JP5687051B2 - Copper-zinc alloy plating method and copper-zinc alloy plating bath used therefor - Google Patents
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Description
本発明は、銅−亜鉛合金めっき方法（以下、単に「めっき方法」とも称する）およびそれに用いる銅−亜鉛合金めっき浴（以下、単に「めっき浴」とも称する）に関し、詳しくは、めっきヤケを生じず、均一な銅−亜鉛合金めっき層（以下、単に「めっき層」とも称する）の生産性を向上させることができる銅−亜鉛合金めっき方法およびそれに用いる銅−亜鉛合金めっき浴に関する。 The present invention relates to a copper-zinc alloy plating method (hereinafter also simply referred to as “plating method”) and a copper-zinc alloy plating bath used therefor (hereinafter also simply referred to as “plating bath”). In particular, the present invention relates to a copper-zinc alloy plating method capable of improving the productivity of a uniform copper-zinc alloy plating layer (hereinafter also simply referred to as “plating layer”) and a copper-zinc alloy plating bath used therefor.
現在、銅−亜鉛合金めっきは、金属製品、プラスチック製品、セラミック製品等に真鍮色の金属光沢および色調を与えるため、装飾めっきとして工業的に広く用いられている。また、銅−亜鉛合金めっきは、タイヤ用スチールコードとゴムとの接着性を向上させる目的としても用いられている。しかしながら、従来のめっき浴はシアン化合物を多量に含んでいるため、その毒性が大きな問題となっており、また、含シアン化合物廃液の処理負担も大きなものであった。 Currently, copper-zinc alloy plating is widely used industrially as decorative plating in order to give a metallic luster and color tone of brass color to metal products, plastic products, ceramic products and the like. Copper-zinc alloy plating is also used for the purpose of improving the adhesion between a steel cord for tire and rubber. However, since the conventional plating bath contains a large amount of cyanide, its toxicity is a big problem, and the treatment load of the cyanide-containing waste liquid is also large.
かかる問題の解決手段として、今日、シアン化合物を用いない銅−亜鉛合金めっき方法が多数報告されている。例えば、逐次めっきは、黄銅めっきを被めっき製品に施すための実際的な方法であり、かかる方法においては、電着によって銅めっき層と亜鉛めっき層が被めっき製品表面に順次めっきされ、ついで、熱拡散工程が施される。逐次黄銅めっきの場合、ピロリン酸銅めっき溶液と酸性の硫酸亜鉛めっき溶液が通常使用されている（例えば、特許文献１）。一方、銅−亜鉛を同時にめっきする方法として、シアン化合物を含まない銅−亜鉛めっき浴も報告されており、グルコヘプトン酸浴や錯化剤としてヒスチジン添加のピロリン酸カリウム浴を用いためっき浴が提案されている（例えば、特許文献２）。 As a means for solving such a problem, many copper-zinc alloy plating methods not using a cyanide have been reported today. For example, sequential plating is a practical method for applying brass plating to a product to be plated. In such a method, a copper plating layer and a zinc plating layer are sequentially plated on the surface of the product to be plated by electrodeposition, A thermal diffusion process is performed. In the case of sequential brass plating, a copper pyrophosphate plating solution and an acidic zinc sulfate plating solution are usually used (for example, Patent Document 1). On the other hand, a copper-zinc plating bath not containing a cyanide compound has also been reported as a method for simultaneously plating copper-zinc, and a plating bath using a glucoheptonic acid bath or a histidine-added potassium pyrophosphate bath as a complexing agent is proposed. (For example, Patent Document 2).
しかしながら、特許文献１記載に記載されているような逐次めっきでは、銅めっき層形成工程、亜鉛めっき層形成工程及び熱拡散工程、と処理工程が多く、複雑であるため作業効率が悪いという欠点がある。また、めっき処理時の電流を大きくすることができず、めっきの生産性においても十分なものとは言えなかった。すなわち、ピロリン酸銅を用いためっき浴においては、陰極電流密度は５〜１０Ａ／ｄｍ２であった。 However, in the sequential plating as described in Patent Document 1, there are a number of copper plating layer forming step, galvanizing layer forming step and thermal diffusion step, and processing steps. is there. In addition, the current during the plating process cannot be increased, and it cannot be said that the plating productivity is sufficient. That is, in the plating bath using a copper pyrophosphate, cathode current density was 5~10A / dm 2.
一方、特許文献２記載の銅−亜鉛合金めっき浴においては、シアン化合物を使用した浴を用いた場合のような毒性の問題はないが、やはり、めっきヤケのない均一なめっき層を形成することが可能な陰極電流密度は５Ａ／ｄｍ２以下であり、めっき層を生産性よく形成するのに必要とされる陰極電流密度と比べて小さいという問題を有していた。 On the other hand, in the copper-zinc alloy plating bath described in Patent Document 2, there is no problem of toxicity as in the case where a bath using a cyanide compound is used, but a uniform plating layer without plating burn is still formed. However, the cathode current density that is possible is 5 A / dm 2 or less, which is a problem that the cathode current density is smaller than the cathode current density required for forming the plating layer with high productivity.
このような問題を解消する手法として、例えば、特許文献３に、所定の組成を有する銅−亜鉛合金めっき浴のｐＨを好適化することにより、めっき処理時の陰極電流密度を大きくする手法が開示されている。これによれば、５Ａ／ｄｍ２を超える高陰極電流密度でめっき処理が可能となる。 As a technique for solving such a problem, for example, Patent Document 3 discloses a technique for increasing the cathode current density during the plating process by optimizing the pH of a copper-zinc alloy plating bath having a predetermined composition. Has been. According to this, the plating process can be performed at a high cathode current density exceeding 5 A / dm 2 .
しかしながら、特許文献３の手法を用いたとしても、めっき処理の際に加える陰極電流密度は１０Ａ／ｄｍ２以下であり、また、その際の電流効率は約６０％程度であるため、めっき層の生産性に関しては必ずしも満足できるものではなく、さらなる改善が望まれているが、高電流密度にて銅−亜鉛合金めっきを施すと、めっき層の表面状態が悪化すると考えられる。そのため、被めっき体がスチールコードの材料である金属鋼線材の場合、めっき処理後の湿式伸線工程において、ダイスによる引き延ばし加工により、金属鋼線材表面のめっき層が破壊され、脱落してしまうおそれがある。 However, even if the technique of Patent Document 3 is used, the cathode current density applied during the plating process is 10 A / dm 2 or less, and the current efficiency at that time is about 60%. Although productivity is not always satisfactory and further improvement is desired, it is considered that when the copper-zinc alloy plating is performed at a high current density, the surface state of the plating layer is deteriorated. Therefore, when the object to be plated is a metal steel wire that is a steel cord material, the plating layer on the surface of the metal steel wire may be destroyed and dropped due to the drawing process using a die in the wet wire drawing process after plating. There is.
このような理由にから、銅−亜鉛合金めっき処理においては、電流密度を大きくすることは、生産効率を向上させる上で重要な因子であるにもかかわらず、十分な検討がなされていないというのが現状である。 For these reasons, in copper-zinc alloy plating, increasing current density is an important factor for improving production efficiency, but has not been sufficiently studied. Is the current situation.
そこで本発明の目的は、めっきヤケを生じず、均一な銅−亜鉛合金めっき層の生産性を向上させることができる銅−亜鉛合金めっき方法およびそれに用いる銅−亜鉛合金めっき浴を提供することにある。 Therefore, an object of the present invention is to provide a copper-zinc alloy plating method and a copper-zinc alloy plating bath used therefor, which can improve the productivity of a uniform copper-zinc alloy plating layer without causing plating burn. is there.
本発明者らは、上記課題を解決するため鋭意検討をした結果、下記構成とすることにより、上記課題を解決することができることを見出して、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-described problems can be solved by adopting the following configuration, and have completed the present invention.
すなわち、本発明の銅−亜鉛合金めっき方法は、銅塩と、亜鉛塩と、ピロリン酸アルカリ金属塩と、アミノ酸またはその塩から選ばれた少なくとも一種と、を含有し、ｐＨが１０．５〜１１．８である銅−亜鉛合金めっき浴を用いた銅−亜鉛合金めっき方法において、
１０Ａ／ｄｍ２を超える陰極電流密度で銅−亜鉛合金めっき処理を行い、かつ、前記銅−亜鉛合金めっき浴が、下記式、
Ｐ比＝Ｐ２Ｏ７の質量／（Ｃｕの質量＋Ｚｎの質量）
で表わされるＰ比が５．５〜７．０を満足し、
前記銅−亜鉛合金めっき浴のアミノ酸またはその塩から選ばれた少なくとも一種の濃度が０．１ｍｏｌ／Ｌ以上であり、ピロリン酸アルカリ金属塩の濃度が０．２〜０．８ｍｏｌ／Ｌであり、前記銅−亜鉛合金めっき浴のアミノ酸またはその塩が、ヒスチジンまたはその塩であることを特徴とするものである。
That is, the copper-zinc alloy plating method of the present invention contains a copper salt, a zinc salt, an alkali metal pyrophosphate, and at least one selected from amino acids or salts thereof, and has a pH of 10.5 to In the copper-zinc alloy plating method using the copper-zinc alloy plating bath which is 11.8,
The copper-zinc alloy plating treatment is performed at a cathode current density exceeding 10 A / dm 2 , and the copper-zinc alloy plating bath has the following formula:
P ratio = mass of P 2 O 7 / (mass of Cu + mass of Zn)
P ratio represented by 5.5 to 7.0 is satisfied,
The concentration of at least one selected from amino acids or salts thereof in the copper-zinc alloy plating bath is 0.1 mol / L or more, and the concentration of alkali metal pyrophosphate is 0.2 to 0.8 mol / L, The amino acid or salt thereof in the copper-zinc alloy plating bath is histidine or a salt thereof.
本発明の銅−亜鉛合金めっき浴においては、ピロリン酸アルカリ金属塩はピロリン酸カリウムであることが好ましく、また、本発明の銅−亜鉛合金めっき浴に含まれる銅および亜鉛の和は０．０３〜０．３ｍｏｌ／Ｌの範囲であることが好ましく、さらに、アルカリ金属水酸化物およびアルカリ土類金属水酸化物から選ばれた少なくとも一種を含有することが好ましい。 In the copper-zinc alloy plating bath of the present invention, the alkali metal pyrophosphate is preferably potassium pyrophosphate, and the sum of copper and zinc contained in the copper-zinc alloy plating bath of the present invention is 0.03. It is preferable that it is the range of -0.3 mol / L, Furthermore, it is preferable to contain at least 1 type chosen from the alkali metal hydroxide and the alkaline-earth metal hydroxide.
本発明の銅−亜鉛合金めっき浴は、上記本発明の銅−亜鉛合金めっき方法に用いるめっき浴である。 The copper-zinc alloy plating bath of the present invention is a plating bath used for the copper-zinc alloy plating method of the present invention.
本発明によれば、めっきヤケを生じず、均一な銅−亜鉛合金めっき層の生産性を向上させることができる銅−亜鉛合金めっき方法およびそれに用いる銅−亜鉛合金めっき浴を提供することができる。 According to the present invention, it is possible to provide a copper-zinc alloy plating method capable of improving the productivity of a uniform copper-zinc alloy plating layer and a copper-zinc alloy plating bath used therefor without causing plating burn. .
以下、本発明の好適な実施の形態について詳細に説明する。
本発明の銅−亜鉛合金めっき方法は、銅塩と、亜鉛塩と、ピロリン酸アルカリ金属塩と、アミノ酸またはその塩から選ばれた少なくとも一種と、を含有し、ｐＨが８．５〜１４である銅−亜鉛合金めっき浴を用いたものである。上記組成を有するめっき浴を用いることにより、従来は困難であると考えられていた、陰極電流密度が１０Ａ／ｄｍ２を超える場合であっても、均一、かつ、めっきヤケのないめっき層を得ることができる。その結果、被めっき体としてスチールコードの材料である金属線鋼材を用いた場合においても、引き延ばし加工の際に生じる不具合を回避することができる。
Hereinafter, preferred embodiments of the present invention will be described in detail.
The copper-zinc alloy plating method of the present invention contains a copper salt, a zinc salt, an alkali metal pyrophosphate, and at least one selected from amino acids or salts thereof, and has a pH of 8.5 to 14 A certain copper-zinc alloy plating bath is used. By using a plating bath having the above composition, a plating layer that is uniform and free of plating burns is obtained even when the cathode current density exceeds 10 A / dm 2, which has been considered difficult in the past. be able to. As a result, even when a metal wire steel material that is a steel cord material is used as the object to be plated, it is possible to avoid problems that occur during the drawing process.
上記めっき浴は、下記式で表わされるＰ比、
Ｐ比＝Ｐ２Ｏ７の質量／（Ｃｕの質量＋Ｚｎの質量）
が３．０〜７．０であることが好ましい。特に、Ｐ比が５．５〜７．０であれば、陰極電流密度が２０Ａ／ｄｍ２以上であっても、均一でめっきヤケのないめっき層を得ることができる。かかる効果は、陰極電流密度が２０〜３０Ａ／ｄｍ２の範囲で顕著である。
The plating bath has a P ratio represented by the following formula:
P ratio = mass of P 2 O 7 / (mass of Cu + mass of Zn)
Is preferably 3.0 to 7.0. In particular, when the P ratio is 5.5 to 7.0, it is possible to obtain a uniform plating layer with no plating burn even if the cathode current density is 20 A / dm 2 or more. This effect is remarkable when the cathode current density is in the range of 20 to 30 A / dm2.
本発明においては、上記めっき浴中のアミノ酸またはその塩から選ばれた少なくとも一種の濃度を０．１ｍｏｌ／Ｌ以上とし、ピロリン酸アルカリ金属塩の濃度を０．２〜０．８ｍｏｌ／Ｌとすることが好ましい。アミノ酸またはその塩から選ばれた少なくとも一種の濃度と、ピロリン酸アルカリ金属塩の濃度が上記範囲外となると、本発明の効果を良好に得ることができない場合があるからである。 In the present invention, the concentration of at least one selected from amino acids or salts thereof in the plating bath is 0.1 mol / L or more, and the concentration of alkali metal pyrophosphate is 0.2 to 0.8 mol / L. It is preferable. This is because if the concentration of at least one selected from amino acids or salts thereof and the concentration of alkali metal pyrophosphate are outside the above ranges, the effects of the present invention may not be obtained satisfactorily.
本発明においては、銅塩としては、めっき浴の銅イオン源として公知のものであればいずれも使用可能であり、例えば、ピロリン酸銅、硫酸銅、塩化第２銅、スルファミン酸銅、酢酸第２銅、塩基性炭酸銅、臭化第２銅、ギ酸銅、水酸化銅、酸化第２銅、リン酸銅、ケイフッ化銅、ステアリン酸銅、クエン酸第２銅等を挙げることができ、これらのうち１種のみを用いてもよいし、２種以上を用いてもよい。 In the present invention, any copper salt can be used as long as it is known as a copper ion source for a plating bath. For example, copper pyrophosphate, copper sulfate, cupric chloride, copper sulfamate, acetic acid 2 copper, basic copper carbonate, cupric bromide, copper formate, copper hydroxide, cupric oxide, copper phosphate, copper fluorosilicate, copper stearate, cupric citrate, etc. Among these, only 1 type may be used and 2 or more types may be used.
亜鉛塩としては、めっき浴の亜鉛イオン源として公知のものであればいずれも使用可能であり、例えば、ピロリン酸亜鉛、硫酸亜鉛、塩化亜鉛、スルファミン酸亜鉛、酸化亜鉛、酢酸亜鉛、臭化亜鉛、塩基性炭酸亜鉛、シュウ酸亜鉛、リン酸亜鉛、ケイフッ化亜鉛、ステアリン酸亜鉛、乳酸亜鉛等を挙げることができ、これらのうち１種のみを用いてもよいし、２種以上を用いてもよい。 Any zinc salt may be used as long as it is a known zinc ion source for a plating bath. For example, zinc pyrophosphate, zinc sulfate, zinc chloride, zinc sulfamate, zinc oxide, zinc acetate, zinc bromide , Basic zinc carbonate, zinc oxalate, zinc phosphate, zinc fluorosilicate, zinc stearate, zinc lactate, etc., and only one of these may be used, or two or more may be used. Also good.
なお、めっき浴に溶解している銅および亜鉛の和は、０．０３〜０．３０ｍｏｌ／Ｌの範囲であることが好ましい。０．０３ｍｏｌ／Ｌ未満であると銅の析出が優先してしまうおそれがあり、良好なめっき層を得ることが難しくなる場合がある。一方、０．３０ｍｏｌ／Ｌを超えるとめっき被膜の表面に光沢が得られなくなってしまう場合がある。 The sum of copper and zinc dissolved in the plating bath is preferably in the range of 0.03 to 0.30 mol / L. If it is less than 0.03 mol / L, the deposition of copper may be prioritized, and it may be difficult to obtain a good plating layer. On the other hand, if it exceeds 0.30 mol / L, gloss may not be obtained on the surface of the plating film.
ピロリン酸アルカリ金属塩としては、公知のものであればいずれでも使用可能であり、例えば、ピロリン酸ナトリウム、ピロリン酸カリウム塩を好適に用いることができる。 Any alkali metal pyrophosphate can be used as long as it is known, and for example, sodium pyrophosphate and potassium pyrophosphate can be suitably used.
アミノ酸としては、公知のものであればいずれでも使用可能であり、例えば、グリシン、アラニン、グルタミン酸、アスパラギン酸、トレオニン、セリン、プロリン、トリプトファン、ヒスチジン等のα−アミノ酸若しくはその塩酸塩、ナトリウム塩等を挙げることができ、好ましくはヒスチジンである。なお、これらのうち１種のみを用いてもよいし、２種以上を用いてもよい。 Any known amino acid can be used, for example, glycine, alanine, glutamic acid, aspartic acid, threonine, serine, proline, tryptophan, histidine, etc. α-amino acid or its hydrochloride, sodium salt, etc. Among them, histidine is preferable. In addition, only 1 type may be used among these and 2 or more types may be used.
本発明においては、上記めっき浴のｐＨは８．５〜１４である。ｐＨが８．５未満であると、本発明の効果を得ることができず、一方、ｐＨが１４を超えると電流効率が低下してしまう。本発明の効果を良好に得るためには、好ましくは１０．５〜１１．８の範囲である。また、本発明のめっき浴のｐＨ調整には、水酸化ナトリウム、水酸化カリウムのようなアルカリ金属水酸化物および水酸化カルシウムのようなアルカリ土類金属水酸化物を好適に用いることができ、好ましくは水酸化カリウムである。 In the present invention, the pH of the plating bath is 8.5-14. If the pH is less than 8.5, the effect of the present invention cannot be obtained. On the other hand, if the pH exceeds 14, the current efficiency decreases. In order to obtain the effect of the present invention favorably, it is preferably in the range of 10.5 to 11.8. Further, for pH adjustment of the plating bath of the present invention, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkaline earth metal hydroxides such as calcium hydroxide can be suitably used. Potassium hydroxide is preferred.
上記めっき浴においては、上記各成分の配合量は特に制限されず、適宜選択することができるが、工業的な取扱いを考慮すると、銅塩を銅換算で２〜４０ｇ／Ｌ、亜鉛塩を亜鉛換算で０．５〜３０ｇ／Ｌ、ピロリン酸アルカリ金属塩１５０〜４００ｇ／Ｌ、アミノ酸又はその塩を０．２〜５０ｇ／Ｌ程度とすることが好ましい。 In the above plating bath, the blending amount of each of the above components is not particularly limited and can be appropriately selected. However, considering industrial handling, the copper salt is 2 to 40 g / L in terms of copper, and the zinc salt is zinc. It is preferable that 0.5-30 g / L in terms of conversion, alkali metal pyrophosphate 150-400 g / L, amino acid or a salt thereof is about 0.2-50 g / L.
本発明のめっき方法を用いてめっき処理を行う場合、通常のめっき処理の条件を採用することができる。例えば、浴温３０〜４０℃程度で、無攪拌下あるいは機械攪拌下又は空気攪拌下で電気めっきをすればよい。この際、陽極としては、通常の銅−亜鉛合金の電気めっきに用いられるものであれば、いずれも使用できる。 When performing a plating process using the plating method of this invention, the conditions of a normal plating process are employable. For example, electroplating may be performed at a bath temperature of about 30 to 40 ° C. with no stirring, mechanical stirring, or air stirring. At this time, any anode can be used as long as it is used for electroplating of a normal copper-zinc alloy.
本発明においては、めっき処理を行う前に、被めっき体には、常法に従ってバフ研磨、脱脂、希酸浸漬等の通常の前処理を施すことができ、あるいは光沢ニッケルめっき等の下地めっきを施すことも可能である。また、めっき後には、水洗、湯洗、乾燥等の通常行われている操作を行ってもよい。 In the present invention, before performing the plating treatment, the object to be plated can be subjected to normal pretreatment such as buffing, degreasing, dilute acid immersion, etc. according to a conventional method, or undercoating such as bright nickel plating. It is also possible to apply. Moreover, you may perform operation normally performed, such as washing with water, hot water washing, and drying, after plating.
本発明では、被めっき体としては特に制限されず、通常、銅−亜鉛合金めっきが施されるものいずれにも適用可能であり、例えば、ゴム物品補強用スチールコードに使用する金属鋼線材をはじめとした金属製品、プラスチック製品、セラミックス製品等を挙げることができる。 In the present invention, the object to be plated is not particularly limited, and is usually applicable to any of those subjected to copper-zinc alloy plating, such as metal steel wire used for steel cords for reinforcing rubber articles. Metal products, plastic products, ceramic products and the like.
本発明の、銅−亜鉛合金めっき浴は、上記本発明のめっき方法に用いるめっき浴である。本発明のめっき浴の組成は上記のとおりであり、これを用いることにより、均一でめっきヤケのない銅−亜鉛合金めっき層を、生産性良く得ることができる。 The copper-zinc alloy plating bath of the present invention is a plating bath used for the plating method of the present invention. The composition of the plating bath of the present invention is as described above, and by using this, a uniform copper-zinc alloy plating layer having no plating burn can be obtained with high productivity.
以下、本発明を実施例を用いてより詳細に説明する。
＜実施例１〜４、比較例１〜３、参考例１〜３＞
下記の表１および２にそれぞれ示す銅−亜鉛合金めっき浴の組成に従い、実施例１〜４、比較例１〜３および参考例１〜３の銅−亜鉛合金めっき浴を調製し、銅−亜鉛合金めっき処理を行った。めっき処理は、めっき浴作製後直ちに行ない、得られためっき層の合金組成を分析した。また、めっきヤケのない均一なめっき層を得ることができる陰極電流密度範囲および電流効率を求めた。得られた結果を下記の表１および２に併記する。
Hereinafter, the present invention will be described in more detail with reference to examples.
<Examples 1-4, Comparative Examples 1-3, Reference Examples 1-3>
The copper-zinc alloy plating baths of Examples 1-4, Comparative Examples 1-3 and Reference Examples 1-3 were prepared according to the compositions of the copper-zinc alloy plating baths shown in Tables 1 and 2 below, respectively. Alloy plating treatment was performed. The plating treatment was performed immediately after the preparation of the plating bath, and the alloy composition of the obtained plating layer was analyzed. Moreover, the cathode current density range and current efficiency which can obtain the uniform plating layer without a plating burn were calculated | required. The obtained results are shown in Tables 1 and 2 below.
表１および２より、本発明によれば、陰極電流密度が１０Ａ／ｄｍ２を超える範囲においても、めっきヤケのない、均一な組成の銅−亜鉛合金めっきを施すことができることが確かめられた。 From Tables 1 and 2, it was confirmed that according to the present invention, even when the cathode current density exceeds 10 A / dm 2 , copper-zinc alloy plating with a uniform composition without plating burn can be applied.
Claims (6)
１０Ａ／ｄｍ２を超える陰極電流密度で銅−亜鉛合金めっき処理を行い、かつ、前記銅−亜鉛合金めっき浴が、下記式、
Ｐ比＝Ｐ２Ｏ７の質量／（Ｃｕの質量＋Ｚｎの質量）
で表わされるＰ比が５．５〜７．０を満足し、
前記銅−亜鉛合金めっき浴のアミノ酸またはその塩から選ばれた少なくとも一種の濃度が０．１ｍｏｌ／Ｌ以上であり、ピロリン酸アルカリ金属塩の濃度が０．２〜０．８ｍｏｌ／Ｌであり、前記銅−亜鉛合金めっき浴のアミノ酸またはその塩が、ヒスチジンまたはその塩であることを特徴とする銅−亜鉛合金めっき方法。 A copper-zinc alloy plating bath containing a copper salt, a zinc salt, an alkali metal pyrophosphate, and at least one selected from amino acids or salts thereof and having a pH of 10.5 to 11.8 is used. In the conventional copper-zinc alloy plating method,
The copper-zinc alloy plating treatment is performed at a cathode current density exceeding 10 A / dm 2 , and the copper-zinc alloy plating bath has the following formula:
P ratio = mass of P 2 O 7 / (mass of Cu + mass of Zn)
P ratio represented by 5.5 to 7.0 is satisfied,
The concentration of at least one selected from amino acids or salts thereof in the copper-zinc alloy plating bath is 0.1 mol / L or more, and the concentration of alkali metal pyrophosphate is 0.2 to 0.8 mol / L, The copper-zinc alloy plating method, wherein the amino acid or salt thereof in the copper-zinc alloy plating bath is histidine or a salt thereof.
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