JP4809934B2 - Dilute copper alloy wire, plated wire and stranded wire - Google Patents

Dilute copper alloy wire, plated wire and stranded wire Download PDF

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JP4809934B2
JP4809934B2 JP2011103376A JP2011103376A JP4809934B2 JP 4809934 B2 JP4809934 B2 JP 4809934B2 JP 2011103376 A JP2011103376 A JP 2011103376A JP 2011103376 A JP2011103376 A JP 2011103376A JP 4809934 B2 JP4809934 B2 JP 4809934B2
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JP2011190540A (en
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正義 青山
亨 鷲見
修二 酒井
隆裕 佐藤
英則 安部
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Hitachi Cable Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a dilute copper alloy wire rod having high productivity and excellent conductivity, softening temperature and surface quality. <P>SOLUTION: The dilute copper alloy wire is obtained by carrying out cold wire-drawing of the wire rod manufactured by a continuous casting and rolling process using copper alloy material comprising 2-12 mass ppm of sulfur, 2-30 mass ppm of oxygen, 4-55 mass ppm of titanium, and a balance consisting of copper as a base material, wherein the conductivity of the wire rod when cold-drawn by 90% working ratio is 98% IACS (International Annealed Copper Standard) and semi-softening temperature is 130-148&deg;C. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

本発明は、生産性が高く、導電率、軟化温度、表面品質に優れた希薄銅合金線、めっき線及び撚線に関するものである。   The present invention relates to a dilute copper alloy wire, a plated wire, and a stranded wire having high productivity and excellent electrical conductivity, softening temperature, and surface quality.

最近の電子機器や自動車などの工業製品では、銅線も過酷に使われることが多い。これらのニーズに対処するために、連続鋳造圧延法などで製造でき、かつ導電性と伸び特性を純銅レベルに保持しつつ、強度を純銅よりも高めた希薄銅合金材料の開発が行われている。   In recent industrial products such as electronic devices and automobiles, copper wires are often used severely. In order to address these needs, a dilute copper alloy material that can be manufactured by a continuous casting and rolling method, etc., and has higher conductivity than pure copper while maintaining conductivity and elongation properties at pure copper level has been developed. .

希薄銅合金材料は、汎用の軟質銅線として、また、やわらかさが必要とされる軟質銅材として、導電率98%以上、更に102%以上の軟質導体が求められてきており、その用途としては、民生用太陽電池向け配線材、モーター用エナメル線用導体、200℃から700℃で使う高温用軟質銅材料、焼きなましが不要な溶融半田めっき材、熱伝導に優れた銅材料、高純度銅代替材料としての使用が挙げられ、これら幅広いニーズに応えるものである。   As a dilute copper alloy material, as a general-purpose soft copper wire and a soft copper material that requires softness, a soft conductor having an electrical conductivity of 98% or more and further 102% or more has been demanded. Are: wiring materials for consumer solar cells, conductors for enameled wires for motors, soft copper materials for high temperatures used at 200 ° C to 700 ° C, molten solder plating materials that do not require annealing, copper materials with excellent thermal conductivity, high-purity copper It can be used as an alternative material and meets these broad needs.

希薄銅合金材料としての素材は、銅中の酸素を10mass ppm以下に制御する技術をベースに用いており、このベースの銅原子に、Tiなどの金属を微量添加して、原子状に固溶させることで、生産性が高く、導電率、軟化温度、表面品質に優れた希薄銅合金材料が得られることが期待されている。   The material used as a dilute copper alloy material is based on a technology that controls oxygen in copper to 10 mass ppm or less, and a small amount of metal such as Ti is added to the copper atom of this base to form a solid solution in an atomic form. By doing so, it is expected that a dilute copper alloy material having high productivity and excellent conductivity, softening temperature and surface quality can be obtained.

従来、軟質化については、非特許文献1に示されるように、電解銅(99.996mass%以上)に、Tiを4〜28mol ppm添加した試料は、添加しないものに比べて、軟化が早く起こる結果が得られている。この原因はTiの硫化物形成による固溶Sの減少のためと、同文献では結論している。   Conventionally, as for softening, as shown in Non-Patent Document 1, softening occurs more quickly in a sample in which 4 to 28 mol ppm of Ti is added to electrolytic copper (99.996 mass% or more) than in a case where Ti is not added. The result is obtained. The literature concludes that this is due to a decrease in the solute S due to Ti sulfide formation.

特許文献1〜3では、連続鋳造装置において、無酸素銅に微量のTiを添加した希薄合金を用いて連続鋳造することが提案され、既に特許されている。   In Patent Documents 1 to 3, it is proposed and continuously patented in a continuous casting apparatus to use a dilute alloy obtained by adding a trace amount of Ti to oxygen-free copper.

ここで、連続鋳造圧延法で酸素を低くする方法についても、特許文献4、5に示されるように公知である。   Here, methods for lowering oxygen by a continuous casting and rolling method are also known as shown in Patent Documents 4 and 5.

特許文献6では、連続鋳造圧延法にて、銅溶湯から直接銅材を製造する際に、酸素量0.005質量%以下の銅溶湯に、Ti、Zr、Vなどの金属を微量(0.0007〜0.005質量%)添加することで軟化温度を低下させることが提案されている。しかし、特許文献6では、導電率に関する検討はなされておらず導電率と軟化温度を両立する製造条件範囲は不明である。   In patent document 6, when manufacturing a copper material directly from a molten copper by a continuous casting and rolling method, metals such as Ti, Zr, and V are contained in a minute amount (0.0007 to 0.005 mass) in a molten copper having an oxygen content of 0.005 mass% or less. %) It has been proposed to lower the softening temperature by addition. However, in Patent Document 6, the study on the electrical conductivity has not been made, and the manufacturing condition range in which the electrical conductivity and the softening temperature are compatible is unknown.

一方特許文献7では、軟化温度が低く、かつ導電率の高い無酸素銅材の製造方法が提案されており、上方引き上げ連続鋳造装置にて、酸素量が0.0001質量%以下の無酸素銅に、Ti、Zr、Vなどの金属を微量(0.0007〜0.005質量%)添加した銅溶湯から銅材を製造する方法が提案されている。   On the other hand, Patent Document 7 proposes a method for producing an oxygen-free copper material having a low softening temperature and a high electrical conductivity, and in an upward pulling continuous casting apparatus, oxygen-free copper having an oxygen content of 0.0001 mass% or less, There has been proposed a method for producing a copper material from a molten copper to which a minute amount (0.0007 to 0.005 mass%) of a metal such as Ti, Zr, or V is added.

しかし、上述したように希薄銅合金材料のベース素材のように、酸素が微量含まれるもの、すなわち酸素濃度がppmオーダーで含まれるものに関しては、いずれの特許文献でも検討されていない。   However, as described above, none of patent documents discusses a material containing a small amount of oxygen, such as a base material of a diluted copper alloy material, that is, a material containing an oxygen concentration in the order of ppm.

特許第3050554号公報Japanese Patent No. 3050554 特許第2737954号号公報Japanese Patent No. 2737954 特許第2737965号公報Japanese Patent No. 2737965 特許第3552043号公報Japanese Patent No. 3555433 特許第3651386号公報Japanese Patent No. 3651386 特開2006−274384号公報JP 2006-274384 A 特開2008−255417号公報JP 2008-255417 A

鈴木寿、菅野幹宏:鉄と鋼(1984)15号1977-1983SUZUKI, Hisashi Minohiro: Iron and Steel (1984) No.15, 1977-1983

よって、生産性が高く、導電率、軟化温度、表面品質に優れた実用的希薄銅合金線とその組成の検討が望まれていた。   Therefore, it has been desired to study a practical dilute copper alloy wire having high productivity, excellent conductivity, softening temperature, and surface quality and its composition.

また、製造方法について検討すると、上述したように連続鋳造による無酸素銅にTiを添加して軟銅化する方法は公知であるが、これはケークやビレットとして鋳造材を製造した後、熱間押出や熱間圧延を行いワイヤロッドを作製している。そのため、製造コストが高く工業的に使うには経済性に問題があった。   Further, when considering the production method, as described above, a method of adding Ti to oxygen-free copper by continuous casting and making it soft is known, but this is a hot extrusion after producing a cast material as a cake or billet. And wire rolling by hot rolling. For this reason, the manufacturing cost is high, and there is a problem in economical efficiency for industrial use.

また、上方引き上げ連続鋳造装置にて、無酸素銅にTiを添加する方法は公知であるが、これも生産速度が遅く経済性に問題があった。   Moreover, although the method of adding Ti to oxygen-free copper with an upward pulling continuous casting apparatus is known, this also has a problem in terms of economy because the production rate is slow.

そこで、SCR連続鋳造圧延システム(Southwire Continuous Rod System)にて検討しようとした。   Therefore, an attempt was made with the SCR continuous casting and rolling system (Southwire Continuous Rod System).

SCR連続鋳造圧延法は、SCR連続鋳造圧延装置の溶解炉内で、ベース素材を溶解して溶湯とし、その溶湯に所望の金属を添加して溶解し、この溶湯を用いて荒引き線(ワイヤロッド:例えばφ8mm)を作製し、その荒引き線を、冷間伸線により例えばφ2.6mmに加工するものである。またφ2.6mm以下のサイズ或いは板材、異形材にも同様に加工することができる。また、丸型線材を角状に或いは異形条に圧延しても有効である。また、ワイヤロッドをコンフォーム押出成形し、異形材を製作することもできる。   In the SCR continuous casting and rolling method, a base material is melted into a molten metal in a melting furnace of an SCR continuous casting and rolling apparatus, and a desired metal is added to the molten metal to be melted. A rod: φ8 mm, for example, is produced, and the rough drawing wire is processed to φ2.6 mm, for example, by cold drawing. Moreover, it can process similarly to the size below φ2.6mm, a board | plate material, and a deformed material. It is also effective to roll a round wire rod into a square shape or an irregular shape. It is also possible to produce a deformed material by extruding a wire rod.

本発明者等が検討した結果、SCR連続鋳造圧延を用いる場合、ベース素材としてのタフピッチ銅では表面傷が発生しやすく、添加条件により軟化温度の変動、チタン酸化物の形成状況が不安定であることがわかった。   As a result of investigations by the present inventors, when using SCR continuous casting and rolling, surface scratches are likely to occur in tough pitch copper as a base material, and the softening temperature variation and the formation state of titanium oxide are unstable depending on the addition conditions. I understood it.

また酸素量が0.0001質量%以下の無酸素銅を用いて検討すると、軟化温度と導電率、表面品質を満足する条件は極めて狭い範囲であった。また軟化温度の低下に限界があり、より低い、高純度銅並みの軟化温度の低下が望まれた。   When oxygen-free copper having an oxygen content of 0.0001% by mass or less was examined, the conditions satisfying the softening temperature, conductivity, and surface quality were in a very narrow range. Further, there is a limit to the decrease in softening temperature, and a lower softening temperature comparable to that of high-purity copper is desired.

そこで、本発明の目的は、上記課題を解決し、生産性が高く、導電率、軟化温度、表面品質に優れた希薄銅合金線を提供することにある。   Accordingly, an object of the present invention is to provide a diluted copper alloy wire that solves the above-described problems, has high productivity, and is excellent in conductivity, softening temperature, and surface quality.

上記目的を達成するために請求項1の発明は、2〜12mass ppmの硫黄と、2〜30mass ppmの酸素と、4〜55mass ppmのTiを含み、残部が銅である希薄銅合金線であって、その導電率が98%IACS以上であり、その半軟化温度が130〜148℃であることを特徴とする希薄銅合金線である。
The invention of claim 1 in order to achieve the above object, and 2~12Mass ppm sulfur, and oxygen 2~30Mass ppm, seen including a Ti of 4~55Mass ppm, in dilute copper alloy wire balance being copper The diluted copper alloy wire is characterized in that its electrical conductivity is 98% IACS or higher and its semi-softening temperature is 130 to 148 ° C.

請求項2の発明は、前記Tiの濃度が37mass ppm以下で、前記導電率が100%IACS以上である請求項1に記載の希薄銅合金線である。   The invention of claim 2 is the diluted copper alloy wire according to claim 1, wherein the concentration of Ti is 37 mass ppm or less and the conductivity is 100% IACS or more.

請求項3の発明は、前記Tiの濃度が25mass ppm以下であり、前記導電率が102%IACS以上である請求項1に記載の希薄銅合金線である。   The invention of claim 3 is the diluted copper alloy wire according to claim 1, wherein the concentration of Ti is 25 mass ppm or less, and the conductivity is 102% IACS or more.

請求項4の発明は、請求項1〜3のいずれかに記載の希薄銅合金線の表面にめっき層を形成したことを特徴とするめっき線である。   The invention of claim 4 is a plated wire characterized in that a plating layer is formed on the surface of the diluted copper alloy wire according to any one of claims 1 to 3.

請求項5の発明は、請求項1〜4いずれかに記載の希薄銅合金線又はめっき線を複数本撚り合わせたことを特徴とする撚線である。   The invention of claim 5 is a stranded wire comprising a plurality of the diluted copper alloy wires or the plated wires according to any one of claims 1 to 4 twisted together.

本発明によれば、生産性が高く、導電率、軟化温度、表面品質に優れた実用的な希薄銅合金線を提供できるという優れた効果を発揮するものである。   According to the present invention, it is possible to provide a practical dilute copper alloy wire having high productivity and excellent conductivity, softening temperature, and surface quality.

TiS粒子のSEM像を示す図である。It is a figure which shows the SEM image of a TiS particle | grain. 図1の分析結果を示す図である。It is a figure which shows the analysis result of FIG. TiO2粒子のSEM像を示す図である。Is a view showing an SEM image of the TiO 2 particles. 図3の分析結果を示す図である。It is a figure which shows the analysis result of FIG. 本発明において、Ti−O−S粒子のSEM像を示す図である。In this invention, it is a figure which shows the SEM image of Ti-O-S particle | grains. 図5の分析結果を示す図である。It is a figure which shows the analysis result of FIG.

以下、本発明の好適な一実施の形態を詳述する。   Hereinafter, a preferred embodiment of the present invention will be described in detail.

先ず、本発明は、SCR連続鋳造圧延設備を用い、表面傷が少なく、製造範囲が広く、安定生産が可能で、加工度90%(例えばφ8mm→φ2.6mm)で冷間加工して得られた線材の半軟化温度が148℃以下で、導電率が98%IACS〔万国標準軟銅(International Anneld Copper Standard)抵抗率1.7241×10-8Ωmを100%とした導電率〕以上、好ましくは102%IACS以上を満足する軟質型銅材としての希薄銅合金線を得ることにある。 First, the present invention is obtained by cold working at a workability of 90% (for example, φ8 mm → φ2.6 mm), using a SCR continuous casting and rolling facility, having few surface scratches, a wide manufacturing range, and capable of stable production. The wire has a semi-softening temperature of 148 ° C. or lower and an electrical conductivity of 98% IACS (conductivity with an International Anneld Copper Standard resistivity of 1.7241 × 10 −8 Ωm as 100%), preferably It is to obtain a diluted copper alloy wire as a soft copper material satisfying 102% IACS or more.

この際、高純度Cu(6N、純度99.9999%)に関しては、冷間加工度90%での軟化温度は130℃である。したがって130℃以上で148℃以下の半軟化温度で軟質材の導電率が98%IACS以上、好ましくは100%IACS以上、更に好ましくは導電率が102%IACS以上である軟質銅を安定して製造できる希薄銅合金材料としての素材とその製造条件を求めることが本発明の課題である。 At this time, for high purity Cu (6N, purity 99.9999%), the semi- softening temperature at a cold work degree of 90% is 130 ° C. Therefore, it is possible to stably produce soft copper having a soft material conductivity of 98% IACS or more, preferably 100% IACS or more, more preferably 102% IACS or more at a semi-softening temperature of 130 ° C. or more and 148 ° C. or less. It is an object of the present invention to obtain a raw material as a dilute copper alloy material and its manufacturing conditions.

ここで、酸素濃度1〜2mass ppmのCu(4N)を用い、実験室にて小型連続鋳造機(小型連鋳機)を用いて、チタンを数mass ppm添加した溶湯から製造したφ8mmのワイヤロッドをφ2.6mm(加工度90%)に加工して軟化温度を測ると160〜168℃であり、これ以上低い軟化温度にはならない。また、導電率は、101.7%IACS程度である。よって、酸素濃度を低くして、Tiを添加しても、軟化温度を下げることができず、また高純度Cu(6N)の導電率102.8%IACSよりも悪くなることがわかった。   Here, a φ8 mm wire rod manufactured from a molten metal added with several mass ppm of titanium using a small continuous casting machine (small continuous casting machine) using Cu (4N) having an oxygen concentration of 1 to 2 mass ppm. When the softening temperature is measured by processing this to φ 2.6 mm (working degree 90%), it is 160 to 168 ° C., and the softening temperature is not further lowered. The conductivity is about 101.7% IACS. Therefore, it was found that even when Ti was added at a low oxygen concentration, the softening temperature could not be lowered, and the conductivity was worse than 102.8% IACS of high purity Cu (6N).

この原因は、溶湯の製造中に不可避的不純物として、硫黄を数mass ppm以上含み、この硫黄とチタンとでTiS等の硫化物が十分形成されないために、軟化温度が下がらないものと推測される。   The cause of this is presumed that the softening temperature does not decrease because sulfur is contained in several mass ppm or more as an inevitable impurity during the production of molten metal, and sulfides such as TiS are not sufficiently formed between this sulfur and titanium. .

そこで、本発明では、軟化温度を下げることと、導電率を向上させるために、2つの方策を検討し、2つの効果を合わせることで目標を達成した。   Therefore, in the present invention, in order to lower the softening temperature and improve the electrical conductivity, the two measures have been studied and the two effects have been combined to achieve the goal.

(a)素材の酸素濃度を2mass ppm以上に増やしてチタンを添加する。これにより、先ず溶銅中ではTiSとチタン酸化物(TiO2)やTi−O−S粒子が形成されると考えられる(図1、図3のSEM像と、図2、図4の分析結果参照)。なお、図2、図4、図6において、PtおよびPdは観察のための蒸着元素である。 (A) Increase the oxygen concentration of the material to 2 mass ppm or more and add titanium. Thereby, it is considered that TiS and titanium oxide (TiO 2 ) and Ti—O—S particles are first formed in the molten copper (the SEM images of FIGS. 1 and 3 and the analysis results of FIGS. 2 and 4). reference). In FIGS. 2, 4, and 6, Pt and Pd are vapor deposition elements for observation.

(b)次に熱間圧延温度を、通常の銅の製造条件(950〜600℃)よりも低く設定(880〜550℃)することで、銅中に転位を導入し、Sが析出し易いようにする。これによって転位上へのSの析出又はチタンの酸化物(TiO2)を核としてSを析出させ、その一例として溶銅と同様Ti−O−S粒子等を形成させる(図5のSEM像と、図6の分析結果参照)。 (B) Next, by setting the hot rolling temperature lower (880 to 550 ° C.) than the normal copper production conditions (950 to 600 ° C.), dislocations are introduced into the copper and S is likely to precipitate. Like that. As a result, precipitation of S on the dislocations or precipitation of S using titanium oxide (TiO 2 ) as a nucleus forms Ti—O—S particles and the like as an example of molten copper (SEM image of FIG. 5 and FIG. 6 shows the analysis result).

(a)と(b)により、銅中での硫黄の晶出と熱間圧延中の硫黄の析出を行い、冷間伸線加工後に軟化温度と導電率を満足する銅ワイヤロッドができる。   According to (a) and (b), crystallization of sulfur in copper and precipitation of sulfur during hot rolling are performed, and a copper wire rod that satisfies the softening temperature and electrical conductivity after cold wire drawing can be obtained.

次に、本発明では、SCR連続鋳造圧延設備での製造条件の制限として(1)〜(4)を制限した。   Next, in this invention, (1)-(4) was restrict | limited as a restriction | limiting of the manufacturing conditions in SCR continuous casting rolling equipment.

(1)組成の制限
導電率が98%IACS以上の軟質銅材を得る場合、不可避的不純物を含む純銅(ベース素材)が、3〜12mass ppmの硫黄と、2〜30mass ppmの酸素と、Tiを4〜55mass ppm含む希薄銅合金材料でワイヤロッド(荒引き線)を製造するものである。
(1) Restriction of composition When obtaining a soft copper material having an electrical conductivity of 98% IACS or higher, pure copper (base material) containing inevitable impurities is 3-12 mass ppm of sulfur, 2-30 mass ppm of oxygen, and Ti. A wire rod (rough drawing wire) is manufactured with a diluted copper alloy material containing 4 to 55 mass ppm.

ここで、導電率が100%IACS以上の軟質銅材を得る場合には、不可避的不純物を含む純銅に2〜12mass ppmの硫黄と、2〜30mass ppmの酸素とTiを4〜37mass ppm含む希薄銅合金材料でワイヤロッドとするのがよい。   Here, when obtaining a soft copper material having an electrical conductivity of 100% IACS or more, a diluted copper containing 2 to 12 mass ppm of sulfur, 2 to 30 mass ppm of oxygen, and 4 to 37 mass ppm of pure copper containing inevitable impurities. The wire rod is preferably made of a copper alloy material.

さらに、導電率が102%IACS以上の軟質銅材を得る場合、不可避的不純物を含む純銅に3〜12mass ppmの硫黄と、2〜30mass ppmの酸素と、Tiを4〜25mass ppm含む希薄銅合金材料でワイヤロッドとするのがよい。   Furthermore, when obtaining a soft copper material having an electrical conductivity of 102% IACS or more, a diluted copper alloy containing 3-12 mass ppm of sulfur, 2-30 mass ppm of oxygen, and 4-25 mass ppm of Ti in pure copper containing inevitable impurities. It is good to use a wire rod with a material.

通常、純銅の工業的製造において、電気銅を製造する際に、硫黄が銅中に取り込まれてしまうため、硫黄を3mass ppm以下とするのは難しい。汎用電解銅の硫黄濃度の上限は12mass ppmである。   Usually, in the industrial production of pure copper, sulfur is taken into copper when producing electrolytic copper, so it is difficult to make sulfur 3 mass ppm or less. The upper limit of the sulfur concentration of general-purpose electrolytic copper is 12 mass ppm.

制御する酸素は、上述したように、少ないと軟化温度が下がり難いので2mass ppm以上とする。また酸素が多すぎると、熱間圧延工程で、表面傷が出やすくなるので30mass ppm以下とする。   As described above, if the amount of oxygen to be controlled is small, the softening temperature is difficult to decrease. Further, if there is too much oxygen, surface scratches are likely to occur in the hot rolling process, so it is set to 30 mass ppm or less.

(2)分散している物質の制限
分散粒子のサイズは小さく沢山分布することが望ましい。その理由は、硫黄の析出サイトとして働くためサイズが小さく数が多いことが要求される。
(2) Restriction of dispersed substances It is desirable that the size of dispersed particles is small and distributed in large numbers. The reason is that the size is small and the number is large because it functions as a sulfur deposition site.

硫黄及びチタンは、TiO、TiO2、TiS、Ti−O−Sの形で化合物または、凝集物を形成し、残りのTiとSが固溶体の形で存在している。TiOのサイズが200nm以下、TiO2は1000nm以下、TiSは200nm以下、Ti−O−Sは300nm以下で結晶粒内に分布している希薄銅合金材料とする。 Sulfur and titanium form compounds or aggregates in the form of TiO, TiO 2 , TiS, and Ti—O—S, and the remaining Ti and S are present in the form of a solid solution. A dilute copper alloy material in which the size of TiO is 200 nm or less, TiO 2 is 1000 nm or less, TiS is 200 nm or less, and Ti—O—S is 300 nm or less is distributed in the crystal grains.

但し、鋳造時の溶銅の保持時間や冷却状況により、形成される粒子サイズが変わるので鋳造条件の設定も必要である。   However, since the size of the formed particles changes depending on the holding time of the molten copper during casting and the cooling condition, it is necessary to set casting conditions.

(3)鋳造条件の制限
SCR連続鋳造圧延によりワイヤロッドを造る。一例として、加工度99.3%でφ8mmのワイヤロッドを造る方法を用いる。
(3) Restriction of casting conditions Wire rods are made by SCR continuous casting and rolling. As an example, a method of manufacturing a wire rod of φ8 mm with a processing degree of 99.3% is used.

(a)溶解炉内での鋳造温度は、1100℃以上1320℃以下とする。溶銅の温度が高いとブローホールが多くなり、傷が発生するとともに粒子サイズが大きくなる傾向にあるので1320℃以下とする。1100℃以上としたのは、銅が固まりやすく製造が安定しないためであるが、鋳造温度は出来るだけ低い温度が望ましい。   (A) The casting temperature in the melting furnace is 1100 ° C. or higher and 1320 ° C. or lower. When the temperature of the molten copper is high, blowholes increase, scratches are generated, and the particle size tends to increase. The reason why the temperature is set to 1100 ° C. or higher is that copper is hardened and the production is not stable, but the casting temperature is preferably as low as possible.

(b)熱間圧延温度は、最初の圧延ロールでの温度が880℃以下、最終圧延ロールでの温度が550℃以上とする。   (B) As for the hot rolling temperature, the temperature at the first rolling roll is 880 ° C. or lower, and the temperature at the final rolling roll is 550 ° C. or higher.

通常の純銅製造条件と異なり、溶銅中での硫黄の晶出と熱間圧延中の硫黄の析出が本発明の課題であるので、その駆動力である固溶限をより小さくするためには、鋳造温度と熱間圧延温度を(a)、(b)とするのがよい。   Unlike normal pure copper production conditions, crystallization of sulfur in molten copper and precipitation of sulfur during hot rolling are the subject of the present invention, so in order to reduce the solid solubility limit that is the driving force. The casting temperature and the hot rolling temperature are preferably (a) and (b).

通常の熱間圧延温度は、最初の圧延ロールでの温度が950℃以下、最終圧延ロールでの温度が600℃以上であるが、固溶限をより小さくするためには、最初の圧延ロールでの温度が880℃以下、最終圧延ロールでの温度が550℃以上に設定する。   The normal hot rolling temperature is such that the temperature at the first rolling roll is 950 ° C. or lower and the temperature at the final rolling roll is 600 ° C. or higher. In order to reduce the solid solution limit, Is set to 880 ° C. or lower and the temperature at the final rolling roll is set to 550 ° C. or higher.

550℃以上にする理由は、この温度以下ではワイヤロッドの傷が多いので製品にならないためである。熱間圧延温度は、最初の圧延ロールでの温度が880℃以下、最終圧延ロールでの温度が550℃以上で、できるだけ低い方が望ましい。こうすることで、ワイヤロッドを冷間加工して得られた銅材(例えばφ8〜φ2.6に加工後)の軟化温度が限りなく高純度Cu(6N、軟化温度130℃)に近くなる。   The reason why the temperature is set to 550 ° C. or higher is that the wire rod has many scratches below this temperature, so that the product is not manufactured. The hot rolling temperature is preferably as low as possible, with the temperature at the first rolling roll being 880 ° C. or lower and the temperature at the final rolling roll being 550 ° C. or higher. By doing so, the softening temperature of the copper material obtained by cold-working the wire rod (for example, after processing to φ8 to φ2.6) becomes as close as possible to high-purity Cu (6N, softening temperature 130 ° C.).

(c)直径φ8mmサイズのワイヤロッドの導電率が98%IACS以上、好ましくは100%IACS以上、更に好ましくは102%IACS以上であり、冷間伸線後のφ2.6mmの線材の半軟化温度が130℃〜148℃である希薄銅合金線を得ることができる。   (C) The conductivity of a wire rod having a diameter of φ8 mm is 98% IACS or more, preferably 100% IACS or more, more preferably 102% IACS or more, and the semi-softening temperature of φ2.6 mm wire after cold drawing A dilute copper alloy wire having a temperature of 130 ° C to 148 ° C can be obtained.

工業的に使うためには、電解銅から製造した工業的に利用される純度の軟質銅線にて98%IACS以上必要であり、軟化温度はその工業的価値から見て148℃以下である。Tiを添加しない場合は、160〜165℃である。
高純度Cu(6N)の軟化温度は127〜130℃であったので、得られたデータから限界値を130℃とする。このわずかな違いは、高純度Cu(6N)にない不可避的不純物にある。
In order to use it industrially, it is necessary to use 98% IACS or more in the industrially used soft copper wire produced from electrolytic copper, and the softening temperature is 148 ° C. or less in view of its industrial value. When Ti is not added, the temperature is 160 to 165 ° C.
Since the softening temperature of high-purity Cu (6N) was 127 to 130 ° C, the limit value is set to 130 ° C from the obtained data. This slight difference is in unavoidable impurities not found in high purity Cu (6N).

導電率は、無酸素銅のレベルで101.7%IACS程度であり、高純度Cu(6N)で102.8%IACSであるため、出来るだけ高純度Cu(6N)に近い導電率であることが望ましい。   The conductivity is about 101.7% IACS at the level of oxygen-free copper, and 102.8% IACS for high-purity Cu (6N), so that the conductivity is as close to high-purity Cu (6N) as possible. Is desirable.

(4)鋳造条件の制限
銅はシャフト炉で溶解の後、還元状態の樋になるように制御した、すなわち還元ガス(CO)雰囲気下で、希薄合金の構成元素の硫黄濃度、Ti濃度、酸素濃度を制御して鋳造し、圧延するワイヤロッドを安定して製造する方法がよい。銅酸化物の混入や粒子サイズが大きいので品質を低下させる。
(4) Restriction of casting conditions Copper was controlled to be in a reduced state after melting in the shaft furnace, that is, in the reducing gas (CO) atmosphere, the sulfur concentration, Ti concentration, oxygen of the constituent elements of the diluted alloy A method of stably producing a wire rod to be cast and rolled while controlling the concentration is preferable. Since the copper oxide is mixed and the particle size is large, the quality is lowered.

ここで、添加物としてTiを選択した理由は次の通りである。   Here, the reason for selecting Ti as an additive is as follows.

(a)Tiは溶融銅の中で硫黄と結合し化合物を造りやすいためである。   (A) Ti is easily bonded to sulfur in molten copper to form a compound.

(b)Zrなど他の添加金属に比べて加工でき扱いやすい。   (B) It can be processed and handled more easily than other additive metals such as Zr.

(c)Nbなどに比べて安価である。   (C) It is less expensive than Nb or the like.

(d)酸化物を核として析出しやすいからである。   (D) It is because it is easy to precipitate using an oxide as a nucleus.

以上により、本発明の希薄銅合金材料は、溶融半田めっき材(線、板、箔)、エナメル線、軟質純銅、高導電率銅、やわらかい銅線として使用でき、生産性が高く、導電率、軟化温度、表面品質に優れた実用的な希薄銅合金材料を得ることが可能となる。
また、本発明の希薄銅合金線の表面にめっき層を形成してもよい。めっき層としては、例えば、錫、ニッケル、銀を主成分とするものを適用可能であり、いわゆるPbフリーめっきを用いてもよい。
また、本発明の希薄銅合金線を複数本撚り合わせた希薄銅合金撚線として使用することも可能である。
また、本発明の希薄銅合金線又は希薄銅合金撚線の周りに、絶縁層を設けたケーブルとして使用することもできる。
また、本発明の希薄銅合金線を複数本撚り合わせて中心導体とし、中心導体の外周に絶縁体被覆を形成し、絶縁体被覆の外周に銅又は銅合金からなる外部導体を配置し、その外周にジャケット層を設けた同軸ケーブルとして使用することもできる。
また、この同軸ケーブルの複数本をシールド層内に配置し、前記シールド層の外周にシースを設けた複合ケーブルとして使用することもできる。
From the above, the diluted copper alloy material of the present invention can be used as a molten solder plating material (wire, plate, foil), enameled wire, soft pure copper, high conductivity copper, soft copper wire, high productivity, conductivity, A practical dilute copper alloy material having excellent softening temperature and surface quality can be obtained.
Further, a plating layer may be formed on the surface of the diluted copper alloy wire of the present invention. As the plating layer, for example, a layer mainly composed of tin, nickel, and silver is applicable, and so-called Pb-free plating may be used.
Moreover, it is also possible to use it as a diluted copper alloy stranded wire obtained by twisting a plurality of diluted copper alloy wires of the present invention.
Moreover, it can also be used as the cable which provided the insulating layer around the diluted copper alloy wire or diluted copper alloy twisted wire of this invention.
Further, a plurality of diluted copper alloy wires of the present invention are twisted to form a central conductor, an insulator coating is formed on the outer periphery of the central conductor, and an outer conductor made of copper or copper alloy is disposed on the outer periphery of the insulator coating, It can also be used as a coaxial cable having a jacket layer on the outer periphery.
Further, a plurality of coaxial cables can be arranged in the shield layer and used as a composite cable in which a sheath is provided on the outer periphery of the shield layer.

また、上述の実施の形態では、SCR連続鋳造圧延によりワイヤロッドを作製し、熱間圧延にて軟質材を作製する例で説明したが、本発明は、双ロール式連続鋳造圧延及びプロペルチ式連続鋳造圧延法により製造するようにしても良い。   Moreover, in the above-mentioned embodiment, although the wire rod was produced by SCR continuous casting rolling and the example which produced a soft material by hot rolling was demonstrated, this invention is a twin roll type continuous casting rolling and a Properti type continuous. You may make it manufacture by a casting rolling method.

表1は実験条件と結果に関するものである。   Table 1 relates to experimental conditions and results.

先ず、実験材として、表1に示した酸素濃度、硫黄濃度、Ti濃度で、φ8mmの銅線(ワイヤロッド:加工度99.3%)をそれぞれ作製し、その実験材を冷間伸線して、φ2.6mmのサイズにおける半軟化温度と導電率を測定し、またφ8mmの銅線における分散粒子サイズを評価した。   First, as an experimental material, φ8 mm copper wires (wire rod: degree of processing 99.3%) were prepared for each of the oxygen concentration, sulfur concentration, and Ti concentration shown in Table 1, and the experimental material was cold-drawn. Then, the semi-softening temperature and conductivity at a size of φ2.6 mm were measured, and the dispersed particle size in a φ8 mm copper wire was evaluated.

酸素濃度、酸素分析器(レコ(Leco;商標)酸素分析器)で測定した。硫黄、Tiの各濃度はICP発光分光分析器で分析した結果である。   The oxygen concentration was measured with an oxygen analyzer (Leco ™ oxygen analyzer). Each concentration of sulfur and Ti is the result of analysis with an ICP emission spectroscopic analyzer.

φ2.6mmのサイズにおける半軟化温度の測定は、400℃以下で各温度1時間の保持後、水中急冷し、引張試験を実施しその結果から求めた。室温での引張試験の結果と400℃で1時間のオイルバス熱処理を施した軟質銅線の引張試験の結果を用いて求めた。引張強さの差の半分の値を示す強度に対応する温度を半軟化温度と定義し求めた。   The measurement of the semi-softening temperature in the size of φ2.6 mm was obtained from the result of quenching in water after holding each temperature at 400 ° C. or less for 1 hour and conducting a tensile test. It calculated | required using the result of the tensile test at room temperature, and the result of the tensile test of the soft copper wire which performed the oil bath heat processing for 1 hour at 400 degreeC. The temperature corresponding to the strength showing half of the difference in tensile strength was defined as the semi-softening temperature.

分散粒子のサイズは小さく沢山分布することが望ましい。その理由は、硫黄の析出サイトとして働くためサイズが小さく数が多いことが要求される。すなわち直径500μm以下の分散粒子が90%以上である場合を合格(○)とした。   It is desirable that the dispersed particles have a small size and are distributed a lot. The reason is that the size is small and the number is large because it functions as a sulfur deposition site. That is, the case where the number of dispersed particles having a diameter of 500 μm or less was 90% or more was determined to be acceptable (◯).

表1において、比較材1は、実験室でAr雰囲気において直径φ8mmの銅線を試作した結果であり、Tiを、0〜18mass ppm添加したものである。   In Table 1, the comparative material 1 is a result of making a trial production of a copper wire having a diameter of 8 mm in an Ar atmosphere in a laboratory, and Ti is added with 0 to 18 mass ppm.

このTi添加で、Ti添加量ゼロの半軟化温度215℃に対して、13mass ppmは160℃まで低下して最小となり、15、18mass ppmの添加で高くなっており、要望の軟化温度148℃以下にはならなかった。しかし工業的に要望がある導電率は98%IACS以上であり満足していたが、総合評価は×であった。   With this Ti addition, 13 mass ppm decreases to 160 ° C. and becomes minimum with a semi-softening temperature of 215 ° C. with no Ti addition, and increases with addition of 15 and 18 mass ppm, and the desired softening temperature is 148 ° C. or less. Did not become. However, although the industrially required conductivity was 98% IACS or more, it was satisfactory, but the overall evaluation was x.

そこで、次にSCR連続鋳造圧延法にて、酸素濃度を7〜8mass ppmに調整してφ8mm銅線(ワイヤロッド)の試作を行った。   Then, the oxygen concentration was adjusted to 7 to 8 mass ppm by the SCR continuous casting and rolling method, and a φ8 mm copper wire (wire rod) was prototyped.

比較材2は、SCR連続鋳造圧延法で試作した中でTi濃度の少ないもの(0.2mass ppm)であり、導電率は102%IACS以上であるが、半軟化温度が164、157℃であり、要求の148℃以下を満足しないので、総合評価で、×となった。   The comparative material 2 is a material with a low Ti concentration (0.2 mass ppm) produced by trial using the SCR continuous casting and rolling method, and the electrical conductivity is 102% IACS or more, but the semi-softening temperature is 164, 157 ° C. Since the required temperature of 148 ° C. or lower was not satisfied, the overall evaluation was x.

実施材1については、酸素濃度と硫黄が、ほぼ一定(7〜8mass ppm、5mass ppm)、Ti濃度の異なる(4〜55mass ppm)試作材の結果である。   About execution material 1, oxygen concentration and sulfur are almost constant (7-8 mass ppm, 5 mass ppm), and it is a result of a trial material from which Ti concentration differs (4-55 mass ppm).

このTi濃度4〜55mass ppmの範囲では、軟化温度148℃以下であり、導電率も98%IACS以上、102%IACS以上であり、分散粒子サイズも500μm以下の粒子が90%以上であり良好である。そしてワイヤロッドの表面もきれいであり、いずれも製品性能として満足している(総合評価○)。   In this Ti concentration range of 4 to 55 mass ppm, the softening temperature is 148 ° C. or lower, the conductivity is 98% IACS or higher, 102% IACS or higher, and the dispersed particle size is 500% or less, which is 90% or higher. is there. And the surface of the wire rod is also clean, and all are satisfied as product performance (overall evaluation ○).

ここで、導電率100%IACS以上を満たすものは、Ti濃度が4〜37mass ppmのときであり、102%IACS以上を満たすものは、Ti濃度が4〜25mass ppmのときである。Ti濃度が13mass ppmのとき導電率が最大値である102.4%IACSを示し、この濃度の周辺では、導電率は、僅かに低い値であった。これは、Tiが13mass ppmのときに、銅中の硫黄分を化合物として捕捉することで、高純度Cu(6N)に近い導電率を示したためである。   Here, what satisfies the conductivity of 100% IACS or more is when the Ti concentration is 4 to 37 mass ppm, and that which satisfies 102% IACS or more is when the Ti concentration is 4 to 25 mass ppm. When the Ti concentration was 13 mass ppm, the maximum conductivity was 102.4% IACS, and the conductivity was slightly lower around this concentration. This is because when Ti was 13 mass ppm, the sulfur content in copper was captured as a compound, thereby showing conductivity close to that of high-purity Cu (6N).

よって、酸素濃度を高くし、Tiを添加することで、半軟化温度と導電率の双方を満足させることができる。   Therefore, both the semi-softening temperature and the conductivity can be satisfied by increasing the oxygen concentration and adding Ti.

比較材3は、Ti濃度を60mass ppmと高くした試作材である。この比較材3は、導電率は要望を満足しているが、半軟化温度は148℃以上であり、製品性能を満足していない。さらにワイヤロッドの表面傷も多い結果であり、製品にすることは難しかった。よって、Tiの添加量は60mass ppm未満がよい。   Comparative material 3 is a prototype material having a Ti concentration as high as 60 mass ppm. In this comparative material 3, the electrical conductivity satisfies the request, but the semi-softening temperature is 148 ° C. or higher, and the product performance is not satisfied. Furthermore, there were many surface damages on the wire rod, making it difficult to produce a product. Therefore, the addition amount of Ti is preferably less than 60 mass ppm.

次に実施材2については、硫黄濃度を5mass ppmとし、Ti濃度を13〜10mass ppmとし、酸素濃度を変えて、酸素濃度の影響を検討した試作材である。   Next, Example Material 2 is a prototype material in which the sulfur concentration is set to 5 mass ppm, the Ti concentration is set to 13 to 10 mass ppm, and the oxygen concentration is changed to examine the influence of the oxygen concentration.

酸素濃度に関しては、2以下から30mass ppmまで、大きく濃度が異なる試作材とした。但し、酸素が2mass ppm未満は、生産が難しく安定した製造できないため、総合評価は△とした。また酸素濃度を30mass ppmと高くしても半軟化温度と導電率の双方を満足することがわかった。   Regarding the oxygen concentration, a prototype material having greatly different concentrations from 2 or less to 30 mass ppm was used. However, when oxygen is less than 2 mass ppm, production is difficult and stable production cannot be performed, so the overall evaluation is Δ. It was also found that even when the oxygen concentration was increased to 30 mass ppm, both the semi-softening temperature and the conductivity were satisfied.

また比較材4に示すように、酸素が40mass ppmの場合には、ワイヤロッド表面の傷が多く、製品にならない状況であった。   Moreover, as shown in the comparative material 4, when oxygen was 40 mass ppm, there were many scratches on the surface of the wire rod, and the product was not a product.

よって、酸素濃度が2〜30mass ppmの範囲とすることで、半軟化温度、導電率102%IACS以上、分散粒子サイズいずれの特性も満足させることができ、またワイヤロッドの表面もきれいであり、いずれも製品性能を満足させることができる。   Therefore, by setting the oxygen concentration in the range of 2 to 30 mass ppm, the characteristics of the semi-softening temperature, the conductivity of 102% IACS or more, and the dispersed particle size can be satisfied, and the surface of the wire rod is clean, Both can satisfy product performance.

次に実施材3は、それぞれ酸素濃度とTi濃度とを比較的近い濃度とし、硫黄濃度を4〜20mass ppmと変えた試作材の例である。この実施材3においては、硫黄が2mass ppmより少ない試作材は、その原料面から実現できなかったが、Tiと硫黄の濃度を制御することで、半軟化温度と導電率の双方を満足させることができる。   Next, the embodiment material 3 is an example of a prototype material in which the oxygen concentration and the Ti concentration are relatively close to each other and the sulfur concentration is changed to 4 to 20 mass ppm. In this material 3, the prototype material with less sulfur than 2 mass ppm could not be realized from the raw material side, but by satisfying both the semi-softening temperature and the conductivity by controlling the concentrations of Ti and sulfur. Can do.

比較材5の硫黄濃度が18mass ppmで、Ti濃度が13mass ppmの場合には、半軟化温度が162℃で高く、必要特性を満足できなかった。また、特にワイヤロッドの表面品質が悪いので、製品化は難しかった。   When the sulfur concentration of the comparative material 5 was 18 mass ppm and the Ti concentration was 13 mass ppm, the semi-softening temperature was high at 162 ° C. and the required characteristics could not be satisfied. Moreover, since the surface quality of the wire rod was particularly poor, it was difficult to commercialize the product.

以上より、硫黄濃度が2〜12mass ppmの場合には、半軟化温度、導電率102%IACS以上、分散粒子サイズいずれの特性も満足しており、ワイヤロッドの表面もきれいですべての製品性能を満足することがわかった。   From the above, when the sulfur concentration is 2 to 12 mass ppm, the properties of semi-softening temperature, conductivity of 102% IACS or more, and dispersed particle size are satisfied, and the surface of the wire rod is clean and all product performance is achieved. I was satisfied.

また比較材6として高純度Cu(6N)を用いた検討結果を示したが、半軟化温度127〜130℃であり、導電率も102.8%IACSであり、分散粒子サイズも、500μm以下の粒子はまったく認められなかった。   Moreover, although the examination result using high purity Cu (6N) was shown as the comparative material 6, it is a semi-softening temperature 127-130 degreeC, and electrical conductivity is 102.8% IACS, and dispersion particle size is also 500 micrometers or less. No particles were observed.

表2は、製造条件としての、溶融銅の温度と圧延温度を示したものである。   Table 2 shows the molten copper temperature and rolling temperature as the production conditions.

比較材7は、溶銅温度が高めの1330〜1350℃で且つ圧延温度が950〜600℃でφ8mmのワイヤロッドを試作した結果を示したものである。   Comparative material 7 shows the result of trial manufacture of a wire rod of φ8 mm at a molten metal temperature of 1330 to 1350 ° C. and a rolling temperature of 950 to 600 ° C.

この比較材7は、半軟化温度と導電率は満足するものの、分散粒子のサイズに関しては、1000μm程度のものもあり500μm以上の粒子も10%を超えていた。よってこれは不適とした。   Although this comparative material 7 satisfies the semi-softening temperature and the electrical conductivity, the dispersed particles have a size of about 1000 μm, and the particle size of 500 μm or more exceeds 10%. Therefore, this was inappropriate.

実施材4は、溶銅温度が1200〜1320℃で且つ圧延温度が低めの880〜550℃でφ8mmのワイヤロッドを試作した結果を示したものである。この実施材4については、ワイヤ表面品質、分散粒子サイズも良好で、総合評価は○であった。   The execution material 4 shows the result of trial manufacture of a φ8 mm wire rod at a molten copper temperature of 1200 to 1320 ° C. and a lower rolling temperature of 880 to 550 ° C. About this implementation material 4, the wire surface quality and the dispersed particle size were also good, and the overall evaluation was good.

比較材8は、溶銅温度が1100℃で且つ圧延温度が低めの880〜550℃でφ8mmのワイヤロッドを試作した結果を示したものである。この比較材8は、溶銅温度が低いため、ワイヤロッドの表面傷が多く製品には適さなかった。これは、溶銅温度が低いため、圧延時に傷が発生しやすいためである。   Comparative material 8 shows the result of trial production of a wire rod of φ8 mm at a molten copper temperature of 1100 ° C. and a lower rolling temperature of 880 to 550 ° C. Since this comparative material 8 had a low molten copper temperature, the wire rod had many surface scratches and was not suitable for the product. This is because scratches are likely to occur during rolling because the molten copper temperature is low.

比較材9は、溶銅温度が1300℃で且つ圧延温度が高めの950〜600℃でφ8mmのワイヤロッドを試作した結果を示したものである。この比較材9は、熱間圧延温度が高いため、ワイヤロッドの表面品質が良いが、分散粒子サイズも大きなものがあり、総合評価は×となった。   Comparative material 9 shows the result of trial manufacture of a wire rod of φ8 mm at a molten metal temperature of 1300 ° C. and a higher rolling temperature of 950 to 600 ° C. Since this comparative material 9 had a high hot rolling temperature, the surface quality of the wire rod was good, but some of the dispersed particles were large, and the overall evaluation was x.

比較材10は、溶銅温度が1350℃で且つ圧延温度が低めの880〜550℃でφ8mmのワイヤロッドを試作した結果を示したものである。この比較材10は、溶銅温度が高いため、分散粒子サイズが大きなものがあり、総合評価は×となった。   Comparative material 10 shows the result of trial manufacture of a φ8 mm wire rod at a molten copper temperature of 1350 ° C. and a lower rolling temperature of 880 to 550 ° C. Since this comparative material 10 had a high molten copper temperature, some of the dispersed particles had a large size, and the overall evaluation was x.

Claims (5)

2〜12mass ppmの硫黄と、2〜30mass ppmの酸素と、4〜55mass ppmのTiを含み、残部が銅である希薄銅合金線であって、その導電率が98%IACS以上であり、その半軟化温度が130〜148℃であることを特徴とする希薄銅合金線。 And 2~12Mass ppm sulfur, and oxygen 2~30Mass ppm, seen including a Ti of 4~55Mass ppm, the balance being a dilute copper alloy wire is copper, and the conductivity thereof is 98% IACS or more, A diluted copper alloy wire having a semi-softening temperature of 130 to 148 ° C. 前記Tiの濃度が37mass ppm以下で、前記導電率が100%IACS以上である請求項1に記載の希薄銅合金線。   2. The diluted copper alloy wire according to claim 1, wherein the Ti concentration is 37 mass ppm or less and the conductivity is 100% IACS or more. 前記Tiの濃度が25mass ppm以下であり、前記導電率が102%IACS以上である請求項1に記載の希薄銅合金線。   The dilute copper alloy wire according to claim 1, wherein the Ti concentration is 25 mass ppm or less, and the conductivity is 102% IACS or more. 請求項1〜3のいずれかに記載の希薄銅合金線の表面にめっき層を形成したことを特徴とするめっき線。   A plated wire, wherein a plated layer is formed on the surface of the diluted copper alloy wire according to claim 1. 請求項1〜4いずれかに記載の希薄銅合金線又はめっき線を複数本撚り合わせたことを特徴とする撚線。   A stranded wire obtained by twisting a plurality of the diluted copper alloy wires or plated wires according to claim 1.
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