WO2022180867A1 - Gold plating liquid containing gold sulfite salt, and replenisher liquid for gold plating liquid containing gold sulfite salt - Google Patents

Gold plating liquid containing gold sulfite salt, and replenisher liquid for gold plating liquid containing gold sulfite salt Download PDF

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WO2022180867A1
WO2022180867A1 PCT/JP2021/014720 JP2021014720W WO2022180867A1 WO 2022180867 A1 WO2022180867 A1 WO 2022180867A1 JP 2021014720 W JP2021014720 W JP 2021014720W WO 2022180867 A1 WO2022180867 A1 WO 2022180867A1
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gold
gold plating
plating solution
sulfite
cyanide
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PCT/JP2021/014720
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French (fr)
Japanese (ja)
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正英 水橋
孝文 久保
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松田産業株式会社
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Application filed by 松田産業株式会社 filed Critical 松田産業株式会社
Priority to CN202180084759.0A priority Critical patent/CN116568866A/en
Priority to KR1020237029559A priority patent/KR20230136651A/en
Publication of WO2022180867A1 publication Critical patent/WO2022180867A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G7/00—Compounds of gold
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a gold plating solution containing gold sulfite and a gold plating solution replenisher containing sodium gold sulfite.
  • a gold sulfite salt such as sodium gold sulfite is used as the gold raw material contained in the gold plating solution and the replenisher for the gold plating solution.
  • Patent Document 2 discloses a method for producing an electroless gold plating solution and a method for producing an aqueous gold sulfite salt solution for a gold plating solution. It is said that it can provide an excellent plating solution for
  • Patent Document 2 Although the method described in Patent Document 2 can suppress the formation of a gold film on the inner wall of the plating bath, etc., no consideration is given to the formed film. As a result of investigations by the present inventors, there was variation in the formed coating when the coating was formed using a gold plating solution containing a gold sulfite salt. Particularly in electroless gold plating, there have been cases where a desired gold plating film thickness cannot be obtained or the gold plating film has a poor color tone.
  • An object of the present invention is to provide a gold plating solution and a replenisher for the gold plating solution that can solve the problem of variations in the gold plating film.
  • the inventors of the present invention conducted extensive studies to solve the above problems, and found that a specific substance present in the gold plating solution and the replenisher for the gold plating solution is the cause of the variation in the gold plating film. Found it. Specifically, the presence of cyanide ions (CN ⁇ ) in the gold plating solution reduces the plating performance of the gold plating solution, such as a decrease in the thickness of the gold plating film and a poor color tone of the gold plating film. It has been found.
  • the inventors have found that the reduction in the plating performance of the gold plating solution can be suppressed by reducing the cyanide ion concentration in the gold plating solution and the replenisher for the gold plating solution to a certain concentration or less. .
  • One form of the present invention is a non-cyanide gold plating solution containing a gold sulfite salt, an electrolyte, and water, and having a cyanide ion concentration of 1 mg/L or less.
  • Another aspect of the present invention is a non-cyanide gold plating solution replenisher containing a gold sulfite and water and having a cyanide ion concentration of 1 mg/L or less.
  • the present invention it is possible to provide a gold plating solution and a replenisher for the gold plating solution that can suppress deterioration in the plating performance of the gold plating solution, such as a decrease in the thickness of the gold plating film and a poor color tone of the gold plating film.
  • One embodiment of the present invention is a non-cyanide gold plating solution containing a gold sulfite salt, an electrolyte and water, and having a cyanide ion concentration of 1 mg/L or less.
  • the plating performance of the gold plating solution ( This is based on the finding that the plating formation ability) is lowered. Based on this knowledge, by setting the cyanide ion concentration in the gold plating solution to 1 mg/L or less, it is possible to suppress the deterioration of the plating performance of the gold plating solution.
  • the gold sulfite in the gold plating solution is not particularly limited, but includes sodium gold sulfite, potassium gold sulfite, and ammonium gold sulfite, with sodium gold sulfite being particularly preferred.
  • the method for preparing the gold plating solution of the present embodiment is not particularly limited, but it can be prepared by adding a gold sulfite salt and an electrolyte to an aqueous medium containing water and mixing.
  • Known electrolytes that can be contained in the gold plating solution can be used as the electrolyte.
  • the content of the gold sulfite in the gold plating solution is not particularly limited, but is usually 0.2 g/L or more and 100 g/L or less, preferably 0.5 g/L or more and 30 g/L or less in terms of gold concentration. be.
  • the content of the electrolyte in the gold plating solution is not particularly limited, but is usually 20 g/L or more and 300 g/L or less.
  • other components that may be contained in the gold plating solution such as pH adjusters and complexing agents, may be contained. Addition of a complexing agent can improve the stability of the gold plating solution.
  • Another embodiment of the present invention is a non-cyanide gold plating solution replenisher containing gold sulfite and water and having a cyanide ion concentration of 1 mg/L or less.
  • the gold plating solution replenisher is a solution for replenishing the gold component in the gold plating solution.
  • the content of the gold sulfite in the replenisher for the gold plating solution is not particularly limited, but is usually 30 g/L or more and 200 g/L or less, preferably 50 g/L or more and 150 g/L or less in terms of gold concentration. .
  • the replenisher for the gold plating solution is a replenisher for replenishing the gold component of the gold plating solution
  • the replenisher for the gold plating solution must also have a cyanide ion concentration of 1 mg/L or less as in the gold plating solution. , the deterioration of the plating performance of the gold plating solution can be suppressed.
  • the molar ratio (SO 3 2 ⁇ /Au) between the gold concentration and the sulfite ion concentration in the gold plating solution replenisher is preferably 2.1 or more and 2.9 or less. According to studies by the present inventors, since sulfite ions affect the oxidation-reduction potential of the plating solution, within the above range, the replenisher for the gold plating solution becomes a stable solution, and good plating performance is achieved. It is preferable because it can be exhibited.
  • the gold concentration in the gold plating solution replenisher can be measured by IPC emission spectroscopy.
  • test piece pure copper plate, thickness 0.3 mm, size 25 mm x 40 mm, substrate: nickel plating 1 ⁇ m, gold strike plating 0.1 ⁇ m
  • substrate nickel plating 1 ⁇ m
  • Example 1 Regard cyanide concentration>
  • the non-cyanide gold plating solution 1 was treated to adsorb and remove cyanide, and the non-cyanide gold plating solution 2 (Example 1) having a cyanide concentration of 0.8 mg / L and a cyanide concentration of 0.4 mg /
  • a non-cyanide gold plating solution 3 Example 2 was prepared.
  • the plating film thicknesses were 9.49 ⁇ m and 9.50 ⁇ m, respectively.
  • Electroless plating (displacement plating) method Using the sodium gold (I) sulfite solutions of Comparative Examples 2 to 6 and Examples 3 to 7 prepared above, the concentration of gold was 2 g/L, and 5.0 g/L of citric acid monohydrate and 5.0 g/L of citric acid trihydrate were used as pH buffer components. Comparative Examples 2 to 6 and Example 3 containing 65.0 g/L of sodium dihydrate, 0.1 g/L of thiourea as a precipitation accelerator, and 5 mg/L of thallium formate (concentration in terms of thallium) as a crystal modifier. An electroless gold plating solution of ⁇ 7 was prepared, and the bath temperature was 70°C and the pH was 6.0.
  • the nickel-plated copper plate material After forming nickel plating of 5 to 7 ⁇ m on the copper plate material using a commercially available pretreatment agent and an electroless nickel plating solution, the nickel-plated copper plate material is immersed in the electroless plating solution prepared above for 15 minutes, then washed with water and dried. did. The presence or absence of gold deposition on the copper plate material was confirmed visually and with a fluorescent X-ray film thickness meter.
  • the lemon yellow gold plating film was deposited with a thickness of 0.1 ⁇ m or more, it was judged as ⁇ , and when the gold plating film was 0.1 ⁇ m or more and slight unevenness in color tone was observed, it was judged as ⁇ .
  • the film thickness was insufficient (less than 0.1 ⁇ m), it was judged as x. O judgment or ⁇ judgment was evaluated as a pass.
  • Gold (I) sodium sulfite solution stability evaluation method 50 mL of the sodium gold(I) sulfite solution prepared above in Comparative Examples 2 to 6 and Examples 3 to 7 was placed in a 100 mL polypropylene container, and a piece of quantitative filter paper cut to 15 ⁇ 15 mm was immersed. After that, the lid of the polypropylene container was closed. Next, the polypropylene container was immersed in a hot water bath maintained at 70° C. to indirectly heat the sodium gold(I) sulfite solution. After 5 hours, the polypropylene container was taken out, the lid was opened, the immersed quantitative filter paper was scooped up with tweezers, and the color of the filter paper was visually confirmed.

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

Abstract

The present invention addresses the problem of providing a gold plating liquid and a replenisher liquid for gold plating liquid, each of which is capable of solving the problem of unevenness in the plating performance. The problem is solved by a non-cyan gold plating liquid and a replenisher liquid for cyan gold plating liquid, each of which contains a gold sulfite salt, an electrolyte and water, while having a cyanide ion concentration of 1 mg/L or less.

Description

亜硫酸金塩を含む金めっき液、及び亜硫酸金塩を含む金めっき液用補充液Gold plating solution containing gold sulfite and replenisher for gold plating solution containing gold sulfite
　本発明は、亜硫酸金塩を含む金めっき液、及び亜硫酸金ナトリウムを含む金めっき液用補充液に関する。 The present invention relates to a gold plating solution containing gold sulfite and a gold plating solution replenisher containing sodium gold sulfite.
　金めっき液及び金めっき液用補充液に含まれる金原料としては、亜硫酸金ナトリウムなどの亜硫酸金塩が用いられており、その製造方法は、例えば特許文献１に開示されている。 A gold sulfite salt such as sodium gold sulfite is used as the gold raw material contained in the gold plating solution and the replenisher for the gold plating solution.
　また、特許文献２には、無電解金めっき液の製造方法、及び金めっき液用亜硫酸金塩水溶液の製造方法が開示され、亜硫酸金水溶液のパーティクル増加率を制御することにより、めっきランニング安定性に優れためっき液を提供できるとされている。 In addition, Patent Document 2 discloses a method for producing an electroless gold plating solution and a method for producing an aqueous gold sulfite salt solution for a gold plating solution. It is said that it can provide an excellent plating solution for
特許第２７７３９３１号Patent No. 2773931 特開２００６－２４９４８５号公報JP 2006-249485 A
　特許文献２に記載の方法では、めっき液槽の内壁等に金被膜が形成することを抑制することができる一方で、形成された被膜については何ら検討されていない。本発明者らが検討したところ、亜硫酸金塩を含む金めっき液により被膜を形成した際に、形成される被膜にばらつきがあった。特に無電解金めっき形成において、所望の金めっき膜厚が得られない場合や、金めっき被膜の色調の不良が生じることがあった。
　本発明は、このような金めっき被膜のバラツキの問題を解決し得る、金めっき液及び金めっき液用補充液を提供することを課題とする。 Although the method described in Patent Document 2 can suppress the formation of a gold film on the inner wall of the plating bath, etc., no consideration is given to the formed film. As a result of investigations by the present inventors, there was variation in the formed coating when the coating was formed using a gold plating solution containing a gold sulfite salt. Particularly in electroless gold plating, there have been cases where a desired gold plating film thickness cannot be obtained or the gold plating film has a poor color tone.
An object of the present invention is to provide a gold plating solution and a replenisher for the gold plating solution that can solve the problem of variations in the gold plating film.
　本発明者らは、上記課題を解決すべく検討を重ねたところ、金めっき液及び金めっき液用補充液中に存在する特定の物質が、金めっき被膜のバラツキを生じさせる原因であることを見出した。具体的には、金めっき液中にシアン化物イオン（ＣＮ－）が存在することで、金めっき被膜の膜厚の低下、金めっき被膜の色調の不良など、金めっき液のめっき性能が低下することが判明した。 The inventors of the present invention conducted extensive studies to solve the above problems, and found that a specific substance present in the gold plating solution and the replenisher for the gold plating solution is the cause of the variation in the gold plating film. Found it. Specifically, the presence of cyanide ions (CN − ) in the gold plating solution reduces the plating performance of the gold plating solution, such as a decrease in the thickness of the gold plating film and a poor color tone of the gold plating film. It has been found.
　そして、上記知見に基づいて、金めっき液及び金めっき液用補充液中のシアン化物イオン濃度を一定濃度以下に低減することで、金めっき液のめっき性能が低下することを抑制できることを見出した。 Based on the above findings, the inventors have found that the reduction in the plating performance of the gold plating solution can be suppressed by reducing the cyanide ion concentration in the gold plating solution and the replenisher for the gold plating solution to a certain concentration or less. .
　本発明の一形態は、亜硫酸金塩と電解質と水とを含み、シアン化物イオン濃度が１ｍｇ／Ｌ以下である、非シアン金めっき液である。また、本発明の別の形態は、亜硫酸金塩と水とを含み、シアン化物イオン濃度が１ｍｇ／Ｌ以下である、非シアン金めっき液用補充液である。 One form of the present invention is a non-cyanide gold plating solution containing a gold sulfite salt, an electrolyte, and water, and having a cyanide ion concentration of 1 mg/L or less. Another aspect of the present invention is a non-cyanide gold plating solution replenisher containing a gold sulfite and water and having a cyanide ion concentration of 1 mg/L or less.
　本発明により、金めっき被膜の膜厚の低下、金めっき被膜の色調の不良など、金めっき液のめっき性能が低下することを抑制できる金めっき液及び金めっき液用補充液を提供できる。 According to the present invention, it is possible to provide a gold plating solution and a replenisher for the gold plating solution that can suppress deterioration in the plating performance of the gold plating solution, such as a decrease in the thickness of the gold plating film and a poor color tone of the gold plating film.
　以下、本発明について詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施形態の一例（代表例）であり、本発明はこれらの内容に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents. Various modifications can be made within the scope of the gist.
　本発明の一実施形態は、亜硫酸金塩と電解質と水とを含み、シアン化物イオン濃度が１ｍｇ／Ｌ以下である、非シアン金めっき液である。
　本発明は、金めっきを形成するに際して、液中に存在する特定の物質、具体的には、金めっき液中にシアン化物イオン（ＣＮ－）が存在することで、金めっき液のめっき性能（めっき形成能）が低下することを見出したことに基づくものである。そして、当該知見を基に、金めっき液中のシアン化物イオン濃度を１ｍｇ／Ｌ以下とすることで、金めっき液のめっき性能が低下することを抑制できる。 One embodiment of the present invention is a non-cyanide gold plating solution containing a gold sulfite salt, an electrolyte and water, and having a cyanide ion concentration of 1 mg/L or less.
In the present invention, when forming a gold plating , the plating performance of the gold plating solution ( This is based on the finding that the plating formation ability) is lowered. Based on this knowledge, by setting the cyanide ion concentration in the gold plating solution to 1 mg/L or less, it is possible to suppress the deterioration of the plating performance of the gold plating solution.
　金めっき液中にシアン化物イオンが混入し得る理由は定かではないが、金はリサイクルにより得られることが多く、そのため金めっき液製造の環境において金精製が行われる場合がある。そして、その際に貴金属の溶剤として使用するシアン化カリウムが揮発して、金めっき液に不可避的に混入してしまうことなどが考えられる。
　金めっき液中のシアン化物イオンを低減させる方法としては、イオン交換樹脂またはキレート樹脂により金めっき液中のシアン化物イオンを除去させる方法があげられる。 Although it is not clear why cyanide ions may be present in the gold plating solution, gold is often obtained by recycling, and therefore gold refining may occur in the environment of gold plating solution production. At that time, it is conceivable that potassium cyanide used as a solvent for noble metals volatilizes and inevitably mixes with the gold plating solution.
As a method for reducing cyanide ions in the gold plating solution, there is a method of removing cyanide ions in the gold plating solution using an ion exchange resin or a chelate resin.
　金めっき液中の亜硫酸金塩としては特に限定されないが、亜硫酸金ナトリウム、亜硫酸金カリウム、亜硫酸金アンモニウムなどが挙げられ、亜硫酸金ナトリウムが特に好ましい。 The gold sulfite in the gold plating solution is not particularly limited, but includes sodium gold sulfite, potassium gold sulfite, and ammonium gold sulfite, with sodium gold sulfite being particularly preferred.
　本実施形態の金めっき液の調製方法は特段限定されないが、水を含む水性媒体に亜硫酸金塩と電解質とを添加して、混合することで調製することができる。電解質は、金めっき液に含有させることができる既知の電解質を用いることができる。
　金めっき液中、亜硫酸金塩の含有量は特段限定されないが、通常金濃度に換算して０．２ｇ／Ｌ以上１００ｇ／Ｌ以下であり、好ましくは０．５ｇ／Ｌ以上３０ｇ／Ｌ以下である。また、金めっき液中、電解質の含有量は特段限定されないが、通常２０ｇ／Ｌ以上３００ｇ／Ｌ以下である。
　その他、金めっき液に含有され得る他の成分、例えばｐＨ調整剤、錯化剤などを含有してもよい。錯化剤の添加により、金めっき液の安定性が向上し得る。 The method for preparing the gold plating solution of the present embodiment is not particularly limited, but it can be prepared by adding a gold sulfite salt and an electrolyte to an aqueous medium containing water and mixing. Known electrolytes that can be contained in the gold plating solution can be used as the electrolyte.
The content of the gold sulfite in the gold plating solution is not particularly limited, but is usually 0.2 g/L or more and 100 g/L or less, preferably 0.5 g/L or more and 30 g/L or less in terms of gold concentration. be. Also, the content of the electrolyte in the gold plating solution is not particularly limited, but is usually 20 g/L or more and 300 g/L or less.
In addition, other components that may be contained in the gold plating solution, such as pH adjusters and complexing agents, may be contained. Addition of a complexing agent can improve the stability of the gold plating solution.
　本発明の別の実施形態は、亜硫酸金塩と水とを含み、シアン化物イオン濃度が１ｍｇ／Ｌ以下である、非シアン金めっき液用補充液である。金めっき液用補充液は、金めっき液中の金成分を補充する液である。金めっき液用補充液中、亜硫酸金塩の含有量は特段限定されないが、通常金濃度に換算して３０ｇ／Ｌ以上２００ｇ／Ｌ以下であり、好ましくは５０ｇ／Ｌ以上１５０ｇ／Ｌ以下である。
　金めっき液用補充液は、金めっき液の金成分を補給する補充液であることから、金めっき補充液についても金めっき液と同様に、シアン化物イオン濃度が１ｍｇ／Ｌ以下であることで、金めっき液のめっき性能が低下することを抑制できる。 Another embodiment of the present invention is a non-cyanide gold plating solution replenisher containing gold sulfite and water and having a cyanide ion concentration of 1 mg/L or less. The gold plating solution replenisher is a solution for replenishing the gold component in the gold plating solution. The content of the gold sulfite in the replenisher for the gold plating solution is not particularly limited, but is usually 30 g/L or more and 200 g/L or less, preferably 50 g/L or more and 150 g/L or less in terms of gold concentration. .
Since the replenisher for the gold plating solution is a replenisher for replenishing the gold component of the gold plating solution, the replenisher for the gold plating solution must also have a cyanide ion concentration of 1 mg/L or less as in the gold plating solution. , the deterioration of the plating performance of the gold plating solution can be suppressed.
　本実施形態では、金めっき液用補充液中の金濃度と亜硫酸イオン濃度とのモル比（ＳＯ３ ２－／Ａｕ）が２．１以上２．９以下であることが好ましい。本発明者の検討によると、亜硫酸イオンはめっき液の酸化還元電位に影響を及ぼすことから、上記範囲内であることで、金めっき液用補充液が安定した液となり、また良好なめっき性能を発揮することができることから好ましい。 In this embodiment, the molar ratio (SO 3 2− /Au) between the gold concentration and the sulfite ion concentration in the gold plating solution replenisher is preferably 2.1 or more and 2.9 or less. According to studies by the present inventors, since sulfite ions affect the oxidation-reduction potential of the plating solution, within the above range, the replenisher for the gold plating solution becomes a stable solution, and good plating performance is achieved. It is preferable because it can be exhibited.
　なお、金めっき液用補充液中の金濃度は、ＩＰＣ発光分光法により測定することができる。 The gold concentration in the gold plating solution replenisher can be measured by IPC emission spectroscopy.
　以下、実施例を用いて本発明をより詳細に説明するが、本発明の範囲が実施例の記載により限定されないことはいうまでもない。 Although the present invention will be described in more detail below using examples, it goes without saying that the scope of the present invention is not limited by the description of the examples.
＜シアン化物濃度に関する比較例１＞
　亜硫酸金（Ｉ）ナトリウムを金濃度で１４ｇ／Ｌ、電解質として亜硫酸ナトリウム８０ｇ／Ｌ、緩衝剤としてエチレンジアミン四酢酸二ナトリウム２０ｇ／Ｌ、結晶調整剤としてギ酸タリウムを１０ｍｇ／Ｌ（タリウム濃度）を水中に含む非シアン金めっき液１を準備した。シアン化物濃度を測定したところ１．１ｍｇ／Ｌであった。
　非シアン金めっき液１に試験片（純銅板、厚さ０．３ｍｍ、大きさ２５ｍｍ×４０ｍｍ、下地：ニッケルめっき１μｍ、金ストライクめっき０．１μｍ）を浴温５０℃で３０分間浸漬し、電流密度０．５Ａ／ｄｍ２で電解めっきを行ったところ、めっき膜厚は９．１２μｍであった。 <Comparative Example 1 Concerning Cyanide Concentration>
Sodium gold (I) sulfite at a gold concentration of 14 g/L, sodium sulfite at 80 g/L as an electrolyte, disodium ethylenediaminetetraacetate at 20 g/L as a buffer, and thallium formate at 10 mg/L (thallium concentration) as a crystal modifier in water. A non-cyanide gold plating solution 1 was prepared. The cyanide concentration was measured to be 1.1 mg/L.
A test piece (pure copper plate, thickness 0.3 mm, size 25 mm x 40 mm, substrate: nickel plating 1 μm, gold strike plating 0.1 μm) was immersed in the non-cyanide gold plating solution 1 for 30 minutes at a bath temperature of 50 ° C. When electroplating was performed at a density of 0.5 A/dm 2 , the plating film thickness was 9.12 µm.
＜シアン化物濃度に関する実施例１～２＞
　非シアン金めっき液１に対し、シアンを吸着・除去する処理を行い、シアン化物濃度が０．８ｍｇ／Ｌである非シアン金めっき液２（実施例１）、シアン化物濃度が０．４ｍｇ／Ｌである非シアン金めっき液３（実施例２）を調製した。これらの非シアン金めっき液についても比較例１と同様に、試験片に対して電解めっきを行ったところ、めっき膜厚はそれぞれ９．４９μｍ、９．５０μｍであった。 <Examples 1 and 2 regarding cyanide concentration>
The non-cyanide gold plating solution 1 was treated to adsorb and remove cyanide, and the non-cyanide gold plating solution 2 (Example 1) having a cyanide concentration of 0.8 mg / L and a cyanide concentration of 0.4 mg / A non-cyanide gold plating solution 3 (Example 2) was prepared. When electroplating was performed on the test piece using these non-cyanide gold plating solutions in the same manner as in Comparative Example 1, the plating film thicknesses were 9.49 μm and 9.50 μm, respectively.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（比較例２～６および実施例３～７）
　亜硫酸金（Ｉ）ナトリウム溶液の準備：
　金濃度を１００ｇ／Ｌとし、シアン化物濃度（ＣＮ－）および亜硫酸イオン濃度（ＳＯ３ ２－）が異なる、比較例２～６及び実施例３～７の種々の亜硫酸金（Ｉ）ナトリウム溶液を準備した。 (Comparative Examples 2-6 and Examples 3-7)
Preparation of sodium gold(I) sulfite solution:
Various gold (I) sodium sulfite solutions of Comparative Examples 2 to 6 and Examples 3 to 7, which had a gold concentration of 100 g/L and differed in cyanide concentration (CN − ) and sulfite ion concentration (SO 3 2− ), were prepared. Got ready.
　無電解めっき（置換めっき）方法：
　上記調製した比較例２～６及び実施例３～７の亜硫酸金（Ｉ）ナトリウム溶液を用い、金濃度２ｇ／Ｌ、ｐＨ緩衝成分としてクエン酸一水和物５．０ｇ／Ｌ及びクエン酸三ナトリウム二水和物６５．０ｇ／Ｌ、析出促進剤としてチオ尿素０．１ｇ／Ｌ、並びに結晶調整剤としてギ酸タリウム５ｍｇ／Ｌ(タリウム換算濃度)を含む、比較例２～６及び実施例３～７の無電解金めっき液を調製し、浴温７０℃、ｐＨ６．０とした。
　銅板材料上に市販の前処理剤および無電解ニッケルめっき液でニッケルめっきを５～７μｍ形成した後、ニッケルめっき付き銅板材料を上記調製した無電解めっき液に１５分間浸漬し、その後水洗後、乾燥した。
　銅板材料上の金析出の有無を目視および蛍光エックス線膜厚計で確認した。レモンイエローの金めっき被膜が０．１μｍ以上の膜厚で析出していたときに○判定、金めっき被膜が０．１μｍ以上で色調にわずかなムラが認められたときに△判定、金めっきの膜厚不足(０．１μｍ未満)のときに×判定とした。〇判定または△判定を合格と評価した。 Electroless plating (displacement plating) method:
Using the sodium gold (I) sulfite solutions of Comparative Examples 2 to 6 and Examples 3 to 7 prepared above, the concentration of gold was 2 g/L, and 5.0 g/L of citric acid monohydrate and 5.0 g/L of citric acid trihydrate were used as pH buffer components. Comparative Examples 2 to 6 and Example 3 containing 65.0 g/L of sodium dihydrate, 0.1 g/L of thiourea as a precipitation accelerator, and 5 mg/L of thallium formate (concentration in terms of thallium) as a crystal modifier. An electroless gold plating solution of ∼7 was prepared, and the bath temperature was 70°C and the pH was 6.0.
After forming nickel plating of 5 to 7 μm on the copper plate material using a commercially available pretreatment agent and an electroless nickel plating solution, the nickel-plated copper plate material is immersed in the electroless plating solution prepared above for 15 minutes, then washed with water and dried. did.
The presence or absence of gold deposition on the copper plate material was confirmed visually and with a fluorescent X-ray film thickness meter. When the lemon yellow gold plating film was deposited with a thickness of 0.1 μm or more, it was judged as ○, and when the gold plating film was 0.1 μm or more and slight unevenness in color tone was observed, it was judged as △. When the film thickness was insufficient (less than 0.1 μm), it was judged as x. O judgment or △ judgment was evaluated as a pass.
　亜硫酸金（Ｉ）ナトリウム溶液安定性評価方法：
　１００ｍＬ容量のポリプロピレン製容器に上記調製した比較例２～６及び実施例３～７の亜硫酸金（Ｉ）ナトリウム溶液を５０ｍＬ入れ、１５×１５ｍｍに切り出した定量ろ紙を１枚浸漬した。その後、ポリプロピレン容器のふたを閉めた。
　次に、７０℃に保持した温水槽にポリプロピレン製容器を浸漬して、亜硫酸金（Ｉ）ナトリウム溶液を間接加温した。５時間後、ポリプロピレン製容器を取り出し、ふたを開けて、浸漬した定量ろ紙をピンセットすくい上げ、ろ紙の色を目視で確認した。
　亜硫酸金（Ｉ）ナトリウム溶液が不安定な場合、加温によって金のコロイド粒子が生成し、これが定量ろ紙に吸着してろ紙の色が、紫色、茶色または黒色に変化する。加温前後で、定量ろ紙の色変化が目視で確認されなかった場合、安定な亜硫酸金ナトリウム溶液を得たと判定し合格(○)とした。加温前後で、定量ろ紙の色変化が目視で確認された場合、亜硫酸金ナトリウム溶液は不安定であったと判定し不合格(×)とした。結果を以下の表２に示す。 Gold (I) sodium sulfite solution stability evaluation method:
50 mL of the sodium gold(I) sulfite solution prepared above in Comparative Examples 2 to 6 and Examples 3 to 7 was placed in a 100 mL polypropylene container, and a piece of quantitative filter paper cut to 15×15 mm was immersed. After that, the lid of the polypropylene container was closed.
Next, the polypropylene container was immersed in a hot water bath maintained at 70° C. to indirectly heat the sodium gold(I) sulfite solution. After 5 hours, the polypropylene container was taken out, the lid was opened, the immersed quantitative filter paper was scooped up with tweezers, and the color of the filter paper was visually confirmed.
If the sodium gold(I) sulfite solution is unstable, heating produces colloidal gold particles that are adsorbed on the quantitative filter paper and change the color of the filter paper to purple, brown or black. When no change in the color of the quantitative filter paper was visually observed before and after heating, it was determined that a stable sodium gold sulfite solution was obtained and was evaluated as acceptable (○). When a change in the color of the quantitative filter paper was visually observed before and after heating, it was determined that the sodium gold sulfite solution was unstable and was rejected (x). The results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000002

Claims (4)

  1. 　亜硫酸金塩と電解質と水とを含み、シアン化物イオン濃度が１ｍｇ／Ｌ以下である、非シアン金めっき液。 A non-cyanide gold plating solution containing a gold sulfite, an electrolyte, and water, and having a cyanide ion concentration of 1 mg/L or less.
  2. 　前記亜硫酸金塩が、亜硫酸金ナトリウムである、請求項１に記載の非シアン金めっき液。 The non-cyanide gold plating solution according to claim 1, wherein the gold sulfite is sodium gold sulfite.
  3. 　亜硫酸金塩と水とを含み、シアン化物イオン濃度が１ｍｇ／Ｌ以下である、非シアン金めっき液用補充液。 A replenisher for a non-cyanide gold plating solution containing gold sulfite and water and having a cyanide ion concentration of 1 mg/L or less.
  4. 　液中の金濃度と亜硫酸イオン濃度とのモル比（ＳＯ３ ２－／Ａｕ）が２．１以上２．９以下である、請求項３に記載の非シアン金めっき液用補充液。 4. The replenisher for a cyanide-free gold plating solution according to claim 3, wherein the molar ratio (SO 3 2− /Au) between the gold concentration and the sulfite ion concentration in the solution is 2.1 or more and 2.9 or less.
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