JP3577345B2 - Stabilization of acidic aqueous hydrogen peroxide solution containing copper and palladium. - Google Patents
Stabilization of acidic aqueous hydrogen peroxide solution containing copper and palladium. Download PDFInfo
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- JP3577345B2 JP3577345B2 JP20123294A JP20123294A JP3577345B2 JP 3577345 B2 JP3577345 B2 JP 3577345B2 JP 20123294 A JP20123294 A JP 20123294A JP 20123294 A JP20123294 A JP 20123294A JP 3577345 B2 JP3577345 B2 JP 3577345B2
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- hydrogen peroxide
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Description
【０００１】
【産業上の利用分野】
本発明は銅およびパラジウムを含む酸性過酸化水素水溶液の安定化法に関する。
【０００２】
【従来の技術とその課題】
酸性過酸化水素水溶液は、銅および銅合金材料の化学的な溶解剤として、すぐれた溶解力を有することが知られており、銅及び銅合金のピックリング、エッチング、ケミカルポリッシング、治具洗浄等に広く利用されている。しかし過酸化水素は分解しやすい化合物であり、特に銅、パラジウム、白金イオン等の存在において触媒的に分解する。このため、酸性過酸化水素水溶液を銅および銅合金の化学的な溶解処理に使用する場合、銅が溶解し、液中に銅イオンが蓄積されると、過酸化水素の分解が促進される。また、銅メッキ工程のステンレス製治具の洗浄に使用する場合は治具に付着する銅およびパラジウムが溶解し、液中に銅イオン、パラジウムイオンが蓄積し著しく過酸化水素の分解が促進され、過酸化水素の有効利用率が著しく低下し、不経済となる欠点がある。
かかる欠点を改良するために従来からフェノール、飽和脂肪族アルコール等種々の化合物が試みられているが、効果的な安定化法は少なく、特に銅及びバラジウムイオンの存在する酸性過酸化水素水溶液に対する効果的な安定化法はほとんど知られていない。
本発明の目的は少量の添加ですぐれた安定化効果を示す新しい添加剤を用いることによる銅およびパラジウムを含む酸性過酸化水素水溶液の安定化法を提供することにある。
【０００３】
【課題を解決するための手段】
本発明は、過酸化水素を触媒的に分解させる銅イオンおよびパラジウムイオンを含有する酸性過酸化水素水溶液にジピリジル化合物を添加することを特徴とする上記酸性過酸化水素水溶液の安定化法にある。
本発明で用いるジピリジル化合物はパラジウムイオンが共存しない系即ち銅イオンを含有する酸性過酸化水素水溶液の安定化に対しても勿論有効である。
【０００４】
銅（銅合金を包含する）の化学的な溶解処理やステンレス治具等に付着する銅およびパラジウムの化学的な溶解処理に用いる酸性過酸化水素水溶液は通常過酸化水素を１０〜１５０ｇ／ｌ、酸を１０〜２００ｇ／ｌ程度含む。酸としては硫酸が一般的だが、硝酸、リン酸等の鉱酸も有用である。
本発明はかかる酸性過酸化水素水溶液に銅およびパラジウムイオンが蓄積されることによって過酸化水素が分解されるのをジピリジル化合物を添加することによって防止するものである。
従って銅イオンやパラジウムイオンが蓄積する前の酸性過酸化水素水溶液にジピリジル化合物を添加する態様も勿論本発明に包含される。
【０００５】
本発明で用いるジピリジル化合物の具体例としては２，２′−ジピリジル、２，３′−ジピリジル、２，４′−ジピリジル，３，３′−ジピリジル、３，４′−ジピリジル、４，４′−ジピリジル等がある。
ジピリジル化合物は通常酸性過酸化水素水溶液に対し０．０１ｇ／ｌ以上添加する。上限には特に制限はないが通常５０ｇ／ｌ以下で十分であり、一般的には０．１〜１０ｇ／ｌ程度用いられる。
かくして銅やパラジウムが溶解して銅イオンおよびパラジウムイオンが蓄積した場合でも過酸化水素の分解を効果的に抑制することができ、化学的溶解剤としての酸性過酸化水素水溶液の使用を一層経済的にすることが可能となる。
次に実施例及び比較例により本発明の効果を例証する。
【０００６】
【実施例】
実施例１
Ｈ２Ｏ２７０ｇ／ｌ、Ｈ２ＳＯ４１５０ｇ／ｌ、ＣｕＳＯ４−５Ｈ２Ｏ５０ｇ／ｌを含む５０℃の水溶液にジピリジル化合物０．１〜１０ｇ／ｌを添加して、過酸化水素の分解量を測定した結果を表１に示す。
【０００７】
【表１】
実施例２
Ｈ２Ｏ２７０ｇ／ｌ、Ｈ２ＳＯ４１５０ｇ／ｌ、ＣｕＳＯ４−５Ｈ２Ｏ５０ｇ／ｌ、ＰｄＳＯ４０．１ｇ／ｌを含む５０℃の水溶液にジピリジル化合物０．１〜１０ｇ／ｌを添加して、過酸化水素の分解量を測定した結果を表２に示す。
【０００９】
【表２】
実施例３
Ｈ２Ｏ２７０ｇ／ｌ、ＨＮＯ３３０ｇ／ｌ、ＣｕＳＯ４−５Ｈ２Ｏ５０ｇ／ｌ、ＰｄＳＯ４０．１ｇ／ｌ、２，２′−ジピリジル１ｇ／ｌを含む水溶液の３０℃における過酸化水素の分解量は０．２９ｇ／ｌ・ｈｒであった。２，２′−ジピリジル無添加で、同一条件での過酸化水素の分解量は１２．４ｇ／ｌ・ｈｒであった。故に過酸化水素の分解量は無添加の場合の１／４３程度にすぎなかった。
【００１１】
実施例４
Ｈ２Ｏ２１００ｇ／ｌ、Ｈ３ＰＯ４５０ｇ／ｌ、ＣｕＳＯ４−５Ｈ２Ｏ５０ｇ／ｌ、ＰｄＳＯ４０．１ｇ／ｌ、２，４′−ジピリジル５ｇ／ｌを含む水溶液の６０℃における過酸化水素の分解量は０．３７ｇ／ｌ・ｈｒであった。２，４′−ジピリジル無添加で、同一条件での過酸化水素の分解量は１０．３ｇ／ｌ・ｈｒであった。故に過酸化水素の分解量は無添加の場合の１／２８程度にすぎなかった。[0001]
[Industrial applications]
The present invention relates to a method for stabilizing an aqueous acidic hydrogen peroxide solution containing copper and palladium.
[0002]
[Prior art and its problems]
Acidic hydrogen peroxide aqueous solution is known to have excellent dissolving power as a chemical dissolving agent for copper and copper alloy materials. Pickling, etching, chemical polishing, jig cleaning, etc. of copper and copper alloys are known. Widely used for However, hydrogen peroxide is a compound that is easily decomposed, and particularly decomposes catalytically in the presence of copper, palladium, platinum ions and the like. Therefore, when an acidic aqueous hydrogen peroxide solution is used for the chemical dissolution treatment of copper and copper alloys, decomposition of hydrogen peroxide is promoted when copper is dissolved and copper ions are accumulated in the solution. In addition, when used for cleaning a stainless steel jig in the copper plating process, copper and palladium adhering to the jig dissolve, copper ions and palladium ions accumulate in the solution, and the decomposition of hydrogen peroxide is remarkably promoted. There is a drawback that the effective utilization rate of hydrogen peroxide is remarkably reduced, which is uneconomical.
Various compounds such as phenol and saturated aliphatic alcohol have been tried in the past to improve such drawbacks, but there are few effective stabilization methods, particularly for aqueous solutions of acidic hydrogen peroxide in which copper and palladium ions are present. Little is known about effective stabilization methods.
An object of the present invention is to provide a method for stabilizing an aqueous solution of acidic hydrogen peroxide containing copper and palladium by using a new additive exhibiting excellent stabilizing effects with a small amount of addition.
[0003]
[Means for Solving the Problems]
The present invention resides in the above-mentioned method for stabilizing an aqueous solution of acidic hydrogen peroxide, which comprises adding a dipyridyl compound to an aqueous solution of acidic hydrogen peroxide containing copper ions and palladium ions that catalytically decomposes hydrogen peroxide.
The dipyridyl compound used in the present invention is, of course, effective for stabilizing a system in which palladium ions do not coexist, that is, an acidic aqueous hydrogen peroxide solution containing copper ions.
[0004]
The aqueous solution of acidic hydrogen peroxide used for the chemical dissolution treatment of copper (including a copper alloy) and the chemical dissolution treatment of copper and palladium adhering to a stainless steel jig usually contains hydrogen peroxide at 10 to 150 g / l. Contains about 10 to 200 g / l of acid. As the acid, sulfuric acid is generally used, but mineral acids such as nitric acid and phosphoric acid are also useful.
The present invention prevents decomposition of hydrogen peroxide due to accumulation of copper and palladium ions in such an aqueous solution of acidic hydrogen peroxide by adding a dipyridyl compound.
Accordingly, the present invention naturally includes a mode in which the dipyridyl compound is added to the acidic aqueous hydrogen peroxide solution before the accumulation of copper ions or palladium ions.
[0005]
Specific examples of the dipyridyl compound used in the present invention include 2,2'-dipyridyl, 2,3'-dipyridyl, 2,4'-dipyridyl, 3,3'-dipyridyl, 3,4'-dipyridyl, and 4,4 ' -Dipyridyl and the like.
The dipyridyl compound is usually added in an amount of 0.01 g / l or more to the aqueous solution of acidic hydrogen peroxide. Although there is no particular upper limit, 50 g / l or less is usually sufficient, and generally about 0.1 to 10 g / l is used.
Thus, decomposition of hydrogen peroxide can be effectively suppressed even when copper and palladium are dissolved and copper ions and palladium ions accumulate, making it even more economical to use acidic hydrogen peroxide aqueous solution as a chemical dissolving agent. It becomes possible to.
Next, the effects of the present invention will be illustrated by examples and comparative examples.
[0006]
【Example】
Example 1
Decomposition of hydrogen peroxide by adding 0.1 to 10 g / l of a dipyridyl compound to a 50 ° C. aqueous solution containing 70 g / l of H 2 O 2, 150 g / l of H 2 SO 4 and 50 g / l of CuSO 4 -5H 2 O Table 1 shows the measurement results.
[0007]
[Table 1]
Example 2
H 2 O 2 70g / l, H 2 SO 4 150g / l, CuSO 4 -5H 2 O50g / l, added dipyridyl compound 0.1 to 10 g / l in an aqueous solution of 50 ° C. containing PdSO 4 0.1 g / l Table 2 shows the results of measuring the decomposition amount of hydrogen peroxide.
[0009]
[Table 2]
Example 3
H 2 O 2 70g / l, HNO 3 30g / l, CuSO 4 -5H 2 O50g / l, PdSO 4 0.1g / l, hydrogen peroxide at 30 ° C. of an aqueous solution containing a 2,2'-dipyridyl 1 g / l Was 0.29 g / l · hr. The amount of hydrogen peroxide decomposed under the same conditions without addition of 2,2'-dipyridyl was 12.4 g / l · hr. Therefore, the decomposition amount of hydrogen peroxide was only about 1/43 of the case without addition.
[0011]
Example 4
An aqueous solution containing 100 g / l of H 2 O 2, 50 g / l of H 3 PO 4, 50 g / l of CuSO 4 -5H 2 O, 0.1 g / l of PdSO 4 and 5 g / l of 2,4′-dipyridyl at 60 ° C. The decomposition amount of hydrogen oxide was 0.37 g / l · hr. The amount of hydrogen peroxide decomposed under the same conditions without addition of 2,4'-dipyridyl was 10.3 g / l · hr. Therefore, the amount of hydrogen peroxide decomposed was only about 1/28 of that in the case of no addition.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20123294A JP3577345B2 (en) | 1994-07-25 | 1994-07-25 | Stabilization of acidic aqueous hydrogen peroxide solution containing copper and palladium. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20123294A JP3577345B2 (en) | 1994-07-25 | 1994-07-25 | Stabilization of acidic aqueous hydrogen peroxide solution containing copper and palladium. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0834602A JPH0834602A (en) | 1996-02-06 |
| JP3577345B2 true JP3577345B2 (en) | 2004-10-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20123294A Expired - Lifetime JP3577345B2 (en) | 1994-07-25 | 1994-07-25 | Stabilization of acidic aqueous hydrogen peroxide solution containing copper and palladium. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3577345B2 (en) |
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1994
- 1994-07-25 JP JP20123294A patent/JP3577345B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH0834602A (en) | 1996-02-06 |
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