EP0155742A2 - Process and coating composition for metallic surface treatment - Google Patents

Process and coating composition for metallic surface treatment Download PDF

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Publication number
EP0155742A2
EP0155742A2 EP85200412A EP85200412A EP0155742A2 EP 0155742 A2 EP0155742 A2 EP 0155742A2 EP 85200412 A EP85200412 A EP 85200412A EP 85200412 A EP85200412 A EP 85200412A EP 0155742 A2 EP0155742 A2 EP 0155742A2
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EP
European Patent Office
Prior art keywords
chromium
coating agent
total
weight ratio
coating
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EP85200412A
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German (de)
French (fr)
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EP0155742A3 (en
EP0155742B1 (en
Inventor
Thomas J. Prescott
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Henkel Corp
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Henkel Corp
Parker Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/33—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 hexavalent chromium compounds containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—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 characterised by the process
    • C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings

Definitions

  • the invention relates to a process for the treatment of metal surfaces by applying chromium-VI, silicate and / or silicic acid, phosphate and chromium-III-containing aqueous acidic coating agents and subsequent drying of the coating agent, its use for the treatment of cold-rolled steel and for the implementation of Appropriate coating agents.
  • the object of the invention is to provide a method and coating agent for treating metal surfaces which does not have the disadvantages of the known methods, is simple to carry out and leads to high-quality, in particular corrosion-protective coatings.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that a coating agent is applied in which the weight ratio of chromium-VI: chromium is in the range from (0.6 to 0.95): 1 lies.
  • Preferred refinements of the method according to the invention provide for a coating agent to be applied
  • the total PO 4 : chromium weight ratio is in the range from (0.1 to 5): 1, preferably from (0.1 to 1): 1, or
  • weight ratio chromium VI: SiO 2 : PO 4 : total chromium is in the range from (0.6 to 0.95): (0.5 to 5.0) : (0.1 to 5.0): 1 or in which the weight ratio of chromium-VI: SiO 2 : PO 4 : total chromium is in the range from (0.75 to 0.95): (1 to 3): (0.1 to 1.0): 1 .
  • the phosphate and chromate component can be introduced into the coating agent intended for carrying out the method according to the invention in any desired form, provided that the quality of the adhesion-promoting coating is not adversely affected thereby.
  • the addition as an alkali metal salt should be kept as low as possible and avoided as far as possible, since this can result in a loss of quality.
  • Phosphate and chromium VI are preferably used as relatively well soluble salts of di- or trivalent metals or of thermally stable ammonium or amine compounds (including the D ouble salts with the aforementioned metals), or as the acid introduced. Suitable divalent or trivalent metals are, for example, zinc, manganese, chromium, nickel, cobalt and iron.
  • the chromate component is preferably added as zinc dichromate or chromic acid and the phosphate component as zinc dihydrogen phosphate.
  • the silicate or the silica should be soluble in the coating agent or - homogeneously dispersible to form a colloidal dispersion. It is therefore preferably used in a finely divided form. Aerosols or precipitated silica are particularly suitable, but naturally occurring and finely ground quartz or diatomaceous earth can also be used if they can be dispersed homogeneously. Silicates such as montmorillonite or synthetic fluorosilicates such as e.g. Magnesium fluorosilicate with the trade name Laponit can be used. The use of soluble sodium or potassium silicates or fluorosilicates is less preferred, since these compounds tend to form glassy coatings with low adhesion. Therefore, preference is given to using water-insoluble silica or silicates that are colloidally distributable.
  • the chromium III content can be reduced by partial reduction aqueous chromic acid, for example with starch under heating, are produced in the customary manner (for example according to US Pat. No. 3,706,603), the resulting solution then containing chromium-VI and chromium-III compounds.
  • the coating agent used in the process according to the invention can also contain further additives. This is e.g. around divalent or trivalent metal cations, such as zinc, manganese, cobalt, nickel or iron, inert color pigments, in order to give the coating a specific color, silicone compounds, conductivity-producing materials, such as powdered metal (see, for example, US Pat. No. 3,671,331) or conductive carbon to increase weldability, and emulsifiers to keep the resin component in the dispersed state.
  • the emulsifier is usually already contained in the commercially available aqueous resin dispersion.
  • the coating agent can be used without pH adjustment. If the ingredients as salt are divalent or trivalent. Metals or added as acids, the pH will normally be below 2.5. When adding the components in the form of the ammonium or amine salts, the pH should be higher.
  • the coating agent can be produced by introducing the individual components in any order taking into account the weight ratios to be set.
  • the silica or the silicate is preferably added after the partial reduction of the hexavalent chromium, if the reduction is carried out with heating, since otherwise the dispersibility of the silica or silicate is impaired.
  • the aforementioned recommendation only applies in the event that the chromium III compound is obtained from chromium VI by reduction.
  • the components of the film on the metal surface are initially present in the same concentration as in the coating agent itself. Therefore, the concentrations of the active components in the supplement are essentially the same as in the working coating agent. This favors bathroom control and product uniformity.
  • the aqueous coating agent can be applied to the metal surface in any manner, as long as care is taken to ensure that the aqueous film has a reasonable and uniform thickness.
  • the film thickness can be checked in the simplest manner by rolling or squeezing rolls, the previous method of application being arbitrary and being able to be carried out, for example, electrostatically or by means of spray technology.
  • the layer thicknesses produced with the aid of the method according to the invention can be chosen within wide limits and can be, for example, 4.3 g / m 2 and higher.
  • the layer weight will normally be in the range of 54 to 1,076 mg / m 2 .
  • Typical coating weights for aluminum are tahlober inhabit surfaces 54 to 162 mg / m 2, for S 162 to 270 mg / m 2 and for zinc surfaces 108-216 mg / m 2.
  • the detailed process conditions are set depending on the desired layer weight.
  • a film of a certain thickness is applied to the metal surface and then dried. During the drying process, the concentration of the components of the coating agent and between it and the metal surface increases the reaction begins.
  • the process is particularly favorable can be carried out when applying a coating agent DES sen content of chromium from 0.8 to 12 wt .-%, preferably 0.8 to 8 wt .-%, is.
  • the coating agent can be applied at ambient temperature.
  • coating agents and / or metal surface can be heated.
  • the temperature of the metal can be brought to 93 ° C. or higher in the immersion or roll-up treatment, without the treatment bath being adversely affected.
  • the spraying technique even higher metal temperatures can be set.
  • the type of drying is not critical as long as the liquid film is not excessively interrupted or torn open, e.g. due to hot air currents or physical contact during drying.
  • the type of drying can influence the temperature required for drying. For example, drying takes place at a lower, maximum object temperature if it is carried out in the infrared oven instead of in the conventional oven.
  • the furnace temperature should be measured so that a metal temperature (maximum object temperature) of 52 to 163 ° C results.
  • Paint, varnish and the like can be applied to the dried layer in the usual way. Even though the paints or varnishes used in individual cases influence the corrosion resistance and the adhesion differently, it has been shown that with most of the commercially available paints and varnishes tested, the method according to the invention leads to results which are comparable to two- or three-stage conventional methods.
  • the method according to the invention is suitable for the treatment of aluminum, zinc, galvanized steel and iron-containing metal surfaces and alloys thereof.
  • a preferred application of the method according to the invention is in the treatment of cold-rolled steel, in particular because of the achievable high corrosion resistance and the achievable perfect deformability of the coated and temporarily stored strip or sheet.
  • Part of the invention is an aqueous coating agent for the treatment of metal surfaces containing chromium VI, silicate and / or silicic acid, phosphate and chromium III, which is characterized in that it contains chromium VI: chromium in total in the weight ratio of (0, 6 to 0.95): 1 contains ..
  • the absolute content of the active components of the coating agent essentially depends on the type of application. In general, the total chromium content is 0.8 to 12% by weight, preferably 0.8 to 8% by weight.
  • the advantage of the invention is, in particular, that coating agent is applied only once without rinsing, yet high corrosion protection - even with low layer weights - and good deformability are achieved as a result of good adhesion of paint or lacquer. A large number of metals can be treated.
  • the coating agent was applied to cold-rolled steel sheets with corrugated squeezing rollers, so that after drying in a conventional oven to a maximum temperature of the metal of 82 to 93 ° C., the layer weight was once 0.4 and once 0.183 g / m 2 . The sheets then rested for two weeks.
  • Example 1 After the procedure of Example 1, three coating compositions were prepared, which contained the components CrVI, PO 4 , Si0 2 and Cr total in the following weight ratios.
  • Coating agent 2a 0.6: 0.32: 2.0: 1.0
  • Coating agent 2b 0.6: 0.65: 2.0: 1.0
  • Coating agent 2c 0.6 0.97: 2.0: 1.0
  • coatings were applied using the aforementioned coating agents at a maximum object temperature of 82 to 93 ° C. in a conventional oven. Then the pre-treated sheets were painted.
  • a coating with 0.215 g / m 2 was applied to cold-rolled steel using a coating agent in which the weight ratio CrVI: PO 4 : SiO 2 : Cr was 0.93: 0.32: 2.0: 1.0 in total (after drying) applied.
  • the coating agent according to Example 3 was applied to the surface of hot-rolled steel sheet which had been preheated to approximately 93 ° C. After about 1 minute, the sheets were provided with a single-layer polyester lacquer or with a two-layer epoxy polyester topcoat. These sheets treated in this way were distinguished by excellent corrosion resistance, excellent paint adhesion and deformability.

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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)
  • Paints Or Removers (AREA)

Abstract

Coatings that provide a good base for paint, especially prior to subsequent forming operations, and that provide corrosion resistance are obtained on sheet steel or other metal surfaces by application of a composition containing hexavalent chromium, silica or silicate, phosphate and optionally trivalent chromium.

Description

Die Erfindung betrifft ein Verfahren zur Behandlung von Metalloberflächen durch Aufbringen von Chrom-VI, Silikat und/oder Kieselsäure, Phosphat und Chrom-III enthaltenden wäßrigen, sauren Überzugsmitteln und anschließendes Auftrocknen des Überzugsmittels, dessen Anwendung zur Behandlung von kaltgewalztem Stahl und für die Durchführung des Verfahrens geeignete Überzugsmittel.The invention relates to a process for the treatment of metal surfaces by applying chromium-VI, silicate and / or silicic acid, phosphate and chromium-III-containing aqueous acidic coating agents and subsequent drying of the coating agent, its use for the treatment of cold-rolled steel and for the implementation of Appropriate coating agents.

Die Notwendigkeit, Überzüge auf Metalloberflächen, insbesondere zur Vorbehandlung vor der nachfolgenden Lackierung, aufzubringen, ist seit langem bekannt. In diesem Zusammenhang wird besondere Beachtung der Lackhaftung auf der Metalloberfläche, der Feuchtigkeitsbeständigkeit der lackierten Metalloberfläche, der Salzsprühbeständigkeit und dem mit weiteren Methoden ermittelten Korrosionsverhalten des lackierten Artikels geschenkt. Sofern eine Verformung der lackierten Oberfläche beabsichtigt ist, ist auch die Verformbarkeit und der Korrosionswiderstand nach der Verformung von Bedeutung.The need to apply coatings to metal surfaces, especially for pretreatment before subsequent painting, has long been known. In this context, special attention is paid to the paint adhesion on the metal surface, the moisture resistance of the painted metal surface, the salt spray resistance and the corrosion behavior of the painted article determined using other methods. If deformation of the painted surface is intended, the deformability and the corrosion resistance after the deformation are also important.

In der Vergangenheit sind häufig Schwierigkeiten bei der Entwicklung von Überzugsmitteln für und Behandlungsverfahren von Metalloberflächen aufgetreten, wenn Produkte gefordert wurden, die bei und nach der Verformung eine zufriedenstellende Lackhaftung und einen zufriedenstellenden Korrosionswiderstand aufweisen sollen. Beispielsweise werden üblicherweise hohe Schichtgewichte im Hinblick auf Korrosionsschutz, aber niedrige Schichtgewichte für die Verformung gefordert. Im allgemeinen läßt sich feststellen, daß konventionelle Überzugsmittel und Verfahren zur Behandlung von Metalloberflächen mehrstufige Behandlungsverfahren mit Wasserspülung nach jeder Behandlungsstufe erfordern. Dies ist jedoch mit einem hohen Personalaufwand, Kontaminierungsproblemen zwischen den Stufen, einer beträchtlichen Anlagenlänge und Abwasserproblemen für die Spülwässer verbunden.In the past, difficulties have often arisen in the development of coating compositions for and treatment processes of metal surfaces when products have been required which are to have satisfactory paint adhesion and corrosion resistance during and after the deformation. For example, high layer weights are usually required with regard to corrosion protection, but low layer weights are required for the deformation. in the In general, it can be stated that conventional coating agents and processes for the treatment of metal surfaces require multi-step treatment processes with water rinsing after each treatment step. However, this is associated with high manpower, contamination problems between the stages, a considerable length of the plant and waste water problems for the rinsing water.

Aufgabe der Erfindung ist es, ein Verfahren und Überzugsmittel zur Behandlung von Metalloberflächen bereitzustellen, das die Nachteile der bekannten Verfahren nicht aufweist, einfach in der Durchführung ist und zu qualitativ hochwertigen, insbesondere korrosionsschützenden Überzügen führt.The object of the invention is to provide a method and coating agent for treating metal surfaces which does not have the disadvantages of the known methods, is simple to carry out and leads to high-quality, in particular corrosion-protective coatings.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art ensprechend der Erfindung derart ausgestaltet wird, daß man ein.Überzugsmittel aufbringt, in dem das Gewichtverhältnis von Chrom-VI : Chrom im Bereich von (0,6 bis 0,95) : 1 liegt.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that a coating agent is applied in which the weight ratio of chromium-VI: chromium is in the range from (0.6 to 0.95): 1 lies.

Bevorzugte Ausgestaltungen des erfindungsgemäßen Verfahrens sehen vor, ein Überzugsmittel aufzubringen,Preferred refinements of the method according to the invention provide for a coating agent to be applied

in dem das Gewichtsverhältnis von PO4 : Chrom gesamt im Bereich von (0,1 bis 5) : 1, vorzugsweise von (0,1 bis l) : 1, liegt bzw.in which the total PO 4 : chromium weight ratio is in the range from (0.1 to 5): 1, preferably from (0.1 to 1): 1, or

in dem das Gewichtsverhältnis Chrom-VI : SiO2 : PO4 : Chrom gesamt im Bereich von (0,6 bis 0,95) : (0,5 bis 5,0) : (0,1 bis 5,0) : 1 liegt bzw. in dem das Gewichtsverhältnis Chrom-VI : SiO2 : PO4 : Chrom gesamt im Bereich von (0,75 bis 0,95) : (1 bis 3) : (0,1 bis 1,0) : 1 liegt.in which the weight ratio chromium VI: SiO 2 : PO 4 : total chromium is in the range from (0.6 to 0.95): (0.5 to 5.0) : (0.1 to 5.0): 1 or in which the weight ratio of chromium-VI: SiO 2 : PO 4 : total chromium is in the range from (0.75 to 0.95): (1 to 3): (0.1 to 1.0): 1 .

Die Phosphat- und Chromatkomponente kann in das zur Durchführung des erfindungsgemäßen Verfahrens bestimmte Überzugsmittel in jeder beliebigen Form eingebracht werden, sofern die Qualität des haftvermittelnden Überzuges hierdurch nicht beeinträchtigt wird. Die Zugabe als Alkalimetallsalz sollte so gering wie möglich gehalten, möglichst ganz vermieden werden, da hierdurch Qualitätseinbußen auftreten können. Phosphat und Chrom-VI werden vorzugsweise als vergleichsweise gut lösliche Salze von zwei- oder dreiwertigen Metallen oder von thermisch stabilen Ammonium- oder Aminverbindungen (einschließlich der Doppelsalze mit den vorgenannten Metallen) oder als Säure eingebracht. Geeignete zwei- oder dreiwertige Metalle sind beispielsweise Zink, Mangan, Chrom, Nickel, Cobalt und Eisen. Die Chromatkomponente wird vorzugsweise als Zinkdichromat oder Chromsäure und die Phosphatkomponente als Zinkdihydrogenphosphat zugegeben.The phosphate and chromate component can be introduced into the coating agent intended for carrying out the method according to the invention in any desired form, provided that the quality of the adhesion-promoting coating is not adversely affected thereby. The addition as an alkali metal salt should be kept as low as possible and avoided as far as possible, since this can result in a loss of quality. Phosphate and chromium VI are preferably used as relatively well soluble salts of di- or trivalent metals or of thermally stable ammonium or amine compounds (including the D ouble salts with the aforementioned metals), or as the acid introduced. Suitable divalent or trivalent metals are, for example, zinc, manganese, chromium, nickel, cobalt and iron. The chromate component is preferably added as zinc dichromate or chromic acid and the phosphate component as zinc dihydrogen phosphate.

Das Silikat oder die Kieselsäure sollte in dem Überzugsmittel löslich oder - unter Bildung einer kolloidalen Dispersion - homogen dispergierbar sein. Es wird daher vorzugsweise in feinverteilter Form verwendet. Besonders geeignet sind Aerosole oder gefällte Kieselsäure, jedoch können auch natürlich vorkommender und fein aufgemahlener Quarz oder Diatomeenerde verwendet werden, sofern sie sich homogen dispergieren lassen. Es können auch Silikate, wie Montmorillonit, oder synthetische Fluorosilikate, wie z.B. Magnesiumfluorosilikat mit der Handelsbezeichnung Laponit, eingesetzt werden. Die Verwendung löslicher Natrium- oder Kaliumsilikate bzw. Fluorosilikate ist weniger bevorzugt, da diese Verbindungen die Neigung besitzen, glasige Überzüge mit geringem Haftvermögen zu bilden. Daher wird der Verwendung wasserunlöslicher Kieselsäure oder Silikate, die kolloidal verteilbar sind, der Vorzug gegeben.The silicate or the silica should be soluble in the coating agent or - homogeneously dispersible to form a colloidal dispersion. It is therefore preferably used in a finely divided form. Aerosols or precipitated silica are particularly suitable, but naturally occurring and finely ground quartz or diatomaceous earth can also be used if they can be dispersed homogeneously. Silicates such as montmorillonite or synthetic fluorosilicates such as e.g. Magnesium fluorosilicate with the trade name Laponit can be used. The use of soluble sodium or potassium silicates or fluorosilicates is less preferred, since these compounds tend to form glassy coatings with low adhesion. Therefore, preference is given to using water-insoluble silica or silicates that are colloidally distributable.

Der Chrom-III-Anteil kann durch partielle Reduktion einer wäßrigen Chromsäure, z.B. mit Stärke unter Erwärmung, auf übliche Weise erzeugt werden (z.B. gemäß US-PS 3 706 603), wobei dann die resultierende Lösung Chrom-VI- und Chrom-III-Verbindungen enthält.The chromium III content can be reduced by partial reduction aqueous chromic acid, for example with starch under heating, are produced in the customary manner (for example according to US Pat. No. 3,706,603), the resulting solution then containing chromium-VI and chromium-III compounds.

Neben den vorgenannten Verbindungen kann das innerhalb des erfindungsgemäßen Verfahrens zum Einsatz kommende Überzugsmittel noch weitere Zusätze erhalten. Hierbei handelt es sich z.B. um zwei- oder dreiwertige Metallkationen, wie Zink, Mangan, Cobalt, Nickel oder Eisen, inerte Farbpigmente, um dem Überzug eine spezifische Farbe zu geben, Silikonverbindungen, Leitfähigkeit herbeiführende Materialien, wie pulverförmiges Metall (vgl. z.B. US-PS 3 671 331) oder leitfähiger Kohlenstoff, um die Schweißbarkeit zu erhöhen, sowie Emulgatoren, die die Harzkomponente im dispergierten Zustand halten. Der Emulgator ist üblicherweise in der handelsüblichen wäßrigen Harzdispersion bereits enthalten.In addition to the aforementioned compounds, the coating agent used in the process according to the invention can also contain further additives. This is e.g. around divalent or trivalent metal cations, such as zinc, manganese, cobalt, nickel or iron, inert color pigments, in order to give the coating a specific color, silicone compounds, conductivity-producing materials, such as powdered metal (see, for example, US Pat. No. 3,671,331) or conductive carbon to increase weldability, and emulsifiers to keep the resin component in the dispersed state. The emulsifier is usually already contained in the commercially available aqueous resin dispersion.

Das Überzugsmittel kann ohne pH-Wert-Einstellung benutzt werden. Wenn die Bestandteile als Salz zwei- oder dreiwertiger. Metalle oder als Säuren zugegeben werden, wird der pH-Wert normalerweise unter 2,5 liegen. Bei Zugabe der Bestandteile in Form der Ammonium- oder Aminsalze dürfte der pH-Wert höher sein.The coating agent can be used without pH adjustment. If the ingredients as salt are divalent or trivalent. Metals or added as acids, the pH will normally be below 2.5. When adding the components in the form of the ammonium or amine salts, the pH should be higher.

Das Überzugsmittel kann hergestellt werden, indem die einzelnen Bestandteile unter Berücksichtigung der einzustellenden Gewichtsverhältnisse in beliebiger Reihenfolge eingebracht werden. Jedoch wird die Kieselsäure oder das Silikat vorzugsweise nach der partiellen Reduktion des sechswertigen Chroms zugegeben, sofern die Reduktion unter Erwärmung durchgeführt wird, da andernfalls die Dispergierbarkeit von Kieselsäure oder Silikat verschlechtert wird. Die vorgenannte Empfehlung gilt jedoch nur für den Fall, daß die Chrom-III-Verbindung aus Chrom-VI durch Reduktion gewonnen wird.The coating agent can be produced by introducing the individual components in any order taking into account the weight ratios to be set. However, the silica or the silicate is preferably added after the partial reduction of the hexavalent chromium, if the reduction is carried out with heating, since otherwise the dispersibility of the silica or silicate is impaired. However, the aforementioned recommendation only applies in the event that the chromium III compound is obtained from chromium VI by reduction.

Da keine wesentliche Reaktion mit der Metalloberfläche vor dem Auftrocknen stattfindet, sind die Komponenten des auf der Metalloberfläche befindlichen Films anfänglich in der gleichen Konzentration vorhanden wie im Überzugsmittel selbst. Daher sind die Konzentrationen der wirksamen Komponenten im Ergänzungsmittel im wesentlichen die gleichen wie im arbeitenden Überzugsmittel. Hierdurch werden Badkontrolle und Produktgleichmäßigkeit begünstigt.Since there is no substantial reaction with the metal surface prior to drying, the components of the film on the metal surface are initially present in the same concentration as in the coating agent itself. Therefore, the concentrations of the active components in the supplement are essentially the same as in the working coating agent. This favors bathroom control and product uniformity.

Die Aufbringung des wäßrigen Überzugsmittels auf die Metalloberfläche kann auf jede beliebige Art erfolgen, solange Sorge dafür getragen wird, daß eine sinnvolle und einheitliche Dicke des wäßrigen Films entsteht. Für ebene Flächen, wie Band oder Blech, kann die Filmdicke in einfachster Weise durch Rollen oder Abquetschrollen kontrolliert werden, wobei die vorherige Art der Aufbringung beliebig ist und beispielsweise elektrostatisch oder mittels Sprühtechnik erfolgen kann.The aqueous coating agent can be applied to the metal surface in any manner, as long as care is taken to ensure that the aqueous film has a reasonable and uniform thickness. For flat surfaces such as strip or sheet metal, the film thickness can be checked in the simplest manner by rolling or squeezing rolls, the previous method of application being arbitrary and being able to be carried out, for example, electrostatically or by means of spray technology.

Die mit Hilfe des erfindungsgemäßen Verfahrens erzeugten Schichtdicken können in weiten Grenzen gewählt werden und z.B. bei 4,3 g/m2 und höher liegen. Normalerweise wird das Schichtgewicht im Bereich von 54 bis 1.076 mg/m2 liegen. Typische Schichtgewichte sind für Aluminiumoberflächen 54 bis 162 mg/m2, für Stahloberflächen 162 bis 270 mg/m2 und für Zinkoberflächen 108 bis 216 mg/m2.The layer thicknesses produced with the aid of the method according to the invention can be chosen within wide limits and can be, for example, 4.3 g / m 2 and higher. The layer weight will normally be in the range of 54 to 1,076 mg / m 2 . Typical coating weights for aluminum are tahloberflächen surfaces 54 to 162 mg / m 2, for S 162 to 270 mg / m 2 and for zinc surfaces 108-216 mg / m 2.

Üblicherweise werden die detaillierte"1 Prozeßbedingungen in Abhängigkeit vom gewünschten Schichtgewicht eingestellt. Je nach Gesamtkonzentration der Bestandteile des Überzugsmittels wird ein Film bestimmter Dicke auf die Metalloberfläche aufgebracht und dann aufgetrocknet. Während des Auftrocknens steigt die Konzentration der Bestandteile des Überzugsmittels und zwischen ihm und der Metalloberfläche beginnt die Reaktion.Usually, the detailed process conditions are set depending on the desired layer weight. Depending on the total concentration of the components of the coating agent, a film of a certain thickness is applied to the metal surface and then dried. During the drying process, the concentration of the components of the coating agent and between it and the metal surface increases the reaction begins.

Es hat sich gezeigt, daß das Verfahren besonders günstig durchführbar ist, wenn man ein Überzugsmittel aufbringt, des- sen Gehalt an Chrom 0,8 bis 12 Gew.-%, vorzugsweise 0,8 bis 8 Gew.-%, beträgt.It has been shown that the process is particularly favorable can be carried out when applying a coating agent DES sen content of chromium from 0.8 to 12 wt .-%, preferably 0.8 to 8 wt .-%, is.

Das Überzugsmittel kann mit Umgebungstemperatur aufgebracht werden. Um den Prozeß zu beschleunigen, können jedoch Überzugsmittel und/oder Metalloberfläche erwärmt werden. Beispielsweise kann bei der Tauch- oder Aufrollbehandlung die Temperatur des Metalles auf 93°C oder höher gebracht werden, ohne daß das Behandlungsbad beeinträchtigt wird. Bei der Aufsprühtechnik können noch höhere Metalltemperaturen eingestellt werden. Die Art der Auftrocknung ist solange nicht kritisch, wie der Flüssigkeitsfilm nicht übermäßig unterbrochen oder aufgerissen wird, z.B. durch heiße Luftströme oder physikalischen Kontakt bei der Trocknung. Jedoch kann die Art der Auftrocknung die für die Auftrocknung erforderliche Temperatur beeinflussen. Beispielsweise wird die Auftrocknung bei niedrigerer, maximaler Objekttemperatur erreicht, wenn sie im Infrarotofen anstatt im konventionellen Ofen erfolgt.The coating agent can be applied at ambient temperature. To accelerate the process, however, coating agents and / or metal surface can be heated. For example, the temperature of the metal can be brought to 93 ° C. or higher in the immersion or roll-up treatment, without the treatment bath being adversely affected. With the spraying technique, even higher metal temperatures can be set. The type of drying is not critical as long as the liquid film is not excessively interrupted or torn open, e.g. due to hot air currents or physical contact during drying. However, the type of drying can influence the temperature required for drying. For example, drying takes place at a lower, maximum object temperature if it is carried out in the infrared oven instead of in the conventional oven.

Unter normalen Bedingungen ist die Verwendung von erhöhten Ofentemperaturen und Warmluftströmen einer Geschwindigkeit, die den Naßfilm nicht nachteilig beeinträchtigen, bevorzugt. Aus praklischer Sicht sollte die Ofentemperatur derart bemessen werden, daß eine Metalltemperatur (maximale Objekttemperatur) von 52 bis 163°C resultiert.Under normal conditions, the use of elevated oven temperatures and hot air streams at a speed that does not adversely affect the wet film is preferred. From a practical point of view, the furnace temperature should be measured so that a metal temperature (maximum object temperature) of 52 to 163 ° C results.

Auf die aufgetrocknete Schicht kann Farbe, Lack und dergl. auf übliche Weise aufgebracht werden. Wenn auch die im einzelnen verwendeten Farben oder Lacke den Korrosionswiderstand und die Haftung unterschiedlich beeinflussen, so hat sich doch gezeigt, daß bei den meisten getesteten handelsüblichen Farben und Lacken das erfindungsgemäße Verfahren zu Ergebnissen führt, die mit zwei- oder dreistufigen konventionellen Verfahren vergleichbar sind.Paint, varnish and the like can be applied to the dried layer in the usual way. Even though the paints or varnishes used in individual cases influence the corrosion resistance and the adhesion differently, it has been shown that with most of the commercially available paints and varnishes tested, the method according to the invention leads to results which are comparable to two- or three-stage conventional methods.

Das erfindungsgemäße Verfahren ist zur Behandlung von Aluminium, Zink, verzinktem Stahl und eisenhaltigen Metalloberflächen und Legierungen hiervon geeignet. Ein bevorzugter Anwendungsfall des erfindungsgemäßen Verfahrens liegt in der Behandlung von kaltgewalztem Stahl, und zwar insbesondere wegen des erzielbaren hohen Korrosionswiderstandes und der erzielbaren einwandfreien Verformbarkeit von lackiertem und zwischengelagertem Band oder Blech.The method according to the invention is suitable for the treatment of aluminum, zinc, galvanized steel and iron-containing metal surfaces and alloys thereof. A preferred application of the method according to the invention is in the treatment of cold-rolled steel, in particular because of the achievable high corrosion resistance and the achievable perfect deformability of the coated and temporarily stored strip or sheet.

Bestandteil der Erfindung ist ein wäßriges Überzugsmittel zur Behandlung von Metalloberflächen mit einem Gehalt an Chrom-VI, Silikat und/oder Kieselsäure, Phospat und Chrom-III, das dadurch gekennzeichnet ist, daß es Chrom-VI : Chrom gesamt im Gewichtsverhältnis von (0,6 bis 0,95) : 1 enthält..Part of the invention is an aqueous coating agent for the treatment of metal surfaces containing chromium VI, silicate and / or silicic acid, phosphate and chromium III, which is characterized in that it contains chromium VI: chromium in total in the weight ratio of (0, 6 to 0.95): 1 contains ..

Bevorzugte Ausgestaltungen sehen ein Überzugsmittel vor, das PO4 : Chrom gesamt im Gewichtsverhältnis von (0,1 bis 5) :

  • 1, vorzugsweise von (0,1 bis 1) : 1 enthält bzw. das Chrom-VI : SiO2 : PO4 : Chrom gesamt im Gewichtsverhältnis von (0,6 bis 0,95) : (0,5 bis 5,0) : (0,1 bis 5,0) : 1, vorzugsweise t
Preferred embodiments provide a coating agent which contains PO 4 : total chromium in a weight ratio of (0.1 to 5):
  • 1, preferably from (0.1 to 1): 1 or the chromium VI: SiO 2 : PO 4 : total chromium in a weight ratio of (0.6 to 0.95): (0.5 to 5.0 ): (0.1 to 5.0): 1, preferably t

von (0,75 bis 0,95) : (1 bis 3) : (0,1 bis 1,0) : 1 enthält.from (0.75 to 0.95): (1 to 3): (0.1 to 1.0): 1 contains.

Der Absolutgehalt der wirksamen Bestandteile des Überzugsmittels hängt im wesentlichen von der Art der Aufbringung ab. Im allgemeinen liegt der Gehalt an Chrom gesamt bei 0,8 bis 12 Gew.-%, vorzugsweise bei 0,8 bis 8 Gew.-%.The absolute content of the active components of the coating agent essentially depends on the type of application. In general, the total chromium content is 0.8 to 12% by weight, preferably 0.8 to 8% by weight.

Der Vorteil der Erfindung besteht insbesondere darin, daß nur ein einmaliger Auftrag von Überzugsmittel ohne Nachspülung erfolgt, dennoch hoher Korrosionsschutz - selbst bei geringen Schichtgewichten - und gute Verformbarkeit infolge guter Haftung von Farbe oder Lack erreicht werden. Es kann eine große Zahl von Metallen behandelt werden.The advantage of the invention is, in particular, that coating agent is applied only once without rinsing, yet high corrosion protection - even with low layer weights - and good deformability are achieved as a result of good adhesion of paint or lacquer. A large number of metals can be treated.

Die Erfindung wird anhand der Beispiele beispielsweise und näher beschrieben.The invention is described by way of example and in more detail.

Beispiel 1example 1

Zur Herstellung eines Überzugsmittels wird eine Chromsäurelösung durch partielle Reduktion des Chrom-VI mit Stärke unter Wärmeeinwirkung in eine Chrom-VI und Chrom-III enthaltende Lösung überführt. Dann wird mit Phosphorsäure und einer 10%igen (Gew.-/Vol.) Aerosildispersion (in Wasser aufgemahlene Kieselsäure) derart versetzt, daß eine Dispersion mit einem Gewichtsverhältnis von Chrom-VI : PO4 : SiO2 :

  • Chromgesamt wie 0,87 : 0,97 : 2,0 : 1,0 resultiert.
To produce a coating agent, a chromic acid solution is converted by partial reduction of the chromium VI with starch under the action of heat into a solution containing chromium VI and chromium III. Then phosphoric acid and a 10% (w / v) aerosil dispersion (silica ground in water) are added such that a dispersion with a weight ratio of chromium-VI: PO 4 : SiO 2 :
  • Total chrome as 0.87: 0.97: 2.0: 1.0 results.

Das Überzugsmittel wurde auf kaltgewalzte Stahlbleche mit geriffelten Abquetschwalzen aufgetragen, so daß sich nach Trocknung in einem konventionellen Ofen auf eine Maximaltemperatur des Metalles auf 82 bis 93°C ein Schichtgewicht von einmal 0,4 und einmal 0,183 g/m2 ergab. Danach ruhten die Bleche zwei Wochen.The coating agent was applied to cold-rolled steel sheets with corrugated squeezing rollers, so that after drying in a conventional oven to a maximum temperature of the metal of 82 to 93 ° C., the layer weight was once 0.4 and once 0.183 g / m 2 . The sheets then rested for two weeks.

Dann wurden einige der Bleche mit einem Einschicht-Polyesterlack, einige mit einem Einschicht-Vinyllack und einige mit einem Zweischicht-Epoxypolyesterlack versehen. Alle Bleche zeigten gute Lackhaftung, gute Korrosionsbeständigkeit und gute Verformbarkeit.Then some of the sheets were coated with a one-layer polyester paint, some with a single-layer vinyl paint and some with a two-layer epoxy polyester paint. All sheets showed good paint adhesion, good corrosion resistance and good ductility.

Beispiel 2Example 2

Nach dem Verfahrensgang des Beispiels 1 wurden drei Überzugsmittel hergestellt, die die Komponenten CrVI, PO4, Si02 und Cr gesamt in folgenden Gewichtsverhältnissen enthielt. Überzugsmittel 2a 0,6 : 0,32 : 2,0 : 1,0 Überzugsmittel 2b 0,6 : 0,65 : 2,0 : 1,0 Überzugsmittel 2c 0,6 0,97 : 2,0 : 1,0 Wie in Beispiel 1 wurden mittels der vorgenannten Überzugsmittel Überzüge bei einer maximalen Objekttemperatur von 82 bis 93°C in einem konventionellen Ofen aufgebracht. Dann wurden die so vorbehandelten Bleche lackiert.After the procedure of Example 1, three coating compositions were prepared, which contained the components CrVI, PO 4 , Si0 2 and Cr total in the following weight ratios. Coating agent 2a 0.6: 0.32: 2.0: 1.0 Coating agent 2b 0.6: 0.65: 2.0: 1.0 Coating agent 2c 0.6 0.97: 2.0: 1.0 As in Example 1, coatings were applied using the aforementioned coating agents at a maximum object temperature of 82 to 93 ° C. in a conventional oven. Then the pre-treated sheets were painted.

Ein Vergleich der behandelten Bleche zeigte, daß sich der Korrosionsschutz (ermittelt im Salzsprühtest) mit steigendem P04-Gehalt verbesserte, jedoch die Verformbarkeit verringerte.A comparison of the treated sheets showed that the corrosion protection (determined in the salt spray test) improved with increasing P0 4 content, but reduced the deformability.

Beispiel 3Example 3

Auf kaltgewalzten Stahl wurde mit einem Überzugsmittel, in dem das Gewichtsverhältnis CrVI : PO4 : SiO2 : Cr gesamt 0,93 : 0,32 : 2,0 : 1,0 war, nach dem Rollenauftragsverfahren ein Überzug mit 0,215 g/m2 (nach der Auftrocknung) aufgebracht.A coating with 0.215 g / m 2 was applied to cold-rolled steel using a coating agent in which the weight ratio CrVI: PO 4 : SiO 2 : Cr was 0.93: 0.32: 2.0: 1.0 in total (after drying) applied.

Die Auftrocknung erfolgte bei einer maximalen Objekttemperatur von 149°C. Nach 30 sec langem Abkühlen im Raum wurden die Bleche, wie in Beispiel 1 angegeben, lackiert. Alle Bleche besaßen guten Korrosionswiderstand, gute Lackhaftungseigenschaften und gute Verformbarkeit.Drying was carried out at a maximum object temperature of 149 ° C. After cooling for 30 seconds in the room, the metal sheets were painted as described in Example 1. All sheets had good corrosion resistance, good paint adhesion properties and good ductility.

Beispiel 4Example 4

Das Überzugsmittel gemäß Beispiel 3 wurde auf die Oberfläche von heißgewalztem Stahlblech, das auf ca. 93°C vorgewärmt worden war, aufgetragen. Nach etwa 1 min wurden die Bleche mit einem Einschicht-Polyesterlack bzw. mit einem Zweischicht-Epoxypolyesterabdecklack versehen. Diese so behandelten Bleche zeichneten sich durch hervorragenden Korrosionswiderstand, hervorragende Lackhaftung und Verformbarkeit aus.The coating agent according to Example 3 was applied to the surface of hot-rolled steel sheet which had been preheated to approximately 93 ° C. After about 1 minute, the sheets were provided with a single-layer polyester lacquer or with a two-layer epoxy polyester topcoat. These sheets treated in this way were distinguished by excellent corrosion resistance, excellent paint adhesion and deformability.

Claims (10)

1. Verfahren zur Behandlung von Metalloberflächen durch Aufbringen von Chrom-VI, Silikat und/oder Kieselsäure, Phosphat und Chrom-III enthaltenden wäßrigen, sauren Überzugsmitteln und anschließendes Auftrocknen des Überzugsmittels, dadurch gekennzeichnet, daß man ein Überzugsmittel aufbringt, in dem das Gewichtsverhältnis von Chrom-VI : Chrom gesamt im Bereich von (0,6 bis 0,95) : 1 liegt.1. Process for the treatment of metal surfaces by applying chromium-VI, silicate and / or silicic acid, phosphate and chromium-III-containing aqueous acidic coating agents and subsequent drying of the coating agent, characterized in that applying a coating agent in which the weight ratio of Chromium VI: Total chromium is in the range from (0.6 to 0.95): 1. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man ein Überzugsmittel aufbringt, in dem das Gewichtsverhältnis von PO4 : Chrom gesamt im Bereich von (0,1 bis 5) : 1, vorzugsweise von (0,1 bis 1) : 1, liegt.2. The method according to claim 1, characterized in that a coating agent is applied in which the weight ratio of PO 4 : chromium total in the range from (0.1 to 5): 1, preferably from (0.1 to 1): 1 , lies. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man ein Überzugsmittel aufbringt, in dem das Gewichtsverhältnis Chrom-VI : SiO2 : PO4 : Chrom gesamt im Bereich von (0,6 bis 0,95) : (0,5 bis 5,0) : (0,1 bis 5,0) : 1 liegt.3. The method according to claim 1 or 2, characterized in that a coating agent is applied in which the weight ratio chromium-VI: SiO 2 : PO 4 : chromium total in the range from (0.6 to 0.95): (0, 5 to 5.0): (0.1 to 5.0): 1 is. 4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man ein Überzugsmittel aufbringt, in dem das Gewichtsverhältnis Chrom-VI : SiO2 : PO4 : Chrom gesamt im Bereich von (0,75 bis 95) : (1 bis 3) : (0,1 bis 1,0) : 1 liegt.4. The method according to claim 1 or 2, characterized in that a coating agent is applied in which the weight ratio chromium-VI: SiO 2 : PO 4 : chromium total in the range from (0.75 to 95): (1 to 3) : (0.1 to 1.0): 1 lies. 5. Verfahren nach Anspruch 1, 2, 3 oder 4, dadurch gekennzeichnet, daß man ein Überzugsmittel aufbringt, dessen Gehalt an Chrom gesamt 0,8 bis 12, vorzugsweise 0,8 bis 8, Gew.-%, beträgt.5. The method according to claim 1, 2, 3 or 4, characterized in that a coating agent is applied, the total chromium content of which is 0.8 to 12, preferably 0.8 to 8,% by weight. 6. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 5 auf die Behandlung von kaltgewalztem Stahl. 6 . Application of the method according to one or more of claims 1 to 5 to the treatment of cold-rolled steel. 7. Wäßriges Überzugsmittel zur Behandlung von Metalloberflächen mit einem Gehalt an Chrom-VI, Silikat und/oder Kieselsäure, Phosphat und Chrom-III, dadurch gekennzeichnet, daß es Chrom-VI : Chrom gesamt im Gewichtsverhältnis von (0,6 bis 0,95) : 1 enthält.7. Aqueous coating agent for the treatment of metal surfaces containing chromium VI, silicate and / or silicic acid, phosphate and chromium III, characterized in that it contains chromium VI: chromium in a total weight ratio of (0.6 to 0.95 ): 1 contains. 8. Überzugsmittel nach Anspruch 7, dadurch gekennzeichnet, das es PO4 : Chrom gesamt im Gewichtsverhältnis von (0,1 bis 5) : 1, vorzugsweise von (0,1 bis l) : 1, enthält.8. Coating composition according to claim 7, characterized in that it contains PO 4 : total chromium in a weight ratio of (0.1 to 5): 1, preferably from (0.1 to 1): 1. 9. Überzugsmittel nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß es Chrom-VI : SiO2 : PO4 : Chrom gesamt im Gewichtsverhältnis von (0,6 bis 0,95) : (0,5 bis 5,0) : (0,1 bis 5,0)': 1, vorzugsweise im Gewichtsverhältnis von (0,75 bis 0,95) : (1 bis 3) : (0,1 bis 1,0) : 1, enthält. 9. Coating composition according to claim 7 or 8, characterized in that it is chromium VI: SiO 2 : PO 4 : Total chromium in the weight ratio of (0.6 to 0.95): (0.5 to 5.0): (0.1 to 5.0) ': 1, preferably in the weight ratio of (0.75 to 0.95 ): (1 to 3): (0.1 to 1.0): 1, contains. 10. Überzugsmittel nach Anspruch 7, 8 oder 9, dadurch gekennzeichnet, daß es 0,8 bis 12 Gew.-%, vorzugsweise 0,8 bis 8 Gew.-%, Chrom gesamt enthält.10. Coating agent according to claim 7, 8 or 9, characterized in that it contains 0.8 to 12 wt .-%, preferably 0.8 to 8 wt .-%, total chromium.
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DE102015104887B4 (en) 2015-03-30 2022-05-19 Benteler Steel/Tube Gmbh Tubular product and method of making same

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GB2155962B (en) 1987-12-31
DE3509556A1 (en) 1985-10-24
GB8507516D0 (en) 1985-05-01
AR242247A1 (en) 1993-03-31
JPS60218483A (en) 1985-11-01
ZA852128B (en) 1985-11-27
GB2155962A (en) 1985-10-02
NZ211485A (en) 1988-07-28
MX166776B (en) 1993-02-03
DE3583512D1 (en) 1991-08-29
AU580041B2 (en) 1988-12-22
BR8501308A (en) 1985-11-19
EP0155742A3 (en) 1987-04-29
CA1256003A (en) 1989-06-20
AU4028085A (en) 1985-09-26
JPH0422986B2 (en) 1992-04-21
EP0155742B1 (en) 1991-07-24

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