EP1969160A1 - Electrolyte and process for depositing a matt metal layer - Google Patents

Electrolyte and process for depositing a matt metal layer

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Publication number
EP1969160A1
EP1969160A1 EP06701821A EP06701821A EP1969160A1 EP 1969160 A1 EP1969160 A1 EP 1969160A1 EP 06701821 A EP06701821 A EP 06701821A EP 06701821 A EP06701821 A EP 06701821A EP 1969160 A1 EP1969160 A1 EP 1969160A1
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EP
European Patent Office
Prior art keywords
electrolyte
mol
wetting agent
emulsion
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06701821A
Other languages
German (de)
French (fr)
Other versions
EP1969160B1 (en
Inventor
Andreas KÖNIGSHOFEN
Danica Elbick
Christoph Werner
Wolfgang Clauberg
Peter Pies
Andreas MÖBIUS
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MacDermid Enthone Inc
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Enthone Inc
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Priority to PL06701821T priority Critical patent/PL1969160T3/en
Publication of EP1969160A1 publication Critical patent/EP1969160A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the present invention relates to an electrolyte and to a method for depositing a matt metal layer on a substrate from an electrolyte comprising an emulsion and / or dispersion former or a wetting agent.
  • the goal in the production of metallic layers on substrates is to obtain as smooth and high-gloss coatings as possible.
  • Fields of application for matt-deposited metal layers on substrates are, for example, the jewelery industry, the valve industry, the automotive industry, but also the optical or precision mechanical industry, in which the glare-free nature of these coatings in particular has to be borne. Matt-deposited nickel or nickel alloy layers and cobalt layers are known from the prior art.
  • the object of the present invention is to provide an electrolyte and a method for depositing matte metal layers on substrates, with the aid of which a multiplicity of metals in different degrees of matting can be deposited on a wide variety of substrates.
  • an electrolyte for depositing a matt metal layer on a substrate from an electrolyte comprising an emulsion and / or dispersion former or a wetting agent which is characterized in that the electrolyte as the metal to be deposited is a metal of the group consisting of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, W, Re, Pt, Au, Tl, Pb, Bi or an alloy of these metals, the emulsion and / or dispersion former is a substituted or unsubstituted polyalkylene oxide or its derivative, the surfactant has fluorinated or perfluorinated hydrophobic chains or is a polyalkylene oxide substituted quaternary ammonium compound, and electrolyte, Emulsion and / or dispersion former or wetting agent form a microemulsion and
  • the object is achieved by a method for the electrolytic deposition of a matt metal layer on a substrate, wherein the substrate is connected to a voltage source in a plating bath comprising an electrolyte according to the invention and a counterelectrode and a voltage is applied between substrate and counterelectrode, which is suitable for depositing a metal layer on the substrate.
  • microemulsions in electrolytes are suitable for matt deposition of a wide variety of metals from the corresponding electrolytes. It has also been found that to form these microemulsions in electrolytes of various metals to be deposited both polyalkylene glycols or their derivatives, wetting agents with fluorinated or perfluorinated hydrophobic chains, as well as polyalkylene oxide substituted quaternary ammonium compounds are suitable. These compounds have a wide range of uses for the production of emulsions in electrolytes of various metals and can be used individually.
  • polyalkylene glycols as emulsion and / or dispersion formers, in addition to polymers of homogeneous structure, in particular polymers having different percentage fractions of hydrophilic and hydrophobic structures, preferably consisting of polyethylene glycols and polypropylene glycols, have been found.
  • the percentage of hydrophilic and hydrophobic structures as a function of the average molar mass decides the degree of dullness of the deposited metal layer, wherein generally average molecular weights> 200 g / mol, for polymers with a high percentage of hydrophobic structures preferably 200 to 2000 g / mol and even more preferably for polymers with a high percentage of hydrophilic structures> 4000 g / mol are suitable.
  • the average molecular weight of the fluorinated or perfluorinated wetting agents according to the invention is between about 550 and about 1000 g / mol, preferably between about 700 and about 1000 g / mol. Again, the average molecular weight influence the matte degree.
  • wetting agents for depositing matt metal layers from electrolytes according to the invention are polyalkylene oxide-substituted quaternary ammonium compounds, which preferably have the general formula
  • the average molecular weight of the quaternary ammonium compounds added to the electrolyte in the present invention is from about 200 to about 1000 g / mol, preferably from about 400 to about 500 g / mol, and more preferably from about 450 to about 460 g / mol.
  • the addition of polytetrafluoroethylene particles to the electrolyte according to the invention exerts an influence on the properties of the deposited matt metal layers.
  • the additional polytetrafluoroethylene particles contain a tactile much softer surface which also compared to matte metal layers, which were deposited from electrolytes according to the invention without the addition of polytetrafluoroethylene particles, even a much lower Sensitivity to finger marks (touch free) shows.
  • the average particle diameter of the added polytetrafluoroethylene particles should be in the range of about 10 to about 1000 nm, preferably about 100 to about 300 nm.
  • the polytetrafluoroethylene particles may be added in a concentration between about 0.1 and 1000 mg / l, preferably between about 0.5 and 5 mg / l.
  • the following examples show embodiments of the electrolyte according to the invention and the method according to the invention, but without the invention being limited to these embodiments.
  • Example 2 When using the parameters described in Example 1, a stable uniform pearlescent effect is achieved at 26 ° C. and addition of 300 mg / l of a polyalkylene glycol of the following block polymer structure instead of the polypropylene glycol described in Example 1:
  • the average molecular weight is 1700 g / mol, wherein the polyethylene oxide content (x + z) makes up 20% of the molecular weight.
  • Example 2 is with 5 mg / l polyalkylene glycol of the block polymer structure given in Example 2 with a molecular weight of 5000 g / mol and a proportion of 20% polyethylene oxide at a current density of 2 A / dm 2 , 25 ° C and a cathode movement of 1 m / min also achieved a uniform pearlescent effect.
  • F- (CF 2 -CF 2 ) ⁇ - (CH 2 -CH 2 -O) y -H produces a uniform matt effect.
  • a uniform matting effect becomes the effect, the structure of which is different from Example 4.
  • a pearlescent brass sheet can be produced by adding 8 mg / l of didecylmethylpoly (oxyethyl) ammonium propionate to a Watts electrolyte analogously to Example 4.
  • Example 5 To the emulsion of polyethyleneglycol-substituted ammonium salt produced in Example 5 was added 1 ml / l PTFE suspension (Zonyl TE3667-N, Dupont). As a result, other structures and layer properties were achieved.
  • the resulting surface has a strongly hydrophobic dirt-repellent effect.

Abstract

An electrolytic composition for the deposition of a matt metal layer onto a substrate and deposition process where the composition comprises a source of metal from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, In, Sn, Sb, Re, Pt, Au, Bi, and combinations thereof; a substituted or unsubstituted polyalkylene oxide or its derivative as an emulsion and/or dispersion former; and a compound comprising fluorated or perfluorated hydrophobic chains or which is a polyalkylene oxide substituted quaternary ammonium compound as wetting agent; wherein the electrolytic composition forms a microemulsion and/or dispersion.

Description

Elektrolyt und Verfahren zur Abscheidunfl einer matten Metallschicht Electrolyte and method for separating a matt metal layer
Die vorliegende Erfindung betrifft einen Elektrolyten sowie ein Verfahren zur Abscheidung einer matten Metallschicht auf einem Substrat aus einem einen Emulsions- und/oder Dispersionsbildner oder ein Netzmittel aufweisenden Elektrolyten.The present invention relates to an electrolyte and to a method for depositing a matt metal layer on a substrate from an electrolyte comprising an emulsion and / or dispersion former or a wetting agent.
Allgemein geht das Bestreben bei der Herstellung metallischer Schichten auf Substraten dahin, möglichst glatte und hochglänzende Überzüge zu erhalten. Anwendungsspezifisch ist es jedoch in vielen Fällen wünschenswert, einen Metallüberzug zu erhalten, der nicht glänzend sondern matt ist. Dies kann einerseits im optischen Erscheinungsbild dieses Überzugs, andererseits auch in den technischen Eigenschaften, sprich der Blendfreiheit, dieser Überzüge begründet liegen. Anwendungsfelder für matt abgeschiedene Metallschichten auf Substraten sind beispielsweise die Schmuckindustrie, die Armaturenindustrie, die Automobilindustrie, aber auch die optische- oder feinmechanische Industrie, bei der insbesondere die Blendfreiheit dieser Überzüge zu tragen kommt. Aus dem Stand der Technik sind matt abgeschiedene Nickel oder Nickellegierungsschichten sowie Cobaltschichten bekannt. Während die Abscheidung solcher potentiell Allergie auslösenden Metalle in vielen Bereichen unkritisch ist, ist eine Vermeidung dieser Metalle im Bereich der Schmuckindustrie oder auch im Bereich der Herstellung von Küchengeräten und -Utensilien erstrebenswert. Im Bereich der optischen- oder feinmechanischen Industrie ist die Abscheidung matter Metallschichten unterschiedlichster Metalle aufgrund der unterschiedlichen Eigenschaften der jeweiligen Metalle wünschenswert. Darüber hinaus ist es wünschenswert den Mattheitsgrad der abgeschiedenen Metallschichten über einen weiten Bereich einstellen zu können.In general, the goal in the production of metallic layers on substrates is to obtain as smooth and high-gloss coatings as possible. However, in many applications, it is desirable to obtain a metal coating that is not glossy but dull. This can be due on the one hand in the visual appearance of this coating, on the other hand, in the technical properties, ie the glare-free, these coatings. Fields of application for matt-deposited metal layers on substrates are, for example, the jewelery industry, the valve industry, the automotive industry, but also the optical or precision mechanical industry, in which the glare-free nature of these coatings in particular has to be borne. Matt-deposited nickel or nickel alloy layers and cobalt layers are known from the prior art. While the deposition of such potentially allergy-inducing metals in many areas is not critical, avoiding these metals in the jewelry industry or in the field of manufacturing kitchen appliances and utensils is desirable. In the field of optical or fine mechanical industry, the deposition of matt metal layers of different metals is desirable because of the different properties of the respective metals. It is beyond that it is desirable to be able to adjust the degree of matting of the deposited metal layers over a wide range.
Die A u f g a b e der vorliegenden Erfindung ist es, einen Elektrolyten sowie ein Verfahren zur Abscheidung matter Metallschichten auf Substraten zur Verfügung zu stellen, mit dessen Hilfe eine Vielzahl von Metallen in unterschiedlichen Mattierungsgraden auf unterschiedlichsten Substraten abgeschieden werden können.The object of the present invention is to provide an electrolyte and a method for depositing matte metal layers on substrates, with the aid of which a multiplicity of metals in different degrees of matting can be deposited on a wide variety of substrates.
G e l ö s t wird diese Aufgabe durch einen Elektrolyten zur Abscheidung einer matten Metallschicht auf einem Substrat aus einem einen Emulsions- und/oder Dispersionsbildner oder ein Netzmittel aufweisenden Elektrolyten, welcher dadurch gekennzeichnet ist, daß der Elektrolyt als abzuscheidendes Metall ein Metall der Gruppe bestehend aus AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, W, Re, Pt, Au, Tl, Pb, Bi oder eine Legierung dieser Metalle aufweist, der Emulsions- und/oder Dispersionsbildner ein substituiertes oder unsubstituiertes Polyalkylenoxid oder dessen Derivat ist, das Netzmittel fluorierte oder perfluorierte hydrophobe Ketten aufweist oder eine Polyalkylenoxid substituierte quartäre Ammoniumverbindung ist, und Elektrolyt, Emulsions- und/oder Dispersionsbildner oder Netzmittel eine Microemulsion und/oder -dispersion bilden.This object is achieved by an electrolyte for depositing a matt metal layer on a substrate from an electrolyte comprising an emulsion and / or dispersion former or a wetting agent, which is characterized in that the electrolyte as the metal to be deposited is a metal of the group consisting of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, W, Re, Pt, Au, Tl, Pb, Bi or an alloy of these metals, the emulsion and / or dispersion former is a substituted or unsubstituted polyalkylene oxide or its derivative, the surfactant has fluorinated or perfluorinated hydrophobic chains or is a polyalkylene oxide substituted quaternary ammonium compound, and electrolyte, Emulsion and / or dispersion former or wetting agent form a microemulsion and / or dispersion.
Hinsichtlich des Verfahrens wird die Aufgabe durch ein Verfahren zur elektrolytischen Abscheidung einer matten Metallschicht auf einem Substrat gelöst, wobei das Substrat in einem Galvanisierungsbad, aufweisend einen erfindungsgemäßen Elektrolyten und eine Gegenelektrode, mit einer Spannungsquelle verbunden wird und eine Spannung zwischen Substrat und Gegenelektrode angelegt wird, die geeignet ist eine Metallschicht auf dem Substrat abzuscheiden.With regard to the method, the object is achieved by a method for the electrolytic deposition of a matt metal layer on a substrate, wherein the substrate is connected to a voltage source in a plating bath comprising an electrolyte according to the invention and a counterelectrode and a voltage is applied between substrate and counterelectrode, which is suitable for depositing a metal layer on the substrate.
Es wurde herausgefunden, daß die Bildung von Microemulsionen in Elektrolyten geeignet ist, unterschiedlichste Metalle aus den entsprechenden Elektrolyten matt abzuscheiden. Des weiteren wurde herausgefunden, daß zur Bildung dieser Microemulsionen in Elektrolyten unterschiedlichster abzuscheidender Metalle sowohl Polyalkylenglykole oder deren Derivate, Netzmittel mit fluorierten oder perfluorierten hydrophoben Ketten, als auch mit Polyalkylenoxidketten substituierte quartäre Ammoniumverbindungen geeignet sind. Diese Verbindungen weisen ein breites Einsatzspektrum zur Erzeugung von Emulsionen in Elektrolyten unterschiedlichster Metalle auf und können einzeln eingesetzt werden.It has been found that the formation of microemulsions in electrolytes is suitable for matt deposition of a wide variety of metals from the corresponding electrolytes. It has also been found that to form these microemulsions in electrolytes of various metals to be deposited both polyalkylene glycols or their derivatives, wetting agents with fluorinated or perfluorinated hydrophobic chains, as well as polyalkylene oxide substituted quaternary ammonium compounds are suitable. These compounds have a wide range of uses for the production of emulsions in electrolytes of various metals and can be used individually.
Im Fall der Polyalkylenglykole als Emulsions- und/oder Dispersionsbildner erwiesen sich neben homogen aufgebauten Polymeren insbesondere Polymere mit unterschiedlichen prozentualen Anteilen an hydrophilen und hydrophoben Strukturen, bevorzugt bestehend aus Polyethlen- und Polypropylenglykolen. Hierbei entscheidet unter anderem der prozentuale Anteil an hydrophilen und hydrophoben Strukturen in Abhängigkeit der mittleren molaren Masse den Mattigkeitsgrad der abgeschiedenen Metallschicht, wobei generell mittlere Molmassen > 200 g/Mol, für Polymere mit hohem prozentualen Anteil hydrophober Strukturen bevorzugt 200 bis 2000 g/Mol und noch bevorzugter für Polymere mit hohem prozentualem Anteil hydrophiler Strukturen > 4000 g/Mol geeignet sind.In the case of the polyalkylene glycols as emulsion and / or dispersion formers, in addition to polymers of homogeneous structure, in particular polymers having different percentage fractions of hydrophilic and hydrophobic structures, preferably consisting of polyethylene glycols and polypropylene glycols, have been found. Among other things, the percentage of hydrophilic and hydrophobic structures as a function of the average molar mass decides the degree of dullness of the deposited metal layer, wherein generally average molecular weights> 200 g / mol, for polymers with a high percentage of hydrophobic structures preferably 200 to 2000 g / mol and even more preferably for polymers with a high percentage of hydrophilic structures> 4000 g / mol are suitable.
Beim Einsatz fluorierter oder perfluorierter Netzmittel erwiesen sich Netzmittel der allgemeinen FormelWhen using fluorinated or perfluorinated wetting agents wetting agents of the general formula proved
R1CH2CH2O(CH2CH2O)xH (Formel 1)R 1 CH 2 CH 2 O (CH 2 CH 2 O) x H (formula 1)
mit Rf = F(CF2CF2)n , wobei X = 6 bis 15 und n = 2 bis 10 ist, als besonders geeignet. Das mittlere Molekulargewicht der fluorierten oder perfluorierten Netzmittel liegt erfindungsgemäß zwischen ungefähr 550 und ungefähr 1000 g/Mol, vorzugsweise zwischen ungefähr 700 und ungefähr 1000 g/Mol. Auch hier nimmt das mittlere Molekulargewicht Einfluß auf den Mattheitsgrad.with R f = F (CF 2 CF 2 ) n, where X = 6 to 15 and n = 2 to 10, as particularly suitable. The average molecular weight of the fluorinated or perfluorinated wetting agents according to the invention is between about 550 and about 1000 g / mol, preferably between about 700 and about 1000 g / mol. Again, the average molecular weight influence the matte degree.
Eine weitere geeignete Art von Netzmitteln zur erfindungsgemäßen Abscheidung matter Metallschichten aus Elektrolyten sind Polyalkylenoxid substituierte quartäre Ammoniumverbindungen, welche vorzugsweise der allgemeinen FormelAnother suitable type of wetting agents for depositing matt metal layers from electrolytes according to the invention are polyalkylene oxide-substituted quaternary ammonium compounds, which preferably have the general formula
(Formel 2) wobei wenigstens ein Rest R1, R2, R3 oder R4 ein Polyalkylenoxid Substituent ist und die verbleibenden Reste unabhängig voneinander gleiche oder unterschiedliche geradkettige oder verzweigte, gesättigte oder ungesättigte Ci bis C18 Alkylketten sind und X" ein Halogenid, ein Sulfatanion oder Anion einer C1 bis C6 Carbonsäure ist, gehorchen. Es hat sich herausgestellt, daß insbesondere quartäre Ammoniumverbindungen der allgemeinen Formel 2 geeignet sind, bei denen R1 und R2 eine Ce bis C-12, bevorzugt eine Ci0 Alkylseitenkette ist, R3 eine Ci bis C-3, bevorzugt eine Ci Alkylseitenkette ist, R4 der allgemeinen Formel [CH2-CH2-O]n H mit n = 1 bis 5 entspricht und X' das Anion einer C2 bis C4 Carbonsäure ist.(Formula 2) wherein at least one radical R 1 , R 2 , R 3 or R 4 is a polyalkylene oxide substituent and the remaining radicals are independently identical or different straight-chain or branched, saturated or unsaturated C 1 to C 18 alkyl chains and X "is a halide, a sulfate anion or anion a C 1 to C 6 carboxylic acid, obey. It has been found that in particular, quaternary ammonium compounds of general formula 2 are suitable in which R 1 and R 2 is a Ce to C 1 2, preferably a Ci 0 alkyl side chain, R 3 is a Ci to C- 3 , preferably a Ci alkyl side chain, R 4 of the general formula [CH 2 -CH 2 -O] n H with n = 1 to 5 and X 'is the anion of a C 2 to C 4 carboxylic acid.
Das mittlere Molekulargewicht der erfindungsgemäß dem Elektrolyten zugesetzten quartären Ammoniumverbindungen liegt zwischen ungefähr 200 bis ungefähr 1000 g/Mol, bevorzugt zwischen ungefähr 400 und ungefähr 500 g/Mol und noch bevorzugter zwischen ungefähr 450 und ungefähr 460 g/Mol.The average molecular weight of the quaternary ammonium compounds added to the electrolyte in the present invention is from about 200 to about 1000 g / mol, preferably from about 400 to about 500 g / mol, and more preferably from about 450 to about 460 g / mol.
Darüber hinaus hat sich herausgestellt, daß der Zusatz von Polytetrafluorethylen- Partikeln zum erfindungsgemäßen Elektrolyten einen Einfluß auf die Eigenschaften der abgeschiedenen matten Metallschichten ausübt. So zeigt sich bei der Abscheidung von matten Metallschichten aus erfindungsgemäßen Elektrolyten die zusätzlich Polytetrafluorethylen-Partikel enthalten eine taktil wesentlich weichere Oberfläche die darüber hinaus im Vergleich zu matten Metallschichten, die aus erfindungsgemäßen Elektrolyten ohne Zusatz von Polytetrafluorethylen-Partikeln abgeschieden wurden, auch noch eine deutlich geringere Empfindlichkeit gegenüber Fingerflecken (touch free) zeigt.In addition, it has been found that the addition of polytetrafluoroethylene particles to the electrolyte according to the invention exerts an influence on the properties of the deposited matt metal layers. Thus, in the deposition of matte metal layers of inventive electrolyte, the additional polytetrafluoroethylene particles contain a tactile much softer surface which also compared to matte metal layers, which were deposited from electrolytes according to the invention without the addition of polytetrafluoroethylene particles, even a much lower Sensitivity to finger marks (touch free) shows.
Es wurde herausgefunden, daß der mittlere Partikeldurchmesser der zugesetzten Polytetrafluorethylen-Partikel im Bereich von ungefähr 10 bis ungefähr 1000 nm, vorzugsweise ungefähr 100 bis ungefähr 300 nm liegen sollte.It has been found that the average particle diameter of the added polytetrafluoroethylene particles should be in the range of about 10 to about 1000 nm, preferably about 100 to about 300 nm.
Erfindungsgemäß können die Polytetrafluorethylen-Partikel in einer Konzentration zwischen ungefähr 0,1 und 1000 mg/l, bevorzugt zwischen ungefähr 0,5 und 5 mg/l zugesetzt werden. Die nachfolgenden Beispiele zeigen Ausführungen des erfindungsgemäßen Elektrolyten sowie des erfindungsgemäßen Verfahrens, ohne daß sich die Erfindung jedoch auf diese Ausführungsbeispiele beschränken läßt.According to the invention, the polytetrafluoroethylene particles may be added in a concentration between about 0.1 and 1000 mg / l, preferably between about 0.5 and 5 mg / l. The following examples show embodiments of the electrolyte according to the invention and the method according to the invention, but without the invention being limited to these embodiments.
Beispiel 1example 1
Ein Cu-Elektrolyt mit folgender Zusammensetzung:A Cu electrolyte with the following composition:
55 g/l Cu2+ 55 g / l Cu 2+
66 g/l H2SO4 66 g / l H 2 SO 4
100 mg/l Cl" 100 mg / l Cl "
200 mg/l Bis-(3-Sulfopropyl)-disulfid, Dinatriumsalz200 mg / l bis (3-sulfopropyl) disulfide, disodium salt
wird mit 2 g/I Polypropylenglykol mit einer Molmasse von 900 g/Mol versetzt. Auf einem Winkelblech wird 10 min bei 5 A/dm2 und 35°C galvanisiert, wobei die Kathode 2 m/min bewegt wird.is added with 2 g / l polypropylene glycol having a molecular weight of 900 g / mol. On an angle plate is galvanized for 10 min at 5 A / dm 2 and 35 ° C, the cathode is moved 2 m / min.
Luftbewegung ist nicht nötig. Erstaunlicherweise erfolgt ein gleichmäßiger Perlglanzeffekt im hohen und niedrigen Stromdichtebereich. Aufgrund der minimalen Mengen an organischen Glanzzusätzen kommt es nicht zu Haftfestigkeitsproblemen bei Stromunterbrechung und können es anschließend haftfest Schichten aus einem sauren Bronzeelektrolyten oder aus einem dreiwertigen Chromelektrolyten abgeschieden werden. Der Mattigkeitsgrad des Perlglanzeffektes kann durch die Konzentration des Polymers gesteuert werden. Durch einfache Filtration über Celite wird der gesamte Perlglanzzμsatz entfernt.Air movement is not necessary. Surprisingly, a uniform pearlescent effect occurs in the high and low current density range. Due to the minimal amount of organic brightener additives, there are no adhesion problems in the case of power interruption and then it can be adhered to layers of an acidic bronze electrolyte or of a trivalent chromium electrolyte. The degree of matte of the pearlescent effect can be controlled by the concentration of the polymer. By simply filtering over Celite, the entire pearlescent additive is removed.
Beispiel 2Example 2
Bei Verwendung der in Beispiel 1 beschriebenen Parameter wird bei 26°C und Zusatz von 300 mg/l eines Polyalkylenglykols nachfolgender Blockpolymerstruktur anstatt des in Beispiel 1 beschriebenen Polyproplyenglykols ein stabiler gleichmäßiger Perlglanzeffekt erzielt:When using the parameters described in Example 1, a stable uniform pearlescent effect is achieved at 26 ° C. and addition of 300 mg / l of a polyalkylene glycol of the following block polymer structure instead of the polypropylene glycol described in Example 1:
HO-(CH2-CH2-O)x-(CH2-CH(CH3)-O)y-(CH2-CH2-O)z-H Die mittlere Molmasse beträgt 1700 g/Mol, wobei der Polyethylenoxid-Anteil (x+z) 20% der Molmasse ausmacht.HO- (CH 2 -CH 2 -O) x - (CH 2 -CH (CH 3 ) -O) y - (CH 2 -CH 2 -O) z -H The average molecular weight is 1700 g / mol, wherein the polyethylene oxide content (x + z) makes up 20% of the molecular weight.
Beispiel 3Example 3
In einem Bronzeelektrolyt der folgenden Zusammensetzung:In a bronze electrolyte of the following composition:
12 g/l Cu(II)12 g / l Cu (II)
2 g/l Sn(II)2 g / l Sn (II)
100 g/l Methansulfonsäure100 g / l methanesulfonic acid
2 g/l Hydrochinon2 g / l hydroquinone
wird mit 5 mg/l Polyalkylenglykols der im Beispiel 2 angeführten Blockpolymerstruktur mit einer Molmasse von 5000 g/Mol und einem Anteil von 20% Polyethylenoxid bei einer Stromdichte von 2 A/dm2, 25°C und einer Kathodenbewegung von 1 m/min ebenfalls ein gleichmäßiger Perglanzeffekt erzielt.is with 5 mg / l polyalkylene glycol of the block polymer structure given in Example 2 with a molecular weight of 5000 g / mol and a proportion of 20% polyethylene oxide at a current density of 2 A / dm 2 , 25 ° C and a cathode movement of 1 m / min also achieved a uniform pearlescent effect.
Beispiel 4Example 4
In einem Watts-Elektrolyten mit folgender Zusammensetzung:In a Watts electrolyte with the following composition:
440 g/l Nickelsulfat 30 g/l Borsäure 40 g/l Nickelchlorid 5 g/l Natriumsaccharinat440 g / l nickel sulphate 30 g / l boric acid 40 g / l nickel chloride 5 g / l sodium saccharinate
wird 10 min bei einer Temperatur von 52°C, einem pH-Wert von 4,2, einer Stromdichte von 5 A/dm2 und einer Kathodenbewegung von 2 m/min durch Zugabe von 10 mg/I des folgenden als Netzmittel bezeichneten CF-substituierten Polyethylenglykols mit einer mittleren Molmasse von 700 g/Mol, wobei die Hauptkomponente durch X = 5 und Y = 10 charakterisiert ist,is heated for 10 minutes at a temperature of 52 ° C., a pH of 4.2, a current density of 5 A / dm 2 and a cathode movement of 2 m / min by adding 10 mg / l of the following CF-surfactant Substituted polyethylene glycol having an average molecular weight of 700 g / mol, wherein the main component is characterized by X = 5 and Y = 10,
F-(CF2-CF2)χ-(CH2-CH2-O)y-H ein gleichmäßiger Matteffekt erzeugt.F- (CF 2 -CF 2 ) χ- (CH 2 -CH 2 -O) y -H produces a uniform matt effect.
Beispiel 5Example 5
Ersetzt man in Beispiel 4 das CF2-substituierte Polyethylenglykol durch polyethylenglykolsubstituierte Ammoniumverbindungen, wird ein gleichmäßiger Mattigkeitseffekt Effekt, dessen Struktur anders als in Beispiel 4 ist. So läßt sich ein perlglanzvemickeltes Messingblech durch Zugabe von 8 mg/1 Didecylmethylpoly- (oxethyl) Ammonium Propionate in einen Watts-Elektrolyten analog Beispiel 4 erzeugen.If the CF 2 -substituted polyethylene glycol is replaced by polyethylene glycol-substituted ammonium compounds in Example 4, a uniform matting effect becomes the effect, the structure of which is different from Example 4. For example, a pearlescent brass sheet can be produced by adding 8 mg / l of didecylmethylpoly (oxyethyl) ammonium propionate to a Watts electrolyte analogously to Example 4.
Beispiel 6Example 6
Zu der in Beispiel 5 erzeugten Emulsion aus polyethylenglykolsubstituiertem Ammoniumsalz wurde 1 ml/l PTFE Suspension (Zonyl TE3667-N, Dupont) zugegeben. Dadurch wurden andere Strukturen und Schichteigenschaften erzielt.To the emulsion of polyethyleneglycol-substituted ammonium salt produced in Example 5 was added 1 ml / l PTFE suspension (Zonyl TE3667-N, Dupont). As a result, other structures and layer properties were achieved.
Die so entstandene Oberfläche besitzt einen stark hydrophoben schmutzabweisenden Effekt. The resulting surface has a strongly hydrophobic dirt-repellent effect.

Claims

Patentansprüche claims
1. Elektrolyt zur Abscheidung einer matten Metallschicht auf einem Substrat aus einem einen Emulsions- und/oder Dispersionsbildner oder ein Netzmittel aufweisenden Elektrolyten, dadurch gekennzeichnet, dass der Elektrolyt als abzuscheidendes Metall ein Metall der Gruppe bestehend aus AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, W, Re, Pt, Au, Tl, Pb, Bi oder eine Legierungen dieser Metalle aufweist, der Emulsions- und/oder Dispersionsbildner ein substituiertes oder unsubstituiertes Polyalkylenoxid oder dessen Derivat ist, das Netzmittel fluorierte oder perfluorierte hydrophobe Ketten aufweist oder eine Polyalkylenoxid substituierte quartäre Ammoniumverbindung ist, und Elektrolyt, Emulsions- und/oder Dispersionsbildner oder Netzmittel eine Microemulsion und/oder -dispersion bilden.1. Electrolyte for depositing a matt metal layer on a substrate comprising an electrolyte comprising an emulsion and / or dispersion former or a wetting agent, characterized in that the electrolyte as the metal to be deposited is a metal of the group consisting of Al, Ti, V, Cr, Mn , Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, W, Re, Pt, Au, Tl, Pb, Bi or a Alloys of these metals, the emulsion and / or dispersion former is a substituted or unsubstituted polyalkylene oxide or its derivative, the wetting agent has fluorinated or perfluorinated hydrophobic chains or a polyalkylene oxide-substituted quaternary ammonium compound, and electrolyte, emulsion and / or dispersion former or wetting agent Microemulsion and / or dispersion form.
2. Elektrolyt gemäß Anspruch 1, wobei der Emulsions- und/oder Dispersionsbildner ein substituiertes oder unsubstituiertes Polyethylenoxid, Polypropylenoxid, Polypropylen-Polyethylenoxid Blockcopolymer oder eine Mischung dieser ist.2. An electrolyte according to claim 1, wherein the emulsion and / or dispersion former is a substituted or unsubstituted polyethylene oxide, polypropylene oxide, polypropylene-polyethylene oxide block copolymer or a mixture thereof.
3. Elektrolyt gemäß Anspruch 2, wobei der Emulsions- und/oder Dipersions- bildner ein mittleres Molekulargewicht >200 g/Mol, für Polymere mit hohem prozentualen Anteil hydrophober Strukturen bevorzugt 200 bis 2000 g/Moi und noch bevorzugter für Polymere mit hohem prozentualem Anteil hydrophiler Strukturen > 4000 g/Mol aufweist.3. An electrolyte according to claim 2, wherein the emulsion and / or Dipersions- bildner an average molecular weight> 200 g / mol, for polymers having a high percentage of hydrophobic structures preferably 200 to 2000 g / Moi and more preferably for polymers with a high percentage hydrophilic structures> 4000 g / mol.
4. Elektrolyt gemäß Anspruch 1, wobei das fluorierte oder perfluorierte Netzmittel vorzugsweise die allgemeine Formel4. The electrolyte according to claim 1, wherein the fluorinated or perfluorinated wetting agent preferably has the general formula
RfCH2CH2O(CH2CH2O)xHR f CH 2 CH 2 O (CH 2 CH 2 O) x H
mit Rf = F(CF2CF2)O, wobei x =6 bis 15 und n = 2 bis 10 ist, aufweist. with R f = F (CF 2 CF 2 ) O , where x = 6 to 15 and n = 2 to 10.
5. Elektrolyt gemäß Anspruch 4, wobei das mittlere Molekulargewicht des Netzmittels zwischen ungefähr 550 und ungefähr 1000 g/Mol, vorzugsweise zwischen ungefähr 700 und ungefähr 1000 g/Mol liegt.The electrolyte of claim 4, wherein the average molecular weight of the wetting agent is between about 550 and about 1000 g / mol, preferably between about 700 and about 1000 g / mol.
6. Elektrolyt gemäß Anspruch 1 , wobei die als Netzmittel eingesetzte Polyalkylenoxid substituierte quartäre Ammoniumverbindung vorzugsweise die allgemeine Formel6. The electrolyte according to claim 1, wherein the polyalkylene oxide-substituted quaternary ammonium compound used as the wetting agent preferably has the general formula
wobei wenigstens ein Rest R1, R2, R3 oder R4 ein Polyalkylenoxid Substituent ist und die verbleibenden Reste unabhängig voneinander gleiche oder unterschiedliche geradkettige oder verzweigte, gesättigte oder ungesättigte Ci bis C1S Alkylketten sind und X" ein Halogenid, Sulfatanion oder Anion einer C1 bis C6 Carbonsäure ist, aufweist.wherein at least one of R 1 , R 2 , R 3 or R 4 is a polyalkylene oxide substituent and the remaining radicals are independently the same or different straight or branched, saturated or unsaturated C 1 to C 1 alkyl chains and X "is a halide, sulfate anion or anion C 1 to C 6 carboxylic acid.
7. Elektrolyt gemäß Anspruch 6, wobei R1 und R2 eine C8 bis C12, bevorzugt eine C10 Alkylseitenkette ist, R3 eine C1 bis C3, bevorzugt eine C1 Alkylseitenkette ist, R4 der allgemeinen Formel [CH2-CH2-O]nH mit n= 1 bis 5 entspricht und X" das Anion eine C2 bis C4 Carbonsäure ist.7. An electrolyte according to claim 6, wherein R 1 and R 2 is a C 8 to C 12 , preferably a C 10 alkyl side chain, R 3 is a C 1 to C 3 , preferably a C 1 alkyl side chain, R 4 of the general formula [CH 2 -CH 2 -O] n H where n = 1 to 5 and X " the anion is a C 2 to C 4 carboxylic acid.
8. Elektrolyt gemäß Anspruch 7, wobei das mittlere Molekulargewicht des Netzmittels zwischen ungefähr 200 und ungefähr 1000 g/Mol, bevorzugt zwischen ungefähr 400 und ungefähr 500 g/Mol, noch bevorzugter zwischen ungefähr 450 und ungefähr 460 g/Mol liegt.The electrolyte of claim 7, wherein the average molecular weight of the wetting agent is between about 200 and about 1000 g / mol, preferably between about 400 and about 500 g / mol, more preferably between about 450 and about 460 g / mol.
9. Elektrolyt gemäß einem der vorhergehenden Ansprüche, wobei der Elektrolyt zusätzlich Polytetrafluorethylen-Partikel mit einem mittleren Partikeldurchmesser von ungefähr 10 bis ungefähr 1000 nm, vorzugsweise ungefähr 100 bis ungefähr 300nm aufweist. 9. An electrolyte according to any one of the preceding claims, wherein the electrolyte additionally comprises polytetrafluoroethylene particles having an average particle diameter of about 10 to about 1000 nm, preferably about 100 to about 300 nm.
10. Elektrolyt gemäß Anspruch 9, wobei der Elektrolyt die Polytetrafluor- ethylenpartikel in einer Konzentration von 0,1 bis 1000 mg/l, bevorzugt ungefähr 0,5 bis 5 mg/l enthält.10. An electrolyte according to claim 9, wherein the electrolyte contains the polytetrafluoro ethylene particles in a concentration of 0.1 to 1000 mg / l, preferably about 0.5 to 5 mg / l.
11. Verfahren zur elektrolytischen Abscheidung einer matten Metallschicht auf einem Substrat, wobei das Substrat in einem Galvanisierungsbad, aufweisend einen Elektrolyten gemäß einem der Ansprüche 1 bis 10 und eine Gegeneiektrode mit einer Spannungsquelle verbunden wird und eine Spannung zwischen Substrat und Gegenelektrode angelegt wird, die geeignet ist, eine Metallschicht auf dem Substrat abzuscheiden. A method of electrodepositing a matte metal layer on a substrate, wherein the substrate is connected in a plating bath comprising an electrolyte according to any of claims 1 to 10 and a counter electrode to a voltage source and a voltage is applied between the substrate and the counter electrode as appropriate is to deposit a metal layer on the substrate.
EP06701821A 2006-01-06 2006-01-06 Electrolyte and process for depositing a matt metal layer Active EP1969160B1 (en)

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