JP2005023405A - Copper electroplating solution and copper electroplating method - Google Patents
Copper electroplating solution and copper electroplating method Download PDFInfo
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本発明は電解銅めっき液及び電解銅めっき方法に関し、更に詳細にはシアン化合物が実質的に非含有の電解銅めっき液及び電解銅めっき方法に関する。 The present invention relates to an electrolytic copper plating solution and an electrolytic copper plating method, and more particularly to an electrolytic copper plating solution and an electrolytic copper plating method that are substantially free of a cyanide compound.
従来から電解銅めっきは、電気・電子部品の製造に広く用いられており、例えば４２材（Fe-Ni合金）から成るリードフレームには、直接銀めっきを施すことができないため、先ず、リードフレームの表面全面に銅のストライクめっきを施す。
かかる銅のストライクめっきは、一般的には、シアン化合物が配合された電解銅めっき液（シアン浴）が採用されている。
しかし、シアン浴を用いる場合には、シアン化合物の毒性のため、電解銅めっき中の安全性及びシアン浴の廃液処理作業中の安全性の確保、廃液処理を施した廃液自体の安全性の確保について細心の注意を払う必要がある。
このため、シアン浴を用いることなく部材表面に銅めっきを施すことのできる電解銅めっき液について検討されており、例えば下記特許文献１に、シアン化合物が非含有の非シアン浴としての電解銅めっき液が提案されている。
Such copper strike plating generally employs an electrolytic copper plating solution (cyan bath) containing a cyanide compound.
However, when a cyan bath is used, due to the toxicity of cyanide compounds, safety during electrolytic copper plating, safety during waste liquid treatment of the cyan bath, and safety of the waste liquid itself after waste liquid treatment are ensured. Need to pay close attention to.
For this reason, an electrolytic copper plating solution that can perform copper plating on the surface of a member without using a cyan bath has been studied. For example, Patent Document 1 listed below discloses an electrolytic copper plating as a non-cyan bath containing no cyanide compound. Liquid has been proposed.
前記特許文献１に提案された非シアン浴としての電解銅めっき液によれば、４２材から成るリードフレームの表面に、銅のストライクめっきを施すことができる。
ところで、電解銅めっき液を廃棄処理する際には、電解銅めっき液中に含有されている種々の金属を沈殿処理すべく、種々の薬品が添加される。
しかし、電解銅めっき液に、前記特許文献１の電解銅めっき液のようにキレート剤が配合されていると、電解銅めっき液の廃棄処理工程で添加された薬品が銅イオンと沈殿を作ることができず、廃液処理を妨げることがある。
According to the electrolytic copper plating solution as a non-cyan bath proposed in Patent Document 1, copper strike plating can be applied to the surface of a lead frame made of 42 materials.
By the way, when the electrolytic copper plating solution is discarded, various chemicals are added in order to precipitate various metals contained in the electrolytic copper plating solution.
However, when a chelating agent is blended in the electrolytic copper plating solution as in the electrolytic copper plating solution of Patent Document 1, the chemical added in the disposal process of the electrolytic copper plating solution creates a precipitate with copper ions. Cannot be performed, and waste liquid treatment may be hindered.
このため、電解銅めっき液を廃棄処理する際には、まず電解銅めっき液中に含有されているキレート剤を除去することが必要となるが、廃棄処理する電解銅めっき液からキレート剤を除去することは困難である。
一方、前記特許文献１に提案された電解銅めっき液では、キレート剤を添加しないと、銅の錯体から成る沈殿物が生成されるため、到底、実用に供し得ないものである。
そこで、本発明の課題は、シアン化合物及びキレート剤が実質的に非含有であって、部材表面に密着性が良好の銅めっき膜を形成し得る電解銅めっき液及び電解銅めっき方法を提供することにある。
For this reason, when the electrolytic copper plating solution is discarded, it is necessary to first remove the chelating agent contained in the electrolytic copper plating solution, but the chelating agent is removed from the electrolytic copper plating solution to be discarded. It is difficult to do.
On the other hand, the electrolytic copper plating solution proposed in Patent Document 1 cannot be put to practical use because a precipitate composed of a copper complex is generated unless a chelating agent is added.
Accordingly, an object of the present invention is to provide an electrolytic copper plating solution and an electrolytic copper plating method that can form a copper plating film that is substantially free of a cyanide compound and a chelating agent and has good adhesion on a member surface. There is.
本発明者等は、前記課題を解決すべく検討を重ねた結果、銅イオンの供給源としての硫酸銅と、伝導塩としての硫酸硫酸カリウムとを配合し、ｐＨを２程度に調整した電解銅めっき液を用い、４２材から成るリードフレームの全面に銅のストライクめっきを施したところ、電解銅めっき液中に銅の沈殿物を生成することがなく銅のストライクめっきを施すことができ、形成された銅めっき膜の密着性も良好であることを見出し、本発明に到達した。 As a result of repeated studies to solve the above problems, the present inventors have blended copper sulfate as a copper ion supply source and potassium sulfate as a conductive salt, and adjusted the pH to about 2. Using the plating solution, copper strike plating was applied to the entire surface of the lead frame made of 42 materials, and copper strike plating could be applied without forming copper precipitates in the electrolytic copper plating solution. The present inventors have found that the adhesion of the copper plating film thus obtained is also good and have reached the present invention.
すなわち、本発明は、シアン化合物及びキレート剤が実質的に非含有の電解銅めっき液であって、該めっき液中に、銅イオンの供給源としての硫酸銅、塩化銅及び炭酸銅のいずれか１種類と、伝導塩としての硫酸塩とが含有され、且つ前記めっき液のｐＨが１〜２．５に調整されていることを特徴とする電解銅めっき液にある。
また、本発明は、部材表面に電解銅めっきを施す際に、前記電解めっき液を用いることを特徴とする電解銅めっき方法でもある。
かかる本発明において、硫酸塩として、硫酸ナトリウム、硫酸カリウム又は硫酸アンモニウム塩を好適に用いることができる。
また、銅めっきを施す部材として、銅又は銅合金以外のFe-Ni合金等の金属材料から成る部材を好適に用いることができる。この部材としては、リードフレームを用いることができ、前記リードフレームの表面に銅のストライクめっきを施す際に、前記電解銅めっき液を用いることができる。
That is, the present invention is an electrolytic copper plating solution substantially free of a cyanide compound and a chelating agent, and any one of copper sulfate, copper chloride and copper carbonate as a supply source of copper ions in the plating solution. One type and a sulfate as a conductive salt are contained, and the pH of the plating solution is adjusted to 1 to 2.5.
Moreover, this invention is also an electrolytic copper plating method characterized by using the said electrolytic plating liquid when performing electrolytic copper plating on the member surface.
In the present invention, sodium sulfate, potassium sulfate or ammonium sulfate can be suitably used as the sulfate.
Moreover, the member which consists of metal materials, such as Fe-Ni alloys other than copper or a copper alloy, can be used suitably as a member which performs copper plating. As this member, a lead frame can be used, and the electrolytic copper plating solution can be used when copper strike plating is applied to the surface of the lead frame.
本発明に係る電解銅めっき液は、毒性の強いシアン化合物が添加されておらず、安全であるため、その取扱は容易である。
更に、キレート剤も非含有であり、電解銅めっき液を廃棄処理する際に、キレート剤を含有する電解銅めっき液に比較して、キレート剤の除去操作を省略でき、めっき液中の金属等を容易に沈殿できる。このため、電解銅めっき液の廃棄処理も容易に行うことができる。
しかも、部材として、４２材から成る部材を用い、その表面に形成した銅めっき膜の密着性も良好である。
The electrolytic copper plating solution according to the present invention does not contain a highly toxic cyanide compound, and is safe and easy to handle.
Furthermore, it does not contain a chelating agent, and when the electrolytic copper plating solution is disposed of, compared with the electrolytic copper plating solution containing the chelating agent, the operation of removing the chelating agent can be omitted, such as the metal in the plating solution, etc. Can be easily precipitated. For this reason, the disposal process of the electrolytic copper plating solution can be easily performed.
In addition, as a member, a member made of 42 materials is used, and the adhesion of the copper plating film formed on the surface is also good.
本発明に係る電解銅めっき液によれば、電解銅めっき液の取扱が容易であって、廃棄処理も容易に行うことができる。
この様に、本発明に係る電解銅めっき液は、リードフレームの製造工程等において大量に用いられる電解銅めっき液を安全に取り扱うことができ、その廃棄処理も容易に行うことができるため、いわゆる「環境にやさしい」電解銅めっき液である。
According to the electrolytic copper plating solution according to the present invention, it is easy to handle the electrolytic copper plating solution, and the disposal process can be easily performed.
As described above, the electrolytic copper plating solution according to the present invention can safely handle the electrolytic copper plating solution used in large quantities in the lead frame manufacturing process and the like, and can easily perform the disposal process. “Environmentally friendly” electrolytic copper plating solution.
本発明に係る電解銅めっき液は、シアン化合物及びキレート剤が実質的に非含有の電解銅めっき液である。
かかる電解銅めっき液中には、銅イオンの供給源としての硫酸銅、塩化銅及び炭酸銅のいずれか１種類と、伝導塩としての硫酸塩とが含有されている。
この硫酸塩としては、硫酸ナトリウム、硫酸カリウム又は硫酸アンモニウム塩を用いることができる。
この様に、シアン化合物及びキレート剤が実質的に非含有の電解銅めっき液では、めっき液のｐHを中性に近づけると、銅の錯体から成る沈殿物が生成する。
この点、本発明に係る電解銅めっき液では、めっき液のｐHを１〜２．５（好ましくは１．２〜２．０）の弱酸に調整することによって、銅の錯体から成る沈殿物の生成を防止している。かかるめっき液のｐH調整は、伝導塩として添加する硫酸塩によって行うことができる。
The electrolytic copper plating solution according to the present invention is an electrolytic copper plating solution substantially free of a cyanide compound and a chelating agent.
Such an electrolytic copper plating solution contains any one of copper sulfate, copper chloride and copper carbonate as a supply source of copper ions and sulfate as a conductive salt.
As this sulfate, sodium sulfate, potassium sulfate or ammonium sulfate can be used.
In this way, in an electrolytic copper plating solution that is substantially free of a cyanide compound and a chelating agent, a precipitate composed of a copper complex is generated when the pH of the plating solution approaches neutral.
In this regard, in the electrolytic copper plating solution according to the present invention, by adjusting the pH of the plating solution to a weak acid of 1 to 2.5 (preferably 1.2 to 2.0), Generation is prevented. The pH of the plating solution can be adjusted with a sulfate added as a conductive salt.
ここで、めっき液のｐHが２．５を越えると、めっき液中に銅と水酸イオンから成る沈殿物が生成され易くなる。
一方、めっき液のｐHが１未満の場合には、４２材から成る部材表面に銅のストライクめっきを施したとき、部材表面を形成する鉄やニッケルが銅イオンと置換される。このため、部材表面に形成された銅めっき膜の密着性が劣るものとなる。
尚、硫酸塩では、めっき液のｐH調整が充分でない場合には、硫酸や塩酸を用いてもよい。
Here, when the pH of the plating solution exceeds 2.5, a precipitate composed of copper and hydroxide ions is easily generated in the plating solution.
On the other hand, when the pH of the plating solution is less than 1, when the strike surface of copper is applied to the member surface made of 42 materials, iron and nickel forming the member surface are replaced with copper ions. For this reason, the adhesiveness of the copper plating film formed on the member surface is inferior.
In the case of sulfate, sulfuric acid or hydrochloric acid may be used when pH adjustment of the plating solution is not sufficient.
かかる本発明に係る電解銅めっき液を用いた電解銅めっきは、通常の電解銅めっきと略同様な条件で行うことができる。
この本発明に係る電解銅めっき液を用いた電解銅めっきでは、銅又は銅合金から成る部材に施すことができることは勿論のこと、銅又は銅合金以外のFe-Ni合金等の金属材料から成る部材にも施すことができる。
このため、銅又は銅合金以外のFe-Ni合金等の金属材料から形成されることが多いリードフレームの全面に施す銅のストライクめっきに、好適に用いることができる。
The electrolytic copper plating using the electrolytic copper plating solution according to the present invention can be performed under substantially the same conditions as normal electrolytic copper plating.
The electrolytic copper plating using the electrolytic copper plating solution according to the present invention can be applied to a member made of copper or a copper alloy, and is made of a metal material such as Fe-Ni alloy other than copper or a copper alloy. It can also be applied to members.
For this reason, it can be suitably used for strike plating of copper applied to the entire surface of the lead frame, which is often formed from a metal material such as copper or an Fe—Ni alloy other than copper alloy.
電解銅めっき液中には、銅イオンの供給源としての硫酸銅・五水和物２００ｇ／ｌと、伝導塩としての硫酸カリウム３０ｇ／ｌとが配合されている。この電解銅めっき液のｐＨは２．０であった。
かかる電解銅めっきを用いて４２材から成るリードフレームの全面に、銅のストライクめっきを施した。このストライクめっきの条件は、２５℃の温度下において、リードフレームの単位表面積（１００ｃｍ2）当り５Ａ（アンペア）の電流を３０秒間流した。
電解銅めっきを施したリードフレームの全面には、厚さ０．３μｍの銅めっき膜が形成されており、銅めっき膜の表面に貼り付けた粘着テープを剥がすテープ試験でも、剥離したテープに銅めっき膜は付着しておらず、銅めっき膜は良好な密着性を呈するものであった。
（比較例１）
実施例１において、硫酸を添加して電解銅めっき液のｐＨを０．５とした他は、実施例１と同様にリードフレームの全面に銅のストライクめっきを施した。
電解銅めっきを施したリードフレームの全面には、厚さ０．５μｍの銅めき膜が形成されていたが、銅めっき膜の表面に貼り付けた粘着テープを剥がすテープ試験では、剥離されたテープに銅めっき膜が付着して剥離されており、形成された銅めっき膜の密着性は劣るものであった。
（比較例２）
実施例１において、０．０１Ｎ水酸化カリウム水溶液を添加して電解銅めっき液のｐＨを３とした他は、実施例１と同様にリードフレームの全面に銅のストライクめっきを施した。
しかし、電解銅めっき液中に銅と水酸イオンから成る沈殿物が形成されるため、電解銅めっきの以後の作業を中止した。
In the electrolytic copper plating solution, copper sulfate pentahydrate 200 g / l as a supply source of copper ions and potassium sulfate 30 g / l as a conductive salt are blended. The pH of this electrolytic copper plating solution was 2.0.
Using this electrolytic copper plating, copper strike plating was applied to the entire surface of the lead frame made of 42 materials. The strike plating condition was that a current of 5 A (ampere) per unit surface area (100 cm 2 ) of the lead frame was passed for 30 seconds at a temperature of 25 ° C.
A copper plating film with a thickness of 0.3 μm is formed on the entire surface of the lead frame that has been subjected to electrolytic copper plating. Even in the tape test in which the adhesive tape attached to the surface of the copper plating film is peeled off, copper is removed from the peeled tape. The plating film did not adhere, and the copper plating film exhibited good adhesion.
(Comparative Example 1)
In Example 1, copper strike plating was performed on the entire surface of the lead frame in the same manner as in Example 1 except that sulfuric acid was added to adjust the pH of the electrolytic copper plating solution to 0.5.
A copper plating film with a thickness of 0.5 μm was formed on the entire surface of the lead frame subjected to electrolytic copper plating. However, in the tape test for peeling the adhesive tape attached to the surface of the copper plating film, the peeled tape The copper plating film adhered and peeled off, and the adhesion of the formed copper plating film was inferior.
(Comparative Example 2)
In Example 1, copper strike plating was performed on the entire surface of the lead frame in the same manner as in Example 1 except that 0.01N potassium hydroxide aqueous solution was added to adjust the pH of the electrolytic copper plating solution to 3.
However, since a precipitate composed of copper and hydroxide ions is formed in the electrolytic copper plating solution, the work after the electrolytic copper plating was stopped.
Claims (5)
該めっき液中に、銅イオンの供給源としての硫酸銅、塩化銅及び炭酸銅のいずれか１種類と、伝導塩としての硫酸塩とが含有され、
且つ前記めっき液のｐＨが１〜２．５に調整されていることを特徴とする電解銅めっき液。 An electrolytic copper plating solution substantially free of cyanide and chelating agent,
In the plating solution, any one of copper sulfate, copper chloride and copper carbonate as a supply source of copper ions, and sulfate as a conductive salt are contained,
The electrolytic copper plating solution is characterized in that the pH of the plating solution is adjusted to 1 to 2.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2003270276A JP2005023405A (en) | 2003-07-02 | 2003-07-02 | Copper electroplating solution and copper electroplating method |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003270276A JP2005023405A (en) | 2003-07-02 | 2003-07-02 | Copper electroplating solution and copper electroplating method |
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| JP2005023405A true JP2005023405A (en) | 2005-01-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362141C (en) * | 2005-09-01 | 2008-01-16 | 山东建筑工程学院材料科学研究所 | Propanetriol non-cyanide bright copper plating liquid |
| CN102171820A (en) * | 2008-09-05 | 2011-08-31 | Lg伊诺特有限公司 | Lead frame and manufacturing method thereof |
-
2003
- 2003-07-02 JP JP2003270276A patent/JP2005023405A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362141C (en) * | 2005-09-01 | 2008-01-16 | 山东建筑工程学院材料科学研究所 | Propanetriol non-cyanide bright copper plating liquid |
| CN102171820A (en) * | 2008-09-05 | 2011-08-31 | Lg伊诺特有限公司 | Lead frame and manufacturing method thereof |
| US8945951B2 (en) | 2008-09-05 | 2015-02-03 | Lg Innotek Co., Ltd. | Lead frame and manufacturing method thereof |
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