EP0137397B1 - Acid galvanic copper bath and process for its preparation - Google Patents
Acid galvanic copper bath and process for its preparation Download PDFInfo
- Publication number
- EP0137397B1 EP0137397B1 EP84111402A EP84111402A EP0137397B1 EP 0137397 B1 EP0137397 B1 EP 0137397B1 EP 84111402 A EP84111402 A EP 84111402A EP 84111402 A EP84111402 A EP 84111402A EP 0137397 B1 EP0137397 B1 EP 0137397B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- bath
- propane derivatives
- bifunctional
- polymers derived
- 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 present invention relates to an aqueous acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and, if appropriate, other bath additives, and to the process for producing the same.
- DE-PS 9 75 247 DE-AS 1 086 508, DE-AS 1 921 845 and DE-AS 2 003 539.
- DE-AS 1 521 061 also discloses copper baths with to produce a content of polymers, a 1,3-dioxolane polymer having terminal hydroxyl groups being described as the polymer.
- the copper baths according to DE-OS 15 21 062 can also contain other polyether polymers.
- the object of the invention is therefore to develop an acidic galvanic copper strip which, apart from an improved scattering capacity, provides fine crystalline, ductile copper deposits, with high elongation at break values and better shock test behavior.
- an acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and optionally other bath additives characterized in that it contains bifunctional propane derivatives of the formulas 1 and / or II, where X and Y represents a hydroxyl group or halogen, X is not Y and Z is oxygen, sulfur or a methylene group, which were polymerized in the presence of 1 to 50 mol% of one or more unsaturated alcohols having 3 to 10 carbon atoms and one or more double and / or triple bonds at a temperature of 100 to 260 ° C.
- the molar ratio of polymers from bifunctional propane derivatives to alcohol should be in the range from 2: 1 to 100: 1, preferably 10: 1 to 80: 1.
- the present invention furthermore relates to a process for the preparation of an acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and, if appropriate, other bath additives, characterized in that the bifunctional propane derivatives are present in the presence of 1 to 50 mol%. polymerizes one or more unsaturated alcohols with 3 to 10 carbon atoms and one or more double and / or triple bonds, dilutes the polymer at temperatures below 100 ° C. with water and optionally small amounts of a lower alcohol and then adds it to the acidic copper bath.
- Typical examples of these substances are monochlorohydrin, epichlorohydrin and glycid (glycidol).
- the bifunctional propane derivatives can be polymerized in a manner known per se by adding catalysts such as protonic acids and Lewis acids.
- catalysts such as protonic acids and Lewis acids.
- Boron trifluoride etherate has proven particularly useful as Lewis acid, but other catalysts are also suitable for the preparation of the polymers used according to the invention.
- the polymers used according to the invention are copolymers of the bifunctional propane derivatives, the end groups of which contain unsaturated alcohols.
- Polymers of glycides include poly ethers with primary or secondary OH groups as well as terminal groups belonging to an unsaturated alcohol. These polymers are viscous in their pure form and can be dissolved in hot water or in hot water with the addition of lower alcohols. They are added to the copper bath in the form of such aqueous or aqueous-alcoholic solutions. If necessary, the undissolved material is filtered off beforehand.
- the amount of additive according to the invention is not critical. It has been shown that amounts of 0.1 to 1 g of polymer per liter of copper bath are completely sufficient to achieve the desired effect. If the solutions of the polymer are adjusted to a concentration of approximately 2.5% by weight, 4 to 40 ml of this solution per liter of copper bath are sufficient.
- the copper baths according to the invention can be used at current densities between 0.5 and 10 Aldm2.
- the copper plating of conductor tracks shows that layer thicknesses are also achieved in the boreholes which are over 90% of the thickness of the layer thicknesses otherwise achieved.
- circuit boards produced with the copper bath according to the invention with copper coatings of 20 to 30 ⁇ m are subjected to a temperature shock test by heating to 250 ° C. in an oil bath and then cooling again to room temperature, no defects and edge breaks in the copper layer are observed even after 10 cycles .
- Copper foils of 50 ⁇ m thickness produced with the aid of the copper bath according to the invention show measured values in the range from 6 to 20% in the test for elongation at break.
- Another advantage of the copper baths according to the invention is that instead of the usual concentration of 10 to 20 g / l copper and 100 to 250 g / l sulfuric acid, now also at concentrations of 40 to 80 g / l copper and 30 to 80 g / l Sulfuric acid can work.
- the copper baths according to the invention can be moved in the usual way by blowing in air.
- the bath temperature is generally 15 to 40 ° C.
- cathodic current densities of 0.5-4 A / dm 2 finely crystalline, ductile copper coatings with excellent scattering capacity are deposited from this electrolyte. If a circuit board with a material thickness of 3 mm and a bore diameter of 0.3 mm is copper-plated in the electrolytes according to the invention, cathodic current densities of 0.5-1.0 Aldm 2 in the holes layer thicknesses of over 90% based on the conductor track.
- the elongation at break is determined on copper foils (50 .mu.m) produced in the electrolyte according to the invention, measurement values in the range of 6-20% are obtained. It is essential that the elongation at break values remain constant even after a long period of operation of the electrolyte, that is to say that no disruptive degradation products are formed.
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)
Description
Gegenstand der vorliegenden Erfindung ist ein wässriges saures galvanisches Kupferbad zur Abscheidung von feinkörnigem duktilem Kupfer mit einem Gehalt an Polymeren aus bifunktionellen Propanderivaten und gegebenenfalls anderen Badzusätzen sowie das Verfahren zur Herstellung derselben.The present invention relates to an aqueous acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and, if appropriate, other bath additives, and to the process for producing the same.
Es ist bekannt, zu sauren galvanischen Kupferbädern zur Abscheidung von feinkörnigem duktilem Kupfer, insbesondere solchen mit glänzender Oberfläche, verschiedenartige Zusätze zuzugeben. Typische derartige Zusätze sind beispielsweise beschrieben in der DE-PS 9 75 247, DE-AS 1 086 508, DE-AS 1 921 845 und DE-AS 2 003 539. Aus der DE-AS 1 521 061 ist weiterhin bekannt, Kupferbäder mit einem Gehalt an Polymeren herzustellen, wobei als Polymere ein 1,3-Dioxolanpolymerisat mit endständigen Hydroxylgruppen beschrieben wird. Die Kupferbäder gemäß der DE-OS 15 21 062 können auch andere Polyätherpolymerisate enthalten. Mit all diesen Zusätzen erhält man zwar mehr oder weniger glatte, feinkristalline Kupferniederschläge, jedoch werden diese den erhöhten Anforderungen der Praxis bei der Verkupferung von Leiterplatten nicht gerecht. Insbesondere sind die erzielbaren Werte für Bruchdehnung und Schocktestverhalten unbefriedigend. Außerdem weisen viele Kupferbäder des Standes der Technik den Nachteil auf, daß sie nur ein geringes Streuvermögen aufweisen, d.h. die Konzentration an Kupfer und Säure sowie die anwendbaren Stromdichten dürfen nur in relativ engen Grenzen variiert werden, ohen die Qualität der Kupferüberzüge zu verschlechtern.It is known to add various additives to acidic galvanic copper baths for the deposition of fine-grained ductile copper, in particular those with a shiny surface. Typical additives of this type are described, for example, in DE-PS 9 75 247, DE-AS 1 086 508, DE-AS 1 921 845 and DE-AS 2 003 539. DE-AS 1 521 061 also discloses copper baths with to produce a content of polymers, a 1,3-dioxolane polymer having terminal hydroxyl groups being described as the polymer. The copper baths according to DE-OS 15 21 062 can also contain other polyether polymers. With all of these additives you get more or less smooth, fine crystalline copper deposits, but they do not meet the increased requirements in practice for copper plating of printed circuit boards. In particular, the achievable values for elongation at break and shock test behavior are unsatisfactory. In addition, many prior art copper baths have the disadvantage that they have little scatterability, i.e. the concentration of copper and acid and the applicable current densities may only be varied within relatively narrow limits without deteriorating the quality of the copper coatings.
Die DE―A―1496767 beschreibt einen Ester aus Glycin und Butindiol zur Verwendung als Additiv zum Elektropolieren galvanischer Überzüge.DE ― A ― 1496767 describes an ester of glycine and butynediol for use as an additive for electropolishing galvanic coatings.
In Chemical Abstracts, Bd. 96, Nr. 24, No 200 379z, wird die Herstellung von Oxaalkinpolyolen aus 2-Butin-1,4 diol und Epichlorhydrin in einem organischen Lösungsmittel bei 30 bis 100°C mit anschließender Hydrolyse in 1 bis 20% Na2C03-Lösung beschrieben. Oxaalkinpolyole werden als Glanzbilder für galvanische Bäder verwendet.Chemical Abstracts, Vol. 96, No. 24, No 200 379z, describes the preparation of oxaalkyne polyols from 2-butyne-1,4-diol and epichlorohydrin in an organic solvent at 30 to 100 ° C with subsequent hydrolysis in 1 to 20% Na 2 CO 3 solution described. Oxaalkine polyols are used as gloss images for galvanic baths.
Die Erfindung hat sich daher die Aufgabe gestellt, ein saures galvanisches Kupferband zu entwickeln, das aüßer einem verbesserten Streuvermögen feinkristalline, duktile Kupferniederschläge liefert, mit hohen Bruchdehnungswerten und besserem Schocktestverhalten.The object of the invention is therefore to develop an acidic galvanic copper strip which, apart from an improved scattering capacity, provides fine crystalline, ductile copper deposits, with high elongation at break values and better shock test behavior.
Diese Aufgabe kann überraschenderweise gelöst werden durch ein saures galvanisches Kupferbad zur Abscheidung von feinkörnigem duktilem Kupfer mit einem Gehalt an Polymeren aus bifunktionellen Propanderivaten und gegebenenfalls anderen Badzusätzen, dadurch gekennzeichnet, daß es bifunktionelle Propanderivate der Formeln 1 und/oder II enthält, wobei X und Y eine Hydroxylgruppe oder Halogen bedeutet, X ungleich Y ist und Z Sauerstoff, Schwefel oder eine Methylengruppe ist,
Gegenstand der vorliegenden Erfindung ist ferner ein Verfahren zur Herstellung eines sauren galvanischen Kupferbades zur Abscheidung von feinkörnigem duktilem Kupfer mit einem Gehalt an Polymeren aus bifunktionellen Propanderivaten und gegebenenfalls anderen Badzusätzen, dadurch gekennzeichnet, daß man die bifunktionellen Propanderivate in Gegenwart von 1 bis 50 Mol-% eines oder mehrerer ungesättigter Alkohole mit 3 bis 10 Kohlenstoffatomen und einer oder mehrerer Doppel- und/oder Dreifachindung polymerisiert, das Polymerisat bei Temperaturen unterhalb von 100°C mit Wasser und gegebenenfalls geringen Mengen eines niederen Alkohols verdünnt und dann dem sauren Kupferbad zufügt.The present invention furthermore relates to a process for the preparation of an acidic galvanic copper bath for the deposition of fine-grained ductile copper containing polymers from bifunctional propane derivatives and, if appropriate, other bath additives, characterized in that the bifunctional propane derivatives are present in the presence of 1 to 50 mol%. polymerizes one or more unsaturated alcohols with 3 to 10 carbon atoms and one or more double and / or triple bonds, dilutes the polymer at temperatures below 100 ° C. with water and optionally small amounts of a lower alcohol and then adds it to the acidic copper bath.
Als bifunktionelle Propanderivate werden die oben genannten Substanzen der allgemeinen Formeln I und II eingesetzt
Typische Beispiele für diese Substanzen sind Monochlorhydrin, Epichlorhydrin und Glycid (Glycidol). Die Polymerisation der bifunktionellen Propanderivate kann in an sich bekannter Weise durch Zusatz von Katalysatoren wie Protonensäuren und Lewis-Säuren erfolgen. Besonders bewährt als Lewis-Säure hat sich Bortrifluorid-Etherat, jedoch sind auch andere Katalysatoren für die Herstellung der erfindungsgemäß verwendeten Polymerisate geeignet.Typical examples of these substances are monochlorohydrin, epichlorohydrin and glycid (glycidol). The bifunctional propane derivatives can be polymerized in a manner known per se by adding catalysts such as protonic acids and Lewis acids. Boron trifluoride etherate has proven particularly useful as Lewis acid, but other catalysts are also suitable for the preparation of the polymers used according to the invention.
Bei den erfindungsgemäß verwendeten Polymerisaten handelt es sich um Copolymerisate der bifunktionellen Propanderivate, an deren Endgruppen sich ungesättigte Alkohole befinden. Polymere des Glycides sich beispielsweise Polyether mit primären oder sekundären OH-Gruppen sowie endständigen Gruppen, die zu einem ungesättigten Alkohol gehören. Diese Polymeren sind in reiner Form viskos und können in heißem Wasser oder in heißem Wasser unter Zusatz niederer Alkohole gelöst werden. Sie werden in form derartiger wässriger oder wässrigalkoholischer Lösungen dem Kupferbad zugegeben. Gegebenenfalls wird vorher von Ungelöstem abfiltriert. Die Menge an erfindungsgemäßem Zusatz ist nich kritisch. Es hat sich gezeigt, daß Mengen von 0,1 bis 1 g Polymerisat pro Liter Kupferbad völlig ausreichen, den gewünschten Effekt zu erzielen. Sofern man die Lösungen des Polymerisats auf eine Konzentration von ca. 2,5 Gew.-% einstellt, genügen 4 bis 40 ml dieser Lösung pro Liter Kupferbad.The polymers used according to the invention are copolymers of the bifunctional propane derivatives, the end groups of which contain unsaturated alcohols. Polymers of glycides include poly ethers with primary or secondary OH groups as well as terminal groups belonging to an unsaturated alcohol. These polymers are viscous in their pure form and can be dissolved in hot water or in hot water with the addition of lower alcohols. They are added to the copper bath in the form of such aqueous or aqueous-alcoholic solutions. If necessary, the undissolved material is filtered off beforehand. The amount of additive according to the invention is not critical. It has been shown that amounts of 0.1 to 1 g of polymer per liter of copper bath are completely sufficient to achieve the desired effect. If the solutions of the polymer are adjusted to a concentration of approximately 2.5% by weight, 4 to 40 ml of this solution per liter of copper bath are sufficient.
Als weitere Zusätze kommen prinzipiell alle sonstigen üblichen Zusätze in Frage. Als vorteilhaft hat es sich erweisen, die Chlor- und/oder Bromionenkonzentration zwischen 10 und 20 mg pro Liter zu halten.In principle, all other customary additives can be considered as additional additives. It has proven to be advantageous to keep the chlorine and / or bromine ion concentration between 10 and 20 mg per liter.
Mit den erfindungsgemäßen Kupferbädern kann bei Stromdichten zwischen 0,5 und 10 Aldm2 gearbeitet werden. Bei der Verkupferung von Leiterbahnen zeigt sich, daß auch in den Bohrlöchern Schichtstärken erreicht werden, die über 90% der Dicke der sonst erzielten Schichtstärken betragen.The copper baths according to the invention can be used at current densities between 0.5 and 10 Aldm2. The copper plating of conductor tracks shows that layer thicknesses are also achieved in the boreholes which are over 90% of the thickness of the layer thicknesses otherwise achieved.
Unterwirft man mit dem erfindungsgemäßen Kupferbad hergstellte Leiterplatten mit Kupferüberzügen von 20 bis 30 um einem Temperaturschocktest, indem man in einem Ölbad auf 250°C erhitzt und anschließend wieder auf Raumtemperatur abkühlt, so werden auch nach 10 Zyklen noch keine Fehler und Kantenabrisse in der Kupferschicht beobachtet. Mit Hilfe des erfindungsgemäßen Kupferbades hergestellte Kupferfolien von 50 µm Stärke zeigen beim Test auf Bruchdehnung Meßwerte im Bereich von 6 bis 20%.If circuit boards produced with the copper bath according to the invention with copper coatings of 20 to 30 μm are subjected to a temperature shock test by heating to 250 ° C. in an oil bath and then cooling again to room temperature, no defects and edge breaks in the copper layer are observed even after 10 cycles . Copper foils of 50 μm thickness produced with the aid of the copper bath according to the invention show measured values in the range from 6 to 20% in the test for elongation at break.
Diese Bruchdehnungswerte werden auch nach langer Betriebsdauer des Elektrolyten erzielt und es bilden sich somit keine störenden Abbauprodukte im Elektrolyten, die zu einer verringerten Lebensdauer des Bades oder verminderter Qualität der Kupferüberzüge führen.These elongation at break values are achieved even after the electrolyte has been in operation for a long time, and therefore no disruptive degradation products are formed in the electrolyte, which lead to a reduced bath life or reduced copper coating quality.
Ein weiterer Vorteil der erfindungsgemäßen Kupferbäder besteht darin, daß man anstelle der üblichen Konzentration von 10 bis 20 g/I Kupfer und 100 bis 250 g/I Schwefelsäure jetzt auch bei Konzentrationen von 40 bis 80 g/I Kupfer und 30 bis 80 g/I Schwefelsäure arbeiten kann. Die erfindungsgemäßen Kupferbäder können in üblicher Weise durch Lufteinblasung bewegt werden. Die Badtemperatur beträgt im allgemeinen 15 bis 40°C.Another advantage of the copper baths according to the invention is that instead of the usual concentration of 10 to 20 g / l copper and 100 to 250 g / l sulfuric acid, now also at concentrations of 40 to 80 g / l copper and 30 to 80 g / l Sulfuric acid can work. The copper baths according to the invention can be moved in the usual way by blowing in air. The bath temperature is generally 15 to 40 ° C.
In den nachfolgenden Beispielen wird die Herstellung der Polymerisate und der erfindungsgemäßen Kupferbäder näher erläutert.The preparation of the polymers and the copper baths according to the invention is explained in more detail in the examples below.
Einer Mischung aus 9,2 g Epichlorhydrin und 2 g Butin-1,4-diol werden unter Rühren 0,1 ml einer 10-%igen Bortrifluorid-Etherat-Lösung vorsichtig tropfenweise zugegeben. Heftige Reaktion. Man läßt langsam abkühlen und verdünnt mit Methanol auf 500 ml und filtriert anschließend.0.1 ml of a 10% boron trifluoride etherate solution is carefully added dropwise to a mixture of 9.2 g epichlorohydrin and 2 g butyne-1,4-diol with stirring. Violent reaction. The mixture is allowed to cool slowly and diluted to 500 ml with methanol and then filtered.
In 11 g Monochlorhydrin werden 5 g 3-Methyl-1-pentin-3-ol eingerührt, dazu werden langsam 0,5 ml 10-%iges Bortrifluorid-Etherat gegeben. Es wird zusätzlich erhitzt, bis eine Temperatur von 200°C erreicht ist. Danach läßt man abkühlen und verdünnt mit Methanol auf 100 ml.5 g of 3-methyl-1-pentin-3-ol are stirred into 11 g of monochlorohydrin, to which 0.5 ml of 10% boron trifluoride etherate is slowly added. It is additionally heated until a temperature of 200 ° C is reached. Then allowed to cool and diluted to 100 ml with methanol.
In 25 g Glycidol werden 2 g Hexin-3-diol-2,5 eingerührt. Zu der Mischung werden langsam tropfenweise 0,5 ml 10-%iges Bortrifluorid-Etherat-Lösung zugegeben. Es stellt sich eine Temperatur von 225°C ein. Die Lösung wird nach langsamer Abkühlung auf unter 100°C mit Wasser dest. auf 200 ml verdünnt und filtriert.2 g of hexin-3-diol-2.5 are stirred into 25 g of glycidol. 0.5 ml of 10% boron trifluoride etherate solution is slowly added dropwise to the mixture. A temperature of 225 ° C is reached. After slow cooling to below 100 ° C., the solution is distilled with water. diluted to 200 ml and filtered.
9,2 g Epichlorhydrin werden mit 1 g Hexin-3- diol-2,5 vermischt und mit 0,1 ml 10-%ige Bortrifluoridlösung vorsichtig versetzt. Nach einer exothermen Reaktion von über 100°C läßt man abkühlen und verdünnt mit Methanol auf 500 ml und filtriert anschließend.9.2 g epichlorohydrin are mixed with 1 g hexin-3-diol-2.5 and carefully mixed with 0.1 ml 10% boron trifluoride solution. After an exothermic reaction of above 100 ° C., the mixture is allowed to cool and diluted to 500 ml with methanol and then filtered.
In 25 g Glycidol werden 5 g 2,4,7,9 Tetramethyl-5-decin-4,7-diol eingerührt, dazu werden langsam 0,5 ml 10-%iges Bortrifluorid-Etherat gegeben. Es stellt sich eine Endtemperatur von ca. 215°C ein. Danach läßt man auf unter 100°C abkühlen und verdünnt mit Wasser dest. auf 500 ml. Anschließend wird filtriert. Die Umsetzung ist in Wasser nicht klar löslich und wird mit 500 ml Isopropanol auf 1000 ml Endvolumen aufgefüllt.5 g of 2,4,7,9 tetramethyl-5-decyne-4,7-diol are stirred into 25 g of glycidol, and 0.5 ml of 10% boron trifluoride etherate are slowly added. A final temperature of approx. 215 ° C is reached. Then allowed to cool to below 100 ° C and diluted with distilled water. to 500 ml. The mixture is then filtered. The reaction is not clearly soluble in water and is made up to 1000 ml final volume with 500 ml isopropanol.
Es wird ein Kupferbad folgender Zusammensetzung hergestellt:
- Zusatz von
- Polymerisat gemäß
- Beispielen 1 bis 4 2-5 ml/I.
- Addition of
- Polymer according to
- Examples 1 to 4 2-5 ml / l.
In diesen Bädern wird bei Temperaturen von 18 bis 30°C gearbeitet.These baths work at temperatures from 18 to 30 ° C.
Bei kathodischen Stromdichten von 0,5-4 A/ dm2 werden aus diesem Elektrolyten feinkristalline, duktile Kupferüberzüge mit ausgezeichnetem Streuvermögen abgeschieden. Verkupfert man in den erfindungsgemäßen Elektrolyten eine Leiterplatte mit einer Materialstärke von 3 mm und einem Bohrungsdurchmesser von 0,3 mm, so erzielt man bei kathodischen Stromdichten von 0,5-1,0 Aldm2 in den Bohrungen Schichtstärken von über 90% bezogen auf die Leiterbahn.At cathodic current densities of 0.5-4 A / dm 2 , finely crystalline, ductile copper coatings with excellent scattering capacity are deposited from this electrolyte. If a circuit board with a material thickness of 3 mm and a bore diameter of 0.3 mm is copper-plated in the electrolytes according to the invention, cathodic current densities of 0.5-1.0 Aldm 2 in the holes layer thicknesses of over 90% based on the conductor track.
Unterwirft man die in obigen Elektrolyten auf Leiterplatten abgeschiedenen Kupferüberzüge (20-30 um) einem Temperaturschocktest (d.h. das Material wird in einem Ölbad auf 250°C erhitzt und anschließend wieder auf Raumtemperatur abgekühlt), so treten nach 10 Zylken noch keinerlei Fehler (Kantenabrisse) in der Kupferschicht auf.If the copper coatings (20-30 µm) deposited in the above electrolytes on printed circuit boards are subjected to a temperature shock test (ie the material is heated in an oil bath to 250 ° C and then cooled back to room temperature), no defects will occur after 10 cycles (edge breaks) in the copper layer.
Ermittelt man an in dem erfindungsgemäßen Elektrolyten hergestellten Kupferfolien (50 um) die Bruchdehnung, so erzielt man Meßwerte, die im Berreich von 6-20% liegen. Wesentlich ist dabei, daß die Bruchdehnungswerte auch nach langer Betriebsdauer des Elektrolyten konstant bleiben, also keine störenden Abbauprodukte gebildet werden.If the elongation at break is determined on copper foils (50 .mu.m) produced in the electrolyte according to the invention, measurement values in the range of 6-20% are obtained. It is essential that the elongation at break values remain constant even after a long period of operation of the electrolyte, that is to say that no disruptive degradation products are formed.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3335079 | 1983-09-28 | ||
| DE3335079 | 1983-09-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0137397A2 EP0137397A2 (en) | 1985-04-17 |
| EP0137397A3 EP0137397A3 (en) | 1988-02-17 |
| EP0137397B1 true EP0137397B1 (en) | 1990-08-29 |
Family
ID=6210272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84111402A Expired - Lifetime EP0137397B1 (en) | 1983-09-28 | 1984-09-25 | Acid galvanic copper bath and process for its preparation |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0137397B1 (en) |
| DE (1) | DE3483078D1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4338148C2 (en) * | 1993-11-04 | 1997-01-30 | Atotech Deutschland Gmbh | Process for the electrolytic deposition of dull and pimple-free copper layers with high elongation at break on substrate surfaces |
| CA2331750A1 (en) | 1998-05-16 | 1999-11-25 | Blasberg Oberflachentechnik Gmbh | Method for electro copperplating substrates |
| AU2002215939A1 (en) * | 2000-10-19 | 2002-04-29 | Atotech Deutschland Gmbh | Copper bath and method of depositing a matt copper coating |
| DE10058896C1 (en) * | 2000-10-19 | 2002-06-13 | Atotech Deutschland Gmbh | Electrolytic copper bath, its use and method for depositing a matt copper layer |
-
1984
- 1984-09-25 DE DE8484111402T patent/DE3483078D1/en not_active Expired - Fee Related
- 1984-09-25 EP EP84111402A patent/EP0137397B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0137397A2 (en) | 1985-04-17 |
| EP0137397A3 (en) | 1988-02-17 |
| DE3483078D1 (en) | 1990-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0010164B1 (en) | Process for the preparation of modified polycarbonate moulded articles | |
| DE3020017C2 (en) | Fluorinated carboxylic acids or their derivatives and processes for their preparation | |
| EP0129698B1 (en) | Process for the preparation of polypyrroles, and film-like products obtained by such a process | |
| DE69935623T2 (en) | Curable resin composition | |
| EP2130948B1 (en) | Pyrophosphate-containing bath for cyanide-free electroplating of copper- tin alloys | |
| EP0099965B1 (en) | Process for preparing high molecular weight polyphenylene oxides | |
| DE2744783A1 (en) | PRIMER AND ITS USE | |
| EP0147708B1 (en) | Polyaryl ethers containing branched, high molecular weight thermoplastic nitrile groups, and their preparation | |
| EP0087038A1 (en) | Use of lightly coloured polyphenylene sulphides in mixtures with thermoplastic polycarbonates and/or thermoplastic polyesters | |
| EP0355654A2 (en) | Cathodically depositable paint binders and method for their manufacture | |
| DE2448168C3 (en) | Curable epoxy resin composition and method for its preparation | |
| DE2463036C2 (en) | ||
| DE2511587C3 (en) | Process for the production of paints | |
| DE69016322T2 (en) | Process for the electrostatic coating of a molded plastic part. | |
| EP0234223A2 (en) | Method for the preparation of aromatic block copolyethers | |
| EP0137397B1 (en) | Acid galvanic copper bath and process for its preparation | |
| AT391475B (en) | METHOD FOR PRODUCING PIGMENT PASTE RESIN FOR CATHODICALLY DEPOSITABLE COATING COMPOSITIONS | |
| DE69120006T2 (en) | Epoxy resin film and process for its production | |
| DE3417433C2 (en) | ||
| DE4032864C2 (en) | ||
| EP0135760A1 (en) | Polyether-polycarbonates for dialysis-membranes | |
| DE1291834B (en) | Process for the electrochemical roughening of heavy metal bodies for their use as electrodes in electrolytic capacitors | |
| DE69016337T2 (en) | Process for improving the electrical conductivity of a plastic object. | |
| DE69016323T2 (en) | Process for improving the electrical conductivity of synthetic resin molds. | |
| DE2948999C2 (en) | Aqueous, acidic bath for the electrodeposition of gold and method for the electrodeposition of hard gold with its use |
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 |
|
| AK | Designated contracting states |
Designated state(s): BE DE FR GB LU NL SE |
|
| RTI1 | Title (correction) | ||
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB LU NL SE |
|
| 17P | Request for examination filed |
Effective date: 19880802 |
|
| 17Q | First examination report despatched |
Effective date: 19890828 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB LU NL SE |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| REF | Corresponds to: |
Ref document number: 3483078 Country of ref document: DE Date of ref document: 19901004 |
|
| ET | Fr: translation filed | ||
| 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 |
|
| 26N | No opposition filed | ||
| EPTA | Lu: last paid annual fee | ||
| EAL | Se: european patent in force in sweden |
Ref document number: 84111402.8 |
|
| 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: GB Payment date: 20020902 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: 20020916 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20020920 Year of fee payment: 19 Ref country code: BE Payment date: 20020920 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20020923 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20021015 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20030917 Year of fee payment: 20 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030925 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030925 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030926 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030930 |
|
| BERE | Be: lapsed |
Owner name: *BLASBERG-OBERFLACHENTECHNIK G.M.B.H. Effective date: 20030930 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20040401 |
|
| EUG | Se: european patent has lapsed | ||
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20030925 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040528 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20040925 |
|
| NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20040925 |