TW200538562A - Copper alloy and method for production thereof - Google Patents

Abstract

A copper alloy which has a specific chemical composition, the balance being Cu and impurities, wherein the total number of pieces of precipitates and inclusions having a particle diameter of 1 μm or more satisfies the relationship represented by the following formula (1): logN ≤ 0.4742 + 17.629 x exp(-0.1133 x X) --- (1) where N represents the total number of pieces of precipitates and inclusions per unit area (number of pieces/mm2), and X represents the particle diameter (μm) of precipitates and inclusions; and a method for producing the copper alloy, which comprises, subsequent to melting and casting, cooling the cast product at a cooling rate of 0.5 DEG C/s or more at least in a temperature region from the temperature of the cast product immediately after casting to 450 DEG C. It is desirable that, after the above cooling, the product is further subjected to a working treatment in a temperature region of 600 DEG C or lower and then to a heat treatment for 30 seconds or longer in a temperature region of 150 to 750 DEG C, and, more desirably, the working and heating treatments are carried out two or more times.

Description

2005385% IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a copper alloy and a manufacturing method, which can be manufactured inexpensively without performing a melt treatment, and has excellent mechanical properties and electrical conductivity. Examples of the use of the copper alloy include power electronic parts, safety tools, and power electronic parts. For example, the following parts can be used. Examples of the electronic field φ include personal computer connectors, semiconductor sockets, optical pickups, coaxial connectors, 1C inspector pins, and the like. In the field of communications, for example: mobile phone parts (connectors, battery terminals, antenna parts), subsea repeater housings, switch connectors, and the like. In the field of automobiles, various types of electrical components such as various switches, micromotors, diaphragms, and various terminals are mentioned. In the aerospace field, for example, ... landing gears for airplanes and the like. Examples of medical and analytical equipment include medical connectors and industrial connectors. In the field of home appliances, Φ includes, for example, electrical appliances for home appliances such as air conditioners, optical pickups for game machines, and card media connectors. In terms of safety tools, there are tools such as digging rods or wrenches, hand-operated cranes, hammers, screwdrivers, pliers, cutters, etc. used in places where there is a danger of explosion due to spark ignition, such as ammunition depots or coal mine pits. [Prior art] In the prior art, as a copper alloy used in the above-mentioned power electronic parts, it is conventionally used to strengthen the purpose of precipitation of beryllium (Be) 2005385 ^

Cu-Be alloy 'This alloy contains a considerable amount of Be. Since this alloy is excellent in both tensile strength and electrical conductivity, it is widely used as a material for springs and the like. However, during the manufacturing process of Cu-Be alloy and the processing of this alloy into various parts, Be oxide is generated.

Be is second to Pb5 Cd harmful to the environment. In particular, the conventional Cu-Be alloy contains a considerable amount of Be. Therefore, in the manufacture and processing of copper alloys, a treatment process of Be oxide must be set up, which results in an increase in φ manufacturing cost and power electronics components. Problems during recycling. Therefore, Cu-Be alloys are problematic materials that highlight environmental issues. Therefore, the industry is expecting that materials that are harmful to the environment such as Be are reduced as much as possible, and materials that are excellent in both tensile strength and electrical conductivity appear. Patent Document 1 proposes a copper alloy capable of precipitating Ni2Si, which is called a Colson system. This Coulson-based alloy has a tensile strength of 750 to 820 MPa and a conductivity of about 40%. Among alloys that do not contain environmentally harmful elements such as Be, the tensile strength and electrical conductivity are considered to be relatively φ balanced. . However, this alloy has limitations in terms of both its high strength and high electrical conductivity, and there are still problems with product changes as shown below. This alloy is aging-hardenable due to the precipitation of Ni2S i. Then, when the content of Ni and Si is decreased to increase the electrical conductivity, the tensile strength is significantly reduced. On the other hand, even when Ni and Si are increased in order to increase the amount of Ni2Si deposited, there is a limit to the increase in tensile strength, and the conductivity is significantly reduced. Therefore, in the field of high tensile strength and high conductivity, the balance of the tensile strength and the conductivity of the Colson-based alloy becomes worse, and the variation range of 2005385¾ ^ products becomes narrow. This is due to the following reasons. The resistance of the alloy (or its inverse number is the conductivity) is determined by the scattering of electrons, which varies greatly depending on the type of element solid-melted in the alloy. As Ni solid-melted in the alloy, the resistance 値 increases significantly (conductivity decreases significantly), so in the above-mentioned Coulson-based alloys, the conductivity decreases when Ni increases. On the other hand, the tensile strength of copper alloys is obtained by aging hardening. The larger the amount of precipitates and the finer the precipitates are dispersed, the higher the φ tensile strength is. In the case of a Coulson-based alloy, the precipitated particles are only Ni2Si, so there is a limit in terms of high strength both in terms of the amount of precipitates and in the state of dispersion. Patent Document 2 discloses a copper alloy that contains elements such as Cr, Zr, and the like, and has good wire bonding properties with predetermined surface hardness and surface roughness. As described in this example, the copper alloy was manufactured on the premise of hot rolling and melt treatment. However, in hot rolling, to prevent hot cracking or descaling, φ surface processing is required, so the yield is reduced. In addition, there are many cases where it is heated in the atmosphere, so that active additive elements such as Si, Mg, and A1 are easily oxidized. Therefore, the generated coarse internal oxides may cause problems such as deterioration of the properties of the final product. In addition, a huge amount of energy is required during hot rolling and melt treatment. Therefore, the copper alloy described in Reference 2 is premised on hot rolling and melt treatment, which has problems from the viewpoint of reduction in manufacturing costs and energy saving, and invites the generation of coarse internal oxides. The product characteristics (in addition to tensile strength and electrical conductivity, there are problems such as bending processing or fatigue characteristics) are deteriorated. 2005385 ^ On the other hand, the above-mentioned materials for safety tools are required to be comparable to tool steel in mechanical properties, such as strength or abrasion resistance, and must not generate sparks that cause explosions, that is, they must have excellent spark resistance . Therefore, "even high-conductivity copper alloys are used even for safety tool materials", especially Cu-Be alloys for the purpose of aging precipitation strengthening of beryllium (Be). As described above, although the Cu-Be alloy is a material having many environmental problems, the Cu-Be alloy is mostly used as a safety tool material φ for the following reasons. Figure 1 shows the relationship between the electrical conductivity [IACS (%)] and the thermal conductivity [TC (W / m · K)] of a copper alloy. As shown in Figure 1, the relationship between the two is approximately 1: 1. Increasing the electrical conductivity [IACS (%)] means increasing the thermal conductivity [TC (W / m · K)] 'In other words, improving the spark resistance and Does not affect other. When a tool is used, when a sharp force is applied due to a shock or the like, sparks are generated due to the combustion of a specific component in the alloy due to the heat generated by the shock or the like. As described in Non-Patent Document 1, the thermal conductivity of steel is as low as / 5 as low as 1/5 of the thermal conductivity of copper, so local temperature rise is prone to occur. Steel contains C, which causes a reaction of "C + 〇2-C02", so sparks are generated. In fact, in pure iron that does not contain C, it is known that no spark is generated. Other metals that are prone to sparks are Ti or Ti alloys. This is because: the thermal conductivity of Ti is extremely low to 1/20 of the thermal conductivity of copper, and it will cause a reaction of "ding 丨 + 02—ding 丨 02". In addition, the first figure is a person who arranges the materials shown in Patent Document 2. However, as mentioned above, the electrical conductivity [IACS (%)] and the thermal conductivity [TC (W / m · K)] are in a balanced relationship, and it is extremely difficult to improve the two at the same time. 2005385 The local tensile strength is, on the one hand, a copper alloy having sufficient thermal conductivity TC on the one hand, and only the above-mentioned Cu-Be alloy. Patent Document 1: Japanese Patent No. 2572042 Patent Document 2: Japanese Patent No. 2 7 1 4 5 6 1 Non-Patent Document 1: Industrial Heating, ν〇 · 36, No. 3 (1999) Japanese Industrial Furnace Issued by the Association, p. 59 φ Non-licensed Document 1: Handbook of copper drawing products, Japan August 1, 2009, Japan Copper Drawing Association, pages 328 ~ 355 [Contents of the Invention] Problems to be Solved by the Invention The Invention The first objective is to provide a copper alloy with a wide variety of products, excellent ductility and processability, and the required properties of safety tool materials, namely thermal conductivity, wear resistance and spark resistance. • different. A second object of the present invention is to provide a method for producing the above-mentioned copper alloy. The so-called "rich product variation" means that the balance between conductivity and tensile strength can be adjusted by fine-adjusting the amount of addition and / or manufacturing conditions to: High grade means low grade to the same degree as the copper alloy known in the prior art. The term "adjust the balance between electrical conductivity and tensile strength to a level equal to or higher than that of Cu-Be alloy" means a state that specifically conforms to the formula (a) below. Hereinafter, this state is referred to as "a state in which the balance between the electrical conductivity and the tensile strength is extremely good." -9- 2005385 TS2 648.06 + 985.48xexp (-0.0513xIACS) ... (a) where TS in the formula (a) For the meaning of tensile strength (MPa), IACS means for electrical conductivity (%). In terms of bending, it is also preferred to be equivalent to or higher than a conventional alloy such as a Cu-Be alloy. Specifically, a bending test of φ 90 ° is performed on the test piece with various curvature radii, and the curvature radius R that does not cause cracking is measured. The folding can be evaluated by the ratio 値 B (= B / t) to the plate thickness t. Bend processability. The range of good bending workability is as follows: when using a plate with a tensile strength TS of 800 MPa or less, it can meet 2 · 0, and a plate with a tensile strength TS of more than 800 MPa, can be made to meet the following (B). 4 1.2686-39.4583xexp [-{(TS-61 5.675) /2358.08} 2] ... (b) φ In the copper alloy as a safety tool, except for the characteristics of tensile strength TS and conductivity iACS as described above In addition, abrasion resistance is also required. Therefore, in the case of a copper alloy for safety tools, it is necessary to have the same level of wear resistance as tool steel. Specifically, when the Vickers hardness is 250 or more at room temperature, the abrasion resistance can be excellent. MEANS TO SOLVE THE PROBLEM This invention is the summary of the manufacturing method of the copper alloy shown by following (A)-(C) and the copper alloy shown by (D) below. -10- 2005385% (A) From Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si,

Mo, V, Nb, Ta, W, Ge, Te, and Se. One or two or more selected in total 0.1 to 20% by mass 'The rest is formed by copper and impurities' Precipitation existing in the alloy The particle size of the particles and inclusions is 1 # m or more, and the total number of precipitates and inclusions is in accordance with the relationship shown in the following formula (1), • logNS 0.4742 + 17.629xexp (-0.1133 xX) ..- (l) where N is the total number of precipitates and inclusions per unit area (pieces / mm2), and X is the particle size m of the precipitates and inclusions. (B) In terms of mass%, it contains any one selected from Ti: 0 · 01 to 5 ° / (), Zr: 0.01 to 5%, and Hf: 0.01 to 5%.

Sn, Ag, Mη, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se. One or two selected in total φ 0.01 to 20%, the rest It is formed of copper and impurities, and the particle size of the precipitates and inclusions in the alloy with a particle size of 1 A m or more, and the total number of precipitates and inclusions are in accordance with the following formula (1) The relationship shown 'logNS 0.4742 + 17.629xexp (-0.11 33xX) ... (1) where N is the total number of precipitates and inclusions per unit area (pieces / mm2), and X is the precipitate and inclusions Particle size (from m). (C) When expressed in mass%, it contains: C r: 0 · 0 1 to 5%, and from -11-2005385 #

Zn, Sn, Ag, Mη, Fe, Co, Al, Ni, Si, Mo, V, Nb,

One, two or more selected from Ta, W, Ge, Te, and Se total 0.0 1 to 20%, and the rest are copper and impurities. The particle size of precipitates and inclusions formed in the alloy. The particle size of 1 # m or more and the total number of precipitates and inclusions are in accordance with the relationship shown in the following formula (1) 'logN ^ 0.4742 + 1 7.629xexp (-〇-l 133xX) ... (1) Among them, N refers to the total number of precipitates and inclusions per unit area (pieces / mm2), and X refers to the particle size m of the precipitates and inclusions. The copper alloy described in any one of (A) to (C) above may also contain: one or two or more selected from Mg, Li, Ca, and rare earth elements in total 0.001 to 2 Mass%, and / or, from P, B, Bi,

Tl, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, Po,

One or two of Sb, Au, Ga, S, Cd, As, and Pb are selected to replace a part of copper with a total of 0.001 to 3% by mass in φ. Alternatively, it may contain Be in an amount of 0.1 to 5% by mass. These alloys preferably have a ratio of the maximum average content to the minimum content of the minimum content of at least one type of alloy element in the micro area of at least one type of alloy element, which is preferably 1.5 or more. The crystal grain size of these alloys is preferably from 0.01 to 35 // m. (D) Smelt obtained by melting and casting a copper alloy having the chemical composition described in any one of (A) to (C) above, from at least the temperature of the slab obtained immediately after casting to 4 5 0 5。 In the temperature range up to ° C, 0.5. (: Cooling at a cooling rate of more than / s, where: copper alloy is precipitates present in the alloy-12- 2005385 # and the particle size of inclusions with a particle size of 1 # m or more, and the total of precipitated impurities The number is in accordance with the relationship shown in the following formula (1), logN ^ 0.4742 + 17.629xexp (-〇.1133xX) (1) where N is the number per unit area of precipitates and inclusions ( (Mm / mm2), X refers to the particle size (#m) of precipitates and inclusions. After the above cooling, keep in the temperature range of 60 (TC or below) or more in the temperature range of 150 ~ 750 ° C More than 30 seconds is preferred. Processing in a temperature range below 600 ° C, and heat treatment for more than 30 seconds in a temperature range of 1 ° C can also be performed after the final heat treatment It can also be processed at a temperature below 600 ° C. The so-called precipitates in the present invention refer to metals or copper and added compounds, or compounds of added elements, for example, Ti is added to Cu4Ti, and Zr is added to Cu9Zr2. Precipitation, and metal Cr in the right admixture. In addition, the so-called inclusions refer to compounds and metal carbon. Compounds, metal nitrides, etc. [Embodiments] Hereinafter, embodiments of the present invention will be described. "In" the content of each element "%" means "mass%"] The copper alloy of the present invention The material and the material are processed in a total amount of 50 to 750 rows of elements in the multiple-degree domain. Cr is added to the metal under oxygen. -13- 2005385% Chemical composition The copper alloy of the present invention includes: Select from Sn, Ag, Mn, Fe, Co, A1, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se (hereinafter, these elements are referred to as "group 1 elements") 0.1 to 20% by mass of one kind, or 0.1 to 20% by mass of two or more kinds in total, and the remainder is a chemical composition formed by copper and impurities. Any of these elements is a flat φ that can maintain strength and conductivity. It has the effect of improving the corrosion resistance and heat resistance. This effect can be exerted when the total content of these elements is 0.1% or more. However, when the content of these elements is too large, Reduce the conductivity. Therefore, when containing these elements In this case, the total content of one or two or more kinds must be in the range of 0.1 to 20%. In particular, Ag and Sn are formed by fine precipitation to increase strength, so it is best to use them actively. In the case of the second element described below, the strength can be ensured by the second element, so the lower limit 値 of the first element can be reduced to 0.001%. Φ The alloy of the present invention may contain Ti: 0.01 to 5% , Zr: 0. 01 to 5% and Hf: 0. 01 to 5%. Any one selected, or containing Cr: 0.01 to 5% to replace a part of copper. Hereinafter, these elements are referred to as "second group elements". Any one of Ti, Zr, or Hf 'selected from Ti: 0 · 01 to 5%, Zr: 0.01 to 5%, and Hf: 0.0 ^ 5% is an effective element for improving tensile strength. The copper alloy of the invention may contain any one of these elements. The effect of the strength raising cylinder becomes significant when the content of these elements is 0.01% or more. However, when the content exceeds 5%, -14-2005385¾ deteriorates the conductivity of the person with increased strength. In addition, segregation of Ti, Zr, or Hf is caused during casting, and it is difficult to obtain a homogeneous slab, and cracking or chipping is likely to occur during subsequent processing. Therefore, the content in the case where either one of Zr and Hf is contained is preferably 0. 0 1 to 5. 0%. In order to obtain a very good balance of tensile strength and electrical conductivity, it is better to make these elements more than 0.1%.

Cr: 0.0 1 to 5% φ Cr does not increase resistance but is an effective element in improving tensile strength. In order to obtain this effect, the content is preferably 0.01% or more. In particular, in order to obtain a state where the balance of tensile strength and electrical conductivity is the same as or higher than that of the Cu-Be alloy, it is preferable to contain 0.1 ° / ◦ or more. On the other hand, when the Cr content exceeds 5%, the metallic Cr is coarsely precipitated, which adversely affects the bending characteristics and fatigue characteristics. Therefore, when Cr is contained, its content is preferably 0.01 to 5%. In order to improve the high-temperature strength of the copper alloy of the present invention, the copper alloy contains φ, which is selected from Mg, Li, Ca, and rare-earth elements. 0 · 0 0 1 ~ 2%, or a total of 2 or more. · 〇1 ～ 2%, it is better to replace a part of copper. These are hereinafter referred to as "third group elements".

Mg, Li, Ca, and rare-earth elements are elements that combine with oxygen atoms in a copper array to generate fine oxides, thereby increasing their high temperature strength. This effect is significant when the total content of these elements is 0.001%. However, when the content exceeds 2%, there are problems that the above-mentioned effects become saturated, the conductivity is lowered, and the bending characteristics are deteriorated. Therefore, the total content of one or two or more selected from Mg, Li, Ca, and rare earth elements is preferably 0.001 to 2%. In addition, the rare earth element means Y and lanthanum, and a monomer of an individual element may be added, and Nd may also be added. When the copper alloy of the present invention is intended to enlarge the width (ΔT) of the liquidus phase line during alloy casting, it is preferred that the copper alloy contains p, B, Tl, Rb, Cs, Sr, Ba, Tc, One of Re, Os, Rh, In, Pd, Sb, Au, Ga, S, Cd, As, and Pb is φ 0.00 1 to 3%, or a total of two or more is 0.001 to 3%. Replace part. As, Pd, and Cd are harmful elements, so avoid them if possible. These are hereinafter referred to as "the fourth group element". On the other hand, in the case of Δ rapid condensation and solidification, although it becomes large due to the so-called supercooling phenomenon, ΔT in consideration of the thermal equilibrium state is taken as a target. These elements all have the effect of lowering the solid phase line and expanding △ T. When △ T is large, it is possible to ensure a certain time from casting to solidification. Therefore, casting is facilitated. When △ T is too wide, The resistance φ in the low-temperature region is reduced, so that cracking occurs at the end of solidification, and so-called weldability occurs. Therefore, it is preferable to make ΔT in the range of 50 to 200 ° C. C, N, and O are elements usually contained as impurities. These elements are carbides, nitrides, and oxides that form metal carbides in the alloy. If the precipitates or inclusions are fine, they are precipitated with compounds of metals or additives described below, or compounds of added elements. The ground has the effect of strengthening the alloy, especially for improving the high temperature strength, so it can be actively added. For example, 0 has the effect of forming an oxide and high temperature strength. This effect is effective when Mg, Li is added, and Bi, P 0, and copper are not added, so that T is effective. In the meantime, the force will be brittle. It is easy to obtain in the alloys of copper and the like, Ca 16-2005385¾ and rare earth elements, oxides of A1, S 1 and so on. However, in this case, it is necessary to select the condition that solid oxide does not remain. Residual solid-melt oxygen will form ’20 gas' during heat treatment in a hydrogen environment and cause water vapor explosion, which will cause so-called hydrogen disease, air bubbles, etc., which may degrade the quality of the product, so be careful. When these elements each exceed 1%, they will become coarse precipitates or inclusions, reducing ductility. Therefore, it is better to limit ’to 1% or less, respectively. It is more preferably 0.1% or less. In addition, when radon is contained as an impurity in the alloy, the radon 2 gas remains in the alloy and causes causes such as rolling defects. Therefore, it is desirable that the content be as small as possible.

Be is an element that contributes to the precipitation strengthening of the alloy without compromising conductivity. In order to obtain the effect, it is preferable to contain 0.1 mass ° /. the above. However, when the content exceeds 5%, not only the conductivity decreases, but also the ductility decreases, which deteriorates workability such as rolling and bending. Therefore, when Be is contained, its content is preferably set to 0.1 to 5%. Regarding the total number of precipitates and inclusions In the copper alloy of the present invention, the particle size of the precipitates and inclusions present in the alloy with a particle diameter of 1 μm or more, and the total number of precipitates and inclusions The number must conform to the relationship expressed by the following formula (1). logNS 0.4742 + 1 7.629xexp (-0.1133xX) (1) where N is the total number of -17-2005385¾ (units / mm2) per unit area of precipitates and inclusions, and X is the precipitate And the particle size of the inclusions (// m). In the formula (1), when the measurement of the particle size of the precipitates and inclusions is greater than or equal to 1 · 0Mm and less than or equal to 1 · 5 μm, X = 1 is substituted, and when "α-0 · 5" / In the case of "α + 0.5" // m or more, it is sufficient to substitute X = α (α is an integer of 2 or more). In the copper alloy of the present invention, when finely precipitating φ of a metal, a compound of copper and additives, or a compound of additive elements, etc., the strength can be improved without lowering the conductivity. This is to increase the strength by precipitation hardening. When it is reduced by precipitation of solid-state Cr, Ti, and Zr, the conductivity of the copper array can be made close to that of pure copper. However, when the particle size of such precipitates and inclusions such as metal oxides, metal carbides, and metal nitrides is coarsely precipitated at 20 μm or more, the ductility is reduced, for example, when processing connectors. It is easy to be cracked or chipped during bending or punching. In addition, it adversely affects fatigue characteristics or impact resistance during use. In particular, when a coarse Ti-Cr compound is produced during cooling after solidification, cracks or nicks are likely to occur during subsequent processing. In addition, the hardness is excessively increased during the aging treatment, which prevents the fine precipitation of such precipitates and the like, so that the copper alloy cannot be made high-strength. In such a problem, among the precipitates and inclusions existing in the alloy, the particle size of one having a particle size of 1 μm or more, and the total number of precipitates and inclusions do not meet the relationship represented by the above formula (1) Becomes significant. Therefore, in the present invention, it is stipulated that the particle size of the precipitates and inclusions existing in the alloy with a particle diameter of 1 μm or more, and the total number of precipitates and inclusions must conform to the above formula (1) The relationship indicated is a necessary condition of -18-2005385¾. The preferred total number of precipitates and inclusions corresponds to the relationship represented by the following formula (2), and more preferably corresponds to the relationship represented by the following formula (3). It should be noted that the particle size, the total number of precipitates, and the total number of inclusions were determined by the methods shown in the examples. logNg 〇4742 + 7.9749xexp (-〇.1133xX) ... (2) logN ^ 0.4742 + 6.3579xexp (-〇.1133xX) ... (3) where N is the per unit area of precipitates and inclusions. The total number (number / mm2), X refers to the particle size (// m) of precipitates and inclusions. At least one type of alloy element in a micro-field has a ratio of the maximum average content to the minimum content of the minimum content of the alloy element in a copper alloy having a micro-mixed structure in which the concentration of the alloy element is different, that is, when the concentration changes periodically, Since the micro-diffusion of each element can be suppressed and the grain boundary movement can be suppressed, the effect of easily obtaining a fine crystal grain structure is obtained. As a result, according to the so-called Hall-Petch rule, the strength and ductility of the copper alloy can be improved. The micro-field refers to a field formed by a diameter of 0.1 to 1 μm, and basically means a field corresponding to an irradiation area during X-ray analysis. The fields in the present invention where the alloy element concentrations differ are the following two types. Although it basically has the same face-centered cubic structure as copper, it is in a state where the alloy element concentrations are different. Because of different alloy element concentrations, on the one hand, they have the same fee structure, and on the other hand, the general lattice constants are different. -19- 2005385 ^ Of course, the degree of work hardening is different. The fine precipitates in the f C C mother phase are in a dispersed state. Because of different alloy element concentrations, the dispersion of precipitates after processing and heat treatment is different. The so-called average content in the micro-field refers to the 上 in the analysis area when the X-ray analysis is focused on a certain beam diameter below 1 // m, which means the average 値 in the field. For X-ray analysis, an analysis device having a field φ emission type electron gun is preferred. In terms of analysis means, an analysis method having a decomposition energy of 1/5 or less, more preferably 1/10 of the concentration cycle is preferred. The reason is that when the analysis area is too large compared to the concentration period, it is difficult to express a difference in concentration when the whole is averaged. Generally, it can be measured by X-ray analysis with a probe diameter of about 1 # m. The material characteristics are determined by the alloy element concentration and the fine precipitates in the mother phase. In the present invention, the difference in the concentration of the fine domain containing the fine precipitates is a problem. Therefore, the signal from coarse precipitates or coarse clips # 1 above 1 // m is the cause of external disturbance. However, it is very difficult to completely remove coarse precipitates or coarse inclusions from industrial materials. During analysis, it is necessary to remove the external disturbance factors from the coarse precipitates or coarse inclusions described above. Therefore, the following method is adopted. That is, first, although it also depends on the material, it is analyzed using an X-ray analyzer with a probe diameter of about 1 to grasp the periodic structure of the concentration. As described above, the analysis method is determined so that the probe diameter becomes 1/5 or less of the concentration cycle. Next, determine: a line analysis length of a sufficient length so that the cycle appears more than three times. Under this condition, X-ray analysis is performed m times (preferably -20-2005385% 10 times or more), and the maximum and minimum values of the concentration are determined according to the individual X-ray analysis results. Although the number of maximum and minimum 値 is m, 20% is removed from the larger of individual 値 and averaged. According to the above aspect, the above-mentioned coarse precipitates and inclusions can be removed from external disturbance factors. The concentration ratio is determined by the ratio of the maximum 値 and the minimum 除去 which eliminates the cause of the disturbance described above. However, the concentration ratio only requires alloying elements with a φ period concentration change of about 1 # m or more, and does not consider local spino dal decomposition or atomic levels below 1 Onm such as fine precipitates. Concentration changes. The reason why the ductility is improved by the fine distribution of the alloy elements will be described in detail. When the concentration of alloying elements changes, the degree of solidification hardening of the material in the high-concentration part and the low-concentration part, or the dispersion state of the precipitates as described above are different, so the mechanical properties of the two parts are different. In this material deformation, first, the relatively soft low-concentration part is processed and hardened, and second, the relatively hard high-concentration part begins to deform. In other words, a plurality of work hardenings occur in the entire material, so that, for example, when the tensile deformation is caused to show a high elongation, another effect of improving the ductility occurs. In this way, in alloys that undergo a change in the concentration of the alloy element over a period of time, it is possible to maintain a balance between electrical conductivity and tensile strength, and at the same time, to exhibit advantageous high ductility such as during bending. However, the resistance (the inverse of the conductivity) is mainly due to the decrease in the movement of electrons caused by the dispersal of solid-solution elements, which has little effect on macro defects such as crystal grain boundaries, so it is not caused by the above-mentioned fine-grained structure. Reduce the conductivity of -21-2005385%. These effects become significant when the ratio of the maximum 値 to the minimum 平均 (hereinafter referred to simply as the "concentration ratio") of the average content in a small area of at least one alloy element in the parent phase is 1.5 or more. Although the upper limit of the concentration ratio is not specifically set, when the concentration ratio is too large, in addition to the failure to maintain the f c c structure of the Cu alloy, the difference in the electrochemical characteristics is too large, and there is a possibility of causing disadvantages such as local corrosion. Therefore, the concentration ratio φ is preferably 20 or less, and more preferably 10 or less. (d) In terms of crystal grain size When the crystal grain size of the copper alloy is made fine, it is advantageous in terms of high strength, and the ductility is improved, and the bendability and the like are also improved. However, when the crystal grain size is reduced to 0.01 μm, the high-temperature strength tends to decrease, and when it exceeds 3 5 μm, the ductility decreases. Therefore, it is preferable that the crystal grain size is 0.01 to 3 5 μm. A more preferable particle size is from 0.05 to 30 μm. The optimum is 0.1 to 25 μm. φ In the method for producing a copper alloy according to the present invention, in the copper alloy according to the present invention, metal oxides, metal carbides, metal nitrides, and the like, which prevent fine precipitation of metals, copper, compounds of added elements, or compounds of added elements, etc. Inclusions are likely to occur immediately after the slab is solidified. If such inclusions are subjected to a melt treatment after casting, even if the melt temperature is increased, it is difficult to solidify the inclusions. The use of high-temperature melt treatment will only cause the aggregation and coarsening of inclusions. Therefore, in the method for producing a copper alloy of the present invention, a slab obtained by melting and casting a copper alloy having the above-mentioned chemical composition is obtained from at least -22-200,385 In the temperature range from the sheet temperature to 45 0 ° C, when cooling at a cooling rate of 0.5 ° C / sec or more, the particle size of the precipitates and inclusions present in the alloy is 1 // m or more The particle size and the total number of precipitates and inclusions are in accordance with the relationship shown in the following formula (1) 'logN ^ 0.4742 + 17.629xexp (-〇.1133xX) ... (1) where N means precipitation The total number of particles and inclusions per unit area (pieces / mm2), X refers to the particle size m of the precipitates and inclusions. After this cooling, processing in a temperature range of 600 ° C or lower 'or more can be performed in a temperature range of 150 to 75 ° C for 30 seconds or more, and a plurality of times are performed. In addition, after the final heat treatment, it can be processed in a temperature range below 600 ° C. The cooling rate in the temperature range from at least the temperature of the slab immediately after casting to 45 0 ° C: 0.5 ° C / second or more Metal or copper and compounds of added elements, or precipitates of compounds of added elements, etc. It is produced in the temperature range above 2 0 0 ° C. In particular, when the cooling rate in the temperature range from the temperature of the slab immediately after casting to 45 0 ° C is slow, the inclusions of metal oxides, metal carbides, metal nitrides, etc. are coarsely formed, and their particle sizes It is more than 20 μm, and more than several hundred μm. In addition, the above-mentioned precipitates were coarsened to 20 μm or more. In the state where such coarse precipitates and inclusions are generated, not only may there be a risk of cracking or breaking during subsequent processing, but also the precipitation hardening effect of the above-mentioned precipitates during aging may be impaired, making the alloy unable to be high. Intensified. -23- 2005385¾ Therefore, at least in this temperature range, the slab must be cooled at a cooling rate of 0.5 t / sec or more. The larger the cooling rate, the better, and 2 is preferred. (: Or more, more preferably 10 ° C / s or more. Processing temperature after cooling: 60 (TC or lower temperature range) In the method for producing a copper alloy according to the present invention, the cast slab obtained is cast under predetermined conditions. After cooling, it does not undergo the φ thermal process such as hot rolling or melt treatment, but only the combination of processing and aging heat treatment is used to make the final product. The processing of calendering, drawing line, etc. can be 600 ° C The following. For example, when continuous casting is used, such processing can be performed during the cooling process after solidification. When processing in a temperature range exceeding 600 ° C, metal or copper and added compounds during processing, or Precipitates such as compounds of added elements are coarsely precipitated, which reduces the ductility, impact resistance, and fatigue characteristics of the final product. In addition, when these precipitates are coarsely precipitated during processing, aging treatment is performed. It is impossible to precipitate finely in the medium, so that the high strength of the copper alloy becomes insufficient. The lower the processing temperature, the higher the dislocation density during processing. During the treatment, the precipitates of metals, copper, compounds of added elements, or compounds of added elements can be precipitated more finely. Therefore, higher strength can be given to the copper alloy. Therefore, the preferred processing temperature is 45 ( Below TC, more preferably below 250 ° C. Most preferably below 200 ° C. It can also be below 25 ° C. However, the processing rate in the above temperature range is preferably its processing rate (section-24-2005385¾ The reduction rate is 20% or more. More preferably, it is 50% or more. If the processing is performed at such a processing rate, the introduced dislocations will change to precipitate nuclei during the aging treatment, resulting in the miniaturization of precipitates and the precipitation. The time is shortened, and the solid solution elements that are detrimental to conductivity can be achieved early. (C) Aging treatment conditions: The aging treatment is held in the temperature range of 150 ~ 75 0 ° C for more than seconds φ aging treatment, which is to metal or copper And precipitates of compounds of added elements, or compounds of added elements, which strengthen copper alloys and reduce solid-solution elements (Cr, Ti, etc.) which are harmful to conductivity at a time, and are therefore effective in improving conductivity However, when the processing temperature is less than 15 ° C, the diffusion of precipitated elements takes a long time, so the properties are reduced. On the other hand, when the processing temperature exceeds 750 ° C, the precipitates become excessively coarse. Precipitation hardening cannot increase strength, or reduce ductility, impact resistance, and fatigue characteristics. Therefore, it is preferable to perform the φ treatment in a temperature range of 150 to 750 ° C. The preferred aging treatment temperature is 200 ~ 700 ° C, more preferably 25 0 ~ 65 0 ° C. The best is 280 ~ 5 50 ° C. When the aging treatment time is less than 30 seconds, even when the aging temperature is set to high, The amount of precipitation cannot be ensured, and when it exceeds 72 hours, the processing cost becomes huge. Therefore, it is preferable to perform the aging treatment in a temperature range of 150 to 750 ° C for 30 seconds or more. The treatment time is preferably 5 minutes or more, and more preferably 10 minutes or more. The best time is 15 minutes. Although the upper limit of the processing time is not particularly limited, it is preferable that the processing time is 72 hours or less from the viewpoint of processing costs. In addition, when the aging treatment temperature needs to be reduced by 30 degrees, the full production change makes the efficiency time temperature higher when the application temperature is -25- 2005385¾, which can shorten the aging treatment time. The aging treatment can be performed in a reducing environment, an inert gas environment, or a vacuum of 20 Pa or less in order to prevent the generation of dirt due to surface oxidation. By processing in such an environment, excellent plating can be ensured. The above-mentioned processing and aging treatment can be repeated iteratively as needed. Repeatedly, the desired amount of precipitation can be obtained in a short time than a single treatment (processing and aging treatment), and the metal or copper φ and the compound of the added element, or the precipitate of the compound of the added element can be obtained Precipitate more finely. At this time, for example, when the treatment is repeated twice, the second aging treatment temperature can be made slightly lower than the first aging treatment temperature. When such heat treatment is performed, the temperature of the second aging treatment is high because the precipitates produced during the first aging treatment are coarsened. Even in the aging treatment from the third time onward, it is better to prepare the aging treatment at a lower temperature than the aging treatment which has been performed before. In addition, after the final heat treatment, it can be processed in a temperature φ range of 600 ° C or lower. Other In the method for producing a copper alloy of the present invention, although conditions other than the above-mentioned production conditions, such as conditions for melting, casting, and the like, are not particularly limited, they can be performed, for example, as follows. Melting can be performed in a non-oxidizing or reducing environment. This is because when there is a large amount of solid oxygen in the molten copper, water vapor is generated in the later process, and bubbles are generated, which causes the so-called hydrogen disease. In addition, solid oxide elements such as Ti, Cr, etc., which are easily oxidized, produce coarse oxides. When these remain in the final product, the ductility or fatigue characteristics are significantly reduced. Although the method of obtaining a cast piece is preferably continuous casting from the viewpoint of productivity or solidification rate, other methods such as an ingot method may be used as long as the method meets the above conditions. In addition, a preferable casting temperature is 1 250 ° C or more. More preferably, it is above 1 350 ° C. As long as it is at this temperature, Cr, Ti, and Zr can be sufficiently melted, and no inclusions such as metal oxides, metal carbides, metal nitrides, metals, copper, compounds of added elements, or added elements can be generated. Precipitates of compounds and the like. When a slab is obtained by continuous casting, a method using a graphite mold usually performed in a copper alloy is recommended from the viewpoint of lubricity. In terms of mold materials, refractory materials that are difficult to react with Cr, Ti, and Zr, such as hafnium oxide, can be used. Example 1 A copper alloy having the chemical composition shown in Tables 1 to 3 was vacuum-melted in a high-frequency melting furnace and cast into a mold made of chromium oxide to obtain a cast sheet having a thickness of 12 mm. Rare earth elements are monomers or Nd with the addition of each element 〇 -27- 2005385¾

I «Valm 锱 _ i Slow Wi Q >P9; Mill I 1 :) 1: h 1 1 1: .1 lliii! -I M: iii 1IMQ! H ^ B '〇r4 • tH BU 丨 · HL 丨 1口: S§5 1! O o Issg-i 1 g〇 * S | TH Θ 〇m IR i KS 〇 · 1 1 ^ 1 1 m 5 «1 § 1 c >; 〇 sound. ¾ ο ^ SMI: g Contains s: Astrology g gs § 0.2Sb O. tlji, Ο, δΡί, 0.lGa 11¾¾ [ill-* G3 6). W〇S is k ^ 〇 " 1 | IS 〇Ills E5 '; φ cp- C > iiua < D 11111 | 3 〖3 | I 3! 丨 1 1 丨 .3 碧 丨. IL Miscellaneous: ： Tear; i § | (1 § M 4 111 6 O _rr ft | 1 O-JlLa, O.OICa ο · ιϊλ, aolMg, o.cmLi o.om. l · | > Ι s §si ί I1 IS M 33 lojcs: damajii! I; 1 1 ί 1 jr: ii I i… ㈣ | 22l1 n III) \ Μ M (('III 3lS M! P t Ml S 濉 M jir (i 1 iiS3 Si1 1 1 " ί 1! 1 l 1 1 i U mis | IM 1. i * iii \ ii \ I \ \ 丨 丨 |〗 3! Ί »π < π mn | SSS2 31¾ 3 m IS 雔 v * h; c3: n 0 ', iH' (« ho fill Hill Mi ifill ω fflil llfil Hill ·· · · ·· «· · ·« r- (· r-ί C2 > Ci · 1 ^ 1 3! 1 Ί! S! P! «Li Mill: cJ: C3 c5 S ¢ 4; 1 & 1 Jl i.il sll ^ l 1 u »-j CS (CO ^ 1β ^ 00 OS g S S3 S S S &?! 5S ^ -28- 2005385¾

$ & W 1 1 Μ) III! ii (! I ί 1 ί M Mil ί 1 ϋΐϊπ < π 1 1: 11¾ dd 05 I i rH% d 〇〇 ^ _i Q.QQ9 〇5 < Ni. §: 1 d Ml; o.ii i 1 group 4 element aqii 1 2 heart · Η: "4 S: Q i〇dod aoois Q..010Sj Ο ^ Θ ^ Βι- D.01P .1? 3P: Qi 2 ;: 〇ΐ? Ιϊΐ · 0 · 〇11 · 1 1 i 〇o 0.5Sb, IJBa, l.OBi iMhi lWd PM2Ψ k) J_ S iii ^ Lu: P u Si σ ....... ο Jilin Q: Q1 0: .01 M * 0.04. 0.11 an 0.01 a: Q6 — Q; 06: I: X4t 0JQ6 丨 _ — Group 3 element aoiMg O.GIMg 1.5¾. l.QLa.! 1 i ! I: 11. ^ 1 If 1 Ci < ¥? · 0fQXLi QMQd 0.01Ca, 0; lSc% li] ί! 1 S | i;,: ii1 1 II-< ά · dq; 1 1 i 丨 • a: i 1: (M l [1 (i Mil • -ί '1, .42 1,4B 1.85 ί: l: t Γ J W.ia: IH: S M.: in ilil 1: \ r ί; ii jl ί .M I- Si — iii:!. i | i LU IM IM im 1 ^ 2 1 1 1 {1 1 i .1 · =: 1 \ 丨 1 丨 丨! 'm3% 5Z 19 »1 1 1. 1 Ί Mill μ ί: iij Μ ί H liiin < Π m: QM \ om m 23.2, 0.95 Lion gall ϋΜ. M 'm e.71. 2.6 MO * 丨 Group 1素 tomb 0.99 Gb mme i% mi Bm, aeNb 0.95C〇. L00, 0.9Me Q.mc〇a Liyi i tA t; III! Mil liil illi! Hill Sill ll: _ 'W. 41 iS-§; § : S | -29- 2005385¾

i 荪 ft u Miscellaneous φ PQ i 1 IM i llll! τί »ri ua. co d: csi C5: PQ o CO OD CD. ρΰ CD c4 < NO ci iN Total 0.2 0.Q0X: 0; 0 !: ΐ): .ιί 0.15 an 0.11: an 0,251 0.5 0,111 0.6 1 Group 4 element 0.1 & ^ 〇, 1〇9 _ΐβ Ο, ΟΐΒί 0; IBa, 0.010s O.liP ^ O.OSBi Q.dl! P4 ·; O.lRe b.OjiP, o; as • S s Φ o '1 1 1 f from 8 d «N; 〇 .: 5Sb 0.01P, 0JB, O.OQlGa 0.3B, aiEe, a.2Rh total 3Ι : Φ «Sg! G μ r " Cloud SS ii 〇 ·; Group 3 element i0.i; Ce, 0,01La.! D: 0iMg = 0; 00: 3! Li: 0. iSc > O.lCa 4 (5 兴 ❶ 惠 a 0..2 (¾. 0.6Mg, 0..lGd 0na d! 〇; iY, 0.5SC • 0.1Aa Q > l.Gd m: 1H & W a 1 Μ 1: i: Mill M 1 i I 1 ": M: S: M 1 ti 1111 1 1 ttt " 1 lt 1 il; HIM: 2:50 i〇0 hij ί: i: I11u ii. t I i. IBM. Na 1.50 .. Mill -rrr 0.5 # i 0.20: Fine π <! — · Ια in US IM 1; 24 MAt. Ϊ3 3 ^ § ¢ 5¾ CD r-ί. CD to ifq;; C? · RH ：. ??? .C? Group 1 element 1: fe «s 1 1 CO | | _l capsule τΗ OQ rH * iH hD · 3 1 iiiil in ii c5 d 〇d cS; I 1 111 I ii £ U ci. tH < N C3 ii < D: 1 Cui 1 till Q · 〇. < S) · Q: MMi c4 c > dd c > ϋ〇SS i〇tg cq co ^ ud CD CD CO CD CO § SSS? -30- 2005385¾ Take the obtained slab from the temperature immediately after casting (temperature immediately after taking out from the mold) of 9 5 (TC to 4 5 In the temperature range of 0 ° C, cooling is performed at a predetermined cooling rate by spray cooling. The temperature change in a predetermined place was measured by a thermocouple embedded in the mold, and the surface temperature of the slab after being taken out of the mold was measured with a contact temperature counting point. Based on these results and the analysis of heat transfer, the average cooling rate on the surface of the slab of 4 5 ° C. was calculated. The starting point of solidification was to prepare 0.2 g of molten liquid with individual components, and use a predetermined rate of cooling with continuous φ. It can be obtained by thermal analysis. From the obtained slab, a rolled material having a thickness of 10 mm X a width of 8 Omm and a length of 150 mm was prepared by cutting and cutting. For comparison, a part of the rolled material was performed at 950 ° C. Melt treatment. These rolled materials are rolled at room temperature with a reduction ratio of 80% (the first rolling), and a sheet with a thickness of 2 mm is made and subjected to aging treatment under the predetermined conditions (first aging). A sample was prepared. A part of the sample was rolled at room temperature with a reduction ratio of 95% (second rolling), and a plate φ material with a thickness of 0.1 mm was prepared and subjected to aging treatment under predetermined conditions (the 2 times aging). These manufacturing conditions are shown in Tables 4 to 7. The thus-produced samples were obtained by the following methods to determine the particle size of precipitates and inclusions, the total number of particles per unit area, and the resistance. Tensile strength, electrical conductivity and folding Workability. The results are shown in Tables 4 to 7. < Total number of precipitates and inclusions > A cross section perpendicular to the rolling surface of each sample and parallel to the rolling direction is used as a mirror surface. The mill was kept in this state, or after being corroded with an ammonia solution -31-2005385¾, the mm field was observed at a magnification of 100 times with an optical microscope. Thereafter, the major diameters of the precipitates and inclusions were measured (the particles were in contact with each other on the way) Under the condition of being drawn into the longest straight line in the grain), the 値 obtained is the particle size. In the formula (1), when the particle size of the precipitates and inclusions is measured from 1.0 μm to 1.5 μm If X = 1, substitute "α-0.5" // m or more and "α + 0 · 5" // m or less, substitute 2 as an integer of 2 or more). In addition, the number of frame-line intersections in a field of view of 1 mm × 1 mm per grain is taken as 1/2, and the total number of frames is calculated as 1 in the frame, and the number of arbitrarily selected 10 views is calculated. ≫ ^ (= 1 ^ + 112 + ... + ηιο) The average 値 (N / 10) is defined as the total number of precipitates and inclusions of each particle size. < Concentration ratio > Honing the cross-section of the alloy, using a beam diameter of 0.5 μm, and analyzing the length of 50 μm with X-rays in a multiple field of view, and naturally performed: • Line analysis to find individual line analysis The content of each alloy element in the alloy is large and minimum. The larger two of the largest 値 and the smallest 値 are respectively removed to obtain the average 値 of the largest 値 and the smallest 値 for the remaining 8 times, and the ratio 値 is used as the concentration ratio. < Tensile strength > From the above-mentioned sample, the tensile direction is parallel to the rolling direction. The test piece No. 1 3 Β specified by Π S ZO 2 2 0 1 is taken, and according to the method specified by Π S ZZ, The field of view of the tensile strength at room temperature (25 t) is not defined. When the maximum division of the sample in the field is 20000 times, it is calculated as 224 1 strength -32- 2005385¾ TS (MPa ). ≪ Conductivity > From the above test sample, a test piece having a width of 10 mm x a length of 60 mm was taken so that the tensile direction was parallel to the rolling direction, and a current was caused to flow in the longitudinal direction of the test piece. The potential difference between the two ends was used to determine the resistance using the 4-terminal method. Then, the resistance (resistivity) per unit volume was calculated from the volume φ product of the test piece measured with a micrometer, and the temperature was measured after annealing with polycrystalline pure copper. The ratio of the resistivity of the standard sample was 1.72 μΩ · οιη, and the conductivity [IACS (%)] was obtained. ≪ Bendability > From the above sample, the width was taken so that the tensile direction was parallel to the rolling direction. l0mmx multiple test pieces with a length of 60mm The curvature radius was changed and a 90 ° bending test was performed. Using an optical microscope, the bent portion of the test piece after the test was observed from the outer diameter side of φ. Then, the minimum radius of curvature that did not cause cracking was R and determined. Ratio B (= R / t) to thickness t of the test piece. -33- 2005385¾ i

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9 * iH Bending processability 1 hit .. & O 0000 oodfeo Θ & 0ΘΟ _ ^ 3- CSi trH: .K) · e:: ^! Mm ms · ^: j. ^ ^ R1: ^ H; • _H. Th remaining 1 1 tf 豸 1; ...........:. J • 川 ... 』J ............ * · " ·· ·· ;. rH · C4: 0 © .051 C! 〇: (jcj. (Nl .. Θ H introduction. Intensity fiVOPa) .gg 丨 change g 3 00 s δ 3 1 review § «f I xm fiber; iae © Marriage 0 Him: 1_ 1150; 0.5 14 i 0.01 0,05 15 m ί§: ¾ Mi: 棼 m lisii iim O f II8IB • Continuous :: bite :: 呀: w 成 Waste · ϋί? α 2.3 ( T〇3'_ 3 · 0 (Τί) 2-7 .. (15) mm IS Si Η -Φ: _Θ ◎ @ @ © @ ◎ 〇〇0 ® @ ◎ Grassen_gen #:. Mmimm ff Η Μ '1 1 :: 丨 ·· 丨 丨. Viol 1: 1 Ml i \' Μ: Η: 丨 "1» iiii ό o '袅 毖 mm < mm .itmI 财 1 fii ii: in ί " l ! 1 g —: .. Khan · —; ri H. ： #; ^. ^: O 〇rH Tt do 11 jr iii ij «ί t! I ¢ 11 mm s. 1.5h 1 fine i: 6h: liml ^ 13L · [IHi lg 35D 350 350 350 350 350 350 35Q 3β〇3Β0 450 〇〇〇〇〇S i2! S i2 ifS oo etc. m CN 濉 Thickness (ππη): * ·· ί rJ: Γι-i -i— »· rrl: o # c5 o dl d r-I. · τ-Η · .r-if.: τΗ 〇: · C ) O 'C5 Ο τΗ oooooyddddoo t4 * -i M13 颏 b IO IQ U3 4D 16 妁 Approximately as kq must be k〇ΙΟ (M: name :: 0¾ slave: 4A n > ΰα C < | (M k〇ΙΩ fM GS | wnm shirt ft: g 1 gangster rhyme 1: leg .: 丨 Λ tX5h ai | g 11111 8 i I § i is S 1 J 〇QD 1 * B 1 · domain m shirt m ».J ο ο ο ο ο .c4 ¢ 5.,. e < i 〇 .: .〇 · φ: φ.: 〇: «ί -csi .:: © q csi: m. ο q ο 〇〇CO 0D CO Ό5 0 ( 5 CO ：: jC〇 · ： Ιώ ud to i〇. Eg: w csi ea 笤 笤 锊 笤 锊 SI til o 〇_ 〇xo XD G4 cooling rate Cc / s) ooooo > —f rH ttH rH 1H Ο ο ο 〇〇 〇: rS rf .yi ΊτΗ * 2 2S3S collar 6 < Snz :: 0SI- CO i〇Wi CD ¢ 0 Φ ¢ 0 «D φcomposite S: c〇c〇: co._ inch but < R bi r-ί (jq pa. i〇IA UD i〇Φ b- φ Φ Qj ίο m ιο us to g 结 ssg tD ^ ς〇QD 0s * N ^ sa ^ w® ^ Ke $ i ^ 「〇」 * NIIIIl (is 「# iH-g« fe 」Thief l ^« fsewffir «^「 sM / « ^ _fr ^ / i} ¥ «^ _ ^ 扣) felDi} Sao« J «e« ^ W6 ¥ WS, MI) such as φϊκφ 「©」 ^ 「〇」, 「〇」 ΝΘ SNia 七 蛔 「M」 ^ 「 ®ia '' -36- 2005385

m .Solution: treatment 1: L_ h ': trf fr: 1 ί; 擗 擗 ί: • 蚺 1 丨 丨: 聛 U 1 ;: 1 bending processability & :: 1 :. .1 lx X] k X ί X x XXXXXX f: bit | 1. \ li ^ — \ A ιό. 1 id tib ^ ίο- ❿1: book; 1; 1 tf. 麦 iCL! Κ hi [秘 绍 g IS 〇〇 | 〇 > Λ csj § < S1 1 __ ί * »| g | 1310 720 320 " if 10; ^ 690: 1 1210 820 873 692 o § 1 < Wi Έ mm # 1! 1 结. 抑: 2 1 钟 ί ί! Ί ΐΐ M ι: .111 f: 杳 议 " r 3 S " 丨 § #: ® M ..: * ........... .:: Money 丨 丨 1: il 1 X x XX 丨 SC x: χ · x Μ 矣 I #: mm Second heat treatment: ·· 酲] IS 丨 1 1 § 鸯 «is 1 System # 5 | C: K i bacteria i bloom aluminum 1 caused waterlog mil mist 丨 丨 m Hall CN moved feil lit · 1 1: l rH rfH i—i rH t—j Q 〇C > ί-1 τΗ τ-Η τΗ ιΗ dl c5 c5 c > ο S 1 «Ci bismuth I!: 丨 end of 脔 脔 1 first heat treatment J ^ < starter 1 sS 1 1 1 II 〇ο 〇ο ο .G2) ·« 〇 . ¢ 5 ¢ 3. -SD · .7J ^ k · * 2 $: £ Β »J ^ S ·. Τι» · Tyi *.. \ J · . · 11111 • o,? 1 First rolling fes: fi 'o: q (¾ 〇io 〇s) cq t-4 vh c4 ο: · ο; m. Ο: & ρ: ρ5 :; d · 〇 4 ¢ ^: Φ ο: θ. M: 〇ο Ό: life ·. 胬 胬 i weaving 1 field like | f: f 锊 鞔 锊 鞔 it cooling rate to ^ bar 笤 __ g |: Q: es m丨 ^ 1¾¾¾ 0D M3 §: sH Wai Congzui: .Cffi_ =. ≪#: · fesr: ΰΰ :: icrs ·: SS SS 3¾ Wu 镒 han 'cs ^^ i ^ wa? ^ Kq) 4n: & i «「. x ^ M} & s 「fflHaiiete」 * 1K «sewffii. * 忉 「(倾 倾 七« ^^^ 如 / 1) + < «忉 _ 擗 扣 £ 1 鼷 ®」 岷 e * 忉 味} 鼷 奥 —Mi > sw ^! Tw (eYa) < nfe 伥«「 X 」^ 0« ^ # 0 岷 岷 ^^ 「酲 Basket」 -37- 2005385 ©) The "Evaluation" of the column of bending workability conforms to a plate having a tensile strength TS of 80 MPa or less In the case of BS2.0, when the tensile strength TS exceeds 800 MPa, if the formula (b) below is satisfied, it is "0", and if it is not, it is recorded as "X". 41.2686-39.4583xexp [-{(TS-6 1 5.675) /2358.08} 2]-(b) φ Figure 2 is a graph showing the relationship between the tensile strength and the electrical conductivity of each example. As shown in Tables 4 to 7 and Figure 2, in Examples 1 to 67 of the present invention, the chemical composition, concentration ratio, and total number of precipitates and inclusions are within the range specified by the present invention, so the tensile strength And the conductivity is in accordance with the above formula (a). Therefore, the balance of electrical conductivity and tensile strength of these alloys can be said to be at the same level as or higher than that of Be-added copper alloys. In this way, it can be understood that the copper alloy of the present invention is rich in changes in electrical conductivity and tensile strength. In addition, in the present invention examples 1, 6, 11, 1, 16, 3, 4, 6, 6, 37, 39, 41, 64, 65, and 66, the addition amount and / or manufacturing conditions were fine-tuned using the same component system Example. These alloys have a relationship between tensile strength and electrical conductivity as indicated by “Δ” in FIG. 2, and thus can be said to be copper alloys having the characteristics of copper alloys known in the prior art. The bending characteristics are also good. On the other hand, the contents of any of Comparative Examples 1 to 4, 6, 10, 12 to 14, 16, and 1 7 'were outside the range specified in the present invention, and the bending workability was poor, and the conductivity was low. Comparative Examples 1 ~ 3 and 17 have severe edge cracks during the second compression delay, and the sample cannot be taken, so it has not reached the level of -38- 2005385¾ for characteristic evaluation. In addition, Comparative Examples 5, 9, 11 and 15 which were melt-treated at 95 ° C were inferior in tensile strength and inferior in bending workability. Example 2 The application to a safety tool must be evaluated. Samples were prepared using the following methods, and the abrasion resistance (Vickers hardness) and spark resistance were evaluated. The alloy having the chemical composition shown in Table 8 was melted in a high-frequency furnace in the atmosphere and die-cast using a durville casting process. That is, the mold 1 is maintained in a state as shown in FIG. 3 (a). 'On the one hand, charcoal powder is used to ensure a reduced environment. On the other hand, 1300 ° C molten water is cast into the mold 1, and the mold 1 is as shown in FIG. 3 ( b) It is tilted as shown in the figure, and is solidified in the state shown in Figure 3 (c) to produce a cast piece. The mold 1 is made of cast iron having a thickness of 50 mm, and cooling holes are provided in the mold 1 to allow piping to be performed by air cooling. For the sake of easy casting, the slab is made wedge-shaped, the lower section is made 30x300, the upper section is 50x400mm, and the height is 7000mm. The part from the lower end of the obtained slab to 300mm is taken for surface honing. Then, cold rolling (30-10 mm)-> heat treatment (3 7 5 ° Cx16h) was performed to obtain a plate having a thickness of 10 mm. Using these plates, the total number of precipitates and inclusions, tensile strength, electrical conductivity, and bending workability were investigated by the methods described above, and the abrasion resistance, thermal conductivity, and spark resistance were also investigated by the following methods Productive. The results are shown in Table 8. 39 · 2005385¾¾ < Abrasion resistance > A test piece with a width of 10 mm and a length of 10 mm was taken from the sample, and the cross section perpendicular to the rolling surface and parallel to the rolling direction was mirror-honed, using JIS Z 2 2 4 The Vickers hardness at 25 ° C and a load of 9.8 N was measured by the method specified in 4. < Thermal conductivity > | The thermal conductivity [TC (W / m · K)] is obtained by substituting the above-mentioned conductivity [IACS (%)] into the formula "TC = 1 4.804 + 3.8 1 72xIACS" And find it. < Spark Resistance >

Using a table type honing machine with a rotation speed of 120,000 rpm, a spark test was performed according to the method specified in jIS G 0 5 66 to visually confirm the presence or absence of sparks. φ In addition, a thermocouple was inserted at a position of 5 mm below the inner wall surface of the mold at a position of 100 mm from the lower section, and the temperature was measured. The average value of 4 5 0 ° C was obtained based on the liquidus line obtained from the heat transfer calculation. The cooling rate was 100 C / s. -40- 2005385¾¾

$ The presence or absence of sparks. Rn, m, ΓΠ- ㈣ Thermal conductivity .:::: fc S: :: f3 'rH::;:] mm ： 1 anti-frizz hair: ¾¾ N t-.o: ^ Φ cSl:; »H ip〇φ :: ^:; · .....: IT "! II | Τ · :: Bending processability] Evaluation 丨 ::,. Όρφ x Μ L. Love. fM # m 1 Electrical conductivity 1 雠; .cp; € SI: 〇p rH. _r ^ Tensile strength® EPaj lg: fe mm: _s Crystal grain size i: Pl-M m _ •. machine carbonyl M w (铤 ss m Μ; aoi am 0.01 0.1 α 秘 0Λ S .. • ί :: reading bait; :: C3: ··· (£ > ·· τ4 is;: P: " i. · 1 .Ρit 1 " mmf I 〇 | distinguish ss comparative example of the present invention e * ^ < n: 6 ^ «「 x 」^ ias ^ s ^ we < nft« 「〇」 s15fc ^ 「iH, Haiieii」 α® ^^ ΒΪ®1 ^ ί} * Νκ® ^ 1τ? δΛΙ) < π & ι «「 χ 」Μ ^ ΜΟ < π: 6®「 © 」^ Θ _.H, f ··--r. i ?:.« n :.-•. • ilf: ·· ':! &Quot; »! J / t &n; vsk Μ 1: / ττ; —i 2005385¾¾ As shown in Table 8, in Examples 6-8 to 70 of the present invention, The abrasion resistance is good, the thermal conductivity is large, and no sparks are observed. Any of Comparative Examples 18 and 19 did not meet the chemical composition prescribed by the present invention and the relationship prescribed by formula (1), and therefore, the thermal conductivity was small and sparks were observed. Feasibility of Industrial Use According to the present invention Can provide a copper alloy with rich product variations, excellent local temperature strength and processability, and properties required for safety tool materials, that is, thermal conductivity, abrasion resistance, and spark resistance. Manufacturing method [Simplified illustration of the drawing] Fig. 1 is a graph showing the relationship between the electrical conductivity and thermal conductivity of the copper alloy. Fig. 2 is a graph showing the relationship between the tensile strength and the electrical conductivity of each embodiment. Fig. 3 It is a schematic diagram showing the use of the Durville casting process. [Description of Symbols of Main Components] 1: Mold-42-

Claims (1)

200538562 (1) X. Application for patent scope 1. A copper alloy, characterized by: containing: from Zn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, Ge, Te and Se selected from one or two types in total 0%; mass%, the rest are formed by copper and impurities, and the particle size of the precipitates and inclusions present in the alloy is 1 // m or more The diameter and the total number of precipitates are in accordance with the relationship shown in the following formula (1): 'W > 1 ~ 20 logN ^ 0.4742 + 1 7.629xexp (-〇. 1 1 33xX) (1) where N is the total number (unit / mm2) of precipitates and inclusions per unit area, and X is the precipitate and Inclusion size «0. 2 · —a copper alloy, characterized in that it is expressed in terms of mass% and consists of any one of Ti: 0.0 1 to 5%, Zr: 0.0 1 to 5%, and Hf: 0.0 1 to 5%, And Zn, Sn, Ag, Mn, Fe, Co, A1, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se, or a total of 0.01 to 20%, and the rest is Copper and impurities, the particle size of precipitates and inclusions in the alloy is 1 // The particle size of the former, and the total number of precipitates and inclusions, is in accordance with the formula (1) Relationship, logN ^ 0.4742 + 1 7.629xexp (-〇.1133xX) ... (l) where N refers to the total number of precipitates and inclusions per unit area are: select Ni, 1 type m is as follows Count 43-200538562 (2) number (piece / mm2), X refers to the particle size (# m) of precipitates and inclusions. 3. A type of copper alloy, characterized in that when expressed in mass%, it contains Cr: 0.01 to 5 ° /. And one or more selected from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se 0.01 ~ 20%, the rest are copper and impurities. The particle size of the precipitates and inclusions in the alloy is 1 // m or more, and the total number of precipitates and inclusions is in accordance with The relationship shown in the following formula (1), logN ^ 0.4742 + 17.629xexp (-〇.1133xX) (1) where N is the total number of precipitates and inclusions per unit area (units / mm2 ), X is the particle size (V m) of precipitates and inclusions. 4. A copper alloy, comprising: from among Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se 0.1 to 20% of one or two or more selected, and 0.001 to 2% by mass of one or two or more selected from Mg, Li, Ca, and rare earth elements' The rest are copper and impurities, The particle size of the precipitates and inclusions formed in the alloy is 1 // m or more, and the total number of precipitates and inclusions is in accordance with the relationship shown in the following formula (1) , LogNg 0.4742 + 1 7.629xexp (-0.1 133χχ) "· (1) -44- 200538562 (3) Where N is the total number of precipitates and inclusions per unit area (units / mm2), X is Refers to the particle size (μm) of precipitates and inclusions. 5. —A copper alloy characterized by being expressed in mass% and containing: from Ti: 0.01 to 5%, Zr: 0 · 01 to 5 ° / And Hf: any one of 0.01 to 5%, from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se Choose from 1 or 2 or more 0.001 to 20% in total, and one or two or more selected from Mg, Li, Ca, and rare earth elements in a total of 0.001 to 2% by mass, 1 the remainder is formed by copper and impurities, The particle size of the precipitates and inclusions present in the alloy is 1 # m or more, and the total number of precipitates and inclusions is in accordance with the relationship shown in the following formula (1): log N ^ 〇 .4742 + 17.629xexp (-0.1133xX) * (1) where N is the total number of precipitates and inclusions per unit area (pieces / mm2), X is the grains of precipitates and inclusions Diameter (# m). 6. A copper alloy characterized by the following: when expressed in mass%, it contains: Cr: 0.01 to 5%, from Zn, Sn, Ag, Mn, Fe, Co, A1, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se. One or two or more selected in total. 0.01 to 20%, and selected from Mg, Ll, Ca, and rare earth elements 1 or 2 of the total is 50 · 001 ~ 2% by mass, the rest are copper and impurities, and the size of the precipitates and inclusions present in the alloy is 1 // m or more Particle size, precipitates and inclusions The total number of objects conforms to the relationship shown in the following formula: -45- 200538562 (4) lo gNS 0.4742 + 17.629xexp (-0.1133xX) ... (1) where N refers to precipitates and inclusions The total number per unit area (pieces / mm2), X refers to the particle size (// m) of precipitates and inclusions. 7. A copper alloy, characterized in that it contains: from Zn, Sn, Ag, Mn, Fe, Co, A1, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se One or two or more selected from the total of 0.1 to 20%, and from P, B, Bi, Tl, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, Po, Sb, Au, Ga, S, Cd, As, and Pb selected from one or two types in total 0.001 ~ 3 mass ° / 0 'The rest are copper and impurities, and the precipitates formed in the alloy and The particle diameter of the inclusions is 1 V π or more, and the total number of precipitates and inclusions is in accordance with the relationship shown in the following formula (1) 'logN ^ 0.4742 + 17.629xexp (-0.1133xX) (1) Among them, N refers to the total number of precipitates and inclusions per unit area (units / mm2), and X refers to the particle size of the precipitates and inclusions m) ° 8.-a copper alloy It is characterized in that it is expressed in terms of mass%. 'Contains: from Ti: 0.01 to 5%, ZΓ: 0.01 to 5 ° /. And Hf: any one selected from 0.01 to 5%, from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, 8b 1 ^ 〇, 乂, 1 ^ 1), Ding & , 〇6, Ding 6 and 36 selected from one or two or more of the total 〇1 ~ 20%, and from P, B, Bi, T1 ,, -46- 200538562 (5) Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, Po, Sb, Au, Ga, S, Cd, As, and Pb are selected from a total of 0.001 to 3% by mass, and the rest It is formed of copper and impurities, and the particle size of the precipitates and inclusions in the alloy is 1 # π or more, and the total number of precipitates and inclusions is in accordance with the following formula (1) The relationship shown is logN ^ 0.4742 + 1 7.629xexp (-〇.1133xX) (1) where N is the total number of precipitates and inclusions per unit area (pieces / mm2), and X is Refers to the particle size of precipitates and inclusions (# πι). 9. A copper alloy, characterized in that when expressed in mass%, it contains: Cr: 0.01 to 5%, from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, One or two or more selected from Nb, Ta, W, Ge, Te, and Se. 〇1 ~ 20%, and from P, B, Bi, Ti, Rb, Cs, Sr, Ba, Tc , Re, Os, Rh, In, Pd, Po, Sb, Au, Ga, S, Cd, As, and Pb, a total of one or two selected from 0.0 0 1 to 3 mass%, the rest are copper and The particle size of the precipitates and inclusions formed in the alloy with a particle size of 1 # m or more and the total number of precipitates and inclusions formed by the impurities are in accordance with the following formula (1) Relationship, logNS 0.4742 + 17.629xexp (-0.1133xX) (1) -47- 200538562 (6) where N is the total number of precipitates and inclusions per unit area (units / mm2), X Refers to the particle size of precipitates and inclusions m) ° 10. —A copper alloy characterized by: from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V , Nb, Ta, W, Ge, Te, and Se A total of 0.1 to 20% by mass, a total of 0.001 to 2% by mass of one or two selected from Mg, Li, Ca, and rare earth elements, and P, B, Bi, scandium, and • Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, P0, Sb, Au, Ga, S, Cd, As, and Pb.A total of 0.001 ~ 3% by mass, the rest are copper and impurities. The particle size of the precipitates and inclusions in the alloy that are 1 # m or more, and the total number of precipitates and inclusions are in accordance with The relationship represented by the following formula (1), logNS 0.4742 + 1 7.629xexp (-0.1133xX). (1) where N is the total number of 1 per unit area of the precipitates and inclusions (pieces / mm2 ), X refers to the particle size of precipitates and inclusions (# πι) ° 11. A copper alloy characterized by: expressed in mass% 'is composed of: from Ti: 0.01 to 5%, Zr: 0.01 to 5 % And Hf: Any one selected from 0.01 to 5%, from Zn, Sn, Ag, Mn, Fe, Co, A1, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te, and Se Choose one or more of them 〇1 ～ 20%, a total of one or two or more selected from Mg, Li, Ca, and rare earth elements. 0.001 ~ 2 mass -48- 200538562 (7)%, and from p, One or two selected from B, Bi, Ti, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, P0, Sb, An, Ga, S, Cd, As, and Pb Total of more than 0.001 to 3% by mass' The remainder is copper and impurities, formed, and the particle size of the precipitates and inclusions present in the alloy is 1 // m or more, and the precipitates and The total number of inclusions conforms to the relationship shown in the following formula (1) '• logN' 0.04742 + 17.629xexp (-0.1133xX) ... ) Among them, N refers to the total number (units / mm2) of the precipitates and inclusions per unit area, and X refers to the particle size m of the precipitates and inclusions). 12. A copper alloy, characterized in that when expressed in mass%, it is composed of: Cr: 0.01 to 5%, from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V , Nb, Ta, W, Ge, Te, and Se. One or two selected from a total of 0.01 to 20%. One or two selected from Mg, Li, Ca, and rare earth ^ elements. Total 0.001 to 2% by mass, and from P, B, Bi, Tl, Rb, Cs, Sr, Ba, Tc, Re, 0 s, Rh, In, P d, P o, Sb, Au, Ga, S , Cd, As, and Pb selected from one or two or more of a total of 0.001 to 3% by mass, and the rest are copper and impurities. The particle size of precipitates and inclusions formed in the alloy is 1 / / m or more, and the total number of precipitates and inclusions is in accordance with the relationship shown in the following formula (1), logN ^ 〇.4742 + 17.629xexp (-0.1133xX) ... (1) -49- 200538562 (8) where N is the total number of precipitates and inclusions per unit area (pieces / mm2), and X is the particle size of the precipitates and inclusions (μ m) ° 1 3 · If any one of the patent application scope items 1 to 12 The carrier copper alloy, which further contains 0.1~5% by mass of Be, to replace one part of the copper. 14. The ratio of the "maximum content of average content" to the minimum content of average content in a small area of at least one alloy element in the copper alloy as described in any one of claims 1 to 12 in the scope of the patent application. It is equal to or greater than 1 · 5 ° 1. According to the copper alloy described in item 13 of the scope of the patent application, at least one of the alloy elements has a maximum average content and a minimum average content. The ratio is 1.5 or more. 16. The copper alloy according to any one of claims 1 to 12 in the scope of the patent application, wherein the crystal grain size is 0.0 1 to 3 5 // m. 17 · The copper alloy as described in item 13 of the scope of patent application, wherein the grain size is 0.01 ~ 35 // m. 18 · The copper alloy as described in item 14 of the scope of patent application, wherein the grain size is 0.01 to 35 // m. 19 · The copper alloy described in item 15 of the scope of patent application, wherein the crystal grain size is 〇1 ~ 35 // m. 20 · A method for manufacturing a copper alloy, characterized in that it is a slab obtained by melting and casting a copper alloy having the chemical composition described in any one of the claims 1 to 13 of the scope of application for a patent, from At least the temperature of the slab obtained immediately after casting is in the temperature range up to 450 ° C, and cooled at a cooling rate of 0.5 ° C / s or more -50- 200538562 (9), wherein: copper alloy is present in the alloy and inclusions The particle size in the case where the particle size is 1 # m or more, and the total number of impurities are in accordance with the following equation (1) logN ^ 0.4742 + 1 7.629xexp (-〇.1133xX) · Among them, N refers to the number of φ (units / mm2) of precipitates and inclusions per unit surface, and X refers to the particle size of precipitates and inclusions (# 21.—Method of Manufacturing Copper Alloys', which is characterized by the scope of patent application The slab obtained by melting and casting the copper alloy according to any one of items 1 to 13 has a cooling rate of 0 from a temperature range of at least the slab just obtained to a temperature of 450 ° C. Cool and in the temperature range below 600 ° C: Copper alloys are precipitates and inclusions in the alloy1 The particle size of m or more and the sum of the precipitates and inclusions φ are in accordance with the relationship shown in the following formula (1), logN ^ 0.4742 + 17.629xexp (-0.1133xX) ·, where N is the precipitate per unit area And the number of inclusions (pieces / mm2), X refers to the particle size of the precipitates and inclusions (// 22 · — a method of manufacturing copper alloys, which is characterized by: any one of the scope of patent applications 1 to 13 The slabs obtained by melting and casting the copper alloys mentioned above have at least a total of m and o deposits from the precipitates and inclusions in the steel, which are obtained by casting the chemical composition that they have. 5 ° C / sec or above, where the particle size is counted, is. (1) Total number of materials m) 〇 It is -51-200538562 (10) obtained by casting the chemical composition with In the temperature range up to 4 5 0 C, it is cooled at a cooling rate of 0.5 / sec or more, and after processing in a temperature range of 6 0 ° C or less, it is provided in a range of 1 500 to 7 5 0 C. In the temperature range, heat treatment for more than 30 seconds is provided. Copper alloys are precipitates and inclusions in the alloy. The particle size of the particles is 1 # m or more, and the total number of precipitates and inclusions is in accordance with the relationship not shown in the following formula (1), φ logN ^ O.4742 + 17.629xexp (-0.1133 xX)-*-(l) where N is the total number of precipitates and inclusions per unit area (pieces / mm2), and X is the particle size of the precipitates and inclusions (// m). 23. The method for manufacturing a copper alloy as described in item 22 of the scope of patent application, wherein the processing is performed in a temperature range of 600 ° C or lower and the heat treatment is maintained for 30 seconds or more in a temperature range of 150 to 750 ° C It is performed a plurality of times. φ 24. The method for manufacturing a copper alloy as described in item 22 or 23 of the scope of patent application, wherein after the final heat treatment, processing is performed in a temperature range below 600 ° C. -52-