JP2009215590A - Copper-zinc alloy electroplating method, steel wire using the same, steel wire-rubber bonded composite and tire - Google Patents

Copper-zinc alloy electroplating method, steel wire using the same, steel wire-rubber bonded composite and tire Download PDF

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JP2009215590A
JP2009215590A JP2008059369A JP2008059369A JP2009215590A JP 2009215590 A JP2009215590 A JP 2009215590A JP 2008059369 A JP2008059369 A JP 2008059369A JP 2008059369 A JP2008059369 A JP 2008059369A JP 2009215590 A JP2009215590 A JP 2009215590A
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copper
steel wire
zinc alloy
zinc
alloy electroplating
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Yuji Sugano
裕士 菅野
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Bridgestone Corp
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    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/30—Inorganic materials
    • D07B2205/3021—Metals
    • D07B2205/3085—Alloys, i.e. non ferrous
    • D07B2205/3089—Brass, i.e. copper (Cu) and zinc (Zn) alloys

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  • Electroplating Methods And Accessories (AREA)
  • Ropes Or Cables (AREA)
  • Tires In General (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper-zinc alloy electroplating method which uses no cyan compound and by which the production of hydrogen is suppressed in the copper-zinc alloy plating on a steel product, a steel wire using the method, a steel wire-rubber bonded composite using the steel wire and a tire using the steel wire-rubber bonded composite. <P>SOLUTION: In the method of copper-zinc alloy electroplating in an aqueous solution containing a copper salt and an zinc salt, the electroplating is carried out by passing the pulse current in the duty ratio of pulse current of 0.05-0.60 for 1-50 msec pulse time. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は銅‐亜鉛合金電気めっき方法、それを用いたスチールワイヤおよびスチールワイヤ‐ゴム接着複合体およびタイヤ、関し、詳しくは、スチール製品に対して銅‐亜鉛合金めっきをする方法において、シアン化合物を使用することなく、かつ、水素の発生を抑制することができる銅‐亜鉛合金電気めっき方法、それを用いたスチールワイヤ、該スチールワイヤを用いたスチールワイヤ‐ゴム接着複合体、および該スチールワイヤ‐ゴム接着複合体を用いたタイヤに関する。   The present invention relates to a copper-zinc alloy electroplating method, a steel wire using the same, and a steel wire-rubber bonded composite and tire, and more particularly, to a method for plating a copper-zinc alloy on a steel product. Copper-zinc alloy electroplating method, steel wire using the same, steel wire-rubber bonded composite using the steel wire, and the steel wire -Related to tires using rubber bonded composites.

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、各種工業用ベルト部材などのゴム物品においては、銅‐亜鉛合金めっきを施したスチールワイヤまたはこれを複数本撚り合わせてなるスチールコードをゴムで被覆してなるものを用いることにより、補強効果を得ることが行われている。しかし、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。   At present, 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. In addition, in rubber articles such as various industrial belt members, the reinforcement effect can be achieved by using a steel wire coated with copper-zinc alloy plating or a steel cord formed by twisting a plurality of these wires and coated with rubber. Is getting done. 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。報告の中には錯化剤としてヒスチジン添加のピロりん酸カリウム浴を用いためっき浴、或いは硫酸銅と硫酸亜鉛を添加した水溶液に水酸化カリウムを添加し、錯化剤として酒石酸を用いた浴などが提案されている（例えば、特許文献１）。
特公平３−２０４７８号公報（特許請求の範囲等） As a solution to this problem, many copper-zinc alloy plating methods that do not use cyanide have been reported today. In the report, a plating bath using a potassium pyrophosphate bath with histidine added as a complexing agent, or a bath using tartaric acid as a complexing agent by adding potassium hydroxide to an aqueous solution containing copper sulfate and zinc sulfate. Etc. have been proposed (for example, Patent Document 1).
Japanese Patent Publication No. 3-20478 (Claims)

しかし、これらのめっき浴を用いれば、シアン浴のような毒性の問題はないが、光沢めっきが得られる電流密度において直流めっきを行うと銅‐亜鉛合金めっき層の形成と同時に水素が発生するため、銅‐亜鉛合金めっき層内に水素が取り込まれ、後工程での加工においてめっき層の脱落が発生し、スチールワイヤ‐ゴム複合体を製造する際に、接着性の低下を招いていた。さらに、水素の発生によりエネルギーが奪われてしまい、銅‐亜鉛合金めっき層の生産性が低いという問題点もある。そのため、いずれの条件においても実用に供するのが困難な状況にあるのが現状である。   However, if these plating baths are used, there is no problem of toxicity as in the case of a cyan bath. However, if direct current plating is performed at a current density at which bright plating can be obtained, hydrogen is generated simultaneously with the formation of the copper-zinc alloy plating layer. However, hydrogen was taken into the copper-zinc alloy plating layer, and the plating layer dropped off during processing in the subsequent process, resulting in a decrease in adhesiveness when manufacturing the steel wire-rubber composite. Furthermore, there is a problem that energy is deprived by the generation of hydrogen and the productivity of the copper-zinc alloy plating layer is low. Therefore, the current situation is that it is difficult to put it to practical use under any conditions.

そこで本発明の目的は、スチール製品に対して銅‐亜鉛合金めっきをする方法において、シアン化合物を使用することなく、かつ、水素の発生を抑制することができる銅‐亜鉛合金電気めっき方法、それを用いたスチールワイヤ、該スチールワイヤを用いたスチールワイヤ‐ゴム接着複合体、および該スチールワイヤ‐ゴム接着複合体を用いたタイヤを提供することにある。   Accordingly, an object of the present invention is to provide a copper-zinc alloy electroplating method capable of suppressing generation of hydrogen without using a cyanide compound in a method for plating a copper product on a steel product. It is an object to provide a steel wire using a steel wire, a steel wire-rubber bonded composite using the steel wire, and a tire using the steel wire-rubber bonded composite.

本発明者は、前記課題を解決するために鋭意検討をした結果、銅塩と亜鉛塩とを含む水溶液中にてスチール製品に対し銅‐亜鉛合金を電気めっきする方法において、所定の条件でパルス電流を通電することにより、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 problems, the present inventor has obtained a pulse under a predetermined condition in a method of electroplating a copper-zinc alloy on a steel product in an aqueous solution containing a copper salt and a zinc salt. The inventors have found that the above problem can be solved by applying a current, and have completed the present invention.

即ち、本発明の銅‐亜鉛合金電気めっき方法は、銅塩と亜鉛塩とを含む水溶液中にてスチール製品に対し銅‐亜鉛合金を電気めっきする方法において、パルス電流を通電し、前記パルス電流のデューティ比が０．０５〜０．６０、かつ、パルス時間が１ｍｓｅｃ〜５０ｍｓｅｃであることを特徴とするものである。   That is, the copper-zinc alloy electroplating method of the present invention is a method in which a copper-zinc alloy is electroplated on a steel product in an aqueous solution containing a copper salt and a zinc salt. The duty ratio is 0.05 to 0.60, and the pulse time is 1 msec to 50 msec.

本発明の銅‐亜鉛合金電気めっき方法においては、パルス電流は正パルスと負パルスとを交互に通電することが好ましい。   In the copper-zinc alloy electroplating method of the present invention, it is preferable that the pulse current is alternately supplied with a positive pulse and a negative pulse.

また、本発明のスチールワイヤは、前記銅‐亜鉛合金電気めっき処理が施されていることを特徴とするものである。   The steel wire of the present invention is characterized in that the copper-zinc alloy electroplating process is performed.

さらに、本発明のスチールワイヤ‐ゴム接着複合体は、前記スチールワイヤを用いたことを特徴とするものである。   Furthermore, the steel wire-rubber bonded composite of the present invention is characterized by using the steel wire.

さらにまた、本発明のタイヤは、一対のビード間でトロイド状に延びるカーカスを骨格とし、該カーカスのタイヤ半径方向外側にベルトを備えるタイヤにおいて、該カーカスおよびベルトのうちのいずれか一方または双方に、前記スチールワイヤ‐ゴム複合体を用いたことを特徴とするものである。   Furthermore, the tire according to the present invention has a carcass extending in a toroidal shape between a pair of beads as a skeleton, and includes a belt on the outer side in the tire radial direction of the carcass. The steel wire-rubber composite is used.

本発明の銅‐亜鉛合金電気めっき方法によれば、上記構成とすることで、スチール製品に対して銅‐亜鉛合金めっきをする方法において、シアン化合物を使用することなく、かつ、水素の発生を抑制することができる銅‐亜鉛合金電気めっき処理が可能となり、また、銅‐亜鉛合金めっき層の生産性の向上を図ることができる。さらに、パルス電流を用いることにより、めっき層形成時の過電圧を十分に大きくできることから、直流めっきに比して微細なめっき層の形成が可能となり、ゴム材料との接着性が向上する。   According to the copper-zinc alloy electroplating method of the present invention, in the above-described configuration, in the method of copper-zinc alloy plating on steel products, the generation of hydrogen is achieved without using a cyanide compound. The copper-zinc alloy electroplating process which can be suppressed becomes possible, and the productivity of the copper-zinc alloy plating layer can be improved. Furthermore, since the overvoltage at the time of forming the plating layer can be sufficiently increased by using the pulse current, a fine plating layer can be formed as compared with the direct current plating, and the adhesion to the rubber material is improved.

また、本発明の銅‐亜鉛合金電気めっき方法をスチールワイヤに適用することにより、銅‐亜鉛合金めっき層の脱落のないスチールワイヤを得ることができ、さらに本発明のスチールワイヤを用いることで、良好な接着性を有するスチールワイヤ‐ゴム複合体を得ることが可能となる。さらに、本発明のスチールワイヤ‐ゴム複合体を用いたタイヤを実現することが可能となる。   In addition, by applying the copper-zinc alloy electroplating method of the present invention to a steel wire, a steel wire without a copper-zinc alloy plating layer can be obtained, and by using the steel wire of the present invention, It becomes possible to obtain a steel wire-rubber composite having good adhesion. Furthermore, a tire using the steel wire-rubber composite of the present invention can be realized.

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‐亜鉛合金電気めっき方法は、銅塩と亜鉛塩とを含む水溶液中にてスチール製品に対し銅‐亜鉛合金を電気めっきする方法において、パルス電流を通電し、前記パルス電流のデューティ比が０．０５〜０．６０、好ましくは０．１〜０．３、かつ、パルス時間が１ｍｓｅｃ〜５０ｍｓｅｃ、好ましくは５ｍｓｅｃ〜３０ｍｓｅｃであることが肝要である。 Hereinafter, preferred embodiments of the present invention will be described in detail.
The copper-zinc alloy electroplating method of the present invention is a method in which a copper-zinc alloy is electroplated on a steel product in an aqueous solution containing a copper salt and a zinc salt. It is important that the ratio is 0.05 to 0.60, preferably 0.1 to 0.3, and the pulse time is 1 msec to 50 msec, preferably 5 msec to 30 msec.

パルス電流を通電し、デューティ比およびパルス時間を上記範囲内とすることにより、水素の発生を抑制することができ、後工程での加工において銅‐亜鉛合金めっき層の脱落を防止することができる。また、パルス電流とすることにより、銅‐亜鉛合金めっき層形成時の過電圧を十分に大きくできることから微細なめっき層形成が可能となり、スチールワイヤとゴム材料との接着性が向上する。   By supplying a pulse current and setting the duty ratio and pulse time within the above ranges, the generation of hydrogen can be suppressed, and the copper-zinc alloy plating layer can be prevented from falling off during subsequent processing. . Further, by setting the pulse current, the overvoltage at the time of forming the copper-zinc alloy plating layer can be sufficiently increased, so that a fine plating layer can be formed, and the adhesion between the steel wire and the rubber material is improved.

パルス電流のデューティ比については、この比が０．６０を超えると水素の発生量が増加し、本発明の所望の効果を得ることができない。一方、デューティ比が０．０５未満では光沢のある銅‐亜鉛合金めっき層を得ることができる電流密度範囲が狭くなってしまう。   Regarding the duty ratio of the pulse current, if this ratio exceeds 0.60, the amount of hydrogen generated increases, and the desired effect of the present invention cannot be obtained. On the other hand, if the duty ratio is less than 0.05, the current density range in which a glossy copper-zinc alloy plating layer can be obtained becomes narrow.

また、パルス時間は５０ｍｓｅｃを超えると、やはり水素の発生量が増加し、本発明の所望の効果を得ることができない。一方、１ｍｓｅｃ未満であると光沢のある銅‐亜鉛合金めっき層を得ることができる電流密度範囲が狭くなってしまう。   In addition, when the pulse time exceeds 50 msec, the amount of hydrogen generated increases, and the desired effect of the present invention cannot be obtained. On the other hand, if it is less than 1 msec, the current density range in which a glossy copper-zinc alloy plating layer can be obtained becomes narrow.

なお、デューティ比、およびパルス時間が上記の範囲内であれば、平均電流密度が２〜１４Ａ／ｄｍ２の範囲で光沢があり均一な銅‐亜鉛合金めっき層を得ることができ、その組成は平均電流密度が２〜１４Ａ／ｄｍ２の範囲内で変動しても影響を受けることはなく、安定して銅‐亜鉛合金めっき層を形成することが可能である。 If the duty ratio and the pulse time are within the above ranges, a glossy and uniform copper-zinc alloy plating layer can be obtained when the average current density is in the range of 2 to 14 A / dm 2. Even if the average current density fluctuates within the range of 2 to 14 A / dm 2 , the copper-zinc alloy plating layer can be stably formed without being affected.

本発明においては、パルス電流を正パルスと負パルスとを交互に通電することが好ましい。正パルスと負パルスとを交互に通電することにより、酸化物を含有した銅‐亜鉛合金めっき層を形成することができ、酸化物層が冷間加工時において粒子の粗大化を抑制することで、十分に粒子サイズを微細に保つことができ、スチールワイヤとゴム材料との接着性を向上させることができる。   In the present invention, it is preferable to apply a positive current and a negative pulse alternately as the pulse current. By alternately energizing the positive pulse and negative pulse, a copper-zinc alloy plating layer containing oxide can be formed, and the oxide layer can suppress grain coarsening during cold working. The particle size can be kept sufficiently fine, and the adhesion between the steel wire and the rubber material can be improved.

本発明に用いる銅‐亜鉛合金電気めっき浴は、銅塩と、亜鉛塩とを含むものであれば特に制限はされず、錯化剤としてヒスチジンを添加したピロりん酸アルカリ金属塩のめっき浴、または、水酸化カリウムを添加し、錯化剤として酒石酸塩を用いためっき浴等、公知の銅‐亜鉛合金電気めっき浴を用いることができる。   The copper-zinc alloy electroplating bath used in the present invention is not particularly limited as long as it contains a copper salt and a zinc salt, a plating bath of an alkali metal pyrophosphate salt to which histidine is added as a complexing agent, Alternatively, a known copper-zinc alloy electroplating bath such as a plating bath using potassium hydroxide and using tartrate as a complexing agent can be used.

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、ピロりん酸銅、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、りん酸銅、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。   Any copper salt may 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, cupric acetate, base Copper carbonate, cupric bromide, copper formate, copper hydroxide, cupric oxide, copper phosphate, copper silicofluoride, copper stearate, cupric citrate, etc. You may use only a seed | species and may use 2 or more types.

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、ピロりん酸亜鉛、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、りん酸亜鉛、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, bromide. Zinc, basic zinc carbonate, zinc oxalate, zinc phosphate, zinc silicofluoride, zinc stearate, zinc lactate, etc. can be mentioned, and only one of these may be used, or two or more may be used May be.

本発明における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、ピロりん酸アルカリ金属塩１５０〜４００ｇ／Ｌ、ヒスチジン又はその塩を０．２〜５０ｇ／Ｌ、また、酒石酸塩を用いた場合は５０〜４００ｇ／Ｌ程度とすることが好ましい。   The compounding amount of each component in the present invention is not particularly limited and can be appropriately selected. However, in consideration of industrial handling, the copper salt is 2 to 40 g / L in terms of copper and the zinc salt is 0 in terms of zinc. .5-30 g / L, alkali metal pyrophosphate 150-400 g / L, 0.2-50 g / L histidine or its salt, or about 50-400 g / L when tartrate is used Is preferred.

銅‐亜鉛合金電気めっきを施すに際しては、通常の電気めっき方法を採用することができる。例えば、浴温は３０〜５０℃程度、ｐＨは８〜１４の範囲で、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。   In performing the copper-zinc alloy electroplating, a normal electroplating method can be employed. For example, the bath temperature may be about 30 to 50 ° C., the pH may be in the range of 8 to 14, and electroplating may be performed with no stirring, mechanical stirring, or air stirring. At this time, any anode can be used as long as it can be used for electroplating of a normal copper-zinc alloy.

本発明における、被めっき体としては特に制限されず、通常、銅‐亜鉛合金電気めっき被膜を施されるものいずれでも使用でき、例えば、ゴム物品補強用スチールコードに使用するスチールワイヤのみならず、金属製品、プラスチック製品、セラミックス製品等に広く適用することができる。   In the present invention, the object to be plated is not particularly limited, and can usually be any of those subjected to a copper-zinc alloy electroplating film. For example, not only steel wires used for steel cords for reinforcing rubber articles, It can be widely applied to metal products, plastic products, ceramic products and the like.

また、本発明の銅‐亜鉛合金電気めっきを行う前に、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く、さらに必要に応じて、重クロム酸希薄溶液への浸漬、クリヤー塗装等を行ってもよい。   In addition, before performing the copper-zinc alloy electroplating of the present invention, the object to be plated can be subjected to usual pretreatments such as buffing, degreasing, dilute acid immersion, etc. according to a conventional method, or bright nickel plating, etc. It is also possible to apply a base plating. In addition, after plating, usual operations such as washing with water, washing with water, and drying may be performed, and if necessary, immersion in dilute dichromate solution, clear coating, and the like may be performed.

本発明のスチールワイヤは、上記銅‐亜鉛合金電気めっきを施されたスチールワイヤであり、ゴム材料との接着性に優れているため、タイヤに好適に用いることができる。   The steel wire of the present invention is a steel wire subjected to the above-described copper-zinc alloy electroplating, and is excellent in adhesiveness with a rubber material, and therefore can be suitably used for tires.

また、本発明のスチールワイヤ‐ゴム接着複合体は、上記銅‐亜鉛合金めっき処理が施されたスチールワイヤを用いたものであればよく、それ以外の具体的な構造、材質等については、特に制限されるものではないが、ゴム、硫黄、酸化亜鉛及び促進剤等を含有するゴムコンパウンド、又はゴムおよび有機ペルオキシド等を含有するゴムコンパウンドとを接触させ、加熱して得られるスチールワイヤ‐ゴム接着複合体を代表的な例として挙げることができる。   The steel wire-rubber bonded composite of the present invention may be any steel wire that has been subjected to the copper-zinc alloy plating treatment, and other specific structures, materials, etc. Although not limited, steel wire-rubber adhesion obtained by contacting and heating rubber compound containing rubber, sulfur, zinc oxide and accelerator, or rubber compound containing rubber and organic peroxide, etc. A complex can be given as a representative example.

また、本発明のタイヤは一対のビード間でトロイド状に延びるカーカスを骨格とし、そのタイヤ半径方向外側にベルトを備えるタイヤにおいて、かかるカーカスおよびベルトのうちのいずれか一方または双方に、上記本発明のスチールワイヤ‐ゴム複合体を用いたものであり、それ以外の具体的な構造、材質等については特に制限されるものではない。   The tire of the present invention has a carcass extending in a toroidal shape between a pair of beads as a skeleton, and includes a belt on the outer side in the tire radial direction. The steel wire-rubber composite is used, and other specific structures, materials, etc. are not particularly limited.

以下、本発明を、実施例を用いてより詳細に説明する。
表１および表２に記載された浴組成を有するめっき浴を用いて、併記された電気めっき条件にて各実施例および比較例の電気めっき処理を行い、得られた銅‐亜鉛合金めっき層の評価を行った。結果を表１、表２に併せて示す。なお、評価はめっき析出効率、および酸素導入比率を用いて行った。 Hereinafter, the present invention will be described in more detail with reference to examples.
Using the plating bath having the bath composition described in Table 1 and Table 2, the electroplating treatment of each example and comparative example was performed under the electroplating conditions described together, and the obtained copper-zinc alloy plating layer Evaluation was performed. The results are shown in Tables 1 and 2. The evaluation was performed using the plating deposition efficiency and the oxygen introduction ratio.

＜めっき析出効率（％）＞
理論析出量に対する実際の析出量の割合を百分率で表したものである。この値が大きいほど、水素の発生量が少なくなり、接着性の優れたスチールワイヤを製造することができ
、また、エネルギーロスも少なく銅‐亜鉛合金めっき層の生産性も優れていることを意味している。 <Plating deposition efficiency (%)>
The ratio of the actual precipitation amount to the theoretical precipitation amount is expressed as a percentage. The higher this value, the smaller the amount of hydrogen generated and the better the steel wire can be produced, and the less energy loss and the better the productivity of the copper-zinc alloy plating layer. is doing.

＜酸素導入比率（％）＞
酸化物として銅‐亜鉛合金めっき層内に取り込まれた酸素の割合（質量％）を示したものであり、この値が大きいほど、合金めっき層内の酸化物の割合が大きく、冷間加工時において合金粒子の粗大化を防止することができることを意味している。 <Oxygen introduction ratio (%)>
This shows the ratio (mass%) of oxygen taken into the copper-zinc alloy plating layer as an oxide. The larger this value, the larger the ratio of oxide in the alloy plating layer. It means that coarsening of alloy particles can be prevented.

Figure 2009215590
※１ Ａ：ピロりん酸カリウム
※２ Ｂ：酒石酸ナトリウム・カリウム４水和物
Figure 2009215590
 * 1 A: Potassium pyrophosphate * 2 B: Sodium potassium tartrate tetrahydrate

Figure 2009215590
※１ Ａ：ピロりん酸カリウム
※２ Ｂ：酒石酸ナトリウム・カリウム４水和物
Figure 2009215590
 * 1 A: Potassium pyrophosphate * 2 B: Sodium potassium tartrate tetrahydrate

実施例１〜６と比較例とを比較すると、めっき電流をパルス電流とすることにより、めっき析出効率が著しく向上している。従って、水素の発生が抑制されることになり、高品質の合金めっき層が効率よく形成されていることがわかる。   When Examples 1-6 are compared with the comparative example, the plating deposition efficiency is remarkably improved by making the plating current a pulse current. Accordingly, it is understood that generation of hydrogen is suppressed, and a high-quality alloy plating layer is efficiently formed.

また、正負交互にパルス電流をかけた実施例１〜５と負パルスをかけていない実施例６、比較例を比較すると、実施例１〜５の酸素導入比率が大きく増大している。このことより、銅‐亜鉛合金めっき層中に酸化物が導入されていることがわかる。   In addition, when Examples 1 to 5 in which positive and negative pulse currents are alternately applied, Example 6 in which negative pulses are not applied, and Comparative Examples are compared, the oxygen introduction ratios in Examples 1 to 5 are greatly increased. This shows that an oxide is introduced into the copper-zinc alloy plating layer.

Claims (5)

銅塩と亜鉛塩とを含む水溶液中にてスチール製品に対し銅‐亜鉛合金を電気めっきする方法において、パルス電流を通電し、前記パルス電流のデューティ比が０．０５〜０．６０、かつ、パルス時間が１ｍｓｅｃ〜５０ｍｓｅｃであることを特徴とする銅‐亜鉛合金電気めっき方法。   In a method of electroplating a copper-zinc alloy on a steel product in an aqueous solution containing a copper salt and a zinc salt, a pulse current is applied, and a duty ratio of the pulse current is 0.05 to 0.60, and A copper-zinc alloy electroplating method, wherein the pulse time is from 1 msec to 50 msec. 正パルスと負パルスとを交互に通電する請求項１記載の銅‐亜鉛合金電気めっき方法。   The copper-zinc alloy electroplating method according to claim 1, wherein the positive pulse and the negative pulse are alternately energized. 請求項１または２記載の銅‐亜鉛合金電気めっき方法によりめっき処理が施されていることを特徴とするスチールワイヤ。   A steel wire, which is plated by the copper-zinc alloy electroplating method according to claim 1 or 2. 請求項３記載のスチールワイヤを用いたことを特徴とするスチールワイヤ‐ゴム接着複合体。   A steel wire-rubber bonded composite comprising the steel wire according to claim 3. 一対のビード間でトロイド状に延びるカーカスを骨格とし、該カーカスのタイヤ半径方向外側にベルトを備えるタイヤにおいて、該カーカスおよびベルトのうちのいずれか一方または双方に、請求項４記載のスチールワイヤ‐ゴム複合体を用いたことを特徴とするタイヤ。   5. A steel wire according to claim 4, wherein a carcass extending in a toroidal shape between a pair of beads is used as a skeleton, and a belt is provided on the outer side of the carcass in the radial direction of the carcass. A tire using a rubber composite.
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