DE1496908C3 - Galvanic nickel bath. Note »M&T Chemicals Inc., New York, N.Y. (V.StA.) - Google Patents

Galvanic nickel bath. Note »M&T Chemicals Inc., New York, N.Y. (V.StA.)

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Publication number
DE1496908C3
DE1496908C3 DE1496908A DE1496908A DE1496908C3 DE 1496908 C3 DE1496908 C3 DE 1496908C3 DE 1496908 A DE1496908 A DE 1496908A DE 1496908 A DE1496908 A DE 1496908A DE 1496908 C3 DE1496908 C3 DE 1496908C3
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Prior art keywords
propargylpyridinium
nickel
brighteners
bath
bromide
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DE1496908A
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DE1496908A1 (en
DE1496908B2 (en
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Frank Detroit Mich. Passal (V.St.A.)
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M&T Chemicals Inc
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79Acids; Esters
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79Acids; Esters
    • C07D213/80Acids; Esters in position 3
    • CCHEMISTRY; METALLURGY
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    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81Amides; Imides
    • C07D213/82Amides; Imides in position 3
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/12Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/12Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18Heterocyclic compounds

Description

N-C-C=CH
H2
NCC = CH
H 2

IOIO

in der A und B Wasserstoff, Carbonsäureamid-, Acetyl- oder Carbomethoxygruppen und X ein Halogen bedeutet und mindestens eines von A und B verschieden von Wasserstoff ist, in einer Menge von 0,005 bis 0,1 g/l enthält.in which A and B are hydrogen, carboxamide, acetyl or carbomethoxy groups and X is Is halogen and at least one of A and B is different from hydrogen, in one Contains amount from 0.005 to 0.1 g / l.

2. Bad nach Anspruch 1, dadurch gekennzeichnet, daß es als N-Propargylpyridiniumsalz 3-Carbonsäureamid - N - propargylpyridiniumbromid, 4 - Carbonsäureamid - N - propargylpyridiniumbromid, 3 - Carbomethoxy - N - propargylpyridiniumbromid, 4 - Carbomethoxy - N - propargylpyridiniumbromid, 4 - Acetyl - N - propargylpyridiniumbromid bzw. 3-Acetyl-N-propargylpyridiniumbromid enthält.2. Bath according to claim 1, characterized in that it is 3-carboxamide as the N-propargylpyridinium salt - N - propargylpyridinium bromide, 4 - carboxamide - N - propargylpyridinium bromide, 3 - carbomethoxy - N - propargylpyridinium bromide, 4 - carbomethoxy - N - propargylpyridinium bromide, 4 - acetyl - N - propargylpyridinium bromide or 3-acetyl-N-propargylpyridinium bromide contains.

3-Sulfo-N-propargyl-pyridmium-bromid vorgeschlagen. Es hat sich jedoch gezeigt, daß der Glanzeffekt dieser Verbindung verhältnismäßig gering ist. Aus diesem Grunde müssen sehr große Mengen dieser Verbindung verwendet werden. Dies ist nicht nur vom wirtschaftlichen Standpunkt aus unerwünscht, sondern führt auch dazu, daß das Bad schnell mit organischen Zersetzungsprodukten verunreinigt wird.3-sulfo-N-propargyl-pyridmium-bromide suggested. However, it has been shown that the gloss effect of this compound is relatively small. Out for this reason, very large amounts of this compound must be used. This is not just dated from an economic point of view undesirable, but also leads to the fact that the bath quickly with organic Decomposition products is contaminated.

Es wurde nunmehr gefunden, daß die obenerwähnten Nachteile dadurch beseitigt werden können, wenn man als primäres Glanzmittel ein spezielles N-Propargylpyridiniumsalz verwendetIt has now been found that the above-mentioned disadvantages can be eliminated if a special N-propargylpyridinium salt is used as the primary brightener

So wird also gemäß der Erfindung ein galvanische N-Propargylpyridiniumsalze als Glanzbildner und sekundäre Glanzmittel enthaltendes Nickelbad vorgeschlagen, das dadurch gekennzeichnet ist, daß das Bad ein N-Propargylpyridiniumsalz der allgemeinen FormelThus, according to the invention, a galvanic Suggested nickel bath containing N-propargylpyridinium salts as brighteners and secondary brighteners, which is characterized in that the bath is an N-propargylpyridinium salt of the general formula

3535

Die Erfindung bezieht sich auf ein galvanisches Nickelbad. Wenn man auf galvanischem Wege Nickelüberzüge herstellen will, dann muß man den Bädern sogenanntes Glanzmittel zusetzen. Man unterscheidet primäre Glanzmittel, die in sehr geringen Konzentrationen von beispielsweise 0,002 bis 0,2 g/l verwendet werden, und sekundäre Glanzmittel, welches beispielsweise in einer Konzentration von 1 bis 30 g/l verwendet werden. Die richtige Kombination dieser Materialien ergibt spiegelglänzende überzüge, wobei unter Umständen auch ein Einebnungseffekt zu verzeichnen ist. ' ' iThe invention relates to a galvanic nickel bath. If you have nickel plating by electroplating want to produce, then you have to add so-called brighteners to the baths. One distinguishes primary brighteners used in very low concentrations of, for example, 0.002 to 0.2 g / l and secondary brighteners, which can be used, for example, in a concentration of 1 to 30 g / l be used. The right combination of these materials results in mirror-like coatings, whereby under certain circumstances a leveling effect can also be recorded. '' i

Es sind bereits Verschiedene Glanznickelsysteme, die aus einer Kombination aus einem primären Glanzmittel und einem sekundären Glanzmittel bestehen, bekannt.There are already various bright nickel systems that consist of a combination of a primary brightening agent and a secondary brightener are known.

So ist in der deutschen Auslegeschrift 1 066 068 ein Glanznickelbad beschrieben, welches neben einem sekundären Glanzmittel, üblicherweise aromatische Sulfonsäuren, als primäres Glanzmittel ein Pyridiniumsalz enthält, das am Stickstoffatom durch eine Kette mit einer dreifachen Umsättigung substituiert ist und am Kern bis zu drei Halogenatome oder Sulfonsäuregruppen enthalten kann. Ein Beispiel für ein solches primäres Glanzmittel ist N-2-Propinpyridin-bromid. Ein Nachteil der mit solchen Bädern hergestellten Nickelüberzüge besteht darin, daß die Nickelüberzüge einen stark irisierenden Schleier innerhalb eines großen Stromdichtebereichs, der üblicherweise für die galvanische Abscheidung verwendet wird, zeigt.Thus, in the German Auslegeschrift 1 066 068, a bright nickel bath is described, which in addition to a secondary brighteners, usually aromatic sulfonic acids, as the primary brightener a pyridinium salt contains, which is substituted on the nitrogen atom by a chain with a triple unsaturation and can contain up to three halogen atoms or sulfonic acid groups on the core. An example one such primary brightener is N-2-propyne pyridine bromide. A disadvantage of the nickel coatings produced with such baths is that the Nickel coatings create a highly iridescent haze within a wide range of current densities that are commonly found used for electrodeposition shows.

Ähnliche Bäder sind aus der USA.-Patentschrift 3 006 822 bekannt. Als primäres Glanzmittel wird dortSimilar baths are known from U.S. Patent 3,006,822. As the primary brightener there is

N-C-C=CH
H2
NCC = CH
H 2

in der A und B Wasserstoff, Carbonsäureamid-, Acetyl- oder Carbomethoxygruppen und X ein Halogen bedeutet und mindestens eines von A und B verschieden von Wasserstoff ist, in einer Menge von 0,005 bis 0,IgA enthält.in which A and B are hydrogen, carboxamide, acetyl or carbomethoxy groups and X is a halogen and at least one of A and B is other than hydrogen, in an amount of 0.005 to 0, contains IgA.

Die erfindungsgemäßen Nickelbäder ergeben brillante Nickelabscheidungen mit einer vorzüglichen Duktilität und einer guten Glanzentwicklung im Bereich niedriger Stromdichte. Außerdem ist die Einebnungsgeschwindigkeit sehr hoch. Ein wesentlicher Vorteil der erfindungsgemäßen Bäder ist, daß die Glanzmittel innerhalb verhältnismäßig großer Konzentrationen enthalten sein können, so daß eine genaue Kontrolle der Konzentrationen der Glanzmittel im Bad nicht nötig ist.The nickel baths according to the invention produce brilliant nickel deposits with an excellent one Ductility and good gloss development in the area of low current density. In addition, the leveling speed is very high. A major advantage of the baths according to the invention is that the brighteners can be used within relatively large concentrations may be included, so that a precise control of the concentrations of the brighteners in the Bath is not necessary.

Ein anderer Vorteil liegt darin, daß die im erfindungsgemäßen Bad enthaltenen Glanzmittel auch bei langer Elektrolyse keine schädlichen Zersetzungsprodukte bilden. Another advantage is that the brighteners contained in the bath according to the invention are also included do not form harmful decomposition products for long periods of electrolysis.

Die primären Glanzmittel sind in einer Konzentration von 0,005 bis 0,10 g/l enthalten. Die jweils gewählte Konzentration hängt von der Badtype und auch von anderen Faktoren, wie z. B. Konzentration der Nickelsalze, den Arbeitsbedingungen, dem gewünschten Glanzgrad und dem gewünschten Einebnungsgrad ab. Konzentrationen zwischen 0,01 und 0,05 g/l werden bevorzugt verwendet.The primary brighteners are contained in a concentration of 0.005 to 0.10 g / l. The each The concentration chosen depends on the type of bath and other factors, such as B. Concentration the nickel salts, the working conditions, the desired degree of gloss and the desired level of flattening away. Concentrations between 0.01 and 0.05 g / l are preferred.

Typische Verbindungen, welche als primäre Glanzmittel wirksam sind, sind die folgenden:Typical compounds that are effective as primary brighteners are the following:

Tabelle ITable I.

A. 3-Carbonsäureamid-N-propargylpyridiniumbromid, A. 3-carboxamide-N-propargylpyridinium bromide,

B. 3-Acety 1-N-propargylpyridiniumbromid,B. 3-Acety 1-N-propargylpyridinium bromide,

C. 3-Carbomethoxy-N-propargylpyridiniumbromid, C. 3-carbomethoxy-N-propargylpyridinium bromide,

D. 4-Carbonsäureamid-N-propargylpyridiniumbromid, D. 4-carboxamide-N-propargylpyridinium bromide,

E. 4-Acetyl-N-propargylpyridiniumbromid,E. 4-acetyl-N-propargylpyridinium bromide,

F. 4-Carbomethoxy-N-propargylpyridiniumbromid.F. 4-Carbomethoxy-N-propargylpyridinium bromide.

Sekundäre Glanzmittel, die beispielsweise in einer , Menge von 1 bis 75 g/l, vorzugsweise 1 bis 20 g/l verwendet werden, sind im allgemeinen aromatische Sulfonate, Sulfonamide und Sulfimide. Spezielle Beispiele hierfür sind aromatische Verbindungen wie 1,3,6-Naphthalintrisulfonat, das Natrium- bzw. Kaliumsalz von Saccharin, das Natrium- oder Kaliumsalz von o-Sulfobenzaldehyd, Benzolsulfonamid, Benzolmonosulfonate usw. Für stark chloridhaltige Bäder wurden bevorzugt Sulfonierungsprodukte von Diphenyl verwendet.Secondary brighteners, used for example in an amount of 1 to 75 g / l, preferably 1 to 20 g / l are generally aromatic sulfonates, sulfonamides, and sulfimides. Specific examples this includes aromatic compounds such as 1,3,6-naphthalene trisulfonate, the sodium or potassium salt of saccharin, the sodium or potassium salt of o-sulfobenzaldehyde, benzenesulfonamide, benzene monosulfonates etc. For baths with a high chloride content, sulfonation products of diphenyl are preferred used.

_ Es können zusätzlich auch sekundäre Hilfsglanzmittel anwesend sein, z. B. das Natriumsalz der 2-Propen-1-sulfonsäure, das Natriumsalz der 3-Chloro-2-buten-l-sulfonsäure, die gemischten Isomere des Natriumsalzes von 2-Buten-2-hydroxy- 1-sulfonsäure und des Natriumsalzes von 2-Buten-l-hydroxy-2-sulfonsäure, oder Phenyl-propiolamid._ Secondary auxiliary gloss agents can also be used be present, e.g. B. the sodium salt of 2-propene-1-sulfonic acid, the sodium salt of 3-chloro-2-butene-l-sulfonic acid, the mixed isomers of the sodium salt of 2-butene-2-hydroxy-1-sulfonic acid and the sodium salt of 2-butene-1-hydroxy-2-sulfonic acid, or phenyl propiolamide.

Typische Watts-Bäder und stark chloridhaltige Bäder sind in den Tabellen II und III zusammengestellt. Typical Watts baths and baths with a high chloride content are listed in Tables II and III.

welche in den Beispielen verwendet wurden, sind in der folgenden Tabelle IV zusammengestellt.which were used in the examples are listed in Table IV below.

Tabelle IVTable IV

Sekundäre GlanzmittelSecondary brighteners

G. o-Benzoesäuresulfimid (Natriumsalz), H. Dibenzolsulfonamidj ίο I. N,N'-Bis-(phenylsulfonyl)-4,4'-diphenyl-G. o-Benzoic acid sulfimide (sodium salt), H. Dibenzenesulfonamidj ίο I. N, N'-bis- (phenylsulfonyl) -4,4'-diphenyl-

disulfonamid,
J. sulfoniertes Dibenzthiophendioxyd.
disulfonamide,
J. sulfonated dibenzothiophene dioxide.

Die sekundären Hilfsglanzmittel, welche in den Beispielen verwendet wurden, sind in der folgenden Tabelle V zusammengestellt.The secondary auxiliary gloss agents, which in the examples are listed in Table V below.

2020th

TabellenTables

Watts-BäderWatts baths

2525th

Nickelsulfat 200 bis 400 g/lNickel sulfate 200 to 400 g / l

Nickelchlorid 30 bis 75 g/lNickel chloride 30 to 75 g / l

Borsäure 30 bis 50 g/lBoric acid 30 to 50 g / l

Temperatur 38 bis 65° CTemperature 38 to 65 ° C

. Bewegung mechanisch .. Mechanical movement.

und/oder Luft
oder Pumpen der Lösung usw.
and / or air
or pumping the solution, etc.

pH-Wert 2,5 bis 4,5pH 2.5 to 4.5

elektrometrischelectrometric

Tabelle III
Stark chloridhaltige Bäder
Table III
Baths with a lot of chloride

Nickelchlorid 150 bis 300 g/lNickel chloride 150 to 300 g / l

Nickelsulfat 40 bis 150 g/lNickel sulfate 40 to 150 g / l

Borsäure 30 bis 50 g/lBoric acid 30 to 50 g / l

Temperatur 38 bis 65° CTemperature 38 to 65 ° C

Bewegung mechanischMechanical movement

und/oder Luft oder Pumpen der Lösung usw.and / or air or pumping the solution, etc.

pH-Wert 2,5 bis 4,5pH 2.5 to 4.5

elektrometrischelectrometric

Die Erfindung wird an Hand der folgenden Beispiele näher erläutert. In jedem der Beispiele wurde ein Nickelbad mit den angegebenen Komponenten hergestellt. Während der Abscheidung wurden die Bäder bewegt. In allen Beispielen wurden glänzende galvanisehe überzüge erhalten.The invention is explained in more detail with reference to the following examples. In each of the examples there was a Nickel bath made with the specified components. During the deposition, the baths were emotional. In all examples, shiny electroplated coatings were obtained.

Beispiele 1 bis 14Examples 1 to 14

In den Beispielen 1 bis 14 einschließlich wurde das folgende Standardbad als Grundlösung verwendet:In Examples 1 to 14 inclusive, the following standard bath was used as the base solution:

Nickelsulfat 300 g/lNickel sulfate 300 g / l

. Nickelchlorid 60 g/l. Nickel chloride 60 g / l

Borsäure 45 g/lBoric acid 45 g / l

Natriumlaurylsulfat 0,25 g/lSodium Lauryl Sulphate 0.25 g / l

Bezüglich der chemischen Bezeichnungen der primären Glanzmittel wird auf die weiter oben stehende Tabelle I hingewiesen. Die sekundären Glanzmittel,Regarding the chemical names of the primary brighteners, see above Table I noted. The secondary brighteners,

Tabelle VTable V

Sekundäre HilfsglanzmittelSecondary auxiliary gloss agents

K. Natriumsalz der 3-Chlor-2-buten-l-sulfonsäure, L. Natriumsalz der Allylsulfonsäure.K. sodium salt of 3-chloro-2-butene-1-sulfonic acid, L. sodium salt of allylsulfonic acid.

Tabelle VITable VI

Beispielexample Zusätzeadditions Mengecrowd StromdichteCurrent density Temperaturtemperature Nr.No. in g/lin g / l in A/dm2 in A / dm 2 in 0Cin 0 C 11 AA. 0,0200.020 44th 6060 GG 2,02.0 KK 3,03.0 22 BB. 0,0200.020 44th 6060 GG 2,02.0 KK 3,03.0 33 CC. 0,0200.020 44th ■ 60■ 60 GG 2,02.0 KK 3,03.0 44th DD. 0,0300.030 44th 6060 GG 4,04.0 KK 4,04.0 55 . E. E. 0,0200.020 44th 6060 GG 2,02.0 KK 3,03.0 66th FF. 0,0200.020 55 5050 GG 2,02.0 KK 3,03.0 7.7th A ■A ■ 0,0300.030 55 6060 HH 4,04.0 KK 4,04.0 88th BB. 0,0300.030 44th 6060 HH 4,04.0 KK 3,03.0 99 BB. 0,0300.030 55 5555 HH 2,02.0 KK 4,04.0 1010 EE. 0,0200.020 44th 6060 GG 4;04; 0 LL. 2,02.0

Fortsetzungcontinuation

Beispielexample Zusätzeadditions Mengecrowd StromdichteCurrent density Temperaturtemperature Nr.No. in g/lin g / l in A/dm2 in A / dm 2 in 0Cin 0 C 1111th EE. 0,0300.030 55 6060 II. 2,02.0 LL. 2,02.0 1212th AA. 0,0200.020 44th 5050 JJ 4,04.0 KK 3,03.0 1313th EE. 0,0200.020 55 6060 GG 2,02.0 KK 3,03.0 1414th AA. 0,0200.020 44th 55 -55 - GG 2,02.0 LL. 2,02.0

Tabelle VIITable VII

Beispielexample •5• 5 1818th 2020th 7u>iät7e7u> iät7e Mengecrowd StromdichteCurrent density Temperaturtemperature 6565 Nr. ■No. ■ in g/lin g / l in A/dm2 in A / dm 2 in°Cin ° C 1515th AA. 0,0200.020 66th 6060 6060 GG 2,02.0 KK 3,03.0 ίο 16ίο 16 AA. 0,015 .0.015. 66th 6060 GG 2,02.0 LL. 2,02.0 1717th EE. 0,0150.015 55 GG 2,02.0 KK 3,03.0 BB. 0,0150.015 55 HH 2,02.0 LL. 3,03.0

Beispielel5bisl8 Die aus Bädern unter Verwendung der neuen GlanzExamples 5 to 8 Die from baths using the new gloss

mittelkombination abgeschiedenen NickelüberzügeMedium combination of deposited nickel coatings

In den Beispielen 15 bis 18 wurde das folgende 25. sind vorteilhaft, indem spiegelglänzende galvanische Standardbad als Grundlösung verwendet: überzüge mit einem hohen Grad von BiegsamkeitIn Examples 15 to 18, the following 25. are advantageous by adding mirror-finish galvanic Standard bath used as the basic solution: coatings with a high degree of flexibility

bzw. Geschmeidigkeit in einem weiten Kathoden-Nickelchlorid 250 g/l stromdichtebereich erhalten werden. Die galvanischenor suppleness can be obtained in a wide cathode nickel chloride 250 g / l current density range. The galvanic

Nickelsulfat 45 g/l Glanznickelüberzüge werden vorzugsweise auf Kup-Nickel sulphate 45 g / l Bright nickel coatings are preferably applied to copper

Borsäure 45 g/l 30 fer- bzw. Kupferlegjerungsgrundmetalle oder auchBoric acid 45 g / l 30 ferrous or copper alloy base metals or else

Natriumlaurylsulfat 0,25 g/l direkt auf Eisen oder Stahl abgeschieden.Sodium lauryl sulfate 0.25 g / l deposited directly on iron or steel.

Claims (1)

Patentansprüche:Patent claims: 1. Galvanisches, N-Propargylpyridiniumsalze als Glanzbildner und sekundäre Glanzmittel enthaltendes Nickelbad, dadurch gekennzeichnet, daß das Bad ein N-Propargylpyridiniumsalz der allgemeinen Formel1. Galvanic containing N-propargylpyridinium salts as brighteners and secondary brighteners Nickel bath, characterized that the bath is an N-propargylpyridinium salt of the general formula
DE1496908A 1964-02-24 1965-02-23 Galvanic nickel bath. Note »M&T Chemicals Inc., New York, N.Y. (V.StA.) Expired DE1496908C3 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US347046A US3296103A (en) 1964-02-24 1964-02-24 Bright nickel electroplating

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DE1496908B2 DE1496908B2 (en) 1973-03-15
DE1496908C3 true DE1496908C3 (en) 1973-10-04

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US (1) US3296103A (en)
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DE (1) DE1496908C3 (en)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2938033A (en) * 1960-05-24 Stabilization of vinylpyridines
BE511322A (en) * 1946-04-20
US2647866A (en) * 1950-07-17 1953-08-04 Udylite Corp Electroplating of nickel
US2749349A (en) * 1956-02-02 1956-06-05 Reilly Tar & Chem Corp Vinylpyridine-nu-oxides and process of making them
US3006822A (en) * 1957-05-08 1961-10-31 Langbein Pfanhauser Werke Ag Electro-deposition of nickel coatings
DE1066068B (en) * 1957-06-05 1959-09-24 Langbein-Pfanhauser Werke Aktiengesellschaft, Neuß Electrolyte for galvanic deposition of mirror-shining, leveled, ductile nickel deposits
US3218244A (en) * 1963-02-01 1965-11-16 M & T Chemicals Inc Nickel electroplating bath containing a 1, 2-dichloropropene pyridinium or quinolinium brightener
US3170855A (en) * 1963-03-18 1965-02-23 Sarki Res And Dev Corp Bright nickel plating baths
US3170854A (en) * 1963-03-18 1965-02-23 Sarki Res And Dev Corp Bright nickel plating bath containing a pyridinium or quinolinium phosphate brightener and method of electroplating therewith

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DE1496908A1 (en) 1969-08-14
NL148657B (en) 1976-02-16
DE1496908B2 (en) 1973-03-15
US3296103A (en) 1967-01-03
GB1097724A (en) 1968-01-03
CH466662A (en) 1968-12-15
NL6502195A (en) 1965-08-25
GB1097723A (en) 1968-01-03

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E77 Valid patent as to the heymanns-index 1977