EP0015021A1 - Process for the pretreatment of metal surfaces for electrophoretic dip painting - Google Patents

Process for the pretreatment of metal surfaces for electrophoretic dip painting Download PDF

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Publication number
EP0015021A1
EP0015021A1 EP80200097A EP80200097A EP0015021A1 EP 0015021 A1 EP0015021 A1 EP 0015021A1 EP 80200097 A EP80200097 A EP 80200097A EP 80200097 A EP80200097 A EP 80200097A EP 0015021 A1 EP0015021 A1 EP 0015021A1
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Prior art keywords
solutions
metal surfaces
phosphate
contain
treatment
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EP80200097A
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German (de)
French (fr)
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EP0015021B1 (en
Inventor
Werner Dr. Rausch
Gerhard Müller
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GEA Group AG
Continentale Parker Ste
Continentale Parker SA
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Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/362—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 fluorides or complex fluorides containing also phosphates containing also zinc cations
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • the solutions are therefore frequently also given various organic or inorganic chelating agents, such as citric acid, tartaric acid, malonic acid, polyphosphoric acid, glycerophosphoric acid, ethylenediaminetetraacetic acid, Nitrilotriacetic acid or its salts added.
  • organic or inorganic chelating agents such as citric acid, tartaric acid, malonic acid, polyphosphoric acid, glycerophosphoric acid, ethylenediaminetetraacetic acid, Nitrilotriacetic acid or its salts added.
  • a disadvantage of the coatings produced with the known solutions based on monozinc phosphate as the basis for the subsequent electrodeposition coating is, in particular, that a considerable part of the phosphate coating is separated off during the coating, passes into the coating film and adversely affects it,
  • Essentially free of ferroions means that one at the treatment of non-ferrous metals does not involve the use of bath solutions which contain substantial amounts of ferro ions and, in the preferred treatment of steel surfaces, brings them into contact with solutions which contain accelerators which oxidize ferro ions.
  • Treatment solutions containing chlorate and / or nitrite are particularly suitable. It is sufficient to use as much chlorate and / or nitrite as is necessary to remove excess ferroions by oxidation. The amounts are thus dependent on the throughput and do not need to be specifically matched to the amount of zinc ions and phosphoric acid or to phosphoric acid, as is required in known processes. However, it has been found that the chlorate content should be set to at least 0.1 g / l. Larger quantities are advisable for high throughputs.
  • Solutions are advantageously used which contain vanadium compounds, preferably in amounts of 0.1 to 10 mg / l vanadium, which has proven to be advantageous particularly at high throughputs.
  • Other polyvalent cations such as Ni, Mn or Ca ions, the amount of which, however, should not exceed 0.5 g / l, bring about a further improvement.
  • alkali metal ions Na, NH 4 etc.
  • the P0 4 content is in the usual range and is about 5 to 20 g / l.
  • the phosphate layers achieved with the method according to the invention impart such a high level of corrosion protection (higher protection against infiltration) that a subsequent treatment with the known rinsing agents, e.g. B. Cr (VI) - or Cr (III) ion-containing, practically no additional improvement.
  • the phosphate layers produced with the invention are of a quality that is otherwise only achieved by using additional rinsing agents.
  • the sheets were then rinsed with water and deionized water and then dried.
  • the coating weight achieved was 1, 8 g / m 2.
  • a modified epoxy resin varnish was then cathodically deposited on the steel sheet pretreated in this way.
  • the electrodeposition bath had room temperature, the deposition voltage and duration were 180 volts or 2 minutes.
  • the varnish was then baked at an object temperature of 190 ° C for 25 minutes.
  • the paint film thickness thus obtained was 15 / um, the paint layer uniform and shiny.
  • the corrosion protection of the sheet, provided with the varnish and scratched crosswise, was tested in a salt spray test (1000 hours).
  • the paint infiltration determined after this was 1 to 2 mm.
  • the paint infiltration determined after the salt spray test was only less than 1 mm.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Bei einem Verfahren zur Vorbereitung von Metalloberflächen, insbesondere solchen aus Stahl, für die elektrophoretische Tauchlackierung ist es bekannt, mit Lösungen zu behandeln, die Zink und PO4 im Gewichtsverhältnis von 1 : (12 bis 110) enthalten. Die dabei erzeugten Phosphatschichten bewirken einen hohen Korrosionsschutz und lösen sich während der elektrophoretischen Lackierung nur wenig ab. Zwecks weiterer Steigerung des Korrosionsschutzes und Verbesserung des Ablöseverhaltens der Phosphatschicht erfolgt die Behandlung mit Phosphatierungslösungen, die zusätzlich einen Gehalt an Fluoborat, vorzugsweise in Mengen von 0,3 bis 2,0 g/l aufweisen und im wesentlichen ferroionenfrei sind. Bei der vorzugsweisen Behandlung von Stab werden zweckmäßigerweise Chlorat und/oder Nitrit Beschleuniger eingesetzt.In a method for preparing metal surfaces, in particular those made of steel, for electrophoretic dip coating, it is known to treat with solutions which contain zinc and PO4 in a weight ratio of 1: (12 to 110). The phosphate layers created thereby provide a high level of corrosion protection and only detach very little during the electrophoretic coating. In order to further increase the corrosion protection and improve the detachment behavior of the phosphate layer, the treatment is carried out with phosphating solutions which additionally contain fluoborate, preferably in amounts of 0.3 to 2.0 g / l and are essentially free of ferroions. Chlorate and / or nitrite accelerators are expediently used in the preferred treatment of rod.

Description

Die Erfindung betrifft ein Verfahren zur Vorbereitung von Metalloberflächen, insbesondere aus Stahl, für die elektrophoretische Tauchlackierung durch Aufbringen von Phosphatschichten mittels Zink- und Phosphationen enthaltender Lösungen, in denen das Gewichtsverhältnis von Zn : P04 = 1 : (12 bis 110), vorzugsweise = 1 : (20 bis 100) ist.The invention relates to a process for the preparation of metal surfaces, in particular steel, for electrophoretic dip coating by applying phosphate layers by means of solutions containing zinc and phosphate ions, in which the weight ratio of Zn: P0 4 = 1: (12 to 110), preferably = 1: (20 to 100).

Es ist seit langem üblich, Metalloberflächen durch Aufbringung eines Phosphatüberzuges für die anschließende Lackierung vorzubereiten, um eine Verbesserung des Korrosionsschutzes und eine Erhöhung der Lackhaftung zu erzielen. Als Grundlage für die Elektrotauchlackierung dienen hauptsächlich Zinkphosphatüberzüge. Zu deren Erzeugung werden üblicherweise wäßrige saure Überzugslösungen auf Basis Monozinkphosphat verwendet, denen Chlorat, Nitrit, Nitrat, organische Nitroverbindungen oder Gemische hiervon als Beschleuniger zugesetzt werden. Die erhaltenen Überzüge sind jedoch häufig für die anschließende Lackierung wegen ihrer Dicke und Grobkristallinität unbefriedigend. Da zur Vorbehandlung vor der Elektrotauchlackierung dünne und feinkörnige Überzüge erwünscht sind, werden deshalb den Lösungen außerdem häufig verschiedene organische oder anorganische Chelatierungsmittel, wie Zitronensäure, Weinsäure, Malonsäure, Polyphosphorsäure, Glycerophosphorsäure, Äthylendiamintetraessigsäure, Nitrilotriessigsäure oder deren Salze zugesetzt. Hierdurch ergeben sich jedoch häufig Schwierigkeiten, die Lösungen zu kontrollieren; auch genügt die Schichtausbildung oft nicht den gestellten Anforderungen.It has long been customary to prepare metal surfaces by applying a phosphate coating for the subsequent painting in order to improve corrosion protection and increase paint adhesion. Mainly zinc phosphate coatings serve as the basis for electrocoating. Aqueous acidic coating solutions based on monozinc phosphate, to which chlorate, nitrite, nitrate, organic nitro compounds or mixtures thereof are added as accelerators, are usually used to produce them. However, the coatings obtained are often unsatisfactory for the subsequent coating because of their thickness and coarse crystallinity. Since thin and fine-grained coatings are desired for the pretreatment prior to electrocoating, the solutions are therefore frequently also given various organic or inorganic chelating agents, such as citric acid, tartaric acid, malonic acid, polyphosphoric acid, glycerophosphoric acid, ethylenediaminetetraacetic acid, Nitrilotriacetic acid or its salts added. However, this often creates difficulties in checking the solutions; the layer formation also often does not meet the requirements.

Ein Nachteil der mit den bekannten Lösungen auf Basis Monozinkphosphat erzeugten Überzüge als Grundlage für die anschließende Elektrotauchlackierung besteht insbesondere darin, daß ein beachtlicher Teil des Phosphatüberzuges bei der Lackierung abgetrennt wird, in den Lackfilm übergeht und diesen nachteilig beeinflußt,A disadvantage of the coatings produced with the known solutions based on monozinc phosphate as the basis for the subsequent electrodeposition coating is, in particular, that a considerable part of the phosphate coating is separated off during the coating, passes into the coating film and adversely affects it,

Zwar ist es bekannt, diese Nachteile weitgehend zu vermeiden, indem man Behandlungslösungen zum Einsatz bringt, in denen der Zinkanteil in Bezug auf die Phosphationen gegenüber den üblichen Lösungen auf Basis Monozinkphosphat erheblich erniedrigt ist (DE-OS 22 32 067). Die Behandlung führt zu verbesserten dünnen und gleichmäßigen Phosphat- überzügen auf Metalloberflächen, insbesondere Stahl, die sehr haftfest und beständig und als Grundlage für die anschließende Elektrotauchlackierung geeignet sind. Die Phosphatschichten vermitteln einen hohen Korrosionsschutz und werden bei der Lackierung zu einem wesentlich geringeren Anteil abgetrennt als die bei Verwendung der bisher üblichen Lösungen erzeugten Überzüge.It is known to largely avoid these disadvantages by using treatment solutions in which the zinc content in relation to the phosphate ions is considerably reduced compared to the conventional solutions based on monozinc phosphate (DE-OS 22 32 067). The treatment leads to improved thin and uniform phosphate coatings on metal surfaces, in particular steel, which are very adhesive and resistant and are suitable as a basis for the subsequent electrocoating. The phosphate layers provide a high level of protection against corrosion and are removed to a much lesser extent during painting than the coatings produced when using the solutions customary hitherto.

Es wurde nun gefunden, daß die mit dem Verfahren gemäß DE-OS 22 32 067 erzielten Vorteile noch vermehrt werden können, wenn man das eingangs genannte Verfahren entsprechend der Erfindung derart ausstattet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die zusätzlich einen Gehalt an Fluoborat, vorzugsweise in Mengen von 0,3 bis 2,0 g/l, aufweisen und im wesentlichen ferroionenfrei sind.It has now been found that the advantages achieved with the method according to DE-OS 22 32 067 can be increased if the method mentioned at the outset according to the invention is equipped in such a way that the metal surfaces are brought into contact with solutions which additionally contain of fluoborate, preferably in amounts of 0.3 to 2.0 g / l, and are essentially free of ferroions.

Im wesentlichen ferroionenfrei bedeutet, daß man bei der Behandlung von Nichteisenmetallen von der Verwendung von Badlösungen absieht, die wesentliche Ferroionenmengen enthalten und bei der vorzugsweise vorgesehenen Behandlung von Stahloberflächen, diese mit Lösungen in Berührung bringt, die Ferro- zu Ferriionen oxydierende Beschleuniger enthalten.Essentially free of ferroions means that one at the treatment of non-ferrous metals does not involve the use of bath solutions which contain substantial amounts of ferro ions and, in the preferred treatment of steel surfaces, brings them into contact with solutions which contain accelerators which oxidize ferro ions.

Besonders geeignet sind Behandlungslösungen, die Chlorat und/oder Nitrit enthalten. Dabei ist es ausreichend, soviel Chlorat und/oder Nitrit zu verwenden, als zur Entfernung von überschüssigen Ferroionen durch Oxidation notwendig sind. Die Mengen sind also vom Durchsatz abhängig und brauchen nicht besonders auf die Menge an Zinkionen und Phosphorsäure oder auf Phosphorsäure abgestimmt zu werden, wie dies bei bekannten Verfahren vorgeschrieben ist. Es hat sich jedoch erwiesen, daß der Gehalt an Chlorat auf mindestens 0,1 g/l eingestellt werden sollte. Bei hohen Durchsätzen sind größere Mengen zweckmäßig.Treatment solutions containing chlorate and / or nitrite are particularly suitable. It is sufficient to use as much chlorate and / or nitrite as is necessary to remove excess ferroions by oxidation. The amounts are thus dependent on the throughput and do not need to be specifically matched to the amount of zinc ions and phosphoric acid or to phosphoric acid, as is required in known processes. However, it has been found that the chlorate content should be set to at least 0.1 g / l. Larger quantities are advisable for high throughputs.

Vorteilhafterweise gelangen Lösungen zum Einsatz, die Vanadin-Verbindungen, vorzugsweise in Mengen von 0,1 bis 10 mg/1 Vanadin, enthalten, was sich besonders bei hohen Durchsätzen als vorteilhaft erwiesen hat. Weitere mehrwertige Kationen, wie Ni-, Mn- oder Ca-Ionen, deren Menge jedoch höchstens 0,5 g/l betragen soll, bewirken eine weitere Verbesserung.Solutions are advantageously used which contain vanadium compounds, preferably in amounts of 0.1 to 10 mg / l vanadium, which has proven to be advantageous particularly at high throughputs. Other polyvalent cations, such as Ni, Mn or Ca ions, the amount of which, however, should not exceed 0.5 g / l, bring about a further improvement.

Um den Anteil an PO4, der den erforderlichen Grad freier Säure übersteigt, zu binden, ist ein Zusatz von Alkalimetallionen (Na, NH4 usw.) erforderlich. Der Gehalt an P04 liegt im-üblichen Bereich und beträgt etwa 5 bis 20 g/l.In order to bind the proportion of PO 4 which exceeds the required degree of free acid, an addition of alkali metal ions (Na, NH 4 etc.) is required. The P0 4 content is in the usual range and is about 5 to 20 g / l.

Die mit dem erfindungsgemäßen Verfahren erzielten Phosphatschichten vermitteln einen so hohen Korrosionsschutz (höherer Unterwanderungsschutz), daß eine Folgebehandlung mit den bekannten Nachspülmitteln, z. B. Cr(VI)- oder Cr(III)-Ionen-haltig, praktisch keine zusätzliche Verbesserung bewirkt. Das heißt, die mit der Erfindung erzeugten Phosphatschichten sind von einer Qualität, die sonst nur durch Verwendung zusätzlicher Nachspülmittel erzielt wird.The phosphate layers achieved with the method according to the invention impart such a high level of corrosion protection (higher protection against infiltration) that a subsequent treatment with the known rinsing agents, e.g. B. Cr (VI) - or Cr (III) ion-containing, practically no additional improvement. This means that the phosphate layers produced with the invention are of a quality that is otherwise only achieved by using additional rinsing agents.

AusführungsbeispielEmbodiment

a) Entfettete Stahlbleche werden innerhalb von 2 Minuten durch Spritzen mit einer Phosphatierungslösung von 58 °C behandelt, die

Figure imgb0001
enthielt. Der Wert für freie Säure lag bei 0,8, für Gesamtsäure bei 14,5.a) Degreased steel sheets are treated within 2 minutes by spraying with a phosphating solution of 58 ° C, the
Figure imgb0001
 contained. The value for free acid was 0.8 and for total acid 14.5.

Die Bleche wurden dann mit Wasser und mit vollentsalztem Wasser gespült und anschließend getrocknet.The sheets were then rinsed with water and deionized water and then dried.

Das erzielte Schichtgewicht betrug 1,8 g/m2.The coating weight achieved was 1, 8 g / m 2.

Anschließend wurde auf dem so vorbehandelten Stahlblech ein modifizierter Epoxyharzlack kathodisch abgeschieden. Das Bad für die Elektrotauchlackierung besaß Raumtemperatur, Abscheidespannung und -dauer lagen bei 180 Volt bzw. 2 Minuten. Danach wurde der Lack bei einer Objekttemperatur von 190 °C während 25 Minuten eingebrannt. Die dabei erhaltene Lackfilmdicke war 15/um, die Lackschicht gleichmäßig und glänzend.A modified epoxy resin varnish was then cathodically deposited on the steel sheet pretreated in this way. The electrodeposition bath had room temperature, the deposition voltage and duration were 180 volts or 2 minutes. The varnish was then baked at an object temperature of 190 ° C for 25 minutes. The paint film thickness thus obtained was 15 / um, the paint layer uniform and shiny.

Der Korrosionsschutz der mit dem Lack versehenen und kreuzweise eingeritzten Blechs wurde im Salzsprühtest (1000 Std.) geprüft. Die danach ermittelte Lackunterwanderung betrug 1 bis 2 mm.The corrosion protection of the sheet, provided with the varnish and scratched crosswise, was tested in a salt spray test (1000 hours). The paint infiltration determined after this was 1 to 2 mm.

b) Der vorstehend skizzierte Verfahrensgang wurde in allen Einzelheiten wiederholt. Es kam jedoch eine Phosphatierungslösung zur Anwendung, die neben den unter a) aufgeführten Bestandteilen zusätzlich
0,8 g/1 BF4 enthielt.b) The procedure outlined above was repeated in every detail. However, a phosphating solution was used, which in addition to the components listed under a)
0.8 g / 1 BF 4 contained.

Die nach dem Salzsprühtest ermittelte Lackunterwanderung lag nur bei kleiner 1 mm.The paint infiltration determined after the salt spray test was only less than 1 mm.

c) Der Behandlungsgang gemäß b) wurde dahingehend variiert, daß anstelle der Spülung mit Wasser einmal mit Chrom(III)-acetat-Lösung (150 mg/l Cr(III)) und einmal mit Chromsäure/Chrom(III)-acetat-Lösung (15Q mg/l Cr(VI), 40 mg/l Cr(III)) gespült wurde.c) The course of treatment according to b) was varied so that instead of rinsing with water once with chromium (III) acetate solution (150 mg / l Cr (III)) and once with chromic acid / chromium (III) acetate solution (15Q mg / l Cr (VI), 40 mg / l Cr (III)).

Der nach der Lackierung etc. vorgenommene Salzsprühtest brachte die gleichen Ergebnisse wie unter b).The salt spray test carried out after painting, etc. gave the same results as under b).

Ein Vergleich der Ergebnisse zeigt, daß der Korrosionsschutz, speziell der Lackunterwanderungsschutz, der mit Fluoborat modifizierten Phosphatierungslösung erheblich besser ist als der, der bei Verwendung einer Fluoboratfreien Phosphatierungslösung erhalten wird. Außerdem ist erkennbar, daß auch ohne Nachspülung mit Cr(III)-bzw. Cr(VI)-Lösungen ein Korrosionsschutz erzielt wird, der dem mit Verwendung der genannten Lösung praktisch gleich ist.A comparison of the results shows that the corrosion protection, especially the paint infiltration protection, of the phosphating solution modified with fluoroborate is considerably better than that which is obtained when using a fluoroborate-free phosphating solution. It can also be seen that even without rinsing with Cr (III) or. Cor (VI) solutions a corrosion protection is achieved, which is practically the same as using the solution mentioned.

Claims (4)

1. Verfahren zur Vorbereitung von Metalloberflächen, insbesondere aus Stahl, für die elektrophoretische Tauchlackierung durch Aufbringen von Phosphatschichten mittels Zink- und Phosphationen enthaltender Lösungen, in denen das Gewichtsverhältnis von Zn : P04 = 1 : (12 bis 110), vorzugsweise = 1 : (20 bis 100) ist, dadurch gekennzeichnet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die zusätzlich einen Gehalt an Fluoborat, vorzugsweise in Mengen von 0,3 bis 2,0 g/l aufweisen und im wesentlichen ferroionenfrei sind.1. Process for preparing metal surfaces, in particular steel, for electrophoretic dip coating by applying phosphate layers by means of solutions containing zinc and phosphate ions, in which the weight ratio of Zn: P0 4 = 1: (12 to 110), preferably = 1: (20 to 100), characterized in that the metal surfaces are brought into contact with solutions which additionally contain fluoborate, preferably in amounts of 0.3 to 2.0 g / l and are essentially free of ferroions. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man bei der Behandlung von Stahloberflächen, diese mit Lösungen in Berührung bringt, die Ferroionen zu Ferriionen oxidierende Beschleuniger enthalten.2. The method according to claim 1, characterized in that in the treatment of steel surfaces, it is brought into contact with solutions which contain ferroions to accelerate oxidizing ferriions. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die Chlorat und/oder Nitrit als Beschleuniger enthalten.3. The method according to claim 2, characterized in that the metal surfaces are brought into contact with solutions which contain chlorate and / or nitrite as an accelerator. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß die Metalloberflächen mit Lösungen in Berührung gebracht werden, die Vanadinverbindungen, vorzugsweise in Mengen von 0,1 bis 10 mg/l Vanadin, enthalten.4. The method according to claim 1, 2 or 3, characterized in that the metal surfaces are brought into contact with solutions containing vanadium compounds, preferably in amounts of 0.1 to 10 mg / l vanadium.
EP80200097A 1979-02-23 1980-02-05 Process for the pretreatment of metal surfaces for electrophoretic dip painting Expired EP0015021B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2907094 1979-02-23
DE19792907094 DE2907094A1 (en) 1979-02-23 1979-02-23 PHOSPHATION SOLUTIONS

Publications (2)

Publication Number Publication Date
EP0015021A1 true EP0015021A1 (en) 1980-09-03
EP0015021B1 EP0015021B1 (en) 1984-10-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP80200097A Expired EP0015021B1 (en) 1979-02-23 1980-02-05 Process for the pretreatment of metal surfaces for electrophoretic dip painting

Country Status (10)

Country Link
US (1) US4265677A (en)
EP (1) EP0015021B1 (en)
JP (1) JPS5914113B2 (en)
AU (1) AU531900B2 (en)
CA (1) CA1134246A (en)
DE (2) DE2907094A1 (en)
ES (1) ES8200408A2 (en)
GB (1) GB2046312A (en)
IT (1) IT1141231B (en)
ZA (1) ZA80915B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0056881A1 (en) * 1981-01-22 1982-08-04 Metallgesellschaft Ag Method of phosphating metals
EP0065950A1 (en) * 1980-12-08 1982-12-08 Chemfil Corp Phosphate coating process and composition.
EP0154367A2 (en) * 1984-03-09 1985-09-11 Metallgesellschaft Ag Process for phosphatizing metals
EP0264811A1 (en) * 1986-10-16 1988-04-27 Nihon Parkerizing Co., Ltd. Process for producing phosphate coatings
GB2203453A (en) * 1986-10-25 1988-10-19 Pyrene Chemical Services Ltd Phosphate coating solutions and processes
EP0018841B1 (en) * 1979-05-02 1989-07-12 Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America Composition and process for zinc-phosphate coating a metal surface, coated metal surface and a process for painting the coated surface
US5904786A (en) * 1994-12-09 1999-05-18 Metallgesellschaft Aktiengesellschaft Method of applying phosphate coatings to metal surfaces

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5811515B2 (en) * 1979-05-11 1983-03-03 日本ペイント株式会社 Composition for forming a zinc phosphate film on metal surfaces
DE3118375A1 (en) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METALS AND ITS APPLICATION FOR PRE-TREATMENT FOR ELECTRO DIP PAINTING
JPS58224172A (en) * 1982-06-24 1983-12-26 Nippon Parkerizing Co Ltd Pretreatment for coating by cationic electrodeposition
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
DE3244715A1 (en) * 1982-12-03 1984-06-07 Gerhard Collardin GmbH, 5000 Köln METHOD FOR PHOSPHATING METAL SURFACES, AND BATH SOLUTIONS SUITABLE FOR THIS
JPS59133375A (en) * 1983-12-03 1984-07-31 Nippon Paint Co Ltd Composition for forming zinc phosphate film on metallic surface
DE3541997A1 (en) * 1985-11-28 1987-06-04 Collardin Gmbh Gerhard IMPROVED METHOD FOR ACTIVATING METAL SURFACES BEFORE ZINC PHOSPHATION
DE58905074D1 (en) * 1988-02-03 1993-09-09 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COATINGS ON METALS.
DE3814287A1 (en) * 1988-04-28 1989-11-09 Henkel Kgaa POLYMERS TITANIUM PHOSPHATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR ACTIVATING METAL SURFACES BEFORE ZINC PHOSPHATION
KR100197145B1 (en) * 1989-12-19 1999-06-15 후지이 히로시 Method for phosphating metal surface with zinc phosphate
DE4409306A1 (en) * 1994-03-18 1995-09-21 Basf Ag Process for modifying metal surfaces
US6193815B1 (en) * 1995-06-30 2001-02-27 Henkel Corporation Composition and process for treating the surface of aluminiferous metals

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT277705B (en) * 1967-10-18 1970-01-12 Metallgesellschaft Ag Process for applying a phosphate coating to metals
DE2049350A1 (en) * 1969-10-08 1971-04-15 Lubrizol Corp Phosphating solutions and their use for the corrosion protection of ferrous metal and zinc surfaces
DE2143957A1 (en) * 1971-09-02 1973-03-08 Metallgesellschaft Ag METHOD OF APPLYING A PHOSPHATUE COATING TO IRON AND STEEL
AT314931B (en) * 1971-07-06 1974-03-15 Metallgesellschaft Ag PHOSPHATING SOLUTIONS
GB1353339A (en) * 1970-10-16 1974-05-15 Lubrizol Corp Phosphating solution with scale suppressing characteristics
US3850700A (en) * 1971-10-18 1974-11-26 Amchem Prod Method and materials for coating metal surfaces

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1235293A (en) * 1967-12-12 1971-06-09 Canadian Ind Cationic electrodeposition systems
US3617393A (en) * 1969-10-08 1971-11-02 Dainippon Toryo Kk Pretreatment before electrophoretic painting

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT277705B (en) * 1967-10-18 1970-01-12 Metallgesellschaft Ag Process for applying a phosphate coating to metals
DE2049350A1 (en) * 1969-10-08 1971-04-15 Lubrizol Corp Phosphating solutions and their use for the corrosion protection of ferrous metal and zinc surfaces
GB1353339A (en) * 1970-10-16 1974-05-15 Lubrizol Corp Phosphating solution with scale suppressing characteristics
AT314931B (en) * 1971-07-06 1974-03-15 Metallgesellschaft Ag PHOSPHATING SOLUTIONS
DE2143957A1 (en) * 1971-09-02 1973-03-08 Metallgesellschaft Ag METHOD OF APPLYING A PHOSPHATUE COATING TO IRON AND STEEL
US3819385A (en) * 1971-09-02 1974-06-25 Oxy Metal Finishing Corp Method for applying a phosphate coating to iron and steel
US3850700A (en) * 1971-10-18 1974-11-26 Amchem Prod Method and materials for coating metal surfaces

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0018841B1 (en) * 1979-05-02 1989-07-12 Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America Composition and process for zinc-phosphate coating a metal surface, coated metal surface and a process for painting the coated surface
EP0065950A1 (en) * 1980-12-08 1982-12-08 Chemfil Corp Phosphate coating process and composition.
EP0065950B1 (en) * 1980-12-08 1987-11-25 Chemfil Corporation Phosphate coating process and composition
EP0056881A1 (en) * 1981-01-22 1982-08-04 Metallgesellschaft Ag Method of phosphating metals
EP0154367A2 (en) * 1984-03-09 1985-09-11 Metallgesellschaft Ag Process for phosphatizing metals
EP0154367A3 (en) * 1984-03-09 1986-08-20 Metallgesellschaft Ag Process for phosphatizing metals
EP0264811A1 (en) * 1986-10-16 1988-04-27 Nihon Parkerizing Co., Ltd. Process for producing phosphate coatings
GB2203453A (en) * 1986-10-25 1988-10-19 Pyrene Chemical Services Ltd Phosphate coating solutions and processes
GB2203453B (en) * 1986-10-25 1990-12-05 Pyrene Chemical Services Ltd Phosphate coating solutions and processes
US5904786A (en) * 1994-12-09 1999-05-18 Metallgesellschaft Aktiengesellschaft Method of applying phosphate coatings to metal surfaces

Also Published As

Publication number Publication date
JPS5914113B2 (en) 1984-04-03
IT8020102A0 (en) 1980-02-22
ES488871A0 (en) 1981-11-01
US4265677A (en) 1981-05-05
JPS55131177A (en) 1980-10-11
GB2046312A (en) 1980-11-12
EP0015021B1 (en) 1984-10-03
DE2907094A1 (en) 1980-09-04
IT1141231B (en) 1986-10-01
ES8200408A2 (en) 1981-11-01
DE3069330D1 (en) 1984-11-08
AU5580480A (en) 1980-08-28
CA1134246A (en) 1982-10-26
AU531900B2 (en) 1983-09-08
ZA80915B (en) 1981-02-25

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