EP0154384B1 - Process for pretreating zinc surfaces before lacquering - Google Patents
Process for pretreating zinc surfaces before lacquering Download PDFInfo
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- EP0154384B1 EP0154384B1 EP19850200318 EP85200318A EP0154384B1 EP 0154384 B1 EP0154384 B1 EP 0154384B1 EP 19850200318 EP19850200318 EP 19850200318 EP 85200318 A EP85200318 A EP 85200318A EP 0154384 B1 EP0154384 B1 EP 0154384B1
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- degreased
- cleaned
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Classifications
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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
- C23C22/78—Pretreatment of the material to be coated
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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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
Definitions
- the invention relates to a method for preparing metal surfaces made of zinc or zinc alloys for the subsequent application of paint, lacquer and the like. By means of alkaline cleaning and passivation through chemical conversion coatings.
- aqueous solutions to form conversion coatings which contain alkali, generally sodium hydroxide, cations of at least one metal other than alkali ions, preferably iron, cobalt and / or nickel, and at least one Contain complexing agents.
- the amount of the complexing agent should be sufficient to keep the aforementioned cations in solution in the alkaline medium from which they would precipitate as metal hydroxide without the complexing agent.
- the most frequently used complexing agents for this are sodium gluconate and sodium glucoheptonate.
- the solutions for producing the chemical conversion coating are usually applied by spraying at a temperature between 40 and 70 ° C. for a period of about 3 to 15 seconds.
- aqueous alkaline solutions for the formation of conversion coatings is associated with significant progress in terms of paint adhesion and corrosion resistance after painting, especially for strip and sheet metal.
- Industrial experience has also confirmed that it is interesting to subject the metal surface to a subsequent treatment with an aqueous acidic solution in accordance with FR-PS-1 487 183 after the formation of a conversion coating in an alkaline medium and water rinsing.
- Such solutions contain 0.001 to 0.25% by weight of chromium (III), 0.01 to 0.06% by weight of fluoride and 0.02 to 0.1% by weight of zinc. They are used in spraying or dipping for 2 to 10 seconds at a temperature between 40 and 70 ° C. The surfaces are then dried immediately so that they can then be painted or painted.
- the object of the present invention is to provide a method which avoids the disadvantages of the known, in particular the aforementioned methods, and which is associated with an improvement in the adhesion of paint, paint and the like and the corrosion resistance.
- the type and amount of alkaline Cleaning agents are preferably chosen such that the pH of the solution is 11.5 to 12.5.
- the alkaline cleaning agents can be hydroxides, phosphates, carbonates and borates of alkali metals with the exception of silicate. These components are usually used in a concentration of 3 to 150 g / l, preferably 7 to 9 g / l.
- the surfactants can in principle be anion-active, non-ionic, cation-active or amphoteric. They must be compatible in the alkaline medium and under the conditions of use of the solution. Your choice depends essentially on the pH of the cleaning and degreasing agent, the conditions of use, i. H. Dip or spray application, and economic considerations. For solutions used in the spray process, nonionic surfactants are preferred. Their concentration should be between 0.1 and 5 g / l, preferably about 1 g / l. Such surfactants can be used alone or in a mixture.
- the metal ions other than alkali ions can be selected from those mentioned in French Patent 1,411,272. These are in particular aluminum, antimony, silver, cadmium, cerium, chromium, cobalt, tin, iron (11 or III-valent), magnesium, manganese, molybdenum, nickel, titanium and tungsten. Cobalt, iron and nickel ions are preferred, especially nickel.
- the anion assigned to the cation for introduction should be compatible with the solution and should not have any adverse effect. For this reason, nitrate is preferably used to introduce the metal ions other than alkali ions.
- the concentration of the metal cations other than alkali ions in the solution depends on the concentration of the alkaline cleaning agent. The higher it is, the higher the concentration of cations should be.
- the concentration of cations other than alkali ions can be between 50 and 5000 mg / l, preferably between 100 and 1000 mg / l. With a concentration of the alkaline-reacting cleaning agent of approx. 10 g / l and a pH of the order of 12, the preferred range of the metal cations is 500 to 700 mg / l.
- the improvement can practically not be greater than that which is usually obtained with the preferred concentration of 500 to 700 mg / l. Due to the high pH, the conditions of use and the high content of cations other than alkali ions, the solution is not entirely sludge-free, which is not harmful, however, if the amount of sludge is small, i.e. is in the order of 2 to 3% by volume, based on the entire solution.
- the complexing agents used in the cleaning and degreasing solution can be the same as those described in FR-PS-1 411 272.
- it can be condensed phosphates, dicarboxylic acids, hydroxy carboxylic acids, benzene carboxylic acids, hydroxy aldehydes and amines.
- the best results in terms of degreasing the metal surface and complexing the metal ions can be achieved with sodium gluconate, sodium glucoheptonate, sorbitol and sodium ethylenediaminotetraacetate.
- the concentration of complexing agent should be sufficient to stabilize the metals other than alkali ions, taking into account their concentration and the pH of the solution in the solution.
- the concentration can range between 0.1 and 30 g / l. It is preferably 0.5 to 1 g / l.
- the aqueous alkaline solution for cleaning and degreasing the metal surface can be obtained by adding a solid concentrate which contains the alkaline-reacting cleaning agent or agents, the surfactant (s), the metal ions other than alkali ions and the complexing agent or agents.
- the solution can also be obtained if solid or liquid concentrates are used, one of which contains the alkaline detergent (s), the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent contains and the other of which contains the metal cations other than alkali ions, the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent.
- solid or liquid concentrates one of which contains the alkaline detergent (s), the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent contains and the other of which contains the metal cations other than alkali ions, the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent.
- the cleaning and degreasing solutions described above can be sprayed or dipped at a temperature in the range from 20 to 90 ° C., preferably from 45 to 65 °, for a period of from about 3 to 180 seconds, preferably from 10 to 30 seconds. be applied.
- the metal surface is then brought into contact with a solution which contains alkali, cations of at least one metal other than alkali ions and at least one complexing agent.
- a solution which contains alkali, cations of at least one metal other than alkali ions and at least one complexing agent can be, for example, a solution as described in FR-PS-1 411 272.
- the passivation solution can contain, for example, chromium-III and / or chromium-IV and have the properties described in FR-PS-1 487 183.
- a conversion coating can be created by applying a dispersion of chromic acid and / or chromium compound with colloidal silicon dioxide.
- the passivation solution applied for the passivation treatment is preferably dried.
- the metal surface treated in this way is then provided with paint, lacquer and the like.
- the inventive method is suitable for the surface treatment of objects which consist of zinc or zinc alloys or a coating of zinc or zinc alloys, such as. B. galvanized steel. It is particularly suitable for the treatment of sheet metal or strip.
- Hot-dip galvanized steel sheets were used to carry out the tests.
- the sheets were then rinsed with cold running water and containing a solution brought into contact. This was also done by spraying at a pressure of 1.5. 10 5 Pa for 10 sec, but at 65 ° C.
- the sheets were coated with a coating of alkyd resin or acrylate resin with a thickness of approx. 30 1 1 m. After drying, the sheets rested for 48 hours.
- Hot-dip galvanized steel sheets were treated according to the procedure in Example 1, but solutions of the following nature were used for cleaning and degreasing:
- the varnishes applied by the roller application process were of the following type: polyvinyl chloride, polyester, silicone-modified polyester, polyvinylidene and polyacrylate.
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Vorbereitung von Metalloberflächen aus Zink oder Zinklegierungen für die anschließende Aufbringung von Farbe, Lack und dergl. mittels alkalischer Reinigung und Passivierung durch chemische Umwandlungsüberzüge.The invention relates to a method for preparing metal surfaces made of zinc or zinc alloys for the subsequent application of paint, lacquer and the like. By means of alkaline cleaning and passivation through chemical conversion coatings.
Es ist seit langem bekannt, auf Oberflächen von Zink und Zinklegierungen sowie verzinktem Stahl einen Umwandlungsüberzug vor der Aufbringung von Lack und dergl. zu erzeugen. Insbesondere ist es aus der FR-PS-1 411 272 bekannt, zur Bildung von Umwandlungsüberzügen wäßrige Lösungen zu benutzen, die Alkali, im allgemeinen Natriumhydroxid, Kationen mindestens eines von Alkaliionen verschiedenen Metalles, vorzugsweise Eisen, Cobalt und/oder Nickel, und wenigstens einen Komplexbildner enthalten. Die Menge des Komplexbildners soll ausreichen, die vorgenannten Kationen im alkalischen Medium in Lösung zu halten, aus dem sie ohne Komplexbildner als Metallhydroxid ausfallen würden. Die hierzu am häufigsten verwendeten Komplexbildner sind Natriumgluconat und Natriumglucoheptonat. Die Lösungen zur Erzeugung des chemischen Umwandlungsüberzuges werden üblicherweise durch Spritzen bei einer Temperatur zwischen 40 und 70°C während einer Zeitdauer von etwa 3 bis 15 sec appliziert.It has long been known to produce a conversion coating on surfaces of zinc and zinc alloys as well as galvanized steel before the application of paint and the like. In particular, it is known from FR-PS-1 411 272 to use aqueous solutions to form conversion coatings which contain alkali, generally sodium hydroxide, cations of at least one metal other than alkali ions, preferably iron, cobalt and / or nickel, and at least one Contain complexing agents. The amount of the complexing agent should be sufficient to keep the aforementioned cations in solution in the alkaline medium from which they would precipitate as metal hydroxide without the complexing agent. The most frequently used complexing agents for this are sodium gluconate and sodium glucoheptonate. The solutions for producing the chemical conversion coating are usually applied by spraying at a temperature between 40 and 70 ° C. for a period of about 3 to 15 seconds.
Der industrielle Einsatz derartiger wäßriger alkalischer Lösungen zur Bildung von Umwandlungeüberzügen ist mit einem deutlichen Fortschritt unter dem Gesichtspunkt der Lackhaftung und des Korrosionswiderstandes nach einer Lackierung, insbesondere für Band und Blech, verbunden. Die industrielle Erfahrung hat zudem bestätigt,-daß es interessant ist, die Metalloberfläche - nach der Erzeugung eines Umwandlungsüberzuges in alkalischem Medium und Wasserspülung - einer Folgebehandlung mit einer wäßrigen, sauren Lösung entsprechend der FR-PS-1 487 183 zu unterwerfen. Derartige Lösungen enthalten 0,001 bis 0,25 Gew.-% Chrom(III), 0,01 bis 0,06 Gew.-% Fluorid und 0,02 bis 0,1 Gew.-% Zink. Sie werden im Spritzen oder Tauchen während 2 bis 10 sec bei einer Temperatur zwischen 40 und 70°C angewendet. Danach werden die Oberflächen unverzüglich getrocknet, um anschließend mit Lack oder Farbe versehen zu werden.The industrial use of such aqueous alkaline solutions for the formation of conversion coatings is associated with significant progress in terms of paint adhesion and corrosion resistance after painting, especially for strip and sheet metal. Industrial experience has also confirmed that it is interesting to subject the metal surface to a subsequent treatment with an aqueous acidic solution in accordance with FR-PS-1 487 183 after the formation of a conversion coating in an alkaline medium and water rinsing. Such solutions contain 0.001 to 0.25% by weight of chromium (III), 0.01 to 0.06% by weight of fluoride and 0.02 to 0.1% by weight of zinc. They are used in spraying or dipping for 2 to 10 seconds at a temperature between 40 and 70 ° C. The surfaces are then dried immediately so that they can then be painted or painted.
Die industrielle Nutzung dieser Verfahren hat gezeigt, welche Bedeutung die Zusammensetzung der Produkte hat, die in der Stufe der Reinigung und Entfettung der Metalloberfläche im alkalischen Medium verwendet werden, die ihrerseits vor den Stufen der Erzeugung des chemischen Umwandlungsüberzuges und der Nachbehandlung - wie vorstehend beschrieben - durchgeführt werden müssen.The industrial use of these processes has shown the importance of the composition of the products used in the step of cleaning and degreasing the metal surface in the alkaline medium, which in turn before the steps of producing the chemical conversion coating and the after-treatment - as described above - must be carried out.
Zwar ist es aus der FR-PS-1 496 683 bekannt, daß eine wesentliche, an die Stufe der alkalischen Entfettung gestellte Bedingung darin besteht, die Bildung des Umwandlungsüberzuges nicht zu inhibieren und daher mit silikatfreien Reinigerlösungen zu arbeiten. Mit Rücksicht auf die Anforderungen der Industrie im Sinne einer stetigen Verbesserung der Qualität der Erzeugnisse wird jedoch selbst bei einer Arbeitsweise entsprechend der FR-PS-1 496 683 eine Lackhaftung und ein Korrosionsschutz erzielt, der für bestimmte Arten von Metalloberflächen und insbesondere für feuerverzinkten Stahl an der Grenze des Akzeptablen liegt.It is known from FR-PS-1 496 683 that an essential condition placed on the stage of alkaline degreasing is not to inhibit the formation of the conversion coating and therefore to work with silicate-free cleaning solutions. With regard to the requirements of the industry in the sense of a constant improvement in the quality of the products, however, even with a method of operation in accordance with FR-PS-1 496 683, paint adhesion and corrosion protection are achieved which apply to certain types of metal surfaces and in particular to hot-dip galvanized steel is the limit of what is acceptable.
Das Studium der diversen beobachteten Probleme hat auch den nachteiligen Einfluß bestimmter Zusätze zu Feuerverzinkungsbädern auf die Grenzfläche Metalloberfläche/Behandlungslösung zum Zeitpunkt der Vorbereitung der Oberfläche, der Bildung des chemischen Umwandlungsüberzuges und der Nachbehandlung deutlich gemacht. Das ist insbesondere der Fall für bestimmte Metalle, wie Aluminium, Zinn und Blei.The study of the various problems observed has also highlighted the adverse impact of certain additives to hot dip galvanizing baths on the metal surface / treatment solution interface at the time of surface preparation, chemical conversion coating formation, and post-treatment. This is particularly the case for certain metals, such as aluminum, tin and lead.
Es ist bekannt, daß die Anreicherung derartiger verunreinigender Metalle auf der Oberfläche von Zink oder von verzinkten Teilen die die Behandlung begleitende Beizreaktion im alkalischen Medium stört. Man hat versucht, Abhilfe zu schaffen, indem die Konzentration an Alkali erhöht und und damit der oberflächige Beizangriff auf die Zinkoberfläche verstärkt wurde. Jedoch wurde im Ergebnis nur eine Verschärfung der bereits festgestellten Mängel, insbesondere hinsichtlich der Haftung des Lackes und dergl., erzielt.It is known that the accumulation of such contaminating metals on the surface of zinc or of galvanized parts interferes with the pickling reaction accompanying the treatment in the alkaline medium. An attempt has been made to remedy this by increasing the concentration of alkali and thus increasing the surface pickling attack on the zinc surface. However, the result was only an exacerbation of the deficiencies already identified, in particular with regard to the liability of the paint and the like.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren bereitzustellen, das die Nachteile der bekannten, insbesondere der vorgenannten Verfahren vermeidet und mit einer Verbesserung der Haftung von Lack, Farbe und dergl. und des Korrosionswiderstandes verbunden ist.The object of the present invention is to provide a method which avoids the disadvantages of the known, in particular the aforementioned methods, and which is associated with an improvement in the adhesion of paint, paint and the like and the corrosion resistance.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberfläche
- a) mit einer silikatfreien Lösung reinigt und entfettet, die wenistens ein alkalisch reagierendes Reinigungsmittel, wenigstens ein Tensid, Kationen wenigstens eines von Alkaliionen verschiedenen Metalles und wenigstens einen Komplexbildner in einer Menge, die ausreicht, die Metallkationen in Lösung zu stabilisieren, enthält,
- b) mit Wasser spült,
- c) mit einer Lösung in Berührung bringt, die Alkali, Kationen von wenigstens einem von Alkaliionen verschiedenen Metall und mindestens einen Komplexbildner enthält,
- d) mit Wasser spült und
- e) anschließend mit einer sauren Passivierungslösung behandelt.
- a) cleans and degreases with a silicate-free solution which contains at least one alkaline-reacting cleaning agent, at least one surfactant, cations of at least one metal other than alkali ions and at least one complexing agent in an amount sufficient to stabilize the metal cations in solution,
- b) rinsed with water,
- c) in contact with a solution which contains alkali, cations of at least one metal other than alkali ions and at least one complexing agent,
- d) rinsing with water and
- e) then treated with an acidic passivation solution.
Die Art und Menge des alkalisch reagierenden Reinigungsmittels werden vorzugsweise derart gewählt, daß der pH-Wert der Lösung bei 11,5 bis 12,5 liegt.The type and amount of alkaline Cleaning agents are preferably chosen such that the pH of the solution is 11.5 to 12.5.
Die alkalisch reagierenden Reinigungsmittel können Hydroxide, Phosphate, Carbonate und Borate von Alkalimetallen mit Ausnahme von Silikat sein. Diese Bestandteile werden üblicherweise in einer Konzentration von 3 bis 150 g/I, vorzugsweise von 7 bis 9 g/I angewendet.The alkaline cleaning agents can be hydroxides, phosphates, carbonates and borates of alkali metals with the exception of silicate. These components are usually used in a concentration of 3 to 150 g / l, preferably 7 to 9 g / l.
Die Tenside können grundsätzlich anionenaktiv, nichtionogen, kationenaktiv oder amphoter sein. Sie müssen im alkalischen Medium und unter den Anwendungsbedingungen der Lösung verträglich sein. Ihre Wahl hängt im wesentlichen vom pH-Wert des Reinigungs- und Entfettungsmittels den Anwendungsbedingungen, d. h. Tauch- oder Spritzanwendung, und wirtschaftlichen Erwägungen ab. Für im Spritzverfahren angewendete Lösungen sind nichtionogene Tenside bevorzugt. Ihre Konzentration sollte zwischen 0,1 und 5 g/I, vorzugsweise bei ca. 1 g/I liegen. Derartige Tenside können allein oder in Mischung verwendet werden.The surfactants can in principle be anion-active, non-ionic, cation-active or amphoteric. They must be compatible in the alkaline medium and under the conditions of use of the solution. Your choice depends essentially on the pH of the cleaning and degreasing agent, the conditions of use, i. H. Dip or spray application, and economic considerations. For solutions used in the spray process, nonionic surfactants are preferred. Their concentration should be between 0.1 and 5 g / l, preferably about 1 g / l. Such surfactants can be used alone or in a mixture.
Die von Alkaliionen verschiedenen Metallionen können aus denen ausgewählt werden, die in der FR-PS-1 411 272 genannt sind. Hierbei handelt es sich insbesondere um Aluminium, Antimon, Silber, Cadmium, Cer, Chrom, Cobalt, Zinn, Eisen(11- oder III-wertig), Magnesium, Mangan, Molybdän, Nickel, Titan und Wolfram. Cobalt-, Eisen- und Nickelionen sind bevorzugt, insbesondere Nickel.The metal ions other than alkali ions can be selected from those mentioned in French Patent 1,411,272. These are in particular aluminum, antimony, silver, cadmium, cerium, chromium, cobalt, tin, iron (11 or III-valent), magnesium, manganese, molybdenum, nickel, titanium and tungsten. Cobalt, iron and nickel ions are preferred, especially nickel.
Das dem Kation zur Einbringung zugeordnete Anion soll mit der Lösung verträglich sein und keine nachteilige Wirkung ausüben. Aus diesem Grunde wird zur Einbringung der von Alkaliionen verschiedenen Metallionen vorzugsweise Nitrat verwendet.The anion assigned to the cation for introduction should be compatible with the solution and should not have any adverse effect. For this reason, nitrate is preferably used to introduce the metal ions other than alkali ions.
Die Konzentration der von Alkaliionen veschiedenen Metallkationen in der Lösung hängt von der Konzentration des alkalisch reagierenden Reinigungsmittels ab. Je höher sie ist, desto höher sollte auch die Konzentration von Kationen sein. Die Konzentration an von Alkaliionen verschiedenen Kationen kann zwischen 50 und 5000 mg/I, vorzugsweise zwischen 100 und 1000 mg/I liegen. Bei einer Konzentration des alkalisch reagierenden Reinigungsmittels von ca. 10 g/I und einem pH-Wert in der Größenordnung von 12 ist der bevorzugte Bereich der Metallkationen bei 500 bis 700 mg/I.The concentration of the metal cations other than alkali ions in the solution depends on the concentration of the alkaline cleaning agent. The higher it is, the higher the concentration of cations should be. The concentration of cations other than alkali ions can be between 50 and 5000 mg / l, preferably between 100 and 1000 mg / l. With a concentration of the alkaline-reacting cleaning agent of approx. 10 g / l and a pH of the order of 12, the preferred range of the metal cations is 500 to 700 mg / l.
Bei hohen Konzentrationen an von Alkaliionen verschiedenen Kationen kann die Verbesserung praktisch nicht über der liegen, die man üblicherweise mit der bevorzugten Konzentration von 500 bis 700 mg/I erhält. Infolge des hohen pH-Wertes, der Anwendungsbedingungen und des hohen Gehaltes an von Alkaliionen verschiedenen Kationen ist die Lösung nicht gänzlich schlammfrei, was jedoch nicht schädlich ist, sofern die Schlammenge gering ist, d.h. in der Größenordnung von 2 bis 3 Vol-OIo, bezogen auf die gesamte Lösung, liegt.At high concentrations of cations other than alkali ions, the improvement can practically not be greater than that which is usually obtained with the preferred concentration of 500 to 700 mg / l. Due to the high pH, the conditions of use and the high content of cations other than alkali ions, the solution is not entirely sludge-free, which is not harmful, however, if the amount of sludge is small, i.e. is in the order of 2 to 3% by volume, based on the entire solution.
Die in der Lösung zur Reinigung und Entfettung verwendeten Komplexbildner können die gleichen wie die sein, die in der FR-PS-1 411 272 beschrieben sind. Es kann sich insbesondere um kondensierte Phosphate, Dicarbonsäuren, Hydroxicarbonsäuren, Benzolcarbonsäuren, Hydroxialdehyde und Amine handeln. Die besten Resultate sowohl hinsichtlich Entfettung der Metalloberfläche als auch hinsichtlich Komplexierung der Metallionen lassen sich mit Natriumgluconat, Natriumglucoheptonat, Sorbitol und Natriumäthylendiaminotetraacetat erzielen.The complexing agents used in the cleaning and degreasing solution can be the same as those described in FR-PS-1 411 272. In particular, it can be condensed phosphates, dicarboxylic acids, hydroxy carboxylic acids, benzene carboxylic acids, hydroxy aldehydes and amines. The best results in terms of degreasing the metal surface and complexing the metal ions can be achieved with sodium gluconate, sodium glucoheptonate, sorbitol and sodium ethylenediaminotetraacetate.
Die Konzentration an Komplexildner sollte ausreichen, um die von Alkaliionen verschiedenen Metalle unter Berücksichtigung ihrer Konzentration und des pH-Wertes der Lösung in der Lösung zu stabilisieren. Die Konzentration kann sich zwischen 0,1 und 30 g/I bewegen. Vorzugsweise beträgt sie 0,5 bis 1 g/I.The concentration of complexing agent should be sufficient to stabilize the metals other than alkali ions, taking into account their concentration and the pH of the solution in the solution. The concentration can range between 0.1 and 30 g / l. It is preferably 0.5 to 1 g / l.
Die wäßrige alkalische Lösung zur Reinigung und Entfettung der Metalloberfläche kann erhalten werden, indem man ein festes Konzentrat, das das oder die alkalisch reagierenden Reinigungsmittel, das oder die Tensid(e), die von Alkaliionen verschiedenen Metallionen und den oder die Komplexbildner enthält.The aqueous alkaline solution for cleaning and degreasing the metal surface can be obtained by adding a solid concentrate which contains the alkaline-reacting cleaning agent or agents, the surfactant (s), the metal ions other than alkali ions and the complexing agent or agents.
Die Lösung kann jedoch auch erhalten werden, wenn man feste oder flüssige Konzentrate verwendet, von denen eines das oder die alkalisch wirkenden Reinigungsmittel, die Gesamtmenge oder nur einen Teil des oder der notwendigen Tensids(e) und die Gesamtmenge oder nur einen Teil des notwendigen Komplexbildners enthält und von denen das andere die von Alkaliionen verschiedenen Metallkationen, die Gesamtmenge oder nur einen Teil des oder der notwendigen Tensids(e) und die Gesamtmenge oder nur einen Teil des notwendigen Komplexbildners enthält.However, the solution can also be obtained if solid or liquid concentrates are used, one of which contains the alkaline detergent (s), the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent contains and the other of which contains the metal cations other than alkali ions, the total amount or only part of the necessary surfactant (s) and the total amount or only part of the necessary complexing agent.
Im allgemeinen können die vorstehend beschriebenen Reinigungs- und Entfettungslösungen bei einer Temperatur im Bereich von 20 bis 90° C, vorzugsweise von 45 bis 65°, im Spritzen oder Tauchen während einer Zeitdauer von etwa 3 bis 180 sec, vorzugsweise von 10 bis 30 sec, angewendet werden.In general, the cleaning and degreasing solutions described above can be sprayed or dipped at a temperature in the range from 20 to 90 ° C., preferably from 45 to 65 °, for a period of from about 3 to 180 seconds, preferably from 10 to 30 seconds. be applied.
Anschließend wird die gereinigte und entfettete Metalloberfläche mit Wasser gespült.Then the cleaned and degreased metal surface is rinsed with water.
Danach wird die Metalloberfläche mit einer Lösung in Berührung gebracht, die Alkali, Kationen von wenigstens einem von Alkaliionen verschiedenen Metall und mindestens einen Komplexbildner enthält. Hierbei kann es sich beispielsweise um eine Lösung, wie in der FR-PS-1 411 272 beschrieben, handeln.The metal surface is then brought into contact with a solution which contains alkali, cations of at least one metal other than alkali ions and at least one complexing agent. This can be, for example, a solution as described in FR-PS-1 411 272.
Anschließend wird erneut mit Wasser gespült und mit einer sauren Passivierungslösung behandelt. Die Passivierungslösung kann beispielsweise Chrom-III und/oder Chrom-IV enthalten und die in der FR-PS-1 487 183 beschriebene Beschaffenheit besitzen.It is then rinsed again with water and treated with an acidic passivation solution. The passivation solution can contain, for example, chromium-III and / or chromium-IV and have the properties described in FR-PS-1 487 183.
Es können auch andere Arten von Passivierungsbehandlungen vorgenommen werden, um dadurch die Haftung von Farbe, Lack und dergl. und den Korrosionsschutz zu verbessern. So kann man beispielsweise einen Umwandlungsüberzug durch Aufbringung einer Dispersion von Chromsäure und/oder Chromverbindung mit kolloidalem Siliziumdioxid erzeugen.Other types of passivation treatments can also be used to reduce the adhesion of paint and varnish and the like. and to improve the corrosion protection. For example, a conversion coating can be created by applying a dispersion of chromic acid and / or chromium compound with colloidal silicon dioxide.
Vorzugsweise wird die zur Passivierungsbehandlung aufgebrachte Passivierungslösung aufgetrocknet. Die so behandelte Metalloberfläche wird abschließend mit Farbe, Lack und dergl. versehen.The passivation solution applied for the passivation treatment is preferably dried. The metal surface treated in this way is then provided with paint, lacquer and the like.
Das erfindungsgemäße Verfahren ist für die Oberflächenbehandlung von Gegenständen geeignet, die aus Zink oder Zinklegierungen bestehen oder aber eine Auflage von Zink oder Zinklegierungen, wie z. B. verzinkter Stahl, besitzen. Es ist insbesondere geeignet für die Behandlung von Blech oder Band.The inventive method is suitable for the surface treatment of objects which consist of zinc or zinc alloys or a coating of zinc or zinc alloys, such as. B. galvanized steel. It is particularly suitable for the treatment of sheet metal or strip.
Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
Zur Durchführung der Versuche wurden feuerverzinkte Stahlbleche verwendet.Hot-dip galvanized steel sheets were used to carry out the tests.
Zur Reinigung und Entfettung wurden die nachfolgende aufgeführten Lösungen verwendet:
Diese Lösungen wurden mit der Metalloberfläche im Spritzen unter einem Druck von 1,5 - 105 Pa während 10 sec bei 50°C in Kontakt gebracht.These solutions were brought into contact with the metal surface by spraying under a pressure of 1.5-10 5 Pa for 10 seconds at 50 ° C.
Anschließend wurden die Bleche mit kaltem fließenden Wasser gespült und mit einer Lösung, enthaltend
Nach erneuter Spülung mit kaltem fließenden Wasser wurde eine Passivierungsbehandlung mit einer Lösung vorgenommen, die
Abschließend wurden die Bleche mit einem Lacküberzug von Alkydharz bzw. Acrylatharz einer Dicke von ca. 30 11m versehen. Nach der Trocknung ruhten die Bleche 48 Stunden.Finally, the sheets were coated with a coating of alkyd resin or acrylate resin with a thickness of approx. 30 1 1 m. After drying, the sheets rested for 48 hours.
Zunächst konnte man feststellen, daß die Bleche, die im Entfettungbad 2 behandelt worden waren, nach der Behandlung in der Chromsäurelösung unterschiedlich aussahen. Sie waren dunkelgrau und matt, wohingegen die anderen Bleche einen praktisch farblosen Überzug aufwiesen.First, it was found that the sheets that had been treated in degreasing bath 2 looked different after the treatment in the chromic acid solution. They were dark gray and matt, whereas the other sheets had a practically colorless coating.
Der Einfluß der Beschaffenheit der Reinigungs-und Entfettungslösung wurde dann durch Biegen um einen konischen Dorn bestimmt. Dabei sind die mit den Lösungen 3 bis 5 (entsprechend der Erfindung) behandelten Bleche zunächst denen überlegen, die mit Lösung 1 (gemäß dem Stand der Technik) behandelt worden waren, aber auch gegenüber den mit Lösung 2 behandelten Blechen. Lösung 2 hatte die gleiche qualitative Beschaffenheit wie Lösung 1 und unterschied sich lediglich durch die doppelte Konzentration der Bestandteile, um den Beizeffekt zu verstärken. Insoweit stimmte Lösung 2 auch mit den Lösungen 3 bis 5 überein, die sich wiederum durch einen Gehalt an von Alkaliionen verschiedenen Metallkationen unterschieden.The influence of the nature of the cleaning and degreasing solution was then determined by bending around a conical mandrel. The sheets treated with solutions 3 to 5 (according to the invention) are initially superior to those which had been treated with solution 1 (according to the prior art), but also compared to the sheets treated with solution 2. Solution 2 had the same qualitative nature as solution 1 and differed only by the double concentration of the components in order to intensify the pickling effect. In this respect, solution 2 also agreed with solutions 3 to 5, which in turn differed in the content of metal cations other than alkali ions.
Im Ergebnis verstärkten sich Rißbildung im Lack und Lackablösung von Beispiel 3, 4, 5 nach 1, gefolgt von 2.As a result, cracking in the lacquer and lacquer detachment increased from Examples 3, 4, 5 to 1, followed by 2.
Die versuche zur ermittlung der Salzsprühbeständigkeit gemäß AFNOR X 41 002 haben nach 1000 Stunden einen deutlichen Vorteil der mit den Lösungen 3, 4 und 5 behandelten Bleche gegenüber den mit Lösung 1 und sogar gegenüber den mit Lösung 2 behandelten Blechen gezeigt.The tests to determine the salt spray resistance according to AFNOR X 41 002 showed after 1000 hours a clear advantage of the sheets treated with solutions 3, 4 and 5 compared to the sheets treated with solution 1 and even compared to the sheets treated with solution 2.
Feuerverzinkte Stahlbleche wurden nach dem Verfahrensgang des Beispiels 1 behandelt, jedoch dienten zur Reinigung und Entfettung Lösungen folgender Beschaffenheit:
Die nach dem Rollenauftragsverfahren aufgebrachten Lacke waren von folgendem Typ: Polyvinylchlorid, Polyester, siliconmodifizierter Polyester, Polyvinyliden und Polyacrylat.The varnishes applied by the roller application process were of the following type: polyvinyl chloride, polyester, silicone-modified polyester, polyvinylidene and polyacrylate.
Es wurden Biegeversuche und Salzsprühtests sowie Versuche zur Erforschung der Oberfläche mittels Spektroskopie durch Lumineszenzentladung angestellt. Die Biegeversuche haben bestätigt, daß die Lackhaftung deutlich steigt, wenn man die Nickelkonzentration in der Reinigungs- und Entfettungslösung erhöht. Beispielsweise erhält man bei Verwendung der Lösung 8 einen Wert, der sowohl aus technischer als auch aus ökonomischer Sicht sehr interessant ist.Bending tests and salt spray tests as well as attempts to investigate the surface by means of spectroscopy by luminescence discharge were carried out. The bending tests have confirmed that the paint adhesion increases significantly if the nickel concentration in the cleaning and degreasing solution is increased. For example, when using solution 8, a value is obtained which is very interesting both from a technical and an economic point of view.
Die Ergebnisse spektroskopischer Analysen zeigten, daß bei Verwendung der Reinigungs-und Entfettungslösung gemäß Beispiel 6, 7 und 8 eine sehr gleichmäße statistische Verteilung des Cobalts und Eisens im auf der Metalloberfläche befindlichen Umwandlungsüberzug erhalten und daß die Oberflächenkonzentration an Aluminium und Blei verringert wird. Bei Aluminium und Blei handelt es sich bekanntlich um Störelemente, die die Qualität des behandelten und lackierten Metallerzeugnisses beeinträchtigen.The results of spectroscopic analyzes showed that when using the cleaning and degreasing solution according to Examples 6, 7 and 8, a very uniform statistical distribution of the cobalt and iron in the conversion coating on the metal surface is obtained and that the surface concentration of aluminum and lead is reduced. Aluminum and lead are known to be interfering elements that impair the quality of the treated and painted metal product.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8403560A FR2560894B1 (en) | 1984-03-07 | 1984-03-07 | PROCESS FOR THE PREPARATION OF ZINC SURFACES, ZINC ALLOYS AND STEEL COATED WITH SUCH MATERIALS FOR RECEIVING PAINTS OR VARNISHES |
| FR8403560 | 1984-03-07 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0154384A2 EP0154384A2 (en) | 1985-09-11 |
| EP0154384A3 EP0154384A3 (en) | 1987-02-04 |
| EP0154384B1 true EP0154384B1 (en) | 1989-06-21 |
Family
ID=9301804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19850200318 Expired EP0154384B1 (en) | 1984-03-07 | 1985-03-05 | Process for pretreating zinc surfaces before lacquering |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0154384B1 (en) |
| DE (2) | DE3507372A1 (en) |
| FR (1) | FR2560894B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6220880A (en) * | 1985-07-19 | 1987-01-29 | Nippon Parkerizing Co Ltd | Surface treatment of zinc-aluminum alloy plated steel sheet |
| JPH0730458B2 (en) * | 1988-08-08 | 1995-04-05 | 日本パーカライジング株式会社 | Blackening treatment method for zinc or zinc-based plating material |
| DE102010001686A1 (en) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Composition for the alkaline passivation of zinc surfaces |
| PL2503025T3 (en) | 2011-03-22 | 2013-12-31 | Henkel Ag & Co Kgaa | Multi-step corrosion-resistant treatment of metallic workpieces having at least partially zinc or zinc alloy surfaces |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2331196A (en) * | 1941-08-22 | 1943-10-05 | Westinghouse Electric & Mfg Co | Protective phosphate coating |
| US3506499A (en) * | 1964-03-16 | 1970-04-14 | Yawata Seitetsu Kk | Method of surface-treating zinc,aluminum and their alloys |
| FR1411272A (en) * | 1964-08-20 | 1965-09-17 | Parker Ste Continentale | Process for coating surfaces of zinc and zinc alloys |
| US3501352A (en) * | 1965-08-02 | 1970-03-17 | Hooker Chemical Corp | Composition and method for treating zinc surfaces |
| FR1487183A (en) * | 1965-08-02 | 1967-06-30 | Parker Ste Continentale | Composition and method for the treatment of metal surfaces |
| SE330305B (en) * | 1965-10-19 | 1970-11-09 | Continentals Parker Sa Soc | |
| FR1596007A (en) * | 1968-04-18 | 1970-06-15 | ||
| US3620949A (en) * | 1969-04-11 | 1971-11-16 | Balm Paints Ltd | Metal pretreatment and coating process |
| JPS51135840A (en) * | 1975-05-21 | 1976-11-25 | Nippon Packaging Kk | Surface treatment process for zinc or zinc alloy |
-
1984
- 1984-03-07 FR FR8403560A patent/FR2560894B1/en not_active Expired
-
1985
- 1985-03-02 DE DE19853507372 patent/DE3507372A1/en not_active Withdrawn
- 1985-03-05 EP EP19850200318 patent/EP0154384B1/en not_active Expired
- 1985-03-05 DE DE8585200318T patent/DE3571148D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0154384A2 (en) | 1985-09-11 |
| DE3507372A1 (en) | 1985-09-26 |
| DE3571148D1 (en) | 1989-07-27 |
| FR2560894B1 (en) | 1988-11-18 |
| FR2560894A1 (en) | 1985-09-13 |
| EP0154384A3 (en) | 1987-02-04 |
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