JP4230813B2 - Gold plating solution - Google Patents
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- JP4230813B2 JP4230813B2 JP2003124443A JP2003124443A JP4230813B2 JP 4230813 B2 JP4230813 B2 JP 4230813B2 JP 2003124443 A JP2003124443 A JP 2003124443A JP 2003124443 A JP2003124443 A JP 2003124443A JP 4230813 B2 JP4230813 B2 JP 4230813B2
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- gold plating
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Description
【０００１】
【発明の属する技術分野】
本発明は、置換型の金めっき液に関し、更に詳しくは電気・電子部品の銅材料部分に直接金めっきをするために用いられる金めっき液に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
金めっき液は、プリント回路基板をはじめとする電気・電子部品を金めっきするために広く使用されている。例えば、電気的特性および耐食性の向上を図るために、ニッケル上に置換型の金めっきや自己触媒型の金めっきが施されている。近年コスト削減等を目的として、金めっき液を用いて銅材料上に直接金めっきを行う試みがなされている。
【０００３】
また銅はマイグレーションを起こしやすいことからその防止を目的として、銅材の表面にニッケルめっきのバリア層を形成し、その上に金めっき層を形成することが行われている。しかし銅材上に直接置換金めっきを行う場合、金とニッケルの置換めっき反応が不均一に生起し、局部的な腐食反応によって密着性及び耐食性が低い金めっき物が形成されてしまう。これらの問題点を解決するために、例えば置換金めっきの前に銅材を表面調整溶液と接触させ、水洗を行うことなく置換金めっきを行うことで、はんだ接合性に優れた金めっき層を形成することが提案されている（特許文献１参照）。しかし、工程の増加に伴うコストの増加の問題があり、また被めっき物の形状によっては金めっき工程の適用が困難になる場合がある。
【０００４】
【特許文献１】
特開２００２−２２０６７６号公報
【０００５】
従って本発明は、密着性や耐食性が高く、高信頼性を有する金めっき物を得ることができる金めっき液を提供することを目的とする。
【０００６】
【課題を解決するための手段】
前記目的を達成すべく本発明者らは鋭意検討した結果、銅材料上に置換型の金めっきを直接行う際に、銅材料からの銅の溶出や銅材料表面の酸化が、金の析出を不安定性にし、また密着性不良の原因となることを知見した。
【０００７】
本発明は前記知見に基づきなされたもので、コハク酸、フタル酸、フマル酸、マレイン酸及びマロン酸からなる群より選ばれた１種又は２種以上の有機酸又はその塩類、エリソルビン酸又はその塩類、シアン化カリウム、及び金イオン源を含有し、銅材料からなる被めっき物の表面に無電解金めっき層を直接形成するために用いられることを特徴とする置換型金めっき液を提供することにより前記目的を達成したものである。
【０００８】
【発明の実施の形態】
以下本発明を、その好ましい実施形態に基づき説明する。本発明の金めっき液は、銅材料からなる被めっき物の表面に置換型の無電解金めっき層を直接形成するために用いられるものである。金めっき液は、（１）コハク酸、フタル酸、フマル酸、マレイン酸及びマロン酸又はその塩類からなる群より選ばれた１種又は２種以上の有機酸又はその塩類（以下これらを総称して有機酸類という）、（２）エリソルビン酸類又はその塩類（以下これらを総称してエルソルビン酸類という）、（３）シアン化カリウム、及び（４）金イオン源を必須成分として含有している水溶液である。
【０００９】
本発明の金めっき液における前記（１）の成分である有機酸類においては、それらのうちの一種又は二種以上を組み合わせて用いることができる。これら有機酸類の塩としてはナトリウム塩、カリウム塩及びアンモニウム塩等が挙げられる。
【００１０】
有機酸類の濃度は、１０〜５０ｇ／リットル、特に１５〜３５ｇ／リットルであることが好ましい。この濃度範囲であれば、経済的に銅の溶解を十分に抑制でき、銅材料からなる被めっき物表面の酸化を効果的に防止できる。また、銅からなる被めっき物の表面全域を金めっき層で均一に被覆することができる。
【００１１】
前記（２）の成分においてエリソルビン酸は、Ｌ−アルコルビン酸の立体異性体であり、イソアルコルビン酸やアラボアスコルビン酸などの別名で呼ばれることもある。本発明者らの検討の結果、無電解めっきにおいてしばしば用いられているＬ−アルコルビン酸よりもエリソルビン酸を、上記した特定の有機酸類と共にめっき液に配合すると、得られるめっき液はこれを長期間繰り返してめっき操作に供しても金の沈殿が起こらない安定なものになることが判明した。この理由は、エリソルビン酸とＬ−アルコルビン酸とで還元力が相違することに起因していると考えられる。エリソルビン酸類の濃度は、０．１〜５ｇ／リットル、特に１〜３ｇ／リットルであることが好ましい。この濃度範囲であれば、経済的に銅の溶解を十分に抑制でき、銅材料からなる被めっき物表面の酸化を効果的に防止できる。また、銅材料からなる被めっき物の表面全域を金めっき層で一層均一に被覆することができる。エリソルビン酸の塩としてはナトリウム塩等が挙げられる。
【００１２】
前記（１）及び（２）の成分に加えて、前記（３）の成分であるシアン化カリウムを併用すると、溶出した銅イオンがマスクされて、金をより均一に析出させることができ、銅材料からなる被めっき物表面全域を金めっき層でより均一に被覆できることが判明した。シアン化カリウムの濃度は、０．１〜３ｇ／リットル、特に０．５〜１．５ｇ／リットルとすることが好ましい。
【００１３】
前記（４）の成分である金イオン源としては、シアン化金カリウム、シアン化金ナトリウム、塩化金酸、亜硫酸金、チオ硫酸金などが用いられ、特にシアン化金カリウムを用いることが好ましい。金めっき中における金イオン源の濃度は０．５〜３ｇ／リットル、特に０．５〜１．５ｇ／リットルであることが、経済性よく十分なめっき速度が得られる点から好ましい。
【００１４】
金めっき液には、錯化剤が含有されていることが好ましい。錯化剤を含有させておくことで、銅材料からなる被めっき物の表面に形成される酸化膜を除去でき、金めっきを均一に行うことができる。錯化剤としては、例えばクエン酸、ヒドロキシ酢酸、酒石酸、リンゴ酸、乳酸、グルコン酸またはそのアルカリ金属塩やアンモニウム塩などの各種カルボン酸又はその塩、グリシンなどのアミノ酸、エチレンジアミン、アルキルアミンなどのアミン類、アンモニウム塩、ＥＤＴＡ、ピロリン酸又はその塩など、金イオンや溶出する銅イオンと錯形成可能な化合物が使用される。これらの錯化剤は１種又は２種類以上を用いることができる。
【００１５】
金めっき液中に含まれる錯化剤の濃度は５〜７０ｇ／リットル、特に１０〜５０ｇ／リットルであることが、銅表面に形成される酸化膜を除去し、金を均一に析出させる点から好ましい。
【００１６】
金めっき液には、前述した各種の成分に加えて非イオン系界面活性剤等を含有させてもよい。
【００１７】
次に、本発明の金めっき液を用いた金めっき物の製造方法について説明する。先ず金めっき液のｐＨを所定の範囲に調整する。ｐＨが低すぎると銅材料から銅イオンが溶出しやすくなり、ｐＨが高すぎると金の析出が粗くなる。これらの観点から、金めっき液のｐＨは３．５〜７．０、特に４．０〜６．０であることが好ましい。ｐＨの調整には塩酸や水酸化カリウムが用いられる。次いで、予め所定の前処理が施された被めっき物を金めっき液中に浸漬し、金イオンを置換析出させる。これによって被めっき物の表面に金からなる無電解めっき層を直接形成する。金めっき液の温度は５０〜９５℃程度、特に６５〜９０℃程度であることが、金の均一析出の点から好ましい。めっき時間はおおよそ５〜１５分とすることができる。このようにして得られた金めっき層は良好な金色の光沢を呈しており、被めっき物である銅材料と良好に密着している。更に、銅材料の表面全域を均一に被覆している。
【００１８】
本発明の金めっき液は、後述する実施例から明らかなように、長期間繰り返してめっき操作に供しても金の沈殿が観察されない安定したものである。この理由は、本発明の金めっき液の作用、特にエリソルビン酸類を配合したことによって銅の酸化及び溶出が抑制されるためと考えられる。
【００１９】
本発明の金めっき液を用いて得ためっき物は、銅材料の表面全域が金めっき層で均一に被覆されており、銅が実質的に表面に露出していないので、耐食性が高く高信頼性を有するものである。従ってこのめっき物は、非常に優れた信頼性が要求される用途に特に適している。しかもこのめっき物は低コストであるという利点もある。
【００２０】
【実施例】
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲はかかる実施例に制限されるものではない。
【００２１】
〔実施例１〕
＜金めっき液の組成＞
・コハク酸 ３０．０ ｇ／ｌ
・エリソルビン酸ナトリウム ３．０ ｇ／ｌ
・シアン化カリウム ０．５ｇ／ｌ
・シアン化金カリウム １．０ ｇ／ｌ
・水 残部
この金めっき液を塩酸および水酸化カリウムによってｐＨ６．０に調整した。予めエッチングおよび硫酸活性などの慣用の前処理を施したプリント回路基板を、この金めっき液中に１０分間浸漬した。金めっき液の温度は８０℃であった。これによってプリント回路基板の銅配線および電極上に置換型の金めっきを行なった。
【００２２】
〔実施例２〕
＜金めっき液の組成＞
・フタル酸 ４０．０ ｇ／１
・エリソルビン酸ナトリウム １．０ ｇ／ｌ
・シアン化カリウム ０．５ｇ／１
・シアン化金カリウム １．０ ｇ／１
・水 残部
この金めっき液を用いて実施例１と同様にして、プリント回路基板の銅配線および電極上に置換型の金めっきを行った。
【００２３】
〔実施例３〕
＜金めっき液の組成＞
・フマル酸 ３０．０ ｇ／１
・エリソルビン酸ナトリウム ３．０ ｇ／１
・シアン化カリウム ０．５ ｇ／１
・シアン化金カリウム １．０ ｇ／１
・水 残部
この金めっき液を用いて実施例１と同様にして、プリント回路基板の銅配線および電極上に置換型の金めっきを行った。
【００２４】
〔実施例４〕
＜金めっき液の組成＞
・マレイン酸 ３０．０ ｇ／１
・エリソルビン酸ナトリウム ３．０ ｇ／１
・シアン化カリウム ０．５ ｇ／１
・シアン化金カリウム １．０ ｇ／１
・水 残部
この金めっき液を用いて実施例１と同様にして、プリント回路基板の銅配線および電極上に置換型の金めっきを行った。
【００２５】
〔実施例５〕
＜金めっき液の組成＞
・マロン酸 ２６．０ ｇ／１
・エリソルビン酸ナトリウム ３．０ ｇ／１
・シアン化カリウム ０．５ ｇ／１
・シアン化金カリウム １．０ ｇ／１
・水 残部
この金めっき液を用いて実施例１と同様にして、プリント回路基板の銅配線および電極上に置換型の金めっきを行った。
【００２６】
〔比較例１〕
＜金めっき液の組成＞
・クエン酸 ４０．０ ｇ／１
・エリソルビン酸ナトリウム ３．０ ｇ／１
この金めっき液を用いて実施例１と同様にして、プリント回路基板の銅配線および電極上に置換型の金めっきを行った。
【００２７】
〔比較例２〕
＜金めっき液の組成＞
・コハク酸 ３０．０ ｇ／１
・シアン化カリウム ０．５ｇ／ｌ
・シアン化金カリウム １．０ｇ／ｌ
・水 残部
この金めっき液を用いて実施例１と同様にして、プリント回路基板の銅配線および電極上に置換型の金めっきを行った。
【００２８】
〔比較例３〕
＜金めっき液の組成＞
・クエン酸 ２０．０ ｇ／１
・Ｌ−アスコルビン酸ナトリウム ３．０ｇ／ｌ
・ＥＤＴＡカリウム １０．０ｇ／ｌ
・シアン化金カリウム ２．０ｇ／ｌ
・水 残部
この金めっき液を用いて実施例１と同様にして、プリント回路基板の銅配線および電極上に置換型の金めっきを行った。
【００２９】
〔性能評価〕
実施例１〜５並びに比較例１〜３で得られた金めっき物について、金めっき層の析出速度及び析出速度のバラツキを以下の方法で求めた。また金めっき層の外観を目視観察した。更に金めっき層の密着性を以下の方法で評価した。結果を以下の表１に示す。
【００３０】
〔析出速度〕
金めっきした基板５枚を準備し、各基板の定められた５箇所のめっき膜厚を蛍光Ｘ線微小膜厚測定装置（セイコー電子工業社製品）により測定し、測定された膜厚の平均値から１０分当たりの析出速度を計算した。
【００３１】
〔析出速度のバラツキ〕
めっき膜厚の測定結果からめっき膜厚の最大値及び最小値を調べ、最大膜厚及び最小膜厚から１０分当たりの析出速度を計算し、その範囲を析出速度のばらつきとした。
【００３２】
〔密着性〕
ＪＩＳ Ｈ８５０４のＺ１５２２に準じて金めっき層の密着性を評価した。
【００３３】
【表１】
表１に示す結果から明らかなように、実施例１〜５で得られためっき物は、比較例１で得られためっき物に比べて金めっき層の析出速度のバラツキが少ないことが判る。また金めっき層は金色光沢を呈し、密着性に優れたものであることが判る。
【００３５】
また、実施例１〜５で得られためっき物は、金めっき層の析出速度、外観および密着性に関して比較例２及び３で得られためっき物と同等であることが判る。しかし、実施例１〜５並びに比較例２及び３の条件でめっきを継続すると、実施例１〜５の金めっき液では３０日経過後も金の沈殿は殆ど認められなかったのに対し、比較例２及び３の金めっき液では３０日経過後に金の沈殿が認められることが判る。
【００３６】
【発明の効果】
以上詳述した通り本発明の金めっき液を用いて置換型の金めっきを行うと、銅の酸化及び溶出が抑制されることに起因して、金の析出が安定する。その結果、形成された金めっき層は良好な金色の光沢を呈し、密着性に優れたものとなる。また本発明のめっき液は、長期間繰り返してめっき操作に供しても金の沈殿が観察されない安定したものである。更に、本発明の金めっき液を用いて得られた金めっき物は電気抵抗が低く、耐食性があり、高温高湿環境下に長時間保存しても抵抗値の上昇が少ない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a substitution type gold plating solution, and more particularly to a gold plating solution used for direct gold plating on a copper material portion of an electric / electronic component.
[0002]
[Prior art and problems to be solved by the invention]
Gold plating solutions are widely used for gold plating of electric and electronic parts such as printed circuit boards. For example, in order to improve electrical characteristics and corrosion resistance, substitutional gold plating or autocatalytic gold plating is performed on nickel. In recent years, for the purpose of cost reduction and the like, attempts have been made to perform gold plating directly on a copper material using a gold plating solution.
[0003]
Further, since copper easily causes migration, a nickel plating barrier layer is formed on the surface of a copper material and a gold plating layer is formed thereon for the purpose of preventing the migration. However, when displacement gold plating is directly performed on a copper material, the displacement plating reaction of gold and nickel occurs non-uniformly, and a gold plating product with low adhesion and corrosion resistance is formed by a local corrosion reaction. In order to solve these problems, for example, by bringing a copper material into contact with the surface conditioning solution before substitution gold plating and performing substitution gold plating without washing with water, a gold plating layer having excellent solderability can be obtained. It has been proposed to form (see Patent Document 1). However, there is a problem of an increase in cost due to an increase in the number of processes, and application of the gold plating process may be difficult depending on the shape of the object to be plated.
[0004]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2002-220676
Therefore, an object of the present invention is to provide a gold plating solution that can provide a highly reliable gold plating product with high adhesion and corrosion resistance.
[0006]
[Means for Solving the Problems]
As a result of diligent investigations by the present inventors to achieve the above object, when direct substitutional gold plating is performed on a copper material, the elution of copper from the copper material and the oxidation of the surface of the copper material cause the deposition of gold. It has been found that it causes instability and causes poor adhesion.
[0007]
The present invention has been made on the basis of the above findings, and one or more organic acids selected from the group consisting of succinic acid, phthalic acid, fumaric acid, maleic acid and malonic acid or salts thereof, erythorbic acid or the like By providing a substitution type gold plating solution containing a salt, potassium cyanide, and a gold ion source and used for directly forming an electroless gold plating layer on the surface of an object to be plated made of a copper material The object has been achieved.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described based on preferred embodiments thereof. The gold plating solution of the present invention is used for directly forming a substitutional electroless gold plating layer on the surface of an object to be plated made of a copper material. The gold plating solution is composed of (1) one or more organic acids selected from the group consisting of succinic acid, phthalic acid, fumaric acid, maleic acid and malonic acid or salts thereof, or salts thereof (hereinafter collectively referred to as (2) erythorbic acids or salts thereof (hereinafter collectively referred to as ersorbic acids), (3) potassium cyanide, and (4) an aqueous solution containing a gold ion source as essential components.
[0009]
In the organic acid which is the component (1) in the gold plating solution of the present invention, one or two or more of them can be used in combination. Examples of salts of these organic acids include sodium salts, potassium salts and ammonium salts.
[0010]
The concentration of the organic acids is preferably 10 to 50 g / liter, more preferably 15 to 35 g / liter. If it is this density | concentration range, melt | dissolution of copper can fully be suppressed economically, and the oxidation of the to-be-plated object surface which consists of copper materials can be prevented effectively. Further, the entire surface of the object to be plated made of copper can be uniformly coated with the gold plating layer.
[0011]
In the component (2), erythorbic acid is a stereoisomer of L-alcorbic acid, and is sometimes called by another name such as isoalcorbic acid or araboascorbic acid. As a result of the study by the present inventors, when erythorbic acid is blended in the plating solution together with the above-mentioned specific organic acids rather than L-alcorbic acid often used in electroless plating, the resulting plating solution is used for a long time. It has been found that even if it is repeatedly subjected to a plating operation, it is stable without gold precipitation. This reason is considered to be due to the difference in reducing power between erythorbic acid and L-alcorbic acid. The concentration of erythorbic acids is preferably 0.1 to 5 g / liter, particularly 1 to 3 g / liter. If it is this density | concentration range, melt | dissolution of copper can fully be suppressed economically, and the oxidation of the to-be-plated object surface which consists of copper materials can be prevented effectively. Further, the entire surface of the object to be plated made of a copper material can be coated more uniformly with the gold plating layer. Examples of the salt of erythorbic acid include sodium salt.
[0012]
In addition to the components (1) and (2), when the potassium cyanide component (3) is used in combination, the eluted copper ions are masked and gold can be deposited more uniformly. It was found that the entire surface of the object to be plated can be more uniformly coated with the gold plating layer. The concentration of potassium cyanide is preferably 0.1 to 3 g / liter, particularly 0.5 to 1.5 g / liter.
[0013]
As the gold ion source that is the component (4), potassium gold cyanide, sodium gold cyanide, chloroauric acid, gold sulfite, gold thiosulfate and the like are used, and it is particularly preferable to use potassium gold cyanide. The concentration of the gold ion source in the gold plating is preferably 0.5 to 3 g / liter, particularly 0.5 to 1.5 g / liter from the viewpoint of obtaining a sufficient plating rate with good economic efficiency.
[0014]
The gold plating solution preferably contains a complexing agent. By containing the complexing agent, the oxide film formed on the surface of the object to be plated made of a copper material can be removed, and gold plating can be performed uniformly. Examples of complexing agents include citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, gluconic acid or various carboxylic acids such as alkali metal salts and ammonium salts thereof or salts thereof, amino acids such as glycine, ethylenediamine, alkylamines, and the like. Compounds capable of complexing with gold ions or eluting copper ions such as amines, ammonium salts, EDTA, pyrophosphoric acid or salts thereof are used. These complexing agents can be used alone or in combination of two or more.
[0015]
The concentration of the complexing agent contained in the gold plating solution is 5 to 70 g / liter, particularly 10 to 50 g / liter from the point of removing the oxide film formed on the copper surface and depositing gold uniformly. preferable.
[0016]
The gold plating solution may contain a nonionic surfactant in addition to the various components described above.
[0017]
Next, a method for producing a gold plating product using the gold plating solution of the present invention will be described. First, the pH of the gold plating solution is adjusted to a predetermined range. If the pH is too low, copper ions are likely to elute from the copper material, and if the pH is too high, gold deposition becomes rough. From these viewpoints, the gold plating solution preferably has a pH of 3.5 to 7.0, particularly 4.0 to 6.0. Hydrochloric acid or potassium hydroxide is used for pH adjustment. Next, the object to be plated that has been subjected to a predetermined pretreatment is dipped in a gold plating solution, and gold ions are substituted and deposited. As a result, an electroless plating layer made of gold is directly formed on the surface of the object to be plated. The temperature of the gold plating solution is preferably about 50 to 95 ° C., particularly about 65 to 90 ° C. from the viewpoint of uniform gold precipitation. The plating time can be approximately 5 to 15 minutes. The gold plating layer thus obtained has a good golden luster and is in good contact with the copper material that is the object to be plated. Further, the entire surface of the copper material is uniformly coated.
[0018]
The gold plating solution of the present invention is a stable one in which no precipitation of gold is observed even when it is repeatedly subjected to a plating operation for a long period of time, as will be apparent from examples described later. The reason for this is considered to be because the oxidation and elution of copper are suppressed by the action of the gold plating solution of the present invention, particularly by the incorporation of erythorbic acids.
[0019]
The plated product obtained using the gold plating solution of the present invention is uniformly coated with a gold plating layer on the entire surface of the copper material, and copper is not substantially exposed on the surface, so that the corrosion resistance is high and the reliability is high. It has sex. Therefore, this plated product is particularly suitable for applications that require extremely excellent reliability. Moreover, this plated product has an advantage of low cost.
[0020]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples.
[0021]
[Example 1]
<Composition of gold plating solution>
・ Succinic acid 30.0 g / l
・ Sodium erythorbate 3.0 g / l
・ Potassium cyanide 0.5g / l
-Potassium cyanide 1.0 g / l
-Water remainder The gold plating solution was adjusted to pH 6.0 with hydrochloric acid and potassium hydroxide. A printed circuit board which had been subjected to conventional pretreatments such as etching and sulfuric acid activity in advance was immersed in this gold plating solution for 10 minutes. The temperature of the gold plating solution was 80 ° C. As a result, substitutional gold plating was performed on the copper wiring and electrodes of the printed circuit board.
[0022]
[Example 2]
<Composition of gold plating solution>
・ Phthalic acid 40.0 g / 1
-Sodium erythorbate 1.0 g / l
・ Potassium cyanide 0.5g / 1
-Potassium gold cyanide 1.0 g / 1
-Remaining water Using this gold plating solution, in the same manner as in Example 1, substitutional gold plating was performed on the copper wiring and electrodes of the printed circuit board.
[0023]
[ Example 3 ]
<Composition of gold plating solution>
・ Fumaric acid 30.0 g / 1
・ Sodium erythorbate 3.0 g / 1
・ Potassium cyanide 0.5 g / 1
-Potassium gold cyanide 1.0 g / 1
-Water remainder Using this gold plating solution, substitution type gold plating was performed on the copper wiring and electrodes of the printed circuit board in the same manner as in Example 1.
[0024]
Example 4
<Composition of gold plating solution>
・ Maleic acid 30.0 g / 1
・ Sodium erythorbate 3.0 g / 1
・ Potassium cyanide 0.5 g / 1
-Potassium gold cyanide 1.0 g / 1
-Remaining water Using this gold plating solution, in the same manner as in Example 1, substitutional gold plating was performed on the copper wiring and electrodes of the printed circuit board.
[0025]
Example 5
<Composition of gold plating solution>
・ Malonic acid 26.0 g / 1
・ Sodium erythorbate 3.0 g / 1
・ Potassium cyanide 0.5 g / 1
-Potassium gold cyanide 1.0 g / 1
-Remaining water Using this gold plating solution, in the same manner as in Example 1, substitutional gold plating was performed on the copper wiring and electrodes of the printed circuit board.
[0026]
[Comparative Example 1]
<Composition of gold plating solution>
・ Citric acid 40.0 g / 1
・ Sodium erythorbate 3.0 g / 1
Using this gold plating solution, substitution-type gold plating was performed on the copper wiring and electrodes of the printed circuit board in the same manner as in Example 1.
[0027]
[Comparative Example 2]
<Composition of gold plating solution>
・ Succinic acid 30.0 g / 1
・ Potassium cyanide 0.5g / l
-Potassium cyanide 1.0 g / l
-Remaining water Using this gold plating solution, in the same manner as in Example 1, substitutional gold plating was performed on the copper wiring and electrodes of the printed circuit board.
[0028]
[Comparative Example 3]
<Composition of gold plating solution>
Citric acid 20.0 g / 1
・ Sodium L-ascorbate 3.0 g / l
・ EDTA potassium 10.0g / l
-Potassium cyanide 2.0 g / l
-Remaining water Using this gold plating solution, in the same manner as in Example 1, substitutional gold plating was performed on the copper wiring and electrodes of the printed circuit board.
[0029]
[Performance evaluation]
About the gold plating products obtained in Examples 1 to 5 and Comparative Examples 1 to 3, the deposition rate of the gold plating layer and the variation in the deposition rate were determined by the following method. The appearance of the gold plating layer was visually observed. Furthermore, the adhesion of the gold plating layer was evaluated by the following method. The results are shown in Table 1 below.
[0030]
[Deposition rate]
Prepare five gold-plated substrates, measure the plating film thickness at five locations on each substrate with a fluorescent X-ray micro-film thickness measuring device (Seiko Electronics Co., Ltd. product), and measure the average thickness From this, the precipitation rate per 10 minutes was calculated.
[0031]
[Variation in deposition rate]
The maximum value and the minimum value of the plating film thickness were examined from the measurement result of the plating film thickness, the deposition rate per 10 minutes was calculated from the maximum film thickness and the minimum film thickness, and the range was regarded as the dispersion of the deposition rate.
[0032]
[Adhesion]
The adhesion of the gold plating layer was evaluated according to JIS H8504 Z1522.
[0033]
[Table 1]
As is clear from the results shown in Table 1, it can be seen that the plated products obtained in Examples 1 to 5 have less variation in the deposition rate of the gold plating layer than the plated product obtained in Comparative Example 1. Moreover, it turns out that a gold plating layer exhibits golden luster and is excellent in adhesiveness.
[0035]
Moreover, it turns out that the plated products obtained in Examples 1 to 5 are equivalent to the plated products obtained in Comparative Examples 2 and 3 with respect to the deposition rate, appearance, and adhesion of the gold plating layer. However, when plating was continued under the conditions of Examples 1 to 5 and Comparative Examples 2 and 3, in the gold plating solutions of Examples 1 to 5, almost no gold precipitation was observed after 30 days, whereas Comparative Example It can be seen that in the gold plating solutions 2 and 3, gold precipitation is observed after 30 days.
[0036]
【The invention's effect】
As described above, when substitutional gold plating is performed using the gold plating solution of the present invention, gold deposition is stabilized due to suppression of copper oxidation and elution. As a result, the formed gold plating layer exhibits a good golden luster and has excellent adhesion. In addition, the plating solution of the present invention is stable so that no gold precipitate is observed even when it is repeatedly subjected to a plating operation for a long period of time. Furthermore, the gold-plated product obtained using the gold plating solution of the present invention has low electrical resistance, corrosion resistance, and little increase in resistance value even when stored for a long time in a high-temperature and high-humidity environment.
Claims (1)
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| JP2003124443A JP4230813B2 (en) | 2003-04-28 | 2003-04-28 | Gold plating solution |
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| JP2003124443A JP4230813B2 (en) | 2003-04-28 | 2003-04-28 | Gold plating solution |
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| JP4230813B2 true JP4230813B2 (en) | 2009-02-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7962054B2 (en) | 2006-09-22 | 2011-06-14 | Ricoh Company, Limited | Image forming apparatus having a function of predicting device deterioration based on a plurality of types of operation control information |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5116956B2 (en) * | 2005-07-14 | 2013-01-09 | 関東化学株式会社 | Electroless hard gold plating solution |
| JP2009102681A (en) * | 2007-10-22 | 2009-05-14 | Ishihara Chem Co Ltd | Displacement gold-plating bath and gold-plating method thereof |
| JP5686939B2 (en) * | 2007-12-25 | 2015-03-18 | メタローテクノロジーズジャパン株式会社 | Replacement gold plating solution for copper substrate and gold plating method using the same |
| JP2012247372A (en) | 2011-05-30 | 2012-12-13 | Nippon Mektron Ltd | Pressure sensor, manufacturing method thereof, and pressure detection module |
| CN102242336B (en) * | 2011-06-24 | 2013-02-13 | 清华大学 | Film preparation method for reducing stress of hard film |
| KR101996915B1 (en) | 2018-09-20 | 2019-07-05 | (주)엠케이켐앤텍 | Substitution type electroless gold plating bath containing purine or pyrimidine-based compound having carbonyl oxygen and substitution type electroless gold plating using the same |
-
2003
- 2003-04-28 JP JP2003124443A patent/JP4230813B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7962054B2 (en) | 2006-09-22 | 2011-06-14 | Ricoh Company, Limited | Image forming apparatus having a function of predicting device deterioration based on a plurality of types of operation control information |
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