Electrical contact material, method of producing an electrical contact material, and terminal

Abstract

An electrical contact material (10) having: a conductive substrate (1) formed from copper or a copper alloy; a first intermediate layer (2) provided on the conductive substrate (1); a second intermediate layer (3) provided on the first intermediate layer (2); and an outermost layer (4) formed from tin or a tin alloy and provided on the second intermediate layer (3), wherein the first intermediate layer (2) is constructed as one layer of grains extending from the conductive substrate (1) side to the second intermediate layer (3) side, and wherein, in the first intermediate layer (2), the density of grain boundaries (5b) extending in a direction in which the angle formed by the grain boundary in interest and the interface between the conductive substrate and the first intermediate layer is 45° or greater, is 4 μm/μm.sup.2 or less; a method of producing the same; and a terminal.

Claims

1. An electrical contact material having: a conductive substrate comprising copper or a copper alloy; a first intermediate layer provided on the conductive substrate; a second intermediate layer provided on the first intermediate layer; and an outermost layer comprising tin or a tin alloy and provided on the second intermediate layer, wherein the first intermediate layer is configured as one layer of grains lined-up side by side, said grains constituting the first intermediate layer: and extending from the conductive substrate side to the second intermediate layer side, such that an interface of grain boundaries of the grains constituting the first intermediate layer penetrates an interface between the conductive substrate and the first intermediate layer to an interface between the first intermediate layer and the second intermediate layer, and wherein a grain boundary of the first intermediate layer can be obtained by performing area reduction working, wherein the first intermediate layer is a single layer configured such that grains are horizontally lined up, and grain boundaries penetrate through the first intermediate layer, wherein, in the first intermediate layer, the density of grain boundaries extending in a direction in which the angle formed by the grain boundary in interest and the interface between the conductive substrate and the first intermediate layer is 45° or greater, is 4 μm/μm.sup.2 or less, wherein the first intermediate layer is subjected to area reduction working, and goes thru recrystallization, wherein said recrystallization is obtained by said area reduction working, wherein said area reduction working is plastic working, wherein the first intermediate layer comprises any one of nickel, a nickel alloy, cobalt, or a cobalt alloy, wherein the second intermediate layer is a single and flat copper strike-plating layer that covers the entire surface of the first intermediate layer, and wherein the first intermediate layer has the grain boundaries.

2. A terminal comprising the electrical contact material as claimed in claim 1.

3. A method of producing the electrical contact material as claimed in claim 1, comprising: plating the first intermediate layer on the conductive substrate at a current density of 10 A/dm.sup.2 or higher; plating the second intermediate layer on the first intermediate layer; and plating the outermost layer on the second intermediate layer; followed by subjecting the resultant electrical contact material to a heat treatment at 100° C. to 700° C. for 30 minutes to 7 seconds.

4. A method of producing the electrical contact material as claimed in claim 1, comprising: plating the first intermediate layer on the conductive substrate at a current density of 5 A/dm.sup.2 or higher; plating the second intermediate layer on the first intermediate layer; and plating the outermost layer on the second intermediate layer, followed by performing area reduction working from above the outermost layer, and subjecting the resultant electrical contact material to a heat treatment at 100° C. to 700° C. for 30 minutes to 7 seconds.

5. The method of producing the electrical contact material as claimed in claim 4, wherein the working ratio for the area reduction working is 30% to 70%.

6. A method of producing the electrical contact material as claimed in claim 1, comprising: plating the first intermediate layer on the conductive substrate at a current density of 5 A/dm.sup.2 or higher, followed by performing area reduction working from above the first intermediate layer; plating the second intermediate layer on the first intermediate aver; and plating the outermost layer on the second intermediate layer, followed by subjecting the resultant electrical contact material to a heat treatment at 100° C. to 700° C. for 30 minutes to 7 seconds.

7. The method of producing the electrical contact material as claimed in claim 6, wherein the working ratio for the area reduction working is 30% to 70%.

8. A method of producing the electrical contact material as claimed in claim 1, comprising: plating the first intermediate layer on the conductive substrate at a current density of 5 A/dm.sup.2 or higher; plating the second intermediate layer on the first intermediate layer, followed by performing area reduction working from above the second intermediate layer; and plating the outermost layer on the second intermediate layer, followed by subjecting the resultant electrical contact material to a heat treatment at 100° C. to 700° C. for 30 minutes to 7 seconds.

9. The method of producing the electrical contact material as claimed in claim 8, wherein the working ratio for the area reduction working is 30% to 70%.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a cross-sectional view diagram of the electrical contact material of the present invention, schematically illustrating the state of the grain boundaries in the first intermediate layer.

(2) FIG. 2 is a diagram schematically illustrating a method of sectioning a sample at a pitch of about 10° when the state of the grain boundaries in the first intermediate layer is analyzed.

MODE FOR CARRYING OUT THE INVENTION

(3) The electrical contact material of the present invention has, on a conductive substrate formed from copper or a copper alloy, a first intermediate layer, a second intermediate layer, and an outermost layer formed from tin or a tin alloy. Further, the first intermediate layer is constructed as one layer of grains extending from the conductive substrate side to the second intermediate layer side. In regard to the first intermediate layer, when the density of the grain boundaries extending such that the angle formed by the grain boundary in interest and the interface between the conductive substrate surface and the first intermediate layer is 45° or greater, is adjusted to 4 μm/μm.sup.2 or less, diffusion of Cu of the conductive substrate into the Sn or Sn alloy layer at the outermost layer is suppressed.

(4) In the first intermediate layer, such as a Ni layer, Cu predominantly undergoes grain boundary diffusion rather than transgranular diffusion. This is assumed that because, particularly, the contribution of diffusion at the grain boundaries where the angle formed by the grain boundary in interest and the conductive substrate is 45° or greater, is larger as compared to the contribution of diffusion at the grain boundaries where the same angle is less than 45°.

(5) For that reason, when the grain boundaries where this angle is 45° or greater are reduced, diffusion of Cu from the conductive substrate and exposure of the Cu at the outermost layer, such as a Sn layer, to form copper oxide, are suppressed. Thus, even in a high-temperature use environment, the increase in contact resistance can be suppressed.

(6) Further, in regard to the electrical contact material of the present invention, the terminology “the first intermediate layer is constructed as one layer of grains extending from the conductive substrate side to the second intermediate layer side” means that the interface of the grain boundaries of the grains constituting the first intermediate layer has come out from the interface between the conductive substrate and the first intermediate layer, such as a Ni layer, to the interface between the first intermediate layer, such as a Ni layer, and the second intermediate layer of Cu. The first intermediate layer is a single layer configured such that grains are horizontally lined up, and grain boundaries penetrate through the first intermediate layer.

(7) This will be explained with reference to FIG. 1.

(8) In the diagram, the electrical contact material 10 is configured such that on a conductive substrate 1 formed from copper or a copper alloy, a first intermediate layer 2 of Ni or the like, a second intermediate layer 3 of copper or the like, and an outermost layer 4 formed from tin or a tin alloy are provided in this order. The first intermediate layer 2 is configured as one layer of grains extending from the conductive substrate 1 side to the second intermediate layer 3 side. As in the above, there are two possible cases concerning grain boundaries 5a and 5b of grains 6 that constitute the first intermediate layer 2: a case in which the angle formed by the grain boundary in interest and the interface between the conductive substrate 1 and the first intermediate layer 2 is less than 45° (5a); and a case in which the same angle is 45° or greater (5b.sub.1, 5b.sub.2, and 5b.sub.3). According to the present invention, the value (μm/μm.sup.2) obtained by dividing the length of grain boundaries (5b.sub.1, 5b.sub.2 and 5b.sub.3) with which the angle thus formed is 45° or greater, by the viewing field area, is 4 μm/μm.sup.2 or less. In the following description, this is also referred to as the grain boundary of the first intermediate layer (2). It is a feature of the present invention to reduce the amount of grain boundaries that are in such a state of grain boundaries (state of grain boundaries penetrating through the first intermediate layer) and have a gradient of 45° or greater. Thereby, diffusion of the substrate components to the outermost layer along these grain boundaries can be suppressed. Meanwhile, since the form of the grain boundaries in the diagram is a conceptual diagram, the grain boundaries are representatively illustrated in the form of straight lines; however, grain boundaries cannot be said to be necessarily straight lines extending from the conductive substrate 1 side to the second intermediate layer 3 side.

(9) Preferred embodiments of the electrical contact material of the present invention and the method of producing the same will be explained.

(10) (Electrical Contact Material)

(11) <Conductive Substrate>

(12) The conductive substrate that can be used in the present invention is formed from copper or a copper alloy. For example, as examples of the copper alloy, use can be made of: “C14410 (Cu-0.15Sn, manufactured by Furukawa Electric Co., Ltd., trade name: EFTEC-3)”, “C19400 (Cu—Fe-based alloy material, Cu-2.3Fe-0.03P-0.15Zn)”, “C18045 (Cu-0.3Cr-0.25Sn-0.5Zn, manufactured by Furukawa Electric Co., Ltd., trade name: EFTEC-64 T)”, “C64770 (Cu—Ni—Si-based alloy material, manufactured by Furukawa Electric Co., Ltd., trade name: FAS-680)”, and “C64775 (Cu—Ni—Si-based alloy material, manufactured by Furukawa Electric Co., Ltd., trade name: FAS-820)”, each of which is an alloy published by CDA (Copper Development Association). (Meanwhile, the numerical units described before the respective elements in the copper alloys represent percentage by mass (mass %) in the copper alloys.) Further, use can also be made of: TPC (tough pitch copper), OFC (oxygen-free copper), phosphor bronze, brass (for example, 70 mass % Cu-30 mass % Zn, abbreviated to 7/3 bronze), and the like. Since these conductive substrates respectively have different electrical conductivities and physical strengths, the conductive substrate is appropriately selected and used according to the required characteristics. However, from the viewpoint of enhancing electrical conductive property and heat dissipation property, it is preferable to use a strip of a copper alloy having an electrical conductivity of 5% IACS or higher. Meanwhile, the “substrate component” according to the present invention on the occasion of handling the copper alloy as the conductive substrate is meant to represent copper, which is a base metal. The thickness of the conductive substrate is not particularly limited, but the thickness is usually 0.05 to 2.00 mm, and preferably 0.1 to 1.2 mm.

(13) <First Intermediate Layer>

(14) The metal that constitutes the first intermediate layer in the present invention is not particularly limited, as long as the metal can prevent diffusion of the conductive substrate components when formed into a predetermined thickness, and can impart heat resistance. It is preferable that the first intermediate layer is formed from any one of nickel, a nickel alloy, cobalt, and a cobalt alloy, all of which are inexpensive and is readily applicable by coating.

(15) The first intermediate layer in the present invention is constructed as one layer of grains extending from the conductive substrate side to the second intermediate layer side. The interfaces of the grain boundaries come out from the “interface between the conductive substrate and the first intermediate layer (Ni layer or the like)” to the “interface between the first intermediate layer (Ni layer or the like) and the second intermediate layer of Cu or the like”. That is, the first intermediate layer is a single layer of grains, and grain boundaries penetrate therethrough. Further, the grain boundaries of the first intermediate layer are such that the density of grain boundaries extending in a direction of 45° or larger at an angle formed by the grain boundary in interest and the interface between the conductive substrate and the first intermediate layer, is 4 μm/μm.sup.2 or less. The density of grain boundaries extending in the direction of 45° or larger at an angle formed by the grain boundary in interest and the interface between the conductive substrate and the first intermediate layer, as schematically illustrated in FIG. 1, is as small as 4 μm/μm.sup.2 or less.

(16) In regard to the density of the grain boundaries of this first intermediate layer, it is effective that the density of grain boundaries extending in the direction of 45° or larger at an angle formed by the grain boundary in interest and the interface between the conductive substrate and the first intermediate layer, is 4 μm/μm.sup.2 or less. The density is more preferably 3 μm/μm.sup.2 or less, and further preferably 2 μm/μm.sup.2 or less. The lower limit value is not limited and is usually 0.5 μm/μm.sup.2 or more. In an electrical contact material in which a first intermediate layer having such grain boundaries is provided, diffusion of the conductive substrate components to the outermost layer can be suppressed.

(17) The thickness of the first intermediate layer is preferably 0.05 to 2 μm, and more preferably 0.2 to 1 μm. This first intermediate layer may also be formed in a usual manner, such as a sputtering method, a vapor deposition method, or a wet plating method. When the ease of control of the grain boundaries or thickness and the productivity are considered, it is particularly preferable to utilize a wet plating method, and it is further preferable to utilize an electroplating method.

(18) The product of the present invention can suppress diffusion of the conductive substrate components into the outermost layer, and has satisfactory heat resistance, as compared to conventional products (the case where regarding the grain boundaries of the first intermediate layer, the density of the grain boundaries extending in a direction of 45° or larger with respect to the interface between the conductive substrate and the first intermediate layer, is 4 μm/μm.sup.2 or more).

(19) <Second Intermediate Layer>

(20) The second intermediate layer in the present invention is preferably formed from copper or a copper alloy. The second intermediate layer is more preferably a copper strike-plating layer. The thickness of the second intermediate layer is preferably 0.05 to 2 μm, and more preferably 0.1 to 1 μm. The second intermediate layer can be formed in a usual manner, such as a sputtering method, a vapor deposition method, or a wet plating method. When the ease of control of coating thickness and the productivity are considered, it is particularly preferable to utilize a wet plating method, and it is further preferable to utilize an electroplating method.

(21) <Outermost Layer>

(22) The outermost layer of the electrical contact material of the present invention is formed from tin or a tin alloy. Since this outermost layer has low contact resistance, the outermost layer has satisfactory connection reliability and satisfactory productivity. The thickness of the outermost layer is preferably 0.05 to 5 μm, and more preferably 0.2 to 3 μm. The outermost layer can be formed in a usual manner, such as a sputtering method, a vapor deposition method, or a wet plating method. When the ease of control of coating thickness and the productivity are considered, it is particularly preferable to utilize a wet plating method, and it is further preferable to utilize an electroplating method.

(23) (Method of Producing Electrical Contact Material)

(24) <Control of Grain Boundaries in First Intermediate Layer 1>

(25) The inventors of the present invention have found that the grain boundaries of the first intermediate layer can be achieved by employing a high-current density at the time of plating the first intermediate layer. When plating is performed using a large current with a current density of 10 A/dm.sup.2 or higher at the time of electroplating the first intermediate layer, desired grain boundaries of the first intermediate layer are obtained. The current density is more preferably 15 A/dm.sup.2 or higher, and further preferably 25 A/dm.sup.2 or higher. On the other hand, in regard to the upper limit of the current density, it is necessary to prevent the surface unevenness after plating from becoming conspicuously noticeable, and it is preferable to set the current density to 40 A/dm.sup.2 or less. At the final step of the process, a heat treatment such as described below is applied to.

(26) According to this method, the area reduction working as described below is not needed.

(27) <Control of Grain Boundaries in First Intermediate Layer 2>

(28) The electroplating current density of the first intermediate layer is set to be 5 A/dm.sup.2 or higher. In this case, desired grain boundaries of the first intermediate layer can be obtained by performing area reduction working that will be described below. The current density is more preferably 10 A/dm.sup.2 or more, and further preferably 20 A/dm.sup.2 or more. On the other hand, the upper limit of the current density is preferably set to be 40 A/dm.sup.2 or less, since it is necessary to prevent the surface unevenness after plating from becoming conspicuously noticeable.

(29) The timing for performing the area reduction working can be selected from among a case of from above the outermost layer after plating the outermost layer, a case of from above the first intermediate layer after plating the first intermediate layer, and a case of from above the second intermediate layer after plating the second intermediate layer. In any case, a heat treatment such as described below is applied to at the end of the process.

(30) In the present invention, as one measure for achieving this state of grain boundaries of the first intermediate layer, for example, the state can be achieved by performing a heat treatment after forming the first intermediate layer, the second intermediate layer, and the surface layer (i.e. the outermost layer). The heat treatment needs to be carried out to the extent that diffusion of the conductive substrate does not proceed. In order to do so, the heat treatment is carried out, for example, at a temperature of 100° C. to 700° C., for 30 minutes to 7 seconds. If the temperature of this heat treatment is too high, or the heating time is too long, the thermal history becomes excessive, diffusion of the conductive substrate components proceeds, and there is a possibility that connection reliability may be deteriorated.

(31) According to the present invention, when the area reduction working is performed, recrystallization-driving force can be introduced into the first intermediate layer, and the first intermediate layer can be made to go through recrystallization readily. It is preferable that the area reduction working in this case is performed by plastic working, such as cold rolling or press working (herein, cold rolling and press working will be together simply described as, for example, area reduction working).

(32) In this case, the rolling-working ratio (or cross-sectional area reduction ratio) at the time of plastic working, such as area reduction working, is preferably set to 30% to 70%. As the rolling-working ratio is higher, plastic working is applied to a larger extent. Thus, the defect energy caused by plastic deformation can be accumulated. Accordingly, when this is released, recrystallization is accelerated. Meanwhile, if the working ratio for the area reduction working and the like exceeds 70%, rupture (breaking) or cracking readily occurs at the time of working, and the energy load (electric power needed for rolling or pressing) also increases. Thus, it is preferable that the working ratio is 70% or lower.

(33) The terms “rolling-working ratio” as defined in the present invention means to represent the ratio (%) represented by: “{(sheet thickness before working)−(sheet thickness after working)}×100/(sheet thickness before working)”.

(34) Further, in the case of performing the area reduction working, for example, in the case of rolling, the rolling process may be repeated any of the number of times. However, if the number of times of rolling is increased, the productivity is deteriorated, and thus, it is preferable that the number of times of rolling is lower. Also, in regard to the rolling machine, for example, rolling is performed using a cold-rolling machine. Examples of the rolling machine usually include: a 2-roll machine, a 4-roll machine, a 6-roll machine, a 12-roll machine, and a 20-roll machine, and any of the rolling machines can be used.

(35) Regarding the rolling roll that can be used for the rolling, when it is considered that if the surface unevenness at a noble metal-coated member surface formed by transfer of rolling lines is large, bending workability or the abrasion resistance on the occasion in which the member is used as a sliding contact is deteriorated, the arithmetic mean (Ra) of the work roll surface roughness is preferably less than 0.20 μm, and more preferably less than 0.08 μm. Herein, cold rolling has been explained as a representative example of plastic working; however, in the case of press working (for example, coining), plastic working can be applied similarly to the case of cold rolling. In the case of a press working method, plastic working can be achieved by adjusting the working ratio through adjustment of the pressure to a press pressure of 0.1 N/mm.sup.2 or more, and thereby applying plastic deformation.

(36) As described above, in a case where plating of various layers is performed, the above-described heat treatment is applied to after the area reduction working is completed.

(37) As discussed above, when the production methods of the control of grain boundaries of the first intermediate layer 1 or 2 is utilized, the grain boundaries of the first intermediate layer after plating can be controlled. As a result, since the grain boundaries of the first intermediate layer can be controlled, and the conductive substrate components do not diffuse into the outermost layer, an electrical contact material having excellent heat resistance and high-connection reliability for an extended period of time can be provided.

(38) (Use of Electrical Contact Material)

(39) The electrical contact material obtained in the present invention has particularly excellent heat resistance, and as a result, surface layer contamination after the passage of thermal history in the various production steps occurs to a reduced extent, and the electrical contact material has excellent long-term reliability. Thus, the electrical contact material is preferably suitable for electrical contact components, such as a terminal, a connector, and a lead frame.

Examples

(40) The present invention will be described in more detail based on examples given below, but the invention is not meant to be limited by these.

(41) Each of the conductive substrates indicated in Table 1, having a thickness of 0.25 mm and a width of 50 mm, was subjected to preliminary treatments as described below (electrolytic degreasing and acid washing steps). Then, a Ni first intermediate layer, a Cu second intermediate layer, and a Sn outermost layer as indicated in Table 1 were provided under the conditions described below, and thereby the electrical contact materials of Examples and Comparative Examples indicated in Table 1 were obtained.

(42) In Table 1, FAS680 and 7/3 bronze are as described above. MSP1 is C18665 (Cu—Mg—P-based alloy material, manufactured by Mitsubishi Shindoh Co., Ltd., trade name: MSP1).

(43) Meanwhile, in an example in which a rolling was performed, after the Ni first intermediate layer was formed, or after the Cu second intermediate layer was formed, or after the Sn outermost layer was formed, cold rolling (using a six-stage rolling machine, manufactured by Hitachi, Ltd., arithmetic mean roughness Ra of working roll≈0.03 μm) was carried out at the rolling-working ratio described in Table 1. The number of times of rolling was set to one time, and rolling was performed after the initial sheet thickness was adjusted such that the sheet thickness after rolling would be 0.25 mm.

(44) Further, regarding the coating thickness of the first intermediate layer, the second intermediate layer, or the outermost layer, the sample was prepared by forming the initial coating thickness to be thick in consideration of the portion adjusted according to the working ratio. Thus, the coating thicknesses described in Table 1 represent the coating thicknesses (expressed in μm) after rolling.

(45) Regarding the heat treatment, the treatment was performed using a tubular furnace in a nitrogen atmosphere, at the heat treatment temperature and time described in Table 1.

(46) In regard to the thickness (coating thickness) of each layer, measurement was made at any arbitrary 10 sites at any viewing field, using a fluorescent X-ray film thickness analyzer (SFT-9400, trade name, manufactured by Seiko Instruments, Inc.), and using a collimator diameter of 0.5 mm, and the average value of the measurement values was calculated. This was designated as the coating thickness, in the respective layer.

(47) Further, in order to determine the grain boundaries of the first intermediate layer, a cross-sectional sample was produced to give nine viewing fields by sectioning the sample at a pitch of about 10° from a direction perpendicular to the rolling direction to a horizontal direction by a FIB method (Focused Ion Beam method), and SIM image (Scanning Ion Microscope) observation was carried out. A cross-section was cut such that the depth of each of the cross-sectional samples would be to the total thickness of the first intermediate layer, and the length would be a length of 12 μm or more as viewed from a viewing field on the substrate, and observation was made on 10 μm within the length. A cross-sectional sample at a position within ±1 mm from the center in the width direction of the conductive substrate was produced. This was done so as to avoid those sites at the end portions in the width direction, at which working deformation, such as slits and cuts, had been introduced.

(48) Herein, sectioning at a pitch of about 10° was done as schematically illustrated in FIG. 2. FIG. 2 shows the observations made on the laminated surface of layers on the substrate from above. This means that nine cross-sections were observed at 0° (horizontal), 10°, 20°, 30°, 40°, 50°, 60°, 70°, 80°, and 90° (vertical) from a direction parallel to the rolling direction.

(49) In regard to the grain boundaries of the first intermediate layer (5a, 5b.sub.1, 5b.sub.2, and 5b.sub.3 in FIG. 1), the intersection points with respect to the interface between the first intermediate layer and the substrate (A1, A2, A3, and A4 in FIG. 1); and in regard to the same grain boundaries as mentioned above (5a, 5b.sub.1, 5b.sub.2, and 5b.sub.3 in FIG. 1), the intersection points with respect to the interface between the first intermediate layer and the second intermediate layer (B1, B2, B3, and B4 in FIG. 1), were connected with straight lines, and the angles formed by the interface between the first intermediate layer and the substrate interface, and the aforementioned straight lines (C1, C2, C3, and C4 in FIG. 1) were measured. Among the angles, smaller ones were employed. That is, acute angles (90° or less) were employed, instead of obtuse angles (more than 90°). It was determined whether the angle was: less than 45° (5a (C4) in FIG. 1); or 45° or more (5b.sub.1 (C1), 5b.sub.2 (C2), and 5b.sub.3 (C3) in FIG. 1). Further, the lengths of the above-mentioned straight lines (the lengths of A1B1, A2B2, A3B3, and A4B4 in FIG. 1) were defined as the lengths of the respective grain boundaries. In a case where the grain boundary is a straight line (A1B1, A2B2, or A4B4), the length was the length of the straight line; and in a case where the grain boundary is a curved line (A3B3), it was the distance from the intersection point A3 to the intersection point B3 (the length connected by a straight line).

(50) The sum total of the lengths of all the grain boundaries having an angle of 45° or more was divided by the area of the viewing field observed (total thickness of the first intermediate layer 0.5 μm×viewing field observed 10 μm=5 μm.sup.2), and the result was designated as the grain boundary density. The average value of nine viewing fields is described in the table. The viewing field to be observed was defined such that the total thickness of the first intermediate layer was to be observed.

(51) Regarding the method of measuring the grain boundaries, first, the viewing field for measurement was defined such that the height was the coating thickness (film thickness) of the Ni layer, and the width was 10 μm irrespective of the film thickness. Then, in a case where the interface between a layer and another layer was undulating, the undulating interface was approximated into a straight line within a range of 10 μm, the intersection point between the grain boundary and an actual interface was extended to touch the aforementioned straight line, and the angle formed thereby was measured.

(52) (Conditions for Preliminary Treatment)

(53) [Cathode Electrolytic Degreasing]

(54) Degreasing solution: NaOH 60 g/liter

(55) Degreasing conditions: 2.5 A/dm.sup.2, temperature 60° C., degreasing time 60 seconds

(56) [Acid Washing]

(57) Acid washing solution: 10% sulfuric acid

(58) Acid washing conditions: immersion for 30 seconds, room temperature

(59) (First Intermediate Layer Plating Conditions)

(60) [Ni Plating] Additive-Free Bath

(61) Plating solution: Ni(SO.sub.3NH.sub.2).sub.2.4H.sub.2O 500 g/liter, NiCl.sub.2 30 g/liter, H.sub.3BO.sub.3 30 g/liter

(62) Plating conditions: temperature 50° C.

(63) Thickness: 0.5 μm

(64) (Second Intermediate Layer Plating Conditions)

(65) [Cu Plating]

(66) Plating solution: copper sulfate 180 g/liter, sulfuric acid 80 g/liter

(67) Plating conditions: temperature 40° C.

(68) Thickness: 0.4 μM

(69) (Outermost Layer Sn Plating)

(70) [Sn Plating]

(71) Plating solution: Sn sulfate 80 g/liter, sulfuric acid 80 g/liter

(72) Plating conditions: temperature 13° C.

(73) Thickness: 1.0 μm

(74) In regard to the electrical contact materials of the thus-obtained Examples and Comparative Examples, the following item was tested and evaluated.

(75) (1a) Contact Resistance after Heating

(76) The contact resistance after retention for 100 hours at 180° C. was tested by a four-terminal method. This is an index for heat resistance. The probe had a semispherical tip with a curvature of 5 mm, and the material was silver. The contact load was 2 N, and the flowing current (electrification current) was set to 10 mA. Measurement was made at 10 sites, and the average value thereof was designated as the contact resistance.

(77) When this value was 30 mΩ or larger, the sample was considered to have poor heat resistance and was rated as “D”. A sample having a contact resistance value of less than 30 mΩ was considered to have excellent heat resistance, and was rated as “A”.

(78) TABLE-US-00001 TABLE 1 Production conditions Density of Contact Rolling- Rolling- grain resistance Intermediate working working Rolling- boundaries after high- layer ratio (%) ratio (%) working in temp current before Cu after Cu ratio (%) intermediate leaving density undercoat undercoat after Sn layer (180° C. × No. Substrate Production method (A/dm.sup.2) plating plating plating Heating (/μm) 100H) Ex  1 FAS680 Ni intermediate layer plating .fwdarw. 5 No rolling No rolling 50 700° C.- 1.9 A   Cu undercoat plating .fwdarw. Sn plating  7 sec   .fwdarw. Rolling .fwdarw. Heating Ex  2 FAS680 Ni intermediate layer plating .fwdarw. 10 No rolling No rolling 50 700° C.- 0.7 A   Cu undercoat plating .fwdarw. Sn plating  7 sec   .fwdarw. Rolling .fwdarw. Heating Ex  3 FAS680 Ni intermediate layer plating .fwdarw. 20 No rolling No rolling 50 700° C.- 0.5 A   Cu undercoat plating .fwdarw. Sn plating  7 sec   .fwdarw. Rolling .fwdarw. Heating Ex  4 FAS680 Ni intermediate layer plating .fwdarw. 10 No rolling No rolling 50 100° C.- 1.6 A   Cu undercoat plating .fwdarw. Sn plating 30 min   .fwdarw. Rolling .fwdarw. Heating Ex  5 FAS680 Ni intermediate layer plating .fwdarw. 10 No rolling No rolling 50 300° C.- 1.2 A   Cu undercoat plating .fwdarw. Sn plating  7 sec   .fwdarw. Rolling .fwdarw. Heating Ex  6 FAS680 Ni intermediate layer plating .fwdarw. 10 No rolling No rolling 50 450° C.- 1.0 A   Cu undercoat plating .fwdarw. Sn plating  7 sec   .fwdarw. Rolling .fwdarw. Heating Ex  7 FAS680 Ni intermediate layer plating .fwdarw. 10 50 No rolling No rolling 700° C.- 1.9 A   Rolling .fwdarw. Cu undercoat plating .fwdarw.  7 sec   Sn plating .fwdarw. Heating Ex  8 FAS680 Ni intermediate layer plating .fwdarw. 10 No rolling 50 No rolling 700° C.- 1.9 A   Cu undercoat plating .fwdarw. Rolling .fwdarw.  7 sec   Sn plating .fwdarw. Heating Ex  9 MSP1 Ni intermediate layer plating .fwdarw. 10 No rolling No rolling 50 700° C.- 2.2 A Cu undercoat plating .fwdarw. Sn plating  7 sec .fwdarw. Rolling .fwdarw. Heating Ex 10 7/3 brass Ni intermediate layer plating .fwdarw. 10 No rolling No rolling 50 700° C.- 3.0 A Cu undercoat plating .fwdarw. Sn plating  7 sec .fwdarw. Rolling .fwdarw. Heating Ex 11 FAS680 Ni intermediate layer plating .fwdarw. 8 No rolling No rolling No rolling 700° C.- 4.0 A Cu undercoat plating .fwdarw. Sn plating  7 sec .fwdarw. Heating Ex 12 FAS680 Ni intermediate layer plating .fwdarw. 10 No rolling No rolling No rolling 700° C.- 3.6 A Cu undercoat plating .fwdarw. Sn plating  7 sec .fwdarw. Heating Ex 13 FAS680 Ni intermediate layer plating .fwdarw. 20 No rolling No rolling No rolling 700° C.- 2.8 A Cu undercoat plating .fwdarw. Sn plating  7 sec .fwdarw. Heating Ex 14 FAS680 Ni intermediate layer plating .fwdarw. 30 No rolling No rolling No rolling 700° C.- 2.0 A Cu undercoat plating .fwdarw. Sn plating  7 sec .fwdarw. Heating CEx  1 FAS680 Ni intermediate layer plating .fwdarw. 5 No rolling No rolling No rolling 700° C.- 4.5 D Cu undercoat plating .fwdarw. Sn plating  7 sec .fwdarw. Heating Note: Ex means Example Note: CEx means Comparative Example

(79) As is apparent from Table 1, Examples 1 to 14 according to the present invention all exhibited satisfactory contact resistance after heating. In Examples 1 to 14, it was confirmed from SIM images as mentioned above that, in all cases, the first intermediate layer was configured as one layer of grains extending from the conductive substrate side to the second intermediate layer side.

(80) Contrary to the above, Comparative Example 1 was an example that was not subjected to area reduction working. Because the current density among the plating conditions for the first intermediate layer was too low, in connection with the grain boundaries of the first intermediate layer, the density of grain boundaries extending in a direction in which the angle formed by the grain boundary in interest and the interface between the conductive substrate and the first intermediate layer was 45° or larger, was too high. As a result, Comparative Example 1 exhibited poor contact resistance after heating.

(81) Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.

REFERENCE SIGNS LIST

(82) 1 Conductive substrate 2 First intermediate layer 3 Second intermediate layer 4 Outermost layer 5a Grain boundaries in which an angle formed by the grain boundary in interest and the interface between the conductive substrate 1 and the first intermediate layer 2 is less than 45° 5b Grain boundaries in which an angle formed by the grain boundary in interest and the interface between the conductive substrate 1 and the first intermediate layer 2 is 45° or greater 6 Grains of constituting the first intermediate layer 10 Electrical contact material