EP1137825B1 - Wässrige lösung zur elektrolytischen abscheidung von zinn-zink-legierungen - Google Patents
Wässrige lösung zur elektrolytischen abscheidung von zinn-zink-legierungen Download PDFInfo
- Publication number
- EP1137825B1 EP1137825B1 EP99960973A EP99960973A EP1137825B1 EP 1137825 B1 EP1137825 B1 EP 1137825B1 EP 99960973 A EP99960973 A EP 99960973A EP 99960973 A EP99960973 A EP 99960973A EP 1137825 B1 EP1137825 B1 EP 1137825B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution according
- alkyl
- tin
- carboxylic acids
- 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 - Lifetime
Links
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 12
- -1 Zn(II) ions Chemical class 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 19
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 6
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 6
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 6
- 150000008365 aromatic ketones Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 102220047090 rs6152 Human genes 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910003202 NH4 Inorganic materials 0.000 claims 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 2
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 159000000011 group IA salts Chemical class 0.000 abstract 2
- 238000009713 electroplating Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000001447 alkali salts Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- OMBBWWNNSCAQJY-UHFFFAOYSA-N zinc tin(2+) Chemical compound [Zn++][Sn++] OMBBWWNNSCAQJY-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Definitions
- the present invention relates to an aqueous solution for Deposition of tin-zinc alloys and especially one Electroplating bath which is used to deposit tin-zinc alloys from a cyanide-free tin (II) -zinc (II) solution with simple bath guidance.
- Products made by electroplating with a tin-zinc alloy are characterized by a excellent corrosion resistance. Especially the Resistance to hydraulic fluid and aqueous Salt solutions leave such coated products for Automotive industry seem interesting. Also in the Broadcasting, electrical and construction industries are made with tin-zinc alloys coated products due to their Corrosion resistance and their excellent solderability used.
- the electroplating baths usual up to now contained tin in the + IV oxidation state and cyanide ions.
- electroplating baths have the disadvantage that for Deposition of tin (IV) ions requires more energy is required as for the separation of tin (II) ions.
- the bath tour includes the difficulty that the dissolution of the anode, which advantageously also consists of a tin-zinc alloy is formed by forming a film the formation of tin (IV) ions is promoted by means of polarization must become.
- the thickness and composition of the deposited tin-zinc alloy on the current density and thus dependent on the geometry of the substrate.
- the Toxicity of the cyanide ions makes industrial use difficult.
- the object of the present invention is therefore Providing an electroplating bath solution for Deposition of tin-zinc alloys that are not cyanide contains, by the deposition of tin from a tin (II) ions containing solution with a low energy consumption the separation, and their bath management over wide Ranges of the freely selectable parameters is not critical and flawless and discolouration-free deposits.
- aqueous solution which, in addition to tin (II) and zinc (II) ions, are aliphatic Carboxylic acids and / or their alkali salts as complexing agents, and a mixture of anionic and non-ionogenic Contains surfactants as grain refiners.
- the aqueous solution according to the invention furthermore contains aromatic aldehydes and / or aromatic ketones as brighteners.
- a special, advantageous compound of formula (II) is o-Cl-benzaldehyde.
- the pH of the solution is preferably 2-8, particularly preferred at 3-5.
- tin (II) and zinc (II) ions are preferred in the form of Chlorides, sulfates or alkyl sulfonates used.
- one or more conductive salts of the corresponding anions are additionally used. NH 4 Cl and / or NH 4 (CH 3 SO 3 ) are preferred.
- Preferred aliphatic carboxylic acids in the invention aqueous solution are hydrocarboxylic acids and aminocarboxylic acids and particularly preferred is citric acid or its Alkali metal salts.
- Aliphatic or aromatic sulfonates are preferably used as anionic surfactants.
- the electroplating bath for the deposition of zinc-tin alloys can also contain aromatic and / or heterocyclic carboxylic acids or their alkali salts according to formula (XIV) contain.
- carboxylic acids are Nicotinic acid and / or Na benzoate.
- the concentrations of the individual components are advantageously chosen within the following ranges: Zinc (II) ions 5 g / l to 50 g / l particularly preferred 20 g / l to 25 g / l Tin (II) ions 0.5 g / l to 5 g / l particularly preferred 1 g / l to 3 g / l aliphatic carboxylic acids 30 g / l to 200 g / l particularly preferred 60 g / l to 140 g / l non-ionic surfactants - according to formula (III) 0 g / l to 10 g / l particularly preferred 0 g / l to 2 g / l - according to formula (IV) or (V) 0 g / l to 10 g / l particularly preferred 0 g / l to 2 g / l anionic surfactants 5 g / l to 30 g / l particularly preferred
- the present invention also includes the use of the above described aqueous solution for the deposition of tin-zinc coatings, especially tin-zinc coatings with a Zinc content from 10 to 50% by weight.
- the invention is based on the following Embodiment explained in more detail.
- An aqueous solution was prepared from the following components:
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)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19852219A DE19852219C1 (de) | 1998-11-12 | 1998-11-12 | Wäßrige Lösung zur elektrolytischen Abscheidung von Zinn-Zink-Legierungen und Verwendung der Lösung |
| DE19852219 | 1998-11-12 | ||
| PCT/EP1999/008724 WO2000029645A2 (de) | 1998-11-12 | 1999-11-12 | Wässrige lösung zur elektrolytischen abscheidung von zinn-zink-legierungen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1137825A2 EP1137825A2 (de) | 2001-10-04 |
| EP1137825B1 true EP1137825B1 (de) | 2002-09-11 |
Family
ID=7887579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99960973A Expired - Lifetime EP1137825B1 (de) | 1998-11-12 | 1999-11-12 | Wässrige lösung zur elektrolytischen abscheidung von zinn-zink-legierungen |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6770185B2 (enExample) |
| EP (1) | EP1137825B1 (enExample) |
| JP (1) | JP4355987B2 (enExample) |
| KR (1) | KR20010086017A (enExample) |
| CN (1) | CN1195904C (enExample) |
| AT (1) | ATE223979T1 (enExample) |
| AU (1) | AU1775200A (enExample) |
| CZ (1) | CZ296310B6 (enExample) |
| DE (2) | DE19852219C1 (enExample) |
| PL (1) | PL194304B1 (enExample) |
| WO (1) | WO2000029645A2 (enExample) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002024979A1 (de) * | 2000-09-20 | 2002-03-28 | Dr.-Ing. Max Schlötter Gmbh & Co. Kg | Elektrolyt und verfahren zur abscheidung von zinn-kupfer-legierungsschichten |
| CN101809200A (zh) * | 2007-09-27 | 2010-08-18 | 日本油漆株式会社 | 表面处理金属材料和金属涂装物的制造方法 |
| CN102443827A (zh) * | 2011-12-19 | 2012-05-09 | 张家港舒马克电梯安装维修服务有限公司镀锌分公司 | 一种Sn-Zn合金电镀液 |
| CN102634827B (zh) * | 2012-05-07 | 2015-04-08 | 东莞市闻誉实业有限公司 | 一种锡-锌合金电镀方法 |
| CN106498453B (zh) * | 2016-09-14 | 2018-08-28 | 湖北大学 | 一种镀锡、锡合金的光亮剂及其制备方法和应用 |
| JP2021116473A (ja) * | 2020-01-27 | 2021-08-10 | 三菱マテリアル株式会社 | 錫又は錫合金電解めっき液、バンプの形成方法、及び回路基板の製造方法 |
| WO2021153160A1 (ja) * | 2020-01-27 | 2021-08-05 | 三菱マテリアル株式会社 | 錫又は錫合金電解めっき液、バンプの形成方法、及び回路基板の製造方法 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE415577B (sv) * | 1977-09-15 | 1980-10-13 | Magnusson H H Produkter | Sett och elektrolyt for att fobereda en stalyta for lackering |
| GB2013241B (en) * | 1977-11-16 | 1982-03-24 | Dipsol Chem | Electroplating bath for depositing tin or tin alloy with brightness |
| DE69106522T2 (de) * | 1990-08-31 | 1995-07-20 | Barry Beresford Thomas K | Elektroplattierung. |
| DE4034304A1 (de) * | 1990-10-29 | 1992-04-30 | Henkel Kgaa | Elektrolytzusatzmittel fuer ein faerbebad zur aluminiumeinfaerbung und verfahren zur einfaerbung von aluminium |
| GB2266894A (en) * | 1992-05-15 | 1993-11-17 | Zinex Corp | Modified tin brightener for tin-zinc alloy electroplating bath |
| JP3279353B2 (ja) * | 1992-09-25 | 2002-04-30 | ディップソール株式会社 | 錫−亜鉛合金電気めっき浴 |
| DE4446329A1 (de) * | 1994-12-23 | 1996-06-27 | Basf Ag | Salze aromatischer Hydroxylverbindungen und deren Verwendung als Glanzbildner |
| JP3609565B2 (ja) * | 1996-12-09 | 2005-01-12 | 株式会社大和化成研究所 | 錫−亜鉛合金めっき浴 |
| JP3816241B2 (ja) * | 1998-07-14 | 2006-08-30 | 株式会社大和化成研究所 | 金属を還元析出させるための水溶液 |
-
1998
- 1998-11-12 DE DE19852219A patent/DE19852219C1/de not_active Expired - Fee Related
-
1999
- 1999-11-12 CN CNB998097950A patent/CN1195904C/zh not_active Expired - Fee Related
- 1999-11-12 WO PCT/EP1999/008724 patent/WO2000029645A2/de not_active Ceased
- 1999-11-12 DE DE59902696T patent/DE59902696D1/de not_active Expired - Lifetime
- 1999-11-12 AT AT99960973T patent/ATE223979T1/de not_active IP Right Cessation
- 1999-11-12 CZ CZ20011633A patent/CZ296310B6/cs not_active IP Right Cessation
- 1999-11-12 PL PL99348755A patent/PL194304B1/pl not_active IP Right Cessation
- 1999-11-12 KR KR1020017005925A patent/KR20010086017A/ko not_active Withdrawn
- 1999-11-12 JP JP2000582620A patent/JP4355987B2/ja not_active Expired - Fee Related
- 1999-11-12 EP EP99960973A patent/EP1137825B1/de not_active Expired - Lifetime
- 1999-11-12 AU AU17752/00A patent/AU1775200A/en not_active Abandoned
-
2001
- 2001-05-11 US US09/854,131 patent/US6770185B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE59902696D1 (de) | 2002-10-17 |
| PL348755A1 (en) | 2002-06-03 |
| US20020046954A1 (en) | 2002-04-25 |
| JP2002530528A (ja) | 2002-09-17 |
| EP1137825A2 (de) | 2001-10-04 |
| WO2000029645A2 (de) | 2000-05-25 |
| PL194304B1 (pl) | 2007-05-31 |
| DE19852219C1 (de) | 2000-05-11 |
| WO2000029645A3 (de) | 2000-09-14 |
| ATE223979T1 (de) | 2002-09-15 |
| AU1775200A (en) | 2000-06-05 |
| US6770185B2 (en) | 2004-08-03 |
| CZ20011633A3 (cs) | 2001-12-12 |
| KR20010086017A (ko) | 2001-09-07 |
| CN1321205A (zh) | 2001-11-07 |
| JP4355987B2 (ja) | 2009-11-04 |
| CN1195904C (zh) | 2005-04-06 |
| CZ296310B6 (cs) | 2006-02-15 |
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