JP2010248593A - Copper alloy material for electrical and electronic component and method for manufacturing the same - Google Patents
Copper alloy material for electrical and electronic component and method for manufacturing the same Download PDFInfo
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Abstract
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本発明は、例えばコネクタやスイッチ部品のような各種電気・電子部品における接点や擦動部などの材料として用いられる電気・電子部品用銅合金材に関する。 The present invention relates to a copper alloy material for electric / electronic parts used as a material for contacts and friction parts in various electric / electronic parts such as connectors and switch parts.
リードフレーム、コネクタ等をはじめとした電気・電子部品用銅合金材には、高い機械的強度、高い熱伝導率、そしてそれが用いられる電気電子部品の製造工程における加熱に対しても容易には軟化することのないような高い耐熱性が要求される。また、このような特性（１次特性）以外にも、めっき性、はんだ濡れ性、エッチング性、プレス性、耐食性、加熱伸縮特性、曲げ加工性、耐応力緩和性等が求められる。
近年、電気・電子部品のさらなる小型化・高集積化が進むにつれて、上記の各種特性向上への要求は、ますます厳しいものとなってきている。
斯様な要求を満たす合金として、Ｃｕ−Ｎｉ−Ｓｉ系合金（コルソン合金）が開発され、各種添加元素を加えたものが使用されるようになってきた。
Copper alloy materials for electrical and electronic parts such as lead frames and connectors have high mechanical strength, high thermal conductivity, and are easy to heat during the manufacturing process of electrical and electronic parts in which they are used. High heat resistance that does not soften is required. In addition to such characteristics (primary characteristics), plating properties, solder wettability, etching properties, press properties, corrosion resistance, heat expansion / contraction properties, bending workability, stress relaxation resistance, and the like are required.
In recent years, as electric and electronic parts are further miniaturized and highly integrated, the above-mentioned demands for improving various characteristics have become increasingly severe.
Cu—Ni—Si based alloys (Corson alloys) have been developed as alloys that satisfy such requirements, and those added with various additive elements have been used.
Ｃｕ−Ｎｉ−Ｓｉ系合金の製造方法は、他の銅合金条とほぼ同様であり、連続鋳造により矩形断面のインゴットを鋳造した後、それを熱間圧延して、厚さ１０〜２０ｍｍの銅板を形成し、さらにそれに時効熱処理、冷間圧延、必要に応じて連続焼鈍、酸洗浄、研熔等を繰り返し施して、最終製品である銅合金条に仕上げるようにしている。
特にリードフレーム用の銅合金条の場合、圧延加工を行った後、歪み除去のための焼鈍を施して、材料の伸びの回復や歪みの除去・機械的特性の均一化等を行うことが一般的である。
The manufacturing method of the Cu-Ni-Si-based alloy is almost the same as other copper alloy strips. After casting an ingot having a rectangular cross section by continuous casting, it is hot-rolled to obtain a copper plate having a thickness of 10 to 20 mm. Further, it is subjected to aging heat treatment, cold rolling, continuous annealing, acid cleaning, polishing, etc., as necessary, to finish the copper alloy strip as the final product.
In particular, in the case of copper alloy strips for lead frames, after rolling, annealing for strain removal is generally performed to recover material elongation, remove strain, and make mechanical properties uniform. Is.
このようなＣｕ−Ｎｉ−Ｓｉ系合金の性能向上に関する技術が、従来から提案されている。それらのうち、強度および導電性を向上させることを企図し、その合金における銅（Ｃｕ）とニッケル（Ｎｉ）とシリコン（Ｓｉ）との成分比率を規定したものとして、例えば特許文献１にて開示された技術（発明）がある。
このような技術によって製造された銅合金条は、各種めっきが施され、また所定のパターン加工等が施されて、リードフレームやコネクタのような電気・電子部品に使用される。
Techniques for improving the performance of such Cu—Ni—Si alloys have been proposed. Among them, it is intended to improve the strength and conductivity, and the component ratio of copper (Cu), nickel (Ni) and silicon (Si) in the alloy is defined, for example, disclosed in Patent Document 1 Technology (invention).
The copper alloy strip manufactured by such a technique is subjected to various types of plating and is subjected to predetermined pattern processing and the like, and is used for electrical / electronic components such as lead frames and connectors.
リードフレームの製造工程においては、プレス加工法やエッチング法などによって銅合金状をリードフレームの形状に加工した後、所定のマスキングを行って部分銀（Ａｇ）めっきを施すが、その下地として、銅（Ｃｕ）ストライクめっきを施すことが一般的である。めっき膜の品質は、めっき前処理条件と共に銅合金材の化学組成や表面品質が顕著に影響を与えることとなる。
そこで、そのようなＣｕ−Ｎｉ−Ｓｉ系合金からなる銅合金条における、優れためっき性を確保するための技術として、例えば特許文献２、特許文献３、特許文献４、特許文献５、特許文献６にて提案された技術等がある。
特許文献２、特許文献３では、介在物の個数を規定することで、銅合金材の表面のめっき性を向上させる、という技術が提案されている。
また、特許文献４、特許文献５では、銅合金材の表面の加工変質層の厚さを規定することで、銅合金材の表面のめっき性を向上させる、という技術が提案されている。
また、特許文献６では、適量のアルミニウム（Ａｌ）を添加して、銅合金材の表面にアルミニウム（Ａｌ）の濃化層を形成することで、銅合金材の表面におけるめっき膜の密着性を向上させ、その結果、銅合金材の表面のめっき性を向上させる、という技術が提案されている。
In the lead frame manufacturing process, a copper alloy is processed into the shape of the lead frame by a press working method or an etching method, and then subjected to predetermined masking to perform partial silver (Ag) plating. It is common to apply (Cu) strike plating. The quality of the plating film is significantly affected by the chemical composition and surface quality of the copper alloy material together with the pretreatment conditions for plating.
Therefore, as a technique for ensuring excellent plating properties in a copper alloy strip made of such a Cu—Ni—Si based alloy, for example, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document There are technologies proposed in Section 6.
In patent document 2 and patent document 3, the technique of improving the plating property of the surface of a copper alloy material by prescribing the number of inclusions is proposed.
Patent Documents 4 and 5 propose a technique for improving the plating property of the surface of the copper alloy material by defining the thickness of the work-affected layer on the surface of the copper alloy material.
Further, in Patent Document 6, by adding an appropriate amount of aluminum (Al) and forming a concentrated layer of aluminum (Al) on the surface of the copper alloy material, the adhesion of the plating film on the surface of the copper alloy material is improved. As a result, a technique for improving the plating property of the surface of the copper alloy material has been proposed.
Ｃｕ−Ｎｉ−Ｓｉ系合金の一般的なニッケル（Ｎｉ）とシリコン（Ｓｉ）との含有量は、ニッケル（Ｎｉ）：１．０〜４．０質量％、シリコン（Ｓｉ）：０．２〜１．２質量％である。また必要に応じて、さらに、マグネシウム（Ｍｇ）、錫（Ｓｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）等の元素が副成分として添加される場合もある。
リードフレーム用の銅合金条の製造工程においては、一般に、歪み除去のための焼鈍が最終工程となるが、その歪み除去焼鈍の際に、銅合金条の表面が酸化する虞がある。そこで、そのような表面の酸化を防止するために、光輝焼鈍炉における還元雰囲気中で、歪み除去焼鈍を行うことが多い。
The general nickel (Ni) and silicon (Si) content of the Cu-Ni-Si alloy is nickel (Ni): 1.0 to 4.0 mass%, silicon (Si): 0.2 to 1.2% by mass. In addition, elements such as magnesium (Mg), tin (Sn), iron (Fe), and cobalt (Co) may be added as subcomponents as necessary.
In the manufacturing process of a copper alloy strip for a lead frame, annealing for strain removal is generally the final step, but the surface of the copper alloy strip may be oxidized during the strain removal annealing. Therefore, in order to prevent such surface oxidation, strain removal annealing is often performed in a reducing atmosphere in a bright annealing furnace.
しかしながら、従来の技術では、そのように表面の酸化を防止するために還元雰囲気中で最終工程の歪み除去焼鈍を行っているにも関わらず、最終的に得られた銅合金材（銅合金材）の表面は、荒れた不均一な状態で、光沢も低い（鈍い）ものとなりやすい傾向にあり、従って、その表面にめっき膜を形成すると、そのめっき膜が粒状やコブ状のような荒れた状態となってしまうことが多いという問題があった。
また、このようなめっき膜や材料表面の荒れの発生を回避するためには、焼鈍温度を低く設定することも考えられるが、そのようにすると、歪み除去焼鈍の本来の目的である材料の伸びの回復や歪みの除去の十分な効果を得ることが困難になってしまう。
本発明は、このような問題に鑑みて成されたもので、その目的は、圧延加工後の材料の伸びの回復および歪み除去が十分に成されていると共に良好なめっき性を備えた電気・電子部品用銅合金材、およびその製造方法を提供することにある。
However, in the conventional technique, the final obtained copper alloy material (copper alloy material) is used in spite of the fact that the final step of strain-relief annealing is performed in a reducing atmosphere to prevent surface oxidation. ) Surface tends to be rough, uneven, and low gloss (dull), so when a plating film is formed on the surface, the plating film becomes rough like a grain or bump There was a problem that it often became a state.
In order to avoid such roughening of the plating film and the material surface, it is conceivable to set the annealing temperature low. However, by doing so, the elongation of the material, which is the original purpose of strain relief annealing, is considered. It becomes difficult to obtain sufficient effects of recovery and distortion removal.
The present invention has been made in view of such problems. The purpose of the present invention is to sufficiently recover the elongation of the material after the rolling process and to remove the distortion, and to provide an electric plate with good plating properties. It is providing the copper alloy material for electronic components, and its manufacturing method.
本発明の発明者達は、上記目的を達成するために、まず、Ｃｕ−Ｎｉ−Ｓｉ系の銅合金材に還元雰囲気中で歪み除去焼鈍のような最終加熱を施した後の、めっき性の低劣化の発生要因について、種々の調査・検討を行った。その結果、Ｃｕ−Ｎｉ−Ｓｉ系の銅合金材に還元雰囲気中で加熱処理を施すと、銅（Ｃｕ）は酸化せずにシリコン（Ｓｉ）やその他の易酸化元素が表層領域へと拡散して来て、それが優先的に酸化するので、このようなシリコン（Ｓｉ）等の酸化膜を有する状態の銅合金条に銅ストライクめっき等のめっきを施した場合、得られるめっき膜は粒状やコブ状等の荒れが多発して極めて不均一な状態になりやすい、ということを確認した。
そして、この知見に基づいて、さらに、Ｃｕ−Ｎｉ−Ｓｉ系の銅合金材についての歪み除去焼鈍のような最終加熱工程における、加熱処埋温度およびその時間ならびにその加熱雰囲気を種々変更し、最終的に得られる銅合金材の表面の化学的状態や銅ストライクめっき膜の形態がどのような様相を呈するか、つまりどのようにすれば歪み除去焼鈍後に易酸化元素が表層領域には存在しないようにすることができ、延いては良好なめっき性を確保することができるかを、鋭意調査・考察した。
その結果、酸化雰囲気中で加熱した後、引き続いて還元雰囲気で加熱することにより、銅合金材の表層領域における、銅（Ｃｕ）以外の、ニッケル（Ｎｉ）やシリコン（Ｓｉ）
などの易酸化元素（銅（Ｃｕ）よりも酸化物生成自由エネルギの低い元素）の酸化膜が表面から深さ１０ｎｍ程度までの表層領域に生成することを極めて効果的に防止することができることを見出した。
そして、上記のような新知見に基づいて、本発明を成すに到ったのであった。
In order to achieve the above-mentioned object, the inventors of the present invention firstly applied the Cu-Ni-Si-based copper alloy material after the final heating such as strain removal annealing in a reducing atmosphere. Various investigations and investigations were conducted on the causes of low degradation. As a result, when a heat treatment is performed on a Cu—Ni—Si based copper alloy material in a reducing atmosphere, copper (Cu) is not oxidized and silicon (Si) and other easily oxidizable elements diffuse into the surface layer region. Since it preferentially oxidizes, when plating such as copper strike plating is applied to a copper alloy strip having an oxide film such as silicon (Si), the resulting plating film is granular or It was confirmed that rough surfaces such as bumps occur frequently and become extremely uneven.
And based on this knowledge, the heat treatment temperature and the time and the heating atmosphere in the final heating process such as strain removal annealing for the Cu-Ni-Si-based copper alloy material are variously changed, and the final Of the chemical state of the surface of the copper alloy material obtained and the form of the copper strike plating film, that is, how to prevent oxidizable elements from being present in the surface layer region after strain relief annealing It was possible to make it possible, and as a result, whether or not a good plating property could be secured was investigated and studied.
As a result, by heating in an oxidizing atmosphere and subsequently in a reducing atmosphere, nickel (Ni) or silicon (Si) other than copper (Cu) in the surface layer region of the copper alloy material
It is possible to extremely effectively prevent the formation of an oxide film of an easily oxidizable element (an element having a lower free energy for oxide generation than copper (Cu)) from the surface to a depth of about 10 nm. I found it.
And based on the above new knowledge, it came to make this invention.
すなわち、本発明の電気・電子部品用銅合金材は、銅（Ｃｕ）を母材とし、当該母材中にニッケル（Ｎｉ）を１．０質量％以上４．０質量％以下含有すると共にシリコン（Ｓｉ）を０．２質量％以上１．２質量％以下含有する、もしくはさらに副成分として燐（Ｐ）、亜鉛（Ｚｎ）、錫（Ｓｎ）、マグネシウム（Ｍｇ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、マンガン（Ｍｎ）、ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、クロム（Ｃｒ）、銀（Ａｇ）のうちの１種類以上の元素を総量で２．０質量％未満含有する銅基合金に圧延加工を施してなる電気・電子部品用銅合金材であって、当該電気・電子部品用銅合金材の少なくとも片面における表面から深さ１０ｎｍ以内の表層領域に、銅（Ｃｕ）よりも酸化物生成自由エネルギの低い元素の酸化物が存在しないことを特徴としている。
また、本発明の電気・電子部品用銅合金材の製造方法は、銅（Ｃｕ）を母材とし、当該母材中にニッケル（Ｎｉ）を１．０質量％以上４．０質量％以下含有すると共にシリコン（Ｓｉ）を０．２質量％以上１．２質量％以下含有する、もしくはさらに副成分として燐（Ｐ）、亜鉛（Ｚｎ）、錫（Ｓｎ）、マグネシウム（Ｍｇ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、マンガン（Ｍｎ）、ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、クロム（Ｃｒ）、銀（Ａｇ）のうちの１種類以上の元素を総量で２．０質量％未満含有する銅基合金に少なくとも圧延加工を施す工程を含む電気・電子部品用銅合金材の製造方法であって、前記圧延加工を施した後、最終加熱処理として、酸化雰囲気中で加熱処理を施す工程と、その後、引き続いて還元雰囲気中で加熱処理を施す工程とを含むことを特徴としている。
That is, the copper alloy material for electric / electronic parts of the present invention uses copper (Cu) as a base material, and nickel (Ni) is contained in the base material in an amount of 1.0% by mass to 4.0% by mass and silicon. (Si) is contained in an amount of 0.2% by mass or more and 1.2% by mass or less, or further, phosphorus (P), zinc (Zn), tin (Sn), magnesium (Mg), iron (Fe), cobalt as subcomponents. Copper-based alloy containing less than 2.0% by mass in total of one or more elements of (Co), manganese (Mn), zirconium (Zr), titanium (Ti), chromium (Cr), and silver (Ag) A copper alloy material for electric / electronic parts formed by rolling on a surface of the copper alloy material for electric / electronic parts at least 10 nm deep from the surface of the copper alloy material for electric / electronic parts than copper (Cu). Element oxides with low free energy for product formation It is characterized in that it does not exist.
Moreover, the manufacturing method of the copper alloy material for electric / electronic parts of this invention uses copper (Cu) as a base material, and nickel (Ni) is contained in the base material in an amount of 1.0% by mass to 4.0% by mass. In addition, silicon (Si) is contained in an amount of 0.2% by mass to 1.2% by mass, or phosphorus (P), zinc (Zn), tin (Sn), magnesium (Mg), iron (Fe ), Cobalt (Co), Manganese (Mn), Zirconium (Zr), Titanium (Ti), Chromium (Cr), and Silver (Ag) in a total amount of less than 2.0% by mass. A method for producing a copper alloy material for electric / electronic parts, comprising at least a step of subjecting a copper-based alloy to a rolling process, wherein the rolling process is followed by a heat treatment in an oxidizing atmosphere as a final heat treatment; And then heated in a reducing atmosphere It is characterized in that it comprises a step of performing management.
本発明によれば、電気・電子部品用銅合金材の表面における良好なめっき性を確保することが可能となると共に、当該電気・電子部品用銅合金材の伸びの回復および歪みの除去を効果的に行うことが可能となる。その結果、圧延加工後の材料の伸びの回復および歪み除去が十分に成されていると共に良好なめっき性を備えた電気・電子部品用銅合金材が実現される。 According to the present invention, it is possible to ensure good plating properties on the surface of a copper alloy material for electric / electronic parts, and at the same time, it is effective for recovery of elongation and removal of distortion of the copper alloy material for electric / electronic parts. Can be performed automatically. As a result, it is possible to realize a copper alloy material for electric / electronic parts that is sufficiently recovered from elongation after the rolling process and is sufficiently strain-removed and has good plating properties.
以下、本発明の実施の形態に係る電気・電子部品用銅合金材およびその製造方法について詳細に説明する。
この電気・電子部品用銅合金材は、銅（Ｃｕ）を母材とし、その母材中にニッケル（Ｎｉ）を１．０質量％以上４．０質量％以下含有すると共にシリコン（Ｓｉ）を０．２質量％以上１．２質量％以下含有する、もしくはさらに副成分として燐（Ｐ）、亜鉛（Ｚｎ）、錫（Ｓｎ）、マグネシウム（Ｍｇ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、マンガン（Ｍｎ）、ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、クロム（Ｃｒ）、銀（Ａｇ）のうちの１種類以上の元素を総量で２．０質量％未満含有する銅基合金に圧延加工を施して、いわゆる銅合金条材や銅合金薄板のような形態とした電気・電子部品用銅合金材であって、この電気・電子部品用銅合金材自体の少なくとも片面（例えばストライクめっきのようなめっき膜が形成される面や、その他の理由から良好な表面粗さが要求される面。あるいは、例えば両面にめっき膜が形成される場合などには、その両面）における、表面から深さ１０ｎｍ以内の表層領域には、銅（Ｃｕ）よりも酸化物生成自由エネルギの低いシリコン（Ｓｉ）のような易酸化元素の酸化物が存在しないようにしたものである。
Hereinafter, the copper alloy material for electric / electronic parts and the manufacturing method thereof according to the embodiment of the present invention will be described in detail.
This copper alloy material for electrical / electronic parts uses copper (Cu) as a base material, and nickel (Ni) is contained in the base material in an amount of 1.0 mass% to 4.0 mass%, and silicon (Si) is contained. 0.2% by mass or more and 1.2% by mass or less, or further, phosphorus (P), zinc (Zn), tin (Sn), magnesium (Mg), iron (Fe), cobalt (Co) as subcomponents, Rolling a copper-based alloy containing less than 2.0% by mass of one or more elements of manganese (Mn), zirconium (Zr), titanium (Ti), chromium (Cr), and silver (Ag) A copper alloy material for electric / electronic parts in the form of a so-called copper alloy strip or copper alloy thin plate, at least one side of the copper alloy material itself for electric / electronic parts (for example, strike plating) The surface on which the plating film is formed and other For example, a surface that requires a good surface roughness, or, for example, in the case where a plating film is formed on both surfaces, the surface layer region within a depth of 10 nm from the surface is copper (Cu). In other words, an oxide of an easily oxidizable element such as silicon (Si) having a lower free energy for generating an oxide is not present.
さらに詳細には、この電気・電子部品用銅合金材を製造するために用いられる銅基合金としては、その合金成分が、ニッケル（Ｎｉ）：１．０質量％以上４．０質量％以下を含有し、かつシリコン（Ｓｉ）：０．２質量％以上１．２質量％以下を含有し、あるいはさらにそれらに加えて、副成分として燐（Ｐ）、亜鉛（Ｚｎ）、錫（Ｓｎ）、マグネシウム（Ｍｇ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、マンガン（Ｍｎ）、ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、クロム（Ｃｒ）、銀（Ａｇ）のうちの少なくともいずれか１種類以上を総量で２．０質量％未満含有し、残部が銅（Ｃｕ）および不可避的不純物からなるものとする。 More specifically, as a copper-based alloy used for producing this copper alloy material for electric / electronic parts, the alloy component is nickel (Ni): 1.0 mass% or more and 4.0 mass% or less. And silicon (Si): 0.2% by mass or more and 1.2% by mass or less, or in addition to them, phosphorus (P), zinc (Zn), tin (Sn) as subcomponents, Total amount of at least one of magnesium (Mg), iron (Fe), cobalt (Co), manganese (Mn), zirconium (Zr), titanium (Ti), chromium (Cr), silver (Ag) The content is less than 2.0% by mass, and the balance is made of copper (Cu) and inevitable impurities.
そのインゴットの鋳造後、熱間圧延、時効熱処理、冷間圧延等を繰り返して、所定の厚さに圧延加工して行くが、上記のような成分構成とすることにより、時効処理によって金属間化合物であるＮｉ２Ｓｉを析出させることで高強度を得ることができる。しかし、これとは対照的に、ニッケル（Ｎｉ）が１．０質量％未満、またはシリコン（Ｓｉ）が０．１質量％未満では、十分な強度を得ることができなくなる虞が極めて高くなる。また、ニッケル（Ｎｉ）が４．０質量％超、またはシリコン（Ｓｉ）が１．２質量％超であると、導電性の低下、加工性の悪化が顕著になる。特に、中間温度脆性が顕著になり、高温加熱時や熱間加工時の粒界割れが発生する虞が極めて高いものとなる。また、Ｎｉ２Ｓｉ等の析出量が過多になるので、酸洗時などにこれらが表面に残渣となって、めっき不良を誘発する要因となる。またさらに、ニッケル（Ｎｉ）が４．０質量％超になると、溶解時に溶湯中に吸収される水素（Ｈ）の量が増大し、鋳塊中に固溶水素となって残存する。これらの水素は中間温度脆性の一因となり、冷間圧延後の焼鈍時に膨れ状の欠陥等の発生要因となりやすい。 After casting the ingot, hot rolling, aging heat treatment, cold rolling, etc. are repeated and rolled to a predetermined thickness. High strength can be obtained by precipitating Ni 2 Si. However, in contrast, if nickel (Ni) is less than 1.0 mass% or silicon (Si) is less than 0.1 mass%, there is a very high possibility that sufficient strength cannot be obtained. Moreover, when nickel (Ni) exceeds 4.0 mass% or silicon (Si) exceeds 1.2 mass%, the decrease in conductivity and the deterioration in workability become remarkable. In particular, the intermediate temperature brittleness becomes remarkable, and the possibility of occurrence of intergranular cracking during high-temperature heating or hot working becomes extremely high. Moreover, since the precipitation amount of Ni 2 Si and the like becomes excessive, these become residues on the surface during pickling and the like, which causes a plating failure. Furthermore, when nickel (Ni) exceeds 4.0 mass%, the amount of hydrogen (H) absorbed in the molten metal at the time of melting increases and remains as a solid solution hydrogen in the ingot. These hydrogens contribute to intermediate temperature brittleness, and are liable to cause blistering defects during annealing after cold rolling.
合金成分の数値的態様は、さらに望ましくは、ニッケル（Ｎｉ）：１．５質量％以上３．０質量％以下、かつシリコン（Ｓｉ）：０．３質量％以上０．７質量％以下とする。ニッケル（Ｎｉ）とシリコン（Ｓｉ）との成分混合比は、金属間化合物であるＮｉ２Ｓｉの組成に近い方が、効率よく強度と導電性との両方を向上させることが可能と考えられることから、その成分比率は、ニッケル（Ｎｉ）：シリコン（Ｓｉ）＝４：１とすることが望ましい。
ここで、上記の成分が基本であるが、さらに、副成分として、燐（Ｐ）、亜鉛（Ｚｎ）、錫（Ｓｎ）、マグネシウム（Ｍｇ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、マンガン（Ｍｎ）、ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、クロム（Ｃｒ）、銀（Ａｇ）のうちの１種類以上の元素を総量で２．０質量％未満含有するようにしても、上記同様の特性を確保しつつ、さらに下記にそれぞれ述べるような特性を副次的に得ることができる。但し、２．０質量％以上含有するようにした場合、導電性の低下および上記の特性の低下が生じる虞
が顕著になる。
More desirably, the numerical aspect of the alloy component is nickel (Ni): 1.5 mass% to 3.0 mass%, and silicon (Si): 0.3 mass% to 0.7 mass%. . The component mixing ratio of nickel (Ni) and silicon (Si) is considered to be able to improve both strength and conductivity more efficiently when the composition is closer to the composition of Ni 2 Si, which is an intermetallic compound. Therefore, the component ratio is desirably nickel (Ni): silicon (Si) = 4: 1.
Here, the above-mentioned components are basic, but further, as subcomponents, phosphorus (P), zinc (Zn), tin (Sn), magnesium (Mg), iron (Fe), cobalt (Co), manganese ( Mn), zirconium (Zr), titanium (Ti), chromium (Cr), silver (Ag), the same characteristics as described above, even if the total amount of one or more elements is less than 2.0% by mass. While ensuring the above, the following characteristics can be obtained as secondary effects. However, when it is made to contain 2.0 mass% or more, there exists a possibility that the fall of electroconductivity and said characteristic may arise.
上記の副成分のうち、燐（Ｐ）は、溶解時の脱酸剤としての効果と共に、若干の機械的強度向上の効果がある。
亜鉛（Ｚｎ）は、はんだ濡れ性の向上、およびその表面にはんだ層が形成されると、その界面に銅（Ｃｕ）と錫（Ｓｎ）との合金層が成長してしまうことを抑制することができるという効果がある。また、溶解時の脱ガス作用および銅（Ｃｕ）のマイグレーション抑制の効果がある。
錫（Ｓｎ）は、母材の銅（Ｃｕ）中に固溶して、その材料全体としての耐熱性、およびばね性、曲げ加工性、耐応力緩和性などの機械的特性を向上させる効果がある。このことから、コネクタとして使用される電気・電子部品用銅合金材の場合には、錫（Ｓｎ）は添加することが望ましい副添加物（副成分）であると云える。但し、その添加量が上記の２．０質量％以上のように多くなると、導電性の低下を招き、またそれと共に、表面にはんだ層を形成する場合にはそのはんだ層との界面に銅（Ｃｕ）と錫（Ｓｎ）との合金層の生成を助長してしまうこととなり、また錫（Ｓｎ）等のウィスカの発生を助長してしまうこととなる。よって、この錫（Ｓｎ）についても、上記のように、添加量は２．０質量％未満とすることが望ましいのである。
マグネシウム（Ｍｇ）は、実用上の不都合が生じるほどの導電性の低下を招くことなく、材料全体としての機械的強度、耐熱性、耐応力緩和性を向上させる効果がある。また、硫黄（Ｓ）は中間温度脆性を助長させる元素であるが、マグネシウム（Ｍｇ）はその硫黄（Ｓ）と化合物を生成して、粒界の硫黄（Ｓ）を固定し、熱間加工性を向上させる効果がある。但し、このマグネシウム（Ｍｇ）は、０．５質量％以上を添加すると、酸化物の巻き込み等の鋳造性の低下を招く虞が高くなる。このため、添加量はそれ未満とすることが望ましい。
鉄（Ｆｅ）は、高温では主に固溶し、高温熱処理時の再結晶を遅らせ、結晶粒の過大な成長を抑制する効果がある。但し、０．１質量％以上の添加量では、導電性の低下を招く虞が高くなり、また上記の効果も飽和する。よって、鉄（Ｆｅ）については、０．１質量％未満の添加が望ましい。
コバルト（Ｃｏ）は、マグネシウム（Ｍｇ）と同様に、硫黄（Ｓ）と化合物を生成して粒界の硫黄（Ｓ）を固定し、熱間加工性を向上させる効果がある。また、マグネシウム（Ｍｇ）と比べて、導電性の低下は少なくて済む傾向にある。
マンガン（Ｍｎ）も、マグネシウム（Ｍｇ）と同様に、硫黄（Ｓ）と化合物を生成して粒界の硫黄（Ｓ）を固定し、熱間加工性を向上させる効果があるが、導電性の低下を招きやすい。
ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、クロム（Ｃｒ）は、材料としての機械的強度および耐熱性を向上させる効果があるが、酸化物の巻き込み等の鋳造性の低下を招く虞がある。
Among the subcomponents described above, phosphorus (P) has an effect of slightly improving mechanical strength as well as an effect as a deoxidizer at the time of dissolution.
Zinc (Zn) improves solder wettability and suppresses the growth of an alloy layer of copper (Cu) and tin (Sn) at the interface when a solder layer is formed on the surface. There is an effect that can be. Moreover, there exists an effect of degassing action at the time of dissolution and copper (Cu) migration suppression.
Tin (Sn) dissolves in copper (Cu) as a base material, and has the effect of improving the mechanical properties such as heat resistance, spring property, bending workability, and stress relaxation resistance of the entire material. is there. From this, it can be said that in the case of a copper alloy material for electric / electronic parts used as a connector, tin (Sn) is a desirable sub-additive (sub-component) to be added. However, if the addition amount is increased to 2.0% by mass or more as described above, the conductivity is lowered, and at the same time, when a solder layer is formed on the surface, copper ( The formation of an alloy layer of Cu) and tin (Sn) is promoted, and the generation of whiskers such as tin (Sn) is promoted. Therefore, it is desirable for the tin (Sn) to be added in an amount of less than 2.0% by mass as described above.
Magnesium (Mg) has the effect of improving the mechanical strength, heat resistance, and stress relaxation resistance of the entire material without causing a decrease in conductivity that causes practical inconvenience. Sulfur (S) is an element that promotes brittleness at intermediate temperature. Magnesium (Mg) forms a compound with sulfur (S) to fix sulfur (S) at the grain boundary, and hot workability. There is an effect of improving. However, if this magnesium (Mg) is added in an amount of 0.5% by mass or more, there is a high possibility that castability such as entanglement of oxides will be lowered. For this reason, it is desirable that the addition amount be less than that.
Iron (Fe) mainly has a solid solution at a high temperature, delays recrystallization during high-temperature heat treatment, and has an effect of suppressing excessive growth of crystal grains. However, when the addition amount is 0.1% by mass or more, there is a high possibility that the conductivity is lowered, and the above effect is saturated. Therefore, about iron (Fe), addition of less than 0.1% by mass is desirable.
Cobalt (Co), like magnesium (Mg), produces a compound with sulfur (S) to fix the grain boundary sulfur (S), and has the effect of improving hot workability. Further, there is a tendency that the decrease in conductivity is less than that of magnesium (Mg).
Manganese (Mn), like magnesium (Mg), produces sulfur (S) and a compound to fix grain boundary sulfur (S) and improves hot workability. It tends to cause a decline.
Zirconium (Zr), titanium (Ti), and chromium (Cr) have an effect of improving mechanical strength and heat resistance as materials, but may cause deterioration of castability such as entanglement of oxides.
このような合金成分を有する銅基合金を用いて、それに圧延加工および歪み除去焼鈍処理等の各種処理を施すことにより（それらの詳細は後述する）、本発明の実施の形態に係る電気・電子部品用銅合金材では、表面から深さ１０ｎｍ以内の表層領域に、銅（Ｃｕ）よりも酸化物生成自由エネルギの低いシリコン（Ｓｉ）のような元素の酸化物が存在しないようにしている。そして、このようにしたことにより、本発明の実施の形態に係る電気・電子部品用銅合金材は、圧延加工後の材料の伸びの回復および歪み除去が十分に成されていると共に、表面に粒状やコブ上などの荒れがなく、良好なめっき性を備えたものとなっている。 By using the copper-based alloy having such an alloy component and subjecting it to various treatments such as rolling and strain-relieving annealing (the details will be described later), the electric / electronic device according to the embodiment of the present invention In the copper alloy material for parts, an oxide of an element such as silicon (Si) having a lower free energy of oxide generation than copper (Cu) does not exist in a surface layer region within a depth of 10 nm from the surface. And by doing in this way, the copper alloy material for electrical / electronic parts according to the embodiment of the present invention has sufficiently recovered the elongation of the material after rolling and removed the strain, and on the surface. There is no roughness on the grain or bump, and it has good plating properties.
次に、本発明の実施の形態に係る電気・電子部品用銅合金材の製造方法について説明する。
坩堝式溶解炉やチャネル式溶解炉等の電気炉で、上記のような所定の成分を溶解した後
、連続鋳造により、例えば厚さ１５０〜２５０ｍｍ、幅４００〜１０００ｍｍ程度の矩形断面鋳塊（ケーク）を鋳造する。そしてそのケークを、８００〜９５０℃の温度で３０分間以上保持した後、熱間圧延機により、厚さ１０〜２０ｍｍ程度に圧延する。このときの熱間圧延の加熱温度が８００℃よりも低いと、熱間圧延時に粒界に割れが生じる虞が極めて高くなる。また、鋳造の冷却過程で析出した粗大なＮｉ２Ｓｉ化合物が十分に固溶しない。これらは最終製品にまで残存し、通常の酸洗液では溶解しないために残渣となり、表面に残存した場合は、めっき性に悪影響を及ぼすこととなる。他方、９５０℃よりも高温であると、再結晶した結晶が粗大化しやすく、また酸化膜が厚くなってしまう。従って、熱間圧延の加熱温度は８００〜９５０℃とすることが望ましい。また、保持時間は３０分より短いと析出物が十分に固溶しない。このため、保持時間は３０分以上とすることが望ましい。
Next, a method for manufacturing a copper alloy material for electric / electronic parts according to an embodiment of the present invention will be described.
After melting the above-mentioned predetermined components in an electric furnace such as a crucible melting furnace or a channel melting furnace, a rectangular cross-section ingot having a thickness of about 150 to 250 mm and a width of about 400 to 1000 mm (cake) is obtained by continuous casting. ). And after holding the cake for 30 minutes or more at the temperature of 800-950 degreeC, it rolls to about 10-20 mm in thickness with a hot rolling mill. When the heating temperature of the hot rolling at this time is lower than 800 ° C., there is an extremely high possibility that cracks will occur at the grain boundaries during hot rolling. Further, the coarse Ni 2 Si compound precipitated during the cooling process of casting does not sufficiently dissolve. These remain in the final product and do not dissolve in a normal pickling solution, and thus become a residue. When remaining on the surface, the plating properties are adversely affected. On the other hand, when the temperature is higher than 950 ° C., the recrystallized crystal is likely to be coarsened and the oxide film becomes thick. Therefore, the heating temperature for hot rolling is desirably 800 to 950 ° C. On the other hand, if the holding time is shorter than 30 minutes, the precipitate is not sufficiently dissolved. For this reason, it is desirable that the holding time be 30 minutes or longer.
リードフレーム用の電気・電子部品用銅合金材の場合には、熱間圧延の後に引き続いて時効処理を突施する。あるいは面削により酸化膜を除去して冷間圧延後に時効処理を実施する。時効処理は３５０〜６００℃の温度で０．５〜２４時間保持する。時効処理温度が３５０℃未満では、析出速度が遅く、２４時間以上加熱しても十分析出しない。また、時効処理温度が６００℃を超えると、微細な析出物を得ることができなくなると共に固溶限が増加し、熱力学的平衡状態に到達しても導電率の低下が顕著になる。また、析出物が粗大化し、めっき性に悪影響を及ぼすこととなる。強度を重視する場合は３５０〜４５０℃の温度で時効、加工性を重視する場合は５００〜６００℃の温度で時効、導電性を重視する場合は５００〜５５０℃の温度で時効しさらにその後に３５０〜４５０℃の温度で時効する、といったプロセス条件設定等の工夫が必要である。また、時効前の冷間圧延の加工率が低過ぎると、析出速度が遅くなると共に十分な機械的強度が得難くなる。時効処理後には、冷間圧延と焼鈍とを繰り返し、必要に応じて酸洗浄、バフ研磨等を行った後、最終圧延を行う。また、必要に応じてテンション・レベリングで板形状を整えた後、下記に述べるような表層領域の成分調整を兼ねた歪み除去焼鈍を実施して、伸びの回復、歪みの除去・均一化を図ると共に、表面から深さ１０ｎｍまでの表層領域における成分中に銅（Ｃｕ）よりも酸化物生成自由エネルギの低いシリコン（Ｓｉ）のような元素の酸化物が存在しないようにする。
すなわち、本発明の実施の形態に係る電気・電子部品用銅合金材の製造方法では、最終段階での歪み除去焼鈍としては、下記のような２通りの方法があり、そのうちのいずれか１つを用いる。
In the case of a copper alloy material for an electrical / electronic component for a lead frame, an aging treatment is applied after hot rolling. Alternatively, the oxide film is removed by chamfering and an aging treatment is performed after cold rolling. The aging treatment is held at a temperature of 350 to 600 ° C. for 0.5 to 24 hours. When the aging temperature is less than 350 ° C., the deposition rate is slow, and even when heated for 24 hours or more, it does not precipitate sufficiently. On the other hand, if the aging temperature exceeds 600 ° C., fine precipitates cannot be obtained, the solid solubility limit increases, and even if a thermodynamic equilibrium state is reached, the decrease in conductivity becomes significant. In addition, the precipitate becomes coarse and adversely affects the plating property. Aging at a temperature of 350 to 450 ° C when emphasizing strength, aging at a temperature of 500 to 600 ° C when emphasizing workability, aging at a temperature of 500 to 550 ° C when emphasizing conductivity, and then It is necessary to devise a process condition setting such as aging at a temperature of 350 to 450 ° C. Moreover, when the processing rate of the cold rolling before aging is too low, it will become difficult to obtain sufficient mechanical strength while the precipitation rate will become slow. After the aging treatment, cold rolling and annealing are repeated, and after the acid cleaning, buffing and the like are performed as necessary, final rolling is performed. In addition, after adjusting the plate shape by tension / leveling as necessary, strain-relief annealing that also adjusts the components of the surface layer as described below is performed to recover the elongation and to remove and homogenize the strain. At the same time, an oxide of an element such as silicon (Si) having a lower free energy of oxide generation than copper (Cu) is not present in components in the surface layer region from the surface to a depth of 10 nm.
In other words, in the method for manufacturing a copper alloy material for electric / electronic parts according to the embodiment of the present invention, there are two methods as described below for strain relief annealing at the final stage, and any one of them is as follows. Is used.
第１の方法は、酸化雰囲気中で加熱し、その後、引き続いて還元雰囲気中で加熱する、というものである。
それらの加熱工程における温度や時間等の具体的なプロセス条件の設定は、焼鈍前の材料の機械的強度、伸び、耐熱性等の諸条件に大きく依存するが、３００℃超４５０℃未満の範囲内の温度、より望ましくは３２５℃以上４２５℃以下の温度で、合計１〜５分間程度の加熱が好適である。
The first method is to heat in an oxidizing atmosphere and then heat in a reducing atmosphere.
The setting of specific process conditions such as temperature and time in these heating steps largely depends on various conditions such as mechanical strength, elongation and heat resistance of the material before annealing, but it is in the range of more than 300 ° C and less than 450 ° C. Heating at a temperature of 325 ° C. or more and 425 ° C. or less, more preferably for a total of about 1 to 5 minutes, is preferable.
使用する加熱炉は、バッチ式でも連続焼鈍炉でもよいが、雰囲気制御が可能なものが必要であり、この点では、連続焼鈍炉が望ましい。また、酸化炉、還元炉を直列したタイプで１回の迎続焼鈍で実施してもよく、もしくは個別に酸化雰囲気、還元雰囲気でそれぞれ１回ずつ焼鈍するようにしてもよい。また、酸化雰囲気中で４２５℃よりも高い温度で加熱すると酸化膜が剥離しやすくなり、３２５℃未満の温度で加熱すると十分な効果が得られないので、酸化雰囲気中では３２５℃以上４２５℃以下の温度で加熱することが望ましい。
この酸化雰囲気中での加熱処理プロセスでは、加工対象の電気・電子部品用銅合金材の表層領域における母材（基相）の銅（Ｃｕ）のマトリクス全体を酸化させて、銅（Ｃｕ）の酸化膜を形成し、その銅の酸化膜（マトリクス）の存在によって、銅（Ｃｕ）以外の例
えばシリコン（Ｓｉ）のような酸化物生成自由エネルギの低い元素が厚さ方向に深い領域から浅い表層領域へと拡散（移動）して来てその表層領域内に濃化することを、阻止する。
但し、この表層領域における銅（Ｃｕ）の酸化膜の厚さが厚すぎると、その酸化膜がいわゆる表層剥離を起こす虞や、次段の還元雰囲気中での加熱を施した後に著しくポーラスな表面状態になる虞が、極めて高くなる。このため、このとき形成する銅（Ｃｕ）の酸化膜の厚さの上限値は、１μｍ以下、さらに望ましくは５００ｎｍ以下とする。なお、下限値については、例えばリードフレーム用のめっき加工に適した良好なめっき性を備えた表面状態を最終的に得るためには、１０ｎｍ以上とすることが望ましい。このようにすることにより、少なくとも表面から深さ１０ｎｍ以内の表層領域には、表面の荒れの要因となるシリコン（Ｓｉ）のような易酸化元素の酸化物が存在しないようにすることができる。
The heating furnace to be used may be either a batch type or a continuous annealing furnace, but a furnace capable of controlling the atmosphere is necessary. In this respect, the continuous annealing furnace is desirable. Further, the oxidation furnace and the reduction furnace may be connected in series, and may be performed by one-time annealing, or may be individually annealed once in an oxidizing atmosphere and a reducing atmosphere. Further, when heated at a temperature higher than 425 ° C. in an oxidizing atmosphere, the oxide film easily peels off, and when heated at a temperature lower than 325 ° C., a sufficient effect cannot be obtained. It is desirable to heat at the temperature.
In the heat treatment process in this oxidizing atmosphere, the entire matrix of copper (Cu) of the base material (base phase) in the surface layer region of the copper alloy material for electric / electronic parts to be processed is oxidized, and the copper (Cu) An oxide film is formed, and due to the presence of the copper oxide film (matrix), an element having a low free energy for generating an oxide such as silicon (Si) other than copper (Cu) is formed from a deep region to a shallow surface layer. It is prevented from diffusing (moving) into the region and thickening in the surface layer region.
However, if the thickness of the copper (Cu) oxide film in this surface layer region is too thick, the oxide film may cause so-called surface layer peeling, or a significantly porous surface after being heated in a reducing atmosphere at the next stage. The risk of becoming a condition is extremely high. For this reason, the upper limit of the thickness of the copper (Cu) oxide film formed at this time is 1 μm or less, more preferably 500 nm or less. The lower limit is desirably 10 nm or more in order to finally obtain a surface state having good plating properties suitable for lead frame plating, for example. By doing so, it is possible to prevent an oxide of an easily oxidizable element such as silicon (Si), which causes surface roughness, at least in the surface layer region within a depth of 10 nm from the surface.
上記のような酸化雰囲気中での加熱処理を行った後、引き続いて、還元雰囲気中での加熱処理を実施する。この還元雰囲気中での加熱プロセスでは、表層領域における酸化した銅（Ｃｕ）のマトリクスに還元反応を施して、元の銅（Ｃｕ）に戻す。但し、このとき過大な熱を与えるなどして還元反応が強過ぎるようになると、シリコン（Ｓｉ）やその他の易酸化元素が表層領域付近に拡散して来て膿化してしまう。従って、酸化雰囲気中での加熱温度および酸素分圧で酸化膜の厚さを設定した後、それに対応して、この還元雰囲気中での加熱処理では、易酸化元素が表層領域付近に拡散して来ることのないように、加熱温度および還元ガス分圧等のプロセス条件を設定することが望ましい。 After performing the heat treatment in the oxidizing atmosphere as described above, the heat treatment in the reducing atmosphere is subsequently performed. In the heating process in the reducing atmosphere, a reduction reaction is performed on the oxidized copper (Cu) matrix in the surface layer region to return to the original copper (Cu). However, if the reduction reaction becomes too strong by applying excessive heat at this time, silicon (Si) and other easily oxidizable elements diffuse into the vicinity of the surface layer region and become suppurated. Therefore, after setting the thickness of the oxide film with the heating temperature and oxygen partial pressure in the oxidizing atmosphere, in this heat treatment in the reducing atmosphere, easily oxidizable elements diffuse near the surface layer region. It is desirable to set process conditions such as heating temperature and reducing gas partial pressure so as not to come.
以上のような、第１の歪み除去焼鈍の方法を含んだ製造方法によれば、まず酸化雰囲気中で適切なプロセス条件で加熱することにより、加工対象である電気・電子部品用銅合金材における、表面から１０ｎｍ〜１μｍ程度の深さまでの表層領域の銅（Ｃｕ）のマトリクスを酸化させて銅（Ｃｕ）の酸化膜を形成し、その酸化膜の存在によって、シリコン（Ｓｉ）のような易酸化元素が表層領域へと拡散して来て濃化することを、阻止することができる。そして、それに引き続いて、還元雰囲気中で適切なプロセス条件で加熱することにより、表層領域に形成されていた銅（Ｃｕ）の酸化膜を還元反応で元の銅（Ｃｕ）へと戻すことができる。また、それらの加熱によって、材料としての伸びの回復および歪み除去等、本来の歪み除去焼鈍の目的についても、十分効果的に達成される。
このようにして、圧延加工後の材料の伸びの回復および歪み除去が十分に成されていると共に、表面に粒状やコブ状などの荒れが生じることのない良好なめっき性を備えた電気・電子部品用銅合金材を製造することができる。
According to the manufacturing method including the first strain-removal annealing method as described above, first, in a copper alloy material for electric / electronic parts to be processed, by heating in an oxidizing atmosphere under appropriate process conditions. The copper (Cu) matrix in the surface layer region from the surface to a depth of about 10 nm to 1 μm is oxidized to form an oxide film of copper (Cu), and the presence of the oxide film makes it easy for silicon (Si). It is possible to prevent the oxidizing element from diffusing into the surface layer region and concentrating. Subsequently, by heating under a suitable process condition in a reducing atmosphere, the copper (Cu) oxide film formed in the surface layer region can be returned to the original copper (Cu) by a reduction reaction. . In addition, the purpose of the original strain removal annealing, such as recovery of elongation as a material and strain removal, can be achieved sufficiently effectively by the heating.
In this way, the recovery of elongation of the material after rolling and the removal of distortion are sufficiently achieved, and the electric and electronic materials have good plating properties that do not cause roughness such as grain or bumps on the surface. A copper alloy material for parts can be manufactured.
第２の方法は、まず、加工対象の電気・電子部品用銅合金材に、還元雰囲気中で加熱処理を施す。その後、その加工対象の電気・電子部品用銅合金材の表層における、銅（Ｃｕ）よりも酸化物生成自由エネルギの低い元素やその酸化物が濃化した領域を、化学研磨や機械研磨等によって除去する。その後、酸化雰囲気中での加熱処理を施す。その後、さらに引き続いて、還元雰囲気中での加熱処理を施す、というものである。このような第２の方法によれば、化学研磨や機械研磨等を行う工程や、最初の還元雰囲気中での加熱処理を行う工程が追加されるという点では上記の第１の方法よりも手間が掛かることとなるが、得られる効果はさらに高いものとなる。 In the second method, first, a copper alloy material for electric / electronic parts to be processed is subjected to heat treatment in a reducing atmosphere. After that, in the surface layer of the copper alloy material for electrical / electronic parts to be processed, an element having a lower free energy of oxide generation than copper (Cu) and a region where the oxide is concentrated are obtained by chemical polishing or mechanical polishing. Remove. Thereafter, heat treatment is performed in an oxidizing atmosphere. Thereafter, heat treatment in a reducing atmosphere is further performed. According to such a second method, it is more troublesome than the first method in that a step of performing chemical polishing or mechanical polishing or a step of performing a heat treatment in the first reducing atmosphere is added. However, the effect obtained is even higher.
この第２の方法では、まず、最初の還元雰囲気中での加熱処理を行う。これにより、加工対象の電気・電子部品用銅合金材の表面付近に、易酸化元素の濃縮層を形成する。これにより、その表面付近よりも深い領域には、易酸化元素の欠乏層が生じることとなる。つまり、敢えて最初に還元雰囲気中で加熱することで、故意に易酸化元素を表面付近へと集合させることにより、その表面付近よりも下の（例えばその表面付近よりも１０ｎｍ程度以上深い）所定の領域内には、易酸化元素の存在を希薄化させる、もしくは易酸化元素が存在しないようにする。 In the second method, first, heat treatment is performed in an initial reducing atmosphere. Thereby, a concentrated layer of easily oxidizable elements is formed in the vicinity of the surface of the copper alloy material for electric / electronic parts to be processed. Thereby, an easily oxidizable element-depleted layer is formed in a region deeper than the vicinity of the surface. That is, by deliberately collecting the oxidizable elements near the surface by first heating in a reducing atmosphere, a predetermined value below the surface (for example, about 10 nm or more deeper than the surface) is predetermined. In the region, the presence of the easily oxidizable element is diluted or no easily oxidizable element is present.
そして、易酸化元素が集合してその濃縮層となった表面付近の領域を、化学研磨または機械研磨もしくはその両方（いわゆるダマシン加工等）によって除去する。そうすると、その表面付近の領域が除去された跡に、新たに表れる表面およびその下に連なる新たな表層領域は、易酸化元素が存在しない、もしくは極めて希薄な表面およびそれに連なる表層領域なのであるから、この段階で、この加工対象の電気・電子部品用銅合金材における表面から少なくとも深さ１０ｎｍ程度以上までの表層領域には、銅（Ｃｕ）よりも酸化物生成自由エネルギの低いシリコン（Ｓｉ）のような易酸化元素が存在しない、もしくは存在が極めて希薄な状態となっている。 Then, the region in the vicinity of the surface where the easily oxidizable elements gather to form the concentrated layer is removed by chemical polishing or mechanical polishing or both (so-called damascene processing or the like). Then, because the surface that appears near the surface has been removed, the newly appearing surface and the new surface region that continues below it are the surfaces where the oxidizable elements do not exist or are extremely dilute and the surface region that continues to it. At this stage, the surface layer region from the surface of the copper alloy material for electrical / electronic parts to be processed to a depth of at least about 10 nm or more is made of silicon (Si) having a lower free energy for oxide generation than copper (Cu). Such an easily oxidizable element does not exist, or the existence is extremely dilute.
続いて、その易酸化元素が存在しない表層領域が露出した状態の電気・電子部品用銅合金材に、第１の方法と同様に、酸化雰囲気中での加熱処理を施すことにより、その表層領域の銅（Ｃｕ）のマトリクスを酸化させて酸化膜を形成する。 Subsequently, by subjecting the copper alloy material for electric / electronic parts in a state where the surface layer region in which the easily oxidizable element does not exist is exposed to heat treatment in an oxidizing atmosphere as in the first method, the surface layer region is obtained. An oxide film is formed by oxidizing the copper (Cu) matrix.
そして引き続き、第１の方法と同様に、還元雰囲気中での加熱処理を実施することにより、表層領域における酸化した銅（Ｃｕ）のマトリクスに還元反応を施して、元の銅（Ｃｕ）に戻す。 Then, similarly to the first method, by performing heat treatment in a reducing atmosphere, a reduction reaction is performed on the oxidized copper (Cu) matrix in the surface layer region to return to the original copper (Cu). .
以上のような、第２の歪み除去焼鈍の方法を含んだ製造方法によれば、最初の還元雰囲気中での加熱処理を施すことにより、加工対象の電気・電子部品用銅合金材の表面付近に易酸化元素が拡散して来て濃化し、その領域が濃縮層となることを、むしろ逆手に取って利用して、表面付近に易酸化元素の濃縮層を積極的に形成する。そしてその易酸化元素の濃縮層を化学研磨や機械研磨によって除去する。これにより、この加工対象の電気・電子部品用銅合金材における表面から深さ１０ｎｍ程度以上までの表層領域に銅（Ｃｕ）よりも酸化物生成自由エネルギの低いシリコン（Ｓｉ）のような、めっき性の低下の要因となる易酸化元素が表層領域には存在しない状態とすることが可能となる。そして、そのように易酸化元素を表層領域からほぼ完全に（但し、実際上不可避的に存在する、あるいはこの処理の後に何らかの外乱的要因等で発生するような酸化物等の存在については、誤差的なものと見做して、本発明では考察の対象外とする）駆逐した状態とした後、第１の方法と同様に、酸化雰囲気中での加熱処理を施し、引き続いて還元雰囲気中での加熱処理を施すことにより、第１の方法の場合によりもさらに確実で効果的に、表面に粒状やコブ状などの荒れが生じることのない良好なめっき性を備えた電気・電子部品用銅合金材を製造することができる。また、このような３段階の加熱処理によって、材料としての伸びの回復および歪み除去等、本来の歪み除去焼鈍の目的についても、十分効果的に達成される。
このようにして、圧延加工後の材料の伸びの回復および歪み除去が十分に成されていると共に、表面に粒状やコブ状などの荒れが生じることのない良好なめっき性を備えた電気・電子部品用銅合金材を製造することができる。
According to the manufacturing method including the second strain-removal annealing method as described above, by performing the heat treatment in the first reducing atmosphere, the vicinity of the surface of the copper alloy material for electric / electronic parts to be processed The oxidizable element diffuses and concentrates, and the region becomes a concentrated layer. Instead, the concentrated layer of the easily oxidizable element is actively formed near the surface. Then, the concentrated layer of easily oxidizable elements is removed by chemical polishing or mechanical polishing. As a result, the surface layer region from the surface to the depth of about 10 nm or more in the copper alloy material for electrical / electronic parts to be processed is plated, such as silicon (Si) having lower free energy of oxide generation than copper (Cu). It is possible to make a state in which an easily oxidizable element that causes a decrease in property does not exist in the surface layer region. Then, the oxidizable elements are almost completely out of the surface layer region (however, the existence of oxides that are inevitably present in practice or that are generated due to some disturbance factor after this treatment) In the present invention, it is excluded from consideration) and after being subjected to heat treatment in an oxidizing atmosphere as in the first method, and subsequently in a reducing atmosphere. By applying this heat treatment, the copper for electric and electronic parts having a good plating property that does not cause roughening such as grain or bumps on the surface more reliably and effectively than in the case of the first method. Alloy materials can be manufactured. In addition, by such three-stage heat treatment, the purpose of the original strain removal annealing, such as recovery of elongation as a material and removal of strain, can be achieved sufficiently effectively.
In this way, the recovery of elongation of the material after rolling and the removal of distortion are sufficiently achieved, and the electric and electronic materials have good plating properties that do not cause roughness such as grain or bumps on the surface. A copper alloy material for parts can be manufactured.
以上説明したように、本発明の実施の形態に係る電気・電子部品用銅合金材およびその製造方法によれば、表面から深さ１０ｎｍ以内の表層領域に、銅（Ｃｕ）よりも酸化物生成自由エネルギの低い易酸化元素の酸化物が存在しないようにする、もしくはそのような易酸化元素の酸化物の発生を抑制してその存在を極めて希薄化なものとするようにしたので、この電気・電子部品用銅合金材の表面における良好なめっき性を確保することが可能となると共に、この電気・電子部品用銅合金材の伸びの回復および歪みの除去を効果的に行うことが可能となる。その結果、圧延加工後の材料の伸びの回復および歪み除去が十分に成されていると共に良好なめっき性を備えた電気・電子部品用銅合金材を実現することができる。また、めっき性のみならず、はんだ濡れ性についても良好なものとすることが可能となる。 As described above, according to the copper alloy material for electric / electronic parts and the manufacturing method thereof according to the embodiment of the present invention, an oxide is generated in a surface layer region within a depth of 10 nm from the surface rather than copper (Cu). This is because the oxides of easily oxidizable elements with low free energy do not exist, or the generation of such easily oxidizable element oxides is suppressed and the existence thereof is extremely diluted. -It is possible to ensure good plating properties on the surface of copper alloy materials for electronic parts, and to effectively recover the elongation and remove distortion of this copper alloy material for electric and electronic parts. Become. As a result, it is possible to realize a copper alloy material for electric / electronic parts that has been sufficiently recovered in elongation and removed from distortion after rolling and has good plating properties. Further, not only the plating property but also the solder wettability can be improved.
これとは対照的に、従来の技術では、歪み除去焼鈍を施した後に得られる電気・電子部
品用銅合金材におけるめっき性が低劣化する場合が多かった。すなわち、Ｃｕ−Ｎｉ−Ｓｉ系合金には、銅（Ｃｕ）よりも酸化物の生成自由エネルギが著しく低いシリコン（Ｓｉ）や、その他の微量成分が含まれている。活性ガスや還元ガスのような酸素分圧の低い雰囲気中での加熱処理では、銅（Ｃｕ）は酸化せずにシリコン（Ｓｉ）やその他の易酸化元素が表層領域へと拡散して来て、優先的に酸化することとなる。このようなシリコン（Ｓｉ）等の酸化膜を有する状態の銅合金条に銅ストライクめっき等のめっきを施した場合、得られるめっき膜は粒状やコブ状等の荒れが多発して極めて不均一な状態になりやすい。具体的には表面粗さが荒く、光沢の少ない外観になりやすい。このような要因から、従来の歪み除去焼鈍工程を含んだ電気・電子部品用銅合金材の製造技術では、その歪み除去焼鈍を施した後に得られる電気・電子部品用銅合金材におけるめっき性が低劣化していた。
これを改善するためには、めっきの前処理で、銅合金材の表面におけるシリコン（Ｓｉ）等の酸化層を除去することや、めっき液およびその他のめっきプロセス条件設定の工夫が必要になる。しかし、めっきを行うリードフレーム・メーカーでは、前処理およびめっき液ならびにめっき条件等の調整に煩雑な手間や時間が掛かることを嫌うため、銅合金条メーカーで何らかの対策を行うことが必要になる。例えば不活性雰囲気や還元雰囲気で焼鈍する場合の有効な対策としては、ガスの水蒸気露点を充分に、例えば−４０℃以下に低くすることや、材料表面に残存した水分や油分を十分に除去・乾燥してから焼鈍を施すことなどが挙げられるが、実際のリードフレームの製造においては、左様な工程の管理が極めて煩雑で困難を伴うものとなる傾向にあり、また十分な効果が得られない場合も多かった。
しかし、本発明の実施の形態に係る電気・電子部品用銅合金材およびその製造方法によれば、以上説明したように第１の歪み除去焼鈍の方法を含んだ製造方法または第２の歪み除去焼鈍の方法を含んだ製造方法によって、工程の管理の煩雑化や困難化を伴うことなく、電気・電子部品用銅合金材の表面における良好なめっき性を確保することが可能となり、かつその材料としての伸びの回復および歪みの除去を効果的に行うことが可能となる。
In contrast to this, in the conventional technique, the plating property in the copper alloy material for electric / electronic parts obtained after the strain relief annealing is often deteriorated. That is, the Cu—Ni—Si-based alloy contains silicon (Si), which has a significantly lower free energy of formation of oxide than copper (Cu), and other trace components. In heat treatment in an atmosphere having a low oxygen partial pressure, such as active gas or reducing gas, copper (Cu) is not oxidized, but silicon (Si) and other oxidizable elements diffuse into the surface layer region. , Will preferentially oxidize. When plating such as copper strike plating is applied to a copper alloy strip having an oxide film such as silicon (Si), the resulting plating film is very uneven due to frequent occurrence of roughness such as grain or bumps. Prone to state. Specifically, the surface roughness is rough and the appearance is less glossy. For these reasons, in the conventional technology for manufacturing copper alloy materials for electric and electronic parts including a strain relief annealing process, the plating properties of the copper alloy material for electric and electronic parts obtained after the strain relief annealing is reduced. The deterioration was low.
In order to improve this, it is necessary to remove an oxide layer such as silicon (Si) on the surface of the copper alloy material and to devise a plating solution and other plating process condition settings in the pretreatment of plating. However, lead frame manufacturers that perform plating hate that it takes time and effort to adjust pretreatment, plating solution, and plating conditions, so it is necessary for copper alloy strip manufacturers to take some measures. For example, as an effective measure when annealing in an inert atmosphere or a reducing atmosphere, the water vapor dew point of the gas is sufficiently lowered, for example, to −40 ° C. or less, and moisture and oil remaining on the material surface are sufficiently removed. Although it is possible to anneal after drying, etc., in actual lead frame production, the management of the process on the left tends to be extremely complicated and difficult, and sufficient effects cannot be obtained There were many cases.
However, according to the copper alloy material for electric / electronic parts and the manufacturing method thereof according to the embodiment of the present invention, as described above, the manufacturing method or the second strain removal including the first strain removing annealing method. Manufacturing methods including annealing methods make it possible to ensure good plating properties on the surface of copper alloy materials for electrical and electronic parts without complicating and difficult process management. As a result, it is possible to effectively recover the elongation and remove the distortion.
上記の実施の形態で説明した製造方法によって、実施例に係る電気・電子部品用銅合金材の試料（試料１、２、３）を作製した。試料１、２は、第１の歪み除去焼鈍を含んだ製造方法によって作製し、また試料３は、第２の歪み除去焼鈍を含んだ製造方法によって作製した。
また、それとの比較のために、上記の実施の形態にて規定したプロセス条件等とは敢えて異なった設定で、比較例に係る電気・電子部品用銅合金材の試料（試料４、５、６、７）、および従来例に係る電気・電子部品用銅合金材の試料（試料８、９、１０）を作製した。そして、それらの試料のそれぞれの表面に、銅（Ｃｕ）のストライクめっきを施した。
Samples (samples 1, 2, and 3) of copper alloy materials for electric / electronic parts according to the examples were manufactured by the manufacturing method described in the above embodiment. Samples 1 and 2 were manufactured by a manufacturing method including the first strain removal annealing, and Sample 3 was manufactured by a manufacturing method including the second strain removal annealing.
In addition, for comparison with the above, samples of copper alloy materials for electric / electronic parts according to comparative examples (samples 4, 5, 6) are set differently from the process conditions defined in the above embodiment. 7), and copper alloy material samples (samples 8, 9, 10) for electric / electronic parts according to the conventional example. And the strike plating of copper (Cu) was given to each surface of those samples.
それらの試料について、めっき膜の表面のＳＥＭ像の撮影、および歪み除去焼鈍後の表層領域のＸＰＳ分析を行った。図１は、本発明の実施例に係る試料Ｎｏ．２（以降、試料２と呼ぶ）の電気・電子部品用銅合金材の表面のＸＰＳ分析結果を示す図であり、図２は、比較例に係る試料Ｎｏ．４（以降、試料４と呼ぶ）の電気・電子部品用銅合金材の表面のＸＰＳ分析結果を示す図であり、図３は、従来例に係る試料Ｎｏ．８（以降、試料８と呼ぶ）の電気・電子部品用銅合金材の表面のＸＰＳ分析結果を示す図であり、図４は、他の従来例に係る試料Ｎｏ．９（以降、試料９と呼ぶ）の電気・電子部品用銅合金材の表面のＸＰＳ分析結果を示す図である。
ここで、図１、図２、図３、図４グラフの横軸にはスパッタ時間（単位：分）をプロットしてあるが、これはＳｉＯ２換算で、１分間が１．４ｎｍの深さに相当する。例えば、スパッタ時間が１０分間ならば、それは深さ１４ｎｍに相当するものであると換算することができる。
図５は、本発明の実施例に係る試料２の電気・電子部品用銅合金材のストライクめっき
後の表面のＳＥＭ像を示す図であり、図６は、比較例に係る試料４の電気・電子部品用銅合金材のストライクめっき後の表面のＳＥＭ像を示す図であり、図７は、従来例に係る試料８の電気・電子部品用銅合金材のストライクめっき後の表面のＳＥＭ像を示す図であり、図８は図７とは別の従来例に係る試料９の電気・電子部品用銅合金材のストライクめっき後の表面のＳＥＭ像を示す図である。
なお、図５、図６、図７、図８では、上段はめっきの均一性を比較するためのＳＥＭ像を、下段は上段のＳＥＭ像を３．５倍に拡大してめっき粒の粗度を比較するためのＳＥＭ像を、それぞれ示している。
About those samples, the imaging | photography of the SEM image of the surface of a plating film and the XPS analysis of the surface layer area | region after distortion removal annealing were performed. 1 shows a sample No. 1 according to an embodiment of the present invention. 2 (hereinafter referred to as sample 2) is a view showing the XPS analysis result of the surface of the copper alloy material for electric and electronic parts, and FIG. 4 (hereinafter referred to as sample 4) is a view showing the XPS analysis result of the surface of the copper alloy material for electric and electronic parts. 8 (hereinafter referred to as sample 8) is a view showing the XPS analysis result of the surface of the copper alloy material for electric and electronic parts, and FIG. It is a figure which shows the XPS analysis result of the surface of the copper alloy material for electrical / electronic parts of 9 (henceforth the sample 9).
Here, the horizontal axis of the graphs of FIGS. 1, 2, 3, and 4 plots the sputtering time (unit: minutes). This is a depth of 1.4 nm per minute in terms of SiO 2. It corresponds to. For example, if the sputtering time is 10 minutes, it can be converted to that corresponding to a depth of 14 nm.
FIG. 5 is a view showing an SEM image of the surface after strike plating of the copper alloy material for electric / electronic parts of sample 2 according to the example of the present invention, and FIG. 6 shows electric / electron characteristics of sample 4 according to the comparative example. It is a figure which shows the SEM image of the surface after strike plating of the copper alloy material for electronic components, FIG. 7: shows the SEM image of the surface after strike plating of the copper alloy material for electrical / electronic components of the sample 8 which concerns on a prior art example. FIG. 8 is a view showing an SEM image of the surface after strike plating of a copper alloy material for electric / electronic parts of a sample 9 according to a conventional example different from FIG.
5, 6, 7, and 8, the upper part is an SEM image for comparing the uniformity of plating, and the lower part is an enlargement of the SEM image of the upper part to 3.5 times to increase the roughness of the plated grains. SEM images for comparing are respectively shown.
まず、中周波誘導型坩堝炉で、Ｃｕ−２．４ｗｔ％Ｎｉ−０．６ｗｔ％Ｓｉ−０．１ｗｔ％Ｍｇの組成の銅基合金を溶解・調製後、銅製鋳型で半連続鋳造し、断面サイズ１８０ｍｍ×１５０ｍｍ、長さ４５００ｍｍの矩形断面鋳塊（ケーク）を鋳造した。そしてそのケークを、９００℃において３時間加熱した後、熱間圧延して厚さ１５ｍｍとし、直ちに水冷した。 First, in a medium frequency induction type crucible furnace, after melting and preparing a copper-based alloy having a composition of Cu-2.4 wt% Ni-0.6 wt% Si-0.1 wt% Mg, semi-continuous casting with a copper mold, A rectangular cross-section ingot (cake) having a size of 180 mm × 150 mm and a length of 4500 mm was cast. The cake was heated at 900 ° C. for 3 hours, then hot-rolled to a thickness of 15 mm, and immediately water-cooled.
続いて、その表面を面削して酸化スケールを除去した後、時効処埋、冷間圧延、中間焼鈍、酸洗浄、バフ研磨を組み合わせて実施し、最終圧延により、厚さ０．１５ｍｍの、歪み除去焼鈍未加工の銅合金条を得た。時効処理、中間焼鈍の雰囲気は、窒素雰囲気とした。 Subsequently, after chamfering the surface to remove the oxide scale, aging treatment, cold rolling, intermediate annealing, acid cleaning, buffing are performed in combination, and by final rolling, a thickness of 0.15 mm, Unstrained annealed copper alloy strips were obtained. The atmosphere of aging treatment and intermediate annealing was a nitrogen atmosphere.
この銅合金条を供試材として、表１に纏めて示した加熱雰囲気および加熱条件で、歪み除去焼鈍を実施した。なお、表１において、「加熱１」とは、最初の還元雰囲気中での加熱処理であり、「加熱２」とは、酸化雰囲気中での加熱処理であり、「加熱３」とは、最後の還元雰囲気中での加熱処理である。また、「研磨」は、最初の還元雰囲気中での加熱処理の直後に引き続いて行った化学研磨による研磨処理（表層の易酸化元素の濃縮層の除去工程）である。 Using this copper alloy strip as a test material, strain-relief annealing was performed in the heating atmosphere and heating conditions summarized in Table 1. In Table 1, “heating 1” is the heat treatment in the first reducing atmosphere, “heating 2” is the heat treatment in the oxidizing atmosphere, and “heating 3” is the last. Heat treatment in a reducing atmosphere. Further, “polishing” is a polishing process (removal step of the concentrated layer of easily oxidizable elements on the surface layer) performed immediately after the heat treatment in the first reducing atmosphere by chemical polishing.
銅（Ｃｕ）のストライクめっきとしては、電流密度５Ａ／ｄｍ２で３０秒間の電解脱脂を施した後、希硫酸で３０秒間酸洗し、引き続いて硫酸銅めっき液（Ｈ２ＳＯ４＋ＣｕＳＯ４）を用いて電流密度５Ａ／ｄｍ２で１０秒間電解めっきを行った。その後、ＢＴＡで防錆した。 For strike plating of copper (Cu), after electrolytic degreasing at a current density of 5 A / dm 2 for 30 seconds, pickling with dilute sulfuric acid for 30 seconds, followed by copper sulfate plating solution (H 2 SO 4 + CuSO 4 ) Was used for electrolytic plating at a current density of 5 A / dm 2 for 10 seconds. Thereafter, rust was prevented with BTA.
そして、そのめっき膜の表面の状態を、ＳＥＭ像によって調べた。また、各試料の材料表面領域における成分分布をＸＰＳ分析によって調べた。そしてそれらの結果に基づいて、各試料の表面状態（表層領域におけるシリコン（Ｓｉ）の酸化物の存在の有無）およびめっき性の良否（銅（Ｃｕ）めっき粒子の均一度ならびに一次特性（材料としての機械的な伸びの回復等の効果）について評価・検討した。
その結果を纏めて表２に示す。ここで、表２では、酸化膜の厚さが３ｎｍ以下でありかつシリコン（Ｓｉ）酸化物が存在していないことを、易酸化元素の存在に関しての評価の合格の条件とし、合格のものについては丸印を付して示した（表２の注１）。また、銅（Ｃｕ）めっき均一性については、めっき膜面の不均一さの要因である粗大めっき粒が存在しないことを、めっき性に関しての評価の合格の条件とし、合格のものについては丸印を付して示した（表２の注２）。また、１次特性については、歪み除去焼鈍後における材料（試料）の伸びの回復等、一般的な評価基準を合格条件とし、合格のものには○印を付し、焼鈍の効果がやや不足気味のものには△印を付し、焼鈍の効果が明らかに不十分のものには×印を付して示してある。
And the state of the surface of the plating film was investigated by the SEM image. Moreover, the component distribution in the material surface area | region of each sample was investigated by XPS analysis. Based on these results, the surface state of each sample (the presence or absence of silicon (Si) oxide in the surface layer region) and the plating quality (uniformity of copper (Cu) plated particles and primary characteristics (as materials) The effect of the recovery of mechanical elongation of the
The results are summarized in Table 2. Here, in Table 2, the thickness of the oxide film is 3 nm or less and no silicon (Si) oxide is present as a condition for passing the evaluation regarding the presence of the easily oxidizable element. Is shown with a circle (Note 1 in Table 2). In addition, for copper (Cu) plating uniformity, the absence of coarse plating grains that are the cause of plating film surface non-uniformity is regarded as a condition for passing the evaluation regarding plating properties. (Note 2 in Table 2). In addition, for primary characteristics, general evaluation criteria such as recovery of material (sample) elongation after strain-relief annealing are used as acceptable conditions, and those that pass are marked with ○, and the effect of annealing is somewhat insufficient. Appearances are marked with a Δ, and those with an apparently insufficient annealing effect are marked with a cross.
本発明の実施例に係る試料１、２、３では、表２、図１、図５から明らかなように、歪み除去焼鈍後の表層領域における、銅（Ｃｕ）よりも酸化物生成自由エネルギの低い易酸化元素の酸化膜の生成は、実質的に全くなかった（不可避的に残存するような極めて若干量の酸化物の存在を除いて）。そしてその結果、粗大なめっき粒のない均一なストライクめっき膜が得られることが確認された。また、１次特性も満足したものとなることが確認
された。
In Samples 1, 2, and 3 according to the examples of the present invention, as is clear from Table 2, FIG. 1 and FIG. There was virtually no formation of oxide films of low oxidizable elements (except for the presence of very small amounts of oxide that would inevitably remain). As a result, it was confirmed that a uniform strike plating film without coarse plating grains was obtained. It was also confirmed that the primary characteristics were satisfied.
また、比較例に係る試料４では、表２、図２、図６から明らかなように、酸化雰囲気中での加熱（加熱２）の温度が３００℃と低かったため、表層領域内にシリコン（Ｓｉ）の酸化膜が発生し、それが要因となって、ストライクめっき膜に粗大なめっき粒が発生して不均一な膜面となった。
比較例に係る試料５では、表２から明らかなように、酸化雰囲気中での加熱（加熱２）の温度を４５０℃と高くし過ぎたため、銅（Ｃｕ）の酸化膜剥離が生じ、また過焼鈍となった。この試料５の結果から、酸化雰囲気中での加熱（加熱２）の温度は、４５０℃未満、より望ましくは４２５℃以下とすることが適切であるものと考えられる。また、その下限値については、試料４の結果からすると、３００℃超、より望ましくは３２５℃以上とすることが適切であるものと考えられる。
比較例に係る試料６では、表２から明らかなように、最後の還元雰囲気中での加熱（加熱３）の温度が３００℃と低かったため、銅（Ｃｕ）の酸化膜が十分には還元できず、仕上った材料の表面に銅（Ｃｕ）の酸化膜が残ってめっき性が低下し、得られためっき膜は不均一なものとなった。また、焼鈍もやや不足した結果となった。
比較例に係る試料７では、表２から明らかなように、最後の還元雰囲気中での加熱（加熱３）の温度を５００℃と高くし過ぎたため、仕上った材料の表面に銅（Ｃｕ）の酸化膜が若干残り、これが要因となって、めっき膜がやや不均一なものとなった。また、過焼鈍となり、仕上った材料の機械的強度が低下した。
In Sample 4 according to the comparative example, as is clear from Table 2, FIG. 2, and FIG. 6, the temperature of heating (heating 2) in the oxidizing atmosphere was as low as 300 ° C., so silicon (Si ) Was generated, and this caused the formation of coarse plating grains on the strike plating film, resulting in a non-uniform film surface.
In sample 5 according to the comparative example, as is clear from Table 2, the temperature of heating (heating 2) in the oxidizing atmosphere was too high at 450 ° C., so that the copper (Cu) oxide film was peeled off, and excessively high. It became annealed. From the results of Sample 5, it is considered that the temperature of heating (heating 2) in an oxidizing atmosphere is appropriate to be less than 450 ° C., more desirably 425 ° C. or less. In addition, the lower limit value is considered to be appropriate to be over 300 ° C., more desirably 325 ° C. or higher, from the results of Sample 4.
In sample 6 according to the comparative example, as apparent from Table 2, the temperature of the last heating (heating 3) in the reducing atmosphere was as low as 300 ° C., so that the copper (Cu) oxide film could be sufficiently reduced. In other words, a copper (Cu) oxide film remained on the surface of the finished material, resulting in a decrease in plating performance, and the resulting plated film was uneven. In addition, annealing was somewhat insufficient.
In the sample 7 according to the comparative example, as apparent from Table 2, the temperature of the last heating in the reducing atmosphere (heating 3) was excessively increased to 500 ° C., so that the surface of the finished material was made of copper (Cu). Some oxide film remained, and this caused the plating film to be slightly non-uniform. Moreover, it became over-annealing and the mechanical strength of the finished material was reduced.
従来例に係る試料８では、従来技術による、Ｈ２２５％＋Ｎ２７５％の還元雰囲気中での４５０℃・１分間の加熱による歪み除去焼鈍のみを施した結果、表２、図３、図７から明らかなように、仕上った材料の表層領域付近にはシリコン（Ｓｉ）の酸化膜が顕著に発生し、その表面に形成しためっき膜は極めて不均一なものとなった。
従来例に係る試料９では、従来技術による、Ｎ２１００％の還元雰囲気中での４５０℃・１分間の加熱による歪み除去焼鈍のみを施したところ、その結果は、表２、図４、図８から明らかなように、試料８の場合ほど顕著ではなかったが、試料８とほぼ同様の傾向を示し、仕上った材料の表層領域付近にはシリコン（Ｓｉ）の酸化膜が発生して、めっき膜は極めて不均一なものとなった。
従来例に係る試料１０では、従来技術による、Ｎ２１００％の還元雰囲気中での３００℃・１分間の加熱による歪み除去焼鈍のみを施した。その結果、表２から明らかなように、温度が３００度と低かったため、表層領域にシリコン（Ｓｉ）の酸化膜は発生しなかったが、本来の目的である歪み除去焼鈍の効果は十分なものが得られなかった。
In the sample 8 according to the conventional example, as a result of performing only the strain removal annealing by heating at 450 ° C. for 1 minute in a reducing atmosphere of H 2 25% + N 2 75% according to the conventional technique, Table 2, FIG. 3, FIG. As apparent from FIG. 7, a silicon (Si) oxide film was prominently generated in the vicinity of the surface layer region of the finished material, and the plating film formed on the surface thereof was extremely uneven.
In the sample 9 according to the conventional example, only the strain removal annealing by heating at 450 ° C. for 1 minute in a reducing atmosphere of N 2 100% according to the prior art was performed. The results are shown in Table 2, FIG. As is clear from FIG. 8, although not as remarkable as in the case of Sample 8, the same tendency as in Sample 8 was exhibited, and an oxide film of silicon (Si) was generated near the surface layer region of the finished material. The film was very uneven.
In the sample 10 according to the conventional example, only the strain removal annealing by heating at 300 ° C. for 1 minute in a reducing atmosphere of N 2 100% according to the conventional technique was performed. As a result, as apparent from Table 2, since the temperature was as low as 300 ° C., an oxide film of silicon (Si) was not generated in the surface layer region, but the effect of strain removal annealing, which was the original purpose, was sufficient. Was not obtained.
以上の結果から、本発明の実施例に係る電気・電子部品用銅合金材およびその製造方法によれば、比較例や従来例に係る試料では不可能であった、歪み除去焼鈍後に粗大なめっき粒のない均一なストライクめっき膜を得ることと、歪み除去焼鈍本来の目的である１次特性も十分なものを得ることとの、両立を達成できることが確認された。 From the above results, according to the copper alloy material for electric and electronic parts and the manufacturing method thereof according to the example of the present invention, coarse plating after strain relief annealing, which was not possible with the samples according to the comparative example and the conventional example, It was confirmed that it was possible to achieve both of obtaining a uniform strike plating film free of grains and obtaining sufficient primary characteristics, which is the original purpose of strain relief annealing.
なお、上記の実施の形態および実施例では、仕上った電気・電子部品用銅合金材の表面の品質の良否を判断するための具体的な一態様として、銅（Ｃｕ）ストライクめっき膜を形成する場合の、めっき性（粗大めっき粒等が存在してめっき膜面が不均一になるか否か）について考察し、そのようなめっき性について、本発明によれば良好な品質を得ることができることを確証したが、この他にも、例えば、はんだ濡れ性などについても、本発明によれば向上せしめることが可能である。すなわち、本発明によれば、電気・電子部品用銅合金材における、めっき性のみならず、はんだ濡れ性についても、極めて良好なものとすることが可能である。 In the above-described embodiments and examples, a copper (Cu) strike plating film is formed as a specific mode for judging the quality of the surface of the finished copper alloy material for electric and electronic parts. In this case, the plating property (whether coarse plating particles etc. are present and the plating film surface becomes non-uniform) is considered, and according to the present invention, good quality can be obtained for such plating property. In addition to this, for example, solder wettability can be improved according to the present invention. That is, according to the present invention, not only the plating property but also the solder wettability in the copper alloy material for electric / electronic parts can be made extremely good.
Claims (6)
当該電気・電子部品用銅合金材の少なくとも片面における表面から深さ１０ｎｍ以内の表層領域に、銅（Ｃｕ）よりも酸化物生成自由エネルギの低い元素の酸化物が存在しないことを特徴とする電気・電子部品用銅合金材。 Copper (Cu) is used as a base material, and nickel (Ni) is contained in the base material in an amount of 1.0% by mass to 4.0% by mass and silicon (Si) is contained in an amount of 0.2% by mass to 1.2% by mass. Contains or further contains phosphorus (P), zinc (Zn), tin (Sn), magnesium (Mg), iron (Fe), cobalt (Co), manganese (Mn), zirconium (Zr), titanium as subcomponents Copper alloy material for electric and electronic parts formed by rolling a copper base alloy containing less than 2.0% by mass of one or more elements of (Ti), chromium (Cr), and silver (Ag) Because
Electricity characterized in that no oxide of an element having a lower free energy of oxide formation than copper (Cu) exists in a surface layer region within a depth of 10 nm from the surface of at least one surface of the copper alloy material for electric / electronic parts. -Copper alloy material for electronic parts.
前記圧延加工を施した後、最終加熱処理として、酸化雰囲気中で加熱処理を施す工程と、その後、引き続いて還元雰囲気中で加熱処理を施す工程とを含む
ことを特徴とする電気・電子部品用銅合金材の製造方法。 Copper (Cu) is used as a base material, and nickel (Ni) is contained in the base material in an amount of 1.0% by mass to 4.0% by mass and silicon (Si) is contained in an amount of 0.2% by mass to 1.2% by mass. Contains or further contains phosphorus (P), zinc (Zn), tin (Sn), magnesium (Mg), iron (Fe), cobalt (Co), manganese (Mn), zirconium (Zr), titanium as subcomponents Copper for electric / electronic parts including a step of rolling at least a copper base alloy containing less than 2.0% by mass of one or more elements of (Ti), chromium (Cr), and silver (Ag) An alloy material manufacturing method comprising:
After the rolling process, the final heat treatment includes a step of performing a heat treatment in an oxidizing atmosphere, and then a step of subsequently performing a heat treatment in a reducing atmosphere. A method for producing a copper alloy material.
前記最終加熱処理を施して、当該電気・電子部品用銅合金材の少なくとも片面における表面から深さ１０ｎｍ以内の表層領域に、銅（Ｃｕ）よりも酸化物生成自由エネルギの低い元素の酸化物が存在しないようにする
ことを特徴とする電気・電子部品用銅合金材の製造方法。 In the manufacturing method of the copper alloy material for electrical / electronic parts according to claim 2,
After the final heat treatment, an oxide of an element having a lower free energy for oxide generation than copper (Cu) is present in a surface layer region within a depth of 10 nm from the surface of at least one surface of the copper alloy material for electric / electronic parts. A method for producing a copper alloy material for electrical and electronic parts, characterized in that it does not exist.
前記還元雰囲気中での加熱処理とは別段に、前記酸化雰囲気中での加熱処理の前に還元雰囲気中での加熱処理を施す工程を、さらに備えた
ことを特徴とする電気・電子部品用銅合金材の製造方法。 In the manufacturing method of the copper alloy material for electrical / electronic components according to claim 2 or 3,
Separately from the heat treatment in the reducing atmosphere, the method further includes a step of performing a heat treatment in the reducing atmosphere before the heat treatment in the oxidizing atmosphere. Manufacturing method of alloy material.
前記酸化雰囲気中での加熱処理の前に行われる最初の還元雰囲気中での加熱処理を施した後、当該電気・電子部品用銅合金材の表層における、銅（Ｃｕ）よりも酸化物生成自由エネルギの低い元素および／またはその酸化物が濃化した領域を、化学研磨および／または機械研磨によって除去する工程を、さらに備えた
ことを特徴とする電気・電子部品用銅合金材の製造方法。 In the manufacturing method of the copper alloy material for electrical / electronic parts according to claim 4,
After the heat treatment in the first reducing atmosphere performed before the heat treatment in the oxidizing atmosphere, the oxide generation is more free than the copper (Cu) in the surface layer of the copper alloy material for electric / electronic parts. A method for producing a copper alloy material for electric / electronic parts, further comprising a step of removing a region where an element having low energy and / or its oxide is concentrated by chemical polishing and / or mechanical polishing.
前記酸化雰囲気中での加熱処理における、当該酸化雰囲気の温度を、３２５℃以上４２５℃以下とする
ことを特徴とする電気・電子部品用銅合金材の製造方法。 In the manufacturing method of the copper alloy material for electrical / electronic parts according to any one of claims 2 to 5,
The method for producing a copper alloy material for electric / electronic parts, wherein the temperature of the oxidizing atmosphere in the heat treatment in the oxidizing atmosphere is set to 325 ° C. or higher and 425 ° C. or lower.
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