TWI522484B - Copper alloy, thin plate of copper alloy and method for producing copper alloy - Google Patents

Copper alloy, thin plate of copper alloy and method for producing copper alloy Download PDF

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TWI522484B
TWI522484B TW103127250A TW103127250A TWI522484B TW I522484 B TWI522484 B TW I522484B TW 103127250 A TW103127250 A TW 103127250A TW 103127250 A TW103127250 A TW 103127250A TW I522484 B TWI522484 B TW I522484B
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TW201520346A (en
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牧一誠
末廣健一郎
有澤周平
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三菱綜合材料股份有限公司
三菱伸銅股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C9/00—Alloys based on copper

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Description

銅合金、銅合金薄板及銅合金之製造方法 Copper alloy, copper alloy sheet and copper alloy manufacturing method

本發明係關於作為使用於例如家電、半導體裝置用導線架等之半導體零件、印刷線路板等之電氣．電子零件材料、開關器零件、匯流條、連接器等之機構零件或產業用機器等之銅合金板條為合適的銅合金、銅合金薄板及銅合金之製造方法。 The present invention relates to electrical equipment used as a semiconductor component such as a home appliance, a lead frame for a semiconductor device, a printed wiring board, or the like. A copper alloy slat such as an electronic component material, a switch component, a bus bar, a connector, or the like, or an industrial machine is a suitable copper alloy, a copper alloy thin plate, and a copper alloy.

本專利申請係基於2013年8月9日於日本國所提出專利申請的特願2013-167063號、及2014年6月4於日本國提出專利申請的特願2014-116297號來主張優先權，並參考該內容而予以援用。 This patent application claims priority based on Japanese Patent Application No. 2013-167063, filed on Sep. 9, 2013, filed on Jan. And refer to this content for reference.

作為上述各種用途之銅合金，以往汎用為含有Fe與P之Cu-Fe-P系之銅合金。作為Cu-Fe-P系之銅合金，可示例一種銅合金(CDA19400合金)，其係包含Fe：2.1質量%以上2.7質量%以下、P：0.015質量%以上0.15質量%以下、Zn：0.05質量%以上0.20質量%以下。 尚，該CDA19400合金係依CDA(Copper Development Association)所規定之國際標準合金。 Copper alloys which are various uses as described above are conventionally used as a Cu-Fe-P-based copper alloy containing Fe and P. As a Cu-Fe-P-based copper alloy, a copper alloy (CDA19400 alloy) containing Fe: 2.1% by mass or more and 2.7% by mass or less, P: 0.015% by mass or more and 0.15% by mass or less, and Zn: 0.05 mass may be exemplified. % or more and 0.20% by mass or less. Further, the CDA 19400 alloy is an international standard alloy specified by the CDA (Copper Development Association).

在此，上述CDA19400合金，係由於使Fe或Fe-P等之金屬間化合物析出於銅母相中之析出強化型合金，且強度、導電性及導熱性為優異，故廣泛地被使用於各種用途。 Here, the above-mentioned CDA19400 alloy is widely used in various types of precipitation-strengthening alloys in which an intermetallic compound such as Fe or Fe-P is precipitated in a copper matrix phase, and is excellent in strength, electrical conductivity, and thermal conductivity. use.

近年，隨著Cu-Fe-P系之銅合金之用途擴大、或電氣、電子機器之輕量化、薄壁化、小型化等，對於CDA19400合金亦要求著更高的強度、或導電性、優異的彎曲加工性。 In recent years, with the expansion of the use of Cu-Fe-P-based copper alloys, or the weight reduction, thinning, and miniaturization of electrical and electronic equipment, CDA19400 alloys are required to have higher strength, conductivity, and excellent performance. Bending workability.

又，上述導線架或連接器等，係藉由蝕刻或沖裁銅合金薄板而製造。在此，將由CDA19400合金等所構成的銅合金薄板進行沖裁加工時，具有模具的摩損劇烈、於短時間的使用則必須更換模具之類的問題。 Further, the lead frame, the connector, and the like are manufactured by etching or punching a copper alloy sheet. Here, when the copper alloy sheet composed of the CDA 19400 alloy or the like is subjected to punching, the mold has a sharp wear and the use of the mold must be replaced in a short period of time.

因此，例如專利文獻1、2中提案著，為了抑制於熱軋延步驟中的裂紋，同時將耐沖裁模具摩損性等之諸特性提昇，故在Cu-Fe-P系合金中添加C。又，提案著為了將Cu-Fe-P系合金之強度等之諸特性提昇，故添加Mg等。 For this reason, for example, in the patent documents 1 and 2, it is proposed to add C to the Cu-Fe-P alloy in order to suppress cracks in the hot rolling step and improve the properties such as the wear resistance of the blanking die. Moreover, in order to improve the characteristics of the strength of the Cu-Fe-P alloy, etc., it is proposed to add Mg or the like.

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開平11-323464號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-323464

[專利文獻2]日本特開平11-350055號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 11-350055

然而，由Cu-Fe-P系合金所構成之銅合金，於軋延鑄塊來製造銅合金薄板之際，有產生很多表面缺陷之情形。若存在上述表面缺陷時，因為大幅地降低製造產率，故有銅合金薄板之製造成本大幅地提昇之類的問題。 However, a copper alloy composed of a Cu-Fe-P alloy has a large number of surface defects when rolling a cast ingot to produce a copper alloy sheet. When the above surface defects are present, there is a problem that the manufacturing cost of the copper alloy sheet is greatly increased because the manufacturing yield is drastically lowered.

又，對於由上述Cu-Fe-P系合金所構成的銅合金薄板進行壓製加工、蝕刻加工或鍍銀之際，會有產生起因為粗大的鐵合金粒子之非平滑的形狀不良之情形。 Further, when the copper alloy sheet composed of the Cu-Fe-P-based alloy is subjected to press working, etching, or silver plating, a non-smooth shape defect of the coarse iron alloy particles may occur.

本發明係有鑑於前述情況之發明，本發明的目的在於提供一種銅合金、銅合金薄板、銅合金之製造方法，其係於Cu-Fe-P系合金中可抑制表面缺陷及形狀不良之產生。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a copper alloy, a copper alloy sheet, and a method for producing a copper alloy, which are capable of suppressing generation of surface defects and shape defects in a Cu-Fe-P alloy. .

為了解決此課題，本發明人經重複深入研究之結果得知，產生於CDA19400合金等之Cu-Fe-P系合金之表面缺陷及形狀不良，係因含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之鐵合金粒子露出於銅合金薄板之表面而形成。 In order to solve this problem, the inventors of the present invention have conducted intensive studies and found that the surface defects and shape defects of the Cu-Fe-P alloy produced in the CDA19400 alloy or the like are due to inclusion of Cr, Mo, W, V, and Nb. At least one or more of the iron alloy particles of Fe and C are exposed on the surface of the copper alloy sheet.

又得知，上述鐵合金粒子，係銅合金熔液中C、及進而的Cr、Mo、W、V、Nb中之至少1種以上為存在一定 量以上時，「以Fe為主成份並含有C、及進而的Cr、Mo、W、V、Nb中之至少1種以上之液相」與「以Cu為主成份之液相」會液相分離，而鑄塊內將生成含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之粗大的結晶物。又得到下述見解：以生成於鑄塊內之粗大的結晶物為起因，而生成露出於銅合金薄板之表面之鐵合金粒子。 Further, it is known that at least one of C, and further Cr, Mo, W, V, and Nb in the molten copper alloy is present in a certain amount. When the amount is more than or equal to "the liquid phase containing Fe as a main component and containing at least one of Cr, Mo, W, V, and Nb" and "liquid phase containing Cu as a main component" Separation is carried out, and at least one of Cr, Mo, W, V, and Nb and a coarse crystal of Fe and C are formed in the ingot. Further, it has been found that iron alloy particles exposed on the surface of the copper alloy sheet are formed by causing coarse crystals formed in the ingot.

本發明係根據如此般見解所完成，本發明之第一樣態所相關之銅合金，其係含有Fe：1.5質量%以上2.7質量%以下、P：0.008質量%以上0.15質量%以下、Zn：0.01質量%以上0.5質量%以下，且殘餘部份為Cu及不可避免之雜質，作為前述不可避免之雜質所包含的C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm。 The present invention is based on the above-described findings, and the copper alloy according to the first aspect of the present invention contains Fe: 1.5% by mass or more and 2.7% by mass or less, and P: 0.008% by mass or more and 0.15% by mass or less, and Zn: 0.01% by mass or more and 0.5% by mass or less, and the residual portion is Cu and unavoidable impurities, and the content of C contained as the unavoidable impurities is less than 5 ppm by mass, and the content of Cr is less than 7 mass. The content of ppm and Mo is less than 5 ppm by mass, the content of W is less than 1 ppm by mass, the content of V is less than 1 ppm by mass, and the content of Nb is less than 1 ppm by mass.

此構成之銅合金中，不可避免之雜質，係分別控制為C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm。如同上述般，因為C、然後Cr、Mo、W、V、Nb之類的元素係具有促進「以Fe為主成份並含有C、及進而的Cr、Mo、W、V、Nb中之至少1種以上之液相」與「以Cu為主成份之液相」之 液相分離之作用的元素，故容易在鑄塊內生成粗大的結晶物。亦即，此等C、Cr、Mo、W、V、Nb之類的元素為可固溶於Fe中，但幾乎無法固溶於Cu中，故將作為結晶物(鐵合金粒子)而殘留於Cu中。 In the copper alloy having such a composition, the unavoidable impurities are controlled so that the content of C is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, and the content of Mo is less than 5 ppm by mass. The content is less than 1 ppm by mass, the content of V is less than 1 ppm by mass, and the content of Nb is less than 1 ppm by mass. As described above, since C, then Cr, Mo, W, V, Nb and the like have a function of promoting "Fe as a main component and containing C, and further, at least 1 of Cr, Mo, W, V, Nb. a liquid phase above and a liquid phase containing Cu as a main component Since the elements of the liquid phase separation function, it is easy to form coarse crystals in the ingot. That is, such elements as C, Cr, Mo, W, V, and Nb are soluble in Fe, but hardly dissolve in Cu, so they remain as crystals (iron alloy particles) and remain in Cu. in.

據此，藉由將C、Cr、Mo、W、V、Nb之類的元素之含有量如上述般控制，可抑制粗大的結晶物之產生，將可大幅減低因鐵合金粒子之表面缺陷。又，可抑制起因於粗大的結晶物之製品的形狀不良。 According to this, by controlling the content of elements such as C, Cr, Mo, W, V, and Nb as described above, generation of coarse crystals can be suppressed, and surface defects due to the iron alloy particles can be greatly reduced. Further, it is possible to suppress the shape defect of the product resulting from the coarse crystal.

在此，本發明之銅合金中，可進而含有Ni：0.003質量%以上0.5質量%以下、Sn：0.003質量%以上0.5質量%以下之任一者或兩者。 Here, the copper alloy of the present invention may further contain any one or both of Ni: 0.003 mass% or more and 0.5 mass% or less, and Sn: 0.003 mass% or more and 0.5 mass% or less.

此時，Ni或Sn藉由固溶於Cu的母相中，可試圖Cu-Fe-P系銅合金之強度提昇。 At this time, Ni or Sn can be attempted to increase the strength of the Cu-Fe-P-based copper alloy by being dissolved in the mother phase of Cu.

再者，本發明之銅合金中，可進而在0.0007質量%以上0.5質量%以下之範圍內含有Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co中之至少1種或2種以上。 Further, in the copper alloy of the present invention, Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, Co may be contained in a range of 0.0007 mass% or more and 0.5 mass% or less. At least one type or two or more types.

此時，藉由Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之類的元素，可試圖Cu-Fe-P系合金之強度提昇及耐沖裁模具摩損性之提昇。 At this time, by using elements such as Mg, Ca, Sr, Ba, rare earth elements, Zr, Si, Al, Be, Ti, Co, etc., the strength of the Cu-Fe-P alloy can be improved and the die-resistant mold can be tried. Increase in wear and tear.

又，本發明之銅合金中，再者以作為前述不可避免之雜質所包含的Mn之含有量為20質量ppm以下、Ta之含有量為1質量ppm以下為較佳。 Further, in the copper alloy of the present invention, the content of Mn contained in the unavoidable impurities is preferably 20 ppm by mass or less, and the content of Ta is 1 ppm by mass or less.

Mn、Ta之類的元素，如上述般於銅合金熔液為液相 分離時，係含有於「以Fe為主成份並含有C、及進而的Cr、Mo、W、V、Nb中之至少1種以上之液相」側中，而有促進液相分離之傾向。因此，若含有不可避免之雜質之Mn及Ta過多時，在鑄塊內有容易生成粗大的結晶物之虞。因此，藉由規定Mn之含有量設為20質量ppm以下、Ta之含有量設為1質量ppm以下，可確實地抑制粗大的結晶物之產生。 An element such as Mn or Ta, as in the above, the copper alloy melt is in the liquid phase In the case of separation, it is contained in the side of the liquid phase containing at least one of Cr, Mo, W, V, and Nb containing Fe as a main component, and tends to promote liquid phase separation. Therefore, when there are too many Mn and Ta containing unavoidable impurities, there is a possibility that coarse crystals are easily formed in the ingot. Therefore, by setting the content of Mn to 20 ppm by mass or less and the content of Ta to 1 ppm by mass or less, it is possible to reliably suppress the generation of coarse crystals.

本發明之第二樣態所相關之銅合金薄板，其係由前述銅合金所構成之銅合金薄板，因含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之鐵合金粒子露出於表面而形成的長度200μm以上的表面缺陷為5個/m2以下。更佳為長度200μm以上的表面缺陷設為2個/m2以下。 The copper alloy sheet according to the second aspect of the present invention is characterized in that the copper alloy sheet composed of the copper alloy contains at least one of Cr, Mo, W, V, and Nb, and Fe and C. The surface defects having a length of 200 μm or more formed by exposing the iron alloy particles to the surface are 5/m 2 or less. More preferably, the surface defects having a length of 200 μm or more are set to 2/m 2 or less.

又，本發明之銅合金薄板，薄板的厚度設為0.5mm以下。 Further, in the copper alloy sheet of the present invention, the thickness of the sheet is set to 0.5 mm or less.

依據該構成之銅合金薄板，係由C、Cr、Mo、W、V、Nb元素之含有量為抑制於低的銅合金所構成，故可抑制含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之鐵合金粒子之產生，並可抑制起因於該鐵合金粒子之表面缺陷之產生。又，可抑制起因於粗大的結晶物之製品的形狀不良。再者，藉由將長度200μm以上的表面缺陷設為5個/m2以下，可顯著地降低於進行壓製加工、蝕刻加工或鍍銀之際所產生之製品不良率。特別是銅合金薄板的板厚為0.5mm以下之情形時，若存在 200μm以上的表面缺陷時，由於厚度方向亦有缺陷成長之虞，例如在進行壓製加工、蝕刻加工等之為了賦予微細形狀之加工時，將成為不良之原因。就上述觀點而言，若銅合金薄板的板厚為0.2mm以下時，可更發揮本案發明之效果。若考量銅合金薄板之製造成本與所得之效果時，較佳為上述薄板的板厚之下限值為0.05mm，但並不限定於此。 The copper alloy sheet having such a configuration is composed of a copper alloy having a low content of C, Cr, Mo, W, V, and Nb elements, so that it can suppress inclusion of Cr, Mo, W, V, and Nb. The generation of at least one or more kinds of iron alloy particles of Fe and C can suppress the occurrence of surface defects caused by the iron alloy particles. Further, it is possible to suppress the shape defect of the product resulting from the coarse crystal. Further, by setting the surface defects having a length of 200 μm or more to 5/m 2 or less, it is possible to remarkably reduce the defect rate of the product which is caused by press working, etching, or silver plating. In particular, when the thickness of the copper alloy sheet is 0.5 mm or less, when there is a surface defect of 200 μm or more, the thickness direction is also defective, and for example, pressing, etching, or the like is performed to impart a fine shape. When processing, it will become a cause of failure. From the above viewpoints, when the thickness of the copper alloy sheet is 0.2 mm or less, the effects of the present invention can be further exerted. When the manufacturing cost of the copper alloy sheet and the obtained effect are considered, it is preferable that the lower limit of the thickness of the thin plate is 0.05 mm, but it is not limited thereto.

本發明之第三樣態所相關之銅合金之製造方法，其係前述銅合金之製造方法，具備下述步驟：熔解原料來生成銅合金熔液之熔解步驟、將前述銅合金熔液保持在1300℃以上之高溫保持步驟、與將保持在1300℃以上之前述銅合金熔液供給於鑄模內而得到鑄塊之鑄造步驟。 A method for producing a copper alloy according to a third aspect of the present invention is the method for producing a copper alloy, comprising the steps of: melting a raw material to form a melting step of a copper alloy melt; and maintaining the copper alloy melt in the molten metal The high temperature holding step of 1300 ° C or higher and the molten copper alloy which is maintained at 1300 ° C or higher are supplied to the mold to obtain a casting step of the ingot.

依據該構成之銅合金之製造方法，由於具備將銅合金熔液保持在1300℃以上之高溫保持步驟、與將保持在1300℃以上之銅合金熔液供給於鑄模內而得到鑄塊之鑄造步驟，故在銅合金熔液中，可抑制「含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之液相」與「以Cu為主成份之液相」之液相分離，並可抑制粗大的結晶物之生成。據此，將可減低起因於鐵合金粒子之表面缺陷。又，可抑制起因於粗大的結晶物之製品的形狀不良。 According to the method for producing a copper alloy having such a configuration, a casting step of obtaining an ingot by providing a high-temperature holding step of holding a copper alloy melt at 1300 ° C or higher and supplying a molten copper alloy held at 1300 ° C or higher to a mold is provided. Therefore, in the copper alloy melt, it is possible to suppress a liquid containing "at least one of Cr, Mo, W, V, and Nb, and a liquid phase of Fe and C" and "liquid phase containing Cu as a main component". The phase is separated and the formation of coarse crystals can be suppressed. Accordingly, the surface defects caused by the iron alloy particles can be reduced. Further, it is possible to suppress the shape defect of the product resulting from the coarse crystal.

依據本發明，可提供一種銅合金、銅合金薄 板、銅合金之製造方法，其係於Cu-Fe-P系合金中可抑制表面缺陷及形狀不良之產生。 According to the present invention, a copper alloy and a copper alloy can be provided A method for producing a plate or a copper alloy which is resistant to surface defects and shape defects in a Cu-Fe-P alloy.

S01‧‧‧熔解步驟 S01‧‧‧ melting step

S02‧‧‧高溫保持步驟 S02‧‧‧High temperature maintenance steps

S03‧‧‧鑄造步驟 S03‧‧‧ casting steps

RD‧‧‧軋延方向 RD‧‧‧Rolling direction

L‧‧‧表面缺陷的長度 L‧‧‧ Length of surface defects

[圖1]銅合金薄板之表面缺陷之光學顯微鏡觀察照片。 [Fig. 1] An optical microscopic observation photograph of a surface defect of a copper alloy sheet.

[圖2]表示本發明之實施形態之銅合金之製造方法的流程圖。 Fig. 2 is a flow chart showing a method of producing a copper alloy according to an embodiment of the present invention.

[實施發明之的最佳形態] [Best Mode for Carrying Out the Invention]

以下，對於本發明之第一實施形態之銅合金進行說明。 Hereinafter, a copper alloy according to a first embodiment of the present invention will be described.

本發明之第一實施形態之銅合金，其係包含Fe：1.5質量%以上2.7質量%以下、P：0.008質量%以上0.15質量%以下、Zn：0.01質量%以上0.5質量%以下，且殘餘部份為Cu及不可避免之雜質，作為不可避免之雜質所包含的C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm。 The copper alloy according to the first embodiment of the present invention contains Fe: 1.5% by mass or more and 2.7% by mass or less, P: 0.008% by mass or more and 0.15% by mass or less, and Zn: 0.01% by mass or more and 0.5% by mass or less, and the residual portion The content of Cu and the unavoidable impurities, the content of C contained as an unavoidable impurity is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, and the content of Mo is less than 5 ppm by mass. The content of W is less than 1 mass ppm, the content of V is less than 1 mass ppm, and the content of Nb is less than 1 mass ppm.

以下，對於將此等元素之含有量設定為前述範圍之理由進行說明。 Hereinafter, the reason why the content of these elements is set to the above range will be described.

(Fe) (Fe)

Fe為固溶於Cu的母相中，同時生成含有P的析出物(Fe-P化合物)。藉由該Fe-P化合物分散於Cu之母相中，不會使導電率降低，並會提昇強度及硬度。 Fe is a solid solution in the mother phase of Cu, and a precipitate containing P (Fe-P compound) is formed at the same time. By dispersing the Fe-P compound in the mother phase of Cu, the electrical conductivity is not lowered, and the strength and hardness are improved.

在此，若Fe之含有量未滿1.5質量%時，強度提昇之效果等為不充分。另一方面，若Fe之含有量超過2.7質量%時，會生成大的結晶物而有損及表面的清淨度之虞。進而有導致導電率及加工性降低之虞。 Here, when the content of Fe is less than 1.5% by mass, the effect of strength improvement or the like is insufficient. On the other hand, when the content of Fe exceeds 2.7% by mass, a large crystal is formed to impair the cleanliness of the surface. Further, there is a problem that the conductivity and the workability are lowered.

因此，本實施形態中，將Fe之含有量設為1.5質量%以上2.7質量%以下。尚，為能確實地達到上述作用效果，較佳為將Fe之含有量設為1.8質量%以上2.6質量%以下之範圍內。 Therefore, in the present embodiment, the content of Fe is set to be 1.5% by mass or more and 2.7% by mass or less. In order to achieve the above-described effects, the content of Fe is preferably in the range of 1.8% by mass or more and 2.6% by mass or less.

(P) (P)

P為具有脫氧作用之元素。又，如上述般，與Fe同時生成Fe-P化合物。藉由該Fe-P化合物分散於Cu之母相中，不會使導電率降低，並會提昇強度及硬度。 P is an element having a deoxidation effect. Further, as described above, an Fe-P compound is formed simultaneously with Fe. By dispersing the Fe-P compound in the mother phase of Cu, the electrical conductivity is not lowered, and the strength and hardness are improved.

在此，若P之含有量未滿0.008質量%時，強度提昇之效果等為不充分。另一方面，若P之含有量超過0.15質量%時，將導致導電率及加工性降低。 Here, when the content of P is less than 0.008% by mass, the effect of strength improvement or the like is insufficient. On the other hand, when the content of P exceeds 0.15% by mass, the electrical conductivity and workability are lowered.

因此，本實施形態中，將P之含有量設定為0.008質量%以上0.15質量%以下。尚，為能確實地達到上述作用效果，較佳為將P之含有量設為0.01質量%以上0.05質 量%以下之範圍內。 Therefore, in the present embodiment, the content of P is set to be 0.008% by mass or more and 0.15% by mass or less. Further, in order to reliably achieve the above-described effects, it is preferred to set the content of P to 0.01% by mass or more and 0.05. Within the range of % by weight or less.

(Zn) (Zn)

Zn為固溶於Cu之母相中，並具有使焊錫耐熱剝離性提昇之作用之元素。 Zn is an element which is solid-solubilized in the mother phase of Cu and has an effect of improving the heat-resistant peelability of the solder.

在此，若Zn之含有量未滿0.01質量%時，無法充份地達到使焊錫耐熱剝離性提昇之作用效果。另一方面，即使Zn之含有量超過0.5質量%，該效果亦為飽和。 Here, when the content of Zn is less than 0.01% by mass, the effect of improving the solder heat-resistant peeling property cannot be sufficiently obtained. On the other hand, even if the content of Zn exceeds 0.5% by mass, the effect is saturated.

因此，本實施形態中，將Zn之含有量設定為0.01質量%以上0.5質量%以下。尚，為能確實地達到上述作用效果，較佳為將Zn之含有量設為0.05質量%以上0.35質量%以下之範圍內。 Therefore, in the present embodiment, the content of Zn is set to be 0.01% by mass or more and 0.5% by mass or less. In order to achieve the above-described effects, the content of Zn is preferably in the range of 0.05% by mass or more and 0.35% by mass or less.

(C、Cr、Mo、W、V、Nb) (C, Cr, Mo, W, V, Nb)

C、Cr、Mo、W、V、Nb係作為不可避免之雜質而含有於上述銅合金中。在此，若C、Cr、Mo、W、V、Nb之含有量多時，則銅合金薄板之表面缺陷會大幅增加。將該表面缺陷之一例經光學顯微鏡觀察之結果表示於圖1。 C, Cr, Mo, W, V, and Nb are contained in the copper alloy as an unavoidable impurity. Here, when the content of C, Cr, Mo, W, V, and Nb is large, the surface defects of the copper alloy sheet are greatly increased. The result of observing one of the surface defects by an optical microscope is shown in Fig. 1.

經EPMA(Electron Probe Micro Analyzer)之解析結果，本實施形態中所觀察之表面缺陷，係起因於含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之鐵合金粒子。 As a result of analysis by EPMA (Electron Probe Micro Analyzer), the surface defects observed in the present embodiment are caused by inclusion of at least one of Cr, Mo, W, V, and Nb, and iron alloy particles of Fe and C.

一般而言，於熔解鑄造上述銅合金時，Fe元素係以熔解之狀態存在於「以Cu為主成份之液相」中。 但，若C、Cr、Mo、W、V、Nb存在一定量以上時，銅合金熔液被分離成「以Cu為主成份之液相」與「以Fe為主成份並含有C、及進而的Cr、Mo、W、V、Nb中之至少1種以上之液相」，其結果為，含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之粗大的結晶物將存在於鑄塊內。之後，藉由軋延鑄塊，而鐵合金粒子將露出於銅合金薄板之表面，故認為產生上述表面缺陷。又，起因於該鐵合金粒子而進行壓製加工、蝕刻加工或鍍銀時，將會產生形狀不良。 In general, when the copper alloy is melt-cast, the Fe element is present in a molten phase in the "liquid phase containing Cu as a main component". However, when C, Cr, Mo, W, V, and Nb are present in a certain amount or more, the copper alloy melt is separated into "liquid phase containing Cu as a main component" and "Fe as a main component and containing C, and further A liquid phase containing at least one of Cr, Mo, W, V, and Nb, and containing at least one of Cr, Mo, W, V, and Nb, and coarse crystals of Fe and C The object will be present in the ingot. Thereafter, by rolling the ingot, the iron alloy particles are exposed on the surface of the copper alloy sheet, and it is considered that the above surface defects are generated. Further, when the iron alloy particles are subjected to press working, etching, or silver plating, a shape defect occurs.

因此，藉由減低C、Cr、Mo、W、V、Nb元素，可抑制起因於鐵合金粒子之表面缺陷及製品之形狀不良。在此，本實施形態中，將C之含有量限制於未滿5質量ppm、Cr之含有量限制於未滿7質量ppm、Mo之含有量限制於未滿5質量ppm、W之含有量限制於未滿1質量ppm、V之含有量限制於1質量ppm、Nb之含有量限制於未滿1質量ppm。為了確實地達成上述表面缺陷及製品之形狀不良之抑制，較佳為C之含有量為設未滿4質量ppm。更佳為3ppm、又較佳為2ppm以下。將Mo之含有量設為未滿1質量ppm、進而設為未滿0.6質量ppm為宜。又，較佳為將Cr之含有量設為未滿5質量ppm、W之含有量設為未滿0.6質量ppm、V之含有量設為未滿0.6質量ppm、Nb之含有量設為未滿0.6質量ppm。 Therefore, by reducing the elements of C, Cr, Mo, W, V, and Nb, surface defects caused by the iron alloy particles and shape defects of the product can be suppressed. Here, in the present embodiment, the content of C is limited to less than 5 ppm by mass, the content of Cr is limited to less than 7 ppm by mass, the content of Mo is limited to less than 5 ppm by mass, and the content of W is limited. When the content is less than 1 mass ppm, the content of V is limited to 1 mass ppm, and the content of Nb is limited to less than 1 mass ppm. In order to reliably achieve the above-mentioned surface defects and suppression of the shape defects of the product, it is preferred that the content of C be less than 4 ppm by mass. More preferably, it is 3 ppm, and it is more preferably 2 ppm or less. The content of Mo is preferably less than 1 ppm by mass, and further preferably less than 0.6 ppm by mass. In addition, it is preferable that the content of Cr is less than 5 ppm by mass, the content of W is less than 0.6 ppm by mass, the content of V is less than 0.6 ppm by mass, and the content of Nb is set to be less than 0.6 mass ppm.

尚，作為C、Cr、Mo、W、V、Nb以外之不可避免之雜質，可舉例：Ni、Sn、Mg、Ca、Sr、Ba、稀土 類元素、Zr、Si、Al、Be、Ti、H、Li、B、N、O、F、Na、S、Cl、K、Mn、Co、Ga、Ge、As、Se、Br、Rb、Tc、Ru、Rh、Pd、Ag、Cd、In、Sb、Te、I、Cs、Hf、Ta、Re、Os、Ir、Pt、Au、Hg、Tl、Pb、Bi等。此等之不可避免之雜質，以總量計為0.3質量%以下為宜。若考量銅合金之製造成本與所得之效果時，上述不可避免之雜質之總量之下限值較佳為0.1質量%，但並不限定於此。 Further, as an unavoidable impurity other than C, Cr, Mo, W, V, and Nb, examples thereof include Ni, Sn, Mg, Ca, Sr, Ba, and rare earth. Class elements, Zr, Si, Al, Be, Ti, H, Li, B, N, O, F, Na, S, Cl, K, Mn, Co, Ga, Ge, As, Se, Br, Rb, Tc , Ru, Rh, Pd, Ag, Cd, In, Sb, Te, I, Cs, Hf, Ta, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, and the like. Such unavoidable impurities are preferably 0.3% by mass or less based on the total amount. When the manufacturing cost of the copper alloy and the effect obtained are considered, the lower limit of the total amount of the unavoidable impurities is preferably 0.1% by mass, but is not limited thereto.

接著，關於本實施形態之銅合金之製造方法，將參考圖2所示之流程圖進行說明。 Next, a method of manufacturing the copper alloy of the present embodiment will be described with reference to a flowchart shown in FIG. 2.

<熔解步驟S01> <melting step S01>

將銅原料、純鐵、Zn或Cu-Zn母合金、P或Cu-P母合金熔解後，生成銅合金熔液。尚，銅原料為純度99.99質量%以上的所謂的4NCu，純鐵為純度99.9質量%以上的所謂的3NFe、或99.99質量%以上的4NFe，氛圍較佳設為Ar。熔解中之溫度，例如1100~1300℃。 The copper raw material, pure iron, Zn or Cu-Zn master alloy, P or Cu-P master alloy is melted to form a copper alloy melt. In addition, the copper raw material is so-called 4NCu having a purity of 99.99% by mass or more, and the pure iron is so-called 3NFe having a purity of 99.9% by mass or more, or 49.7% by mass or more, and the atmosphere is preferably Ar. The temperature in the melting, for example, 1100 to 1300 °C.

<高溫保持步驟S02> <High temperature maintaining step S02>

接著，將所得之銅合金熔液昇溫至1300℃以上並保持。藉由以高溫來保持銅合金熔液，可抑制銅合金熔液中之液相分離。尚，該高溫保持步驟S02中，較佳為將溫度設為1300℃以上1500℃以下、保持時間設為1min以上24h以下之範圍內。 Next, the obtained copper alloy melt was heated to 1300 ° C or higher and held. By maintaining the copper alloy melt at a high temperature, liquid phase separation in the copper alloy melt can be suppressed. In the high temperature holding step S02, the temperature is preferably 1300 ° C or more and 1500 ° C or less, and the holding time is set to be in the range of 1 min or more and 24 h or less.

<鑄造步驟S03> <Casting step S03>

又，將1300℃以上之銅合金熔液，從高溫保持之狀態澆注至模具中來製作出鑄塊。以如此之方式，可製作出本實施形態之銅合金之鑄塊。 Further, a molten alloy of 1300 ° C or higher is poured into a mold from a state of being maintained at a high temperature to produce an ingot. In this manner, the ingot of the copper alloy of the present embodiment can be produced.

在此，鑄造時之冷卻速度較佳為速度快者，例如從1300℃至900℃止之冷卻速度以5℃/s以上，進而以10℃/s以上為宜。若考量銅合金之製造成本與所得之效果時，上述冷卻速度之上限值較佳為200℃/s，但並不限定於此。 Here, the cooling rate at the time of casting is preferably a high speed. For example, the cooling rate from 1300 ° C to 900 ° C is preferably 5 ° C / s or more, and more preferably 10 ° C / s or more. When the manufacturing cost of the copper alloy and the obtained effect are considered, the upper limit of the cooling rate is preferably 200 ° C / s, but is not limited thereto.

對於所得之鑄塊實施熱軋延後，藉由適當重複冷軋延與熱處理，可製作出指定厚度之銅合金薄板。熱軋延係在還元性氛圍中以750℃~1000℃之條件來實施。冷軋延的壓下率為40~95%，熱處理為在400~700℃下進行，於最終軋延之後以200~350℃來進行最終退火。 After the hot rolling is performed on the obtained ingot, a copper alloy sheet having a specified thickness can be produced by appropriately repeating cold rolling and heat treatment. The hot rolling extension is carried out in a reductive atmosphere at a temperature of 750 ° C to 1000 ° C. The reduction ratio of the cold rolling is 40 to 95%, the heat treatment is performed at 400 to 700 ° C, and the final annealing is performed at 200 to 350 ° C after the final rolling.

該銅合金薄板中，因含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之鐵合金粒子露出於表面而形成的長度200μm以上的表面缺陷設為5個/m2以下。適宜為200μm以上的表面缺陷設為2個/m2以下。進而以1個/m2以下為宜。 In the copper alloy sheet, surface defects having a length of 200 μm or more formed by exposing at least one of Cr, Mo, W, V, and Nb and iron alloy particles of Fe and C to the surface are 5/m 2 . the following. The surface defect of 200 μm or more is preferably 2/m 2 or less. Further, it is preferably 1/m 2 or less.

依據如以上般所構成的本實施形態，因C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm，故可抑制鑄塊內粗大的結晶物之 生成。據此，可抑制起因於該粗大的結晶物之鐵合金粒子之形成，而可大幅減低表面缺陷之產生。又，可抑制製品的形狀不良。 According to the embodiment configured as described above, the content of C is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, the content of Mo is less than 5 ppm by mass, and the content of W is When the content of V is less than 1 ppm by mass, the content of V is less than 1 ppm by mass, and the content of Nb is less than 1 ppm by mass, coarse crystals in the ingot can be suppressed. generate. According to this, formation of the iron alloy particles due to the coarse crystals can be suppressed, and the occurrence of surface defects can be greatly reduced. Moreover, the shape defect of a product can be suppressed.

再者，本實施形態之製造方法，係因具備將前述銅合金熔液保持在1300℃以上之高溫之高溫保持步驟S02、與將保持在1300℃以上之銅合金熔液供給鑄模後來製造鑄塊之鑄造步驟S03，故可抑制含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之粗大的結晶物之生成。 Further, in the production method of the present embodiment, the high temperature holding step S02 for maintaining the copper alloy melt at a high temperature of 1300 ° C or higher and the copper alloy melt held at 1300 ° C or higher are supplied to the mold to produce an ingot. Since the casting step S03 is performed, it is possible to suppress the formation of a crystal containing at least one of Cr, Mo, W, V, and Nb and coarse crystals of Fe and C.

以下，對於本發明之第二實施形態之銅合金進行說明。 Hereinafter, a copper alloy according to a second embodiment of the present invention will be described.

本發明之第二實施形態之銅合金，其係含有Fe：1.5質量%以上2.7質量%以下、P：0.008質量%以上0.15質量%以下、Zn：0.01質量%以上0.5質量%以下，同時含有Ni：0.003質量%以上0.5質量%以下、Sn：0.003質量%以上0.5質量%以下之任一者或兩者，進而在0.0007質量%以上0.5質量%以下之範圍內含有Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co中之至少1種或2種以上，且殘餘部份為Cu及不可避免之雜質，作為前述不可避免之雜質所包含的C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm。 The copper alloy according to the second embodiment of the present invention contains Fe: 1.5% by mass or more and 2.7% by mass or less, P: 0.008% by mass or more and 0.15% by mass or less, and Zn: 0.01% by mass or more and 0.5% by mass or less, and contains Ni. Any one or both of 0.003 mass% or more and 0.5 mass% or less and Sn: 0.003 mass% or more and 0.5 mass% or less, and further contains Mg, Ca, Sr, Ba in a range of 0.0007 mass% or more and 0.5 mass% or less. At least one or more of rare earth elements, Zr, Si, Al, Be, Ti, and Co, and the residual portion is Cu and unavoidable impurities, and the content of C contained as the unavoidable impurity When the content is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, the content of Mo is less than 5 ppm by mass, the content of W is less than 1 ppm by mass, and the content of V is less than 1 ppm by mass. The content of Nb is less than 1 mass ppm.

以下，對於將此等元素之含有量設定為前述範圍之理由進行說明。尚，關於與第一實施形態相同的元素將省略 說明。 Hereinafter, the reason why the content of these elements is set to the above range will be described. Further, the same elements as those of the first embodiment will be omitted. Description.

(Ni) (Ni)

Ni為固溶於Cu之母相中，並具有使強度及耐引線彎曲疲勞特性(耐重複彎曲疲勞特性)提昇之作用。 Ni is a solid solution in the mother phase of Cu and has an effect of improving the strength and resistance to bending fatigue of the lead (resistance to repeated bending fatigue).

在此，若Ni之含有量未滿0.003質量%時，無法充份達到上述效果。另一方面，若Ni之含有量超過0.5質量%時，導電率會顯著地降低。 Here, when the content of Ni is less than 0.003 mass%, the above effects cannot be sufficiently obtained. On the other hand, when the content of Ni exceeds 0.5% by mass, the electrical conductivity is remarkably lowered.

因此，本實施形態中，將Ni之含有量設定為0.003質量%以上0.5質量%以下。尚，為能確實地達到上述作用效果，較佳為將Ni之含有量設為0.008質量%以上0.2質量%以下之範圍內。 Therefore, in the present embodiment, the content of Ni is set to be 0.003% by mass or more and 0.5% by mass or less. In order to achieve the above-described effects, the content of Ni is preferably in the range of 0.008% by mass or more and 0.2% by mass or less.

(Sn) (Sn)

Sn為固溶於Cu之母相中，並具有使強度及焊接性提昇之作用。 Sn is a solid solution in the mother phase of Cu and has an effect of improving strength and weldability.

在此，若Sn之含有量未滿0.003質量%時，無法充份地達成上述效果。另一方面，若Sn之含有量超過0.5質量%時，導電率會顯著地降低。 Here, when the content of Sn is less than 0.003 mass%, the above effects cannot be satisfactorily achieved. On the other hand, when the content of Sn exceeds 0.5% by mass, the electrical conductivity is remarkably lowered.

因此，本實施形態中，將Sn之含有量設定為0.003質量%以上0.5質量%以下。尚，為能確實地達到上述作用效果，較佳為將Sn之含有量設為0.008質量%以上0.2質量%以下之範圍內。 Therefore, in the present embodiment, the content of Sn is set to be 0.003% by mass or more and 0.5% by mass or less. In order to achieve the above-described effects, the content of Sn is preferably in the range of 0.008% by mass or more and 0.2% by mass or less.

(Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co) (Mg, Ca, Sr, Ba, rare earth elements, Zr, Si, Al, Be, Ti, Co)

Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co為固溶於銅之母相中，或以作為析出物、結晶物而存在，並具有使Cu-Fe-P系合金之強度一定程度地提昇之作用，進而亦具有使耐沖裁模具摩損性之作用。 Mg, Ca, Sr, Ba, rare earth elements, Zr, Si, Al, Be, Ti, Co are solid-dissolved in the mother phase of copper, or exist as precipitates or crystals, and have Cu-Fe The strength of the -P alloy increases to a certain extent, and further has the effect of making the punch-resistant mold wear-resistant.

在此，若Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之含有量未滿0.0007質量%時，無法充份達成上述效果。另一方面，若Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之含有量超過0.5質量%時，導電率會降低，同時容易生成大的氧化物或析出物或結晶物，進而有損及表面之清淨度之虞。 Here, when the content of Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, and Co is less than 0.0007 mass%, the above effects cannot be sufficiently obtained. On the other hand, when the content of Mg, Ca, Sr, Ba, rare earth elements, Zr, Si, Al, Be, Ti, and Co exceeds 0.5% by mass, the electrical conductivity is lowered and a large oxide or a large oxide is easily formed. Precipitates or crystals, which in turn impair the cleanliness of the surface.

因此，本實施形態之銅合金，係將Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之含有量設定為0.0007質量%以上0.5質量%以下。尚，為能確實地達到上述作用效果，較佳為將Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之含有量設為0.005質量%以上0.15質量%以下之範圍內。 Therefore, the copper alloy of the present embodiment has a content of Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, and Co of 0.0007 mass% or more and 0.5 mass% or less. In order to reliably achieve the above-described effects, the content of Mg, Ca, Sr, Ba, rare earth elements, Zr, Si, Al, Be, Ti, and Co is preferably 0.005% by mass or more and 0.15% by mass. Within the scope below.

在此，所謂稀土類元素，係指Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu。 Here, the rare earth element means Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

尚，作為C、Cr、Mo、W、V、Nb以外之不可避免之雜質，可舉例：H、Li、B、N、O、F、Na、S、Cl、K、Mn、Ga、Ge、As、Se、Br、Rb、Tc、Ru、Rh、Pd、Ag、Cd、In、Sb、Te、I、Cs、Hf、Ta、Re、Os、 Ir、Pt、Au、Hg、Tl、Pb、Bi等。此等之不可避免之雜質，以總量計為0.3質量%以下為宜。若考量銅合金之製造成本與所得之效果時，上述不可避免之雜質之總量之下限值較佳為0.1質量%，但並不限定於此。 Further, as an unavoidable impurity other than C, Cr, Mo, W, V, Nb, for example, H, Li, B, N, O, F, Na, S, Cl, K, Mn, Ga, Ge, As, Se, Br, Rb, Tc, Ru, Rh, Pd, Ag, Cd, In, Sb, Te, I, Cs, Hf, Ta, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, and the like. Such unavoidable impurities are preferably 0.3% by mass or less based on the total amount. When the manufacturing cost of the copper alloy and the effect obtained are considered, the lower limit of the total amount of the unavoidable impurities is preferably 0.1% by mass, but is not limited thereto.

該第二實施形態之銅合金，係藉由與上述第一實施形態相同之熔解步驟S01、熔液之高溫保持步驟S02、鑄造步驟S03而來製造。在熔解步驟S01中，對於Ni、Sn、Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之添加，係使用金屬元素單質或包含上述元素之母合金。 The copper alloy according to the second embodiment is produced by the melting step S01, the high temperature holding step S02 of the melt, and the casting step S03 which are the same as those of the first embodiment. In the melting step S01, for the addition of Ni, Sn, Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, and Co, a single element of a metal element or a mother alloy containing the above element is used.

依據如以上般所構成的本實施形態，由於含有Ni、Sn，故可試圖藉由固溶硬化來提昇強度。 According to the present embodiment configured as described above, since Ni and Sn are contained, it is possible to attempt to increase the strength by solid solution hardening.

又，由於在0.0007質量%以上0.5質量%以下之範圍內含有Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co中之至少1種或2種以上，故可試圖Cu-Fe-P系合金之更進一步之高強度化，同時試圖提昇耐沖裁模具摩損性。 In addition, at least one or two or more of Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, and Co are contained in a range of 0.0007 mass% or more and 0.5 mass% or less. Attempts can be made to further increase the strength of the Cu-Fe-P alloy while attempting to improve the wear resistance of the blanking die.

又，因C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm，故可抑制含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之鐵合金粒子之形成，將可大幅減低表面缺陷之產生。又，可抑制製品的形狀不良。 In addition, the content of C is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, the content of Mo is less than 5 ppm by mass, and the content of W is less than 1 ppm by mass, and the content of V is contained. When the amount is less than 1 mass ppm and the content of Nb is less than 1 mass ppm, formation of at least one of Cr, Mo, W, V, and Nb and iron alloy particles of Fe and C can be suppressed. Can significantly reduce the occurrence of surface defects. Moreover, the shape defect of a product can be suppressed.

以下，對於本發明之第三實施形態之銅合金進行說明。 Hereinafter, a copper alloy according to a third embodiment of the present invention will be described.

本發明之第三實施形態之銅合金，其係包含Fe：1.5質量%以上2.7質量%以下、P：0.008質量%以上0.15質量%以下、Zn：0.01質量%以上0.5質量%以下，且殘餘部份為Cu及不可避免之雜質，作為不可避免之雜質所包含的C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm、Mn之含有量為20質量ppm以下、Ta之含有量為1質量ppm以下。 The copper alloy according to the third embodiment of the present invention contains Fe: 1.5% by mass or more and 2.7% by mass or less, P: 0.008% by mass or more and 0.15% by mass or less, and Zn: 0.01% by mass or more and 0.5% by mass or less, and the residual portion The content of Cu and the unavoidable impurities, the content of C contained as an unavoidable impurity is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, and the content of Mo is less than 5 ppm by mass. The content of W is less than 1 mass ppm, the content of V is less than 1 mass ppm, the content of Nb is less than 1 mass ppm, the content of Mn is 20 mass ppm or less, and the content of Ta is 1 mass. Below ppm.

以下，對於將此等元素之含有量設定為前述範圍之理由進行說明。尚，關於與第一實施形態相同的元素將省略說明。 Hereinafter, the reason why the content of these elements is set to the above range will be described. The same elements as those of the first embodiment will be omitted.

(Mn、Ta) (Mn, Ta)

Mn、Ta係作為不可避免之雜質而被含有於上述銅合金中。 Mn and Ta are contained in the copper alloy as an unavoidable impurity.

一般而言，於熔解鑄造上述銅合金時，Fe元素係以熔解之狀態存在於「以Cu為主成份之液相」中。但，若C、Cr、Mo、W、V、Nb存在一定量以上時，銅合金熔液被分離成「以Cu為主成份之液相」與「以Fe為主成份並含有C、及進而的Cr、Mo、W、V、Nb中之至少1種以上之液相」。在此，銅合金熔液以如上述般液相分離時， Mn、Ta係被含有於「以Fe為主成份並含有C、及進而的Cr、Mo、W、V、Nb中之至少1種以上之液相」中，且為有促進液相分離之虞的元素。 In general, when the copper alloy is melt-cast, the Fe element is present in a molten phase in the "liquid phase containing Cu as a main component". However, when C, Cr, Mo, W, V, and Nb are present in a certain amount or more, the copper alloy melt is separated into "liquid phase containing Cu as a main component" and "Fe as a main component and containing C, and further A liquid phase of at least one of Cr, Mo, W, V, and Nb. Here, when the copper alloy melt is separated in the liquid phase as described above, Mn and Ta are contained in a liquid phase containing at least one of Cr, Mo, W, V, and Nb containing Fe as a main component and further promoting liquid phase separation. Elements.

因此，藉由減低C、Cr、Mo、W、V、Nb元素，同時減低Mn、Ta之含有量，可抑制銅合金熔液之液相分離而抑制粗大的結晶物之生成，並抑制起因於鐵合金粒子之表面缺陷及形狀不良。因此，本實施形態之銅合金中，將C之含有量限制於未滿5質量ppm、Cr之含有量限制於未滿7質量ppm、Mo之含有量限制於未滿5質量ppm、W之含有量限制於未滿1質量ppm、V之含有量限制於未滿1質量ppm、Nb之含有量限制於未滿1質量ppm、Mn之含有量限制於20質量ppm以下、Ta之含有量限制於1質量ppm以下。為了確實地達成上述表面缺陷及製品之形狀不良之抑制，較佳為C之含有量為未滿4質量ppm。更佳為3ppm、又較佳為2ppm以下。將Mo之含有量設為未滿1質量ppm、進而設為未滿0.6質量ppm為宜。又，較佳為將Cr之含有量設為未滿5質量ppm、W之含有量設為未滿0.6質量ppm、V之含有量設為未滿0.6質量ppm、Nb之含有量設為未滿0.6質量ppm。又較佳為Mn之含有量設為未滿15質量ppm、Ta之含有量設為未滿0.7質量ppm。 Therefore, by reducing the C, Cr, Mo, W, V, and Nb elements and reducing the content of Mn and Ta, the liquid phase separation of the copper alloy melt can be suppressed, and the formation of coarse crystals can be suppressed, and the cause of the formation can be suppressed. The surface defects and shape of the ferroalloy particles are poor. Therefore, in the copper alloy of the present embodiment, the content of C is limited to less than 5 ppm by mass, the content of Cr is limited to less than 7 ppm by mass, and the content of Mo is limited to less than 5 ppm by mass, and the content of W is contained. The amount of V is limited to less than 1 mass ppm, the content of V is limited to less than 1 mass ppm, the content of Nb is limited to less than 1 mass ppm, the content of Mn is limited to 20 mass ppm or less, and the content of Ta is limited to 1 mass ppm or less. In order to reliably achieve the above-mentioned surface defects and suppression of shape defects of the product, it is preferred that the content of C is less than 4 ppm by mass. More preferably, it is 3 ppm, and it is more preferably 2 ppm or less. The content of Mo is preferably less than 1 ppm by mass, and further preferably less than 0.6 ppm by mass. In addition, it is preferable that the content of Cr is less than 5 ppm by mass, the content of W is less than 0.6 ppm by mass, the content of V is less than 0.6 ppm by mass, and the content of Nb is set to be less than 0.6 mass ppm. Further, it is preferable that the content of Mn is less than 15 ppm by mass and the content of Ta is less than 0.7 ppm by mass.

尚，作為C、Cr、Mo、W、V、Nb、Mn、Ta以外之不可避免之雜質，可舉例：Ni、Sn、Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、H、Li、B、N、 O、F、Na、S、Cl、K、Co、Ga、Ge、As、Se、Br、Rb、Tc、Ru、Rh、Pd、Ag、Cd、In、Sb、Te、I、Cs、Hf、Re、Os、Ir、Pt、Au、Hg、Tl、Pb、Bi等。此等之不可避免之雜質，以總量計為0.3質量%以下為宜。若考量銅合金之製造成本與所得之效果時，上述不可避免之雜質之總量之下限值較佳為0.1質量%，但並不限定於此。 Further, as an unavoidable impurity other than C, Cr, Mo, W, V, Nb, Mn, and Ta, for example, Ni, Sn, Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, H, Li, B, N, O, F, Na, S, Cl, K, Co, Ga, Ge, As, Se, Br, Rb, Tc, Ru, Rh, Pd, Ag, Cd, In, Sb, Te, I, Cs, Hf, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, and the like. Such unavoidable impurities are preferably 0.3% by mass or less based on the total amount. When the manufacturing cost of the copper alloy and the effect obtained are considered, the lower limit of the total amount of the unavoidable impurities is preferably 0.1% by mass, but is not limited thereto.

該第三實施形態之銅合金，係藉由與上述第一實施形態及第二實施形態相同之熔解步驟S01、熔液之高溫保持步驟S02、鑄造步驟S03而來製造。 The copper alloy according to the third embodiment is produced by the melting step S01, the high temperature holding step S02 of the melt, and the casting step S03 which are the same as those of the first embodiment and the second embodiment.

在熔解步驟S01中，較佳為使用Mn及Ta之含有量為少的原料。特別是由於Mn元素由鐵系原料等混入之可能性為高，故較佳為嚴選鐵系原料來使用。較佳以使用Mn為0.1質量%以下、Ta為0.005質量%以下之Fe原料。 In the melting step S01, it is preferred to use a raw material having a small content of Mn and Ta. In particular, since the possibility that the Mn element is mixed by the iron-based raw material or the like is high, it is preferable to use the iron-based raw material strictly. It is preferable to use a Fe raw material having Mn of 0.1% by mass or less and Ta of 0.005% by mass or less.

依據如以上般所構成的本實施形態，因作為不可避免之雜質所包含的C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm、Mn之含有量為20質量ppm以下、Ta之含有量為1質量ppm以下，故可抑制銅合金熔液之液相分離、並抑制鐵合金粒子之形成，可大幅減低表面缺陷之產生。又，可抑制製品的形狀不良。 According to the present embodiment, the content of C contained as an unavoidable impurity is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, and the content of Mo is less than 5 The content of ppm and W is less than 1 mass ppm, the content of V is less than 1 mass ppm, the content of Nb is less than 1 mass ppm, the content of Mn is 20 mass ppm or less, and the content of Ta is Since it is 1 mass ppm or less, the liquid phase separation of the copper alloy melt can be suppressed, and the formation of the iron alloy particles can be suppressed, and the occurrence of surface defects can be greatly reduced. Moreover, the shape defect of a product can be suppressed.

以上，對於本發明之實施形態之銅合金、銅 合金薄板、銅合金之製造方法進行說明，但本發明並不限定於此，能夠在不超出本發明的技術思想的範圍內進行適當變更。 Above, the copper alloy and copper of the embodiment of the present invention The method of producing the alloy sheet and the copper alloy is described, but the present invention is not limited thereto, and can be appropriately modified without departing from the scope of the technical idea of the present invention.

例如熔解銅原料而生成銅熔液，並對該銅熔液中添加各種元素之情形進行說明，但並不限定於此，熔解廢鋼原料等來進行成份調製亦可。 For example, a copper melt is melted to form a copper melt, and various elements are added to the copper melt. However, the present invention is not limited thereto, and the scrap steel raw material or the like may be melted to prepare a component.

又，本實施形態中雖已對具備高溫保持步驟S02之情形進行說明，但並不限定於此，藉由其他的手段來減低含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之粗大的結晶物之含有量亦可。例如藉由嚴選所使用之原料亦可防止C、Cr、Mo、W、V、Nb元素之混入。由於C、Cr、Mo、W、V、Nb元素由鐵系原料等混入之可能性為高，故較佳為嚴選鐵系原料來使用。 In the present embodiment, the high temperature holding step S02 is described. However, the present invention is not limited thereto, and at least one of Cr, Mo, W, V, and Nb is reduced by another means. The content of the coarse crystals of Fe and C may also be. For example, the incorporation of C, Cr, Mo, W, V, and Nb elements can be prevented by strictly selecting the materials used. Since the possibility that the C, Cr, Mo, W, V, and Nb elements are mixed by the iron-based raw material or the like is high, it is preferable to use the iron-based raw material strictly.

再者，第三實施形態中，亦可含有Ni：0.003質量%以上0.5質量%以下、Sn：0.003質量%以上0.5質量%以下之任一者或兩者，可進而在0.0007質量%以上0.5質量%以下之範圍內含有Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co中之至少1種或2種以上。 In addition, in the third embodiment, Ni: 0.003 mass% or more and 0.5 mass% or less, and Sn: 0.003 mass% or more and 0.5 mass% or less may be contained, and further, it may be 0.0007 mass% or more and 0.5 mass. In the range of % or less, at least one or two or more of Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, and Co are contained.

[實施例] [Examples]

以下，對於為確認本發明的效果而進行的確認實驗的結果進行說明。 Hereinafter, the results of the confirmation experiment performed to confirm the effects of the present invention will be described.

(實施例1) (Example 1)

準備由純度為99.99質量%以上、C含有量為1質量ppm以下的無氧銅(ASTM B152 C10100)所構成的銅原料，將此裝入氧化鋁製坩堝內，藉由設為Ar氛圍之高周波熔解爐來進行熔解。 A copper raw material composed of oxygen-free copper (ASTM B152 C10100) having a purity of 99.99% by mass or more and a C content of 1 ppm by mass or less is prepared, and this is placed in a crucible made of alumina, and is set to a high cycle of an Ar atmosphere. The melting furnace is used for melting.

在所得的銅熔液內中，因應所需地添加作為原料的純鐵、Fe-C母合金、Fe-Cr母合金、Fe-Mo母合金、Fe-W母合金、Fe-V母合金、Fe-Nb母合金、Cu-Zn母合金、Cu-Ni母合金、Cu-Sn母合金、Cu-P母合金、及Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之原料或母合金，藉由Ar氛圍中以1200℃熔解，調製成如表1、2所示之成份組成，並澆注水冷銅鑄模中來製作出鑄塊。尚，各原料的C含有量為10質量ppm以下。所製作出的鑄塊之大小設為厚度約30mm×寬度約150mm×長度約200mm。尚，於本發明例1-27中，使用高純度鐵(純度99.99質量%)來作為鐵原料。 In the obtained copper melt, pure iron, Fe-C master alloy, Fe-Cr master alloy, Fe-Mo master alloy, Fe-W master alloy, Fe-V master alloy, as a raw material, are added as needed. Fe-Nb master alloy, Cu-Zn master alloy, Cu-Ni master alloy, Cu-Sn master alloy, Cu-P master alloy, and Mg, Ca, Sr, Ba, rare earth elements, Zr, Si, Al, Be The raw materials or master alloys of Ti and Co were melted at 1200 ° C in an Ar atmosphere to prepare a composition as shown in Tables 1 and 2, and poured into a water-cooled copper mold to prepare an ingot. In addition, the C content of each raw material is 10 mass ppm or less. The size of the ingot produced was set to a thickness of about 30 mm, a width of about 150 mm, and a length of about 200 mm. Further, in Inventive Example 1-27, high-purity iron (purity: 99.99% by mass) was used as the iron raw material.

又，於本發明例23-26中，將所得之熔液一度由1200℃昇溫至1300℃，之後再製作出鑄塊。 Further, in Inventive Examples 23 to 26, the obtained melt was once heated from 1200 ° C to 1300 ° C, and then an ingot was produced.

又，比較例1-4中，添加C粉末並藉由與熔液接觸而使C量增加。比較例5-9中，添加Mo、Cr、V、W、Nb來調整成份。 Further, in Comparative Example 1-4, C powder was added and the amount of C was increased by contact with the melt. In Comparative Examples 5-9, Mo, Cr, V, W, and Nb were added to adjust the components.

將上述熔液溫度設為1300℃時的由1300℃至900℃之冷卻速度、及將熔液溫度設為1200℃時的由1200℃至900℃之冷卻速度，設為約10℃/s以上。 The cooling rate from 1300 ° C to 900 ° C when the melt temperature is 1300 ° C and the cooling rate from 1200 ° C to 900 ° C when the melt temperature is 1200 ° C is set to be about 10 ° C / s or more. .

將所得的鑄塊加熱至950℃，實施至厚度5.0mm為止的熱軋延。該熱軋延後，為除去氧化膜而實施表面磨削，並使成為厚度4.0mm。 The obtained ingot was heated to 950 ° C and subjected to hot rolling until a thickness of 5.0 mm. After the hot rolling, surface grinding was performed to remove the oxide film, and the thickness was 4.0 mm.

之後，實施粗軋延並使成為厚度0.4mm。接著，實施550℃×1小時的加熱步驟，再者實施冷軋延並使厚度成為0.2mm。 Thereafter, the rough rolling was performed to have a thickness of 0.4 mm. Next, a heating step of 550 ° C × 1 hour was carried out, and further, cold rolling was performed to have a thickness of 0.2 mm.

接著，實施450℃×1小時的加熱步驟，並實施最終冷軋延來製作出厚度約0.1mm×寬度約150mm的棒料。 Next, a heating step of 450 ° C × 1 hour was carried out, and final cold rolling was performed to prepare a bar having a thickness of about 0.1 mm × a width of about 150 mm.

又，作為最終退火實施250℃×1小時的加熱步驟，將得的棒料作為特性評估用棒料。在此，上述所有的熱處理係在Ar氛圍中來實施。 Further, as a final annealing, a heating step of 250 ° C × 1 hour was carried out, and the obtained bar was used as a bar for property evaluation. Here, all of the above heat treatments are carried out in an Ar atmosphere.

使用所得的特性評估用棒料來實施以下的特性評估。 The following characteristics evaluation was carried out using the obtained property evaluation bar.

(Fe、P、Zn、其他添加元素及雜質含有量之測定方法) (Method for measuring Fe, P, Zn, other added elements and impurity content)

表1之組成，Fe、P、Zn、其他添加元素、Cr、Mo、W、V、Nb為使用輝光放電質量分析裝置(GD-MS)來進行測定，C為使用紅外線吸收法來進行測定。 In the composition of Table 1, Fe, P, Zn, and other additive elements, Cr, Mo, W, V, and Nb were measured using a glow discharge mass spectrometer (GD-MS), and C was measured by an infrared absorption method.

(機械性特性) (mechanical properties)

依JIS Z 2241：2011(依據ISO 6892-1：2009)之規定，由特性評估用棒料中取樣13B號試片，藉由支距法(offset method)來測定0.2%耐力。 According to JIS Z 2241:2011 (according to ISO 6892-1:2009), sample No. 13B was sampled from the bar for property evaluation, and 0.2% proof force was measured by an offset method.

尚，試片係將拉伸試驗之拉伸方向以相對於特性評估 用棒料之軋延方向為呈平行之方式來進行取樣。 Still, the test piece evaluates the tensile direction of the tensile test in relation to the characteristics. Sampling was carried out in a parallel manner with the rolling direction of the bars.

(缺陷個數) (number of defects)

由特性評估用棒料中，對於0.2m2的銅條25片，檢查因異物露出於表面而形成的長度200μm以上的表面缺陷之個數。缺陷的長度，係以異物露出於表面之表面傷痕之軋延方向之最大長度來設定之。藉由上述評估方法來算出平均缺陷個數(個/m2)。 In the bar for property evaluation, the number of surface defects having a length of 200 μm or more formed by exposing foreign matter to the surface was examined for 25 pieces of copper strips of 0.2 m 2 . The length of the defect is set by the maximum length of the rolling direction of the surface flaw of the foreign matter exposed on the surface. The number of average defects (number/m 2 ) was calculated by the above evaluation method.

將評估結果表示於表1、2。 The evaluation results are shown in Tables 1 and 2.

於不可避免之雜質之C、Cr、Mo、W、V、Nb之含有量為超過本發明範圍之比較例1-9中，缺陷個數為非常多的7.8個/m2以上。 In Comparative Example 1-9 in which the content of C, Cr, Mo, W, V, and Nb which are unavoidable impurities is more than the range of the present invention, the number of defects is 7.8 pieces/m 2 or more.

相較於此，於不可避免之雜質的C、Cr、Mo、W、V、Nb之含有量為本發明範圍內之本發明例1-27中，缺陷個數皆為4.4個/m2以下，相較於比較例可確認到大幅減低。 In contrast, the content of C, Cr, Mo, W, V, and Nb in the unavoidable impurities is in the range of 4.4/m 2 or less in the inventive example 1-27 within the scope of the present invention. Compared with the comparative example, it was confirmed that the reduction was drastically reduced.

又，於添加Ni、Sn、Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co之本發明例8-22、24-26中，0.2%耐力為500MPa左右，可確認到強度特性之提昇。 Further, in Examples 8-22 and 24-26 of the present invention in which Ni, Sn, Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti, Co were added, 0.2% of the endurance was about 500 MPa. , the improvement of the strength characteristics can be confirmed.

再者，將銅合金熔液以1300℃保持後製作出鑄塊，於實施熔液之高溫保持之本發明例23-26中，缺陷個數更為減低。由此可確認到，藉由實施銅合金熔液之高溫保持，可進而抑制銅合金薄板之表面缺陷。 Further, the copper alloy melt was held at 1300 ° C to prepare an ingot, and in the inventive examples 23 to 26 in which the high temperature of the melt was maintained, the number of defects was further reduced. From this, it was confirmed that the surface defects of the copper alloy sheet can be further suppressed by performing high temperature retention of the copper alloy melt.

(實施例2) (Example 2)

準備由純度99.99質量%以上、C含有量為1質量ppm以下、Mn含有量為0.1質量ppm以下、Ta含有量為0.1質量ppm以下的無氧銅(ASTM B152 C10100)所構成的銅原料，將此裝入氧化鋁製坩堝內，並藉由設為Ar氛圍之高周波熔解爐來進行熔解。 A copper raw material composed of oxygen-free copper (ASTM B152 C10100) having a purity of 99.99% by mass or more, a C content of 1 ppm by mass or less, a Mn content of 0.1 ppm by mass or less, and a Ta content of 0.1 ppm by mass or less is prepared. This was placed in an alumina crucible and melted by a high-frequency melting furnace set to an Ar atmosphere.

在所得的銅熔液內，因應所需地添加作為原料的純鐵、Fe-C母合金、Fe-Cr母合金、Fe-Mo母合金、Fe-W母合金、Fe-V母合金、Fe-Nb母合金、Fe-Mn母合金、Fe-Ta母合金、Cu-Zn母合金、Cu-Ni母合金、Cu-Sn母合金、Cu-P母合金、及Mg、Ca、Sr、Ba、稀土類元 素、Zr、Si、Al、Be、Ti、Co的原料或母合金，與實施例1以相同之方法，製作出如表3所示之成份組成的鑄塊(厚度約30mm×寬度約150mm×長度約200mm)。尚，於本發明例49-51中，將所得之熔液一度由1200℃昇溫至1300℃，之後再製作出鑄塊。 In the obtained copper melt, pure iron, Fe-C master alloy, Fe-Cr master alloy, Fe-Mo master alloy, Fe-W master alloy, Fe-V master alloy, Fe as a raw material are added as needed. -Nb master alloy, Fe-Mn master alloy, Fe-Ta master alloy, Cu-Zn master alloy, Cu-Ni master alloy, Cu-Sn master alloy, Cu-P master alloy, and Mg, Ca, Sr, Ba, Rare earth element A raw material or a master alloy of Z, Z, Si, Al, Be, Ti, Co, in the same manner as in Example 1, an ingot having a composition as shown in Table 3 (thickness of about 30 mm × width of about 150 mm ×) was produced. The length is about 200mm). Further, in Inventive Examples 49 to 51, the obtained melt was once heated from 1200 ° C to 1300 ° C, and then an ingot was produced.

使用此鑄塊，藉由與實施例1以相同之方法來製作厚度約0.1mm×寬度約150mm的特性評估用棒料。 Using this ingot, a property evaluation bar having a thickness of about 0.1 mm and a width of about 150 mm was produced in the same manner as in Example 1.

使用所得的特性評估用棒料來實施以下的特性評估。 The following characteristics evaluation was carried out using the obtained property evaluation bar.

尚，關於缺陷個數，係進行較實施例1為更詳細評估，故由特性評估用棒料來觀察0.2m2的銅條50片的正反兩面，並檢查因異物露出於表面而形成的長度200μm以上的表面缺陷之個數。缺陷的長度，係以異物露出於表面之表面傷痕之軋延方向之最大長度來設定之。藉由上述評估方法來算出平均缺陷個數(個/m2)。 Further, regarding the number of defects, the evaluation is performed in more detail than in the first embodiment. Therefore, the front and back sides of 50 pieces of 0.2 m 2 copper strips are observed from the bar for characteristic evaluation, and the foreign matter is exposed on the surface. The number of surface defects having a length of 200 μm or more. The length of the defect is set by the maximum length of the rolling direction of the surface flaw of the foreign matter exposed on the surface. The average number of defects (number/m 2 ) was calculated by the above evaluation method.

(Fe、P、Zn、Mn、Ta、其他添加元素及雜質含有量之測定方法) (Method for measuring Fe, P, Zn, Mn, Ta, other added elements and impurity content)

Fe、P、Zn為使用感應耦合電漿發光分光分析裝置(ICP-AES)來進行測定。Mn、Ta、其他添加元素、Cr、Mo、W、V、Nb為使用輝光放電質量分析裝置(GD-MS)來進行測定。 Fe, P, and Zn were measured using an inductively coupled plasma luminescence spectrometer (ICP-AES). Mn, Ta, and other additive elements, Cr, Mo, W, V, and Nb were measured using a glow discharge mass spectrometer (GD-MS).

C為使用紅外線吸收法來進行測定。 C is measured by an infrared absorption method.

將評估結果表示於表3。 The evaluation results are shown in Table 3.

於規定不可避免之雜質的Mn之含有量為20質量ppm以下、Ta之含有量為1質量ppm以下之本發明例40-51中，平均缺陷個數更為減低。 In the present invention examples 40 to 51 in which the content of Mn which is an unavoidable impurity is 20 mass ppm or less and the content of Ta is 1 mass ppm or less, the number of average defects is further reduced.

由此可確認到，藉由將不可避免之雜質的Mn之含有量設為20質量ppm以下、Ta之含有量設為1質量ppm以下，可進而抑制銅合金薄板之表面缺陷。 From this, it was confirmed that the surface defect of the copper alloy sheet can be further suppressed by setting the content of Mn of the unavoidable impurities to 20 ppm by mass or less and the content of Ta to 1 ppm by mass or less.

[產業利用性] [Industry Utilization]

根據本發明相關之銅合金、銅合金薄板及銅合金之製造方法，可抑制於Cu-Fe-P系合金中之表面缺陷及形狀不良之產生。 According to the method for producing a copper alloy, a copper alloy sheet, and a copper alloy according to the present invention, surface defects and shape defects in the Cu-Fe-P alloy can be suppressed.

Claims (5)

一種銅合金薄板，其係由含有Fe：1.5質量%以上2.7質量%以下、P：0.008質量%以上0.15質量%以下、Zn：0.01質量%以上0.5質量%以下，且殘餘部份為Cu及不可避免之雜質，作為前述不可避免之雜質所包含的C之含有量為未滿5質量ppm、Cr之含有量為未滿7質量ppm、Mo之含有量為未滿5質量ppm、W之含有量為未滿1質量ppm、V之含有量為未滿1質量ppm、Nb之含有量為未滿1質量ppm、Mn之含有量為20質量ppm以下、Ta之含有量為1質量ppm以下之銅合金所構成，因含有Cr、Mo、W、V、Nb中之至少1種以上、和Fe與C之鐵合金粒子露出於表面而形成的長度200μm以上的表面缺陷為5個/m2以下。 A copper alloy sheet containing Fe: 1.5% by mass or more and 2.7% by mass or less, P: 0.008% by mass or more and 0.15% by mass or less, Zn: 0.01% by mass or more and 0.5% by mass or less, and the residual portion being Cu and not The amount of C contained in the unavoidable impurities is less than 5 ppm by mass, the content of Cr is less than 7 ppm by mass, and the content of Mo is less than 5 ppm by mass, and the content of W is contained. It is less than 1 mass ppm, the content of V is less than 1 mass ppm, the content of Nb is less than 1 mass ppm, the content of Mn is 20 mass ppm or less, and the content of Ta is 1 mass ppm or less. In the alloy, the surface defects having a length of 200 μm or more formed by exposing at least one of Cr, Mo, W, V, and Nb and the iron alloy particles of Fe and C to the surface are 5/m 2 or less. 如請求項1之銅合金薄板，其中，進而含有Ni：0.003質量%以上0.5質量%以下、Sn：0.003質量%以上0.5質量%以下之任一者或兩者。 The copper alloy sheet according to claim 1, which further contains Ni: 0.003 mass% or more and 0.5 mass% or less, and Sn: 0.003 mass% or more and 0.5 mass% or less. 如請求項1或請求項2之銅合金薄板，其中，進而在0.0007質量%以上0.5質量%以下之範圍內含有Mg、Ca、Sr、Ba、稀土類元素、Zr、Si、Al、Be、Ti、Co中之至少1種或2種以上。 The copper alloy sheet according to claim 1 or claim 2, further comprising Mg, Ca, Sr, Ba, a rare earth element, Zr, Si, Al, Be, Ti in a range of 0.0007 mass% or more and 0.5 mass% or less. At least one or two or more of Co. 如請求項1之銅合金薄板，其中，前述薄板之厚度為0.5mm以下。 The copper alloy sheet according to claim 1, wherein the thickness of the thin plate is 0.5 mm or less. 一種銅合金薄板之製造方法，其係請求項1至請求 項3中任一項之銅合金薄板之製造方法，具備下述步驟：熔解原料來生成銅合金熔液之熔解步驟、將前述銅合金熔液保持在1300℃以上之高溫保持步驟、與將保持在1300℃以上之前述銅合金熔液供給於鑄模內而得到鑄塊之鑄造步驟。 A method for manufacturing a copper alloy sheet, which is a request 1 to a request The method for producing a copper alloy sheet according to any one of the preceding claims, comprising the steps of: melting a raw material to form a copper alloy melt, and maintaining the copper alloy melt at a high temperature holding step of 1300 ° C or higher; The copper alloy melt at 1300 ° C or higher is supplied into the mold to obtain a casting step of the ingot.
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