JPS581089A - Heat resistant copper wire covered with silver and its manufacture - Google Patents
Heat resistant copper wire covered with silver and its manufactureInfo
- Publication number
- JPS581089A JPS581089A JP9798781A JP9798781A JPS581089A JP S581089 A JPS581089 A JP S581089A JP 9798781 A JP9798781 A JP 9798781A JP 9798781 A JP9798781 A JP 9798781A JP S581089 A JPS581089 A JP S581089A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- copper
- zinc
- wire
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は銀被覆銅線、特に、゛電子部品用等の信頼性を
要求される導線として用いられる耐熱銀被覆銅線および
その製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver-coated copper wire, particularly to a heat-resistant silver-coated copper wire used as a conductive wire for electronic parts requiring reliability, and a method for manufacturing the same.
銀被覆導線は、銀が酸化被膜を形成しにくいという特性
によって、接触抵抗の経時変化が少なく。Silver-coated conductor wires have a property that silver does not easily form an oxide film, so the contact resistance changes little over time.
半田付性が優れ、熱劣化が起りにくい等の特性を有し、
信頼性の要求される分野に広く使用されている。It has characteristics such as excellent solderability and resistance to thermal deterioration.
Widely used in fields where reliability is required.
しかしながら、導体となる銅や銅合金上に直接銀を被覆
した銀被覆銅線においては、加熱されると銅が拡散して
銀表面にまで露呈し変色を起したり、高湿環境中での使
用時にはピンホール腐蝕が増長されてしまう等の欠点を
具有し、それ故、銀被覆層の厚さを３μ以上に設けねば
ならず、銀被覆銅線の価格が高価とならざるものであっ
た。However, in silver-coated copper wires, in which silver is directly coated on the copper or copper alloy that serves as the conductor, when heated, the copper diffuses and is exposed to the silver surface, causing discoloration or in high-humidity environments. It has disadvantages such as increased pinhole corrosion during use, and therefore the silver coating layer must be thicker than 3μ, making the silver-coated copper wire expensive. .
このような耐熱性、耐蝕性を改善するために、銅表面に
ニッケルめっきを行った後に銀を被覆するという手段が
一般的に用いられている。しかし、この手段においても
、銀が他の金属と比較して酸素を容易に通過するという
性質を有するために、酸化雰囲気中で加熱されると、銀
被覆層を通過する酸素によって下地であるニッケル層表
面が酸化されてしまい、それにより、銀被覆層のニッケ
ル表面への密着力が低下して銀被覆層が剥離してしまう
ような密着性の不良や、半田付を行う際にニッケル下地
層表面で半田されることに起因する半田付不良等の現象
を生じるものであった。In order to improve such heat resistance and corrosion resistance, a method is generally used in which the copper surface is plated with nickel and then coated with silver. However, even with this method, since silver has the property of passing oxygen more easily than other metals, when it is heated in an oxidizing atmosphere, the oxygen passing through the silver coating layer causes the underlying nickel to pass through. The surface of the layer is oxidized, which reduces the adhesion of the silver coating layer to the nickel surface, resulting in poor adhesion such as the silver coating layer peeling off, or when soldering the nickel base layer. Phenomena such as poor soldering occur due to soldering on the surface.
また、同様な目的を達成するために、特開昭４６−２８
４５９号において、銅表面に真鍮を０．５μ以上の厚さ
で被覆した後に銀を被覆する手段が開示されている。し
かしながら、この真鍮下地銀被覆銅線は銅に直接に銀被
覆したものよりは耐熱性が良好ではあるが、ニッケル下
地銀被覆銅線に比較すると耐熱性が不足するものであり
、更に、真鍮被覆層にある銅が銀被覆層中に拡散し易い
ために銅に直接銀被覆した場合と同等な特性まで劣化さ
れがちなものであった。In addition, in order to achieve the same purpose,
No. 459 discloses a means of coating a copper surface with brass to a thickness of 0.5 μm or more and then coating with silver. However, although this brass-undercoated, silver-coated copper wire has better heat resistance than copper coated directly with silver, it lacks heat resistance compared to nickel-undercoated, silver-coated copper wire. Since the copper in the layer easily diffuses into the silver coating layer, the properties tend to deteriorate to the same level as when copper is directly coated with silver.
従って、本発明の目的は酸化雰囲気中における熱負荷に
対して、銀被覆層の密着性および半田付性の向上を確保
出来、それにより、安価でかつ信頼性の高い銀被覆銅線
を提供することにある。Therefore, an object of the present invention is to provide an inexpensive and highly reliable silver-coated copper wire that can ensure improved adhesion and solderability of the silver coating layer against heat loads in an oxidizing atmosphere. There is a particular thing.
本発明の特色とするところは、銅、銅合金または銅被鋼
線のように銅または銅を主体とする合金を少なくとも表
面に有する導線（以下、これを「銅線」と総称する。）
の表面に、適当な厚さ、望ましくは、０．０１〜０．５
μの厚さの亜鉛めっき下地層を設け、さらに銀被覆をそ
の上に設けた点であり、その製造に当っては適当な厚さ
の亜・鉛メッキおよび銀メッキの後に周知の伸延加工お
よび熱処理を行う点である。The present invention is characterized by a conductive wire having copper or an alloy mainly composed of copper on at least its surface, such as copper, copper alloy, or copper-coated wire (hereinafter collectively referred to as "copper wire").
on the surface to a suitable thickness, preferably 0.01 to 0.5
The point is that a galvanized base layer with a thickness of μ is provided, and a silver coating is further provided on top of it, and in manufacturing it, after zinc-lead plating and silver plating of an appropriate thickness, well-known drawing processing and This is the point of heat treatment.
次に、本発明による銀被覆銅線の実施例を、従来のもの
との比較と共に以下で説明する。Next, examples of silver-coated copper wires according to the present invention will be described below along with comparisons with conventional ones.
実施例 １
直径１．６龍の配線用銅線上にシアン化浴により電気亜
鉛めっきを厚さ０．２μまで行って下地めっきし、その
上に、シアン化浴で電気銀めっきを厚さ３μまでめっき
した。このめっきした線を還元雰囲気中で８０００．５
秒間の熱処理を施してめつきの密着性を向上させた後、
直径０．８順に伸延加工し、再度熱処理を行い、所定の
硬度の銀被覆銅線を本発明に従って作成した。このとき
、完成後の銅線１上の亜鉛めっき層２および銀めっき層
乙の厚さはそれぞれ０１μおよび１．５μであった。Example 1 On a wiring copper wire with a diameter of 1.6 mm, conduct electrogalvanizing to a thickness of 0.2 μm in a cyanide bath to provide base plating, and then electrolytic silver plating to a thickness of 3 μm in a cyanide bath on top of the base plating. Plated. 8000.5 in a reducing atmosphere.
After applying heat treatment for seconds to improve plating adhesion,
The wires were stretched in order of 0.8 diameter and heat treated again to produce silver-coated copper wires of a predetermined hardness according to the present invention. At this time, the thicknesses of the zinc plating layer 2 and the silver plating layer B on the copper wire 1 after completion were 01 μm and 1.5 μm, respectively.
比較例 １
一方、従来における銀被覆線として、直径１．６肩冨の
配線用銅線上に直接６μと７μ厚さの銀めっきをそれぞ
れ設け、上述した本発明法による場合と同様に、直径０
，８朋に伸延加工および熱処理された銀被覆銅線と、直
径１．６朋の配線用銅線上に、シアン化浴で７００ｕ−
３０Ｚｎの合成比の厚さ１μの真鍮めっきおよび０．６
μのニッケルめっきをそれぞれ設けた後に銀めっきを厚
さ３μで設け、上述と同様にして、直径０．８ ｔｓｍ
の銀被覆銅線をそれぞれ作成した。Comparative Example 1 On the other hand, as a conventional silver-coated wire, silver plating with a thickness of 6μ and 7μ was respectively provided directly on a wiring copper wire with a diameter of 1.6mm, and as in the case according to the method of the present invention described above, silver plating with a diameter of 0
A silver-coated copper wire that had been drawn and heat treated to a diameter of 1.6 mm and a wiring copper wire of 1.6 mm in diameter was coated with a cyanide bath at a temperature of 700 μm.
30Zn composition ratio 1μ thick brass plating and 0.6
After providing each μ nickel plating, silver plating was applied to a thickness of 3μ, and the diameter was 0.8 tsm in the same manner as above.
silver-coated copper wires were prepared.
このようにして作成された本発明および従来の銀被覆線
を大気中、１８０ｃの温度条件で夫々０時間、２４時間
、４８時間および９６時間露呈したときのそれぞれの外
観の変色性と半田付性とを判定したところ、第１表に示
すような結果を得た。Discoloration and solderability of the appearance and solderability of the silver coated wires of the present invention and the conventional silver coated wires prepared in this way were exposed in the atmosphere at a temperature of 180°C for 0 hours, 24 hours, 48 hours and 96 hours, respectively. The results shown in Table 1 were obtained.
尚、外観の変色性の評価は、
変色無を良（○）、若干変色有を普通（△）、黄変を不
良（×）として行い、半田付性の評価はぬれ面積により
、９０係以上を良（○）、７０〜９０％を普通（△）、
７０係未満を不良（×）として行った。Appearance discoloration was evaluated as good (○) with no discoloration, fair (△) with slight discoloration, and poor (×) with yellowing, and solderability was evaluated based on the wetted area with a coefficient of 90 or higher. Good (○), 70-90% fair (△),
Those with a score of less than 70 were classified as defective (x).
第１表
この結果、本発明による銀被覆銅線は、銀めっき厚が１
．５μと、比較的薄にも拘らず外観および半田付性が長
時間にわたり全て良好であるのに対し、従来の下地めっ
きのない銀被覆銅線では２倍以上の厚さである３、５μ
の銀めっきが必要であり、また、真鍮下地めっきおよび
ニッケルめっきを施されかつ同一厚（１，５μ）の銀め
っきを有する銀被覆銅線では経時的劣化を生ずる。Table 1 As a result, the silver-coated copper wire according to the present invention has a silver plating thickness of 1
．． Although it is relatively thin at 5μ, its appearance and solderability are good over a long period of time, whereas conventional silver-coated copper wire without base plating has a thickness of 3.5μ, which is more than twice the thickness.
silver plating is required, and silver-coated copper wires that have been subjected to brass underplating and nickel plating and have the same thickness (1.5 μm) of silver plating will deteriorate over time.
このことは、本発明によれば信頼性を低下させることな
しに、銀の使用量を減少でき、それにより、安価な耐熱
銀被覆銅線を提供できることを示している。This shows that according to the present invention, the amount of silver used can be reduced without deteriorating reliability, and thereby an inexpensive heat-resistant silver-coated copper wire can be provided.
実施例 ２
本発明による亜鉛下地めっき層の厚さと銀被覆銅線の伸
延性この関係を次のようにして調べた。Example 2 The relationship between the thickness of the zinc undercoating layer and the extensibility of the silver-coated copper wire according to the present invention was investigated as follows.
直径１．６ ｍｙｉの配線用銅線に、実施例１と同様に
して、最終めっき厚が０，０１μ、０．１μ、０．５μ
および１μの各厚さとなるよう亜鉛めっきし、それぞれ
に３μの銀めっきをしたのち、最終銀めっき厚１．５μ
を有する直径０．８龍の各銀被覆銅線に加工した。Copper wiring for wiring with a diameter of 1.6 myi was coated with final plating thicknesses of 0.01μ, 0.1μ, and 0.5μ in the same manner as in Example 1.
After galvanizing each layer to a thickness of 1μ and silver plating to a thickness of 3μ, the final silver plating thickness is 1.5μ.
Each silver-coated copper wire with a diameter of 0.8 mm was processed.
比較例 ２
この伸延加工後における銀被覆銅線の外観により伸線性
を判定し、また、９６時間経過後における熱劣化試験に
よる外観の変色性および半田付性も判定した。Comparative Example 2 The wire drawability was determined based on the appearance of the silver-coated copper wire after drawing, and the discoloration of the appearance and solderability were also determined by a heat deterioration test after 96 hours had elapsed.
尚、亜鉛めっき厚“Ｏ”は参考のために作成した下地め
っきなしの銀被覆銅線である。Note that the zinc plating thickness "O" is a silver-coated copper wire without base plating prepared for reference.
伸線性の評価は、
銀剥離無しを良（○）、銀剥離有りを普通、へとして行
い、外観の変色性および半田付性については比較例１の
評価と同じである。The wire drawability was evaluated as good (◯) if there was no silver peeling, and fair or poor if there was silver peeling, and the evaluation of discoloration of appearance and solderability was the same as in Comparative Example 1.
これらの結果を第２表に示す。These results are shown in Table 2.
この結果から、伸線性、変色性および半田付性の全ての
特性を満足できる亜鉛メッキの厚さは′００１〜０．５
μの場合であり、１μ厚の亜鉛めっきの場合、伸延加工
後に銀めっき層が剥離してしまい変色性および半田付性
の評価は行えなかった。From this result, the thickness of zinc plating that satisfies all the characteristics of wire drawability, discoloration, and solderability is '001~0.5.
In the case of 1 μ thick zinc plating, the silver plating layer peeled off after stretching, making it impossible to evaluate discoloration and solderability.
このことは銀めっき層の密着性の低下に起因すると判断
された。It was determined that this was due to a decrease in the adhesion of the silver plating layer.
また、０．０１μ未満の亜鉛下地めっきを有する場合の
試料として、０．００８μの厚さで同様にして銀被覆銅
線を作成し、同様な実験を行ったところ、亜鉛めっきが
施されていない銀被覆銅線の特性と、変色の程度が少な
いとはいえ、実質的に同等であった。このことは、亜鉛
下地めっき層が加熱中における銅の拡散を抑制するに足
る厚さを有していないことが顕微鏡観察により確認され
た。In addition, as a sample with a zinc underplating of less than 0.01μ, a silver-coated copper wire with a thickness of 0.008μ was similarly prepared and a similar experiment was conducted, and it was found that no zinc plating was applied. The characteristics were substantially the same as those of the silver-coated copper wire, although the degree of discoloration was less. This was confirmed by microscopic observation that the zinc underplating layer did not have a thickness sufficient to suppress copper diffusion during heating.
実施例 ６
本発明における所定の最終線径の銀被覆銅線を作成する
場合の伸延加工および熱処理による影響を確認するため
に次のようにして銀被覆銅線を得た。Example 6 In order to confirm the influence of stretching and heat treatment when producing a silver-coated copper wire with a predetermined final wire diameter in the present invention, a silver-coated copper wire was obtained in the following manner.
直径０．８關の配線用銅線に亜鉛下地めっきの後に銀め
っきを施した銀被覆銅線であって伸延加工および熱処理
されていないものと、直径０．８２ ｖｒｍの配線用銅
線に亜鉛下地めっきを施こした後鍋めつきを行ない、更
に伸延加工および熱処理により直径０．８ ｍｒｘとさ
れた銀被覆銅線と、直径１．２ ｍｔｎおよび直径１．
６１ｍの各配線用銅線に亜鉛下地めっきおよび銀めっき
をそれぞれ行ない、伸延加工および熱処理によってそれ
ぞれ直径０．８朋とされて、銀被覆銅線を用意すると共
に夫々について亜鉛メッキを施さない銀被覆銅線を比較
用として準備し、それらについて、熱劣化試験を行った
。試験方法およびその評価については比較例１で行った
のと同様である。このとき、・銀めっき厚は全て１．５
μに設定した。A silver-coated copper wire with a diameter of 0.8 vrm that has been subjected to zinc underplating and then silver plating, and which has not been stretched or heat treated, and a copper wire with a diameter of 0.82 vrm that has been zinc-plated. A silver-coated copper wire that was subjected to base plating and then pan-plated, and further stretched and heat-treated to a diameter of 0.8 mrx, a diameter of 1.2 mtn, and a diameter of 1.2 mrx.
Each 61 m copper wire for wiring was subjected to zinc underplating and silver plating, and each was made into a diameter of 0.8 mm by stretching processing and heat treatment, and silver-coated copper wire was prepared, and each was silver-coated without zinc plating. Copper wires were prepared for comparison and a thermal deterioration test was conducted on them. The test method and evaluation were the same as those performed in Comparative Example 1. At this time, the silver plating thickness is all 1.5
It was set to μ.
これらの各銀被覆銅線について、比較例１と同様な試験
による結果を第３表に示す。評価もまた比較例１の評価
と同様である。Table 3 shows the results of the same tests as in Comparative Example 1 for each of these silver-coated copper wires. The evaluation is also the same as that of Comparative Example 1.
この結果において、特に注目すべきことの１つは、亜鉛
下地めっきを有する銀被覆銅線の直接めっきしたものが
９６時間経過時に鉛いて外観に変色を生ずるのに対し、
直径０．８２朋を直＆ ０．８ ｒｎｘの線径へと非常
に微少ではあるが伸延加工されたものは変色しないこと
である。また、下地めっき層のない銀被覆銅線において
も、伸延加工を施されたものの方が直接めっきしたもの
より変色性が優れていることである。One thing that is particularly noteworthy about these results is that directly plated silver-coated copper wire with a zinc undercoat becomes leaded and discolored in appearance after 96 hours.
A wire that has been stretched from a diameter of 0.82 mm to a wire diameter of 0.8 rnx will not change color, albeit very slightly. Furthermore, even in silver-coated copper wires without a base plating layer, those that have been subjected to drawing processing have better discoloration than those that have been directly plated.
このことは下地めっき層の有無に掛わらず、伸延加工を
受けることにより、銀めっき層のめっき粒子間の間隙が
実質的に閉鎖されてしまうことに起因することを顕微鏡
観察により確認された。It was confirmed by microscopic observation that this was due to the fact that the gaps between the plating particles in the silver plating layer were substantially closed by the stretching process, regardless of the presence or absence of the base plating layer.
上述の各実験において、銅線上の下地めっき層を亜鉛単
体で設けるよう説明したが、この下地層となる亜鉛は、
銅と銀との間に介在することにより、鋼中への拡散を抑
制して変色の防止および半田付性の低下防止するために
用いられるものであり、従って、亜鉛の代りにＡｙ−Ｚ
ｒＬ合金や５ｙｔ＝ｚｙｔ合金等により下地めっき層を
作成しても同等な効果を有することは容易に理解されよ
う。In each of the above experiments, it was explained that the base plating layer on the copper wire was provided with zinc alone, but the zinc that was the base layer was
By intervening between copper and silver, it is used to suppress diffusion into the steel and prevent discoloration and deterioration of solderability. Therefore, Ay-Z is used instead of zinc.
It is easily understood that the same effect can be obtained even if the base plating layer is made of rL alloy, 5yt=zyt alloy, or the like.
また、亜鉛めっき厚は、実験例２の結果から、０．０１
〜０．５μに選定されるのが好ましいが、伸線畑土誤差
や次土程への移送時の機械的世傷や原価低減等の観点か
ら０．１μ前後の厚さに選定されるのが好ましい。同様
に、銀めっき厚についても加工誤差や機械的損傷あるい
は生産性や原価低減等の観点から、０．７〜６μの範囲
に選定するのが好ましい。In addition, from the results of Experimental Example 2, the zinc plating thickness is 0.01
It is preferable to select a thickness of ~0.5μ, but from the viewpoints of errors in the field soil for wire drawing, mechanical damage during transfer to the next stage, and cost reduction, it is recommended to select a thickness of around 0.1μ. is preferred. Similarly, the silver plating thickness is preferably selected in the range of 0.7 to 6 μm from the viewpoint of processing errors, mechanical damage, productivity, cost reduction, etc.
上述の如く、本発明によれば、銅線の表面に下地めっき
層として亜鉛または亜鉛合金めっきな行つた後に銀めっ
きを行うことにより、熱劣化による外観の変色性および
半田付性の低下を防止できることとなる。As described above, according to the present invention, silver plating is performed after zinc or zinc alloy plating is performed as a base plating layer on the surface of the copper wire, thereby preventing discoloration of the appearance and deterioration of solderability due to thermal deterioration. It becomes possible.
また、所定の最終線径よりも太い線径のものに亜鉛また
は亜鉛合金下地めっきと銀めっきを施した後に、伸線加
工や熱処理等によって所定の線径な有する銀被覆銅線を
作成することにより銀めっき層のめつき粒子が密となり
熱劣化特性を向上できることとなる。In addition, after applying zinc or zinc alloy base plating and silver plating to a wire with a diameter thicker than the predetermined final wire diameter, a silver-coated copper wire having a predetermined wire diameter is created by wire drawing, heat treatment, etc. As a result, the plating particles of the silver plating layer become denser and the thermal deterioration characteristics can be improved.
更に、亜鉛めっき厚を０．０１〜０．５μに設けること
により、銅の鋏中への拡散を確実に防止でき、かつ、伸
線加工による銀めっき層の剥離を回付できることとなる
。Further, by setting the zinc plating thickness to 0.01 to 0.5 μm, diffusion of copper into the scissors can be reliably prevented, and peeling of the silver plating layer due to wire drawing can be avoided.
第１図は本発明による銀被覆銅線の断面図である。
１・・・銅＃ｊｌ ２・・・亜鉛めっき層 ６・・・銀
めっき層ｆ ｒ 囚FIG. 1 is a cross-sectional view of a silver-coated copper wire according to the present invention. 1...Copper #jl 2...Zinc plating layer 6...Silver plating layer f r
Claims (1)
に有する導線の表面に亜鉛または亜鉛合金下地めっき層
を有しかつ前記下地めっき層上に銀めっき層を有するこ
とを特徴とする耐熱銀被覆銅線。 （２）前記亜鉛または亜鉛合金下地めっき層の厚さが０
．０１〜０．５μであることを特徴とする特許請求の範
−囲第（１）項記載の耐熱銀被覆銅線。 （３）銅または銅を主体とした合金を少なくとも表面に
有しかつ所定の最終線径よりも太い線径な有する導線に
亜鉛または亜鉛合金めっきを行い、次いで銀めっきを行
った後に伸線加工および熱処理を施すことを特徴とする
耐熱銀被覆銅線の製造方法。 （４）前記亜鉛または亜鉛合金めっきはｏ、ｏｉ〜０５
μの厚さとなるよう行われることを特徴とする特許請求
の範囲第（３）項記載の製造方法。[Scope of Claims] (11) A conductive wire having copper or a copper-based alloy on at least its surface has a zinc or zinc alloy base plating layer on the surface and a silver plating layer on the base plating layer. Heat-resistant silver-coated copper wire characterized by: (2) The thickness of the zinc or zinc alloy base plating layer is 0.
．． 01 to 0.5μ. (3) Zinc or zinc alloy plating is applied to a conductor wire that has copper or a copper-based alloy on at least the surface and has a wire diameter thicker than the predetermined final wire diameter, and then wire drawing after silver plating. and a method for producing a heat-resistant silver-coated copper wire, characterized by subjecting it to heat treatment. (4) The zinc or zinc alloy plating is o, oi~05
The manufacturing method according to claim 3, wherein the manufacturing method is performed so that the thickness is μ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9798781A JPS6036000B2 (en) | 1981-06-24 | 1981-06-24 | Heat-resistant silver coated copper wire and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9798781A JPS6036000B2 (en) | 1981-06-24 | 1981-06-24 | Heat-resistant silver coated copper wire and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS581089A true JPS581089A (en) | 1983-01-06 |
| JPS6036000B2 JPS6036000B2 (en) | 1985-08-17 |
Family
ID=14207014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9798781A Expired JPS6036000B2 (en) | 1981-06-24 | 1981-06-24 | Heat-resistant silver coated copper wire and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6036000B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60115542A (en) * | 1983-11-25 | 1985-06-22 | Nippon Zeon Co Ltd | Production of cycloalkanol |
| US7491449B2 (en) * | 2006-02-24 | 2009-02-17 | Hon Hai Precision Industry Co., Ltd. | Copper-silver alloy wire and method for manufacturing the same |
| KR200467442Y1 (en) * | 2011-11-11 | 2013-06-13 | 주식회사 제이투엘에프에이 | Heat generating inner wear |
| CN103219311A (en) * | 2013-03-01 | 2013-07-24 | 溧阳市虹翔机械制造有限公司 | Palladium-plated silver-plated double-plating bonding copper wire |
| CN105063705A (en) * | 2015-07-30 | 2015-11-18 | 柳州市旭平首饰有限公司 | Method for preventing color change of copper ornament plated with silver |
| WO2021181901A1 (en) * | 2020-03-09 | 2021-09-16 | Ｄｏｗａメタルテック株式会社 | Silver-plated material and method for manufacturing same |
-
1981
- 1981-06-24 JP JP9798781A patent/JPS6036000B2/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60115542A (en) * | 1983-11-25 | 1985-06-22 | Nippon Zeon Co Ltd | Production of cycloalkanol |
| JPH0459304B2 (en) * | 1983-11-25 | 1992-09-21 | Nippon Zeon Co | |
| US7491449B2 (en) * | 2006-02-24 | 2009-02-17 | Hon Hai Precision Industry Co., Ltd. | Copper-silver alloy wire and method for manufacturing the same |
| KR200467442Y1 (en) * | 2011-11-11 | 2013-06-13 | 주식회사 제이투엘에프에이 | Heat generating inner wear |
| CN103219311A (en) * | 2013-03-01 | 2013-07-24 | 溧阳市虹翔机械制造有限公司 | Palladium-plated silver-plated double-plating bonding copper wire |
| CN105063705A (en) * | 2015-07-30 | 2015-11-18 | 柳州市旭平首饰有限公司 | Method for preventing color change of copper ornament plated with silver |
| WO2021181901A1 (en) * | 2020-03-09 | 2021-09-16 | Ｄｏｗａメタルテック株式会社 | Silver-plated material and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6036000B2 (en) | 1985-08-17 |
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