JPH1112751A - Method for electroless plating with nickel and/or cobalt - Google Patents
Method for electroless plating with nickel and/or cobaltInfo
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- JPH1112751A JPH1112751A JP17134797A JP17134797A JPH1112751A JP H1112751 A JPH1112751 A JP H1112751A JP 17134797 A JP17134797 A JP 17134797A JP 17134797 A JP17134797 A JP 17134797A JP H1112751 A JPH1112751 A JP H1112751A
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- plating
- nickel
- cobalt
- electroless plating
- bath
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気めっき皮膜や
溶融めっき皮膜等の、密着性向上等の機能向上を目的と
してなされるニッケルやコバルトのプレめっきに好適な
無電解めっき方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless plating method suitable for pre-plating nickel or cobalt for the purpose of improving functions such as adhesion of an electroplating film or a hot-dip coating film. .
【０００２】[0002]
【従来の技術】従来から電気めっき皮膜や溶融めっき皮
膜等の機能向上を目的として、ニッケルやコバルトのプ
レめっきが用いられている。例えば特開昭５９−２００
７８９号公報では、電気めっき鋼板を施す前にあらかじ
めＮｉやＣｏを付着させて、密着性を向上させている。
また、特許第１３３０５５３号公報では、溶融めっきを
施す前にあらかじめニッケルやコバルトのプレめっきを
施すことで密着性を向上させている。さらに、特開平４
−２２１０９７号公報ではステンレス鋼へＮｉやＣｏを
プレめっきすることでステンレス鋼とめっき金属層との
密着性を向上させている。いずれも、ニッケルやコバル
トの付着量は数ｍｇ／ｍ2 から数ｇ／ｍ2と、非常に少
量で効果を発現している。2. Description of the Related Art Conventionally, nickel or cobalt pre-plating has been used for the purpose of improving the functions of an electroplating film and a hot-dip plating film. For example, JP-A-59-200
In Japanese Patent No. 789, Ni or Co is attached in advance before applying an electroplated steel sheet to improve the adhesion.
In Japanese Patent No. 1330553, adhesion is improved by pre-plating nickel or cobalt before hot-dip plating. Further, Japanese Unexamined Patent Publication No.
In Japanese Patent No. 2221097, the adhesion between stainless steel and a plated metal layer is improved by pre-plating Ni or Co on stainless steel. In each case, the effect is exhibited with a very small amount of nickel or cobalt of several mg / m 2 to several g / m 2 .
【０００３】ニッケルやコバルトのプレめっき方法とし
ては、電気めっき法が主流である。この理由として、電
気めっき法では付着時間の短時間化（数秒以内）が容
易である、付着量の制御が容易である、めっき浴の
管理や分析方法が容易である等があげられる。特に、鋼
板を通板させる生産ラインにおいては、付着時間の短時
間化は、通板速度の増加、すなわち、生産性の向上を可
能とするため、電気めっき法は付着方法として優れてい
る。しかし一方で、電気めっき法はその設備コストが大
きいという課題がある。ニッケルやコバルトの電気めっ
き法以外での付着方法としては、無電解めっき法が一般
的である。[0003] As a pre-plating method for nickel or cobalt, an electroplating method is mainly used. The reasons for this are that the electroplating method can easily shorten the deposition time (within several seconds), easily control the deposition amount, and easily manage and analyze the plating bath. In particular, in a production line in which a steel sheet is passed, since the shortening of the adhesion time enables an increase in the sheet passing speed, that is, an improvement in productivity, the electroplating method is an excellent adhesion method. However, on the other hand, the electroplating method has a problem that its equipment cost is large. As a method of attaching nickel or cobalt other than the electroplating method, an electroless plating method is generally used.
【０００４】無電解めっき方法の例として、例えば特開
昭６２−３５４７７号公報、特開昭６３−２４１１８７
号公報、特開平１−２２５７７７号公報等が公知であ
り、いずれも該金属イオンに還元剤を配合することでめ
っき浴中での酸化皮膜の生成を抑制し、無電解めっきを
行うものである。還元剤は、該金属の還元補助剤であ
り、本発明者らの検討結果では、還元剤を有しないめっ
き浴では、無電解めっきの速度は著しく遅くなり、数ｍ
ｇ／ｍ2 のめっき量を得るために数分以上の時間を要し
た。したがって、還元剤は無電解めっきの速度を向上さ
せる効果を有している。[0004] Examples of the electroless plating method include, for example, JP-A-62-35477 and JP-A-63-241187.
And Japanese Patent Application Laid-Open No. 1-225777, all of which are known to suppress the formation of an oxide film in a plating bath by adding a reducing agent to the metal ions and perform electroless plating. . The reducing agent is a reducing auxiliary agent for the metal. According to the results of studies by the present inventors, in a plating bath having no reducing agent, the speed of electroless plating is significantly reduced, and several m
It took several minutes or more to obtain a plating amount of g / m 2 . Therefore, the reducing agent has the effect of improving the speed of electroless plating.
【０００５】しかし、還元剤（例えば、次亜りん酸塩
等）は該金属イオンを還元した後、自身は酸化され、酸
化反応物となり（例えば、亜りん酸塩等）、その後は無
電解めっきの速度向上に何ら寄与しない。還元剤が消費
された後は、還元剤を再添加する必要があり、コスト的
な負担を来す。また、無電解めっき液中に還元剤の酸化
反応物（例えば、亜りん酸塩等）が増大してめっきの品
質へ悪影響を与える可能性があるため、めっき液を一部
あるいは全量を廃液して再度、所定濃度のめっき浴を作
製しなければならず、コストの増加を招くだけでなく廃
液処理が必要になるので、環境への負荷をも招き、環境
上好ましくない。また酸化還元反応工程で、還元剤の濃
度を把握するための分析工程をも必要となるため、操業
の管理が複雑化する問題もある。さらには還元剤中の元
素（例えば、Ｎｉ無電解めっきの添加剤である次亜りん
酸ナトリウム中のＰ等）が該金属（Ｎｉ、Ｃｏ等）を還
元する過程で無電解めっき皮膜に混入及び／又は付着し
て、目的の機能を有する皮膜が得られない可能性もあ
る。However, the reducing agent (eg, hypophosphite) reduces the metal ion and then oxidizes itself to become an oxidation reactant (eg, phosphite). It does not contribute to the speed improvement at all. After the reducing agent is consumed, it is necessary to re-add the reducing agent, resulting in a cost burden. In addition, since an oxidation reactant (for example, phosphite) of a reducing agent may increase in the electroless plating solution and adversely affect plating quality, a part or the entire amount of the plating solution may be discarded. In this case, a plating bath having a predetermined concentration must be prepared again, which not only increases the cost but also necessitates waste liquid treatment. Further, in the oxidation-reduction reaction step, an analysis step for grasping the concentration of the reducing agent is also required, so that there is a problem that the management of the operation is complicated. Further, elements in the reducing agent (for example, P in sodium hypophosphite which is an additive of Ni electroless plating) are mixed into the electroless plating film in the process of reducing the metal (Ni, Co, etc.). There is also a possibility that a film having a desired function may not be obtained due to adhesion.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記の問題点
に鑑み、還元剤を積極的に使用することなく、低コスト
で、環境にやさしく、短時間でめっきが可能なニッケル
及び／又はコバルトの無電解めっき方法及びそのめっき
浴を提供することを目的としている。SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a low-cost, environmentally-friendly nickel- and / or cobalt-free plating method without the active use of a reducing agent. An electroless plating method and a plating bath thereof are provided.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、還元剤を
実質的に含まない該金属イオンだけからなる無電解めっ
きのめっき速度が小さいのは、鋼板表面に存在する酸化
皮膜が無電解めっきの障害となっているためであること
を見出した。そこで、鋼板を酸洗して酸化皮膜を除去し
て無電解めっきしたところ、酸洗後、鋼板が大気に触れ
ると、直ちに酸化皮膜が形成し、無電解めっきの速度は
向上しなかった。次に、めっき液を強酸性（ｐＨ≦１）
に保ち無電解めっきしたところ、水素発生が優先的に起
こり、めっきは生成しなかった。そこで、酸化皮膜を除
去する方法として強酸を用いない手段を種々検討した結
果、めっき液中にハロゲン化合物を添加することで、無
電解めっきのめっき速度（析出速度）が著しく向上する
ことを見出した。Means for Solving the Problems The present inventors have found that the plating speed of electroless plating consisting of only metal ions substantially containing no reducing agent is low because the oxide film existing on the surface of the steel sheet is electroless. It was found that this was because it was an obstacle to plating. Then, when the steel sheet was pickled to remove the oxide film and subjected to electroless plating, when the steel sheet was exposed to the air after the pickling, an oxide film was immediately formed, and the speed of electroless plating did not improve. Next, make the plating solution strongly acidic (pH ≦ 1)
, The generation of hydrogen occurred preferentially, and no plating was generated. Therefore, as a result of various investigations on a method that does not use a strong acid as a method for removing the oxide film, it was found that the addition of a halogen compound to the plating solution significantly improved the plating rate (deposition rate) of electroless plating. .
【０００８】本発明は、これらの知見に基づいてなされ
たもので、本発明の要旨とするところは、（１）易酸化
素材にニッケル及び／又はコバルトを無電解めっきする
に際して、めっき浴中にハロゲン化合物を含有せしめ、
該浴浸漬前に該素材表面に形成した酸化膜をめっき浴中
で除去しつつ無電解めっきを施すことを特徴とするニッ
ケル及び／又はコバルトの無電解めっき方法、（２）易
酸化素材が鋼材であることを特徴とする前記（１）に記
載のニッケル及び／又はコバルトの無電解めっき方法、
（３）無電解めっきがニッケル塩及び／又はコバルト塩
を溶解しためっき浴中に易酸化素材を浸漬してなされる
ことを特徴とする前記（１）または前記（２）に記載の
ニッケル及び／又はコバルトの無電解めっき方法、
（４）めっき浴中にニッケル、コバルトの１種または２
種を各金属イオン濃度で０．０１ｍｏｌ／１〜１ｍｏｌ
／１、１種または２種以上のハロゲン化物を総ハロゲン
濃度として０．０５ｍｏｌ／１〜１ｍｏｌ／１含有せし
めたことを特徴とする前記（１）または前記（２）また
は前記（３）に記載のニッケル及び／又はコバルトの無
電解めっき方法、The present invention has been made on the basis of these findings. The gist of the present invention is as follows. (1) When electroless plating nickel and / or cobalt on an easily oxidizable material, the plating bath is required. Containing a halogen compound,
An electroless plating method for nickel and / or cobalt, wherein an oxide film formed on the surface of the material is removed in a plating bath before immersion in the bath; An electroless plating method for nickel and / or cobalt according to the above (1),
(3) The method according to (1) or (2), wherein the electroless plating is performed by immersing the easily oxidizable material in a plating bath in which a nickel salt and / or a cobalt salt is dissolved. Or cobalt electroless plating method,
(4) One or two of nickel and cobalt in the plating bath
Species at each metal ion concentration 0.01mol / 1 ~ 1mol
(1), (2) or (3), characterized in that one or more halides are contained in a total halogen concentration of 0.05 mol / 1 to 1 mol / 1. Nickel and / or cobalt electroless plating method,
【０００９】（５）めっき浴温を６０℃以上とすること
を特徴とする前記（１）または前記（２）または前記
（３）または前記（４）に記載のニッケル及び／又はコ
バルトの無電解めっき方法、（６）ハロゲン化合物がフ
ッ化物であることを特徴とする前記（１）または前記
（２）または前記（３）または前記（４）または前記
（５）に記載のニッケル及び／又はコバルトの無電解め
っき方法、（７）フッ化物が、ＮＨ4 Ｆ、ＮａＦ、Ｋ
Ｆ、ＮｉＦ2 、ＣｏＦ2 のいづれかであることを特徴と
する前記（６）に記載のニッケルまたはコバルトの無電
解めっき方法である。(5) The electroless nickel and / or cobalt according to (1), (2), (3) or (4), wherein the plating bath temperature is 60 ° C. or higher. (6) The nickel and / or cobalt according to (1), (2), (3), (4), or (5), wherein the halogen compound is a fluoride. Electroless plating method, (7) when the fluoride is NH 4 F, NaF, K
The electroless plating method of nickel or cobalt according to the above (6), wherein the method is any one of F, NiF 2 , and CoF 2 .
【００１０】[0010]
【発明の実施の形態】以下、本発明について詳細に説明
する。易酸化素材としては例えば、鋼、Ａｌ、Ｔｉ等が
あげられる。これらの易酸化素材には通常大気下で、数
ｎｍ〜数μｍ程度の酸化膜厚さを有している。ニッケル
やコバルトの無電解めっきを短時間でかつ均一に施すた
めには、１ｓ以内での除去が好ましく、ハロゲン化合物
を添加することで、これを可能とする。ハロゲン化合物
を添加することで無電解めっきのめっき速度が向上する
理由は明らかではないが、ハロゲン化物イオン（Ｆ- 、
Ｃｌ- 等）が易酸化素材（例えば鋼中の鉄など）上の酸
化膜を溶解させて、該素材の新生面を露出させること
で、新生面での易酸化素材とニッケルイオンあるいはコ
バルトイオンの置換反応が生じやすくなったためと本発
明者らは推察している。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the easily oxidizable material include steel, Al, and Ti. These easily oxidizable materials usually have an oxide film thickness of several nm to several μm in the atmosphere. In order to apply nickel and cobalt electroless plating in a short time and uniformly, removal within 1 s is preferable, and this can be achieved by adding a halogen compound. It is not clear why the addition of the halogen compound improves the plating rate of the electroless plating, but the halide ion (F − ,
Cl − etc.) dissolves the oxide film on the easily oxidizable material (for example, iron in steel) and exposes a new surface of the material, thereby replacing the easily oxidizable material with nickel ions or cobalt ions on the new surface. The present inventors presume that the occurrence of the problem has easily occurred.
【００１１】ニッケルまたはコバルトの濃度は０．０１
ｍｏｌ／ｌ未満では、付着時間が遅くなるため好ましく
ない。また、１ｍｏｌ／ｌを超えると、付着時間の短時
間化効果が飽和するため、それを超える添加はコスト上
得策でない。ハロゲン化合物は総ハロゲン濃度として
０．０５ｍｏｌ／ｌ未満では、付着時間の短時間化に対
する効果が乏しい。また、１ｍｏｌ／ｌを超えると、付
着時間の短時間化効果が飽和するため、それを超える添
加はコスト上得策でない。めっき液の浴温は、２０℃以
上でハロゲン化合物の効果が発揮でき、６０℃以上で効
果が顕著である。ただし、９０℃超では、めっき液の沸
騰の始まりにより該金属の析出が妨げられる可能性があ
るため、９０℃以下が好ましい。The concentration of nickel or cobalt is 0.01
If the amount is less than mol / l, the adhesion time is undesirably long. On the other hand, if it exceeds 1 mol / l, the effect of shortening the adhesion time is saturated, so that addition exceeding that is not advantageous in terms of cost. If the total halogen concentration of the halogen compound is less than 0.05 mol / l, the effect of shortening the adhesion time is poor. On the other hand, if it exceeds 1 mol / l, the effect of shortening the adhesion time is saturated, so that addition exceeding that is not advantageous in terms of cost. The effect of the halogen compound can be exhibited at a bath temperature of the plating solution of 20 ° C. or higher, and the effect is remarkable at a bath temperature of 60 ° C. or higher. However, if the temperature is higher than 90 ° C., the deposition of the metal may be hindered by the start of the boiling of the plating solution.
【００１２】ハロゲンの種類としては、フッ素、塩素、
臭素、よう素など、いずれのハロゲンにおいても効果が
見られるが、とりわけフッ素の効果が著しく、フッ素の
化合物がさらに好ましい。ハロゲン化合物の種類として
は、水溶液中で化合物が解離して、ハロゲン化物イオン
（Ｆ- 、Ｃｌ- 、Ｂｒ- 、Ｉ- ）が生成するものであれ
ばいずれでもかまわないが、ハロゲン化アンモニウム、
無電解めっきする金属（ニッケル、コバルト）のハロゲ
ン化物、アルカリ金属（ナトリウム、カリウム等）のハ
ロゲン化合物、ハロゲンガスが水への溶解のしやすさを
考慮すると好ましい。The types of halogen include fluorine, chlorine,
Although an effect can be seen with any halogen such as bromine and iodine, the effect of fluorine is remarkable, and a fluorine compound is more preferable. The type of the halogen compound may be any as long as the compound is dissociated in an aqueous solution to generate halide ions (F − , Cl − , Br − , I − ).
It is preferable that the halide of the metal (nickel, cobalt), the halogen compound of the alkali metal (sodium, potassium, etc.) and the halogen gas to be electrolessly plated are easily dissolved in water.
【００１３】ニッケル塩、コバルト塩は水溶液に溶解し
たときに、解離して該金属のイオンが生成するなら、ど
のような化合物で添加しても本発明には何ら影響なく、
例えば、硫酸塩、硝酸塩、ハロゲン化物等が使用でき
る。なお、めっき液は該金属が主体のめっき液であれ
ば、不可避的にＰｂ、Ｓｎ、Ｃｕ、Ｚｎ、Ｆｅ、Ａｌ、
Ｃｒ、Ｃｄ等を含んでいても本発明の発現に何ら影響は
ない。無電解めっき浴のｐＨは特に定めないが、強酸性
（ｐＨ≦１）では水素発生が起きやすいので、水素発生
が優先的に起こらない範囲ｐＨ≧２、さらにはｐＨ≧３
が好ましい。また、めっき液が中性に近づくと、水に難
溶性のコバルトまたはニッケルの水酸化物が生成して沈
殿が発生しやすくなるため、ｐＨ≦６が好ましい。If the nickel salt and the cobalt salt dissociate to form ions of the metal when dissolved in the aqueous solution, the addition of any compound will not affect the present invention at all.
For example, sulfates, nitrates, halides and the like can be used. When the plating solution is a plating solution mainly composed of the metal, Pb, Sn, Cu, Zn, Fe, Al,
The presence of Cr, Cd, etc. has no effect on the expression of the present invention. Although the pH of the electroless plating bath is not particularly defined, hydrogen generation is likely to occur in strongly acidic (pH ≦ 1), so that a range in which hydrogen generation does not occur preferentially is pH ≧ 2, and furthermore, pH ≧ 3.
Is preferred. Further, when the plating solution approaches neutrality, a hydroxide of cobalt or nickel, which is hardly soluble in water, is formed and precipitation is likely to occur, so that pH ≦ 6 is preferable.
【００１４】めっきに用いる設備については、易酸化素
材を流動のないめっき液に浸漬させる液静止型、めっき
液を循環させながら、易酸化素材を浸漬する液循環型、
静止しためっき液中に連続的に易酸化素材を浸漬させる
あるいは循環しているめっき液に連続的に易酸化素材を
浸漬させる通板型など、いずれの設備を用いても本発明
の効果発現に直接の影響はなく、従来からの無電解めっ
き設備に応じた方式を用いることができる。めっきに用
いる易酸化素材が鋼材の場合には、低炭素鋼、極低炭素
鋼、低合金鋼、高合金鋼、ステンレス鋼等各種組成の鋼
材で本発明の無電解めっき方法は効果があり、また、加
工形態では熱延鋼帯、冷延鋼帯、各種形状鋼板（例えば
鋼管など）、線材等に適用できる。The equipment used for plating includes a liquid stationary type in which the easily oxidizable material is immersed in a plating solution having no flow, and a liquid circulation type in which the easily oxidizable material is immersed while circulating the plating solution.
The effect of the present invention can be realized by using any equipment such as a continuous plate type in which the easily oxidizable material is continuously immersed in the stationary plating solution or the continuously oxidizable material is continuously immersed in the circulating plating solution. There is no direct effect, and a method according to the conventional electroless plating equipment can be used. When the easily oxidizable material used for plating is a steel material, the electroless plating method of the present invention is effective for steel materials of various compositions such as low carbon steel, extremely low carbon steel, low alloy steel, high alloy steel, and stainless steel, Further, in the form of processing, the present invention can be applied to a hot-rolled steel strip, a cold-rolled steel strip, steel sheets of various shapes (eg, steel pipes), wires, and the like.
【００１５】[0015]
【実施例】次に、本発明の実施例を比較例とともにあげ
る。無電解めっきは静止浴に鋼板を浸漬して施した。め
っき条件は表１に示す金属化合物、金属イオン濃度、浴
温度にて、０．７ｍｍ厚の冷延鋼板にめっきを施した。
また、評価はめっき速度の絶対評価（めっき速度）と相
対効果（めっき速度改善度）、めっき外観、ハロゲン化
合物ありなしで作製したプレめっき性の比較（めっき後
の密着性変化）にて行い、これらの結果を表２に示し
た。絶対評価（めっき速度）は、めっき時間とめっき厚
さの関係から調べた。また、めっき浴温度によってめっ
き速度も変化するため、同一浴温度でハロゲン化合物を
含まない場合のめっき速度の相対比較（めっき速度改善
度）をし、ハロゲン化合物の添加によりめっき速度が５
００％以上向上したものを〇、それ未満を×とした。Next, examples of the present invention will be described together with comparative examples. The electroless plating was performed by immersing the steel sheet in a static bath. Plating conditions were such that a 0.7 mm thick cold-rolled steel sheet was plated at the metal compound, metal ion concentration and bath temperature shown in Table 1.
In addition, the evaluation was performed based on the absolute evaluation of the plating rate (plating rate) and the relative effect (degree of improvement of the plating rate), the plating appearance, and the comparison of the pre-plating property prepared with and without the halogen compound (adhesion change after plating). Table 2 shows the results. The absolute evaluation (plating speed) was examined from the relationship between the plating time and the plating thickness. In addition, since the plating rate also changes depending on the plating bath temperature, a relative comparison (plating rate improvement) of the plating rate when no halogen compound is contained at the same bath temperature is performed.
Those that were improved by 00% or more were rated as Δ, and less than that were rated as x.
【００１６】めっき外観は、無電解めっき量を１ｇ／ｍ
2 としたサンプルを作製し、目視にて、外観にむら等が
なく均一外観であるものを〇、外観にむら等が生じ実用
不可のものを×で評価した。プレめっき性の比較（めっ
き後の密着性変化）は、ニッケルまたはコバルトを１ｇ
／ｍ2 以下、本発明の方法にてプレめっきした後に、電
気めっき（電気Ｚｎめっき）を２０ｇ／ｍ2 施し、密着
曲げ後の密着曲げ部分のめっき剥離状況から評価し、ハ
ロゲン化合物を使用せずに同一量のニッケルまたはコバ
ルトをプレめっきした場合の剥離状況と比較して、改善
されたあるいはほぼ同等のものを〇、悪化したものを×
とした。The plating appearance is such that the amount of electroless plating is 1 g / m
Samples designated as No. 2 were prepared, and those having a uniform appearance without any unevenness in appearance were evaluated as “A”, and those with non-practical appearance due to unevenness in the external appearance were evaluated as “X”. Comparison of pre-plating properties (adhesion change after plating): 1 g of nickel or cobalt
/ M 2 or less, after pre-plating by the method of the present invention, electroplating (electro-Zn plating) is performed at 20 g / m 2 , and evaluation is made based on the state of peeling of the plating at the contact bending portion after the contact bending, and a halogen compound is used. Compared with the peeling situation when the same amount of nickel or cobalt was pre-plated without improving or almost equivalent, and
And
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】実施例１〜１６は、本発明であるが、いず
れもめっき速度向上の効果が著しく、あるいはめっき速
度の改善が見られ、外観も良好であるとともに、ハロゲ
ン化合物を添加したことによるプレめっき性の悪化は見
られなかった。一方、比較例において、ハロゲン化合物
が存在しないまたは添加量が少なすぎた比較例１７、１
８、２１、２３ではめっき速度は非常に遅く、ハロゲン
化合物が存在する場合と比べ、約１／１０程度であっ
た。無電解金属種が少なすぎた比較例１９、２２でも同
様にめっき速度は遅かった。また、浴温度が９８℃の比
較例２０では、めっき液のフェライトが始まり、水蒸気
の発生によって無電解めっきが抑制されるだけでなく、
めっき外観やめっき後の密着性も悪化した。Examples 1 to 16 are the present invention, all of which have a remarkable effect of improving the plating rate, or show an improvement in the plating rate, have a good appearance, and have a good appearance due to the addition of a halogen compound. No deterioration in plating properties was observed. On the other hand, in Comparative Examples, Comparative Examples 17 and 1 in which no halogen compound was present or the addition amount was too small
In 8, 21, and 23, the plating rate was very slow, which was about 1/10 compared to the case where a halogen compound was present. In Comparative Examples 19 and 22, where the electroless metal species was too small, the plating rate was similarly low. In Comparative Example 20 in which the bath temperature was 98 ° C., not only ferrite of the plating solution started, but also generation of water vapor suppressed electroless plating,
The plating appearance and the adhesion after plating also deteriorated.
【００２０】[0020]
【発明の効果】本発明により、無電解めっき法でも短時
間でニッケルやコバルトの付着が可能となり、設備コス
トの大きな電気めっき法を用いずに低コストでの製造を
可能とすることを提供する。さらには、これまで無電解
めっきに一般的に使用されてきた還元剤を用いないこと
で、めっき廃液を少なくし、環境への影響を極力低減し
たものである。したがって、本発明の産業に貢献するこ
とは極めて大きい。According to the present invention, it is possible to attach nickel and cobalt in a short time even by an electroless plating method, and to provide a low-cost production without using an electroplating method having a large equipment cost. . Furthermore, by not using a reducing agent that has been generally used in electroless plating, the amount of plating waste liquid is reduced, and the effect on the environment is reduced as much as possible. Therefore, contribution to the industry of the present invention is extremely large.
Claims (7)
トを無電解めっきするに際して、めっき浴中にハロゲン
化合物を含有せしめ、該浴浸漬前に該素材表面に形成し
た酸化膜をめっき浴中で除去しつつ無電解めっきを施す
ことを特徴とするニッケル及び／又はコバルトの無電解
めっき方法。1. When electroless plating nickel and / or cobalt on an easily oxidizable material, a halogen compound is contained in a plating bath, and an oxide film formed on the surface of the material before immersion in the bath is removed in the plating bath. An electroless plating method for nickel and / or cobalt, wherein the electroless plating is performed while performing electroless plating.
る請求項１に記載のニッケル及び／又はコバルトの無電
解めっき方法。2. The method for electroless plating nickel and / or cobalt according to claim 1, wherein the easily oxidizable material is a steel material.
バルト塩を溶解しためっき浴中に易酸化素材を浸漬して
なされることを特徴とする請求項１または請求項２に記
載のニッケル及び／又はコバルトの無電解めっき方法。3. The method according to claim 1, wherein the electroless plating is performed by immersing the easily oxidizable material in a plating bath in which a nickel salt and / or a cobalt salt are dissolved. Or a cobalt electroless plating method.
または２種を各金属イオン濃度で０．０１ｍｏｌ／ｌ〜
１ｍｏｌ／１、１種または２種以上のハロゲン化合物を
総ハロゲン濃度として０．０５ｍｏｌ／ｌ〜１ｍｏｌ／
ｌ含有せしめたことを特徴とする請求項１または請求項
２または請求項３に記載のニッケル及び／又はコバルト
の無電解めっき方法。4. One or two kinds of nickel and cobalt in a plating bath at a concentration of each metal ion of 0.01 mol / l or more.
1 mol / 1, one or more halogen compounds in a total halogen concentration of 0.05 mol / l to 1 mol /
The electroless plating method for nickel and / or cobalt according to claim 1, wherein the metal is l-containing.
徴とする請求項１または請求項２または請求項３または
請求項４に記載のニッケル及び／又はコバルトの無電解
めっき方法。5. The method for electroless plating nickel and / or cobalt according to claim 1, wherein the plating bath temperature is set to 60 ° C. or higher.
特徴とする請求項１または請求項２または請求項３また
は請求項４または請求項５に記載のニッケル及び／又は
コバルトの無電解めっき方法。6. The electroless plating method of nickel and / or cobalt according to claim 1, wherein the halogen compound is a fluoride.
ＮｉＦ2 、ＣｏＦ2のいづれか１種または２種以上であ
ることを特徴とする請求項６に記載のニッケルまたはコ
バルトの無電解めっき方法。7. The method according to claim 7, wherein the fluoride is NH 4 F, NaF, KF,
NiF 2, electroless plating method of a nickel or cobalt according to claim 6, characterized in that CoF is 2 Izure one kind or two or more kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17134797A JPH1112751A (en) | 1997-06-27 | 1997-06-27 | Method for electroless plating with nickel and/or cobalt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17134797A JPH1112751A (en) | 1997-06-27 | 1997-06-27 | Method for electroless plating with nickel and/or cobalt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1112751A true JPH1112751A (en) | 1999-01-19 |
Family
ID=15921530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17134797A Withdrawn JPH1112751A (en) | 1997-06-27 | 1997-06-27 | Method for electroless plating with nickel and/or cobalt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1112751A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007266324A (en) * | 2006-03-28 | 2007-10-11 | Matsushita Electric Works Ltd | Stainless transfer base, stainless transfer base having plated circuit layer, circuit board, and module incorporating component |
| JP2007270298A (en) * | 2006-03-31 | 2007-10-18 | Tdk Corp | Electroless plating solution, and ceramic electronic component manufacturing method |
| JP2011099161A (en) * | 2009-10-09 | 2011-05-19 | Tosoh Corp | Nickel plating liquid |
| CN103882492A (en) * | 2014-02-24 | 2014-06-25 | 哈尔滨工程大学 | Chemical plating posttreatment method of metallic matrix |
| CN105297085A (en) * | 2015-08-27 | 2016-02-03 | 中国科学院兰州化学物理研究所 | Nickel plating liquid and method for preparing nickel-based plating layer by using same |
-
1997
- 1997-06-27 JP JP17134797A patent/JPH1112751A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007266324A (en) * | 2006-03-28 | 2007-10-11 | Matsushita Electric Works Ltd | Stainless transfer base, stainless transfer base having plated circuit layer, circuit board, and module incorporating component |
| JP4508141B2 (en) * | 2006-03-28 | 2010-07-21 | パナソニック電工株式会社 | Stainless steel transfer substrate, stainless steel transfer substrate with plating circuit layer |
| JP2007270298A (en) * | 2006-03-31 | 2007-10-18 | Tdk Corp | Electroless plating solution, and ceramic electronic component manufacturing method |
| JP4582044B2 (en) * | 2006-03-31 | 2010-11-17 | Ｔｄｋ株式会社 | Electroless plating solution and method for manufacturing ceramic electronic component |
| JP2011099161A (en) * | 2009-10-09 | 2011-05-19 | Tosoh Corp | Nickel plating liquid |
| CN103882492A (en) * | 2014-02-24 | 2014-06-25 | 哈尔滨工程大学 | Chemical plating posttreatment method of metallic matrix |
| CN105297085A (en) * | 2015-08-27 | 2016-02-03 | 中国科学院兰州化学物理研究所 | Nickel plating liquid and method for preparing nickel-based plating layer by using same |
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