JP5587593B2 - Method for producing copper alloy - Google Patents
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本発明は、例えばリードフレームやコネクター等の電気・電子機器用部品に用いられる熱間加工性に優れた銅合金の製造方法に関する。 The present invention relates to a method for producing a copper alloy having excellent hot workability used for parts for electrical and electronic equipment such as lead frames and connectors.
近年の電気・電子機器の高性能化・高密度化に伴い、例えばリードフレームやコネクター等の部品に用いられる銅合金条には、より優れた導電性と強度が必要とされており、この要求に応え得る合金として、Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素を０．０１〜５質量％含有し、残部がＣｕと不可避不純物である銅合金材料が知られている。 With the recent increase in performance and density of electrical and electronic equipment, for example, copper alloy strips used in parts such as lead frames and connectors are required to have better conductivity and strength. 0.01-5 mass of at least one element selected from Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag A copper alloy material containing 0.5% and the balance being Cu and inevitable impurities is known.
一方、一般に銅および銅合金には中間温度脆性と呼ばれるものが存在し、中高温域において、残留している水素等のガスの影響により、延性が著しく低下して加工が困難となり、粒界割れを起こし易くなる現象が知られている。例えばＣｕ−Ｎｉ−Ｓｉ系銅合金ではこの現象が特に顕著であり、銅合金の製造における熱間圧延に先立つ加熱過程において粒界割れを起こし、後工程である焼鈍等の熱処理によって銅合金表面にフクレ等の不良が発生し、製造歩留まりが低下してしまう恐れがある。 On the other hand, copper and copper alloys generally have a so-called brittleness at intermediate temperature, and in the middle and high temperature range, due to the effect of residual gas such as hydrogen, the ductility is remarkably lowered, making it difficult to process and intergranular cracking. There is a known phenomenon that makes it easy to cause. For example, this phenomenon is particularly prominent in Cu-Ni-Si based copper alloys, causing intergranular cracking in the heating process prior to hot rolling in the production of copper alloys, and on the surface of the copper alloy by heat treatment such as annealing, which is a subsequent process. There is a risk that defects such as blisters occur and the manufacturing yield decreases.
そこで特許文献１には、銅合金材料を溶解し、この溶湯中に含まれる水素等のガスを不活性ガスで置換することで脱ガス処理を行い、中間温度脆性を抑制する銅合金の製造方法が開示されている。
Therefore,
しかしながら、上記特許文献１に記載の銅合金の製造方法では、粒界割れの原因となる水素等のガスの脱ガス処理を、銅合金材料を溶解させた溶湯の状態で行うか、あるいは、熱間圧延の前に銅合金材料を融点程度の温度まで加熱しなくてはならず、エネルギー効率の面で効率的でないという問題点があった。
However, in the method for producing a copper alloy described in
そこで、上記問題点に鑑み本発明の目的は、エネルギー効率よく比較的低温でもって脱ガス熱処理を効率的に行い、後工程での粒界割れの発生する恐れがないような銅合金の製造方法を提供することにある。 Accordingly, in view of the above problems, an object of the present invention is to provide a copper alloy manufacturing method that efficiently performs degassing heat treatment at a relatively low temperature with high energy efficiency and does not cause the occurrence of intergranular cracking in the subsequent process. Is to provide.
上記目的を達成するため、本発明によれば、Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素を合計で０．０１〜５質量％含有し、残部がＣｕと不可避不純物である銅合金材料を形成し、前記銅合金材料を３００℃〜７００℃で１〜３時間保持することで脱ガス熱処理を行い、脱ガス熱処理後の銅合金材料に熱間圧延、冷間圧延、熱処理を施すことによって銅合金を得る、銅合金の製造方法が提供される。
In order to achieve the above object, according to the present invention, at least one element of Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag is used. Is formed in a total amount of 0.01 to 5% by mass, and the balance is Cu and an inevitable impurity copper alloy material, and the copper alloy material is held at 300 ° C. to 700 ° C. for 1 to 3 hours for degassing heat treatment A copper alloy manufacturing method is provided in which a copper alloy is obtained by performing hot rolling, cold rolling, and heat treatment on the copper alloy material after the degassing heat treatment.
また、別な観点からの本発明によれば、Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素を合計で０．０１〜５質量％含有し、残部がＣｕと不可避不純物である銅合金材料を形成し、前記銅合金材料を４００℃〜６００℃で１〜２時間保持することで脱ガス熱処理を行い、脱ガス熱処理後の銅合金材料に熱間圧延、冷間圧延、熱処理を施すことによって銅合金を得る、銅合金の製造方法が提供される。 According to another aspect of the present invention, at least one element of Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag Degassing heat treatment by forming a copper alloy material containing 0.01 to 5 mass% in total , the balance being Cu and inevitable impurities, and holding the copper alloy material at 400 ° C to 600 ° C for 1 to 2 hours A copper alloy manufacturing method is provided in which a copper alloy is obtained by performing hot rolling, cold rolling, and heat treatment on the copper alloy material after the degassing heat treatment.
本発明によれば、エネルギー効率よく比較的低温でもって脱ガス熱処理を効率的に行い、後工程での粒界割れの発生する恐れがないような銅合金の製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a copper alloy which performs degassing heat processing efficiently and comparatively low temperature efficiently, and does not have a possibility of generating a grain boundary crack in a post process is provided.
以下、本発明の実施の形態について説明する。前述したように、Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素を０．０１〜５質量％含有し、残部がＣｕと不可避不純物である銅合金材料には中間温度脆性と呼ばれるものが存在し、熱間圧延工程等の中高温域において、残留している水素等のガスの影響により、延性が著しく低下して加工が困難となり、粒界割れを起こし易くなる現象が知られている。また、通常、熱間圧延工程の後に、冷間圧延および熱処理の繰り返しで銅合金板材を作製するが、この熱処理後にフクレ不良の発生がみられ歩留まりを低下させることがある。 Embodiments of the present invention will be described below. As described above, 0.01 to 5% by mass of at least one element of Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag. Copper alloy materials that contain Cu and inevitable impurities in the balance contain what is called intermediate temperature brittleness, and in the middle and high temperature range such as hot rolling process, due to the effect of residual gas such as hydrogen, ductility It is known that the phenomenon of remarkably lowering makes processing difficult, and easily causes grain boundary cracking. Usually, after the hot rolling process, a copper alloy sheet is produced by repeating cold rolling and heat treatment. However, after this heat treatment, the occurrence of blister defects may occur and the yield may be lowered.
従来、粒界割れやフクレ不良発生の原因となる水素等の脱ガスを行うためには、銅合金材料を融点以上の温度まで加熱し、溶解させた状態で脱ガス処理を行うことが必要とされていた。しかしながら、本発明者らは、鋭意研究の結果、銅合金材料を熱間圧延する前に、その融点温度より低い温度である３００℃〜７００℃、好ましくは４００℃〜６００℃の条件下で１〜３時間もしくは１〜２時間程度保持しておく工程を行うことによって、銅合金材料に十分な脱ガス処理が施されることを発見し、本発明の実現に至った。なお、以下では銅合金材料を、その融点温度より低い温度で保持する工程を脱ガス熱処理と呼称する。 Conventionally, in order to perform degassing such as hydrogen, which causes grain boundary cracking and blister failure, it is necessary to heat the copper alloy material to a temperature equal to or higher than the melting point and perform degassing treatment in a dissolved state. It had been. However, as a result of intensive studies, the present inventors have found that before hot rolling the copper alloy material, the temperature is lower than the melting point of 300 ° C. to 700 ° C., preferably 400 ° C. to 600 ° C. It was discovered that a sufficient degassing treatment was performed on the copper alloy material by performing the step of holding for about 3 hours or about 1 to 2 hours, thereby realizing the present invention. Hereinafter, the process of holding the copper alloy material at a temperature lower than its melting point temperature is referred to as degassing heat treatment.
図１は、本発明者らが知見した銅合金材料の脱ガス熱処理における水素放出速度と加熱温度の関係（図１（ａ））および水素放出量と加熱温度の関係（図１（ｂ））を示すグラフである。なお、図１は室温から９００℃まで５℃／ｍｉｎおよび１０℃／ｍｉｎの昇温速度でもって昇温する条件下で銅合金材料を加熱した場合の水素放出速度および水素放出量を測定することで得られたデータである。 FIG. 1 shows the relationship between the hydrogen release rate and the heating temperature in the degassing heat treatment of the copper alloy material discovered by the present inventors (FIG. 1 (a)) and the relationship between the hydrogen release amount and the heating temperature (FIG. 1 (b)). It is a graph which shows. In addition, FIG. 1 measures the hydrogen release rate and the amount of hydrogen release when the copper alloy material is heated from room temperature to 900 ° C. at a temperature increase rate of 5 ° C./min and 10 ° C./min. It is the data obtained by.
図１（ａ）に示すように、加熱時の銅合金材料からの水素放出は、約２００℃〜３００℃に加熱した状態殻始まり、約５００℃付近でピークとなり、約７００℃で水素の放出は終了する。また、昇温速度が５℃／ｍｉｎの場合と１０℃／ｍｉｎの場合を比較すると、水素放出速度のピーク値は５℃／ｍｉｎの時が１０℃／ｍｉｎの場合に比べ半分程度の値であり、ピーク値に対応する材料の温度が約３０℃程度低温側へシフトする。また、図１（ｂ）に示すように、約７００℃まで銅合金材料を加熱していくと昇温速度が５℃／ｍｉｎの場合も１０℃／ｍｉｎの場合もほぼ同じ水素放出量（図１（ｂ）中に示すように３．２ｗｔｐｐｍ）となる。また、ここで測定された約７００℃まで昇温した時の水素放出量は、同じ銅合金材料の水素放出量を例えば溶解法で測定した場合の水素放出量と同等の値であることから、昇温させることによって銅合金材料から放出された水素の量は、銅合金材料に含有される水素のほぼ全量であることが推定される。 As shown in FIG. 1 (a), hydrogen release from the copper alloy material during heating starts from a shell heated to about 200 ° C. to 300 ° C., peaks at about 500 ° C., and releases hydrogen at about 700 ° C. Ends. Further, comparing the case where the temperature rising rate is 5 ° C./min and the case where it is 10 ° C./min, the peak value of the hydrogen release rate is about half of the value when the rate of 5 ° C./min is 10 ° C./min. Yes, the temperature of the material corresponding to the peak value shifts to the low temperature side by about 30 ° C. Further, as shown in FIG. 1 (b), when the copper alloy material is heated to about 700 ° C., almost the same hydrogen release amount is obtained regardless of whether the rate of temperature increase is 5 ° C./min or 10 ° C./min. 1 (b), which is 3.2 wtppm). In addition, the amount of hydrogen released when the temperature is increased to about 700 ° C. measured here is a value equivalent to the amount of hydrogen released when the amount of hydrogen released from the same copper alloy material is measured by, for example, the dissolution method. It is estimated that the amount of hydrogen released from the copper alloy material by raising the temperature is almost the total amount of hydrogen contained in the copper alloy material.
また、図２は銅合金材料の脱ガス熱処理における水素放出速度と加熱時間の関係（図２（ａ））および水素放出量と加熱時間の関係（図２（ｂ））を示すグラフである。なお、図２は室温から９００℃まで５℃／ｍｉｎおよび１０℃／ｍｉｎの昇温速度でもって昇温する条件下で銅合金材料を異なる加熱時間でもって加熱した場合の水素放出速度および水素放出量を測定することで得られたデータである。 FIG. 2 is a graph showing the relationship between the hydrogen release rate and the heating time in the degassing heat treatment of the copper alloy material (FIG. 2A) and the relationship between the hydrogen release amount and the heating time (FIG. 2B). FIG. 2 shows the hydrogen release rate and hydrogen release when the copper alloy material is heated with different heating times under conditions where the temperature is raised from room temperature to 900 ° C. at a rate of 5 ° C./min and 10 ° C./min. It is the data obtained by measuring the quantity.
図２（ａ）に示すように、昇温速度が増加した場合（図２（ａ）中では５℃／ｍｉｎ→１０℃／ｍｉｎ）、水素放出速度は速くなる（図２（ａ）中では約２倍）。また、図２（ｂ）に示すように、昇温速度が増加した場合、水素放出速度が速くなるため水素放出終了時間については約半分程度に短縮されているが、最終的に法尾出される水素放出量は５℃／ｍｉｎの場合も１０℃／ｍｉｎの場合も同程度の量となっている。 As shown in FIG. 2A, when the rate of temperature increase increases (5 ° C./min→10° C./min in FIG. 2A), the hydrogen release rate increases (in FIG. 2A). About twice). In addition, as shown in FIG. 2B, when the temperature increase rate is increased, the hydrogen release rate is increased, so that the hydrogen release end time is shortened to about half, but it is finally calculated. The amount of hydrogen released is the same in both cases of 5 ° C./min and 10 ° C./min.
即ち、図１および図２に示されるデータから昇温速度が異なる場合、水素放出終了時間は異なるものの、約７５０℃以上の温度域に到達すれば、昇温温度によらず、全水素放出量はほぼ同等の量となる。 That is, when the rate of temperature rise is different from the data shown in FIG. 1 and FIG. 2, although the hydrogen release end time is different, if the temperature reaches about 750 ° C. or higher, the total hydrogen release amount is independent of the temperature rise temperature. Are almost the same amount.
以上説明した知見に基づき、以下のような方法でもって、脱ガス熱処理が効率的に行われ後工程での粒界割れやフクレ不良の発生する恐れがないような銅合金が製造される。先ず、Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素を０．０１〜５質量％含有し、残部がＣｕと不可避不純物である銅合金の原料を準備し、これらの原料を溶解させた後、鋳造を行い銅合金材料を形成する。次いで鋳造後の銅合金材料に上述した知見から得られた条件である３００℃〜７００℃で１〜３時間保持を行う、脱ガス熱処理を施して水素量１ｗｔｐｐｍ未満の銅合金材料が得られる。その後熱間圧延、冷間圧延と熱処理の繰り返し（ただし、熱処理とは再結晶焼鈍、低温焼鈍、溶体化処理、時効処理等を指す）を順次行うことによって水素量１ｗｔｐｐｍ未満の製品である銅合金が得られる。なお、ここでの脱ガス熱処理の条件は水素の放出が十分に行われる条件であれば適宜変更可能であり、例えば銅合金材料を４００℃〜６００℃の条件下で１〜２時間程度保持するような脱ガス熱処理を行うこととしても良い。 Based on the knowledge described above, a copper alloy is manufactured by the following method so that the degassing heat treatment is efficiently performed and there is no risk of occurrence of grain boundary cracking or blister failure in the subsequent process. First, it contains 0.01 to 5% by mass of at least one element of Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag, After preparing the raw material of the copper alloy whose remainder is Cu and inevitable impurities and dissolving these raw materials, casting is performed to form a copper alloy material. Next, a copper alloy material having a hydrogen content of less than 1 wtppm is obtained by subjecting the copper alloy material after casting to a degassing heat treatment that is maintained for 1 to 3 hours at 300 ° C. to 700 ° C., which is the condition obtained from the above-described knowledge. Thereafter, a copper alloy that is a product with a hydrogen content of less than 1 wtppm by sequentially performing hot rolling, cold rolling and heat treatment (however, heat treatment means recrystallization annealing, low temperature annealing, solution treatment, aging treatment, etc.) Is obtained. Note that the degassing heat treatment conditions here can be appropriately changed as long as hydrogen is sufficiently released. For example, the copper alloy material is held at 400 ° C. to 600 ° C. for about 1 to 2 hours. Such degassing heat treatment may be performed.
ここで、本発明における脱ガス熱処理によって、中間脆性の発生が抑制される理由としては、従来のように９００℃まで急速加熱した場合は、中間脆性温度域で鋳造中に生じた圧縮応力部に水素が集まり粒界割れを生じるが、上述したように、３００℃〜７００℃で１〜３時間保持した場合はこの圧縮応力部が緩和されるために水素中間脆性を抑制できると考えられる。 Here, the reason why the generation of intermediate brittleness is suppressed by the degassing heat treatment in the present invention is that, when heated rapidly to 900 ° C. as in the prior art, the compressive stress portion generated during casting in the intermediate brittle temperature range. Although hydrogen gathers and causes intergranular cracking, as described above, it is considered that when held at 300 ° C. to 700 ° C. for 1 to 3 hours, this compressive stress portion is relaxed, so that hydrogen intermediate brittleness can be suppressed.
脱ガス熱処理を行うことで製造された銅合金は上記知見から明らかなように、脱ガス熱処理時に銅合金材料に含有される水素のほぼ全量が放出されているため、後工程の熱処理時に銅合金（材料）表面にフクレ等の不良が発生してしまう恐れが軽減される。そのため、製品として良質な銅合金を得ることが可能となる。また、従来行われていた、銅合金材料を溶解させた溶湯の状態で脱ガス熱処理を行う場合に比べ、本実施の形態では約３００℃〜７００℃の低温で銅合金材料を溶解させずに脱ガス熱処理を行うため、エネルギー効率の面で非常に優れている。また、従来のように溶湯状態での脱ガス熱処理を十分に行うためには、ある程度の真空雰囲気で行う必要があるため、設備コストの面でコスト高であり、本実施の形態で行う脱ガス熱処理はコストの面でも従来の方法に比べ優れている。
なお、脱ガス熱処理温度までの昇温、脱ガス熱処理から熱間圧延温度までの昇温については通常２〜５０℃／ｍｉｎ程度であるが特に規定する必要はない。
As is clear from the above knowledge, the copper alloy produced by performing the degassing heat treatment releases almost all of the hydrogen contained in the copper alloy material during the degassing heat treatment. (Material) The risk of defects such as blistering on the surface is reduced. Therefore, it becomes possible to obtain a high-quality copper alloy as a product. Moreover, compared with the case where the degassing heat treatment is performed in the state of the molten metal in which the copper alloy material is dissolved, which is conventionally performed, the present embodiment does not dissolve the copper alloy material at a low temperature of about 300 ° C. to 700 ° C. Since degassing heat treatment is performed, it is very excellent in terms of energy efficiency. In addition, in order to sufficiently perform the degassing heat treatment in the molten state as in the prior art, it is necessary to perform in a certain vacuum atmosphere, which is expensive in terms of equipment cost, and degassing performed in this embodiment Heat treatment is superior to conventional methods in terms of cost.
The temperature rise to the degassing heat treatment temperature and the temperature rise from the degassing heat treatment to the hot rolling temperature are usually about 2 to 50 ° C./min, but need not be specified.
本発明の脱ガス処理による銅合金の製造方法は、Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素を０．０１〜５質量％含有し、残部がＣｕと不可避不純物である銅合金材料に適用される。
合金系としては、Ｎｉ−Ｓｉ系銅合金（コルソン合金）、Ｆｅ−Ｐ系銅合金、Ｆｅ−Ｍｇ−Ｐ系銅合金、Ｍｇ−Ｐ系銅合金、ベリリウム銅、チタン銅、Ｃｒ−Ｚｒ系銅合金などが好ましい。これらの合金系の元素に加えて合計で５質量％を超えない添加元素が加わっても良い。
上記合金は、コネクタやリードフレームなどの電子材料用途として使用されるが、Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素が０．１質量％未満であると、強度やばね性などが電子材料として低すぎるおそれがある。また、５質量％を超えると導電率や熱伝導率が低下が大きく、上記電子材料用途として使用される範囲が限られる。Ｎｉ、Ｓｉ、Ｆｅ、Ｃｏ、Ｔｉ、Ｂｅ、Ｐ、Ｍｇ、Ｓｎ、Ｚｎ、Ａｌ、Ｍｎ、Ｃｒ、Ｚｒ、Ａｇの内少なくとも１種以上の元素を０．５〜５質量％含有することがさらに好ましい
The method for producing a copper alloy by degassing treatment of the present invention comprises at least one of Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag. It is applied to a copper alloy material containing 0.01 to 5% by mass of elements and the balance being Cu and inevitable impurities.
Alloys include Ni-Si copper alloy (Corson alloy), Fe-P copper alloy, Fe-Mg-P copper alloy, Mg-P copper alloy, beryllium copper, titanium copper, Cr-Zr copper Alloys are preferred. In addition to these alloy elements, additional elements not exceeding 5 mass% in total may be added.
The above alloys are used for electronic materials such as connectors and lead frames. Among these, Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, Ag If at least one element is less than 0.1% by mass, the strength and springiness may be too low as an electronic material. On the other hand, if it exceeds 5% by mass, the electrical conductivity and thermal conductivity are greatly reduced, and the range used for the electronic material is limited. It further contains 0.5 to 5% by mass of at least one element selected from Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag. preferable
以上、本発明の実施の形態の一例を説明したが、本発明は上記の形態に限定されない。当業者であれば、特許請求の範囲に記載された思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。 As mentioned above, although an example of embodiment of this invention was demonstrated, this invention is not limited to said form. It is obvious for those skilled in the art that various modifications or modifications can be conceived within the scope of the idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood.
質量％で組成が１．６％Ｎｉ−０．４％Ｓｉ−０．５％Ｓｎ−０．４％Ｚｎ−残部Ｃｕである銅合金材料を溶解鋳造した後、鋳塊を寸法３０ｍｍ×５０ｍｍ×５０ｍｍに切り出し、以下の温度保持条件で脱ガス熱処理を行った。そして脱ガス熱処理後の水素濃度を、鋳塊の中心部（約５ｍｍ角）を切り出して熱伝導度法（堀場製作所製 ＥＭＧＡ６２１Ｗ型）で測定した。 After melting and casting a copper alloy material having a composition of 1.6% Ni-0.4% Si-0.5% Sn-0.4% Zn-remainder Cu in mass%, the ingot is dimensioned to 30 mm × 50 mm × It cut out to 50 mm and degassed heat processing was performed on the following temperature holding conditions. Then, the hydrogen concentration after the degassing heat treatment was measured by a thermal conductivity method (EMGA621W type manufactured by Horiba, Ltd.) by cutting out the center part (about 5 mm square) of the ingot.
（実施例１）
試料（上記鋳塊）を室温の状態から１０℃／ｍｉｎの昇温速度でもって５００℃まで昇温させ、その５００℃の状態で試料を６０ｍｉｎ保持することで脱ガス熱処理を行った。そして脱ガス熱処理後の試料を３．３℃／ｍｉｎで９００℃まで昇温させ、次いで熱間圧延機で３０ｍｍから１０ｍｍまで圧延した。以上述べた工程を経た試料の水素濃度を測定した結果０．６ｗｔｐｐｍであった。
その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。なお、脱ガス熱処理後、熱間圧延を行わずに水冷した試料を作製して水素濃度を測定したが、上記熱間圧延後とほとんど（０．５ｗｔｐｐｍ）変わらなかった。
Example 1
The sample (the above ingot) was heated from a room temperature state to 500 ° C. at a temperature increase rate of 10 ° C./min, and the sample was held at the 500 ° C. for 60 minutes to perform degassing heat treatment. The sample after the degassing heat treatment was heated to 900 ° C. at 3.3 ° C./min, and then rolled from 30 mm to 10 mm with a hot rolling mill. It was 0.6 wtppm as a result of measuring the hydrogen concentration of the sample which passed through the process described above.
Thereafter, it was rolled to 0.2 mm by repeating cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment. Note that, after the degassing heat treatment, a water-cooled sample was prepared without performing hot rolling, and the hydrogen concentration was measured. However, the hydrogen concentration was almost the same as that after the hot rolling (0.5 wtppm).
（実施例２）
試料（上記鋳塊）を室温の状態から１０℃／ｍｉｎの昇温速度でもって５００℃まで昇温させ、その５００℃の状態で試料を１２０ｍｉｎ保持することで脱ガス熱処理を行った。そして脱ガス熱処理後の試料を５℃／ｍｉｎで９００℃まで昇温させ、次いで熱間圧延機で３０ｍｍから１０ｍｍまで圧延した。以上述べた工程を経た試料の水素濃度を測定した結果０．５ｗｔｐｐｍであった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。なお、脱ガス熱処理後、熱間圧延を行わずに水冷した試料を作製して水素濃度を測定したが、上記熱間圧延後とほとんど（０．５ｗｔｐｐｍ）変わらなかった。
(Example 2)
The sample (the above ingot) was heated from a room temperature state to 500 ° C. at a rate of temperature increase of 10 ° C./min, and degassing heat treatment was performed by holding the sample at the 500 ° C. state for 120 min. The sample after the degassing heat treatment was heated to 900 ° C. at 5 ° C./min, and then rolled from 30 mm to 10 mm with a hot rolling mill. It was 0.5 wtppm as a result of measuring the hydrogen concentration of the sample which passed through the process described above.
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment. Note that, after the degassing heat treatment, a water-cooled sample was prepared without performing hot rolling, and the hydrogen concentration was measured. However, the hydrogen concentration was almost the same as that after the hot rolling (0.5 wtppm).
（比較例１）
比較例１として、脱ガス熱処理等を行う前の試料（上記鋳塊）の水素濃度を測定した結果、１．４ｗｔｐｐｍであった。
この試料を室温の状態から１０℃／ｍｉｎの昇温速度でもって９００℃まで昇温させ、次いで熱間圧延機で３０ｍｍから１０ｍｍまで圧延したところ、熱間圧延で試料全面に割れが発生した。以上述べた工程を経た試料（熱間圧延後）の水素濃度を測定した結果１．０ｗｔｐｐｍであった。
(Comparative Example 1)
As a comparative example 1, as a result of measuring the hydrogen concentration of the sample (the above ingot) before performing the degassing heat treatment or the like, it was 1.4 wtppm.
When this sample was heated from room temperature to 900 ° C. at a temperature increase rate of 10 ° C./min and then rolled from 30 mm to 10 mm with a hot rolling mill, cracking occurred on the entire surface of the sample by hot rolling. It was 1.0 wtppm as a result of measuring the hydrogen concentration of the sample (after hot rolling) which passed through the above-mentioned process.
（比較例２）
比較例２として、試料（上記鋳塊）を室温の状態から１０℃／ｍｉｎの昇温速度でもって９００℃まで昇温させ３時間保持した後（すなわち途中の温度での保持することなしで、高温で脱ガス熱処理を行った。）、次いでこの試料を熱間圧延機で３０ｍｍから１０ｍｍまで圧延したところ、熱間圧延で圧延方向に周期的な割れが発生した。以上述べた工程を経た試料の水素濃度を測定した結果０．５ｗｔｐｐｍであった。
(Comparative Example 2)
As Comparative Example 2, the sample (the above ingot) was heated from a room temperature state to 900 ° C. at a heating rate of 10 ° C./min and held for 3 hours (that is, without holding at an intermediate temperature) Degassing heat treatment was performed at a high temperature.) Then, when this sample was rolled from 30 mm to 10 mm with a hot rolling mill, periodic cracks occurred in the rolling direction by hot rolling. It was 0.5 wtppm as a result of measuring the hydrogen concentration of the sample which passed through the process described above.
（実施例３）
質量％で組成が１．９％Ｂｅ−０．４％Ｃｏ−残部Ｃｕである銅合金原料を溶解鋳造して銅合金材を得、６５０℃で２時間保持する以外は実施例２と同様の方法で脱ガス熱処理を行った。そして脱ガス熱処理後の試料を５℃／ｍｉｎで９００℃まで昇温させ、次いで熱間圧延機で３０ｍｍから１０ｍｍまで圧延した。以上述べた工程を経た試料の水素濃度を測定した結果０．５ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 3)
A copper alloy material having a composition of 1.9% Be-0.4% Co-remainder Cu by mass is cast by melting to obtain a copper alloy material, which is the same as in Example 2 except that it is held at 650 ° C for 2 hours. The degassing heat treatment was performed by this method. The sample after the degassing heat treatment was heated to 900 ° C. at 5 ° C./min, and then rolled from 30 mm to 10 mm with a hot rolling mill. It was 0.5 wtppm (sample center part) as a result of measuring the hydrogen concentration of the sample which passed through the process described above.
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例４）
質量％で組成が０．４％Ｂｅ−１．９％Ｎｉ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．６ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
Example 4
A sample after hot rolling was produced in the same manner as in Example 3 except that a copper alloy material having a composition of 0.4% Be-1.9% Ni-remainder Cu was melt cast. The hydrogen concentration of this sample was measured and found to be 0.6 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例５）
質量％で組成が０．３％Ｂｅ−２．０％Ｎｉ−０．５％Ａｌ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．７ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 5)
Except for melting and casting a copper alloy material having a composition of 0.3% Be-2.0% Ni-0.5% Al-remainder Cu in mass%, it was subjected to hot rolling in the same manner as in Example 3. A sample was prepared. As a result of measuring the hydrogen concentration of this sample, it was 0.7 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例６）
質量％で組成が２．３％Ｆｅ−０．０３％Ｐ−残部Ｃｕである銅合金原料を溶解鋳造して銅合金材料を得、４００℃で２時間保持する以外は、実施例２と同様の方法で脱ガス熱処理を行った。そして脱ガス熱処理後の試料を５℃／ｍｉｎで９００℃まで昇温させ、次いで熱間圧延機で３０ｍｍから１０ｍｍまで圧延した。以上述べた工程を経た試料の水素濃度を測定した結果０．５ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 6)
A copper alloy material having a composition of 2.3% Fe-0.03% P-remainder Cu in mass% is melt-cast to obtain a copper alloy material, which is the same as Example 2 except that the material is held at 400 ° C. for 2 hours. The degassing heat treatment was performed by the method described above. The sample after the degassing heat treatment was heated to 900 ° C. at 5 ° C./min, and then rolled from 30 mm to 10 mm with a hot rolling mill. It was 0.5 wtppm (sample center part) as a result of measuring the hydrogen concentration of the sample which passed through the process described above.
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例７）
質量％で組成が１．８％Ｎｉ−０．５％Ｓｉ−０．５％Ｓｎ−１．０％Ｚｎ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．６ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 7)
The same method as in Example 3 except that a copper alloy material having a composition of 1.8% Ni-0.5% Si-0.5% Sn-1.0% Zn-remainder Cu was melt cast. A sample after hot rolling was prepared. The hydrogen concentration of this sample was measured and found to be 0.6 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例８）
質量％で組成が２．７％Ｎｉ−０．７％Ｓｉ−０．５％Ｓｎ−０．５％Ｚｎ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．７ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 8)
The same method as in Example 3 except that a copper alloy material having a composition of 2.7% Ni-0.7% Si-0.5% Sn-0.5% Zn-remainder Cu was melt cast. A sample after hot rolling was prepared. As a result of measuring the hydrogen concentration of this sample, it was 0.7 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例９）
質量％で組成が１．８％Ｎｉ−０．４％Ｓｉ−０．１％Ｓｎ−１．１％Ｚｎ−０．０１％Ｍｇ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．６ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
Example 9
Except for melting and casting a copper alloy material having a composition of 1.8% Ni-0.4% Si-0.1% Sn-1.1% Zn-0.01% Mg-remainder Cu in mass%. A sample after hot rolling was produced in the same manner as in Example 3. The hydrogen concentration of this sample was measured and found to be 0.6 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１０）
質量％で組成が０．２２％Ｆｅ−０．１３％Ｍｇ−０．１０％Ｐ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．６ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 10)
Except for melting and casting a copper alloy material having a composition of 0.22% Fe-0.13% Mg-0.10% P-remainder Cu in mass%, it was subjected to hot rolling in the same manner as in Example 3. A sample was prepared. The hydrogen concentration of this sample was measured and found to be 0.6 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１１）
質量％で組成が０．７％Ｍｇ−０．００５％Ｐ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．６ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 11)
A sample after hot rolling was produced in the same manner as in Example 3 except that a copper alloy material having a composition of 0.7% Mg-0.005% P-remainder Cu was melt cast. The hydrogen concentration of this sample was measured and found to be 0.6 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１２）
質量％で組成が３．２％Ｔｉ−０．２％Ｆｅ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．８ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 12)
A sample after hot rolling was prepared in the same manner as in Example 3 except that a copper alloy material having a composition of 3.2% Ti-0.2% Fe-remainder Cu was melt cast. The hydrogen concentration of this sample was measured and found to be 0.8 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１３）
質量％で組成が０．３％Ｃｒ−０．２５％Ｓｎ−０．２％Ｚｎ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．７ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 13)
Except for melting and casting a copper alloy material having a composition of 0.3% Cr-0.25% Sn-0.2% Zn-remainder Cu in mass%, it was subjected to hot rolling in the same manner as in Example 3. A sample was prepared. As a result of measuring the hydrogen concentration of this sample, it was 0.7 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１４）
質量％で組成が０．５％Ｃｒ−０．１％Ａｇ−０．０８％Ｆｅ−０．０６％Ｔｉ−０．０３％Ｓｉ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．８ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 14)
Except for melting and casting a copper alloy material having a composition of 0.5% Cr-0.1% Ag-0.08% Fe-0.06% Ti-0.03% Si-remainder Cu in mass% A sample after hot rolling was produced in the same manner as in Example 3. The hydrogen concentration of this sample was measured and found to be 0.8 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１５）
質量％で組成が０．３％Ｃｒ−０．１５％Ｚｒ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．８ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 15)
A sample after hot rolling was produced in the same manner as in Example 3 except that a copper alloy material having a composition of 0.3% Cr-0.15% Zr-remainder Cu was melt cast. The hydrogen concentration of this sample was measured and found to be 0.8 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１６）
質量％で組成が０．１５％Ｚｒ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．９ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 16)
A sample after hot rolling was produced in the same manner as in Example 3 except that a copper alloy material having a composition of 0.15% by mass and 0.15% Zr-remainder Cu was melt cast. As a result of measuring the hydrogen concentration of this sample, it was 0.9 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（実施例１７）
質量％で組成が０．３％Ｃｒ−０．３Ｓｎ−０．２％Ｚｎ−残部Ｃｕである銅合金材料を溶解鋳造した以外は、実施例３と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果０．５ｗｔｐｐｍ（試料中心部）であった。
この試料を、その後冷間圧延と熱処理（焼鈍）の繰り返しにより０．２ｍｍまで圧延した。このとき熱間圧延で割れは発生せず、また熱処理後もフクレの発生はみられなかった。
(Example 17)
A sample after hot rolling was prepared in the same manner as in Example 3 except that a copper alloy material having a composition of 0.3% Cr-0.3Sn-0.2% Zn-remainder Cu was melt cast. Produced. The hydrogen concentration of this sample was measured and found to be 0.5 wtppm (sample center).
This sample was then rolled to 0.2 mm by repeated cold rolling and heat treatment (annealing). At this time, no crack was generated by hot rolling, and no blistering was observed after the heat treatment.
（比較例３）
実施例３の合金組成である以外は比較例１と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果３．０ｗｔｐｐｍ（試料中心部）であった。また、熱間圧延で割れが発生した。
(Comparative Example 3)
A sample after hot rolling was produced in the same manner as in Comparative Example 1 except that the alloy composition of Example 3 was used. The hydrogen concentration of this sample was measured and found to be 3.0 wtppm (sample center). Moreover, the crack generate | occur | produced by hot rolling.
（比較例４）
実施例６の合金組成である以外は比較例１と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果２．８ｗｔｐｐｍ（試料中心部）であった。また、熱間圧延で割れが発生した。
(Comparative Example 4)
A sample after hot rolling was produced in the same manner as in Comparative Example 1 except that the alloy composition of Example 6 was used. The hydrogen concentration of this sample was measured and found to be 2.8 wtppm (sample center). Moreover, the crack generate | occur | produced by hot rolling.
（比較例５）
実施例７の合金組成である以外は比較例１と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果２．９ｗｔｐｐｍ（試料中心部）であった。また、熱間圧延で割れが発生した。
(Comparative Example 5)
A sample after hot rolling was produced in the same manner as in Comparative Example 1 except that the alloy composition of Example 7 was used. The hydrogen concentration of this sample was measured and found to be 2.9 wtppm (sample center). Moreover, the crack generate | occur | produced by hot rolling.
（比較例６）
実施例１０の合金組成である以外は比較例１と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果２．９ｗｔｐｐｍ（試料中心部）であった。また、熱間圧延で割れが発生した。
(Comparative Example 6)
A sample after hot rolling was produced in the same manner as in Comparative Example 1 except that the alloy composition of Example 10 was used. The hydrogen concentration of this sample was measured and found to be 2.9 wtppm (sample center). Moreover, the crack generate | occur | produced by hot rolling.
（比較例７）
実施例１２の合金組成である以外は比較例１と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果３．０ｗｔｐｐｍ（試料中心部）であった。
この試料を熱間圧延機で３０ｍｍから１０ｍｍまで圧延したところ、熱間圧延で割れが発生した。
(Comparative Example 7)
A sample after hot rolling was produced in the same manner as in Comparative Example 1 except that the alloy composition of Example 12 was used. The hydrogen concentration of this sample was measured and found to be 3.0 wtppm (sample center).
When this sample was rolled from 30 mm to 10 mm with a hot rolling mill, cracks occurred during hot rolling.
（比較例８）
実施例１３の合金組成である以外は比較例１と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果３．１ｗｔｐｐｍ（試料中心部）であった。また、熱間圧延で割れが発生した。
(Comparative Example 8)
A sample after hot rolling was produced in the same manner as in Comparative Example 1 except that the alloy composition of Example 13 was used. The hydrogen concentration of this sample was measured and found to be 3.1 wtppm (sample center). Moreover, the crack generate | occur | produced by hot rolling.
（比較例９）
実施例１５の合金組成である以外は比較例１と同様の方法で熱間圧延後の試料を作製した。この試料の水素濃度を測定した結果２．９ｗｔｐｐｍ（試料中心部）であった。また、熱間圧延で割れが発生した。
(Comparative Example 9)
A sample after hot rolling was produced in the same manner as in Comparative Example 1 except that the alloy composition of Example 15 was used. The hydrogen concentration of this sample was measured and found to be 2.9 wtppm (sample center). Moreover, the crack generate | occur | produced by hot rolling.
上記各実施例の測定結果と各比較例との比較により本発明にかかる脱ガス熱処理によって、試料からの十分な水素ガスの放出が実現されていることが分かった。 From the comparison of the measurement results of the above examples and the comparative examples, it was found that sufficient hydrogen gas was released from the sample by the degassing heat treatment according to the present invention.
本発明は、例えばリードフレームやコネクター等の電気・電子機器用部品に用いられる熱間加工性に優れた銅合金の製造方法に適用できる。 The present invention can be applied to a method for producing a copper alloy having excellent hot workability used for parts for electrical and electronic equipment such as lead frames and connectors.
Claims (2)
前記銅合金材料を３００℃〜７００℃で１〜３時間保持することで脱ガス熱処理を行い、
脱ガス熱処理後の銅合金材料に熱間圧延、冷間圧延、熱処理を施すことによって銅合金を得る、銅合金の製造方法。 Containing at least one element of at least one of Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag in a total amount of 0.01 to 5 mass%, Forming a copper alloy material with the balance being inevitable impurities with Cu,
Degassing heat treatment is performed by holding the copper alloy material at 300 ° C. to 700 ° C. for 1 to 3 hours,
The manufacturing method of a copper alloy which obtains a copper alloy by performing hot rolling, cold rolling, and heat processing to the copper alloy material after degassing heat processing.
前記銅合金材料を４００℃〜６００℃で１〜２時間保持することで脱ガス熱処理を行い、
脱ガス熱処理後の銅合金材料に熱間圧延、冷間圧延、熱処理を施すことによって銅合金を得る、銅合金の製造方法。
Containing at least one element of at least one of Ni, Si, Fe, Co, Ti, Be, P, Mg, Sn, Zn, Al, Mn, Cr, Zr, and Ag in a total amount of 0.01 to 5 mass%, Forming a copper alloy material with the balance being inevitable impurities with Cu,
A degassing heat treatment is performed by holding the copper alloy material at 400 ° C. to 600 ° C. for 1 to 2 hours,
The manufacturing method of a copper alloy which obtains a copper alloy by performing hot rolling, cold rolling, and heat processing to the copper alloy material after degassing heat processing.
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