JPS6133911B2 - - Google Patents
Info
- Publication number
- JPS6133911B2 JPS6133911B2 JP4237080A JP4237080A JPS6133911B2 JP S6133911 B2 JPS6133911 B2 JP S6133911B2 JP 4237080 A JP4237080 A JP 4237080A JP 4237080 A JP4237080 A JP 4237080A JP S6133911 B2 JPS6133911 B2 JP S6133911B2
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- thiourea
- copper
- liquid
- hydrochloric acid
- 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
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 108010088249 Monogen Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 241000565357 Fraxinus nigra Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002699 waste material Substances 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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/48—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 aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
【発明の詳細な説明】
銅を用いた製品ないし銅で表面を被覆した製品
は、装飾的目的で表面をいぶすことが多い。従来
の銅表面のいぶし処理は、市販されている処理液
を使用して行うけれども、市販の処理液は高価で
あり、また処理表面も耐候性が悪く、色ムラが発
生するなどの問題があつた。さらに処理後の廃液
の処理に要する費用が大きかつた。そこで本発明
は、そのような問題、欠点のない新しい銅のいぶ
し処理方法を開発する目的でなされた。
従来行われていたいぶし処理をさらに詳しく説
明すると、次のようなステツプで行われる。すな
わち、
〔酸洗〕→〔水洗〕→〔硫化液処理〕→〔水
洗〕→〔ヘアーライン〕→〔水洗〕→〔防錆処
理〕
以上の方法で使用される硫化処理液は、硫化カ
リ〔K2S〕、次亜硫酸ソーダなどと塩化アンモン
の混合液を使用していた。このような処理液を使
用した場合は排水処理が必要で、それだけに工程
も複雑化し、費用も嵩むのであつた。さらに、黒
色の着色も均一に行い難く、処理後約１〜２月位
で黒色から黒灰出に変色する欠点があつた。
本発明は以上のような事情に鑑みてなされたも
ので、下記配合の処理液を提供するものである。
チオ尿素 ４〜15重量％
塩化アンモン 0.1〜５ 〃
硝酸アンモン 0.1〜５ 〃
酸性硫酸ソーダ 0.1〜１ 〃
アンモニア（NH3） １〜５ 〃
界面活性剤 0.01〜0.5 〃
増粘剤 ０〜１ 〃
水 残 余
以上の配合においてアンモニアはNH3換算の量
である。界面活性剤としてはノニオン系、アニオ
ン系または両者の混合物の何れでもよい。ノニオ
ン系界面活性剤としては、たとえば第一工業製薬
(株)社のノイゲンSS、ノイゲンET、ノイゲン
EA、エマルジツトなどが用いられる。アニオン
系界面活性剤としては、第一工業製薬(株)社のモノ
ゲン170、モノゲンＰ、ラベリンＰ、ネオゲンＴ
などがある。増粘剤としては処理液の粘度が50〜
1000cpsになるように加えるもので、たとえばメ
チルセルロース、ポリエチレンオキサイドなどが
用いられる。
以上の処理液を用いて銅の硫化処理を行う場合
のプロセスは、希塩酸で銅表面を洗浄する前処理
の工程、硫化処理の工程の２工程からなる。前処
理は１〜５重量％の塩酸水溶液で２〜10分間処理
することによつて行われる。硫化処理は、前記処
理液中に、処理物を浸漬するか、または処理液を
塗布することにより行う。これらの主要な工程を
終えた後は、180℃で５分間位の見当で乾燥を行
う。
なお、前処理工程の前に、必要であれば脱脂処
理を行う。また塩酸以外の硫酸、リン酸などを用
いてもよいが、いぶしの色、液のハジキなどの点
からみて、塩酸の方が好ましい。塩酸の濃度は、
むしろ低濃度（たとえば１〜３重量％）で長時間
行うのが好ましい。
硫化処理の条件について言及するならば、処理
液中のチオ尿素の分解は、PH、温度、時間によつ
て異なり、それに伴い銅板の黒化（硫化）状態も
違つてくる。また処理液自身のPHが中性、アルカ
リ性であるとチオ尿素の分解は遅いので処理中の
PHは酸性域になければならない。さらに、主剤で
あるチオ尿素の分解は150℃位でも起るが黒化を
早く、かつ完全に進めるためには更に高い温度が
必要である。通常180〜190℃が適当である。時間
は10分位が適当である。
処理液中に界面活性剤を添加することにより、
浸水性が向上し、処理が均一に行えるが、若し添
加しない場合は、処理ムラが起り、処理面がマダ
ラ模様になつてしまう。また増粘剤は、黒化処理
（いぶし処理）の程度を変えるのに有効であり、
必要に応じて加えればよい。もつとも黒化の程度
はチオ尿素の濃度によつても変えられる。
以上に説明したように、本発明の処理液を使用
すれば次の効果が得られる。
(1) 耐候性が、従来の場合に比べて向上した。従
来の場合１月位で変色したが、本発明の場合６
月位安定である。
(2) 安価である。
(3) 処理ムラがない。
実施例
次の配合の処理液を用いて、銅板の処理を行つ
た。銅板は３％塩酸で10分間前処理した。
チオ尿素 10％
塩化アンモン １％
硝酸アンモン １％
酸性硫酸ソーダ １％
アンモニア １％
ノイゲンSS 0.01％
メチルセルロース 0.5％
水 残 り
黒化処理は次のような条件で行つた。
【表】DETAILED DESCRIPTION OF THE INVENTION Copper-based products or copper-coated products often have an oxidized surface for decorative purposes. Conventional oxidation treatment of copper surfaces is carried out using commercially available treatment liquids, but commercially available treatment liquids are expensive, and the treated surfaces have poor weather resistance, causing problems such as color unevenness. Ta. Furthermore, the cost required to treat the waste liquid after treatment was high. Therefore, the present invention was made for the purpose of developing a new method for oxidizing copper that is free from such problems and drawbacks. To explain in more detail the conventional oxidizing process, it is performed in the following steps. That is, [pickling] → [water washing] → [sulfiding solution treatment] → [water washing] → [hairline] → [water washing] → [rust prevention treatment] The sulfurizing solution used in the above method is potassium sulfide [K 2 S], a mixture of sodium hyposulfite and ammonium chloride was used. When such a treatment liquid is used, wastewater treatment is required, which complicates the process and increases costs. Furthermore, it was difficult to achieve uniform black coloring, and the color changed from black to black ash about one to two months after treatment. The present invention has been made in view of the above circumstances, and provides a processing liquid having the following composition. Thiourea 4-15% by weight Ammonium chloride 0.1-5 Ammonium nitrate 0.1-5 Acidic sodium sulfate 0.1-1 Ammonia (NH 3 ) 1-5 Surfactant 0.01-0.5 Thickener 0-1 Water Residual Ammonia in the above formulations is the amount in terms of NH 3 . The surfactant may be nonionic, anionic, or a mixture of both. Examples of nonionic surfactants include Daiichi Kogyo Seiyaku Co., Ltd.
Neugen SS, Neugen ET, Neugen Co., Ltd.
EA, emulsion, etc. are used. Examples of anionic surfactants include Monogen 170, Monogen P, Labelin P, and Neogen T manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
and so on. As a thickener, the viscosity of the processing liquid is 50~
It is added to a concentration of 1000 cps, such as methylcellulose or polyethylene oxide. The process for sulfurizing copper using the above treatment liquid consists of two steps: a pretreatment step of cleaning the copper surface with dilute hydrochloric acid, and a sulfurization step. Pretreatment is carried out by treatment with a 1-5% by weight aqueous hydrochloric acid solution for 2-10 minutes. The sulfurization treatment is carried out by immersing the object to be treated in the treatment liquid or by applying the treatment liquid. After completing these main steps, dry at 180°C for approximately 5 minutes. Note that before the pretreatment step, a degreasing treatment is performed if necessary. Although sulfuric acid, phosphoric acid, etc. other than hydrochloric acid may be used, hydrochloric acid is preferable in terms of the color of the oxidation and the repellency of the liquid. The concentration of hydrochloric acid is
Rather, it is preferable to carry out the treatment at a low concentration (for example, 1 to 3% by weight) for a long period of time. Regarding the conditions of sulfiding treatment, the decomposition of thiourea in the treatment solution varies depending on the pH, temperature, and time, and the blackening (sulfiding) state of the copper plate also varies accordingly. Also, if the pH of the treatment solution itself is neutral or alkaline, the decomposition of thiourea will be slow, so
PH must be in the acidic range. Furthermore, the decomposition of thiourea, the main ingredient, occurs even at around 150°C, but higher temperatures are required for rapid and complete blackening. Usually 180 to 190°C is appropriate. Appropriate time is about 10 minutes. By adding a surfactant to the treatment solution,
Water permeability is improved and processing can be carried out uniformly, but if it is not added, uneven processing will occur, resulting in a spotted pattern on the treated surface. In addition, thickeners are effective in changing the degree of blackening treatment (oxidation treatment).
You can add it if necessary. Of course, the degree of blackening also changes depending on the concentration of thiourea. As explained above, the following effects can be obtained by using the treatment liquid of the present invention. (1) Weather resistance has improved compared to the conventional case. In the conventional case, the color changed in about January, but in the case of the present invention, it changed color in about 6 months.
It is stable for about a month. (2) It is inexpensive. (3) No uneven processing. Example A copper plate was treated using a treatment liquid with the following composition. The copper plate was pretreated with 3% hydrochloric acid for 10 minutes. Thiourea 10% Ammonium chloride 1% Ammonium nitrate 1% Sodium acid sulfate 1% Ammonia 1% Neugen SS 0.01% Methyl cellulose 0.5% Water remainder The blackening treatment was carried out under the following conditions. 【table】
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4237080A JPS56139680A (en) | 1980-03-31 | 1980-03-31 | Composition for oxidizing solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4237080A JPS56139680A (en) | 1980-03-31 | 1980-03-31 | Composition for oxidizing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56139680A JPS56139680A (en) | 1981-10-31 |
| JPS6133911B2 true JPS6133911B2 (en) | 1986-08-05 |
Family
ID=12634149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4237080A Granted JPS56139680A (en) | 1980-03-31 | 1980-03-31 | Composition for oxidizing solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56139680A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193700U (en) * | 1987-05-29 | 1988-12-13 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19819925A1 (en) * | 1998-05-05 | 1999-11-11 | Km Europa Metal Ag | Process for creating a protective layer on the inner surface of a copper pipe |
| JP4783885B1 (en) * | 2011-03-28 | 2011-09-28 | 寛 中西 | Method for producing hairline-tanned stainless steel sheet and hairline-tanned stainless steel sheet |
-
1980
- 1980-03-31 JP JP4237080A patent/JPS56139680A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193700U (en) * | 1987-05-29 | 1988-12-13 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56139680A (en) | 1981-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4264418A (en) | Method for detersifying and oxide coating removal | |
| JP3606604B2 (en) | Liquid composition and method for removing dirt and oxides | |
| US3140203A (en) | Method of and composition for treating aluminum and aluminum alloys | |
| US3625908A (en) | Composition for cleaning photographic equipment | |
| US2846343A (en) | Product and method for effecting a cold chemical oxidation of aluminum and its alloys | |
| US3899367A (en) | Compositions and methods for blackening hardened steel | |
| US4065327A (en) | Black chromate coatings | |
| JPS6133911B2 (en) | ||
| US2148331A (en) | Method and composition for coating iron and steel articles | |
| US2519672A (en) | Composition for bluing metal | |
| US2557509A (en) | Composition and process for protecting ferrous metals from rusting in moist air | |
| US2895848A (en) | Method of preserving the wooden structure of cooling towers by impregnating | |
| US2200615A (en) | Method of and composition for cleaning and rendering metal surfaces immune from rust | |
| US2437441A (en) | Coloring metal surfaces | |
| JPS642200B2 (en) | ||
| CN113860914A (en) | Soak solution for removing white cobblestone rust yellow spots, preparation method of soak solution and method for removing white cobblestone rust yellow spots | |
| DE1521919B1 (en) | Use of mercapto compounds to remove and prevent tarnish layers on metals | |
| US2086123A (en) | Compositions of hydrogen peroxide and iron salts and method of stabilizing them | |
| JPS57156411A (en) | Hair-treating agent | |
| JP2002180264A (en) | Copper sheet with patina-colored dotted pattern and treatment method therefor | |
| DE1291169B (en) | Pickling bath and method of using the same | |
| US2878149A (en) | Product for effecting a cold chemical oxidation of copper and its alloys | |
| US2716618A (en) | Process of coloring glass fabrics | |
| ES2141546T3 (en) | SULFUR COMPOUNDS COATED WITH A ZINC COMPOUND. | |
| GB815756A (en) | Method for coating surfaces and, particularly, metal surfaces |