US20070199827A1 - Method for electroplating with tin-zinc alloy - Google Patents

Method for electroplating with tin-zinc alloy Download PDF

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Publication number
US20070199827A1
US20070199827A1 US11/704,805 US70480507A US2007199827A1 US 20070199827 A1 US20070199827 A1 US 20070199827A1 US 70480507 A US70480507 A US 70480507A US 2007199827 A1 US2007199827 A1 US 2007199827A1
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Prior art keywords
tin
plating bath
zinc alloy
acid
zinc
Prior art date
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Abandoned
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US11/704,805
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English (en)
Inventor
Satoshi Yuasa
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Dipsol Chemicals Co Ltd
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Dipsol Chemicals Co Ltd
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Assigned to DIPSOL CHEMICALS CO., LTD. reassignment DIPSOL CHEMICALS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YUASA, SATOSHI
Publication of US20070199827A1 publication Critical patent/US20070199827A1/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • 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
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating

Definitions

  • the present invention relates to a method for electroplating with a tin-zinc alloy.
  • the systems that are still used include a rack system (maximum current density about 3 A/dm 2 ) in which the articles to be plated are treated upon mounting them on a jig and a barrel system (maximum current density 1 A/dm 2 ) in which the articles to be plated are treated in a barrel.
  • the present invention is based on a discovery that electroplating with a tin-zinc alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
  • the present invention provides a method for electroplating with a tin-zinc alloy that is performed under the following conditions: a plating bath temperature of 30 to 90° C., plating bath stirring rate of 5 to 300 m/min, and cathode current density of 5 to 200 A/dm 2 .
  • electroplating with a tin-lead alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
  • the temperature of the plating bath in the electroplating method in accordance with the present invention is 30 to 90° C., preferably 40 to 60° C., and the stirring rate of the plating solution is 5 to 300 m/min, preferably 10 to 100 m/min.
  • Stirring of the plating solution is specifically carried out by a plating apparatus of a jet flow system in which the solution is circulated with a pump or by a plating apparatus for steel sheets.
  • the plating apparatus can be made from any material, provided it has heat resistance and chemical resistance, and metals such as stainless steel and titanium or polyvinyl chloride, Teflon (registered trade name), and an ABS resin can be used.
  • a device enabling the stirring of the plating solution that is uniform with respect to the entire plated article is preferred from the standpoint of increasing the uniformity of the plated alloy composition and plated film thickness.
  • any plating bath well known to a person skilled in the art can be used as the bath for the tin-zinc alloy electroplating bath employed in the electroplating method in accordance with the present invention, but a plating bath comprising a hydroxycarboxylic acid or a salt thereof is preferred.
  • a compound having one or more hydroxyl groups and one or more carboxyl groups in a molecule is preferred as the hydroxycarboxylic acid.
  • hydroxycarboxylic acids include citric acid, tartaric acid, malic acid, glycolic acid, glyceric acid, lactic acid, ⁇ -hydroxypropionic acid, and gluconic acid.
  • citric acid, tartaric acid, malic acid, and gluconic acid are preferred among them.
  • hydroxycarboxylic acid salts include alkali metal salts (sodium, potassium, lithium salts) alkaline earth metal salts (magnesium, calcium, barium salts, and the like), divalent tin salts, zinc salts, ammonium salts, and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.) of the aforementioned hydroxycarboxylic acids.
  • alkali metal salts sodium, potassium, lithium salts
  • divalent tin salts alkaline earth metal salts (magnesium, calcium, barium salts, and the like
  • organic amine salts monomethylamine, dimethylamine, trimethylamine, methylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.
  • the preferred among them are sodium salts, potassium salts, lithium salts, divalent tin salts, and zinc salts of citric acid, tartaric
  • hydroxycarboxylic acids and salts thereof may be used individually or in a mixture of two or more thereof, and the concentration thereof in the plating bath is 0.25 to 3 mol/L, preferably 0.3 to 1.5 mol/L.
  • concentration thereof in the plating bath is 0.25 to 3 mol/L, preferably 0.3 to 1.5 mol/L.
  • the hydroxycarboxylic acid which is a counterion of the metal ions also constitutes part of the aforementioned concentration.
  • the pH of the plating bath comprising the hydroxycarboxylic acid or salt thereof is preferably 2 to 10, more preferably 3 to 9.
  • the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid.
  • suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • a plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and phthalic anhydride also can be utilized as the tin-zinc alloy electroplating bath used in the electroplating method in accordance with the present invention. More specifically, for example, a water-soluble compound can be used that is obtained by reacting 0.2 to 3 moles of an organic acid ester per 1 mole of an aliphatic amine for 10 to 60 min. at a temperature of 50 to 99° C. and then reacting phthalic anhydride with the obtained reactive product at a weight ratio of 0.1 to 1:1 for 30 to 180 min at a temperature of 60 to 130° C.
  • amphoteric surfactants include imidazoline-type, betaine-type, alanine-type, glycine-type, and amide-type surfactants.
  • aliphatic amines suitable for the reaction of the water-soluble compound include ethylenediamine, triethylenetetramine, isobutylamine, 3-methoxypropylamine, iminobispropylamine, diethylamine, hexamethylenetetramine, and dimethylaminopropylamine.
  • suitable organic acid esters include dimethyl manolate, diethyl succinate, diethyl maleate, dimethyl fumarate, diethyl tartarate, dimethyl malate, and diethyl tartronate.
  • These water-soluble compounds and amphoteric surfactants may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.00.1 to 50 g/L, preferably 0.01 to 30 g/L.
  • the pH of the plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and phthalic anhydride is preferably 2 to 10, more preferably 3 to 9.
  • the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid.
  • suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water
  • acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • a plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds also can be used as the tin-zinc alloy electroplating bath employed in the electroplating method in accordance with the present invention.
  • tertiary amine compounds include imidazole compounds and aliphatic amine compounds
  • examples of quaternary amine compounds include reaction products of tertiary amine compounds and halogenated alkyls.
  • tertiary amine compounds include imidazole compounds, such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, and 1, 5-dimethylimidazole, and aliphatic amines such as monoethanolamine, diethanolamine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, iminobispropylamine, triethylenetetramine, tetraethylenepentamine, and N,N-bis-(3-aminopropyl)ethylenediamine.
  • imidazole compounds such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, and 1, 5-dimethylimidazole
  • tertiary amine compounds and quaternary amine compounds may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.1 to 30 g/L, preferably 0.2 to 20 g/L.
  • the pH of the plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds is preferably 10 to 14, more preferably 12 to 14.
  • the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate.
  • suitable compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water.
  • the plating bath used in the electroplating method in accordance with the present invention can additionally contain at least one surfactant selected from the group consisting of a nonionic surfactant, anionic surfactant, and cationic surfactant. Introducing such surfactants into the plating bath enables denser precipitation at a high current density and, therefore, makes it possible to implement more smoothly the electroplating method in accordance with the present invention.
  • the divalent tin ion concentration is 1 to 100 g/L, preferably 5 to 80 g/L, and the zinc ion concentration is 0.2 to 80 g/L, preferably 1 to 50 g/L.
  • sources of such metal ions include various metal hydroxides, oxides, sulfates, chlorides, sulfamates, pyrophosphates, hydroxycarboxylates, sulfonates, and amino acid salts.
  • Various metal oxides, sulfates, chlorides, and hydroxides are preferred. Specific examples of hydroxycarboxylic acid salts are presented hereinabove.
  • sulfonates include alkanesulfonates, alkanolsulfonates, and phenolsulfonates.
  • alkanesulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, and hexanesulfonic acid.
  • alkanolsulfonic acids include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, and 2-hydroxybutanesulfonic acid.
  • phenolsulfonic acids include phenolsulfonic acid, cresolsulfonic acid, and dimethylphenolsulfonic acid.
  • amino acids include glycine, glutamic acid, and alanine.
  • alkali metal salts sodium, potassium, lithium salts
  • alkaline earth metal salts magnesium, calcium, barium salts
  • ammonium salts and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, ispropylamine, ethylenediamine, diethylenetriamine, etc.) of sulfuric acid, hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxides and carbonates
  • sulfuric acid hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxides and carbonates
  • salts include ammonium sulfate, ammonium chloride, sodium pyrophosphate, monomethyl sulfamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and among these especially preferred are ammonium sulfate, ammonium chloride, potassium hydroxide, and potassium carbonate.
  • the content of these salts is 10 to 300 g/L, preferably 50 to 200 g/L.
  • the plating bath used in the electroplating method in accordance with the present invention can contain water in addition to the above-described components and also can contain additives that have been used as a brightener for tin and zinc.
  • suitable additives include synthetic polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, and the like), ketones (benzalacetone, acetophenone, and the like), aliphatic aldehydes (formalin, acetaldehyde, crotonaldehyde, and the like), aromatic aldehydes (vanillin, salicylaldehyde, orthochlorobenzaldehyde, and the like), reaction products of unsaturated aliphatic aldehydes and amine compounds, sulfur compounds (thiourea, mercaptobenzimidazole, and the like), and also Cu, Ni, Mn, Bi, In, and the like.
  • additives are contained at 0.001 to 50 g/L, preferably 0.005 to 30 g/L.
  • hydroxyphenyl compounds such as catechol, pyrogallol, hydroquinone, sulfosalicylic acid, potassium dihydroxybenzenesulfonate and salts thereof and L-ascorbic acid, sorbitol and the like also can be used as oxidation preventing agents for tin.
  • the articles to be plated by the plating method in accordance with the present invention are metal materials such as Fe, Ni, Cu, or alloys based thereon, and the plating is carried out by using them as cathodes.
  • a carbon electrode and insoluble electrode obtained by plating Pt on a Ti material or tin-zinc alloy can be used as a counter electrode thereof.
  • the concentration of metals in the plating bath that is being used can be maintained by directly dissolving the aforementioned tin and zinc salts in the plating bath or by supplying an aqueous solution in which tin and zinc salts are dissolved into a high concentration.
  • the high-concentration aqueous solution of the metals may contain the above-described hydroxycarboxylic acid or salt thereof and an alkali hydroxide compound.
  • the cathode current density is 5 to 200 A/dm 2 , preferably 10 to 120 A/dm 2 .
  • the film thickness can be within a wide range, but is generally 0.5 to 500 ⁇ m, preferably 2 to 20 ⁇ m.
  • Tin-zinc alloy plating can be performed within a wide range of alloy compositions by changing the ratio of tin ions and zinc ions in the plating bath that is being used.
  • tin-zinc alloy coatings with a zinc content of 3 to 15% can be obtained on electronic components.
  • a tin-zinc alloy coating with a zinc content of 15 to 45% can be obtained.
  • a tin-zinc alloy coating with a zinc content of 50 to 90% can be produced.
  • the article to be plated is subjected to plating after a pretreatment conducted by the usual method. At least one operation selected from immersion degreasing, pickling, electrolytic washing, and activation is performed in the pretreatment process.
  • the film obtained may be washed with water and dried, or can be further coated by a chromating and conversion treatment, or with an inorganic or organic material by the usual method.
  • the present invention will be described below based on embodiments thereof, but the present invention is not limited to the embodiments, and the plating solution temperature, flow rate of the plating solution, and the composition of the plating bath can be freely changed according to the article to be plated.
  • a steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 50 m/min.
  • Tin (I) sulfate (as tin) 30 g/L
  • Zinc sulfate (as zinc) 25 g/L
  • Product obtained by reacting 1 mole 10 mL/L of ethylene diamine and 1 mole of dimethyl malonate for 60 mins. at 85° C. and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.5:1 for 90 mins. at 95° C. pH 4 (adjusted with ammonia water)
  • a steel sheet was pretreated, Nymin NAG-1001 manufactured by Nippon Oils & Fats Co., Ltd. was added as a nonionic surfactant at 5 g/L to the plating solution of Embodiment 1, and electroplating was conducted under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 30 m/min.
  • a steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 30 m/min.
  • Potassium stannate (as tin) 55 g/L
  • Zinc oxide (as zinc) 5 g/L
  • Potassium hydroxide 80 g/L
  • Potassium carbonate 100 g/L
  • a phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 50° C. and a plating bath stirring rate of 60 m/min.
  • Product obtained by reacting 1 mole of 10 mL/L triethylene tetramine and 1.2 mole of diethyl succinate for 40 mins. at 80° C. and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.7:1 for 120 mins. at 90° C.
  • a phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 60 m/min.
  • Tin methanesulfonate (as tin) 30 g/L
  • Zinc methanesulfonate (as zinc) 15 g/L
  • Sodium gluconate 150 g/L (0.69 mole/L)
  • Methanesulfonic acid 100 g/L
  • Product obtained by reacting 1 mole of 8 mL/L ethylene diamine and 1 mole of dimethyl maleate for 60 mins. at 90° C. and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.5:1 for 150 mins. at 110° C.
  • a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 23° C. and a plating bath stirring rate of 50 m/min.
  • a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 2 m/min.
  • a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 3 under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 3 m/min.
  • Example 1 Example 2
  • Example 3 Plated Film Plated Film Plated Film precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness state (wt. %) time ( ⁇ m) state (wt. %) time ( ⁇ m) state (wt. %) time ( ⁇ m) state (wt.
  • Example 5 Plated Film Plated Film precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness state (wt. %) time ( ⁇ m) state (wt. %) time ( ⁇ m) 10 A/dm 2 ⁇ 88/12 120 9.4 ⁇ 85/15 120 9.0 20 A/dm 2 ⁇ 90/10 60 9.2 ⁇ 80/20 60 8.5 30 A/dm 2 ⁇ 90/10 40 9.2 ⁇ 80/20 40 8.5 40 A/dm 2 ⁇ 90/10 30 9.2 ⁇ 80/20 30 8.0 50 A/dm 2 ⁇ 90/10 25 9.0 ⁇ 80/20 25 7.9 60 A/dm 2 ⁇ 90/10 20 8.6 ⁇ 85/15 20 7.6 70 A/dm 2 ⁇ 91/9 17 7.2 ⁇ 84/16 17 7.3 80 A/dm 2 ⁇ 91/9 15 6.4 ⁇ 88/12 15 6.0 90 A/dm 2 x — 13 — ⁇ 90/10 13 5.4 100 A/dm 2 x — 12 —

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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)
  • Electroplating Methods And Accessories (AREA)
US11/704,805 2004-08-10 2007-02-09 Method for electroplating with tin-zinc alloy Abandoned US20070199827A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2004-233633 2004-08-10
JP2004233633A JP4594672B2 (ja) 2004-08-10 2004-08-10 錫−亜鉛合金電気めっき方法
PCT/JP2005/014648 WO2006016603A1 (ja) 2004-08-10 2005-08-10 錫－亜鉛合金電気めっき方法

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PCT/JP2005/014648 Continuation WO2006016603A1 (ja) 2004-08-10 2005-08-10 錫－亜鉛合金電気めっき方法

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US (1) US20070199827A1 (pt)
EP (1) EP1811063B1 (pt)
JP (1) JP4594672B2 (pt)
KR (1) KR100929761B1 (pt)
CN (1) CN101001982B (pt)
BR (1) BRPI0514210B1 (pt)
ES (1) ES2526430T3 (pt)
WO (1) WO2006016603A1 (pt)

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CN105002526A (zh) * 2015-06-30 2015-10-28 安徽飞达新材料科技股份有限公司 一种冷轧钢板光亮剂
CN111188069A (zh) * 2019-12-31 2020-05-22 大连长丰实业总公司 一种镀锡铋合金溶液及其制备方法
CN111394734A (zh) * 2020-05-06 2020-07-10 苏州清飙科技有限公司 压铸锌合金用脱膜抛光液及其制备方法

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CN102634827B (zh) * 2012-05-07 2015-04-08 东莞市闻誉实业有限公司 一种锡-锌合金电镀方法
CN102690975B (zh) * 2012-06-11 2014-12-03 东莞市闻誉实业有限公司 一种三元锡-锌合金及其电镀方法
CN104213159A (zh) * 2014-09-17 2014-12-17 朱忠良 电镀液及电镀方法
CN104357884A (zh) * 2014-11-14 2015-02-18 无锡伊佩克科技有限公司 一种钢铁材料镀锌锡合金方法
CN105350056B (zh) * 2015-11-24 2017-12-01 安徽天思朴超精密模具股份有限公司 耐磨损电镀液材料组合物和耐磨损电镀液的制备方法及应用
KR101678013B1 (ko) * 2016-02-15 2016-11-21 주식회사 베프스 금속성분의 액중 농도 지시체를 포함하는 도금액 및 이를 이용한 도금 방법
KR102621912B1 (ko) * 2018-12-24 2024-01-05 현대자동차주식회사 휘스커 저항성이 우수한 전기전자부품용 아연 도금 방법 및 아연 도금 강판

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CN105002526A (zh) * 2015-06-30 2015-10-28 安徽飞达新材料科技股份有限公司 一种冷轧钢板光亮剂
CN111188069A (zh) * 2019-12-31 2020-05-22 大连长丰实业总公司 一种镀锡铋合金溶液及其制备方法
CN111394734A (zh) * 2020-05-06 2020-07-10 苏州清飙科技有限公司 压铸锌合金用脱膜抛光液及其制备方法

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BRPI0514210A2 (pt) 2009-04-28
WO2006016603A1 (ja) 2006-02-16
EP1811063A4 (en) 2009-03-04
ES2526430T3 (es) 2015-01-12
EP1811063A1 (en) 2007-07-25
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EP1811063B1 (en) 2014-12-03
CN101001982B (zh) 2010-09-08
JP4594672B2 (ja) 2010-12-08

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