EP2129476B1 - Multi-coated metal substrate and method for the production thereof - Google Patents

Abstract

A metal sheet, inclusive of a metal strip, having a front side and a back side, both the front side and the back side comprising a first coating having an average thickness in the range from 0.5 to 10 mum, wherein the first coating of the front side contains particles, which release divalent or multivalent metal ions upon the action of an acid, in such an amount that a self-depositing coating agent forms, upon contact with the front side, a second coating thereon, whereas this is not the case for the first coating of the back side. The first coating of the front side can be overcoated with a self-depositing coating agent. Cut edges that do not have a first coating can be covered with the self-depositing coating agent. Correspondingly coated metal sheets, as well as a method for the manufacture thereof, are furthermore within the scope of the invention.

Description

The present invention relates to a metal substrate which has at least two different coatings for corrosion protection, to a method for producing such a metal substrate, and to the use of such a metal substrate for the production of articles.

Base metals must be protected against corrosion. This applies to all conventional construction metals such as iron, steel, zinc, titanium, aluminum, magnesium or their alloys. Usually, these metals are provided with one or more inorganic and / or organic coatings. In addition to the corrosion protection desired aesthetic effects are achieved here. For this purpose, different coating types and coating methods are known and used in the prior art.

For example, it is customary to subject, if necessary, cleaned metal surfaces to a so-called conversion treatment. This forms a coating in which ions of the metal surface are incorporated. Examples of these are: chromating, layer-forming or non-layer-forming phosphating or treatment with an acidic aqueous solution of complex fluorides of at least one of the elements B, Si, Ti and / or Zr. In addition, such conversion solutions may contain organic polymers.

For low or only temporary corrosive stress, it may be sufficient to confine oneself to such a conversion treatment. Typically, however, the conversion-treated metal surfaces are overcoated with one or more organic coatings of varying thickness. These organic coatings usually contain (crosslinked) organic polymers. With a suitable choice of the organic coating agent, however, can also be dispensed with a conversion treatment. This means that an organic coating composition based on (preferably crosslinked or crosslinking) polymers can also be applied directly to a bare metal surface. Different types of organic coating agents are known for this purpose. The crosslinking of the organic polymers is generally carried out by one or more of the following reaction types: Polymerization of Compounds with carbon-carbon multiple bonds, formation of urethane bonds by reaction of isocyanates, ring-opening reaction of epoxides, formation of polyesters.

Such crosslinking reactions can occur on the coated sheet during, for example, thermally or radiation-chemically induced curing of the coating. However, it is also possible to use coating compositions which comprise already crosslinked organic polymers which are dissolved or dispersed in a liquid medium. The finished coating is produced by so-called "drying" during evaporation of the liquid medium.

The organic coating compositions or coatings formed therewith can contain, in addition to the organic polymers, further components which improve the chemical and physical properties of the coating. For example, inorganic and / or organic pigments are frequently used for coloring, for adjusting the tribological properties and / or for improved corrosion protection. A special class of pigments are the so-called "conductive pigments". These impart sufficient electrical conductivity to the coating in order to be able to electroweld the coated metal sheet and / or to coat it with an electrodeposition paint. Examples of such conductive pigments are: powdered elemental metals such as iron, zinc, aluminum, nickel, manganese, magnesium or their alloys, metal phosphides, metal sulfides, metal oxides, graphite and carbon black. Such coating agents with which conductive organic coatings can be formed on metal substrates are described below.

Furthermore, so-called "self-precipitating" coating compositions are known. Examples of this are in the documents WO 97/07163 . US 6,312,820 . WO 03/026888 . WO 03/042275 and the literature cited therein. The process of self-deposition (also referred to as autophoretic deposition) is based on the fact that by the action of an acid in the coating agent di- or polyvalent metal ions are dissolved out of the metal surface to be coated. The dissolved metal ions react with negatively charged groups of organic polymers suspended in the coating agent. This destabilizes the suspension of organic polymers, coagulates the suspended polymer particles, and deposits as a film on the metal surface. This process stops automatically when the metal surface is completely covered with the polymer film, so no further Acid attack on the metal surface can be done. The resulting polymer layer on the metal surface is baked and cured in a subsequent step. This results in layers which generally have a thickness in the range of 5 to 25 microns.

The formation of an autodeposited coating thus presupposes that divalent or polyvalent metal ions can be dissolved out of the substrate, which destabilize the polymer emulsion. Typically, this is done by allowing the self-depositing coating to act on a bare metal surface. An alternative that leads to a dual coating is in WO 96/02384 described. According to this document, a metal surface is first coated with a first coating containing a powdered metal. In a second step, a second, self-depositing coating is deposited on this first layer. This is evidently possible because when the acid contained in the second coating agent is exposed to powder from the metal in the first coating, a sufficient amount of divalent or polyvalent metal ions is dissolved out in order to deposit the self-depositing coating agent as a second coating. For concrete examples of first and second coating agent for forming this double coating, reference is made to said document.

The present invention develops the teaching of WO 96/02384 further. It solves the problem of depositing a second coating on a first coating only where it is required due to the increased corrosive stress. This is to avoid unnecessary coating and thus unnecessary material consumption. In a further development of the concept according to the invention, the further object of providing cut edges on pre-coated metal sheets with a sufficient corrosion-protective coating is also achieved. As a result, sufficient corrosion protection is achieved in beaded or flanged regions of a component produced from such a sheet, without the need for additional sealing.

In a first aspect, the present invention relates to a metal sheet having a front side and a back side, wherein both the front side and the rear side have a first coating with an average thickness in the range of 0.5 to 10 microns, characterized in that the first coating the front particles that at Exposure of an acid to release divalent or polyvalent metal ions in such proportion that a self-depositing coating composition forms a second coating upon contact with the front surface, while the first coating on the backside does not form particles which upon exposure to an acid are divalent or polyvalent metal ions in such an amount that a self-depositing coating agent forms a second coating upon contact with the back side thereon. The term "self-depositing coating agent" and its deposition mechanism has already been explained in the introduction.

The invention also includes a metal sheet as defined above having a deposited self-depositing coating agent on the first coating of the front side. This may be freshly deposited and not yet cured or in the cured state.

By "sheet metal" is meant a sheet of any shape or a metal strip. In this case, as mentioned in the introduction, the metal sheet consist of the usual structural metals, such as iron or steel, which may be galvanized or alloyed or aluminated or alloyed aluminized, zinc, aluminum, magnesium, titanium and alloys containing at least 50% by weight. % consist of one of the metals mentioned. In particular, the metal sheet may be made of electrolytically galvanized or hot dip galvanized steel.

The terms "front side" and "back side" are defined by the coating method according to the invention: "front side" is understood to mean that side of the metal sheet which is to receive or have received a coating of a self-depositing coating agent. In the later use of the coated metal sheet for making articles such as vehicles in which the metal sheet is reshaped or joined so as to form voids, the front surface lies on the outside of these cavities. The back side forms the inside of the cavities and is thus exposed to less corrosive attacks and must meet lower aesthetic needs. For these purposes, the first coating of the inside is sufficient and no further overcoating of the first coating is required. To save material and weight, such a further coating should even be avoided according to the invention. The same applies if metal sheet according to the invention is joined by crimping or flanging: here The back of the metal sheet comes to lie on the inside of the flange or the crimp fold, while the front of the metal sheet forms the outside.

In this case, the term "first coating" is understood as meaning the first coating of the respective side, which is applied to the respective side. However, this does not rule out that the respective page was previously subjected to a conversion treatment. This will be discussed below. This layer formed by a potential conversion treatment is disregarded in the count of coating order because it is optional and not mandatory. According to the invention, the first coatings of the front and the back differ in that a self-depositing coating agent (also referred to as autodeposition agent or autodeposition resin) can be deposited on the first coating of the front side. On the first coating of the back, this invention should not be the case. This requires that the composition of the first coating of the front side be different from that of the backside.

The first coating of the front side differs from the first coating of the back at least in that the first coating of the front side can release bi-valent or polyvalent metal ions in such an amount upon exposure to the acid of the self-depositing coating agent that destabilizes the resin dispersion of the self-depositing coating agent so that this is reflected on the first coating of the front. In contrast, the first coating of the back should contain no or only a few particles which, on exposure to the acid component of the self-depositing coating agent, can release divalent or polyvalent metal ions such that their concentration on the backside is insufficient to cause the resin component of the self-depositing coating composition to precipitate.

Due to this different structure of the first coating of the front and the back, the metal sheet provided with the respective first coating can be completely brought into contact with the self-depositing coating agent. This is reflected here only on the front, but not down on the back. On the one hand, this simplifies the targeted application of the second coating only to the front side. On the other hand, however, it may happen that the first coating of the back has cracks or imperfections on which in the later Use a corrosive attack can be done. Since the acid of the self-depositing coating agent can attack at such defects and metal ions can be leached out of the metal substrate, the resin component of the self-depositing coating agent deposits on such defects and covers them. This selective deposition of the self-depositing coating agent on defects in the first coating of the back there improves the corrosion protection and is therefore desirable.

The average thickness of the first coating of both the front and the back should each be at least 0.5 .mu.m, preferably at least 1 .mu.m. However, an average thickness of more than 10 μm is not required. The maximum value of the average thickness is preferably 5 μm and in particular 3 μm. In this case, the term "average thickness" takes into account that the surface of the first coating, in particular of the front side, can be uneven due to the presence of particles. The first coating should therefore have on average the said thickness, with local deviations upwards and downwards depending on the distribution of the particles and their thickness are possible. The average thickness can be determined, for example, with an eddy current method. Alternatively, it can be measured on a cross section of the coated sheet with a scanning electron microscope. Furthermore, the average thickness can be determined by peeling off the coating and calculating the average thickness of the coating with known density of the coating from the weight difference.

Accordingly, therefore, the first coating of the front must contain a sufficient amount of particles which release di- or polyvalent metal ions upon the action of an acid. The first coating on the back should preferably not contain any such particles at all. In a small amount, however, such particles in the first coating of the back do not harm. It merely has to be ensured that the action of the self-depositing coating agent on the rear side of the metal sheet does not release divalent or polyvalent metal ions in such an amount from the first coating that the resin component of the self-depositing coating composition is precipitated there. These conditions are met, for example, if the first coating of the front side contains at least 10% by volume, preferably at least, with increasing preference, 20% by volume, 30% by volume, 40% by volume or 50% by volume of particles which release di- or polyvalent metal ions upon the action of an acid. What percentage of weight this corresponds to depends on the specific weight Weight of these particles, which can be very different. Conversely, it is preferred that the first coating of the backside contains not more than 5% by volume, preferably not more than 3% by volume and in particular not more than 1% by volume of particles which, when exposed to an acid, are 2- or release polyvalent metal ions.

The size of the particles that release divalent or polyvalent metal ions upon exposure to an acid must be limited to match the desired average thickness of the first coating. In the direction of their least extension, the particles should not exceed the desired average thickness of the coating by more than 100%. Preferably, at the location of their least extent, the particles have a thickness of not more than the desired mean thickness of the coating, preferably the thickness of the particles is at the location of their least extent below. Therefore, it is preferred that the particles which release divalent or polyvalent metal ions upon the action of an acid have a shortest axis with a length in the range of 0.01 to 5 μm, preferably to 3 μm. In the case of approximately spherical particles, this can be determined by light scattering methods or by filtration through filters of defined pore size. For strongly deviating from the spherical shape particles such as platelets, this is preferably determined by scanning electron microscopy. For exactly spherical particles, the length of the shortest axis corresponds to the particle diameter. For platelet-shaped particles, the shortest axis is that which is perpendicular to the platelet plane.

The particles that release divalent or polyvalent metal ions when exposed to an acid can be made of different materials. For example, they may be metallic particles, in particular particles of iron, zinc, nickel, manganese, magnesium or aluminum or alloys containing at least 50 wt .-% of one of these metals. Furthermore, the particles may, for example, represent compounds of divalent or polyvalent metals, in particular phosphates, oxides or hydroxides, from which the metal ions are liberated upon the action of an acid. Examples of these are phosphates, oxides or hydroxides of the abovementioned metals, but also TiO ₂ , ZrO ₂ and calcium or magnesium phosphate.

Preferably, both the first front and back coating and the second coating contain organic polymers. In this case, in particular in the first coating, the polymers can be uncrosslinked. Examples include: polyvinyl alcohol, Polymers or copolymers of vinylpyrrolidone, polymers or copolymers of acrylic acid, methacrylic acid or maleic acid, polyesters, linear polyurethanes, polymers or copolymers of amino-substituted polyvinylphenols. However, the polymers can also be crosslinked before the formation of the coating or crosslink after the formation of the coating. In the former case, they cure by physical drying during evaporation of the solvent or suspending agent. In the second case, they crosslink by chemical reaction, which can be induced for example by heating or by radiation.

For this purpose, in each case crosslinked or crosslinking organic polymers can be used which are known in the art for such coating purposes. This has already been discussed in the introduction. The polymer types, crosslinking and curing or drying mechanisms mentioned there can be transferred to the coatings or coating agents to be used in the context of this invention.

The first coating can be formed with coating agents known in the art. For example, the first coating of the front according to embodiments 1 to 3 of WO 96/02384 getting produced. Coating agents known in the art as "weld primers" or as "weldable coatings" can also be used for the first coating of the front side. These contain, in an organic polymer matrix, electrically conductive pigments which give the coating sufficient electrical conductivity in order to make the sheets coated therewith electroweldable. If the conductivity pigments used here are metals or metal compounds, such as oxides, which release divalent or polyvalent metal ions upon attack by an acid, such weldable coatings are suitable as first front coating in the context of the present invention. For example, such known weldable coatings are suitable which contain metallic zinc, aluminum, iron or iron oxides as the conductive pigment.

An example of such a coating agent that can be used to form the first front coating is shown in FIG WO 99/24515 described. This document discloses conductive and weldable anticorrosive compositions based on (blocked) polyurethane resins, epoxy resins, and nitrogen-containing curing agents and conductive fillers. If one selects zinc or aluminum from the selection of conductive fillers given in this document, this is appropriate coating suitable for the present purpose. For a more detailed composition, reference is made to said document.

WO 01/30923 also describes an electrically conductive coating which, when selecting zinc or aluminum as the conductive pigment, may serve as the first front coating in the present invention. The organic binder used here is characterized in that it cures at a relatively low object temperature in the range of 130 to 159 ° C. This binder may, for example, be selected from polyurethane / acrylate copolymer dispersions, polyurethane / polycarbonate dispersions, polyurethane / polyester dispersions and acrylate / copolymer dispersions, and mixtures thereof. Further details of suitable compositions can be found in the working examples of this document, wherein the iron phosphide used there as a conductive pigment would have to be replaced by zinc or aluminum. It also comes to compositions which can be used as the first coating of the front, when replaced in the embodiments of said document, the iron phosphide by other components such as metallic iron or iron oxide or in general by metals or metal compounds, which in attack an acid two- or release polyvalent metal ions.

Further coating compositions disclosed as the first coating of the front side are disclosed WO 01/85860 if one chooses as the conductive pigment zinc or aluminum, or instead of the conductivity pigments mentioned therein uses a metal or a metal compound which delivers divalent or polyvalent metal ions upon attack of an acid. According to this document, the coating composition contains an organic binder containing at least one epoxy resin, at least one hardener selected from cyanoguanidine, benzoguanamine and plasticized urea resin and at least one amine adduct selected from polyoxyalkylenetriamine and epoxy resin-amine adducts. More details on the composition can be found in the cited document and in particular in its working examples, wherein iron phosphide as conductive pigment would have to be replaced by the metals or compounds already mentioned by way of example, which liberate divalent or polyvalent metal ions on the action of an acid.

The first coating of the rear side may be formed analogously to the first coating of the front side described above, but in contrast to there no pigments are used, which are di- or polyvalent upon exposure to an acid Release metal ions. This means dispensing with the conductivity pigments mentioned in the documents cited above, or selecting them from carbon black or graphite. This procedure reduces the variety of products to be used, since it is possible to use the same base product for the first coating of the front and the back, wherein the product for coating the front side additionally adds one of the said pigments two or two on exposure to an acid provide polyvalent metal ions.

However, the composition of the means for depositing the first coating on the back can also be chosen independently of the means for depositing the first coating on the front side. In general, suitable coating materials are those which are known in the art as so-called "primers". To these only the above-mentioned condition is to be placed on the maximum proportion of particles which release di- or polyvalent metal ions on contact with acid. For example, a coating agent can be used, as described in the German patent application DE 10 2006 039 633 is described. It contains: fluorocomplex ions of titanium and / or zirconium (which are incorporated into the finished layer so that they do not dissolve to such an extent under the influence of an acid that a self-depositing coating agent deposits on this coating), at least one anticorrosive pigment and at least a water-soluble or water-dispersible organic polymer in the pH range of 1 to 3, which has a pH in the range of 1 to 3 as such in aqueous solution at a concentration of 50% by weight. Further information on the structure of this polymer can be found in the cited document, as well as concrete examples of such compositions. However, the cations mentioned there as further optional components of the coating agent should be dispensed with.

As means for depositing the first coating on the back side, it is furthermore possible to select those compositions which are described in the German patent application 10 2007 001 653 are described. However, one must either completely omit the conductivity pigment used there or select carbon black or graphite as conductive pigment. Furthermore, it is necessary to dispense with the pigments listed there as optional components, which can release two or more valent metal ions under the action of an acid.

The second coating can for example be applied by the action of a self-depositing coating agent, as described in Example 4 of WO 96/02384 is described. This is an aqueous solution or suspension of acrylic resin latex, carbon black, iron fluoride and hydrofluoric acid and has a pH in the range of 1 to 4. In addition, it contains hydrogen peroxide. The solids content (sum of resin and carbon black) is 4 to 10 wt.%. Other suitable means for producing the second coating are in the cited documents WO 97/07163 . US 6,312,820 . WO 03/026888 . WO 03/042275 and mentioned in the other documents cited therein. For example, the self-depositing coating compositions may consist of anionically functionalized epoxy resins as described in US Pat WO 03/042275 are described in more detail. The anionic functionalization of the epoxy resins can be carried out, for example, by incorporation of sulfonate, sulfate, phosphate, phosphonate or carboxylate groups. Preferably, this epoxy resin dispersion contains additional curing agents, as described in said document on page 12, line 25 to page 14, line 22. In addition, the self-depositing coating agent contains therein a so-called "self-deposition accelerator" which can dissolve the metal surface and thereby release the metal ions which cause the deposition of the resin. For this purpose preferably to be selected compounds are in WO 03/042275 on page 15, line 19 to page 16, line 17 described. In particular, suitable acids for this purpose, for example hydrofluoric acid, hexafluorosilicic acid, hexafluorotitanic acid, acetic acid, phosphoric acid, sulfuric acid, nitric acid, peroxyacids, citric acid or tartaric acid. Furthermore, this function can take over hydrogen peroxide or iron (II) ions. Such substances are generally known as "deposition accelerators" in self-depositing coating agents and can also be used in the present invention, regardless of which organic polymer component contains the self-depositing coating agent.

A self-depositing coating composition also useful in the present invention contains a mixture of dispersed epoxy resin and dispersed acrylic resin as described in U.S. Pat WO 03/026888 is explained in more detail. Here, too, hardeners are preferably present in addition, as described in more detail in the cited document on page 7, line 15 to page 9, line 23. In addition, "self-deposition accelerators" are again preferably present, as enumerated above, for example.

Self-depositing coating agents may also be based on other anionically functionalized resins. For example, polymers or copolymers of acrylic acid, methacrylic acid and maleic acid can be used. Another group of self-depositing coating agents contains as the resin component poly (alkylene chloride), for example, the one in US 6,312,820 more specifically described stabilized vinylidene chloride resin. This may be present as a copolymer with vinyl chloride. Anionically functionalized polyvinyl chloride can in turn serve as the basis of a self-depositing coating agent.

Preferably, the second coating contains black or colored pigments, in particular carbon black. This serves for aesthetic purposes and allows on the other hand a simple optical control of the uniformity and closure of the second coating. In addition to or instead of these black or colored pigments, the second coating may contain other pigments. Examples are lamellar or non-lamellar pigments, which in particular improve the corrosion protection. A specific example of this is calcium-containing silicates, which are known, for example, under the name "ShieIdex ^R ". Furthermore, the second coating may contain components that reduce friction and thereby improve formability. Examples of these are waxes or inorganic pigments with a layer structure such as, for example, graphite or molybdenum sulfide. Also phyllosilicates such as talc are suitable for this purpose.

The second coating of the front side preferably has an average thickness with a lower limit of at least 5, preferably at least 10 μm and an upper limit of 25, preferably of 20 μm. For example, the average thickness may be in the range of 11 to 14 microns. For the term "average thickness" the above statements apply in connection with the average thickness of the first coating accordingly. This also applies to the methods to determine the average thickness.

The first coating can be applied directly to a bare metal surface. However, in order to improve the corrosion protection and / or the adhesive strength of the first coating on the metal surface, the metal sheet may have a conversion layer on at least one side below the first coating. This is understood to mean a layer which is produced by a conversion treatment known in the prior art, metal ions from the metal sheet being incorporated into the coating. The best known examples of such conversion treatments are: Chromatization, layer-forming or non-layer-forming phosphating and the action of an acidic solution of complex fluorides, in particular the elements B, Si, Ti and / or Zr. In particular, the latter may also contain organic polymers. Common examples of these are polymers or copolymers of acrylic acid, methacrylic acid and maleic acid, polyvinyl alcohol, polyamines, polyimines and amino-substituted polyvinylphenols. In the context of the present invention it is preferred that the metal sheet has been subjected to a conversion treatment by the action of such a solution of complex fluorides before the deposition of the first coating.

The metal sheet can be already cut pieces to which the corresponding coatings are applied after cutting. The cut edges are then coated with. Preferably, however, the metal sheet according to the invention is formed by applying the respective first coating to metal sheet in the strip process, if desired after a conversion treatment, on the front and back of the strip. In addition, it is possible to apply the second coating to the side of the band that is thereby becoming the front side. In this state, the tape can be transported to the user and processed there, in particular cut, formed by pressing and joined into components. Due to the coating according to the invention a reduced amount of forming oil is required for forming by pressing. Forming oil can even be completely dispensed with, which simplifies the cleaning required after pressing and saves material.

However, the metal sheet coated according to the invention can also be obtained by applying the first coating of the front and the back in the steelwork on metal strip in the strip process and transporting the strip in this state to the further processor. There, the metal strip is cut into sheets of the required size, resulting in cut edges that extend from the front to the back. This also happens when holes are punched in such a metal sheet. These cut edges are then free of first coating. If such cut edges come to lie in the interior of a hem flange or a flange, they are particularly sensitive to corrosion because of their unprotected state. However, if one brings metal sheet, which has only the first coating on the front and back, after cutting or punching for depositing the second coating in contact with the self-depositing coating agent, this does not separate only on the front side of the sheet, but also on the cut edges, since there are also bivalent or polyvalent metal ions in sufficient quantity in solution. As a result, not only the front side but also the cut edges are coated with the second coating (the "second coating" on the cut edge being the only coating). This gives the cut edges a sufficient corrosion protection, so that after flanging or folding no further corrosion protection measures are required. In this particular embodiment, the metal sheet according to the invention is thus characterized in that it has at least one edge which extends from the front to the back and which does not have a coating corresponding to the first coating of the front or back, but a coating corresponding to the second coating of the front having.

In the further processing of the parts made of the metal sheet according to the invention, such as parts of vehicle bodies, the second coating can be further painted over. On the first coating of the back, this can be avoided if it comes to lie in the interior of resulting from the assembly cavities.

In a second aspect, the present invention relates to an article which at least partially consists of the metal sheet according to the invention. This can have further lacquer layers above the second coating. Such items may represent, for example, vehicles, architectural elements, metal furniture or household appliances ("white goods") or parts thereof. Furthermore, the objects according to the invention can represent components of aircraft or ships.

In addition, the present invention relates to the use of a metal sheet according to the invention for the production of said articles. As already described, the metal sheet according to the invention is deformed and joined and optionally painted over for the production of these objects.

• a) erforderlichenfalls reinigt
• b) erwünschtenfalls einer Konversionsbehandlung unterzieht,
• c1) die Vorderseite mit einem ersten Beschichtungsmittel in Kontakt bringt, das nach Trocknen und/oder Einbrennen die erste Beschichtung der Vorderseite erzeugt,
• c2) die Rückseite mit einem ersten Beschichtungsmittel in Kontakt bringt, das nach Trocknen und/oder Einbrennen die erste Beschichtung der Rückseite erzeugt,
  wobei die Schritte c1) und c2) gleichzeitig oder in beliebiger Reihenfolge ausgeführt werden können, und
• d) das auf Vorder- und Rückseite mit der ersten Beschichtung versehene Metallblech mit einem selbstabscheidenden Beschichtungsmittel in Kontakt bringt, wodurch auf der Vorderseite die zweite Beschichtung ausgebildet wird,
• e) die zweite Beschichtung trocknet und/oder einbrennt. Dabei wird unter "Trocknen" ein physikalisches Härten des Polymersystems durch Abdampfen des Lösungs- oder Suspensionsmittels verstanden. "Einbrennen" bezeichnet ein Aushärten des Polymersystems durch chemische Reaktionen, wie sie einleitend beispielsweise genannt wurden. Dieses Aushärten durch chemische Reaktion kann durch Erwärmen oder durch energiereiche Strahlung (so genannte "aktinische Strahlung" wie beispielsweise UV- oder Elektronenstrahlung) ausgelöst werden.

Another aspect of the present invention resides in a method for producing a metal sheet as described above, wherein an uncoated metal sheet or metal strip

• a) cleans if necessary
• b) if desired, subject to a conversion treatment,
• c1) bringing the front into contact with a first coating agent, which after Drying and / or firing produces the first coating of the front,
• c2) brings the back side into contact with a first coating agent which, after drying and / or baking, produces the first coating on the back side,
  wherein steps c1) and c2) can be carried out simultaneously or in any order, and
• d) bringing the metal sheet provided with the first coating on the front and back sides into contact with a self-depositing coating agent, thereby forming the second coating on the front side,
• e) the second coating dries and / or burns. By "drying" is meant a physical curing of the polymer system by evaporation of the solvent or suspending agent. "Baking" refers to curing of the polymer system by chemical reactions, as mentioned in the introduction, for example. This curing by chemical reaction can be triggered by heating or by high-energy radiation (so-called "actinic radiation" such as UV or electron radiation).

For the composition of the metal sheet and the conversion solutions and coating compositions to be used, the above statements apply accordingly.

If the first coating is applied directly to a freshly made metal strip, for example on galvanized steel strip after galvanizing, a cleaning is not required. However, if the metal sheet or metal strip has been stored, transported or oiled before the application of the first coating agent and is therefore contaminated, it may be advisable to clean it before applying the first coating agent. Such cleaning processes are common and known in the art prior to coating. In particular, aqueous alkaline cleaners are used for this purpose. If desired, as already explained above, a conversion treatment can be carried out before the application of the first coating agent.

Methods, in particular strip methods, with which the first coating agent can be applied to the front and the back of the metal sheet or metal strip, are likewise known and customary in the prior art. Since the front and back are to be treated differently, dipping methods are less suitable. It is preferable to separate the front and the back separately (simultaneously or in any order) with the first coating means of the front and the back in FIG To bring contact. This can be done for example by spraying and subsequent squeezing or by roller application. By adjusting the nip of the squeegee rollers, the wet film thickness can be adjusted to give the desired dry film thickness after drying and / or baking. As already described in the introduction, different processes for drying or baking in particular organic coatings are known in the prior art. These can be used for the process according to the invention.

As already explained, the application of the second coating can be carried out immediately after the first coating has dried or baked in the part or strip process. For this purpose, in particular spraying or dipping methods are suitable. In this case, it is preferable to bring both the front and rear sides into contact with the self-depositing coating agent, since this makes it possible to compensate for defects in the coating on the backside by local deposition of the self-depositing coating agent.

However, between the application of the respective first coating and the second coating, the metal sheet or metal strip can also be stored and / or transported. A particular embodiment of the method according to the invention consists in cutting the metal sheet or metal strip after application of the respective first coating and before applying the second coating, so that at least one edge is formed, which extends from the front to the back and which does not correspond to a coating the first coating of the front or back has. If the metal sheet cut in this way is brought into contact with the self-depositing coating agent, the second coating agent is deposited not only on the front side but also on the cut edge, so that it is protected against corrosion.

If the metal sheet is stored and / or transported or even oiled between the application of the first and the second coating, whereby the first coating can become dirty, it is advisable to clean the metal sheet provided with the first coating before applying the second coating, for example using commercially available alkaline cleaner. This corresponds, for example, to the procedure in exemplary embodiment 4 of FIG WO 96/02384 ,

The present invention thus simplifies the production of corrosion-protected components by reducing the cost of materials and work steps. Inner surfaces of cavities, hemispheres and flanges are adequately protected against corrosion by the first coating on the reverse side. Additional corrosion protection measures as usual in the prior art are no longer necessary at these locations. In the particularly preferred embodiment of the method according to the invention, cut edges are covered with a layer of the self-depositing coating agent and thereby protected against corrosion. The flooding of cavities with wax or an electrolytic dip coating are no longer necessary.

For low corrosion loads and aesthetic requirements, such as in mechanical or plant engineering, the second coating on the front can be the final coating. To improve corrosion protection and for higher aesthetic requirements, such as in vehicle construction, the second coating can be overcoated, for example, as in the automotive industry usual with filler and topcoat. However, the previously customary cathodic electrodeposition coating as the first coating step can be saved. Rather, the second coating takes over the function of the electrolytic dip coating.

Claims (13)

1. A metal sheet having a front side and a back side, wherein both the front side and the back side comprise a first coating having an average thickness in the range from 0.5 to 10 µm, characterized in that the first coating of the front side contains at least 10 vol% particles that, upon the action of an acid, release divalent or polyvalent metal ions selected from particles of iron, zinc, nickel, manganese, magnesium or aluminium, from particles of alloys that contain at least 50 wt% of one of said metals, and from particles of compounds of divalent or polyvalent metals, so that a self-depositing coating agent forms, upon contact with the front side, a second coating thereon, whilst the first coating of the back side contains no more than 5 vol% particles that, upon the action of an acid, release divalent or polyvalent metal ions selected from particles of iron, zinc, nickel, manganese, magnesium, or aluminium, from particles of alloys that contain at least 50 wt% of one of said metals, and from particles of compounds of divalent or polyvalent metals.
2. The metal sheet according to Claim 1, characterized in that the particles that release divalent or polyvalent metal ions upon the action of an acid have a shortest axis having a length in the range from 0.01 to 5 µm.
3. The metal sheet according to one of both of Claims 1 and 2, characterized in that the first coating of the front side and/or of the back side contains organic polymers.
4. The metal sheet according to one or more of Claims 1 to 3, characterized in that it comprises a conversion layer on the front side and/or back side beneath the first coating.
5. The metal sheet according to one or more of Claims 1 to 4, characterized in that it comprises on the first coating of the front side, as a second coating, a deposited self-depositing coating agent.
6. The metal sheet according to Claim 5, characterized in that the second coating contains organic polymers.
7. The metal sheet according to one or both of Claims 5 and 6, characterized in that the second coating contains black or coloured pigments.
8. The metal sheet according to one or more of Claims 5 to 7, characterized in that the second coating has an average thickness in the range from 5 to 25 µm, in particular in the range from 10 to 20 µm.
9. The metal sheet according to one or more of Claims 5 to 8, characterized in that it comprises at least one edge that extends from the front side to the back side and that does not comprise a coating corresponding to the first coating of the front side or back side, but does comprise a coating corresponding to the second coating of the front side.
10. An article that is made up at least in part of metal sheet according to one or more of Claims 1 to 9.
11. Use of a metal sheet according to one or more of Claims 1 to 9 for the manufacture of an article according to Claim 10.
12. A method for manufacturing a metal sheet according to one or more of Claims 5 to 9, characterized in that an uncoated metal sheet or metal strip
    is cleaned if necessary,
    is subjected, if desired, to a conversion treatment,

    c1) the front side is brought into contact with a first coating agent that, after drying and/or baking, generates the first coating of the front side,

    c2) the back side is brought into contact with a first coating agent that, after drying and/or baking, generates the first coating of the back side,
    wherein steps c1) and c2) can be carried out simultaneously or in any sequence, and

    d) the metal sheet, equipped on the front side and back side with the first coating, is brought into contact with a self-depositing coating agent, with the result that the second coating is constituted on the front side,

    e) the second coating is dried and/or baked.
13. A method for manufacturing a metal sheet according to Claim 9, characterized in that the procedure is in accordance with Claim 12, and the metal sheet or metal strip is in that context cut up between steps c) and d) so that at least one edge is produced which extends from the front side to the back side and which has no coating corresponding to the first coating of the front side or back side.