EP0621908A1 - Process for producing nickel-plated mouldings. - Google Patents
Process for producing nickel-plated mouldings.Info
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- EP0621908A1 EP0621908A1 EP93902188A EP93902188A EP0621908A1 EP 0621908 A1 EP0621908 A1 EP 0621908A1 EP 93902188 A EP93902188 A EP 93902188A EP 93902188 A EP93902188 A EP 93902188A EP 0621908 A1 EP0621908 A1 EP 0621908A1
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- nickel
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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
Definitions
- the present invention relates to an improved process for the production of nickel-plated moldings by electrodeposition of nickel from aqueous acid baths which contain, as essential components, one or more nickel salts, one or more inorganic acids and at least two brighteners.
- the invention further relates to a gloss agent mixture that can be used for this purpose.
- Such brighteners which are generally divided into primary brighteners (“brighteners”) and secondary brighteners (“brighteners”), are usually used as a combination of several of these agents in order to increase the effect.
- Sulfonimides e.g. Benzoic acid sulfi id sulfonamides
- Benzenesulfonic acids e.g. Mono-, di- and tribenzenesulfonic acid
- naphthalenesulfonic acids e.g. Mono-, di- and trinaphthalenesulfonic acid
- Alkylsulfonic acids sulfinic acid arylsulfone sulfonates aliphatic compounds with ethylene and / or acetylene compounds, e.g. Butynediol mono- and polynuclear nitrogen-containing heterocycles, which can also contain further heteroatoms such as sulfur or selenium
- Saccharin. DE-B 11 91 652 (2) describes mono- or polynuclear heterocyclic nitrogen bases of the aromatic type in quaternized form, such as pyridinium salts, for example 2-pyridinium-l-sulfatoethane, as leveling agents, ie brighteners, for acidic galvanic nickel baths described. These agents are used together with conventional basic gloss agents such as benzene-m-disulfonic acid, diaryl disulfimides or sulfonamides.
- a disadvantage of the agents known from the prior art is, on the one hand, the generally relatively high use concentrations in the nickel electrolyte baths used, on the other hand, the gloss and the leveling that can be achieved with these agents are still in need of improvement.
- the object of the invention was therefore to remedy the shortcomings of the prior art described.
- N atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two C 1 -C 4 -alkyl substituents or halogen atoms,
- R 1 'R 3 and R 4 are hydrogen or -C ⁇ to C alkyl
- R 2 denotes hydrogen or methyl
- m stands for a number from 0 to 4
- n stands for a number from 1 to 4 and denotes an n-valent inorganic or organic anion which promotes water solubility
- C 1 -C 4 -alkyl radicals are generally n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially methyl and ethyl.
- alkyl-substituted or halogen-substituted heterocyclic ring systems for I:
- halogen atom here includes fluorine, iodine and especially bromine and chlorine.
- Unsubstituted pyridinium is preferred.
- the radicals R 1 , R 3 and R 4 are preferably hydrogen.
- variable m preferably stands for 1.
- Suitable n-valent anions X are the customary inorganic or organic anions which normally promote water solubility, in particular chloride, bromide, fluoride, sulfate, hydrogen sulfate, methanesulfonate, trifluoromethanesulfonate, 2-hydroxyethanesulfonate, p-toluenesulfonate , Nitrate, tetrafluoroborate, perchlorate, 1-hydroxyethane-l, 1-diphosphonate, dihydrogen phosphate, phosphate, formate, acetate, oxalate and tartrate.
- cyclic N-allylammonium compounds of the general formula Ia are used as component A.
- the cyclic N-allyl or N-vinylammonium compounds I and Ia can best be known in a known manner by reacting the corresponding precursor of the general formula
- Z represents a nucleofugic leaving group, preferably chlorine or bromine, with a heterocycle of the general formula IV
- the reaction of components III and IV is advantageously carried out in an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture carried out from here.
- an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture carried out from here.
- the reaction can also be carried out in water or in a single-phase or two-phase mixture of water and one or more organic solvents.
- a customary phase transfer catalyst can be used. It is usually carried out
- Component B uses acetylenically unsaturated compounds II which carry at least one polar functional group, preferably in the ⁇ -position of the C 1 -C 4 -alkyl radicals.
- Unfunctionalized acetylenically unsaturated hydrocarbons are unsuitable mainly because of their low solubility in aqueous media and their high volatility.
- these can be alkoxylated by a C 2 -C alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide or a mixture of such alkylene oxides.
- the degree of alkoxylation is preferably 1 to 3, in particular 1.
- Sulfo group-containing compounds II can be in the form of the free acid or preferably in the form of their alkali metal, e.g. Sodium or potassium or ammonium salts can be used.
- component B uses acetylenically unsaturated compounds II in which the radicals R 4 and R 5 are identical or different and denote methyl or ethyl substituted by hydroxyl, sulfo or dimethyl- or diethylamino, hydroxyl groups having 1 up to 3 mol of a 0. 2 - to C 4 -alkylene oxide or a mixture of such alkylene oxides can be reacted and one of the radicals R 4 or R 5 can also be hydrogen, methyl or ethyl.
- examples of compounds II are:
- Ethoxylate, monoethoxylate, diethoxylate, propoxylate, monopropoxylate and dipropoxylate are to be understood here as meaning the reaction products with 1 mol of alkylene oxide per hydroxyl group in the compounds II.
- the mixture of the cyclic N-allyl or N-vinylammonium compounds I and the acetylenically unsaturated compounds II is preferably composed of 10 to 90% by weight, in particular 25 to 75% by weight of component A and 90 to 10% by weight .-%, in particular 75 to 25 wt .-% of component B.
- a mixture of 28 to 50% by weight of A and 72 to 50% by weight of B is very particularly preferred.
- a mixture of one or more cyclic N-allyl or N-vinylammonium compounds I is used as component A and at least three, in particular three to seven, acetylenically unsaturated compounds II as component B.
- mixtures of components A and B can additionally be used together with other customary brighteners, for example with saccharin, allylsulfonic acid or their alkali metal or ammonium salts, vinylsulfonic acid or their alkali metal or ammonium salts, bisbenzenesulfonylimide or commercially available brighteners based on a thio compound.
- other customary brighteners for example with saccharin, allylsulfonic acid or their alkali metal or ammonium salts, vinylsulfonic acid or their alkali metal or ammonium salts, bisbenzenesulfonylimide or commercially available brighteners based on a thio compound.
- the aqueous-acidic nickel electrolyte baths contain one or usually more nickel salts, for example nickel sulfate and nickel chloride, one or more inorganic acids, preferably boric acid and sulfuric acid, as a brightening agent, the mixture of components A and B alone or in combination with other usual - Chen gloss agents and, if appropriate, other conventional auxiliaries and additives in the concentrations customary for this, for example wetting agents and pore-preventing agents.
- nickel salts for example nickel sulfate and nickel chloride
- inorganic acids preferably boric acid and sulfuric acid
- the pH of the electrolyte baths is usually between 3 and 6, preferably between 4 and 5.
- a strong mineral acid preferably sulfuric acid, is expediently used to set this pH.
- the mixture of components A and B is present in the electrolyte baths in low concentrations, generally between 0.05 and 1.0 g / 1, preferably between 0.1 and 0.5 g / 1.
- concentrations of other customary brighteners are normally in the range from 0.1 to 10 g / 1, in particular 0.1 to 2.0 g / 1.
- the nickel electrolyte baths described above can be used to produce nickel coatings on molded parts made of steel, but also on molded parts made of other materials, for example brass, which have been pretreated as usual. This is usually done at temperatures of 30 to 80 ° C, preferably 40 to 60 ° C.
- the present invention furthermore relates to a mixture of brighteners for aqueous-acidic galvanic baths for the deposition of nickel, comprising a mixture of
- N atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two Ci to C alkyl substituents or halogen atoms,
- R 1 'R 3 and R 4 are hydrogen or -C ⁇ to C 4 alkyl
- R 2 is hydrogen or methyl
- m stands for a number from 0 to 4
- n stands for a number from 1 to 4
- xP denotes an n-valent inorganic or organic anion which promotes water solubility
- radicals R 4 and R 5 are identical or different and are substituted by hydroxyl, sulfo, amino, C 1 -C 4 -alkylamino or di (C 1 -C 4 -alkyl) amino-substituted C 1 -C 4 -alkyl draw, with hydroxyl groups with 1 to 10 mol of one
- C 2 - to C 4 -alkylene oxide or a mixture of such alkylene oxides can be reacted and one of the radicals R 4 or R 5 can also be hydrogen or C 1 -C 4 -alkyl.
- the mixture of gloss agents according to the invention is distinguished by an extraordinarily high gloss formation. As a rule, it achieves a stronger shine and a better leveling than with the usual brighteners at a significantly lower dosage in the nickel electrolyte baths.
- the aqueous nickel electrolyte used had the following composition:
- the pH of the electrolyte was adjusted to 4.2 with sulfuric acid.
- Brass sheets were used, which were degreased cathodically in an alkaline electrolyte according to the usual methods before the coating with nickel.
- the nickel deposition was carried out in a 250 ml Hull cell at 55 ° C. and a current of 2A over a period of 10 minutes. The sheets were then rinsed with water and dried with compressed air.
- Comparative mixtures A and B are known from reference (3).
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- 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)
- Chemically Coating (AREA)
- Detergent Compositions (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
PCT No. PCT/EP93/00063 Sec. 371 Date Jul. 25, 1994 Sec. 102(e) Date Jul. 25, 1994 PCT Filed Jan. 14, 1993 PCT Pub. No. WO93/15241 PCT Pub. Date Aug. 5, 1993.Nickelized shaped articles are produced by electrodeposition of nickel from aqueous acidic baths containing as essential constituents one or more nickel salts, one or more inorganic acids and at least two brighteners by using as brighteners a mixture of A) from 2 to 98% by weight of one or more cyclic N-allylammonium or N-vinylammonium compounds I <IMAGE> (I) where the nitrogen atom is part of a pyridine, quinoline or isoquinoline ring system which may additionally carry one or two C1- to C4-alkyl substituents or halogen atoms, R1, R3 and R4 are each hydrogen or C1- to C4-alkyl, R2 is hydrogen or methyl, m is from 0 to 4, n is from 1 to 4, and X(-) is an n-valent inorganic or organic anion which promotes solubility in water, and B) from 98 to 2% by weight of one or more acetylenically unsaturated compounds II R4-C 3BOND C-R5(II) where R4 and R5 are identical or different and each is C1- to C4-alkyl substituted by hydroxyl, sulfo, amino, C1- to C4-alkylamino or di(C1- to C4-alkyl)amino, although hydroxyl groups may have been reacted with from 1 to 10 mol of a C2- to C4-alkylene oxide or a mixture of such alkylene oxides and one of the radicals R4 and R5 may also be hydrogen or C1- to C4-alkyl.
Description
Verfahren zur Herstellung vernickelter FormteileProcess for the production of nickel-plated molded parts
Beschreibungdescription
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung vernickelter Formteile durch galvanisches Abscheiden von Nickel aus wäßrig-sauren Bädern, die als wesentliche Bestand¬ teile ein oder mehrere Nickelsalze, ein oder mehrere anorganische Säuren und mindestens zwei Glanzmittel enthalten. Weiterhin be¬ trifft die Erfindung eine hierzu verwendbare Glanzmittelmischung.The present invention relates to an improved process for the production of nickel-plated moldings by electrodeposition of nickel from aqueous acid baths which contain, as essential components, one or more nickel salts, one or more inorganic acids and at least two brighteners. The invention further relates to a gloss agent mixture that can be used for this purpose.
Es ist bekannt, daß saure Nickelelektrolyte in geringer Menge or¬ ganische Substanzen enthalten müssen, wenn bei der galvanischen Nickelabscheidung eine glänzende, duktile und an der Oberfläche ebene Abscheidung des Metalls erzielt werden soll. Derartige Glanzmittel, die man in der Regel in primäre Glanzmittel ("Glanz¬ träger") und sekundäre Glanzmittel ("Glanzbildner") unterteilt, werden üblicherweise als Kombination aus mehreren dieser Mittel eingesetzt, um die Wirkung zu steigern.It is known that acidic nickel electrolytes must contain small amounts of organic substances if a shiny, ductile and even surface deposition of the metal is to be achieved in the electrodeposition of nickel. Such brighteners, which are generally divided into primary brighteners ("brighteners") and secondary brighteners ("brighteners"), are usually used as a combination of several of these agents in order to increase the effect.
In der Literaturstelle "Praktische Galvanotechnik", Eugen G. Len¬ ze Verlag, Saulgau, 4. Auflage 1984, Seite 268 bis 271 (1) werden Substanzklassen für übliche Glanzmittel für Nickelelektrolyte be- schrieben. Eine Einteilung in primäre und sekundäre Glanzmittel und Einebner wird zwar getroffen, es wird aber gleichzeitig da¬ rauf hingewiesen, daß diese Einteilung nicht immer eindeutig vor¬ genommen werden kann. Als glanzerzeugende Substanzklassen werden genannt:In the reference "Practical Electroplating", Eugen G. Lenze Verlag, Saulgau, 4th edition 1984, pages 268 to 271 (1), substance classes for conventional brighteners for nickel electrolytes are described. A division into primary and secondary brighteners and levelers is made, but at the same time it is pointed out that this division cannot always be made clearly. The following are mentioned as gloss-producing substance classes:
- Sulfonimide, z.B. Benzoesäuresulfi id SulfonamideSulfonimides, e.g. Benzoic acid sulfi id sulfonamides
Benzolsulfonsäuren, z.B. Mono-, Di- und Tribenzolsulfonsäure Naphthalinsulfonsäuren, z.B. Mono-, Di- und Trinaphthalinsul- fonsäureBenzenesulfonic acids, e.g. Mono-, di- and tribenzenesulfonic acid naphthalenesulfonic acids, e.g. Mono-, di- and trinaphthalenesulfonic acid
- Alkylsulfonsäuren Sulfinsäure Arylsulfonsulfonate aliphatische Verbindungen mit Ethylen- und/oder Acetylenver- bindungen, z.B. Butindiol ein- und mehrkernige stickstoffhaltige Heterocyclen, welche noch weitere Heteroatome wie Schwefel oder Selen enthalten könnenAlkylsulfonic acids sulfinic acid arylsulfone sulfonates aliphatic compounds with ethylene and / or acetylene compounds, e.g. Butynediol mono- and polynuclear nitrogen-containing heterocycles, which can also contain further heteroatoms such as sulfur or selenium
Cumarin - Amine und quaternäre Ammoniumverbindungen als Einebnungsmit- telCoumarin - amines and quaternary ammonium compounds as leveling agents
Saccharin.
In der DE-B 11 91 652 (2) werden ein- oder mehrkernige heterocy- clische Stickstoffbasen vom aromatischen Typ in quaternisierter Form wie Pyridiniumsalze, z.B. 2-Pyridinium-l-sulfatoethan, als Einebnungsmittel, d.h. Glanzmittel, für saure galvanische Nickel- bäder beschrieben. Diese Mittel werden zusammen mit üblichen Grundglanzmitteln wie Benzol-m-disulfonsäure, Diaryldisulfimiden oder Sulfonamiden verwendet.Saccharin. DE-B 11 91 652 (2) describes mono- or polynuclear heterocyclic nitrogen bases of the aromatic type in quaternized form, such as pyridinium salts, for example 2-pyridinium-l-sulfatoethane, as leveling agents, ie brighteners, for acidic galvanic nickel baths described. These agents are used together with conventional basic gloss agents such as benzene-m-disulfonic acid, diaryl disulfimides or sulfonamides.
In der US-A 2 647 866 (3) werden Mischungen von N-substituierten Pyridiniumverbindungen, z.B. N-Allyl- oder N-Methallylpyridinium- halogeniden, mit bestimmten schwefelhaltigen Verbindungen, z.B. Allylsulfonsäure, als gut wirksame Glanzmittel bei der galvani¬ schen Abscheidung von Nickel beschrieben. Dabei wird für Allyl¬ sulfonsäure eine Einsatzkonzentration von 4 bis 12 g/1 empfohlen.In U.S.-A 2,647,866 (3) mixtures of N-substituted pyridinium compounds, e.g. N-allyl or N-methallylpyridinium halides, with certain sulfur-containing compounds, e.g. Allylsulfonic acid, described as a highly effective brightening agent in the electrodeposition of nickel. A use concentration of 4 to 12 g / l is recommended for allyl sulfonic acid.
Nachteilig bei den aus dem Stand der Technik bekannten Mitteln sind allerdings zum einen die in der Regel relativ hohen Einsatz¬ konzentrationen in den verwendeten Nickelelektrolyt-Bädern, zum anderen sind der Glanz und die Einebnung, die mit diesen Mitteln erzielt werden können, noch verbesserungsbedürftig.A disadvantage of the agents known from the prior art is, on the one hand, the generally relatively high use concentrations in the nickel electrolyte baths used, on the other hand, the gloss and the leveling that can be achieved with these agents are still in need of improvement.
Der Erfindung lag daher als Aufgabe zugrunde, den geschilderten Mängeln des Standes der Technik abzuhelfen.The object of the invention was therefore to remedy the shortcomings of the prior art described.
Demgemäß wurde eine Verfahren zur Herstellung vernickelter Form¬ teile durch galvanisches Abscheiden von Nickel aus wäßrig-sauren Bädern, die als wesentliche Bestandteile ein oder mehrere Nickel¬ salze, eine oder mehrere anorganische Säuren und mindestens zwei Glanzmittel enthalten, gefunden, welches dadurch gekennzeichnet ist, daß man als Glanzmittel eine Mischung ausAccordingly, a process for the production of nickel-plated moldings by electrodeposition of nickel from aqueous-acid baths, which contain as essential constituents one or more nickel salts, one or more inorganic acids and at least two brighteners, was found, which is characterized in that that a mixture of
A) 2 bis 98 Gew.-% einer oder mehrerer cyclischer N-Allyl- oder N-Vinylammoniumverbindungen der allgemeinen Formel IA) 2 to 98% by weight of one or more cyclic N-allyl or N-vinylammonium compounds of the general formula I.
in der das N-Atom Bestandteil eines Pyridin-, Chinolin- oder Isochinolin-Ringsystems ist, welches zusätzlich ein oder zwei Cι~ bis C4-Alkylsubstituenten oder Halogenatome tragen kann,in which the N atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two C 1 -C 4 -alkyl substituents or halogen atoms,
R1' R3 und R4 für Wasserstoff oder Cι~ bis C -Alkyl stehen,
R2 Wasserstoff oder Methyl bedeutet, m für eine Zahl von 0 bis 4 steht, n für eine Zahl von 1 bis 4 steht und ein n-wertiges anorganisches oder organisches Anion, wel¬ ches die Wasserlöslichkeit fördert, bezeichnet, undR 1 'R 3 and R 4 are hydrogen or -C ~ to C alkyl, R 2 denotes hydrogen or methyl, m stands for a number from 0 to 4, n stands for a number from 1 to 4 and denotes an n-valent inorganic or organic anion which promotes water solubility, and
B) 98 bis 2 Gew.-% einer oder mehrerer acetylenisch ungesättig¬ ter Verbindungen der allgemeinen Formel IIB) 98 to 2% by weight of one or more acetylenically unsaturated compounds of the general formula II
R4. C ≡s C R5 (II) in der die Reste R4 und R5 gleich oder verschieden sind und durch Hydroxyl, Sulfo, Amino, Cι~ bis C -Alkylamino oder Di(Cι~ bis C4-alkyl)amino substituiertes Cι~ bis C -Alkyl be¬ zeichnen, wobei Hydroxylgruppen mit 1 bis 10 mol eines C2- bis C -Alkylenoxids oder einer Mischung solcher Alkyleno- xide umgesetzt sein können und einer der Reste R4 oder R5 auch Wasserstoff oder Cι~ bis C4-Alkyl sein kann, R4 . C ≡s CR 5 (II) in which the radicals R 4 and R 5 are the same or different and are substituted by hydroxyl, sulfo, amino, Cι ~ to C -alkylamino or di (Cι ~ to C 4 -alkyl) amino Cι ~ to C be alkyl, where hydroxyl groups can be reacted with 1 to 10 mol of a C 2 to C alkylene oxide or a mixture of such alkylene oxides and one of the radicals R 4 or R 5 can also be hydrogen or C 1 -C 4 -Alkyl can be
einsetzt.starts.
Als Cι~ bis C -Alkylreste kommen generell n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl und vor allem Methyl und Ethyl in Betracht.C 1 -C 4 -alkyl radicals are generally n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially methyl and ethyl.
Als alkylsubstituierte oder halogensubstituierte heterocyclische Ringsysteme für I seinen beispielhaft genannt:Examples of alkyl-substituted or halogen-substituted heterocyclic ring systems for I:
2-, 3- oder 4-Methylpyridinium,2-, 3- or 4-methylpyridinium,
2-, 3- oder 4-Chlorpyridinium,2-, 3- or 4-chloropyridinium,
2-, 3- oder 4-Brompyridinium,2-, 3- or 4-bromopyridinium,
2-, 3- oder 4-Ethylpyridinium,2-, 3- or 4-ethylpyridinium,
3- oder 4-n-Propylpyridinium, 3- oder 4-iso-Propylpyridinium,3- or 4-n-propylpyridinium, 3- or 4-iso-propylpyridinium,
3- oder 4-n-Butylpyridinium,3- or 4-n-butylpyridinium,
4-tert.-Butylpyridinium,4-tert-butylpyridinium,
2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-Dimethylpyridinium,2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylpyridinium,
3-Methy1-4-isopropylpyridinium, 4-tert.-Butyl-3-methylpyridinium,3-methyl-4- isopropylpyridinium, 4-tert-butyl-3-methylpyridinium,
2-, 3-, 4-, 5-, 6-, 7- oder 8-Methylchninolinium,2-, 3-, 4-, 5-, 6-, 7- or 8-methylquinolinium,
2- oder 6-Bromchinolinium,2- or 6-bromoquinolinium,
2,4-Dichlorchinolinium,2,4-dichloroquinolinium,
2,4-, 2,8- oder 5,8-Dimethylchinolinium und 1-, 3-, 4-, 5-, 6-, 7- oder 8-Methylisochinolinium.
Der Begriff Halogenatom umfaßt hierbei Fluor, Jod und vor allem Brom und Chlor.2,4-, 2,8- or 5,8-dimethylquinolinium and 1-, 3-, 4-, 5-, 6-, 7- or 8-methylisoquinolinium. The term halogen atom here includes fluorine, iodine and especially bromine and chlorine.
Bevorzugt wird unsubstituiertes Pyridinium.Unsubstituted pyridinium is preferred.
Die Reste R1, R3 und R4 stehen vorzugsweise für Wasserstoff.The radicals R 1 , R 3 and R 4 are preferably hydrogen.
Die Variable m steht vorzugsweise für 1.The variable m preferably stands for 1.
Als n-wertige Anionen X kommen die üblichen, normalerweise die Wasserlöslichkeit fördernden anorganischen oder organischen Anio¬ nen in Betracht, so vor allem Chlorid, Bro id, Fluorid, Sulfat, Hydrogensulfat, Methansulfonat, Trifluormethansulfonat, 2-Hydro- xyethansulfonat, p-Toluolsulfonat, Nitrat, Tetrafluoroborat, Per- chlorat, 1-Hydroxyethan-l,1-diphosphonat, Dihydrogenphosphat, Phosphat, Formiat, Acetat, Oxalat und Tartrat.Suitable n-valent anions X are the customary inorganic or organic anions which normally promote water solubility, in particular chloride, bromide, fluoride, sulfate, hydrogen sulfate, methanesulfonate, trifluoromethanesulfonate, 2-hydroxyethanesulfonate, p-toluenesulfonate , Nitrate, tetrafluoroborate, perchlorate, 1-hydroxyethane-l, 1-diphosphonate, dihydrogen phosphate, phosphate, formate, acetate, oxalate and tartrate.
Hiervon werden ein- oder zweifach (n = 1 oder 2) geladene Anio¬ nen, vor allem Fluorid, Sulfat, Methansulfonat, Nitrat und Tetra- fluoroborat, insbesondere jedoch Chlorid und Bromid bevorzugt.Of these, one or two (n = 1 or 2) charged anions, especially fluoride, sulfate, methanesulfonate, nitrate and tetrafluoroborate, but especially chloride and bromide, are preferred.
In einer bevorzugten Ausführungsform setzt man als Komponente A cyclische N-Allylammoniumverbindungen der allgemeinen Formel IaIn a preferred embodiment, cyclic N-allylammonium compounds of the general formula Ia are used as component A.
in der R2, n und X® die oben genannten Bedeutungen haben, ein.in which R 2 , n and X® have the meanings given above.
Die cyclischen N-Allyl- oder N-Vinylammoniumverbindungen I bzw. Ia lassen sich am besten in bekannter Weise durch Umsetzung der entsprechenden Vorstufe der allgemeinen FormelThe cyclic N-allyl or N-vinylammonium compounds I and Ia can best be known in a known manner by reacting the corresponding precursor of the general formula
in der Z eine nucleofuge Abgangsgruppe, vorzugsweise Chlor oder Brom, darstellt, mit einem Heterocyclus der allgemeinen Formel IV
in which Z represents a nucleofugic leaving group, preferably chlorine or bromine, with a heterocycle of the general formula IV
und gewünschtenfalls anschließenden Austausch des Anions Z gegen X® herstellen.and if necessary, then exchange the anion Z for X®.
Die Umsetzung der Komponenten III und IV wird zweckmäßigerweise in einem inerten organischen Lösungsmittel wie Toluol, Xylol, Pe- trolether, Ligroin, Cyclohexan, Aceton, Tetrahydrofuran, Dioxan, Methanol, Ethanol, iso-Propanol, Essigsäureethylester oder Ben- zoesäuremethylester oder in einer Mischung hieraus durchgeführt. Man kann die Umsetzung aber auch in Wasser oder in einem einpha¬ sigen oder zweiphasigen Gemisch aus Wasser und einem oder mehre- ren organischen Lösungsmitteln, vornehmen. Bei Zweiphasengemi¬ schen kann ein üblicher Phasentransferkatalysator eingesetzt wer¬ den. Man arbeitet in der Regel bei Temperaturen von 40 bis 130°C, insbesondere bei 60 bis 110°C, und bei Normaldruck.The reaction of components III and IV is advantageously carried out in an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture carried out from here. However, the reaction can also be carried out in water or in a single-phase or two-phase mixture of water and one or more organic solvents. In the case of two-phase mixtures, a customary phase transfer catalyst can be used. It is usually carried out at temperatures from 40 to 130 ° C, in particular at 60 to 110 ° C, and at normal pressure.
Als Komponente B setzt man acetylenisch ungesättigte Verbindun¬ gen II ein, die mindestens eine polare funktioneile Gruppe, vor¬ zugsweise in der α-Position der Ci- bis C4-Alkylreste, tragen. Nicht funktionalisierte acetylenisch ungesättigte Kohlenwasser¬ stoffe sind hauptsächlich wegen ihrer geringen Löslichkeit in wäßrigen Medien und ihrer hohen Flüchtigkeit ungeeignet.Component B uses acetylenically unsaturated compounds II which carry at least one polar functional group, preferably in the α-position of the C 1 -C 4 -alkyl radicals. Unfunctionalized acetylenically unsaturated hydrocarbons are unsuitable mainly because of their low solubility in aqueous media and their high volatility.
Bei Verwendung von Hydroxylgruppen enthaltenden Verbindungen II können diese durch ein C2- bis C -Alkylenoxid wie Ethylenoxid, Propylenoxid oder Butylenoxid oder eine Mischung solcher Alkylen- oxide alkoxyliert sein. Der Alkoxylierungsgrad beträgt hierbei vorzugsweise 1 bis 3, insbesondere 1.When using compounds II containing hydroxyl groups, these can be alkoxylated by a C 2 -C alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide or a mixture of such alkylene oxides. The degree of alkoxylation is preferably 1 to 3, in particular 1.
Sulfogruppenhal ige Verbindungen II können in Form der freien Säure oder vorzugsweise in Form ihrer Alkalimetall-, z.B. Natri- um- oder Kalium-, oder Ammoniumsalze eingesetzt werden.Sulfo group-containing compounds II can be in the form of the free acid or preferably in the form of their alkali metal, e.g. Sodium or potassium or ammonium salts can be used.
In einer bevorzugten Ausführungsform setzt man als Komponente B acetylenisch ungesättigte Verbindungen II ein, bei denen die Re¬ ste R4 und R5 gleich oder verschieden sind und durch Hydroxyl, Sulfo oder Dimethyl- oder Diethylamino substituiertes Methyl oder Ethyl bezeichnen, wobei Hydroxylgruppen mit 1 bis 3 mol eines 0.2- bis C4-Alkylenoxids oder einer Mischung solcher Alkylenoxide umgesetzt sein können und einer der Reste R4 oder R5 auch Wasser¬ stoff, Methyl oder Ethyl sein kann.
Als Beispiele für Verbindungen II lassen sich nennen:In a preferred embodiment, component B uses acetylenically unsaturated compounds II in which the radicals R 4 and R 5 are identical or different and denote methyl or ethyl substituted by hydroxyl, sulfo or dimethyl- or diethylamino, hydroxyl groups having 1 up to 3 mol of a 0. 2 - to C 4 -alkylene oxide or a mixture of such alkylene oxides can be reacted and one of the radicals R 4 or R 5 can also be hydrogen, methyl or ethyl. Examples of compounds II are:
Prop-2-in-l-ol,Prop-2-in-l-ol,
But-2-in-l,4-diol, Hex-3-in-2,5-diol,But-2-in-l, 4-diol, hex-3-in-2,5-diol,
Prop-2-in-l-ol-ethoxylat,Prop-2-in-l-ol ethoxylate,
Prop-2-in-l-ol-propoxylat,Prop-2-in-l-ol propoxylate,
But-2-in-l,4-diol-monoethoxylat,But-2-in-l, 4-diol-monoethoxylate,
But-2-in-l,4-diol-diethoxylat, But-2-in-l,4-diol-monopropoxylat,But-2-in-l, 4-diol-diethoxylate, but-2-in-l, 4-diol-monopropoxylate,
But-2-in-l,4-diol-dipropoxylat,But-2-in-l, 4-diol dipropoxylate,
Prop-2-in-l-sulfonsäure,Prop-2-in-1-sulfonic acid,
1-Dimeth lamino-p op-2-in, l-Diethylamino-prop-2-in, l-Diethylamino-pent-2-in-4-ol und1-dimeth lamino-p op-2-in, l-diethylamino-prop-2-in, l-diethylamino-pent-2-in-4-ol and
1-Amino-l,l-dimethylprop-2-in.1-amino-l, l-dimethylprop-2-in.
Unter Ethoxylat, Monoethoxylat, Diethoxylat, Propoxylat, Monopro- poxylat und Dipropoxylat sind hier jeweils die Umsetzungsprodukte mit 1 mol Alkylenoxid pro Hydroxylgruppe in den Verbindungen II zu verstehen.Ethoxylate, monoethoxylate, diethoxylate, propoxylate, monopropoxylate and dipropoxylate are to be understood here as meaning the reaction products with 1 mol of alkylene oxide per hydroxyl group in the compounds II.
Die Mischung aus den cyclischen N-Allyl- oder N-Vinylammoniumver- bindungen I und den acetylenisch ungesättigten Verbindungen II setzt sich vorzugsweise aus 10 bis 90 Gew.-%, insbesondere 25 bis 75 Gew.-% der Komponente A und 90 bis 10 Gew.-%, insbesondere 75 bis 25 Gew.-% der Komponente B zusammen. Ganz besonders bevorzugt wird eine Mischung aus 28 bis 50 Gew.-% A und 72 bis 50 Gew.-% B.The mixture of the cyclic N-allyl or N-vinylammonium compounds I and the acetylenically unsaturated compounds II is preferably composed of 10 to 90% by weight, in particular 25 to 75% by weight of component A and 90 to 10% by weight .-%, in particular 75 to 25 wt .-% of component B. A mixture of 28 to 50% by weight of A and 72 to 50% by weight of B is very particularly preferred.
In einer bevorzugten Ausführungsform setzt man eine Mischung aus einer oder mehreren cyclischen N-Allyl- oder N-Vinylammoniumver- bindungen I als Komponente A und mindestens drei, insbesondere drei bis sieben acetylenisch ungesättigten Verbindungen II als Komponente B ein.In a preferred embodiment, a mixture of one or more cyclic N-allyl or N-vinylammonium compounds I is used as component A and at least three, in particular three to seven, acetylenically unsaturated compounds II as component B.
Weiterhin können die Mischungen aus den Komponenten A und B zu¬ sätzlich noch zusammen mit anderen üblichen Glanzmitteln einge¬ setzt werden, beispielsweise mit Saccharin, Allylsulfonsäure oder ihren Alkalimetall- oder Ammoniumsalzen, Vinylsulfonsäure oder ihren Alkalimetall- oder Ammoniumsalzen, Bisbenzolsulfonylimid oder handelsüblichen Glanzmitteln auf Basis einer Thioverbindung.Furthermore, the mixtures of components A and B can additionally be used together with other customary brighteners, for example with saccharin, allylsulfonic acid or their alkali metal or ammonium salts, vinylsulfonic acid or their alkali metal or ammonium salts, bisbenzenesulfonylimide or commercially available brighteners based on a thio compound.
Die verwendeten wäßrig-sauren Nickelelektrolyt-Bäder enthalten ein oder meist mehrere Nickelsalze, z.B. Nickelsulfat und Nik- kelchlorid, eine oder mehrere anorganische Säuren, vorzugsweise Borsäure und Schwefelsäure, als Glanzmittel die Mischung aus den Komponenten A und B allein oder in Kombination mit weiteren übli-
chen Glanzmitteln sowie gegebenenfalls weitere übliche Hilfsmit¬ tel und Zusätze in den hierfür üblichen Konzentrationen, z.B. Netzmittel und Porenverhütungsmittel. Gebräuchlich wäßrig-saύre Nickelelektrolyte ("Watts-Elektrolyte") haben die folgende Grund- Zusammensetzung:The aqueous-acidic nickel electrolyte baths contain one or usually more nickel salts, for example nickel sulfate and nickel chloride, one or more inorganic acids, preferably boric acid and sulfuric acid, as a brightening agent, the mixture of components A and B alone or in combination with other usual - Chen gloss agents and, if appropriate, other conventional auxiliaries and additives in the concentrations customary for this, for example wetting agents and pore-preventing agents. Commonly aqueous acidic nickel electrolytes ("Watts electrolytes") have the following basic composition:
200 bis 350 g/1 NiS04 • 7 H20 30 bis 150 g/1 NiCl2 • 6 H20 30 bis 50 g/1 H3BO3.200 to 350 g / 1 NiS0 4 • 7 H 2 0 30 to 150 g / 1 NiCl 2 • 6 H 2 0 30 to 50 g / 1 H 3 BO 3 .
Der pH-Wert der Elektrolyt-Bäder liegt üblicherweise zwischen 3 und 6, vorzugsweise zwischen 4 und 5. Zur Einstellung dieses pH- Wertes dient zweckmäßigerweise eine starke Mineralsäure, vorzugs¬ weise Schwefelsäure.The pH of the electrolyte baths is usually between 3 and 6, preferably between 4 and 5. A strong mineral acid, preferably sulfuric acid, is expediently used to set this pH.
Die Mischung aus den Komponenten A und B liegt in den Elektrolyt- Bädern in niedrigen Konzentrationen, in der Regel zwischen 0,05 und 1,0 g/1, vorzugsweise zwischen 0,1 und 0,5 g/1, vor. Die Kon¬ zentrationen weiterer üblicher Glanzmittel liegen normalerweise im Bereich von jeweils 0,1 bis 10 g/1, insbesondere 0,1 bis 2,0 g/1.The mixture of components A and B is present in the electrolyte baths in low concentrations, generally between 0.05 and 1.0 g / 1, preferably between 0.1 and 0.5 g / 1. The concentrations of other customary brighteners are normally in the range from 0.1 to 10 g / 1, in particular 0.1 to 2.0 g / 1.
Mit den beschriebenen Nickelelektrolyt-Bädern können vor allem Nickelüberzüge auf Formteilen aus Stahl, daneben aber auch auf Formteilen aus anderen Materialien, beispielsweise Messing, die wie üblich vorbehandelt worden sind, galvanisch erzeugt werden. Hierzu arbeitet man in der Regel bei Temperaturen von 30 bis 80°C, vorzugsweise 40 bis 60°C.The nickel electrolyte baths described above can be used to produce nickel coatings on molded parts made of steel, but also on molded parts made of other materials, for example brass, which have been pretreated as usual. This is usually done at temperatures of 30 to 80 ° C, preferably 40 to 60 ° C.
Gegenstand der vorliegenden Erfindung ist weiterhin eine Glanz¬ mittelmischung für wäßrig-saure galvanische Bäder zur Abscheidung von Nickel, enthaltend eine Mischung ausThe present invention furthermore relates to a mixture of brighteners for aqueous-acidic galvanic baths for the deposition of nickel, comprising a mixture of
A) 2 bis 98 Gew.-% einer oder mehrerer cyclischer N-Allyl- oder N-Vinylammoniumverbindungen der allgemeinen Formel IA) 2 to 98% by weight of one or more cyclic N-allyl or N-vinylammonium compounds of the general formula I.
in der das N-Atom Bestandteil eines Pyridin-, Chinolin- oder Isochinolin-Ringsystems ist, welches zusätzlich ein oder zwei Ci- bis C -Alkylsubstituenten oder Halogenatome tragen kann, in which the N atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two Ci to C alkyl substituents or halogen atoms,
R1' R3 und R4 für Wasserstoff oder Cι~ bis C4-Alkyl stehen, R2 Wasserstoff oder Methyl bedeutet.
m für eine Zahl von 0 bis 4 steht, n für eine Zahl von 1 bis 4 steht und xP ein n-wertiges anorganisches oder organisches Anion, wel- ches die Wasserlöslichkeit fördert, bezeichnet, undR 1 'R 3 and R 4 are hydrogen or -C ~ to C 4 alkyl, R 2 is hydrogen or methyl. m stands for a number from 0 to 4, n stands for a number from 1 to 4 and xP denotes an n-valent inorganic or organic anion which promotes water solubility, and
B) 98 bis 2 Gew.-% einer oder mehrerer acetylenisch ungesättig¬ ter Verbindungen der allgemeinen Formel IIB) 98 to 2% by weight of one or more acetylenically unsaturated compounds of the general formula II
R4 c Έ_B C R5 (II)R4 c Έ_B CR 5 (II)
in der die Reste R4 und R5 gleich oder verschieden sind und durch Hydroxyl, Sulfo, Amino, Ci- bis C4-Alkylamino oder Di(Cι~ bis C4-alkyl)amino substituiertes Cι~ bis C4-Alkyl be- zeichnen, wobei Hydroxylgruppen mit 1 bis 10 mol einesin which the radicals R 4 and R 5 are identical or different and are substituted by hydroxyl, sulfo, amino, C 1 -C 4 -alkylamino or di (C 1 -C 4 -alkyl) amino-substituted C 1 -C 4 -alkyl draw, with hydroxyl groups with 1 to 10 mol of one
C2- bis C4-Alkylenoxids oder einer Mischung solcher Alkyleno- xide umgesetzt sein können und einer der Reste R4 oder R5 auch Wasserstoff oder Cι~ bis C4-Alkyl sein kann.C 2 - to C 4 -alkylene oxide or a mixture of such alkylene oxides can be reacted and one of the radicals R 4 or R 5 can also be hydrogen or C 1 -C 4 -alkyl.
Die erfindungsgemäße Glanzmittelmischung zeichnet sich durch eine außerordentlich hohe Glanzbildung aus. Man erreicht mit ihr in der Regel einen stärkeren Glanz und eine bessere Einebnung als mit den üblichen Glanzbildnern bei deutlich niedrigerer Dosierung in den Nickelelektrolyt-Bädern.The mixture of gloss agents according to the invention is distinguished by an extraordinarily high gloss formation. As a rule, it achieves a stronger shine and a better leveling than with the usual brighteners at a significantly lower dosage in the nickel electrolyte baths.
AnwendungsbeispieleExamples of use
Die in der folgenden Tabelle als Beispiele 1 bis 11 aufgeführten Mischungen wurden als Glanzmittel in schwach sauren galvanischen Bädern zur Abscheidung von Nickel eingesetzt.The mixtures listed in the following table as Examples 1 to 11 were used as brighteners in weakly acidic galvanic baths for the deposition of nickel.
Der dabei verwendete wäßrige Nickelelektrolyt hatte folgende Zu¬ sammensetzung:The aqueous nickel electrolyte used had the following composition:
300 g/1 NiS04 • 7 H20 60 g/1 NiCl2 • 6 H0 45 g/1 H3BO3 0,5 g/1 eines Fettalkoholderivates der Formel300 g / 1 NiS0 4 • 7 H 2 0 60 g / 1 NiCl 2 • 6 H0 45 g / 1 H 3 BO 3 0.5 g / 1 of a fatty alcohol derivative of the formula
Ci2H25 Ci4H29-0-(CH2CH2θ)2-S03Na als NetzmittelCi 2 H 25 Ci 4 H 29 -0- (CH 2 CH 2 θ) 2 -S0 3 Na as wetting agent
Die jeweiligen Konzentrationen an Glanzbildnern sind in der fol¬ genden Tabelle angegeben.The respective concentrations of brighteners are given in the table below.
Der pH-Wert des Elektrolyten wurde mit Schwefelsäure auf 4,2 ein- gestellt.
Es wurden Messingbleche verwendet, die vor der Beschichtung mit Nickel in einem alkalischen Elektrolyten nach den üblichen Metho¬ den kathodisch entfettet wurden. Die Nickelabscheidung erfolgte in einer 250 ml-Hull-Zelle bei 55°C und einer Stromstärke von 2A während eines Zeitraums von 10 Minuten. Anschließend wurden die Bleche mit Wasser gespült und mit Preßluft getrocknet.The pH of the electrolyte was adjusted to 4.2 with sulfuric acid. Brass sheets were used, which were degreased cathodically in an alkaline electrolyte according to the usual methods before the coating with nickel. The nickel deposition was carried out in a 250 ml Hull cell at 55 ° C. and a current of 2A over a period of 10 minutes. The sheets were then rinsed with water and dried with compressed air.
Die folgende Tabelle zeigt die Ergebnisse dieser Versuche. Man erkennt, daß mit der erfindungsgemäßen Glanzmittelmischung ein stärkerer Glanz und eine bessere Einebnung erzielt wurde als mit den Glanzbildnern des Standes der Techni, und das zum Teil bei deutlich niedrigerer Dosierung in den Nickelelektrolyt-Bädern.
The following table shows the results of these tests. It can be seen that a greater gloss and a better leveling were achieved with the gloss agent mixture according to the invention than with the gloss agents of the prior art, and in some cases with a significantly lower dosage in the nickel electrolyte baths.
Tabelletable
Prüfergebnisse der galvanischen NickelabscheidungTest results of galvanic nickel deposition
Die Vergleichsmischungen A und B sind aus der Literaturstelle (3) bekannt.Comparative mixtures A and B are known from reference (3).
BenotungsSchema für den Glanz:Grading scheme for the shine:
5 * hervorragend (perfekter Spiegelglanz)5 * excellent (perfect mirror gloss)
4 - gut (nahezu Spiegelglanz)4 - good (almost mirror finish)
3 « mäßig3 «moderate
2 = schlecht2 = bad
1 = kein Glanz1 = no shine
BenotungsSchema für die Einebnung: 2 - hoch 1 * mittel 0 = mäßig
Grading scheme for leveling: 2 - high 1 * medium 0 = moderate
Claims
Verfahren zur Herstellung vernickelter Formteile durch galva¬ nisches Abscheiden von Nickel aus wäßrig-sauren Bädern, die als wesentliche Bestandteile ein oder mehrere Nickelsalze, eine oder mehrere anorganische Säuren und mindestens zwei Glanzmittel enthalten, dadurch gekennzeichnet, daß man als Glanzmittel eine Mischung ausProcess for the production of nickel-plated moldings by galvanic deposition of nickel from aqueous acid baths which contain as essential components one or more nickel salts, one or more inorganic acids and at least two brighteners, characterized in that a mixture of
A) 2 bis 98 Gew.-% einer oder mehrerer cyclischer N-Al¬ lyl- oder N-Vinylammoniumverbindungen der allgemeinen Formel IA) 2 to 98% by weight of one or more cyclic N-alkyl or N-vinylammonium compounds of the general formula I.
in der das N-Atom Bestandteil eines Pyridin-, Chino- lin- oder Isochinolin-Ringsystems ist, welches zusätzlich ein oder zwei Cι~ bis C4-Alkylsubstituenten oder Haloge¬ natome tragen kann,in which the N atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two C 1 -C 4 -alkyl substituents or halogen atoms,
R1, R3 und R4 für Wasserstoff oder Ci- bis C -Alkyl ste¬ hen,R 1 , R 3 and R 4 represent hydrogen or C 1 -C 4 -alkyl,
R2 Wasserstoff oder Methyl bedeutet, m für eine Zahl von 0 bis 4 steht, n für eine Zahl von 1 bis 4 steht und ® ein n-wertiges anorganisches oder organisches Anion, welches die Wasserlöslichkeit fördert, bezeichnet, undR 2 is hydrogen or methyl, m is a number from 0 to 4, n is a number from 1 to 4 and ® denotes an n-valent inorganic or organic anion which promotes water solubility, and
B) 98 bis 2 Gew.-% einer oder mehrerer acetylenisch ungesät¬ tigter Verbindungen der allgemeinen Formel IIB) 98 to 2% by weight of one or more acetylenically unsaturated compounds of the general formula II
R4 C R5 (II)R4 C R5 (II)
in der die Reste R4 und R5 gleich oder verschieden sind und durch Hydroxyl, Sulfo, Amino, Ci- bis C4-Alkyland.n0 oder Di(Cι~ bis C4-alkyl)amino substituiertes Cι~ bis C4-Alkyl bezeichnen, wobei Hydroxylgruppen mit 1 bis 10 mol eines C2- bis C4-Alkylenoxids oder einer Mischung solcher Alkylenoxide umgesetzt sein können und einer der Reste R4 oder R5 auch Wasserstoff oder Ci- bis C4-Alkyl sein kann,in which the radicals R 4 and R 5 are the same or different and are substituted by hydroxyl, sulfo, amino, Ci- to C 4 -Alkyl.n0 or di (C 1 -C 4 -alkyl) amino C 1 -C 4 -alkyl denote where hydroxyl groups can be reacted with 1 to 10 mol of a C 2 - to C 4 -alkylene oxide or a mixture of such alkylene oxides and one of the R 4 or R 5 may also be hydrogen or C 1 -C 4 -alkyl,
einsetzt.starts.
2. Verfahren zur Herstellung vernickelter Formteile nach An¬ spruch 1, dadurch gekennzeichnet, daß man als Komponente A cyclische N-Allylammoniumverbindungen der allgemeinen For¬ mel Ia2. Process for the production of nickel-plated moldings according to claim 1, characterized in that cyclic N-allylammonium compounds of the general formula Ia are used as component A.
in der R2, n und x die oben genannten Bedeutungen haben, einsetzt.in which R 2 , n and x have the meanings given above.
3. Verfahren zur Herstellung vernickelter Formteile nach An¬ spruch 1 oder 2, dadurch gekennzeichnet, daß man als Kompo¬ nente B acetylenisch ungesättigte Verbindungen II einsetzt, bei denen die Reste R4 und R5 gleich oder verschieden sind und durch Hydroxyl, Sulfo oder Dimethyl- oder Diethylamino sub- stituiertes Methyl oder Ethyl bezeichnen, wobei Hydroxylgrup¬ pen mit 1 bis 3 mol eines C2- bis C4-Alkylenoxids oder einer Mischung solcher Alkylenoxide umgesetzt sein können und einer der Reste R4 oder R5 auch Wasserstoff, Methyl oder Ethyl sein kann.3. A process for the production of nickel-plated moldings according to claim 1 or 2, characterized in that acetylenically unsaturated compounds II are used as component B in which the radicals R 4 and R 5 are identical or different and are substituted by hydroxyl, sulfo or Denote dimethyl- or diethylamino-substituted methyl or ethyl, where hydroxyl groups can be reacted with 1 to 3 mol of a C 2 -C 4 -alkylene oxide or a mixture of such alkylene oxides and one of the radicals R 4 or R 5 may also be hydrogen, Can be methyl or ethyl.
4. Verfahren zur Herstellung vernickelter Formteile nach den An¬ sprüchen 1 bis 3, dadurch gekennzeichnet, daß man eine Mi¬ schung aus einer oder mehreren cyclischen N-Allyl- oder N-Vi- nylammoniumverbindungen I als Komponente A und mindestens drei acetylenisch ungesättigten Verbindungen II als Komponen¬ te B einsetzt.4. Process for the production of nickel-plated molded parts according to claims 1 to 3, characterized in that a mixture of one or more cyclic N-allyl or N-vinylammonium compounds I as component A and at least three acetylenically unsaturated compounds II used as component B.
Glanzmittelmischung für wäßrig-saure galvanische Bäder zur Abscheidung von Nickel, enthaltend eine Mischung ausBrightener mixture for aqueous acidic galvanic baths for the deposition of nickel, containing a mixture of
A) 2 bis 98 Gew.-% einer oder mehrerer cyclischer N-Al¬ lyl- oder N-Vinylammoniumverbindungen der allgemeinen Formel I A) 2 to 98% by weight of one or more cyclic N-alkyl or N-vinylammonium compounds of the general formula I.
in der das N-Atom Bestandteil eines Pyridin-, Chino- lin- oder Isochinolin-Ringsystems ist, welches zusätzlich ein oder zwei Cι~ bis C4-Alkylsubstituenten oder Haloge¬ natome tragen kann,in which the N atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two C 1 -C 4 -alkyl substituents or halogen atoms,
R1' R3 und R4 für Wasserstoff oder Cι~ bis C4-Alkyl ste¬ hen,R 1 'R 3 and R 4 stand for hydrogen or C 1 -C 4 -alkyl,
R2 Wasserstoff oder Methyl bedeutet, m für eine Zahl von 0 bis 4 steht, n für eine Zahl von 1 bis 4 steht undR 2 is hydrogen or methyl, m is a number from 0 to 4, n is a number from 1 to 4 and
X® ein n-wertiges anorganisches oder organisches Anion, welches die Wasserlöslichkeit fördert, bezeichnet, undX ® denotes an n-valent inorganic or organic anion which promotes water solubility, and
B) 98 bis 2 Gew.-% einer oder mehrerer acetylenisch ungesät¬ tigter Verbindungen der allgemeinen Formel IIB) 98 to 2% by weight of one or more acetylenically unsaturated compounds of the general formula II
R4 C ≡ C" R5 (II) in der die Reste R4 und R5 gleich oder verschieden sind und durch Hydroxyl, Sulfo, Amino, Cι~ bis C4-Alkyla1ru.no oder Di(Cι~ bis C4-alkyl)amino substituiertes Ci- bis C4-Alkyl bezeichnen, wobei Hydroxylgruppen mit 1 bis 10 mol eines C2- bis C4-Alkylenoxids oder einer Mischung solcher Alkylenoxide umgesetzt sein können und einer der Reste R4 oder R5 auch Wasserstoff oder Ci- bis C4~Alkyl sein kann,R4 C ≡ C "R5 (II) in which the radicals R 4 and R 5 are the same or different and are hydroxyl, sulfo, amino, Cι ~ to C 4 -Alkyla1ru.no or di (Cι ~ to C 4 -alkyl) denote amino substituted C 1 -C 4 -alkyl, where hydroxyl groups can be reacted with 1 to 10 mol of a C 2 -C 4 -alkylene oxide or a mixture of such alkylene oxides and one of the radicals R 4 or R 5 may also be hydrogen or Ci-bis C 4 ~ alkyl can be
einsetz , insert,
Applications Claiming Priority (3)
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|---|---|---|---|
| DE4202003 | 1992-01-25 | ||
| DE4202003 | 1992-01-25 | ||
| PCT/EP1993/000063 WO1993015241A1 (en) | 1992-01-25 | 1993-01-14 | Process for producing nickel-plated mouldings |
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| EP0621908B1 EP0621908B1 (en) | 1995-09-06 |
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| US (1) | US5445727A (en) |
| EP (1) | EP0621908B1 (en) |
| JP (1) | JPH07503282A (en) |
| AT (1) | ATE127541T1 (en) |
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| WO2004072320A2 (en) * | 2003-02-07 | 2004-08-26 | Pavco, Inc. | Use of n-allyl substituted amines and their salts as brightening agents in nickel plating baths |
| DE102005011708B3 (en) | 2005-03-11 | 2007-03-01 | Atotech Deutschland Gmbh | A polyvinylammonium compound and process for the production thereof, and an acidic solution containing the compound and a process for electrolytically depositing a copper precipitate |
| 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 |
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|---|---|---|---|---|
| US2647866A (en) * | 1950-07-17 | 1953-08-04 | Udylite Corp | Electroplating of nickel |
| DE1191652B (en) * | 1963-05-15 | 1965-04-22 | Dehydag Gmbh | Acid galvanic nickel bath |
| GB1192036A (en) * | 1966-10-18 | 1970-05-13 | M & T Chemicals Inc | Improvements in or relating to Nickel Electroplating |
| DE1496832C3 (en) * | 1966-11-26 | 1978-04-06 | Henkel Kgaa, 4000 Duesseldorf | Acid galvanic nickel bath |
| US3758389A (en) * | 1971-11-30 | 1973-09-11 | Okuno Chem Ind Co | Process for nickel and chromium plating |
| US3862019A (en) * | 1974-04-26 | 1975-01-21 | R O Hull & Company Inc | Composition of electroplating bath for the electrodeposition of bright nickel |
| FR2292057A1 (en) * | 1974-11-20 | 1976-06-18 | Popescu Francine | Bright nickel electroplating bath - contg. pyridinium cpd. as primary brightener for level ductile deposits |
-
1993
- 1993-01-14 AT AT93902188T patent/ATE127541T1/en not_active IP Right Cessation
- 1993-01-14 EP EP93902188A patent/EP0621908B1/en not_active Expired - Lifetime
- 1993-01-14 US US08/256,374 patent/US5445727A/en not_active Expired - Fee Related
- 1993-01-14 ES ES93902188T patent/ES2076056T3/en not_active Expired - Lifetime
- 1993-01-14 DE DE59300569T patent/DE59300569D1/en not_active Expired - Lifetime
- 1993-01-14 CA CA002128022A patent/CA2128022A1/en not_active Abandoned
- 1993-01-14 WO PCT/EP1993/000063 patent/WO1993015241A1/en active IP Right Grant
- 1993-01-14 JP JP5512888A patent/JPH07503282A/en active Pending
-
1995
- 1995-09-27 GR GR950402652T patent/GR3017532T3/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9315241A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2128022A1 (en) | 1993-08-05 |
| US5445727A (en) | 1995-08-29 |
| DE59300569D1 (en) | 1995-10-12 |
| ATE127541T1 (en) | 1995-09-15 |
| WO1993015241A1 (en) | 1993-08-05 |
| ES2076056T3 (en) | 1995-10-16 |
| JPH07503282A (en) | 1995-04-06 |
| EP0621908B1 (en) | 1995-09-06 |
| GR3017532T3 (en) | 1995-12-31 |
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