JP2022123819A - Palladium plating solution and palladium plating solution replenisher - Google Patents
Palladium plating solution and palladium plating solution replenisher Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 114
- 238000007747 plating Methods 0.000 title claims abstract description 110
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 150000002940 palladium Chemical class 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
本発明は、パラジウムめっき液及びパラジウムめっき補充液に関する。 The present invention relates to a palladium plating solution and a palladium plating replenisher.
パラジウムめっき液及びパラジウムめっき補充液に含まれる可溶性のパラジウム塩として、アンモニア系のパラジウム錯体が用いられている。当該錯体として、例えば特許文献１には、テトラアンミンパラジウムクロライドの製造方法が開示されている。 Ammonia-based palladium complexes are used as soluble palladium salts contained in palladium plating solutions and palladium plating replenishers. As the complex, for example, Patent Document 1 discloses a method for producing tetraamminepalladium chloride.
一方でパラジウムめっきは、めっき被膜層が厚くなると、被膜にクラックが生じやすいという問題があり、特許文献２においては、パラジウムめっき液に添加剤としてカルボキシル基を２個以上有するカルボン酸を加えることで、クラックの問題を解決しようとする試みが開示されている。 On the other hand, palladium plating has a problem that cracks are likely to occur in the coating when the plating coating layer becomes thick. , an attempt to solve the cracking problem is disclosed.
また、パラジウムめっき液への添加剤として、特許文献３にはゲルマニウムが開示されており、ゲルマニウムの添加によりパラジウムめっき被膜のバリア作用が向上し、耐熱性
の高い接合部を形成できることが開示されている。
Further, Patent Document 3 discloses germanium as an additive to the palladium plating solution, and discloses that the addition of germanium improves the barrier action of the palladium plating film and enables the formation of highly heat-resistant joints. there is
本発明者らは、特許文献２に提案された方法を用いてパラジウムめっきの厚付けを検討したところ、クラックの問題が解決されない場合があった。本発明は、上記特許文献２に開示された方法とは異なる方法で、パラジウムめっきの厚付けが可能となるパラジウムめっき液及びパラジウムめっき補充液を提供することを課題とする。 When the inventors of the present invention investigated thickening the palladium plating using the method proposed in Patent Document 2, there were cases where the problem of cracks could not be resolved. An object of the present invention is to provide a palladium plating solution and a palladium plating replenisher that enable thick palladium plating by a method different from the method disclosed in Patent Document 2 above.
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、パラジウムめっき液及びパラジウムめっき補充液中に存在する特定の物質が、パラジウムめっき被膜のクラックを生じさせる原因であることを見出した。特許文献３のように、ゲルマニウムを添加することでパラジウムめっき被膜のバリア作用が向上するという報告があり、添加物によりめっき特性が改善する場合がある。しかしながら本発明者らの検討により、パラジウムめっき液中にシアン化物イオン（ＣＮ－）、又はリン（Ｐ）が存在することで、パラジウムめっき被膜にクラックが生じやすいことが判明した。 The present inventors have made extensive studies to solve the above problems, and found that a specific substance present in the palladium plating solution and the palladium plating replenisher causes cracks in the palladium plating film. . As in Patent Document 3, there is a report that the addition of germanium improves the barrier action of a palladium plating film, and the plating properties may be improved by the additive. However, the present inventors have found that the presence of cyanide ions (CN − ) or phosphorus (P) in the palladium plating solution is likely to cause cracks in the palladium plating film.
具体的には、パラジウムめっき液中にシアン化物イオンが存在することで、急速にパラジウムめっき成膜速度が遅くなり、成膜したパラジウムめっき被膜にクラックが生じやすいことが判明した。また、パラジウムめっき液中にリンが存在することで、他の不純物、例えば銀との間で反応しリン化銀となり、めっき界面にリン化銀が存在することでクラックが生じやすいことが判明した。
そして、上記知見に基づいて、シアン化物イオン濃度、及びリン濃度を一定濃度以下に低減することで、クラックが生じず、パラジウムめっきの厚付けが可能となるパラジウムめっき液及びパラジウムめっき補充液を提供できることを見出した。
Specifically, it was found that the presence of cyanide ions in the palladium plating solution abruptly slows down the palladium plating film formation rate, and cracks tend to occur in the formed palladium plating film. In addition, it was found that the presence of phosphorus in the palladium plating solution reacts with other impurities such as silver to form silver phosphide, and the presence of silver phosphide at the plating interface is likely to cause cracks. .
Then, based on the above knowledge, by reducing the cyanide ion concentration and the phosphorus concentration to a certain concentration or less, a palladium plating solution and a palladium plating replenisher are provided that do not cause cracks and enable thick palladium plating. I found what I could do.
本発明は、可溶性のパラジウム塩と電解質と水とを含むパラジウムめっき液であって、パラジウムめっき液中のシアン化物イオン濃度が１．０ｍｇ／Ｌ以下である、及び／又はパラジウムめっき液中のリン濃度が１０ｍｇ／Ｌ以下である、パラジウムめっき液である。
また、本発明の別の形態は、可溶性のパラジウム塩と水とを含むパラジウムめっき補充液であって、パラジウムめっき補充液中のシアン化物イオン濃度が１．０ｍｇ／Ｌ以下である、及び／又はパラジウムめっき液中のリン濃度が１０ｍｇ／Ｌ以下である。
The present invention provides a palladium plating solution containing a soluble palladium salt, an electrolyte, and water, wherein the cyanide ion concentration in the palladium plating solution is 1.0 mg/L or less; A palladium plating solution having a concentration of 10 mg/L or less.
Another aspect of the present invention is a palladium plating replenisher containing a soluble palladium salt and water, wherein the cyanide ion concentration in the palladium plating replenisher is 1.0 mg/L or less, and/or The phosphorus concentration in the palladium plating solution is 10 mg/L or less.
本発明により、めっき被膜にクラックが生じず、パラジウムめっきの厚付けが可能となるパラジウムめっき液及びパラジウムめっき補充液を提供できる。 The present invention can provide a palladium plating solution and a palladium plating replenishing solution that do not cause cracks in the plating film and enable thick palladium plating.
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、可溶性のパラジウム塩と電解質と水とを含むパラジウムめっき液である。本実施形態では、パラジウムめっき液中のシアン化物イオン濃度が１．０ｍｇ／Ｌ以下であり、及び／又はパラジウムめっき液中のリン濃度が１０ｍｇ／Ｌ以下である。
本発明は、パラジウムめっき被膜のクラックを生じさせる原因を見出したことに基づくものである。具体的には、パラジウムめっき液中にシアン化物イオンが存在することで、急速にパラジウムめっき成膜速度が遅くなり、成膜したパラジウムめっき被膜にクラックが生じやすいことを、本発明者らは見出した。当該知見を基に、パラジウム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、パラジウムめっき被膜のクラックを抑制することができる。
One embodiment of the invention is a palladium plating solution comprising a soluble palladium salt, an electrolyte and water. In this embodiment, the cyanide ion concentration in the palladium plating solution is 1.0 mg/L or less and/or the phosphorus concentration in the palladium plating solution is 10 mg/L or less.
The present invention is based on the discovery of the cause of cracks in palladium plating films. Specifically, the present inventors found that the presence of cyanide ions in the palladium plating solution rapidly slows down the palladium plating film formation rate, and cracks are likely to occur in the formed palladium plating film. rice field. Based on this finding, cracking of the palladium plating film can be suppressed by setting the cyanide ion concentration in the palladium plating solution to 1 mg/L or less.
パラジウム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、パラジウムはリサイクルにより得られることが多く、そのためパラジウムめっき液製造の環境においてパラジウム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、パラジウム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。
パラジウム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シアン化物イオンを除去する方法があげられる。
Although the reason why cyanide ions can be mixed in the palladium plating solution is not clear, palladium is often obtained by recycling, and therefore palladium purification may be performed in the environment of palladium 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 palladium plating solution.
A method of reducing cyanide ions in the palladium plating solution includes a method of removing cyanide ions using an ion exchange resin or a chelate resin.
また本発明者らは、パラジウムめっき液中にリンが存在することで、他の不純物、例えば銀との間で反応しリン化銀となり、めっき界面にリン化銀が存在することでクラックが生じやすいことを見出した。当該知見を基に、パラジウムめっき液中のリン濃度を１０ｍｇ／Ｌ以下とすることで、パラジウムめっき被膜のクラック発生を抑制することができる。特にパラジウム被膜を厚付けした際のパラジウムめっき被膜のクラック発生を抑制することができる。 The present inventors also found that the presence of phosphorus in the palladium plating solution reacts with other impurities such as silver to form silver phosphide, and the presence of silver phosphide at the plating interface causes cracks. I found it easy. Based on this knowledge, the occurrence of cracks in the palladium plating film can be suppressed by setting the phosphorus concentration in the palladium plating solution to 10 mg/L or less. In particular, it is possible to suppress the occurrence of cracks in the palladium plated coating when the palladium coating is thickened.
パラジウムめっき液中にリンが混入し得る理由は定かではないが、パラジウムを精製する際に溶媒抽出を用いて精製する際の、抽出溶媒中へのリン混入などが考えられる。
パラジウムめっき液中のリン濃度を低減させる方法としては、活性炭による吸着除去があげられる。
The reason why phosphorus can be mixed in the palladium plating solution is not clear, but it is conceivable that phosphorus is mixed in the extraction solvent when purifying palladium by solvent extraction.
As a method for reducing the phosphorus concentration in the palladium plating solution, adsorption removal using activated carbon can be cited.
パラジウムめっき液中の可溶性のパラジウム塩は特に限定されないが、ジクロロジアン
ミンパラジウム、ジクロロテトラアンミンパラジウム、ジニトロジアンミンパラジウム、ジニトロテトラアンミンパラジウム、などが挙げられ、ジクロロテトラアンミンパラジウム（ＩＩ）が特に好ましい。
The soluble palladium salt in the palladium plating solution is not particularly limited, but includes dichlorodiamminepalladium, dichlorotetraamminepalladium, dinitrodiamminepalladium, dinitrotetraamminepalladium, etc. Dichlorotetraamminepalladium (II) is particularly preferred.
本実施形態のパラジウム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パラジウム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、パラジウム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。
パラジウムめっき液中、パラジウム塩の含有量は特段限定されないが、通常パラジウム濃度に換算して１ｇ／Ｌ以上１５０ｇ／Ｌ以下であり、好ましくは２ｇ／Ｌ以上１００ｇ／Ｌ以下である。また、パラジウムめっき液中、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、パラジウムめっき液に含有され得る他の成分、例えばｐＨ調整剤などを含有してもよい。
Although the method for preparing the palladium plating solution of the present embodiment is not particularly limited, it can be prepared by adding a palladium salt and an electrolyte to an aqueous medium containing water and mixing. A known electrolyte that can be contained in a palladium plating solution can be used as the electrolyte.
Although the content of the palladium salt in the palladium plating solution is not particularly limited, it is usually 1 g/L or more and 150 g/L or less, preferably 2 g/L or more and 100 g/L or less in terms of palladium concentration. Also, the electrolyte content in the palladium 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 palladium plating solution, such as pH adjusters, may be contained.
本発明の別の実施形態は、可溶性のパラジウム塩と水とを含むパラジウムめっき補充液であって、パラジウムめっき補充液中のシアン化物イオン濃度が１．０ｍｇ／Ｌ以下であり、及び／又はパラジウムめっき液中のリン濃度が１０ｍｇ／Ｌ以下である。パラジウムめっき補充液は、パラジウムめっき液中のパラジウムを補充する液である。パラジウムめっき補充液中、パラジウム塩の含有量は特段限定されないが、通常パラジウム濃度に換算して１ｇ／Ｌ以上１５０ｇ／Ｌ以下であり、好ましくは２ｇ／Ｌ以上１５０ｇ／Ｌ以下である。
パラジウムめっき補充液は、パラジウムめっき液のパラジウム成分を補給する補充液であり、パラジウムめっき補充液についてもパラジウムめっき液と同様に、シアン化物イオン濃度が１．０ｍｇ／Ｌ以下であり、及び／又はパラジウムめっき液中のリン濃度が１０ｍｇ／Ｌ以下であることで、パラジウム被膜のクラック発生を抑制できる。
Another embodiment of the present invention is a palladium plating replenisher solution comprising a soluble palladium salt and water, wherein the cyanide ion concentration in the palladium plating replenisher is 1.0 mg/L or less, and/or palladium The phosphorus concentration in the plating solution is 10 mg/L or less. A palladium plating replenishing solution is a solution for replenishing palladium in a palladium plating solution. Although the content of the palladium salt in the palladium plating replenisher is not particularly limited, it is usually 1 g/L or more and 150 g/L or less, preferably 2 g/L or more and 150 g/L or less in terms of palladium concentration.
The palladium plating replenisher is a replenisher for replenishing the palladium component of the palladium plating solution, and the palladium plating replenisher has a cyanide ion concentration of 1.0 mg/L or less, and/or When the phosphorus concentration in the palladium plating solution is 10 mg/L or less, it is possible to suppress the occurrence of cracks in the palladium coating.
本発明に係る実施形態は、特にパラジウムめっきを厚付けした場合、例えば１μｍ以上、好ましくは３μｍ以上のパラジウムめっき被膜を形成する際に、好ましく適用できる。 The embodiment according to the present invention can be preferably applied particularly when palladium plating is thickened, for example, when forming a palladium plating film having a thickness of 1 μm or more, preferably 3 μm or more.
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。 EXAMPLES The present invention will be described in more detail below using examples, but it goes without saying that the scope of the present invention is not limited by the description of the examples.
＜シアン濃度に関する比較例１＞
ジクロロテトラアンミンパラジウム（ＩＩ）をパラジウム濃度で１５ｇ／Ｌ、電解質として塩化アンモニウムを８５ｇ／Ｌ、を水中に含むパラジウムめっき液１を準備した。シアン濃度を測定したところ、１．２ｍｇ／Ｌであった。
パラジウムめっき液１に試験片（純銅板、厚さ０．３ｍｍ、大きさ２５ｍｍ×４０ｍｍ）を、浴温５５℃で６０分間浸漬し、電流密度１Ａ／ｄｍ２で電解めっきを行ったところ、めっきの析出速度は８．７μｍ／ｈであった。
<Comparative Example 1 Regarding Cyan Density>
A palladium plating solution 1 containing dichlorotetraamminepalladium (II) at a palladium concentration of 15 g/L and 85 g/L of ammonium chloride as an electrolyte in water was prepared. The cyan concentration was measured and found to be 1.2 mg/L.
A test piece (pure copper plate, thickness 0.3 mm, size 25 mm x 40 mm) was immersed in palladium plating solution 1 at a bath temperature of 55°C for 60 minutes, and electrolytic plating was performed at a current density of 1 A/dm 2 . was 8.7 μm/h.
＜シアン濃度に関する実施例１～２＞
パラジウムめっき液１に対し、シアンを揮発させる処理を行い、シアン濃度が０．９ｍｇ／Ｌであるパラジウムめっき液２（実施例１）、シアン濃度が０．５ｍｇ／Ｌであるパラジウムめっき液３（実施例２）を調製した。これらのパラジウムめっき液についても同様に、試験片に対して電解めっきを行ったところ、めっきの析出速度はそれぞれ１４．８μｍ／ｈ、１５．１μｍ／ｈであった。
<Examples 1 and 2 regarding cyan density>
Palladium plating solution 1 was subjected to cyanide volatilization treatment, and palladium plating solution 2 having a cyan concentration of 0.9 mg/L (Example 1) and palladium plating solution 3 having a cyan concentration of 0.5 mg/L ( Example 2) was prepared. Electroplating was also performed on test pieces using these palladium plating solutions, and the deposition rates of plating were 14.8 μm/h and 15.1 μm/h, respectively.
＜リン濃度に関する比較例２＞
ジクロロテトラアンミンパラジウム（ＩＩ）をパラジウム濃度で１５ｇ／Ｌ、電解質として塩化アンモニウムを８５ｇ／Ｌ、を水中に含むパラジウムめっき液４を準備した。リン濃度を測定したところ、１１ｍｇ／Ｌであった。
パラジウムめっき液４に試験片（純銅板、厚さ０．３ｍｍ、大きさ２５ｍｍ×４０ｍｍ）を、浴温５５℃で１５分間浸漬し、電流密度１Ａ／ｄｍ２で電解めっきを行い、めっき厚３．８μｍのパラジウムめっき被膜Ａを得た。
<Comparative Example 2 Concerning Phosphorus Concentration>
A palladium plating solution 4 containing dichlorotetraamminepalladium (II) at a palladium concentration of 15 g/L and 85 g/L of ammonium chloride as an electrolyte in water was prepared. The phosphorus concentration was measured and found to be 11 mg/L.
A test piece (pure copper plate, thickness 0.3 mm, size 25 mm x 40 mm) was immersed in the palladium plating solution 4 for 15 minutes at a bath temperature of 55 ° C., and electrolytic plating was performed at a current density of 1 A / dm 2 to obtain a plating thickness of 3. A palladium plating film A of 0.8 μm was obtained.
＜リン濃度に関する実施例３～４＞
パラジウムめっき液４に対し、リンを除去する処理、具体的には活性炭による吸着処理を行い、リン濃度が１０ｍｇ／Ｌであるパラジウムめっき液５（実施例３）、リン濃度が４ｍｇ／Ｌであるパラジウムめっき液６（実施例４）を調製した。これらのパラジウムめっき液についても同様に、試験片に対して電解めっきを行い、それぞれめっき厚３．７μｍのパラジウムめっき被膜Ｂ、Ｃを得た。
得られたパラジウムめっき被膜を観察したところ、パラジウムめっき液のリン濃度が１０ｍｇ／Ｌを超えるパラジウムめっき被膜Ａは、クラックが生じていた。一方で、パラジウムめっき液のリン濃度が１０ｍｇ／Ｌ以下であるパラジウムめっき被膜Ｂ及びＣは、クラックの発生が見られなかった。
<Examples 3 to 4 regarding phosphorus concentration>
The palladium plating solution 4 was subjected to a treatment to remove phosphorus, specifically an adsorption treatment with activated carbon, and a palladium plating solution 5 (Example 3) having a phosphorus concentration of 10 mg/L and a phosphorus concentration of 4 mg/L. A palladium plating solution 6 (Example 4) was prepared. Using these palladium plating solutions, electroplating was performed on the test pieces in the same manner to obtain palladium plating films B and C each having a plating thickness of 3.7 μm.
When the obtained palladium plating films were observed, cracks were found in the palladium plating film A in which the phosphorus concentration of the palladium plating solution exceeded 10 mg/L. On the other hand, no cracks were observed in the palladium plating films B and C, in which the phosphorus concentration of the palladium plating solution was 10 mg/L or less.
Claims (4)
パラジウムめっき液中のリン濃度が１０ｍｇ／Ｌ以下である、パラジウムめっき液。 A palladium plating solution containing a soluble palladium salt, an electrolyte and water,
A palladium plating solution having a phosphorus concentration of 10 mg/L or less.
パラジウムめっき補充液中のリン濃度が１０ｍｇ／Ｌ以下である、パラジウムめっき補充液。 A palladium plating replenisher comprising a soluble palladium salt, an electrolyte and water,
A palladium plating replenisher having a phosphorus concentration of 10 mg/L or less.
4. The palladium plating replenisher solution according to claim 3, wherein said soluble palladium salt is tetraamminepalladium chloride.
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| JP2015175049A (en) * | 2014-03-17 | 2015-10-05 | 松田産業株式会社 | Palladium plating solution, palladium plating method, palladium plating product, sliding contact material, and sliding contact |
| CN105401182A (en) * | 2015-10-14 | 2016-03-16 | 佛山科学技术学院 | Plating solution formula and electroplating method for electroplating thick palladium on stainless steel |
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| JPS58130297A (en) * | 1983-01-21 | 1983-08-03 | Nippon Mining Co Ltd | Semi-gloss palladium plating bath |
| JPS59211588A (en) * | 1983-05-13 | 1984-11-30 | ヴエ−・ツエ−・ヘレウス・ゲゼルシヤフト・ミツト・ベシユレンクタ−・ハフツング | Palladium coating electroplating aqueous bath and process |
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| JP2001335986A (en) * | 2000-05-30 | 2001-12-07 | Matsuda Sangyo Co Ltd | Palladium plating liquid |
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| JP2015175049A (en) * | 2014-03-17 | 2015-10-05 | 松田産業株式会社 | Palladium plating solution, palladium plating method, palladium plating product, sliding contact material, and sliding contact |
| CN105401182A (en) * | 2015-10-14 | 2016-03-16 | 佛山科学技术学院 | Plating solution formula and electroplating method for electroplating thick palladium on stainless steel |
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