JP5988794B2 - Copper alloy sheet and manufacturing method thereof - Google Patents

Description

  The present invention relates to a copper alloy sheet and a method for manufacturing the same, and more particularly to a Cu—Fe—P copper alloy sheet used for a lead frame and the method for manufacturing the same.

  Materials used for electrical and electronic parts such as lead frames are required to have high strength and excellent electrical conductivity and heat resistance. As such materials, Cu-Fe-P-based copper alloys such as C1940 alloy are required. Is used.

  In recent years, with the increase in capacity, miniaturization, and high functionality of semiconductor devices that use lead frames and the like, materials used for lead frames and the like are required to have higher strength and conductivity. In addition, the lead frame is generally processed into a shape having a large number of pins by stamping (press punching), and is heat-treated at a high temperature in order to remove distortion at the time of stamping, and therefore has excellent heat resistance. Is required. In particular, in materials used for lead frames and the like, there is a tendency to increase the number of cases where heat treatment is performed at a high temperature for a short time in order to improve productivity, and thus heat resistance to heat treatment at a high temperature of 500 ° C. or higher is required. Has been.

  However, in the Cu-Fe-P-based copper alloy sheet, there is a trade-off relationship between electrical conductivity, strength, and heat resistance, and it is not easy to improve these simultaneously. That is, in the Cu—Fe—P based copper alloy sheet, the electrical conductivity, strength, and heat resistance depend on the amount and size of Fe precipitates (a small amount of Fe—P). The size (diameter) of the Fe precipitate is not uniform and is generally distributed within a range of several nm to several μm. The types of Fe precipitates differ depending on the size. Fe deposits of several nm are mainly γFe particles, Fe precipitates of several tens to several hundreds of nm are mainly αFe particles, and Fe precipitates of 1 μm or more are mainly used. Fe-P particles. In addition, the electrical conductivity almost depends only on the amount of precipitates, regardless of the size of the Fe precipitates, and increases as the amount of Fe precipitates increases. On the other hand, the strength and heat resistance increase as the amount of matched γFe particles increases, and the influence of non-matched αFe particles and Fe—P particles is small. In addition, recrystallization near the coarse Fe—P particles tends to occur, and the heat resistance may be significantly reduced.

  Therefore, in the Cu—Fe—P-based copper alloy sheet, it is necessary to generate a large amount of γFe particles in order to improve conductivity, strength, and heat resistance at the same time. However, in order to obtain higher strength (for example, hardness HV160 or more) in the Cu—Fe—P-based copper alloy sheet, not only the precipitate (the amount and size of γFe particles) but also dislocation strengthening. (That is, work hardening by finish rolling after aging treatment) is necessary. However, when dislocation strengthening is performed, it is known that some γFe particles are cut by dislocation during finish rolling and re-dissolved, whereby the electrical conductivity is significantly reduced.

  Therefore, it has been proposed to improve the strength and heat resistance of the Cu—Fe—P-based copper alloy by performing solution treatment and intermediate cold rolling before aging treatment (see, for example, Patent Document 1). . In addition, Cu-Fe-P-based copper alloys are subjected to two-stage aging treatment, high temperature aging treatment and low temperature aging treatment after hot working and before cold working, without impairing high strength and conductivity and heat resistance. Has been proposed (see, for example, Patent Documents 2 and 3).

JP 2002-241873 (paragraph number 0007) JP-A-10-324935 (paragraph number 0014) JP 2011-174142 A (paragraph number 0015)

  However, when the solution treatment is performed before the aging treatment as in the method of Patent Document 1, the precipitate can be controlled more finely, but the decrease in the conductivity due to the finish rolling after the aging treatment is prevented. Can not be. In addition, in order to ensure a constant finish rolling ratio, it is necessary to make the plate material after the solution treatment relatively thick, which cannot be handled by a general continuous solution forming apparatus (a dedicated plate solution forming facility is required). Therefore, currently, in the production of Cu-Fe-P-based copper alloys, solution treatment is generally not performed.

  In addition, when the two-stage aging treatment of high temperature aging treatment and low temperature aging treatment is performed after hot working and before cold working as in the methods of Patent Document 2 and Patent Document 3, generally, non-uniform precipitation occurs (grain boundaries). Therefore, it is difficult to obtain a good balance between the density of γFe particles and αFe particles. In addition, since Fe—P particles precipitated during casting remain, sufficient heat resistance cannot be obtained.

  As described above, since the conventional Cu—Fe—P copper alloy manufacturing method cannot sufficiently eliminate the trade-off relationship between conductivity, strength, and heat resistance, some of the existing copper alloys such as C1940 alloy are partially used. In some cases, it may not be possible to deal with.

  Therefore, in view of such a conventional problem, an object of the present invention is to provide a Cu—Fe—P-based copper alloy sheet having high strength and excellent conductivity and heat resistance, and a method for producing the same.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain 1.5 to 3.0% by mass of Fe and 0.01 to 0.2% by mass of P, with the balance being Cu and inevitable. An ingot obtained by melting and casting a raw material of a copper alloy composed of impurities is heated to 1020 to 1080 ° C. and held for 2 hours or more, and then a rolling rate of 60% or more and 600 to 450 ° C. in a temperature range of 1800 to 750 ° C. Hot rolling is performed at 1080 to 450 ° C. so that the rolling rate becomes 30% or more in the temperature range, then cold rolling is performed at a rolling rate of 0 to 80%, and then at 520 to 600 ° C. for 30 minutes to 6 hours. Cu-Fe-P-based copper alloy sheet having high strength and excellent electrical conductivity and heat resistance by performing low-temperature aging treatment at 400 to 500 ° C. for 3 to 20 hours after the high-temperature aging treatment and manufacturing thereof Found that can provide a method This has led to the completion of the present invention.

  That is, the copper alloy sheet according to the present invention is a copper alloy raw material containing 1.5 to 3.0 mass% Fe and 0.01 to 0.2 mass% P, with the balance being Cu and inevitable impurities. After the molten and cast ingot is heated to 1020 to 1080 ° C. and held for 2 hours or more, the rolling rate is 60% or more in the temperature range of 1,080 to 750 ° C., and the rolling rate is 30% or more in the temperature range of 600 to 450 ° C. After performing hot rolling at 1080 to 450 ° C., followed by cold rolling at a rolling rate of 0 to 80%, and then performing high temperature aging treatment at 520 to 600 ° C. for 30 minutes to 6 hours. A low temperature aging treatment is performed at 400 to 500 ° C. for 3 to 20 hours.

  In this method for producing a copper alloy sheet, it is preferable to perform finish cold rolling at a rolling rate of 70% or more after performing low temperature aging treatment, and perform low temperature annealing at 250 to 600 ° C. after performing this finish cold rolling. Is preferred. The composition of the copper alloy further includes one or more elements selected from the group consisting of 0.2 mass% or less of Sn, 0.15 mass% or less of Mg, and 0.3 mass% or less of Zn. You may have. Further, the raw material of the copper alloy is selected from the group consisting of Ni, Ca, Al, Si, Cr, Mn, Zr, Ag, Cd, Be, Ti, Co, S, Au, Pt, Pb, Bi and Sb. You may have the composition which further contains an element more than a seed | species in the range of a total of 0.4 mass% or less.

  Further, the copper alloy sheet according to the present invention has a composition containing 1.5 to 3.0% by mass of Fe and 0.01 to 0.2% by mass of P, with the balance being Cu and inevitable impurities, The electrical conductivity is 60% IACS or more, the Vickers hardness HV is 150 or more, and the Vickers hardness HV after holding at 500 ° C. for 30 minutes is 140 or more.

In this copper alloy sheet, the density of Fe-P particles having a particle size of 1 μm or more is preferably 30 particles / mm ² or less, and the magnetization is preferably 1.0 to 4.0 emu / g. Further, the copper alloy sheet material has a composition further including at least one element selected from the group consisting of Sn of 0.2% by mass or less, Mg of 0.15% by mass or less, and Zn of 0.3% by mass or less. May be. Further, the copper alloy sheet is one selected from the group consisting of Ni, Ca, Al, Si, Cr, Mn, Zr, Ag, Cd, Be, Ti, Co, S, Au, Pt, Pb, Bi and Sb. You may have the composition which further contains the above element in the range of 0.4 mass% or less in total.

  According to the present invention, it is possible to produce a Cu—Fe—P-based copper alloy sheet having high strength and excellent electrical conductivity and heat resistance.

  In the embodiment of the method for producing a copper alloy sheet according to the present invention, it contains 1.5 to 3.0% by mass of Fe and 0.01 to 0.2% by mass of P, with the balance being Cu and inevitable impurities. An ingot obtained by melting and casting a copper alloy raw material is heated to 1020 to 1080 ° C. and held for 2 hours or more, and then a rolling rate (working degree) is 60% or more and 600 to 450 ° C. in a temperature range of 1800 to 750 ° C. In this temperature range, hot rolling is performed at 1080 to 450 ° C. so that the rolling rate (working degree) is 30% or more, then cold rolling is performed at a rolling rate of 0 to 80%, and then at 520 to 600 ° C. After performing high temperature aging treatment for 30 minutes to 6 hours (continuously), low temperature aging treatment is performed at 400 to 500 ° C. for 3 to 20 hours (two-step aging treatment of high temperature aging treatment and low temperature aging treatment is performed).

  Fe has an effect of improving the strength of the copper alloy sheet, but if the content is less than 1.5% by mass, the strength is not sufficiently improved, and if it exceeds 3.0% by mass, the conductivity decreases. The Fe content is preferably 1.5 to 3.0 mass%, more preferably 1.8 to 2.5 mass%.

  P has a deoxidizing action of the molten metal and has an action of improving conductivity and strength by forming and precipitating a compound with Fe. However, when its content is less than 0.01% by mass, these actions are not achieved. When it exceeds 0.2% by mass, these actions are saturated, and the precipitate is liable to be coarsened. Therefore, the P content is preferably 0.01 to 0.2% by mass, More preferably, it is 0.015-0.15 mass%.

  The composition of the copper alloy further includes one or more elements selected from the group consisting of 0.2 mass% or less of Sn, 0.15 mass% or less of Mg, and 0.3 mass% or less of Zn. You may have. Sn has the effect of improving the heat resistance of the copper alloy sheet, but if its content exceeds 0.2% by mass, the conductivity decreases, so the Sn content is 0.2% by mass or less. Is preferable, and it is further more preferable that it is 0.1 mass% or less. Mg has the effect of improving the heat resistance of the copper alloy sheet, and the decrease in conductivity due to its addition is relatively small. However, when its content exceeds 0.15% by mass, the productivity decreases. Therefore, the Mg content is preferably 0.15% by mass or less, and more preferably 0.1% by mass or less. Zn has a deoxidizing action of the molten metal like P, but if its content exceeds 0.3% by mass, the deoxidizing action is saturated and the conductivity decreases, so the Zn content is 0.3% by mass. % Or less is preferable, and 0.2% by mass or less is more preferable.

  In addition, when using the scrap of an electronic material etc. as a raw material of a copper alloy board | plate material, the element mixed in the scrap may be inevitably mixed in the raw material. Moreover, when manufacturing many types of copper alloys, if the raw materials of the respective copper alloys are melted in the same melting furnace, the components of the previous copper alloy may be mixed in the raw materials, though only slightly. As such inevitable impurities, for example, Ni, Ca, Al, Si, Cr, Mn, Zr, Ag, Cd, Be, Ti, Co, S, Au, Pt, Pb, Bi, Sb, etc. are each set to 0. It may be included in a range of 1% by mass or less and a total of 0.4% by mass or less.

  According to the embodiment of the method for producing a copper alloy sheet according to the present invention, an ingot for melting and casting a copper alloy raw material can be produced by a normal copper alloy continuous casting method or semi-continuous casting method.

  The ingot is hot-rolled after being heated to about 1020 to 1080 ° C. by a heating furnace and held for 2 hours or more. The heating prior to the hot rolling has the effect of solid-dissolving Fe—P particles, which causes a decrease in heat resistance, in addition to the effect of reducing segregation and crystallized matter generated during casting.

  In addition, since a Cu-Fe-P type copper alloy precipitates during hot rolling, it is relatively difficult for (dynamic) recrystallization to occur. Therefore, during this hot rolling, by performing strong rolling at a high temperature range of 1800 to 750 ° C., it is possible to suppress the precipitation of the Cu—Fe—P-based copper alloy and generate dynamic recrystallization. In the hot rolling in the temperature range of 1,080 to 750 ° C., the rolling rate is preferably 60% or more, more preferably 65% or more, and further preferably 70% or more. Subsequently, it is considered that fine Fe or Fe—P-based compounds are precipitated in the copper matrix by performing hot rolling at a rolling rate of 30% or more in a temperature range of 600 to 450 ° C. In addition, in hot rolling in a low temperature region of 600 to 450 ° C., there is an effect that the intermetallic compound is dynamically precipitated, thereby generating precipitates and refining, and by subsequent aging annealing treatment, γFe particles and The balance of the density of the αFe particles can be adjusted.

  In the cold rolling performed after the hot rolling, the rolling rate is set to 0 to 80%. If the rolling rate at this stage exceeds 80%, the rolling rate of the final finish rolling may not be ensured. In order to improve productivity, cold rolling at this stage may be omitted. In addition, when this rolling rate is 0%, it means performing an aging process directly, without performing this cold rolling.

  The aging treatment after cold rolling is performed to precipitate solid solution elements. In a normal aging treatment, when the aging temperature is relatively low (for example, 450 ° C.), the precipitation rate is slow, and the aging treatment time required to obtain a precipitation amount that secures a desired conductivity is several tens of hours. Further, the particle size of the precipitate is small, and it is easy to re-dissolve by cutting by dislocation during the subsequent finish rolling, and the final conductivity is lowered. On the other hand, when the aging temperature is relatively high (for example, 600 ° C.), the precipitation rate is high and the precipitates are also easily coarsened, so that it is difficult to adjust the density balance of γFe particles and αFe particles. In addition, even when the aging treatment temperature is an intermediate temperature (for example, 550 ° C.), it generally precipitates non-uniformly (precipitates preferentially at grain boundaries, deformation bands, etc.), so a good balance between the density of γFe particles and αFe particles is achieved. It becomes difficult to obtain.

  The aging treatment is performed in two steps: a high temperature aging treatment at 520 to 600 ° C. for 30 minutes to 6 hours and a low temperature aging treatment at 400 to 500 ° C. for 3 to 20 hours. The plate after hot rolling has fine and uniform precipitated particles due to dynamic precipitation, but by performing high temperature aging treatment at 520 to 600 ° C. for 30 minutes to 6 hours, Things grow into αFe particles in a relatively short time. If the temperature of this high temperature aging treatment is too low or the time is too short, the density of αFe particles is insufficient, and if the temperature is too high or too long, the density of Fe—P particles increases. . In the subsequent low temperature aging treatment at 400 to 500 ° C. for 3 to 20 hours, the density of γFe particles increases, but the αFe particles produced by the high temperature aging treatment do not grow excessively. If the temperature of this low temperature aging treatment is too low or the time is too short, the density of γFe particles will be insufficient, and if the temperature is too high or too long, the αFe particles will become coarse.

  This two-stage aging treatment, high temperature aging treatment and low temperature aging treatment, can be performed by adjusting the temperature of the annealing furnace. You may go.

  In order to obtain a desired plate thickness after the aging treatment, finish cold rolling is preferably performed. Generally, as the rolling rate (working degree) of the plate material increases, the strength increases, but the electrical conductivity and heat resistance are considered to decrease. However, the copper alloy sheet produced by the method for producing a copper alloy sheet according to the present embodiment has a finish cold rolling reduction rate (working degree) of 70% or more, preferably 80% or more, more preferably 90% or more. Even if it exists, it has the outstanding heat resistance. Further, depending on the required strength and plate thickness, it is necessary to perform low-temperature annealing after finish cold rolling (preferably at 250 to 600 ° C., more preferably at 350 to 500 ° C.). This low-temperature annealing is a strain relief annealing and can partially recover the conductivity lowered by finish cold rolling.

The embodiment of the copper alloy sheet according to the present invention has a composition containing 1.5 to 3.0 mass% Fe and 0.01 to 0.2 mass% P, with the balance being Cu and inevitable impurities. The electrical conductivity is 60% IACS or higher, the Vickers hardness HV is 150 or higher, and the Vickers hardness HV after holding at 500 ° C. for 30 minutes is 140 or higher. In this copper alloy sheet, the density of Fe-P particles having a particle size of 1 μm or more is preferably 30 particles / mm ² or less, and the magnetization is preferably 1.0 to 4.0 emu / g.

  As described above, the types of Fe precipitates in the Cu—Fe—P-based copper alloy sheet vary depending on the size. Fe deposits of several nm are mainly γFe particles, Fe precipitates of several tens to several hundreds of nm. Are mainly αFe particles, and Fe precipitates of 1 μm or more are mainly Fe—P particles.

  The γFe particles have a pinning effect of dislocation and grain boundary movement, and the higher the density, the better the strength and heat resistance of the plate material. The αFe particles have the effect of improving the strength and heat resistance of the plate material (however, they are less effective than the γFe particles). In particular, the γFe particles generated after the aging treatment are cut by dislocation and then re-dissolved during finish rolling for improving the strength of the plate material, and the conductivity of the plate material is likely to decrease. Therefore, αFe particles that are difficult to be cut by a certain dislocation are required. If the density of the αFe particles is too low, the effect of suppressing the decrease in the conductivity of the plate material is insufficient, and if the density of the αFe particles is too high, the density of the γFe particles inevitably decreases.

  Although the particle diameters of γFe particles and αFe particles are very small and need to be observed with a transmission electron microscope (TEM), the observation with TEM is local, and it is difficult to evaluate the entire plate. In addition, since it is difficult to distinguish γFe particles and αFe particles only from the particle size, a measurement method that replaces observation by TEM is required.

  The present inventors paid attention to the fact that αFe particles are ferromagnetic and determined the ratio of γFe particles to αFe particles by measuring the magnetization and conductivity of the plate material. Cu-Fe-P copper having high strength, excellent conductivity and heat resistance when the ratio of γFe particles to αFe particles is 4.0 emu / g, more preferably 1.5 to 3.5 emu / g. It has been found that an alloy sheet can be produced.

In addition, coarse Fe—P particles having a particle size of 1 μm or more have little effect of improving strength and heat resistance, and the density of γFe particles and αFe particles increases relatively as the density is lower. Therefore, the density of coarse Fe—P particles having a particle diameter of 1 μm or more is preferably 30 particles / mm ² or less, and more preferably 20 particles / mm ² or less.

  Hereinafter, examples of the copper alloy sheet material and the manufacturing method thereof according to the present invention will be described in detail.

[Example 1]
A copper alloy having a chemical composition shown in Table 1 (2.33 mass% Fe, 0.022 mass% P, and the balance copper alloy consisting of Cu and inevitable impurities) was melted in a high-frequency melting furnace, and the thickness was 30 mm. An ingot having a width of 50 mm and a length of 150 mm was produced.

  The ingot was heated to 1050 ° C. in a heating furnace and held for 3 hours, and then hot rolling was performed for 6 passes at a rolling rate of 67% in a temperature range of 750 ° C. or higher to obtain a rolled material having a plate thickness of 10 mm. In order to prevent the temperature from decreasing between passes of this hot rolling, it was kept in a heating furnace at 950 ° C. for 2 minutes. Then, after hold | maintaining for 2 minutes in a 600 degreeC heating furnace, hot rolling was performed by the rolling rate of 40% in the temperature range of 600-450 degreeC, and the rolling material with a plate | board thickness of 6 mm was obtained.

  Next, the obtained hot-rolled material was subjected to high-temperature aging annealing at 600 ° C. for 6 hours in an annealing furnace and then low-temperature aging annealing at 450 ° C. for 4 hours.

  Next, after polishing the surface and the back surface of the rolled material after two-stage aging annealing of these high temperature and low temperature, after performing finish cold rolling (rolling rate 98%) until the plate thickness becomes 0.127 mm, A low temperature annealing was performed in a 425 ° C. annealing furnace for 1 minute to produce a copper alloy sheet having a thickness of 0.127 mm.

  These production conditions are shown in Tables 2 and 3.

  About the obtained copper alloy board | plate material, while calculating the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains, heat resistance was evaluated.

The density of Fe-P particles is SEM-EDX (S-3000 manufactured by Hitachi High-Tech Fielding Co., Ltd. as a scanning electron microscope (SEM), and EMAX- manufactured by Horiba, Ltd. as an energy dispersive X-ray analyzer (EDX). 7000), an accelerating voltage of 20 kV and a magnification of 500 times (observation field of view 180 μm × 260 μm) were observed at any 20 locations on the copper alloy sheet, and the number of precipitates having a particle size of 1 μm or more was counted. The density of the precipitates (number per unit area) was determined. In addition, it confirmed that the deposit was Fe-P particle | grains by analyzing using EDX. As a result, the density of Fe—P particles was 14 particles / mm ² .

  Magnetization was measured by cutting a copper alloy sheet into 8 mm square and using a sample vibration magnetometer (VSM) so that a magnetic field was applied in the rolling direction of the copper alloy sheet under the conditions of an applied magnetic field of 5 kOe and a vibration frequency of 80 Hz. . As a result, the magnetization was 3.3 emu / g.

  The electrical conductivity was measured according to the electrical conductivity measurement method of JIS H0505. As a result, the conductivity was 64.2% IACS.

  Hardness measured Vickers hardness HV as test load 500gf based on JISZ2244. As a result, the Vickers hardness HV was 154.

  The heat resistance was evaluated by measuring the Vickers hardness HV after holding the copper alloy plate material in a furnace (atmosphere) heated to 500 ° C. for 30 minutes, taking it out of the furnace and cooling it to room temperature. As a result, the Vickers hardness HV after holding at 500 ° C. for 30 minutes was 146.

  These results are shown in Table 4.

[Examples 2 to 7]
Copper alloy having chemical components shown in Table 1 (in Example 2, 2.05 mass% Fe, 0.034 mass% P, 0.04 mass% Sn, 0.067 mass% Zn, In the third example, a copper alloy consisting of Cu and inevitable impurities, in Example 3, 1.68% by mass of Fe and 0.071% by mass of P, and in the fourth example, a copper alloy consisting of Cu and inevitable impurities. 2.48% by mass of Fe, 0.018% by mass of P, 0.05% by mass of Mg, and the balance being Cu and an inevitable impurity copper alloy, in Example 5, 2.41% by mass Fe, 0.028% by mass of P, 0.254% by mass of Zn, the balance being Cu and an inevitable impurity copper alloy, in Example 6, 1.93% by mass of Fe and 0.048% by mass % P, 0.073 mass% Sn, the balance being Cu and inevitable impurities In Example 7, a copper alloy consisting of: 2.32 wt% Fe, 0.032 wt% P, 0.097 wt% Ni, 0.005 wt% Mn, the balance being Cu and An ingot is made from an inevitable impurity), high temperature aging annealing is performed at 600 ° C. for 4 hours, low temperature aging annealing is performed at 450 ° C. for 8 hours (Example 2), high temperature aging annealing is performed at 600 ° C. for 1 hour, and low temperature. Aging annealing at 450 ° C. for 12 hours (Example 3), high temperature aging annealing at 550 ° C. for 6 hours, low temperature aging annealing at 420 ° C. for 4 hours (Example 4), high temperature aging annealing at 550 ° C. for 4 hours, low temperature Aging annealing at 420 ° C. for 8 hours (Example 5), high temperature aging annealing at 550 ° C. for 1 hour, low temperature aging annealing at 450 ° C. for 12 hours (Example 6), high temperature aging annealing at 600 ° C. for 6 hours, low temperature Except for performing aging annealing at 450 ° C. for 4 hours (Example 7), In the same manner as in Example 1, to prepare a copper alloy sheet. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles, respectively 8 / mm ² (Example 2), 18 / mm ² (Example 3), 13 / mm ² (Example 4), 9 / mm ² (Example 5), 16 pieces / mm ² (Example 6), and 10 pieces / mm ² (Example 7). The magnetizations were 2.9 emu / g (Example 2), 3.4 emu / g (Example 3), 2.2 emu / g (Example 4), 2.7 emu / g (Example 5), respectively. It was 2.1 emu / g (Example 6) and 3.1 emu / g (Example 7). In addition, the conductivity was 62.1% IACS (Example 2), 67.9% IACS (Example 3), 65.1% IACS (Example 4), and 62.8% IACS (Example 5), respectively. 66.1% IACS (Example 6) and 63.2% IACS (Example 7). The Vickers hardness HV was 164 (Example 2), 151 (Example 3), 162 (Example 4), 150 (Example 5), 154 (Example 6), and 172 (Example 7), respectively. Met. Further, the Vickers hardness HV after holding the copper alloy sheet at 500 ° C. for 30 minutes is 157 (Example 2), 142 (Example 3), 158 (Example 4), 145 (Example 5), 150 (Example 6) and 165 (Example 7). These results are shown in Table 4.

[Examples 8 to 10]
Copper alloys of chemical components shown in Table 1 (in Example 8, 2.15 mass% Fe, 0.026 mass% P, 0.054 mass% Co, 0.030 mass% Si, In Example 9, the remainder is a copper alloy consisting of Cu and inevitable impurities. In Example 9, 2.24 mass% Fe, 0.024 mass% P, 0.045 mass% Ti, and 0.009 mass% Copper alloy consisting of Al and the balance Cu and inevitable impurities, Example 10, 2.06 mass% Fe, 0.016 mass% P, 0.006 mass% Cr, 0.005 mass % Zr and the balance is a copper alloy consisting of Cu and inevitable impurities), and cold rolling is performed at a rolling rate of 75% between hot rolling and aging annealing, and the rolling rate of finish cold rolling A copper alloy sheet was produced in the same manner as in Example 1 except that the content was 92%. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles was 15 particles / mm ² (Example 8), 10 particles / mm ² (Example 9), and 19 particles / mm ² (Example 10), respectively. The magnetizations were 3.5 emu / g (Example 8), 2.5 emu / g (Example 9), and 1.7 emu / g (Example 10), respectively. The electrical conductivity was 66.9% IACS (Example 8), 64.2% IACS (Example 9), and 63.8% IACS (Example 10), respectively. The Vickers hardness HV was 174 (Example 8), 168 (Example 9), and 171 (Example 10), respectively. Further, the Vickers hardness HV after holding the copper alloy sheet at 500 ° C. for 30 minutes was 162 (Example 8), 163 (Example 9), and 167 (Example 10), respectively. These results are shown in Table 4.

[Examples 11 to 12]
Copper alloys having chemical components shown in Table 1 (in Example 11, 2.34% by mass of Fe, 0.019% by mass of P, and the balance of Cu and inevitable impurities, in Example 12, 2 An ingot was prepared from 40 mass% Fe, 0.030 mass% P, and the balance being a copper alloy consisting of Cu and inevitable impurities. In Example 11, the heating temperature during hot rolling was 1050 ° C. Instead, the rolling rate in the temperature range of 1080 ° C. and 750 ° C. or higher is set to 60%, the rolling rate in the temperature range of 600 to 450 ° C. is set to 50%, and in Example 12, the heating temperature during hot rolling is set to 1050 ° C. Instead, a copper alloy sheet was produced in the same manner as in Example 1 except that the rolling rate in the temperature range of 1020 ° C. and 750 ° C. or higher was 70% and the rolling rate in the temperature range of 600 to 450 ° C. was 33%. did. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles was 7 particles / mm ² (Example 11) and 16 particles / mm ² (Example 12), respectively. The magnetizations were 2.8 emu / g (Example 11) and 1.9 emu / g (Example 12), respectively. The electrical conductivity was 65.4% IACS (Example 11) and 63.3% IACS (Example 12), respectively. The Vickers hardness HV was 165 (Example 11) and 169 (Example 12), respectively. Furthermore, the Vickers hardness HV after holding the copper alloy sheet at 500 ° C. for 30 minutes was 160 (Example 11) and 165 (Example 12), respectively. These results are shown in Table 4.

[Comparative Example 1]
A copper alloy sheet was produced in the same manner as in Example 1 except that the heating temperature at the time of hot rolling was changed to 950 ° C. instead of 1050 ° C. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe—P particles is 63 particles / mm ² , the magnetization is 3.3 emu / g, the conductivity is 63.8% IACS, the Vickers hardness HV is 152, and the copper alloy sheet is held at 500 ° C. for 30 minutes. After that, the Vickers hardness HV was 108. These results are shown in Table 4.

[Comparative Example 2]
The heating temperature at the time of hot rolling was changed to 950 ° C. instead of 1050 ° C., except that the high temperature aging annealing was performed at 550 ° C. for 6 hours and the low temperature aging annealing was performed at 420 ° C. for 4 hours (as in Example 4). A copper alloy sheet was produced in the same manner as in Example 1. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles was 91 particles / mm ² , the magnetization was 3.0 emu / g, the conductivity was 65.1% IACS, the Vickers hardness HV was 157, and the copper alloy sheet was held at 500 ° C. for 30 minutes. After the Vickers hardness HV was 91. These results are shown in Table 4.

[Comparative Examples 3 to 5]
Instead of two-stage aging treatment of high temperature aging annealing and low temperature aging annealing, 600 ° C. for 10 hours (Comparative Example 3), 450 ° C. for 24 hours (Comparative Example 4), and 550 ° C. for 14 hours (Comparative Example 5) A copper alloy sheet was produced in the same manner as in Example 1 except that the isothermal aging was performed. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles was 20 particles / mm ² (Comparative Example 3), 14 particles / mm ² (Comparative Example 4), and 10 particles / mm ² (Comparative Example 5), respectively. The magnetizations were 4.7 emu / g (Comparative Example 3), 0.9 emu / g (Comparative Example 4), and 4.1 emu / g (Comparative Example 5), respectively. The electrical conductivities were 64.7% IACS (Comparative Example 3), 45.4% IACS (Comparative Example 4), and 63.1% IACS (Comparative Example 5), respectively. The Vickers hardness HV was 119 (Comparative Example 3), 159 (Comparative Example 4), and 158 (Comparative Example 5), respectively. Further, the Vickers hardness HV after holding the copper alloy sheet at 500 ° C. for 30 minutes was 98 (Comparative Example 3), 146 (Comparative Example 4), and 134 (Comparative Example 5), respectively. These results are shown in Table 4.

[Comparative Examples 6-7]
In Comparative Example 6, the rolling rate in the temperature range of 750 ° C. or higher is 40%, the rolling rate in the temperature range of 600 to 450 ° C. is 44%, and the rolling rate of finish cold rolling is 99%. A copper alloy sheet was produced in the same manner as in Example 1 except that hot rolling in a temperature range of ˜450 ° C. was not performed and the rolling rate of finish cold rolling was 99%. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles was 18 particles / mm ² (Comparative Example 6) and 12 particles / mm ² (Comparative Example 7), respectively. The magnetizations were 4.2 emu / g (Comparative Example 6) and 1.2 emu / g (Comparative Example 7), respectively. Moreover, the electrical conductivity was 65.6% IACS (Comparative Example 6) and 48.6% IACS (Comparative Example 7), respectively. The Vickers hardness HV was 142 (Comparative Example 6) and 177 (Comparative Example 7), respectively. Further, the Vickers hardness HV after holding the copper alloy sheet at 500 ° C. for 30 minutes was 113 (Comparative Example 6) and 146 (Comparative Example 7), respectively. These results are shown in Table 4.

[Comparative Examples 8-9]
Copper alloys having the chemical components shown in Table 1 (in Comparative Example 8, 3.48% by mass of Fe, 0.051% by mass of P, and the balance being Cu and inevitable impurities, in Comparative Example 9, A copper alloy sheet was produced in the same manner as in Example 1 except that an ingot was produced from .21 mass% Fe, 0.044 mass% P, and the balance being a copper alloy consisting of Cu and inevitable impurities. Produced. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles was 128 particles / mm ² (Comparative Example 8) and 16 particles / mm ² (Comparative Example 9), respectively. The magnetizations were 2.6 emu / g (Comparative Example 8) and 3.5 emu / g (Comparative Example 9), respectively. The electrical conductivity was 46.9% IACS (Comparative Example 8) and 61.9% IACS (Comparative Example 9), respectively. The Vickers hardness HV was 157 (Comparative Example 8) and 136 (Comparative Example 9), respectively. Further, the Vickers hardness HV after holding the copper alloy sheet at 500 ° C. for 30 minutes was 124 (Comparative Example 8) and 104 (Comparative Example 9), respectively. These results are shown in Table 4.

[Comparative Example 10]
The heating temperature at the time of hot rolling was changed to 950 ° C. instead of 1050 ° C., and after the cold rolling at a rolling rate of 75% between hot rolling and aging annealing, solution treatment was performed at 900 ° C. for 3 minutes. Until the temperature reaches 300 ° C. or less, water cooling is performed at a cooling rate of 50 ° C./min or more, high temperature aging annealing is performed at 600 ° C. for 2 hours, and low temperature aging annealing is performed at 450 ° C. for 2 hours. A copper alloy sheet was produced in the same manner as in Example 1 except that. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles was 79 particles / mm ² , the magnetization was 3.0 emu / g, the conductivity was 47.2% IACS, the Vickers hardness HV was 172, and the copper alloy sheet was held at 500 ° C. for 30 minutes. After that, the Vickers hardness HV was 151. These results are shown in Table 4.

[Comparative Example 11]
The heating temperature at the time of hot rolling was changed to 950 ° C. instead of 1050 ° C., cold rolling was performed at a rolling rate of 80% between hot rolling and aging annealing, and high temperature aging annealing was performed at 600 ° C. for 23 hours, low temperature aging A copper alloy sheet was produced in the same manner as in Example 1 except that annealing was performed at 500 ° C. for 23 hours and the rolling rate of finish cold rolling was 89%. These production conditions are shown in Tables 2 and 3.

About the obtained copper alloy board | plate material, the density, magnetization, electrical conductivity, and hardness of Fe-P particle | grains were calculated | required by the method similar to Example 1, and heat resistance was evaluated. As a result, the density of Fe-P particles is 106 particles / mm ² , the magnetization is 4.6 emu / g, the conductivity is 69.0% IACS, the Vickers hardness HV is 167, and the copper alloy sheet is held at 500 ° C. for 30 minutes. After the Vickers hardness HV was 101. These results are shown in Table 4.

  As shown in Table 4, all of the copper alloy sheet materials of Examples 1 to 10 have an electrical conductivity of 60% IACS or more, a Vickers hardness HV of 150 or more, and a Vickers hardness HV after being held at 500 ° C. for 30 minutes. 140 or more.

  On the other hand, in the copper alloy sheet materials of Comparative Examples 1 and 2, the heating temperature at the time of hot rolling is too low, the Fe—P particles cannot be dissolved, and the density of the Fe—P particles is too high. The Vickers hardness HV after holding for a minute was lowered, and the heat resistance was lowered.

  In the copper alloy sheet of Comparative Example 3, since the isothermal aging was performed at a high temperature of 600 ° C. for a long time, the magnetization increased (the density of γFe particles decreased, and the density of αFe particles and Fe—P particles increased). The electrical conductivity was high, but the strength was reduced and the heat resistance was reduced. In the copper alloy sheet of Comparative Example 4, since the isothermal aging was performed for a long time at a temperature as low as 450 ° C., the magnetization decreased (the density of γFe particles increased after aging, but re-solidified after finish rolling), and the conductivity Had fallen. In the copper alloy sheet of Comparative Example 5, since the isothermal aging was performed at an intermediate temperature of 550 ° C. for a long time, the magnetization was slightly increased (the balance between γFe particles and αFe particles was not good) and the heat resistance was reduced. It was.

  In the copper alloy sheet of Comparative Example 6, since the hot rolling rate in the temperature range of 1800 to 750 ° C. was too low as 40%, Fe—P particles precipitated without sufficient recrystallization, and the hardness and heat resistance Both were low. In the copper alloy sheet of Comparative Example 7, since hot rolling was not performed in the temperature range of 600 ° C. to 450 ° C., the magnetization was reduced (the amount of αFe particles generated during high temperature aging was reduced), and the strength and heat resistance were Although it was good, the electrical conductivity was decreasing.

  In the copper alloy sheet of Comparative Example 8, since the Fe content was too large, the amount of solid solution was high, and part of Fe could not be dissolved during hot rolling, and remained as Fe-P particles until the end. Both conductivity and heat resistance were reduced. On the other hand, in the copper alloy sheet of Comparative Example 9, the amount of Fe was too small and the hardness and heat resistance were reduced.

  In the copper alloy sheet of Comparative Example 10, since the solution treatment was performed between hot rolling and aging annealing, the density of Fe-P particles was too high and the conductivity was lowered. In the copper alloy sheet of Comparative Example 11, since the aging treatment time was too long, the density of Fe—P particles was high, the magnetization was increased, and the heat resistance was reduced.

Claims (5)

It has a composition containing 1.5 to 3.0% by mass of Fe and 0.01 to 0.2% by mass of P, the balance being Cu and inevitable impurities, and having an electrical conductivity of 60% IACS or more, Vickers hardness A copper alloy sheet material having a thickness HV of 150 or more and a Vickers hardness HV after holding at 500 ° C. for 30 minutes of 140 or more. The copper alloy sheet according to claim 1 , wherein the density of Fe-P particles having a particle size of 1 µm or more is 30 particles / mm ² or less. The copper alloy sheet according to claim 1 or 2 , wherein the magnetization is 1.0 to 4.0 emu / g. The copper alloy sheet has a composition further containing one or more elements selected from the group consisting of Sn of 0.2% by mass or less, Mg of 0.15% by mass or less, and Zn of 0.3% by mass or less. The copper alloy sheet material according to any one of claims 1 to 3 , wherein The copper alloy sheet is one or more selected from the group consisting of Ni, Ca, Al, Si, Cr, Mn, Zr, Ag, Cd, Be, Ti, Co, S, Au, Pt, Pb, Bi and Sb. The copper alloy sheet according to any one of claims 1 to 4 , wherein the copper alloy sheet has a composition further containing a total of 0.4% by mass or less of these elements.