JP4231936B2 - Method for producing Sn-coated copper - Google Patents
Method for producing Sn-coated copper Download PDFInfo
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- JP4231936B2 JP4231936B2 JP2003376526A JP2003376526A JP4231936B2 JP 4231936 B2 JP4231936 B2 JP 4231936B2 JP 2003376526 A JP2003376526 A JP 2003376526A JP 2003376526 A JP2003376526 A JP 2003376526A JP 4231936 B2 JP4231936 B2 JP 4231936B2
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- 229910052802 copper Inorganic materials 0.000 title claims description 24
- 239000010949 copper Substances 0.000 title claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000007747 plating Methods 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 238000006386 neutralization reaction Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 48
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 6
- 235000019801 trisodium phosphate Nutrition 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- ZRBROGSAUIUIJE-UHFFFAOYSA-N azanium;azane;chloride Chemical compound N.[NH4+].[Cl-] ZRBROGSAUIUIJE-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Description
本発明は，リフロー処理を伴うＳｎ被覆銅材の製法に関する。 The present invention relates to a method for producing a Sn-coated copper material with reflow treatment.
銅または銅合金の表面にＳｎまたはＳｎ合金めっきを施すＳｎ被覆銅材では，めっきの表面性状や耐ウイスカ性の改善のために，めっき層を加熱溶融して凝固させるいわゆるリフロー処理が施されるのが通常である。リフロー処理を行うに際しては，その前に種々の予備処理が施される。その代表的なものとしてアルカリ水溶液，特にリン酸三ナトリウム水溶液を用いる前処理が知られている。 In the Sn-coated copper material in which Sn or Sn alloy plating is applied to the surface of copper or copper alloy, so-called reflow treatment is performed in which the plating layer is heated and melted and solidified in order to improve the surface properties and whisker resistance of the plating. It is normal. Before performing the reflow process, various preliminary processes are performed. A typical example is a pretreatment using an alkaline aqueous solution, particularly a trisodium phosphate aqueous solution.
リフロー前処理剤としてリン酸三ナトリウム水溶液を用いると，リフロー条件を安定化し，外観光沢を向上させることができるが，リン酸三ナトリウム懸濁粒子が表面に強く付着し，水洗によっても取れずに残ることがあり，これが表面欠陥となることがある。その改善法として，塩化アンモニウム−アンモニア緩衝溶液を用いて，表面に処理薬品を残さないような方法も提案されているが，微量不純物が残存しやすく光沢の低下が起きるおそれがある。 When trisodium phosphate aqueous solution is used as a reflow pretreatment agent, reflow conditions can be stabilized and appearance gloss can be improved, but trisodium phosphate suspended particles adhere strongly to the surface and cannot be removed by washing with water. It may remain and this may be a surface defect. As an improvement method, a method has been proposed in which an ammonium chloride-ammonia buffer solution is used so as not to leave a treatment chemical on the surface. However, there is a possibility that a slight amount of impurities easily remain and the gloss is lowered.
この点を改善する方法として，特許文献１は，水分を金属表面から取り除く機能をもつ有機系の液体，例えばアルコール類，グリコール類，トリクロールエチレン等の水置換剤を用いれば，微量不純物も水分とともに取り除くことができると教示している。 As a method for improving this point, Patent Document 1 discloses that an organic liquid having a function of removing moisture from a metal surface, for example, a water substitution agent such as alcohols, glycols, trichlorethylene or the like can be used to remove trace impurities. And can be removed.
特許文献２には，リフロー前処理剤としてＳｎ塩の水溶液をフラックスとして用いると表面異常が改善され，はんだ付け性，耐食性も向上すると教示している。 Patent Document 2 teaches that when an aqueous solution of Sn salt is used as a reflow pretreatment agent as a flux, surface abnormality is improved and solderability and corrosion resistance are also improved.
リフロー前処理剤として，アルカリ性のリン酸三ナトリウムを水溶液を用いた場合に発生する懸濁粒子の残存に対して，アルコール，グリコール，トリクロールエチレンなど有機系の液体を用いて除去する方法は，設備汚染や排水処理の問題が懸念され，Ｓｎ塩の水溶液をフラックスとして用いる方法はそれなりの効果が期待されるが，新たに試薬を使用する点では変わりはなく，費用が嵩む。 As a reflow pretreatment agent, the method of removing the remaining suspended particles generated by using an aqueous solution of alkaline trisodium phosphate with an organic liquid such as alcohol, glycol, trichlorethylene, There is concern about equipment contamination and wastewater treatment, and the method of using an aqueous solution of Sn salt as a flux is expected to have a certain effect, but it does not change in terms of newly using a reagent, and costs increase.
したがって，本発明は，従来のアルカリ水溶液を用いる予備処理工程において，新たな試薬を使用することなく，場合によっては工程を簡略化して，リフローの前処理効果を高めることを目的としたものである。 Accordingly, an object of the present invention is to enhance the pretreatment effect of reflow by simplifying the process in some cases without using a new reagent in the conventional pretreatment process using an alkaline aqueous solution. .
本発明者らは，Ｓｎめっき後の酸性成分の除去に対してはアルカリ水溶液による中和処理を実施したうえで，温水による付着成分の除去と，引き続き酸化防止のための速やかな乾燥処理を実施すれば，前記の課題が解決できることがわかった。場合によっては，アルカリ水溶液による中和処理を省略して，ｐＨ４以下の酸性温水による洗浄を行ったうえ，乾燥しても同様の目的が達成可能であることがわかった。 The present inventors performed neutralization treatment with an alkaline aqueous solution for removal of acidic components after Sn plating, followed by removal of adhering components with hot water and subsequent rapid drying treatment for preventing oxidation. It was found that the above problems could be solved. In some cases, it was found that neutralization treatment with an alkaline aqueous solution was omitted, washing with acidic warm water having a pH of 4 or less, and drying could achieve the same purpose.
したがって、本発明によれば、銅または銅合金の表面にＳｎまたはＳｎ合金めっきを施したあと、該めっき表面を予備処理してから該めっき層のリフロー処理を施すＳｎ被覆銅材の製法において、該予備処理として、（１）ｐＨ４以下で５０℃以上の酸性温水による酸性温水洗浄処理および乾燥処理を順に行うこと、更には、（２）アルカリ性水溶液による付着めっき液の中和処理、ｐＨ４以下で５０℃以上の酸性温水による酸性温水洗浄処理および乾燥処理を順に行うこと、を特徴とするＳｎ被覆銅材の製法を提供する。 Therefore, according to the present invention, after the Sn or Sn alloy plating is performed on the surface of the copper or copper alloy, the plating surface is pretreated and then the reflow treatment of the plating layer is performed. As the preliminary treatment, (1) an acidic hot water washing treatment and a drying treatment with acidic hot water at a pH of 4 or lower and 50 ° C. or higher are sequentially performed; and (2) an adhesion plating solution neutralization treatment with an alkaline aqueous solution; Provided is a method for producing a Sn-coated copper material, characterized in that an acidic hot water washing treatment and a drying treatment with acidic hot water of 50 ° C. or higher are sequentially performed.
本発明法では，従来と同様のアルカリ性水溶液による付着めっき液の中和処理をリフロー前処理として施したうえ，温水による洗浄と洗浄水の乾燥を行うことで前記の課題を解決したものであるから，新たな試薬の使用や設備の増設は実質的に不要であり，このために非常に廉価にしてリフロー処理後のＳｎ被覆銅材の表面性状を改善することができ，あわせてめっき密着性や耐食性も改善することができる。 In the method of the present invention, the above-mentioned problems are solved by performing neutralization treatment of the adhesion plating solution with an alkaline aqueous solution as before as reflow pretreatment, and washing with warm water and drying of the washing water. The use of new reagents and the addition of new equipment are virtually unnecessary. Therefore, the surface properties of the Sn-coated copper material after reflow treatment can be improved at a very low price, and the plating adhesion and Corrosion resistance can also be improved.
本発明のＳｎ被覆銅材の製法において，銅または銅合金の表面にＳｎまたはＳｎ合金めっきを施す点は従来と同様であり，ＳｎまたはＳｎ合金めっき層のリフロー処理を施す点も従来と同様である。したがって，ここまでは従来の技術をそのまま採用することができる。また，リフロー処理の予備処理として，Ｓｎめっきのあとにアルカリ水溶液による付着めっき液の中和処理を行う点でも，従来技術と特に変わりはない。 In the production method of the Sn-coated copper material of the present invention, the point that the Sn or Sn alloy plating is applied to the surface of the copper or copper alloy is the same as the conventional method, and the point that the reflow treatment of the Sn or Sn alloy plating layer is performed is the same as the conventional method. is there. Therefore, the conventional technology can be used as it is so far. Further, as a pretreatment for the reflow treatment, there is no particular difference from the prior art in that the plating treatment solution is neutralized with an alkaline aqueous solution after Sn plating.
しかし，アルカリ水溶液による付着めっき液の中和処理を行ったあとは，特許文献１や特許文献２の方法とは異なり，温水洗浄と乾燥処理を行う。温水洗浄は，５０℃以上の温水または５０℃以上の硫酸酸性水溶液を使用する。乾燥処理は温風乾燥が好ましい。 However, after the neutralization treatment of the adhesion plating solution with an alkaline aqueous solution, unlike the methods of Patent Document 1 and Patent Document 2, warm water cleaning and drying treatment are performed. Hot water washing uses hot water of 50 ° C. or higher or sulfuric acid aqueous solution of 50 ° C. or higher. The drying treatment is preferably hot air drying.
以下に，本発明法で特定する事項について説明する。
まず，酸性のＳｎまたはＳｎ合金めっき浴にてＳｎまたはＳｎ合金めっきを行った後，アルカリ水溶液を塗布して，めっき後表面に残留している酸性成分の中和を行うが，この中和処理に用いるアルカリ水溶液は排水処理やコスト等の点から従来と同様のリン酸三ナトリウム水溶液が望ましい。その処理としては，例えば２〜８％程度のリン酸三ナトリウム水溶液を２０〜５０℃に保持した浴に，めっき処理品を２〜８秒間浸漬する方法が簡便である。この浸漬に代えて，同様のアルカリ水溶液を噴霧する方法でもよい。
The matters specified by the method of the present invention will be described below.
First, after Sn or Sn alloy plating is carried out in an acidic Sn or Sn alloy plating bath, an alkaline aqueous solution is applied to neutralize acidic components remaining on the surface after plating. The alkaline aqueous solution used in the above is preferably a trisodium phosphate aqueous solution similar to the conventional one from the viewpoint of wastewater treatment and cost. As the treatment, for example, a method of immersing the plated product in a bath in which about 2 to 8% trisodium phosphate aqueous solution is maintained at 20 to 50 ° C. for 2 to 8 seconds is convenient. Instead of this immersion, a method of spraying a similar alkaline aqueous solution may be used.
なお，前記のＳｎまたはＳｎ合金めっきの前に，母材表面に対して電解脱脂や化学研磨等の前処理を施すことにより，母材とめっきの密着性あるいは耐熱性の向上を図ることが望ましい。また，ＳｎまたはＳｎ合金めっきの前に下地処理として母材にＣｕまたはＣｕ合金あるいはＮｉまたはＮｉ合金のめっきを施すこともできる。 In addition, it is desirable to improve adhesion between the base material and the plating or heat resistance by performing pretreatment such as electrolytic degreasing and chemical polishing on the surface of the base material before the Sn or Sn alloy plating. . Further, before the Sn or Sn alloy plating, the base material can be plated with Cu or Cu alloy or Ni or Ni alloy as a base treatment.
一般に，めっき後表面にめっき浴の酸性成分が残ったままリフロー処理に供すると，めっき表面に形成したＳｎの酸化物によって表面の溶融温度に変化が生じ，リフローの均一性が損なわれる結果，リフロー後に得られるめっき材の外観光沢が損なわれる。しかし，前記のようにアルカリ水溶液の塗布により表面がエッチングされ（Ｓｎは両性金属であるから酸にもアルカリにも溶解する），Ｓｎの酸化物の生成も防止されると共に表面が平滑化される効果も生ずると考えられる。なお，このアルカリ水溶液による中和処理を行うさいには，めっき浴の液の持ち込みをできるだけ防ぐために，めっき後，水洗してからこの中和処理を行うのが好ましい。 In general, if reflow treatment is performed with the acidic components of the plating bath remaining on the surface after plating, the surface melting temperature is changed by the Sn oxide formed on the plating surface, and the reflow uniformity is impaired. The appearance gloss of the plating material obtained later is impaired. However, as described above, the surface is etched by application of an alkaline aqueous solution (Sn is an amphoteric metal, so it dissolves in both acid and alkali), and the formation of Sn oxide is prevented and the surface is smoothed. An effect is also expected to occur. In performing the neutralization treatment with the alkaline aqueous solution, it is preferable to carry out the neutralization treatment after plating and washing with water in order to prevent the introduction of the solution in the plating bath as much as possible.
前記のアルカリ水溶液による中和処理のあとは，引き続き温水洗浄処理と乾燥処理を実施する。温水洗浄処理は，中和処理のあとのめっき品を，好ましくは水洗したあと，５０℃以上の温水を収容した温水槽に浸漬する処理を行う。温水槽への浸漬に代えて温水スプレーを噴射する処理を行ってもよい。この温水洗浄処理を行うことによって，めっき品表面の水分が直ちに乾燥しやすくなり，Ｓｎめっき表面が酸化するのを防止することができる。その効果を助成するために，乾燥処理もブロワーによる空気吹き付け或いは温風吹き付けを実施するのが好ましい。アルカリ水溶液による中和処理のあと水洗したとしても，その状態では乾燥するのに時間を要し，その間に，Ｓｎめっき表面にＳｎの酸化物がところどころに不均一に生成し，これがリフロー処理の条件変化をもたらす原因となっていることがわかった。したがって，水洗だけでは不十分であり，適当な温度，すなわち５０℃以上，好ましくは６０℃以上の温水を用いた温水洗浄と積極的な乾燥処理を組み合わせることによって，アルカリ水溶液による中和処理のあとは，可及的速やかに付着水分を除去することが本発明の目的を達成するうえで肝要である。 After the neutralization treatment with the alkaline aqueous solution, a hot water washing treatment and a drying treatment are subsequently performed. In the hot water washing treatment, the plated product after the neutralization treatment is preferably washed and then immersed in a hot water tank containing hot water of 50 ° C. or higher. You may perform the process which sprays a warm water spray instead of being immersed in a warm water tank. By performing this warm water cleaning treatment, the moisture on the surface of the plated product can be easily dried immediately, and the Sn plating surface can be prevented from being oxidized. In order to subsidize the effect, it is preferable that the drying process is performed by air blowing or hot air blowing by a blower. Even if it is washed with water after neutralization treatment with an alkaline aqueous solution, it takes time to dry in that state, and during that time, Sn oxides are unevenly formed on the surface of the Sn plating, and this is the condition of the reflow treatment. It turns out that it is the cause of change. Therefore, washing with water alone is not sufficient, and after neutralization with an alkaline aqueous solution by combining warm water washing with warm water at an appropriate temperature, ie, 50 ° C. or more, preferably 60 ° C. or more, and aggressive drying treatment. In order to achieve the object of the present invention, it is important to remove adhering water as quickly as possible.
この温水洗浄処理は，洗浄水として温度が５０℃以上の硫酸または塩酸酸性水溶液を使用することもできる。とくに，ｐＨ４以下の硫酸または塩酸酸性水溶液を使用するのが好ましい。このような酸性水溶液を使用することによって，アルカリ水溶液による中和処理を行ったさいに，付着残存しているアルカリ水溶液を除去することができ，これによって，単に温水を使用する場合に比べて，水分の乾燥の他にアルカリ水溶液の除去もできるので，リフロー処理後の表面外観を一層良好なものとすることができる。この酸性水溶液を使用する場合にもその温度は５０℃以上，好ましくは６０℃以上とするのがよい。また，ｐＨは４以下とすることによってアルカリ水溶液を効率よく除去できる。 In this warm water washing treatment, sulfuric acid or hydrochloric acid acidic aqueous solution having a temperature of 50 ° C. or higher can be used as washing water. In particular, it is preferable to use a sulfuric acid or hydrochloric acid acidic aqueous solution having a pH of 4 or less. By using such an acidic aqueous solution, it is possible to remove the remaining alkaline aqueous solution during neutralization treatment with an alkaline aqueous solution, and as a result, compared to simply using warm water, Since the aqueous alkali solution can be removed in addition to drying the moisture, the surface appearance after the reflow treatment can be further improved. Even when this acidic aqueous solution is used, the temperature is 50 ° C. or higher, preferably 60 ° C. or higher. Moreover, alkaline aqueous solution can be efficiently removed by making pH into 4 or less.
最も簡略な方法として，アルカリ水溶液による中和処理を省略し，ｐＨ４以下で５０℃以上の硫酸または塩酸酸性水溶液による洗浄処理と乾燥処理だけでリフロー予備処理を実施することもでき，この場合にも，リフロー後のめっき表面は良好な外観を有し，且つはんだ付け性や耐食性も充分なものが得られる。これは，アルカリ水溶液による中和処理の省略により懸濁粒子の発生を回避することができるうえ，酸性水溶液によるＳｎめっき表面の平滑化と温熱効果による乾燥が速やかに行われる結果，めっき表面にＳｎ酸化物の不均一な生成が回避されるからであろうと推察される。酸性水溶液のｐＨは４以下としたが，ｐＨが４を超える領域では平滑化のためのエッチング効果も十分得られない。 As the simplest method, the neutralization treatment with an alkaline aqueous solution can be omitted, and the reflow pretreatment can be carried out only by washing with sulfuric acid or hydrochloric acid acidic solution at pH 4 or lower and 50 ° C. or higher, and drying treatment. The plated surface after reflow has a good appearance, and has sufficient solderability and corrosion resistance. This is because the generation of suspended particles can be avoided by omitting the neutralization treatment with the alkaline aqueous solution, and the Sn plating surface is smoothed by the acidic aqueous solution and the heating effect is quickly dried. It is surmised that this would be due to the avoidance of non-uniform oxide formation. The pH of the acidic aqueous solution is 4 or less, but in the region where the pH exceeds 4, the etching effect for smoothing cannot be sufficiently obtained.
このようにして，本発明によるリフロー前処理によれば，リフロー前のＳｎめっき表面は酸化物層が薄く且つ平滑なものとなるので，リフロー条件が安定し，その結果，外観光沢に優れ，且つはんだ付け性および耐食性に優れたＳｎ被覆銅材を得ることができる。また，リフロー条件が安定化することにより，リフロー炉における温度範囲を，優れた外観光沢を得ることができるように，広くすることができ，高品質のＳｎ被覆銅材を操業性よく製造することができる。 Thus, according to the reflow pretreatment according to the present invention, the Sn plating surface before reflow has a thin and smooth oxide layer, so that the reflow conditions are stable, and as a result, the appearance gloss is excellent, and An Sn-coated copper material excellent in solderability and corrosion resistance can be obtained. In addition, by stabilizing the reflow conditions, the temperature range in the reflow furnace can be widened so that excellent appearance gloss can be obtained, and high-quality Sn-coated copper material is manufactured with good operability. Can do.
〔実施例１〕
下記の銅合金の条材に対して，下記のめっき条件で電気Ｓｎめっきを施した。
被めっき条材・・Ｎｉ：1.0 mass％, Ｓｎ：0.9 mass％, Ｐ：0.05mass％, 残部残部が銅からなる幅180 mmのＣＤＡ：C19025の銅合金条。
Ｓｎめっき浴・・ＳｎＳＯ4：６０ｇ／Ｌ，Ｈ2ＳＯ4：６０ｇ／Ｌ，光沢剤入り。
めっき条件・・電流密度 0.055Ａ／cm2(5.5Ａ／dm2),めっき厚 7.3×10-12ｇ／m2 (１μｍ) 。
[Example 1]
The following copper alloy strips were electroplated under the following plating conditions.
Plate material to be plated ···: Ni: 1.0 mass%, Sn: 0.9 mass%, P: 0.05 mass%, the balance is 180 mm width CDA: C19025 copper alloy strip.
Sn plating bath · SnSO 4 : 60 g / L, H 2 SO 4 : 60 g / L, with brightener.
Plating conditions: Current density 0.055 A / cm 2 (5.5 A / dm 2 ) , plating thickness 7.3 × 10 -12 g / m 2 (1 μm).
得られたＳｎめっき銅条を，水洗したあと，アルカリ水溶液による中和処理を行った。この中和処理は，浴温４０℃に保持された５％Ｎａ3ＰＯ4の透明水溶液（ｐＨ＝１１）に対し，Ｓｎめっき銅条を約５秒間浸漬する処理である。 The obtained Sn-plated copper strip was washed with water and then neutralized with an aqueous alkaline solution. This neutralization treatment is a treatment in which Sn-plated copper strips are immersed in a transparent aqueous solution (pH = 11) of 5% Na 3 PO 4 kept at a bath temperature of 40 ° C. for about 5 seconds.
次いで，水洗したあと，６０℃の水を蓄えた水槽に約２秒間浸漬する温水洗浄処理を施し（温水のｐＨは約８であった），水槽から出たＳｎめっき銅条をブロワーで空気を吹きつけて乾燥し，リフロー処理に供した。 Next, after washing with water, a hot water washing treatment is performed by immersing in a water tank storing 60 ° C. water for about 2 seconds (the pH of the hot water was about 8), and the Sn-plated copper strip from the water tank was blown with a blower. It sprayed and dried and used for reflow processing.
リフロー処理では乾燥後のＳｎめっき銅条をバーナー炉に装入し，大気中で炉内温度 600〜800 ℃に３〜５秒間保持し，その後水冷した。得られた処理品の表面状態を観察し，下記の基準で表面外観を評価すると共に，はんだ付け性試験，耐食性試験および耐ウイスカ性試験を行ない，それらの結果を下記の基準で評価した。評価結果は表１に示した。 In the reflow treatment, the dried Sn-plated copper strip was charged into a burner furnace, kept in the furnace at 600 to 800 ° C. in the atmosphere for 3 to 5 seconds, and then cooled with water. The surface condition of the obtained treated product was observed, the surface appearance was evaluated according to the following criteria, and the solderability test, the corrosion resistance test, and the whisker resistance test were performed. The results were evaluated according to the following criteria. The evaluation results are shown in Table 1.
〔表面外観〕：中心線平均粗さＲａを測定し，次の基準によって評価した。
◎印・・Ｒａ：0.02μｍ未満 (光沢良好)
○印・・Ｒａ：0.02〜0.04μｍ未満 (光沢やや良好)
×印・・Ｒａ：0.04μｍ以上( 光沢不良)
[Surface appearance]: Centerline average roughness Ra was measured and evaluated according to the following criteria.
◎ mark ・ ・ Ra: Less than 0.02μm (good gloss)
○ mark Ra: 0.02 to less than 0.04 μm (slightly good gloss)
× mark Ra: 0.04μm or more (Poor gloss)
〔はんだ性〕
はんだ付け性試験方法：JIA C 0053 (平衡法) に準じて試験し，下記基準で評価した。
はんだ付け性評価基準
◎印・・ゼロクロスタイム：1.0 秒未満
○印・・ゼロクロスタイム：1.0 秒〜1.5 秒未満
×印・・ゼロクロスタイム：1.5 秒以上
[Solderability]
Solderability test method: Tested according to JIA C 0053 (equilibrium method) and evaluated according to the following criteria.
Solderability Evaluation Criteria ◎ mark ・ ・ Zero cross time: Less than 1.0 second ○ mark ・ ・ Zero cross time: 1.0 to less than 1.5 seconds × mark ・ ・ Zero cross time: 1.5 seconds or more
〔耐食性〕
耐食性試験方法：JIS Z 2371 (塩水噴霧試験法) に準じて試験し，下記基準で評価した。
耐食性評価基準
◎印・・レイティングＮo.６（腐食面積率：0.5 〜1.0 ％未満)
○印・・レイティングＮo.５（腐食面積率：1.0 〜2.5 ％未満)
×印・・レイティングＮo.４（腐食面積率：2.5 〜5.0 ％)
[Corrosion resistance]
Corrosion resistance test method: Tested according to JIS Z 2371 (salt spray test method) and evaluated according to the following criteria.
Corrosion resistance evaluation criteria ◎ mark Rating No. 6 (corrosion area rate: 0.5 to less than 1.0%)
○ Rating No. 5 (corrosion area rate: 1.0 to less than 2.5%)
× Rating No. 4 (corrosion area ratio: 2.5 to 5.0%)
〔耐ウイスカ性〕
耐ウイスカ性試験方法：厚さ0.25ｍｍ×幅10ｍｍ×長さ40ｍｍのサンプルを，−３５℃×１５分保持したあと＋１２５℃×１５分保持を１サイクルとして，１０００サイクルのヒートサイクルに供し，試験後のサイプルの表面を電子顕微鏡（ＳＥＭ）観察し，ウイスカの発生の有無を調べ，次の基準で耐ウイスカ性を評価した。
耐ウイスカ性評価基準
○印・・サンプル表面にウイスカの発生が見られなかったもの
×印・・サンプル表面にウイスカの発生が見られたもの
[Whisker resistance]
Whisker resistance test method: A sample having a thickness of 0.25 mm, a width of 10 mm, and a length of 40 mm is held at -35 ° C. for 15 minutes, and then + 125 ° C. for 15 minutes. The surface of the subsequent sipele was observed with an electron microscope (SEM), the presence or absence of whisker generation was examined, and whisker resistance was evaluated according to the following criteria.
Evaluation standard for whisker resistance ○ mark ··· No whisker generation on the sample surface × · · · Whisker generation observed on the sample surface
〔実施例２〕
温水洗浄処理を，６０℃の温水に代えて，温度６０℃でｐＨ＝約３の硫酸酸性水溶液に代えた以外は実施例１を繰り返した。得られた処理品の表面性状，はんだ性，耐食性および耐ウイスカ性を実施例１と同様に評価した結果を表１に併記した。
[Example 2]
Example 1 was repeated except that the hot water washing treatment was replaced with 60 ° C. warm water and a sulfuric acid aqueous solution having a pH of about 3 at a temperature of 60 ° C. The results of evaluating the surface properties, solderability, corrosion resistance, and whisker resistance of the treated products in the same manner as in Example 1 are also shown in Table 1.
〔実施例３〕
アルカリ水溶液による中和処理を行わなかった以外は，実施例２を繰り返した。得られた処理品の表面性状，はんだ性，耐食性および耐ウイスカ性を実施例１と同様に評価した結果を表１に併記した。
Example 3
Example 2 was repeated except that neutralization with an alkaline aqueous solution was not performed. The results of evaluating the surface properties, solderability, corrosion resistance, and whisker resistance of the treated products in the same manner as in Example 1 are also shown in Table 1.
〔比較例１〕
アルカリ水溶液による中和処理も温水洗浄も行わなかった以外は，実施例１を繰り返した。得られた処理品の表面性状，はんだ性，耐食性および耐ウイスカ性を実施例１と同様に評価した結果を表１に併記した。
[Comparative Example 1]
Example 1 was repeated except that neither the neutralization treatment with the alkaline aqueous solution nor the warm water washing was performed. The results of evaluating the surface properties, solderability, corrosion resistance, and whisker resistance of the treated products in the same manner as in Example 1 are also shown in Table 1.
〔比較例２〕
アルカリ水溶液による中和処理を行わずに６０℃の温水（ｐＨ＝約８）による温水洗浄処理を行った以外は，実施例１を繰り返した。得られた処理品の表面性状，はんだ性，耐食性および耐ウイスカ性を実施例１と同様に評価した結果を表１に併記した。
[Comparative Example 2]
Example 1 was repeated except that the hot water washing treatment with 60 ° C. warm water (pH = about 8) was performed without the neutralization treatment with the alkaline aqueous solution. The results of evaluating the surface properties, solderability, corrosion resistance, and whisker resistance of the treated products in the same manner as in Example 1 are also shown in Table 1.
表１の結果から次のことがわかる。
(1) アルカリ水溶液による中和処理を行うか否かに拘わらず, ６０℃の酸性水溶液で洗浄したものは，外観光沢，はんだ付け性および耐食性が良好である。
(2) とくに，アルカリ水溶液による中和処理を行ない，且つ６０℃の酸性水溶液で洗浄したものは，外観光沢，はんだ付け性および耐食性がすべて非常に良好である。
(3) アルカリ水溶液による中和処理を行っても，６０℃の温水洗浄を行わなかったものは外観が不良である。
(4) アルカリ水溶液による中和処理を行なわず，６０℃の温水洗浄も行わなかったものは外観およびはんだ付け性とも不良である。
(5) アルカリ水溶液による中和処理，６０℃の酸性水溶液での洗浄を行っても，良好な耐ウイスカ性が保持される。
The following can be seen from the results in Table 1.
(1) Regardless of whether or not neutralization is performed with an alkaline aqueous solution, the one washed with an acidic aqueous solution at 60 ° C has good appearance gloss, solderability and corrosion resistance.
(2) In particular, those that are neutralized with an alkaline aqueous solution and washed with an acidic aqueous solution at 60 ° C are all excellent in terms of appearance, solderability, and corrosion resistance.
(3) Even if neutralization with an alkaline aqueous solution was performed, the appearance of the product that was not washed with warm water at 60 ° C was poor.
(4) Those that were not neutralized with an alkaline aqueous solution and not washed with hot water at 60 ° C had poor appearance and solderability.
(5) Good whisker resistance is maintained even after neutralization with an alkaline aqueous solution and washing with an acidic aqueous solution at 60 ° C.
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