EP0469011A1 - Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films. - Google Patents

Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films.

Info

Publication number
EP0469011A1
EP0469011A1 EP90906149A EP90906149A EP0469011A1 EP 0469011 A1 EP0469011 A1 EP 0469011A1 EP 90906149 A EP90906149 A EP 90906149A EP 90906149 A EP90906149 A EP 90906149A EP 0469011 A1 EP0469011 A1 EP 0469011A1
Authority
EP
European Patent Office
Prior art keywords
zinc
iron
nickel
manganese
dipping
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90906149A
Other languages
German (de)
French (fr)
Other versions
EP0469011B1 (en
Inventor
Joerg Riesop
Kurt Hosemann
Karl-Heinz Gottwald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0469011A1 publication Critical patent/EP0469011A1/en
Application granted granted Critical
Publication of EP0469011B1 publication Critical patent/EP0469011B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations

Definitions

  • the present invention relates to a method for phosphating metal surfaces, in particular a method for producing manganese and nickel-containing zinc phosphate layers on steel, zinc and / or their alloys. These nickel and manganese-containing zinc phosphate layers are applied by spraying, splash-dipping and dipping with aqueous solutions.
  • Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components.
  • the pH of such solutions is usually in the range between 2.8 and 3.4.
  • the process consists essentially of two reactions: the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
  • manganese-modified zinc phosphate coatings are known as a liability for modern coatings.
  • the use of manganese ions in addition to zinc and nickel ions in Low-zinc phosphating processes have been shown to improve corrosion protection, especially when using surface-coated sheet metal.
  • the incorporation of manganese into the zinc phosphate coatings leads to smaller and more compact crystals with increased alkali stability.
  • the working width of phosphating baths is increased; Aluminum can also be phosphated in combination with steel and galvanized steel to form a layer, whereby the generally achieved quality standard is guaranteed.
  • the object of the present invention was to provide a phosphating process which is free of both nitrite and chlorate and which, in particular, does not cause so-called "specks".
  • crater-shaped openings are created, which are known in the English terminology as "nubbing”.
  • the systems usually used contain chlorate, broat, nitrate, nitrite, peroxide and / or organic accelerators Nitro compounds such as 3-nitrobenzenesulfonate.
  • 3-Nitrobe ⁇ zolsulfonat has been generally used in the prior art together with chlorate and / or nitrite accelerators.
  • the 3-nitrobenzenesulfonic acid / chlorate system usually used produces the abovementioned specks in the presence of nitrate on electrolytically galvanized steel, so that it is usually necessary to work without nitrates.
  • the above-mentioned object is achieved by a chlorate- and nitrite-free process for the production of nickel and manganese-containing zinc phosphate layers on steel, zinc and / or their alloys by spraying, splash-dipping and / or dipping with an aqueous solution
  • aqueous solution having a free acid content of 0.5 to 1.8 points and a total acid content of 15 to 35 points and Na + in that for adjustment the necessary amount of free acid is present.
  • a low-zinc process which has a defined iron (II) content.
  • iron (II) is oxidized to iron (III) and removed from the system as iron phosphate sludge. If the iron (II) content rises above the claimed level of 0.8 g / 1 in certain types of plants, the desired iron (II) can be added to the sludge elimination system through the targeted addition of hydrogen peroxide and / or potassium perganate.
  • -Value can be adjusted by the oxidation of iron (II) to iron (III).
  • the advantage of the process according to the invention is, in particular, that if the maximum limits for iron (II) mentioned and the use of a single accelerator, namely an organic oxidizing agent, are observed, no nitrous gases are formed. Nor do the problems which are usually extremely great in the prior art when using nitrate-free phosphating baths occur when using the process according to the invention.
  • the iron (II) concentration is determined continuously and / or discontinuously. Such analytical determinations are known to the person skilled in the art.
  • oxidizing agents especially in the sludge elimination system, an excessively high iron (II) concentration can be changed so that iron (III) is formed.
  • the precise control of the iron (II) content is an extremely important point of the present invention.
  • the present invention is therefore a zinc phosphating process which can be used in particular in the low zinc range. With the aid of this process, phosphate layers are produced which, in addition to zinc and iron, also contain nickel and manganese as cations.
  • the organic oxidizing agent to be used is selected according to the invention in such a way that it does not contribute or makes little contribution to the oxidation of iron (II) to iron (III). This is mainly used to depolarize the nascent hydrogen.
  • the chlorate- and nitrite-free process for producing zinc phosphate layers on steel, zinc and / or their alloys is modified by dipping, spray-dipping and / or dipping with an aqueous solution in such a way that an aqueous solution is obtained
  • the free acid content as well as the total acid content corresponds to the above as does the amount of sodium.
  • 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
  • a preferred embodiment of the present invention consists in limiting the upper limit of the concentration of iron (II) in the aqueous solution to less than or equal to 0.3 g / l. Atmospheric oxygen is primarily used for this. However, other oxidizing agents, such as hydrogen peroxide, oxygen and / or potassium permanganate, can in principle also be used.
  • the sodium salt of 3-nitrobenzenesulfonic acid is used as the preferred organic oxidizing agent.
  • alkaline detergents containing tensides in spraying and / or dipping (e.g. RIDOLINE C1250) at 50 to 60 ° C and treatment times of 1 to 5 minutes.
  • agents containing titanium salt e.g. FIXODINE C9I12
  • spraying or dipping at 20 to 40 ° C and treatment times of 30 to 180 s when used separately.
  • the activation stage can be omitted if this activating agent is added to the cleaning stage.
  • chrome-containing or chrome-free post-passivation agents e.g. DEOXYLYTE 41 or 80
  • spraying or dipping at 20 to 50 ° C and treatment times of 30 to 180 s.
  • Bath parameters spraying (A) spraying / dipping (B) dipping (C)
  • the iron (II) content in the bath solution was continuously increased by means of oxidizing agents such as hydrogen peroxide, potassium and / or sodium permanganate, ozone, oxygen and / or atmospheric oxygen or were added batchwise in the amounts required to adjust the iron (II) concentration, below the values given in Table 1.
  • oxidizing agents such as hydrogen peroxide, potassium and / or sodium permanganate, ozone, oxygen and / or atmospheric oxygen
  • Corrosion tests in an alternating climate according to VW standard P 1210 were carried out with the test sheet using the application types (B) spray-immersion and (C) immersion with a test period of 30/60 days: (The standard KET-Pri er FT 85 7042 was used as the coating , Manufacturer BASF Paints and Varnishes, related)
  • Z hot-dip galvanized steel, coating 10 ⁇ m on both sides
  • blistering that occurs in paints is defined by specifying the degree of blistering.
  • the degree of blistering according to this standard is a measure of a blistering that has occurred on a coating according to the frequency of the blisters per unit area and size of the blisters.
  • the degree of bubbles is indicated by a code letter and a code number for the frequency of the bubbles per unit area, as well as a code letter and a code number for the size of the bubbles.
  • the code letter and the code mO means no bubbles, while m5 defines a certain frequency of bubbles per unit area according to the degree of bubbles according to DIN 53 209.
  • the size of the bubbles is given the code letter g and the code number in the range from 0 to 5.
  • the code letter and code number gO has the meaning - no bubbles - while g5 is shown in accordance with the size of the bubbles in accordance with the degree of bubbles in DIN 53 209.
  • the degree of blistering is determined, the image of which is most similar to the appearance of the coating.
  • the salt spray test according to this standard serves to determine the behavior of paints, coatings and similar coatings when exposed to sprayed sodium chloride solution. If the coating has weak points, pores or injuries, the coating is preferably infiltrated from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic substrate.
  • the salt spray test is used so that such errors can be recognized and the infiltration can be determined.
  • Infiltration within the meaning of this standard is the penetration of sodium chloride solution into the interface between coating and substrate or into the interface between individual coatings starting from a defined point of injury (crack) or from existing weak points (e.g. pores, edges)
  • the width of the zone with reduced or lost adhesion serves as a measure of the resistance of the coating on the respective substrate to the action of sprayed sodium chloride solution.
  • the VW standard P-VW 1210 is an alternating test that consists of a combination of different standardized test methods.
  • a test cycle is maintained which consists of a 4-hour salt spray test in accordance with DIN 50021, a 4-hour rest period at room temperature and a 16-hour condensation water constant in accordance with DIN 50017.
  • test bone is bombarded with a defined amount of steel shot with a certain grain size distribution. After the test period has expired, a key figure is assigned to the degree of corrosion.
  • the key figure 1 denotes an invisible corrosion, while with a key figure 10 the entire surface is practically corroded.

Landscapes

  • 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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Cosmetics (AREA)

Abstract

PCT No. PCT/EP90/00592 Sec. 371 Date Dec. 10, 1991 Sec. 102(e) Date Dec. 10, 1991 PCT Filed Apr. 14, 1990 PCT Pub. No. WO90/12901 PCT Pub. Date Nov. 1, 1990.The invention concerns a process, not using chlorate or nitrite, for the production of nickel and manganese containing zinc phosphate films on steel, zinc, and/or zinc alloys by spraying, spray-dipping, and/or dipping, using an aqueous solution. An organic oxidizing agent is added, primarily to depolarize the nascent hydrogen produced.

Description

Chlorat- und nitritfreies Verfahren zur Herstellung von nicke!- und manqanhaltiqen ZinkphosphatschichtenChlorate- and nitrite-free process for the production of nickel! And man-made zinc phosphate layers
Die vorliegende Erfindung betrifft ein Verfahren zur Phosphatierung von Metalloberflächen, insbesondere ein Verfahren zur Herstellung von mangan- und nickelhaltigen Zinkphosphatschichten auf Stahl, Zink und/oder deren Legierungen. Diese nickel- und manganhaltigen Zinkphosphatschichten werden durch Spritzen, Spritztauchen und Tau¬ chen mit wäßrigen Lösungen aufgebracht.The present invention relates to a method for phosphating metal surfaces, in particular a method for producing manganese and nickel-containing zinc phosphate layers on steel, zinc and / or their alloys. These nickel and manganese-containing zinc phosphate layers are applied by spraying, splash-dipping and dipping with aqueous solutions.
Verfahren zum Phosphatieren von Oberflächen aus Eisen, Stahl, Zink und deren Legierungen sowie Aluminium sind seit langem Stand der Technik (Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, Band 15, Seiten 686 und 687). Das Phosphatieren der genannten Ober¬ flächen dient zur Erhöhung der Haftfestigkeit von Lackschichten und zur Verbesserung des Korrosionsschutzes.Processes for phosphating surfaces made of iron, steel, zinc and their alloys as well as aluminum have long been state of the art (Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 15, pages 686 and 687). Phosphating the surfaces mentioned serves to increase the adhesive strength of lacquer layers and to improve corrosion protection.
Die größte Bedeutung als Phosphatierverfahren besitzen saure Zink- und Alkaliphosphatlösungen. Zinkphosphatierbäder können beispiels¬ weise Monozinkphosphat, freie Phosphorsäure, Zinknitrat und Oxida¬ tionsmittel als Hauptkomponenten enthalten. Der pH-Wert solcher Lösungen liegt üblicherweise im Bereich zwischen 2,8 und 3,4. Der Verfahrensablauf besteht aus im wesentlichen zwei Reaktionen: der Beizreaktion und der Bildung einer Zinkphosphatschicht auf der zu phosphatierenden Oberfläche.Acidic zinc and alkali phosphate solutions are of the greatest importance as phosphating processes. Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components. The pH of such solutions is usually in the range between 2.8 and 3.4. The process consists essentially of two reactions: the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
Aus W.A. Roland und K.-H. Gottwald, "Metalloberflache", 42. Jahr¬ gang 1988/6 sind manganmodifizierte Zinkphosphatüberzüge als Haf¬ tungsgrund für moderne Lackierungen bekannt. Hier wird ausgeführt, daß der Einsatz von Manganionen neben Zink- und Nickelionen in Niedrigzink-Phosphatierverfahren den Korrosionsschutz nachweislich verbessert, insbesondere bei der Verwendung oberflächenveredelter Feinbleche. Der Einbau von Mangan in die Zinkphosphatüberzüge führt zu kleineren und kompakteren Kristallen mit erhöhter Alkalistabili¬ tät. Gleichzeitig wird die Arbeitsbreite von Phosphatierbädern er¬ höht; auch Aluminium kann im Verbund mit Stahl und verzinktem Stahl schichtbildend phosphatiert werden, wobei der allgemein erreichte Qualitätsstandard gewährleistet ist.From WA Roland and K.-H. Gottwald, "Metalloberflache", 42nd year 1988/6, manganese-modified zinc phosphate coatings are known as a liability for modern coatings. Here it is stated that the use of manganese ions in addition to zinc and nickel ions in Low-zinc phosphating processes have been shown to improve corrosion protection, especially when using surface-coated sheet metal. The incorporation of manganese into the zinc phosphate coatings leads to smaller and more compact crystals with increased alkali stability. At the same time, the working width of phosphating baths is increased; Aluminum can also be phosphated in combination with steel and galvanized steel to form a layer, whereby the generally achieved quality standard is guaranteed.
Die Phosphatierung unter Zusatz von Oxidationsmittel ist in der Automobilindustrie seit langem Stand der Technik. Im Kaltformge¬ bungssektor werden dagegen eine Reihe von Verfahren auf der Eisen¬ seite, d.h. mit einem erhöhten Gehalt an Eisen(II) ohne Zusatz Sauerstoffabgebender Beschleuniger betrieben.Phosphating with the addition of oxidizing agents has long been state of the art in the automotive industry. In the cold forming sector, on the other hand, a number of processes on the iron side, i.e. operated with an increased iron (II) content without the addition of oxygen-releasing accelerators.
Der Nachteil üblicher im Stand der Technik verwendeter Phosphatier- bäder besteht insbesondere in der Verwendung von Nitriten und/oder Chloraten als Beschleuniger der Phosphatierungsreaktion. Die bei der Verwendung von Nitriten entstehenden nitrosen Gase führen be¬ kanntermaßen zu einer Beeinträchtigung der Verwendbarkeit derarti¬ ger* Bäder.The disadvantage of conventional phosphating baths used in the prior art is in particular the use of nitrites and / or chlorates as accelerators of the phosphating reaction. The result produced during the use of nitrites nitrous gases be¬ can purportedly to impairment of usability derarti¬ ger * bathrooms.
Die Aufgabe der vorliegenden Erfindung bestand darin, ein sowohl πitrit- als auch chloratfreies Phosphatierungsverfahren zur Ver¬ fügung zu stellen, das insbesondere keine sogenannten "Stippen" verursacht. Hierunter werden zum einen Aufwachsungen von Zinksalzen verstanden, die im englischen Sprachgebrauch als "white staining" bezeichnet und durch die Reinigerlösung verursacht werden. Zum an¬ deren entstehen bei der Phosphatierung kraterförmige Öffnungen, die in der englischen Terminologie als "nubbing" bekannt sind. Die üb¬ licherweise benutzten Systeme enthalten als Beschleuniger Chlorat, Bro at, Nitrat, Nitrit, Peroxid und/oder organische Nitroverbindungen, wie 3-Nitrobenzolsulfonat. 3-Nitrobeπzolsulfonat wurde bisher nach dem Stand der Technik allgemein zusammen mit Chlorat- und/oder Nitritbeschleunigern eingesetzt. Das üblicherweise verwendete System 3-Nitrobenzolsulfonsäure/Chlorat erzeugt jedoch bei Anwesenheit von Nitrat auf elektrolytisch verzinktem Stahl die obengenannten Stippen, so daß üblicherweise nitratfrei gearbeitet werden muß.The object of the present invention was to provide a phosphating process which is free of both nitrite and chlorate and which, in particular, does not cause so-called "specks". This means, on the one hand, growths of zinc salts, which are referred to in English as "white staining" and are caused by the cleaning solution. On the other hand, during the phosphating, crater-shaped openings are created, which are known in the English terminology as "nubbing". The systems usually used contain chlorate, broat, nitrate, nitrite, peroxide and / or organic accelerators Nitro compounds such as 3-nitrobenzenesulfonate. 3-Nitrobeπzolsulfonat has been generally used in the prior art together with chlorate and / or nitrite accelerators. However, the 3-nitrobenzenesulfonic acid / chlorate system usually used produces the abovementioned specks in the presence of nitrate on electrolytically galvanized steel, so that it is usually necessary to work without nitrates.
Die vorstehend genannte Aufgabe wird gelöst durch ein chlorat- und nitritfreies Verfahren zur Herstellung von nickel- und manganhalti- gen Zinkphosphatschichten auf Stahl, Zink und/oder deren Legierun¬ gen durch Spritzen, Spritztauchen und/oder Tauchen mit einer wäßri¬ gen Lösung enthaltendThe above-mentioned object is achieved by a chlorate- and nitrite-free process for the production of nickel and manganese-containing zinc phosphate layers on steel, zinc and / or their alloys by spraying, splash-dipping and / or dipping with an aqueous solution
0,3 bis 1,5 g/1 Zink(II),0.3 to 1.5 g / 1 zinc (II),
0,01 bis 2,0 g/1 Mangan(II),0.01 to 2.0 g / 1 manganese (II),
0,01 bis 0,8 g/1 Eisen(II),0.01 to 0.8 g / 1 iron (II),
0,3 bis 2,0 g/1 Nickel(II), 10,0 bis 20,0 g/1 Phosphat-Ionen,0.3 to 2.0 g / 1 nickel (II), 10.0 to 20.0 g / 1 phosphate ions,
2,0 bis 10,0 g/1 Nitrat-Ionen und2.0 to 10.0 g / 1 nitrate ions and
0,1 bis 2,0 g/1 eines organischen Oxidationsmittels, wobei die wäßrige Lösung einen Gehalt an freier Säure von 0,5 bis 1,8 Punkten und einen Gesamtsäuregehalt von 15 bis 35 Punkten auf¬ weist und Na+ in der zur Einstellung der freien Säure notwendigen Menge vorhanden ist.0.1 to 2.0 g / l of an organic oxidizing agent, the aqueous solution having a free acid content of 0.5 to 1.8 points and a total acid content of 15 to 35 points and Na + in that for adjustment the necessary amount of free acid is present.
Gemäß der vorliegenden Erfindung wird somit ein Niedrigzink-Ver¬ fahren beschrieben, das einen definierten Gehalt an Eisen(II) auf¬ weist. Durch den Kontakt der Badlösung mit Luftsauerstoff beim Um¬ wälzen und Spritzen wird ein Teil dieses Eisen(II) zu Eisen(III) oxidiert und als Eisenphosphatschlamm dem System entzogen. Falls bei bestimmten Anlagetypen der Eisen(II)-Gehalt über das be¬ anspruchte Maß von 0,8 g/1 ansteigt, kann im Schlamm-Elimiπations- syste durch gezielte Zugabe von Wasserstoffperoxid und/oder Kal umper anganat der gewünschte Eisen(II)-Wert durch die Oxidation von Eisen(II) zu Eisen(III) eingestellt werden.According to the present invention, a low-zinc process is thus described which has a defined iron (II) content. When the bath solution comes into contact with atmospheric oxygen during circulation and spraying, some of this iron (II) is oxidized to iron (III) and removed from the system as iron phosphate sludge. If the iron (II) content rises above the claimed level of 0.8 g / 1 in certain types of plants, the desired iron (II) can be added to the sludge elimination system through the targeted addition of hydrogen peroxide and / or potassium perganate. -Value can be adjusted by the oxidation of iron (II) to iron (III).
Der Vorteil des erfindungsgemäßen Verfahrens besteht insbesondere darin, daß bei Einhaltung der genannten Höchstgrenzen für Eisen(II) und der Verwendung eines einzigen Beschleunigers, nämlich eines organischen Oxidations ittels, keine Bildung von nitrosen Gasen stattfindet. Auch treten die nach dem Stand der Technik üblicher¬ weise außerordentlich großen Probleme bei der Verwendung von ni¬ tratfreien Phosphatierbädern bei der Anwendung des erfindungsge¬ mäßen Verfahrens nicht auf. Bei der Anwendung des erfindungsgemäßen Verfahrens wird die Eisen(II)-Konzentration kontinuierlich und/oder diskontinuierlich bestimmt. Derartige analytische Bestimmungen sind dem Fachmann bekannt. Durch Anwendung von Oxidationsmitteln, insbe¬ sondere im Schlammeliminationssystem, kann eine zu hohe Eisen(II)- Konzentration dahingehend verändert werden, daß Eisen(III) gebildet wird. Somit ist die genaue Kontrolle des Eisen(II)-Gehalts ein außerordentlich wesentlicher Punkt der vorliegenden Erfindung.The advantage of the process according to the invention is, in particular, that if the maximum limits for iron (II) mentioned and the use of a single accelerator, namely an organic oxidizing agent, are observed, no nitrous gases are formed. Nor do the problems which are usually extremely great in the prior art when using nitrate-free phosphating baths occur when using the process according to the invention. When using the method according to the invention, the iron (II) concentration is determined continuously and / or discontinuously. Such analytical determinations are known to the person skilled in the art. By using oxidizing agents, especially in the sludge elimination system, an excessively high iron (II) concentration can be changed so that iron (III) is formed. Thus, the precise control of the iron (II) content is an extremely important point of the present invention.
Bei der vorliegenden Erfindung handelt es sich somit um ein Zink- phosphatierverfahren, das insbesondere im Niedrigzinkbereich ein¬ gesetzt werden kann. Mit Hilfe dieses Verfahrens werden Phosphat¬ schichten erzeugt, die als Kationen neben Zink und Eisen auch Nickel und Mangan enthalten.The present invention is therefore a zinc phosphating process which can be used in particular in the low zinc range. With the aid of this process, phosphate layers are produced which, in addition to zinc and iron, also contain nickel and manganese as cations.
Das einzusetzende organische Oxidationsmittel wird erfindungsgemäß derart ausgewählt, daß es nicht oder nur wenig zur Oxidation von Eisen(II) zu Eisen(III) beiträgt. Dieses dient hauptsächlich zur Depolarisierung des naszierenden Wasserstoffes. Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung wird das chlorat- und nitritfreie Verfahren zur Herstellung von Zinkphosphatschichten auf Stahl, Zink und/oder deren Legierungen durch Tauchen, Spritztauchen und/oder Tauchen mit einer wäßrigen Lösung derart modifiziert, daß man eine wäßrige Lösung enthaltendThe organic oxidizing agent to be used is selected according to the invention in such a way that it does not contribute or makes little contribution to the oxidation of iron (II) to iron (III). This is mainly used to depolarize the nascent hydrogen. According to a preferred embodiment of the present invention, the chlorate- and nitrite-free process for producing zinc phosphate layers on steel, zinc and / or their alloys is modified by dipping, spray-dipping and / or dipping with an aqueous solution in such a way that an aqueous solution is obtained
0,8 bis 1,0 g/1 Zink(II),0.8 to 1.0 g / 1 zinc (II),
0,8 bis 1,0 g/1 Mangan(II),0.8 to 1.0 g / 1 manganese (II),
0,2 bis 0,4 g/1 Eisen(II),0.2 to 0.4 g / 1 iron (II),
0,5 bis 0,7 g/1 Nickel(II), 12,0 bis 16,0 g/1 Phosphat-Ionen,0.5 to 0.7 g / 1 nickel (II), 12.0 to 16.0 g / 1 phosphate ions,
3,0 bis 6,0 g/1 Nitrat-Ionen und3.0 to 6.0 g / 1 nitrate ions and
0,3 bis 0,8 g/1 eines organischen Oxidations ittels einsetzt. Der Gehalt an freier Säure sowie der Gesamtsäuregehalt entspricht dem oben genannten ebenso wie die Menge an Natrium.0.3 to 0.8 g / 1 of an organic oxidizing agent. The free acid content as well as the total acid content corresponds to the above as does the amount of sodium.
Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung wird als organisches Oxidationsmittel 3-Nitrobenzolsulfonsäure ein¬ gesetzt.According to a preferred embodiment of the present invention, 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
Eine bevorzugte Ausführungsform der vorliegenden Erfindung besteht darin, daß man die Obergrenze der Konzentration an Eisen(II) in der wäßrigen Lösung auf weniger oder gleich 0,3 g/1 begrenzt. Hierzu wird in erster Linie Luftsauerstoff eingesetzt. Jedoch sind prin¬ zipiell auch andere Oxidationsmittel, wie Wasserstoffperoxid, Sauerstoff und/oder Kaliumpermanganat, einsetzbar.A preferred embodiment of the present invention consists in limiting the upper limit of the concentration of iron (II) in the aqueous solution to less than or equal to 0.3 g / l. Atmospheric oxygen is primarily used for this. However, other oxidizing agents, such as hydrogen peroxide, oxygen and / or potassium permanganate, can in principle also be used.
Als bevorzugtes organisches Oxidationsmittel wird das Natriumsalz der 3-Nitrobenzolsulfonsäure eingesetzt.The sodium salt of 3-nitrobenzenesulfonic acid is used as the preferred organic oxidizing agent.
Beispiele von BadzusammensetzunqenExamples of bath compositions
Innerhalb der üblichen Prozeßfolge mit den Stufen: 1. Reinigen und Entfetten:Within the usual process sequence with the stages: 1.Cleaning and degreasing:
Verwendung von tensidhaltigen alkalischen Reinigungsmitteln im Spritzen und/oder Tauchen (z.B. RIDOLINE C1250) bei 50 bis 60 °C und Behandlungszeiten von 1 bis 5 min.Use of alkaline detergents containing tensides in spraying and / or dipping (e.g. RIDOLINE C1250) at 50 to 60 ° C and treatment times of 1 to 5 minutes.
2. Spülen2. Rinse
3. Aktivieren:3. Activate:
Verwendung von titansalzhaltigen Mitteln (z.B. FIXODINE C9I12) im Spritzen oder Tauchen bei 20 bis 40 °C und Be¬ handlungszeiten von 30 bis 180 s bei separater Anwendung. Die Aktivierungsstufe kann entfallen, wenn dieses aktivie¬ rende Mittel der Reinigungsstufe zugesetzt wird.Use of agents containing titanium salt (e.g. FIXODINE C9I12) in spraying or dipping at 20 to 40 ° C and treatment times of 30 to 180 s when used separately. The activation stage can be omitted if this activating agent is added to the cleaning stage.
4. Phosphatieren:4. Phosphating:
Zusammensetzung siehe Tabelle 1.For composition, see table 1.
5. Spülen5. Rinse
6. Nachpassivieren:6. Post-passivation:
Verwendung von chromhaltigen oder chromfreien Nachpassivierungsmitteln (z.B. DEOXYLYTE 41 oder 80) im Spritzen oder Tauchen bei 20 bis 50 °C und Behandlungszeiten von 30 bis 180 s.Use of chrome-containing or chrome-free post-passivation agents (e.g. DEOXYLYTE 41 or 80) in spraying or dipping at 20 to 50 ° C and treatment times of 30 to 180 s.
7. VE-Spülen7. VE flushing
erfolgte die Oberflächenbehandlung bei folgenden Bedingungen: Tabelle 1the surface treatment was carried out under the following conditions: Table 1
PhosphatierungPhosphating
A p p l i k a t i o n s a r tA p p l i k a t i o n s a r t
Badparameter Spritzen(A) Spritz-/Tauchen(B) Tauchen(C)Bath parameters spraying (A) spraying / dipping (B) dipping (C)
FS1) (Punkte) 0,7 1,1 1,3FS 1 ) (points) 0.7 1.1 1.3
GS2) (Punkte) 20 22 26GS 2 ) (points) 20 22 26
Zn + gi-1 0,8 0,9 1,0Zn + gi-1 0.8 0.9 1.0
Mn2+ gl"1 0,8 0,8 0,8Mn 2+ gl " 1 0.8 0.8 0.8
Ni2+ gl"1 0,6 0,6 0,6Ni 2+ gl " 1 0.6 0.6 0.6
Fe2+ gl-1 0,2 0,2 0,3Fe 2+ gl-1 0.2 0.2 0.3
P03- gl-1 12,6 14,0 15,8P03-gl-1 12.6 14.0 15.8
MBS3) gl"1 0,3 0,4 0,5MBS 3 ) gl "1 0.3 0.4 0.5
Temp. °C 50 52 54Temp. ° C 50 52 54
Zeit s 90 30 S/180 T 180Time s 90 30 S / 180 T 180
1) FS = Freie Säure ) GS = Gesamtsäure1) FS = free acid) GS = total acid
3) MBS = 3-Nitrobenzolsulfonsäure, Na-Salz3) MBS = 3-nitrobenzenesulfonic acid, Na salt
Mit den oben genannten Varianten Spritzen (A), Spritz-Tauchen (B) und Tauchen (C) wurden flächenbezogene Massen der Phosphatschicht von 1,3 bis 2,5 gm-2 erzeugt. Bei der Applikationsart (B) wurde nach 30 s Spritzen 180 s getaucht.With the above-mentioned variants spraying (A), spray-immersion (B) and immersion (C), area-based masses of the phosphate layer of 1.3 to 2.5 gm -2 were generated. For application type (B), immersion was carried out for 180 s after 30 s of spraying.
Der Eisen(II)-Gehalt in der Badlösung wurde mittels Oxidationsmit¬ tel wie Wasserstoffperoxid, Kalium- und/oder Natriumpermanganat, Ozon, Sauerstoff und/oder Luftsauerstoff, welche kontinuierlich oder diskontinuierlich in den erforderlichen Mengen zur Einstellung der Eisen(II)-Konzentration zugegeben wurden, unterhalb der in Tabelle 1 genannten Werte limitiert.The iron (II) content in the bath solution was continuously increased by means of oxidizing agents such as hydrogen peroxide, potassium and / or sodium permanganate, ozone, oxygen and / or atmospheric oxygen or were added batchwise in the amounts required to adjust the iron (II) concentration, below the values given in Table 1.
Nach Applikationsart B behandelte Stahlbleche der Qualität St.1405 zeigen folgende Schichtzusammensetzung:Steel sheets of quality St.1405 treated according to application type B show the following layer composition:
52 % Hopeit (einschließlich Zn2Mn(P04)2 x 4 H2O)52% Hopeit (including Zn2Mn (P04) 2 x 4 H2O)
48 % Phosphophyllit.48% phosphophyllite.
Mit den mit Hilfe der Applikationsart (B) Spritz-Tauchen und (C) Tauchen erhaltenen Blechen wurden Korrosionstests im Wechselklima nach VW-Norm P 1210 mit 30/60 Tagen Prüfzeit durchgeführt: (Als Lackbeschichtung wurde der Standard KET-Pri er FT 85 7042, Hersteller BASF Farben und Lacke, verwandt)Corrosion tests in an alternating climate according to VW standard P 1210 were carried out with the test sheet using the application types (B) spray-immersion and (C) immersion with a test period of 30/60 days: (The standard KET-Pri er FT 85 7042 was used as the coating , Manufacturer BASF Paints and Varnishes, related)
Applikationsart BApplication type B
30 Tage 60 Tage30 days 60 days
CRSl) Z2) ZE3) CRS Z ZECRSl) Z 2 ) ZE3) CRS Z ZE
Fläche nachArea after
DIN 53209^) mO/gO mO/gO mO/gO mO/gO mO/gO mO/gODIN 53209 ^) mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO
Schnitt nachCut after
DIN- 53167 0,3 0,7 0,7 0,5 1,0 1,1 in mmDIN-53167 0.3 0.7 0.7 0.5 1.0 1.1 in mm
Steinschlag nach VW-Norm K 2 K 4 K 2 K 3 K 7 K 2 Applikationsart CStone chips according to VW standard K 2 K 4 K 2 K 3 K 7 K 2 Application type C
30 Tage 60 Tage30 days 60 days
CRS ) Z2) ZE3) CRS Z ZECRS) Z 2 ) ZE3) CRS Z ZE
Fläche nachArea after
DIN 53209 mO/gO mO/gO mO/gO mO/gO mO/gO mO/gODIN 53209 MO / GO MO / GO MO / GO MO / GO MO / GO MO / GO
Schnitt nachCut after
DIN 53167 0,3 0,4 0,5 0,5 0,6 0,5 in mmDIN 53167 0.3 0.4 0.5 0.5 0.6 0.5 in mm
Steinschlag nach VW-Norm K 2 K 3 K 1 K 3 K 6 K 2Stone chips according to VW standard K 2 K 3 K 1 K 3 K 6 K 2
1) CRS = kaltgewalzter Stahl St 14051) CRS = cold rolled steel St 1405
2) Z = schmelztauchverzinkter Stahl, Auflage 10 μm beidseitig 2 ) Z = hot-dip galvanized steel, coating 10 μm on both sides
3) ZE = elektrolytisch verzinkter Stahl, Auflage 7,5 μm beid¬ seitig3) ZE = electrolytically galvanized steel, coating 7.5 μm on both sides
4) Verhältnis von Blasengrad/Blasengröße 4 ) Bubble degree / bubble size ratio
Bei der Bestimmung des Blasengrades von Anstrichen gemäß DIN 53 209 wird eine bei Anstrichen auftretende Blasenbildung durch Angabe des Blasengrades definiert. Der Blasengrad nach dieser Norm ist ein Maß für eine an einem Anstrich aufgetretene Blasenbildung nach Häufig¬ keit der Blasen je Flächeneinheit und Größe der Blasen. Der Blasen¬ grad wird durch einen Kennbuchstaben und eine Kennzahl für die Häu¬ figkeit der Blasen je Flächeneinheit sowie einen Kennbuchstaben und eine Kennzahl für die Größe der Blasen angegeben. Der Kennbuchstabe und die Kennzahl mO bedeutet keine Blasen, während m5 entsprechend den Blasengradbildern gemäß der DIN 53 209 eine gewisse Häufigkeit der Blasen je Flächeneinheit definiert.When determining the degree of blistering of paints in accordance with DIN 53 209, blistering that occurs in paints is defined by specifying the degree of blistering. The degree of blistering according to this standard is a measure of a blistering that has occurred on a coating according to the frequency of the blisters per unit area and size of the blisters. The degree of bubbles is indicated by a code letter and a code number for the frequency of the bubbles per unit area, as well as a code letter and a code number for the size of the bubbles. The code letter and the code mO means no bubbles, while m5 defines a certain frequency of bubbles per unit area according to the degree of bubbles according to DIN 53 209.
Die Größe der Blasen wird mit dem Kennbuchstaben g und der Kennzahl im Bereich von 0 bis 5 versehen. Kennbuchstabe und Kennzahl gO hat die Bedeutung - keine Blasen - während g5 gemäß der Größe der Bla¬ sen entsprechend den Blasengradbildern der DIN 53 209 wiedergegeben ist.The size of the bubbles is given the code letter g and the code number in the range from 0 to 5. The code letter and code number gO has the meaning - no bubbles - while g5 is shown in accordance with the size of the bubbles in accordance with the degree of bubbles in DIN 53 209.
Durch Vergleich des Anstriches mit den Blasengradbildern wird der Blasengrad ermittelt, dessen Bild dem Aussehen des Anstrichs am ähnlichsten ist.By comparing the coating with the blistering images, the degree of blistering is determined, the image of which is most similar to the appearance of the coating.
Gemäß DIN 53 167 dient die Salzsprühnebelprüfung nach dieser Norm dazu, das Verhalten von Lackierungen, Anstrichen und ähnlichen Be¬ schichtungen bei Einwirkung versprühter Natriumchloridlösung zu ermitteln. Weist die Beschichtung Schwachstellen, Poren oder Ver¬ letzungen auf, dann findet von dort aus bevorzugt eine Unterwan¬ derung der Beschichtung statt. Dies führt zu einer Haftungsvermin¬ derung oder zu Haftungsverlust und Korrosion des metallischen Un¬ tergrundes.According to DIN 53 167, the salt spray test according to this standard serves to determine the behavior of paints, coatings and similar coatings when exposed to sprayed sodium chloride solution. If the coating has weak points, pores or injuries, the coating is preferably infiltrated from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic substrate.
Die Salzsprühnebelprüfung wird angewendet, damit solche Fehler er¬ kannt und die Unterwanderung ermittelt werden kann. Unterwanderung im Sinne dieser Norm ist das von einer definiert angebrachten Verletzungsstelle (Ritze) oder von vorhandenen Schwachstellen (z. B. Poren, Kanten) ausgehende Eindringen von Na¬ triumchloridlösung in die Grenzfläche zwischen Beschichtung und Untergrund oder in die Grenzfläche zwischen einzelnen Beschichtun¬ gen. Die Breite der Zone mit verminderter oder verlorener Haftung dient als Maß für die Widerstandsfähigkeit der Beschichtung auf dem jeweiligen Untergrund gegen das Einwirken versprühter Natriumchlo¬ ridlösung.The salt spray test is used so that such errors can be recognized and the infiltration can be determined. Infiltration within the meaning of this standard is the penetration of sodium chloride solution into the interface between coating and substrate or into the interface between individual coatings starting from a defined point of injury (crack) or from existing weak points (e.g. pores, edges) The width of the zone with reduced or lost adhesion serves as a measure of the resistance of the coating on the respective substrate to the action of sprayed sodium chloride solution.
Die VW-Norm P-VW 1210 stellt einen Wechseltest dar, der aus einer Kombination verschieden genormter Prüfverfahren besteht. So wird im Verlauf von im vorliegenden Fall 30/60 Tagen ein Prüfzyklus einge¬ halten, der besteht aus 4 h Salzsprüh-Test gemäß DIN 50021, 4 h Ruhezeit bei Raumtemperatur und 16 h Schwitzwasser-Konstantklima gemäß DIN 50017.The VW standard P-VW 1210 is an alternating test that consists of a combination of different standardized test methods. Thus, in the course of 30/60 days in the present case, a test cycle is maintained which consists of a 4-hour salt spray test in accordance with DIN 50021, a 4-hour rest period at room temperature and a 16-hour condensation water constant in accordance with DIN 50017.
Zu Beginn des Tests wird das Prüfgrät mit einer definierten Menge Stahlschrot bestimmter Korngrößenverteilung beschossen. Nach Ablauf der Prüfzeit wird dem Korrosionsgrad eine Kennzahl zugeordnet.At the beginning of the test, the test bone is bombarded with a defined amount of steel shot with a certain grain size distribution. After the test period has expired, a key figure is assigned to the degree of corrosion.
Entsprechend den Kennzahlen von 1 bis 10 bezeichnet die Kennzahl 1 eine nicht sichtbare Korrosion, während bei einer Kennzahl 10 prak¬ tisch die gesamte Oberfläche korrodiert ist. Corresponding to the key figures from 1 to 10, the key figure 1 denotes an invisible corrosion, while with a key figure 10 the entire surface is practically corroded.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Chlorat- und nitritfreies Verfahren zur Herstellung von nickel- und manganhaltigen Zinkphosphatschichten auf Stahl, Zink und/oder deren Legierungen durch Spritzen, Spritztauchen und/oder Tauchen mit einer wäßrigen Lösung enthaltend1. Chlorate- and nitrite-free process for the production of nickel and manganese-containing zinc phosphate layers on steel, zinc and / or their alloys by spraying, splash-dipping and / or dipping with an aqueous solution
0,3 bis 1,5 g/1 Zink(II),0.3 to 1.5 g / 1 zinc (II),
0,01 bis 2,0 g/1 Mangan(II),0.01 to 2.0 g / 1 manganese (II),
0,01 bis 0,8 g/1 Eisen(II),0.01 to 0.8 g / 1 iron (II),
0,3 bis 2,0 g/1 Nickel(II), 10",© bis 20,0 g/1 Phosphat-Ionen,0.3 to 2.0 g / 1 nickel (II), 10 " , © to 20.0 g / 1 phosphate ions,
2,0 bis 10,0 g/1 Nitrat-Ionen und2.0 to 10.0 g / 1 nitrate ions and
0,1 bis 2,0 g/1 eines organischen Oxidationsmittels, wobei die wäßrige Lösung einen Gehalt an freier Säure von 0,5 bis 1,8 Punkten und einen Gesamtsäuregehalt von 15 bis 35 Punkten auf¬ weist und Na+ in der zur Einstellung der freien Säure notwendigen Menge vorhanden ist.0.1 to 2.0 g / l of an organic oxidizing agent, the aqueous solution having a free acid content of 0.5 to 1.8 points and a total acid content of 15 to 35 points and Na + in that for adjustment the necessary amount of free acid is present.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die wä߬ rige Lösung2. The method according to claim 1, characterized in that the aqueous solution
0,8 bis 1,0 g/1 Zink(II),0.8 to 1.0 g / 1 zinc (II),
0,8 bis 1,0 g/1 Mangan(II),0.8 to 1.0 g / 1 manganese (II),
0,2 bis 0,4 g/1 Eisen(II),0.2 to 0.4 g / 1 iron (II),
0,5 bis 0,7 g/1 Nickel(II),0.5 to 0.7 g / 1 nickel (II),
12,0 bis 16,0 g/1 Phosphat-Ionen,12.0 to 16.0 g / 1 phosphate ions,
3,0 bis 6,0 g/1 Nitrat-Ionen und3.0 to 6.0 g / 1 nitrate ions and
0,3 bis 0,8 g/1 eines organischen Oxidationsmittels aufweist. 3. Verfahren nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß als organisches Oxidationsmittel 3-Nitrobenzolsulfonsäure einge¬ setzt wird.Has 0.3 to 0.8 g / 1 of an organic oxidizing agent. 3. Process according to claims 1 or 2, characterized in that 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die wäßrige Lösung weniger oder gleich 0,3 g/1 Eisen(II) enthält.4. Process according to Claims 1 to 3, characterized in that the aqueous solution contains less than or equal to 0.3 g / 1 iron (II).
5. Verfahren nach einem der Ansprüche 3 bis 4, dadurch gekenn¬ zeichnet, daß man das Natriumsalz der 3-Nitrobenzolsulfonsäure ein¬ setzt.5. The method according to any one of claims 3 to 4, characterized gekenn¬ characterized in that one uses the sodium salt of 3-nitrobenzenesulfonic acid.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekenn¬ zeichnet, daß man den Eisen(II)-Gehalt durch Oxidationsmittel ein¬ stellt, die ausgewählt sind aus Luftsauerstoff, Sauerstoff, Was¬ serstoffperoxid und/oder Kaliumpermanganat. 6. The method according to any one of claims 1 to 5, characterized gekenn¬ characterized in that one adjusts the iron (II) content by oxidizing agents, which are selected from atmospheric oxygen, oxygen, hydrogen peroxide and / or potassium permanganate.
EP19900906149 1989-04-21 1990-04-14 Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films Expired - Lifetime EP0469011B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3913089 1989-04-21
DE3913089A DE3913089A1 (en) 1989-04-21 1989-04-21 CHLORATE- AND NITRITE-FREE METHOD FOR THE PRODUCTION OF NICKEL- AND MANGANE-CONTAINING ZINC PHOSPHATE LAYERS
PCT/EP1990/000592 WO1990012901A1 (en) 1989-04-21 1990-04-14 Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films

Publications (2)

Publication Number Publication Date
EP0469011A1 true EP0469011A1 (en) 1992-02-05
EP0469011B1 EP0469011B1 (en) 1995-01-04

Family

ID=6379116

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900906149 Expired - Lifetime EP0469011B1 (en) 1989-04-21 1990-04-14 Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films

Country Status (9)

Country Link
US (1) US5312492A (en)
EP (1) EP0469011B1 (en)
JP (1) JPH04504881A (en)
AT (1) ATE116693T1 (en)
BR (1) BR9007301A (en)
CA (1) CA2053244A1 (en)
DE (2) DE3913089A1 (en)
ES (1) ES2066200T3 (en)
WO (1) WO1990012901A1 (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2111949T3 (en) * 1993-09-06 1998-03-16 Henkel Kgaa NICKEL-FREE PHOSPHATE PROCEDURE.
US5932292A (en) * 1994-12-06 1999-08-03 Henkel Corporation Zinc phosphate conversion coating composition and process
ATE226648T1 (en) * 1994-12-06 2002-11-15 Henkel Corp COMPOSITION AND METHOD FOR ZINC PHOSPHATE CONVERSION COATING
KR960023240A (en) * 1994-12-06 1996-07-18 사토미 유타카 Aqueous zinc phosphate treatment solution and treatment method
WO1996027693A1 (en) * 1995-03-07 1996-09-12 Henkel Corporation Composition and process for simultaneously cleaning and conversion coating metal surfaces
AU699822B2 (en) * 1995-03-07 1998-12-17 Henkel Corporation Composition and process for forming an underpaint coating on metals
US5888315A (en) * 1995-03-07 1999-03-30 Henkel Corporation Composition and process for forming an underpaint coating on metals
AU1407697A (en) * 1995-12-06 1997-06-27 Henkel Corporation Composition and process for zinc phosphate conversion coating
US6231688B1 (en) * 1995-12-06 2001-05-15 Henkel Corporation Composition and process for zinc phosphate conversion coating
WO2009017535A2 (en) * 2007-06-07 2009-02-05 Henkel Ag & Co. Kgaa High manganese cobalt-modified zinc phosphate conversion coating
EP2341164A1 (en) * 2008-09-17 2011-07-06 Hoden Seimitsu Kako Kenkyusho Co., Ltd. Aqueous solution for blackening chemical conversion treatment of zinc or zinc alloy surface and method for forming blackened antirust coating film using the aqueous solution for the treatment

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1258855A (en) * 1960-02-18 1961-04-21 Parker Ste Continentale Advanced process for phosphating metal surfaces
DE3101866A1 (en) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METALS
JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting
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
GB8329250D0 (en) * 1983-11-02 1983-12-07 Pyrene Chemical Services Ltd Phosphating processes
ATE99002T1 (en) * 1985-08-27 1994-01-15 Nippon Paint Co Ltd ACIDIC AQUEOUS PHOSPHATE COATING SOLUTIONS FOR A PROCESS FOR PHOSPHATE COATING METALLIC SURFACE.
DE3630246A1 (en) * 1986-09-05 1988-03-10 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COVER AND ITS APPLICATION
DE3712339A1 (en) * 1987-04-11 1988-10-20 Metallgesellschaft Ag METHOD FOR PHOSPHATIZING BEFORE ELECTROPLATING
DE3742634A1 (en) * 1987-12-16 1989-06-29 Collardin Gmbh Gerhard METHOD FOR THE COLLIGHTING OF PHOSPHATING BAEDERS AND DEVICE FOR THIS METHOD
ES2058464T3 (en) * 1988-02-03 1994-11-01 Metallgesellschaft Ag PROCEDURE FOR THE GENERATION OF PHOSPHATE COATING ON METALS.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9012901A1 *

Also Published As

Publication number Publication date
DE3913089A1 (en) 1990-10-25
CA2053244A1 (en) 1990-10-22
ES2066200T3 (en) 1995-03-01
WO1990012901A1 (en) 1990-11-01
JPH04504881A (en) 1992-08-27
ATE116693T1 (en) 1995-01-15
BR9007301A (en) 1991-12-10
DE59008202D1 (en) 1995-02-16
EP0469011B1 (en) 1995-01-04
US5312492A (en) 1994-05-17

Similar Documents

Publication Publication Date Title
EP0478648B1 (en) Process for producing zinc phosphate coatings containing manganese and magnesium
EP0633950B1 (en) Nickel-free phosphatization process
EP0064790A1 (en) Method of phosphating metals, as well as its use in the electrodip painting pretreatment
EP0717787B1 (en) Nickel-free phosphatization process
EP0469011B1 (en) Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films
DE3234558A1 (en) WATER-ACID ZINC PHOSPHATE COATING SOLUTIONS, LOW-TEMPERATURE METHODS USING SUCH SOLUTIONS FOR THE FORMATION OF CHEMICAL CONVERSION TRANSFORMERS ON IRON AND / OR ZINCO SURFACES AND THE USEFUL LIQUID DETERMINANT
EP0155547B1 (en) Process for the zinc-calcium phosphatizing of metal surfaces at a low treating temperature
EP0134895B1 (en) Process and compounds for applying accelerated and grain-refined phosphate coatings to metallic surfaces
DE3828676A1 (en) PHOSPHATING PROCESS
DE19808440C2 (en) Aqueous solution and method for phosphating metallic surfaces and use of the solution and method
EP0486576B1 (en) Process for producing manganese-containing zinc phosphate coatings on galvanized steel
EP0264811B1 (en) Process for producing phosphate coatings
EP0111223A1 (en) Process for phosphatizing metallic surfaces, and solutions for use therein
DE3927614A1 (en) METHOD OF GENERATING PHOSPHATURE SUPPLIES ON METALS
EP0121274A1 (en) Process for phosphating metal surfaces
DE69730711T2 (en) Manganese Phosphate Conversion Coating Composition and Method for Use at Moderate Temperatures
EP1019564A1 (en) Method for phosphatizing a steel strip
DE2213781C3 (en) Process for the phosphating of steel
EP1230423B1 (en) Method for applying manganese phosphate layers
DE2931693A1 (en) Phosphating soln. for metallic surfaces - contg. zinc and manganese phosphate and nitrate, chlorate and sodium nitrite accelerator, applied by spraying at low temp.
DE19504723C2 (en) Aqueous, acidic solution containing phosphate ions, process for phosphating metal surfaces and use of the solution
DE19905479A1 (en) Process for the phosphatisation of zinc or aluminum surfaces
DE2240049B2 (en) PROCESS FOR THE PRODUCTION OF PHOSPHATE COATINGS ON IRON AND STEEL AND CONCENTRATES FOR THE PRODUCTION AND ADDITION OF THE PHOSPHATIZING SOLUTION USED IN THIS SITE
EP0866888A1 (en) Method of phosphating metal surfaces
DE19541285C2 (en) Process and means for phosphating metal surfaces

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19911014

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19931216

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

REF Corresponds to:

Ref document number: 116693

Country of ref document: AT

Date of ref document: 19950115

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59008202

Country of ref document: DE

Date of ref document: 19950216

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2066200

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950405

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
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19960501

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19961231

Year of fee payment: 7

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: 19970414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980406

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19980415

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19980416

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19980428

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990409

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990414

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990414

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: 19990415

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19990426

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19990614

Year of fee payment: 10

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 NON-PAYMENT OF DUE FEES

Effective date: 19991101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990414

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19991101

EUG Se: european patent has lapsed

Ref document number: 90906149.1

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: 20000430

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 20000430

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: 20001229

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: 20010201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20040416

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050415

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20050415