistance values between products and lots. Can be done.
  • the proportion of the area where the KAM value is 6 ° or more and less than 15 ° is more preferably 5% or more and 25% or less.
  • KAM is measured by the backscattered electron diffraction method using JSM-7001FA manufactured by JEOL Ltd.
  • the cross section of the copper alloy strip parallel to the rolling direction is mirror-finished by resin filling, electrolytic polishing, etc., and used as a measurement sample.
  • the surface of the sample can be mirror-finished by immersing the copper alloy strip in a phosphoric acid solution and energizing for 60 seconds for electrolytic polishing.
  • a visual field region of 100 ⁇ m ⁇ 100 ⁇ m at the center of the plate thickness is targeted for measurement, and measurement is performed with a step size of 0.05 ⁇ m.
  • the average value of KAM is calculated for all points using the measured values of the first adjacent to each other with the crystal orientation difference of 15 ° or more as the boundary. Further, in the visual field region, the range of 0 ° or more and less than 15 ° is divided into 15 and the area ratio for each 1 ° is obtained, so that the area measured by KAM is 1 ° or more with respect to the entire measured area. The ratio of the area less than 4 ° and the ratio of the area of 6 ° or more and less than 15 ° are calculated. Such measurement was performed at 5 arbitrary points, and the average value was calculated.
  • the Vickers hardness of the alloy strip of the present invention is not particularly limited, but is preferably 150 or more and 200 or less, and more preferably 150 or more and 190 or less. When the Vickers hardness is within such a range, strain due to press working can be suppressed, and changes in characteristics such as resistance value due to heat can be suppressed.
  • the Vickers hardness is measured from the surface of the copper alloy material in accordance with the method specified in JIS Z2244 (2009).
  • the load (test force) at this time is 2.9 N, and the indenter reduction time is 15 s.
  • the copper alloy strip of the present invention is extremely useful as a resistance material for resistors such as shunt resistors and chip resistors.
  • This manufacturing method includes a first heat treatment step of heating a copper alloy material having substantially the same alloy composition as the alloy composition of the copper alloy strip in a high temperature range of 800 ° C. or higher and 950 ° C. or lower, a hot working step, and 50.
  • One set process or more when the first cold processing process of performing cold processing at a high processing rate of% or more and the second heat treatment process of heating in a medium temperature range of 400 ° C. or more and 700 ° C. or less are set as one set process.
  • the second cold rolling process in which cold working is performed at a low processing rate of 5% or more and less than 50%, and holding for 10 to 55 seconds after reaching 200 ° C or more and less than 400 ° C at a heating rate of 200 ° C / min or more. After that, it is characterized by including a third heat treatment step of cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or more.
  • a third heat treatment step of cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or more.
  • the copper alloy material has substantially the same alloy composition as the alloy composition of the copper alloy strip.
  • the copper alloy material include ingots produced by casting, but are not particularly limited.
  • the alloy composition of the copper alloy material is set to be "substantially the same” as the alloy composition of the copper alloy strip in the copper alloy material in each process from the copper alloy material to the production of the copper alloy strip.
  • the first heat treatment step is a step of heating the copper alloy material in a high temperature range of 800 ° C. or higher and 950 ° C. or lower.
  • the heating temperature in the first heat treatment step is set to a high temperature range of 800 ° C. or higher and 950 ° C. or lower, solidification segregation, crystallizations and precipitates generated during casting can be eliminated and the material can be made uniform.
  • the heating time in the first heat treatment step is not particularly limited, but is preferably 10 minutes or more and 10 hours or less.
  • the hot working step is a step of machining (for example, rolling) to a desired plate thickness at a temperature of, for example, about 800 ° C. to 950 ° C.
  • the hot working is not particularly limited to either rolling or extrusion.
  • the first cold working step is a step of performing cold working at a high working rate of 50% or more.
  • cold working is appropriately performed according to a conventional method.
  • the second heat treatment step is a step of heating in a medium temperature range of 400 ° C. or higher and 700 ° C. or lower.
  • the heating temperature in the second heat treatment step is set to a medium temperature range of 400 ° C. or higher and 700 ° C. or lower.
  • recrystallization can be obtained to obtain a uniform structure from which strain has been removed.
  • heat treatment is appropriately performed according to a conventional method.
  • the heating time in the second heat treatment is not particularly limited, but is preferably 10 seconds or more and 10 hours or less.
  • the above-mentioned first cold working step and second heat treatment step may be performed only by one set step or may be repeated by two or more set steps when these two steps are regarded as one set step.
  • the second cold rolling step is a step of performing cold working at a low working rate of 5% or more and less than 50%.
  • the processing rate in the second cold rolling step is 50% or more, even if heating is applied in the third heat treatment step in the subsequent stage, the strain generated here is maintained as non-uniform and press molding is performed. It is possible to suppress variations in resistance values between products manufactured in the above-mentioned products and lots. Further, by setting it to 20% or more and less than 50%, the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured can be set to an appropriate range.
  • ⁇ Third heat treatment process> In the third heat treatment step, after reaching 200 ° C. or higher and lower than 400 ° C. at a heating rate of 200 ° C./min or more, holding for 10 to 55 seconds, and then cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or higher. 3 This is a step of heating in the heat treatment step.
  • the distortion in the crystal is suppressed and adjusted without recrystallization of the crystal grains, and the average value of KAM measured by the backscattered electron diffraction method is 1 ° or more. It will be less than 5 °.
  • the temperature to 250 ° C.
  • the ratio occupied by the area whose value is 1 ° or more and less than 4 ° can be set as an appropriate range.
  • the above method for producing a copper alloy strip may be provided with a process other than the above-mentioned process.
  • a surface milling process for removing a thick oxide film formed after a hot working process by mechanical polishing a degreasing process for removing rolling oil, and a polishing process for mechanically or chemically removing a thin oxide film generated by heat treatment.
  • a first cold working step with a high working rate of 90% or more and a second heat treatment step of heating in a medium temperature range of 400 ° C. or higher and 700 ° C. or lower were performed.
  • the first cold working step and the second heat treatment step were performed once (one set) in Examples 1 to 5, 7, 8, 10 to 15 of the present invention and Comparative Examples 1 to 5, respectively. Further, in Examples 6 and 9 of the present invention, the processing rate and the heating conditions were changed between the first set and the second set, and the treatment was performed twice (2 sets) each.
  • composition of copper alloy strip The chemical composition of the copper alloy strip was measured by ICP analysis and is shown in Table 1 below.
  • the range of 0 ° or more and less than 15 ° is divided into 15 (0 ° or more and less than 1 °, 1 ° or more and less than 2 °, 2 ° or more and less than 3 °, ... 14 ° or more and less than 15 °).
  • the area ratio for each 1 ° the ratio of the area having KAM of 1 ° or more and less than 4 ° and the area having KAM of 6 ° or more and less than 15 ° occupy in the 100 ⁇ m ⁇ 100 ⁇ m field of view as the measurement target.
  • the ratio was calculated. Such measurement was performed at 5 arbitrary points, and the average value was calculated.
  • a chip with a plate thickness of 0.2 mm, a width of 2 mm, and a length of 60 mm is formed by a press, and after heat treatment at 260 ° C. for 30 minutes in an argon gas atmosphere, assuming the influence of heat during mounting, the distance between the voltage terminals is set to 30 mm.
  • the variation in resistance value is "A" for the test material (copper alloy strip) whose value obtained by the formula (standard deviation / average value x 100) is 0.50% or less, and more than 0.50% 0.55.
  • test material of% or less was evaluated as “B”, the test material of more than 0.55% and 0.60% or less was evaluated as “C”, and the test material of more than 0.60% was evaluated as “D”. If the value obtained by the formula (standard deviation / average value ⁇ 100) is 0.60% or less (that is, A to C evaluation), the variation in resistance value is evaluated as a passing level.
  • the copper alloy strips of Examples 1 to 15 of the present invention have a composition containing manganese of 3% by mass or more and 20% by mass or less, and the average of KAM measured by the backscattered electron diffraction method. Since the value was 1 ° or more and less than 5 °, which was within the appropriate range of the present invention, it was found that there was little variation in the resistance value even after heat treatment at 260 ° C. for 30 minutes after press molding.
  • the test material (copper alloy strip) of Comparative Example 1 has a composition containing 12% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 0. Since it was 5.5 °, which was smaller than the appropriate range of the present invention, it was found that the resistance value varied widely after heat treatment at 260 ° C. for 30 minutes after press molding.
  • test material (copper alloy strip) of Comparative Example 2 has a composition containing 12% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 12.1. Since ° is larger than the appropriate range of the present invention, it was found that the resistance value varies widely after heat treatment at 260 ° C. for 30 minutes after press molding.
  • test material (copper alloy strip) of Comparative Example 3 has a composition containing 7% by mass of manganese, but by heating at 700 ° C. as the third heat treatment, a backscattered electron diffraction method was performed. It was found that the average value of KAM measured by the above was 0.6 °, which was smaller than the appropriate range of the present invention, and the resistance value varied widely after heat treatment at 260 ° C. for 30 minutes after press molding. It was.
  • the test material (copper alloy strip) of Comparative Example 4 has a composition containing 10% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 13.8 °. Since it is larger than the appropriate range of the present invention, it was found that the resistance value varies widely after heat treatment at 260 ° C. for 30 minutes after press molding.
  • the test material (copper alloy strip) of Comparative Example 5 has a composition containing 5% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 0.9 °. Since it is larger than the appropriate range of the present invention, it was found that the resistance value varies widely after heat treatment at 260 ° C. for 30 minutes after press molding.

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Abstract

A copper alloy strip according to the present invention has an alloy composition containing 3-20 mass% of manganese with the remainder comprising copper and inevitable impurities, wherein the average value of KAM is at least 1° and less than 5° as measured by an electron backscatter diffraction method. The copper alloy strip is suitable for manufacturing chips, etc. by press processing, and has a small variation in resistance values between products or lots.

Description

銅合金条材およびその製造方法、それを用いた抵抗器用抵抗材料ならびに抵抗器Copper alloy strips and their manufacturing methods, resistor materials for resistors using them, and resistors
　本発明は、銅合金条材およびその製造方法、それを用いた抵抗器用抵抗材料ならびに抵抗器に関し、特に、プレス加工を施してチップを製造するのに適した銅合金条材であって、製造されるチップの抵抗値のばらつきが少ない銅合金条材に関する。 The present invention relates to a copper alloy strip and a method for manufacturing the same, a resistor material for a resistor using the copper alloy strip, and a resistor. In particular, a copper alloy strip suitable for producing a chip by pressing. The present invention relates to a copper alloy strip having little variation in the resistance value of the chip.
　抵抗器に使用される抵抗材の金属材料には、環境温度が変化しても抵抗器の抵抗が安定するように、その指標である抵抗温度係数（ＴＣＲ）が小さいことが要求される。抵抗温度係数とは、温度による抵抗値の変化の大きさを１℃当たりの百万分率（ｐｐｍ）で表したものであり、ＴＣＲ（×１０－６／Ｋ）＝{（Ｒ－Ｒ０）／Ｒ０}×{１／（Ｔ－Ｔ０）}×１０６という式で表される。ここで、式中のＴは試験温度（℃）、Ｔ０は基準温度（℃）、Ｒは試験温度Ｔにおける抵抗値（Ω）、Ｒ０は基準温度Ｔ０における抵抗値（Ω）を示す。Ｃｕ－Ｍｎ－Ｎｉ合金やＣｕ－Ｍｎ－Ｓｎ合金はＴＣＲが非常に小さいため、抵抗材を構成する合金材料として広く使用されている。 The metal material of the resistor used for the resistor is required to have a small temperature coefficient of resistance (TCR), which is an index thereof, so that the resistance of the resistor is stable even if the ambient temperature changes. The temperature coefficient of resistance represents the magnitude of the change in resistance value with temperature as a fraction (ppm) per 1 ° C., and TCR (× 10-6 / K) = {(RR 0). ) / that R 0} × {1 / ( T-T 0)} × 10 6 is represented by the formula. Here, T in the equation indicates the test temperature (° C.), T 0 indicates the reference temperature (° C.), R indicates the resistance value (Ω) at the test temperature T, and R 0 indicates the resistance value (Ω) at the reference temperature T 0 . .. Since Cu-Mn-Ni alloys and Cu-Mn-Sn alloys have a very small TCR, they are widely used as alloy materials constituting resistance materials.
　ところで、このような合金材料をプレス成形して製造される抵抗材においては、プレス成形時に当該合金材料中に歪みが導入され、抵抗値にばらつきが生じ、安定的に抵抗材を生産できないことがある。 By the way, in a resistance material produced by press-molding such an alloy material, strain is introduced into the alloy material during press molding, and the resistance value varies, so that the resistance material cannot be stably produced. is there.
　特許文献１においては、銅合金素材に対し高圧下率で圧延処理を施した後、水素ガスによる非酸化性雰囲気で加熱することにより、残留歪を除去でき、その結果として抵抗温度係数を低下させることができることが開示されている。しかしながら、このようにして製造される合金材料であっても、なお歪みが不均一に残留しており、抵抗値にばらつきが生じ得るものであった。 In Patent Document 1, after rolling a copper alloy material at a high pressure reduction rate, residual strain can be removed by heating in a non-oxidizing atmosphere with hydrogen gas, and as a result, the temperature coefficient of resistance is lowered. It is disclosed that it can be done. However, even in the alloy material produced in this way, the strain still remains non-uniformly, and the resistance value may vary.
特開２０１６－６９７２４号公報Japanese Unexamined Patent Publication No. 2016-69724
　本発明は、以上の実情に鑑みてなされたものであり、プレス加工を施してチップを製造するのに適した銅合金条材であって、製品やロット間に生じる抵抗値のばらつきが少ない銅合金条材およびその銅合金条材を製造する方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a copper alloy strip suitable for producing chips by press working, and copper with little variation in resistance value generated between products and lots. It is an object of the present invention to provide a method for producing an alloy strip and a copper alloy strip thereof.
　本発明者らは、鋭意検討を重ねた結果、銅合金条材が、３質量％以上２０質量％以下のマンガンを含有し、残部が銅および不可避不純物からなる合金組成を有する銅合金条材であって、後方散乱電子回折法により測定されるＫＡＭの平均値が１°以上５°未満であることによって、そのような銅合金条材に、プレス加工を施して製造されるチップにおいて、製品やロット間に生じる抵抗値のばらつきが少ないこと、およびそのような銅合金条材は、前記銅合金条材の合金組成と実質同じ合金組成を有する銅合金素材に、８００℃以上９５０℃以下の高温域で加熱する第１熱処理工程と、熱間加工工程と、５０％以上の高加工率で冷間加工を施す第１冷間加工工程、および４００℃以上７００℃以下の中温域で加熱する第２熱処理工程を１セット工程とするときの１セット工程以上と、５％以上５０％未満の低加工率で冷間加工を施す第２冷間圧延工程と、２００℃／ｍｉｎ以上の昇温速度で２００℃以上４００℃未満に到達した後、１０～５５秒保持後、１００℃／ｍｉｎ以上の冷却速度で５０℃未満まで冷却する第３熱処理工程とを含む製造方法により製造できることを見出し、かかる知見に基づき本発明を完成するに至った。 As a result of diligent studies, the present inventors have found that the copper alloy strip contains 3% by mass or more and 20% by mass or less of manganese, and the balance is a copper alloy strip having an alloy composition consisting of copper and unavoidable impurities. Therefore, when the average value of KAM measured by the backscattered electron diffraction method is 1 ° or more and less than 5 °, the product or a chip manufactured by pressing such a copper alloy strip is used. There is little variation in the resistance value that occurs between lots, and such a copper alloy strip is a copper alloy material that has substantially the same alloy composition as the alloy composition of the copper alloy strip, and has a high temperature of 800 ° C. or higher and 950 ° C. or lower. A first heat treatment step of heating in a region, a hot working step, a first cold working step of performing cold working at a high working rate of 50% or more, and a first heating in a medium temperature range of 400 ° C. or higher and 700 ° C. or lower. One set process or more when the two heat treatment steps are one set process, the second cold rolling process in which cold processing is performed at a low processing rate of 5% or more and less than 50%, and the temperature rise rate of 200 ° C./min or more. It was found that it can be produced by a production method including a third heat treatment step of cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or more after reaching 200 ° C. or more and less than 400 ° C. and holding for 10 to 55 seconds. The present invention has been completed based on the findings.
　すなわち、本発明の要旨構成は以下のとおりである。
　（１）３質量％以上２０質量％以下のマンガンを含有し、残部が銅および不可避不純物からなる合金組成を有する銅合金条材であって、後方散乱電子回折法により測定されるＫＡＭの平均値が１°以上５°未満であることを特徴とする、銅合金条材。
　（２）後方散乱電子回折法によりＫＡＭを測定した面積全体に対して、ＫＡＭの値が１°以上４°未満である面積が占める割合は、５０％以上であることを特徴とする、上記（１）に記載の銅合金条材。
　（３）後方散乱電子回折法によりＫＡＭを測定した面積全体に対して、ＫＡＭの値が６°以上１５°未満である面積が占める割合は、３％以上２５％以下であることを特徴とする、上記（１）または（２）に記載の銅合金条材。
　（４）ビッカース硬さが１５０以上２００以下であることを特徴とする、上記（１）～（３）のいずれかに記載の銅合金条材。
　（５）前記合金組成は、０．０１質量％以上５質量％以下のニッケル、０．０１質量％以上５質量％以下の錫、０．０１質量％以上５質量％以下の亜鉛、０．０１質量％以上０．５質量％以下の鉄、０．０１質量％以上０．５質量％以下のケイ素、０．０１質量％以上０．５質量％以下のクロム、０．０１質量％以上０．５質量％以下のジルコニウム、０．０１質量％以上０．５質量％以下のチタン、０．０１質量％以上０．５質量％以下の銀、０．０１質量％以上０．５質量％以下のマグネシウム、０．０１質量％以上０．５質量％以下のコバルト、および、０．０１質量％以上０．５質量％以下のリンからなる群より選択される１種以上の元素をさらに含有することを特徴とする、上記（１）～（４）のいずれかに記載の銅合金条材。
　（６）上記（１）～（５）のいずれかに記載の銅合金条材の製造方法であって、前記銅合金条材の合金組成と実質同じ合金組成を有する銅合金素材に、８００℃以上９５０℃以下の高温域で加熱する第１熱処理工程と、熱間加工工程と、５０％以上の高加工率で冷間加工を施す第１冷間加工工程、および４００℃以上７００℃以下の中温域で加熱する第２熱処理工程を１セット工程とするときの１セット工程以上と、５％以上５０％未満の低加工率で冷間加工を施す第２冷間加工工程と、２００℃／ｍｉｎ以上の昇温速度で２００℃以上４００℃未満に到達した後、１０～５５秒保持後、１００℃／ｍｉｎ以上の冷却速度で５０℃未満まで冷却する第３熱処理工程とを含むことを特徴とする、銅合金条材の製造方法。
　（７）上記（１）～（５）のいずれかに記載の銅合金条材を用いた抵抗器用抵抗材料。
　（８）上記（７）に記載の抵抗材料を有する抵抗器。 That is, the gist structure of the present invention is as follows.
(1) A copper alloy strip containing 3% by mass or more and 20% by mass or less of manganese and having an alloy composition in which the balance is copper and unavoidable impurities, and the average value of KAM measured by the backscattered electron diffraction method. A copper alloy strip, characterized in that the temperature is 1 ° or more and less than 5 °.
(2) The ratio of the area where the KAM value is 1 ° or more and less than 4 ° to the entire area where KAM is measured by the backscattered electron diffraction method is 50% or more. The copper alloy strip described in 1).
(3) The ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured by the backscattered electron diffraction method is 3% or more and 25% or less. , The copper alloy strip according to (1) or (2) above.
(4) The copper alloy strip according to any one of (1) to (3) above, wherein the Vickers hardness is 150 or more and 200 or less.
(5) The alloy composition is 0.01% by mass or more and 5% by mass or less of nickel, 0.01% by mass or more and 5% by mass or less of tin, 0.01% by mass or more and 5% by mass or less of zinc, 0.01. Iron of mass% or more and 0.5 mass% or less, silicon of 0.01 mass% or more and 0.5 mass% or less, chromium of 0.01 mass% or more and 0.5 mass% or less, 0.01 mass% or more and 0. 5% by mass or less of zirconium, 0.01% by mass or more and 0.5% by mass or less of titanium, 0.01% by mass or more and 0.5% by mass or less of silver, 0.01% by mass or more and 0.5% by mass or less Further containing one or more elements selected from the group consisting of magnesium, 0.01% by mass or more and 0.5% by mass or less of cobalt, and 0.01% by mass or more and 0.5% by mass or less of phosphorus. The copper alloy strip according to any one of (1) to (4) above, which comprises the above.
(6) The method for producing a copper alloy strip according to any one of (1) to (5) above, wherein a copper alloy material having substantially the same alloy composition as the alloy composition of the copper alloy strip is used at 800 ° C. The first heat treatment step of heating in a high temperature range of 950 ° C. or lower, the hot working step, the first cold working step of performing cold working at a high working rate of 50% or more, and 400 ° C. or higher and 700 ° C. or lower. One set step or more when the second heat treatment step of heating in a medium temperature range is one set step, a second cold working step of performing cold working at a low working rate of 5% or more and less than 50%, and 200 ° C./ It is characterized by including a third heat treatment step of reaching 200 ° C. or higher and lower than 400 ° C. at a heating rate of min or more, holding for 10 to 55 seconds, and then cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or higher. A method for manufacturing copper alloy strips.
(7) A resistor material for a resistor using the copper alloy strip according to any one of (1) to (5) above.
(8) A resistor having the resistance material according to (7) above.
　本発明によれば、プレス加工を施してチップを製造するのに適した銅合金条材であって、製品やロット間に生じる抵抗値のばらつきが少ない銅合金条材およびその銅合金条材を製造する方法を提供することができる。 According to the present invention, a copper alloy strip suitable for producing chips by press working, and a copper alloy strip having a small variation in resistance value between products and lots, and a copper alloy strip thereof. A method of manufacturing can be provided.
（１）銅合金条材
　以下、本発明の銅合金条材の好ましい実施形態について、詳細に説明する。本発明に従う銅合金条材は、３質量％以上２０質量％以下のマンガンを含有し、残部が銅および不可避不純物からなる合金組成を有する銅合金条材であって、後方散乱電子回折法により測定されるＫＡＭの平均値が１°以上５°未満であることを特徴とするものである。 (1) Copper Alloy Strips Hereinafter, preferred embodiments of the copper alloy strips of the present invention will be described in detail. The copper alloy strip according to the present invention is a copper alloy strip containing 3% by mass or more and 20% by mass or less of manganese and having an alloy composition in which the balance is copper and unavoidable impurities, and is measured by the backscattered electron diffraction method. The average value of KAM produced is 1 ° or more and less than 5 °.
　このような銅合金条材においては、Ｍｎを３質量％以上含有していることにより、当該銅合金条材内に適切な歪みを生じさせ、適切なＫＡＭの値が得られる。一方で、銅合金条材において、後方散乱電子回折法により測定されるＫＡＭの平均値が１°以上５°未満であることにより、当該銅合金条材がごく僅かな歪みを有するものとなり、この歪みによりプレス加工で生じる歪みを抑制（相殺）し、製品やロット間の抵抗値のばらつきを抑制することができる。 In such a copper alloy strip, when Mn is contained in an amount of 3% by mass or more, an appropriate strain is generated in the copper alloy strip, and an appropriate KAM value can be obtained. On the other hand, in the copper alloy strip, when the average value of KAM measured by the backscattered electron diffraction method is 1 ° or more and less than 5 °, the copper alloy strip has a very slight strain. It is possible to suppress (cancel) the strain generated by press working due to the strain, and suppress the variation in the resistance value between products and lots.
＜銅合金条材の組成＞
　〔マンガン：３質量％以上２０質量％以下〕
　本発明の銅合金条材は、３質量％以上２０質量％以下のマンガンを含有するものである。マンガン（Ｍｎ）は、本発明では必須の含有成分である。マンガン含有量がこのような範囲にあることにより、当該銅合金材料の抵抗温度係数を低下させることができる。これに対し、マンガンの含有量が３質量％未満であると、抵抗温度係数を小さくする効果が十分に得られない。また、マンガンの含有量が２０質量％より多い場合、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。抵抗温度係数の観点から、マンガン含有量は、５質量％以上であることが好ましい。 <Composition of copper alloy strip>
[Manganese: 3% by mass or more and 20% by mass or less]
The copper alloy strip of the present invention contains 3% by mass or more and 20% by mass or less of manganese. Manganese (Mn) is an essential component in the present invention. When the manganese content is in such a range, the temperature coefficient of resistance of the copper alloy material can be lowered. On the other hand, if the manganese content is less than 3% by mass, the effect of reducing the temperature coefficient of resistance cannot be sufficiently obtained. Further, when the manganese content is more than 20% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. From the viewpoint of the temperature coefficient of resistance, the manganese content is preferably 5% by mass or more.
＜銅合金条材の任意成分＞
　また、本発明の合金条材は、任意添加成分として、０．０１質量％以上５質量％以下のニッケル、０．０１質量％以上５質量％以下の錫、０．０１質量％以上５質量％以下の亜鉛、０．０１質量％以上０．５質量％以下の鉄、０．０１質量％以上０．５質量％以下のケイ素、０．０１質量％以上０．５質量％以下のクロム、０．０１質量％以上０．５質量％以下のジルコニウム、０．０１質量％以上０．５質量％以下のチタン、０．０１質量％以上０．５質量％以下の銀、０．０１質量％以上０．５質量％以下のマグネシウム、０．０１質量％以上０．５質量％以下のコバルト、および、０．０１質量％以上０．５質量％以下のリンからなる群より選択される１種以上の元素をさらに含有することができる。これらの元素は、いずれも抵抗温度係数の改善、体積抵抗率の調整等を目的として添加するものであるが、それぞれの所定の範囲を超えて添加すると、使用温度が４００℃未満であっても、抵抗値等の特性が変動したり、原料コストの増加等が生じたりするおそれがある。以下、各金属元素についてそれぞれ説明する。 <Arbitrary component of copper alloy strip>
Further, in the alloy strip material of the present invention, as optional additive components, nickel of 0.01% by mass or more and 5% by mass or less, tin of 0.01% by mass or more and 5% by mass or less, 0.01% by mass or more and 5% by mass. The following zinc, 0.01% by mass or more and 0.5% by mass or less of iron, 0.01% by mass or more and 0.5% by mass or less of silicon, 0.01% by mass or more and 0.5% by mass or less of chromium, 0 0.01 mass% or more and 0.5 mass% or less zirconium, 0.01 mass% or more and 0.5 mass% or less titanium, 0.01 mass% or more and 0.5 mass% or less silver, 0.01 mass% or more One or more selected from the group consisting of magnesium of 0.5% by mass or less, cobalt of 0.01% by mass or more and 0.5% by mass or less, and phosphorus of 0.01% by mass or more and 0.5% by mass or less. Elements can be further contained. All of these elements are added for the purpose of improving the temperature coefficient of resistance, adjusting the volume resistivity, etc. However, if they are added beyond their respective predetermined ranges, even if the operating temperature is less than 400 ° C. , Characteristics such as resistance value may fluctuate, and raw material cost may increase. Hereinafter, each metal element will be described.
　〔ニッケル：０．０１質量％以上５質量％以下〕
　ニッケル（Ｎｉ）の含有量は、特に限定されないが、０．０１質量％以上５質量％以下であることが好ましい。ニッケルの含有量が０．０１％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、ニッケルの含有量が５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、ニッケルの含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Nickel: 0.01% by mass or more and 5% by mass or less]
The content of nickel (Ni) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less. If the nickel content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the nickel content exceeds 5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The nickel content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔錫：０．０１質量％以上５質量％以下〕
　錫（Ｓｎ）の含有量は、特に限定されないが、０．０１質量％以上５質量％以下であることが好ましい。錫の含有量が０．０１％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、錫の含有量が５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、錫の含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Tin: 0.01% by mass or more and 5% by mass or less]
The content of tin (Sn) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less. If the tin content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the tin content exceeds 5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The tin content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔鉄：０．０１質量％以上０．５質量％以下〕
　鉄（Ｆｅ）の含有量は、特に限定されないが、０．０１質量％以上０．５質量％以下であることが好ましい。鉄の含有量が０．０１％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、鉄の含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、鉄の含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Iron: 0.01% by mass or more and 0.5% by mass or less]
The content of iron (Fe) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less. If the iron content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the iron content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The iron content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔亜鉛：０．０１質量％以上５質量％以下〕
　亜鉛（Ｚｎ）の含有量は、特に限定されないが、０．０１質量％以上５質量％以下であることが好ましい。亜鉛の含有量が０．０１％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、亜鉛の含有量が５質量％超であると、脱亜鉛現象に起因する抵抗値のばらつきが生じるおそれがある。なお、亜鉛の含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Zinc: 0.01% by mass or more and 5% by mass or less]
The content of zinc (Zn) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less. If the zinc content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the zinc content is more than 5% by mass, the resistance value may vary due to the dezincification phenomenon. The zinc content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔ケイ素：０．０１質量％以上０．５質量％以下〕
　ケイ素（Ｓｉ）の含有量は、特に限定されないが、０．０１質量％以上０．５質量％以下であることが好ましい。ケイ素の含有量が０．０１質量％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、ケイ素の含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、ケイ素の含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Silicon: 0.01% by mass or more and 0.5% by mass or less]
The content of silicon (Si) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less. If the silicon content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the silicon content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The silicon content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔クロム：０．０１質量％以上０．５質量％以下〕
　クロム（Ｃｒ）の含有量は、特に限定されないが、銅合金条材１００質量％に対して０．０１質量％以上０．５質量％以下であることが好ましい。クロムの含有量が０．０１質量％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、クロムの含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、クロムの含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Chromium: 0.01% by mass or more and 0.5% by mass or less]
The content of chromium (Cr) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the chromium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the chromium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The chromium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔ジルコニウム：０．０１質量％以上０．５質量％以下〕
　ジルコニウム（Ｚｒ）の含有量は、特に限定されないが、銅合金条材１００質量％に対して０．０１質量％以上０．５質量％以下であることが好ましい。ジルコニウムの含有量が０．０１質量％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、ジルコニウムの含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、ジルコニウムの含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Zirconium: 0.01% by mass or more and 0.5% by mass or less]
The content of zirconium (Zr) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the zirconium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the zirconium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The zirconium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔チタン：０．０１質量％以上０．５質量％以下〕
　チタン（Ｔｉ）の含有量は、特に限定されないが、銅合金条材１００質量％に対して０．０１質量％以上０．５質量％以下であることが好ましい。チタンの含有量が０．０１質量％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、チタンの含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、チタンの含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Titanium: 0.01% by mass or more and 0.5% by mass or less]
The content of titanium (Ti) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the titanium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the titanium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The titanium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔銀：０．０１質量％以上０．５質量％以下〕
　銀（Ａｇ）の含有量は、特に限定されないが、銅合金条材１００質量％に対して０．０１質量％以上０．５質量％以下であることが好ましい。銀の含有量が０．０１％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、銀の含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、銀の含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Silver: 0.01% by mass or more and 0.5% by mass or less]
The content of silver (Ag) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the silver content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the silver content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The silver content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔マグネシウム：０．０１質量％以上０．５質量％以下〕
　マグネシウム（Ｍｇ）の含有量は、特に限定されないが、銅合金条材１００質量％に対して０．０１質量％以上０．５質量％以下であることが好ましい。マグネシウムの含有量が０．０１質量％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、マグネシウムの含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、マグネシウムの含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Magnesium: 0.01% by mass or more and 0.5% by mass or less]
The content of magnesium (Mg) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the magnesium content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the magnesium content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The magnesium content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔コバルト：０．０１質量％以上０．５質量％以下〕
　コバルト（Ｃｏ）の含有量は、特に限定されないが、銅合金条材１００質量％に対して０．０１質量％以上０．５質量％以下であることが好ましい。コバルトの含有量が０．０１質量％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、コバルトの含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、コバルトの含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Cobalt: 0.01% by mass or more and 0.5% by mass or less]
The content of cobalt (Co) is not particularly limited, but is preferably 0.01% by mass or more and 0.5% by mass or less with respect to 100% by mass of the copper alloy strip. If the cobalt content is less than 0.01% by mass, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the cobalt content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The cobalt content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔リン：０．０１質量％以上０．５質量％以下〕
　リン（Ｐ）の含有量は、特に限定されないが、銅合金条材１００質量％に対して０．０１質量％以上５質量％以下であることが好ましい。リンの含有量が０．０１％未満であると、抵抗温度係数の改善および体積抵抗率の調整の効果が十分に得られない可能性がある。一方で、リンの含有量が０．５質量％超であると、加工時の歪み量が増し、低温域で熱処理する際に適切な歪み分布を得ることが難しくなる。なお、リンの含有量は、例えば０質量％以上（非含有の場合を含む）、０．００１質量％以上、０．００５質量％以上であってもよい。 [Phosphorus: 0.01% by mass or more and 0.5% by mass or less]
The content of phosphorus (P) is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less with respect to 100% by mass of the copper alloy strip. If the phosphorus content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the resistivity may not be sufficiently obtained. On the other hand, if the phosphorus content exceeds 0.5% by mass, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution during heat treatment in a low temperature range. The phosphorus content may be, for example, 0% by mass or more (including the case where it is not contained), 0.001% by mass or more, and 0.005% by mass or more.
　〔残部：銅および不可避不純物〕
　上述した必須含有成分および任意添加成分以外は、残部がＣｕ（銅）および不可避不純物からなる。なお、ここでいう「不可避不純物」とは、おおむね銅系製品において、原料中に存在するものや、製造工程において不可避的に混入するもので、本来は不要なものであるが、微量であり、銅系製品の特性に影響を及ぼさないため許容されている不純物である。不可避不純物として挙げられる成分としては、例えば、硫黄（Ｓ）、酸素（Ｏ）等の非金属元素やアルミニウム（Ａｌ）やアンチモン（Ｓｂ）等の金属元素が挙げられる。なお、これらの成分含有量の上限は、上記成分毎に０．０５質量％、上記成分の総量で０．２０質量％とすればよい。 [Remaining: Copper and unavoidable impurities]
Except for the above-mentioned essential components and optional additives, the balance consists of Cu (copper) and unavoidable impurities. The "unavoidable impurities" referred to here are generally those that are present in the raw materials of copper-based products and those that are unavoidably mixed in the manufacturing process, which are originally unnecessary, but are in trace amounts. It is an acceptable impurity because it does not affect the characteristics of copper-based products. Examples of the components listed as unavoidable impurities include non-metal elements such as sulfur (S) and oxygen (O) and metal elements such as aluminum (Al) and antimony (Sb). The upper limit of the content of these components may be 0.05% by mass for each of the above components and 0.20% by mass for the total amount of the above components.
＜銅合金条材の結晶構造＞
　本発明の合金条材は、後方散乱電子回折法（ＥＢＳＤ法）により測定されるＫＡＭの平均値が１°以上５°未満であることを特徴とするものである。 <Crystal structure of copper alloy strip>
The alloy strip of the present invention is characterized in that the average value of KAM measured by the backscattered electron diffraction method (EBSD method) is 1 ° or more and less than 5 °.
　上述したとおり、ＫＡＭの平均値が１°以上５°未満であることにより、該銅合金条材がごく僅かな歪みを有するものとなり、この歪みによりプレス加工で生じる歪みを抑制（相殺）し、製品やロット間の抵抗値のばらつきを抑制することができる。一方で、ＫＡＭの平均値が１°未満であると、当該銅合金条材には歪みが少ない状態（再結晶後の状態）であり、プレス加工により歪みが導入されることにより商品やロット間に抵抗値のばらつきが生じる。また、ＫＡＭの平均値が５°以上であると、例えば使用時や実装時等に生じる熱の影響によって抵抗値が変動し、また、製品やロット間の抵抗値のばらつきが生じるおそれもある。 As described above, when the average value of KAM is 1 ° or more and less than 5 °, the copper alloy strip has a very slight strain, and the strain generated by the press working is suppressed (offset) by this strain. It is possible to suppress variations in resistance values between products and lots. On the other hand, if the average value of KAM is less than 1 °, the copper alloy strip has little strain (after recrystallization), and strain is introduced by press working to introduce strain between products and lots. The resistance value varies. Further, when the average value of KAM is 5 ° or more, the resistance value fluctuates due to the influence of heat generated at the time of use or mounting, for example, and the resistance value may fluctuate between products and lots.
　後方散乱電子回折法によりＫＡＭを測定した面積全体に対して、ＫＡＭの値が１°以上４°未満である面積が占める割合は、５０％以上であることが好ましい。ＫＡＭを測定した面積全体に対して、ＫＡＭの値が１°以上４°未満である面積が占める割合を５０％以上とすることにより、製品やロット間の抵抗値のばらつきをより有効に抑制することができる。ＫＡＭの値が１°以上４°未満である面積が占める割合が少ない場合、１°未満が多いこと、あるいは、４°以上が多いことを意味するが、１°未満が多い場合は、歪みが少ない状態が多く、４°以上が多い場合では高歪み域が多く、例えば、実装時の熱影響を受けやすくなり、多少の温度のぶれ、時間の短調に抵抗値が大きく左右され、ばらつきが大きく成る。ＫＡＭの値が１°以上４°未満である面積が占める割合は５０％以上が好ましく、さらに５０％以上７０％未満がより好ましい。 The ratio of the area where the KAM value is 1 ° or more and less than 4 ° to the entire area where KAM is measured by the backscattered electron diffraction method is preferably 50% or more. By setting the ratio of the area where the KAM value is 1 ° or more and less than 4 ° to 50% or more of the total area where KAM is measured, the variation in resistance value between products and lots can be suppressed more effectively. be able to. If the area where the KAM value is 1 ° or more and less than 4 ° occupies a small proportion, it means that there are many less than 1 °, or there are many 4 ° or more, but if there are many less than 1 °, the distortion is There are many small states, and when there are many 4 ° or more, there are many high distortion regions, for example, it is easily affected by heat during mounting, the resistance value is greatly affected by slight temperature fluctuations and time minors, and variations are large. Become. The ratio of the area where the KAM value is 1 ° or more and less than 4 ° is preferably 50% or more, and more preferably 50% or more and less than 70%.
　また、後方散乱電子回折法によりＫＡＭを測定した面積全体に対して、ＫＡＭの値が６°以上１５°未満である面積が占める割合は、３％以上２５％以下であることが好ましい。ＫＡＭを測定した面積全体に対して、ＫＡＭの値が６°以上１５°未満である面積が占める割合が３％以上２５％以下であるということは、延性が乏しい領域が存在することを意味し、そこがプレス時に破断の起点となることで、合金中に歪み量が増えることなくプレス加工ができ、寸法精度の向上、及び、製品やロット間の抵抗値のばらつきをより有効に抑制することができる。さらにＫＡＭの値が６°以上１５°未満である面積が占める割合は、５％以上２５％以下であることがより好ましい。 Further, the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured by the backscattered electron diffraction method is preferably 3% or more and 25% or less. The ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the total area where KAM is measured is 3% or more and 25% or less, which means that there is a region with poor ductility. Since this is the starting point of fracture during pressing, press working can be performed without increasing the amount of strain in the alloy, improving dimensional accuracy and more effectively suppressing variations in resistance values between products and lots. Can be done. Further, the proportion of the area where the KAM value is 6 ° or more and less than 15 ° is more preferably 5% or more and 25% or less.
　なお、ＫＡＭは、日本電子株式会社製、ＪＳＭ－７００１ＦＡを用いて後方散乱電子回折法により測定する。銅合金条材を、圧延方向に平行な断面を、樹脂埋め、電解研磨等によって鏡面仕上げし、測定試料とする。なお、例えば、銅合金条材をりん酸溶液に浸漬し、６０秒間通電して電解研磨を行うことにより、試料表面を鏡面仕上げすることができる。その断面試料のうち、板厚中央部の１００μｍ×１００μｍの視野領域を測定対象とし、ステップサイズ０．０５μｍにて測定を行う。ＴＳＬ社製の解析ソフトＯＩＭ　Ａｎａｌｙｓｉｓを用いて、すべての点を対象に、結晶方位差が１５°以上の場合を境界とした第一隣接の測定値を用いてＫＡＭの平均値を算出する。なお、また、当該視野領域において、０°以上１５°未満の範囲を１５分割し、１°ごとの面積率を求めることで、この面積を測定したＫＡＭを測定した面積全体に対し、１°以上４°未満である面積が占める割合及び６°以上１５°未満である面積が占める割合を求める。このような測定を任意の箇所５箇所で行い、その平均値を算出した。
  KAM is measured by the backscattered electron diffraction method using JSM-7001FA manufactured by JEOL Ltd. The cross section of the copper alloy strip parallel to the rolling direction is mirror-finished by resin filling, electrolytic polishing, etc., and used as a measurement sample. For example, the surface of the sample can be mirror-finished by immersing the copper alloy strip in a phosphoric acid solution and energizing for 60 seconds for electrolytic polishing. Among the cross-sectional samples, a visual field region of 100 μm × 100 μm at the center of the plate thickness is targeted for measurement, and measurement is performed with a step size of 0.05 μm. Using the analysis software OIM Analysis manufactured by TSL, the average value of KAM is calculated for all points using the measured values of the first adjacent to each other with the crystal orientation difference of 15 ° or more as the boundary. Further, in the visual field region, the range of 0 ° or more and less than 15 ° is divided into 15 and the area ratio for each 1 ° is obtained, so that the area measured by KAM is 1 ° or more with respect to the entire measured area. The ratio of the area less than 4 ° and the ratio of the area of 6 ° or more and less than 15 ° are calculated. Such measurement was performed at 5 arbitrary points, and the average value was calculated.
＜銅合金条材の物性＞
　本発明の合金条材のビッカース硬さは、特に限定されないが、１５０以上２００以下であることが好ましく、１５０以上１９０以下であることがより好ましい。ビッカース硬さがこのような範囲内では、特にプレス加工による歪みを抑制し、また、熱による抵抗値等の特性の変化を抑制することができる。 <Physical properties of copper alloy strips>
The Vickers hardness of the alloy strip of the present invention is not particularly limited, but is preferably 150 or more and 200 or less, and more preferably 150 or more and 190 or less. When the Vickers hardness is within such a range, strain due to press working can be suppressed, and changes in characteristics such as resistance value due to heat can be suppressed.
　なお、ビッカース硬さは、ＪＩＳ　Ｚ２２４４（２００９）に規定の方法に準拠して、銅合金材料の表面からビッカース硬さを測定する。このときの荷重（試験力）は２．９Ｎであり、圧子の圧下時間は１５ｓである。 The Vickers hardness is measured from the surface of the copper alloy material in accordance with the method specified in JIS Z2244 (2009). The load (test force) at this time is 2.9 N, and the indenter reduction time is 15 s.
　本発明の銅合金条材は、抵抗器、例えばシャント抵抗器やチップ抵抗器用の抵抗材料として極めて有用である。 The copper alloy strip of the present invention is extremely useful as a resistance material for resistors such as shunt resistors and chip resistors.
（２）銅合金条材の製造方法
　以上のような本発明の一実施形態による銅合金条材の製造方法を詳しく説明する。この製造方法は、前記銅合金条材の合金組成と実質同じ合金組成を有する銅合金素材に、８００℃以上９５０℃以下の高温域で加熱する第１熱処理工程と、熱間加工工程と、５０％以上の高加工率で冷間加工を施す第１冷間加工工程、および４００℃以上７００℃以下の中温域で加熱する第２熱処理工程を１セット工程とするときの１セット工程以上と、５％以上５０％未満の低加工率で冷間加工を施す第２冷間圧延工程と、２００℃／ｍｉｎ以上の昇温速度で２００℃以上４００℃未満に到達した後、１０～５５秒保持後、１００℃／ｍｉｎ以上の冷却速度で５０℃未満まで冷却する第３熱処理工程とを含むことを特徴としている。以下、各工程について説明する。 (2) Method for producing copper alloy strips The method for producing copper alloy strips according to the above embodiment of the present invention will be described in detail. This manufacturing method includes a first heat treatment step of heating a copper alloy material having substantially the same alloy composition as the alloy composition of the copper alloy strip in a high temperature range of 800 ° C. or higher and 950 ° C. or lower, a hot working step, and 50. One set process or more when the first cold processing process of performing cold processing at a high processing rate of% or more and the second heat treatment process of heating in a medium temperature range of 400 ° C. or more and 700 ° C. or less are set as one set process. The second cold rolling process in which cold working is performed at a low processing rate of 5% or more and less than 50%, and holding for 10 to 55 seconds after reaching 200 ° C or more and less than 400 ° C at a heating rate of 200 ° C / min or more. After that, it is characterized by including a third heat treatment step of cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or more. Hereinafter, each step will be described.
＜銅合金素材の作製工程＞
　銅合金素材は、前記銅合金条材の合金組成と実質同じ合金組成を有している。銅合金素材としては、例えば鋳造によって製造された鋳塊（インゴット）などが挙げられるが、特に限定はしない。ここで、銅合金素材の合金組成を、銅合金条材の合金組成と「実質同じ」としたのは、銅合金素材から銅合金条材を製造するまでの各工程において、銅合金素材中に、揮発（気化）しやすい成分等を含有する場合には、気化（蒸発）により消失することも想定されることから、そのような場合を含めるためである。 <Copper alloy material manufacturing process>
The copper alloy material has substantially the same alloy composition as the alloy composition of the copper alloy strip. Examples of the copper alloy material include ingots produced by casting, but are not particularly limited. Here, the alloy composition of the copper alloy material is set to be "substantially the same" as the alloy composition of the copper alloy strip in the copper alloy material in each process from the copper alloy material to the production of the copper alloy strip. , When a component or the like that easily volatilizes (vaporizes) is contained, it is assumed that it disappears due to vaporization (evaporation), and such a case is included.
＜第１熱処理工程＞
　第１熱処理工程は、銅合金素材に、８００℃以上９５０℃以下の高温域で加熱する工程である。第１熱処理工程での加熱温度を８００℃以上９５０℃以下の高温域にすることで、鋳造時に生じた凝固偏析や、晶出物、析出物を消失させ素材を均一化することができる。 <First heat treatment process>
The first heat treatment step is a step of heating the copper alloy material in a high temperature range of 800 ° C. or higher and 950 ° C. or lower. By setting the heating temperature in the first heat treatment step to a high temperature range of 800 ° C. or higher and 950 ° C. or lower, solidification segregation, crystallizations and precipitates generated during casting can be eliminated and the material can be made uniform.
　第１熱処理工程における加熱時間としては、特に限定されないが、１０分間以上１０時間以下であることが好ましい。 The heating time in the first heat treatment step is not particularly limited, but is preferably 10 minutes or more and 10 hours or less.
＜熱間加工工程＞
　熱間加工工程は、例えば８００℃～９５０℃程度の温度で、所望の板厚になるように加工（例えば圧延）する工程である。熱間加工については、圧延加工、もしくは押出加工のどちらでも特に制限はない。 <Hot working process>
The hot working step is a step of machining (for example, rolling) to a desired plate thickness at a temperature of, for example, about 800 ° C. to 950 ° C. The hot working is not particularly limited to either rolling or extrusion.
＜第１冷間加工工程＞
　第１冷間加工工程は、５０％以上の高加工率で冷間加工を施す工程である。第１冷間加工工程では、常法にしたがい、適宜冷間加工を施す。第１冷間加工工程における加工率を、５０％以上の高加工率とすることで、再結晶の駆動力となる歪み量を確保でき、次工程での再結晶を容易にさせることができる。 <First cold working process>
The first cold working step is a step of performing cold working at a high working rate of 50% or more. In the first cold working step, cold working is appropriately performed according to a conventional method. By setting the processing rate in the first cold processing step to a high processing rate of 50% or more, the amount of strain that is the driving force for recrystallization can be secured, and recrystallization in the next step can be facilitated.
＜第２熱処理工程＞
　第２熱処理工程は、４００℃以上７００℃以下の中温域で加熱を施す工程である。第２熱処理工程での加熱温度を４００℃以上７００℃以下の中温域にすることで、再結晶させ、歪みが除去された均一な組織を得ることができる。第２熱処理工程では、常法にしたがい、適宜熱処理を施す。 <Second heat treatment process>
The second heat treatment step is a step of heating in a medium temperature range of 400 ° C. or higher and 700 ° C. or lower. By setting the heating temperature in the second heat treatment step to a medium temperature range of 400 ° C. or higher and 700 ° C. or lower, recrystallization can be obtained to obtain a uniform structure from which strain has been removed. In the second heat treatment step, heat treatment is appropriately performed according to a conventional method.
　第２熱処理における加熱時間としては、特に限定されないが、１０秒以上１０時間以下とすることが好ましい。 The heating time in the second heat treatment is not particularly limited, but is preferably 10 seconds or more and 10 hours or less.
　なお、上記の第１冷間加工工程及び第２熱処理工程は、これら２つの工程を１セットの工程とするとき、１セット工程のみを行ってよく、又は２セット工程以上繰り返し行ってもよい。 The above-mentioned first cold working step and second heat treatment step may be performed only by one set step or may be repeated by two or more set steps when these two steps are regarded as one set step.
＜第２冷間圧延工程＞
　第２冷間圧延工程は、５％以上５０％未満の低加工率で冷間加工を施す工程である。このようにして低加工率で冷間加工を施すことにより、合金材料中の歪みの不均一さを抑制して圧延することができる。一方で、第２冷間圧延工程における加工率が５０％以上であると、後段の第３熱処理工程で加熱を施しても、ここで生じた歪みが不均一なまま維持して、プレス成形して製造される製品やロット間での抵抗値のばらつきを抑制することができる。さらには２０％以上５０％未満とすることで、ＫＡＭを測定した面積全体に対して、ＫＡＭの値が６°以上１５°未満である面積が占める割合を適正な範囲とすることができる。 <Second cold rolling process>
The second cold rolling step is a step of performing cold working at a low working rate of 5% or more and less than 50%. By performing cold working at a low working rate in this way, it is possible to suppress the non-uniformity of strain in the alloy material and roll. On the other hand, if the processing rate in the second cold rolling step is 50% or more, even if heating is applied in the third heat treatment step in the subsequent stage, the strain generated here is maintained as non-uniform and press molding is performed. It is possible to suppress variations in resistance values between products manufactured in the above-mentioned products and lots. Further, by setting it to 20% or more and less than 50%, the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured can be set to an appropriate range.
＜第３熱処理工程＞
　第３熱処理工程は、２００℃／ｍｉｎ以上の昇温速度で２００℃以上４００℃未満に到達した後、１０～５５秒保持後、１００℃／ｍｉｎ以上の冷却速度で５０℃未満まで冷却する第３熱処理工程で加熱を施す工程である。このようにして低温域で加熱を施すことにより、結晶粒が再結晶することなく、結晶内の歪みが抑制されて調整され、後方散乱電子回折法により測定されるＫＡＭの平均値が１°以上５°未満となる。さらには２５０℃以上とすることで、ＫＡＭを測定した面積全体に対して、ＫＡＭの値が６°以上１５°未満である面積が占める割合および、ＫＡＭを測定した面積全体に対して、ＫＡＭの値が１°以上４°未満である面積が占める割合を適正な範囲とすることができる。 <Third heat treatment process>
In the third heat treatment step, after reaching 200 ° C. or higher and lower than 400 ° C. at a heating rate of 200 ° C./min or more, holding for 10 to 55 seconds, and then cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or higher. 3 This is a step of heating in the heat treatment step. By heating in the low temperature range in this way, the distortion in the crystal is suppressed and adjusted without recrystallization of the crystal grains, and the average value of KAM measured by the backscattered electron diffraction method is 1 ° or more. It will be less than 5 °. Furthermore, by setting the temperature to 250 ° C. or higher, the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured, and the area where KAM is measured, the KAM The ratio occupied by the area whose value is 1 ° or more and less than 4 ° can be set as an appropriate range.
　なお、以上の銅合金条材の製造方法は、上述した工程以外の他の工程を設けてもよい。例えば、熱間加工工程の後に形成された厚い酸化被膜を機械研磨によって除去する面削工程や、圧延油を取り除く脱脂工程、熱処理によって生じた薄い酸化被膜を機械的または化学的に除去する研磨工程、変色を防止するために行う防錆工程などが挙げられる。 The above method for producing a copper alloy strip may be provided with a process other than the above-mentioned process. For example, a surface milling process for removing a thick oxide film formed after a hot working process by mechanical polishing, a degreasing process for removing rolling oil, and a polishing process for mechanically or chemically removing a thin oxide film generated by heat treatment. , Anti-rust process to prevent discoloration, etc.
　以上、本発明の実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、本発明の概念および特許請求の範囲に含まれるあらゆる態様を含み、本発明の範囲内で種々に改変することができる。 Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, but includes all aspects included in the concept of the present invention and the scope of claims, and varies within the scope of the present invention. Can be modified to.
　次に、本発明の効果をさらに明確にするために、本発明例および比較例について説明するが、本発明はこれらの実施例に限定されるものではない。 Next, in order to further clarify the effect of the present invention, examples of the present invention and comparative examples will be described, but the present invention is not limited to these examples.
　（発明例１～１５、比較例１～５）
　表１の「合金組成」欄に記載した合金組成を有する鋳塊（１０ｋｇ）を鋳造により製造した。この鋳塊に対し、加熱温度８００℃以上９５０℃以下、加熱時間１０分以上１０時間以下の条件で第１熱処理工程を行い、合金成分を均質化した後に、加工率７０％超とする熱間加工工程により板状（サイズ：長さ５００ｍｍ、幅１００ｍｍ、厚さ１０ｍｍ）に成形し水冷し、板状物を得た。 (Invention Examples 1 to 15, Comparative Examples 1 to 5)
An ingot (10 kg) having the alloy composition described in the “Alloy composition” column of Table 1 was produced by casting. The ingot is subjected to the first heat treatment step under the conditions of a heating temperature of 800 ° C. or higher and 950 ° C. or lower and a heating time of 10 minutes or longer and 10 hours or lower, and after homogenizing the alloy components, the hot working rate is increased to 70% or more. It was formed into a plate shape (size: length 500 mm, width 100 mm, thickness 10 mm) by a processing step and cooled with water to obtain a plate shape.
　次いで、９０％以上の高加工率での第１冷間加工工程、および４００℃以上７００℃以下の中温域で加熱する第２熱処理工程を行った。なお、第１冷間加工工程および第２熱処理工程は、本発明例１～５、７、８、１０～１５および比較例１～５では、それぞれ１回ずつ（１セット）行った。また、本発明例６および９では、１セット目と２セット目とで加工率および加熱条件を変更し、それぞれ２回ずつ（２セット）処理を行った。 Next, a first cold working step with a high working rate of 90% or more and a second heat treatment step of heating in a medium temperature range of 400 ° C. or higher and 700 ° C. or lower were performed. The first cold working step and the second heat treatment step were performed once (one set) in Examples 1 to 5, 7, 8, 10 to 15 of the present invention and Comparative Examples 1 to 5, respectively. Further, in Examples 6 and 9 of the present invention, the processing rate and the heating conditions were changed between the first set and the second set, and the treatment was performed twice (2 sets) each.
　その後、５％以上５０％未満の低加工率での第２冷間加工工程、および２００℃／ｍｉｎ以上の昇温速度で２００℃以上４００℃未満に到達した後、１０～５５秒保持後、１００℃／ｍｉｎ以上の冷却速度で５０℃未満まで冷却する第３熱処理工程を行った。なお、比較例１については、第２冷間加工工程および第３熱処理工程を行わず、また、比較例４については、第３熱処理工程を行わなかったため、表１では、行わなかった工程の欄に「－」と表記した。 Then, after the second cold working step at a low processing rate of 5% or more and less than 50%, and after reaching 200 ° C. or more and less than 400 ° C. at a heating rate of 200 ° C./min or more, holding for 10 to 55 seconds, A third heat treatment step of cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or more was performed. In addition, in Comparative Example 1, the second cold working step and the third heat treatment step were not performed, and in Comparative Example 4, the third heat treatment step was not performed. Therefore, in Table 1, the column of the steps not performed is performed. Was written as "-".
［銅合金条材の組成］
　銅合金条材の化学組成は、ＩＣＰ分析により測定し、下記表１に示した。 [Composition of copper alloy strip]
The chemical composition of the copper alloy strip was measured by ICP analysis and is shown in Table 1 below.
［後方散乱電子回折］
　ＫＡＭは、日本電子株式会社製、ＪＳＭ－７００１ＦＡを用いて後方散乱電子回折法により測定した。銅合金条材を、圧延方向に平行な断面を、樹脂埋め、電解研磨等によって鏡面仕上げし、測定試料とした。その断面試料のうち、板厚中央部の１００μｍ×１００μｍの視野領域を測定対象とし、ステップサイズ０．０５μｍにて測定を行った。ＴＳＬ社製の解析ソフトＯＩＭ　Ａｎａｌｙｓｉｓを用いて、結晶方位差が１５°以上を境界として、ＫＡＭの平均値を算出した。また、当該視野において、０°以上１５°未満の範囲を１５分割（０°以上１°未満、１°以上２°未満、２°以上３°未満、・・・１４°以上１５°未満）し、１°ごとの面積率を求めることで、測定対象とした１００μｍ×１００μｍ視野における、１°以上４°未満のＫＡＭを有する面積が占める割合及び６°以上１５°未満のＫＡＭを有する面積が占める割合を求めた。このような測定を任意の箇所５箇所で行い、その平均値を算出した。 [Backscattered electron diffraction]
KAM was measured by the backscattered electron diffraction method using JSM-7001FA manufactured by JEOL Ltd. The cross section of the copper alloy strip parallel to the rolling direction was mirror-finished by resin filling, electrolytic polishing, etc., and used as a measurement sample. Among the cross-sectional samples, a visual field region of 100 μm × 100 μm at the center of the plate thickness was set as the measurement target, and the measurement was performed with a step size of 0.05 μm. Using the analysis software OIM Analysis manufactured by TSL, the average value of KAM was calculated with the crystal orientation difference of 15 ° or more as the boundary. In addition, in the field of view, the range of 0 ° or more and less than 15 ° is divided into 15 (0 ° or more and less than 1 °, 1 ° or more and less than 2 °, 2 ° or more and less than 3 °, ... 14 ° or more and less than 15 °). By obtaining the area ratio for each 1 °, the ratio of the area having KAM of 1 ° or more and less than 4 ° and the area having KAM of 6 ° or more and less than 15 ° occupy in the 100 μm × 100 μm field of view as the measurement target. The ratio was calculated. Such measurement was performed at 5 arbitrary points, and the average value was calculated.
［ビッカース硬さ］
　ビッカース硬さは、ＪＩＳ　Ｚ２２４４（２００９）に規定の方法に準拠して、銅合金材料の表面からビッカース硬さを測定した。このときの荷重（試験力）は２．９Ｎであり、圧子の圧下時間は１５ｓである。 [Vickers hardness]
The Vickers hardness was measured from the surface of the copper alloy material in accordance with the method specified in JIS Z2244 (2009). The load (test force) at this time is 2.9 N, and the indenter reduction time is 15 s.
［抵抗値のばらつき］
　板厚０．２ｍｍ、幅２ｍｍ、長さ６０ｍｍのチップをプレスによって成形し、実装時の熱の影響を想定し、アルゴンガス雰囲気で２６０℃、３０分熱処理した後、電圧端子間距離を３０ｍｍとした四端子法により抵抗値を測定した。測定はｎ＝５００で行い、その結果より標準偏差と平均値を求めた。抵抗値のばらつきは、（標準偏差／平均値×１００）の式で求められる値が０．５０％以下の供試材（銅合金条材）を「Ａ」、０．５０％超０．５５％以下の供試材を「Ｂ」、０．５５％超０．６０％以下の供試材を「Ｃ」、０．６０％超の供試材を「Ｄ」として評価した。なお、（標準偏差／平均値×１００）の式で求められる値が０．６０％以下（すなわち、Ａ～Ｃ評価）であれば、抵抗値のばらつきは、合格レベルであると評価した。 [Variation of resistance value]
A chip with a plate thickness of 0.2 mm, a width of 2 mm, and a length of 60 mm is formed by a press, and after heat treatment at 260 ° C. for 30 minutes in an argon gas atmosphere, assuming the influence of heat during mounting, the distance between the voltage terminals is set to 30 mm. The resistance value was measured by the four-terminal method. The measurement was performed at n = 500, and the standard deviation and the average value were obtained from the results. The variation in resistance value is "A" for the test material (copper alloy strip) whose value obtained by the formula (standard deviation / average value x 100) is 0.50% or less, and more than 0.50% 0.55. The test material of% or less was evaluated as “B”, the test material of more than 0.55% and 0.60% or less was evaluated as “C”, and the test material of more than 0.60% was evaluated as “D”. If the value obtained by the formula (standard deviation / average value × 100) is 0.60% or less (that is, A to C evaluation), the variation in resistance value is evaluated as a passing level.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から分かるように、本発明例１～１５の銅合金条材は、３質量％以上２０質量％以下のマンガンを含有する組成を有し、後方散乱電子回折法により測定されるＫＡＭの平均値が１°以上５°未満と本発明の適正範囲内であるため、プレス成形してから２６０℃、３０分間の熱処理を行った後も、抵抗値のばらつきが少ないことが分かった。 As can be seen from Table 1, the copper alloy strips of Examples 1 to 15 of the present invention have a composition containing manganese of 3% by mass or more and 20% by mass or less, and the average of KAM measured by the backscattered electron diffraction method. Since the value was 1 ° or more and less than 5 °, which was within the appropriate range of the present invention, it was found that there was little variation in the resistance value even after heat treatment at 260 ° C. for 30 minutes after press molding.
　これに対し、比較例１の供試材（銅合金条材）は、１２質量％のマンガンを含有する組成を有しているが、後方散乱電子回折法により測定されるＫＡＭの平均値が０．５°と本発明の適正範囲よりも小さいため、プレス成形してから２６０℃、３０分間の熱処理を行った後の抵抗値のばらつきが大きいことが分かった。 On the other hand, the test material (copper alloy strip) of Comparative Example 1 has a composition containing 12% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 0. Since it was 5.5 °, which was smaller than the appropriate range of the present invention, it was found that the resistance value varied widely after heat treatment at 260 ° C. for 30 minutes after press molding.
　また、比較例２の供試材（銅合金条材）は、１２質量％のマンガンを含有する組成を有しているが、後方散乱電子回折法により測定されるＫＡＭの平均値が１２．１°と本発明の適正範囲よりも大きいため、プレス成形してから２６０℃、３０分間の熱処理を行った後の抵抗値のばらつきが大きいことが分かった。 Further, the test material (copper alloy strip) of Comparative Example 2 has a composition containing 12% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 12.1. Since ° is larger than the appropriate range of the present invention, it was found that the resistance value varies widely after heat treatment at 260 ° C. for 30 minutes after press molding.
　また、比較例３の供試材（銅合金条材）は、７質量％のマンガンを含有する組成を有しているが、第３熱処理として７００℃で加熱したことにより、後方散乱電子回折法により測定されるＫＡＭの平均値が０．６°と本発明の適正範囲よりも小さくなり、プレス成形してから２６０℃、３０分間の熱処理を行った後の抵抗値のばらつきが大きいことが分かった。 Further, the test material (copper alloy strip) of Comparative Example 3 has a composition containing 7% by mass of manganese, but by heating at 700 ° C. as the third heat treatment, a backscattered electron diffraction method was performed. It was found that the average value of KAM measured by the above was 0.6 °, which was smaller than the appropriate range of the present invention, and the resistance value varied widely after heat treatment at 260 ° C. for 30 minutes after press molding. It was.
　比較例４の供試材（銅合金条材）は、１０質量％のマンガンを含有する組成を有しているが、後方散乱電子回折法により測定されるＫＡＭの平均値が１３．８°と本発明の適正範囲よりも大きいため、プレス成形してから２６０℃、３０分間の熱処理を行った後の抵抗値のばらつきが大きいことが分かった。 The test material (copper alloy strip) of Comparative Example 4 has a composition containing 10% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 13.8 °. Since it is larger than the appropriate range of the present invention, it was found that the resistance value varies widely after heat treatment at 260 ° C. for 30 minutes after press molding.
　比較例５の供試材（銅合金条材）は、５質量％のマンガンを含有する組成を有しているが、後方散乱電子回折法により測定されるＫＡＭの平均値が０．９°と本発明の適正範囲よりも大きいため、プレス成形してから２６０℃、３０分間の熱処理を行った後の抵抗値のばらつきが大きいことが分かった。
  The test material (copper alloy strip) of Comparative Example 5 has a composition containing 5% by mass of manganese, but the average value of KAM measured by the backscattered electron diffraction method is 0.9 °. Since it is larger than the appropriate range of the present invention, it was found that the resistance value varies widely after heat treatment at 260 ° C. for 30 minutes after press molding.

Claims (8)

  1. 　３質量％以上２０質量％以下のマンガンを含有し、残部が銅および不可避不純物からなる合金組成を有する銅合金条材であって、
    　後方散乱電子回折法により測定されるＫＡＭの平均値が１°以上５°未満であることを特徴とする、銅合金条材。     A copper alloy strip containing 3% by mass or more and 20% by mass or less of manganese and having an alloy composition in which the balance is copper and unavoidable impurities.
    A copper alloy strip having an average value of KAM measured by a backscattered electron diffraction method of 1 ° or more and less than 5 °.
  2. 　後方散乱電子回折法によりＫＡＭを測定した面積全体に対して、ＫＡＭの値が１°以上４°未満である面積が占める割合は、５０％以上であることを特徴とする、請求項１に記載の銅合金条材。 The first aspect of claim 1, wherein the ratio of the area where the KAM value is 1 ° or more and less than 4 ° to the entire area where KAM is measured by the backscattered electron diffraction method is 50% or more. Copper alloy strip material.
  3. 　後方散乱電子回折法によりＫＡＭを測定した面積全体に対して、ＫＡＭの値が６°以上１５°未満である面積が占める割合は、３％以上２５％以下であることを特徴とする、請求項１または２に記載の銅合金条材。 The claim is characterized in that the ratio of the area where the KAM value is 6 ° or more and less than 15 ° to the entire area where KAM is measured by the backscattered electron diffraction method is 3% or more and 25% or less. The copper alloy strip according to 1 or 2.
  4. 　ビッカース硬さが１５０以上２００以下であることを特徴とする、請求項１～３のいずれか１項に記載の銅合金条材。 The copper alloy strip according to any one of claims 1 to 3, characterized in that the Vickers hardness is 150 or more and 200 or less.
  5. 　前記合金組成は、
    　０．０１質量％以上５質量％以下のニッケル、
    　０．０１質量％以上５質量％以下の錫、
    　０．０１質量％以上５質量％以下の亜鉛、
    　０．０１質量％以上０．５質量％以下の鉄、
    　０．０１質量％以上０．５質量％以下のケイ素、
    　０．０１質量％以上０．５質量％以下のクロム、
    　０．０１質量％以上０．５質量％以下のジルコニウム、
    　０．０１質量％以上０．５質量％以下のチタン、
    　０．０１質量％以上０．５質量％以下の銀、
    　０．０１質量％以上０．５質量％以下のマグネシウム、
    　０．０１質量％以上０．５質量％以下のコバルト、および、
    　０．０１質量％以上０．５質量％以下のリンからなる群より選択される１種以上の元素をさらに含有することを特徴とする、請求項１～４のいずれか１項に記載の銅合金条材。     The alloy composition is
    Nickel of 0.01% by mass or more and 5% by mass or less,
    Tin of 0.01% by mass or more and 5% by mass or less,
    Zinc of 0.01% by mass or more and 5% by mass or less,
    Iron of 0.01% by mass or more and 0.5% by mass or less,
    Silicon of 0.01% by mass or more and 0.5% by mass or less,
    Chromium of 0.01% by mass or more and 0.5% by mass or less,
    Zirconium of 0.01% by mass or more and 0.5% by mass or less,
    Titanium of 0.01% by mass or more and 0.5% by mass or less,
    0.01% by mass or more and 0.5% by mass or less of silver,
    Magnesium of 0.01% by mass or more and 0.5% by mass or less,
    Cobalt of 0.01% by mass or more and 0.5% by mass or less, and
    The copper according to any one of claims 1 to 4, further containing one or more elements selected from the group consisting of 0.01% by mass or more and 0.5% by mass or less of phosphorus. Alloy strip.
  6. 　請求項１～５のいずれか１項に記載の銅合金条材の製造方法であって、
    　前記銅合金条材の合金組成と実質同じ合金組成を有する銅合金素材に、８００℃以上９５０℃以下の高温域で加熱する第１熱処理工程と、
    　熱間加工工程と、
    　５０％以上の高加工率で冷間加工を施す第１冷間加工工程、および４００℃以上７００℃以下の中温域で加熱する第２熱処理工程を１セット工程とするときの１セット工程以上と、
    　５％以上５０％未満の低加工率で冷間加工を施す第２冷間加工工程と、
    　２００℃／ｍｉｎ以上の昇温速度で２００℃以上４００℃未満に到達した後、１０～５５秒保持後、１００℃／ｍｉｎ以上の冷却速度で５０℃未満まで冷却する第３熱処理工程とを含むことを特徴とする、銅合金条材の製造方法。     The method for producing a copper alloy strip according to any one of claims 1 to 5.
    A first heat treatment step of heating a copper alloy material having substantially the same alloy composition as the alloy composition of the copper alloy strip material in a high temperature range of 800 ° C. or higher and 950 ° C. or lower.
    Hot working process and
    One set process or more when the first cold processing process of performing cold processing at a high processing rate of 50% or more and the second heat treatment process of heating in a medium temperature range of 400 ° C. or more and 700 ° C. or less are set as one set process. ,
    The second cold working process, in which cold working is performed at a low working rate of 5% or more and less than 50%,
    It includes a third heat treatment step of reaching 200 ° C. or higher and lower than 400 ° C. at a heating rate of 200 ° C./min or higher, holding for 10 to 55 seconds, and then cooling to less than 50 ° C. at a cooling rate of 100 ° C./min or higher. A method for manufacturing a copper alloy strip, which is characterized in that.
  7. 　請求項１～５のいずれか１項に記載の銅合金条材を用いた抵抗器用抵抗材料。 A resistor material for a resistor using the copper alloy strip according to any one of claims 1 to 5.
  8. 　請求項７に記載の抵抗材料を有する抵抗器。 A resistor having the resistance material according to claim 7.
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