WO2024160509A1 - Rinçage de réaction durable dans un procédé de production de surfaces métalliques revêtues de manière organique - Google Patents

Rinçage de réaction durable dans un procédé de production de surfaces métalliques revêtues de manière organique Download PDF

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Publication number
WO2024160509A1
WO2024160509A1 PCT/EP2024/050619 EP2024050619W WO2024160509A1 WO 2024160509 A1 WO2024160509 A1 WO 2024160509A1 EP 2024050619 W EP2024050619 W EP 2024050619W WO 2024160509 A1 WO2024160509 A1 WO 2024160509A1
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Prior art keywords
process according
particularly preferably
metal surface
inositol
aqueous composition
Prior art date
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PCT/EP2024/050619
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German (de)
English (en)
Inventor
Ulrich Dawidowski
Nicole Auweiler
Original Assignee
Henkel Ag & Co. Kgaa
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Publication of WO2024160509A1 publication Critical patent/WO2024160509A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the present invention relates to an at least two-stage process for the corrosion-protective treatment of metal surfaces, in which in a first step (i) an organic coating made of an aqueous phase (A) is applied to the metal surface and in a subsequent step (ii) the organic coating applied to the metal surface is brought into contact with an acidic aqueous composition (B) which contains at least one or more polyphosphoric acid esters of inositol and optionally at least one depolarizer.
  • the present invention furthermore comprises a metallic component which is made at least partially from 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 of the same in automobile construction and in the construction sector as well as for the manufacture of household appliances and electronic housings.
  • the automotive industry primarily uses dip painting, in which the body shells that have been pre-treated to protect against corrosion are placed in a dip tank containing a dispersed paint system in a continuous process, with the paint being deposited either by applying an external voltage (electrodecoating) or self-depositing through mere contact with the metal surfaces (autophoretic dip painting). The body shell is then heat treated so that the paint system deposited on the metal surface forms a film and crosslinks, which ensures a high level of corrosion protection and allows the subsequent application of further coatings.
  • dip painting in which the body shells that have been pre-treated to protect against corrosion are placed in a dip tank containing a dispersed paint system in a continuous process, with the paint being deposited either by applying an external voltage (electrodecoating) or self-depositing through mere contact with the metal surfaces (autophoretic dip painting).
  • the body shell is then heat treated so that the paint system deposited on the metal surface forms a film and crosslinks, which ensures a high level of corrosion
  • Autophoretic baths are used for the organic coating of metallic surfaces, mostly iron surfaces, as a corrosion-protective primer coating of metallic components or as an adhesive intermediate layer in the production of metal-elastomer compounds, for example for vibration-damping components in the automotive industry.
  • Autophoretic coating is therefore a dip coating which, in contrast to electrocoating, is carried out without external current, i.e. without the Application of an external voltage source.
  • the self-depositing compositions are mostly aqueous dispersions of organic resins or polymers which, upon contact with the metallic surface, coagulate in a thin liquid layer directly on the surface of the component due to the removal of metal cations by pickling, thus causing the layer to build up.
  • the prior art proposes an aqueous reaction rinse following the initial organic coating with the dip paint.
  • such a reaction rinse corresponds to a passivating post-treatment of the uncrosslinked coating and causes an inorganic conversion of free metal surface at so-called micro-defects, for example with the help of phosphate-containing solutions, which can also contain alkali and/or alkaline earth metal cations and also transition metal cations and their fluorocomplexes.
  • WO 02/42008 A1 discloses that water-soluble salts of metals from groups Ila and IIb, preferably zinc salts, are used for a reaction rinse, wherein soluble phosphates and so-called accelerators, which have an oxidative effect, are additionally to be contained in the reaction rinse.
  • reaction rinses are known which are based on water-soluble calcium salts, primarily nitrates, or on fluoro complexes of the element Zr. These reaction rinses also have the disadvantage that compounds are used which are extracted from mined ores.
  • the object of the present invention is to establish a process for the reaction rinse of freshly deposited, curable organic binder systems on metal surfaces, in which the reaction rinse is essentially based on renewable raw materials and in particular the use of phosphoric acid and soluble phosphates can be dispensed with, without, however, having to accept losses with regard to the achieved corrosion resistance of the metal surface protected with the cured organic binder system.
  • the object is achieved by means of a multi-stage process for the corrosion-protective treatment of metal surfaces, in which in a first step (i) an organic coating from an aqueous phase (A) is applied to the metal surface, wherein the metal surface having the organic coating is brought into contact in a subsequent step (ii) with an acidic aqueous composition (B) which contains at least one or more polyphosphoric acid esters of inositol.
  • the metal surface which is provided with an organic coating in a first step (i) can represent a free metal surface which is freed of organic contaminants in a cleaning and/or pickling step preceding the method according to the invention.
  • a free metal surface is characterized by the fact that it is largely free of organic contaminants, for example anti-corrosive oils, and that there is no or only an ultra-thin oxidic covering layer on its surface, which consists mainly of metallic elements of the metal substrate and has a layer thickness of only a few nanometers.
  • a metal surface is largely free of organic contaminants if the surface has a carbon coating of less than 0.10 g of carbon per square meter of said surface after cleaning and degreasing.
  • the carbon coating can be determined by means of pyrolytic decomposition.
  • the substrate is placed in a Oxygen atmosphere is brought to 550°C substrate temperature (PMT) and the amount of carbon dioxide released is quantitatively recorded as the amount of carbon using an infrared sensor, for example using the LECO® RC-412 Multiphase Carbon Determinator analyzer (Leco Corp.).
  • metal surfaces according to the invention can also be surfaces which have undergone a conversion treatment prior to the process step (i) according to the invention, during which an inorganic covering layer was formed.
  • inorganic conversion layers can consist of both metallic elements of the metal substrate and foreign metals.
  • Typical conversion coatings are formed when free metal surfaces come into contact with acidic aqueous solutions which contain water-soluble compounds of the elements Zr, Ti, Si, Hf, V, Ce, Mo, Zn, Mn, Fe and optionally additionally poorly soluble salt-forming anions such as phosphates and/or complexing anions such as fluoride ions.
  • amorphous or crystalline inorganic covering layers are formed on the metal surface, whereby metal surfaces are still in accordance with the invention and can be used for the process according to the invention if the area-related layer weight of the inorganic covering layers is not more than 3 g/m 2 .
  • An organic coating which is applied to the metal surface in the first process step (i) is in accordance with the invention if it contains a curable organic binder system.
  • the process step (i) according to the invention only comprises 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 are, for example, the heat treatment (thermal curing) or the actinic irradiation (radiation curing) of an organic coating applied in step (i) which contains the curable binder system.
  • the process step (i) optionally comprises a heat treatment of the metal surface treated with the aqueous phase (A) to evaporate some of the water which remains in the wet film on the treated metal surface, although the heat treatment was carried out below the curing temperature of the organic binder system.
  • the organic coating which was applied from the aqueous phase (A) therefore also contains some water.
  • the organic coating can contain leveling agents, surfactants, Corrosion inhibitors, salts, pigments and other active ingredients and auxiliary substances known to those skilled in the art of paint technology.
  • the solids content of the organic coating is at least 20% by weight.
  • the organic coating is understood to be that part of a wet film of the aqueous phase (A) containing a curable organic binder system applied in step (i) which remains on the metal surface as an adhering film containing the curable organic binder system after a rinsing step immediately following step (i), usually after three immersions in deionized water (K ⁇ 1pScm -1 ) with subsequent complete immersion in each case.
  • the organic coating is deposited in step (i) of the process according to the invention from an aqueous phase (A).
  • the type of deposition is not tied to specific technical measures and can be carried out by electrocoating the metal surface or by electroless processes such as autophoretic deposition and the mechanical application processes known in the prior art (roller application process, spray process).
  • the process according to the invention shows the most significant improvement in the corrosion resistance of the metal surfaces treated in the process according to the invention, particularly in the case of electroless deposition of the organic coating in process step (i) from an aqueous phase (A). Accordingly, those processes according to the invention are preferred in which the organic coating is applied in the first step (i) without the use of external current, in particular autophoretically, by bringing the metallic surface into contact with an aqueous phase (A) containing the organic binder.
  • the aqueous phase (A) preferably has a pH of less than 4 and preferably contains a) at least one dispersed organic binder system which is thermally curable, preferably at temperatures below 300 °C, preferably below 200 °C, b) iron(III) ions and c) fluoride ions in such a proportion that the molar ratio of fluoride ions to iron(III) ions from water-soluble compounds is at least 2:1.
  • the aqueous phase (A) in step (i) of the process according to the invention preferably contains at least 1 wt.% of the organic binder system.
  • Thermally curable organic binder systems are those binder systems that have curing temperatures above 20 °C and below the specified 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 exothermic heat quantity released by the sample volume of the solid mixture and recorded by DSC is carried out in accordance with DIN 53 765, taking into account DIN EN ISO 11357-1.
  • a solid mixture of the organic binder system used is accessible by vacuum freeze-drying 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 weight of solid mixture in the sample crucible can be determined by differential weighing.
  • the aqueous phase (A) is particularly suitable as an aqueous dispersion.
  • Thermally crosslinkable or curable organic binder systems according to component a) of the aqueous phase (A), which are applied to the metal surface in step (i) of a preferred process according to the invention without external current by autophoretic deposition, consist of organic oligomeric or polymeric compounds with at least two functional groups and are therefore able to react with one another in condensation or addition reactions to form covalent bonds and thereby build 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 with two different or identical functional groups for the reaction functional groups that are capable of interacting with one another or at least two different oligomeric or polymeric compounds that crosslink with one another due to their functionalization.
  • the organic binder system according to component a) dispersed in water, which is applied to the metal surface without external current in step (i) of a process preferred 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 resin and an organic hardener which can react with the crosslinkable functionalities of the organic polymer or resin in an addition or condensation reaction.
  • the organic hardener can also be an organic polymer or resin.
  • the organic binder system dispersed in the aqueous phase (A) in step (i) of the process according to the invention has a film formation temperature of not more than 80 °C, particularly preferably not more than 40 °C. If the film formation 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 can result, which cannot be cured even in the curing process that usually follows the process according to the invention. Such an inhomogeneous coating of the metal surface with the organic binder system has a detrimental effect on the corrosion resistance and the visual impression 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 processes according to the invention are preferred in which the acidic aqueous composition (B) in step (ii) is brought into contact with the metal surface having the organic coating at a temperature of at least 30 °C, particularly preferably at least 40 °C, but preferably not more than 80 °C.
  • the dispersed organic binder system used in step (i) of the process preferred according to the invention for electroless deposition preferably consists from at least one copolymer and/or polymer mixture of acrylates with at least one oligomeric and/or polymeric compound selected from epoxy resins, phenolic resins and/or polyurethane resins.
  • Water-dispersible epoxy resins as a cross-linked coating on a metal surface, provide a particularly good barrier effect against corrosive media and are therefore a preferred component of the dispersed binder system in a process preferred according to the invention, in which in step (i) the organic coating is applied without external current, i.e. via a self-deposition process.
  • cross-linking hardeners preferably at least partially based on phenolic resins, can be used in addition to the epoxy resin in order to accelerate the curing process and increase the degree of cross-linking.
  • Other hardeners that cross-link the epoxy resin are those based on isocyanate resins, the isocyanate groups of which can also be blocked.
  • Moderately reactive isocyanates are preferred as preferred blocked isocyanate resins, for example aliphatic isocyanates and sterically hindered and/or acid-stable blocked isocyanates.
  • bisphenol A-based epoxy resins are preferably used in the present invention, which correspond to the following general structural formula (III):
  • the structural component A corresponds to the following general formula (IV): with n as an integer from 1 to 50.
  • Preferred epoxides 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 molar equivalent (g/eq).
  • Incompletely crosslinked oligomers or polymeric polycondensation products of formaldehydes with phenols which preferably have at least partially etherified hydroxyl groups and whose preferred average molecular mass is not less than 500 u and not greater than 10,000 u, can be dispersed as phenol resins in the aqueous phase (A) in step (i) of the preferred process according to the invention for the electroless deposition of the organic coating.
  • the hydroxyl groups are preferably methoxylated, ethoxylated, propoxylated, butoxylated or ethenyloxylated.
  • Both resoles and novolaks can be used as phenolic resin types.
  • aqueous phase (A) which, upon contact with metal surfaces, cause an autophoretic deposition of an organic coating within the meaning of this invention are leveling agents, such as glycol ethers and alcohol esters, for better film formation of the deposited organic coating on the metallic surface, micronized inorganic fillers such as sulfates, oxides and phosphates with average particle sizes below 5 pm, preferably below 1 pm, for increasing the scratch resistance and corrosion resistance of the organic coating in the cured state, and pigments for coloring, for example carbon black or titanium dioxide.
  • leveling agents such as glycol ethers and alcohol esters, for better film formation of the deposited organic coating on the metallic surface
  • micronized inorganic fillers such as sulfates, oxides and phosphates with average particle sizes below 5 pm, preferably below 1 pm, for increasing the scratch resistance and corrosion resistance of the organic coating in the cured state
  • pigments for coloring for example carbon black or titanium dioxide.
  • composition (B) of the reaction rinse in step (ii) of the process according to the invention it applies firstly that the polyphosphoric acid esters necessarily contained as an adequate phosphoric acid substitute each comprise both the acid form and the corresponding water-soluble salts of the polyphosphoric acid esters, in particular the sodium salts.
  • the polyphosphoric acid esters of inositol comprise at least one polyphosphoric acid ester of myo-inositol and particularly preferably at least one tri-, tetra-, penta- and/or hexaphosphoric acid ester of myo-inositol.
  • phytic acid is particularly preferred as a polyphosphoric acid ester of inositol.
  • step (ii) preference is given to those acidic aqueous compositions (B) in which the proportion of polyphosphoric acid esters of myo-inositol, preferably of tri-, tetra-, penta- and/or hexaphosphoric acid esters of myo-inositol, particularly preferably of phytic acid, in each case calculated as CeH ⁇ Oe and based on the total proportion of polyphosphoric acid esters of inositol, is at least 40% by weight, particularly preferably at least 60% by weight and very particularly preferably at least 80% by weight.
  • the acidic aqueous composition in step (ii) of the process according to the invention contains a total of at least 0.5 g/kg, preferably at least 1.0 g/kg, particularly preferably at least 2.0 g/kg, very particularly preferably at least 5.0 g/kg, but preferably not more than 100.0 g/kg, particularly preferably not more than 50.0 g/kg, especially preferably not more than 30.0 g/kg and very particularly preferably not more than 10.0 g/kg of polyphosphoric acid esters of inositol.
  • the proportion of polyphosphoric acid esters of inositol is significantly below 1.0 g/kg, the healing of defects in the organic coating deposited from the aqueous phase is often inadequate.
  • the property of the reaction rinse to improve the corrosion resistance of the metal surface provided with the cured organic binder system is comparable to reaction rinses based on phosphoric acid or fluorozirconic acid established in the state of the art.
  • the reaction rinse to be carried out in step (ii) of the process according to the invention by bringing the metal surface having the organic coating into contact is preferably carried out at a pH of the acidic aqueous composition (B) of not less than 2.0, particularly preferably not less than 2.5, very particularly preferably not less than 3.0, but preferably not greater than 6.0, particularly preferably not greater than 5.5, especially preferably not greater than 5.0 and very particularly preferably not greater than 4.5.
  • a pH of the acidic aqueous composition (B) of not less than 2.0, particularly preferably not less than 2.5, very particularly preferably not less than 3.0, but preferably not greater than 6.0, particularly preferably not greater than 5.5, especially preferably not greater than 5.0 and very particularly preferably not greater than 4.5.
  • lower pH values can chemically change the organic coating and initiate decomposition reactions.
  • increased acid corrosion of the metallic substrate and the formation of nascent hydrogen can cause lasting damage to the interface between the metal and the organic coating.
  • the acidic compositions used in step (ii) of the process according to the invention can additionally contain so-called depolarizers which, due to their mild oxidation effect, prevent the formation of nascent hydrogen on the free metal surface during the reaction rinse.
  • 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-nitrobenzene sulfonate ions, m-nitrobenzoate ions, p-nitrophenol, N-methylmorpholine-N-oxide, nitroguanidine.
  • the proportion of depolarizers is preferably at least 1 g/kg, particularly preferably at least 2 g/kg, but preferably not more than 20 g/kg based on the acidic aqueous composition in process step (ii).
  • the presence of fluoride ions in the acidic aqueous composition (B) can have a detrimental effect on corrosion protection, so that the proportion of fluoride ions in the composition (B) preferably assumes values for which the measured free fluoride content is less than 40 mg/kg, particularly preferably less than 20 mg/kg. particularly preferably less than 10 mg/kg and most preferably less than 1.0 mg/kg.
  • the free fluoride content is determined potentiometrically in the acidic aqueous composition (B) at 20°C using fluoride-sensitive glass electrodes after calibration with suitable standard solutions.
  • a composition (B) in the reaction rinse i.e. in step (ii) of the process according to the invention, contains a total of less than 100 mg/kg, particularly preferably a total of less than 10 mg/kg, very particularly preferably a total of less than 1 mg of phosphoric acid and soluble phosphates calculated as PO4.
  • the present invention is also characterized by the fact that the presence of phosphoric acid and soluble phosphates in step (ii) of the process can be dispensed with and yet good corrosion resistance of the metal substrates treated according to the invention results.
  • reaction rinse in process step (ii) is preferably substantially free of chromium-containing compounds, so that the acidic aqueous composition (B) contains a total of less than 10 mg/kg, particularly preferably less than 1 mg/kg of chromium-containing compounds calculated as Cr and very preferably contains no chromium-containing compounds at all or no such compounds are actively added to the composition (B).
  • the aqueous phase (A) in step (i) and the acidic aqueous composition in step (ii) are brought into contact with the metallic substrate or the metallic component preferably by dipping or spraying, the dipping process being particularly preferred due to the more homogeneous wetting of the surface.
  • a rinsing step for removing components of the aqueous phase (A) from the treated metal surface. This measure also increases the effectiveness of the reaction rinse with the acidic aqueous composition (B), since polymer particles that are not or only insufficiently adhering to the metal surface are removed, so that the acidic aqueous composition can act directly on firmly adhering organic coating.
  • the contact times with the respective aqueous compositions are not critical for the process according to the invention, but should preferably be selected in step i) such that the layer weight of the uncured but firmly adhering organic coating applied in step (i) of the process according to the invention immediately before the reaction rinse with the acidic aqueous composition (B) in step (ii) is preferably at least 10 g/m 2 , particularly preferably at least 20 g/m 2 , but preferably not more than 80 g/m 2 .
  • lower layer weights lead to non-homogeneous coatings which impart lower corrosion resistance to the metal surface, while higher layer weights do not significantly improve the corrosion resistance of the coated metal substrate.
  • 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 running deionized water, the rinsing being carried out until the rinsing water flowing off the metal substrate is apparently clear.
  • the contact times for the reaction rinse to be carried out in step (ii) of the process according to the invention with the acidic aqueous composition (B) 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 rinsing step to remove components of the acidic aqueous composition (B) from the treated metal surface in order to crosslink the polymer coating as completely and sustainably as possible and thus 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 process according to the invention, wherein the component is preferably made at least partially from steel, iron, zinc and/or aluminum and their alloys, preferably at least partially from iron and/or steel.
  • Such a component according to the invention is used in automobile manufacturing and in the construction sector as well as for the manufacture of household appliances and electronic housings.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un procédé en au moins deux étapes pour le traitement de protection contre la corrosion de surfaces métalliques, selon lequel, dans une première étape (i), un revêtement organique constitué d'une phase aqueuse (A) est appliqué sur la surface métallique et, dans une étape suivante (ii), le revêtement organique appliqué sur la surface métallique est mis en contact avec une composition aqueuse acide (B) comprenant au moins un ou plusieurs esters d'acide polyphosphorique d'inositol et éventuellement au moins un dépolariseur. L'invention concerne en outre un composant métallique, qui est réalisé au moins en partie en acier, en fer, en zinc et/ou en aluminium et leurs alliages, et qui a été traité par le procédé selon l'invention. et son utilisation dans la construction automobile et dans le secteur du bâtiment, ainsi que pour la fabrication d'appareils domestiques et de boîtiers électroniques.
PCT/EP2024/050619 2023-01-30 2024-01-11 Rinçage de réaction durable dans un procédé de production de surfaces métalliques revêtues de manière organique WO2024160509A1 (fr)

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DE102023200702.9 2023-01-30
DE102023200702.9A DE102023200702A1 (de) 2023-01-30 2023-01-30 Nachhaltige Reaktionsspüle in einem Verfahren zur Bereitstellung organisch beschichteter Metalloberflächen

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Citations (10)

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US20020076498A1 (en) 1999-05-21 2002-06-20 Zhiqi Yang Autodeposition post-bath rinse process
DE102007059969A1 (de) 2007-12-11 2009-06-18 Henkel Ag & Co. Kgaa Stabile wässrige Epoxid-Harz Dispersion enthaltend Phenolharze zur autophoretischen Beschichtung von Metallen
US20140223740A1 (en) * 2011-09-21 2014-08-14 Nippon Paint Co., Ltd. Method for treating surface of aluminum heat exchanger
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