JP2006052425A - Soft-etching solution and plating method - Google Patents
Soft-etching solution and plating method Download PDFInfo
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- JP2006052425A JP2006052425A JP2004233205A JP2004233205A JP2006052425A JP 2006052425 A JP2006052425 A JP 2006052425A JP 2004233205 A JP2004233205 A JP 2004233205A JP 2004233205 A JP2004233205 A JP 2004233205A JP 2006052425 A JP2006052425 A JP 2006052425A
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- 238000007747 plating Methods 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 58
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Landscapes
- Manufacturing Of Printed Wiring (AREA)
- Chemically Coating (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
本発明は、プリント回路板の最終表面処理後の外観及び半田付け性に優れ、しかも生産工程で好適に用いることが可能なソフトエッチング液、及びめっき方法に関する。 The present invention relates to a soft etching solution that is excellent in appearance and solderability after final surface treatment of a printed circuit board and that can be suitably used in a production process, and a plating method.
プリント配線基板において、チップを実装する基板の導体回路表面としては、外観が良好で、かつ半田付け性にも優れた状態となっていることが望まれる。このような表面状態を得る方法としては金属材料や有機材料を用いた様々な方法があり、例えば、半田レベラー法（ＨＡＳＬ法）、耐熱プリフラックス法（ＯＳＰ法）、無電解ニッケルめっき−無電解金めっき法、といった方法が挙げられる。 In the printed wiring board, it is desired that the surface of the conductor circuit of the board on which the chip is mounted has a good appearance and excellent solderability. As a method for obtaining such a surface state, there are various methods using a metal material or an organic material. For example, solder leveler method (HASL method), heat-resistant preflux method (OSP method), electroless nickel plating-electroless Examples thereof include a gold plating method.
ＨＡＳＬ法は加熱して溶融させた半田浴中にプリント回路板を浸漬し引き上げ、余剰の半田を熱風で吹き飛ばすことにより、プリント回路部分（銅部分）を半田で覆う方法である。当該方法には、被覆される半田の厚さを均一にすることが難しいこと、パターン回路の高密度化により複雑かつスペースの微細化が進んでいるためブリッジ発生問題の多発が予想されること、鉛フリー半田を使用する場合には半田浴温度が高くなるためプリント回路板に従来以上の熱負荷がかかること、といったことが問題視されている。
ＯＳＰ法は、プリント回路板の銅回路を有機膜で保護する方法である。処理が簡便である上、微細な回路パターンに対しても適用可能であるため広く普及しているが、複数回の実装工程では銅回路上に形成された有機膜が酸化してしまうため、回路外観や半田付け性を維持することが困難であることが問題視されている。今後、鉛フリー半田実装が一般化して実装温度が上昇すれば、この問題はより深刻になる可能性がある。
The HASL method is a method in which a printed circuit board (copper part) is covered with solder by immersing and lifting a printed circuit board in a solder bath heated and melted, and blowing off excess solder with hot air. In this method, it is difficult to make the thickness of the solder to be coated uniform, and it is expected that frequent occurrence of a bridge problem will occur because the pattern circuit is densified and the space is complicated and miniaturized. When lead-free solder is used, the problem is that the printed circuit board is subjected to more heat load than before because the solder bath temperature is high.
The OSP method is a method of protecting a copper circuit of a printed circuit board with an organic film. Although it is easy to process and can be applied to fine circuit patterns, it is widespread, but the organic film formed on the copper circuit is oxidized in multiple mounting processes, so the circuit It is regarded as a problem that it is difficult to maintain the appearance and solderability. In the future, if lead-free solder mounting becomes common and the mounting temperature rises, this problem may become more serious.
一方、無電解ニッケルめっき−無電解金めっき法は、上記２つの方法に比してプリント回路板に対する熱負荷が穏やかである点で優れた方法と云えるが、最終的な無電解金めっきを行なう前に予め無電解ニッケルめっきを施す工程が含まれるため処理工程が複雑で長くなる傾向となり、また、高価な薬剤が必要となる場合があるため製造工程が高コストになる傾向となる。しかも、安定して良好な無電解金めっき皮膜を実現するためには無電解ニッケルめっき−無電解金めっきの全工程について工程管理を比較的厳密に行なう必要がある点で、なお改善の余地を有する方法であった。 On the other hand, the electroless nickel plating-electroless gold plating method is an excellent method in that the thermal load on the printed circuit board is gentle compared to the above two methods. Since a process of performing electroless nickel plating before the process is included, the process is likely to be complicated and long, and an expensive chemical may be required, and the manufacturing process tends to be expensive. Moreover, in order to realize a stable and good electroless gold plating film, it is necessary to perform process control relatively strictly for all the processes of electroless nickel plating-electroless gold plating, and there is still room for improvement. It was a method that had.
ここで、無電解ニッケルめっき−無電解金めっき法を採用する場合には、無電解ニッケルめっき工程の前にプリント回路板を予めソフトエッチングする工程が導入されることがある。
このようなソフトエッチング工程は、プリント回路（銅）表面の汚れや酸化皮膜を除去し、銅表面と無電解ニッケルめっき皮膜との密着性を向上させることを目的として行われるものであり、用いられるエッチング液としては、例えばリン酸やホウ素化合物を用いた過酸化水素系エッチング液（特許文献１：特開平３−１９３８８６号公報参照）、フッ素化合物を用いたエッチング液（引用文献２：特開平９−１８４０８１号公報参照）、グリコールエーテル類を用いたエッチング液（引用文献３：特公平４−０２７３０６号公報参照）、クエン酸を用いたエッチング液（引用文献４：特許３３８７５２９号公報参照）、ジカルボン酸とアルコールを用いたエッチング液（引用文献５：特公昭５５−０３００７３号公報参照）、カルボン酸と安定剤を用いたエッチング液（引用文献６：特開平７−０１８４７２号公報参照）、鉄の溶解を目的としてエチレングリコールとグルタル酸を用いたエッチング液（引用文献７：特開平１１−３５０１７０号公報参照）、グリコールエーテルを用いたエッチング液（引用文献８：特公昭５０−０３７１５９号公報参照）、等が挙げられる。また、本発明者は先に、ヒドラジド誘導体を用いたソフトエッチング液を開示（特願２００３−３０２９９７号）している。
Here, when the electroless nickel plating-electroless gold plating method is adopted, a step of soft etching the printed circuit board in advance may be introduced before the electroless nickel plating step.
Such a soft etching process is performed for the purpose of removing dirt and oxide film on the surface of the printed circuit (copper) and improving the adhesion between the copper surface and the electroless nickel plating film. As the etchant, for example, a hydrogen peroxide-based etchant using phosphoric acid or a boron compound (see Patent Document 1: Japanese Patent Laid-Open No. 3-193886), an etchant using a fluorine compound (Cited Document 2: Japanese Patent Laid-open No. Hei 9). No. 184081), an etching solution using glycol ethers (cited document 3: Japanese Patent Publication No. 4-027306), an etching solution using citric acid (cited document 4: refer to Japanese Patent No. 3387529), dicarboxylic acid Etching solution using acid and alcohol (reference document 5: see Japanese Patent Publication No. 55-030073), carboxylic acid and Etching solution using a fixing agent (cited document 6: see JP-A-7-018472), etching solution using ethylene glycol and glutaric acid for the purpose of dissolving iron (cited document 7: JP-A-11-350170) And an etching solution using glycol ether (cited document 8: see Japanese Patent Publication No. 50-037159). The present inventor previously disclosed a soft etching solution using a hydrazide derivative (Japanese Patent Application No. 2003-302997).
しかしながら、上記ソフトエッチング液にてプリント回路板をエッチング処理し、直接に無電解金めっきを行なった場合に得られるめっき皮膜については、外観や半田付け特性といった観点から十分に満足し得る皮膜であるとは云い難かった。従って、めっき法により外観が良好でかつ半田付け性にも優れたプリント回路板の表面状態を実現するためには、最終表面層となる置換めっき皮膜を形成する前に予め下地となるめっき皮膜層を形成することが必要とされていた。
プリント回路板の表面状態を整える方法として、プリント回路板への熱負荷の観点から優れる方法であるめっき法を採用するに際し、簡便且つ低コストにめっきを行ない得る技術の開発が望まれていた。
However, the plating film obtained when the printed circuit board is etched with the soft etchant and directly electrolessly plated with gold is sufficiently satisfactory from the viewpoint of appearance and soldering characteristics. It was difficult to say. Therefore, in order to realize a surface state of a printed circuit board having a good appearance and excellent solderability by plating, a plating film layer as a base in advance before forming a replacement plating film as a final surface layer Was required to form.
As a method for adjusting the surface state of a printed circuit board, it has been desired to develop a technique capable of performing plating easily and at low cost when adopting a plating method which is an excellent method from the viewpoint of thermal load on the printed circuit board.
本発明は上記事情に鑑みなされたもので、銅又は銅合金表面の置換めっき前処理用のソフトエッチング液であって、置換めっき後の外観及び半田付け性に優れるソフトエッチング液、及び、当該ソフトエッチング液を用いためっき方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a soft etching solution for pretreatment of replacement plating on the surface of copper or a copper alloy, the soft etching solution having excellent appearance and solderability after replacement plating, and the soft etching solution. An object is to provide a plating method using an etching solution.
本発明者は、上記目的を達成するため鋭意検討を行った結果、過酸化水素又は過硫酸塩と、無機酸と、カルボキシル基を２個以上有する有機酸と、を含むことを特徴とするソフトエッチング液が、プリント回路を形成する銅又は銅合金表面を良好にエッチングすることができるため、当該エッチング後にプリント回路板上に直接に置換めっき皮膜を形成する場合であっても、外観が良好でかつ半田付け性にも優れた置換めっき皮膜を形成し得ることを見出し、更に、プリント回路板の表面状態を整える方法としてめっき法を採用するに際し、当該ソフトエッチング液を用いることにより簡便で低コストなめっき方法を実現し得ることを知見し、本発明をなすに至った。 As a result of intensive investigations to achieve the above object, the present inventor has found that a software comprising hydrogen peroxide or a persulfate, an inorganic acid, and an organic acid having two or more carboxyl groups. Since the etching solution can satisfactorily etch the copper or copper alloy surface that forms the printed circuit, the appearance is good even when the displacement plating film is formed directly on the printed circuit board after the etching. In addition, it has been found that a displacement plating film with excellent solderability can be formed, and furthermore, when adopting a plating method as a method for adjusting the surface state of a printed circuit board, it is simple and low-cost by using the soft etching solution. The present inventors have found that a simple plating method can be realized, and have made the present invention.
即ち、本発明は、下記のソフトエッチング液及びめっき方法を提供するものである。
請求項１：
銅又は銅合金表面の置換めっき前処理用ソフトエッチング液であって、過酸化水素又は過硫酸塩と、無機酸と、カルボキシル基を２個以上有する有機酸と、を含むことを特徴とするソフトエッチング液。
請求項２：
前記カルボキシル基を２個以上有する有機酸が、シュウ酸、リンゴ酸、グルタル酸、マレイン酸、フマル酸、酒石酸、コハク酸、マロン酸、フタル酸、イタコン酸、シトラコン酸、クエン酸、グルタミン酸、及びアスパラギン酸よりなる群から選択された１種又は２種以上である請求項１記載のソフトエッチング液。
請求項３：
更に、浴安定剤としてエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、メチルプロピレンジグリコール、及びメチルプロピレングリコールよりなる群から選択された１種又は２種以上を含む請求項１又は２記載のソフトエッチング液。
請求項４：
前記浴安定剤が、エチレングリコールモノエチルエーテル、及び／又はジエチレングリコールジエチルエーテルである請求項３記載のソフトエッチング液。
請求項５：
請求項１乃至４のいずれかに記載のソフトエッチング液にて銅又は銅合金表面をソフトエッチングした後、直接に置換めっき皮膜を形成することを特徴とするめっき方法。
That is, the present invention provides the following soft etching solution and plating method.
Claim 1:
A soft etching solution for pretreatment of substitutional plating on the surface of copper or copper alloy, comprising: hydrogen peroxide or persulfate; an inorganic acid; and an organic acid having two or more carboxyl groups. Etching solution.
Claim 2:
The organic acid having two or more carboxyl groups is oxalic acid, malic acid, glutaric acid, maleic acid, fumaric acid, tartaric acid, succinic acid, malonic acid, phthalic acid, itaconic acid, citraconic acid, citric acid, glutamic acid, and The soft etching solution according to claim 1, wherein the soft etching solution is one or more selected from the group consisting of aspartic acid.
Claim 3:
The bath stabilizer according to claim 1 or 2, further comprising one or more selected from the group consisting of ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methylpropylene diglycol, and methylpropylene glycol. Soft etchant.
Claim 4:
The soft etching solution according to claim 3, wherein the bath stabilizer is ethylene glycol monoethyl ether and / or diethylene glycol diethyl ether.
Claim 5:
5. A plating method comprising: forming a displacement plating film directly after soft etching of a copper or copper alloy surface with the soft etching solution according to claim 1.
置換めっき皮膜は、素地である銅又は銅合金と金属成分が置換することにより素地表面に置換金属層が形成されるものである。本発明者は、素地である銅又は銅合金の表面状態が置換めっき皮膜形成後にもそのまま維持される傾向にある点に着目し、置換めっき皮膜表面に求められる表面状態（外観や半田付け性に優れた表面状態）を素地表面に実現させるべく検討を重ねた結果、過酸化水素又は過硫酸塩と無機酸とカルボキシル基を２個以上有する有機酸とを含む本発明のソフトエッチング液にて銅又は銅合金素地の表面を処理することにより、該素地表面を外観や半田付け性に優れた表面状態に調整することが可能であることを見出した。従って、本発明のソフトエッチング液を用いて調整した銅又は銅合金素地表面に対して置換めっき皮膜を形成すれば、外観と半田付け性に優れた置換めっき皮膜が得られることとなる。 The displacement plating film is a substrate in which a substitution metal layer is formed on the substrate surface by substitution of copper or copper alloy as a substrate with a metal component. The inventor pays attention to the fact that the surface state of the base copper or copper alloy tends to be maintained as it is after the formation of the replacement plating film, and the surface state (appearance and solderability) required for the surface of the replacement plating film. As a result of repeated studies to realize an excellent surface state) on the substrate surface, copper was obtained with the soft etching solution of the present invention containing hydrogen peroxide or persulfate, an inorganic acid, and an organic acid having two or more carboxyl groups. Alternatively, it has been found that by treating the surface of the copper alloy substrate, the substrate surface can be adjusted to a surface state excellent in appearance and solderability. Therefore, if a displacement plating film is formed on the copper or copper alloy substrate surface prepared using the soft etching solution of the present invention, a displacement plating film excellent in appearance and solderability can be obtained.
よって、本発明のソフトエッチング液を用いれば、最終的な置換めっき皮膜を形成する前に予め下地めっき皮膜層を形成しておく必要がなくなるため、従来めっき法が有していた処理工程の複雑化、高コスト化といった問題点を解決し得るめっき法が実現される。 Therefore, if the soft etching solution of the present invention is used, it is not necessary to form a base plating film layer in advance before forming the final displacement plating film, so that the complicated process steps of the conventional plating method are required. A plating method capable of solving the problems of increasing the cost and cost is realized.
なお、本発明のソフトエッチング液が銅又は銅合金素地表面を外観及びめっき特性に優れた状態に調整し得るメカニズムは定かではないが、従来のエッチング液は銅粒界面の溶解の進行が早いことから素地表面の凹凸を解消し得なかったものと考えられる。
本発明においては銅と錯体を形成しやすいジカルボン酸若しくは３つ以上カルボキシル基を有する有機化合物を用いるため、これが銅粒界面若しくは表面全体に吸着することにより、通常の溶解速度よりも銅粒界面部分の溶解速度を遅くさせる、乃至、全体的に均一に溶解させる傾向となるものと考えられる。このような作用により、表面処理後に光沢に寄与する平滑性と、半田付け性に寄与する微細な凹凸性を両立した表面を実現し得ると考えられる。
The mechanism by which the soft etching solution of the present invention can adjust the surface of the copper or copper alloy substrate to have excellent appearance and plating characteristics is not clear, but the conventional etching solution has a fast progress of dissolution at the copper grain interface. It is considered that the unevenness of the substrate surface could not be eliminated.
In the present invention, a dicarboxylic acid that easily forms a complex with copper or an organic compound having three or more carboxyl groups is used. Therefore, when this adsorbs to the copper grain interface or the entire surface, the copper grain interface part rather than the normal dissolution rate. It is considered that the dissolution rate of the solution tends to be slowed or dissolved uniformly. By such an action, it is considered that a surface having both smoothness that contributes to gloss after surface treatment and fine unevenness that contributes to solderability can be realized.
本発明のソフトエッチング液は、銅又は銅合金表面の置換めっき前処理用のソフトエッチング液であり、置換めっき後の外観及び半田付け性に優れるソフトエッチング液である。また、本発明のめっき方法は、プリント回路板の表面状態を簡便且つ低コストに調整し得るめっき方法である。 The soft etching solution of the present invention is a soft etching solution for pretreatment of substitution plating on the surface of copper or a copper alloy, and is a soft etching solution excellent in appearance and solderability after substitution plating. In addition, the plating method of the present invention is a plating method that can easily and inexpensively adjust the surface state of the printed circuit board.
以下、本発明につき更に詳しく説明する。
本発明のソフトエッチング液は、銅又は銅合金（以下、「銅基材」と略記することがある）表面の置換めっき前処理用ソフトエッチング液であって、以下の（Ａ）〜（Ｃ）の各成分、
（Ａ）過酸化水素又は過硫酸塩、
（Ｂ）無機酸、
（Ｃ）カルボキシル基を２個以上有する有機酸、
を含有することを特徴とするソフトエッチング液であり、
より好ましくは更に以下の（Ｄ）成分、
（Ｄ）浴安定剤、
を含有することを特徴とするエッチング液である。
Hereinafter, the present invention will be described in more detail.
The soft etching solution of the present invention is a soft etching solution for displacement plating pretreatment on the surface of copper or a copper alloy (hereinafter sometimes abbreviated as “copper substrate”), and includes the following (A) to (C): Each ingredient of
(A) hydrogen peroxide or persulfate,
(B) inorganic acid,
(C) an organic acid having two or more carboxyl groups,
A soft etching solution characterized by containing
More preferably, the following component (D):
(D) a bath stabilizer,
It is an etching liquid characterized by containing.
上記（Ａ）成分として過酸化水素を用いる場合、本発明のソフトエッチング液における過酸化水素の配合量としては、３５％過酸化水素水の配合量として通常５〜１００ｍｌ／Ｌ、好ましくは１０〜８０ｍｌ／Ｌである。過酸化水素の配合量が少なすぎるとエッチング不足となる場合があり、一方、多すぎると過剰エッチングかつ外観不良（光沢度低下）となる場合がある。 When hydrogen peroxide is used as the component (A), the compounding amount of hydrogen peroxide in the soft etching solution of the present invention is usually 5 to 100 ml / L, preferably 10 to 35% as a compounding amount of 35% hydrogen peroxide solution. 80 ml / L. If the amount of hydrogen peroxide is too small, etching may be insufficient. On the other hand, if the amount is too large, excessive etching and poor appearance (decrease in gloss) may occur.
上記（Ａ）成分の過硫酸塩としては、従来公知の過硫酸塩を用いることができ、特に制限されるものではないが、例えば過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等が挙げられる。これらは１種を単独で、又は２種以上を併用してもよい。
上記（Ａ）成分として過硫酸塩を用いる場合、本発明のソフトエッチング液における過硫酸塩の配合量としては通常１０〜５００ｇ／Ｌ、好ましくは５０〜２００ｇ／Ｌである。過硫酸塩の配合量が少なすぎるとエッチング不足となる場合があり、一方、多すぎると過剰エッチングかつ外観不良（光沢度低下）となる場合がある。
As the persulfate of the component (A), a conventionally known persulfate can be used, and is not particularly limited, and examples thereof include ammonium persulfate, sodium persulfate, and potassium persulfate. These may be used alone or in combination of two or more.
When persulfate is used as the component (A), the amount of persulfate in the soft etching solution of the present invention is usually 10 to 500 g / L, preferably 50 to 200 g / L. If the amount of persulfate is too small, etching may be insufficient. On the other hand, if it is too large, excessive etching and poor appearance (decrease in gloss) may occur.
上記（Ｂ）成分としては、従来公知の無機酸を用いることができ、特に制限されるものではないが、例えば硝酸、塩酸、硫酸等が挙げられる。これらは１種を単独で、又は２種以上を併用してもよい。
本発明のソフトエッチング液における上記（Ｂ）成分の配合量としては、（Ｂ）成分として６２．５％硫酸を用いる場合には通常１０〜５００ｍｌ／Ｌ、好ましくは２０〜１００ｍｌ／Ｌである。（Ｂ）成分の配合量が少なすぎるとエッチング不足や外観不良が生じる場合がある。
As said (B) component, a conventionally well-known inorganic acid can be used, Although it does not restrict | limit in particular, For example, nitric acid, hydrochloric acid, a sulfuric acid etc. are mentioned. These may be used alone or in combination of two or more.
The blending amount of the component (B) in the soft etching solution of the present invention is usually 10 to 500 ml / L, preferably 20 to 100 ml / L when 62.5% sulfuric acid is used as the component (B). If the blending amount of the component (B) is too small, etching may be insufficient or appearance may be poor.
上記（Ｃ）成分としては、例えばシュウ酸、リンゴ酸、グルタル酸、マレイン酸、フマル酸、酒石酸、コハク酸、マロン酸、フタル酸、イタコン酸、シトラコン酸、クエン酸、グルタミン酸、アスパラギン酸等が挙げられる。これらは１種を単独で、又は２種以上を併用しても良い。
中でも、上記（Ｃ）成分としてクエン酸、グルタル酸、グルタミン酸、フタル酸を用いた場合には、エッチング後の置換めっき皮膜の外観に優れるのみならず、半田付け特性に優れることとなるため好適である。
Examples of the component (C) include oxalic acid, malic acid, glutaric acid, maleic acid, fumaric acid, tartaric acid, succinic acid, malonic acid, phthalic acid, itaconic acid, citraconic acid, citric acid, glutamic acid, aspartic acid and the like. Can be mentioned. These may be used alone or in combination of two or more.
Among these, when citric acid, glutaric acid, glutamic acid, and phthalic acid are used as the component (C), it is preferable because not only the appearance of the displacement plating film after etching is excellent, but also the soldering characteristics are excellent. is there.
このような（Ｃ）成分が本発明のソフトエッチング液に占める濃度としては、通常０．００１〜１Ｍ、好ましくは０．００５〜０．１Ｍである。（Ｃ）成分の濃度が０．００１Ｍ未満であると光沢度が低下する場合があり、一方、１Ｍを超えると溶解しなくなる場合や不経済になる場合がある。 The concentration of such component (C) in the soft etching solution of the present invention is usually 0.001 to 1M, preferably 0.005 to 0.1M. When the concentration of the component (C) is less than 0.001M, the glossiness may be lowered. On the other hand, when it exceeds 1M, it may not be dissolved or may be uneconomical.
本発明における上記（Ｄ）成分としては、公知のメタノールやエタノール等のアルコール類、グリコール類、グリコールエーテル類やフェノール類を使用することができる。
グリコール類としては、例えばエチレングリコール、ジメチルグリコール、ジメチルジグリコール、エチレングリコールモノフェニルエーテル、イソブチレングリコール、エチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノブチルエーテル、メチルプロピレンジグリコール、メチルプロピレングリコール、ポリプロピレングリコール等が挙げられる。これらは１種を単独で、又は２種以上を併用しても良い。
中でも、上記（Ｄ）成分としてエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、メチルプロピレンジグリコール、及びメチルプロピレングリコールよりなる群から選択された１種又は２種以上を用いた場合には、エッチング液中の銅（エッチング液により基材である積層銅箔が溶解された銅）の濃度が上昇してしまった後（いわゆる、「浴老化」後）であっても、エッチングされた基材表面の外観が良好であり、エッチング速度低下も比較的小さいため好適である。
As said (D) component in this invention, well-known alcohols, such as methanol and ethanol, glycols, glycol ethers, and phenols can be used.
Examples of glycols include ethylene glycol, dimethyl glycol, dimethyl diglycol, ethylene glycol monophenyl ether, isobutylene glycol, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, methylpropylene diglycol, methylpropylene glycol. And polypropylene glycol. These may be used alone or in combination of two or more.
Among them, when using one or more selected from the group consisting of ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methylpropylene diglycol, and methylpropylene glycol as the component (D), Even after the concentration of copper in the etching solution (copper in which the laminated copper foil as the substrate has been dissolved by the etching solution) has increased (after so-called “bath aging”), the etched substrate The surface appearance is good and the etching rate decrease is relatively small, which is preferable.
ここで、エッチング液中の安定剤濃度を分析する方法としてはガスクロマトグラフィー法等が挙げられるが、多くの場合特殊な機器を必要とするものであって簡便な方法とは云い難い。従って、エッチング液中の安定剤濃度が変動してもエッチング速度が大幅に変動しないという特性は、浴管理の観点からも、安定したエッチングを連続して行なう観点からも非常に重要な特性である。安定剤の多くは、エッチング液中の安定剤濃度の微細な変動がエッチング速度の大幅な変動を引き起こす傾向にある。
上記（Ｄ）成分としてエチレングリコールモノエチルエーテル及び／又はジエチレングリコールジエチルエーテルを用いた場合には、エッチング速度に対する（Ｄ）成分配合量の寄与が比較的小さく、浴管理の観点から好適であり、基材のエッチング膜厚を厳密に管理することも可能である。エッチング膜厚を厳密に管理することは銅基材を確実に残存させることにつながり、その後の置換めっき工程を良好に行なうことが可能となる。
Here, as a method for analyzing the concentration of the stabilizer in the etching solution, a gas chromatography method and the like can be mentioned. However, in many cases, a special instrument is required and it is difficult to say that it is a simple method. Therefore, the characteristic that the etching rate does not vary greatly even when the concentration of the stabilizer in the etching solution varies is a very important characteristic from the viewpoint of bath management and from the viewpoint of performing stable etching continuously. . In many stabilizers, fine fluctuations in the concentration of the stabilizer in the etching solution tend to cause significant fluctuations in the etching rate.
When ethylene glycol monoethyl ether and / or diethylene glycol diethyl ether is used as the component (D), the contribution of the component (D) to the etching rate is relatively small, which is preferable from the viewpoint of bath management. It is also possible to strictly control the etching film thickness of the material. Strictly managing the etching film thickness leads to reliably leaving the copper substrate, and the subsequent displacement plating process can be performed satisfactorily.
エッチング液中の浴安定剤濃度が変動してもエッチング速度が大幅に変動しないという特性の指標として、より具体的な指標を示すために、３５％過酸化水素水 ５０ｍｌ／Ｌ、６２．５％硫酸 ５０ｍｌ／Ｌ、カルボキシル基を２個以上有する有機酸 ０．０２Ｍに対して浴安定剤を０．００１Ｍ，０．００５Ｍ，０．０１Ｍ，０．０５Ｍの濃度となるように配合してエッチング液を調製し、整面研磨を行なっていないＦＲ−４銅張り積層板を処理温度３０℃、処理時間２分間の条件下でエッチングした場合に、上記０．００１〜０．０５Ｍ濃度の中で最もエッチング量の大きかったエッチング液のエッチング量を最大エッチング量Ｅmax（μｍ）とし、最もエッチング量の小さかったエッチング液のエッチング量を最小エッチング量Ｅmin（μｍ）として、これらＥmax値及びＥmin値から溶解量変動率Ｒ（％）＝１００×（Ｅmax−Ｅmin）／Ｅminを定義する。本発明のソフトエッチング液の有する上記Ｒ（％）の値としては、通常２０％以下、好ましくは１０％以下、より好ましくは５％以下である。 In order to show a more specific index as a characteristic index that the etching rate does not vary greatly even when the bath stabilizer concentration in the etching solution varies, 35% hydrogen peroxide solution 50 ml / L, 62.5% Etching solution containing 50 ml / L of sulfuric acid and 0.02M of organic acid having 2 or more carboxyl groups, and bath stabilizer added at concentrations of 0.001M, 0.005M, 0.01M and 0.05M. When the FR-4 copper clad laminate not prepared for surface polishing is etched under the conditions of a processing temperature of 30 ° C. and a processing time of 2 minutes, the highest concentration among the above 0.001 to 0.05 M concentration the etching amount of greater were etchant etching amount and the maximum etching amount E max (μm), most minimum etching amount the etching amount of etching amount of less was etchant E min (mu ) As to define these E max value and E min dissolution amount change rate from value R (%) = 100 × ( E max -E min) / E min. The R (%) value of the soft etching solution of the present invention is usually 20% or less, preferably 10% or less, more preferably 5% or less.
なお、このような（Ｄ）成分が本発明のソフトエッチング液に占める濃度としては、通常０．００１〜０．１Ｍ、好ましくは０．００５〜０．０１Ｍである。（Ｄ）成分の濃度が０．００１Ｍ未満であると過酸化水素の消耗量が増大する場合があり、一方、０．１Ｍを超えると効果が変らず不経済となったり、溶解しなくなったりする場合がある。 In addition, as a density | concentration which such (D) component occupies for the soft etching liquid of this invention, it is 0.001-0.1M normally, Preferably it is 0.005-0.01M. If the concentration of component (D) is less than 0.001M, the consumption of hydrogen peroxide may increase. On the other hand, if the concentration exceeds 0.1M, the effect will not change and it will be uneconomical or will not dissolve. There is a case.
本発明のソフトエッチング液には、更に必要に応じ、メタノールやエタノール等のアルコール類、ＥＤＴＡ、ＨＥＤＴＡ、ＴＥＴＡ、ＥＤＡ、ＤＥＴＡ、ＴＥＡ、ＤＥＡ、ＭＥＡ等のアミン化合物を添加することも可能である。アミン化合物の添加は、エッチング液の銅溶解許容量向上につながり、エッチング液寿命の延長につながるため好適である。 If necessary, an alcohol compound such as methanol or ethanol, or an amine compound such as EDTA, HEDTA, TETA, EDA, DETA, TEA, DEA, or MEA can be added to the soft etching solution of the present invention. Addition of an amine compound is preferable because it leads to an increase in the copper dissolution tolerance of the etching solution and extends the life of the etching solution.
本発明のソフトエッチング液を用いてエッチングを行なう場合、エッチング液の温度としては通常２５〜５０℃、エッチング処理時間としては通常３０秒〜３分程度であるが、特に限定されるものではない。浸漬または水平装置などによる噴霧エッチングも可能である。 When etching is performed using the soft etching solution of the present invention, the temperature of the etching solution is usually 25 to 50 ° C. and the etching treatment time is usually about 30 seconds to 3 minutes, but is not particularly limited. Spray etching by dipping or horizontal equipment is also possible.
本発明のソフトエッチング液により銅基材をエッチングする場合、エッチング処理後の銅基材表面の光沢度としては通常１５〜４０、好ましくは２５〜３５である。ここで、本発明において光沢度とは、ＪＩＳ Ｚ ８７４１に準拠し、光沢度計Ｇｌｏｓｓ Ｍｅｔｅｒ ＶＧ２０００（日本電色工業社製）を用い、光源（ハロゲンランプ）の入射角が２０度の条件で測定する光沢度を意味する。
また、本発明のソフトエッチング液により銅基材をエッチングする場合、エッチング処理後の銅基材表面の半田ボイド発生率（半田付け特性の指標、（％））としては通常０〜２０％、好ましくは０〜１０％である。ここで、本発明において半田ボイド発生率とは、シリーズ４０００（Ｄａｇｅ社製）を用い、ボールシェア試験により評価した値を意味する。半田ボールをＢＧＡパターンに実装し、シェア試験を行ない、破断した断面にボイドが発生しているかどうかを確認した。試験条件は、ホットプレート：２３０℃×６０秒、フラックス：非活性ロジンフラックス、半田ボール：Ｓｎ／Ｐｂ＝６３／３７、直径０．７５ｍｍ、シェア速度：１７０μｍ／ｓｅｃ、ツール高：５０μｍとした。
When etching a copper substrate with the soft etching solution of the present invention, the glossiness of the copper substrate surface after the etching treatment is usually 15 to 40, preferably 25 to 35. Here, the glossiness in the present invention is measured in accordance with JIS Z 8741, using a gloss meter Gloss Meter VG2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) under the condition that the incident angle of the light source (halogen lamp) is 20 degrees. Means glossiness
Moreover, when etching a copper substrate with the soft etching solution of the present invention, the solder void generation rate (index of soldering characteristics, (%)) on the surface of the copper substrate after the etching treatment is usually 0 to 20%, preferably Is 0 to 10%. Here, in the present invention, the solder void generation rate means a value evaluated by a ball shear test using a series 4000 (manufactured by Dage). Solder balls were mounted on a BGA pattern, a shear test was performed, and it was confirmed whether voids occurred in the fractured cross section. The test conditions were: hot plate: 230 ° C. × 60 seconds, flux: inactive rosin flux, solder ball: Sn / Pb = 63/37, diameter 0.75 mm, shear rate: 170 μm / sec, tool height: 50 μm.
本発明のソフトエッチング液のエッチング速度としては、通常１〜５μｍ／ｍｉｎ、好ましくは１〜３μｍ／ｍｉｎ、より好ましくは１．５〜２μｍ／ｍｉｎである。エッチング速度が大きすぎても小さすぎても、特にソフトエッチングを行なう場合に作業性が悪化する場合がある。 The etching rate of the soft etching solution of the present invention is usually 1 to 5 μm / min, preferably 1 to 3 μm / min, more preferably 1.5 to 2 μm / min. If the etching rate is too high or too low, workability may be deteriorated particularly when soft etching is performed.
本発明のめっき方法は、上述した本発明のソフトエッチング液にて銅又は銅合金表面をソフトエッチングした後、直接に置換めっき皮膜を形成することを特徴とするめっき方法である。
本発明のめっき方法の具体的なプロセスを例示すると、例えば、
（ｉ）クリーナー処理→水洗→本発明のソフトエッチング液を用いたエッチング処理→水洗→酸洗浄→水洗→置換めっき、という工程、
（ｉｉ）クリーナー処理→水洗→本発明のソフトエッチング液を用いたエッチング処理→水洗→酸洗浄→水洗→置換めっき（パラジウム等の金属めっき）→水洗→置換めっき（金）、という工程、
を挙げることができる。
The plating method of the present invention is a plating method characterized in that after a copper or copper alloy surface is soft etched with the above-described soft etching solution of the present invention, a displacement plating film is directly formed.
Illustrating a specific process of the plating method of the present invention, for example,
(I) Cleaner treatment → water washing → etching process using the soft etching solution of the present invention → water washing → acid washing → water washing → displacement plating,
(Ii) Cleaner process → Washing → Etching process using the soft etching solution of the present invention → Washing → Acid cleaning → Washing → Displacement plating (metal plating such as palladium) → Washing → Substitution plating (gold)
Can be mentioned.
なお、本発明のめっき方法において形成される置換めっき皮膜の金属材料としては、特に限定されるものではないが、例えば金、銀、スズ、パラジウム等が好適である。特に置換めっき皮膜の金属材料が金や銀の場合には、（Ｃ）成分としてクエン酸、グルタル酸、グルタミン酸、又はフタル酸を用いることが好適である。
また、上記置換めっき皮膜の膜厚としても、特に限定されないが、置換銀めっきを行なう場合の膜厚としては通常０．０５〜１μｍ、置換金めっきを行なう場合の膜厚としては通常０．０１〜０．５μｍ、置換スズめっきを行なう場合の膜厚としては通常０．１〜２μｍ、置換パラジウムめっきを行なう場合の膜厚としては通常０．０１〜１μｍである。
In addition, as a metal material of the displacement plating film formed in the plating method of this invention, although it does not specifically limit, gold | metal | money, silver, tin, palladium etc. are suitable, for example. In particular, when the metal material of the displacement plating film is gold or silver, it is preferable to use citric acid, glutaric acid, glutamic acid, or phthalic acid as the component (C).
Further, the thickness of the displacement plating film is not particularly limited, however, the thickness when replacing silver plating is usually 0.05 to 1 μm, and the thickness when replacing gold plating is usually 0.01. ˜0.5 μm, usually 0.1 to 2 μm as the film thickness when the displacement tin plating is performed, and 0.01 to 1 μm as the film thickness when the displacement palladium plating is performed.
以下、実施例及び比較例を示し、本発明をより具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.
［実施例１〜６、比較例１〜５］
本発明の（Ａ）〜（Ｃ）成分、及びジエチレングリコールジエチルエーテル ０．０１Ｍを下表１に示す濃度で配合してエッチング液を調製した。整面研磨を行なっていないＦＲ−４銅張り積層板を処理温度３０℃、エッチング膜厚が２μｍとなるような処理時間にて当該エッチング液に浸漬した。その後水洗、酸洗浄、水洗を行ない、乾燥させて光沢度を測定した。その後、更に置換めっき皮膜を形成し、めっき後の光沢度、外観、及び半田ボイド発生率を観察した。結果を表１に示す。
[Examples 1-6, Comparative Examples 1-5]
Etching liquids were prepared by blending the components (A) to (C) of the present invention and diethylene glycol diethyl ether 0.01M in the concentrations shown in Table 1 below. The FR-4 copper-clad laminate that had not been surface-polished was immersed in the etching solution for a treatment time of 30 ° C. and an etching film thickness of 2 μm. Thereafter, washing with water, washing with acid, washing with water were performed, and drying was performed to measure glossiness. Thereafter, a replacement plating film was further formed, and the glossiness, appearance, and solder void generation rate after plating were observed. The results are shown in Table 1.
置換銀めっき
無電解銀めっき浴ＲＧＡ−１４（上村工業社製）に５０℃×１分間浸漬し、０．２μｍ膜厚の置換めっき皮膜を形成した。
置換金めっき
無電解金めっき浴ＴＣＵ−３６（上村工業社製）に８５℃×２０分間浸漬し、０．０６μｍ膜厚の置換めっき皮膜を形成した。
無電解Ｎｉ−無電解Ａｕめっき
プレディップ液ＭＳＲ−２８Ｐ（上村工業社製）に室温で１分間浸漬し、アクチベーター液ＭＳＲ−２８（上村工業社製）に３０℃で２分間浸漬し、無電解ニッケルめっき浴ＮＰＲ−４（上村工業社製）に８０℃×３０分間浸漬し、更に無電解金めっき浴ＴＳＢ−７１（上村工業社製）に８５℃×１０分間浸漬して、０．０５μｍ膜厚の置換めっき皮膜を形成した。
過酸化水素
３５％過酸化水素水。
硫酸
６２．５％硫酸。
光沢度
ＪＩＳ Ｚ ８７４１に準拠し、光沢度計Ｇｌｏｓｓ Ｍｅｔｅｒ ＶＧ２０００（日本電色工業社製）を用い、光源（ハロゲンランプ）の入射角が２０度の条件で光沢度を測定した。
めっき後外観
目視観察を行ない、下記基準にて評価した。
○：光沢があり、ムラがない。
×：光沢がない、若しくはムラがある。
半田ボイド発生率（％）
シリーズ４０００（Ｄａｇｅ社製）を用い、ボールシェア試験により評価した値を意味する。半田ボールをＢＧＡパターンに実装し、シェア試験を行ない、破断した断面にボイドが発生しているかどうかを確認した。試験条件は、ホットプレート：２３０℃×６０秒、フラックス：非活性ロジンフラックス、半田ボール：Ｓｎ／Ｐｂ＝６３／３７、直径０．７５ｍｍ、シェア速度：１７０μｍ／ｓｅｃ、ツール高：５０μｍとした。
Substitution silver plating electroless silver plating bath RGA-14 (manufactured by Uemura Kogyo Co., Ltd.) was immersed at 50 ° C. for 1 minute to form a substitution plating film having a thickness of 0.2 μm.
It was immersed in a displacement gold plating electroless gold plating bath TCU-36 (manufactured by Uemura Kogyo Co., Ltd.) at 85 ° C. for 20 minutes to form a displacement plating film having a thickness of 0.06 μm.
Immerse in electroless Ni-electroless Au plating pre-dip liquid MSR-28P (manufactured by Uemura Kogyo Co., Ltd.) for 1 minute at room temperature, soak in activator liquid MSR-28 (manufactured by Uemura Kogyo Co., Ltd.) for 2 minutes at 30 ° C. Immerse in electrolytic nickel plating bath NPR-4 (manufactured by Uemura Kogyo Co., Ltd.) at 80 ° C. for 30 minutes, and further immerse in electroless gold plating bath TSB-71 (manufactured by Uemura Kogyo Co., Ltd.) at 85 ° C. for 10 min, 0.05 μm A displacement plating film having a film thickness was formed.
Hydrogen peroxide 35% hydrogen peroxide solution.
Sulfuric acid 62.5% sulfuric acid.
Conforming to gloss JIS Z 8741, using a glossmeter Gloss Meter VG2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the incident angle of the light source (halogen lamp) was measured glossiness at 20 degrees condition.
After plating, the appearance was visually observed and evaluated according to the following criteria.
○: There is gloss and there is no unevenness.
X: No gloss or unevenness.
Solder void generation rate (%)
It means a value evaluated by a ball share test using series 4000 (manufactured by Dage). Solder balls were mounted on a BGA pattern, a shear test was performed, and it was confirmed whether voids occurred in the fractured cross section. The test conditions were: hot plate: 230 ° C. × 60 seconds, flux: inactive rosin flux, solder ball: Sn / Pb = 63/37, diameter 0.75 mm, shear rate: 170 μm / sec, tool height: 50 μm.
表１の結果から、本発明のめっき方法により得られた置換めっき皮膜は、従来の無電解ニッケル−無電解金めっき法（比較例５）により得られた置換めっき皮膜と同等の半田付け性、外観を示すものである。
また、実施例（カルボキシル基を２つ以上有する有機酸を使用する場合）と、比較例１（カルボキシル基を有しない有機酸を使用する場合）、比較例２（カルボキシル基を１つ有する有機酸を使用する場合）、比較例３，４（有機酸を使用しない場合）とを比較すると、実施例により得られる置換めっき皮膜は外観良好で、半田付け特性も格段に改善されていることが明らかである。
なお、ボールシェア強度（シリーズ４０００（Ｄａｇｅ社製）にて測定）については、全ての実施例及び比較例において１５００ｇ以上あり、結果に有意差はなかった。
From the results shown in Table 1, the displacement plating film obtained by the plating method of the present invention has the same solderability as the displacement plating film obtained by the conventional electroless nickel-electroless gold plating method (Comparative Example 5). Appearance is shown.
Further, Examples (when using an organic acid having two or more carboxyl groups), Comparative Example 1 (when using an organic acid having no carboxyl group), and Comparative Example 2 (organic acid having one carboxyl group) ) And Comparative Examples 3 and 4 (when no organic acid is used), it is clear that the displacement plating film obtained by the examples has a good appearance and the soldering characteristics are remarkably improved. It is.
The ball shear strength (measured with a series 4000 (manufactured by Dage)) was 1500 g or more in all examples and comparative examples, and there was no significant difference in the results.
［実施例７〜１２］
３５％過酸化水素水 ５０ｍｌ／Ｌ、６２．５％硫酸 ５０ｍｌ／Ｌ、グルタミン酸 ０．０１Ｍ、及び下表２に示したグリコール類 ０．００５Ｍを配合してエッチング液を調製した。これを「建浴初期エッチング液」とする。整面研磨を行なっていないＦＲ−４銅張り積層板を処理温度３０℃、処理時間２分間の条件下にて当該エッチング液に浸漬し、エッチング処理後の銅表面の外観及び銅表面の溶解量を観察した。
また、上記と同様に調製した「建浴初期エッチング液」にさらに銅を２０ｇ／Ｌの濃度となるように溶解させ、いわゆる浴老化状態のエッチング液を仮想（当該エッチング液を「浴老化後エッチング液」とする）して、上記と同様に整面研磨を行なっていないＦＲ−４銅張り積層板を処理温度３０℃、処理時間２分間の条件下で浸漬し、エッチング処理後の銅表面の外観、銅表面の溶解量を観察した。結果を表２に示す。
[Examples 7 to 12]
An etching solution was prepared by blending 35% hydrogen peroxide solution 50 ml / L, 62.5% sulfuric acid 50 ml / L, glutamic acid 0.01M, and glycols 0.005M shown in Table 2 below. This is referred to as “building bath initial etching solution”. An FR-4 copper-clad laminate that has not been surface-polished is immersed in the etching solution under conditions of a processing temperature of 30 ° C. and a processing time of 2 minutes, and the appearance of the copper surface after etching and the amount of dissolution of the copper surface Was observed.
Further, copper is further dissolved in the “building bath initial etching solution” prepared in the same manner as described above so as to have a concentration of 20 g / L, and a so-called bath aging etching solution is virtually used (the etching solution is “etched after bath aging”). In the same manner as described above, the FR-4 copper-clad laminate that has not been surface-polished is immersed in a treatment temperature of 30 ° C. for a treatment time of 2 minutes, and the copper surface after the etching treatment is immersed. The appearance and the amount of dissolution on the copper surface were observed. The results are shown in Table 2.
溶解量（μｍ）
処理前後の重量差から算出した。
外観
目視観察を行ない、下記基準にて評価した。
○：光沢があり、ムラがない。
×：光沢がない、若しくはムラがある。
溶解比（％）
浴老化後のエッチング液の溶解量が、建浴初期のエッチング液の溶解量に占める割合。
Dissolved amount (μm)
It was calculated from the weight difference before and after the treatment.
The appearance was visually observed and evaluated according to the following criteria.
○: There is gloss and there is no unevenness.
X: No gloss or unevenness.
Dissolution ratio (%)
The ratio of the dissolved amount of the etching solution after bath aging to the dissolved amount of the etching solution in the early stage of the bath.
［実施例１３〜１７、比較例６］
上記表２と同様の条件下、グリコール類の濃度変化によるエッチング速度の推移を調べた。結果を表３に示す。溶解量及び外観については上記表２の場合と同様に評価した。
[Examples 13 to 17, Comparative Example 6]
Under the same conditions as in Table 2 above, changes in etching rate due to changes in the concentration of glycols were examined. The results are shown in Table 3. The dissolution amount and appearance were evaluated in the same manner as in Table 2 above.
Ｒ（％）
グリコール類の濃度が０．００１，０．００５，０．０１，０．０５Ｍの場合を比較し、エッチング量の最大値Ｅmax（μｍ）、エッチング量の最小値Ｅmin（μｍ）として定義される溶解量変動率Ｒ（％）＝１００×（Ｅmax−Ｅmin）／Ｅminの値である。
R (%)
Comparing the case where the concentration of glycols is 0.001, 0.005, 0.01, 0.05M, it is defined as the maximum etching amount E max (μm) and the minimum etching amount E min (μm). Fluctuation amount fluctuation rate R (%) = 100 × (E max −E min ) / E min
表２，３の結果から、カルボキシル基を２つ以上有するカルボン酸と、エチレングリコールモノエチルエーテル又はジエチレングリコールジエチルエーテルとを併用する場合、浴老化によってエッチング処理後の外観が悪化したりエッチング速度が低下したりすることが少ないのみならず、グリコール類の添加濃度によるエッチング速度の変化（溶解量変動率）が他浴に比べて少ないソフトエッチング液が実現される。 From the results shown in Tables 2 and 3, when a carboxylic acid having two or more carboxyl groups and ethylene glycol monoethyl ether or diethylene glycol diethyl ether are used in combination, the appearance after the etching treatment deteriorates or the etching rate decreases due to bath aging. As a result, a soft etching solution is realized in which the change in the etching rate (dissolution rate fluctuation rate) due to the addition concentration of glycols is small compared to other baths.
Claims (5)
5. A plating method comprising: forming a displacement plating film directly after soft etching of a copper or copper alloy surface with the soft etching solution according to claim 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8377325B2 (en) | 2010-03-18 | 2013-02-19 | Samsung Display Co., Ltd. | Etchant for metal wiring and method for manufacturing metal wiring using the same |
| CN103966606A (en) * | 2014-05-06 | 2014-08-06 | 汕头超声印制板（二厂）有限公司 | Copper reduction etching liquid for printed circuit boards |
| CN109563623A (en) * | 2016-08-10 | 2019-04-02 | 上村工业株式会社 | The preparation method of the chemical plating pretreatment liquid and printed circuit board that are used simultaneously with reduction treatment |
| CN114574863A (en) * | 2022-03-10 | 2022-06-03 | 上海富柏化工有限公司 | Low-loss black hole micro-etching solution and preparation method and application thereof |
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| US8377325B2 (en) | 2010-03-18 | 2013-02-19 | Samsung Display Co., Ltd. | Etchant for metal wiring and method for manufacturing metal wiring using the same |
| CN103966606A (en) * | 2014-05-06 | 2014-08-06 | 汕头超声印制板（二厂）有限公司 | Copper reduction etching liquid for printed circuit boards |
| CN103966606B (en) * | 2014-05-06 | 2016-04-06 | 汕头超声印制板（二厂）有限公司 | A kind ofly subtract copper etching solution for printed circuit board |
| CN109563623A (en) * | 2016-08-10 | 2019-04-02 | 上村工业株式会社 | The preparation method of the chemical plating pretreatment liquid and printed circuit board that are used simultaneously with reduction treatment |
| US20190264329A1 (en) * | 2016-08-10 | 2019-08-29 | C. Uyemura & Co., Ltd. | Pretreating liquid for electroless plating to be used during reduction treatment, and process for producing printed wiring board |
| EP3498884A4 (en) * | 2016-08-10 | 2020-04-01 | C. Uyemura & Co., Ltd. | Pretreating liquid for electroless plating to be used during reduction treatment, and process for producing printed wiring board |
| US10927463B2 (en) | 2016-08-10 | 2021-02-23 | C. Uyemura & Co., Ltd. | Pretreating liquid for electroless plating to be used during reduction treatment, and process for producing printed wiring board |
| CN114574863A (en) * | 2022-03-10 | 2022-06-03 | 上海富柏化工有限公司 | Low-loss black hole micro-etching solution and preparation method and application thereof |
| CN114574863B (en) * | 2022-03-10 | 2023-12-01 | 上海富柏化工有限公司 | Low-loss black hole microetching solution and preparation method and application thereof |
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