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EP0379948A2 - 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 PDF

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Publication number
EP0379948A2
EP0379948A2 EP90100870A EP90100870A EP0379948A2 EP 0379948 A2 EP0379948 A2 EP 0379948A2 EP 90100870 A EP90100870 A EP 90100870A EP 90100870 A EP90100870 A EP 90100870A EP 0379948 A2 EP0379948 A2 EP 0379948A2
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EP
European Patent Office
Prior art keywords
tin
optionally
lead
aqueous
weight
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.)
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Application number
EP90100870A
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German (de)
French (fr)
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EP0379948A3 (en
EP0379948B1 (en
Inventor
Willi Metzger
Manfred Schmitz
Karl-Jürgen Schmidt
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Blasberg-Oberflachentechnik GmbH
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Blasberg-Oberflachentechnik GmbH
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    • 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 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 process 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 poor resilience 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 ° C atoms, non-ionic wetting agent and optionally aromatic short-chain aldehydes and / or optionally aromatic ketones and / or optionally short-chain unsaturated carboxylic acids, characterized in that a mixture of a reaction product of acetaldehyde and / or its as a further brightener Aldol condensation products containing ammonia and / or acyclic ketones and / or aliphatic amines, amides, amino acids and / or hydrazine compounds.
  • 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 brightening agent, 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 mixture in a preferred manner.
  • 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 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 the 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 in accordance with 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.
  • 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.
  • 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 deposition was milky matt.
  • the sheet After adding 10 ml / l of the additive according to the invention, the sheet was uniformly shiny from 0.2 to 10 A / dm 2.

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  • 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)

Abstract

A description is given of aqueous acid solutions for the electrodeposition of tin and/or lead/tin alloys to improve electroplating in the high current density range and obtain uniform lustre throwing power in metals deposited in the low current density range. The solutions according to the invention contain a mixture of metal salts, free alkanesulphonic acid, nonionic wetting agents and, optionally, aromatic short-chain aldehydes and/or, optionally, aromatic ketones and/or, optionally, short-chain unsaturated carboxylic acids. The solutions according to the invention are therefore characterised in that tin and/or lead salts of the alkanesulphonic acid are used as metal salts, the alkyl group of the alkanesulphonic acid consisting of 1 to 5 carbon atoms, and the free alkanesulphonic acid containing alkyl groups with 1 to 5 carbon atoms. As a further brightener, the solutions contain a mixture of a reaction product of acetaldehyde and/or its aldol condensation products with ammonia and/or acyclic ketones and/or aliphatic amines, amides, amino acids and/or hydrazine compounds.

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 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 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 process 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 poor resilience 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 kurzkettigen Aldehyden und/oder gegebenen­falls aromatischen Ketonen und/oder gegebenenfalls kurz­kettigen ungesättigten Carbonsäuren, dadurch gekennzeich­net, daß als weiterer Glanzbildner ein Gemisch aus einem Reaktionsprodukt aus Acetaldehyd und/oder seinen Aldolkon­densationsprodukten mit Ammoniak und/oder acyclischen Ketonen und/ oder aliphatischen Aminen, Amiden, Amino­säuren und/oder Hydrazinverbindungen enthalten ist.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 ° C atoms, non-ionic wetting agent and optionally aromatic short-chain aldehydes and / or optionally aromatic ketones and / or optionally short-chain unsaturated carboxylic acids, characterized in that a mixture of a reaction product of acetaldehyde and / or its as a further brightener Aldol condensation products containing ammonia and / or acyclic ketones and / or aliphatic amines, amides, amino acids and / or hydrazine compounds.

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 im Gemisch 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 brightening agent, 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 mixture in a preferred manner.

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, gegebenen­ falls 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 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 the 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 useful results in terms of gloss formation in the high current density range were only obtained after adding about 10 ml / L of the aldol condensation product according to the invention, known from DE-PS 1 260 262.

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 in accordance with 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.

Beispiel 1example 1

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.%

Beispiel 2Example 2

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

Beispiel 3Example 3

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

Beispiel 4Example 4

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.-%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.%

Die Beispiele 1 bis 4 gewährleisten jeweils eine sehr gute galvanische Abscheidung im hohen Stromdichtebereich und gewährleisten gleichzeitig eine gleichmäßige Glanz­streuung im niedrigen Stromdichtebereich.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.

Vergleichsbeispiel 1Comparative Example 1

20 g/l Zinn-(II) als Zinnmethansulfonat
100 g/l Methansulfonsäure
g/l Lutensol AP 10 (Nonylphenolpolyglykolether mit 10 Mol ÄO)
0,2 g/l Benzalaceton
1 g/l Methylmethacrylat20 g / l tin (II) as tin methanesulfonate
100 g / l methanesulfonic acid
g / l Lutensol AP 10 (nonylphenol polyglycol ether with 10 mol AO)
0.2 g / l benzal acetone
1 g / l methyl methacrylate

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.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 deposition 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 shiny 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)

1. 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 kurzkettigen Aldehyden und/oder gegebe­nenfalls kurzkettigen ungesättigten Carbonsäuren, dadurch gekennzeichnet, daß als weiterer Glanz­bildner ein Gemisch aus einem Reaktionsprodukt aus Acetaldehyd und/oder seinen Aldolkondensa­tionsprodukten mit Ammoniak und/oder acyclischen Ketonen und/oder aliphatischen Aminen, Amiden, Aminosäuren und/oder Hydrazinverbindungen ent­halten ist.1. 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, not ionogenic Wetting agents and optionally aromatic short-chain aldehydes and / or optionally short-chain unsaturated carboxylic acids, characterized in that a further brightener is a mixture of a reaction product of acetaldehyde and / or its aldol condensation products with ammonia and / or acyclic ketones and / or aliphatic amines, amides, amino acids and / or hydrazine compounds is included. 2. Wäßrige, saure Lösung nach Anspruch 1, dadurch gekennzeichnet, daß das nicht-ionogene Netzmit­tel, ein Alkylarylpolyglykolether ist.2. Aqueous, acidic solution according to claim 1, characterized in that the non-ionic wetting agent is an alkylaryl polyglycol ether. 3. Wäßrige, saure Lösung nach Anspruch 1 oder 2, da­durch gekennzeichnet, daß das acyclische Keton ein aliphatisches Keton mit bis zu 10 C-Atomen im Molekül ist.3. Aqueous, acidic solution according to claim 1 or 2, characterized in that the acyclic ketone is an aliphatic ketone with up to 10 carbon atoms in the molecule. 4. Wäßrige, saure Lösungen nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als aromati­scher Aldehyd Naphthaldehyd, als aromatisches Keton Chloracetophenon oder Benzalaceton, als kurzkettiger Aldehyd Formaldehyd oder Acetaldehyd sowie als ungesättigte Carbonsäure Methacrylsäure oder Methylmethacrylsäure im Gemisch enthalten ist.4. Aqueous, acidic solutions according to one of claims 1 to 3, characterized in that the aromatic aldehyde is naphthaldehyde, the aromatic ketone is chloroacetophenone or benzalacetone, the short-chain aldehyde is formaldehyde or acetaldehyde and the unsaturated carboxylic acid is methacrylic acid or methyl methacrylic acid in the mixture. 5. Wäßrige, saure Lösung nach einem der Ansprüche 1 bis 4 dadurch gekennzeichnet, daß sich die Menge der Komponenten bezogen auf mit Wasser auf 1 Li­ter fertige Lösungen einzustellendes Gemisch beläuft auf a) 5 bis 25 Gew.-% des oder der entsprechenden Metallsalze, b) 6 bis 20 Gew.-% der Alkansulfonsäure, c) 0,1 bis 5 Gew.-% nicht-ionogenen Netzmittels, d) 0,1 bis 5 Gew.-% des Aldolkondensationsprodukts, e) gegebenenfalls 0,1 bis 3 % des aromatischen Aldehyds, f) gegebenenfalls 0,01 bis 1,0 Gew.-% des aroma­tischen Ketons, g) gegebenenfalls 0,01 bis 1,0 Gew.-% des kurz­kettigen aliphatischen Aldehyds, h) gegebenenfalls 0,01 bis l % der ungesättigten Carbonsäure. 5. Aqueous, acidic solution according to one of claims 1 to 4, characterized in that the amount of the components is based on the mixture to be adjusted with water to 1 liter of finished solutions a) 5 to 25% by weight of the corresponding metal salt or salts, b) 6 to 20% by weight of the alkanesulfonic acid, c) 0.1 to 5% by weight of non-ionic wetting agent, d) 0.1 to 5% by weight of the aldol condensation product, e) optionally 0.1 to 3% of the aromatic aldehyde, f) optionally 0.01 to 1.0% by weight of the aromatic ketone, g) optionally 0.01 to 1.0% by weight of the short-chain aliphatic aldehyde, h) optionally 0.01 to 1% of the unsaturated carboxylic acid. 6. Verwendung einer waßrigen, säuren Lösung gemäß einem der Ansprüche 1 bis 5 in einem Verfahren zur elektrolytischen Abscheidung von Zinn und/­oder Blei/Zinnlegierungen.6. Use of an aqueous, acidic solution according to one of claims 1 to 5 in a process for the electrolytic deposition of tin and / or lead / tin alloys.
EP90100870A 1989-01-25 1990-01-17 Aqueous acid solutions for the electrodeposition of tin and/or lead/tin alloys Expired - Lifetime EP0379948B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3902042 1989-01-25
DE3902042A DE3902042A1 (en) 1989-01-25 1989-01-25 AQUEOUS, ACID SOLUTIONS FOR THE ELECTROLYTIC DEPOSITION OF TIN AND / OR LEAD / TIN ALLOYS

Publications (3)

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EP0379948A2 true EP0379948A2 (en) 1990-08-01
EP0379948A3 EP0379948A3 (en) 1991-07-31
EP0379948B1 EP0379948B1 (en) 1994-03-09

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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)

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US (1) US5021130A (en)
EP (1) EP0379948B1 (en)
JP (1) JP3096465B2 (en)
DD (1) DD291785A5 (en)
DE (2) DE3902042A1 (en)

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WO2004007809A2 (en) * 2002-07-13 2004-01-22 Dana Corporation Plain bearing having an overlay alloy layer
EP1705267A1 (en) * 2005-03-24 2006-09-27 Dowa Mining Co., Ltd Tin-plated product and method for producing same

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US5651873A (en) * 1994-06-30 1997-07-29 Mitsubishi Materials Corporation Electroplating solution for forming Pb-Sn alloy bump electrodes on semiconductor wafer surface
US5976712A (en) * 1994-12-09 1999-11-02 Federal-Mogul Wiesbaden Gmbh Multilayer material for sliding elements and process and means for the production thereof
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
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
CN110428939B (en) * 2019-08-09 2020-06-30 常州大学 Preparation method of high-conductivity graphene copper/aluminum composite wire

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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

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US2525942A (en) * 1945-06-29 1950-10-17 Standard Oil Co Electrodepositing bath and process

Patent Citations (3)

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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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004007809A2 (en) * 2002-07-13 2004-01-22 Dana Corporation Plain bearing having an overlay alloy layer
WO2004007809A3 (en) * 2002-07-13 2004-04-15 Dana Corp Plain bearing having an overlay alloy layer
US7174637B2 (en) 2002-07-13 2007-02-13 Dana Corporation Bearings
US7455458B2 (en) 2002-07-13 2008-11-25 Mahle Engine Systems Ltd. Bearings
EP1705267A1 (en) * 2005-03-24 2006-09-27 Dowa Mining Co., Ltd Tin-plated product and method for producing same

Also Published As

Publication number Publication date
DE3902042C2 (en) 1991-05-02
DE59004841D1 (en) 1994-04-14
DD291785A5 (en) 1991-07-11
US5021130A (en) 1991-06-04
DE3902042A1 (en) 1990-07-26
JP3096465B2 (en) 2000-10-10
EP0379948A3 (en) 1991-07-31
JPH02232389A (en) 1990-09-14
EP0379948B1 (en) 1994-03-09

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