TW201738394A - Copper alloy for electronic/electric device, copper alloy sheet or strip for electronic/electric device, component for electronic/electric device, terminal, bus bar, and movable piece for relay - Google Patents
Copper alloy for electronic/electric device, copper alloy sheet or strip for electronic/electric device, component for electronic/electric device, terminal, bus bar, and movable piece for relay Download PDFInfo
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- C22C9/00—Alloys based on copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H50/00—Details of electromagnetic relays
- H01H50/14—Terminal arrangements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H50/00—Details of electromagnetic relays
- H01H50/54—Contact arrangements
- H01H50/56—Contact spring sets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members
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Abstract
Description
本發明係有關適用於連接器或壓入配合等之端子、導線架、匯流條、中繼用可動片等之電子.電氣機器用零件之電子.電氣機器用銅合金、及由該電子.電氣機器用銅合金所成之電子.電氣機器用銅合金板條材、電子.電氣機器用零件、端子、匯流條、及中繼用可動片者。 The present invention relates to an electronic device suitable for a connector, a press-fit terminal, a lead frame, a bus bar, a relay movable piece, and the like. Electronics for electrical machine parts. Copper alloy for electrical equipment, and by the electron. An electronic device made of copper alloy for electrical equipment. Copper alloy sheet and strip for electrical equipment, electronics. Parts for electrical equipment, terminals, bus bars, and movable parts for relays.
本申請案係基於2016年3月30日於日本提出申請之日本特願2016-069080號及2017年3月28日於日本提出申請之日本特願2017-063418號而主張優先權,其內容援用於本文。 This application claims priority based on Japanese Patent Application No. 2016-069080 filed in Japan on March 30, 2016, and Japanese Patent Application No. 2017-063418 filed on March 28, 2017 in Japan. In this article.
以往,連接器或壓入配合等之端子、中繼用 可動片、導線架、匯流條等等之電子.電氣機器用零件係使用導電性高的銅或銅合金。 In the past, terminals and relays for connectors or press fits The movable piece, the lead frame, the bus bar, etc. For electrical equipment parts, copper or copper alloy with high conductivity is used.
此處,隨著電子機器或電氣機器等小型化,亦實現該等電子機器或電氣機器等所使用之電子.電氣機器用零件之小型化及薄片化。因此,對構成電子.電氣機器用零件之材料,要求高強度及良好彎曲加工性。且,對於於汽車等之引擎室等之高溫環境下使用之連接器之端子等亦要求耐應力緩和特性。 Here, with the miniaturization of electronic equipment or electrical equipment, the electronic equipment used in such electronic equipment or electrical equipment is also realized. Miniaturization and thinning of parts for electrical equipment. Therefore, the composition of the electrons. Materials for electrical machine parts require high strength and good bending workability. Further, the terminal of the connector used in a high-temperature environment such as an engine room of an automobile or the like is also required to have stress relaxation resistance.
作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件所使用之材料,於例如專利文獻1、2中提案有Cu-Mg系合金。 As a connector or press-fit terminal, relay movable piece, lead frame, bus bar, etc. For the materials used for the parts for electrical equipment, for example, Patent Documents 1 and 2 propose a Cu-Mg-based alloy.
[專利文獻1]日本專利第5045783號公報(B) [Patent Document 1] Japanese Patent No. 5045783 (B)
[專利文獻2]日本特開2014-114464號公報(A) [Patent Document 2] Japanese Laid-Open Patent Publication No. 2014-114464 (A)
此處,專利文獻1中記載之Cu-Mg系合金中,由於Mg含量多,故導電性不充分,難以適用於要求高導電性之用途。 In the Cu-Mg-based alloy described in Patent Document 1, since the Mg content is large, the conductivity is insufficient, and it is difficult to apply it to applications requiring high conductivity.
且,專利文獻2中記載之Cu-Mg系合金中,Mg含量設為0.01~0.5mass%及P含量設為0.01~0.5mass%,並未 針對冷加工性及彎曲加工性大為劣化之粗大化合物加以考慮,故冷加工性及彎曲加工性不充分。 Further, in the Cu-Mg-based alloy described in Patent Document 2, the Mg content is set to 0.01 to 0.5 mass%, and the P content is set to 0.01 to 0.5 mass%, which is not In consideration of the coarse compound which is greatly deteriorated in cold workability and bending workability, cold workability and bending workability are insufficient.
再者,上述之Cu-Mg系合金中,由於Mg而使銅合金熔浴黏度上升,故未添加P時,會有鑄造性降低之問題。 Further, in the Cu-Mg-based alloy described above, since the viscosity of the molten alloy of the copper alloy is increased by Mg, when P is not added, there is a problem that the castability is lowered.
且,最近,隨著電子.電氣機器之輕量化,而實現該等電子機器或電氣機器等所使用之連接器等之端子、中繼用可動片、導線架等之電子.電氣機器用零件之薄片化。因此,連接器等之端子中,為了確保壓接,有必要進行嚴格的彎曲加工,而要求比以往更增加之彎曲加工性。 And, recently, with electronics. The weight of the electric equipment is reduced, and the terminals such as connectors, relay movable sheets, and lead frames used in such electronic equipment and electric equipment are realized. Thinning of parts for electrical equipment. Therefore, in the terminals of the connector or the like, in order to secure the pressure bonding, it is necessary to perform a strict bending process, and it is required to have more bending workability than ever.
本發明係鑑於前述情況者,其目的在於提供導電性、彎曲加工性優異之電子.電氣機器用銅合金、電子.電氣機器用銅合金板條材、電子.電氣機器用零件、端子、匯流條、及中繼用可動片。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an electron having excellent conductivity and bending workability. Copper alloys and electronics for electrical equipment. Copper alloy sheet and strip for electrical equipment, electronics. Parts for electrical equipment, terminals, bus bars, and movable sheets for relays.
為了解決該課題,本發明一樣態之電子.電氣機器用銅合金(以下稱為「本發明之電子.電氣機器用銅合金」),其特徵係以0.15mass%以上、未達0.35mass%之範圍內含有Mg,以0.0005mass%以上、未達0.01mass%之範圍內含有P,其餘部分由Cu及不可避免雜質所成,且導電率超過75%IACS,並且於掃描型電子顯微鏡觀察中,粒徑0.1μm以上之含有Mg及P之化合物的平均個數為0.5個/μm2以下。 In order to solve this problem, the present invention is the same state of the art. Copper alloy for electric equipment (hereinafter referred to as "the copper alloy for electric and electric equipment of the present invention") is characterized in that it contains Mg in a range of 0.15 mass% or more and less than 0.35 mass%, and is 0.0005 mass% or more. P is contained in the range of 0.01 mass%, and the remainder is formed of Cu and unavoidable impurities, and the conductivity is more than 75% IACS, and the compound containing Mg and P having a particle diameter of 0.1 μm or more is observed by scanning electron microscopy. The average number is 0.5/μm 2 or less.
依據上述構成之電子.電氣機器用銅合金,由於Mg含量設為0.15mass%以上、未達0.35mass%之範圍內,故銅之母相中固熔Mg,因此不使導電率大幅降低,而可提高強度、耐應力緩和特性。具體而言,由於導電率超過75%IACS,故亦可適用於要求高導電性之用途。且,由於以0.0005mass%以上、未達0.01mass%之範圍內含有P,故可使包含Mg之銅合金熔浴黏度降低,可提高鑄造性。 According to the above composition of the electron. In the copper alloy for electric equipment, since the Mg content is in the range of 0.15 mass% or more and less than 0.35 mass%, the mother phase of copper solid-melts Mg, so that the electrical conductivity is not greatly lowered, and the strength and stress resistance can be improved. Moderate properties. Specifically, since the electrical conductivity exceeds 75% IACS, it can also be applied to applications requiring high electrical conductivity. Further, since P is contained in a range of 0.0005 mass% or more and less than 0.01 mass%, the molten bath of the copper alloy containing Mg can be lowered, and the castability can be improved.
而且,於掃描型電子顯微鏡觀察中,粒徑0.1μm以上之含有Mg及P之化合物的平均個數為0.5個/μm2以下,故母相中,成為龜裂起點之粗大含有Mg及P之化合物多數未分散,故成為彎曲加工性提高。因此,可成形複雜形狀之連接器等之端子、中繼用可動片、導線架等之電子.電氣機器用零件等。 In addition, in the observation by scanning electron microscopy, the average number of compounds containing Mg and P having a particle diameter of 0.1 μm or more is 0.5/μm 2 or less, so that the mother's phase is coarse and contains Mg and P. Since many of the compounds are not dispersed, the bending workability is improved. Therefore, it is possible to form a connector such as a connector of a complicated shape, a movable piece for relay, a lead frame, or the like. Parts for electrical equipment, etc.
此處,本發明之電子.電氣機器用銅合金中,較好Mg之含量[Mg](mass%)與P之含量[P](mass%)滿足下述之關係式:[Mg]+20×[P]<0.5。 Here, the electron of the present invention. In the copper alloy for electric equipment, the content of Mg [Mg] (mass%) and the content of P [P] (mass%) satisfy the following relationship: [Mg] + 20 × [P] < 0.5.
該情況,可抑制含有Mg及P之粗大化合物之生成,可抑制冷加工性及彎曲加工性降低。 In this case, the formation of a coarse compound containing Mg and P can be suppressed, and the cold workability and the bending workability can be suppressed from being lowered.
且,本發明之電子.電氣機器用銅合金中,較好Mg之含量[Mg](mass%)與P之含量[P](mass%)滿足下述之關係式:[Mg]/[P]≦400。 Moreover, the electron of the present invention. In the copper alloy for electric equipment, the content of Mg [Mg] (mass%) and the content of P [P] (mass%) satisfy the following relationship: [Mg] / [P] ≦ 400.
該情況,使鑄造性降低之Mg含量與使鑄造性提高之P含量之比率藉由如上述般規定,可確實提高鑄造性。 In this case, the ratio of the Mg content at which the castability is lowered to the P content at which the castability is improved is defined as described above, and the castability can be surely improved.
再者,本發明之電子.電氣機器用銅合金中,較好於對於壓延方向正交之方向進行拉伸試驗時之0.2%耐力為300MPa以上。 Furthermore, the electron of the present invention. In the copper alloy for electric equipment, it is preferable that the 0.2% proof force in the tensile test in the direction orthogonal to the rolling direction is 300 MPa or more.
該情況下,由於於對於壓延方向正交之方向進行拉伸試驗時之0.2%耐力如上述般規定,故不容易變形,特別適合作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件之銅合金。 In this case, since the 0.2% proof force in the tensile test in the direction perpendicular to the rolling direction is defined as described above, it is not easily deformed, and is particularly suitable as a terminal for a connector or a press fit, and a movable piece for relay. , lead frame, bus bar and other electronic. Copper alloy for parts used in electrical equipment.
又,本發明之電子.電氣機器用銅合金中,較好殘留應力率於150℃、1000小時為50%以上。 Also, the electron of the present invention. In the copper alloy for electrical equipment, the preferable residual stress rate is 150 ° C and 50% or more in 1000 hours.
該情況下,由於應力緩和率如上述般規定,故即使於高溫環境下使用時亦可將永久變形抑制為較小,例如可抑制連接器端子等之壓接降低。因此,可適用作為於引擎室等之高溫環境下使用之電子機器用零件之材料。 In this case, since the stress relaxation rate is defined as described above, the permanent deformation can be suppressed to be small even when used in a high-temperature environment, and for example, the pressure contact of the connector terminal or the like can be suppressed from being lowered. Therefore, it can be applied to a material for an electronic device component used in a high temperature environment such as an engine room.
本發明之其他樣態之電子.電氣機器用銅合金板條材(以下稱為「本發明之電子.電氣機器用銅合金板條材」),其特徵係由上述之電子.電氣機器用銅合金所成。 Other forms of the invention. Copper alloy strips for electrical equipment (hereinafter referred to as "the copper alloy sheet strips for electronic and electrical equipment of the present invention") are characterized by the above-mentioned electrons. Electrical equipment is made of copper alloy.
依據該構成之電子.電氣機器用銅合金板條材,由於以上述之電子.電氣機器用銅合金所構成,故導電性、強度、彎曲加工性、耐應力緩和特性優異,特別適合作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件之材料。 According to the composition of the electron. Copper alloy strips for electrical machines, due to the above mentioned electrons. Since the electrical equipment is made of a copper alloy, it is excellent in electrical conductivity, strength, bending workability, and stress relaxation resistance, and is particularly suitable as a terminal for a connector or a press fit, a movable piece for relay, a lead frame, a bus bar, and the like. electronic. Material for parts used in electrical equipment.
又,本發明之電子.電氣機器用銅合金板條材,係包含板材即將其捲取為線圈狀之條材。 Also, the electron of the present invention. A copper alloy sheet material for an electrical machine is a strip containing a sheet which is to be wound into a coil shape.
此處,本發明之電子.電氣機器用銅合金板條材中,較好表面具有Sn鍍敷層或Ag鍍敷層。 Here, the electron of the present invention. In the copper alloy sheet material for electric equipment, it is preferred that the surface has a Sn plating layer or an Ag plating layer.
該情況下,由於表面具有Sn鍍敷層或Ag鍍敷層,故特別適合作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件之材料。又,本發明中,「Sn鍍敷」包含純Sn鍍敷或Sn合金鍍敷,「Ag鍍敷」包含純Ag鍍敷或Ag合金鍍敷。 In this case, since the surface has a Sn plating layer or an Ag plating layer, it is particularly suitable as a connector, a terminal for press fitting or the like, a relay movable sheet, a lead frame, a bus bar, and the like. Material for parts used in electrical equipment. Further, in the present invention, "Sn plating" includes pure Sn plating or Sn alloy plating, and "Ag plating" includes pure Ag plating or Ag alloy plating.
本發明之其他樣態之電子.電氣機器用零件(以下稱為「本發明之電子.電氣機器用零件」),其特徵係由上述之電子.電氣機器用銅合金板條材所成。又,本發明之電子.電氣機器用零件係包含連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等者。該構成之電子.電氣機器用零件由於係使用上述之電子.電氣機器用銅合金板條材製造,故即使於小型化及薄片化時亦可發揮優異特性。 Other forms of the invention. The parts for electrical equipment (hereinafter referred to as "the parts of the electronic and electrical equipment of the present invention") are characterized by the above-mentioned electrons. Electrical machines are made of copper alloy strips. Also, the electron of the present invention. The parts for electrical equipment include terminals such as connectors and press fits, movable sheets for relays, lead frames, bus bars, and the like. The composition of the electron. Parts for electrical equipment use the above-mentioned electronics. Since the electrical equipment is made of a copper alloy sheet material, it can exhibit excellent characteristics even when it is miniaturized and thinned.
又,本發明之電子.電氣機器用零件中,表面亦可具有Sn鍍敷層或Ag鍍敷層。又,Sn鍍敷層及Ag鍍敷層亦可預先形成於電子.電氣機器用銅合金板條材,亦可於成形電子.電氣機器用零件後形成。 Also, the electron of the present invention. In the parts for electrical equipment, the surface may also have a Sn plating layer or an Ag plating layer. Moreover, the Sn plating layer and the Ag plating layer may be formed in advance in the electron. Copper alloy sheet metal for electrical equipment can also be used to form electrons. Formed after parts for electrical equipment.
本發明其他樣態之端子(以下稱為「本發明之端子」),其特徵係由上述之電子.電氣機器用銅合金板條材所成。 Other terminals of the present invention (hereinafter referred to as "terminals of the present invention") are characterized by the above-mentioned electrons. Electrical machines are made of copper alloy strips.
該構成之端子,由於係使用上述之電子.電氣機器用銅合金板條材製造,故即使於小型化及薄片化時亦可發揮 優異特性。 The terminal of this configuration is due to the use of the above mentioned electrons. Electrical equipment is made of copper alloy strips, so it can be used even when miniaturized and thinned. Excellent characteristics.
且,本發明之端子中,表面亦可具有Sn鍍敷層或Ag鍍敷層。又,Sn鍍敷層及Ag鍍敷層亦可預先形成於電子.電氣機器用銅合金板條材,亦可於成形端子後形成。 Further, in the terminal of the present invention, the surface may have a Sn plating layer or an Ag plating layer. Moreover, the Sn plating layer and the Ag plating layer may be formed in advance in the electron. Copper alloy strips for electrical equipment can also be formed after forming the terminals.
本發明其他樣態之匯流條(以下稱為「本發明之匯流條」),其特徵係由上述之電子.電氣機器用銅合金板條材所成。 The bus bar of other aspects of the present invention (hereinafter referred to as "the bus bar of the present invention") is characterized by the above-mentioned electrons. Electrical machines are made of copper alloy strips.
此構成之匯流條由於係使用上述之電子.電氣機器用銅合金板條材製造,故即使於小型化及薄片化時亦可發揮優異特性。 This constituent bus bar uses the above-mentioned electrons. Since the electrical equipment is made of a copper alloy sheet material, it can exhibit excellent characteristics even when it is miniaturized and thinned.
又,本發明之匯流條中,表面亦可具有Sn鍍敷層或Ag鍍敷層。又,Sn鍍敷層及Ag鍍敷層亦可預先形成於電子.電氣機器用銅合金板條材,亦可於成形匯流條後形成。 Further, in the bus bar of the present invention, the surface may have a Sn plating layer or an Ag plating layer. Moreover, the Sn plating layer and the Ag plating layer may be formed in advance in the electron. Copper alloy sheet strips for electrical equipment can also be formed after forming bus bars.
本發明其他樣態之中繼用可動片(以下稱為「本發明之中繼用可動片」),其特徵係由上述之電子.電氣機器用銅合金板條材所成。 Another embodiment of the relay movable sheet (hereinafter referred to as "the relay movable sheet of the present invention") is characterized by the above-mentioned electronic. Electrical machines are made of copper alloy strips.
該構成之中繼用可動片由於係使用上述之電子.電氣機器用銅合金板條材製造,故即使於小型化及薄片化時亦可發揮優異特性。 The relay movable piece of this configuration uses the above-mentioned electrons. Since the electrical equipment is made of a copper alloy sheet material, it can exhibit excellent characteristics even when it is miniaturized and thinned.
又,本發明之中繼用可動片中,表面亦可具有Sn鍍敷層或Ag鍍敷層。又,Sn鍍敷層及Ag鍍敷層亦可預先形成於電子.電氣機器用銅合金板條材,亦可於成形中繼用可動片後形成。 Further, in the movable movable sheet of the present invention, the surface may have a Sn plating layer or an Ag plating layer. Moreover, the Sn plating layer and the Ag plating layer may be formed in advance in the electron. Copper alloy strips for electrical equipment can also be formed after the movable piece for forming the relay.
依據本發明,可提供導電性、彎曲加工性優異之電子.電氣機器用銅合金、電子.電氣機器用銅合金板條材、電子.電氣機器用零件、端子、匯流條、及中繼用可動片。 According to the present invention, an electron having excellent conductivity and bending workability can be provided. Copper alloys and electronics for electrical equipment. Copper alloy sheet and strip for electrical equipment, electronics. Parts for electrical equipment, terminals, bus bars, and movable sheets for relays.
圖1係本實施形態之電子.電氣機器用銅合金之製造方法之流程圖。 Figure 1 is the electron of this embodiment. Flowchart of a method for producing a copper alloy for electrical equipment.
圖2A係顯示本實施例之化合物之觀察結果的一例之照片。 Fig. 2A is a photograph showing an example of the observation result of the compound of the present example.
圖2B係顯示本實施例之化合物之觀察結果的一例之EDX分析結果。 Fig. 2B is a result of EDX analysis showing an example of the observation result of the compound of the present example.
以下,針對本發明一實施形態之電子.電氣機器用銅合金加以說明。 Hereinafter, an electron according to an embodiment of the present invention. The electrical machine is described by a copper alloy.
本實施形態之電子.電氣機器用銅合金具有如下組成:以0.15mass%以上、未達0.35mass%之範圍內含有Mg,以0.0005mass%以上、未達0.01mass%之範圍內含有P,其餘部分由Cu及不可避免雜質所成。 The electron of this embodiment. The copper alloy for electric equipment has a composition containing Mg in a range of 0.15 mass% or more and less than 0.35 mass%, P in a range of 0.0005 mass% or more, less than 0.01 mass%, and the balance being Cu and inevitable. Made up of impurities.
又,本實施形態之電子.電氣機器用銅合金中,導電 率超過75%IACS。 Moreover, the electron of this embodiment. Conductive in copper alloys for electrical equipment The rate is over 75% IACS.
而且,本實施形態之電子.電氣機器用銅合金中,於掃描型電子顯微鏡觀察中,粒徑0.1μm以上之含有Mg及P之化合物的平均個數為0.5個/μm2以下。 Moreover, the electron of this embodiment. In the copper alloy for electric equipment, the average number of compounds containing Mg and P having a particle diameter of 0.1 μm or more is 0.5/μm 2 or less in scanning electron microscope observation.
又,本實施形態之電子.電氣機器用銅合金中,Mg之含量[Mg](mass%)與P之含量[P](mass%)滿足下述之關係式: Moreover, the electron of this embodiment. In the copper alloy for electrical equipment, the content of Mg [Mg] (mass%) and the content of P [P] (mass%) satisfy the following relationship:
[Mg]+20×[P]<0.5。 [Mg] + 20 × [P] < 0.5.
再者,本實施形態中,Mg之含量[Mg](mass%)與P之含量[P](mass%)滿足下述之關係式: [Mg]/[P]≦400。 Further, in the present embodiment, the content [Mg] (mass%) of Mg and the content [P] (mass%) of P satisfy the following relationship: [Mg]/[P]≦400.
又,本實施形態之電子.電氣機器用銅合金中,於對於壓延方向正交之方向進行拉伸試驗時之0.2%耐力為300MPa以上。亦即,本實施形態中,作成電子.電氣機器用銅合金之壓延材,於壓延之最終步驟中於對於壓延方向正交之方向進行拉伸試驗時之0.2%耐力係如上述般規定。 Moreover, the electron of this embodiment. In the copper alloy for electric equipment, the 0.2% proof force when the tensile test is performed in the direction orthogonal to the rolling direction is 300 MPa or more. That is, in the present embodiment, an electron is created. The rolled material of the copper alloy for electrical equipment is 0.2% in the tensile test in the final step of rolling in the direction perpendicular to the rolling direction.
再者,本實施形態之電子.電氣機器用銅合金中,殘留應力率於150℃、1000小時為50%以上。 Furthermore, the electron of this embodiment. In the copper alloy for electric equipment, the residual stress rate is 50% or more at 150 ° C for 1,000 hours.
此處,針對規定如上述之成分組成、化合物、各種特性之理由說明如下。 Here, the reason for specifying the component composition, the compound, and various characteristics as described above will be described below.
Mg係藉由固熔於銅合金之母相中,而不會使導電率 大幅降低,具有提高強度及耐應力緩和特性之作用的元素。 Mg is solidified in the mother phase of the copper alloy without causing conductivity It is greatly reduced and has an effect of improving strength and stress relaxation properties.
此處,Mg含量未達0.15mass%時,有無法充分發揮其作用效果之虞。另一方面Mg含量為0.35mass%以上時,導電率大幅降低同時銅合金熔浴黏度上升,而有鑄造性降低之虞。 Here, when the Mg content is less than 0.15 mass%, the effect of the action cannot be sufficiently exhibited. On the other hand, when the Mg content is 0.35 mass% or more, the electrical conductivity is largely lowered and the viscosity of the molten alloy of the copper alloy is increased, and the castability is lowered.
基於以上,本實施形態中,將Mg含量設定於0.15mass%以上、未達0.35mass%之範圍內。 Based on the above, in the present embodiment, the Mg content is set to be in the range of 0.15 mass% or more and less than 0.35 mass%.
又,為了進一步提高強度及耐應力緩和特性,Mg含量之下限較好設為0.16mass%以上,又更好設為0.17mass%以上。且,為了確實抑制導電率降低及鑄造性降低,Mg含量之上限較好設為0.30mass%以下,又更好設為0.28mass%以下。 Moreover, in order to further improve the strength and the stress relaxation resistance, the lower limit of the Mg content is preferably 0.16 mass% or more, and more preferably 0.17 mass% or more. Further, in order to surely suppress a decrease in electrical conductivity and a decrease in castability, the upper limit of the Mg content is preferably set to 0.30 mass% or less, and more preferably 0.28 mass% or less.
P係具有提高鑄造性之作用效果之元素。 The P system has an effect of improving the effect of casting properties.
此處,P含量未達0.0005mass%時,有其作用效果無法充分發揮之虞。另一方面P含量為0.01mass%以上時,由於容易生成含有Mg及P之粒徑0.1μm以上之粗大化合物,故有以該化合物為破壞起點,於冷加工時或彎曲加工時產生龜裂之虞。 Here, when the P content is less than 0.0005 mass%, the effect is not sufficiently exhibited. On the other hand, when the P content is 0.01 mass% or more, since a coarse compound containing a particle diameter of Mg and P of 0.1 μm or more is easily formed, the compound may be used as a fracture starting point, and cracks may occur during cold working or bending. .
基於以上,本實施形態中,P含量設定於0.0005mass%以上、未達0.01mass%之範圍內。又,為了確實提高鑄造性,P含量之下限較好為0.0007mass%以 上,又更好為0.001mass%以上。且,為了確實抑制粗大化合物之生成,P含量之上限較好未達0.009mass%,更好未達0.008mass%,又更好為0.0075mass%以下,再更好為0.0050mass%以下。 Based on the above, in the present embodiment, the P content is set to be in the range of 0.0005 mass% or more and less than 0.01 mass%. Further, in order to surely improve the castability, the lower limit of the P content is preferably 0.0007 mass%. Above, it is better than 0.001 mass%. Further, in order to surely suppress the formation of the coarse compound, the upper limit of the P content is preferably less than 0.009 mass%, more preferably less than 0.008 mass%, still more preferably 0.0075 mass% or less, still more preferably 0.0050 mass% or less.
如上述,藉由Mg與P共存,而生成含有Mg及P之化合物。 As described above, by coexisting Mg and P, a compound containing Mg and P is produced.
此處,以質量比計,設定Mg之含量[Mg]與P之含量[P]時,於[Mg]+20×[P]為0.5以上時,Mg及P之總量較多,含有Mg及P之化合物粗大化並且高密度分佈,而有冷加工時或彎曲加工時易產生龜裂之虞。 Here, when the content of Mg [Mg] and the content of P [P] are set in the mass ratio, when [Mg] + 20 × [P] is 0.5 or more, the total amount of Mg and P is large, and Mg is contained. The compound of P and P are coarsened and have a high density distribution, and are prone to cracking during cold working or bending.
基於以上,本實施形態中,[Mg]+20×[P]設定為未達0.5。又,為了確實抑制化合物粗大化及高密度分佈,且抑制冷加工時或彎曲加工時易產生龜裂之發生,較好[Mg]+20×[P]設定為未達0.48,更好未達0.46。又更好未達0.44。 Based on the above, in the present embodiment, [Mg] + 20 × [P] is set to be less than 0.5. Further, in order to suppress the coarsening and high-density distribution of the compound, and to suppress the occurrence of cracks during cold working or bending, it is preferable that [Mg] + 20 × [P] is set to be less than 0.48, preferably less than 0.46. . It is even better than 0.44.
由於Mg係具有使銅合金熔浴之黏度上升、使鑄造性降低之作用之元素,故為了確實提高鑄造性,有必要使Mg與P之含量適當化。 Since Mg has an element which increases the viscosity of the copper alloy molten bath and lowers the castability, it is necessary to appropriately increase the content of Mg and P in order to surely improve the castability.
此處,以質量比計,設定Mg之含量[Mg]與P之含量[P]時,[Mg]/[P]超過400時,Mg含量相對於P變多,有 藉由添加P所致之鑄造性提高效果變小之虞。 Here, when the content of Mg [Mg] and the content of P [P] are set by mass ratio, when [Mg]/[P] exceeds 400, the Mg content increases with respect to P, and The effect of improving the castability by adding P becomes small.
基於以上,本實施形態中,將[Mg]/[P]設定為400以下。為了更提高鑄造性,[Mg]/[P]較好為350以下,更好為300以下。 Based on the above, in the present embodiment, [Mg]/[P] is set to 400 or less. In order to further improve the castability, [Mg]/[P] is preferably 350 or less, more preferably 300 or less.
又,[Mg]/[P]過度低時,Mg作為化合物被消耗,而有無法獲得Mg之固熔所致之效果之虞。為了抑制含有Mg及P之化合物之生成、確實實現藉由Mg之固熔所致之耐力、耐應力緩和特性之提高,較好[Mg]/[P]之下限超過20,更好超過25。 Further, when [Mg]/[P] is excessively low, Mg is consumed as a compound, and there is a possibility that the effect of solidification of Mg cannot be obtained. In order to suppress the formation of a compound containing Mg and P, and to achieve an improvement in endurance and stress relaxation resistance by solid solution of Mg, the lower limit of [Mg]/[P] is preferably more than 20, more preferably more than 25.
作為其他不可避免雜質,舉例為Ag、B、Ca、sr、Ba、Sc、Y、稀土類元素、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Se、Te、Rh、Ir、Ni、Pd、Pt、Au、Zn、Cd、Hg、Al、Ga、In、Ge、Sn、As、Sb、Tl、Pb、Bi、Be、N、C、Si、Li、H、O、S等。該等不可避免雜質由於具有使導電率降低之作用,故總量為0.1mass%以下。 As other unavoidable impurities, for example, Ag, B, Ca, sr, Ba, Sc, Y, rare earth elements, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Se, Te, Rh, Ir, Ni, Pd, Pt, Au, Zn, Cd, Hg, Al, Ga, In, Ge, Sn, As, Sb, Tl, Pb, Bi, Be, N, C, Si, Li, H, O, S, etc. These inevitable impurities have an effect of lowering the electrical conductivity, so the total amount is 0.1 mass% or less.
又,由於Ag、Zn、Sn容易混入銅中使導電率降低,故總量較好未達500massppm。尤其Sn使導電率大為減少,故較好單獨為未達50massppm。 Further, since Ag, Zn, and Sn are easily mixed into copper to lower the electrical conductivity, the total amount is preferably less than 500 mass ppm. In particular, Sn greatly reduces the electrical conductivity, so it is preferably less than 50 mass ppm alone.
再者,Si、Cr、Ti、Zr、Fe、Co尤其可使導電率大幅減少並且因形成化合物而使彎曲加工性劣化,故該等元素總量較好未達500massppm。 Further, Si, Cr, Ti, Zr, Fe, and Co particularly deteriorate the electrical conductivity and deteriorate the bending workability by forming a compound. Therefore, the total amount of these elements is preferably less than 500 mass ppm.
本實施形態之電子.電氣機器用銅合金中,於掃描型電子顯微鏡觀察中,粒徑0.1μm以上之含有Mg及P之化合物的平均個數為0.5個/μm2以下。該等尺寸較大之化合物若多量存在,則以該等化合物成為龜裂起點,而使彎曲加工性大幅劣化。 The electron of this embodiment. In the copper alloy for electric equipment, the average number of compounds containing Mg and P having a particle diameter of 0.1 μm or more is 0.5/μm 2 or less in scanning electron microscope observation. When such a large-sized compound is present in a large amount, the compound becomes a crack origin, and the bending workability is largely deteriorated.
調查組織之結果,粒徑0.1μm以上之含有Mg及P之化合物的平均個數為0.5個/μm2以下時,亦即,不存在或少量存在含有Mg及P之化合物時,獲得良好之彎曲加工性。 As a result of investigation, when the average number of the compound containing Mg and P having a particle diameter of 0.1 μm or more is 0.5/μm 2 or less, that is, when there is no or a small amount of a compound containing Mg and P, good bending is obtained. Processability.
再者,為了確實發揮上述作用效果,更好合金中之粒徑0.05μm以上之含有Mg及P之化合物的平均個數為0.5個/μm2以下。 In addition, in order to surely exhibit the above-described effects, the average number of compounds containing Mg and P having a particle diameter of 0.05 μm or more in the alloy is preferably 0.5/μm 2 or less.
又,含有Mg及P之化合物的平均個數係使用場射出型掃描電子顯微鏡,以倍率:5萬倍,視野:約4.8μm2進行10視野觀察,算出其平均值。 Further, the average number of the compounds containing Mg and P was observed by a field emission type scanning electron microscope at a magnification of 50,000 times and a field of view of about 4.8 μm 2 to obtain an average value.
且,含有Mg及P之化合物之粒徑係設為化合物之長徑(於期間與粒界不相切之條件下於粒內拉出最長直線之長度)與短徑(於與長徑直角相交之方向,於期間與粒界不相切之條件下拉出最長直線之長度)之平均值。粒徑0.1μm以上之含有Mg及P之化合物的每單位面積之平均個數(個數密度)主要可藉由鑄造速度與中間熱處理溫度、熱處理時間而控制。為了減低上述化合物每單位面積 之平均個數(個數密度)時,可藉由將鑄造速度設定為快速、中間熱處理設定為高溫短時間而達成。鑄造速度與中間熱處理條件係適當選擇。 Further, the particle diameter of the compound containing Mg and P is defined as the long diameter of the compound (the length of the longest straight line drawn in the grain under the condition that the period is not tangent to the grain boundary) and the short diameter (intersecting with the right angle of the long diameter) The direction is the average of the length of the longest straight line when the period is not tangent to the grain boundary. The average number per unit area (number density) of the compound containing Mg and P having a particle diameter of 0.1 μm or more can be mainly controlled by the casting speed, the intermediate heat treatment temperature, and the heat treatment time. In order to reduce the above compound per unit area The average number (number density) can be achieved by setting the casting speed to fast and the intermediate heat treatment to a high temperature for a short period of time. The casting speed and the intermediate heat treatment conditions are appropriately selected.
本實施形態之電子.電氣機器用銅合金中,藉由將導電率設為超過75%IACS,而可良好地使用作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件。 The electron of this embodiment. In the copper alloy for electrical equipment, by setting the electrical conductivity to more than 75% IACS, it is possible to use electrons such as terminals for connectors, press-fits, relay movable sheets, lead frames, bus bars, and the like. Parts for electrical machines.
又,導電率較好超過76%IACS,更好超過77%IACS,又更好超過78%IACS,再更好超過80%IACS。 Also, the conductivity is preferably more than 76% IACS, more preferably more than 77% IACS, more preferably more than 78% IACS, and even more preferably more than 80% IACS.
本實施形態之電子.電氣機器用銅合金中,藉由將0.2%耐力設為300MPa以上,成為特別適合作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件之材料。又,本實施形態中,對於壓延方向正交之方向進行拉伸試驗時之0.2%耐力設為300MPa以上。 The electron of this embodiment. In the copper alloy for electric equipment, by setting the 0.2% proof force to 300 MPa or more, it is particularly suitable as a terminal for a connector or press fit, a movable piece for relay, a lead frame, a bus bar, and the like. Material for parts used in electrical equipment. Further, in the present embodiment, the 0.2% proof force when the tensile test is performed in the direction in which the rolling direction is orthogonal is 300 MPa or more.
此處,上述之0.2%耐力較好為325MPa以上,更好350MPa以上。 Here, the above-mentioned 0.2% proof stress is preferably 325 MPa or more, more preferably 350 MPa or more.
本實施形態之電子.電氣機器用銅合金中,如上述,殘留應力率於150℃、1000小時設為50%以上。 The electron of this embodiment. In the copper alloy for electric equipment, as described above, the residual stress rate is 50% or more at 1000 ° C for 1,000 hours.
該條件下之殘留應力率高時,即使於高溫環境下使用時,亦可將永久變形抑制為較小,可抑制壓接之降低。因此,本實施形態之電子機器用銅合金可適合作為在如汽車之引擎室周圍之高溫環境下使用之端子。本實施形態中,對於壓延方向正交之方向進行應力緩和試驗時之殘留應力率於150℃、1000小時設為50%以上。 When the residual stress rate under these conditions is high, even when used in a high-temperature environment, the permanent deformation can be suppressed to be small, and the reduction in pressure bonding can be suppressed. Therefore, the copper alloy for an electronic device of the present embodiment can be suitably used as a terminal for use in a high-temperature environment around an engine room such as an automobile. In the present embodiment, the residual stress rate in the stress relaxation test in the direction in which the rolling direction is orthogonal is 150% or more and 1000% in 1000 hours.
此處,上述殘留應力率較好於150℃、1000小時為60%以上,更好於150℃、1000小時為70%以上。 Here, the residual stress rate is preferably 150 ° C, 60 hours or more in 1000 hours, more preferably 150 ° C, and 70% or more in 1000 hours.
以下,針對如此構成之本實施形態之電子.電氣機器用銅合金之製造方法參考圖1所示之流程圖加以說明。 Hereinafter, the electron of the present embodiment thus constituted is described. The manufacturing method of the copper alloy for electric equipment is demonstrated with reference to the flowchart shown in FIG.
首先,於熔解銅原料所得之銅熔浴中,添加前述元素進行成分調整,製出銅合金熔浴。又,各種元素之添加中,可使用元素單體或母合金。且,亦可將含上述元素之原料作為銅原料並熔解。又,亦可使用本合金之回收材及廢料材。此處,銅熔浴較好為純度99.99mass%以上之所謂4NCu或99.999mass%以上之所謂5NCu。熔解步驟中,為了抑制Mg之氧化,且為了減低氫濃度,較好藉由H2O之蒸氣壓低的惰性環境(例如Ar氣體)進行環境熔解,熔解時之保持時間較好侷限於最小限度。 First, in the copper melting bath obtained by melting the copper raw material, the above elements are added to adjust the composition to prepare a copper alloy molten bath. Further, in the addition of various elements, an elemental monomer or a mother alloy can be used. Further, a raw material containing the above element may be used as a copper raw material and melted. Further, the recycled material and the scrap material of the alloy can also be used. Here, the copper melting bath is preferably a so-called 4NCu or 99.999 mass% or more so-called 5NCu having a purity of 99.99 mass% or more. In the melting step, in order to suppress the oxidation of Mg, and to reduce the hydrogen concentration, it is preferred to carry out environmental melting by an inert atmosphere (for example, Ar gas) having a low vapor pressure of H 2 O, and the holding time during melting is preferably limited to a minimum.
接著,將經成分調整之銅合金熔浴注入鑄模中製出鑄塊。又,考慮量產時,較好使用連續鑄造法或半連續鑄造法。 Next, the composition-adjusted copper alloy molten bath is injected into the mold to produce an ingot. Further, in consideration of mass production, it is preferred to use a continuous casting method or a semi-continuous casting method.
此時,熔浴凝固時,含有Mg及P之化合物作為晶析物而形成,故藉由加快凝固速度,可使含有Mg及P之化合物尺寸更微細。因此,熔浴之冷卻速度較好為0.5℃/sec以上,更好為1℃/sec以上,最好為15℃/sec以上。 At this time, when the molten bath is solidified, a compound containing Mg and P is formed as a crystallization product. Therefore, by increasing the solidification rate, the compound containing Mg and P can be made finer in size. Therefore, the cooling rate of the molten bath is preferably 0.5 ° C / sec or more, more preferably 1 ° C / sec or more, and most preferably 15 ° C / sec or more.
其次,為了使所得鑄塊均質化及熔體化而進行加熱處理。鑄塊內部,存在有於凝固過程中因Mg偏析並濃縮而發生之以Cu及Mg為主成分之金屬間化合物等。因此,為了使該等偏析及金屬間化合物等消失或減低,而藉由進行將鑄塊加熱至300℃以上900℃以下之加熱處理,而於鑄塊內,使Mg均質擴散,使Mg固熔於母相中。又,該均質化/熔體化步驟S02較好在非氧化性或還原性環境中實施。 Next, heat treatment is performed in order to homogenize and melt the obtained ingot. Inside the ingot, there is an intermetallic compound containing Cu and Mg as main components due to segregation and concentration of Mg during solidification. Therefore, in order to cause the segregation and the intermetallic compound or the like to disappear or decrease, the ingot is heated to a temperature of 300 ° C or more and 900 ° C or less, whereby Mg is uniformly diffused in the ingot to solidify the Mg. In the mother phase. Further, the homogenization/melting step S02 is preferably carried out in a non-oxidizing or reducing environment.
此處,加熱溫度未達300℃時,熔體化變不完全,有於母相中殘存較多以Cu及Mg為主成分之金屬間化合物之虞。另一方面,加熱溫度超過900℃時,銅材料之一部分成為液相,有組織或表面狀態變不均一之虞。因此,加熱溫度設定於300℃以上900℃以下之範圍。 Here, when the heating temperature is less than 300 ° C, the melt formation is incomplete, and there is a residual amount of an intermetallic compound containing Cu and Mg as a main component in the mother phase. On the other hand, when the heating temperature exceeds 900 ° C, a part of the copper material becomes a liquid phase, and the structure or surface state becomes uneven. Therefore, the heating temperature is set to a range of from 300 ° C to 900 ° C.
又,為了後述之粗加工效率化與組織均一化,亦可於前述均質化/熔體化步驟S02之後進行熱加工。該情況, 加工方法並未特別限定,可採用例如壓延、拉線、擠出、溝槽壓延、鍛造、壓製等。且,熱加工溫度較好為300℃以上900℃以下之範圍內。 Further, for the roughing efficiency and the uniformity of the structure to be described later, hot working may be performed after the homogenization/melting step S02. In this case, The processing method is not particularly limited, and for example, calendering, wire drawing, extrusion, groove rolling, forging, pressing, or the like can be employed. Further, the hot working temperature is preferably in the range of from 300 ° C to 900 ° C.
為了加工為特定形狀而進行粗加工。又,該粗加工步驟S03中之溫度條件並未特別限定,但為了抑制再結晶,或為了提高尺寸精度,較好設為冷加工或溫加工之-200℃至200℃之範圍內,特佳為常溫。關於加工率(壓延率),較好為20%以上,更好為30%以上。且關於加工方法並未特別限定,可採用例如壓延、拉線、擠出、溝槽壓延、鍛造、壓製等。 Roughing is performed for processing into a specific shape. Further, the temperature condition in the roughing step S03 is not particularly limited, but in order to suppress recrystallization or to improve dimensional accuracy, it is preferably in the range of -200 ° C to 200 ° C in cold working or warm working, particularly preferably Normal temperature. The processing ratio (rolling ratio) is preferably 20% or more, more preferably 30% or more. Further, the processing method is not particularly limited, and for example, calendering, wire drawing, extrusion, groove rolling, forging, pressing, or the like can be employed.
於粗加工步驟S03後,基於用以徹底熔體化、再結晶組織化或加工性提高之軟化為目的而實施熱處理。熱處理方法並未特別限定,但為了不使藉由晶析等所形成之上述化合物之粒徑增大,有必要為高溫、短時間之熱處理步驟,故較佳以400℃以上900℃以下之保持溫度、5秒以上1小時以下之保持時間,更好500℃以上900℃以下之保持溫度、5秒以上30分鐘以下之保持時間進行熱處理。且於非氧化環境或還原性環境中進行熱處理。 After the roughening step S03, heat treatment is performed for the purpose of softening for thorough melt, recrystallization, or improvement in workability. The heat treatment method is not particularly limited. However, in order not to increase the particle diameter of the compound formed by crystallization or the like, it is necessary to carry out a heat treatment step at a high temperature and for a short period of time. Therefore, it is preferably maintained at 400 ° C or higher and 900 ° C or lower. The temperature is maintained for 5 seconds or more and 1 hour or less, more preferably 500 ° C or more and 900 ° C or less, and a holding time of 5 seconds or more and 30 minutes or less. The heat treatment is carried out in a non-oxidizing environment or a reducing environment.
又,加熱後之冷卻方法並未特別限定,但較好採用水淬冷等之冷卻速度為200℃/min以上之方法。 Further, the cooling method after heating is not particularly limited, but a method in which the cooling rate such as water quenching is 200 ° C / min or more is preferably employed.
又,粗加工步驟S03及中間熱處理步驟S04亦可重複實施。 Further, the roughing step S03 and the intermediate heat treatment step S04 may be repeated.
為了將中間熱處理步驟S04後之銅材料加工為特定形狀,而進行整飾加工。又,該經整飾加工步驟S05中之溫度條件並未特別限定,但為了抑制再結晶,或為了抑制軟化,較好設為冷加工或溫加工之-200℃至200℃之範圍內,特佳為常溫。且,加工率雖適當選擇為近似於最終形狀,但為了於整飾加工步驟S05中藉由加工硬化而提高強度,加工率較好為20%以上。且於實現強度進一步提高時,更好加工率設為30%以上,又更好加工率設為40%以上,最好設為60%以上。且由於加工率增加而使彎曲加工性劣化,故較好設為99%以下。 In order to process the copper material after the intermediate heat treatment step S04 into a specific shape, finishing processing is performed. Further, the temperature condition in the finishing processing step S05 is not particularly limited, but in order to suppress recrystallization or to suppress softening, it is preferably in the range of -200 ° C to 200 ° C in cold working or warm working. It is normal temperature. Further, although the processing ratio is appropriately selected to approximate the final shape, in order to improve the strength by work hardening in the finishing processing step S05, the processing ratio is preferably 20% or more. Further, when the strength is further improved, the processing ratio is preferably 30% or more, and the processing ratio is preferably 40% or more, preferably 60% or more. Further, since the bending workability is deteriorated due to an increase in the processing rate, it is preferably set to 99% or less.
其次,對於藉由整飾加工步驟S05所得之塑性加工材,為了提高耐應力緩和特性及低溫燒鈍硬化,且為了去除殘留變形,而實施整飾熱處理。 Next, the plastic working material obtained by the finishing process step S05 is subjected to finishing heat treatment in order to improve the stress relaxation resistance and the low-temperature burn-off hardening, and to remove the residual deformation.
熱處理溫度較好設為100℃以上800℃以下之範圍內,更好為200℃以上700℃以下之範圍內。又,該整飾熱處理步驟S06中,有必要以避免因再結晶而使強度大幅降低之方式,設定熱處理條件(溫度、時間、冷卻速度)。 The heat treatment temperature is preferably in the range of from 100 ° C to 800 ° C, more preferably in the range of from 200 ° C to 700 ° C. Further, in the finishing heat treatment step S06, it is necessary to set the heat treatment conditions (temperature, time, and cooling rate) so as to prevent the strength from being greatly lowered by recrystallization.
例如較好設為於300℃保持1秒至120秒左右。該熱處理較好於非氧化環境或還原性環境中進行。 For example, it is preferably kept at 300 ° C for about 1 second to 120 seconds. The heat treatment is preferably carried out in a non-oxidizing environment or a reducing environment.
熱處理方法並未特別限定,但基於製造成本減低之效果,較好為利用連續燒鈍爐之短時間熱處理。 The heat treatment method is not particularly limited, but it is preferably a short-time heat treatment using a continuous blister furnace based on the effect of reducing the production cost.
再者,上述之整飾加工步驟S05及整飾熱處理步驟S06亦可重複實施。 Furthermore, the finishing process step S05 and the finishing heat treatment step S06 described above may be repeated.
如此,製出本實施形態之電子.電氣機器用銅合金板條材(板材或將其作成線圈形狀之條材)。又,該電子.電氣機器用銅合金板條材之板厚設為超過0.05mm且3.0mm以下之範圍內,較好設為超過0.1mm且未達3.0mm之範圍內。電子.電氣機器用銅合金板條材之板厚為0.05mm以下時,不利於使用作為大電流用途之導體,板厚超過3.0mm時,難以壓製沖壓加工。 Thus, the electron of the embodiment is produced. Copper alloy sheet strips for electrical machines (sheets or strips made into coil shapes). Again, the electron. The thickness of the copper alloy sheet material for electrical equipment is in the range of more than 0.05 mm and 3.0 mm or less, preferably in the range of more than 0.1 mm and less than 3.0 mm. electronic. When the thickness of the copper alloy sheet material for electrical equipment is 0.05 mm or less, it is disadvantageous for use as a conductor for high current use, and when the thickness exceeds 3.0 mm, it is difficult to press press processing.
此處,本實施形態之電子.電氣機器用銅合金板條材可直接使用於電子.電氣機器用零件,但亦可於板面之一面或兩面上,形成膜厚0.1~100μm左右之Sn鍍敷層或Ag鍍敷層。此時,電子.電氣機器用銅合金板條材之板厚較好為鍍敷層厚之10~1000倍。 Here, the electron of this embodiment. Copper alloy strips for electrical machines can be used directly in electronics. For electrical equipment parts, it is also possible to form a Sn plating layer or an Ag plating layer having a thickness of about 0.1 to 100 μm on one or both sides of the board surface. At this time, electronics. The thickness of the copper alloy sheet strip for electrical equipment is preferably 10 to 1000 times the thickness of the plating layer.
再者,藉由將本實施形態之電子.電氣機器用銅合金(電子.電氣機器用銅合金板條材)作為材料,實施沖壓加工或彎曲加工等,而可成形例如連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條之電子.電氣機器用零件。 Furthermore, by using the electrons of this embodiment. A copper alloy for electrical equipment (a copper alloy sheet material for electric and electric equipment) is used as a material, and a press or a bending process or the like is formed, and a terminal such as a connector or a press fit, a relay movable piece, and a lead frame can be formed. The electrons of the bus bar. Parts for electrical machines.
依據如以上構成之本實施形態的電子.電氣 機器用銅合金,由於Mg含量設為0.15mass%以上、未達0.35mass%之範圍內,故藉由Mg於銅之母相中固熔,而不使導電率大幅降低,可提高強度、耐應力緩和特性。又,由於P設為0.0005mass%以上、未達0.01mass%之範圍內,故可使含Mg之銅合金熔浴黏度降低,而可提高鑄造性。 According to the electronic embodiment of the present embodiment constructed as above. electric In the copper alloy for machine, since the Mg content is in the range of 0.15 mass% or more and less than 0.35 mass%, Mg is solid-melted in the mother phase of copper without significantly lowering the electrical conductivity, thereby improving strength and resistance. Stress relaxation properties. Further, since P is made 0.0005 mass% or more and less than 0.01 mass%, the viscosity of the molten copper alloy containing Mg can be lowered, and the castability can be improved.
且,本實施形態之電子.電氣機器用銅合金中,由於導電率設為超過75%IACS,故亦可適用於要求高導電性之用途。 Moreover, the electron of this embodiment. In the copper alloy for electric equipment, since the electrical conductivity is set to more than 75% IACS, it can also be applied to applications requiring high electrical conductivity.
而且,本實施形態之電子.電氣機器用銅合金中,由於於掃描型電子顯微鏡觀察中,粒徑0.1μm以上之含有Mg及P之化合物的平均個數設為0.5個/μm2以下,故於母相中,並未多數分散成為龜裂起點之粗大的含有Mg及P之化合物,而提高彎曲加工性。因此,可成形複雜形狀之連接器等之端子、中繼用可動片、導線架等之電子.電氣機器用零件。 Moreover, the electron of this embodiment. In the copper alloy for electrical equipment, the average number of compounds containing Mg and P having a particle diameter of 0.1 μm or more is 0.5/μm 2 or less in the observation by scanning electron microscopy. The coarse Mg/P-containing compound is dispersed as a crack initiation point to improve bending workability. Therefore, it is possible to form a connector such as a connector of a complicated shape, a movable piece for relay, a lead frame, or the like. Parts for electrical machines.
又,本實施形態之電子.電氣機器用銅合金中,由於Mg之含量[Mg](mass%)與P之含量[P](mass%)滿足[Mg]+20×[P]<0.5之關係式,故可抑制Mg及P之粗大化合物之生成,可抑制冷加工性及彎曲加工性降低。 Moreover, the electron of this embodiment. In the copper alloy for electric equipment, since the content of Mg [Mg] (mass%) and the content of P [P] (mass%) satisfy the relationship of [Mg] + 20 × [P] < 0.5, Mg and The formation of a coarse compound of P suppresses a decrease in cold workability and bending workability.
再者,本實施形態之電子.電氣機器用銅合金中,由於Mg之含量[Mg](mass%)與P之含量[P](mass%)滿足[Mg]/[P]≦400之關係式,故使鑄造性降低之Mg含量 與使鑄造性提高之P含量之比率適當化,藉由P之添加效果而可確實提高鑄造性。 Furthermore, the electron of this embodiment. In the copper alloy for electric equipment, since the content of Mg [Mg] (mass%) and the content of P [P] (mass%) satisfy the relationship of [Mg] / [P] ≦ 400, Mg which reduces castability is obtained. content The ratio of the P content which improves the castability is made appropriate, and the casting effect can be surely improved by the addition effect of P.
又,本實施形態之電子.電氣機器用銅合金中,由於0.2%耐力設為300MPa以上,殘留應力率於150℃、1000小時設為50%以上,故強度、耐應力緩和特性優異,特別適合作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件之材料。 Moreover, the electron of this embodiment. In the copper alloy for electrical equipment, the 0.2% proof stress is 300 MPa or more, and the residual stress rate is 150° C. and 1000 hours is set to 50% or more. Therefore, the strength and stress relaxation resistance are excellent, and it is particularly suitable as a connector or a press fit. The terminal, relay movable piece, lead frame, bus bar and other electronic. Material for parts used in electrical equipment.
又,本實施形態之電子.電氣機器用銅合金板條材,由於係以上述之電子.電氣機器用銅合金構成,故藉由對該電子.電氣機器用銅合金板條材進行彎曲加工等,可製造連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件。 Moreover, the electron of this embodiment. Copper alloy strips for electrical machines, due to the above-mentioned electronics. The electrical machine is made of a copper alloy, so by means of the electron. For bending of copper alloy plates and strips for electrical equipment, it is possible to manufacture terminals such as connectors or press-fit terminals, relay movable sheets, lead frames, bus bars, and the like. Parts for electrical machines.
又,於表面形成Sn鍍敷層或Ag鍍敷層時,特別適合作為連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等之電子.電氣機器用零件之材料。 Further, when a Sn plating layer or an Ag plating layer is formed on the surface, it is particularly suitable as a terminal for a connector or a press-fit, a relay movable sheet, a lead frame, a bus bar, or the like. Material for parts used in electrical equipment.
再者,本實施形態之電子.電氣機器用零件(連接器或壓入配合等之端子、中繼用可動片、導線架、匯流條等),由於係以上述之電子.電氣機器用銅合金構成,故即使小型化及薄片化亦可發揮優異特性。 Furthermore, the electron of this embodiment. Parts for electrical equipment (terminals for connectors or press-fits, movable sheets for relays, lead frames, bus bars, etc.), due to the above-mentioned electronics. Since the electrical equipment is made of a copper alloy, it can exhibit excellent characteristics even in miniaturization and flaking.
以上雖針對本發明實施形態之電子.電氣機器用銅合金、電子.電氣機器用銅合金板條材、電子.電氣機器用零件(端子、匯流條等)加以說明,但本發明不限定於該等,在不脫離本發明技術思想之範圍內可適當變 更。 Although the above is directed to the electronic body of the embodiment of the present invention. Copper alloys and electronics for electrical equipment. Copper alloy sheet and strip for electrical equipment, electronics. The components for electrical equipment (terminals, bus bars, etc.) are described, but the present invention is not limited to these, and may be appropriately changed without departing from the technical idea of the present invention. more.
例如,上述實施形態係針對電子.電氣機器用銅合金之製造方法之一例加以說明,但電子.電氣機器用銅合金之製造方法不限於實施形態中記載者,亦可適當選擇既有製造方法製造。 For example, the above embodiment is directed to electronics. An example of a method for manufacturing a copper alloy for electrical equipment, but an electron. The method for producing the copper alloy for electric equipment is not limited to those described in the embodiment, and may be produced by appropriately selecting a conventional manufacturing method.
以下,針對欲確認本發明效果而進行之確認實驗結果加以說明。 Hereinafter, the results of the confirmation experiment performed to confirm the effects of the present invention will be described.
準備由純度99.99mass%以上之無氧銅(ASTM B152 C10100)所成銅原料,將其裝入高純度石墨坩鍋內,於設為Ar氣體環境之環境爐內進行高頻熔解。於所得銅熔浴內,添加各種添加元素調製為表1所示之成分組成,注液於鑄模中製出鑄塊。又,本發明例2、19、20係使用隔熱材(ISOWOOL)鑄模,本發明例21、22係使用碳鑄模,本發明例1、3~18、23~34、比較例1~3係使用具備水冷功能之銅合金鑄模,比較例4、5係使用具備加熱功能之附加熱器之鐵製鑄模作為鑄造用之鑄模。鑄塊大小設為厚約100mm×寬約150mm×長約300mm。 A copper raw material made of oxygen-free copper (ASTM B152 C10100) having a purity of 99.99 mass% or more was prepared, placed in a high-purity graphite crucible, and subjected to high-frequency melting in an atmosphere furnace set to an Ar gas atmosphere. In the obtained copper melting bath, various additive elements were added to prepare a composition shown in Table 1, and an ingot was injected into the mold to prepare an ingot. Further, in the examples 2, 19, and 20 of the present invention, a heat insulating material (ISOWOOL) mold was used, and in the inventive examples 21 and 22, a carbon mold was used, and the present invention examples 1, 3 to 18, 23 to 34, and comparative examples 1 to 3 were used. A copper alloy mold having a water-cooling function was used, and in Comparative Examples 4 and 5, an iron mold having a heater having a heating function was used as a mold for casting. The size of the ingot was set to be about 100 mm thick by about 150 mm wide and about 300 mm long.
面研削該鑄塊之澆鑄表面附近,以成為最終製品板厚為0.5mm之方式,切出鑄塊並調整大小。 The surface of the ingot was ground near the casting surface, and the ingot was cut and resized so that the final product thickness was 0.5 mm.
該塊體於Ar氣體環境中,以表2記載之溫度條件進行4小時加熱,進行均質化/熔體化處理。 The block was heated in an Ar gas atmosphere for 4 hours under the temperature conditions shown in Table 2 to carry out homogenization/melting treatment.
隨後,以表2記載之條件實施粗壓延後,使 用鹽浴以表2記載之溫度條件進行熱處理。 Subsequently, after the rough rolling was carried out under the conditions described in Table 2, The heat treatment was carried out under the temperature conditions described in Table 2 using a salt bath.
進行熱處理之銅材料,為了作成適於適當最終形狀而實施切斷,並且為了去除氧化被膜而實施表面研削。隨後於常溫以表2記載之壓延率實施整飾壓延(整飾加工),製出厚0.5mm、寬約150mm、長200mm之薄板。 The copper material subjected to the heat treatment is subjected to cutting in order to prepare an appropriate final shape, and surface grinding is performed in order to remove the oxide film. Subsequently, finishing rolling (finishing processing) was carried out at room temperature at a rolling ratio as described in Table 2, and a sheet having a thickness of 0.5 mm, a width of about 150 mm, and a length of 200 mm was produced.
接著,於整飾壓延(整飾加工)後,以表2所示之條件,於Ar環境中實施整飾熱處理,隨後,進行水淬冷,作成特性評價用薄板。 Next, after finishing rolling (finishing processing), finishing heat treatment was performed in an Ar environment under the conditions shown in Table 2, followed by water quenching to prepare a sheet for property evaluation.
作為鑄造性評價,觀察前述鑄造時有無表面粗糙。以目視幾乎完全未見到表面粗糙者記為A,發生深度未達1mm之小表面粗糙者記為B,發生深度1mm以上且未達2mm之表面粗糙者記為C。且發生深度2mm以上之大的表面粗糙者記為D,並於期間停止評價。評價結果示於表3。 As the evaluation of the castability, it was observed whether or not the surface roughness was observed at the time of casting. Those who barely saw surface roughness at all were recorded as A, those with a small surface roughness of less than 1 mm were recorded as B, and those with a surface roughness of 1 mm or more and less than 2 mm were recorded as C. Further, a surface roughness having a depth of 2 mm or more was recorded as D, and the evaluation was stopped during the period. The evaluation results are shown in Table 3.
又,所謂表面粗糙深度係指自鑄塊端部朝向中央之表面粗糙深度。 Further, the term "surface roughness depth" means the surface roughness depth from the end portion of the ingot toward the center.
對於各試料之壓延面,進行鏡面研磨、離子蝕刻。為了確認含有Mg及P之化合物,使用FE-SEM(場射出型掃描電子顯微鏡),以1萬倍視野(約120μm2/視野)進行觀察。 For the rolling surface of each sample, mirror polishing and ion etching were performed. In order to confirm the compound containing Mg and P, it was observed by FE-SEM (field emission type scanning electron microscope) with a 10,000-fold field of view (about 120 μm 2 / field of view).
其次,為了調查含有Mg及P之化合物之密度(個/μm2),選擇1萬倍視野(約120μm2/視野),於該區域,以5萬倍連續進行10視野(約4.8μm2/視野)之拍攝。關於金屬間化合物之粒徑,係設為金屬間化合物之長徑(於期間與粒界不相切之條件下於粒內拉出最長直線之長度)與短徑(於與長徑直角相交之方向,於期間與粒界不相切之條件下拉出最長直線之長度)之平均值。接著,求出粒徑0.1μm以上之含有Mg及P之化合物與粒徑0.05μm以上之含有Mg及P之化合物之密度(個/μm2)。化合物之觀察結果之一例示於圖2A及圖2B。 Next, in order to investigate the density (unit/μm 2 ) of the compound containing Mg and P, a 10,000-fold field of view (about 120 μm 2 / field of view) was selected, and in this region, 10 fields of view (about 4.8 μm 2 /) were continuously performed at 50,000 times. Shooting). The particle size of the intermetallic compound is defined as the long diameter of the intermetallic compound (the length of the longest straight line drawn in the grain under the condition that the grain boundary is not tangent to the grain boundary) and the short diameter (intersecting with the right angle of the long diameter) The average value of the direction, which is the length of the longest straight line when the period is not tangent to the grain boundary. Next, the density (unit/μm 2 ) of the compound containing Mg and P having a particle diameter of 0.1 μm or more and the compound containing Mg and P having a particle diameter of 0.05 μm or more was determined. One of the observation results of the compound is exemplified in Figs. 2A and 2B.
自特性評價用條材採取由JIS Z 2241所規定之13B號試驗片,藉由JIS Z 2241之支距法(offset method),測定0.2%耐力。又,試驗片係於與壓延方向正交方向採取。評價結果示於表3。 From the strip for characteristic evaluation, a test piece No. 13B prescribed by JIS Z 2241 was used, and 0.2% proof stress was measured by the offset method of JIS Z 2241. Further, the test piece was taken in a direction orthogonal to the rolling direction. The evaluation results are shown in Table 3.
自特性評價用條材採取寬10mm×長150mm之試驗片,藉由4端子法求出電阻。且使用微米進行試驗片之尺寸測定,算出試驗片體積。接著,自所測定之電阻值與體積,算出導電率。又,試驗片係以其長度方向對於特定評價用條材之壓延方向垂直之方式採取。評價結果示於表3。 A test piece having a width of 10 mm and a length of 150 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 micrometers, and the test piece volume was calculated. Next, the conductivity was calculated from the measured resistance value and volume. Further, the test piece was taken such that its longitudinal direction was perpendicular to the rolling direction of the specific evaluation strip. The evaluation results are shown in Table 3.
耐應力緩和特性試驗係藉由根據日本伸銅協會技術標準JCBA-T309:2004之單端螺固式之方法負荷應力,測定於150℃之溫度保持1000小時後之殘留應力率。評價結果示於表3。 The stress relaxation resistance test was carried out by measuring the load stress at a temperature of 150 ° C for 1000 hours by a single-end screw-type method according to the Japanese copper-clad association technical standard JCBA-T309:2004. The evaluation results are shown in Table 3.
作為試驗方法,係自特性評價用條材於對於壓延方向正交之方向採取試驗片(寬10mm),以將試驗片之表面最大應力成為耐力之80%之方式,將初期撓曲位移設定為2mm,調整跨距長。以下式決定上述表面最大應力。 As a test method, a test piece (width: 10 mm) was taken from the strip for characteristic evaluation in the direction perpendicular to the rolling direction, and the initial deflection of the surface of the test piece was set to 80% of the endurance, and the initial deflection displacement was set to 2mm, adjustable span length. The following formula determines the maximum stress of the above surface.
表面最大應力(MPa)=1.5Etδ0/Ls 2 Surface maximum stress (MPa) = 1.5Etδ 0 /L s 2
惟, but,
E:楊氏模數(MPa) E: Young's modulus (MPa)
t:試料厚度(t=0.5mm) t: sample thickness (t=0.5mm)
δ0:初期撓曲位移(2mm) δ 0 : initial deflection displacement (2mm)
Ls:跨距長(mm) L s : span length (mm)
於150℃之溫度保持1000小時後之彎曲傾向後,測定殘留應力率,評價耐應力緩和特性。又使用下式算出殘留應力率。 After the bending tendency was maintained at a temperature of 150 ° C for 1,000 hours, the residual stress rate was measured, and the stress relaxation resistance was evaluated. Further, the residual stress rate was calculated using the following formula.
殘留應力率(%)=(1-δt/δ0)×100 Residual stress rate (%) = (1 - δ t / δ 0 ) × 100
惟, but,
δt:於150℃之溫度保持1000小時後之永久撓曲位移(mm)-於常溫保持24小時後之永久撓曲位移(mm) δ t : permanent deflection displacement (mm) after 1000 hours at a temperature of 150 ° C - permanent deflection displacement (mm) after 24 hours at room temperature
δ0:初期撓曲位移(mm) δ 0 : initial deflection displacement (mm)
根據日本伸銅協會技術標準JCBA-T307:2007之4試驗方法進行彎曲加工。以彎曲軸對於壓延方向成為正交方向之方式,自特性評價用薄板採取複數片寬10mm×長30mm之試驗片,使用彎曲角度為90度,且彎曲半徑於整飾壓延率超過85%時為0.5mm(R/t=1.0),於整飾壓延率為85%以下時彎曲半徑為0.3mm(R/t=0.6)之W型治具,進行W彎曲試驗。 The bending process was carried out according to the test method of the Japanese Copper Association Technical Standard JCBA-T307:2007. A test piece having a width of 10 mm and a length of 30 mm was used for the self-characteristic evaluation sheet so that the bending axis was orthogonal to the rolling direction, and the bending angle was 90 degrees, and the bending radius was 85% when the finishing rolling ratio was more than 85%. 0.5 mm (R/t = 1.0), W-bending test was carried out on a W-shaped jig having a bending radius of 0.3 mm (R/t = 0.6) when the finishing rolling ratio was 85% or less.
以目視觀察彎曲部之外周部觀察到龜裂時記為「C」,觀察到較大皺褶時記為B,未見到斷裂或微細龜裂、較大皺褶時記為A進行判定。又,A及B係判斷為可容許之彎曲加工性。評價結果示於表3。 When the crack was observed on the outer peripheral portion of the curved portion, "C" was observed, and when large wrinkles were observed, it was recorded as B, and when no crack or fine crack was observed, and A large wrinkle was observed, it was judged as A. Further, A and B are judged to be allowable bending workability. The evaluation results are shown in Table 3.
比較例1係Mg含量少於本發明範圍(0.15mass%以上、未達0.35mass%之範圍),耐力及耐應力緩和特性不充分。 In Comparative Example 1, the Mg content was less than the range of the present invention (0.15 mass% or more and less than 0.35 mass%), and the endurance and stress relaxation resistance were insufficient.
比較例2係Mg含量多於本發明範圍(0.15mass%以上、未達0.35mass%之範圍),導電率低。 In Comparative Example 2, the Mg content was more than the range of the present invention (0.15 mass% or more and less than 0.35 mass%), and the electrical conductivity was low.
比較例3係P含量多於本發明範圍(0.0005mass%以上、未達0.01mass%之範圍),於中間壓延發生龜裂,無法評價。 In Comparative Example 3, the P content was more than the range of the present invention (0.0005 mass% or more and less than 0.01 mass%), and cracking occurred in the intermediate rolling, which was not evaluated.
比較例4、5係Mg及P含量較多,且鑄造時之冷卻速度慢,故化合物多,彎曲加工性差。 In Comparative Examples 4 and 5, the content of Mg and P was large, and the cooling rate at the time of casting was slow, so that there were many compounds and the bending workability was poor.
相對於此,本發明例中,確認鑄造性、強度(0.2%耐力)、導電率、耐應力緩和特性(殘留應力率)、彎曲加工性優異。基於以上,確認依據本發明例,可提供導電性、彎曲加工性優異之電子.電氣機器用銅合金、電子.電氣機器用銅合金板條材。 On the other hand, in the examples of the present invention, it was confirmed that the castability, the strength (0.2% proof), the electrical conductivity, the stress relaxation resistance (residual stress ratio), and the bending workability were excellent. Based on the above, it was confirmed that an electron having excellent conductivity and bending workability can be provided according to the example of the present invention. Copper alloys and electronics for electrical equipment. Copper alloy sheet strip for electrical equipment.
本發明提供即使使用於伴隨小型化而薄片化之構件時,亦具備優異導電性及彎曲加工性之電子.電氣機器用銅合金、電子.電氣機器用銅合金板條材、電子.電氣機器用零件、端子、匯流條、及中繼用可動片。 The present invention provides an electron having excellent conductivity and bending workability even when used for a member which is thinned with miniaturization. Copper alloys and electronics for electrical equipment. Copper alloy sheet and strip for electrical equipment, electronics. Parts for electrical equipment, terminals, bus bars, and movable sheets for relays.
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