TWI521074B - Copper alloy for electronic and/or electrical device, copper alloy thin plate, and conductive member - Google Patents

Description

電子/電氣機器用銅合金、銅合金薄板及導電構件Copper alloy, copper alloy sheet and conductive member for electronic/electrical equipment

本發明係關於作為半導體裝置之接頭、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。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, and more particularly to Cu-Zn obtained by adding Sn to brass (Cu-Zn alloy). -Sn is a copper alloy for electronic/electrical equipment, a copper alloy sheet and a conductive member using the same.

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2011-30908號而主張優先權，且於此援用其內容。The present application claims priority based on Japanese Patent Application No. 2011-5164, filed on Jan.

作為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，主要為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。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. .

如上所述，以Cu-Zn合金作為基材，於其表面施以鍍Sn之接頭等之導電零件中，為了在提高鍍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作為合金成分之Cu-Zn-Sn系合金的情況。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.

以半導體之接頭或其他端子為代表之電子/電氣機器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，為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。A manufacturing process for an electronic/electrical machine conductive component represented by a semiconductor joint or other terminal is generally formed by rolling a copper alloy of a material to form a thin plate (bar) having a thickness of about 0.05 to 1.0 mm. The stamping is applied to a specified shape, and at least a portion thereof is further subjected to bending processing. 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 such a manner as to maintain 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 desirable that the conductivity is excellent and the strength is high. Moreover, it is desirable that the rolling process and the press workability are excellent by press-forming a thin plate (bar). 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.

作為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雖與本發明中作為主要用途之接頭等端子的用途相異，但作為引線框架用之Cu-Zn-Sn系合金，亦有揭示用以提高耐應力緩和特性之策略。As a strategy for improving the stress relaxation resistance of the Cu-Zn-Sn-based alloy used for the terminal such as a joint, the proprietors of Patent Document 1 to Patent Document 3 have been conventionally used. Further, although Patent Document 4 differs from the use of a terminal such as a joint as a main use in the present invention, a Cu-Zn-Sn-based alloy for a lead frame has a strategy for improving stress relaxation resistance.

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一起添加，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。Patent Document 1 discloses that Ni 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.

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、研究，已知僅有如此個別含量的調整時，並不一定能夠確實且充分地提高耐應力緩和特性。The inventors of the present invention have confirmed that the addition of Ni, Fe, and P to the Cu-Zn-Sn-based alloy is effective for improving the stress relaxation resistance characteristics. 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 individual content adjustment, and it is not necessarily true and sufficient. Improve the stress relaxation resistance.

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。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 trace addition of Fe is also effective for improving the stress relaxation resistance.

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，但是專利文獻3之提案中，關於生成P化合物之Fe、Ni等元素，完全沒有考慮其含量與耐應力緩和特性之關係，本發明者等之實驗中，若僅依照專利文獻3之提案，已知無法實現充分且確實地提高耐應力緩和特性。The adjustment of the Ni/Sn ratio shown in the proposal of Patent Document 3 is effective for improving the stress relaxation resistance, but the relationship between the P compound and the stress relaxation resistance is not touched at all. In other words, as shown in Patent Documents 1 and 2, the P compound has a large influence on the stress relaxation resistance. However, in the proposal of Patent Document 3, the elements such as Fe and Ni which form the P compound are not considered at all. In the experiments of the inventors of the present invention, it is known that the stress relaxation property is not sufficiently and surely improved in the experiments of the inventors and the like.

以引線框架為對象的專利文獻4提案中，記載了於Cu-Zn-Sn系合金中，將Ni、Fe與P一起添加，同時將(Fe+Ni)/P之原子比調整為0.2~3之範圍內，而生成Fe-P系化合物、Ni-P系化合物、或Fe-Ni-P系化合物，藉以可提高耐應力緩和特性。In the proposal of Patent Document 4 for the lead frame, it is described that 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 0.2 - 3 Within the range, an Fe-P compound, a Ni-P compound, or an Fe-Ni-P compound is formed, whereby stress relaxation resistance can be improved.

然而，依據本發明者等的實驗，若僅如專利文獻4之規定地調整Fe、Ni、P之合計量、與(Fe+Ni)/P之原子比，已知無法實現充分提高耐應力緩和特性。其理由雖尚未特定，但為了確實且充分地提高耐應力緩和特性，除了調整Fe、Ni、P之合計量與(Fe+Ni)/P以外，Fe/Ni比之調整、進而Sn/(Ni+Fe)之調整亦為重要，藉由本發明者等之實驗、研究，已知若不將該等各含量比率平衡良好地調整，則耐應力緩和特性無法確實且充分地提高。However, according to experiments by the inventors of the present invention, it is known that it is impossible to sufficiently improve the stress relaxation resistance by adjusting the total amount of Fe, Ni, and P and the atomic ratio of (Fe + Ni) / P as specified in Patent Document 4. characteristic. Although the reason is not specified, in order to reliably and sufficiently improve the stress relaxation resistance, in addition to adjusting the total amount of Fe, Ni, and P and (Fe + Ni) / P, the Fe/Ni ratio is adjusted, and further, Sn / (Ni The adjustment of +Fe) is also important, and it has been known by experiments and studies by the inventors of the present invention that the stress relaxation characteristics are not reliably and sufficiently improved unless the respective content ratios are adjusted in a well-balanced manner.

如以上所述，以往的提案、即作為Cu-Zn-Sn系合金所構成之電子/電氣機器導電零件用銅合金，而用以提高耐應力緩和特性之提案，耐應力緩和特性之提高效果尚不確實且充分，而期望進一步改良。換言之，如接頭般之具有對薄板(條)進行軋延且施以彎曲加工的彎曲部分，且於該彎曲部分附近與對側導電構件接觸，藉由彎曲部分的彈簧性以維持與對側導電構件之接觸狀態的方式而使用的零件中，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。為了迴避如此問題，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。As described above, the conventional proposal, that is, a copper alloy for conductive parts for electronic/electrical equipment composed of a Cu-Zn-Sn-based alloy, is proposed to improve stress relaxation resistance, and the effect of improving stress relaxation resistance is still Not sure and sufficient, and further improvement is expected. In other words, as the joint has a curved portion for rolling a thin plate (strip) and applying a bending process, and is in contact with the opposite side conductive member in the vicinity of the curved portion, and maintaining the opposite side conduction by the spring property of the curved portion In the parts used in the contact state of the member, the residual stress is moderated over time or in a high temperature environment, and the contact pressure with the opposite side conductive member cannot be maintained, and as a result, it is easy to cause contact failure in advance. The problem of the shortcomings. In order to avoid such a problem, it has to be made thicker in the conventional material, which leads to an increase in material cost and an increase in weight.

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]　日本特開平5-33087號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-33087

[專利文獻2]　日本特開2006-283060號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-283060

[專利文獻3]　日本專利第3953357號公報[Patent Document 3] Japanese Patent No. 3953357

[專利文獻4]　日本專利第3717321號公報[Patent Document 4] Japanese Patent No. 3717321

如前所述，作為附有鍍Sn的黃銅條基材所使用之習知Cu-Zn-Sn系合金，為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)之耐應力緩和特性尚未確實且充分優良。因而強烈期望耐應力緩和特性更加確實且充分的改善。As described above, a conventional Cu-Zn-Sn-based alloy used as a base material for a Sn-plated brass strip is subjected to bending processing in order to obtain a joint or other various terminals, and is adjacent to the bent portion thereof. The contact-resistance characteristics of the sheet material (bar) used for the contact of the side conductive members are not yet sure and sufficiently excellent. Therefore, it is strongly desired that the stress relaxation resistance property is more sure and sufficiently improved.

本發明係以上述情形為背景而完成者，其課題為提供一種銅合金，其係作為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。The present invention has been made in view of the above circumstances, and an object thereof is to provide a copper alloy which is a copper alloy, particularly a Cu-Zn-Sn alloy, which is used as a conductive member of an electronic/electrical machine such as a joint or other terminal. The stress relaxation resistance is indeed excellent and excellent, and the copper material of the part material can be thinned, and the strength, the rolling property, the electrical conductivity and the like are excellent, and the copper alloy sheet and the conductive material using the same are provided. member.

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/研究後，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。The inventors of the present invention have tried to repeat the experiment and research on the solution strategy of the above-mentioned problems, and 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 is added. P (phosphorus), and not only adjust the individual content of these alloying elements, but also the ratio of Ni, Fe, P, and Sn in the alloy, especially the ratio of Fe and Ni to Fe/Ni, Ni and The ratio of the total content of Fe (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), When the atomic ratio is adjusted to an appropriate range, the stress relaxation resistance can be surely and sufficiently improved, and a copper alloy having excellent properties such as joints or other terminals required for strength, rolling property, electrical conductivity, and the like can be obtained, thereby achieving this invention.

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。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.

本發明之基本形態(第1形態)之電子/電氣機器用銅合金為一種銅合金，其特徵為：以mass%計含有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%、P 0.005~0.05%，且Fe含量與Ni含量之比Fe/Ni，以原子比計滿足0.05<Fe/Ni<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<15，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，且剩餘部分為Cu及不可避的雜質所構成。 A copper alloy for an electric/electrical device according to a first aspect of the present invention is a copper alloy characterized by containing Zn 23 to 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, which satisfies 0.05<Fe/Ni<1.5 in atomic ratio, and Ni content and Fe The ratio of the total content of the content (Ni + Fe) to the content of P (Ni + Fe) / P, in terms of atomic ratio, satisfies 3 < (Ni + Fe) / P < 15, and the content of Sn and the content of Ni and Fe The ratio of the combined (Ni + Fe) ratio of Sn / (Ni + Fe) is composed of an atomic ratio of 0.5 < Sn / (Ni + Fe) < 5, and the remainder is Cu and an unavoidable impurity.

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一起同時添加適當量，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，依實際之材料中該等元素的含量而可能無法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。 According to the basic form of the present invention, in addition to an appropriate amount of Sn, Ni and Fe are simultaneously added with P in an appropriate amount, and the ratio of addition of Sn, Ni, Fe, and P to each other 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. In other words, when only the individual contents of Sn, Ni, Fe, and P are simply adjusted within the specified range, sufficient stress-relieving characteristics may not be achieved depending on the content of the elements in the actual material, and others. The characteristics may be insufficient. However, by standardizing the relative ratio of the contents of the elements to the ranges defined by the above formulas, it is possible to surely and sufficiently improve the stress relaxation resistance characteristics, and at the same time, it is possible to satisfy the requirements of the terminal materials such as joints. characteristic.

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、Zn、Sn；雜質之O、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。Here, the [Ni,Fe]-P-based precipitate refers to a ternary precipitate of Ni-Fe-P or a ternary precipitate of Fe-P or Ni-P, and further refers to these. It may include multi-component precipitates containing other elements such as Cu, Zn, and Sn as main components; O, S, C, Co, Cr, Mo, etc. of impurities. Further, the [Ni,Fe]-P-based precipitate is present in the form of a phosphide or an alloy in which phosphorus is dissolved.

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，其特徵為：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)/Ni＜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，且剩餘部分為Cu及不可避的雜質所構成。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)/Ni<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 Satisfying 3<(Ni+Fe+Co)/P<15, and the ratio of the Sn content to the total content of Ni, Fe, and Co (Ni+Fe+Co), Sn/(Ni+Fe+Co), in atomic ratio It satisfies 0.5<Sn/(Ni+Fe+Co)<5, and the remainder is Cu and unavoidable impurities.

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Co，藉由作成[Ni,Fe,Co]-P系析出物適當地存在的組織，可更加提高耐應力緩和特性。In the copper alloy for electric/electrical equipment according to the second aspect, an appropriate amount of Co is added simultaneously with Ni, Fe, and P as described above, and a [Ni, Fe, Co]-P-based precipitate is appropriately formed. The organization can improve the stress relaxation resistance.

此處[Ni,Fe,Co]-P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O、S、C、Cr、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。Here, the [Ni, Fe, Co]-P-based 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 precipitate, which may include Cu, Zn, Sn containing other elements, such as a main component; Multicomponent precipitates of impurities such as O, S, C, Cr, Mo, etc. 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.

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，且厚度為0.05~1.0mm之範圍內的銅合金薄板。Further, the copper alloy sheet for an electric/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.

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。Such a strip of rolled sheet (bar) can be suitably used for joints and other terminals.

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。Further, the copper alloy sheet for an electronic/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.

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為鍍Sn黃銅系合金之廢料而回收，以確保良好的回收再利用性。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 component such as a used joint as a scrap of a Sn-plated brass alloy. To ensure good recycling.

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。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.

以下，對本發明之電子/電氣機器用銅合金更詳細地說明。Hereinafter, the copper alloy for electronic/electrical equipment of the present invention will be described in more detail.

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%、P 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0.05＜Fe/Ni＜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)/P，以原子比計滿足下述(2)式3＜(Ni+Fe)/P＜15　‧‧‧(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　‧‧‧(3)，上述各合金元素之剩餘部分係Cu及不可避免的雜質。The copper alloy for electronic/electrical equipment of the present invention has an individual content of alloying elements, in mass%, containing Zn 23 to 36.5%, Sn 0.1 to 0.8%, Ni 0.05% or more and less than 0.15%, and Fe 0.005. % or more and less than 0.10%, P 0.005 to 0.05%, further, the content ratio of each alloy element, the ratio of Fe content to Ni content, Fe/Ni, satisfy the following formula (1) by atomic ratio 0.05<Fe/Ni<1.5 ‧‧‧(1), and the ratio of the Ni content and the Fe content (Ni+Fe) to the P content (Ni+Fe)/P, in atomic ratio, satisfies the following (2) ) 3 < (Ni + Fe) / P < 15 ‧ ‧ (2), and the ratio of Sn content to the total content of Ni and Fe (Ni + Fe) Sn / (Ni + Fe), atomic ratio The system satisfies the following formula (3): 0.5 < Sn / (Ni + Fe) < 5 ‧ ‧ (3), and the remainder of each of the above alloy elements is Cu and unavoidable impurities.

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(1′)式0.05＜(Fe+Co)/Ni＜1.5　‧‧‧(1′)，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′)式3＜(Ni+Fe+Co)/P＜15　‧‧‧(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為Cu及不可避的雜質。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 Ratio, ratio of total content of Fe and Co to Ni content (Fe + Co) / Ni, in atomic ratio, satisfying the following formula (1') 0.05 < (Fe + Co) / Ni < 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 formula (2′) <(Ni+Fe+Co)/P<15 ‧‧‧(2'), moreover, the ratio of the Sn content to the total content of Ni, Fe, and Co (Ni+Fe+Co) Sn/(Ni+Fe+ Co), in terms of atomic ratio, satisfies the following formula (3'): 0.5<Sn/(Ni+Fe+Co)<5 ‧‧‧(3'), and the remainder of each of the above alloying elements is Cu and an unavoidable impurity .

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。Next, the reason for limiting the chemical composition of the copper alloy of the present invention and the ratio of these mutual ratios will be described first.

Zn：以mass%計，為23~36.5%Zn: in terms of mass%, 23 to 36.5%

Zn為以本發明為對象之銅合金(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β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含量成為23~36.5%之範圍內。另外，Zn量於上述範圍內，特別以24~36%之範圍內為佳。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 lower than that of Cu, and therefore 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 β phase is simultaneously suppressed. It is produced in a large amount, so cold rolling ductility and bending workability are also lowered. Therefore, the Zn content is in the range of 23 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，為0.05%以上且少於0.15%Ni: 0.05% or more and less than 0.15% in mass%

Ni，與Fe、P一同皆為本發明中作為特徵的添加元素，藉由於Cu-Zn-Sn合金中添加適量的Ni，且使Ni與Fe、P共存，能夠使[Ni,Fe]-P系析出物由母相(α相主體)析出，又，藉由使Ni與Fe、Co、P共存，能夠使[Ni,Fe,Co]-P系析出物由母相(α相主體)析出，藉由該等之[Ni,Fe]-P系析出物或[Ni,Fe,Co]-P系析出物的存在，能夠大幅提高耐應力緩和特性。此處，Ni之添加量少於0.05%時，無法充分提高耐應力緩和特性。另一方面，Ni之添加量為0.15%以上時，固溶Ni變多，導電率降低，且因為高價之Ni原料之使用量增大，而導致成本上昇。因而，使Ni之添加量成為0.05%以上且少於0.15%之範圍內。另外Ni之添加量，於上述範圍內，特別以0.05%以上且少於0.10%之範圍內為佳。Ni, together with Fe and P, are additive elements characterized by the present invention. By adding an appropriate amount of Ni to the Cu-Zn-Sn alloy and allowing Ni to coexist with Fe and P, [Ni,Fe]-P can be made. The precipitates are precipitated from the parent phase (α phase host), and by depositing Ni with Fe, Co, and P, the [Ni, Fe, Co]-P precipitates can be precipitated from the parent phase (α phase host). By the presence of such [Ni,Fe]-P-based precipitates or [Ni,Fe,Co]-P-based precipitates, the stress relaxation resistance can be greatly improved. Here, when the addition amount of Ni is less than 0.05%, the stress relaxation resistance cannot be sufficiently improved. On the other hand, when the addition amount of Ni is 0.15% or more, the amount of solid solution Ni increases, the electrical conductivity decreases, and the use amount of the expensive Ni raw material increases, resulting in an increase in cost. Therefore, the amount of Ni added is in the range of 0.05% or more and less than 0.15%. Further, the amount of addition 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，為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一同皆為本發明中作為特徵的添加元素，藉由於Cu-Zn-Sn合金中添加適量之Fe，且使Fe與Ni、P共存，能夠使[Ni,Fe]-P系析出物由母相(α相主體)析出，又，藉由使Fe與Ni、Co、P共存，能夠使[Ni,Fe,Co]-P系析出物由母相(α相主體)析出。藉由該等[Ni,Fe]-P系析出物或[Ni,Fe,Co]-P系析出物之存在，能夠大幅提高銅合金之耐應力緩和特性。此處，Fe添加量少於0.005%時，無法充分提高耐應力緩和特性。另一方面Fe添加量為0.10%以上時，無法觀察到更加提高耐應力緩和特性，且固溶Fe增多，導電率降低，冷軋延性亦降低。因而，係使Fe添加量為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%之範圍內為佳。Fe, together with Ni and P, is an additive element characterized by the present invention. By adding an appropriate amount of Fe to the Cu-Zn-Sn alloy and coexisting Fe with Ni and P, [Ni, Fe]- can be made. The P-based precipitates are precipitated from the parent phase (α-phase body), and by allowing Fe to coexist with Ni, Co, and P, the [Ni, Fe, Co]-P-based precipitates can be made from the parent phase (α-phase body). Precipitate. The presence of such [Ni,Fe]-P-based precipitates or [Ni,Fe,Co]-P-based precipitates can greatly improve the stress relaxation resistance of the copper alloy. Here, when the Fe addition amount 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, it is not observed that the stress relaxation resistance is further improved, the solid solution Fe is increased, the electrical conductivity is lowered, and the cold rolling ductility is also lowered. Therefore, the Fe addition amount 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，為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添加量為0.10%以上時，固溶Co增多，導電率降低，且因為高價格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添加量成為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%之範圍內為佳。再者，不積極地添加Co時，亦可能含有作為雜質的少於0.005%之Co。Co 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 amount of use of the high-priced Co raw material increases, so that the cost 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 amount of Co added is in 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：以mass%計，為0.005~0.05%P: 0.007~0.05% in mass%

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[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%之範圍內為佳。P-based, Fe, Ni, and further have high binding property to Co. In addition to Fe and Ni, if an appropriate amount of P is contained, [Ni,Fe]-P-based precipitates can be precipitated, and Fe, Ni, and Co can be deposited. In addition, when an appropriate amount of P is contained, [Ni, Fe, Co]-P-based precipitates can be precipitated, and the stress relaxation characteristics of the copper alloy can be improved by the presence of the precipitates. When the amount of P is less than 0.005%, it is difficult to sufficiently precipitate [Ni,Fe]-P-based precipitates or [Ni,Fe,Co]-P-based precipitates, and the stress relaxation resistance is not sufficiently improved. 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 preferably in the above range, particularly preferably in the range of 0.01% to 0.04%.

再者，P為經常不可避免地由銅合金之熔解原料混入之元素。因此，為了如上述般規範P量，係期望適當地選定熔解原料。Further, P is an element which is often inevitably mixed with a melting raw material of a copper alloy. Therefore, in order to regulate the amount of P as described above, it is desirable to appropriately select the molten raw material.

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、Al、Mn、Si、(Co)、Cr、Ag、Ca、Sr、Ba、Sc、Y、Hf、V、Nb、Ta、Mo、W、Re、Ru、Os、Se、Te、Rh、Ir、Pd、Pt、Au、Cd、Ga、In、Li、Ge、As、Sb、Ti、Tl、Pb、Bi、S、O、C、Be、N、H、Hg、B、Zr、稀土類等。該等之不可避免雜質，期望總量為0.3質量%以下。The remainder of each of the above elements is basically a Cu and an unavoidable impurity. Examples of the unavoidable impurities herein include Mg, Al, Mn, Si, (Co), Cr, Ag, Ca, Sr, Ba, Sc, Y, Hf, V, Nb, Ta, Mo, W, Re, Ru, Os, Se, Te, Rh, Ir, Pd, Pt, Au, Cd, Ga, In, Li, Ge, As, Sb, Ti, Tl, Pb, Bi, S, O, C, Be, N, H, Hg, B, Zr, rare earths, and the like. The inevitable impurities are desirably 0.3% by mass or less.

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(1′)~(3′)式。因而，以下說明(1)~(3)式、(1′)~(3′)式之限定理由。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 (1') to (3') are satisfied. Therefore, the reasons for limiting the formulas (1) to (3) and (1') to (3') will be described below.

(1)式：0.05<Fe/Ni<1.5(1) Formula: 0.05<Fe/Ni<1.5

依據本發明者等詳細的實驗，Fe/Ni比會對銅合金之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各自的含量調整為如前所述，且使該等之比Fe/Ni，以原子比計成為超過0.05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比為1.5以上時，耐應力緩和特性會降低，又，Fe/Ni比低於0.05時耐應力緩和特性亦會降低。又，Fe/Ni比低於0.05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比規範為上述範圍內。另外，Fe/Ni比於上述範圍內，尤以0.1~1.2之範圍內為佳。According to a detailed experiment by the inventors of the present invention, the Fe/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 improved. In other words, it has been found that not only Fe and Ni are coexisted, but also the content of each of Fe and Ni is adjusted as described above, and the ratio of Fe/Ni is more than 0.05 and less than 1.5 in atomic ratio. In the meantime, it is possible to achieve sufficient improvement in stress relaxation resistance. Here, when the Fe/Ni ratio is 1.5 or more, the stress relaxation resistance is lowered, and when the Fe/Ni ratio is less than 0.05, the stress relaxation resistance is also lowered. Further, when the Fe/Ni ratio is less than 0.05, the use amount of the Ni raw material having a high price tends to increase relatively, resulting in an increase in cost. Therefore, the Fe/Ni ratio specification is 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)式：3<(Ni+Fe)/P<15(2) Formula: 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)，則因為固溶之Ni、Fe的比例增大，耐應力緩和特性會降低，因而為了充分地提高耐應力緩和特性，(Ni+Fe)/P比亦為重要。(Ni+Fe)/P比為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，且同時因為固溶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比為15以上時，因為固溶之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以下的範圍內為佳。By allowing Ni and Fe to coexist with P, [Ni,Fe]-P-based precipitates are formed, and by the dispersion of the [Ni,Fe]-P-based precipitates, the stress relaxation characteristics of the copper alloy can be improved. 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 dissolved Ni and Fe 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 or more, the conductivity of the copper alloy is lowered because the ratio of Ni and Fe which are solid solution is increased. 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)式：0.5<Sn/(Ni+Fe)<5(3) Formula: 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)比為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之範圍內為佳。When Sn is coexisted with Ni and Fe as described above, Sn contributes to an improvement in stress relaxation resistance of the copper alloy, but the stress relaxation property is improved when the Sn/(Ni+Fe) ratio is out of a specific range. It cannot be fully utilized. In other words, when the Sn/(Ni+Fe) ratio is 0.5 or less, the effect of improving the stress relaxation resistance is not exhibited. On the other hand, when the Sn/(Ni+Fe) ratio exceeds 5, the relative (Ni+Fe) is relatively (Ni+Fe). When the amount is small, the amount of [Ni,Fe]-P-based precipitates is small, and the stress relaxation resistance is lowered. Further, Sn/(Ni + Fe) is preferably in the range of from 1 to 4.5 in the above range.

(1′)式：0.05<(Fe+Co)/Ni<1.5(1') formula: 0.05 < (Fe + Co) / Ni < 1.5

添加有Co的情況時，可考慮為將Fe的一部分取代為Co，因此(1′)式基本上亦以(1)式為準。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各自的含量調整為如前所述，且使Fe與Co合計含量與Ni含量的比(Fe+Co)/Ni，以原子比計為超過0.05且低於1.5的範圍內時，能夠實現耐應力緩和特性的充分提高。此處，(Fe+Co)/Ni比為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+Co)/Ni比規範於上述範圍內。When Co is added, it is considered that a part of Fe is substituted with Co, and therefore, the formula (1') is basically also based on the formula (1). That is, when Co is added in addition to Fe or 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 resistance can be sufficiently improved. Here, when the (Fe + Co) / Ni ratio is 1.5 or more, the stress relaxation resistance is lowered, and the (Fe + Co) / Ni ratio is less than 0.05, and the stress relaxation resistance is also lowered. Therefore, the (Fe + Co) / Ni ratio is specified within the above range.

再者，(Fe+Co)/Ni比於上述範圍內，尤以0.1~1.2之範圍內為佳。Further, the (Fe + Co) / Ni ratio is preferably in the range of 0.1 to 1.2.

(2′)式：3<(Ni+Fe+Co)/P<15(2'): 3<(Ni+Fe+Co)/P<15

添加Co之情況時，(2′)式亦以前述(2)式為準。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，為了充分提高耐應力緩和特性，(Ni+Fe+Co)/P比亦為重要。(Ni+Fe+Co)/P比為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，且同時因為固溶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比為15以上時，因為固溶之Ni、Fe、Co的比例增大，而導電率會降低。因而，係使(Ni+Fe+Co)/P比規範為上述範圍內。再者，(Ni+Fe+Co)/P比於上述範圍內，尤以超過3、且10以下之範圍內為佳。When Co is added, the formula (2') is also based on the above formula (2). In other words, by coexisting Ni, Fe, and Co with P, [Ni, Fe, Co]-P-based precipitates are formed, and the dispersion of the [Ni, Fe, Co]-P-based precipitates can be improved. The stress relaxation characteristics of 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 the stress relaxation resistance, the (Ni + Fe + Co) / P ratio is also important. When the ratio of (Ni+Fe+Co)/P is 3 or less, the ratio of the solid solution P increases, the stress relaxation resistance 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 liable to occur. The cold rolling is broken and the bending workability is also lowered. On the other hand, when the ratio of (Ni + Fe + Co) / P is 15 or more, the ratio of Ni, Fe, and Co in solid solution increases, and the electrical conductivity decreases. Therefore, the (Ni + Fe + Co) / P ratio specification is within the above range. Further, the (Ni + Fe + Co) / P ratio is preferably in the range of more than 3 and not more than 10 in the above range.

(3′)式：0.5<Sn/(Ni+Fe+Co)<5(3'): 0.5<Sn/(Ni+Fe+Co)<5

添加Co的情況時，(3′)式亦以前述(3)式為準。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)比為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之範圍內為佳。When Co is added, the formula (3') is also based on the above formula (3). That is, when Sn coexists with Ni, Fe, and Co, Sn contributes to the improvement of the stress relaxation resistance of the copper alloy, but the stress relaxation property is improved when the Sn/(Ni+Fe+Co) ratio is not in a specific range. It cannot be fully utilized when it is inside. Specifically, when the ratio of Sn/(Ni + Fe + Co) is 0.5 or less, the effect of improving the stress relaxation resistance is not exhibited sufficiently. On the other hand, when the ratio of Sn/(Ni + Fe + Co) exceeds 5, the ratio is relatively The amount of (Ni + Fe + Co) is 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 in the above range.

如以上所述，將各合金元素不僅是個別含量，且將各元素相互比率調整為滿足(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系析出物會成為由母相(α相主體)分散析出者，可認為藉由如此之析出物的分散析出，會提高耐應力緩和特性。As described above, each alloying element is not only an individual content, but also the ratio of each element to a copper alloy for electronic/electrical equipment satisfying the formula (1) to (3) or (1') to (3'). As described above, [Ni,Fe]-P-based precipitates or [Ni,Fe,Co]-P-based precipitates are dispersed by the parent phase (α phase host), and it is considered that The dispersion of the precipitates increases the stress relaxation resistance.

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。具體的結晶粒徑值雖無特殊限定，較佳為在後述製造製程中，於用以再結晶及析出之中間熱處理後的階段，使平均結晶粒徑為20μm以下。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 the 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 value is not particularly limited, and it is preferred to have an average crystal grain size of 20 μm or less in a stage after the intermediate heat treatment for recrystallization and precipitation in a production process to be described later.

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)的情況為例子來說明。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 taking a case of producing a thin plate (bar) having a thickness of about 0.05 to 1.0 mm.

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，但亦可將廢料作為原料使用。又，熔解步驟中，可使用大氣環境爐，但為了控制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。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 environment furnace may be used. However, in order to control the oxidation of Zn, a vacuum furnace or an environmental furnace in an inert gas atmosphere or a reducing atmosphere may be used.

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)。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.). ).

之後，依照需要，為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℃加熱5分鐘~24小時即可。均質化處理溫度低於600℃、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℃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。Thereafter, in order to eliminate segregation, the ingot structure is uniformized as needed, and homogenization treatment is performed. Although the conditions of the 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 ° C or the homogenization treatment time is less than 5 minutes, a sufficient homogenization effect may not be obtained. On the other hand, when the homogenization treatment temperature exceeds 950 ° C, a part of the segregation site is melted; and 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 production is performed as needed.

接著，對鑄塊進行熱軋延，得到板厚0.5~50mm左右的熱延板。此熱軋延之條件亦無特殊限定，但通常較佳為使開始溫度為600~950℃、結束溫度為300~850℃、軋延率為10~90%左右。再者至熱軋延開始溫度為止的鑄塊加熱，亦可與前述鑄塊均質化處理一併進行。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。Next, the ingot is hot rolled to obtain a heat spreader having a thickness of about 0.5 to 50 mm. The conditions of the hot rolling are also not particularly limited. However, it is usually preferred to have 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 together with the 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.

熱軋延後，施以一次冷軋延(中間軋延)，成為板厚0.05~5mm左右的中間板厚。此一次冷軋延之軋延率雖無特殊限定，但通常為20~99%左右。一次冷軋延後，係施以中間熱處理。該中間熱處理，係為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為300~800℃，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為使該等析出物充分生成的時間、亦即通常為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，故較佳為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。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. Since the temperature region in which the precipitates are formed is 300 to 800 ° C, the intermediate heat treatment may be 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 exerts a certain influence on the stress relaxation resistance. Therefore, it is preferred to measure the recrystallized grain 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.

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。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.

亦即，作為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。此外中間熱處理之較佳加熱條件，在使用批次式加熱爐的情況期望為300~800℃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為300~800℃、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為非氧化性環境(氮氣環境、惰性氣體環境、或還原性環境)。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, in the case of using a batch type heating furnace, it is desirable to use a batch type heating furnace at a temperature of 300 to 800 ° C for 5 minutes to 24 hours. When a continuous annealing line is used, 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).

中間熱處理後之冷卻條件雖無特殊限定，但通常以2000℃/秒~100℃/小時左右的冷卻速度來冷卻即可。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 100 ° C / hr.

中間熱處理之後，為了修飾至產品板厚(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為5~99%。修飾冷軋延率低於5%時，會有無法得到作為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。After the intermediate heat treatment, in order to modify to the product sheet thickness (about 0.05 to 1.0 mm) and at the same time to obtain the required strength by work hardening, cold rolling (refining cold rolling) is performed again. 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.

修飾冷軋延後，依照需要進行低溫熱處理(修飾退火)，以作為應力釋放退火。此低溫熱處理較期望在50~500℃範圍內的溫度進行1秒~24小時。低溫熱處理之溫度低於50℃、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℃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。After the modified cold rolling is delayed, 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 crystallization of recrystallization; further, the time of the low-temperature heat treatment exceeds 24 hours, which only causes an increase in cost.

如以上所述，可得到由α相主體之母相分散析出[Ni,Fe]-P系析出物或[Ni,Fe,Co]-P系析出物之板厚0.05~1.0mm左右的Cu-Zn-Sn系合金薄板(條材)。如此之薄板，可將其直接使用於電子/電氣機器用導電零件，但通常係於板面之一面、或兩面施以膜厚0.1~10μm左右的鍍Sn，並作為附有鍍Sn之銅合金條而使用於接頭或其他端子等電子/電氣機器用導電零件。此時鍍Sn之方法無特殊限定，可依照通常方法應用電鍍、或依情況在電鍍後施以回流處理。As described above, it is possible to obtain Cu-separation of [Ni,Fe]-P-based precipitates or [Ni,Fe,Co]-P-based precipitates having a thickness of about 0.05 to 1.0 mm from the mother phase of the α phase main body. Zn-Sn alloy sheet (bar). Such a thin plate can be directly used for a conductive member for an electronic/electrical device, but is usually applied on one side of the plate surface or on both sides with a film thickness of about 0.1 to 10 μm, and is used as a copper alloy with Sn plating. It is used for conductive parts for electronic/electrical equipment such as connectors or other terminals. The method of plating Sn at this time is not particularly limited, and plating may be applied according to a usual method, or may be subjected to a reflow treatment after plating.

再者，實際使用於接頭或其他端子時，如之前所述，通常係對薄板施以彎曲加工。又，一般係以在其彎曲加工部分附近，藉由彎曲部分之彈簧性而壓接於對側導電構件，而確保與對側導電構件之電導通的樣態來使用。對於如此樣態的使用而言，本發明之銅合金最為適宜。Further, when actually used for a joint or other terminal, as described above, the thin plate is usually subjected to a bending process. Further, it is generally used in the vicinity of the bent portion thereof by crimping the opposite side conductive member 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 such a state.

以下，將為了確認本發明效果而進行的確認實驗的結果，一併顯示於於本發明的實施例、比較例。此外，以下的實施例為用以說明本發明效果者，實施例所記載之構成、製程、條件並非為限定本發明之技術範圍者。Hereinafter, the results of the confirmation experiment performed to confirm the effects of the present invention are shown together in the examples and comparative examples of the present invention. In addition, the following examples are intended to explain the effects of the present invention, and the configurations, processes, and conditions described in the examples are not intended to limit the technical scope of the present invention.

[實施例][Examples]

準備由Cu-35% Zn母合金及純度99.99質量%以上之無氧銅(ASTM B152 C10100)所構成之原料，將之裝入高純度石墨坩堝內，於N₂氣體環境中使用電氣爐熔解。於銅合金熔融金屬內添加各種添加元素，作為本發明例，熔製表1及表2之No.1~No.39所示成分組成的合金、及作為比較例，熔製表3之No.41~No.57所示成分組成之合金熔融金屬，將熔融金屬注入碳鑄模，製出鑄塊。再者，鑄塊的大小設為厚度約25mm×寬度約25mm×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、850℃保存指定時間作為均質化處理後，實施水淬硬。A raw material composed of Cu-35% Zn master alloy and oxygen-free copper (ASTM B152 C10100) having a purity of 99.99% by mass or more was prepared and placed in a high-purity graphite crucible, and melted in an electric furnace in an N ₂ gas atmosphere. Various addition elements were added to the copper alloy molten metal, and as an example of the present invention, alloys of the composition shown in No. 1 to No. 39 of Tables 1 and 2 were melted, and as a comparative example, the No. of Table 3 was melted. An alloy molten metal having a composition of 41 to No. 57 is injected into a carbon mold to produce an ingot. 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.

接著，再加熱使熱軋延開始溫度成為850℃，進行軋延率約50%之熱軋延，由軋延結束溫度500~700℃進行水淬火，實施表面研削後，製出厚度約11mm×寬度約25mm之熱軋延材。Then, the hot rolling is started at a temperature of 850 ° C, and a rolling rolling rate of about 50% is performed, and water quenching is performed at a rolling end temperature of 500 to 700 ° C, and after surface grinding, a thickness of about 11 mm is produced. Hot rolled strands with a width of about 25 mm.

之後，進行軋延率約80%之軋延作為一次冷軋延(表4~表6中之中間軋延)後，於550℃實施熱處理，使中間熱處理後之平均結晶粒徑成為約10μm，作為中間熱處理(再結晶及析出處理)。Thereafter, rolling was performed at a rolling ratio of about 80% as a primary cold rolling (intermediate rolling in Tables 4 to 6), and then heat treatment was performed at 550 ° C to obtain an average crystal grain size after the intermediate heat treatment of about 10 μm. As an intermediate heat treatment (recrystallization and precipitation treatment).

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研磨、蝕刻，以光學顯微鏡攝影，使中間軋延方向成為照片的橫向，於1000倍視野(約300μm×200μm)進行觀察。接著，依照JIS H 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值作為平均結晶粒徑。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。At the stage after the intermediate heat treatment, the average crystal grain size was observed in the following manner. That is, each sample after the intermediate heat treatment was subjected to mirror polishing and etching, and the film was observed by an optical microscope, and the intermediate rolling direction was made into a lateral direction of the photograph, and observed in a 1000-fold field of view (about 300 μm × 200 μm). Next, according to the cutting method of JIS H 0501, five lines of a predetermined length were drawn vertically and horizontally, and the number of crystal grains completely cut was counted, and the average value of the cut lengths was defined as an average crystal grain size. The average crystal grain size of the stage after the intermediate heat treatment observed in this manner is shown in Tables 4 to 6.

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0.25mm×寬度約25mm之條材(薄板)。Thereafter, the modified cold rolling was carried out at the rolling ratio shown in Tables 4 to 6, to obtain a strip (thin sheet) having a thickness of about 0.25 mm and a width of about 25 mm.

最後，作為修飾之應力釋放退火(低溫熱處理)，於Ar氣體環境中，於200℃保持1小時保持後，實施水淬硬，實施表面研削後，製出特性評估用條材。Finally, as a modified stress relief annealing (low temperature heat treatment), it was held at 200 ° C for 1 hour in an Ar gas atmosphere, and then subjected to water hardening, and subjected to surface grinding to prepare a strip for property evaluation.

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。The strips for evaluation of the properties were observed, and the ductility, electrical conductivity, and mechanical properties (endurance) were observed, and the stress relaxation resistance was observed, and the structure 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.

[軋延性評估][Rolling property evaluation]

觀察前述修飾冷軋延時之邊緣裂縫有無，作為軋延性評估。以目視完全無觀察到邊緣裂縫、或幾乎無觀察到者為A、產生長度低於1mm之小的邊緣裂縫者為B、產生長度1mm以上且低於3mm之邊緣裂縫者為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為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。The presence or absence of the edge crack of 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 characteristics are significantly difficult to evaluate, 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.

[機械特性][Mechanical characteristics]

由特性評估用條材採取JIS Z 2201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σ_0.2。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。The test piece No. 13B prescribed in JIS Z 2201 was used for the property evaluation strip, and the 0.2% proof stress σ _{0.2 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.

[導電率][Conductivity]

由特性評估用條材採取寬度10mm×長度60mm之試驗片，藉由4端子法求得電阻。又，使用測微器進行試驗片之尺寸測定，算出試驗片的體積。此外，由測定後之電阻值與體積算出導電率。再者，試驗片係以其長度方向平行於特性評估用條材之軋延方向的方式採取。A test piece having a width of 10 mm and a length of 60 mm was taken from the strip for characteristic evaluation, and the electric resistance was obtained by a 4-terminal method. Further, the size of the test piece was measured using a micrometer, and the volume of the test piece was calculated. Further, the conductivity was calculated from the measured resistance value and volume. Further, the test piece was taken in such a manner that its longitudinal direction was parallel to the rolling direction of the property evaluation strip.

[耐應力緩和特性][Resistance to stress relaxation characteristics]

耐應力緩和特性試驗，係根據日本伸銅協會技術標準JCBA-T309：2004之懸臂樑螺桿式的方法來負荷應力，測定於150℃之溫度下保持指定時間後之殘留應力率。The stress relaxation resistance test was carried out according to the cantilever beam type method of the Japan Copper Association Technical Standard JCBA-T309:2004, and the residual stress rate after the specified time was maintained at a temperature of 150 ° C.

作為試驗方法，係由各供試材以與長度方向平行地採取試驗片(寬度10mm)，以使試驗片之表面最大應力成為耐力之80%的方式，將初期撓曲位移設定為2mm，來調整跨距長度。上述表面最大應力係以次式規定。As a test method, a test piece (width: 10 mm) was taken from each of the test materials in parallel with the longitudinal direction so that the maximum surface stress of the test piece became 80% of the endurance, and the initial deflection displacement was set to 2 mm. Adjust the span length. The above surface maximum stress is defined by the following formula.

表面應力(MPa)=1.5Etδ₀/L_s ²，惟Surface stress (MPa) = 1.5Etδ ₀ /L _s ² ,

E：撓曲係數(MPa)E: deflection coefficient (MPa)

t：試樣之厚度(t=0.25mm)t: thickness of the sample (t = 0.25 mm)

δ₀：初期撓曲位移(2mm)δ ₀ : initial deflection displacement (2mm)

L_s：跨距長度(mm)。L _s : span length (mm).

於150℃之溫度，由保持80h後之彎曲習慣來測定殘留應力率，以其值為70%以上者定為A、60%以上且低於70%者定為B、50%以上且低於60%者定為C、低於50%者定為D來評估。再者殘留應力率係使用次式算出。At a temperature of 150 ° C, the residual stress rate is determined by the bending habit after 80 h, and the value of A, 60% or more and less than 70% is determined to be B, 50% or more and lower than 70% or more. 60% of those who are classified as C and less than 50% are assessed as D. Furthermore, the residual stress rate is calculated using the following formula.

殘留應力率(%)=(1-δ_t/δ₀)×100，惟Residual stress rate (%) = (1 - δ _t / δ ₀ ) × 100,

δ_t：於150℃保持80h後之永久撓曲位移(mm)δ _t : permanent deflection displacement (mm) after holding at 150 ° C for 80 h

δ₀：初期撓曲位移(mm)。δ ₀ : initial deflection displacement (mm).

[析出物之觀察][observation of precipitates]

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研磨、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。The strips for each characteristic evaluation were subjected to observation of the structure for confirming the precipitates. The rolling surface of each sample was mirror-polished and etched, and observed by an FE-SEM (Field Emission Scanning Electron Microscope) at about 40,000 times. Moreover, the component of the precipitate was confirmed by EDX (energy dispersive X-ray spectroscopy).

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，作為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。The results of the above evaluations are shown in Tables 7 to 9. Moreover, the FE-SEM observation photograph of the No. 2 sample of the present invention example is shown in Fig. 1 as an example of the above-described tissue observation. Further, the results of EDX (energy dispersive X-ray spectroscopy) analysis of the precipitates in the No. 2 sample of the present invention example are shown in Fig. 2 .

[表1][Table 1]

[本發明例][Example of the invention]

[表2][Table 2]

[本發明例][Example of the invention]

[表3][table 3]

[比較例][Comparative example]

[表4][Table 4]

[本發明例][Example of the invention]

[表5][table 5]

[本發明例][Example of the invention]

[表6][Table 6]

[比較例][Comparative example]

[表7][Table 7]

[本發明例][Example of the invention]

[表8][Table 8]

[本發明例][Example of the invention]

[表9][Table 9]

[比較例][Comparative example]

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)，確認了該析出物為含有Fe、P者、亦即已定義之[Ni,Fe]-P系析出物的一種。In Fig. 1, the white elliptical portion near the center is a 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.

進一步地，說明各試樣之評估結果。再者，No.1~No.16為以含有30%左右之Zn的Cu-30Zn合金為基質的本發明例、No.17~No.27為以含有25%左右之Zn的Cu-25Zn合金為基質的本發明例、No.28~No.39為以含有35%左右之Zn的Cu-35Zn合金為基質的本發明例、又No.41、No.42、No.44~No.54、No.56、No.57為以含有30%左右之Zn的Cu-30Zn合金為基質的比較例、No.42為含有37.1%之Zn的比較例、No.55為以含有25%左右之Zn的Cu-25Zn合金為基質的比較例。Further, the evaluation results of the respective samples will be described. In addition, No. 1 to No. 16 are examples of the present invention based on a Cu-30Zn alloy containing about 30% of Zn, and No. 17 to No. 27 are Cu-25Zn alloys containing about 25% of Zn. The present invention example of the substrate, No. 28 to No. 39, is an example of the present invention based on a Cu-35Zn alloy containing about 35% of Zn, and No. 41, No. 42, No. 44 to No. 54. No. 56 and No. 57 are comparative examples in which Cu-30Zn alloy containing about 30% of Zn is used as a matrix, No. 42 is a comparative example containing 37.1% of Zn, and No. 55 is contained in about 25%. A comparative example of a Cu-25Zn alloy of Zn as a matrix.

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，殘留應力率均為60%以上，其耐應力緩和特性優良，此外，導電率亦為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3mm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。As shown in Tables 7 and 8, not only the individual content of each alloying element is within the range specified by the present invention, but also the ratio of each alloy component to each other within the range specified by the present invention is No. 1 to No. 39 of the present invention. The residual stress rate is 60% or more, and the stress relaxation resistance is excellent. In addition, the electrical conductivity is also 21% IACS or more, and can be sufficiently applied to joints or other terminal members, and the edge crack of the rolling delay is hardly changed. Or even if it is less than 3 mm in length, it is confirmed that the rolling property is good and the strength is not inferior to the conventional material.

另一方面，如表9所示，比較例之No.41為由Cu-30Zn合金所成之習知材料、比較例之No.42為於Cu-30Zn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-30Zn合金為基質的本發明例No.1~No.16為劣。On the other hand, as shown in Table 9, the comparative example No. 41 is a conventional material formed of a Cu-30Zn alloy, and the comparative example No. 42 is a conventional one in which only Sn is added to the Cu-30Zn alloy. The material, the stress relaxation resistance characteristics of these are inferior to the inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy.

又，比較例之No.43因Zn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。Further, in No. 43 of the comparative example, since the amount of Zn was excessive, cracking occurred during cold rolling (modification rolling), and subsequent low-temperature heat treatment could not be carried out, and evaluation of each performance could not be carried out.

進一步地比較例No.44因為Sn量過剩，故熱軋延時會發生破裂，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因為無添加Sn，故相較於以Cu-30Zn合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。Further, in Comparative Example No. 44, since the amount of Sn was excessive, the hot rolling delay occurred, and the subsequent steps could not be carried out, and each performance evaluation could not be carried out. On the other hand, in Comparative Example No. 45, since Sn was not added, the stress relaxation characteristics were inferior to those of the inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy.

又，比較例No.46因為Ni量過剩，故相較於以Cu-30Zn合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。另一方面，比較例No.47因為無添加Ni，故相較於以Cu-30Zn合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。Further, in Comparative Example No. 46, since the amount of Ni was excessive, the stress relaxation characteristics of the present invention were inferior to those of the inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy. 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.

又，比較例No.48因為Fe量過剩，故導電率低達20%IACS以下，而且相較於以Cu-30Zn合金為基質之本發明例No.1~No.16其耐應力緩和特性亦劣。另一方面，比較例No.49因為無添加Fe，故相較於以Cu-30Zn合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。Further, in Comparative Example No. 48, since the amount of Fe was excessive, the electrical conductivity was as low as 20% IACS or less, and the stress relaxation resistance was also inferior to the inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy. inferior. On the other hand, in Comparative Example No. 49, since Fe was not added, the stress relaxation characteristics were inferior to those of the inventive examples No. 1 to No. 16 based on the Cu-30Zn alloy.

比較例No.50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No.51，因為無添加P，故相較於以Cu-30Zn合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。In Comparative Example No. 50, since the amount of P was excessive, cracking occurred during cold rolling (modification rolling), and subsequent low-temperature heat treatment could not be carried out, and evaluation of each property could not be carried out. On the other hand, in Comparative Example No. 51, since no P 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.

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。In the comparative examples, No. 52 to No. 57, the respective contents of the respective alloying elements are within the range defined by the present invention, but the content ratio (atomic ratio) of each of the alloying elements is outside the range specified by the present invention. .

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合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。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合金為基質之本發明例No.1~No.16，其耐應力緩和特性亦劣。First, in the comparative example of No. 52, the Fe/Ni ratio is lower than the lower limit of the formula (1), and in this case, compared with the inventive examples No. 1 to No. 16, which are based on the Cu-30Zn alloy, 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, the inventive examples No. 1 to No are based on the Cu-30Zn alloy. .16, its stress relaxation characteristics are also inferior.

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合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。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合金為基質之本發明例No.17~No.27，其耐應力緩和特性為劣。Further, in the comparative example of No. 54, the (Ni + Fe) / P ratio is lower than the lower limit of the formula (2), and in this case, the inventive example No. 1 ~ 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.

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合金為基質之本發明例No.1~No.16，其耐應力緩和特性為劣。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, its stress relaxation resistance is inferior.

另一方面，No.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合金為基質之本發明例No.1~No.16，其耐應力緩和特性亦劣。On the other hand, in the comparative example of No. 57, the Sn/(Ni+Fe) ratio is higher than the upper limit of the formula (3), and in this case, the present invention No. is based on the Cu-30Zn alloy. .1~No.16, its stress relaxation resistance is also inferior.

[產業上之可利用性][Industrial availability]

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、其他端子等之導電構件，可提供優良特性之電子/電氣機器用零件。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.

圖1為對本發明之實施例的本發明例No.2的合金以FE-SEM(場發射型掃描電子顯微鏡)觀察而得之含有析出物之部位的組織照片。Fig. 1 is a photograph showing the structure of a portion containing an precipitate obtained by an FE-SEM (field emission type scanning electron microscope) of an alloy of the invention example No. 2 according to an example of the present invention.

圖2為顯示對圖1中之析出物以EDX(能量分散型X射線分光法)之分析結果的圖表。Fig. 2 is a graph showing the results of analysis of the precipitates in Fig. 1 by EDX (energy dispersive X-ray spectroscopy).

Claims (6)

一種電子/電氣機器用銅合金，其特徵為：含有Zn 23~36.5%(mass%、以下相同)、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0.05＜Fe/Ni＜1.5，且Ni及Fe之合計含量(Ni+Fe)與P含量之比(Ni+Fe)/P，以原子比計滿足3＜(Ni+Fe)/P＜15，進一步地，Sn含量與Ni及Fe之合計量(Ni+Fe)的比Sn/(Ni+Fe)，以原子比計滿足0.5＜Sn/(Ni+Fe)＜5，剩餘部分為Cu及不可避免之雜質所構成。A copper alloy for an electronic/electrical machine, 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 than 0.15%, Fe 0.005% or more and less 0.10%, P 0.005~0.05%, and the ratio of Fe content to Ni content Fe/Ni, which satisfies 0.05<Fe/Ni<1.5 in atomic ratio, and the total content of Ni and Fe (Ni+Fe) and P content The ratio (Ni+Fe)/P satisfies 3<(Ni+Fe)/P<15 in atomic ratio, and further, the ratio of Sn content to the total amount of Ni and Fe (Ni+Fe) Sn/(Ni+ Fe) is composed of 0.5<Sn/(Ni+Fe)<5 in atomic ratio, and the remainder is Cu and unavoidable impurities. 一種電子/電氣機器用銅合金，其特徵為：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)/Ni＜1.5，且Ni、Fe及Co之合計含量(Ni+Fe+Co)與P含量的比(Ni+Fe+Co)/P，以原子比計滿足3＜(Ni+Fe+Co)/P＜15，進一步地，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，剩餘部分為Cu及不可避免之雜質所構成。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%, and Co 0.005% or more And less than 0.10%, P 0.005~0.05%, and the ratio of the total content of Fe and Co to the content of Ni (Fe+Co)/Ni, which satisfies 0.05<(Fe+Co)/Ni<1.5 in atomic ratio, and The ratio of the total content of Ni, Fe, and Co (Ni+Fe+Co) to the P content (Ni+Fe+Co)/P, which satisfies 3<(Ni+Fe+Co)/P<15 in atomic ratio, further Ground, the ratio of the Sn content to the total content of Ni, Fe, and Co (Ni+Fe+Co), Sn/(Ni+Fe+Co), satisfies 0.5<Sn/(Ni+Fe+Co)<5 in atomic ratio. The remainder is composed of Cu and unavoidable impurities. 一種電子/電氣機器用銅合金薄板，其係由如申請專利範圍第1項或第2項之銅合金的軋延材所構成，且厚度在0.05~1.0mm之範圍內。A copper alloy sheet for an electronic/electrical machine, which is composed of a rolled material of a copper alloy according to the first or second aspect of the patent application, and has a thickness in the range of 0.05 to 1.0 mm. 一種電子/電氣機器用銅合金薄板，其係於如申請專利範圍第3項之銅合金薄板的表面施以有鍍Sn。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 paragraph of the patent application. 一種電子/電氣機器用導電構件，其係由如申請專利範圍第3項之銅合金薄板所構成，且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，其中，於板面之至少一部分施以有彎曲加工，且係以藉由該彎曲部分之彈簧性來維持與對側導電材之接觸的方式構成。A conductive member for an electronic/electrical machine, which is composed of a copper alloy sheet as claimed in claim 3, and is used to contact the opposite side conductive member to obtain a conductive member electrically connected to the opposite side conductive member, wherein At least a part of the plate surface is subjected to bending processing, and is configured to maintain contact with the opposite side conductive material by the spring property of the curved portion. 一種電子/電氣機器用導電構件，其係由如申請專利範圍第4項之銅合金薄板所構成，且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，其中，於板面之至少一部分施以有彎曲加工，且係以藉由該彎曲部分之彈簧性來維持與對側導電材之接觸的方式構成。A conductive member for an electronic/electrical machine, which is composed of a copper alloy sheet as in claim 4, and is used to contact the opposite side conductive member to obtain a conductive member electrically connected to the opposite side conductive member, wherein At least a part of the plate surface is subjected to bending processing, and is configured to maintain contact with the opposite side conductive material by the spring property of the curved portion.