US20020127133A1 - Copper alloy material for parts of electronic and electric machinery and tools - Google Patents

Copper alloy material for parts of electronic and electric machinery and tools Download PDF

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US20020127133A1
US20020127133A1 US10/005,880 US588001A US2002127133A1 US 20020127133 A1 US20020127133 A1 US 20020127133A1 US 588001 A US588001 A US 588001A US 2002127133 A1 US2002127133 A1 US 2002127133A1
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copper alloy
electronic
parts
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Takayuki Usami
Takao Hirai
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Assigned to FURUKAWA ELECTRIC CO., LTD., THE reassignment FURUKAWA ELECTRIC CO., LTD., THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HIRAI, TAKAO, USAMI, TAKAYUKI
Publication of US20020127133A1 publication Critical patent/US20020127133A1/en
Priority to US10/354,151 priority Critical patent/US7172662B2/en
Priority to US11/130,134 priority patent/US20050208323A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12715—Next to Group IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12889—Au-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

Definitions

  • the present invention relates to a copper alloy material for parts of electronic and electric machinery and tools, in particular to the copper alloy material for parts of electronic and electric machinery and tools, which is excellent in bending property and stress relaxation property, and which can sufficiently cope with miniaturization of parts of electronic and electric machinery and tools, such as terminals, connectors, switches and relays.
  • Cu—Zn alloys such as Cu—Zn alloys, Cu—Fe-alloys that are excellent in heat resistance, and Cu—Sn alloys
  • Cu—Zn alloys While inexpensive Cu—Zn alloys have been used frequently, for example, in automobiles, the Cu—Zn alloys as well as Cu—Fe alloys and Cu—Sn alloys have been unable to currently cope with the requirements for the automobile, since recent trends urgently require the terminals and connectors to be small size, and they are mostly used under severe conditions (high temperature and corrosive environment) in an engine room and the like.
  • the structure of the terminals have been variously devised for ensuring connection strength at the spring parts in relation to miniaturization of the parts.
  • the materials are more strictly required to be excellent in bending property, since cracks have been often observed at the bent portion in conventional Cu—Ni—Si alloys.
  • the materials are also required to be excellent in stress relaxation property, and the conventional Cu—Ni—Si alloys cannot be used for a long period of time, due to increased stress load on the material and high temperatures in the working environments.
  • plating characteristics have been also addressed, with respect to improvement in compatibility to plating for plating the copper alloy material for parts of electronic and electric machinery and tools, and in resistance to deterioration of plate after plating (which are collectively called as plating characteristics).
  • Cu plating is generally applied on the material as an underlayer followed by Sn plating on the surface thereof, for improving reliability when copper-based materials are used for the above automobile connector such as a box-type connector.
  • unevenness (roughness) of the material surface is larger than the thickness of the plating layer, the plating is repelled from convex portions without being plated to make it impossible to uniformly plate.
  • the interface area between the material and plating layer is increased to readily cause mutual diffusion between Cu and Sn, thereby the plating layer is readily peeled off due to formation of voids and a Cu—Sn compound. Accordingly, the surface of the material should be as smooth as possible.
  • FIG. 1 is an explanatory view on the method for determining the crystal grain diameter and the crystal grain shape, each of which is defined in the present invention.
  • a copper alloy material for parts of electronic and electric machinery and tools comprising 1.0 to 3.0% by mass of Ni, 0.2 to 0.7% by mass of Si, 0.01 to 0.2% by mass of Mg, 0.05 to 1.5% by mass of Sn, 0.2 to 1.5% by mass of Zn, and less than 0.005% by mass (including 0% by mass) of S, with the balance being Cu and inevitable impurities,
  • a crystal grain diameter is more than 0.001 mm and 0.025 mm or less; and the ratio (a/b), between a longer diameter a of a crystal grain on a cross section parallel to a direction of final plastic working, and a longer diameter b of a crystal grain on a cross section perpendicular to the direction of final plastic working, is 1.5 or less.
  • a copper alloy material for parts of electronic and electric machinery and tools comprising 1.0 to 3.0% by mass of Ni, 0.2 to 0.7% by mass of Si, 0.01 to 0.2% by mass of Mg, 0.05 to 1.5% by mass of Sn, 0.2 to 1.5% by mass of Zn, 0.005 to 2.0% by mass in a total amount of at least one selected from the group consisting of Ag, Co and Cr (with the proviso that the Cr content is 0.2% by mass or less), and less than 0.005% by mass (including 0% by mass) of S, with the balance being Cu and inevitable impurities,
  • a crystal grain diameter is more than 0.001 mm and 0.025 mm or less; and the ratio (a/b), between a longer diameter a of a crystal grain on a cross section parallel to a direction of final plastic working, and a longer diameter b of a crystal grain on a cross section perpendicular to the direction of final plastic working, is 1.5 or less.
  • a copper alloy material for parts of electronic and electric machinery and tools comprising 1.0 to 3.0% by mass of Ni, 0.2 to 0.7% by mass of Si, 0.01 to 0.2% by mass of Mg, 0.05 to 1.5% by mass of Sn, 0.2 to 1.5% by mass of Zn, and less than 0.005% by mass (including 0% by mass) of S, with the balance being Cu and inevitable impurities,
  • a surface roughness Ra after final plastic working is more than 0 ⁇ m and less than 0.1 ⁇ m, or a surface roughness Rmax is more than 0 ⁇ m and less than 2.0 ⁇ m.
  • a copper alloy material for parts of electronic and electric machinery and tools comprising 1.0 to 3.0% by mass of Ni, 0.2 to 0.7% by mass of Si, 0.01 to 0.2% by mass of Mg, 0.05 to 1.5% by mass of Sn, 0.2 to 1.5% by mass of Zn, 0.005 to 2.0% by mass in a total amount of at least one selected from the group consisting of Ag, Co and Cr (with the proviso that the Cr content is 0.2% by mass or less), and less than 0.005% by mass (including 0% by mass) of S, with the balance being Cu and inevitable impurities,
  • a surface roughness Ra after final plastic working is more than 0 ⁇ m and less than 0.1 ⁇ m, or a surface roughness Rmax is more than 0 ⁇ m and less than 2.0 ⁇ m.
  • the present invention means to include both the first and second embodiments, unless otherwise specified.
  • examples of the preferable copper alloy materials for parts of electronic and electric machinery and tools in the present invention include the followings:
  • a copper alloy material for parts of electronic and electric machinery and tools comprising 1.0 to 3.0% by mass (having the same meaning as % by wt) of Ni, 0.2 to 0.7% by mass of Si, 0.01 to 0.2% by mass of Mg, 0.05 to 1.5% by mass of Sn, 0.2 to 1.5% by mass of Zn, and less than 0.005% by mass (including 0% by mass) of S, with the balance being Cu and inevitable impurities,
  • a crystal grain diameter is more than 0.001 mm and 0.025 mm or less; the ratio (a/b), between a longer diameter a of a crystal grain on a cross section parallel to a direction of final plastic working, and a longer diameter b of a crystal grain on a cross section perpendicular to the direction of final plastic working, is 1.5 or less; and a surface roughness Ra after the final plastic working is more than 0 ⁇ m and less than 0.1 ⁇ m, or a surface roughness Rmax is more than 0 ⁇ m and less than 2.0 ⁇ m.
  • a copper alloy material for parts of electronic and electric machinery and tools comprising 1.0 to 3.0% by mass of Ni, 0.2 to 0.7% by mass of Si, 0.01 to 0.2% by mass of Mg, 0.05 to 1.5% by mass of Sn, 0.2 to 1.5% by mass of Zn, 0.005 to 2.0% by mass in a total amount of at least one selected from the group consisting of Ag, Co and Cr (with the proviso that the Cr content is 0.2% by mass or less), and less than 0.005% by mass (including 0% by mass) of S, with the balance being Cu and inevitable impurities,
  • a crystal grain diameter is more than 0.001 mm and 0.025 mm or less; the ratio (a/b), between a longer diameter a of a crystal grain on a cross section parallel to a direction of final plastic working, and a longer diameter b of a crystal grain on a cross section perpendicular to the direction of final plastic working, is 1.5 or less; and a surface roughness Ra after the final plastic working is more than 0 ⁇ m and less than 0.1 ⁇ m, or a surface roughness Rmax is more than 0 ⁇ m and less than 2.0 ⁇ m.
  • Ni and Si as alloy forming elements in the present invention precipitate as a Ni—Si compound in the Cu matrix to maintain required mechanical properties without compromising heat and electric conductivity.
  • Ni and Si are defined in the ranges of 1.0 to 3.0% by mass and 0.2 to 0.7% by mass, respectively, because the effect of adding these elements cannot be sufficiently attained when the content of either Ni or Si is less than its lower limit; while when the content of either Ni or Si exceeds its upper limit, giant compounds that do not contribute to the improvement in mechanical strength are recrystallized (precipitated) during casting or hot-working, not only to fail in obtaining a mechanical strength rewarding their contents, but also to cause problems of adversely affecting hot-working property and bending property.
  • the preferable content of Ni is in the range of 1.7 to 3.0% by mass, more preferably 2.0 to 2.8% by mass
  • the preferable content of Si is in the range of 0.4 to 0.7% by mass, more preferably 0.45 to 0.6% by mass. It is best to adjust the blending ratio between Si and Ni to the proportion of them in a Ni 2 Si compound, since the compound between Ni and Si mainly comprises the Ni 2 Si phase. The optimum amount of Si to be added is determined by determining the amount of Ni to be added.
  • Mg, Sn and Zn are important alloy elements in the alloy that constitute the copper alloy material of the present invention. These elements in the alloy are correlated with each other to improve the balance among various characteristics.
  • Mg largely improves stress relaxation property, but it adversely affects bending property.
  • the content is restricted in the range of 0.01 to 0.2 by mass, because stress relaxation improving effect cannot be sufficiently obtained when the content is less than 0.01 by mass, while, when the content is more than 0.2 by mass, bending property decreases.
  • Sn is able to more improve stress relaxation property, mutually correlated with Mg. While Sn has a stress relaxation improving effect as seen in phosphor bronze, its effect is not so large as Mg.
  • the content of Sn is restricted in the range of 0.05 to 1.5% by mass, because sufficient effects for adding Sn cannot be sufficiently manifested when the Sn content is less than 0.05% by mass, while, when the Sn content exceeds 1.5% by mass, electric conductivity decreases.
  • Zn does not contribute to the stress relaxation property, it can improve bending property. Therefore, decrease of bending property may be ameliorated by allowing Mg to be contained.
  • Zn When Zn is added in the range of 0.2 to 1.5% by mass, bending property in the practically non-problematic level may be achieved even by adding Mg in maximum 0.2% by mass.
  • Zn can improve resistance to peeling under heat of a tin plating layer or solder plating layer, as well as anti-migration characteristics.
  • the content of Zn is restricted in the range of 0.2 to 1.5% by mass, because the effect of adding Zn cannot be sufficiently manifested when the Zn content is less than 0.2% by mass, while, when the Zn content exceeds 1.5% by mass, electric conductivity decreases.
  • the content of Mg is preferably in the range of 0.03 to 0.2% by mass, more preferably 0.05 to 0.15% by mass;
  • the content of Sn is preferably in the range of 0.05 to 1.0% by mass, more preferably 0.1 to 0.5% by mass;
  • the content of Zn is preferably in the range of 0.2 to 1.0% by mass, more preferably 0.4 to 0.6% by mass.
  • the content of S as an impurity element is restricted to be less than 0.005% by mass, since hot-working property is worsened by the presence of S.
  • the content of S is particularly preferably less than 0.002% by mass.
  • At least one element selected from the group consisting of Ag, Co and Cr is further allowed to contain in the copper alloy material according to the item (1), (3) or (10).
  • These elements in the alloy described above can contribute to further improvement of the mechanical strength.
  • the total content of these elements in the alloy is in the range of 0.005 to 2.0% by mass, preferably in the range of 0.005 to 0.5% by mass.
  • the total content of the elements in the alloy is defined in the range of 0.005 to 2.0% by mass, because the effect of adding these elements cannot be sufficiently manifested when the content is less than 0.005% by mass.
  • the content of Ag of exceeding 2.0% by mass results in a high manufacturing cost of the alloy, while adding Co and Cr of exceeding 2.0% by mass result in recrystallization (precipitation) of giant compounds during casting or hot-working, not only to fail in obtaining a mechanical strength rewarding their contents, but also to cause problems of adversely affecting hot-working property and bending property.
  • the content of Ag is preferably 0.3% by mass, since it is an expensive element.
  • Ag also has an effect for improving heat resistance and for improving bending property by preventing the crystal grains from becoming giant.
  • Co is also expensive, it has the same as or larger function than Ni. Stress relaxation property is also improved since the Co—Si compound is high in hardening ability by precipitation. Accordingly, it is effective to replace a part of Ni with Co in the members in which heat and electric conductivity is emphasized.
  • the content of Co is preferably less than 2.0% by mass since it is expensive.
  • Cr forms fine precipitates in Cu, to contribute to the increased mechanical strength.
  • the content of Cr should be 0.2% by mass or less, preferably 0.1% by mass, because bending property decreases by adding Cr.
  • the present invention it is possible to add elements, such as Fe, Zr, P, Mn, Ti, V, Pb, Bi and Al, in a total content, for example, of 0.01 to 0.5% by mass for improving various characteristics in an extent not decreasing essential characteristics.
  • elements such as Fe, Zr, P, Mn, Ti, V, Pb, Bi and Al
  • hot-working property may be improved by adding Mn in the range that does not decrease electric conductivity (0.01 to 0.5% by mass).
  • the copper alloy material to be used in the present invention can be manufactured by a usual manner, which is not particularly restrictive, the method comprises, for example, hot-rolling of an ingot, cold-rolling, heat treatment for forming a solid solution, heat treatment for aging, final cold-rolling, and low-temperature annealing.
  • the copper alloy material may be also produced by after cold-rolling, applying a heat treatment for recrystallization and for forming a solid solution, followed by immediate quenching. An aging treatment may be applied, if necessary.
  • bending property and stress relaxation property are particularly improved, without compromising essential characteristics such as mechanical property, heat and electric conductivity, and plating property, by allowing the alloy elements in the above copper alloy material such as Ni, Si, Mg, Sn and Zn to contain in appropriate quantities while suppressing the content of S in a trace amount, and by defining the crystal grain diameter and the shape of the crystal grain.
  • the crystal grain diameter is defined to be from more than 0.001 mm to 0.025 mm. This is because the recrystallized texture tends to be a mixed grain texture to decrease bending property and stress relaxation property when the crystal grain diameter is 0.001 mm or less, while, when the crystal grain diameter exceeds 0.025 mm, bending property decreases.
  • the crystal grain diameter may be determined by usual methods for measuring the grain diameter, which is not in particular restrictive.
  • the shape of the crystal grain is expressed with the ratio (a/b), between the longer diameter a of the crystal grain on the cross section parallel to the direction of final plastic working, and the longer diameter b of the crystal grain on the cross section perpendicular to the direction of final plastic working.
  • the ratio (a/b) is defined to be 1.5 or less, because the stress relaxation decreases when the ratio (a/b) exceeds 1.5.
  • the stress relaxation tends to be decreased when the ratio (a/b) is less than 0.8. Therefore, the ratio (a/b) is preferably 0.8 or more.
  • the longer diameter a and the longer diameter b each are determined by an average value obtained from 20 or more crystal grains.
  • the crystal grain diameter and the shape of the crystal grain can be controlled by adjusting heat-treatment conditions, rolling reduction, direction of rolling, back-tension in rolling, lubrication conditions in rolling, the number of paths in rolling, and the like, in the manufacturing process of the copper alloy.
  • the crystal grain diameter and the shape of crystal grain can be controlled as intended, for example, by changing heat-treatment conditions (such as the temperature and period of time in the heat-treatment for forming a solid solution and heat treatment for aging) or by a low reduction in the final cold-rolling.
  • the direction of final plastic working as used in the present invention refers to the direction of rolling when the rolling is the finally carried out plastic working, or to the direction of drawing when the drawing (linear drawing) is the plastic working finally carried out.
  • the plastic working refers to workings such as rolling and drawing, but working for the purpose of leveling (vertical leveling) using, for example, a tension leveler, is not included in this plastic working.
  • the second embodiment of the present invention is the copper alloy material for parts of electronic and electric machinery and tools that can be used in the preset invention as described in the above, in which the surface roughness of the alloy is defined so that the surface becomes smooth, particularly property of plating of Sn and the like is improved.
  • the inventors of the present invention have been able to realize practically excellent materials for the parts of electronic and electric machinery and tools by precisely defining the contents of the components of the alloy material and the surface roughness of the alloy material.
  • the surface roughness is used as an index representing the surface state of the material.
  • Ra defined in the second embodiment of the present invention means an arithmetic average of the surface roughness, and is described in JIS B 0601.
  • Rmax denotes the maximum height of roughness, and is described as Ry in JIS B 0601.
  • the copper alloy material for parts of electronic and electric machinery and tools in the second embodiment of the present invention is manufactured so that the surface of the copper alloy material having the foregoing composition after the final plastic working has the given surface roughness Ra or Rmax as described above.
  • the Ra or Rmax for example, may be adjusted by rolling, grinding, or the like.
  • the surface roughness of the copper alloy material may be practically adjusted, by (1) rolling with a roll having a controlled surface roughness, (2) grinding after intermediate working and final working, with a buff having a controlled roughness, (3) cutting after intermediate working and final working, by changing cutting conditions, (4) surface dissolution treatment after intermediate working and final working, and a combination thereof.
  • Examples of practical embodiments include cold-rolling as final plastic working with a roll having different roughness (coarse/fine), grinding with a buff having different counts, surface dissolution with a solution having different solubility, and a combination of cold-rolling as a final plastic working with a roll having different roughness and dissolution treatment with a solution having a different dissolution time. Desired surface roughness may be attained by using any one of the methods described above.
  • the copper alloy material for parts of electronic and electric machinery and tools according to the present invention It is preferable to plate the copper alloy material for parts of electronic and electric machinery and tools according to the present invention.
  • the plating method is not particularly restricted, and any usual methods may be used. Although not restrictive in the present invention, it is more preferable to plate the copper alloy material for parts of electronic and electric machinery and tools according to the second embodiment, and it is particularly preferable to plate the copper alloy material for parts of electronic and electric machinery and tools described in the item (10) or (11).
  • Repulsion may occur when Ra or Rmax is too large in plating with Sn of the copper alloy material for parts of electronic and electric machinery and tools according to the present invention. Too large Ra or Rmax also arise large interface areas between the material and the Sn plating layer, where Cu atoms in the material and Sn atoms in the plating layer are readily diffused with each other. Consequently, Cu—Sn compounds and voids tend to occur to readily result in peeling of the plating layer after maintaining at a high temperature.
  • pin-holes may occur to deteriorate corrosion resistance after plating with Au of the copper alloy material for parts of electronic and electric machinery and tools according to the present invention, when Ra or Rmax is too large. Accordingly, plating property can be improved by adjusting Ra to be larger than 0 ⁇ m and smaller than 0.1 ⁇ m, or by adjusting Rmax to be larger than 0 ⁇ m and smaller than 2.0 ⁇ m. Preferably, Ra is smaller than 0.09 ⁇ m or Rmax is smaller than 0.8 ⁇ m.
  • the thickness of the Sn or Sn alloy plating layer is preferably more than 0.1 ⁇ m and 10 ⁇ m or less. A sufficient plating effect cannot be obtained at a thickness of the plating layer of less than 0.1 ⁇ m, while the plating effect is saturated at a thickness of more than 10 ⁇ m with increasing the plating cost.
  • Providing a Cu or Cu alloy plating layer under the Sn plating layer is more preferable for preventing repulsion of the plating layer.
  • the preferable thickness of the Cu or Cu alloy plating layer is 1.0 ⁇ m or less.
  • the Sn alloy usable includes, for example, Sn—Pb alloys and Sn—Sb—Cu alloys
  • the Cu alloy usable includes, for example, Cu—Ag alloys and Cu—Cd alloys.
  • the reflow treatment refers to a heat-melting treatment, by which the plating material is heat-melted followed by solidification of the plate layer after cooling.
  • the surface of the copper alloy material for parts of electronic and electric machinery and tools according to the present invention is plated with Au or an Au alloy for improving reliability of electric connection such as a connector. More preferably, the copper alloy material is plated with Au or Au alloy at a thickness of larger than 0.01 ⁇ m and smaller than 2.0 ⁇ m.
  • a Ni or Ni alloy plating layer may be provided under the Au plating layer for improving the plug-in and plug-out service life. The thickness of the Ni or Ni ally plating layer is preferably 2.0 ⁇ m or less.
  • the Au alloy usable includes, for example, Au—Cu alloys, Au—Cu—Au alloys, and the Ni alloy usable includes, for example, Ni—Cu alloys and Ni—Fe alloys.
  • Examples of the preferable embodiments in the present invention further include the foregoing item (10) or (11).
  • the surface roughness defined in the second embodiment is satisfied, while maintaining the crystal grain diameter and crystal grain shape defined in the first embodiment.
  • Specific embodiments of these include those in which the first embodiment and the second embodiment are combined.
  • the copper alloy material for parts of electronic and electric machinery and tools according to the present invention is excellent in mechanical properties (tensile strength and elongation), electric conductivity, stress relaxation property, and bending property.
  • bending property and stress relaxation property are particularly improved while being excellent in essential characteristics such as mechanical properties, electric conductivity and adhesion property of tin plating.
  • the copper alloy material is also excellent in compatibility to plating (repulsion preventive property of plating), and additional effects such as excellent deterioration preventing property of the plating layer (peeling resistance and corrosion resistance of the plating layer) may also be exhibited when plating.
  • the present invention can favorably cope with the recent requirements for miniaturization and high performance of the electronic and electric machinery and tools.
  • the present invention is preferably applied to materials for terminals, connectors, as well as switches, relays, and other general-purpose conductive materials for electronic and electric machinery and tools.
  • Copper alloys each having the composition as defined in the present invention, shown in Table 1 (Nos. A to F), were melted in a microwave melting furnace, to cast into ingots with a thickness of 30 mm, a width of 100 mm and a length of 150 mm, by a DC method, respectively. Then, these ingots were heated at 900° C. After holding the ingots at this temperature for 1 hour, they were hot-rolled to a sheet with a thickness of 12 mm, followed by rapid cooling. Then, both end faces of the hot-rolled sheet each were cut (chamfered) by 1.5 mm, to remove oxidation films. The resultant sheets were worked to a thickness of 0.25 to 0.50 mm by cold rolling.
  • the cold-rolled sheets were then heat-treated at a temperature of 750 to 850° C. for 30 seconds, after that, immediately followed by cooling at a cooling rate of 15° C./sec or more. Some samples were subjected to rolling with a reduction of 50% or less. Then, aging treatment was carried out at 515° C. for 2 hours in an inert gas atmosphere, and cold rolling as a final plastic working was carried out thereafter, to adjust to the final sheet thickness of 0.25 mm. After the final plastic working, the samples were subjected to low-temperature annealing at 350° C. for 2 hours, to carry out evaluation on the following characteristics.
  • Copper alloy sheets were manufactured in the same manner as in Example A-1, except that copper alloys (Nos. G to O) out of the composition defined in the present invention, as shown in Table 1, were used.
  • Example A-1 and Comparative example A-1 were investigated with respect to (1) crystal grain diameter, (2) crystal grain shape, (3) tensile strength and elongation, (4) electric conductivity, (5) bending property, (6) stress relaxation property, and (7) plate adhesion property.
  • the crystal grain diameter (1) and crystal grain shape (2) were calculated based on the measurement of the crystal grain diameter by a cutting method defined by JIS (JIS H 0501).
  • the cross section A parallel to the direction of the final cold-rolling of the sheet (the direction of the final plastic working), and the cross section B perpendicular to the direction of the final cold-rolling, were used as the cross sections for measuring the crystal grain diameter.
  • the crystal grain diameters were measured in two directions that were the direction parallel to or the direction perpendicular to the final cold-rolling direction on the cross section A, and among the measured values, a larger one was referred to as the longer diameter a, and a smaller one was referred to as a shorter diameter, respectively.
  • the crystal grain diameters were measured in two directions, one of which was the direction parallel to the direction of the normal line of the sheet surface, and the other of which was the direction perpendicular to the direction of the normal line of the sheet surface, and among the measured values, a larger one was referred to as the longer diameter b, and a smaller one was referred to as a shorter diameter, respectively.
  • the crystal grain diameter is shown by rounding the average value of the four values among the two longer diameters and the two shorter diameters each obtained on the cross sections A and B, to the nearest number that is a product of an integer and 0.005 mm.
  • the shape of the crystal grain is shown as a value (a/b) that is obtained by dividing the longer diameter a on the cross section A by the longer diameter b on the cross section B.
  • the adhesion property of the plating layer was evaluated in the following manner. A test piece of each of the sample sheets was subjected to glossy tin plating with a thickness of 1 ⁇ m, and the resultant test piece was heated at 150° C. for 1,000 hours in the atmospheric air, followed by 180-degree contact bending and bending back. After that, the adhesion state of the tin plating layer at the bent portion was observed with the naked eye. The sample in which no peeling off of the plating layer was recognized is judged to be good in the adhesion property ( ⁇ ), while the sample in which the plate was peeled off is judged to be poor in the adhesion property ( ⁇ ). The results are shown in Table 2.
  • the prescribed mechanical strength could not be attained in the samples in the comparative example No. 7 since the contents of Ni and Si were too small.
  • the samples of Nos. 8 and 9 were poor in the stress relaxation property due to too small content of Mg.
  • the sample of No. 10 showed poor bending property due to too large content of Mg.
  • the sample of No. 11 was poor in the stress relaxation property due to too small content of Sn.
  • Electric conductivity was poor in the sample of No. 12 due to too large content of Sn.
  • the sample of No. 13 showed poorly low plate adhesion property due to too small amount of Zn content, while the sample of No. 14 was poor in bending property due to too large content of Cr. Production of the sample of No. 15 was stopped since cracks occurred during hot-rolling due to too large content of S.
  • Copper alloys each having the composition as defined in the present invention, shown in Table 1 (Nos. A to D), were melted in a microwave melting furnace, to cast into ingots with a thickness of 30 mm, a width of 100 mm and a length of 150 mm, by a DC method, respectively. Then, these ingots were heated at 900° C. After holding the ingots at this temperature for 1 hour, they were hot-rolled to a sheet with a thickness of 12 mm, followed by rapid cooling. Then, both end faces of the hot-rolled sheet each were cut (chamfered) by 1.5 mm, to remove oxidation films. The resultant sheets were worked to a thickness of 0.25 to 0.50 mm by cold rolling.
  • the cold-rolled sheets were then heat-treated at a temperature of 750 to 850° C. for 30 seconds, after that, immediately followed by cooling at a cooling rate of 15° C./sec or more. Some samples were subjected to rolling of 50% or less. Then, aging treatment was carried out at 515° C. for 2 hours in an inert gas atmosphere, and cold rolling as a final plastic working was carried out thereafter, to adjust to the final sheet thickness of 0.25 mm. After the final plastic working, the samples were subjected to low-temperature annealing at 350° C. for 2 hours, thereby manufacturing copper alloy sheets, respectively.
  • the crystal grain diameter and the shape of the crystal grain of the copper alloy sheets were variously changed within the defined range (the examples according to the present invention) and outside of the defined range (comparative examples), by adjusting heat-treatment conditions, rolling reduction, direction of rolling, back-tension in rolling, the number of paths in rolling, and lubrication conditions in rolling, in the manufacturing process of the copper alloy.
  • the alloys having the compositions listed in Table 4 were melted in a microwave melting furnace, to cast into ingots with a dimension of 30 mm ⁇ 100 mm ⁇ 150 mm. Then, these ingots were heated at 900° C. After holding the ingots at this temperature for 1 hour, they were hot-rolled from 30 mm to a sheet with a thickness of 12 mm, followed by rapid cooling. Then, both end faces of the hot-rolled sheet each were cut (chamfered) to a thickness of 9 mm, to remove surface oxide films. The resultant sheets were worked to a thickness of 0.27 mm by cold rolling. The cold-rolled sheets were then heat-treated at a temperature of 750 to 850° C.
  • the surface roughnesses Ra and Rmax were measured for each 4 mm interval-length at arbitrary sites of the sample in the direction perpendicular to the direction of rolling, and an average of five times measurements was used as Ra and Rmax.
  • Various characteristics were evaluated with respect to the copper alloy material for parts of electronic and electric machinery and tools obtained as described above.
  • the sample above was plated with Sn with a Sn-plating thickness of 1.0 ⁇ m on the Cu underlayer plating with a thickness of 0.2 ⁇ m.
  • the sample above was plated with Au with a Au-plating thickness of 0.2 ⁇ m on the Ni underlayer plating with a thickness of 1.0 ⁇ m.
  • Plate adhesion property of the Sn plating layer was poor in the sample of No. 157 due to a too small content of Zn, while bending property was poor in the sample of No. 158 due to a too large content of Cr.
  • Production of the sample of No. 159 was stopped since cracks occurred during hot-rolling due to a too large content of S.
  • Electric conductivity was poor in the sample of No. 160 due to a too large content of Zn.
  • Bending property was poor in the sample No. 161 due to a too large content of Ni.
  • Electric conductivity was poor and bending property was poor in the sample of No. 162 due to a too large content of Si.
  • Production of the sample of No. 163 was stopped since cracks occurred during hot-rolling due to too large contents of Ni and Si.
  • the copper alloy material for parts of electronic and electric machinery and tools of the present invention is particularly improved in bending property and stress relaxation property while being excellent in essential characteristics such as mechanical property, electric conductivity, and adhesion property of the tin plating layer. Consequently, the copper alloy material of the present invention is able to sufficiently cope with the requirements of miniaturization of parts of electronic and electric machinery and tools such as terminals, connectors, switches and relays. In addition, some embodiments of the copper alloy material for parts of electronic and electric machinery and tools of the present invention can sufficiently match the required plating characteristics. Accordingly, the present invention can preferably cope with recent requirements in miniaturization, high performance, and high reliability, of any types of electronic and electric machinery and tools.

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US7172662B2 (en) 2007-02-06
EP1325964B1 (fr) 2007-12-05
CN1366556A (zh) 2002-08-28
DE60131763T2 (de) 2008-10-30
JP3520034B2 (ja) 2004-04-19
DE60131763D1 (de) 2008-01-17
EP1325964A1 (fr) 2003-07-09
CN1183263C (zh) 2005-01-05
JP2002038228A (ja) 2002-02-06
EP1325964A4 (fr) 2003-07-30
WO2002008479A1 (fr) 2002-01-31
US20030165708A1 (en) 2003-09-04
KR20020040677A (ko) 2002-05-30
TWI225519B (en) 2004-12-21
KR100519850B1 (ko) 2005-10-07
US20050208323A1 (en) 2005-09-22

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