TW201233818A

TW201233818A - Copper alloy for electronic and/or electrical device, copper alloy thin plate, and conductive member

Info

Publication number: TW201233818A
Application number: TW101101106A
Authority: TW
Inventors: Kazunari Maki; Hiroyuki Mori
Original assignee: Mitsubishi Materials Corp
Priority date: 2011-01-13
Filing date: 2012-01-11
Publication date: 2012-08-16
Also published as: TWI521074B; CN103282525B; JP5088425B2; WO2012096237A1; JP2012158829A; CN103282525A

Abstract

A copper alloy for electronic and/or electrical device containing, in mass %, 23 to 36.5% of Zn, 0.1 to 0.8% of Sn, 0.05% or more and less than 0.15% of Ni, 0.005% or more and less than 0.10% of Fe, 0.005 to 0.05% of P, and the balance consisting of Cu and unavoidable impurities, wherein ratio Fe/Ni of Fe content and Ni content satisfies, in atomic ratio, 0.05 < Fe/Ni < 1.5, a ratio (Ni+Fe)/P of total content of Fe and Ni expressed as (Ni+Fe) and P content satisfies, in atomic ratio, 3 < (Ni+Fe)/P < 15, and a ratio Sn/(Ni+Fe) of Sn content and total content of Ni and Fe expressed as (Ni+Fe) satisfies, in atomic ratio, 0.5 < Sn/(Ni+Fe) < 5.

Description

201233818 六、發明說明：【發明所屬之技術領域】本發明係關於作爲半導體裝置之接頭、或其他端子所代表的電子/電氣機器用導電零件而使用的銅合金，特別是關於於黃銅（Cu-Zn合金）中添加Sn而成的Cu-Zn-Sn 系電子/電氣機器用銅合金、與使用其之銅合金薄板及導電構件。本案係基於2011年1月13日於日本申請之日本特願 2011-5164號及2011年2月16日於日本申請之日本特願 2011 -3 0 90 8號而主張優先權，且於此援用其內容。【先前技術】作爲半導體裝置之接頭或其他端子所代表之電子/電氣機器用導電零件，係使用銅或銅合金。其中，由強度、加工性、成本之平衡等觀點而言，尤以黃銅（Cu-Zn合金 )以往至今就被廣泛使用。’又接頭等之端子的情況時，主要爲了能夠提高與對側之導電構件接觸的信賴性，常在由 Cu-Zn合金所構成的基材（原板）表面上施以鍍錫（Sn) 來使用。如上所述，以Cu-Zn合金作爲基材，於其表面施以鍍 Sn之接頭等之導電零件中，爲了在提高鍍Sn材之回收再利用性，同時提高強度，關於基材之Cu-Zn合金本身，亦有使用添加Sn作爲合金成分之Cu-Zn-Sn系合金的情況。以半導體之接頭或其他端子爲代表之電子/電氣機器 -5- 201233818 導電零件的製造製程，通常一般係藉由將素材之銅合金軋延加工，作成厚度0.05〜1 .0mm左右之薄板（條材），藉由沖壓加工作成指定形狀，進一步對其至少一部分施以彎曲加工。此時，經常於彎曲部分附近與對側導電構件接觸而得到與對側導電構件之電連接，同時藉由彎曲部分之彈簧性以維持與對側導電材之接觸狀態的方式來使用。如此之接頭或其他端子中，爲了抑制通電時之電阻發熱，係期望導電性優良及強度高。又，由對薄板（條材）軋延而施以沖壓加工而言，係期望軋延性或沖壓加工性優良。進一步地，如前所述，藉著施以彎曲加工而使該彎曲部分有彈簧性，而使彎曲部分附近以維持與對側導電材之接觸狀態的方式來使用的接頭等的情況時，不僅彎曲加工性優，亦要求耐應力緩和特性優良，以使得於彎曲部分附近與對側導電材的接觸可長時間（或於高溫環境）保持良好。亦即，於利用彎曲部分之彈簧性以維持與對側導電材之接觸狀態的接頭等端子中，若耐應力緩和特性不佳，而隨著時間經過，使彎曲部分之殘留應力緩和、或於高溫之使用環境下，彎曲部分之殘留應力緩和的話，與對側導電構件之接觸壓則變得無法充分保持，會容易提早產生接觸不良之問題。作爲提高接頭等端子所使用之Cu-Zn-Sn系合金的耐應力緩和特性的策略，以往有例如專利文獻1 ~專利文獻3 所示的提案者。進一步地，專利文獻4雖與本發明中作爲主要用途之接頭等端子的用途相異，但作爲引線框架用之 -6- 201233818201233818 VI. Description of the Invention: [Technical Field] The present invention relates to a copper alloy used as a conductive member for an electronic/electrical device represented by a joint of a semiconductor device or other terminals, particularly regarding brass (Cu A copper alloy for Cu-Zn-Sn-based electronic/electrical equipment in which Sn is added to a -Zn alloy, and a copper alloy sheet and a conductive member using the same. This case claims priority based on Japanese Patent Application No. 2011-5164, which was filed in Japan on January 13, 2011, and Japan's Japanese Patent Application No. 2011-309, No. 2011, filed on February 16, 2011 in Japan. Its content. [Prior Art] As a conductive member for an electronic/electrical device represented by a joint or other terminal of a semiconductor device, copper or a copper alloy is used. Among them, brass (Cu-Zn alloy) has been widely used in the past from the viewpoints of balance of strength, workability, and cost. In the case of a terminal such as a joint, it is mainly used to apply tin (Sn) to the surface of a base material (original plate) made of a Cu-Zn alloy in order to improve the reliability of contact with the conductive member on the opposite side. use. As described above, in the case of using a Cu-Zn alloy as a substrate, a conductive member such as a Sn-plated joint is applied to the surface thereof, in order to improve the recycling property of the Sn-plated material and at the same time improve the strength, Cu- on the substrate. The Zn alloy itself also has a case of using a Cu-Zn-Sn-based alloy in which Sn is added as an alloy component. Electronic/Electrical Equipment Represented by Semiconductor Joints or Other Terminals-5-201233818 The manufacturing process of conductive parts is usually made by rolling a copper alloy of a material to form a thin plate having a thickness of about 0.05 to 1.0 mm. The material is further subjected to a bending process by at least a part of the specified shape by press working. At this time, the electric connection with the opposite side conductive member is often obtained in contact with the opposite side conductive member in the vicinity of the bent portion, and is used in a manner of maintaining the contact state with the opposite side conductive member by the spring property of the bent portion. In such a joint or other terminal, in order to suppress the resistance heat generation at the time of energization, it is expected that the conductivity is excellent and the strength is high. Further, in the press working for rolling a thin plate (bar), it is desirable that the rolling property or the press workability is excellent. Further, as described above, when the bent portion is spring-like by bending, and the joint is used in the vicinity of the curved portion to maintain the contact state with the opposite-side conductive material, The bending workability is excellent, and the stress relaxation resistance is also required to be excellent so that the contact with the opposite side conductive material in the vicinity of the bent portion can be maintained well for a long time (or in a high temperature environment). In other words, in the terminal such as the joint which maintains the contact state with the opposite side conductive material by the spring property of the bent portion, if the stress relaxation resistance is not good, the residual stress of the bent portion is alleviated over time, or In the high-temperature use environment, if the residual stress in the bent portion is relaxed, the contact pressure with the opposite-side conductive member may not be sufficiently maintained, and the problem of contact failure may be easily caused in advance. As a strategy for improving the stress relaxation resistance of a Cu-Zn-Sn-based alloy used for a terminal such as a joint, there have been known, for example, those disclosed in Patent Documents 1 to 3. Further, Patent Document 4 differs from the use of terminals such as joints as main applications in the present invention, but is used as a lead frame -6-201233818

Cu-Zn-Sn系合金’亦有揭示用以提高耐應力緩和特性之策略。專利文獻1中，揭示了於Cu-Zn-Sn系合金中含有Ni ’而生成Ni-P系化合物，藉以可提高耐應力緩和特性、且Fe之添加亦有效於耐應力緩和特性之提高。又，專利文獻2的提案中，記載了於Cu-Zn-Sn系合金中將Ni、Fe 與P —起添加，而生成化合物，藉以可提高強度、彈性、耐熱性。此處雖無直接記載耐應力緩和特性，但上述之強度、彈性、耐熱性的提高，即意指耐應力緩和特性之提高〇如該等專利文獻1、2之提案所示，對於在Cu-Zn-Sn 系合金中添加Ni、Fe、P有效於耐應力緩和特性之提高此事本身，本發明者等亦已確認。但是，專利文獻1、2之提案中，僅考慮Ni、Fe、P之個別含量，藉由本發明者等的實驗、硏究，已知僅有如此個別含量的調整時，並不一定能夠確K且充分地提高耐應力緩和特性。另一方面，專利文獻3之提案中，記載了於Cu-Zn-Sn系合金中添加Ni，同時將Ni/Sn比調整在特定之範圍內，藉以可提高耐應力緩和特性。又，記載了 Fe之微量添加亦有效於耐應力緩和特性之提高。如此之專利文獻3提案所示之Ni/Sn比的調整’雖確實有效於耐應力緩和特性之提高，但關於P化合物與耐應力緩和特性的關係則全無觸及。亦即如專利文獻1、2所示，P化合物對耐應力緩和特性會有大的影響’但是專利 201233818 文獻3之提案中，關於生成P化合物之Fe、Ni 完全沒有考慮其含量與耐應力緩和特性之關係，等之實驗中，若僅依照專利文獻3之提案，已知充分且確實地提高耐應力緩和特性。以引線框架爲對象的專利文獻4提案中， Cu-Zn-Sn系合金中，將Ni、Fe與P —起添加， Fe + Ni ) /P之原子比調整爲〇.2~3之範圍內，而系化合物、Ni-P系化合物、或Fe-Ni-P系化合物提高耐應力緩和特性。然而，依據本發明者等的實驗，若僅如專利規定地調整Fe、Ni、P之合計量、與（Fe + Ni ) 比，已知無法實現充分提高耐應力緩和特性。其未特定，但爲了確實且充分地提高耐應力緩和特調整Fe、Ni、P之合計量與（Fe + Ni ) /P以外，之調整、進而 Sn/ ( Ni + Fe )之調整亦爲重要，明者等之實驗、硏究，已知若不將該等各含量比好地調整，則耐應力緩和特性無法確實且充分地如以上所述，以往的提案、即作爲Cu-Zn-S 所構成之電子/電氣機器導電零件用銅合金，而耐應力緩和特性之提案，耐應力緩和特性之提高確實且充分，而期望進一步改良。換言之，如接有對薄板（條）進行軋延且施以彎曲加工的彎曲於該彎曲部分附近與對側導電構件接觸，藉由彎彈簧性以維持與對側導電構件之接觸狀態的方式等元素，本發明者丨無法實現記載了於同時將（生成Fe-P I，藉以可文獻4之 /P之原子理由雖尙性，除了 Fe/Ni 比藉由本發率平衡良提高。 ;η系合金用以提高效果尙不頭般之具部分，且曲部分的而使用的 -8 - 201233818 零件中，隨時間經過，或在高溫環境下，殘留應力會緩和，而變得無法保持與對側導電構件之接觸壓，結果會有容易提前產生接觸不良等缺點的問題。爲了迴避如此問題，不得不使以往的材料變厚，因此會導致材料成本上昇，同時導致重量的增大。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平5-3 3087號公報 [專利文獻2]日本特開2006-283060號公報 [專利文獻3]曰本專利第3953357號公報 [專利文獻4]日本專利第3717321號公報【發明內容】 [發明所欲解決之課題] 如前所述，作爲附有鍍Sn的黃銅條基材所使用之習知Cu-Zn-Sn系合金，爲了得到接頭或其他各種端子等經施以彎曲加工且於其彎曲部附近與對側導電構件的接觸，其使用之薄板材料（條材）之耐應力緩和特性尙未確實且充分優良。因而強烈期望耐應力緩和特性更加確實且充分的改善。本發明係以上述情形爲背景而完成者，其課題爲提供一種銅合金’其係作爲接頭或其他端子等使用於電子/電氣機器之導電零件的銅合金、特別是Cu-Zn-Sn系合金之 -9 - 201233818 耐應力緩和特性確實且充分優良，相較於以往，可實現零件素材之薄型化，而且強度或軋延性、導電率等眾特性亦優良的銅合金；以及提供使用其之銅合金薄板與導電構件 [用以解決課題之手段] 本發明者等，關於上述課題之解決策略進行努力重複地實驗/硏究後，發現於Cu-Zn-Sn系合金中同時添加適當量的Ni (鎳）及Fe (鐵），並添加適當量的P (磷），而且不僅調整該等各合金元素之個別含量，亦分別將合金中之Ni、Fe、P、及Sn相互間之比率，特別是Fe及Ni 之含量比Fe/Ni、Ni及Fe之合計含量（Ni + Fe)與P之含量的比（Ni + Fe) /P、以及Sn之含量與Ni及Fe之合計含量（Ni + Fe )的比Sn/ ( Ni + Fe )，以原子比計調整至適當範圍內，藉以能夠確實且充分地提高耐應力緩和特性，而且可得到強度或軋延性、導電率等之接頭或其他端子所要求之眾特性亦優良的銅合金，因而達成本發明。再者，發現了藉由與上述之Ni、Fe、P同時地，添加適量之Co，可更加提高耐應力緩和特性。本發明之基本形態（第1形態）之電子/電氣機器用銅合金爲一種銅合金，其特徵爲：以mass%計含有Ζη 23-36.5%、Sn 0.1 〜0.8%、Ni 0.05% 以上且少於 0.15% 、Fe 0.005% 以上且少於 0.10%、P 0.005〜0.05%，且 Fe 含量與Ni含量之比Fe/Ni，以原子比計滿足 -10- 201233818 Ο. Ο 5<F e/N i < 1. 5 ，且Ni含量及Fe含量之合計量（Ni + Fe )與P含量的比 (Ni + Fe) /P，以原子比計滿足 3 < (Ni+Fe) /P< 1 5 ，更且Sn含量與Ni含量及Fe含量之合計量（Ni + Fe)的比Sn/ ( Ni + Fe)，以原子比滿足 0.5<Sn/ ( Ni + Fe) <5 ，且剩餘部分爲Cu及不可避的雜質所構成。依據如此之本發明的基本形態，於適當量之Sn外，亦將Ni及Fe與P —起同時添加適當量，而且將Sn、Ni 、Fe、及P之相互間的添加比率做適當規範，藉以能夠得到由母相（α相主體）析出之〔Ni，Fe〕-P系析出物適當存在之組織的Cu-Zn-Sn系合金。如此之Cu-Zn-Sn系合金中，耐應力緩和特性確實且充分地優良，同時強度或軋延性、導電率等之接頭其他端子所要求的眾特性亦優良。亦即’單純僅將Sn、Ni、Fe、及P之個別含量調整至指定範圍內時，可能無法因實際之材料中該等元素的含量而實現充分之耐應力緩和特性的改善，又其他之特性可能不充分’但藉由將該等元素之含量的相對比率規範至前述各式所規定的範圍內’能夠確實且充分地提高耐應力緩和特性，同時能夠滿足接頭等端子材所要求的眾特性。此處〔Ni，Fe〕-P系析出物’係指Ni_Fe_P之3元系析出物、或Fe-P或Ni-P之2元系析出物，進一步地係指於該等當中’可能包括含有其他元素、例如主成分之Cu -11 - 201233818 、Zn、Sn ;雜質之Ο、S、C、Co、Cr、Mo等的多元系析出物。又，此〔Ni，Fe〕-P系析出物，係以磷化物、或固溶有磷之合金的形態存在者。本發明之第2形態之電子/電氣機器用銅合金，係一種銅合金，其特徵爲：以mass%計係含有Zn 23~36.5% 、Sn 0.1~0.8%、Ni 0.05% 以上且少於 0.15%、Fe 0.005 %以上且少於0.10%、Co 0.005%以上且少於0.10%、p 0.005~0.05%，且Fe及Co之合計含量與Ni含量之比（ Fe + Co ) /Ni，以原子比計滿足 0. 05< (Fe+Co) /N i < 1. 5 ’且Ni、Fe及Co之合計含量（Ni + Fe + Co)與P含量之比（Ni + Fe + Co ) /P，以原子比計滿足 3< (Ni+Fe+Co) /P<15 ’此外Sn含量與Ni、Fe及Co之合計含量（Ni + Fe + Co) 的比Sn/ ( Ni + Fe + Co )，以原子比計滿足 0. 5<Sn/ (Ni+Fe+Co) <5 ’且剩餘部分爲CU及不可避的雜質所構成。如此之第2形態之電子/電氣機器用銅合金中，與如上述之Ni、Fe、P同時地，添加適量的C〇，藉由作成〔 Ni，Fe，Co〕-P系析出物適當地存在的組織，可更力卩提高耐應力緩和特性。此處〔Ni，Fe，Co〕-Ρ系析出物，係指Ni-Fe-Co-P之4 元系析出物；或Ni-Fe-P、Ni-Co-P、或Fe-Co-P之3元系析出物；或Fe-P、Ni-P、或Co-P之2元系析出物，係指 -12- 201233818 於該等當中，可能包括含有其他元素、例如主成分之Cu 、zn、Sn;雜質之〇、S、C、Cl·、Mo等的多元系析出物。又’此〔Ni，Fe，Co〕-P系析出物，能夠以磷化物、或固溶有磷之合金的形態存在。又’本發明之第3形態之電子/電氣機器用銅合金薄板，係由前述第1或第2形態之銅合金的軋延材所構成，且厚度爲0.05〜1.0mm之範圍內的銅合金薄板。如此之厚度的軋延板薄板（條材），可適宜使用於接頭、其他端子。進一步，本發明之第4形態之電子/電氣機器用銅合金薄板，係於前述第3形態之銅合金薄板的表面施以鍍 Sn者。此時，鍍Sn之基底基材係由含有0.1〜0.8 %之Sn的 Cu-Zn-Sn系合金所構成，因此能夠將使用過之接頭等零件作爲鍍Sn黃銅系合金之廢料而回收，以確保良好的回收再利用性。又，本發明之第5形態之電子/電氣機器用導電構件，係由前述第3或第4形態之銅合金薄板所構成，且係用以與對側導電構件接觸而得到與對側導電構件之電連接的導電構件，而且板面之至少一部分係經施以彎曲加工，藉由該彎曲部分之彈簧性，以維持與對側導電材之接觸的方式構成之導電構件。【實施方式】 -13- 201233818 以下，對本發明之電子/電氣機器用銅合金更詳細地說明。本發明之電子/電氣機器用銅合金，基本上合金元素之個別含量，以mass%計，係含有Zn 23-36.5%、Sn 0.1 〜0.8%、Ni 0·05% 以上且少於 0.15%、Fe 0.005% 以上且少於 0.10%、Ρ 0.005~0·05%者，進一步地，各合金元素相互間之含量比率，Fe含量與Ni含量之比Fe/Ni，以原子比計係滿足下述（1 )式 0. 0 5 <F e/N i < 1. 5 ...(1) ，且Ni含量及Fe含量之合計量（Ni + Fe)與P含量之比 (Ni + Fe) /f，以原子比計滿足下述（2 )式 3 < (N i +F e) /P< 1 5 ...(2) ，而且Sn含量與Ni含量及Fe含量之合計量（Ni + Fe)的比Sn/ ( Ni + Fe)，以原子比計係滿足下述（3 )式 0. 5<Sn/ (Ni+Fe) <5 ...⑶ ，上述各合金元素之剩餘部分係Cu及不可避免的雜質。又，本發明之電子/電氣機器用銅合金，亦可於上述 Zn、Sn、Ni、Fe、P之外，進一步含有Co 0.005%以上且少於0.10%，且該等合金元素相互間之含量比率，Fe及 Co之合計含量與Ni含量之比（Fe + Co ) /Ni，以原子比計，滿足下述（厂）式 0. 05< (Fe+Co) /N i < 1. 5 ...(1 一），進一步地，Ni、Fe及Co之合計含量（Ni + Fe + Co)與P 含量之比（Ni + Fe + Co ) /P，以原子比計，滿足下述（2') 14 - 201233818 式 3< (N i+F e+Co) /P< 1 5 .·· (2。，更且，Sn含量與Ni、Fe及Co之合計含量（Ni + Fe + Co )之比Sn/ ( Ni + Fe + Co )，以原子比計，滿足下述（3') 式 0. 5<Sn/(Ni+Fe+Co)<5 ·.· (3。，上述各合金元素之剩餘部分爲Cu及不可避的雜質。接著首先說明該等本發明銅合金之成分組成及該等之相互間比率的限定理由。The Cu-Zn-Sn-based alloy' also discloses a strategy for improving the stress relaxation resistance. Patent Document 1 discloses that Ni-'-based compound is contained in a Cu-Zn-Sn-based alloy to form a Ni-P-based compound, whereby stress-relieving properties can be improved, and addition of Fe is also effective for improving stress relaxation resistance. Further, in the proposal of Patent Document 2, it is described that Ni, Fe, and P are added together in a Cu-Zn-Sn-based alloy to form a compound, whereby strength, elasticity, and heat resistance can be improved. Here, although the stress relaxation resistance is not directly described, the improvement in strength, elasticity, and heat resistance described above means improvement in stress relaxation resistance characteristics, as shown in the proposals of Patent Documents 1 and 2, and in Cu- The inventors of the present invention have confirmed that the addition of Ni, Fe, and P to the Zn-Sn-based alloy is effective for improving the stress relaxation resistance. However, in the proposals of Patent Documents 1 and 2, only the individual contents of Ni, Fe, and P are considered, and it is known that the experiment and the like of the present inventors have only such an adjustment of the individual content, and it is not always possible to confirm K. And the stress relaxation resistance is sufficiently improved. On the other hand, in the proposal of Patent Document 3, it is described that Ni is added to the Cu-Zn-Sn-based alloy, and the Ni/Sn ratio is adjusted within a specific range, whereby the stress relaxation resistance can be improved. Further, it is described that the addition of Fe in a small amount is also effective for improving the stress relaxation resistance. The adjustment of the Ni/Sn ratio shown in the patent document 3 is effective in improving the stress relaxation resistance, but the relationship between the P compound and the stress relaxation property is not touched. That is, as shown in Patent Documents 1 and 2, the P compound has a large influence on the stress relaxation resistance characteristic. However, in the proposal of Patent No. 201233818 Document 3, the Fe and Ni which form the P compound have not considered the content and the stress relaxation resistance at all. In the experiment of the relationship between the characteristics and the like, it is known to sufficiently and surely improve the stress relaxation resistance characteristics only in accordance with the proposal of Patent Document 3. In the proposal of Patent Document 4 for the lead frame, in the Cu-Zn-Sn-based alloy, Ni, Fe and P are added together, and the atomic ratio of Fe + Ni ) /P is adjusted to be in the range of 〇. 2 to 3. Further, the compound, the Ni-P compound, or the Fe-Ni-P compound improves the stress relaxation resistance. However, according to experiments by the inventors of the present invention, it is known that it is not possible to sufficiently improve the stress relaxation resistance characteristics by adjusting the total amount of Fe, Ni, and P and the ratio of (Fe + Ni) as specified in the patent. Although it is not specified, in order to surely and sufficiently improve the stress relaxation, the total amount of Fe, Ni, and P, and the adjustment of (Fe + Ni ) /P, and the adjustment of Sn / (Ni + Fe ) are also important. In addition, it is known that the stress relaxation characteristics are not reliably and sufficiently as described above, and the conventional proposal, that is, Cu-Zn-S, is known. The copper alloy for conductive parts of electronic/electrical equipment is proposed, and the stress relaxation resistance is proposed, and the improvement of the stress relaxation resistance is ensured and sufficient, and further improvement is desired. In other words, if the thin plate (strip) is rolled and bent, the bending is applied to the vicinity of the curved portion to contact the opposite side conductive member, and the spring contact property is maintained to maintain the contact state with the opposite side conductive member. The element, the inventors of the present invention cannot be described at the same time (the formation of Fe-P I, whereby the atomicity of the atom of the document 4/P can be improved, except that the Fe/Ni ratio is improved by the balance of the present rate. Alloys are used to improve the effect of the parts that are not in the head, and the parts used in the -8 - 201233818 parts, the residual stress will be relaxed over time, or in the high temperature environment, and become unable to maintain and contralateral As a result of the contact pressure of the conductive member, there is a problem that it is easy to cause a defect such as contact failure in advance. In order to avoid such a problem, the conventional material has to be thickened, which causes an increase in material cost and an increase in weight. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-283060 [Patent Document 3] [Patent Document 4] Japanese Patent No. 3717321 [Disclosure] [Problems to be Solved by the Invention] As described above, conventional Cu-Zn used as a brass strip substrate coated with Sn is used. -Sn-based alloy, in order to obtain a joint of a joint or other various terminals and the like, and to contact the opposite side conductive member in the vicinity of the bent portion thereof, the stress relaxation property of the sheet material (bar material) used therein is not The present invention is based on the above-mentioned circumstances, and the object of the present invention is to provide a copper alloy which is used as a joint or other terminal for electronic/electrical use. The copper alloy of the conductive parts of the machine, especially the Cu-Zn-Sn alloy -9 - 201233818, is excellent and excellent in stress relaxation resistance. Compared with the past, the material of the parts can be thinned, and the strength or rolling property, A copper alloy excellent in electrical conductivity and the like; and a copper alloy sheet and a conductive member using the same (a means for solving the problem), the inventors, etc. The solution strategy of the subject is repeated. After repeated experiments/investigations, it is found that an appropriate amount of Ni (nickel) and Fe (iron) are simultaneously added to the Cu-Zn-Sn-based alloy, and an appropriate amount of P (phosphorus) is added. Moreover, not only the individual contents of the various alloying elements are adjusted, but also the ratio of Ni, Fe, P, and Sn in the alloy, especially the content of Fe and Ni, the total content of Fe/Ni, Ni, and Fe ( The ratio of the content of Ni + Fe) to the content of P (Ni + Fe) /P, and the ratio of the content of Sn to the total content of Ni and Fe (Ni + Fe ), Sn / (Ni + Fe ), adjusted to an atomic ratio to In the appropriate range, the stress-relieving property can be surely and sufficiently improved, and a copper alloy having excellent properties such as strength, rolling property, electrical conductivity, and the like, which are excellent in characteristics required for joints or other terminals, can be obtained. Further, it has been found that by adding an appropriate amount of Co to the above-mentioned Ni, Fe, and P, the stress relaxation resistance can be further improved. A copper alloy for an electric/electrical device according to a first aspect of the present invention is a copper alloy characterized by containing Ζη 23-36.5%, Sn 0.1 to 0.8%, and Ni 0.05% or more in mass%. 0.15%, Fe 0.005% or more and less than 0.10%, P 0.005~0.05%, and the ratio of Fe content to Ni content Fe/Ni, in atomic ratio, meets -10- 201233818 Ο. Ο 5<F e/N i < 1. 5 , and the ratio of the Ni content and the Fe content (Ni + Fe ) to the P content (Ni + Fe) / P, in atomic ratio, satisfy 3 < (Ni + Fe) / P < 1 5 , and the ratio of the content of Sn to the total content of Ni and Fe (Ni + Fe), Sn / (Ni + Fe), satisfies 0.5 < Sn / (Ni + Fe) < 5 in atomic ratio, and The remainder is composed of Cu and unavoidable impurities. According to the basic form of the present invention, in addition to an appropriate amount of Sn, Ni and Fe are added together with P in an appropriate amount, and the ratio of addition of Sn, Ni, Fe, and P is appropriately regulated. A Cu-Zn-Sn-based alloy having a structure in which a [Ni,Fe]-P-based precipitate precipitated from a parent phase (α-phase body) is appropriately present can be obtained. In such a Cu-Zn-Sn-based alloy, the stress relaxation resistance property is surely and sufficiently excellent, and the characteristics required for other terminals of the joint such as strength, rolling property, and electrical conductivity are also excellent. That is, when only the individual contents of Sn, Ni, Fe, and P are simply adjusted within the specified range, it is impossible to achieve sufficient improvement in stress relaxation resistance due to the content of such elements in the actual material, and other The characteristics may not be sufficient 'but by the relative ratio of the contents of the elements to the range specified by the above formulas', the stress relaxation resistance characteristics can be surely and sufficiently improved, and the requirements for the terminal materials such as joints can be satisfied. characteristic. Here, the "Ni,Fe]-P-based precipitates" means a ternary precipitate of Ni_Fe_P or a ternary precipitate of Fe-P or Ni-P, and further means that it may include Other elements, such as Cu -11 - 201233818, Zn, Sn of the main component; bismuth of impurities, S, C, Co, Cr, Mo, etc. Further, the [Ni,Fe]-P-based precipitates are in the form of a phosphide or an alloy in which phosphorus is dissolved. A copper alloy for an electric/electrical device according to a second aspect of the present invention is a copper alloy characterized by containing Zn 23 to 36.5%, Sn 0.1 to 0.8%, Ni 0.05% or more, and less than 0.15 in terms of mass%. %, Fe 0.005% or more and less than 0.10%, Co 0.005% or more and less than 0.10%, p 0.005 to 0.05%, and the ratio of the total content of Fe and Co to the Ni content (Fe + Co ) /Ni, as an atom The ratio satisfies 0. 05 < (Fe + Co) / N i < 1. 5 ' and the ratio of the total content of Ni, Fe and Co (Ni + Fe + Co) to the P content (Ni + Fe + Co ) / P, in atomic ratio, satisfies 3 < (Ni + Fe + Co) / P < 15 ' in addition to the ratio of Sn content to the total content of Ni, Fe and Co (Ni + Fe + Co) Sn / ( Ni + Fe + Co The atomic ratio satisfies 0.5 lt; Sn / (Ni + Fe + Co) < 5 ' and the remainder is composed of CU and unavoidable impurities. In the copper alloy for electric/electrical equipment according to the second aspect, an appropriate amount of C 添加 is added simultaneously with Ni, Fe, and P as described above, and a [Ni, Fe, Co]-P-based precipitate is appropriately formed. The existing organization can improve the stress relaxation resistance. Here, [Ni,Fe,Co]-antimony precipitate refers to a 4-membered precipitate of Ni-Fe-Co-P; or Ni-Fe-P, Ni-Co-P, or Fe-Co-P a ternary system precipitate; or a Fe-P, Ni-P, or Co-P ternary system precipitate, which means -12-201233818, among which may include Cu containing other elements, such as a main component, Zn, Sn; multicomponent precipitates of impurities, S, C, Cl, Mo, and the like. Further, the [Ni, Fe, Co]-P-based precipitates can be present in the form of a phosphide or an alloy in which phosphorus is dissolved. Further, the copper alloy sheet for an electronic/electrical device according to the third aspect of the present invention is a copper alloy having a thickness of 0.05 to 1.0 mm, which is composed of a rolled material of the copper alloy of the first or second aspect. sheet. A rolled sheet (bar) having such a thickness can be suitably used for a joint or other terminal. Further, the copper alloy sheet for an electric/electrical device according to the fourth aspect of the present invention is characterized in that the surface of the copper alloy sheet according to the third aspect is coated with Sn. In this case, since the Sn-plated base material is composed of a Cu-Zn-Sn-based alloy containing 0.1 to 0.8% of Sn, it is possible to recover a part such as a used joint as a scrap of a Sn-plated brass alloy. To ensure good recycling. Further, the conductive member for an electronic/electrical device according to the fifth aspect of the present invention is the copper alloy thin plate according to the third or fourth aspect, and is used to contact the opposite side conductive member to obtain the opposite side conductive member. The electrically conductive member is electrically connected, and at least a part of the plate surface is subjected to bending processing, and the conductive member is configured to maintain contact with the opposite side conductive material by the spring property of the bent portion. [Embodiment] -13-201233818 Hereinafter, the copper alloy for electronic/electrical equipment of the present invention will be described in more detail. The copper alloy for electronic/electrical equipment of the present invention, which is an alloy element, contains Zn 23-36.5%, Sn 0.1 to 0.8%, Ni 0·05% or more and less than 0.15%, in mass%. Fe 0.005% or more and less than 0.10%, Ρ 0.005 to 0. 05%, further, the content ratio of each alloying element, the ratio of Fe content to Ni content, Fe/Ni, in atomic ratio, satisfy the following (1) Formula 0. 0 5 <F e/N i < 1. 5 (1) , and the ratio of the Ni content and the Fe content (Ni + Fe) to the P content (Ni + Fe /f, in the atomic ratio, satisfies the following formula (2) 3 < (N i +F e) /P< 1 5 (2), and the sum of the Sn content and the Ni content and the Fe content ( The ratio of Sn / (Ni + Fe) of Ni + Fe) in the atomic ratio system satisfies the following formula (3): 0.5 < Sn / (Ni + Fe) < 5 (3), each of the above alloying elements The remainder is Cu and unavoidable impurities. Further, the copper alloy for an electric/electrical device of the present invention may further contain Co 0.005% or more and less than 0.10% in addition to the above-mentioned Zn, Sn, Ni, Fe, and P, and the content of the alloy elements is mutually The ratio, the ratio of the total content of Fe and Co to the content of Ni (Fe + Co ) /Ni, in atomic ratio, satisfies the following (factory) formula: 0.05 < (Fe + Co) / N i < 1. 5 (1) Further, the ratio of the total content of Ni, Fe, and Co (Ni + Fe + Co) to the P content (Ni + Fe + Co ) /P, in atomic ratio, satisfies the following ( 2') 14 - 201233818 Equation 3<(N i+F e+Co) /P< 1 5 .·· (2. Further, the content of Sn and the total content of Ni, Fe and Co (Ni + Fe + Co The ratio of Sn/(Ni + Fe + Co ), in atomic ratio, satisfies the following (3') formula: 0.5 <Sn/(Ni+Fe+Co)<5 ·.· (3. The remainder of each alloying element is Cu and an unavoidable impurity. Next, the reason why the composition of the copper alloy of the present invention and the ratio of the mutual ratios thereof are limited will be described.

Zn:以 mass% 計，爲 23 〜36.5%Zn: 23 to 36.5% in mass%

Zn爲以本發明爲對象之銅合金（黃銅）中的基本合金元素，其係有效於提高強度及彈簧性之元素。再者’ Zn 之價格比Cu便宜，因此對銅合金之材料成本降低亦有效果。Zn少於23%時，無法充分得到該等效果。另一方面，Zn超過36.5%時，耐應力緩和特性會降低，即使如後述般依照本發明而添加Fe、Ni、P，亦難以確保充分之耐應力緩和特性，且耐蝕性降低，同時沒相大量產生’因此冷軋延性及彎曲加工性亦會降低。因此，使Zn含量成爲 2 3〜36.5%之範圍內。另外，Zn量於上述範圍內，特別以 24〜36%之範圍內爲佳。Zn is a basic alloying element in a copper alloy (brass) to which the present invention is applied, and is an element effective for improving strength and springability. Furthermore, the price of 'Zn is cheaper than Cu, so the material cost of the copper alloy is also reduced. When Zn is less than 23%, such effects cannot be sufficiently obtained. On the other hand, when Zn exceeds 36.5%, the stress relaxation resistance is lowered. Even if Fe, Ni, and P are added according to the present invention as described later, it is difficult to ensure sufficient stress relaxation resistance, and corrosion resistance is lowered, and no phase is observed. A large amount produces 'so cold rolling ductility and bending workability are also reduced. Therefore, the Zn content is made to be in the range of 2 3 to 36.5%. Further, the amount of Zn is in the above range, and particularly preferably in the range of 24 to 36%.

Ni ··以mass%計，爲0.05%以上且少於0.15%Ni · · in mass%, 0.05% or more and less than 0.15%

Ni，與Fe、P —同皆爲本發明中作爲特徵的添加元素 -15- 201233818 ’藉由於Cu-Zn— Sn合金中添加適量的Ni，且使Ni 、P共存，能夠使〔Ni，Fe〕-P系析出物由母相（α 體）析出，又，藉由使Ni與Fe、Co、Ρ共存，能夠 Ni，Fe，Co〕-P系析出物由母相（〇；相主體）析出，藉等之〔Ni，Fe〕-Ρ系析出物或〔Ni，Fe，Co〕-Ρ系析出存在，能夠大幅提高耐應力緩和特性。此處，Ni之量少於0.05%時，無法充分提高耐應力緩和特性，另面，Ni之添加量爲0.15%以上時，固溶Ni變多，導降低，且因爲高價之Ni原料之使用量增大，而導致上昇。因而’使Ni之添加量成爲0.05%以上且少於 %之範圍內。另外Ni之添加量，於上述範圍內，特 0.05%以上且少於0.10%之範圍內爲佳。Ni, together with Fe and P, is an additive element characterized by the present invention-15-201233818 'By adding an appropriate amount of Ni to the Cu-Zn-Sn alloy and allowing Ni and P to coexist, [Ni, Fe can be made 】-P-precipitate precipitates from the parent phase (α-form), and by co-existing Ni with Fe, Co, and yttrium, Ni, Fe, Co]-P-based precipitates can be derived from the parent phase (〇; phase body) Precipitation, by the precipitation of [Ni,Fe]-antimony-based precipitates or [Ni,Fe,Co]-antimony, can greatly improve the stress relaxation resistance. Here, when the amount of Ni is less than 0.05%, the stress relaxation resistance cannot be sufficiently improved. On the other hand, when the amount of addition of Ni is 0.15% or more, the amount of solid solution Ni is increased, the conductance is lowered, and the use of a high-priced Ni raw material is used. The amount increases and causes an increase. Therefore, the amount of Ni added is in the range of 0.05% or more and less than %. Further, the addition amount of Ni is preferably in the range of 0.05% or more and less than 0.10% in the above range.

Fe:以mass%計，爲0.005%以上且少於0.10%Fe: 0.00% or more and less than 0.10% in mass%

Fe’係與Ni、P —同皆爲本發明中作爲特徵的添素，藉由於Cu-Zn-Sn合金中添加適量之Fe，且使f Ni、P共存，能夠使〔Ni，Fe〕-P系析出物由母相（主體）析出，又，藉由使Fe與Ni、Co、P共存，能〔Ni，Fe，Co〕-P系析出物由母相（α相主體）析出。該等〔Ni,Fe〕-Ρ系析出物或〔Ni，Fe，Co〕-Ρ系析出存在，能夠大幅提高銅合金之耐應力緩和特性。此處添加量少於0.005 %時，無法充分提高耐應力緩和特另一方面Fe添加量爲0.10%以上時，無法觀察到更高耐應力緩和特性，且固溶Fe增多，導電率降低，與Fe 相主使〔由該物的添加一方電率成本 0.15 別以加元 e與 α相夠使藉由物之，F e 性。加提冷軋 -16- 201233818 延性亦降低。因而’係使Fe添加量爲0·005%以上且少於 0.10%之範圍內。另外’ Fe之添加量於上述範圍內，特別以0.005%~0.08%之範圔內爲佳。The Fe' system, which is characterized by Ni and P, is a feature of the present invention. By adding an appropriate amount of Fe to the Cu-Zn-Sn alloy and coexisting f Ni and P, [Ni, Fe]- can be made. The P-based precipitates are precipitated from the parent phase (main body), and by the coexistence of Fe, Ni, Co, and P, the [Ni, Fe, Co]-P-based precipitates can be precipitated from the parent phase (α phase host). These [Ni,Fe]-antimony precipitates or [Ni,Fe,Co]-antimony are precipitated, and the stress relaxation characteristics of the copper alloy can be greatly improved. When the amount added is less than 0.005%, the stress relaxation resistance cannot be sufficiently improved. On the other hand, when the Fe addition amount is 0.10% or more, higher stress relaxation resistance cannot be observed, and solid solution Fe increases, and electrical conductivity decreases. The main phase of the Fe phase [from the addition of the material, the electrical cost is 0.15, and the Canadian dollar e and α are sufficient to cause the object, and the F e property. Jiati Cold Rolling -16- 201233818 Ductility is also reduced. Therefore, the amount of Fe added is in the range of 0. 005% or more and less than 0.10%. Further, the addition amount of Fe is in the above range, and particularly preferably in the range of 0.005% to 0.08%.

Co:以mass%計，爲0.005%以上且少於0.10%Co: 0.00% or more and less than 0.10% in mass%

Co雖非一定必須的添加元素，但在Ni、Fe、P之外添加少量的Co，〔 Ni，Fe，Co〕-P系析出物會生成，能夠更加提高耐應力緩和特性。此處Co添加量少於0.005 % 時，無法得到因Co添加所造成之耐應力緩和特性更提高之效果。另一方面，Co添加量爲0.10%以上時，固溶Co 增多，導電率降低，且因爲高價格Co原料之使用量增大，使得成本上昇。因而，添加Co的情況時，係使Co添加量成爲0.005 %以上且少於0.10%之範圍內。另外，Co 添加量於上述範圍內，特別以0.005 %〜0.08%之範圍內爲佳。再者，不積極地添加Co時，亦可能含有作爲雜質的少於0.005%之Co。 P:以 mass% 計，爲〇.〇〇5~0.05% P係與Fe、Ni、進一步地與Co的結合性高，於Fe、 Ni之外’若含有適量P，能夠使〔Ni,Fe〕-P系析出物析出，又，於Fe、Ni、Co之外，若含有適量P，能夠使〔 Ni，Fe，Co〕-P系析出物析出，且藉由該等析出物之存在，能夠提高銅合金之耐應力緩和特性。此處，P量少於 0.005%時’難以充分地析出〔Ni，Fe〕-P系析出物或〔 -17- 201233818Co is not necessarily an additive element, but a small amount of Co is added in addition to Ni, Fe, and P, and [Ni, Fe, Co]-P-based precipitates are formed, and stress relaxation resistance can be further improved. When the amount of Co added is less than 0.005%, the effect of improving the stress relaxation resistance due to the addition of Co cannot be obtained. On the other hand, when the amount of Co added is 0.10% or more, the amount of solid solution Co increases, the electrical conductivity decreases, and the cost is increased because the amount of use of the high-priced Co raw material increases. Therefore, when Co is added, the amount of Co added is in the range of 0.005% or more and less than 0.10%. Further, the Co addition amount is within the above range, and particularly preferably in the range of 0.005 % to 0.08%. Further, when Co is not actively added, it may contain less than 0.005% of Co as an impurity. P: in terms of mass%, 〇.〇〇5~0.05% P is highly compatible with Fe, Ni, and Co, and other than Fe and Ni, if it contains an appropriate amount of P, [Ni, Fe can be made. -P-precipitate precipitates, and in addition to Fe, Ni, and Co, if an appropriate amount of P is contained, [Ni, Fe, Co]-P-based precipitates can be precipitated, and by the presence of such precipitates, It can improve the stress relaxation resistance of copper alloy. Here, when the amount of P is less than 0.005%, it is difficult to sufficiently precipitate [Ni,Fe]-P-based precipitates or [ -17- 201233818

Ni，Fe，Co〕-P系析出物，會變得無法充分提高耐應力緩和特性。另一方面P量超過0.05%時，P固溶量增多，銅合金之導電率降低，而且軋延性會降低，冷軋延破裂容易產生。因而，係使P含量於0.005~0.05%之範圍內，另外， P量於上述範圍內，特別以0.01%〜0.04%之範圍內爲佳〇再者，P爲經常不可避免地由銅合金之熔解原料混入之元素。因此，爲了如上述般規範P量，係期望適當地選定熔解原料。以上各元素之剩餘部分，基本上只要係Cu及不可避的雜質即可。此處之不可避免的雜質，可列舉Mg、A1、The Ni, Fe, Co]-P-based precipitates do not sufficiently improve the stress relaxation resistance. On the other hand, when the amount of P exceeds 0.05%, the amount of P solid solution increases, the electrical conductivity of the copper alloy decreases, and the rolling property is lowered, and cold rolling cracking is likely to occur. Therefore, the P content is in the range of 0.005 to 0.05%, and the P amount is in the above range, particularly in the range of 0.01% to 0.04%, and P is often inevitably composed of a copper alloy. Melting the elements in which the raw materials are mixed. Therefore, in order to regulate the amount of P as described above, it is desirable to appropriately select the melting raw material. The remainder of each of the above elements is basically a Cu and an unavoidable impurity. Here, the inevitable impurities, for example, Mg, A1

Mn ' S i ' (Co ) 、Cr 、Ag > C a、Sr、B a 、S c、Y、 Hf、V 、N b、 Ta 、Μ o、W、 Re、 Ri l、Os、S e、 T e、R h、 Ir、Pd 、Pt、 Au 、Cd、Ga、 In、 Li 、Ge 、 As 、 Sb 、 Ti 、 Tl、Pb 、Bi、 S、 0、C、B e、 N、 H 、Hg、B、Z] r、稀土類等。該等之不可避免雜質，期望總量爲0.3質量％以下。進一步地，本發明之電子/電氣機器用銅合金中，不僅將各合金元素之個別添加量範圍調整至如上所述，重要的是將各自元素之含量相互的比率，以原子比計，規範至滿足前述（1)〜（3)式、或（r)〜（3-)式。因而，以下說明（1)〜（3)式、（Γ)〜（3_)式之限定理由。， (1)式：0.05<Fe/Ni<l.5 依據本發明者等詳細的實驗，Fe/Ni比會對銅合金之 -18- 201233818 耐應力緩和特性帶來大的影響，已知該比在特定範圍內時 ’耐應力緩和特性才能充分提高。亦即，發現了不僅使 Fe與Ni共存、且使Fe、Ni各自的含量調整爲如前所述，且使該等之比Fe/Ni，以原子比計成爲超過〇.〇5且低於 1_5的範圍內時，能夠實現充分之耐應力緩和特性的提高。此處’ Fe/Ni比爲1.5以上時，耐應力緩和特性會降低，又，Fe/Ni比低於〇.〇5時耐應力緩和特性亦會降低。又 ’ Fe/Ni比低於〇.〇5時，高價格的Ni原料使用量會相對地變多，招致成本上昇。因而係使Fe/Ni比規範爲上述範圍內。另外，Fe/Ni比於上述範圍內，尤以0.1〜1.2之範圍內爲佳。 (2)式：3< ( Ni + Fe) /P<15 藉由使Ni及Fe與P共存，〔Ni，Fe〕-P系析出物會生成，藉由該〔Ni，Fe〕-P系析出物之分散，能夠提高銅合金之耐應力緩和特性。但是，相對於（Ni + Fe )若過度地含有P，因固溶P之比例增大，耐應力緩和特性反而會降低，又，相對於P若過度地含有（Ni + Fe)，則因爲固溶之Ni、Fe的比例增大，耐應力緩和特性會降低，因而爲了充分地提高耐應力緩和特性，（Ni + Fe ) /P比亦爲重要。（Ni + Fe ) /P比爲3以下時，伴隨著固溶P之比例增大，銅合金之耐應力緩和特性會降低，且同時因爲固溶P ，導電率降低、並且軋延性降低，容易產生冷軋延破裂，進而彎曲加工性亦降低。另一方面，（Ni + Fe) /P比爲15 -19- 201233818 以上時，因爲固溶之Ni、Fe比例增大，銅合金的導電率會降低。因而，係使（Ni + Fe ) /P比規範於上述範圍內。再者，（Ni + Fe )/P比於上述範圍內，尤以超過3、且10 以下的範圍內爲佳。 (3 )式：0.5<Sn/ ( Ni + Fe ) <5 如前所述使Sn與Ni及Fe共存時，Sn可對銅合金之耐應力緩和特性提高作出貢獻，但該耐應力緩和特性提高效果，當Sn/ ( Ni + Fe )比不在特定範圍內時就無法充分發揮。亦即，Sn/ ( Ni + Fe )比爲0.5以下時，不會發揮充分的耐應力緩和特性提高效·果，另一方面Sn/ ( Ni + Fe ) 比超過5時，相對地（Ni + Fe)量變少，〔Ni，Fe〕-P系析出物之量變少，耐應力緩和特性會降低。再者，Sn/ ( Ni + Fe)比於上述範圍內，尤以1〜4.5之範圍內爲佳。 (Γ)式：0.05< ( Fe + Co) /Ni<1.5 添加有Co的情況時，可考慮爲將Fe的一部分取代爲 Co，因此（厂）式基本上亦以（1 )式爲準。亦即，在Fe 、Ni之外添加Co時，（Fe + Co ) /Ni比對銅合金之耐應力緩和特性會帶來大的影響，該比在特定範圍內時，耐應力緩和特性才能充分地提高。因此，不僅使Ni與Fe及Co 共存、且將Fe、Ni、Co各自的含量調整爲如前所述，且使Fe與Co合計含量與Ni含量的比（Fe + Co ) /Ni，以原子比計爲超過0.05且低於1.5的範圍內時，能夠實現耐 -20- 201233818 應力緩和特性的充分提高。此處，（Fe + Co) /Ni比爲1.5 以上時，耐應力緩和特性會降低，又，（Fe + Co ) /Ni比低於0.05，耐應力緩和特性亦會降低。因而係將（Fe + C〇 )/Ni比規範於上述範圍內。再者，（Fe + Co) /Ni比於上述範圍內，尤以〇.1〜1.2 之範圍內爲佳。 (2。式：3< ( Ni + Fe + Co ) /P<1 5 添加Co之情況時，（2~)式亦以前述（2)式爲準。亦即，藉由使Ni、Fe及Co與P共存’會生成〔Ni,Fe，Co 〕-P系析出物，藉由.該〔Ni，Fe，Co〕-P系析出物之分散，能夠提高銅合金之耐應力緩和特性。另一方面，相對於（ Ni + Fe + Co )，若過度地含有P，則因固溶P之比例增大，耐應力緩和特性反而會降低。因此’爲了充分提高耐應力緩和特性，（Ni + Fe + Co ) /P比亦爲重要。（Ni + Fe + Co ) /P比爲3以下時，伴隨著固溶P之比例增大，耐應力緩和特性會降低，且同時因爲固溶P，導電率降低、且軋延性降低，容易產生冷軋延破裂，進而彎曲加工性亦降低。另一方面，（Ni + Fe + Co) /P比爲15以上時，因爲固溶之 N i、F e、C 〇的比例增大，而導電率會降低。因而，係使 (Ni + Fe + Co ) /P 比規範爲上述範圍內。再者，（ Ni + Fe + Co ) /P比於上述範圍內，尤以超過3、且1 〇以下之範圍內爲佳。 201233818 (3* )式：0.5<Sn/ ( Ni + Fe + Co ) <5 添加Co的情況時，（3")式亦以前述（3 )式爲準。亦即，Sn與Ni、Fe及Co共存時，Sn可對銅合金之耐應力緩和特性提高作出貢獻，但該耐應力緩和特性提高效果，當Sn/(Ni + Fe + Co)比不在特定範圍內時就無法充分發揮。具體而言，Sn/ ( Ni + Fe + Co )比爲0.5以下時，不會發揮充分之耐應力緩和特性提高效果，另一方面Sn/ ( Ni + Fe + Co )比超過 5時，相對地（Ni + Fe + Co )量變少、〔Ni，Fe，Co〕-P系析出物之量變少，耐應力緩和特性會降低。再者，Sn/ ( Ni + Fe + Co )比於上述範圍內，尤以 1〜4.5之範圍內爲佳。如以上所述，將各合金元素不僅是個別含量1且將各元素相互比率調整爲滿足（1)〜（3)式或（1')〜（3。式的電子/電氣機器用銅合金中，如已經提過的，〔Ni,Fe 〕.-P系析出物或〔Ni，Fe，Co〕-P系析出物會成爲由母相（ α相主體）分散析出者，可認爲藉由如此之析出物的分散析出，會提高耐應力緩和特性。再者，已知材料之結晶粒徑亦對耐應力緩和特性有某種程度的影響，一般而言結晶粒徑愈小，耐應力緩和特性愈低，但強度與彎曲加工性會提高。本發明之合金的情況，藉由適當調整成分組成與各合金元素之比率，能夠確保良好的耐應力緩和特性，因此能夠實現使結晶粒徑變小、提高強度與彎曲加工性。具體的結晶粒徑値雖無特殊限定，較佳爲在後述製造製程中，於用以再結晶及析出之中間 -22- 201233818 熱處理後的階段，使平均結晶粒徑爲20 // m以下。接著’針對本發明之電子/電氣機器用銅合金之製造方法的較佳例子，以製造厚度0.05〜1.0mm左右之薄板（條材）的情況爲例子來說明。首先熔製如前述成分組成之銅合金熔融金屬。此處，熔解原料中的銅原料，期望使用純度99.99%以上的所謂 4NCu、例如無氧銅，但亦可將廢料作爲原料使用。又，熔解步驟中，可使用大氣環境爐，但爲了控制Zn的氧化 ’亦可使用真空爐、或惰性氣體環境或還原性環境之環境爐。接著將經成分調整之銅合金熔融金屬，以適宜的鑄造法、例如模具鑄造等批次式鑄造法，或連續鑄造法、半連續鑄造法等來鑄造而製成鑄塊（平板狀鑄塊等）。之後，依照需要，爲了消除偏析而使鑄塊組織均勻化，進行均質化處理。此均質化處理的條件雖無特殊限定，但通常於600~950°C加熱5分鐘〜24小時即可。均質化處理溫度低於600t、或均質化處理時間低於5分鐘時，會有無法得到充分均質化效果之虞。另一方面均質化處理溫度超過950°C時，會有偏析部位的一部分熔解之虞；進一步地均質化處理時間超過24小時，僅會導致成本上昇。均質化處理後之冷卻條件雖適當決定即可，但通常係進行水淬火。再者，均質化處理後係依照需要來進行機械光製〇接著，對鑄塊進行熱軋延，得到板厚0.5〜50mm左右 -23- 201233818 的熱延板。此熱軋延之條件亦無特殊限定，但通常較佳爲使開始溫度爲600〜950°C、結束溫度爲300〜850°C、軋延率爲10〜90%左右。再者至熱軋延開始溫度爲止的鑄塊加熱，亦可與前述鑄塊均質化處理一倂進行。亦即均質化處理後不冷卻至接近室溫，而亦可在經冷卻至熱軋延開始溫度的狀態下開始熱軋延。熱軋延後，施以一次冷軋延（中間軋延），成爲板厚 0.05~5 mm左右的中間板厚。此一次冷軋延之軋延率雖無特殊限定，但通常爲20~99%左右。一次冷軋延後，係施以中間熱處理。該中間熱處理，係爲用以在使組織再結晶的同時，使〔Ni，Fe〕-P系析出物或〔Ni，Fe，Co〕-P系析出物分散析出的重要步驟，只要應用可使該等析出物生成的加熱溫度、加熱時間之條件即可。該等析出物生成的溫度區域爲300〜8 00°C，因此中間熱處理只要係在此溫度區域內進行即可。又，於該溫度區域之加熱時間只要係爲使該等析出物充分生成的時間、亦即通常爲1秒~24小時即可。但是，如之前所述，結晶粒徑亦會對耐應力緩和特性造成某種程度的影響，故較佳爲測定中間熱處理之再結晶粒，適當地選擇加熱溫度、加熱時間之條件。再者，亦可依照需要重複複數次上述之冷軋延與中間熱處理。中間熱處理之較佳加熱溫度、加熱時間，如下述說明，係依照具體的熱處理手法不同而相異。亦即，作爲中間熱處理之具體手法者，可使用批次式加熱爐、或使用連續退火線來連續加熱。此外中間熱處理 -24- 201233818 之較佳加熱條件，在使用批次式加熱爐的情況期望爲 300~800°C的溫度、加熱5分鐘〜24小時。使用連續退火線的情況時，較佳使加熱到達溫度爲300〜800°C、且以該範圍內的溫度，不保持或者保持1秒〜5分鐘左右。又，此中間熱處理之環境較佳爲非氧化性環境（氮氣環境、惰性氣體環境、或還原性環境）。中間熱處理後之冷卻條件雖無特殊限定，但通常以 2000°C /秒~l〇〇°C /小時左右的冷卻速度來冷卻即可。中間熱處理之後，爲了修飾至產品板厚（0.05~1.0mm 左右），同時藉由加工硬化以得到所需要之強度，再度進行冷軋延（修飾冷軋延）。該修飾冷軋延的軋延率通常較. 佳爲5〜99%。修飾冷軋延率低於5%時，會有無法得到作爲最終板的充分強度之虞，另一方面，超過99%時，會有產生邊緣裂縫之虞。再者，不需要強度的情況時，亦可省略修飾冷軋延。修飾冷軋延後，依照需要進行低溫熱處理（修飾退火 )，以作爲應力釋放退火。此低溫熱處理較期望在 5 0~5 00 °C範圍內的溫度進行1秒〜24小時。低溫熱處理之溫度低於50°C、或低溫熱處理的時間低於1秒時，會有無法得到充分之應力釋放效果之虞。另一方面，低溫熱處理的溫度超過500°C時，有再結晶之虞；進一步地，低溫熱處理的時間超過24小時，僅會招致成本上昇。如以上所述’可得到由α相主體之母相分散析出〔 Ni，Fe〕-Ρ系析出物或〔Ni,Fe，Co〕-Ρ系析出物之板厚 -25- 201233818 0.05〜1.0mm左右的Cu-Zn-Sn系合金薄板（條材）》之薄板，可將其直接使用於電子/電氣機器用導電零但通常係於板面之一面、或兩面施以膜厚0.1〜l〇#m 的鍍Sn，並作爲附有鍍Sn之銅合金條而使用於接頭他端子等電子/電氣機器用導電零件。此時鍍Sn之方特殊限定，可依照通常方法應用電鍍、或依情況在電施以回流處理。再者，實際使用於接頭或其他端子時，如之前所通常係對薄板施以彎曲加工。又，一般係以在其彎曲部分附近，藉由彎曲部分之彈簧性而壓接於對側導電，而確保與對側導電構件之電導通的樣態來使用。對此樣態的使用而言，本發明之銅合金最爲適宜。以下，將爲了確認本發明效果而進行的確認實驗果，一倂顯示於於本發明的實施例、比較例。此外，的實施例爲用以說明本發明效果者，實施例所記載之、製程、條件並非爲限定本發明之技術範圍者。 [實施例] 準備由Cu-35%Zn母合金及純度99.99質量％以無氧銅（ASTM B152 C10100)所構成之原料，將之高純度石墨坩堝內，於N2氣體環境中使用電氣爐熔於銅合金熔融金屬內添加各種添加元素，作爲本發明熔製表1及表2之No. 1〜No.39所示成分組成的合金作爲比較例，熔製表3之No. 4 1〜No . 5 7所示成分組成如此件，左右或其法無鍍後述，加工構件於如的結以下構成上之裝入解。例，、及之合 -26- 201233818 金熔融金屬’將熔融金屬注入碳鑄模，製出鑄塊。再者，鑄塊的大小設爲厚度約25 mm X寬度約25 mm X長度約 150mm。以表4〜表6所示條件處理各鑄塊。亦即，首先對鑄塊於Ar氣體環境中、8 50°C保存指定時間作爲均質化處理後，實施水淬硬。接著，再加熱使熱軋延開始溫度成爲8 5 0 °C，進行軋延率約50%之熱軋延，由軋延結束溫度500~70(TC進行水萍火，實施表面硏削後，製出厚度約llmmx寬度約25mm 之熱軋延材。之後，進行軋延率約80%之軋延作爲一次冷軋延（表4〜表6中之中間軋延）後，於550°C實施熱處理，使中間熱處理後之平均結晶粒徑成爲約1 〇 # m，作爲中間熱處理（再結晶及析出處理）。於中間熱處理後之階段，以如下所述之方式觀察平均結晶粒徑。亦即，於中間熱處理後之各試樣進行鏡面硏磨、蝕刻，以光學顯微鏡攝影，使中間軋延方向成爲照片的橫向，於1〇〇〇倍視野（約300 // mx200 // m )進行觀察。接著，依照JIS Η 0501切斷法，將照片縱、橫各拉出5 條指定長度的線，數出完全被切割之結晶粒數，將該切斷長度之平均値作爲平均結晶粒徑。將如此方式觀察之於中間熱處理後之階段的平均結晶粒徑示於表4〜表6中。之後，以表4〜表6中所示的軋延率實施修飾冷軋延，製出厚度約〇.25mmx寬度約25mm之條材（薄板）。最後，作爲修飾之應力釋放退火（低溫熱處理）’於 -27- 201233818Mn ' S i ' (Co ) , Cr , Ag > C a, Sr, B a , S c, Y, Hf, V, N b, Ta, Μ o, W, Re, Ri l, Os, S e , T e , R h, Ir, Pd, Pt, Au, Cd, Ga, In, Li, Ge, As, Sb, Ti, Tl, Pb, Bi, S, 0, C, B e, N, H, Hg, B, Z] r, rare earths, and the like. The inevitable impurities such as these are desirably 0.3% by mass or less. Further, in the copper alloy for an electric/electrical machine of the present invention, not only the range of the respective addition amounts of the respective alloying elements is adjusted to be as described above, but it is important to adjust the ratio of the contents of the respective elements to each other in atomic ratio to The above formulas (1) to (3) or (r) to (3-) are satisfied. Therefore, the reasons for limiting the formulas (1) to (3) and (Γ) to (3_) will be described below. (1) Formula: 0.05 <Fe/Ni<l.5 According to the detailed experiments of the present inventors, the Fe/Ni ratio has a large influence on the stress relaxation resistance of the copper alloy -18-201233818, and is known. When the ratio is within a specific range, the stress relaxation resistance can be sufficiently improved. In other words, it has been found that not only Fe and Ni are coexistent, but also the content of each of Fe and Ni is adjusted as described above, and the ratio of Fe/Ni is more than 〇.〇5 and lower than the ratio of Fe/Ni. When the range of 1_5 is within the range, sufficient stress relaxation resistance can be improved. Here, when the Fe/Ni ratio is 1.5 or more, the stress relaxation resistance is lowered, and when the Fe/Ni ratio is lower than 〇.〇5, the stress relaxation resistance is also lowered. Further, when the Fe/Ni ratio is lower than 〇.〇5, the amount of Ni raw materials used at a high price will increase relatively, resulting in an increase in cost. Therefore, the Fe/Ni ratio is specified to be within the above range. Further, the Fe/Ni ratio is preferably in the range of 0.1 to 1.2 in the above range. (2) Formula: 3 < (Ni + Fe) / P < 15 By allowing Ni and Fe to coexist with P, [Ni, Fe]-P-based precipitates are formed by the [Ni, Fe]-P system The dispersion of the precipitates can improve the stress relaxation resistance of the copper alloy. However, if P is excessively contained in (Ni + Fe ), the ratio of solid solution P increases, and the stress relaxation resistance property is rather lowered. Further, if P is excessively contained (Ni + Fe), it is solid. The ratio of Ni and Fe dissolved increases, and the stress relaxation resistance is lowered. Therefore, in order to sufficiently improve the stress relaxation resistance, the (Ni + Fe ) /P ratio is also important. When the ratio of (Ni + Fe ) /P is 3 or less, the ratio of the solid solution P increases, and the stress relaxation resistance of the copper alloy is lowered, and at the same time, since the solid solution P is lowered, the electrical conductivity is lowered, and the rolling property is lowered, which is easy. Cold rolling cracking occurs, and the bending workability is also lowered. On the other hand, when the (Ni + Fe) /P ratio is 15 -19 to 201233818 or more, since the ratio of Ni and Fe which are solid solution increases, the electrical conductivity of the copper alloy decreases. Therefore, the (Ni + Fe ) /P ratio is specified within the above range. Further, the (Ni + Fe )/P ratio is preferably in the range of more than 3 and not more than 10 in the above range. (3) Formula: 0.5 <Sn/(Ni + Fe) <5 When Sn is coexisted with Ni and Fe as described above, Sn contributes to improvement of stress relaxation resistance of the copper alloy, but the stress relaxation is moderated. The characteristic improvement effect cannot be fully exerted when the Sn/(Ni + Fe ) ratio is out of a specific range. In other words, when the Sn/(Ni + Fe ) ratio is 0.5 or less, sufficient stress relaxation resistance is not exhibited, and on the other hand, when the Sn/(Ni + Fe ) ratio exceeds 5, relatively (Ni + ) When the amount of Fe) is small, the amount of [Ni,Fe]-P-based precipitates is small, and the stress relaxation resistance is lowered. Further, the Sn/(Ni + Fe) ratio is preferably in the range of from 1 to 4.5, more preferably in the range of from 1 to 4.5. (Γ): 0.05 < (Fe + Co) / Ni < 1.5 When Co is added, it is considered that a part of Fe is substituted with Co, so the (factory) formula is basically based on the formula (1). . That is, when Co is added in addition to Fe and Ni, the (Fe + Co ) /Ni ratio has a large influence on the stress relaxation resistance of the copper alloy, and when the ratio is within a specific range, the stress relaxation resistance can be sufficiently obtained. Improve the ground. Therefore, not only Ni is coexisted with Fe and Co, but also the content of each of Fe, Ni, and Co is adjusted as described above, and the ratio of the total content of Fe to Co to the content of Ni (Fe + Co ) /Ni is atomized. When the ratio is in the range of more than 0.05 and less than 1.5, the stress relaxation characteristics of the resistance of -20 to 201233818 can be sufficiently improved. Here, when the (Fe + Co) /Ni ratio is 1.5 or more, the stress relaxation resistance is lowered, and when the (Fe + Co ) /Ni ratio is less than 0.05, the stress relaxation resistance is also lowered. Therefore, the (Fe + C 〇 ) / Ni ratio is specified within the above range. Further, the (Fe + Co) /Ni ratio is preferably in the range of 〇.1 to 1.2 in the above range. (2. Formula: 3 < (Ni + Fe + Co ) / P < 1 5 When Co is added, the formula (2~) is also based on the above formula (2). That is, by making Ni, Fe and The coexistence of Co and P 'produces a [Ni, Fe, Co]-P-based precipitate, and the dispersion of the [Ni, Fe, Co]-P-based precipitate can improve the stress relaxation resistance of the copper alloy. On the other hand, when P is excessively contained in (Ni + Fe + Co ), the ratio of solid solution P increases, and the stress relaxation resistance property is rather lowered. Therefore, in order to sufficiently improve stress relaxation resistance, (Ni + The Fe + Co ) /P ratio is also important. When the (Ni + Fe + Co ) /P ratio is 3 or less, the ratio of the solid solution P increases, the stress relaxation resistance is lowered, and at the same time, because of the solid solution P, When the electrical conductivity is lowered and the rolling property is lowered, cold rolling cracking is likely to occur, and the bending workability is also lowered. On the other hand, when the (Ni + Fe + Co) /P ratio is 15 or more, the solid solution N i, F The ratio of e and C 增大 increases, and the electrical conductivity decreases. Therefore, the (Ni + Fe + Co ) /P ratio is within the above range. Furthermore, (Ni + Fe + Co ) /P is as described above. Fan In particular, it is preferably in the range of more than 3 and less than 1 。. 201233818 (3* ) Formula: 0.5 <Sn/ ( Ni + Fe + Co ) <5 When Co is added, (3") In other words, when Sn and Ni, Fe, and Co coexist, Sn contributes to the improvement of the stress relaxation resistance of the copper alloy, but the stress relaxation property is improved when Sn/( When the ratio of the Ni + Fe + Co) is not in the specific range, the Sn/(Ni + Fe + Co ) ratio is not more than 0.5, and the effect of improving the stress relaxation resistance is not exhibited. When the Sn/(Ni + Fe + Co ) ratio exceeds 5, the amount of (Ni + Fe + Co ) is relatively small, and the amount of [Ni, Fe, Co]-P-based precipitates is small, and the stress relaxation resistance is lowered. Further, Sn/(Ni + Fe + Co ) is preferably in the range of from 1 to 4.5, more preferably in the range of from 1 to 4.5. As described above, each alloying element is not only individual content 1 but also the ratio of each element is adjusted. In the copper alloy for electronic/electrical equipment of the formula (1) to (3) or (1') to (3), as described above, [Ni,Fe].-P-based precipitates [Ni, Fe, Co] -P precipitates become dispersed and precipitated by the parent phase (main phase [alpha]), could be so considered by dispersing and precipitating a precipitate, it will improve the resistance property of stress relaxation. Further, the crystal grain size of the known material also has a certain influence on the stress relaxation resistance. Generally, the smaller the crystal grain size, the lower the stress relaxation resistance, but the strength and bending workability are improved. In the case of the alloy of the present invention, by appropriately adjusting the ratio of the component composition to the respective alloying elements, it is possible to ensure good stress relaxation resistance, and therefore, it is possible to reduce the crystal grain size, and to improve the strength and the bending workability. The specific crystal grain size 値 is not particularly limited, and it is preferred to have an average crystal grain size of 20 // m or less at a stage after heat treatment in the middle of -22-201233818 for recrystallization and precipitation in a manufacturing process to be described later. Next, a preferred example of the method for producing a copper alloy for an electric/electrical device according to the present invention will be described by way of an example in which a thin plate (a strip) having a thickness of about 0.05 to 1.0 mm is produced. First, a copper alloy molten metal having the composition of the foregoing components is melted. Here, it is desirable to use a so-called 4NCu having a purity of 99.99% or more, for example, oxygen-free copper, in the copper raw material in the raw material, but the waste material may be used as a raw material. Further, in the melting step, an atmospheric furnace can be used, but in order to control the oxidation of Zn, a vacuum furnace or an environmental furnace in an inert gas atmosphere or a reducing atmosphere can be used. Then, the composition-adjusted copper alloy molten metal is cast by a suitable casting method, a batch casting method such as die casting, or a continuous casting method, a semi-continuous casting method, or the like to form an ingot (a flat ingot, etc.). ). Thereafter, in order to eliminate segregation, the ingot structure is uniformized as needed, and homogenization treatment is performed. Although the conditions of this homogenization treatment are not particularly limited, they are usually heated at 600 to 950 ° C for 5 minutes to 24 hours. When the homogenization treatment temperature is lower than 600 t or the homogenization treatment time is less than 5 minutes, there is a possibility that a sufficient homogenization effect cannot be obtained. On the other hand, when the homogenization treatment temperature exceeds 950 °C, a part of the segregation site is melted; further homogenization treatment time exceeds 24 hours, which only causes an increase in cost. Although the cooling conditions after the homogenization treatment are appropriately determined, they are usually subjected to water quenching. Further, after the homogenization treatment, mechanical light is produced as needed. Next, the ingot is hot rolled to obtain a heat-expanded plate having a thickness of about 0.5 to 50 mm -23 to 201233818. The conditions of the hot rolling are not particularly limited, but it is usually preferably a starting temperature of 600 to 950 ° C, an end temperature of 300 to 850 ° C, and a rolling ratio of about 10 to 90%. Further, the ingot heating up to the hot rolling start temperature may be carried out in the same manner as the above-mentioned ingot homogenization treatment. That is, after the homogenization treatment, it is not cooled to near room temperature, and the hot rolling may be started in a state of being cooled to the hot rolling start temperature. After the hot rolling is delayed, a cold rolling (intermediate rolling) is applied to form an intermediate plate thickness of about 0.05 to 5 mm. Although the rolling rate of this cold rolling is not particularly limited, it is usually about 20 to 99%. After a cold rolling delay, an intermediate heat treatment is applied. This intermediate heat treatment is an important step for dispersing and depositing [Ni,Fe]-P-based precipitates or [Ni,Fe,Co]-P-based precipitates while recrystallizing the structure, as long as it is applied. The conditions of the heating temperature and the heating time for the formation of the precipitates may be sufficient. The temperature region in which the precipitates are formed is 300 to 800 ° C, so that the intermediate heat treatment is carried out in this temperature region. Further, the heating time in the temperature region may be a period of time sufficient for the formation of the precipitates, that is, usually 1 second to 24 hours. However, as described above, the crystal grain size also has a certain influence on the stress relaxation resistance. Therefore, it is preferred to measure the recrystallized grains of the intermediate heat treatment, and appropriately select the conditions of the heating temperature and the heating time. Further, the above-described cold rolling and intermediate heat treatment may be repeated as many times as necessary. The preferred heating temperature and heating time for the intermediate heat treatment are as described below, and are different depending on the specific heat treatment method. That is, as a specific method of the intermediate heat treatment, a batch type heating furnace or a continuous annealing line may be used for continuous heating. Further, the preferred heating conditions of the intermediate heat treatment -24 - 201233818 are desirably 300 to 800 ° C in the case of using a batch type heating furnace, and heating is carried out for 5 minutes to 24 hours. In the case of using a continuous annealing line, it is preferred that the heating reaches a temperature of 300 to 800 ° C and the temperature within the range is not maintained or maintained for about 1 second to 5 minutes. Further, the environment of the intermediate heat treatment is preferably a non-oxidizing environment (nitrogen atmosphere, inert gas atmosphere, or reducing environment). Although the cooling conditions after the intermediate heat treatment are not particularly limited, they are usually cooled at a cooling rate of about 2,000 ° C / sec to 10 ° C / hr. After the intermediate heat treatment, in order to modify the thickness of the product (about 0.05 to 1.0 mm) and at the same time to obtain the required strength by work hardening, cold rolling (modified cold rolling) is again performed. The rolling rate of the modified cold rolling is usually preferably from 5 to 99%. When the modified cold rolling rate is less than 5%, sufficient strength as a final sheet may not be obtained. On the other hand, when it exceeds 99%, edge cracks may occur. Further, when the strength is not required, the modified cold rolling may be omitted. After the cold rolling is modified, a low-temperature heat treatment (modified annealing) is performed as needed to perform stress relief annealing. This low-temperature heat treatment is more preferably carried out at a temperature in the range of 50 to 500 ° C for 1 second to 24 hours. When the temperature of the low-temperature heat treatment is lower than 50 ° C or the time of the low-temperature heat treatment is less than 1 second, a sufficient stress release effect may not be obtained. On the other hand, when the temperature of the low-temperature heat treatment exceeds 500 °C, there is a recrystallization enthalpy; further, the low-temperature heat treatment time exceeds 24 hours, which only causes an increase in cost. As described above, it is possible to obtain a plate thickness of the [Ni,Fe]-antimony precipitate or [Ni,Fe,Co]-antimony precipitate by the mother phase of the α phase main body -25 - 201233818 0.05~1.0mm The thin plate of the left and right Cu-Zn-Sn-based alloy sheets (bars) can be directly used for conductive zeros in electronic/electrical equipment, but usually on one side of the board surface or on both sides with a film thickness of 0.1 to l. #m is plated with Sn, and is used as a conductive alloy part for electronic/electrical equipment such as a terminal that is attached with a copper-plated alloy strip. In this case, the side of the Sn plating is particularly limited, and plating may be applied according to a usual method or, depending on the case, by reflow. Further, when it is actually used for a joint or other terminal, the thin plate is subjected to bending as usual. Further, it is generally used in the vicinity of the curved portion thereof by being crimped to the opposite side by the spring property of the bent portion to ensure electrical conduction with the opposite side conductive member. The copper alloy of the present invention is most suitable for use in this state. Hereinafter, the results of the confirmation experiments performed to confirm the effects of the present invention are shown in the examples and comparative examples of the present invention. Further, the embodiments are intended to explain the effects of the present invention, and the processes, conditions, and conditions described in the examples are not intended to limit the technical scope of the present invention. [Examples] A raw material composed of a Cu-35% Zn master alloy and an oxygen-free copper (ASTM B152 C10100) having a purity of 99.99% by mass was prepared, and it was melted in a high-purity graphite crucible in an N 2 gas atmosphere using an electric furnace. Various alloying elements were added to the copper alloy molten metal, and the alloys of the composition shown in Nos. 1 to No. 39 of Table 1 and Table 2 of the present invention were used as a comparative example, and No. 4 1 to No. of Table 3 were melted. The components shown in 5 7 are composed of such a piece, and the left and right or the method thereof is not plated, and the processed member is placed on the following structure. Examples, and combinations -26- 201233818 Gold molten metal 'Injected molten metal into a carbon mold to produce ingots. Further, the size of the ingot is set to a thickness of about 25 mm, a width of about 25 mm, and a length of about 150 mm. Each ingot was treated under the conditions shown in Tables 4 to 6. That is, first, the ingot was stored in an Ar gas atmosphere at 850 ° C for a predetermined period of time as a homogenization treatment, and then water hardened. Then, the hot rolling is started at a temperature of 850 ° C, and the rolling rate is about 50%, and the rolling temperature is 500 to 70 (the TC is subjected to water tempering, and after surface boring is performed, A hot rolled product having a thickness of about llmm x a width of about 25 mm is produced. Thereafter, a rolling reduction of about 80% is carried out as a primary cold rolling (intermediate rolling in Table 4 to Table 6), and then carried out at 550 ° C. The heat treatment is performed so that the average crystal grain size after the intermediate heat treatment is about 1 〇# m as an intermediate heat treatment (recrystallization and precipitation treatment). At the stage after the intermediate heat treatment, the average crystal grain size is observed as follows. After the intermediate heat treatment, each sample was mirror-honed and etched, and photographed by optical microscopy, so that the intermediate rolling direction became the lateral direction of the photograph, and the observation was performed at 1 〇〇〇 field of view (about 300 // mx200 // m). Next, according to the cutting method of JIS Η 0501, five lines of a predetermined length are drawn vertically and horizontally, and the number of crystal grains completely cut is counted, and the average 値 of the cut length is taken as the average crystal grain size. Will be observed in this way after the intermediate heat treatment The average crystal grain size at the stage is shown in Tables 4 to 6. Thereafter, the modified cold rolling was performed at the rolling ratios shown in Tables 4 to 6, to produce a strip having a thickness of about 2525 mmx and a width of about 25 mm. (thin plate). Finally, as a modified stress relief annealing (low temperature heat treatment) '-27-201233818

Ar氣體環境中，於200°C保持1小時保持後，實施水淬硬 ’實施表面硏削後，製出特性評估用條材。對該等特性評估用條材，觀察軋延性、導電率、機械特性（耐力），並且觀察耐應力緩和特性，進一步地進行組織觀察。對各評估項目之試驗方法、測定方法係如下所述，且其結果示於表7〜表9。 [軋延性評估] 觀察前述修飾冷軋延時之邊緣裂縫有無，作爲軋延性評估。以目視完全無觀察到邊緣裂縫、或幾乎無觀察到者爲A、產生長度低於1mm之小的邊緣裂縫者爲B、產生長度1mm以上且低於3mm之邊緣裂縫者爲C、產生長度 3mm以上之大的邊緣裂縫，且特性評估顯著困難者爲D 而分別評估。再者，邊緣裂縫之長度，意指由軋延材之寬度方向端部朝向寬度方向中央部之邊緣裂縫的長度。 [機械特性] 由特性評估用條材採取JIS Z 220 1所規定之13B號試驗片，藉由JIS Z 2241之偏置（offset)法，測定0.2 %耐力C7 〇. 2。再者，試驗片係以拉伸試驗之拉伸方向平行於特性評估用條材之軋延方向的方式採取。 [導電率] 由特性評估用條材採取寬度l〇mmx長度60mm之試驗 -28- 201233818 片，藉由4端子法求得電阻。又，使用測微器進之尺寸測定，算出試驗片的體積。此外’由測定値與體積算出導電率。再者，試驗片係以其長度於特性評估用條材之軋延方向的方式採取。 [耐應力緩和特性] 耐應力緩和特性試驗，係根據日本伸銅協會 JCBA-T309: 2004之懸臂樑螺桿式的方法來負荷定於1 5 0 °C之溫度下保持指定時間後之殘留應力〗作爲試驗方法，係由各供試材以與長度方向取試驗片（寬度10mm)，以使試驗片之表面最爲耐力之80%的方式，將初期撓曲位移設定爲調整跨距長度。上述表面最大應力係以次式規定表面應力（MPa) =1.5Et5〇/Ls2，惟 E :撓曲係數（MPa) t:試樣之厚度（t = 0.25mm) 5 〇 :初期撓曲位移（2mm)In the Ar gas atmosphere, after holding at 200 ° C for 1 hour, water quenching was performed to perform surface boring, and a strip for property evaluation was produced. For the evaluation of the properties, the properties of the ductility, electrical conductivity, and mechanical properties (endurance) were observed, and the stress relaxation resistance was observed, and the microstructure was further observed. The test methods and measurement methods for each evaluation item are as follows, and the results are shown in Tables 7 to 9. [Toughness Evaluation] The presence or absence of edge cracks in the aforementioned modified cold rolling delay was observed as the evaluation of the rolling property. Obviously no edge cracks were observed visually, or almost no observed is A, a small edge crack with a length less than 1 mm is B, and an edge crack having a length of 1 mm or more and less than 3 mm is produced as C, and the length is 3 mm. The above-mentioned large edge cracks, and those whose characteristic evaluation is significantly difficult, are evaluated separately for D. Further, the length of the edge crack means the length of the edge crack from the end portion in the width direction of the rolled web toward the central portion in the width direction. [Mechanical characteristics] The test piece No. 13B specified in JIS Z 220 1 was used for the property evaluation strip, and the 0.2% proof force C7 〇. 2 was measured by the offset method of JIS Z 2241. Further, the test piece was taken in such a manner that the stretching direction of the tensile test was parallel to the rolling direction of the property evaluation strip. [Electrical conductivity] From the strip for characteristic evaluation, a test was carried out with a width of l〇mmx and a length of 60 mm, -28-201233818, and the electric resistance was obtained by a 4-terminal method. Further, the volume of the test piece was calculated by measuring the size using a micrometer. In addition, the conductivity was calculated from the measured enthalpy and volume. Further, the test piece was taken in such a manner that its length was in the rolling direction of the property evaluation strip. [Resistance to stress relaxation characteristics] The stress relaxation resistance test is based on the cantilever beam type of the JCBA-T309: 2004 method of the Japanese Extension Copper Association. The residual stress after the specified time is maintained at a temperature of 150 °C. As a test method, the initial deflection displacement was set to the adjustment span length so that the test piece (width: 10 mm) was taken in the longitudinal direction from each test material so that the surface of the test piece was 80% of the maximum endurance. The maximum stress on the surface is defined by the secondary formula (MPa) = 1.5Et5〇/Ls2, but E: deflection coefficient (MPa) t: thickness of the sample (t = 0.25mm) 5 〇: initial deflection displacement ( 2mm)

Ls:跨距長度（mm)。於1 50°C之溫度，由保持80h後之彎曲習慣留應力率，以其値爲70%以上者定爲A、60% 於70%者定爲B、50%以上且低於60%者定爲 50%者定爲D來評估。再者殘留應力率係使用〇殘留應力率（％) = (1-δ“δ〇)χ1〇〇，惟行試驗片後之電阻方向平行技術標準應力，測 ^ 〇平行地採大應力成 2mm，來來測定殘以上且低 C、低於次式算出 -29 - 201233818 (5t:於15(TC保持80h後之永久撓曲位移（mm) <5〇:初期撓曲位移（mm)。 [析出物之觀察] 對各特性評估用條材實施用以確認析出物之組織觀察。對各試樣之軋延面進行鏡面硏磨、蝕刻，使用FE-SEM (場發射型掃描電子顯微鏡），於約40000倍進行觀察。又，對於析出物之成分，使用EDX (能量分散型X射線分光法）確認。關於上述各評估結果，係示於表7〜表9中。又，將本發明例之No.2試樣的FE-SEM觀察照片示於圖1，作爲上述組織觀察之一例。進一步地將該本發明例之No.2試樣中之析出物的EDX (能量分散型X射線分光法）分析結果示於圖2。 -30- 201233818 [表1] [本發明例] No. 合金成分組成(單位:mass%) 合金元素原子比 Zn Sn Ni Fe P Co Cu (Fe+Co) /Ni 原子比 (Ni+Fe+Co) /P 原子比 Sn/ (Ni+Fe+Co) 原子比 1 29.6 0.51 0.12 0.052 0.021 - 剰餘部分 0.46 4.4 1.5 2 29.9 0.48 0.09 0.047 0.019 - 剩餘部分 0.55 3.9 1.7 3 27.1 0.47 0.09 0.051 0.024 - 剩餘部分 0. 60 3.1 1.6 4 32.5 0.46 0.08 0.048 0.018 — 剩餘部分 0. 63 3.8 1.8 5 30.9 0.15 0.09 0.049 0.022 - 剩餘部分 0.57 3.3 0.54 6 30.2 0.31 0.08 0.048 0.019 - 剩餘部分 0. 63 3.6 1.2 7 29.1 0.72 0.07 0.012 0.011 剩餘部分 0.18 4.0 4.4 8 29.5 0.48 0.06 0.053 0.018 - 剩餘部分 0.93 3.4 2.1 9 30.4 0.46 0.14 0.048 0.020 剩餘部分 0.36 5.0 1.2 10 30.4 0.45 0.10 0.010 0.019 - 剩餘部分 0.11 3.1 2.0 11 30.2 0.55 0.09 0.091 0.024 - 剩餘部分 1.06 4.1 1.5 12 30.8 0.59 0.09 0.053 0.009 - 剩餘部分 0.62 8.5 2.0 13 30.7 0.51 0.14 0.089 0.041 剩餘部分 0.65 3.1 1.1 14 29.6 0.52 0.08 0.054 0.021 0.009 剩餘部分 0.81 3.6 t.8 15 29.9 0.48 0.09 0.047 0.020 0.049 剩餘部分 1.05 4.9 1.3 16 29.7 0.46 0.09 0.009 0.017 0.084 剩餘部分 0.97 5.5 1.3 17 24.6 0.47 0.11 0.048 0.023 - 剩餘部分 0.44 Γ 3.8 1.4 18 23.2 0.46 0.09 0.046 0.021 - 剩餘部分 0.54 3.5 1.7 19 25.8 0.14 0.09 0.038 0.018 - 剩餘部分 0.44 3.7 0.6 20 25.4 0.32 0.09 0.051 0.021 - 剩餘部分 0.60 3.6 1.) 21 25.1 0.76 0.06 0.017 0.013 - 剩餘部分 0.30 3.2 4.9 22 24.5 0.48 0.06 0.051 0.017 剩餘部分 0.89 3.5 2.1 23 25.9 0.46 0.14 0. 048 0.022 - 剩餘部分 0.36 4.6 1.2 24 25.2 0.45 0.14 0.008 0.023 - 剩餘部分 0.06 3.4 1.5 25 24.4 0.52 0.07 0.096 0.019 - 剩餘部分 1.44 4.7 1.5 26 24.7 0.49 0.14 0.051 0.007 - 剰餘部分 0.39 14.6 1J____ 27 25.5 0.51 0.14 0.096 0.041 - 剩餘部分 0.71 3.1 1.1 201233818 [表2] [本發明例] No. 合金成分組成< 單位:mass%) 合金元素原子比 Zn Sn Νί Fe P Co Cu (Fe+Co) /Ni 原子比 (Ni+Fe+Co) /P 原子比 Sn/ (Ni+Fe+Co) 原子比 28 34.6 0.47 0.09 0.046 0.021 一剩餘部分 0. 54 3.5 1.7 29 36.2 0.44 0.09 0.045 0.017 - 剩餘部分 0. 53 4.3 1.6 30 34.4 0.14 0.08 0.046 0.021 - 剩餘部分 0. 60 3.2 0.56. 31 34.7 0.31 0.08 0.048 0.019 - 剩餘部分 0.63 3.6 1.2 32 34.6 0. 70 0.07 0.010 0.011 一剩餘部分 0.15 3.9 4.4 33 34.0 0.48 0.06 0.049 0.019 - 剩餘部分 0.86 3.1 2.2 34 35.1 0. 46 0.14 0.044 0.022 - 剩餘部分 0. 33 4.5 1.2 35 34.9 0.44 0.10 0.011 0.018 一剩餘部分 0.12 3.3 2.0 36 34.6 0. 55 0.09 0.091 0.024 - 剩餘部分 1.06 4.1 1.5 37 34.3 0.54 0.09 0.047 0.009 - 剩餘部分 0.55 8.2 2.0 38 34.4 0.51 0.14 0.089 0.037 - 剩餘部分 0. 66 3.4 1.1 39 34.3 0. 46 0.09 0.037 0.019 0.034 剩餘部分 0. 78 4.5 1.4 -32- 201233818 [表3] [比較例]Ls: span length (mm). At a temperature of 150 ° C, the bending habit retention stress rate after 80 h is maintained, and the enthalpy of 70% or more is determined as A, 60%, and 70% is determined to be B, 50% or more and less than 60%. Those who are determined to be 50% are assessed as D. In addition, the residual stress rate is the residual stress rate (%) = (1 - δ "δ 〇) χ 1 〇〇, but the resistance direction after the test piece is parallel to the technical standard stress, and the measurement is performed in parallel with a large stress of 2 mm. , to determine the residual above and low C, lower than the sub-calculation -29 - 201233818 (5t: at 15 (TC keeps the permanent deflection displacement after 80h (mm) < 5〇: initial deflection displacement (mm). Observation of precipitates] The strips for evaluation of each characteristic were subjected to observation of the structure of the precipitates, and the rolling surface of each sample was mirror-honed and etched using FE-SEM (field emission scanning electron microscope). The observation was carried out at about 40,000 times. The components of the precipitates were confirmed by EDX (energy dispersive X-ray spectroscopy). The results of the above evaluations are shown in Tables 7 to 9. Further, the examples of the present invention are shown. The FE-SEM observation photograph of the No. 2 sample is shown in Fig. 1 as an example of the above-described structure observation. Further, EDX (energy dispersive X-ray spectrometry) of the precipitate in the No. 2 sample of the present invention example The results of the analysis are shown in Fig. 2. -30-201233818 [Table 1] [Example of the present invention] No. Alloy composition (unit: mass%) Alloy element atomic ratio Zn Sn Ni Fe P Co Cu (Fe + Co) / Ni atomic ratio (Ni + Fe + Co) / P atomic ratio Sn / (Ni + Fe + Co Atomic ratio 1 29.6 0.51 0.12 0.052 0.021 - The remaining part 0.46 4.4 1.5 2 29.9 0.48 0.09 0.047 0.019 - The remaining part 0.55 3.9 1.7 3 27.1 0.47 0.09 0.051 0.024 - The remaining part 0. 60 3.1 1.6 4 32.5 0.46 0.08 0.048 0.018 — Remaining Part 0. 63 3.8 1.8 5 30.9 0.15 0.09 0.049 0.022 - Remaining part 0.57 3.3 0.54 6 30.2 0.31 0.08 0.048 0.019 - Remaining part 0. 63 3.6 1.2 7 29.1 0.72 0.07 0.012 0.011 Remaining part 0.18 4.0 4.4 8 29.5 0.48 0.06 0.053 0.018 - Remaining part 0.93 3.4 2.1 9 30.4 0.46 0.14 0.048 0.020 Remaining part 0.36 5.0 1.2 10 30.4 0.45 0.10 0.010 0.019 - Remaining part 0.11 3.1 2.0 11 30.2 0.55 0.09 0.091 0.024 - Remaining part 1.06 4.1 1.5 12 30.8 0.59 0.09 0.053 0.009 - Remaining part 0.62 8.5 2.0 13 30.7 0.51 0.14 0.089 0.041 Remaining part 0.65 3.1 1.1 14 29.6 0.52 0.08 0.054 0.021 0.009 Remaining part 0.81 3.6 t.8 15 29.9 0 .48 0.09 0.047 0.020 0.049 Remaining part 1.05 4.9 1.3 16 29.7 0.46 0.09 0.009 0.017 0.084 Remaining part 0.97 5.5 1.3 17 24.6 0.47 0.11 0.048 0.023 - Remaining part 0.44 Γ 3.8 1.4 18 23.2 0.46 0.09 0.046 0.021 - Remaining part 0.54 3.5 1.7 19 25.8 0.14 0.09 0.038 0.018 - remainder 0.44 3.7 0.6 20 25.4 0.32 0.09 0.051 0.021 - remainder 0.60 3.6 1.) 21 25.1 0.76 0.06 0.017 0.013 - remainder 0.30 3.2 4.9 22 24.5 0.48 0.06 0.051 0.017 remainder 0.89 3.5 2.1 23 25.9 0.46 0.14 0. 048 0.022 - Remaining part 0.36 4.6 1.2 24 25.2 0.45 0.14 0.008 0.023 - Remaining part 0.06 3.4 1.5 25 24.4 0.52 0.07 0.096 0.019 - Remaining part 1.44 4.7 1.5 26 24.7 0.49 0.14 0.051 0.007 - Remaining part 0.39 14.6 1J____ 27 25.5 0.51 0.14 0.096 0.041 - Remaining part 0.71 3.1 1.1 201233818 [Table 2] [Inventive Example] No. Alloy composition &composition; unit: mass%) Alloying element atomic ratio Zn Sn Νί Fe P Co Cu (Fe+Co) /Ni Atomic ratio (Ni+Fe+Co) /P atomic ratio Sn/(Ni+Fe+Co) atomic ratio 28 34.6 0.47 0.09 0.04 6 0.021 A remainder 0. 54 3.5 1.7 29 36.2 0.44 0.09 0.045 0.017 - Remaining part 0. 53 4.3 1.6 30 34.4 0.14 0.08 0.046 0.021 - Remaining part 0. 60 3.2 0.56. 31 34.7 0.31 0.08 0.048 0.019 - Remaining part 0.63 3.6 1.2 32 34.6 0. 70 0.07 0.010 0.011 A remainder 0.15 3.9 4.4 33 34.0 0.48 0.06 0.049 0.019 - Remaining part 0.86 3.1 2.2 34 35.1 0. 46 0.14 0.044 0.022 - Remaining part 0. 33 4.5 1.2 35 34.9 0.44 0.10 0.011 0.018 Remaining part 0.12 3.3 2.0 36 34.6 0. 55 0.09 0.091 0.024 - Remaining part 1.06 4.1 1.5 37 34.3 0.54 0.09 0.047 0.009 - Remaining part 0.55 8.2 2.0 38 34.4 0.51 0.14 0.089 0.037 - Remaining part 0. 66 3.4 1.1 39 34.3 0. 46 0.09 0.037 0.019 0.034 Remaining part 0. 78 4.5 1.4 -32- 201233818 [Table 3] [Comparative example]

No. 合金成分組成(單位:mass%) 合金元素原子比 Zn Sn Νί Fe Ρ Co Cu (Fe+Co) /Ni 原子比 (Ni+Fe+Co) /Ρ 原子比 Sn/ (Ni+Fe+Co) 原子比 41 30.5 - - - - - 剩餘部分 - - - 42 30.3 0.54 - - - 剩餘部分 - - — 43 37.1 0. 64 0.06 0.008 0.007 - 剩餘部分 0.14 5.2 4.7 44 29.1 2. 21 0.13 0.049 0.031 - 剩餘部分 0.40 3.1 6.1 45 29.8 - 0.09 0.047 0.016 - 剩餘部分 0.55 4.6 0 46 31.7 0.48 0. 20 0.005 0.006 - 剩餘部分 0.03 18.1 1.2 47 30.3 0. 49 - 0.020 0.018 - 剩餘部分 - 0.6 11.7 48 30.9 0.47 0.05 0.15 0.006 - 剩餘部分 3.2 18.4 1.1 49 29.9 0.46 0.11 - 0.017 - 剩餘部分 0 3.4 2.1 50 29.6 0. 49 0. 08 0.051 0.096 剩餘部分 0. 67 0.7 1.8 51 30.3 0. 50 0. 07 0.009 - - 剩餘部分 0.1 - 3.2 52 30.7 0. 49 0. 13 0.005 0.019 - 剩餘部分 0.04 3.8 1.8 53 30.1 0.51 0. 05 0.080 0.017 - 剩餘部分 1.7 4.2 1.9 54 30.4 0. 54 0.06 0.006 0.017 - 剩餘部分 0.1 2.1 4.1 55 25.7 0.42 0. 13 0.047 0.005 - 剩餘部分 0.4 18.9 1.2 56 30.8 0.10 0.11 0.052 0.017 - 剩餘部分 0.5 5.1 0.30 57 | 31.7 0.73 0.05 0.006 0.006 - 剩餘部分 0.1 5.0 6.5 -33- 201233818 [表4] [本發明例]No. Alloy composition (unit: mass%) Alloy element atomic ratio Zn Sn Νί Fe Ρ Co Cu (Fe+Co) /Ni atomic ratio (Ni+Fe+Co) /Ρ atomic ratio Sn/ (Ni+Fe+Co Atomic ratio 41 30.5 - - - - - Remaining part - - - 42 30.3 0.54 - - - Remaining part - - — 43 37.1 0. 64 0.06 0.008 0.007 - Remaining part 0.14 5.2 4.7 44 29.1 2. 21 0.13 0.049 0.031 - Remaining Part 0.40 3.1 6.1 45 29.8 - 0.09 0.047 0.016 - Remaining part 0.55 4.6 0 46 31.7 0.48 0. 20 0.005 0.006 - Remaining part 0.03 18.1 1.2 47 30.3 0. 49 - 0.020 0.018 - Remaining part - 0.6 11.7 48 30.9 0.47 0.05 0.15 0.006 - Remaining part 3.2 18.4 1.1 49 29.9 0.46 0.11 - 0.017 - Remaining part 0 3.4 2.1 50 29.6 0. 49 0. 08 0.051 0.096 Remaining part 0. 67 0.7 1.8 51 30.3 0. 50 0. 07 0.009 - - Remaining part 0.1 - 3.2 52 30.7 0. 49 0. 13 0.005 0.019 - Remaining part 0.04 3.8 1.8 53 30.1 0.51 0. 05 0.080 0.017 - Remaining part 1.7 4.2 1.9 54 30.4 0. 54 0.06 0.006 0.017 - Remaining part 0.1 2.1 4.1 55 25.7 0.42 0. 13 0.047 0.005 - Remaining part 0.4 18.9 1.2 56 30.8 0.10 0.11 0.052 0.017 - Remaining part 0.5 5.1 0.30 57 | 31.7 0.73 0.05 0.006 0.006 - Remaining part 0.1 5.0 6.5 -33- 201233818 [Table 4] [Example of the invention]

No. 步驟均質化溫度 (°C) 熱軋延開始溫度 (°C) 中間軋延率 (%) 再結晶酿 (°C) 平均結晶粒徑 ("m) 修飾軋延率 (%) 低溫熱處理酿 (°C) 1 850 850 80 550 10 88 200 2 850 850 80 550 9 88 200 3 850 850 80 550 9 88 200 4 850 850 80 550 10 88 200 5 850 850 80 550 8 88 200 6 850 850 80 550 10 88 200 7 850 850 80 550 10 88 200 8 850 850 80 550 11 88 200 9 850 850 80 550 10 88 200 10 850 850 80 550 10 88 200 11 850 850 80 550 9 88 200 12 850 850 80 550 8 88 200 13 850 850 80 550 10 88 200 14 850 850 80 550 10 88 200 15 850 850 80 550 10 88 200 16 850 850 80 550 11 88 200 17 850 850 80 550 11 88 200 18 850 850 80 550 11 88 200 19 850 850 80 550 10 88 200 20 850 850 80 550 11 88 200 21 850 850 80 550 8 88 200 22 850 850 80 550 9 88 200 23 850 850 80 550 11 88 200 24 850 850 80 550 10 88 200 25 850 850 80 550 8 88 200 26 850 850 80 550 10 88 200 27 850 850 80 550 9 88 200 -34- 201233818 [表5] [本發明例] No. 步驟均質化溫度 (°C) 熱車1¾ 開始酿 (°C) 中間車LM奉 (%) 再結晶溫度 (°C) 平均結晶粒徑 ("m) 修飾觀率 (%) 低溫熱處理溫度 (0〇 28 850 850 80 550 8 88 200 29 850 850 80 550 10 88 200 30 850 850 80 550 8 88 200 31 850 850 80 550 10 88 200 32 850 850 80 550 9 88 200 33 850 850 80 550 11 88 200 34 850 850 80 550 10 88 200 35 850 850 80 550 10 88 200 36 850 850 80 550 10 88 200 37 850 850 80 550 8 88 200 38 850 850 80 550 10 88 200 39 850 850 80 550 10 88 200 -35- 201233818 [表6] [比較例] No. 步驟均質化溫度 (0〇熱軋延開始溫度 (°C) 中間軋延率 (%) 再結晶溫度 (°C) 平均結晶粒徑 ("π0 修飾軋延率 (%) 低溫熱處理溫度 (°C) 41 850 850 80 550 12 88 200 42 850 850 80 550 10 88 200 43 850 850 80 550 10 88 — 44 850 850 - - - - - 45 850 850 80 550 10 88 200 46 850 850 80 550 10 88 200 47 850 850 80 550 9 88 200 48 850 850 80 550 10 88 200 49 850 850 80 550 10 88 200 50 850 850 80 550 8 88 - 51 850 850 80 550 8 88 200 52 850 850 80 550 11 88 200 53 850 850 80 550 10 88 200 54 850 850 80 550 11 88 200 55 850 850 80 550 8 88 200 56 850 850 80 550 9 88 200 57 850 850 80 550 9 88 200 -36- 201233818 [表7]No. Step homogenization temperature (°C) Hot rolling start temperature (°C) Intermediate rolling rate (%) Recrystallization brewing (°C) Average crystal grain size ("m) Modified rolling rate (%) Low temperature Heat treatment brewing (°C) 1 850 850 80 550 10 88 200 2 850 850 80 550 9 88 200 3 850 850 80 550 9 88 200 4 850 850 80 550 10 88 200 5 850 850 80 550 8 88 200 6 850 850 80 550 10 88 200 7 850 850 80 550 10 88 200 8 850 850 80 550 11 88 200 9 850 850 80 550 10 88 200 10 850 850 80 550 10 88 200 11 850 850 80 550 9 88 200 12 850 850 80 550 8 88 200 13 850 850 80 550 10 88 200 14 850 850 80 550 10 88 200 15 850 850 80 550 10 88 200 16 850 850 80 550 11 88 200 17 850 850 80 550 11 88 200 18 850 850 80 550 11 88 200 19 850 850 80 550 10 88 200 20 850 850 80 550 11 88 200 21 850 850 80 550 8 88 200 22 850 850 80 550 9 88 200 23 850 850 80 550 11 88 200 24 850 850 80 550 10 88 200 25 850 850 80 550 8 88 200 26 850 850 80 550 10 88 200 27 850 850 80 550 9 88 200 -34- 201233818 [Table 5] [Example of the invention] No. Qualification temperature (°C) Hot car 13⁄4 Start brewing (°C) Intermediate car LM (%) Recrystallization temperature (°C) Average crystal grain size ("m) Modification rate (%) Low temperature heat treatment temperature (0 〇28 850 850 80 550 8 88 200 29 850 850 80 550 10 88 200 30 850 850 80 550 8 88 200 31 850 850 80 550 10 88 200 32 850 850 80 550 9 88 200 33 850 850 80 550 11 88 200 34 850 850 80 550 10 88 200 35 850 850 80 550 10 88 200 36 850 850 80 550 10 88 200 37 850 850 80 550 8 88 200 38 850 850 80 550 10 88 200 39 850 850 80 550 10 88 200 -35- 201233818 [Table 6] [Comparative Example] No. Step homogenization temperature (0〇 hot rolling start temperature (°C) Intermediate rolling rate (%) Recrystallization temperature (°C) Average crystal grain size ("π0 modification Rolling rate (%) Low temperature heat treatment temperature (°C) 41 850 850 80 550 12 88 200 42 850 850 80 550 10 88 200 43 850 850 80 550 10 88 — 44 850 850 - - - - - 45 850 850 80 550 10 88 200 46 850 850 80 550 10 88 200 47 850 850 80 550 9 88 200 48 850 850 80 550 10 88 200 49 850 850 80 550 10 88 200 50 850 850 80 550 8 88 - 51 850 850 80 550 8 88 200 52 850 850 80 550 11 88 200 53 850 850 80 550 10 88 200 54 850 850 80 550 11 88 200 55 850 850 80 550 8 88 200 56 850 850 80 550 9 88 200 57 850 850 80 550 9 88 200 -36- 201233818 [Table 7]

[本發明例] m. 評估軋延性評估導電率 (%IAGS) 耐力 (MPa) 耐應力緩和特性殘留應力率(％) 評估 1 A 25 776 67 B 2 A 25 774 67 B 3 A 26 753 68 B 4 A 23 780 62 B 5 A 26 733 62 B 6 A 25 755 63 B 7 B 21 801 61 B 8 A 25 764 63 B 9 A 23 785 66 B 10 A 25 771 63 B 11 A 2-1 787 64 B 12 A 23 765 61 B 13 B 21 808 66 B 14 A 25 772 68 B 15 A 21 783 69 B 16 A 21 786 68 B 17 A 26 732 71 A 18 A 27 725 73 A 19 A 26 714 66 B 20 A 25 736 67 B 21 B 23 753 67 B 22 A 25 735 65 B 23 A 24 743 68 B 24 A 26 723 64 B 25 A 22 739 67 B 26 A 23 722 63 B 27 C 21 755 70 A -37- 201233818 [表8][Example of the invention] m. Evaluation of rolling ductility evaluation Conductivity (% IAGS) Endurance (MPa) Stress relaxation resistance Residual stress rate (%) Evaluation 1 A 25 776 67 B 2 A 25 774 67 B 3 A 26 753 68 B 4 A 23 780 62 B 5 A 26 733 62 B 6 A 25 755 63 B 7 B 21 801 61 B 8 A 25 764 63 B 9 A 23 785 66 B 10 A 25 771 63 B 11 A 2-1 787 64 B 12 A 23 765 61 B 13 B 21 808 66 B 14 A 25 772 68 B 15 A 21 783 69 B 16 A 21 786 68 B 17 A 26 732 71 A 18 A 27 725 73 A 19 A 26 714 66 B 20 A 25 736 67 B 21 B 23 753 67 B 22 A 25 735 65 B 23 A 24 743 68 B 24 A 26 723 64 B 25 A 22 739 67 B 26 A 23 722 63 B 27 C 21 755 70 A -37- 201233818 [Table 8]

[本發明例] 評估 No. 軋延性導電率耐力耐應力緩和特性評估 (%IAGS) (MPa) 殘留應力率(％) 評估 28 B 24 779 62 B 29 C 23 784 60 B 30 A 24 738 61 B 31 A 23 757 62 B 32 B 22 803 61 B 33 B 23 768 62 B 34 B 24 790 62 B 35 B 23 776 61 B 36 B 21 785 62 B 37 B 22 770 61 B 38 C 22 808 62 B 39 B 21 786 63 B -38- 201233818[Inventive Example] Evaluation No. Rollability Electrical Conductivity Endurance and stress relaxation resistance evaluation (% IAGS) (MPa) Residual stress rate (%) Evaluation 28 B 24 779 62 B 29 C 23 784 60 B 30 A 24 738 61 B 31 A 23 757 62 B 32 B 22 803 61 B 33 B 23 768 62 B 34 B 24 790 62 B 35 B 23 776 61 B 36 B 21 785 62 B 37 B 22 770 61 B 38 C 22 808 62 B 39 B 21 786 63 B -38- 201233818

[表9] [比較例] No. m___ 軋延性評估導電率 _S) 耐力 (MPa) 耐應力緩和特性殘留應力率(％) 評估 41 A 26 722 45 D 42 A 25 751 51 C 43 D 未評估未評估未評估未龍 44 未評估未挪未評估未評估未評估 — 45 A 24 726 53 C 46 B 24 784 55 C 47 A 24 779 54 C 48 C 19 776 55 C 49 A 24 731 ' 56 C 50 D 未評估未評估未評估未評估 51 A 24 759 52 C 52 A 24 774 57 C 53 A 22 779 56 C 54 A 21 785 57 C 55 A 20 773 58 C 56 A 23 778 56 C 57 B 22 791 54 C 圖1中，中央附近之白色橢圓狀的部分就是析出物。此外由此圖1中的析出物的EDX分析結果（圖2 )’確認了該析出物爲含有Fe、P者、亦即已定義之〔Ni，Fe〕- P系析出物的一種。進一步地，說明各試樣之評估結果。再者’ >^〇.1〜>^〇.16爲以含有30%左右之211的（：11-30211合金爲 -39- 201233818 基質的本發明例、No.17〜No.27爲以含有25%左右之Zn 的Cu-25Zn合金爲基質的本發明例、Νο.28~Νο·39爲以含有35%左右之Ζη的Cu-35Ζη合金爲基質的本發明例、又 Νο·41、Νο.42、Νο·44~Νο·54、Νο.56、Νο.57 爲以含有 30 %左右之Ζη的Cu-30Zn合金爲基質的比較例、No.42爲含有37.1%之Ζη的比較例、No.55爲以含有25%左右之 Ζη的Cu-2 5Zn合金爲基質的比較例》如表7、表8所示，不僅各合金元素之個別含量係在本發明規定的範圍內，各合金成分相互間的比率亦在本發明規定範圍內之本發明例No.1〜No.39，殘留應力率均爲 60%以上，·其耐應力緩和特性優良，此外，導電率亦爲 21% IACS以上，可充分應用於接頭或其他端子構件，進一步地修飾軋延時之邊緣裂縫幾乎不發生、或即使發生亦係少於長度3 mm的微量，確認了軋延性良好，且強度相較於習知材料亦不遜色。另一方面，如表9所示，比較例之No.41爲由Cu-30Zn合金所成之習知材料、比較例之No.42爲於Cu-3 OZn合金中僅添加Sn而成的習知材料，該等之耐應力緩和特性均較以 Cu-30Zii合金爲基質的本發明例 No. 1 〜No. 1 6 爲劣。又，比較例之No .43因Ζη量過剩，故冷軋延（修飾軋延）時會發生破裂，之後的低溫熱處理無法實施，且各性能評估亦無法實施。進一步地比較例Νο·44因爲Sn量過剩，故熱軋延時 -40- 201233818 會發生破裂，之後的步驟無法實施，且各性能評估亦無法實施。另一方面，比較例No. 45因爲無添加Sn，故相較於以（：11-30211合金爲基質之本發明例1^〇.1〜：^.16，其耐應力緩和特性爲劣。又，比較例No.46因爲Ni量過剩，故相較於以Cu-30Zn合金爲基質之本發明例No.l~No.16，其耐應力緩和特性爲劣。另一方面，比較例No. 47因爲無添加Ni，故相較於以Cu-30Zn合金爲基質之本發明例No.l~No.16, 其耐應力緩和特性爲劣。又，比較例No.48因爲Fe量過剩，故導電率低達20 %IACS以下，而且相較於以Cu-30Zn合金爲基質之本發明例No. l~No. 16其耐應力緩和特性亦劣。另一方面，比較例No.49因爲無添加Fe，故相較於以Cu-30Zn合金爲基質之本發明例No. 1〜No. 16，其耐應力緩和特性爲劣。比較例Νο·5〇因P量過剩，故冷軋延（修飾軋延）時會發生破裂，之後的低溫熱處理無法實施，且各性能評估亦無法實施。另一方面，比較例Νο.51，因爲無添加Ρ，故相較於以 Cu-30Zn合金爲基質之本發明例No.l~No.16 ，其耐應力緩和特性爲劣。比較例之No.52〜No.57其各合金元素之個別含量雖均在本發明所規定之範圍內，但各合金元素相互間之含量比率（原子比）係在本發明所規定之範圍外。其中首先，No.52之比較例其Fe/Ni比相較於（1 )式之下限更低，此時相較於以Cu-30Zn合金爲基質之本發明 -41 - 201233818 例Νο·1〜Νο·16，其耐應力緩和特性爲劣。另一方面， No. 53之比較例，其Fe/Ni比相較於（1 )式之上限更高，此時，相較於以 Cu-30Zn合金爲基質之本發明例 /[Table 9] [Comparative Example] No. m___ Rollability evaluation Conductivity_S) Endurance (MPa) Stress relaxation resistance Residual stress rate (%) Evaluation 41 A 26 722 45 D 42 A 25 751 51 C 43 D Not evaluated Unassessed unevaluated unfinished 44 unevaluated unrecognized unevaluated unevaluated unevaluated — 45 A 24 726 53 C 46 B 24 784 55 C 47 A 24 779 54 C 48 C 19 776 55 C 49 A 24 731 ' 56 C 50 D Not evaluated Not evaluated Not evaluated Not evaluated 51 A 24 759 52 C 52 A 24 774 57 C 53 A 22 779 56 C 54 A 21 785 57 C 55 A 20 773 58 C 56 A 23 778 56 C 57 B 22 791 54 C In Fig. 1, the white elliptical portion near the center is the precipitate. Further, from the EDX analysis result (Fig. 2) of the precipitate in Fig. 1, it was confirmed that the precipitate was one of Fe, P, or a defined [Ni, Fe]-P-based precipitate. Further, the evaluation results of the respective samples will be described. Further, '>^〇.1~>^〇.16 is an example of the present invention containing No. 211 of about 211 (: 11-30211 alloy is -39-201233818, No. 17 to No. 27 is The present invention, which is based on a Cu-25Zn alloy containing about 25% Zn, is an example of the present invention based on a Cu-35Ζη alloy containing about 35% of Ζη, and Νο·41 Νο.42, Νο·44~Νο·54, Νο.56, Νο.57 are comparative examples with a Cu-30Zn alloy containing about 30% Ζη, and No.42 is a comparison with 37.1% Ζη. In the example, No. 55 is a comparative example in which Cu-2 5Zn alloy containing 25% of Ζη is used as a matrix. As shown in Tables 7 and 8, not only the individual contents of the respective alloy elements are within the range specified by the present invention. In the present invention examples No. 1 to No. 39 in which the ratio of each of the alloy components is within the range specified by the present invention, the residual stress rate is 60% or more, and the stress relaxation resistance is excellent, and the electric conductivity is also 21 % IACS or more, can be fully applied to joints or other terminal members, further modifying the edge delay of the rolling delay, hardly occurs, or even if it occurs, it is less than 3 mm in length. In a small amount, it was confirmed that the rolling property was good and the strength was not inferior to the conventional materials. On the other hand, as shown in Table 9, the comparative example No. 41 is a conventional material formed by Cu-30Zn alloy, and compared. In the example No. 42 is a conventional material in which only Sn is added to the Cu-3 OZn alloy, and the stress relaxation resistance characteristics are the same as those of the present invention No. 1 to No. 1 based on the Cu-30Zii alloy. In addition, in the comparative example No. 43, because the amount of Ζη is excessive, cracking occurs during cold rolling (modification rolling), and subsequent low-temperature heat treatment cannot be performed, and performance evaluation cannot be performed. Further Comparative Example Νο·44 Because the amount of Sn is excessive, the hot rolling delay -40-201233818 will break, the subsequent steps cannot be carried out, and the performance evaluation cannot be carried out. On the other hand, the comparative example No. 45 has no added Sn, so the phase Compared with the inventive example 1^〇.1~:^.16 which is based on (11-30211 alloy), the stress relaxation resistance is inferior. Moreover, Comparative Example No. 46 is excessive in amount of Ni, so compared with The inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy were inferior in stress relaxation resistance. On the other hand, in Comparative Example No. 47, since no Ni was added, the stress relaxation characteristics were inferior to those of the inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy. Further, Comparative Example No. Since the amount of Fe is excessive, the electrical conductivity is as low as 20% IACS or less, and the stress relaxation characteristics of the present invention No. 1 to No. 16 which are based on the Cu-30Zn alloy are also inferior. On the other hand, in Comparative Example No. 49, since Fe was not added, the stress relaxation characteristics of the present invention were inferior to those of the inventive examples No. 1 to No. 16 which were based on Cu-30Zn alloy. In the comparative example Νο·5〇, the amount of P was excessive, so that cracking occurred during cold rolling (modification rolling), and the subsequent low-temperature heat treatment could not be carried out, and evaluation of each performance could not be carried out. On the other hand, in Comparative Example Νο.51, since no yttrium was added, the stress relaxation characteristics were inferior to those of the inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy. In the comparative examples, No. 52 to No. 57, although the individual contents of the respective alloying elements are within the range defined by the present invention, the content ratio (atomic ratio) of each of the alloying elements is outside the range specified by the present invention. . First, in the comparative example No. 52, the Fe/Ni ratio is lower than the lower limit of the formula (1), and the present invention is compared with the case of the Cu-30Zn alloy-41-201233818 Νο·1~ Νο·16, its resistance to stress relaxation is inferior. On the other hand, in the comparative example of No. 53, the Fe/Ni ratio is higher than the upper limit of the formula (1), and in this case, compared to the present invention based on the Cu-30Zn alloy /

No.卜No. 16，其耐應力緩和特性亦劣。又，No.54之比較例，其（Ni + Fe ) /P比相較於（2 ) 式之下限更低，此時相較於以Cu-30Zn合金爲基質之本發明例No.l〜No.16，其耐應力緩和特性爲劣。另一方面， No· 55之比較例，其（Ni + Fe ) /P比相較於（2 )式之上限更高，此時，相較於以Cu-25Zn合金爲基質之本發明例 No.17~No.27，其耐應力緩和特性爲劣。進一步地，No.56之比較例，其Sn/ ( Ni + Fe)比相較於（3 )式之下限更低，此時，相較於以Cu-30Zn合金爲基質之本發明例No. 1〜No. 16，其耐應力緩和特性爲劣》另一方面，Νο·57之比較例，其Sn/ ( Ni + Fe)比相較於（3)式之上限更高，此時，相較於以Cu-30Zn合金爲基質之本發明例No. 1〜No. 16，其耐應力緩和特性亦劣。 [產業上之可利用性] 依照本發明，能夠提供強度、軋延性、導電率優良、且耐應力緩和特性優良的銅合金。如此之銅合金，適合用於構成接頭、其他端子> 之導電構件，可提供優良特性之電子/電氣機器用零件。【圖式簡單說明】 -42- 201233818 圖1爲對本發明之實施例的本發明例 FE-SEM (場發射型掃描電子顯微鏡）觀！出物之部位的組織照片。圖2爲顯示對圖1中之析出物以EDX 射線分光法）之分析結果的圖表。No. Bu No. 16, which is also inferior in stress relaxation resistance. Further, in the comparative example of No. 54, the (Ni + Fe ) / P ratio is lower than the lower limit of the formula (2), and the present invention No. 1 to the present invention is based on the Cu-30Zn alloy. No.16, its stress relaxation resistance is inferior. On the other hand, in the comparative example of No. 55, the (Ni + Fe ) / P ratio is higher than the upper limit of the formula (2), and in this case, the present invention No. is based on the Cu-25Zn alloy. .17~No.27, its stress relaxation resistance is inferior. Further, in the comparative example of No. 56, the Sn/(Ni + Fe) ratio is lower than the lower limit of the formula (3), and in this case, the inventive example No. is based on the Cu-30Zn alloy. 1~No. 16, the stress relaxation resistance is inferior. On the other hand, in the comparative example of Νο·57, the Sn/(Ni + Fe) ratio is higher than the upper limit of the formula (3). Inventive Examples No. 1 to No. 16, which are based on a Cu-30Zn alloy, are also inferior in stress relaxation resistance. [Industrial Applicability] According to the present invention, it is possible to provide a copper alloy which is excellent in strength, rolling ductility, electrical conductivity, and excellent in stress relaxation resistance. Such a copper alloy is suitable for use as a conductive member constituting a joint or other terminal, and can provide an electronic/electrical machine component having excellent characteristics. BRIEF DESCRIPTION OF THE DRAWINGS - 42 - 201233818 FIG. 1 is an example of the present invention of the present invention. FE-SEM (Field Emission Scanning Electron Microscope) View! A photograph of the organization of the part of the object. Fig. 2 is a graph showing the results of analysis of the precipitates in Fig. 1 by EDX ray spectroscopy).

N 〇 . 2的合金以 ;而得之含有析 (能量分散型X -43-The alloy of N 〇 . 2 is obtained by the analysis of the energy dispersion type X -43-

Claims

201233818 VII. Patent application scope: 1. A copper alloy for electronic/electrical equipment, characterized by containing Zn 23 to 36.5% (mass%, the same below), Sn 0.1 to 0.8%, Ni 0.05% or more and less 0 5 < F e/; 0.15, Fe 0.005% or more and less than 〇·10%, Ρ 0.005~0·05%, and the ratio of Fe content to Ni content Fe/Ni 'in an atomic ratio of 0. 0 5 < F e / N i < 1. 5 , and the ratio of the total content of Ni and Fe (Ni + Fe) to the P content (Ni + Fe) / P, in atomic ratio, satisfies 3 < (Ni + Fe) ^ Ρ < 1 5之间。 Further, the ratio of Sn content to the total amount of Ni and Fe (Ni + Fe) Sn / (Ni + Fe), in atomic ratio of 0. 5 < Sn / (Ni + Fe) < 5 , the remaining Part of it consists of Cu and unavoidable impurities. 2. A copper alloy for an electronic/electrical machine, characterized by containing Zn 23 to 36.5%, Sn 0.1 to 0.8%, Ni 0.05% or more and less than 0.15%, Fe 0.005% or more and less than 0.10%, Co 0.00质量以上为为0. 05< (Fe) The ratio of the total content of Fe and Co to the Ni content (Fe + Co) / Ni, in an atomic ratio of 0. 05 < (Fe +Co) /N i < 1. 5 , and the ratio of the total content of Ni, Fe and Co (Ni + Fe + Co) to the content of P (Ni + Fe + Co) / Ρ, which satisfies 3 < (Ni+Fe+Co) /P< 1 5 , further, the ratio of the Sn content to the total content of Ni, Fe and Co (-44-201233818 Ni + Fe + Co ) Sn / ( Ni + Fe + Co ) The atomic ratio satisfies 0.5 Å < Sn / (Ni + Fe + Co) < 5 , and the remainder is composed of Cu and unavoidable impurities. 3. A copper alloy sheet for an electronic/electrical machine, which is composed of a rolled material of a copper alloy as claimed in claim 1 or 2, and having a thickness in the range of 0.05 to 1.0 mm. A copper alloy sheet for an electronic/electrical machine which is coated with Sn on the surface of a copper alloy sheet as in the third application of the patent application. 5. A conductive member for an electronic/electrical machine, which is composed of a copper alloy sheet as in claim 3, and which is in contact with the opposite side conductive member to obtain an electrical connection with the opposite side conductive member. The member is configured to have a bending process on at least a portion of the plate surface and to maintain contact with the opposite side conductive material by the spring property of the curved portion. 6. A conductive member for an electronic/electrical machine, which is composed of a copper alloy sheet as in claim 4, and which is in contact with the opposite side conductive member to obtain an electrical connection with the opposite side conductive member. The member is configured to have a bending process on at least a portion of the plate surface and to maintain contact with the opposite side conductive material by the spring property of the curved portion. -45-