EP2129476B1 - Substrat métallique à plusieurs revêtements et procédé de fabrication dudit substrat - Google Patents

Substrat métallique à plusieurs revêtements et procédé de fabrication dudit substrat Download PDF

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Publication number
EP2129476B1
EP2129476B1 EP20070857255 EP07857255A EP2129476B1 EP 2129476 B1 EP2129476 B1 EP 2129476B1 EP 20070857255 EP20070857255 EP 20070857255 EP 07857255 A EP07857255 A EP 07857255A EP 2129476 B1 EP2129476 B1 EP 2129476B1
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EP
European Patent Office
Prior art keywords
coating
front side
metal sheet
particles
back side
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP20070857255
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German (de)
English (en)
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EP2129476A1 (fr
Inventor
Manfred HOLZMÜLLER
Simone Cortellaro
Ulrich JÜPTNER
Marcel Roth
Peter Kuhm
Patrick Droniou
Pamela Cziesla
Giorgio Cortellaro
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP2129476A1 publication Critical patent/EP2129476A1/fr
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Not-in-force legal-status Critical Current
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/10—Applying the material on both sides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24752—Laterally noncoextensive components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24777—Edge feature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31605—Next to free metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers

Definitions

  • 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.
  • conversion treatment 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.
  • the conversion-treated metal surfaces are overcoated with one or more organic coatings of varying thickness.
  • These organic coatings usually contain (crosslinked) organic polymers.
  • the organic coating agent 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • sheet metal is meant a sheet of any shape or a metal strip.
  • 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.
  • the metal sheet may be made of electrolytically galvanized or hot dip galvanized steel.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m is not required.
  • the maximum value of the average thickness is preferably 5 ⁇ m and in particular 3 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m, preferably to 3 ⁇ m.
  • the length of the shortest axis corresponds to the particle diameter.
  • 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.
  • 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.
  • 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.
  • both the first front and back coating and the second coating contain organic polymers.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • such known weldable coatings are suitable which contain metallic zinc, aluminum, iron or iron oxides as the conductive pigment.
  • FIG WO 99/24515 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.
  • 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.
  • 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.
  • composition 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.
  • 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.
  • 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.
  • a coating agent can be used, as described in the German patent application DE 10 2006 039 633 is described.
  • 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.
  • 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.
  • 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.
  • this epoxy resin dispersion contains additional curing agents, as described in said document on page 12, line 25 to page 14, line 22.
  • 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.
  • preferably to be selected compounds are in WO 03/042275 on page 15, line 19 to page 16, line 17 described.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ".
  • 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 ⁇ m and an upper limit of 25, preferably of 20 ⁇ m.
  • the average thickness may be in the range of 11 to 14 microns.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the objects according to the invention can represent components of aircraft or ships.
  • the present invention relates to the use of a metal sheet according to the invention for the production of said articles.
  • the metal sheet according to the invention is deformed and joined and optionally painted over for the production of these objects.
  • first coating is applied directly to a freshly made metal strip, for example on galvanized steel strip after galvanizing, a cleaning is not required.
  • 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.
  • cleaning processes are common and known in the art prior to coating.
  • aqueous alkaline cleaners are used for this purpose.
  • 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.
  • 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.
  • spraying or dipping methods are suitable.
  • 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.
  • 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.
  • 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.
  • the second coating on the front can be the final coating.
  • the second coating can be overcoated, for example, as in the automotive industry usual with filler and topcoat.
  • 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.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (13)

  1. Tôle métallique, dotée d'une face avant et d'une face arrière, la face avant ainsi que la face arrière présentant un premier revêtement d'une épaisseur moyenne dans la plage de 0,5 à 10 µm, caractérisée en ce que le premier revêtement de la face avant contient au moins 10% en volume de particules qui libèrent des ions métalliques divalents ou polyvalents sous l'effet d'un acide, choisies parmi les particules de fer, de zinc, de nickel, de manganèse, de magnésium ou d'aluminium, parmi les particules d'alliages qui contiennent au moins 50% en poids d'un de ces métaux et parmi les particules de composés de métaux divalents ou polyvalents, de telle sorte qu'un agent de revêtement d'auto-déposition, au contact avec la face avant, forme un deuxième revêtement sur celle-ci, alors que le premier revêtement de la face arrière ne contient pas plus de 5% en volume de particules qui libèrent des ions métalliques divalents ou polyvalents sous l'effet d'un acide, choisies parmi les particules de fer, de zinc, de nickel, de manganèse, de magnésium ou d'aluminium, parmi les particules d'alliages qui contiennent au moins 50% en poids d'un de ces métaux et parmi les particules de composés de métaux divalents ou polyvalents.
  2. Tôle métallique selon la revendication 1, caractérisée en ce que les particules, qui libèrent des ions métalliques divalents ou polyvalents sous l'effet d'un acide, présentent un axe le plus court d'une longueur dans la plage de 0,01 à 5 µm.
  3. Tôle métallique selon l'une des revendications ou les deux revendications 1 et 2, caractérisée en ce que le premier revêtement de la face avant et/ou de la face arrière contient des polymères organiques.
  4. Tôle métallique selon l'une ou plusieurs des revendications 1 à 3, caractérisée en ce qu'elle présente une couche de conversion sur la face avant et/ou la face arrière, sous le premier revêtement.
  5. Tôle métallique selon l'une ou plusieurs des revendications 1 à 4, caractérisée en ce qu'elle présente, sur le premier revêtement de la face avant, comme deuxième revêtement, un agent de revêtement d'auto-déposition déposé.
  6. Tôle métallique selon la revendication 5, caractérisée en ce que le deuxième revêtement contient des polymères organiques.
  7. Tôle métallique selon l'une des revendications ou les deux revendications 5 et 6, caractérisée en ce que le deuxième revêtement contient des pigments noirs ou colorés.
  8. Tôle métallique selon l'une ou plusieurs des revendications 5 à 7, caractérisée en ce que le deuxième revêtement présente une épaisseur moyenne dans la plage de 5 à 25 µm, en particulier dans la plage de 10 à 20 µm.
  9. Tôle métallique selon l'une ou plusieurs des revendications 5 à 8, caractérisée en ce qu'elle présente au moins un bord qui s'étend de la face avant à la face arrière et qui ne présente pas de revêtement correspondant au premier revêtement de la face avant ou de la face arrière, mais un revêtement correspondant au deuxième revêtement de la face avant.
  10. Objet, qui est constitué au moins partiellement de la tôle métallique selon l'une ou plusieurs des revendications 1 à 9.
  11. Utilisation d'une tôle métallique selon l'une ou plusieurs des revendications 1 à 9 pour la fabrication d'un objet selon la revendication 10.
  12. Procédé pour la production d'une tôle métallique selon l'une ou plusieurs des revendications 5 à 9, caractérisé en ce qu'on
    a) nettoie, si nécessaire, une tôle ou une bande métallique
    b) la soumet, le cas échéant, à un traitement de conversion,
    c1) met en contact la face avant avec un premier agent de revêtement, qui génère, après séchage et/ou calcination, le premier revêtement de la face avant,
    c2) met en contact la face arrière avec un premier agent de revêtement, qui génère, après séchage et/ou calcination, le premier revêtement de la face arrière, les étapes c1) et c2) pouvant être exécutées simultanément ou dans un ordre quelconque, et
    d) met en contact la tôle métallique pourvue du premier revêtement sur la face avant et la face arrière avec un agent de revêtement d'autodéposition, suite à quoi le deuxième revêtement se forme sur la face avant,
    e) sèche et/ou calcine le deuxième revêtement.
  13. Procédé pour la production d'une tôle métallique selon la revendication 9, caractérisé en ce qu'on procède selon la revendication 12 et on découpe la tôle ou la bande métallique entre les étapes c) et d), de telle sorte qu'il se forme au moins un bord qui s'étend de la face avant à la face arrière et qui ne présente pas de revêtement correspondant au premier revêtement de la face avant ou de la face arrière.
EP20070857255 2007-03-28 2007-12-05 Substrat métallique à plusieurs revêtements et procédé de fabrication dudit substrat Not-in-force EP2129476B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710015393 DE102007015393A1 (de) 2007-03-28 2007-03-28 Mehrfach beschichtetes Metallsubstrat und Verfahren zu seiner Herstellung
PCT/EP2007/063332 WO2008116510A1 (fr) 2007-03-28 2007-12-05 Substrat métallique à plusieurs revêtements et procédé de fabrication dudit substrat

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EP2129476A1 EP2129476A1 (fr) 2009-12-09
EP2129476B1 true EP2129476B1 (fr) 2014-01-29

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US (1) US8545967B2 (fr)
EP (1) EP2129476B1 (fr)
JP (1) JP2010522104A (fr)
KR (1) KR20090125210A (fr)
DE (1) DE102007015393A1 (fr)
WO (1) WO2008116510A1 (fr)

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CN102802937B (zh) * 2009-06-17 2015-04-22 东洋钢钣株式会社 深冲压罐用复合Al材
WO2015125185A1 (fr) 2014-02-21 2015-08-27 Ｊｆｅスチール株式会社 Feuille métallique revêtue de résine pour récipient et son procédé de fabrication
WO2015125184A1 (fr) * 2014-02-21 2015-08-27 Ｊｆｅスチール株式会社 Feuille métallique revêtue de résine pour un récipient et procédé de fabrication associé
JP6619920B2 (ja) * 2015-12-16 2019-12-11 株式会社Uacj プレコートアルミニウム材
DE102016209364B4 (de) * 2016-05-31 2020-11-19 BSH Hausgeräte GmbH Verfahren zum Umformen eines Edelstahlfeinblechs unter Verwendung einer Schutzschicht als partieller Auftrag von Polymerpartikeln

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US8545967B2 (en) 2013-10-01
KR20090125210A (ko) 2009-12-03
WO2008116510A1 (fr) 2008-10-02
EP2129476A1 (fr) 2009-12-09
DE102007015393A1 (de) 2008-10-02
JP2010522104A (ja) 2010-07-01
US20100112302A1 (en) 2010-05-06

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