EP0526497A1 - Acid nickel baths containing 1-(2-sulfoethyl)-pyridinium betaine. - Google Patents

Acid nickel baths containing 1-(2-sulfoethyl)-pyridinium betaine.

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Publication number
EP0526497A1
EP0526497A1 EP91907848A EP91907848A EP0526497A1 EP 0526497 A1 EP0526497 A1 EP 0526497A1 EP 91907848 A EP91907848 A EP 91907848A EP 91907848 A EP91907848 A EP 91907848A EP 0526497 A1 EP0526497 A1 EP 0526497A1
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EP
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Prior art keywords
nickel baths
concentrations
acidic nickel
baths according
sulfoethyl
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EP91907848A
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German (de)
French (fr)
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EP0526497B1 (en
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Wolfgang Dahms
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Atotech Deutschland GmbH and Co KG
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Schering AG
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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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18—Heterocyclic compounds

Definitions

  • the invention relates to acidic nickel baths containing l- (2-sulfoethyl) pyridinium betaine.
  • Acidic nickel baths are known, for example from the documents US Pat. No. 3,862,019, DE-PS 36 32 514, EP-A-0343 559, DD-PS 0266 814 and EP-A 0341 167.
  • a group of the additives also called basic gloss, are unsaturated, mostly aromatic sulfonic acids, sulfinic acids, sulfonamides, or their salts.
  • the best known compounds are, for example, m-benzene disulfonic acid or benzoic acid sulfimide (saccharin).
  • leveling agents substances which are referred to as leveling agents. They are practically always used together with one or more basic glosses.
  • levelers are, for example, triple unsaturated alcohols or triple unsaturated amines. They show above all during continuous operation and even with a slight overdose, dark deposits in the low current density range. It is often the case that no deposition occurs in the low current density range and the background material remains visible.
  • levelers quaternary aromatic nitrogen-containing compounds such as pyridinium or quinolinium compounds are known as levelers. All these leveling agents have in common that they embrittle the nickel deposit either at the beginning, but mostly in continuous operation. Subsequent deformation of the nickel-plated parts is no longer possible, and cracks also spontaneously occur that extend into the base material and cause corrosion (for example, rust).
  • the object of the present invention is to avoid the disadvantages described and to provide a bath which, with a sufficiently good depth spread, prevents a good leveling and, in the case of prolonged operation of the acidic nickel baths, prevents the deposition of brittle precipitates, with the lowest consumption of bath constituents.
  • 1- (2-Sulfoethyl) pyridinium betaine is a known substance (U.S. Patent 3,131,189, J. Org. Chem., 29, 2489 (1964), J. Org. Chem., 26, 4520 (1961) and differs of l- (3-sulfopropyl) pyridinium betaine (DE-PS 1004011) through a better effectiveness in the approach and consumption.
  • the bath for the deposition of nickel deposits with the addition of the substance according to the invention generally consists of a nickel salt solution, to which a weak acid is additionally added for buffering.
  • the pH is between 3 and 5.5; mainly between 4 and 5.
  • the temperature can be up to 75 ° C to increase the current density, usually it is between 50 ° and 60 ° C.
  • High-performance electrolytes have a chloride content of 10-50 g / 1 and show the best results when using the compounds according to the invention. Some or all of the nickel chloride can be replaced by sodium chloride.
  • the current density can be up to 10 A / dm 2 at 55 ° C for the designated high-performance electrolytes.
  • the substance according to the invention can be added to the electrolyte on its own, but optimum results can only be achieved by combining it with known base glossers and leveling agents (Tables 1 and 2). In this way, an excellent leveling can be achieved over the entire current density range required in practice, without the precipitation becoming brittle in continuous operation.
  • the concentration of the compounds according to the invention in nickel electrolytes is very low and can be between 0.005 and 5 g / 1, generally between 0.05 and 0.4 g / 1.
  • the concentration is particularly in the lower range when the - h - Compounds according to the invention can be used in combination of base glosses together with triple unsaturated compounds.
  • the basic glosses according to Table 1 are generally added to the electrolyte in amounts of 0.1-10 g / l.
  • Levelers according to Table 2 are expediently metered in between 0.005 and 0.25 g / l.
  • Wetting agents to prevent porous deposition can be added in amounts of up to 10 g / l.
  • levelers that can be added to the bath.
  • Example 1.0 In addition to the compound according to the invention, 1 g / 1 saccharin, sodium salt is added to the electrolyte according to Example 1.0.
  • the sheet shows a high-gloss and well-leveled deposition in the current density range of 2-8 A / dm 2 .
  • Example 2.0 If in Example 2.0 the N, N-diethylaminopropin is replaced by 0.07 g / 1 2-butynediol (1.4), a highly glossy and very good leveled separation is obtained in the range from 0.3 to 8 A / dm 2 .
  • Example 2.0 If, in Example 2.0, the N, N-diethylaminopropin is replaced by 0.03 g / 1 ethylene glycol monopropargyl ether, a high-gloss and very well-leveled deposit is obtained in the range from 0.2 to 8.2 A / dm 2 .
  • N-diethylaminopropin is replaced by 0.007 g / l of propargyl alcohol, the result is in the range from 0.3 to
  • Example 2 If in Example 2, .0 the N, N-diethylaminopropin is replaced by 0.15 g / 1 hydroxypropinsulfonic acid, sodium salt, a high-gloss and very well-leveled deposit is obtained in the range from 0.1 to 8 A / dm 2 .
  • Example 2.0 If in Example 2.0 the N, N-diethylaminopropin is replaced by 0.05 g / 1 propynesulfonic acid, sodium salt, the result is - a - range from 0.2 to 9 A / dm 2 a high-gloss and well-leveled deposition.
  • a consumption of 60 g is determined based on a charge passage of 1000 Ah.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Pyridine Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemically Coating (AREA)

Abstract

PCT No. PCT/DE91/00336 Sec. 371 Date Nov. 19, 1992 Sec. 102(e) Date Nov. 19, 1992 PCT Filed Apr. 22, 1991 PCT Pub. No. WO91/16474 PCT Pub. Date Oct. 31, 1991.The invention concerns acid nickel baths containing 1-(2-sulfoethyl)-pyridinium betaine

Description

SAURE NICKELBÄDER, ENTHALTEND l-(2-Sulfoethyl)-pyridiniumbetain ACID NICKEL BATHS, CONTAINING l- (2-sulfoethyl) pyridinium betaine
Die Erfindung betrifft saure Nickelbäder, enthaltend l-(2- sulfoethyl)-pyridiniumbetain.The invention relates to acidic nickel baths containing l- (2-sulfoethyl) pyridinium betaine.
Saure Nickelbäder sind bekannt, beispielsweise aus den Schriften US-PS 3,862,019, DE-PS 36 32 514, EP-A- 0343 559, DD-PS 0266 814 und EP-A 0341 167.Acidic nickel baths are known, for example from the documents US Pat. No. 3,862,019, DE-PS 36 32 514, EP-A-0343 559, DD-PS 0266 814 and EP-A 0341 167.
Es ist ebenfalls bekannt, daß sauren, insbesondere schwach sauren Nickelelektrolyten, bestimmte organische Substanzen in geringen Mengen zugesetzt werden, um statt einer matten Abscheidung eine glänzende Nickelabscheidung zu erhalten.It is also known that acidic, in particular weakly acidic nickel electrolytes, certain organic substances are added in small amounts in order to obtain a shiny nickel deposit instead of a matt deposit.
Eine Gruppe der Zusätze, auch Grundglänzer genannt, sind ungesättigte, meist aromatische Sulfonsäuren, Sulfinsäuren, S lfonamide, beziehungsweise deren Salze. Die bekanntesten Verbindungen sind zum Beispiel m-Benzoldistflfonsäure oder Benzoesäuresulfimid (Saccharin).A group of the additives, also called basic gloss, are unsaturated, mostly aromatic sulfonic acids, sulfinic acids, sulfonamides, or their salts. The best known compounds are, for example, m-benzene disulfonic acid or benzoic acid sulfimide (saccharin).
Diese Zusätze (Grundglanzbildner) erzeugen, allein dem galvanischen Bad zugesetzt, über einen gewissen Stromdichtebereich einen glänzenden, aber nicht eingeebneten Niederschlag. Ihre alleinige Anwendung hat deshalb keinerlei praktische Bedeutung, da die Qualität der mit ihnen erhaltenen Nickelüberzüge nicht den heutigen Anforderungen entspricht.These additives (basic brighteners), added to the galvanic bath alone, produce a shiny but not leveled precipitate over a certain current density range. Their sole use is therefore of no practical importance, since the quality of the nickel coatings obtained with them does not meet today's requirements.
Ihr offensichtlicher Mangel ist die Fähigkeit, rauhe Oberflächen einzuebnen, ohne den Niederschlag zu verspröden.Their obvious shortcoming is the ability to level rough surfaces without embrittling the precipitate.
Es sind auch hier Substanzen bekannt, die als Einebner bezeichnet werden. Sie werden praktisch immer zusammen mit einem oder mehreren Grundglänzern angewendet.Here, too, substances are known which are referred to as leveling agents. They are practically always used together with one or more basic glosses.
Bekannte Einebner sind zum Beispiel dreifach ungesättigte Alkohole oder dreifach ungesättigte Amine. Sie zeigen vor allem beim Dauerbetrieb und schon bei leichter Überdosierung dunkle Abscheidungen im niedrigen Stromdichtebereich. Häufig tritt sogar der Fall ein, daß keine Abscheidung im niedrigen Stromdichtebereich auftritt und das Untergrundmaterial sichtbar bleibt.Known levelers are, for example, triple unsaturated alcohols or triple unsaturated amines. They show above all during continuous operation and even with a slight overdose, dark deposits in the low current density range. It is often the case that no deposition occurs in the low current density range and the background material remains visible.
Weiter sind als Einebner quΦternäre, aromatische stickstoffhaltige Verbindungen wie Pyridinium- oder Chinoliniumverbindungen als Einebner bekannt. Allen diesen Einebnern ist gemeinsam, daß sie entweder schon beim Ansatz , meist aber im Dauerbetrieb den Nickelniederschlag verspröden. Dadurch ist ein nachträgliches Verformen der vernickelten Teile nicht mehr möglich, es entstehen auch spontan Risse, die bis in das Grundmaterial reichen und dadurch Korrosion (zum Beispiel Rost) hervorrrufen.In addition, quaternary aromatic nitrogen-containing compounds such as pyridinium or quinolinium compounds are known as levelers. All these leveling agents have in common that they embrittle the nickel deposit either at the beginning, but mostly in continuous operation. Subsequent deformation of the nickel-plated parts is no longer possible, and cracks also spontaneously occur that extend into the base material and cause corrosion (for example, rust).
Aufgabe der vorliegenden Erfindung ist es, diese beschriebenen Nachteile zu vermeiden und ein Bad bereitzustellen, das bei ausreichend guter Tiefenstreuung eine gute Einebnung und bei längerem Betrieb der sauren Nickelbäder die Abscheidung spröder Niederschläge verhindert, bei geringstem Verbrauch an Badinhaltsstoffen.The object of the present invention is to avoid the disadvantages described and to provide a bath which, with a sufficiently good depth spread, prevents a good leveling and, in the case of prolonged operation of the acidic nickel baths, prevents the deposition of brittle precipitates, with the lowest consumption of bath constituents.
Diese Aufgabe wird durch den Erfindungsgegenstand gemäß den Patentansprüchen gelöst.This object is achieved by the subject matter of the invention according to the patent claims.
Es zeigte sich, daß der Zusatz von l-(2-Sulfoethyl)- pyridiniumbetain als NickelglanzbildnerIt was shown that the addition of 1- (2-sulfoethyl) pyridinium betaine as a nickel shine
sich besonders gut eignet. l-(2-Sulfoethyl)-pyridiniumbetain ist eine bekannte Substanz (US-PS 3 131,189, J. Org.Chem. ,29, 2489 (1964), J.Org. Chem.,26, 4520 (1961) und unterscheidet sich von l-(3-Sulfopropyl)-pyridiniumbetain (DE- PS 1004011) durch eine bessere Wirksamkeit im Ansatz und Verbrauch. works particularly well. 1- (2-Sulfoethyl) pyridinium betaine is a known substance (U.S. Patent 3,131,189, J. Org. Chem., 29, 2489 (1964), J. Org. Chem., 26, 4520 (1961) and differs of l- (3-sulfopropyl) pyridinium betaine (DE-PS 1004011) through a better effectiveness in the approach and consumption.
Mit dieser Verbindung gelingt es in hervorragender Weise, eine sehr gute Einebnung in Verbindung mit einem hervorragenden Glanz zu erzielen. Eine Versprödung tritt nicht auf. Durch Kombination mit den Einebnern aus Tabelle 2 mit einer dreifach ungesättigten Gruppe kann der Glanzbereich bis in den niedrigsten Stromdichtebereich erzielt werden.With this connection, it succeeds in an excellent way, a very good leveling in connection with an excellent gloss to achieve. Embrittlement does not occur. By combining with the levelers from Table 2 with a triple unsaturated group, the gloss range can be achieved down to the lowest current density range.
Das Bad zur Abscheidung von Nickelniederschlägen unter Zusatz der erfindungsgemäßen Substanz besteht im allgemeinen aus einer Nickelsalzlösung, der man zusätzlich eine schwache Säure zur Pufferung zusetzt.The bath for the deposition of nickel deposits with the addition of the substance according to the invention generally consists of a nickel salt solution, to which a weak acid is additionally added for buffering.
In der Praxis wird hauptsächlich der Watts'sehe Ansatz verwendet, der etwa folgende Zusammensetzung hat:In practice, the Watts's approach is mainly used, which has the following composition:
200 - 400 g/1 Nickelsulfat (NiS04 . 7H20) 30 - 200 g/1 Nickelchlorid (NiCl2 • 6H20) 30 - 50 g/1 Borsäure (H3BO3)200 - 400 g / 1 nickel sulfate (NiS0 4. 7H 2 0) 30 - 200 g / 1 nickel chloride (NiCl 2 • 6H 2 0) 30 - 50 g / 1 boric acid (H 3 BO 3 )
Der pH-Wert liegt zwischen 3 und 5, 5; hauptsächlich zwischen 4 und 5. Die Temperatur kann zur Erhöhung der Stromdichten bis zu 75°C betragen, in der Regel liegt sie zwischen 50° und 60°C.The pH is between 3 and 5.5; mainly between 4 and 5. The temperature can be up to 75 ° C to increase the current density, usually it is between 50 ° and 60 ° C.
Hochleistungselektrolyte haben einen Chloridgehalt von 10 - 50 g/1 und zeigen beim Verwenden der erfindungsgemäßen Verbindungen die besten Ergebnisse. Das Nickelchlorid kann teilweise oder ganz durch Natriumchlorid ersetzt werden. Die Sromdichte kann bei 55°C bei den bezeichneten Hochleistungselektrolyten bis zu 10 A/dm2 betragen.High-performance electrolytes have a chloride content of 10-50 g / 1 and show the best results when using the compounds according to the invention. Some or all of the nickel chloride can be replaced by sodium chloride. The current density can be up to 10 A / dm 2 at 55 ° C for the designated high-performance electrolytes.
Die erfindungsgemäße Substanz kann zwar für sich allein dem Elektrolyten zugesetzt werden, optimale Ergebnisse erzielt man jedoch erst durch Kombination mit bekannten Grundglänzern und Einebnern (Tabelle 1 und 2). Man kann so über den gesamten für die Praxis erforderlichen Stromdichtebereich eine ausgezeichnete Einebnung erzielen, ohne daß die Niederschläge im Dauerbetrieb verspröden.The substance according to the invention can be added to the electrolyte on its own, but optimum results can only be achieved by combining it with known base glossers and leveling agents (Tables 1 and 2). In this way, an excellent leveling can be achieved over the entire current density range required in practice, without the precipitation becoming brittle in continuous operation.
Die Konzentration der erfindungsgemäßen Verbindungen in Nickelelektrolyten ist sehr gering und kann zwischen 0,005 und 5 g/1, in der Regel zwischen 0,05 und 0,4 g/1 liegen. Die Konzentration liegt besonders im unteren Bereich, wenn die - h - erfindungsgemäßen Verbindungen in Kombination von Grundglänzern zusammen mit dreifach ungesättigten Verbindungen angewendet werden.The concentration of the compounds according to the invention in nickel electrolytes is very low and can be between 0.005 and 5 g / 1, generally between 0.05 and 0.4 g / 1. The concentration is particularly in the lower range when the - h - Compounds according to the invention can be used in combination of base glosses together with triple unsaturated compounds.
Die Grundglänzer nach Tabelle 1 werden in der Regel in Mengen von 0,1 - 10 g/1, dem Elektrolyten zugesetzt. Einebner nach Tabelle 2 werden zweckmäßigerweise zwischen 0,005 und 0,25 g/1 dosiert. Netzmittel zur Verhinderung einer porigen Abscheidung können in Mengen bis zu 10 g/1 zugesetzt werden.The basic glosses according to Table 1 are generally added to the electrolyte in amounts of 0.1-10 g / l. Levelers according to Table 2 are expediently metered in between 0.005 and 0.25 g / l. Wetting agents to prevent porous deposition can be added in amounts of up to 10 g / l.
_ T___a__b___e__l__l___e___1____ Table 1___
Beispiele für Grundglänzer (die zumeist in Form ihrer Natrium¬ oder Kaliumsalze eingesetzt werden) , die dem Bad zugesetzt werden können.Examples of basic glosses (which are mostly used in the form of their sodium or potassium salts) which can be added to the bath.
Benzolsulfinsäure m-BenzoldisulfonsäureBenzenesulfinic acid m-benzenedisulfonic acid
PhenylpropinsulfonsäurePhenylpropinsulfonic acid
VinylsulfonsäureVinyl sulfonic acid
AllylsulfonsäureAllylsulfonic acid
Propinsulfonsäure p-Toluolsulfonsäure p-Toluolsulfinsäure p-ToluolsulfonamidPropinsulfonic acid p-toluenesulfonic acid p-toluenesulfinic acid p-toluenesulfonamide
Benzoesäuresulfi idBenzoic acid sulfi id
1,3,6-Naphthalintrisulfonsäure1,3,6-naphthalene trisulfonic acid
N-BeiöflylbenzolsulfonamidN-Beioflylbenzenesulfonamide
SulfonessigsäurebutindiolesterSulfonic acetic acid butynediol ester
Tabelle 2Table 2
Beispiele für Einebner, die den Bad zugesetzt werden können.Examples of levelers that can be added to the bath.
Propargylalkohol 2-Butindiol-(l,4) Äthylenglycolmonopropargyläther Äthylenglycol - bis - propargyläther Diäthylenglycol - monopropargyläther N,N,-Dimethylaminopropin N , N-Diäthylaminopropin 2-Butindiol-bis-(hydroxyäthyläther) 2-Butindiol-mono(hydroxy-isopropyläther) 2 , 5-Hexindiol 2 - ( 3 -Propin- ( 1 ) -oxy ) -propanol Propargyl alcohol 2-butynediol- (1,4) Ethylene glycol monopropargyl ether Ethylene glycol - bis - propargyl ether Diethylene glycol - monopropargyl ether N, N, -Dimethylaminopropin N, N-diethylaminopropin 2-butynediol-bis (hydroxyethyl ether) 2-butynediol-mono (hydroxy-isopropyl ether) 2,5-hexynediol 2 - (3-propyne (1) -oxy) -propanol
Die folgenden Beispiele sollen die Erfindung näher erläutern:The following examples are intended to illustrate the invention:
Beispiel 1,0Example 1.0
Zu einem Elektrolyten mit folgender Zusammensetzung 270 g/1 Nickelsulfat (NiS04 . 7H20)To an electrolyte with the following composition 270 g / 1 nickel sulfate (NiS0 4. 7H 2 0)
40 g/1 Nickelchlorid(NiCl2 . 6H2o)40 g / 1 nickel chloride (NiCl 2. 6H 2 o)
40 g /lBorsäure (H3BO3) 0,5 g/1 2-Äthylhexylsulfat, Natriumsalz als Netzmittel werden 0,25 g/1 der erfindungsgemäßen Verbindung zugesetzt.40 g / l boric acid (H 3 BO 3 ) 0.5 g / 1 2-ethylhexyl sulfate, sodium salt as wetting agent, 0.25 g / 1 of the compound according to the invention are added.
Die alleinige Zugabe bewirkt bereits eine noch glänzende und eigeebnete Abscheidung in einem Stromdichtebereich von 2 - 5 A/dm2» Die Prüfung erfolgte in der Hull-The addition alone results in a still shiny and leveled deposit in a current density range of 2 - 5 A / dm 2 »The test was carried out in the Hull
Zelle bei 55°C mit Lufteinblasung. Ein gekratztes Kupferblech 7 x 10 cm wurde 10 Minuten bei 2,5 Ampere galvanisiert.Cell at 55 ° C with air injection. A scratched copper sheet 7 x 10 cm was galvanized at 2.5 amps for 10 minutes.
BEISPIEL 1,1EXAMPLE 1.1
Zum Elektrolyten nach Beispiel 1,0 wird zusätzlich zur erfindungsgemäßen Verbindung als Grundglänzer 1 g/1 Saccharin, Natriumsalz zugesetzt. Das Blech zeigt eine hochglänzende und gut eingeebnete Abscheidung im Stromdichtebereich von 2-8 A/dm2.In addition to the compound according to the invention, 1 g / 1 saccharin, sodium salt is added to the electrolyte according to Example 1.0. The sheet shows a high-gloss and well-leveled deposition in the current density range of 2-8 A / dm 2 .
BEISPIEL 2,0EXAMPLE 2.0
Zu einem Elektrolyten mit der Zusammensetzung 250 g/1 Nickelsulfat (NiS04 *7H20)To an electrolyte with the composition 250 g / 1 nickel sulfate (NiS0 4 * 7H 2 0)
80 g/1 Nickelchlorid (NiS04 »6H20)80 g / 1 nickel chloride (NiS0 4 »6H 2 0)
40 g/1 Borsäure (H3BO3) 0,5 g/1 2-Äthylhexysulfat, Natriumsalz als Netzmittel, werden 0,1 g/1 N,N-Diäthylaminopropin und 1 g/1 Saccharin (Benzoesäuresulfimid, Natriumsalz) zugesetzt.40 g / 1 boric acid (H 3 BO 3 ) 0.5 g / 1 2-ethylhexysulfate, sodium salt as wetting agent, 0.1 g / 1 N, N-diethylaminopropin and 1 g / 1 saccharin (benzoic acid sulfimide, sodium salt) are added.
Man erzielt eine glänzende, etwas eingeebnete Abscheidung in einem Stromdichtebereich von 0,1 - 8 A/dm2. Durch Zugabe von nur 0,1 g/1 der erfindungsgemäßen Verbindung erhält man in diesem Bereich eine hochglänzende und sehr gut eingeebnete Abscheidung. BEISPIEL 2 , 1A glossy, somewhat leveled deposition is achieved in a current density range of 0.1 - 8 A / dm 2 . By adding only 0.1 g / 1 of the compound according to the invention, a high-gloss and very well leveled deposition is obtained in this area. EXAMPLE 2, 1
Ersetzt man im Beispiel 2,0 das N,N-Diäthylaminopropin durch 0,07 g/1 2-Butindiol(1.4) so erhält man in dem Bereich von 0,3 bis 8 A/dm2 eine hochglänzende und sehr gute eingeebnete Abscheidung.If in Example 2.0 the N, N-diethylaminopropin is replaced by 0.07 g / 1 2-butynediol (1.4), a highly glossy and very good leveled separation is obtained in the range from 0.3 to 8 A / dm 2 .
BEISPIEL 2,2EXAMPLE 2.2
Ersetzt man im Beispiel 2,0 das N,N-Diäthylaminopropin durch 0,05 g/1 2-Butindiol-bis-hydroxyäthyläther (1.4), so erhält man in dem Bereich von 0.2 bis 8,2 A/dm2 eine hochglänzende und sehr gut eingeebnete Abscheidung.Replacing the N, N-diethylaminopropine in Example 2.0 with 0.05 g / l of 2-butynediol-bis-hydroxyethyl ether (1.4) gives a high-gloss and in the range from 0.2 to 8.2 A / dm 2 very well leveled separation.
BEISPIEL 2,3EXAMPLE 2.3
Ersetzt man im Beispiel 2,0 das N,N-Diäthylaminopropin durch 0,03 g/1 Äthylenglycolmonopropargyläther, so erhält man in dem Bereich von 0,2 bis 8,2 A/dm2 eine hochglänzende und sehr gut eingeebnete Abscheidung.If, in Example 2.0, the N, N-diethylaminopropin is replaced by 0.03 g / 1 ethylene glycol monopropargyl ether, a high-gloss and very well-leveled deposit is obtained in the range from 0.2 to 8.2 A / dm 2 .
BEISPEIL 2,4EXAMPLE 2.4
Ersetzt man im Beispiel 2,0 N,N-Diäthylaminopropin durch 0,007 g/1 Propargylalkohol, so erhält man in dem Bereich von 0,3 bisIf in the example 2.0 N, N-diethylaminopropin is replaced by 0.007 g / l of propargyl alcohol, the result is in the range from 0.3 to
7,2 A/dm2 eine hochglänzenden und sehr gut eingeebnete Abscheidung.7.2 A / dm 2 a high-gloss and very well leveled separation.
BEISPIEL 2,5EXAMPLE 2.5
Ersetzt man im Beispiel 2,.0 das N,N-Diäthylaminopropin durch 0,15 g/1 Hydroxypropinsulfonsäure, Natriumsalz, so erhält man in dem Bereich von 0,1 bis 8 A/dm2 eine hochglänzende und sehr gut eingeebnete Abscheidung.If in Example 2, .0 the N, N-diethylaminopropin is replaced by 0.15 g / 1 hydroxypropinsulfonic acid, sodium salt, a high-gloss and very well-leveled deposit is obtained in the range from 0.1 to 8 A / dm 2 .
BEISPIEL 2,6EXAMPLE 2.6
Ersetzt man im Beispiel 2,0 das N,N-Diäthylaminopropin durch 0,05 g/1 Propinsulfonsäure, Natriumsalz, so erhält man in dem - a - Bereich von 0,2 bis 9 A/dm2 eine hochglänzende und gut eingeebnete Abscheidung.If in Example 2.0 the N, N-diethylaminopropin is replaced by 0.05 g / 1 propynesulfonic acid, sodium salt, the result is - a - range from 0.2 to 9 A / dm 2 a high-gloss and well-leveled deposition.
BEISPIEL 2,7EXAMPLE 2.7
Ersetzt man im Beiepiel 2,0 N,N-Diäthylaminopropin durch 0,25 g/1 Vinylsulfonsäure, Natriumsalz, so erhält man in dem Bereich von 0,1 bis 10 A/dm2 eine hochglänzende und gut eingeebnete Abscheidung.If, for example, 2.0 N, N-diethylaminopropin is replaced by 0.25 g / 1 vinylsulfonic acid, sodium salt, a highly glossy and well-leveled deposit is obtained in the range from 0.1 to 10 A / dm 2 .
BEISPIEL 3EXAMPLE 3
Ein Elektrolyt mit folgender Zusammensetzung 270 g/1 Nickelsulfat (NiS04 «7H20)An electrolyte with the following composition 270 g / 1 nickel sulfate (NiS0 4 «7H 2 0)
40 g/1 Nickelchlorid (NiCl2 .6H20)40 g / 1 nickel chloride (NiCl 2 .6H 2 0)
40 g/1 Borsäure (H3B03) 0,5 g/1 2-Äthylhexylsulfat, Natriumsalz als Netzmittel 1 g/1 Saccharin, Natriumsalz 1 g/1 Formalin (37%ig) und 0,3 g/1 der erfindungsgemäßen Verbindung wird im Dauerbetrieb mit 4 A/dm2 belastet. Die jeweils fehlende Menge an Zusätzen wird nach der Prüfung in der Hull-Zelle ergänzt. Der Verbrauch liegt bei 50 g der erfindungsgemäßen Verbindung bezogen auf einen Ladungsdurchgang von 1000 Ah.40 g / 1 boric acid (H 3 B0 3 ) 0.5 g / 1 2-ethylhexyl sulfate, sodium salt as wetting agent 1 g / 1 saccharin, sodium salt 1 g / 1 formalin (37%) and 0.3 g / 1 of the invention Connection is loaded with 4 A / dm 2 in continuous operation. The missing amount of additives is added after the test in the Hull cell. The consumption is 50 g of the compound according to the invention based on a charge of 1000 Ah.
BEISPIEL 3,1EXAMPLE 3.1
Ersetzt man im Beispiel 3 die erfindungsmäße Verbindung durch 1- (3-Sulfσpropyl^pyridiniumbetain, so wird ein Verbrauch von 60 g bezogen auf einen Ladungsdurchgang von 1000 Ah ermittelt. Somit erzielt man durch die erfindugsgemäße Verbindung bei gleichem galvanotechnischen Effekt eine mengenmäßige Einsparung. If the compound according to the invention is replaced by 1- (3-sulfσpropyl ^ pyridinium betaine in example 3), a consumption of 60 g is determined based on a charge passage of 1000 Ah.

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1. Saure Nickelbäder, enthaltend l-(2-Sulfoethyl)- pyridiniumbetain.1. Acidic nickel baths containing l- (2-sulfoethyl) pyridinium betaine.
2. Saure Nickelbäder gemäß Anspruch 1, enthaltend l-(2- Sulfoethyl)-pyridiniumbetain in einer Konzentration von 0,005 bis 5 g/1.2. Acidic nickel baths according to claim 1, containing 1- (2-sulfoethyl) pyridinium betaine in a concentration of 0.005 to 5 g / 1.
3. Saure Nickelbäder gemäß Ansprüchen 1 und 2 enthaltend Grundglänzer in Konzentrationen von 0,005 bis 10 g/1.3. Acidic nickel baths according to claims 1 and 2 containing base gloss in concentrations of 0.005 to 10 g / 1.
4. Saure Nickelbäder gemäß Ansprüchen 1 und 2, enthaltend Einebner in Konzentrationen von 0,005 bis 0,25 g/1.4. Acidic nickel baths according to claims 1 and 2, containing leveling agents in concentrations of 0.005 to 0.25 g / 1.
5. Saure Nickelbäder gemäß Anspruch 4, enthaltend Propargylalkohol in Konzentrationen von 0,01 bis 0,15 g/1.5. Acidic nickel baths according to claim 4, containing propargyl alcohol in concentrations of 0.01 to 0.15 g / 1.
6. Saure Nickelbäder gemäß Anspruch 4, enthaltend 2- Butindiolr(1,4) in Konzentrationen von 0,02 bis 0,25 g/1.6. Acidic nickel baths according to claim 4, containing 2-butynediol (1.4) in concentrations of 0.02 to 0.25 g / 1.
7. Saure Nickelbäder gemäß Anspruch 4, enthaltend Äthylenglycolmonopropargyläther in Konzentrationen von 0,01 bis 0,1 g/1.7. Acidic nickel baths according to claim 4, containing ethylene glycol monopropargyl ether in concentrations of 0.01 to 0.1 g / 1.
8. Saure Nickelbäder gemäß Anspruch 4, enthaltend N,N- Diäthylaminopropin in Konzentrationen von 0,02 bis 0,25 g/1.8. Acidic nickel baths according to claim 4, containing N, N-diethylaminopropin in concentrations of 0.02 to 0.25 g / 1.
9. Saure Nickelbäder gemäß Anspruch 4, enthaltend 2-Butindiol- bis-(hydroxyäthyläther) oder 2-Butindiol-mono(Hydroxy- isopropyläther) in Konzentrationen von 0,02 bis 0,25 g/1.9. Acidic nickel baths according to claim 4, containing 2-butynediol bis (hydroxyethyl ether) or 2-butynediol mono (hydroxyisopropyl ether) in concentrations of 0.02 to 0.25 g / 1.
10. Saure Nickelbäder gemäß Anspruch 4, enthaltend Hydroxypropinsulfonsäure, oder 2,5-Hexindiol ihrer Salze in Konzentrationen von 0,02 bis 0,25 g/1.10. Acidic nickel baths according to claim 4, containing hydroxypropinsulfonic acid, or 2,5-hexindiol of their salts in concentrations of 0.02 to 0.25 g / 1.
11. Saure Nickelbäder gemäß Ansprüchen 1 und 2 , enthaltend Netzmitel in Konzentrationen von 0,1 - 10 g/1. 11. Acidic nickel baths according to claims 1 and 2, containing wetting agents in concentrations of 0.1-10 g / 1.
EP91907848A 1990-04-23 1991-04-22 Acid nickel baths containing 1-(2-sulfoethyl)-pyridinium betaine Expired - Lifetime EP0526497B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4013349A DE4013349A1 (en) 1990-04-23 1990-04-23 1- (2-SULFOAETHYL) PYRIDINIUMBETAIN, METHOD FOR THE PRODUCTION THEREOF AND ACID NICKEL BATH CONTAINING THIS COMPOUND
DE4013349 1990-04-23
PCT/DE1991/000336 WO1991016474A1 (en) 1990-04-23 1991-04-22 Acid nickel baths containing 1-(2-sulfoethyl)-pyridinium betaine

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EP0526497A1 true EP0526497A1 (en) 1993-02-10
EP0526497B1 EP0526497B1 (en) 1995-02-08

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EP (1) EP0526497B1 (en)
JP (1) JP3199729B2 (en)
AT (1) ATE118253T1 (en)
DE (2) DE4013349A1 (en)
ES (1) ES2068577T3 (en)
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ATE289993T1 (en) 1997-08-01 2005-03-15 Reilly Ind Inc SUPERNUCLEOPHILIC 4-POSITION SUBSTITUTED PYRIDINE CATALYST AND METHODS USEFUL FOR THE PRODUCTION THEREOF
DE19805487A1 (en) * 1998-02-11 1999-08-12 Basf Ag Synthesis of 1- (2-sulfoethyl) pyridinium betaine
DE102014207778B3 (en) * 2014-04-25 2015-05-21 Kiesow Dr. Brinkmann GmbH & Co. KG Use of a mixture for use in a plating bath or plating bath to produce a bright nickel plating, and to a method of making an article having a bright nickel plating
US10458032B2 (en) * 2017-06-15 2019-10-29 Rohm And Haas Electronic Materials Llc Environmentally friendly nickel electroplating compositions and methods
US10718059B2 (en) * 2017-07-10 2020-07-21 Rohm And Haas Electronic Materials Llc Nickel electroplating compositions with cationic polymers and methods of electroplating nickel
EP3456870A1 (en) * 2017-09-13 2019-03-20 ATOTECH Deutschland GmbH A bath and method for filling a vertical interconnect access or trench of a work piece with nickel or a nickel alloy

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NL100419C (en) * 1955-03-16
US3131189A (en) * 1961-10-16 1964-04-28 Pure Oil Co Preparation of quaternary ammonium betaine salts
FR1529883A (en) * 1967-05-11 1968-06-21 Conservatoire Nat Arts Process for sulfoethylation of tertiary amines and new compounds obtained
DE1621157A1 (en) * 1967-08-16 1971-05-19 Riedel & Co Acid galvanic nickel bath
US3862019A (en) * 1974-04-26 1975-01-21 R O Hull & Company Inc Composition of electroplating bath for the electrodeposition of bright nickel
CA1242809A (en) * 1985-12-20 1988-10-04 Mitel Corporation Data storage system
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DD266814A1 (en) * 1987-10-13 1989-04-12 Leipzig Galvanotechnik METHOD FOR THE ELECTROLYTIC SEPARATION OF GLAZING NICKEL LAYERS
FR2630753B1 (en) * 1988-05-02 1992-01-03 Piolat Ind PERFORATED NICKEL FRAMES AND THEIR MANUFACTURING METHOD
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HK3596A (en) 1996-01-12
ES2068577T3 (en) 1995-04-16
US5264112A (en) 1993-11-23
DE4013349A1 (en) 1991-10-24
EP0526497B1 (en) 1995-02-08
DE59104555D1 (en) 1995-03-23
JP3199729B2 (en) 2001-08-20
WO1991016474A1 (en) 1991-10-31
JPH05506695A (en) 1993-09-30
ATE118253T1 (en) 1995-02-15

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