EP1137825A2 - Aqueous solution for electrodepositing tin-zinc alloys - Google Patents

Aqueous solution for electrodepositing tin-zinc alloys

Info

Publication number
EP1137825A2
EP1137825A2 EP99960973A EP99960973A EP1137825A2 EP 1137825 A2 EP1137825 A2 EP 1137825A2 EP 99960973 A EP99960973 A EP 99960973A EP 99960973 A EP99960973 A EP 99960973A EP 1137825 A2 EP1137825 A2 EP 1137825A2
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.)
Granted
Application number
EP99960973A
Other languages
German (de)
French (fr)
Other versions
EP1137825B1 (en
Inventor
Manfred Jordan
Gernot Strube
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dr Ing Max Schloetter GmbH and Co KG
Original Assignee
Dr Ing Max Schloetter GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dr Ing Max Schloetter GmbH and Co KG filed Critical Dr Ing Max Schloetter GmbH and Co KG
Publication of EP1137825A2 publication Critical patent/EP1137825A2/en
Application granted granted Critical
Publication of EP1137825B1 publication Critical patent/EP1137825B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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 the deposition of tin-zinc alloys and in particular to an electroplating bath which enables the deposition of tin-zinc alloys from a cyanide-free tin (II) -zinc (II) solution with a simple bath control.
  • Products that are electroplated with a tin-zinc alloy are characterized by excellent corrosion resistance.
  • the resistance to hydraulic fluid and aqueous salt solutions make products coated in this way appear interesting for the automotive industry.
  • Products coated with tin-zinc alloys are also used in the broadcasting, electrical and construction industries due to their corrosion resistance and excellent solderability.
  • electroplating baths have the disadvantage that a higher energy expenditure is required for the deposition of tin (IV) ions than for the deposition of tin (II) ions.
  • the bath management involves the difficulty that when the anode is dissolved, which advantageously also consists of a tin-zinc alloy, the formation of tin (IV) ions must be promoted by forming a film by means of polarization.
  • the thickness and composition of the deposited tin-zinc alloy depend on the current density and thus dependent on the geometry of the substrate. The toxicity of the cyanide ions also complicates industrial use.
  • an electroplating bath which allows the deposition of tin from the stage of the divalent tin, so that the required energy expenditure is reduced.
  • the dependence of the speed and composition of the tin-zinc deposition on the current density was also reduced.
  • the amphoteric surface-active surfactants proposed in this publication mean that the bath guidance remains critical and must be set and monitored very precisely in order to prevent dark and disturbed deposits.
  • aqueous solution which, in addition to tin (II) and zinc (II) ions, contains aliphatic carboxylic acids and / or their alkali metal salts as complexing agents, and also a mixture of anionic and nonionic surfactants as grain refiners.
  • the aqueous solution according to the invention further contains aromatic aldehydes and / or aromatic ketones as brighteners. Aldehydes or ketones of the following formulas (I) or (II) are preferably used:
  • a special, advantageous compound of formula (II) is o-Cl-benzaldehyde.
  • the pH of the solution is preferably 2-8, particularly preferably 3-5.
  • tin (II) and zinc (II) ions are preferably used in the form of chlorides, sulfates or alkyl sulfonates.
  • one or more conductive salts of the corresponding anions are additionally used. NH 4 C1 and / or NH (CH 3 S0 3 ) are preferred.
  • Preferred aliphatic carboxylic acids in the aqueous solution according to the invention are hydrocarboxylic acids and aminocarboxylic acids and particularly preferred is citric acid or its alkali salts.
  • the nonionic surfactants of the present invention preferably have the formula (III):
  • Aliphatic or aromatic sulfonates are preferably used as anionic surfactants.
  • one or more compounds of the formulas (VI) to (IX) are selected:
  • R C 3 _ 12 alkyl
  • X H, -S0 3 M
  • M Na, K, NH 4 b ') R'-O- (C 2 H 4 O) ⁇ r -R'iSO 3 M (VII)
  • R ' C 3 _ 12 alkyl
  • R » C 2 _ 5 alkyl
  • M Na, K, NH 4
  • R "' H, C-L_5-alkyl. 0- (C 2 H 4 0) n -X;
  • R " 1 H, C 1 _ 5 alkyl, 0- (C 2 H 4 0) n -X;
  • anionic surfactants according to the following formulas (X) to (XIII)
  • 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)
  • carboxylic acids are nicotinic acid and / or Na benzoate.
  • V orteilhaft stock be selected, the concentrations of the individual components within the following ranges:
  • the present invention also includes the use of the aqueous solution described above for the deposition of tin Zinc coatings, in particular tin-zinc coatings with a zinc content of 10 to 50% by weight.
  • An aqueous solution was prepared from the following components:
  • Nicotinic acid 0.1 g / 1 o-Cl-benzaldehyde 0.05 g / 1
  • Substrate surface with a thickness of 10 microns and deposited with a light gray color.
  • aqueous solution according to the invention can be used to deposit tin-zinc alloys of uniform thickness and composition with a uniform light color without the use of cyanide ions with low energy consumption.

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)

Abstract

The invention relates to an aqueous solution comprising the following components: Zn(II) ions, Sn(II) ions, aliphatic carboxylic acids and/or their alkaline salts, anionic surfactants, non-ionogenic surfactants and optionally aromatic aldehydes, aromatic ketones, aromatic carboxylic acids and heterocyclic carboxylic acids or their alkaline salts or conducting salts. The inventive solution provides a means for electrodepositing uniform light-colored tin-zinc alloys without having to use cyanide ions, allowing low energy consumption and few requirements in terms of the control of the bath.

Description

Wäßrige Lösung zur elektrolytischen Abscheidung von Zinn-Zink-Legierungen. W ä ß ri e g solution elektrolytisc h s Ab sc h ei d ung of tin-zinc alloys.
Die vorliegende Erfindung betrifft eine wäßrige Lösung zur Abscheidung von Zinn-Zink-Legierungen und insbesondere ein Elektroplattierungsbad welches die Abscheidung von Zinn-Zink- Legierungen aus einer cyanidfreien Zinn (II) -Zink (II) -Lösung bei einfacher Badführung ermöglicht.The present invention relates to an aqueous solution for the deposition of tin-zinc alloys and in particular to an electroplating bath which enables the deposition of tin-zinc alloys from a cyanide-free tin (II) -zinc (II) solution with a simple bath control.
Produkte die durch Elektroplattierung mit einer Zinn-Zink- Legierung beschichtet werden, zeichnen sich durch eine ausgezeichnete Korrosionsbeständigkeit aus. Speziell die Beständigkeit gegenüber Hydraulikflüssigkeit und wäßrigen Salzlösungen lassen derartig beschichtete Produkte für die Automobilindustrie interessant erscheinen. Auch in der Rundfunk-, Elektro- und Bauindustrie werden mit Zinn-Zink- Legierungen beschichtete Produkte aufgrund ihrer Korrosionsbeständigkeit sowie ihrer hervorragenden Lötbarkeit eingesetzt.Products that are electroplated with a tin-zinc alloy are characterized by excellent corrosion resistance. In particular, the resistance to hydraulic fluid and aqueous salt solutions make products coated in this way appear interesting for the automotive industry. Products coated with tin-zinc alloys are also used in the broadcasting, electrical and construction industries due to their corrosion resistance and excellent solderability.
Die bislang üblichen Elektroplattierungsbäder enthielten Zinn in der Oxidationsstufe +iv sowie Cyanidionen. Derartige Elektroplattierungsbäder haben jedoch den Nachteil, daß zur Abscheidung von Zinn (IV) -Ionen ein höherer Energieaufwand erforderlich ist als zur Abscheidung von Zinn (II) -Ionen. Zudem beinhaltet die Badführung die Schwierigkeit, daß bei der Auflösung der Anode, die vorteilhafterweise ebenfalls aus einer Zinn-Zink-Legierung besteht, durch Bildung eines Films mittels Polarisation die Bildung von Zinn (IV) -Ionen gefördert werden muß. Weiterhin ist die Dicke und Zusammensetzung der abgeschiedenen Zinn-Zink-Legierung von der Stromdichte und damit von der Geometrie des Substrats abhängig. Auch die Toxizitat der Cyanidionen erschwert die industrielle Nutzung.The electroplating baths that were common until now contained tin in the + iv oxidation state and cyanide ions. However, such electroplating baths have the disadvantage that a higher energy expenditure is required for the deposition of tin (IV) ions than for the deposition of tin (II) ions. In addition, the bath management involves the difficulty that when the anode is dissolved, which advantageously also consists of a tin-zinc alloy, the formation of tin (IV) ions must be promoted by forming a film by means of polarization. Furthermore, the thickness and composition of the deposited tin-zinc alloy depend on the current density and thus dependent on the geometry of the substrate. The toxicity of the cyanide ions also complicates industrial use.
Letztgenanntes Problem wurde in US-5,378,346 gelöst, indem die Cyanidionen durch Alkalitartrate als Komplexbildner ersetzt wurden. Die durch die Verwendung von Zinn (IV) -Ionen entstehenden Probleme werden jedoch hier nicht gelöst.The latter problem was solved in US 5,378,346 by replacing the cyanide ions with alkali tartrates as complexing agents. However, the problems arising from the use of tin (IV) ions are not solved here.
Gemäß EP 0 663 460 ist ein Elektroplattierungsbad bekannt, welches die Abscheidung von Zinn aus der Stufe des zweiwertigen Zinns erlaubt, so daß der erforderliche Energieaufwand gesenkt wird. Auch die Abhängigkeit der Geschwindigkeit und Zusammensetzung der Zinn-Zink-Abscheidung von der Stromdichte wurde verringert. Die in dieser Druckschrift vorgeschlagenen amphoteren oberflächenaktiven Tenside führen jedoch dazu, daß die Badführung nach wie vor kritisch bleibt und sehr genau eingestellt und überwacht werden muß, um dunkle und gestörte Abscheidungen zu verhindern.According to EP 0 663 460, an electroplating bath is known which allows the deposition of tin from the stage of the divalent tin, so that the required energy expenditure is reduced. The dependence of the speed and composition of the tin-zinc deposition on the current density was also reduced. However, the amphoteric surface-active surfactants proposed in this publication mean that the bath guidance remains critical and must be set and monitored very precisely in order to prevent dark and disturbed deposits.
Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung einer Elektroplattierungsbadlösung zur Abscheidung von Zinn-Zink-Legierungen, die kein Cyanid enthält, die durch Abscheidung von Zinn aus einer Zinn ( II) - Ionen enthaltenden Lösung einen geringen Energieverbrauch bei der Abscheidung ermöglicht, und deren Badführung über weite Bereiche der frei wählbaren Parameter unkritisch ist und fehler- und verfärbungsfreie Abscheidungen ermöglicht.It is therefore an object of the present invention to provide an electroplating bath solution for the deposition of tin-zinc alloys which does not contain cyanide, which enables a low energy consumption in the deposition by deposition of tin from a tin (II) ion solution, and the bath management thereof is uncritical over wide ranges of the freely selectable parameters and enables flawless and discoloration-free depositions.
Die obige Aufgabe wird mit einer wäßrigen Lösung erreicht, die neben Zinn(II)- und Zink (II) -Ionen aliphatische Carbonsäuren und/oder deren Alkalisalze als Komplexbildner, sowie ein Gemisch aus anionischen und nicht ionogenen Tensiden als Kornverfeinerer beinhaltet. Die erfindungsgemäße wäßrige Lösung enthält in einer vorteilhaften Ausgestaltung weiterhin aromatische Aldehyde und/oder aromatische Ketone als Glanzbildner. Vorzugsweise werden Aldehyde bzw. Ketone der folgenden Formeln (I) bzw. (II) eingesetzt:The above object is achieved with an aqueous solution which, in addition to tin (II) and zinc (II) ions, contains aliphatic carboxylic acids and / or their alkali metal salts as complexing agents, and also a mixture of anionic and nonionic surfactants as grain refiners. In an advantageous embodiment, the aqueous solution according to the invention further contains aromatic aldehydes and / or aromatic ketones as brighteners. Aldehydes or ketones of the following formulas (I) or (II) are preferably used:
AR-R-CO-R' (I)AR-R-CO-R '(I)
mit AR = Phenyl, Naphtyl; R _ CH2, CH = CH und R' = H, Cτ__3- Alkyl ;with AR = phenyl, naphthyl; R _ CH 2 , CH = CH and R '= H, Cτ__ 3 - alkyl;
mit X = H, CH3, OCH3, Cl, Br.with X = H, CH 3 , OCH 3 , Cl, Br.
Eine spezielle, vorteilhafte Verbindung der Formel (II) ist o-Cl-Benzaldehyd.A special, advantageous compound of formula (II) is o-Cl-benzaldehyde.
Der pH-Wert der Lösung liegt vorzugsweise bei 2-8, insbesondere bevorzugt bei 3-5.The pH of the solution is preferably 2-8, particularly preferably 3-5.
Die Zinn(II)- und Zink (II) -Ionen werden bevorzugt in Form von Chloriden, Sulfaten oder Alkylsulfonaten eingesetzt.The tin (II) and zinc (II) ions are preferably used in the form of chlorides, sulfates or alkyl sulfonates.
Gegebenenfalls werden zusätzlich ein oder mehrere Leitsalze der entsprechenden Anionen eingesetzt. Bevorzugt sind NH4C1 und/oder NH (CH3S03) .If necessary, one or more conductive salts of the corresponding anions are additionally used. NH 4 C1 and / or NH (CH 3 S0 3 ) are preferred.
Bevorzugte aliphatische Carbonsäuren in der erfindungsgemäßen wäßrigen Lösung sind Hydrocarbonsäuren und Aminocarbonsäuren und besonders bevorzugt ist Zitronensäure oder deren Alkalisalze.Preferred aliphatic carboxylic acids in the aqueous solution according to the invention are hydrocarboxylic acids and aminocarboxylic acids and particularly preferred is citric acid or its alkali salts.
Die nichtionogenen Tenside der vorliegenden Erfindung haben bevorzugt die Formel (III) :The nonionic surfactants of the present invention preferably have the formula (III):
R-0-(C2H40)nH (III)R-0- (C 2 H 4 0) n H (III)
mit R = Alkyl, Aryl, Alkylaryl; und n = 1 - 100. Besonders bevorzugt ist n = 6 -15 und eine Gesamtsumme von 8-20 Kohlenstoffatomen im Arylrest.with R = alkyl, aryl, alkylaryl; and n = 1-100. Particularly preferred is n = 6-15 and a total of 8-20 carbon atoms in the aryl radical.
Zusätzlich zu diesen nichtionogenen Tensiden können Thioether oder Amine mit den Formeln (IV) und (V)In addition to these nonionic surfactants, thioethers or amines with the formulas (IV) and (V)
R*-S- (C2H40)nH (IV)R * -S- (C 2 H 4 0) n H (IV)
R"-N[(C2H4θ)nH]2 (V) R "-N [(C 2 H4θ) n H] 2 ( V )
mit R' = Cτ__3-Alkyl oder -(C2H40)nH und R" = C5_2o-Alky1 mit n = 1 - 100, insbesondere bevorzugt n = 6 - 15, als nichtionogene Tenside eingesetzt werden. Besonders vorteilhaft sind H(C2H 0) n-S- (C2H40) nH mit n = 8 - 12 und C12H25-N[(C2H40)nH]2 mit n = 15 - 25 .with R '= Cτ__ 3 -alkyl or - (C 2 H 4 0) n H and R "= C 5 _ 2 o- Alk y 1 with n = 1 - 100, particularly preferably n = 6 - 15, as nonionic surfactants H (C 2 H 0) n -S- (C 2 H 4 0) n H with n = 8-12 and C 12 H 25 -N [(C 2 H 4 0) n H] are particularly advantageous. 2 with n = 15 - 25.
Als anionische Tenside werden vorzugsweise aliphatische oder aromatische Sulfonate eingesetzt. In einer bevorzugten Ausführungsform werden eine oder mehrere Verbindungen der Formeln (VI) bis (IX) ausgewählt:Aliphatic or aromatic sulfonates are preferably used as anionic surfactants. In a preferred embodiment, one or more compounds of the formulas (VI) to (IX) are selected:
mit R = C3_12-Alkyl; X = H, -S03M; M = Na, K, NH4 b') R'-O- (C2H4O)ιr-R'iSO3M (VII)with R = C 3 _ 12 alkyl; X = H, -S0 3 M; M = Na, K, NH 4 b ') R'-O- (C 2 H 4 O) ιr -R'iSO 3 M (VII)
mit R' = C3_12-Alkyl; R» = C2_5-Alkyl; M = Na, K, NH4 with R '= C 3 _ 12 alkyl; R » = C 2 _ 5 alkyl; M = Na, K, NH 4
mit R"' = H, C-L_5-Alkyl. 0- (C2H40) n-X;with R "'= H, C-L_5-alkyl. 0- (C 2 H 4 0) n -X;
oder und X = S03 mit M = Na, K, NH4 or and X = S0 3 with M = Na, K, NH 4
mit R"1 = H, C1_5-Alkyl, 0- (C2H40)n-X;with R " 1 = H, C 1 _ 5 alkyl, 0- (C 2 H 4 0) n -X;
oder und X = S03M mit M = Na, K, NH4 mit n = 8 - 14 . or and X = S0 3 M with M = Na, K, NH 4 with n = 8 - 14.
Eine besonders bevorzugte Auswahl aus der obigen Reihe sind die anioniεchen Tenside gemäß den folgenden Formeln (X) bis (XIII) A particularly preferred selection from the series above is the anionic surfactants according to the following formulas (X) to (XIII)
(XI)(XI)
C12H25-O-(C2H4θ)n-C3H6SO3KC 12 H25-O- (C2H4θ) nC 3 H 6 SO 3 K
undand
mit n = 8 - 14 .with n = 8 - 14.
Optional kann das Elektroplattierungsbad zur Abscheidung von Zink-Zinn-Legierungen auch aromatische und/oder heterocyclische Carbonsäuren oder deren Alkalisalze nach Formel (XIV)Optionally, 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)
R-COOM, it R = ' und M= H, Na, K, Ntt, (XIV) R-COOM, it R = 'and M = H, Na, K, Ntt, (XIV)
enthalten. Bevorzugte Ausführungsformen dieser Carbonsäuren sind Nikotinsäure und/oder Na-Benzoat.contain. Preferred embodiments of these carboxylic acids are nicotinic acid and / or Na benzoate.
Vorteilhafterweise werden die Konzentrationen der einzelnen Komponenten innerhalb der folgenden Bereiche gewählt: V orteilhafterweise be selected, the concentrations of the individual components within the following ranges:
Zink (II) -Ionen 5 g/i bis 50 g/1 insbesondere bevorzugt 20 g/1 bis 25 g/1 Zinn (II) -Ionen 0,5 g/1 bis 5 g/1 insbesondere bevorzugt i g/i bis 3 g/1 aliphatische Carbonsäuren 30 g/1 bis 200 g/1 insbesondere bevorzugt 60 g/1 bis 140 g/1 nicht ionogene TensideZinc (II) ions 5 g / i to 50 g / 1, particularly preferably 20 g / 1 to 25 g / 1 tin (II) ions 0.5 g / 1 to 5 g / 1, particularly preferably ig / i to 3 g / 1 aliphatic carboxylic acids 30 g / 1 to 200 g / 1 particularly preferably 60 g / 1 to 140 g / 1 non-ionic surfactants
- gemäß Formel (III) 0 g/1 bis 10 g/1 insbesondere bevorzugt o g/i bis 2 g/i- According to formula (III) 0 g / 1 to 10 g / 1, particularly preferably o g / i to 2 g / i
- gemäß Formel (IV) oder (V) o g/i bis 10 g/1 insbesondere bevorzugt o g/l bis 2 g/1 anionische Tenside 5 g/l bis 30 g/1 insbesondere bevorzugt 10 g/l bis 15 g/1 aromatische Aldehyde und/oder aromatische Ketone o g/l bis 0,5 g/1 insbesondere bevorzugt o g/l bis 0,2 g/1 aromatische und/oder heterocyclische Carbonsäuren oder deren Alkalisalze 0,5 g/1 bis 10 g/1 insbesondere bevorzugt i g/i bis 3 g/1 Leitsalze 10 g/1 bis 150 g/1 insbesondere bevorzugt 30 g/1 bis 70 g/1- According to formula (IV) or (V) og / i to 10 g / 1, particularly preferably og / l to 2 g / 1, anionic surfactants 5 g / l to 30 g / 1, particularly preferably 10 g / l to 15 g / 1 aromatic aldehydes and / or aromatic ketones og / l to 0.5 g / 1 particularly preferably og / l to 0.2 g / 1 aromatic and / or heterocyclic carboxylic acids or their alkali metal salts 0.5 g / 1 to 10 g / 1 in particular preferably ig / i to 3 g / 1 conductive salts 10 g / 1 to 150 g / 1, particularly preferably 30 g / 1 to 70 g / 1
Die vorliegende Erfindung umfaßt auch die Verwendung der oben beschriebenen wäßrigen Lösung zur Abscheidung von Zinn- Zinküberzügen, insbesondere von Zinn-Zinküberzügen mit einem Zinkgehalt von 10 bis 50 Gew.-%.The present invention also includes the use of the aqueous solution described above for the deposition of tin Zinc coatings, in particular tin-zinc coatings with a zinc content of 10 to 50% by weight.
Die Erfindung wird anhand des nachfolgenden Ausführungsbeispiels näher erläutert.The invention is explained in more detail using the following exemplary embodiment.
Es wurde .eine wäßrige Lösung aus den folgenden Komponenten hergestellt :An aqueous solution was prepared from the following components:
Zitronensäure 100 g/1Citric acid 100 g / 1
NH4C1 50 g/1NH 4 C1 50 g / 1
NH40H, 25% 90 g/1NH 4 0H, 25% 90 g / 1
H3B03 30 g/1H 3 B0 3 30 g / 1
Sn2+ als Sn (CH3S03 ) 2 3 ST 1 Sn 2 + as Sn (CH 3 S0 3 ) 2 3 ST 1
ZnCl2 33 g/1ZnCl 2 33 g / 1
C12H25 -0-(C2H4O)n-C3H6SO3K 5 g/1 C 12 H 2 5 -0- (C 2 H 4 O) n C 3 H 6 SO 3 K 5 g / 1
Nonyl — QV-0— (C2H4θ)14H 2 g/1 Na-Benzoat 2 g/1Nonyl - QV- 0 - (C 2 H 4 θ) 14 H 2 g / 1 Na benzoate 2 g / 1
Nikotinsäure 0.1 g/1 o-Cl-Benzaldehyd 0.05 g/1Nicotinic acid 0.1 g / 1 o-Cl-benzaldehyde 0.05 g / 1
Mit dieser Lösung wurde unter den folgenden Bedingungen eine Zinn-Zink-Legierung mit 30 % Zink auf einerThis solution was used to make a tin-zinc alloy with 30% zinc on one under the following conditions
Substratoberfläche mit einer Dicke von 10 μm und mit einer hellgrauen Farbe abgeschieden.Substrate surface with a thickness of 10 microns and deposited with a light gray color.
1 = 1 A/dm2 t = 20 min T = 40 °C1 = 1 A / dm 2 t = 20 min T = 40 ° C
Das obige Ergebnis zeigt, daß mit der erfindungsgemäßen wäßrigen Lösung Zinn-Zink-Legierungen einheitlicher Dicke und Zusammensetzung mit gleichmäßiger heller Farbe ohne die Verwendung von Cyanidionen bei geringem Energieverbrauch abgeschieden werden können. The above result shows that the aqueous solution according to the invention can be used to deposit tin-zinc alloys of uniform thickness and composition with a uniform light color without the use of cyanide ions with low energy consumption.

Claims

Patentansprücheclaims
1. Wäßrige Lösung zur elektrolytischen Abscheidung von Zinn- Zink-Legierungen, die folgende Bestandteile umfaßt1:1. Aqueous solution for the electrolytic deposition of tin-zinc alloys, which comprises the following components 1 :
a) Zn (II) -Ionen; b) Sn (II) -Ionen; c) aliphatische Carbonsäuren und/oder deren Alkalisalze; d) anionische Tenside; e) nichtionogene Tenside.a) Zn (II) ions; b) Sn (II) ions; c) aliphatic carboxylic acids and / or their alkali salts; d) anionic surfactants; e) nonionic surfactants.
2. Lösung nach Anspruch 1, wobei zusätzlich auch aromatische Aldehyde und/oder aromatische Ketone umfaßt sind.2. Solution according to claim 1, wherein aromatic aldehydes and / or aromatic ketones are additionally included.
3. Lösung nach Anspruch 2, wobei die aromatischen Aldehyde und/oder aromatischen Ketone die Formel (I)3. Solution according to claim 2, wherein the aromatic aldehydes and / or aromatic ketones have the formula (I)
AR-R-CO-R' (I)AR-R-CO-R '(I)
besitzen, wobei AR = Phenyl, Naphtyl ; R = CH2, CH = CH und R' = H, Cτ__3 -Alkyl sein kann.have, where AR = phenyl, naphthyl; R = CH 2 , CH = CH and R '= H, Cτ__ 3 alkyl.
4. Lösung nach Anspruch 2, dadurch gekennzeichnet, daß die aromatischen Aldehyde die Formel (II)4. Solution according to claim 2, characterized in that the aromatic aldehydes have the formula (II)
mit X = H, CH3, OCH , Cl, Br aufweisen. with X = H, CH 3 , OCH, Cl, Br.
5. Lösung nach einem der Ansprüche 1 bis 4, wobei die Lösung einen pH-Wert von 2 - 8, insbesondere von 3 - 5, aufweist .5. Solution according to one of claims 1 to 4, wherein the solution has a pH of 2-8, in particular 3-5.
6. Lösung nach einem der Ansprüche 1 bis 5, wobei die Sn(II)- und Zn (II) -Ionen als Chloride, Sulfate oder Alkylsulfonate und gegebenenfalls zusätzlich Leitsalze entsprechender Anionen enthalten sind.6. Solution according to one of claims 1 to 5, wherein the Sn (II) - and Zn (II) ions are present as chlorides, sulfates or alkyl sulfonates and optionally additional conductive salts of corresponding anions.
7. Lösung nach einem der Ansprüche 1 bis 6, wobei die aliphatischen Carbonsäuren Hydroxycarbonsäuren und/oder A inocarbonsäuren oder deren Alkalisalze sind.7. Solution according to one of claims 1 to 6, wherein the aliphatic carboxylic acids are hydroxycarboxylic acids and / or A inocarboxylic acids or their alkali metal salts.
8. Lösung nach Anspruch 7, wobei die Carbonsäuren Zitronensäure oder deren Alkalisalze sind.8. Solution according to claim 7, wherein the carboxylic acids are citric acid or its alkali salts.
9. Lösung nach einem der Ansprüche 1 bis 8, wobei die nichtionogenen Tenside die Formel (III)9. Solution according to one of claims 1 to 8, wherein the nonionic surfactants have the formula (III)
R-O- (C2H40)nH (III)RO- (C 2 H 4 0) n H (III)
aufweisen, wobei R einen Alkyl-, Aryl-, Alkyl-arylrest darstellt und n = 1 - 100 ist.have, wherein R represents an alkyl, aryl, alkyl-aryl radical and n = 1 - 100.
10. Lösung nach Anspruch 9, wobei zusätzlich nichtionogene Tenside der Formel (IV)10. Solution according to claim 9, wherein additionally nonionic surfactants of the formula (IV)
R'-S- (C2H40)nH (IV)R'-S- (C 2 H 4 0) n H (IV)
und/oder der Formel (V)and / or the formula (V)
R"N[(C2H40)nH]2 (V)R "N [(C 2 H 4 0) n H] 2 (V)
enthalten sind, wobei R' = C1_3-Alkyl oder -(C2H40)nH;are contained, wherein R '= C 1 _ 3 alkyl or - (C 2 H 4 0) n H;
R" = c5-20_Alky1 und n = 1-100 ist. Lösung nach einem der Ansprüche 1 bis 10, wobei die anionischen Tenside eine oder mehrere der Verbindungen mit den Formeln (VI) bis (IX) beinhalten: R "= c 5-20 _Alk y 1 and n = 1-100. Solution according to one of claims 1 to 10, wherein the anionic surfactants contain one or more of the compounds of the formulas (VI) to (IX):
a')R-<ö>- 0-(C2H4θ)n-SO3M (VI> a ' ) R- < ö> - 0- (C 2 H4θ) n -SO 3 M (VI >
mit R = C3_12-Alkyl; X = H, -S03M; M = Na, K, NH4 with R = C 3 _ 12 alkyl; X = H, -S0 3 M; M = Na, K, NH 4
b1) R'-O- (C2H4θ)n-R'iSθ3M (VII) b 1 ) R'-O- (C2H4θ) n-R'iSθ 3 M ( VII )
mit R« = C3_12-Alkyl; R" = C2_5-Alkyl; M = Na, K, NH4 with R "= C 3 _ 12 alkyl; R "= C 2 _ 5 alkyl; M = Na, K, NH 4
mit R"' = H, Ci-^-Alkyl, 0- (C2H40) n-X; oderwith R "'= H, Ci - ^ - alkyl, 0- (C 2 H 4 0) n -X; or
und X = S03M mit M = Na, K, NH and X = S0 3 M with M = Na, K, NH
mit R'" 0- (C2H40) n-X; oder und X = S03M mit M = Na, K, NH4 mit n = 0 - 100, vorzugsweise 6 - 15.with R '" 0- (C 2 H 4 0) n -X; or and X = S0 3 M with M = Na, K, NH 4 with n = 0-100, preferably 6-15.
12. Lösung nach einem der Ansprüche 1 bis 11, wobei zusätzlich aromatische und/oder heterocyclische Carbonsäuren oder deren Alkalisalze enthalten sind.12. Solution according to one of claims 1 to 11, wherein aromatic and / or heterocyclic carboxylic acids or their alkali metal salts are additionally contained.
13. Lösung nach Anspruch 12, wobei die Carbonsäuren die Formel (XIV)13. Solution according to claim 12, wherein the carboxylic acids have the formula (XIV)
R-COOM, (χιv) R-COOM, (χιv)
ώR= O'IQJ' 0> JUJund M= H, Na,K,NH4ώR = O'IQJ ' 0> JUJ and M = H, Na, K, NH4
aufweisen.exhibit.
14. Verwendung einer wäßrigen Lösung nach einem der Ansprüche 1 bis 13 zur Abscheidung von Zinn- Zinküberzügen.14. Use of an aqueous solution according to one of claims 1 to 13 for the deposition of tin-zinc coatings.
15. Verwendung einer wäßrigen Lösung nach Anspruch 14 zur Abscheidung von Zinn-Zinküberzügen mit einem Zinkanteil von 10 bis 50 Gew.-%. 15. Use of an aqueous solution according to claim 14 for the deposition of tin-zinc coatings with a zinc content of 10 to 50 wt .-%.
EP99960973A 1998-11-12 1999-11-12 Aqueous solution for electrodepositing tin-zinc alloys Expired - Lifetime EP1137825B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19852219 1998-11-12
DE19852219A DE19852219C1 (en) 1998-11-12 1998-11-12 Aqueous solution for the electrolytic deposition of tin-zinc alloys and use of the solution
PCT/EP1999/008724 WO2000029645A2 (en) 1998-11-12 1999-11-12 Aqueous solution for electrodepositing tin-zinc alloys

Publications (2)

Publication Number Publication Date
EP1137825A2 true EP1137825A2 (en) 2001-10-04
EP1137825B1 EP1137825B1 (en) 2002-09-11

Family

ID=7887579

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99960973A Expired - Lifetime EP1137825B1 (en) 1998-11-12 1999-11-12 Aqueous solution for electrodepositing tin-zinc alloys

Country Status (11)

Country Link
US (1) US6770185B2 (en)
EP (1) EP1137825B1 (en)
JP (1) JP4355987B2 (en)
KR (1) KR20010086017A (en)
CN (1) CN1195904C (en)
AT (1) ATE223979T1 (en)
AU (1) AU1775200A (en)
CZ (1) CZ296310B6 (en)
DE (2) DE19852219C1 (en)
PL (1) PL194304B1 (en)
WO (1) WO2000029645A2 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE50106133D1 (en) * 2000-09-20 2005-06-09 Schloetter Fa Dr Ing Max ELECTROLYTE AND METHOD OF DEPOSITING TIN COPPER ALLOY LAYERS
US8784629B2 (en) * 2007-09-27 2014-07-22 Chemetall Gmbh Method of producing surface-treated metal material and method of producing coated metal item
CN102443827A (en) * 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 Sn-Zn alloy electroplating solution
CN102634827B (en) * 2012-05-07 2015-04-08 东莞市闻誉实业有限公司 Tin-zinc alloy electroplating method
CN106498453B (en) * 2016-09-14 2018-08-28 湖北大学 A kind of tin plating, tin alloy brightener and its preparation method and application
KR20220132528A (en) * 2020-01-27 2022-09-30 미쓰비시 마테리알 가부시키가이샤 A tin or tin alloy electrolytic plating solution, a method for forming a bump, and a method for manufacturing a circuit board

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE415577B (en) * 1977-09-15 1980-10-13 Magnusson H H Produkter SET AND ELECTROLYTE TO FABRICATE A STALYTE FOR PAINTING
GB2013241B (en) * 1977-11-16 1982-03-24 Dipsol Chem Electroplating bath for depositing tin or tin alloy with brightness
JP3135915B2 (en) * 1990-08-31 2001-02-19 バリー，ベレズフォド トマス キングカム Cyanide-free plating bath for electrodeposition of tin-zinc alloys
DE4034304A1 (en) * 1990-10-29 1992-04-30 Henkel Kgaa ELECTROLYTE ADDITIVES FOR A COLORING BATHROOM FOR ALUMINUM COLORING AND METHOD FOR COLORING ALUMINUM
GB2266894A (en) * 1992-05-15 1993-11-17 Zinex Corp Modified tin brightener for tin-zinc alloy electroplating bath
JP3279353B2 (en) * 1992-09-25 2002-04-30 ディップソール株式会社 Tin-zinc alloy electroplating bath
DE4446329A1 (en) * 1994-12-23 1996-06-27 Basf Ag Salts of aromatic hydroxyl compounds and their use as brighteners
JP3609565B2 (en) * 1996-12-09 2005-01-12 株式会社大和化成研究所 Tin-zinc alloy plating bath
JP3816241B2 (en) * 1998-07-14 2006-08-30 株式会社大和化成研究所 Aqueous solution for reducing and precipitating metals

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0029645A2 *

Also Published As

Publication number Publication date
JP4355987B2 (en) 2009-11-04
CN1195904C (en) 2005-04-06
DE19852219C1 (en) 2000-05-11
JP2002530528A (en) 2002-09-17
US20020046954A1 (en) 2002-04-25
US6770185B2 (en) 2004-08-03
ATE223979T1 (en) 2002-09-15
AU1775200A (en) 2000-06-05
DE59902696D1 (en) 2002-10-17
KR20010086017A (en) 2001-09-07
WO2000029645A2 (en) 2000-05-25
CZ20011633A3 (en) 2001-12-12
WO2000029645A3 (en) 2000-09-14
CZ296310B6 (en) 2006-02-15
EP1137825B1 (en) 2002-09-11
PL194304B1 (en) 2007-05-31
PL348755A1 (en) 2002-06-03
CN1321205A (en) 2001-11-07

Similar Documents

Publication Publication Date Title
DE69808415T2 (en) ELECTROPLATING NICKEL PHOSPHORUS ALLOY COATINGS
DE69808497T2 (en) CYANIDE-FREE, MONOVALENT COPPER ELECTRIC COATING SOLUTION
EP1325175B1 (en) Electrolyte and method for depositing tin-copper alloy layers
EP2089561B1 (en) Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates
DE1062079B (en) Cyanide bath and process for the galvanic deposition of copper coatings
EP1408141B1 (en) Process and electrolyte for the galvanic deposition of bronze
EP1285104B1 (en) Electrolyte and method for depositing tin-silver alloy layers
DE4023444C2 (en) A method of electrodepositing copper from an aqueous, alkaline, cyanide-free bath using both a soluble and an insoluble anode
DE3447813A1 (en) AQUEOUS ACID BATH AND A METHOD FOR GALVANIC DEPOSITION OF ZINC OR ZINC ALLOYS
DE1496917A1 (en) Electrolytic baths and processes for the production of galvanic coatings
WO2000079030A1 (en) Bath system for galvanic deposition of metals
DE3628361C2 (en)
DE19852219C1 (en) Aqueous solution for the electrolytic deposition of tin-zinc alloys and use of the solution
EP1295967A2 (en) Process for depositing a zinc-nickel alloy from an electrolyte
DE2830441A1 (en) AQUATIC BATH FOR GALVANIC DEPOSITION OF ZINC AND ITS USE
DE2114119A1 (en) Process for the electrolytic deposition of ruthenium and electrolysis bath to carry out this process
DE10006128B4 (en) Plating bath for depositing an Sn-Bi alloy and its use
DE3013191A1 (en) IN THE ESSENTIAL CYANIDE-FREE BATH FOR THE ELECTROLYTIC DEPOSITION OF SILVER OR SILVER ALLOY
CH636909A5 (en) METHOD FOR THE GALVANIC DEPOSITION OF AN IRON AND NICKEL AND / OR COBALT CONTAINING RAIN AND A SUITABLE BATH FOR THIS.
DE68905429T2 (en) METHOD FOR TIN ELECTROPLATING METALLIC MATERIAL.
CH640888A5 (en) METHOD FOR THE GALVANIC DEPOSITION OF AN IRON AND NICKEL AND / OR COBALT CONTAINING RAIN AND A SUITABLE BATH FOR THIS.
DE3889667T2 (en) ELECTRIC DEPOSITION OF TIN-BISMUT ALLOYS.
EP1442160A2 (en) Electrolysis bath for electrodepositing silver-tin alloys
DE102020133188B4 (en) Use of a silver-bismuth electrolyte for the deposition of hard silver layers
DE2450133A1 (en) PROCESS AND GALVANIC BATH FOR DEPOSITING NICKEL / IRON AND NICKEL / COBALT / IRON ALLOYS

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

17P Request for examination filed

Effective date: 20010507

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20011113

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020911

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020911

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020911

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020911

REF Corresponds to:

Ref document number: 223979

Country of ref document: AT

Date of ref document: 20020915

Kind code of ref document: T

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

XX Miscellaneous (additional remarks)

Free format text: DERZEIT SIND DIE WIPO-PUBLIKATIONSDATEN A3 NICHT VERFUEGBAR.

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20020911

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 59902696

Country of ref document: DE

Date of ref document: 20021017

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: 20021112

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021112

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20021130

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20021211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20021218

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030328

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

Ref document number: 1137825E

Country of ref document: IE

BERE Be: lapsed

Owner name: MAX *SCHLOTTER G.M.B.H. & CO. K.G.

Effective date: 20021130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030601

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

Effective date: 20030612

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20061130

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20081112

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071112

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20091030

Year of fee payment: 11

Ref country code: FR

Payment date: 20091103

Year of fee payment: 11

EUG Se: european patent has lapsed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091113

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20101112

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110801

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: 20101130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101112

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20181126

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59902696

Country of ref document: DE