Cu—Ni—Si-based copper alloy sheet having excellent mold abrasion resistance and shear workability and method for manufacturing same

Abstract

A CuNiSi-based copper alloy sheet of the invention has excellent mold abrasion resistance and shear workability while maintaining strength and conductivity, in which 1.0 mass % to 4.0 mass % of Ni is contained, 0.2 mass % to 0.9 mass % of Si is contained, the remainder is made up of Cu and inevitable impurities. The number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in a surface layer that is as thick as 20% of the entire sheet thickness from the surface is represented by a particles/mm.sup.2, and the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in a portion below the surface layer is represented by b particles/mm.sup.2, a/b is in a range of 0.5 to 1.5.

Claims

1. A CuNiSi-based copper alloy sheet, comprising: 1. 0 mass % to 4.0 mass % of Ni; and 0.2 mass % to 0.9 mass % of Si, with a remainder made up of Cu and inevitable impurities, wherein the CuNiSi-based copper alloy sheet has a surface and a surface layer which represents a portion of the sheet that is as thick as 20% of the entire sheet thickness measured from the surface of the sheet; the number of NiSi precipitate particles having a grain diameter in a range of 20 nm to 80nm on the surface is in a range of 1.510.sup.6 particles/mm.sup.2 to 5.010.sup.6 particles/mm.sup.2; the number of NiSi precipitate particles having a grain diameter of greater than 100 nm on the surface is in a range of 0.510.sup.5 particles/mm.sup.2 to 4.010.sup.5 particles/mm.sup.2; the number of the NiSi precipitate particles/mm.sup.2 having a grain diameter in a range of 20nm to 80 nm in the surface layer is represented by a; the number of the NiSi precipitate particles/mm.sup.2 having a grain diameter in a range of 20nm to 80 nm in an interior portion of the surface layer is represented by b; the ratio of a/b is in a range of 0.5 to 1.5; and the concentration of Si forming a solid solution in crystal grains in an area that is less than 10 m thickness from the surface is in a range of 0.03 mass % to 0.4 mass %.

2. The CuNiSi-based copper alloy sheet according to claim 1, further comprising: 0.2 mass % to 0.8 mass % of Sn; and 0.3 mass % to 1.5 mass % of Zn.

3. The CuNiSi-based copper alloy sheet according to claim 1, further comprising: 0.001 mass % to 0.2 mass % of Mg.

4. The CuNiSi-based copper alloy sheet according to claim 1, further comprising one or more of: 0.007 mass % to 0.25 mass % of Fe; 0.001 mass % to 0.2 mass % of P; 0.0001 mass % to 0.001 mass % of C; 0.001 mass % to 0.3 mass % of Cr; and 0.001 mass % to 0.3 mass % of Zr.

5. The CuNiSi-based copper alloy sheet according to claim 3, further comprising one or more of: 0.007 mass % to 0.25 mass % of Fe; 0.001 mass % to 0.2 mass % of P; 0.0001 mass % to 0.001 mass % of C; 0.001 mass % to 0.3 mass % of Cr; and 0.001 mass % to 0.3 mass % of Zr.

6. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 1, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

7. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 3, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

8. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 4, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

9. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 5, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

10. The CuNiSi-based copper alloy sheet according to claim 2, further comprising: 0.001 mass % to 0.2 mass % of Mg.

11. The CuNiSi-based copper alloy sheet according to claim 2, further comprising one or more of: 0.007 mass % to 0.25 mass% of Fe; 0.001 mass % to 0.2 mass % of P; 0.0001 mass % to 0.001 mass % of C; 0.001 mass % to 0.3 mass % of Cr; and 0.001 mass % to 0.3 mass % of Zr.

12. The CuNiSi-based copper alloy sheet according to claim 10, further comprising one or more of: 0.007 mass % to 0.25 mass % of Fe; 0.001 mass % to 0.2 mass % of P; 0.0001 mass % to 0.001 mass % of C; 0.001 mass % to 0.3 mass % of Cr; and 0.001 mass % to 0.3 mass % of Zr.

13. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 2, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

14. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 10, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

15. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 11, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

16. A method for manufacturing the CuNiSi-based copper alloy sheet according to claim 12, wherein, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

Description

DESCRIPTION OF EMBODIMENTS

(1) Hereinafter, an embodiment of the invention will be described.

(2) [the Component Composition of a Copper-Based Alloy Sheet]

(3) (1) A CuNiSi-based copper alloy sheet of the invention having excellent mold abrasion resistance and shear workability has a composition including 1.0 mass % to 4.0 mass % of Ni and 0.2 mass % to 0.9 mass % of Si with a remainder made up of Cu and inevitable impurities.

(4) Ni and Si form fine particles of an intermetallic compound mainly containing Ni.sub.2Si when being subjected to an appropriate thermal treatment. As a result, the strength of the alloy significantly increases, and the electric conductivity also increases at the same time.

(5) Ni is added in a range of 1.0 mass % to 4.0 mass %. When the content of Ni is less than 1.0 mass %, it is not possible to obtain a sufficient strength. When the content of Ni exceeds 4.0 mass %, cracking occurs during hot rolling.

(6) Si is added in a range of 0.2 mass % to 0.9 mass %. When the content of Si is less than 0.2 mass %, the strength is decreased. When the content of Si exceeds 4.0 mass %, Si does not contribute to the strength, and the conductivity is decreased due to excessive Si.

(7) (2) The CuNiSi-based copper alloy sheet of the invention having excellent mold abrasion resistance and shear workability further contains 1.0 mass % to 4.0 mass % of Ni, 0.2 mass % to 0.9 mass % of Si, 0.2 mass % to 0.8 mass % of Sn, and 0.3 mass % to 1.5 mass % of Zn.

(8) Sn and Zn have an action that improves the strength and the thermal resistance. Furthermore, Sn has an action that improves the stress relaxation resistance, and Zn has an action that improves the thermal resistance of solder joint. Sn is added in a range of 0.2 mass % to 0.8 mass %, and Zn is added in a range of 0.3 mass % to 1.5 mass %. When the contents of Sn and Zn are below the above-described ranges, the desired effects cannot be obtained, and when the contents are above the above-described ranges, the conductivity decreases.

(9) (3) The CuNiSi-based copper alloy sheet of the invention having excellent mold abrasion resistance and shear workability further contains 1.0 mass % to 4.0 mass % of Ni, 0.2 mass % to 0.9 mass % of Si and 0.001 mass % to 0.2 mass % of Mg or 1.0 mass % to 4.0 mass % of Ni, 0.2 mass % to 0.9 mass % of Si, 0.2 mass % to 0.8 mass % of Sn, 0.3 mass % to 1.5 mass % of Zn, and 0.001 mass % to 0.2 mass % of Mg.

(10) While Mg has an effect that improves the stress relaxation characteristic and the hot workability, the effects are not developed when the content of Mg is less than 0.001 mass %, and when the content of Mg exceeds 0.2 mass %, the casting property (the degradation of the quality of the casting surface), hot workability and the thermal ablation resistance of a plate degrade.

(11) The CuNiSi-based copper alloy sheet of the invention having excellent mold abrasion resistance and shear workability further contains, in addition to the components of (1), (2) or (3), one or more of 0.007 mass % to 0.25 mass % of Fe, 0.001 mass % to 0.2 mass % of P, 0.0001 mass % to 0.001 mass % of C, 0.001 mass % to 0.3 mass % of Cr, and 0.001 mass % to 0.3 mass % of Zr.

(12) Fe has effects that improve the hot rolling property (so as to suppress the occurrence of surface cracking or cracked edges), refine the precipitate compound of Ni and Si, and improve the plate heating adhesion. However, when the content thereof is less than 0.007%, the desired effects cannot be obtained, and on the other hand, when the content thereof exceeds 0.25%, the effect that improves the hot rolling property is saturated, and the conductivity is also adversely influenced. Therefore, the content of Fe is specified in a range of 0.007% to 0.25%.

(13) P has an effect that suppresses the degradation of the spring property caused by bending working. However, when the content thereof is less than 0.001%, the desired effects cannot be obtained, and on the other hand, when the content thereof exceeds 0.2%, the thermal ablation resistance of a solder is significantly degraded. Therefore, the content of P is specified in a range of 0.001% to 0.2%.

(14) C has effects that improve the press punching workability and furthermore refine the precipitate compound of Ni and Si so as to improve the strength of an alloy. However, when the content thereof is less than 0.0001%, the desired effects cannot be obtained, and on the other hand, when the content thereof exceeds 0.001%, the hot workability is adversely influenced, which is not preferable. Therefore, the content of C is specified in a range of 0.0001% to 0.001%.

(15) Cr and Zr have effects that make C easily contained in a Cu alloy through their strong affinity to C, further refine the precipitate compound of Ni and Si so as to improve the strength of an alloy, and further improve the strength through precipitation. However, when the content thereof is less than 0.001%, the effect that improves the strength of an alloy cannot be obtained, and when the content thereof exceeds 0.3%, a large Cr and/or Zr precipitate is generated, the plating property deteriorates, the press punching workability deteriorates, and furthermore the hot workability is impaired, which is not preferable. Therefore, the contents of Cr and Zr are specified in a range of 0.001% to 0.3% respectively.

(16) Furthermore, in the CuNiSi-based copper alloy sheet of the invention having excellent mold abrasion resistance and shear workability, the number of NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm on a surface is in a range of 1.510.sup.6 particles/mm.sup.2 to 5.010.sup.6 particles/mm.sup.2, the number of NiSi precipitate particles having a grain diameter of greater than 100 nm on the surface is in a range of 0.510.sup.5 particles/mm.sup.2 to 4.010.sup.5 particles/mm.sup.2, in a case in which the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in a surface layer that is as thick as 20% of the entire sheet thickness from the surface is represented by a particles/mm.sup.2, and the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in a portion below the surface layer is represented by b particles/mm.sup.2, a/b is in a range of 0.5 to 1.5, and the concentration of Si forming a solid solution in crystal grains in an area that is less than 10 m thickness from the surface is in a range of 0.03 mass % to 0.4 mass %.

(17) [the Number of the NiSi Precipitate Particles and the Concentration of Si]

(18) In the invention, the number of the NiSi precipitate particles per square micrometer in the surface, the surface layer or the portion below the surface layer of the copper alloy sheet were obtained in the following manner.

(19) After being immersed in 10% sulfuric acid for ten minutes as a pretreatment, a 10 mm10 mm0.3 mm specimen was washed using water, hit by air blow so as to scatter water, and then a surface treatment was carried out using a flat trimming (ion milling) apparatus manufactured by Hitachi High-Technologies Corporation at an acceleration voltage of 5 kV, an incident angle of 5 and a radiation time of one hour.

(20) Next, the surface of the specimen was observed using a field emission scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation at a magnification of 20000 times, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in 100 m.sup.2 and the number of the NiSi precipitate particles having a grain diameter of more than 100 nm in 100 m.sup.2 were counted, and were converted to the number of particles per square millimeter. The measurement was carried out ten times at changed measurement positions, and the average value was used as the number of the NiSi precipitate particles.

(21) Next, the surface layer (a point at a depth of 20% of the entire sheet thickness from the surface in the thickness direction) and the portion below the surface layer were observed, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in 100 m.sup.2 were counted, and were converted to the number of particles per square millimeter. The measurement was carried out ten times at changed measurement positions, and the average value was used as the number of the NiSi precipitate particles.

(22) From the above-described results, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in the surface layer that was as thick as 20% of the entire sheet thickness from the surface was represented by a particles/mm.sup.2, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in the portion below the surface layer was represented by b particles/mm.sup.2, and the a/b was obtained.

(23) In the invention, the concentration of Si forming a solid solution in crystal grains in a crystal structure in a thickness range of less than 10 m from the surface was obtained in the following manner.

(24) The concentration of Si forming a solid solution in crystal grains at a point 8 m deep from the surface on a cross section of the specimen perpendicular to the rolling direction was observed using a transmission electron microscope JEM-2010F manufactured by JEOL Ltd. at a magnification of 50000 times. The measurement was carried out ten times at changed measurement positions, and the average value was used as the concentration of Si.

(25) [Method for Manufacturing the Copper-Based Alloy Sheet]

(26) In a method for manufacturing the CuNiSi-based copper alloy sheet of the invention having excellent mold abrasion resistance and shear workability, when the CuNiSi-based copper alloy sheet is manufactured using a process including hot rolling, cold rolling, a solution treatment, an aging treatment, final cold rolling, and stress-relieving annealing in this order, cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, and the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours.

(27) When the cooling is carried out with a cooling start temperature after the end of the final pass of the hot rolling in a range of 350 C. to 450 C., coarse precipitate particles are generated. When the cold rolling before the solution treatment is carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, a state in which the precipitate particles form a solid solution again is obtained through strong rolling. When the solution treatment is carried out at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, precipitate particles other than the coarse precipitate particles are made to form a solid solution as much as possible so that (1) the number of NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm on a surface is set in a range of 1.510.sup.6 particles/mm.sup.2 to 5.010.sup.6 particles/mm.sup.2, (2) the number of NiSi precipitate particles having a grain diameter of greater than 100 nm on the surface is set in a range of 0.510.sup.5 particles/mm.sup.2 to 4.010.sup.5 particles/mm.sup.2, (3) in a case in which the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in a surface layer that is as thick as 20% of the entire sheet thickness from the surface is represented by a particles/mm.sup.2, and the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in a portion below the surface layer is represented by b particles/mm.sup.2, a/b is in a range of 0.5 to 1.5. Then, it is possible to obtain excellent mold abrasion resistance while maintaining tensile strength and conductivity.

(28) When any one of the cooling start temperature after the end of the final pass of the hot rolling, the average rolling reduction per pass and the total rolling reduction of the cold rolling before the solution treatment, and the solution treatment fail to be within the above-described numeric value ranges, the copper alloy structure is incapable of satisfying all of (1), (2) and (3).

(29) Furthermore, when the aging treatment is carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours, the concentrations of Si forming a solid solution in crystal grains in areas that are less than 10 m thickness from both surfaces of the rolled sheet is set in a range of 0.03 mass % to 0.4 mass %. Therefore, it is possible to obtain excellent shear workability.

(30) When the aging treatment conditions are not within the above-described ranges, the concentrations of Si forming a solid solution in crystal grains in areas that are less than 10 m thickness from both surfaces of the rolled sheet is not within the above-described range.

(31) A specific example of the manufacturing method is as described below.

(32) First, a material was prepared so as to be capable of producing the CuNiSi-based copper alloy sheet of the invention, melting and casting were carried out using a low-frequency melting furnace having a reducing atmosphere, thereby obtaining a copper alloy ingot. Next, the copper alloy ingot was heated to a temperature in a range of 900 C. to 980 C., and then hot-rolled so as to produce a hot-rolled sheet having an appropriate thickness. The cooling start temperature after the end of the final pass of the hot rolling was set in a range of 350 C. to 450 C., the hot-rolled sheet was cooled using water, and both surfaces were faced to an appropriate extent.

(33) Next, the cold rolling was carried out with a rolling reduction in a range of 60% to 90% so as to produce a cold-rolled sheet having an appropriate thickness, and continuous annealing was carried out under conditions in which the cold-rolled sheet was held at a temperature in a range of 710 C. to 750 C. for 7 seconds to 15 seconds. The cold-rolled sheet was pickled, surface polishing was carried out, and then the cold rolling was carried out with an average rolling reduction per pass in a range of 15% to 30% and a total rolling reduction of 70% or more, thereby producing a cold-rolled thin sheet having an appropriate thickness.

(34) Next, the solution treatment was carried out on the cold-rolled thin sheet at a temperature in a range of 800 C. to 900 C. for 60 seconds to 120 seconds, then, the aging treatment was carried out at a temperature in a range of 400 C. to 500 C. for 7 hours to 14 hours, a pickling treatment was carried out, furthermore, the final cold rolling was carried out with a workability in a range of 10% to 30%, and the stress-relieving annealing was carried out if necessary.

EXAMPLES

(35) A material was prepared so as to be capable of producing the components described in Table 1, and the material was melted and then cast using a low-frequency melting furnace having a reducing atmosphere, thereby manufacturing a copper alloy ingot having dimensions of a thickness of 80 mm, a width of 200 mm and a length of 800 mm. After the copper alloy ingot was heated to a temperature in a range of 900 C. to 980 C., hot rolling was carried out with the cooling start temperature after the end of the final pass of the hot rolling changed as described in Table 1 so as to produce a hot-rolled sheet having a thickness of 11 mm, the hot-rolled sheet was cooled using water, and then both surfaces were 0.5 mm-faced. Next, cold rolling is carried out with a rolling reduction of 87% so as to produce a cold-rolled thin sheet, continuous annealing in which the cold-rolled thin sheet was held at a temperature in a range of 710 C. to 750 C. for 7 seconds to 15 seconds was carried out. Subsequently, the cold-rolled thin sheet was pickled, surface polishing was carried out, and furthermore, cold rolling was carried out with the average rolling reduction per pass and the total rolling reduction changed as described in Table 1, thereby producing a cold-rolled thin sheet having a thickness of 0.3 mm.

(36) A solution treatment was carried out on the cold-rolled sheet with the temperature and the time changed as described in Table 1, subsequently, an aging treatment was carried out with the temperature and the time changed as described in Table 1, a pickling treatment was carried out, and final cold rolling was carried out, thereby producing thin copper alloy sheets of Examples 1 to 11 and Comparative Examples 1 to 9.

(37) TABLE-US-00001 TABLE 1 Solution Aging Cold rolling treatment treatment Hot rolling Average Total Tem- Tem- Cooling start rolling rolling per- per- Component composition (mass %) temperature reduction reduction ature Time ature Time Cu alloy Ni Si Sn Zn Mg Fe P C Cr Zr ( C.) (%) per pass (%) ( C.) (S) ( C.) (H) Example 1 1.9 0.4 0.5 1.1 450 18 75 850 90 450 8 Example 2 2.0 0.5 0.4 0.9 0.03 0.01 350 26 80 900 60 400 14 Example 3 1.6 0.3 0.5 0.3 0.005 400 21 85 850 120 500 7 Example 4 3.0 0.7 0.3 1.3 0.12 0.0006 0.007 0.007 400 30 80 800 90 500 10 Example 5 1.0 0.2 0.7 0.8 0.001 450 20 70 850 120 400 8 Example 6 1.9 0.4 0.02 350 22 90 900 100 450 7 Example 7 1.9 0.4 0.12 400 25 80 850 110 480 8 Example 8 1.9 0.4 450 25 75 800 100 450 8 Example 9 1.2 0.3 0.6 1.5 0.003 0.18 0.07 400 15 80 850 90 450 7 Example 10 3.8 0.8 0.19 0.07 0.02 350 18 85 900 60 500 8 Example 11 2.8 0.7 0.015 450 20 80 800 90 450 8 Comparative 2.1 0.6 0.5 1.0 0.004 600 13 65 950 150 450 20 Example 1 Comparative 2.8 0.6 0.4 0.7 650 10 60 750 180 400 20 Example 2 Comparative 1.6 0.5 0.4 1.0 0.003 700 12 60 750 30 550 4 Example 3 Comparative 2.3 0.7 1.1 0.1 0.0005 600 8 55 950 30 500 5 Example 4 Comparative 4.4 1.1 1.0 0.5 650 14 65 700 150 500 7 Example 5 Comparative 0.7 0.1 0.1 0.5 600 12 60 750 30 500 4 Example 6 Comparative 2.0 0.6 1.0 1.9 0.05 550 12 60 750 150 550 6 Example 7 Comparative 4.6 1.2 0.1 0.1 650 10 65 800 150 450 5 Example 8 Comparative 4.8 1.5 600 12 55 750 120 400 15 Example 9

(38) Next, for specimens obtained from the respective thin copper alloy sheets, the number of the NiSi precipitate particles per square micrometer in the surface, the surface layer or the portion below the surface layer of the copper alloy sheet and the concentration (mass %) of Si forming a solid solution in crystal grains in a thickness range of less than 10 m from the surface were measured.

(39) The number of the NiSi precipitate particles per square micrometer in the surface, the surface layer or the portion below the surface layer of the copper alloy sheet were obtained in the following manner.

(40) After being immersed in 10% sulfuric acid for ten minutes as a pretreatment, a 10 mm10 mm0.3 mm specimen was washed using water, hit by air blow so as to scatter water, and then a surface treatment was carried out using a flat trimming (ion milling) apparatus manufactured by Hitachi High-Technologies Corporation at an acceleration voltage of 5 kV, an incident angle of 5 and a radiation time of one hour.

(41) Next, the surface of the specimen was observed using a field emission scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation at a magnification of 20000 times, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in 100 m.sup.2 and the number of the NiSi precipitate particles having a grain diameter of more than 100 nm in 100 m.sup.2 were counted, and were converted to the number of particles per square millimeter. The measurement was carried out ten times at changed measurement positions, and the average value was used as the number of the NiSi precipitate particles.

(42) Next, the surface layer (a point at a depth of 20% of the entire sheet thickness from the surface in the thickness direction) and the portion below the surface layer were observed, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in 100 m.sup.2 were counted, and were converted to the number of particles per square millimeter.

(43) The measurement was carried out ten times at changed measurement positions, and the average value was used as the number of the NiSi precipitate particles.

(44) From the above-described results, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in the surface layer that was as thick as 20% of the entire sheet thickness from the surface is represented by a particles/mm.sup.2, the number of the NiSi precipitate particles having a grain diameter in a range of 20 nm to 80 nm in the portion below the surface layer was represented by b particles/mm.sup.2, and the a/b was obtained.

(45) In the crystal structure in a thickness range of less than 10 m from the surface, the concentration of Si forming a solid solution in crystal grains was obtained in the following manner.

(46) The concentration of Si forming a solid solution in crystal grains at a point 8 m deep from the surface on a cross section of the specimen perpendicular to the rolling direction was observed using a transmission electron microscope JEM-2010F manufactured by JEOL Ltd. at a magnification of 50000 times. The measurement was carried out ten times at changed measurement positions, and the average value was used as the concentration of Si.

(47) The results are described in Table 2.

(48) Next, for specimens obtained from the respective thin copper alloy sheets, the tensile strength, the conductivity, the shear workability and the mold abrasion resistance were measured.

(49) The tensile strength was measured using a JIS No. 5 test specimen.

(50) The conductivity was measured based on JIS-H0505.

(51) Regarding the mold abrasion resistance, the shear stress was measured by carrying out a shear working test with a round punch shape having a diameter of 10 mm, a clearance of 5% and a shear rate of 25 mm/min using a 4204-type universal material test manufactured by Instron Japan Co., Ltd. according to the test method of the Japan Copper and Brass Association technical standard JCBA T310, and the shear resistivity (the shear stress of a material/the tensile strength of the material) was computed. It is assumed that the mold abrasion resistance improves as the shear resistivity decreases.

(52) The shear workability was evaluated using the length of a burr during the shearing of a material, and a shear working test was carried out with a round punch shape having a diameter of 10 mm, a clearance of 5% and a shear rate of 25 mm/min using a 4204-type universal material test manufactured by Instron Japan Co., Ltd. according to the test method of the Japan Copper and Brass Association technical standard JCBA T310. Regarding the length of a burr, the lengths of burrs were measured at four positions present at 90 intervals in the circumferential direction of a punched test specimen, and the average value of the measured values was used as the length of a burr.

(53) The results are described in Table 2.

(54) TABLE-US-00002 TABLE 2 20 nm to 80 nm 100 nm or Si Mold abrasion Shear Ni.sub.2Si more Ni.sub.2Si concentration in Tensile Shear resistance workability precipitate (10.sup.6 precipitate (10.sup.5 crystal grains strength Conductivity stress (shear stress/ and burr Cu alloy particles/mm.sup.2) particles/mm.sup.2) a/b (mass %) (N/mm.sup.2) (% IACS) (N/mm.sup.2) tensile strength) length (mm) Example 1 2.24 2.71 0.72 0.22 682 41 512 75 0.018 Example 2 2.70 1.84 1.41 0.30 673 42 518 77 0.021 Example 3 2.32 3.53 1.24 0.17 626 45 476 76 0.013 Example 4 3.98 3.82 0.92 0.35 776 41 598 77 0.022 Example 5 1.86 0.95 0.87 0.08 684 44 513 75 0.019 Example 6 2.10 2.90 1.08 0.26 659 43 514 78 0.020 Example 7 2.35 3.11 1.10 0.22 670 42 510 75 0.021 Example 8 2.40 3.49 1.33 0.16 678 41 502 74 0.024 Example 9 1.92 2.72 0.72 0.11 592 43 450 76 0.021 Example 10 4.22 3.61 0.81 0.32 824 40 626 76 0.017 Example 11 3.64 2.58 1.22 0.29 783 42 603 77 0.021 Comparative 5.72 0.21 1.62 0.48 616 39 505 82 0.033 Example 1 Comparative 0.85 0.35 1.70 0.52 613 34 509 83 0.035 Example 2 Comparative 1.32 0.42 1.74 0.43 458 36 371 81 0.029 Example 3 Comparative 5.94 0.24 1.70 0.45 679 40 557 82 0.031 Example 4 Comparative 0.79 0.33 1.60 0.78 574 34 488 85 0.037 Example 5 Comparative 1.04 0.36 1.68 0.02 528 35 438 83 0.038 Example 6 Comparative 1.13 0.37 1.81 0.44 514 34 432 84 0.034 Example 7 Comparative 6.12 0.28 1.73 0.82 683 38 560 82 0.039 Example 8 Comparative 1.29 0.39 1.87 0.91 627 35 502 80 0.032 Example 9

(55) From the above-described results, it is found that the CuNiSi-based copper alloy sheet of the invention of the example has excellent mold abrasion resistance and shear workability while maintaining tensile strength and conductivity.

(56) Thus far, the manufacturing method of the embodiment of the invention has been described, but the invention is not limited thereto, and a variety of modifications can be added within the scope of the purpose of the invention.

INDUSTRIAL APPLICABILITY

(57) The CuNiSi-based copper alloy sheet of the invention having excellent mold abrasion resistance and shear workability can be used as a conductive member such as a connector for vehicle electric connection or a connection terminal for a print substrate.