TW202309303A - Copper alloy material, and resistive material for resistor and resistor using same - Google Patents

Abstract

Provided is a copper alloy material which, as, for example, a resistive material, has sufficiently high volume resistivity, and for which the absolute value of the thermoelectromotive force against copper is small and the resistance temperature coefficient over a wide temperature range from normal temperature (for example, 20 DEG C) to a high temperature (for example, 150 DEG C) is small, and the absolute value thereof is small. Also provided is a resistive material for a resistor and a resistor using said copper alloy material. The copper alloy material contains: Mn, 20.0% to 35.0% by mass; Ni, 5.0% to 15.0% by mass; Fe, 0.01% to 0.50% by mass; and Co, 1.50% by mass or less (including a case in which the amount of Co is 0% by mass). The total amount of Fe and Co is in the range of 0.10% to 2.00% by mass, and the remainder is Cu and unavoidable impurities.

Description

Copper alloy material, resistance material for resistor using the copper alloy material, and resistor

The present invention relates to a copper alloy material, a resistance material for a resistor using the copper alloy material, and a resistor.

The absolute value of the temperature coefficient of resistance (TCR) of the index is required to be small in order to make the resistance of the resistor stable even if the ambient temperature changes, as for the metal material used as the resistance material for the resistor. The so-called temperature coefficient of resistance refers to the change in resistance value due to temperature in parts per million (ppm) per 1 °C, and is based on TCR (×10 ^-6 /°C) = {(R - R ₀ )/ R ₀ }×{1/(T−T ₀ )}×10 ⁶ is represented. Here, in the formula, T represents the test temperature (°C), T ₀ represents the reference temperature (°C), R represents the resistance value (Ω) at the test temperature T, and R ₀ represents the resistance value (Ω) at the reference temperature T ₀ . In particular, Cu—Mn—Ni alloys and Cu—Mn—Sn alloys have been widely used as alloy materials for constituting resistance materials because of their very small TCR.

However, when these Cu-Mn-Ni alloys and Cu-Mn-Sn alloys are used as the resistance material in a resistor designed to a predetermined resistance value by using the resistance material to form a circuit (pattern), for example, the volume The resistivity is less than 50×10 ^-8 (Ω·m), and the cross-sectional area of the resistive material must be reduced to increase the resistance value of the resistor. In such a resistor, there are disadvantages such as: Joule heat generated in a resistance material with a small cross-sectional area when a large current temporarily flows into the circuit and when a large current continues to flow to a certain extent. It rises to generate heat, and as a result, the resistance material is easily broken (fusing) due to heat.

Therefore, in order to suppress the decrease in the cross-sectional area of the resistive material, a resistive material having a higher volume resistivity is being sought.

For example, in Patent Document 1, it is considered that in a copper alloy containing Mn in the range of 23% by mass to 28% by mass and Ni in the range of 9% by mass to 13% by mass, the resistance to copper is reduced. The mass fraction of Mn and the mass fraction of Ni are formed in such a way that the thermoelectromotive force decreases more than ±1 μV/°C at 20°C, that is, a copper alloy can be obtained, which can obtain more than 50×10 ^-8 [Ω·m] High resistance (volume resistivity ρ), and small thermal electromotive force to copper (thermal electromotive force to copper, EMF), low temperature coefficient of resistance, and high stability to time (time invariance) of intrinsic resistance.

In addition, in Patent Document 2, it is considered that in a copper alloy containing Mn in the range of 21.0% by mass to 30.2% by mass and Ni in the range of 8.2% by mass to 11.0% by mass, the temperature will be reduced from 20°C to 11.0% by mass. The TCR value x[ppm/°C] in the temperature range up to 60°C is in the range of -10≦x≦-2 or 2≦x≦10, and the volume resistivity ρ is set at 80×10 ^-8 [Ω・m] and 115×10 ^-8 [Ω・m] or less, that is, it is possible to suppress the decrease in the cross-sectional area of a circuit using resistors such as chip resistors using resistive materials and suppress the increase in Joule heat of resistive materials. [Prior Art Document] (Patent Document)

Patent Document 1: Japanese PCT Publication No. 2016-528376 Patent Document 2: Japanese Patent Laid-Open No. 2017-053015

[Problem to be solved by the invention] In recent years, resistors such as shunt resistors and chip resistors in electrical equipment systems of electric vehicles, etc., have not only a large volume resistivity ρ, but also high precision that can withstand higher temperature usage environments. Copper alloys used in such resistors are also seeking high precision that can withstand higher temperature usage environments.

Regarding this point, in the copper alloy described in Patent Document 1, it is described that the thermal electromotive force (EMF) against copper at 20° C. is reduced more than ±1 μV/° C. In addition, in the copper alloy described in Patent Document 1, as described in FIG. 3 , in the temperature range from 20° C. to 150° C. including a higher temperature range, the temperature dependence of the resistance becomes larger. It is known that the resistance value tends to produce errors in the high-temperature region, but it is difficult to reduce its absolute value.

In addition, in the copper alloy described in Patent Document 2, it is described that the thermal electromotive force (EMF) generated between 20°C and 100°C for copper is set to be ±2 μV/°C or less, and the resistance The temperature-dependent temperature coefficient of resistance (TCR) is set to be within the range of ±50× ^10-6 [°C ^{- 1} ] in the temperature range from 20°C to 60°C, but the absolute value of reducing EMF has been sought until now , and controlling the temperature coefficient of resistance (TCR) in a wide temperature range from normal temperature (for example, 20° C.) to high temperature (for example, 150° C.) to a negative number with a small absolute value.

As described above, the copper alloys described in Patent Documents 1 and 2 have room for further improvement in that the volume resistivity ρ is increased, and the use in a wide temperature range from room temperature to high temperature is also considered. Environmental temperature coefficient of resistance (TCR) and copper thermal electromotive force (EMF), reduce the absolute value of copper thermal electromotive force (EMF) and will be in a wide temperature range from normal temperature (such as 20°C) to high temperature (such as 150°C) The temperature coefficient of resistance (TCR) in is set to a negative number with a small absolute value.

Therefore, an object of the present invention is to provide a copper alloy material having a sufficiently high volume resistivity as a resistance material and a resistance to copper thermoelectromotive force, and a resistor material for a resistor using the copper alloy material and a resistor. The absolute value is small, and the temperature coefficient of resistance in a wide temperature range from normal temperature (for example, 20° C.) to high temperature (for example, 150° C.) is negative and the absolute value is small. [Technical means to solve the problem]

The inventors of the present invention completed the present invention by discovering the fact that an alloy composition contains the following components: Mn 20.0% by mass to 35.0% by mass; Ni 5.0% by mass to 15.0% by mass; and Fe is 0.01 mass% or more and 0.50 mass% or less; and the Co content is in the range of 0 mass% or more and 1.50 mass% or less, including the case where the Co content is 0 mass%, and the total amount of Fe and Co is 0.10 In the range of not less than mass % and not more than 2.00 mass %, the balance is composed of Cu and unavoidable impurities, that is, a copper alloy material can be obtained, which has, for example, a sufficiently high volume resistivity p as a resistive material, and for The absolute value of copper thermoelectromotive force is small, and the temperature coefficient of resistance in a wide temperature range from normal temperature (for example, 20° C.) to high temperature (for example, 150° C.) is negative and small in absolute value.

In order to achieve the above objects, the gist of the present invention is constituted as follows. (1) A copper alloy material having an alloy composition containing the following components: Mn: 20.0% by mass to 35.0% by mass; Ni: 5.0% by mass to 15.0% by mass; and Fe: 0.01 Mass % to 0.50 mass %; and Co in the range of 0 mass % to 1.50 mass %, including the case where the Co content is 0 mass %, and the total amount of Fe and Co is 0.10 mass % or more and Within the range of 2.00% by mass or less, the balance is composed of Cu and unavoidable impurities. (2) The copper alloy material according to the above (1), wherein the alloy composition contains: Mn: 20.0% by mass to 30.0% by mass. (3) The copper alloy material according to (1) or (2) above, wherein the alloy composition contains: Fe: 0.01% by mass to 0.30% by mass; and Co: 0.01% by mass to 1.50% by mass . (4) The copper alloy material according to any one of the above (1) to (3), wherein the content of Mn is expressed as w mass %, the content of Ni is expressed as x mass %, and the content of Fe is expressed as When y mass % and the content of Co are taken as z mass %, w, x, y and z satisfy the relationship of the formula (1) shown below: 0.8w－10.5≦x＋10y＋5z≦0.8w－6.5・・・(I). (5) The copper alloy material according to any one of the above (1) to (4), wherein when the content of Mn is represented by w mass % and the content of Ni is represented by x mass %, the ratio of x to w is The ratio was less than 0.40. (6) The copper alloy material according to any one of the above (1) to (5), wherein the copper alloy material is a plate, rod, strip, or wire, and has an average grain size of 60 μm or less . (7) The copper alloy material according to any one of (1) to (6) above, wherein the alloy composition further contains at least one selected from the group consisting of: Sn: 0.01 mass % to 3.00 mass %; Zn: 0.01 mass % to 5.00 mass %; Cr: 0.01 mass % to 0.50 mass %; Ag: 0.01 mass % to 0.50 mass %; Al: 0.01 mass % or more and 1.00 mass % or less; Mg: 0.01 mass % or more and 0.50 mass % or less; Si: 0.01 mass % or more and 0.50 mass % or less; and P: 0.01 mass % or more and 0.50 mass % or less. (8) A resistance material for a resistor, comprising the copper alloy material described in any one of (1) to (7) above. (9) A resistor which is a shunt resistor or a chip resistor comprising the resistive material for resistors according to (8) above. [effect]

According to the present invention, it is possible to provide a copper alloy material having, for example, a sufficiently high volume resistivity as a resistance material, and a resistance material for a resistor using the copper alloy material, and a resistance material for a resistor using the copper alloy material. It is small, and the temperature coefficient of resistance in a wide temperature range from normal temperature (for example, 20° C.) to high temperature (for example, 150° C.) is negative and the absolute value is small.

Preferred embodiments of the copper alloy material of the present invention will be described in detail below. In addition, in the composition of the alloy of the present invention, "mass %" may be expressed only as "%".

The copper alloy material of the present invention has an alloy composition containing the following components: Mn: 20.0% by mass to 35.0% by mass; Ni: 5.0% by mass to 15.0% by mass; and Fe: 0.01% by mass or more and 0.50 mass % or less; and Co is in the range of 0 mass % to 1.50 mass %, including the case where the Co content is 0 mass %, and the total amount of Fe and Co is 0.10 mass % to 2.00 mass % Within the following range, the balance is composed of Cu and unavoidable impurities.

As described above, in the copper alloy material of the present invention, Mn is contained in the range of 20.0% by mass to 35.0% by mass, Ni is contained in the range of 5.0% by mass to 15.0% by mass, and Ni is contained in the range of 0.01% by mass to 15.0% by mass. Fe is contained within the range of 0.50% by mass or less, and the content of Co is set within the range of 0% by mass or more and 1.50% by mass or less, including the case where the Co content is 0% by mass, and the temperature between 0°C and 80°C The absolute value of the copper thermal electromotive force (EMF) generated between the environment (hereinafter sometimes simply referred to as "copper thermal electromotive force") decreases, and the temperature coefficient of resistance (TCR) in the temperature range of 20°C to 150°C ) (hereinafter sometimes simply referred to as "temperature coefficient of resistance") becomes a negative number with a small absolute value, so it is possible to increase the precision of the resistor even in a high-temperature environment. In addition, by containing Mn in the range of 20.0% by mass to 35.0% by mass and Ni in the range of 5.0% by mass to 15.0% by mass, the volume resistivity ρ can be increased and the thermal electromotive force ( EMF), and set the temperature coefficient of resistance (TCR) in the temperature range of 20°C to 150°C as a negative number with a small absolute value. As a result, with the copper alloy material of the present invention, it is possible to provide a copper alloy material having a sufficiently high volume resistivity p as a resistance material, and a resistance material for a resistor using the copper alloy material and a resistor. And the absolute value of the copper thermal electromotive force (EMF) is small, and the temperature coefficient of resistance is negative and the absolute value is small.

[1] Composition of copper alloy material ＜Must contain ingredients＞ The alloy composition of the copper alloy material of the present invention contains the following components: Mn 20.0 mass % to 35.0 mass %; Ni 5.0 mass % to 15.0 mass %; Fe 0.01 mass % to 0.50 mass %; and Co The content of Co is within the range of 0% by mass to 1.50% by mass, including the case where the Co content is 0% by mass. In other words, the alloy composition of the copper alloy material of the present invention contains Mn, Ni, and Fe as essential components.

(Mn: 20.0% by mass to 35.0% by mass) Mn (manganese) is an element that increases the volume resistivity ρ and adjusts a negative temperature coefficient of resistance (TCR) toward a positive value, thereby reducing the absolute value of the temperature coefficient of resistance (TCR). In order to exert this function and obtain a homogeneous copper alloy material, Mn is preferably contained at least 20.0% by mass, more preferably at least 22.0% by mass, and still more preferably at least 24.0% by mass. Here, increasing the Mn content to 22.0 mass % or more, 24.0 mass % or more, or 25.0 mass % or more can further increase the volume resistivity ρ of the copper alloy material. On the other hand, when the Mn content exceeds 35.0% by mass, the temperature coefficient of resistance (TCR) tends to become a positive number, and the absolute value of the thermal electromotive force (EMF) to copper also tends to increase. Therefore, the Mn content is preferably in the range of 20.0% by mass or more and 35.0% by mass or less. On the other hand, if the Mn content exceeds 30.0% by mass, a second phase different from the first phase, which is the parent phase, is likely to be generated during the long-term use of the copper alloy material as a resistance material, etc. Time passes and changes. Therefore, from the viewpoint of improving the stability of electrical properties against heat and the like, it is preferable to set the Mn content to 30.0% by mass or less.

(Ni: 5.0% by mass to 15.0% by mass) Ni (nickel) is an element that reduces the absolute value of thermal electromotive force (EMF) to copper. In order to exert this function, Ni is preferably contained in an amount of 5.0% by mass or more. On the other hand, when the Ni content is large, the absolute value of the temperature coefficient of resistance (TCR) tends to increase toward a negative value. Therefore, the Ni content is preferably in the range of 5.0% by mass or more and 15.0% by mass or less. In particular, in the copper alloy material of the present invention, the Ni content is preferably such that the ratio of x to w is less than 0.40 when the Mn content is w mass % and the Ni content is x mass %. Reducing the ratio of x to w further reduces the absolute value of the temperature coefficient of resistance (TCR). Therefore, the ratio of x to w is preferably less than 0.40, more preferably not more than 0.35. Furthermore, from the viewpoint of reducing the absolute value of the temperature coefficient of resistance (TCR), the content of Ni in the copper alloy material may be in the range of 5.0 mass % or more and 15.0 mass % or less, or may be 5.0 mass % or more And the range of 12.0 mass % or less can also be set as the range of 5.0 mass % or more and 9.0 mass % or less.

(Fe: 0.01% by mass to 0.50% by mass) Fe (iron) is an element that adjusts the thermal electromotive force (EMF) against copper toward a positive value and reduces the absolute value of the thermal electromotive force (EMF) against copper. In particular, since Fe is expected to have a greater effect on the absolute value of copper thermal electromotive force (EMF) than Co described later, and the raw material price is also low, Fe must be contained in an amount of 0.01% by mass or more. On the other hand, Fe is an element that is difficult to maintain a solid solution state in the matrix (matrix phase), and easily forms a second phase. In particular, if the Fe content exceeds 0.50% by mass, crystallization of the second phase occurs, and the absolute value of the temperature coefficient of resistance (TCR) tends to increase, and the absolute value of the thermal electromotive force (EMF) to copper also tends to increase. Therefore, the Fe content is preferably in the range of 0.01% by mass to 0.50% by mass. In particular, from the standpoint of further improving the stability of electrical properties against heat and the like, thereby further improving reliability when used as a resistance material for a long period of time, the Fe content is more preferably 0.30% by mass or less. More preferably, it is 0.20 mass % or less.

＜The first optional additive (Co)＞ (Co: 0% by mass to 1.50% by mass, including 0% by mass) The copper alloy material of the present invention may contain Co in addition to Mn, Ni and Fe which are essential components. Co (cobalt) is an element that adjusts the thermal electromotive force (EMF) against copper toward a positive value and reduces the absolute value of the thermal electromotive force (EMF) against copper. In addition, Co is an element that can make up for the lack of Fe content and has a wide range of content that can obtain a uniform structure. When used together with Fe, it is easy to obtain the desired thermal electromotive force (EMF) for copper. The Co content may be 0% by mass, but from the viewpoint of exhibiting this function, the Co content is preferably 0.01% by mass or more, more preferably 0.10% by mass or more. On the other hand, since Co is an expensive element, the Co content is preferably 1.50% by mass or less. In addition, since Co is an element that does not easily generate a second phase unlike Fe, it is preferably contained instead of Fe, and therefore, both Fe and Co are preferably contained. In particular, by containing 0.01% by mass or more of Co and setting the Fe content in the range of 0.01% by mass to 0.30% by mass, even if the Mn content exceeds 30.0% by mass, it is possible to improve the stability of electrical characteristics to heat, etc. This further improves reliability when used as a resistance material for a long period of time.

(Total of Fe and Co: 0.10% by mass to 2.00% by mass) Both Fe and Co are elements that will adjust the thermoelectromotive force (EMF) against copper toward a positive direction and reduce the absolute value of the thermoelectromotive force (EMF) against copper. In particular, from the viewpoint of easily obtaining the desired thermal electromotive force (EMF) for copper, one or both of Fe and Co are added, and the total content of these is 0.10% by mass or more. Even if the content of Fe is like 0.01 Such a trace amount by mass % and the absence of Co can still reduce the absolute value of the thermal electromotive force (EMF) to copper. On the other hand, if the total amount of Fe and Co exceeds 2.00% by mass, it will be difficult to obtain a uniform structure, so the electrical characteristics will easily vary. Therefore, the total amount of Fe and Co is preferably in the range of 0.10% by mass to 2.00% by mass, more preferably in the range of 0.30% by mass to 1.65% by mass.

In the copper alloy material of the present invention, it is preferable that the content of Mn be w mass%, the content of Ni be x mass%, the content of Fe be y mass%, and the content of Co be z mass%. When, w, x, y and z satisfy the relation of (I) formula of following expression: 0.8w－10.5≦x＋10y＋5z≦0.8w－6.5・・・(I).

Among them, the relationship of 0.8w-10.5≦x+10y+5z is satisfied, and it is not easy to obtain a large value in the negative direction for copper thermal electromotive force (EMF). On the other hand, satisfying the relationship of x+10y+5z≦0.8w-6.5, it is not easy to obtain a large value in the positive direction for copper thermal electromotive force (EMF).

Fig. 1 shows that when the content of Mn is set as w mass %, the content of Ni is set as x mass %, and the copper alloy material containing Mn, Ni, Fe, and Co, A graph of the relationship between x and (x+10y+5z) when the content of Fe is y% by mass and the content of Co is z% by mass, with x on the horizontal axis and (x+10y+5z) on the vertical axis. In the graph in Fig. 1, the copper alloy material whose absolute value of the thermal electromotive force (EMF) against copper is 0.5 μV/℃ or less is punctuated as a good resistance material with a small absolute value of the thermal electromotive force (EMF) against copper is "○". In addition, the copper alloy material whose absolute value of the thermal electromotive force (EMF) to copper exceeds 0.5 μV/℃ is regarded as an unqualified resistance material with a large absolute value of the thermal electromotive force (EMF) to copper, and is punctuated with "×".

Here, the copper alloy material, more specifically, the copper alloy material of Examples 1 to 20 of the present invention and Comparative Example 4 described later satisfies the relationship of the above formula (1) and the total amount of Fe and Co is 0.10% by mass or more. The absolute value of the thermal electromotive force (EMF) of copper is less than 0.5 μV/°C, and all of them are marked with "○" in the chart in Figure 1. On the other hand, copper alloy materials, such as the copper alloy materials of Comparative Examples 3 and 5 described later, contain Mn, Ni, and Fe or contain Mn, Ni, Fe, and Co and do not satisfy the relationship of the above-mentioned formula (1) and the sum of Fe and Co The amount is more than 0.10% by mass, and the absolute value of the thermal electromotive force (EMF) to copper is more than 0.5 μV/°C, and they are marked with "×" in the graph of Fig. 1 .

As mentioned above, the composition of the copper alloy material satisfies the relationship of the above formula (1), that is, it is easy to obtain a small absolute value of the thermal electromotive force (EMF) for copper (for example, the absolute value of the thermal electromotive force (EMF) for copper becomes 0.5 μV/°C Below) copper alloy material.

Furthermore, in Fig. 1, although the copper alloy material containing Mn, Ni, and Fe and the copper alloy material containing Mn, Ni, Fe, and Co are described in addition to Comparative Examples 3 and 5, as not satisfying the above-mentioned (1 ) formula and the total amount of Fe and Co is 0.10 mass % or more copper alloy material, but the absolute value of copper thermal electromotive force (EMF) exceeds 0.5 μV/°C, and in the chart of Figure 1 are marked as "×".

<Second optional additive (optional additive other than Co)> In addition, the copper alloy material of the present invention can further contain at least one selected from the group consisting of: Sn: 0.01% by mass to 3.00% by mass; Zn: 0.01% by mass to 5.00% by mass ; Cr: 0.01 mass % to 0.50 mass %; Ag: 0.01 mass % to 0.50 mass %; Al: 0.01 mass % to 1.00 mass %; Mg: 0.01 mass % to 0.50 mass %; : not less than 0.01% by mass and not more than 0.50% by mass; and P: not less than 0.01% by mass and not more than 0.50% by mass, as optional additive components.

(Sn: 0.01% by mass to 3.00% by mass) Sn (tin) is a component that can be used to adjust the volume resistivity ρ. In order to exert this function, it is preferable to contain Sn at 0.01% by mass or more. On the other hand, when the Sn content is 3.00% by mass or less, it is possible to prevent the manufacturability from being reduced due to embrittlement of the copper alloy material.

(Zn: 0.01% by mass to 5.00% by mass) Zn (zinc) is a component that can be used to adjust the volume resistivity ρ. In order to exert this function, it is preferable to contain Zn at least 0.01% by mass. On the other hand, since it may adversely affect the stability of electrical properties of resistors such as volume resistivity ρ, temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) of copper, it is preferable to set the Zn content It is 5.00 mass % or less.

(Cr: 0.01% by mass to 0.50% by mass) Cr (chromium) is a component that can be used to adjust the volume resistivity ρ. In order to exert this function, it is preferable to contain Cr at least 0.01% by mass. On the other hand, since it may adversely affect the stability of electrical properties of resistors such as volume resistivity ρ, temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) of copper, the Cr content is preferably set at It is 0.50 mass % or less.

(Ag: 0.01% by mass to 0.50% by mass) Ag (silver) is a component that can be used to adjust the volume resistivity ρ. In order to exert this function, it is preferable to contain Ag at 0.01% by mass or more. On the other hand, since it may adversely affect the stability of electrical properties of resistors such as volume resistivity ρ, temperature coefficient of resistance (TCR), and thermal electromotive force (EMF) of copper, it is preferable to set the Ag content as low as possible. It is 0.50 mass % or less.

(Al: 0.01% by mass to 1.00% by mass) Al (aluminum) is a component that can be used to adjust the volume resistivity ρ. In order to exert this function, it is preferable to contain Al at least 0.01% by mass. On the other hand, since the copper alloy material may become embrittled, the Al content is preferably 1.00% by mass or less.

(Mg: not less than 0.01% by mass and not more than 0.50% by mass) Mg (magnesium) is a component that can be used to adjust the volume resistivity ρ. In order to exert this function, it is preferable to contain Mg in an amount of 0.01% by mass or more. On the other hand, since the copper alloy material may become embrittled, the Mg content is preferably 0.50% by mass or less.

(Si: not less than 0.01% by mass and not more than 0.50% by mass) Si (silicon) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, it is preferable to contain Si at least 0.01% by mass. On the other hand, since the copper alloy material may become embrittled, the Si content is preferably 0.50% by mass or less.

(P: 0.01% by mass to 0.50% by mass) P (phosphorus) is a component that can be used to adjust the volume resistivity ρ. In order to exhibit this function, it is preferable to contain P 0.01 mass % or more. On the other hand, since the copper alloy material may become embrittled, the P content is preferably 0.50% by mass or less.

(Total amount of optional added components: 0.01% by mass to 5.00% by mass) These optional additional components are preferably contained in a total of 0.01% by mass or more in order to obtain the effects obtained from the above optional additional components. On the other hand, if these optional additive components are contained in large amounts, compounds are likely to be generated between the essential components, so the total is preferably 5.00% by mass or less.

<Remainder: Cu and unavoidable impurities> In addition to the above-mentioned essential ingredients and optional added ingredients, the balance is composed of Cu (copper) and unavoidable impurities. Furthermore, the so-called "unavoidable impurity" referred to here refers to an impurity, which generally exists in the raw materials in copper-based products, and is inevitably mixed in the manufacturing process and is not originally intended. It is necessary, but it can be tolerated because it is a trace amount and does not adversely affect the properties of copper-based products. Components that can be cited as unavoidable impurities include, for example, non-metal elements such as sulfur (S), carbon (C), and oxygen (O); and metal elements such as antimony (Sb). In addition, the upper limit of content of these components can be made into 0.05 mass % for each of the said components, and 0.20 mass % of the total amount of the said components.

[2] Shape and metal structure of copper alloy material The shape of the copper alloy material of the present invention is not particularly limited, but it is preferably a plate, rod, strip, or wire from the viewpoint of ease of processing by heating or cooling as described later. Among them, in the case of copper alloy materials formed by rolling such as plates and strips, the rolling direction can be defined as the extending direction. In addition, copper alloy materials such as flat-angle wires and round wires and rods formed by drawing, drawing, and extruding can be drawn in any direction, drawing direction, and extrusion direction. Direction is set to Extend Direction.

In addition, the copper alloy material of the present invention is preferably a plate, rod, strip, or wire, and has an average grain size of 60 μm or less. Here, the average grain size of the crystal is set to be 60 μm or less, and it is not easy to form coarse grains in the copper alloy material, so the absolute value of the temperature coefficient of resistance (TCR) can be compared with the thermal electromotive force (EMF) of copper. decrease in absolute value. In particular, among the copper alloy materials of the present invention, such a copper alloy material having an average grain size of 60 μm or less can be easily obtained. On the other hand, the lower limit of the average grain size is not particularly limited, but may be 0.1 μm or more from the viewpoint of production. Furthermore, when the crystal is not formed in an equiaxed shape but the grain size is anisotropic due to processing such as rolling and wire drawing along the extending direction, the average grain size of the crystal is assumed to be in the same direction as the extending direction. Orthogonal surfaces are measured.

Here, in this specification, the measurement of an average crystal grain size can be performed according to the test method of the grain size of a copper-drawn product described in JIS H0501. More specifically, it can be carried out by embedding the copper alloy material in resin so that the cross section of the copper alloy material is exposed to produce a test material, grinding the cross section perpendicular to the extending direction, and then using an aqueous chromic acid solution After performing wet etching, the exposed crystal grains were observed using a scanning electron microscope (SEM), and the crystal grain size (or crystal grain size) was measured. In particular, when measuring the average crystal grain size of the plane perpendicular to the extending direction, the copper alloy material was embedded in a resin so that the cross section perpendicular to the extending direction was exposed to prepare a test material.

[3] An example of the production method of copper alloy material The above-mentioned copper alloy material can be realized in the following way: control the composition of the alloy and the combination of the manufacturing process, and the manufacturing process is not particularly limited. Among them, an example of a process capable of obtaining the above-mentioned copper alloy material may include, for example, the following method.

An example of the production method of the copper alloy material of the present invention is to perform at least sequentially on a copper alloy material having an alloy composition substantially the same as that of the above-mentioned copper alloy material: a casting step [step 1], a homogenization heat treatment step [step 2], a hot working step [step 3], a cold working step [step 4], and an annealing step [step 5]. However, in the homogenization heat treatment step [step 2], the heating temperature is set to be in the range of 750° C. to 900° C., and the holding time is set to be in the range of 10 minutes to 10 hours. In addition, in the cold working step [step 4], the total working ratio is set to 50% or more. In addition, in the annealing step [Step 5], the heating temperature is set in the range of 600° C. to 800° C., and the holding time is set in the range of 1 minute to 2 hours.

(i) Casting step [Step 1] The casting step [step 1] is to make a predetermined shape (for example, thickness 30mm, width 50mm , length 300 mm) ingot (ingot). Furthermore, although the alloy composition of the copper alloy material is not necessarily completely consistent with the alloy composition of the manufactured copper alloy material, although it is sometimes attached to the melting furnace or volatilized according to the added components in each step of manufacture, it has the same The alloy composition of the alloy material is substantially the same alloy composition.

(ii) Homogenization heat treatment step [step 2] The homogenization heat treatment step [step 2] is a step of performing a heat treatment for homogenizing the ingot after the casting step [step 1]. Here, from the viewpoint of suppressing the coarsening of crystal grains, in the homogenization heat treatment step [step 2], the conditions for the heat treatment are preferably such that the heating temperature is set in the range of 750° C. to 900° C. The holding time of temperature is set to the range of 10 minutes or more and 10 hours or less.

(iii) Thermal processing step [step 3] The hot working step [step 3] is a step of producing a hot working material by performing rolling and wire drawing with heat on the homogenized ingot until it becomes a predetermined thickness and size. Here, the heat processing step [step 3] includes both the heat rolling step and the heat drawing (wire drawing) step. In addition, the conditions of the thermal processing step [Step 3] are preferably such that the processing temperature is in the range of 750° C. to 900° C., which may be the same as the heating temperature in the homogenization treatment step [Step 2]. In addition, the processing ratio in the thermal processing step [Step 3] is preferably 10% or more.

Here, the "processing ratio" is a value obtained by subtracting the cross-sectional area after processing from the cross-sectional area before processing such as rolling and wire drawing, divided by the cross-sectional area before processing, multiplied by 100, and expressed as a percentage , is shown in the following formula. [Processing rate]={([Cross-sectional area before processing]-[Cross-sectional area after processing])/[Cross-sectional area before processing]}×100(%)

The heat-processed material after the heat-processing step [Step 3] is preferably cooled. Here, the means for cooling the hot-worked material is not particularly limited. From the viewpoint of making it difficult to coarsen the crystal grains, it is preferable to increase the cooling rate as much as possible, preferably by means such as water cooling. To set the cooling rate to 10°C/sec or more.

Here, planar cutting for scraping the surface of the cooled hot-worked material can be performed. Plane cutting is performed, that is, the oxide film and defects on the surface generated in the thermal processing step [Step 3] can be removed. The conditions for flat cutting are not particularly limited as long as they are usually performed. The amount to be removed from the surface of the hot-worked material by planar cutting can be appropriately adjusted according to the conditions of the hot-working step [Step 3], and can be set to about 0.5 to 4 mm from the surface of the hot-worked material, for example.

(v) Cold working step [step 4] The cold working step [step 4] is to carry out processing such as rolling and wire drawing by cold at any processing rate in accordance with the plate thickness, wire diameter, and size of the product after the thermal processing step [step 3]. step. Here, the cold working step [step 4] includes both the cold rolling step and the cold drawing (drawing) step. In addition, in the cold working step [step 4], processing conditions such as rolling and wire drawing can be set according to the size of the hot-worked material. In particular, in the annealing step [Step 5] described later, it is preferable to set the total processing ratio in the cold working step [Step 4] to 50% or more from the viewpoint of promoting uniform crystal grains by recrystallization.

(vi) Annealing step [step 5] The annealing step [step 5] is an annealing step in which the cold-rolled material subjected to the cold working step [step 4] is recrystallized by heat treatment. Here, in the annealing step (step 5), the heat treatment conditions are: the heating temperature is in the range of 600°C to 800°C, and the holding time at the heating temperature is in the range of 1 minute to 2 hours. On the other hand, when the heating temperature is less than 600° C. and when the holding time is less than 1 minute, it is difficult to recrystallize the copper alloy material. In addition, when the heating temperature exceeds 800° C. and when the holding time exceeds 2 hours, the absolute value of the temperature coefficient of resistance (TCR) and the thermal electromotive force (EMF) to copper tends to increase due to grain coarsening. In addition, by suppressing the formation of the second phase in the copper alloy material after the annealing step [step 5], it is possible to stably produce copper having a small absolute value of the temperature coefficient of resistance (TCR) and the absolute value of the thermal electromotive force (EMF) to copper From the viewpoint of the alloy material, it is preferable to cool to a temperature of 200° C. or lower within 20 seconds after heat treatment at a heating temperature of 600° C. or higher in the annealing step [Step 5].

Here, the cold-rolled material after the annealing step [Step 5] may be repeatedly performed on the cold working step [Step 4] and the annealing step [Step 5]. In this way, the copper alloy material will become a plate, rod, strip, and wire having a desired shape, and it is not easy to form coarse grains, so a copper alloy material can be obtained, which is excellent in volume resistivity, temperature coefficient of resistance and Shows desirable properties for copper thermo-EMF.

[4] Application of Copper Alloy Materials The copper alloy material of the present invention can also take the form of strips such as ribbons, flat wires and round wires in addition to plates and rods, and is very useful as a resistance material for resistors used in resistors. The resistor is, for example, a shunt resistor, a chip resistor, or the like. In other words, the resistive material for the resistor is preferably composed of the above-mentioned copper alloy material. In addition, resistors such as shunt resistors and chip resistors preferably have a resistive material for resistors made of the above-mentioned copper alloy material.

Embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various changes can be made within the scope of the present invention including various aspects included in the concept of the present invention and claims. [Example]

Next, in order to clarify the effects 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.

(Examples 1-15 of the present invention and Comparative Examples 1-5) After melting the copper alloy material having the alloy composition shown in Table 1, a casting step (step 1) of cooling from the molten metal and casting was performed to obtain an ingot. Here, the alloy composition of Comparative Example 1 has the same alloy composition as the copper alloy described in Patent Document 1 above.

For this ingot, a homogenization heat treatment step [step 2] in which heat treatment was performed at a heating temperature of 800° C. and a holding time of 5 hours was performed, and then a processing temperature of 800° C. was performed so that the total processing rate became 67% (processing The pre-processed thickness is 30 mm, and the processed thickness is 10 mm) to perform the thermal processing step [step 3] of extending along the long side direction to obtain a thermally processed material. Then, after cooling to room temperature by water cooling, planar cutting is performed to remove the oxide film formed on the surface.

The hot-worked material after the hot-working step [Step 3] is cold-worked by rolling along the longitudinal direction at a total working rate of 88% (thickness before working: 8 mm, thickness after working: 1 mm) Step [Step 4]. An annealing step [Step 5] of heat-treating the cold-rolled material after the cold working step [Step 4] at a heating temperature in the range of 600° C. to 800° C. for a holding time of 1 minute to 2 hours. .

In addition, the hot-worked material after the annealing step [step 5] was rolled along the longitudinal direction at a total working rate of 70% (the thickness before working was 1 mm, and the thickness after working was 0.3 mm). 2nd cold working step [step 4]. For the cold-rolled material after the second cold working step [Step 4], a second heat treatment is performed at a heating temperature in the range of 600° C. to 800° C. for a holding time of 1 minute to 2 hours. Annealing step [step 5]. In the manner described above, the copper alloy sheets of Examples 1 to 15 of the present invention and Comparative Examples 1 to 5 whose crystal grain sizes were adjusted were produced.

In addition, in Table 1, a horizontal line "-" is written in the column of the component not included in the alloy composition of the copper alloy material, so that the fact that the corresponding component is not contained, or even if contained, does not reach the detection limit value more specific.

(Examples 16-18 of the present invention) After melting the copper alloy material having the alloy composition shown in Table 1, a casting step [Step 1] of cooling the molten metal to 300° C. and casting was performed to obtain an ingot with a diameter of 30 mm. This ingot is subjected to a homogenization heat treatment step [Step 2] of heat treatment at a heating temperature of 800°C and a holding time of 5 hours, and then a processing temperature of 800°C so that the total processing rate becomes 11%. Extend the thermal processing step [step 3] along the longitudinal direction with one rolling to obtain a rod of the thermally processed material (the diameter of the ingot before processing is 30 mm, and the diameter of the rod after processing is 10 mm. mm). Then, after cooling to room temperature by water cooling, planar cutting is performed to remove the oxide film formed on the surface.

The rod after the hot working step [step 3] is drawn using a circular die to draw the wire in a cold working step [step 4] (the diameter of the rod before processing is 10 mm, the diameter of the processed round wire is 1.95 mm). An annealing step [Step 5] of heat-treating the cold-rolled material after the cold working step [Step 4] at a heating temperature in the range of 600° C. to 800° C. for a holding time of 1 minute to 2 hours. . In the manner described above, the copper alloy wires of Examples 16 to 18 of the present invention whose crystal grain sizes were adjusted were produced.

(Examples 19-22 of the present invention) The rod after the hot working step [step 3] obtained in the same manner as Examples 16 to 18 of the present invention was subjected to a cold working step of drawing a wire using a 0.1 mm flat-angle die to achieve a total working rate of 99%. Step 4] (the diameter of the rod before processing is 10 mm, the thickness of the processed boxer line is 1 mm, and the width is 3 mm). An annealing step [Step 5] of heat-treating the cold-rolled material after the cold working step [Step 4] at a heating temperature in the range of 600° C. to 800° C. for a holding time of 1 minute to 2 hours. .

In addition, the hot-worked material after the annealing step [step 5] was rolled along the longitudinal direction at a total working rate of 70% (the thickness before working was 1 mm, and the thickness after working was 0.3 mm). 2nd cold working step [step 4]. For the cold-rolled material after the second cold working step [Step 4], a second heat treatment is performed at a heating temperature in the range of 600° C. to 800° C. for a holding time of 1 minute to 2 hours. Annealing step [step 5]. In the manner described above, the copper alloy wires of Examples 19 to 22 of the present invention whose crystal grain sizes were adjusted were produced.

[Various measurement and evaluation methods] Using the copper alloy materials (copper alloy sheet material, copper alloy wire material) of the examples of the present invention and the comparative examples described above, the characteristic evaluations shown below were performed. The evaluation conditions of each characteristic are as follows.

[1] Measurement of average grain size The obtained copper alloy material was embedded in resin so that the cross section perpendicular to the extending direction of the copper alloy material was exposed to produce a test material, and then the cross section perpendicular to the extending direction was polished. Then, after wet-etching the polished test material using an aqueous chromic acid solution, the exposed crystal grains were examined using a scanning electron microscope (SEM) (manufactured by Shimadzu Corporation, model: SSX-550). Observe 3 fields of view at a magnification of 50 times to 2000 times to measure the average grain size, and measure the grain size by the cutting method in the grain size test method of copper-drawn products recorded in JIS H 0501, and use 3 The average grain size was calculated as the average value of the grain sizes in each field of view. The results are shown in Table 2.

[2] Measurement of volume resistivity In Examples 1 to 15 of the present invention and Comparative Examples 1 to 5 obtained as boards, the obtained boards with a thickness of 0.3 mm were cut into widths of 10 mm and lengths of 300 mm to prepare test materials. In addition, in Examples 16 to 22 of the present invention in which round wires or flat-angled wires were obtained, the obtained round wires or flat-angled wires were cut into lengths of 300 mm to produce test materials.

The volume resistivity ρ was measured by setting the distance between the voltage terminals to 200 mm and the measurement current to 100 mA at a room temperature of 20°C by the four-terminal method in accordance with the method specified in JIS C2525. The volume resistivity ρ [μΩ·cm] was obtained from the obtained value.

Regarding the measured volume resistivity ρ, the case where the volume resistivity ρ was greater than 80 μΩ·cm was regarded as an excellent resistive material with a sufficiently large volume resistivity ρ and evaluated as “◎”. In addition, the case where the volume resistivity ρ is 70 μΩ·cm or more and less than 80 μΩ·cm is regarded as a good resistive material with a large volume resistivity ρ, and evaluated as “○”. On the other hand, when the volume resistivity ρ was less than 70 μΩ·cm, the volume resistivity ρ was considered to be a poor resistive material and evaluated as “×”. In this embodiment, "⊚" and "◯" are evaluated as passing grades. The results are shown in Table 2.

[3] Determination method for copper thermal electromotive force (EMF) In Examples 1 to 15 of the present invention and Comparative Examples 1 to 5 obtained as boards, the obtained boards with a thickness of 0.3 mm were cut into widths of 10 mm and lengths of 1000 mm to prepare test materials. In addition, in Examples 16 to 22 of the present invention in which round wires or flat-angled wires were obtained, the obtained round wires or flat-angled wires were cut into lengths of 1000 mm to prepare test materials.

The measurement of the copper thermal electromotive force (EMF) of the test material was performed in accordance with JIS C2527. More specifically, as shown in Figure 2, the measurement of the thermal electromotive force (EMF) of the test material 1 is to use a fully annealed pure copper wire with a diameter of 1 mm as the standard copper wire 2, and use the voltage measurement 43 to measure the electromotive force at the following time: the temperature-measuring contact point P1 connected to one of the ends of the test material 1 and the standard copper wire ₂ is immersed in warm water kept in the constant temperature bath 41 at 80°C, In addition, the reference contacts P ₂₁ and P ₂₂ , which were connected to the copper wires 31 and 32 by connecting the other ends of the test material 1 and the standard copper wire 2 , were immersed in ice water at 0° C. kept cold in the freezing point device 42 . The obtained electromotive force was divided by the temperature difference, that is, 80 [° C.], to obtain thermal electromotive force (EMF) (μV/° C.) for copper.

Regarding the measured thermal electromotive force (EMF) against copper, the case where the absolute value was 0.5 μV/°C or less was evaluated as "◎" as a good resistance material with a small absolute value of thermal electromotive force (EMF) against copper. On the other hand, when the absolute value of the thermal electromotive force (EMF) to copper was greater than 0.5 μV/°C, it was evaluated as “×” as a resistance material with a large absolute value of the thermal electromotive force (EMF) to copper. The results are shown in Table 2.

[4] Measurement method of temperature coefficient of resistance (TCR) In Examples 1 to 15 of the present invention and Comparative Examples 1 to 5 obtained as boards, the obtained boards with a thickness of 0.3 mm were cut into widths of 10 mm and lengths of 300 mm to prepare test materials. In addition, in Examples 16 to 22 of the present invention in which round wires or flat-angled wires were obtained, the obtained round wires or flat-angled wires were cut into lengths of 300 mm to produce test materials.

The measurement of the temperature coefficient of resistance (TCR) is to measure the temperature of the test material by the four-terminal method according to the method specified in JIS C2526, with the distance between the voltage terminals set to 200 mm and the measured current set to 100 mA. The voltage after heating to 150°C, and the resistance value R _{150 °C} [mΩ] at 150°C was obtained from the obtained value. Then, the voltage after cooling the test material to 20°C was measured, and the resistance value R _{20 °C} [mΩ] at 20°C was obtained from the obtained value. Then, from the obtained resistance values of R _{150 ℃} and R _{20 ℃} , TCR={(R _{150 ℃} [mΩ]－R _{20 ℃} [mΩ])/R _{20 ℃} [mΩ]}×{1/(150 Calculate the temperature coefficient of resistance (TCR) (ppm/°C) using the formula [°C]-20[°C])}×10 ⁶ .

For the measured temperature coefficient of resistance (TCR), the case where -50 ppm/°C or more and 0 ppm/°C or less is regarded as excellent at the point where the temperature coefficient of resistance (TCR) is negative and the absolute value is small and evaluated is "◎". In addition, when the temperature coefficient of resistance (TCR) is -60 ppm/°C or more and less than -50 ppm/°C, it is considered good at the point where the temperature coefficient of resistance (TCR) is negative and the absolute value is small, and evaluated as " ○". On the other hand, when the temperature coefficient of resistance (TCR) was less than -60 ppm/°C, the temperature coefficient of resistance (TCR) was negative but the absolute value was large, and it was evaluated as "×". In addition, when the temperature coefficient of resistance (TCR) exceeds 0 ppm/°C, the point where the temperature coefficient of resistance (TCR) is positive is not excellent and evaluated as "×". The results are shown in Table 2.

[5] Evaluation for reliability In addition, for Examples 1 to 22 of the present invention and Comparative Examples 1 to 5, in order to study the reliability when copper alloy materials are used as resistance materials and the like for a long period of time, especially the stability of electrical characteristics to heat, etc., and The test material whose volume resistivity was measured in the above [2] Measurement of volume resistivity was heated at 400° C. for 2 hours, and an accelerated test was performed on the stability of electrical characteristics against heat. After the acceleration test is carried out by heating, the volume resistivity of the test material is measured by the same method as the measurement of the volume resistivity in the above [2], and the volume after subtracting the volume after heating from the volume resistivity before heating is obtained respectively. The difference in volume resistivity obtained from resistivity. Here, when the volume resistivity difference obtained by subtracting the volume resistivity after heating from the volume resistivity before heating is 1.0 μΩ·cm or less, it is assumed that the decrease in volume resistivity due to heating is sufficiently small and The reliability was excellent and evaluated as "◎". In addition, when the volume resistivity difference obtained by subtracting the volume resistivity after heating from the volume resistivity before heating is more than 1.0 μΩ・cm and 2.0 μΩ・cm or less, the volume resistance caused by heating The rate decrease was small and the reliability was good, and the evaluation was "○". In addition, when the difference in volume resistivity obtained by subtracting the volume resistivity after heating from the volume resistivity before heating exceeds 2.0 μΩ·cm, it is considered that the decrease in volume resistivity due to heating is large and reliable. It is relatively unfavorable in terms of sex and rated as "△". The results are shown in Table 2.

[6] Comprehensive evaluation For the three evaluation results of volume resistivity ρ, thermal electromotive force (EMF) to copper, and temperature coefficient of resistance (TCR) among these evaluation results, the case where all three are evaluated as “◎” is defined as volume resistivity ρ , Copper thermal electromotive force (EMF) and temperature coefficient of resistance (TCR) are excellent and evaluated as "◎". In addition, the cases where one or two of these three evaluation results were evaluated as "◎" and the rest were evaluated as "○" were set as volume resistivity ρ, thermal electromotive force (EMF) to copper, and temperature coefficient of resistance The characteristics of (TCR) were good and evaluated as "◯". On the other hand, the case where any one of the evaluation results of the volume resistivity ρ, the thermal electromotive force (EMF) for copper, and the temperature coefficient of resistance (TCR) is “×” is defined as the volume resistivity ρ, The characteristics of copper thermal electromotive force (EMF) and temperature coefficient of resistance (TCR) are insufficient and evaluated as "×". The results are shown in Table 2.

[Table 1]

[Table 2]

From the results of Table 1 and Table 2, it can be seen that the alloy composition of the copper alloy materials of Examples 1 to 22 of the present invention is within the appropriate and correct range of the present invention and the volume resistivity ρ, thermal electromotive force (EMF) to copper and temperature coefficient of resistance (TCR) was evaluated as "◎" or "○" in all three evaluation results, and was also evaluated as "◎" or "○" in the comprehensive evaluation.

Therefore, since the copper alloy materials of Examples 1 to 22 of the present invention are all evaluated as "◎" or "○" in the comprehensive evaluation, they have sufficiently high volume resistivity as a resistive material, and the absolute value of the thermal electromotive force to copper is small. , and the temperature coefficient of resistance in a wide temperature range from normal temperature (for example, 20° C.) to high temperature (for example, 150° C.) is negative and has a small absolute value.

On the other hand, the alloy compositions of the copper alloy materials of Comparative Examples 1 to 5 were all outside the appropriate and accurate range of the present invention. Therefore, the copper alloy materials of Comparative Examples 1 to 5 were evaluated as "x" in at least any one of volume resistivity ρ, thermal electromotive force (EMF) for copper, and temperature coefficient of resistance (TCR).

In addition, when the Mn content exceeds 30.0% by mass, the content of Fe is set to be 0.30% by mass or less in Example 5 of the present invention, and the Fe content of Examples 2 and 4 of the present invention is 0.40% by mass or more, and the evaluation results of the reliability are evaluated as "△", and compared with Examples 2 and 4 of the present invention, Example 5 of the present invention was evaluated as "◯" in the reliability evaluation results because the stability of the electrical characteristics against heat and the like was further improved.

In addition, in Examples 1, 3, 6, 7, 10-15, 17-19, 21, and 22 of the present invention, the content of Fe was set to 0.20% by mass or less, and Examples 2, 4, 5, 8, 9, and 16 of the present invention The content of Fe in , 20 is more than 0.25% by mass and the evaluation result of reliability is evaluated as "○" or "△". Compared with Examples 2, 4, 5, 8, 9, 16, 20 of the present invention, the Examples 1, 3, 6, 7, 10-15, 17-19, 21, and 22 were evaluated as "◎" in the reliability evaluation results because the stability of the electrical characteristics against heat and the like was further improved.

1: Test material 2: Standard copper wire 31, 32: Copper wire 41: Constant temperature tank 42: Freezing point device 43: Voltage measuring device P ₁ : Temperature measuring contact P ₂₁ , P ₂₂ : Reference contact

Fig. 1 shows that when the content of Mn is set as w mass %, the content of Ni is set as x mass %, and the copper alloy material containing Mn, Ni, Fe, and Co, A graph of the relationship between w and (x+10y+5z) when the content of Fe is y% by mass and the content of Co is z% by mass, with w on the horizontal axis and (x+10y+5z) on the vertical axis axis. Fig. 2 is a schematic diagram for explaining the method of obtaining the thermal electromotive force (EMF) for copper for the test materials of the examples of the present invention and the comparative examples.

Domestic deposit information (please note in order of depositor, date, and number) none Overseas storage information (please note in order of storage country, institution, date, and number) none

Claims (9)

A copper alloy material having an alloy composition comprising the following components: Mn: not less than 20.0% by mass and not more than 35.0% by mass; Ni: 5.0% by mass or more and 15.0% by mass or less; and Fe: not less than 0.01% by mass and not more than 0.50% by mass; and Co is in the range of 0% by mass to 1.50% by mass, including the case where the Co content is 0% by mass, and The total amount of Fe and Co is in the range of not less than 0.10% by mass and not more than 2.00% by mass, and the balance is composed of Cu and unavoidable impurities. The copper alloy material as described in Claim 1, wherein the aforementioned alloy composition contains: Mn: 20.0 mass % or more and 30.0 mass % or less. The copper alloy material as described in Claim 1, wherein the aforementioned alloy composition contains: Fe: not less than 0.01% by mass and not more than 0.30% by mass; and Co: 0.01% by mass to 1.50% by mass. The copper alloy material according to claim 1, wherein the content of Mn is set to w mass %, the content of Ni is set to x mass %, the content of Fe is set to y mass %, and the content of Co is set to z During mass %, w, x, y and z satisfy the relation of (1) formula of following expression: 0.8w－10.5≦x＋10y＋5z≦0.8w－6.5・・・(I). In the copper alloy material according to claim 1, when the content of Mn is w% by mass and the content of Ni is x% by mass, the ratio of x to w is less than 0.40. The copper alloy material according to claim 1, wherein the aforementioned copper alloy material is a plate, rod, strip, or wire, and the average grain size is 60 μm or less. The copper alloy material according to claim 1, wherein the alloy composition further includes at least one selected from the group consisting of: Sn: not less than 0.01% by mass and not more than 3.00% by mass; Zn: not less than 0.01% by mass and not more than 5.00% by mass; Cr: not less than 0.01% by mass and not more than 0.50% by mass; Ag: not less than 0.01% by mass and not more than 0.50% by mass; Al: not less than 0.01% by mass and not more than 1.00% by mass; Mg: not less than 0.01% by mass and not more than 0.50% by mass; Si: not less than 0.01% by mass and not more than 0.50% by mass; and P: not less than 0.01% by mass and not more than 0.50% by mass. A resistance material for a resistor, which is composed of the copper alloy material described in any one of Claims 1 to 7. A resistor, which is a shunt resistor or a chip resistor having the resistive material for resistors according to Claim 8.

Images