WO2025142000A1 - Solution d'électrodéposition et procédé d'électrodéposition d'un article par dépôt électrolytique l'utilisant - Google Patents

Solution d'électrodéposition et procédé d'électrodéposition d'un article par dépôt électrolytique l'utilisant Download PDF

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Publication number
WO2025142000A1
WO2025142000A1 PCT/JP2024/034779 JP2024034779W WO2025142000A1 WO 2025142000 A1 WO2025142000 A1 WO 2025142000A1 JP 2024034779 W JP2024034779 W JP 2024034779W WO 2025142000 A1 WO2025142000 A1 WO 2025142000A1
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WO
WIPO (PCT)
Prior art keywords
electroplating solution
electroplating
nickel
solution according
mol
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.)
Pending
Application number
PCT/JP2024/034779
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English (en)
Japanese (ja)
Inventor
瞭 緒方
和則 小野
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.)
Dipsol Chemicals Co Ltd
Original Assignee
Dipsol Chemicals 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 Dipsol Chemicals Co Ltd filed Critical Dipsol Chemicals Co Ltd
Priority to KR1020267012360A priority Critical patent/KR20260071271A/ko
Priority to CN202480071239.XA priority patent/CN122161962A/zh
Publication of WO2025142000A1 publication Critical patent/WO2025142000A1/fr
Anticipated expiration legal-status Critical
Pending 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated

Definitions

  • the present invention relates to an electroplating solution and a method for electroplating an article using the same, and in particular to an electroplating nickel solution that is less likely to corrode articles that contain zinc, such as ceramic electronic components.
  • Electronic nickel plating is used in the manufacture of ceramic electronic components such as varistors, thermistors, inductors, and capacitors.
  • electronic nickel plating is used when forming a base electrode of silver or copper on the surface of a ceramic electronic component having an internal electrode, and then forming a terminal electrode consisting of a nickel plating layer and a tin plating layer on the surface of the base electrode.
  • nickel sulfate or nickel sulfamate is used as a source of nickel ions, as described in Patent Documents 1 and 2, for example.
  • Patent Documents 3 and 4 describe electronic nickel plating solutions containing nickel alkanesulfonate, such as nickel methanesulfonate, as a source of nickel ions.
  • Patent Document 5 describes that the use of nickel chloride instead of nickel sulfate as a source of nickel ions makes it easier to suppress erosion of the element.
  • the inorganic halogen compound includes chloride and/or bromide, and/or The concentration of halide ions is 0.03 mol/L or more and less than 1.7 mol/L.
  • the nickel ion-equivalent molar concentration (C Ni ) of the nickel ion source, the molar concentration (C sulfo ) of the sulfonic acid or a salt thereof, and the molar concentration (C Halo ) of the halide ion satisfy the following relational expression: 0 ⁇ (C sulfo +C Halo -2 ⁇ C Ni ) ⁇ 0.6
  • the concentration of each component is: the nickel ion source has a concentration of 0.15 mol/L to 1.7 mol/L (in terms of nickel ions); and/or - for the sulfonic acid or its salt, from 0.3 mol/L to 4 mol/L;
  • the pH buffer contains boric acid or a salt thereof.
  • a sulfonic acid or its salt represented by formula 1 in combination with sodium hydroxide in an electroplating solution containing a nickel ion source, it is possible to suppress the erosion of articles containing zinc, such as ceramic electronic components. Therefore, it is possible to improve the quality of ceramic electronic components manufactured by electroplating nickel.
  • the electroplating solution of the present invention comprises: A source of nickel ions; an alkane sulfonic acid or hydroxyalkane sulfonic acid represented by formula 1: R-SO 3 H (R is an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms), or a salt thereof; Sodium hydroxide,
  • R-SO 3 H R is an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms
  • the electroplating solution of the present invention is used for nickel electroplating, and is particularly suitable for electroplating articles containing zinc, such as ceramic electronic components.
  • nickel ion source refers to a compound that supplies nickel ions used in electrolytic nickel plating, and in the electrolytic plating solution of the present invention, it is either ionized to generate nickel ions or forms a salt with a counter ion.
  • concentration of the nickel ion source is not particularly limited as long as electrolytic nickel plating can be performed, but may be, for example, a concentration (nickel ion equivalent concentration) such that the concentration of nickel ions generated when the nickel ion source is completely ionized is about 0.15 mol/L to about 1.7 mol/L or about 0.3 mol/L to about 1.3 mol/L. Note that in this specification, when a numerical range is expressed with "to", the upper and lower limits are also included in the numerical range.
  • the nickel ion source is not particularly limited as long as it can supply nickel ions to the electroplating solution, but may include, for example, at least one selected from the group consisting of nickel sulfonate, basic nickel carbonate, anhydrous nickel carbonate, nickel chloride, nickel bromide, and nickel iodide, and may not include conventional nickel sulfate or nickel sulfamate. That is, in one embodiment, the electroplating solution is substantially free of sulfate ions and/or sulfamic acid or a salt thereof.
  • the nickel sulfonate as the nickel ion source is not particularly limited as long as it can perform nickel electroplating.
  • Formula 2 R'(SO 3 H) n (R' is a hydrocarbon group which may have a hydroxyl group, and n is an integer of 1 to 3).
  • R' may be a saturated chain hydrocarbon group having 1 to 15 carbon atoms (e.g., 1 to 7, 1 to 5, or 1 to 3 carbon atoms) which may have a hydroxy group, or a cyclic or heterocyclic hydrocarbon group having 4 to 16 carbon atoms (e.g., 6 to 14 carbon atoms) which may have a hydroxy group.
  • R' may be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, or isopentyl and linear or branched isomers thereof, or a hydroxyalkyl group in which the alkyl group is hydroxy-substituted, a saturated or unsaturated alicyclic hydrocarbon group such as cyclobutyl, cyclobutenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cyclooctanyl, and cyclooctadienyl, or an aromatic hydrocarbon group such as phenyl.
  • alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, or isopentyl and linear or branched isomers thereof
  • the alkane sulfonic acid or hydroxyalkane sulfonic acid or a salt thereof contained as an essential component in the electroplating solution of the present invention functions as a conductivity imparting substance in the electroplating solution, and may be the same as or different from the nickel sulfonate serving as the nickel ion source.
  • the alkane sulfonic acid and hydroxyalkane sulfonic acid contained as essential components in the electroplating solution of the present invention are Formula 1: R-SO 3 H (R is an alkyl group having 1 to 5 carbon atoms or 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms or 1 to 3 carbon atoms).
  • the concentration of the sulfonic acid or salt thereof represented by formula 1 is not particularly limited as long as nickel electroplating can be performed, but may be, for example, about 0.3 mol/L to about 4 mol/L, or about 0.7 mol/L to about 2.6 mol/L.
  • the sulfonic acid or salt thereof represented by formula 1 includes at least one selected from the group consisting of methanesulfonic acid, 2-hydroxyethanesulfonic acid (isethionic acid), and salts thereof.
  • the pH of the electroplating solution of the present invention is not particularly limited as long as it is adjusted by a pH adjuster containing sodium hydroxide, but may be, for example, about 4.5 to about 5.5.
  • a pH adjuster containing sodium hydroxide containing sodium hydroxide
  • the sodium hydroxide is used in combination with the sulfonic acid or a salt thereof, it is possible to suppress erosion of the article to be plated in electronic nickel plating, particularly articles containing zinc such as ceramic electronic components.
  • the electroplating solution is substantially free of ammonia as a pH adjuster. In such an embodiment, erosion of the article to be plated can be further suppressed.
  • the pH buffer is not particularly limited as long as it is capable of performing nickel electroplating, but may include, for example, boric acid, metaboric acid, or 2-morpholinoethanesulfonic acid or a salt thereof.
  • the concentration of the pH buffer is not particularly limited, but may be, for example, about 7 to about 20 g/L or about 10 to about 17 g/L for boric acid.
  • the pH buffer is substantially free of a chelating agent such as an organic carboxylic acid or a salt thereof. In such an embodiment, erosion of the article to be plated can be further suppressed.
  • the organic carboxylic acid or a salt thereof include citric acid, glutamic acid, gluconic acid, and/or glycolic acid.
  • the electroplating solution of the present invention may contain an inorganic halide compound.
  • the inorganic halide compound provides halide ions in the electroplating solution and may be the same as or different from the nickel ion source.
  • the inorganic halide compound is not particularly limited, but may include, for example, a chloride that generates chloride ions and/or a bromide that generates bromide ions.
  • the concentration of the halide ions in the electroplating solution is not particularly limited as long as nickel electroplating can be performed, but may be, for example, about 0.03 mol/L or more and less than about 1.7 mol/L, about 0.1 mol/L to about 0.5 mol/L, or about 0.1 to about 0.34 mol/L.
  • the ratio (C Ni /C Halo ) of the nickel ion equivalent molar concentration (C Ni ) of the nickel ion source to the molar concentration (C Halo ) of the halide ions is greater than 1 and less than about 57, greater than 1 and less than about 35, or greater than 1 and less than about 12.
  • the nickel ion molar concentration (C Ni ) of the nickel ion source, the molar concentration (C sulfo ) of the sulfonic acid or salt thereof, and the molar concentration (C Halo ) of the halide ion satisfy the following relationship: 0 ⁇ (C sulfo +C Halo -2 ⁇ C Ni ) ⁇ approximately 0.6 and the relational expression is: 0 ⁇ (C sulfo + C Halo ⁇ 2 ⁇ C Ni ) ⁇ about 0.5 or about 0.4
  • the ions derived from the sulfonic acid or a salt thereof and the halide ions can serve as counter ions of the nickel ions. When the nickel ions and the counter ions satisfy this relational formula, the nickel ions can be present stably while suppressing erosion of the ceramic body.
  • the electroplating solution of the present invention may further contain any component that is commonly used in the art, so long as it does not impair the purpose of the solution.
  • the optional component may include an organic compound additive that is added to the plating bath for electroplating.
  • the type of the organic compound additive is not particularly limited, but may be, for example, at least one selected from the group consisting of a brightener, a water conditioner, and an antifoaming agent.
  • the present invention also relates to a method for electroplating an article, the method including a step of passing a current through a plating bath containing the electroplating solution described above as one aspect of the present invention.
  • the article to which the method is applied is not particularly limited, but since the electroplating solution inhibits erosion of articles containing zinc, the method is suitable for electroplating articles containing zinc. Examples of such articles include ceramic electronic components such as varistors, thermistors, inductors, and capacitors.
  • the temperature of the plating bath is not particularly limited, but may be, for example, about 40°C to about 60°C, or about 45°C to about 55°C.
  • a soluble electrode such as a nickel plate or an insoluble electrode such as a platinum plate may be used as the anode used in the plating bath. By using the soluble electrode, nickel ions can be efficiently replenished to the electroplating bath.
  • the method of the present invention may further include any step commonly used in the art, so long as it does not impair the object of the method.
  • the method may include a step of washing the article before the current application step, or a step of washing the article after the current application step.

Landscapes

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

Abstract

La présente invention a pour objet de fournir une solution de nickelage électrolytique dans laquelle un corps d'élément céramique est difficilement érodable. Une solution d'électrodéposition selon la présente invention comprend : une source d'alimentation en ions nickel ; un acide sulfonique représenté par la formule 1 : R-SO3H (dans laquelle R est un groupe alkyle ou un groupe hydroxyalkyle ayant 1 à 5 atomes de carbone), ou un sel de celui-c i; de l'hydroxyde de sodium ; et un agent tampon de pH.
PCT/JP2024/034779 2023-12-25 2024-09-27 Solution d'électrodéposition et procédé d'électrodéposition d'un article par dépôt électrolytique l'utilisant Pending WO2025142000A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020267012360A KR20260071271A (ko) 2023-12-25 2024-09-27 전기 도금액 및 그것을 사용하여 물품을 전기 도금하는 방법
CN202480071239.XA CN122161962A (zh) 2023-12-25 2024-09-27 电镀液和使用该电镀液对物品进行电镀的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023217702 2023-12-25
JP2023-217702 2023-12-25

Publications (1)

Publication Number Publication Date
WO2025142000A1 true WO2025142000A1 (fr) 2025-07-03

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PCT/JP2024/034779 Pending WO2025142000A1 (fr) 2023-12-25 2024-09-27 Solution d'électrodéposition et procédé d'électrodéposition d'un article par dépôt électrolytique l'utilisant

Country Status (3)

Country Link
KR (1) KR20260071271A (fr)
CN (1) CN122161962A (fr)
WO (1) WO2025142000A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5334632A (en) * 1976-09-13 1978-03-31 Daiwa Kasei Kenkyusho Nickel plating bath
JPH1171695A (ja) * 1997-06-18 1999-03-16 Atotech Deutsche Gmbh 低ストレスニッケルの電気メッキ
JP2010209427A (ja) * 2009-03-11 2010-09-24 Tdk Corp 電気ニッケルめっき液および電子部品の製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4678194B2 (ja) 2005-02-02 2011-04-27 株式会社村田製作所 電子部品の製造方法、及び電子部品
JP2008285732A (ja) 2007-05-21 2008-11-27 Meltex Inc ニッケルめっき液及びそのニッケルめっき液を用いた電気めっき方法並びにその電気めっき方法でニッケルめっき皮膜を形成したチップ部品
JP4986167B2 (ja) 2008-06-30 2012-07-25 Ｔｄｋ株式会社 電気ニッケルめっき液およびめっき方法
JP2012077324A (ja) 2010-09-30 2012-04-19 Tdk Corp Ｎｉめっき液

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5334632A (en) * 1976-09-13 1978-03-31 Daiwa Kasei Kenkyusho Nickel plating bath
JPH1171695A (ja) * 1997-06-18 1999-03-16 Atotech Deutsche Gmbh 低ストレスニッケルの電気メッキ
JP2010209427A (ja) * 2009-03-11 2010-09-24 Tdk Corp 電気ニッケルめっき液および電子部品の製造方法

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Publication number Publication date
CN122161962A (zh) 2026-06-05
KR20260071271A (ko) 2026-05-19

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