JP2010255042A - Copper alloy and method for producing copper alloy - Google Patents
Copper alloy and method for producing copper alloy Download PDFInfo
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本発明は、銅合金及び銅合金の製造方法に関する。特に、本発明は、電子部品用の銅合金及び銅合金の製造方法に関する。 The present invention relates to a copper alloy and a method for producing a copper alloy. In particular, the present invention relates to a copper alloy for electronic parts and a method for producing the copper alloy.
近年、携帯電話、ノート型パソコン等の各種の電気・電子機器の小型化、薄型化、及び軽量化に伴い、電気・電子機器に用いられる部品も小型化している。そして、部品の小型化に伴い、部品の端子又はコネクタ部品についても、小型化及び電極間ピッチの狭小化が進んでいる。このような部品の小型化により、各種部品に用いられる電極等の材料が従来に比べて薄肉になっている。ここで、薄肉の電極であってもばね材として高い接触圧を得て電気的な接続の信頼性を保つべく、電極等の材料にばね性の高い材料を用いることが要求されている。そして、これら各種部品は複雑な曲げ加工が施されて製造されるので、加工時において割れが発生しない程度の曲げ加工性が要求される。 In recent years, with the reduction in size, thickness, and weight of various electric / electronic devices such as mobile phones and notebook computers, parts used in electric / electronic devices have also been downsized. With the miniaturization of components, miniaturization and narrowing of the inter-electrode pitch are also progressing with respect to component terminals or connector components. Due to such downsizing of parts, materials such as electrodes used for various parts are thinner than conventional ones. Here, in order to obtain a high contact pressure as a spring material and maintain the reliability of electrical connection even for a thin electrode, it is required to use a material having a high spring property as a material such as an electrode. And since these various parts are manufactured by performing a complicated bending process, the bending processability of the grade which does not generate | occur | produce a crack at the time of a process is requested | required.
また、電気・電子機器の高機能化に伴う電極数の増加、及び通電する電流の増加によって、電極等において発生するジュール熱も増加しており、従来より導電性の良い材料を用いることに対する要求も強まっている。更に、高温下、長期間の使用においても接触圧を維持できる耐応力緩和性等の特性も要求される。すなわち、電気・電子機器に用いられる端子又はコネクタ部品を構成する材料は、高強度、高耐力、及び良好な曲げ加工性を有すると共に、良好な導電性、並びに高い耐応力緩和性等を有することが求められている。 In addition, due to the increase in the number of electrodes accompanying the increase in functionality of electric and electronic devices and the increase in current to be applied, the Joule heat generated in the electrodes and the like is also increasing, and there is a demand for using a material having better conductivity than before. Is also getting stronger. Furthermore, characteristics such as stress relaxation resistance that can maintain the contact pressure even under long-term use at high temperatures are required. That is, the materials constituting the terminals or connector parts used in electrical and electronic equipment have high strength, high yield strength, and good bending workability, as well as good electrical conductivity and high stress relaxation resistance. Is required.
従来、０．５〜２．５質量％のＮｉと、０．５〜２．５質量％のＣｏと、０．３０〜１．２質量％のＳｉと、０．０９〜０．５質量％のＣｒとを含有し、残部がＣｕ及び不可避的不純物から構成される銅合金において、合金組成中のＮｉとＣｏとの合計量のＳｉに対する質量濃度比（［Ｎｉ＋Ｃｏ］／Ｓｉ比）が４≦［Ｎｉ＋Ｃｏ］／Ｓｉ≦５であり、合金組成中のＮｉとＣｏの質量濃度比（Ｎｉ／Ｃｏ比）が０．５≦Ｎｉ／Ｃｏ≦２であり、材料中に分散する大きさが１μｍ以上の介在物の個数（Ｐ）、そのうち、含有炭素濃度が１０質量％以上である介在物の個数（Ｐｃ）について、Ｐｃが１５個／１０００μｍ２以下であると共に、その比（Ｐｃ／Ｐ）が０．３以下である電子材料用Ｃｕ−Ｎｉ−Ｓｉ−Ｃｏ−Ｃｒ系銅合金が知られている（例えば、特許文献１参照）。 Conventionally, 0.5 to 2.5 mass% Ni, 0.5 to 2.5 mass% Co, 0.30 to 1.2 mass% Si, and 0.09 to 0.5 mass% In a copper alloy containing the remaining Cr and the balance consisting of Cu and inevitable impurities, the mass concentration ratio ([Ni + Co] / Si ratio) of the total amount of Ni and Co in the alloy composition to Si is 4 ≦ [Ni + Co] / Si ≦ 5, the mass concentration ratio of Ni and Co (Ni / Co ratio) in the alloy composition is 0.5 ≦ Ni / Co ≦ 2, and the size dispersed in the material is 1 μm or more. The number of inclusions (P), of which the inclusion carbon concentration is 10% by mass or more (Pc), Pc is 15 pieces / 1000 μm 2 or less, and the ratio (Pc / P) is Cu-Ni-Si-Co-Cr-based copper alloys for electronic materials that are 0.3 or less are known That (for example, see Patent Document 1).
特許文献１に記載の銅合金は、上記構成を備えているので、銅合金の強度を損なわずに導電性を向上させることができる。 Since the copper alloy described in Patent Document 1 has the above-described configuration, the conductivity can be improved without impairing the strength of the copper alloy.
しかし、特許文献１に記載の銅合金は、強度の低下を抑制して導電性を向上させることができるものの、銅合金の強度と銅合金の曲げ加工性とはトレードオフの関係にある（すなわち、材料の強度を向上させることに伴い、良好な曲げ加工性を維持することが困難になる）ことから、当該銅合金の強度を向上させると共に当該銅合金の曲げ加工性を向上させるには不十分な場合がある。例えば、小型化が進む電子部品材料の用途に銅合金を提供するという観点からは、特許文献１に記載の銅合金では、曲げ加工性を更に向上させることが困難な場合がある。 However, although the copper alloy described in Patent Document 1 can suppress the decrease in strength and improve conductivity, the strength of the copper alloy and the bending workability of the copper alloy are in a trade-off relationship (that is, As the strength of the material is improved, it becomes difficult to maintain good bending workability). Therefore, it is not possible to improve the strength of the copper alloy and the bending workability of the copper alloy. It may be enough. For example, from the viewpoint of providing a copper alloy for use in electronic component materials that are becoming smaller in size, it may be difficult to further improve the bending workability with the copper alloy described in Patent Document 1.
したがって、本発明の目的は、高強度及び良好な導電性を備えると共に、優れた曲げ加工性を備える銅合金及び銅合金の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a copper alloy having high strength and good electrical conductivity, and an excellent bending workability and a method for producing the copper alloy.
本発明は、上記目的を達成するため、圧延加工を経て製造される銅合金であって、Ｓｉと、Ｓｉと反応してシリコン化合物を形成するＮｉ及びＣｏと、銅合金に含まれる結晶粒の成長を抑制するＳｎ及びＺｎとを含有すると共に、残部がＣｕと不可避的不純物とからなり、ＮｉとＣｏとの合計量のＳｉに対する質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉが４以上５以下であり、ＮｉのＣｏに対する質量濃度比Ｎｉ／Ｃｏが０．５以上２以下であり、圧延加工の圧延方向に対して平行な断面における銅合金の結晶粒の長径ａと短径ｂとの比ａ／ｂが１．０以上２．５以下であると共に、長径ａと短径ｂとの相加平均値（ａ＋ｂ）／２が１０μｍ以下である銅合金が提供される。 In order to achieve the above object, the present invention is a copper alloy manufactured through rolling, and includes Si, Ni and Co that react with Si to form a silicon compound, and crystal grains contained in the copper alloy. In addition to containing Sn and Zn for suppressing growth, the balance consists of Cu and inevitable impurities, and the mass concentration ratio (Ni + Co) / Si with respect to Si of the total amount of Ni and Co is 4 or more and 5 or less, The ratio of Ni / Co to Ni concentration ratio Ni / Co is 0.5 or more and 2 or less, and the ratio a / b between the major axis a and the minor axis b of the crystal grains of the copper alloy in a cross section parallel to the rolling direction of rolling. Is not less than 1.0 and not more than 2.5, and a copper alloy in which the arithmetic average value (a + b) / 2 of the major axis “a” and the minor axis “b” is 10 μm or less is provided.
また、上記銅合金は、Ｎｉは、１．０質量％以上２．５質量％以下含有され、Ｃｏは、０．５質量％以上２．０質量％以下含有され、Ｓｉは、０．３質量％以上１．０質量％以下含有され、Ｓｎは、０．０５質量％以上０．３質量％以下含有され、Ｚｎは、０．０５質量％以上０．５質量％以下含有されてもよい。 In the copper alloy, Ni is contained in an amount of 1.0% by mass to 2.5% by mass, Co is contained in an amount of 0.5% by mass to 2.0% by mass, and Si is 0.3% by mass. % Sn to 1.0% by mass, Sn may be 0.05% to 0.3% by mass, and Zn may be 0.05% to 0.5% by mass.
また、上記銅合金は、Ｔｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料を総量で０．０３質量％以上０．３質量％以下、更に含有することもできる。 The copper alloy further contains at least one material selected from the group consisting of Ti, Zr, Hf, B, Ga, and In in a total amount of 0.03% by mass to 0.3% by mass. You can also.
また、上記銅合金は、８００ＭＰａ以上の引張強さと、１０％以上の伸びと、５０％ＩＡＣＳ以上の導電率とを有することが好ましい。 The copper alloy preferably has a tensile strength of 800 MPa or more, an elongation of 10% or more, and a conductivity of 50% IACS or more.
また、本発明は、上記目的を達成するため、板材を呈する銅合金の製造方法であって、複数の金属元素を含む原料としての銅合金を準備する原料準備工程と、原料としての銅合金を溶製してインゴットを鋳造する鋳造工程と、インゴットに押出加工を施して板状部材を形成する押出加工工程と、板状部材を、板材の厚さよりも厚い厚さまで冷間圧延して第１の板材を形成する第１冷間圧延工程と、第１の板材に加熱処理を施した後、冷却する第１の熱処理工程と、第１の熱処理工程の後に、板材の厚さまで冷間圧延して第２の板材を形成する第２冷間圧延工程と、第２の冷間圧延工程の後に、第２の板材に加熱処理を施した後、冷却する第２の熱処理工程とを備える銅合金の製造方法が提供される。 In order to achieve the above object, the present invention is a method for producing a copper alloy exhibiting a plate material, comprising a raw material preparation step of preparing a copper alloy as a raw material containing a plurality of metal elements, and a copper alloy as a raw material. A casting process for melting and casting an ingot, an extrusion process for forming the plate-like member by subjecting the ingot to extrusion processing, and cold-rolling the plate-like member to a thickness thicker than the thickness of the plate material is first performed. The first cold rolling step for forming the plate material, the first heat treatment step for cooling the first plate material, and the cold treatment after the first heat treatment step and the first heat treatment step are cold rolled to the thickness of the plate material. A copper alloy comprising: a second cold rolling step for forming the second plate material; and a second heat treatment step for cooling the second plate material after the second cold rolling step and after the second cold rolling step. A manufacturing method is provided.
また、上記銅合金の製造方法は、第１冷間圧延工程は、第１の板材の厚さが板材の１．１倍以上１．３倍以下の厚さになるまで冷間圧延し、第１の熱処理工程は、第１の板材に８００℃以上９００℃以下の温度の加熱処理を施した後、毎分２５℃以上の降温速度で３００℃まで冷却し、第２の熱処理工程は、第２の板材に４００℃以上５５０℃以下の温度の加熱処理を施した後、当該温度下で３０分以上８時間以下、保持してもよい。 Further, in the method for producing a copper alloy, the first cold rolling step is performed by cold rolling until the thickness of the first plate is 1.1 times or more and 1.3 times or less that of the plate. In the first heat treatment step, the first plate material is subjected to a heat treatment at a temperature of 800 ° C. or more and 900 ° C. or less, and then cooled to 300 ° C. at a temperature lowering rate of 25 ° C. or more per minute. After performing the heat processing of the temperature of 400 to 550 degreeC to the board | plate material of 2, you may hold | maintain for 30 minutes or more and 8 hours or less under the said temperature.
また、上記銅合金の製造方法は、製造される銅合金は、Ｓｉと、Ｓｉと反応してシリコン化合物を形成するＮｉ及びＣｏと、銅合金に含まれる結晶粒の成長を抑制するＳｎ及びＺｎとを含有すると共に、残部がＣｕと不可避的不純物とからなり、ＮｉとＣｏとの合計量のＳｉに対する質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉが４以上５以下であり、ＮｉのＣｏに対する質量濃度比Ｎｉ／Ｃｏが０．５以上２以下であり、圧延加工の圧延方向に対して平行な断面における銅合金の結晶粒の長径ａと短径ｂとの比ａ／ｂが１．０以上２．５以下であると共に、長径ａと短径ｂとの相加平均値（ａ＋ｂ）／２が１０μｍ以下であることが好ましい。 The copper alloy manufacturing method includes: Si, Ni and Co that react with Si to form a silicon compound, and Sn and Zn that suppress the growth of crystal grains contained in the copper alloy. And the balance is made of Cu and inevitable impurities, the mass concentration ratio of Ni and Co to the total amount of Si (Ni + Co) / Si is 4 or more and 5 or less, and the mass concentration ratio of Ni to Co Ni / Co is 0.5 or more and 2 or less, and the ratio a / b between the major axis a and the minor axis b of the copper alloy crystal grains in a cross section parallel to the rolling direction of rolling is 1.0 or more. It is preferable that the arithmetic average value (a + b) / 2 of the major axis “a” and the minor axis “b” is 10 μm or less.
また、上記銅合金の製造方法は、Ｎｉは、１．０質量％以上２．５質量％以下含有され、Ｃｏは、０．５質量％以上２．０質量％以下含有され、Ｓｉは、０．３質量％以上１．０質量％以下含有され、Ｓｎは、０．０５質量％以上０．３質量％以下含有され、Ｚｎは、０．０５質量％以上０．５質量％以下含有されることが好ましい。 In the above copper alloy manufacturing method, Ni is contained in an amount of 1.0% by mass or more and 2.5% by mass or less, Co is contained in an amount of 0.5% by mass or more and 2.0% by mass or less, and Si is 0% by mass. 0.3 mass% or more and 1.0 mass% or less, Sn is contained 0.05 mass% or more and 0.3 mass% or less, and Zn is contained 0.05 mass% or more and 0.5 mass% or less. It is preferable.
また、上記銅合金の製造方法は、銅合金は、Ｔｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料を総量で０．０３質量％以上０．３質量％以下、更に含有することが好ましい。 Further, in the above copper alloy manufacturing method, the copper alloy is at least one material selected from the group consisting of Ti, Zr, Hf, B, Ga, and In in a total amount of 0.03% by mass or more and 0.3%. It is preferable to further contain by mass% or less.
また、上記銅合金の製造方法は、第２の熱処理工程を経て製造される銅合金は、８００ＭＰａ以上の引張強さと、１０％以上の伸びと、５０％ＩＡＣＳ以上の導電率とを有することが好ましい。 In the copper alloy manufacturing method, the copper alloy manufactured through the second heat treatment step may have a tensile strength of 800 MPa or more, an elongation of 10% or more, and a conductivity of 50% IACS or more. preferable.
本発明に係る銅合金及び銅合金の製造方法によれば、高強度及び良好な導電性を備えると共に、優れた曲げ加工性を備える銅合金及び銅合金の製造方法を提供できる。 According to the copper alloy and the method for producing a copper alloy according to the present invention, it is possible to provide a copper alloy and a method for producing a copper alloy that have high strength and good electrical conductivity and also have excellent bending workability.
［実施の形態］
本実施の形態に係る銅合金は、一例として、圧延加工を経て製造される銅合金である。そして、当該銅合金は、シリコン（Ｓｉ）と、Ｓｉと反応してシリコン化合物（Ｓｉ化合物）を形成するニッケル（Ｎｉ）及びコバルト（Ｃｏ）と、当該銅合金に含まれる結晶粒の成長を抑制するスズ（Ｓｎ）及び亜鉛（Ｚｎ）とを含有すると共に、残部が銅（Ｃｕ）と不可避的不純物とから形成される。銅としては、無酸素銅が挙げられる。
[Embodiment]
The copper alloy which concerns on this Embodiment is a copper alloy manufactured through rolling as an example. The copper alloy suppresses growth of silicon (Si), nickel (Ni) and cobalt (Co) that react with Si to form a silicon compound (Si compound), and crystal grains contained in the copper alloy. In addition to containing tin (Sn) and zinc (Zn), the balance is formed from copper (Cu) and inevitable impurities. An example of copper is oxygen-free copper.
また、本実施の形態において、Ｎｉの添加量とＣｏの添加量との合計量のＳｉの添加量に対する質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉが４以上５以下に制御されると共に、Ｎｉの添加量のＣｏの添加量に対する質量濃度比Ｎｉ／Ｃｏが０．５以上２以下に制御される。更に、圧延加工の圧延方向に対して平行な断面における当該銅合金の結晶粒の長径ａと短径ｂとの比ａ／ｂが１．０以上２．５以下に制御されると共に、長径ａと短径ｂとの相加平均値（ａ＋ｂ）／２が１０μｍ以下に制御される。また、本実施の形態に係る銅合金には、Ｔｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料を添加することもできる。 In the present embodiment, the mass concentration ratio (Ni + Co) / Si with respect to the addition amount of Si of the total addition amount of Ni and the addition amount of Co is controlled to 4 or more and 5 or less, and the addition amount of Ni The mass concentration ratio Ni / Co with respect to the added amount of Co is controlled to 0.5 or more and 2 or less. Further, the ratio a / b between the major axis a and the minor axis b of the copper alloy crystal grains in a cross section parallel to the rolling direction of the rolling process is controlled to 1.0 or more and 2.5 or less, and the major axis a And the average value (a + b) / 2 of the minor axis b are controlled to 10 μm or less. Further, at least one material selected from the group consisting of Ti, Zr, Hf, B, Ga, and In can be added to the copper alloy according to the present embodiment.
（Ｎｉ、Ｃｏ、及びＳｉについて）
Ｃｕ中にＮｉと、Ｃｏと、Ｓｉとを共に添加することにより、銅合金中にＳｉ化合物を析出させることができる。Ｓｉ化合物を銅合金中に分散、析出させることにより、銅合金の良好な導電率が維持されると共に、銅合金の強度が向上する。すなわち、本実施の形態に係る銅合金は、銅の母材中にＳｉ化合物が分散して存在することにより、銅の導電性を維持しつつ、銅合金の強度を向上させることができる。ここで、Ｎｉ、Ｃｏ、及びＳｉの質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉを特定の範囲に規定することにより、Ｃｕ中に添加したＮｉ、Ｃｏ、及び／又はＳｉがＣｕ中に元素単体として残存することを抑制できるので（すなわち、Ｃｕ中におけるこれらの元素の固溶量を抑制できる）、これらの元素がＣｕ中に単体で存在することに起因する銅合金の導電率の低下を抑制できる。
(About Ni, Co, and Si)
By adding together Ni, Co, and Si into Cu, a Si compound can be precipitated in the copper alloy. By dispersing and precipitating the Si compound in the copper alloy, good conductivity of the copper alloy is maintained and the strength of the copper alloy is improved. That is, the copper alloy according to the present embodiment can improve the strength of the copper alloy while maintaining the conductivity of the copper because the Si compound is dispersed in the copper base material. Here, by defining the mass concentration ratio (Ni + Co) / Si of Ni, Co, and Si within a specific range, Ni, Co, and / or Si added to Cu remain as elemental elements in Cu. Since this can be suppressed (that is, the solid solution amount of these elements in Cu can be suppressed), the decrease in the conductivity of the copper alloy due to the presence of these elements alone in Cu can be suppressed.
また、Ｎｉ及びＣｏの添加量は、銅合金が有する所望の強度と所望の導電率が実現できる範囲に規定される。すなわち、電子部品等への適用において十分な強度を有すると共に、銅の導電率と同程度の導電率を維持できる銅合金を提供することを目的として、１．０質量％以上２．５質量％以下のＮｉと、０．５質量％以上２．０質量％以下のＣｏとが銅合金に添加される。 Further, the addition amounts of Ni and Co are defined within a range in which the desired strength and desired conductivity of the copper alloy can be realized. That is, for the purpose of providing a copper alloy having sufficient strength in application to electronic parts and the like and capable of maintaining the same conductivity as that of copper, 1.0% by mass to 2.5% by mass The following Ni and 0.5 mass% or more and 2.0 mass% or less Co are added to a copper alloy.
また、Ｎｉ及びＣｏとＳｉとの間で形成されるＳｉ化合物により銅合金の強度を向上させて電子部品等へ適用しても十分な強度を有する銅合金を提供すると共に、銅と同程度の導電率を維持できる銅合金を提供することを目的として、０．３質量％以上１．０質量％以下のＳｉが銅合金に添加される。 In addition, the strength of the copper alloy is improved by the Si compound formed between Ni and Co and Si to provide a copper alloy having sufficient strength even when applied to an electronic component or the like, and at the same level as copper. In order to provide a copper alloy that can maintain electrical conductivity, 0.3 mass% or more and 1.0 mass% or less of Si is added to the copper alloy.
また、質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉは、ＳｉとＮｉ及びＣｏとの間でＳｉ化合物が形成され、Ｓｉ化合物の形成に関与しないＳｉ、Ｎｉ、及びＣｏが実質的に銅合金中に残存しない範囲に規定される。すなわち、質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉを上記の範囲に規定することにより、Ｎｉ及びＣｏの添加量に対してＳｉの添加量が過剰になること、又はＳｉの添加量に対してＮｉ及びＣｏの添加量が過剰になることがない量のＳｉ、Ｎｉ、及びＣｏが銅合金に添加される。これにより、Ｓｉ化合物の形成に関与しないＳｉ、Ｎｉ、及びＣｏがＣｕ中に固溶することを抑制できるので、Ｃｕ中に固溶する金属元素に起因する銅合金の導電率の低下を抑制できる。 Further, in the mass concentration ratio (Ni + Co) / Si, a Si compound is formed between Si, Ni, and Co, and Si, Ni, and Co that are not involved in the formation of the Si compound are substantially not left in the copper alloy. Specified in range. That is, by defining the mass concentration ratio (Ni + Co) / Si within the above range, the addition amount of Si becomes excessive with respect to the addition amount of Ni and Co, or Ni and Co with respect to the addition amount of Si. Si, Ni, and Co are added to the copper alloy in such an amount that does not become excessive. Thereby, since it can suppress that Si, Ni, and Co which do not participate in formation of Si compound dissolve in Cu, the fall of the electrical conductivity of the copper alloy resulting from the metal element which dissolves in Cu can be suppressed. .
なお、Ｎｉの添加量のＣｏの添加量に対する質量濃度比は、銅合金の強度及び導電率が目的とする範囲内になるように規定される。すなわち、銅合金の強度を目的とする強度以上にすることを目的として、所定量以下のＣｏを銅合金に添加すると共に、銅合金の導電率を所定の導電率以上にすることを目的として、所定量以下のＮｉを銅合金に添加する。 The mass concentration ratio of the addition amount of Ni to the addition amount of Co is defined so that the strength and conductivity of the copper alloy are within the intended ranges. That is, for the purpose of making the strength of the copper alloy equal to or higher than the target strength, while adding a predetermined amount or less of Co to the copper alloy, and for the purpose of setting the conductivity of the copper alloy to be equal to or higher than the predetermined conductivity, A predetermined amount or less of Ni is added to the copper alloy.
（Ｓｎ、Ｚｎについて）
Ｃｕ中にＳｎを添加することにより、本実施の形態に係る銅合金の強度、ばね性、及び耐熱性が向上する。銅合金の耐熱性が向上することにより、高温下での銅合金の耐応力緩和性が改善される。なお、本実施の形態において高温とは、例えば、１５０℃以上１８０℃以下程度の温度である。また、ＳｎをＣｕ中に添加することにより、銅合金に高温の熱処理が施された場合に、銅合金を構成する金属結晶の結晶粒の成長が抑制される。これにより、銅合金を構成する金属結晶の粒径を、微細な粒径に維持できる。なお、本実施の形態において微細な粒径とは、例えば、１０μｍ以下程度の粒径である。
(About Sn and Zn)
By adding Sn to Cu, the strength, springiness, and heat resistance of the copper alloy according to the present embodiment are improved. By improving the heat resistance of the copper alloy, the stress relaxation resistance of the copper alloy at high temperatures is improved. In the present embodiment, the high temperature is, for example, a temperature of about 150 ° C. to 180 ° C. Further, by adding Sn to Cu, the growth of the crystal grains of the metal crystals constituting the copper alloy is suppressed when the copper alloy is subjected to high-temperature heat treatment. Thereby, the particle size of the metal crystal which comprises a copper alloy can be maintained at a fine particle size. In the present embodiment, the fine particle size is, for example, a particle size of about 10 μm or less.
Ｃｕ中にＺｎを添加することにより、本実施の形態に係る銅合金の強度、ばね性、及び耐応力緩和性が向上する。また、Ｓｎと同様に、ＺｎをＣｕ中に添加することにより、銅合金を構成する金属結晶の結晶粒の成長が抑制される。また、銅合金中にＳｎ及びＺｎが含まれていることにより、電気部品材料に要求されるＳｎめっき密着性、はんだ濡れ性が改善される。 By adding Zn to Cu, the strength, springiness, and stress relaxation resistance of the copper alloy according to the present embodiment are improved. Similarly to Sn, by adding Zn into Cu, growth of crystal grains of metal crystals constituting the copper alloy is suppressed. In addition, Sn and Zn contained in the copper alloy improves Sn plating adhesion and solder wettability required for the electrical component material.
本実施の形態においては、銅合金の強度、ばね性、及び耐応力緩和性を十分に向上させると共に、銅と同程度の導電率を維持できる銅合金を提供することを目的として、０．０５質量％以上０．３質量％以下のＳｎが銅合金に添加される。また、銅合金の強度、ばね性の向上、Ｓｎめっきに対する密着性の向上、及びはんだ濡れ性の向上を図ると共に、銅と同程度の導電率を維持できる銅合金を提供することを目的として、０．０５質量％以上０．５質量％以下のＺｎが銅合金に添加される。 In the present embodiment, for the purpose of providing a copper alloy capable of sufficiently improving the strength, springiness, and stress relaxation resistance of a copper alloy and maintaining the same degree of conductivity as copper, 0.05. Sn of 0.3% by mass or more is added to the copper alloy. In addition, with the aim of providing a copper alloy that can maintain the same electrical conductivity as copper, while improving the strength, springiness of copper alloy, improving adhesion to Sn plating, and improving solder wettability, 0.05% by mass or more and 0.5% by mass or less of Zn is added to the copper alloy.
（銅合金を構成する結晶粒について）
銅合金の金属組織の結晶粒の大きさが微細であるほど、当該銅合金の曲げ加工性が向上する。ここで、通常の銅合金に圧延加工を施した場合、圧延加工が施された銅合金の金属組織の結晶粒が圧延方向に引き伸ばされた形状になる。そして、この銅合金に、圧延方向に平行な曲げ軸に沿って曲げ加工を施すと、銅合金に割れが生じる場合がある。
(Crystal grains constituting copper alloy)
The finer the crystal grain size of the metal structure of the copper alloy, the better the bending workability of the copper alloy. Here, when a normal copper alloy is rolled, the crystal grains of the metal structure of the copper alloy that has been rolled are stretched in the rolling direction. And when this copper alloy is bent along a bending axis parallel to the rolling direction, the copper alloy may be cracked.
そこで、本実施の形態に係る銅合金の金属組織は、銅合金に曲げ加工を施した場合における割れの発生の抑制を目的として、異方性の小さい微細な結晶粒から構成される。具体的に、本実施の形態に係る銅合金は、圧延方向に平行な曲げ軸に沿って曲げ加工を施した場合に銅合金に割れが発生することを抑制すべく、圧延加工方向に対して平行な断面における銅合金の結晶粒の長径ａと短径ｂとの比ａ／ｂを１．０以上２．５以下に制御される。また、銅合金の良好な曲げ加工性を維持することを目的として、長径ａと短径ｂとの相加平均値（ａ＋ｂ）／２を、１０μｍ以下の範囲に制御される。本実施の形態に係る銅合金がこのような微細な結晶粒の金属組織を有することにより、銅合金の曲げ加工性が向上する。 Therefore, the metal structure of the copper alloy according to the present embodiment is composed of fine crystal grains with small anisotropy for the purpose of suppressing the occurrence of cracking when the copper alloy is bent. Specifically, the copper alloy according to the present embodiment is formed with respect to the rolling direction in order to suppress cracking in the copper alloy when bending is performed along a bending axis parallel to the rolling direction. The ratio a / b between the major axis a and the minor axis b of the copper alloy crystal grains in the parallel cross section is controlled to 1.0 or more and 2.5 or less. Further, for the purpose of maintaining good bending workability of the copper alloy, the arithmetic average value (a + b) / 2 of the major axis “a” and the minor axis “b” is controlled within a range of 10 μm or less. When the copper alloy according to the present embodiment has such a fine crystal grain metal structure, the bending workability of the copper alloy is improved.
また、Ｔｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料を銅合金に添加することにより、微細な結晶粒の金属組織からなる銅合金が得やすくなる。Ｔｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料を銅合金に添加すると、当該銅合金に高温の熱処理を施して再結晶させた後に、熱処理後の銅合金の金属組織の結晶粒径が微細化される。これにより、Ｔｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料が添加されていない銅合金に比べて、これらの材料のうち少なくとも１種類の材料が添加された銅合金に対しては、広い温度範囲における熱処理を施しても微細な結晶粒の金属組織が形成される。 Further, by adding at least one material selected from the group consisting of Ti, Zr, Hf, B, Ga, and In to the copper alloy, it becomes easy to obtain a copper alloy having a metal structure of fine crystal grains. . When at least one material selected from the group consisting of Ti, Zr, Hf, B, Ga, and In is added to a copper alloy, the copper alloy is subjected to high-temperature heat treatment and recrystallized, and then subjected to heat treatment. The crystal grain size of the metal structure of the copper alloy is refined. Accordingly, at least one of these materials is added compared to a copper alloy to which at least one material selected from the group consisting of Ti, Zr, Hf, B, Ga, and In is not added. Even if the copper alloy is subjected to heat treatment in a wide temperature range, a metal structure of fine crystal grains is formed.
なお、結晶粒径の微細化により曲げ加工性の向上を目的として、総量で０．０３質量％以上のＴｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料を銅合金に添加することが好ましい。また、銅合金の導電率を所定の導電率以上に維持することを目的として、総量で０．３質量％以下のＴｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の材料を銅合金に添加することが好ましい。 For the purpose of improving the bending workability by refining the crystal grain size, at least one kind selected from the group consisting of Ti, Zr, Hf, B, Ga, and In having a total amount of 0.03% by mass or more is used. It is preferred to add the material to the copper alloy. Further, for the purpose of maintaining the electrical conductivity of the copper alloy at a predetermined electrical conductivity or higher, at least selected from the group consisting of Ti, Zr, Hf, B, Ga, and In having a total amount of 0.3% by mass or less It is preferable to add one type of material to the copper alloy.
（銅合金の製造方法）
図１は、本発明の実施の形態に係る銅合金の製造工程の流れの一例を示す。
(Copper alloy manufacturing method)
FIG. 1 shows an example of the flow of a manufacturing process of a copper alloy according to an embodiment of the present invention.
本実施の形態に係る銅合金の製造方法により製造される銅合金は、一例として、板形状を有する銅合金である。まず、銅、例えば、無酸素銅を母材として、当該母材に複数の金属元素（すなわち、Ｎｉ、Ｃｏ、及びＳｉ、並びに、Ｔｉ、Ｚｒ、Ｈｆ、Ｂ、Ｇａ、及びＩｎからなる群から選択される少なくとも１種類の金属元素）が添加された原料としての銅合金を準備する（原料準備工程）。そして、この所定の組成を有する銅合金を無酸素銅を母材にして溶製することにより、銅合金からなるインゴットを鋳造する（鋳造工程：ステップ１０。以下、ステップを「Ｓ」と称する。）。次に、インゴットに押出加工を施して板状部材を形成する（押出加工工程：Ｓ２０）。 The copper alloy manufactured by the manufacturing method of the copper alloy which concerns on this Embodiment is a copper alloy which has a plate shape as an example. First, using copper, for example, oxygen-free copper as a base material, the base material includes a plurality of metal elements (ie, Ni, Co, and Si, and Ti, Zr, Hf, B, Ga, and In). A copper alloy is prepared as a raw material to which at least one selected metal element is added (raw material preparation step). Then, an ingot made of a copper alloy is cast by melting the copper alloy having the predetermined composition using oxygen-free copper as a base material (casting process: step 10; hereinafter, step is referred to as “S”). ). Next, the ingot is extruded to form a plate member (extrusion process: S20).
続いて、板状部材に冷間圧延を施して、第１の板材を形成する（第１冷間圧延工程：Ｓ３０）。第１の板材の厚さは、製造すべき板材の厚さよりも厚い厚さに制御する。具体的に、第１冷間圧延工程は、後述する第１の熱処理工程後の第２冷間圧延工程において、冷間圧延を施す材料に適切な量の格子欠陥を導入することを目的として、第１の板材の厚さが製造すべき板材の１．１倍以上１．３倍以下の厚さになるまで冷間圧延する。より具体的には、第１冷間圧延工程においては、第１の熱処理工程後の第２冷間圧延工程での板材の伸びの低下を抑制して良好な曲げ加工性を確保することを目的として、１．３倍以下の厚さまで冷間圧延する。また、第１冷間圧延工程においては、第２冷間圧延工程において導入される格子欠陥が少ないことに起因する、製造されるべき板材の耐力の低下の抑制を目的として、１．１倍以上の厚さまで冷間圧延する。 Subsequently, the plate member is cold rolled to form a first plate (first cold rolling step: S30). The thickness of the first plate is controlled to be thicker than the thickness of the plate to be manufactured. Specifically, the first cold rolling step is intended to introduce an appropriate amount of lattice defects in the material subjected to cold rolling in the second cold rolling step after the first heat treatment step described later. Cold rolling is performed until the thickness of the first plate becomes 1.1 to 1.3 times that of the plate to be manufactured. More specifically, in the first cold rolling process, the purpose is to ensure good bending workability by suppressing a decrease in the elongation of the plate material in the second cold rolling process after the first heat treatment process. As described above, it is cold-rolled to a thickness of 1.3 times or less. Further, in the first cold rolling process, 1.1 times or more for the purpose of suppressing the decrease in the proof stress of the plate material to be manufactured due to the small number of lattice defects introduced in the second cold rolling process. Cold-roll to a thickness of.
次に、第１の板材に加熱処理を施した後、加熱処理後の第１の板材を冷却する（第１の熱処理工程：Ｓ４０）。具体的に、第１の熱処理工程は、溶体化（すなわち、複数の金属元素、例えば、Ｃｏ、Ｎｉ、及びＳｉをＣｕ中に十分に固溶させる処理）を目的としており、第１の板材に８００℃以上９００℃以下の温度の加熱処理を施した後、毎分２５℃以上の降温速度で３００℃まで冷却する。なお、降温速度は毎分２５℃以上である限り上限を設けることを要さない。すなわち、冷却中の第１の板材中に析出物が生じること、及び仮に析出物が生じたとしても当該析出物の粗大化を抑制して機械的強度の弱い箇所の残存を抑制することを目的として、第１の熱処理工程における降温は急冷であることが好ましい。詳細には、第１の熱処理工程は、溶体化を十分に進行させることを目的として、加熱処理の温度を８００℃以上に設定すると共に、加熱処理により生成される結晶粒の粗大化により製造される銅合金の曲げ加工性の低下を抑制すべく９００℃以下の温度に設定する。そして、第１の熱処理工程は、冷却中の第１の板材中に粗大な析出物が再形成されることを防止すべく、降温速度を毎分２５℃以上に規定することが好ましい。 Next, after heat-processing a 1st board | plate material, the 1st board | plate material after heat processing is cooled (1st heat treatment process: S40). Specifically, the first heat treatment step is intended to form a solution (that is, a process in which a plurality of metal elements such as Co, Ni, and Si are sufficiently dissolved in Cu). After performing heat treatment at a temperature of 800 ° C. or higher and 900 ° C. or lower, it is cooled to 300 ° C. at a temperature lowering rate of 25 ° C. or more per minute. Note that it is not necessary to set an upper limit for the rate of temperature decrease as long as it is 25 ° C. or more per minute. That is, the purpose is to prevent precipitates from occurring in the first plate during cooling, and to suppress the remaining of the weak mechanical strength by suppressing the coarsening of the precipitates even if the precipitates are generated. As for temperature fall in the 1st heat treatment process, it is preferred that it is rapid cooling. Specifically, the first heat treatment step is produced by setting the temperature of the heat treatment to 800 ° C. or higher and coarsening the crystal grains generated by the heat treatment for the purpose of sufficiently progressing the solution treatment. The temperature is set to 900 ° C. or lower in order to suppress a decrease in bending workability of the copper alloy. In the first heat treatment step, it is preferable to regulate the temperature lowering rate to 25 ° C. or more per minute in order to prevent coarse precipitates from being re-formed in the first plate material being cooled.
第１の熱処理工程の後に、製造すべき板材の厚さ（すなわち、最終板厚）まで冷間圧延して第２の板材を形成する（第２冷間圧延工程：Ｓ５０）。続いて、第２の板材に、時効を目的とした第２の熱処理を施す。すなわち、第２の熱処理工程は、銅合金中に微細な析出物を形成することで、銅合金の導電率及び強度を向上させる。具体的には、第２の冷間圧延工程を経て得られる第２の板材に加熱処理を施した後、冷却する（第２の熱処理工程：Ｓ６０）。より具体的に、第２の熱処理工程は、第２の板材に４００℃以上５５０℃以下の温度の加熱処理を施した後、当該温度下において第２の板材を、３０分以上８時間以下、保持する。 After the first heat treatment step, the second plate is formed by cold rolling to the thickness of the plate to be manufactured (that is, the final plate thickness) (second cold rolling step: S50). Subsequently, a second heat treatment for aging is performed on the second plate material. That is, the second heat treatment step improves the electrical conductivity and strength of the copper alloy by forming fine precipitates in the copper alloy. Specifically, the second plate material obtained through the second cold rolling step is subjected to heat treatment and then cooled (second heat treatment step: S60). More specifically, in the second heat treatment step, after the heat treatment at a temperature of 400 ° C. or more and 550 ° C. or less is performed on the second plate material, the second plate material is treated at the temperature for 30 minutes or more and 8 hours or less, Hold.
なお、第２の熱処理工程における加熱処理の温度が５５０℃を超えると共に、保持時間が８時間を超える場合、銅合金中に析出する析出物が粗大化して、製造される銅合金の強度が低下する。また、第２の熱処理工程における加熱処理の温度が４００℃未満の場合、及び保持時間が３０分未満の場合、銅合金中に析出物が十分に析出しないので、製造される銅合金の導電率及び強度は十分な導電率及び強度にならない。 In addition, when the temperature of the heat treatment in the second heat treatment step exceeds 550 ° C. and the holding time exceeds 8 hours, precipitates precipitated in the copper alloy are coarsened and the strength of the produced copper alloy is reduced. To do. Further, when the temperature of the heat treatment in the second heat treatment step is less than 400 ° C. and when the holding time is less than 30 minutes, the precipitate does not sufficiently precipitate in the copper alloy, so the conductivity of the produced copper alloy And the strength is not sufficient conductivity and strength.
以上の工程を経ることにより、異方性の小さな結晶粒を有する銅合金を製造することができる。 By passing through the above process, the copper alloy which has a crystal grain with small anisotropy can be manufactured.
（実施の形態の効果）
本実施の形態に係る銅合金は上記のような構成を備えるので、８００ＭＰａ以上の引張強さ、１０％以上の伸び、５０％ＩＡＣＳ以上の導電率を有すると共に、金属組織の異方性が小さいことに起因する曲げ加工性の優れた高強度・高導電性の銅合金を提供できる。例えば、本実施の形態に係る銅合金は、優れた強度に加えて、良好な曲げ加工性を備えるので、端子、コネクタ、リレー、スイッチ等の電気・電子部品用（例えば、小型化された電気・電子部品用）の材料に用いることができる。
(Effect of embodiment)
Since the copper alloy according to the present embodiment has the above-described configuration, it has a tensile strength of 800 MPa or more, an elongation of 10% or more, a conductivity of 50% IACS or more, and a small metal structure anisotropy. Therefore, it is possible to provide a high-strength and high-conductivity copper alloy having excellent bending workability. For example, since the copper alloy according to the present embodiment has good bending workability in addition to excellent strength, it is used for electrical / electronic parts such as terminals, connectors, relays, switches, etc. -It can be used as a material for electronic parts).
また、本実施の形態に係る銅合金は、少なくとも従来のりん青銅、従来のＣｕ−Ｎｉ−Ｓｉ系合金等の銅合金よりも良好な強度、ばね性、導電性を有すると共に、優れた曲げ加工性を有しているので、当該銅合金から形成される電子部品の設計の自由度を拡大することができる。 Moreover, the copper alloy according to the present embodiment has at least better strength, springiness, and conductivity than copper alloys such as conventional phosphor bronze and conventional Cu-Ni-Si alloys, and has excellent bending work. Therefore, the degree of freedom in designing an electronic component formed from the copper alloy can be expanded.
実施の形態に基づいて製造した実施例１〜１１に係る銅合金と、比較例１〜１６に係る銅合金とについて説明する。 The copper alloy which concerns on Examples 1-11 manufactured based on Embodiment, and the copper alloy which concerns on Comparative Examples 1-16 are demonstrated.
（実施例１）
実施例１に係る銅合金は以下のようにして製造した。まず、１．５質量％のＮｉと、１．２質量％のＣｏと、０．６質量％のＳｉと、０．１５質量％のＳｎと、０．１５質量％のＺｎと、残部が無酸素銅及び不可避的不純物とからなる銅合金を母材にして、高周波溶解炉において溶製することにより、直径３０ｍｍ、長さ２５０ｍｍのインゴットを鋳造した（鋳造工程）。次に、得られたインゴットを９００℃で押出加工することにより幅２０ｍｍ、長さ８ｍｍの板状部材を製造した（押出加工工程）。更に、この板状部材に冷間圧延加工を施して、厚さ０．３ｍｍの第１の板材を形成した（第１冷間圧延工程）。
Example 1
The copper alloy according to Example 1 was manufactured as follows. First, 1.5 mass% Ni, 1.2 mass% Co, 0.6 mass% Si, 0.15 mass% Sn, 0.15 mass% Zn, and the balance An ingot having a diameter of 30 mm and a length of 250 mm was cast by using a copper alloy composed of oxygen copper and inevitable impurities as a base material and melting in a high frequency melting furnace (casting process). Next, the obtained ingot was extruded at 900 ° C. to produce a plate-like member having a width of 20 mm and a length of 8 mm (extrusion process). Furthermore, the plate member was cold rolled to form a first plate member having a thickness of 0.3 mm (first cold rolling step).
次に、第１の板材に８５０℃、１０分間の加熱処理を施した後、水中に投入して約３００℃／分の降温速度で室温（約２０℃）まで第１の板材を冷却した（第１の熱処理工程）。続いて、第１の板材に冷間圧延加工を施して、０．２５ｍｍの厚さの第２の板材を製造して（第２冷間圧延工程）、第２の板材に、４７０℃、２時間の第２の熱処理を施すことにより（第２の熱処理工程）、実施例１（試料Ｎｏ．１）に係る銅合金を製造した。 Next, after heat-treating the first plate material at 850 ° C. for 10 minutes, it was poured into water and the first plate material was cooled to room temperature (about 20 ° C.) at a temperature drop rate of about 300 ° C./minute ( First heat treatment step). Subsequently, the first plate material is cold-rolled to produce a second plate material having a thickness of 0.25 mm (second cold rolling process), and the second plate material is subjected to 470 ° C., 2 The copper alloy which concerns on Example 1 (sample No. 1) was manufactured by giving the 2nd heat processing for time (2nd heat processing process).
以上のようにして製造した実施例１に係る銅合金の引張強さ、伸び、導電率の各特性値を測定した。引張強さ及び伸びについてはＪＩＳ Ｚ ２２４１に準拠して測定した。また、導電率は、ＪＩＳ Ｈ ０５０５に準拠して測定した。その結果、実施例１に係る銅合金の引張強さは８２６ＭＰａであり、伸びは１２％であり、導電率は５３％ＩＡＣＳであった。 Each characteristic value of tensile strength, elongation, and conductivity of the copper alloy according to Example 1 manufactured as described above was measured. Tensile strength and elongation were measured according to JIS Z 2241. The conductivity was measured according to JIS H 0505. As a result, the tensile strength of the copper alloy according to Example 1 was 826 MPa, the elongation was 12%, and the conductivity was 53% IACS.
（実施例２〜１１）
表１に示す組成を有するインゴットを実施例１に係るインゴットと同様に鋳造した。そして、鋳造して得られたインゴットから、実施例１と同様の工程により実施例２〜１１（試料Ｎｏ．２〜１１）に係る厚さが０．２５ｍｍの銅合金を製造した。そして、実施例２〜１１に係る銅合金のそれぞれについて、実施例１と同様にして引張強さ、伸び、及び導電率の各特性値を測定した。測定結果を表２に示す。
(Examples 2 to 11)
An ingot having the composition shown in Table 1 was cast in the same manner as the ingot according to Example 1. And from the ingot obtained by casting, the copper alloy whose thickness which concerns on Examples 2-11 (sample No. 2-11) based on the process similar to Example 1 is 0.25 mm was manufactured. And about each of the copper alloys which concern on Examples 2-11, it carried out similarly to Example 1, and measured each characteristic value of tensile strength, elongation, and electrical conductivity. The measurement results are shown in Table 2.
表２を参照すると分かるように、実施例１〜１１に係る銅合金はすべて、優れた引張強さ、伸び、及び導電率を示した。 As can be seen with reference to Table 2, all of the copper alloys according to Examples 1-11 exhibited excellent tensile strength, elongation, and conductivity.
また、実施例１〜１１に係る銅合金について、圧延加工方向に対して平行な断面の結晶組織を観察した。具体的には、実施例１〜１１に係る銅合金をＪＩＳ Ｈ ０５０１に規定された切断方法で切断して、その切断面において観察される結晶粒の長径ａ及び短径ｂを測定した。そして、長径の短径に対する比ａ／ｂと平均値（ａ＋ｂ）／２とを算出した。更に、実施例１〜１１に係る銅合金について、曲げ加工についての異方性を確認することを目的として曲げ試験を実施した。曲げ試験の試験方法は、ＪＩＳ Ｈ ３１１０に規定されたＷ曲げ試験に準拠して実施した。すなわち、銅合金を曲げ半径０ｍｍで９０度に曲げ、曲げ部分の表面を観察することにより亀裂の発生の有無を観察した。ここで、曲げ軸の方向が圧延方向に直角になるように曲げた場合、及び圧延方向に平行になるように曲げた場合のそれぞれについて観察して異方性の有無を確認した。測定結果を表３に示す。 Moreover, about the copper alloy which concerns on Examples 1-11, the crystal structure of the cross section parallel to the rolling direction was observed. Specifically, the copper alloys according to Examples 1 to 11 were cut by the cutting method defined in JIS H 0501, and the major axis “a” and the minor axis “b” of the crystal grains observed on the cut surface were measured. And ratio a / b and average value (a + b) / 2 with respect to the minor axis of a major axis were computed. Furthermore, the bending test was implemented about the copper alloy which concerns on Examples 1-11 in order to confirm the anisotropy about a bending process. The test method for the bending test was carried out in accordance with the W bending test defined in JIS H3110. That is, the presence or absence of cracks was observed by bending the copper alloy at 90 ° with a bending radius of 0 mm and observing the surface of the bent portion. Here, the presence or absence of anisotropy was confirmed by observing the case where the bending axis was bent so as to be perpendicular to the rolling direction and the case where the bending axis was bent parallel to the rolling direction. Table 3 shows the measurement results.
実施例１〜１１に係る銅合金はすべて、圧延方向に平行な方向と圧延方向に直角な方向との双方について、良好な曲げ加工性を有することが確認された。特に、実施例１に係る銅合金に対して、０．０５質量％のＴｉを更に添加した実施例６に係る銅合金、０．０５質量％のＺｒを更に添加した実施例７に係る銅合金、０．０５質量％のＨｆを更に添加した実施例８に係る銅合金、０．０５質量％のＢを更に添加した実施例９に係る銅合金、０．０５質量％のＧａを更に添加した実施例１０に係る銅合金、及び０．０５質量％のＩｎを更に添加した実施例１１に係る銅合金はいずれも、結晶粒の微細化が顕著であり、これらの金属元素の添加により、強度と曲げ加工性との双方を更に向上させることができることが示された。 It was confirmed that all the copper alloys according to Examples 1 to 11 have good bending workability in both the direction parallel to the rolling direction and the direction perpendicular to the rolling direction. In particular, the copper alloy according to Example 6 in which 0.05% by mass of Ti is further added to the copper alloy according to Example 1, and the copper alloy according to Example 7 in which 0.05% by mass of Zr is further added. The copper alloy according to Example 8 to which 0.05 mass% of Hf was further added, the copper alloy according to Example 9 to which 0.05 mass% of B was further added, and 0.05 mass% of Ga were further added. Both the copper alloy according to Example 10 and the copper alloy according to Example 11 to which 0.05% by mass of In was further added had remarkable crystal grain refinement. By adding these metal elements, the strength was increased. It was shown that both the bending workability and the bending workability can be further improved.
（比較例）
比較例１〜１０（試料Ｎｏ．１２〜２１）に係る銅合金として、表１に示した組成を有するインゴットをそれぞれ鋳造した。そして、実施例と同様に、インゴットに所定の加工、熱処理等を施して、厚さ０．２５ｍｍの比較例１〜１０に係る銅合金を製造した。そして、比較例１〜１０に係る銅合金のそれぞれについて、実施例と同様にして、引張強さ、伸び、及び導電率の各特性値を測定した。測定結果を表２に示す。
(Comparative example)
As the copper alloys according to Comparative Examples 1 to 10 (Sample Nos. 12 to 21), ingots having the compositions shown in Table 1 were cast. And like the Example, predetermined processing, heat processing, etc. were given to the ingot, and the copper alloy which concerns on Comparative Examples 1-10 of thickness 0.25mm was manufactured. And about each of the copper alloys which concern on Comparative Examples 1-10, it carried out similarly to the Example, and measured each characteristic value of tensile strength, elongation, and electrical conductivity. The measurement results are shown in Table 2.
比較例１及び比較例２に係る銅合金は、本実施の形態に係る銅合金のＮｉ、Ｃｏ、及びＳｉの含有量の範囲外の量のＮｉ、Ｃｏ、及びＳｉを含有する銅合金である。そして、比較例１に係る銅合金は、Ｎｉ、Ｃｏ、及びＳｉの含有量が少ないことに起因して、十分な引張強さが得られなかった。また、比較例２に係る銅合金においては、Ｎｉ、Ｃｏ、及びＳｉの含有量が多いことに起因して、銅合金の導電率が低下した。 The copper alloys according to Comparative Example 1 and Comparative Example 2 are copper alloys containing Ni, Co, and Si in amounts outside the range of Ni, Co, and Si contents of the copper alloy according to the present embodiment. . And the copper alloy which concerns on the comparative example 1 was not able to obtain sufficient tensile strength resulting from there being little content of Ni, Co, and Si. Moreover, in the copper alloy which concerns on the comparative example 2, the electrical conductivity of a copper alloy fell because of having much content of Ni, Co, and Si.
比較例３及び比較例４に係る銅合金は、本実施の形態に係る銅合金のＮｉとＣｏとの合計量とＳｉの量との比率の範囲外の量のＮｉ、Ｃｏ、及びＳｉを含有する銅合金である。表２に示すように、比較例３及び比較例４に係る銅合金の特性を参照すると、ＮｉとＣｏとの合計量がＳｉの量より過剰になった場合、及びＳｉの量がＮｉとＣｏとの合計量より過剰になった場合のいずれも、導電率が悪化すると共に、良好な引張強さが得られないことが示された。 The copper alloys according to Comparative Example 3 and Comparative Example 4 contain Ni, Co, and Si in amounts outside the range of the ratio of the total amount of Ni and Co and the amount of Si in the copper alloy according to the present embodiment. Copper alloy. As shown in Table 2, referring to the characteristics of the copper alloys according to Comparative Example 3 and Comparative Example 4, when the total amount of Ni and Co exceeds the amount of Si, the amount of Si is Ni and Co. It was shown that in any case where the total amount was excessive, the electrical conductivity deteriorated and good tensile strength could not be obtained.
比較例５及び比較例６に係る銅合金は、本実施の形態に係る銅合金のＮｉの量とＣｏの量との比率の範囲外の量のＮｉ、及びＣｏを含有する銅合金である。表２に示すように、比較例５及び比較例６に係る銅合金の特性を参照すると、Ｎｉの量がＣｏの量に対して過剰になると導電率が低下することが示され、Ｃｏの量がＮｉの量に対して過剰になると十分な引張強さが得られないことが示された。 The copper alloys according to Comparative Example 5 and Comparative Example 6 are copper alloys containing Ni and Co in amounts outside the range of the ratio between the amount of Ni and the amount of Co in the copper alloy according to the present embodiment. As shown in Table 2, referring to the characteristics of the copper alloys according to Comparative Example 5 and Comparative Example 6, it is shown that the conductivity decreases when the amount of Ni is excessive with respect to the amount of Co. It has been shown that sufficient tensile strength cannot be obtained when the amount of is excessive with respect to the amount of Ni.
比較例７〜比較例９に係る銅合金は、本実施の形態に係る銅合金のＳｎの量とＺｎの量との範囲外の量のＳｎ、及びＺｎを含有する銅合金である。表２に示すように、比較例７〜９に係る銅合金の特性を参照すると、Ｓｎ及びＺｎを含まない比較例７に係る銅合金は引張強さが不足していることが示され、Ｓｎ及びＺｎを実施例１〜１１に比べて過剰に含有している比較例８及び比較例９に係る銅合金は、導電率が悪化していることが示された。また、比較例１０に係る銅合金は、添加するＴｉの量が実施例に比べて過剰である銅合金である。表２を参照すると、比較例１０に係る銅合金の導電率の悪化が顕著であることが示された。 The copper alloys according to Comparative Examples 7 to 9 are copper alloys containing Sn and Zn in amounts outside the range of the Sn content and the Zn content of the copper alloy according to the present embodiment. As shown in Table 2, referring to the characteristics of the copper alloys according to Comparative Examples 7 to 9, it is shown that the copper alloy according to Comparative Example 7 containing no Sn and Zn has insufficient tensile strength, Sn And it was shown that the copper alloy which concerns on the comparative example 8 and the comparative example 9 which contains Zn excessively compared with Examples 1-11 has deteriorated electrical conductivity. Moreover, the copper alloy which concerns on the comparative example 10 is a copper alloy in which the quantity of Ti to add is excess compared with an Example. When Table 2 was referred, it was shown that the deterioration of the electrical conductivity of the copper alloy which concerns on the comparative example 10 is remarkable.
続いて、実施例１に係る銅合金の製造条件を所定の製造条件に代えて製造した比較例１１〜１６（試料Ｎｏ．２２〜２７）に係る銅合金について説明する。具体的に、実施例１に係る銅合金と同一のインゴットを鋳造した。そして、第１の熱処理工程の前の冷間圧延材（すなわち、熱処理を施す前の第１の板材）と第２の熱処理後の最終材（すなわち、最終的に製造される銅合金）との板厚比（以下、「熱処理前と最終材との板厚比」という）、第１の熱処理工程の加熱条件、及び第２の熱処理工程の加熱条件を表４に示す条件で実施することにより、比較例１１〜１６に係る銅合金をそれぞれ製造した。 Then, the copper alloy which concerns on Comparative Examples 11-16 (sample No. 22-27) manufactured by replacing the manufacturing conditions of the copper alloy which concerns on Example 1 with predetermined manufacturing conditions is demonstrated. Specifically, the same ingot as the copper alloy according to Example 1 was cast. And the cold-rolled material before the first heat treatment step (that is, the first plate material before the heat treatment) and the final material after the second heat treatment (that is, the finally produced copper alloy) By carrying out the plate thickness ratio (hereinafter referred to as “plate thickness ratio before heat treatment and final material”), the heating conditions of the first heat treatment step, and the heating conditions of the second heat treatment step under the conditions shown in Table 4. The copper alloys according to Comparative Examples 11 to 16 were produced.
比較例１１〜１６に係る銅合金のそれぞれについて実施例と同様に引張強さ、導電率の各特性値を測定した。また、圧延加工方向に平行な断面における金属組織の結晶粒の長径及び短径を測定して、長径の短径に対する比ａ／ｂ、及び平均値（ａ＋ｂ）／２を算出した。更に、実施例と同様にしてＷ曲げ試験によって曲げ加工性を確認した。これらの測定結果を表５に示す。 About each of the copper alloys which concern on Comparative Examples 11-16, each characteristic value of tensile strength and electrical conductivity was measured similarly to the Example. Further, the major axis and minor axis of the crystal grains of the metal structure in the cross section parallel to the rolling direction were measured, and the ratio a / b of the major axis to the minor axis and the average value (a + b) / 2 were calculated. Furthermore, bending workability was confirmed by a W bending test in the same manner as in the examples. These measurement results are shown in Table 5.
比較例１１及び比較例１２に係る銅合金は、熱処理前と最終材との板厚比が本実施の形態に係る銅合金の製造方法における１．１倍以上１．３倍以下の範囲から外れた条件で製造された銅合金である。表５を参照すると、比較例１１のように熱処理前の板厚（すなわち、熱処理を施す前の第１の板材の厚さ）が薄いと、不十分な引張強さを有する銅合金になることが示された。また、比較例１２のように熱処理を施す前の第１の板材の厚さが厚いと、第２の冷間圧延工程において結晶粒が大きく変形することに起因して、結晶粒の長径の短径に対する比率が、本実施の形態の範囲外になる。これにより、比較例１２においては、曲げ試験において、特に、圧延方向に平行な曲げ軸に沿って銅合金を曲げたときに割れが発生した。 In the copper alloys according to Comparative Example 11 and Comparative Example 12, the plate thickness ratio between the pre-heat treatment and the final material is out of the range of 1.1 to 1.3 times in the copper alloy manufacturing method according to the present embodiment. Copper alloy manufactured under different conditions. Referring to Table 5, when the plate thickness before heat treatment (that is, the thickness of the first plate material before heat treatment) is thin as in Comparative Example 11, the copper alloy has insufficient tensile strength. It has been shown. Further, if the thickness of the first plate before the heat treatment as in Comparative Example 12 is large, the crystal grains are greatly deformed in the second cold rolling process, so that the major axis of the crystal grains is short. The ratio to the diameter is out of the range of the present embodiment. Thereby, in the comparative example 12, the crack generate | occur | produced when bending a copper alloy along the bending axis | shaft parallel to a rolling direction in the bending test.
比較例１３及び比較例１４に係る銅合金は、第１の熱処理工程の加熱温度を、本実施の形態に係る銅合金の製造方法における温度範囲外の温度にして製造された銅合金である。表５を参照すると、第１の熱処理工程の加熱温度が本実施の形態における加熱温度よりも低いと、十分な強度を有した銅合金が得られず、第１の熱処理工程の加熱温度が本実施の形態における加熱温度よりも高いと、結晶粒径が大きくなることに起因して曲げ試験における割れが発生しやすいことが示された。 The copper alloys according to Comparative Example 13 and Comparative Example 14 are copper alloys manufactured by setting the heating temperature in the first heat treatment step to a temperature outside the temperature range in the copper alloy manufacturing method according to the present embodiment. Referring to Table 5, when the heating temperature in the first heat treatment step is lower than the heating temperature in the present embodiment, a copper alloy having sufficient strength cannot be obtained, and the heating temperature in the first heat treatment step is It was shown that when the heating temperature is higher than that in the embodiment, cracks in the bending test are likely to occur due to an increase in the crystal grain size.
比較例１５及び比較例１６に係る銅合金は、第２の熱処理工程の加熱温度を、本実施の形態に係る銅合金の製造方法における温度範囲外の温度にして製造された銅合金である。表５を参照すると、第２の熱処理工程の加熱温度が本実施の形態における加熱温度よりも低いと、導電率が低いと共に不十分な引張強さを有する銅合金が製造され、第１の熱処理工程の加熱温度が本実施の形態における加熱温度よりも高いと、結晶粒径が大きくなると共に、不十分な引張強さを有する銅合金が製造されることが示された。 The copper alloys according to Comparative Example 15 and Comparative Example 16 are copper alloys manufactured by setting the heating temperature in the second heat treatment step to a temperature outside the temperature range in the copper alloy manufacturing method according to the present embodiment. Referring to Table 5, when the heating temperature in the second heat treatment step is lower than the heating temperature in the present embodiment, a copper alloy having low electrical conductivity and insufficient tensile strength is manufactured, and the first heat treatment is performed. It has been shown that when the heating temperature in the process is higher than the heating temperature in the present embodiment, the crystal grain size increases and a copper alloy having insufficient tensile strength is produced.
以上、本発明の実施の形態及び実施例を説明したが、上記に記載した実施の形態及び実施例は特許請求の範囲に係る発明を限定するものではない。また、実施の形態及び実施例の中で説明した特徴の組合せの全てが発明の課題を解決するための手段に必須であるとは限らない点に留意すべきである。 While the embodiments and examples of the present invention have been described above, the embodiments and examples described above do not limit the invention according to the claims. It should be noted that not all combinations of features described in the embodiments and examples are necessarily essential to the means for solving the problems of the invention.
Claims (10)
Ｓｉと、前記Ｓｉと反応してシリコン化合物を形成するＮｉ及びＣｏと、前記銅合金に含まれる結晶粒の成長を抑制するＳｎ及びＺｎとを含有すると共に、残部がＣｕと不可避的不純物とからなり、
前記Ｎｉと前記Ｃｏとの合計量の前記Ｓｉに対する質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉが４以上５以下であり、
前記Ｎｉの前記Ｃｏに対する質量濃度比Ｎｉ／Ｃｏが０．５以上２以下であり、
前記圧延加工の圧延方向に対して平行な断面における前記銅合金の結晶粒の長径ａと短径ｂとの比ａ／ｂが１．０以上２．５以下であると共に、前記長径ａと前記短径ｂとの相加平均値（ａ＋ｂ）／２が１０μｍ以下である銅合金。 A copper alloy manufactured through rolling,
It contains Si, Ni and Co that react with Si to form a silicon compound, Sn and Zn that suppress the growth of crystal grains contained in the copper alloy, and the balance is Cu and inevitable impurities. Become
The mass concentration ratio (Ni + Co) / Si of the total amount of Ni and Co to Si is 4 or more and 5 or less,
The mass concentration ratio Ni / Co to Co of Ni is 0.5 or more and 2 or less,
The ratio a / b of the major axis a and the minor axis b of the copper alloy crystal grains in a cross section parallel to the rolling direction of the rolling process is 1.0 or more and 2.5 or less, and the major axis a and the A copper alloy having an arithmetic average value (a + b) / 2 with a minor axis b of 10 μm or less.
前記Ｃｏは、０．５質量％以上２．０質量％以下含有され、
前記Ｓｉは、０．３質量％以上１．０質量％以下含有され、
前記Ｓｎは、０．０５質量％以上０．３質量％以下含有され、
前記Ｚｎは、０．０５質量％以上０．５質量％以下含有される請求項１に記載の銅合金。 The Ni is contained in an amount of 1.0% by mass to 2.5% by mass,
Co is contained in an amount of 0.5% by mass or more and 2.0% by mass or less,
The Si is contained in an amount of 0.3% by mass to 1.0% by mass,
The Sn is contained in an amount of 0.05% by mass to 0.3% by mass,
2. The copper alloy according to claim 1, wherein the Zn is contained in an amount of 0.05% by mass or more and 0.5% by mass or less.
複数の金属元素を含む原料としての銅合金を準備する原料準備工程と、
前記原料としての銅合金を溶製してインゴットを鋳造する鋳造工程と、
前記インゴットに押出加工を施して板状部材を形成する押出加工工程と、
前記板状部材を、前記板材の厚さよりも厚い厚さまで冷間圧延して第１の板材を形成する第１冷間圧延工程と、
前記第１の板材に加熱処理を施した後、冷却する第１の熱処理工程と、
前記第１の熱処理工程の後に、前記板材の厚さまで冷間圧延して第２の板材を形成する第２冷間圧延工程と、
前記第２の冷間圧延工程の後に、前記第２の板材に加熱処理を施した後、冷却する第２の熱処理工程と
を備える銅合金の製造方法。 A method for producing a copper alloy exhibiting a plate material,
A raw material preparation step of preparing a copper alloy as a raw material containing a plurality of metal elements;
A casting process in which an ingot is cast by melting a copper alloy as the raw material;
An extrusion process for forming a plate-like member by performing extrusion on the ingot;
A first cold rolling step of cold-rolling the plate-like member to a thickness greater than the thickness of the plate material to form a first plate material;
A first heat treatment step of cooling the first plate after the heat treatment;
A second cold rolling step of forming a second plate by cold rolling to the thickness of the plate after the first heat treatment step;
After the said 2nd cold rolling process, after giving a heat processing to the said 2nd board | plate material, the manufacturing method of a copper alloy provided with the 2nd heat treatment process cooled.
前記第１の熱処理工程は、前記第１の板材に８００℃以上９００℃以下の温度の加熱処理を施した後、毎分２５℃以上の降温速度で３００℃まで冷却し、
前記第２の熱処理工程は、前記第２の板材に４００℃以上５５０℃以下の温度の加熱処理を施した後、当該温度下で３０分以上８時間以下、保持する請求項５に記載の銅合金の製造方法。 In the first cold rolling step, cold rolling is performed until the thickness of the first plate is 1.1 times or more and 1.3 times or less that of the plate,
In the first heat treatment step, the first plate material is subjected to a heat treatment at a temperature of 800 ° C. or more and 900 ° C. or less, and then cooled to 300 ° C. at a temperature lowering rate of 25 ° C. or more per minute.
6. The copper according to claim 5, wherein in the second heat treatment step, the second plate material is subjected to a heat treatment at a temperature of 400 ° C. or more and 550 ° C. or less and then held at the temperature for 30 minutes or more and 8 hours or less. Alloy manufacturing method.
前記Ｎｉと前記Ｃｏとの合計量の前記Ｓｉに対する質量濃度比（Ｎｉ＋Ｃｏ）／Ｓｉが４以上５以下であり、
前記Ｎｉの前記Ｃｏに対する質量濃度比Ｎｉ／Ｃｏが０．５以上２以下であり、
前記圧延加工の圧延方向に対して平行な断面における前記銅合金の結晶粒の長径ａと短径ｂとの比ａ／ｂが１．０以上２．５以下であると共に、前記長径ａと前記短径ｂとの相加平均値（ａ＋ｂ）／２が１０μｍ以下である請求項６に記載の銅合金の製造方法。 The manufactured copper alloy contains Si, Ni and Co that react with Si to form a silicon compound, Sn and Zn that suppress the growth of crystal grains contained in the copper alloy, and the balance Consists of Cu and inevitable impurities,
The mass concentration ratio (Ni + Co) / Si of the total amount of Ni and Co to Si is 4 or more and 5 or less,
The mass concentration ratio Ni / Co to Co of Ni is 0.5 or more and 2 or less,
The ratio a / b of the major axis a and the minor axis b of the copper alloy crystal grains in a cross section parallel to the rolling direction of the rolling process is 1.0 or more and 2.5 or less, and the major axis a and the The method for producing a copper alloy according to claim 6, wherein the arithmetic average value (a + b) / 2 with the minor axis b is 10 μm or less.
前記Ｃｏは、０．５質量％以上２．０質量％以下含有され、
前記Ｓｉは、０．３質量％以上１．０質量％以下含有され、
前記Ｓｎは、０．０５質量％以上０．３質量％以下含有され、
前記Ｚｎは、０．０５質量％以上０．５質量％以下含有される請求項７に記載の銅合金の製造方法。 The Ni is contained in an amount of 1.0% by mass to 2.5% by mass,
Co is contained in an amount of 0.5 mass% to 2.0 mass%,
The Si is contained in an amount of 0.3% by mass to 1.0% by mass,
The Sn is contained in an amount of 0.05% by mass to 0.3% by mass,
The said Zn is a manufacturing method of the copper alloy of Claim 7 contained 0.05 mass% or more and 0.5 mass% or less.
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