JP5797531B2 - Method for manufacturing brass-plated steel wire - Google Patents
Method for manufacturing brass-plated steel wire Download PDFInfo
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- JP5797531B2 JP5797531B2 JP2011249673A JP2011249673A JP5797531B2 JP 5797531 B2 JP5797531 B2 JP 5797531B2 JP 2011249673 A JP2011249673 A JP 2011249673A JP 2011249673 A JP2011249673 A JP 2011249673A JP 5797531 B2 JP5797531 B2 JP 5797531B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 99
- 239000010959 steel Substances 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 23
- 238000007747 plating Methods 0.000 claims description 53
- 238000011282 treatment Methods 0.000 claims description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 35
- 238000009792 diffusion process Methods 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 238000005246 galvanizing Methods 0.000 claims description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 229910001369 Brass Inorganic materials 0.000 description 20
- 239000010951 brass Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005491 wire drawing Methods 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- -1 for example Chemical compound 0.000 description 5
- 230000003449 preventive effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- WUGCLPOLOCIDHW-UHFFFAOYSA-N 2-aminoethanol;benzoic acid Chemical compound [NH3+]CCO.[O-]C(=O)C1=CC=CC=C1 WUGCLPOLOCIDHW-UHFFFAOYSA-N 0.000 description 1
- LODWDQOANQTUGD-UHFFFAOYSA-N 2-carboxyphenolate;dicyclohexylazanium Chemical compound OC(=O)C1=CC=CC=C1[O-].C1CCCCC1[NH2+]C1CCCCC1 LODWDQOANQTUGD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BAPVPOOWCZUVGA-UHFFFAOYSA-N benzoic acid;n-propan-2-ylpropan-2-amine Chemical compound CC(C)[NH2+]C(C)C.[O-]C(=O)C1=CC=CC=C1 BAPVPOOWCZUVGA-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- RIBMRDXQOWISQN-UHFFFAOYSA-N cyclohexanamine;cyclohexanecarboxylic acid Chemical compound NC1CCCCC1.OC(=O)C1CCCCC1 RIBMRDXQOWISQN-UHFFFAOYSA-N 0.000 description 1
- FNPGYAQZEUKTCV-UHFFFAOYSA-N cyclohexanamine;prop-2-enoic acid Chemical compound OC(=O)C=C.NC1CCCCC1 FNPGYAQZEUKTCV-UHFFFAOYSA-N 0.000 description 1
- BNAFKNQBXIKNDQ-UHFFFAOYSA-N cyclohexanecarboxylate;dicyclohexylazanium Chemical compound [O-]C(=O)C1CCCCC1.C1CCCCC1[NH2+]C1CCCCC1 BNAFKNQBXIKNDQ-UHFFFAOYSA-N 0.000 description 1
- CIFYUXXXOJJPOL-UHFFFAOYSA-N cyclohexylazanium;benzoate Chemical compound [NH3+]C1CCCCC1.[O-]C(=O)C1=CC=CC=C1 CIFYUXXXOJJPOL-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZFAKTZXUUNBLEB-UHFFFAOYSA-N dicyclohexylazanium;nitrite Chemical compound [O-]N=O.C1CCCCC1[NH2+]C1CCCCC1 ZFAKTZXUUNBLEB-UHFFFAOYSA-N 0.000 description 1
- CYYRAVBQFCQGFE-UHFFFAOYSA-N dicyclohexylazanium;prop-2-enoate Chemical compound [O-]C(=O)C=C.C1CCCCC1[NH2+]C1CCCCC1 CYYRAVBQFCQGFE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
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Classifications
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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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- Ropes Or Cables (AREA)
- Metal Extraction Processes (AREA)
Description
本発明は、ブラスめっき鋼線の製造方法（以下、単に「製造方法」とも称する）に関し、詳しくは、ブラスめっき鋼線の品質の向上と製造プロセスにおける省エネルギー化とを両立したブラスめっき鋼線の製造方法に関する。 The present invention relates to a method for manufacturing a brass-plated steel wire (hereinafter, also simply referred to as “manufacturing method”), and more specifically, a brass-plated steel wire that achieves both improved quality of the brass-plated steel wire and energy saving in the manufacturing process. It relates to a manufacturing method.
タイヤ用補強材のスチールコードを代表とするブラスめっき鋼線の製造過程は、主に乾式伸線による前段伸線を行い、その後にパテンティング熱処理によりパーライト鉄鋼組織の作り込みを行い、続いて鋼線材の表面にブラスめっきを施し最終伸線工程である湿式伸線に供する。ブラスめっきの手段として、銅めっき層の上に亜鉛めっきを行い、その後熱拡散によりブラスめっき層を形成する熱拡散めっき法が一般的に採用されている。 The manufacturing process of brass-plated steel wires, typically steel cords for tire reinforcements, is mainly pre-drawn by dry drawing, and then the pearlite steel structure is built by patenting heat treatment, followed by steel. The surface of the wire is subjected to brass plating and used for wet wire drawing, which is the final wire drawing step. As a means of brass plating, a thermal diffusion plating method is generally employed in which zinc plating is performed on a copper plating layer, and then a brass plating layer is formed by thermal diffusion.
ブラスめっきは銅と亜鉛との合金であり、表面傷等により鋼線の鉄地が露出すると、めっき−鉄地間に局部電池が形成される。鉄は黄銅よりも自然電位が低くアノードとして作用するため、溶出して腐食が促進されることになる。また、ブラスめっき自体も空気中に放置されると脱亜鉛現象による劣化が生じ、ゴムとの一次接着性の不良を招きやすい。そのため、最終伸線後のブラスめっき鋼線に防錆剤を被膜することが提案されている（例えば、特許文献１）。 Brass plating is an alloy of copper and zinc. When the iron ground of the steel wire is exposed due to surface scratches or the like, a local battery is formed between the plating and the iron ground. Since iron has a lower natural potential than brass and acts as an anode, it elutions and promotes corrosion. In addition, when the brass plating itself is left in the air, it deteriorates due to a dezincing phenomenon, and tends to cause poor primary adhesion with rubber. For this reason, it has been proposed to coat a rust preventive agent on the brass-plated steel wire after the final wire drawing (for example, Patent Document 1).
近年、タイヤの高性能化が進み、スチールコード用のブラスめっき鋼線の品質の向上が望まれている。このような要望に応えるためには、ブラスめっき鋼線の製造プロセスについてもさらなる検討が必要となってきている。また、スチールコード用ブラスめっき鋼線の製造プロセスにおける省エネルギー化や、製造設備のメンテナンス等も重要な課題となっている。 In recent years, as the performance of tires has improved, it is desired to improve the quality of brass-plated steel wires for steel cords. In order to meet such demands, further studies are necessary for the manufacturing process of brass-plated steel wires. In addition, energy saving in the manufacturing process of brass-plated steel wires for steel cords, maintenance of manufacturing facilities, etc. are also important issues.
そこで、本発明の目的は、ブラスめっき鋼線の品質の向上と製造プロセスにおける省エネルギー化とを両立したブラスめっき鋼線の製造方法およびそれにより得られたブラスめっき鋼線を提供することにある。 Therefore, an object of the present invention is to provide a method for producing a brass-plated steel wire that achieves both improvement in the quality of the brass-plated steel wire and energy saving in the production process, and a brass-plated steel wire obtained thereby.
本発明者は、上記課題を解消するためにブラスめっき鋼線の製造方法について鋭意検討した結果、以下の知見を得た。すなわち、熱拡散めっき法によりブラスめっき層を形成する場合、熱拡散時にブラスめっき層の表面に酸化亜鉛が生成する。この酸化亜鉛は、一般に針状で非常に硬質であるため、最終伸線工程における潤滑性を阻害する。そのため、鋼線材に対して熱拡散めっき法によりブラスめっき施した場合、引き抜き力の増大による消費電力のロスが生じる。また、ブラスめっき鋼線の表面の酸化亜鉛により潤滑性が損なわれることにより、ブラスめっき鋼線とダイとの摩擦が増大し、ブラスめっき鋼線の品質が低下することになる。さらに、ダイの寿命が短命化するといった弊害も生じることになる。 As a result of intensive studies on a method for producing a brass-plated steel wire in order to solve the above-mentioned problems, the present inventor has obtained the following knowledge. That is, when the brass plating layer is formed by the thermal diffusion plating method, zinc oxide is generated on the surface of the brass plating layer during thermal diffusion. Since this zinc oxide is generally acicular and very hard, it inhibits lubricity in the final wire drawing process. Therefore, when the steel wire is subjected to brass plating by a thermal diffusion plating method, a loss of power consumption due to an increase in pulling force occurs. Further, since the lubricity is impaired by the zinc oxide on the surface of the brass-plated steel wire, the friction between the brass-plated steel wire and the die increases, and the quality of the brass-plated steel wire is deteriorated. In addition, there is an adverse effect that the life of the die is shortened.
このような問題を解消する手法としては、熱拡散処理後にブラスめっき鋼線材を表面処理することにより、酸化亜鉛を低減させることが考えられる。しかしながら、熱拡散処理後に酸化亜鉛を低減させる工程を設けることは、工程スペースの制約、設備コスト、運転コストの観点からは好ましくない。 As a technique for solving such a problem, it is conceivable to reduce zinc oxide by surface-treating the brass-plated steel wire after the thermal diffusion treatment. However, providing a step of reducing zinc oxide after the thermal diffusion treatment is not preferable from the viewpoint of process space restriction, facility cost, and operation cost.
本発明者は、上記知見に基づいてさらに鋭意検討した結果、ブラスめっき層を形成するための熱拡散処理時に、ブラスめっき表面に酸化亜鉛が生成し難い条件とすることにより、上記課題を解消することができることを見出し、本発明を完成するに至った。 As a result of further intensive studies based on the above findings, the present inventor has solved the above problem by making it difficult for zinc oxide to be generated on the surface of the brass plating during the thermal diffusion treatment for forming the brass plating layer. As a result, the present invention has been completed.
すなわち、本発明のブラスめっき鋼線の製造方法は、鋼線材に銅めっきを施す銅めっき工程と、得られた銅めっき鋼線材に亜鉛めっきを施す亜鉛めっき工程と、鋼線材表面の銅と亜鉛とを熱拡散させブラスめっき鋼線材を得る熱拡散工程と、を含むブラスめっき鋼線の製造方法において、
前記銅めっき工程後前記亜鉛めっき工程前および／または前記亜鉛めっき工程後前記熱拡散工程前に、前記鋼線材に酸化防止処理を施すことを特徴とするものである。
That is, the method for producing a brass-plated steel wire according to the present invention includes a copper plating process for performing copper plating on a steel wire, a galvanizing process for performing galvanization on the obtained copper-plated steel wire, and copper and zinc on the surface of the steel wire. And a thermal diffusion step of obtaining a brass-plated steel wire by thermally diffusing, and a method for producing a brass-plated steel wire,
The steel wire material is subjected to an antioxidant treatment after the copper plating step and before the galvanizing step and / or after the galvanizing step and before the thermal diffusion step.
本発明の製造方法おいては、前記酸化防止処理を気相中で施してもよく、または液相中で施してもよい。また、本発明の製造方法においては、前記酸化防止処理をベンゾトリアゾールを用いて行うことが好ましい。 In the production method of the present invention, the antioxidant treatment may be performed in the gas phase or in the liquid phase. Moreover, in the manufacturing method of this invention, it is preferable to perform the said antioxidant process using benzotriazole.
本発明の他のブラスめっき鋼線の製造方法は、鋼線材に銅めっきを施す銅めっき工程と、得られた銅めっき鋼線材に亜鉛めっきを施す亜鉛めっき工程と、鋼線材表面の銅と亜鉛とを熱拡散させブラスめっき鋼線材を得る熱拡散工程と、を含むブラスめっき鋼線の製造方法において、
前記熱拡散工程を気化性防錆剤雰囲気中で行うことを特徴とするものである。
The other brass-plated steel wire manufacturing methods of the present invention include a copper plating step for copper plating on a steel wire, a galvanization step for galvanizing the obtained copper plated steel wire, and copper and zinc on the surface of the steel wire. And a thermal diffusion step of obtaining a brass-plated steel wire by thermally diffusing, and a method for producing a brass-plated steel wire,
The thermal diffusion step is performed in a vaporizable rust inhibitor atmosphere.
本発明によれば、ブラスめっき鋼線の品質の向上と製造プロセスにおける省エネルギー化とを両立したブラスめっき鋼線の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the brass plating steel wire which made compatible the improvement of the quality of a brass plating steel wire, and the energy-saving in a manufacturing process can be provided.
以下、本発明のブラスめっき鋼線の製造方法について、図面を用いて詳細に説明する。
本発明のブラスめっき鋼線の製造方法は、鋼線材に銅めっきを施す銅めっき工程と、得られた銅めっき鋼線材に亜鉛めっきを施す亜鉛めっき工程と、鋼線材表面の銅と亜鉛とを熱拡散させブラスめっき鋼線材を得る熱拡散工程と、を含む。図１は、パテンティングから最終伸線にかけての工程の一例を示すフローチャートである。図示例においては、まず、巻き出された鋼線材はパテンティング処理が施され、次いで酸洗および水洗を経て、銅めっき処理がなされている。その後、水洗、亜鉛めっき処理、水洗を経て、鋼線材の表面に銅および亜鉛が順次めっきされる。その後、熱拡散処理により銅めっきおよび亜鉛めっきが合金化されブラスめっきとなり、最終伸線に供される。
Hereinafter, the manufacturing method of the brass plating steel wire of the present invention is explained in detail using a drawing.
The method of manufacturing a brass-plated steel wire according to the present invention includes a copper plating process for performing copper plating on a steel wire, a galvanizing process for performing galvanization on the obtained copper-plated steel wire, and copper and zinc on the surface of the steel wire. And a thermal diffusion step of obtaining a brass-plated steel wire by thermal diffusion. FIG. 1 is a flowchart showing an example of a process from patenting to final wire drawing. In the illustrated example, first, the unrolled steel wire is subjected to a patenting treatment, and then subjected to a copper plating treatment through pickling and water washing. Then, copper and zinc are sequentially plated on the surface of the steel wire through water washing, galvanizing treatment, and water washing. Thereafter, copper plating and zinc plating are alloyed by thermal diffusion treatment to become brass plating, which is used for final wire drawing.
本発明の一好適な実施の形態としては、銅めっき工程後亜鉛めっき工程前および／または亜鉛めっき工程後熱拡散工程前に、鋼線材に酸化防止処理を施す。このように、熱拡散処理を行う前に、鋼線材に酸化防止処理が施されることにより、ブラスめっき層表面が酸化され難くなる。これにより、ブラスめっき鋼線材の表面の酸化亜鉛の生成量を低減させることができる。その結果、その後の最終伸線における引き抜き力が低下し、伸線電力を減らすことができ、省エネルギー化を図ることができる。 As a preferred embodiment of the present invention, the steel wire is subjected to an antioxidant treatment after the copper plating step and before the galvanizing step and / or after the galvanizing step and before the thermal diffusion step. As described above, the surface of the brass plating layer is hardly oxidized by subjecting the steel wire to the antioxidant treatment before the thermal diffusion treatment. Thereby, the production amount of zinc oxide on the surface of the brass-plated steel wire can be reduced. As a result, the drawing force in the subsequent final wire drawing is reduced, the wire drawing power can be reduced, and energy saving can be achieved.
また、引抜き力を低下させることにより、工具負担が減り、摩耗低減およびダイ等の工具の寿命が改善される。すなわち、ダイ内面の摩耗状態が改善され、ブラスめっき鋼線材によるダイのめっき凝着、縦キズ、リング摩耗が抑制される。さらに、酸化防止処理がなされていないブラスめっき鋼線は、伸線加工の際の線速が増加するに従い引抜き力が増大する傾向が見られるが、酸化防止処理により表面の酸化亜鉛量が低減されたブラスめっき鋼線においては、引抜き力には速度依存性が見られない。そのため、ブラスめっき鋼線材とダイとの摩擦によるブラスめっき鋼線の品質の低下を抑制することができる。 Also, by reducing the pulling force, the tool burden is reduced, wear is reduced, and the life of tools such as dies is improved. That is, the wear state of the inner surface of the die is improved, and die plating adhesion, vertical scratches, and ring wear due to the brass-plated steel wire are suppressed. In addition, brass-plated steel wires that have not undergone anti-oxidation treatment tend to increase the drawing force as the wire speed increases during wire drawing, but the amount of zinc oxide on the surface is reduced by the anti-oxidation treatment. In brass-plated steel wires, the drawing force does not depend on speed. Therefore, the deterioration of the quality of the brass-plated steel wire due to the friction between the brass-plated steel wire and the die can be suppressed.
本発明の製造方法においては、鋼線材に対する酸化防止処理を気相中で施してもよく、または液相中で施してもよい。酸化防止処理を気相中で行う場合、例えば、銅めっき処理後の水洗処理後、および／または亜鉛めっき処理後の水洗処理後に酸化防止処理を行う。また、気相中で酸化防止処理を行う場合、常温にて行ってもよいが、熱風を吹き付けたり、ホットプレートを用いて直接加熱し、気化性防錆剤を融点またはそれ以上の温度に加熱して、行うことが好ましい。例えば、気化性防錆剤としてベンゾトリアゾールを用いる場合は、ベンゾトリアゾールを５０〜２００℃に加熱し、得られた気体をブラスめっき鋼線材に吹き付ければよい。 In the production method of the present invention, the antioxidant treatment for the steel wire may be performed in the gas phase or in the liquid phase. When the antioxidant treatment is performed in the gas phase, for example, the antioxidant treatment is performed after the water washing treatment after the copper plating treatment and / or the water washing treatment after the galvanization treatment. In addition, when performing an antioxidant treatment in the gas phase, it may be carried out at room temperature, but it is heated by blowing hot air or directly using a hot plate to heat the vaporizable rust inhibitor to a melting point or higher. Therefore, it is preferable to carry out. For example, when benzotriazole is used as the vaporizable rust inhibitor, the benzotriazole may be heated to 50 to 200 ° C. and the resulting gas may be sprayed onto the brass-plated steel wire.
気化性防錆剤としては、ベンゾトリアゾール以外にも、例えば、トリルトリアゾール、ジシクロヘキシルアンモニウムナイトライト、ジシクロヘキシルアンモニウムサリシレート、モノエタノールアミンベンゾエート、ジイソプロピルアンモニウムベンゾエート、シクロヘキシルアミンベンゾエート、ジシクロヘキシルアンモニウムシクロヘキサンカルボキシレート、シクロヘキシルアミンシクロヘキサンカルボキシレート、ジシクロヘキシルアンモニウムアクリレート、シクロヘキシルアミンアクリレート等を用いることができる。好適には、ベンゾトリアゾールである。 As the vaporizable rust preventive, in addition to benzotriazole, for example, tolyltriazole, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, diisopropylammonium benzoate, cyclohexylamine benzoate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylamine cyclohexane Carboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate and the like can be used. Preferred is benzotriazole.
酸化防止処理を液相中で行う場合、例えば、銅めっき処理後の水洗処理の水浴および／または亜鉛処理後の水洗処理の水浴にベンゾトリアゾールやトリルトリアゾール等のトリアゾール化合物を添加することにより行うことができる。好適にはベンゾトリアゾールである。この場合、水浴中のベンゾトリアゾールの濃度は、０．１〜５．０ｍｇ／Ｌ程度とするのが好ましい。なお、処理時間は、トリアゾール化合物の濃度に応じて適宜決定することができ、トリアゾール化合物濃度が低ければ処理時間は長く、濃度が高ければ処理時間を短くすることができる。例えば、トリアゾール化合物濃度を０．１ｇ／Ｌとした場合は、１０〜３０秒とすればよい。 When the antioxidant treatment is performed in the liquid phase, for example, it is performed by adding a triazole compound such as benzotriazole or tolyltriazole to the water bath of the water washing treatment after the copper plating treatment and / or the water bath of the water washing treatment after the zinc treatment. Can do. Benzotriazole is preferred. In this case, the concentration of benzotriazole in the water bath is preferably about 0.1 to 5.0 mg / L. The treatment time can be appropriately determined according to the concentration of the triazole compound. If the triazole compound concentration is low, the treatment time is long, and if the concentration is high, the treatment time can be shortened. For example, when the triazole compound concentration is 0.1 g / L, it may be 10 to 30 seconds.
また、本発明の他の好適な実施の形態は、鋼線材に銅めっきを施す銅めっき工程と、得られた銅めっき鋼線材に亜鉛めっきを施す亜鉛めっき工程と、鋼線材表面の銅と亜鉛とを熱拡散させブラスめっき鋼線材を得る熱拡散工程と、を含み、熱拡散工程を気化性防錆剤雰囲気中で行う。熱拡散処理を気化性防錆剤雰囲気下で行うことにより、ブラスめっき表面に酸化亜鉛が生成し難くなる。本実施の形態においても、気化性防錆剤としては、上記のものと同様のものを用いることができる。 In addition, another preferred embodiment of the present invention includes a copper plating step for copper plating on a steel wire, a galvanization step for galvanizing the obtained copper plated steel wire, and copper and zinc on the surface of the steel wire. And a heat diffusion step of obtaining a brass-plated steel wire by performing heat diffusion, and performing the heat diffusion step in a vaporizable rust preventive agent atmosphere. By performing the thermal diffusion treatment in a vaporizable rust preventive atmosphere, zinc oxide is hardly generated on the surface of the brass plating. Also in the present embodiment, as the vaporizable rust preventive agent, the same ones as described above can be used.
本発明の製造方法は、ブラスめっき層を形成するための熱拡散処理時に、ブラスめっき表面に酸化亜鉛が生成し難い条件とすることが重要であり、それ以外の銅めっき処理、亜鉛めっき処理等の他の工程における条件等については常法に従い適宜選定して実施することができ、特に制限されるものではない。 In the production method of the present invention, it is important that the thermal diffusion treatment for forming the brass plating layer is performed under conditions that make it difficult for zinc oxide to be generated on the brass plating surface, and other copper plating treatments, zinc plating treatments, etc. The conditions in the other steps can be appropriately selected and carried out according to a conventional method, and are not particularly limited.
また、本発明のブラスめっき鋼線の製造方法に用いる鋼線材としては、通常、スチールコード用として用いられている鋼線材であればよく、その径や材質等については、公知のものであればいずれも使用可能であるが、鋼線材としては炭素含有量０．７０質量％以上の高炭素鋼線が好適である。なお、伸線工程についても、鋼線材の伸線工程において通常使用される伸線機を用いて、常法に従い伸線加工を行うものであれば、伸線条件等に特に制限はない。 Moreover, as a steel wire used for the method of manufacturing the brass-plated steel wire of the present invention, it is sufficient if it is a steel wire usually used for steel cords. Any of them can be used, but a high carbon steel wire having a carbon content of 0.70% by mass or more is suitable as the steel wire. In addition, the wire drawing process is not particularly limited as long as the wire drawing is performed in accordance with a conventional method using a wire drawing machine usually used in the wire drawing process of a steel wire.
以下、本発明の製造方法について、実施例を用いてより詳細に説明する。
＜実施例１〜３および比較例＞
線径１．７２ｍｍの鋼線材に対して銅めっき、水洗、亜鉛めっき、水洗を順次施し、その後、熱拡散処理によりブラスめっき鋼線材を得た。この際、表１に示す条件となるように銅めっき後の水洗浴および亜鉛めっき後の水洗浴に、防錆剤としてベンゾトリアゾール（ＢＴＡ）を添加し、鋼線材に対して酸化防止処理を実施した。その後、銅めっきおよび亜鉛がめっきが施された鋼線材に熱拡散処理を施し、ブラスめっき鋼線材とした。得られたブラスめっき鋼線材の表面上に残存している酸化亜鉛の量を同表に併記する。その後、得られたブラスめっき鋼線材に対して、線径０．３０ｍｍまで最終湿式伸線を施してブラスめっき鋼線を得た。
Hereinafter, the production method of the present invention will be described in more detail with reference to examples.
<Examples 1-3 and a comparative example>
Copper plating, water washing, zinc plating, and water washing were sequentially applied to a steel wire having a wire diameter of 1.72 mm, and then a brass-plated steel wire was obtained by thermal diffusion treatment. At this time, benzotriazole (BTA) was added as a rust inhibitor to the water washing bath after copper plating and the water washing bath after zinc plating so that the conditions shown in Table 1 were satisfied, and the steel wire was subjected to an antioxidant treatment. did. Thereafter, the steel wire material plated with copper plating and zinc was subjected to thermal diffusion treatment to obtain a brass-plated steel wire material. The amount of zinc oxide remaining on the surface of the obtained brass-plated steel wire is also shown in the same table. Thereafter, the obtained brass-plated steel wire was subjected to final wet drawing to a wire diameter of 0.30 mm to obtain a brass-plated steel wire.
＜ダイの寿命＞
実施例１〜３および比較例のブラスめっき鋼線材に最終湿式伸線を施すに際し、湿式伸線機の最初のダイの寿命を、比較例を１００とする指数にて評価した。この数値が大なるほど、ダイの寿命が長いことを意味する。得られた結果を同表に併記する。
<Die life>
When the final wet drawing was performed on the brass-plated steel wires of Examples 1 to 3 and the comparative example, the life of the first die of the wet drawing machine was evaluated by an index with the comparative example being 100. A larger value means a longer die life. The obtained results are also shown in the table.
＜消費電力＞
実施例１〜３および比較例のブラスめっき鋼線材に最終湿式伸線を施すに際し、最終湿式伸線に要した電力を測定し、比較例を基準とて消費電力の変化量を算出した。得られた結果を同表に併記する。
<Power consumption>
When final wet drawing was performed on the brass-plated steel wires of Examples 1 to 3 and the comparative example, the power required for the final wet drawing was measured, and the amount of change in power consumption was calculated based on the comparative example. The obtained results are also shown in the table.
＜捻回特性＞
実施例１〜３および比較例のブラスめっき鋼線について、直線状となるよう保持したブラスめっき鋼線に、ブラスめっき鋼線の直径の１００倍の長さあたり３回に相当する量の捻りを加えてから元の状態に捻り戻すことを繰り返す繰返し捻り試験を行って、ブラスめっき鋼線にクラックが発生するまでに加えた捻りおよび捻り戻しの総量（回／１００Ｄ）を測定した。得られた結果を同表に併記する。
<Twisting characteristics>
For the brass-plated steel wires of Examples 1 to 3 and the comparative example, the brass-plated steel wire held so as to be linear is twisted in an amount equivalent to three times per 100 times the diameter of the brass-plated steel wire. A repeated twist test in which the twisting was repeated after the addition was repeated, and the total amount of twisting and untwisting (times / 100 D) applied until the crack was generated in the brass-plated steel wire was measured. The obtained results are also shown in the table.
表１より本発明の製造方法によれば、ブラスめっき鋼線材表面上の酸化亜鉛を低減できていることがわかる。これにより、ダイ寿命が長くなり、また、消費電力が低減されており、製造プロセスにおける省エネルギー化が可能であることが確かめられた。また、捻回特性も向上しており、ブラスめっき鋼線の品質も向上していることがわかる。 Table 1 shows that according to the manufacturing method of the present invention, zinc oxide on the surface of the brass-plated steel wire can be reduced. As a result, it was confirmed that the die life was extended, the power consumption was reduced, and energy saving in the manufacturing process was possible. Moreover, it turns out that the twist characteristic is also improved and the quality of the brass plating steel wire is also improving.
Claims (5)
前記銅めっき工程後前記亜鉛めっき工程前および／または前記亜鉛めっき工程後前記熱拡散工程前に、前記鋼線材に酸化防止処理を施すことを特徴とするブラスめっき鋼線の製造方法。 Copper plating process for copper plating on steel wire, galvanization process for galvanizing the obtained copper plated steel wire, and thermal diffusion process for obtaining brass-plated steel wire by thermally diffusing copper and zinc on the surface of the steel wire In a method for manufacturing a brass-plated steel wire including:
Manufacturing method of the copper plating step after the galvanizing step before and / or before the thermal diffusion step after the galvanizing step, brass-plated steel wire characterized by the antioxidant treatment is subjected before Symbol steel wires.
前記熱拡散工程を気化性防錆剤雰囲気中で行うことを特徴とするブラスめっき鋼線の製造方法。 Copper plating process for copper plating on steel wire, galvanization process for galvanizing the obtained copper plated steel wire, and thermal diffusion process for obtaining brass-plated steel wire by thermally diffusing copper and zinc on the surface of the steel wire In a method for manufacturing a brass-plated steel wire including:
A method for producing a brass-plated steel wire, wherein the thermal diffusion step is performed in a vaporizable rust inhibitor atmosphere.
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