WO2023167230A1 - Copper alloy material and method for manufacturing copper alloy material - Google Patents

Copper alloy material and method for manufacturing copper alloy material Download PDF

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WO2023167230A1
WO2023167230A1 PCT/JP2023/007544 JP2023007544W WO2023167230A1 WO 2023167230 A1 WO2023167230 A1 WO 2023167230A1 JP 2023007544 W JP2023007544 W JP 2023007544W WO 2023167230 A1 WO2023167230 A1 WO 2023167230A1
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copper alloy
alloy material
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PCT/JP2023/007544
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French (fr)
Japanese (ja)
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佳紀 山本
達也 外木
健二 児玉
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株式会社プロテリアル
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • the present invention relates to a copper alloy material and a method for producing a copper alloy material, and for example, to a copper alloy material and a method for producing a copper alloy material used as materials for electrical and electronic parts such as lead frames, connectors, and terminals.
  • Cu--Fe--Zn--P-based copper alloy is said to have a good balance of mechanical strength, electrical conductivity, and thermal conductivity.
  • One of the typical Cu—Fe—Zn—P-based copper alloys is, for example, C1940 defined in JIS-H3100:2018.
  • C1940 is a precipitation hardening copper alloy containing, by mass, about 2.2% Fe, about 0.03% P, and about 0.12% Zn.
  • C1940 has an electrical conductivity of about 60% IACS and a tensile strength of about 400 MPa to 550 MPa, and is internationally recognized as a standard copper alloy and used in many applications.
  • a Cu--Ni--Si based copper alloy is often used.
  • a Cu—Ni—Si-based copper alloy is a precipitation-hardening copper alloy that obtains high strength by precipitating particles of a compound containing Ni and Si in a Cu-based parent phase of the copper alloy.
  • One of the representative copper alloys of the Cu—Ni—Si system is, for example, C7025 called Corson alloy.
  • C7025 is a copper alloy containing about 3.0% Ni, about 0.65% Si, and about 0.15% Mg, in terms of percentages by mass, although it is not specified in the above JIS. .
  • C7025 has a tensile strength of about 600 MPa to 700 MPa and an electrical conductivity of about 45.0% IACS, and although it is inferior to C1940 in bending workability, it is also used for the lead frame described above.
  • a solder plating layer or a silver plating layer is provided on the surface of the copper alloy material made of copper alloy for the purpose of facilitating mounting of the silicon chip and mounting on the wiring board. That is commonly done.
  • chemical polishing is generally performed as a pretreatment for chemically dissolving an oxidized layer or a work-affected layer on the surface with an acid solution.
  • chemical polishing with an acidic liquid (chemical polishing liquid) containing sulfuric acid and hydrogen peroxide is common.
  • a copper alloy material made of a Cu--Fe--Zn--P based copper alloy such as C1940 does not have the problem of smut remaining on the surface of the copper alloy material (hereinafter referred to as residual smut), which will be described later.
  • a copper alloy material made of a higher-strength copper alloy for example, a copper alloy material made of a Cu—Ni—Si-based copper alloy such as C7025, Ni and Si are removed when a chemical polishing liquid of the same quality as C1940 is used. Particles of compound containing are not dissolved. Therefore, the particles of the compound containing Ni and Si become residue (smut) and remain on the surface of the copper alloy material in large quantities. Residual smut on the surface of copper alloy materials is not easily removed by general surface cleaning after chemical polishing. Therefore, smut may be mixed in the plated layer provided thereafter, which may greatly affect the appearance and characteristics of the copper alloy material.
  • Patent Document 1 discloses controlling the particle size and shape of a compound containing Ni and Si to improve the surface of the copper alloy material.
  • Disclosed is a copper alloy material containing ⁇ 1.0%, Mg: 0-1.0%, Sn: 0-0.8% and Zn: 0-0.8%, the balance being Cu and impurities.
  • Patent Document 2 proposes a method for improving adhesion with resin by leaving unevenness on the surface of the copper alloy material by adjusting the amount of residual smut on the surface of the copper alloy material.
  • Ni 1.5 to 4.5%
  • Si 0.4 to 1.1%
  • the balance is Cu and impurities, and has a tensile strength of 800 MPa or more and an electrical conductivity of 30% IACS or more.
  • a Cu--Ni--Si based copper alloy strip is disclosed.
  • both the proposals of Patent Documents 1 and 2 allow residual smut on the surface of the copper alloy material, and do not fundamentally solve the problem of residual smut occurring on the surface of the copper alloy material.
  • the present invention there is no problem of residual smut as with copper alloy materials made of Cu-Fe-Zn-P-based copper alloys such as C1940, and higher strength Cu-Ni-Si-based materials such as C7025
  • a copper alloy material having approximately the same tensile strength and electrical conductivity as those of the copper alloy material of (1) and desirably good bending workability, and a method for producing the copper alloy material.
  • copper alloy materials containing a large amount of additive elements such as those described above (for example, Ni, Si, Cr, Mg, Sn, Zn, etc.) generally have poor rolling workability, and cracks occur particularly at the stage of hot rolling. It's easy to do. Therefore, the present invention desirably provides a copper alloy material and a method for producing a copper alloy material that are excellent in rolling workability, particularly resistant to cracking during hot rolling.
  • the inventor has developed a copper alloy material composed of a Cu--Fe--Zn--P-based copper alloy having no problem of residual smut, and a copper alloy material composed of a Cu--Ni--Si-based copper alloy having a problem of residual smut.
  • a copper alloy material composed of a Cu--Ni--Si-based copper alloy having a problem of residual smut.
  • the copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe and 0.01% or more and 0.3% or less of P and 0.01% or more and 0.3% or less of Zn, 0.3% or more and 0.8% or less of Sn, the balance being Cu and impurity elements, in a temperature environment of 20 ° C., A copper alloy material having a tensile strength of 620 MPa or more and an electrical conductivity of 40.0% IACS or more.
  • the copper alloy material according to the present invention is preferably a copper alloy material containing 0.01% or more and 0.20% or less of P in terms of mass % content.
  • the content in mass % is, as essential elements, Fe, P, Zn, and Sn, and Mn of 0.002% or more and 0.025% or less. with the balance being Cu and impurity elements, and having a breaking elongation of more than 20% in a temperature environment of 950°C.
  • the content in mass % is (Mn content + total impurity element content) / (Fe content + P content + Sn content) x 100. 1 or less, preferably a copper alloy material.
  • the content in mass% is 1.6% or more and 2.6% or less of Fe and 0.01% or more and 0.3% as essential elements.
  • a copper alloy casting material containing the following P, 0.01% or more and 0.3% or less of Zn, 0.3% or more and 0.8% or less of Sn, and the balance being Cu and impurity elements A melting and casting process for producing, a hot rolling process for producing a hot rolled material by performing hot rolling using the copper alloy cast material, and a cold rolling process using the hot rolled material to perform the first
  • a first cold-rolling step of producing a cold-rolled material, and a first heat-treated material is produced by heating and holding the first cold-rolled material at a temperature of 500 ° C.
  • 1 heat treatment step a second cold rolling step of cold rolling at a rolling reduction rate of 20% or more and 90% or less using the first heat treated material to produce a second cold rolled material
  • a second heat treatment step of producing a second heat treated material by heating and holding the cold rolled material at a temperature of 380 ° C. or higher and 480 ° C. or lower for 1 hour or more and 12 hours or less, and 60% or more using the second heat treated material.
  • a third heat treatment step of producing a copper alloy material by heating and holding for 4 hours or less wherein the melting and casting step, the hot rolling step, the first cold rolling step, the first heat treatment step, the By performing the second cold rolling step, the second heat treatment step, the third cold rolling step, and the third heat treatment step in this order, a tensile strength of 620 MPa or more is obtained in a temperature environment of 20 ° C. and having an electrical conductivity of 40.0% IACS or higher.
  • a method for producing a copper alloy material according to the present invention is a method for producing a copper alloy material containing 0.01% or more and 0.20% or less of P in terms of mass% content. Preferably.
  • the content in mass % is, as the essential elements, Fe, P, Zn, and Sn, and 0.002% or more and 0.025% or less
  • the content in mass% is (Mn content + total impurity element content) / (Fe content + P content + Sn content) x 100. , 1.1 or less.
  • the present invention there is no problem of residual smut as with a copper alloy material made of a Cu-Fe-Zn-P-based copper alloy such as C1940, and a higher strength Cu-Ni-Si-based material such as C7025 It is possible to provide a copper alloy material and a method for producing a copper alloy material that have substantially the same tensile strength and electrical conductivity as a copper alloy material made of a copper alloy of.
  • a copper alloy material with good bending workability and a method for producing a copper alloy material A method for manufacturing an alloy material and a copper alloy material can be provided.
  • FIG. 1 is a diagram showing a flow of main steps in a method of manufacturing a copper alloy material according to the present invention
  • the structure of the copper alloy material according to the present invention will be described below, and then the method for manufacturing the copper alloy material will be described along the flow of the main steps shown in FIG. It should be noted that the copper alloy material and the method for producing the copper alloy material according to the present invention are indicated by the scope of claims, and can be understood to include all modifications within the meaning and scope of equivalents of the scope of the claims. Considerable. The contents (numerical values) of elements and the chemical components (numerical values) of materials are expressed in % by mass unless otherwise specified.
  • the copper alloy material according to the present invention contains, as essential elements, Fe (iron) of 1.6% or more and 2.6% or less, P (phosphorus) of 0.01% or more and 0.3% or less, and 0.5% or more. Contains 01% or more and 0.3% or less of Zn (zinc) and 0.3% or more and 0.8% or less of Sn (tin) (preferably more than 0.3% and 0.8% or less)
  • the balance consists of Cu (copper) and impurity elements, and has a tensile strength of 620 MPa or more (preferably 625 MPa or more, more preferably 630 MPa or more) in a temperature environment of 20 ° C. and 40.0% IACS or more. (preferably 45.0% IACS or higher).
  • the copper alloy constituting the copper alloy material according to the present invention is a Cu--Fe--P--Zn--Sn based copper alloy from the viewpoint of alloy composition.
  • the copper alloy material according to the present invention preferably contains 0.01% or more and 0.20% or less of P.
  • the copper alloy material according to the present invention preferably contains Fe (1.6% or more and 2.6% or less) and P (0.01% or more and 0.3% or less, preferably 0 .01% or more and 0.20% or less), the Zn (0.01% or more and 0.3% or less), and the Sn (0.3% or more and 0.8% or less, preferably more than 0.3% 0.8% or less), and furthermore, 0.002% or more and 0.025% or less of Mn, the balance being Cu and impurity elements, and breaking more than 20% in a temperature environment of 950 ° C. have elongation.
  • the copper alloy material according to the present invention preferably has a value obtained by (Mn content + total content of impurity elements)/(Fe content + P content + Sn content) x 100 (hereinafter referred to as "MI value"). ) is less than or equal to 1.1.
  • the copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe as an essential element.
  • Fe dissolves in a matrix mainly composed of Cu of the copper alloy.
  • a part of Fe is dispersed and precipitated in the matrix phase as a compound containing Fe or Fe and P.
  • Such action of Fe contributes to the improvement of the mechanical strength and heat resistance of the copper alloy material. Therefore, a copper alloy material containing an appropriate amount of Fe can have higher mechanical strength and heat resistance while reasonably maintaining electrical conductivity.
  • the copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe, preferably 2.1% or more and 2.4% or less in order to obtain more well-balanced characteristics. do.
  • the copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe (preferably 2.1% or more and 2.4% or less), and the Sn content is considered as described later. A good balance between tensile strength and electrical conductivity is obtained. In this case, for example, the copper alloy material has a tensile strength of 630 MPa or more and an electrical conductivity of 45.0% IACS or more.
  • the copper alloy material according to the present invention contains 0.01% or more and 0.3% or less of P as an essential element.
  • P acts as a deoxidizing agent that removes excess oxygen present in the molten metal (molten metal) in the melting and casting process, which will be described later.
  • a part of P forms a compound containing Fe and P, and is dispersed and precipitated in the matrix phase mainly composed of Cu of the copper alloy.
  • Such action of P contributes to the improvement of the mechanical strength and heat resistance of the copper alloy material. Therefore, a copper alloy material containing an appropriate amount of P can have higher mechanical strength and heat resistance while maintaining the electrical conductivity accordingly.
  • the copper alloy material according to the present invention has a P content of 0.01% or more and 0.3% or less, more preferably 0.01% or more and 0.20% or less for improving bending workability. .
  • the copper alloy material according to the present invention contains 0.01% or more and 0.3% or less of Zn as an essential element.
  • Zn improves the wettability of the surface of the copper alloy material to solder and improves the weather resistance of the solder-plated layer provided on the surface of the copper alloy material.
  • Such an effect of Zn is particularly required when a solder plating layer is provided on the surface of a copper alloy material such as the lead frame described above. Therefore, a copper alloy material containing an appropriate amount of Zn has high practical applicability.
  • the copper alloy material contains too little Zn (less than 0.01%), the above effects of Zn cannot be sufficiently exhibited. Moreover, when the Zn content in the copper alloy material is excessively large (exceeding 0.3%), the effects of Zn described above are saturated, and this may cause a decrease in electrical conductivity of the copper alloy material. From this point of view, the copper alloy material according to the present invention contains 0.01% or more and 0.3% or less of Zn, preferably 0.05% or more and 0.2% or less in order to obtain more well-balanced properties. do.
  • the copper alloy material according to the present invention contains 0.3% or more and 0.8% or less (preferably, more than 0.3% and 0.8% or less) of Sn as an essential element.
  • Sn forms a solid solution in the parent phase of the copper alloy, which is mainly composed of Cu, and contributes to further improvement of the mechanical strength and heat resistance of the copper alloy material. Therefore, a copper alloy material containing an appropriate amount of Sn can have higher mechanical strength and heat resistance while maintaining a corresponding amount of electrical conductivity, compared to a copper alloy material that does not contain an appropriate amount of Sn.
  • the copper alloy material according to the present invention has a Sn content of 0.3% or more and 0.8% or less, preferably more than 0.3% and 0 in order to stably obtain a tensile strength of 625 MPa or more. .8% or less. For this point, refer also to the section on the effect of Sn, which will be described later.
  • the copper alloy material according to the present invention has a preferable balance between tensile strength and electrical conductivity when the Sn content is 0.5% or more and 0.7% or less and the Fe content is considered as described above.
  • the copper alloy material has a tensile strength of 630 MPa or more and an electrical conductivity of 45.0% IACS or more.
  • the copper alloy material according to the present invention contains, as essential elements, Fe, P, Zn, and Sn within the above ranges, and preferably 0.002% or more and 0.025% or less of Mn.
  • the copper alloy material according to the present invention is, as described above, a copper alloy material made of a Cu--Fe--P--Zn--Sn based copper alloy. While Fe and P contained in this copper alloy material are essential elements, they are also elements that cause work cracks and deterioration of hot workability as described above.
  • this copper alloy material may contain S (sulfur), which is an impurity element, derived from a generally used manufacturing raw material (copper material).
  • the copper alloy material Due to the solid solution of S, the copper alloy material has poor rolling workability, and cracks are likely to occur particularly at the stage of hot rolling. . Therefore, the copper alloy material preferably further contains Mn as an essential element to actively generate MnS, thereby reducing the amount of S that forms a solid solution.
  • the S content in the raw material for general production of this copper alloy material can be considered to be about 0.001% to 0.005%.
  • the composition ratio (Mn:S) of MnS is 1:1 in atomic ratio and 63:37 in mass ratio. Therefore, assuming that the entire amount of S reacts with Mn, about 1.7 times as much Mn as S is required in mass ratio.
  • a copper alloy material containing 0.001% or more and 0.005% or less of S in mass % needs to contain 0.0017% or more and 0.0085% or less of Mn in terms of calculation.
  • the copper alloy material when the S content is expected to be 0.001% or more and 0.005% or less, it is preferable that Mn is 0.002% or more and 0.002% or more in correspondence with the S amount. Set within a range of 0.025% or less. Moreover, if S is 0.002% or less, Mn is preferably set in the range of 0.010% or less corresponding to the amount of S. As a result, the copper alloy material has good rolling workability and is particularly resistant to cracking during hot rolling.
  • the copper alloy material according to the present invention is composed of Cu and impurity elements except for Fe, P, Zn, and Sn, which are the above-described essential elements.
  • the copper alloy material according to the present invention consists of Cu and impurity elements except for Fe, P, Zn, Sn, and Mn, which are the above-described essential elements.
  • Cu is contained in a range of approximately 96% or more and 98% or less according to the content of the essential elements described above.
  • the remainder excluding Cu and the above-described essential elements is impurity elements.
  • Cu copper
  • copper is the main element that constitutes the parent phase of the copper alloy, and is contained in the largest amount.
  • Copper materials made of copper and copper alloy materials made of copper alloys have excellent electrical conductivity and are widely used as materials for electrical and electronic parts.
  • a copper material made of oxygen-free copper such as C1020 or C1100 standardized by JIS has a conductivity of about 100% IACS and a tensile strength of about 195 MPa (temper O) to 315 MPa (temper H).
  • a copper alloy material made of C1940 has an electrical conductivity of 60% IACS or more and less than 100% IACS and a tensile strength of about 275 MPa (O3 temper) to 590 MPa (ESH temper).
  • a copper alloy material made of C7025 has an electrical conductivity of about 45.0% IACS and a tensile strength of about 650 MPa (temper classification 1/2 ⁇ H).
  • the copper alloy material according to the present invention contains impurity elements.
  • This impurity element is inevitably mixed in during the manufacturing process of the copper alloy material and is not intentionally added.
  • the impurity elements depend on the manufacturing raw materials and manufacturing equipment used, but include elements such as Ag (silver), Pb (lead), Ni (nickel) and S (sulfur). If these impurity elements are excessively mixed, there is a risk of deteriorating various properties (tensile strength, electrical conductivity, bending workability, etc.) of the copper alloy material.
  • S in a solid solution state causes deterioration of rolling workability, particularly cracking at the stage of hot rolling. From this point of view, the content of impurity elements in the copper alloy material is suppressed as low as possible, for example, the total is suppressed to 0.05% or less, preferably 0.03% or less, more preferably 0.01% or less. .
  • the copper alloy material according to the present invention preferably contains Mn.
  • the value obtained by (Mn content + total content of impurity elements)/(Fe content + P content + Sn content) x 100 (hereinafter referred to as "MI value") is considered.
  • the MI value is, for example, 1.1 or less (>0), preferably 1.0 or less (>0), thereby improving the rolling workability (especially hot workability) of the copper alloy material according to the present invention. ) can be sufficiently enhanced.
  • the copper alloy material according to the present invention contains Fe, P, Zn, and Sn as essential elements within the ranges described above, with the balance being Cu and impurity elements.
  • this copper alloy material has a tensile strength of 620 MPa or more (preferably 625 MPa or more, more preferably 630 MPa or more) and 40.0% IACS or more (preferably 45.0 MPa or more) in a temperature environment of 20°C. It has a conductivity of 0% IACS or more), and the generation of residual smut is suppressed as described later.
  • This copper alloy material has the above-described tensile strength and conductivity, and since the generation of residual smut is suppressed, it is practically a copper alloy material made of a Cu-Fe-Zn-P-based copper alloy such as C1940. It is considered that it can be sufficiently used as a substitute material for a copper alloy material composed of C7025, which has a higher strength.
  • the copper alloy material according to the present invention contains Fe, P, Zn, Sn, and Mn as essential elements within the ranges described above, with the balance being Cu and impurity elements.
  • the copper alloy material has an elongation at break of more than 20% in a temperature environment of 950° C., improves rolling workability, and is particularly resistant to cracking during hot rolling.
  • This copper alloy material has the above-mentioned tensile strength, electrical conductivity and elongation at break, and since the generation of residual smut is suppressed, it is practically made of a Cu-Fe-Zn-P-based copper alloy such as C1940. It is considered that it can be sufficiently used as a copper alloy material or a substitute material for a copper alloy material composed of C7025, which has a higher strength.
  • the tensile strength of the copper alloy material according to the present invention mainly depends on precipitation strengthening due to dispersed precipitation of particles of Fe or a compound containing Fe and P and work hardening due to cold rolling.
  • the strengthening mechanism of the copper alloy structure by precipitation strengthening and work hardening can be controlled by specifying the manufacturing conditions.
  • the effect of precipitation strengthening can be obtained by controlling the holding conditions of the heat treatment within a specific range and uniformly dispersing and precipitating particles of an appropriate size that can act as obstacles to the deformation of the copper alloy structure.
  • the effect of work hardening can be obtained by controlling the working conditions of cold rolling within a specific range and by appropriately accumulating crystals containing dislocations that can act as obstacles to deformation of the copper alloy structure.
  • the electrical conductivity of the copper alloy material according to the present invention substantially depends on Cu, it also utilizes the action of increasing the purity of Cu in the parent phase due to the precipitation of the particles described above.
  • a copper alloy material made of a Cu-Fe-P-Zn-Sn-based copper alloy has a tensile strength of 620 MPa or more (preferably 625 MPa or more, more preferably 630 MPa or more) in a temperature environment of 20 ° C.
  • the manufacturing method is important in order to have a conductivity of 40.0% IACS or more (preferably 45.0% IACS or more). That is, the method for producing a copper alloy material according to the present invention has the following steps (1) to (8), and the steps (1) to (8) are carried out in this order.
  • the copper alloy cast material is prepared to have an MI value of, for example, 1.1 or less (>0), preferably 1.0 or less (>0).
  • the steps (2) to (8) described above are performed in this order.
  • Fe, P, Zn, and Sn are contained within the ranges described above, and further, 0.002% or more and 0.025% or less of Mn is contained, and the balance is Cu and impurity elements.
  • a preferred copper alloy material can be produced.
  • This preferred copper alloy material has a tensile strength of 620 MPa or more and an electrical conductivity of 40.0% IACS or more in the temperature environment of 20° C., and further, in a temperature environment of 950° C., It can have an elongation at break greater than 20%.
  • a method for manufacturing a copper alloy material according to the present invention will be described below along the main process flow shown in FIG.
  • the first cold rolling step and the first heat treatment step may be combined and repeated as necessary. It is also possible to combine and repeat the first heat treatment step and the second cold rolling step.
  • a copper alloy cast material to which Fe, P, Zn and Sn are added is produced.
  • the copper alloy material obtained through the third heat treatment step is, in mass%, 1.6% or more and 2.6% or less of Fe, 0.01% or more and 0.3% or less of P, It contains 0.01% or more and 0.3% or less of Zn and 0.3% or more and 0.8% or less of Sn (preferably more than 0.3% and 0.8% or less), and the balance is
  • a copper alloy casting material is produced by preparing a material containing Cu and impurity elements.
  • the S content of the raw material for general production of this copper alloy material is, for example, about 0.001% to 0.005%.
  • the copper alloy material preferably further contains Mn.
  • the Mn content is adjusted to 0.002% or more and 0.025% or less, and preferably the MI value is also adjusted.
  • the MI value is adjusted to, for example, 1.1 or less (>0), preferably 1.0 or less (>0).
  • the copper alloy cast material produced in the melting and casting process is hot rolled to produce a hot rolled material.
  • the hot rolling conditions such as the heat holding temperature and the degree of rolling workability may be arbitrarily selected from general conditions. Generally, in the case of copper materials and copper alloy materials, hot rolling is performed at a wide temperature range of 700° C. to 1000° C. depending on the composition. In the case of a copper alloy material with a relatively large total content of additive elements, hot rolling is performed at a higher temperature of 900°C to 1000°C. From this point of view, the high-temperature characteristics of the copper alloy material according to the present invention are evaluated at a temperature near the center of 900° C. to 1000° C. (approximately 950° C.).
  • the hot rolled material produced in the hot rolling step is cold rolled to produce the first cold rolled material.
  • Cold rolling conditions such as the degree of rolling workability may be arbitrary.
  • the first cold-rolled material produced in the first cold rolling step is heated and held at a temperature of 500°C or higher and 600°C or lower for 4 hours or less. to produce a first heat-treated material.
  • This first heat treatment step is a heat treatment that is performed after the first cold rolling, which is the first rolling, and is a heat treatment that is performed to sufficiently release the strain accumulated in the copper alloy structure during the cold rolling.
  • the heat treatment at this stage is performed by heating and holding at a relatively high temperature (for example, 700° C. or more and 900° C. or less).
  • heating and holding is performed at a relatively low temperature of 500° C.
  • the heating and holding temperature in the first heat treatment step is excessively low (less than 500° C.), not only will the release of strain in the copper alloy structure be insufficient, but precipitation of the above particles into the copper alloy structure will be inadequate. be enough. Further, when the heating and holding temperature in the first heat treatment step is excessively high (exceeding 600 ° C.) or the heating and holding time is excessively long (exceeding 4 hours), the strain of the copper alloy structure is sufficiently released, The particles precipitated in the copper alloy structure may be excessively coarsened and hinder the improvement of the tensile strength of the copper alloy material. In addition, when the heating and holding temperature in the first heat treatment step is the above-described relatively high temperature (for example, 700° C. or higher and 900° C.
  • the first cold-rolled material is heated and held at a temperature of 500 ° C. or higher and 600 ° C. or lower for 4 hours or less, preferably to release strain and precipitate the particles.
  • heating and holding should be performed at a temperature of 550° C. or higher and 600° C. or lower for 4 hours or less (preferably 2 hours or less).
  • Second cold rolling step the first heat treated material produced in the first heat treatment step is used to perform cold rolling at a rolling reduction rate of 20% or more and 90% or less. to produce a second cold rolled material.
  • This second cold rolling step is a step of introducing and appropriately accumulating dislocations in the copper alloy structure of the first heat-treated material produced in the first heat treatment step, and moderately work hardening the copper alloy structure.
  • the dislocations introduced into the crystals forming the copper alloy structure act as starting points for precipitating particles responsible for precipitation strengthening of the copper alloy structure.
  • the particles responsible for precipitation strengthening of the copper alloy structure are evenly distributed in the copper alloy structure in the next second heat treatment step. can be precipitated. As a result, the tensile strength of the finally obtained copper alloy material can be further improved.
  • the degree of rolling reduction in the second cold rolling step is excessively small (less than 20%), introduction and accumulation of dislocations into the copper alloy structure will be insufficient, and in the following second heat treatment step, The number of particles deposited on the surface tends to be insufficient.
  • the degree of rolling reduction in the second cold rolling step is excessively large (more than 90%), the particles precipitated in the copper alloy structure in the following second heat treatment step grow excessively large, resulting in the effect of precipitation strengthening. is difficult to obtain.
  • the first heat-treated material produced in the first heat treatment step is cold-rolled at a rolling reduction rate of 20% or more and 90% or less.
  • cold rolling is performed at a rolling workability of 40% or more and 75% or less.
  • Second heat treatment step the second cold-rolled material produced in the second cold rolling step is heated and held at a temperature of 380 ° C. or higher and 480 ° C. or lower for 1 hour or more and 12 hours or less. to produce a second heat-treated material.
  • This second heat treatment step is a heat treatment performed after the second cold rolling described above, and utilizes dislocations introduced and accumulated during cold rolling to sufficiently disperse particles responsible for precipitation strengthening in the copper alloy structure.
  • This is the step of aging treatment for precipitation.
  • heating and holding for aging treatment is performed at a temperature of, for example, 400.degree. C.
  • the second heat treatment step of the present invention heating and holding is performed for 1 hour or more and 12 hours or less at a temperature of 380° C. or more and 480° C. or less, which is on the relatively low temperature side.
  • a temperature of 380° C. or more and 480° C. or less which is on the relatively low temperature side.
  • particles of Fe or a compound containing Fe and P precipitated in the copper alloy structure can be made finer and dispersed more uniformly.
  • the effect of precipitation strengthening on the copper alloy structure can be sufficiently obtained.
  • the synergistic effect of precipitation strengthening and work hardening obtained by the second cold rolling process can be obtained sufficiently.
  • the heating and holding temperature in the second heat treatment step is excessively low (less than 380°C) or the heating and holding time is excessively short (less than 1 hour), the precipitation of the particles into the copper alloy structure is insufficient. resulting in insufficient tensile strength and electrical conductivity of the finally obtained copper alloy material.
  • the heating and holding temperature in the second heat treatment step is excessively high (over 480°C) or the heating and holding time is excessively long (over 12 hours)
  • the particles precipitated in the copper alloy structure grow large. As a result, the effect of precipitation strengthening decreases, and the release of strain in the copper alloy structure progresses sufficiently beyond the intended degree, and the synergistic effect of precipitation strengthening and work hardening obtained by the second cold rolling process Effect is lost.
  • the second cold-rolled material is heated and held at a temperature of 380 ° C. or higher and 480 ° C. or lower for 1 hour or more and 12 hours or less.
  • heating and holding is performed at a temperature of 400° C. or higher and 460° C. or lower for 1 hour or longer and 12 hours or shorter (preferably 2 hours or longer and 8 hours or shorter).
  • Third cold rolling step the second heat treated material produced in the second heat treatment step is used to perform cold rolling at a rolling reduction rate of 60% or more and 80% or less. to produce a third cold rolled material. Also, in this step, the final desired thickness of the copper alloy material (product thickness) can be obtained.
  • dislocations are further introduced into and sufficiently accumulated in the copper alloy structure in which the particles of the second heat treated material produced in the second heat treatment step are dispersed and precipitated, and the copper alloy structure is changed. It is a step of further work hardening. As a result, the synergistic effect of precipitation strengthening and work hardening obtained by the second heat treatment step is sufficiently enhanced, so that the tensile strength of the finally obtained copper alloy material can be sufficiently improved.
  • the degree of rolling reduction in the third cold rolling step is excessively small (less than 60%), the copper alloy structure may not be sufficiently work hardened, and the synergistic effect of precipitation strengthening and work hardening may not be sufficiently enhanced. .
  • the rolling reduction rate in the third cold rolling step is excessively large (more than 80%), the strain in the copper alloy structure is excessively accumulated, and the excessively accumulated strain is used in the following third heat treatment step. In some cases, the tensile strength of the finally obtained copper alloy material is not sufficiently improved due to excessive release beyond the degree of release.
  • the second heat treated material produced in the second heat treatment step is cold rolled at a rolling reduction rate of 60% or more and 80% or less. In order to finally obtain a synergistic effect of precipitation strengthening and work hardening in a well-balanced manner, cold rolling is performed at a rolling workability of 65% or more and 75% or less.
  • Third heat treatment step In the third heat treatment step, the third cold rolled material produced in the third cold rolling step is heated and held at a temperature of 250°C or higher and 380°C or higher for 4 hours or less. Then, the desired copper alloy material is produced.
  • the heating and holding in this step may have a holding time of 0 h, that is, the temperature may be lowered as soon as the target holding temperature is reached after raising the temperature.
  • This third heat treatment step moderately releases the strain accumulated in the copper alloy structure of the third cold-rolled material produced by the third cold rolling described above, and the target copper alloy material elongation and bending This is a process for improving mechanical properties such as workability.
  • heat treatment for the purpose of releasing strain is maintained at a temperature of, for example, 400° C. or higher and 500° C. or lower. done.
  • heating and holding is performed for 4 hours or less at a temperature of 250° C. or higher and 380° C. or lower, which is on the lower temperature side.
  • the heating and holding temperature in the third heat treatment step is excessively low (less than 250°C)
  • the release of strain in the copper alloy structure of the third cold-rolled material becomes insufficient, resulting in the desired copper alloy material. Mechanical properties such as elongation and bendability may not be improved.
  • the heating and holding temperature in the third heat treatment step is excessively high (over 380 ° C.) or the heating and holding time is excessively long (over 4 hours)
  • the strain in the copper alloy structure of the third cold rolled material is excessively released, and the desired tensile strength of the copper alloy material may not be obtained.
  • the third cold-rolled material is heated and held at a temperature of 250 ° C. or higher and 380 ° C. or lower for 4 hours or less. In order to obtain a copper alloy structure with a good balance of elongation and bending workability, heating and holding at a temperature of 280° C. or more and 350° C. or less for 1 hour or less is performed.
  • Table 1 summarizes information such as compositions (additional elements), main manufacturing conditions, and mechanical properties of copper alloy materials of samples 1 to 29 (examples of the present invention and comparative examples).
  • the copper alloy materials of Samples 30 and 31 are also shown as reference examples.
  • Mn was not intentionally added to samples 1 to 29.
  • the remainder of samples 1 to 29 other than additive elements may be interpreted as Cu and impurity elements, and impurity elements (Ag, Pb, Ni, S, etc.) less than 0.01% are omitted.
  • the copper alloy material of Sample 1 shown in Table 1 contains 2.2% by mass of Fe, 0.03% by mass of P, 0.12% by mass of Zn, and 0.60% by mass of Sn. , the balance being Cu and impurity elements.
  • This copper alloy material was produced through the following steps (1) to (8). (1) In the melting and casting process, using a high-frequency melting furnace, an additive containing a predetermined additive element is added to a molten base material made of oxygen-free copper, and the like is added and melted in a nitrogen atmosphere. A copper alloy casting having a thickness of 25 mm, a width of about 30 mm and a length of about 150 mm was produced.
  • the copper alloy cast material was hot rolled while being heated to a temperature of about 950°C to produce a hot rolled material having a thickness of about 8 mm.
  • the hot-rolled material is cold-rolled to a rolling reduction rate of about 83% in total to produce a first cold-rolled material having a thickness of about 1.4 mm. did.
  • the first heat treatment step the first cold-rolled material was heated and held at a temperature of about 580°C for about 3 minutes to produce a first heat-treated material.
  • the first heat-treated material is cold-rolled to a rolling reduction rate of about 64% in total to produce a second cold-rolled material having a thickness of about 0.5 mm. did. In this case, the total rolling workability of the first cold rolling step and the second cold rolling step is about 94%.
  • the second cold-rolled material was heated and held at a temperature of about 450°C for about 4 hours to produce a second heat-treated material.
  • the third cold-rolling step the second heat-treated material is cold-rolled to a rolling reduction rate of about 70% in total to produce a third cold-rolled material having a thickness of about 0.15 mm. did.
  • the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%
  • the rolling workability of the first cold rolling step, the second cold rolling step and the third cold rolling step is The total rolling workability is about 98%.
  • the third cold-rolled material is heated and held at a temperature of about 350 ° C. for about 1 minute, and finally the copper alloy of sample 1 having a thickness of about 0.15 mm got the wood.
  • the copper alloy material of Sample 1 is an example of the present invention.
  • the copper alloy material of sample 2 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the second heat treatment step is set to a temperature of about 420 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1.
  • the copper alloy material of sample 2 is an example of the present invention.
  • the heating and holding temperature in the second heat treatment step is set to about 420 ° C.
  • the heating and holding temperature in the third heat treatment step is set to about 280 ° C. It was manufactured through substantially the same manufacturing process as the copper alloy material of sample 1 except that the temperature was set to 10°C, and finally had the same thickness as the copper alloy material of sample 1.
  • the copper alloy material of Sample 3 is an example of the present invention.
  • the heating and holding in the first heat treatment step was set to a temperature of about 550 ° C.
  • the rolling workability in the second cold rolling step was set to about 73%
  • the heating and holding in the second heat treatment step was set to a temperature of about 420 ° C.
  • the rolling reduction in the third cold rolling step was set to about 60%, except that the copper alloy of sample 1 After going through substantially the same manufacturing process as the material, it was finally manufactured to have the same thickness as the copper alloy material of sample 1.
  • the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%.
  • the copper alloy material of sample 5 is an example of the present invention.
  • the heating and holding in the first heat treatment step was set to a temperature of about 550 ° C.
  • the rolling workability in the second cold rolling step was was set to about 46%
  • the rolling workability in the third cold rolling step was set to about 80%. It is manufactured so as to have the same thickness as the alloy material. In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%.
  • the copper alloy material of Sample 6 is an example of the present invention.
  • the rolling reduction in the second cold rolling step was set to about 73%, and the heating and holding in the second heat treatment step was set to about 73%. Except that the temperature was set to 420 ° C. and the rolling workability in the third cold rolling step was set to about 60%, the manufacturing process was substantially the same as that of the copper alloy material of sample 1, and finally the copper of sample 1 It is manufactured so as to have the same thickness as the alloy material.
  • the copper alloy material of sample 7 is an example of the present invention.
  • the heating and holding in the first heat treatment step was set to a temperature of about 600 ° C.
  • the rolling workability in the second cold rolling step was set to about 73%
  • the heating and holding in the second heat treatment step was set to a temperature of about 420 ° C.
  • the rolling reduction in the third cold rolling step was set to about 60%, except that the copper alloy of sample 1 After going through substantially the same manufacturing process as the material, it was finally manufactured to have the same thickness as the copper alloy material of sample 1.
  • the copper alloy material of Sample 8 is an example of the present invention.
  • the heating and holding in the first heat treatment step was set to a temperature of about 600 ° C.
  • the rolling workability in the second cold rolling step was set to about 46%
  • the rolling workability in the third cold rolling step was set to about 80%. It is manufactured so as to have the same thickness as the alloy material.
  • the copper alloy material of sample 9 is an example of the present invention.
  • Fe contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 1.50% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally.
  • the copper alloy material of Sample 10 is a comparative example in which the Fe content is outside the scope of the present invention.
  • Fe contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 2.80% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally.
  • the copper alloy material of sample 11 is a comparative example, and the Fe content is outside the scope of the present invention.
  • the P contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 0.22% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally.
  • the copper alloy material of sample 12 is an example of the present invention.
  • the copper alloy material of sample 13 shown in Table 1 in the manufacturing process of the copper alloy material of sample 1, about 0.40% by mass of Zn is contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally.
  • the copper alloy material of sample 13 is a comparative example, and the Zn content is outside the scope of the present invention.
  • the copper alloy material of sample 15 shown in Table 1 in the manufacturing process of the copper alloy material of sample 1, Sn contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 0.90% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally.
  • the copper alloy material of sample 15 is a comparative example, and the Sn content is outside the scope of the present invention.
  • the copper alloy material of sample 17 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the first heat treatment step is set to a temperature of about 650 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1.
  • the copper alloy material of sample 17 is a comparative example, and the first heat treatment step is outside the scope of the present invention.
  • the copper alloy material of sample 18 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding time in the first heat treatment step was set to about 5 hours in the manufacturing process of the copper alloy material of sample 1. Through the manufacturing process of 1, it was finally manufactured to have a thickness equivalent to that of the copper alloy material of sample 1.
  • the copper alloy material of sample 18 is a comparative example, and the first heat treatment step is outside the scope of the present invention.
  • the rolling reduction rate in the second cold rolling step was set to about 17%
  • the rolling reduction in the third cold rolling step was Except for setting the degree of hardness to about 80%, it was manufactured to have a thickness equivalent to that of the copper alloy material of Sample 1 after undergoing substantially the same manufacturing process as that of the copper alloy material of Sample 1. .
  • the total rolling workability of the second cold rolling step and the third cold rolling step is about 83%.
  • the copper alloy material of sample 19 is a comparative example, and the second cold rolling step is outside the scope of the present invention.
  • the rolling reduction rate in the second cold rolling step was set to about 91%
  • the rolling reduction in the third cold rolling step was except for setting the degree of hardness to about 60%
  • the copper alloy material was manufactured through substantially the same manufacturing process as the copper alloy material of sample 1, and finally manufactured to have the same thickness as the copper alloy material of sample 1.
  • the total rolling workability of the second cold rolling step and the third cold rolling step is about 96%.
  • the copper alloy material of sample 20 is a comparative example, and the second cold rolling step is outside the scope of the present invention.
  • the copper alloy material of sample 21 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the second heat treatment step was set to a temperature of about 350 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1.
  • the copper alloy material of sample 21 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
  • the copper alloy material of sample 22 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the second heat treatment step was set to a temperature of about 500 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1.
  • the copper alloy material of Sample 22 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
  • the copper alloy material of sample 23 shown in Table 1 is the sample 1 except that the heating and holding in the second heat treatment step is set to a temperature of about 420 ° C. for about 0.5 hours in the manufacturing process of the copper alloy material of sample 1. After going through substantially the same manufacturing process as the copper alloy material of sample 1, it was finally manufactured to have the same thickness as the copper alloy material of sample 1.
  • the copper alloy material of sample 23 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
  • the copper alloy material of sample 24 shown in Table 1 is the manufacturing process of the copper alloy material of sample 1, except that the heating and holding in the second heat treatment step is set to a temperature of about 450 ° C. for about 20 hours. It was manufactured so as to have a thickness equivalent to that of the copper alloy material of the sample 1 through a manufacturing process substantially equivalent to that of the copper alloy material.
  • the copper alloy material of Sample 24 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
  • the rolling reduction rate in the second cold rolling process was set to about 79%
  • the rolling reduction in the third cold rolling process was Except for setting the degree of hardness to about 50%
  • the copper alloy material of sample 1 was manufactured through substantially the same manufacturing process as that of the copper alloy material of sample 1, and finally manufactured to have the same thickness as the copper alloy material of sample 1.
  • the total rolling workability of the second cold rolling step and the third cold rolling step is about 90%.
  • the copper alloy material of sample 25 is a comparative example, and the third cold rolling step is outside the scope of the present invention.
  • the rolling reduction rate in the second cold rolling step was set to about 28%, and the rolling reduction in the third cold rolling step was Except for setting the degree of hardness to about 85%, it was manufactured so as to have the same thickness as the copper alloy material of Sample 1 after undergoing substantially the same manufacturing process as that of the copper alloy material of Sample 1. .
  • the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%.
  • the copper alloy material of sample 26 is a comparative example, and the third cold rolling step is outside the scope of the present invention.
  • the copper alloy material of sample 27 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the third heat treatment step was set to a temperature of about 200 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1.
  • the copper alloy material of sample 27 is a comparative example, and the third heat treatment step is outside the scope of the present invention.
  • the copper alloy material of sample 28 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the third heat treatment step was set to a temperature of about 400 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1.
  • the copper alloy material of sample 28 is a comparative example, and the third heat treatment step is outside the scope of the present invention.
  • the copper alloy material of sample 29 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding time in the third heat treatment step was set to about 5 hours in the manufacturing process of the copper alloy material of sample 1. Through the manufacturing process of 1, it was finally manufactured to have a thickness equivalent to that of the copper alloy material of sample 1.
  • the copper alloy material of sample 29 is a comparative example, and the third heat treatment step is outside the scope of the present invention.
  • the copper alloy material of sample 30 shown in Table 1 has a composition corresponding to C1940 (Cu-2.2% by mass Fe-0.03% by mass P-0.12% by mass Zn), and the temper is ESH. It is a commercially available material having the same thickness as the copper alloy material of Sample 1.
  • the copper alloy material of sample 30 is a reference example.
  • the copper alloy material of Sample 31 shown in Table 1 has a composition equivalent to C7025 (Cu-3% by mass Ni-0.65% by mass Si-0.15% by mass Mg) and has a temper of 1/2 H It is a commercially available material having a thickness equivalent to that of the copper alloy material of Sample 1.
  • the copper alloy material of sample 31 is a reference example.
  • the properties of the copper alloy materials of Samples 1 to 31 described above as shown in Table 1, attention was focused on tensile strength, electrical conductivity, bending workability, and the presence or absence of residual smut, and they were actually confirmed and evaluated.
  • the tensile strength of the copper alloy material was measured in accordance with JIS-Z2241:2011, which defines a tensile test method for metallic materials, under a normal temperature environment (approximately 20°C).
  • the electrical conductivity of the copper alloy material was measured in a room temperature environment (approximately 20° C.) in accordance with JIS-Z0505:1975, which defines methods for measuring the electrical conductivity of non-ferrous metal materials.
  • the bending workability of the copper alloy material was evaluated by the W bending test, which is adopted as a bending test in JIS-H3110:2018, in a room temperature environment (about 20°C). Specifically, when the test piece (copper alloy material) is bent with a bending radius (inner radius) of 0.15 mm, the case where no cracks are confirmed on the outer surface of the bending of the test piece is evaluated as "excellent”. A case where cracks were confirmed even if they were minute was evaluated as "poor”. The presence or absence of residual smut was confirmed by observing the surface of the test piece (copper alloy material) that had been pretreated, immersed in a chemical polishing liquid for about 1 minute, washed with water, and dried.
  • the chemical polishing liquid was an acidic aqueous solution containing about 20% by mass of sulfuric acid and about 8% by mass of hydrogen peroxide, and was kept at about 40.degree.
  • the surface area of the test piece to be immersed in the chemical polishing liquid was set to about 2000 mm 2 (front and back surfaces with a width of 20 mm and a length of 50 mm).
  • the pretreatment of the specimen to be tested was carried out in the order of ethanol degreasing, alkaline electrolytic degreasing, immersion (neutralization) in a 5% sulfuric acid aqueous solution, washing with water, and drying.
  • the copper alloy material of sample 30 had a tensile strength of 540 MPa, which was less than 620 MPa.
  • the electrical conductivity was 63.0%IACS, which was 40.0%IACS or more.
  • the bending workability was "excellent” and the residual smut was "absent”.
  • the copper alloy material of sample 31 had a tensile strength of 650 MPa, which was 620 MPa or more.
  • the electrical conductivity was 45.0%IACS, which was 40.0%IACS or more.
  • the bending workability was evaluated as "excellent", and the residual smut was evaluated as "present”.
  • the tensile strength was 670 MPa for sample 1 and 672 MPa for sample 11, both of which were 620 MPa or more.
  • Sample 10 was 575 MPa, which was less than 620 MPa.
  • the electrical conductivity was 48.2%IACS for sample 1 and 56.3%IACS for sample 10, both of which were 40.0%IACS or higher.
  • sample 11 resulted in 38.8% IACS and less than 40.0% IACS.
  • the bending workability of sample 11 was "poor" while samples 1 and 10 were "excellent”.
  • all of Samples 1, 10 and 11 had "no" residual smut.
  • a comparative evaluation of the copper alloy materials of Samples 1, 10 and 11 with different Fe contents showed that when the Fe content was small and outside the above range, the tensile strength of the copper alloy material decreased and reached 620 MPa. It turned out not to. Further, it was found that when the Fe content becomes large and falls outside the above range, the electrical conductivity of the copper alloy material decreases and does not reach 40.0% IACS. It was also found that the Fe content hardly affects the bending workability and residual smut of the copper alloy material.
  • the copper alloy materials of samples 1 and 12 shown in Table 3 are substantially the same except that the P content of the finally obtained copper alloy material is changed by adjusting the composition in the melting and casting process. It is manufactured so as to have substantially the same thickness through the manufacturing process of Specifically, since the P content of Sample 1 is 0.03%, it falls within the range of 0.01% or more and 0.3% or less specified in the present invention. Further, the content of sample 12 is 0.22% by mass, which is larger than that of sample 1, which is within the above range, but is outside the range of 0.01% or more and 0.20% or less, which the inventor considers more preferable.
  • the tensile strength of both samples 1 and 12 was 620 MPa or more, and sample 12 was 675 MPa, which was larger than sample 1 (670 MPa).
  • the electrical conductivity was 40.0% IACS or more for both samples 1 and 12, and sample 12 was 48.8% IACS, which is higher than sample 1 (48.2% IACS).
  • the bending workability of sample 12 was "poor” while sample 1 was “excellent”.
  • residual smut was "absent" for both samples 1 and 12.
  • a comparative evaluation of the copper alloy materials of samples 1 and 12 with different P contents revealed that the P content hardly affected the tensile strength and electrical conductivity of the copper alloy materials. In addition, it was found that when the P content increases, the bending workability of the copper alloy material tends to deteriorate. It was also found that the P content hardly affects the residual smut of the copper alloy material. Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, and having an electrical conductivity of 40.0% IACS or more, it is practically 0.01% or more and 0.3% or less specified in this invention. A copper alloy material containing P is effective. In addition, from the viewpoint of good bending workability, a copper alloy material containing 0.01% or more and 0.20% or less of P is practically effective.
  • the tensile strength of both samples 1 and 12 was 620 MPa or more, and sample 13 was 674 MPa, which was larger than sample 1 (670 MPa).
  • the electrical conductivity of sample 13 was 39.2%IACS, which was less than 40.0%IACS, compared to sample 1 (48.2%IACS), which was 40.0%IACS or more.
  • the bending workability of sample 13 was "poor” while sample 1 was “excellent”.
  • residual smut was "absent" for both samples 1 and 13.
  • the tensile strength of samples 1, 4 and 15 was 620 MPa or more, and sample 14 was less than 620 MPa. Specifically, compared to the tensile strength of sample 1 (670 MPa), sample 4 was smaller at 624 MPa, sample 14 was even smaller at 604 MPa, while sample 15 was larger at 690 MPa. In terms of electrical conductivity, Samples 1, 4 and 14 were 40.0%IACS or more, and Sample 15 was less than 40.0%IACS. Specifically, relative to the conductivity of sample 1 (48.2% IACS), sample 4 was greater at 51.0% IACS and sample 14 was even greater at 55.0% IACS, whereas sample 15 was smaller at 39.8% IACS. Further, the bending workability of Sample 15 was "poor" while Samples 1, 4 and 14 were "excellent". In addition, all of samples 1, 4, 14 and 15 were found to have no residual smut.
  • a comparative evaluation of the copper alloy materials of samples 1, 4, 14 and 15 with different Sn contents revealed that the tensile strength of the copper alloy materials tended to decrease as the Sn content decreased. In addition, it was found that when the Sn content was further decreased and fell outside the above range, the tensile strength of the copper alloy material did not reach 620 MPa. Further, a comparative evaluation of the copper alloy materials of Samples 1 and 4 revealed that when the copper alloy material contained more than 0.3% Sn, a tensile strength of 625 MPa or more was obtained. It was also found that the electrical conductivity of the copper alloy material tends to increase as the Sn content decreases.
  • Samples 1 and 4 are heated at 580° C. for about 3 minutes.
  • sample 16 is at a lower temperature of 450° C.
  • sample 17 is at a higher temperature of 650° C., so the retention times are similar to samples 1 and 4, but outside the above range.
  • sample 18 is longer, about 5 hours, the holding temperature is similar to samples 1 and 4, but outside the above range.
  • sample 1 (670 MPa), which is 620 MPa or more, was as small as 624 MPa due to the Sn content of sample 4 being smaller than that of sample 1, but 620 MPa. That was it.
  • sample 16 which is out of the above range for low temperature retention, has a value of 610 MPa
  • sample 17, which is out of the above range for high temperature retention, has a value of 596 MPa
  • sample 18, which is out of the above range for long term retention. was 612 MPa, and both of these were less than 620 MPa.
  • the electrical conductivity is 51.0% IACS for samples 4 and 18, 50.5% IACS for sample 16, and 50.5% IACS for sample 1 (48.2% IACS), which is 40.0% IACS or more. 17 resulted in 51.8% IACS, both of which were greater than Sample 1.
  • the bending workability of samples 1, 16, 17 and 18 were all "excellent".
  • all samples 1, 16, 17 and 18 were found to have no residual smut.
  • Comparative evaluation of the copper alloy materials of samples 1 and 17 with different heating and holding temperatures in the first heat treatment step and comparative evaluation of the copper alloy materials of samples 4 and 16 showed that the heating and holding temperature in the first heat treatment step was high or low. It has been found that if the tensile strength is outside the above range, the tensile strength of the copper alloy material tends to decrease and not reach 620 MPa. Further, according to a comparative evaluation of the copper alloy materials of Samples 1 and 18, if the heating and holding in the first heat treatment step is prolonged and is outside the above range, the tensile strength of the copper alloy material decreases and does not reach 620 MPa. It turned out that there is a trend.
  • the tensile strength of sample 1 (670 MPa), which is 620 MPa or more, is as small as 654 MPa for sample 6, which has a reduced degree of rolling. Although the sample 19 with the same value was further reduced to 624 MPa, all of them were 620 MPa or more.
  • Sample 20 in which the degree of rolling was increased to be outside the above range was 610 MPa, which was even lower, and was less than 620 MPa.
  • the electrical conductivity of sample 1 48.2% IACS
  • IACS which is 40.0% IACS or more
  • is 48.8% IACS for sample 20 which is out of the above range by increasing the degree of rolling. was at the same level.
  • Sample 6 in which the degree of rolling work was reduced, was as small as 45.8% IACS.
  • Sample 19 in which the degree of rolling work was further reduced to be outside the above range, was further reduced to 39.6%IACS, which was less than 40.0%IACS.
  • the bending workability of samples 1, 6, 19 and 20 were all "excellent”.
  • all of samples 1, 6, 19 and 20 were "absent" with respect to residual smut.
  • a comparative evaluation of the copper alloy materials of Samples 1, 6, 19 and 20 revealed that when the degree of rolling work in the second cold rolling step is excessively outside the above range, the tensile strength of the copper alloy material decreases. It was found that the pressure did not reach 620 MPa. Further, by comparative evaluation of the copper alloy materials of Samples 1, 6, 19 and 20, even if the degree of rolling workability in the second cold rolling step is excessively outside the above range, the electrical conductivity of the copper alloy material does not change.
  • sample 22 is at a higher temperature of 500° C., so the retention time is similar to sample 1, but outside the ranges given above. Also, sample 23 is shorter, about 0.5 hours, and sample 24 is longer, about 20 hours, so the holding temperature is within the above range, but the holding time is outside the above range.
  • the tensile strength is sample 1 (670 MPa), which is 620 MPa or more, and sample 21 (606 MPa) and sample 22 (575 MPa), which are outside the above range for low or high temperature retention, and , Sample 23 (598 MPa) and Sample 24 (602 MPa), both of which were out of the above range for short-term or long-term retention, decreased to less than 620 MPa.
  • the electrical conductivity of sample 1 48.2% IACS
  • sample 21 38.0% IACS
  • Sample 23 39.7% IACS
  • a comparative evaluation of the copper alloy materials of Samples 1, 22 and 24 revealed that the electrical conductivity of the copper alloy material tends to increase when the heating and holding time in the second heat treatment step is high or long.
  • a comparative evaluation of the copper alloy materials of Samples 1, 21, 22, 23 and 24 revealed that the heating and holding conditions in the second heat treatment step had little effect on the bending workability and residual smut of the copper alloy materials. . Therefore, there is no residual smut, it has a tensile strength of 620 MPa or more, has an electrical conductivity of 40.0% IACS or more, and in addition, has good bending workability.
  • a second heat treatment step in which the rolled material is heated and held at a temperature of 380° C. or more and 480° C. or less for 1 hour or more and 12 hours or less to produce the second heat treated material is effective.
  • the tensile strength is sample 1 (670 MPa), which is 620 MPa or more, and sample 25 (569 MPa), which is out of the above range by reducing the degree of rolling, and increasing the degree of rolling.
  • All of Sample 26 (580 MPa), which was out of the above range, decreased to less than 620 MPa.
  • the electrical conductivity of sample 1 48.2% IACS
  • 40.0% IACS 40.0% IACS or more
  • sample 25 48.2% IACS
  • Sample 26 (46.0% IACS) which was made to be outside the above range by increasing the degree of rolling, did not fall below 40.0% IACS, but was smaller than Sample 1.
  • the bendability of samples 1, 25 and 26 was all "excellent".
  • all of samples 1, 25 and 26 were "absent" with respect to residual smut.
  • a comparative evaluation of the copper alloy materials of Samples 1, 25 and 26 with different degrees of rolling reduction in the third cold rolling step revealed that when the degree of rolling reduction in the third cold rolling step was outside the above range, the copper alloy material It was found that the tensile strength tends to decrease and not reach 620 MPa. Further, it was found that even if the degree of rolling workability in the third cold rolling step becomes smaller and falls outside the above range, there is a tendency that the electrical conductivity of the copper alloy material is less likely to be affected. Further, it was found that when the degree of rolling workability in the third cold rolling step becomes large and falls outside the above range, the electrical conductivity of the copper alloy material tends to decrease.
  • the degree of rolling workability in the third cold rolling step does not easily affect the bending workability and residual smut of the copper alloy material. Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, having a conductivity of 40.0% IACS or more, and having good bending workability, the second heat-treated material is practically used.
  • the third cold-rolling step of producing the third cold-rolled material by cold-rolling at a rolling reduction ratio of 60% or more and 80% or less using is effective.
  • sample 28 is at a higher temperature of 400° C., so the retention times are similar to those of sample 1, but outside the ranges given above. Also, sample 29 is longer, about 5 hours, so the holding temperature is similar to sample 1, but the holding time is outside the above range.
  • Comparative evaluation of the copper alloy materials of samples 1 and 28 with different heating and holding temperatures in the third heat treatment step and comparative evaluation of the copper alloy materials of samples 1 and 29 showed that the heating and holding temperature in the third heat treatment step was high or long. It has been found that if the tensile strength is outside the above range, the tensile strength of the copper alloy material tends to decrease and not reach 620 MPa. In addition, a comparative evaluation of the copper alloy materials of Samples 1 and 27 revealed that the tensile strength of the copper alloy material tended to increase when the heating and holding temperature in the third heat treatment step was lowered.
  • ⁇ Influence of Mn> a copper alloy material intentionally not containing Mn (Sample 1A) and a copper alloy material intentionally containing Mn (Samples 1B to 1F) were produced.
  • the copper alloy materials of Samples 1A to 1F were substantially the same as those of Sample 1 shown in Table 1, except that the components were prepared in the melting and casting process so that the Mn content of the finally obtained copper alloy material was different. Through the manufacturing process, it was produced so as to have substantially the same thickness.
  • Table 11 summarizes information such as the composition (additional elements), main manufacturing conditions, and mechanical properties of the copper alloy materials of Samples 1A to 1F (examples of the present invention).
  • the rest of the samples 1A to 1F shown in Table 11 other than the additive elements may be interpreted as Cu and impurity elements, and the impurity elements (Ag, Pb, Ni, S, etc.) less than 0.01% are omitted. ing.
  • the Mn content of Sample 1A, to which Mn is not intentionally added is less than 0.001%.
  • the Mn content of the copper alloy material to which Mn is intentionally added is about 0.001% for sample 1B, about 0.002% for sample 1C, about 0.006% for sample 1D, and about 0.006% for sample 1E. about 0.010% and sample 1F about 0.020%. Therefore, the Mn contents of the samples 1C to 1F are within the range of the Mn contents (0.002% or more and 0.025% or less) described above as the preferred copper alloy materials of the present invention.
  • the tensile strength, electrical conductivity, and bending workability of Samples 1A to 1F were evaluated under a normal temperature environment (about 20°C), and the presence or absence of residual smut was evaluated. As a result, as shown in Table 11, the tensile strength was All of them were 620 MPa or more and within the range of 650 to 670 MPa. When Mn is 0.002% or less (Samples 1A to 1C), the tensile strength is less than 660 MPa, and when Mn exceeds 0.002% (Samples 1D to 1F), it is 660 MPa or more.
  • the tensile strength is less likely to be substantially affected by the Mn content, and there is a high possibility that the tensile strength will be 620 MPa or more even if the Mn content is 0.002% or more and 0.025% or less.
  • the electrical conductivity of samples 1A to 1F was all 40%IACS or higher and within the range of 46.0 to 47.2%IACS. From this, the electrical conductivity is less likely to be substantially affected by the Mn content, and there is a high possibility that the electrical conductivity will be 40% IACS or higher even if the Mn content is 0.002% or more and 0.025% or less.
  • the bending workability of samples 1A to 1F was all "excellent".
  • the bending workability is not substantially affected by the Mn content, and it is highly likely that the bending property will be "excellent” even if the Mn content is 0.002% or more and 0.025% or less.
  • the residual smut of Samples 1A to 1F was "absent". From this, the residual smut is less likely to be substantially affected by the Mn content, and there is a high possibility that the residual smut is "absent” even if the Mn content is 0.002% or more and 0.025% or less.
  • the elongation at break of samples 1A to 1F was evaluated in a high temperature environment (about 950°C). As a result, as shown in Table 11, the elongation at break of Samples 1A to 1F was generally 20% or more. Specifically, the elongation at break can be less than 20% when Mn is 0.001% or less (Samples 1A, 1B), and when Mn is 0.002% or more (Samples 1C-1F). It was found that the content definitely exceeds 20% and becomes 30% or more when Mn is 0.006% or more (Samples 1D to 1F).
  • the elongation at break reaches a maximum of 37.0% when Mn is 0.010% (Sample 1E), and decreases to 32.0% when Mn is 0.020% (Sample 1F). I understand. From this, the elongation at break is easily affected by the Mn content, and the Mn content of 0.002% or more and 0.025% or less reliably exceeds 20%, and the Mn content of 0.005% or more and 0.020% or less is likely to be 30% or more due to the content of
  • the MI value is a value obtained by (Mn content+total content of impurity elements)/(Fe content+P content+Sn content) ⁇ 100.
  • the total content of Fe, P and Sn is 2.82%.
  • the increase in Mn content from 0% (Sample 1A) to 0.020% (Sample 1F) is proportional to It can be confirmed that the MI value increases from 0.04 (Sample 1A) to 0.74 (Sample 1F).
  • the total content of impurity elements is set to 0.010% (low purity), 0.005% (ordinary purity), and 0.001% ( high purity), the Mn content (measured value) and the MI value (conditionally calculated value) based on the measured value shown in Table 11
  • a first model was derived, and further, the MI value A second model was derived to show the relationship between (conditional calculated value) and elongation at break (actual value).
  • a first model was then used to predict a range of MI values corresponding to a range of Mn contents, and a second model was used to predict a range of elongation at break corresponding to a range of MI values.
  • the first model is a graph (scatter diagram) of the Mn content (actual value) and the MI value (conditionally calculated value) using general-purpose spreadsheet software (Microsoft Excel), considering practicality and ease. ) was created, and a linear (first-order) approximation formula was obtained and used as a regression model.
  • the Mn content (set value) is the independent variable x
  • the MI value (predicted value) is the first dependent variable p.
  • the prediction interval is 0.000 ⁇ x ⁇ 0.030.
  • the second model was used as a regression model by creating a graph (scatter diagram) of MI values (calculated values with conditions) and elongation at break (actual values), obtaining a multinomial (quadratic) approximation formula.
  • the MI value (predicted value) of the first dependent variable p of the first model is the independent variable
  • the elongation at break (predicted value) is the second dependent variable y.
  • the reliability of the first model and the second model is unconditionally “reliable” if the coefficient of determination (R 2 ) is 0.7 or more (R 2 ⁇ 1) with reference to the way of thinking in the field of machine learning. I decided.
  • Tables 12 and 13 show the total impurity element content of 0.010% (low purity), 0.005% (ordinary purity) and 0.001% (high purity) based on the measured values shown in Table 11. 3 shows the prediction results of the Mn content (set value), MI value (predicted value), and elongation at break (predicted value) under the following three conditions.
  • S which has a particularly large effect on rolling workability, etc.
  • the S content of general manufacturing raw materials is considered to be about 0.001% to 0.005%, and actual measurement is not possible.
  • the total content of impurity elements can be selectively set and predicted from 0.001% to 0.005%.
  • the impurity elements are mainly Ag, Pb, Ni and S
  • the total content of Ag, Pb, Ni and S can be set as the total content of the impurity elements for prediction.
  • the prediction result by the first model is For example, p is 0.37 when x is 0.000, p is 0.44 when x is 0.002, p is 1.00 when x is 0.018, and x is 0.00. 025, p became 1.25.
  • the prediction result by the second model is, for example, y is 21.1 when p is 0.37, y is 25.5 when p is 0.44, and y is 1.00 when p is 1.00. 34.0 and y was 22.6 when p was 1.25.
  • Both the R 2 (0.9895) of the first model and the R 2 (0.8590) of the second model are sufficiently larger than 0.7, which is a criterion of reliability. Therefore, the prediction results of the first model and the second model are less likely to be significantly affected by outliers, and therefore can be judged to be "reliable".
  • the MI value is, for example, 0.45 or more (preferably 0.50 or more) and 1.1 or less (preferably, 1.0 or less, more preferably 0.9 or less).
  • the prediction result by the first model is as follows. For example, p is 0.19 when x is 0.000, p is 0.26 when x is 0.002, p is 1.00 when x is 0.023, and x is 0.00. 025 p became 1.07.
  • the prediction result by the second model is, for example, y is 20.8 when p is 0.19, y is 25.4 when p is 0.26, and y is 26.6, and y was 22.3 when p was 1.07.
  • Both the R 2 (0.9950) of the first model and the R 2 (0.8712) of the second model are sufficiently larger than 0.7, which is a criterion of reliability. Therefore, the prediction results of the first model and the second model are less likely to be significantly affected by outliers, and therefore can be judged to be "reliable”.
  • the MI value is, for example, 0.30 or more (preferably 0.35 or more) and 1.1 or less (preferably, 1.0 or less, more preferably 0.9 or less).
  • the prediction result by the first model is, for example, p is 0.04 when x is 0.000, p is 0.05 when x is 0.0003, p is 0.11 when x is 0.002, and p is 0.025 when x is 0.025. p was 1.00 when x was 0.93 and x was 0.027.
  • the prediction result by the second model is, for example, y is 20.5 when p is 0.04, y is 21.2 when p is 0.05, and y is 25.3, y was 22.0 when p was 0.93, and y was 16.4 when p was 1.00.
  • Both the R 2 (0.9980) of the first model and the R 2 (0.8808) of the second model are sufficiently larger than 0.7, which is a criterion of reliability. Therefore, the prediction results of the first model and the second model are less likely to be significantly affected by outliers, and therefore can be judged to be "reliable".
  • the MI value when Mn is contained in a high-purity product, considering practicality and stability, the MI value is, for example, 0.15 or more (preferably 0.20 or more) and 0.9 or less (preferably, 0.85 or less, more preferably 0.80 or less).
  • the content of the additive elements (Fe, P, Zn and Sn) constituting the copper alloy structure of the copper alloy material is controlled within a specific range, and in the manufacturing process of the copper alloy material shown in FIG.
  • Cu-Fe-Zn-P such as C1940

Abstract

Provided are: a copper alloy material that does not have problems with residual smut, similar to C1940 and other Cu–Fe–Zn–P copper alloy materials, that has tensile strength and conductivity roughly comparable to those of C7025 and other Cu–Ni–Si copper alloy materials, and that preferably has good bending workability; and a method for manufacturing the copper alloy material. A copper alloy casting material is obtained by adding iron, phosphorous, zinc, and tin and performing melt casting. The manufacturing method proceeds through: hot rolling; cold rolling; heat treatment under sustained conditions of 500–600°C for up to four hours; cold rolling at 20–90% draft; heat treatment under sustained conditions of 380–480°C for one to twelve hours; cold rolling at 60–80% draft; and heat treatment under sustained conditions of 250–380°C for up to four hours. By said method, obtained is a copper alloy material that contains, by mass percentage, 1.6–2.6% iron, 0.01–0.35% phosphorus, 0.01–0.30% zinc, and 0.3–0.8% tin, the remainder consisting of copper and impurity elements, that has tensile strength of at least 620 MPa, and that has conductivity of at least 40.0% IACS.

Description

銅合金材および銅合金材の製造方法COPPER ALLOY MATERIAL AND METHOD FOR MANUFACTURING COPPER ALLOY MATERIAL
　この発明は、銅合金材および銅合金材の製造方法に関し、たとえば、リードフレーム、コネクタ、端子などの電気・電子部品の材料として用いられる、銅合金材および銅合金材の製造方法に関する。 The present invention relates to a copper alloy material and a method for producing a copper alloy material, and for example, to a copper alloy material and a method for producing a copper alloy material used as materials for electrical and electronic parts such as lead frames, connectors, and terminals.
　従来、銅合金は良好な強度と導電性を持つことから、リードフレームを始めとする電気・電子部品の材料として一般的に用いられている。銅合金の中でも、たとえば、Ｃｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金は、機械的強さと導電性と熱伝導性のバランスがよいとされている。Ｃｕ－Ｆｅ－Ｚｎ－Ｐ系の代表的な銅合金の一つは、たとえば、ＪＩＳ－Ｈ３１００：２０１８に規定されているＣ１９４０である。Ｃ１９４０は、質量％で、約２．２％のＦｅと約０．０３％のＰと約０．１２％のＺｎとを含有する析出硬化型の銅合金である。Ｃ１９４０は、６０％ＩＡＣＳ程度の導電率を有するとともに４００ＭＰａ～５５０ＭＰａ程度の引張強さを有しており、国際的にも標準的な銅合金として認知され、多くの用途で利用されている。 Conventionally, copper alloys have good strength and conductivity, so they are commonly used as materials for electrical and electronic parts such as lead frames. Among copper alloys, for example, a Cu--Fe--Zn--P-based copper alloy is said to have a good balance of mechanical strength, electrical conductivity, and thermal conductivity. One of the typical Cu—Fe—Zn—P-based copper alloys is, for example, C1940 defined in JIS-H3100:2018. C1940 is a precipitation hardening copper alloy containing, by mass, about 2.2% Fe, about 0.03% P, and about 0.12% Zn. C1940 has an electrical conductivity of about 60% IACS and a tensile strength of about 400 MPa to 550 MPa, and is internationally recognized as a standard copper alloy and used in many applications.
　近年、電気・電子部品の高機能・高集積化に伴って、たとえば、リードフレームの分野では、リードフレームそのものの薄肉化が進んでいる。薄肉化されたリードフレームは変形しやすく、上記Ｃ１９４０では機械的強さが不十分である。このような場合、たとえば、Ｃｕ－Ｎｉ－Ｓｉ系の銅合金が利用されることが多い。Ｃｕ－Ｎｉ－Ｓｉ系の銅合金は、銅合金のＣｕを主とする母相中にＮｉとＳｉを含む化合物の粒子を析出させることによって高強度を得る析出硬化型の銅合金である。Ｃｕ－Ｎｉ－Ｓｉ系の代表的な銅合金の一つは、たとえば、コルソン合金と呼ばれるＣ７０２５である。Ｃ７０２５は、上記ＪＩＳの規定外であるが、質量％で示す含有率で、約３．０％のＮｉと約０．６５％のＳｉと約０．１５％のＭｇを含有する銅合金である。Ｃ７０２５は、６００ＭＰａ～７００ＭＰａ程度の引張強さを有するとともに４５．０％ＩＡＣＳ程度の導電率を有しており、Ｃ１９４０よりも曲げ加工性は劣るが、上記したリードフレームにも利用されている。 In recent years, in the field of lead frames, for example, lead frames themselves are becoming thinner as electrical and electronic components become more sophisticated and highly integrated. A thin lead frame is easily deformed, and the above C1940 is insufficient in mechanical strength. In such cases, for example, a Cu--Ni--Si based copper alloy is often used. A Cu—Ni—Si-based copper alloy is a precipitation-hardening copper alloy that obtains high strength by precipitating particles of a compound containing Ni and Si in a Cu-based parent phase of the copper alloy. One of the representative copper alloys of the Cu—Ni—Si system is, for example, C7025 called Corson alloy. C7025 is a copper alloy containing about 3.0% Ni, about 0.65% Si, and about 0.15% Mg, in terms of percentages by mass, although it is not specified in the above JIS. . C7025 has a tensile strength of about 600 MPa to 700 MPa and an electrical conductivity of about 45.0% IACS, and although it is inferior to C1940 in bending workability, it is also used for the lead frame described above.
日本国特許第６３０１６１８号公報Japanese Patent No. 6301618 日本国特許第６８１１１３６号公報Japanese Patent No. 6811136
　上記したリードフレームを始めとする電気・電子部品では、シリコンチップの装着や配線基板への実装を容易にする目的で、銅合金から成る銅合金材の表面に半田めっき層や銀めっき層を設けることが一般的に行われている。銅合金材の表面にめっき層を設ける場合、その前処理として、その表面の酸化層や加工変質層を酸性液で化学的に溶解する化学研磨が一般的に行われている。たとえば、Ｃ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材の場合、硫酸と過酸化水素を含む酸性液（化学研磨液）による化学研磨が一般的である。このＣ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材では、後述する銅合金材の表面に残留するスマット（以下、残留スマットという。）の問題はない。 In the electric and electronic parts including the lead frame described above, a solder plating layer or a silver plating layer is provided on the surface of the copper alloy material made of copper alloy for the purpose of facilitating mounting of the silicon chip and mounting on the wiring board. that is commonly done. When providing a plated layer on the surface of a copper alloy material, chemical polishing is generally performed as a pretreatment for chemically dissolving an oxidized layer or a work-affected layer on the surface with an acid solution. For example, in the case of a copper alloy material made of a Cu--Fe--Zn--P based copper alloy such as C1940, chemical polishing with an acidic liquid (chemical polishing liquid) containing sulfuric acid and hydrogen peroxide is common. A copper alloy material made of a Cu--Fe--Zn--P based copper alloy such as C1940 does not have the problem of smut remaining on the surface of the copper alloy material (hereinafter referred to as residual smut), which will be described later.
　しかし、より高強度な銅合金から成る銅合金材、たとえば、Ｃ７０２５などのＣｕ－Ｎｉ－Ｓｉ系の銅合金から成る銅合金材の場合、Ｃ１９４０と同質の化学研磨液を用いるとＮｉとＳｉを含む化合物の粒子が溶解されない。そのため、ＮｉとＳｉを含む化合物の粒子が残渣（スマット）となって、銅合金材の表面に大量に残留する。銅合金材の表面の残留スマットは、化学研磨後の一般的な表面洗浄では容易に除去されない。そのため、その後に設けためっき層にスマットが混在し、銅合金材の外観や特性に大きな影響を及ぼすことおそれがある。 However, in the case of a copper alloy material made of a higher-strength copper alloy, for example, a copper alloy material made of a Cu—Ni—Si-based copper alloy such as C7025, Ni and Si are removed when a chemical polishing liquid of the same quality as C1940 is used. Particles of compound containing are not dissolved. Therefore, the particles of the compound containing Ni and Si become residue (smut) and remain on the surface of the copper alloy material in large quantities. Residual smut on the surface of copper alloy materials is not easily removed by general surface cleaning after chemical polishing. Therefore, smut may be mixed in the plated layer provided thereafter, which may greatly affect the appearance and characteristics of the copper alloy material.
　このＣ７０２５などのより高強度な銅合金材の表面の残留スマットの問題に対して、たとえば、特許文献１は、ＮｉとＳｉを含む化合物の粒子径や形状を制御して銅合金材の表面の残留スマットの残存面積率を３％未満にする方法を提案し、質量％で示す含有率で、Ｎｉ：２．０～６．０％、Ｓｉ：０．３～２．０％、Ｃｒ：０～１．０％、Ｍｇ：０～１．０％、Ｓｎ：０～０．８％およびＺｎ：０～０．８％を含有し、残部がＣｕおよび不純物からなる銅合金材を開示する。また、特許文献２は、銅合金材の表面の残留スマットを適量にすることで、銅合金材の表面に凹凸を残して樹脂との密着性を向上させる方法を提案し、質量％で示す含有率で、Ｎｉ：１．５～４．５％、Ｓｉ：０．４～１．１％を含有し、残部がＣｕおよび不純物から成り、８００ＭＰａ以上の引張強さと３０％ＩＡＣＳ以上の導電率を有するＣｕ－Ｎｉ－Ｓｉ系の銅合金条を開示する。しかし、特許文献１、２のいずれの提案も、銅合金材の表面の残留スマットを許容するものであって、銅合金材の表面に残留スマットが発生する問題が根本的に解決されていない。 To solve the problem of residual smut on the surface of higher-strength copper alloy materials such as C7025, for example, Patent Document 1 discloses controlling the particle size and shape of a compound containing Ni and Si to improve the surface of the copper alloy material. We propose a method to reduce the residual area ratio of residual smut to less than 3%, and the content percentages expressed in mass% are Ni: 2.0 to 6.0%, Si: 0.3 to 2.0%, and Cr: 0. Disclosed is a copper alloy material containing ~1.0%, Mg: 0-1.0%, Sn: 0-0.8% and Zn: 0-0.8%, the balance being Cu and impurities. In addition, Patent Document 2 proposes a method for improving adhesion with resin by leaving unevenness on the surface of the copper alloy material by adjusting the amount of residual smut on the surface of the copper alloy material. At a rate, Ni: 1.5 to 4.5%, Si: 0.4 to 1.1%, the balance is Cu and impurities, and has a tensile strength of 800 MPa or more and an electrical conductivity of 30% IACS or more. A Cu--Ni--Si based copper alloy strip is disclosed. However, both the proposals of Patent Documents 1 and 2 allow residual smut on the surface of the copper alloy material, and do not fundamentally solve the problem of residual smut occurring on the surface of the copper alloy material.
　そこで、この発明により、Ｃ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材と同様に上記した残留スマットの問題がなく、より高強度なＣ７０２５などのＣｕ－Ｎｉ－Ｓｉ系の銅合金から成る銅合金材と略同等の引張強さと導電率を有し、望ましくは曲げ加工性の良い、銅合金材および銅合金材の製造方法を提供する。なお、上記したような添加元素（たとえば、Ｎｉ、Ｓｉ、Ｃｒ、Ｍｇ、Ｓｎ、Ｚｎなど）を多く含有する銅合金材は、一般に圧延加工性が悪く、特に熱間圧延の段階で割れが発生しやすい。そこで、望ましくは、この発明により、圧延加工性の良い、特に熱間圧延の段階で割れにくい、銅合金材および銅合金材の製造方法を提供する。 Therefore, according to the present invention, there is no problem of residual smut as with copper alloy materials made of Cu-Fe-Zn-P-based copper alloys such as C1940, and higher strength Cu-Ni-Si-based materials such as C7025 Provided are a copper alloy material having approximately the same tensile strength and electrical conductivity as those of the copper alloy material of (1) and desirably good bending workability, and a method for producing the copper alloy material. In addition, copper alloy materials containing a large amount of additive elements such as those described above (for example, Ni, Si, Cr, Mg, Sn, Zn, etc.) generally have poor rolling workability, and cracks occur particularly at the stage of hot rolling. It's easy to do. Therefore, the present invention desirably provides a copper alloy material and a method for producing a copper alloy material that are excellent in rolling workability, particularly resistant to cracking during hot rolling.
　この発明者は、残留スマットの問題がないＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材と、残留スマットの問題があるＣｕ－Ｎｉ－Ｓｉ系の銅合金から成る銅合金材とについて、その組織の形態や性状、機械的や電気的な性質、製造条件などを多面的に精査した。その結果、Ｃｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金の合金組成に更なる工夫を加えるとともに、その銅合金から成る銅合金材の製造条件に更なる工夫を加えることで、上記の課題が解決できることを見出し、この発明に想到した。 The inventor has developed a copper alloy material composed of a Cu--Fe--Zn--P-based copper alloy having no problem of residual smut, and a copper alloy material composed of a Cu--Ni--Si-based copper alloy having a problem of residual smut. We investigated the morphology and properties of the structure, mechanical and electrical properties, manufacturing conditions, etc. from various aspects. As a result, the above problem was solved by further devising the alloy composition of the Cu-Fe-Zn-P-based copper alloy and further devising the manufacturing conditions of the copper alloy material made of the copper alloy. I found that it can be done, and came up with this invention.
　すなわち、この発明に係る銅合金材は、質量％で示す含有率で、含有必須元素として、１．６％以上２．６％以下のＦｅと、０．０１％以上０．３％以下のＰと、０．０１％以上０．３％以下のＺｎと、０．３％以上０．８％以下のＳｎとを含有し、残部がＣｕおよび不純物元素から成り、２０℃の温度環境下において、６２０ＭＰａ以上の引張強さを有するとともに、４０．０％ＩＡＣＳ以上の導電率を有する、銅合金材である。 That is, the copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe and 0.01% or more and 0.3% or less of P and 0.01% or more and 0.3% or less of Zn, 0.3% or more and 0.8% or less of Sn, the balance being Cu and impurity elements, in a temperature environment of 20 ° C., A copper alloy material having a tensile strength of 620 MPa or more and an electrical conductivity of 40.0% IACS or more.
　この発明に係る銅合金材は、質量％で示す含有率で、０．０１％以上０．２０％以下のＰを含有する、銅合金材であることが好ましい。 The copper alloy material according to the present invention is preferably a copper alloy material containing 0.01% or more and 0.20% or less of P in terms of mass % content.
　この発明に係る銅合金材は、質量％で示す含有率で、含有必須元素として、前記Ｆｅと前記Ｐと前記Ｚｎと前記Ｓｎと、さらに、０．００２％以上０．０２５％以下のＭｎとを含有し、残部がＣｕおよび不純物元素から成り、９５０℃の温度環境下において、２０％を超える破断伸びを有する、銅合金材であることが好ましい。 In the copper alloy material according to the present invention, the content in mass % is, as essential elements, Fe, P, Zn, and Sn, and Mn of 0.002% or more and 0.025% or less. with the balance being Cu and impurity elements, and having a breaking elongation of more than 20% in a temperature environment of 950°C.
　この発明に係る銅合金材は、質量％で示す含有率で、（Ｍｎ含有率＋不純物元素の総含有率）／（Ｆｅ含有率＋Ｐ含有率＋Ｓｎ含有率）×１００で求まる値が、１．１以下である、銅合金材であることが好ましい。 In the copper alloy material according to the present invention, the content in mass % is (Mn content + total impurity element content) / (Fe content + P content + Sn content) x 100. 1 or less, preferably a copper alloy material.
　また、この発明に係る銅合金材の製造方法は、質量％で示す含有率で、含有必須元素として、１．６％以上２．６％以下のＦｅと、０．０１％以上０．３％以下のＰと、０．０１％以上０．３％以下のＺｎと、０．３％以上０．８％以下のＳｎとを含有し、残部がＣｕおよび不純物元素から成る、銅合金鋳造材を作製する溶解鋳造工程と、前記銅合金鋳造材を用いて熱間圧延を行って熱間圧延材を作製する熱間圧延工程と、前記熱間圧延材を用いて冷間圧延を行って第１冷間圧延材を作製する第１冷間圧延工程と、前記第１冷間圧延材に対して５００℃以上６００℃以下の温度で４ｈ以下の加熱保持を行って第１熱処理材を作製する第１熱処理工程と、前記第１熱処理材を用いて２０％以上９０％以下の圧延加工度で冷間圧延を行って第２冷間圧延材を作製する第２冷間圧延工程と、前記第２冷間圧延材に対して３８０℃以上４８０℃以下の温度で１ｈ以上１２ｈ以下の加熱保持を行って第２熱処理材を作製する第２熱処理工程と、前記第２熱処理材を用いて６０％以上８０％以下の圧延加工度で冷間圧延を行って第３冷間圧延材を作製する第３冷間圧延工程と、前記第３冷間圧延材に対して２５０℃以上３８０℃以上の温度で４ｈ以下の加熱保持を行って銅合金材を作製する第３熱処理工程と、を有し、前記溶解鋳造工程、前記熱間圧延工程、前記第１冷間圧延工程、前記第１熱処理工程、前記第２冷間圧延工程、前記第２熱処理工程、前記第３冷間圧延工程、および、前記第３熱処理工程の順に実施することにより、２０℃の温度環境下において、６２０ＭＰａ以上の引張強さを有するとともに、４０．０％ＩＡＣＳ以上の導電率を有する、銅合金材を作製する、銅合金材の製造方法である。 In addition, in the method for producing a copper alloy material according to the present invention, the content in mass% is 1.6% or more and 2.6% or less of Fe and 0.01% or more and 0.3% as essential elements. A copper alloy casting material containing the following P, 0.01% or more and 0.3% or less of Zn, 0.3% or more and 0.8% or less of Sn, and the balance being Cu and impurity elements A melting and casting process for producing, a hot rolling process for producing a hot rolled material by performing hot rolling using the copper alloy cast material, and a cold rolling process using the hot rolled material to perform the first A first cold-rolling step of producing a cold-rolled material, and a first heat-treated material is produced by heating and holding the first cold-rolled material at a temperature of 500 ° C. or higher and 600 ° C. or lower for 4 hours or less. 1 heat treatment step, a second cold rolling step of cold rolling at a rolling reduction rate of 20% or more and 90% or less using the first heat treated material to produce a second cold rolled material, A second heat treatment step of producing a second heat treated material by heating and holding the cold rolled material at a temperature of 380 ° C. or higher and 480 ° C. or lower for 1 hour or more and 12 hours or less, and 60% or more using the second heat treated material. A third cold rolling step of cold rolling at a rolling reduction rate of 80% or less to produce a third cold rolled material, and subjecting the third cold rolled material to a temperature of 250 ° C. or higher and 380 ° C. or higher. a third heat treatment step of producing a copper alloy material by heating and holding for 4 hours or less, wherein the melting and casting step, the hot rolling step, the first cold rolling step, the first heat treatment step, the By performing the second cold rolling step, the second heat treatment step, the third cold rolling step, and the third heat treatment step in this order, a tensile strength of 620 MPa or more is obtained in a temperature environment of 20 ° C. and having an electrical conductivity of 40.0% IACS or higher.
　この発明に係る銅合金材の製造方法は、質量％で示す含有率で、０．０１％以上０．２０％以下のＰを含有する、銅合金材を作製する、銅合金材の製造方法であることが好ましい。 A method for producing a copper alloy material according to the present invention is a method for producing a copper alloy material containing 0.01% or more and 0.20% or less of P in terms of mass% content. Preferably.
　この発明に係る銅合金材の製造方法は、質量％で示す含有率で、含有必須元素として、前記Ｆｅと前記Ｐと前記Ｚｎと前記Ｓｎと、さらに、０．００２％以上０．０２５％以下のＭｎとを含有し、残部がＣｕおよび不純物元素から成る、銅合金鋳造材を作製する溶解鋳造工程とし、この後に、前記熱間圧延工程、前記第１冷間圧延工程、前記第１熱処理工程、前記第２冷間圧延工程、前記第２熱処理工程、前記第３冷間圧延工程、および、前記第３熱処理工程の順に実施することにより、
　９５０℃の温度環境下において、２０％を超える破断伸びを有する、銅合金材を作製する、銅合金材の製造方法であることが好ましい。 In the method for producing a copper alloy material according to the present invention, the content in mass % is, as the essential elements, Fe, P, Zn, and Sn, and 0.002% or more and 0.025% or less A melting and casting step for producing a copper alloy casting material containing Mn and the balance consisting of Cu and impurity elements, followed by the hot rolling step, the first cold rolling step, and the first heat treatment step , the second cold rolling step, the second heat treatment step, the third cold rolling step, and the third heat treatment step in this order,
It is preferable that the method for producing a copper alloy material produces a copper alloy material having a breaking elongation of more than 20% in a temperature environment of 950°C.
　この発明に係る銅合金材の製造方法は、質量％で示す含有率で、（Ｍｎ含有率＋不純物元素の総含有率）／（Ｆｅ含有率＋Ｐ含有率＋Ｓｎ含有率）×１００で求まる値が、１．１以下である、銅合金鋳造材を作製する溶解鋳造工程とする、銅合金材の製造方法であることが好ましい。 In the method for producing a copper alloy material according to the present invention, the content in mass% is (Mn content + total impurity element content) / (Fe content + P content + Sn content) x 100. , 1.1 or less.
　この発明によれば、Ｃ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材と同様に上記した残留スマットの問題がなく、より高強度なＣ７０２５などのＣｕ－Ｎｉ－Ｓｉ系の銅合金から成る銅合金材と略同等の引張強さと導電率を有する、銅合金材および銅合金材の製造方法を提供することができる。また、この発明によれば、構成の適切な選択により、曲げ加工性の良い、銅合金材および銅合金材の製造方法や、圧延加工性の良い、特に熱間圧延の段階で割れにくい、銅合金材および銅合金材の製造方法を提供することができる。 According to the present invention, there is no problem of residual smut as with a copper alloy material made of a Cu-Fe-Zn-P-based copper alloy such as C1940, and a higher strength Cu-Ni-Si-based material such as C7025 It is possible to provide a copper alloy material and a method for producing a copper alloy material that have substantially the same tensile strength and electrical conductivity as a copper alloy material made of a copper alloy of. In addition, according to the present invention, by appropriately selecting the configuration, a copper alloy material with good bending workability and a method for producing a copper alloy material, A method for manufacturing an alloy material and a copper alloy material can be provided.
この発明に係る銅合金材の製造方法における主工程の流れを示す図である。1 is a diagram showing a flow of main steps in a method of manufacturing a copper alloy material according to the present invention; FIG.
　以下、この発明に係る銅合金材の構成について説明し、次いで、銅合金材の製造方法について図１に示す主工程の流れに沿って説明する。なお、この発明に係る銅合金材および銅合金材の製造方法は、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれると解することが相当である。なお、元素の含有率（数値）や材料の化学成分（数値）は、特段の断りがない限り、質量％で記載する。 The structure of the copper alloy material according to the present invention will be described below, and then the method for manufacturing the copper alloy material will be described along the flow of the main steps shown in FIG. It should be noted that the copper alloy material and the method for producing the copper alloy material according to the present invention are indicated by the scope of claims, and can be understood to include all modifications within the meaning and scope of equivalents of the scope of the claims. Considerable. The contents (numerical values) of elements and the chemical components (numerical values) of materials are expressed in % by mass unless otherwise specified.
　この発明に係る銅合金材は、含有必須元素として、１．６％以上２．６％以下のＦｅ（鉄）と、０．０１％以上０．３％以下のＰ（燐）と、０．０１％以上０．３％以下のＺｎ（亜鉛）と、０．３％以上０．８％以下（好ましくは、０．３％を超えて０．８％以下）のＳｎ（錫）とを含有し、残部がＣｕ（銅）および不純物元素から成り、２０℃の温度環境下において、６２０ＭＰａ以上（好ましくは６２５ＭＰａ以上、より好ましくは６３０ＭＰａ以上）の引張強さを有するとともに、４０．０％ＩＡＣＳ以上（好ましくは４５．０％ＩＡＣＳ以上）の導電率を有する。なお、この発明に係る銅合金材を構成する銅合金は、合金組成の観点からいえば、Ｃｕ－Ｆｅ－Ｐ－Ｚｎ－Ｓｎ系の銅合金である。 The copper alloy material according to the present invention contains, as essential elements, Fe (iron) of 1.6% or more and 2.6% or less, P (phosphorus) of 0.01% or more and 0.3% or less, and 0.5% or more. Contains 01% or more and 0.3% or less of Zn (zinc) and 0.3% or more and 0.8% or less of Sn (tin) (preferably more than 0.3% and 0.8% or less) The balance consists of Cu (copper) and impurity elements, and has a tensile strength of 620 MPa or more (preferably 625 MPa or more, more preferably 630 MPa or more) in a temperature environment of 20 ° C. and 40.0% IACS or more. (preferably 45.0% IACS or higher). The copper alloy constituting the copper alloy material according to the present invention is a Cu--Fe--P--Zn--Sn based copper alloy from the viewpoint of alloy composition.
　この発明に係る銅合金材は、好ましくは、０．０１％以上０．２０％以下のＰを含有する。 The copper alloy material according to the present invention preferably contains 0.01% or more and 0.20% or less of P.
　この発明に係る銅合金材は、好ましくは、含有必須元素として、前記Ｆｅ（１．６％以上２．６％以下）と、前記Ｐ（０．０１％以上０．３％以下、好ましくは０．０１％以上０．２０％以下）と、前記Ｚｎ（０．０１％以上０．３％以下）と、前記Ｓｎ（０．３％以上０．８％以下、好ましくは０．３％を超えて０．８％以下）と、さらに、０．００２％以上０．０２５％以下のＭｎとを含有し、残部がＣｕおよび不純物元素から成り、９５０℃の温度環境下において、２０％を超える破断伸びを有する。 The copper alloy material according to the present invention preferably contains Fe (1.6% or more and 2.6% or less) and P (0.01% or more and 0.3% or less, preferably 0 .01% or more and 0.20% or less), the Zn (0.01% or more and 0.3% or less), and the Sn (0.3% or more and 0.8% or less, preferably more than 0.3% 0.8% or less), and furthermore, 0.002% or more and 0.025% or less of Mn, the balance being Cu and impurity elements, and breaking more than 20% in a temperature environment of 950 ° C. have elongation.
　この発明に係る銅合金材は、好ましくは、（Ｍｎ含有率＋不純物元素の総含有率）／（Ｆｅ含有率＋Ｐ含有率＋Ｓｎ含有率）×１００で求まる値（以下、「ＭＩ値）という。）が、１．１以下である。 The copper alloy material according to the present invention preferably has a value obtained by (Mn content + total content of impurity elements)/(Fe content + P content + Sn content) x 100 (hereinafter referred to as "MI value"). ) is less than or equal to 1.1.
　この発明に係る銅合金材を構成する銅合金に含有される元素の限定理由は、以下の通りである。 The reasons for limiting the elements contained in the copper alloy constituting the copper alloy material according to the present invention are as follows.
＜Ｆｅ（鉄）＞
　この発明に係る銅合金材は、含有必須元素として、１．６％以上２．６％以下のＦｅを含有する。銅合金材において、Ｆｅは、銅合金のＣｕを主とする母相中に固溶する。また、一部のＦｅは、ＦｅまたはＦｅとＰを含む化合物として、母相中に分散析出する。こうしたＦｅの作用は、銅合金材の機械的強さや耐熱性の向上に寄与する。それゆえ、適量のＦｅを含有する銅合金材は、導電性を相応に維持しながらより高い機械的強さや耐熱性を有することができる。 <Fe (iron)>
The copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe as an essential element. In the copper alloy material, Fe dissolves in a matrix mainly composed of Cu of the copper alloy. A part of Fe is dispersed and precipitated in the matrix phase as a compound containing Fe or Fe and P. Such action of Fe contributes to the improvement of the mechanical strength and heat resistance of the copper alloy material. Therefore, a copper alloy material containing an appropriate amount of Fe can have higher mechanical strength and heat resistance while reasonably maintaining electrical conductivity.
　なお、銅合金材に含有するＦｅが過度に少ない（１．６％未満）場合、上記したＦｅの作用効果が十分に発揮されない。また、銅合金材に含有するＦｅが過度に多い（２．６％超）場合、後述する銅合金鋳造材にＦｅの過大な晶出物が形成され、表面清浄性の劣化や加工割れの原因になることがある。この観点で、この発明に係る銅合金材は、Ｆｅを１．６％以上２．６％以下とし、好ましくは、よりバランスの良い特性を得るために２．１％以上２．４％以下とする。また、この発明に係る銅合金材は、Ｆｅを１．６％以上２．６％以下（好ましくは、２．１％以上２．４％以下）とし、後述するようにＳｎ含有率を考慮すれば、引張強さと導電率のバランスが好ましいものとなる。この場合、たとえば、６３０ＭＰａ以上の引張強さと４５．０％ＩＡＣＳ以上の導電率を有する銅合金材となる。 If the amount of Fe contained in the copper alloy material is excessively low (less than 1.6%), the effects of Fe described above are not sufficiently exhibited. In addition, when the amount of Fe contained in the copper alloy material is excessively large (exceeding 2.6%), excessive Fe crystallized substances are formed in the copper alloy cast material described later, which causes deterioration of surface cleanliness and work cracks. can be From this point of view, the copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe, preferably 2.1% or more and 2.4% or less in order to obtain more well-balanced characteristics. do. In addition, the copper alloy material according to the present invention contains 1.6% or more and 2.6% or less of Fe (preferably 2.1% or more and 2.4% or less), and the Sn content is considered as described later. A good balance between tensile strength and electrical conductivity is obtained. In this case, for example, the copper alloy material has a tensile strength of 630 MPa or more and an electrical conductivity of 45.0% IACS or more.
＜Ｐ（燐）＞
　この発明に係る銅合金材は、含有必須元素として、０．０１％以上０．３％以下のＰを含有する。銅合金材において、Ｐは、後述する溶解鋳造工程で溶融金属（溶湯）に存在する余分な酸素を取り除く脱酸剤として作用する。また、一部のＰはＦｅとＰを含む化合物を形成し、銅合金のＣｕを主とする母相中に分散析出する。こうしたＰの作用は、銅合金材の機械的強さや耐熱性の向上に寄与する。それゆえ、適量のＰを含有する銅合金材は、導電性を相応に維持しながらより高い機械的強さや耐熱性を有することができる。 <P (Phosphorus)>
The copper alloy material according to the present invention contains 0.01% or more and 0.3% or less of P as an essential element. In the copper alloy material, P acts as a deoxidizing agent that removes excess oxygen present in the molten metal (molten metal) in the melting and casting process, which will be described later. In addition, a part of P forms a compound containing Fe and P, and is dispersed and precipitated in the matrix phase mainly composed of Cu of the copper alloy. Such action of P contributes to the improvement of the mechanical strength and heat resistance of the copper alloy material. Therefore, a copper alloy material containing an appropriate amount of P can have higher mechanical strength and heat resistance while maintaining the electrical conductivity accordingly.
　なお、銅合金材に含有するＰが過度に少ない（０．０１％未満）場合、上記したＰの作用効果が十分に発揮されない。また、銅合金材に含有するＰが過度に多い（０．３％超）場合、後述する熱間圧延工程での熱間加工性の低下や銅合金材の導電率の低下の原因になることがある。この観点で、この発明に係る銅合金材は、Ｐを０．０１％以上０．３％以下、より好ましくは、曲げ加工性の向上のために０．０１％以上０．２０％以下とする。 It should be noted that if the amount of P contained in the copper alloy material is excessively low (less than 0.01%), the action and effect of P described above cannot be sufficiently exhibited. In addition, when the P content in the copper alloy material is excessively large (exceeding 0.3%), it may cause a decrease in hot workability in the hot rolling process described later and a decrease in the electrical conductivity of the copper alloy material. There is From this point of view, the copper alloy material according to the present invention has a P content of 0.01% or more and 0.3% or less, more preferably 0.01% or more and 0.20% or less for improving bending workability. .
＜Ｚｎ（亜鉛）＞
　この発明に係る銅合金材は、含有必須元素として、０．０１％以上０．３％以下のＺｎを含有する。銅合金材において、Ｚｎは、銅合金材の表面の半田に対する濡れ性を向上させるとともに、銅合金材の表面に設けた半田めっき層の耐候性を向上させる。こうしたＺｎの作用は、上記したリードフレームなどのように銅合金材の表面に半田めっき層を設ける場合には特に必要とされる。それゆえ、適量のＺｎを含有する銅合金材は、実用上、利用可能性が高い。 <Zn (zinc)>
The copper alloy material according to the present invention contains 0.01% or more and 0.3% or less of Zn as an essential element. In the copper alloy material, Zn improves the wettability of the surface of the copper alloy material to solder and improves the weather resistance of the solder-plated layer provided on the surface of the copper alloy material. Such an effect of Zn is particularly required when a solder plating layer is provided on the surface of a copper alloy material such as the lead frame described above. Therefore, a copper alloy material containing an appropriate amount of Zn has high practical applicability.
　なお、銅合金材に含有するＺｎが過度に少ない（０．０１％未満）場合、上記したＺｎの作用効果が十分に発揮されない。また、銅合金材に含有するＺｎが過度に多い（０．３％超）場合、上記したＺｎの作用効果が飽和するとともに、銅合金材の導電率の低下の原因になることがある。この観点で、この発明に係る銅合金材は、Ｚｎを０．０１％以上０．３％以下とし、好ましくは、よりバランスの良い特性を得るために０．０５％以上０．２％以下とする。 If the copper alloy material contains too little Zn (less than 0.01%), the above effects of Zn cannot be sufficiently exhibited. Moreover, when the Zn content in the copper alloy material is excessively large (exceeding 0.3%), the effects of Zn described above are saturated, and this may cause a decrease in electrical conductivity of the copper alloy material. From this point of view, the copper alloy material according to the present invention contains 0.01% or more and 0.3% or less of Zn, preferably 0.05% or more and 0.2% or less in order to obtain more well-balanced properties. do.
＜Ｓｎ（錫）＞
　この発明に係る銅合金材は、含有必須元素として、０．３％以上０．８％以下（好ましくは、０．３％を超えて０．８％以下）のＳｎを含有する。銅合金材において、Ｓｎは、銅合金のＣｕを主とする母相中に固溶し、銅合金材の機械的強さや耐熱性の更なる向上に寄与する。そのため、適量のＳｎを含有する銅合金材は、適量のＳｎを含有しない銅合金材と比べて、導電性を相応に維持しながらより高い機械的強さや耐熱性を有することができる。このＳｎの作用を利用し、Ｃｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材の機械的強さをＣｕ－Ｎｉ－Ｓｉ系の銅合金から成る銅合金材と略同等の水準に引き上げることができる。なお、このＳｎは、上記したＣ１９４０やＣ７０２５には添加されない。また、Ｃｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材が更に適量のＳｎを含有させても、上記した残留スマットの問題は発生しない。この点は、後述する表１などを参照されたい。 <Sn (tin)>
The copper alloy material according to the present invention contains 0.3% or more and 0.8% or less (preferably, more than 0.3% and 0.8% or less) of Sn as an essential element. In a copper alloy material, Sn forms a solid solution in the parent phase of the copper alloy, which is mainly composed of Cu, and contributes to further improvement of the mechanical strength and heat resistance of the copper alloy material. Therefore, a copper alloy material containing an appropriate amount of Sn can have higher mechanical strength and heat resistance while maintaining a corresponding amount of electrical conductivity, compared to a copper alloy material that does not contain an appropriate amount of Sn. Using the action of Sn, the mechanical strength of a copper alloy material made of a Cu-Fe-Zn-P-based copper alloy is brought to a level substantially equivalent to that of a copper alloy material made of a Cu-Ni-Si-based copper alloy. can be lifted. In addition, this Sn is not added to C1940 and C7025 described above. Further, even if a copper alloy material made of a Cu--Fe--Zn--P system copper alloy further contains an appropriate amount of Sn, the problem of residual smut does not occur. For this point, refer to Table 1, etc., which will be described later.
　なお、銅合金材に含有するＳｎが過度に少ない（０．３％未満）場合、上記したＳｎの作用効果が十分に発揮されない。また、銅合金材に含有するＳｎが過度に多い（０．８％超）場合、銅合金材の機械的強さはより向上されるが、銅合金材の導電率が大きく低下する原因になる。この観点で、この発明に係る銅合金材は、Ｓｎを０．３％以上０．８％以下とし、好ましくは６２５ＭＰａ以上の引張強さを安定的に得るために０．３％を超えて０．８％以下とする。この点は、後述するＳｎの影響の項も参照されたい。また、この発明に係る銅合金材は、Ｓｎを０．５％以上０．７％以下とし、Ｆｅ含有率を上記のように考慮すれば、引張強さと導電率のバランスが好ましいものとなる。この場合、たとえば、６３０ＭＰａ以上の引張強さと４５．０％ＩＡＣＳ以上の導電率を有する銅合金材となる。 It should be noted that if the amount of Sn contained in the copper alloy material is excessively low (less than 0.3%), the effects of Sn cannot be sufficiently exhibited. In addition, when the amount of Sn contained in the copper alloy material is excessively large (exceeding 0.8%), the mechanical strength of the copper alloy material is further improved, but the electrical conductivity of the copper alloy material is greatly reduced. . From this point of view, the copper alloy material according to the present invention has a Sn content of 0.3% or more and 0.8% or less, preferably more than 0.3% and 0 in order to stably obtain a tensile strength of 625 MPa or more. .8% or less. For this point, refer also to the section on the effect of Sn, which will be described later. Further, the copper alloy material according to the present invention has a preferable balance between tensile strength and electrical conductivity when the Sn content is 0.5% or more and 0.7% or less and the Fe content is considered as described above. In this case, for example, the copper alloy material has a tensile strength of 630 MPa or more and an electrical conductivity of 45.0% IACS or more.
＜Ｍｎ（マンガン）＞
　この発明に係る銅合金材は、含有必須元素として、ＦｅとＰとＺｎとＳｎとを上記範囲で含有し、好ましくは、さらに、０．００２％以上０．０２５％以下のＭｎを含有する。この発明に係る銅合金材は、上記したように、Ｃｕ－Ｆｅ－Ｐ－Ｚｎ－Ｓｎ系の銅合金からなる銅合金材である。この銅合金材に含有するＦｅとＰは、含有必須元素である一方、上記したように加工割れや熱間加工性の低下に係る元素である。また、この銅合金材は、一般的に使用される製造原料（銅材料）に由来して、不純物元素のＳ（硫黄）を含有する可能性がある。この銅合金材は、Ｓの固溶に起因して、圧延加工性が低下し、特に熱間圧延の段階での割れが発生しやすくなる。。そこで、この銅合金材では、好ましくは、含有必須元素として、さらにＭｎを含有し、積極的にＭｎＳを生成させることより、固溶状態になるＳを低減する。 <Mn (manganese)>
The copper alloy material according to the present invention contains, as essential elements, Fe, P, Zn, and Sn within the above ranges, and preferably 0.002% or more and 0.025% or less of Mn. The copper alloy material according to the present invention is, as described above, a copper alloy material made of a Cu--Fe--P--Zn--Sn based copper alloy. While Fe and P contained in this copper alloy material are essential elements, they are also elements that cause work cracks and deterioration of hot workability as described above. In addition, this copper alloy material may contain S (sulfur), which is an impurity element, derived from a generally used manufacturing raw material (copper material). Due to the solid solution of S, the copper alloy material has poor rolling workability, and cracks are likely to occur particularly at the stage of hot rolling. . Therefore, the copper alloy material preferably further contains Mn as an essential element to actively generate MnS, thereby reducing the amount of S that forms a solid solution.
　この銅合金材の一般的な製造原料に含有するＳは、実用上、０．００１％～０．００５％程度と考えることができる。ＭｎＳの組成比（Ｍｎ：Ｓ）は、原子比で１：１、質量比で６３：３７である。したがって、Ｓの全量がＭｎと反応すると仮定すれば、質量比で、Ｓの約１．７倍のＭｎが必要になる。たとえば、質量％で、０．００１％以上０．００５％以下のＳを含有する銅合金材は、計算上、０．００１７％以上０．００８５％以下のＭｎを含有する必要になる。しかし、実際に、Ｍｎの全量がＳと反応してＭｎＳを生成するとは限らない。そのため、Ｓ量に対して十分に余裕のあるＭｎ量とし、Ｓに対して２倍～５倍（質量比）のＭｎを含有させることが実用的である。この観点から、この発明に係る銅合金材では、０．００１％以上０．００５％以下のＳの含有が予測される場合、好ましくはＳ量に対応させて、Ｍｎを０．００２％以上０．０２５％以下の範囲で設定する。また、Ｓが０．００２％以下であれば、好ましくはＳ量に対応させて、Ｍｎを０．０１０％以下の範囲で設定する。これにより、圧延加工性の良い、特に熱間圧延の段階で割れにくい、銅合金材となる。 Practically, the S content in the raw material for general production of this copper alloy material can be considered to be about 0.001% to 0.005%. The composition ratio (Mn:S) of MnS is 1:1 in atomic ratio and 63:37 in mass ratio. Therefore, assuming that the entire amount of S reacts with Mn, about 1.7 times as much Mn as S is required in mass ratio. For example, a copper alloy material containing 0.001% or more and 0.005% or less of S in mass % needs to contain 0.0017% or more and 0.0085% or less of Mn in terms of calculation. However, not all of the Mn actually reacts with S to form MnS. Therefore, it is practical to set the amount of Mn sufficiently large relative to the amount of S, and to contain Mn two to five times the amount of S (mass ratio). From this point of view, in the copper alloy material according to the present invention, when the S content is expected to be 0.001% or more and 0.005% or less, it is preferable that Mn is 0.002% or more and 0.002% or more in correspondence with the S amount. Set within a range of 0.025% or less. Moreover, if S is 0.002% or less, Mn is preferably set in the range of 0.010% or less corresponding to the amount of S. As a result, the copper alloy material has good rolling workability and is particularly resistant to cracking during hot rolling.
＜Ｃｕ（銅）＞
　この発明に係る銅合金材は、上記した含有必須元素のＦｅとＰとＺｎとＳｎを除く残部が、Ｃｕおよび不純物元素から成る。そして、さらにＭｎを含む場合、この発明に係る銅合金材は、上記した含有必須元素のＦｅとＰとＺｎとＳｎとＭｎを除く残部が、Ｃｕおよび不純物元素から成る。この銅合金材において、Ｃｕは、上記した含有必須元素の含有率に応じて、概ね９６％以上９８％以下の範囲で含有される。この銅合金材において、Ｃｕと上記した含有必須元素を除く残部は、不純物元素である。銅合金材において、Ｃｕ（銅）は、銅合金の母相を構成する主元素であり、最も多く含有されている。銅から成る銅材や銅合金から成る銅合金材は優れた導電率を有し、電気・電子部品の材料として多用されている。たとえば、ＪＩＳに規格されるＣ１０２０やＣ１１００などの無酸素銅から成る銅材は、１００％ＩＡＣＳ程度の導電率と１９５ＭＰａ（質別Ｏ）から３１５ＭＰａ（質別Ｈ）程度の引張強さを有する。また、Ｃ１９４０から成る銅合金材は、６０％ＩＡＣＳ以上１００％ＩＡＣＳ未満の導電率と２７５ＭＰａ（質別Ｏ３）から５９０ＭＰａ（質別ＥＳＨ）程度の引張強さを有する。また、Ｃ７０２５から成る銅合金材は、４５．０％ＩＡＣＳ程度の導電率と６５０ＭＰａ程度（質別１／２・Ｈ）の引張強さを有する。 <Cu (copper)>
The copper alloy material according to the present invention is composed of Cu and impurity elements except for Fe, P, Zn, and Sn, which are the above-described essential elements. When Mn is further included, the copper alloy material according to the present invention consists of Cu and impurity elements except for Fe, P, Zn, Sn, and Mn, which are the above-described essential elements. In this copper alloy material, Cu is contained in a range of approximately 96% or more and 98% or less according to the content of the essential elements described above. In this copper alloy material, the remainder excluding Cu and the above-described essential elements is impurity elements. In a copper alloy material, Cu (copper) is the main element that constitutes the parent phase of the copper alloy, and is contained in the largest amount. Copper materials made of copper and copper alloy materials made of copper alloys have excellent electrical conductivity and are widely used as materials for electrical and electronic parts. For example, a copper material made of oxygen-free copper such as C1020 or C1100 standardized by JIS has a conductivity of about 100% IACS and a tensile strength of about 195 MPa (temper O) to 315 MPa (temper H). A copper alloy material made of C1940 has an electrical conductivity of 60% IACS or more and less than 100% IACS and a tensile strength of about 275 MPa (O3 temper) to 590 MPa (ESH temper). A copper alloy material made of C7025 has an electrical conductivity of about 45.0% IACS and a tensile strength of about 650 MPa (temper classification 1/2·H).
＜不純物元素＞
　この発明に係る銅合金材は、不純物元素を含む。この不純物元素は、銅合金材の製造過程で不可避的に混入し、意図的に添加しない。この不純物元素は、使用する製造原料や製造設備などにも拠るが、たとえば、Ａｇ（銀）、Ｐｂ（鉛）、Ｎｉ（ニッケル）およびＳ（硫黄）などの元素が挙げられる。これらの不純物元素が過大に混入していると、銅合金材の諸特性（引張強さ、導電率、曲げ加工性など）を劣化させるおそれがある。また、この銅合金材において、上記したように、固溶状態となったＳは圧延加工性の低下、特に熱間圧延の段階での割れの原因になる。この観点で、銅合金材の不純物元素の含有率は可能な限り小さく抑制し、たとえば、合計で０．０５％以下、好ましくは０．０３％以下、より好ましくは０．０１％以下に抑制する。 <Impurity element>
The copper alloy material according to the present invention contains impurity elements. This impurity element is inevitably mixed in during the manufacturing process of the copper alloy material and is not intentionally added. The impurity elements depend on the manufacturing raw materials and manufacturing equipment used, but include elements such as Ag (silver), Pb (lead), Ni (nickel) and S (sulfur). If these impurity elements are excessively mixed, there is a risk of deteriorating various properties (tensile strength, electrical conductivity, bending workability, etc.) of the copper alloy material. In addition, in this copper alloy material, as described above, S in a solid solution state causes deterioration of rolling workability, particularly cracking at the stage of hot rolling. From this point of view, the content of impurity elements in the copper alloy material is suppressed as low as possible, for example, the total is suppressed to 0.05% or less, preferably 0.03% or less, more preferably 0.01% or less. .
　また、この発明に係る銅合金材において、上記したように、ＦｅおよびＰは、加工割れや熱間加工性の低下に係る。また、Ｓｎは、機械的強さや耐熱性に係る。また、Ａｇ、Ｐｂ、ＮｉおよびＳなどの不純物元素は、引張強さや曲げ加工性の劣化に係る。また、さらにＭｎを含有する場合、ＭｎとＳとの関係は、圧延加工性の低下や熱間圧延の段階での割れに係る。上記したＦｅ、Ｐ、Ｓｎ、ＭｎおよびＳなどの不純物元素の影響を総合的に考慮し、この発明に係る銅合金材は、Ｍｎを含有することが好ましい。その場合、好ましくは、（Ｍｎ含有率＋不純物元素の総含有率）／（Ｆｅ含有率＋Ｐ含有率＋Ｓｎ含有率）×１００で求まる値（以下、「ＭＩ値）という。）を考慮する。そして、ＭＩ値を、たとえば１．１以下（＞０）とし、好ましくは１．０以下（＞０）とする。これにより、この発明に係る銅合金材の圧延加工性（特に、熱間加工性）などを十分に高めることができる。 In addition, in the copper alloy material according to the present invention, as described above, Fe and P are related to work cracking and deterioration of hot workability. Further, Sn relates to mechanical strength and heat resistance. In addition, impurity elements such as Ag, Pb, Ni and S are related to deterioration of tensile strength and bending workability. Further, when Mn is further contained, the relationship between Mn and S relates to deterioration of rolling workability and cracking at the stage of hot rolling. Considering the effects of impurity elements such as Fe, P, Sn, Mn and S, the copper alloy material according to the present invention preferably contains Mn. In that case, preferably, the value obtained by (Mn content + total content of impurity elements)/(Fe content + P content + Sn content) x 100 (hereinafter referred to as "MI value") is considered. , the MI value is, for example, 1.1 or less (>0), preferably 1.0 or less (>0), thereby improving the rolling workability (especially hot workability) of the copper alloy material according to the present invention. ) can be sufficiently enhanced.
　この発明に係る銅合金材は、含有必須元素として、ＦｅとＰとＺｎとＳｎとを上記した範囲で含有し、残部がＣｕおよび不純物元素から成る。これにより、この銅合金材は、２０℃の温度環境下において、６２０ＭＰａ以上（好ましくは６２５ＭＰａ以上、より好ましくは６３０ＭＰａ以上）の引張強さを有するとともに４０．０％ＩＡＣＳ以上（好ましくは、４５．０％ＩＡＣＳ以上）の導電率を有し、後述するように残留スマットの発生が抑制される。この銅合金材は、上記した引張強さおよび導電率を有し、残留スマットの発生が抑制されるため、実用上、Ｃ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材や、より高強度のＣ７０２５から成る銅合金材の代替材として、十分に利用可能と考えられる。 The copper alloy material according to the present invention contains Fe, P, Zn, and Sn as essential elements within the ranges described above, with the balance being Cu and impurity elements. As a result, this copper alloy material has a tensile strength of 620 MPa or more (preferably 625 MPa or more, more preferably 630 MPa or more) and 40.0% IACS or more (preferably 45.0 MPa or more) in a temperature environment of 20°C. It has a conductivity of 0% IACS or more), and the generation of residual smut is suppressed as described later. This copper alloy material has the above-described tensile strength and conductivity, and since the generation of residual smut is suppressed, it is practically a copper alloy material made of a Cu-Fe-Zn-P-based copper alloy such as C1940. It is considered that it can be sufficiently used as a substitute material for a copper alloy material composed of C7025, which has a higher strength.
　また、この発明に係る銅合金材は、含有必須元素として、ＦｅとＰとＺｎとＳｎとＭｎとを上記した範囲で含有し、残部がＣｕおよび不純物元素から成る。これにより、この銅合金材は、９５０℃の温度環境下において、２０％を超える破断伸びを有し、圧延加工性が向上し、特に熱間圧延の段階で割れにくくなる。この銅合金材は、上記した引張強さ、導電率および破断伸びを有し、残留スマットの発生が抑制されるため、実用上、Ｃ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材や、より高強度のＣ７０２５から成る銅合金材の代替材として、十分に利用可能と考えられる。 In addition, the copper alloy material according to the present invention contains Fe, P, Zn, Sn, and Mn as essential elements within the ranges described above, with the balance being Cu and impurity elements. As a result, the copper alloy material has an elongation at break of more than 20% in a temperature environment of 950° C., improves rolling workability, and is particularly resistant to cracking during hot rolling. This copper alloy material has the above-mentioned tensile strength, electrical conductivity and elongation at break, and since the generation of residual smut is suppressed, it is practically made of a Cu-Fe-Zn-P-based copper alloy such as C1940. It is considered that it can be sufficiently used as a copper alloy material or a substitute material for a copper alloy material composed of C7025, which has a higher strength.
　この発明に係る銅合金材の引張強さは、主に、ＦｅまたはＦｅとＰを含む化合物の粒子の分散析出による析出強化と冷間圧延による加工硬化に依存するものである。この析出強化と加工硬化による銅合金組織の強化機構は、製造条件の特定によって制御可能である。析出強化の効果は、熱処理の保持条件を特定範囲に制御し、銅合金組織の変形の障害として作用可能な適度な大きさの粒子を均一的に分散析出させることにより得ることができる。加工硬化の効果は、冷間圧延の加工条件を特定範囲に制御し、銅合金組織の変形の障害として作用可能な転位を含む結晶の適度な蓄積により得ることができる。また、この発明に係る銅合金材の導電率は、実質的にＣｕに依存しているが、上記した粒子の析出により母相のＣｕ純度が高まる作用も利用している。 The tensile strength of the copper alloy material according to the present invention mainly depends on precipitation strengthening due to dispersed precipitation of particles of Fe or a compound containing Fe and P and work hardening due to cold rolling. The strengthening mechanism of the copper alloy structure by precipitation strengthening and work hardening can be controlled by specifying the manufacturing conditions. The effect of precipitation strengthening can be obtained by controlling the holding conditions of the heat treatment within a specific range and uniformly dispersing and precipitating particles of an appropriate size that can act as obstacles to the deformation of the copper alloy structure. The effect of work hardening can be obtained by controlling the working conditions of cold rolling within a specific range and by appropriately accumulating crystals containing dislocations that can act as obstacles to deformation of the copper alloy structure. In addition, although the electrical conductivity of the copper alloy material according to the present invention substantially depends on Cu, it also utilizes the action of increasing the purity of Cu in the parent phase due to the precipitation of the particles described above.
　Ｃｕ－Ｆｅ－Ｐ－Ｚｎ－Ｓｎ系の銅合金からなる銅合金材が、２０℃の温度環境下において、６２０ＭＰａ以上（好ましくは６２５ＭＰａ以上、より好ましくは６３０ＭＰａ以上）の引張強さを有するとともに、４０．０％ＩＡＣＳ以上（好ましくは、４５．０％ＩＡＣＳ以上）の導電率を有するためには、その製造方法が重要である。すなわち、この発明に係る銅合金材の製造方法は、次の（１）から（８）の工程を有し、この（１）から（８）の工程をこの順に実施する製造方法である。 A copper alloy material made of a Cu-Fe-P-Zn-Sn-based copper alloy has a tensile strength of 620 MPa or more (preferably 625 MPa or more, more preferably 630 MPa or more) in a temperature environment of 20 ° C., The manufacturing method is important in order to have a conductivity of 40.0% IACS or more (preferably 45.0% IACS or more). That is, the method for producing a copper alloy material according to the present invention has the following steps (1) to (8), and the steps (1) to (8) are carried out in this order.
（１）含有必須元素として、１．６％以上２．６％以下のＦｅと、０．０１％以上０．３％以下（好ましくは、０．０１％以上０．２０％以下）のＰと、０．０１％以上０．３％以下のＺｎと、０．３％以上０．８％以下のＳｎとを含有し、残部がＣｕおよび不純物元素から成る、銅合金鋳造材を作製する溶解鋳造工程
（２）銅合金鋳造材を用いて熱間圧延を行って熱間圧延材を作製する熱間圧延工程
（３）熱間圧延材を用いて冷間圧延を行って第１冷間圧延材を作製する第１冷間圧延工程（４）第１冷間圧延材に対して５００℃以上６００℃以下の温度で４ｈ以下の加熱保持を行って第１熱処理材を作製する第１熱処理工程
（５）第１熱処理材を用いて２０％以上９０％以下の圧延加工度で冷間圧延を行って第２冷間圧延材を作製する第２冷間圧延工程
（６）第２冷間圧延材に対して３８０℃以上４８０℃以下の温度で１ｈ以上１２ｈ以下の加熱保持を行って第２熱処理材を作製する第２熱処理工程
（７）第２熱処理材を用いて６０％以上８０％以下の圧延加工度で冷間圧延を行って第３冷間圧延材を作製する第３冷間圧延工程
（８）第３冷間圧延材に対して２５０℃以上３８０℃以上の温度で４ｈ以下の加熱保持を行って銅合金材を作製する第３熱処理工程 (1) Fe of 1.6% or more and 2.6% or less and P of 0.01% or more and 0.3% or less (preferably 0.01% or more and 0.20% or less) as essential elements to be contained , containing 0.01% or more and 0.3% or less of Zn, 0.3% or more and 0.8% or less of Sn, and the balance being Cu and impurity elements, melting and casting for producing a copper alloy casting material Step (2) Hot-rolling step of hot-rolling the copper alloy cast material to produce a hot-rolled material (3) Cold-rolling the hot-rolled material to produce the first cold-rolled material First cold-rolling step (4) for producing the first cold-rolled material The first heat-treatment step ( 5) Second cold-rolling step of cold-rolling the first heat-treated material at a rolling reduction rate of 20% or more and 90% or less to produce a second cold-rolled material (6) Second cold-rolled material Second heat treatment step of producing a second heat treated material by heating and holding at a temperature of 380 ° C. to 480 ° C. for 1 h to 12 h (7) Using the second heat treated material Third cold-rolling step of cold-rolling at a rolling reduction to produce a third cold-rolled material (8) Heating the third cold-rolled material at a temperature of 250° C. or higher and 380° C. or higher for 4 hours or less A third heat treatment step of holding and producing a copper alloy material
　上記した（１）から（８）の主工程の流れを有する製造方法によれば、１．６％以上２．６％以下のＦｅと、０．０１％以上０．３％以下（好ましくは、０．０１％以上０．２０％以下）のＰと、０．０１％以上０．３％以下のＺｎと、０．３％以上０．８％以下のＳｎとを含有し、残部がＣｕおよび不純物元素から成り、２０℃の温度環境下において、６２０ＭＰａ以上の引張強さを有するとともに、４０．０％ＩＡＣＳ以上の導電率を有する、銅合金材を作製することができる。 According to the production method having the main process flow of (1) to (8) described above, Fe of 1.6% or more and 2.6% or less and 0.01% or more and 0.3% or less (preferably, 0.01% or more and 0.20% or less) of P, 0.01% or more and 0.3% or less of Zn, and 0.3% or more and 0.8% or less of Sn, and the balance is Cu and A copper alloy material containing impurity elements and having a tensile strength of 620 MPa or more and an electrical conductivity of 40.0% IACS or more in a temperature environment of 20° C. can be produced.
　また、上記した（１）の工程において、好ましくは、含有必須元素として、ＦｅとＰとＺｎとＳｎと、さらに、０．００２％以上０．０２５％以下のＭｎとを含有し、残部がＣｕおよび不純物元素から成る、銅合金鋳造材を作製する。また、その場合、上記した（１）の工程において、ＭＩ値を、たとえば１．１以下（＞０）とし、好ましくは１．０以下（＞０）に調製した銅合金鋳造材を作製する。その後、上記した（２）～（８）の工程を、この順に実施する。この製造方法によれば、ＦｅとＰとＺｎとＳｎとを上記した範囲で含有し、さらに、０．００２％以上０．０２５％以下のＭｎを含有し、残部がＣｕおよび不純物元素から成る、好ましい銅合金材を作製することができる。この好ましい銅合金材は、上記した２０℃の温度環境下において、６２０ＭＰａ以上の引張強さを有するとともに、４０．０％ＩＡＣＳ以上の導電率を有し、さらに、９５０℃の温度環境下において、２０％を超える破断伸びを有することができる。 Further, in the step (1) described above, preferably, as essential elements to be contained, Fe, P, Zn, and Sn, and 0.002% or more and 0.025% or less of Mn are contained, and the balance is Cu. and an impurity element to produce a copper alloy casting material. In this case, in the step (1) described above, the copper alloy cast material is prepared to have an MI value of, for example, 1.1 or less (>0), preferably 1.0 or less (>0). After that, the steps (2) to (8) described above are performed in this order. According to this manufacturing method, Fe, P, Zn, and Sn are contained within the ranges described above, and further, 0.002% or more and 0.025% or less of Mn is contained, and the balance is Cu and impurity elements. A preferred copper alloy material can be produced. This preferred copper alloy material has a tensile strength of 620 MPa or more and an electrical conductivity of 40.0% IACS or more in the temperature environment of 20° C., and further, in a temperature environment of 950° C., It can have an elongation at break greater than 20%.
　以下、図１に示す主工程の流れに沿って、この発明に係る銅合金材の製造方法について説明する。なお、この発明に係る銅合金材の製造方法では、図１に示す主工程の流れにおいて、必要に応じて、第１冷間圧延工程と第１熱処理工程とを組み合わせて繰り返す工程にすることも、第１熱処理工程と第２冷間圧延工程とを組み合わせて繰り返す工程にすることも可能である。 A method for manufacturing a copper alloy material according to the present invention will be described below along the main process flow shown in FIG. In the method for producing a copper alloy material according to the present invention, in the flow of the main steps shown in FIG. 1, the first cold rolling step and the first heat treatment step may be combined and repeated as necessary. It is also possible to combine and repeat the first heat treatment step and the second cold rolling step.
（１）溶解鋳造工程
　溶解鋳造工程では、ＦｅとＰとＺｎとＳｎとを添加した銅合金鋳造材を作製する。具体的には、第３熱処理工程まで経て得られる銅合金材が、質量％で、１．６％以上２．６％以下のＦｅと、０．０１％以上０．３％以下のＰと、０．０１％以上０．３％以下のＺｎと、０．３％以上０．８％以下（好ましくは、０．３％を超えて０．８％以下）のＳｎとを含有し、残部がＣｕおよび不純物元素から成るように調製し、銅合金鋳造材を作製する。なお、この銅合金材の一般的な製造原料のＳ含有率は、たとえば、０．００１％～０．００５％程度である。そのため、Ｓの影響を抑止または緩和するために、この銅合金材は、さらにＭｎを含有することが好ましい。その場合、Ｍｎ含有率を０．００２％以上０．０２５％以下に調製し、好ましくはＭＩ値も調整する。ＭＩ値は、たとえば１．１以下（＞０）、好ましくは１．０以下（＞０）となるように調製する。 (1) Melting and casting process In the melting and casting process, a copper alloy cast material to which Fe, P, Zn and Sn are added is produced. Specifically, the copper alloy material obtained through the third heat treatment step is, in mass%, 1.6% or more and 2.6% or less of Fe, 0.01% or more and 0.3% or less of P, It contains 0.01% or more and 0.3% or less of Zn and 0.3% or more and 0.8% or less of Sn (preferably more than 0.3% and 0.8% or less), and the balance is A copper alloy casting material is produced by preparing a material containing Cu and impurity elements. Incidentally, the S content of the raw material for general production of this copper alloy material is, for example, about 0.001% to 0.005%. Therefore, in order to suppress or mitigate the influence of S, the copper alloy material preferably further contains Mn. In that case, the Mn content is adjusted to 0.002% or more and 0.025% or less, and preferably the MI value is also adjusted. The MI value is adjusted to, for example, 1.1 or less (>0), preferably 1.0 or less (>0).
（２）熱間圧延工程
　熱間圧延工程では、上記溶解鋳造工程で作製された銅合金鋳造材を用いて、熱間圧延を行って熱間圧延材を作製する。加熱保持温度や圧延加工度などの熱間圧延条件は、一般的な条件から任意に選定すればよい。一般に、銅材や銅合金材の場合、その組成に応じて、７００℃～１０００℃の幅広い温度下で熱間圧延が行われる。そして、添加元素の総含有率が比較的大きい銅合金材の場合、より高温側の９００℃～１０００℃の温度下で熱間圧延が行われる。この観点で、この発明に係る銅合金材では、その高温特性の評価を９００℃～１０００℃の中央付近の温度（約９５０℃）下で行っている。 (2) Hot Rolling Step In the hot rolling step, the copper alloy cast material produced in the melting and casting process is hot rolled to produce a hot rolled material. The hot rolling conditions such as the heat holding temperature and the degree of rolling workability may be arbitrarily selected from general conditions. Generally, in the case of copper materials and copper alloy materials, hot rolling is performed at a wide temperature range of 700° C. to 1000° C. depending on the composition. In the case of a copper alloy material with a relatively large total content of additive elements, hot rolling is performed at a higher temperature of 900°C to 1000°C. From this point of view, the high-temperature characteristics of the copper alloy material according to the present invention are evaluated at a temperature near the center of 900° C. to 1000° C. (approximately 950° C.).
（３）第１冷間圧延工程
　第１冷間圧延工程では、上記熱間圧延工程で作製された熱間圧延材を用いて、冷間圧延を行って第１冷間圧延材を作製する。なお、圧延加工度などの冷間圧延条件は、任意でよい。 (3) First Cold Rolling Step In the first cold rolling step, the hot rolled material produced in the hot rolling step is cold rolled to produce the first cold rolled material. Cold rolling conditions such as the degree of rolling workability may be arbitrary.
（４）第１熱処理工程
　第１熱処理工程では、上記第１冷間圧延工程で作製された第１冷間圧延材に対して、５００℃以上６００℃以下の温度で４ｈ以下の加熱保持を行って第１熱処理材を作製する。この第１熱処理工程は、最初の圧延である第１冷間圧延後に行う熱処理であって、冷間圧延で銅合金組織に蓄積された歪を十分に開放するために行う熱処理である。従来の一般的な銅合金材の製造方法では、この段階の熱処理を比較的高温（たとえば７００℃以上９００℃以下）の加熱保持を行う。これに対して、この発明の第１熱処理工程では、比較的低温の５００℃以上６００℃以下の温度で４ｈ以下の加熱保持を行う。この比較的低温の加熱保持により、銅合金組織の歪を適度に解放する作用だけではなく、銅合金組織中にＦｅまたはＦｅとＰを含む化合物の粒子を適度に析出させる作用を得る。この段階で銅合金組織中に適度に分散析出された上記粒子は、最終的に得られる銅合金材の引張強さをより向上させるように作用する。 (4) First heat treatment step In the first heat treatment step, the first cold-rolled material produced in the first cold rolling step is heated and held at a temperature of 500°C or higher and 600°C or lower for 4 hours or less. to produce a first heat-treated material. This first heat treatment step is a heat treatment that is performed after the first cold rolling, which is the first rolling, and is a heat treatment that is performed to sufficiently release the strain accumulated in the copper alloy structure during the cold rolling. In the conventional general copper alloy material manufacturing method, the heat treatment at this stage is performed by heating and holding at a relatively high temperature (for example, 700° C. or more and 900° C. or less). On the other hand, in the first heat treatment step of the present invention, heating and holding is performed at a relatively low temperature of 500° C. or more and 600° C. or less for 4 hours or less. By heating and holding at a relatively low temperature, not only the effect of moderately releasing strain in the copper alloy structure but also the effect of appropriately precipitating particles of Fe or a compound containing Fe and P in the copper alloy structure can be obtained. The particles appropriately dispersed and precipitated in the copper alloy structure at this stage act to further improve the tensile strength of the finally obtained copper alloy material.
　なお、第１熱処理工程における加熱保持の温度が過度に低い（５００℃未満）場合、銅合金組織の歪の解放が不十分になるだけでなく、銅合金組織中への上記粒子の析出が不十分になる。また、第１熱処理工程における加熱保持の温度が過度に高い（６００℃超）場合または加熱保持の時間が過度に長い（４ｈ超）場合、銅合金組織の歪の解放は十分になされるが、銅合金組織中に析出した上記粒子が過度に粗大化し、銅合金材の引張強さの向上を妨げるおそれがある。また、第１熱処理工程における加熱保持の温度が上記した比較的高温（たとえば７００℃以上９００℃以下）の場合、上記粒子の析出そのものが起こらないおそれがある。この観点で、第１熱処理工程では、第１冷間圧延材に対して５００℃以上６００℃以下の温度で４ｈ以下の加熱保持を行うものとし、好ましくは、歪の解放と上記粒子の析出のバランスの良い銅合金組織を得るために５５０℃以上６００℃以下の温度で４ｈ以下（好ましくは２ｈ以下）の加熱保持を行うものとする。 If the heating and holding temperature in the first heat treatment step is excessively low (less than 500° C.), not only will the release of strain in the copper alloy structure be insufficient, but precipitation of the above particles into the copper alloy structure will be inadequate. be enough. Further, when the heating and holding temperature in the first heat treatment step is excessively high (exceeding 600 ° C.) or the heating and holding time is excessively long (exceeding 4 hours), the strain of the copper alloy structure is sufficiently released, The particles precipitated in the copper alloy structure may be excessively coarsened and hinder the improvement of the tensile strength of the copper alloy material. In addition, when the heating and holding temperature in the first heat treatment step is the above-described relatively high temperature (for example, 700° C. or higher and 900° C. or lower), there is a possibility that the particles may not be precipitated. From this point of view, in the first heat treatment step, the first cold-rolled material is heated and held at a temperature of 500 ° C. or higher and 600 ° C. or lower for 4 hours or less, preferably to release strain and precipitate the particles. In order to obtain a well-balanced copper alloy structure, heating and holding should be performed at a temperature of 550° C. or higher and 600° C. or lower for 4 hours or less (preferably 2 hours or less).
（５）第２冷間圧延工程
　第２冷間圧延工程では、上記第１熱処理工程で作製された第１熱処理材を用いて、２０％以上９０％以下の圧延加工度で冷間圧延を行って第２冷間圧延材を作製する。この第２冷間圧延工程は、第１熱処理工程で作製された第１熱処理材の銅合金組織に転位を導入して適度に蓄積させるとともに、銅合金組織を適度に加工硬化させる工程である。銅合金組織を構成する結晶に導入された転位は、銅合金組織の析出強化を担う粒子を析出させるための起点として作用する。そのため、この段階で銅合金組織に転位を均等的に導入して適度に蓄積させておくことにより、次の第２熱処理工程で銅合金組織の析出強化を担う粒子を銅合金組織中に均等的に析出させることができる。その結果、最終的に得られる銅合金材の引張強さをより向上させることができる。 (5) Second cold rolling step In the second cold rolling step, the first heat treated material produced in the first heat treatment step is used to perform cold rolling at a rolling reduction rate of 20% or more and 90% or less. to produce a second cold rolled material. This second cold rolling step is a step of introducing and appropriately accumulating dislocations in the copper alloy structure of the first heat-treated material produced in the first heat treatment step, and moderately work hardening the copper alloy structure. The dislocations introduced into the crystals forming the copper alloy structure act as starting points for precipitating particles responsible for precipitation strengthening of the copper alloy structure. Therefore, by uniformly introducing dislocations into the copper alloy structure at this stage and accumulating them appropriately, the particles responsible for precipitation strengthening of the copper alloy structure are evenly distributed in the copper alloy structure in the next second heat treatment step. can be precipitated. As a result, the tensile strength of the finally obtained copper alloy material can be further improved.
　なお、第２冷間圧延工程における圧延加工度が過度に小さい（２０％未満）場合、銅合金組織への転位の導入と蓄積が不十分になり、次の第２熱処理工程において銅合金組織中に析出される粒子数が不足しやすい。また、第２冷間圧延工程における圧延加工度が過度に大きい（９０％超）場合、次の第２熱処理工程において銅合金組織中に析出される粒子が過度に大きく成長し、析出強化の効果が得られにくい場合がある。この観点で、第２冷間圧延工程では、上記第１熱処理工程で作製された第１熱処理材に対して２０％以上９０％以下の圧延加工度で冷間圧延を行うものとし、好ましくは、最終的に析出強化と加工硬化の相乗効果をバランス良く得るために４０％以上７５％以下の圧延加工度で冷間圧延を行うものとする。 If the degree of rolling reduction in the second cold rolling step is excessively small (less than 20%), introduction and accumulation of dislocations into the copper alloy structure will be insufficient, and in the following second heat treatment step, The number of particles deposited on the surface tends to be insufficient. In addition, if the degree of rolling reduction in the second cold rolling step is excessively large (more than 90%), the particles precipitated in the copper alloy structure in the following second heat treatment step grow excessively large, resulting in the effect of precipitation strengthening. is difficult to obtain. From this point of view, in the second cold rolling step, the first heat-treated material produced in the first heat treatment step is cold-rolled at a rolling reduction rate of 20% or more and 90% or less. In order to finally obtain a synergistic effect of precipitation strengthening and work hardening in a well-balanced manner, cold rolling is performed at a rolling workability of 40% or more and 75% or less.
（６）第２熱処理工程
　第２熱処理工程では、上記第２冷間圧延工程で作製された第２冷間圧延材に対して、３８０℃以上４８０℃以下の温度で１ｈ以上１２ｈ以下の加熱保持を行って第２熱処理材を作製する。この第２熱処理工程は、上記した第２冷間圧延後に行う熱処理であって、冷間圧延で導入して蓄積された転位を利用し、析出強化を担う粒子を銅合金組織中に十分に分散析出させる時効処理の工程である。従来の一般的なＣｕ－Ｆｅ－Ｐ系の銅合金から成る銅合金材の製造方法の場合、時効処理の加熱保持はたとえば４００℃以上６００℃以下の温度で行われる。これに対して、この発明の第２熱処理工程では、比較的低温側の３８０℃以上４８０℃以下の温度で１ｈ以上１２ｈ以下の加熱保持を行う。この比較的低温側の加熱保持により、銅合金組織中に析出されるＦｅまたはＦｅとＰを含む化合物の粒子がより微細化されるとともに、より均一的に分散させることができる。その結果、銅合金組織に対する析出強化の効果を十分に得ることができる。また、この比較的低温側の加熱保持により、意図的に銅合金組織中の歪みの解放を不十分にすることで、第２冷間圧延工程までに得られた析出強化と加工硬化の相乗効果を十分に得ることができる。 (6) Second heat treatment step In the second heat treatment step, the second cold-rolled material produced in the second cold rolling step is heated and held at a temperature of 380 ° C. or higher and 480 ° C. or lower for 1 hour or more and 12 hours or less. to produce a second heat-treated material. This second heat treatment step is a heat treatment performed after the second cold rolling described above, and utilizes dislocations introduced and accumulated during cold rolling to sufficiently disperse particles responsible for precipitation strengthening in the copper alloy structure. This is the step of aging treatment for precipitation. In the case of a conventional method for producing a copper alloy material composed of a general Cu--Fe--P-based copper alloy, heating and holding for aging treatment is performed at a temperature of, for example, 400.degree. C. or higher and 600.degree. On the other hand, in the second heat treatment step of the present invention, heating and holding is performed for 1 hour or more and 12 hours or less at a temperature of 380° C. or more and 480° C. or less, which is on the relatively low temperature side. By heating and holding at the relatively low temperature side, particles of Fe or a compound containing Fe and P precipitated in the copper alloy structure can be made finer and dispersed more uniformly. As a result, the effect of precipitation strengthening on the copper alloy structure can be sufficiently obtained. In addition, by intentionally making the release of strain in the copper alloy structure insufficient by heating and holding at this relatively low temperature side, the synergistic effect of precipitation strengthening and work hardening obtained by the second cold rolling process can be obtained sufficiently.
　なお、第２熱処理工程における加熱保持の温度が過度に低い（３８０℃未満）場合や加熱保持の時間が過度に短い（１ｈ未満）場合は、銅合金組織中への上記粒子の析出が不十分になり、最終的に得られる銅合金材の引張強さや導電率が不十分になる場合がある。また、第２熱処理工程における加熱保持の温度が過度に高い（４８０℃超）場合や加熱保持の時間が過度に長い（１２ｈ超）場合は、銅合金組織中に析出させた上記粒子が大きく成長して析出強化の効果が減少するとともに、銅合金組織中の歪の解放が意図した程度を超えて十分に進んでしまい、第２冷間圧延工程までに得られた析出強化と加工硬化の相乗効果が消失される。その結果、最終的に得られる銅合金材の引張強さが不十分になる場合がある。この観点で、第２熱処理工程では、第２冷間圧延材に対して３８０℃以上４８０℃以下の温度で１ｈ以上１２ｈ以下の加熱保持を行うものとし、好ましくは、歪の解放と上記粒子の析出のバランスの良い銅合金組織を得るために４００℃以上４６０℃以下の温度で１ｈ以上１２ｈ以下（好ましくは２ｈ以上８ｈ以下）の加熱保持を行うものとする。 If the heating and holding temperature in the second heat treatment step is excessively low (less than 380°C) or the heating and holding time is excessively short (less than 1 hour), the precipitation of the particles into the copper alloy structure is insufficient. resulting in insufficient tensile strength and electrical conductivity of the finally obtained copper alloy material. Further, when the heating and holding temperature in the second heat treatment step is excessively high (over 480°C) or the heating and holding time is excessively long (over 12 hours), the particles precipitated in the copper alloy structure grow large. As a result, the effect of precipitation strengthening decreases, and the release of strain in the copper alloy structure progresses sufficiently beyond the intended degree, and the synergistic effect of precipitation strengthening and work hardening obtained by the second cold rolling process Effect is lost. As a result, the tensile strength of the finally obtained copper alloy material may be insufficient. From this point of view, in the second heat treatment step, the second cold-rolled material is heated and held at a temperature of 380 ° C. or higher and 480 ° C. or lower for 1 hour or more and 12 hours or less. In order to obtain a copper alloy structure with well-balanced precipitation, heating and holding is performed at a temperature of 400° C. or higher and 460° C. or lower for 1 hour or longer and 12 hours or shorter (preferably 2 hours or longer and 8 hours or shorter).
（７）第３冷間圧延工程
　第３冷間圧延工程では、上記第２熱処理工程で作製された第２熱処理材を用いて、６０％以上８０％以下の圧延加工度で冷間圧延を行って第３冷間圧延材を作製する。また、この工程で、最終的に所望する銅合金材の厚さ（製品厚さ）に調製することができる。この第３冷間圧延工程は、第２熱処理工程で作製された第２熱処理材の上記粒子が分散析出している銅合金組織に更に転位を導入して十分に蓄積させるとともに、銅合金組織を更に加工硬化させる工程である。これにより、第２熱処理工程までに得られた析出強化と加工硬化の相乗効果が十分に高まるため、最終的に得られる銅合金材の引張強さを十分に向上させることができる。 (7) Third cold rolling step In the third cold rolling step, the second heat treated material produced in the second heat treatment step is used to perform cold rolling at a rolling reduction rate of 60% or more and 80% or less. to produce a third cold rolled material. Also, in this step, the final desired thickness of the copper alloy material (product thickness) can be obtained. In the third cold rolling step, dislocations are further introduced into and sufficiently accumulated in the copper alloy structure in which the particles of the second heat treated material produced in the second heat treatment step are dispersed and precipitated, and the copper alloy structure is changed. It is a step of further work hardening. As a result, the synergistic effect of precipitation strengthening and work hardening obtained by the second heat treatment step is sufficiently enhanced, so that the tensile strength of the finally obtained copper alloy material can be sufficiently improved.
　なお、第３冷間圧延工程における圧延加工度が過度に小さい（６０％未満）場合、銅合金組織が十分に加工硬化されず、析出強化と加工硬化の相乗効果が十分に高まらない場合がある。また、第３冷間圧延工程における圧延加工度が過度に大きい（８０％超）場合、銅合金組織中の歪みが過度に蓄積され、過剰に蓄積された歪が次の第３熱処理工程で意図した程度を超えて過度に解放され、最終的に得られる銅合金材の引張強さが十分に向上されない場合がある。この観点で、第３冷間圧延工程では、上記第２熱処理工程で作製された第２熱処理材に対して６０％以上８０％以下の圧延加工度で冷間圧延を行うものとし、好ましくは、最終的に析出強化と加工硬化の相乗効果をバランス良く得るために６５％以上７５％以下の圧延加工度で冷間圧延を行うものとする。 If the degree of rolling reduction in the third cold rolling step is excessively small (less than 60%), the copper alloy structure may not be sufficiently work hardened, and the synergistic effect of precipitation strengthening and work hardening may not be sufficiently enhanced. . In addition, if the rolling reduction rate in the third cold rolling step is excessively large (more than 80%), the strain in the copper alloy structure is excessively accumulated, and the excessively accumulated strain is used in the following third heat treatment step. In some cases, the tensile strength of the finally obtained copper alloy material is not sufficiently improved due to excessive release beyond the degree of release. From this point of view, in the third cold rolling step, the second heat treated material produced in the second heat treatment step is cold rolled at a rolling reduction rate of 60% or more and 80% or less. In order to finally obtain a synergistic effect of precipitation strengthening and work hardening in a well-balanced manner, cold rolling is performed at a rolling workability of 65% or more and 75% or less.
（８）第３熱処理工程
　第３熱処理工程では、上記第３冷間圧延工程で作製された第３冷間圧延材に対して、２５０℃以上３８０℃以上の温度で４ｈ以下の加熱保持を行って、目的とする銅合金材を作製する。この工程の加熱保持は、保持時間が０ｈであってもよく、つまり、昇温して目標の保持温度に達したら直ちに降温に入ってもよい。この第３熱処理工程は、上記した第３冷間圧延で作製された第３冷間圧延材の銅合金組織中に蓄積された歪を適度に解放し、目的とする銅合金材の伸びや曲げ加工性などの機械的特性を向上させる工程である。従来の一般的なＣｕ－Ｆｅ－Ｐ系の銅合金から成る銅合金材の製造方法の場合、歪の解放を目的とする熱処理（焼鈍）の加熱保持はたとえば４００℃以上５００℃以下の温度で行われる。これに対して、この発明の第３熱処理工程では、これよりも低温側の２５０℃以上３８０℃以下の温度で４ｈ以下の加熱保持を行う。この従来よりも低温側で行う加熱保持により、圧延加工に起因する銅合金組織中の歪が適度に解放されながらも過度に解放されない状態とし、歪を適度に含む銅合金組織を得ることにより、目的とする銅合金材の引張強さの低下を最小限に抑制することができる。 (8) Third heat treatment step In the third heat treatment step, the third cold rolled material produced in the third cold rolling step is heated and held at a temperature of 250°C or higher and 380°C or higher for 4 hours or less. Then, the desired copper alloy material is produced. The heating and holding in this step may have a holding time of 0 h, that is, the temperature may be lowered as soon as the target holding temperature is reached after raising the temperature. This third heat treatment step moderately releases the strain accumulated in the copper alloy structure of the third cold-rolled material produced by the third cold rolling described above, and the target copper alloy material elongation and bending This is a process for improving mechanical properties such as workability. In the case of a conventional method for producing a copper alloy material made of a general Cu--Fe--P-based copper alloy, heat treatment (annealing) for the purpose of releasing strain is maintained at a temperature of, for example, 400° C. or higher and 500° C. or lower. done. On the other hand, in the third heat treatment step of the present invention, heating and holding is performed for 4 hours or less at a temperature of 250° C. or higher and 380° C. or lower, which is on the lower temperature side. By heating and holding at a lower temperature than in the past, the strain in the copper alloy structure caused by rolling is moderately released but not excessively released, and a copper alloy structure containing moderate strain is obtained. A decrease in tensile strength of the intended copper alloy material can be minimized.
　なお、第３熱処理工程における加熱保持の温度が過度に低い（２５０℃未満）場合、第３冷間圧延材の銅合金組織中の歪の解放が不十分になり、目的とする銅合金材の伸びや曲げ加工性などの機械的特性が向上されない場合がある。また、第３熱処理工程における加熱保持の温度が過度に高い（３８０℃超）場合や加熱保持の時間が過度に長い（４ｈ超）場合は、第３冷間圧延材の銅合金組織中の歪の解放が過度になり、目的とする銅合金材の引張強さが得られない場合がある。この観点で、第３熱処理工程では、第３冷間圧延材に対して２５０℃以上３８０℃以下の温度で４ｈ以下の加熱保持を行うものとし、好ましくは、目的とする銅合金材の引張強さと伸びや曲げ加工性のバランスの良い銅合金組織を得るために２８０℃以上３５０℃以下の温度で１ｈ以下の加熱保持を行うものとする。 If the heating and holding temperature in the third heat treatment step is excessively low (less than 250°C), the release of strain in the copper alloy structure of the third cold-rolled material becomes insufficient, resulting in the desired copper alloy material. Mechanical properties such as elongation and bendability may not be improved. In addition, if the heating and holding temperature in the third heat treatment step is excessively high (over 380 ° C.) or the heating and holding time is excessively long (over 4 hours), the strain in the copper alloy structure of the third cold rolled material is excessively released, and the desired tensile strength of the copper alloy material may not be obtained. From this point of view, in the third heat treatment step, the third cold-rolled material is heated and held at a temperature of 250 ° C. or higher and 380 ° C. or lower for 4 hours or less. In order to obtain a copper alloy structure with a good balance of elongation and bending workability, heating and holding at a temperature of 280° C. or more and 350° C. or less for 1 hour or less is performed.
　以上より、この発明によれば、Ｃ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金から成る銅合金材と同様に上記した残留スマットの問題がなく、より高強度なＣ７０２５などのＣｕ－Ｎｉ－Ｓｉ系の銅合金から成る銅合金材と略同等の導電性（導電率）と機械的強さ（引張強さ）を有する、銅合金材および銅合金材の製造方法を提供することができる。 As described above, according to the present invention, there is no problem of residual smut as with a copper alloy material made of a Cu-Fe-Zn-P-based copper alloy such as C1940, and a higher strength Cu-Ni such as C7025 - It is possible to provide a copper alloy material and a method for producing a copper alloy material that have substantially the same electrical conductivity (conductivity) and mechanical strength (tensile strength) as a copper alloy material made of a Si-based copper alloy. .
　この発明に係る銅合金材および銅合金材の製造方法の有効性について、実際の評価結果を挙げて、説明する。初めに、表１に、試料１～２９（本発明例、比較例）の銅合金材の組成（添加元素）、主な製造条件、および機械的特性などの情報を纏めて示す。また、参考例として、試料３０、３１の銅合金材を併記する。なお、試料１～２９では、意図的にＭｎを添加していない。また、試料１～２９の添加元素以外の残部はＣｕおよび不純物元素と解してよく、０．０１％未満の不純物元素（Ａｇ、Ｐｂ、ＮｉおよびＳなど）は記載を略している。 The effectiveness of the copper alloy material and the method of manufacturing the copper alloy material according to the present invention will be explained by citing actual evaluation results. First, Table 1 summarizes information such as compositions (additional elements), main manufacturing conditions, and mechanical properties of copper alloy materials of samples 1 to 29 (examples of the present invention and comparative examples). In addition, the copper alloy materials of Samples 30 and 31 are also shown as reference examples. Note that Mn was not intentionally added to samples 1 to 29. In addition, the remainder of samples 1 to 29 other than additive elements may be interpreted as Cu and impurity elements, and impurity elements (Ag, Pb, Ni, S, etc.) less than 0.01% are omitted.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示す試料１の銅合金材は、２．２質量％のＦｅと、０．０３質量％のＰと、０．１２質量％のＺｎと、０．６０質量％のＳｎとを含有し、残部がＣｕおよび不純物元素から成る。この銅合金材は、下記（１）から（８）の工程を経て、作製されたものである。
（１）溶解鋳造工程において、高周波溶解炉を用いて、無酸素銅から成る溶解母材に所定の添加元素を含む添加材などを加えて窒素雰囲気下で溶解し、成分調整後に鋳造し、約２５ｍｍの厚さ、約３０ｍｍの幅、約１５０ｍｍの長さの銅合金鋳造材を作製した。
（２）熱間圧延工程において、銅合金鋳造材を約９５０℃の温度に加熱した状態で熱間圧延し、約８ｍｍの厚さの熱間圧延材を作製した。
（３）第１冷間圧延工程において、熱間圧延材を合計で約８３％の圧延加工度になるように冷間圧延し、約１．４ｍｍの厚さの第１冷間圧延材を作製した。
（４）第１熱処理工程において、第１冷間圧延材に対して約５８０℃の温度で約３分の加熱保持を行って、第１熱処理材を作製した。
（５）第２冷間圧延工程において、第１熱処理材を合計で約６４％の圧延加工度になるように冷間圧延し、約０．５ｍｍの厚さの第２冷間圧延材を作製した。この場合、第１冷間圧延工程と第２冷間圧延工程による合計の圧延加工度は約９４％になる。
（６）第２熱処理工程において、第２冷間圧延材に対して約４５０℃の温度で約４ｈの加熱保持を行って、第２熱処理材を作製した。
（７）第３冷間圧延工程において、第２熱処理材を合計で約７０％の圧延加工度になるように冷間圧延し、約０．１５ｍｍの厚さの第３冷間圧延材を作製した。この場合、第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約８９％になり、第１冷間圧延工程と第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約９８％になる。
（８）第３熱処理工程において、第３冷間圧延材に対して約３５０℃の温度で約１分の加熱保持を行って、最終的に約０．１５ｍｍの厚さの試料１の銅合金材を得た。試料１の銅合金材は本発明例である。 The copper alloy material of Sample 1 shown in Table 1 contains 2.2% by mass of Fe, 0.03% by mass of P, 0.12% by mass of Zn, and 0.60% by mass of Sn. , the balance being Cu and impurity elements. This copper alloy material was produced through the following steps (1) to (8).
(1) In the melting and casting process, using a high-frequency melting furnace, an additive containing a predetermined additive element is added to a molten base material made of oxygen-free copper, and the like is added and melted in a nitrogen atmosphere. A copper alloy casting having a thickness of 25 mm, a width of about 30 mm and a length of about 150 mm was produced.
(2) In the hot rolling step, the copper alloy cast material was hot rolled while being heated to a temperature of about 950°C to produce a hot rolled material having a thickness of about 8 mm.
(3) In the first cold-rolling step, the hot-rolled material is cold-rolled to a rolling reduction rate of about 83% in total to produce a first cold-rolled material having a thickness of about 1.4 mm. did.
(4) In the first heat treatment step, the first cold-rolled material was heated and held at a temperature of about 580°C for about 3 minutes to produce a first heat-treated material.
(5) In the second cold rolling step, the first heat-treated material is cold-rolled to a rolling reduction rate of about 64% in total to produce a second cold-rolled material having a thickness of about 0.5 mm. did. In this case, the total rolling workability of the first cold rolling step and the second cold rolling step is about 94%.
(6) In the second heat treatment step, the second cold-rolled material was heated and held at a temperature of about 450°C for about 4 hours to produce a second heat-treated material.
(7) In the third cold-rolling step, the second heat-treated material is cold-rolled to a rolling reduction rate of about 70% in total to produce a third cold-rolled material having a thickness of about 0.15 mm. did. In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%, and the rolling workability of the first cold rolling step, the second cold rolling step and the third cold rolling step is The total rolling workability is about 98%.
(8) In the third heat treatment step, the third cold-rolled material is heated and held at a temperature of about 350 ° C. for about 1 minute, and finally the copper alloy of sample 1 having a thickness of about 0.15 mm got the wood. The copper alloy material of Sample 1 is an example of the present invention.
　表１に示す試料２の銅合金材は、試料１の銅合金材の製造工程において、第２熱処理工程の加熱保持を約４２０℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２の銅合金材は本発明例である。 The copper alloy material of sample 2 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the second heat treatment step is set to a temperature of about 420 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1. The copper alloy material of sample 2 is an example of the present invention.
　表１に示す試料３の銅合金材は、試料１の銅合金材の製造工程において、第２熱処理工程の加熱保持を約４２０℃の温度に設定し、第３熱処理工程の加熱保持を約２８０℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料３の銅合金材は本発明例である。 For the copper alloy material of sample 3 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the heating and holding temperature in the second heat treatment step is set to about 420 ° C., and the heating and holding temperature in the third heat treatment step is set to about 280 ° C. It was manufactured through substantially the same manufacturing process as the copper alloy material of sample 1 except that the temperature was set to 10°C, and finally had the same thickness as the copper alloy material of sample 1. The copper alloy material of Sample 3 is an example of the present invention.
　表１に示す試料４の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＳｎが約０．３０質量％になるようにした以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料４の銅合金材は本発明例である。 In the copper alloy material of sample 4 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, Sn contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 0.30% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally. The copper alloy material of Sample 4 is an example of the present invention.
　表１に示す試料５の銅合金材は、試料１の銅合金材の製造工程において、第１熱処理工程の加熱保持を約５５０℃の温度に設定し、第２冷間圧延工程の圧延加工度を約７３％に設定し、第２熱処理工程の加熱保持を約４２０℃の温度に設定し、第３冷間圧延工程の圧延加工度を約６０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。この場合、第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約８９％になる。試料５の銅合金材は本発明例である。 For the copper alloy material of sample 5 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the heating and holding in the first heat treatment step was set to a temperature of about 550 ° C., and the rolling workability in the second cold rolling step was was set to about 73%, the heating and holding in the second heat treatment step was set to a temperature of about 420 ° C., and the rolling reduction in the third cold rolling step was set to about 60%, except that the copper alloy of sample 1 After going through substantially the same manufacturing process as the material, it was finally manufactured to have the same thickness as the copper alloy material of sample 1. In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%. The copper alloy material of sample 5 is an example of the present invention.
　表１に示す試料６の銅合金材は、試料１の銅合金材の製造工程において、第１熱処理工程の加熱保持を約５５０℃の温度に設定し、第２冷間圧延工程の圧延加工度を約４６％に設定し、第３冷間圧延工程の圧延加工度を約８０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。この場合、第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約８９％になる。試料６の銅合金材は本発明例である。 For the copper alloy material of sample 6 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the heating and holding in the first heat treatment step was set to a temperature of about 550 ° C., and the rolling workability in the second cold rolling step was was set to about 46%, and the rolling workability in the third cold rolling step was set to about 80%. It is manufactured so as to have the same thickness as the alloy material. In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%. The copper alloy material of Sample 6 is an example of the present invention.
　表１に示す試料７の銅合金材は、試料１の銅合金材の製造工程において、第２冷間圧延工程の圧延加工度を約７３％に設定し、第２熱処理工程の加熱保持を約４２０℃の温度に設定し、第３冷間圧延工程の圧延加工度を約６０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料７の銅合金材は本発明例である。 For the copper alloy material of sample 7 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the rolling reduction in the second cold rolling step was set to about 73%, and the heating and holding in the second heat treatment step was set to about 73%. Except that the temperature was set to 420 ° C. and the rolling workability in the third cold rolling step was set to about 60%, the manufacturing process was substantially the same as that of the copper alloy material of sample 1, and finally the copper of sample 1 It is manufactured so as to have the same thickness as the alloy material. The copper alloy material of sample 7 is an example of the present invention.
　表１に示す試料８の銅合金材は、試料１の銅合金材の製造工程において、第１熱処理工程の加熱保持を約６００℃の温度に設定し、第２冷間圧延工程の圧延加工度を約７３％に設定し、第２熱処理工程の加熱保持を約４２０℃の温度に設定し、第３冷間圧延工程の圧延加工度を約６０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料８の銅合金材は本発明例である。 For the copper alloy material of sample 8 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the heating and holding in the first heat treatment step was set to a temperature of about 600 ° C., and the rolling workability in the second cold rolling step was was set to about 73%, the heating and holding in the second heat treatment step was set to a temperature of about 420 ° C., and the rolling reduction in the third cold rolling step was set to about 60%, except that the copper alloy of sample 1 After going through substantially the same manufacturing process as the material, it was finally manufactured to have the same thickness as the copper alloy material of sample 1. The copper alloy material of Sample 8 is an example of the present invention.
　表１に示す試料９の銅合金材は、試料１の銅合金材の製造工程において、第１熱処理工程の加熱保持を約６００℃の温度に設定し、第２冷間圧延工程の圧延加工度を約４６％に設定し、第３冷間圧延工程の圧延加工度を約８０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料９の銅合金材は本発明例である。 For the copper alloy material of sample 9 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the heating and holding in the first heat treatment step was set to a temperature of about 600 ° C., and the rolling workability in the second cold rolling step was was set to about 46%, and the rolling workability in the third cold rolling step was set to about 80%. It is manufactured so as to have the same thickness as the alloy material. The copper alloy material of sample 9 is an example of the present invention.
　表１に示す試料１０の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＦｅが約１．５０質量％になるようにした以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１０の銅合金材はＦｅ含有率がこの発明の範囲外となる比較例である。 In the copper alloy material of sample 10 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, Fe contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 1.50% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally. The copper alloy material of Sample 10 is a comparative example in which the Fe content is outside the scope of the present invention.
　表１に示す試料１１の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＦｅが約２．８０質量％になるようにした以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１１の銅合金材は比較例であり、Ｆｅ含有率がこの発明の範囲外となる。 In the copper alloy material of sample 11 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, Fe contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 2.80% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally. The copper alloy material of sample 11 is a comparative example, and the Fe content is outside the scope of the present invention.
　表１に示す試料１２の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＰが約０．２２質量％になるようにした以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１２の銅合金材は本発明例である。 In the copper alloy material of sample 12 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the P contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 0.22% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally. The copper alloy material of sample 12 is an example of the present invention.
　表１に示す試料１３の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＺｎが約０．４０質量％になるようにした以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１３の銅合金材は比較例であり、Ｚｎ含有率がこの発明の範囲外となる。 In the copper alloy material of sample 13 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, about 0.40% by mass of Zn is contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally. The copper alloy material of sample 13 is a comparative example, and the Zn content is outside the scope of the present invention.
　表１に示す試料１４の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＳｎが約０．２０質量％になるようにした以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１４の銅合金材は比較例であり、Ｓｎ含有率がこの発明の範囲外となる。 In the copper alloy material of sample 14 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, Sn contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 0.20% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally. The copper alloy material of sample 14 is a comparative example, and the Sn content is outside the scope of the present invention.
　表１に示す試料１５の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＳｎが約０．９０質量％になるようにした以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１５の銅合金材は比較例であり、Ｓｎ含有率がこの発明の範囲外となる。 In the copper alloy material of sample 15 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, Sn contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 0.90% by mass. It was produced through substantially the same manufacturing process as the copper alloy material of sample 1 except that it was made to have a thickness equivalent to that of the copper alloy material of sample 1 finally. The copper alloy material of sample 15 is a comparative example, and the Sn content is outside the scope of the present invention.
　表１に示す試料１６の銅合金材は、試料１の銅合金材の製造工程において、溶解鋳造工程の成分調整で最終的に得られる銅合金材に含有されるＳｎが約０．３０質量％になるようにし、第１熱処理工程の加熱保持を約４５０℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１６の銅合金材は比較例であり、第１熱処理工程がこの発明の範囲外となる。 In the copper alloy material of sample 16 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, Sn contained in the copper alloy material finally obtained by adjusting the composition in the melting and casting process is about 0.30% by mass. Except that the heating and holding in the first heat treatment step was set to a temperature of about 450 ° C., the manufacturing process was substantially the same as the copper alloy material of sample 1, and finally the same as the copper alloy material of sample 1. It is made to have a thickness of The copper alloy material of sample 16 is a comparative example, and the first heat treatment step is outside the scope of the present invention.
　表１に示す試料１７の銅合金材は、試料１の銅合金材の製造工程において、第１熱処理工程の加熱保持を約６５０℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１７の銅合金材は比較例であり、第１熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 17 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the first heat treatment step is set to a temperature of about 650 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1. The copper alloy material of sample 17 is a comparative example, and the first heat treatment step is outside the scope of the present invention.
　表１に示す試料１８の銅合金材は、試料１の銅合金材の製造工程において、第１熱処理工程の加熱保持を約５ｈの時間に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料１８の銅合金材は比較例であり、第１熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 18 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding time in the first heat treatment step was set to about 5 hours in the manufacturing process of the copper alloy material of sample 1. Through the manufacturing process of 1, it was finally manufactured to have a thickness equivalent to that of the copper alloy material of sample 1. The copper alloy material of sample 18 is a comparative example, and the first heat treatment step is outside the scope of the present invention.
　表１に示す試料１９の銅合金材は、試料１の銅合金材の製造工程において、第２冷間圧延工程の圧延加工度を約１７％に設定し、第３冷間圧延工程の圧延加工度を約８０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。この場合、第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約８３％になる。試料１９の銅合金材は比較例であり、第２冷間圧延工程がこの発明の範囲外となる。 For the copper alloy material of sample 19 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the rolling reduction rate in the second cold rolling step was set to about 17%, and the rolling reduction in the third cold rolling step was Except for setting the degree of hardness to about 80%, it was manufactured to have a thickness equivalent to that of the copper alloy material of Sample 1 after undergoing substantially the same manufacturing process as that of the copper alloy material of Sample 1. . In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 83%. The copper alloy material of sample 19 is a comparative example, and the second cold rolling step is outside the scope of the present invention.
　表１に示す試料２０の銅合金材は、試料１の銅合金材の製造工程において、第２冷間圧延工程の圧延加工度を約９１％に設定し、第３冷間圧延工程の圧延加工度を約６０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。この場合、第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約９６％になる。試料２０の銅合金材は比較例であり、第２冷間圧延工程がこの発明の範囲外となる。 For the copper alloy material of sample 20 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the rolling reduction rate in the second cold rolling step was set to about 91%, and the rolling reduction in the third cold rolling step was Except for setting the degree of hardness to about 60%, the copper alloy material was manufactured through substantially the same manufacturing process as the copper alloy material of sample 1, and finally manufactured to have the same thickness as the copper alloy material of sample 1. . In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 96%. The copper alloy material of sample 20 is a comparative example, and the second cold rolling step is outside the scope of the present invention.
　表１に示す試料２１の銅合金材は、試料１の銅合金材の製造工程において、第２熱処理工程の加熱保持を約３５０℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２１の銅合金材は比較例であり、第２熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 21 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the second heat treatment step was set to a temperature of about 350 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1. The copper alloy material of sample 21 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
　表１に示す試料２２の銅合金材は、試料１の銅合金材の製造工程において、第２熱処理工程の加熱保持を約５００℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２２の銅合金材は比較例であり、第２熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 22 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the second heat treatment step was set to a temperature of about 500 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1. The copper alloy material of Sample 22 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
　表１に示す試料２３の銅合金材は、試料１の銅合金材の製造工程において、第２熱処理工程の加熱保持を約４２０℃の温度で約０．５ｈの時間に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２３の銅合金材は比較例であり、第２熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 23 shown in Table 1 is the sample 1 except that the heating and holding in the second heat treatment step is set to a temperature of about 420 ° C. for about 0.5 hours in the manufacturing process of the copper alloy material of sample 1. After going through substantially the same manufacturing process as the copper alloy material of sample 1, it was finally manufactured to have the same thickness as the copper alloy material of sample 1. The copper alloy material of sample 23 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
　表１に示す試料２４の銅合金材は、試料１の銅合金材の製造工程において、第２熱処理工程の加熱保持を約４５０℃の温度で約２０ｈの時間に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２４の銅合金材は比較例であり、第２熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 24 shown in Table 1 is the manufacturing process of the copper alloy material of sample 1, except that the heating and holding in the second heat treatment step is set to a temperature of about 450 ° C. for about 20 hours. It was manufactured so as to have a thickness equivalent to that of the copper alloy material of the sample 1 through a manufacturing process substantially equivalent to that of the copper alloy material. The copper alloy material of Sample 24 is a comparative example, and the second heat treatment step is outside the scope of the present invention.
　表１に示す試料２５の銅合金材は、試料１の銅合金材の製造工程において、第２冷間圧延工程の圧延加工度を約７９％に設定し、第３冷間圧延工程の圧延加工度を約５０％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。この場合、第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約９０％になる。試料２５の銅合金材は比較例であり、第３冷間圧延工程がこの発明の範囲外となる。 For the copper alloy material of sample 25 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the rolling reduction rate in the second cold rolling process was set to about 79%, and the rolling reduction in the third cold rolling process was Except for setting the degree of hardness to about 50%, the copper alloy material of sample 1 was manufactured through substantially the same manufacturing process as that of the copper alloy material of sample 1, and finally manufactured to have the same thickness as the copper alloy material of sample 1. . In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 90%. The copper alloy material of sample 25 is a comparative example, and the third cold rolling step is outside the scope of the present invention.
　表１に示す試料２６の銅合金材は、試料１の銅合金材の製造工程において、第２冷間圧延工程の圧延加工度を約２８％に設定し、第３冷間圧延工程の圧延加工度を約８５％に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。この場合、第２冷間圧延工程と第３冷間圧延工程による合計の圧延加工度は約８９％になる。試料２６の銅合金材は比較例であり、第３冷間圧延工程がこの発明の範囲外となる。 For the copper alloy material of sample 26 shown in Table 1, in the manufacturing process of the copper alloy material of sample 1, the rolling reduction rate in the second cold rolling step was set to about 28%, and the rolling reduction in the third cold rolling step was Except for setting the degree of hardness to about 85%, it was manufactured so as to have the same thickness as the copper alloy material of Sample 1 after undergoing substantially the same manufacturing process as that of the copper alloy material of Sample 1. . In this case, the total rolling workability of the second cold rolling step and the third cold rolling step is about 89%. The copper alloy material of sample 26 is a comparative example, and the third cold rolling step is outside the scope of the present invention.
　表１に示す試料２７の銅合金材は、試料１の銅合金材の製造工程において、第３熱処理工程の加熱保持を約２００℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２７の銅合金材は比較例であり、第３熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 27 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the third heat treatment step was set to a temperature of about 200 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1. The copper alloy material of sample 27 is a comparative example, and the third heat treatment step is outside the scope of the present invention.
　表１に示す試料２８の銅合金材は、試料１の銅合金材の製造工程において、第３熱処理工程の加熱保持を約４００℃の温度に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２８の銅合金材は比較例であり、第３熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 28 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding in the third heat treatment step was set to a temperature of about 400 ° C. in the manufacturing process of the copper alloy material of sample 1. Through the same manufacturing process, it was finally manufactured to have the same thickness as the copper alloy material of Sample 1. The copper alloy material of sample 28 is a comparative example, and the third heat treatment step is outside the scope of the present invention.
　表１に示す試料２９の銅合金材は、試料１の銅合金材の製造工程において、第３熱処理工程の加熱保持を約５ｈの時間に設定した以外は、試料１の銅合金材と実質同等の製造工程を経て、最終的に試料１の銅合金材と同等の厚さを有するように作製されたものである。試料２９の銅合金材は比較例であり、第３熱処理工程がこの発明の範囲外となる。 The copper alloy material of sample 29 shown in Table 1 is substantially the same as the copper alloy material of sample 1 except that the heating and holding time in the third heat treatment step was set to about 5 hours in the manufacturing process of the copper alloy material of sample 1. Through the manufacturing process of 1, it was finally manufactured to have a thickness equivalent to that of the copper alloy material of sample 1. The copper alloy material of sample 29 is a comparative example, and the third heat treatment step is outside the scope of the present invention.
　表１に示す試料３０の銅合金材は、Ｃ１９４０相当の組成（Ｃｕ－２．２質量％Ｆｅ－０．０３質量％Ｐ－０．１２質量％Ｚｎ）を有し、質別がＥＳＨで、試料１の銅合金材と同等の厚さを有する市販材である。試料３０の銅合金材は参考例である。 The copper alloy material of sample 30 shown in Table 1 has a composition corresponding to C1940 (Cu-2.2% by mass Fe-0.03% by mass P-0.12% by mass Zn), and the temper is ESH. It is a commercially available material having the same thickness as the copper alloy material of Sample 1. The copper alloy material of sample 30 is a reference example.
　表１に示す試料３１の銅合金材は、Ｃ７０２５相当の組成（Ｃｕ－３質量％Ｎｉ－０．６５質量％Ｓｉ－０．１５質量％Ｍｇ）を有し、質別が１／２・Ｈで、試料１の銅合金材と同等の厚さを有する市販材である。試料３１の銅合金材は参考例である。 The copper alloy material of Sample 31 shown in Table 1 has a composition equivalent to C7025 (Cu-3% by mass Ni-0.65% by mass Si-0.15% by mass Mg) and has a temper of 1/2 H It is a commercially available material having a thickness equivalent to that of the copper alloy material of Sample 1. The copper alloy material of sample 31 is a reference example.
　上記した試料１～３１の銅合金材の特性等について、表１に示すように、引張強さ、導電率、曲げ加工性および残留スマットの有無に着目し、実際に確認して評価した。具体的に、銅合金材の引張強さは、常温環境下（約２０℃）において、金属材料引張試験方法を規定するＪＩＳ－Ｚ２２４１：２０１１に準拠して測定した。また、銅合金材の導電率は、常温環境下（約２０℃）において、非鉄金属材料の導電率測定方法を規定するＪＩＳ－Ｚ０５０５：１９７５に準拠して測定した。また、銅合金材の曲げ加工性は、常温環境下（約２０℃）において、ＪＩＳ－Ｈ３１１０：２０１８で曲げ試験として採用されているＷ曲げ試験で評価した。具体的には、被試験体（銅合金材）を０．１５ｍｍの曲げ半径（内側半径）で曲げたとき、試験体の曲げの外側面に割れが確認されなかった場合を「優」とし、微細であっても割れが確認された場合を「劣」とした。また、残留スマットの有無は、被試験体（銅合金材）を前処理し、化学研磨液中に約１分間浸漬し、水洗し、乾燥させた被試験体の表面を観察して確認した。このとき、化学研磨液は、約２０質量％の硫酸と約８質量％の過酸化水素とを含む酸性水溶液とし、約４０℃に保温した。化学研磨液に浸漬する被試験体の表面積は、約２０００ｍｍ２（幅２０ｍｍで長さ５０ｍｍの表裏面）とした。被試験体の前処理は、エタノール脱脂、アルカリ電解脱脂、濃度５％の硫酸水溶液に浸漬（中和）、水洗、乾燥の順に行った。 Regarding the properties of the copper alloy materials of Samples 1 to 31 described above, as shown in Table 1, attention was focused on tensile strength, electrical conductivity, bending workability, and the presence or absence of residual smut, and they were actually confirmed and evaluated. Specifically, the tensile strength of the copper alloy material was measured in accordance with JIS-Z2241:2011, which defines a tensile test method for metallic materials, under a normal temperature environment (approximately 20°C). Further, the electrical conductivity of the copper alloy material was measured in a room temperature environment (approximately 20° C.) in accordance with JIS-Z0505:1975, which defines methods for measuring the electrical conductivity of non-ferrous metal materials. In addition, the bending workability of the copper alloy material was evaluated by the W bending test, which is adopted as a bending test in JIS-H3110:2018, in a room temperature environment (about 20°C). Specifically, when the test piece (copper alloy material) is bent with a bending radius (inner radius) of 0.15 mm, the case where no cracks are confirmed on the outer surface of the bending of the test piece is evaluated as "excellent". A case where cracks were confirmed even if they were minute was evaluated as "poor". The presence or absence of residual smut was confirmed by observing the surface of the test piece (copper alloy material) that had been pretreated, immersed in a chemical polishing liquid for about 1 minute, washed with water, and dried. At this time, the chemical polishing liquid was an acidic aqueous solution containing about 20% by mass of sulfuric acid and about 8% by mass of hydrogen peroxide, and was kept at about 40.degree. The surface area of the test piece to be immersed in the chemical polishing liquid was set to about 2000 mm 2 (front and back surfaces with a width of 20 mm and a length of 50 mm). The pretreatment of the specimen to be tested was carried out in the order of ethanol degreasing, alkaline electrolytic degreasing, immersion (neutralization) in a 5% sulfuric acid aqueous solution, washing with water, and drying.
　なお、表１に示す参考例に関し、試料３０の銅合金材は、引張強さが５４０ＭＰａとなり、６２０ＭＰａ未満であった。導電率は６３．０％ＩＡＣＳとなり、４０．０％ＩＡＣＳ以上であった。曲げ加工性は「優」となり、残留スマットは「無」となった。また、試料３１の銅合金材は、引張強さが６５０ＭＰａとなり、６２０ＭＰａ以上であった。導電率は４５．０％ＩＡＣＳとなり、４０．０％ＩＡＣＳ以上であった。曲げ加工性は「優」となり、残留スマットは「有」となった。 Regarding the reference example shown in Table 1, the copper alloy material of sample 30 had a tensile strength of 540 MPa, which was less than 620 MPa. The electrical conductivity was 63.0%IACS, which was 40.0%IACS or more. The bending workability was "excellent" and the residual smut was "absent". Moreover, the copper alloy material of sample 31 had a tensile strength of 650 MPa, which was 620 MPa or more. The electrical conductivity was 45.0%IACS, which was 40.0%IACS or more. The bending workability was evaluated as "excellent", and the residual smut was evaluated as "present".
＜Ｆｅの影響＞
　表２（表１から抽出）に示す試料１、１０および１１の銅合金材は、溶解鋳造工程の成分調整で最終的に得られる銅合金材のＦｅ含有率を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、Ｆｅ含有率は、試料１は２．２０％であるため、この発明で規定する１．６％以上２．６％以下の範囲内である。これに対して、試料１０はより小さい１．５０質量％であり、試料１１はより大きい２．８０％であるため、上記の範囲外である。 <Influence of Fe>
The copper alloy materials of samples 1, 10 and 11 shown in Table 2 (extracted from Table 1) were different in Fe content of the copper alloy material finally obtained by adjusting the composition in the melting and casting process. They are manufactured to have substantially the same thickness through substantially the same manufacturing process. Specifically, since the Fe content of sample 1 is 2.20%, it falls within the range of 1.6% or more and 2.6% or less defined in the present invention. In contrast, Sample 10 has a lower 1.50% by weight and Sample 11 has a higher 2.80%, which is outside the above range.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、引張強さは、試料１が６７０ＭＰａとなり、試料１１が６７２ＭＰａとなり、いずれも６２０ＭＰａ以上となった。これに対して、試料１０は５７５ＭＰａとなり、６２０ＭＰａ未満となった。また、導電率は、試料１が４８．２％ＩＡＣＳとなり、試料１０が５６．３％ＩＡＣＳとなり、いずれも４０．０％ＩＡＣＳ以上となった。これに対して、試料１１は３８．８％ＩＡＣＳとなり、４０．０％ＩＡＣＳ未満となった。また、曲げ加工性は、試料１、１０の「優」に対して、試料１１は「劣」となった。また、残留スマットは、試料１、１０および１１のいずれも「無」となった。 As shown in Table 2, the tensile strength was 670 MPa for sample 1 and 672 MPa for sample 11, both of which were 620 MPa or more. On the other hand, Sample 10 was 575 MPa, which was less than 620 MPa. The electrical conductivity was 48.2%IACS for sample 1 and 56.3%IACS for sample 10, both of which were 40.0%IACS or higher. In contrast, sample 11 resulted in 38.8% IACS and less than 40.0% IACS. Further, the bending workability of sample 11 was "poor" while samples 1 and 10 were "excellent". Moreover, all of Samples 1, 10 and 11 had "no" residual smut.
　Ｆｅ含有率を異ならせた試料１、１０および１１の銅合金材の比較評価により、Ｆｅ含有率が小さくなって上記の範囲外になると、銅合金材の引張強さが低下して６２０ＭＰａに達しないことが判明した。また、Ｆｅ含有率が大きくなって上記の範囲外になると、銅合金材の導電率が低下して４０．０％ＩＡＣＳに達しないことが判明した。また、Ｆｅ含有率は、銅合金材の曲げ加工性や残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、１．６％以上２．６％以下のＦｅを含有する銅合金材は、有効である。 A comparative evaluation of the copper alloy materials of Samples 1, 10 and 11 with different Fe contents showed that when the Fe content was small and outside the above range, the tensile strength of the copper alloy material decreased and reached 620 MPa. It turned out not to. Further, it was found that when the Fe content becomes large and falls outside the above range, the electrical conductivity of the copper alloy material decreases and does not reach 40.0% IACS. It was also found that the Fe content hardly affects the bending workability and residual smut of the copper alloy material. Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, having a conductivity of 40.0% IACS or more, and having good bending workability, it is practically 1.6% A copper alloy material containing 2.6% or more of Fe is effective.
＜Ｐの影響＞
　表３（表１から抽出）に示す試料１、１２の銅合金材は、溶解鋳造工程の成分調整で最終的に得られる銅合金材のＰ含有率を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、Ｐ含有率は、試料１は０．０３％であるため、この発明で規定する０．０１％以上０．３％以下の範囲内である。また、試料１２は試料１よりも大きい０．２２質量％であり、上記の範囲内であるが、発明者がより好ましいと考える０．０１％以上０．２０％以下の範囲外である。 <Influence of P>
The copper alloy materials of samples 1 and 12 shown in Table 3 (extracted from Table 1) are substantially the same except that the P content of the finally obtained copper alloy material is changed by adjusting the composition in the melting and casting process. It is manufactured so as to have substantially the same thickness through the manufacturing process of Specifically, since the P content of Sample 1 is 0.03%, it falls within the range of 0.01% or more and 0.3% or less specified in the present invention. Further, the content of sample 12 is 0.22% by mass, which is larger than that of sample 1, which is within the above range, but is outside the range of 0.01% or more and 0.20% or less, which the inventor considers more preferable.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３に示すように、引張強さは、試料１、１２ともに６２０ＭＰａ以上となり、試料１２は試料１（６７０ＭＰａ）よりも大きい６７５ＭＰａとなった。また、導電率は、試料１、１２ともに４０．０％ＩＡＣＳ以上となり、試料１２は試料１（４８．２％ＩＡＣＳ）よりも大きい４８．８％ＩＡＣＳとなった。また、曲げ加工性は、試料１の「優」に対して、試料１２は「劣」となった。また、残留スマットは、試料１、１２ともに「無」となった。 As shown in Table 3, the tensile strength of both samples 1 and 12 was 620 MPa or more, and sample 12 was 675 MPa, which was larger than sample 1 (670 MPa). Also, the electrical conductivity was 40.0% IACS or more for both samples 1 and 12, and sample 12 was 48.8% IACS, which is higher than sample 1 (48.2% IACS). In addition, the bending workability of sample 12 was "poor" while sample 1 was "excellent". Also, residual smut was "absent" for both samples 1 and 12.
　Ｐ含有率を異ならせた試料１、１２の銅合金材の比較評価により、Ｐ含有率は、銅合金材の引張強さや導電率に影響を及ぼしにくいことが判明した。また、Ｐ含有率が大きくなると、銅合金材の曲げ加工性が劣化する傾向があることが判明した。また、Ｐ含有率は、銅合金材の残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有する観点で、実用上、この発明で規定する０．０１％以上０．３％以下のＰを含有する銅合金材は、有効である。加えて、良好な曲げ加工性を有する観点で、実用上、０．０１％以上０．２０％以下のＰを含有する銅合金材は、有効である。 A comparative evaluation of the copper alloy materials of samples 1 and 12 with different P contents revealed that the P content hardly affected the tensile strength and electrical conductivity of the copper alloy materials. In addition, it was found that when the P content increases, the bending workability of the copper alloy material tends to deteriorate. It was also found that the P content hardly affects the residual smut of the copper alloy material. Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, and having an electrical conductivity of 40.0% IACS or more, it is practically 0.01% or more and 0.3% or less specified in this invention. A copper alloy material containing P is effective. In addition, from the viewpoint of good bending workability, a copper alloy material containing 0.01% or more and 0.20% or less of P is practically effective.
＜Ｚｎの影響＞
　表４（表１から抽出）に示す試料１、１３の銅合金材は、溶解鋳造工程の成分調整で最終的に得られる銅合金材のＺｎ含有率を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、Ｚｎ含有率は、試料１は０．１２％であるため、この発明で規定する０．０１％以上０．３％以下の範囲内である。これに対して、試料１３はより大きい０．４０％であるため、上記の範囲外である。 <Influence of Zn>
The copper alloy materials of samples 1 and 13 shown in Table 4 (extracted from Table 1) are substantially the same except that the Zn content of the finally obtained copper alloy material is changed by adjusting the composition in the melting and casting process. It is manufactured so as to have substantially the same thickness through the manufacturing process of Specifically, since the Zn content in Sample 1 is 0.12%, it falls within the range of 0.01% to 0.3% specified in the present invention. In contrast, Sample 13 has a higher 0.40% and is therefore outside the above range.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４に示すように、引張強さは、試料１、１２ともに６２０ＭＰａ以上となり、試料１３は試料１（６７０ＭＰａ）よりも大きい６７４ＭＰａとなった。また、導電率は、４０．０％ＩＡＣＳ以上となった試料１（４８．２％ＩＡＣＳ）に対して、試料１３は３９．２％ＩＡＣＳとなり、４０．０％ＩＡＣＳ未満となった。また、曲げ加工性は、試料１の「優」に対して、試料１３は「劣」となった。また、残留スマットは、試料１、１３ともに「無」となった。 As shown in Table 4, the tensile strength of both samples 1 and 12 was 620 MPa or more, and sample 13 was 674 MPa, which was larger than sample 1 (670 MPa). Also, the electrical conductivity of sample 13 was 39.2%IACS, which was less than 40.0%IACS, compared to sample 1 (48.2%IACS), which was 40.0%IACS or more. In addition, the bending workability of sample 13 was "poor" while sample 1 was "excellent". Also, residual smut was "absent" for both samples 1 and 13.
　Ｚｎ含有率を異ならせた試料１、１３の銅合金材の比較評価により、Ｚｎ含有率が大きくなって上記の範囲外になると、銅合金材の導電率が低下して４０．０％ＩＡＣＳに達しないとともに、銅合金材の曲げ加工性が劣化する傾向があることが判明した。また、Ｚｎ含有率は、銅合金材の引張強さや残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、０．０１％以上０．３％以下のＺｎを含有する銅合金材は、有効である。 According to a comparative evaluation of the copper alloy materials of Samples 1 and 13 with different Zn contents, when the Zn content increases and falls outside the above range, the electrical conductivity of the copper alloy material decreases to 40.0% IACS. It was found that the bending workability of the copper alloy material tended to deteriorate. It was also found that the Zn content hardly affects the tensile strength and residual smut of the copper alloy material. Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, having a conductivity of 40.0% IACS or more, and having good bending workability, it is practically 0.01% A copper alloy material containing 0.3% or more of Zn is effective.
＜Ｓｎの影響＞
　表５（表１から抽出）に示す試料１、４、１４および１５の銅合金材は、溶解鋳造工程の成分調整で最終的に得られる銅合金材のＳｎ含有率を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、Ｓｎ含有率は、試料１は０．６０％であり、試料１３は０．３０％であるため、この発明で規定する０．３％以上０．８％以下の範囲内である。これに対して、試料４はより小さい０．２０質量％であり、試料１４はより大きい０．９０％であるため、上記の範囲外である。 <Influence of Sn>
The copper alloy materials of samples 1, 4, 14 and 15 shown in Table 5 (extracted from Table 1) were different in Sn content of the copper alloy material finally obtained by adjusting the composition in the melting and casting process. are manufactured to have substantially the same thickness through substantially the same manufacturing process. Specifically, the Sn content is 0.60% in Sample 1 and 0.30% in Sample 13, and is within the range of 0.3% to 0.8% specified in the present invention. . In contrast, Sample 4 has a lower 0.20% by weight and Sample 14 has a higher 0.90%, which is outside the above range.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表５に示すように、引張強さは、試料１、４および１５が６２０ＭＰａ以上となり、試料１４が６２０ＭＰａ未満となった。具体的に、試料１（６７０ＭＰａ）の引張強さに対して、試料４は６２４ＭＰａで小さくなり、試料１４は６０４ＭＰａでさらに小さくなったが、試料１５は６９０ＭＰａでより大きくなった。また、導電率は、試料１、４および１４が４０．０％ＩＡＣＳ以上となり、試料１５が４０．０％ＩＡＣＳ未満となった。具体的に、試料１（４８．２％ＩＡＣＳ）の導電率に対して、試料４は５１．０％ＩＡＣＳでより大きくなり、試料１４は５５．０％ＩＡＣＳでより一層大きくなったが、試料１５は３９．８％ＩＡＣＳでより小さくなった。また、曲げ加工性は、試料１、４および１４の「優」に対して、試料１５は「劣」となった。また、残留スマットは、試料１、４、１４および１５ともに「無」となった。 As shown in Table 5, the tensile strength of samples 1, 4 and 15 was 620 MPa or more, and sample 14 was less than 620 MPa. Specifically, compared to the tensile strength of sample 1 (670 MPa), sample 4 was smaller at 624 MPa, sample 14 was even smaller at 604 MPa, while sample 15 was larger at 690 MPa. In terms of electrical conductivity, Samples 1, 4 and 14 were 40.0%IACS or more, and Sample 15 was less than 40.0%IACS. Specifically, relative to the conductivity of sample 1 (48.2% IACS), sample 4 was greater at 51.0% IACS and sample 14 was even greater at 55.0% IACS, whereas sample 15 was smaller at 39.8% IACS. Further, the bending workability of Sample 15 was "poor" while Samples 1, 4 and 14 were "excellent". In addition, all of samples 1, 4, 14 and 15 were found to have no residual smut.
　Ｓｎ含有率を異ならせた試料１、４、１４および１５の銅合金材の比較評価により、Ｓｎ含有率が小さくなると、銅合金材の引張強さが低下する傾向があることが判明した。また、Ｓｎ含有率がさらに小さくなって上記の範囲外になると、銅合金材の引張強さが６２０ＭＰａに達しないことが判明した。また、試料１、４の銅合金材の比較評価により、銅合金材が０．３％を超えるＳｎを含有していると、６２５ＭＰａ以上の引張強さが得られることが判明した。また、Ｓｎ含有率が小さくなると、銅合金材の導電率が大きくなる傾向があることが判明した。また、Ｓｎ含有率が大きくなって上記の範囲外になると、銅合金材の導電率がさらに低下して４０．０％ＩＡＣＳに達しないことが判明した。また、Ｓｎ含有率が大きくなると、銅合金材の曲げ加工性が劣化する傾向があることが判明した。また、Ｓｎ含有率は、残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、０．３％以上０．８％以下のＳｎを含有する銅合金材は、有効である。 A comparative evaluation of the copper alloy materials of samples 1, 4, 14 and 15 with different Sn contents revealed that the tensile strength of the copper alloy materials tended to decrease as the Sn content decreased. In addition, it was found that when the Sn content was further decreased and fell outside the above range, the tensile strength of the copper alloy material did not reach 620 MPa. Further, a comparative evaluation of the copper alloy materials of Samples 1 and 4 revealed that when the copper alloy material contained more than 0.3% Sn, a tensile strength of 625 MPa or more was obtained. It was also found that the electrical conductivity of the copper alloy material tends to increase as the Sn content decreases. Further, it was found that when the Sn content becomes large and falls outside the above range, the electrical conductivity of the copper alloy material further decreases and does not reach 40.0%IACS. In addition, it was found that when the Sn content increases, the bending workability of the copper alloy material tends to deteriorate. Also, it was found that the Sn content hardly affects the residual smut. Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, having a conductivity of 40.0% IACS or more, and having good bending workability, it is practically 0.3% A copper alloy material containing 0.8% or more of Sn is effective.
＜第１熱処理工程の影響＞
　表６（表１から抽出）に示す試料１、４、１６、１７および１８の銅合金材に着目し、第１熱処理工程の影響について説明する。試料１、１６、１７および１８の銅合金材は、第１熱処理工程の加熱保持条件を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。また、試料１、１７および１８の銅合金材はＳｎ含有率が０．６０％となるように成分調整されたものであり、試料４、１６の銅合金材は０．３０％になるように成分調整されたものである。具体的に、第１熱処理工程の加熱保持条件は、試料１、４は５８０℃で約３分であるため、この発明で規定する５００℃以上６００℃以下で４ｈ以下の範囲内である。これに対して、試料１６はより低温の４５０℃であり、試料１７はより高温の６５０℃であるため、保持時間は試料１、４と同等であるが、上記の範囲外である。また、試料１８はより長時間の約５ｈであるため、保持温度は試料１、４と同等であるが、上記の範囲外である。 <Influence of the first heat treatment step>
Focusing on the copper alloy materials of samples 1, 4, 16, 17 and 18 shown in Table 6 (extracted from Table 1), the influence of the first heat treatment step will be described. The copper alloy materials of Samples 1, 16, 17 and 18 were manufactured to have substantially the same thickness through substantially the same manufacturing process except that the heating and holding conditions in the first heat treatment step were changed. It is a thing. In addition, the copper alloy materials of samples 1, 17 and 18 were adjusted so that the Sn content was 0.60%, and the copper alloy materials of samples 4 and 16 were adjusted so that the Sn content was 0.30%. The ingredients are adjusted. Specifically, the heating and holding conditions in the first heat treatment step are within the range of 500° C. or higher and 600° C. or lower and 4 hours or shorter as defined in the present invention, since Samples 1 and 4 are heated at 580° C. for about 3 minutes. In contrast, sample 16 is at a lower temperature of 450° C. and sample 17 is at a higher temperature of 650° C., so the retention times are similar to samples 1 and 4, but outside the above range. Also, since sample 18 is longer, about 5 hours, the holding temperature is similar to samples 1 and 4, but outside the above range.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表６に示すように、引張強さは、６２０ＭＰａ以上である試料１（６７０ＭＰａ）に対して、試料４はＳｎ含有率が試料１よりも小さいことに起因して６２４ＭＰａと小さくなったが、６２０ＭＰａ以上であった。これに対して、低温の保持として上記の範囲外とした試料１６は６１０ＭＰａとなり、高温の保持として上記の範囲外とした試料１７は５９６ＭＰａとなり、長時間の保持として上記の範囲外とした試料１８は６１２ＭＰａとなり、これらのいずれもが６２０ＭＰａ未満となった。また、導電率は、４０．０％ＩＡＣＳ以上である試料１（４８．２％ＩＡＣＳ）に対して、試料４、１８は５１．０％ＩＡＣＳとなり、試料１６は５０．５％ＩＡＣＳとなり、試料１７は５１．８％ＩＡＣＳとなり、これらのいずれもが試料１よりも大きくなった。また、曲げ加工性は、試料１、１６、１７および１８ともに「優」となった。また、残留スマットは、試料１、１６、１７および１８ともに「無」となった。 As shown in Table 6, the tensile strength of sample 1 (670 MPa), which is 620 MPa or more, was as small as 624 MPa due to the Sn content of sample 4 being smaller than that of sample 1, but 620 MPa. That was it. On the other hand, sample 16, which is out of the above range for low temperature retention, has a value of 610 MPa, sample 17, which is out of the above range for high temperature retention, has a value of 596 MPa, and sample 18, which is out of the above range for long term retention. was 612 MPa, and both of these were less than 620 MPa. Also, the electrical conductivity is 51.0% IACS for samples 4 and 18, 50.5% IACS for sample 16, and 50.5% IACS for sample 1 (48.2% IACS), which is 40.0% IACS or more. 17 resulted in 51.8% IACS, both of which were greater than Sample 1. In addition, the bending workability of samples 1, 16, 17 and 18 were all "excellent". In addition, all samples 1, 16, 17 and 18 were found to have no residual smut.
　第１熱処理工程の加熱保持温度を異ならせた試料１、１７の銅合金材の比較評価および試料４、１６の銅合金材の比較評価により、第１熱処理工程の加熱保持が高温または低温になって上記の範囲外になると、銅合金材の引張強さが低下して６２０ＭＰａに達しない傾向があることが判明した。また、試料１、１８の銅合金材の比較評価により、第１熱処理工程の加熱保持が長時間になって上記の範囲外になると、銅合金材の引張強さが低下して６２０ＭＰａに達しない傾向があることが判明した。また、試料１、４、１６、１７および１８の銅合金材の比較評価により、第１熱処理工程の加熱保持条件は、銅合金材の導電率や曲げ加工性や残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、第１冷間圧延材に対して５００℃以上６００℃以下の温度で４ｈ以下の加熱保持を行って第１熱処理材を作製する第１熱処理工程は、有効である。 Comparative evaluation of the copper alloy materials of samples 1 and 17 with different heating and holding temperatures in the first heat treatment step and comparative evaluation of the copper alloy materials of samples 4 and 16 showed that the heating and holding temperature in the first heat treatment step was high or low. It has been found that if the tensile strength is outside the above range, the tensile strength of the copper alloy material tends to decrease and not reach 620 MPa. Further, according to a comparative evaluation of the copper alloy materials of Samples 1 and 18, if the heating and holding in the first heat treatment step is prolonged and is outside the above range, the tensile strength of the copper alloy material decreases and does not reach 620 MPa. It turned out that there is a trend. In addition, a comparative evaluation of the copper alloy materials of Samples 1, 4, 16, 17 and 18 revealed that the heating and holding conditions in the first heat treatment step do not easily affect the electrical conductivity, bending workability, and residual smut of the copper alloy material. There was found. Therefore, it has no residual smut, has a tensile strength of 620 MPa or more, has a conductivity of 40.0% IACS or more, and in addition has good bending workability. The first heat treatment step of producing the first heat-treated material by heating and holding the rolled material at a temperature of 500° C. or more and 600° C. or less for 4 hours or less is effective.
＜第２冷間圧延工程の圧延加工度の影響＞
　表７（表１から抽出）に示す試料１、６、１９および２０の銅合金材に着目し、第２冷間圧延工程の影響について説明する。試料１、６、１９および３０の銅合金材は、第２冷間圧延工程の圧延加工度を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、第２冷間圧延工程の圧延加工度は、試料１は６４％であり、試料６は４６％であるため、この発明で規定する２０％以上９０％以下の範囲内である。これに対して、試料１９は１７％であり、試料２０は９１％であるため、上記の範囲外である。 <Influence of rolling workability in the second cold rolling step>
Focusing on the copper alloy materials of samples 1, 6, 19 and 20 shown in Table 7 (extracted from Table 1), the influence of the second cold rolling step will be described. The copper alloy materials of Samples 1, 6, 19 and 30 were made to have substantially the same thickness through substantially the same manufacturing process except that the degree of rolling work in the second cold rolling process was changed. It is manufactured. Specifically, the degree of rolling reduction in the second cold rolling step is 64% for sample 1 and 46% for sample 6, and therefore falls within the range of 20% to 90% specified in the present invention. In contrast, sample 19 is 17% and sample 20 is 91%, which are outside the above range.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表７に示すように、引張強さは、６２０ＭＰａ以上である試料１（６７０ＭＰａ）に対して、圧延加工度を小さくした試料６は６５４ＭＰａと小さくなり、圧延加工度を小さくして上記の範囲外とした試料１９は６２４ＭＰａと更に小さくなったが、これらのいずれもが６２０ＭＰａ以上であった。これに対して、圧延加工度を大きくして上記の範囲外とした試料２０は６１０ＭＰａとより一層小さくなり、６２０ＭＰａ未満となった。また、導電率は、４０．０％ＩＡＣＳ以上である試料１（４８．２％ＩＡＣＳ）に対して、圧延加工度を大きくして上記の範囲外とした試料２０は、４８．８％ＩＡＣＳで同程度であった。これに対して、圧延加工度を小さくした試料６は、４５．８％ＩＡＣＳと小さくなった。また、圧延加工度を更に小さくして上記の範囲外とした試料１９は、３９．６％ＩＡＣＳと更に小さくなって、４０．０％ＩＡＣＳ未満となった。また、曲げ加工性は、試料１、６、１９および２０ともに「優」となった。また、残留スマットは、試料１、６、１９および２０ともに「無」となった。 As shown in Table 7, the tensile strength of sample 1 (670 MPa), which is 620 MPa or more, is as small as 654 MPa for sample 6, which has a reduced degree of rolling. Although the sample 19 with the same value was further reduced to 624 MPa, all of them were 620 MPa or more. On the other hand, Sample 20, in which the degree of rolling was increased to be outside the above range, was 610 MPa, which was even lower, and was less than 620 MPa. Further, the electrical conductivity of sample 1 (48.2% IACS), which is 40.0% IACS or more, is 48.8% IACS for sample 20, which is out of the above range by increasing the degree of rolling. was at the same level. On the other hand, Sample 6, in which the degree of rolling work was reduced, was as small as 45.8% IACS. Sample 19, in which the degree of rolling work was further reduced to be outside the above range, was further reduced to 39.6%IACS, which was less than 40.0%IACS. In addition, the bending workability of samples 1, 6, 19 and 20 were all "excellent". In addition, all of samples 1, 6, 19 and 20 were "absent" with respect to residual smut.
　第２冷間圧延工程の圧延加工度を異ならせた試料１、６および１９の銅合金材の比較評価により、第２冷間圧延工程の圧延加工度が小さくなると銅合金材の引張強さが低下する傾向があることが判明した。また、試料１、６、１９および２０の銅合金材の比較評価により、第２冷間圧延工程の圧延加工度が過大になって上記の範囲外になると、銅合金材の引張強さが低下して６２０ＭＰａに達しないことが判明した。また、試料１、６、１９および２０の銅合金材の比較評価により、第２冷間圧延工程の圧延加工度は、過大になって上記の範囲外になっても銅合金材の導電率に影響を及ぼしにくく、過小になって上記の範囲外になると銅合金材の導電率が低下して４０．０％ＩＡＣＳに達しないことが判明した。また、試料１、６、１９および２０の銅合金材の比較評価により、第２冷間圧延工程の圧延加工度は、銅合金材の曲げ加工性や残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、第１熱処理材を用いて２０％以上９０％以下の圧延加工度で冷間圧延を行って第２冷間圧延材を作製する第２冷間圧延工程は、有効である。 Comparative evaluation of the copper alloy materials of Samples 1, 6 and 19, which differed in the degree of rolling reduction in the second cold rolling process, showed that the tensile strength of the copper alloy material increased as the degree of rolling reduction in the second cold rolling process decreased. A decreasing trend was found. In addition, a comparative evaluation of the copper alloy materials of Samples 1, 6, 19 and 20 revealed that when the degree of rolling work in the second cold rolling step is excessively outside the above range, the tensile strength of the copper alloy material decreases. It was found that the pressure did not reach 620 MPa. Further, by comparative evaluation of the copper alloy materials of Samples 1, 6, 19 and 20, even if the degree of rolling workability in the second cold rolling step is excessively outside the above range, the electrical conductivity of the copper alloy material does not change. It has been found that the electrical conductivity of the copper alloy material is lowered and does not reach 40.0% IACS when it is too small and is outside the above range. In addition, a comparative evaluation of the copper alloy materials of Samples 1, 6, 19 and 20 revealed that the degree of rolling workability in the second cold rolling step does not easily affect the bending workability and residual smut of the copper alloy material. . Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, having a conductivity of 40.0% IACS or more, and having good bending workability, it is practically the first heat-treated material The second cold rolling step of cold rolling at a rolling reduction ratio of 20% or more and 90% or less to produce the second cold rolled material is effective.
＜第２熱処理工程の加熱保持条件の影響＞
　表８（表１から抽出）に示す試料１、２１、２２、２３および２４の銅合金材に着目し、第２熱処理工程の影響について説明する。試料１、２１、２２、２３および２４の銅合金材は、第２熱処理工程の加熱保持条件を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、第２熱処理工程の加熱保持条件は、試料１は４５０℃で約４ｈであるため、この発明で規定する３８０℃以上４８０℃以下で１ｈ以上１２ｈ以下の範囲内である。これに対して、試料２１はより低温の３５０℃であり、試料２２はより高温の５００℃であるため、保持時間は試料１と同等であるが、上記の範囲外である。また、試料２３はより短時間の約０．５ｈであり、試料２４はより長時間の約２０ｈであるため、保持温度は上記の範囲内であるが、保持時間は上記の範囲外である。 <Influence of heating and holding conditions in the second heat treatment step>
Focusing on the copper alloy materials of samples 1, 21, 22, 23 and 24 shown in Table 8 (extracted from Table 1), the influence of the second heat treatment step will be described. The copper alloy materials of Samples 1, 21, 22, 23 and 24 were made to have substantially the same thickness through substantially the same manufacturing process except that the heating and holding conditions in the second heat treatment step were changed. It is manufactured. Specifically, the heating and holding conditions in the second heat treatment step are within the range of 380° C. to 480° C. and 1 hour to 12 hours as defined in the present invention, since the sample 1 is heated at 450° C. for about 4 hours. In contrast, sample 21 is at a lower temperature of 350° C. and sample 22 is at a higher temperature of 500° C., so the retention time is similar to sample 1, but outside the ranges given above. Also, sample 23 is shorter, about 0.5 hours, and sample 24 is longer, about 20 hours, so the holding temperature is within the above range, but the holding time is outside the above range.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表８に示すように、引張強さは、６２０ＭＰａ以上である試料１（６７０ＭＰａ）に対して、低温または高温の保持として上記の範囲外とした試料２１（６０６ＭＰａ）と試料２２（５７５ＭＰａ）、および、短時間または長時間の保持として上記の範囲外とした試料２３（５９８ＭＰａ）と試料２４（６０２ＭＰａ）のいずれもが小さくなり、６２０ＭＰａ未満となった。また、導電率は、４０．０％ＩＡＣＳ以上である試料１（４８．２％ＩＡＣＳ）に対して、低温の保持として上記の範囲外とした試料２１（３８．０％ＩＡＣＳ）と短時間の保持として上記の範囲外とした試料２３（３９．７％ＩＡＣＳ）のいずれもが小さくなり、４０．０％ＩＡＣＳ未満となった。また、導電率は、高温の保持として上記の範囲外とした試料２２（５０．５％ＩＡＣＳ）と長時間の保持として上記の範囲外とした試料２４（５２．０％ＩＡＣＳ）のいずれもが大きくなった。また、曲げ加工性は、試料１、２１、２２、２３および２４ともに「優」となった。また、残留スマットは、試料１、２１、２２、２３および２４ともに「無」となった。 As shown in Table 8, the tensile strength is sample 1 (670 MPa), which is 620 MPa or more, and sample 21 (606 MPa) and sample 22 (575 MPa), which are outside the above range for low or high temperature retention, and , Sample 23 (598 MPa) and Sample 24 (602 MPa), both of which were out of the above range for short-term or long-term retention, decreased to less than 620 MPa. In addition, the electrical conductivity of sample 1 (48.2% IACS), which is 40.0% IACS or more, is out of the above range for low temperature retention, and sample 21 (38.0% IACS) is used for a short time. Sample 23 (39.7% IACS), whose retention was outside the above range, both decreased to less than 40.0% IACS. In addition, both Sample 22 (50.5% IACS), which is outside the above range for high temperature retention, and Sample 24 (52.0% IACS), which is outside the above range for long-term retention, are got bigger. In addition, the bending workability of samples 1, 21, 22, 23 and 24 were all "excellent". In addition, all samples 1, 21, 22, 23 and 24 were found to have no residual smut.
　第２熱処理工程の加熱保持温度を異ならせた試料１、２１、２２、２３および２４の銅合金材の比較評価により、第２熱処理工程の加熱保持が高温または低温になって上記の範囲外になると、銅合金材の引張強さが低下して６２０ＭＰａに達しない傾向があることが判明した。また、試料１、２１および２３の銅合金材の比較評価により、第２熱処理工程の加熱保持が低温または短時間になって上記の範囲外になると、銅合金材の導電率が小さくなって４０．０％ＩＡＣＳに達しない傾向があることが判明した。また、試料１、２２および２４の銅合金材の比較評価により、第２熱処理工程の加熱保持が高温または長時間になると、銅合金材の導電率が大きくなる傾向があることが判明した。また、試料１、２１、２２、２３および２４の銅合金材の比較評価により、第２熱処理工程の加熱保持条件は、銅合金材の曲げ加工性や残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、第２冷間圧延材に対して３８０℃以上４８０℃以下の温度で１ｈ以上１２ｈ以下の加熱保持を行って第２熱処理材を作製する第２熱処理工程は、有効である。 By comparative evaluation of the copper alloy materials of Samples 1, 21, 22, 23 and 24 with different heating and holding temperatures in the second heat treatment step, the heating and holding temperature in the second heat treatment step became high or low and fell outside the above range. Then, it was found that the tensile strength of the copper alloy material tended to decrease and not reach 620 MPa. Further, according to a comparative evaluation of the copper alloy materials of Samples 1, 21 and 23, when the heating and holding in the second heat treatment step is at a low temperature or for a short time and is outside the above range, the electrical conductivity of the copper alloy material decreases to 40%. It was found that there was a tendency to not reach .0% IACS. Further, a comparative evaluation of the copper alloy materials of Samples 1, 22 and 24 revealed that the electrical conductivity of the copper alloy material tends to increase when the heating and holding time in the second heat treatment step is high or long. In addition, a comparative evaluation of the copper alloy materials of Samples 1, 21, 22, 23 and 24 revealed that the heating and holding conditions in the second heat treatment step had little effect on the bending workability and residual smut of the copper alloy materials. . Therefore, there is no residual smut, it has a tensile strength of 620 MPa or more, has an electrical conductivity of 40.0% IACS or more, and in addition, has good bending workability. A second heat treatment step in which the rolled material is heated and held at a temperature of 380° C. or more and 480° C. or less for 1 hour or more and 12 hours or less to produce the second heat treated material is effective.
＜第３冷間圧延の圧延加工度の影響＞
　表９（表１から抽出）に示す試料１、２５および２６の銅合金材に着目し、第３冷間圧延工程の影響について説明する。試料１、２５および２６の銅合金材は、第３冷間圧延工程の圧延加工度を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、第３冷間圧延工程の圧延加工度は、試料１は７０％であるため、この発明で規定する６０％以上８０％以下の範囲内である。これに対して、試料２５は５０％であり、試料２６は８５％であるため、上記の範囲外である。 <Influence of rolling workability of the third cold rolling>
Focusing on the copper alloy materials of samples 1, 25 and 26 shown in Table 9 (extracted from Table 1), the influence of the third cold rolling process will be described. The copper alloy materials of Samples 1, 25, and 26 were manufactured to have substantially the same thickness through substantially the same manufacturing process, except that the degree of rolling workability in the third cold rolling step was made different. It is a thing. Specifically, since the rolling workability of the third cold rolling step is 70% for the sample 1, it falls within the range of 60% or more and 80% or less specified in the present invention. On the other hand, sample 25 is 50% and sample 26 is 85%, which are outside the above range.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表９に示すように、引張強さは、６２０ＭＰａ以上である試料１（６７０ＭＰａ）に対して、圧延加工度を小さくして上記の範囲外とした試料２５（５６９ＭＰａ）と圧延加工度を大きくして上記の範囲外とした試料２６（５８０ＭＰａ）のいずれもが小さくなり、６２０ＭＰａ未満となった。また、導電率は、４０．０％ＩＡＣＳ以上である試料１（４８．２％ＩＡＣＳ）に対して、圧延加工度を小さくして上記の範囲外とした試料２５（４８．２％ＩＡＣＳ）は同程度となり、圧延加工度を大きくして上記の範囲外とした試料２６（４６．０％ＩＡＣＳ）は４０．０％ＩＡＣＳ未満にはならなかったものの試料１よりも小さくなった。また、曲げ加工性は、試料１、２５および２６ともに「優」となった。また、残留スマットは、試料１、２５および２６ともに「無」となった。 As shown in Table 9, the tensile strength is sample 1 (670 MPa), which is 620 MPa or more, and sample 25 (569 MPa), which is out of the above range by reducing the degree of rolling, and increasing the degree of rolling. All of Sample 26 (580 MPa), which was out of the above range, decreased to less than 620 MPa. In addition, the electrical conductivity of sample 1 (48.2% IACS), which is 40.0% IACS or more, is reduced to the extent of rolling and is outside the above range, sample 25 (48.2% IACS). Sample 26 (46.0% IACS), which was made to be outside the above range by increasing the degree of rolling, did not fall below 40.0% IACS, but was smaller than Sample 1. In addition, the bendability of samples 1, 25 and 26 was all "excellent". In addition, all of samples 1, 25 and 26 were "absent" with respect to residual smut.
　第３冷間圧延工程の圧延加工度を異ならせた試料１、２５および２６の銅合金材の比較評価により、第３冷間圧延工程の圧延加工度が上記の範囲外になると銅合金材の引張強さが低下して６２０ＭＰａに達しない傾向があることが判明した。また、第３冷間圧延工程の圧延加工度が小さくなって上記の範囲外になっても、銅合金材の導電率に影響を及ぼしにくい傾向があることが判明した。また、第３冷間圧延工程の圧延加工度が大きくなって上記の範囲外になると、銅合金材の導電率が小さくなる傾向があることが判明した。また、第３冷間圧延工程の圧延加工度は、銅合金材の曲げ加工性や残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、第２熱処理材を用いて６０％以上８０％以下の圧延加工度で冷間圧延を行って第３冷間圧延材を作製する第３冷間圧延工程は、有効である。 A comparative evaluation of the copper alloy materials of Samples 1, 25 and 26 with different degrees of rolling reduction in the third cold rolling step revealed that when the degree of rolling reduction in the third cold rolling step was outside the above range, the copper alloy material It was found that the tensile strength tends to decrease and not reach 620 MPa. Further, it was found that even if the degree of rolling workability in the third cold rolling step becomes smaller and falls outside the above range, there is a tendency that the electrical conductivity of the copper alloy material is less likely to be affected. Further, it was found that when the degree of rolling workability in the third cold rolling step becomes large and falls outside the above range, the electrical conductivity of the copper alloy material tends to decrease. Moreover, it was found that the degree of rolling workability in the third cold rolling step does not easily affect the bending workability and residual smut of the copper alloy material. Therefore, from the viewpoint of having no residual smut, having a tensile strength of 620 MPa or more, having a conductivity of 40.0% IACS or more, and having good bending workability, the second heat-treated material is practically used. The third cold-rolling step of producing the third cold-rolled material by cold-rolling at a rolling reduction ratio of 60% or more and 80% or less using is effective.
＜第３熱処理工程の加熱保持条件の影響＞
　表１０（表１から抽出）に示す試料１、２７、２８および２９の銅合金材に着目し、第３熱処理工程の影響について説明する。試料１、２７、２８および２９の銅合金材は、第３熱処理工程の加熱保持条件を異ならせるようにした以外は、実質同等の製造工程を経て、実質同等の厚さを有するように作製されたものである。具体的に、第３熱処理工程の加熱保持条件は、試料１は４３０℃で約１分であるため、この発明で規定する２５０℃以上３８０℃以上で４ｈ以下の範囲内である。これに対して、試料２７はより低温の２００℃であり、試料２８はより高温の４００℃であるため、保持時間は試料１と同等であるが、上記の範囲外である。また、試料２９はより長時間の約５ｈであるため、保持温度は試料１と同等であるが、保持時間は上記の範囲外である。 <Influence of heating and holding conditions in the third heat treatment step>
Focusing on the copper alloy materials of samples 1, 27, 28 and 29 shown in Table 10 (extracted from Table 1), the influence of the third heat treatment step will be described. The copper alloy materials of Samples 1, 27, 28, and 29 were manufactured to have substantially the same thickness through substantially the same manufacturing process, except that the heating and holding conditions in the third heat treatment step were changed. It is a thing. Specifically, the heating and holding conditions of the third heat treatment step are within the range of 250° C. or higher and 380° C. or higher and 4 hours or shorter as defined in the present invention, since the sample 1 is heated at 430° C. for about 1 minute. In contrast, sample 27 is at a lower temperature of 200° C. and sample 28 is at a higher temperature of 400° C., so the retention times are similar to those of sample 1, but outside the ranges given above. Also, sample 29 is longer, about 5 hours, so the holding temperature is similar to sample 1, but the holding time is outside the above range.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　表１０に示すように、引張強さは、６２０ＭＰａ以上である試料１（６７０ＭＰａ）に対して、低温の保持として上記の範囲外とした試料２７（７１８ＭＰａ）は大きくなったが、高温の保持として上記の範囲外とした試料２８（６０３ＭＰａ）は小さくなって６２０ＭＰａ未満となった。また、導電率は、４０．０％ＩＡＣＳ以上である試料１（４８．２％ＩＡＣＳ）に対して、高温の保持として上記の範囲外とした試料２８（４８．２％ＩＡＣＳ）は同程度になったが、低温の保持として上記の範囲外とした試料２７（３９．８％ＩＡＣＳ）は小さくなって４０．０％ＩＡＣＳ未満となった。また、曲げ加工性は、試料１、２８および２９の「優」に対して、試料２７は「劣」となった。また、残留スマットは、試料１、２７、２８および２９ともに「無」となった。 As shown in Table 10, the tensile strength of Sample 1 (670 MPa), which is 620 MPa or more, is higher than that of Sample 27 (718 MPa), which is outside the above range for low temperature retention. Sample 28 (603 MPa), which was outside the above range, decreased to less than 620 MPa. In addition, the conductivity of sample 1 (48.2% IACS), which is 40.0% IACS or more, is about the same for sample 28 (48.2% IACS), which is outside the above range for maintaining high temperatures. However, Sample 27 (39.8% IACS), which was outside the above range for low temperature retention, decreased to less than 40.0% IACS. Further, the bending workability of sample 27 was "poor" while samples 1, 28 and 29 were "excellent". In addition, all of samples 1, 27, 28 and 29 had residual smut of "no".
　第３熱処理工程の加熱保持温度を異ならせた試料１、２８の銅合金材の比較評価および試料１、２９の銅合金材の比較評価により、第３熱処理工程の加熱保持が高温または長時間になって上記の範囲外になると、銅合金材の引張強さが低下して６２０ＭＰａに達しない傾向があることが判明した。また、試料１、２７の銅合金材の比較評価により、第３熱処理工程の加熱保持が低温になると、銅合金材の引張強さが大きくなる傾向があることが判明した。また、第３熱処理工程の加熱保持温度を異ならせた試料１、２７の銅合金材の比較評価により、第３熱処理工程の加熱保持が低温になって上記の範囲外になると、銅合金材の導電率が小さくなって４０．０％ＩＡＣＳに達しない傾向があることが判明した。また、試料１、２８の銅合金材の比較評価により、第３熱処理工程の加熱保持が高温になると、銅合金材の導電率が大きくなる傾向があることが判明した。また、試料１、２７の銅合金材の比較評価により、第３熱処理工程の加熱保持が低温になって上記の範囲外になると、銅合金材の曲げ加工性が劣化する傾向があることが判明した。また、試料１、２７、２８および２９の銅合金材の比較評価により、第３熱処理工程の加熱保持条件は、銅合金材の残留スマットに影響を及ぼしにくいことが判明した。したがって、残留スマットが無く、６２０ＭＰａ以上の引張強さを有し、４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有する観点で、実用上、第３冷間圧延材に対して２５０℃以上３８０℃以上の温度で４ｈ以下の加熱保持を行って銅合金材を作製する第３熱処理工程は、有効である。 Comparative evaluation of the copper alloy materials of samples 1 and 28 with different heating and holding temperatures in the third heat treatment step and comparative evaluation of the copper alloy materials of samples 1 and 29 showed that the heating and holding temperature in the third heat treatment step was high or long. It has been found that if the tensile strength is outside the above range, the tensile strength of the copper alloy material tends to decrease and not reach 620 MPa. In addition, a comparative evaluation of the copper alloy materials of Samples 1 and 27 revealed that the tensile strength of the copper alloy material tended to increase when the heating and holding temperature in the third heat treatment step was lowered. Further, by comparative evaluation of the copper alloy materials of Samples 1 and 27 with different heating and holding temperatures in the third heat treatment step, it was found that when the heating and holding temperature in the third heat treatment step was low and outside the above range, the copper alloy material It was found that the conductivity tended to decrease and not reach 40.0% IACS. Further, a comparative evaluation of the copper alloy materials of Samples 1 and 28 revealed that the electrical conductivity of the copper alloy material tends to increase when the heating and holding temperature in the third heat treatment step becomes high. In addition, a comparative evaluation of the copper alloy materials of Samples 1 and 27 revealed that the bending workability of the copper alloy material tends to deteriorate when the temperature of the third heat treatment step is outside the above range. did. In addition, a comparative evaluation of the copper alloy materials of Samples 1, 27, 28 and 29 revealed that the heating and holding conditions in the third heat treatment step had little effect on the residual smut of the copper alloy materials. Therefore, there is no residual smut, it has a tensile strength of 620 MPa or more, has an electrical conductivity of 40.0% IACS or more, and in addition, has good bending workability. The third heat treatment step of heating and holding the rolled material at a temperature of 250° C. or higher and 380° C. or higher for 4 hours or less to produce a copper alloy material is effective.
＜Ｍｎの影響＞
　Ｍｎの影響を評価するために、意図的にＭｎを含有していない銅合金材（試料１Ａ）および意図的にＭｎを含有している銅合金材（試料１Ｂ～１Ｆ）を作製した。試料１Ａ～１Ｆの銅合金材は、最終的に得られる銅合金材のＭｎ含有率を異ならせるように溶解鋳造工程で成分を調製した以外は、表１に示す試料１の場合と実質同等の製造工程を経て、実質同等の厚さを有するように作製した。そして、試料１Ａ～１Ｆの銅合金材について、表１に示す試料１の場合と同様に、常温（約２０℃）の引張強さ、導電率および曲げ加工性を測定・確認し、残留スマットの有無を確認した。また、上記したように、約９５０℃の高温環境下において、高温引張試験方法を規定するＪＩＳ－Ｇ０５６７：２０２０に準拠し、破断伸びを測定した。 <Influence of Mn>
In order to evaluate the effect of Mn, a copper alloy material intentionally not containing Mn (Sample 1A) and a copper alloy material intentionally containing Mn (Samples 1B to 1F) were produced. The copper alloy materials of Samples 1A to 1F were substantially the same as those of Sample 1 shown in Table 1, except that the components were prepared in the melting and casting process so that the Mn content of the finally obtained copper alloy material was different. Through the manufacturing process, it was produced so as to have substantially the same thickness. Then, for the copper alloy materials of Samples 1A to 1F, the tensile strength at normal temperature (about 20 ° C.), the electrical conductivity and the bending workability were measured and confirmed in the same manner as in the case of Sample 1 shown in Table 1, and the residual smut was measured. Checked for presence. In addition, as described above, the elongation at break was measured in a high temperature environment of about 950° C. in accordance with JIS-G0567:2020, which defines the high temperature tensile test method.
　表１１に、試料１Ａ～１Ｆ（本発明例）の銅合金材の組成（添加元素）、主な製造条件、および機械的特性などの情報を纏めて示す。なお、表１１に示す試料１Ａ～１Ｆの添加元素以外の残部は、Ｃｕおよび不純物元素と解してよく、０．０１％未満の不純物元素（Ａｇ、Ｐｂ、ＮｉおよびＳなど）は記載を略している。 Table 11 summarizes information such as the composition (additional elements), main manufacturing conditions, and mechanical properties of the copper alloy materials of Samples 1A to 1F (examples of the present invention). The rest of the samples 1A to 1F shown in Table 11 other than the additive elements may be interpreted as Cu and impurity elements, and the impurity elements (Ag, Pb, Ni, S, etc.) less than 0.01% are omitted. ing.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表１１に示すように、意図的にＭｎを添加していない試料１ＡのＭｎ含有率は、０．００１％未満である。また、意図的にＭｎを添加している銅合金材のＭｎ含有率は、試料１Ｂが約０．００１％、試料１Ｃが約０．００２％、試料１Ｄが約０．００６％、試料１Ｅが約０．０１０％、および、試料１Ｆが約０．０２０％である。したがって、試料１Ｃ～１ＦのＭｎ含有率は、この発明で好ましい銅合金材として上記したＭｎ含有率（０．００２％以上０．０２５％以下）の範囲内である。 As shown in Table 11, the Mn content of Sample 1A, to which Mn is not intentionally added, is less than 0.001%. In addition, the Mn content of the copper alloy material to which Mn is intentionally added is about 0.001% for sample 1B, about 0.002% for sample 1C, about 0.006% for sample 1D, and about 0.006% for sample 1E. about 0.010% and sample 1F about 0.020%. Therefore, the Mn contents of the samples 1C to 1F are within the range of the Mn contents (0.002% or more and 0.025% or less) described above as the preferred copper alloy materials of the present invention.
　常温環境下（約２０℃）において、試料１Ａ～１Ｆの引張強さ、導電率および曲げ加工性を評価し、残留スマットの有無を評価した結果、表１１に示すように、引張強さは、いずれも６２０ＭＰａ以上であり、６５０～６７０ＭＰａの範囲内であった。そして、Ｍｎが０．００２％以下の場合（試料１Ａ～１Ｃ）に６６０ＭＰａ未満となり、Ｍｎが０．００２％を超える場合（試料１Ｄ～１Ｆ）に６６０ＭＰａ以上となった。これより、引張強さは、Ｍｎ含有による実質的な影響を受けにくく、０．００２％以上０．０２５％以下のＭｎを含有しても６２０ＭＰａ以上になる可能性が高い。また、試料１Ａ～１Ｆの導電率は、いずれも４０％ＩＡＣＳ以上であり、４６．０～４７．２％ＩＡＣＳの範囲内であった。これより、導電率は、Ｍｎ含有による実質的な影響を受けにくく、０．００２％以上０．０２５％以下のＭｎを含有しても４０％ＩＡＣＳ以上になる可能性が高い。また、試料１Ａ～１Ｆの曲げ加工性は、いずれも「優」となった。これより、曲げ加工性は、Ｍｎ含有による実質的な影響を受けにくく、０．００２％以上０．０２５％以下のＭｎを含有しても「優」になる可能性が高い。また、試料１Ａ～１Ｆの残留スマットは、いずれも「無」となった。これより、残留スマットは、Ｍｎ含有による実質的な影響を受けにくく、０．００２％以上０．０２５％以下のＭｎを含有しても「無」である可能性が高い。 The tensile strength, electrical conductivity, and bending workability of Samples 1A to 1F were evaluated under a normal temperature environment (about 20°C), and the presence or absence of residual smut was evaluated. As a result, as shown in Table 11, the tensile strength was All of them were 620 MPa or more and within the range of 650 to 670 MPa. When Mn is 0.002% or less (Samples 1A to 1C), the tensile strength is less than 660 MPa, and when Mn exceeds 0.002% (Samples 1D to 1F), it is 660 MPa or more. From this, the tensile strength is less likely to be substantially affected by the Mn content, and there is a high possibility that the tensile strength will be 620 MPa or more even if the Mn content is 0.002% or more and 0.025% or less. In addition, the electrical conductivity of samples 1A to 1F was all 40%IACS or higher and within the range of 46.0 to 47.2%IACS. From this, the electrical conductivity is less likely to be substantially affected by the Mn content, and there is a high possibility that the electrical conductivity will be 40% IACS or higher even if the Mn content is 0.002% or more and 0.025% or less. In addition, the bending workability of samples 1A to 1F was all "excellent". From this, the bending workability is not substantially affected by the Mn content, and it is highly likely that the bending property will be "excellent" even if the Mn content is 0.002% or more and 0.025% or less. In addition, the residual smut of Samples 1A to 1F was "absent". From this, the residual smut is less likely to be substantially affected by the Mn content, and there is a high possibility that the residual smut is "absent" even if the Mn content is 0.002% or more and 0.025% or less.
　また、高温環境下（約９５０℃）において、試料１Ａ～１Ｆの破断伸びを評価した。その結果、表１１に示すように、試料１Ａ～１Ｆの破断伸びは概ね２０％以上であった。具体的には、破断伸びは、Ｍｎが０．００１％以下の場合（試料１Ａ、１Ｂ）に２０％未満になる可能性があり、Ｍｎが０．００２％以上の場合（試料１Ｃ～１Ｆ）に確実に２０％を超えて、Ｍｎが０．００６％以上の場合（試料１Ｄ～１Ｆ）に３０％以上になることが分った。また、破断伸びは、Ｍｎが０．０１０％の場合（試料１Ｅ）に最大の３７．０％になり、Ｍｎが０．０２０％の場合（試料１Ｆ）に低下して３２．０％になることが分った。これより、破断伸びは、Ｍｎ含有による影響を受けやすく、０．００２％以上０．０２５％以下のＭｎの含有により確実に２０％を超えて、０．００５％以上０．０２０％以下のＭｎの含有により３０％以上になる可能性が高い。 In addition, the elongation at break of samples 1A to 1F was evaluated in a high temperature environment (about 950°C). As a result, as shown in Table 11, the elongation at break of Samples 1A to 1F was generally 20% or more. Specifically, the elongation at break can be less than 20% when Mn is 0.001% or less (Samples 1A, 1B), and when Mn is 0.002% or more (Samples 1C-1F). It was found that the content definitely exceeds 20% and becomes 30% or more when Mn is 0.006% or more (Samples 1D to 1F). Further, the elongation at break reaches a maximum of 37.0% when Mn is 0.010% (Sample 1E), and decreases to 32.0% when Mn is 0.020% (Sample 1F). I understand. From this, the elongation at break is easily affected by the Mn content, and the Mn content of 0.002% or more and 0.025% or less reliably exceeds 20%, and the Mn content of 0.005% or more and 0.020% or less is likely to be 30% or more due to the content of
　上記したように、残留スマットが無く、常温環境下（約２０℃）で６２０ＭＰａ以上の引張強さを有するとともに４０．０％ＩＡＣＳ以上の導電率を有し、加えて、良好な曲げ加工性を有し、さらに、高温環境下（約９５０℃）で２０％を超える破断伸びを有する観点で、実用上、上記範囲でＦｅとＰとＺｎとＳｎとを含有し、さらに上記範囲でＭｎを含有する銅合金材は、有効である。 As described above, there is no residual smut, it has a tensile strength of 620 MPa or more in a normal temperature environment (about 20 ° C.), has an electrical conductivity of 40.0% IACS or more, and in addition, has good bending workability. In addition, from the viewpoint of having a breaking elongation of more than 20% in a high temperature environment (about 950 ° C.), practically, Fe, P, Zn and Sn are contained in the above range, and Mn is contained in the above range. A copper alloy material that
　次に、表１１に示すＦｅ、Ｐ、ＳｎおよびＭｎの各含有率（実測値）に基いて、ＭＩ値の算定を試みた。ＭＩ値は、上記したように、（Ｍｎ含有率＋不純物元素の総含有率）／（Ｆｅ含有率＋Ｐ含有率＋Ｓｎ含有率）×１００で求まる値である。ＦｅとＰとＳｎの合計の含有率は、２．８２％である。たとえば、不純物元素の総含有率が０．００１％の場合、表１１に示す実測値に基づき、Ｍｎ含有率の０％（試料１Ａ）から０．０２０％（試料１Ｆ）への増加に比例して、ＭＩ値は０．０４（試料１Ａ）から０．７４（試料１Ｆ）へと大きくなることを確認することができる。しかし、試料１Ａ～１Ｆにおいて、幾つかの不純物元素の含有率は０．０１％未満であるが、全ての不純物元素を実測するのは現実的ではなく、不純物元素の総含有率の正確な値は不明である。そこで、不純物元素の総含有率を仮定して、表１１に示す実測値に基づき、Ｍｎ含有率とＭＩ値と破断伸びとの関係の予測を試みた。 Next, an attempt was made to calculate the MI value based on the Fe, P, Sn and Mn contents (measured values) shown in Table 11. As described above, the MI value is a value obtained by (Mn content+total content of impurity elements)/(Fe content+P content+Sn content)×100. The total content of Fe, P and Sn is 2.82%. For example, when the total content of impurity elements is 0.001%, based on the measured values shown in Table 11, the increase in Mn content from 0% (Sample 1A) to 0.020% (Sample 1F) is proportional to It can be confirmed that the MI value increases from 0.04 (Sample 1A) to 0.74 (Sample 1F). However, in Samples 1A to 1F, the content of some impurity elements is less than 0.01%, but it is not realistic to actually measure all the impurity elements, and the exact value of the total content of impurity elements is is unknown. Therefore, an attempt was made to predict the relationship between the Mn content, the MI value, and the elongation at break based on the measured values shown in Table 11, assuming the total content of impurity elements.
　具体的には、不純物元素の総含有率を、実用的に妥当と考えられる不純物元素の総含有率を０．０１０％（低純度）、０．００５％（普通純度）および０．００１％（高純度）の３条件とし、Ｍｎ含有率（実測値）と、表１１に示す実測値に基づくＭＩ値（条件付き計算値）との関係性を示す第１モデルを導出し、さらに、ＭＩ値（条件付き計算値）と破断伸び（実測値）との関係性を示す第２モデルを導出した。次いで、第１モデルを利用してＭｎ含有率の範囲に対応するＭＩ値の範囲を予測し、さらに、第２モデルを利用してＭＩ値の範囲に対応する破断伸びの範囲を予測した。第１モデルは、実用性および容易性を考慮し、汎用の表計算ソフト（Ｍｉｃｒｏｓｏｆｔ製Ｅｘｃｅｌ）を用いて、Ｍｎ含有率（実測値）とＭＩ値（条件付き計算値）とのグラフ（散布図）を作成し、線形（１次）近似式を求めて回帰モデルとして利用した。 Specifically, the total content of impurity elements is set to 0.010% (low purity), 0.005% (ordinary purity), and 0.001% ( high purity), the Mn content (measured value) and the MI value (conditionally calculated value) based on the measured value shown in Table 11 A first model was derived, and further, the MI value A second model was derived to show the relationship between (conditional calculated value) and elongation at break (actual value). A first model was then used to predict a range of MI values corresponding to a range of Mn contents, and a second model was used to predict a range of elongation at break corresponding to a range of MI values. The first model is a graph (scatter diagram) of the Mn content (actual value) and the MI value (conditionally calculated value) using general-purpose spreadsheet software (Microsoft Excel), considering practicality and ease. ) was created, and a linear (first-order) approximation formula was obtained and used as a regression model.
　第１モデルでは、Ｍｎ含有率（設定値）が独立変数ｘとなり、ＭＩ値（予測値）が第１従属変数ｐとなる。予測の区間は、０．０００≦ｘ≦０．０３０である。同様に、第２モデルは、ＭＩ値（条件付き計算値）と破断伸び（実測値）とのグラフ（散布図）を作成し、多項（２次）近似式を求めて回帰モデルとして利用した。第２モデルでは、第１モデルの第１従属変数ｐのＭＩ値（予測値）が独立変数となり、破断伸び（予測値）が第２従属変数ｙとなる。第１モデルおよび第２モデルの信頼性は、機械学習の分野の考え方を参考し、決定係数（Ｒ２）が０．７以上（Ｒ２≦１）であれば無条件で「信頼性あり」と判断した。 In the first model, the Mn content (set value) is the independent variable x, and the MI value (predicted value) is the first dependent variable p. The prediction interval is 0.000≦x≦0.030. Similarly, the second model was used as a regression model by creating a graph (scatter diagram) of MI values (calculated values with conditions) and elongation at break (actual values), obtaining a multinomial (quadratic) approximation formula. In the second model, the MI value (predicted value) of the first dependent variable p of the first model is the independent variable, and the elongation at break (predicted value) is the second dependent variable y. The reliability of the first model and the second model is unconditionally “reliable” if the coefficient of determination (R 2 ) is 0.7 or more (R 2 ≤ 1) with reference to the way of thinking in the field of machine learning. I decided.
　表１２～表１３に、表１１に示す実測値に基づいて、不純物元素の総含有率を０．０１０％（低純度）、０．００５％（普通純度）および０．００１％（高純度）の３条件とした場合のＭｎ含有率（設定値）とＭＩ値（予測値）と破断伸び（予測値）との予測結果を示す。なお、圧延加工性などへの影響が特に大きいＳが不純物元素の主体である場合、一般的な製造原料のＳ含有率が０．００１％～０．００５％程度と考えられことや、実測が簡易で実用性が高い観点で、不純物元素の総含有率を０．００１％～０．００５％から選択的に設定して予測することもできる。また、不純物元素の主体が上記したＡｇ、Ｐｂ、ＮｉおよびＳである場合、Ａｇ、Ｐｂ、ＮｉおよびＳの合計の含有率を不純物元素の総含有率に設定して予測することもできる。 Tables 12 and 13 show the total impurity element content of 0.010% (low purity), 0.005% (ordinary purity) and 0.001% (high purity) based on the measured values shown in Table 11. 3 shows the prediction results of the Mn content (set value), MI value (predicted value), and elongation at break (predicted value) under the following three conditions. In addition, when S, which has a particularly large effect on rolling workability, etc., is the main impurity element, the S content of general manufacturing raw materials is considered to be about 0.001% to 0.005%, and actual measurement is not possible. From the viewpoint of simplicity and high practicality, the total content of impurity elements can be selectively set and predicted from 0.001% to 0.005%. Further, when the impurity elements are mainly Ag, Pb, Ni and S, the total content of Ag, Pb, Ni and S can be set as the total content of the impurity elements for prediction.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表１２に示すように、ＦｅとＰとＳｎの合計の含有率（２．８２％）に対する不純物元素の総含有率が０．０１０％（低純度）の場合、第１モデルによる予測結果は、たとえば、ｘが０．０００のときにｐが０．３７、ｘが０．００２のときにｐが０．４４、ｘが０．０１８のときにｐが１．００、および、ｘが０．０２５のときにｐが１．２５となった。そして、第２モデルによる予測結果は、たとえば、ｐが０．３７のときにｙが２１．１、ｐが０．４４のときにｙが２５．５、ｐが１．００のときにｙが３４．０、および、ｐが１．２５のときにｙが２２．６となった。なお、第１モデルのＲ２（０．９８９５）および第２モデルのＲ２（０．８５９０）は、いずれも信頼性の目安とした０．７よりも十分に大きい。したがって、第１モデルおよび第２モデルの予測結果は、外れ値の影響を大きく受けている可能性が小さいと考えられるため、「信頼性あり」と判断することができる。 As shown in Table 12, when the total content of impurity elements is 0.010% (low purity) with respect to the total content of Fe, P, and Sn (2.82%), the prediction result by the first model is For example, p is 0.37 when x is 0.000, p is 0.44 when x is 0.002, p is 1.00 when x is 0.018, and x is 0.00. 025, p became 1.25. The prediction result by the second model is, for example, y is 21.1 when p is 0.37, y is 25.5 when p is 0.44, and y is 1.00 when p is 1.00. 34.0 and y was 22.6 when p was 1.25. Both the R 2 (0.9895) of the first model and the R 2 (0.8590) of the second model are sufficiently larger than 0.7, which is a criterion of reliability. Therefore, the prediction results of the first model and the second model are less likely to be significantly affected by outliers, and therefore can be judged to be "reliable".
　これより、ｘが０．０００でもｙが２０以上になる、ということが分る。また、ｘが０．０１８よりも大きくなってｐが１．００よりも大きくなるとｙが小さくなる、ということが分る。また、ｙが最大（３５．７）になるときのｐは０．７２でｘは０．０１０である、ということが分る。よって、Ｍｎ含有率を０．００２％～０．０２５％に調製すれば、ＭＩ値が０．４４～１．２５となって、２５．５％～２２．６％（最大３５．７％）の破断伸びを得ることができる。また、Ｍｎ含有率を０．０１０％～０．０１８％に調製すれば、ＭＩ値が０．７２～１．００となって、３４．０％～３５．７％のより大きな破断伸びを得ることができる。よって、低純度のものにＭｎを含有させる場合、実用性や安定性などを考慮し、ＭＩ値を、たとえば、０．４５以上（好ましくは、０．５０以上）１．１以下（好ましくは、１．０以下、より好ましくは０．９以下）になるように調製すればよい。 From this, it can be seen that even if x is 0.000, y will be 20 or more. It can also be seen that y decreases when x is greater than 0.018 and p is greater than 1.00. It can also be seen that p is 0.72 and x is 0.010 when y reaches its maximum (35.7). Therefore, if the Mn content is adjusted to 0.002% to 0.025%, the MI value is 0.44 to 1.25, which is 25.5% to 22.6% (maximum 35.7%). of breaking elongation can be obtained. Also, if the Mn content is adjusted to 0.010% to 0.018%, the MI value will be 0.72 to 1.00, and a larger elongation at break of 34.0% to 35.7% will be obtained. be able to. Therefore, when Mn is contained in a low-purity product, considering practicality and stability, the MI value is, for example, 0.45 or more (preferably 0.50 or more) and 1.1 or less (preferably, 1.0 or less, more preferably 0.9 or less).
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表１３に示すように、ＦｅとＰとＳｎの合計の含有率（２．８２％）に対する不純物元素の総含有率が０．００５％（中純度）の場合、第１モデルによる予測結果は、たとえば、ｘが０．０００のときにｐが０．１９、ｘが０．００２のときにｐが０．２６、ｘが０．０２３のときにｐが１．００、および、ｘが０．０２５のときにｐが１．０７となった。そして、第２モデルによる予測結果は、たとえば、ｐが０．１９のときにｙが２０．８、ｐが０．２６のときにｙが２５．４、ｐが１．００のときにｙが２６．６、および、ｐが１．０７のときにｙが２２．３となった。なお、第１モデルのＲ２（０．９９５０）および第２モデルのＲ２（０．８７１２）は、いずれも信頼性の目安とした０．７よりも十分に大きい。したがって、第１モデルおよび第２モデルの予測結果は、外れ値の影響を大きく受けている可能性が小さいと考えられるため、「信頼性あり」と判断することができる。 As shown in Table 13, when the total content of impurity elements is 0.005% (medium purity) with respect to the total content of Fe, P, and Sn (2.82%), the prediction result by the first model is as follows. For example, p is 0.19 when x is 0.000, p is 0.26 when x is 0.002, p is 1.00 when x is 0.023, and x is 0.00. 025 p became 1.07. The prediction result by the second model is, for example, y is 20.8 when p is 0.19, y is 25.4 when p is 0.26, and y is 26.6, and y was 22.3 when p was 1.07. Both the R 2 (0.9950) of the first model and the R 2 (0.8712) of the second model are sufficiently larger than 0.7, which is a criterion of reliability. Therefore, the prediction results of the first model and the second model are less likely to be significantly affected by outliers, and therefore can be judged to be "reliable".
　これより、ｘが０．０００でもｙが２０以上になる、ということが分る。また、ｘが０．０１０よりも大きくなってｐが０．５４よりも大きくなるとｙが小さくなる、ということが分る。また、ｙが最大（３６．０）になるときのｐは０．５４でｘは０．０１０である、ということが分る。よって、Ｍｎ含有率を０．００２％～０．０２５％に調製すれば、ＭＩ値が０．２６～１．０７となって、２５．４％～２２．３％（最大３６．０％）の破断伸びを得ることができる。また、Ｍｎ含有率を０．００６％～０．０２０％に調製すれば、ＭＩ値が０．４０～０．８９となって、３１．８％～３６．０％のより大きな破断伸びを得ることができる。よって、普通純度のものにＭｎを含有させる場合、実用性や安定性などを考慮し、ＭＩ値を、たとえば、０．３０以上（好ましくは、０．３５以上）１．１以下（好ましくは、１．０以下、より好ましくは０．９以下）になるように調製すればよい。 From this, it can be seen that even if x is 0.000, y will be 20 or more. It can also be seen that y decreases when x is greater than 0.010 and p is greater than 0.54. It can also be seen that p is 0.54 and x is 0.010 when y is at its maximum (36.0). Therefore, if the Mn content is adjusted to 0.002% to 0.025%, the MI value is 0.26 to 1.07, which is 25.4% to 22.3% (maximum 36.0%). of breaking elongation can be obtained. Also, if the Mn content is adjusted to 0.006% to 0.020%, the MI value will be 0.40 to 0.89, and a larger elongation at break of 31.8% to 36.0% will be obtained. be able to. Therefore, when Mn is contained in a product of ordinary purity, considering practicality and stability, the MI value is, for example, 0.30 or more (preferably 0.35 or more) and 1.1 or less (preferably, 1.0 or less, more preferably 0.9 or less).
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　表１４に示すように、ＦｅとＰとＳｎの合計の含有率（２．８２％）に対する不純物元素の総含有率が０．００１％の場合、第１モデルによる予測結果は、たとえば、ｘが０．０００のときにｐが０．０４、ｘが０．０００３のときにｐが０．０５、ｘが０．００２のときにｐが０．１１、ｘが０．０２５のときにｐが０．９３、および、ｘが０．０２７のときにｐが１．００となった。そして、第２モデルによる予測結果は、たとえば、ｐが０．０４のときにｙが２０．５、ｐが０．０５のときにｙが２１．２、ｐが０．１１のときにｙが２５．３、ｐが０．９３のときにｙが２２．０、および、ｐが１．００のときにｙが１６．４となった。なお、第１モデルのＲ２（０．９９８０）および第２モデルのＲ２（０．８８０８）は、いずれも信頼性の目安とした０．７よりも十分に大きい。したがって、第１モデルおよび第２モデルの予測結果は、外れ値の影響を大きく受けている可能性が小さいと考えられるため、「信頼性あり」と判断することができる。 As shown in Table 14, when the total content of impurity elements is 0.001% with respect to the total content of Fe, P, and Sn (2.82%), the prediction result by the first model is, for example, p is 0.04 when x is 0.000, p is 0.05 when x is 0.0003, p is 0.11 when x is 0.002, and p is 0.025 when x is 0.025. p was 1.00 when x was 0.93 and x was 0.027. Then, the prediction result by the second model is, for example, y is 20.5 when p is 0.04, y is 21.2 when p is 0.05, and y is 25.3, y was 22.0 when p was 0.93, and y was 16.4 when p was 1.00. Both the R 2 (0.9980) of the first model and the R 2 (0.8808) of the second model are sufficiently larger than 0.7, which is a criterion of reliability. Therefore, the prediction results of the first model and the second model are less likely to be significantly affected by outliers, and therefore can be judged to be "reliable".
　これより、ｘが０．０００でもｙが２０以上になる、ということが分る。また、ｘが０．０２７以上になるとｙが２０未満になる、ということが分る。また、ｘが０．０１０よりも大きくなってｐが０．３９よりも大きくなるとｙが小さくなる、ということが分る。また、ｙが最大（３６．３）になるときのｐは０．３９でｘは０．０１０である、ということが分る。よって、Ｍｎ含有率を０．００２％～０．０２５％に調製すれば、ＭＩ値が０．１１～０．９３となって、２５．３～２２．０％（最大３６．３％）の破断伸びを得ることができる。また、Ｍｎ含有率を０．００６％～０．０２０％に調製すれば、ＭＩ値が０．２５～０．７５となって、３１．８％～３６．３％のより大きな破断伸びを得ることができる。よって、高純度のものにＭｎを含有させる場合、実用性や安定性などを考慮し、ＭＩ値を、たとえば、０．１５以上（好ましくは、０．２０以上）０．９以下（好ましくは、０．８５以下、より好ましくは０．８０以下）になるように調製すればよい。 From this, it can be seen that even if x is 0.000, y will be 20 or more. Also, it can be seen that y is less than 20 when x is 0.027 or more. It can also be seen that y decreases when x is greater than 0.010 and p is greater than 0.39. It can also be seen that p is 0.39 and x is 0.010 when y is at its maximum (36.3). Therefore, if the Mn content is adjusted to 0.002% to 0.025%, the MI value is 0.11 to 0.93, which is 25.3 to 22.0% (maximum 36.3%). Elongation at break can be obtained. Also, if the Mn content is adjusted to 0.006% to 0.020%, the MI value will be 0.25 to 0.75, and a larger elongation at break of 31.8% to 36.3% will be obtained. be able to. Therefore, when Mn is contained in a high-purity product, considering practicality and stability, the MI value is, for example, 0.15 or more (preferably 0.20 or more) and 0.9 or less (preferably, 0.85 or less, more preferably 0.80 or less).
　以上より、銅合金材の銅合金組織を構成する添加元素（Ｆｅ、Ｐ、ＺｎおよびＳｎ）の含有率を特定の範囲内に制御し、図１に示す銅合金材の製造工程において、第１熱処理工程、第２冷間圧延工程、第２熱処理工程、第３冷間圧延工程および第３熱処理工程の製造条件を特定の範囲内に制御することによって、Ｃ１９４０などのＣｕ－Ｆｅ－Ｚｎ－Ｐ系の銅合金材と同様に残留スマットの問題がなく、Ｃ７０２５などのＣｕ－Ｎｉ－Ｓｉ系の銅合金材と略同等の引張強さと導電率を有する、銅合金材が得られることが確認された。また、上記添加元素の含有率と上記製造条件をより適切に制御することによって、曲げ加工性の良い銅合金材が得られることが確認された。また、上記４種の添加元素とともにＭｎを添加し、上記４種の添加元素およびＭｎの含有率を適切に制御することによって、高温での破断伸びが良好になり、圧延加工性の良い、特に熱間圧延の段階で割れにくい、銅合金材が得られることが確認された。

  As described above, the content of the additive elements (Fe, P, Zn and Sn) constituting the copper alloy structure of the copper alloy material is controlled within a specific range, and in the manufacturing process of the copper alloy material shown in FIG. By controlling the manufacturing conditions of the heat treatment process, the second cold rolling process, the second heat treatment process, the third cold rolling process and the third heat treatment process within a specific range, Cu-Fe-Zn-P such as C1940 It has been confirmed that a copper alloy material can be obtained that has almost the same tensile strength and electrical conductivity as Cu--Ni--Si-based copper alloy materials such as C7025, without the problem of residual smut, as with C7025-based copper alloy materials. Ta. Further, it was confirmed that a copper alloy material having good bending workability can be obtained by more appropriately controlling the content of the additive element and the manufacturing conditions. In addition, by adding Mn together with the above four additive elements and appropriately controlling the contents of the four additive elements and Mn, the elongation at break at high temperatures is improved, and the rolling processability is improved. It was confirmed that a copper alloy material that is resistant to cracking during hot rolling can be obtained.

Claims (8)

  1. 　質量％で示す含有率で、含有必須元素として、１．６％以上２．６％以下のＦｅと、０．０１％以上０．３％以下のＰと、０．０１％以上０．３％以下のＺｎと、０．３％以上０．８％以下のＳｎとを含有し、残部がＣｕおよび不純物元素から成り、
    　２０℃の温度環境下において、６２０ＭＰａ以上の引張強さを有するとともに、４０．０％ＩＡＣＳ以上の導電率を有する、銅合金材。     In terms of the content in mass %, the essential elements are 1.6% or more and 2.6% or less of Fe, 0.01% or more and 0.3% or less of P, and 0.01% or more and 0.3% containing the following Zn and 0.3% or more and 0.8% or less of Sn, the balance being Cu and impurity elements,
    A copper alloy material having a tensile strength of 620 MPa or more and an electrical conductivity of 40.0% IACS or more in a temperature environment of 20°C.
  2. 　質量％で示す含有率で、０．０１％以上０．２０％以下のＰを含有する、請求項１に記載の銅合金材。 The copper alloy material according to claim 1, which contains 0.01% or more and 0.20% or less of P in terms of mass% content.
  3. 　質量％で示す含有率で、含有必須元素として、前記Ｆｅと前記Ｐと前記Ｚｎと前記Ｓｎと、さらに、０．００２％以上０．０２５％以下のＭｎとを含有し、残部がＣｕおよび不純物元素から成り、
    　９５０℃の温度環境下において、２０％を超える破断伸びを有する、請求項１または２に記載の銅合金材。     The content is expressed in mass %, and contains, as essential elements, Fe, P, Zn, and Sn, and 0.002% or more and 0.025% or less of Mn, and the balance is Cu and impurities. made up of elements,
    The copper alloy material according to claim 1 or 2, which has an elongation at break exceeding 20% in a temperature environment of 950°C.
  4. 　質量％で示す含有率で、（Ｍｎ含有率＋不純物元素の総含有率）／（Ｆｅ含有率＋Ｐ含有率＋Ｓｎ含有率）×１００で求まる値が、１．１以下である、請求項３に記載の銅合金材。 Claim 3, wherein the content in mass% is 1.1 or less, which is obtained by (Mn content + total impurity element content)/(Fe content + P content + Sn content) x 100. A copper alloy material as described.
  5. 　質量％で示す含有率で、含有必須元素として、１．６％以上２．６％以下のＦｅと、０．０１％以上０．３％以下のＰと、０．０１％以上０．３％以下のＺｎと、０．３％以上０．８％以下のＳｎとを含有し、残部がＣｕおよび不純物元素から成る、銅合金鋳造材を作製する溶解鋳造工程と、
    　前記銅合金鋳造材を用いて熱間圧延を行って熱間圧延材を作製する熱間圧延工程と、
    　前記熱間圧延材を用いて冷間圧延を行って第１冷間圧延材を作製する第１冷間圧延工程と、
    　前記第１冷間圧延材に対して５００℃以上６００℃以下の温度で４ｈ以下の加熱保持を行って第１熱処理材を作製する第１熱処理工程と、
    　前記第１熱処理材を用いて２０％以上９０％以下の圧延加工度で冷間圧延を行って第２冷間圧延材を作製する第２冷間圧延工程と、
    　前記第２冷間圧延材に対して３８０℃以上４８０℃以下の温度で１ｈ以上１２ｈ以下の加熱保持を行って第２熱処理材を作製する第２熱処理工程と、
    　前記第２熱処理材を用いて６０％以上８０％以下の圧延加工度で冷間圧延を行って第３冷間圧延材を作製する第３冷間圧延工程と、
    　前記第３冷間圧延材に対して２５０℃以上３８０℃以上の温度で４ｈ以下の加熱保持を行って銅合金材を作製する第３熱処理工程と、を有し、
    　前記溶解鋳造工程、前記熱間圧延工程、前記第１冷間圧延工程、前記第１熱処理工程、前記第２冷間圧延工程、前記第２熱処理工程、前記第３冷間圧延工程、および、前記第３熱処理工程の順に実施することにより、２０℃の温度環境下において、６２０ＭＰａ以上の引張強さを有するとともに、４０．０％ＩＡＣＳ以上の導電率を有する、銅合金材を作製する、銅合金材の製造方法。     In terms of the content in mass %, the essential elements are 1.6% or more and 2.6% or less of Fe, 0.01% or more and 0.3% or less of P, and 0.01% or more and 0.3% a melting and casting step of producing a copper alloy casting material containing the following Zn and 0.3% or more and 0.8% or less of Sn, the balance being Cu and impurity elements;
    A hot rolling step of performing hot rolling using the copper alloy cast material to produce a hot rolled material;
    A first cold-rolling step of cold-rolling the hot-rolled material to produce a first cold-rolled material;
    A first heat treatment step of heating and holding the first cold rolled material at a temperature of 500 ° C. or more and 600 ° C. or less for 4 hours or less to produce a first heat treated material;
    A second cold rolling step of cold rolling at a rolling reduction rate of 20% or more and 90% or less using the first heat treated material to produce a second cold rolled material;
    a second heat treatment step of heating and holding the second cold-rolled material at a temperature of 380° C. or more and 480° C. or less for 1 hour or more and 12 hours or less to produce a second heat treated material;
    A third cold rolling step of cold rolling at a rolling reduction rate of 60% or more and 80% or less using the second heat treated material to produce a third cold rolled material;
    a third heat treatment step of heating and holding the third cold-rolled material at a temperature of 250° C. or higher and 380° C. or higher for 4 hours or less to produce a copper alloy material;
    The melting and casting process, the hot rolling process, the first cold rolling process, the first heat treatment process, the second cold rolling process, the second heat treatment process, the third cold rolling process, and the A copper alloy material having a tensile strength of 620 MPa or more and an electrical conductivity of 40.0% IACS or more in a temperature environment of 20° C. by performing the third heat treatment step in order. How the material is made.
  6. 　質量％で示す含有率で、０．０１％以上０．２０％以下のＰを含有する、銅合金材を作製する、請求項５に記載の銅合金材の製造方法。 The method for producing a copper alloy material according to claim 5, wherein the copper alloy material contains 0.01% or more and 0.20% or less of P in terms of mass% content.
  7. 　質量％で示す含有率で、含有必須元素として、前記Ｆｅと前記Ｐと前記Ｚｎと前記Ｓｎと、さらに、０．００２％以上０．０２５％以下のＭｎとを含有し、残部がＣｕおよび不純物元素から成る、銅合金鋳造材を作製する溶解鋳造工程とし、この後に、前記熱間圧延工程、前記第１冷間圧延工程、前記第１熱処理工程、前記第２冷間圧延工程、前記第２熱処理工程、前記第３冷間圧延工程、および、前記第３熱処理工程の順に実施することにより、
    　９５０℃の温度環境下において、２０％を超える破断伸びを有する、銅合金材を作製する、請求項５または６に記載の銅合金材の製造方法。     The content is expressed in mass %, and contains, as essential elements, Fe, P, Zn, and Sn, and 0.002% or more and 0.025% or less of Mn, and the balance is Cu and impurities. A melting and casting step for producing a copper alloy cast material made of elements, followed by the hot rolling step, the first cold rolling step, the first heat treatment step, the second cold rolling step, and the second By performing the heat treatment step, the third cold rolling step, and the third heat treatment step in this order,
    The method for producing a copper alloy material according to claim 5 or 6, wherein the copper alloy material having a breaking elongation exceeding 20% is produced in a temperature environment of 950°C.
  8. 　質量％で示す含有率で、（Ｍｎ含有率＋不純物元素の総含有率）／（Ｆｅ含有率＋Ｐ含有率＋Ｓｎ含有率）×１００で求まる値が、０．０５以上１．０以下である、銅合金鋳造材を作製する溶解鋳造工程とする、請求項７に記載の銅合金材の製造方法。

          The content in mass% is (Mn content + total content of impurity elements) / (Fe content + P content + Sn content) x 100, and the value is 0.05 or more and 1.0 or less. 8. The method for producing a copper alloy material according to claim 7, wherein the step of melting and casting produces a copper alloy cast material.
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JP2010229438A (en) * 2009-03-26 2010-10-14 Dowa Metaltech Kk Copper alloy sheet and manufacturing method therefor
JP2015017286A (en) * 2013-07-09 2015-01-29 三菱伸銅株式会社 Plating-fitted copper alloy sheet having excellent glossiness
JP2019173090A (en) * 2018-03-28 2019-10-10 三菱マテリアル株式会社 Copper alloy
JP2019173091A (en) * 2018-03-28 2019-10-10 三菱マテリアル株式会社 Copper alloy

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