WO2021131340A1 - Bain galvanoplastique au zinc nickel et procédé de placage faisant appel à celui-ci - Google Patents

Bain galvanoplastique au zinc nickel et procédé de placage faisant appel à celui-ci Download PDF

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Publication number
WO2021131340A1
WO2021131340A1 PCT/JP2020/041350 JP2020041350W WO2021131340A1 WO 2021131340 A1 WO2021131340 A1 WO 2021131340A1 JP 2020041350 W JP2020041350 W JP 2020041350W WO 2021131340 A1 WO2021131340 A1 WO 2021131340A1
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zinc
nickel
plating bath
nickel plating
plating
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PCT/JP2020/041350
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English (en)
Japanese (ja)
Inventor
将義 三上
悠司 橋本
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ディップソール株式会社
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Priority to JP2021566885A priority Critical patent/JPWO2021131340A1/ja
Publication of WO2021131340A1 publication Critical patent/WO2021131340A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys

Definitions

  • the present invention relates to a zinc-nickel plating bath.
  • the present invention relates to an electrozinc nickel plating bath that is hard to burn and prevents nickel hydroxide from depositing on the cathode, and a plating method using the bath, which can be used as a general surface treatment for corrosion prevention.
  • This zinc-nickel alloy plating usually uses an alkaline or weakly acidic plating solution containing zinc ions and nickel ions, and uses the object to be plated as a cathode and energizes the surface of the cathode to be plated with zinc nickel. It is alloy plated.
  • an alkaline plating solution bath
  • the current efficiency is poor and the plating speed is slow.
  • a weakly acidic plating solution containing potassium chloride (conductive salt) and ammonium chloride (buffer) is used in a barrel bath (a plating solution (eclectic bath) in which the object to be plated is placed in a basket).
  • a plating solution eclectic bath
  • Burning may occur at the same time.
  • Patent Document 2 contains a conductive salt, metallic zinc, and a brightener as an acidic zinc plating bath having improved stability over time even at a high temperature of 30 to 50 ° C., as a component of the brightener.
  • An acidic zinc-plated bath containing at least one of a cumylphenol-based anionic surfactant has been proposed.
  • Patent Document 2 does not mention the acidic zinc-nickel alloy electroplating solution at all.
  • An object of the present invention is to provide an electrozinc-nickel plating bath that is hard to burn and nickel hydroxide is hard to precipitate on the cathode. It is also an object of the present invention to provide an electrozinc-nickel plating method.
  • the pH of the zinc-nickel plating bath is adjusted in the range of 3.5 to 6.9, and a cumylphenol-based anionic surfactant and an amine-based chelating agent are used in combination with zinc ions, nickel ions, and chloride ions. Then, it was made based on the finding that the above-mentioned problems can be solved efficiently. That is, the present invention has the following aspects. 1. Zinc nickel plating bath with a pH of 3.5 to 6.9, zinc ion, nickel ion, chloride ion, cumylphenol anionic surfactant and amine chelating agent. A zinc-nickel plating bath characterized by. 2.
  • the amine-based chelating agent is at least one selected from the group consisting of an alkylene amine compound having 1 to 12 carbon atoms, an ethylene oxide adduct thereof, and a propylene oxide adduct. 4.
  • the zinc-nickel plating bath according to any one of 1 to 6 above which contains an aromatic aldehyde and / or an aromatic ketone.
  • the zinc-nickel plating bath according to 7 above wherein the aromatic aldehyde and the aromatic ketone are O-chlorobenzaldehyde and benzalacetone, respectively.
  • the zinc-nickel plating bath according to any one of 1 to 8 above which contains at least one selected from the group consisting of ammonia, ammonium salts, acetic acid, acetates, boric acid and borates.
  • the zinc-nickel plating bath according to any one of 1 to 9 above which does not contain sulfate ions. 11.
  • the object to be plated is used as a cathode, zinc, nickel or both are used as anodes, and the object to be plated is plated with zinc nickel using the zinc-nickel plating bath according to any one of 1 to 10 above.
  • a plating method characterized by subjecting an anode to zinc-nickel plating using a bath.
  • the plating bath of the present invention is a weakly acidic plating solution (chloride bath)
  • the obtained zinc-nickel film is hard to burn and hydroxylation is performed during the electroplating process, while maintaining the advantage that high-speed plating can be performed. It has an excellent effect of suppressing the phenomenon of nickel depositing and adhering to the cathode.
  • the pH of the bath is set to 3.5 to 6.9 in order to make it a weakly acidic bath.
  • a chloride bath is most preferable.
  • the pH of the plating bath is preferably 4.5 to 6.0, most preferably 5.2 to 5.8.
  • the pH of the plating bath can be easily adjusted by using hydrochloric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia water, sodium carbonate aqueous solution, potassium carbonate aqueous solution, acetic acid, sodium acetate aqueous solution, potassium acetate aqueous solution and the like.
  • the plating bath of the present invention contains zinc ion, nickel ion, chloride ion (Cl-), a cumylphenol anionic surfactant and an amine chelating agent as essential components.
  • Zinc ions are derived from water-soluble zinc salts, and zinc chloride is preferable as the water-soluble zinc salt.
  • the concentration is preferably 40 to 130 g / L. More preferably, it is 60 to 110 g / L.
  • Nickel ions are derived from water-soluble nickel salts, and nickel chloride is preferable as the water-soluble nickel salt.
  • the concentration is preferably 70 to 150 g / L in terms of nickel chloride hexahydrate. More preferred is 75-120 g / L.
  • Chloride ions come from the above zinc chloride and nickel chloride, but also from other water-soluble chlorides added to the plating bath.
  • the amount of chloride ions is the total amount of chloride ions resulting from the water-soluble chloride in the plating bath.
  • the concentration is preferably 100 to 300 g / L. More preferred is 120-240 g / L.
  • Examples of the cumylphenol-based anionic surfactant include sulfonates in which ethylene oxide and / and propylene oxide are added in a total amount of 3 to 65 mol, preferably 8 to 62 mol to cumylphenol.
  • Examples of the sulfonate include potassium salt, sodium salt, amine salt and the like. Specific examples thereof include sodium polyoxyethylene p-cumylphenyl ether sulfate (3 to 65 mol, preferably 8 to 62 mol) of EO addition moles.
  • the concentration of ethylene oxide and / and propylene oxide added to cumylphenol in the plating bath is preferably 0.1 to 10 g / L, more preferably 0.2 to 5 g / L.
  • amine-based chelating agent examples include alkyleneamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, ethylene oxide adducts and propylene oxide adducts of the alkyleneamines; N- (2-aminoethyl) ethanolamine.
  • Amino alcohols such as 2-hydroxyethylaminopropylamine; N-2 (-hydroxyethyl) -N, N', N'-triethylethylenediamine, N, N'-di (2-hydroxyethyl) -N, N' Poly (hydroxyalkyl) alkylenes such as -diethylethylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl) propylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine.
  • Diamine Poly (alkyleneimine) obtained from ethyleneimine, 1,2-propyleneimine and the like, poly (alkyleneamine) or poly (aminoalcohol) obtained from ethylenediamine, triethylenetetramine, ethanolamine, diethanolamine and the like can be mentioned. ..
  • alkyleneamine compounds having 1 to 12 carbon atoms (preferably 2 to 10 carbon atoms) and 2 to 7 nitrogen atoms (preferably 2 to 6 nitrogen atoms), ethylene oxide adducts and propylene oxide adducts thereof. Is preferable.
  • These amine-based chelating agents may be used alone or in combination of two or more.
  • the concentration of the amine-based chelating agent in the plating bath is preferably 0.5 to 50 g / L, more preferably 1 to 5 g / L.
  • the plating bath of the present invention may contain one or more conductive salts.
  • Conductive salts used in the present invention include, for example, chlorides, sulfates, carbonates and the like. Among them, it is preferable to use at least one chloride of potassium chloride, ammonium chloride, and sodium chloride. In particular, potassium chloride and ammonium chloride alone or in combination are preferable.
  • the concentration of potassium chloride is preferably 150 to 250 g / L when used alone, and the concentration of ammonium chloride is preferably 150 to 300 g / L when used alone.
  • potassium chloride is preferably 70 to 200 g / L, and ammonium chloride is preferably 15 to 150 g / L.
  • Ammonium chloride also acts as a buffer.
  • ammonium chloride it is preferable to use an acetate such as ammonia, ammonium salt, borate or borate, acetic acid, potassium acetate or sodium acetate as a buffer.
  • the total concentration of boric acid and / or borate is preferably 15-90 g / L.
  • the total concentration of acetic acid and / or acetate is preferably 5 to 140 g / L, more preferably 7 to 140 g / L, and even more preferably 8 to 120 g / L. Further, even when ammonium chloride is used, these buffers can be appropriately used.
  • the plating bath of the present invention preferably contains an aromatic aldehyde having 7 to 10 carbon atoms or an aromatic ketone having 8 to 14 carbon atoms.
  • aromatic aldehyde examples include o-carboxybenzaldehyde, benzaldehyde, o-chlorobenzaldehyde, p-tolvaldehyde, anisaldehyde, p-dimethylaminobenzaldehyde, and terephthalaldehyde.
  • the aromatic ketone include benzalacetone, benzophenone, acetophenone, terephthaloylbenzyl chloride and the like.
  • particularly preferable compounds are benzalacetone and o-chlorbenzaldehyde.
  • concentration in each bath is preferably 0.1 to 20 mg / L, more preferably 0.3 to 10 mg / L.
  • the rest of the plating bath of the present invention is water.
  • Electroplating is used as a plating method using the zinc-nickel plating bath of the present invention. Electroplating can be performed by direct current or pulse current.
  • the bath temperature is usually in the range of 25 to 50 ° C, preferably in the range of 30 to 45 ° C.
  • the current density is usually preferably carried out under electrolytic conditions in the range of 0.1 to 15 A / dm2, preferably in the range of 0.5 to 10 A / dm2. Further, when plating is performed, it is preferable to stir the liquid by air blow or jet jet. By doing so, the current density can be further increased.
  • As the anode a zinc plate, a nickel plate, a zinc ball, a nickel chip or the like is desirable.
  • a metal article to which the zinc-nickel plating film of the present invention is applied is used.
  • this metal article various metals such as iron, nickel and copper, and alloys thereof, or electrically conductive articles such as metals and alloys such as aluminum which have been subjected to zinc substitution treatment are used, and the shape thereof is pre- Any material such as a flat plate such as a metal or an article having a complicated appearance, for example, a fastening part such as a bolt or a nut, or various cast parts such as a brake caliper can be used.
  • the object to be plated is used as a cathode, zinc and nickel are used as anodes, and a part or all of the zinc anode is installed in an anode chamber separated by an ion exchange diaphragm, and the zinc-nickel plating bath is used.
  • Zinc-nickel plating can be applied to the plated body. According to this method, an increase in metal concentration (particularly zinc concentration) in the plating solution due to operation can be suppressed and controlled, so that there is an advantage that a plating film having stable quality can be obtained.
  • the nickel eutectoid rate in the zinc nickel plating film obtained by using the electrozinc nickel plating bath of the present invention is preferably 5 to 18% by weight, more preferably 10 to 18% by weight, and most preferably 12 ⁇ 15% by weight.
  • the balance is preferably zinc.
  • Example 1 Zinc chloride 73 g / L (zinc concentration 35 g / L), nickel chloride hexahydrate 89 g / L (nickel concentration 22 g / L), potassium chloride 180 g / L (total chlorine concentration 170 g / L), ammonium chloride 30 g / L L, polyoxyethylene p-cumylphenyl ether sulfate sodium salt (EO addition mol 40 mol: Neucol CMP-40-SN) 0.25 g / L, benzalacetone 6 mg / L, diethylenetriamine 2.5 g / L, 1.5 g / L of sodium benzoate and 90 g / L of potassium acetate were mixed and dissolved in water, and the pH was adjusted to 5.4 with hydrochloric acid to prepare a plating bath (1 liter).
  • EO addition mol 40 mol: Neucol CMP-40-SN polyoxyethylene p-cumylphenyl ether sulfate sodium salt
  • the iron plate was pretreated in the steps of alkaline degreasing, water washing, pickling, water washing, alkaline electrolysis washing, water washing, hydrochloric acid activation, and water washing, and this was used as a cathode.
  • a nickel plate was used as the anode, and plating was performed at a bath temperature of 35 ° C. and a DC power supply at a cathode current density of 4 A / dm 2 for 10 minutes.
  • the plating bath was stirred at a rotation speed of 1200 rpm using a regular stirrer having a diameter of 8 ⁇ 30 mm and a magnetic stirrer.
  • the iron plate is a long panel for Halcel test having a length of 65 mm, a width of 200 mm, and a thickness of 0.5 mm
  • the nickel plate is a plate having a length of 65 mm, a width of 65 mm, and a thickness of 2 mm.
  • a plating test similar to the Halcel test was performed, and the nickel elution rate (%) of the zinc nickel plating film, the film thickness distribution, the precipitation of nickel hydroxide at the cathode, and the burnt appearance and appearance of the zinc nickel plating film (Halcel). Appearance) was evaluated by the following method. The evaluation results are shown in Table 1.
  • the nickel eutectoid rate (%) and the film thickness of the plating film were measured using a fluorescent X-ray analyzer (Microelement Monitor SEA5120, manufactured by SII Nanotechnology Co., Ltd.).
  • SEA5120 fluorescent X-ray analyzer
  • the cathode surface at the end of the zinc-nickel plating treatment was visually observed, and the precipitation of nickel hydroxide on the cathode was evaluated according to the following criteria.
  • Precipitation width is less than 6 mm from the left end (high current part side) of the Hull cell test panel (allowable range)
  • C Precipitation width is 6 mm or more from the left end (high current part side) of the Hull cell test panel (cannot be used) (Zinc-nickel plating film burnt) The occurrence of burns on the zinc-nickel plating film at the end of the zinc-nickel plating treatment was evaluated according to the following criteria. If the evaluations in the Halsel test are A and B, no burning will occur on the object to be plated when actually plating with an article.
  • A Burn width is less than 6 mm (good) from the left end (high current part side) of the Hull cell test panel.
  • B Burn width is less than 9 mm from the left end (high current part side) of the Hull cell test panel (allowable range)
  • C Burn width is 9 mm or more from the left end (high current part side) of the Hull cell test panel (cannot be used) (Appearance of zinc-nickel plating film (Halcel appearance)) The appearance of Halsel in the zinc-nickel plating film at the end of the zinc-nickel plating treatment was evaluated according to the following criteria.
  • A Hull cell test panel 3mm from the left end (high current part side) to the right side, cloudy and stain-free appearance (very good)
  • B Hull cell test panel 6mm from the left end (high current part side) to the right side, cloudy and stain-free appearance (good)
  • C Hull cell test panel 9 mm from the left end (high current part side) to the right side, cloudy and stain-free appearance (allowable range)
  • D Appearance with light cloudiness and stains on the entire Halsel test panel (unusable)
  • E Appearance with dark cloudiness and stains on the entire Halsel test panel (unusable)
  • Example 2 Zinc chloride 73 g / L (zinc concentration 35 g / L), nickel chloride hexahydrate 89 g / L (nickel concentration 22 g / L), potassium chloride 180 g / L (total chlorine concentration 170 g / L), ammonium chloride 30 g / L L, polyoxyethylene p-cumylphenyl ether sulfate sodium salt (EO addition mol 60 mol: Neucol CMP-60-SN) 1 g / L, benzalacetone 6 mg / L, diethylenetriamine 2.5 g / L, benzoic acid 1.5 g / L of sodium and 90 g / L of potassium acetate were mixed and dissolved in water, and the pH was adjusted to 5.4 with hydrochloric acid to prepare a plating bath (1 liter).
  • polyoxyethylene p-cumylphenyl ether sulfate sodium salt EO addition mol 60 mol: Neucol CMP-60-SN
  • Example 3 Zinc chloride 73 g / L (zinc concentration 35 g / L), nickel chloride hexahydrate 89 g / L (nickel concentration 22 g / L), potassium chloride 180 g / L (total chlorine concentration 170 g / L), ammonium chloride 30 g / L L, polyoxyethylene p-cumylphenyl ether sulfate sodium salt (EO addition mol 11 mol: Neucol CMP-11-SN) 1 g / L, benzalacetone 6 mg / L, diethylenetriamine 2.5 g / L, benzoic acid 1.5 g / L of sodium and 90 g / L of potassium acetate were mixed and dissolved in water, and the pH was adjusted to 5.4 with hydrochloric acid to prepare a plating bath (1 liter).
  • polyoxyethylene p-cumylphenyl ether sulfate sodium salt EO addition mol 11 mol: Neucol CMP-11-SN
  • Example 4 Zinc chloride 73 g / L (zinc concentration 35 g / L), nickel chloride hexahydrate 89 g / L (nickel concentration 22 g / L), potassium chloride 180 g / L (total chlorine concentration 170 g / L), ammonium chloride 30 g / L L, polyoxyethylene p-cumylphenyl ether sulfate sodium salt (EO addition mol 20 mol: Neucol CMP-20-SN) 1 g / L, benzalacetone 6 mg / L, diethylenetriamine 2.5 g / L, benzoic acid 1.5 g / L of sodium and 90 g / L of potassium acetate were mixed and dissolved in water, and the pH was adjusted to 5.4 with hydrochloric acid to prepare a plating bath (1 liter).
  • polyoxyethylene p-cumylphenyl ether sulfate sodium salt EO addition mol 20 mol: Neucol CMP-20-SN
  • Example 5 Zinc chloride 73 g / L (zinc concentration 35 g / L), nickel chloride hexahydrate 89 g / L (nickel concentration 22 g / L), potassium chloride 220 g / L (total chlorine concentration 170 g / L), polyoxyethylene p -Cumylphenyl ether sulfate sodium salt (EO addition mol 11 mol: Neucol CMP-11-SN) 1 g / L, benzal acetone 6 mg / L, diethylenetriamine 2.5 g / L, sodium benzoate 1.5 g / L , 90 g / L of potassium acetate was mixed and dissolved in water, and the pH was adjusted to 5.4 with hydrochloric acid to prepare a plating bath (1 liter).
  • Comparative Example 3 Instead of 0.25 g / L of polyoxyethylene p-cumylphenyl ether sulfate sodium salt (EO addition mol 40 mol: Neucol CMP-40-SN) in Example 1, a cumylphenol-based nonionic surfactant ( 11 mol of EO addition: Newcol CMP-11 manufactured by Nippon Emulsifier Co., Ltd.
  • Table 1 Measurement results of Ni elution rate (%) of zinc nickel plating film, film thickness distribution, precipitation of nickel hydroxide at the cathode, and burnt and appearance (Halcel appearance) of zinc nickel plating film.
  • a zinc nickel plating film capable of preventing precipitation of nickel hydroxide at the cathode, suppressing the occurrence of burning of the zinc nickel plating film, and having an excellent appearance can be obtained. It can be seen that it can be obtained (Examples 1 to 5).
  • Comparative Examples 1 and 2 in which a conventional surfactant other than the cumylphenol anionic surfactant was used, precipitation of nickel hydroxide was prevented at the cathode, burnt generation of the zinc nickel plating film was suppressed, and burning was suppressed. It can be seen that the three requirements of a zinc-nickel plating film having an excellent appearance cannot be achieved at the same time.
  • Example 6 Zinc chloride 73 g / L (zinc concentration 35 g / L), nickel chloride hexahydrate 89 g / L (nickel concentration 22 g / L), potassium chloride 180 g / L (total chlorine concentration 170 g / L), ammonium chloride 30 g / L L, polyoxyethylene p-cumylphenyl ether sulfate sodium salt (EO addition mol 11 mol: Neucol CMP-11-SN) 1 g / L, benzalacetone 6 mg / L, diethylenetriamine 2.5 g / L, benzoic acid 1.5 g / L of sodium and 90 g / L of potassium acetate were mixed and dissolved in water, and the pH was adjusted to 5.4 with hydrochloric acid to prepare a plating bath (15 liters).
  • EO addition mol 11 mol: Neucol CMP-11-SN polyoxyethylene p-cumylphenyl ether sulfate sodium salt
  • the iron bolts were pretreated in the steps of alkaline degreasing, washing with water, pickling, washing with water, alkaline electrolytic washing, washing with water, activating hydrochloric acid, and washing with water.
  • a zinc plate and a nickel plate were used as anodes, and plating was carried out at a bath temperature of 35 ° C. and a cathode current density of 0.75 A / dm 2 for 45 minutes using a DC power supply.
  • the plating was performed using an auto guilder while rotating at 4 to 6 rpm.
  • the iron bolt is an M8 x 55 size hexagon bolt (half-screw type), and the zinc plate and nickel plate are 300 mm long, 100 mm wide, 20 mm thick, and the nickel plate is 300 mm long, 150 mm wide, and thick. It is a plate with a diameter of 15 mm.
  • the nickel elution rate (%) of the zinc-nickel plating film, the film thickness, the precipitation of nickel hydroxide on the hexagon bolt and the auto-guilder cathode (dangler), and the burnt and plated appearance of the zinc-nickel plating film are shown in the examples. It was evaluated by the method of 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

L'objet de la présente invention est de fournir un bain d'électroplacage au zinc nickel grâce auquel il est difficile de produire des dépôts brûlés et il est difficile de produire un dépôt d'hydroxyde de nickel sur une cathode.　La présente invention porte sur un bain galvanoplastique au zinc nickel. Le bain galvanoplastique au zinc nickel présente un pH de 3,5 à 6,9 et contient un ion zinc, un ion nickel, un ion chlorure, un tensioactif anionique de cumylphénol et un agent chélatant aminé.
PCT/JP2020/041350 2019-12-23 2020-11-05 Bain galvanoplastique au zinc nickel et procédé de placage faisant appel à celui-ci WO2021131340A1 (fr)

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JP2019-231533 2019-12-23

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007002274A (ja) * 2005-06-21 2007-01-11 Nippon Hyomen Kagaku Kk 亜鉛−ニッケル合金めっき方法
WO2010055917A1 (fr) * 2008-11-14 2010-05-20 ユケン工業株式会社 Bain de zingage acide
JP2016069725A (ja) * 2015-03-24 2016-05-09 ユケン工業株式会社 酸性亜鉛合金めっき浴用添加剤、酸性亜鉛合金めっき浴および亜鉛合金めっき部材の製造方法
JP2017538032A (ja) * 2014-10-27 2017-12-21 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ 酸性亜鉛および亜鉛−ニッケル合金めっき浴組成物ならびに電気めっき法
JP6582353B1 (ja) * 2019-02-15 2019-10-02 ディップソール株式会社 亜鉛又は亜鉛合金電気めっき方法及びシステム
JP2019530800A (ja) * 2017-02-07 2019-10-24 デーエル．−イーエヌゲー． エムアーイクス シュロッター ゲーエムベーハー ウント コー． カーゲー 有機浴添加物の分解が低減されたアルカリ性コーティング浴から亜鉛及び亜鉛合金被膜をガルバニック堆積するための方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007002274A (ja) * 2005-06-21 2007-01-11 Nippon Hyomen Kagaku Kk 亜鉛−ニッケル合金めっき方法
WO2010055917A1 (fr) * 2008-11-14 2010-05-20 ユケン工業株式会社 Bain de zingage acide
JP2017538032A (ja) * 2014-10-27 2017-12-21 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ 酸性亜鉛および亜鉛−ニッケル合金めっき浴組成物ならびに電気めっき法
JP2016069725A (ja) * 2015-03-24 2016-05-09 ユケン工業株式会社 酸性亜鉛合金めっき浴用添加剤、酸性亜鉛合金めっき浴および亜鉛合金めっき部材の製造方法
JP2019530800A (ja) * 2017-02-07 2019-10-24 デーエル．−イーエヌゲー． エムアーイクス シュロッター ゲーエムベーハー ウント コー． カーゲー 有機浴添加物の分解が低減されたアルカリ性コーティング浴から亜鉛及び亜鉛合金被膜をガルバニック堆積するための方法
JP6582353B1 (ja) * 2019-02-15 2019-10-02 ディップソール株式会社 亜鉛又は亜鉛合金電気めっき方法及びシステム

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