EP0379948B1 - Aqueous acid solutions for the electrodeposition of tin and/or lead/tin alloys - Google Patents
Aqueous acid solutions for the electrodeposition of tin and/or lead/tin alloys Download PDFInfo
- Publication number
- EP0379948B1 EP0379948B1 EP90100870A EP90100870A EP0379948B1 EP 0379948 B1 EP0379948 B1 EP 0379948B1 EP 90100870 A EP90100870 A EP 90100870A EP 90100870 A EP90100870 A EP 90100870A EP 0379948 B1 EP0379948 B1 EP 0379948B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- optionally
- weight
- lead
- aromatic
- 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
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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin 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
-
- 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 aqueous, acidic solutions for the electrolytic deposition of tin and / or lead / tin alloys containing a mixture of tin and / or lead salts of an alkanesulfonic acid, free alkanesulfonic acid, the alkyl group of the alkanesulfonic acid consisting of 1 to 5 carbon atoms , non-ionic wetting agent and optionally aromatic and / or short-chain aldehydes and / or optionally aromatic ketones and / or optionally short-chain unsaturated carboxylic acids.
- DE-PS 1 260 262 describes aldol condensation products which are added to aqueous baths for the electrodeposition of tin as brighteners.
- US Pat. No. 2,525,942 relates to the use of alkanesulfonic acid derivatives in solution for metal deposition.
- US Pat. No. 4,582,576 describes a method which deposits shiny tin-tin / lead layers from baths containing alkanesulfonic acid.
- aqueous, acidic solutions described therein contain metal salts, free alkane or alkanol sulfonic acid, wetting agents, a short-chain aliphatic aldehyde, an aromatic aldehyde, optionally an aromatic ketone and an unsaturated, short-chain carboxylic acid.
- the compositions described there have the disadvantage that they have only a poor load capacity in the high current density range.
- the object on which the invention is based is to provide aqueous, acidic solutions which have a better load-bearing capacity in the high current density range and enable uniform gloss scattering over the entire current density range.
- an aqueous, acidic solution for the electrolytic deposition of tin and / or lead / tin alloys containing a mixture of tin and / or lead salts of an alkanesulfonic acid, free alkanesulfonic acid, the alkyl group of the alkanesulfonic acid consists of 1 to 5 carbon atoms, non-ionic wetting agent and optionally aromatic and / or short-chain aldehydes and / or optionally aromatic ketones and / or optionally short-chain unsaturated carboxylic acids, characterized in that one or more reaction product (s) from acetaldehyde as a further brightener and / or an aldol condensation product of acetaldehyde with ammonia and / or acyclic ketones and / or aliphatic amines, amides, amino acids and / or hydrazine compounds, the concentration of the further brightener being 0.1
- a non-ionic wetting agent of the alkylaryl polyglycol ether type is preferably selected as the wetting agent. If a mixture of a reaction product of acetaldehyde and / or its aldol condensation products with acyclic ketones is chosen as the brightener, the aliphatic ketone preferably contains 10 carbon atoms in the molecule. Naphthaldehyde, chloroacetophenone or benzalacetone, formaldehyde or acetaldehyde and, as unsaturated carboxylic acid, methacrylic acid or methyl methacrylic acid are preferably added to the aqueous, acidic solutions.
- the aqueous, acidic solutions according to the invention preferably contain 5 to 25% by weight of the corresponding metal salt or salts, 6 to 20% by weight of the alkanesulfonic acid, 0.1 to 5% by weight of non-ionic wetting agent, 0.1 to 5 %
- the aldol condensation product if appropriate 0.1 to 3% of the aromatic aldehyde, optionally 0.01 to 1.0% by weight of the aromatic ketone, optionally 0.01 to 1.0% by weight of the short-chain aliphatic aldehyde, and optionally 0.01 to 1 % of unsaturated carboxylic acid.
- the information relates to mixtures that are adjusted to 1 liter of finished solution.
- aldol condensation products according to DE-PS 1 260 262 in a process for the electrolytic deposition of tin and / or lead / tin alloys surprisingly leads to improved galvanic deposition in the high current density range, and at the same time uniform gloss scattering is achieved in the low current density range.
- Process parameters The usability of the electrolyte was tested for tin and / or lead / tin deposition in a Hull cell according to DIN 50 957. Temperature: 20 - 25 ° C, exposure time: 5 minutes with mechanical stirring, anode tin or lead-tin analogous to the composition of the precipitation. Sheet steel cathode material, cell current 2, 3 or 4 amps per cell.
- the sheet After adding 10 ml / l of the additive according to the invention, the sheet was uniformly glossy from 0.2 to 10 A / dm 2.
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)
Description
Gegenstand der vorliegenden Erfindung sind wäßrige, saure Lösungen für die elektrolytische Abscheidung von Zinn und/oder Blei/Zinnlegierungen enthaltend ein Gemisch aus Zinn- und/oder Bleisalzen einer Alkansulfonsäure, freier Alkansulfonsäure, wobei die Alkylgruppe der Alkansulfonsäure aus 1 bis 5 C-Atomen besteht, nicht ionogenem Netzmittel und gegebenenfalls aromatischen und/oder kurzkettigen Aldehyden und/oder gegebenenfalls aromatischen Ketonen und/oder gegebenenfalls kurzkettigen ungesättigten Carbonsäuren.The present invention relates to aqueous, acidic solutions for the electrolytic deposition of tin and / or lead / tin alloys containing a mixture of tin and / or lead salts of an alkanesulfonic acid, free alkanesulfonic acid, the alkyl group of the alkanesulfonic acid consisting of 1 to 5 carbon atoms , non-ionic wetting agent and optionally aromatic and / or short-chain aldehydes and / or optionally aromatic ketones and / or optionally short-chain unsaturated carboxylic acids.
In der DE-PS 1 260 262 werden Aldolkondensationsprodukte beschrieben, die wäßrigen Bädern zur galvanischen Abscheidung von Zinn als Glanzbildner zugegeben werden. Die US-PS 2,525,942 betrifft die Verwendung von Alkansulfonsäurederivaten in Lösung zur Metallabscheidung. In der US-PS 4,582,576 wird ein Verfahren beschrieben, das aus alkansulfonsäurehaltigen Bädern glänzende Zinn- Zinn/Bleischichten abscheidet. Die dort beschriebenen wäßrigen, sauren Lösungen enthalten Metallsalze, freie Alkan- oder Alkanolsulfonsäure, Netzmittel, einen kurzkettigen aliphatischen Aldehyd, einen aromatischen Aldehyd, gegebenenfalls ein aromatisches Keton und eine ungesättigte, kurzkettige Carbonsäure. Die dort beschriebenen Zusammensetzungen haben den Nachteil, daß sie nur eine schlechte Belastbarkeit im hohen Stromdichtebereich aufweisen.DE-PS 1 260 262 describes aldol condensation products which are added to aqueous baths for the electrodeposition of tin as brighteners. US Pat. No. 2,525,942 relates to the use of alkanesulfonic acid derivatives in solution for metal deposition. US Pat. No. 4,582,576 describes a method which deposits shiny tin-tin / lead layers from baths containing alkanesulfonic acid. The aqueous, acidic solutions described therein contain metal salts, free alkane or alkanol sulfonic acid, wetting agents, a short-chain aliphatic aldehyde, an aromatic aldehyde, optionally an aromatic ketone and an unsaturated, short-chain carboxylic acid. The compositions described there have the disadvantage that they have only a poor load capacity in the high current density range.
Die der Erfindung zugrunde liegende Aufgabe besteht darin, wäßrige, saure Lösungen bereitzustellen, die eine bessere Belastbarkeit im hohen Stromdichtebereich aufweisen und eine gleichmäßige Glanzstreuung über den gesamten Stromdichtebereich ermöglichen.The object on which the invention is based is to provide aqueous, acidic solutions which have a better load-bearing capacity in the high current density range and enable uniform gloss scattering over the entire current density range.
Es wurde nun gefunden, daß diese Aufgaben gelöst werden durch eine wäßrige, saure Lösung für die elektrolytische Abscheidung von Zinn und/oder Blei/Zinnlegierungen, enthaltend ein Gemisch aus Zinn- und/oder Bleisalzen einer Alkansulfonsäure, freier Alkansulfonsäure, wobei die Alkylgruppe der Alkansulfonsäure aus 1 bis 5 C-Atomen besteht, nicht ionogenem Netzmittel und gegebenenfalls aromatischen und/oder kurzkettigen Aldehyden und/oder gegebenenfalls aromatischen Ketonen und/oder gegebenenfalls kurzkettigen ungesättigten Carbonsäuren, dadurch gekennzeichnet, daß als weiterer Glanzbildner ein oder mehrere Reaktionsprodukt(e) aus Acetaldehyd und/oder einem Aldolkondensationsprodukte von Acetaldehyd mit Ammoniak und/oder acyclischen Ketonen und/ oder aliphatischen Aminen, Amiden, Aminosäuren und/oder Hydrazinverbindungen enthalten sind, wobei die Konzentration des weiterer Glanzbildners 0,1-5 Gew.-% beträft, bezogen auf 1 Liter fertige wäßrige Lösung.It has now been found that these objects are achieved by an aqueous, acidic solution for the electrolytic deposition of tin and / or lead / tin alloys, containing a mixture of tin and / or lead salts of an alkanesulfonic acid, free alkanesulfonic acid, the alkyl group of the alkanesulfonic acid consists of 1 to 5 carbon atoms, non-ionic wetting agent and optionally aromatic and / or short-chain aldehydes and / or optionally aromatic ketones and / or optionally short-chain unsaturated carboxylic acids, characterized in that one or more reaction product (s) from acetaldehyde as a further brightener and / or an aldol condensation product of acetaldehyde with ammonia and / or acyclic ketones and / or aliphatic amines, amides, amino acids and / or hydrazine compounds, the concentration of the further brightener being 0.1-5% by weight, based on 1 Liter of finished aqueous solution.
Als Netzmittel wird bevorzugt ein nicht-ionogenes Netzmittel des Alkylarylpolyglykolethertyps gewählt. Wird als Glanzbildner ein Gemisch aus einem Reaktionsprodukt aus Acetaldehyd und/oder seinen Aldolkondensationsprodukten mit acyclischen Ketonen gewählt, so enthält das aliphatische Keton vorzugsweise 10 C-Atome im Molekül. In bevorzugter Weise werden den wäßrigen, säuren Lösungen gegebenenfalls Naphthaldehyd, Chloracetophenon oder Benzalaceton, Formaldehyd oder Acetaldehyd sowie als ungesättigte Carbonsäure Methacrylsäure oder Methylmethacrylsäure zugesetzt.A non-ionic wetting agent of the alkylaryl polyglycol ether type is preferably selected as the wetting agent. If a mixture of a reaction product of acetaldehyde and / or its aldol condensation products with acyclic ketones is chosen as the brightener, the aliphatic ketone preferably contains 10 carbon atoms in the molecule. Naphthaldehyde, chloroacetophenone or benzalacetone, formaldehyde or acetaldehyde and, as unsaturated carboxylic acid, methacrylic acid or methyl methacrylic acid are preferably added to the aqueous, acidic solutions.
Die erfindungsgemäßen wäßrigen, sauren Lösungen enthalten vorzugsweise 5 bis 25 Gew.-% des oder der entsprechenden Metallsalze, 6 bis 20 Gew.-% der Alkansulfonsäure, 0,1 bis 5 Gew.-% nicht-ionogenen Netzmittels, 0,1 bis 5 Gew.-% des Aldolkondensationsprodukts, gegebenenfalls 0,1 bis 3 % des aromatischen Aldehyds, gegebenenfalls 0,01 bis 1,0 Gew.-% des aromatischen Ketons, gegebenenfalls 0,01 bis 1,0 Gew.-% des kurzkettigen aliphatischen Aldehyds, sowie gegebenenfalls 0,01 bis 1 % der ungesättigten Carbonsäure. Die Angaben beziehen sich auf Mischungen, die auf 1 Liter fertige Lösung eingestellt werden.The aqueous, acidic solutions according to the invention preferably contain 5 to 25% by weight of the corresponding metal salt or salts, 6 to 20% by weight of the alkanesulfonic acid, 0.1 to 5% by weight of non-ionic wetting agent, 0.1 to 5 % By weight of the aldol condensation product, if appropriate 0.1 to 3% of the aromatic aldehyde, optionally 0.01 to 1.0% by weight of the aromatic ketone, optionally 0.01 to 1.0% by weight of the short-chain aliphatic aldehyde, and optionally 0.01 to 1 % of unsaturated carboxylic acid. The information relates to mixtures that are adjusted to 1 liter of finished solution.
In einem Vergleich wurde eine Lösung gemäß Beispiel 1 der US-PS 4,582,576 nachgestellt. Dabei zeigte sich, daß erst nach Zugabe von etwa 10 ml/L des erfindungsgemäß verwendeten Aldolkondensationsproduktes, bekannt aus der DE-PS 1 260 262, brauchbare Ergebnisse hinsichtlich der Glanzbildung im hohen Stromdichtebereich zu verzeichnen waren.In a comparison, a solution according to Example 1 of US Pat. No. 4,582,576 was simulated. It was found that it was only after adding about 10 ml / L of the aldol condensation product used in accordance with the invention, known from DE-PS 1 260 262, that useful results with regard to the formation of gloss in the high current density range were recorded.
Die Verwendung von Aldolkondensationsprodukten gemäß der DE-PS 1 260 262 in einem Verfahren zur elektrolytischen Abscheidung von Zinn und/oder Blei/Zinnlegierungen führt überraschenderweise zu einer verbesserten galvanischen Abscheidung im hohen Stromdichtebereich, und gleichzeitig wird eine gleichmäßige Glanzstreuung im niedrigen Stromdichtebereich erzielt.The use of aldol condensation products according to DE-PS 1 260 262 in a process for the electrolytic deposition of tin and / or lead / tin alloys surprisingly leads to improved galvanic deposition in the high current density range, and at the same time uniform gloss scattering is achieved in the low current density range.
Die Erfindung wird anhand der nachfolgenden Beispiele näher erläutert.The invention is illustrated by the following examples.
Verfahrensparameter: Die Brauchbarkeit des Elektrolyten wurde zur Zinn- und/oder Blei/Zinn-Abscheidung in einer Hull-Zelle nach DIN 50 957 geprüft. Temperatur: 20 - 25°C, Expositionszeit: 5 Minuten mit mechanischer Rührbewegung, Anoden Zinn bzw. Blei-Zinn analog der Zusammensetzung des Niederschlags. Kathodenmaterial Stahlblech, Zellstrom 2, 3 oder 4 Ampere pro Zelle.Process parameters: The usability of the electrolyte was tested for tin and / or lead / tin deposition in a Hull cell according to DIN 50 957. Temperature: 20 - 25 ° C, exposure time: 5 minutes with mechanical stirring, anode tin or lead-tin analogous to the composition of the precipitation. Sheet steel cathode material, cell current 2, 3 or 4 amps per cell.
20 g/l Zinn-(II) als Zinnmethansulfonat
70 g/l Methansulfonsäure
5 g/l Arkopal N-150 (Nonylphenolpolyglykolether mit 10 Mol ÄO)
10 g/l Aldolkondensationsprodukt nach DPA 1 260 262
1 g/l Methanal 40 Vol.-%20 g / l tin (II) as tin methanesulfonate
70 g / l methanesulfonic acid
5 g / l Arkopal N-150 (nonylphenol polyglycol ether with 10 mol ÄO)
10 g / l aldol condensation product according to DPA 1 260 262
1 g / l methanal 40 vol .-%
25 g/l Zinn-(II) als Zinnmethansulfonat
2,5 g/l Blei-(II) als Bleimethansulfonat
100 g/l Methansulfonsäure
10 g/l Sapogenat T 130 (Tributylphenolpolyglykolether mit 13 Mol ÄO)
2 g/l 1-Naphthaldehyd
2 g/l Methacrylsäure
2 ml/l Aldolkondensationsprodukt25 g / l tin (II) as tin methanesulfonate
2.5 g / l lead (II) as lead methanesulfonate
100 g / l methanesulfonic acid
10 g / l Sapogenat T 130 (tributylphenol polyglycol ether with 13 mol ÄO)
2 g / l 1-naphthaldehyde
2 g / l methacrylic acid
2 ml / l aldol condensation product
18 g/l Zinn-(II) als Zinnmethansulfonat
2 g/l Blei-(II) als Bleimethansulfonat
50 g/l Methansulfonsäure
14 g/l Lutensol AP 10 (Nonylphenolpolyglykolether mit 10 Mol ÄO)
10 g/l Aldolkondensationsprodukt nach DPA 1 260 262
0,04g/l Benzalaceton
0,8 g/l Naphthaldehyd
0,8 g/l Methanal 40 %
1,6 g/l Methacrylsäure18 g / l tin (II) as tin methanesulfonate
2 g / l lead (II) as lead methanesulfonate
50 g / l methanesulfonic acid
14 g / l Lutensol AP 10 (nonylphenol polyglycol ether with 10 mol ÄO)
10 g / l aldol condensation product according to DPA 1 260 262
0.04 g / l benzal acetone
0.8 g / l naphthaldehyde
0.8 g / l methanal 40%
1.6 g / l methacrylic acid
12 g/l Zinn-(II) als Zinnmethansulfonat
8 g/l Blei-(II) als Bleimethansulfonat
150 g/l Methansulfonsäure
5 g/l Arkopal N-150 (Nonylphenolpolyglykolether mit 15 Mol ÄO)
6 g/l Aldolkondensationsprodukt nach DPA 1 260 262
0,8 g/l Naphthaldehyd
4 ml/l Methanal 40 Vol.-%
Die Beispiele 1 bis 4 gewährleisten jeweils eine sehr gute galvanische Abscheidung im hohen Stromdichtebereich und gewährleisten gleichzeitig eine gleichmäßige Glanzstreuung im niedrigen Stromdichtebereich.12 g / l tin (II) as tin methanesulfonate
8 g / l lead (II) as lead methanesulfonate
150 g / l methanesulfonic acid
5 g / l Arkopal N-150 (nonylphenol polyglycol ether with 15 mol ÄO)
6 g / l aldol condensation product according to DPA 1 260 262
0.8 g / l naphthaldehyde
4 ml / l methanal 40 vol.%
Examples 1 to 4 each ensure very good galvanic deposition in the high current density range and at the same time ensure uniform gloss scattering in the low current density range.
20 g/l Zinn-(II) als Zinnmethansulfonat
100 g/l Methansulfonsäure
5 g/l Lutensol AP 10 (Nonylphenolpolyglykolether mit 10 Mol ÄO)
0,2 g/l Benzalaceton
1 g/l Methylmethacrylat
Bei der Zusammensetzung des Beispiels 1 der US-Patentschrift wurde bei 2 Ampere Zellenstrom ein gleichmäßiger Glanz nur im Bereich von 1 - 8 Ampere/dm² erreicht. Oberhalb 8 A/dm² traten amorphe Anbrennungen auf. Im niedrigen Stromdichtebereich < 1 A/dm² war die Abscheidung milchig matt.20 g / l tin (II) as tin methanesulfonate
100 g / l methanesulfonic acid
5 g / l Lutensol AP 10 (nonylphenol polyglycol ether with 10 mol ÄO)
0.2 g / l benzal acetone
1 g / l methyl methacrylate
In the composition of Example 1 of the US patent, a uniform gloss was only achieved in the range of 1-8 amperes / dm 2 at 2 ampere cell current. Amorphous burns occurred above 8 A / dm². In the low current density range <1 A / dm², the deposit was milky matt.
Nach Zugabe von 10 ml/l des erfindungsgemäßen Zusatzes war das Blech von 0,2 bis 10 A/dm² gleichmäßig glänzend.After adding 10 ml / l of the additive according to the invention, the sheet was uniformly glossy from 0.2 to 10 A / dm 2.
Bei einem Zellenstrom von 3 A konnte die Belastbarkeit im hohen Stromdichtebereich sogar auf 20 A/dm² erhöht werden.With a cell current of 3 A, the load capacity in the high current density range could even be increased to 20 A / dm².
Claims (6)
- Aqueous acidic solutions for the electrodeposition of tin and/or of lead/tin alloys containing a mixture of tin and/or lead salts of an alkanesulfonic acid, of free alkanesulfonic acid, the alkyl moiety of the alkanesulfonic acid consisting of from 1 to 5 carbon atoms, of a non-ionic wetting agent and optionally aromatic and/or short-chain aliphatic aldehydes and/or optionally aromatic ketones and/or optionally short-chain unsaturated carboxylic acids, characterized in that they contain, as a further brightener, one or more reaction product(s) of acetaldehyde and/or an aldol condensation product of acetaldehyde with ammonia and/or acyclic ketones and/or aliphatic amines, amides, amino acids and or hydrazine compounds, the concentration of the further brightener being from 0.1 to 5 % by weight, based on 1 liter of the final aqueous solution.
- An aqueous acidic solution according to claim 1, characterized in that the non-ionic wetting agent is an alkylarylpolyglycolether.
- An aqueous acidic solution according to claims 1 or 2, characterized in that the acyclic ketone is an aliphatic ketone having up to 10 carbon atoms in its molecule.
- The aqueous acidic solutions according to any of claims 1 to 3, characterized in that there are contained naphthaldehyde as the aromatic aldehyde, chloroacetophenone or benzalacetone as the aromatic ketone, formaldehyde or acetaldehyde as the short-chain aldehyde, as well as methacrylic acid or methyl-methacrylic acid as the unsaturated carboxylic acid.
- An aqueous acidic solution according to any of clains 1 to 4, characterized in that the amounts of the components, based on 1 liter, adjusted with water, of the final solution, area) from 5 to 25% by weight of the respective metal salt(s),b) from 6 to 20% by weight of the alkanesulfonic acid,c) from 0.1 to 5% by weight of the non-ionic wetting agent,d) from 0.1 to 5% by weight of the further brightener,e) optionally from 0.1 to 3% of the aromatic aldehyde,f) optionally from 0.01 to 1.0% by weight of the aromatic ketone,g) optionally from 0.01 to 1.0% by weight of the short-chain aliphatic aldehyde, andh) optionally from 0.01 to 1.0% of the unsaturated carboxylic acid.
- Use of an aqueous acidic solution according to any of claims 1 to 5 in a process for the electrodeposition of tin and/or lead/tin alloys.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3902042A DE3902042A1 (en) | 1989-01-25 | 1989-01-25 | AQUEOUS, ACID SOLUTIONS FOR THE ELECTROLYTIC DEPOSITION OF TIN AND / OR LEAD / TIN ALLOYS |
| DE3902042 | 1989-01-25 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0379948A2 EP0379948A2 (en) | 1990-08-01 |
| EP0379948A3 EP0379948A3 (en) | 1991-07-31 |
| EP0379948B1 true EP0379948B1 (en) | 1994-03-09 |
Family
ID=6372697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90100870A Expired - Lifetime EP0379948B1 (en) | 1989-01-25 | 1990-01-17 | Aqueous acid solutions for the electrodeposition of tin and/or lead/tin alloys |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5021130A (en) |
| EP (1) | EP0379948B1 (en) |
| JP (1) | JP3096465B2 (en) |
| DD (1) | DD291785A5 (en) |
| DE (2) | DE3902042A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5651873A (en) * | 1994-06-30 | 1997-07-29 | Mitsubishi Materials Corporation | Electroplating solution for forming Pb-Sn alloy bump electrodes on semiconductor wafer surface |
| WO1996017980A1 (en) * | 1994-12-09 | 1996-06-13 | Glyco-Metall-Werke Glyco B.V. & Co. Kg | Laminated material for sliding components and method and means for its production |
| DE19728777C2 (en) * | 1997-07-05 | 2001-03-15 | Federal Mogul Wiesbaden Gmbh | Layered composite material for plain bearings and method for manufacturing bearing shells |
| US6267863B1 (en) * | 1999-02-05 | 2001-07-31 | Lucent Technologies Inc. | Electroplating solution for electroplating lead and lead/tin alloys |
| DE60226196T2 (en) * | 2001-05-24 | 2009-05-14 | Shipley Co., L.L.C., Marlborough | Tin-plating |
| US6730209B2 (en) * | 2002-02-22 | 2004-05-04 | Lucent Technologies Inc. | Solder electroplating bath including brighteners having reduced volatility |
| GB0216331D0 (en) | 2002-07-13 | 2002-08-21 | Dana Corp | Bearings |
| WO2004034427A2 (en) * | 2002-10-08 | 2004-04-22 | Honeywell International Inc. | Semiconductor packages, lead-containing solders and anodes and methods of removing alpha-emitters from materials |
| JP4749746B2 (en) * | 2005-03-24 | 2011-08-17 | Ｄｏｗａメタルテック株式会社 | Tin plating material and method for producing the same |
| CN110428939B (en) * | 2019-08-09 | 2020-06-30 | 常州大学 | Preparation method of high-conductivity graphene copper/aluminum composite wire |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2525942A (en) * | 1945-06-29 | 1950-10-17 | Standard Oil Co | Electrodepositing bath and process |
| DE1260262B (en) * | 1963-05-06 | 1968-02-01 | Friedr Blasberg G M B H | Galvanic bath and process for the electrolytic deposition of high-gloss tin coatings |
| US4132610A (en) * | 1976-05-18 | 1979-01-02 | Hyogo Prefectural Government | Method of bright electroplating of tin-lead alloy |
| US4582576A (en) * | 1985-03-26 | 1986-04-15 | Mcgean-Rohco, Inc. | Plating bath and method for electroplating tin and/or lead |
-
1989
- 1989-01-25 DE DE3902042A patent/DE3902042A1/en active Granted
-
1990
- 1990-01-17 EP EP90100870A patent/EP0379948B1/en not_active Expired - Lifetime
- 1990-01-17 DE DE90100870T patent/DE59004841D1/en not_active Expired - Lifetime
- 1990-01-23 US US07/469,066 patent/US5021130A/en not_active Expired - Lifetime
- 1990-01-24 JP JP02014730A patent/JP3096465B2/en not_active Expired - Lifetime
- 1990-01-24 DD DD90337314A patent/DD291785A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP3096465B2 (en) | 2000-10-10 |
| DD291785A5 (en) | 1991-07-11 |
| EP0379948A2 (en) | 1990-08-01 |
| DE3902042A1 (en) | 1990-07-26 |
| DE59004841D1 (en) | 1994-04-14 |
| DE3902042C2 (en) | 1991-05-02 |
| US5021130A (en) | 1991-06-04 |
| JPH02232389A (en) | 1990-09-14 |
| EP0379948A3 (en) | 1991-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1207177B (en) | Process for the production of shiny galvanic metal coatings | |
| DE2122263C2 (en) | Process for the production of a primary brightener for acid electroplating tinning baths and its use | |
| WO2007147605A2 (en) | Tripyridinium compounds used as additives in aqueous alkaline baths, devoid of cyanide, for the deposition of electroplated zinc and zinc alloy coatings | |
| WO2000014305A1 (en) | Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings | |
| EP2103717B1 (en) | Pyrophosphate-based bath for depositing tin alloy layers | |
| EP0379948B1 (en) | Aqueous acid solutions for the electrodeposition of tin and/or lead/tin alloys | |
| DE3447813A1 (en) | AQUEOUS ACID BATH AND A METHOD FOR GALVANIC DEPOSITION OF ZINC OR ZINC ALLOYS | |
| CH619987A5 (en) | ||
| DE69724324T2 (en) | Process for the production of semi-glossy and glossy electro-galvanic coatings using high current densities in a bath containing a zinc salt of a sulfur-containing acid and composition therefor | |
| DE2319197B2 (en) | AQUATIC BATH AND METHOD FOR GALVANIC DEPOSITION OF A DUCTILE, ADHESIVE ZINC COATING | |
| DE2231988A1 (en) | METHOD OF ELECTRICAL DEPOSITION OF TIN | |
| CH629541A5 (en) | METHOD FOR ELECTROLYTICALLY DEPOSITING AN IRON ALLOY. | |
| EP3067444B1 (en) | Deposition of decorative palladium iron alloy coatings on metallic substances | |
| EP0343559B1 (en) | Use of 2-substituted ethane sulfone compounds as galvanic auxiliary agents | |
| DE2658934B2 (en) | Aqueous, cyanide-free, alkaline zinc bath for the galvanic production of high-gloss zinc coatings | |
| DE2326300A1 (en) | Aqueous ACID ZINC GALVANIZATION BATH AND PROCESS | |
| EP0526497B1 (en) | Acid nickel baths containing 1-(2-sulfoethyl)-pyridinium betaine | |
| DE1952218A1 (en) | Process and means for electroplating | |
| DE3228911C2 (en) | ||
| DE1016527B (en) | Bath and process for the galvanic production of leveling iron, iron-nickel or iron-nickel-zinc coatings | |
| DE2740592C2 (en) | Galvanic zinc bath | |
| DE1621117A1 (en) | Process for the electrolytic deposition of nickel coating | |
| DE2815786A1 (en) | AQUATIC BATH FOR EDECTROCHEMICAL DEPOSITION OF GLOSSY IRON-NICKEL COATING | |
| DE2948999C2 (en) | Aqueous, acidic bath for the electrodeposition of gold and method for the electrodeposition of hard gold with its use | |
| DE3139641A1 (en) | "GALVANIC BATH AND METHOD FOR SEPARATING SEMI-GLOSSY DUCTILERS AND TENSION-FREE NICKEL COATINGS" |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB LU NL |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB LU NL |
|
| 17P | Request for examination filed |
Effective date: 19910917 |
|
| 17Q | First examination report despatched |
Effective date: 19920817 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB LU NL |
|
| REF | Corresponds to: |
Ref document number: 59004841 Country of ref document: DE Date of ref document: 19940414 |
|
| ET | Fr: translation filed | ||
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19940607 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20030127 Year of fee payment: 14 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040117 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20060207 Year of fee payment: 17 |
|
| BERE | Be: lapsed |
Owner name: *BLASBERG-OBERFLACHENTECHNIK G.M.B.H. Effective date: 20070131 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070131 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20080115 Year of fee payment: 19 Ref country code: GB Payment date: 20080124 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20080111 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20090122 Year of fee payment: 20 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20090117 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20090801 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20091030 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090801 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090117 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090202 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20100117 |