JPH02240277A - Method for coloring copper - Google Patents
Method for coloring copperInfo
- Publication number
- JPH02240277A JPH02240277A JP5951789A JP5951789A JPH02240277A JP H02240277 A JPH02240277 A JP H02240277A JP 5951789 A JP5951789 A JP 5951789A JP 5951789 A JP5951789 A JP 5951789A JP H02240277 A JPH02240277 A JP H02240277A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- copper
- ammonium
- soln
- hue
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 34
- 239000010949 copper Substances 0.000 title claims description 23
- 229910052802 copper Inorganic materials 0.000 title claims description 22
- 238000004040 coloring Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000005486 sulfidation Methods 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 8
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007654 immersion Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract 3
- 238000000576 coating method Methods 0.000 abstract 3
- 235000019646 color tone Nutrition 0.000 abstract 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 abstract 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 101100478187 Arabidopsis thaliana MOS4 gene Proteins 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- QLRJKPHPWDKCGG-UHFFFAOYSA-K O[Sb](O)(O)=S.N.N.N Chemical compound O[Sb](O)(O)=S.N.N.N QLRJKPHPWDKCGG-UHFFFAOYSA-K 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は銅を薄い干渉色から真黒色とすることにより
、この着色を生かした屋内外の銅系装飾品、電気部品、
機械部品に関するものである。[Detailed Description of the Invention] <Industrial Application Fields> This invention changes copper from a pale interference color to a true black color, thereby making use of this coloring to produce indoor and outdoor copper-based ornaments, electrical parts,
It concerns mechanical parts.
〈従来の技術〉〈発明が解決すべき課題〉従来銅の表面
着色方法としては強アルカリ性酸化剤による高熱酸化に
よって酸化銅を生成する黒化処理が知られている。<Prior Art><Problems to be Solved by the Invention> As a conventional method for coloring the surface of copper, blackening treatment is known in which copper oxide is produced by high-temperature oxidation using a strong alkaline oxidizing agent.
この方法は具体的には亜塩素酸ナトリウムと水酸化ナト
リウムを数％添加したアルカリ水溶液を９０℃以上に加
熱して、この中に銅を１乃至数分間浸漬する方法であっ
て、黒化処理した銅製品に処理液が残留すると浴成分が
製品上に晶出し、黒化した製品の外観を損なうとともに
他の物体と接触すると残留成分による腐食や変色等を起
す問題がある。Specifically, this method involves heating an alkaline aqueous solution containing a few percent of sodium chlorite and sodium hydroxide to 90°C or higher, and immersing the copper in this solution for one to several minutes. If the treatment solution remains on a copper product, the bath components will crystallize on the product, impairing the appearance of the blackened product, and when it comes into contact with other objects, the remaining components will cause corrosion and discoloration.
又、黒化処理にあたって、９０℃以上に加熱しないと均
一な酸化反応が起り難く、黒化処理すべき銅製品が大型
のものになると、そのもの自体を予熱したり浴加熱設備
も大型化する必要が生じたり種々の問題が発生する。In addition, during blackening treatment, it is difficult for a uniform oxidation reaction to occur unless the copper product is heated to 90°C or higher, and if the copper product to be blackened is large, it is necessary to preheat the product itself or use larger bath heating equipment. or various other problems may occur.
更に処理液の廃水処理に当り中和することにかなりの困
難を伴ない、この方法で生成される酸化膜は最高数μｍ
厚の酸化第二銅（Ｃｕｂ）で母体への密着は良好である
が、若干の絶縁性を示すために、良好な導電性を要求さ
れる用途に使用することが出来ない。Furthermore, it is quite difficult to neutralize the treated liquid during wastewater treatment, and the oxide film produced by this method is at most several μm thick.
Although the thick cupric oxide (Cub) has good adhesion to the base material, it exhibits some insulating properties and cannot be used in applications requiring good conductivity.
またこのような処理により銅の表面の色相は赤茶乃至黒
色であり、赤、紫、青紫と云った色を出すことは出来な
い。Furthermore, due to such treatment, the hue of the copper surface is reddish-brown to black, and colors such as red, purple, and bluish-purple cannot be produced.
本発明はこのような問題点を解決する方法を目的とする
ものである。The object of the present invention is to provide a method for solving these problems.
く課題を解決するための手段〉
本発明の概要は、銅を金属のチオ酸水溶液中に浸漬し、
硫化反応によって銅を着色する方法である。Means for Solving the Problems> The outline of the present invention is to immerse copper in a metal thioic acid aqueous solution,
This is a method of coloring copper through a sulfurization reaction.
〈作 用〉
上記の金属のチオ酸塩として実用的なものはチオモリブ
デン酸アンモニウム、チオタングステン酸アンモニウム
、チオスズ酸アンモニウム、チオアンチモン酸アンモニ
ウム、チオ銅酸カリウム等があげられる。<Function> Practical thioacid salts of the above metals include ammonium thiomolybdate, ammonium thiotungstate, ammonium thiostannate, ammonium thioantimonate, potassium thiocuprate, and the like.
銅の着色のメカニズムは浴成分である金属のチオ酸塩と
銅との二次反応により硫化銅を生成させるもので、テト
ラチオモリブデン酸アンモニウム（ＮＨ４）！ ＭＯ３
４を例にして説明すると以下の反応式に従って着色した
硫化銅が生成される。The mechanism of copper coloring is the formation of copper sulfide through a secondary reaction between the metal thioate salt, which is a bath component, and copper, ammonium tetrathiomolybdate (NH4)! MO3
To explain using Example 4 as an example, colored copper sulfide is produced according to the following reaction formula.
２ （ＮＨ４ｈ ＭＯ３４＋Ｃｕ＋４８ｚＯ→２ＮＨ，
ＯＨ＋ＣｕＳ＋２Ｍ０３ｚ 十ＨｘＳ （１）Ｑ ｕ
＋ ＨｌＳ−Ｃｕ Ｓ ＋ Ｈｚ ・曲−（
２）上記（１）、（２）の反応により非常に緻密な硫化
銅上記（１１の皮膜が生成する。このとき浴温および処
理時間（反応時間）により、硫化銅の膜厚が変化するが
、比較的短時間で数μの膜厚を付けることができる。
これによって色相が微妙に変化したものが得られるので
ある。金属のチオ酸水溶液の濃度としては０，０１重量
％以上あれば着色処理が容易であり好ましいが、より好
ましい濃度としては０．５〜３．０重量％である。2 (NH4h MO34+Cu+48zO→2NH,
OH+CuS+2M03z 1HxS (1) Q u
+ HlS-Cu S + Hz ・Song-(
2) The reactions of (1) and (2) above produce a very dense copper sulfide film (No. 11 above). At this time, the thickness of the copper sulfide film changes depending on the bath temperature and treatment time (reaction time). , a film thickness of several microns can be formed in a relatively short time.
This results in an image with a slightly changed hue. The concentration of the metal thioic acid aqueous solution is preferably 0.01% by weight or more since coloring treatment is easy, but the more preferred concentration is 0.5 to 3.0% by weight.
０．５〜３．０重量％を特定する理由は０．５重量％未
満では反応に時間がかかり過ぎ生産能率が悪（、また３
、０重量％を超えると浴が高価となるにも拘わらず効率
が増すわけではないので不経済である。又、浴温は室温
でも良いが、反応を促進するために、チオ酸塩の分解が
進み過ぎない範囲で加温してもよく、好ましい温度は６
０℃以内である。又、銅の着色処理をするための銅製品
の前処理は、通常の脱脂と活性化方法でよいが、特に銅
が線材である場合には、これらの金属のチオ酸塩に潤滑
性能があるため、ダイス等で銅線材を軽く塑性変形して
銅の新生面を作り得るのでこの面とチオ酸浴で前記した
（１）、 （２）の反応を生ゼしめて、ＣｕＳ （硫化
銅）を形成させることができる。The reason for specifying 0.5 to 3.0% by weight is that if it is less than 0.5% by weight, the reaction will take too long and the production efficiency will be poor (also 3.0% by weight).
If the content exceeds 0% by weight, the bath becomes expensive but the efficiency does not increase, which is uneconomical. In addition, the bath temperature may be room temperature, but in order to promote the reaction, it may be heated within a range where the decomposition of the thioate salt does not progress too much, and the preferred temperature is 6
It is within 0℃. In addition, the pretreatment of copper products for copper coloring can be done by ordinary degreasing and activation methods, but especially when the copper is a wire rod, the thioates of these metals have lubricating properties. Therefore, a new surface of copper can be created by lightly plastically deforming the copper wire with a die, etc., and the above-mentioned reactions (1) and (2) are generated in this surface and a thioacid bath to form CuS (copper sulfide). can be done.
又、金属のチオ酸塩としてテトラチオタングステン酸ア
ンモニウム（Ｎ Ｈ４） ！ Ｗ Ｓ ａを例として説
明すると以下の反応式に従って着色した硫化銅が生成さ
れる。In addition, ammonium tetrathiotungstate (NH4) is used as a metal thioate salt! Taking W Sa as an example, colored copper sulfide is produced according to the following reaction formula.
２ （ＮＨａ）ｚ ＷＳａ ／’ ＋ Ｃｕ ＋ ４
Ｈ！ ０−２ＮＨａ ＯＨ＋ＣｕＳ＋２ＷＳｓ ＋）（
、Ｓ−・−（１）Ｃｕ＋Ｈ，５−ＣｕＳ＋Ｈｚ
−（２）上記（１）、（２）の反応により非常に緻密
な硫化銅の皮膜が生成する。2 (NHa)z WSa /' + Cu + 4
H! 0-2NHa OH+CuS+2WSs+)(
, S-・-(1)Cu+H,5-CuS+Hz
-(2) A very dense copper sulfide film is formed by the reactions in (1) and (2) above.
この時の浴温、処理時間、濃度の関係が前記テトラチオ
モリブデン酸アンモニウムの場合と大略同様である。The relationship among bath temperature, treatment time, and concentration at this time is approximately the same as in the case of ammonium tetrathiomolybdate.
（実施例）
例１．テトラチオモリブデン酸アンモニウム（ＮＨ４）
、ＭＯ３４（７）０．５％水溶液を４０＋２℃に保持し
た浴槽中に５０μφの硬銅線を浸漬し、浸漬時間を変え
て色相を変化させた。処理に当っては硬銅線を予め市販
の中性脱脂液（アイソレートクリーナ・ＡＸ、アイソレ
ート化学研究所製）で十分に洗滌脱脂して用いた。(Example) Example 1. Ammonium tetrathiomolybdate (NH4)
A hard copper wire of 50 μφ was immersed in a bath containing a 0.5% aqueous solution of MO34(7) at 40+2° C., and the hue was changed by changing the immersion time. In the treatment, the hard copper wire was thoroughly cleaned and degreased with a commercially available neutral degreasing solution (Isolate Cleaner AX, manufactured by Isolate Kagaku Kenkyusho).
この硬銅線の浸漬時間と色相を示せば下表のとおりであ
る。The immersion time and hue of this hard copper wire are shown in the table below.
着色した硬銅線を１００℃、３０分間加熱したところ、
いずれの試料も色相の変化は認められなかった。When colored hard copper wire was heated at 100℃ for 30 minutes,
No change in hue was observed in any of the samples.
次にテトラチオモリブデン酸アンモニウムの浴濃度を変
化させ、浸漬時間を３０秒、浴温を４０±２℃とした場
合の色相の変化を示せば次表のとおりである。Next, the following table shows the change in hue when the bath concentration of ammonium tetrathiomolybdate was changed, the immersion time was 30 seconds, and the bath temperature was 40±2°C.
着色した硬銅線を１００℃、３０分間加熱したところ、
いずれの試料も色相の変化は認められなかった。When colored hard copper wire was heated at 100℃ for 30 minutes,
No change in hue was observed in any of the samples.
又、テトラチオモリブデン酸アンモニウム（ＮＨ４：ｈ
ＭＯＳ４の０．５％水溶液を処理浴とし、浴温を変化
させながら、３０秒間硬銅線を浸漬した場合の色相を示
せば次表のとおりである。Also, ammonium tetrathiomolybdate (NH4:h
The following table shows the hue when a hard copper wire was immersed in a 0.5% aqueous solution of MOS4 for 30 seconds while changing the bath temperature.
着色した硬銅線を１００℃、３０分間加熱したところ、
いずれの試料も色相の変化は認められなかった。When colored hard copper wire was heated at 100℃ for 30 minutes,
No change in hue was observed in any of the samples.
以上のように処理浴の種類、濃度、温度、処理時間を変
化させることによって、薄い干渉色から真黒色に至る広
範囲の環系着色を施すことができた。By changing the type of treatment bath, concentration, temperature, and treatment time as described above, it was possible to apply a wide range of ring-based coloring, from pale interference colors to deep black.
例２テトラチオタングステン酸アンモニウム（Ｎ Ｈａ
）ｔ Ｗ Ｓ ａの０．５％水溶液を４０±２℃に保持
した浴槽中に５０μφの硬銅線を浸漬し、浸漬時間を変
えて色相を変化させた。処理に当っては硬銅線を予め市
販の中性脱脂液（アイソレートクリーナ・ＡＸ、アイソ
レート化学研究断裂）で十分に洗滌脱脂して用いた。Example 2 Ammonium tetrathiotungstate (N Ha
) A hard copper wire of 50 μΦ was immersed in a bath containing a 0.5% aqueous solution of t W Sa at 40±2° C., and the hue was changed by changing the immersion time. In the treatment, the hard copper wire was thoroughly cleaned and degreased with a commercially available neutral degreasing solution (Isolate Cleaner AX, Isolate Kagaku Kenkyusha).
この硬銅線の浸漬時間と色相を示せば下表のとおりであ
る。The immersion time and hue of this hard copper wire are shown in the table below.
着色した硬銅線を１００℃、３０分間加熱したところい
ずれの試料も色相の変化は認められなかった。When colored hard copper wires were heated at 100° C. for 30 minutes, no change in hue was observed in any of the samples.
次にテトラチオタングステン酸アンモニウムの浴濃度を
変化させ、浸漬時間を３０秒、浴温を４０±２℃とした
場合の色相の変化を示せば次表のとおりである。Next, the following table shows the change in hue when the bath concentration of ammonium tetrathiotungstate was changed, the immersion time was 30 seconds, and the bath temperature was 40±2°C.
又、テトラチオタングステン酸アンモニウム（ＮＨ４）
ｚ ＷＳａの０．５％水溶液を処理浴とし、浴温を変化
させながら、３０秒間硬銅線を浸漬した場合の色相を示
せば次表のとおりである。Also, ammonium tetrathiotungstate (NH4)
The following table shows the hue when a hard copper wire was immersed in a 0.5% aqueous solution of WSa for 30 seconds while changing the bath temperature.
着色した硬銅線を１００℃、３０分間加熱したところい
ずれの試料も色相の変化は認められなかった。When colored hard copper wires were heated at 100° C. for 30 minutes, no change in hue was observed in any of the samples.
着色した硬銅線を１００℃、３０分間加熱したところい
ずれの試料も色相の変化は認められなかった。When colored hard copper wires were heated at 100° C. for 30 minutes, no change in hue was observed in any of the samples.
以上のように処理浴の種類、濃度、温度、処理時間を変
化させることによって、薄い干渉色から真黒色に至る広
範囲の環系着色を施すことができた。By changing the type of treatment bath, concentration, temperature, and treatment time as described above, it was possible to apply a wide range of ring-based coloring, from pale interference colors to deep black.
〈発明の効果〉
本発明によれば金属のチオ酸水溶液を用い、その処理条
件を変化させることによって種々の黒糸着色を与えるこ
とができるので、その処理は安全性のある薬品処理であ
るため、作業の安全性が高く、しかも、芸術的もしくは
意匠的美観を備えた着色製品を得ることができる。<Effects of the Invention> According to the present invention, various black yarn colors can be given by using a metal thioic acid aqueous solution and changing the treatment conditions, and the treatment is a safe chemical treatment. , it is possible to obtain a colored product with high work safety and an artistic or design aesthetic.
Claims (1)
着色せしめることを特徴とする銅の着色方法A method for coloring copper, which is characterized by immersing copper in a metal thioic acid aqueous solution and coloring it through a sulfidation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5951789A JPH02240277A (en) | 1989-03-14 | 1989-03-14 | Method for coloring copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5951789A JPH02240277A (en) | 1989-03-14 | 1989-03-14 | Method for coloring copper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02240277A true JPH02240277A (en) | 1990-09-25 |
Family
ID=13115537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5951789A Pending JPH02240277A (en) | 1989-03-14 | 1989-03-14 | Method for coloring copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02240277A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100862990B1 (en) * | 2006-07-07 | 2008-10-13 | 양인규 | A color making method for copper materials |
| JP2014205871A (en) * | 2013-04-11 | 2014-10-30 | 日本ニュークローム株式会社 | Method of treating surface of copper-based metal to color blue |
-
1989
- 1989-03-14 JP JP5951789A patent/JPH02240277A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100862990B1 (en) * | 2006-07-07 | 2008-10-13 | 양인규 | A color making method for copper materials |
| JP2014205871A (en) * | 2013-04-11 | 2014-10-30 | 日本ニュークローム株式会社 | Method of treating surface of copper-based metal to color blue |
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