JP2004076026A - Electrolytic hard gold-plating liquid and plating method using it - Google Patents
Electrolytic hard gold-plating liquid and plating method using it Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、電子部品等のめっきに用いられる電解硬質金めっき液及びめっき方法に関する。
【０００２】
【従来の技術】
金めっきは、その優れた電気的特性と耐食性から電子、電気部品等の工業分野において広く利用されている。特に硬質金めっきは、高硬度、低接触抵抗であって耐摩耗性が優れているために、コネクターなどの差込部材、又はスイッチなどの接点材料に使用されている。
【０００３】
通常、コネクター等の電子部品の材質は主に銅又は銅合金が使用される。銅や銅合金の電子部品に金めっきを行う場合には、銅のバリア金属としてまずニッケルめっきを行い、その上に金めっきを行っている。
【０００４】
電子部品への硬質金めっき方法としては、通常、連続リールめっき、又はフープめっき方法が使用されている。これらの方法による析出速度は、一般的に１μｍめっきするのに１０秒前後である。
【０００５】
近年、電子機器の生産増大に伴い、電子部品の生産性向上が求められており、より析出速度が速い金めっきが望まれている。
【０００６】
また、コネクターには、硬質金めっきと半田めっきが施される仕様があり、この場合には硬質金めっきを行った後２３０℃前後でリフロー処理が入る。このために、コネクターへの金めっきは、金めっき後にリフロー処理等の加熱処理を行ってもめっき皮膜の接触抵抗が低下しにくくめっき皮膜が耐熱安定性を有する金めっきを行うことがますます重要になっている。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、析出速度が速く生産性に優れ、リフロー処理等の加熱処理を行ってもめっき皮膜の接触抵抗が低下しない金めっき皮膜を形成することができる電解硬質金めっき液及びめっき方法を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者は上記課題を解決するために種々検討した結果、硬質金めっき液中に脂肪族アルコールを添加することにより、めっきが可能な電流密度範囲の最大値が高くなり、金めっき皮膜の析出速度が向上し、金めっき後に加熱処理を行っても接触抵抗が低下せず安定な接触抵抗を示すめっき皮膜が得られることを見出した。
【０００９】
上記課題を解決する本発明は以下に記載するものである。
【００１０】
〔１〕 金イオン源として可溶性金塩又は金錯体を用い、伝導塩として有機酸塩及び／又は無機酸塩と、硬質化剤とを含有する電解硬質金めっき液であって、脂肪族アルコールを含有することを特徴とする電解硬質金めっき液。
【００１１】
〔２〕 脂肪族アルコールが炭素数８以下の直鎖又は分岐鎖のアルキル基を有する飽和脂肪族アルコールである〔１〕に記載の電解硬質金めっき液。
【００１２】
〔３〕 硬質化剤がコバルト及び／又はニッケルの可溶性塩である〔１〕に記載の電解硬質金めっき液。
【００１３】
〔４〕 〔１〕に記載の電解硬質金めっき液を用いて電流密度０．１〜６０Ａ／ｄｍ２でめっきする電解硬質金めっき方法。
【００１４】
【発明の実施の形態】
本発明で使用することができる脂肪族アルコールは公知のものであれば特に制限されないが、炭素数が８以下の直鎖又は分岐鎖のアルキル基を有する飽和脂肪族アルコールが好ましい。かかるアルコールは工業的にめっきを行うに際して水溶液に容易に溶解し均一に混合することができる。特に、飽和脂肪族アルコールのアルキル基の炭素数は４〜８がより好ましい。
【００１５】
本発明において好ましく用いることができる飽和脂肪族アルコールとしては、ｎ−ブチルアルコール、イソブチルアルコール、イソアミルアルコール、１−ヘキシルアルコール、１−へプタノ−ル、２−メチル−３−ヘキサノール、５−メチル−１−ヘキサノール、２−エチル−１−ヘキサノール等を挙げることができる。
【００１６】
これらの脂肪族アルコールのめっき液に対する添加量は、めっき液に対する溶解度等により異なるが、下記の範囲内であれば微量でも十分な効果が得られ、好ましく使用することができる。またそれぞれの脂肪族アルコールの溶解度の範囲内で多量に添加しても本発明の効果が損なわれることはない。脂肪族アルコールの添加量は０．０５〜１００ｍｌ／ｌの範囲が好ましく、０．１〜１０ｍｌ／ｌの範囲がより好ましい。
【００１７】
脂肪族アルコールを金めっき液に添加すると、水素発生電位をより卑にし、電流効率の低下をまねく水素発生を抑制するとともに、金皮膜の結晶成長をコントロールし、より結晶粒が細かい緻密な金めっき皮膜を形成する。このため、金めっき皮膜の耐熱性が向上し、加熱処理後の接触抵抗が低下しない。
【００１８】
本発明の金めっき液の金イオン供給源としては、可溶性の金化合物であれば何の制限もなく使用できる。入手の容易さ、めっき液への溶解性、めっき液中での金イオンの安定性の観点から、シアン化金、シアン化第一金カリウム、亜硫酸金カリウム、チオ硫酸金の金塩から選ばれるものが特に好ましい。
【００１９】
また、使用する金化合物に応じて金と錯イオンを形成する錯化剤を添加して金錯体とし、金イオン供給源としてもよい。錯化剤を添加して金錯体とすることにより、金イオンの安定性を制御することができる。錯化剤は公知のものが使用できるが、エチレンジアミン、ＥＤＴＡ等を挙げることができる。
【００２０】
金塩又は金錯体のめっき液への添加量は、金イオンとして１〜２０ｇ／ｌが好ましい。
【００２１】
伝導塩として添加する有機酸塩及び／又は無機酸塩は、クエン酸、酒石酸等のカルボン酸等の有機酸；リン酸、亜硫酸等の無機酸のアルカリ金属塩が好ましい。またこれらの２種以上を組み合わせて使用してもよい。
伝導塩の添加量は、５０〜３００ｇ／ｌとすることが好ましい。
【００２２】
また、本発明の金めっき液は、金皮膜の硬質化のために、硬質化剤を含有させる。硬質化剤としては、公知のものを使用できるが、コバルト、ニッケルの可溶性塩を用いることが好ましい。コバルト、ニッケルの可溶性塩としては、硫酸コバルト、硫酸ニッケル、塩化コバルト、塩化ニッケル等を例示できる。これらを硬質化剤として含有する金めっき液は、金めっき皮膜の結晶粒が細かく、結晶成長に伴う転位や原子空隙が生じにくくなり、長期間にわたり、一定の金めっき皮膜の成長を維持することが容易になる。
【００２３】
硬質化剤のめっき液への添加量は、コバルト、ニッケル等の金属イオンとして０．０５〜５ｇ／ｌとすることが好ましい。
【００２４】
さらに、本発明の硬質金めっき液には上記の必須成分に加えてｐＨ緩衝剤を添加することが好ましい。ｐＨ緩衝剤としては、ホウ酸、コハク酸、フタル酸、酒石酸、クエン酸、リン酸、亜硫酸等又はこれらの塩類を挙げることができる。ｐＨ緩衝剤はこれらの２種以上を使用してもよい。ｐＨ緩衝剤を含有させることにより、金めっき液を使用してもｐＨが大きく変動することがなく一定に維持することができ、長期間の使用に際して一層好ましいものとなる。ｐＨ緩衝剤の含有量は常法による。
【００２５】
本発明の硬質電解金めっき液を用いて電解金めっき処理を行う場合、めっき液のｐＨ、液温、電流密度は下記の範囲とすることが好ましい。
金めっき液のｐＨは、緩衝剤と伝導塩の濃度によってｐＨ４．０〜５．０の範囲とするのが好ましい。この範囲であれば析出する金めっきの外観に異常が発生しない。また、ｐＨが４．０未満になると、電流効率の低下が生じやすい。一方、５．０を越えると、許容電流密度範囲が狭くなり、硬質化剤がめっき膜中に取り込まれにくくなり、その結果、めっき皮膜は硬度が低下し、耐摩耗性が低下しやすい。
【００２６】
金めっき液の液温は２０〜８０℃が好ましい。２０℃未満では実質上温度制御が容易でなくめっき処理のばらつきが大きくなるため操業に適さず、８０℃を越えると、操業中のめっき液の蒸発による容量減少が大きくめっき液中の各成分の濃度維持が困難になる。
【００２７】
電解時の電流密度は０．１〜６０Ａ／ｄｍ２が好ましい。上述のめっき液のｐＨ値、液温、金濃度を考慮し、この範囲の電流密度で析出する金めっきの性状が良好な状態となる。
【００２８】
【実施例】
以下、実施例を用いて本発明を更に詳細に説明する。
【００２９】
実施例１〜１２
シアン化金カリウム（金として１５ｇ／ｌ）、クエン酸三カリウム１００ｇ／ｌ、リン酸水素二カリウム３０ｇ／ｌ、硫酸コバルト（コバルトとして０．５ｇ／ｌ）を含む金めっき液に、表１に示す各種の脂肪族アルコールを添加し、ｐＨ４．５に調整した液５００ｍｌを温度６０℃に維持した状態で、直径６ｍｍのノズルから陰極（被めっき物）に向けて、めっき液を約５ｍ／ｍｉｎで吹きつけながらめっきする構造からなる噴流式金めっき装置を用いて、１μｍ厚の金めっきを行い、その際に使用可能な最大電流密度範囲、析出速度を調べた。また、電流密度３０Ａ／ｄｍ２においてめっきした皮膜の接触抵抗値を測定した。
【００３０】
接触抵抗の測定は、白金製プローブを用いた４探針法により行い、ＭＳ−９８０型接触抵抗測定器（ケイエス部品研究所製）にて測定電流１ｍＡ、測定荷重１０ｇの条件で測定した。
【００３１】
その結果、すべての実施例において、電流密度６０Ａ／ｄｍ２までめっき可能であり、皮膜外観は良好で、最高析出速度は、６−７ｓｅｃ／μｍを示した。また、接触抵抗値は耐熱前１５〜１７ｍΩ、２３０℃で３０分間加熱後は２２〜２９ｍΩであり、加熱処理後も安定した接触抵抗値を示した。
【００３２】
比較例１
比較として、シアン化金カリウム（金として１５ｇ／ｌ）、クエン酸三カリウム１００ｇ／ｌ、リン酸水素二カリウム３０ｇ／ｌ、硫酸コバルト（コバルトとして０．５ｇ／ｌ）のみを含む金めっき液５００ｍｌを、水酸化カリウム水溶液でｐＨ４．５に調整した後、温度６０℃に維持した状態で、噴流式金めっき装置を用いて、１μｍ厚の金めっきを行い、その際に使用可能な最大電流密度範囲、析出速度を調べた。また、電流密度３０Ａ／ｄｍ２において得られためっき皮膜の接触抵抗値を測定した。
【００３３】
その結果、良好な皮膜外観が得られる最大の電流密度は３０Ａ／ｄｍ２であり、４０Ａ／ｄｍ２以上ではムラ状の不均一な皮膜外観となった。このめっき液の最高析出速度は、１０ｓｅｃ／μｍを示した。また、このめっき皮膜の接触抵抗値は耐熱前１７ｍΩで実施例と同等だったが、２３０℃で３０分間加熱した後は１１０ｍΩと急激に上昇し、電気特性が劣化することを示した。
【００３４】
脂肪族アルコールを添加した場合（実施例１〜実施例１２）と添加しない場合（比較例１）とを比較すると、使用可能な電流密度範囲、析出速度、加熱処理前後での接触抵抗値の安定性（耐熱性）のいずれにおいても脂肪族アルコールを添加した実施例の方が優れていることが確認された。また、脂肪族アルコールの添加量については、０．１ｍｌ／ｌ、１．０ｍｌ／ｌの両方においてその効果が十分且つ同等に発現し、微量でも顕著な効果があることが判明した。
【００３５】
【表１】
【発明の効果】
本発明の電解硬質金めっき液及びめっき方法によれば、めっき可能な電流密度範囲が広く最大電流密度が高いため、めっき皮膜の析出速度が速く生産性が向上する。さらに、めっき後加熱処理を行っても接触抵抗が低下せず、耐熱安定性が高い金めっき皮膜を形成することができる。
【００３７】
本発明は、特にコネクター、接点材料等の電子、電気機器用部品の表面処理に適したものであるが、これに限られるものではなく装飾などの分野においても有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrolytic hard gold plating solution and a plating method used for plating electronic parts and the like.
[0002]
[Prior art]
Gold plating is widely used in industrial fields such as electronics and electrical components due to its excellent electrical properties and corrosion resistance. In particular, hard gold plating is used for a plug-in member such as a connector or a contact material such as a switch because of its high hardness, low contact resistance, and excellent wear resistance.
[0003]
Usually, copper or a copper alloy is mainly used as a material of an electronic component such as a connector. When gold plating is performed on a copper or copper alloy electronic component, nickel plating is first performed as a copper barrier metal, and then gold plating is performed thereon.
[0004]
As a hard gold plating method for an electronic component, a continuous reel plating method or a hoop plating method is usually used. The deposition rate by these methods is generally around 10 seconds for plating 1 μm.
[0005]
In recent years, with the increase in production of electronic devices, there has been a demand for an improvement in the productivity of electronic components, and gold plating with a higher deposition rate has been desired.
[0006]
Further, the connector has a specification in which hard gold plating and solder plating are applied. In this case, reflow treatment is performed at about 230 ° C. after hard gold plating is performed. For this reason, it is increasingly important that the gold plating on the connector does not reduce the contact resistance of the plating film even if heat treatment such as reflow treatment is performed after the gold plating, and the plating film has heat resistance stability. It has become.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide an electrolytic hard gold plating solution and a plating method capable of forming a gold plating film having a high deposition rate and excellent productivity, and having a reduced contact resistance of the plating film even when subjected to a heat treatment such as a reflow treatment. Is to provide.
[0008]
[Means for Solving the Problems]
The present inventor has conducted various studies to solve the above-described problems, and as a result of adding an aliphatic alcohol to the hard gold plating solution, the maximum value of the current density range in which plating can be performed is increased, and deposition of a gold plating film is performed. It has been found that the speed is improved, and even if a heat treatment is performed after gold plating, a plated film exhibiting stable contact resistance without reducing the contact resistance can be obtained.
[0009]
The present invention that solves the above-mentioned problems is described below.
[0010]
[1] An electrolytic hard gold plating solution containing a soluble gold salt or a gold complex as a gold ion source, an organic acid salt and / or an inorganic acid salt as a conductive salt, and a hardening agent, wherein an aliphatic alcohol is used. An electrolytic hard gold plating solution characterized by containing.
[0011]
[2] The electrolytic hard gold plating solution according to [1], wherein the aliphatic alcohol is a saturated aliphatic alcohol having a linear or branched alkyl group having 8 or less carbon atoms.
[0012]
[3] The electrolytic hard gold plating solution according to [1], wherein the hardening agent is a soluble salt of cobalt and / or nickel.
[0013]
[4] An electrolytic hard gold plating method of plating at a current density of 0.1 to 60 A / dm 2 using the electrolytic hard gold plating solution according to [1].
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The aliphatic alcohol that can be used in the present invention is not particularly limited as long as it is a known one, but a saturated aliphatic alcohol having a linear or branched alkyl group having 8 or less carbon atoms is preferable. Such an alcohol can be easily dissolved in an aqueous solution and uniformly mixed when performing industrial plating. Particularly, the alkyl group of the saturated aliphatic alcohol preferably has 4 to 8 carbon atoms.
[0015]
As the saturated aliphatic alcohol which can be preferably used in the present invention, n-butyl alcohol, isobutyl alcohol, isoamyl alcohol, 1-hexyl alcohol, 1-heptanol, 2-methyl-3-hexanol, 5-methyl- Examples thereof include 1-hexanol and 2-ethyl-1-hexanol.
[0016]
The amount of the aliphatic alcohol to be added to the plating solution varies depending on the solubility in the plating solution and the like. The effect of the present invention is not impaired even if a large amount is added within the range of the solubility of each aliphatic alcohol. The addition amount of the aliphatic alcohol is preferably in the range of 0.05 to 100 ml / l, more preferably in the range of 0.1 to 10 ml / l.
[0017]
When an aliphatic alcohol is added to the gold plating solution, the hydrogen generation potential becomes lower, and the generation of hydrogen, which leads to a decrease in current efficiency, is suppressed, and the crystal growth of the gold film is controlled, and the finer grains are finer and denser. Form a film. Therefore, the heat resistance of the gold plating film is improved, and the contact resistance after the heat treatment does not decrease.
[0018]
As a gold ion supply source of the gold plating solution of the present invention, any soluble gold compound can be used without any limitation. From the viewpoints of availability, solubility in the plating solution, and stability of gold ions in the plating solution, selected from gold cyanide, potassium potassium cyanide, potassium potassium sulfite, and gold salts of gold thiosulfate. Those are particularly preferred.
[0019]
Further, a complexing agent which forms complex ions with gold according to the gold compound used may be added to form a gold complex, which may be used as a gold ion supply source. By adding a complexing agent to form a gold complex, the stability of gold ions can be controlled. A known complexing agent can be used, and examples thereof include ethylenediamine and EDTA.
[0020]
The amount of the gold salt or gold complex added to the plating solution is preferably 1 to 20 g / l as gold ions.
[0021]
The organic acid salt and / or inorganic acid salt to be added as a conductive salt is preferably an organic acid such as a carboxylic acid such as citric acid or tartaric acid; or an alkali metal salt of an inorganic acid such as phosphoric acid or sulfurous acid. Also, two or more of these may be used in combination.
The addition amount of the conductive salt is preferably 50 to 300 g / l.
[0022]
Further, the gold plating solution of the present invention contains a hardening agent for hardening the gold film. Known hardening agents can be used, but it is preferable to use soluble salts of cobalt and nickel. Examples of the soluble salts of cobalt and nickel include cobalt sulfate, nickel sulfate, cobalt chloride, nickel chloride and the like. A gold plating solution containing these as a hardening agent has a fine crystal grain of the gold plating film, makes it difficult for dislocations and atomic vacancies to occur due to crystal growth, and maintains a constant growth of the gold plating film for a long time. Becomes easier.
[0023]
The amount of the hardening agent added to the plating solution is preferably 0.05 to 5 g / l as metal ions such as cobalt and nickel.
[0024]
Further, it is preferable to add a pH buffer to the hard gold plating solution of the present invention in addition to the above essential components. Examples of the pH buffer include boric acid, succinic acid, phthalic acid, tartaric acid, citric acid, phosphoric acid, sulfurous acid and the like, and salts thereof. Two or more of these pH buffers may be used. By containing a pH buffer, the pH can be kept constant without a large fluctuation even when a gold plating solution is used, which is more preferable for long-term use. The content of the pH buffer is determined by a conventional method.
[0025]
When performing the electrolytic gold plating treatment using the hard electrolytic gold plating solution of the present invention, it is preferable that the pH, the solution temperature, and the current density of the plating solution be in the following ranges.
The pH of the gold plating solution is preferably in the range of 4.0 to 5.0 depending on the concentrations of the buffer and the conductive salt. Within this range, no abnormality occurs in the appearance of the deposited gold plating. If the pH is less than 4.0, the current efficiency tends to decrease. On the other hand, if it exceeds 5.0, the allowable current density range becomes narrow, and it becomes difficult for the hardening agent to be taken into the plating film. As a result, the plating film tends to have low hardness and low wear resistance.
[0026]
The temperature of the gold plating solution is preferably from 20 to 80C. If the temperature is less than 20 ° C., the temperature control is practically not easy, and the plating process becomes uneven, so that it is not suitable for the operation. If the temperature exceeds 80 ° C., the volume decrease due to the evaporation of the plating solution during the operation is large, and It becomes difficult to maintain the concentration.
[0027]
The current density during electrolysis is preferably 0.1 to 60 A / dm 2 . In consideration of the pH value, the solution temperature, and the gold concentration of the above-mentioned plating solution, the properties of the gold plating deposited at a current density in this range are good.
[0028]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
[0029]
Examples 1 to 12
Table 1 shows a gold plating solution containing potassium potassium cyanide (15 g / l as gold), tripotassium citrate 100 g / l, dipotassium hydrogen phosphate 30 g / l, and cobalt sulfate (0.5 g / l as cobalt). The following various aliphatic alcohols were added, and while maintaining 500 ml of the solution adjusted to pH 4.5 at a temperature of 60 ° C., the plating solution was sprayed at about 5 m / min from a nozzle having a diameter of 6 mm toward a cathode (plate). Using a jet-type gold plating apparatus having a structure in which plating is performed while spraying, gold plating having a thickness of 1 μm was performed, and the maximum current density range and deposition rate usable at that time were examined. Further, the contact resistance value of the plated film at a current density of 30 A / dm 2 was measured.
[0030]
The contact resistance was measured by a four-probe method using a platinum probe, and was measured with an MS-980 type contact resistance measuring device (manufactured by KS Components) under the conditions of a measurement current of 1 mA and a measurement load of 10 g.
[0031]
As a result, in all the examples, plating was possible up to a current density of 60 A / dm 2 , the film appearance was good, and the maximum deposition rate was 6-7 sec / μm. In addition, the contact resistance value was 15 to 17 mΩ before heat resistance, and 22 to 29 mΩ after heating at 230 ° C. for 30 minutes, showing a stable contact resistance value even after the heat treatment.
[0032]
Comparative Example 1
For comparison, gold plating solution containing only potassium potassium cyanide (15 g / l as gold), tripotassium citrate 100 g / l, dipotassium hydrogen phosphate 30 g / l, and cobalt sulfate (0.5 g / l as cobalt) only 500 ml Was adjusted to pH 4.5 with an aqueous solution of potassium hydroxide, and then, while maintaining the temperature at 60 ° C., a 1 μm-thick gold plating was performed using a jet-type gold plating apparatus. The range and deposition rate were examined. Further, the contact resistance value of the plating film obtained at a current density of 30 A / dm 2 was measured.
[0033]
As a result, the maximum current density at which a good film appearance was obtained was 30 A / dm 2 , and at 40 A / dm 2 or more, the film appearance became uneven and uneven. The maximum deposition rate of this plating solution was 10 sec / μm. The contact resistance value of this plating film was 17 mΩ before heat resistance, which was equivalent to that of the example. However, after heating at 230 ° C. for 30 minutes, the contact resistance value sharply increased to 110 mΩ, indicating that the electrical characteristics were deteriorated.
[0034]
When the case where the aliphatic alcohol is added (Examples 1 to 12) and the case where it is not added (Comparative Example 1) are compared, the usable current density range, the deposition rate, and the stability of the contact resistance value before and after the heat treatment are compared. It was confirmed that the examples in which the aliphatic alcohol was added were superior in all of the properties (heat resistance). Regarding the amount of the aliphatic alcohol to be added, the effect was sufficiently and equally exhibited at both 0.1 ml / l and 1.0 ml / l.
[0035]
[Table 1]
【The invention's effect】
According to the electrolytic hard gold plating solution and the plating method of the present invention, the current density range in which plating is possible is wide and the maximum current density is high, so that the deposition rate of the plating film is high and the productivity is improved. Furthermore, even if a heat treatment is performed after plating, the contact resistance does not decrease and a gold plating film having high heat stability can be formed.
[0037]
INDUSTRIAL APPLICABILITY The present invention is particularly suitable for surface treatment of components for electronic and electric devices such as connectors and contact materials, but is not limited thereto, and is also useful in the field of decoration and the like.
Claims (4)
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| JP2002233648A JP3989795B2 (en) | 2002-08-09 | 2002-08-09 | Electrolytic hard gold plating solution and plating method using the same |
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| JP2002233648A JP3989795B2 (en) | 2002-08-09 | 2002-08-09 | Electrolytic hard gold plating solution and plating method using the same |
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| JP3989795B2 JP3989795B2 (en) | 2007-10-10 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007023324A (en) * | 2005-07-14 | 2007-02-01 | Kanto Chem Co Inc | Electroless hard gold plating liquid |
| JP2007070730A (en) * | 2005-09-07 | 2007-03-22 | Rohm & Haas Electronic Materials Llc | Metal duplex and method |
| JP2007092156A (en) * | 2005-09-30 | 2007-04-12 | Ne Chemcat Corp | Non-cyanogen based gold electroplating bath for forming bump |
| JP4719822B2 (en) * | 2008-06-11 | 2011-07-06 | 日本高純度化学株式会社 | Electrolytic gold plating solution and gold film obtained using the same |
| DE112010000791T5 (en) | 2009-02-17 | 2012-07-26 | Kanto Kagaku K.K. | MIXED-MICROCRYSTALLINE-AMORPHIC GOLD ALLOYING OF ELECTROCHEMICALLY DISPOSED FILM AND BATHING SOLUTION, AND METHOD FOR PRODUCING AN ELECTROCHEMICALLY DISPOSED FILM THEREFOR |
-
2002
- 2002-08-09 JP JP2002233648A patent/JP3989795B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007023324A (en) * | 2005-07-14 | 2007-02-01 | Kanto Chem Co Inc | Electroless hard gold plating liquid |
| JP2007070730A (en) * | 2005-09-07 | 2007-03-22 | Rohm & Haas Electronic Materials Llc | Metal duplex and method |
| JP2007092156A (en) * | 2005-09-30 | 2007-04-12 | Ne Chemcat Corp | Non-cyanogen based gold electroplating bath for forming bump |
| KR101319745B1 (en) | 2005-09-30 | 2013-10-17 | 메타로 테쿠노로지 쟈판 가부시키가이샤 | Non-cyanogen type electrolytic gold plating bath for bump forming |
| JP4719822B2 (en) * | 2008-06-11 | 2011-07-06 | 日本高純度化学株式会社 | Electrolytic gold plating solution and gold film obtained using the same |
| DE112010000791T5 (en) | 2009-02-17 | 2012-07-26 | Kanto Kagaku K.K. | MIXED-MICROCRYSTALLINE-AMORPHIC GOLD ALLOYING OF ELECTROCHEMICALLY DISPOSED FILM AND BATHING SOLUTION, AND METHOD FOR PRODUCING AN ELECTROCHEMICALLY DISPOSED FILM THEREFOR |
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| JP3989795B2 (en) | 2007-10-10 |
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