JPH0734254A - Electroless plating method to aluminum material - Google Patents
Electroless plating method to aluminum materialInfo
- Publication number
- JPH0734254A JPH0734254A JP17831093A JP17831093A JPH0734254A JP H0734254 A JPH0734254 A JP H0734254A JP 17831093 A JP17831093 A JP 17831093A JP 17831093 A JP17831093 A JP 17831093A JP H0734254 A JPH0734254 A JP H0734254A
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- plating
- metal
- aqueous solution
- film
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルミニウム系材料へ
の無電解めっき方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for electroless plating on aluminum-based materials.
【０００２】[0002]
【従来の技術及びその課題】アルミニウム系材料は、材
料固有の特性である軽量性、耐食性、外観性、加工性、
放熱性、電気特性等の性質から、建築、車両、機器、器
物、装飾等の幅広い産業分野で利用されている。特に、
近年、自動車関連産業では、車体の軽量化のために、ア
ルミニウム系素材の装着率が増加しており、また、電子
関連産業においても、前述したようなアルミニウム素材
の特性を生かして広い範囲の利用が検討されている。2. Description of the Related Art Aluminum-based materials are characterized by their unique properties of lightness, corrosion resistance, appearance, workability,
It is used in a wide range of industrial fields such as construction, vehicles, devices, articles and decorations due to its heat dissipation and electrical properties. In particular,
In recent years, in the automobile-related industry, the mounting rate of aluminum-based materials has been increasing in order to reduce the weight of vehicle bodies, and also in the electronics-related industry, it is possible to utilize a wide range by utilizing the characteristics of aluminum materials as described above. Is being considered.
【０００３】従来、アルミニウム系材料の表面処理方法
としては、陽極酸化処理方法が一般的であったが、各産
業分野での要求特性が高度化する中で、これでは十分に
対応できない場合があり、アルミニウム系材料の特性の
改善として、例えば、耐食性、硬度、耐摩耗性、光沢性
（外観性）、はんだ付け性等の向上のために、めっき皮
膜を形成する方法が着目されている。Conventionally, an anodizing method has been generally used as a surface treatment method for an aluminum-based material. However, as the required characteristics in each industrial field become more sophisticated, this may not be sufficient. In order to improve the properties of aluminum-based materials, for example, a method of forming a plating film has attracted attention in order to improve corrosion resistance, hardness, wear resistance, glossiness (appearance), solderability, and the like.
【０００４】従来、アルミニウム系材料にめっきを行な
う方法としては、各種方法が報告されているが、工業的
に最も多く利用されている方法は、アルミニウム系素材
上に、置換法によって、亜鉛、錫などの金属皮膜を形成
した後、めっき処理を行なう方法である。しかしなが
ら、置換法によって形成される金属皮膜は、鱗片状又は
霜降り状となっており、アルミニウム系素材との間に無
数の間隙があり、均一な置換皮膜とはならない。この様
な間隙部分に置換皮膜を形成するために、置換液の濃
度、温度、置換時間等を増加させたとしても、置換皮膜
が粉末化し、かえってアルミニウム系素材との密着性を
阻害することとなる。Conventionally, various methods have been reported as a method for plating an aluminum-based material. The most industrially used method is to use zinc or tin on an aluminum-based material by a substitution method. It is a method of performing plating after forming a metal film such as. However, the metal film formed by the substitution method is in the form of scales or marbling, and there are innumerable gaps between the metal film and the aluminum-based material, and a uniform substitution film cannot be obtained. In order to form a displacement film in such a gap portion, even if the concentration, temperature, displacement time, etc. of the displacement liquid are increased, the displacement film is pulverized and rather the adhesion with the aluminum-based material is hindered. Become.
【０００５】この様な欠点を改善する方法として、置換
浴組成を改善する方法（特公昭４５−２４４号、特公昭
４１−１７７３１号、特公平２−２０７０８号等）、電
解エッチングにより前処理する方法（特公平２−４３２
号、特開平３−２０７８８９号、特開平１−２３４５７
１号、特開平４−３６４７４号等）、亜鉛置換後に炭酸
水素ナトリウム等の無機塩水溶液に浸漬する方法（特公
平２−５０９８７号）等が提案されているが、これらの
方法では、特定のアルミニウム系材料に対しては良好な
結果が得られる場合があるが、工程的に複雑であった
り、工業的実施に当たり、コスト的に高価な場合が多
く、十分なものとはいえない。As a method for improving such a defect, a method for improving the composition of the displacement bath (Japanese Patent Publication No. 244/244, Japanese Patent Publication No. 41-17731, Japanese Patent Publication No. 2-20708, etc.) and pretreatment by electrolytic etching are carried out. Method (Tokuhei 2-432
JP-A-3-207889, JP-A-1-23457
No. 1, JP-A-4-36474, etc.), a method of immersing in an aqueous solution of an inorganic salt such as sodium hydrogencarbonate after substitution with zinc (Japanese Patent Publication No. 50987/1990), and the like have been proposed. Although good results may be obtained for aluminum-based materials, they are often not sufficient because they are complicated in process and often costly in industrial implementation.
【０００６】特に、アルミニウムにケイ素、マグネシウ
ム、銅、亜鉛等の金属元素を添加したアルミニウム合金
を素材とする場合には、アルミニウム金属と添加金属と
の間に電位の不均一性が存在するために、均一な置換皮
膜を形成することが困難であり、この上に形成されるめ
っき皮膜は密着性、耐食性、つき回り性等の点で十分な
ものとはいえない。特に、無電解めっき皮膜は、形成さ
れるめっき皮膜の特性が被処理物の表面状態に大きく影
響されるために、従来の金属置換皮膜を形成する方法で
はアルミニウム系合金上に良好な無電解めっき皮膜を形
成することは困難である。In particular, when an aluminum alloy in which a metal element such as silicon, magnesium, copper, or zinc is added to aluminum is used as a material, there is a non-uniform potential between the aluminum metal and the added metal. However, it is difficult to form a uniform substitution film, and the plating film formed thereon is not sufficient in terms of adhesion, corrosion resistance, throwing power, and the like. In particular, since the characteristics of the formed electroless plating film are greatly influenced by the surface condition of the object to be treated, the conventional method for forming a metal displacement coating film provides good electroless plating on an aluminum alloy. It is difficult to form a film.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記した如
き従来技術の課題に鑑みて、鋭意研究を重ねた結果、ア
ルミニウム系材料に亜鉛、錫等の金属置換皮膜を形成し
た後、還元剤を含有する水溶液で処理を行ない、次いで
無電解めっき処理を行なう場合には、還元剤を含有する
水溶液により金属置換皮膜の表面を均一に活性化するこ
とができ、形成される無電解めっき皮膜は、外観性、密
着性、耐食性、つき回り性等が飛躍的に改善されること
を見出し、ここに本発明を完成するに至った。The inventors of the present invention have conducted extensive studies in view of the problems of the prior art as described above, and as a result, after forming a metal substitution film of zinc, tin or the like on an aluminum material, reduction When the treatment is performed with an aqueous solution containing an agent and then electroless plating is performed, the surface of the metal displacement coating can be uniformly activated by the aqueous solution containing a reducing agent. Found that the appearance, adhesion, corrosion resistance, throwing power, etc. were dramatically improved, and thus completed the present invention.
【０００８】即ち、本発明は、アルミニウム系材料上
に、亜鉛又は錫を主成分とする金属置換皮膜を形成し、
次いで、還元剤を含有する水溶液で処理を行なった後、
無電解めっき処理を行なうことを特徴とするアルミニウ
ム系材料への無電解めっき方法に係る。That is, according to the present invention, a metal substitution coating containing zinc or tin as a main component is formed on an aluminum material,
Then, after treatment with an aqueous solution containing a reducing agent,
The present invention relates to a method for electroless plating on an aluminum-based material, which is characterized by performing electroless plating.
【０００９】本発明では、処理対象となるアルミニウム
系材料としては、純アルミニウム金属の他に、アルミニ
ウムにケイ素、マグネシウム、マンガン、銅、亜鉛等の
金属元素を添加したアルミニウム系合金も含まれ、日本
工業規格に規定される各種の展伸材、ダイカスト、鋳物
合金等をいずれも使用できる。In the present invention, the aluminum-based material to be treated includes, in addition to pure aluminum metal, aluminum-based alloys obtained by adding metal elements such as silicon, magnesium, manganese, copper and zinc to aluminum. Any of various wrought materials, die castings, casting alloys, etc. defined by industrial standards can be used.
【００１０】本発明方法では、まず、アルミニウム系材
料上に、亜鉛又は錫を主成分とする金属置換皮膜を形成
する。置換皮膜の形成方法は、常法に従えばよく、アル
ミニウム系材料を脱脂し、必要に応じて、エッチング、
中和、スマット除去等の処理を行なった後、金属置換皮
膜形成用の水溶液に浸漬すればよい。In the method of the present invention, first, a metal substitution film containing zinc or tin as a main component is formed on an aluminum material. The method of forming the substitution film may be according to a conventional method, such as degreasing the aluminum-based material, and if necessary, etching,
After performing treatments such as neutralization and smut removal, it may be immersed in an aqueous solution for forming a metal displacement coating.
【００１１】金属置換皮膜形成用の水溶液としては、従
来、アルミニウム系材料上に、亜鉛又は錫を主成分とす
る金属置換皮膜を形成するために用いられている公知の
溶液をいずれも用いることができる。この様な溶液とし
ては、金属成分として亜鉛化合物又は錫化合物のみを含
むものの他、亜鉛化合物又は錫化合物に加えて、置換皮
膜の特性の改善のために、ニッケル、銅、鉄等の各種の
金属化合物を配合したものが知られている。本発明で
は、この様な各種の公知の置換皮膜形成用の水溶液をい
ずれも使用することができる。As the aqueous solution for forming the metal displacement coating, any known solution which has been used for forming a metal displacement coating containing zinc or tin as a main component on an aluminum material can be used. it can. Such a solution contains not only a zinc compound or a tin compound as a metal component, but also various metals such as nickel, copper and iron in addition to the zinc compound or the tin compound in order to improve the characteristics of the displacement coating. A compound containing a compound is known. In the present invention, any of these various known aqueous solutions for forming a displacement film can be used.
【００１２】本発明では、金属置換皮膜の形成条件も公
知の方法と同様でよい。従来、金属置換皮膜の形成方法
として、金属置換皮膜を形成した後、硝酸等を含有する
水溶液に浸漬して、置換皮膜を一部溶解し、その後再度
金属置換皮膜を形成することによって、均一な置換皮膜
を形成する方法が知られており、本発明では、この様な
いわゆるダブル置換法を適用することもできる。In the present invention, the conditions for forming the metal displacement coating may be the same as those known in the art. Conventionally, as a method for forming a metal displacement coating, after the metal displacement coating is formed, it is immersed in an aqueous solution containing nitric acid or the like to partially dissolve the substitution coating, and then the metal substitution coating is formed again to obtain a uniform metal substitution coating. A method for forming a substitution film is known, and in the present invention, such a so-called double substitution method can also be applied.
【００１３】本発明では、置換皮膜の膜厚は特に限定的
ではなく、均一な金属置換皮膜を形成できる厚さとすれ
ばよく、従来の処理条件では、通常、０．１〜０．７μ
ｍ程度の皮膜が形成されるので、この程度の厚さのもの
をそのまま使用すればよい。In the present invention, the thickness of the displacement coating is not particularly limited, and may be any thickness that can form a uniform metal displacement coating. Under conventional processing conditions, it is usually 0.1 to 0.7 μm.
Since a film having a thickness of about m is formed, a film having such a thickness may be used as it is.
【００１４】本発明で使用し得る金属置換皮膜形成用の
水溶液及び処理条件の一例を以下に示す。An example of an aqueous solution for forming a metal displacement coating and treatment conditions which can be used in the present invention is shown below.
【００１５】亜鉛皮膜置換液 酸化亜鉛 １５０〜２４０ｇ／ｌ 水酸化ナトリウム ５００〜５５０ｇ／ｌ フッ化アンモニウム １０〜１５ｇ／ｌ シアン化ナトリウム ５〜１０ｇ／
ｌ 温度 １０〜１５℃ 時間 ２０〜９０秒亜鉛−銅皮膜置換液 硫酸銅 ４ｇ／ｌ 硫酸亜鉛 １０ｇ／ｌ 水酸化ナトリウム １５ｇ／ｌ 青化カリウム １３ｇ／ｌ 温度 ４０℃ 時間 ２０〜９０秒錫皮膜置換液 すず酸ナトリウム １５〜３０ｇ／ｌ 水酸化ナトリウム ４〜１１ｇ／ｌ 温度 ５０〜６０℃ 時間 ３〜４分間 本発明方法では、金属置換皮膜を形成した後、還元剤を
含有する水溶液で処理を行なう。還元剤としては、例え
ば、次亜りん酸ソーダ等の次亜りん酸塩類、水素化ホウ
素ナトリウム等のアルカリ金属水素化ホウ素塩、ジメチ
ルアミンボラン等のアミンボラン類、ホルムアルデヒド
等のアルデヒド類等を用いることができる。還元剤の濃
度は、５〜４０ｇ／ｌ程度とすればよい。 Zinc coating replacement liquid zinc oxide 150 to 240 g / l sodium hydroxide 500 to 550 g / l ammonium fluoride 10 to 15 g / l sodium cyanide 5 to 10 g /
20 to 90 seconds zinc l Temperature 10 to 15 ° C. Time - copper film substitution solution of copper sulfate 4g / l Zinc sulfate 10 g / l sodium hydroxide 15 g / l cyanide Potassium 13 g / l Temperature 40 ° C. Time 20 to 90 seconds tin film substituent in the liquid sodium stannate 15 to 30 g / l sodium hydroxide 4~11g / l temperature 50-60 ° C. time 3-4 minutes present invention method, after forming a metal displacement film, performs processing with an aqueous solution containing a reducing agent . Examples of the reducing agent include hypophosphites such as sodium hypophosphite, alkali metal borohydrides such as sodium borohydride, amineboranes such as dimethylamineborane, and aldehydes such as formaldehyde. You can The concentration of the reducing agent may be about 5-40 g / l.
【００１６】還元剤含有水溶液は、ｐＨ４〜１２程度で
用いることが好ましい。ｐＨが高くなると還元電位が高
くなり、金属置換皮膜の表面もそれだけ活性化される
が、次工程のめっき浴のｐＨと大きく異なるｐＨ値とす
ると、めっき浴に悪影響を与える可能性がある。このた
めの、還元剤含有水溶液のｐＨは、次工程のめっき浴の
ｐＨ値と近似した値とすることが好ましい。また、ｐＨ
値が小さすぎると、還元力が弱くなり、処理温度、処理
時間などを増加する必要があるので好ましくない。ｐＨ
調整は、還元剤含有水溶液中の配合成分の種類に応じ
て、硫酸、塩酸、酢酸等の酸類、苛性ソーダ、アンモニ
ア、炭酸ナトリウム等のアルカリ化合物から適宜選択し
て使用すればよい。The reducing agent-containing aqueous solution is preferably used at a pH of about 4-12. The higher the pH, the higher the reduction potential and the more the surface of the metal displacement coating is activated. However, if the pH value is significantly different from the pH of the plating bath in the next step, the plating bath may be adversely affected. For this purpose, the pH of the reducing agent-containing aqueous solution is preferably set to a value close to the pH value of the plating bath in the next step. Also, the pH
If the value is too small, the reducing power becomes weak and it is necessary to increase the treatment temperature, the treatment time and the like, which is not preferable. pH
The adjustment may be carried out by appropriately selecting from acids such as sulfuric acid, hydrochloric acid and acetic acid, alkali compounds such as caustic soda, ammonia and sodium carbonate, depending on the kind of the components blended in the reducing agent-containing aqueous solution.
【００１７】また、連続処理を行なう場合においても還
元剤含有水溶液のｐＨ値が大きく変動しないように、還
元剤含有水溶液中に緩衝剤を添加することが好ましい。
緩衝剤としては、クエン酸ナトリウム、酢酸ナトリウム
等の有機酸系緩衝剤、ホウ酸、炭酸等の無機酸系緩衝剤
等を使用できる。緩衝剤の添加量は、次工程の無電解め
っき液の種類により異なるが、一般的には１０〜１５０
ｇ／ｌ程度とすればよい。Further, it is preferable to add a buffering agent to the reducing agent-containing aqueous solution so that the pH value of the reducing agent-containing aqueous solution does not largely change even when continuous treatment is performed.
As the buffer, an organic acid buffer such as sodium citrate and sodium acetate, an inorganic acid buffer such as boric acid and carbonic acid, and the like can be used. The amount of the buffer agent added varies depending on the type of electroless plating solution used in the next step, but is generally 10 to 150.
It may be about g / l.
【００１８】また、還元剤の作用により、金属置換皮膜
に含まれる金属分が還元されて還元剤含有水溶液中に含
まれる場合があり、この様な金属イオンやその沈殿物
は、めっき浴中に持ち込まれるとめっき浴の老化、分解
を促進し、メッキ皮膜のザラやピットの原因となりやす
い。これを防ぐためには、還元剤含有水溶液中に、錯化
剤を添加して、金属分を錯体イオンとすることが好まし
い。錯化剤としては、グリコール酸、クエン酸、酒石酸
等の有機酸のアルカリ塩類、チオグリコール酸、アンモ
ニア、ヒドラジン、トリエタノールアミン、エチレンジ
アミン、グリシン、ｏ−アミノフェノール、ピリジン等
を用いることができ、これらのうちから、次工程の無電
解めっき浴に含まれる錯化剤と同一または類似した性質
を有するものを選択して使用することが好ましい。錯化
剤の添加量は、５〜１００ｇ／ｌ程度とすればよい。Further, the metal component contained in the metal displacement coating may be reduced by the action of the reducing agent and may be contained in the reducing agent-containing aqueous solution. Such metal ions and their precipitates may be contained in the plating bath. If they are brought in, they will accelerate the aging and decomposition of the plating bath, and will easily cause rust and pits in the plating film. In order to prevent this, it is preferable to add a complexing agent to the reducing agent-containing aqueous solution so that the metal component becomes a complex ion. As the complexing agent, alkali salts of organic acids such as glycolic acid, citric acid, tartaric acid, thioglycolic acid, ammonia, hydrazine, triethanolamine, ethylenediamine, glycine, o-aminophenol, pyridine and the like can be used. Of these, it is preferable to select and use one having the same or similar properties as the complexing agent contained in the electroless plating bath in the next step. The addition amount of the complexing agent may be about 5 to 100 g / l.
【００１９】更に、必要に応じて、還元剤含有水溶液中
に界面活性剤を添加することができる。界面活性剤を添
加すると、被処理剤表面に気泡が付着しやすい場合に
も、湿潤効果を与えて反応を円滑化することができる。
界面活性剤としては特に限定はないが、従来の無電解め
っき液に配合されているものと同様のもの、例えば、ポ
リオキシエチレンアルキルフェニルエーテル、ポリオキ
シエチレンアルキルエーテル等を用いることができる。
界面活性剤の使用量は、０．０００１〜１０ｍｌ／ｌ程
度とすればよい。Further, a surfactant may be added to the reducing agent-containing aqueous solution, if necessary. When a surfactant is added, even if bubbles are likely to adhere to the surface of the agent to be treated, a wetting effect can be given to smooth the reaction.
The surfactant is not particularly limited, but the same ones as those compounded in the conventional electroless plating solution, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether and the like can be used.
The amount of the surfactant used may be about 0.0001 to 10 ml / l.
【００２０】還元剤含有水溶液による処理方法は、特に
限定的ではないが、６０〜１００℃程度の液温の還元剤
含有水溶液中に１〜１０分間程度浸漬すればよい。液温
が高くなる程還元作用が強くなる傾向にあり、液温が低
すぎる場合には、金属置換皮膜の表面を均一に活性化す
る働きが小さくなくなり、良好な無電解めっき皮膜を形
成できないので好ましくない。また、処理時間が短か過
ぎる場合にも、やはり金属置換皮膜の表面を均一に活性
化することができない。本発明方法では、通常、各処理
工程の間に水洗を行なうが、例えば、大型の処理品を用
いる場合には、還元剤含有水溶液の液温をめっき浴の温
度と同様とし、水洗工程を省略して処理品を直接無電解
めっき液に入れることにより、めっき浴中での局部的な
温度差の発生を防ぎ、めっきの析出速度の均一化を図る
ことができる。The method of treatment with the reducing agent-containing aqueous solution is not particularly limited, but it may be immersed for 1 to 10 minutes in the reducing agent-containing aqueous solution having a liquid temperature of about 60 to 100 ° C. The higher the liquid temperature, the stronger the reducing action tends to be, and when the liquid temperature is too low, the function of uniformly activating the surface of the metal displacement coating becomes small, and a good electroless plating film cannot be formed. Not preferable. Moreover, even if the treatment time is too short, the surface of the metal displacement coating cannot be uniformly activated. In the method of the present invention, washing is usually performed between each treatment step. For example, when a large-sized treated product is used, the solution temperature of the reducing agent-containing aqueous solution is the same as the temperature of the plating bath, and the washing step is omitted. By directly putting the treated product into the electroless plating solution, it is possible to prevent a local temperature difference from occurring in the plating bath and to make the deposition rate of the plating uniform.
【００２１】本発明では、上記した方法で還元剤含有水
溶液による処理を行なった後、無電解めっきを行なう。
無電解めっき液としては、従来公知の各種めっき液を用
いることができる。例えば、無電解ニッケルめっき液と
しては、Ｎｉ−Ｐ系無電解めっき液、Ｎｉ−Ｂ系無電解
めっき液等を用いることができ、高温タイプのめっき
液、低温タイプのめっき液等、各種の公知の無電解めっ
き液ををいずれも用いることができる。また、無電解銅
めっき液としても、公知のめっき液をいずれも用いるこ
とができる。また、Ｎｉ−Ｆｅ−Ｐ系無電解めっき液、
Ｎｉ−Ｃｕ−Ｐ系無電解めっき液等の合金めっき用無電
解めっき液、ポリテトラフルオロエチレン、炭化ケイ
素、窒化硼素等の微粒子を分散させた共析めっき用無電
解めっき液も使用できる。In the present invention, electroless plating is performed after the treatment with the reducing agent-containing aqueous solution by the above-mentioned method.
As the electroless plating solution, various conventionally known plating solutions can be used. For example, as the electroless nickel plating solution, a Ni-P-based electroless plating solution, a Ni-B-based electroless plating solution, or the like can be used, and various known types such as a high-temperature type plating solution and a low-temperature type plating solution can be used. Any of the above electroless plating solutions can be used. Further, as the electroless copper plating solution, any known plating solution can be used. In addition, a Ni-Fe-P-based electroless plating solution,
An electroless plating solution for alloy plating such as a Ni-Cu-P-based electroless plating solution, and an electroless plating solution for eutectoid plating in which fine particles such as polytetrafluoroethylene, silicon carbide and boron nitride are dispersed can also be used.
【００２２】無電解めっきの条件は、従来と同様でよ
く、その膜厚も目的に応じて適宜決定すればよい。The electroless plating conditions may be the same as in the conventional case, and the film thickness may be appropriately determined according to the purpose.
【００２３】無電解めっき後は、目的に応じて、各種の
電気めっき又は無電解めっきを常法に従って行なうこと
ができる。After electroless plating, various kinds of electroplating or electroless plating can be performed according to a conventional method depending on the purpose.
【００２４】[0024]
【発明の効果】本発明によれば、亜鉛又は錫を主成分と
する金属置換皮膜を形成した後、還元剤含有水溶液で処
理を行なうことにより、金属置換皮膜の表面を均一に活
性化することができ、この上に形成される無電解めっき
皮膜は、外観性、密着性、耐食性、つき回り性等に非常
に優れたものとなる。また、使用する還元剤含有水溶液
は比較的安価であり、処理方法も容易であるために、本
発明方法は工業的利用に適したものである。According to the present invention, the surface of the metal displacement coating is uniformly activated by forming a metal displacement coating containing zinc or tin as a main component and then treating it with an aqueous solution containing a reducing agent. The electroless plating film formed thereon has excellent appearance, adhesion, corrosion resistance, throwing power, and the like. Further, the reducing agent-containing aqueous solution used is relatively inexpensive and the treatment method is easy, so that the method of the present invention is suitable for industrial use.
【００２５】また、この還元剤含有水溶液で処理するこ
とによって、密着の弱い金属置換皮膜が還元剤含有水溶
液中に溶出するので、無電解めっき液中でこれらの金属
類が溶出してめっき液が分解することが少なくなり、無
電解めっき液の浴寿命を延長させてコスト低減を図るこ
とができる。Further, by treating with this reducing agent-containing aqueous solution, the metal substitution film having weak adhesion is eluted into the reducing agent-containing aqueous solution, so that these metals are eluted in the electroless plating solution to form a plating solution. Decomposition is reduced, the bath life of the electroless plating solution can be extended, and the cost can be reduced.
【００２６】[0026]
【実施例】以下、実施例を示して本発明を更に詳細に説
明する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００２７】実施例１ ５０×３０×２０ｍｍのボックス型のアルミニウムダイ
キャスト成形品（ＪＩＳ ＡＤＣ−１２）を被処理物と
し、下記の工程でめっき処理を行なった。尚、各処理工
程の間には、水洗を行なった。Example 1 A 50 × 30 × 20 mm box-type aluminum die-cast molded product (JIS ADC-12) was used as an object to be treated, and plating treatment was performed in the following steps. Note that washing was performed between each treatment step.
【００２８】（１）脱脂 硫酸１００ｍｌ／ｌ及びトップＡＤＤ−１００（商標：
奥野製薬工業（株）製）１００ｍｌ／ｌを含有する脱脂
液に、４０℃で５分間浸漬した。(1) Degreasing Sulfuric acid 100 ml / l and Top ADD-100 (trademark:
It was immersed in a degreasing liquid containing 100 ml / l of Okuno Chemical Industries Co., Ltd. at 40 ° C. for 5 minutes.
【００２９】（２）エッチング 苛性ソーダ６０ｇ／ｌ及びグルコン酸ソーダ５ｇ／ｌを
含有するエッチング液に、５０℃で２分間浸漬した。(2) Etching An etching solution containing 60 g / l of caustic soda and 5 g / l of sodium gluconate was immersed at 50 ° C. for 2 minutes.
【００３０】（３）中和 硝酸１００ｍｌ／ｌ水溶液に、室温で３０秒間浸漬し
た。(3) Neutralization It was immersed in a 100 ml / l aqueous solution of nitric acid at room temperature for 30 seconds.
【００３１】（４）スマット除去 硝酸２００ｍｌ／ｌ及び酸性フッ化アンモニウム２０ｇ
／ｌを含有する水溶液に室温で６０秒間浸漬した。(4) Smut removal 200 ml / l nitric acid and 20 g of ammonium acid fluoride
It was immersed in an aqueous solution containing 1 / l for 60 seconds at room temperature.
【００３２】（５）亜鉛置換皮膜形成 （ｉ）第一置換皮膜形成 苛性ソーダ１０５ｇ／ｌ、硫酸亜鉛４０ｇ／ｌ、硫酸ニ
ッケル３０ｇ／ｌ、硫酸銅５ｇ／ｌ、塩化第二鉄２ｇ／
ｌ、ロッシェル塩４０ｇ／ｌ及びシアン化カリウム１０
ｇ／ｌを含む水溶液からなる亜鉛置換浴に２５℃で２０
秒間浸漬した。(5) Zinc substitution film formation (i) First substitution film formation Caustic soda 105 g / l, zinc sulfate 40 g / l, nickel sulfate 30 g / l, copper sulfate 5 g / l, ferric chloride 2 g / l
1, Rochelle salt 40 g / l and potassium cyanide 10
20 at 25 ° C in a zinc displacement bath consisting of an aqueous solution containing g / l
Soaked for 2 seconds.
【００３３】（ｉｉ）置換皮膜剥離 ６２％硝酸６００ｍｌ／ｌ水溶液に室温で２０秒間浸漬
した。(Ii) Peeling of the displacement coating A 62% nitric acid 600 ml / l aqueous solution was immersed for 20 seconds at room temperature.
【００３４】（ｉｉｉ）第二置換皮膜形成 上記亜鉛置換浴に室温で３０秒間浸漬した。(Iii) Formation of Second Substitution Film The above zinc substitution bath was immersed for 30 seconds at room temperature.
【００３５】（６）還元剤含有水溶液による処理 下記表１に示す濃度の次亜リン酸ソーダ、酢酸ソーダ２
６ｇ／ｌ及びクエン酸ソーダ１５ｇ／ｌを含有する処理
液をＮａＯＨ又はＨ2 ＳＯ4 で表１に示すｐＨ値に調整
し、表１に示す条件で処理した。(6) Treatment with an aqueous solution containing a reducing agent Sodium hypophosphite and sodium acetate 2 having the concentrations shown in Table 1 below.
The treatment liquid containing 6 g / l and 15 g / l of sodium citrate was adjusted to pH values shown in Table 1 with NaOH or H 2 SO 4 and treated under the conditions shown in Table 1.
【００３６】（７）無電解ニッケルめっき 硫酸ニッケル２６ｇ／ｌ、酢酸ソーダ２６ｇ／ｌ、クエ
ン酸ソーダ１５ｇ／ｌ次亜リン酸ソーダ１６ｇ／ｌ及び
チオ尿素４ｐｐｍを含有する無電解ニッケルめっき浴
（ｐＨ５．３）に、９０℃で３０分間浸漬した。(7) Electroless Nickel Plating An electroless nickel plating bath (pH 5) containing nickel sulfate 26 g / l, sodium acetate 26 g / l, sodium citrate 15 g / l sodium hypophosphite 16 g / l and thiourea 4 ppm. .3) was immersed at 90 ° C. for 30 minutes.
【００３７】得られた試料の外観、密着性、耐食性、つ
き回り性及び無電解めっき浴の分解性について、下記の
方法で評価を行なった。The appearance, adhesion, corrosion resistance, throwing power and degradability of the electroless plating bath of the obtained sample were evaluated by the following methods.
【００３８】（１）外観 目視によりめっき状態を判定し、下記の基準で評価し
た。(1) Appearance The plating state was visually judged and evaluated according to the following criteria.
【００３９】Ａ：全面均一めっき Ｂ：非めっき面積１０％以下 Ｃ：非めっき面積１０〜２０％ Ｄ：非めっき面積２０％以上 （２）密着性 ＪＩＳ Ｈ ８５０４に基づいて、熱風循環加熱炉で２
００℃、６０分間保持した後、速やかに取り出し、常温
の水中に入れて急冷して、倍率４倍の拡大鏡でめっき状
態を観察し、下記の基準で評価した。A: Uniform plating over the entire surface B: Non-plating area 10% or less C: Non-plating area 10 to 20% D: Non-plating area 20% or more (2) Adhesion Based on JIS H 8504, in a hot air circulation heating furnace. Two
After holding at 00 ° C. for 60 minutes, it was immediately taken out, put in water at room temperature to be rapidly cooled, and the plated state was observed with a magnifying glass having a magnification of 4 times, and evaluated according to the following criteria.
【００４０】Ａ：めっきの剥離、フクレが全くない。A: No peeling or blistering of plating.
【００４１】Ｂ：めっきの剥離、フクレが全面積の１％
以下 Ｃ：めっきの剥離、フクレが全面積の１〜５％ Ｄ：めっきの剥離、フクレが全面積の５％以上 （３）耐食性 ＪＩＳ Ｚ ２３７１に基づく塩水噴霧試験法により、
２４時間を１サイクルとして３サイクル連続噴霧を行な
い、錆の発生状態をレイティングナンバーで表示した。
レイティングナンバーが１０の場合に錆が全くなく、レ
イティングナンバーの値が小さいほど錆の発生量が多
い。B: Stripping of plating, blistering is 1% of the total area
Below C: peeling of plating, blister is 1 to 5% of the total area D: peeling of plating, blister is 5% or more of the total area (3) Corrosion resistance According to the salt spray test method based on JIS Z2371
Continuous spraying was performed for 3 cycles with 24 hours as one cycle, and the state of rust generation was displayed by a rating number.
When the rating number is 10, there is no rust, and the smaller the rating number, the greater the amount of rust.
【００４２】（４）つき回り性 めっき膜厚を１０箇所測定し、次式によりつき回り性を
評価した。(4) Covering property The plating film thickness was measured at 10 points and the covering property was evaluated by the following formula.
【００４３】つき回り性（％）＝（（最大膜厚−最小膜
厚）／平均膜厚）×１００ Ａ：０〜１０％ Ｂ：１１〜２０％ Ｃ：２０〜３０％
Ｄ：３０％以上 （５）めっき浴分解性 １０００ｍｌの無電解めっき浴のビーカー壁又は底部に
金属が析出するまでのターン数を求めた。１ターンと
は、建浴に使用した金属量と同量の金属分を補給した時
点をいう。Throwing power (%) = ((maximum film thickness-minimum film thickness) / average film thickness) × 100 A: 0 to 10% B: 11 to 20% C: 20 to 30%
D: 30% or more (5) Degradability of plating bath The number of turns until the metal was deposited on the beaker wall or bottom of a 1000 ml electroless plating bath was determined. One turn means the time when the same amount of metal as that used in the building bath is replenished.
【００４４】結果を下記表１に示す。The results are shown in Table 1 below.
【００４５】[0045]
【表１】 [Table 1]
【００４６】実施例２ ５０×１００×３ｍｍのアルミニウム合金（ＪＩＳ Ａ
３００３Ｐ）を被処理物とし、脱脂、エッチング、中
和及びスマット除去の各処理を実施例１と同様にして行
なった。次いで、下記の亜鉛置換皮膜形成用組成物又は
錫置換皮膜形成用組成物を用いて金属置換皮膜を形成し
た。Example 2 50 × 100 × 3 mm aluminum alloy (JIS A
3003P) was used as the object to be treated, and degreasing, etching, neutralization and smut removal were performed in the same manner as in Example 1. Then, a metal displacement coating was formed using the following zinc substitution coating forming composition or tin substitution coating forming composition.
【００４７】亜鉛置換組成物 （ａ）組成 酸化亜鉛 ２１０ｇ／ｌ 水酸化ナトリウム ５２０ｇ／ｌ フッ化アンモニウム １２ｇ／ｌ 青化ナトリウム ７ｇ／ｌ （ｂ）処理条件 （ｉ）シングル置換法 １５℃の置換用組成物中に３０秒間浸漬した。 Zinc-substituted composition (a) composition Zinc oxide 210 g / l Sodium hydroxide 520 g / l Ammonium fluoride 12 g / l Sodium bromide 7 g / l (b) Treatment conditions (i) Single substitution method For substitution at 15 ° C. It was immersed in the composition for 30 seconds.
【００４８】（ｉｉ）ダブル置換法 １５℃の置換用組成物中に２０秒間浸漬し、６２％硝酸
６００ｍｌ／ｌ水溶液に室温で２０秒間浸漬した後、再
度１５℃の置換用組成物中に３０秒間浸漬した。(Ii) Double displacement method: Immersed in a displacement composition at 15 ° C. for 20 seconds, immersed in an aqueous solution of 62% nitric acid at 600 ml / l for 20 seconds at room temperature, and again in the displacement composition at 15 ° C. for 30 seconds. Soaked for 2 seconds.
【００４９】錫置換用組成物 （ａ）組成 すず酸ナトリウム ２５ｇ／ｌ 水酸化ナトリウム ８ｇ／ｌ （ｂ）処理条件 （ｉ）シングル置換法 ５５℃の置換用組成物中に４分間浸漬した。 Composition for Tin Replacement (a) Composition Sodium stannate 25 g / l Sodium hydroxide 8 g / l (b) Treatment conditions (i) Single replacement method Immersed in the replacement composition at 55 ° C. for 4 minutes.
【００５０】（ｉｉ）ダブル置換法 ５５℃の置換用組成物中に２分間浸漬し、６２％硝酸６
００ｍｌ／ｌ水溶液に室温で２０秒間浸漬した後、再度
５５℃の置換用組成物中に４分間浸漬した。(Ii) Double displacement method: Immersed in a displacement composition at 55 ° C. for 2 minutes to prepare 62% nitric acid 6%.
After immersing in a 00 ml / l aqueous solution for 20 seconds at room temperature, it was again immersed in the replacement composition at 55 ° C. for 4 minutes.
【００５１】次いで、下記の還元剤含有水溶液Ａ又はＢ
により処理した後、下記無電解めっき液Ａ又はＢを用い
て無電解めっき皮膜を形成した。Then, the following reducing agent-containing aqueous solution A or B
After the treatment, the electroless plating solution A or B described below was used to form an electroless plating film.
【００５２】還元剤含有水溶液Ａ （ａ）組成 次亜リン酸ナトリウム ２０ｇ／ｌ クエン酸ナトリウム １０ｇ／ｌ 酢酸ナトリウム ２０ｇ／ｌ （ｂ）処理条件 ｐＨ ９．０ 温度 ９０℃ 時間 ５分還元剤含有水溶液Ｂ （ａ）組成 水素化ホウ素ナトリウム ０．５ｇ／ｌ エチレンジアミン ５０ｇ／ｌ 水酸化ナトリウム ３０ｇ／ｌ （ｂ）処理条件 ｐＨ １４ 温度 ６５℃ 時間 １０分無電解めっき液Ａ （ａ）組成 硫酸ニッケル ２６ｇ／ｌ 酢酸ナトリウム ２６ｇ／ｌ クエン酸ナトリウム １５ｇ／ｌ 次亜リン酸ナトリウム ３０ｇ／ｌ チオ尿素 ３〜５ｐｐｍ Ｐｂ++ １ｐｐｍ （ｂ）処理条件 ｐＨ ５〜５．５ 温度 ９０℃ 時間 ６０分無電解めっき液Ｂ （ａ）組成 塩化ニッケル ３０ｇ／ｌ 水素化ホウ素ナトリウム ０．６ｇ／ｌ エチレンジアミン ６０ｇ／ｌ 水酸化ナトリウム ４０ｇ／ｌ （ｂ）処理条件 ｐＨ １４ 温度 ６５℃ 時間 １２０分 処理条件及び得られた試料の試験結果を下記表２に示
す。 Reducing agent-containing aqueous solution A (a) composition Sodium hypophosphite 20 g / l Sodium citrate 10 g / l Sodium acetate 20 g / l (b) Treatment conditions pH 9.0 Temperature 90 ° C. time 5 minutes Reducing agent-containing aqueous solution B (a) composition Sodium borohydride 0.5 g / l Ethylenediamine 50 g / l Sodium hydroxide 30 g / l (b) Treatment conditions pH 14 Temperature 65 ° C. time 10 minutes Electroless plating solution A (a) composition Nickel sulfate 26 g / l Sodium acetate 26 g / l Sodium citrate 15 g / l Sodium hypophosphite 30 g / l Thiourea 3-5 ppm Pb ++ 1 ppm (b) Treatment conditions pH 5 to 5.5 Temperature 90 ° C. Time 60 minutes Electroless plating solution B (a) composition Nickel chloride 30 g / l sodium borohydride 0.6 g / l ethylenediamine 60 g / l sodium hydroxide 40 g / l (b) treatment conditions pH 14 temperature 65 ° C. time 120 minutes treatment conditions and test results of the obtained samples are shown in Table 2 below.
【００５３】[0053]
【表２】 [Table 2]
Claims (1)
成分とする置換皮膜を形成し、次いで、還元剤を含有す
る水溶液で処理を行なった後、無電解めっき処理を行な
うことを特徴とするアルミニウム系材料への無電解めっ
き方法。1. A method comprising: forming a substitutional film containing zinc or tin as a main component on an aluminum-based material; then performing treatment with an aqueous solution containing a reducing agent; and then performing electroless plating. Method for electroless plating on aluminum-based material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17831093A JPH0734254A (en) | 1993-07-19 | 1993-07-19 | Electroless plating method to aluminum material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17831093A JPH0734254A (en) | 1993-07-19 | 1993-07-19 | Electroless plating method to aluminum material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0734254A true JPH0734254A (en) | 1995-02-03 |
Family
ID=16046246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17831093A Pending JPH0734254A (en) | 1993-07-19 | 1993-07-19 | Electroless plating method to aluminum material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0734254A (en) |
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| JP2013540205A (en) * | 2010-10-13 | 2013-10-31 | ユニバーシティ・オブ・ウィンザー | Electroless metal deposition using highly alkaline plating bath |
| KR101453423B1 (en) * | 2013-07-31 | 2014-10-22 | 주식회사 두인 | Method of manufacturing of metal plated layer on the flexible printed circuit board |
| JP2019052327A (en) * | 2017-09-12 | 2019-04-04 | 奥野製薬工業株式会社 | Method of forming electroless nickel phosphorus plating coating on aluminum material |
| CN111364030A (en) * | 2020-04-07 | 2020-07-03 | 上海交通大学 | Pretreatment method for improving flatness of electroless NiP plating layer on aluminum substrate |
-
1993
- 1993-07-19 JP JP17831093A patent/JPH0734254A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180179B1 (en) | 1997-06-02 | 2001-01-30 | Nihon Parkerizing Co., Ltd. | Displace deposition-plated and doping-modified metal material and process for producing same |
| KR100389258B1 (en) * | 2000-12-22 | 2003-06-25 | 학교법인 한양학원 | zincating method accompanied with ultrasonic agitation on aluminum pad of silicon wafer |
| WO2004076724A1 (en) * | 2003-02-26 | 2004-09-10 | Toyo Kohan Co., Ltd. | SURFACE-TREATED Al SHEET EXCELLENT IN SOLDERABILITY, HEAT SINK USING THE SAME, AND METHOD FOR PRODUCING SURFACE-TREATED Al SHEET EXCELLENT IN SOLDERABILITY |
| JP2008223147A (en) * | 2008-06-13 | 2008-09-25 | Toyo Kohan Co Ltd | SURFACE-TREATED Al SHEET HAVING EXCELLENT SOLDERABILITY AND METHOD FOR PRODUCING THE SAME |
| JP2011001619A (en) * | 2009-06-20 | 2011-01-06 | Ritsuhin Ri | Electroless nickel plating bath and electroless nickel plating method |
| KR100960683B1 (en) * | 2009-09-11 | 2010-05-31 | 씨앤지머트리얼즈(주) | Preparation method of al shaped body with plating layer and the shaped body |
| JP2013540205A (en) * | 2010-10-13 | 2013-10-31 | ユニバーシティ・オブ・ウィンザー | Electroless metal deposition using highly alkaline plating bath |
| KR101453423B1 (en) * | 2013-07-31 | 2014-10-22 | 주식회사 두인 | Method of manufacturing of metal plated layer on the flexible printed circuit board |
| JP2019052327A (en) * | 2017-09-12 | 2019-04-04 | 奥野製薬工業株式会社 | Method of forming electroless nickel phosphorus plating coating on aluminum material |
| CN111364030A (en) * | 2020-04-07 | 2020-07-03 | 上海交通大学 | Pretreatment method for improving flatness of electroless NiP plating layer on aluminum substrate |
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