COPPER ALLOY SHEET MATERIAL AND METHOD FOR PRODUCING COPPER ALLOY SHEET MATERIAL

Abstract

A copper alloy sheet material which contains 0.5 to 2.5% by mass of Ni, 0.5 to 2.5% by mass of Co, 0.30 to 1. 2% by mass of Si and 0.0 to 0.5% by mass of Cr, the balance being Cu and unavoidable impurities. The material fulfills the relationships 1.0≦I {200}/I.sub.0 {200}≦5.0 and 5.0 μm≦GS≦60.0 μm, and these have the relationship (Equation 1): 5.0≦{(I {200}/I.sub.0 {200})/GS}×100≦21.0, in which the I {200} represents an X-ray diffraction intensity of a {200} crystal plane, the I.sub.0 {200} represents an X-ray diffraction intensity of a {200} crystal plane of standard pure copper powder, and the GS (μm) represents an average crystal grain size. An electrical conductivity is 43.5% to 55.0% IACS and 0.2% yield strength is 720 to 900 MPa.

Claims

1. A copper alloy sheet material comprising 0.5 to 2.5% by mass of Ni, 0.5 to 2.5% by mass of Co, 0.30 to 1. 2% by mass of Si and 0.0 to 0.5% by mass of Cr, the balance being Cu and unavoidable impurities, wherein the copper alloy sheet material fulfills the relationships 1.0≦I {200}/I.sub.0 {200}≦5.0 and 5.0 μm≦GS≦60.0 μm, and these have the relationship (Equation 1): 5.0≦{(I {200}/I.sub.0 {200})/GS}×100≦21.0, in which the I {200} represents an X-ray diffraction intensity of a {200} crystal plane on the plate surface, the I.sub.0 {200} represents an X-ray diffraction intensity of a {200} crystal plane of standard pure copper powder, and the GS (μm) represents an average crystal grain size as determined by a cutting method of JIS H 0501, and wherein the copper alloy sheet material has an electrical conductivity of 43.5% IACS or more and 55.0% IACS or less, and 0.2% yield strength of 720 MPa or more and 900 MPa or less.

2. The copper alloy sheet material according to claim 1, further comprising a total of up to 0.5% by mass of one or more elements selected from the group consisting of Mg, Sn, Ti, Fe, Zn and Ag.

3. A method for producing a copper alloy sheet material, comprising the successive steps of: melting and casting a raw material of a copper alloy comprising 0.5 to 2.5% by mass of Ni, 0.5 to 2.5% by mass of Co, 0.30 to 1.2% by mass of Si, and 0.0 to 0.5% by mass of Cr, the balance being Cu and unavoidable impurities; hot-rolling the material while lowering the temperature from 950° C. to 400° C.; cold-rolling the material at a rolling rate of 30% or more; pre-annealing the material by carrying out a heat treatment for the purpose of deposition, at a heating temperature of 350 to 500° C. for 5.0 to 9.5 hours (calculation formula (Equation 2): t=38.0×exp (−0.004 K) is satisfied between the time of the pre-annealing step (t) and a temperature K (° C.); cold-rolling the material at a rolling rate of 70% or more; solutionizing the material at a heating temperature of 700 to 980° C.; aging-treating the material at 350 to 600° C.; and finish-cold-rolling the material at a rolling rate of 10% or more and 40% or less, wherein the producing conditions are adjusted such that calculation formula (Equation 3): K=4.5×(I {200}/I.sub.0 {200}×exp (0.049a)+76.3) is satisfied among a degree of processing a in the finish cold rolling step, I {200}/I.sub.0 {200} after the finish cold rolling step, and a temperature K (° C.) in the pre-annealing step.

4. The method for producing the copper alloy sheet material according to claim 3, wherein the copper apply sheet material further comprises a total of up to 0.5% by mass of one or more elements selected from the group consisting of Mg, Sn, Ti, Fe, Zn and Ag.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0020] FIG. 1 is a flowchart of producing steps according to an embodiment of the present invention;

[0021] FIG. 2 is a graph showing an equation for material properties according to an embodiment of the present invention;

[0022] FIG. 3 is a graph showing an equation for producing steps according to an embodiment of the present invention;

[0023] FIG. 4 is a schematic view for explaining a press test method; and

[0024] FIG. 5 is a schematic view for explaining an evaluation method of a fracture surface after pressing.

DESCRIPTION OF EMBODIMENTS

[0025] Hereinafter, a copper alloy sheet material according to an embodiment of the present invention will be described. The copper alloy sheet material according to the present invention relates a copper alloy sheet material having a composition comprising 0.5% to 2.5% by mass of Ni, 0.5% to 2.5% by mass of Co, 0.3% to 1.2% by mass of Si, 0.0% to 0.5% by mass of Cr, the balance being Cu and unavoidable impurities, wherein the copper alloy sheet material has a crystal orientation that satisfies the equation: 1.0≦I {200}/I.sub.0 {200}≦5.0 in which the I {200} represents an X-ray diffraction intensity of a {200} crystal plane on the plate surface; the I.sub.0 {200} represents an X-ray diffraction intensity of a {200} crystal plane of pure copper standard powder.

[0026] Further, the copper alloy sheet material has an average crystal grain size GS of 5.0 μm to 60.0 μm, preferably 10 μm to 40 μm, as determined by distinguishing the crystal grain boundary from the twin boundary on the surface of the copper alloy sheet material, and using a cutting method of JIS H 0501 without including the twin boundary, and has the relationship: 5.0≦{(I {200}/I.sub.0 {200})/GS}×100≦21.0 for the crystal orientation and the average crystal grain size. The conductivity of such a copper alloy sheet material is 43.5% IACS or more and 55.0% IACS or less, and in further embodiments 44.5% IACS to 52.5% IACS, and more particularly 46.0 IACS to 50.0% IACS. The 0.2% yield strength is 720 MPa or more and 900 MPa or less, and in further embodiments 760 to 875 MPa, and more preferably 800 to 850 MPa. Hereinafter, the copper alloy sheet material and the method for producing the same will be described in detail.

(Alloy Composition)

[0027] An embodiment of the copper alloy sheet material according to the present invention comprises a Cu—Ni—Co—Si—Cr based copper alloy sheet material containing Cu, Ni, Co, and Si, and further containing impurities unavoidable for casting. Ni, Co and Si form Ni—Co—Si based intermetallic compounds by performing an appropriate heat treatment, and can achieve the high strength without deteriorating the conductivity.

[0028] Ni and Co requires amounts of about 0.5% to about 2.5% by mass of Ni and about 0.5% to about 2.5% by mass of Co for the high strength and the high conductivity targeted by the present invention, and preferably about 1.0% to about 2.0% by mass of Ni and about 1.0% to about 2.0% by mass of Co, and more preferably about 1.2% to about 1. 8% by mass of Ni and about 1.2% by mass to about 1.8% by mass of Co. However, if the amounts of Ni and Co are less than about 0.5%, respectively, any desired strength will not be obtained, and conversely, if the amounts of Ni and Co are more than about 2.5% by mass, the high strength can be achieved but the conductivity will be remarkably lowered, and further hot rolling formability will be decreased, which cases are not preferred. Si requires an amount of about 0.30% to about 1.2% by mass, for satisfying the targeted strength and conductivity, and preferably about 0.5% to about 0.8% by mass. However, if the amount of Si is less than about 0.3% by mass, any desired strength will not be obtained, and if it is more than about 1.2% by mass, the high strength can be achieved but the conductivity will be remarkably lowered and further the hot rolling formability will be decreased, which cases are not preferred.

(Mass Ratio of (Ni+Co)/Si)

[0029] The Ni—Co—Si based deposits formed by Ni, Co and Si are considered to be intermetallic compounds based on (Co+Ni) Si. However, all Ni, Co and Si in the alloy are not always deposited by the aging treatment, and some of them are present in a solid solution state in the Cu matrix. Ni and Si in the solid solution state slightly improve the strength of the copper alloy sheet material, but its effect is smaller as compared with the deposition state, and also may be a factor of decreasing the conductivity. Therefore, it is preferable that the ratio of the contents of Ni, Co and Si is as close as possible to the composition ratio of the deposit (Ni+Co) Si. Accordingly, the mass ratio [Ni+Co]/Si is preferably adjusted to 3.5 to 6.0, and more preferably to 4.2 to 4.7.

(Amount of Cr Added)

[0030] In the present invention, Cr is preferably added in an amount of about 0.0% to about 0.5% by mass, and preferably about 0.09% to about 0.5% by mass, and more preferably about 0.1% to about 0.3% by mass, to the Cu—Ni—Si based copper alloy containing Co as stated above. Cr can be deposited as Cr alone or a compound with Si in the Cu matrix by an appropriate heat treatment, thereby increasing the conductivity without impairing the strength. However, if the amount of Cr is more than about 0.5% by mass, it will cause undesirable coarse inclusions which will not contribute to strengthening, so that the formability and the plating properties will be impaired.

(Other Additive Elements)

[0031] The addition of certain amounts of Mg, Sn, Ti, Fe, Zn and Ag is effective in improving the manufacturability including improvement of plating properties and improvement of hot rolling formability due to refinement of the ingot structure. Therefore, one or more of these elements can be optionally added to the Cu—Ni—Si based copper alloy containing Co as stated above depending on the required properties. In such a case, the total amount of these elements may be at most about 0.5% by mass, and preferably about 0.01% to 0.1% by mass. If the total amount of these elements exceeds about 0.5% by mass, the decrease in the conductivity and the deterioration of the manufacturability will be remarkable, which will not be preferred.

[0032] One of ordinary skill in the art will be able to understand that the individual amounts of the elements added may vary depending on the combination of the elements to be added. In one embodiment, the individual contents include, but not limited to, for example 0.5% or less of Mg, 0.5% or less of Sn, 0.5% or less of Ti, 0.5% or less of Fe, 0.5% or less of Zn, and 0.5% or less of Ag. It should be noted that the copper alloy sheet materials of the present invention are not limited to those having these upper limits, as long as they have a combination of the additive elements or added amounts of the elements such that the finally obtained copper alloy sheet materials maintain the 0.2% yield strength of 720 MPa or more and 900 MPa or less, and exhibits the conductivity of 43.5% IACS or more and 55.0% IACS or less.

[0033] The method for producing the copper alloy sheet material comprises the successive steps of:

[0034] melting and casting a raw material of the copper alloy having the composition as stated above;

[0035] hot-rolling the material while lowering the temperature from 950° C. to 400° C.;

[0036] cold-rolling the material at a rolling rate of 30% or more (hereinafter, this step is referred to as “first rolling” step);

[0037] pre-annealing the material by carrying out a heat treatment for the purpose of deposition, at a heating temperature of 350 to 500° C. for 5.0 to 9.5 hours;

[0038] cold-rolling the material at a rolling rate of 70% or more (hereinafter, this step is referred to as “second rolling” step); [0039] solutionizing the material at a heating temperature of 700 to 980° C. for 10 seconds to 10 minutes;

[0040] aging-treating the material at 350 to 600° C. for 1 to 20 hours; and finally finish-cold-rolling the material at a rolling rate of 10% or more and 40% or less (hereinafter, this step is also referred to as “finish rolling step”),

wherein the producing conditions are adjusted such that calculation formula (Equation 3): K=4.5×(I {200}/I.sub.0 {200}×exp (0.049a)+76.3) is satisfied among a degree of processing a in the finish rolling step, I {200}/I.sub.0 {200} after the finish rolling step and a temperature K (° C.) in the pre-annealing step, and calculation formula (Equation 2): t=38.0×exp (−0.004 K) is satisfied between the time of the pre-annealing step (t) and the temperature K (° C.).

[0041] After the finish rolling step, a heat treatment (low temperature annealing) can be optionally performed at 150° C. to 550° C. This can lead to a reduction of the residual stress inside the copper alloy sheet material with little decrease in the strength, thereby improving the spring limit value and the stress relaxation resistance.

[0042] After the hot rolling, surface cutting may be carried out as needed, and after the heat treatment, pickling, polishing and degreasing may be carried out as needed. These can be easily carried out by one of ordinary skill in the art. Hereinafter, these steps will be described in detail.

(Melting and Casting Step)

[0043] A slab is produced by melting a raw material of the copper alloy and then casting it by continuous casting or semi-continuous casting according to the same manner as the general melting and casting method of the copper alloy sheet material. For example, raw materials such as electrolytic copper, Ni, Si, Co and Cr may be first melted using an atmospheric melting furnace to obtain a molten metal having the desired composition, and the molten metal may be then casted into an ingot. In one embodiment of the production method according to the present invention, one or more selected from the group consisting of Mg, Sn, Ti, Fe, Zn and Ag can be contained in the total amount of up to about 0.5% by mass.

(Hot Rolling Step)

[0044] The hot rolling is carried out in the same manner as the general copper alloy producing method. The hot rolling of the slab is performed in several passes while lowering the temperature from 950° C. to 400° C. It should be noted that the hot rolling is performed in one or more passes at a temperature lower than 600° C. The total rolling rate may be preferably approximately 80% or more. After the hot rolling, it is preferable to perform rapid cooling by water cooling or the like. After the hot processing, surface cutting or pickling may be conducted as necessary.

(First Rolling Step)

[0045] The first rolling step can be carried out in the same manner as the general rolling method of the copper alloy, and the rolling rate of 30% or more is sufficient. However, if the rolling rate is too high, the degree of processing in the second rolling step must be inevitably reduced. Therefore, the rolling rate should be preferably from 50 to 80%.

(Pre-Annealing Step)

[0046] Then, pre-annealing is carried out for the purpose of developing Cube orientation in the subsequent solutionizing step. In the conventional method, the pre-annealing is carried out at 400° C. to 650° C. for about 1 to 20 hours for the purpose of depositing Ni, Co, Si, Cr and the like. However, such producing conditions are insufficient to achieve all the high strength, the high conductivity, the improved bending formability and the improved press property, targeted by the present invention.

[0047] The present inventors have studied the compatibility of those various properties and found that all the high strength, the high conductivity, the improved bending formability and improved press formability can be achieved, only in the case of proper balance between the crystal grain size (GS) and the {200} crystal plane on the plate surface in the final product (after the finish rolling step). More particularly, the present inventors found that the balance of the 0.2% yield strength, the conductivity, the bending formability and the press formability have been excellent when the relationships: 1.0≦I {200}/I.sub.0 {200}≦5.0 and 5.0 μm≦GS≦60.0 μm, and 5.0≧{(I {200}/I.sub.0 {200})/GS}×100≦21.0 (Equation 1) have been satisfied, in which relationships, the I {200} represents an X-ray diffraction intensity of the {200} crystal plane on the plate surface, the I.sub.0 {200} represents an X-ray diffraction intensity of the {200} crystal plane of the pure copper standard powder, and the GS (μm) represents an average crystal grain size as determined by the cutting method of JIS H 0501.

[0048] In order to produce the final product satisfying the Equation 1, producing steps must be designed, which control the crystal grain size and the {200} crystal plane after the finish rolling step. One of ordinary skill in the art will be able to easily achieve the control of the crystal grain size after the finish rolling step by controlling the temperature and time of the solutionizing treatment. It is generally known that for the method of controlling the {200} crystal plane after the finish rolling step, the larger amounts of deposits after the pre-annealing step cause stronger development of the {200} crystal plane in the subsequent solutionizing step, and the higher degree of processing leads to development of a rolling texture having the {220} crystal plane as a principal orientation component and hence a decrease in the {200} crystal plane. Therefore, in order to control the {200} crystal plane in the final product, the conditions of the pre-annealing step and the finish rolling step must be optimized.

[0049] Regarding the producing conditions in the pre-annealing step and the finish rolling step, the inventors have evaluated the {200} crystal plane in the final product under various producing conditions, and found that the Equation 1 can be satisfied when producing the product such that the relationship: K=4.5×(I {200}/I.sub.0 {200}×exp (0.049a)+76.3) (Equation 3) is satisfied among the degree of processing a in the finish rolling step, I {200}/I.sub.0 {200} after the finish rolling step and a temperature K (° C.) in the pre-annealing step (the pre-annealing time t must establish the equation: t=38.0×exp (−0.004 K), with the temperature K (° C.) in the pre-annealing step).

(Second Rolling Step)

[0050] Next, the second rolling is performed. The second rolling is also performed in the same manner as the general rolling method of the copper alloy, and the rolling rate would be preferably 70% or more.

(Solutionizing Step)

[0051] In the solutionizing treatment, heating is carried out at an elevated temperature of about 700 to about 980° C. for 10 seconds to 10 minutes to allow solid solution of a Co—Ni—Si based compound in the Cu matrix while at the same time recrystallizing the Cu matrix. In this step, the recrystallization and formation of the {200} crystal plane are carried out, but for solving the problem of the present invention, it is very important to control the crystal grain size in this step, as described above. The controlling of the crystal grain size is carried out by controlling the temperature and time of the solutionizing treatment, as described above. The crystal grain size varies depending on the cold rolling rate and the chemical composition before the solutionizing treatment. However, one of ordinary skill in the art will be able to readily set the retention time and attainment temperature within a temperature range of 700 to 980° C. based on previously experimentally determined relationship between the heat pattern of the solutionizing treatment and the crystal grain size for the alloy having each composition.

[0052] More particularly, the strength and the conductivity can be effectively increased by carrying out the cooling from about 400° C. to room temperature at a cooling rate of about 10° C. or higher per a second, and preferably about 15° C. or higher per a second, and more preferably about 20° C. or higher per a second or more. However, if the cooling rate is too high, any sufficient effect of increasing the strength may not be obtained. Therefore, the cooling rate may be preferably about 30° C. or lower per a second, and more preferably about 25° C. or lower per a second. The cooling rate can be adjusted by any method known to one of ordinary skill in the art. Generally, a decreased amount of water per unit time may cause a decreased cooling rate. Therefore, for example, the increase in the cooling rate can be achieved by increasing the number of the water cooling nozzle or increasing the amount of water per unit time. The “cooling rate” as used herein refers to a value (° C./s) calculated from the equation: “(solutionizing temperature−400) (° C.)/cooling time (s)”, based on the measured cooling time from the solutionizing temperature (700° C. to 980° C.) to 400° C.

(Aging Treatment Step)

[0053] The aging treatment may be carried out in the same manner as the general copper alloy producing method. For example, the aging treatment may be carried out by heating the Ni—Co—Si compound solutionized in the solutionalizing step in a temperature range of from about 350 to about 600° C. for about 1 to 20 hours to deposit the solutionized compound as a fine particle. The aging treatment can increase the strength and the conductivity.

(Finish Rolling Step)

[0054] A cold rolling may be performed after aging in order to obtain higher strength after aging. In this case, the cold rolling step must be carried out under such conditions that the rolling rate for the finish rolling is 10% or more and 40% or less, and furthermore the relationship (Equation 3): K=4.5×(I {200}/I.sub.0 {200}×exp (0.049a)+76.3) is satisfied among the degree of processing a in the finish rolling step, I {200}/I.sub.0 {200} after the finish rolling step and a temperature K (° C.) in the pre-annealing step, as described above. The final plate thickness may be preferably about 0.05 to 1.0 mm, and more preferably 0.08 to 0.5 mm.

(Low Temperature Annealing Step)

[0055] When the cold rolling is carried out after aging, stress relief annealing (low temperature annealing) may be optionally carried out after the cold rolling. This can reduce the residual stress in the copper alloy sheet material and improve the spring limit value and the stress relaxation resistance with little decrease in strength. The heating temperature is preferably set to be 150 to 550° C. If the heating temperature is too high, softening will occurs in a short time so that variation in properties will tend to occur. On the other hand, if the heating temperature is too low, sufficient effect of improving the above properties cannot be obtained. The heating time may be preferably at least 5 seconds, and good results will be usually obtained within one hour.

[0056] In addition, one of ordinary skill in the art would understand that any step such as grinding for removing oxided scales on the surface, polishing and shot-blast pickling may be carried out in the intervals of the respective steps, as needed.

EXAMPLES

[0057] Hereinafter, although Examples of the copper alloy sheet material and the method for producing the same according to the present invention will be described in detail, these Examples are intended to provide better understanding of the present invention and its advantages, and in no way intended to limit the present invention.

[0058] The copper alloys having various component compositions as shown in Tables 1 and 2 were melted at 1100° C. or higher using a high frequency melting furnace according to the flow as shown in FIG. 1, and cast into ingots each having a thickness of 25 mm. Each ingot was then heated at 400 to 950° C., and then hot-rolled to a thickness of 10 mm, and immediately cooled. The surface cutting was performed for each ingot to a thickness of 9 mm in order to removing scales on the surface, and the faced ingot was then cold-rolled to a plate thickness of 1.8 mm. The cold-rolled ingot was then subjected to the pre-annealing at 350 to 500° C. for about 8.5 hours, followed by the cold rolling and the subsequent solutionizing treatment at 700 to 980° C. for 5 to 3600 seconds, which was then immediately cooled to 100° C. or lower at the cooling rate of about 10° C./s. The ingot was then subjected to the cold rolling to 0.15 mm, and finally subjected to the aging treatment in an inert atmosphere at 350 to 600° C. over 1 to 24 hours depending on the added amount of each element of the copper alloy sheet materials, and a sample was produced by the finish cold rolling. The producing conditions for each copper alloy sheet material are shown in Tables 3 and 4.

[0059] For each sheet material thus obtained, characterizations of the strength and the conductivity were carried out. For the strength, the 0.2% yield strength (YS) in a direction parallel to the rolling direction was measured using a tensile tester according to the standard JIS Z 2241. For the conductivity, each specimen was taken such that the longitudinal direction of the specimen was parallel to the rolling direction, and the conductivity of the specimen was determined by volume resistivity measurement using a double bridge method according to the standard JIS H 0505. For the bending formability, the 180° bending in directions parallel to the rolling direction (GW) and perpendicular to the rolling direction (BW) was evaluated according to the standard JIS Z 2248. The sheet material with R/t=0 was evaluated as good (∘), and the sheet material with R/t>0 was evaluated as poor (x). For the press formability, 100 press tests in total were carried out by punching the sheet material into a circle shape having a radius of 1.0 mm by means of dies and a punch, as shown in FIG. 4, and the sag length of the scrap fracture surface was then quantified by the method as shown in FIG. 5, and the case where an average of 100 sag lengths was less than the plate thickness×0.05 was evaluated as good (∘) and the case where the average was more than or equal to the plate thickness×0.05 was evaluated as poor (x).

[0060] For the integrated intensity ratio, the integrated intensity: I {200} at the {200} diffraction peak was evaluated by X-ray diffraction in the thickness direction of the copper alloy sheet surface, and the integrated intensity: I.sub.0 {200} at the {200} diffraction peak was further evaluated by X-ray diffraction of the fine powder copper, using HINT 2500 available from Rigaku Corporation. Subsequently, the ratio of these: I {200}/I.sub.0 {200} was calculated. For the grain size, an average grain size was determined as GS (μm) by a cutting method of the standard JIS H 0501 in a direction parallel to the rolling direction of the specimen.

[0061] The plating adhesion for each copper alloy sheet material was evaluated by carrying out the following method defined in the standard JIS H 8504. More particularly, the specimen having a width of 10 mm was bended at 90° and then returned to the original angle (bending radius of 0.4 mm, in the direction parallel to the rolling direction (GW)), and the bended portion was then observed using an optical microscope (magnification 10×) to determine the presence or absence of peeling of the plated layer. The case where no peeling of the plated layer was observed was evaluated as good (∘), and the case where the peeling of the plated layer was observed was evaluated as poor (x). The respective characterization results are shown in Table 5 and Table 6.

TABLE-US-00001 TABLE 1 Alloy Composition Other Ni Co Si Cr Elements Example 1 1.30 1.30 0.60 0.20 — Example 2 1.30 1.30 0.60 0.20 — Example 3 1.30 1.30 0.60 0.20 — Example 4 1.30 1.30 0.60 0.20 — Example 5 1.30 1.30 0.60 0.20 — Example 6 1.30 1.30 0.60 0.20 — Example 7 1.30 1.30 0.60 0.20 — Example 8 1.30 1.30 0.60 0.20 — Example 9 1.30 1.30 0.60 0.20 — Example 10 1.30 1.30 0.60 0.20 — Example 11 1.30 1.30 0.60 0.20 — Example 12 1.30 1.30 0.60 0.20 — Example 13 1.30 1.30 0.60 0.20 — Example 14 0.55 1.30 0.60 0.20 — Example 15 2.45 1.30 0.60 0.20 — Example 16 1.30 0.52 0.60 0.20 — Example 17 1.30 2.48 0.60 0.20 — Example 18 1.30 1.30 0.32 0.20 — Example 19 1.30 1.30 1.18 0.20 — Example 20 1.30 1.30 0.60 0.00 — Example 21 1.30 1.30 0.60 0.11 — Example 22 1.30 1.30 0.60 0.48 — Example 23 1.30 1.30 0.60 0.20 0.1 Mg Example 24 1.30 1.30 0.60 0.20 0.48 Mg Example 25 1.30 1,30 0.60 0.20 0.1 Sn Example 26 1.30 1.30 0.60 0.20 0.46 Sn Example 27 1.30 1.30 0.60 0.20 0.1 Zn Example 28 1.30 1.30 0.60 0.20 0.48 Zn Example 29 1.30 1.30 0.60 0.20 0.1 Ag Example 30 1.30 1.30 0.60 0.20 0.47 Ag Example 31 1.30 1.30 0.60 0.20 0.1 Ti Example 32 1.30 1.30 0.60 0.20 0.49 Ti Example 33 1.30 1.30 0.60 0.20 0.1 Fe Example 34 1.30 1.30 0.60 0.20 0.49 Fe

TABLE-US-00002 TABLE 2 Alloy Composition Other Ni Co Si Cr Elements Comparative 1.30 1.30 0.60 0.20 — Example 1 Comparative 1.30 1.30 0.60 0.20 — Example 2 Comparative 1.30 1.30 0.60 0.20 — Example 3 Comparative 1.30 1.30 0.60 0.20 — Example 4 Comparative 1.30 1.30 0.60 0.20 — Example 5 Comparative 1.30 1.30 0.60 0.20 — Example 6 Comparative 1.30 1.30 0.60 0.20 — Example 7 Comparative 1.30 1.30 0.60 0.20 — Example 8 Comparative 1.30 1.30 0.60 0.20 — Example 9 Comparative 1.30 1.30 0.60 0.20 — Example 10 Comparative 1.30 1.30 0.60 0.20 — Example 11 Comparative 1.30 1.30 0.60 0.20 — Example 12 Comparative 1.30 1.30 0.60 0.20 — Example 13 Comparative 1.30 1.30 0.60 0.20 — Example 14 Comparative 1.30 1.30 0.60 0.20 — Example 15 Comparative 1.30 1.30 0.60 0.20 — Example 16 Comparative 1.30 1.30 0.60 0.20 — Example 17 Comparative 1.30 1.30 0.60 0.20 — Example 18 Comparative 1.30 1.30 0.60 0.20 — Example 19 Comparative 1.30 1.30 0.60 0.20 — Example 20 Comparative 1.30 1.30 0.60 0.20 — Example 21 Comparative 1.30 1.30 0.60 0.20 — Example 22 Comparative 1.30 1.30 0.60 0.20 — Example 23 Comparative 0.40 1.30 0.60 0.20 — Example 24 Comparative 2.60 1.30 0.60 0.20 — Example 25 Comparative 1.30 0.47 0.60 0.20 — Example 26 Comparative 1.30 2.62 0.60 0.20 — Example 27 Comparative 1.30 1.30 0.28 0.20 — Example 28 Comparative 1.30 1.30 1.22 0.20 — Example 29 Comparative 1.30 1.30 0.60 0.52 — Example 30 Comparative 1.30 1.30 0.60 0.20 0.54Mg Example 31 Comparative 1.30 1.30 0.60 0.20 0.54Sn Example 32 Comparative 1,30 1.30 0.60 0.20 0.52Zn Example 33 Comparative 1.30 1.30 0.60 0.20 0.51Ag Example 34 Comparative 1.30 1.30 0.60 0.20 0.53Ti Example 35 Comparative 1.30 1.30 0.60 0.20 0.52Fe Example 36

TABLE-US-00003 TABLE 3 Producing Conditions Degree of Degree of Processing Pre- Processing of Aging Degree of of First annealing Second Solutionizing Treatment Processing of Rolling Conditions Rolling Conditions Conditions Finish Rolling (%) (° C.) (h) (%) (° C. 20 s) (° C.) (h) (%) Example 1 40 365.4 8.8 70 980 396.3 8.0 10 Example 2 30 376.9 8.4 70 870 368.2 8.0 20 Example 3 40 387.8 8.1 80 814 505.4 8.0 25 Example 4 30 400.1 7.7 80 783 433.3 8.0 30 Example 5 30 432.8 6.7 90 760 564.5 8.0 40 Example 6 30 350.7 9.3 80 802 362.5 6.0 10 Example 7 40 360.2 9.0 80 726 381.2 6.0 25 Example 8 40 378.5 8.4 80 702 404.8 6.0 40 Example 9 30 357.3 9.1 80 899 368.2 8.0 10 Example 10 40 370.9 8.6 80 765 359.4 8.0 25 Example 11 30 404.0 7.5 80 730 370.6 8.0 40 Example 12 40 419.7 7.1 80 860 423.3 8.0 30 Example 13 30 499.9 5.1 80 825 479.2 8.0 40 Example 14 30 399.1 7.7 80 782 436.7 8.0 30 Example 15 30 398.2 7.7 80 775 437.7 8.0 30 Example 16 30 398.8 7.7 80 783 432.9 8.0 30 Example 17 30 398.8 7.7 80 778 436.5 8.0 30 Example 18 30 399.2 7.7 80 783 430.9 8.0 30 Example 19 30 398.6 7.7 80 778 436.2 8.0 30 Example 20 30 398.6 7.7 80 780 430.6 8.0 30 Example 21 30 402.1 7.6 80 781 433.2 8.0 30 Example 22 30 400.1 7.7 80 781 436.5 8.0 30 Example 23 30 398.8 7.7 80 776 430.6 8.0 30 Example 24 30 398.3 7.7 80 779 430.8 8.0 30 Example 25 30 399.1 7.7 80 780 434.5 8.0 30 Example 26 30 399.8 7.7 80 778 437.8 8.0 30 Example 27 30 398.4 7.7 80 776 430.5 8.0 30 Example 28 30 398.8 7.7 80 773 435.8 8.0 30 Example 29 30 399.7 7.7 80 779 437.2 8.0 30 Example 30 30 399.3 7.7 80 773 431.8 8.0 30 Example 31 30 398.2 7.7 80 782 438.7 8.0 30 Example 32 30 399.4 7.7 80 777 437.2 8.0 30 Example 33 30 398.6 7.7 80 778 438.4 8.0 30 Example 34 30 399.5 7.7 80 776 433.2 8.0 30

TABLE-US-00004 TABLE 3 Producing Conditions Degree of Degree of Processing Pre- Processing of Aging Degree of of First annealing Second Solutionizing Treatment Processing of Rolling Conditions Rolling Conditions Conditions Finish Rolling (%) (° C.) (h) (%) (° C. 20 s) (° C.) (h) (%) Comparative 40 450.0 5.8 70 750.0 356.5 8 10 Example 1 Comparative 30 450.0 5.8 70 729.1 587.2 8 30 Example 2 Comparative 40 500.0 4.5 80 700.0 587.2 8 30 Example 3 Comparative 40 500.0 4.5 80 820.1 587.1 8 30 Example 4 Comparative 40 500.0 4.5 80 808.2 370.6 8 30 Example 5 Comparative 40 500.0 4.5 80 980.2 390.0 8 30 Example 6 Comparative 40 450.0 5.8 80 962.8 437.5 8 10 Example 7 Comparative 40 450.0 5.8 80 868.8 435.4 8 20 Example 8 Comparative 40 450.0 5.8 80 813.0 429.2 8 25 Example 9 Comparative 40 450.0 5.8 80 783.2 419.4 8 30 Example 10 Comparative 40 500.0 4.5 80 760.2 425.2 8 40 Example 11 Comparative 30 450.0 5.8 70 962.8 636.0 8 10 Example 12 Comparative 30 450.0 5.8 70 868.3 673.5 8 20 Example 13 Comparative 30 500.0 4.5 70 812.4 611.1 8 25 Example 14 Comparative 30 500.0 4.6 90 783.8 625.2 8 30 Example 15 Comparative 30 500.0 4.5 90 761.5 677.4 8 40 Example 16 Comparative 30 450.0 5.8 80 962.8 344.8 8 10 Example 17 Comparative 30 500.0 4.5 80 867.2 343.1 8 20 Example 18 Comparative 30 450.0 5.8 80 813.0 350.4 8 25 Example 19 Comparative 30 400.0 7.2 80 783.8 343.1 8 30 Example 20 Comparative 30 400.0 7.2 80 762.2 342.5 8 40 Example 21 Comparative 40 450.0 5.8 80 962.8 662.0 8 10 Example 22 Comparative 40 450.0 5.8 80 766.9 669.7 8 10 Example 23 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 24 Comparative 30 400.1 7.2 80 783.2 337.7 8 30 Example 25 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 26 Comparative 30 400.1 7.2 80 783.2 336.3 8 30 Example 27 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 28 Comparative 30 400.1 7.2 80 783.2 347.1 8 30 Example 29 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 30 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 31 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 32 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 33 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 34 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 35 Comparative 30 400.1 7.2 80 783.2 433.3 8 30 Example 36

TABLE-US-00005 TABLE 5 Properties Bending Formability (R/t) Grain Size (um) I{200}/I.sub.0{200} [00001]$\frac{I.Math.\left\{200\right\}/I_0.Math.\left\{200\right\}}{\mathrm{Grain}.Math..Math.\mathrm{Size}}\times 100$ Conductivity (% IACS) 0.2% Yield Strength (MPa) Good Way Bad Way Press Formability Plating Adhesion and Hot Rolling Formability Example 1 60.0 3.0 5.0 47.0 822 ◯ ◯ ◯ ◯ Example 2 32.0 2.8 8.8 45.0 805 ◯ ◯ ◯ ◯ Example 3 22.0 2.9 13.2 52.0 760 ◯ ◯ ◯ ◯ Example 4 17.0 2.9 17.1 49.0 800 ◯ ◯ ◯ ◯ Example 5 13.4 2.8 20.9 54.0 723 ◯ ◯ ◯ ◯ Example 6 20.0 1.0 5.0 44.5 805 ◯ ◯ ◯ ◯ Example 7 8.6 1.1 12.8 46.0 810 ◯ ◯ ◯ ◯ Example 8 5.3 1.1 20.8 47.5 822 ◯ ◯ ◯ ◯ Example 9 38.0 1.9 5.0 45.0 800 ◯ ◯ ◯ ◯ Example 10 14.2 1.8 12.7 44.2 830 ◯ ◯ ◯ ◯ Example 11 9.1 1.9 20.9 45.2 890 ◯ ◯ ◯ ◯ Example 12 30.2 3.9 12.9 48.5 870 ◯ ◯ ◯ ◯ Example 13 23.8 4.9 20.6 51.0 820 ◯ ◯ ◯ ◯ Example 14 17.1 2.8 16.7 49.3 796 ◯ ◯ ◯ ◯ Example 15 17.3 2.8 16.2 49.4 800 ◯ ◯ ◯ ◯ Example 16 17.3 2.8 16.4 49.1 796 ◯ ◯ ◯ ◯ Example 17 17.0 2.8 16.6 48.5 796 ◯ ◯ ◯ ◯ Example 18 16.6 2.9 17.0 49.0 798 ◯ ◯ ◯ ◯ Example 19 16.7 2.8 16.9 49.2 804 ◯ ◯ ◯ ◯ Example 20 17.0 2.8 16.6 44.0 805 ◯ ◯ ◯ ◯ Example 21 17.4 3.0 17.2 51.5 798 ◯ ◯ ◯ ◯ Example 22 17.4 2.9 16.5 52.1 802 ◯ ◯ ◯ ◯ Example 23 16.9 2.8 16.8 49.3 802 ◯ ◯ ◯ ⊚ Example 24 17.2 2.8 16.4 49.0 800 ◯ ◯ ◯ ⊚ Example 25 16.8 2.8 17.0 48.6 800 ◯ ◯ ◯ ⊚ Example 26 17.4 2.9 16.5 48.8 798 ◯ ◯ ◯ ⊚ Example 27 16.9 2.8 16.7 49.5 800 ◯ ◯ ◯ ⊚ Example 28 17.1 2.8 16.6 48.8 799 ◯ ◯ ◯ ⊚ Example 29 17.3 2.9 16.7 48.6 803 ◯ ◯ ◯ ⊚ Example 30 17.4 2.9 16.5 49.1 798 ◯ ◯ ◯ ⊚ Example 31 16.7 2.8 16.8 49.1 800 ◯ ◯ ◯ ⊚ Example 32 16.8 2.9 17.0 49.2 803 ◯ ◯ ◯ ⊚ Example 33 17.0 2.8 16.6 49.0 798 ◯ ◯ ◯ ⊚ Example 34 16.5 2.9 17.4 48.6 800 ◯ ◯ ◯ ⊚

TABLE-US-00006 TABLE 6 Properties Bending Formability (R/t) Grain Size (um) I{200}/I.sub.0{200} [00002]$\frac{I.Math.\left\{200\right\}/I_0.Math.\left\{200\right\}}{\mathrm{Grain}.Math..Math.\mathrm{Size}}\times 100$ Conductivity (% IACS) 0.2% Yield Strength (MPa) Good Way Bad Way Press Formability Plating Adhesion and Hot Rooling Formability Comparative 12.0 3.3 27.5 43.9 740 ∘ ∘ x ∘ Example 1 Comparative 9.0 3.7 41.1 54.7 820 ∘ ∘ x ∘ Example 2 Comparative 5.0 1.1 22.0 54.7 802 ∘ ∘ x ∘ Example 3 Comparative 23.0 5.0 21.7 48.2 815 ∘ ∘ x ∘ Example 4 Comparative 21.0 1.0 4.8 45.2 805 ∘ ∘ x ∘ Example 5 Comparative 60.0 2.8 4.7 46.5 820 ∘ ∘ x ∘ Example 6 Comparative 54.2 2.8 5.2 49.2 903 ∘ ∘ x ∘ Example 7 Comparative 31.8 2.9 9.1 49.1 901 ∘ ∘ x ∘ Example 8 Comparative 21.8 2.8 12.8 48.8 902 ∘ ∘ x ∘ Example 9 Comparative 17.0 2.8 16.5 48.3 905 ∘ ∘ x ∘ Example 10 Comparative 13.5 2.8 20.7 48.6 910 ∘ ∘ x ∘ Example 11 Comparative 54.2 2.8 5.2 56.1 713 ∘ ∘ x ∘ Example 12 Comparative 31.7 2.9 9.1 57.1 715 ∘ ∘ x ∘ Example 13 Comparative 21.7 2.8 12.9 55.4 719 ∘ ∘ x ∘ Example 14 Comparative 17.1 2.8 16.4 55.8 714 ∘ ∘ x ∘ Example 15 Comparative 13.7 2.8 20.4 57.2 711 ∘ ∘ x ∘ Example 16 Comparative 54.2 2.8 5.2 42.4 723 ∘ ∘ x ∘ Example 17 Comparative 31.5 2.9 9.2 42.1 745 ∘ ∘ x ∘ Example 18 Comparative 21.8 2.8 12.8 43.2 753 ∘ ∘ x ∘ Example 19 Comparative 17.1 2.8 16.4 42.1 820 ∘ ∘ x ∘ Example 20 Comparative 13.8 2.9 21.0 42.0 856 ∘ ∘ x ∘ Example 21 Comparative 54.2 3.0 5.5 56.8 718 ∘ ∘ x ∘ Example 22 Comparative 14.5 3.0 20.7 57 715 ∘ ∘ x ∘ Example 23 Comparative 17.0 2.9 17.1 49.0 710 ∘ ∘ x ∘ Example 24 Comparative 17.0 2.9 17.1 38.5 800 ∘ ∘ x x Example 25 Comparative 17.0 2.9 17.1 49.0 705 ∘ ∘ x ∘ Example 26 Comparative 17.0 2.9 17.1 39.5 800 ∘ ∘ x x Example 27 Comparative 17.0 2.9 17.1 49.0 695 ∘ ∘ x ∘ Example 28 Comparative 17.0 2.9 17.1 36.5 842 ∘ ∘ x x Example 29 Comparative 17.0 2.9 17.1 49.0 800 ∘ ∘ x x Example 30 Comparative 17.0 2.9 17.1 40.0 800 ∘ ∘ x ∘ Example 31 Comparative 17.0 2.9 17.1 40.0 800 ∘ ∘ x ∘ Example 32 Comparative 17.0 2.9 17.1 49.0 800 ∘ ∘ x ∘ Example 33 Comparative 17.0 2.9 17.1 49.0 800 ∘ ∘ x ∘ Example 34 Comparative 17.0 2.9 17.1 49.0 800 ∘ ∘ x ∘ Example 35 Comparative 17.0 2.9 17.1 40.0 800 ∘ ∘ x ∘ Example 36

[0062] All of Examples 1 to 34 could provide the copper alloy materials that achieved all the high strength, the high conductivity and improved bending formability, and had improved press formability. However, Comparative Examples 1 to 6 in which the value of {(I {200}/I.sub.0 {200})/GS}×100 was beyond the range of 5 to 21 did not provide the optimum producing conditions for the pre-annealing and the finish rolling and did not satisfy the predetermined relationship (Equation 3) between the temperature in the pre-annealing step and the finish rolling, so that the balance between the I {200}/I.sub.0 {200} of the final product and the grain size was poor, and the press formability was poor as compared with Examples 1 to 34.

[0063] Comparative Examples 7 to 11 in which the value of {(I {200}/I.sub.0 {200})/GS}×100 was within the range of 5 to 21 but the 0.2% yield strength exceeded 900 MPa provided higher spring back during the press working because of the high strength, and also provided poor press formability as compared with Examples 1 to 34.

[0064] Comparative Examples 12 to 16 in which the value of {(I {200}/I.sub.0 {200})/GS}×100 was within the range of 5 to 21 but the conductivity was higher than 55% IACS and the 0.2% yield strength was below 720 MPa provided higher ductility because of lower strength and also extremely larger sag or burr during the press working, so that the press formability was poor as compared with Examples 1 to 34.

[0065] Comparative Examples 17 to 21 in which the value of {(I {200}/I.sub.0 {200})/GS}×100 was within the range of 5-21 but the conductivity was below 43.5% IACS provided poor press formability as compared with Examples 1 to 34, due to ununiform deposition of the Ni—Si based intermetallic compound particles.

[0066] Comparative Example 22 and 23 in which the value of {(I {200}/I.sub.0 {200})/GS}×100 was within the range of 5 to 21 but the conductivity exceeded 55% IACS and the 0.2% yield strength was below 720 MPa provided poor press formability as compared with Examples 1 to 34, for the same reasons as described above.

[0067] Comparative Examples 24 to 30 illustrates the case where the amounts of the main elements Ni, Co, Si, Cr and the like added are beyond the predetermined range. It can be seen that each strength or conductivity is very poor as compared with Examples 1 to 34. Further, Comparative Examples 24 to 30 also provided poor press formability for the reasons that have already been stated.

[0068] Comparative Examples 31 to 36 illustrates the case where the amounts of Mg, Sn, Zn, Ag, Ti and Fe that can be added in the present invention exceed 0.5% by mass. Comparison of these Comparative Examples with Examples 23 to 34 that added appropriate amounts demonstrates that the plating adhesion and hot rolling formability are not effectively improved. Further, the press formability in each comparative example was also poor because coarse inclusions derived from these added elements would extremely wear the mold during the press working.