WO2019117230A1 - Solution de placage de chrome trivalent et procédé de placage de chrome trivalent l'employant - Google Patents

Solution de placage de chrome trivalent et procédé de placage de chrome trivalent l'employant Download PDF

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Publication number
WO2019117230A1
WO2019117230A1 PCT/JP2018/045799 JP2018045799W WO2019117230A1 WO 2019117230 A1 WO2019117230 A1 WO 2019117230A1 JP 2018045799 W JP2018045799 W JP 2018045799W WO 2019117230 A1 WO2019117230 A1 WO 2019117230A1
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WIPO (PCT)
Prior art keywords
trivalent chromium
plating solution
chromium plating
chloride
plating
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PCT/JP2018/045799
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English (en)
Japanese (ja)
Inventor
雄斗 森川
真雄 堀
まどか 中上
Original Assignee
株式会社Ｊｃｕ
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 株式会社Ｊｃｕ filed Critical 株式会社Ｊｃｕ
Priority to EP18888525.5A priority Critical patent/EP3725919A4/fr
Priority to CN201880080667.3A priority patent/CN111479956A/zh
Priority to JP2019559193A priority patent/JPWO2019117230A1/ja
Priority to KR1020207017355A priority patent/KR20200096932A/ko
Priority to US16/771,066 priority patent/US20210198797A1/en
Publication of WO2019117230A1 publication Critical patent/WO2019117230A1/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
    • 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.
  • Chrome plating is used as a coating film for decoration because it has a silver-white appearance.
  • hexavalent chromium was used for this chromium plating, since this hexavalent chromium affects the environment in recent years, its use has been limited, and the technology has shifted to the technique using trivalent chromium. ing.
  • Patent Document 1 Many techniques using such trivalent chromium have been reported by various manufacturers (see, for example, Patent Document 1).
  • An object of the present invention is to provide a trivalent chromium plating solution which does not cause problems such as non-deposition of plating and occurrence of color unevenness such as brown stripes in plating even if metal impurities enter the plating solution. It is.
  • a trivalent chromium plating solution containing a chloride as a conductive salt contains an unsaturated sulfonic acid compound having a specific structure, thereby achieving plating. It was found that even if metal impurities were contained in the solution, problems such as non-deposition of plating and occurrence of color unevenness such as brown streaks did not occur in plating, and the present invention was completed. In addition to the above problems, it has been found that by actively incorporating nickel as a metal impurity in a trivalent chromium plating solution, it is possible to prevent burnout at a high current density when plating, and the present invention has been completed.
  • the present invention is a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent, Furthermore, the following general formula (1) (Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate It is a trivalent chromium plating solution characterized by containing the unsaturated sulfonic acid compound represented by these.
  • the present invention is a method of trivalent chromium plating on an object to be plated, characterized in that the object to be plated is electroplated with the above-mentioned trivalent chromium plating solution.
  • the present invention is further directed to a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent, further comprising the following general formula (1) (Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate It is the method of containing the unsaturated sulfonic acid compound represented by these, and improving the tolerance when the said trivalent chromium plating liquid contains a metal impurity.
  • the present invention is further directed to a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, a complexing agent, and a compound represented by the following general formula (1) (Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate And the nickel is contained, and it is the method of preventing the burn in the high current density at the time of plating using said trivalent chromium plating liquid.
  • R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen
  • R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms
  • X represents a hydrogen or an alkali metal Indicate
  • the nickel is contained, and it is the method of preventing the burn in the high current density
  • the present invention is a chromium plated product obtained by electroplating a material to be plated with the above trivalent chromium plating solution.
  • the trivalent chromium plating solution of the present invention is an excellent one that does not cause problems such as non-deposition of plating and occurrence of color unevenness such as brown stripes in plating even if metal impurities are contained.
  • FIG. 7 is a view showing the position at which the distance around the stick was measured in the Hull cell test of Example 1;
  • Example 4 it is a figure which shows the Hull cell external appearance of the brass plate (with a koge) which performed nickel plating after plating by the plating solution without nickel addition.
  • Example 4 it is a figure which shows the Hull cell external appearance of the brass plate (it is not shown) which plated nickel by plating liquid which added nickel 10 ppm.
  • the trivalent chromium plating solution of the present invention (hereinafter referred to as "the plating solution of the present invention") is a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent. , Furthermore, the following general formula (1) It contains the unsaturated sulfonic acid compound represented by these.
  • R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or halogen
  • R 2 represents no or a hydrocarbon group having 1 to 10 carbon atoms
  • X represents hydrogen or an alkali metal.
  • R 1 represents a hydrocarbon group having 1 to 6 carbon atoms or hydrogen
  • R 2 represents no or a hydrocarbon group having 1 to 6 carbon atoms
  • X represents hydrogen, sodium or potassium.
  • Specific unsaturated sulfonic acid compounds represented by the above formula (1) include sodium vinylsulfonate, sodium allylsulfonate, sodium p-styrenesulfonate, sodium ⁇ -styrenesulfonate and the like.
  • These unsaturated sulfonic acid compounds may be used alone or in combination of two or more.
  • the content of the unsaturated sulfonic acid compound in the plating solution of the present invention is not particularly limited, and is, for example, 0.01 to 20 g / L, and preferably 0.1 to 5 g / L.
  • the trivalent chromium compound used in the plating solution of the present invention is not particularly limited, and is, for example, basic chromium sulfate, chromium sulfate, chromium chloride, chromium sulfamate, chromium acetate, preferably basic chromium sulfate, chromium sulfate, It is chromium chloride.
  • These trivalent chromium compounds may be used alone or in combination of two or more.
  • the content of the trivalent chromium compound in the plating solution of the present invention is not particularly limited, it is, for example, 1 to 20 g / L as metal chromium, preferably 5 to 15 g / L.
  • the conductive salt used in the plating solution of the present invention is a chloride.
  • the type of chloride is not particularly limited, and examples include potassium chloride, ammonium chloride, sodium chloride and the like. These chlorides may be used alone or in combination of two or more.
  • the content of chloride in the plating solution of the present invention is not particularly limited, and is, for example, 150 to 400 g / L, preferably 200 to 350 g / L.
  • the pH buffer used in the plating solution of the present invention is not particularly limited, and examples thereof include boric acid, sodium borate, potassium borate, phosphoric acid, and dipotassium hydrogen phosphate, preferably boric acid and sodium borate. It is. These pH buffers may be used alone or in combination of two or more.
  • the content of the pH buffer in the plating solution of the present invention is not particularly limited, and is, for example, 10 to 150 g / L, preferably 50 to 100 g / L.
  • the complexing agent used in the plating solution of the present invention is not particularly limited, and examples thereof include formic acid, ammonium formate, potassium formate, citric acid, triammonium citrate and the like. Among these, ammonium formate and triammonium citrate are preferable. These complexing agents can be used alone or in combination of two or more. Although the content of the complexing agent in the plating solution of the present invention is not particularly limited, it is, for example, 0.3 to 2 times by mole, preferably 0.8 to 1.5 times by mole, the metal 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 long as it is acidic, and is preferably, for example, 2 to 4, and more preferably 2.5 to 3.5.
  • the preparation method of the plating solution of the present invention is not particularly limited.
  • trivalent chromium compound, chloride salt, pH buffer, complexing agent and unsaturated sulfonic acid compound are added to water at 40 to 50 ° C. If necessary, it can be prepared by adding and mixing other components and adjusting the pH.
  • the plating solution of the present invention even if metal impurities are contained, there is no problem such as non-deposition of plating or occurrence of color unevenness such as brown stripes in plating (that is, resistance to metal impurities) ).
  • the plating solution of the present invention does not have the above problems even if the metal impurity is contained in a large amount at a concentration of about several hundreds ppm for long-term use or suddenly.
  • the metal impurities are metals derived from the plating used as the base and other chemicals accompanying the plating. Specific metals include, for example, nickel, zinc, copper, hexavalent chromium and the like, preferably nickel or copper which is often used for base plating.
  • the plating solution of the present invention when nickel is positively contained as a metal impurity, it is possible to prevent burnout at a high current density when plating.
  • the high current density means a portion where current tends to be concentrated, such as a corner or a tip of an item.
  • the nickel that can be used in the plating solution of the present invention is not particularly limited, and examples thereof include nickel salts such as nickel chloride and nickel sulfate.
  • the content of nickel in the plating solution of the present invention is not particularly limited, but is, for example, 10 to 500 ppm, preferably 15 to 200 ppm, and more preferably 20 to 100 ppm.
  • Nickel is a trivalent chromium compound obtained by removing the unsaturated sulfonic acid compound represented by the general formula (1) from the plating solution of the present invention, a chloride as a conductive salt, a pH buffer, and a complexing agent. Even with a chromium plating solution, it prevents burnout at high current density when plating at the same concentration.
  • the trivalent chromium compound, the chloride, the pH buffer, and the complexing agent are the same kind and concentration as the plating solution of the present invention.
  • the normal trivalent chromium plating solution contains iron and cobalt in order to improve the low current density
  • the above-mentioned plating solution of the present invention does not contain iron and / or cobalt. Even so, the enthusiasm improves.
  • the corrosion resistance tends to decrease due to the co-precipitation of iron or cobalt in the plating film. Therefore, it is preferable that the plating solution of the present invention does not substantially contain iron and / or cobalt.
  • the plating solution of the present invention contains substantially no iron and / or cobalt, it means that iron and / or cobalt is 2 ppm or less, preferably 1 ppm or less, more preferably 0.5 ppm or less.
  • the amount of iron and / or cobalt can be analyzed by ICP-MS, atomic absorption spectrophotometry, or the like.
  • the plating solution of the present invention can be plated with chromium on a material to be plated by electroplating the material to be plated with the plating solution of the present invention, as in the conventional chromium plating solution.
  • electroplating may be performed for 1 to 15 minutes at a bath temperature of 25 to 45 ° C., an anode of carbon or iridium oxide, and a cathode current density of 4 to 20 A / dm 2 .
  • metals such as iron, stainless steel, and brass, resin, such as ABS and PC / ABS, are mentioned, for example.
  • the member to be plated may be treated beforehand with copper plating, nickel plating or the like before being treated with the plating solution of the present invention.
  • the chromium plating thus obtained is a chromium plating having the same appearance, throwing power and deposition rate as hexavalent chromium.
  • the unsaturated sulfonic acid compound represented by the formula (1) can suppress the darkening of the color tone of the obtained chromium plating as compared with other unsaturated sulfonic acid compounds. Therefore, this chrome-plated product is suitable for use as parts such as automobile exterior parts such as door handles and emblems, accessories, flush fittings, tools and the like.
  • the resulting chromium plated product also contains substantially no iron and / or cobalt.
  • the chromium plating product of the present invention contains substantially no iron and / or cobalt, it means that iron and / or cobalt is less than 0.5 at%, preferably 0.3 at% or less during chromium plating.
  • the amount of iron and / or cobalt can be analyzed by EDS, XPS or the like.
  • Example 1 Chrome-plated The following basic compositions and the compounds described in Table 1 were respectively dissolved in water to prepare a trivalent chromium plating solution.
  • a Hull cell test was performed using a nickel-plated brass plate for these trivalent chromium plating solutions.
  • the conditions for the Hull cell test are a current of 5 A and a plating time of 3 minutes.
  • the distance at which the plating film was deposited from the left end of the brass plate was measured as shown in FIG. 1, and from this, the reduction rate was calculated as follows.
  • color tone evaluation and appearance evaluation were performed as follows.
  • the color tone after plating was evaluated by L * value using a colorimeter (manufactured by Konica Minolta Co., Ltd.). These results are also shown in Table 1.
  • the standard value is the value at the time of no addition, and the test value is the actually measured value at the time of testing under each condition.
  • the standard values are, respectively, a base composition 1:71 mm, a base composition 2:73 mm, and a base composition 3:74 mm.
  • the unsaturated sulfonic acid compound contained in the plating solution of the present invention is not a material that impairs the color tone, appearance, and throwing power of chromium plating due to its use.
  • Example 2 Chrome plating in the presence of impurities: A trivalent chromium plating solution was prepared in the same manner as in Example 1 except that a watt bath containing 100 ppm of nickel was added as a metal impurity. The same tests as in Example 1 were conducted on these trivalent chromium plating solutions. The results are shown in Table 2.
  • the trivalent chromium plating solution (implementation article) of the present invention which is a chloride bath and contains an unsaturated sulfonic acid compound having a specific structure, has 100 ppm of nickel as a metal impurity in the plating solution, It was found that the performance of the plating was not affected. On the other hand, even in the case of the sulfuric acid bath (the basic composition 3 of the comparative product), even if it is the same trivalent chromium plating solution, there is no metal impurity resistance even if it contains the unsaturated sulfonic acid compound of a specific structure I understand. In addition, it was also found that the plating performance is affected when the plating solution contains 100 ppm of nickel as a metal impurity unless it has a specific structure, even in a chloride bath.
  • Example 3 Chrome plating in the presence of impurities: A trivalent chromium plating solution was prepared containing the compounds described in Basic Composition 1 and Table 3 used in Example 1 and an aqueous solution of copper chloride as a metal impurity in such an amount that copper becomes 20 ppm. The same test as in Example 1 was conducted on this trivalent chromium plating solution. The results are shown in Table 3. In addition, as a comparison, the same test was conducted with a trivalent chromium plating solution containing no unsaturated sulfonic acid compound having a specific structure. The results are also shown in Table 3.
  • the trivalent chromium plating solution (implemented product) of the present invention did not affect the plating performance even when 20 ppm of copper was contained as a metal impurity in the plating solution.
  • Example 4 Chrome-plated: The following basic composition 4, a 25% aqueous solution of sodium vinyl sulfonate and nickel (added as nickel chloride) were dissolved in water at the concentrations shown in Table 4 to prepare a trivalent chromium plating solution.
  • a Hull cell test was performed using a nickel-plated brass plate for these trivalent chromium plating solutions. The conditions for the Hull cell test are a current of 5 A and a plating time of 3 minutes. The same test as in Example 1 was conducted on this trivalent chromium plating solution. Further, the presence or absence of burnt at high current density (left end in FIG. 1) was visually evaluated. The results are also shown in Table 4. To show an example of the presence or absence of burnt, Figure 2 shows the appearance of a brass plate (without burnt) after plating with a plating solution containing 10 ppm of nickel. It showed to 3.
  • the trivalent chromium plating solution (implemented product) of the present invention can prevent darkening at high current density when plating by positively containing nickel as a metal impurity in the plating solution.
  • a trivalent chromium plating solution was prepared by adding 0, 10, 30, 50 ppm of nickel to the plating solution of the basic composition 4 without adding a 25% aqueous solution of sodium vinyl sulfonate.
  • a Hull cell test was performed using a nickel-plated brass plate for these trivalent chromium plating solutions. The conditions for the Hull cell test are a current of 5 A and a plating time of 3 minutes. With respect to this trivalent chromium plating solution, the same test as in Example 1 and the presence or absence of a high current density burnout as in Example 4 were evaluated.
  • the color tone and appearance of the plating obtained by positively containing nickel as a metal impurity in the plating solution of the trivalent chromium plating solution of the present invention were obtained by adding a 25% aqueous solution of sodium vinyl sulfonate of Examples 1 to 3. It was found that it is possible to prevent darkening at high current density when plating, which is the same as when plating with copper. In the case of no addition of nickel, burnt occurred at high current density when plating.
  • the trivalent chromium plating solution of the present invention can be used in various applications as the plating using hexavalent chromium. That's all

Abstract

L'invention concerne : une solution de placage de chrome trivalent qui contient un composé de chrome trivalent, un chlorure qui sert de sel conducteur, un agent tamponnant le pH et un agent complexant, et qui est caractérisé en ce qu'il contient en outre un acide sulfonique insaturé représenté par la formule générale (1) (dans la formule générale (1), R1 représente un atome d'hydrogène, un atome d'halogène ou un groupe hydrocarboné contenant 1 à 10 atomes de carbone ; R2 est absent ou représente un groupe hydrocarboné contenant de 1 à 10 atomes de carbone ; et X représente un atome d'hydrogène ou un atome de métal alcalin) ; et un procédé de placage de chrome trivalent qui utilise cette solution de placage de chrome trivalent. La solution de placage de chrome trivalent et le procédé de placage de chrome trivalent selon la présente invention sont par conséquent affranchis des problèmes tels que la défaillance de dépôt d'un placage et la génération d'une irrégularité de couleur telle que des bandes brunes dans un placage même si une impureté métallique est contenue dans la solution de placage.
PCT/JP2018/045799 2017-12-14 2018-12-13 Solution de placage de chrome trivalent et procédé de placage de chrome trivalent l'employant WO2019117230A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP18888525.5A EP3725919A4 (fr) 2017-12-14 2018-12-13 Solution de placage de chrome trivalent et procédé de placage de chrome trivalent l'employant
CN201880080667.3A CN111479956A (zh) 2017-12-14 2018-12-13 三价铬镀液以及使用其的三价铬镀敷方法
JP2019559193A JPWO2019117230A1 (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
KR1020207017355A KR20200096932A (ko) 2017-12-14 2018-12-13 3 가 크롬 도금액 및 이를 사용한 3 가 크롬 도금 방법
US16/771,066 US20210198797A1 (en) 2017-12-14 2018-12-13 Trivalent chromium plating solution and trivalent chromium plating method using same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017239216 2017-12-14
JP2017-239216 2017-12-14
JP2018-121196 2018-06-26
JP2018121196 2018-06-26

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

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JPS57152483A (en) * 1981-02-09 1982-09-20 W Kiyaningu Materiaruzu Ltd Chromium electrodeposition
JP2009074170A (ja) 2007-08-30 2009-04-09 Nissan Motor Co Ltd クロムめっき部品およびその製造方法
JP2016172933A (ja) * 2011-05-03 2016-09-29 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 電気めっき浴及び黒色クロム層の製造方法

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US4167460A (en) * 1978-04-03 1979-09-11 Oxy Metal Industries Corporation Trivalent chromium plating bath composition and process
US4450052A (en) * 1982-07-28 1984-05-22 M&T Chemicals Inc. Zinc and nickel tolerant trivalent chromium plating baths
CA1223547A (fr) * 1983-07-27 1987-06-30 Louis Gianelos Electrodeposition en bain de chrome trivalent
GB8503019D0 (en) * 1985-02-06 1985-03-06 Canning W Materials Ltd Electroplating
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
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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Publication number Priority date Publication date Assignee Title
JPS57152483A (en) * 1981-02-09 1982-09-20 W Kiyaningu Materiaruzu Ltd Chromium electrodeposition
JP2009074170A (ja) 2007-08-30 2009-04-09 Nissan Motor Co Ltd クロムめっき部品およびその製造方法
JP2016172933A (ja) * 2011-05-03 2016-09-29 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 電気めっき浴及び黒色クロム層の製造方法

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Publication number Publication date
EP3725919A1 (fr) 2020-10-21
JPWO2019117230A1 (ja) 2020-12-17
CN111479956A (zh) 2020-07-31
EP3725919A4 (fr) 2021-09-01
KR20200096932A (ko) 2020-08-14
US20210198797A1 (en) 2021-07-01

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