JP5748945B2 - Copper alloy material manufacturing method and copper alloy material obtained thereby - Google Patents
Copper alloy material manufacturing method and copper alloy material obtained thereby Download PDFInfo
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本発明は端子・コネクタなどの電子部品用に好適な、強度、導電率、および打ち抜き加工性に優れた電子機器用の銅合金材を製造する方法と、それにより得られる銅合金材に関する。 The present invention relates to a method for producing a copper alloy material for an electronic device excellent in strength, electrical conductivity, and punchability, suitable for electronic parts such as terminals and connectors, and a copper alloy material obtained thereby.
近年、大電流を通電する電子機器の小型軽量化が進展し、電子部品材料は導電率が高くかつ強度に優れることが強く求められている。ＣｏとＳｉを主添加元素とした銅合金は優れた機械的強度、導電率を有しているため、上記電子部品に適しているとされる。これら電子部品は金型を用いた高速プレスによる打ち抜き加工を行って製造されるものが主であり、製造時、材料は金型のパンチによりせん断変形、破断変形を生じて所定の形状に打ち抜かれる。しかし、プレスショット数が増すにつれて金型のパンチの刃先の磨耗が進み、破断形状が乱れて製品形状を保てなくなる。金型メンテナンスのコスト削減の手段として、金型磨耗を軽減する、もしくは初期の金型形状から磨耗が進んだ時点においてもプレス形状を維持できる、打ち抜き加工性に優れる銅合金が求められている（特許文献１〜６参照）。 In recent years, electronic devices that carry a large current have been reduced in size and weight, and electronic component materials are strongly required to have high conductivity and excellent strength. A copper alloy containing Co and Si as main additive elements is considered to be suitable for the electronic component because it has excellent mechanical strength and electrical conductivity. These electronic components are mainly manufactured by punching with a high-speed press using a mold, and at the time of manufacturing, the material is punched into a predetermined shape by causing shear deformation or fracture deformation by the punch of the mold. . However, as the number of press shots increases, the cutting edge of the die punch advances and the fracture shape is disturbed, making it impossible to maintain the product shape. As a means of reducing the cost of mold maintenance, there is a need for a copper alloy with excellent punchability that can reduce mold wear or maintain the press shape even when the wear progresses from the initial mold shape ( Patent References 1 to 6).
しかしながら、特許文献１〜６で提案されているＣｏ、Ｓｉを主添加元素とした銅合金は、いずれも高強度、高導電性や熱間加工性などに着目したもので、プレス打ち抜き性についての記載はない。これらの文献に記載された銅合金の製造方法においては、プレス打ち抜き加工性向上に必要な化合物制御がなされていないことが伺える。
そこで、本発明は、Ｃｕ−Ｃｏ−Ｓｉ系合金において、コネクタ用端子など電子部品に要求される強度と導電性を維持しつつ打ち抜き加工性に優れる銅合金材を製造する方法と、それにより得られる銅合金材を提供することを課題とする。
However, the copper alloys with Co and Si as the main additive elements proposed in Patent Documents 1 to 6 are all focused on high strength, high conductivity, hot workability, etc. There is no description. In the copper alloy manufacturing methods described in these documents, it can be seen that the compound control necessary for improving the press punching processability is not performed.
Accordingly, the present invention provides a method for producing a copper alloy material excellent in punching workability while maintaining strength and conductivity required for electronic parts such as connector terminals in a Cu-Co-Si based alloy, and thereby obtained. It is an object of the present invention to provide a copper alloy material.
本発明者等は、Ｃｕ−Ｃｏ−Ｓｉ系合金において打ち抜き加工性を向上させる化合物を制御することにより、上記の課題を解決できることを見出した。すなわち、合金組成と鋳造・熱処理などの製造条件を特定の条件に規定して、得られる銅合金中の化合物サイズ、密度を特定の範囲内にコントロールすることによって、従来の銅合金の強度、導電率特性を維持しつつ、打ち抜き加工性を改善しうることを見出し、この知見に基づき本発明をなすに至った。 The present inventors have found that the above problem can be solved by controlling a compound that improves the punching workability in a Cu—Co—Si based alloy. That is, by specifying the manufacturing conditions such as the alloy composition and casting / heat treatment to specific conditions, and controlling the compound size and density in the obtained copper alloy within a specific range, the strength and conductivity of conventional copper alloys are controlled. It has been found that the punching processability can be improved while maintaining the rate characteristics, and the present invention has been made based on this finding.
上記課題は以下の発明により解決される。
（１）Ｃｏを０．５〜２．５ｍａｓｓ％含有し、ＣｏとＳｉの含有量の比Ｃｏ／Ｓｉが２．５〜４．５の間にあり、さらにＣｒ、Ｆｅ、Ｎｉ、Ａｌ、Ｎｂ、Ｔｉ、Ｖ及びＺｒからなる群から選ばれる少なくとも１種の添加元素を合計で０．０１〜０．２ｍａｓｓ％含み、残部がＣｕおよび不可避不純物からなる銅合金原料を溶解し、鋳造時の冷却速度が１〜３０℃／秒の条件で鋳造して鋳塊を得、
均質処理、
熱間圧延、
水冷却、
冷間圧延、
８００〜１０２５℃で１〜１００秒間の溶体化熱処理、
３００〜６００℃で１〜１０時間の時効熱処理、
加工率が０％を超えて３０％以下の仕上げ圧延、
２００〜４５０℃で０．５〜５時間の歪取り焼鈍を施す
各工程をこの順に施し、
直径が０．０５〜５μｍで、密度が１０ ３ 〜１０ ５ 個／ｍｍ ２ の、前記添加元素及びＣｏからなる群から選ばれる少なくとも１種の元素とＳｉからなる化合物を含有する銅合金材を得ることを特徴とする銅合金材の製造方法。
（２）Ｃｏを１．４ｍａｓｓ％以上２．５ｍａｓｓ％以下含有し、ＣｏとＳｉの含有量の比Ｃｏ／Ｓｉが３．０〜５．０の間にあり、残部がＣｕおよび不可避不純物からなる銅合金原料を溶解し、鋳造時の冷却速度が１〜３０℃／秒の条件で鋳造して鋳塊を得、
均質処理、
熱間圧延、
水冷却、
冷間圧延、
８００〜１０２５℃で１〜１００秒間の溶体化熱処理、
３００〜６００℃で１〜１０時間の時効熱処理、
加工率が０％を超えて３０％以下の仕上げ圧延、
２００〜４５０℃で０．５〜５時間の歪取り焼鈍を施す
各工程をこの順に施し、
直径が０．０５〜５μｍで、密度が１０ ３ 〜１０ ５ 個／ｍｍ ２ のＣｏ及びＳｉで構成される化合物を含有する銅合金材を得ることを特徴とする銅合金材の製造方法。
（３）（１）項に記載の方法で製造される銅合金材であって、得られる銅合金材が、直径が０．０５〜５μｍで、密度が１０３〜１０５個／ｍｍ２の、前記添加元素及びＣｏからなる群から選ばれる少なくとも１種の元素とＳｉからなる化合物を含有する銅合金材。
（４）（２）項に記載の方法で製造される銅合金材であって、得られる銅合金材が、直径が０．０５〜５μｍで、密度が１０３〜１０５個／ｍｍ２のＣｏ及びＳｉで構成される化合物を含有する銅合金材。
なお、本発明における「化合物」は上記２種以上の元素からなる金属間化合物であり、晶出物（液体から固体に変態する際あらわれる金属間化合物）と析出物（固体から固体に変態する際、例えば固溶状態から、あらわれる金属間化合物）の両方を含む。
The above problems are solved by the following invention.
(1) Co is contained at 0.5 to 2.5 mass%, Co / Si content ratio Co / Si is between 2.5 and 4.5, and Cr, Fe, Ni, Al, Nb , Including at least one additive element selected from the group consisting of Ti, V and Zr in a total amount of 0.01 to 0.2 mass%, with the balance being a copper alloy raw material consisting of Cu and inevitable impurities, and cooling during casting Casting at a speed of 1-30 ° C / sec to obtain an ingot,
Homogeneous treatment,
Hot rolling,
Water cooling,
Cold rolling,
Solution heat treatment for 1 to 100 seconds at 800 to 1025 ° C.,
Aging heat treatment at 300-600 ° C. for 1-10 hours,
Working ratio of 30% or less of finish rolling exceeds 0%,
Each step of at 200 to 450 ° C. performing stress relief annealing of 0.5-5 hours facilities in this order,
A copper alloy material containing a compound comprising Si and at least one element selected from the group consisting of the additive element and Co, having a diameter of 0.05 to 5 μm and a density of 10 3 to 10 5 pieces / mm 2. A method for producing a copper alloy material, comprising: obtaining a copper alloy material.
(2) Co is contained in an amount of 1.4 mass% to 2.5 mass%, the Co / Si content ratio Co / Si is between 3.0 and 5.0, and the balance is made of Cu and inevitable impurities. A copper alloy raw material is melted and cast at a cooling rate of 1-30 ° C./second during casting to obtain an ingot,
Homogeneous treatment,
Hot rolling,
Water cooling,
Cold rolling,
Solution heat treatment for 1 to 100 seconds at 800 to 1025 ° C.,
Aging heat treatment at 300-600 ° C. for 1-10 hours,
Working ratio of 30% or less of finish rolling exceeds 0%,
Each step of at 200 to 450 ° C. performing stress relief annealing of 0.5-5 hours facilities in this order,
A method for producing a copper alloy material, comprising: obtaining a copper alloy material containing a compound composed of Co and Si having a diameter of 0.05 to 5 μm and a density of 10 3 to 10 5 pieces / mm 2 .
(3 ) A copper alloy material produced by the method according to (1 ) , wherein the obtained copper alloy material has a diameter of 0.05 to 5 μm and a density of 10 3 to 10 5 pieces / mm 2 . A copper alloy material comprising a compound comprising Si and at least one element selected from the group consisting of the additive element and Co.
( 4 ) A copper alloy material produced by the method according to (2 ) , wherein the obtained copper alloy material has a diameter of 0.05 to 5 μm and a density of 10 3 to 10 5 pieces / mm 2 . A copper alloy material containing a compound composed of Co and Si.
The “compound” in the present invention is an intermetallic compound composed of two or more elements described above, and a crystallized product (intermetallic compound that appears when transforming from liquid to solid) and a precipitate (when transforming from solid to solid). For example, an intermetallic compound appearing from a solid solution state).
本発明の銅合金材の製造方法により得られる銅合金材（以下、本書において単に「本発明の銅合金材」ともいう。）は、強度、導電率を損なわずに打ち抜き加工性を向上させたものである。よって、電子機器用の部品、例えば端子・コネクタ等としたときに銅合金材に要求される高レベルの特性を有し、かつ、打ち抜き加工における金型長寿命化によってコストパフォーマンスの改善が行われる。 The copper alloy material obtained by the method for producing a copper alloy material of the present invention (hereinafter, also simply referred to as “the copper alloy material of the present invention” in this document) has improved punching workability without impairing strength and electrical conductivity. Is. Therefore, it has high-level characteristics required for copper alloy materials when used as parts for electronic equipment such as terminals and connectors, etc., and cost performance is improved by extending the die life in stamping. .
以下に、本発明の好ましい実施の形態を述べる。なお、本発明において銅合金材とは、圧延工程によって、例えば板材、条材、箔などの特定の形状に加工された銅合金を意味する。
本発明の銅合金材の第一の実施形態における組成は、Ｃｏ、Ｓｉとその他の添加元素（Ｃｒ、Ｆｅ、Ｎｉ、Ａｌ、Ｎｂ、Ｔｉ、Ｖ及びＺｒからなる群から選ばれる少なくとも１種）とを含有し、残部がＣｕおよび不可避的不純物を含むものである。
The preferred embodiments of the present invention will be described below. In the present invention, the copper alloy material means a copper alloy processed into a specific shape such as a plate material, a strip material, or a foil by a rolling process.
The composition of the first embodiment of the copper alloy material of the present invention is Co, Si and other additive elements (at least one selected from the group consisting of Cr, Fe, Ni, Al, Nb, Ti, V, and Zr). And the balance contains Cu and inevitable impurities.
本実施形態の銅合金材において、Ｃｏの含有量は０．５〜２．５ｍａｓｓ％とする。この理由は、製品として十分な強度を確保するためである。０．５ｍａｓｓ％未満ではＳｉとの析出によって得られる強度が不十分となる。また、２．５ｍａｓｓ％を超えると固溶しきれなくなり、銅合金の強化に寄与しなくなるほか、地金コストの高いコバルトの添加量増加によって、価格面で競争力に劣る銅合金となってしまう。好ましくは０．６〜２．２ｍａｓｓ％であり、より好ましくは０．７〜２．０ｍａｓｓ％である。 In the copper alloy material of the present embodiment, the Co content is 0.5 to 2.5 mass%. The reason for this is to ensure sufficient strength as a product. If it is less than 0.5 mass%, the strength obtained by precipitation with Si becomes insufficient. Moreover, if it exceeds 2.5 mass%, it will not be able to be completely dissolved and will not contribute to strengthening of the copper alloy, and it will become a copper alloy that is inferior in competitiveness in terms of price due to an increase in the amount of cobalt added with high metal costs. . Preferably it is 0.6-2.2 mass%, More preferably, it is 0.7-2.0 mass%.
Ｓｉの含有量は、少なくとも０．１〜１ｍａｓｓ％の範囲を満足するようにすることが好ましい。この理由も、製品として十分な強度を確保するためである。少なすぎるとＣｏとの析出によって得られる強度が不十分となる場合がある。また、多すぎると固溶によって導電率が低下する場合がある。本実施形態では、ＣｏとＳｉの質量比、Ｃｏ／Ｓｉが２．５〜４．５となるようにする。 It is preferable that the Si content satisfies a range of at least 0.1 to 1 mass%. This is also for ensuring sufficient strength as a product. If the amount is too small, the strength obtained by precipitation with Co may be insufficient. Moreover, when there is too much, electrical conductivity may fall by solid solution. In the present embodiment, the mass ratio of Co and Si and Co / Si are set to 2.5 to 4.5.
本実施形態では、Ｃｏ、Ｓｉの他に、Ｃｒ、Ｆｅ、Ｎｉ、Ａｌ、Ｎｂ、Ｔｉ、Ｖ及びＺｒからなる群から選ばれる少なくとも１種の添加元素を有する。
Ｃｒ、Ｆｅ、Ｎｉ、Ａｌ、Ｎｂ、Ｔｉ、Ｖ、Ｚｒは、Ｃｏ、Ｓｉと共に化合物として晶出し、打ち抜き加工性の向上に有効である。前記添加元素の合計の含有量は０．０１〜０．２ｍａｓｓ％とする。０．０１ｍａｓｓ％未満では打ち抜き加工性向上の効果が十分得られない。また、０．２ｍａｓｓ％を超えると、Ｃｏ、Ｓｉの多くが強度に寄与しない化合物となることで、材料強度が要求強度よりも低下してしまう。
In this embodiment, in addition to Co and Si, at least one additive element selected from the group consisting of Cr, Fe, Ni, Al, Nb, Ti, V, and Zr is included.
Cr, Fe, Ni, Al, Nb, Ti, V, and Zr crystallize as a compound together with Co and Si, and are effective in improving the punching workability. The total content of the additive elements is 0.01 to 0.2 mass%. If it is less than 0.01 mass%, the effect of improving the punching workability cannot be obtained sufficiently. On the other hand, if it exceeds 0.2 mass%, most of Co and Si become compounds that do not contribute to the strength, so that the material strength is lower than the required strength.
本実施形態では、銅合金中に、Ｃｏ及び他の添加元素（Ｃｒ、Ｆｅ、Ｎｉ、Ａｌ、Ｎｂ、Ｔｉ、Ｖ、Ｚｒ）から選ばれる少なくとも１種の元素とＳｉからなる、直径０．０５〜５μｍサイズの化合物を１０３〜１０５個／ｍｍ２含有する。この化合物とは、具体的には、Ｃｏ２Ｓｉの他にＣｏ２−ｘＣｒｘＳｉ、Ｃｏ２−ｘＦｅｘＳｉ（ｘは１または２）などである。
なお、化合物の直径と密度は、圧延平行方向の断面を走査型電子顕微鏡で写真撮影して、その写真上で化合物の粒径と密度を測定したものである。
ＣｏとＳｉの添加量については、Ｃｏ（ｍａｓｓ％）とＳｉ（ｍａｓｓ％）の比、Ｃｏ／Ｓｉを２．５〜４．５とする。このような比率とする理由は、時効熱処理時に、同系にて強化、導電率の回復に最も寄与するＣｏ２Ｓｉ化合物の析出を促進しやすいためである。Ｃｏ、Ｓｉ以外の元素を含む本実施形態では、Ｃｏ、Ｓｉとその他の元素にて上記化合物を形成し、ややＳｉ量を多く含んだ化合物となるために、Ｃｏ２Ｓｉ析出を促すＣｏ／Ｓｉ比の固溶状態が維持できるよう、後述する他の元素を含まない形態に比べ、ややＳｉ量が多くなるような比になっている。上記比を満たすことによって目的の銅合金材を得ることができる。この実施形態におけるＣｏ／Ｓｉは好ましくは２．５〜４であり、より好ましくは３〜３．５である。
In the present embodiment, the copper alloy contains at least one element selected from Co and other additive elements (Cr, Fe, Ni, Al, Nb, Ti, V, Zr) and Si, and has a diameter of 0.05. Contains 10 3 to 10 5 compounds / mm 2 of ˜5 μm size. And the compound, specifically, (the x 1 or 2) in addition to Co 2-x Cr x Si, Co 2-x Fe x Si of Co 2 Si and the like.
The diameter and density of the compound are obtained by taking a photograph of a cross section in the rolling parallel direction with a scanning electron microscope and measuring the particle size and density of the compound on the photograph.
About the addition amount of Co and Si, ratio of Co (mass%) and Si (mass%), Co / Si shall be 2.5-4.5. The reason for this ratio is that during the aging heat treatment, it is easy to promote the precipitation of the Co 2 Si compound that contributes most to strengthening and electrical conductivity recovery in the same system. In the present embodiment including elements other than Co and Si, the above compound is formed with Co, Si and other elements, and becomes a compound containing a slightly large amount of Si, so that Co / Si promotes Co 2 Si precipitation. In order to maintain the solid solution state of the ratio, the ratio is such that the amount of Si is slightly increased as compared with a form not including other elements described later. By satisfying the above ratio, a target copper alloy material can be obtained. Co / Si in this embodiment is preferably 2.5-4, more preferably 3-3.5.
化合物の直径を０．０５〜５μｍとする理由は、この直径の化合物粒子が打ち抜き加工性を向上させるからである。直径が０．０５μｍ未満の粒子では、打ち抜き加工性を向上させることができず、直径が５μｍを超える粒子は化合物による材料強化、プレス性向上の双方への寄与が非常に小さい。好ましくは０．１〜１μｍである。 The reason why the diameter of the compound is 0.05 to 5 μm is that the compound particles having this diameter improve the punching processability. Particles having a diameter of less than 0.05 μm cannot improve punching processability, and particles having a diameter of more than 5 μm contribute very little to both material strengthening and pressability improvement by the compound. Preferably it is 0.1-1 micrometer.
化合物の密度を１０３〜１０５個／ｍｍ２に規定したのは、打ち抜き加工性の向上と材料強度を両立させるからである。１０３個／ｍｍ２未満であると、打ち抜き加工する時の破断のクラックの起点が少ないため、打ち抜き加工性を向上させることができない。１０５個／ｍｍ２を超えると、直径０．０５μｍ未満の化合物と比べ比較的強度に対する寄与の小さい０．０５〜５μｍの化合物が全体の大きな割合を占め、材料の強度化が出来ず、製品に求められる特性が得られない。好ましくは５×１０３〜５×１０４個／ｍｍ２である。 The reason why the density of the compound is defined as 10 3 to 10 5 pieces / mm 2 is that the improvement of the punching workability and the material strength are compatible. If it is less than 10 3 pieces / mm 2, the number of cracks at the start of the punching process is small, and therefore the punching processability cannot be improved. If it exceeds 10 5 pieces / mm 2 , the compound of 0.05 to 5 μm, which has a relatively small contribution to strength compared to the compound of less than 0.05 μm in diameter, occupies a large proportion of the whole, and the material cannot be strengthened, resulting in a The required characteristics cannot be obtained. Preferably it is 5 * 10 < 3 > -5 * 10 < 4 > piece / mm < 2 >.
本発明の銅合金材の第二の実施形態における組成は、Ｃｏを１．４ｍａｓｓ％以上２．５ｍａｓｓ％以下含有し、ＣｏとＳｉの含有量の比Ｃｏ／Ｓｉが３．０〜５．０の間にあり、残部がＣｕおよび不可避的不純物を含むものである。 The composition of the second embodiment of the copper alloy material of the present invention is that Co is contained in an amount of 1.4 mass% to 2.5 mass%, and the Co / Si content ratio Co / Si is 3.0 to 5.0. And the balance contains Cu and inevitable impurities.
この実施形態の銅合金材において、Ｃｏの含有量を１．４ｍａｓｓ％以上２．５ｍａｓｓ％以下とする理由は、打ち抜き加工性を良好にする化合物、強度を良好にする化合物の析出量を双方において適量にするためであり、特に高強度材の要求に応えるためである。Ｃｏの含有量を上記範囲内とし、銅合金材の製造方法における熱処理条件等を制御することで、化合物の晶出、析出を、打ち抜き性が良好で、かつ、高強度材とすることができるような量にすることができる。Ｃｏの含有量は好ましくは１．４ｍａｓｓ％以上２．０ｍａｓｓ％以下である。 In the copper alloy material of this embodiment, the reason why the Co content is 1.4 mass% or more and 2.5 mass% or less is that the precipitation amount of the compound that improves the punching workability and the compound that improves the strength is both This is to make the amount suitable, and in particular to meet the demand for high strength materials. By controlling the heat treatment conditions and the like in the method for producing a copper alloy material with the Co content within the above range, the crystallization and precipitation of the compound can be made into a high-strength material with good punchability. The amount can be as follows. The content of Co is preferably 1.4 mass% or more and 2.0 mass% or less.
Ｓｉの含有量は、少なくとも０．３〜１．０ｍａｓｓ％の範囲を満足するようにすることが好ましい。この理由は、Ｃｏの添加量と同様に、打ち抜き加工性を良好にする化合物、強度を良好にする化合物の析出量を双方において適量にするためであり、特に高強度材の要求に応えるためである。少なすぎると打ち抜き性、強度双方を良好にするための析出総量を満たせなくなってしまい、どちらか一方の特性が劣化してしまう場合がある。また、多すぎると有効に寄与する化合物の晶出、析出量が飽和してしまうことがある。本実施形態では、ＣｏとＳｉの質量比、Ｃｏ／Ｓｉが３．０〜５．０となるようにする。 It is preferable that the Si content satisfies at least a range of 0.3 to 1.0 mass%. The reason for this is to make the amount of precipitation of the compound that improves the punching workability and the compound that improves the strength appropriate for both, as well as the amount of Co added, especially to meet the demand for high strength materials. is there. If the amount is too small, the total amount of precipitation for improving both punchability and strength may not be satisfied, and either one of the properties may be deteriorated. On the other hand, if the amount is too large, the amount of crystallization and precipitation of compounds that contribute effectively may be saturated. In the present embodiment, the mass ratio of Co and Si and Co / Si are set to 3.0 to 5.0.
本実施形態では、銅合金中にＣｏ及びＳｉの化合物を有する。この化合物とは、具体的にはＣｏ２Ｓｉである。化合物の直径及び密度は上記他の添加元素を含有する実施形態と同様であり、その好ましい範囲も同様である。
Ｃｏ／Ｓｉは３．０〜５．０とする。このような添加比とする理由は、時効熱処理時に、同系にて強化、導電率の回復に最も寄与するＣｏ２Ｓｉ化合物の析出を促進しやすいためである。この実施形態におけるＣｏ／Ｓｉは好ましくは３．２〜４．５であり、より好ましくは３．５〜４．２である。
In this embodiment, the copper alloy has Co and Si compounds. Specifically, this compound is Co 2 Si. The diameter and density of the compound are the same as those in the embodiment containing the other additive elements, and the preferred ranges thereof are also the same.
Co / Si is set to 3.0 to 5.0. The reason for setting such an addition ratio is that during the aging heat treatment, it is easy to promote precipitation of the Co 2 Si compound that contributes most to strengthening and restoring electrical conductivity in the same system. Co / Si in this embodiment is preferably 3.2 to 4.5, more preferably 3.5 to 4.2.
本発明の銅合金材の製造方法においては、鋳造時の冷却速度が１〜３０℃／秒、好ましくは３〜２５℃／秒の条件下で作製された鋳塊を均質処理後、熱間圧延、冷間圧延、溶体化熱処理、時効熱処理をこの順に施した後、仕上げ圧延、歪取り焼鈍をこの順に施すことにより銅合金材を製造する。
本発明の銅合金材の製造方法の好ましい実施形態の一例を挙げると、ＣｏとＳｉと、実施形態によってはその他の添加元素と、残部がＣｕからなる銅合金を高周波溶解炉等により溶解して鋳造の冷却速度を１〜３０℃／秒の条件で鋳造し、鋳塊を得る。この条件により直径０．０５〜５μｍサイズの上記化合物を１０３〜１０５個／ｍｍ２含有する組織制御をすることができる。その鋳塊を均質処理に付した後、例えば、熱間圧延によって厚さ８〜１５ｍｍになるまで加工後、速やかに水冷却（急速冷却）にて焼入れを施し、表面上の酸化皮膜除去のため、圧延された表面を片側０．５〜２ｍｍ面削して４〜１３ｍｍにした後、冷間圧延にて厚さ約０．１〜０．３ｍｍとなるように加工する。さらに溶体化熱処理（温度８００〜１０２５℃、１〜１００秒間）を加え、水冷後、材料に３００〜６００℃で１〜１０時間の時効熱処理を行う。この熱処理後に、加工率が０％を超えて３０％以下の圧延（仕上げ圧延）を加え、さらに２００〜４５０℃で０．５〜５時間の低温熱処理（歪取り焼鈍）を行うことにより目的の銅合金材を得ることができる。
In the method for producing a copper alloy material of the present invention, an ingot produced under conditions of a cooling rate during casting of 1 to 30 ° C./second, preferably 3 to 25 ° C./second is subjected to homogenization treatment, and then hot rolled. After performing cold rolling, solution heat treatment, and aging heat treatment in this order, finish rolling and strain relief annealing are performed in this order to produce a copper alloy material.
An example of a preferred embodiment of the method for producing a copper alloy material of the present invention is as follows. Co and Si, and depending on the embodiment, other additive elements, and a copper alloy with the balance being Cu are melted by a high-frequency melting furnace or the like. An ingot is obtained by casting at a cooling rate of 1 to 30 ° C./sec. Under these conditions, it is possible to control the tissue containing 10 3 to 10 5 / mm 2 of the above compound having a diameter of 0.05 to 5 μm. After the ingot is subjected to a homogenous treatment, for example, after being processed to a thickness of 8 to 15 mm by hot rolling, it is rapidly quenched with water cooling (rapid cooling) to remove the oxide film on the surface. The rolled surface is chamfered to 0.5 to 2 mm on one side to 4 to 13 mm, and then processed to a thickness of about 0.1 to 0.3 mm by cold rolling. Further, solution heat treatment (temperature 800 to 1025 ° C., 1 to 100 seconds) is added, and after water cooling, the material is subjected to aging heat treatment at 300 to 600 ° C. for 1 to 10 hours. After this heat treatment, rolling (finish rolling) with a processing rate exceeding 0 % and 30% or less is added, and further, low-temperature heat treatment (distortion annealing) is performed at 200 to 450 ° C. for 0.5 to 5 hours. A copper alloy material can be obtained.
本発明の銅合金材の製造方法により得られる銅合金材は、特に限定されるものではないが、例えば、コネクタ、端子、リレー、スイッチ、さらにはリードフレームなどの電子電気機器部品に好適に用いることができる。 Although the copper alloy material obtained by the manufacturing method of the copper alloy material of the present invention is not particularly limited, for example, it is suitably used for electronic and electrical equipment parts such as connectors, terminals, relays, switches, and lead frames. be able to.
以下に、本発明を実施例に基づきさらに詳細に説明するが、本発明はそれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
下記表１、表２に示す銅合金材を以下のように作製した。表１は本発明の効果を確認するための参考例での評価結果を示すものであり、この参考例で良好な特性を示すサンプルの組成について、表２に示す各種評価を行っている。表２は第一の実施形態および第二の実施形態に関する評価結果である。 The copper alloy materials shown in Tables 1 and 2 below were produced as follows. Table 1 shows the evaluation results in a reference example for confirming the effects of the present invention, and various evaluations shown in Table 2 are performed on the composition of a sample exhibiting good characteristics in this reference example. Table 2 is an evaluation result for the first embodiment and the second embodiment.
（銅合金材の製造条件）
各表に記載する量のＣｏとＳｉとその他の添加元素と残部がＣｕからなる銅合金を高周波溶解炉により溶解し、これを鋳造して、厚さ３０ｍｍ、幅１００ｍｍ、長さ１５０ｍｍの鋳塊を得た。鋳造時の冷却速度については、表１の各サンプルについては５℃／秒とし、表２の各サンプルについては表２に示した。各サンプルにおいては、冷却速度の速いサンプルは厚さ５ｍｍにて、遅いサンプルにおいては厚さ１００ｍｍにし、モールドに断熱材を使用するなどして、冷却速度を変えた。
(Manufacturing conditions for copper alloy materials)
The amount of Co and Si described in each table, a copper alloy composed of other additive elements and the balance Cu are melted in a high-frequency melting furnace, and this is cast, and an ingot having a thickness of 30 mm, a width of 100 mm, and a length of 150 mm Got. The cooling rate during casting was set at 5 ° C./second for each sample in Table 1, and Table 2 for each sample in Table 2 . In each sample, the sample having a fast cooling rate was 5 mm in thickness, the sample having a slow cooling rate was 100 mm, and the cooling rate was changed by using a heat insulating material for the mold.
次にこの鋳塊に９５０℃で１時間加熱する均質化処理を施した直後に熱間圧延を行い（６００℃までの降温速度は３０℃／秒）、両面をそれぞれ１ｍｍ面削して酸化皮膜を除去した。次いで冷間圧延にて板厚を０．１〜０．３ｍｍにした後、不活性化ガス雰囲気中で溶体化熱処理（１０００℃到達、昇温、降温速度とも５０℃／秒）を行った。 Next, this ingot was hot-rolled immediately after being subjected to a homogenization treatment at 950 ° C. for 1 hour (the temperature decreasing rate up to 600 ° C. was 30 ° C./second), and both sides were each 1 mm chamfered to form an oxide film. Was removed. Next, the plate thickness was reduced to 0.1 to 0.3 mm by cold rolling, and then solution heat treatment (reaching 1000 ° C., both heating and cooling rates were 50 ° C./second) was performed in an inert gas atmosphere.
水冷後、材料に時効熱処理（４７５〜５７５℃、２時間で最も強度の高い温度を選定）を行った。この熱処理後０％を超えて３０％以下の圧延を加え、さらに２００〜４５０℃で０．５〜５時間の低温熱処理（歪取り焼鈍）を行った。 After water cooling, the material was subjected to an aging heat treatment (select the temperature having the highest strength in 2 hours at 475 to 575 ° C.). After this heat treatment, rolling exceeding 0 % and 30% or less was added, and further low-temperature heat treatment (strain relief annealing) was performed at 200 to 450 ° C. for 0.5 to 5 hours.
このようにして得られた各々の板材を供試材として下記の特性調査を行った。各評価項目の測定方法は以下の通りである。
ａ．引張強度（ＴＳ、ＹＳ）：
試験片の圧延平行方向から切り出したＪＩＳ Ｚ２２０１−１３Ｂ号の試験片をＪＩＳ Ｚ２２４１に準じて３本測定しその平均値を表１に示した。また、評価として表１に示される特性に対し、表２における同じ組成の銅合金の強度（引張強度（ＴＳ）、０．２％耐力（ＹＳ）共に）の低下が３０ＭＰａ未満なら製品に求められる強度を満たすとして○、３０ＭＰａ以上なら満たさないとして×と評価し、表２に示した。なお、表１において、引張強度（ＴＳ）が５５０ＭＰａ以上、０．２％耐力（ＹＳ）が４００ＭＰａ以上である組成について、表２に記載の条件で銅合金材を製造し、評価対象とすることとした。
ｂ．導電率（ＥＣ）測定：
四端子法を用いて、２０℃（±１℃）に管理された恒温槽中で、各試験片の２本について導電率（ＥＣ）を測定し、その平均値（％ＩＡＣＳ）を表１、表２に示した。このとき端子間距離は１００ｍｍとした。なお、評価基準として、導電率（ＥＣ）が５７％ＩＡＣＳ以上であるものを、導電性がすぐれているものとした。
ｃ．プレス打ち抜き加工性
金型を研磨した後に、各サンプルで連続プレス加工を実施し、１０万回おきにサンプルプレス破面のバリ測定をした。材料のプレス破面に５μｍを越えるバリが発生した段階を限界ショット数として、ショット数２００万回を満たすものを打ち抜き性が特に優れているとして◎、１００万回以上２００万回未満のものを打ち抜き性が良好であるとして○、１００万回未満のものを打ち抜き性が劣っているとして×として表２中に記載した。
The following characteristic investigation was performed by using each plate material thus obtained as a test material. The measurement method for each evaluation item is as follows.
a. Tensile strength (TS, YS):
Three test pieces of JIS Z2201-13B cut out from the rolling parallel direction of the test pieces were measured according to JIS Z2241, and the average values are shown in Table 1. Further, with respect to properties shown in Table 1 as an evaluation, determined the strength of the copper alloy of the definitive same composition in Table 2 for less reduction of the (tensile strength (TS), 0.2% yield strength (YS) both) is 30MPa Product ○ as meet strength to, and evaluated as × as not satisfied if more than 30 MPa, are shown in Table 2. In Table 1, for a composition having a tensile strength (TS) of 550 MPa or more and a 0.2% proof stress (YS) of 400 MPa or more, a copper alloy material is produced under the conditions shown in Table 2 and is to be evaluated. It was.
b. Conductivity (EC) measurement:
Using a four-terminal method, in a thermostat controlled at 20 ° C. (± 1 ° C.), the electrical conductivity (EC) was measured for two of each test piece, and the average value (% IACS) is shown in Table 1. It is shown in Table 2 . At this time, the distance between terminals was set to 100 mm. Note that, as an evaluation standard, one having an electrical conductivity (EC) of 57% IACS or more is considered to have excellent conductivity.
c. Press punching process After polishing the mold, each sample was subjected to continuous pressing, and the burr on the fracture surface of the sample press was measured every 100,000 times. A stage where a burr exceeding 5 μm is generated on the press fracture surface of the material is considered to be particularly excellent in punching performance that satisfies the number of shots of 2 million shots, ◎, those of 1 million times to less than 2 million times Table 2 shows that the punchability is good, and that less than 1,000,000 times is shown as x that the punchability is inferior.
なお、晶出、析出物（化合物）の比は、直径０．０５〜５μｍの晶出、析出物をＳＥＭ付属のＥＤＸにて１０個測定し構成元素を判断し、定量測定にて平均値をとった（化合物種類が複数あれば、全て列記した）。
直径０．０５〜５μｍの化合物の１ｍｍ２あたりの個数は、４００μｍ２の面積内に存在するサイズ該当化合物を、測定場所を１０回変えてカウントし、その平均値を２５００倍した結果を示した。
The ratio of crystallization and precipitates (compounds) was determined by measuring 10 crystallization and precipitates having a diameter of 0.05 to 5 μm with the EDX attached to the SEM, determining the constituent elements, and calculating the average value by quantitative measurement. (If there are multiple types of compounds, all are listed).
The number per 1 mm 2 of the compound having a diameter of 0.05 to 5 μm is the result of counting the size corresponding compound existing in the area of 400 μm 2 by changing the measurement place 10 times and multiplying the average value by 2500 times. .
参考例
表１に示す組成の銅合金材（第一の実施形態の組成：試験Ｎｏ．１０１〜１０７、第二の実施形態の組成：試験Ｎｏ．１０８〜１０９、比較組成：試験Ｎｏ．１５１〜１６７）を上記のようにして作製し、引張強度（ＴＳ、ＹＳ）及び導電性（ＥＣ）を測定した。結果を表１に併せて示す。比較組成の銅合金材は、強度、導電率のいずれかもしくは両方が試験Ｎｏ．１０１〜１０９に対し低下している。詳しくは以下の通りである。
比較組成の試験Ｎｏ．１５１〜１６２は、ＣｏとＳｉの添加比が本発明で規定する範囲に入っていない。試験Ｎｏ．１０１〜１０９に対し強度、または導電率のいずれかもしくは両方が劣っている。また、試験Ｎｏ．１６３〜１６７はその他の添加元素の添加量が多すぎるため、試験Ｎｏ．１０１〜１０９に対し強度、または導電率のいずれかもしくは両方が劣っている。
これに対し、試験Ｎｏ．１０１〜１０９はいずれも、強度、導電率ともに良好であった。
なお、晶出物、析出物（化合物）が与える影響については、添加元素についてＣｏまたはＳｉと化合物をつくると、強度に寄与するＣｏ２Ｓｉ化合物の全体量が減ってしまう。また、添加元素とＣｏ−Ｓｉの組成比がＣｏ２Ｓｉと異なるため、ＣｏやＳｉの添加量を調整して強度に寄与するＣｏ２Ｓｉ化合物の全体量を確保しなければ特性値が劣化してしまう傾向がある。
The composition of the copper alloy material (the first embodiment of the composition shown in Example Table 1: Test No.101~ 107, the composition of the second embodiment: Test No. 108 ~ 109, comparison composition: Test No.151 ˜167) were prepared as described above, and tensile strength (TS, YS) and conductivity (EC) were measured. The results are also shown in Table 1. The copper alloy material of the comparative composition has a test number of either or both of strength and conductivity. It has declined for the 101-109. Details are as follows.
Comparative composition test no. In 151 to 162, the addition ratio of Co and Si is not within the range defined by the present invention. Test No. Either 101 or 109 is inferior in strength or conductivity, or both. In addition, Test No. Since Nos. 163 to 167 have too much addition amount of other additive elements, Either 101 or 109 is inferior in strength or conductivity, or both.
In contrast, test no. All of 101 to 109 were good in strength and conductivity.
Regarding the influence of crystallized substances and precipitates (compounds), if a compound of Co or Si is made for the additive element, the total amount of Co 2 Si compound that contributes to the strength is reduced. Further, since the composition ratio of the additive element and Co—Si is different from that of Co 2 Si, the characteristic value deteriorates unless the total amount of the Co 2 Si compound contributing to the strength is secured by adjusting the addition amount of Co or Si. There is a tendency to end up.
実施例１
表２に示す組成で、上記のようにして得た銅合金材サンプルについて、プレス性と強度を評価した。結果を表２に示す。表２は第一の実施形態および第二の実施形態に関する評価結果であり、所定の製造工程に従って製造するとともに、鋳造時の冷却速度が１〜３０℃／秒の範囲内であれば、Ｃｏ−Ｓｉ系化合物の直径と密度がコントロールされ、プレス打ち抜き加工性と強度のバランスの取れた銅合金材が得られている。鋳造時の冷却速度が遅すぎる場合は所望のサイズのＣｏ−Ｓｉ系化合物が多くなりすぎ、強度低下している。また、鋳造時の冷却速度が速すぎる場合は所望のサイズのＣｏ−Ｓｉ系化合物が少なすぎ、プレス打ち抜き加工性が低下している。なお、選択元素（Ｃｒ、Ｆｅ、Ｎｉ、Ａｌ、Ｎｂ、Ｔｉ、Ｖ、Ｚｒ）を含まない場合で、化合物が適正に生成していない場合は、プレス打ち抜き加工性が低下している。
Example 1
With the compositions shown in Table 2, the pressability and strength of the copper alloy material samples obtained as described above were evaluated. The results are shown in Table 2. Table 2 shows the evaluation results relating to the first embodiment and the second embodiment, and is manufactured according to a predetermined manufacturing process, and if the cooling rate during casting is within the range of 1 to 30 ° C./second, Co— The diameter and density of the Si-based compound are controlled, and a copper alloy material having a balance between press punching workability and strength is obtained. When the cooling rate at the time of casting is too slow, the amount of the Co-Si compound having a desired size is excessive, and the strength is reduced. Moreover, when the cooling rate at the time of casting is too high, there are too few Co-Si type compounds of desired size, and press punching workability is falling. In the case where the selective element (Cr, Fe, Ni, Al, Nb, Ti, V, Zr) is not included and the compound is not properly generated, the press punching processability is lowered.
Claims (4)
均質処理、
熱間圧延、
水冷却、
冷間圧延、
８００〜１０２５℃で１〜１００秒間の溶体化熱処理、
３００〜６００℃で１〜１０時間の時効熱処理、
加工率が０％を超えて３０％以下の仕上げ圧延、
２００〜４５０℃で０．５〜５時間の歪取り焼鈍を施す
各工程をこの順に施し、
直径が０．０５〜５μｍで、密度が１０ ３ 〜１０ ５ 個／ｍｍ ２ の、前記添加元素及びＣｏからなる群から選ばれる少なくとも１種の元素とＳｉからなる化合物を含有する銅合金材を得ることを特徴とする銅合金材の製造方法。 Co containing 0.5 to 2.5 mass%, Co / Si content ratio Co / Si is between 2.5 and 4.5, and Cr, Fe, Ni, Al, Nb, Ti, A total of at least one additive element selected from the group consisting of V and Zr is contained in an amount of 0.01 to 0.2 mass%, and the remainder of the copper alloy raw material consisting of Cu and inevitable impurities is dissolved, and the cooling rate during casting is 1 Casting under conditions of -30 ° C / second to obtain an ingot,
Homogeneous treatment,
Hot rolling,
Water cooling,
Cold rolling,
Solution heat treatment for 1 to 100 seconds at 800 to 1025 ° C.,
Aging heat treatment at 300-600 ° C. for 1-10 hours,
Working ratio of 30% or less of finish rolling exceeds 0%,
Each step of at 200 to 450 ° C. performing stress relief annealing of 0.5-5 hours facilities in this order,
A copper alloy material containing a compound comprising Si and at least one element selected from the group consisting of the additive element and Co, having a diameter of 0.05 to 5 μm and a density of 10 3 to 10 5 pieces / mm 2. A method for producing a copper alloy material, comprising: obtaining a copper alloy material.
均質処理、
熱間圧延、
水冷却、
冷間圧延、
８００〜１０２５℃で１〜１００秒間の溶体化熱処理、
３００〜６００℃で１〜１０時間の時効熱処理、
加工率が０％を超えて３０％以下の仕上げ圧延、
２００〜４５０℃で０．５〜５時間の歪取り焼鈍を施す
各工程をこの順に施し、
直径が０．０５〜５μｍで、密度が１０３〜１０５個／ｍｍ２のＣｏ及びＳｉで構成される化合物を含有する銅合金材を得ることを特徴とする銅合金材の製造方法。 Copper alloy raw material containing Co in an amount of 1.4 mass% to 2.5 mass%, Co / Si content ratio Co / Si being between 3.0 and 5.0, the balance being Cu and inevitable impurities And the ingot is obtained by casting at a cooling rate of 1 to 30 ° C./second during casting,
Homogeneous treatment,
Hot rolling,
Water cooling,
Cold rolling,
Solution heat treatment for 1 to 100 seconds at 800 to 1025 ° C.,
Aging heat treatment at 300-600 ° C. for 1-10 hours,
Finish rolling with a processing rate exceeding 0% to 30%,
Each step of applying strain relief annealing at 200 to 450 ° C. for 0.5 to 5 hours is performed in this order,
A method for producing a copper alloy material, comprising: obtaining a copper alloy material containing a compound composed of Co and Si having a diameter of 0.05 to 5 μm and a density of 10 3 to 10 5 pieces / mm 2 .
The copper alloy material manufactured by the method according to claim 2 , wherein the obtained copper alloy material is Co and Si having a diameter of 0.05 to 5 μm and a density of 10 3 to 10 5 pieces / mm 2. A copper alloy material containing a compound composed.
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