[go: up one dir, main page]

WO2009093499A1 - Bain de placage au chrome trivalent - Google Patents

Bain de placage au chrome trivalent Download PDF

Info

Publication number
WO2009093499A1
WO2009093499A1 PCT/JP2009/050300 JP2009050300W WO2009093499A1 WO 2009093499 A1 WO2009093499 A1 WO 2009093499A1 JP 2009050300 W JP2009050300 W JP 2009050300W WO 2009093499 A1 WO2009093499 A1 WO 2009093499A1
Authority
WO
WIPO (PCT)
Prior art keywords
trivalent chromium
chromium plating
plating bath
trivalent
plating
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.)
Ceased
Application number
PCT/JP2009/050300
Other languages
English (en)
Japanese (ja)
Inventor
Junichi Katayama
Shingo Nagamine
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.)
Okuno Chemical Industries Co Ltd
Original Assignee
Okuno Chemical Industries Co Ltd
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 Okuno Chemical Industries Co Ltd filed Critical Okuno Chemical Industries Co Ltd
Publication of WO2009093499A1 publication Critical patent/WO2009093499A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • the present invention relates to a plating bath containing a trivalent chromium compound, a plating method using the plating bath, and an article on which a chromium plating film is formed.
  • Chrome plating is widely used in various fields such as decoration and industrial use.
  • Conventionally used chromium plating baths contain a large amount of hexavalent chromium as a chromium component.
  • the toxicity of hexavalent chromium has become a problem, and development of a plating solution with low toxicity is strongly desired from the viewpoint of work environment and wastewater treatment.
  • chromium plating baths containing trivalent chromium that is less toxic than hexavalent chromium (see Patent Documents 1 to 3 and Non-Patent Documents 1 to 3 below).
  • the valent chromium ion concentration is 0.4 mol or more, and at least one component selected from the group consisting of an aqueous aliphatic carboxylic acid and a salt thereof is added in an amount of 1.0 to 3.0 with respect to 1 mol of trivalent chromium ions.
  • a chromium plating bath containing a molar range has been reported.
  • Such a trivalent chrome plating bath has been partially put into practical use as a decorative chrome plating with a thin plating thickness.
  • Plating baths such as Canning), trade name: trichlorite (Eugelite), trade name: trichrome plus (Atotech Japan) are commercially available.
  • the plating film formed from the conventional trivalent chromium plating bath has a darker appearance and is inferior in decorativeness than the plating film formed from the hexavalent chromium plating bath. For this reason, there is a strong demand for a trivalent chromium plating bath that can form a chromium plating film having a white appearance similar to a chromium plating film obtained from a hexavalent chromium bath.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and its main object is the problem of the above-described conventional trivalent chromium plating bath, particularly plating formed from a hexavalent chromium bath.
  • An object of the present invention is to provide a novel trivalent chromium plating bath that can be used effectively for industrial purposes by solving the problems that the appearance of the film is darker than the film and the decorativeness is poor.
  • the trivalent chromium ion concentration in the plating bath is 0.003 to 0.12 mol / L, which is lower than the conventional trivalent chromium plating bath, and the concentration of the aqueous aliphatic carboxylic acids is trivalent.
  • the amount By limiting the amount to 0.3 mol or less with respect to 1 mol of chromium ions, it is possible to form a chromium plating film having a white appearance with a high decorativeness similar to a chromium plating film formed from a plating bath containing a hexavalent chromium compound. I found it.
  • the chrome plating bath has a good turnability even immediately after the building bath, can form a good chrome plating film in a wide current density range, and the formed chrome plating film has good corrosion resistance and high hardness. It has been found that it can be thickened and is highly industrially useful, and the present invention has been completed here.
  • the present invention provides the following trivalent chromium plating bath, a plating method using the plating bath, and an article on which a chromium plating film is formed.
  • 1. 3 comprising an aqueous solution containing a water-soluble trivalent chromium compound, a conductive salt and a pH buffer, wherein the concentration of trivalent chromium ions in the aqueous solution is 0.003 to 0.12 mol / L. Valent chromium plating bath.
  • the trivalent according to Item 1 comprising an aqueous solution containing 0.003 to 0.12 mol / L of trivalent chromium ions, 50 to 400 g / L of conductive salt, and 60 to 120 g / L of pH buffering agent. Chrome plating bath. 3. 3. The trivalent chromium plating bath according to item 1 or 2, further comprising 1 to 10 g / L of at least one sulfur-containing compound selected from the group consisting of a compound having an SO 2 group and a compound having an SO 3 group. 4). Item 4.
  • the trivalent chromium plating bath of the present invention contains a water-soluble trivalent chromium compound, a conductive salt, and a pH buffer as essential components.
  • the trivalent chromium compound may be a water-soluble compound containing trivalent chromium, and for example, chromium sulfate, chromium nitrate, chromium acetate, basic chromium sulfate and the like can be used. These trivalent chromium compounds can be used individually by 1 type or in mixture of 2 or more types.
  • the trivalent chromium ion concentration needs to be in the range of 0.003 to 0.12 mol / L.
  • Conventional trivalent chromium plating baths usually contain about 0.4 mol / L or more of trivalent chromium ions.
  • the trivalent chromium ion concentration in the plating bath increases, the film forming speed increases, but the color tone of the plating film becomes dark, while the trivalent chromium ion concentration is low. It became clear that although the color tone of the film became brighter, the film forming speed decreased.
  • the valent chromium ion concentration needs to be in the range of about 0.003 to 0.12 mol / L, and preferably in the range of about 0.04 to 0.1 mol / L. became.
  • the concentration of the water-soluble aliphatic carboxylic acid is 0.3 mol with respect to 1 mol of the trivalent chromium ion. It is necessary that: In conventional trivalent chromium plating baths, water-soluble aliphatic carboxylic acids are considered to be essential in order to maintain the stability of the plating bath, and usually about equimolar or more with respect to trivalent chromium ions. Water-soluble carboxylic acids are used.
  • the trivalent chromium plating bath of the present invention by setting the trivalent chromium ion concentration to a relatively low concentration of about 0.003 to 0.12 mol / L, water-soluble aliphatic carboxylic acids can be obtained. Even if it is not included, the stability of the plating bath is not hindered.
  • the plating film formed from such a low trivalent chromium ion concentration plating bath is hexavalent chromium. It has a white appearance excellent in decorativeness similar to a chromium plating film formed from a plating bath containing a compound, and further has good corrosion resistance and high hardness.
  • the trivalent chromium plating bath of the present invention may contain water-soluble aliphatic carboxylic acids as long as the properties of the formed chromium plating film are not affected.
  • water-soluble aliphatic carboxylic acids may be contained with respect to 1 mol of trivalent chromium ions.
  • the amount of the water-soluble aliphatic carboxylic acids is preferably 0.2 mol or less with respect to 1 mol of trivalent chromium ions.
  • the water-soluble aliphatic carboxylic acids are water-soluble aliphatic carboxylic acids or salts thereof, for example, aliphatic monocarboxylic acids such as formic acid and acetic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid.
  • Aliphatic hydroxy monocarboxylic acid such as gluconic acid: Aliphatic hydroxy dicarboxylic acid such as malic acid; Carboxylic acid such as aliphatic hydroxy tricarboxylic acid such as citric acid, Water-soluble salt of these carboxylic acids, for example, sodium salt Examples thereof include alkali metal salts such as potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, ammonium salts and the like.
  • the trivalent chromium plating bath of the present invention does not contain water-soluble aliphatic carboxylic acids at all, or its content is very small. Since the conventional trivalent chromium plating bath contains a relatively large amount of water-soluble aliphatic carboxylic acids, a long electrolytic treatment is required to stabilize the complex after the plating bath is constructed. However, since the plating bath of the present invention does not contain water-soluble aliphatic carboxylic acids or its content is very small, a good white chrome plating similar to a hexavalent chromium film immediately after the building bath is obtained. A film can be formed. This eliminates the need for long-term electrolytic treatment and greatly improves work efficiency. Further, when replenishing the chromium compound, time for stabilizing the complex is not required, and the management of the plating bath is easy.
  • the conductive salt for example, sulfates such as potassium sulfate, sodium sulfate and ammonium sulfate, alkali metal chlorides such as potassium chloride and sodium chloride can be used. These conductive salts can be used singly or in combination of two or more.
  • the concentration of the conductive salt is not particularly limited, but when the concentration is low, the bath voltage rises and the bath temperature rises during electrolysis, so that it is necessary to cool the electrolytic cell in order to maintain a constant temperature. In addition, when the conductive salt concentration is high, the bath voltage decreases, but it is difficult to dissolve at the time of bathing, and when the plating operation is stopped and the temperature of the plating bath decreases, precipitation or the like may occur. Will be generated. From these points, the concentration of the conductive salt is preferably about 50 to 400 g / L, and more preferably about 150 to 300 g / L.
  • pH buffering agents that can be used include boric acid, sodium borate, potassium borate, phosphoric acid, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium carbonate, sodium hydrogen carbonate, and the like.
  • concentration of the pH buffering agent is preferably about 60 to 120 g / L, more preferably about 80 to 100 g / L.
  • the trivalent chromium plating bath of the present invention may further contain at least one sulfur-containing compound selected from the group consisting of a compound having an SO 2 group and a compound having an SO 3 group, if necessary. These sulfur-containing compounds are effective components for providing a dense and good appearance to the formed chromium film.
  • examples of the compound having an SO 2 group include saccharin and sodium saccharin
  • examples of the compound having an SO 3 group include sulfobenzaldehyde, benzenesulfonic acid, toluenesulfonic acid, and salts thereof.
  • sulfur-containing compounds can be used singly or in combination of two or more.
  • the concentration of the sulfur-containing compound is not particularly limited, but is usually preferably about 1 to 10 g / L, and more preferably about 2 to 7 g / L.
  • the trivalent chromium plating bath of the present invention is obtained by dissolving the above components in water, and the order of dissolving the components is arbitrary.
  • the pH of the trivalent chromium plating solution bathed with each of the above components varies somewhat depending on the type of complexing agent used, but is usually preferably in the range of about pH 2-4. By setting the pH range to this level, it is possible to prevent the precipitation due to chromium hydroxide even when water-soluble aliphatic carboxylic acids are not included.
  • the trivalent chromium plating of the present invention when the bath temperature during the plating operation is low, the throwing power is improved, but the film-forming speed tends to decrease. Conversely, when the bath temperature is high, the product is manufactured. Although the film speed is improved, the throwing power to the low current density region tends to decrease.
  • An appropriate bath temperature may be determined in consideration of this point, but generally, a temperature range of about 30 to 60 ° C. is preferable as a bath temperature for industrial use.
  • the anode used for plating is not particularly limited, and a known insoluble anode such as a Ti—Pt electrode can be usually used.
  • a Ti electrode covered with an Ir—Ta composite oxide thin film it is advantageous in that generation of hexavalent chromium can be suppressed.
  • the trivalent chrome plating bath of the present invention has good coverage, and can form a good chrome plating film even at a low current density of about 1 A / dm 2 , for example. Therefore, a chromium plating film having a good appearance can be formed in a wide cathode current density range of about 1 to 20 A / dm 2 .
  • a good chromium plating film can be formed on the object to be plated by energizing the object to be plated as a cathode in the chromium plating bath according to a conventional method.
  • chromium hydroxide may precipitate in the washing water after the plating treatment.
  • the addition of a trivalent chromium complexing agent in the washing water immediately after the chromium plating treatment can prevent the precipitation in the washing water.
  • any compound having a complexing power with respect to trivalent chromium can be used without particular limitation.
  • the above-mentioned water-soluble aliphatic carboxylic acids can be used.
  • Complexes such as tetraacetic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, water-soluble salts thereof and the like can be used.
  • concentration of the complexing agent in the washing water is not particularly limited, but may be, for example, about 1 to 10 g / L.
  • the trivalent chromium plating bath of the present invention the following remarkable effects are exhibited.
  • a good white chromium plating film similar to a hexavalent chromium film can be formed immediately after the bathing. This eliminates the need for long-term electrolytic treatment and greatly improves work efficiency.
  • It has excellent throwing power in a low current density region and can form a good chromium plating film in a wide current density range.
  • the plating film grows according to the plating time, it is possible to apply a thickness exceeding 1 ⁇ m.
  • a good chromium plating film having high film hardness and excellent corrosion resistance can be obtained.
  • the plating test method is as follows. The results are shown in Table 2 below.
  • (Plating test method) 1) Color tone evaluation of film Using each trivalent chrome plating bath immediately after the building bath, the color tone of the test piece formed in a 500 mL Haring cell was visually evaluated.
  • the test piece is a 0.48 dm 2 brass plate with a bright Ni plating film of about 3 ⁇ m.
  • the current density is 7.5 A / dm 2
  • the plating time is 5 minutes
  • the anode is an Ir—Ta composite oxide thin film.
  • a coated Ti electrode was used.
  • FIG. 1 the measurement result of a reflectance is shown in FIG. 1 about the chromium plating film formed from the hexavalent chromium plating bath, and the plating film obtained in Example 1 and Comparative Example 1.
  • FIG. 1 the measurement result of a reflectance is shown in FIG. 1 about the chromium plating film formed from the hexavalent chromium plating bath, and the plating film obtained in Example 1 and Comparative Example 1.
  • Hull cell test Using each trivalent chromium plating bath immediately after the building bath, a Hull cell test was performed using a product obtained by forming a bright Ni plating on a brass plate with a thickness of about 3 ⁇ m.
  • the Hull cell test conditions were a cell current of 5 A and a plating time of 5 minutes, and a Ti electrode coated with an Ir—Ta composite oxide thin film was used as the anode.
  • Vickers hardness measurement The Vickers hardness was measured about the to-be-plated object which could be thickened by the said test.
  • the film forming speed is greatly reduced after about 60 minutes from the start of plating, and the chromium plating film is about 3 ⁇ m even if the film forming time is increased.
  • the film could not be thickened.

Landscapes

  • 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'invention porte sur un bain de placage au chrome trivalent qui est caractérisé en ce qu'il est composé d'une solution aqueuse contenant un composé de chrome trivalent soluble dans l'eau, un sel conducteur et un agent de tamponnage de pH. Le bain de placage au chrome trivalent est également caractérisé en ce que la solution aqueuse a une concentration d'ions chrome trivalents de 0,003 à 0,12 mole/l. L'invention porte également sur un procédé de placage au chrome comprenant une étape de formation d'un film de placage au chrome sur un objet devant être plaqué en utilisant l'objet comme cathode dans le bain de placage au chrome trivalent puis en lavant l'objet plaqué avec une eau de lavage contenant un agent de complexion pour les ions chrome trivalents, et sur un article ayant un film de placage au chrome formé à l'aide du bain de placage au chrome trivalent. Le bain de placage au chrome selon la présente invention est un nouveau bain de placage au chrome trivalent efficace du point de vue commercial, qui a résolu divers problèmes posés par des bains de placage au chrome trivalent classiques.
PCT/JP2009/050300 2008-01-24 2009-01-13 Bain de placage au chrome trivalent Ceased WO2009093499A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-013585 2008-01-24
JP2008013585A JP2011099126A (ja) 2008-01-24 2008-01-24 ３価クロムめっき浴

Publications (1)

Publication Number Publication Date
WO2009093499A1 true WO2009093499A1 (fr) 2009-07-30

Family

ID=40901007

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/050300 Ceased WO2009093499A1 (fr) 2008-01-24 2009-01-13 Bain de placage au chrome trivalent

Country Status (2)

Country Link
JP (1) JP2011099126A (fr)
WO (1) WO2009093499A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240352612A1 (en) * 2021-07-28 2024-10-24 Jcu Corporation White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015037391A1 (ja) * 2013-09-12 2017-03-02 奥野製薬工業株式会社 ３価クロムめっき浴
JP6332677B2 (ja) * 2014-05-01 2018-05-30 奥野製薬工業株式会社 ３価クロムめっき方法
JP6547232B2 (ja) * 2017-02-08 2019-07-24 テクノロール株式会社 めっき液ならびにめっき製品の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5395134A (en) * 1976-12-16 1978-08-19 Ibm Chrome or chrome alloy electroplating liquid
JPS57152483A (en) * 1981-02-09 1982-09-20 W Kiyaningu Materiaruzu Ltd Chromium electrodeposition
JPS61588A (ja) * 1984-06-14 1986-01-06 Nippon Kokan Kk <Nkk> 片面電気めつき鋼板の後処理方法
JPS61235592A (ja) * 1985-02-06 1986-10-20 ダブリユ−　キヤニング　マテリアルズ　リミテツド 改良された電気メツキ方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5395134A (en) * 1976-12-16 1978-08-19 Ibm Chrome or chrome alloy electroplating liquid
JPS57152483A (en) * 1981-02-09 1982-09-20 W Kiyaningu Materiaruzu Ltd Chromium electrodeposition
JPS61588A (ja) * 1984-06-14 1986-01-06 Nippon Kokan Kk <Nkk> 片面電気めつき鋼板の後処理方法
JPS61235592A (ja) * 1985-02-06 1986-10-20 ダブリユ−　キヤニング　マテリアルズ　リミテツド 改良された電気メツキ方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240352612A1 (en) * 2021-07-28 2024-10-24 Jcu Corporation White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using same

Also Published As

Publication number Publication date
JP2011099126A (ja) 2011-05-19

Similar Documents

Publication Publication Date Title
JP5322083B2 (ja) ３価クロムめっき浴及びその製造方法
JP6227062B2 (ja) 電気めっき浴及び黒色クロム層の製造方法
CN106103809B (zh) 由三价电解质沉积的微不连续铬的钝化
JPH08209379A (ja) アルカリ亜鉛および亜鉛合金電気めっき浴およびプロセス
JP5299887B2 (ja) ３価クロムめっき皮膜用電解処理液
EP0151235B1 (fr) Procédé de préparation des bandes d&#39;acier électroplaquées en alliage Zn-Fe
JP5652585B2 (ja) ３価クロムめっき浴
US4142948A (en) Chromium deposition solution
WO2012114737A1 (fr) Procédé pour la production d&#39;un article moulé plaqué de chrome trivalent et article moulé plaqué de chrome trivalent
JP5336762B2 (ja) 銅‐亜鉛合金電気めっき浴およびこれを用いためっき方法
JP7349427B2 (ja) ３価クロムメッキ液およびこれを用いたクロムメッキ方法
CA1132940A (fr) Solution d&#39;electroplacage renfermant du chrome trivalent, du formate, et un agent reducteur
WO2009093499A1 (fr) Bain de placage au chrome trivalent
TWI546422B (zh) Trivalent chromium plating bath
JP5549837B2 (ja) クロムめっき皮膜の防錆用浸漬処理液及び防錆処理方法
JP5867761B2 (ja) 黒色Ｃｒ−Ｃｏ合金めっき皮膜用黒化処理液
JP2012082475A (ja) バレルめっきによる３価クロムめっき方法
JP6218473B2 (ja) 無電解Ｎｉ−Ｐ−Ｓｎめっき液
WO2010027021A1 (fr) Bain galvanoplastique d&#39;alliage cuivre-zinc
US7204871B2 (en) Metal plating process
JP6517501B2 (ja) ストライク銅めっき液およびストライク銅めっき方法
WO2010101212A1 (fr) Bain d&#39;électro-placage d&#39;alliage de cuivre et de zinc et procédé de placage au moyen de celui-ci
CN111465720A (zh) 提高包含铬合金最外层的基材的耐腐蚀性的方法
KR102014342B1 (ko) 무전해 크롬도금 조성물 및 이를 이용하는 무전해 크롬도금 방법
WO2022224901A1 (fr) Solution de placage au chrome trivalent et procédé de placage au chrome l&#39;utilisant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09703492

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09703492

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP