JP2005097669A - Liquid and method for post-treating plated surface - Google Patents
Liquid and method for post-treating plated surface Download PDFInfo
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Abstract
Description
本発明はメッキ表面の後処理液、並びに当該後処理液を用いたメッキ表面の後処理方法に関して、メッキ表面のハンダ濡れ性を良好に保持し、摩擦抵抗を軽減するとともに、表面処理を迅速・簡便化できるものを提供する。 The present invention relates to a post-treatment liquid for the plating surface and a post-treatment method for the plating surface using the post-treatment liquid. The solder wettability of the plating surface is maintained well, the frictional resistance is reduced, and the surface treatment is rapidly performed. Provide what can be simplified.
金属材料にハンダ付けをする場合、ハンダ濡れ性を確保するため、予め金属材料にスズ又はスズ合金などのメッキ皮膜を形成するが、一般の金属表面と同様に、このメッキ面も酸化により経時劣化し易く、変色してしまって表面特性が損なわれる。
また、環境保護・生産性向上・保管の省スペース化の見地から、最近、チップ部品の実装手段がテープ実装システムからバルク実装システムに移って来ているが、このバルク実装システムでは、バルクケース内やホッパーで摩擦により電極が劣化したり、メッキ皮膜の削れ屑が発生してパーツフィーダーが運転不良を起こすなどの問題が発生し、メッキ表面の摩擦抵抗の改善が要望されている。
When soldering a metal material, in order to ensure solder wettability, a plating film such as tin or tin alloy is previously formed on the metal material. Like a general metal surface, this plating surface also deteriorates over time due to oxidation. It is easy to do and discolors and the surface properties are impaired.
In addition, from the viewpoint of environmental protection, productivity improvement, and storage space saving, chip component mounting methods have recently moved from tape mounting systems to bulk mounting systems. In this bulk mounting system, Problems such as electrode deterioration due to friction in the hopper and plating film scraps, and parts feeders causing poor operation, have been demanded to improve the frictional resistance of the plating surface.
表面特性を改善する目的で、金属材料に形成したメッキ表面を後処理する技術としては、次のものがある。
先ず、特許文献１には、耐酸化性、耐食性などの改善を目的として、スズメッキを形成した鋼板に、リン酸などを主成分とする水溶液中で陰極電解、陽極電解を施し、リン酸などとマグネシウムイオンを含有する水溶液(ｐＨ２〜３.５)を塗布することが開示されている(請求の範囲及び段落２１参照)。そして、処理液中のマグネシウムイオンの濃度は０.０５ｇ／Ｌ〜５ｇ／Ｌが好ましいことが記載されている(段落２２参照)。
As a technique for post-processing the plating surface formed on the metal material for the purpose of improving the surface characteristics, there are the following.
First, in Patent Document 1, for the purpose of improving oxidation resistance, corrosion resistance, etc., a steel plate on which tin plating is formed is subjected to cathodic electrolysis and anodic electrolysis in an aqueous solution containing phosphoric acid as a main component. It is disclosed to apply an aqueous solution (pH 2 to 3.5) containing magnesium ions (see claims and paragraph 21). And it is described that the concentration of magnesium ions in the treatment liquid is preferably 0.05 g / L to 5 g / L (see paragraph 22).
特許文献２には、耐食性の向上を目的として、亜鉛系メッキ鋼板又はアルミニウム系メッキ鋼板を、アルミニウム、マグネシウムなどの金属イオンと、シリカ又はシリカゾル、リン酸イオンなどの他の成分とを含有する水溶液で処理することが開示されている。上記金属イオンの水溶液中での濃度は０.００１〜３モル／Ｌであることが記載されている(請求項１参照)。 In Patent Document 2, for the purpose of improving corrosion resistance, a zinc-based plated steel sheet or an aluminum-based plated steel sheet is an aqueous solution containing metal ions such as aluminum and magnesium and other components such as silica or silica sol and phosphate ions. Is disclosed. It is described that the concentration of the metal ion in the aqueous solution is 0.001 to 3 mol / L (see claim 1).
特許文献３には、亜鉛又は亜鉛合金メッキを施した金属材料を、アルミニウム、マグネシウム、モリブデン、３価クロムなどの金属を含有する水性液状組成物で処理して、メッキ表面に保護皮膜を形成して、耐食性を向上できる(防錆皮膜を形成する)ことが開示されている(段落８、段落４１参照)。アルミニウム、マグネシウム、モリブデンなどの金属イオン濃度は０.０１〜１００ｇ／Ｌであることが記載されている(段落４３参照)。 In Patent Document 3, a metal material plated with zinc or zinc alloy is treated with an aqueous liquid composition containing a metal such as aluminum, magnesium, molybdenum, or trivalent chromium to form a protective film on the plating surface. Thus, it is disclosed that the corrosion resistance can be improved (form a rust preventive film) (see paragraphs 8 and 41). It is described that the metal ion concentration of aluminum, magnesium, molybdenum or the like is 0.01 to 100 g / L (see paragraph 43).
特許文献４には、鋼材表面を、ニッケル、コバルト、クロム、鉄などのＡ群イオンを含む湿潤液で湿潤して、腐食を促進して錆層の形成を迅速化するとともに、形成された錆層を緻密にして耐食性を高め、或は、さらに、モリブデン、チタン、タングステン、アルミニウム、マグネシウムなどのＢ群イオンを含む湿潤液で湿潤して、さらに錆層を緻密化して、鋼材の耐候性をより良く向上させることが記載されている(段落１１〜〜１５、段落２２〜２３参照)。 In Patent Document 4, the surface of a steel material is wetted with a wetting liquid containing group A ions such as nickel, cobalt, chromium, iron, etc. to accelerate corrosion and speed up the formation of a rust layer, and the formed rust. The layer is made dense to improve the corrosion resistance, or further wetted with a wetting liquid containing group B ions such as molybdenum, titanium, tungsten, aluminum, magnesium, etc. It is described that it is improved better (see paragraphs 11 to 15 and paragraphs 22 to 23).
上記特許文献１〜４の技術は、耐食性、防錆目的であり、メッキ皮膜のハンダ濡れ性や摩擦抵抗の改善を目的としたものではないうえ、特に、特許文献１ではｐＨ２〜３.５の酸性液を用いるため、メッキ面が腐食する恐れがある。また、特許文献１〜３は、同文献１を除いて、亜鉛系メッキ面などを対象とし、スズ又はスズ合金メッキ面、或は金、銀、銅、ニッケルメッキ面を対象とするものではなく、しかも、特許文献４にあっては、メッキ形成していない鋼材を対象として、その耐候性を高めようとするものである。
さらに、特許文献１は、陰極電解、陽極電解を施してから、所定金属イオンを含む液で処理するもので、操作が煩雑である。
本発明は、スズ系又はその他のメッキ表面の後処理において、簡便な処理でメッキ皮膜のハンダ濡れ性や摩擦抵抗を改善することを技術的課題とする。
The techniques of Patent Documents 1 to 4 are for the purpose of corrosion resistance and rust prevention, and are not intended to improve solder wettability and frictional resistance of the plating film. In particular, Patent Document 1 has a pH of 2 to 3.5. Since the acidic liquid is used, the plated surface may be corroded. Patent Documents 1 to 3 are not intended for zinc-based plated surfaces, but tin or tin alloy-plated surfaces, or gold, silver, copper, or nickel-plated surfaces, except for Reference 1 above. And in patent document 4, it intends to improve the weather resistance for the steel materials which are not plating-formed.
Further, in Patent Document 1, after performing cathodic electrolysis and anodic electrolysis, treatment with a liquid containing a predetermined metal ion is complicated, and the operation is complicated.
This invention makes it a technical subject to improve the solder wettability and frictional resistance of a plating film by simple processing in the post-processing of a tin type or other plating surface.
本発明者らは、アルミニウム、マンガン、マグネシウムなどの特定金属のイオンを含有する処理液でスズ又はスズ合金メッキ面を後処理すると、メッキ皮膜のハンダ濡れ性が増し、摩擦抵抗が軽減すること、金属イオンの含有量は０.０５ｇ／Ｌのごく少量以上で足りること、そして、上記特定金属以外の他種の金属イオン、例えば、上記特許文献１〜３に開示されたカルシウムやバリウムなどの他種イオンでは同様の効果は得られないことを突き止めるとともに、金、銀、銅、ニッケルの各メッキ面に対しても同様の効果を奏することを見い出し、本発明を完成した。 When the present inventors post-treat the tin or tin alloy plating surface with a treatment liquid containing ions of a specific metal such as aluminum, manganese, magnesium, the solder wettability of the plating film is increased, and the frictional resistance is reduced. A metal ion content of 0.05 g / L or more is sufficient, and other types of metal ions other than the specific metal, such as calcium and barium disclosed in Patent Documents 1 to 3 above. The inventors have found out that the same effect cannot be obtained with seed ions, and have found that the same effect can be exerted on gold, silver, copper, and nickel plating surfaces, thereby completing the present invention.
即ち、本発明１は、被メッキ物にスズ、スズ合金、金、銀、銅、ニッケルのいずれかのメッキ皮膜を形成した後に、そのメッキ表面を後処理する液であって、
上記後処理液が、アルミニウム、マンガン、マグネシウム、ニッケル、亜鉛、コバルト、タングステンよりなる群から選ばれた少なくとも一種の金属イオンを含有する水溶液であることを特徴とするメッキ表面の後処理液である。
That is, the present invention 1 is a liquid for post-treating the plating surface after forming a plating film of tin, tin alloy, gold, silver, copper, or nickel on an object to be plated,
The plating surface post-treatment liquid, wherein the post-treatment liquid is an aqueous solution containing at least one metal ion selected from the group consisting of aluminum, manganese, magnesium, nickel, zinc, cobalt, and tungsten. .
本発明２は、上記本発明１において、後処理液にアルミニウムイオンとマグネシウムイオンを含有することを特徴とするメッキ表面の後処理液である。 The present invention 2 is the post-treatment liquid for the plating surface according to the first invention, wherein the post-treatment liquid contains aluminum ions and magnesium ions.
本発明３は、上記本発明１又は２において、金属イオンの含有量が０.０５ｇ／Ｌ以上であることを特徴とするメッキ表面の後処理液である。 The present invention 3 is the post-treatment liquid for the plating surface according to the present invention 1 or 2, wherein the metal ion content is 0.05 g / L or more.
本発明４は、上記本発明１〜３のいずれかにおいて、スズ合金が、スズと、銀、ビスマス、銅、インジウム、ニッケル、コバルト、金、アンチモン、鉛から選ばれた金属との合金であることを特徴とするメッキ表面の後処理液である。 Invention 4 is the alloy of any one of Inventions 1 to 3, wherein the tin alloy is an alloy of tin and a metal selected from silver, bismuth, copper, indium, nickel, cobalt, gold, antimony, and lead. This is a post-treatment liquid for the plating surface.
本発明５は、メッキ皮膜を形成した被メッキ物を上記本発明１〜４のいずれかの後処理液に接触させることを特徴とするメッキ表面の後処理方法である。 The present invention 5 is a post-treatment method for a plating surface, characterized in that an object to be plated on which a plating film is formed is brought into contact with the post-treatment liquid according to any one of the first to fourth aspects of the present invention.
本発明６は、上記本発明５の後処理方法を施した半導体デバイス、プリント基板、フレキシブルプリント基板、フィルムキャリア、ＩＣ、コネクタ、スイッチ、抵抗、可変抵抗、コンデンサ、フィルタ、インダクタ、サーミスタ、水晶振動子、リード線などの電子部品である。 The present invention 6 includes a semiconductor device, a printed board, a flexible printed board, a film carrier, an IC, a connector, a switch, a resistor, a variable resistor, a capacitor, a filter, an inductor, a thermistor, and a crystal vibration which have been subjected to the post-treatment method of the present invention 5. It is an electronic component such as a child or lead wire.
(1)ハンダ濡れ性を確保する目的で、金属材料にスズ又はスズ合金などのメッキ皮膜を形成しているが、メッキ面は酸化により経時劣化し易い。
本発明では、このメッキ面をアルミニウム、ニッケル、コバルト、タングステンなどの特定の金属イオンを含む後処理液で表面処理するため、メッキ面には所定の金属が吸着して保護作用を発揮することが推定できる。このため、後処理したスズ又はスズ合金などのメッキ面は経時劣化を起こさずにハンダ濡れ性を良好に保持できる。
また、後処理したメッキ表面には上記吸着作用が推測されることから、メッキ面の摩擦係数が低下し、その摩擦抵抗を有効に軽減できるため、チップ部品の実装システムとして最近注目されて来たバルク実装システムに本発明の後処理方法を適用すると、摩擦により電極が劣化したり、メッキ皮膜の削れ屑が発生してパーツフィーダーが運転不良を起こすなどの弊害を円滑に防止できる。
さらには、後処理液にアルミニウムイオンとマグネシウムイオンを共存させると、アルミニウムイオンを単独で含有する場合に比べて、アルミニウムイオン濃度を低減しながら、メッキ面のハンダ濡れ性の向上と摩擦抵抗の軽減を図れる。
(1) Although a plating film such as tin or tin alloy is formed on a metal material for the purpose of ensuring solder wettability, the plated surface is likely to deteriorate over time due to oxidation.
In the present invention, since the plated surface is surface-treated with a post-treatment liquid containing specific metal ions such as aluminum, nickel, cobalt, and tungsten, a predetermined metal can be adsorbed on the plated surface to exert a protective action. Can be estimated. For this reason, the plated surface such as post-treated tin or tin alloy can maintain good solder wettability without causing deterioration over time.
In addition, since the above-mentioned adsorption action is presumed on the post-processed plating surface, the friction coefficient of the plating surface is reduced, and the frictional resistance can be effectively reduced. Therefore, it has recently been attracting attention as a chip component mounting system. When the post-processing method of the present invention is applied to a bulk mounting system, it is possible to smoothly prevent problems such as deterioration of electrodes due to friction and generation of scraps from the plating film, resulting in malfunction of the parts feeder.
Furthermore, when aluminum ions and magnesium ions coexist in the post-treatment liquid, the solder surface wettability and frictional resistance are reduced while reducing the aluminum ion concentration compared to the case where aluminum ions are contained alone. Can be planned.
(2)前記特許文献１では、陰極電解、陽極電解を施してから、所定金属イオンを含む液で処理する必要があり、操作が煩雑である。
また、ベンゾトリアゾールなどを有効成分とする後処理液(例えば、特開平７−１７３６７５号公報など)が公知であるが、この後処理液では、有効成分をエタノール、ＩＰＡなどの有機溶媒に溶解したり、水に懸濁する必要があり、処理が煩雑であるうえ、有機溶媒の使用は環境や労働衛生に悪影響を与え、引火の危険もある。また、水性エマルションの場合は金属表面への吸着が均一にならない。
これに対して、本発明では、アルミニウム、ニッケル、コバルト、タングステンなどの特定金属の可溶性塩を溶解した水溶液でメッキ面を接触処理するだけなので、処理を簡便化できる。即ち、本発明の後処理液はアルミニウムなどの特定金属の可溶性塩を水に溶解した水溶液の形態なので、上記ベンゾトリアゾールなどを有効成分とする後処理液に比べても、処理が容易で、環境保全や労働衛生に資するうえ、引火の危険もなく、水溶液なので金属表面への吸着も均一になる。
しかも、後処理液の濃度は０.０５ｇ／Ｌのごく少量を下限とするため、コスト的にも優れている。
(2) In Patent Document 1, after performing cathodic electrolysis and anodic electrolysis, it is necessary to treat with a liquid containing a predetermined metal ion, and the operation is complicated.
Further, post-treatment liquids containing benzotriazole or the like as an active ingredient (for example, JP-A-7-173675) are known. In this post-treatment liquid, the active ingredient is dissolved in an organic solvent such as ethanol or IPA. In addition, the treatment is complicated, and the use of an organic solvent adversely affects the environment and occupational health, and there is a risk of ignition. In the case of an aqueous emulsion, the adsorption to the metal surface is not uniform.
On the other hand, in this invention, since a plating surface is only contact-treated with the aqueous solution which melt | dissolved soluble salts of specific metals, such as aluminum, nickel, cobalt, and tungsten, a process can be simplified. That is, since the post-treatment liquid of the present invention is in the form of an aqueous solution in which a soluble salt of a specific metal such as aluminum is dissolved in water, the treatment is easier than the post-treatment liquid containing benzotriazole or the like as an active ingredient. Contributes to conservation and occupational health, and there is no danger of ignition, and since it is an aqueous solution, adsorption onto the metal surface is uniform.
Moreover, since the concentration of the post-treatment liquid is set to a very small amount of 0.05 g / L, the cost is excellent.
本発明は、第一に、アルミニウム、ニッケル、コバルト、タングステンなどの特定金属イオンを含有するスズ又はスズ合金などのメッキ表面の後処理液であり、第二に、この後処理液でメッキ表面を後処理する方法であり、第三に、当該後処理方法を施した電子部品である。 The present invention is firstly a post-treatment liquid for a plating surface such as tin or a tin alloy containing specific metal ions such as aluminum, nickel, cobalt, tungsten, etc., and secondly, the plating surface is treated with this post-treatment liquid. This is a post-processing method, and thirdly, an electronic component subjected to the post-processing method.
本発明の後処理液は、アルミニウム、マグネシウム、マンガン、ニッケル、亜鉛、コバルト、タングステンよりなる群から選ばれた少なくとも一種の金属のイオンを含有する水溶液であり、これらの特定金属の可溶性塩を水に溶解して調製される。
上記特定金属の可溶性塩は、基本的に水中で相当するＡｌ3+、Ｍｇ2+、Ｍｎ2+、Ｎｉ2+、Ｚｎ2+、Ｃｏ2+、Ｃｏ3+、Ｗ2+、Ｗ5+、Ｗ6+などの金属イオンを発生させるものであれば特に制限はなく、難溶性塩も排除されない。
可溶性アルミニウム塩としては、アルミニウムの酸化物、水酸化物、硫酸塩、ハロゲン化物、硝酸塩、酢酸塩、リン酸塩、ホウ酸塩、アルミン酸塩、アルミノケイ酸塩、或は、明ばん等の複塩などが挙げられ、具体的には、硫酸アルミニウム、塩化アルミニウム、酢酸アルミニウム、臭化アルミニウム、硝酸アルミニウム、水酸化アルミニウム、シュウ酸アルミニウム、乳酸アルミニウム、ホウ酸アルミニウム、ヨウ化アルミニウム、硫酸アルミニウムアンモニウム、リン酸アルミニウムなどであり、好ましくは硫酸アルミニウム、塩化アルミニウムである。
可溶性マグネシウム塩としては、塩化マグネシウム、臭化マグネシウム、フッ化マグネシウム、硫酸マグネシウム、硫酸アンモニウムマグネシウム、硝酸マグネシウム、リン酸マグネシウム、酢酸マグネシウム、シュウ酸マグネシウム、乳酸マグネシウム、安息香酸マグネシウムなどが挙げられ、塩化マグネシウム、硫酸マグネシウムが好ましい。
また、マンガン、ニッケル、亜鉛などの他の特定金属の可溶性塩としては、これらの特定金属のハロゲン化物、酸化物、硫酸、硝酸などの無機酸塩、酢酸、有機スルホン酸などの有機酸塩、或はタングステンなどではタングステン酸カリウムなどの各種複塩などが挙げられる。
The post-treatment liquid of the present invention is an aqueous solution containing ions of at least one metal selected from the group consisting of aluminum, magnesium, manganese, nickel, zinc, cobalt, and tungsten. It is prepared by dissolving.
The above-mentioned soluble salts of specific metals are basically Al 3+ , Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ , Co 2+ , Co 3+ , W 2+ , W 5+ in water. As long as it generates metal ions such as W 6+ , there is no particular limitation, and hardly soluble salts are not excluded.
Soluble aluminum salts include aluminum oxides, hydroxides, sulfates, halides, nitrates, acetates, phosphates, borates, aluminates, aluminosilicates, or complex compounds such as alum. Examples include salts such as aluminum sulfate, aluminum chloride, aluminum acetate, aluminum bromide, aluminum nitrate, aluminum hydroxide, aluminum oxalate, aluminum lactate, aluminum borate, aluminum iodide, aluminum ammonium sulfate, Aluminum phosphate and the like, preferably aluminum sulfate and aluminum chloride.
Examples of soluble magnesium salts include magnesium chloride, magnesium bromide, magnesium fluoride, magnesium sulfate, magnesium magnesium sulfate, magnesium nitrate, magnesium phosphate, magnesium acetate, magnesium oxalate, magnesium lactate, magnesium benzoate, etc. Magnesium sulfate is preferred.
In addition, as soluble salts of other specific metals such as manganese, nickel, zinc, etc., halides of these specific metals, oxides, inorganic acid salts such as sulfuric acid and nitric acid, organic acid salts such as acetic acid and organic sulfonic acid, Or, for tungsten or the like, various double salts such as potassium tungstate can be cited.
後処理液に含有する上記特定金属のイオンとしては、上述の通り、アルミニウム、マグネシウム、マンガン、ニッケル、亜鉛、コバルト、タングステンの各イオンを単用しても良いし、これらのイオンを併用しても良く、特に、アルミニウム、ニッケル、コバルト、タングステンの各イオンは比較的少量を含有してもハンダ濡れ性を有効に改善できる点で好ましい。
また、本発明２に示すように、後処理液にアルミニウムイオンを含有する場合、マグネシウムイオンを共存させると、メッキ面のハンダ濡れ性や摩擦抵抗の軽減を図るうえで、アルミニウムイオンの濃度を低減でき、マグネシウムイオンにはアルミニウムイオンの作用を補強する効果が窺える。即ち、本発明の特定金属イオン同士の併用では、アルミニウムイオンとマグネシウムイオンの併用が好ましい。
本発明３に示すように、上記特定金属イオンの濃度は０.０５ｇ／Ｌ以上が適当であり、好ましくは０.１〜５０ｇ／Ｌ、より好ましくは０.１〜３０ｇ／Ｌである。
特定金属イオンの濃度が少な過ぎるとメッキ面のハンダ濡れ性を確保できず、また、摩擦抵抗を軽減できず、多過ぎても後処理効果にあまり変化はなく、コストの無駄であり、また、ハンダ付けに悪影響を及ぼす恐れがある。
As the ions of the specific metal contained in the post-treatment liquid, as described above, each ion of aluminum, magnesium, manganese, nickel, zinc, cobalt, tungsten may be used alone, or these ions may be used in combination. In particular, aluminum, nickel, cobalt, and tungsten ions are preferable because they can effectively improve the solder wettability even if they contain a relatively small amount.
In addition, as shown in the present invention 2, when the post-treatment liquid contains aluminum ions, the presence of magnesium ions reduces the aluminum ion concentration in order to reduce solder wettability and frictional resistance of the plating surface. In addition, magnesium ions have the effect of reinforcing the action of aluminum ions. That is, in the combined use of specific metal ions of the present invention, the combined use of aluminum ions and magnesium ions is preferable.
As shown in Invention 3, the concentration of the specific metal ion is suitably 0.05 g / L or more, preferably 0.1 to 50 g / L, more preferably 0.1 to 30 g / L.
If the concentration of the specific metal ion is too small, solder wettability of the plated surface cannot be secured, the frictional resistance cannot be reduced, and if it is too much, the post-treatment effect does not change much, which is a waste of cost, There is a risk of adversely affecting soldering.
本発明の後処理液は、アルミニウム、マンガン、ニッケル、タングステンなどの特定金属の可溶性塩を水に溶解して調製されるもので、これらの金属イオンを有効成分として含有する水溶液であるが、これらの特定金属の可溶性塩と共に、公知の耐食処理剤であるリン酸塩を併用できることはいうまでもない。
上記リン酸塩としては、第三リン酸、リン酸一ナトリウム、リン酸三ナトリウム、リン酸亜鉛などの第三リン酸塩、リン酸水素二ナトリウム、リン酸水素カルシウム、次亜リン酸、次亜リン酸ナトリウム、次亜リン酸ニッケルなどの次亜リン酸塩、亜リン酸、亜リン酸カルシウム、亜リン酸二カリウムなどの亜リン酸塩、ピロリン酸、ピロリン酸亜鉛、ピロリン酸カリウムなどのピロリン酸塩、メタリン酸、メタリン酸カリウム、メタリン酸ナトリウムなどのメタリン酸塩、グリセロリン酸、グリセロリンリン酸カルシウムなどが挙げられる。
The post-treatment liquid of the present invention is prepared by dissolving a soluble salt of a specific metal such as aluminum, manganese, nickel, or tungsten in water, and is an aqueous solution containing these metal ions as an active ingredient. It goes without saying that a known anti-corrosion treatment phosphate can be used in combination with the soluble salt of the specific metal.
Examples of the phosphate include tertiary phosphates such as triphosphate, monosodium phosphate, trisodium phosphate, zinc phosphate, disodium hydrogen phosphate, calcium hydrogen phosphate, hypophosphorous acid, Hypophosphites such as sodium phosphite and nickel hypophosphite, phosphites such as phosphorous acid, calcium phosphite and dipotassium phosphite, pyrrolines such as pyrophosphoric acid, zinc pyrophosphate and potassium pyrophosphate Examples thereof include metaphosphates such as acid salts, metaphosphoric acid, potassium metaphosphate, and sodium metaphosphate, glycerophosphoric acid, and calcium glycerophosphate.
また、本発明の後処理液には、メッキ表面への液の浸透力を向上する目的で、界面活性剤を含有することができる。
上記界面活性剤としては、モノアルキルリン酸エステル、ジアルキルリン酸エステルを初め、通常のノニオン系、アニオン系、両性、或はカチオン系などの各種界面活性剤を使用できる。
上記アニオン系界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩などが挙げられる。カチオン系界面活性剤としては、モノ〜トリアルキルアミン塩、ジメチルジアルキルアンモニウム塩、トリメチルアルキルアンモニウム塩などが挙げられる。ノニオン系界面活性剤としては、Ｃ1〜Ｃ20アルカノール、フェノール、ナフトール、ビスフェノール類、Ｃ1〜Ｃ25アルキルフェノール、アリールアルキルフェノール、Ｃ1〜Ｃ25アルキルナフトール、Ｃ1〜Ｃ25アルコキシルリン酸(塩)、ソルビタンエステル、ポリアルキレングリコール、Ｃ1〜Ｃ22脂肪族アミドなどにエチレンオキシド(ＥＯ)及び／又はプロピレンオキシド(ＰＯ)を２〜３００モル付加縮合させたものなどが挙げられる。両性界面活性剤としては、カルボキシベタイン、イミダゾリンベタイン、スルホベタイン、アミノカルボン酸などが挙げられる。
Further, the post-treatment liquid of the present invention can contain a surfactant for the purpose of improving the penetrating power of the liquid to the plating surface.
Examples of the surfactant include monoalkyl phosphate esters and dialkyl phosphate esters, as well as various nonionic, anionic, amphoteric, and cationic surfactants.
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, and alkyl naphthalene sulfonates. Examples of the cationic surfactant include mono-trialkylamine salts, dimethyldialkylammonium salts, and trimethylalkylammonium salts. Examples of the nonionic surfactant, C 1 -C 20 alkanols, phenol, naphthol, bisphenol, C 1 -C 25 alkyl phenols, aryl phenols, C 1 -C 25 alkyl naphthol, C 1 -C 25 alkoxyl phosphoric acid (salt ), Sorbitan esters, polyalkylene glycols, C 1 -C 22 aliphatic amides and the like, and 2-300 mol addition-condensation of ethylene oxide (EO) and / or propylene oxide (PO). Examples of amphoteric surfactants include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid.
本発明の後処理液には金属イオンを安定化させる見地から、さらにｐＨ調整剤などを含有できる。
上記ｐＨ調整剤としては、塩酸、硫酸、リン酸、ホウ酸、シュウ酸などの無機酸とその塩、メタンスルホン酸、イセチオン酸、フェノールスルホン酸、酢酸、プロピオン酸、シュウ酸、酒石酸、クエン酸、グルコン酸、リンゴ酸、乳酸、コハク酸、フタル酸などの有機酸とその塩、或は、アンモニア水、水酸化カリウム、水酸化ナトリウム、４級アンモニウム塩を含む各種アミンなどの塩基が挙げられる。
From the standpoint of stabilizing metal ions, the post-treatment liquid of the present invention can further contain a pH adjuster and the like.
Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and oxalic acid and salts thereof, methanesulfonic acid, isethionic acid, phenolsulfonic acid, acetic acid, propionic acid, oxalic acid, tartaric acid, and citric acid. , Organic acids such as gluconic acid, malic acid, lactic acid, succinic acid and phthalic acid and salts thereof, or bases such as various amines including aqueous ammonia, potassium hydroxide, sodium hydroxide and quaternary ammonium salts. .
本発明５は、上記処理液を用いたメッキ表面の後処理方法である。この後処理方法は、銅或は銅合金製などの金属材料(即ち、被メッキ物)にメッキ皮膜を形成した後に、後処理液をこのメッキ面に接触させることにより実施される。
被メッキ物に形成されるメッキ皮膜は、本発明４に示すように、ハンダ付け性を良好に確保する見地から、スズ、又はスズ−銅合金、スズ−銀合金、スズ−ビスマス合金、スズ−鉛合金などのスズ合金、或は、金、銀、銅、ニッケルの各皮膜が好ましい。メッキ方法は電気メッキ、無電解メッキを問わない。
本発明の後処理方法を施す被メッキ物としては特に制限されないが、本発明６に示すように、半導体デバイス、プリント基板、フレキシブルプリント基板、フィルムキャリア、ＩＣ、コネクタ、スイッチ、抵抗、可変抵抗、コンデンサ、フィルタ、インダクタ、サーミスタ、水晶振動子、リード線などの電子部品が代表例である。
The present invention 5 is a post-treatment method for a plating surface using the above treatment liquid. This post-treatment method is performed by forming a plating film on a metal material (that is, an object to be plated) such as copper or a copper alloy, and then bringing a post-treatment liquid into contact with the plating surface.
As shown in the present invention 4, the plating film formed on the object to be plated is tin, tin-copper alloy, tin-silver alloy, tin-bismuth alloy, tin--, from the viewpoint of ensuring good solderability. A tin alloy such as a lead alloy, or a coating of gold, silver, copper, or nickel is preferable. The plating method may be electroplating or electroless plating.
Although it does not restrict | limit especially as a to-be-plated object which performs the post-processing method of this invention, As shown in this invention 6, a semiconductor device, a printed circuit board, a flexible printed circuit board, a film carrier, IC, a connector, a switch, resistance, variable resistance, Representative examples include electronic components such as capacitors, filters, inductors, thermistors, crystal resonators, and lead wires.
上記接触方法は、メッキ材を後処理液に浸漬することを基本とするが、メッキ材に処理液を塗布しても良いし、噴霧しても良い。
後処理時間は１秒〜１５分が適当であり、３０秒〜５分が好ましい。浸漬温度は必要に応じて任意に調整できるが、０〜７０℃程度が好ましく、エネルギーコストでは室温程度がより好ましい。浸漬時間は浸漬温度により適宜増減でき、また、メッキ材の形状や材質又はメッキ装置に応じて処理時間と温度を適宜選択できる。
The above contact method is based on immersing the plating material in the post-treatment liquid, but the treatment liquid may be applied to the plating material or may be sprayed.
The post-treatment time is suitably 1 second to 15 minutes, preferably 30 seconds to 5 minutes. Although immersion temperature can be adjusted arbitrarily as needed, about 0-70 degreeC is preferable and about room temperature is more preferable at energy cost. The immersion time can be appropriately increased or decreased depending on the immersion temperature, and the treatment time and temperature can be appropriately selected according to the shape and material of the plating material or the plating apparatus.
以下、銅板にスズ又はスズ−銅合金メッキを施したメッキ表面を本発明の液で後処理する実施例、当該後処理方法を施したメッキ表面のハンダ濡れ性試験例、並びに当該メッキ表面の摩擦試験例を順次説明する。
尚、本発明は下記の実施例、試験例に拘束されるものではなく、本発明の技術的思想の範囲内で任意の変形をなし得ることは勿論である。
Hereinafter, examples in which a plated surface obtained by performing tin or tin-copper alloy plating on a copper plate is post-treated with the liquid of the present invention, solder wettability test examples on the plated surface subjected to the post-treatment method, and friction on the plated surface Test examples will be described sequentially.
The present invention is not limited to the following examples and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.
《スズメッキ表面を後処理する実施例》
下記の実施例１〜８のうち、実施例１〜６は特定金属イオンを単用して、その種類と含有濃度を変えた例、実施例７はアルミニウムとマグネシウムの両イオンを共存させた例、実施例８はアルミニウムイオンと共に公知の耐食処理剤であるリン酸塩を併用した例である。
一方、比較例１〜３のうち、比較例１はメッキ表面を後処理しないブランク例、比較例２は上記特許文献１〜３に開示された本発明とは異なる他種金属であるバリウムのイオンを含有させた例、比較例３は同様に他種金属であるカルシウムのイオンを含有させた例である。
<< Example of post-processing the tin plating surface >>
Among Examples 1 to 8 below, Examples 1 to 6 are examples in which a specific metal ion is used alone and the type and concentration are changed, and Example 7 is an example in which both ions of aluminum and magnesium coexist. Example 8 is an example in which a phosphate which is a known anticorrosive treatment agent is used in combination with aluminum ions.
On the other hand, among Comparative Examples 1 to 3, Comparative Example 1 is a blank example in which the plating surface is not post-treated, and Comparative Example 2 is an ion of barium that is a different kind of metal different from the present invention disclosed in Patent Documents 1 to 3 above. Similarly, Comparative Example 3 is an example in which calcium ions which are other kinds of metals are contained.
(1)実施例１
(ａ)スズメッキ処理
先ず、下記の組成でスズメッキ浴を建浴した。
メタンスルホン酸第一スズ(Ｓｎ2+として) １０ｇ／Ｌ
メタンスルホン酸 １００ｇ／Ｌ
β−ナフトールポリエトキシレート(EO10モル) １０ｇ／Ｌ
次いで、２５mm×２５mmの銅板を試験片として、上記スズメッキ浴を用いて、浴温２５℃、陰極電流密度２.０Ａ／ｄｍ2、メッキ時間１２分間の条件で電気メッキを行い、膜厚１０μｍでスズメッキ皮膜を形成した。
その後、スズメッキを施した上記試験片を５％第三リン酸ナトリウムの水溶液に７０℃、３０秒の条件で浸漬した後、純水で水洗した。
(ｂ)メッキ表面の後処理
硫酸アルミニウムの１４水和物(Ａｌ2(ＳＯ4)3・１４Ｈ2Ｏ)を水に溶解することにより、アルミニウムイオンを含有する後処理液を得た。後処理液中の当該アルミニウム塩の含有量は金属換算で３ｇ／Ｌに調整した。
次いで、前記試験片をこの後処理溶液に２５℃、３０秒の条件で浸漬した後、純水で水洗し、ドライヤーで乾燥した。
(1) Example 1
(a) Tin plating treatment First, a tin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn 2+ ) 10g / L
Methanesulfonic acid 100g / L
β-naphthol polyethoxylate (EO10 mol) 10g / L
Next, using a tin plate of 25 mm × 25 mm as a test piece, electroplating was performed using the above tin plating bath at a bath temperature of 25 ° C., a cathode current density of 2.0 A / dm 2 , and a plating time of 12 minutes. A tin plating film was formed.
Thereafter, the test piece plated with tin was immersed in an aqueous solution of 5% sodium triphosphate at 70 ° C. for 30 seconds, and then washed with pure water.
(b) Post-treatment of plating surface An aluminum sulfate-containing post-treatment liquid was obtained by dissolving aluminum sulfate 14-hydrate (Al 2 (SO 4 ) 3 .14H 2 O) in water. The content of the aluminum salt in the post-treatment liquid was adjusted to 3 g / L in terms of metal.
Next, the test piece was immersed in the post-treatment solution at 25 ° C. for 30 seconds, washed with pure water, and dried with a drier.
(2)実施例２
上記実施例１を基本として、硫酸アルミニウム水和物を硫酸マンガンに代替し、後処理液中のマンガン塩の含有量を金属換算で３０ｇ／Ｌに変更するとともに、後処理温度を６０℃に変更した以外は、上記実施例１と同様の条件で、メッキ処理(ａ)と後処理(ｂ)を行った。
(2) Example 2
Based on Example 1 above, aluminum sulfate hydrate was replaced with manganese sulfate, the content of manganese salt in the post-treatment liquid was changed to 30 g / L in terms of metal, and the post-treatment temperature was changed to 60 ° C. Except for the above, the plating treatment (a) and the post-treatment (b) were performed under the same conditions as in Example 1 above.
(3)実施例３
上記実施例１を基本として、硫酸アルミニウム水和物を硫酸ニッケルに代替し、後処理液中のニッケル塩の含有量を金属換算で０.１ｇ／Ｌに変更するとともに、後処理温度を５０℃に変更した以外は、上記実施例１と同様の条件により、メッキ処理と後処理を行った。
(3) Example 3
Based on Example 1 above, aluminum sulfate hydrate was replaced with nickel sulfate, the content of nickel salt in the post-treatment liquid was changed to 0.1 g / L in terms of metal, and the post-treatment temperature was 50 ° C. A plating process and a post-treatment were performed under the same conditions as in Example 1 except for changing to.
(4)実施例４
上記実施例１を基本として、硫酸アルミニウム水和物を硫酸亜鉛に代替し、後処理液中の亜鉛塩の含有量を金属換算で５０ｇ／Ｌに変更するとともに、後処理温度を３５℃に変更した以外は、上記実施例１と同様の条件で、メッキ処理と後処理を行った。
(4) Example 4
Based on the above Example 1, aluminum sulfate hydrate was replaced with zinc sulfate, the content of zinc salt in the post-treatment liquid was changed to 50 g / L in terms of metal, and the post-treatment temperature was changed to 35 ° C. Except for the above, plating and post-treatment were performed under the same conditions as in Example 1 above.
(5)実施例５
上記実施例１を基本として、硫酸アルミニウム水和物を硫酸コバルトに代替し、後処理液中のコバルト塩の含有量を金属換算で１０ｇ／Ｌに変更するとともに、後処理温度を１５℃に変更した以外は、上記実施例１と同様の条件で、メッキ処理と後処理を行った。
(5) Example 5
Based on Example 1 above, aluminum sulfate hydrate was replaced with cobalt sulfate, the content of cobalt salt in the post-treatment liquid was changed to 10 g / L in terms of metal, and the post-treatment temperature was changed to 15 ° C. Except for the above, plating and post-treatment were performed under the same conditions as in Example 1 above.
(6)実施例６
上記実施例１を基本として、硫酸アルミニウム水和物をタングステン酸カリウムに代替し、後処理液中のタングステン塩の含有量を金属換算で０.３ｇ／Ｌに変更するとともに、後処理温度を０℃に変更した以外は、上記実施例１と同様の条件で、メッキ処理と後処理を行った。
(6) Example 6
Based on the above Example 1, aluminum sulfate hydrate was replaced with potassium tungstate, the content of tungsten salt in the post-treatment liquid was changed to 0.3 g / L in terms of metal, and the post-treatment temperature was 0. Plating treatment and post-treatment were performed under the same conditions as in Example 1 except that the temperature was changed to ° C.
(7)実施例７
上記実施例１を基本として、硫酸アルミニウム水和物に加えて硫酸マグネシウムを共存させ、後処理液中のアルミニウム塩とマグネシウム塩の含有量を金属換算で夫々１ｇ／Ｌに変更した以外は、上記実施例１と同様の条件で、メッキ処理と後処理を行った。
(7) Example 7
Based on the above Example 1, except that magnesium sulfate was coexisted in addition to aluminum sulfate hydrate, and the contents of aluminum salt and magnesium salt in the post-treatment liquid were changed to 1 g / L in terms of metal, respectively. Plating treatment and post-treatment were performed under the same conditions as in Example 1.
(8)実施例８
上記実施例１を基本として、硫酸アルミニウム水和物に加えて５％第三リン酸ナトリウム水溶液を併用し、後処理液中のアルミニウム塩の含有量を金属換算で１ｇ／Ｌに変更するとともに、後処理温度を７０℃に変更した以外は、上記実施例１と同様の条件で、メッキ処理と後処理を行った。
(8) Example 8
Based on the above Example 1, in addition to aluminum sulfate hydrate, 5% aqueous sodium phosphate solution is used in combination, and the content of aluminum salt in the post-treatment liquid is changed to 1 g / L in terms of metal, Plating treatment and post-treatment were performed under the same conditions as in Example 1 except that the post-treatment temperature was changed to 70 ° C.
(9)比較例１
上記試験片に上記実施例１のスズメッキ処理(ａ)だけを施し、後処理(ｂ)は行わなかった。
(9) Comparative Example 1
Only the tin plating treatment (a) of Example 1 was applied to the test piece, and the post-treatment (b) was not performed.
(10)比較例２
上記実施例１を基本として、硫酸アルミニウム水和物を酢酸バリウムに代替し、後処理液中のバリウム塩の含有量を金属換算で１ｇ／Ｌに変更した以外は、上記実施例１と同様の条件で、メッキ処理と後処理を行った。
(10) Comparative example 2
Based on Example 1 above, aluminum sulfate hydrate was replaced with barium acetate, and the content of barium salt in the post-treatment liquid was changed to 1 g / L in terms of metal, and was the same as Example 1 above. Under conditions, plating treatment and post-treatment were performed.
(11)比較例３
上記実施例１を基本として、硫酸アルミニウム水和物を塩化カルシウムに代替し、後処理液中のカルシウム塩の含有量を金属換算で３ｇ／Ｌに調整した以外は、上記実施例１と同様の条件で、メッキ処理と後処理を行った。
(11) Comparative Example 3
Based on Example 1 above, aluminum sulfate hydrate was replaced with calcium chloride, and the content of calcium salt in the post-treatment liquid was adjusted to 3 g / L in terms of metal, similar to Example 1 above. Under conditions, plating treatment and post-treatment were performed.
そこで、上記実施例１〜８及び比較例２〜３の後処理方法、或は、比較例１のメッキ方法で得られた試験片のメッキ面のハンダ濡れ性を調べた。
《スズメッキ面のハンダ濡れ性試験例》
下記のハンダ濡れ性試験では加速試験を加えて、後処理を行ったメッキ表面を苛酷な雰囲気中に置いてハンダ濡れ性を評価した。
即ち、上記実施例１〜８及び比較例１〜３の処理を行った試験片を下記の条件でハンダ濡れ性試験に供して、ゼロクロスタイム(秒)を測定した。
(Ａ)加速試験
プレッシャークッカーに基づき、温度１０５℃、相対湿度１００％、８時間とした。
(Ｂ)濡れ性試験の条件
ハンダバス：Sn63／Pb37
フラックス：２５％ロジンフラックス／イソプロピルアルコール溶液
バス温度：２１５℃
浸漬深さ：５ｍｍ
Then, the solder wettability of the plating surface of the test piece obtained by the post-processing method of Examples 1 to 8 and Comparative Examples 2 to 3 or the plating method of Comparative Example 1 was examined.
《Solder wettability test example of tin plating surface》
In the following solder wettability test, an accelerated test was added, and the soldered wettability was evaluated by placing the post-treated plating surface in a harsh atmosphere.
That is, the test piece which processed the said Examples 1-8 and the comparative examples 1-3 was used for the solder wettability test on the following conditions, and the zero crossing time (second) was measured.
(A) Acceleration test Based on a pressure cooker, the temperature was 105 ° C., the relative humidity was 100%, and the time was 8 hours.
(B) Wetting test conditions Solder bath: Sn63 / Pb37
Flux: 25% rosin flux / isopropyl alcohol bath temperature: 215 ° C
Immersion depth: 5mm
《スズメッキ面の摩擦試験例》
次いで、下記の条件により、上記実施例１〜８及び比較例２〜３の後処理方法、或は、比較例１のメッキ方法で得られた試験片のメッキ面上で負荷を掛けた鋼材を摺動させて、最大動摩擦係数を測定し、メッキ表面の摩擦の度合を調べた。
［摩擦測定試験条件］
装置 ：新東科学(株)製の表面性試験器
相手材：鋼材
荷重 ：１０gf
速度 ：６０mm／分
<Example of friction test on tin plating surface>
Next, a steel material subjected to a load on the plating surface of the test piece obtained by the post-treatment method of Examples 1 to 8 and Comparative Examples 2 to 3 or the plating method of Comparative Example 1 under the following conditions. The maximum dynamic friction coefficient was measured by sliding, and the degree of friction on the plating surface was examined.
[Friction measurement test conditions]
Equipment: Surface property tester manufactured by Shinto Kagaku Co., Ltd. Counterpart material: Steel material Load: 10 gf
Speed: 60mm / min
ハンダ濡れ性と摩擦試験の結果は次の通りである。
ハンダ濡れ性試験 摩擦試験
ゼロクロスタイム(秒) 最大動摩擦係数
実施例１ １.４ ０.６
実施例２ １.３ ０.６
実施例３ １.４ ０.６
実施例４ １.４ ０.６
実施例５ １.３ ０.６
実施例６ １.３ ０.６
実施例７ １.４ ０.６
実施例８ １.４ ０.６
比較例１ ２.６ １.５
比較例２ ３.３ ０.６
比較例３ ３.３ ０.６
The results of solder wettability and friction test are as follows.
Solder wettability test Friction test
Zero cross time (sec) Maximum dynamic friction coefficient Example 1 1.4 0.6
Example 2 1.3 0.6
Example 3 1.4 0.6
Example 4 1.4 0.6
Example 5 1.3 0.6
Example 6 1.3 0.6
Example 7 1.4 0.6
Example 8 1.4 0.6
Comparative Example 1 2.6 1.5
Comparative Example 2 3.3 0.6
Comparative Example 3 3.3 0.6
《スズ−銅合金メッキ表面を後処理する実施例》
下記の実施例９〜１６のうち、実施例９〜１４は特定金属イオンを単用して、その種類と含有濃度を変えた例、実施例１５はアルミニウムとマグネシウムの両イオンを共存させた例、実施例１６はアルミニウムイオンと共に公知の耐食処理剤であるリン酸塩を併用した例である。尚、スズ−銅合金メッキ表面の実施例ｎ(ｎは９〜１６の整数)の可溶性金属塩の種類、後処理温度と時間は、前記スズメッキ表面の実施例(ｎ−８)と同じであり、例えば、実施例９は実施例１に、実施例１０は実施例２に夫々共通する。
一方、比較例４〜６のうち、比較例４はメッキ表面を後処理しないブランク例、比較例５は上記特許文献１〜３に開示された本発明とは異なる他種金属であるバリウムのイオンを含有させた例、比較例６は同様に他種金属であるカルシウムのイオンを含有させた例である。尚、スズ−銅合金メッキ表面の比較例ｍ(ｍは４〜６の整数)の可溶性金属塩の種類、後処理温度と時間は、前記スズメッキ表面の比較例(ｍ−３)と同じであり、例えば、比較例５は比較例２に、実施例６は実施例３に夫々共通する。
<< Example of post-processing the tin-copper alloy plating surface >>
Of the following Examples 9 to 16, Examples 9 to 14 are examples in which specific metal ions are used alone, and the type and concentration are changed, and Example 15 is an example in which both ions of aluminum and magnesium coexist. Example 16 is an example in which a phosphate, which is a known anticorrosion treatment agent, is used in combination with aluminum ions. The type, post-treatment temperature and time of the soluble metal salt of Example n (n is an integer of 9 to 16) on the tin-copper alloy plating surface are the same as those of Example (n-8) of the tin plating surface. For example, Example 9 is common to Example 1 and Example 10 is common to Example 2.
On the other hand, among Comparative Examples 4 to 6, Comparative Example 4 is a blank example in which the plating surface is not post-treated, and Comparative Example 5 is an ion of barium which is a different kind of metal different from the present invention disclosed in Patent Documents 1 to 3 above. Similarly, Comparative Example 6 is an example in which calcium ions which are other kinds of metals are contained. In addition, the kind of the soluble metal salt of the comparative example m (m is an integer of 4 to 6), the post-treatment temperature and the time of the tin-copper alloy plating surface are the same as the comparative example (m-3) of the tin plating surface. For example, Comparative Example 5 is common to Comparative Example 2, and Example 6 is common to Example 3.
(1)実施例９
(ａ)スズ−銅合金メッキ処理
先ず、下記の組成でスズ−銅合金メッキ浴を建浴した。
メタンスルホン酸第一スズ(Ｓｎ2+として) ２０ｇ／Ｌ
硫酸銅(Ｃｕ2+として) ０.１７ｇ／Ｌ
メタンスルホン酸 １６０ｇ／Ｌ
２,２′−ジチオジアニリン ２ｇ／Ｌ
α−ナフトールポリエトキシレート(EO10モル) ５ｇ／Ｌ
カテコール １ｇ／Ｌ
次いで、２５mm×２５mmの銅板を試験片として、上記スズメッキ浴を用いて、浴温２５℃、陰極電流密度０.４Ａ／ｄｍ2、メッキ時間６０分間の条件で電気メッキを行い、膜厚１０μｍでスズ−銅合金メッキ皮膜を形成した。
その後、スズ−銅合金メッキを施した上記試験片を５％第三リン酸ナトリウムの水溶液に７０℃、３０秒の条件で浸漬した後、純水で水洗した。
(ｂ)メッキ表面の後処理
硫酸アルミニウムの１４水和物(Ａｌ2(ＳＯ4)3・１４Ｈ2Ｏ)を水に溶解することにより、アルミニウムイオンを含有する後処理液を得た。後処理液中の当該アルミニウム塩の含有量は金属換算で２ｇ／Ｌに調整した。
次いで、前記試験片をこの後処理溶液に２５℃、３０秒の条件で浸漬した後、純水で水洗し、ドライヤーで乾燥した。
(1) Example 9
(a) Tin-copper alloy plating treatment First, a tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn 2+ ) 20g / L
Copper sulfate (as Cu 2+ ) 0.17 g / L
Methanesulfonic acid 160g / L
2,2'-dithiodianiline 2g / L
α-Naphthol polyethoxylate (EO10mol) 5g / L
Catechol 1g / L
Next, using a 25 mm × 25 mm copper plate as a test piece, electroplating was performed using the above tin plating bath under conditions of a bath temperature of 25 ° C., a cathode current density of 0.4 A / dm 2 , and a plating time of 60 minutes. A tin-copper alloy plating film was formed.
Thereafter, the test piece subjected to tin-copper alloy plating was immersed in an aqueous solution of 5% sodium triphosphate at 70 ° C. for 30 seconds, and then washed with pure water.
(b) Post-treatment of plating surface An aluminum sulfate-containing post-treatment liquid was obtained by dissolving aluminum sulfate 14-hydrate (Al 2 (SO 4 ) 3 .14H 2 O) in water. The content of the aluminum salt in the post-treatment liquid was adjusted to 2 g / L in terms of metal.
Next, the test piece was immersed in the post-treatment solution at 25 ° C. for 30 seconds, washed with pure water, and dried with a drier.
(2)実施例１０
上記実施例９を基本として、硫酸アルミニウム水和物を硫酸マンガンに代替し、後処理液中のマンガン塩の含有量を金属換算で２０ｇ／Ｌに変更するとともに、後処理温度を６０℃に変更した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(2) Example 10
Based on Example 9 above, aluminum sulfate hydrate was replaced with manganese sulfate, the content of manganese salt in the post-treatment liquid was changed to 20 g / L in terms of metal, and the post-treatment temperature was changed to 60 ° C. Except for the above, plating and post-treatment were performed under the same conditions as in Example 9.
(3)実施例１１
上記実施例９を基本として、硫酸アルミニウム水和物を硫酸ニッケルに代替し、後処理液中のニッケル塩の含有量を金属換算で０.１ｇ／Ｌに変更するとともに、後処理温度を５０℃に変更した以外は、上記実施例９と同様の条件により、メッキ処理と後処理を行った。
(3) Example 11
Based on Example 9 above, aluminum sulfate hydrate was replaced with nickel sulfate, the content of nickel salt in the post-treatment liquid was changed to 0.1 g / L in terms of metal, and the post-treatment temperature was 50 ° C. A plating process and a post-treatment were performed under the same conditions as in Example 9 except for changing to.
(4)実施例１２
上記実施例９を基本として、硫酸アルミニウム水和物を硫酸亜鉛に代替し、後処理液中の亜鉛塩の含有量を金属換算で５０ｇ／Ｌに変更するとともに、後処理温度を３５℃に変更した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(4) Example 12
Based on Example 9 above, aluminum sulfate hydrate was replaced with zinc sulfate, the content of zinc salt in the post-treatment liquid was changed to 50 g / L in terms of metal, and the post-treatment temperature was changed to 35 ° C. Except for the above, plating and post-treatment were performed under the same conditions as in Example 9.
(5)実施例１３
上記実施例９を基本として、硫酸アルミニウム水和物を硫酸コバルトに代替し、後処理液中のコバルト塩の含有量を金属換算で２０ｇ／Ｌに変更するとともに、後処理温度を１５℃に変更した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(5) Example 13
Based on Example 9 above, aluminum sulfate hydrate was replaced with cobalt sulfate, the content of cobalt salt in the post-treatment liquid was changed to 20 g / L in terms of metal, and the post-treatment temperature was changed to 15 ° C. Except for the above, plating and post-treatment were performed under the same conditions as in Example 9.
(6)実施例１４
上記実施例９を基本として、硫酸アルミニウム水和物をタングステン酸カリウムに代替し、後処理液中のコバルト塩の含有量を金属換算で０.６ｇ／Ｌに変更するとともに、後処理温度を０℃に変更した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(6) Example 14
Based on Example 9 above, aluminum sulfate hydrate was replaced with potassium tungstate, the content of cobalt salt in the post-treatment liquid was changed to 0.6 g / L in terms of metal, and the post-treatment temperature was 0. Plating treatment and post-treatment were performed under the same conditions as in Example 9 except that the temperature was changed to ° C.
(7)実施例１５
上記実施例９を基本として、硫酸アルミニウム水和物に加えて硫酸マグネシウムを共存させ、後処理液中のアルミニウム塩とマグネシウム塩の含有量を金属換算で夫々１ｇ／Ｌに変更した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(7) Example 15
Based on the above Example 9, except that magnesium sulfate was coexisted in addition to aluminum sulfate hydrate, and the contents of aluminum salt and magnesium salt in the post-treatment liquid were changed to 1 g / L in terms of metal, respectively. Plating treatment and post-treatment were performed under the same conditions as in Example 9.
(8)実施例１６
上記実施例９を基本として、硫酸アルミニウム水和物に加えて５％第三リン酸ナトリウム水溶液を併用し、後処理液中のアルミニウム塩の含有量を金属換算で１ｇ／Ｌに変更するとともに、後処理温度を７０℃に変更した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(8) Example 16
Based on Example 9 above, in addition to aluminum sulfate hydrate, a 5% aqueous sodium phosphate solution was used in combination, and the content of the aluminum salt in the post-treatment liquid was changed to 1 g / L in terms of metal, Plating treatment and post-treatment were performed under the same conditions as in Example 9 except that the post-treatment temperature was changed to 70 ° C.
(9)比較例４
上記試験片に上記実施例９のスズ−銅合金メッキ処理(ａ)だけを施し、後処理(ｂ)は行わなかった。
(9) Comparative Example 4
Only the tin-copper alloy plating treatment (a) of Example 9 was applied to the test piece, and the post-treatment (b) was not performed.
(10)比較例５
上記実施例９を基本として、硫酸アルミニウム水和物を酢酸バリウムに代替し、後処理液中のバリウム塩の含有量を金属換算で１ｇ／Ｌに変更した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(10) Comparative Example 5
Based on Example 9 above, aluminum sulfate hydrate was replaced with barium acetate, and the content of barium salt in the post-treatment liquid was changed to 1 g / L in terms of metal, similar to Example 9 above. Under conditions, plating treatment and post-treatment were performed.
(11)比較例６
上記実施例９を基本として、硫酸アルミニウム水和物を塩化カルシウムに代替し、後処理液中のカルシウム塩の含有量を金属換算で３ｇ／Ｌに調整した以外は、上記実施例９と同様の条件で、メッキ処理と後処理を行った。
(11) Comparative Example 6
Based on Example 9 above, aluminum sulfate hydrate was replaced with calcium chloride, and the content of calcium salt in the post-treatment liquid was adjusted to 3 g / L in terms of metal, similar to Example 9 above. Under conditions, plating treatment and post-treatment were performed.
《スズ−銅合金メッキ面のハンダ濡れ性試験例》
そこで、上記実施例９〜１６及び比較例５〜６の後処理方法、或は、比較例４のメッキ方法で得られた試験片のメッキ面について、前記スズメッキ面の場合と同様の条件で加速試験も加えて、ハンダ濡れ性試験に供して、ゼロクロスタイム(秒)を測定した。
<Example of solder wettability test on tin-copper alloy plating surface>
Therefore, the plating surface of the test piece obtained by the post-treatment method of Examples 9 to 16 and Comparative Examples 5 to 6 or the plating method of Comparative Example 4 was accelerated under the same conditions as in the case of the tin plating surface. In addition to the test, it was subjected to a solder wettability test, and the zero cross time (seconds) was measured.
《スズ−銅合金メッキ面の摩擦試験例》
次いで、上記実施例９〜１６及び比較例４〜６の試験片のメッキ面について、前記スズメッキ面の場合と同様の条件で最大動摩擦係数を測定し、メッキ表面の摩擦の度合を調べた。
<Example of friction test on tin-copper alloy plating surface>
Next, for the plated surfaces of the test pieces of Examples 9 to 16 and Comparative Examples 4 to 6, the maximum dynamic friction coefficient was measured under the same conditions as those for the tin-plated surface, and the degree of friction on the plated surface was examined.
ハンダ濡れ性と摩擦試験の結果は次の通りである。
ハンダ濡れ性試験 摩擦試験
ゼロクロスタイム(秒) 最大動摩擦係数
実施例９ １.５ ０.７
実施例１０ １.５ ０.７
実施例１１ １.６ ０.７
実施例１２ １.７ ０.７
実施例１３ １.４ ０.７
実施例１４ １.６ ０.７
実施例１５ １.５ ０.７
実施例１６ １.６ ０.７
比較例４ ２.８ １.８
比較例５ ３.６ ０.７
比較例６ ３.５ ０.７
The results of solder wettability and friction test are as follows.
Solder wettability test Friction test
Zero cross time (sec) Maximum dynamic friction coefficient Example 9 1.5 0.7
Example 10 1.5 0.7
Example 11 1.6 0.7
Example 12 1.7 0.7
Example 13 1.4 0.7
Example 14 1.6 0.7
Example 15 1.5 0.7
Example 16 1.6 0.7
Comparative Example 4 2.8 1.8
Comparative Example 5 3.6 0.7
Comparative Example 6 3.5 0.7
《後処理したメッキ表面のハンダ濡れ性の評価》
スズメッキ表面を後処理した実施例１〜８では、後処理を行わなかった比較例１に対して、明らかにゼロクロスタイムが短縮され、後処理がメッキ面のハンダ濡れ性を確実に向上させていることが確認できた。
この場合、後処理液に含有する金属イオンがアルミニウム、マンガン、ニッケル、亜鉛、コバルト、タングステンの各イオンに変化しても、同様のレベルでハンダ濡れ性を改善でき、例えば、アルミニウムイオンでは単位リットル当たり１ケタのグラム数で、また、ニッケルやタングステンのイオンでは１ｇ未満でも有効であり、ごく少量濃度の液に試験片を浸漬してもメッキ表面のハンダ濡れ性を向上できることが確認できた。さらに、後処理温度は室温を中心として、０℃の冷温でも有効であることが確認できた。
また、アルミニウムとマグネシウムの両イオンが共存した実施例７では、アルミニウムイオンを単用した実施例１に比べて、アルミニウムの含有濃度を低減しても同様のハンダ濡れ性の改善効果が得られた。アルミニウムイオンとリン酸塩を併用した実施例８も、アルミニウムイオンの含有濃度を低減しながら、同様にハンダ濡れ性の改善効果が認められた。
<< Evaluation of solder wettability of post-treated plating surface >>
In Examples 1 to 8 where the tin-plated surface was post-treated, the zero cross time was clearly shortened compared to Comparative Example 1 where no post-treatment was performed, and the post-treatment reliably improved the solder wettability of the plated surface. I was able to confirm.
In this case, even if the metal ions contained in the post-treatment liquid are changed to aluminum, manganese, nickel, zinc, cobalt, and tungsten ions, the solder wettability can be improved at the same level. It was confirmed that it was effective in the order of 1 gram per gram, and less than 1 g for nickel and tungsten ions, and the solder wettability of the plating surface could be improved even when the test piece was immersed in a very small concentration of liquid. Further, it was confirmed that the post-treatment temperature was effective even at a cold temperature of 0 ° C., centering on room temperature.
Further, in Example 7 in which both ions of aluminum and magnesium coexisted, the same solder wettability improving effect was obtained even if the aluminum concentration was reduced as compared with Example 1 in which aluminum ions were used alone. . In Example 8 in which aluminum ions and phosphates were used in combination, the effect of improving solder wettability was also observed while reducing the concentration of aluminum ions.
さらに、冒述の特許文献１〜３に開示されたバリウムやカルシウムのイオンを含有させた比較例２〜３を、本発明の特定金属のイオンを含有する実施例１〜８に対比すると、比較例２〜３のゼロクロスタイムはブランク例である比較例１よりも悪いことから、アルミニウムを初めとする本発明の特定金属のイオンは、バリウムやカルシウムのイオンに対してスズメッキ表面のハンダ濡れ性を改善する点で顕著な優位性があることが確認できた。 Further, when Comparative Examples 2 to 3 containing ions of barium and calcium disclosed in Patent Documents 1 to 3 described above are compared with Examples 1 to 8 containing ions of a specific metal of the present invention, a comparison is made. Since the zero cross time of Examples 2 to 3 is worse than that of Comparative Example 1 which is a blank example, the ions of specific metals of the present invention including aluminum have solder wettability on the surface of tin plating against ions of barium and calcium. It was confirmed that there was a significant advantage in terms of improvement.
一方、実施例９〜１６をそのブランク例である比較例４に対比すると、本発明の特定金属のイオンを溶解した水溶液をスズ−銅合金メッキ表面に適用しても、スズメッキ面の場合と同様に、ハンダ濡れ性を顕著に改善できることが判った。
以上のように、プリント基板、チップ部品などの電子部品を初めとする金属材料にスズ系メッキなどの各種メッキを行い、そのメッキ面をハンダ付けに供する場合、予め、アルミニウム、ニッケル、コバルト、タングステンなどのような本発明の特定金属のイオンを含有する水溶液で当該メッキ面を後処理すると、スズやスズ合金を初めとする各種メッキ面のハンダ濡れ性を確実に向上することができる。従って、上記電子部品などをハンダ付けする際の信頼性を良好に担保できる。
On the other hand, when Examples 9-16 are compared with the comparative example 4 which is the blank example, even if the aqueous solution which melt | dissolved the ion of the specific metal of this invention is applied to the tin-copper alloy plating surface, it is the same as the case of a tin plating surface. It was also found that the solder wettability can be remarkably improved.
As described above, when various plating such as tin plating is performed on metal materials such as electronic parts such as printed circuit boards and chip parts, and the plated surface is used for soldering, aluminum, nickel, cobalt, tungsten in advance. When the plated surface is post-treated with an aqueous solution containing specific metal ions of the present invention such as the above, the solder wettability of various plated surfaces including tin and tin alloys can be reliably improved. Therefore, it is possible to satisfactorily ensure the reliability when soldering the electronic parts and the like.
《後処理したメッキ表面の摩擦度合の評価》
スズメッキ表面を本発明の特定金属のイオンで後処理した実施例１〜８では、後処理を行わなかった比較例１に対して、明らかに最大動摩擦係数は低減され、後処理がメッキ面の摩擦抵抗を確実に軽減していることが確認できた。
一方、スズ−銅合金メッキ表面を本発明の特定金属のイオンで後処理した実施例９〜１６では、後処理を行わなかった比較例４に対して、やはり最大動摩擦係数は明らかに低減しており、スズメッキ面と同様に、スズ−銅合金メッキ面についても、後処理がメッキ面の摩擦抵抗の軽減に寄与していることが確認できた。
従って、スズやスズ合金を初めとする各種メッキ面を本発明の特定金属のイオンで後処理すると、メッキ表面の摩擦抵抗を有効に軽減して、バルク実装システムでの電極の擦れによる劣化や削れ屑の発生によるパーツフィーダーへの当該屑の付着を円滑に阻止でき、この面からもプリント基板、チップ部品等の電子部品の信頼性を高めることができる。
尚、バリウムやカルシウムの他種金属のイオンで後処理しても、摩擦抵抗の軽減に関して、本発明の特定金属イオンと同様の作用が認められた(比較例２〜３、比較例５〜６参照)。
<Evaluation of the degree of friction of the post-treated plating surface>
In Examples 1 to 8 where the tin-plated surface was post-treated with ions of the specific metal of the present invention, the maximum dynamic friction coefficient was clearly reduced as compared with Comparative Example 1 where no post-treatment was performed, and the post-treatment was the friction of the plated surface. It was confirmed that the resistance was reliably reduced.
On the other hand, in Examples 9 to 16 in which the tin-copper alloy plating surface was post-treated with ions of the specific metal of the present invention, the maximum dynamic friction coefficient was clearly reduced as compared with Comparative Example 4 in which no post-treatment was performed. As with the tin-plated surface, it was confirmed that the post-treatment also contributed to the reduction of the frictional resistance of the plated surface on the tin-copper alloy-plated surface.
Therefore, post-treatment of various plating surfaces such as tin and tin alloys with ions of the specific metal of the present invention effectively reduces the frictional resistance of the plating surface and causes deterioration and scraping due to electrode rubbing in bulk mounting systems. It is possible to smoothly prevent the scraps from adhering to the parts feeder due to the generation of scraps, and also from this surface, the reliability of electronic components such as printed circuit boards and chip components can be improved.
In addition, even if it post-processes with the ion of the other metal of barium and calcium, the effect | action similar to the specific metal ion of this invention was recognized regarding reduction of frictional resistance (Comparative Examples 2-3, Comparative Examples 5-6). reference).
Claims (6)
上記後処理液が、アルミニウム、マンガン、マグネシウム、ニッケル、亜鉛、コバルト、タングステンよりなる群から選ばれた少なくとも一種の金属イオンを含有する水溶液であることを特徴とするメッキ表面の後処理液。 After forming a plating film of tin, tin alloy, gold, silver, copper, or nickel on the object to be plated, a liquid for post-processing the plating surface,
A post-treatment liquid for a plating surface, wherein the post-treatment liquid is an aqueous solution containing at least one metal ion selected from the group consisting of aluminum, manganese, magnesium, nickel, zinc, cobalt, and tungsten.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056286A (en) * | 2005-08-22 | 2007-03-08 | Rohm & Haas Electronic Materials Llc | Aqueous solution for treating metal surface and method for preventing metal surface from discoloring |
| JP2008248332A (en) * | 2007-03-30 | 2008-10-16 | Nikko Kinzoku Kk | Tin-plated strip and its production method |
| JP2010209391A (en) * | 2009-03-10 | 2010-09-24 | Dowa Metaltech Kk | Method of manufacturing nickel plated material |
| JP2012255205A (en) * | 2011-05-13 | 2012-12-27 | C Uyemura & Co Ltd | Post-treatment agent for tin or tin alloy plating film, and method for treating tin or tin alloy plating film |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11335865A (en) * | 1998-05-21 | 1999-12-07 | Nippon Hyomen Kagaku Kk | Processing agent for forming protective coating film on metal and its formation |
| JP2001032085A (en) * | 1999-07-22 | 2001-02-06 | Nippon Steel Corp | Sn-BASED OR Al-BASED SURFACE TREATED STEEL SHEET USING NO Cr AND CHEMICAL FOR POST-TREATMENT |
| JP2001214280A (en) * | 2000-01-28 | 2001-08-07 | Nippon Steel Corp | Sn SERIES AND Al SERIES PLATED STEEL SHEET COATED WITH Cr- FREE FILM EXCELLENT IN LUBRICITY |
| JP2002158105A (en) * | 2000-11-16 | 2002-05-31 | Tdk Corp | Magnet and its manufacturing method |
| JP2002249885A (en) * | 2001-02-22 | 2002-09-06 | Nippon Steel Corp | Surface treated steel sheet for environmentally friendly electronic parts having excellent solder wettability, rust resistance and whisker resistance |
| JP2003105587A (en) * | 2001-09-27 | 2003-04-09 | Toyo Kohan Co Ltd | Surface treated steel sheet for electronic part, and production method therefor |
| JP2003193256A (en) * | 2001-12-21 | 2003-07-09 | Toshio Odajima | Chromium-free surface treatment agent for metallic material and surface treated metallic material |
| JP2004042630A (en) * | 2002-05-22 | 2004-02-12 | Jfe Steel Kk | Surface-treated metallic sheet |
| JP2004099997A (en) * | 2002-09-11 | 2004-04-02 | Surtec Kariya:Kk | Post treatnig agent for nickel plating film |
| JP2004149889A (en) * | 2002-10-31 | 2004-05-27 | Jfe Steel Kk | Surface treated metallic sheet having excellent press formability and corrosion resistance |
-
2003
- 2003-09-24 JP JP2003332098A patent/JP2005097669A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11335865A (en) * | 1998-05-21 | 1999-12-07 | Nippon Hyomen Kagaku Kk | Processing agent for forming protective coating film on metal and its formation |
| JP2001032085A (en) * | 1999-07-22 | 2001-02-06 | Nippon Steel Corp | Sn-BASED OR Al-BASED SURFACE TREATED STEEL SHEET USING NO Cr AND CHEMICAL FOR POST-TREATMENT |
| JP2001214280A (en) * | 2000-01-28 | 2001-08-07 | Nippon Steel Corp | Sn SERIES AND Al SERIES PLATED STEEL SHEET COATED WITH Cr- FREE FILM EXCELLENT IN LUBRICITY |
| JP2002158105A (en) * | 2000-11-16 | 2002-05-31 | Tdk Corp | Magnet and its manufacturing method |
| JP2002249885A (en) * | 2001-02-22 | 2002-09-06 | Nippon Steel Corp | Surface treated steel sheet for environmentally friendly electronic parts having excellent solder wettability, rust resistance and whisker resistance |
| JP2003105587A (en) * | 2001-09-27 | 2003-04-09 | Toyo Kohan Co Ltd | Surface treated steel sheet for electronic part, and production method therefor |
| JP2003193256A (en) * | 2001-12-21 | 2003-07-09 | Toshio Odajima | Chromium-free surface treatment agent for metallic material and surface treated metallic material |
| JP2004042630A (en) * | 2002-05-22 | 2004-02-12 | Jfe Steel Kk | Surface-treated metallic sheet |
| JP2004099997A (en) * | 2002-09-11 | 2004-04-02 | Surtec Kariya:Kk | Post treatnig agent for nickel plating film |
| JP2004149889A (en) * | 2002-10-31 | 2004-05-27 | Jfe Steel Kk | Surface treated metallic sheet having excellent press formability and corrosion resistance |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056286A (en) * | 2005-08-22 | 2007-03-08 | Rohm & Haas Electronic Materials Llc | Aqueous solution for treating metal surface and method for preventing metal surface from discoloring |
| EP1757715A3 (en) * | 2005-08-22 | 2014-12-24 | Rohm and Haas Electronic Materials LLC | Aqueous solution for surface treatment of tin films and method for preventing discoloration of a tin film surface |
| JP2008248332A (en) * | 2007-03-30 | 2008-10-16 | Nikko Kinzoku Kk | Tin-plated strip and its production method |
| JP2010209391A (en) * | 2009-03-10 | 2010-09-24 | Dowa Metaltech Kk | Method of manufacturing nickel plated material |
| JP2012255205A (en) * | 2011-05-13 | 2012-12-27 | C Uyemura & Co Ltd | Post-treatment agent for tin or tin alloy plating film, and method for treating tin or tin alloy plating film |
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