CN115516122B - Copper alloy strip, method for producing same, resistor material for resistor using copper alloy strip, and resistor - Google Patents
Copper alloy strip, method for producing same, resistor material for resistor using copper alloy strip, and resistor Download PDFInfo
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- CN115516122B CN115516122B CN202180032140.5A CN202180032140A CN115516122B CN 115516122 B CN115516122 B CN 115516122B CN 202180032140 A CN202180032140 A CN 202180032140A CN 115516122 B CN115516122 B CN 115516122B
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000463 material Substances 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 238000002003 electron diffraction Methods 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 77
- 238000005482 strain hardening Methods 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims 1
- 238000005259 measurement Methods 0.000 abstract description 17
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 9
- 230000000694 effects Effects 0.000 description 15
- 238000012545 processing Methods 0.000 description 15
- 238000009826 distribution Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001887 electron backscatter diffraction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The copper alloy strip of the present invention is a product, a copper alloy strip having a small variation in resistance value between batches, or the like, and has an alloy composition containing 3 to 20 mass% of manganese, the balance copper and unavoidable impurities, wherein the average value of KAM when KAM is measured by a back-scattered electron diffraction method is 1 to less than 4 °, and the proportion of the area of 1 to less than 4 ° in the entire area where KAM measurement is performed is 20 to less than 50%.
Description
Technical Field
The present invention relates to a copper alloy strip, a method for producing the same, a resistor material for a resistor using the copper alloy strip, and a resistor, and more particularly, to a copper alloy strip suitable for producing a substrate (chip) by press working, and having small variations in the resistance value of the produced substrate.
Background
The metal material of the resistor used in the resistor is required to have a stable resistance even when the ambient temperature changes, that is, a low Temperature Coefficient of Resistance (TCR) as an index thereof. The temperature coefficient of resistance is a parameter expressed in parts per million (ppm) per 1℃as TCR (10 6 /K)＝{(R-R 0 )/R 0 }×{1/(T-T 0 )}×10 6 Is expressed by the expression of (3). Here, T in the formula represents a test temperature (. Degree. C.), T 0 The reference temperature (. Degree. C.) is represented by R, the resistance value (. OMEGA.) at the test temperature T is represented by R 0 Indicating a reference temperature T 0 Resistance value (Ω) at that time. Since the TCR of cu—mn—ni alloy or cu—mn—sn alloy is very small, it is widely used as an alloy material constituting a resistor.
However, in the resistor manufactured by press molding such an alloy material, strain is induced in the alloy material during press molding, and there is a case where the resistance value is deviated, and the resistor cannot be stably manufactured.
Patent document 1 discloses that the residual strain can be removed by heating a copper alloy raw material in a non-oxidizing atmosphere formed of hydrogen after subjecting the copper alloy raw material to a rolling treatment at a high reduction rate, and as a result, the temperature coefficient of resistance can be reduced. However, even in the alloy material manufactured in this way, strain is unevenly remained, and the resistance value is deviated.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2016-69724
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a copper alloy strip suitable for manufacturing a substrate by press working, which is small in variation in resistance value between products and batches, and a method for manufacturing the copper alloy strip.
Means for solving the problems
As a result of intensive studies, the inventors of the present application have found that, by providing a copper alloy strip having an alloy composition containing 3 mass% or more and 20 mass% or less of manganese and the balance copper and unavoidable impurities, and by providing a KAM average value of 1 ° or more and less than 4 ° when KAM is measured and calculated by a back-scattered electron diffraction method, in a substrate produced by subjecting such a copper alloy strip to press working, variations in resistance values occurring between products and batches are small, and that such a copper alloy strip can be produced by a production method comprising the steps of: a 1 st heat treatment step of heating a copper alloy raw material having substantially the same alloy composition as the copper alloy strip in a high temperature range of 800 ℃ to 950 ℃; a hot working procedure; a 1 st cold working step of cold working at a high working rate of 50% or more and a 2 nd heat treatment step of heating at a medium temperature range of 400 ℃ to 700 ℃ inclusive are set to 1 or more steps in a single step; a 2 nd cold working step of performing cold working at a low working rate of 5% or more and less than 50%; and a 3 rd heat treatment step in which the substrate is heated at 200 ℃ or higher and 400 ℃ or lower for 2 hours or longer and 6 hours or shorter, and the inventors of the present application have completed the present invention based on the above findings.
That is, the gist of the present invention is as follows.
(1) A copper alloy strip having an alloy composition containing 3 to 20 mass% of manganese, the balance copper and unavoidable impurities, wherein the average value of KAM when KAM is measured by a back-scattered electron diffraction method and calculated is 1 to less than 4 DEG, and the proportion of the area of 1 to less than 4 DEG to the entire area of KAM measured is 20 to less than 50%.
(2) The copper alloy strip according to (1) above, wherein the ratio of the area of KAM having a value of 6 ° or more and less than 15 ° to the entire area of KAM measured is 1% or more and 5% or less.
(3) The copper alloy strip according to the above (1) or (2), wherein the Vickers hardness is 150 to 200.
(4) The copper alloy strip according to any one of the above (1) to (3), wherein the alloy composition further contains one or more elements selected from the group consisting of 0.01 to 5 mass% of nickel, 0.01 to 5 mass% of tin, 0.01 to 5 mass% of zinc, 0.01 to 0.5 mass% of iron, 0.01 to 0.5 mass% of silicon, 0.01 to 0.5 mass% of chromium, 0.01 to 0.5 mass% of zirconium, 0.01 to 0.5 mass% of titanium, 0.01 to 0.5 mass% of silver, 0.01 to 0.5 mass% of magnesium, 0.01 to 0.5 mass% of cobalt, and 0.01 to 0.5 mass% of phosphorus.
(5) A method for producing a copper alloy strip according to any one of the above (1) to (4), comprising the steps of: a 1 st heat treatment step of heating a copper alloy raw material having substantially the same alloy composition as the copper alloy strip in a high temperature range of 800 ℃ to 950 ℃; a hot working procedure; a 1 st cold working step of cold working at a high working rate of 50% or more and a 2 nd heat treatment step of heating at a medium temperature range of 400 ℃ to 700 ℃ inclusive are set to 1 or more steps in 1 group of steps; a 2 nd cold working step of performing cold working at a low working rate of 5% or more and less than 50%; and a 3 rd heat treatment step in which the substrate is heated at 200 ℃ or higher and 400 ℃ or lower for 2 hours or more and 6 hours or less.
(6) A resistor material for a resistor, which comprises the copper alloy strip according to any one of the above (1) to (4).
(7) A resistor having the resistive material according to (6) above.
Effects of the invention
According to the present invention, a copper alloy strip suitable for manufacturing a substrate by press working and having small variations in resistance value between products and batches, and a method for manufacturing the copper alloy strip can be provided.
Detailed Description
(1) Copper alloy strip
Hereinafter, preferred embodiments of the copper alloy strip according to the present invention will be described in detail. The copper alloy strip of the present invention has an alloy composition containing 3 to 20 mass% of manganese, the balance copper and unavoidable impurities, and is characterized in that the average value of KAM when KAM is measured by a back-scattered electron diffraction method is 1 to less than 4 DEG, and the ratio of the area of 1 to less than 4 DEG to the total area where KAM measurement is performed is 20 to less than 50%.
The reason why the composition and crystal structure of the copper alloy strip of the present invention are limited will be described below.
Composition of copper alloy strip
[ manganese: 3 mass% or more and 20 mass% or less
The copper alloy strip contains 3 to 20 mass% of manganese. Manganese (Mn) is an essential component in the present invention. By setting the manganese content in such a range, the temperature coefficient of resistance of the copper alloy material can be reduced. On the other hand, if the content of manganese is less than 3 mass%, the effect of reducing the temperature coefficient of resistance cannot be sufficiently obtained. When the manganese content is more than 20 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution during heat treatment in a low temperature region. From the viewpoint of temperature coefficient of resistance, the manganese content is preferably 5 mass% or more.
< optional component of copper alloy strip >
In addition, the alloy strip of the present invention may further contain, as an optional additive component, one or two or more elements selected from the group consisting of: 0.01 to 5 mass% nickel, 0.01 to 5 mass% tin, 0.01 to 5 mass% zinc, 0.01 to 0.5 mass% iron, 0.01 to 0.5 mass% silicon, 0.01 to 0.5 mass% chromium, 0.01 to 0.5 mass% zirconium, 0.01 to 0.5 mass% titanium, 0.01 to 0.5 mass% silver, 0.01 to 0.5 mass% magnesium, 0.01 to 0.5 mass% cobalt, and 0.01 to 0.5 mass% phosphorus. All of these elements are added for improving the temperature coefficient of resistance, adjusting the volume resistivity, and the like, but if the addition exceeds the respective predetermined ranges, there is a possibility that characteristic variations such as the resistance value, and the like, and an increase in raw material cost, and the like may occur even if the use temperature is lower than 400 ℃. The respective metal elements are described below.
[ Nickel: 0.01 mass% or more and 5 mass% or less
The nickel (Ni) content is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less. If the nickel content is less than 0.01%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the nickel content exceeds 5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The nickel content may be, for example, 0 mass% or more (including the case of no nickel), 0.001 mass% or more, or 0.005 mass% or more.
[ tin: 0.01 mass% or more and 5 mass% or less
The content of tin (Sn) is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less. If the tin content is less than 0.01%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the tin content exceeds 5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The tin content may be, for example, 0 mass% or more (including the case of no tin), 0.001 mass% or more, or 0.005 mass% or more.
[ iron: 0.01 mass% or more and 0.5 mass% or less
The content of iron (Fe) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less. If the iron content is less than 0.01%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the iron content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The iron content may be, for example, 0 mass% or more (including the case of no iron), 0.001 mass% or more, or 0.005 mass% or more.
[ zinc: 0.01 mass% or more and 5 mass% or less
The content of zinc (Zn) is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less. If the zinc content is less than 0.01%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the zinc content exceeds 5 mass%, there is a possibility that the resistance value deviation due to the dezincification phenomenon may occur. The zinc content may be, for example, 0 mass% or more (including the case of no zinc), 0.001 mass% or more, or 0.005 mass% or more.
[ silicon: 0.01 mass% or more and 0.5 mass% or less
The content of silicon (Si) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less. If the silicon content is less than 0.01 mass%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the silicon content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The silicon content may be, for example, 0 mass% or more (including the case of no silicon), 0.001 mass% or more, or 0.005 mass% or more.
[ chromium: 0.01 mass% or more and 0.5 mass% or less
The content of chromium (Cr) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of chromium is less than 0.01 mass%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the chromium content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The content of chromium may be, for example, 0 mass% or more (including the case of no chromium), 0.001 mass% or more, or 0.005 mass% or more.
[ zirconium: 0.01 mass% or more and 0.5 mass% or less
The content of zirconium (Zr) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of zirconium is less than 0.01 mass%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the zirconium content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The content of zirconium may be, for example, 0 mass% or more (including the case of no zirconium), 0.001 mass% or more, or 0.005 mass% or more.
[ titanium: 0.01 mass% or more and 0.5 mass% or less
The content of titanium (Ti) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of titanium is less than 0.01 mass%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the titanium content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The content of titanium may be, for example, 0 mass% or more (including the case of no titanium), 0.001 mass% or more, or 0.005 mass% or more.
[ silver: 0.01 mass% or more and 0.5 mass% or less
The content of silver (Ag) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the silver content is less than 0.01%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the silver content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The silver content may be, for example, 0 mass% or more (including the case of no silver), 0.001 mass% or more, or 0.005 mass% or more.
[ magnesium: 0.01 mass% or more and 0.5 mass% or less
The content of magnesium (Mg) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of magnesium is less than 0.01 mass%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the magnesium content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The content of magnesium may be, for example, 0 mass% or more (including the case of no magnesium), 0.001 mass% or more, or 0.005 mass% or more.
[ cobalt: 0.01 mass% or more and 0.5 mass% or less
The content of cobalt (Co) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the cobalt content is less than 0.01 mass%, the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the cobalt content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The cobalt content may be, for example, 0 mass% or more (including the case of no cobalt), 0.001 mass% or more, or 0.005 mass% or more.
[ phosphorus: 0.01 mass% or more and 0.5 mass% or less
The content of phosphorus (P) is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less with respect to 100 mass% of the copper alloy strip. If the phosphorus content is less than 0.01%, there is a possibility that the effect of improving the temperature coefficient of resistance and adjusting the volume resistivity cannot be sufficiently obtained. On the other hand, if the phosphorus content exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat-treating in a low-temperature region. The phosphorus content may be, for example, 0 mass% or more (including the case of no phosphorus), 0.001 mass% or more, or 0.005 mass% or more.
[ the balance: copper and unavoidable impurities
The balance other than the essential components and optional added components described above is Cu (copper) and unavoidable impurities. The "unavoidable impurities" herein are mainly substances that are present in the raw material in the copper-based product or are inevitably mixed in during the production process, and are impurities that are not originally required, but are allowed because the amount is small and do not affect the characteristics of the copper-based product. Examples of the component which is an unavoidable impurity include nonmetallic elements such as sulfur (S) and oxygen (O), and metallic elements such as aluminum (Al) and antimony (Sb). The upper limit of the content of these components may be set to 0.05 mass% of each of the above components and 0.20 mass% of the total amount of the above components.
Crystalline structure of copper alloy strip
The alloy strip of the present invention is characterized in that the average value of KAM when KAM is measured by a back-scattered electron diffraction (EBSD) method and calculated is 1 DEG or more and less than 4 DEG, and the ratio of the area of KAM to the entire area where KAM measurement is performed is 20% or more and less than 50%.
In such a copper alloy strip, since the average value of KAM when KAM is measured by a back-scattered electron diffraction method and calculated is 1 ° or more and less than 4 °, the copper alloy strip has a very small strain, and strain generated during press working can be suppressed (offset) by the strain, and variations in the resistance values between products and batches can be suppressed. On the other hand, if the average value of KAM is smaller than 1 °, strain is induced in the copper alloy strip (recrystallized state), and variations in resistance value occur between products and batches due to the strain induced by press working. If KAM has an average value of 4 ° or more, diffusion occurs excessively in the case of a use method of heat bonding such as plating or welding of copper alloy strips, and variations in the resistance values between products and batches occur.
In addition, the copper alloy strip of the present invention can more effectively suppress variations in the resistance value between products and batches by setting the area of KAM to a value of 1 ° or more and less than 4 ° to a ratio of 20% or more and less than 50%, preferably 20% or more and 45% or less.
If the KAM value is 1 ° or more and the area ratio of less than 4 ° is less than 20%, the area ratio of at least one of less than 1 ° and 4 ° increases, and as in the above, strain is likely to be induced by press working, or diffusion is likely to occur excessively in the case of a use method in which a copper alloy strip is subjected to heat bonding such as plating or welding, and there is a possibility that variations in the product and lot-to-lot resistance values occur. On the other hand, even if KAM is set to a value of 1 ° or more and a ratio of an area smaller than 4 ° is set to 50% or more, diffusion occurs excessively in the case of a use method of heat bonding such as plating or welding to a copper alloy strip, and there is a possibility that variations in the resistance values between products and batches may occur.
Thus, the copper alloy strip of the present invention has a stable resistance even after press working and in a use mode in which the copper alloy strip is subjected to heat bonding such as plating or welding by measuring and calculating KAM by the back-scattered electron diffraction (EBSD method) and the average value of KAM is 1 ° or more and less than 4 °, and the ratio of the area of KAM to the entire area in which KAM measurement is performed is 20% or more and less than 50% by weight.
In addition, relative to the whole area by back scattering electron diffraction method for KAM determination, preferably KAM value is 6 DEG to less than 15 DEG area of the ratio of 1% to 5%. The percentage of the area of KAM ranging from 6 ° to less than 15 ° to 1% to 5% relative to the entire area where KAM measurement is performed means that the high strain region having poor ductility is moderately provided and the structure is thermally stable. The high strain region serves as a starting point of fracture during punching, and thus punching can be performed without increasing the strain amount in the copper alloy strip, and dimensional accuracy can be improved and variation in the resistance value between products and batches can be more effectively suppressed.
KAM was measured by a back-scattered electron diffraction method using JSM-7001FA manufactured by japan electronics corporation. The copper alloy strip was subjected to resin embedding in a cross section parallel to the rolling direction and mirror finishing by electrolytic polishing or the like to prepare a measurement sample. For example, the surface of the sample may be mirror finished by immersing the copper alloy strip in a phosphoric acid solution and applying electricity for 60 seconds to perform electrolytic polishing. Further, on a cross section of the copper alloy strip located on the sample surface, a rectangular field of view (for example, 100 μm×100 μm) located in a region divided by a virtual line drawn out to be 1/4 of the thickness position of the copper alloy strip from each of the two surfaces of the copper alloy strip was set as a measurement target, and measurement was performed with a step size of 0.05 μm. The average value of KAM was calculated using Analysis software OIM by TSL corporation, using the first adjacent measurement values bordered by the case where the difference in crystal orientation was 15 ° or more, for all points. In the visual field region, the area ratio per 1 ° was obtained by dividing the range of 0 ° or more and less than 15 ° into 15 parts, and the ratio of 1 ° or more and less than 4 ° and the ratio of 6 ° or more and less than 15 ° with respect to the entire area measured by KAM for measuring the area were obtained. Such measurements were performed at arbitrary 5 sites, and the average value thereof was calculated.
Physical Properties of copper alloy strip
The vickers hardness HV of the alloy strip of the present invention is not particularly limited, and is preferably 150 to 200, more preferably 150 to 190. When the vickers hardness is within such a range, strain due to press working can be suppressed in particular, and a change in characteristics such as resistance value due to heat can be suppressed.
The vickers hardness was measured from the surface of the copper alloy strip according to the method defined in JIS Z2244 (2009). The load (test force) at this time was 2.9N, and the pressing time of the indenter was 15s.
The copper alloy strip of the present invention is useful as a resistive material for resistors, such as shunt resistors and chip resistors.
(2) Method for producing copper alloy strip
The method for producing a copper alloy strip according to one embodiment of the present invention described above will be described in detail. The manufacturing method is characterized by comprising the following steps: a 1 st heat treatment step of heating a copper alloy raw material having substantially the same alloy composition as the alloy composition of the copper alloy strip in a high temperature range of 800 ℃ to 950 ℃; a hot working procedure; a 1 st cold working step of cold working at a high working rate of 50% or more and a 2 nd heat treatment step of heating at a medium temperature range of 400 ℃ to 700 ℃ inclusive are set to 1 or more steps in 1 group of steps; a 2 nd cold working step of performing cold working at a low working rate of 5% or more and less than 50%; and a 3 rd heat treatment step of heating at 200 ℃ or more and 400 ℃ or less for 2 hours or more and 6 hours or less. The respective steps are described below.
< procedure for producing copper alloy raw Material >)
The alloy composition of the copper alloy raw material is substantially the same as the alloy composition of the copper alloy strip. Examples of the copper alloy raw material include an ingot (ingot) produced by casting, but are not particularly limited. The reason why the alloy composition of the copper alloy raw material is "substantially the same as the alloy composition of the copper alloy strip here is that the copper alloy raw material is considered to be lost due to vaporization (evaporation) when volatile (vaporized) components are contained in the copper alloy raw material in each step from the copper alloy raw material to the production of the copper alloy strip.
< 1 st Heat treatment Process >
The 1 st heat treatment step is a step of heating the copper alloy raw material in a high temperature range of 800 to 950 ℃. By setting the heating temperature in the 1 st heat treatment step to a high temperature range of 800 ℃ to 950 ℃, solidification segregation, crystal formation, and precipitation occurring during casting can be eliminated, and the raw material can be homogenized.
The heating time in the 1 st heat treatment step is not particularly limited, but is preferably 10 minutes to 10 hours.
< Heat Process >)
The hot working step is a step of working (for example, rolling) at a temperature of, for example, about 800 to 950 ℃ so as to have a desired plate thickness. The hot working may be either rolling working or extrusion working, and is not particularly limited.
< cold working procedure 1 >)
The 1 st cold working step is a step of performing cold working at a high working rate of 50% or more. In the 1 st cold working step, cold working is suitably performed using a conventional method. By setting the working ratio in the 1 st cold working step to a high working ratio of 50% or more, the strain amount serving as the driving force for recrystallization can be ensured, and recrystallization in the next step can be facilitated.
< 2 nd Heat treatment Process >
The 2 nd heat treatment step is a step of heating at a medium temperature range of 400 to 700 ℃. By setting the heating temperature in the 2 nd heat treatment step to a medium temperature range of 400 ℃ to 700 ℃, a uniform structure from which recrystallization and strain are removed can be obtained. In the 2 nd heat treatment step, heat treatment is suitably performed using a conventional method.
The heating time in the 2 nd heat treatment is not particularly limited, but is preferably 10 seconds to 10 hours.
When the two steps of the 1 st cold working step and the 2 nd heat treatment step are 1 set of steps, only 1 set of steps may be performed, or 2 or more sets of steps may be repeated.
< procedure 2 cold rolling >
The 2 nd cold rolling step is a step of cold working at a low reduction ratio of 5% or more and less than 50%. By performing cold working at a low working rate in this way, rolling can be performed while suppressing strain unevenness in the alloy material. On the other hand, if the reduction ratio in the 2 nd cold rolling step is 50% or more, the strain generated at this time can be maintained in a non-uniform state even when heating is performed in the 3 rd heat treatment step in the subsequent stage, and variations in the resistance value between press-molded products and batches can be suppressed. Further, by setting the processing ratio to more preferably 20% or more and less than 50%, the ratio of the area of KAM to 6 ° or more and less than 15 ° can be set to an appropriate range with respect to the entire area where KAM measurement is performed.
< Heat treatment procedure 3 >
The 3 rd heat treatment step is a step of heating at 200 ℃ or more and 400 ℃ or less for 2 hours or more and 6 hours or less. By performing heating in the low temperature region for a long period of time in this way, strain in the crystal can be suppressed and regulated without recrystallization of the crystal grains. By setting the heating time to 2 hours or longer, the low strain region where KAM is less than 1 ° is increased, and thus the ratio of the area where KAM is 1 ° or more and less than 4 ° can be adjusted to a range of 20% or more and less than 50%. On the other hand, if the heating time exceeds 6 hours, the low strain region is excessively enlarged, so that the average value of KAM is less than 1 °, and it is difficult to obtain desired characteristics. If the heating temperature is lower than 200 ℃, diffusion is less likely to occur, and strain in the crystal is less likely to be suppressed, whereby desired characteristics cannot be obtained, whereas if the heating temperature is 400 ℃ or higher, the average value of KAM becomes smaller than 1 ° due to recrystallization, and desired characteristics cannot be obtained. Further, by performing the long-time heat treatment at a heating temperature of 250 ℃ or higher in the 3 rd heat treatment step, the strain in the highly strained region having a KAM value of 6 ° or more and less than 15 ° can be effectively reduced, and the proportion of the area having a KAM value of 6 ° or more and less than 15 ° to the entire area where KAM measurement is performed can be 1% or more and 5% or less.
The above method for producing a copper alloy strip may be provided with steps other than the above steps. For example, a surface cutting step of removing a thick oxide film formed after a thermal processing step by mechanical polishing, a degreasing step of removing rolling oil, a polishing step of mechanically or chemically removing a thin oxide film produced by heat treatment, a rust prevention step for preventing discoloration, and the like can be given.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various modifications are possible within the scope of the present invention, including the concept of the present invention and all aspects contained in the claims.
Examples
Next, examples of the present invention and comparative examples will be described in order to further clarify the effects of the present invention, but the present invention is not limited to these examples.
(inventive examples 1 to 15 and comparative examples 1 to 5)
An ingot (10 kg) having the alloy composition described in the column "alloy composition" of table 1 was produced by casting. The ingot is subjected to a 1 st heat treatment step under conditions of a heating temperature of 800 to 950 ℃ and a heating time of 10 minutes to 10 hours, and after homogenizing the alloy components, the ingot is formed into a plate shape (dimensions: length 500mm, width 100mm, thickness 10 mm) by a heat treatment step having a working ratio of more than 70%, and water-cooled to obtain a plate-like article.
Then, a 1 st cold working step with a high working ratio of 90% or more and a 2 nd heat treatment step of heating in a medium temperature range of 400 ℃ to 700 ℃ are performed. The 1 st cold working step and the 2 nd heat treatment step were performed once (in one set) in each of invention examples 1 to 5, 7, 8, 10 to 15 and comparative examples 1 to 5. In invention examples 6 and 9, the processing rate and the heating conditions were changed in groups 1 and 2, and two (two groups) of treatments were performed.
Thereafter, a 2 nd cold working step of a low working ratio of 5% or more and less than 50% and a 3 rd heat treatment step of heating at 200 ℃ or more and less than 400 ℃ for 2 hours or more and 6 hours or less are performed. In comparative example 1, the 2 nd cold working step and the 3 rd heat treatment step were not performed, and in comparative example 4, the 3 rd heat treatment step was not performed, and thus "-" is marked in the column of the non-performed step in table 1.
[ composition of copper alloy strip ]
The alloy composition (mass%) of the copper alloy strip was measured by ICP analysis and is shown in table 1 below.
[ Back-scattered electron diffraction ]
KAM was measured by a back scattering electron diffraction method using JSM-7001FA manufactured by japan electronics corporation. The copper alloy strip was subjected to resin embedding in a cross section parallel to the rolling direction and mirror finishing by electrolytic polishing or the like to prepare a measurement sample. The measurement was performed with a step size of 0.05 μm using a 100 μm×100 μm field area in the center of the plate thickness of the cross-section sample as a measurement target. The average value of KAM was calculated using Analysis software OIM Analysis manufactured by TSL corporation, with a difference in crystal orientation of 15 ° or more as a boundary. In this field of view, the area ratio of at least 0 ° and less than 15 ° is divided into 15 parts (at least 0 ° and less than 1 °, at least 1 ° and less than 2 °, at least 2 ° and less than 3 °, at least … … °, and less than 15 °), and the area ratio of at least 1 ° and less than 4 ° in the 100 μm×100 μm field of view to be measured is obtained, whereby the ratio of the area of KAM having at least 1 ° and less than 4 ° and the ratio of the area of KAM having at least 6 ° and less than 15 ° are obtained. Such measurements were performed at arbitrary 5 sites, and the average value thereof was calculated.
[ Vickers hardness ]
The vickers hardness was measured from the surface of the copper alloy material according to the method defined in JIS Z2244 (2009). The load (test force) at this time was 2.9N, and the pressing time of the indenter was 15s.
[ deviation of resistance value ]
A copper alloy substrate having a thickness of 0.2mm, a width of 2mm and a length of 60mm was plated with tin (Sn) having a thickness of 5 μm on one side to form a substrate, and the substrate was press-molded to obtain a sample. The thermal influence at the time of mounting was expected, and after the sample was subjected to a heat treatment at 260℃for 30 minutes, the resistance value was measured by a four terminal method in which the distance between voltage terminals was 50 mm. The measurement was performed at n=500, and standard deviation and average value were obtained. In terms of the deviation of the resistance values, samples having a value of 0.50% or less obtained by the expression ((standard deviation/average) ×100) were rated as "class a", samples having a value of more than 0.50% and 0.55% or less were rated as "class B", samples having a value of more than 0.55% and 0.60% or less were rated as "class C", and samples having a value of more than 0.60% were rated as "class D". When the value obtained by the expression ((standard deviation/average value) ×100) is 0.60% or less (i.e., a-C level evaluation), the deviation of the resistance value is evaluated as a satisfactory level.
Sn plating is performed after pretreatment and acid washing. Pretreatment conditions, pickling conditions and Sn plating conditions were as follows.
(pretreatment conditions)
[ cathode electrolytic degreasing ]
Degreasing fluid: naOH 60g/L
Current density: 2.5A/dm 2
Treatment temperature: 60 ℃ of,
The treatment time is as follows: 60 seconds
[ Pickling conditions ]
Pickling solution: 10% H 2 SO 4
Treatment temperature: 23 DEG C
Treatment (impregnation) time: 30 seconds
[ Sn plating Condition ]
Plating bath composition: snSO 4 50g/L
H 2 SO 4 80g/L
Cresolsulfonic acid 50g/L
Beta-naphthol 1g/L
Gelatin 2g/L
Current density: 1.5A/dm 2
Bath temperature: 30 DEG C
The thickness of the Sn plating was measured using a fluorescent X-ray film thickness meter (trade name: SFT-9400) manufactured by Hitech, and the plating treatment time was adjusted so that each surface was 5 μm and each surface was 10 μm, whereby Sn plating was performed on both surfaces of the copper alloy base material.
TABLE 1
As is clear from table 1, since the copper alloy strips of invention examples 1 to 15 have compositions containing 3 mass% to 20 mass% of manganese, and the average value of KAM measured and calculated by the back-scattered electron diffraction method is 1 ° to less than 4 °, it is within the proper range of the present invention, and it is clear that the variation in resistance value is small even after heat treatment at 260 ℃ for 30 minutes after press molding.
In contrast, the sample (copper alloy strip) of comparative example 1 had a composition containing 12 mass% of manganese, but since the average value of KAM measured and calculated by the back-scattered electron diffraction method was 0.5 ° and smaller than the appropriate range of the present invention, it was found that the variation in resistance value after heat treatment at 260 ℃ for 30 minutes after press molding was large.
The sample (copper alloy strip) of comparative example 2 had a composition containing 12 mass% of manganese, but the average value of KAM measured and calculated by the back-scattered electron diffraction method was 12.1 ° and was larger than the appropriate range of the present invention, and it was found that the variation in resistance value after heat treatment at 260 ℃ for 30 minutes after press molding was large.
The sample (copper alloy strip) of comparative example 3 had a composition containing 7 mass% of manganese, but the average value of KAM measured and calculated by the back-scattered electron diffraction method was 0.6 ° by heating at 500 ℃ as the 3 rd heat treatment, and it was found that the variation in resistance value after heat treatment at 260 ℃ for 30 minutes after press molding was large, which was smaller than the appropriate range of the present invention.
The sample (copper alloy strip) of comparative example 4 had a composition containing 10 mass% of manganese, but the average value of KAM measured by the back-scattered electron diffraction method was 13.8 ° and was larger than the appropriate range of the present invention, and it was found that the variation in resistance value after heat treatment at 260 ℃ for 30 minutes after press molding was large.
The sample (copper alloy bar) of comparative example 5 had a composition containing 6 mass% of manganese, but the average value of KAM measured by the back-scattered electron diffraction method was 4.1 ° and was larger than the appropriate range of the present invention, and it was found that the variation in resistance value after heat treatment at 260 ℃ for 30 minutes after press molding was large.
Claims (7)
1. A copper alloy strip having an alloy composition containing 3 to 20 mass% of manganese and the balance copper and unavoidable impurities, characterized in that,
the average value of KAM when KAM is measured by a back-scattered electron diffraction method and calculated is 1 ° or more and less than 4 °, and the proportion of the area of KAM having a value of 1 ° or more and less than 4 ° in the whole area of the measured KAM is 20% or more and less than 50%.
2. The copper alloy strip according to claim 1, wherein the ratio of the area of KAM having a value of 6 ° or more and less than 15 ° to the entire area of KAM measured is 1% or more and 5% or less.
3. The copper alloy strip according to claim 1, wherein the vickers hardness is 150 or more and 200 or less.
4. A copper alloy strip according to any one of claims 1 to 3, wherein the alloy composition further comprises a metal selected from the group consisting of
0.01 to 5 mass% of nickel,
0.01 to 5 mass% of tin,
0.01 to 5 mass% of zinc,
0.01 to 0.5 mass% of iron,
0.01 to 0.5 mass% of silicon,
0.01 to 0.5 mass% of chromium,
0.01 to 0.5 mass% of zirconium,
0.01 to 0.5 mass% of titanium,
0.01 to 0.5 mass% of silver,
0.01 to 0.5 mass% of magnesium,
0.01 to 0.5 mass% of cobalt
0.01 to 0.5 mass% of one or more elements selected from the group consisting of phosphorus.
5. A method for producing a copper alloy strip according to any one of claims 1 to 4, comprising the steps of:
a 1 st heat treatment step of heating a copper alloy raw material having substantially the same alloy composition as the copper alloy strip in a high temperature range of 800 ℃ to 950 ℃;
a hot working procedure;
a 1 st cold working step of cold working at a high working rate of 50% or more and a 2 nd heat treatment step of heating at a medium temperature range of 400 ℃ to 700 ℃ inclusive are set to 1 or more steps in 1 group of steps;
a 2 nd cold working step of performing cold working at a low working rate of 5% or more and less than 50%; and
and a 3 rd heat treatment step in which the substrate is heated at 200 ℃ or higher and 400 ℃ or lower for 2 hours or more and 6 hours or less.
6. A resistor material for a resistor, which comprises the copper alloy strip according to any one of claims 1 to 4.
7. A resistor having the resistive material of claim 6.
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| WO2024135786A1 (en) * | 2022-12-23 | 2024-06-27 | 古河電気工業株式会社 | Copper alloy material, resistive material for resistor, and resistor |
| WO2024135787A1 (en) * | 2022-12-23 | 2024-06-27 | 古河電気工業株式会社 | Copper alloy material, resistive material including same for resistor, and resistor |
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| CN102534298A (en) * | 2010-12-13 | 2012-07-04 | 株式会社神户制钢所 | Copper alloy |
| CN110168120A (en) * | 2017-01-10 | 2019-08-23 | 古河电气工业株式会社 | Resistance material Cu alloy material and its manufacturing method and resistor |
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| JP6471494B2 (en) | 2014-09-29 | 2019-02-20 | 日立金属株式会社 | Cu alloy material and method for producing the same |
| KR102702060B1 (en) * | 2018-06-20 | 2024-09-02 | 후루카와 덴키 고교 가부시키가이샤 | Resistive material for resistors and method for manufacturing the same and resistors |
| CN113454253B (en) * | 2019-03-28 | 2022-09-06 | 古河电气工业株式会社 | Copper alloy strip, method for producing same, resistance material for resistor using same, and resistor |
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| CN102534298A (en) * | 2010-12-13 | 2012-07-04 | 株式会社神户制钢所 | Copper alloy |
| CN110168120A (en) * | 2017-01-10 | 2019-08-23 | 古河电气工业株式会社 | Resistance material Cu alloy material and its manufacturing method and resistor |
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