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
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/78—Pretreatment of the material to be coated
• • 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
  • B05D2202/00—Metallic substrate
• • 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
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
  • B05D3/107—Post-treatment of applied coatings

Definitions

• the present invention relates to an at least two-stage process for the corrosion-protective treatment of metal surfaces, wherein in a first step (i) on the metal surface, an organic coating of an aqueous phase (A) is applied and in a subsequent step (ii) on the metal surface applied organic coating with an acidic aqueous composition (B) is brought into contact containing at least one or more water-soluble compounds containing at least one atom selected from the elements Zr, Ti, Si, Hf, V and / or Ce and one or more water-soluble compounds comprising copper ions.
• the present invention comprises a metallic component, which is at least partially made of steel, iron, zinc and / or aluminum and their alloys and has been treated in the process according to the invention, as well as the use thereof in the automotive industry and in the construction sector and for the production of household appliances and electronic enclosures.
• the automotive industry primarily uses dip-coating, in which the corrosion-protected pretreated green bodies are introduced in a continuous process into a dip tank containing a dispersed coating system, wherein the deposition of the paint either by applying an external voltage (electrocoating) orsabscheidend by mere contact with the Metal surfaces (autophoretic dip coating) takes place. Subsequently, the body shell undergoes a heat treatment, so that a filming and crosslinking of the deposited on the metal surface paint system takes place, which ensures a high corrosion protection and allows the subsequent application of additional coatings.
• dip-coating in which the corrosion-protected pretreated green bodies are introduced in a continuous process into a dip tank containing a dispersed coating system, wherein the deposition of the paint either by applying an external voltage (electrocoating) orsabscheidend by mere contact with the Metal surfaces (autophoretic dip coating) takes place. Subsequently, the body shell undergoes a heat treatment, so that a filming
• Autophoretic baths thus serve the organic coating of metallic surfaces, mostly iron surfaces, as a corrosion-protecting primer coating of metallic components or as an adhesive interlayer in the production of metal-elastomer compounds, for example for vibration damping components in the automotive industry.
• the autophoretic coating is therefore a dip coating, which in the Contrary to the electrocoating occurs without external power, ie without the application of an external voltage source.
• the self-precipitating compositions are usually aqueous dispersions of organic resins or polymers, which coagulate on contact with the metallic surface due to the Beizabtrages of metal cations in a thin liquid layer directly to the surface of the component and thus cause the layer structure.
• an aqueous reaction rinse following the organic primary coating with the dip coating is proposed in the prior art.
• Such a reaction rinse corresponds loudly DE 10 2007 059969 a passivating after-treatment of the uncrosslinked coating and causes an inorganic conversion of free metal surface to so-called micro-defects, for example with the aid of phosphate-containing solutions, which may also contain alkali and / or alkaline earth metal cations and transition metal cations and their fluorocomplexes.
• the US 6410092 a chromium-free reaction rinse based on water-soluble alkaline earth metal salts, preferably calcium nitrate, while in the WO 02/42008 water-soluble salts of metals of groups IIa and IIb, preferably zinc salts are used, with additional soluble phosphates and so-called accelerators which act oxidatively, should be included in the reaction rinse.
• WO 96/10461 discloses a reaction sink based on fluoro complexes.
• the object of the present invention is to develop a method for the first deposition of hardenable organic binder systems on metal surfaces and from aqueous phase, which further improves the corrosion resistance of the cured with the cured organic binder system metal surface.
• the object is achieved by means of a multi-stage process for the corrosion-protective treatment of metal surfaces, according to claim 1.
• the metal surface which is provided with an organic coating in a first step (i), may represent a free metal surface which is freed of organic impurities in a cleaning and / or pickling step preceding the process according to the invention.
• a free metal surface is characterized by the fact that it is substantially free of organic impurities, for example anticorrosive oils, and on its surface no or only an ultrathin oxide cover layer is present, which consists mainly of metallic elements of the metal substrate and has only a few nanometers layer thickness.
• metal surfaces according to the invention are also those surfaces which, prior to the method step (i) according to the invention, have undergone a conversion treatment in the course of which an inorganic cover layer has been formed.
• Such inorganic conversion layers may consist of both metallic elements of the metal substrate and of foreign metals.
• Typical conversion coatings are formed when free metal surfaces come into contact with acidic aqueous solutions containing water-soluble compounds of the elements Zr, Ti, Si, Hf, V, Ce, Mo, Zn, Mn, Fe and, if appropriate, additionally sparingly soluble salts forming anions such as phosphates and / or complexing Anions such as fluoride ions.
• amorphous or crystalline inorganic cover layers are formed on the metal surface, whereby metal surfaces are still according to the invention and can be used for the method according to the invention if the surface-related layer weight of the inorganic cover layers is not more than 3 g / m 2 .
• An organic coating which is brought onto the metal surface in the first process step (i) is according to the invention if it contains a curable organic binder system.
• the process step (i) according to the invention comprises only the application of this organic coating, but not the curing of the same by means of additional technical measures for crosslinking the binder system.
• additional Technical measures include, for example, the heat treatment (thermal curing) or the actinic radiation (radiation curing) of an organic coating applied in step (i), which contains the curable binder system.
• process step (i) optionally comprises heat treating the aqueous surface treated with (A) metal surface to evaporate a portion of the water remaining in the wet film on the treated metal surface, but wherein the heat treatment was conducted below the curing temperature of the organic binder system.
• the organic coating applied from the aqueous phase (A) therefore also contains a part of water.
• the organic coating can contain leveling agents, surfactants, corrosion inhibitors, salts, pigments and other active substances and auxiliaries known to the person skilled in the lacquer art.
• the solids content of the organic coating is at least 20% by weight.
• the organic coating is that part of a wet film of the aqueous phase (A) applied in step (i) comprising a curable organic binder system which, following a rinsing step immediately following step (i), is applied as a firmly adhering film under flowing water to the metal surface curable organic binder system remains.
• the deposition of the organic coating in step (i) of the process according to the invention takes place from an aqueous phase (A).
• the nature of the deposition is not bound to specific technical measures and can be carried out by electrodeposition of the metal surface or by electroless processes such as autodeposition and the known in the art mechanical application method (roller coating method, spray method).
• the process according to the invention exhibits the most significant improvement for the corrosion resistance of the metal surfaces treated in the process according to the invention, especially in the case of electroless deposition of the organic coating in process step (i) from an aqueous phase (A). Accordingly, such inventive methods are preferred in which the application of the organic coating in the first step (i) without external current, in particular autophores, by contacting the metallic surface with an aqueous phase (A) containing the organic binder.
• the aqueous phase (A) in step (i) of the process according to the invention preferably contains at least 1% by weight of the organic binder system.
• Thermally curable organic binder systems are those binder systems which have curing temperatures above 20 ° C and below the stated temperatures of 300 ° C, preferably below 200 ° C.
• the curing temperature is the highest temperature that marks the maximum of an exothermic process in a dynamic differential calorimetric analysis (DSC) of a solid mixture of the organic binder system used in a temperature range of 20 ° C to 400 ° C at a heating rate of 10 K / min.
• DSC dynamic differential calorimetric analysis
• the calorimetric analysis of the test volume of the solid mixture and registered by DSC exothermic heat quantity is carried out according to DIN 53 765, taking into account the DIN EN ISO 11357-1.
• a solid mixture of the organic binder system used is accessible by vacuum freeze-drying of an aqueous dispersion of the binder system.
• the aqueous dispersion of the binder system can be dried at room temperature in the sample crucible for the DSC measurement and the initial weight of solid mixture in the sample crucible can be determined by differential weighing.
• the aqueous dispersion the aqueous phase (A) is particularly suitable.
• Thermally crosslinkable or curable organic binder systems according to component a) of the aqueous phase (A), which are applied to the metal surface by autophoretic deposition in step (i) of a preferred process according to the invention, consist of organic oligomeric or polymeric compounds having at least two functional groups and thus are able to react in condensation or addition reactions to form covalent bonds with one another, thereby building up a network of covalently linked oligomeric or polymeric compounds.
• Thermally crosslinkable or curable binder systems can either consist of a self-crosslinking oligomeric or polymeric compound having two different or the same functional groups capable of reacting with each other or of at least two different oligomeric or polymeric compounds which crosslink with one another due to their functionalization.
• the water-dispersed organic binder system according to component a), which is applied to the metal surface without external current in step (i) of a preferred method according to the invention contains at least one thermally self-crosslinking organic polymer and / or a mixture of at least one crosslinkable organic polymer or a resin and an organic hardener which can react with the crosslinkable functionalities of the organic polymer or the resin in an addition or condensation reaction.
• the organic hardener may likewise be an organic polymer or a resin.
• the organic binder system dispersed in the aqueous phase (A) in step (i) of the process according to the invention to have a film-forming temperature of not more than 80 ° C., more preferably not more than 40 ° C. If the film-forming temperature of the binder is above the preferred 80 ° C., an inhomogeneous organic coating of the metal surface during the reaction rinse with an acidic aqueous composition (B) in step (ii) of the process according to the invention may also be the result, which is also present in the curing process Procedure follows, is not curable.
• Such an inhomogeneous coating of the metal surface with the organic binder system has an adverse effect on the corrosion resistance and the visual appearance of the coated metal surface.
• step (i) Since the film formation of the organic binder system deposited on the metal surface in step (i) is already advantageous during the reaction rinse in step (ii), those inventive methods are preferred in which the acidic aqueous composition (B) in step (ii) at a temperature of at least 30 ° C, more preferably at least 40 ° C, but preferably not more than 80 ° C is brought into contact with the organic coating having metal surface.
• the dispersed organic binder system used in step (i) of the invention's preferred method for electroless deposition preferably consists of at least one copolymer and / or polymer mixture of acrylates having at least one oligomeric and / or polymeric compound selected from epoxy resins, phenolic resins and / or polyurethane resins.
• water-dispersible epoxy resins have a particularly good barrier effect against corrosive media and are Therefore, preferred component of the dispersed binder system in a preferred method according to the invention, in which in step (i) the organic coating without external power, that is applied via a self-deposition process.
• the organic coating without external power that is applied via a self-deposition process.
• the epoxy resin crosslinking hardener preferably at least partially based on phenolic resins, can be used to accelerate the curing process and to increase the degree of crosslinking.
• Further curing agents curing the epoxy resin are those based on isocyanate resins whose isocyanate groups may also be blocked.
• Preferred blocked isocyanate resins are moderately reactive isocyanates, for example aliphatic isocyanates and sterically hindered and / or acid-stable blocked isocyanates.
• epoxide resins which are not completely crosslinked, oligomeric or polymeric compounds having free, for example terminally bonded, epoxide groups can be used whose preferred molecular weight is not less than 500 ⁇ and not greater than 5000 ⁇ .
• Examples of such epoxy resins are those based on bisphenol A and bisphenol F, as well as epoxy-phenol novalacets. For reasons of economy and commercial availability, preference is given in the context of the present invention to bisphenol A-based epoxy resins which correspond to the following general structural formula (III):
• Structural component A corresponds to the following general formula (IV): with n as integer number from 1 to 50.
• Preferred epoxies have an epoxy equivalent weight (EEW) of not less than 100 g / eq but not more than 5000 g / eq.
• the EEW represents the average molecular weight per mole of epoxy functionality in the epoxy resin in grams per mole equivalent (g / eq).
• For specific epoxy resins have particularly preferred ranges for the epoxy equivalent weight: Brominated epoxy resins 300-1000 g / eq, in particular 350-600 Polyalkylene glycol epoxy resins 100-700 g / eq, in particular 250-400 Liquid epoxy resins 150-250 g / eq Solid / pasty epoxy resins 400-5000 g / eq, in particular 600-1000
• phenolic resins incompletely crosslinked, oligomeric or polymeric polycondensation products of formaldehydes with phenols which are preferably at least partially etherified hydroxyl groups may be present in the aqueous phase (A) in step (i) of the preferred novel process for electroless deposition of the organic coating and their preferred average molecular weight is not less than 500 ⁇ and not more than 10,000 ⁇ .
• the hydroxyl groups are preferably methoxylated, ethoxylated, propoxylated, butoxylated or ethenyloxylated.
• phenolic resin types both resoles and novolaks can be used.
• aqueous phase (A) which on contact with metal surfaces cause an autodeposition of an organic coating in the sense of this invention, are leveling agents, such as glycol ethers and alcohol esters, for better filming of the deposited organic coating on the metallic surface, micronized inorganic fillers such as sulfates, oxides and phosphates with average particle sizes below 5 microns, preferably below 1 micron, to increase the scratch resistance and corrosion resistance of the organic coating in the cured state, and pigments for coloring, for example AQUABLACK ® 255A Fa. Solutions Inc.
• leveling agents such as glycol ethers and alcohol esters
• micronized inorganic fillers such as sulfates, oxides and phosphates with average particle sizes below 5 microns, preferably below 1 micron, to increase the scratch resistance and corrosion resistance of the organic coating in the cured state
• pigments for coloring for example AQUABLACK ® 255A Fa. Solutions Inc.
• the reaction rinse to be carried out in step (ii) of the process of the invention by contacting the metal surface having the organic coating is preferably carried out at a pH of the acidic aqueous composition (B) of not less than 2 and not greater than 5.
• Lower pH Values can chemically alter the organic coating and initiate decomposition reactions depending on the organic binder system used.
• increased acid corrosion of the metallic substrate and the formation of nascent hydrogen can permanently damage the interface of metal with the organic coating.
• Compositions having pH's above 5 are also less preferred because compositions (B) tend to form sparingly soluble precipitates due to hydrolysis reactions of the water-soluble compounds of component a).
• fluoride ions may additionally be present in the acidic aqueous composition (B).
• the proportion of fluoride ions in the composition (B) does not exceed values for which the measured free fluoride content is greater than 400 ppm, however, for enhanced pickling effect on the substrate and effective complexation of the metal cations is at least 1 ppm of free fluoride in the composition (B).
• the source of fluoride ions are, for example, hydrogen fluoride, alkali fluorides, ammonium fluoride and / or ammonium bifluoride.
• Preferred water-soluble compounds of component a) in step (ii) of the process according to the invention are compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements zirconium, titanium and / or silicon, particularly preferably fluorocomplexes of the elements zirconium and / or titanium.
• Such preferred compounds are, for example, H 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF 6 and (NH 4 ) 2 ZrF 6 and the analogous titanium or silicon compounds.
• fluorine-containing compounds according to component a) are at the same time a source of free fluoride.
• Fluorine-free compounds of the elements titanium and / or zirconium can also be used according to the invention as water-soluble compounds according to component A), for example (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 or TiO (SO 4 ).
• Preferred water-soluble compounds of component b) in step (ii) of the process according to the invention are all water-soluble copper salts which do not contain any chloride ions. Particularly preferred are copper sulfate, copper nitrate and copper acetate.
• the acidic compositions used in step (ii) of the process according to the invention may additionally contain what are known as depolarizers which, because of their mild oxidation action, prevent the formation of nascent hydrogen on the free metal surface during the reaction.
• depolarizers which are known in the technical field of phosphating metal surfaces, is therefore also preferred according to the invention.
• Typical representatives of depolarizers are chlorate ions, nitrite ions, hydroxylamine, hydrogen peroxide in free or bound form, nitrate ions, m-nitrobenzenesulfonate ion, m-nitrobenzoate ion, p-nitrophenol, N-methylmorpholine-N-oxide, nitroguanidine.
• a composition (B) in the reaction rinse, ie in step (ii) of the process according to the invention contains not more than 1 ppm of soluble phosphates and chromates calculated as the sum of PO 4 and CrO 4 , particularly preferably no soluble phosphates and chromates.
• the present invention is also distinguished by the fact that the presence of soluble phosphates and chromates in step (ii) of the method can be dispensed with and yet an excellent corrosion resistance of the metal substrates treated according to the invention results.
• step (i) The contacting of the aqueous phase (A) in step (i) and the acidic aqueous composition in step (ii) with the metallic substrate or the metallic component takes place in the process according to the invention preferably in the dipping or spraying process, wherein the dipping method the more homogeneous wetting of the surface is particularly preferable.
• preferred processes according to the invention are those in which a rinsing step is carried out between the first step (i) and the subsequent step (ii) for removing components of the aqueous phase (A) from the treated metal surface.
• a rinsing step is carried out between the first step (i) and the subsequent step (ii) for removing components of the aqueous phase (A) from the treated metal surface.
• the contact times with the respective aqueous compositions are not critical to the process according to the invention, but should preferably be selected in step i) such that the coating weight of the uncured but firmly adhering organic coating applied in step (i) of the process according to the invention is immediately before Reaction rinse with the acidic aqueous composition (B) in step (ii) is preferably at least 10 g / m 2 , more preferably at least 20 g / m 2 , but preferably not more than 80 g / m 2 .
• the layer weight of the uncured but firmly adhering organic coating is determined after rinsing the metal substrate coated in step i) of the process according to the invention under flowing deionized water, wherein the rinsing is carried out until the rinse water draining from the metal substrate is apparently clear.
• the contact times for the reaction rinse with the acidic aqueous composition (B) to be carried out in step (ii) of the process according to the invention are preferably 50-100% of the contact time with the aqueous phase (A) in step (i).
• the organic coating applied to the metal surface in step (i) and post-treated in step (ii) is preferably cured at elevated temperature with or without an intermediate rinse step to remove components of the acidic aqueous composition (B) from the treated metal surface to form the polymeric coating to crosslink as completely and sustainably as possible and thus to increase the corrosion resistance.
• the process of curing the organic coating is preferably carried out at temperatures above the curing temperature of the binder system dispersed in the aqueous phase (A) and below 300 ° C.
• the present invention also encompasses the metallic component produced in the method according to the invention, wherein the component is preferably made at least partially from steel, iron, zinc and / or aluminum and their alloys.
• Such an inventive component is used in the automotive industry and in the construction sector and for the production of household appliances and electronic housings.
• step ii) of the process according to the invention which improves the corrosion resistance of the coated metal substrate, will be explained below by way of example for specific organic binder systems which are applied to the steel surfaces by the autodepositing method.
• the CRS sheets were degreased with a strong alkaline cleaner (3 wt .-% ACL ® 1773, 0.3 wt .-% ACL ® 1773T, Fa. Henkel) for 7 minutes and then cleaned with city and deionized water ,
• the sheets are then immersed for 2 minutes in the respective self-depositing bath for application of the organic coating (step i), then rinsed for one minute under running demineralised water and in step (ii) for one minute in a reaction rinse (ARR ® E2, Fa. Henkel KGaA) and rinsed again with deionised water.
• the coated panels were filmed and cured in a subsequent step in a convection oven.
• the layer thickness was both process of this invention and in the comparative experiments after curing approximately 20 .mu.m and was purified by PosiTector ® (Fa. DeFelsco Corp.). Subsequently, the corrosion resistance of the thus coated and treated steel sheets was quantified on the basis of the infiltration in the NSS test according to DIN 50021. The results for this are listed in Table 1.
• the organic coatings applied to the steel surface in the autophoretic process from aqueous self-depositing dispersions of the particular binder system in step (i) are all based on a polymer mixture of epoxy resin (EEW: 500-575 g / eq, Mn: 1200 g / mol DER ® 664 UE, Dow Chemicals) and polyacrylates, wherein in addition an amount of a curing agent is contained such that the weight ratio of epoxy resin to hardener is 70:30 each.
• the organic solids content of the aqueous dispersions is about 4 wt .-% and the proportion of the epoxy resin in the solids content at about 45 wt .-%.
• aqueous phase 0.14% by weight of iron (III) fluoride, 0.05% by weight of hydrogen fluoride and 2.1% by weight of hydrogen peroxide are contained in the aqueous phase for the autodeposition of the binder system.
• the component of the organic binder system in the aqueous phase (A) (Ashland-Südchemie-core-4,4 'isopropylidenediphenol, GP-Phenolic Resin ® BKS 7550, Fa.),
• an isocyanate resin is either a phenolic resin ( Vestagon ® B1530, Fa. Evonik) (used see Table 1).
• Table 1 shows the corrosive infiltration after 504 hours NSS test for the respective applied and cured organic coating on steel sheet applied in the previously described method. It turns out that even small amounts of copper ions in the acidic aqueous composition (B) in the process according to the invention bring about a significant improvement in the underflow values, as becomes clear from the comparison of Examples V1-B1, V2-B6 and V3-B10. Especially at high Zr contents in the acidic aqueous composition, the addition of copper ions is advantageous for the corrosion resistance of the steel surfaces provided with the cured organic coating.
• Examples Hardener in the binder system of the aqueous phase (A) Acid composition (B), pH 4 Neutral Salt Spray Test * infiltration / mm Zr 1 / ppm Cu 2 / ppm V1 Isocyanate resin 400 - 5.0 V2 phenolic resin 400 - 4.5 V3 phenolic resin 1200 - 6.0 B1 Isocyanate resin 400 5 3.5 B2 Isocyanate resin 400 10 3.0 B3 Isocyanate resin 400 20 3.5 B4 Isocyanate resin 400 50 4.0 V B5 Isocyanate resin 400 120 5.5 B6 phenolic resin 400 3 3.0 B7 phenolic resin 400 5 3.0 B8 phenolic resin 400 10 3.0 B9 phenolic resin 400 20 4.0 B10 phenolic resin 1200 3 4.0 B11 phenolic resin 1200 5 4.0 B12 phenolic resin 1200 10 4.0 B13 phenolic resin 1200 20 4.0 * according to DIN 50021 1 as H 2 ZrF 6 2 as Cu (NO 3

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• 2009
  • 2009-09-10 DE DE102009029334A patent/DE102009029334A1/de not_active Ceased
• 2010
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  • 2010-08-10 MX MX2012003024A patent/MX344297B/es active IP Right Grant
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  • 2010-08-10 JP JP2012528292A patent/JP2013504687A/ja active Pending
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  • 2012-03-01 US US13/409,824 patent/US9403188B2/en not_active Expired - Fee Related

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