JP2015212417A - Electrolytic bath for precipitation of bright nickel layer, mixture for use in electrolytic bath for precipitation of bright nickel layer and production method of article having bright nickel layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolytic bath for production of a bright nickel layer on a constituent element of a part for a water conduit tube and a mixture for use in an electrolytic bath.SOLUTION: An electrolytic bath or a mixture comprises (c) benzoic acid sulfimide and/or benzoic acid sulfimide anion, (h) one or more or all the compounds selected from chloral hydrate, bromal hydrate, formic acid, formate, acetic acid, acetate and substituted/unsubstituted aliphatic aldehydes, (a) nickel ion, (b) one ore more acids, (e) one or more acetylene-based unsaturated compounds of formula (I), (f) one or more betaines of formula (II) and (g) one or more humectants.

Description

  The invention relates to an electrolytic bath for depositing a bright nickel layer, a corresponding mixture for use in an electrolytic bath for depositing a bright nickel layer, and a gloss by depositing nickel on the corresponding workpiece. The invention relates to a corresponding method for producing articles having 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 bright nickel layers, and articles comprising the bright nickel layers according to the invention.

Electrolytic baths and methods for the electrodeposition of bright nickel layers are known from the prior art.
Here, an international patent application having publication number WO 93/15241 A1 is for example from an aqueous acidic bath containing one or more nickel salts, one or more inorganic acids, and at least two brighteners as essential components. The present invention relates to a method for producing a nickel-plated molded member by electrodepositing nickel. This publication further relates to brightener mixtures that can be used for the process. As a kind of the substance that gives gloss,
-Sulfonimides, such as benzoic acid sulfimides,
-Sulfonamides,
Benzene sulfonic acids, such as monobenzene sulfonic acid, dibenzene sulfonic acid and tribenzene sulfonic acid,
-Naphthalenesulfonic acid, for example mononaphthalenesulfonic acid, dinaphthalenesulfonic acid and trinaphthalenesulfonic acid,
-Alkyl sulfonic acids,
-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.

  A German patent application with publication number DE 19610361 A1 discloses a bath and method for the electro-deposition of semi-bright nickel. For the electrodeposition of a semi-bright nickel layer on a support, one or more cyclic N-allylammonium compounds, or N-vinylammonium compounds, in particular pyridinium compounds, are used as brighteners. Said patent document itself points out a series of publications from the prior art relating to the electro-deposition of semi-bright nickel. Furthermore, various chemical compounds that can be used in the electrolytic bath are mentioned. Accordingly, there is always always at least one or two and possibly a plurality of nickel salts, such as nickel sulfate, nickel chloride, nickel fluoride and other nickel salts, and at least one inorganic acid, such as sulfuric acid or boric acid. The inorganic acid is contained in the bath.

  Furthermore, the German patent having the publication number DE102008056470B3 describes a method for inspecting a metal layer, either alone or on a component of a multilayer metal layer system, and the deposition of such a metal layer. Describes a method for analytical management of the deposited electrolyte used for the purpose. In a preferred embodiment of the present invention, the metal layer is an electrolytically deposited nickel layer. As mentioned in the introductory part of the German patent specification with publication number DE102008056470B3, the electrolytically deposited multilayer nickel layer can be made of various materials as anticorrosion coating, for example copper, brass Alternatively, it is applied on a member made of steel or plastic. In that case, the multiple nickel layers are deposited in a fixed order with different qualities, i.e., for example as semi-glossy nickel layers, glossy nickel layers, optionally with a sulfur-rich intermediate layer. And again as a semi-glossy nickel layer, optionally deposited with a plurality of particles.

The basic composition of the nickel deposition electrolyte is, according to publication number DE102008056470B3, typically a so-called nickel watt bath, which contains nickel ions, chloride ions, sulfate 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 deposited electrolyte is generally 2.5 to 6.0, preferably 3 to 4.5, and particularly about 4.0. Said precipitation is carried out at a temperature of 40 to 70 ° C., preferably 50 to 60 ° C., in particular about 55 ° C. Each layer is electrolytically deposited from a deposited electrolyte solution having a different composition, particularly having a different composition in terms of additives. The semi-gloss base layer on the substrate material generally contains salicylic acid, ethyne derivatives such as hexynediol or butynediol, propargyl alcohol derivatives, formaldehyde and / or chloral hydrate or even a mixture of these compounds Contains as an agent. Sulfur-rich glossy or matte interlayers that can optionally be deposited generally contain saccharin, sulfonic acid and / or ethyne derivatives as additives. The bright nickel layer generally contains, as additives, sulfur-containing compounds such as toluene sulfonic acid or propargyl sulfonate, saccharin instead of salicylic acid, or a mixture 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 additives, and optionally additionally, for example SiO ₂ , Contains particles made of Al ₂ O ₃ . Furthermore, the deposited electrolyte may contain further additive substances such as brighteners and wetting agents.

  CH 514683 relates to "Method for electrolytic nickel plating and electrolytic nickel plating bath" (title).

  The publications mentioned above and the prior art mentioned in these publications relate to the anticorrosion, leveling, ductility, gloss and coverage of the electrodeposited semi-bright nickel layer or nickel layer of individual compounds and combinations thereof. Each advantage is described. In particular, improving the corrosion resistance of each nickel layer is a major challenge in the prior art, and that challenge should mostly be solved by the use of anticorrosive double nickel and triple nickel systems. . Such systems are often formed from a semi-bright nickel layer, a bright nickel layer, and a chromium layer, which utilizes the potential difference between the semi-bright nickel layer and the bright nickel layer. In this case, if the upper chromium layer breaks, the first more basic bright nickel layer (so-called sacrificial anode) is attacked by the corrosive medium that reaches through the broken chromium layer, after which it is more noble The semi-bright nickel layer and ultimately the substrate itself is attacked. In this case, the bright nickel layer is based on the chemical introduction of the sulfur-containing organic component and has a higher base than the semi-bright nickel layer present thereunder. As long as the sulfur-containing organic component is used, saccharin is usually used as a component of the bright nickel layer.

  The conventional electrolytic bath or nickel-plated molded part manufacturing method disclosed in the prior art for the deposition of the respective nickel layer is the most preferential corrosion in view of the protection of the electrolytically coated substrate. If the goal was to reduce, especially by the new drinking water directive, the requirements on the migration resistance of the chemical components of the layer applied electrolytically on the substrate will eventually increase. Yes. Therefore, in addition to reducing or preventing corrosion as a general purpose, preventing or reducing migration of components of a metal protective layer that has been electrolytically applied on a substrate is a new additional challenge or requirement. . Among other things, the migration of nickel as one of the metals often used in electrolysis technology from coatings that protect the substrate, nickel is considered one of the most common triggers for contact allergies (nickel dermatitis) In view of this, it is a health risk for consumers. Considering this recognition, in Germany, in particular, the second command for the change of the Drinking Water Command (TrinkwV 2001), which came into effect on December 14, 2012. Thus, in each so-called stagnation test of the alloy or coating to be investigated, a maximum of 10 μg of nickel must be released in one liter of drinking water. The coatings used so far, regardless of whether they are double coating or triple coating, do not meet the requirements of the new drinking water directive.

WO93 / 15241A1 DE19610361A1 DE102008056470B3 CH514683

The first object of the present invention is to provide an electrolytic bath for the deposition of bright nickel layers and for the deposition of bright nickel layers, which helps to prevent or at least obviously reduce nickel migration, especially in drinking water. It is to provide a corresponding mixture for use in an electrolytic bath.
Preferably, the electrolytic bath or corresponding mixture mentioned should inherently allow the deposition of a bright nickel layer which also has certain typical properties of a semi-bright nickel layer. One of these properties is, in particular, the columnar layer structure, which was previously known only for the semi-bright nickel layer, and between the semi-bright and bright nickel layers. It can be identified by measuring a clear potential difference. Thus, an effective anticorrosion will already occur with a layer system consisting of such a bright nickel layer and a chromium layer confining it.

According to the invention, the first problem imposed 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 according to claim 1. Solved by the corresponding compound for use in. A mixture in an aqueous solution according to the invention or an electrolytic bath in an aqueous solution according to the invention comprises
(C) 1 selected from the group consisting of benzoic acid sulfimide and / or benzoic acid sulfimide anion and (h) chloral hydrate, bromaric hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehyde Species, two species, more than two species or all compounds,
including.
The electrolytic baths according to the invention or the mixtures according to the invention are therefore benzoic acid sulfimides (saccharin, E954, 1,2-benzisothiazol-3 (2H) -one-1,1-dioxide, CAS number: 81-07- 2) and / or a bright nickel layer produced using an electrolytic bath according to the invention or a mixture according to the invention with a sulfur source comprising sulfimide benzoic acid anion as a sulfur source, is disclosed in the prior art. It is electrochemically less noble than the bright nickel layer.

  Furthermore, 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 present invention is based on the surprising finding that the bright nickel layer produced by the electrolytic bath according to the invention or the mixture according to the invention releases significantly less nickel into the drinking water than the usual nickel protective layer.
The electrolytic bath according to the invention or the mixture according to the invention in aqueous solution further comprises the following components:
(A) nickel ions,
(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)
,
(Where
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 Means
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 1-24,
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) includes one or more wetting agents.

The electrolysis bath according to the invention or the mixture according to the invention in an aqueous solution (preferably the electrolysis bath according to the invention or the mixture according to the invention, which is referred to below as “preferred”) is preferably further
(D) Contains allyl sulfonic acid and / or allyl sulfonate.
The ring represented by formula (II), which contains a positively charged nitrogen atom as a characteristic constituent of all betaines of formula (II), in this case is 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 nickel salts, for example nickel salts such as nickel sulfate, nickel chloride, nickel fluoride, The salts are contemplated as components of the electrolytic baths according to the invention or the mixtures 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 form dissociated at the respective pH value. Both compounds and undissociated forms of the compound are included. The acid or acids are used in particular for buffering the pH value during the electrolysis process.
The components benzoic acid sulfimide and / or benzoic acid sulfimide anion (component (c)) and optionally allyl sulfonic acid and / or allyl sulfonate (component (d)) according to the present invention comprise a basic brightener (primary Also called a brightener). Glossing means in particular the balancing or leveling of irregularities in the base material and is usually based on the use of low molecular organic surface active compounds in the electrodeposited layer. The term “leveling” refers to the smoothing of irregularities on a surface (layer), such as remaining after polishing (polishing streaks) on the surface (layer). The polishing of the surface (layer) is a usual processing measure performed before electroplating, in particular on parts, particularly preferably on brass parts, zinc parts or zinc die cast parts.

The brightener is 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 throughout the current density region and for the deposition of a ductile and undistorted nickel layer. Particularly preferably, in this case, benzoic acid sulfimide-sodium salt (CAS No. 128-44-9) is used as component (c) or in component (c) and / or as component (d) Alternatively, in the component (d), allylsulfonic acid-sodium salt (sodium prop-2-ene-1-sulfonate, sodium allylsulfonate, prop-2-ene-1-sulfonic acid-sodium salt, CAS No .: 2495- 39-8) is used.
Further named components of the electrolytic bath according to the invention or the mixture according to the invention, such as 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 others, brightening a bright nickel layer applied on a substrate by an electrolytic bath according to the invention or a mixture according to the invention Promote.

Betaines of formula (II) (component (f)) and 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 present invention or the mixture according to the present invention causes a reduction in surface tension that facilitates the rapid removal of hydrogen adhering to the cathode that occurs during electroplating processes.
Particularly preferably used compounds of the formula (I) (component (e)) are propargyl alcohol (2-propyn-1-ol, CAS No. 107-19-7), 2-butyne-1,4. -Diol (but-2-yne-1,4-diol, 1,4-butynediol, bis (hydroxymethane) acetylene, butynediol, CAS No. 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 the formula (II) (component (f)) are pyridinium propyl sulfobetaine (PPS, 1- (3-sulfopropyl) pyridinium betaine, NDSB 201, 3- (1-pyridinium) -1- Propanesulfonate, 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 each other. Preferred compounds of the formula (II) are preferably used together with further components which are preferred above or below.

The electrolytic bath according to the present invention preferably comprises one, more or all of the following components, or the mixture according to the present invention preferably 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 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 wetting agent or the plurality of wetting agents are (i) a fatty alcohol ether sulfate, and / or Or an acid produced by protonation from the salt,
(Ii) acids generated by protonation from fatty alcohol sulfates and / or their salts;
(Iii) a fatty alcohol ether sulfate, and a mixture comprising or consisting of a fatty alcohol sulfate,
(Iv) a fatty alcohol ether sulfate, and a mixture comprising or consisting of an acid of a fatty alcohol sulfate,
(V)-fatty alcohol ether sulfate, and-a mixture comprising or consisting of an acid of fatty alcohol sulfate, and (vi)-an acid of fatty alcohol ether sulfate, and-comprising a fatty alcohol sulfate, or One selected wetting agent selected from the group consisting of a mixture of them carries a branched or unbranched alkyl group as the carbon chain, or a plurality of selected wetting agents as the carbon chain. Each independently carry a branched or unbranched alkyl group.

  Alternatively or additionally, salts of sulfosuccinic acid (preferably the sodium salt) are often preferred as wetting agents in the electrolytic baths or mixtures according to the invention.

The acid or acids used are particularly preferably then selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid. Particularly preferred wetting agents, C ₁₃ ~C ₁₅ - oxo alcohol ether sulfates (CAS Number: 78330-30-0) is used. Similarly, sodium lauryl sulfate (sodium dodecyl sulfate, dodecyl sulfate-sodium salt, dodecyl sulfate-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 together with further components which are preferred above or below.

Preferably, the electrolytic bath according to the invention or the mixture according to the invention comprises, as described above, the fatty alcohol ether sulfate and / or the fatty alcohol ether sulfate and / or the fatty alcohol ether sulfate acid and / or the fatty alcohol sulfate. Containing acid,
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 fatty alcohol ether sulfates selected from the group consisting of Li, Na, K, Rb, Cs and NH ₄ , and / or acids formed by protonation from salts thereof; and / Or the fatty alcohol sulfate is of 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 ranging from 1 to 24, and 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 acids of fatty alcohol sulfates produced by protonation from salts thereof.

Particularly preferred compounds of the formula (IV) are in this case 2-ethylhexyl sulphate-sodium salt (CAS: 126-92-1) and sodium lauryl sulphate (see above). These compounds can be used alone or in combination and are preferably used together with further components which are preferred above or below.
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 as “preferred” above), 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)
,
(Where

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

  2-butyne-1,4-diol ethoxylate (2,2 ′-(but-2-yne-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-ylsulfite-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 together with further components which are preferred above or below.

In practice particularly preferred electrolytic baths comprise the following components, or indeed particularly preferred mixtures comprise one, several or all of the following components in aqueous solution (at the concentrations indicated):
(A) nickel ions having 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, and / or malic acid, citric acid, lactic acid and a total amount of 0.485 to 0.97 mol / L One or more organic acids selected from the group consisting of amidosulfonic acids,
And / or (c) a total amount of 0.0055-0.0274 mol / L benzoic acid sulfimide and benzoic acid sulfimide anion,
And / or (d) allyl sulfonic acid and allyl sulfonate in a total amount of 0.006 to 0.025 mol / L,
And / or (e) a total amount of 0.00036 to 0.1438 mol / L of 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)
,
(Where
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 Means
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) a total amount of 0.00025 to 0.0025 mol / L of 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 component of the aromatic ring system is selected from the group consisting of pyridine, quinoline and isoquinoline, and m represents an integer ranging from 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 wetting agent or the plurality of wetting agents are (i) Acids produced by protonation from fatty alcohol ether sulfates and / or their salts;
(Ii) acids produced by protonation from fatty alcohol sulfates and / or their salts;
(Iii) a fatty alcohol ether sulfate, and a mixture comprising or consisting of a fatty alcohol sulfate,
(Iv) a fatty alcohol ether sulfate acid, and a mixture comprising or consisting of a fatty alcohol sulfate acid,
(V)-fatty alcohol ether sulfate, and-a mixture comprising or consisting of an acid of fatty alcohol sulfate, and (vi)-an acid of fatty alcohol ether sulfate, and-comprising a fatty alcohol sulfate, or A fatty alcohol ether sulfate selected from the group consisting of a mixture comprising them of 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
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 fatty alcohol ether sulfates selected from the group consisting of Li, Na, K, Rb, Cs and NH ₄ , and / or acids formed by protonation from salts thereof; and / Or fatty alcohol sulfate is of 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 1-24,
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 ) and / or a wetting agent selected from the group consisting of acids formed by protonation from salts thereof And / or (h) 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 two or all compounds,
And / or (i) a total amount of 0-0.0025 mol / L, 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)
,
(Where

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,
Wherein R ⁵ and R ⁶ do not mean hydrogen at the same time, and the broken line means a single bond).

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

In practice, the individual components mentioned above of the electrolytic baths according to the invention or the particularly preferred mixtures according to the invention depend on the course of the electroplating process and on the respective consumption of the components described above. To the bath or the mixture according to the invention, it is fed as needed by means of management analysis (for example by HPLC analysis).
Of course, the electrolytic bath according to the invention or the mixture according to the invention contains the necessary amount of counterions for charge compensation in the presence of cations.

Preferably, the mixture (preferably, the mixtures according to the electrolytic bath according to the invention or the invention as a "preferred" above) by the electrolytic bath according to the invention or the invention, in addition to the above ingredients other, F ^- , Cl ⁻ , Br ⁻ , I ⁻ , SO ₄ ²⁻ , OH ⁻ and ClO ₄ ⁻ , containing one, two, more than one 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+. Contains one, two, more, or all cations.
Actually particularly preferred electrolytic baths according to the invention or particularly preferred mixtures according to the invention are
(H) chloral hydrate, bromomar hydrate, formaldehyde and acetaldehyde,
It is particularly preferable that one, two or all compounds selected from the group consisting of: chloral hydrate is one of the one compound or compounds.

In practice, an electrolytic bath according to the invention or a mixture according to the invention which is a single-phase solution is even more particularly preferred.
Particular preference is given to an electrolytic bath according to the invention or a mixture according to the invention which does not contain suspended silicon oxide particles and aluminum oxide particles.
Particularly preferred are electrolytic baths according to the invention or mixtures according to the invention which do not contain suspended oxide particles.
Moreover, the electrolytic bath according to the present invention or the mixture according to the present invention, which does not contain particles suspended in the electrolytic bath or the mixture, is preferable.

Particular preference is given to electrolytic baths according to the invention or mixtures according to the invention having 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 baths according to the invention or the preferred mixtures according to the invention exhibit particularly good water solubility.
Particularly preferred are electrolytic baths according to the invention or mixtures according to the invention, which can be produced by mixing several components, wherein the 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 represents a saturated, branched or saturated unbranched alkyl group having 1-20 carbon atoms) fatty alcohol ether sulfate sodium salt,
(H1) Chloral hydrate,
(I1) Selected from the group consisting of prop-2-yn-1-ol-ethoxynate.

Even more particularly preferred are electrolytic baths according to the present invention (preferably electrolytic baths according to the present invention which have been referred to as “preferred” above), which can be prepared by mixing several components,
(A) nickel ions having a total amount of 1.12 to 1.67 mol / L,
(B1) boric acid having a total amount of 0.485 to 0.97 mol / L,
(C) A total amount of 0.0055 to 0.0274 mol / L benzoic acid sulfimide anion,
(D) Allyl sulfonate having 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 0-0.0045 mol / L,
(E3) 0-3-0.0088 mol / L of hexa-3-yne-2,5-diol,
(F1) pyridinium propyl sulfobetaine having a total amount of 0.00025 to 0.0025 mol / L,
(G) Formula (VI) of total amount 0.0006-0.025 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)
,
(Where
each n independently represents an integer in the range of 1-24,
R ⁴ each independently represents a saturated branched or saturated unbranched alkyl group having 1 to 20 carbon atoms) fatty alcohol ether sulfate sodium salt,
(H1) chloral hydrate having a total amount of 0.003 to 0.018 mol / L,
And (i1) selected from the group consisting of prop-2-yn-1-ol-ethoxynate in a total amount of 0-0.0025 mol / L.

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

  Preferably, in the process according to the invention, the temperature of the electrolytic bath or mixture is in the range from 40 to 70 ° C., preferably in the range from 50 to 60 ° C., in step (b). At such a temperature, the individual components of the preferred electrolytic bath according to the invention or the preferred inventive mixture 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 workpiece.
Particularly preferred is a method according to the invention, wherein the article is a component of a conduit or a component of a component for a conduit.
Even more particularly preferred is the process according to the invention in which the above-described deposition on the surface of the workpiece takes place and this 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 electrodepositing, preferably electrodepositing a chromium layer on the bright nickel layer;
Particularly preferred is the process according to the invention having
In the process according to the invention, it is preferred to blow air into the electrolytic bath according to the invention and / or to move the workpiece in which nickel is to be electrodeposited in the electrolytic bath or mixture. Blowing air or moving the workpiece in the electrolytic bath according to the invention or the mixture according to the invention, in this case, serves for a better electrolyte exchange on the workpiece surface on which nickel is to be electrodeposited.

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

Similarly, the analytical control of the composition of the electrolytic bath according to the invention or the mixture according to the invention as part of the method according to the invention is preferably carried out by titration in the case of acid and chloride concentrations, and gloss In the case of agent concentration, it is done by HPLC analysis, in the case of wetting agent, it is done by measuring surface tension, and in the case of nickel (ion) concentration, by chemical analysis or AAS (atomic absorption spectroscopy) Done. Atomic absorption spectroscopy (AAS) can further measure the concentration of impurity metals that may be present in the electrolytic bath or mixture.
The invention also relates to the use of the above electrolytic bath or mixture for the deposition or production of bright nickel layers. The above description for the preferred embodiments of the bath or mixture according to the invention applies accordingly.

The invention further relates to the use of the electrolytic bath or mixture as described above for the deposition or production of a bright nickel layer on components of a conduit component. The above description for the preferred embodiments of the bath or mixture according to the invention applies accordingly.
The invention also relates to an article comprising a bright nickel layer, particularly preferably a component of a conduit or a component for a conduit, wherein the bright nickel layer is
By depositing nickel on the corresponding workpiece using the electrolytic bath or mixture described above, or by the method described above
Articles that can be manufactured, particularly preferably components of conduits or components of components for water conduits.

In the following, the invention is 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) benzoic acid sulfimide and / or benzoic acid sulfimide 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,
Electrolytic bath or mixture wherein the electrolytic bath additionally comprises the following components or the mixture additionally comprises the following components:
(A) nickel ions,
(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)
,
(Where
R ¹ represents C ₁ -C ₄ -alkyl or hydrogen or C ₁ -C ₄ -alkyl substituted by hydroxy, amino, C ₁ -C ₄ -alkylamino or di (C ₁ -C ₄ -alkyl) amino. Means
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 1-24,
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. An electrolytic bath or mixture according to embodiment 1, wherein the electrolytic bath comprises the following components or the mixture comprises one, more than one 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 organics 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 wetting agent or the plurality of wetting agents are:
(I) acids produced by protonation from fatty alcohol ether sulfates and / or salts thereof,
(Ii) acids produced by protonation from fatty alcohol sulfates and / or their salts,
(Iii) a mixture comprising or consisting of a fatty alcohol ether sulfate and a fatty alcohol sulfate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulfate acid and fatty alcohol sulfate acid;
(V) a group comprising or consisting of fatty alcohol ether sulfates and fatty alcohol sulfate acids and (vi) a group comprising or consisting of fatty alcohol ether sulfate acids and fatty alcohol sulfates Selected from
One selected wetting agent carries a branched or unbranched alkyl group as a carbon chain, or a plurality of selected wetting agents as a carbon chain, each independently, branched or Carrying an unbranched alkyl group,
And / or one wetting agent or one or more or all of the plurality of wetting agents selected from the group consisting of salts of sulfosuccinic acid.
3. The fatty alcohol ether sulfate is of 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 represents an integer within 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 formed by protonation from fatty alcohol ether sulfates and / or salts thereof;
And / or the fatty alcohol sulfate is of 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 represents an integer within 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
The electrolytic bath or mixture according to embodiment 2, selected from the group consisting of acids formed by protonation from fatty alcohol sulfates and / or salts thereof.
4). The electrolytic bath or mixture according to one of the preceding embodiments, wherein the electrolytic bath additionally comprises the following components or the mixture additionally comprises one, more or all of the following components in an aqueous solution:
(I) Formula (V)

(V)
,
（式中、

(V)
,
(Where

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 a salt thereof,
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. An electrolytic bath or mixture according to one of the previous embodiments, wherein the electrolytic bath comprises the following components or the mixture comprises one, more than one or all of the following components in an aqueous solution:
(A) a total amount of 1.12 to 1.67 mol / L 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 of benzoic acid sulfimide and benzoic acid sulfimide anion, and / or (d) a total amount of 0.006 to 0.025 mol / L of allyl sulfonic acid and allyl sulfo And (e) a total amount of 0.00036 to 0.1438 mol / L of 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)
,
(Where
R ¹ represents C ₁ -C ₄ -alkyl or hydrogen or C ₁ -C ₄ -alkyl substituted by hydroxy, amino, C ₁ -C ₄ -alkylamino or di (C ₁ -C ₄ -alkyl) amino. Means
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 and / or (f) a total amount of 0.00025-0.0025 mol / L of 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、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 1-24,
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 wetting agents or one or more wetting agents or Multiple or all
(I) acids produced by protonation from fatty alcohol ether sulfates and / or salts thereof,
(Ii) acids produced by protonation from fatty alcohol sulfates and / or their salts,
(Iii) a mixture comprising or consisting of a fatty alcohol ether sulfate and a fatty alcohol sulfate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulfate acid and fatty alcohol sulfate acid;
(V) a mixture comprising or consisting of fatty alcohol ether sulfate and fatty alcohol sulfate acid,
And (vi) selected from the group consisting of a mixture comprising or consisting of an acid of a fatty alcohol ether sulfate and a fatty alcohol sulfate, wherein the fatty alcohol ether sulfate is of 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 represents an integer within 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 formed by protonation from fatty alcohol ether sulfates and / or salts thereof;
And / or the fatty alcohol sulfate is of 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 represents an integer within 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 acids produced by protonation from fatty alcohol sulfates and / or salts thereof, and / or (h) a total amount of 0.003 to 0.018 mol / L,
One, two, more than one or all compounds selected from the group consisting of chloral hydrate, bromaric hydrate, formate, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehydes and / or ( i) Formula (V) with a total amount of 0 to 0.0025 mol / L

(V)
,
（式中、

(V)
,
(Where

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 a salt thereof,
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). In addition,
F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , SO ₄ ²⁻ , OH ⁻ and ClO ₄ ⁻
An electrolytic bath or mixture according to one of the preceding embodiments, comprising one, two, more than one or all anions selected from the group consisting of:

7). In addition,
Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ and Sr ²⁺
An electrolytic bath or mixture according to one of the preceding embodiments, comprising one, two, more than two or all cations selected from the group consisting of:
8). Electrolyzer or mixture in aqueous solution
(H) comprising one, two or all compounds selected from the group consisting of chloral hydrate, bromaric hydrate, formaldehyde and acetaldehyde;
The electrolytic bath or mixture according to one of the preceding embodiments, wherein the compound or compounds is preferably chloral hydrate.
9. The electrolytic bath or mixture according to one of the previous embodiments, which is a single phase solution.
10. An electrolytic bath or mixture according to one of the preceding embodiments, wherein the electrolytic bath or mixture does not comprise silicon oxide particles and aluminum oxide particles suspended in the electrolytic bath or mixture.
11. An electrolytic bath or mixture according to one of the previous embodiments, wherein the electrolytic bath or mixture does not comprise oxide particles suspended in the electrolytic bath or mixture.

12 An electrolysis bath or mixture according to one of the preceding embodiments, wherein the electrolysis bath or mixture does not comprise particles suspended in the electrolysis bath or mixture.
13. Electrolytic bath or mixture according to one of the preceding embodiments, having a pH value in the range of 2.8 to 5.2, preferably 3.8 to 4.8.
14 Multiple 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)
,
(Where
n represents an integer within 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 sulfate,
(H1) Chloral hydrate,
(I1) The electrolytic bath or mixture according to one of the preceding embodiments, which can be produced by mixing a plurality of components selected from the group consisting of prop-2-yn-1-ol-ethoxylate.
15. Multiple ingredients
(A) nickel ions having a total amount of 1.12 to 1.67 mol / L,
(B1) boric acid having a total amount of 0.485 to 0.97 mol / L,
(C) A total amount of 0.0055 to 0.0274 mol / L benzoic acid sulfimide anion,
(D) Allyl sulfonate having 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 0-0.0045 mol / L,
(E3) 0-3-0.0088 mol / L of hexa-3-yne-2,5-diol,
(F1) pyridinium propyl sulfobetaine having a total amount of 0.00025 to 0.0025 mol / L,
(G) Formula (VI) of total amount 0.0006-0.025 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)
,
(Where
each n 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 sulfate,
(H1) chloral hydrate having a total amount of 0.003 to 0.018 mol / L,
And (i1) one of the preceding embodiments, which can be prepared by mixing a plurality of components selected from the group consisting of prop-2-yn-1-ol-ethoxylate in a total amount of 0-0.0025 mol / L Electrolytic bath.

16. A method for producing an article having a bright nickel layer by depositing nickel on a corresponding workpiece, comprising the following steps:
(A) preparing and / or producing an electrolytic bath or mixture according to one of the preceding embodiments;
(B) producing a bright nickel layer by electrodepositing nickel onto the work piece from a prepared or produced electrolytic bath or mixture.
17. Embodiment 17. The method of embodiment 16, wherein the temperature of the electrolytic bath or mixture is in the range of 40-70 ° C. in step (b).
18. A 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 workpiece.
19. A method according to one of aspects 16 to 18, wherein the article is a component of a conduit or a component of a component for a conduit.

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

24. A bright nickel layer
Depositing nickel on a corresponding workpiece using an electrolytic bath or mixture according to one of aspects 1 to 15;
Or using the method according to one of aspects 16 to 21,
An article comprising a bright nickel layer, preferably a component of a conduit or a component of a component for a conduit, that is manufacturable.
25. Use of an electrolytic bath for the production of a bright nickel layer on a component of (i) a mixture for use in an electrolytic bath or (ii) a component for a conduit.
(I) the mixture, or (ii) the electrolytic bath is in an aqueous solution,
(C) benzoic acid sulfimide and / or benzoic acid sulfimide anion,
And (h) one, two, more than one or all compounds selected from the group consisting of chloral hydrate, bromaric hydrate, formate, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehyde ,
Use in which the electrolytic bath additionally comprises the following components or the mixture additionally comprises all of the following components in an aqueous solution:
(A) nickel ions,
(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)
,
(Where
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 And
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 1-24,
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 on the workpiece using the electrolytic bath of the present invention or the mixture of the present invention causes nickel ions to be introduced into the aqueous solution in contact with the nickel layer as compared with a conventional bright nickel layer. Indicates a low tendency to release. This is confirmed by measuring the potential of the deposited nickel layer.

Potential measurement: General reference and examples:
The measurement of the potential of individual nickel layers and combinations of nickel layers deposited on corresponding workpieces using the electrolytic baths of the present invention or the mixtures of the present invention is usually performed by the so-called STEP test (STEP: thickness and electrodes). It is performed by simultaneous determination of potential (electron potential thick electrode and electrical potential potential). Reference is made to DIN 50022 regarding the experimental conditions and experimental construction of the STEP test.

  Using the STEP test, which is a method for the verification of the quality of the deposited nickel layer or deposited nickel layer system, parameters related to the corrosion process, ie the thickness of the individual nickel layers and their mutual potential difference Can be measured in just one working step. When using the STEP test method, it is utilized that the electric potential measured with respect to the standard electrode during dissolution changes rapidly after the nickel layer is peeled off. This change takes place after the respective nickel layer has melted, in which the measured melting potential depends 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 opening of the potential is hardly measurable. 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 using a couloscope. The potential change, measured by electrical delamination of individual nickel layers from the nickel system, can indicate the turning point from one nickel layer to the next in such a layer system in the case of abrupt changes. The end point of the measurement of the STEP test is the arrival of the substrate, for example a copper layer. In general, the 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 from -120 mV when measured in the electrolyte described above.

  The following test setup is used to measure the natural potential of a nickel coating produced using the electrolytic bath or mixture of the present invention: a test nickel coating whose composition is determined by the components of the bright nickel electrolyte Is immersed in a Corrodkote solution containing ammonium chloride, copper nitrate and iron (III) chloride, and its natural potential is compared with a reference electrode (half-cell electrode) similarly immersed in the above solution. To measure. The reference electrode consists of a silver / silver chloride electrode (Messkette). As the measuring device, a high resistance measuring device, for example, a pH meter or a multiple measuring device is useful. In this regard, the average measurement time is between 45 and about 60 minutes. A stable potential usually occurs within this time frame and its value is relative. Such measured relative values can be compared with the relative values of different configurations of 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 the coroad coat solution, Brugger, Robert (1984), “Die galvanische Vernickelung”, 2. Aufl. Saulgau (Eugen G. Leutze Verlag Bd. 12) S. 301, 20 g / l ammonium chloride; 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 natural potential of nickel coatings produced using an electrolytic bath in a corroded coating solution:

note:
The comparative and inventive baths 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 inventive bath with 1 g / l chloral hydrate was +582 mV. The above notes apply appropriately.

Use Examples 1 to 7: Production of an electrolytic bath by mixing water and 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 ingredients are placed in an aqueous solution at the above concentrations. The order in which the individual components are added in the aqueous solution is then not critical. All concentration descriptions are for the electrolytic bath.

Use Examples 8 to 14: Production of electrolytic bath by mixing water and 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 ingredients are placed in an aqueous solution at the above concentrations. The order in which the individual components are added in the aqueous solution is then not critical. All concentration descriptions are for the electrolytic bath.
General Example H1: Production of the electrolytic bath of the invention:
Selected components (containing components) of the electrolytic bath of the present invention present as a salt are dissolved in fully demineralized water. The water then preferably has a temperature in the range of 30-70 ° C. Activated carbon 0.16-0.25 mol / L is added to the resulting aqueous solution. In that case, mixing with activated carbon and aqueous solution is performed 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 in the range of 3.5 to 5.0.

In a further step, selected components (containing components) of the electrolytic bath of the present invention that are not present as salts are added to this purified solution.
Stagnation test: Inspection of nickel transfer from bright nickel layer of the present invention into municipal water:
(A) For comparison purposes, a bright nickel layer was provided on a copper tube having a length of 10 cm and a diameter of 2 cm using a normal electrolytic bath (without chloral hydrate). 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) Parallel to this, a similar such copper tube, in an electrolytic bath of the invention of the same composition as the comparative bath except that it additionally contains 500 mg / l chloral hydrate, for comparative purposes A bright nickel layer was first electrically provided and a chromium layer was electrically provided in the second step under conditions equivalent to those performed in
(C) Additionally parallel to this, in the same manner, a similar such copper tube is first bright nickel in a further electrolytic bath of the present invention containing 1000 mg / l chloral hydrate. The layer was electrically provided with the last chromium layer in the second step.

  Subsequently, the copper tubes electroplated as in (a), (b) and (c) (one for comparison; two for the present invention) were immersed in city water separately from each other. The concentration of nickel / nickel ions in city water was measured after 72 hours of standing time. 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 each rinsed 10 times with 150 ml of city water before further use. The measurement results are confirmed with an ICP-OES spectrometer and are shown in the following table. The numerical value indicates the measured nickel ion concentration (μg / l).

For each measurement, 5 tubes each plated with (a), (b) or (c) were used. The displayed value is an arithmetic average.
With the addition of chloral hydrate, the tendency of nickel / nickel ion release into the surrounding medium (here city water) is clearly reduced, especially with long contact times (second to fifth measurements). This can be clearly confirmed.

Use Example 15: Production of a specific electrolytic bath of the invention:
Certain of the inventive electrolytic bath components (containing components) present as salts, ie, containing components a, c, d and f, are dissolved at the indicated concentrations in fully demineralized water. The water then preferably has a temperature of 55 ° C. Activated carbon 0.16-0.25 mol / L is added to the resulting aqueous solution. In that case, mixing with activated carbon and aqueous solution is performed 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 of 4.2.

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

The plating time, that is, the time required for deposition of the bright nickel layer using a particular inventive bath is about 15 minutes for a current density of 4 A / dm ² .
Use and Comparative Example 16: Production of certain inventive articles (bathroom parts as examples of water conduits) with a bright nickel layer:
The components of the specific electrolytic bath (components) to be used according to the present invention for the manufacture of the articles of the present invention (bathroom parts having a bright nickel layer) are listed in the following table "Usage Example 16" Dissolved at the indicated concentration in brine (preferably water temperature 55 ° C.).

The components of the electrolysis bath not according to the invention produced for comparison purposes are the same as those according to the table “Use Example 16” and these components are likewise indicated in fully demineralised water (preferably water temperature 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 to deposit a bright nickel layer using a specific inventive bath or a non-inventive electrolytic bath produced for comparative purposes, is about 15 for a current density of 4 A / dm < ² > respectively. Minutes.

A bathroom part body constructed in the same way was used.
(A) Production of the article of the invention:
Using the electrolytic bath of the present invention, a bright nickel layer was provided on a brass bathroom component body. The thickness of this layer was about 10 μm. In the second step, a chromium layer was electrically deposited on the 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):
Using an electrolytic bath not according to the present invention, a bright nickel layer was provided on a brass bathroom component body. The thickness of this layer was about 10 μm. In the second step, a chromium layer was electrically deposited on the 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 inspection of nickel transfer from bright nickel layer of the present invention and non-present bright nickel layer into city water:
The brass parts electroplated as in (a) and (b) above were immersed in city water separately from each other. The concentration of nickel / nickel ions in city water was measured after 1 week of standing time. Further measurements are taken after 2, 3, 4 and 5 weeks, respectively. In all cases, the city water was changed after the measurement. In addition, the test brass parts were rinsed 10 times with 150 ml each of city water before being dipped again. The measurement results are confirmed with an ICP-OES spectrometer and are shown in the following table. The numerical value indicates 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 displayed value is the arithmetic average of 4 measurements each.

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

Claims (15)

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 cell is in an aqueous solution,
(C) benzoic acid sulfimide and / or benzoic acid sulfimide 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 cell or mixture wherein the electrolytic cell additionally comprises the following components or the mixture additionally comprises the following components:
(A) nickel ions,
(B) one or more acids,
(E) Formula (I)

(I)
,
(Where
R ¹ represents C ₁ -C ₄ -alkyl or hydrogen or C ₁ -C ₄ -alkyl substituted by hydroxy, amino, C ₁ -C ₄ -alkylamino or di (C ₁ -C ₄ -alkyl) amino. Means
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)
,
(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 1-24,
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. The electrolytic bath or mixture of claim 1, wherein the electrolytic bath comprises the following components or the mixture comprises one, more than one, 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 organics 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 wetting agent or the plurality of wetting agents are:
(I) acids produced by protonation from fatty alcohol ether sulfates and / or salts thereof,
(Ii) acids produced by protonation from fatty alcohol sulfates and / or their salts,
(Iii) a mixture comprising or consisting of a fatty alcohol ether sulfate and a fatty alcohol sulfate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulfate acid and fatty alcohol sulfate acid;
(V) a mixture comprising or consisting of fatty alcohol ether sulfate and fatty alcohol sulfate acid,
And (vi) selected from the group consisting of a mixture comprising or consisting of an acid of a fatty alcohol ether sulfate and a fatty alcohol sulfate,
One selected wetting agent carries a branched or unbranched alkyl group as a carbon chain, or a plurality of selected wetting agents as a carbon chain, each independently, branched or A wetting agent bearing an unbranched alkyl group. The electrolytic bath or mixture according to claim 1 or 2, wherein the electrolytic bath comprises the following components or the mixture comprises one, more or all of the following components in an aqueous solution:
(A) a total amount of 1.12 to 1.67 mol / L 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 of benzoic acid sulfimide and benzoic acid sulfimide anion, and / or (d) a total amount of 0.006 to 0.025 mol / L of allyl sulfonic acid and allyl sulfo And (e) a total amount of 0.00036 to 0.1438 mol / L of formula (I)

(I)
,
(Where
R ¹ represents C ₁ -C ₄ -alkyl or hydrogen or C ₁ -C ₄ -alkyl substituted by hydroxy, amino, C ₁ -C ₄ -alkylamino or di (C ₁ -C ₄ -alkyl) amino. Means
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 and / or (f) a total amount of 0.00025-0.0025 mol / L of formula (II)

(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 1-24,
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 wetting agents or one or more wetting agents or Multiple or all
(I) acids produced by protonation from fatty alcohol ether sulfates and / or salts thereof,
(Ii) acids produced by protonation from fatty alcohol sulfates and / or their salts,
(Iii) a mixture comprising or consisting of a fatty alcohol ether sulfate and a fatty alcohol sulfate,
(Iv) a mixture comprising or consisting of fatty alcohol ether sulfate acid and fatty alcohol sulfate acid;
(V) a mixture comprising or consisting of fatty alcohol ether sulfate and fatty alcohol sulfate acid,
And (vi) selected from the group consisting of a mixture comprising or consisting of an acid of a fatty alcohol ether sulfate and a fatty alcohol sulfate,
The fatty alcohol ether sulfate is of the formula (III)

(III)
,
(In the formula, each independently,
n represents an integer within 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 formed by protonation from fatty alcohol ether sulfates and / or salts thereof;
And / or the fatty alcohol sulfate is of the formula (IV)

(IV)
,
(In the formula, each independently,
n represents an integer within the range of 1 to 24;
R ⁴ means 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 ), a wetting agent selected from the group consisting of acids generated by protonation from fatty alcohol sulfates and / or salts thereof; And / or (h) a total amount of 0.003 to 0.018 mol / L,
One, two, more than one or all compounds selected from the group consisting of chloral hydrate, bromaric hydrate, formate, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehydes and / or ( i) Formula (V) with a total amount of 0-0.0025 mol / L

(V)
,
(Where

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 a salt thereof,
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 In addition,
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⁺
4. The electrolytic bath or mixture according to claim 1, comprising one, two, more or all cations selected from the group consisting of:   Electrolytic bath or mixture according to one of claims 1 to 4, which is a single-phase solution.   6. 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, preferably 3.8 to 4.8. A method for producing an article having a bright nickel layer by depositing nickel on a corresponding workpiece, comprising the following steps:
(A) preparing and / or producing an electrolytic bath or mixture according to one of claims 1 to 6;
(B) producing a bright nickel layer by electrodepositing nickel onto the work piece from a prepared or produced electrolytic bath or mixture.   The method according to claim 7, wherein the temperature of the electrolytic bath or mixture is in the range of 40-70 ° C in step (b).   9. A method according to claim 7 or 8, wherein in step (b) a bright nickel layer is deposited on the copper, brass or zinc surface of the workpiece.   The method according to one of claims 7 to 9, wherein the article is a component of a conduit or a component of a component for a conduit.   11. A method according to claim 7, wherein in step (b), a deposition on the surface of the workpiece is performed, the surface being part of the semi-bright nickel layer of the workpiece. The following additional steps:
12. A method according to claim 7, comprising (c) depositing a further metal layer on the bright nickel layer, preferably electrodepositing, preferably electrodepositing a chromium layer on the bright nickel layer. The method according to item.   Use of an electrolytic bath or mixture according to one of claims 1 to 6 for the deposition or production of a bright nickel layer.   14. Use according to claim 13, for the deposition or production of a bright nickel layer on a component of a component for a conduit. A bright nickel layer
Depositing nickel on the corresponding workpiece using the electrolytic bath or mixture according to one of claims 1 to 6;
Or an article comprising a bright nickel layer, preferably a component of a conduit or a component of a conduit for a conduit, which can be produced using the method according to one of claims 7-12.