JP6687331B2 - Electrolytic bath for the deposition of a bright nickel layer, or a mixture for use in an electrolytic bath for the deposition of a bright nickel layer, and a method of making an article having a bright nickel layer - Google Patents

Description

  The invention relates to an electrolytic bath for the deposition of a bright nickel layer, a corresponding mixture for use in an electrolytic bath for the deposition of a bright nickel layer, a gloss by depositing nickel on the corresponding workpiece. A corresponding method for producing an article with a nickel layer, the use of an electrolytic bath according to the invention or a mixture according to the invention for the deposition or production of a bright nickel layer, and an article comprising a bright nickel layer according to the invention.

Electrolytic baths and methods for the electrodeposition of bright nickel layers are known from the prior art.
Here, the international patent application with publication number WO93 / 15241A1 describes, for example, from an aqueous acidic bath containing one or more nickel salts as essential components, one or more inorganic acids, and at least two brighteners. The present invention relates to a method for producing a nickel-plated molded member by electrolytically depositing nickel. This publication further relates to brightener mixtures which can be used for the process. The types of substances that produce luster are:
A sulfonimide, such as sulfimide benzoate,
-Sulfonamide,
-Benzenesulfonic acid, such as monobenzenesulfonic acid, dibenzenesulfonic acid and tribenzenesulfonic acid,
-Naphthalene sulfonic acids, such as mononaphthalene sulfonic acid, dinaphthalene sulfonic acid and trinaphthalene sulfonic acid,
-Alkyl sulfonic acid,
-Sulfinic acid,
-Arylsulfonsulfonate,
An aliphatic compound having an ethylene bond and / or an acetylene bond, such as butynediol,
-Mononuclear and polynuclear nitrogen-containing heterocyclic compounds which may further contain other heteroatoms such as sulfur or selenium,
-Coumarin,
Amines and quaternary ammonium compounds as leveling agents,
-Saccharin,
Is mentioned.

  The German patent application with publication number DE19610361A1 discloses baths and methods for the electrodeposition of semi-bright nickel. One or more cyclic N-allylammonium compounds, or N-vinylammonium compounds, in particular pyridinium compounds, are used as brighteners for the electrodeposition of a semi-bright nickel layer on a support. The patent document itself points to a series of publications from the prior art relating to the electrodeposition of semi-bright nickel. Further included are various chemical compounds that can be used in the electrolytic bath. Thus, always at least one and possibly two or more nickel salts, for example nickel salts such as nickel sulphate, nickel chloride, nickel fluoride, and at least one inorganic acid such as sulfuric acid or boric acid. Inorganic acid and are included in the bath.

  Furthermore, the German patent with publication number DE 102008056470B3 describes a method for inspecting a metal layer, either alone on a substrate or on a component of a multi-layer metal layer system, and the deposition of such a metal layer. Describes a method for analytical control of the deposited electrolyte used for. In a preferred embodiment of the invention, the metal layer is an electrolytically deposited nickel layer. As mentioned in the introductory part of the specification of the said German patent with the publication number DE 102008056470B3, the electrolytically deposited multi-layer nickel layer is made of a material made of various materials as an anticorrosion coat, for example made of copper, brass Alternatively, it is applied on a steel or plastic member. The multi-layer nickel layer is then deposited in a defined sequence of various qualities, that is to say for example as a semi-bright nickel layer, a bright nickel layer, optionally with a particularly sulfur-rich intermediate layer. , And again deposited as a semi-bright nickel layer, which layer is optionally deposited with a plurality of particles.

The basic composition of the nickel deposition electrolyte is, according to Publication No. DE 102008056470B3, typically a so-called Nickel Watt bath, said bath containing nickel ions, chloride ions, sulphate ions and boric acid, for example: Composition: 60 g / l NiCl ₂ .6H ₂ O, 270 g / l NiSO ₄ .6H ₂ O, 45 g / l H ₃ BO ₃ . The pH value of the deposition electrolyte is generally 2.5 to 6.0, preferably 3 to 4.5, and particularly about 4.0. The precipitation is carried out at a temperature of 40 to 70 ° C, preferably 50 to 60 ° C, especially about 55 ° C. Each layer is electrodeposited from a deposition electrolyte having a different composition, in particular in terms of additives. The semi-glossy base layer on the substrate material is generally loaded with salicylic acid, ethyne derivatives such as hexyne diol or butyne diol, propargyl alcohol derivatives, formaldehyde and / or chloral hydrate or even mixtures of these compounds. Included as an agent. The sulfur-rich, glossy or matte intermediate layer, which can be optionally deposited, generally contains saccharin, sulphonic acid and / or ethyne derivatives as additives. The bright nickel layer generally contains, as additives, sulfur-containing compounds, for example toluenesulphonic acid or propargylsulphonate, and also saccharin instead of salicylic acid, or mixtures of these compounds. The upper semi-glossy nickel layer generally contains saccharin or a saccharin salt, chloral hydrate and / or formaldehyde or even a mixture of these compounds as an additive and optionally additionally, for example SiO ₂ , It contains particles made of Al ₂ O ₃ . In addition, the deposition electrolyte may contain further additives such as brighteners and wetting agents.

  CH514683 relates to "Method for electrolytic nickel plating and electrolytic nickel plating bath" (title).

  The above mentioned publications and the prior art cited therein relate to the corrosion resistance, leveling, ductility, gloss and coverage of the individual compounds and their combinations of the electrodeposited semi-bright nickel layer or nickel layer. The advantages of each are listed. In particular, improving the corrosion protection of the respective nickel layers is a major problem in the prior art, which problem should usually be solved by the use of corrosion resistant dual nickel and triple nickel systems. . Such systems are often formed from a semi-bright nickel layer, a bright nickel layer and a chrome layer, which system utilizes the potential difference between the semi-bright nickel layer and the bright nickel layer. In this case, when the upper chrome layer breaks, the more base bright nickel layer (the so-called sacrificial anode) is attacked by the corrosive medium reaching through the broken chrome layer, after which it becomes more noble. The semi-bright nickel layer and eventually the substrate itself is attacked. In this case, the bright nickel layer is more noble than the underlying semi-bright nickel layer due to the chemical introduction of the sulfur-containing organic component. As far as the sulfur-containing organic component is concerned, saccharin is usually used as a component of the bright nickel layer.

  The prior art methods for producing electrolytic baths or nickel-plated molded parts for the deposition of the respective nickel layers have given top priority to corrosion in consideration of the protection of the electrolytically coated substrate. If the aim was to reduce it, the new drinking water directive, in particular, would ultimately increase the demands on the migration resistance of its chemical constituents of the electrolytically applied layer on the substrate. There is. Therefore, in addition to reduction or prevention of corrosion as a general purpose, prevention or reduction of migration of components of the metal protective layer electrolytically applied on the substrate is added as a new additional problem or requirement. . Notably, the migration of nickel, as one of the metals often used in electrolysis technology, from coatings that protect the substrate is considered to be one of the most common contributors to contact allergies (nickel dermatitis). In view of this, it is a health risk for consumers. In view of this recognition, in Germany, among other things, is the second Directive for changes to the Drinking Water Directive (TrinkwV 2001), which came into effect on December 14, 2012. Therefore, in so-called stagnation tests of the alloys or coatings to be investigated respectively, at most 10 μg of nickel should be released in 1 liter of drinking water. The coatings used up to now, whether double-coated or triple-coated, do not meet the requirements of the new drinking water directive.

WO93 / 15241A1 DE19610361A1 DE102008056470B3 CH514683

A first subject of the invention is an electrolytic bath for the deposition of a bright nickel layer and a deposition of the bright nickel layer, which serves in particular to prevent or at least significantly reduce nickel migration in drinking water. To provide a corresponding mixture for use in an electrolytic bath.
Preferably, the electrolytic baths mentioned or the corresponding mixtures should inherently allow the deposition of bright nickel layers, which also have the particular typical properties of semi-bright nickel layers. One of these properties is, inter alia, the columnar layer structure, which has hitherto only been known for semi-bright nickel layers, between the semi-bright nickel layer and the bright nickel layer. It can be specified by measuring the apparent potential difference. Therefore, a layer system consisting of such a bright nickel layer and a chromium layer enclosing it will already result in effective corrosion protection.

According to the invention, said first problem posed is in an electrolytic bath for the deposition of a bright nickel layer and an electrolytic bath for the deposition of a bright nickel layer as defined in claim 1. Solved by the corresponding mixture for use. The mixture in the aqueous solution according to the invention or the electrolytic bath in the aqueous solution according to the invention is
1 selected from the group consisting of (c) sulfimide benzoate and / or sulfimide benzoate anion and (h) chloral hydrate, bromal hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehyde One, two, two or more or all compounds,
including.
The electrolytic bath according to the invention or the mixture according to the invention thus comprises sulfimide benzoate (saccharin, E954, 1,2-benzisothiazol-3 (2H) -one-1,1-dioxide, CAS number: 81-07- 2) and / or a bright nickel layer produced by using an electrolytic bath according to the invention or a mixture according to the invention, which contains as sulfinimide anion a benzoate anion as a sulfur source. It is electrochemically less precious than the bright nickel layer.

  Further, the electrolytic bath according to the present invention or the mixture according to the present invention is one or two selected from the group consisting of chloral hydrate, bromal hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehyde. More than two or all compounds, particularly preferably chloral hydrate (trichloroaldehyde hydrate, 2,2,2-trichloroacetaldehyde hydrate, 2,2,2-trichloro-1,1-ethanediol) , CAS number: 302-17-0).

The invention is based on the surprising finding that bright nickel layers produced by the electrolytic bath according to the invention or the mixture according to the invention release significantly less nickel into the drinking water than conventional nickel protective layers.
The electrolytic bath according to the invention or the mixture according to the invention in aqueous solution further comprises the following components:
(A) nickel ion,
(B) one or more acids,
(E) Formula (I)

(I)
,
（式中、
Ｒ¹は、ヒドロキシ、アミノ、Ｃ₁〜Ｃ₄−アルキルアミノもしくはジ（Ｃ₁〜Ｃ₄−アルキル）アミノによって置換されたＣ₁〜Ｃ₄−アルキルまたは水素またはＣ₁〜Ｃ₄−アルキルを意味し、
Ｒ²は、ヒドロキシ、アミノ、Ｃ₁〜Ｃ₄−アルキルアミノもしくはジ（Ｃ₁〜Ｃ₄−アルキル）アミノによって置換されたＣ₁〜Ｃ₄−アルキルを意味する）の１種または複数のアセチレン性不飽和化合物、
（ｆ）式（ＩＩ）

(I)
,
(In the formula,
R ¹ is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C substituted by amino ₄ - alkyl or hydrogen or C ₁ -C ₄ - alkyl Meaning,
R ² is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C ₄ substituted by amino - refers to an alkyl) one or more of acetylene Unsaturated compounds,
(F) Formula (II)

(II)
,
（式中、それぞれ相互に独立して、
芳香族環系の窒素原子構成部は、ピリジン、キノリンおよびイソキノリンから成る群から選択され、
ｍは、１〜２４の範囲の整数を意味し、
各Ｒ³は、独立して、炭素原子１〜２０個を有する分岐もしくは非分岐のアルキル基または水素またはヒドロキシを意味する）の１種または複数のベタイン、
（ｇ）１種または複数の湿潤剤
を含む。

(II)
,
(In the formula, each independently,
The nitrogen atom component of the aromatic ring system is selected from the group consisting of pyridine, quinoline and isoquinoline,
m means an integer in the range of 1 to 24,
Each R ³ independently represents a branched or unbranched alkyl group having 1 to 20 carbon atoms or hydrogen or hydroxy) one or more betaines,
(G) Contains one or more wetting agents.

The electrolysis bath according to the invention or the mixture according to the invention in aqueous solution (preferably the electrolysis bath according to the invention or the mixture according to the invention which is referred to below as “preferred”) preferably further comprises:
(D) Containing allyl sulfonic acid and / or allyl sulfonate.
The ring of formula (II), which contains a positively charged nitrogen atom as a characteristic constituent of all betaines of formula (II), is in this case from the group consisting of pyridine, quinoline and isoquinoline. Refers to the selected aromatic ring system.

The nickel ions (component (a)) are then derived from one, two, or more than two nickel salts, for example nickel salts such as nickel sulphate, nickel chloride, nickel fluoride. Salts are contemplated as components of the electrolytic bath according to the invention or the mixture according to the invention in anhydrous form or in various hydrate forms. Furthermore, the electrolytic bath according to the invention or the mixture according to the invention comprises one or more acids (component (b)), the term "acid" being in the dissociated form at the respective pH value. Both compounds and undissociated forms of the compounds are included. The one or more acids are used in particular for buffering the pH value in the electrolysis process.
The components according to the invention of sulfimide and / or sulfimide benzoate anion (component (c)) and optionally allylsulfonic acid and / or allylsulfonate (component (d)) are based on the basic brightening agent (primary It is also called brightener). Brightening refers to the balancing or leveling of irregularities, especially in the base material, and is usually based on the use of low molecular weight organic surface-active compounds in the electrodeposited layer. The term "leveling" refers to the smoothing of irregularities on a surface (layer), such as those that remain after previous polishing (polishing scratches) on the surface (layer). The polishing of the surface (layer) is a common processing measure, especially for parts, particularly preferably for brass parts, zinc parts or zinc die-cast parts, before electroplating.

Brighteners are therefore used for the uniform distribution of the nickel layer applied by the electrolytic bath according to the invention or the mixture according to the invention over the region of the current density and for the deposition of a ductile, strain-free nickel layer. Particularly preferably, in this case, as component (c), or in component (c), benzoic acid sulfimide-sodium salt (CAS number: 128-44-9) is used and / or as component (d), Alternatively, in the component (d), allylsulfonic acid-sodium salt (sodium prop-2-ene-1-sulfonic acid, sodium allylsulfonic acid, propa-2-ene-1-sulfonic acid-sodium salt, CAS number: 2495- 39-8) is used.
Further mentioned components of the electrolytic bath according to the invention or of the mixture according to the invention, for example one or more acetylenically unsaturated compounds of formula (I) (component (e)), one or more betaines of formula (II). (Component (f)), and one or more wetting agents (Component (g)), among other things, brightening the bright nickel layer applied on the substrate by the electrolytic bath according to the invention or the mixture according to the invention. Promote.

The betaines of formula (II) (component (f)) and the acetylenically unsaturated compounds of formula (I) (component (e)) are likewise called brighteners (also called secondary brighteners). The wetting agent contained in the electrolytic bath according to the invention or in the mixture according to the invention causes a reduction in the surface tension which facilitates the rapid removal of hydrogen adhering to the cathode which occurs during the electroplating process.
Particularly preferably used compounds of the formula (I) (component (e)) are then propargyl alcohol (2-propyn-1-ol, CAS number: 107-19-7), 2-butyne-1,4. -Diol (but-2-yne-1,4-diol, 1,4-butynediol, bis (hydroxymethane) acetylene, butynediol, CAS number: 110-65-6), hexa-3-yne-2, 5-diol (3-hexyne-2,5-diol, di (1-hydroxyethyl) acetylene, bis (1-hydroxyethyl) acetylene, CAS number: 3031-66-1) and 1-diethylamino-prop-2- In (N, N-diethylprop-2-yn-1-amine). These compounds can be used alone or in combination.

  Particularly preferably used compounds of formula (II) (component (f)) are pyridinium propyl sulfobetaine (PPS, 1- (3-sulfopropyl) pyridinium betaine, NDSB 201, 3- (1-pyridinium) -1- Propane sulfonate, CAS number: 15471-17-7) and 1- (2-hydroxy-3-sulfopropyl) pyridinium betaine (PPS-OH, CAS number: 3918-73-8). These compounds can be used alone or in combination with one another. The preferred compounds of formula (II) are preferably used together with further components which are mentioned above or below as being preferred.

The electrolysis bath according to the invention preferably comprises one, more or all of the following components, or the mixture according to the invention comprises one, more or all of the following components, preferably in aqueous solution. :
(B) one or more inorganic acids selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid, and / or one or more inorganic acids selected from the group consisting of malic acid, citric acid, lactic acid and amidosulfonic acid An organic acid, and / or (g) one or more wetting agents, wherein one or more or all of the one or more wetting agents is (i) a fatty alcohol ether sulfate, and / or Or an acid produced from its salt by protonation,
(Ii) an acid generated by protonation from a fatty alcohol sulfate and / or a salt thereof,
(Iii) -fatty alcohol ether sulphates, and-a mixture comprising or consisting of fatty alcohol sulphates,
(Iv) a fatty alcohol ether sulphate, and-a mixture comprising or consisting of an acid of a fatty alcohol sulphate,
(V) -fatty alcohol ether sulphate, and-a mixture comprising or consisting of an acid of fatty alcohol sulphate, and (vi) -an acid of fatty alcohol ether sulphate, and-a fatty alcohol sulphate, or One selected wetting agent selected from the group consisting of a mixture thereof comprises as a carbon chain a branched or unbranched alkyl group, or a plurality of selected wetting agents comprises a carbon chain. Independently of each other, carrying a branched or unbranched alkyl group.

  Alternatively or additionally, in many cases the salt of sulfosuccinic acid (preferably the sodium salt) is preferred as the wetting agent in the electrolytic bath according to the invention or the mixture according to the invention.

The acid or acids used are then particularly preferably selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid. As a particularly preferable wetting agent, C ₁₃ -C ₁₅ -oxo alcohol ether sulfate (CAS number: 78330-30-0) is used. Similarly, sodium lauryl sulfate (sodium dodecyl sulfate, dodecyl sulfate-sodium salt, sulfate dodecyl ester-sodium salt, SLS, SDS, NLS, CAS number: 151-21-3) is preferably used as a wetting agent. These compounds can be used alone or in combination and are preferably used with further components which are mentioned above or below as being preferred.

Preferably, the electrolytic bath according to the invention or the mixture according to the invention comprises, as mentioned above, a fatty alcohol ether sulphate and / or a fatty alcohol sulphate and / or an acid of a fatty alcohol ether sulphate and / or a fatty alcohol sulphate. Contains acid, in which case
The fatty alcohol ether sulfate has the formula (III)

(III)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲の整数を意味し、かつ
Ｒ⁴は、炭素原子１〜２０個を有する分岐もしくは非分岐のアルキル基を意味し、
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄から成る群から選択される）の脂肪アルコールエーテルスルファート、および／もしくはその塩からプロトン化によって生成する酸
から成る群から選択され、かつ／または
前記脂肪アルコールスルファートが、式（ＩＶ）

(III)
,
(In the formula, each independently,
n represents an integer in the range of 1 to 24, and R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms,
X is selected from the group consisting of Li, Na, K, Rb, Cs and NH ₄ ) fatty alcohol ether sulphate) and / or an acid formed by protonation from a salt thereof, and / Or the fatty alcohol sulphate has the formula (IV)

(IV)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲の整数を意味し、かつ
Ｒ⁴は、炭素原子１〜２０個を有する分岐もしくは非分岐のアルキル基を意味し、かつ
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄から成る群から選択される）の脂肪アルコールスルファート、および／もしくはその塩からプロトン化によって生成する脂肪アルコールスルファートの酸
から成る群から選択される。

(IV)
,
(In the formula, each independently,
n represents an integer in the range of 1 to 24, R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms, and X represents Li, Na, K, Rb, Selected from the group consisting of Cs and NH ₄ ) and / or the acid of a fatty alcohol sulfate formed by protonation from a salt thereof.

Particularly preferred compounds of formula (IV) are then 2-ethylhexylsulfate-sodium salt (CAS: 126-92-1) and sodium lauryl sulfate (see above). These compounds can be used alone or in combination and are preferably used with further components which are mentioned above or below as being preferred.
Preferably, the electrolysis bath according to the invention or the mixture according to the invention (preferably the electrolysis bath according to the invention or the mixture according to the invention which has been referred to above as "preferred"), in addition to the other components mentioned above,
(I) Formula (V)

(V)
,
（式中、

は、シスもしくはトランス配置の二重結合または三重結合を意味し、かつ
Ｒ⁵は、ヒドロキシによって置換されたＣ₁〜Ｃ₄−アルキルまたは水素またはＣＨ₂ＯＲ⁶を意味し、
Ｒ⁶は、ヒドロキシによって置換されたＣ₁〜Ｃ₄−アルキルまたは水素またはスルホン酸残基もしくはその塩を意味し、その際、
Ｒ⁵およびＲ⁶は、同時に水素を意味することはなく、かつ
破線は、単結合を意味する）の１種または複数の化合物
を含む。

(V)
,
(In the formula,

Means a double or triple bond in the cis or trans configuration, and R ⁵ means C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or CH ₂ OR ⁶ ;
R ⁶ represents C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or a sulphonic acid residue or salt thereof, wherein
R ⁵ and R ⁶ do not mean simultaneously hydrogen and the broken line means a single bond).

  2-butyne-1,4-diol ethoxylate (2,2 ′-(but-2-yn-1,4-diylbis (oxy)) bis (ethane-1-ol)), 2-butyne-1,4 -Diol propoxylate (4- (3-hydroxypropoxy) but-2-yn-1-ol), propargyl alcohol ethoxylate (2- (prop-2-yn-1-yloxy) ethane-1-ol), propargyl Sodium sulfonate (prop-2-yn-1-yl sulfite-sodium salt, CAS number: 55947-46-1) and sodium vinyl sulfonate (SVS, sodium ethylene sulfonate, vinyl sulfonic acid-sodium salt, ethylene sulfonic acid) A compound of formula (V) selected from the group consisting of sodium salts, CAS number: 3039-83-6). It is particularly preferred. These compounds can be used alone or in combination and are preferably used with further components which are mentioned above or below as being preferred.

A very particularly preferred electrolysis bath comprises the following components, or a very particularly preferred mixture comprises in aqueous solution one, more or all of the following components (at the concentrations indicated):
(A) Nickel ions in a total amount of 1.12 to 1.67 mol / L,
And / or (b) one or more inorganic acids selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid in a total amount of 0.485 to 0.97 mol / L, and / or malic acid, citric acid, lactic acid and One or more organic acids selected from the group consisting of amidosulfonic acids;
And / or (c) a total amount of 0.0055 to 0.0274 mol / L of sulfimide and benzoate sulfimide anion,
And / or (d) a total amount of 0.006-0.025 mol / L of allyl sulfonic acid and allyl sulfonate,
And / or (e) the total amount of 0.00036 to 0.1438 mol / L of the formula (I)

(I)
,
（式中、
Ｒ¹は、ヒドロキシ、アミノ、Ｃ₁〜Ｃ₄−アルキルアミノもしくはジ（Ｃ₁〜Ｃ₄−アルキル）アミノによって置換されたＣ₁〜Ｃ₄−アルキルまたは水素またはＣ₁〜Ｃ₄−アルキルを意味し、
Ｒ²は、ヒドロキシ、アミノ、Ｃ₁〜Ｃ₄−アルキルアミノもしくはジ（Ｃ₁〜Ｃ₄−アルキル）アミノによって置換されたＣ₁〜Ｃ₄−アルキルを意味する）の１種または複数のアセチレン性不飽和化合物、
ならびに／あるいは
（ｆ）全量０．０００２５〜０．００２５ｍｏｌ／Ｌの、式（ＩＩ）

(I)
,
(In the formula,
R ¹ is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C substituted by amino ₄ - alkyl or hydrogen or C ₁ -C ₄ - alkyl Meaning,
R ² is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C ₄ substituted by amino - refers to an alkyl) one or more of acetylene Unsaturated compounds,
And / or (f) the total amount of 0.00025 to 0.0025 mol / L of the formula (II)

(II)
,
（式中、それぞれ相互に独立して、
芳香族環系の窒素原子構成部は、ピリジン、キノリンおよびイソキノリンから成る群から選択され、かつ
ｍは、１〜２４の範囲の整数を意味し、
各Ｒ³は、独立して、炭素原子１〜２０個を有する分岐もしくは非分岐のアルキル基または水素またはヒドロキシを意味する）の１種もしくは複数のベタイン、
ならびに／あるいは
（ｇ）全量０．０００６〜０．０２５ｍｏｌ／Ｌの１種または複数の湿潤剤であって、１種の湿潤剤または複数の湿潤剤の１種もしくは複数もしくは全てが、（ｉ）脂肪アルコールエーテルスルファート、および／またはその塩からプロトン化によって生成する酸、
（ｉｉ）脂肪アルコールスルファート、および／またはその塩からプロトン化によって生成する酸、
（ｉｉｉ） − 脂肪アルコールエーテルスルファート、および
− 脂肪アルコールスルファート
を含む、もしくはそれらから成る混合物、
（ｉｖ） − 脂肪アルコールエーテルスルファートの酸、および
− 脂肪アルコールスルファートの酸
を含む、もしくはそれらから成る混合物、
（ｖ） − 脂肪アルコールエーテルスルファート、および
− 脂肪アルコールスルファートの酸
を含む、もしくはそれらから成る混合物、ならびに
（ｖｉ） − 脂肪アルコールエーテルスルファートの酸、および
− 脂肪アルコールスルファート
を含む、またはそれらから成る混合物
から成る群から選択され、脂肪アルコールエーテルスルファートが、式（ＩＩＩ）

(II)
,
(In the formula, each independently,
The nitrogen atom constituent of the aromatic ring system is selected from the group consisting of pyridine, quinoline and isoquinoline, and m means an integer in the range 1 to 24,
Each R ³ independently represents a branched or unbranched alkyl group having 1 to 20 carbon atoms or hydrogen or hydroxy) one or more betaines,
And / or (g) one or more wetting agents in a total amount of 0.0006 to 0.025 mol / L, wherein one or more or all of the one or more wetting agents are (i) Acids produced by protonation from fatty alcohol ether sulphates, and / or salts thereof,
(Ii) an acid produced by protonation from a fatty alcohol sulfate, and / or a salt thereof,
(Iii) -fatty alcohol ether sulphates, and-a mixture comprising or consisting of fatty alcohol sulphates,
(Iv) -a mixture of fatty alcohol ether sulphate acids, and-a mixture of fatty alcohol sulphate acids, or
(V) -fatty alcohol ether sulphate, and-a mixture comprising or consisting of fatty alcohol sulphate acid, and (vi) -fatty alcohol ether sulphate acid, and-fatty alcohol sulphate, or A fatty alcohol ether sulphate selected from the group consisting of mixtures thereof

(III)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲の整数を意味し、かつ
Ｒ⁴は、炭素原子１〜２０個を有する分岐もしくは非分岐のアルキル基を意味し、
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄から成る群から選択される）の脂肪アルコールエーテルスルファート、および／もしくはその塩からプロトン化によって生成する酸
から成る群から選択され、かつ／または
脂肪アルコールスルファートが、式（ＩＶ）

(III)
,
(In the formula, each independently,
n represents an integer in the range of 1 to 24, and R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms,
X is selected from the group consisting of Li, Na, K, Rb, Cs and NH ₄ ) fatty alcohol ether sulphate) and / or an acid formed by protonation from a salt thereof, and / Or fatty alcohol sulphate has the formula (IV)

(IV)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲の整数を意味し、
Ｒ⁴は、炭素原子１〜２０個を有する分岐もしくは非分岐のアルキル基を意味し、
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄から成る群から選択される）の脂肪アルコールスルファート、および／もしくはその塩からプロトン化によって生成する酸
から成る群から選択される湿潤剤、ならびに／あるいは
（ｈ）全量０．００３〜０．０１８ｍｏｌ／Ｌの、抱水クロラール、抱水ブロマール、ギ酸、ホルマート、酢酸、アセタート、置換もしくは非置換の脂肪族アルデヒドから成る群から選択される１種、２種、２種を超えるまたは全ての化合物、
ならびに／あるいは
（ｉ）全量０〜０．００２５ｍｏｌ／Ｌの、式（Ｖ）

(IV)
,
(In the formula, each independently,
n means an integer in the range of 1 to 24,
R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms,
X is a fatty alcohol sulfate selected from the group consisting of Li, Na, K, Rb, Cs and NH ₄ ) and / or a wetting agent selected from the group consisting of acids formed by protonation from salts thereof. And / or (h) is selected from the group consisting of chloral hydrate, bromal hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehyde in a total amount of 0.003 to 0.018 mol / L. One, two, more than or all compounds,
And / or (i) the total amount of 0 to 0.0025 mol / L of the formula (V)

(V)
,
（式中、

は、シスもしくはトランス配置の二重結合または三重結合を意味し、
Ｒ⁵は、ヒドロキシによって置換されたＣ₁〜Ｃ₄−アルキルまたは水素またはＣＨ₂ＯＲ⁶を意味し、
Ｒ⁶は、ヒドロキシによって置換されたＣ₁〜Ｃ₄−アルキルまたは水素またはスルホン酸残基もしくはその塩を意味するが、
但し、Ｒ⁵およびＲ⁶は、同時に水素を意味せず、かつ
但し、破線は、単結合を意味する）の１種または複数の化合物。

(V)
,
(In the formula,

Means a double or triple bond in the cis or trans configuration,
R ⁵ means C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or CH ₂ OR ⁶ ;
R ⁶ represents C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or a sulfonic acid residue or salt thereof,
Provided that R ⁵ and R ⁶ do not mean hydrogen at the same time, and the broken line means a single bond).

  The present invention containing all of the above-mentioned components (a), (b), (c), (d), (e), (f), (g), (h) and (i) in the above-mentioned concentration. Particularly preferred are the electrolytic baths according to (1) or the mixtures according to the invention.

In fact, the individual abovementioned components of the particularly preferred electrolysis bath according to the invention or of the particularly preferred mixture according to the invention can be electrolyzed according to the invention depending on the course of the electroplating process and depending on the consumption of each of the abovementioned components. The bath or the mixture according to the invention is optionally supplied by controlled analysis (eg by HPLC analysis).
Of course, the electrolytic bath according to the invention or the mixture according to the invention comprises the necessary amount of counterions for charge compensation in the presence of cations.

Preferably, the electrolytic bath according to the present invention or the mixture according to the present invention (preferably the electrolytic bath according to the present invention or the mixture according to the present invention which has been referred to above as "preferred") comprises, in addition to the other components mentioned above, F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , SO ₄ ²⁻ , OH ⁻ and ClO ₄ ⁻ , containing one, two, two or more or all anions.
Preferably, the electrolytic bath according to the invention or the mixture according to the invention is further selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ and Sr ^2+. It contains one, two, more than two or all cations.
Indeed a particularly preferred electrolytic bath according to the invention or a particularly preferred mixture according to the invention is
(H) chloral hydrate, bromal hydrate, formaldehyde and acetaldehyde,
It is particularly preferred that it comprises one, two, or all compounds selected from the group consisting of, wherein said one compound or one of the compounds is chloral hydrate.

In practice, electrolytic baths according to the invention or mixtures according to the invention which are single-phase solutions are particularly particularly preferred.
Particular preference is given to electrolytic baths according to the invention or mixtures according to the invention which are free of suspended silicon oxide particles and aluminum oxide particles.
Especially preferred are electrolytic baths according to the invention or mixtures according to the invention which do not contain suspended oxide particles.
Also preferred is an electrolysis bath according to the invention or a mixture according to the invention, which does not contain particles suspended in said electrolysis bath or mixture.

Particular preference is given to electrolytic baths according to the invention or mixtures according to the invention which have a pH value in the range from 2.8 to 5.2, preferably 3.8 to 4.8. At such pH values and suitable temperatures, the individual components of the preferred electrolytic bath according to the invention or the preferred mixture according to the invention exhibit particularly good water solubility.
Particularly preferred is an electrolytic bath according to the invention or a mixture according to the invention, which can be prepared by mixing several components, wherein said several components are
(A1) nickel sulfate,
(A2) nickel chloride,
(B1) boric acid,
(C1) benzoic acid sulfimide-sodium salt,
(D1) allylsulfonic acid-sodium salt,
(E1) 2-propyn-1-ol,
(E2) 1-diethylamino-prop-2-yne,
(E3) hexa-3-yne-2,5-diol,
(F1) pyridinium propyl sulfobetaine,
(G-VI) formula (VI)

(VI)
,
（式中、ｎは、１〜２４の範囲の整数を意味し、
Ｒ⁴は、炭素原子１〜２０個を有する飽和で分岐もしくは飽和非分岐のアルキル基を意味する）の脂肪アルコールエーテルスルファートのナトリウム塩、
（ｈ１）抱水クロラール、
（ｉ１）プロパ−２−イン−１−オール−エトキシナート
から成る群から選択される。

(VI)
,
(In the formula, n means an integer in the range of 1 to 24,
R ⁴ means a saturated, branched or saturated unbranched alkyl group having 1 to 20 carbon atoms), the sodium salt of a fatty alcohol ether sulphate,
(H1) Chloral hydrate,
(I1) selected from the group consisting of prop-2-yn-1-ol-ethoxynate.

Even more particularly preferred is an electrolysis bath according to the invention (preferably an electrolysis bath according to the invention which has been designated as “preferred” above) which can be prepared by mixing several components, wherein said some components are
(A) Nickel ions in a total amount of 1.12 to 1.67 mol / L,
(B1) boric acid in a total amount of 0.485 to 0.97 mol / L,
(C) Total amount of 0.0055 to 0.0274 mol / L sulfimide anion benzoate,
(D) Allyl sulfonate in a total amount of 0.006 to 0.025 mol / L,
(E1) 2-propyn-1-ol in a total amount of 0.00036 to 0.0089 mol / L,
(E2) 1-diethylamino-prop-2-yne in a total amount of 0 to 0.0045 mol / L,
(E3) Hex-3-yne-2,5-diol in a total amount of 0 to 0.0088 mol / L,
(F1) Pyridinium propyl sulfobetaine in a total amount of 0.00025 to 0.0025 mol / L,
(G) Formula (VI) with a total amount of 0.0006 to 0.025 mol / L.

(VI)
,
（式中、
ｎは、それぞれ独立して、１〜２４の範囲の整数を意味し、
Ｒ⁴は、それぞれ独立して、炭素原子１〜２０個を有する飽和分岐もしくは飽和非分岐のアルキル基を意味する）の脂肪アルコールエーテル硫酸のナトリウム塩、
（ｈ１）全量０．００３〜０．０１８ｍｏｌ／Ｌの抱水クロラール、
および
（ｉ１）全量０〜０．００２５ｍｏｌ／Ｌのプロパ−２−イン−１−オール−エトキシナート
から成る群から選択される。

(VI)
,
(In the formula,
n each independently represents an integer in the range of 1 to 24,
R ⁴ each independently represents a saturated branched or saturated unbranched alkyl group having 1 to 20 carbon atoms), the sodium salt of a fatty alcohol ether sulfuric acid,
(H1) 0.003 to 0.018 mol / L of chloral hydrate,
And (i1) selected from the group consisting of a total amount of 0-0.0025 mol / L of prop-2-yn-1-ol-ethoxynate.

In this case, all concentration notations are based on the electrolytic bath.
The present invention is also a method of making an article having a bright nickel layer by depositing nickel on a corresponding workpiece, comprising the steps of:
(A) providing and / or producing an electrolytic bath or mixture according to any one of the preceding claims,
(B) electrolytically depositing nickel on the work piece from the prepared or produced electrolytic bath or mixture to produce a bright nickel layer;
With respect to.

  Preferably, in the process according to the invention, the temperature of said electrolysis bath or mixture in step (b) is in the range 40 to 70 ° C, preferably in the range 50 to 60 ° C. At such temperatures, the individual components of the preferred electrolytic bath according to the invention or the preferred mixture according to the invention exhibit particularly good water solubility.

Preferably, in the method according to the invention in step (b) a bright nickel layer is deposited on the copper, brass or zinc surface of the work piece.
Particularly preferred is the method according to the invention, wherein the article is a component of a conduit or a component of a component for a water conduit.
More particularly preferred is the process according to the invention, wherein the above-described precipitation of a workpiece is carried out on a surface, which surface is part of the bright nickel layer of the workpiece.
The following additional steps:
(C) depositing a further metal layer on the bright nickel layer, preferably electrodeposition, preferably depositing a chromium layer on the bright nickel layer,
Particularly preferred is the method according to the invention having
In the method according to the invention, it is preferred to blow air into the electrolytic bath according to the invention and / or to move the work piece in which nickel is to be electrodeposited in the electrolytic bath or mixture. Bubbling air and moving the work piece in the electrolytic bath according to the invention or the mixture according to the invention serves in this case for better electrolyte exchange on the work piece surface on which nickel is to be electrodeposited.

Preference is furthermore given to the process according to the invention in which the electrolytic nickel deposition is carried out in a steel container having a sufficient acid-resistant lining (for example PVC) for a given purpose or in a plastic container.
The above-defined (preferred) components of the electrolytic bath according to the invention or the mixture according to the invention are usually dissolved in demineralized water at a temperature of 50 ° C. with stirring. Metallic nickel is used as the anode material in the form of plates, squares, or crowns, or in any other suitable form. The nickel-plated work piece is connected as the cathode, and their electrodes are usually supplied with direct current via a rectifier. The amount of current required is generally 2-8 amps per dm ^{2 of} cathode surface (A / dm ² ). The nickel deposition rate on the workpiece connected as the cathode is generally about 1 μm nickel / min at a current of 5 A / dm ² . To ensure optimal electrolyte exchange on the cathode surface, it is often necessary to move the cathode (movement relative to the electrolyte). Alternatively or additionally, the circulation of the electrolytic bath according to the invention or the mixture according to the invention can be carried out by blowing in compressed air (air movement). During the proceeding process, it is generally necessary to filter the electrolytic bath according to the invention or the mixture according to the invention.

Also as part of the method according to the invention, the analytical control of the composition of the electrolytic bath according to the invention or the mixture according to the invention described above is preferably carried out by titration in the case of acid and chloride concentrations, In the case of agent concentration, by HPLC analysis, in the case of wetting agent by surface tension measurement, and in the case of nickel (ion) concentration, by chemical analysis or AAS (Atomic Absorption Spectroscopy) Done. Atomic absorption spectroscopy (AAS) can also determine the concentration of impurity metals that may be present in the electrolytic bath or mixture.
The invention also relates to the use of the abovementioned electrolytic baths or mixtures for the deposition or production of bright nickel layers. The above remarks on the preferred embodiments of the bath or mixture according to the invention apply correspondingly.

The invention further relates to the use of an electrolysis bath or mixture as defined above for depositing or producing a bright nickel layer on a component of a component for a water conduit. The above remarks on the preferred embodiments of the bath or mixture according to the invention apply correspondingly.
The invention also relates to an article comprising a bright nickel layer, particularly preferably a component of a conduit or a component for a water conduit, wherein the bright nickel layer comprises
By depositing nickel on the corresponding work piece using the electrolytic bath or mixture described above, or
Articles which can be produced, particularly preferably, components of conduits or components of parts for water conduits.

The invention will now be described in more detail by means of various specific embodiments:
1. An electrolytic bath for the deposition of a bright nickel layer, or a mixture for use in an electrolytic bath for the deposition of a bright nickel layer, wherein the mixture is in an aqueous solution or the electrolytic bath is in an aqueous solution,
(C) sulfimide benzoate and / or sulfimide benzoate anion and (h) one selected from the group consisting of chloral hydrate, bromal hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehyde Including two, more than two or all compounds,
An electrolytic bath or mixture in which the electrolytic bath additionally contains the following components or the mixture additionally contains the following components:
(A) nickel ion,
(B) one or more acids,
(E) Formula (I)

(I)
,
（式中、
Ｒ¹は、ヒドロキシ、アミノ、Ｃ₁−Ｃ₄−アルキルアミノもしくはジ（Ｃ₁−Ｃ₄−アルキル）アミノによって置換されたＣ₁−Ｃ₄−アルキルまたは水素またはＣ₁−Ｃ₄−アルキルを意味し、
Ｒ²は、ヒドロキシ、アミノ、Ｃ₁−Ｃ₄−アルキルアミノもしくはジ（Ｃ₁−Ｃ₄−アルキル）アミノによって置換されたＣ₁−Ｃ₄−アルキルを意味する）
の１種または複数のアセチレン系不飽和化合物、
（ｆ）式（ＩＩ）

(I)
,
(In the formula,
R ¹ is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C substituted by amino ₄ - alkyl or hydrogen or C ₁ -C ₄ - alkyl Meaning,
R ² is hydroxy, amino, C ₁ -C ₄ - refers to an alkyl) - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C ₄ substituted by amino
One or more acetylenically unsaturated compounds of
(F) Formula (II)

(II)
,
（式中、それぞれ相互に独立して、
芳香族環系の窒素原子構成部は、ピリジン、キノリンおよびイソキノリンからなる群から選択され、
ｍは、１〜２４の範囲内の整数を意味し、
各Ｒ³は、独立して、炭素原子１〜２０個を有する分枝もしくは非分枝アルキル基または水素またはヒドロキシを意味する）
の１種または複数のベタイン、
（ｇ）１種または複数の湿潤剤。

(II)
,
(In the formula, each independently,
The nitrogen atom component of the aromatic ring system is selected from the group consisting of pyridine, quinoline and isoquinoline,
m means an integer in the range of 1 to 24,
Each R ³ independently represents a branched or unbranched alkyl group having 1 to 20 carbon atoms or hydrogen or hydroxy)
One or more betaines of
(G) One or more wetting agents.

2. The electrolysis bath or mixture according to aspect 1, wherein the electrolysis bath comprises the following components, or the mixture comprises one, more or all of the following components in aqueous solution:
(B) one or more inorganic acids selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid and / or one or more organic compounds selected from the group consisting of malic acid, citric acid, lactic acid and amidosulfonic acid An acid and / or (g) one or more wetting agents, wherein one or more or all of the one or more wetting agents,
(I) an acid produced from a fatty alcohol ether sulfate and / or a salt thereof by protonation,
(Ii) an acid produced from a fatty alcohol sulfate and / or a salt thereof by protonation,
(Iii) a mixture comprising or consisting of fatty alcohol ether sulphate and fatty alcohol sulphate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulphate acid and fatty alcohol sulphate acid,
(V) a mixture comprising or consisting of a fatty alcohol ether sulphate and an acid of a fatty alcohol sulphate and (vi) a mixture comprising or consisting of an acid of a fatty alcohol ether sulphate and a fatty alcohol sulphate. Selected from
One selected wetting agent carries a branched or unbranched alkyl group as a carbon chain, or a plurality of selected wetting agents each have a carbon chain, independently of each other, as a branched or unbranched alkyl group. Carries an unbranched alkyl group,
And / or one or more or all of the one or more wetting agents are selected from the group consisting of salts of sulfosuccinic acid.
3. The fatty alcohol ether sulfate has the formula (III)

(III)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲内の整数を意味し、
Ｒ⁴は、炭素原子１〜２０個を有する分枝もしくは非分枝アルキル基を意味し、
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄から成る群から選択される）
の脂肪アルコールエーテルスルファート
および／もしくは
その塩からプロトン化によって生成する酸
から成る群から選択され、
かつ／または
脂肪アルコールスルファートが、式（ＩＶ）

(III)
,
(In the formula, each independently,
n means an integer in the range of 1 to 24,
R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms,
X is selected from the group consisting of Li, Na, K, Rb, Cs and NH _4. )
Selected from the group consisting of acids produced by protonation from fatty alcohol ether sulphates and / or salts thereof,
And / or the fatty alcohol sulphate has the formula (IV)

(IV)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲内の整数を意味し、
Ｒ⁴は、炭素原子１〜２０個を有する分枝もしくは非分枝アルキル基を意味し、
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄
から成る群から選択される）
の脂肪アルコールスルファート
および／もしくは
その塩からプロトン化によって生成する酸
から成る群から選択される、態様２に記載の電解浴または混合物。
４． 電解浴が、以下の成分を追加的に含むか、または混合物が、水溶液中に以下の成分の１種、複数もしくは全てを追加的に含む、前記態様の１つに記載の電解浴または混合物：
（ｉ）式（Ｖ）

(IV)
,
(In the formula, each independently,
n means an integer in the range of 1 to 24,
R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms,
X is Li, Na, K, Rb, Cs and NH _4.
Selected from the group consisting of)
3. The electrolytic bath or mixture according to embodiment 2, selected from the group consisting of the acids formed by protonation from the fatty alcohol sulphates and / or salts thereof according to claim 2.
4. The electrolysis bath or mixture according to one of the preceding aspects, wherein the electrolysis bath additionally comprises the following components, or the mixture additionally comprises one, more or all of the following components in aqueous solution:
(I) Formula (V)

(V)
,
（式中、

(V)
,
(In the formula,

は、シスもしくはトランス配置の二重結合または三重結合を意味し、
Ｒ⁵は、ヒドロキシによって置換されたＣ₁−Ｃ₄−アルキルまたは水素またはＣＨ₂ＯＲ⁶を意味し、
Ｒ⁶は、ヒドロキシによって置換されたＣ₁−Ｃ₄−アルキルまたは水素またはスルホン酸基もしくはその塩を意味するが、
但し、Ｒ⁵およびＲ⁶は、同時には水素を意味せず、かつ
但し、破線は単結合を意味する）
の１種または複数の化合物。

Means a double or triple bond in the cis or trans configuration,
R ⁵ means C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or CH ₂ OR ⁶ ;
R ⁶ represents C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or a sulfonic acid group or salt thereof,
However, R ⁵ and R ⁶ do not mean hydrogen at the same time, and the broken line means a single bond.)
One or more compounds of.

5. The electrolysis bath or mixture according to one of the preceding aspects, wherein the electrolysis bath comprises the following components, or the mixture comprises one, more or all of the following components in aqueous solution:
(A) a total amount of 1.12 to 1.67 mol / L of nickel ions, and / or (b) a total amount of 0.485 to 0.97 mol / L,
One or more inorganic acids selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid, and / or one or more organic acids selected from the group consisting of malic acid, citric acid, lactic acid and amidosulfonic acid, And / or (c) a total amount of 0.0055 to 0.0274 mol / L sulfimide and benzoic acid sulfimide anion, and / or (d) a total amount of 0.006 to 0.025 mol / L allylsulfonic acid and allylsulfo. And / or (e) a total amount of 0.00036 to 0.1438 mol / L of the formula (I)

(I)
,
（式中、
Ｒ¹は、ヒドロキシ、アミノ、Ｃ₁−Ｃ₄−アルキルアミノもしくはジ（Ｃ₁−Ｃ₄−アルキル）アミノによって置換されたＣ₁−Ｃ₄−アルキルまたは水素またはＣ₁−Ｃ₄−アルキルを意味し、
Ｒ²は、ヒドロキシ、アミノ、Ｃ₁−Ｃ₄−アルキルアミノもしくはジ（Ｃ₁−Ｃ₄−アルキル）アミノによって置換されたＣ₁−Ｃ₄−アルキルを意味する）
の１種または複数のアセチレン系不飽和化合物、ならびに／あるいは
（ｆ）全量０．０００２５〜０．００２５ｍｏｌ／Ｌの、式（ＩＩ）

(I)
,
(In the formula,
R ¹ is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C substituted by amino ₄ - alkyl or hydrogen or C ₁ -C ₄ - alkyl Meaning,
R ² is hydroxy, amino, C ₁ -C ₄ - refers to an alkyl) - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C ₄ substituted by amino
One or more acetylenically unsaturated compounds of the formula (II), and / or (f) a total amount of 0.00025 to 0.0025 mol / L,

(II)
,
（式中、それぞれ相互に独立して、
芳香族環系の窒素原子構成部は、ピリジン、キノリンおよびイソキノリンからなる群から選択され、
ｍは、１〜２４の範囲内の整数を意味し、
各Ｒ³は、独立して、炭素原子１〜２０個を有する分枝もしくは非分枝アルキル基または水素またはヒドロキシを意味する）
の１種または複数のベタイン、ならびに／あるいは
（ｇ）全量０．０００６〜０．０２５ｍｏｌ／Ｌの１種または複数の湿潤剤であって、１種の湿潤剤または複数の湿潤剤の１種もしくは複数もしくは全てが、
（ｉ）脂肪アルコールエーテルスルファート
および／または
その塩からプロトン化によって生成する酸、
（ｉｉ）脂肪アルコールスルファート
および／または
その塩からプロトン化によって生成する酸、
（ｉｉｉ）脂肪アルコールエーテルスルファート
および
脂肪アルコールスルファート
を含む、またはそれらから成る混合物、
（ｉｖ）脂肪アルコールエーテルスルファートの酸
および
脂肪アルコールスルファートの酸
を含む、またはそれらから成る混合物、
（ｖ）脂肪アルコールエーテルスルファート
および
脂肪アルコールスルファートの酸
を含む、またはそれらから成る混合物、
ならびに
（ｖｉ）脂肪アルコールエーテルスルファートの酸
および
脂肪アルコールスルファート
を含む、またはそれらから成る混合物
から成る群から選択され、脂肪アルコールエーテルスルファートが、式（ＩＩＩ）

(II)
,
(In the formula, each independently,
The nitrogen atom component of the aromatic ring system is selected from the group consisting of pyridine, quinoline and isoquinoline,
m means an integer in the range of 1 to 24,
Each R ³ independently represents a branched or unbranched alkyl group having 1 to 20 carbon atoms or hydrogen or hydroxy)
And / or (g) one or more wetting agents having a total amount of 0.0006 to 0.025 mol / L, wherein one wetting agent or one or more wetting agents or Multiple or all
(I) an acid produced from a fatty alcohol ether sulfate and / or a salt thereof by protonation,
(Ii) an acid produced from a fatty alcohol sulfate and / or a salt thereof by protonation,
(Iii) a mixture comprising or consisting of fatty alcohol ether sulphate and fatty alcohol sulphate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulphate acid and fatty alcohol sulphate acid,
(V) a mixture comprising or consisting of fatty alcohol ether sulphate and fatty alcohol sulphate acid,
And (vi) selected from the group consisting of mixtures of acids of fatty alcohol ether sulphates and fatty alcohol sulphates, or mixtures thereof, the fatty alcohol ether sulphates having the formula (III)

(III)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲内の整数を意味し、
Ｒ⁴は、炭素原子１〜２０個を有する分枝もしくは非分枝アルキル基を意味し、
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄から成る群から選択される）
の脂肪アルコールエーテルスルファート
および／もしくは
その塩からプロトン化によって生成する酸
から成る群から選択され、
かつ／または
脂肪アルコールスルファートが、式（ＩＶ）

(III)
,
(In the formula, each independently,
n means an integer in the range of 1 to 24,
R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms,
X is selected from the group consisting of Li, Na, K, Rb, Cs and NH _4. )
Selected from the group consisting of acids produced by protonation from fatty alcohol ether sulphates and / or salts thereof,
And / or the fatty alcohol sulphate has the formula (IV)

(IV)
,
（式中、それぞれ相互に独立して、
ｎは、１〜２４の範囲内の整数を意味し、
Ｒ⁴は、炭素原子１〜２０個を有する分枝もしくは非分枝アルキル基を意味し、
Ｘは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＮＨ₄
から成る群から選択される）
の脂肪アルコールスルファート
および／もしくは
その塩からプロトン化によって生成する酸
から成る群から選択される湿潤剤、ならびに／あるいは
（ｈ）全量０．００３〜０．０１８ｍｏｌ／Ｌの、
抱水クロラール、抱水ブロマール、ギ酸、ホルマート、酢酸、アセタート、置換もしくは非置換脂肪族アルデヒド
から成る群から選択される、１種、２種、２種を超えるまたは全ての化合物、ならびに／あるいは
（ｉ）全量０から０．００２５ｍｏｌ／Ｌの、式（Ｖ）

(IV)
,
(In the formula, each independently,
n means an integer in the range of 1 to 24,
R ⁴ represents a branched or unbranched alkyl group having 1 to 20 carbon atoms,
X is Li, Na, K, Rb, Cs and NH _4.
Selected from the group consisting of)
A wetting agent selected from the group consisting of the acids produced by protonation from the fatty alcohol sulphates and / or salts thereof, and / or (h) a total amount of 0.003 to 0.018 mol / L,
One, two, two or more or all compounds selected from the group consisting of chloral hydrate, bromal hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehydes, and / or ( i) Total amount 0 to 0.0025 mol / L of the formula (V)

(V)
,
（式中、

(V)
,
(In the formula,

は、シスもしくはトランス配置の二重結合または三重結合を意味し、
Ｒ⁵は、ヒドロキシによって置換されたＣ₁−Ｃ₄−アルキルまたは水素またはＣＨ₂ＯＲ⁶を意味し、
Ｒ⁶は、ヒドロキシによって置換されたＣ₁−Ｃ₄−アルキルまたは水素またはスルホン酸基もしくはその塩を意味するが、
但し、Ｒ⁵およびＲ⁶は、同時には水素を意味せず、かつ
但し、破線は単結合を意味する）
の１種または複数の化合物。
６． 追加的に、
Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、ＳＯ₄ ^2-、ＯＨ^-およびＣｌＯ₄ ^-
から成る群から選択される１種、２種、２種を超えるまたは全ての陰イオンを含有する、前記態様の１つに記載の電解浴または混合物。

Means a double or triple bond in the cis or trans configuration,
R ⁵ means C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or CH ₂ OR ⁶ ;
R ⁶ represents C ₁ -C ₄ -alkyl substituted by hydroxy or hydrogen or a sulfonic acid group or salt thereof,
However, R ⁵ and R ⁶ do not mean hydrogen at the same time, and the broken line means a single bond.)
One or more compounds of.
6. Additionally,
F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , SO ₄ ²⁻ , OH ⁻ and ClO ₄ ^−.
An electrolysis bath or mixture according to one of the preceding aspects, containing one, two, more than two or all anions selected from the group consisting of:

7. Additionally,
Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ and Sr ²⁺
An electrolysis bath or mixture according to one of the preceding aspects, containing one, two, more than two or all cations selected from the group consisting of:
8. If the electrolytic cell or mixture is in an aqueous solution,
(H) contains one, two or all compounds selected from the group consisting of chloral hydrate, bromal hydrate, formaldehyde and acetaldehyde,
Electrolytic bath or mixture according to one of the previous embodiments, wherein the compound or compounds is preferably chloral hydrate.
9. Electrolytic bath or mixture according to one of the previous aspects, which is a single-phase solution.
10. The electrolytic bath or mixture according to one of the previous embodiments, which is free of silicon oxide particles and aluminum oxide particles suspended in the electrolytic bath or mixture.
11. The electrolysis bath or mixture according to one of the previous aspects, which is free of oxide particles suspended in the electrolysis bath or mixture.

12. The electrolysis bath or mixture according to one of the previous embodiments, which is free of particles suspended in the electrolysis bath or mixture.
13. Electrolytic bath or mixture according to one of the preceding aspects, having a pH value in the range of 2.8 to 5.2, preferably 3.8 to 4.8.
14. Multiple components
(A1) nickel sulfate,
(A2) nickel chloride,
(B1) boric acid,
(C1) benzoic acid sulfimide sodium salt,
(D1) allylsulfonic acid sodium salt,
(E1) 2-propyn-1-ol,
(E2) 1-diethylamino-prop-2-yne,
(E3) hexa-3-yne-2,5-diol,
(F1) pyridinium propyl sulfobetaine,
(G-VI) formula (VI)

(VI)
,
（式中、
ｎは、１〜２４の範囲内の整数を意味し、
Ｒ⁴は、炭素原子１〜２０個を有する飽和分枝もしくは飽和非分枝アルキル基を意味する）
の脂肪アルコールエーテルスルファートのナトリウム塩、
（ｈ１）抱水クロラール、
（ｉ１）プロパ−２−イン−１−オール−エトキシラート
から成る群から選択される、複数の構成成分の混合によって製造可能な、前記態様の１つに記載の電解浴または混合物。
１５． 複数の成分が、
（ａ）全量１．１２〜１．６７ｍｏｌ／Ｌのニッケルイオン、
（ｂ１）全量０．４８５〜０．９７ｍｏｌ／Ｌのホウ酸、
（ｃ）全量０．００５５〜０．０２７４ｍｏｌ／Ｌの安息香酸スルフィミド陰イオン、
（ｄ）全量０．００６〜０．０２５ｍｏｌ／Ｌのアリルスルホナート、
（ｅ１）全量０．０００３６〜０．００８９ｍｏｌ／Ｌの２−プロピン−１−オール、
（ｅ２）全量０〜０．００４５ｍｏｌ／Ｌの１−ジエチルアミノ−プロパ−２−イン、
（ｅ３）全量０〜０．００８８ｍｏｌ／Ｌのヘキサ−３−イン−２，５−ジオール、
（ｆ１）全量０．０００２５〜０．００２５ｍｏｌ／Ｌのピリジニウムプロピルスルホベタイン、
（ｇ）全量０．０００６〜０．０２５ｍｏｌ／Ｌの、式（ＶＩ）

(VI)
,
(In the formula,
n means an integer in the range of 1 to 24,
R ⁴ represents a saturated branched or saturated unbranched alkyl group having 1 to 20 carbon atoms)
Sodium salt of fatty alcohol ether sulphate,
(H1) Chloral hydrate,
(I1) An electrolytic bath or mixture according to one of the previous aspects, which is producible by mixing a plurality of constituents selected from the group consisting of prop-2-yn-1-ol-ethoxylate.
15. Multiple ingredients
(A) Nickel ions in a total amount of 1.12 to 1.67 mol / L,
(B1) boric acid in a total amount of 0.485 to 0.97 mol / L,
(C) Total amount of 0.0055 to 0.0274 mol / L sulfimide anion benzoate,
(D) Allyl sulfonate in a total amount of 0.006 to 0.025 mol / L,
(E1) 2-propyn-1-ol in a total amount of 0.00036 to 0.0089 mol / L,
(E2) 1-diethylamino-prop-2-yne in a total amount of 0 to 0.0045 mol / L,
(E3) Hex-3-yne-2,5-diol in a total amount of 0 to 0.0088 mol / L,
(F1) Pyridinium propyl sulfobetaine in a total amount of 0.00025 to 0.0025 mol / L,
(G) Formula (VI) with a total amount of 0.0006 to 0.025 mol / L.

(VI)
,
（式中、
ｎは、それぞれ独立して、１〜２４の範囲内の整数を意味し、
Ｒ⁴は、それぞれ独立して、炭素原子１〜２０個を有する飽和分枝もしくは飽和非分枝アルキル基を意味する）
の脂肪アルコールエーテルスルファートのナトリウム塩、
（ｈ１）全量０．００３〜０．０１８ｍｏｌ／Ｌの抱水クロラール、
および
（ｉ１）全量０〜０．００２５ｍｏｌ／Ｌのプロパ−２−イン−１−オール−エトキシラート
から成る群から選択される、複数の成分の混合によって製造可能な、前記態様の１つに記載の電解浴。

(VI)
,
(In the formula,
n each independently represents an integer in the range of 1 to 24,
R ⁴ independently represents a saturated branched or saturated unbranched alkyl group having 1 to 20 carbon atoms)
Sodium salt of fatty alcohol ether sulphate,
(H1) 0.003 to 0.018 mol / L of chloral hydrate,
And (i1) one of the above aspects, which can be prepared by mixing a plurality of components selected from the group consisting of propa-2-yn-1-ol-ethoxylates in a total amount of 0-0.0025 mol / L. Electrolytic bath.

16. A method of manufacturing an article having a bright nickel layer by depositing nickel on a corresponding workpiece, comprising the steps of:
(A) preparing and / or producing an electrolytic bath or mixture according to one of the above aspects,
(B) a method comprising the step of electrodepositing nickel from a prepared or prepared electrolytic bath or mixture onto a workpiece to produce a bright nickel layer.
17. The method according to aspect 16, wherein the temperature of the electrolytic bath or mixture is in the range of 40-70 ° C. in step (b).
18. The method according to one of aspects 16 to 17, wherein in step (b) a bright nickel layer is deposited on the copper, brass or zinc surface of the work piece.
19. 19. The method according to one of aspects 16-18, wherein the article is a component of a conduit or a component of a part for a water conduit.

20. 20. The method according to one of aspects 16 to 19, wherein in step (b) the deposition is performed on the surface of the work piece, which surface is part of the semi-bright nickel layer of the work piece.
21. The following additional steps:
21. One of aspects 16 to 20, comprising (c) depositing a further metal layer on the bright nickel layer, preferably electrodepositing, preferably depositing a chromium layer on the bright nickel layer. the method of.
22. Use of the electrolytic bath or mixture according to one of the embodiments 1 to 15 for depositing or producing a bright nickel layer.
23. The use according to aspect 22, for the manufacture of a bright nickel layer on a component of a part for a water conduit.

24. The bright nickel layer
By depositing nickel on the corresponding workpiece using the electrolytic bath or mixture according to one of the embodiments 1 to 15,
Or using the method according to one of aspects 16 to 21,
Articles that are manufacturable and that comprise a bright nickel layer, preferably components of conduits or components of components for water conduits.
25. Use of (i) a mixture for use in an electrolytic bath or (ii) an electrolytic bath for the production of a bright nickel layer on a component of a component for a water conduit.
(I) the mixture or (ii) the electrolytic bath in an aqueous solution,
(C) sulfimide benzoate and / or sulfimide benzoate anion,
And (h) one, two, more than two or all compounds selected from the group consisting of chloral hydrate, bromal hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehydes ,
Use in which the electrolytic bath additionally contains the following components, or the mixture additionally contains all of the following components in aqueous solution:
(A) nickel ion,
(B) one or more acids,
(D) allyl sulfonic acid and / or allyl sulfonate,
(E) Formula (I)

(I)
,
（式中、
Ｒ¹はヒドロキシ、アミノ、Ｃ₁−Ｃ₄−アルキルアミノもしくはジ（Ｃ₁−Ｃ₄−アルキル）アミノによって置換されたＣ₁−Ｃ₄−アルキルまたは水素またはＣ₁−Ｃ₄−アルキルを意味し、
Ｒ²は、ヒドロキシ、アミノ、Ｃ₁−Ｃ₄−アルキルアミノもしくはジ（Ｃ₁−Ｃ₄−アルキル）アミノによって置換されたＣ₁−Ｃ₄−アルキルを意味する）
の１種または複数のアセチレン系不飽和化合物、
（ｆ）式（ＩＩ）

(I)
,
(In the formula,
R ¹ is hydroxy, amino, C ₁ -C ₄ - refers to an alkyl - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C substituted by amino ₄ - alkyl or hydrogen or C ₁ -C ₄ Then
R ² is hydroxy, amino, C ₁ -C ₄ - refers to an alkyl) - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C ₄ substituted by amino
One or more acetylenically unsaturated compounds of
(F) Formula (II)

(II)
,
（式中、それぞれ相互に独立して、
芳香族環系の窒素原子構成部は、ピリジン、キノリンおよびイソキノリンからなる群から選択され、
ｍは、１〜２４の範囲内の整数を意味し、
各Ｒ³は、独立して、炭素原子１〜２０個を有する分枝もしくは非分枝アルキル基または水素またはヒドロキシを意味する）
の１種または複数のベタイン、
（ｇ）１種または複数の湿潤剤。

(II)
,
(In the formula, each independently,
The nitrogen atom component of the aromatic ring system is selected from the group consisting of pyridine, quinoline and isoquinoline,
m means an integer in the range of 1 to 24,
Each R ³ independently represents a branched or unbranched alkyl group having 1 to 20 carbon atoms or hydrogen or hydroxy)
One or more betaines of
(G) One or more wetting agents.

  For example, a nickel layer deposited using the electrolytic bath of the present invention or the mixture of the present invention on a work piece will produce more nickel ions in the aqueous solution in contact with this nickel layer than conventional bright nickel layers. It shows a low tendency to release. This is confirmed by measuring the potential of the deposited nickel layer.

Potential measurement: General reference and examples:
The determination of the potentials of the individual nickel layers and the combination of nickel layers deposited on the corresponding workpieces using the electrolytic baths of the invention or the mixtures of the invention is usually carried out by the so-called STEP test (STEP: thickness and electrode). It is performed by simultaneous determination of potentials (simultaneous thickness and electordepotential determination). For experimental conditions and experimental construction of STEP tests, reference is made to DIN 50022.

  Using the STEP test, which is a method for verifying the quality of the deposited nickel layer or the deposited nickel layer system, the parameters relevant to the corrosion process, namely the layer thickness of the individual nickel layers and their mutual potential difference are used. Can be measured in just one working step. When using the STEP test method, it is exploited that the potential measured on the standard electrode upon dissolution changes rapidly after the nickel layer is stripped. This change takes place after the respective nickel layer has melted, the measured potential of the melting being dependent, inter alia, on the nature of the respective nickel layer. This is the case for sulfur-containing and sulfur-free nickel layers. However, in the case of two sulfur-containing nickel layers, the large potential difference is almost unmeasurable. The STEP test is a measurement method that destroys the nickel layer to be analyzed or the nickel layer system to be analyzed and is carried out with a Coulosk. The change in potential, which can be measured and illustrated by the electrical detachment of the individual nickel layers from the nickel system, indicates, in the case of an abrupt change, the turning point from one nickel layer to the next in such a layer system. The endpoint of the measurement of the STEP test is the arrival at the substrate, eg the copper layer. Generally, nickel potential is measured in a solution of nickel chloride hexahydrate, sodium chloride and boric acid. A sufficient potential between the semi-bright nickel layer and the bright nickel layer is given by -120 mV when measured in the electrolyte described above.

  To determine the spontaneous potential of nickel coatings produced with the electrolytic bath of the invention or the mixture of the invention, the test setup described below is used: Test nickel coating whose composition is defined by the components of the bright nickel electrolyte. Was immersed in a Corrodkote solution containing ammonium chloride, copper nitrate and iron (III) chloride, and its spontaneous potential was compared to a reference electrode (half cell electrode) also immersed in the above solution. To measure. The reference electrode consists of a silver / silver chloride electrode (Messkette). A high resistance measuring device, such as a pH meter or a multiple measuring device, serves as the measuring device. In this regard, the average measurement time is between 45 and about 60 minutes. Stable potentials usually occur within this time frame and their values are relative. Such measured relative values can be compared to relative values of differently configured nickel coatings, also determined in the manner described above. A preferred potential difference between the semi-bright nickel layer and the bright nickel layer is, for example, about -70 mV.

  For the approach of corrode coat solution, 20 g / l ammonium chloride by Brugger, Robert (1984), "Die galvanische Vernickelung", 2. Aufl. Saulgau (Eugen G. Leutze Verlag Bd. 12) S. 301, 3. An aqueous solution of 3 g / l iron (III) chloride and 0.7 g / l copper (II) nitrate trihydrate is used.

result:
Measurement of the self-potential in nickel-coated corrode coat solution produced using an electrolytic bath:

note:
The comparative bath and the bath of the invention had the same composition except for the chloral hydrate share.

Measurement by Step test:
The potential of the nickel coating produced using the comparative bath was +484 mV and the potential of the nickel coating produced using the bath of the invention with 1 g / l chloral hydrate was +582 mV. The above notes apply accordingly.

Use Examples 1 to 7: Production of an electrolytic bath by mixing water with selected components (containing components); unit of concentration mol / L:

  The pH value of the electrolytic bath is between 3.8 and 4.8 after mixing. The above components are placed in an aqueous solution at the above concentrations. The order in which the individual components are added to the aqueous solution is then not critical. All concentration statements are for the electrolytic bath.

Use Examples 8 to 14: Production of electrolytic bath by mixing water with selected component (containing component); unit of concentration mol / L:

The pH value of the electrolytic bath is between 3.8 and 4.8 after mixing. The above components are placed in an aqueous solution at the above concentrations. The order in which the individual components are added to the aqueous solution is then not critical. All concentration statements are for the electrolytic bath.
General Example H1: Manufacture of the electrolytic bath of the invention:
Selected components (contained components) of the electrolytic bath according to the invention, which are present as salts, are dissolved in completely demineralized water. The water then preferably has a temperature in the range from 30 to 70 ° C. Activated carbon 0.16 to 0.25 mol / L is added to the resulting aqueous solution. At that time, the activated carbon and the aqueous solution are mixed by stirring or precoat filtration with a circulation pump. Subsequently, the activated carbon is removed by filtration and the pH value of the remaining purified solution is adjusted to a value within the range 3.5-5.0.

In a further step, selected components of the electrolysis bath of the invention (contained components), which are not present as salts, are added to this purified solution.
Stagnation test: Inspection of nickel migration from the bright nickel layer of the invention into municipal water:
(A) For comparison purposes, a conventional electrolytic bath (without chloral hydrate) was used to provide a bright nickel layer on a copper tube 10 cm long and 2 cm in diameter. A chromium layer was electrically deposited on the bright nickel layer in a second step. These layers each had a thickness of about 10 μm nickel or about 0.2-0.3 μm chromium.
(B) In parallel therewith, a similar such copper tube was used for comparison purposes in an electrolytic bath of the invention of the same composition as the comparative bath except that it additionally contained 500 mg / l chloral hydrate. A bright nickel layer was first applied, and a chromium layer was electrically applied in the second step, under the same conditions as the tests carried out in.
(C) In parallel with this, in the same way, in the same way, a similar such copper tube is first added in a further inventive electrolytic bath containing 1000 mg / l of chloral hydrate first to bright nickel. The layer was electrically applied with the last chromium layer in the second step.

  Subsequently, the copper tubes electroplated as in (a), (b) and (c) above (one for comparison; two of the present invention) were separately immersed in city water. The concentration of nickel / nickel ions in the municipal water was measured after each standing time of 72 hours. Further measurements are taken after a further 48 hours, 120 hours, 72 hours and 144 hours, respectively. In all cases, the water was changed after the measurement. In addition, the test copper tubes were rinsed 10 times with 150 ml of municipal water each before further use. The measurement results were confirmed with an ICP-OES spectrometer and are shown in the following table. The numerical values indicate the measured nickel ion concentration (μg / l).

Five tubes each plated with (a), (b) or (c) were used for each measurement. The displayed value is the arithmetic mean.
The addition of chloral hydrate significantly reduces the tendency of nickel / nickel ion release into the surrounding medium (here municipal water), especially for long contact times (2nd-5th measurements). That can be clearly confirmed.

Use Example 15: Preparation of a specific inventive electrolytic bath:
The particular components of the inventive electrolytic bath, which are present as salts (components), namely components a, c, d and f, are dissolved in the fully demineralized water at the indicated concentrations. The water then preferably has a temperature of 55 ° C. Activated carbon 0.16 to 0.25 mol / L is added to the resulting aqueous solution. At that time, the activated carbon and the aqueous solution are mixed by stirring or precoat filtration with a circulation pump. The activated carbon is subsequently removed by filtration and the pH value of the remaining purified solution is adjusted to a value of 4.2.

In a further step, selected components of the electrolysis bath of the invention (contained components), which are not present as salts, are added to this purified solution.
Specific electrolytic bath components (contained components) of the present invention:

The plating time, i.e. the time required to deposit the bright nickel layer using the particular bath of the invention, is about 15 minutes at a current density of 4 A / dm ² .
Use and Comparative Example 16: Manufacture of certain inventive articles having a bright nickel layer (bathroom components as examples of water conduits):
The components (contained components) of the particular electrolytic bath to be used according to the invention for the production of the article according to the invention (bathroom parts with a bright nickel layer) are listed in the following table "Use example 16" and are It was dissolved in salt water (preferably water temperature 55 ° C.) at the indicated concentration.

The components of the electrolytic bath not according to the invention prepared for comparison purposes are the same as those according to the table "Use example 16", which components are likewise indicated in completely demineralized water (preferably at a water temperature of 55 ° C.). Dissolved in concentration. However, the electrolytic bath produced for comparison purposes does not contain chloral hydrate.
The plating time, i.e. the time until the deposition of a bright nickel layer with a particular inventive bath or an electrolytic bath not according to the invention prepared for comparison purposes, is approximately 15 for a current density of 4 A / dm ² , respectively. It was a minute.

A bathroom component body constructed in the same manner was used.
(A) Manufacture of the article of the invention:
A bright nickel layer was provided on a brass bathroom component body using the electrolytic bath of the present invention. The thickness of this layer was about 10 μm. In the second step, a chromium layer was electrically deposited on this bright nickel layer (temperature: 36-44 ° C., current density 5-20 A / dm ² , time: 2-5 minutes). The thickness of this layer was 0.2 to 0.3 μm.
(B) Manufacture of articles not according to the invention (comparison):
A bright nickel layer was provided on a brass bathroom component body using an electrolytic bath not according to the present invention. The thickness of this layer was about 10 μm. In the second step, a chromium layer was electrically deposited on this bright nickel layer (temperature: 36-44 ° C., current density 5-20 A / dm ² , time: 2-5 minutes). The thickness of this layer was 0.2 to 0.3 μm.

Stagnation test for bathroom parts: Comparative examination of nickel migration from bright nickel layer of the invention and bright nickel layer not according to the invention into municipal water:
The brass parts electroplated as in (a) and (b) above were separately immersed in municipal water. The concentration of nickel / nickel ion in municipal water was measured after each one week of standing time. Further measurements are made after 2, 3, 4 and 5 weeks, respectively. In all cases, the municipal water was changed after the measurement. In addition, the tested brass parts were rinsed 10 times with 150 ml each of municipal water before re-soaking. The measurement results are confirmed by the ICP-OES spectrometer and are shown in the following table. The numerical values indicate the measured nickel ion concentration (μg / l).

表示した値は、それぞれ４回の測定の算術平均である。

The values shown are the arithmetic average of 4 measurements each.

  It can clearly be seen that the bathroom component body plated according to the invention (as an example of an article of the invention) liberated less nickel than the plated bathroom component body not according to the invention. The bath of the present invention used contained chloral hydrate, which clearly reduced the tendency of nickel / nickel ion release into the surrounding medium (here municipal water). In particular, the results of weeks 4 and 5 show that the nickel release was stagnant, at the same time being significantly less than the nickel release of the brass parts plated without the invention.

Claims (19)

An electrolytic bath for the deposition of a bright nickel layer, or a mixture for use in an electrolytic bath for the deposition of a bright nickel layer, said mixture being in an aqueous solution, or said electrolytic bath being in an aqueous solution,
(C) containing sulfimide benzoate and / or sulfimide benzoate anion and (h) chloral hydrate,
The electrolysis bath or mixture as described above, wherein the electrolysis bath additionally comprises the following components, or the mixture additionally comprises the following components:
(A) nickel ion,
(B) one or more acids,
(E) Formula (I)

(I)
(In the formula,
R ¹ is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C substituted by amino ₄ - alkyl or hydrogen, or C ₁ -C _4, - Alkyl,
R ² is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C ₄ substituted by amino - alkyl)
One or more acetylenically unsaturated compounds of
(F) Formula (II)

(II)
(In the formula, each independently,
The nitrogen atom is part of an aromatic ring system selected from the group consisting of pyridine, quinoline and isoquinoline,
m is an integer in the range of 1 to 24,
Each R ³ is independently a branched or unbranched alkyl group having 1 to 20 carbon atoms, or hydrogen, or hydroxy)
One or more betaines of
(G) One or more wetting agents. The electrolysis bath or mixture according to claim 1, wherein the electrolysis bath or mixture comprises one, more or all of the following components in an aqueous solution:
(B) one or more inorganic acids selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid and / or one or more organic compounds selected from the group consisting of malic acid, citric acid, lactic acid and amidosulfonic acid An acid and / or (g) one or more wetting agents, wherein one or more or all of the one or more wetting agents,
(I) an aliphatic alcohol ether sulphate and / or an acid produced therefrom by protonation,
(Ii) an aliphatic alcohol sulfate and / or an acid produced therefrom by protonation,
(Iii) a mixture comprising or consisting of an aliphatic alcohol ether sulphate and an aliphatic alcohol sulphate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulphate acid and fatty alcohol sulphate acid,
(V) a mixture containing or consisting of an acid of an aliphatic alcohol ether sulfate and an aliphatic alcohol sulfate,
And (vi) an acid of an aliphatic alcohol ether sulphate and a mixture comprising or consisting of an aliphatic alcohol sulphate,
One selected wetting agent carries a branched or unbranched alkyl group as the carbon chain,
Alternatively, a plurality of selected wetting agents carry, as carbon chains, independently of one another, a branched or unbranched alkyl group. The electrolysis bath or mixture according to claim 1 or 2, wherein the electrolysis bath or the mixture comprises one, a plurality or all of the following components in an aqueous solution:
(A) a total amount of 1.12 to 1.67 mol / L of nickel ions, and / or (b) a total amount of 0.485 to 0.97 mol / L,
One or more inorganic acids selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid, and / or one or more organic acids selected from the group consisting of malic acid, citric acid, lactic acid and amidosulfonic acid, And / or (c) 0.0055 to 0.0274 mol / L of benzoic acid sulfimide and benzoic acid sulfimide anion, and / or (d) 0.006 to 0.025 mol / L of allyl sulfonic acid and allyl sulfo. And / or (e) a total amount of 0.00036 to 0.1438 mol / L of the formula (I)

(I)
(In the formula,
R ¹ is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C substituted by amino ₄ - alkyl or hydrogen or, C ₁ -C _4, - Alkyl,
R ² is hydroxy, amino, C ₁ -C ₄ - alkylamino or di (C ₁ -C ₄ - alkyl) C ₁ -C ₄ substituted by amino - alkyl)
One or more acetylenically unsaturated compounds of the formula (II), and / or (f) a total amount of 0.00025 to 0.0025 mol / L,

(II)
(In the formula, each independently,
The nitrogen atom is part of an aromatic ring system selected from the group consisting of pyridine, quinoline and isoquinoline,
m is an integer in the range of 1 to 24,
Each R ³ is independently a branched or unbranched alkyl group having 1 to 20 carbon atoms, or hydrogen, or hydroxy)
And / or (g) a total amount of 0.0006 to 0.025 mol / L, one or more wetting agents, one wetting agent or one of a plurality of wetting agents Or multiple or all,
(I) an aliphatic alcohol ether sulphate and / or an acid produced therefrom by protonation,
(Ii) an aliphatic alcohol sulfate and / or an acid produced therefrom by protonation,
(Iii) a mixture comprising or consisting of an aliphatic alcohol ether sulphate and an aliphatic alcohol sulphate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulphate acid and fatty alcohol sulphate acid,
(V) a mixture containing or consisting of an acid of an aliphatic alcohol ether sulfate and an aliphatic alcohol sulfate,
And (vi) a wetting agent selected from the group consisting of a mixture of acids of fatty alcohol ether sulphates and fatty alcohol sulphates, or
The aliphatic alcohol ether sulfate has the formula (III)

(III)
(In the formula, each independently,
n is an integer in the range of 1 to 24,
R ⁴ is a branched or unbranched alkyl group having 1 to 20 carbon atoms, and X is selected from the group consisting of Li, Na, K, Rb, Cs and NH _4.
Selected from the group consisting of aliphatic alcohol ether sulphates and / or acids formed therefrom by protonation,
And / or the fatty alcohol sulphate has the formula (IV)

(IV)
(In the formula, each independently,
n is an integer in the range of 1 to 24,
R ⁴ is a branched or unbranched alkyl group having 1 to 20 carbon atoms, and X is selected from the group consisting of Li, Na, K, Rb, Cs and NH ₄ ) aliphatic) The above wetting agent selected from the group consisting of alcohol sulphate and / or an acid formed therefrom by protonation, and / or (h) a total amount of 0.003 to 0.018 mol / L chloral hydrate, and / or ( i) Total amount of 0 to 0.0025 mol / L, formula (V)

(V)
(In the formula,

Is a double or triple bond in the cis or trans configuration,
R ⁵ is C ₁ -C ₄ -alkyl or hydrogen substituted by hydroxy or CH ₂ OR ⁶ and R ⁶ is C ₁ -C ₄ -alkyl or hydrogen substituted by hydroxy or a sulfonic acid group or That salt,
However, R ⁵ and R ⁶ are not hydrogen at the same time, and the broken line means a single bond.)
One or more compounds of. Additionally,
F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , SO ₄ ²⁻ , OH ⁻ and ClO ₄ ^−.
Containing one, two, more than two or all anions selected from the group consisting of and / or additionally:
Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ and Sr ²⁺
Electrolytic bath or mixture according to one of claims 1 to 3, containing one, two, more than two or all cations selected from the group consisting of:   Electrolytic bath or mixture according to claim 1, which is a single-phase solution.   Electrolytic bath or mixture according to one of claims 1 to 5, having a pH value in the range of 2.8 to 5.2.   7. The electrolytic bath or mixture according to claim 6, which has a pH value in the range of 3.8 to 4.8.   8. Any of claims 1-7, wherein the betaine of formula (II) is at least one selected from 1- (3-sulfopropyl) pyridinium betaine and 1- (2-hydroxy-3-sulfopropyl) pyridinium betaine. The electrolytic bath or mixture as described in 1 above.   9. The electrolytic bath or mixture according to claim 1, which is free of suspended silicon oxide particles and aluminum oxide particles. A method of manufacturing an article having a bright nickel layer by depositing nickel on a corresponding workpiece, comprising the steps of:
(A) preparing and / or producing an electrolytic bath or mixture according to claim 1 to 9,
(B) a method comprising the step of electrodepositing nickel from a prepared or prepared electrolytic bath or mixture onto a workpiece to produce a bright nickel layer.   The method according to claim 10, wherein the temperature of the electrolytic bath or the mixture of step (b) is in the range of 40 to 70 ° C.   The method according to claim 10 or 11, wherein in step (b) a bright nickel layer is deposited on the copper, brass or zinc surface of the work piece.   13. Method according to one of claims 10 to 12, wherein the article is a component of a conduit or a component of a part for a water conduit.   14. The method according to claim 10, wherein in step (b) deposition is carried out on the surface of the work piece, the surface being part of the semi-bright nickel layer of the work piece. The following additional steps:
15. The method according to claim 10, comprising the step of (c) depositing a further metal layer on the bright nickel layer.   The method according to claim 15, wherein the deposition is electro-deposition.   17. The method of claim 16, wherein the electrodeposition is the electrodeposition of a chromium layer on a bright nickel layer.   Use of the electrolytic bath or mixture according to claim 1 to 9 for depositing or producing a bright nickel layer.   19. Use according to claim 18 for the deposition or production of a bright nickel layer on a component of a component for a water conduit.