JP4177221B2 - Copper alloy for electronic equipment - Google Patents
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Description
本発明は、エッチング、プレス加工により所望の形状に加工される銅合金、例えばリードフレーム材、端子・コネクター材、スイッチ材等に適用する電気電子機器用銅合金とその製造方法に関する。 The present invention relates to a copper alloy processed into a desired shape by etching and pressing, for example, a copper alloy for electrical and electronic equipment applied to a lead frame material, a terminal / connector material, a switch material, and the like, and a method for producing the same.
半導体のリードフレーム材や携帯電話等の電子機器の端子・コネクター材には、電気伝導性及び熱伝導性に優れた銅合金が多く用いられている。近年は半導体及び電子機器の高集積化や小型化が進み、これらに使用される銅合金も電気伝導性や熱伝導性ばかりでなく、強度、耐熱性、及び貴金属（Ａｇ、Ｐｄ等）や半田とのめっき性が優れていることが求められている。このめっき性を確保するには優れた表面平滑性も必要となっている。更に前記要求特性が長期に保持されること、即ち経時的信頼性も重要である。
このような要求に応えるために、様々な銅合金が開発されたが、その多くは淘汰され現在では数種類が用いられているだけであり、その中でもＣｕ−Ｃｒ系合金は高い導電性と強度を兼備する合金として、広く使用されている合金系の一つである（例えば、特許文献１、２、３参照）。
Copper alloys excellent in electrical conductivity and thermal conductivity are often used for terminals / connectors of semiconductor lead frame materials and electronic devices such as mobile phones. In recent years, semiconductors and electronic devices have been highly integrated and miniaturized, and copper alloys used for these have not only electrical and thermal conductivity, but also strength, heat resistance, precious metals (Ag, Pd, etc.) and solder. It is required to have excellent plating properties. Excellent surface smoothness is also required to ensure this plating property. Further, it is important that the required characteristics are maintained for a long time, that is, reliability over time.
In order to meet such demands, various copper alloys have been developed, but many of them have been rejected and only a few types are currently used. Among them, Cu-Cr alloys have high conductivity and strength. It is one of the alloy systems that are widely used as a combined alloy (see, for example, Patent Documents 1, 2, and 3).
リードフレーム等の成形加工には、通常エッチング加工法またはプレス打抜き加工法が用いられる。特にＣｕ−Ｃｒ系合金はエッチング加工性に優れていることからエッチング加工法が有利な多ピンリードフレーム材料に広く用いられていたが、近年のプレス技術の革新により、プレス打抜き加工法でも多ピンリードフレームの製造が可能となってきており、生産性の面ではエッチング加工法より優れるプレス打抜き加工法が採用されてきている。 For forming a lead frame or the like, an etching method or a press punching method is usually used. In particular, Cu-Cr alloys have been widely used in multi-pin lead frame materials where etching is advantageous because of their excellent etching processability. However, due to recent innovations in press technology, multi-pins are also used in press punching. Lead frames can be manufactured, and a press punching method that is superior to an etching method in terms of productivity has been adopted.
しかしながら、従来のＣｕ−Ｃｒ系合金のプレス打抜き加工性は必ずしも良好ではなく、加工の際にバリや加工粉が発生してリード間の短絡を起こしたり、またリードフレームの寸法精度が低下したりする不具合が発生していた。また、この様な不具合は金型のメンテナンスサイクルを短くするため、生産性を低下させ、製造コストを高くする一因ともなっている。 However, the press-punching processability of conventional Cu-Cr alloys is not always good, and burrs and processing powder are generated during processing, causing short circuit between leads, and dimensional accuracy of the lead frame is reduced. A problem occurred. In addition, such a defect shortens the maintenance cycle of the mold, and thus contributes to a decrease in productivity and an increase in manufacturing cost.
即ち、リードフレームを安価に早く提供するためには、如何にプレス加工設備の稼働率を上げるか、如何に不良品を減らして製造歩留まりを高めるかが重要な課題となり、特にＣｕ−Ｃｒ系合金においてはプレス打抜き加工性の大幅な改善が強く望まれた。 That is, in order to provide a lead frame at a low cost and quickly, how to increase the operating rate of the press processing equipment and how to reduce defective products and increase the production yield are important issues, particularly Cu-Cr alloys. Therefore, a significant improvement in press punching workability was strongly desired.
このような要求に対して、Ｃｕ−Ｃｒ系合金に微量元素を添加し、Ｃｕマトリックス中に添加元素によるＣｒ化合物を析出させ、これを加工時の破壊の起点とし、プレス打抜き加工性を改善する方法が提案されている（例えば特許文献３参照）。
しかし、Ｃｒ化合物は粗大化し易いと共に、圧延加工により圧延方向に長く伸び易い性質があるため、ヒゲ状の形態となり、エッチング加工時に溶解されないヒゲ状のＣｒ化合物がリード端面から突出し、リード間の短絡原因となると共にヒゲ状の化合物上のＡｇめっきがこぶ状になるめっき不良を発生させていた。
In response to such a demand, a trace element is added to the Cu-Cr alloy, and a Cr compound by the additive element is precipitated in the Cu matrix, which is used as a starting point of fracture during processing to improve press punching workability. A method has been proposed (see, for example, Patent Document 3).
However, the Cr compound is easy to coarsen and has the property of easily extending in the rolling direction due to the rolling process. Therefore, the bearded form is formed, and the bearded Cr compound that is not dissolved during the etching process protrudes from the end face of the lead, and the short circuit between the leads. In addition to this, plating defects in which the Ag plating on the beard-like compound became hump-like were generated.
そこで、本発明ではエッチング加工とプレス打抜き加工の双方に好適に使用できるＣｕ−Ｃｒ系合金の提供を目的とする。 Therefore, an object of the present invention is to provide a Cu—Cr-based alloy that can be suitably used for both etching and press punching.
請求項１記載の発明は、Ｃｒを０．１〜０．２５ｗｔ％、Ｓｉを０．００５〜０．１ｗｔ％、Ｚｎを０．１〜０．５ｗｔ％、Ｓｎを０．０５〜０．５ｗｔ％含み、ＣｒとＳｉの重量比Ｃｒ／Ｓｉが３〜２５の範囲で、残部銅及び不可避的不純物からなる銅合金において、銅母相中に、０．０５μｍ〜１０μｍの大きさを有するＣｒＳｉ化合物が１×１０３〜５×１０５個／ｍｍ２の個数密度で存在し、且つ、ＣｒＳｉ化合物以外のＣｒ化合物の大きさが１０μｍ以下であることを特徴とするエッチング加工性及び打ち抜き加工性の両方に優れた電子機器用銅合金である。
According to the first aspect of the present invention, Cr is 0.1 to 0.25 wt%, Si is 0.005 to 0.1 wt%, Zn is 0.1 to 0.5 wt%, and Sn is 0.05 to 0.5 wt%. CrSi compound having a size of 0.05 μm to 10 μm in a copper matrix in a copper alloy comprising the balance copper and inevitable impurities in a Cr / Si weight ratio of Cr / Si in the range of 3 to 25 there exist in the number density of 1 × 10 3 ~5 × 10 5 cells / mm 2, and the etching workability and punching workability size of Cr compounds other than CrSi compound is characterized der Rukoto below 10μm It is an excellent copper alloy for electronic devices.
本発明に係る銅合金は、プレス打抜き加工性とエッチング加工性が共に優れ、また、強度や導電率、並びに半田付け性やめっき性等にも優れるもので、近年、微細加工性が要求される多ピン、狭ピッチのリードフレームを始め、端子、コネクター、スイッチ、リレー等の小型化する電子機器部品用として好適に使用できる。依って、本発明は産業上有用かつ顕著な効果を奏するものである。 The copper alloy according to the present invention is excellent in both press punching workability and etching workability, and is excellent in strength, electrical conductivity, solderability, plating ability, etc., and has recently required fine workability. It can be suitably used for electronic device parts such as multi-pin, narrow-pitch lead frames, terminals, connectors, switches, relays, and the like that are miniaturized. Therefore, the present invention has industrially useful and remarkable effects.
本発明の合金は、Ｃｕマトリックス中に、プレス打抜き加工性を改善しながら、エッチング加工性を確保するために、所定の大きさ及び個数密度を有するＣｒＳｉ化合物を微細に析出させること及びＣｒＳｉ以外のＣｒ化合物の大きさを制限することを骨子としている。
本発明者らはこのＣｒを含む銅合金系について研究を行い、ＣｒＳｉ化合物が打ち抜き加工性の改善に寄与しながら、展延性が低いために圧延加工時に圧延方向に伸び難く、ヒゲ状に変形しないことを新たに知見した。又、ＣｒＳｉ化合物以外のＣｒ−Ｃｕ化合物、Ｃｒ−Ｓ化合物、Ｃｒ−Ｐ化合物などのＣｒ化合物は、展延性が高く、圧延加工時に圧延方向に伸びてヒゲ状になることを見出した。即ち、このＣｒＳｉ化合物を適正に生成させてプレス打抜き加工性を改善し、かつＣｒＳｉ以外のＣｒ化合物の大きさを制御することで、ヒゲ状化合物の生成を抑制し、エッチング加工性も満足する銅合金を見出したのである。
The alloy according to the present invention is a method in which a CrSi compound having a predetermined size and number density is finely precipitated and other than CrSi in order to ensure etching processability while improving press punching processability in a Cu matrix. The main point is to limit the size of the Cr compound.
The present inventors have studied the copper alloy system containing Cr, and while the CrSi compound contributes to the improvement of the punching workability, it is difficult to extend in the rolling direction at the time of rolling due to low ductility, and does not deform into a beard shape. I found out that. Moreover, it discovered that Cr compounds, such as Cr-Cu compound, Cr-S compound, Cr-P compound other than a CrSi compound, had high ductility, and extended in the rolling direction at the time of a rolling process, and became whisker-like. In other words, copper is produced by properly producing this CrSi compound to improve press punching workability, and by controlling the size of the Cr compound other than CrSi, thereby suppressing the production of mustache-like compounds and satisfying etching workability. I found an alloy.
本発明においては、成分の限定と製造条件を合わせて制御することにより、プレス打抜き加工性の改善に理想的なＣｒＳｉ化合物の析出状態を達成しつつ、エッチング加工性の低下原因となるＣｒＳｉ以外のＣｒ化合物の大きさを制御することで、実用性に優れる本発明に係る銅合金を得たものである。
本発明に係る銅合金は、ＣｒＳｉ化合物を理想的に析出させ、且つ、ＣｒＳｉ以外のＣｒ化合物の大きさを制御するために、熱間加工前に８５０℃から９８０℃の加熱処理を施し、又、リードフレーム材としてのバランスの取れた特性を満足させるために、熱間加工後に冷間加工と４００℃から６００℃の温度での熱処理の組み合わせによる工程を一回、若しくは、繰返し複数回施すことが必要である。
In the present invention, by controlling the combination of the component limitations and the manufacturing conditions, while achieving the precipitation state of the CrSi compound ideal for improving the press punching processability, other than CrSi that causes the etching processability to deteriorate By controlling the size of the Cr compound, a copper alloy according to the present invention having excellent practicality is obtained.
The copper alloy according to the present invention is subjected to heat treatment from 850 ° C. to 980 ° C. before hot working in order to ideally precipitate the CrSi compound and to control the size of the Cr compound other than CrSi. In order to satisfy the balanced characteristics as a lead frame material, a process by a combination of cold working and heat treatment at a temperature of 400 ° C. to 600 ° C. is performed once or repeatedly after hot working. is required.
次に本発明合金の成分限定理由を説明する。
Ｃｒを０．１〜０．２５ｗｔ％としたのは、Ｃｒ量が０．１ｗｔ％未満では熱間加工前に８５０℃〜９８０℃の温度での加熱処理を施しても、ＣｒＳｉ化合物の生成量が少なく、プレス打抜き加工性の改善効果が不十分であるためである。逆に、Ｃｒ量が０．２５ｗｔ％を超えると、ＣｒＳｉ以外のＣｒ化合物が１０μｍより粗大化するため、圧延加工後にヒゲ状になり、エッチング加工後のリード短絡の原因となったり、めっき性を低下させるためである。
Next, the reasons for limiting the components of the alloy of the present invention will be described.
The reason why Cr is 0.1 to 0.25 wt% is that if the Cr amount is less than 0.1 wt%, the amount of CrSi compound produced even if heat treatment is performed at a temperature of 850 ° C. to 980 ° C. before hot working. This is because the effect of improving the press punching workability is insufficient. Conversely, if the Cr content exceeds 0.25 wt%, Cr compounds other than CrSi will become coarser than 10 μm, and thus will become whiskered after rolling, leading to lead shorts after etching, and plating properties. It is for lowering.
Ｓｉ量を０．００５〜０．１ｗｔ％とするのは、Ｓｉ量が０．００５ｗｔ％未満では、ＣｒＳｉ化合物のサイズ及び分散密度が小さくプレス打抜き加工性が改善されない。逆に、０．１ｗｔ％を超えると１０μｍを超える粗大なＣｒＳｉ化合物が生成するため、エッチング加工後のリード短絡の原因となると共に、Ｃｕ中に固溶するＳｉ量が多くなり、導電率が低下するためである。
更に、Ｃｒ／Ｓｉの成分比を３〜２５とするのは、成分比が３未満では、Ｃｒが少ない場合にはＣｒＳｉ化合物の生成量が少なくプレス打抜き加工性の改善効果が弱い。又、Ｓｉ量が多い場合にはＣｒＳｉ化合物が１０μｍを超えて粗大化するため、エッチング加工後のリード短絡の原因となると共に、導電率も低下するためである。成分比が２５を超えるとＣｒＳｉ化合物以外のＣｒ化合物が１０μｍを超え粗大化するため、圧延加工により伸びてヒゲ状になり、エッチング加工後のリード短絡の原因となるためである。
The reason why the Si amount is 0.005 to 0.1 wt% is that when the Si amount is less than 0.005 wt%, the size and dispersion density of the CrSi compound are small and the press punching processability is not improved. On the other hand, if it exceeds 0.1 wt%, a coarse CrSi compound exceeding 10 μm is generated, causing lead short circuit after etching and increasing the amount of Si dissolved in Cu, resulting in a decrease in conductivity. It is to do.
Furthermore, the Cr / Si component ratio is set to 3 to 25. When the component ratio is less than 3, when the amount of Cr is small, the amount of CrSi compound produced is small and the effect of improving the press punching workability is weak. Further, when the amount of Si is large, the CrSi compound is coarsened to exceed 10 μm, which causes a lead short circuit after the etching process and also decreases the conductivity. When the component ratio exceeds 25, Cr compounds other than the CrSi compound become larger than 10 μm and become coarse, so that they become elongated due to the rolling process and become a beard shape, causing a lead short circuit after the etching process.
先に述べたように本発明は、ＣｒＳｉ化合物を打ち抜き加工時の破壊の起点とすることでプレス打抜き性を改善するものであるが、その最大径が０．０５μｍより小さいと打ち抜き性の改善に寄与せず、逆に最大径が１０μｍを超えるとエッチング加工時にリード短絡の原因となる。従って、各々の最大径が０．０５〜１０μｍの化合物が適量分散している状態が理想的である。
更に、これらの化合物の分散密度が、１×１０３個／ｍｍ２未満ではプレス打抜き加工性の改善効果が少なく、５×１０５個／ｍｍ２を超えると打ち抜き加工性は良好であるが、強度特性および耐熱性が低下し、リードフレーム材としての機能を果たさない。
As described above, the present invention improves the press punchability by using a CrSi compound as a starting point of fracture at the time of punching. However, if the maximum diameter is smaller than 0.05 μm, the punchability is improved. Conversely, if the maximum diameter exceeds 10 μm without contributing, a lead short circuit may occur during etching. Therefore, it is ideal that each compound having a maximum diameter of 0.05 to 10 μm is dispersed in an appropriate amount.
Furthermore, when the dispersion density of these compounds is less than 1 × 10 3 pieces / mm 2 , the effect of improving the press punching workability is small, and when it exceeds 5 × 10 5 pieces / mm 2 , the punching workability is good. Strength characteristics and heat resistance are reduced, and it does not function as a lead frame material.
ＣｒＳｉ化合物以外のＣｒ化合物の大きさを１０μｍ以下とするのは、１０μｍを超えると前述のように、このＣｒ化合物は圧延加工により圧延方向に長く伸びるため、エッチング加工時にヒゲ状に端面から突出し、リード短絡の原因となる。
なお、本発明においては、Ｃｕ−Ｃｒ合金における前記ＣｒＳｉ化合物とＣｒＳｉ化合物以外のＣｒ化合物の役割と影響を分離したことが最重要ポイントであり、これらのサイズと分散密度を個別に制御する成分と製造方法を見いだしたことで、エッチング加工性とプレス打抜き加工性の双方を良好に満足させることを可能としたものである。
The size of the Cr compound other than the CrSi compound is 10 μm or less, as described above when the Cr compound exceeds 10 μm, because this Cr compound extends long in the rolling direction by rolling, so that it protrudes from the end face in a beard shape during etching processing, It may cause lead short circuit.
In the present invention, it is the most important point that the role and influence of the Cr compound other than the CrSi compound and the CrSi compound in the Cu-Cr alloy are separated, and the components for individually controlling the size and the dispersion density By finding the manufacturing method, it is possible to satisfactorily satisfy both the etching processability and the press punching processability.
Ｓｎは、材料の強度を高める効果を有する。添加量が０．０５ｗｔ％に満たない場合、所定の強度が達成できず、逆に添加量が多いと、導電性が低下する。従って、Ｓｎの添加範囲は０．０５〜０．５ｗｔ％が最適である。 Sn has the effect of increasing the strength of the material. When the addition amount is less than 0.05 wt%, the predetermined strength cannot be achieved. Conversely, when the addition amount is large, the conductivity is lowered. Therefore, the addition range of Sn is optimally 0.05 to 0.5 wt%.
ＺｎはＳｎめっきやはんだの耐熱剥離性及び耐マイグレーション特性を改善する効果を有する。特に電子機器用のリードフレームやコネクターに使用される場合、実装後の半田付け部の経時劣化が重視されるため、Ｚｎ添加が不可欠である。その含有量が０．１ｗｔ％未満では充分な効果が得られず、０．５ｗｔ％を超えて添加しても、その効果は飽和し、逆に、導電性を低下させる。従って、Ｚｎの添加範囲は０．１〜０．５ｗｔ％とする。 Zn has the effect of improving the heat resistance peelability and migration resistance characteristics of Sn plating and solder. In particular, when used for lead frames and connectors for electronic equipment, Zn addition is indispensable because deterioration with time of the soldered portion after mounting is emphasized. If the content is less than 0.1 wt%, a sufficient effect cannot be obtained. Even if the content exceeds 0.5 wt%, the effect is saturated, and conversely, the conductivity is lowered. Therefore, the addition range of Zn shall be 0.1-0.5 wt%.
更に、強度、耐熱性、耐応力緩和特性等の電子機器用途としての要求特性を改善するために、必要に応じて、Ｍｇ、Ｔｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ａｇ、Ａｌ、Ｉｎ、Ｐｂ、Ｂｉ、Ｔｅ、Ｃａ、Ｂ、Ｃ、Ｐなどの添加元素を導電率が阻害されない範囲として０．５ｗｔ％未満添加しても良い。 Furthermore, Mg, Ti, Mn, Fe, Co, Ni, Ag, Al, In, Pb may be used as necessary in order to improve the properties required for electronic equipment applications such as strength, heat resistance, and stress relaxation resistance. , Bi, Te, Ca, B, C, P and the like may be added in an amount that does not hinder the conductivity, and less than 0.5 wt%.
次に、前記本発明の構成を用いて良好な特性を実現するためには、その製造方法が重要である。
プレス打抜き加工性の改善にはＣｒＳｉ化合物の生成が大きく寄与しているが、前記熱間加工前の加熱処理温度が９８０℃より高いと、最大径が０．０５〜１０μｍのＣｒＳｉ化合物の個数密度が低くなり、プレス打抜き加工性が改善されない。逆に加熱処理温度が８５０℃未満では、Ｃｒ化合物（ＣｒＳｉ化合物以外）の大きさが１０μｍを超えるか、その個数密度が１×１０３個／ｍｍ２以上となり、Ｃｒ化合物が圧延加工により圧延方向に長く伸びるか、又は隣接した化合物同士が断続的につながり易いため、エッチング加工時にリード短絡の原因となる。このような観点から、熱間加工前の加熱処理温度は８５０℃〜９８０℃とする。特に、８８０℃〜９５０℃が好ましい範囲である。
Next, in order to achieve good characteristics using the configuration of the present invention, the manufacturing method is important.
The production of CrSi compounds greatly contributes to the improvement of press punching workability. However, when the heat treatment temperature before hot working is higher than 980 ° C., the number density of CrSi compounds having a maximum diameter of 0.05 to 10 μm. The press punching processability is not improved. Conversely, when the heat treatment temperature is less than 850 ° C., the size of the Cr compound (other than the CrSi compound) exceeds 10 μm, or the number density is 1 × 10 3 pieces / mm 2 or more, and the Cr compound is rolled in the rolling direction. In other words, the adjacent compounds are likely to be intermittently connected to each other. From such a viewpoint, the heat treatment temperature before hot working is set to 850 ° C to 980 ° C. In particular, 880 ° C. to 950 ° C. is a preferable range.
更にリードフレーム材としてのバランスの取れた強度と導電率を満足させるためには、熱間加工後に冷間加工と４００℃から６００℃の温度での熱処理との組み合わせによる工程を一回、若しくは、繰返し複数回施すことが必要である。なお、最終冷間加工後に比較的低温での熱処理を施して加工歪みを減じておくことが望ましく、バッチ式焼鈍方法では２００℃〜４５０℃の温度で０．５〜５時間、走間式焼鈍方法では６００℃〜８００℃の温度で５〜１２０秒間施すことが好ましい。また、最終熱処理の前または後にテンションレベラーやローラーレベラーなどで矯正加工を行っても良い。 Furthermore, in order to satisfy the balanced strength and electrical conductivity as the lead frame material, a process by a combination of cold working and heat treatment at a temperature of 400 ° C. to 600 ° C. is performed once after hot working, or It is necessary to apply repeatedly several times. In addition, it is desirable to reduce the processing strain by applying a heat treatment at a relatively low temperature after the final cold working, and in the batch type annealing method, running annealing at a temperature of 200 ° C. to 450 ° C. for 0.5 to 5 hours. In the method, it is preferably applied at a temperature of 600 ° C. to 800 ° C. for 5 to 120 seconds. Further, straightening may be performed with a tension leveler or a roller leveler before or after the final heat treatment.
以下に本発明を実施例により詳細に説明する。
表１に示す本発明例合金を高周波溶解炉にて溶解し、厚さ３０ｍｍ、幅１００ｍｍ、長さ１５０ｍｍの鋳塊を作製した。この鋳塊を９４０℃で２時間加熱後、厚さ１１ｍｍまで熱間圧延し、熱間圧延後、直ちに水中に浸漬して速やかに冷却した。次に両面を各１ｍｍづつ面削した後、０．２５ｍｍまで冷間圧延し、この冷間圧延材を不活性ガス雰囲気中において５３０℃の温度で２時間の熱処理を施し、その後０．１５ｍｍまで仕上げ冷間圧延した後、３５０℃の温度で２時間の低温焼鈍処理を施し、表２に示す本発明例のＮｏ．１からＮｏ．９の銅合金板供試材を得た。
Hereinafter, the present invention will be described in detail with reference to examples.
Inventive alloys shown in Table 1 were melted in a high-frequency melting furnace to produce an ingot having a thickness of 30 mm, a width of 100 mm, and a length of 150 mm. The ingot was heated at 940 ° C. for 2 hours, and then hot-rolled to a thickness of 11 mm. After hot rolling, the ingot was immediately immersed in water and quickly cooled. Next, both sides of each side are chamfered by 1 mm, and then cold-rolled to 0.25 mm. The cold-rolled material is heat-treated at 530 ° C. for 2 hours in an inert gas atmosphere, and then to 0.15 mm. After the finish cold rolling, a low temperature annealing treatment was performed at a temperature of 350 ° C. for 2 hours. 1 to No. 9 copper alloy sheet test materials were obtained.
表１に示す比較例合金も本発明例合金と同じ方法により作製し、表２の比較例Ｎｏ．２１からＮｏ．２６の銅合金板供試材を得た。 The comparative example alloys shown in Table 1 were also produced by the same method as the inventive example alloys. 21 to No. 26 copper alloy plate test materials were obtained.
作製した供試材から試験片を切り出して、化合物相の個数密度、引張強さ、伸び、導電率、プレス打抜き加工性、はんだ耐熱剥離性を評価した。結果を表２、表３に示す。
化合物の種類と大きさは、試験片を酸性水溶液（６体積％Ｈ２ＳＯ４＋７体積％Ｈ２Ｏ２）中に３０秒間浸漬してエッチングし、走査型電子顕微鏡（１０００倍）にて無作為に選んだ１０視野に存在する化合物全てをＸ線マイクロアナライザーにて分析して、各々の化合物の種類（ＣｒＳｉ化合物又はＣｒ化合物）を決定した後、視野を写真撮影して、化合物の大きさの平均値を算出した。ここで大きさとは最大径であり、化合物が球形の場合はその径、楕円状の場合は長径、棒状の場合は最大長さと定義する。
個数密度は、化合物の大きさの測定と同様に１０視野内のおける各々の化合物の個数を数え、その密度の平均値を算出した。
Test pieces were cut out from the prepared test materials, and the number density, tensile strength, elongation, electrical conductivity, press punching workability, and solder heat release property of the compound phases were evaluated. The results are shown in Tables 2 and 3.
The type and size of the compound were determined by immersing the test piece in an acidic aqueous solution (6 volume% H 2 SO 4 +7 volume% H 2 O 2 ) for 30 seconds and etching it, and using a scanning electron microscope (1000 times). Analyze all the compounds present in the 10 fields of view selected for the purpose with an X-ray microanalyzer and determine the type of each compound (CrSi compound or Cr compound), then photograph the field of view to determine the size of the compound. The average value of was calculated. Here, the size is the maximum diameter, which is defined as the diameter when the compound is spherical, the long diameter when it is elliptical, and the maximum length when it is rod-shaped.
For the number density, the number of each compound in 10 fields of view was counted as in the measurement of the size of the compound, and the average value of the densities was calculated.
引張強さ（ＴＳ）及び伸び（Ｅｌ）はＪＩＳ Ｚ２２４１に準じ、熱・電気の伝導性を示す導電率はＪＩＳ Ｈ０５０５に準じて各々測定した。 Tensile strength (TS) and elongation (El) were measured according to JIS Z2241, and conductivity indicating thermal and electrical conductivity was measured according to JIS H0505.
プレス打抜き加工性は、金型で角孔（１ｍｍ×５ｍｍ）を多数打ち抜いて、ＦＡＲ（Ｆｒａｃｔｕｒｅ Ａｒｅａ Ｒａｔｉｏ：せん断／破断面を示す打抜き面での板厚に対する破断部長さ比）、及びバリの高さを測定した。金型のダイ、パンチは超硬合金製のものを用い、両者のクリアランスは９μｍ（対板厚比６％）とした。
前記ＦＡＲは角孔加工面を観察して破断部の厚さｔを測定し、これをプレス打抜き加工前の試験片の厚さＴで除した値（ｔ／Ｔ）を各２０箇所について求め、その平均値で評価した。ＦＡＲは大きいほどプレス打抜き加工性に優れる。
バリ高さは、角孔縁部のバリ高さを接触式形状測定器で各２０箇所測定し、その平均値で示した。
The press punching workability is such that a large number of square holes (1 mm × 5 mm) are punched with a mold, FAR (Fracture Area Ratio: the ratio of the fractured part length to the plate thickness at the punched surface showing the shear / fracture surface), and the high burr Was measured. The die and punch of the mold were made of cemented carbide, and the clearance between them was 9 μm (vs. thickness ratio 6%).
The FAR was measured for the thickness t of the fractured portion by observing the square hole processed surface, and the value (t / T) obtained by dividing this by the thickness T of the test piece before press punching was obtained for each of 20 locations. The average value was evaluated. The larger the FAR, the better the press punching processability.
The burr height was measured by measuring 20 burr heights at the edge of the square hole with a contact-type shape measuring device, and the average value was shown.
エッチング性は試験片を塩化第二鉄溶液にてエッチング加工し、圧延方向に対し垂直方向に幅０．５ｍｍのリード部を形成した。このエッチング端面を顕微鏡観察（５０倍）し、突起物の有無を調べた。この顕微鏡観察で明瞭に突起物が認められる場合は、不良とした。 The etching property was obtained by etching a test piece with a ferric chloride solution to form a lead portion having a width of 0.5 mm in a direction perpendicular to the rolling direction. The etching end face was observed with a microscope (50 times) to examine the presence or absence of protrusions. If the projections were clearly observed by microscopic observation, it was judged as defective.
はんだ耐熱剥離性は試験片にロジン系フラックスを塗布し、２３０℃の共晶半田（Ｐｂ−６３ｗｔ％Ｓｎ合金）浴中に５秒間浸漬してはんだを付着させ、これを１５０℃で１０００時間大気加熱した後、１８０度密着曲げを施し、次いで曲げ戻して、その曲げ戻し部分のはんだ剥離の有無を目視観察して評価した。この目視観察ではんだの剥離が観察された場合を不良として記した。 For heat-resistant peelability, rosin-based flux is applied to the test piece and immersed in a 230 ° C. eutectic solder (Pb-63 wt% Sn alloy) bath for 5 seconds to allow the solder to adhere, and this is at 150 ° C. for 1000 hours. After heating, 180 degree contact bending was performed, and then bent back, and the presence or absence of solder peeling at the bent back portion was visually observed and evaluated. The case where peeling of the solder was observed by this visual observation was marked as defective.
表１、表２，表３から明らかなように、本発明例のＮｏ．１〜Ｎｏ．９は、いずれも優れたプレス打抜き加工性を示し、又はんだ耐熱剥離性も良好に維持された。
これに対し、Ｃｒ量が少なくＣｒ／Ｓｉが小さい比較例のＮｏ．２１では、析出するＣｒＳｉ化合物の個数密度が小さくプレス打抜き加工性に劣っている。又Ｓｉ量が少なくＣｒ／Ｓｉが大きい比較例のＮｏ．２２は、ＣｒＳｉ化合物が小さく、且つ個数密度も小さいためにプレス打抜き加工性に劣っている。Ｃｒ量の多い比較例のＮｏ．２３はＣｒＳｉ化合物以外のＣｒ化合物が粗大化しエッチング性に劣っている。Ｓｉ量が多い比較例のＮｏ．２４はＣｒ／Ｓｉが小さく、ＣｒＳｉ化合物が大きいためエッチング性に劣り、Ｓｎ量の多い比較例のＮｏ．２５は導電率が低く、Ｚｎ量の少ない比較例のＮｏ．２６ははんだ耐熱剥離性が劣った。
As is clear from Table 1, Table 2, and Table 3, No. of the present invention example. 1-No. No. 9 showed excellent press punching workability, or the heat resistant peelability was maintained well.
On the other hand, No. of the comparative example with small Cr amount and small Cr / Si. In No. 21, the number density of the precipitated CrSi compound is small and the press punching processability is poor. No. of the comparative example with a small amount of Si and a large Cr / Si. No. 22 is inferior in press punching workability because the CrSi compound is small and the number density is also small. Comparative Example No. with a large amount of Cr. In No. 23, the Cr compound other than the CrSi compound is coarsened and has poor etching properties. The comparative example No. with a large amount of Si. No. 24 has a small Cr / Si and a large CrSi compound, so that the etching property is inferior, and the comparative example No. 24 with a large amount of Sn. No. 25 is a comparative example having a low conductivity and a small amount of Zn. No. 26 was inferior in solder heat resistance.
表1の本発明合金ａ、ｂ、ｄを用い、熱間圧延前の加熱処理条件および仕上げ冷間圧延前の熱処理条件を請求項３記載の本発明範囲内の条件で種々変化させて、本発明例のＮｏ．１０〜Ｎｏ．１６の銅合金板供試材を作製した。なお、それ以外の条件は実施例1と同様に行っている。
比較例として表１の本発明合金ａ、ｂを用い、熱間圧延前の加熱処理条件および仕上げ冷間圧延前の熱処理条件を本発明範囲外とした比較例のＮｏ．２７〜Ｎｏ.３１の銅合金板供試材を作製した。なお、それ以外の条件は実施例1と同様に行っている。
Using the alloys a, b and d of the present invention shown in Table 1, the heat treatment conditions before hot rolling and the heat treatment conditions before finish cold rolling were variously changed under the conditions within the scope of the present invention according to claim 3, Invention Example No. 10-No. Sixteen copper alloy plate specimens were prepared. The other conditions were the same as in Example 1.
As comparative examples, the alloys a and b of the present invention in Table 1 were used, and the heat treatment conditions before hot rolling and the heat treatment conditions before finish cold rolling were outside the scope of the present invention. 27 to No. 31 copper alloy plate specimens were prepared. The other conditions were the same as in Example 1.
作製した各々の銅合金板から試験片を切り出し、実施例1と同じ方法により種々特性を評価した。製造条件及び化合物相の状態を表４に示し、その他の評価結果を表５に示す。 Test pieces were cut out from each of the produced copper alloy plates, and various characteristics were evaluated by the same method as in Example 1. The production conditions and the state of the compound phase are shown in Table 4, and other evaluation results are shown in Table 5.
表４、５より明らかなように、本発明例のＮｏ．１０〜Ｎｏ．１６は、いずれも優れたプレス打抜き加工性を示し、又はんだ耐熱剥離性も良好に維持されているのが判る。
これに対し、比較例のＮｏ．２７では、熱間圧延前の加熱温度が低いためにＣｒＳｉ化合物が粗大化しエッチング性が劣った。一方、比較例のＮｏ．２８とＮｏ．２９は、熱間圧延前の加熱温度が高いために、ＣｒＳｉ化合物が小さく且つその個数密度が低いためにプレス打抜き加工性に劣っている。又、仕上げ圧延前の熱処理温度が低い比較例のＮｏ．３０及びＮｏ．３１では導電率が低下した。
As is clear from Tables 4 and 5, No. 10-No. It can be seen that No. 16 shows excellent press punching workability, or that the heat-resistant peelability is well maintained.
In contrast, No. of the comparative example. In No. 27, since the heating temperature before hot rolling was low, the CrSi compound was coarsened and the etching property was inferior. On the other hand, no. 28 and No. No. 29 is inferior in press punching workability because the CrSi compound is small and its number density is low because the heating temperature before hot rolling is high. In addition, the comparative example No. having a low heat treatment temperature before finish rolling. 30 and no. In 31, the conductivity decreased.
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