EP0312176A1 - Process for applying conversion coatings - Google Patents

Process for applying conversion coatings Download PDF

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Publication number
EP0312176A1
EP0312176A1 EP88202291A EP88202291A EP0312176A1 EP 0312176 A1 EP0312176 A1 EP 0312176A1 EP 88202291 A EP88202291 A EP 88202291A EP 88202291 A EP88202291 A EP 88202291A EP 0312176 A1 EP0312176 A1 EP 0312176A1
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EP
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Prior art keywords
tin
solution
metal surfaces
phosphate
treatment
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Granted
Application number
EP88202291A
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German (de)
French (fr)
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EP0312176B1 (en
Inventor
Yasunobu Matsushima
Shigeo Tanaka
Tomoyuki Aoki
Yohiji Ono
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/23—Condensed phosphates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising

Definitions

  • the invention relates to a method for applying conversion coatings on metal surfaces with the aid of aqueous solutions containing phosphate, tin and accelerator.
  • metal surfaces e.g. made of iron or steel, galvanized steel or tinplate
  • metal surfaces e.g. made of iron or steel, galvanized steel or tinplate
  • the pH of these solutions is said to be in the range from 3 to 6 (GB-A-2 068 418).
  • a conversion coating with very good corrosion protection is achieved.
  • a disadvantage of using these known solutions is that when the treatment systems are at a standstill, the tin content in the solution drops, so that conversion coatings of inferior quality are produced when the system is restarted, unless an additional addition of tin to the treatment solution is carried out beforehand.
  • the object of the invention is to provide a method for applying conversion coatings on metal surfaces which does not have the disadvantages of the known methods, in particular also leads to conversion coatings with excellent corrosion resistance in the treatment of tinplate with small tin deposits and a decrease in the tin concentration in the treatment solution in the treatment solution Excludes downtime of treatment plants.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a solution which, in addition to 1 to 50 g / l phosphate (calculated as PO4) 0.01 to 5 g / l tin 0.2 to 20 g / l accelerator additionally contains complexing agents in an amount of 0.01 to 5 g / l and has a pH of 2 to 6.
  • a solution which, in addition to 1 to 50 g / l phosphate (calculated as PO4) 0.01 to 5 g / l tin 0.2 to 20 g / l accelerator additionally contains complexing agents in an amount of 0.01 to 5 g / l and has a pH of 2 to 6.
  • the complexing agent content suppresses the tin precipitation from the treatment solution, but at the same time its deposition on the workpiece surface is not prevented when the conversion coating is formed.
  • the complexing agent also accelerates the pickling attack on the metal surface and is responsible for a balance between the tin which dissolves (as a result of the pickling attack) and the tin which deposits as a coating component.
  • fluctuations in the tin concentration in the treatment solution largely become avoided, which ultimately has a favorable effect on the quality, in particular the high corrosion resistance of the conversion coating.
  • the phosphate can be introduced as an alkali phosphate, such as sodium, potassium or ammonium monohydrogen phosphate or dihydrogen phosphate. It can also be formed from phosphoric acid and sodium, potassium or ammonium hydroxide. Solutions with phosphate concentrations outside the range of 1 to 50 g / l are unable to produce conversion coatings with the desired excellent properties. Concentrations within the range of 2 to 25 g / l lead to particularly high-quality conversion coatings.
  • the metal surfaces are brought into contact with a solution which contains oxo acids, in particular chlorate and / or bromate, as accelerators.
  • oxo acids in particular chlorate and / or bromate
  • nitrite and hydroxylamine salts are also suitable.
  • the chlorides and / or sulfates of divalent or tetravalent tin can be used in particular as the source of tin ions.
  • Sodium stannate is also suitable.
  • the range from 0.01 to 5 g / l applies to tin II or tin IV ions, or to the sum of tin II and tin IV ions.
  • Concentrations below 0.01 g / l reduce the corrosion resistance of the conversion coatings produced.
  • concentrations above 5 g / l there is a risk that the treatment solution will become unstable. An additional improvement in the coating quality is also not achieved.
  • Specific examples of this are sodium, potassium or ammonium pyrophosphate, tripolyphosphate or tetrapolyphosphate.
  • phosphoric acid hydrochloric acid, sulfuric acid or sodium, potassium or ammonium hydroxide are expediently used.
  • the pH range to be set from 2 to 6 is important insofar as the corrosion resistance of the conversion coating formed becomes low at a pH value below 2 and the tendency at a pH value above 6 that tin ions precipitate out of the solution and therefore proper coating formation is no longer guaranteed.
  • the conversion coating is produced in two stages, first chemically, then electrochemically. This will increase the corrosion resistance again achieved.
  • Tin-II or tin-IV and phosphate are the essential constituents forming the conversion coating.
  • the layer formation begins with the pickling attack of the acidic solution on the metal surface. It is intensified by the action of the accelerators, especially the oxo acids.
  • the complexing agent controls the tin deposition by forming a chelate complex with tin, which would otherwise easily precipitate out of the treatment solution, and provides the tin ions required for coating formation in a controlled manner.
  • Another role for the complexing agent is to bind the metal ions released from the metal surface by the pickling attack and to make them available again in a controlled manner for coating formation.
  • the complexing agent is responsible for uniform coating formation by influencing the pickling attack.
  • the coatings also have excellent properties as the basis for subsequent painting, printing and the like in terms of corrosion resistance, adhesion and gloss.
  • the treatment solution experiences practically no reduction in the tin content even after long downtimes, so that the process can then be resumed immediately and perfect conversion coatings are immediately obtained.
  • Cans made from tinplate were cleaned in a mildly alkaline cleaner with a concentration of 1% by weight in water. The coating was then sprayed for 20 seconds using the solutions listed below. After a water rinse, deionized water of a quality of at least 300,000 ohm ⁇ cm was sprayed for a period of 10 seconds and then dried in a hot air oven at 200 ° C. within 3 minutes. The conversion coating was applied in each case with a freshly prepared coating solution and one which had stood for a day for 10 cans per liter of solution.
  • H3PO4 (75% by weight) 15 g / l (PO4 11 g / l) NaClO3 6 g / l SnCl4 ⁇ 5H2O 0.6 g / l (Sn 0.2 g / l) Na4P2O7 ⁇ 10H2O 1.5 g / l (P2O7 0.6 g / l) pH 3.1 adjusted with sodium hydroxide solution
  • Tinplate cans were treated according to the procedure described in Example 1 with the following solution: H3PO4 (75% by weight) 2.8 g / l (PO4 2 g / l) NaClO3 0.3 g / l SnCl2 ⁇ 2H2O 0.04 g / l (Sn 0.02 g / l) Na4P2O7 ⁇ 10H2O 0.05 g / l (P2O7 0.02 g / l) pH 5.7 adjusted with sodium hydroxide solution Treatment temperature 70 ° C
  • tinplate cans were treated with the following solution: H3PO4 (75% by weight) 55 g / l (PO4 40 g / l) NaBrO3 17 g / l SnCl4 ⁇ 5H2O 13.2 g / l (Sn 4.5 g / l) Na5P3O10 6.5 g / l (P3O10 4.5 g / l) pH 2.2 adjusted with sodium hydroxide solution Treatment temperature 60 ° C
  • tinplate cans were treated with the following solution: H3PO4 (75% by weight) 15 g / l (PO4 11 g / l) NaClO3 6 g / l SnCl4 ⁇ 5H2O 0.6 g / l (Sn 0.2 g / l) Na4P2O7 ⁇ 10H2O 21 g / l (P2O7 8 g / l) pH 3.1 adjusted with sodium hydroxide solution Treatment temperature 60 ° C
  • the tin content was determined after the batch and after standing for one day.
  • the tinplate cans provided with conversion coatings were subjected to the corrosion test and the paint adhesion test.
  • the treated cans were immersed in tap water at 60 ° C. for 30 minutes and the rust development was assessed.
  • an epoxy / urea paint with a thickness of 5 to 7 ⁇ m was applied to the cans provided with the conversion coatings and baked at 210 ° C. (duration 10 min). After standing for 24 hours, the cans were immersed in a 1% by weight aqueous citric acid solution at 95 to 97 ° C and left therein for 60 minutes. It was then rinsed with water and dried.
  • the samples were provided with a cross cut reaching to the metal surface and then with cellophane adhesive tape by pressing firmly. After the adhesive tape was torn off, it was found that the paint adhesion was consistently excellent, i.e. no paint detachment was found.

Abstract

In a process for applying conversion coatings of outstanding corrosion resistance to metal surfaces, solutions are used which, in addition to 1 to 50 g/l of phosphate (calculated as PO4> 0.01 to 5 g/l of tin 0.2 to 20 g/l of accelerator, additionally contain complexing agents in a quantity from 0.01 to 5 g/l and show a pH from 2 to 6. The complexing agents used are preferably condensed phosphates, in particular polyphosphates, and the accelerators used are preferably chlorate or bromate. The formation of the conversion coating can be effected electrochemically or in two stages, first chemically and then electrochemically.

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen von Konversionsüberzügen auf Metalloberflächen mit Hilfe von Phosphat, Zinn und Beschleuniger enthaltenden wäßrigen Lösungen.The invention relates to a method for applying conversion coatings on metal surfaces with the aid of aqueous solutions containing phosphate, tin and accelerator.

Als Beispiel für die Behandlung mittels chromfreier Lösung ist es bekannt, Metalloberflächen, z.B. aus Eisen oder Stahl, verzinktem Stahl oder Weißblech, mit Lösungen in Kontakt zu bringen, die 1 bis 50 g/l Alkaliphosphat (ber. als PO₄-Ion), 0,2 bis 20 g/l Chlorat und/oder Bromat und 0,01 bis 0,5 g/l Zinnionen enthalten und ein Gewichtsverhältnis von Chlorat zu Zinn von 0,6 bis 6 aufweist. Der pH-Wert dieser Lösungen soll im Bereich von 3 bis 6 liegen (GB-A-2 068 418). Insbesondere bei der Behandlung von aus Weißblech gefertigten Dosen wird dabei ein Konversionsüberzug mit sehr gutem Korrosionsschutz erzielt.As an example of treatment using a chrome-free solution, it is known to metal surfaces, e.g. made of iron or steel, galvanized steel or tinplate, in contact with solutions containing 1 to 50 g / l alkali phosphate (calculated as PO₄ ion), 0.2 to 20 g / l chlorate and / or bromate and 0, 01 to 0.5 g / l of tin ions and has a weight ratio of chlorate to tin of 0.6 to 6. The pH of these solutions is said to be in the range from 3 to 6 (GB-A-2 068 418). In particular when treating cans made of tinplate, a conversion coating with very good corrosion protection is achieved.

Nachteilig bei Anwendung dieser bekannten Lösungen ist, daß bei Stillstand der Behandlungsanlagen der Zinngehalt in der Lösung absinkt, so daß bei erneuter Inbetriebnahme Konversionsüberzüge mit minderer Qualität entstehen, es sei denn, es erfolgt zuvor eine zusätzliche Ergänzung von Zinn in der Behandlungslösung.A disadvantage of using these known solutions is that when the treatment systems are at a standstill, the tin content in the solution drops, so that conversion coatings of inferior quality are produced when the system is restarted, unless an additional addition of tin to the treatment solution is carried out beforehand.

Bei dem in den letzten Jahren bestehenden Trend, Weißblech mit geringerer Zinnauflage herzustellen, kommt erschwerend hinzu, daß die bekannten Behandlungsverfahren die gestellten Anforderungen an den Korrosionsschutz der erzeugten Konversionsüberzüge nicht mehr erfüllen.With the trend in recent years to produce tinplate with a smaller tin coating, it is made more difficult that the known treatment processes no longer meet the requirements placed on the corrosion protection of the conversion coatings produced.

Aufgabe der Erfindung ist es, ein Verfahren zum Aufbringen von Konversionsüberzügen auf Metalloberflächen bereitzustellen, das die Nachteile der bekannten Verfahren nicht besitzt, insbesondere auch bei der Behandlung von Weißblech mit geringen Zinnauflagen zu Konversionsüberzügen mit hervorragendem Korrosionswiderstand führt und ein Absinken der Zinnkonzentration in der Behandlungslösung beim Stillstand von Behandlungsanlagen ausschließt.The object of the invention is to provide a method for applying conversion coatings on metal surfaces which does not have the disadvantages of the known methods, in particular also leads to conversion coatings with excellent corrosion resistance in the treatment of tinplate with small tin deposits and a decrease in the tin concentration in the treatment solution in the treatment solution Excludes downtime of treatment plants.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die neben

1 bis 50 g/l Phosphat (ber. als PO₄)
0,01 bis 5 g/l Zinn
0,2 bis 20 g/l Beschleuniger

zusätzlich Komplexbildner in einer Menge von 0,01 bis 5 g/l enthält und einen pH-Wert von 2 bis 6 aufweist.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a solution which, in addition to

1 to 50 g / l phosphate (calculated as PO₄)
0.01 to 5 g / l tin
0.2 to 20 g / l accelerator

additionally contains complexing agents in an amount of 0.01 to 5 g / l and has a pH of 2 to 6.

Bei der Konzeption der vorliegenden Erfindung wurde festgestellt, daß durch den Komplexbildnergehalt die Zinnausfällung aus der Behandlungslösung unterdrückt, gleichzeitig aber dessen Abscheidung auf der Werkstückoberfläche bei der Ausbildung des Konversionsüberzuges nicht unterbunden wird. Der Komplexbildner beschleunigt darüber hinaus den Beizangriff auf die Metalloberfläche und ist für ein Gleichgewicht zwischen sich lösendem Zinn (infolge des Beizangriffes) und sich als Überzugsbestandteil abscheidenden Zinnes verantwortlich. Dadurch werden Schwankungen hinsichtlich der Zinnkonzentration in der Behandlungslösung weitgehend vermieden, was sich letztlich auf die Qualität, insbesondere den hohen Korrosionswiderstand des Konversionsüberzuges günstig auswirkt.In the design of the present invention, it was found that the complexing agent content suppresses the tin precipitation from the treatment solution, but at the same time its deposition on the workpiece surface is not prevented when the conversion coating is formed. The complexing agent also accelerates the pickling attack on the metal surface and is responsible for a balance between the tin which dissolves (as a result of the pickling attack) and the tin which deposits as a coating component. As a result, fluctuations in the tin concentration in the treatment solution largely become avoided, which ultimately has a favorable effect on the quality, in particular the high corrosion resistance of the conversion coating.

Das Phosphat kann als Alkaliphosphat, wie Natrium-, Kalium- oder Ammoniummonohydrogenphosphat oder -dihydrogenphosphat, eingebracht werden. Auch kann es aus Phosphorsäure und Natrium-, Kalium- oder Ammoniumhydroxid gebildet werden. Lösungen mit Phosphatkonzentrationen außerhalb des Bereiches von 1 bis 50 g/l sind nicht in der Lage, Konversionsüberzüge mit den erwünschten hervorragenden Eigenschaften zu erzeugen. Konzentrationen innerhalb des Bereiches von 2 bis 25 g/l führen zu besonders hochwertigen Konversionsüberzügen.The phosphate can be introduced as an alkali phosphate, such as sodium, potassium or ammonium monohydrogen phosphate or dihydrogen phosphate. It can also be formed from phosphoric acid and sodium, potassium or ammonium hydroxide. Solutions with phosphate concentrations outside the range of 1 to 50 g / l are unable to produce conversion coatings with the desired excellent properties. Concentrations within the range of 2 to 25 g / l lead to particularly high-quality conversion coatings.

Bei Beschleunigerkonzentrationen unter 0,2 g/l ist die Beschleunigungswirkung bezüglich der Ausbildung des Konversionsüberzuges unzureichend. Bei Konzentrationen über 20 g/l wird kein zusätzlicher Effekt erzielt, so daß wegen der Badüberwachung und auch bereits aus wirtschaftlichen Erwägungen heraus höhere Konzentrationen nicht sinnvoll sind.At accelerator concentrations below 0.2 g / l, the acceleration effect with regard to the formation of the conversion coating is insufficient. At concentrations above 20 g / l, no additional effect is achieved, so that higher concentrations are not sensible because of the bath monitoring and also for economic reasons.

Gemäß einer bevorzugten Ausgestaltung der Erfindung bringt man die Metalloberflächen mit einer Lösung in Kontakt, die als Beschleuniger Oxosäuren, insbesondere Chlorat und/oder Bromat, enthält. Es sind jedoch auch Nitrit und Hydroxylaminsalze geeignet.According to a preferred embodiment of the invention, the metal surfaces are brought into contact with a solution which contains oxo acids, in particular chlorate and / or bromate, as accelerators. However, nitrite and hydroxylamine salts are also suitable.

Als Quelle für Zinnionen können insbesondere die Chloride und/oder Sulfate zwei- oder vierwertigen Zinns eingesetzt werden. Auch ist Natriumstannat geeignet. Der Bereich von 0,01 bis 5 g/l gilt für Zinn-II- bzw. Zinn-IV-Ionen, oder aber für die Summe von Zinn-II- und Zinn-IV-Ionen. Bei Konzentrationen unter 0,01 g/l läßt der Korrosionswiderstand der erzeugten Konversionsüberzüge nach. Bei Konzentrationen über 5 g/l besteht die Gefahr, daß die Behandlungslösung instabil wird. Eine zusätzliche Verbesserung der Überzugsqualität wird zudem nicht erreicht.The chlorides and / or sulfates of divalent or tetravalent tin can be used in particular as the source of tin ions. Sodium stannate is also suitable. The range from 0.01 to 5 g / l applies to tin II or tin IV ions, or to the sum of tin II and tin IV ions. At Concentrations below 0.01 g / l reduce the corrosion resistance of the conversion coatings produced. At concentrations above 5 g / l there is a risk that the treatment solution will become unstable. An additional improvement in the coating quality is also not achieved.

Eine weitere bevorzugte Ausgestaltung der Erfindung besteht darin, die Metalloberflächen mit einer Lösung in Kontakt zu bringen, die als Komplexbildner kondensierte Phosphate, insbesondere Polyphosphate der allgemeinen Formel PnO3n+1 mit n = 2, 3 oder 4 enthält. Konkrete Beispiele hierfür sind Natrium-, Kalium- oder Ammoniumpyrophosphat, -tripolyphosphat oder -tetrapolyphosphat. Bei Konzentrationen unter 0,01 g/l ist die komplexbildende Wirkung der kondensierten Phosphate nicht mehr genügend ausgeprägt, d.h. die Fähigkeit, die Zinnausfällung zu verhindern, schwindet. Mit Konzentrationen über 5 g/l kann insbesondere ein zu starker Beizangriff an der Metalloberfläche verbunden sein, auch kann die Abscheidung des Zinns im Konversionsüberzug behindert werden. Anstelle der kondensierten Phosphate sind auch organische Säuren, wie Phosphonsäure, Weinsäure, Ascorbinsäure, Zitronensäure und Gluconsäure als Komplexbildner geeignet.A further preferred embodiment of the invention consists in bringing the metal surfaces into contact with a solution which contains phosphates condensed as complexing agents, in particular polyphosphates of the general formula P n O 3n + 1 with n = 2, 3 or 4. Specific examples of this are sodium, potassium or ammonium pyrophosphate, tripolyphosphate or tetrapolyphosphate. At concentrations below 0.01 g / l, the complex-forming effect of the condensed phosphates is no longer sufficiently pronounced, ie the ability to prevent the tin precipitation decreases. Concentrations above 5 g / l can in particular be associated with excessive pickling attack on the metal surface, and the deposition of the tin in the conversion coating can also be hindered. Instead of the condensed phosphates, organic acids such as phosphonic acid, tartaric acid, ascorbic acid, citric acid and gluconic acid are also suitable as complexing agents.

Zur Einstellung des pH-Wertes wird zweckmäßigerweise Phosphorsäure, Salzsäure, Schwefelsäure oder aber Natrium-, Kalium- oder Ammoniumhydroxid verwendet. Der einzustellende pH-Bereich von 2 bis 6 ist insofern von Bedeutung, als bei einem pH-Wert unter 2 der Korrosionswiderstand des gebildeten Konversionsüberzuges gering wird und bei einem pH-Wert oberhalb 6 die Tendenz besteht, daß Zinnionen aus der Lösung ausfallen und mithin eine ordnungsgemäße Überzugsbildung nicht mehr gewährleistet ist.To adjust the pH, phosphoric acid, hydrochloric acid, sulfuric acid or sodium, potassium or ammonium hydroxide are expediently used. The pH range to be set from 2 to 6 is important insofar as the corrosion resistance of the conversion coating formed becomes low at a pH value below 2 and the tendency at a pH value above 6 that tin ions precipitate out of the solution and therefore proper coating formation is no longer guaranteed.

Die Ausbildung des Konversionsüberzuges erfolgt üblicherweise nach dem Verfahrensschema

  • 1. Reinigung mit einem mildalkalischen Reiniger
  • 2. Wasserspülen
  • 3. Behandlung zur Ausbildung des Konversionsüberzuges bei Temperaturen von Raumtemperatur bis 90°C, zwecks Beschleunigung der Schichtausbildung zweckmäßigerweise bei 50 bis 60°C, im Tauchen oder Spritzen für die Dauer von 10 bis 120 sec
  • 4. Wasserspülen
  • 5. Trocknen.
Entsprechend einer vorteilhaften Ausführungsform der Erfindung, die mit einer Verkürzung der Behandlungsdauer verbunden ist, erfolgt die Ausbildung des Konversionsüberzuges auf elektrochemischem Wege. Diese Ausführungsform ist insbesondere für die Behandlung von Bandmaterial aus Weißblech von Vorteil. Außerdem ist der Korrosionswiderstand des gebildeten Konversionsüberzuges besonders hoch. Hierzu wird das Weißblech als Anode gegen Graphit, Edelstahl und dergleichen als Kathode geschaltet, ein Elektrodenabstand von etwa 10 bis 500 mm sowie eine Stromdichte von ca. 0,1 A/dm² für die Dauer von 0,5 bis 60 sec eingestellt. Es kann Gleich- oder Wechselstrom verwendet werden.The conversion coating is usually designed according to the process scheme
  • 1. Cleaning with a mildly alkaline cleaner
  • 2. Rinse water
  • 3. Treatment to form the conversion coating at temperatures from room temperature to 90 ° C, for the purpose of accelerating the layer formation, expediently at 50 to 60 ° C, in immersion or spraying for a period of 10 to 120 seconds
  • 4. Rinse water
  • 5. Drying.
According to an advantageous embodiment of the invention, which is associated with a reduction in the duration of treatment, the conversion coating is formed electrochemically. This embodiment is particularly advantageous for the treatment of strip material made of tinplate. In addition, the corrosion resistance of the conversion coating formed is particularly high. For this purpose, the tinplate is switched as the anode against graphite, stainless steel and the like as the cathode, an electrode spacing of approximately 10 to 500 mm and a current density of approximately 0.1 A / dm 2 are set for a period of 0.5 to 60 seconds. Direct or alternating current can be used.

Gemäß einer besonders vorteilhaften Ausgestaltung der Erfindung wird der Konversionsüberzug in zwei Stufen, zunächst chemisch, dann elektrochemisch erzeugt. Hierdurch wird eine nochmalige Steigerung des Korrosionswiderstandes erzielt. Zinn-II bzw. Zinn-IV und Phosphat sind die wesentlichen, den Konversionsüberzug bildenden Bestandteile. Die Schichtausbildung beginnt mit dem Beizangriff der sauren Lösung auf die Metalloberfläche. Sie wird durch die Wirkung der Beschleuniger, insbesondere der Oxosäuren, intensiviert. Der Komplexbildner kontrolliert die Zinnabscheidung durch Ausbildung eines Chelatkomplexes mit Zinn, welches anderenfalls leicht aus der Behandlungslösung ausfallen würde, und stellt die zur Überzugsausbildung jeweils erforderlichen Zinnionen in kontrollierter Weise zur Verfügung. Eine andere, dem Komplexbildner zukommende Rolle besteht darin, die durch den Beizangriff aus der Metalloberfläche herausgelösten Metallionen zu binden und in kontrollierter Weise wieder zur Überzugsausbildung zur Verfügung zu stellen. Schließlich ist der Komplexbildner für eine gleichmäßige Überzugsausbildung verantwortlich, indem er auf den Beizangriff Einfluß nimmt.According to a particularly advantageous embodiment of the invention, the conversion coating is produced in two stages, first chemically, then electrochemically. This will increase the corrosion resistance again achieved. Tin-II or tin-IV and phosphate are the essential constituents forming the conversion coating. The layer formation begins with the pickling attack of the acidic solution on the metal surface. It is intensified by the action of the accelerators, especially the oxo acids. The complexing agent controls the tin deposition by forming a chelate complex with tin, which would otherwise easily precipitate out of the treatment solution, and provides the tin ions required for coating formation in a controlled manner. Another role for the complexing agent is to bind the metal ions released from the metal surface by the pickling attack and to make them available again in a controlled manner for coating formation. Finally, the complexing agent is responsible for uniform coating formation by influencing the pickling attack.

Wenn sämtliche verfahrenswesentlichen Parameter eingehalten werden, ist die Entstehung hochwertiger, insbesondere hochkorrosionsfester Konversionsüberzüge gewährleistet. Die Überzüge besitzen ferner hervorragende Eigenschaften als Basis für eine anschließende Lackierung, Bedruckung und dergleichen hinsichtlich Korrosionswiderstand, Haftung und Glanz.If all process-essential parameters are observed, the creation of high-quality, especially highly corrosion-resistant conversion coatings is guaranteed. The coatings also have excellent properties as the basis for subsequent painting, printing and the like in terms of corrosion resistance, adhesion and gloss.

Die Behandlungslösung erfährt selbst nach langen Stillstandzeiten praktisch keine Verringerung des Zinngehaltes, so daß das Verfahren danach unverzüglich wiederaufgenommen werden kann und sogleich einwandfreie Konversionsüberzüge erhalten werden.The treatment solution experiences practically no reduction in the tin content even after long downtimes, so that the process can then be resumed immediately and perfect conversion coatings are immediately obtained.

Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.

Beispiel 1example 1

Aus Weißblech gefertigte Dosen wurden in einem mildalkalischen Reiniger einer Konzentration von 1 Gew.-% in Wasser gereinigt. Danach erfolgte die Überzugsausbildung im Spritzen während 20 sec mit den nachfolgend aufgeführten Lösungen. Nach einer Wasserspülung wurde mit vollentsalztem Wasser einer Qualität von mindestens 300.000 Ohm x cm für die Dauer von 10 sec gespritzt und abschließend in einem Heißluftofen bei 200°C innerhalb von 3 min getrocknet. Die Aufbringung des Konversionsüberzuges erfolgte jeweils mit einer frisch angesetzten Überzugslösung und einer solchen, die einen Tag gestanden hatte, für jeweils 10 Dosen pro Liter Lösung.Cans made from tinplate were cleaned in a mildly alkaline cleaner with a concentration of 1% by weight in water. The coating was then sprayed for 20 seconds using the solutions listed below. After a water rinse, deionized water of a quality of at least 300,000 ohm × cm was sprayed for a period of 10 seconds and then dried in a hot air oven at 200 ° C. within 3 minutes. The conversion coating was applied in each case with a freshly prepared coating solution and one which had stood for a day for 10 cans per liter of solution.

Beschaffenheit der verwendeten Behandlungslösung: H₃PO₄ (75 Gew.-%) 15 g/l (PO₄ 11 g/l) NaClO₃ 6 g/l SnCl₄·5H₂O 0,6 g/l (Sn 0,2 g/l) Na₄P₂O₇·10H₂O 1,5 g/l (P₂O₇ 0,6 g/l) pH 3,1 mit Natronlauge eingestellt Behandlungstemperatur 60°C Condition of the treatment solution used: H₃PO₄ (75% by weight) 15 g / l (PO₄ 11 g / l) NaClO₃ 6 g / l SnCl₄ · 5H₂O 0.6 g / l (Sn 0.2 g / l) Na₄P₂O₇ · 10H₂O 1.5 g / l (P₂O₇ 0.6 g / l) pH 3.1 adjusted with sodium hydroxide solution Treatment temperature 60 ° C

Beispiel 2Example 2

Die Behandlung von Weißblechdosen erfolgte nach dem in Beispiel 1 beschriebenen Verfahrensgang mit folgender Lösung: H₃PO₄ (75 Gew.-%) 2,8 g/l (PO₄ 2 g/l) NaClO₃ 0,3 g/l SnCl₂·2H₂O 0,04 g/l (Sn 0,02 g/l) Na₄P₂O₇·10H₂O 0,05 g/l (P₂O₇ 0,02 g/l) pH 5,7 mit Natronlauge eingestellt Behandlungstemperatur 70°C Tinplate cans were treated according to the procedure described in Example 1 with the following solution: H₃PO₄ (75% by weight) 2.8 g / l (PO₄ 2 g / l) NaClO₃ 0.3 g / l SnCl₂ · 2H₂O 0.04 g / l (Sn 0.02 g / l) Na₄P₂O₇ · 10H₂O 0.05 g / l (P₂O₇ 0.02 g / l) pH 5.7 adjusted with sodium hydroxide solution Treatment temperature 70 ° C

Beispiel 3Example 3

Nach dem Verfahrensgang von Beispiel 1 wurden Weißblechdosen mit folgender Lösung behandelt: H₃PO₄ (75 Gew.-%) 55 g/l (PO₄ 40 g/l) NaBrO₃ 17 g/l SnCl₄·5H₂O 13,2 g/l (Sn 4,5 g/l) Na₅P₃O₁₀ 6,5 g/l (P₃O₁₀ 4,5 g/l) pH 2,2 mit Natronlauge eingestellt Behandlungstemperatur 60°C After the procedure of Example 1, tinplate cans were treated with the following solution: H₃PO₄ (75% by weight) 55 g / l (PO₄ 40 g / l) NaBrO₃ 17 g / l SnCl₄ · 5H₂O 13.2 g / l (Sn 4.5 g / l) Na₅P₃O₁₀ 6.5 g / l (P₃O₁₀ 4.5 g / l) pH 2.2 adjusted with sodium hydroxide solution Treatment temperature 60 ° C

Beispiel 4Example 4

Zur Behandlung gemäß Beispiel 1 diente folgende Lösung: H₃PO₄ (75 Gew.-%) 15 g/l (PO₄ 11 g/l) NaClO₃ 6 g/l SnCl₂·2H₂O 0,2 g/l (Sn 0,1 g/l) SnCl₄·5H₂O 0,3 g/l (Sn 0,1 g/l) Na₆P₄O₁₃ 0,9 g/l (P₄O₁₃ 0,6 g/l) pH 3,8 mit Natronlauge eingestellt Behandlungstemperatur 60°C The following solution was used for the treatment according to Example 1: H₃PO₄ (75% by weight) 15 g / l (PO₄ 11 g / l) NaClO₃ 6 g / l SnCl₂ · 2H₂O 0.2 g / l (Sn 0.1 g / l) SnCl₄ · 5H₂O 0.3 g / l (Sn 0.1 g / l) Na₆P₄O₁₃ 0.9 g / l (P₄O₁₃ 0.6 g / l) pH 3.8 adjusted with sodium hydroxide solution Treatment temperature 60 ° C

Vergleichsbeispiel 1Comparative Example 1

Zur Behandlung von Weißblechdosen entsprechend dem Verfahrensgang von Beispiel 1 diente folgende Lösung: H₃PO₄ (75 Gew.-%) 15 g/l (PO₄ 11 g/l) NaClO₃ 6 g/l SnCl₄·5H₂O 0,6 g/l (Sn 0,2 g/l) pH 3,8 mit Natronlauge eingestellt Behandlungstemperatur 60°C The following solution was used to treat tin cans in accordance with the procedure of Example 1: H₃PO₄ (75% by weight) 15 g / l (PO₄ 11 g / l) NaClO₃ 6 g / l SnCl₄ · 5H₂O 0.6 g / l (Sn 0.2 g / l) pH 3.8 adjusted with sodium hydroxide solution Treatment temperature 60 ° C

Vergleichsbeispiel 2Comparative Example 2

Entsprechend dem Verfahrensgang von Beispiel 1 wurden Weißblechdosen mit folgender Lösung behandelt: H₃PO₄ (75 Gew.-%) 15 g/l (PO₄ 11 g/l) NaClO₃ 6 g/l SnCl₄·5H₂O 0,6 g/l (Sn 0,2 g/l) Na₄P₂O₇·10H₂O 21 g/l (P₂O₇ 8 g/l) pH 3,1 mit Natronlauge eingestellt Behandlungstemperatur 60°C In accordance with the procedure of Example 1, tinplate cans were treated with the following solution: H₃PO₄ (75% by weight) 15 g / l (PO₄ 11 g / l) NaClO₃ 6 g / l SnCl₄ · 5H₂O 0.6 g / l (Sn 0.2 g / l) Na₄P₂O₇ · 10H₂O 21 g / l (P₂O₇ 8 g / l) pH 3.1 adjusted with sodium hydroxide solution Treatment temperature 60 ° C

In den Behandlungslösungen von Beispiel 1 bis 4 und Vergleichsbeispiel 1 und 2 wurde der Zinngehalt nach Ansatz und nach eintägigem Stehen ermittelt. Außerdem wurden die mit Konversionsüberzügen versehenen Weißblechdosen dem Korrosionstest und dem Lackhaftungstest unterworfen.In the treatment solutions of Examples 1 to 4 and Comparative Examples 1 and 2, the tin content was determined after the batch and after standing for one day. In addition, the tinplate cans provided with conversion coatings were subjected to the corrosion test and the paint adhesion test.

Zur Ermittlung des Korrosionswiderstandes wurden die behandelten Dosen in Leitungswasser von 60°C für die Dauer von 30 min eingetaucht und die Rostentwicklung bewertet.To determine the corrosion resistance, the treated cans were immersed in tap water at 60 ° C. for 30 minutes and the rust development was assessed.

Aus der nachfolgenden Tabelle ergibt sich, daß die nach dem erfindungsgemäßen Verfahren behandelten Weißblechdosen einen deutlich besseren Korrosionswiderstand aufweisen als die gemäß den Vergleichsversuchen behandelten Dosen. Tabelle Ergebnisse des Korrosionstestes frisch angesetzte Lösung nach eintägigem Stehen * Sn-Gehalt (ppm) Entwicklung v. rotem Rost (%) Sn-Gehalt (ppm) Entwicklung v. rotem Rost (%) Beispiele 1 200 0 200 0 2 20 8 20 8 3 4500 5 4500 5 4 200 0 200 0 Vergleichsbeispiele 1 200 10 0 100 2 200 20 200 20 * und Behandlung von 10 Dosen/l The table below shows that the tinplate cans treated by the process according to the invention have a significantly better corrosion resistance than the cans treated according to the comparative tests. table Results of the corrosion test freshly prepared solution after standing for one day * Sn content (ppm) Development of red rust (%) Sn content (ppm) Development of red rust (%) Examples 1 200 0 200 0 2nd 20th 8th 20th 8th 3rd 4500 5 4500 5 4th 200 0 200 0 Comparative examples 1 200 10th 0 100 2nd 200 20th 200 20th * and treatment of 10 doses / l

Zur Ermittlung der Lackhaftung wurden auf die mit den Konversionsüberzügen versehenen Dosen ein Epoxy-/Harnstofflack einer Dicke von 5 bis 7 µm aufgebracht und bei 210°C eingebrannt (Dauer 10 min). Nach 24-stündigem Stehenlassen wurden die Dosen in eine 1 Gew.-% wäßrige Zitronensäurelösung von 95 bis 97°C getaucht und 60 min darin belassen. Anschließend wurde mit Wasser gespült und getrocknet.To determine the paint adhesion, an epoxy / urea paint with a thickness of 5 to 7 µm was applied to the cans provided with the conversion coatings and baked at 210 ° C. (duration 10 min). After standing for 24 hours, the cans were immersed in a 1% by weight aqueous citric acid solution at 95 to 97 ° C and left therein for 60 minutes. It was then rinsed with water and dried.

Danach wurden die Proben mit einem bis auf die Metalloberfläche reichenden Gitterschnitt und dann mit Cellophan-Klebeband durch kräftiges Andrücken versehen. Nach dem Abreißen des Klebebandes zeigte sich, daß die Lackhaftung durchgängig hervorragend war, d.h. keinerlei Lackablösung festzustellen war.Thereafter, the samples were provided with a cross cut reaching to the metal surface and then with cellophane adhesive tape by pressing firmly. After the adhesive tape was torn off, it was found that the paint adhesion was consistently excellent, i.e. no paint detachment was found.

Claims (6)

1. Verfahren zum Aufbringen von Konversionsüberzügen auf Metalloberflächen mit Hilfe von Phosphat, Zinn und Beschleuniger enthaltenden wäßrigen Lösungen, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die neben

1 bis 50 g/l Phosphat (ber. als PO₄)
0,01 bis 5 g/l Zinn
0,2 bis 20 g/l Beschleuniger

zusätzlich Komplexbildner in einer Menge von 0,01 bis 5 g/l enthält und einen pH-Wert von 2 bis 6 aufweist.1. A process for applying conversion coatings on metal surfaces with the aid of phosphate, tin and accelerator-containing aqueous solutions, characterized in that the metal surfaces are brought into contact with a solution which, in addition to

1 to 50 g / l phosphate (calculated as PO₄)
0.01 to 5 g / l tin
0.2 to 20 g / l accelerator

additionally contains complexing agents in an amount of 0.01 to 5 g / l and has a pH of 2 to 6. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die 2 bis 25 g/l Phosphat enthält.2. The method according to claim 1, characterized in that the metal surfaces are brought into contact with a solution which contains 2 to 25 g / l phosphate. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die als Beschleuniger Oxosäuren, insbesondere Chlorat und/oder Bromat, enthält.3. The method according to claim 1 or 2, characterized in that the metal surfaces are brought into contact with a solution which contains oxo acids, in particular chlorate and / or bromate, as accelerators. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die als Komplexbildner kondensierte Phosphate, insbesondere Polyphosphate der allgemeinen Formel

PnO3n+1

mit n = 2,3 oder 4 enthält.4. The method according to claim 1, 2 or 3, characterized in that the metal surfaces are brought into contact with a solution which contains condensed phosphates as complexing agents, in particular polyphosphates of the general formula

P n O 3n + 1

with n = 2, 3 or 4. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man den Konversionsüberzug auf elektrochemischem Wege erzeugt.5. The method according to one or more of claims 1 to 4, characterized in that one generates the conversion coating by electrochemical means. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man den Konversionsüberzug in zwei Stufen, zunächst chemisch, anschließend elektrochemisch, erzeugt.6. The method according to one or more of claims 1 to 5, characterized in that the conversion coating is produced in two stages, first chemically, then electrochemically.
EP88202291A 1987-10-13 1988-10-13 Process for applying conversion coatings Expired - Lifetime EP0312176B1 (en)

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JP257678/87 1987-10-13

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WO1991019828A1 (en) * 1990-06-19 1991-12-26 Henkel Corporation Liquid composition and process for treating aluminium or tin cans to impart corrosion resistance and reduced friction coefficient
US5370909A (en) * 1990-06-19 1994-12-06 Henkel Corporation Liquid composition and process for treating aluminum or tin cans to impart corrosion resistance and mobility thereto
WO1992009720A1 (en) * 1990-11-21 1992-06-11 Henkel Corporation Composition and method for treating tin plated steel surface
US5356491A (en) * 1990-11-21 1994-10-18 Henkel Corporation Composition and method for treating tin plated steel surface
WO1993012268A1 (en) * 1991-12-12 1993-06-24 Henkel Corporation A process and composition for treating the surface of tin-plated steel
EP0673445A1 (en) * 1992-12-09 1995-09-27 Henkel Corporation Composition and process for treating tinplate
EP0673445A4 (en) * 1992-12-09 1997-05-02 Henkel Corp Composition and process for treating tinplate.
EP0678595A1 (en) * 1994-04-20 1995-10-25 Nippon Paint Co., Ltd. Surface treatment aqueous solution for metal
US5942052A (en) * 1994-04-20 1999-08-24 Nippon Paint Co., Ltd. Surface treatment aqueous solution for metal
EP1433879A1 (en) * 2002-12-24 2004-06-30 Chemetall GmbH Process for metal surface coating with an alkali phosphate solution, aqueous concentrate and use of such coated metal surfaces
CN103210126A (en) * 2010-10-06 2013-07-17 塔塔钢铁艾默伊登有限责任公司 Process for producing an iron-tin layer on a packaging steel substrate
WO2014012703A1 (en) * 2012-07-18 2014-01-23 Henkel Ag & Co. Kgaa Tinning pretreatment of galvanized steel in the presence of pyrophosphate

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GB2210900B (en) 1991-11-20
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