JP2015133324A - aluminum alloy wire - Google Patents

aluminum alloy wire Download PDF

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JP2015133324A
JP2015133324A JP2015029938A JP2015029938A JP2015133324A JP 2015133324 A JP2015133324 A JP 2015133324A JP 2015029938 A JP2015029938 A JP 2015029938A JP 2015029938 A JP2015029938 A JP 2015029938A JP 2015133324 A JP2015133324 A JP 2015133324A
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wire
alloy
terminal
layer
conductor
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美里 草刈
Misato Kusakari
美里 草刈
中井 由弘
Yoshihiro Nakai
由弘 中井
西川 太一郎
Taichiro Nishikawa
太一郎 西川
義幸 高木
Yoshiyuki Takagi
義幸 高木
崇康 杉原
Takayasu Sugihara
崇康 杉原
茂吉 中山
Mokichi Nakayama
茂吉 中山
能章 山野
Yoshiaki Yamano
能章 山野
直也 西村
Naoya Nishimura
直也 西村
一成 佐倉
Kazunari Sakura
一成 佐倉
大塚 保之
Yasuyuki Otsuka
保之 大塚
古川 欣吾
Kingo Furukawa
欣吾 古川
Original Assignee
住友電気工業株式会社
Sumitomo Electric Ind Ltd
株式会社オートネットワーク技術研究所
Auto Network Gijutsu Kenkyusho:Kk
住友電装株式会社
Sumitomo Wiring Syst Ltd
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Priority to JP2015029938A priority Critical patent/JP2015133324A/en
Publication of JP2015133324A publication Critical patent/JP2015133324A/en
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Abstract

PROBLEM TO BE SOLVED: To provide an aluminum alloy wire and an aluminum alloy stranded wire each having excellent corrosion resistance, an insulated electric wire using the alloy stranded wire as a conductor, and an electric wire with a terminal including the insulated electric wire.SOLUTION: There is provided the aluminum alloy wire for use in a conductor of an electric wire for an automobile, which has a cross sectional area of 8 mmor less, and which includes a coating layer on an external surface of an end of the alloy wire to which a terminal member made of copper or copper alloy is attached. The outermost layer of the coating layer is composed of tin or a tin alloy. In the aluminum alloy wire having the cross sectional area of 8 mmor less, electric corrosion is likely to occur in the vicinity of a terminal member made of copper or copper alloy since an exposed area of copper or copper alloy with respect to an exposed area of aluminum alloy becomes larger. However, since tin or tin alloy exists between the aluminum alloy and the terminal member made of copper or copper alloy, electric corrosion between aluminum alloy and terminal member can be reduced.

Description

本発明は、電線の導体に用いられるアルミニウム合金線及びアルミニウム合金撚り線、この合金線などを導体とする絶縁電線、この絶縁電線と端子部材とを具える端子付き電線に関するものである。特に、耐食性に優れるアルミニウム合金線及び端子付き電線に関するものである。   The present invention relates to an aluminum alloy wire and an aluminum alloy stranded wire used for a conductor of an electric wire, an insulated wire using the alloy wire as a conductor, and an electric wire with a terminal including the insulated wire and a terminal member. In particular, the present invention relates to an aluminum alloy wire and a terminal-attached electric wire having excellent corrosion resistance.
従来、自動車や飛行機などの搬送機器、ロボットなどの産業機器の電線は、その端部において、絶縁層を除去して導体を露出させ、この導体部分に端子を取り付けて利用されている。電線の導体や端子の構成材料は、導電性に優れた銅や銅合金といった銅系材料が主流である。   Conventionally, electric wires of transport equipment such as automobiles and airplanes and industrial equipment such as robots are used by removing an insulating layer and exposing a conductor at an end thereof, and attaching a terminal to the conductor. Copper-based materials such as copper and copper alloys, which are excellent in conductivity, are the mainstream as constituent materials for conductors and terminals of electric wires.
昨今、自動車の高性能化や高機能化が急速に進められてきており、車載される各種電気機器、制御機器などの増加に伴い、これらの機器に使用される電線も増加傾向にある。一方、近年、環境保全のため、自動車や飛行機などの燃費の向上が望まれている。軽量化すると、燃費を向上できる。そこで、電線の軽量化のために、比重が銅の約1/3であるアルミニウムやその合金を導体に用いることが検討されている(特許文献1)。   In recent years, the performance and functionality of automobiles have been rapidly increased, and with the increase of various electric devices and control devices mounted on the vehicle, the number of electric wires used for these devices is also increasing. On the other hand, in recent years, improvement of fuel consumption of automobiles, airplanes and the like is desired for environmental protection. When the weight is reduced, fuel consumption can be improved. Therefore, in order to reduce the weight of the electric wire, use of aluminum having a specific gravity of about 1/3 of copper or an alloy thereof as a conductor has been studied (Patent Document 1).
特開2005-108608号公報Japanese Patent Laid-Open No. 2005-108608
アルミニウム合金線を導体とした電線に対して、耐食性を向上することが望まれている。   It is desired to improve the corrosion resistance of an electric wire using an aluminum alloy wire as a conductor.
上述のように端子は、銅や銅合金からなるものが多い。そのため、導体の構成材料がアルミニウム合金である場合、導体の構成材料と端子の構成材料とが異種の金属であることから、アルミニウム合金からなる導体と銅などからなる端子との間で電気腐食(電食)が生じ得る。   As described above, the terminal is often made of copper or a copper alloy. Therefore, when the constituent material of the conductor is an aluminum alloy, since the constituent material of the conductor and the constituent material of the terminal are dissimilar metals, the electric corrosion between the conductor made of the aluminum alloy and the terminal made of copper or the like ( Electric corrosion) can occur.
特許文献1では、電食を低減するために、アルミニウムの露出面積に対する銅の露出面積を小さくすること、具体的には、端子において導体が溶接される箇所を除く部分に錫メッキを施すことを提案している。しかし、特許文献1では、上記露出面積をどの程度にすればよいかについて、具体的に検討されていない。   In Patent Document 1, in order to reduce electrolytic corrosion, it is necessary to reduce the exposed area of copper relative to the exposed area of aluminum, and specifically, to apply tin plating to a portion other than the portion where the conductor is welded at the terminal. is suggesting. However, Patent Document 1 does not specifically examine how much the exposed area should be.
そこで、本発明の目的は、自動車用電線の導体に好適であり、耐食性に優れるアルミニウム合金線、及びアルミニウム合金撚り線を提供することにある。また、本発明の他の目的は、上記合金線や撚り線を導体とした耐食性に優れる絶縁電線、及び端子付き電線を提供することにある。   Then, the objective of this invention is suitable for the conductor of the electric wire for motor vehicles, and is providing the aluminum alloy wire and aluminum alloy strand wire which are excellent in corrosion resistance. Another object of the present invention is to provide an insulated wire excellent in corrosion resistance using the alloy wire or stranded wire as a conductor, and a wire with terminal.
アルミニウム合金の露出面積に対する銅や銅合金の露出面積の割合が小さいほど、電食を低減することができる。本発明者らが更に検討したところ、アルミニウム合金からなる導体と、銅といったアルミニウムよりも貴な金属からなる端子部材との間に、アルミニウムよりも貴な金属、具体的には錫又は錫合金からなる層を存在させると、腐食電流を小さくすることができることから、電食を効果的に低減することができるとの知見を得た。特に、導体の断面積が特定の範囲である場合に、電食の低減効果が大きいとの知見を得た。本発明は、上記知見に基づくものである。   As the ratio of the exposed area of copper or the copper alloy to the exposed area of the aluminum alloy is smaller, the electrolytic corrosion can be reduced. Further examination by the present inventors revealed that a conductor made of an aluminum alloy and a terminal member made of a metal more precious than aluminum such as copper, a metal precious than aluminum, specifically, tin or a tin alloy. It was found that the presence of such a layer can reduce the corrosion current, and thus can effectively reduce the electrolytic corrosion. In particular, when the cross-sectional area of the conductor is in a specific range, it has been found that the effect of reducing electrolytic corrosion is large. The present invention is based on the above findings.
本発明のアルミニウム合金線(以下、Al合金線と呼ぶ)は、自動車用電線の導体に用いられるものであって、断面積が8mm2以下である。このAl合金線の外面の少なくとも一部に被覆層を具えており、この被覆層の最外層は、錫又は錫合金から構成されている。 The aluminum alloy wire (hereinafter referred to as Al alloy wire) of the present invention is used for a conductor of an automobile electric wire and has a cross-sectional area of 8 mm 2 or less. A coating layer is provided on at least a part of the outer surface of the Al alloy wire, and the outermost layer of the coating layer is made of tin or a tin alloy.
本発明Al合金線は、外面(表面)の少なくとも一部に錫層又は錫合金層を具えることで、異種の金属、特に、アルミニウムよりも貴な銅や銅合金といった金属からなる端子部材が接続されても、この端子部材とAl合金線との間に、アルミニウムよりも貴な錫や錫合金からなる層を存在させることできる。この錫層や錫合金層の存在により、本発明Al合金線は、腐食速度を遅くすることができ、端子部材との間で生じる電食を効果的に低減することができる。特に、本発明Al合金線では、断面積を8mm2(8sq)以下に限定している。ここで、断面積が8mm2超である太いAl合金線では、銅や銅合金からなる端子部材が取り付けられる端部において、銅や銅合金の露出面積に対するAl合金の露出面積の比(以下、Al露出比と呼ぶ)が相対的に大きくなることから、電食が生じ難くなる。しかし、断面積が8mm2(8sq)以下である細いAl合金線では、Al露出比が小さくなる(銅などの露出面積が多くなる)ことから、電食が比較的進行し易い。図3は、黄銅に対するアルミニウム合金の面積比と腐食電流の密度との関係を示すグラフである。面積が異なる複数の黄銅板及びアルミニウム合金板(1.05質量%Fe-0.15質量%Mg-Al)を用意し、両板の一端を導線で繋ぐと共に、両板を0.5質量%濃度のNaCl水溶液に含浸する。この状態で、上記導線に電流計を取り付けて腐食電流を測定する。測定した電流値をアルミニウム合金板の面積で除して電流密度を求めた。そして、黄銅に対するアルミニウム合金の面積比(Al露出比)と上記電流密度との関係を図3に示す。図3から、面積比(Al露出比)が大きいほど、即ち、銅合金に対してアルミニウム合金の露出面積が大きいほど、電流密度が小さくなっていることが分かる。また、図3から、この面積比と電流密度との関係は比例的な関係ではなく、当該面積比が小さくなると電流密度が急激に大きくなることが分かる。従って、本発明Al合金線で規定するように、断面積が8mm2以下といった細いAl合金線の外面に上記被覆層を具えることで、電食をより効果的に低減することができると言える。そのため、本発明Al合金線は、耐食性に優れることが望まれる自動車用電線の導体に好適に利用することができる。以下、本発明をより詳細に説明する。 The Al alloy wire of the present invention comprises a tin layer or a tin alloy layer on at least a part of the outer surface (surface), so that a terminal member made of a different kind of metal, in particular, a metal such as copper or a copper alloy which is more noble than aluminum. Even if connected, a layer made of tin or a tin alloy, which is more noble than aluminum, can be present between the terminal member and the Al alloy wire. Due to the presence of the tin layer and the tin alloy layer, the Al alloy wire of the present invention can slow the corrosion rate and can effectively reduce the electrolytic corrosion generated between the terminal member and the aluminum alloy wire. In particular, in the Al alloy wire of the present invention, the cross-sectional area is limited to 8 mm 2 (8 sq) or less. Here, the thick Al alloy wire cross-sectional area is 8 mm 2, greater than at the end of the terminal member made of copper or a copper alloy is attached, the ratio of the exposed area of the Al alloy for the exposed area of the copper or copper alloy (hereinafter, Electrolytic corrosion is less likely to occur because the Al exposure ratio is relatively large. However, in a thin Al alloy wire having a cross-sectional area of 8 mm 2 (8 sq) or less, since the Al exposure ratio is small (the exposed area of copper or the like is increased), electrolytic corrosion is relatively easy to proceed. FIG. 3 is a graph showing the relationship between the area ratio of the aluminum alloy to brass and the density of the corrosion current. Prepare multiple brass plates and aluminum alloy plates (1.05 mass% Fe-0.15 mass% Mg-Al) with different areas, connect one end of both plates with a conductor, and impregnate both plates with 0.5 mass% NaCl aqueous solution To do. In this state, an ammeter is attached to the conducting wire and the corrosion current is measured. The current density was determined by dividing the measured current value by the area of the aluminum alloy plate. FIG. 3 shows the relationship between the area ratio of aluminum alloy to brass (Al exposure ratio) and the current density. FIG. 3 shows that the current density decreases as the area ratio (Al exposure ratio) increases, that is, as the exposed area of the aluminum alloy relative to the copper alloy increases. In addition, FIG. 3 shows that the relationship between the area ratio and the current density is not a proportional relationship, and that the current density increases rapidly as the area ratio decreases. Therefore, as defined by the Al alloy wire of the present invention, it can be said that by providing the coating layer on the outer surface of a thin Al alloy wire having a cross-sectional area of 8 mm 2 or less, electrolytic corrosion can be more effectively reduced. . Therefore, the Al alloy wire of the present invention can be suitably used for a conductor of an automotive electric wire that is desired to have excellent corrosion resistance. The present invention will be described in detail below.
[Al合金線及びAl合金撚り線]
《組成》
本発明Al合金線を構成するAl合金は、添加元素を含有し、残部がAl及び不可避的不純物からなる種々の組成のものが利用できる。添加元素は、例えば、Fe、Mg、Si、Cu、Zn、Ni、Mn、Ag、Cr及びZrから選択される1種以上が挙げられる。添加元素の好ましい合計含有量は0.005質量%以上5.0質量%以下、より好ましくは0.1質量%以上2.0質量%以下である。各元素の好ましい含有量は、質量%で、Fe:0.005%以上2.2%以下、Mg:0.05%〜1.0%、Mn,Ni,Zr,Zn,Cr及びAg:合計で0.005%以上0.2%以下、Cu:0.05%以上0.5%以下、Si:0.04%以上1.0%以下である。これらの添加元素は、1種でも2種以上を組み合わせて含有していてもよい。このような合金として、例えば、Al-Fe合金、Al-Fe-Mg合金、Al-Fe-Si合金、Al-Fe-Mg-(Mn,Ni,Zr,Ag)合金、Al-Fe-Cu合金、Al-Fe-Cu-(Mg,Si)合金、Al-Mg-Si-Cu合金などが挙げられる。
[Al alloy wire and Al alloy stranded wire]
"composition"
As the Al alloy constituting the Al alloy wire of the present invention, those having various compositions containing an additive element and the balance of Al and inevitable impurities can be used. Examples of the additive element include one or more selected from Fe, Mg, Si, Cu, Zn, Ni, Mn, Ag, Cr, and Zr. A preferable total content of additive elements is 0.005% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 2.0% by mass or less. Preferable content of each element is mass%, Fe: 0.005% to 2.2%, Mg: 0.05% to 1.0%, Mn, Ni, Zr, Zn, Cr and Ag: 0.005% to 0.2% in total, Cu: 0.05% to 0.5%, Si: 0.04% to 1.0%. These additive elements may be contained alone or in combination of two or more. Examples of such alloys include Al-Fe alloys, Al-Fe-Mg alloys, Al-Fe-Si alloys, Al-Fe-Mg- (Mn, Ni, Zr, Ag) alloys, and Al-Fe-Cu alloys. Al-Fe-Cu- (Mg, Si) alloy, Al-Mg-Si-Cu alloy, and the like.
Al合金の具体的な組成として、例えば、以下の(1)〜(6)が挙げられる。
(1) 質量%で、Feを0.90%以上1.20%以下、Mgを0.10%以上0.25%以下含有し、残部がAl及び不可避的不純物。
(2) 質量%で、Feを1.01%以上2.2%以下、Mgを0.05%以上0.5%以下、Mn,Ni,Zr,及びAgから選択される1種以上の元素を合計で0.005%以上0.2%以下含有し、残部がAl及び不可避的不純物。
(3) 質量%で、Feを1.01%以上2.2%以下、Cuを0.05%以上0.5%以下含有し、残部がAl及び不可避的不純物。
(4) 質量%で、Feを1.0%以上2.2%以下、Cuを0.05%以上0.5%以下含有し、更にMgを0.1%以上0.5%以下及びSiを0.04%以上0.3%以下の少なくとも1種を含有し、残部がAl及び不可避的不純物。
(5) 質量%で、Mgを0.2%以上1.0%以下、Siを0.1%以上1.0%以下、Cuを0.1%以上0.5%以下含有し、残部がAl及び不可避的不純物。
(6) 質量%で、Mgを0.2%以上1.0%以下、Siを0.1%以上1.0%以下、Cuを0.1%以上0.5%以下含有し、残部がAl及び不可避的不純物。但し、Mg及びSiの質量比Mg/Siが0.8≦Mg/Si≦2.7を満たす。
Specific examples of the Al alloy include the following (1) to (6).
(1) By mass%, Fe is 0.90% or more and 1.20% or less, Mg is 0.10% or more and 0.25% or less, and the balance is Al and inevitable impurities.
(2) By mass%, Fe is 1.01% or more and 2.2% or less, Mg is 0.05% or more and 0.5% or less, and one or more elements selected from Mn, Ni, Zr, and Ag are combined in a total of 0.005% or more and 0.2%. Contains below, the balance being Al and inevitable impurities.
(3) By mass%, Fe contains 1.01% or more and 2.2% or less, Cu contains 0.05% or more and 0.5% or less, and the balance is Al and inevitable impurities.
(4) Containing at least one of Fe by 1.0% to 2.2%, Cu by 0.05% to 0.5%, Mg by 0.1% to 0.5%, and Si by 0.04% to 0.3% by mass. Contains, the balance being Al and inevitable impurities.
(5) By mass%, Mg is 0.2% to 1.0%, Si is 0.1% to 1.0%, Cu is 0.1% to 0.5%, the balance being Al and inevitable impurities.
(6) By mass%, Mg is 0.2% to 1.0%, Si is 0.1% to 1.0%, Cu is 0.1% to 0.5%, the balance being Al and inevitable impurities. However, the mass ratio Mg / Si of Mg and Si satisfies 0.8 ≦ Mg / Si ≦ 2.7.
Feは、強度に優れるAl合金線が得られ、含有量が高いほどAl合金の強度が高まるが、導電率や靭性が低下し易く、伸線加工時などで断線が生じ易くなるため、Fe:2.2質量%以下が好ましい。Mn,Ni,Zr,Crは、導電率の低下が大きいものの、強度の向上効果が高い元素であり、Ag,Znは、導電率の低下が少なく、強度の向上効果をある程度有する。Cuは、導電率の低下が少なく、強度を向上することができる。Mgは、導電率の低下が大きいものの、強度の向上効果が高く、特にSiと同時に含有することで、強度をより向上できる。また、MgとSiを含有する場合に時効を行うと、時効硬化による強度の向上が期待できる。   Fe has an Al alloy wire with excellent strength, and the higher the content, the higher the strength of the Al alloy, but the electrical conductivity and toughness tend to decrease, and wire breakage tends to occur, so Fe: 2.2 mass% or less is preferable. Mn, Ni, Zr, and Cr are elements that have a high effect of improving the strength, although the decrease in conductivity is large. Ag and Zn have a small effect of reducing the conductivity and have a certain effect on improving the strength. Cu has little decrease in conductivity and can improve strength. Although Mg has a large decrease in electrical conductivity, the effect of improving the strength is high, and in particular, the strength can be further improved by containing it together with Si. In addition, when aging is performed when Mg and Si are contained, an improvement in strength due to age hardening can be expected.
更に、上記Al合金は、Ti及びBの少なくとも一方を含有すると、鋳造時のAl合金の結晶組織を微細にする効果があり、微細な結晶組織による強度の向上が期待できる。この微細化効果を十分に得るには、質量割合で、Tiを100ppm以上500ppm以下、Bを10ppm以上50ppm以下含有することが好ましい。   Furthermore, when the Al alloy contains at least one of Ti and B, there is an effect of making the crystal structure of the Al alloy at the time of casting fine, and an improvement in strength due to the fine crystal structure can be expected. In order to sufficiently obtain this fine effect, it is preferable that Ti is contained in a mass ratio of 100 ppm to 500 ppm and B is contained in an amount of 10 ppm to 50 ppm.
《特性》
上記組成のAl合金から構成されると共に後述するように伸線後に適宜軟化処理を施すことで、導電率:58%IACS以上、伸び:10%以上といった導電性及び靭性に優れるAl合金線とすることができる。添加元素の種類や量、軟化条件にもよるが、本発明Al合金線は、導電率:59%IACS以上、伸び:25%以上を満たすこともできる。靭性に優れることで、導体における端子部材との境界近傍で導体が破断し難く、本発明Al合金線は、端子付き電線の導体に好適に利用することができる。また、本発明Al合金線は、引張強さが110MPa以上200MPa以下であると、高靭性と高強度とを両立することができて好ましい。添加元素(種類や含有量)、製造条件(伸線加工時の加工度(断面減少率)、軟化条件など)を適宜調整することで、導電率、伸び、引張強さが上記特定の範囲を満たすAl合金線が得られる。
"Characteristic"
It is composed of an Al alloy having the above composition and, as will be described later, by appropriately performing a softening treatment after drawing, an Al alloy wire having excellent conductivity and toughness such as conductivity: 58% IACS or more and elongation: 10% or more is obtained. be able to. Although depending on the kind and amount of additive elements and softening conditions, the Al alloy wire of the present invention can also satisfy electrical conductivity: 59% IACS or more and elongation: 25% or more. By being excellent in toughness, the conductor hardly breaks in the vicinity of the boundary between the conductor and the terminal member, and the Al alloy wire of the present invention can be suitably used for the conductor of the electric wire with terminal. The Al alloy wire of the present invention preferably has a tensile strength of 110 MPa or more and 200 MPa or less because both high toughness and high strength can be achieved. By appropriately adjusting additive elements (type and content), manufacturing conditions (working degree during wire drawing (cross-sectional reduction rate), softening conditions, etc.), conductivity, elongation, and tensile strength are within the above specified ranges. A satisfying Al alloy wire is obtained.
《断面積》
本発明Al合金線の断面積は、伸線加工時の加工度を適宜調整することで変化させることができる。本発明Al合金線では、特に断面積を8mm2以下とする。例えば、Al合金線の断面形状を円形状とする場合、線径(直径)を3.2mm以下とする。断面積が8mm2超の線材では、上記Al露出比が十分に大きいことから、被覆層が存在することによる電食の低減効果が得られ難い。特に断面積が3mm2以下、更には断面積が1mm2以下のAl合金線の場合、被覆層が存在することによる電食の低減効果が顕著である。
<Cross-sectional area>
The cross-sectional area of the Al alloy wire of the present invention can be changed by appropriately adjusting the degree of processing at the time of wire drawing. In the Al alloy wire of the present invention, the cross-sectional area is particularly 8 mm 2 or less. For example, when the cross-sectional shape of the Al alloy wire is circular, the wire diameter (diameter) is set to 3.2 mm or less. In the wire having a cross-sectional area exceeding 8 mm 2 , the Al exposure ratio is sufficiently large, and therefore it is difficult to obtain the effect of reducing electrolytic corrosion due to the presence of the coating layer. In particular, in the case of an Al alloy wire having a cross-sectional area of 3 mm 2 or less, and further a cross-sectional area of 1 mm 2 or less, the effect of reducing electrolytic corrosion due to the presence of the coating layer is remarkable.
《断面形状》
本発明Al合金線は、伸線加工時のダイス形状によって種々の断面形状を有することができる。断面円形状が代表的であり、その他、楕円形状、矩形や六角形などの多角形状などの断面形状が挙げられる。形状は特に問わない。
"Cross-sectional shape"
The Al alloy wire of the present invention can have various cross-sectional shapes depending on the die shape at the time of wire drawing. A cross-sectional circular shape is typical, and other cross-sectional shapes such as an elliptical shape, a polygonal shape such as a rectangle or a hexagon are listed. The shape is not particularly limited.
《線材の形態》
<単線>
上記本発明Al合金線は、単線のまま利用することができる。
<撚り線>
上記本発明Al合金線を複数用意して撚り合わせた撚り線とすることもできる。細径のAl合金線(単線)であっても撚り合わせることで、強度の高い線材とすることができる。撚り合わせ本数は、特に問わない。例えば、7,11,19,37本が挙げられる。また、本発明Al合金撚り線は、撚り合わせた後、圧縮成形した圧縮線材とすると、単に撚り合わせた状態よりも線径が小さい線材とすることができる。この撚り線や圧縮線材は、撚り線や圧縮線材の断面積が8mm2以下となるように、撚り合せる各Al合金線の断面積を調整したり、圧縮度合いを調整する。
《Wire form》
<Single wire>
The Al alloy wire of the present invention can be used as it is.
<Stranded wire>
A plurality of the above-described Al alloy wires of the present invention can be prepared and twisted together. Even a thin Al alloy wire (single wire) can be made into a high strength wire by twisting together. The number of twists is not particularly limited. For example, 7,11,19,37 are mentioned. In addition, when the Al alloy stranded wire of the present invention is a compression wire that is compression-molded after being twisted, the wire diameter can be made smaller than that of a simply twisted state. For the stranded wire and the compressed wire, the cross-sectional area of each Al alloy wire to be twisted is adjusted and the degree of compression is adjusted so that the cross-sectional area of the stranded wire and the compressed wire is 8 mm 2 or less.
[被覆層]
《組成》
本発明Al合金線の外面に具える被覆層は、少なくとも最外層が錫(Sn)又は錫合金からなる。Snは、Alよりも貴な金属であり、Al合金と銅や銅合金との間に存在させることで、Alの腐食電流を低減することができるため、Al合金と銅や銅合金との間での電食を低減できる。錫合金は、Cu-Sn合金などが挙げられ、錫よりも腐食電流を低減し易い傾向にある。
[Coating layer]
"composition"
In the coating layer provided on the outer surface of the Al alloy wire of the present invention, at least the outermost layer is made of tin (Sn) or a tin alloy. Sn is a noble metal than Al. Since it can be reduced between Al alloy and copper or copper alloy, it can reduce the corrosion current of Al. Can reduce electric corrosion. Examples of the tin alloy include a Cu—Sn alloy, and the corrosion current tends to be reduced more easily than tin.
被覆層は、錫又は錫合金のみからなる単層でもよいし、錫又は錫合金からなる最外層とAl合金線との間に別の材質からなる中間層を具える多層構造、即ち、Al合金線の直上に設けられた中間層と、この中間層の上に設けられた上記最外層とを具える構成でもよい。中間層の構成材料は、ニッケル(Ni)、ニッケル合金、銅(Cu)、銅合金、亜鉛(Zn)、及び亜鉛合金から選択される少なくとも1種の金属が挙げられる。これらの金属は、Al合金と錫や錫合金との双方になじみがよく、Al合金と錫や錫合金との間に存在されることで、最外層とAl合金線との間を密着させ易い。中間層は、1層でも2層以上でもよい。ニッケル合金は、Zn-Ni合金、銅合金は、Cu-Sn合金、Cu-Zn合金、亜鉛合金は、Zn-Sn合金が挙げられる。   The coating layer may be a single layer made of only tin or tin alloy, or a multilayer structure including an intermediate layer made of another material between the outermost layer made of tin or tin alloy and the Al alloy wire, that is, an Al alloy. A configuration including an intermediate layer provided immediately above the line and the outermost layer provided on the intermediate layer may be employed. The constituent material of the intermediate layer includes at least one metal selected from nickel (Ni), nickel alloy, copper (Cu), copper alloy, zinc (Zn), and zinc alloy. These metals are well-suited to both Al alloys and tin and tin alloys, and because they exist between Al alloys and tin or tin alloys, it is easy to bring the outermost layer into close contact with Al alloy wires. . The intermediate layer may be one layer or two or more layers. Nickel alloys include Zn-Ni alloys, copper alloys include Cu-Sn alloys, Cu-Zn alloys, and zinc alloys include Zn-Sn alloys.
なお、上記Al合金線の外面に上記金属による被覆層に加えて樹脂層を具えることでも、Al合金の露出面積自体を無くすことができるため、電食を低減できる。例えば、Al合金線の周面に上記被覆層を具え、端面に樹脂層を具える構成とすることができる。或いは、上記被覆層を具えていないAl合金線であっても、端子部材の表面においてAl合金線と直接接触しない箇所の少なくとも一部、好ましくは当該箇所の全域に錫、錫合金から選択される少なくとも1種からなる層を設けたり、Al合金線の端部と端子部材との間に錫又は錫合金からなる薄板を存在させたり、Al合金線の端部を錫又は錫合金からなる有底筒状体で覆ってもよい。上記被覆層を具えるAl合金線に対して、更に、表面に上記錫などからなる層を具える端子部材を利用すると、Al合金線の電食をより効果的に低減することができる。   In addition, by providing a resin layer on the outer surface of the Al alloy wire in addition to the coating layer made of the metal, the exposed area of the Al alloy itself can be eliminated, so that electric corrosion can be reduced. For example, it can be set as the structure which provides the said coating layer in the surrounding surface of Al alloy wire, and provides the resin layer in an end surface. Alternatively, even if the Al alloy wire does not include the coating layer, at least a part of the surface of the terminal member that is not in direct contact with the Al alloy wire, preferably the entire region is selected from tin or a tin alloy. A layer made of at least one kind is provided, a thin plate made of tin or tin alloy is present between the end of the Al alloy wire and the terminal member, or the end of the Al alloy wire is made of a bottom made of tin or a tin alloy You may cover with a cylindrical body. When a terminal member having a layer made of tin or the like on the surface thereof is further used for the Al alloy wire having the coating layer, the electrolytic corrosion of the Al alloy wire can be more effectively reduced.
《厚さ》
最外層の厚さは、0超10μm以下といった非常に薄くても、電食抑制に十分に効果がある。10μm超と厚いと、端子部材を取り付ける際に被覆層が剥離し易くなる。被覆層が多層構造である場合、合計厚さは15μm以下が好ましく、そのうち最外層は、上記厚さを満たすことが好ましい。被覆層が多層構造である場合、合計厚さが15μm超と厚いと、端子部材を取り付ける際に被覆層が剥離し易くなる。一方、被覆層が薄過ぎるとピンホールが出来易くなる。ピンホールが存在すると、ピンホール部分で電食が加速的に進む。そのため、被覆層が錫又は錫合金からなる単層の場合、厚さは0.5μm以上10μm以下が好ましい。被覆層が多層構造である場合、下層にピンホールが存在しても、その上の層によりピンホールが埋められるため、各層は薄くてもよく、合計厚さは0.5μm以上10μm以下がより好ましく、各層の厚さは0.2μm以上7μm以下が好ましい。
"thickness"
Even if the thickness of the outermost layer is very thin, such as more than 0 and 10 μm or less, it is sufficiently effective in suppressing electrolytic corrosion. If it is thicker than 10 μm, the coating layer is easily peeled off when the terminal member is attached. When the coating layer has a multilayer structure, the total thickness is preferably 15 μm or less, and the outermost layer preferably satisfies the above thickness. When the coating layer has a multilayer structure, if the total thickness is thicker than 15 μm, the coating layer is easily peeled off when the terminal member is attached. On the other hand, if the coating layer is too thin, pinholes are easily formed. When pinholes exist, electrolytic corrosion proceeds at the pinholes at an accelerated rate. Therefore, when the coating layer is a single layer made of tin or a tin alloy, the thickness is preferably 0.5 μm or more and 10 μm or less. When the coating layer has a multilayer structure, even if pinholes exist in the lower layer, the pinholes are filled with the upper layer, so each layer may be thin, and the total thickness is more preferably 0.5 μm or more and 10 μm or less The thickness of each layer is preferably 0.2 μm or more and 7 μm or less.
《被覆領域》
上記被覆層は、Al合金線の外面の少なくとも一部、特に、端子部材が取り付けられるAl合金線の端部においてその周方向の領域の少なくとも一部に設けられていることが好ましい。Al合金線を絶縁電線の導体として利用する場合、絶縁電線の端部は絶縁層が除去され、露出されたAl合金線(導体)に端子部材が取り付けられる。この露出箇所のうち、端子部材で覆われる箇所(端子部材に直接接触する箇所)は、Al合金線が大気(特に、大気中の水分の溶存酸素など)に接触し難いことから、Al合金線が腐食し難い。一方、上記露出箇所のうち、端子部材に覆われず、かつ絶縁層にも覆われていない端子部材近傍の箇所(以下、導体露出箇所と呼ぶ)は、Al合金が腐食し易い。そのため、Al合金線の端部において、少なくとも導体露出箇所となり得る領域は、上記被覆層を具えることが好ましく、当該端部においてその周方向の全域に上記被覆層を具えていてもよい。他方、Al合金線において端子部材が取り付けられず、端子部材から十分に離れた箇所は、通常、絶縁層で覆われるため、上記被覆層が無くてもよい。また、端子部材が取り付けられるAl合金線の端部において、その周方向だけでなく、端面にも上記被覆層が設けられていると、Al合金の露出部分を無くすことができるため、電食の低減効果を更に高められる。
<Coating area>
The coating layer is preferably provided on at least a part of the outer surface of the Al alloy wire, in particular, at least a part of the circumferential region at the end of the Al alloy wire to which the terminal member is attached. When an Al alloy wire is used as a conductor of an insulated wire, the insulating layer is removed from the end of the insulated wire, and a terminal member is attached to the exposed Al alloy wire (conductor). Of these exposed locations, the locations covered with the terminal members (locations that are in direct contact with the terminal members) are difficult for Al alloy wires to contact the atmosphere (especially dissolved oxygen in the atmosphere). Is difficult to corrode. On the other hand, among the exposed portions, a portion in the vicinity of the terminal member that is not covered by the terminal member and not covered by the insulating layer (hereinafter referred to as a conductor exposed portion) is easily corroded by the Al alloy. Therefore, it is preferable that at least a region that can be exposed to the conductor in the end portion of the Al alloy wire includes the coating layer, and the end layer may include the coating layer in the entire circumferential direction. On the other hand, since the terminal member is not attached to the Al alloy wire and the portion sufficiently separated from the terminal member is usually covered with an insulating layer, the coating layer may not be provided. Moreover, in the end portion of the Al alloy wire to which the terminal member is attached, when the coating layer is provided not only in the circumferential direction but also on the end surface, the exposed portion of the Al alloy can be eliminated. The reduction effect can be further enhanced.
《形成方法》
被覆層は、めっき法、CVD法やPVD法といった蒸着法などの種々の形成方法が利用できる。電気めっきや無電解めっき、溶融めっきといっためっき法は、被覆層を容易に形成することができる。また、中間層のZn層の形成には、ジンケート処理やダブルジンケート処理などを好適に利用することができる。被覆層の構成材料に応じて適宜形成方法を選択するとよい。被覆層の形成時期は、後述する。
<Formation method>
For the coating layer, various forming methods such as a plating method, a vapor deposition method such as a CVD method and a PVD method can be used. Plating methods such as electroplating, electroless plating, and hot dipping can easily form a coating layer. In addition, zincate treatment, double zincate treatment, or the like can be suitably used for forming the intermediate Zn layer. A formation method may be appropriately selected according to the constituent material of the coating layer. The formation time of the coating layer will be described later.
[絶縁電線]
上記Al合金線(単線)やAl合金撚り線、圧縮線材は、電線用導体に好適に利用することができる。用途に応じて、このまま導体として使用することもできるし、この導体の外周に絶縁材料により形成した絶縁層を具える絶縁電線として使用することもできる。絶縁材料は、適宜選択することができる。例えば、ポリ塩化ビニル(PVC)やノンハロゲン樹脂、難燃性に優れる材料などが挙げられる。絶縁層の厚さは、所望の絶縁強度を考慮して適宜選択することができ、特に限定されない。
[Insulated wire]
The Al alloy wire (single wire), the Al alloy twisted wire, and the compressed wire can be suitably used as a conductor for electric wires. Depending on the application, it can be used as a conductor as it is, or can be used as an insulated wire having an insulating layer formed of an insulating material on the outer periphery of the conductor. The insulating material can be selected as appropriate. For example, polyvinyl chloride (PVC), a non-halogen resin, a material excellent in flame retardancy, and the like can be given. The thickness of the insulating layer can be appropriately selected in consideration of desired insulating strength, and is not particularly limited.
[端子付き電線]
Al合金線やAl合金撚り線、圧縮線材を導体とした絶縁電線であって、例えば、導体の全周(端面を含んでもよい)に亘って上記被覆層を具える場合、この絶縁電線の端部において絶縁層を剥がして導体部分を露出させ、この露出させた導体部分に、外部機器などの接続対象に接続できるように端子部材を取り付けることで、本発明端子付き電線が得られる。或いは、Al合金線やAl合金撚り線、圧縮線材であって、その外周に上記錫などの被覆層を具えていないものを導体とした絶縁電線の場合、この絶縁電線の端部において絶縁層を剥がして、導体部分を露出させ、この露出させた導体部分に上記被覆層を設けてから端子部材を取り付けることで、或いは露出させた導体部分に端子部材を取り付けてから、端子部材に覆われずに露出されている導体露出箇所を覆うように上記被覆層を設けることで、本発明端子付き電線が得られる。
[Wire with terminal]
An insulated wire having a conductor made of an Al alloy wire, an Al alloy stranded wire, or a compressed wire, for example, when the covering layer is provided over the entire circumference of the conductor (which may include an end face), the end of the insulated wire The insulating layer is peeled off at the portion to expose the conductor portion, and a terminal member is attached to the exposed conductor portion so as to be connected to a connection target such as an external device, whereby the electric wire with terminal of the present invention is obtained. Alternatively, in the case of an insulated wire using an Al alloy wire, an Al alloy twisted wire, or a compressed wire that does not have a coating layer of tin or the like on its outer periphery as a conductor, an insulating layer is provided at the end of the insulated wire. The conductor part is exposed by peeling off, and the terminal layer is attached after the covering layer is provided on the exposed conductor part, or after the terminal member is attached to the exposed conductor part, the terminal member is not covered. An electric wire with a terminal of the present invention is obtained by providing the covering layer so as to cover the exposed conductor portion exposed to the wire.
上記端子付き電線は、複数の絶縁電線に対して一つの端子部材を共有するような電線群を含んでいてもよい。複数の絶縁電線は、結束具などにより一纏まりに束ねることで、ハンドリング性に優れる。このような端子付き電線は、軽量化が望まれている種々の分野、特に、燃費の向上のために更なる軽量化が望まれている自動車に好適に利用することができる。端子部材は、電線の端部にかしめる(圧着する)ことで装着される圧着端子を好適に利用することができる。   The said electric wire with a terminal may contain the electric wire group which shares one terminal member with respect to a some insulated wire. A plurality of insulated wires are excellent in handling property by being bundled together by a binding tool or the like. Such a terminal-attached electric wire can be suitably used in various fields in which weight reduction is desired, particularly in automobiles in which further weight reduction is desired in order to improve fuel consumption. As the terminal member, a crimp terminal attached by crimping (crimping) on the end of the electric wire can be preferably used.
[製造方法]
上記被覆層を具える本発明Al合金線は、例えば、鋳造→熱間圧延→(ビレット鋳造材の場合:均質化処理)→冷間伸線加工→(適宜、軟化処理)→被覆層形成という工程により形成することができる。
[Production method]
The Al alloy wire of the present invention comprising the coating layer is, for example, casting → hot rolling → (in the case of billet cast material: homogenization treatment) → cold wire drawing → (appropriate softening treatment) → coating layer formation It can be formed by a process.
鋳造は、ビレット鋳造でもよいが、急冷凝固により結晶粒や晶析出物を微細化して微細組織を有する鋳造材が得られる連続鋳造が好ましい。連続鋳造により、結晶の微細化による強度の向上や、微細な晶析出物の分散による靭性の向上を図ることができる。急冷には、水冷銅鋳型や強制水冷機構などを利用するとよい。冷却速度は、600〜700℃において20℃/sec以上が好ましい。   The casting may be billet casting, but continuous casting is preferred in which a cast material having a microstructure is obtained by refining crystal grains and crystal precipitates by rapid solidification. By continuous casting, it is possible to improve strength by refining crystals and toughness by dispersing fine crystal precipitates. For rapid cooling, a water-cooled copper mold or a forced water cooling mechanism may be used. The cooling rate is preferably 20 ° C./sec or more at 600 to 700 ° C.
TiやBを添加する場合、溶湯を鋳型に注湯する直前に添加すると、Tiなどの局所的な沈降を抑制して、Tiなどが均等に混合された鋳造材を製造することができて好ましい。   When adding Ti or B, adding just before pouring the molten metal into the mold is preferable because it suppresses local sedimentation of Ti and the like and can produce a cast material in which Ti and the like are evenly mixed. .
上記鋳造工程と圧延工程とは、連続的に行うと、鋳造材に蓄積される熱を利用して熱間圧延を容易に行えて、エネルギー効率がよい上に、バッチ式の鋳造方法と比較して、鋳造圧延材の生産性に優れる。   When the above casting process and rolling process are carried out continuously, it is possible to easily perform hot rolling using the heat accumulated in the cast material, and it is energy efficient and compared with a batch casting method. In addition, it is excellent in productivity of cast rolled material.
伸線加工工程において、加工度は、所望の線径に応じて適宜選択することができる。得られた伸線材は、所望の本数を用意して撚り合わせ、撚り線とすることもできる。   In the wire drawing step, the degree of processing can be appropriately selected according to the desired wire diameter. As for the obtained wire drawing material, a desired number can be prepared and twisted together to form a stranded wire.
軟化処理は、結晶組織の微細化、及び加工硬化によって高めた線材の強度を極端に低下させることなく軟化して、線材の靭性を高めるために行う。軟化処理の条件は、適宜選択するとよく、例えば、処理後の線材(単線材又は撚り線)の伸びが10%以上となるような条件により行う。軟化処理には、連続処理又はバッチ処理のいずれも利用できる。   The softening treatment is performed in order to increase the toughness of the wire by softening without extremely reducing the strength of the wire that has been increased by refinement of the crystal structure and work hardening. The conditions for the softening treatment may be appropriately selected. For example, the softening treatment is performed under such a condition that the elongation of the treated wire (single wire or stranded wire) is 10% or more. For the softening treatment, either continuous treatment or batch treatment can be used.
撚り線は、複数の伸線材又は軟材を撚り合わせることで得られ、圧縮線材は、この撚り線を圧縮成形することで得られる。撚り線や圧縮線材の場合、上記軟化処理は、撚り合わせ前の線材のみに施してもよいし、撚り合わせ前後の双方で行ってもよいし、撚り合わせ前の伸線材に施さず、撚り線や圧縮線材にのみ施してもよい。   The stranded wire is obtained by twisting together a plurality of wire drawing materials or soft materials, and the compression wire material is obtained by compression molding the stranded wire. In the case of a stranded wire or a compressed wire, the softening treatment may be performed only on the wire before twisting, may be performed both before and after the twisting, or not on the wire drawing material before the twisting. Or may be applied only to the compressed wire.
伸線材や軟材、これらを撚り合わせた撚り線、圧縮線材に被覆層を形成することで、本発明Al合金線やAl合金撚り線が得られる。被覆層は、伸線材などの全長に亘って形成してもよいし、上述のように端子部材が取り付けられる端部のみに形成してもよい。撚り線や圧縮線材の場合、撚り合わされた状態で被覆層を形成してもよいが、撚り合わせる前の線材(伸線材、軟材)に被覆層を形成しておくと、撚り合せた線材間に被覆層が存在することにより、電食の低減効果を高められる。また、長尺な伸線材や軟材、これら撚り合わせた撚り線、圧縮線材を切断して、所定長のAl合金線やAl合金撚り線を作製する場合、Al合金線やAl合金線の端面に被覆層を有していないものが得られる。この場合、別途、端面に被覆層を設けてもよい。軟化処理を行う場合であって、軟化処理時の加熱温度よりも融点が低い材料からなる被覆層を具えるときには、軟化処理後に被覆層を形成する。軟化処理時の加熱温度よりも融点が高い材料からなる被覆層を具えるときには、軟化処理の前後のいずれでも、被覆層を形成することができる。   The Al alloy wire of the present invention and the Al alloy stranded wire can be obtained by forming a coating layer on a wire drawing material, a soft material, a stranded wire obtained by twisting these together, or a compression wire. The covering layer may be formed over the entire length of the wire drawing material or the like, or may be formed only at the end portion to which the terminal member is attached as described above. In the case of a stranded wire or a compressed wire, the coating layer may be formed in a twisted state, but if a coating layer is formed on the wire (drawn wire, soft material) before being twisted, the space between the twisted wires When the coating layer is present on the surface, the effect of reducing electrolytic corrosion can be enhanced. Also, when cutting long wire or soft wire, twisted stranded wire, or compression wire, to produce a predetermined length of Al alloy wire or Al alloy stranded wire, end faces of Al alloy wire or Al alloy wire Without the coating layer is obtained. In this case, you may provide a coating layer in an end surface separately. When a softening process is performed and a covering layer made of a material having a melting point lower than the heating temperature during the softening process is provided, the covering layer is formed after the softening process. When a coating layer made of a material having a melting point higher than the heating temperature during the softening treatment is provided, the coating layer can be formed either before or after the softening treatment.
本発明Al合金線、本発明Al合金撚り線、本発明絶縁電線、及び本発明端子付き電線は、耐食性に優れる。   The Al alloy wire of the present invention, the twisted Al alloy wire of the present invention, the insulated wire of the present invention, and the electric wire with terminal of the present invention are excellent in corrosion resistance.
端子付き電線の概略を示す部分構成図である。It is a partial block diagram which shows the outline of an electric wire with a terminal. 端子付き電線の腐食状況を説明する顕微鏡写真(25倍)であり、(A)は、試料No.1-5のB-B断面における部分拡大写真、(B)は、試料No.1-100のB-B断面における部分拡大写真、(C)は絶縁電線の断面写真を示す。It is a micrograph (25 times) explaining the corrosion situation of the electric wire with terminal, (A) is a partial enlarged photograph in the BB cross section of sample No. 1-5, (B) is a BB of sample No. 1-100 (C) shows a cross-sectional photograph of an insulated wire. 黄銅に対するアルミニウム合金の面積比と、腐食電流密度との関係を示すグラフである。It is a graph which shows the relationship between the area ratio of the aluminum alloy with respect to brass, and a corrosion current density.
(試験例1)
Al合金線を導体とする絶縁電線の端部に圧着端子を取り付けた端子付き電線を作製して腐食試験を行い、耐食性を評価した。
(Test Example 1)
A terminal-attached electric wire with a crimp terminal attached to the end of an insulated electric wire using an Al alloy wire as a conductor was prepared and subjected to a corrosion test to evaluate the corrosion resistance.
試料のうち、電線は、鋳造→圧延→伸線→軟化→被覆層の形成→撚り線→圧縮→絶縁層の形成という手順で作製した。具体的には、ベースとして純アルミニウム(99.7質量%以上Al)を用意して溶解し、得られた溶湯(溶融アルミニウム)に表1に示す添加元素を表1に示す含有量となるように投入して、Al合金溶湯を作製する。成分調整を行ったAl合金溶湯は、適宜、水素ガス除去処理や、異物除去処理を行うことが望ましい。   Among the samples, the electric wire was produced by the procedure of casting → rolling → drawing → softening → formation of coating layer → twisted wire → compression → formation of insulating layer. Specifically, pure aluminum (99.7% by mass or more Al) is prepared and melted as a base, and the obtained molten metal (molten aluminum) is charged with the additive elements shown in Table 1 to the contents shown in Table 1. Then, an Al alloy molten metal is produced. It is desirable that the Al alloy molten metal whose components have been adjusted is appropriately subjected to a hydrogen gas removal treatment or a foreign matter removal treatment.
ベルト-ホイール式の連続鋳造圧延機を用いて、用意したAl合金溶湯に鋳造及び熱間圧延を連続的に施し、φ9.5mmのワイヤーロッド(連続鋳造圧延材)を作製する。   Using a belt-wheel type continuous casting and rolling machine, the prepared molten Al alloy is continuously cast and hot-rolled to produce a φ9.5 mm wire rod (continuously cast rolled material).
上記ワイヤーロッドに冷間伸線加工を施して、線径φ0.3mmの伸線材を作製し、得られた伸線材に350℃×3時間の軟化処理(バッチ処理、還元ガス雰囲気)を施して軟材を作製する。なお、得られた軟材の導電率、伸び、引張強さを調べたところ、いずれの軟材も、導電率:58%IACS以上、伸び:10%以上、引張強さ:110〜200MPaであった。   The wire rod is subjected to cold wire drawing to produce a wire drawing material with a diameter of 0.3 mm, and the obtained wire material is subjected to softening treatment (batch treatment, reducing gas atmosphere) at 350 ° C. for 3 hours. Make softwood. When the conductivity, elongation, and tensile strength of the obtained soft material were examined, all of the soft materials had conductivity: 58% IACS or more, elongation: 10% or more, and tensile strength: 110 to 200 MPa. It was.
上記軟材に公知の電気めっき法やジンケート処理、ダブルジンケート処理により、表1に示す組成の被覆層を施し、軟材の全周面及び端面に被覆層を有する被覆線材を作製する。表1に示す被覆層は、欄の左側がAl合金線側、欄の右側が最外側であり、()内は光学顕微鏡の観察像を利用して測定した厚さを示し、「-」は、被覆層を有していないことを示す。なお、ジンケート処理、ダブルジンケート処理によるZn層は、せいぜい数十ナノオーダーの厚さであり、この厚さは、例えば、TEM(透過型電子顕微鏡)による観察像を利用して測定することができる。   The above-mentioned soft material is coated with a coating layer having the composition shown in Table 1 by a known electroplating method, zincate treatment, or double zincate treatment to produce a coated wire having a coating layer on the entire peripheral surface and end surface of the soft material. In the coating layer shown in Table 1, the left side of the column is the Al alloy wire side, the right side of the column is the outermost side, () indicates the thickness measured using an observation image of an optical microscope, ``-'' , Indicating that it does not have a coating layer. Note that the zinc layer by the zincate treatment and the double zincate treatment has a thickness of several tens of nanometers at most, and this thickness can be measured using an observation image by a TEM (transmission electron microscope), for example. .
上記被覆線材を複数本撚り合わせて、撚り線を作製する。ここでは、内側3本、外側8本の合計11本の被覆線材を撚り合わせた。   A plurality of the above-mentioned covered wire materials are twisted together to produce a stranded wire. Here, a total of 11 covered wires, 3 inside and 8 outside, were twisted together.
得られた撚り線(断面積:約0.77mm2)の外周に、絶縁材料(ここでは、ハロゲンフリー絶縁材料)により、絶縁層(厚さ0.2mm)を形成して、絶縁電線を作製する。この絶縁電線の端部に圧着端子を取り付けて、図1に示す端子付き電線を作製する。 An insulating layer (thickness 0.2 mm) is formed on the outer periphery of the obtained stranded wire (cross-sectional area: about 0.77 mm 2 ) with an insulating material (here, a halogen-free insulating material) to produce an insulated wire. A crimp terminal is attached to the end portion of the insulated wire to produce a terminal-attached wire shown in FIG.
端子付き電線10は、複数のAl合金線を撚り合わせてなる導体11と、導体11の外周を覆う絶縁層12とを具え、一端側の絶縁層12が剥ぎ取られて露出された導体11に端子部材(圧着端子)20が取り付けられている。端子部材20は、銅合金板の両縁側に適宜切り込みを入れてできた切片を折り曲げて形成したものであり、一端側の両切片22a,22bの縁が接するように二つ折りにされてなる平坦な雄端子部22を有する。また、電線10の絶縁層12部分を挟持するように、端子部材20の他端側の両切片21a,21bが折り曲げられている。端子部材20において上記絶縁層部分の挟持箇所と雄端子部22との間の中間部には、絶縁層12から露出された導体11が縦添えされ、この導体11を挟持するように両切片23a,23bが折り曲げられている。従って、露出された導体11の大部分は、切片23a,23bに覆われており、端面及びその近傍が切片23a,23bから露出した状態である。試料No.1-1〜1-7は、この露出部分に被覆層を具えており、Al露出比が実質的にゼロになっている。   The terminal-attached electric wire 10 includes a conductor 11 formed by twisting a plurality of Al alloy wires, and an insulating layer 12 covering the outer periphery of the conductor 11, and the insulating layer 12 on one end side is peeled off to expose the conductor 11. A terminal member (crimp terminal) 20 is attached. The terminal member 20 is formed by bending a piece made by appropriately making cuts on both edge sides of the copper alloy plate, and is flattened so that the edges of both pieces 22a, 22b on one end side are in contact with each other. A male terminal portion 22 is provided. Further, both pieces 21a and 21b on the other end side of the terminal member 20 are bent so as to sandwich the insulating layer 12 portion of the electric wire 10. In the terminal member 20, a conductor 11 exposed from the insulating layer 12 is vertically attached to an intermediate portion between the sandwiched portion of the insulating layer portion and the male terminal portion 22, and both pieces 23a are sandwiched so as to sandwich the conductor 11. 23b is bent. Therefore, most of the exposed conductor 11 is covered with the segments 23a and 23b, and the end surface and the vicinity thereof are exposed from the segments 23a and 23b. Sample Nos. 1-1 to 1-7 have a coating layer on the exposed portion, and the Al exposure ratio is substantially zero.
耐食性は、以下のように評価した。耐食性の試験として、塩水噴霧試験が知られているが、この試験の試料のように、異種金属で構成され、電食が生じ得る試料に塩水噴霧試験を適用すると、電食による試料の損傷が大き過ぎて、耐食性の評価が実質的にできない。そこで、このような電食が生じ得る試料に対して耐食性を適切に評価するために、腐食の進行が比較的緩やかに行われる環境を模擬した、以下の試験方法を採用した。   Corrosion resistance was evaluated as follows. The salt spray test is known as a corrosion resistance test. However, if the salt spray test is applied to a sample that is composed of dissimilar metals and can undergo electrolytic corrosion, such as the sample in this test, the sample may be damaged by electrolytic corrosion. It is too large to evaluate the corrosion resistance substantially. Therefore, in order to appropriately evaluate the corrosion resistance of a sample in which such electrolytic corrosion can occur, the following test method simulating an environment where the progress of corrosion is performed relatively slowly was adopted.
まず、NaCl(電解質)を超純水(溶媒)に溶かして、濃度が26質量%の中性水溶液(200g)を作製する。また、平均粒径が100μm程度のシリカ(SiO2)の粉末:100gを用意する。用いた電解質、溶媒、粒状体はいずれも市販品である。 First, NaCl (electrolyte) is dissolved in ultrapure water (solvent) to prepare a neutral aqueous solution (200 g) having a concentration of 26% by mass. Further, 100 g of silica (SiO 2 ) powder having an average particle diameter of about 100 μm is prepared. The electrolyte, solvent, and granular material used are all commercially available products.
用意したシリカの粉末を濾紙上に載せ、用意した上記水溶液(26%NaCl)をシリカの粉末の上から滴下した後、150℃に加熱した恒温槽中に入れて乾燥し、NaClが付着した粉末を得る(Cl-付着量:35000ppm)。得られた粉末を試料の一部が目視により確認できる程度に、試料(特に、電線と端子部材との接合部分)に満遍なく振り掛けて(厚さ1mm以下)、60℃、95%RHに設定した恒温恒湿槽に入れ、6日間(144時間)保持する。6日後、恒温恒湿槽から試料を取り出し、腐食状況を調べた。具体的には、図1において、絶縁層12が除去されて導体11が露出された部分であって、切片23a,23bで挟持されている箇所付近を切断し(B-B切断)、この断面を観察して、残存率(%)={(残存しているAl合金線の面積)/(作製したAl合金線の面積)}×100を求め、この残存率により耐食性を評価する。面積は、断面写真に画像処理などを施すことで容易に求められる。上記残存率が高いほど、耐食性が高いと言える。その結果を表2に示す。なお、塩水噴霧試験を行ったところ、残存するAl合金線の面積の測定が困難なほど、試料の損傷が酷かった。 The prepared silica powder is placed on a filter paper, and the prepared aqueous solution (26% NaCl) is dropped from above the silica powder, then placed in a thermostatic chamber heated to 150 ° C., dried, and the NaCl adheres. the obtained (Cl - deposition amount: 35,000 ppm). Sprinkle the obtained powder evenly over the sample (especially the joint between the wire and the terminal member) to the extent that a part of the sample can be visually confirmed (thickness 1 mm or less), and set to 60 ° C and 95% RH. Put in a thermo-hygrostat and hold for 6 days (144 hours). Six days later, the sample was taken out from the thermo-hygrostat and the corrosion state was examined. Specifically, in FIG. 1, the portion where the insulating layer 12 is removed and the conductor 11 is exposed, and the vicinity of the portion sandwiched between the sections 23a and 23b is cut (BB cutting), and this cross section is observed. Then, the residual rate (%) = {(the area of the remaining Al alloy wire) / (the area of the produced Al alloy wire)} × 100 is obtained, and the corrosion resistance is evaluated based on the residual rate. The area can be easily obtained by performing image processing or the like on the cross-sectional photograph. It can be said that the higher the residual ratio, the higher the corrosion resistance. The results are shown in Table 2. In addition, when the salt spray test was conducted, the sample was so severely damaged that it was difficult to measure the area of the remaining Al alloy wire.
表2に示すように、最外層に錫又は錫合金からなる被覆層を具えるAl合金線を導体とした試料は、残存率が高く、耐食性に優れることが分かる。図2(A)は、試料No.1-5のB-B断面の顕微鏡写真、図2(B)は、試料No.1-100のB-B断面の顕微鏡写真、図2(C)は、被覆電線の断面の顕微鏡写真である。なお、図2(C)の写真は、軟材を撚り合せた後、断面外形が円形状となるように圧縮加工を施した圧縮線材を導体とした被覆電線を示す。図2(A)〜(C)において、白っぽい領域がAl合金からなる部分であり、図2(A),(B)は、導体の一部を示す。図2(B)に示すように、上記被覆層を具えていない試料No.1-100は、Al合金線が腐食して欠損し、外形が崩れており、耐食性に劣ることが分かる。これに対して、上記被覆層を具えている試料No.1-5は、Al合金線が十分に残っており、耐食性に優れることが分かる。   As shown in Table 2, it can be seen that a sample using a conductor made of an Al alloy wire having a coating layer made of tin or a tin alloy as the outermost layer has a high residual rate and excellent corrosion resistance. 2A is a micrograph of the BB cross section of sample No. 1-5, FIG. 2B is a micro photo of the BB cross section of sample No. 1-100, and FIG. It is a microscope picture of a section. The photograph in FIG. 2 (C) shows a covered electric wire using a compressed wire that has been subjected to compression processing so that the cross-sectional outer shape becomes a circular shape after twisting soft materials. 2A to 2C, the whitish region is a portion made of an Al alloy, and FIGS. 2A and 2B show a part of the conductor. As shown in FIG. 2 (B), it can be seen that Sample No. 1-100, which does not have the coating layer described above, is inferior in corrosion resistance because the Al alloy wire is corroded and lost, and the outer shape is broken. On the other hand, it can be seen that Sample No. 1-5 having the coating layer has a sufficient Al alloy wire and is excellent in corrosion resistance.
また、表2に示すように、被覆層にZnなどからなる中間層を具える場合、耐食性により優れていた。この理由は、中間層を具えることで、錫又は錫合金からなる最外層が形成し易く、この最外層が十分に存在したためであると考えられる。   Further, as shown in Table 2, when the coating layer was provided with an intermediate layer made of Zn or the like, it was superior in corrosion resistance. The reason is considered to be that the outermost layer made of tin or a tin alloy is easily formed by providing the intermediate layer, and this outermost layer is sufficiently present.
更に、全周面にのみ被覆層を具え、端面に被覆層を具えない被覆線材を作製し、この被覆線材を用いて上述のように端子付き電線を作製して、上述のNaClが付着した粉末を用いた腐食試験を行い、耐食性を評価した。その結果、線材の端面にも被覆層を具える試料の方が、耐食性に優れていることを確認した。   Further, a coated wire material having a coating layer only on the entire peripheral surface and not having a coating layer on the end surface is produced. Using this coated wire material, an electric wire with a terminal is produced as described above, and the above-mentioned NaCl is adhered. A corrosion test was conducted to evaluate the corrosion resistance. As a result, it was confirmed that the sample having the coating layer on the end face of the wire rod was superior in corrosion resistance.
(試験例2)
導体が同一組成のAl合金線からなり、導体断面積が異なる絶縁電線を複数用意し、これらの絶縁電線を用いて、試験例1と同様にして端子付き電線を作製し、試験例1と同様にして耐食性を評価した。その結果を表3に示す。
(Test Example 2)
Prepare multiple insulated wires with conductors consisting of Al alloy wires with the same composition and different conductor cross-sectional areas, and use these insulated wires to make a terminal-attached wire in the same way as in Test Example 1, and as in Test Example 1. Thus, the corrosion resistance was evaluated. The results are shown in Table 3.
この試験では、表3に示す電線サイズを有する導体であって、導体を構成するAl合金線として被覆層を具えるものを用いた絶縁電線の試料No.2-1,2-2,2-3と、被覆層を具えていないものを用いた絶縁電線の試料No.2-110,2-120,2-130,2-200とを作製して、耐食性を比較した。導体は、試験例1と同様にして種々の線径の軟材を用意し、適宜な本数を撚り合わせた後、圧縮加工することで作製した圧縮線材を利用した。例えば、試料No.2-1の導体は、試験例1と同様にして線径φ0.3mmの軟材を合計11本撚り合せた後、試料No.2-200の導体は、試験例1と同様にして線径φ0.32mmの軟材を用意し、この軟材を合計128本撚り合わせた後、圧縮加工することで作製した圧縮線材を利用した。   In this test, sample Nos. 2-1, 2-2, 2- of insulated wires using conductors having the wire sizes shown in Table 3 and having a coating layer as an Al alloy wire constituting the conductors. 3 and sample Nos. 2-110, 2-120, 2-130, and 2-200 of insulated wires using those that did not have a coating layer were produced and their corrosion resistance was compared. As the conductor, soft wires having various wire diameters were prepared in the same manner as in Test Example 1, and a compressed wire prepared by compressing after twisting an appropriate number of wires was used. For example, the conductor of sample No. 2-1 was twisted a total of 11 soft materials having a wire diameter of φ0.3 mm in the same manner as in Test Example 1, and then the conductor of Sample No. 2-200 was the same as that of Test Example 1. Similarly, a soft wire having a wire diameter of 0.32 mm was prepared, and a total of 128 soft materials were twisted together, and then a compressed wire prepared by compression processing was used.
この試験結果により、Al合金線を導体とし、この導体の端部に端子部材が取り付けられた端子付き電線では、導体の断面積が8mm2超であれば、最外層に錫又は錫合金からなる被覆層を具えていなくても、ある程度耐食性が高いことが分かる。一方、導体の断面積が8mm2以下である場合、最外層に錫又は錫合金からなる被覆層を具えることで、耐食性を高められることが分かる。 According to this test result, in an electric wire with a terminal in which an Al alloy wire is a conductor and a terminal member is attached to the end of the conductor, the outermost layer is made of tin or a tin alloy if the cross-sectional area of the conductor exceeds 8 mm 2. It can be seen that even if no coating layer is provided, the corrosion resistance is high to some extent. On the other hand, when the cross-sectional area of the conductor is 8 mm 2 or less, it can be seen that the corrosion resistance can be improved by providing the outermost layer with a coating layer made of tin or a tin alloy.
なお、上述した実施形態は、本発明の要旨を逸脱することなく、適宜変更することが可能であり、上述した構成に限定されるものではない。例えば、Al合金線の組成、被覆層の組成及び厚さ、端子部材の組成を適宜変化させてもよい。また、撚り合わせる線材の大きさや形状、撚り本数を変更してもよい。   The above-described embodiment can be appropriately changed without departing from the gist of the present invention, and is not limited to the above-described configuration. For example, the composition of the Al alloy wire, the composition and thickness of the coating layer, and the composition of the terminal member may be appropriately changed. Moreover, you may change the magnitude | size and shape of a wire to twist together, and the number of twists.
本発明端子付き電線は、耐食性に優れる上に、軽量であることから、例えば、自動車の他、飛行機などの輸送機器、ロボットなどの産業機器の配線に好適に利用することができる。本発明絶縁電線は、上記本発明端子付き電線の構成材料に好適に利用することができる。本発明アルミニウム合金線及び本発明アルミニウム撚り線は、上記本発明絶縁電線の導体に好適に利用することができる。   Since the electric wire with terminal of the present invention is excellent in corrosion resistance and lightweight, it can be suitably used for wiring of, for example, automobiles, transportation equipment such as airplanes, and industrial equipment such as robots. The insulated wire of the present invention can be suitably used as a constituent material for the above-described wire with a terminal of the present invention. The aluminum alloy wire of the present invention and the aluminum strand wire of the present invention can be suitably used for the conductor of the above insulated wire of the present invention.
10 端子付き電線 11 導体 12 絶縁層 20 端子部材
21a,21b,22a,22b,23a,23b 切片 22 雄端子部
10 Electric wire with terminal 11 Conductor 12 Insulation layer 20 Terminal material
21a, 21b, 22a, 22b, 23a, 23b Section 22 Male terminal

Claims (9)

  1. 自動車用電線の導体に用いられるアルミニウム合金線であって、
    前記合金線は、断面積が8mm2以下であり、
    前記合金線の外面の少なくとも一部に被覆層を具えており、
    前記被覆層の最外層が錫又は錫合金から構成されていることを特徴とするアルミニウム合金線。
    An aluminum alloy wire used for conductors of automobile wires,
    The alloy wire has a cross-sectional area of 8 mm 2 or less,
    A coating layer is provided on at least a part of the outer surface of the alloy wire;
    An aluminum alloy wire, wherein the outermost layer of the coating layer is made of tin or a tin alloy.
  2. 前記被覆層は、前記合金線の直上に設けられた中間層と、この中間層の上に設けられた前記最外層とを具え、
    前記中間層は、ニッケル、ニッケル合金、銅、銅合金、亜鉛、及び亜鉛合金かから選択される少なくとも1種の金属から構成されていることを特徴とする請求項1に記載のアルミニウム合金線。
    The coating layer comprises an intermediate layer provided immediately above the alloy wire, and the outermost layer provided on the intermediate layer,
    2. The aluminum alloy wire according to claim 1, wherein the intermediate layer is made of at least one metal selected from nickel, nickel alloy, copper, copper alloy, zinc, and zinc alloy.
  3. 前記最外層の厚さが10μm以下であることを特徴とする請求項1又は2に記載のアルミニウム合金線。   3. The aluminum alloy wire according to claim 1, wherein a thickness of the outermost layer is 10 μm or less.
  4. 前記被覆層の合計厚さが15μm以下であることを特徴とする請求項2又は3に記載のアルミニウム合金線。   4. The aluminum alloy wire according to claim 2, wherein the total thickness of the coating layer is 15 μm or less.
  5. 前記合金線の周面の少なくとも一部及び端面に前記被覆層を具えることを特徴とする請求項1〜4のいずれか1項に記載のアルミニウム合金線。   5. The aluminum alloy wire according to claim 1, wherein the coating layer is provided on at least a part and an end surface of a peripheral surface of the alloy wire.
  6. 請求項1〜5のいずれか1項に記載の複数のアルミニウム合金線を撚り合わせてなり、この撚り線の断面積が8mm2以下であることを特徴とするアルミニウム合金撚り線。 An aluminum alloy stranded wire comprising a plurality of aluminum alloy wires according to any one of claims 1 to 5 twisted together, and a cross-sectional area of the stranded wire being 8 mm 2 or less.
  7. アルミニウム合金からなる導体と、この導体の外周に絶縁層を具える絶縁電線であって、
    前記導体は、請求項1〜5のいずれか1項に記載のアルミニウム合金線、複数の当該アルミニウム合金線を撚り合わせた撚り線、及び撚り線を圧縮成形した圧縮線材のいずれかであることを特徴とする絶縁電線。
    但し、前記撚り線の断面積、及び前記圧縮線材の断面積は、8mm2以下とする。
    An insulated wire having a conductor made of an aluminum alloy and an insulating layer on the outer periphery of the conductor,
    The conductor is any one of the aluminum alloy wire according to any one of claims 1 to 5, a stranded wire obtained by twisting a plurality of the aluminum alloy wires, and a compressed wire material obtained by compression-molding a stranded wire. Characterized insulated wire.
    However, the cross-sectional area of the stranded wire and the cross-sectional area of the compressed wire are 8 mm 2 or less.
  8. 前記絶縁電線の端部は、前記絶縁層が除去されて導体が露出されており、この露出された導体の外面の少なくとも一部に前記被覆層を具えることを特徴とする請求項7に記載の絶縁電線。   8. The end portion of the insulated wire is characterized in that the insulating layer is removed and a conductor is exposed, and the covering layer is provided on at least a part of the outer surface of the exposed conductor. Insulated wires.
  9. 請求項8に記載の絶縁電線と、この絶縁電線の端部に取り付けられた、銅又は銅合金から構成される端子部材とを具え、
    前記絶縁電線において絶縁層が除去されて導体が露出された箇所であって、端子部材に覆われていない箇所の外面の少なくとも一部に前記被覆層を具えることを特徴とする端子付き電線。
    The insulated wire according to claim 8, and a terminal member made of copper or a copper alloy attached to an end portion of the insulated wire,
    An electric wire with a terminal, wherein the covering layer is provided on at least a part of an outer surface of a portion of the insulated wire where the insulating layer is removed and the conductor is exposed and is not covered with the terminal member.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5211112A (en) * 1975-07-18 1977-01-27 Tokyo Alum Senzai Kk Highly corrosion resistant soft aluminum alloy for electric conductanc e
JPS5460232A (en) * 1977-10-21 1979-05-15 Mitsubishi Electric Corp Manufacture of anti-corrosive aluminium conductor
JP2000207940A (en) * 1999-01-18 2000-07-28 Furukawa Electric Co Ltd:The Conductor of al alloy for automobile
JP2003229192A (en) * 2002-02-05 2003-08-15 Auto Network Gijutsu Kenkyusho:Kk Terminal structure of aluminum wire preventing electric corrosion
JP2005336549A (en) * 2004-05-27 2005-12-08 Aluminum Senzai Kk Aluminum alloy for conductive wire for automobile, and method for manufacturing wire of the alloy
JP2008112620A (en) * 2006-10-30 2008-05-15 Auto Network Gijutsu Kenkyusho:Kk Electric wire conductor and its manufacturing method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5211112A (en) * 1975-07-18 1977-01-27 Tokyo Alum Senzai Kk Highly corrosion resistant soft aluminum alloy for electric conductanc e
JPS5460232A (en) * 1977-10-21 1979-05-15 Mitsubishi Electric Corp Manufacture of anti-corrosive aluminium conductor
JP2000207940A (en) * 1999-01-18 2000-07-28 Furukawa Electric Co Ltd:The Conductor of al alloy for automobile
JP2003229192A (en) * 2002-02-05 2003-08-15 Auto Network Gijutsu Kenkyusho:Kk Terminal structure of aluminum wire preventing electric corrosion
JP2005336549A (en) * 2004-05-27 2005-12-08 Aluminum Senzai Kk Aluminum alloy for conductive wire for automobile, and method for manufacturing wire of the alloy
JP2008112620A (en) * 2006-10-30 2008-05-15 Auto Network Gijutsu Kenkyusho:Kk Electric wire conductor and its manufacturing method

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