EP3725919A1 - Dreiwertige chromplattierungslösung und dreiwertiges chrombeschichtungsverfahren damit - Google Patents

Dreiwertige chromplattierungslösung und dreiwertiges chrombeschichtungsverfahren damit Download PDF

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Publication number
EP3725919A1
EP3725919A1 EP18888525.5A EP18888525A EP3725919A1 EP 3725919 A1 EP3725919 A1 EP 3725919A1 EP 18888525 A EP18888525 A EP 18888525A EP 3725919 A1 EP3725919 A1 EP 3725919A1
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EP
European Patent Office
Prior art keywords
trivalent chromium
plating solution
chromium plating
plating
chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP18888525.5A
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English (en)
French (fr)
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EP3725919A4 (de
Inventor
Yuto Morikawa
Masao Hori
Madoka NAKAGAMI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JCU Corp
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JCU Corp
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Filing date
Publication date
Application filed by JCU Corp filed Critical JCU Corp
Publication of EP3725919A1 publication Critical patent/EP3725919A1/de
Publication of EP3725919A4 publication Critical patent/EP3725919A4/de
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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used

Definitions

  • the present invention relates to a trivalent chromium plating solution and a trivalent chromium plating method using the same.
  • Chromium plating is used as a coating film for decoration owing to the silvery white color thereof.
  • Hexavalent chromium has been used for the chromium plating, but the use of hexavalent chromium is restricted in recent years due to the environmental implications thereof, and the technology is shifted to the use of trivalent chromium.
  • the trivalent chromium plating solution has problems including the occurrence of deposition failure of the plating and color unevenness, such as a brown stripe pattern, in the plating caused by the incorporation of metal impurities derived from the first plating and the chemicals and the like associated with the plating.
  • An object of the present invention is to provide a trivalent chromium plating solution that does not cause the problems including the occurrence of deposition failure of the plating and color unevenness, such as a brown stripe pattern, in the plating even though metal impurities are incorporated into the plating solution.
  • the present invention also relates to a trivalent chromium plating method including electroplating an article to be plated with the trivalent chromium plating solution.
  • R 1 represents a hydrocarbon group having a number of carbon atoms of from 1 to 10, hydrogen, or a halogen
  • R 2 represents nothing or a hydrocarbon group having a number of carbon atoms of from 1 to
  • the present invention still more further relates to a chromium-plated product including an article to be plated, electroplated with the trivalent chromium plating solution.
  • the trivalent chromium plating solution of the present invention is an excellent one that does not cause the problems including the occurrence of deposition failure of the plating and color unevenness, such as a brown stripe pattern, in the plating even through metal impurities are incorporated into the plating solution.
  • the trivalent chromium plating solution of the present invention (which may be hereinafter referred to as a "plating solution of the present invention") is a trivalent chromium plating solution that contains a trivalent chromium compound, a chloride as a conductive salt, a pH buffering agent, and a complexing agent, and further contains an unsaturated sulfonic acid compound represented by the following general formula (1) .
  • R 1 -CH CH-R 2 -SO 3 X (1)
  • R 1 represents a hydrocarbon group having a number of carbon atoms of from 1 to 10, hydrogen, or a halogen
  • R 2 represents nothing or a hydrocarbon group having a number of carbon atoms of from 1 to 10
  • X represents hydrogen or an alkali metal
  • R 1 represents a hydrocarbon group having a number of carbon atoms of from 1 to 6 or hydrogen
  • R 2 represents nothing or a hydrocarbon group having a number of carbon atoms of from 1 to 6
  • X represents hydrogen, sodium, or potassium.
  • the unsaturated sulfonic acid compound represented by the formula (1) include sodium vinylsulfonate, sodium allylsulfonate, sodium p-styrenesulfonate, and sodium ⁇ -styrenesulfonate.
  • the unsaturated sulfonic acid compound may be used alone or as a combination of two or more kinds thereof.
  • the content of the unsaturated sulfonic acid compound in the plating solution of the present invention is not particularly limited, and for example, is from 0.01 to 20 g/L, and preferably from 0.1 to 5 g/L.
  • the trivalent chromium compound used in the plating solution of the present invention is not particularly limited, examples of which include basic chromium sulfate, chromium sulfate, chromium chloride, chromium sulfamate, and chromium acetate, and basic chromium sulfate, chromium sulfate, and chromium chloride are preferred.
  • the trivalent chromium compound may be used alone or as a combination of two or more kinds thereof.
  • the content of the trivalent chromium compound in the plating solution of the present invention is not particularly limited, and for example, is from 1 to 20 g/L, and preferably from 5 to 15 g/L, in terms of metallic chromium.
  • the conductive salt used in the plating solution of the present invention is a chloride.
  • the kind of the chloride is not particularly limited, examples of which include potassium chloride, ammonium chloride, and sodium chloride.
  • the chloride may be used alone or as a combination of two or more kinds thereof.
  • the content of the chloride in the plating solution of the present invention is not particularly limited, and for example, is from 150 to 400 g/L, and preferably from 200 to 350 g/L.
  • the pH buffering agent used in the plating solution of the present invention is not particularly limited, examples of which include boric acid, sodium borate, potassium borate, phosphoric acid, and dipotassium hydrogen phosphate, and boric acid and sodium borate are preferred.
  • the pH buffering agent may be used alone or as a combination of two or more kinds thereof.
  • the content of the pH buffering agent in the plating solution of the present invention is not particularly limited, and for example, is from 10 to 150 g/L, and preferably from 50 to 100 g/L.
  • the complexing agent used in the plating solution of the present invention is not particularly limited, examples of which include formic acid, ammonium formate, potassium formate, citric acid, and triammonium citrate. Among these, ammonium formate and triammonium citrate are preferred.
  • the complexing agent may be used alone or as a combination of two or more kinds thereof.
  • the content of the complexing agent in the plating solution of the present invention is not particularly limited, and for example, is from 0.3 to 2 times by mol, and preferably from 0.8 to 1.5 times by mol, the metallic chromium concentration.
  • the plating solution of the present invention may further contain ammonium bromide, potassium bromide, and the like.
  • the pH of the plating solution of the present invention is not particularly limited, as far as the solution is acidic, and for example, is preferably from 2 to 4, and more preferably from 2.5 to 3.5.
  • the preparation method of the plating solution of the present invention is not particularly limited, and for example, the solution can be prepared by adding and mixing the trivalent chromium compound, the chloride salt, the pH buffering agent, the complexing agent, and the unsaturated sulfonic acid compound with water at from 40 to 50°C, adding and mixing the other components therewith depending on necessity, and controlling the pH thereof.
  • the plating solution of the present invention does not cause the problems including the occurrence of deposition failure of the plating and color unevenness, such as a brown stripe pattern, in the plating even though metal impurities are contained therein (i.e., has resistance against metal impurities).
  • the plating solution of the present invention does not cause the problems even though a large amount of metal impurities are contained in a concentration of approximately several hundred ppm during the long-term use or suddenly.
  • the metal impurities herein are metals derived from the first plating and the chemicals and the like associated with the plating. Specific examples of the metals include nickel, zinc, copper, and hexavalent chromium, and preferably include nickel and copper, which are frequently used as the first plating.
  • the plating solution of the present invention positively uses nickel as a metal impurity contained therein, burnt deposit in a high current density in plating can be prevented from occurring.
  • the high current density herein means portions where the current is concentrated, such as a corner part and an apex part of an article.
  • Nickel that can be used in the plating solution of the present invention is not particularly limited, and examples thereof include a nickel salt, such as nickel chloride and nickel sulfate.
  • the content of nickel in the plating solution of the present invention is not particularly limited, and for example, is from 10 to 500 ppm, preferably from 15 to 200 ppm, and more preferably from 20 to 100 ppm.
  • Nickel can prevent burnt deposit in a high current density from occurring also in plating with a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffering agent, and a complexing agent, obtained by excluding the unsaturated sulfonic acid compound represented by the general formula (1) from the plating solution of the present invention, at the same concentration.
  • the kinds and the concentrations of the trivalent chromium compound, the chloride, the pH buffering agent, and the complexing agent may be the same as in the plating solution of the present invention.
  • An ordinary trivalent chromium plating solution contains iron or cobalt for the enhancement of the throwing power for a low current density, but the plating solution of the present invention can have enhanced throwing power without the addition of iron and/or cobalt.
  • a plating solution containing iron or cobalt has a tendency that the corrosion resistance of the plating film is decreased due to codeposition of iron or cobalt therein. Accordingly, it is preferred that the plating solution of the present invention contains substantially no iron and/or cobalt.
  • the plating solution of the present invention that contains substantially no iron and/or cobalt means that the content of iron and/or cobalt is 2 ppm or less, preferably 1 ppm or less, and more preferably 0.5 ppm or less.
  • the amount of iron and/or cobalt can be analyzed by the ICP-MS method, the atomic absorption spectrometry, or the like.
  • Chromium plating can be formed on an article to be plated by electroplating the article to be plated with the plating solution of the present invention in the same manner as for the ordinary chromium plating solution.
  • the condition of the electroplating is not particularly limited, and for example, the electroplating may be performed at a bath temperature of from 25 to 45°C, with carbon or iridium oxide as an anode, at a cathode current density of from 4 to 20 A/dm 2 , for a period of from 1 to 15 minutes.
  • Examples of the article to be plated capable of being electroplated include a metal, such as iron, stainless steel, and brass, and a resin, such as ABS and PC/ABS.
  • the article to be plated may be subjected to a treatment, such as copper plating and nickel plating, in advance before the treatment with the plating solution of the present invention.
  • the chromium plating thus obtained becomes chromium plating having an appearance, throwing power, and a deposition rate that are equivalent to the use of hexavalent chromium.
  • the unsaturated sulfonic acid compound represented by the formula (1) can suppress the color tone of the resulting chromium plating from becoming dark, as compared to other unsaturated sulfonic acid compounds. Accordingly, the chromium-plated product is favorably applied to automobile exterior components, such as a door handle and an emblem, and components of an accessory, a faucet, a tool, and the like.
  • the resulting chromium-plated product also contains substantially no iron and/or cobalt.
  • the chromium-plated product of the present invention that contains substantially no iron and/or cobalt means that the content of iron and/or chromium in the chromium plating is less than 0.5% by atom, and preferably 0.3% by atom or less.
  • the amount of iron and/or cobalt can be analyzed by EDS, XPS, or the like.
  • the compounds shown in the following basic formulation and Table 1 each were dissolved in water to prepare a trivalent chromium plating solution.
  • the trivalent chromium plating solution was subjected to the Hull cell test using a brass plate having nickel plating formed thereon.
  • the condition of the Hull cell test was a current of 5 A and a plating time of 3 minutes.
  • the distance of the deposition of the plating film from the left end of the brass plate was measured as shown in Fig. 1 , and the throwing power decreasing rate was calculated in the manner described later.
  • the color tone and the appearance were evaluated in the manners described later.
  • the color tone after plating was evaluated in terms of the L* value with a color-difference meter (produced by Konica Minolta, Inc.).
  • the standard value is a value of throwing power with no compound added
  • the test value is the measured value in the test under the condition.
  • the values of the standard value are 71 mm for the basic formulation 1, 73 mm for the basic formulation 2, and 74 mm for the basic formulation 3.
  • L* of 78 or more poor L* of less than 78
  • the unsaturated sulfonic acid compound contained in the plating solution of the present invention was not a substance that the use thereof deteriorated the color tone, the appearance, and the throwing power of the chromium plating.
  • the contents of iron and cobalt in the trivalent chromium plating solutions each were less than 0.5 ppm, as measured by the ICP-MS method.
  • the contents of iron and cobalt in the resulting chromium plating each were less than 0.3% by atom, as measured by the EDS elemental analysis.
  • a trivalent chromium plating solution was prepared in the same manner as in Example 1 except that a Watts solution was added in an amount that provided 100 ppm of nickel as a metal impurity.
  • the trivalent chromium plating solution was subjected to the same test as in Example 1. The results are shown in Table 2.
  • the plating capability of the trivalent chromium plating solution of the present invention (i.e., the example product), which was a chloride bath and contained the unsaturated sulfonic acid compound having the particular structure, was not influenced by 100 ppm of nickel contained as a metal impurity in the plating solution. It was also found that irrespective of the same trivalent chromium plating solution, the sulfuric acid bath (i.e., the comparative product having the basic formulation 3) had no resistance against metal impurities even though the unsaturated sulfonic acid compound having the particular structure was contained. It was further found that irrespective of the chloride bath, in the case where the particular structure was not used, the plating capability was influenced by 100 ppm of nickel contained as a metal impurity in the plating solution.
  • the contents of iron and cobalt in the trivalent chromium plating solutions each were less than 0.5 ppm, as measured by the ICP-MS method.
  • the contents of iron and cobalt in the resulting chromium plating each were less than 0.3% by atom, as measured by the EDS elemental analysis.
  • a trivalent chromium plating solution containing the compounds shown in the basic formulation 1 used in Example 1 and the Table 3 below, and a copper chloride aqueous solution in an amount that provided 20 ppm of copper as a metal impurity was prepared.
  • the trivalent chromium plating solution was subjected to the same test as in Example 1. The results are shown in Table 3.
  • a trivalent chromium plating solution containing no unsaturated sulfonic acid compound having the particular structure was subjected to the same test. The results are also shown in Table 3.
  • the plating capability of the trivalent chromium plating solution of the present invention was not influenced by 20 ppm of copper contained as a metal impurity in the plating solution.
  • the contents of iron and cobalt in the trivalent chromium plating solutions each were less than 0.5 ppm, as measured by the ICP-MS method.
  • the contents of iron and cobalt in the resulting chromium plating each were less than 0.3% by atom, as measured by the EDS elemental analysis.
  • the compounds shown in the following basic formulation 4, a sodium vinylsulfonate 25% aqueous solution, and nickel (added in the form of nickel chloride) were dissolved in water in the concentrations shown in Table 4 to prepare a trivalent chromium plating solution.
  • the trivalent chromium plating solution was subjected to the Hull cell test using a brass plate having nickel plating formed thereon. The condition of the Hull cell test was a current of 5 A and a plating time of 3 minutes.
  • the trivalent chromium plating solution was subjected to the same test as in Example 1. The presence of burnt deposit in a high current density (which was the left end portion in Fig. 1 ) was visually evaluated. The results are shown in Table 4.
  • the brass plate after plating with a plating solution containing no nickel (with burnt deposit) is shown in Fig. 2
  • the appearance of the brass plate after plating with a plating solution containing 10 ppm of nickel (without burnt deposit) is shown in Fig. 3 .
  • the contents of iron and cobalt in the trivalent chromium plating solutions each were less than 0.5 ppm, as measured by the ICP-MS method.
  • the contents of iron and cobalt in the resulting chromium plating each were less than 0.3% by atom, as measured by the EDS elemental analysis.
  • a sodium vinylsulfonate 25% aqueous solution was not added, but nickel was added in an amount of 0, 10, 30, or 50 ppm, so as to prepare a trivalent chromium plating solution.
  • the trivalent chromium plating solution was subjected to the Hull cell test using a brass plate having nickel plating formed thereon. The condition of the Hull cell test was a current of 5 A and a plating time of 3 minutes.
  • the trivalent chromium plating solution was subjected to the same test as in Example 1 and the same evaluation of the presence of burnt deposit in a high current density as in Example 4.
  • the trivalent chromium plating solution of the present invention can be applied to various purposes as similar to plating with hexavalent chromium.

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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)
EP18888525.5A 2017-12-14 2018-12-13 Dreiwertige chromplattierungslösung und dreiwertiges chrombeschichtungsverfahren damit Withdrawn EP3725919A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017239216 2017-12-14
JP2018121196 2018-06-26
PCT/JP2018/045799 WO2019117230A1 (ja) 2017-12-14 2018-12-13 ３価クロムメッキ液およびこれを用いた３価クロムメッキ方法

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EP3725919A1 true EP3725919A1 (de) 2020-10-21
EP3725919A4 EP3725919A4 (de) 2021-09-01

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EP18888525.5A Withdrawn EP3725919A4 (de) 2017-12-14 2018-12-13 Dreiwertige chromplattierungslösung und dreiwertiges chrombeschichtungsverfahren damit

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US (1) US20210198797A1 (de)
EP (1) EP3725919A4 (de)
JP (1) JPWO2019117230A1 (de)
KR (1) KR20200096932A (de)
CN (1) CN111479956A (de)
WO (1) WO2019117230A1 (de)

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US4167460A (en) * 1978-04-03 1979-09-11 Oxy Metal Industries Corporation Trivalent chromium plating bath composition and process
GB2093861B (en) * 1981-02-09 1984-08-22 Canning Materials W Ltd Bath for electrodeposition of chromium
US4450052A (en) * 1982-07-28 1984-05-22 M&T Chemicals Inc. Zinc and nickel tolerant trivalent chromium plating baths
CA1223547A (en) * 1983-07-27 1987-06-30 Louis Gianelos Electrodeposition from trivalent chromium bath
GB8503019D0 (en) * 1985-02-06 1985-03-06 Canning W Materials Ltd Electroplating
JP5379426B2 (ja) 2007-08-30 2013-12-25 日産自動車株式会社 クロムめっき部品およびその製造方法
US9765437B2 (en) * 2009-03-24 2017-09-19 Roderick D. Herdman Chromium alloy coating with enhanced resistance to corrosion in calcium chloride environments
CN101792917A (zh) * 2010-03-31 2010-08-04 哈尔滨工业大学 常温环保型硫酸盐三价铬电镀液的制备方法和电镀方法
ES2774265T3 (es) * 2011-05-03 2020-07-20 Atotech Deutschland Gmbh Baño de galvanoplastia y método para producir capas de cromo oscuro
CN105671599A (zh) * 2016-04-11 2016-06-15 济南德锡科技有限公司 一种硫酸盐三价铬电镀液及其制备方法

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JPWO2019117230A1 (ja) 2020-12-17
KR20200096932A (ko) 2020-08-14
CN111479956A (zh) 2020-07-31
WO2019117230A1 (ja) 2019-06-20
US20210198797A1 (en) 2021-07-01
EP3725919A4 (de) 2021-09-01

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