WO2002103084A9 - Solution de galvanoplastie de palladium - Google Patents
Solution de galvanoplastie de palladiumInfo
- Publication number
- WO2002103084A9 WO2002103084A9 PCT/JP2001/005107 JP0105107W WO02103084A9 WO 2002103084 A9 WO2002103084 A9 WO 2002103084A9 JP 0105107 W JP0105107 W JP 0105107W WO 02103084 A9 WO02103084 A9 WO 02103084A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- palladium
- acid
- plating solution
- salt
- ammonium
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Definitions
- the present invention relates to a palladium plating solution, and in particular, to a palladium plating solution suitable for providing a palladium plating decoration material that avoids the problem of the occurrence of a decorative material, Nikkerallergi.
- Palladium plating solutions have been studied extensively for a long time. The physical properties of the deposits are excellent in light resistance, corrosion resistance, discoloration resistance, abrasion resistance, etc. It is used for a wide range of applications such as, connectors and circuit boards.
- conventional surface treatment technology for example, to apply white-colored plating to jewelry such as watch cases, watch bands, eyeglass frames, necklaces, and rings, it is necessary to use palladium plating, palladium-nickel alloy plating, palladium plating. Commonly used are cobalt alloy plating, rhodium plating, platinum plating and silver plating.
- accessories such as watch cases, watch bands, eyeglass frames, necklaces, earrings, and rings for Europe have a high-purity, stable, thick metal plating with a white metal plating that can prevent the occurrence of nickel allergy.
- a palladium plating solution that can be used.
- an object of the present invention is to provide a palladium plating solution from which a palladium deposit having high purity and stable physical properties can be obtained. Disclosure of the invention
- the present inventors have conducted intensive studies to obtain a palladium plating solution that can be used on an industrial scale and that can form a highly pure palladium deposit.
- Salt, pyridinecarboxylic acid and z or soluble trace metal salts, amide derivatives of pyridinecarboxylic acid and anionic or amphoteric surfactants are suitable for palladium plating solutions. It has a high deposition rate, is excellent in stability, and has a plating film thickness of 5 ⁇ m or more, has excellent specular gloss, and has a high purity with almost no cracks. As a result, the present invention has been reached.
- Soluble palladium salt in terms of palladium amount 0.0! To 40.0 g Zl, pyridine carboxylic acid 0.01 to: 10 g Z1 and Z or soluble iron salt, zinc salt, 0.002 to 1.0 g / l in terms of metal of at least one selected from the group consisting of lime salts, selenium salts, and tellurium salts; amine derivatives of pyridinecarponic acid 0.005 to 10 g_l A palladium plating solution containing an aldehyde benzoic acid derivative and an anionic surfactant or an amphoteric surfactant 0.001 to 1.2 gZl;
- the pyridinecarboxylic acid is at least one selected from nicotinic acid, picolinic acid, isonicotinic acid, 2,3-quinolinic acid, 2,4-lutidic acid and 2,6-dipicolinic acid.
- Soluble iron, zinc, thallium, selenium and tellurium salts are iron sulfate, ferric ammonium sulfate, zinc sulfate, thallium sulfate, thallium acetate, selenic acid, selenite, sodium selenite 2.
- Claim 1 wherein the amine derivative of pyridinecarboxylic acid is at least one selected from nicotinamide, picolineamide, isonicotinic acid amide and nicotinic acid amide. Described palladium plating solution,
- Aldehydebenzoic acid derivatives are p-phthalaldehyde, o-phthalaldehyde, o-phthalaldehyde acid, p-phthalaldehyde acid, m-phthalaldehyde, iso-phthalaldehyde acid and aldehyde ammonium
- Anionic surfactant or amphoteric surfactant is dodecylamine acetate, Cetylpyridinium bromide, di-2-ethylethyl sulfosuccinate, sorbitan monopalmitate, polyoxyethylene stearate, sorbitan monostearate, dimethylalkyl betaine, dodecyltrimethylammonium chloride and poly
- the soluble palladium salt used in the present invention includes, for example, palladium chloride, dichlorodiamine palladium, dichlorotetraamine palladium and the like. These salts can be used alone or in combination of two or more.
- the use concentration of the soluble palladium salt in the palladium plating solution is preferably in the range of 1.0 to 40.0 g / 1 as the amount of palladium. A concentration of 1.01 or less is not preferable because the deposition rate of the plating film becomes slow, and a concentration of 40.Og / 1 or more is not practical because the deposition rate does not further improve.
- examples of the pyridinecarboxylic acid used in the present invention include nicotinic acid, picolinic acid, isonicotinic acid, 2,3-quinolinic acid, 2,4-rutidic acid, and 2,6-dipicolinic acid.
- the above pyridinecarboxylic acids can be used alone or in combination of two or more.
- the working concentration of the pyridine carboxylic acid in the palladium plating solution is 0.01 to 20 OgZl, preferably 1.0 OgZl to: L O. OgZl. 0. O lg If it is less than / 1, there is no effect of improving gloss, and if it is 20. OgZl or more, the gloss will not be further improved, so it is not practical.
- a soluble metal salt is added to the pyridine carboxylic acid in combination with the pyridine carboxylic acid, or a soluble metal salt is added instead of the pyridine carboxylic acid.
- the soluble metal salts include soluble iron salts, zinc salts, talmium salts, selenium salts, and tellurium salts. Specific examples include iron sulfate, ferric sulfate ammonium, zinc sulfate, thallium sulfate, thallium acetate, selenic acid, selenous acid, sodium selenite, and lithium selenite.
- the above-mentioned soluble metal salts can be used alone or in combination of two or more.
- the concentration of the soluble metal salt used is 0.002 to 1.0 g / 1, preferably 0.005 to 0.7 gZl in terms of metal. Below 0.002Z1, there is no effect of lowering the internal stress of the palladium precipitate, and above 1.Og / 1, it is not practical because the internal stress of the palladium precipitate cannot be further improved. .
- examples of the amide derivative of pyridine carboxylic acid used in the present invention include nicotinamide, picoline amide, isonicotinic acid amide, nicotinic acid amide and the like. These amide derivatives of pyridinecarboxylic acid can be used alone or in combination of two or more.
- the use concentration of the amide derivative of pyridine carboxylic acid in the palladium plating solution is 0.002 to 20. Og / 1, preferably 0.005 to; L. OgZl. If it is less than 0.002 gZl, there is no effect of improving the gloss, and if it exceeds 20.0 gZl, the gloss does not improve further, so it is not practical.
- aldehyde benzoic acid derivatives used in the present invention include, for example, p-phthalaldehyde, 0-phthalaldehyde, o-phthalaldehyde, p-phthalaldehyde, m-phthalaldehyde, iso-aldehyde And aldehyde Ammonymum and the like.
- the above aldehyde benzoic acid derivatives can be used alone or in combination of two or more.
- the use concentration of the aldehyde benzoic acid derivative in the palladium plating solution is 0.002 to 20. OgZl, preferably 0.005 to 10. OgZl. If it is less than 0.002 g / 1, there is no effect to improve the gloss, and if it exceeds 20 g OgZl, the gloss will not be further improved, so it is not practical.
- the anionic surfactant or the amphoteric surfactant used in the present invention is for preventing the generation of pits, and is particularly effective for those having a complicated shape. Specifically, dodecylamine acetate, cetylpyridinium bromide, di-2-ethylhexyl sodium sulfosuccinate, sorbitan monopalmitate, polyoxyethylene stearate, sorbitan monostearate, dimethyl alkyl betaine, Dodecyltrimethylammonium chloride and polyoxyethylene sorbitan monopalmitate.
- anionic surfactants or amphoteric surfactants can be used alone or in combination of two or more.
- the used concentration of the anionic surfactant or the amphoteric surfactant in the palladium plating solution is 0.001 to 1.2 g / 1.
- the amount of the conductive salt used in the plating solution of the present invention is 15.0 to 300.0 gZl. 15. 0 Bruno 1 below, conductive I 1 Raw plating solution is deteriorated, 300. heavier specific gravity of the plated solution at 0 g / 1 or more, fogging palladium precipitate force Puri, turbocharger Ke like occurs Is not preferred.
- the plating solution of the present invention is used in a pH range of 7 to 12, preferably 7.5 to 9.5. In this pH range, a good plating film can be formed.
- the pH of the plating solution is adjusted with an acid such as hydrochloric acid or sulfuric acid, or an alkaline substance such as sodium hydroxide, hydrating power, or aqueous ammonia.
- the plating solution of the present invention can be plated at a temperature of 30 to 55 ° C, and a smooth, glossy and good plating film can be obtained particularly at a solution temperature of 40 to 55 ° C.
- the deposition rate of the plating film tends to increase as the liquid temperature increases, and an arbitrary deposition rate can be obtained by appropriately setting the temperature within the above-mentioned temperature range.
- the deposition rate of the plating film depends not only on the temperature of the plating solution but also on the palladium concentration. It is easy to control the thickness of the plating film.
- the current density at the time of plating is 0.3 to: 1.2 A / dm 2 .
- Tellurous acid (as the amount of Te metal) 0.05 g / 1 80 g / 1 Ammonium hydrogen phosphate 20 g / l Ecotinamide 0.8 g / 1 Di-2-ethyl ethyl sulfosuccinate
- Dodecyltrimethylammonium chloride '0.1 g The above plating solution was adjusted to pH 8.3 with ammonia water, bath temperature 42 ° C, current density 1. OAZdm 2 , pre-plated with nickel 25 As a result of immersing the copper plate of X 35 mm brass plate for 30 minutes, a shiny palladium plated product with an average film thickness of 7 ⁇ m was obtained. As a result of performing an ammonia violence test (12 hours at room temperature) on the obtained palladium plating, no crack was observed.
- the above plating solution was adjusted to pH 8.2 with ammonia water, bath temperature 50 ° (: Current density 1. 25 x 35 mm brass plate previously plated with nickel at OAZdm 2 After immersing the copper plate for 30 minutes, a shiny palladium-plated product with an average film thickness of 7 ⁇ was obtained, and the obtained palladium-plated product was subjected to an ammonia violence test (12 hours at room temperature). The palladium plated article was subjected to an artificial sweat immersion test (at room temperature for 48 hours), and no discoloration was observed.
- Telluric acid and nicotinamide were removed from the palladium plating solution of Example 1, and instead, a palladium plating solution having a composition containing 1.0 gZl of EDTA was added. 2 and plating was performed under the same plating conditions as in Example 1. As a result of performing an ammonia violence test on the obtained palladium plated product, a crack occurred at room temperature for 6 hours.
- Plating was performed under the same plating conditions as in Example 2 using a palladium plating solution having a composition obtained by removing nicotinamide from the palladium plating solution of Example 2. The resulting palladium plating was uneven and did not have luster.
- Example 3 The same plating as in Example 3 was performed using a palladium plating solution having a composition in which ferric sulfate ammonium and -cotinamide were removed from the palladium plating solution of Example 3 and 1.0 g Zl of EDTA was added instead. Plating was performed according to the conditions. The obtained palladium-plated product was subjected to an ammonia anaerobic test. As a result, cracks occurred at room temperature for 6 hours.
- the palladium plating solution of the present invention has extremely good storage stability of the solution, good workability, and a good work environment.
- the deposition rate depends on the concentration and the station temperature, it is easy to control the winding of the plating.
- the plating film obtained by the plating solution of the present invention is glossy and has low stress even if it has a thickness of 5 m or more, has no cracking, has excellent spreadability, and has a beautiful white mirror gloss. Present. Further, the plating film does not crack even in an ammonia anaerobic test at room temperature for 12 hours. Room temperature 48 ° C No discoloration occurs in the test in which the sample was fully immersed or partially immersed in artificial sweat (No. 3), and an excellent palladium film was obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000211927A JP3601005B2 (ja) | 1999-10-27 | 2000-06-09 | パラジウムめっき液 |
EP01941060A EP1396559A4 (en) | 1999-10-27 | 2001-06-15 | PALLADIUM GALVANOPLASTY SOLUTION |
AU2001274534A AU2001274534B2 (en) | 2001-06-15 | 2001-06-15 | Palladium plating solution |
CNB01801111XA CN1249270C (zh) | 1999-10-27 | 2001-06-15 | 钯镀液 |
GB0128788A GB2382353B (en) | 1999-10-27 | 2001-06-15 | Palladium Plating Solution |
PCT/JP2001/005107 WO2002103084A1 (fr) | 1999-10-27 | 2001-06-15 | Solution de galvanoplastie de palladium |
HK03106516.9A HK1054250A1 (zh) | 2001-06-15 | 2003-09-11 | 鈀鍍液 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34239299 | 1999-10-27 | ||
JP2000211927A JP3601005B2 (ja) | 1999-10-27 | 2000-06-09 | パラジウムめっき液 |
PCT/JP2001/005107 WO2002103084A1 (fr) | 1999-10-27 | 2001-06-15 | Solution de galvanoplastie de palladium |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002103084A1 WO2002103084A1 (fr) | 2002-12-27 |
WO2002103084A9 true WO2002103084A9 (fr) | 2003-04-24 |
Family
ID=27278780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/005107 WO2002103084A1 (fr) | 1999-10-27 | 2001-06-15 | Solution de galvanoplastie de palladium |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1396559A4 (ja) |
CN (1) | CN1249270C (ja) |
GB (1) | GB2382353B (ja) |
WO (1) | WO2002103084A1 (ja) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102400190A (zh) * | 2010-09-17 | 2012-04-04 | 日本电镀工程股份有限公司 | 铱电镀液及其电镀方法 |
GB201200482D0 (en) * | 2012-01-12 | 2012-02-22 | Johnson Matthey Plc | Improvements in coating technology |
ITFI20120098A1 (it) * | 2012-05-22 | 2013-11-23 | Bluclad Srl | Bagno galvanico a base di palladio e fosforo, suo uso in processi galvanici e leghe ottenute applicando il processo galvanico a detti bagni. |
JP6620103B2 (ja) * | 2014-09-04 | 2019-12-11 | 日本高純度化学株式会社 | パラジウムめっき液及びそれを用いて得られたパラジウム皮膜 |
AT516876B1 (de) * | 2015-03-09 | 2016-11-15 | Ing W Garhöfer Ges M B H | Abscheidung von dekorativen Palladium-Eisen-Legierungsbeschichtungen auf metallischen Substanzen |
CN105441998A (zh) * | 2015-10-30 | 2016-03-30 | 无锡市嘉邦电力管道厂 | 含亚硝酸钠、四正丙基溴化铵的钯电镀镀及其电镀方法 |
CN105332021A (zh) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | 含亚硝酸钠、四苯基溴化砷鎓的钯电镀液及其电镀方法 |
CN105332023A (zh) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | 一种含四正丙基溴化铵的钯电镀液及其电镀方法 |
CN105332024A (zh) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | 一种含溴化异丙基三苯基磷鎓的钯电镀液及其电镀方法 |
CN105316722A (zh) * | 2015-11-20 | 2016-02-10 | 无锡市嘉邦电力管道厂 | 一种含四苯基溴化砷鎓的钯电镀液及其电镀方法 |
CN105543913A (zh) * | 2016-02-25 | 2016-05-04 | 盈昌集团有限公司 | 钯钴合金电镀液及用其电镀眼镜框架的工艺 |
CN106757203A (zh) * | 2016-11-29 | 2017-05-31 | 江苏澳光电子有限公司 | 一种钼合金表面化学镀钯的渡液及其应用 |
CN106757207A (zh) * | 2016-11-29 | 2017-05-31 | 江苏澳光电子有限公司 | 一种用于pcb板化学镀镍钯合金的方法 |
CN106757204A (zh) * | 2016-11-29 | 2017-05-31 | 江苏澳光电子有限公司 | 一种在不锈钢表面镀钯的渡液及其应用 |
CN108004573B (zh) * | 2017-12-12 | 2020-10-16 | 安徽启东热能科技有限公司 | 一种气液分离盘盘体的表面处理工艺 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3317493A1 (de) * | 1983-05-13 | 1984-11-15 | W.C. Heraeus Gmbh, 6450 Hanau | Galvanische abscheidung von palladium-ueberzuegen |
US4911799A (en) * | 1989-08-29 | 1990-03-27 | At&T Bell Laboratories | Electrodeposition of palladium films |
JPH0711476A (ja) * | 1993-06-23 | 1995-01-13 | Kojima Kagaku Yakuhin Kk | パラジウムめっき液 |
JPH07278870A (ja) * | 1994-04-08 | 1995-10-24 | Kojima Kagaku Yakuhin Kk | パラジウムめっき液 |
DE19528800C2 (de) * | 1995-08-04 | 1999-05-06 | Ami Doduco Gmbh | Alkalisches oder neutrales Bad zur galvanischen Abscheidung von Palladium oder Legierungen des Palladiums |
JP3379412B2 (ja) * | 1997-05-30 | 2003-02-24 | 松下電器産業株式会社 | パラジウムめっき液とこれを用いたパラジウムめっき皮膜及びこのパラジウムめっき皮膜を有する半導体装置用リードフレーム |
JP4249292B2 (ja) * | 1998-07-10 | 2009-04-02 | 株式会社大和化成研究所 | 錫及び錫合金メッキ浴 |
JP2000303199A (ja) * | 1999-02-17 | 2000-10-31 | Nisshin Kasei Kk | パラジウム合金めっき液、パラジウム−銅合金めっき部材及び殺菌性部材 |
JP3601005B2 (ja) * | 1999-10-27 | 2004-12-15 | 小島化学薬品株式会社 | パラジウムめっき液 |
-
2001
- 2001-06-15 GB GB0128788A patent/GB2382353B/en not_active Expired - Fee Related
- 2001-06-15 CN CNB01801111XA patent/CN1249270C/zh not_active Expired - Fee Related
- 2001-06-15 WO PCT/JP2001/005107 patent/WO2002103084A1/ja active Search and Examination
- 2001-06-15 EP EP01941060A patent/EP1396559A4/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CN1249270C (zh) | 2006-04-05 |
CN1420947A (zh) | 2003-05-28 |
EP1396559A1 (en) | 2004-03-10 |
GB0128788D0 (en) | 2002-01-23 |
GB2382353B (en) | 2004-10-27 |
WO2002103084A1 (fr) | 2002-12-27 |
GB2382353A (en) | 2003-05-28 |
EP1396559A4 (en) | 2006-10-11 |
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