EP0554275B1 - Acid bath for copper plating, and a process using a bath of this type for this purpose - Google Patents
Acid bath for copper plating, and a process using a bath of this type for this purpose Download PDFInfo
- Publication number
- EP0554275B1 EP0554275B1 EP91917496A EP91917496A EP0554275B1 EP 0554275 B1 EP0554275 B1 EP 0554275B1 EP 91917496 A EP91917496 A EP 91917496A EP 91917496 A EP91917496 A EP 91917496A EP 0554275 B1 EP0554275 B1 EP 0554275B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- naphthol
- phenazonium
- ethoxylate
- thiourea
- compounds
- 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.)
- Expired - Lifetime
Links
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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- the invention relates to an acid bath for the electrodeposition of shiny and leveled copper coatings and the use.
- DE-PS 1246347 organic thio compounds
- DE-AS 1521062 polyvinyl compounds
- DE-AS 1521062 also describes an acidic copper bath which, in addition to a polymeric acidic compound with a hydrophilic group, also contains at least one substituted phenazonium compound in solution.
- Baths containing polymeric phenazonium compounds have made progress and are mainly used in combination with nonionic wetting agents and organic sulfur compounds.
- ⁇ -naphthol polyglycol ether as an additive to a copper bath is disclosed in DE-OS 37 21 985 (example 2) and GB-A-2075063, but not in combination with polymeric phenazonium compounds.
- DE-PS 3104108 describes a fluoroborate bath which contains ⁇ -naphthol ethoxylate in combination with a phthalocyanine dye.
- the electrolyte itself shows only a moderate leveling in comparison to polymeric phenazonium compounds.
- a disadvantage of these baths is the high leveling of a fine roughness (pittings, nodules) on the layer, which sensitively disturbs the decorative appearance of particularly large parts.
- This roughness is not due to floating particles in the electrolyte, but is due to a disturbed deposition in the cathodic double layer. This occurs particularly with nitrogen-containing sulfur compounds (so-called thiourea derivatives) and with phenazonium compounds.
- the object of this invention is to avoid the disadvantages described and, moreover, not to worsen the advantageous leveling.
- Thiourea and thiourea derivatives and S- and N-containing heterocyclic compounds are used as nitrogen-containing thio compounds.
- Table 2 contains examples of nitrogen-containing thio compounds (so-called thiourea derivatives) or S- and N-containing heterocyclic compounds and Table 3 for polymeric phenazonium compounds.
- the preferred amount in which the ⁇ -naphthol ethoxylate must be added in order to achieve a significant improvement in copper deposition is approximately 0.005 to 3 g / liter, preferably 0.01 to 0.25 g / liter.
- ⁇ -naphthol ethoxylates are known or can be prepared by processes known per se by reacting ⁇ -naphthol with ethylene oxide and / or propylene oxide.
- the individual components of the copper bath according to the invention can in general advantageously be present in the ready-to-use bath within the following limit concentrations: Usual oxygen-containing, high-molecular compounds 0.005 - 20 g / liter preferably 0.01 - 5 g / liter Common organic thio compounds with hydrophilic groups 0.0005 - 0.2 g / liter preferably 0.001 - 0.03 g / liter Usual nitrogen-containing thio compounds (so-called thiourea derivatives) and / or polymeric phenazonium compounds 0.0001 - 0.50 g / liter preferably 0.0005 - 0.04 g / liter
- the basic composition of the bath according to the invention can vary within wide limits.
- An aqueous solution of the following composition is generally used: Copper sulfate (CuSO4. 5H2O) 20 - 250 g / liter preferably 60 - 80 g / liter or 180 - 220 g / liter sulfuric acid 50 - 350 g / liter preferably 180 - 220 g / liter or 50 - 90 g / liter Sodium chloride 0.02 - 0.25 g / liter, preferably 0.05-0.12 g / liter
- copper sulfate instead of copper sulfate, other copper salts can also be used, at least in part.
- Some or all of the sulfuric acid can be replaced by fluoroboric acid, methanesulfonic acid or other acids.
- the addition of sodium chloride can be omitted in whole or in part if the additives already contain halogen ions.
- customary brighteners, levelers or wetting agents can also be present in the bathroom.
- the working conditions of the bath are as follows: PH value: ⁇ 1 Temperature: 15 ° C - 45 ° C, preferably 20 ° C - 30 ° C cath. Current density: 0.5 - 12 A / dm2, preferably 2-4 A / dm2
- the electrolyte movement is achieved by blowing in air.
- Copper with a content of 0.02 to 0.067% phosphorus is used as the anode
- the invention also includes methods using the baths according to the invention according to the claims.
- CuSO4.5 H2O copper sulfate
- 0.2 g / liter sodium chloride are used as brighteners 0.2 g / liter polyethylene glycol, 0.01 g / liter bis (w-sulfopropyl) disulfide, disodium salt, and 0.02 g / liter polymeric 7-dimethylamino-5-phenyl-phenazonium chloride admitted.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
Die Erfindung betrifft ein saures Bad zur galvanischen Abscheidung glänzender und eingeebneter Kupferüberzüge und die Verwendung.The invention relates to an acid bath for the electrodeposition of shiny and leveled copper coatings and the use.
Es ist seit langem bekannt, daß sauren, insbesondere den am meisten verbreiteten Schwefelsauren Kupferelektrolyten bestimmte organische Substanzen in geringen Mengen zugesetzt werden können, um statt einer kristallin-matten Abscheidung glänzende Kupferüberzüge zu erhalten. Für diesen Zweck werden zum Beispiel Polyäthylenglycol, Thioharnstoff, Gelatine,
Melasse, Kaffee-Extrakt, "basische" Farbstoffe und Thiophosphorsäureester verwendet.Solche Bäder besitzen jedoch keinerlei praktische Bedeutung mehr, da die Qualität der erhaltenen Kupferüberzüge nicht den heutigen Anforderungen entspricht. So sind die Überzüge entweder zu spröde oder sie besitzen einen zu geringen Glanz bzw. fallen in bestimmten Stromdichtebereichen reliefartig aus.It has long been known that acidic, in particular the most widespread sulfuric acid copper electrolytes, certain organic substances can be added in small amounts in order to obtain shiny copper coatings instead of a crystalline matt deposition. For this purpose, for example, polyethylene glycol, thiourea, gelatin,
Molasses, coffee extract, "basic" dyes and thiophosphoric acid esters are used. However, such baths no longer have any practical significance, since the quality of the copper coatings obtained does not meet today's requirements. For example, the coatings are either too brittle or have a low gloss or are relief-like in certain current density ranges.
Bekannt ist der Zusatz von Polyalkyliminen in Verbindung mit organischen Thioverbindungen (DE-PS 1246347) und Polyvinylverbindungen in Mischung mit sauerstoffhaltigen hochmolekularen Verbindungen und organischen, insbesondere aromatischen Thioverbindungen (De-AS 1521062). Derartige Kupferelektrolyte erlauben aber nicht den Einsatz höherer kathodischer Stromdichten, und die abgeschiedenen Kupferüberzüge können außerdem nur nach einer voarusgegangenen Zwischenbehandlung vernickelt werden. In der genannten DE-AS 1521062 wird außerdem ein saures Kupferbad beschrieben, das neben einer polymeren saurestoffhaltigen Verbindung mit hydrophiler Gruppe noch mindestens eine substituierte Phenazoniumverbindung gelöst enthält.It is known to add polyalkylimines in conjunction with organic thio compounds (DE-PS 1246347) and polyvinyl compounds in a mixture with oxygen-containing high molecular compounds and organic, in particular aromatic thio compounds (DE-AS 1521062). However, such copper electrolytes do not allow the use of higher cathodic current densities, and the deposited copper coatings can also only be nickel-plated after an intermediate treatment. DE-AS 1521062 also describes an acidic copper bath which, in addition to a polymeric acidic compound with a hydrophilic group, also contains at least one substituted phenazonium compound in solution.
Bei diesen monomeren Phenazoniumverbindungen ist die anwendbare Stromdichte sowie das Alterungsverhalten verbesserungswürdig. Weiter sind Kombinationen von organischen Thioverbindungen und nichtionogenen Netzmitteln mit anderen Farbstoffen wie zum Beispiel Kristall-Violett (EP-PS 71512), Amiden (DE-PS 2746938), Phthalocyanin-Derivaten mit Apo-Safranin (DE-PS 3420999) bekannt. Anstelle des Farbstoffes werden auch undefinierte Umsetzungsprodukte von Polyaminen mit Benzylchlorid (DE-PS 2541897) bzw. Epichlorhydrin (EU-PS 68807) oder solche mit Thioverbindungen und Acrylamid (EU-PS 107109) verwendet.In the case of these monomeric phenazonium compounds, the current density which can be used and the aging behavior are in need of improvement. Combinations of organic thio compounds and nonionic wetting agents with other dyes such as, for example, crystal violet (EP-PS 71512), amides (DE-PS 2746938), phthalocyanine derivatives with aposafranine (DE-PS 3420999) are known. Instead of the dye, undefined reaction products of polyamines with benzyl chloride (DE-PS 2541897) or epichlorohydrin (EU-PS 68807) or those with thio compounds and acrylamide (EU-PS 107109) are also used.
Die bisher bekannten Bäder ergeben alle ungleichmäßige Abscheidungen; insbesondere die Kombination mit stickstoffhaltigen Thioverbindungen.The previously known baths all result in uneven deposits; especially the combination with nitrogen-containing thio compounds.
Einen Fortschritt erbrachten Bäder, die polymere Phenazoniumverbindungen (DE-PS 2039831) enthalten;diese finden hauptsächlich in Kombination mit nichtionogenen Netzmitteln und organischen Schwefelverbindungen Anwendung.Baths containing polymeric phenazonium compounds (DE-PS 2039831) have made progress and are mainly used in combination with nonionic wetting agents and organic sulfur compounds.
Zwar ist es Stand der Technik, nichtionogene Netzmittel den sauren Kupferbädern zuzusetzen, die Entfernung der feinen Rauheit gelang damit jedoch nicht.Although it is state of the art to add nonionic wetting agents to the acidic copper baths, the removal of the fine roughness was not successful.
Die Verwendung von β-Naphthol-Polyglycoläther als Zusatz eines Kupferbades werden in der DE-OS 37 21 985 (Beispiel 2) und GB-A-2075063 offenbart, jedoch nicht in der Kombination mit polymeren Phenazoniumverbindungen.The use of β-naphthol polyglycol ether as an additive to a copper bath is disclosed in DE-OS 37 21 985 (example 2) and GB-A-2075063, but not in combination with polymeric phenazonium compounds.
In der DE-PS 3104108 wid ein Fluorboratbad beschrieben, das β-Naphtholäthoxylat in Kombination mit einem Phthalocyanin-Farbstoff enthält. Der Elektrolyt selbst zeigt nur eine mäßige Einebnung im Vergelich zu polymeren Phenazoniumverbindungen.DE-PS 3104108 describes a fluoroborate bath which contains β-naphthol ethoxylate in combination with a phthalocyanine dye. The electrolyte itself shows only a moderate leveling in comparison to polymeric phenazonium compounds.
Nachteilig bei diesen Bädern ist bei hoher Einebnung eine feine Rauheit (Pittings, Nodules) auf der Schicht, welche das dekorative Aussehen besonders großflächiger Teile empfindlich stört. Diese Rauheit rührt nicht von Schwebeteilchen im Elektrolyten her, sondern beruht auf einer gestörten Abscheidung in der kathodischen Doppelschicht. Diese tritt besonders bei stickstoffhaltigen Schwefelverbindungen (sog. Thioharnstoffderivaten) und bei Phenazoniumverbindungen auf.A disadvantage of these baths is the high leveling of a fine roughness (pittings, nodules) on the layer, which sensitively disturbs the decorative appearance of particularly large parts. This roughness is not due to floating particles in the electrolyte, but is due to a disturbed deposition in the cathodic double layer. This occurs particularly with nitrogen-containing sulfur compounds (so-called thiourea derivatives) and with phenazonium compounds.
Aufgabe dieser Erfindung ist es, diese beschriebenen Nachteile zu vermeiden und darüber hinaus die vorteilhafte Einebnung nicht zu verschlechtern.The object of this invention is to avoid the disadvantages described and, moreover, not to worsen the advantageous leveling.
Diese Aufgabe wird erfindungsgemäß durch ein saures Bad gelöst, das mindestens eine Mischung bestehend aus β-Naphtholalkoxylaten der allgemeinen Formel I
in der n = 0 - 50, vorzugsweise 10 - 25, und m = 0 - 50, vorzugsweise 0 - 10, bedeuten, wobei n + m ≧ 3 ist, Thioharnstoff oder Thioharnstoffderivat und polymere Phenazoniumverbindung enthält.This object is achieved according to the invention by an acid bath containing at least one mixture consisting of β-naphthol alkoxylates of the general formula I.
in which n = 0-50, preferably 10-25, and m = 0-50, preferably 0-10, where n + m ≧ 3, contains thiourea or thiourea derivative and polymeric phenazonium compound.
Als β-Naphtholalkoxylate der allgemeinen Formel I eignen sich besonders Verbindungen der
Als Stickstoffhaltige Thioverbindungen finden Thioharnstoff und Thioharnstoffderivate sowie S- und N-haltige heterocyclische Verbindungen Anwendung.Thiourea and thiourea derivatives and S- and N-containing heterocyclic compounds are used as nitrogen-containing thio compounds.
Tabelle 2 enthält Beispiele für stickstoffhaltige Thioverbindungen (sog. Thioharnstoffderivate) oder S- und N-haltige heterocyclische Verbindungen und Tabelle 3 für polymere Phenazoniumverbindungen.
Für die erfindungsgemäßen Lösungen werden Gemische der in den Tabellen 1,2 und 3 aufgeführten Verbindungen eingesetzt.Mixtures of the compounds listed in Tables 1, 2 and 3 are used for the solutions according to the invention.
Die bevorzugte Menge, in der das β-Naphtholäthoxylat zugegeben werden muß, um eine deutliche Verbesserung der Kupferabscheidung zu erzielen, beträgt etwa 0,005 bis 3 g/Liter vorzugsweise 0,01 bis 0,25 g/Liter.The preferred amount in which the β-naphthol ethoxylate must be added in order to achieve a significant improvement in copper deposition is approximately 0.005 to 3 g / liter, preferably 0.01 to 0.25 g / liter.
Die β-Naphtholäthoxylate sind bekannt oder können nach an sich bekannten Verfahren durch Umsetzen von β - Naphthol mit Äthylenoxyd und/oder Propylenoxyd hergestellt werden.The β-naphthol ethoxylates are known or can be prepared by processes known per se by reacting β-naphthol with ethylene oxide and / or propylene oxide.
Die Einzelkomponenten des erfindungsgemäßen Kupferbades können im allgemeinen vorteilhaft innerhalb folgender Grenzkonzentrationen im anwendungsfertigen Bad enthalten sein:
Die Grundzusammensetzung des erfindungsgemäßen Bades kann in weiten Grenzen schwanken. Im allgemeinen wird eine wässrige Lösung folgender Zusammensetzung benutzt:
Anstelle von Kupfersulfat können zumindest teilweise auch andere Kupfersalze benutzt werden. Auch die Schwefelsäure kann teilweise oder ganz durch Fluoroborsäure, Methansulfonsäure oder andere Säuren ersetzt werden. Die Zugabe von Natriumchlorid kann ganz oder teilweise entfallen, wenn in den Zusätzen bereits Halogenionen enthalten sind.Instead of copper sulfate, other copper salts can also be used, at least in part. Some or all of the sulfuric acid can be replaced by fluoroboric acid, methanesulfonic acid or other acids. The addition of sodium chloride can be omitted in whole or in part if the additives already contain halogen ions.
Außerdem können im Bad auch zusätzlich übliche Glanzbildner, Einebner oder Netzmittel enthalten sein.In addition, customary brighteners, levelers or wetting agents can also be present in the bathroom.
Zur Herstellung des erfindungsgemäßen Bades werden die Einzelkomponenten der Grundzusammensetzung hinzugefügt.To produce the bath according to the invention, the individual components of the basic composition are added.
Die Arbeitsbedingungen des Bades sind wie folgt:
Die Elektrolytbewegung wird durch Einblasen von Luft erreicht.The electrolyte movement is achieved by blowing in air.
Als Anode wird Kupfer mit einem Gehalt von 0,02 bis 0,067 % Phosphor verwendet
Die Erfindung beinhaltet auch Verfahren unter Verwendung der erfindungsgemäßen Bäder gemäß den Patentansprüchen.Copper with a content of 0.02 to 0.067% phosphorus is used as the anode
The invention also includes methods using the baths according to the invention according to the claims.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung:The following examples serve to illustrate the invention:
Einem Kupferbad der Zusammensetzung
200,0 g/Liter Kupfersulfat (CuSO₄.5 H₂O)
65,0 g/Liter Schwefelsäure
0,2 g/Liter Natriumchlorid
werden als Glanzbildner
0,2 g/Liter Polyäthylenglycol,
0,01 g/Liter Bis-(w-sulfopropyl)-disulfid, Dinatriumsalz,
und
0,02 g/Liter polymeres 7-Dimethylamino-5-phenyl-phenazonium-chlorid
zugegeben. Bei einer Elektrolyttemperatur von 27 °C erhält man bei einer Stromdichte von 4 A/dm² und Lufteinblasung einen gut eingeebneten glänzenden Kupferüberzug, der auf poliertem Messingblech beim genauen Hinsehen feine Rauhigkeiten (Pittings) zeigt.A copper bath of the composition
200.0 g / liter copper sulfate (CuSO₄.5 H₂O)
65.0 g / liter sulfuric acid
0.2 g / liter sodium chloride
are used as brighteners
0.2 g / liter polyethylene glycol,
0.01 g / liter bis (w-sulfopropyl) disulfide, disodium salt,
and
0.02 g / liter polymeric 7-dimethylamino-5-phenyl-phenazonium chloride
admitted. At an electrolyte temperature of 27 ° C, with a current density of 4 A / dm² and air injection, a well-leveled, shiny copper coating is obtained, which shows a fine roughness (pitting) when you look closely at the polished brass sheet.
Gibt man dem Bad zusätzlich 0,025 g/Liter β-Naphtholalkoxylate der allgemeinen Formel I mit n = 12 und m = 0 zu, so ist die Abscheidung spiegelglänzend und gut eingeebnet. Man erkennt keine Fehlstellen.If 0.025 g / liter of β-naphthol alkoxylates of the general formula I with n = 12 and m = 0 are added to the bath, the deposition is mirror-like and well leveled. You can see no defects.
Einem Kupferbad der Zusammensetzung
80 g/Liter Kupfersulfat (CuSO₄.5 H₂O)
180 g/Liter Schwefelsäure konz.
0,08 g/Liter Natriumchlorid
werden als Glanzbildner
0,6 g/Liter Polypropylenglycol und
0,02 g/Liter 3-Mercaptopropan-1-sulfonsäure, Natriumsalz
und
0,003 g/Liter N-Acetylthioharnstoff
zugegeben. Bei einer Elektrolyttemperatur von 30 °C enthält man auf gekratztem Kupferlaminat bei einer Stromdichte von 2 A/dm² glänzende Abscheidungen, bei der feine Rauhigkeiten (Pittings) sichtbar sind.A copper bath of the composition
80 g / liter copper sulfate (CuSO₄.5 H₂O)
180 g / liter sulfuric acid conc.
0.08 g / liter sodium chloride
are used as brighteners
0.6 g / liter polypropylene glycol and
0.02 g / liter 3-mercaptopropan-1-sulfonic acid, sodium salt
and
0.003 g / liter of N-acetylthiourea
admitted. At an electrolyte temperature of 30 ° C there are shiny deposits on scraped copper laminate with a current density of 2 A / dm², at which fine roughness (pittings) are visible.
Setzt man dem Bad 0,05 g/Liter der erfindungsgemäßen Substanz der allgemeinen Formel I mit n = 24 und m = 0 zu, so ist der Kupferüberzug blank und enthält keine Störungen.If 0.05 g / liter of the substance of the general formula I according to the invention with n = 24 and m = 0 is added to the bath, the copper coating is bare and contains no defects.
Claims (14)
- Aqueous acidic bath for the electrodeposition of shiny and smooth copper coatings, including at least one mixture comprising β-naphthol alkoxylate of the general formula I
- Bath according to claim 1, including as the β-naphthol alkoxylate of the general formula I
β-naphthol-tetracosa(ethoxylate)
β-naphthol-eicosa(ethoxylate)
β-naphthol-octadeca(ethoxylate)
β-naphthol-hexadeca(ethoxylate)
β-naphthol-tetradeca(ethoxylate)
β-naphthol-trideca(ethoxylate)
β-naphthol-dodeca(ethoxylate)
β-naphthol-deca(ethoxylate)
β-naphthol-octa(ethoxylate)
β-naphthol-hexa(ethoxylate)
β-naphthol-tetracosa(propoxylate)
β-naphthol-tetracosa(ethoxy)-mono(propoxylate)
β-naphthol-octadeca(ethoxy)-di(propoxylate)
β-naphthol-mono(propoxy)-tetracosa(ethoxylate)
β-naphthol-di(propoxy)-octadeca(ethoxylate)
or mixtures of these compounds. - Bath according to claim 1 or 2, including β-naphthol alkoxylate of the general formula I in concentrations of between 0.005 and 3 g/litre.
- Bath according to claim 1, including as the thiourea derivative or S- and N-containing heterocyclic compounds
N-acetyl thiourea,
N-trifluoroacetyl thiourea
N-ethyl thiourea
N-cyanoacetyl thiourea
N-allyl thiourea
o-tolyl thiourea
N,N'-butylene thiourea
thiazolidine thiol(2)
4-thiazoline thiol (2)
imidazolidine thiol(2) (N,N'-ethylene thiourea)
4-methyl-2-pyrimidine thiol
2-thiouracil
or mixtures of these compounds. - Bath according to claim 1 or 4, including thiourea or thiourea derivatives in concentrations of between 0.0001 and 0.5 g/litre.
- Bath according to claim 1, including as the polymeric phenazonium compound
poly(6-methyl-7-dimethylamino-5-phenyl-phenazonium sulphate)
poly(2-methyl-7-diethylamino-5-phenyl-phenazonium chloride)
poly(2-methyl-7-dimethylamino-5-phenyl-phenazonium sulphate)
poly(5-methyl-7-dimethylamino-phenazonium acetate)
poly(2-methyl-7-anilino-5-phenyl-phenazonium sulphate)
poly(2-methyl-7-dimethylamino-phenazonium sulphate)
poly(7-methylamino-5-phenyl-phenazonium acetate)
poly(7-ethylamino-2,5-diphenyl-phenazonium chloride)
poly(2,8-dimethyl-7-diethylamino-5-p-tolyl-phenazonium chloride)
poly(2,5,8-triphenyl-7-dimethylamino-phenazonium sulphate)
poly(2,8-dimethyl-7-amino-5-phenyl-phenazonium sulphate)
poly(7-dimethylamino-5-phenyl-phenazonium chloride)
or mixtures of these compounds. - Bath according to claim 1 or 6, including polymeric phenazonium compounds in concentrations of between 0.0001 and 0.5 g/litre.
- Bath according to claim 1, characterised by an additional content of at least one oxygen-containing, high-molecular compound.
- Bath according to claim 8, including as the oxygen-containing, high-molecular compounds
polyvinyl alcohol
carboxymethyl cellulose
polyethylene glycol
polypropylene glycol
stearic acid polyglycol ester
oleic acid polyglycol ester
stearyl alcohol polyglycol ether
nonyl phenol polyglycol ether
octonal polyalkylene glycol ether
octane diol-bis(polyalkylene glycol ether)
polyoxypropylene glycol
polyethylene-propylene glycol
or mixtures of these compounds. - Bath according to claim 9, including oxygen-containing, high-molecular compounds in concentrations of between 0.005 and 20 g/litre.
- Bath according to claim 1, characterised by an additional content of an organic, nitrogen-free thio compound with water-soluble, hydrophilic groups.
- Bath according to claim 11, including as the organic, nitrogen-free thio compound
3-mercaptopropane-1-sulphonic acid, sodium salt
thiophosphoric acid-o-ethyl-bis-(w-sulphopropyl)-ester, disodium salt
thiophosphoric acid-tris-(w-sulphopropyl)-ester, trisodium salt
ethylene dithiodipropyl sulphonic acid, sodium salt
di-n-propyl thioether-di-w-sulphonic acid, disodium salt
bis-(w-sulphopropyl)disulphide, disodium salt
bis(w-sulphohydroxypropyl)disulphide, disodium salt
bis(w-sulphobutyl)disulphide, disodium salt
methyl-(w-sulphopropyl)disulphide, sodium salt
methyl-(w-sulphobutyl)trisulphide, sodium salt
or mixtures of these compounds. - Bath according to claim 12, including the organic, nitrogen-free thio compounds with water-soluble, hydrophilic groups in concentrations of between 0.0005 and 0.2 g/litre.
- Use of the bath according to at least one of claims 1 to 13 for the electrodeposition of copper.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4032864 | 1990-10-13 | ||
| DE4032864A DE4032864A1 (en) | 1990-10-13 | 1990-10-13 | ACIDIC BATH FOR THE GALVANIC DEPOSITION OF COPPER COVERS AND METHODS USING THIS COMBINATION |
| PCT/DE1991/000811 WO1992007116A1 (en) | 1990-10-13 | 1991-10-11 | Acid bath for copper plating, and a process using a bath of this type for this purpose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0554275A1 EP0554275A1 (en) | 1993-08-11 |
| EP0554275B1 true EP0554275B1 (en) | 1994-12-14 |
Family
ID=6416407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91917496A Expired - Lifetime EP0554275B1 (en) | 1990-10-13 | 1991-10-11 | Acid bath for copper plating, and a process using a bath of this type for this purpose |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0554275B1 (en) |
| JP (1) | JPH06501986A (en) |
| AT (1) | ATE115651T1 (en) |
| CA (1) | CA2093924C (en) |
| DE (2) | DE4032864A1 (en) |
| ES (1) | ES2066477T3 (en) |
| WO (1) | WO1992007116A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE202015003382U1 (en) | 2014-05-09 | 2015-06-16 | Dr. Hesse GmbH & Cie. KG | Electrolytic deposition of copper from water-based electrolytes |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10261852B3 (en) * | 2002-12-20 | 2004-06-03 | Atotech Deutschland Gmbh | Mixture of di-, tri- and other oligomeric phenazinium compounds, used in copper electroplating bath for decorative plating or plating circuit board or semiconductor substrate, is prepared from monomer by diazotization and boiling |
| DE10337669B4 (en) * | 2003-08-08 | 2006-04-27 | Atotech Deutschland Gmbh | Aqueous, acid solution and process for the electrodeposition of copper coatings and use of the solution |
| DE102004041701A1 (en) * | 2004-08-28 | 2006-03-02 | Enthone Inc., West Haven | Process for the electrolytic deposition of metals |
| US7282602B2 (en) * | 2004-09-21 | 2007-10-16 | Bionumerik Pharmaceuticals, Inc. | Medicinal disulfide salts |
| KR101362062B1 (en) * | 2006-01-27 | 2014-02-11 | 오꾸노 케미칼 인더스트리즈 컴파니,리미티드 | Additive added to solution for electrolytic copper plating using anode of phosphorated copper, solution for electrolytic copper plating and method of electrolytic copper plating |
| US11035051B2 (en) | 2016-08-15 | 2021-06-15 | Atotech Deutschland Gmbh | Acidic aqueous composition for electrolytic copper plating |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL291575A (en) * | 1962-04-16 | |||
| DE1246347B (en) * | 1966-03-08 | 1967-08-03 | Schering Ag | Acid galvanic copper bath |
| DE2039831C3 (en) * | 1970-06-06 | 1979-09-06 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Acid bath for the galvanic deposition of shiny copper coatings |
| NL7510771A (en) * | 1975-03-11 | 1976-09-14 | Oxy Metal Industries Corp | PROCEDURE FOR ELECTROLYTIC DEPOSITION OF COPPER FROM Aqueous ACID GALVANIZING BATHS. |
| DE2721985A1 (en) * | 1977-05-14 | 1978-11-16 | Bayer Ag | PROCESS FOR THE PRODUCTION OF POLYISOCYANATE POLYADDITION PRODUCTS CONTAINING URETHANE AND / OR UREA GROUPS |
| DE2746938C2 (en) * | 1977-10-17 | 1987-04-09 | Schering AG, 1000 Berlin und 4709 Bergkamen | Aqueous acid bath for the galvanic deposition of shiny and crack-free copper coatings and use of this bath |
| US4272335A (en) * | 1980-02-19 | 1981-06-09 | Oxy Metal Industries Corporation | Composition and method for electrodeposition of copper |
| US4374709A (en) * | 1980-05-01 | 1983-02-22 | Occidental Chemical Corporation | Process for plating polymeric substrates |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| FR2510145B1 (en) * | 1981-07-24 | 1986-02-07 | Rhone Poulenc Spec Chim | ADDITIVE FOR AN ACID ELECTROLYTIC COPPER BATH, ITS PREPARATION METHOD AND ITS APPLICATION TO COPPER PRINTED CIRCUITS |
| WO1984001393A1 (en) * | 1982-09-30 | 1984-04-12 | Learonal Inc | Electrolytic copper plating solutions |
| DE3402999A1 (en) * | 1984-01-28 | 1985-08-01 | Skw Trostberg Ag, 8223 Trostberg | Fertiliser solutions |
| DE3721985A1 (en) * | 1987-06-30 | 1989-01-12 | Schering Ag | AQUEOUS ACID BATH FOR GALVANIC DEPOSITION OF GLOSSY AND LEVELED COPPER COATINGS |
-
1990
- 1990-10-13 DE DE4032864A patent/DE4032864A1/en active Granted
-
1991
- 1991-10-11 AT AT91917496T patent/ATE115651T1/en not_active IP Right Cessation
- 1991-10-11 WO PCT/DE1991/000811 patent/WO1992007116A1/en not_active Ceased
- 1991-10-11 JP JP3516095A patent/JPH06501986A/en active Pending
- 1991-10-11 EP EP91917496A patent/EP0554275B1/en not_active Expired - Lifetime
- 1991-10-11 CA CA002093924A patent/CA2093924C/en not_active Expired - Lifetime
- 1991-10-11 ES ES91917496T patent/ES2066477T3/en not_active Expired - Lifetime
- 1991-10-11 DE DE59103933T patent/DE59103933D1/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE202015003382U1 (en) | 2014-05-09 | 2015-06-16 | Dr. Hesse GmbH & Cie. KG | Electrolytic deposition of copper from water-based electrolytes |
| DE102014208733A1 (en) | 2014-05-09 | 2015-11-12 | Dr. Hesse Gmbh & Cie Kg | Process for the electrolytic deposition of copper from water-based electrolytes |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0554275A1 (en) | 1993-08-11 |
| ATE115651T1 (en) | 1994-12-15 |
| DE59103933D1 (en) | 1995-01-26 |
| JPH06501986A (en) | 1994-03-03 |
| CA2093924C (en) | 2002-02-05 |
| WO1992007116A1 (en) | 1992-04-30 |
| CA2093924A1 (en) | 1992-04-14 |
| DE4032864C2 (en) | 1993-01-07 |
| DE4032864A1 (en) | 1992-04-16 |
| ES2066477T3 (en) | 1995-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AT395603B (en) | AQUEOUS ACID BATH FOR GALVANIC DEPOSITION OF GLOSSY AND CRACK-FREE COPPER COATINGS AND USE OF THIS BATH | |
| EP0598763B1 (en) | Acid bath for the galvanic deposition of copper, and the use of such a bath | |
| DE19653681C2 (en) | Process for the electrolytic deposition of copper layers with a uniform layer thickness and good optical and metal-physical properties and application of the process | |
| EP1042538B1 (en) | Aqueous bath and method for electrolytic deposition of copper coatings | |
| DE2255584C2 (en) | Acid copper plating bath | |
| DE3210286A1 (en) | AQUEOUS ACID ELECTROLYT FOR THE GALVANIC DEPOSITION OF COPPER | |
| CH642686A5 (en) | ACID GALVANIC COPPER BATH. | |
| DE69714446T2 (en) | ALCOXYLATED MERCAPTAINS AS A COPPER ADDITIVE | |
| US5849171A (en) | Acid bath for copper plating and process with the use of this combination | |
| DE60022480T2 (en) | copper plating | |
| DE2056954C2 (en) | Aqueous acid bath for the galvanic deposition of a tin coating and process for this | |
| EP0554275B1 (en) | Acid bath for copper plating, and a process using a bath of this type for this purpose | |
| AT396946B (en) | AQUEOUS ACID BATH FOR GALVANIC DEPOSITION OF SHINY AND LEVELED COPPER COATINGS | |
| DE602004011520T2 (en) | AQUEOUS, SOFT SOLUTION AND METHOD FOR THE ELECTROLYTIC DECOMPOSITION OF COPPER COATS AND THE USE OF THE SOLUTION | |
| DE2835539C2 (en) | ||
| DE2459428C2 (en) | Process for the production of a brightener for acidic galvanic tin baths and its use | |
| DE3611627A1 (en) | CONNECTION, COMPOSITION AND METHOD FOR ELECTROPLATING | |
| EP0785297B1 (en) | An aqueous acid bath for the electrodeposition of a shiny and tear-free copper coating and its application | |
| DE3149043A1 (en) | "BATH FOR GALVANIC DEPOSITION OF THIN WHITE PALLADIUM COATINGS AND METHOD FOR THE PRODUCTION OF SUCH COATINGS USING THE BATH" | |
| DE3139815A1 (en) | "METHOD FOR MAINTAINING A GOLD COATING WITH IMPROVED CORROSION RESISTANCE ON A SUBSTRATE" | |
| DE1952218C3 (en) | Aqueous acid bath for the galvanic deposition of tin coatings and its use | |
| DE3027982C2 (en) | Aqueous bath and method for the electrodeposition of a black nickel layer | |
| DE2948999C2 (en) | Aqueous, acidic bath for the electrodeposition of gold and method for the electrodeposition of hard gold with its use | |
| DE2256025C2 (en) | Aqueous acid bath for the galvanic deposition of tin / lead alloy deposits | |
| DE1804970B2 (en) | GALVANIC CYANIDIC ORGANIC SELENIUM COMPOUND, SHINY COPPER BATH |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19930317 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ATOTECH DEUTSCHLAND GMBH |
|
| 17Q | First examination report despatched |
Effective date: 19940126 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19941214 Ref country code: DK Effective date: 19941214 Ref country code: BE Effective date: 19941214 |
|
| REF | Corresponds to: |
Ref document number: 115651 Country of ref document: AT Date of ref document: 19941215 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 59103933 Country of ref document: DE Date of ref document: 19950126 |
|
| ITF | It: translation for a ep patent filed | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2066477 Country of ref document: ES Kind code of ref document: T3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19950314 |
|
| ET | Fr: translation filed | ||
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950315 |
|
| NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Effective date: 19951031 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19951031 Ref country code: LI Effective date: 19951031 |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20091015 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20101104 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20101022 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20101021 Year of fee payment: 20 Ref country code: IT Payment date: 20101026 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20101025 Year of fee payment: 20 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101011 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59103933 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59103933 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20111010 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111010 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111012 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20140826 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111012 |