DE3408573A1 - METHOD FOR TREATING METAL SURFACES - Google Patents
METHOD FOR TREATING METAL SURFACESInfo
- Publication number
- DE3408573A1 DE3408573A1 DE19843408573 DE3408573A DE3408573A1 DE 3408573 A1 DE3408573 A1 DE 3408573A1 DE 19843408573 DE19843408573 DE 19843408573 DE 3408573 A DE3408573 A DE 3408573A DE 3408573 A1 DE3408573 A1 DE 3408573A1
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- solution
- metal surfaces
- conversion coating
- chemical conversion
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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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
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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
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
NIHON PARKERIZING CO., LTD. 3 7. März 1984NIHON PARKERIZING CO., LTD. 3 March 7, 1984
Tokyo 103, Japan DROZ/LWÜ/1590PTokyo 103, Japan DROZ / LWÜ / 1590P
Prov. Nr. 9141 MProv. No. 9141 M.
Verfahren zum Behandeln von MetalloberflächenProcess for treating metal surfaces
Die Erfindung betrifft ein Verfahren zum Behandeln von gegebenenfalls mit einem chemischen ümwandlungsuberzug versehenen Metalloberflächen durch In-Berührung-bringen mit einer wäßrigen Lösung, die reaktives Organosilan enthält, und anschließendes Auftrocknen der Lösung.The invention relates to a method for treating possibly provided with a chemical conversion coating Metal surfaces by bringing them into contact with an aqueous solution containing reactive organosilane, and then Drying up the solution.
Es ist bekannt, auf Metalloberflächen Schutzüberzüge aufzubringen, um die Korrosionsbeständigkeit und die Haftung eines nachfolgend aufgetragenen Lackes zu verbessern. Hierzu werden üblicherweise die Metalloberflächen mit Lösungen in Berührung gebracht, die einen Phosphatüberzug und/oder Metalloxidüberzug ausbilden. Schutzüberzüge mit ähnlicher Wirkung können auch mit Lösungen auf Basis Oxalationen, Chromationen und dergl. erzeugt werden.It is known to apply protective coatings to metal surfaces, to improve the corrosion resistance and the adhesion of a subsequently applied paint. To do this will be Usually the metal surfaces are brought into contact with solutions that have a phosphate coating and / or metal oxide coating form. Protective coatings with a similar effect can also be combined with solutions based on oxalate ions, chromate ions and the like. be generated.
Die Erzeugung der sogenannten ümwandlungsuberzuge geschieht im allgemeinen nach dem VerfahrensschemaThe generation of the so-called Umwandlungsüberzuge takes place in the general according to the procedural scheme
Reinigung,Cleaning,
Wasserspülung,Water flush,
Bildung der Umwandlungsüberzüge,Formation of conversion coatings,
Wasserspülung.Water flush.
Zur weiteren Verbesserung des so erhaltenen ümwandlungsuberzuges ist es üblich, eine Behandlung mit einer Nachbehand-To further improve the conversion coating obtained in this way it is common to start treatment with an after-treatment
lungslösung anzuschließen. Hierfür sind insbesondere Lösungen auf Chromatbasis gebräuchlich. Obgleich diese Form der Nachbehandlung durchaus wirksam ist, ist infolge der Toxizität der Chromatlösungen, die besondere Vorsichtsmaßnahmen bei der Applikation erforderlich macht, und der Abwasserprobleme zunehmend eine Abkehr von derartigen Nachbehandlungslösungen erkennbar. Auch kann bei der Bildung von Umwandlungsüberzügen auf Behältermaterial für Lebensmittel und Getränke eine Beeinflussung des Behälterinhaltes nicht ausgeschlossen werden.solution solution. For this purpose, solutions based on chromate are used in particular. Although this form of follow-up treatment is quite effective, as a result of the toxicity of the chromate solutions, which special precautions are taken when using Application makes it necessary, and the wastewater problems increasingly a move away from such aftertreatment solutions recognizable. It can also have an impact on the formation of conversion coatings on container material for food and beverages the contents of the container cannot be excluded.
Bei der Nachbehandlung von Umwandlungsüberzügen ist es bekannt, eine nicht zusammenhängende Dichtungsschicht eines hydrophobmachenden Mittels, z.B. unter Verwendung organischer Stoffe, etwa auf Basis Polyisocyanat modifizierter Harzkondensationsprodukte (DE-AS 11 47 820) zu erzeugen bzw. mit trocknenden ölen oder niedrigviskosen Lacken abzudichten (H. Fortmann "Nachbehandlungsverfahren phosphatierter Eisenteile", Metallwaren-Industrie und Galvanotechnik MSV Nr. 6 (1943), Seite 229). Diese Mittel konnten sich jedoch gegenüber den chromhaltigen Nachbehandlungslösungen aus Gründen niederer Qualität nicht durchsetzen. Zudem führten zahlreiche dieser Mittel nicht zu brauchbaren Ergebnissen.In the aftertreatment of conversion coatings, it is known to use a discontinuous sealing layer hydrophobizing agent, e.g. using organic substances, e.g. resin condensation products modified on the basis of polyisocyanate (DE-AS 11 47 820) to produce or to seal with drying oils or low-viscosity paints (H. Fortmann "Post-treatment process for phosphated iron parts", metal goods industry and electroplating MSV No. 6 (1943), Page 229). However, these means could be lower than the chromium-containing aftertreatment solutions for reasons Quality does not enforce. In addition, many of these agents did not produce useful results.
Ein ebenfalls zur Nachbehandlung chemisch aufgebrachter Umwandlungsüberzüge, insbesondere Phosphatüberzüge, bestimmtes Verfahren sieht vor, Lösungen einzusetzen, die eine bestimmte Poly-4-vinylphenolverbindung enthält (DE-OS 31 46 265).A conversion coating, in particular phosphate coatings, also chemically applied for post-treatment The method provides for using solutions which contain a certain poly-4-vinylphenol compound (DE-OS 31 46 265).
Der pH-Wert der zum Einsatz kommenden Lösung liegt üblicherweise im alkalischen Bereich, was bei der Behandlung von mit Umwandlungsüberzügen versehenen Metalloberflächen gegebenenfalls mit dem Nachteil einer teilweisen Schichtablösung verbunden sein kann.The pH value of the solution used is usually in the alkaline range, which is the case when treating with Metal surfaces provided with conversion coatings may have the disadvantage of partial delamination can be.
Mit einer anderen in bestimmter Weise substituierten PoIyvinylphenolverbindung können sowohl metallische OberflächenWith another polyvinylphenol compound substituted in a certain way can be both metallic surfaces
als auch solche, die zuvor mit einem ümwandlungsuberzug versehen worden sind, behandelt werden (EP-OS 91 166).as well as those that were previously provided with a conversion coating have been treated (EP-OS 91 166).
Schließlich ist es bekannt, Organosilane als Haftvermittler zur Erzeugung gut haftender Beschichtungen auf Metalloberflächen oder zuvor mit einem ümwandlungsuberzug versehenen Metalloberflächen einzusetzen (Ulimann, Encyklopädie der techn. Chemie, 4. Auflage, Band 21, Seiten 496 ff.; DE-OS 25 43 519). Obgleich die vorgenannte Arbeitsweise mit gewissen Vorteilen, insbesondere hinsichtlich der Haftung, verbunden ist, haftet ihr der Nachteil an, daß der Korrosionsschutz der so behandelten und anschließend lackierten Metalloberfläche nicht befriedigend ist.Finally, it is known that organosilanes can be used as adhesion promoters for producing well-adhering coatings on metal surfaces or to use metal surfaces previously provided with a conversion coating (Ulimann, Encyklopadie der techn. Chemie, 4th Edition, Volume 21, pages 496 ff .; DE-OS 25 43 519). Although the aforementioned way of working with certain Advantages, especially with regard to adhesion, is associated with the disadvantage that the corrosion protection of the so treated and then painted metal surface is not satisfactory.
Aufgabe der Erfindung ist es, ein Verfahren zum Behandeln von gegebenenfalls mit einem chemischen ümwandlungsuberzug versehenen Metalloberflächen bereitzustellen, das zusätzlich insbesondere den Korrosionsschutz der Metalloberfläche verbessert und mit keinerlei Umwelt- und Applikationsproblemen behaftet ist.The object of the invention is to provide a method for treating those which may have been provided with a chemical conversion coating To provide metal surfaces, which additionally improves the corrosion protection of the metal surface in particular and is not associated with any environmental or application problems.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die gegebenenfalls mit einem chemischen Umwandlungsüberzug versehenen Metalloberflächen mit einer Lösung in Berührung bringt, die neben Organosilan zusätzlich Titan- und/oder Zirkonfluorid-Verbindung enthält.The object is achieved in that the method of the type mentioned at the outset is configured in accordance with the invention in this way that you can optionally with a chemical conversion coating brings metal surfaces into contact with a solution which, in addition to organosilane, also contains titanium and / or contains zirconium fluoride compound.
Der Begriff "wäßrige Lösung" schließt Lösungen ein, die als Lösungsvermittler gewisse Mengen Alkohol oder ähnliche wasserlösliche Lösungsmittel enthalten.The term "aqueous solution" includes solutions as Solubilizers contain certain amounts of alcohol or similar water-soluble solvents.
Besonders vorteilhaft ist es, wenn man in bevorzugter Ausgestaltung der Erfindung die gegebenenfalls mit einem chemischen Umwandlungsüberzug versehenen Metalloberflächen mit einerIt is particularly advantageous if you have a preferred embodiment of the invention, the metal surfaces optionally provided with a chemical conversion coating with a
Lösung in Berührung bringt, die ein Organosilan mit mindestens 2 reaktiven Gruppen enthält.Solution that brings an organosilane into contact with at least Contains 2 reactive groups.
Für die Durchführung des erfindungsgemäßen Verfahrens geeignete Organosilane sind bei Ulimann I.e., insbesondere in den Tabellen 6 bis 8 auf den Seiten 499, 501 und 503 beschrieben. Insbesondere geeignete Organosilane sind Trimethylmethoxysilan, /"-Aminopropyltriethoxysilan,^-Aminopropyltrimethoxysilan, N-ß-(aminoethyl)^-aminopropylmethyldiethoxysilan, Vinyl tr iethoxysilan, Vir;yltris(ß-inethoxyethoxy)silan, Divinyldimethoxysilan^-Glycidoxypropyltrimethoxysilany^-Methacryloxypropyltrimethoxysilan. Diese Substanzen enthalten im Molekül anorganische Stoffe chemisch bindende reaktive Gruppen, wie Methoxy-, Ethoxy- und Silanolgruppen, sowie organische Stoffe, wie Kunststoffe, chemisch bindende reaktive Gruppen, wie Vinyl-, Epoxy-, Methacryl- und Aminogruppen.Organosilanes suitable for carrying out the process according to the invention are described in Ulimann Ie , in particular in Tables 6 to 8 on pages 499, 501 and 503. Particularly suitable organosilanes are trimethylmethoxysilane, / "- aminopropyltriethoxysilane, ^ - aminopropyltrimethoxysilane, N-ß- (aminoethyl) ^ - aminopropylmethyldiethoxysilane, vinyl triethoxysilane, vir; yltris (ß-inethoxyimethoxy) silane, these substances In the molecule, inorganic substances contain chemically binding reactive groups such as methoxy, ethoxy and silanol groups, as well as organic substances such as plastics, chemically binding reactive groups such as vinyl, epoxy, methacrylic and amino groups.
Als Titan- bzw. Zirkonfluorid-Verbindungen kommen insbesondere Fluorotitan- oder -zirkonwasserstoffsäure, Ammoniumfluorotitanat oder -zirkonat zum Einsatz. Sie können gegebenenfalls in der Behandlungslösung durch Umsetzung von z.B. metallischem Titan oder Zirkon, Titan- oder Zirkonoxid, -hydroxid und dergl. mit Flußsäure, gegebenenfalls in Gegenwart von Ammoncarbonat, gebildet werden.Particularly suitable titanium or zirconium fluoride compounds are fluorotitanic or hydrofluoric zirconic acid and ammonium fluorotitanate or zirconate. You can optionally in the treatment solution by reaction of e.g. metallic Titanium or zirconium, titanium or zirconium oxide, hydroxide and the like. With hydrofluoric acid, optionally in the presence of Ammonium carbonate.
Die im erfindungsgemäßen Verfahren einzusetzende Lösung zeichnet sich durch hohe Stabilität aus, d.h. bei ihrer Verwendung fallen keine Bestandteile aus.The solution to be used in the method according to the invention is characterized are characterized by high stability, i.e. no components fail when they are used.
Die Applikation der Behandlungslösung kann auf beliebige Weise erfolgen. Geeignete Aufbringungsformen sind z.B. Aufstreichen, Aufsprühen, Aufrollen, Tauchen oder Fluten.The treatment solution can be applied in any way. Suitable forms of application are e.g. brushing, Spray on, roll up, dip or flood.
Die Trocknungstemperatur ist in weiten Grenzen wählbar und liegt im allgemeinen im Bereich von 60 bis 300 0C.The drying temperature can be selected within wide limits and is generally in the range from 60 to 300 ° C.
Mit dem erfindungsgemäßen Verfahren können insbesondere Stähle, legierte Stähle, Aluminium und Zink sowie deren Legierungen, mit Zink oder Zinn plattierte Stähle bzw. anderweitig verzinkte oder verzinnte Stähle behandelt werden. Auch können die vorgenannten Substrate zuvor mit zink- oder Eisenphosphatschichten bzw. Chromatschichten versehen worden sein. Obgleich die mit dem erfindungsgemäßen Verfahren auf Metalloberflächen erzeugten Überzüge einen hohen Korrosionsschutz und hervorragende Haftungseigenschaften für die anschließende Lackierung vermitteln, läßt sich die Wirkung noch verstärken, wenn das Verfahren zur Nachbehandlung von zuvor mit einem Umwandlungsüberzug versehenen Metalloberflächen eingesetzt wird. With the method according to the invention, in particular Steels, alloy steels, aluminum and zinc and their alloys, steels plated with zinc or tin, or otherwise galvanized or tinned steels are treated. The aforementioned substrates can also be coated beforehand with zinc or iron phosphate layers or chromate layers have been provided. Although those with the method according to the invention on metal surfaces coatings produced a high level of corrosion protection and excellent adhesion properties for the subsequent painting convey, the effect can be increased if the process is used for the aftertreatment of metal surfaces previously provided with a conversion coating.
Bevorzugte Ausgestaltungen der Erfindung sehen vor, die gegebenenfalls mit einem chemischen ümwandlungsuberzug versehenen Metalloberflächen mit einer Lösung in Berührung zu bringen, die Organosilan in einer Konzentration von 0,5 bis 100 g/l, vorzugsweise von 1 bis 50 g/l, enthält bzw. die Titan- und/oder Zirkonfluorid-Verbindung in einer Konzentration von 0,01 bis 5 g/l, vorzugsweise in einer Konzentration von 0,05 bis 1 g/l, enthält bzw. in der das Verhältnis von Organosilan zu Titan- und/oder Zirkonfluorid-Verbindung im Bereich von (10 bis 200) : 1, vorzugsweise von (20 bis 100) : 1, liegt.Preferred embodiments of the invention provide, if necessary Bringing metal surfaces provided with a chemical conversion coating into contact with a solution, the organosilane in a concentration of 0.5 to 100 g / l, preferably from 1 to 50 g / l or the titanium and / or zirconium fluoride compound in a concentration of 0.01 to 5 g / l, preferably in one Concentration from 0.05 to 1 g / l, contains or in which the ratio of organosilane to titanium and / or Zirconium fluoride compound in the range from (10 to 200): 1, preferably from (20 to 100): 1.
Außerhalb der genannten Bereiche ist entweder keine ausreichende Wirkung der Lösungsbestandteile mehr feststellbar oder aber keine wesentliche Steigerung der Wirkung erkennbar.Outside of the ranges mentioned, either the solution constituents no longer have a sufficient effect or but no significant increase in the effect can be seen.
Eine weitere bevorzugte Ausführungsform der Erfindung sieht vor, die gegebenenfalls mit einem chemischen ümwandlungsuberzug versehenen Metalloberflächen mit der Lösung derart in Berührung zu bringen, daß nach der anschließenden Auftrocknung des Lösungsfilms ein Schichtgewicht von 10 bis 300 mg/mAnother preferred embodiment of the invention provides, optionally with a chemical conversion coating to bring metal surfaces provided with the solution in such a way that after the subsequent drying of the solution film has a layer weight of 10 to 300 mg / m
erhalten wird.is obtained.
Ä 3Λ08573Ä 3Λ08573
Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by way of example and in greater detail on the basis of the following examples.
Es wurden vier Behandlungslösungen hergestellt, die folgende Beschaffenheit aufwiesen:Four treatment solutions were prepared which were as follows:
Lösung 1:Solution 1:
10 g Vinyltriethoxysilan 100 g Methanol10 g vinyl triethoxysilane 100 g methanol
1 g Ammoniumhexafluorotitanat.1 g ammonium hexafluorotitanate.
Es wurde mit Wasser von 1 1 verdünnt. Der pH-Wert der Lösung betrug 4,0.It was diluted 1 liter with water. The pH of the solution was 4.0.
Lösung 2:Solution 2:
5 g Methacryloxypropyltrimethoxysilan 20 g Ethanol5 g methacryloxypropyltrimethoxysilane 20 g ethanol
0,2 g HexafIuoro2irkonwasserstoffsäure 0,2 g Hexafluorotitanwasserstoffsäure0.2 g hexafluoro2irconic acid 0.2 g of hexafluorotitanic acid
Die mfct 1 1 Wasser versetzte Mischung wies einen pH-Wert von 3,0 auf.The mixture mixed with mfct 1 l of water had a pH of 3.0 on.
Lösung 3:Solution 3:
30 g N-ß-CAminoethyDjf^aminopropyltrimethoxysilan 3 g Ammoniumhexafluorotitanat30 g of N-ß-CAminoethyDjf ^ aminopropyltrimethoxysilane 3 g ammonium hexafluorotitanate
wurden mit 1 1 Wasser versetzt. Der pH-Wert der Lösung betrug 11,0.1 l of water were added. The pH of the solution was 11.0.
Lösung 4:Solution 4:
10 g 3^-Aminopropyltriethoxysilan 1 g Hexafluorozirkonwasserstoffsäure10 g of 3 ^ -aminopropyltriethoxysilane 1 g of hexafluorozirconic acid
wurden mit 1 1 Wasser versetzt. Der pH-Wert der erhaltenen Lösung lag bei 10,0.1 l of water were added. The pH of the solution obtained was 10.0.
Stahlbleche, verzinkte Stahlbleche und Aluminiumbleche, die zuvor mit einem alkalischen Entfettungsmittel gereinigt worden waren, wurden 5 see in die oben genannten Behandlungslösungen getaucht, durch Abquetschrollen von überschüssiger Lösung befreit und während einer Zeitdauer von 30 see im Heißluftstrom von 120 0C getrocknet.Steel sheets, galvanized steel sheets and aluminum sheets, which had previously been cleaned with an alkaline degreasing agent, were immersed for 5 seconds in the treatment solutions mentioned above, freed from excess solution by squeezing rollers and dried in a hot air stream of 120 ° C. for a period of 30 seconds.
Anschließend wurden die beschichteten Bleche mit einem Acrylatlack von 20 bis 25 ,um Dicke versehen. Der Lack wurde bei 200 0C 3 min eingebrannt.The coated metal sheets were then provided with an acrylate varnish from 20 to 25 μm thick. The paint was baked at 200 ° C. for 3 minutes.
Parallel hierzu wurden Probebleche der gleichen Beschaffenheit mit Lösungen 1 bis 4 behandelt, die mit den vorgenannten Lösungen übereinstimmten, jedoch keine Titan-und/oder Zirkonfluorid-Verbindung enthielten. Behandlungsart und Lackierung stimmten überein.At the same time, test panels of the same nature were treated with solutions 1 to 4, which were treated with the aforementioned Solutions matched, but did not contain any titanium and / or zirconium fluoride compounds. Type of treatment and painting agreed.
Schließlich wurden noch alkalisch gereinigte Aluminiumbleche mit einer 7 Gew.-%igen Chromatierungslösung chromatiert, wassergespült und mit Acrylatlack wie vorstehend beschrieben behandelt.Finally, aluminum sheets that had been cleaned under alkaline conditions were chromated with a 7% strength by weight chromating solution and rinsed with water and treated with acrylate varnish as described above.
Dann wurden die Bleche verschiedenen Tests unterworfen.The panels were then subjected to various tests.
Der salzwasser-Sprühtest erfolgte entsprechend JIS z-2317, bei dem ein bis auf die Metalloberfläche reichender Gitterschnitt vor der Sprühbehandlung angebracht wurde. Es wurde die ZeitThe salt water spray test was carried out in accordance with JIS z-2317 at to which a cross-cut reaching down to the metal surface was made before the spray treatment. It was time
registriert, bis die kreuzweise gekerbte Anstrichschicht abplatzte. registered until the cross-notched layer of paint flaked off.
Erichsen-Schachbrettfeld-Test: Hierbei kerbt man die Lackschicht in 100 Schachbrettfelder zu je 1 mm . Dann drückt man von der Rückseite der mit den Schachbrettfeldern versehenen Oberfläche mit dem Erichsen-Testgerät 3 mm durch und klebt auf die Wölbung der Lackfläche Klebeband auf. Danach reißt man das Klebeband rasch von der Lackfläche ab und registriert die Zahl der Schachbrettfelder, deren Lackschicht erhalten blieb.Erichsen checkerboard test: This is where the lacquer layer is notched in 100 chessboard fields of 1 mm each. Then press from the back of the checkerboard squares 3 mm through the surface with the Erichsen tester and stick adhesive tape to the curvature of the paint surface. Then you tear quickly removes the adhesive tape from the lacquer surface and registers the number of checkerboard fields whose lacquer layer was retained.
Erichsen-Schachbrettfeld-Test nach Zeitablauf: Hierbei wurden die behandelten Bleche zunächst 7 Tage bei 40 0C liegengelassen, dann lackiert und anschließend entsprechend dem Erichsen-Schachbrettfeld-Test unterworfen.Erichsen chessboard field test after the lapse of time: Here, the treated metal sheets were initially left to lie for 7 days at 40 ° C., then painted and then subjected to the Erichsen chessboard field test in accordance with the requirements.
Die Ergebnisse der Tests sind nachstehend tabellarisch wiedergegeben. Hierbei sind die nach dem erfindungsgemäßen Verfahren behandelten Bleche als Durchführungsbeispiele (Durchf.Bsp.), die anderen als Vergleichsbeispiele (Vergl.Bsp.) bezeichnet. Außerdem sind die Ergebnisse für gänzlich unbehandelte, also lediglich gereinigte und lackierte Bleche angegeben.The results of the tests are tabulated below. The sheets treated according to the method according to the invention are shown as implementation examples (implementation example), the others referred to as comparative examples (Comp. Ex.). Also, the results are for completely untreated, so only cleaned and varnished sheets indicated.
Ein Vergleich der Ergebnisse der Durchführungs- und Vergleichsbeispiele zeigt, daß der Korrosionsschutz der nach dem erfindungsgemäßen Verfahren behandelten Bleche unter Beibehaltung einer optimalen Lackhaftung durchgehend erheblich verbessert ist.A comparison of the results of the working and comparative examples shows that the corrosion protection of the sheets treated by the process according to the invention is maintained an optimal paint adhesion is consistently considerably improved.
Das lediglich chromatierte Aluminiumblech zeigt zwar einen ebenfalls hervorragenden Korrosionsschutz, läßt aber wesentliche Mangel beim Erichsen-Schachbrettfeld-Test erkennen.The only chromated aluminum sheet shows one also excellent corrosion protection, but shows significant deficiencies in the Erichsen checkerboard test.
Gegenstandtreated
object
wasser
sprühtestsalt
water
sprayed
Schac
feld-Eric
Schac
field-
n- Erichsen- n- Erichsen-
Schachbrett- Schachbrettfeld-Test
st nach ZeitablaufCheckerboard checkerboard test
st after the passage of time
behandelter Gegenstandtreated item
Behandlungtreatment
Salz- Erichsenwasser-Schachbrettsprühtest feld-TestSalt-Erichsenwasser checkerboard spray test field test
Erichsen-Erichsen-
Schachbrett-Checkerboard
feld-Testfield test
nach Zeitablaufafter the passage of time
100 100 100 100 100 100 100 100 50100 100 100 100 100 100 100 100 50
2020th
Claims (6)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17167182A JPS6022067B2 (en) | 1982-09-30 | 1982-09-30 | Method for forming film on metal surface |
Publications (1)
Publication Number | Publication Date |
---|---|
DE3408573A1 true DE3408573A1 (en) | 1985-09-12 |
Family
ID=15927531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19843408573 Ceased DE3408573A1 (en) | 1982-09-30 | 1984-03-09 | METHOD FOR TREATING METAL SURFACES |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0153973A1 (en) |
JP (1) | JPS6022067B2 (en) |
DE (1) | DE3408573A1 (en) |
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---|---|---|---|---|
DE10014035B4 (en) * | 2000-03-22 | 2006-07-13 | Electro Chemical Engineering Gmbh | Colored conversion layer, a solution for their preparation and their use |
Also Published As
Publication number | Publication date |
---|---|
JPS6022067B2 (en) | 1985-05-30 |
EP0153973A1 (en) | 1985-09-11 |
JPS5964781A (en) | 1984-04-12 |
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