JPH0348274B2 - - Google Patents
Info
- Publication number
- JPH0348274B2 JPH0348274B2 JP3488886A JP3488886A JPH0348274B2 JP H0348274 B2 JPH0348274 B2 JP H0348274B2 JP 3488886 A JP3488886 A JP 3488886A JP 3488886 A JP3488886 A JP 3488886A JP H0348274 B2 JPH0348274 B2 JP H0348274B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- patina
- hydrogen peroxide
- water
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229940116318 copper carbonate Drugs 0.000 claims description 7
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 241001311547 Patina Species 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- -1 chlorine ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- NMLJPOYVNGSKLU-UHFFFAOYSA-N [NH4+].[NH4+].[NH4+].[Cl-].[O-]S([O-])(=O)=O Chemical compound [NH4+].[NH4+].[NH4+].[Cl-].[O-]S([O-])(=O)=O NMLJPOYVNGSKLU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は表面と反応性媒体との反応による金属
質材料の化学的表面処理の分野に属し、銅及び銅
合金表面に人工的に緑青被膜を発生させるために
利用される。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention belongs to the field of chemical surface treatment of metallic materials by reaction of the surface with a reactive medium. is used to generate.
（従来の技術）
従来の銅表面に人工的に緑青を発生させる一般
的なものとしては、アンモニウム塩や硫酸塩や銅
塩その他の塩類や酸または塩基を適当な割合で浸
合した水溶液や塩基性炭酸銅を含む樹脂を塗布す
る等の手法が採られているが、これ等の方法では
処理工程中に有毒なガスを発生したり、緑青がす
ぐに剥離したり、剥離した後の天然の緑青が発生
するまでに数年の歳月を要する等の問題があつ
た。(Prior art) Conventional methods for artificially producing patina on copper surfaces include aqueous solutions or bases in which ammonium salts, sulfates, copper salts, other salts, acids, or bases are impregnated in appropriate proportions. However, these methods generate toxic gas during the treatment process, cause the patina to peel off immediately, or cause the natural color to fade after peeling. There were problems such as the fact that it took several years for patina to develop.
（発明が解決しようとする問題点）
本発明は上記欠陥を解消して安定した緑青を効
率的に銅表面に生成し得る人工緑青発生液を提供
しようとするものである。(Problems to be Solved by the Invention) The present invention aims to provide an artificial patina generation liquid that can eliminate the above-mentioned defects and efficiently generate a stable patina on a copper surface.
（問題点を解決するための手段）
本発明は上記課題を達成するため、所定量の水
に対して塩基性炭酸銅、塩酸、硫酸アンモニウ
ム、塩化アンモニウム、過酸化水素水をそれぞれ
適量に含有させた水溶液から成るものである。(Means for Solving the Problems) In order to achieve the above-mentioned problems, the present invention contains appropriate amounts of basic copper carbonate, hydrochloric acid, ammonium sulfate, ammonium chloride, and hydrogen peroxide in a predetermined amount of water. It consists of an aqueous solution.
（作用）
本発明の水溶液では、塩基性炭酸銅は溶液中で
銅イオンと二酸化炭素と水に分解される。このう
ちの銅イオンは後述の過酸化水素によつて形成さ
れた銅イオンと共に溶液及び空気中の二酸化炭
素、硫酸アンモニウム、塩化アンモニウムの硫酸
イオン、塩素イオンと反応し同じくアンモニウム
イオンによつて生じた水酸化銅と共に塩基性炭酸
銅になつて緑青の色をよくする。残りの二酸化炭
素は塩基性炭酸銅の形成を促す。次に、過酸化水
素は反応性が強く、銅表面の酸化銅や銅地金を酸
化して銅イオンとして溶かし出す。そのとき過酸
化水素は水酸イオンに還元されて水酸化銅の形成
を促す。また、過酸化水素でエツチングされた銅
表面は非常に凹凸があるために、形成された塩基
性炭酸銅などは投錨効果により剥離は流出が起こ
りにくくなる。(Function) In the aqueous solution of the present invention, basic copper carbonate is decomposed into copper ions, carbon dioxide, and water in the solution. Among these, the copper ions react with the copper ions formed by hydrogen peroxide, which will be described later, with carbon dioxide, ammonium sulfate, ammonium chloride sulfate ions, and chlorine ions in the solution and air, and the water generated by the ammonium ions also reacts. Together with copper oxide, it becomes basic copper carbonate and improves the patina color. The remaining carbon dioxide promotes the formation of basic copper carbonate. Next, hydrogen peroxide is highly reactive and oxidizes the copper oxide on the copper surface and the copper base metal, dissolving it as copper ions. Hydrogen peroxide is then reduced to hydroxide ions, promoting the formation of copper hydroxide. Furthermore, since the copper surface etched with hydrogen peroxide is very uneven, the formed basic copper carbonate is less likely to peel off or flow out due to the anchoring effect.
（実施例）
本発明による人工緑青発生液は種々試験の結
果、水1000c.c.に対して塩基性炭酸銅20ｇ〜60ｇ、
塩酸60c.c.〜90c.c.、硫酸アンモニウム15ｇ〜50ｇ、
塩化アンモニウム15ｇ〜50ｇ、炭酸化水素水50c.c.
〜90c.c.から成る混合液にして、上記各配合物質に
おいて各個に対応した配合割合の範囲内で一定の
緑青生成効果を確認したものである。(Example) As a result of various tests, the artificial patina generating liquid according to the present invention has a basic copper carbonate of 20 to 60 g per 1000 c.c. of water.
Hydrochloric acid 60 c.c. ~ 90 c.c., ammonium sulfate 15 g ~ 50 g,
Ammonium chloride 15g to 50g, hydrogen carbonate water 50c.c.
A certain patina-producing effect was confirmed within the range of the proportions of each of the above-mentioned compounded substances in a mixed solution consisting of ~90 c.c.
上記した人工緑青発生液は常温で銅表面に刷毛
またはスプレー等で塗布され、銅表面はエツチン
グされながら該表面に密着性の良い天然緑青に近
い人工緑青が生成する。 The above-mentioned artificial patina generation liquid is applied to the copper surface with a brush or spray at room temperature, and as the copper surface is etched, an artificial patina close to natural patina with good adhesion is generated on the surface.
（発明の効果）
本発明によれば、過酸化水素は反応性が強いた
めに常温以下の温度で充分反応が進行する。ま
た、従来の反応性の低い溶液の場合では水分の蒸
発をゆつくりにして反応を進行させるために水銀
などを加えていたが本発明では加えなくて済むた
め有害ガスや蒸発を発生しないの特長をもつて人
工緑青を強固に生成する効果がある。(Effects of the Invention) According to the present invention, since hydrogen peroxide has strong reactivity, the reaction proceeds sufficiently at a temperature below room temperature. In addition, in the case of conventional solutions with low reactivity, mercury or the like was added to slow the evaporation of water and allow the reaction to proceed, but this invention does not require the addition of mercury, so no harmful gases or evaporation are generated. It has the effect of strongly producing artificial patina.
Claims (1)
酸アンモニウム、塩化アンモニウム、過酸化水素
水を適量に配合した水溶液から成る人工緑青発生
液。1. An artificial patina-generating solution consisting of an aqueous solution containing appropriate amounts of basic copper carbonate, hydrochloric acid, ammonium sulfate, ammonium chloride, and hydrogen peroxide in the required amount of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3488886A JPS62192586A (en) | 1986-02-18 | 1986-02-18 | Artificial patina producing solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3488886A JPS62192586A (en) | 1986-02-18 | 1986-02-18 | Artificial patina producing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62192586A JPS62192586A (en) | 1987-08-24 |
| JPH0348274B2 true JPH0348274B2 (en) | 1991-07-23 |
Family
ID=12426691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3488886A Granted JPS62192586A (en) | 1986-02-18 | 1986-02-18 | Artificial patina producing solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62192586A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2588036B2 (en) * | 1990-02-13 | 1997-03-05 | 日鉱金属株式会社 | How to form patina |
| DE19809904A1 (en) * | 1998-03-07 | 1999-09-09 | Km Europa Metal Ag | Process and reaction solution to create a patina |
-
1986
- 1986-02-18 JP JP3488886A patent/JPS62192586A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62192586A (en) | 1987-08-24 |
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